Formation of secondary organic aerosol from isoprene oxidation over Europe

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M. Karl

2009-09-01

Full Text Available The role of isoprene as a precursor to secondary organic aerosol (SOA over Europe is studied with the two-way nested global chemistry transport model TM5. The inclusion of the formation of SOA from isoprene oxidation in our model almost doubles the atmospheric burden of SOA over Europe compared to SOA formation from terpenes and aromatics. The reference simulation, which considers SOA formation from isoprene, terpenes and aromatics, predicts a yearly European production rate of 1.0 Tg SOA yr⁻¹ and an annual averaged atmospheric burden of about 50 Gg SOA over Europe. A fraction of 35% of the SOA produced in the boundary layer over Europe is transported to higher altitudes or to other world regions. Summertime measurements of organic matter (OM during the extensive EMEP OC/EC campaign 2002/2003 are better reproduced when SOA formation from isoprene is taken into account, reflecting also the strong seasonality of isoprene and other biogenic volatile organic compounds (BVOC emissions from vegetation. However, during winter, our model strongly underestimates OM, likely caused by missing wood burning in the emission inventories. Uncertainties in the parameterisation of isoprene SOA formation have been investigated. Maximum SOA production is found for irreversible sticking (non-equilibrium partitioning of condensable vapours on particles, with tropospheric SOA production over Europe increased by a factor of 4 in summer compared to the reference case. Completely neglecting SOA formation from isoprene results in the lowest estimate (0.51 Tg SOA yr⁻¹. The amount and the nature of the absorbing matter are shown to be another key uncertainty when predicting SOA levels. Consequently, smog chamber experiments on SOA formation should be performed with different types of seed aerosols and without seed aerosols in order to derive an improved treatment of the absorption of SOA in the models. Consideration of a number of recent insights

Different roles of water in secondary organic aerosol formation from toluene and isoprene

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Jia, Long; Xu, YongFu

2018-06-01

Roles of water in the formation of secondary organic aerosol (SOA) from the irradiations of toluene-NO2 and isoprene-NO2 were investigated in a smog chamber. Experimental results show that the yield of SOA from toluene almost doubled as relative humidity increased from 5 to 85 %, whereas the yield of SOA from isoprene under humid conditions decreased by 2.6 times as compared to that under dry conditions. The distinct difference of RH effects on SOA formation from toluene and isoprene is well explained with our experiments and model simulations. The increased SOA from humid toluene-NO2 irradiations is mainly contributed by O-H-containing products such as polyalcohols formed from aqueous reactions. The major chemical components of SOA in isoprene-NO2 irradiations are oligomers formed from the gas phase. SOA formation from isoprene-NO2 irradiations is controlled by stable Criegee intermediates (SCIs) that are greatly influenced by water. As a result, high RH can obstruct the oligomerization reaction of SCIs to form SOA.

Isoprene photochemistry over the Amazon rainforest.

Science.gov (United States)

Liu, Yingjun; Brito, Joel; Dorris, Matthew R; Rivera-Rios, Jean C; Seco, Roger; Bates, Kelvin H; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N; Kim, Saewung; Goldstein, Allen H; Guenther, Alex B; Manzi, Antonio O; Souza, Rodrigo A F; Springston, Stephen R; Watson, Thomas B; McKinney, Karena A; Martin, Scot T

2016-05-31

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (Amazon rainforest.

VIIRS Marine Isoprene Product and Initial Applications

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Tong, D.; Wang, M.; Wang, B.; Pan, L.; Lee, P.; Goldberg, M.

2017-12-01

Isoprene is a reactive biogenic hydrocarbon that affects atmospheric chemistry, aerosol loading, and cloud formation. We have developed a marine isoprene emission algorithm based on ocean color data from the Visible Infrared Imaging Radiometer Suite (VIIRS) onboard the Suomi National Polar-orbiting Partnership (SNPP). and global meteorology simulated by NOAA Global Forecasting System (GFS). This algorithm is implemented to generate a multi-year data record (2012-2015) of marine isoprene. The product was validated using historic ocean observations of marine isoprene, as well as in-situ data collected during two recent cruises (SPACES/OASIS in 2014 and ASTRA-OMZ in 2015). Result shows that the VIIRS product has captured the seasonal and spatial variability of global oceanic isoprene emission, which is controlled by a myriad of biological and environmental variables including chlorophyll-a concentration, phytoplankton functional types, seawater light attenuation rate, wind speed, and sea surface temperature. The VIIRS isoprene emission displays considerable seasonal and spatial variations, with peaks in spring over seawater abundant with nutrient inputs. Year to year variations are small, with the annual global emissions ranging from 0.20 to 0.25 Tg C/yr. This new dataset provides the first multi-year observations of global isoprene emissions that can be used to study a variety of environmental issues such as coastal air quality, global aerosol, and cloud formation. Some "early-adopter" applications of this product are briefly discussed.

Timber resource of Missouri's Northwest Ozarks.

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W. Brad Smith

1990-01-01

In 1989 the fourth forest inventory of the Norwest Ozarks found 2.2 million acres of timberland, an increase of nearly 13% since 1972. This bulletin presents highlights and statistics on area, volume, growth, removals, and mortality.

Isoprene emission from tropical tree species

International Nuclear Information System (INIS)

Padhy, P.K.; Varshney, C.K.

2005-01-01

Foliar emission of isoprene was measured in nine commonly growing tree species of Delhi, India. Dynamic flow enclosure technique was used and gas samples were collected onto Tenax-GC/Carboseive cartridges, which were then attached to the sample injection system in the gas chromatograph (GC). Eluting compounds were analysed using a flame ionisation detector (FID). Out of the nine tree species, isoprene emission was found in six species (Eucalyptus sp., Ficus benghalensis, Ficus religiosa, Mangifera indica, Melia azedarach, and Syzygium jambolanum), whereas, in the remaining three tree species (Alstonia scholaris, Azadirachta indica, and Cassia fistula) no isoprene emission was detected or the levels of emission were negligible or below the detection limit (BDL). Among six tree species, the highest hourly emission (10.2±6.8 μg g -1 leaf dry weight, average of five seasons) was observed in Ficus religiosa, while minimum emission was from Melia azedarach (2.2±4.9 μg g -1 leaf dry weight, average of five seasons). Isoprene emission (average of six species), over five seasons, was found to vary between 3.9 and 8.5 μg g -1 leaf dry weight during the rainy season. In addition, significant diurnal variation in isoprene emission was observed in each species. The preliminary estimate made in this study on the annual biogenic VOC emission from India may probably be the first of its kind from this part of the world. - Isoprene flux (diurnal and seasonal) from some tropical tree species was estimated and a regional comparison was made

Isoprene emission from tropical tree species

Energy Technology Data Exchange (ETDEWEB)

Padhy, P.K. [School of Environmental Sciences, Jawaharlal Nehru University, New Delhi 110 067 (India)]. E-mail: padhypk2003@yahoo.com; Varshney, C.K. [School of Environmental Sciences, Jawaharlal Nehru University, New Delhi 110 067 (India)

2005-05-01

Foliar emission of isoprene was measured in nine commonly growing tree species of Delhi, India. Dynamic flow enclosure technique was used and gas samples were collected onto Tenax-GC/Carboseive cartridges, which were then attached to the sample injection system in the gas chromatograph (GC). Eluting compounds were analysed using a flame ionisation detector (FID). Out of the nine tree species, isoprene emission was found in six species (Eucalyptus sp., Ficus benghalensis, Ficus religiosa, Mangifera indica, Melia azedarach, and Syzygium jambolanum), whereas, in the remaining three tree species (Alstonia scholaris, Azadirachta indica, and Cassia fistula) no isoprene emission was detected or the levels of emission were negligible or below the detection limit (BDL). Among six tree species, the highest hourly emission (10.2{+-}6.8 {mu}g g{sup -1} leaf dry weight, average of five seasons) was observed in Ficus religiosa, while minimum emission was from Melia azedarach (2.2{+-}4.9 {mu}g g{sup -1} leaf dry weight, average of five seasons). Isoprene emission (average of six species), over five seasons, was found to vary between 3.9 and 8.5 {mu}g g{sup -1} leaf dry weight during the rainy season. In addition, significant diurnal variation in isoprene emission was observed in each species. The preliminary estimate made in this study on the annual biogenic VOC emission from India may probably be the first of its kind from this part of the world. - Isoprene flux (diurnal and seasonal) from some tropical tree species was estimated and a regional comparison was made.

Ecosystem-scale volatile organic compound fluxes during an extreme drought in a broadleaf temperate forest of the Missouri Ozarks (central USA)

Energy Technology Data Exchange (ETDEWEB)

Seco, Roger [Univ. of California, Irvine, CA (United States); Karl, Thomas [Univ. of Innsbruck (Austria); Guenther, Alex B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States); Hosman, Kevin P. [Univ. of Missouri, Columbia, MO (United States); Pallardy, Stephen G. [Univ. of Missouri, Columbia, MO (United States); Gu, Lianhong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Geron, Chris [U.S. Environmental Protection Agency, Research Triangle Park, NC (United States); Harley, Peter [National Center for Atmospheric Research, Boulder, CO (United States); Kim, Saewung [Univ. of California, Irvine, CA (United States)

2015-07-07

Considerable amounts and varieties of biogenic volatile organic compounds (BVOCs) are exchanged between vegeta-tion and the surrounding air. These BVOCs play key ecological and atmospheric roles that must be adequately repre-sented for accurately modeling the coupled biosphere–atmosphere–climate earth system. One key uncertainty in existing models is the response of BVOC fluxes to an important global change process: drought. We describe the diur-nal and seasonal variation in isoprene, monoterpene, and methanol fluxes from a temperate forest ecosystem before, during, and after an extreme 2012 drought event in the Ozark region of the central USA. BVOC fluxes were domi-nated by isoprene, which attained high emission rates of up to 35.4 mg m^-2h^-1 at midday. Methanol fluxes were characterized by net deposition in the morning, changing to a net emission flux through the rest of the daylight hours. Net flux of CO₂ reached its seasonal maximum approximately a month earlier than isoprenoid fluxes, which high-lights the differential response of photosynthesis and isoprenoid emissions to progressing drought conditions. Never-theless, both processes were strongly suppressed under extreme drought, although isoprene fluxes remained relatively high compared to reported fluxes from other ecosystems. Methanol exchange was less affected by drought throughout the season, conflrming the complex processes driving biogenic methanol fluxes. The fraction of daytime (7–17 h) assimilated carbon released back to the atmosphere combining the three BVOCs measured was 2% of gross primary productivity (GPP) and 4.9% of net ecosystem exchange (NEE) on average for our whole measurement cam-paign, while exceeding 5% of GPP and 10% of NEE just before the strongest drought phase. The _MEGANv2.1 model correctly predicted diurnal variations in fluxes driven mainly by light and temperature, although further research is needed to address model BVOC fluxes

Ground-based intercomparison of two isoprene measurement techniques

Directory of Open Access Journals (Sweden)

E. Leibrock

2003-01-01

Full Text Available An informal intercomparison of two isoprene (C5H8 measurement techniques was carried out during Fall of 1998 at a field site located approximately 3 km west of Boulder, Colorado, USA. A new chemical ionization mass spectrometric technique (CIMS was compared to a well-established gas chromatographic technique (GC. The CIMS technique utilized benzene cation chemistry to ionize isoprene. The isoprene levels measured by the CIMS were often larger than those obtained with the GC. The results indicate that the CIMS technique suffered from an anthropogenic interference associated with air masses from the Denver, CO metropolitan area as well as an additional interference occurring in clean conditions. However, the CIMS technique is also demonstrated to be sensitive and fast. Especially after introduction of a tandem mass spectrometric technique, it is therefore a candidate for isoprene measurements in remote environments near isoprene sources.

Isoprene biosynthesis in hybrid poplar impacts ozone tolerance

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Behnke, K.; Kleist, E.; Uerlings, R.; Wildt, J.; Rennenberg, H.; Schnitzler, J. P.

2009-04-01

Isoprene is the most abundant volatile compound emitted by vegetation. It influences air chemistry and is thought to take part in plant defense reactions against abiotic stress such as high temperature or ozone. However, whether or not isoprene emission interacts with ozone tolerance of plants is still in discussion. We exploited transgenic non-isoprene emitting Grey poplar (Populus x canescens) in a biochemical and physiological model study to investigate the effect of acute ozone stress on the elicitation of defense-related emissions of plant volatiles, photosynthesis and the antioxidative system. We recorded that non-isoprene emitting poplars are more resistant to ozone as indicated by less damaged leaf area and higher assimilation rates compared to ozone-exposed wild type plants. The integral of green leaf volatile (GLV) emissions was different between the two poplar phenotypes and a reliable early marker for subsequent leaf damage. For other stress-induced volatiles like mono-, homo-, and sesquiterpenes, and methyl salicylate similar time profiles, pattern and emission intensities were observed in both transgenic and wild type plants. However, un-stressed non-isoprene emitting poplars are characterized by elevated levels of ascorbate and α-tocopherol as well as a more effective de-epoxidation ratio of xanthophylls than in wild type plants. Since ozone quenching properties of ascorbate are much higher than those of isoprene and furthermore α-tocopherol also is an essential antioxidant, non-isoprene emitting poplars might benefit from changes within the antioxidative system by providing them with enhanced ozone tolerance.

Sensitivities in global scale modeling of isoprene

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R. von Kuhlmann

2004-01-01

Full Text Available A sensitivity study of the treatment of isoprene and related parameters in 3D atmospheric models was conducted using the global model of tropospheric chemistry MATCH-MPIC. A total of twelve sensitivity scenarios which can be grouped into four thematic categories were performed. These four categories consist of simulations with different chemical mechanisms, different assumptions concerning the deposition characteristics of intermediate products, assumptions concerning the nitrates from the oxidation of isoprene and variations of the source strengths. The largest differences in ozone compared to the reference simulation occured when a different isoprene oxidation scheme was used (up to 30-60% or about 10 nmol/mol. The largest differences in the abundance of peroxyacetylnitrate (PAN were found when the isoprene emission strength was reduced by 50% and in tests with increased or decreased efficiency of the deposition of intermediates. The deposition assumptions were also found to have a significant effect on the upper tropospheric HOx production. Different implicit assumptions about the loss of intermediate products were identified as a major reason for the deviations among the tested isoprene oxidation schemes. The total tropospheric burden of O3 calculated in the sensitivity runs is increased compared to the background methane chemistry by 26±9  Tg( O3 from 273 to an average from the sensitivity runs of 299 Tg(O3. % revised Thus, there is a spread of ± 35% of the overall effect of isoprene in the model among the tested scenarios. This range of uncertainty and the much larger local deviations found in the test runs suggest that the treatment of isoprene in global models can only be seen as a first order estimate at present, and points towards specific processes in need of focused future work.

Diurnal Variation in the Basal Emission Rate of Isoprene

Science.gov (United States)

Jennifer Funk; Clive G. Jones; Christine J. Baker; Heather M. Fuller; Christian P. Giardina; Manuel T. Lerdua

2003-01-01

Isoprene is emitted from numerous plant species and profoundly influences tropospheric chemistry. Due to the short lifetime of isoprene in the atmosphere, developing an understanding of emission patterns at small time scales is essential for modeling regional atmospheric chemistry processes. Previous studies suggest that diurnal fluctuations in isoprene emission may be...

Circadian control of isoprene emissions from oil palm (Elaeis guineensis).

Science.gov (United States)

Wilkinson, Michael J; Owen, Susan M; Possell, Malcolm; Hartwell, James; Gould, Peter; Hall, Anthony; Vickers, Claudia; Nicholas Hewitt, C

2006-09-01

The emission of isoprene from the biosphere to the atmosphere has a profound effect on the Earth's atmospheric system. Until now, it has been assumed that the primary short-term controls on isoprene emission are photosynthetically active radiation and temperature. Here we show that isoprene emissions from a tropical tree (oil palm, Elaeis guineensis) are under strong circadian control, and that the circadian clock is potentially able to gate light-induced isoprene emissions. These rhythms are robustly temperature compensated with isoprene emissions still under circadian control at 38 degrees C. This is well beyond the acknowledged temperature range of all previously described circadian phenomena in plants. Furthermore, rhythmic expression of LHY/CCA1, a genetic component of the central clock in Arabidopsis thaliana, is still maintained at these elevated temperatures in oil palm. Maintenance of the CCA1/LHY-TOC1 molecular oscillator at these temperatures in oil palm allows for the possibility that this system is involved in the control of isoprene emission rhythms. This study contradicts the accepted theory that isoprene emissions are primarily light-induced.

Effect of temperature on postillumination isoprene emission in oak and poplar.

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Li, Ziru; Ratliff, Ellen A; Sharkey, Thomas D

2011-02-01

Isoprene emission from broadleaf trees is highly temperature dependent, accounts for much of the hydrocarbon emission from plants, and has a profound effect on atmospheric chemistry. We studied the temperature response of postillumination isoprene emission in oak (Quercus robur) and poplar (Populus deltoides) leaves in order to understand the regulation of isoprene emission. Upon darkening a leaf, isoprene emission fell nearly to zero but then increased for several minutes before falling back to nearly zero. Time of appearance of this burst of isoprene was highly temperature dependent, occurring sooner at higher temperatures. We hypothesize that this burst represents an intermediate pool of metabolites, probably early metabolites in the methylerythritol 4-phosphate pathway, accumulated upstream of dimethylallyl diphosphate (DMADP). The amount of this early metabolite(s) averaged 2.9 times the amount of plastidic DMADP. DMADP increased with temperature up to 35°C before starting to decrease; in contrast, the isoprene synthase rate constant increased up to 40°C, the highest temperature at which it could be assessed. During a rapid temperature switch from 30°C to 40°C, isoprene emission increased transiently. It was found that an increase in isoprene synthase activity is primarily responsible for this transient increase in emission levels, while DMADP level stayed constant during the switch. One hour after switching to 40°C, the amount of DMADP fell but the rate constant for isoprene synthase remained constant, indicating that the high temperature falloff in isoprene emission results from a reduction in the supply of DMADP rather than from changes in isoprene synthase activity.

Potential controls of isoprene in the surface ocean

Science.gov (United States)

Hackenberg, S. C.; Andrews, S. J.; Airs, R.; Arnold, S. R.; Bouman, H. A.; Brewin, R. J. W.; Chance, R. J.; Cummings, D.; Dall'Olmo, G.; Lewis, A. C.; Minaeian, J. K.; Reifel, K. M.; Small, A.; Tarran, G. A.; Tilstone, G. H.; Carpenter, L. J.

2017-04-01

Isoprene surface ocean concentrations and vertical distribution, atmospheric mixing ratios, and calculated sea-to-air fluxes spanning approximately 125° of latitude (80°N-45°S) over the Arctic and Atlantic Oceans are reported. Oceanic isoprene concentrations were associated with a number of concurrently monitored biological variables including chlorophyll a (Chl a), photoprotective pigments, integrated primary production (intPP), and cyanobacterial cell counts, with higher isoprene concentrations relative to all respective variables found at sea surface temperatures greater than 20°C. The correlation between isoprene and the sum of photoprotective carotenoids, which is reported here for the first time, was the most consistent across all cruises. Parameterizations based on linear regression analyses of these relationships perform well for Arctic and Atlantic data, producing a better fit to observations than an existing Chl a-based parameterization. Global extrapolation of isoprene surface water concentrations using satellite-derived Chl a and intPP reproduced general trends in the in situ data and absolute values within a factor of 2 between 60% and 85%, depending on the data set and algorithm used.

Progress Report: DE-FG03-97ER20274, ''Microbial Production of Isoprene''

International Nuclear Information System (INIS)

Ray Fall

2002-01-01

We have discovered that microorganisms produce and emit the hydrocarbon isoprene (2-methyl-1,3-butadiene), and have suggested that if isoprene-producing enzymes and their genes can be harnessed, useful hydrocarbon-producing systems might be constructed. The main goal of the proposed work is to establish the biochemical mechanism and regulation of isoprene formation in the bacterial system, Bacillus subtilis. Specific objectives of the proposed work are the following: (A) to characterize the physiological regulation of isoprene formation in B. subtilis; (B) to characterize mutations in B. subtilis 168 that suppress isoprene formation, clone these genes, and determine how isoprene and isoprenoid carbon flow are regulated; and (C) to test ''overflow'' and ''signaling'' models for Bacillus isoprene formation. We are also pursuing the isolation and cloning of B. subtilis isoprene synthase, which we believe may be a regulatory enzyme

Large Drought-induced Variations in Oak Leaf Volatile Organic Compound Emissions during PINOT NOIR 2012

Data.gov (United States)

U.S. Environmental Protection Agency — Leaf level oak isoprene emissions and co2/H2O exchange in the Ozarks, USA BAGeron.csv is the speciated biomass displayed in Figure 1. Biomass Dry Weights.xlsx is...

Reconciling functions and evolution of isoprene emission in higher plants.

Science.gov (United States)

Loreto, Francesco; Fineschi, Silvia

2015-04-01

Compilation and analysis of existing inventories reveal that isoprene is emitted by c. 20% of the perennial vegetation of tropical and temperate regions of the world. Isoprene emitters are found across different plant families without any clear phylogenetic thread. However, by critically appraising information in inventories, several ecological patterns of isoprene emission can be highlighted, including absence of emission from C4 and annual plants, and widespread emission from perennial and deciduous plants of temperate environments. Based on this analysis, and on available information on biochemistry, ecology and functional roles of isoprene, it is suggested that isoprene may not have evolved to help plants face heavy or prolonged stresses, but rather assists C3 plants to run efficient photosynthesis and to overcome transient and mild stresses, especially during periods of active plant growth in warm seasons. When the stress status persists, or when evergreen leaves cope with multiple and repeated stresses, isoprene biosynthesis is replaced by the synthesis of less volatile secondary compounds, in part produced by the same biochemical pathway, thus indicating causal determinism in the evolution of isoprene-emitting plants in response to the environment. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

Impact of isoprene and nitrogen oxides on O3 chemistry at the local and the regional scale : the ESCOMPTE experiment

Science.gov (United States)

Cortinovis, J.; Solmon, F.; Personne, E.; Serça, D.; Rosset, R.

2003-04-01

Concentrations of nitrogen oxides (NOx = NO+NO2) and volatile organic compounds (VOCs) play a crucial role in the atmospheric chemistry through the production-destruction of tropospheric O3. In rural areas, NOx concentrations are much lower than in urban areas, whereas VOCs emissions can be relatively high. This is due to a relative longer residence time of VOCs, and to the substantial contribution of Biogenic VOCs (BVOCs) representing more than 85% of all the VOCs emitted at the Earth surface (half of it being isoprene). For these reasons, O3 production in rural areas is most of the time NOx-limited. Taking into account biogenic emissions of isoprene in global scale atmospheric chemistry modeling adds from 10 to 40% to the ozone produced when compared to the same simulation without isoprene. This suggests that BVOCs and NOx emissions must be accounted for in models of atmospheric pollution forecasting at local and regional scales. In this study, we present a sensitivity analysis on the impact of the isoprene and nitrogen oxides emissions at the local and the regional scale. This study is done from data collected during the ESCOMPTE campaign which took place in June and July 2001 in the Marseille region (Southwest France) characterized by both strong natural and anthropogenic sources of trace gases. Isoprene emission experimental data from a Quercus Pubescens Mediterranean forest are used to constrain the 1Dz Soil-Vegetation-Atmospheric-Transfer ISBA model. This SVAT is used in the 3D MESO-NH-Chemistry model to simulate scenarios of pollution at the regional scale including the measured biogenic source for isoprene, and GENEMIS anthropogenic sources for other trace gases. To focus on the chemistry aspect of these simulations, the atmospheric dynamics are set to an "ideal" configuration. We have investigated the impact of the relative position and distance between the biogenic and anthropogenic sources on the O3 budget. According to this, and to the intensity of the

Isoprene emission and photosynthesis during heatwaves and drought in black locust

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Bamberger, Ines; Ruehr, Nadine K.; Schmitt, Michael; Gast, Andreas; Wohlfahrt, Georg; Arneth, Almut

2017-08-01

Extreme weather conditions like heatwaves and drought can substantially affect tree physiology and the emissions of isoprene. To date, however, there is only limited understanding of isoprene emission patterns during prolonged heat stress and next to no data on emission patterns during coupled heat-drought stress or during post-stress recovery. We studied gas exchange and isoprene emissions of black locust trees under episodic heat stress and in combination with drought. Heatwaves were simulated in a controlled greenhouse facility by exposing trees to outside temperatures +10 °C, and trees in the heat-drought treatment were supplied with half of the irrigation water given to heat and control trees. Leaf gas exchange of isoprene, CO2 and H2O was quantified using self-constructed, automatically operating chambers, which were permanently installed on leaves (n = 3 per treatment). Heat and combined heat-drought stress resulted in a sharp decline of net photosynthesis (Anet) and stomatal conductance. Simultaneously, isoprene emissions increased 6- to 8-fold in the heat and heat-drought treatment, which resulted in a carbon loss that was equivalent to 12 and 20 % of assimilated carbon at the time of measurement. Once temperature stress was released at the end of two 15-day-long heatwaves, stomatal conductance remained reduced, while isoprene emissions and Anet recovered quickly to values of the control trees. Further, we found that isoprene emissions covaried with Anet during nonstress conditions, while during the heatwaves, isoprene emissions were not related to Anet but to light and temperature. Under standard air temperature and light conditions (here 30 °C and photosynthetically active radiation of 500 µmol m-2 s-1), isoprene emissions of the heat trees were by 45 % and the heat-drought trees were by 27 % lower than in control trees. Moreover, temperature response curves showed that not only the isoprene emission factor changed during both heat and heat

Isoprene emission and photosynthesis during heatwaves and drought in black locust

Directory of Open Access Journals (Sweden)

I. Bamberger

2017-08-01

Full Text Available Extreme weather conditions like heatwaves and drought can substantially affect tree physiology and the emissions of isoprene. To date, however, there is only limited understanding of isoprene emission patterns during prolonged heat stress and next to no data on emission patterns during coupled heat–drought stress or during post-stress recovery. We studied gas exchange and isoprene emissions of black locust trees under episodic heat stress and in combination with drought. Heatwaves were simulated in a controlled greenhouse facility by exposing trees to outside temperatures +10 °C, and trees in the heat–drought treatment were supplied with half of the irrigation water given to heat and control trees. Leaf gas exchange of isoprene, CO2 and H2O was quantified using self-constructed, automatically operating chambers, which were permanently installed on leaves (n = 3 per treatment. Heat and combined heat–drought stress resulted in a sharp decline of net photosynthesis (Anet and stomatal conductance. Simultaneously, isoprene emissions increased 6- to 8-fold in the heat and heat–drought treatment, which resulted in a carbon loss that was equivalent to 12 and 20 % of assimilated carbon at the time of measurement. Once temperature stress was released at the end of two 15-day-long heatwaves, stomatal conductance remained reduced, while isoprene emissions and Anet recovered quickly to values of the control trees. Further, we found that isoprene emissions covaried with Anet during nonstress conditions, while during the heatwaves, isoprene emissions were not related to Anet but to light and temperature. Under standard air temperature and light conditions (here 30 °C and photosynthetically active radiation of 500 µmol m−2 s−1, isoprene emissions of the heat trees were by 45 % and the heat–drought trees were by 27 % lower than in control trees. Moreover, temperature response curves showed that not only the isoprene emission

Modulation of Protein S-Nitrosylation by Isoprene Emission in Poplar.

Science.gov (United States)

Vanzo, Elisa; Merl-Pham, Juliane; Velikova, Violeta; Ghirardo, Andrea; Lindermayr, Christian; Hauck, Stefanie M; Bernhardt, Jörg; Riedel, Katharina; Durner, Jörg; Schnitzler, Jörg-Peter

2016-04-01

Researchers have been examining the biological function(s) of isoprene in isoprene-emitting (IE) species for two decades. There is overwhelming evidence that leaf-internal isoprene increases the thermotolerance of plants and protects them against oxidative stress, thus mitigating a wide range of abiotic stresses. However, the mechanisms of abiotic stress mitigation by isoprene are still under debate. Here, we assessed the impact of isoprene on the emission of nitric oxide (NO) and the S-nitroso-proteome of IE and non-isoprene-emitting (NE) gray poplar (Populus × canescens) after acute ozone fumigation. The short-term oxidative stress induced a rapid and strong emission of NO in NE compared with IE genotypes. Whereas IE and NE plants exhibited under nonstressful conditions only slight differences in their S-nitrosylation pattern, the in vivo S-nitroso-proteome of the NE genotype was more susceptible to ozone-induced changes compared with the IE plants. The results suggest that the nitrosative pressure (NO burst) is higher in NE plants, underlining the proposed molecular dialogue between isoprene and the free radical NO Proteins belonging to the photosynthetic light and dark reactions, the tricarboxylic acid cycle, protein metabolism, and redox regulation exhibited increased S-nitrosylation in NE samples compared with IE plants upon oxidative stress. Because the posttranslational modification of proteins via S-nitrosylation often impacts enzymatic activities, our data suggest that isoprene indirectly regulates the production of reactive oxygen species (ROS) via the control of the S-nitrosylation level of ROS-metabolizing enzymes, thus modulating the extent and velocity at which the ROS and NO signaling molecules are generated within a plant cell. © 2016 American Society of Plant Biologists. All Rights Reserved.

Seasonal cycles of isoprene concentrations in the Amazonian rainforest

Science.gov (United States)

Trostdorf, C. R.; Gatti, L. V.; Yamazaki, A.; Potosnak, M. J.; Guenther, A.; Martins, W. C.; Munger, J. W.

2004-03-01

Tropical forests are an important global source of volatile organic compounds (VOCs) and other atmospheric trace gases. The high biodiversity in tropical rainforests complicates the extrapolation of biogenic volatile organic compound (BVOC) emissions from leaf-level measurements to landscape and regional or global scales. In Amazónia, a significant fraction of the carbon emitted from the biosphere to the atmosphere is emitted in the form of BVOCs, and the knowledge of these emissions is important to our understanding of tropical and global atmospheric chemistry and carbon cycling. As part of the Large scale Biosphere-atmosphere experiment in Amazónia (LBA). VOC concentrations were measured at two sites near Santarém, Para State, Brazil. The two sites are located in the National Forest of Tapajós, the first corresponding to primary forest and the second to a forest, that was selectively logged. The samples were collected simultaneously at heights of 65 and 55 m (20 and 10 m above forest canopy, respectively). The average isoprene mixing ratio was 2.2-2.5 ppb at the two sites and the standard deviations within a site ranged from 1 to 1.2 ppb. A strong seasonality of isoprene mixing ratio was observed and associated with the wet and dry seasons. The lowest mixing ratios were found during the transition between the wet to dry season, while at the start of the biomass burning season the mixing ratios increase. A qualitative analysis of a one dimensional model demonstrates that the seasonal cycle in concentrations reflects changes in isoprene production by the ecosystem, not changes in boundary layer dynamics or chemistry. The magnitude of the cycle indicates that the physiological capacity of the ecosystem to emit isoprene may depend on water availability although phenological changes could also contribute to the observed variations. A simple 1-D model that assumes mean daytime isoprene fluxes of 1.5 mg m-2h-1 and 0.9 mg m-2h-1 scaled by an algorithm depending on

Modeling Global Biogenic Emission of Isoprene: Exploration of Model Drivers

Science.gov (United States)

Alexander, Susan E.; Potter, Christopher S.; Coughlan, Joseph C.; Klooster, Steven A.; Lerdau, Manuel T.; Chatfield, Robert B.; Peterson, David L. (Technical Monitor)

1996-01-01

Vegetation provides the major source of isoprene emission to the atmosphere. We present a modeling approach to estimate global biogenic isoprene emission. The isoprene flux model is linked to a process-based computer simulation model of biogenic trace-gas fluxes that operates on scales that link regional and global data sets and ecosystem nutrient transformations Isoprene emission estimates are determined from estimates of ecosystem specific biomass, emission factors, and algorithms based on light and temperature. Our approach differs from an existing modeling framework by including the process-based global model for terrestrial ecosystem production, satellite derived ecosystem classification, and isoprene emission measurements from a tropical deciduous forest. We explore the sensitivity of model estimates to input parameters. The resulting emission products from the global 1 degree x 1 degree coverage provided by the satellite datasets and the process model allow flux estimations across large spatial scales and enable direct linkage to atmospheric models of trace-gas transport and transformation.

Temperature Dependence of Factors Controlling Isoprene Emissions

Science.gov (United States)

Duncan, Bryan N.; Yoshida, Yasuko; Damon, Megan R.; Douglass, Anne R.; Witte, Jacquelyn C.

2009-01-01

We investigated the relationship of variability in the formaldehyde (HCHO) columns measured by the Aura Ozone Monitoring Instrument (OMI) to isoprene emissions in the southeastern United States for 2005-2007. The data show that the inferred, regional-average isoprene emissions varied by about 22% during summer and are well correlated with temperature, which is known to influence emissions. Part of the correlation with temperature is likely associated with other causal factors that are temperature-dependent. We show that the variations in HCHO are convolved with the temperature dependence of surface ozone, which influences isoprene emissions, and the dependence of the HCHO column to mixed layer height as OMI's sensitivity to HCHO increases with altitude. Furthermore, we show that while there is an association of drought with the variation in HCHO, drought in the southeastern U.S. is convolved with temperature.

North American isoprene influence on intercontinental ozone pollution

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A. M. Fiore

2011-02-01

Full Text Available Changing land-use and climate may alter emissions of biogenic isoprene, a key ozone (O₃ precursor. Isoprene is also a precursor to peroxy acetyl nitrate (PAN and thus affects partitioning among oxidized nitrogen (NO_y species, shifting the balance towards PAN, which more efficiently contributes to long-range transport relative to nitric acid (HNO₃ which rapidly deposits. With a suite of sensitivity simulations in the MOZART-2 global tropospheric chemistry model, we gauge the relative importance of the intercontinental influence of a 20% increase in North American (NA isoprene and a 20% decrease in NA anthropogenic emissions (nitrogen oxides (NO_x, non-methane volatile organic compounds (NMVOC and NO_x + NMVOC + carbon monoxide + aerosols. The surface O₃ response to NA isoprene emissions (ΔO₃_ISOP in surface air over NA is about one third of the response to all NA anthropogenic emissions (ΔO₃_ANTH; although with different signs. Over intercontinental distances, ΔO₃_ISOP is relatively larger; in summer and fall, ΔO₃_ISOP in surface air over Europe and North Africa (EU region is more than half of ΔO₃_ANTH. Future increases in NA isoprene emissions could thus offset decreases in EU surface O₃ resulting from controls on NA anthropogenic emissions. Over the EU region, ΔPAN_ISOP at 700 hPa is roughly the same magnitude as ΔPAN_ANTH (oppositely signed. Outside of the continental source region, the percentage changes in PAN are at least twice as large as for surface O₃, implying that long-term PAN measurements at high altitude sites may help to detect O₃ precursor emission changes. We find that neither the baseline level of isoprene emissions nor the fate of isoprene nitrates contributes to the large diversity in model estimates of the anthropogenic emission influence on intercontinental surface O

Microbial cycling of isoprene, the most abundantly produced biological volatile organic compound on Earth.

Science.gov (United States)

McGenity, Terry J; Crombie, Andrew T; Murrell, J Colin

2018-04-01

Isoprene (2-methyl-1,3-butadiene), the most abundantly produced biogenic volatile organic compound (BVOC) on Earth, is highly reactive and can have diverse and often detrimental atmospheric effects, which impact on climate and health. Most isoprene is produced by terrestrial plants, but (micro)algal production is important in aquatic environments, and the relative bacterial contribution remains unknown. Soils are a sink for isoprene, and bacteria that can use isoprene as a carbon and energy source have been cultivated and also identified using cultivation-independent methods from soils, leaves and coastal/marine environments. Bacteria belonging to the Actinobacteria are most frequently isolated and identified, and Proteobacteria have also been shown to degrade isoprene. In the freshwater-sediment isolate, Rhodococcus strain AD45, initial oxidation of isoprene to 1,2-epoxy-isoprene is catalyzed by a multicomponent isoprene monooxygenase encoded by the genes isoABCDEF. The resultant epoxide is converted to a glutathione conjugate by a glutathione S-transferase encoded by isoI, and further degraded by enzymes encoded by isoGHJ. Genome sequence analysis of actinobacterial isolates belonging to the genera Rhodococcus, Mycobacterium and Gordonia has revealed that isoABCDEF and isoGHIJ are linked in an operon, either on a plasmid or the chromosome. In Rhodococcus strain AD45 both isoprene and epoxy-isoprene induce a high level of transcription of 22 contiguous genes, including isoABCDEF and isoGHIJ. Sequence analysis of the isoA gene, encoding the large subunit of the oxygenase component of isoprene monooxygenase, from isolates has facilitated the development of PCR primers that are proving valuable in investigating the ecology of uncultivated isoprene-degrading bacteria.

Modulation of Protein S-Nitrosylation by Isoprene Emission in Poplar1

Science.gov (United States)

Vanzo, Elisa; Velikova, Violeta; Ghirardo, Andrea; Lindermayr, Christian; Hauck, Stefanie M.; Riedel, Katharina; Durner, Jörg

2016-01-01

Researchers have been examining the biological function(s) of isoprene in isoprene-emitting (IE) species for two decades. There is overwhelming evidence that leaf-internal isoprene increases the thermotolerance of plants and protects them against oxidative stress, thus mitigating a wide range of abiotic stresses. However, the mechanisms of abiotic stress mitigation by isoprene are still under debate. Here, we assessed the impact of isoprene on the emission of nitric oxide (NO) and the S-nitroso-proteome of IE and non-isoprene-emitting (NE) gray poplar (Populus × canescens) after acute ozone fumigation. The short-term oxidative stress induced a rapid and strong emission of NO in NE compared with IE genotypes. Whereas IE and NE plants exhibited under nonstressful conditions only slight differences in their S-nitrosylation pattern, the in vivo S-nitroso-proteome of the NE genotype was more susceptible to ozone-induced changes compared with the IE plants. The results suggest that the nitrosative pressure (NO burst) is higher in NE plants, underlining the proposed molecular dialogue between isoprene and the free radical NO. Proteins belonging to the photosynthetic light and dark reactions, the tricarboxylic acid cycle, protein metabolism, and redox regulation exhibited increased S-nitrosylation in NE samples compared with IE plants upon oxidative stress. Because the posttranslational modification of proteins via S-nitrosylation often impacts enzymatic activities, our data suggest that isoprene indirectly regulates the production of reactive oxygen species (ROS) via the control of the S-nitrosylation level of ROS-metabolizing enzymes, thus modulating the extent and velocity at which the ROS and NO signaling molecules are generated within a plant cell. PMID:26850277

The influence of auxins on the biosynthesis of isoprene derivatives in callus cultures of Vaccinium corymbosum var. bluecrop.

Science.gov (United States)

Migas, Piotr; Luczkiewicz, Maria; Cisowski, Wojciech

2006-01-01

Callus cultures of Vaccinium corymbosum var. bluecrop were optimized for their isoprene derivatives production by supplementing Schenk-Hildebrandt (SH) medium with constant concentration of kinetin (2.32 microM) and two different amounts of selected auxins. Every auxin, except for IBA, used in 10-time higher concentration (2,4D, NAA, IAA, NOA) stimulated biosynthesis of beta-sitosterol and inhibited triterpene synthesis. Quantitative analysis of isoprene derivatives in callus biomass collected on the 25th day of the experiment proved that the analyzed callus of Vaccinium corymbosum var. bluecrop synthesized the highest amount of isoprene derivatives after subculturing on SH medium modified with 22.6 microM of 2,4D and 2.32 microM of kinetin.

Contribution of vegetation and water table on isoprene emission from boreal peatland microcosms

DEFF Research Database (Denmark)

Tiiva, Päivi; Faubert, Patrick; Räty, Sanna

2009-01-01

emission in these naturally wet ecosystems, although water table is predicted to decline due to climate warming. We studied the relative contribution of mosses vs. vascular plants to isoprene emission in boreal peatland microcosms in growth chambers by removing either vascular vegetation or both vascular...... hollows with intact vegetation, 45 ± 6 µg m-2 h-1, was decreased by 25% under water table drawdown. However, water table drawdown reduced net ecosystem carbon dioxide (CO2) exchange more dramatically than isoprene emission. Isoprene emission strongly correlated with both CO2 exchange and methane emission......Boreal peatlands are substantial sources of isoprene, a reactive hydrocarbon. However, it is not known how much mosses, vascular plants and peat each contribute to isoprene emission from peatlands. Furthermore, there is no information on the effects of declining water table depth on isoprene...

Formaldehyde production from isoprene oxidation across NOx regimes

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G. M. Wolfe

2016-03-01

Full Text Available The chemical link between isoprene and formaldehyde (HCHO is a strong, nonlinear function of NOx (i.e., NO + NO2. This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall photochemical mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the southeast US, we quantify HCHO production across the urban–rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly emitted isoprene and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons. Over the range of observed NOx values (roughly 0.1–2 ppbv, the prompt yield increases by a factor of 3 (from 0.3 to 0.9 ppbv ppbv−1, while background HCHO increases by a factor of 2 (from 1.6 to 3.3 ppbv. We apply the same method to evaluate the performance of both a global chemical transport model (AM3 and a measurement-constrained 0-D steady-state box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models underestimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or underestimated hydroxyl radical concentrations. Detailed process rates from the box model simulation demonstrate a 3-fold increase in HCHO production across the range of observed NOx values, driven by a 100 % increase in OH and a 40 % increase in branching of organic peroxy radical reactions to produce HCHO.

A new physically-based quantification of marine isoprene and primary organic aerosol emissions

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N. Meskhidze

2009-07-01

Full Text Available The global marine sources of organic carbon (OC are estimated here using a physically-based parameterization for the emission of marine isoprene and primary organic matter. The marine isoprene emission model incorporates new physical parameters such as light sensitivity of phytoplankton isoprene production and dynamic euphotic depth to simulate hourly marine isoprene emissions totaling 0.92 Tg C yr⁻¹. Sensitivity studies using different schemes for the euphotic zone depth and ocean phytoplankton speciation produce the upper and the lower range of marine-isoprene emissions of 0.31 to 1.09 Tg C yr⁻¹, respectively. Established relationships between sea spray fractionation of water-insoluble organic carbon (WIOC and chlorophyll-a concentration are used to estimate the total primary sources of marine sub- and super-micron OC of 2.9 and 19.4 Tg C yr⁻¹, respectively. The consistent spatial and temporal resolution of the two emission types allow us, for the first time, to explore the relative contributions of sub- and super-micron organic matter and marine isoprene-derived secondary organic aerosol (SOA to the total OC fraction of marine aerosol. Using a fixed 3% mass yield for the conversion of isoprene to SOA, our emission simulations show minor (<0.2% contribution of marine isoprene to the total marine source of OC on a global scale. However, our model calculations also indicate that over the tropical oceanic regions (30° S to 30° N, marine isoprene SOA may contribute over 30% of the total monthly-averaged sub-micron OC fraction of marine aerosol. The estimated contribution of marine isoprene SOA to hourly-averaged sub-micron marine OC emission is even higher, approaching 50% over the vast regions of the oceans during the midday hours when isoprene emissions are highest. As it is widely believed that sub-micron OC has the potential to influence the cloud droplet activation of marine aerosols, our

Understanding the impact of recent advances in isoprene photooxidation on simulations of regional air quality

Directory of Open Access Journals (Sweden)

Y. Xie

2013-08-01

Full Text Available The CMAQ (Community Multiscale Air Quality us model in combination with observations for INTEX-NA/ICARTT (Intercontinental Chemical Transport Experiment–North America/International Consortium for Atmospheric Research on Transport and Transformation 2004 are used to evaluate recent advances in isoprene oxidation chemistry and provide constraints on isoprene nitrate yields, isoprene nitrate lifetimes, and NOx recycling rates. We incorporate recent advances in isoprene oxidation chemistry into the SAPRC-07 chemical mechanism within the US EPA (United States Environmental Protection Agency CMAQ model. The results show improved model performance for a range of species compared against aircraft observations from the INTEX-NA/ICARTT 2004 field campaign. We further investigate the key processes in isoprene nitrate chemistry and evaluate the impact of uncertainties in the isoprene nitrate yield, NOx (NOx = NO + NO2 recycling efficiency, dry deposition velocity, and RO2 + HO2 reaction rates. We focus our examination on the southeastern United States, which is impacted by both abundant isoprene emissions and high levels of anthropogenic pollutants. We find that NOx concentrations increase by 4–9% as a result of reduced removal by isoprene nitrate chemistry. O3 increases by 2 ppbv as a result of changes in NOx. OH concentrations increase by 30%, which can be primarily attributed to greater HOx production. We find that the model can capture observed total alkyl and multifunctional nitrates (∑ANs and their relationship with O3 by assuming either an isoprene nitrate yield of 6% and daytime lifetime of 6 hours or a yield of 12% and lifetime of 4 h. Uncertainties in the isoprene nitrates can impact ozone production by 10% and OH concentrations by 6%. The uncertainties in NOx recycling efficiency appear to have larger effects than uncertainties in isoprene nitrate yield and dry deposition velocity. Further progress depends on improved understanding of

Isoprene emission from wetland sedges

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A. Ekberg

2009-04-01

Full Text Available High latitude wetlands play an important role for the surface-atmosphere exchange of carbon dioxide (CO₂ and methane (CH₄, but fluxes of biogenic volatile organic compounds (BVOC in these ecosystems have to date not been extensively studied. This is despite BVOC representing a measurable proportion of the total gaseous C fluxes at northern locations and in the face of the high temperature sensitivity of these systems that requires a much improved process understanding to interpret and project possible changes in response to climate warming. We measured emission of isoprene and photosynthetic gas exchange over two growing seasons (2005–2006 in a subarctic wetland in northern Sweden with the objective to identify the physiological and environmental controls of these fluxes on the leaf scale. The sedge species Eriophorum angustifolium and Carex rostrata were both emitters of isoprene. Springtime emissions were first detected after an accumulated diurnal mean temperature above 0^°C of about 100 degree days. Maximum measured growing season standardized (basal emission rates (20^°C, 1000 μmol m⁻² s⁻¹ were 1075 (2005 and 1118 (2006 μg C m⁻² (leaf area h⁻¹ in E. angustifolium, and 489 (2005 and 396 (2006 μg C m⁻² h⁻¹ in C. rostrata. Over the growing season, basal isoprene emission varied in response to the temperature history of the last 48 h. Seasonal basal isoprene emission rates decreased with leaf nitrogen (N, which may be explained by the typical growth and resource allocation pattern of clonal sedges as the leaves age. The observations were used to model emissions over the growing season, accounting for effects of temperature history, links to leaf assimilation rate and the light and temperature dependencies of the cold-adapted sedges.

Biogenic and anthropogenic isoprene in the near-surface urban atmosphere--a case study in Essen, Germany.

Science.gov (United States)

Wagner, Patrick; Kuttler, Wilhelm

2014-03-15

Isoprene is emitted in large quantities by vegetation, exhaled by human beings and released in small quantities by road traffic. As a result of its high reactivity, isoprene is an important ozone precursor in the troposphere and can play a key role in atmospheric chemistry. Measurements of isoprene in urban areas in Central Europe are scarce. Thus, in Essen, Germany, the isoprene concentration was measured at various sites during different seasons using two compact online GC-PID systems. Isoprene concentrations were compared with those of benzene and toluene, which represent typical anthropogenic VOCs. In the summer, the diurnal variation in isoprene concentration was dependent on the biogenic emissions in the city. It was found that its maximum concentration occurred during the day, in contrast to the benzene and toluene concentrations. During the measurement period in the summer of 2012, the average hourly isoprene concentrations reached 0.13 to 0.17 ppb between 10 and 20 LST. At high air temperatures, the isoprene concentration exceeded the benzene and toluene concentrations at many of the sites. Isoprene became more important than toluene with regard to ozone formation in the city area during the afternoon hours of summer days with high air temperatures. This finding was demonstrated by the contributions to OH reactivity and ozone-forming potential. It contradicts the results of other studies, which were based on daily or seasonal average values. With an isoprene/benzene ratio of 0.02, the contribution of anthropogenic isoprene decreased substantially to a very low level during the last 20 years in Central Europe due to a strong reduction in road traffic emissions. In the vicinity of many people, isoprene concentrations of up to 0.54 ppb and isoprene/benzene ratios of up to 1.34 were found in the atmosphere due to isoprene exhaled by humans. Copyright © 2013. Published by Elsevier B.V.

Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(-)-myrtenol nitrate.

Science.gov (United States)

Bew, Sean P; Hiatt-Gipson, Glyn D; Mills, Graham P; Reeves, Claire E

2016-01-01

Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a 'halide for nitrate' substitution. Employing readily available starting materials, reagents and Horner-Wadsworth-Emmons chemistry the synthesis of easily separable, synthetically versatile 'key building blocks' (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, 'off the shelf' materials. Exploiting their reactivity we have studied their ability to undergo an 'allylic halide for allylic nitrate' substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates ('isoprene nitrates') in 66-80% overall yields. Using NOESY experiments the elucidation of the carbon-carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our 'halide for nitrate' substitution chemistry we outline the straightforward transformation of (1R,2S)-(-)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(-)-myrtenol nitrate.

Isoprene Production on Enzymatic Hydrolysate of Peanut Hull Using Different Pretreatment Methods

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Sumeng Wang

2016-01-01

Full Text Available The present study is about the use of peanut hull for isoprene production. In this study, two pretreatment methods, hydrogen peroxide-acetic acid (HPAC and popping, were employed prior to enzymatic hydrolysis, which could destroy the lignocellulosic structure and accordingly improve the efficiency of enzymatic hydrolysis. It is proven that the isoprene production on enzymatic hydrolysate with HPAC pretreatment is about 1.9-fold higher than that of popping pretreatment. Moreover, through High Performance Liquid Chromatography (HPLC analysis, the amount and category of inhibitors such as formic acid, acetic acid, and HMF were assayed and were varied in different enzymatic hydrolysates, which may be the reason leading to a decrease in isoprene production during fermentation. To further increase the isoprene yield, the enzymatic hydrolysate of HPAC was detoxified by activated carbon. As a result, using the detoxified enzymatic hydrolysate as the carbon source, the engineered strain YJM21 could accumulate 297.5 mg/L isoprene, which accounted for about 90% of isoprene production by YJM21 fermented on pure glucose (338.6 mg/L. This work is thought to be the first attempt on isoprene production by E. coli using peanut hull as the feedstock. More importantly, it also shows the prospect of peanut hull to be considered as an alternative feedstock for bio-based chemicals or biofuels production due to its easy access and high polysaccharide content.

Progress Report: DE-FG03-97ER20274, ''Microbial Production of Isoprene''

Energy Technology Data Exchange (ETDEWEB)

Ray Fall

2002-03-13

We have discovered that microorganisms produce and emit the hydrocarbon isoprene (2-methyl-1,3-butadiene), and have suggested that if isoprene-producing enzymes and their genes can be harnessed, useful hydrocarbon-producing systems might be constructed. The main goal of the proposed work is to establish the biochemical mechanism and regulation of isoprene formation in the bacterial system, Bacillus subtilis. Specific objectives of the proposed work are the following: (A) to characterize the physiological regulation of isoprene formation in B. subtilis; (B) to characterize mutations in B. subtilis 168 that suppress isoprene formation, clone these genes, and determine how isoprene and isoprenoid carbon flow are regulated; and (C) to test ''overflow'' and ''signaling'' models for Bacillus isoprene formation. We are also pursuing the isolation and cloning of B. subtilis isoprene synthase, which we believe may be a regulatory enzyme.

Airborne measurements of isoprene and monoterpene emissions from southeastern U.S. forests

Energy Technology Data Exchange (ETDEWEB)

Yu, Haofei; Guenther, Alex; Gu, Dasa; Warneke, Carsten; Geron, Chris; Goldstein, Allen; Graus, Martin; Karl, Thomas; Kaser, Lisa; Misztal, Pawel; Yuan, Bin

2017-10-01

Isoprene and monoterpene emission rates are essential inputs for atmospheric chemistry models that simulate atmospheric oxidant and particle distributions. Process studies of the biochemical and physiological mechanisms controlling these emissions are advancing our understanding and the accuracy of model predictions but efforts to quantify regional emissions have been limited by a lack of constraints on regional distributions of ecosystem emission capacities. We used an airborne wavelet-based eddy covariance measurement technique to characterize isoprene and monoterpene fluxes with high spatial resolution during the 2013 SAS (Southeast Atmosphere Study) in the southeastern United States. The fluxes measured by direct eddy covariance were comparable to emissions independently estimated using an indirect inverse modeling approach. Isoprene emission factors based on the aircraft wavelet flux estimates for high isoprene chemotypes (e.g., oaks) were similar to the MEGAN2.1 biogenic emission model estimates for landscapes dominated by oaks. Aircraft flux measurement estimates for landscapes with fewer isoprene emitting trees (e.g., pine plantations), were about a factor of two lower than MEGAN2.1 model estimates. The tendency for high isoprene emitters in these landscapes to occur in the shaded understory, where light dependent isoprene emissions are diminished, may explain the lower than expected emissions. This result demonstrates the importance of accurately representing the vertical profile of isoprene emitting biomass in biogenic emission models. Airborne measurement-based emission factors for high monoterpene chemotypes agreed with MEGAN2.1 in landscapes dominated by pine (high monoterpene chemotype) trees but were more than a factor of three higher than model estimates for landscapes dominated by oak (relatively low monoterpene emitting) trees. This results suggests that unaccounted processes, such as floral emissions or light dependent monoterpene emissions, or

Elevated atmospheric CO2 concentration leads to increased whole-plant isoprene emission in hybrid aspen (Populus tremula × Populus tremuloides).

Science.gov (United States)

Sun, Zhihong; Niinemets, Ülo; Hüve, Katja; Rasulov, Bahtijor; Noe, Steffen M

2013-05-01

Effects of elevated atmospheric [CO2] on plant isoprene emissions are controversial. Relying on leaf-scale measurements, most models simulating isoprene emissions in future higher [CO2] atmospheres suggest reduced emission fluxes. However, combined effects of elevated [CO2] on leaf area growth, net assimilation and isoprene emission rates have rarely been studied on the canopy scale, but stimulation of leaf area growth may largely compensate for possible [CO2] inhibition reported at the leaf scale. This study tests the hypothesis that stimulated leaf area growth leads to increased canopy isoprene emission rates. We studied the dynamics of canopy growth, and net assimilation and isoprene emission rates in hybrid aspen (Populus tremula × Populus tremuloides) grown under 380 and 780 μmol mol(-1) [CO2]. A theoretical framework based on the Chapman-Richards function to model canopy growth and numerically compare the growth dynamics among ambient and elevated atmospheric [CO2]-grown plants was developed. Plants grown under elevated [CO2] had higher C : N ratio, and greater total leaf area, and canopy net assimilation and isoprene emission rates. During ontogeny, these key canopy characteristics developed faster and stabilized earlier under elevated [CO2]. However, on a leaf area basis, foliage physiological traits remained in a transient state over the whole experiment. These results demonstrate that canopy-scale dynamics importantly complements the leaf-scale processes, and that isoprene emissions may actually increase under higher [CO2] as a result of enhanced leaf area production. © 2013 The Authors. New Phytologist © 2013 New Phytologist Trust.

Understanding the impact of recent advances in isoprene photooxidation on simulations of regional air quality

OpenAIRE

Xie, Y; Paulot, F; Carter, WPL; Nolte, CG; Luecken, DJ; Hutzell, WT; Wennberg, PO; Cohen, RC; Pinder, RW

2013-01-01

The CMAQ (Community Multiscale Air Quality) us model in combination with observations for INTEX-NA/ICARTT (Intercontinental Chemical Transport Experiment–North America/International Consortium for Atmospheric Research on Transport and Transformation) 2004 are used to evaluate recent advances in isoprene oxidation chemistry and provide constraints on isoprene nitrate yields, isoprene nitrate lifetimes, and NOx recycling rates. We incorporate recent advances in isoprene oxidation ch...

Understanding the impact of recent advances in isoprene photooxidation on simulations of regional air quality

OpenAIRE

Xie, Y.; Carter, W. P. L.; Nolte, C. G.; Luecken, D. J.; Hutzell, W. T.; Wennberg, P. O.; Cohen, R. C.; Pinder, R. W.

2013-01-01

The CMAQ (Community Multiscale Air Quality) us model in combination with observations for INTEX-NA/ICARTT (Intercontinental Chemical Transport Experiment–North America/International Consortium for Atmospheric Research on Transport and Transformation) 2004 are used to evaluate recent advances in isoprene oxidation chemistry and provide constraints on isoprene nitrate yields, isoprene nitrate lifetimes, and NO_x recycling rates. We incorporate recent advances in isoprene oxidation chemistry int...

Isoprene emission by poplar is not important for the feeding behaviour of poplar leaf beetles

OpenAIRE

M?ller, Anna; Kaling, Moritz; Faubert, Patrick; Gort, Gerrit; Smid, Hans M; Van Loon, Joop JA; Dicke, Marcel; Kanawati, Basem; Schmitt-Kopplin, Philippe; Polle, Andrea; Schnitzler, J?rg-Peter; Rosenkranz, Maaria

2015-01-01

Background Chrysomela populi (poplar leaf beetle) is a common herbivore in poplar plantations whose infestation causes major economic losses. Because plant volatiles act as infochemicals, we tested whether isoprene, the main volatile organic compound (VOC) produced by poplars (Populus x canescens), affects the performance of C. populi employing isoprene emitting (IE) and transgenic isoprene non-emitting (NE) plants. Our hypothesis was that isoprene is sensed and affects beetle orientation or ...

Photosynthesis-dependent isoprene emission from leaf to planet in a global carbon-chemistry-climate model

Science.gov (United States)

Unger, N.; Harper, K.; Zheng, Y.; Kiang, N. Y.; Aleinov, I.; Arneth, A.; Schurgers, G.; Amelynck, C.; Goldstein, A.; Guenther, A.; Heinesch, B.; Hewitt, C. N.; Karl, T.; Laffineur, Q.; Langford, B.; McKinney, K. A.; Misztal, P.; Potosnak, M.; Rinne, J.; Pressley, S.; Schoon, N.; Serça, D.

2013-10-01

We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar-Ball-Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present-day climatic state that uses 8 plant functional types (PFTs), prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis) reproduces 50% of the variability across different ecosystems and seasons in a global database of 28 measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at 9 select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R2 = 64-96%) and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr-1 that increases by 30% in the artificial absence of plant water stress and by 55% for potential natural vegetation.

Photosynthesis-dependent Isoprene Emission from Leaf to Planet in a Global Carbon-chemistry-climate Model

Science.gov (United States)

Unger, N.; Harper, K.; Zeng, Y.; Kiang, N. Y.; Alienov, I.; Arneth, A.; Schurgers, G.; Amelynck, C.; Goldstein, A.; Guenther, A.;

Photosynthesis-dependent isoprene emission from leaf to planet in a global carbon-chemistry-climate model

Energy Technology Data Exchange (ETDEWEB)

Unger, N.; Harper, K.; Zheng, Y.; Kiang, N. Y.; Aleinov, I.; Arneth, Almut; Schurgers, G.; Amelynck, C.; Goldstein, Allen H.; Guenther, Alex B.; Heinesch, B.; Hewitt, C. N.; Karl, T.; Laffineur, Q.; Langford, B.; McKinney, Karena A.; Misztal, P.; Potosnak, M.; Rinne, J.; Pressley, S.; Schoon, N.; Serca, D.

2013-10-22

We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar/Ball- Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present day climatic state that uses plant functional types (PFTs), prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis) reproduces 50% of the variability across different ecosystems and seasons in a global database of measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R² = 64-96 %) and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr^-1 that increases by 30% in the artificial absence of plant water stress and by 55% for potential natural vegetation.

Analysis of riparian afforestation methods in the Missouri Ozarks

Science.gov (United States)

Kyle L. Steele; John M. Kabrick; Randy G. Jensen; Michael J. Wallendorf; Daniel C. Dey

2008-01-01

We evaluated the first-year survival and growth of 13 bottomland species in several different management treatments replicated at three sites in the Missouri Ozarks. Treatments were: 1) Roundup® site preparation only; and Roundup® site preparation plus a: 2) growing season application of Poast Plus® (a grass-selective herbicide); 3) redtop...

Densification and state transition across the Missouri Ozarks landscape

Science.gov (United States)

Brice B. Hanberry; John M. Kabrick; Hong S. He

2014-01-01

World-wide, some biomes are densifying, or increasing in dense woody vegetation, and shifting to alternative stable states. We quantified densification and state transition between forests ecosystems in historical (ca. 1815-1850) and current (2004-2008) surveys of the Missouri Ozark Highlands, a 5-million ha landscape in southern Missouri, USA. To estimate density of...

Isoprene Emission Factors for Subtropical Street Trees for Regional Air Quality Modeling.

Science.gov (United States)

Dunn-Johnston, Kristina A; Kreuzwieser, Jürgen; Hirabayashi, Satoshi; Plant, Lyndal; Rennenberg, Heinz; Schmidt, Susanne

2016-01-01

Evaluating the environmental benefits and consequences of urban trees supports their sustainable management in cities. Models such as i-Tree Eco enable decision-making by quantifying effects associated with particular tree species. Of specific concern are emissions of biogenic volatile organic compounds, particularly isoprene, that contribute to the formation of photochemical smog and ground level ozone. Few studies have quantified these potential disservices of urban trees, and current models predominantly use emissions data from trees that differ from those in our target region of subtropical Australia. The present study aimed (i) to quantify isoprene emission rates of three tree species that together represent 16% of the inventoried street trees in the target region; (ii) to evaluate outputs of the i-Tree Eco model using species-specific versus currently used, generic isoprene emission rates; and (iii) to evaluate the findings in the context of regional air quality. Isoprene emission rates of (Myrtaceae) and (Proteaceae) were 2.61 and 2.06 µg g dry leaf weight h, respectively, whereas (Sapindaceae) was a nonisoprene emitter. We substituted the generic isoprene emission rates with these three empirical values in i-Tree Eco, resulting in a 182 kg yr (97%) reduction in isoprene emissions, totaling 6284 kg yr when extrapolated to the target region. From these results we conclude that care has to be taken when using generic isoprene emission factors for urban tree models. We recommend that emissions be quantified for commonly planted trees, allowing decision-makers to select tree species with the greatest overall benefit for the urban environment. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Airborne measurements of isoprene and monoterpene emissions from southeastern U.S. forests.

Science.gov (United States)

Yu, Haofei; Guenther, Alex; Gu, Dasa; Warneke, Carsten; Geron, Chris; Goldstein, Allen; Graus, Martin; Karl, Thomas; Kaser, Lisa; Misztal, Pawel; Yuan, Bin

2017-10-01

Isoprene and monoterpene emission rates are essential inputs for atmospheric chemistry models that simulate atmospheric oxidant and particle distributions. Process studies of the biochemical and physiological mechanisms controlling these emissions are advancing our understanding and the accuracy of model predictions but efforts to quantify regional emissions have been limited by a lack of constraints on regional distributions of ecosystem emission capacities. We used an airborne wavelet-based eddy covariance measurement technique to characterize isoprene and monoterpene fluxes with high spatial resolution during the 2013 SAS (Southeast Atmosphere Study) in the southeastern United States. The fluxes measured by direct eddy covariance were comparable to emissions independently estimated using an indirect inverse modeling approach. Isoprene emission factors based on the aircraft wavelet flux estimates for high isoprene chemotypes (e.g., oaks) were similar to the MEGAN2.1 biogenic emission model estimates for landscapes dominated by oaks. Aircraft flux measurement estimates for landscapes with fewer isoprene emitting trees (e.g., pine plantations), were about a factor of two lower than MEGAN2.1 model estimates. The tendency for high isoprene emitters in these landscapes to occur in the shaded understory, where light dependent isoprene emissions are diminished, may explain the lower than expected emissions. This result demonstrates the importance of accurately representing the vertical profile of isoprene emitting biomass in biogenic emission models. Airborne measurement-based emission factors for high monoterpene chemotypes agreed with MEGAN2.1 in landscapes dominated by pine (high monoterpene chemotype) trees but were more than a factor of three higher than model estimates for landscapes dominated by oak (relatively low monoterpene emitting) trees. This results suggests that unaccounted processes, such as floral emissions or light dependent monoterpene emissions, or

How light, temperature, and measurement and growth [CO2] interactively control isoprene emission in hybrid aspen.

Science.gov (United States)

Niinemets, Ülo; Sun, Zhihong

2015-02-01

Plant isoprene emissions have been modelled assuming independent controls by light, temperature and atmospheric [CO2]. However, the isoprene emission rate is ultimately controlled by the pool size of its immediate substrate, dimethylallyl diphosphate (DMADP), and isoprene synthase activity, implying that the environmental controls might interact. In addition, acclimation to growth [CO2] can shift the share of the control by DMADP pool size and isoprene synthase activity, and thereby alter the environmental sensitivity. Environmental controls of isoprene emission were studied in hybrid aspen (Populus tremula × Populus tremuloides) saplings acclimated either to ambient [CO2] of 380 μmol mol(-1) or elevated [CO2] of 780 μmol mol(-1). The data demonstrated strong interactive effects of environmental drivers and growth [CO2] on isoprene emissions. Light enhancement of isoprene emission was the greatest at intermediate temperatures and was greater in elevated-[CO2]-grown plants, indicating greater enhancement of the DMADP supply. The optimum temperature for isoprene emission was higher at lower light, suggesting activation of alternative DMADP sinks at higher light. In addition, [CO2] inhibition of isoprene emission was lost at a higher temperature with particularly strong effects in elevated-[CO2]-grown plants. Nevertheless, DMADP pool size was still predicted to more strongly control isoprene emission at higher temperatures in elevated-[CO2]-grown plants. We argue that interactive environmental controls and acclimation to growth [CO2] should be incorporated in future isoprene emission models at the level of DMADP pool size. © The Author 2014. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Influence of isoprene chemical mechanism on modelled changes in tropospheric ozone due to climate and land use over the 21st century

Science.gov (United States)

Squire, O. J.; Archibald, A. T.; Griffiths, P. T.; Jenkin, M. E.; Smith, D.; Pyle, J. A.

2015-05-01

additional isoprene-derived HOx recycling pathways). These have implications for secondary organic aerosol formation, as does the inclusion of an epoxide formation pathway in one of the mechanisms. By combining the emissions and O3 data from all of the global model integrations, we are able to construct isopleth plots comparable to those from the box model analysis. We find that the global and box model isopleths show good qualitative agreement, suggesting that comparing chemical mechanisms with a box model in this framework is a useful tool for assessing mechanistic performance in complex global models. We conclude that as the choice of reduced isoprene mechanism may alter both the magnitude and sign of the ozone response, how isoprene chemistry is parameterised in perturbation experiments such as these is a crucially important consideration. More measurements and laboratory studies are needed to validate these reduced mechanisms especially under high-volatile-organic-compound, low-NOx conditions.

Photosynthesis-dependent isoprene emission from leaf to planet in a global carbon-chemistry-climate model

Directory of Open Access Journals (Sweden)

N. Unger

2013-10-01

Full Text Available We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar–Ball–Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present-day climatic state that uses 8 plant functional types (PFTs, prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis reproduces 50% of the variability across different ecosystems and seasons in a global database of 28 measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at 9 select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R2 = 64–96% and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr−1 that increases by 30% in the artificial absence of plant water stress and by 55% for potential natural vegetation.

Shortleaf pine restoration and ecology in the Ozarks: proceedings of a symposium

Science.gov (United States)

John M. Kabrick; Daniel C. Dey; David Gwaze

2007-01-01

Contains 27 papers and 14 extended abstracts from the symposium "Shortleaf pine restoration and ecology in the Ozarks" held November 7-9, 2006, at the University Plaza Hotel and Convention Center in Springfield, MO.

Synergy between methylerythritol phosphate pathway and mevalonate pathway for isoprene production in Escherichia coli.

Science.gov (United States)

Yang, Chen; Gao, Xiang; Jiang, Yu; Sun, Bingbing; Gao, Fang; Yang, Sheng

2016-09-01

Isoprene, a key building block of synthetic rubber, is currently produced entirely from petrochemical sources. In this work, we engineered both the methylerythritol phosphate (MEP) pathway and the mevalonate (MVA) pathway for isoprene production in E. coli. The synergy between the MEP pathway and the MVA pathway was demonstrated by the production experiment, in which overexpression of both pathways improved the isoprene yield about 20-fold and 3-fold, respectively, compared to overexpression of the MEP pathway or the MVA pathway alone. The (13)C metabolic flux analysis revealed that simultaneous utilization of the two pathways resulted in a 4.8-fold increase in the MEP pathway flux and a 1.5-fold increase in the MVA pathway flux. The synergy of the dual pathway was further verified by quantifying intracellular flux responses of the MEP pathway and the MVA pathway to fosmidomycin treatment and mevalonate supplementation. Our results strongly suggest that coupling of the complementary reducing equivalent demand and ATP requirement plays an important role in the synergy of the dual pathway. Fed-batch cultivation of the engineered strain overexpressing the dual pathway resulted in production of 24.0g/L isoprene with a yield of 0.267g/g of glucose. The synergy of the MEP pathway and the MVA pathway also successfully increased the lycopene productivity in E. coli, which demonstrates that it can be used to improve the production of a broad range of terpenoids in microorganisms. Copyright © 2016 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

Challenges in modelling isoprene and monoterpene emission dynamics of Arctic plants

DEFF Research Database (Denmark)

Tang, Jing; Schurgers, Guy; Valolahti, Hanna Maritta

2016-01-01

test. The model showed reasonable agreement to the observed vegetation CO2 fluxes in the main growing season as well as day-to-day variability of isoprene and monoterpene emissions. The observed relatively high WRs were better captured by the adjusted T response curve than by the common one. During...... 1999-2012, the modelled annual mean isoprene and monoterpene emissions were 20 and 8 mg C mg-2 yrg-1, with an increase by 55 and 57 % for 2 °C summertime warming, respectively. Warming by 4 and 8 °C for the same period further elevated isoprene emission for all years, but the impacts on monoterpene...

Evidence for a significant proportion of Secondary Organic Aerosol from isoprene above a maritime tropical forest

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N. H. Robinson

2011-02-01

Full Text Available Isoprene is the most abundant non-methane biogenic volatile organic compound (BVOC, but the processes governing secondary organic aerosol (SOA formation from isoprene oxidation are only beginning to become understood and selective quantification of the atmospheric particulate burden remains difficult. Organic aerosol above a tropical rainforest located in Danum Valley, Borneo, Malaysia, a high isoprene emission region, was studied during Summer 2008 using Aerosol Mass Spectrometry and offline detailed characterisation using comprehensive two dimensional gas chromatography. Observations indicate that a substantial fraction (up to 15% by mass of atmospheric sub-micron organic aerosol was observed as methylfuran (MF after thermal desorption. This observation was associated with the simultaneous measurements of established gas-phase isoprene oxidation products methylvinylketone (MVK and methacrolein (MACR. Observations of MF were also made during experimental chamber oxidation of isoprene. Positive matrix factorisation of the AMS organic mass spectral time series produced a robust factor which accounts for an average of 23% (0.18 μg m⁻³, reaching as much as 53% (0.50 μg m⁻³ of the total oraganic loading, identified by (and highly correlated with a strong MF signal. Assuming that this factor is generally representative of isoprene SOA, isoprene derived aerosol plays a significant role in the region. Comparisons with measurements from other studies suggest this type of isoprene SOA plays a role in other isoprene dominated environments, albeit with varying significance.

Global isoprene and monoterpene emissions under changing climate, vegetation, CO2 and land use

DEFF Research Database (Denmark)

Hantson, Stijn; Knorr, Wolfgang; Schurgers, Guy

2017-01-01

Plants emit large quantities of isoprene and monoterpenes, the main components of global biogenic volatile organic compound (BVOC) emissions. BVOCs have an important impact on the atmospheric composition of methane, and of short-lived radiative forcing agents (e.g. ozone, aerosols etc.). It is th......Plants emit large quantities of isoprene and monoterpenes, the main components of global biogenic volatile organic compound (BVOC) emissions. BVOCs have an important impact on the atmospheric composition of methane, and of short-lived radiative forcing agents (e.g. ozone, aerosols etc.......). It is therefore necessary to know how isoprene and monoterpene emissions have changed over the past and how future changes in climate, land-use and other factors will impact them. Here we present emission estimates of isoprene and monoterpenes over the period 1901–2 100 based on the dynamic global vegetation...... model LPJ-GUESS, including the effects of all known important drivers. We find that both isoprene and monoterpene emissions at the beginning of the 20th century were higher than at present. While anthropogenic land-use change largely drives the global decreasing trend for isoprene over the 20th century...

Isoprene emissions over Asia 1979-2012 : impact of climate and land use changes

Science.gov (United States)

Stavrakou, Trissevgeni; Müller, Jean-Francois; Bauwens, Maite; Guenther, Alex; De Smedt, Isabelle; Van Roozendael, Michel

2014-05-01

Due to the scarcity of observational contraints and the rapidly changing environment in East and Southeast Asia, isoprene emissions predicted by models are expected to bear substantial uncertainties. This study aims at improving upon current bottom-up estimates, and investigate the temporal evolution of isoprene fluxes in Asia over 1979-2012. For that, we use the MEGAN model and incorporate (i) changes in land use, including the rapid expansion of oil palms, (ii) meteorological variability, (iii) long-term changes in solar radiation constrained by surface network measurements, and (iv) recent experimental evidence that South Asian forests are much weaker isoprene emitters than previously assumed. These effects lead to a significant reduction of the total isoprene fluxes over the studied domain compared to the standard simulation. The bottom-up emissions are evaluated using satellite-based emission estimates derived from inverse modelling constrained by GOME-2/MetOp-A formaldehyde columns through 2007-2012. The top-down estimates support our assumptions and confirm the lower isoprene emission rate in tropical forests of Indonesia and Malaysia.

Effect of isoprene emissions from major forests on ozone formation in the city of Shanghai, China

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F. Geng

2011-10-01

Full Text Available Ambient surface level concentrations of isoprene (C₅H₈ were measured in the major forest regions located south of Shanghai, China. Because there is a large coverage of broad-leaved trees in this region, high concentrations of isoprene were measured, ranging from 1 to 6 ppbv. A regional dynamical/chemical model (WRF-Chem is applied for studying the effect of such high concentrations of isoprene on the ozone production in the city of Shanghai. The evaluation of the model shows that the calculated isoprene concentrations agree with the measured concentrations when the measured isoprene concentrations are lower than 3 ppb, but underestimate the measurements when the measured values are higher than 3 ppb. Isoprene was underestimated only at sampling sites near large bamboo plantations, a high isoprene source, indicating the need to include geospatially resolved bamboo distributions in the biogenic emission model. The assessment of the impact of isoprene on ozone formation suggests that the concentrations of peroxy radicals (RO₂ are significantly enhanced due to the oxidation of isoprene, with a maximum of 30 ppt. However, the enhancement of RO₂ is confined to the forested regions. Because the concentrations of NO_x were low in the forest regions, the ozone production due to the oxidation of isoprene (C₅H₈ + OH → → RO₂ + NO → → O₃ is low (less than 2–3 ppb h⁻¹. The calculation further suggests that the oxidation of isoprene leads to the enhancement of carbonyls (such as formaldehyde and acetaldehyde in the regions downwind of the forests, due to continuous oxidation of isoprene in the forest air. As a result, the concentrations of HO₂ radical are enhanced, resulting from the photo-disassociation of formaldehyde and acetaldehyde. Because the enhancement of HO₂ radical occurs in regions downwind of the forests

Coregulation of terpenoid pathway genes and prediction of isoprene production in Bacillus subtilis using transcriptomics

Energy Technology Data Exchange (ETDEWEB)

Hess, Becky M.; Xue, Junfeng; Markillie, Lye Meng; Taylor, Ronald C.; Wiley, H. S.; Ahring, Birgitte K.; Linggi, Bryan E.

2013-06-19

The isoprenoid pathway converts pyruvate to isoprene and related isoprenoid compounds in plants and some bacteria. Currently, this pathway is of great interest because of the critical role that isoprenoids play in basic cellular processes as well as the industrial value of metabolites such as isoprene. Although the regulation of several pathway genes has been described, there is a paucity of information regarding the system level regulation and control of the pathway. To address this limitation, we examined Bacillus subtilis grown under multiple conditions and then determined the relationship between altered isoprene production and the pattern of gene expression. We found that terpenoid genes appeared to fall into two distinct subsets with opposing correlations with respect to the amount of isoprene produced. The group whose expression levels positively correlated with isoprene production included dxs, the gene responsible for the commitment step in the pathway, as well as ispD, and two genes that participate in the mevalonate pathway, yhfS and pksG. The subset of terpenoid genes that inversely correlated with isoprene production included ispH, ispF, hepS, uppS, ispE, and dxr. A genome wide partial least squares regression model was created to identify other genes or pathways that contribute to isoprene production. This analysis showed that a subset of 213 regulated genes was sufficient to create a predictive model of isoprene production under different conditions and showed correlations at the transcriptional level. We conclude that gene expression levels alone are sufficiently informative about the metabolic state of a cell that produces increased isoprene and can be used to build a model which accurately predicts production of this secondary metabolite across many simulated environmental conditions.

Upland forest vegetation of the Ozark Mountains in Northwestern Arkansas

Science.gov (United States)

Steven L. Stephenson; Harold S. Adams; Cynthia D. Huebner

2007-01-01

Quantitative data on structure and composition of all strata of vegetation were collected from 20 study sites in the Boston Mountains Subsection of the Ozark Mountains of northwestern Arkansas in June 2004. All study sites were located at upper slope or ridgetop positions and occurred at elevations > 457 m. Oaks (Quercus spp.) were dominants in...

Isoprene emissions at the canopy scale: measurements in the Escompte program

Science.gov (United States)

Serça, D.; Fotiadi, A.; Bouchou, P.; Cortinovis, J.

2003-04-01

Concentrations of biogenic volatile organic compounds (BVOCs) play a crucial role in the atmospheric chemistry through their role in the production-destruction cycle of tropospheric O3. Half of these BVOCs would be made of isoprene (C5H8), a compound predominantly emitted by ligneous species. Measurements presented here were collected during the ESCOMPTE campaign carried out in the Marseille region, South-West of France. Meteorological parameters, microclimate and fluxes were measured at the canopy scale of a Quercus pubescens forest. Latent and sensible heat, CO2 and isoprene fluxes were calculated using the eddy covariance method. Isoprene fluxes followed the expected diurnal evolution, with maximum emissions at noon reaching about 5 to 10 mgC m-2 h-1. Significant regression coefficient (r2 between 0.61 and 0.76) were found between isoprene emission and PAR, isoprene concentrations and energy fluxes (latent and sensible). The strongest correlation (r2 = 0.8) was found between mean emission and temperature averaged each day between 6 am and 6pm. A cumulative effect of temperature was observed with a constant flux increase (max from 5 to 15 mgCm-2h-1) along a one week period corresponding to an increase in maximum temperature from 24°C to 30°C. The calculated mean emission factor (37.2 µg g-1dw h-1) is in the order of values found in the literature for oak Mediterranean forests.

The influence of small-scale variations in isoprene concentrations on atmospheric chemistry over a tropical rainforest

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T. A. M. Pugh

2011-05-01

Full Text Available Biogenic volatile organic compounds (BVOCs such as isoprene constitute a large proportion of the global atmospheric oxidant sink. Their reactions in the atmosphere contribute to processes such as ozone production and secondary organic aerosol formation. However, over the tropical rainforest, where 50 % of the global emissions of BVOCs are believed to occur, atmospheric chemistry models have been unable to simulate concurrently the measured daytime concentration of isoprene and that of its principal oxidant, hydroxyl (OH. One reason for this model-measurement discrepancy may be incomplete mixing of isoprene within the convective boundary layer, leading to patchiness or segregation in isoprene and OH mixing ratios and average concentrations that appear to be incompatible with each other. One way of capturing this effect in models of atmospheric chemistry is to use a reduced effective rate constant for their reaction. Recent studies comparing atmospheric chemistry global/box models with field measurements have suggested that this effective rate reduction may be as large as 50 %; which is at the upper limit of that calculated using large eddy simulation models. To date there has only been one field campaign worldwide that has reported co-located measurements of isoprene and OH at the necessary temporal resolution to calculate the segregation of these compounds. However many campaigns have recorded sufficiently high resolution isoprene measurements to capture the small-scale fluctuations in its concentration. Assuming uniform distributions of other OH production and loss processes, we use a box model of atmospheric chemistry, constrained by the spectrum of isoprene concentrations measured, as a virtual instrument, to estimate the variability in OH at a point and hence, to estimate the segregation intensity of isoprene and OH from high-frequency isoprene time series. The method successfully reproduces the only directly observed segregation, using

Selective measurements of isoprene and 2-methyl-3-buten-2-ol based on NO+ ionization mass spectrometry

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W. Jud

2012-12-01

Full Text Available Biogenic VOC emissions are often dominated by 2-methyl-1,3-butadiene (isoprene and 2-methyl-3-buten-2-ol (232 MBO. Here we explore the possibility to selectively distinguish these species using NO+ as a primary ion in a conventional PTR-MS equipped with an SRI unit. High purity of NO+ (>90% as a primary ion was utilized in laboratory and field experiments using a conventional PTR-TOF-MS. Isoprene is ionized via charge transfer leading to the major product ion C5H8+ (>99% (e.g. Spanel and Smith, 1998. 232 MBO undergoes a hydroxide ion transfer reaction resulting in the major product ion channel C5H9+ (>95% (e.g. Amelynck et al., 2005. We show that both compounds are ionized with little fragmentation (>5% under standard operating conditions. Typical sensitivities of 11.1 ± 0.1 (isoprene and 12.9 ± 0.1 (232 MBO ncps ppbv−1 were achieved, which correspond to limit of detections of 18 and 15 pptv respectively for a 10 s integration time. Sensitivities decreased at higher collisional energies. Calibration experiments showed little humidity dependence. We tested the setup at a field site in Colorado dominated by ponderosa pine, a 232 MBO emitting plant species. Our measurements confirm 232 MBO as the dominant biogenic VOC at this site, exhibiting typical average daytime concentrations between 0.2–1.4 ppbv. The method is able to detect the presence of trace levels of isoprene at this field site (90–250 ppt without any interference from 232 MBO, which would not be feasible using H3O+ ionization chemistry, and which currently also remains a challenge for other analytical techniques (e.g. gas chromatographic methods.

Secondary organic aerosols over oceans via oxidation of isoprene and monoterpenes from Arctic to Antarctic.

Science.gov (United States)

Hu, Qi-Hou; Xie, Zhou-Qing; Wang, Xin-Ming; Kang, Hui; He, Quan-Fu; Zhang, Pengfei

2013-01-01

Isoprene and monoterpenes are important precursors of secondary organic aerosols (SOA) in continents. However, their contributions to aerosols over oceans are still inconclusive. Here we analyzed SOA tracers from isoprene and monoterpenes in aerosol samples collected over oceans during the Chinese Arctic and Antarctic Research Expeditions. Combined with literature reports elsewhere, we found that the dominant tracers are the oxidation products of isoprene. The concentrations of tracers varied considerably. The mean average values were approximately one order of magnitude higher in the Northern Hemisphere than in the Southern Hemisphere. High values were generally observed in coastal regions. This phenomenon was ascribed to the outflow influence from continental sources. High levels of isoprene could emit from oceans and consequently have a significant impact on marine SOA as inferred from isoprene SOA during phytoplankton blooms, which may abruptly increase up to 95 ng/m³ in the boundary layer over remote oceans.

Measurement of endogenous acetone and isoprene in exhaled breath during sleep

International Nuclear Information System (INIS)

King, Julian; Kupferthaler, Alexander; Unterkofler, Karl; Amann, Anton; Frauscher, Birgit; Hackner, Heinz; Högl, Birgit; Teschl, Gerald; Hinterhuber, Hartmann

2012-01-01

This explorative study aims at characterizing the breath behavior of two prototypic volatile organic compounds, acetone and isoprene, during normal human sleep and to possibly relate changes in the respective concentration time courses to the underlying sleep architecture. For this purpose, six normal healthy volunteers (two females, four males, age 20–29 years) were monitored over two consecutive nights (the first one being an adaption night) by combining real-time proton-transfer-reaction mass spectrometry measurements from end-tidal exhalation segments with laboratory-based polysomnographic data. Breath acetone concentrations increased overnight in all measurements, with an average relative change by a factor of up to 4 (median 2.5). Nighttime concentration maxima were usually recorded 2–3 h before lights on. For breath isoprene, a nocturnal increase in baseline concentrations of about 74% was observed, with individual changes ranging from 36–110%. Isoprene profiles exhibited pronounced concentration peaks, which were highly specific for leg movements as scored by tibial electromyography. Furthermore, relative to a linear trend, baseline isoprene concentrations decreased during the transition from the NREM to the REM phase of a complete sleep cycle. (paper)

Photosynthesis-dependent isoprene emission from leaf to planet in a global carbon-chemistry-climate model

OpenAIRE

Unger, N.; Harper, K.; Zheng, Y.; Kiang, N. Y.; Aleinov, I.; Arneth, A.; Schurgers, G.; Amelynyck, C.; Goldstein, A.; Guenther, A.; Heinesch, B.; Hewitt, C. N.; Karl, T.; Laffineur, Q.; Langford, B.

2013-01-01

We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar–Ball–Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. Th...

Understanding isoprene photooxidation using observations and modeling over a subtropical forest in the southeastern US

Directory of Open Access Journals (Sweden)

L. Su

2016-06-01

Full Text Available The emission, dispersion, and photochemistry of isoprene (C5H8 and related chemical species in the convective boundary layer (CBL during sunlit daytime were studied over a mixed forest in the southeastern United States by combining ground-based and aircraft observations. Fluxes of isoprene and monoterpenes were quantified at the top of the forest canopy using a high-resolution proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS. Snapshot (∼  2 min sampling duration vertical profiles of isoprene, methyl vinyl ketone (MVK + methacrolein (MACR, and monoterpenes were collected from aircraft every hour in the CBL (100–1000 m. Both ground-based and airborne collected volatile organic compound (VOC data are used to constrain the initial conditions of a mixed-layer chemistry model (MXLCH, which is applied to examine the chemical evolution of the O3–NOx–HOx–VOC system and how it is affected by boundary layer dynamics in the CBL. The chemical loss rate of isoprene (∼  1 h is similar to the turbulent mixing timescale (0.1–0.5 h, which indicates that isoprene concentrations are equally dependent on both photooxidation and boundary layer dynamics. Analysis of a model-derived concentration budget suggests that diurnal evolution of isoprene inside the CBL is mainly controlled by surface emissions and chemical loss; the diurnal evolution of O3 is dominated by entrainment. The NO to HO2 ratio (NO : HO2 is used as an indicator of anthropogenic impact on the CBL chemical composition and spans a wide range (1–163. The fate of hydroxyl-substituted isoprene peroxyl radical (HOC5H8OO·; ISOPOO is strongly affected by NO : HO2, shifting from NO-dominant to NO–HO2-balanced conditions from early morning to noontime. This chemical regime change is reflected in the diurnal evolution of isoprene hydroxynitrates (ISOPN and isoprene hydroxy hydroperoxides (ISOPOOH.

Two-year concurrent observation of isoprene at 20 sites over China: comparison with MEGAN-REAM model simulation

Science.gov (United States)

Zhang, Y.; Yang, W.; Zhang, R.; Zhang, Z.; Lyu, S.; Yu, J.; Wang, Y.; Wang, G.; Wang, X.

2017-12-01

Isoprene, the most abundant non-methane hydrocarbon emitted from plants, directly and indirectly affects atmospheric photochemistry and radiative forcing, yet narrowing its emission uncertainties is a continuous challenge. Comparison of observed and modelled isoprene on large spatiotemporal scales would help recognize factors that control isoprene variability, systematic field observation data are however quite lacking. Here we collected ambient air samples with 1 L silonite-treated stainless steel canisters simultaneously at 20 sites over China on every Wednesday at approximately 14:00 pm Beijing time from 2012 to 2014, and analyzed isoprene mixing ratios by preconcentrator-GC-MSD/FID. Observed isoprene mixing ratios were also compared with that simulated by coupling MEGAN 2.0 (Guenther et al., 2006) with a 3-D Regional chEmical trAnsport Model (REAM) (Zhang et al., 2017). Similar seasonal variations between observation and model simulation were obtained for most of sampling sites, but overall the average isoprene mixing ratios during growing months (May to October) was 0.37 ± 0.08 ppbv from model simulation, about 32% lower than that of 0.54 ± 0.20 ppbv based on ground-based observation, and this discrepancy was particularly significant in north China during wintertime. Further investigation demonstrated that emission of biogenic isoprene in northwest China might be underestimated and non-biogenic emission, such burning biomass/biofuel, might contribute to the elevated levels of isoprene during winter time. The observation-based empirical formulas for changing isoprene emission with solar radiation and temperature were also derived for different regions of China.

Uncertainty in biogenic isoprene emissions and its impacts on tropospheric chemistry in East Asia

International Nuclear Information System (INIS)

Han, K.M.; Park, R.S.; Kim, H.K.; Woo, J.H.; Kim, J.; Song, C.H.

2013-01-01

In this study, the accuracy of biogenic isoprene emission fluxes over East Asia during two summer months (July and August) was examined by comparing two tropospheric HCHO columns (Ω HCHO ) obtained from the SCIAMACHY sensor and the Community Multi-scale Air Quality (CMAQ v4.7.1) model simulations, using three available biogenic isoprene emission inventories over East Asia: i) GEIA, ii) MEGAN and iii) MOHYCAN. From this comparative analysis, the tropospheric HCHO columns from the CMAQ model simulations, using the MEGAN and MOHYCAN emission inventories (Ω CMAQ, MEGAN and Ω CMAQ, MOHYCAN ), were found to agree well with the tropospheric HCHO columns from the SCIAMACHY observations (Ω SCIA ). Secondly, the propagation of such uncertainties in the biogenic isoprene emission fluxes to the levels of atmospheric oxidants (e.g., OH and HO 2 ) and other atmospheric gaseous/particulate species over East Asia during the two summer months was also investigated. As the biogenic isoprene emission fluxes decreased from the GEIA to the MEGAN emission inventories, the levels of OH radicals increased by factors of 1.39 and 1.75 over Central East China (CEC) and South China, respectively. Such increases in the OH radical mixing ratios subsequently influence the partitioning of HO y species. For example, the HO 2 /OH ratios from the CMAQ model simulations with GEIA isoprene emissions were 2.7 times larger than those from the CMAQ model simulations based on MEGAN isoprene emissions. The large HO 2 /OH ratios from the CMAQ model simulations with the GEIA biogenic emission were possibly due to the overestimation of GEIA biogenic isoprene emissions over East Asia. It was also shown that such large changes in HO x radicals created large differences on other tropospheric compounds (e.g., NO y chemistry) over East Asia during the summer months. - Highlights: • GEIA isoprene emissions were possibly overestimated over East Asia. • Using MEGAN or MOHYCAN emissions in CMAQ well captured

Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene

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R. M. Healy

2008-06-01

Full Text Available A new denuder-filter sampling technique has been used to investigate the gas/particle partitioning behaviour of the carbonyl products from the photooxidation of isoprene and 1,3,5-trimethylbenzene. A series of experiments was performed in two atmospheric simulation chambers at atmospheric pressure and ambient temperature in the presence of NO_x and at a relative humidity of approximately 50%. The denuder and filter were both coated with the derivatizing agent O-(2,3,4,5,6-pentafluorobenzyl-hydroxylamine (PFBHA to enable the efficient collection of gas- and particle-phase carbonyls respectively. The tubes and filters were extracted and carbonyls identified as their oxime derivatives by GC-MS. The carbonyl products identified in the experiments accounted for around 5% and 10% of the mass of secondary organic aerosol formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene respectively.

Experimental gas/particle partitioning coefficients were determined for a wide range of carbonyl products formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene and compared with the theoretical values based on standard absorptive partitioning theory. Photooxidation products with a single carbonyl moiety were not observed in the particle phase, but dicarbonyls, and in particular, glyoxal and methylglyoxal, exhibited gas/particle partitioning coefficients several orders of magnitude higher than expected theoretically. These findings support the importance of heterogeneous and particle-phase chemical reactions for SOA formation and growth during the atmospheric degradation of anthropogenic and biogenic hydrocarbons.

Potential sensitivity of photosynthesis and isoprene emission to direct radiative effects of atmospheric aerosol pollution

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Strada, Susanna; Unger, Nadine

2016-04-01

A global Earth system model is applied to quantify the impacts of direct anthropogenic aerosol effective radiative forcing on gross primary productivity (GPP) and isoprene emission. The impacts of different pollution aerosol sources (anthropogenic, biomass burning, and non-biomass burning) are investigated by performing sensitivity experiments. The model framework includes all known light and meteorological responses of photosynthesis, but uses fixed canopy structures and phenology. On a global scale, our results show that global land carbon fluxes (GPP and isoprene emission) are not sensitive to pollution aerosols, even under a global decline in surface solar radiation (direct + diffuse) by ˜ 9 %. At a regional scale, GPP and isoprene emission show a robust but opposite sensitivity to pollution aerosols in regions where forested canopies dominate. In eastern North America and Eurasia, anthropogenic pollution aerosols (mainly from non-biomass burning sources) enhance GPP by +5-8 % on an annual average. In the northwestern Amazon Basin and central Africa, biomass burning aerosols increase GPP by +2-5 % on an annual average, with a peak in the northwestern Amazon Basin during the dry-fire season (+5-8 %). The prevailing mechanism varies across regions: light scattering dominates in eastern North America, while a reduction in direct radiation dominates in Europe and China. Aerosol-induced GPP productivity increases in the Amazon and central Africa include an additional positive feedback from reduced canopy temperatures in response to increases in canopy conductance. In Eurasia and northeastern China, anthropogenic pollution aerosols drive a decrease in isoprene emission of -2 to -12 % on an annual average. Future research needs to incorporate the indirect effects of aerosols and possible feedbacks from dynamic carbon allocation and phenology.

Contribution of various carbon sources toward isoprene biosynthesis in poplar leaves mediated by altered atmospheric CO2 concentrations.

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Amy M Trowbridge

Full Text Available Biogenically released isoprene plays important roles in both tropospheric photochemistry and plant metabolism. We performed a (13CO(2-labeling study using proton-transfer-reaction mass spectrometry (PTR-MS to examine the kinetics of recently assimilated photosynthate into isoprene emitted from poplar (Populus × canescens trees grown and measured at different atmospheric CO(2 concentrations. This is the first study to explicitly consider the effects of altered atmospheric CO(2 concentration on carbon partitioning to isoprene biosynthesis. We studied changes in the proportion of labeled carbon as a function of time in two mass fragments, M41(+, which represents, in part, substrate derived from pyruvate, and M69(+, which represents the whole unlabeled isoprene molecule. We observed a trend of slower (13C incorporation into isoprene carbon derived from pyruvate, consistent with the previously hypothesized origin of chloroplastic pyruvate from cytosolic phosphenolpyruvate (PEP. Trees grown under sub-ambient CO(2 (190 ppmv had rates of isoprene emission and rates of labeling of M41(+ and M69(+ that were nearly twice those observed in trees grown under elevated CO(2 (590 ppmv. However, they also demonstrated the lowest proportion of completely labeled isoprene molecules. These results suggest that under reduced atmospheric CO(2 availability, more carbon from stored/older carbon sources is involved in isoprene biosynthesis, and this carbon most likely enters the isoprene biosynthesis pathway through the pyruvate substrate. We offer direct evidence that extra-chloroplastic rather than chloroplastic carbon sources are mobilized to increase the availability of pyruvate required to up-regulate the isoprene biosynthesis pathway when trees are grown under sub-ambient CO(2.

Distribution and sea-to-air flux of isoprene in the East China Sea and the South Yellow Sea during summer.

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Li, Jian-Long; Zhang, Hong-Hai; Yang, Gui-Peng

2017-07-01

Spatial distribution and sea-to-air flux of isoprene in the East China Sea and the South Yellow Sea in July 2013 were investigated. This study is the first to report the concentrations of isoprene in the China marginal seas. Isoprene concentrations in the surface seawater during summer ranged from 32.46 to 173.5 pM, with an average of 83.62 ± 29.22 pM. Distribution of isoprene in the study area was influenced by the diluted water from the Yangtze River, which stimulated higher in-situ phytoplankton production of isoprene rather than direct freshwater input. Variations in isoprene concentrations were found to be diurnal, with high values observed during daytime. A significant correlation was observed between isoprene and chlorophyll a in the study area. Relatively higher isoprene concentrations were recorded at stations where the phytoplankton biomass was dominated by Chaetoceros, Skeletonema, Pennate-nitzschia, and Thalassiosira. Positive correlation was observed between isoprene and methyl iodide. In addition, sea-to-air fluxes of isoprene approximately ranged from 22.17 nmol m -2  d -1 -537.2 nmol m -2  d -1 , with an average of 161.5 ± 133.3 nmol m -2  d -1 . These results indicate that the coastal and shelf areas may be important sources of atmospheric isoprene. Copyright © 2017 Elsevier Ltd. All rights reserved.

Concentrations and fluxes of isoprene and oxygenated VOCs at a French Mediterranean oak forest

International Nuclear Information System (INIS)

Kalogridis, C.; Gros, V.; Sarda-Esteve, R.; Bonsang, B.; Bonnaire, N.; Boissard, C.; Baisnee, D.; Lathiere, J.

2014-01-01

The CANOPEE project aims to better understand the biosphere-atmosphere exchanges of biogenic volatile organic compounds (BVOCs) in the case of Mediterranean ecosystems and the impact of in-canopy processes on the atmospheric chemical composition above the canopy. Based on an intensive field campaign, the objective of our work was to determine the chemical composition of the air inside a canopy as well as the net fluxes of reactive species between the canopy and the boundary layer. Measurements were carried out during spring 2012 at the field site of the Oak Observatory of the Observatoire de Haute Provence (O3HP) located in the southeast of France. The site is a forest ecosystem dominated by downy oak, Quercus pubescens Willd., a typical Mediterranean species which features large isoprene emission rates. Mixing ratios of isoprene, its degradation products methylvinylketone (MVK) and methacrolein (MACR) and several other oxygenated VOC (OxVOC) were measured above the canopy using an online proton transfer reaction mass spectrometer (PTR-MS), and fluxes were calculated by the disjunct eddy covariance approach. The O3HP site was found to be a very significant source of isoprene emissions, with daily maximum ambient concentrations ranging between 2-16 ppbv inside and 2-5 ppbv just above the top of the forest canopy. Significant isoprene fluxes were observed only during daytime, following diurnal cycles with midday net emission fluxes from the canopy ranging between 2.0 and 9.7 mgm -2 h -1 . Net isoprene normalized flux (at 30 C, 1000 μmol quantam -2 s -1 ) was estimated at 7.4 mgm -2 h -1 . Evidence of direct emission of methanol was also found exhibiting maximum daytime fluxes ranging between 0.2 and 0.6 mgm -2 h -1 , whereas flux values for monoterpenes and others OxVOC such as acetone and acetaldehyde were below the detection limit. The MVK+MACR-to-isoprene ratio provided useful information on the oxidation of isoprene, and is in agreement with recent findings

Uncertainty in biogenic isoprene emissions and its impacts on tropospheric chemistry in East Asia.

Science.gov (United States)

Han, K M; Park, R S; Kim, H K; Woo, J H; Kim, J; Song, C H

2013-10-01

In this study, the accuracy of biogenic isoprene emission fluxes over East Asia during two summer months (July and August) was examined by comparing two tropospheric HCHO columns (ΩHCHO) obtained from the SCIAMACHY sensor and the Community Multi-scale Air Quality (CMAQ v4.7.1) model simulations, using three available biogenic isoprene emission inventories over East Asia: i) GEIA, ii) MEGAN and iii) MOHYCAN. From this comparative analysis, the tropospheric HCHO columns from the CMAQ model simulations, using the MEGAN and MOHYCAN emission inventories (Ω(CMAQ, MEGAN) and Ω(CMAQ, MOHYCAN)), were found to agree well with the tropospheric HCHO columns from the SCIAMACHY observations (Ω(SCIA)). Secondly, the propagation of such uncertainties in the biogenic isoprene emission fluxes to the levels of atmospheric oxidants (e.g., OH and HO2) and other atmospheric gaseous/particulate species over East Asia during the two summer months was also investigated. As the biogenic isoprene emission fluxes decreased from the GEIA to the MEGAN emission inventories, the levels of OH radicals increased by factors of 1.39 and 1.75 over Central East China (CEC) and South China, respectively. Such increases in the OH radical mixing ratios subsequently influence the partitioning of HO(y) species. For example, the HO2/OH ratios from the CMAQ model simulations with GEIA isoprene emissions were 2.7 times larger than those from the CMAQ model simulations based on MEGAN isoprene emissions. The large HO2/OH ratios from the CMAQ model simulations with the GEIA biogenic emission were possibly due to the overestimation of GEIA biogenic isoprene emissions over East Asia. It was also shown that such large changes in HO(x) radicals created large differences on other tropospheric compounds (e.g., NO(y) chemistry) over East Asia during the summer months. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Airborne observations of total RONO2: new constraints on the yield and lifetime of isoprene nitrates

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W. H. Brune

2009-02-01

Full Text Available Formation of isoprene nitrates (INs is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Isoprene nitrates also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Current assessments indicate that formation rates of isoprene nitrates are uncertain to a factor of 2–3 and the subsequent fate of isoprene nitrates remains largely unconstrained by laboratory, field or modeling studies. Measurements of total alkyl and multifunctional nitrates (ΣANs, NO2, total peroxy nitrates (ΣPNs, HNO3, CH2O, isoprene and other VOC were obtained from the NASA DC-8 aircraft during summer 2004 over the continental US during the INTEX-NA campaign. These observations represent the first characterization of ΣANs over a wide range of land surface types and in the lower free troposphere. ΣANs were a significant, 12–20%, fraction of NOy throughout the experimental domain and ΣANs were more abundant when isoprene was high. We use the observed hydrocarbon species to calculate the relative contributions of ΣAN precursors to their production. These calculations indicate that isoprene represents at least three quarters of the ΣAN source in the summertime continental boundary layer of the US. An observed correlation between ΣANs and CH2O is used to place constraints on nitrate yields from isoprene oxidation, atmospheric lifetimes of the resulting nitrates and recycling efficiencies of nitrates during subsequent oxidation. We find reasonable fits to the data using sets of production rates, lifetimes and recycling efficiencies of INs as follows (4.4%, 16 h, 97%, (8%, 2.5 h, 79% and (12%, 95 min, 67%. The analysis indicates that the lifetime of ΣANs as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates to reaction with OH, implying that

Drought impact on Quercus pubescens Willd. isoprene emissions over the Mediterranean area: what future?

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Cyrielle Genard-Zielinski, Anne; Boissard, Christophe; Ormeño, Elena; Lathière, Juliette; Guenet, Bertrand; Gauquelin, Thierry; Fernandez, Catherine

2015-04-01

Biogenic Volatile Organic Compounds (BVOCs) released by plants mostly originate from their secondary metabolism. Their emissions are modulated, in terms of intensity and molecule diversity, by environmental conditions. Among BVOCs, isoprene has been especially studied due to its high emission fluxes and its contribution to tropospheric photochemistry, both in the gaseous and particulate phases. However, the way isoprene emissions are impacted by some abiotic factors, especially water stress, is still under debate. In a world facing climatic changes, global climate models expect air temperature and drought intensity to strengthen in the Mediterranean area by 2100. Our work focuses on the impact of water stress on isoprene emissions (ERiso) from Quercus pubescens Willd. This species covers large areas of the Mediterranean area where it appears to be the main isoprene emitter. An in situ experimentation was performed at the O3HP (Oak Observatory at OHP, southern France) in a pubescent oak forest with trees adapted to long lasting stress periods. We investigated during a whole seasonal cycle (from June 2012 to June 2013) the course of ERiso under both natural water stress (control treatment: C) and intensified water stress (stress treatment: S) by artificially reducing rain by 30% using a specific rain exclusion device. Restricted rain did not modify either the net CO2 assimilation or ERiso during the whole season. However, isoprene emission factors (Is) for trees under S were significantly higher (a factor of ˜ 2) than for trees growing under C in August (137.8 compared to 75.3 μgC.gDM-1.h-1 respectively) and September (75.3 compared to 40.2 μgC.gDM-1.h-1 respectively). Based on our experimental emission database, an appropriate isoprene emission algorithm (GZ2014) was developed using a statistic approach (an artificial neural network). Using ambient and edaphic environmental parameters integrated over up to 3 weeks, GZ2014 was found to represent more than 80% of

High-resolution inversion of OMI formaldehyde columns over the Southeast US to infer isoprene emissions

Science.gov (United States)

Kaiser, J.; Zhu, L.; Travis, K.; Jacob, D.

2017-12-01

In the South East United States, biogenic isoprene fuels tropospheric ozone formation, and its oxidation products contribute significantly to organic aerosol. Bottom-up emission inventories rely on very limited isoprene emission and land-cover data, yielding uncertainties of a factor of 2 or more. Here, we use formaldehyde columns from the Ozone Monitoring Instrument in a high-resolution (0.25 x 0.325o) adjoint-based inversion to constrain isoprene emissions over the SE US during Aug-Sept of 2013. We find that the MEGANv2.1 inventory is biased high over most of the SE US. Our derived scaling factors show significant spatial variability, with the largest corrections applied to Louisiana and the Edwards Plateau in Texas. We test our inversion results against a comprehensive set of isoprene oxidation product observations from the NASA SEAC4RS flight campaign. The SEAC4RS data provides new confidence in the satellite retrievals and in mechanism linking isoprene oxidation to formaldehyde production. Finally, we relate the posterior scaling factors to the underlying land-type, and examine potential sources of observed biases.

Isoprene emission inventory for the BOREAS southern study area

International Nuclear Information System (INIS)

Westberg, H.; Lamb, B.; Kempf, K.; Allwine, G.

2000-01-01

The Boreal Ecosystem-Atmosphere Study (BOREAS) was designed to measure trace gas fluxes, nutrient cycling, hydrologic budgets and other ecosystem features in order to establish relationships between ecosystem processes and various global climate change scenarios. During the 1994 BOREAS field study isoprene and terpene emissions have been measured at several sites in the Southern Study Area (SSA). Ambient measurements were also made to help establish the chemical importance of these biogenic species in boreal atmosphere. The data was used to test and improve algorithms for predicting emission rates as a function of species, environmental conditions and biomass dynamics and to provide an expanded database describing the relationship of volatile organic compounds emissions to ecosystem dynamics. The study also sought to provide the foundation for improved understanding of physical exchange processes, and define hydrocarbon reactivity in the boundary layer at high latitudes. Details of the biogenic emission rate measurements made in the SSA are also discussed, including the creation of an isoprene emission inventory for the area. The study has been helpful in eliminating major sources of uncertainty associated with estimates of carbon loss due to isoprene emission on the BOREAS SSA. 28 refs., 4 tabs., 5 figs

Uncertainty in biogenic isoprene emissions and its impacts on tropospheric chemistry in East Asia

Energy Technology Data Exchange (ETDEWEB)

Han, K.M.; Park, R.S. [School of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju, 500-712 (Korea, Republic of); Advanced Environmental Monitoring Research Center (ADEMRC), Gwangju Institute of Science and Technology (GIST), Gwangju, 500-712 (Korea, Republic of); Kim, H.K.; Woo, J.H. [Department of Advanced Technology Fusion, Konkuk University, 1 Hwayang dong, Gwangjin-gu, Seoul, 143-701 (Korea, Republic of); Kim, J. [Department of Atmospheric Sciences, Yonsei University, 134 Sinchon-dong, Seodaemoon-gu, Seoul, 120-749 (Korea, Republic of); Song, C.H., E-mail: chsong@gist.ac.kr [School of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju, 500-712 (Korea, Republic of); Advanced Environmental Monitoring Research Center (ADEMRC), Gwangju Institute of Science and Technology (GIST), Gwangju, 500-712 (Korea, Republic of)

2013-10-01

In this study, the accuracy of biogenic isoprene emission fluxes over East Asia during two summer months (July and August) was examined by comparing two tropospheric HCHO columns (Ω{sub HCHO}) obtained from the SCIAMACHY sensor and the Community Multi-scale Air Quality (CMAQ v4.7.1) model simulations, using three available biogenic isoprene emission inventories over East Asia: i) GEIA, ii) MEGAN and iii) MOHYCAN. From this comparative analysis, the tropospheric HCHO columns from the CMAQ model simulations, using the MEGAN and MOHYCAN emission inventories (Ω{sub CMAQ,} {sub MEGAN} and Ω{sub CMAQ,} {sub MOHYCAN}), were found to agree well with the tropospheric HCHO columns from the SCIAMACHY observations (Ω{sub SCIA}). Secondly, the propagation of such uncertainties in the biogenic isoprene emission fluxes to the levels of atmospheric oxidants (e.g., OH and HO{sub 2}) and other atmospheric gaseous/particulate species over East Asia during the two summer months was also investigated. As the biogenic isoprene emission fluxes decreased from the GEIA to the MEGAN emission inventories, the levels of OH radicals increased by factors of 1.39 and 1.75 over Central East China (CEC) and South China, respectively. Such increases in the OH radical mixing ratios subsequently influence the partitioning of HO{sub y} species. For example, the HO{sub 2}/OH ratios from the CMAQ model simulations with GEIA isoprene emissions were 2.7 times larger than those from the CMAQ model simulations based on MEGAN isoprene emissions. The large HO{sub 2}/OH ratios from the CMAQ model simulations with the GEIA biogenic emission were possibly due to the overestimation of GEIA biogenic isoprene emissions over East Asia. It was also shown that such large changes in HO{sub x} radicals created large differences on other tropospheric compounds (e.g., NO{sub y} chemistry) over East Asia during the summer months. - Highlights: • GEIA isoprene emissions were possibly overestimated over East Asia. �

The Ozark Plateaus Regional Aquifer Study—Documentation of a groundwater-flow model constructed to assess water availability in the Ozark Plateaus

Science.gov (United States)

Clark, Brian R.; Richards, Joseph M.; Knierim, Katherine J.

2018-03-30

Recent short-term drought conditions have emphasized the need to better understand the delicate balance between abundance, sustainability, and scarcity of groundwater in the Ozark Plateaus aquifer system. In 2014, the U.S. Geological Survey began construction of a groundwater-flow model as a tool for the assessment of groundwater availability in the Ozark Plateaus aquifer system. The model was developed to benefit concurrent and future investigations involving groundwater-pumping scenarios, optimization, particle transport, and groundwater-monitoring network analysis.The groundwater model simulates 116 years (1900–2015) of hydrologic conditions and the response of the groundwater system to changes in stress including changes in recharge and groundwater pumping for water supply. Semiseasonal stress periods were simulated from the later part of 1991 to 2015 and represent higher demand and lower recharge in the spring and summer months and lower demand and higher recharge in the fall and winter months. Groundwater pumping increases throughout the simulation period with a maximum rate of about 600 million gallons per day (Mgal/d).The process of matching historical hydrologic data for the Ozark Plateaus aquifer system model was accomplished by a combination of manual changes to parameter values and automated calibration methods. Observation data used in the development and evaluation of the model included 19,045 hydraulic-head observations from 6,683 wells within the model area. Observation data also included stream leakage estimates summed to calculate a net gain or net loss value for approximately 81 named streams.The majority (mean of over 95 percent) of the recharge component is discharged through streams simulated in the model. The total simulated discharge to streams fluctuates seasonally between 7,500 and 17,500 Mgal/d with a mean outflow of 11,500 Mgal/d. Much of the remaining balance between modeled recharge inflows and stream outflows is made up by water

Spatio-Temporal Trends of Oak Decline and Mortality under Periodic Regional Drought in the Ozark Highlands of Arkansas and Missouri

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Stephen R. Shifley

2012-08-01

Full Text Available At the forest landscape/region level, based on annual Forest Inventory and Analysis plot data from 1999 to 2010, oak decline and mortality trends for major oak species (groups were examined in the Ozark Highlands of Arkansas and Missouri. Oak decline has elevated cumulative mortality of red oak species to between 11 and 15 percent in terms of relative density and basal area of standing dead oak trees, respectively. These values are three to five times higher than for white oak group and non-oak species. Oak decline and associated escalating mortality have occurred primarily in red oak species while the white oak group has maintained a relatively stable mortality rate that is comparable to non-oak species. Cross-correlation analyses indicate that mortality in the red oak group was significantly correlated with the growing season Palmer drought severity index (PDSI and usually lagged two to three years following single drought events. Moreover, based on the past 17 years PDSI data, it appears that the cumulative impacts of drought may last up to 10 years. The Ozark Highlands experienced a severe drought extending from 1998 to 2000 and another milder drought from 2005 to 2006. These drought events triggered the escalation of mortality starting around year 2000. Spatially, high red oak mortality sites (hot spots with proportional basal area mortality > 0.12 initially occurred in the central Ozarks and spread gradually over most of the Ozark Highlands as regional droughts continued. In contrast, sites with elevated white oak and non-oak mortality occurred sporadically, mainly in the southern portion (Arkansas of the Ozark Highlands. During the most recent inventory period (2006–2010, over 60%, 7% and 5% of red oak, white oak and non-oak groups, respectively, had relative mortality rates of > 12%.

Global terrestrial isoprene emission models: sensitivity to variability in climate and vegetation

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A. Arneth

2011-08-01

Full Text Available Due to its effects on the atmospheric lifetime of methane, the burdens of tropospheric ozone and growth of secondary organic aerosol, isoprene is central among the biogenic compounds that need to be taken into account for assessment of anthropogenic air pollution-climate change interactions. Lack of process-understanding regarding leaf isoprene production as well as of suitable observations to constrain and evaluate regional or global simulation results add large uncertainties to past, present and future emissions estimates. Focusing on contemporary climate conditions, we compare three global isoprene models that differ in their representation of vegetation and isoprene emission algorithm. We specifically aim to investigate the between- and within model variation that is introduced by varying some of the models' main features, and to determine which spatial and/or temporal features are robust between models and different experimental set-ups. In their individual standard configurations, the models broadly agree with respect to the chief isoprene sources and emission seasonality, with maximum monthly emission rates around 20–25 Tg C, when averaged by 30-degree latitudinal bands. They also indicate relatively small (approximately 5 to 10 % around the mean interannual variability of total global emissions. The models are sensitive to changes in one or more of their main model components and drivers (e.g., underlying vegetation fields, climate input which can yield increases or decreases in total annual emissions of cumulatively by more than 30 %. Varying drivers also strongly alters the seasonal emission pattern. The variable response needs to be interpreted in view of the vegetation emission capacities, as well as diverging absolute and regional distribution of light, radiation and temperature, but the direction of the simulated emission changes was not as uniform as anticipated. Our results highlight the need for modellers to evaluate their

Isoprene emissions modelling for West Africa: MEGAN model evaluation and sensitivity analysis

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J. Ferreira

2010-09-01

Full Text Available Isoprene emissions are the largest source of reactive carbon to the atmosphere, with the tropics being a major source region. These natural emissions are expected to change with changing climate and human impact on land use. As part of the African Monsoon Multidisciplinary Analyses (AMMA project the Model of Emissions of Gases and Aerosols from Nature (MEGAN has been used to estimate the spatial and temporal distribution of isoprene emissions over the West African region. During the AMMA field campaign, carried out in July and August 2006, isoprene mixing ratios were measured on board the FAAM BAe-146 aircraft. These data have been used to make a qualitative evaluation of the model performance.

MEGAN was firstly applied to a large area covering much of West Africa from the Gulf of Guinea in the south to the desert in the north and was able to capture the large scale spatial distribution of isoprene emissions as inferred from the observed isoprene mixing ratios. In particular the model captures the transition from the forested area in the south to the bare soils in the north, but some discrepancies have been identified over the bare soil, mainly due to the emission factors used. Sensitivity analyses were performed to assess the model response to changes in driving parameters, namely Leaf Area Index (LAI, Emission Factors (EF, temperature and solar radiation.

A high resolution simulation was made of a limited area south of Niamey, Niger, where the higher concentrations of isoprene were observed. This is used to evaluate the model's ability to simulate smaller scale spatial features and to examine the influence of the driving parameters on an hourly basis through a case study of a flight on 17 August 2006.

This study highlights the complex interactions between land surface processes and the meteorological dynamics and chemical composition of the PBL. This has implications for quantifying the impact of biogenic emissions

Methanol and isoprene emissions from the fast growing tropical pioneer species Vismia guianensis (Aubl. Pers. (Hypericaceae in the central Amazon forest

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K. J. Jardine

2016-05-01

Full Text Available Isoprene (Is emissions by plants represent a loss of carbon and energy resources leading to the initial hypothesis that fast growing pioneer species in secondary tropical forests allocate carbon primarily to growth at the expense of isoprenoid defenses. In this study, we quantified leaf isoprene and methanol emissions from the abundant pantropical pioneer tree species Vismia guianensis and ambient isoprene concentrations above a diverse secondary forest in the central Amazon. As photosynthetically active radiation (PAR was varied (0 to 3000 µmol m−2 s−1 under standard leaf temperature (30 °C, isoprene emissions from V. guianensis increased without saturation up to 80 nmol m−2 s−1. A nonlinear increase in isoprene emissions with respect to net photosynthesis (Pn resulted in the fraction of Pn dedicated to isoprene emissions increasing with light intensity (up to 2 % of Pn. Emission responses to temperature under standard light conditions (PAR of 1000 µmol m−2 s−1 resulted in the classic uncoupling of isoprene emissions (Topt, iso > 40 °C from net photosynthesis (Topt, Pn = 30.0–32.5 °C with up to 7 % of Pn emitted as isoprene at 40 °C. Under standard environmental conditions of PAR and leaf temperature, young V. guianensis leaves showed high methanol emissions, low Pn, and low isoprene emissions. In contrast, mature leaves showed high Pn, high isoprene emissions, and low methanol emissions, highlighting the differential control of leaf phenology over methanol and isoprene emissions. High daytime ambient isoprene concentrations (11 ppbv were observed above a secondary Amazon rainforest, suggesting that isoprene emissions are common among neotropical pioneer species. The results are not consistent with the initial hypothesis and support a functional role of methanol during leaf expansion and the establishment of photosynthetic machinery and a protective role of isoprene for

Potential sensitivity of photosynthesis and isoprene emission to direct radiative effects of atmospheric aerosol pollution

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S. Strada

2016-04-01

Full Text Available A global Earth system model is applied to quantify the impacts of direct anthropogenic aerosol effective radiative forcing on gross primary productivity (GPP and isoprene emission. The impacts of different pollution aerosol sources (anthropogenic, biomass burning, and non-biomass burning are investigated by performing sensitivity experiments. The model framework includes all known light and meteorological responses of photosynthesis, but uses fixed canopy structures and phenology. On a global scale, our results show that global land carbon fluxes (GPP and isoprene emission are not sensitive to pollution aerosols, even under a global decline in surface solar radiation (direct + diffuse by  ∼ 9 %. At a regional scale, GPP and isoprene emission show a robust but opposite sensitivity to pollution aerosols in regions where forested canopies dominate. In eastern North America and Eurasia, anthropogenic pollution aerosols (mainly from non-biomass burning sources enhance GPP by +5–8 % on an annual average. In the northwestern Amazon Basin and central Africa, biomass burning aerosols increase GPP by +2–5 % on an annual average, with a peak in the northwestern Amazon Basin during the dry-fire season (+5–8 %. The prevailing mechanism varies across regions: light scattering dominates in eastern North America, while a reduction in direct radiation dominates in Europe and China. Aerosol-induced GPP productivity increases in the Amazon and central Africa include an additional positive feedback from reduced canopy temperatures in response to increases in canopy conductance. In Eurasia and northeastern China, anthropogenic pollution aerosols drive a decrease in isoprene emission of −2 to −12 % on an annual average. Future research needs to incorporate the indirect effects of aerosols and possible feedbacks from dynamic carbon allocation and phenology.

Above Canopy Emissions of Isoprene and Monoterpenes from a Southeast Asian Tropical Forest

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Baker, B.; Johnson, C.; Cai, Z.; Guenther, A.; Greenberg, J.; Bai, J.; Li, Q.

2003-12-01

Fluxes of isoprene were measured using the eddy covariance technique and an ozone chemiluminescence isoprene sensor above a secondary tropical forest/rubber tree plantation located in the Xishuangbanna region of southern China during the wet and dry seasons. Fluxes of monoterpenes were inferred from ambient boundary layer concentrations (wet season) and from relaxed eddy accumulation measurements (dry season). Isoprene emissions were comparable to what has been observed from other tropical forests in Africa and South America. In this forest, monoterpene emissions were much higher during the wet season due to the senescence of the rubber trees during the dry season. These flux measurements represent the first ecosystem level flux measurements reported from Southeast Asian tropical forests.

Direct Observations of Isoprene Secondary Organic Aerosol Formation in Ambient Cloud Droplets

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Zelenyuk, A.; Bell, D.; Thornton, J. A.; Fast, J. D.; Shrivastava, M. B.; Berg, L. K.; Imre, D. G.; Mei, F.; Shilling, J.; Suski, K. J.; Liu, J.; Tomlinson, J. M.; Wang, J.

2017-12-01

Multiphase chemistry of isoprene photooxidation products has been shown to be one of the major sources of secondary organic aerosol (SOA) in the atmosphere. A number of recent studies indicate that aqueous aerosol phase provides a medium for reactive uptake of isoprene photooxidation products, and in particular, isomeric isoprene epoxydiols (IEPOX), with reaction rates and yields being dependent on aerosol acidity, water content, sulfate concentration, and organic coatings. However, very few studies focused on chemistry occurring within actual cloud droplets. We will present data acquired during recent Holistic Interactions of Shallow Clouds, Aerosols, and Land Ecosystems (HI-SCALE) Campaign, which provide direct evidence for IEPOX-SOA formation in cloud droplets. Single particle mass spectrometer, miniSPLAT, and a high-resolution, time-of-flight aerosol mass spectrometer were used to characterize the composition of aerosol particles and cloud droplet residuals, while a high-resolution, time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) was used to characterize gas-phase compounds. We find that the composition of cloud droplet residuals was markedly different than that of aerosol particles sampled outside the cloud. Cloud droplet residuals were comprised of individual particles with high relative fractions of sulfate and nitrate and significant fraction of particles with mass spectra that are nearly identical to those of laboratory-generated IEPOX-SOA particles. The observed cloud-induced formation of IEPOX-SOA was accompanied by simultaneous decrease in measured concentrations of IEPOX and other gas-phase isoprene photooxidation products. Ultimately, the combined cloud, aerosol, and gas-phase measurements conducted during HI-SCALE will be used to develop and evaluate model treatments of aqueous-phase isoprene SOA formation.

Wildlife diversity of restored shortleaf pine-oak woodlands in the northern Ozarks

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Corinne S. Mann; Andrew R. Forbes

2007-01-01

Historic changes in land use have altered the plant composition and structure of shortleaf pine-oak woodlands in the northern Ozarks. As a result, the composition of wildlife communities in these landscapes has shifted to species that are more associated with closed canopy oak forests. For example, the red-cockaded woodpecker (Picoides borealis) has...

Potentiometric Surfaces in the Springfield Plateau and Ozark Aquifers of Northwestern Arkansas, Southeastern Kansas, Southwestern Missouri, and Northeastern Oklahoma, 2006

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Gillip, Jonathan A.; Czarnecki, John B.; Mugel, Douglas N.

2008-01-01

The Springfield Plateau and Ozark aquifers are important sources of ground water in the Ozark Plateaus aquifer system. Water from these aquifers is used for agricultural, domestic, industrial, and municipal water sources. Changing water use over time in these aquifers presents a need for updated potentiometric-surface maps of the Springfield Plateau and Ozark aquifers. The Springfield Plateau aquifer consists of water-bearing Mississippian-age limestone and chert. The Ozark aquifer consists of Late Cambrian to Middle Devonian age water-bearing rocks consisting of dolostone, limestone, and sandstone. Both aquifers are complex with areally varying lithologies, discrete hydrologic units, varying permeabilities, and secondary permeabilities related to fractures and karst features. During the spring of 2006, ground-water levels were measured in 285 wells. These data, and water levels from selected lakes, rivers, and springs, were used to create potentiometric-surface maps for the Springfield Plateau and Ozark aquifers. Linear kriging was used initially to construct the water-level contours on the maps; the contours were subsequently modified using hydrologic judgment. The potentiometric-surface maps presented in this report represent ground-water conditions during the spring of 2006. During the spring of 2006, the region received less than average rainfall. Dry conditions prior to the spring of 2006 could have contributed to the observed water levels as well. The potentiometric-surface map of the Springfield Plateau aquifer shows a maximum measured water-level altitude within the study area of about 1,450 feet at a spring in Barry County, Missouri, and a minimum measured water-level altitude of 579 feet at a well in Ottawa County, Oklahoma. Cones of depression occur in Dade, Lawrence and Newton Counties in Missouri and Delaware and Ottawa Counties in Oklahoma. These cones of depression are associated with private wells. Ground water in the Springfield Plateau aquifer

Can the capacity for isoprene emission acclimate to environmental modifications during autumn senescence in temperate deciduous tree species Populus tremula?

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Sun, Zhihong; Copolovici, Lucian; Niinemets, Ülo

2012-03-01

Changes in isoprene emission (Φ(isoprene)), and foliage photosynthetic (A) rates, isoprene precursor dimethylallyldiphosphate (DMADP), and nitrogen and carbon contents were studied from late summer to intensive leaf fall in Populus tremula to gain insight into the emission controls by temperature and endogenous, senescence-induced, modifications. Methanol emissions, characterizing degradation of cell wall pectins, were also measured. A rapid reduction in Φ(isoprene) and A of 60-70% of the initial value was observed in response to a rapid reduction of ambient temperature by ca. 15°C (cold stress). Later phases of senescence were associated with further reductions in Φ(isoprene) and A, with simultaneous major decrease in nitrogen content. However, during episodes of temperature increase, A and in particular, Φ(isoprene) partly recovered. Variation in Φ(isoprene) during senescence was correlated with average temperature of preceding days, with the highest degree of explained variance observed with average temperature of 6 days. Throughout the study, methanol emissions were small, but a large burst of methanol emission was associated with leaf yellowing and abscission. Overall, these data demonstrate that the capacity for isoprene emission can adjust to environmental conditions in senescing leaves as well, but the responsiveness is low compared with mid-season and is also affected by stress.

Sustaining recruitment of oak reproduction in uneven-aged stands in the Ozark Highlands.

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David R. Larsen; Edward F. Loewenstein; Paul S. Johnson

1999-01-01

Successful application of the single-tree selection system in Ozark oak forests depends on sustaining adequate recruitment of reproduction into the overstory. In turn, this requires maintaining stand density at ecologically appropriate levels. The ecological requirements for oak recruitment are discussed and guiding curves are presented that meet those requirements...

Determination of breath isoprene and acetone concentration with a needle-type extraction device in gas chromatography-mass spectrometry.

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Ueta, Ikuo; Mizuguchi, Ayako; Okamoto, Mitsuyoshi; Sakamaki, Hiroyuki; Hosoe, Masahiko; Ishiguro, Motoyuki; Saito, Yoshihiro

2014-03-20

Isoprene in human breath is said to be related to cholesterol metabolism, and the possibility of the correlations with some clinical parameters has been studied. However, at this stage, no clear benefit of breath isoprene has been reported for clinical diagnosis. In this work, isoprene and acetone concentrations were measured in the breath of healthy and obese subjects using a needle-type extraction device for subsequent analysis in gas chromatography-mass spectrometry (GC-MS) to investigate the possibility of these compounds as an indicator of possible diseases. After measuring intraday and interday variations of isoprene and acetone concentrations in breath samples of healthy subjects, their concentrations were also determined in 80 healthy and 17 obese subjects. In addition, correlation between these breath concentrations and the blood tests result was studied for these healthy and obese subjects. The results indicated successful determination of breath isoprene and acetone in this work, however, no clear correlation was observed between these measured values and the blood test results. Breath isoprene concentration may not be a useful indicator for obesity or hypercholesterolemia. Copyright © 2014 Elsevier B.V. All rights reserved.

Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

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E. A. Marais

2016-02-01

Full Text Available Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA, but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS and ground-based (SOAS observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx  ≡  NO + NO2 over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2 react significantly with both NO (high-NOx pathway and HO2 (low-NOx pathway, leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA and formaldehyde (a product of isoprene oxidation. Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA from the low-NOx pathway and glyoxal (28 % from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the effect of sulfate on aerosol acidity and volume. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation, but decrease more strongly as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume. The US Environmental Protection Agency (EPA projects 2013–2025 decreases in

Stomatal uptake and stomatal deposition of ozone in isoprene and monoterpene emitting plants.

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Fares, S; Loreto, F; Kleist, E; Wildt, J

2008-01-01

Volatile isoprenoids were reported to protect plants against ozone. To understand whether this could be the result of a direct scavenging of ozone by these molecules, the stomatal and non-stomatal uptake of ozone was estimated in plants emitting isoprene or monoterpenes. Ozone uptake by holm oak (Quercus ilex, a monoterpene emitter) and black poplar (Populus nigra, an isoprene emitter) was studied in whole plant enclosures (continuously stirred tank reactors, CSTR). The ozone uptake by plants was estimated measuring ozone concentration at the inlet and outlet of the reactors, after correcting for the uptake of the enclosure materials. Destruction of ozone at the cuticle or at the plant stems was found to be negligible compared to the ozone uptake through the stomata. For both plant species, a relationship between stomatal conductance and ozone uptake was found. For the poplar, the measured ozone losses were explained by the uptake of ozone through the stomata only, and ozone destruction by gas phase reactions with isoprene was negligible. For the oak, gas phase reactions of ozone with the monoterpenes emitted by the plants contributed significantly to ozone destruction. This was confirmed by two different experiments showing a) that in cases of high stomatal conductance but under low CO(2) concentration, a reduction of monoterpene emission was still associated with reduced O(3) uptake; and b) that ozone losses due to the gas phase reactions only can be measured when using the exhaust from a plant chamber to determine the gas phase reactivity in an empty reaction chamber. Monoterpenes can therefore relevantly scavenge ozone at leaf level contributing to protection against ozone.

Interaction between isoprene and ozone fluxes at ecosystem level in a poplar plantation and its impact at European level

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Zenone, T.; Hendriks, C.; Brilli, F.; Gioli, B.; Portillo Estrada, M.; Schaap, M.; Ceulemans, R.

2015-12-01

The emissions of Biogenic volatile organic compounds (BVOCs) from vegetation, mainly in form of isoprenoids, play an important role in the tropospheric ozone (O3) formation. The potential large expansion of isoprene emitter species (e.g. poplar) as biofuels feedstock might impact the ground level O3 formation. Here we report the simultaneous observations, using the eddy covariance (EC) technique, of isoprene, O3 and CO2 fluxes in a short rotation coppice (SRC) of poplar. The impact of current poplar plantations and associated isoprene emissions on ground level ozone concentrations for Europe was evaluated using a chemistry transport model (CTM) LOTOS-EUROS. The isoprene fluxes showed a well-defined seasonal and daily cycle that mirrored with the stomata O3 uptake. The isoprene emission and the stomata O3 uptake showed significant statistical relationship especially at elevated temperature. Isoprene was characterized by a remarkable peak of emissions (e.g. 38 nmol m-2s-1) occurring for few days as a consequence of the rapid variation of the air and surface temperature. During these days the photosynthetic apparatus (i.e. the CO2 fluxes) and transpiration rates did not show significant variation while we did observe a variation of the energy exchange and a reduction of the bowen ratio. The response of isoprene emissions to ambient O3 concentration follows the common form of the hormetic dose-response curve with a considerable reduction of the isoprene emissions at [O3] > 80 ppbv indicating a potential damping effect of the O3 levels on isoprene. Under the current condition the impact of SRC plantations on ozone concentrations / formation is very limited in Europe. Our findings indicate that, even with future scenarios with more SRC, or conventional poplar plantations, the impact on Ozone formation is negligible.

Marine isoprene production and consumption in the mixed layer of the surface ocean - a field study over two oceanic regions

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Booge, Dennis; Schlundt, Cathleen; Bracher, Astrid; Endres, Sonja; Zäncker, Birthe; Marandino, Christa A.

2018-02-01

Parameterizations of surface ocean isoprene concentrations are numerous, despite the lack of source/sink process understanding. Here we present isoprene and related field measurements in the mixed layer from the Indian Ocean and the eastern Pacific Ocean to investigate the production and consumption rates in two contrasting regions, namely oligotrophic open ocean and the coastal upwelling region. Our data show that the ability of different phytoplankton functional types (PFTs) to produce isoprene seems to be mainly influenced by light, ocean temperature, and salinity. Our field measurements also demonstrate that nutrient availability seems to have a direct influence on the isoprene production. With the help of pigment data, we calculate in-field isoprene production rates for different PFTs under varying biogeochemical and physical conditions. Using these new calculated production rates, we demonstrate that an additional significant and variable loss, besides a known chemical loss and a loss due to air-sea gas exchange, is needed to explain the measured isoprene concentration. We hypothesize that this loss, with a lifetime for isoprene between 10 and 100 days depending on the ocean region, is potentially due to degradation or consumption by bacteria.

WET AND DRY SEASON ECOSYSTEM LEVEL FLUXES OF ISOPRENE AND MONOTERPENES FROM A SOUTHEAST ASIAN SECONDARY FOREST AND RUBBER TREE PLANTATION

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Canopy scale fluxes of isoprene and monoterpenes were investigated in both wet and dry seasons above a rubber tree (Hevea brasiliensis)/secondary tropical forest in the Yunnan province of southwestern China. Drought conditions were unusually high during the dry season experiment....

The Forest as a Resource: From Prehistory to History in the Arkansas Ozarks

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George Sabo; Jami Joe Lockhart; Jerry E. Hilliard

2004-01-01

Study of past human land use in the Lee Creek Unit of the Ozark National Forest challenges the existence of "pristine" forests predating the arrival of historic Americans. The distribution of early nineteenth century American settlements corresponds closely to the distribution of late prehistoric Native American archeological sites. One explanation for this...

Effects of climate-induced changes in isoprene emissions after the eruption of Mount Pinatubo

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P. J. Telford

2010-08-01

Full Text Available In the 1990s the rates of increase of greenhouse gas concentrations, most notably of methane, were observed to change, for reasons that have yet to be fully determined. This period included the eruption of Mt. Pinatubo and an El Niño warm event, both of which affect biogeochemical processes, by changes in temperature, precipitation and radiation. We examine the impact of these changes in climate on global isoprene emissions and the effect these climate dependent emissions have on the hydroxy radical, OH, the dominant sink for methane. We model a reduction of isoprene emissions in the early 1990s, with a maximum decrease of 40 Tg(C/yr in late 1992 and early 1993, a change of 9%. This reduction is caused by the cooler, drier conditions following the eruption of Mt. Pinatubo. Isoprene emissions are reduced both directly, by changes in temperature and a soil moisture dependent suppression factor, and indirectly, through reductions in the total biomass. The reduction in isoprene emissions causes increases of tropospheric OH which lead to an increased sink for methane of up to 5 Tg(CH₄/year, comparable to estimated source changes over the time period studied. There remain many uncertainties in the emission and oxidation of isoprene which may affect the exact size of this effect, but its magnitude is large enough that it should remain important.

In situ measurements of isoprene and monoterpenes within a south-east Asian tropical rainforest

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C. E. Jones

2011-07-01

Full Text Available Biogenic volatile organic compounds (BVOCs emitted from tropical rainforests comprise a substantial fraction of global atmospheric VOC emissions, however there are only relatively limited measurements of these species in tropical rainforest regions. We present observations of isoprene, α-pinene, camphene, Δ-3-carene, γ-terpinene and limonene, as well as oxygenated VOCs (OVOCs of biogenic origin such as methacrolein, in ambient air above a tropical rainforest in Malaysian Borneo during the Oxidant and Particle Photochemical Processes above a south-east Asian tropical rainforest (OP3 project in 2008. Daytime composition was dominated by isoprene, with an average mixing ratio of the order of ~1 ppb. γ-terpinene, limonene and camphene were the most abundant monoterpenes, with average daytime mixing ratios of 102, 71 and 66 ppt respectively, and with an average monoterpene toisoprene ratio of 0.3 during sunlit hours, compared to 2.0 at night. Limonene and camphene abundances were seen to be related to both temperature and light conditions. In contrast, γ-terpinene emission continued into the late afternoon/evening, under relatively low temperature and light conditions. The contributions of isoprene, monoterpenes and other classes of VOC to the volatile carbon budget and OH reactivity have been summarised for this rainforest location. We observe good agreement between surface and aircraft measurements of boundary layer isoprene and methacrolein above the natural rainforest, suggesting that the ground-level observations are broadly representative of isoprene emissions from this region.

Height-Diameter Equations for 12 Upland Species in the Missouri Ozark Highlands

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J.R. Lootens; David R. Larsen; Stephen R. Shifley

2007-01-01

We calibrated a model predicting total tree height as a function of tree diameter for nine tree species common to the Missouri Ozarks. Model coefficients were derived from nearly 10,000 observed trees. The calibrated model did a good job predicting the mean height-diameter trend for each species (pseudo-R2 values ranged from 0.56 to 0.88), but...

The effects of isoprene and NOx on secondary organic aerosols formed through reversible and irreversible uptake to aerosol water

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El-Sayed, Marwa M. H.; Ortiz-Montalvo, Diana L.; Hennigan, Christopher J.

2018-01-01

Isoprene oxidation produces water-soluble organic gases capable of partitioning to aerosol liquid water. The formation of secondary organic aerosols through such aqueous pathways (aqSOA) can take place either reversibly or irreversibly; however, the split between these fractions in the atmosphere is highly uncertain. The aim of this study was to characterize the reversibility of aqSOA formed from isoprene at a location in the eastern United States under substantial influence from both anthropogenic and biogenic emissions. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was characterized in Baltimore, Maryland, USA, using measurements of particulate water-soluble organic carbon (WSOCp) in alternating dry and ambient configurations. WSOCp evaporation with drying was observed systematically throughout the late spring and summer, indicating reversible aqSOA formation during these times. We show through time lag analyses that WSOCp concentrations, including the WSOCp that evaporates with drying, peak 6 to 11 h after isoprene concentrations, with maxima at a time lag of 9 h. The absolute reversible aqSOA concentrations, as well as the relative amount of reversible aqSOA, increased with decreasing NOx / isoprene ratios, suggesting that isoprene epoxydiol (IEPOX) or other low-NOx oxidation products may be responsible for these effects. The observed relationships with NOx and isoprene suggest that this process occurs widely in the atmosphere, and is likely more important in other locations characterized by higher isoprene and/or lower NOx levels. This work underscores the importance of accounting for both reversible and irreversible uptake of isoprene oxidation products to aqueous particles.

Future changes in biogenic isoprene emissions: how might they affect regional and global atmospheric chemistry?

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Christine Wiedinmyer; Xuexi Tie; Alex Guenther; Ron Neilson; Claire. Granier

2006-01-01

Isoprene is emitted from vegetation to the atmosphere in significant quantities, and it plays an important role in the reactions that control tropospheric oxidant concentrations. As future climatic and land-cover changes occur, the spatial and temporal variations, as well as the magnitude of these biogenic isoprene emissions, are expected to change. This paper presents...

Smog chamber study on aging of combustion soot in isoprene/SO2/NOx system: Changes of mass, size, effective density, morphology and mixing state

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Li, Kangwei; Chen, Linghong; Han, Ke; Lv, Biao; Bao, Kaiji; Wu, Xuecheng; Gao, Xiang; Cen, Kefa

2017-02-01

Atmospheric soot aging process is always accompanied by secondary particle formation, which is a comprehensive environmental issue that deserves great attention. On one hand, aging of primary soot could change its own physicochemical properties; on the other hand, complex air pollution caused by pollutant emission from various sources (e.g., vehicle exhausts, coal-fired flue gases and biogenic VOCs emission) may contribute to secondary particle formation onto primary particle surface. In this study, aging of combustion soot in isoprene/SO2/NOx system was investigated under controlled laboratory conditions in several smog chamber experiments. During the evolution of soot, several physical properties such as mass, size, effective density, morphology and mixing state were determined simultaneously by an integrated aerosol analytical system of Scanning Mobility Particle Sizer (SMPS), Differential Mobility Analyzer-Aerosol Particle Mass Analyzer-Condensation Particle Counter (DMA-APM-CPC) and Transmission Electron Microscopy coupled with Energy-dispersive X-ray Spectrometry (TEM/EDX) techniques. Here, based on the experimental results of soot aging under different gas-phase composition and relative humidity (RH), we firstly proposed possible aging pathways of soot in isoprene/SO2/NOx system. A synergetic effect was speculated to exist between SO2 and isoprene on soot aging process, which led to more secondary particle formation. At the same time, TEM/EDX analysis showed that a competitive mechanism between H2SO4(g) and isoprene oxidation vapor may exist: H2SO4(g) firstly condensed onto fresh soot, then an acceleration of isoprene oxidation products formed onto H2SO4 pre-coated soot. In isoprene/SO2/NOx system, high RH conditions could contribute to soot aging and new particle formation. The changes of effective density and dynamic shape factor of soot also indicated that high RH conditions could accelerate soot aging process, and led chain-like soot into more spherical

78 FR 9410 - Ozark Plateau National Wildlife Refuge; Adair, Cherokee, Craig, Delaware, Mayes, Ottawa, and...

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2013-02-08

... 5: Wind Energy Farms. data of bird/bat migration populations corridors; use GIS affected by wind to delineate high- turbines and risk areas; determine locations quantify impacts; to minimize impacts...- hickory-pine Ozark forest, beneficial to nesting and migrating Neotropical birds as well as cave species...

Relating past land-use, topography, and forest dynamics in the Illinois Ozark hills

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Saskia van de Gevel; Trevor B. Ozier; Charles M. Ruffner; John W. Groninger

2003-01-01

Trail of Tears State Forest is a 5,200 acre tract in the Illinois Ozark Hills and represents one of the largest blocks of contiguous forest in the lower Midwest. A highly dissected terrain with long, narrow ridges that fall away sharply on either side characterizes the area. The forest cover is a mosaic of oak-hickory approaching "old growth" condition...

Determination of the Ecological and Geographic Distributions of Armillaria Species in Missouri Ozark Forest Ecosystems

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Johann N. Bruhn; James J. Wetteroff; Jeanne D. Mihail; Susan. Burks

1997-01-01

Armillaria root rot contributes to oak decline in the Ozarks. Three Armillaria species were detected in Ecological Landtypes (ELT's) representing south- to west-facing side slopes (ELT 17), north- to east-facing side slopes (ELT 18), and ridge tops (ELT 11). Armillaria mellea was detected in 91 percent...

Discrepancies between modeled and observed nocturnal isoprene in an urban environment and the possible causes: A case study in Houston

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Diao, Lijun; Choi, Yunsoo; Czader, Beata; Li, Xiangshang; Pan, Shuai; Roy, Anirban; Souri, Amir Hossein; Estes, Mark; Jeon, Wonbae

2016-11-01

Air quality simulations were conducted using the Community Multiscale Air Quality (CMAQ) model for nocturnal isoprene in September 2013 using the United States Environmental Protection Agency's (EPA's) National Emissions Inventory of 2011 (NEI, 2011). The results were evaluated against measurements collected at eight Texas Commission on Environmental Quality (TCEQ) Automated Gas Chromatographs (AutoGCs) monitoring stations. The comparisons demonstrated two distinctive behaviors: overestimation before midnight (20:00-23:00 p.m. local time) versus underestimation after midnight (00:00-06:00 a.m.). Analyses identify the uncertainties in nitrate radical (NO3) concentration and vertical mixing as the possible minor factors contributing to the underestimation, and the underestimated wind speed as the major factor contributing to the overestimation. Further analysis links isoprene underestimation to the uncertainties in the nocturnal isoprene anthropogenic emissions in the NEI (2011) over industrial areas in Houston. This can be substantiated by the fact that the observed nighttime isoprene concentrations increased when the wind direction veered back from southeast to northeast, placing the stations downwind of industrial facilities. A sensitivity run with adjusted anthropogenic isoprene emissions in the later part of the night (i.e., the emissions were multiplied by the hourly underestimation factors ranging from 3.81 to 14.82) yielded closer isoprene predictions after midnight with slightly improved model mean (0.15 to 0.20 ppb), mean error (- 0.10 to - 0.04 ppb), mean absolute error (0.18 to 0.15 ppb), root mean squared error (RMSE, 0.27 to 0.25 ppb), and index of agreement (IOA, 0.66 to 0.68). The insignificant improvement was likely due to the uncertainties in the location of the high-peaked anthropogenic emissions. The impacts of the nighttime-adjusted isoprene emissions on the isoprene oxidation products, organic nitrate and ozone, were found to be minimal. This

Environmental and hydrologic setting of the Ozark Plateaus study unit, Arkansas, Kansas, Missouri, and Oklahoma

Science.gov (United States)

Adamski, James C.; Petersen, James C.; Freiwald, David A.; Davis, Jerri V.

1995-01-01

The environmental and hydrologic setting of the Ozark Plateaus National Water-Quality Assessment (NAWQA) study unit and the factors that affect water quality are described in this report. The primary natural and cultural features that affect water- quality characteristics and the potential for future water-quality problems are described. These environmental features include climate, physio- graphy, geology, soils, population, land use, water use, and surface- and ground-water flow systems. The study-unit area is approximately 47,600 square miles and includes most of the Ozark Plateaus Province and parts of the adjacent Osage Plains and Mississippi Alluvial Plain in parts of Arkansas, Kansas, Missouri, and Oklahoma. The geology is characterized by basement igneous rocks overlain by a thick sequence of dolomites, limestones, sandstones, and shales of Paleozoic age. Land use in the study unit is predominantly pasture and forest in the southeastern part, and pasture and cropland in the northwestern part. All or part of the White, Neosho-lllinois, Osage, Gasconade, Meramec, St. Francis, and Black River Basins are within the study unit. Streams in the Boston Mountains contain the least mineralized water, and those in the Osage Plains contain the most mineralized water. The study unit contains eight hydrogeologic units including three major aquifers--the Springfield Plateau, Ozark, and St. Francois aquifers. Streams and aquifers in the study unit generally contain calcium or calcium-magnesium bicarbonate waters. Ground- and surface-water interactions are greatest in the Salem and Springfield Plateaus and least in the Boston Mountains and Osage Plains. Geology, land use, and population probably are the most important environmental factors that affect water quality.

Spatial patterns of modern period human-caused fire occurrence in the Missouri Ozark Highlands

Science.gov (United States)

Jian Yang; Hong S. Healy; Stephen R. Shifley; Eric J. Gustafson

2007-01-01

The spatial pattern of forest fire locations is important in the study of the dynamics of fire disturbance. In this article we used a spatial point process modeling approach to quantitatively study the effects of land cover, topography, roads, municipalities, ownership, and population density on fire occurrence reported between 1970 and 2002 in the Missouri Ozark...

Similarities in STXM-NEXAFS Spectra of Atmospheric Particles and Secondary Organic Aerosol Generated from Glyoxal, α-Pinene, Isoprene, 1,2,4-Trimethylbenzene, and d-Limonene

Energy Technology Data Exchange (ETDEWEB)

Shakya, Kabindra M.; Liu, Shang; Takahama, Satoshi; Russell, Lynn M.; Keutsch, Frank N.; Galloway, Melissa M.; Shilling, John E.; Hiranuma, Naruki; Song, Chen; Kim, Hwajin; Paulson, Suazanne E.; Pfaffenberger, Lisa; Barmet, Peter; Slowik, J. G.; Prevot, A. S. H.; Dommen, J.; Baltensperger, Urs

2013-02-06

Functional group composition of particles produced in smog chambers are examined using scanning transmission X-ray microscopy (STXM) with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in order to identify characteristic spectral signatures for secondary organic aerosol (SOA). Glyoxal uptake studies showed absorption for mainly alkyl, carbon-nitrogen (C-N), and carboxylic carbonyl groups. The SOA formed from the photooxidation of α-pinene (with and without isoprene) showed stronger absorptions for alkyl and carbonyl groups than the glyoxal studies. The mass ratio of carbonyl to acid group was larger in α-pinene-only experiments relative to the mixed α-pinene-isoprene experiments. The chamber particle spectra were compared with the ambient particle spectra from multiple field campaigns to understand the potential SOA sources. One hundred nineteen particles from six field campaigns had spectral features that were considered similar to the chamber-SOA particles: MILAGRO-2006 (9 particles), VOCALS-2008 (42 particles), Whistler-2008 (22 particles), Scripps Pier-2009 (9 particles), Bakersfield-2010 (25 particles), and Whistler-2010 (12 particles). These similarities with SOA formed from glyoxal, α-pinene (with and without isoprene), 1,2,4-trimethylbenzene, and limonene provide spectroscopic evidence of SOA products from these precursors in ambient particles.

Modeling the response of forest isoprene emissions to future increases in atmospheric CO2 concentration and changes in climate (Invited)

Science.gov (United States)

Monson, R. K.; Heald, C. L.; Guenther, A. B.; Wilkinson, M.

2009-12-01

Isoprene emissions from plants to the atmosphere are sensitive to changes in temperature, light and atmospheric CO2 concentration in both the short- (seconds-to-minutes) and long-term (hours-to-months). We now understand that the different time constants for these responses are due to controls by different sets of biochemical and physiological processes n leaves. Progress has been made in the past few years toward converting this process-level understanding into quantitative models. In this talk, we consider this progress with special emphasis on the short- and long-term responses to atmospheric CO2 concentration and temperature. A new biochemically-based model is presented for describing the CO2 responses, and the model is deployed in a global context to predict interactions between the influences of temperature and CO2 on the global isoprene emission rate. The model is based on the theory of enzyme-substrate kinetics, particularly with regard to those reactions that produce puruvate or glyceraldehyde 3-phosphate, the two chloroplastic substrates for isoprene biosynthesis. In the global model, when we accounted for CO2 inhibition of isoprene emission in the long-term response, we observed little impact on present-day global isoprene emission (increase from 508 to 523 Tg C yr-1). However, the large increases in future isoprene emissions predicted from past models which are due to a projected warmer climate, were entirely offset by including the CO2 effects. The isoprene emission response to CO2 was dominated by the long-term growth environment effect, with modulations of 10% or less from the short-term effect. We use this analysis as a framework for grounding future global models of isoprene emission in biochemical and physiological observations.

Isoprene emission potentials from European oak forests derived from canopy flux measurements: an assessment of uncertainties and inter-algorithm variability

Science.gov (United States)

Langford, Ben; Cash, James; Acton, W. Joe F.; Valach, Amy C.; Hewitt, C. Nicholas; Fares, Silvano; Goded, Ignacio; Gruening, Carsten; House, Emily; Kalogridis, Athina-Cerise; Gros, Valérie; Schafers, Richard; Thomas, Rick; Broadmeadow, Mark; Nemitz, Eiko

2017-12-01

Biogenic emission algorithms predict that oak forests account for ˜ 70 % of the total European isoprene budget. Yet the isoprene emission potentials (IEPs) that underpin these model estimates are calculated from a very limited number of leaf-level observations and hence are highly uncertain. Increasingly, micrometeorological techniques such as eddy covariance are used to measure whole-canopy fluxes directly, from which isoprene emission potentials can be calculated. Here, we review five observational datasets of isoprene fluxes from a range of oak forests in the UK, Italy and France. We outline procedures to correct the measured net fluxes for losses from deposition and chemical flux divergence, which were found to be on the order of 5-8 and 4-5 %, respectively. The corrected observational data were used to derive isoprene emission potentials at each site in a two-step process. Firstly, six commonly used emission algorithms were inverted to back out time series of isoprene emission potential, and then an average isoprene emission potential was calculated for each site with an associated uncertainty. We used these data to assess how the derived emission potentials change depending upon the specific emission algorithm used and, importantly, on the particular approach adopted to derive an average site-specific emission potential. Our results show that isoprene emission potentials can vary by up to a factor of 4 depending on the specific algorithm used and whether or not it is used in a big-leaf or canopy environment (CE) model format. When using the same algorithm, the calculated average isoprene emission potential was found to vary by as much as 34 % depending on how the average was derived. Using a consistent approach with version 2.1 of the Model for Emissions of Gases and Aerosols from Nature (MEGAN), we derive new ecosystem-scale isoprene emission potentials for the five measurement sites: Alice Holt, UK (10 500 ± 2500 µg m-2 h-1); Bosco Fontana, Italy (1610 �

Top-down Estimates of Isoprene Emissions in Australia Inferred from OMI Satellite Data.

Science.gov (United States)

Greenslade, J.; Fisher, J. A.; Surl, L.; Palmer, P. I.

2017-12-01

Australia is a global hotspot for biogenic isoprene emission factors predicted by process-based models such as the Model of Emissions of Gases and Aerosols from Nature (MEGAN). It is also prone to increasingly frequent temperature extremes that can drive episodically high emissions. Estimates of biogenic isoprene emissions from Australia are poorly constrained, with the frequently used MEGAN model overestimating emissions by a factor of 4-6 in some areas. Evaluating MEGAN and other models in Australia is difficult due to sparse measurements of emissions and their ensuing chemical products. In this talk, we will describe efforts to better quantify Australian isoprene emissions using top-down estimates based on formaldehyde (HCHO) observations from the OMI satellite instrument, combined with modelled isoprene to HCHO yields obtained from the GEOS-Chem chemical transport model. The OMI-based estimates are evaluated using in situ observations from field campaigns conducted in southeast Australia. We also investigate the impact on the inferred emission of horizontal resolution used for the yield calculations, particularly in regions on the boundary between low- and high-NOx chemistry. The prevalence of fire smoke plumes roughly halves the available satellite dataset over Australia for much of the year; however, seasonal averages remain robust. Preliminary results show that the top-down isoprene emissions are lower than MEGAN estimates by up to 90% in summer. The overestimates are greatest along the eastern coast, including areas surrounding Australia's major population centres in Sydney, Melbourne, and Brisbane. The coarse horizontal resolution of the model significantly affects the emissions estimates, as many biogenic emitting regions lie along narrow coastal stretches. Our results confirm previous findings that the MEGAN biogenic emission model is poorly calibrated for the Australian environment and suggests that chemical transport models driven by MEGAN are likely

Oak mortality associated with crown dieback and oak borer attack in the Ozark Highlands

Science.gov (United States)

Zhaofei Fan; John M. Kabrick; Martin A. Spetich; Stephen R. Shifley; Randy G. Jensen

2008-01-01

Oak decline and related mortality have periodically plagued upland oak–hickory forests, particularly oak species in the red oak group, across the Ozark Highlands of Missouri, Arkansas and Oklahoma since the late 1970s. Advanced tree age and periodic drought, as well as Armillaria root fungi and oak borer attack are believed to contribute to oak decline and mortality....

The role of environmental factors in oak decline and mortality in the Ozark Highlands

Science.gov (United States)

John M. Kabrick; Daniel C. Dey; Randy G. Jensen; Michael Wallendorf

2008-01-01

Oak decline is a chronic problem in Missouri Ozark forests. Red oak group species are most susceptible and decline is reportedly more severe on droughty, nutrient-poor sites. However, it was not clear whether greater decline severity was caused by poor site conditions or is simply due to the greater abundance of red oak group species found on poorer sites. We conducted...

Inhalation developmental toxicology studies: Teratology study of isoprene in mice and rats: Final report

Energy Technology Data Exchange (ETDEWEB)

Mast, T.J.; Evanoff, J.J.; Stoney, K.H.; Westerberg, R.B.; Rommereim, R.L.; Weigel, R.J.

1989-01-01

Isoprene, a reactive, branched diene, is used in large quantities in the manufacture of polyisoprene and as a copolymer in the synthesis of butyl rubber. The potential for isoprene to cause developmental toxicity was assessed in rodents, by exposing four groups each of Sprague-Dawley rats and Swiss (CD-1) mice to 0, 280, 1400, or 7000 ppM isoprene vapors, 6 h/day, 7 day/wk. Each treatment group consisted of 10 virgin females (for comparison), and approx.30 positively mated rats or mice. Positively mated mice were exposed on days 6-17 of gestation (dg), and rats on 6-19 dg. The day of plug or sperm detection was designated as 0 dg. Body weights were obtained throughout the study period, and uterine and fetal body weights were obtained at sacrifice (rats, 20 dg; mice, 18 dg). Implants were enumerated and their status recorded. Live fetuses were sexed and examined for gross, visceral, skeletal, and soft-tissue craniofacial defects. 31 refs., 6 figs., 19 tabs.

Measuring urinary N-acetyl-S-(4-hydroxy-2-methyl-2-buten-1-yl)-L-cysteine (IPMA3) as a potential biomarker of isoprene exposure.

Science.gov (United States)

Alwis, K Udeni; Bailey, T Liz; Patel, Dhrusti; Wang, Liqun; Blount, Benjamin C

2016-10-19

Isoprene, the 2-methyl analog of 1,3-butadiene, is identified as a possible human carcinogen by the International Agency for Research on Cancer (IARC). Isoprene is ubiquitous in the environment with numerous natural and anthropogenic sources. Tobacco smoke is the main exogenous source of isoprene exposure in indoor environments. Among smoke constituents, isoprene is thought to contribute significantly to cancer risk; however, no selective urinary biomarkers of isoprene exposure have been identified for humans. In this manuscript, we measured the minor isoprene metabolite IPMA1 (mixture of N-acetyl-S-(1-[hydroxymethyl]-2-methyl-2-propen-1-yl)-L-cysteine and N-acetyl-S-(2-hydroxy-3-methyl-3-buten-1-yl)-L-cysteine), and we identified IPMA3 (N-acetyl-S-(4-hydroxy-2-methyl-2-buten-1-yl)-L-cysteine) as a major isoprene metabolite and novel isoprene exposure biomarker for humans. Urinary isoprene metabolites were measured using ultra high performance liquid chromatography coupled with electrospray ionization triple quad tandem mass spectrometry (UPLC/ESI-MSMS). The detection rates of IPMA1 and IPMA3 are <20% and 82%, respectively. The selectivity and abundance of IPMA3 make it a useful urinary biomarker of isoprene exposure. The limit of detection of IPMA3 in urine was 0.5 ng mL -1 . IPMA3 was stable under different storage temperatures and following ten freeze-thaw cycles. The average recovery of urine spiked with IPMA3 at three different levels was 99%. IPMA3 was measured in urine samples received from 75 anonymous subjects; the median (25th percentile, 75th percentile) IPMA3 level in smokers was 36.2 (18.2, 56.8) ng mL -1 and non-smokers 2.31 (2.31, 4.38) ng mL -1 . Application of this method to large population studies will help to characterize isoprene exposure and assess potential health impact. Published by Elsevier B.V.

Real-Time Analysis of Isoprene in Breath by Using Ultraviolet-Absorption Spectroscopy with a Hollow Optical Fiber Gas Cell.

Science.gov (United States)

Iwata, Takuro; Katagiri, Takashi; Matsuura, Yuji

2016-12-05

A breath analysis system based on ultraviolet-absorption spectroscopy was developed by using a hollow optical fiber as a gas cell for real-time monitoring of isoprene in breath. The hollow optical fiber functions as an ultra-small-volume gas cell with a long path. The measurement sensitivity of the system was evaluated by using nitric-oxide gas as a gas sample. The evaluation result showed that the developed system, using a laser-driven, high-intensity light source and a 3-m-long, aluminum-coated hollow optical fiber, could successfully measure nitric-oxide gas with a 50 ppb concentration. An absorption spectrum of a breath sample in the wavelength region of around 200-300 nm was measured, and the measured spectrum revealed the main absorbing components in breath as water vapor, isoprene, and ozone converted from oxygen by radiation of ultraviolet light. The concentration of isoprene in breath was estimated by multiple linear regression. The regression analysis results showed that the proposed analysis system enables real-time monitoring of isoprene during the exhaling of breath. Accordingly, it is suitable for measuring the circadian variation of isoprene.

Real-Time Analysis of Isoprene in Breath by Using Ultraviolet-Absorption Spectroscopy with a Hollow Optical Fiber Gas Cell

Directory of Open Access Journals (Sweden)

Takuro Iwata

2016-12-01

Full Text Available A breath analysis system based on ultraviolet-absorption spectroscopy was developed by using a hollow optical fiber as a gas cell for real-time monitoring of isoprene in breath. The hollow optical fiber functions as an ultra-small-volume gas cell with a long path. The measurement sensitivity of the system was evaluated by using nitric-oxide gas as a gas sample. The evaluation result showed that the developed system, using a laser-driven, high-intensity light source and a 3-m-long, aluminum-coated hollow optical fiber, could successfully measure nitric-oxide gas with a 50 ppb concentration. An absorption spectrum of a breath sample in the wavelength region of around 200–300 nm was measured, and the measured spectrum revealed the main absorbing components in breath as water vapor, isoprene, and ozone converted from oxygen by radiation of ultraviolet light. The concentration of isoprene in breath was estimated by multiple linear regression. The regression analysis results showed that the proposed analysis system enables real-time monitoring of isoprene during the exhaling of breath. Accordingly, it is suitable for measuring the circadian variation of isoprene.

Single-tree harvesting reduces survival and growth of oak stump sprouts in the Missouri Ozark Highlands

Science.gov (United States)

Daniel C. Dey; Randy G. Jensen; Michael J. Wallendorf

2008-01-01

Regeneration and recruitment into the overstory is critical to the success of using uneven-aged systems to sustain oak forests. We evaluated survival and growth of white oak (Quercus alba L.), black oak (Q. velutina Lam.), and scarlet oak (Q. coccinea Muenchh.) stump sprouts 10 years after harvesting Ozark...

Isoprene emissions over Asia 1979-2012: impact of climate and land use changes

Science.gov (United States)

Stavrakou, T.; Müller, J.-F.; Bauwens, M.; De Smedt, I.; Van Roozendael, M.; Guenther, A.; Wild, M.; Xia, X.

2013-11-01

Due to the scarcity of observational constraints and the rapidly changing environment in East and Southeast Asia, isoprene emissions predicted by models are expected to bear substantial uncertainties. The aim of this study is to improve upon the existing bottom-up estimates, and investigate the temporal evolution of the fluxes in Asia over 1979-2012. To this purpose, we calculate the hourly emissions at 0.5° × 0.5° resolution using the MEGAN-MOHYCAN model driven by ECMWF ERA-Interim climatology. This study incorporates (i) changes in land use, including the rapid expansion of oil palms, (ii) meteorological variability according to ERA-Interim, (iii) long-term changes in solar radiation (dimming/brightening) constrained by surface network radiation measurements, and (iv) recent experimental evidence that South Asian tropical forests are much weaker isoprene emitters than previously assumed, and on the other hand, that oil palms hold a strong isoprene emission capacity. These effects lead to a significant lowering (factor of two) in the total isoprene fluxes over the studied domain, and to emission reductions reaching a~factor of 3.5 in Southeast Asia. The bottom-up annual isoprene emissions for 2005 are estimated at 7.0, 4.8, 8.3, 2.9 Tg in China, India, Indonesia and Malaysia, respectively. Changes in temperature and solar radiation are the major drivers of the interannual variability and trend in the emissions. An annual positive flux trend of 0.2% and 0.52% is found in Asia and China, respectively, through the entire period, related to positive trend in temperature and solar radiation. The impact of oil palm expansion in Indonesia and Malaysia is to enhance the trends over that region, e.g. from 1.17% to 1.5% in 1979-2005 in Malaysia. A negative emission trend is derived in India (-0.4%), owing to the negative trend in solar radiation data associated to the strong dimming effect likely due to increasing aerosol loadings. The bottom-up emissions are evaluated

A multi-century analysis of disturbance dynamics in pine-oak forests of the Missouri Ozark Highlands

Science.gov (United States)

Chad King; Rose-Marie. Muzika

2013-01-01

Using dendrochronology and growth release approaches, we analyzed the disturbance history of shortleaf pine (Pinus echinata Mich.) white oak (Quercus alba L.) forests in the Missouri Ozark Highlands. The objectives of this study were to (1) identify growth release events using living and remnant shortleaf pine and white oak, (2)...

Isoprene emission potentials from European oak forests derived from canopy flux measurements: an assessment of uncertainties and inter-algorithm variability

Directory of Open Access Journals (Sweden)

B. Langford

2017-12-01

Full Text Available Biogenic emission algorithms predict that oak forests account for ∼ 70 % of the total European isoprene budget. Yet the isoprene emission potentials (IEPs that underpin these model estimates are calculated from a very limited number of leaf-level observations and hence are highly uncertain. Increasingly, micrometeorological techniques such as eddy covariance are used to measure whole-canopy fluxes directly, from which isoprene emission potentials can be calculated. Here, we review five observational datasets of isoprene fluxes from a range of oak forests in the UK, Italy and France. We outline procedures to correct the measured net fluxes for losses from deposition and chemical flux divergence, which were found to be on the order of 5–8 and 4–5 %, respectively. The corrected observational data were used to derive isoprene emission potentials at each site in a two-step process. Firstly, six commonly used emission algorithms were inverted to back out time series of isoprene emission potential, and then an average isoprene emission potential was calculated for each site with an associated uncertainty. We used these data to assess how the derived emission potentials change depending upon the specific emission algorithm used and, importantly, on the particular approach adopted to derive an average site-specific emission potential. Our results show that isoprene emission potentials can vary by up to a factor of 4 depending on the specific algorithm used and whether or not it is used in a big-leaf or canopy environment (CE model format. When using the same algorithm, the calculated average isoprene emission potential was found to vary by as much as 34 % depending on how the average was derived. Using a consistent approach with version 2.1 of the Model for Emissions of Gases and Aerosols from Nature (MEGAN, we derive new ecosystem-scale isoprene emission potentials for the five measurement sites: Alice Holt, UK (10 500 ± 2500�

Growth regulating properties of isoprene and isoprenoid-based essential oils.

Science.gov (United States)

Jones, Andrew Maxwell P; Shukla, Mukund R; Sherif, Sherif M; Brown, Paula B; Saxena, Praveen K

2016-01-01

Essential oils have growth regulating properties comparable to the well-documented methyl jasmonate and may be involved in localized and/or airborne plant communication. Aromatic plants employ large amounts of resources to produce essential oils. Some essential oils are known to contain compounds with plant growth regulating activities. However, the potential capacity of essential oils as airborne molecules able to modulate plant growth/development has remained uninvestigated. Here, we demonstrate that essential oils from eight taxonomically diverse plants applied in their airborne state inhibited auxin-induced elongation of Pisum sativum hypocotyls and Avena sativa coleoptiles. This response was also observed using five monoterpenes commonly found in essential oils as well as isoprene, the basic building block of terpenes. Upon transfer to ambient conditions, A. sativa coleoptiles resumed elongation, demonstrating an antagonistic relationship rather than toxicity. Inclusion of essential oils, monoterpenes, or isoprene into the headspace of culture vessels induced abnormal cellular growth along hypocotyls of Arabidopsis thaliana. These responses were also elicited by methyl jasmonate (MeJA); however, where methyl jasmonate inhibited root growth essential oils did not. Gene expression studies in A. thaliana also demonstrated differences between the MeJA and isoprenoid responses. This series of experiments clearly demonstrate that essential oils and their isoprenoid components interact with endogenous plant growth regulators when applied directly or as volatile components in the headspace. The similarities between isoprenoid and MeJA responses suggest that they may act in plant defence signalling. While further studies are needed to determine the ecological and evolutionary significance, the results of this study and the specialized anatomy associated with aromatic plants suggest that essential oils may act as airborne signalling molecules.

Why are estimates of global terrestrial isoprene emissions so similar (and why is this not so for monoterpenes?

Directory of Open Access Journals (Sweden)

A. Arneth

2008-08-01

Full Text Available Emissions of biogenic volatile organic compounds (BVOC are a chief uncertainty in calculating the burdens of important atmospheric compounds like tropospheric ozone or secondary organic aerosol, reflecting either imperfect chemical oxidation mechanisms or unreliable emission estimates, or both. To provide a starting point for a more systematic discussion we review here global isoprene and monoterpene emission estimates to-date. We note a surprisingly small variation in the predictions of global isoprene emission rate that is in stark contrast with our lack of process understanding and the small number of observations for model parameterisation and evaluation. Most of the models are based on similar emission algorithms, using fixed values for the emission capacity of various plant functional types. In some cases, these values are very similar but differ substantially in other models. The similarities with regard to the global isoprene emission rate would suggest that the dominant parameters driving the ultimate global estimate, and thus the dominant determinant of model sensitivity, are the specific emission algorithm and isoprene emission capacity. But the models also differ broadly with regard to their representation of net primary productivity, method of biome coverage determination and climate data. Contrary to isoprene, monoterpene estimates show significantly larger model-to-model variation although variation in terms of leaf algorithm, emission capacities, the way of model upscaling, vegetation cover or climatology used in terpene models are comparable to those used for isoprene. From our summary of published studies there appears to be no evidence that the terrestrial modelling community has been any more successful in "resolving unknowns" in the mechanisms that control global isoprene emissions, compared to global monoterpene emissions. Rather, the proliferation of common parameterization schemes within a large variety of model platforms

Remote sensing estimation of isoprene and monoterpene emissions generated by natural vegetation in Monterrey, Mexico.

Science.gov (United States)

Gastelum, Sandra L; Mejía-Velázquez, G M; Lozano-García, D Fabián

2016-06-01

In addition to oxygen, hydrocarbons are the most reactive chemical compounds produced by plants into the atmosphere. These compounds are part of the family of volatile organic compounds (VOCs) and are discharged in a great variety of forms. Among the VOCs produced by natural sources such as vegetation, the most studied until today are the isoprene and monoterpene. These substances can play an important role in the chemical balance of the atmosphere of a region. In this project, we develop a methodology to estimate the natural (vegetation) emission of isoprene and monoterpenes and applied it to the Monterrey Metropolitan Area, Mexico and its surrounding areas. Landsat-TM data was used to identify the dominant vegetation communities and field work to determine the foliage biomass density of key species. The studied communities were submontane scrub, oak, and pine forests and a combination of both. We carried out the estimation of emissions for isoprene and monoterpenes compounds in the different plant communities, with two different criteria: (1) taking into account the average foliage biomass density obtained from the various sample point in each vegetation community, and (2) using the foliage biomass density obtained for each transect, associated to an individual spectral class within a particular vegetation type. With this information, we obtained emission maps for each case. The results show that the main producers of isoprene are the communities that include species of the genus Quercus, located mainly on the Sierra Madre Oriental and Sierra de Picachos, with average isoprene emissions of 314.6 ton/day and 207.3 ton/day for the two methods utilized. The higher estimates of monoterpenes were found in the submontane scrub areas distributed along the valley of the metropolitan zone, with an estimated average emissions of 47.1 ton/day and 181.4 tons for the two methods respectively.

Quantification of volatile organic compounds in exhaled human breath. Acetonitrile as biomarker for passive smoking. Model for isoprene in human breath; Quantifizierung organischer Spurenkomponenten in der menschlichen Atemluft. Acetonitril als Biomarker fuer Passivrauchen. Modell fuer Isopren im Atem, Zusammenhang Isoprenkonzentration, Cholesterinsynthese, lebensmittelchemische Untersuchungen an Knoblauch und Zwiebel

Energy Technology Data Exchange (ETDEWEB)

Prazeller, P

2000-03-01

The topic of this thesis is the quantification of volatile organic compounds in human breath under various circumstances. The composition of exhaled breath reflects metabolic processes in the human body. Breath analysis is a non invasive technique which makes it most interesting especially for medical or toxicological applications. Measurements were done with Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS). This technique combines the advantage of small fragmentation of chemical ionization with highly time resolved mass spectrometry. A big part of this work is about investigations of exposition due to tobacco smoke. After smoking cigarettes the initial increase and time dependence of some compounds in the human breath are monitored . The calculated decrease resulting only from breathing out the compounds is presented and compared to the measured decline in the breath. This allows the distinction whether breathing is the dominant loss of a compound or a different metabolic process remover it more efficiently. Acetonitrile measured in human breath is presented as a biomarker for exposition to tobacco smoke. Especially its use for quantification of passive smoking, the exposition to environmental tobacco smoke (ETS) is shown. The reached accuracy and the fast way of measuring of acetonitrile in human breath using PTR-MS offer a good alternative to common used biomarkers. Numerous publications have described measurements of breath isoprene in humans, and there has been a hope that breath isoprene analyses could be a non-invasive diagnostic tool to assess serum cholesterol levels or cholesterol synthesis rate. However, significant analytical problems in breath isoprene analysis and variability in isoprene levels with age, exercise, diet, etc. have limited the usefulness of these measurements. Here, we have applied proton-transfer-reaction mass spectrometry (PTR-MS) to this problem, allowing on-line detection of breath isoprene. We show that breath isoprene

Isoprene emissions over Asia 1979-2012: impact of climate and land-use changes

Science.gov (United States)

Stavrakou, T.; Müller, J.-F.; Bauwens, M.; De Smedt, I.; Van Roozendael, M.; Guenther, A.; Wild, M.; Xia, X.

2014-05-01

Due to the scarcity of observational constraints and the rapidly changing environment in East and Southeast Asia, isoprene emissions predicted by models are expected to bear substantial uncertainties. The aim of this study is to improve upon the existing bottom-up estimates, and to investigate the temporal evolution of the fluxes in Asia over 1979-2012. To this purpose, we calculate the hourly emissions at 0.5°×0.5° resolution using the MEGAN-MOHYCAN model driven by ECMWF ERA-Interim climatology. In order to remedy for known biases identified in previous studies, and to improve the simulation of interannual variability and trends in emissions, this study incorporates (i) changes in land use, including the rapid expansion of oil palms, (ii) meteorological variability according to ERA-Interim, (iii) long-term changes in solar radiation (dimming/brightening) constrained by surface network radiation measurements, and (iv) recent experimental evidence that South Asian tropical forests are much weaker isoprene emitters than previously assumed, and on the other hand, that oil palms have a strong isoprene emission capacity. These effects lead to a significant lowering (factor of 2) in the total isoprene fluxes over the studied domain, and to emission reductions reaching a factor of 3.5 in Southeast Asia. The bottom-up annual isoprene emissions for 2005 are estimated at 7.0, 4.8, 8.3, and 2.9 Tg in China, India, Indonesia and Malaysia, respectively. The isoprene flux anomaly over the whole domain and studied period is found to be strongly correlated with the Oceanic Niño Index (r = 0.73), with positive (negative) anomalies related to El Niño (La Niña) years. Changes in temperature and solar radiation are the major drivers of the interannual variability and trends in the emissions, except over semi-arid areas such as northwestern China, Pakistan and Kazakhstan, where soil moisture is by far the main cause of interannual emission changes. In our base simulation, annual

Quantification of volatile organic compounds in exhaled human breath. Acetonitrile as biomarker for passive smoking. Model for isoprene in human breath

International Nuclear Information System (INIS)

Prazeller, P.

2000-03-01

The topic of this thesis is the quantification of volatile organic compounds in human breath under various circumstances. The composition of exhaled breath reflects metabolic processes in the human body. Breath analysis is a non invasive technique which makes it most interesting especially for medical or toxicological applications. Measurements were done with Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS). This technique combines the advantage of small fragmentation of chemical ionization with highly time resolved mass spectrometry. A big part of this work is about investigations of exposition due to tobacco smoke. After smoking cigarettes the initial increase and time dependence of some compounds in the human breath are monitored . The calculated decrease resulting only from breathing out the compounds is presented and compared to the measured decline in the breath. This allows the distinction whether breathing is the dominant loss of a compound or a different metabolic process remover it more efficiently. Acetonitrile measured in human breath is presented as a biomarker for exposition to tobacco smoke. Especially its use for quantification of passive smoking, the exposition to environmental tobacco smoke (ETS) is shown. The reached accuracy and the fast way of measuring of acetonitrile in human breath using PTR-MS offer a good alternative to common used biomarkers. Numerous publications have described measurements of breath isoprene in humans, and there has been a hope that breath isoprene analyses could be a non-invasive diagnostic tool to assess serum cholesterol levels or cholesterol synthesis rate. However, significant analytical problems in breath isoprene analysis and variability in isoprene levels with age, exercise, diet, etc. have limited the usefulness of these measurements. Here, we have applied proton-transfer-reaction mass spectrometry (PTR-MS) to this problem, allowing on-line detection of breath isoprene. We show that breath isoprene

Elevated [CO2] magnifies isoprene emissions under heat and improves thermal resistance in hybrid aspen

OpenAIRE

Sun, Zhihong; H?ve, Katja; Vislap, Vivian; Niinemets, ?lo

2013-01-01

Isoprene emissions importantly protect plants from heat stress, but the emissions become inhibited by instantaneous increase of [CO2], and it is currently unclear how isoprene-emitting plants cope with future more frequent and severe heat episodes under high [CO2]. Hybrid aspen (Populus tremula x Populus tremuloides) saplings grown under ambient [CO2] of 380 ?mol mol?1 and elevated [CO2] of 780 ?mol mol?1 were used to test the hypothesis that acclimation to elevated [CO2] reduces the inhibito...

Concentration- and time-dependent genotoxicity profiles of isoprene monoepoxides and diepoxide, and the cross-linking potential of isoprene diepoxide in cells

Directory of Open Access Journals (Sweden)

Yan Li

2014-01-01

Full Text Available Isoprene, a possible carcinogen, is a petrochemical and a natural product being primarily produced by plants. It is biotransformed to 2-ethenyl-2-methyloxirane (IP-1,2-O and 2-(1-methylethenyloxirane (IP-3,4-O, both of which can be further metabolized to 2-methyl-2,2′-bioxirane (MBO. MBO is mutagenic, but IP-1,2-O and IP-3,4-O are not. While IP-1,2-O has been reported being genotoxic, the genotoxicity of IP-3,4-O and MBO, and the cross-linking potential of MBO have not been examined. In the present study, we used the comet assay to investigate the concentration- and time-dependent genotoxicity profiles of the three metabolites and the cross-linking potential of MBO in human hepatocyte L02 cells. For the incubation time of 1 h, all metabolites showed positive concentration-dependent profiles with a potency rank order of IP-3,4-O > MBO > IP-1,2-O. In human hepatocellular carcinoma (HepG2 and human leukemia (HL60 cells, IP-3,4-O was still more potent in inducing DNA breaks than MBO at high concentrations (>200 μM, although at low concentrations (≤200 μM IP-3,4-O exhibited slightly lower or similar potency to MBO. Interestingly, their time-dependent genotoxicity profiles (0.5–4 h in L02 cells were different from each other: IP-1,2-O and MBO (200 μM exhibited negative and positive profiles, respectively, with IP-3,4-O lying in between, namely, IP-3,4-O-caused DNA breaks did not change over the exposure time. Further experiments demonstrated that hydrolysis of IP-1,2-O contributed to the negative profile and MBO induced cross-links at high concentrations and long incubation times. Collectively, the results suggested that IP-3,4-O might play a significant role in the toxicity of isoprene.

Stability of diameter distributions in a managed uneven-aged oak forest in the Ozark Highlands

Science.gov (United States)

Zhiming Wang; Paul S. Johnson; H. E. Garrett; Stephen R. Shifley

1997-01-01

We studied a privately owned 156,000-acre oak-dominated forest in the Ozark Highlands of southern Missouri. The forest has been managed by the single-tree selection method since 1952. Using 40 years of continuous forest inventory records, we analyzed the stability of the shape of tree diameter distributions at the forest-wide scale. Results show that for trees ...

Chamber simulation of photooxidation of dimethyl sulfide and isoprene in the presence of NOx

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M. Jang

2012-11-01

Full Text Available To improve the model prediction for the formation of H2SO4 and methanesulfonic acid (MSA, aerosol-phase reactions of gaseous dimethyl sulfide (DMS oxidation products [e.g., dimethyl sulfoxide (DMSO] in aerosol have been included in the DMS kinetic model with the recently reported gas-phase reactions and their rate constants. To determine the rate constants of aerosol-phase reactions of both DMSO and its major gaseous products [e.g., dimethyl sulfone (DMSO2 and methanesulfinic acid (MSIA], DMSO was photooxidized in the presence of NOx using a 2 m3 Teflon film chamber. The rate constants tested in the DMSO kinetic mechanisms were then incorporated into the DMS photooxidation mechanism. The model simulation using the newly constructed DMS oxidation mechanims was compared to chamber data obtained from the phototoxiation of DMS in the presence of NOx. Within 120-min simulation, the predicted concentrations of MSA increase by 200–400% and those of H2SO4, by 50–200% due to aerosol-phase chemistry. This was well substantiated with experimental data. To study the effect of coexisting volatile organic compounds, the photooxidation of DMS in the presence of isoprene and NOx has been simulated using the newly constructed DMS kinetic model integrated with the Master Chemical Mechanism (MCM for isoprene oxidation, and compared to chamber data. With the high concentrations of DMS (250 ppb and isoprene (560–2248 ppb, both the model simulation and experimental data showed an increase in the yields of MSA and H2SO4 as the isoprene concentration increased.

Isomerization of Second-Generation Isoprene Peroxy Radicals

DEFF Research Database (Denmark)

D'Ambro, Emma L.; Møller, Kristian Holten; Lopez-Hilfiker, Felipe D.

2017-01-01

kinetics box model, we find that to explain the behavior of low-volatility products and SOA mass yields relative to input H2O2 concentrations, the second-generation dihydroxy hydroperoxy peroxy radical (C5H11O6·) must undergo an intramolecular H-shift with a net forward rate constant of order 0.1 s-1...... products under atmospheric conditions and, thus, on the importance of nonreactive gas-particle partitioning of isoprene oxidation products as an SOA source....

Comparing single-tree selection, group selection, and clearcutting for regenerating oaks and pines in the Missouri Ozarks

Science.gov (United States)

Randy G. Jensen; John M. Kabrick

2008-01-01

In the Missouri Ozarks, there is considerable concern about the effectiveness of the uneven-aged methods of single-tree selection and group selection for oak (Quercus L.) and shortleaf pine (Pinus echinata Mill.) regeneration. We compared the changes in reproduction density of oaks and pine following harvesting by single-tree...

Sensitivity of isoprene emissions estimated using MEGAN to the time resolution of input climate data

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K. Ashworth

2010-02-01

Full Text Available We evaluate the effect of varying the temporal resolution of the input climate data on isoprene emission estimates generated by the community emissions model MEGAN (Model of Emissions of Gases and Aerosols from Nature. The estimated total global annual emissions of isoprene is reduced from 766 Tg y⁻¹ when using hourly input data to 746 Tg y⁻¹ (a reduction of 3% for daily average input data and 711 Tg y⁻¹ (down 7% for monthly average input data. The impact on a local scale can be more significant with reductions of up to 55% at some locations when using monthly average data compared with using hourly data. If the daily and monthly average temperature data are used without the imposition of a diurnal cycle the global emissions estimates fall by 27–32%, and local annual emissions by up to 77%. A similar pattern emerges if hourly isoprene fluxes are considered. In order to better simulate and predict isoprene emission rates using MEGAN, we show it is necessary to use temperature and radiation data resolved to one hour. Given the importance of land-atmosphere interactions in the Earth system and the low computational cost of the MEGAN algorithms, we recommend that chemistry-climate models and the new generation of Earth system models input biogenic emissions at the highest temporal resolution possible.

SCIAMACHY formaldehyde observations: constraint for isoprene emission estimates over Europe?

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G. Dufour

2009-03-01

Full Text Available Formaldehyde (HCHO is an important intermediate compound in the degradation of volatile organic compounds (VOCs in the troposphere. Sources of HCHO are largely dominated by its secondary production from VOC oxidation, methane and isoprene being the main precursors in unpolluted areas. As a result of the moderate lifetime of HCHO, its spatial distribution is determined by reactive hydrocarbon emissions. We focus here on Europe and investigate the influence of the different emissions on HCHO tropospheric columns with the CHIMERE chemical transport model in order to interpret the comparisons between SCIAMACHY and simulated HCHO columns. Europe was never specifically studied before for these purposes using satellite observations. The bias between measurements and model is less than 20% on average. The differences are discussed according to the errors on the model and the observations and remaining discrepancies are attributed to a misrepresentation of biogenic emissions. This study requires the characterisation of: (1 the model errors and performances concerning formaldehyde. The errors on the HCHO columns, mainly related to chemistry and mixed emission types, are evaluated to 2×10¹⁵ molecule/cm² and the model performances evaluated using surface measurements are satisfactory (~13%; (2 the observation errors that define the needs in spatial and temporal averaging for meaningful comparisons. Using SCIAMACHY observations as constraint for biogenic isoprene emissions in an inverse modelling scheme reduces their uncertainties by about a factor of two in region of intense emissions. The retrieved correction factors for the isoprene emissions range from a factor of 0.15 (North Africa to a factor of 2 (Poland, the United Kingdom depending on the regions.

Analysis of trends in isoprene and monoterpenes in a remote forest and an anthropogenic influenced forest

Science.gov (United States)

Usenko, S.; Sheesley, R. J.; Winfield, Z.; Yoon, S.; Erickson, M.; Flynn, J. H., III; Alvarez, S. L.; Wallace, H. W., IV; Griffin, R. J.

2017-12-01

The University of Houston Mobile Air Quality Laboratory (MAQL) was deployed to the University of Michigan Biological Station (UMBS) in July 2016 as part of the PROPHET-AMOS study and then was deployed to Jones Forest located north of Houston, TX from August 12 through September 23, 2016. Both sites are heavily forested, but UMBS is remote with no anthropogenic influence while Jones Forest sees frequent pollution transport from Houston. UMBS experienced periods of high isoprene:monoterpenes and periods of equivalent isoprene:monoterpenes, while Jones Forest had a consistently high isoprene:monoterpenes. This provided for a test bed to look at the interactions within two forested environments as well as the influence of anthropogenic sources. The MAQL was outfitted to measure O3 (2B Technology), NOy and SO2 (Thermo Scientific), NO/NOx (Air Quality Design), CO (Los Gatos), and select biogenic volatile organic carbon (BVOC) with their oxidation products (Ionicon PTR-MS). The instruments sampled from MAQL's 6 m tower at both sites. The UMBS site was below canopy and the Jones Forest site was in an open field surrounded by forest. The trends in isoprene and monoterpenes were explored in relation to time-of-day, temperature, and precipitation for both locations. In addition, the production of methyl vinyl ketone and methacrolein under these different conditions of meteorology, trace gas composition and BVOC composition was explored.

Risk factors of oak decline and regional mortality patterns in the Ozark Highlands of Arkansas and Missouri

Science.gov (United States)

Martin A. Spetich; Zhaofei Fan; Xiuli Fan; Hong He; Stephen R. Shifley; W. Keith Moser

2011-01-01

Since the late 1970s, oak decline and mortality have plagued Midwestern-upland oak-hickory forests, particularly species in the red oak group (Quercus Section Lobatae) across the Ozark Highlands of Missouri, Arkansas, and Oklahoma (Dwyer and others 1995). Drought is a common inciting factor in oak decline, while advanced tree age is considered a...

A Matrix Transition Model for an Uneven-Aged, Oak-Hickory Forest in the Missouri Ozark Highlands

Science.gov (United States)

James R. Lootens; David R. Larsen; Edward F. Loewenstein

1999-01-01

We present a matrix growth model for an uneven-aged, oak-hickory forest in the Ozark Highlands of Missouri. The model was developed to predict ingrowth, growth of surviving trees, and mortality by diameter class for a five-year period. Tree removal from management activities is accounted for in the model. We evaluated a progression of models from a static, fixed-...

The use of isoprene as a novel dopant in negative ion atmospheric pressure photoionization mass spectrometry coupled to high-performance liquid chromatography.

Science.gov (United States)

Dousty, Faezeh; O'Brien, Rob

2015-06-15

As in the case with positive ion atmospheric pressure photoionization (PI-APPI), the addition of dopants significantly improves the sensitivity of negative ion APPI (NI-APPI). However, the research on dopant-assisted-NI-APPI has been quite limited compared to the studies on dopant-assisted PI-APPI. This work presents the potential of isoprene as a novel dopant for NI-APPI. Thirteen compounds, possessing suitable gas-phase ion energetic properties in order to make stable negative ions, were selected. Dopants were continuously introduced into a tee junction prior to the ion source through a fused-silica capillary, while analytes were directly injected into the same tee. Then both were mixed with the continuous solvent from high-performance liquid chromatography (HPLC), nebulized, and entered the source. The nebulized stream was analyzed by APPI tandem quadrupole mass spectrometry in the negative ion mode. The results obtained using isoprene were compared with those obtained by using toluene as a dopant and dopant-free NI-APPI. Isoprene enhanced the ionization intensities of the studied compounds, which were found to be comparable and, in some cases, more effective than toluene. The mechanisms leading to the observed set of negative analyte ions were also discussed. Because in NI-APPI, thermal electrons, which are produced during the photoionization of a dopant, are considered the main reagent ions, both isoprene and toluene promoted the ionization of analytes through the same mechanisms, as expected. Isoprene was shown to perform well as a novel dopant for NI-APPI. Isoprene has a high photoabsorption cross section in the VUV region; therefore, its photoionization leads to a highly effective production of thermal electrons, which further promotes the ionization of analytes. In addition, isoprene is environmentally benign and less toxic compared to currently used dopants. Copyright © 2015 John Wiley & Sons, Ltd.

Investigation of OH Radical Regeneration from Isoprene Oxidation Across Different NOx Regimes in the Atmosphere Simulation Chamber SAPHIR

Science.gov (United States)

Novelli, A.; Bohn, B.; Dorn, H. P.; Häseler, R.; Hofzumahaus, A.; Kaminski, M.; Yu, Z.; Li, X.; Tillmann, R.; Wegener, R.; Fuchs, H.; Kiendler-Scharr, A.; Wahner, A.

2017-12-01

The hydroxyl radical (OH) is the dominant daytime oxidant in the troposphere. It starts the degradation of volatile organic compounds (VOC) originating from both anthropogenic and biogenic emissions. Hence, it is a crucial trace species in model simulations as it has a large impact on many reactive trace gases. Many field campaigns performed in isoprene dominated environment in low NOx conditions have shown large discrepancies between the measured and the modelled OH radical concentrations. These results have contributed to the discovery of new regeneration paths for OH radicals from isoprene-OH second generation products with maximum efficiency at low NO. The current chemical models (e.g. MCM 3.3.1) include this novel chemistry allowing for an investigation of the validity of the OH regeneration at different chemical conditions. Over 11 experiments focusing on the OH oxidation of isoprene were performed at the SAPHIR chamber in the Forschungszentrum Jülich. Measurements of VOCs, NOx, O3, HONO were performed together with the measurement of OH radicals (by both LIF-FAGE and DOAS) and OH reactivity. Within the simulation chamber, the NO mixing ratio was varied between 0.05 to 2 ppbv allowing the investigation of both the "new" regeneration path for OH radicals and the well-known NO+HO2 mechanism. A comparison with the MCM 3.3.1 that includes the upgraded LIM1 mechanism showed very good agreement (within 10%) for the OH data at all concentrations of NOx investigated. Comparison with different models, without LIM1 and with updated rates for the OH regeneration, will be presented together with a detailed analysis of the impact of this study on results from previous field campaigns.

Mathematical modeling of blood-gas kinetics for the volatile organic compounds isoprene and acetone

International Nuclear Information System (INIS)

King, J.

2010-01-01

Breath gas analysis is based on the compelling concept that the exhaled breath levels of endogenously produced volatile organic compounds (VOCs) can provide a direct, non-invasive window to the blood and hence, by inference, to the body. In this sense, breath VOCs are regarded as a comprehensive repository of valuable physiological and clinical information, that might be exploited in such diverse areas as diagnostics, therapeutic monitoring or general dynamic assessments of metabolic function, pharmacodynamics (e.g., in drug testing) and environmental exposure (e.g., in occupational health). Despite this enormous potential, the lack of standardized breath sampling regimes as well as the poor mechanistic understanding of VOC exhalation kinetics could cast a cloud over the widespread use of breath gas analysis in the biomedical sciences. In this context, a primary goal of the present thesis is to provide a better quantitative insight into the breath behavior of two prototypic VOCs, isoprene and acetone. A compartmental modeling framework is developed and validated by virtue of real-time breath measurements of these trace gases during distinct physiological states. In particular, the influence of various hemodynamic and ventilatory parameters on VOC concentrations in exhaled breath is investigated. This approach also complements previous steady state investigations in toxicology. From a phenomenological point of view, both acetone and isoprene concentrations in end-tidal breath are demonstrated to exhibit a reproducible non-steady state behavior during moderate workload challenges on a stationary bicycle. However, these dynamics depart drastically from what is expected on the basis of classical pulmonary inert gas elimination theory. More specifically, the start of exercise is accompanied by an abrupt increase in breath isoprene levels, usually by a factor of 3 to 4 compared with the steady state value during rest. This phase is followed by a gradual decline and the

Bayesian spatial prediction of the site index in the study of the Missouri Ozark Forest Ecosystem Project

Science.gov (United States)

Xiaoqian Sun; Zhuoqiong He; John Kabrick

2008-01-01

This paper presents a Bayesian spatial method for analysing the site index data from the Missouri Ozark Forest Ecosystem Project (MOFEP). Based on ecological background and availability, we select three variables, the aspect class, the soil depth and the land type association as covariates for analysis. To allow great flexibility of the smoothness of the random field,...

Assessment of high to low frequency variations of isoprene emission rates using a neural network approach

Science.gov (United States)

Boissard, C.; Chervier, F.; Dutot, A. L.

2007-08-01

Using a statistical approach based on artificial neural networks, an emission algorithm (ISO_LF) accounting for high (instantaneous) to low (seasonal) frequency variations was developed for isoprene. ISO_LF was optimised using an isoprene emission data base (ISO-DB) specifically designed for this work. ISO-DB consists of 1321 emission rates collected in the literature, together with 34 environmental variables, measured or assessed using NCDC (National Climatic Data Center) or NCEP (National Centers for Environmental Predictions) meteorological databases. ISO-DB covers a large variety of emitters (25 species) and environmental conditions (10° S to 60° N). When only instantaneous environmental regressors (air temperature and photosynthetic active radiation, PAR) were used, a maximum of 60% of the overall isoprene variability was assessed and the highest emissions were underestimated. Considering a total of 9 high (instantaneous) to low (up to 3 weeks) frequency regressors, ISO_LF accounts for up to 91% of the isoprene emission variability, whatever the emission range, species or climate. Diurnal and seasonal variations are correctly reproduced for textit{Ulex europaeus} with a maximum factor of discrepancy of 4. ISO-LF was found to be mainly sensitive to air temperature cumulated over 3 weeks T21 and to instantaneous light L0 and air temperature T0 variations. T21, T0 and L0 only accounts for 76% of the overall variability. The use of ISO-LF for non stored monoterpene emissions was shown to give poor results.

Isoprene emissions over Asia 1979–2012: impact of climate and land-use changes

Energy Technology Data Exchange (ETDEWEB)

Stavrakou, T.; Müller, J. -F.; Bauwens, M.; De Smedt, I.; Van Roozendael, M.; Guenther, A.; Wild, M.; Xia, X.

2014-01-01

Due to the scarcity of observational constraints and the rapidly changing environment in East and Southeast Asia, isoprene emissions predicted by models are expected to bear substantial uncertainties. The aim of this study is to improve upon the existing bottom-up estimates, and to investigate the temporal evolution of the fluxes in Asia over 1979–2012. To this purpose, we calculate the hourly emissions at 0.5°×0.5° resolution using the MEGAN–MOHYCAN model driven by ECMWF ERA-Interim climatology. In order to remedy for known biases identified in previous studies, and to improve the simulation of interannual variability and trends in emissions, this study incorporates (i) changes in land use, including the rapid expansion of oil palms, (ii) meteorological variability according to ERA-Interim, (iii) long-term changes in solar radiation (dimming/brightening) constrained by surface network radiation measurements, and (iv) recent experimental evidence that South Asian tropical forests are much weaker isoprene emitters than previously assumed, and on the other hand, that oil palms have a strong isoprene emission capacity. These effects lead to a significant lowering (factor of 2) in the total isoprene fluxes over the studied domain, and to emission reductions reaching a factor of 3.5 in Southeast Asia. The bottom-up annual isoprene emissions for 2005 are estimated at 7.0, 4.8, 8.3, and 2.9 Tg in China, India, Indonesia and Malaysia, respectively. The isoprene flux anomaly over the whole domain and studied period is found to be strongly correlated with the Oceanic Niño Index (r = 0.73), with positive (negative) anomalies related to El Niño (La Niña) years. Changes in temperature and solar radiation are the major drivers of the interannual variability and trends in the emissions, except over semi-arid areas such as northwestern China, Pakistan and Kazakhstan, where soil moisture is by far the main cause of interannual emission changes. In our base simulation

Engineering isoprene synthesis in cyanobacteria.

Science.gov (United States)

Chaves, Julie E; Melis, Anastasios

2018-04-24

The renewable production of isoprene (Isp) hydrocarbons, to serve as fuel and synthetic chemistry feedstock, has attracted interest in the field recently. Isp (C 5 H 8 ) is naturally produced from sunlight, CO 2 and H 2 O photosynthetically in terrestrial plant chloroplasts via the terpenoid biosynthetic pathway and emitted in the atmosphere as a response to heat stress. Efforts to institute a high capacity continuous and renewable process have included heterologous expression of the Isp synthesis pathway in photosynthetic microorganisms. This review examines the premise and promise emanating from this relatively new research effort. Also examined are the metabolic engineering approaches applied in the quest of renewable Isp hydrocarbons production, the progress achieved so far, and barriers encountered along the way. © 2018 Federation of European Biochemical Societies.

Effect of humidity on the composition of isoprene photooxidation secondary organic aerosol

Directory of Open Access Journals (Sweden)

T. B. Nguyen

2011-07-01

Full Text Available The effect of relative humidity (RH on the composition and concentrations of gas-phase products and secondary organic aerosol (SOA generated from the photooxidation of isoprene under high-NO_x conditions was investigated. Experiments were performed with hydrogen peroxide as the OH precursor and in the absence of seed aerosol. The relative yields of most gas-phase products were the same regardless of initial water vapor concentration with exception of hydroxyacetone and glycolaldehyde, which were considerably affected by RH. A significant change was observed in the SOA composition, with many unique condensed-phase products formed under humid (90 % RH vs. dry (<2 % RH conditions, without any detectable effect on the rate and extent of the SOA mass growth. There is a 40 % reduction in the number and relative abundance of distinct particle-phase nitrogen-containing organic compounds (NOC detected by high resolution mass spectrometry. The suppression of condensation reactions, which produce water as a product, is the most important chemical effect of the increased RH. For example, the total signal from oligomeric esters of 2-methylglyceric acid was reduced by about 60 % under humid conditions and the maximum oligomer chain lengths were reduced by 7–11 carbons. Oligomers formed by addition mechanisms, without direct involvement of water, also decreased at elevated RH but to a much smaller extent. The observed reduction in the extent of condensation-type oligomerization at high RH may have substantial impact on the phase characteristics and hygroscopicity of the isoprene aerosol. The reduction in the amount of organic nitrates in the particle phase has implications for understanding the budget of NOC compounds.

The Insect Guild of White Oak Acorns: Its Effect on Mast Quality in the Ozark and Ouachita National Forests

Science.gov (United States)

Alex C. Mangini; Roger W. Perry

2004-01-01

Abstract - Hardwood regeneration, especially of oaks, is an essential component of ecosystem management in the Ouachita and Ozark Mountains of Arkansas. In addition, oak mast is an important wildlife food. Several species of insects inhabit and consume acorns. Data on the insect guild inhabiting white oak (Quercus alba L.) acorns...

Geologic context of large karst springs and caves in the Ozark National Scenic Riverways, Missouri

Science.gov (United States)

Weary, David J.; Orndorff, Randall C.

2016-01-01

The ONSR is a karst park, containing many springs and caves. The “jewels” of the park are large springs, several of first magnitude, that contribute significantly to the flow and water quality of the Current River and its tributaries. Completion of 1:24,000-scale geologic mapping of the park and surrounding river basin, along with synthesis of published hydrologic data, allows us to examine the spatial relationships between the springs and the geologic framework to develop a conceptual model for genesis of these springs. Based on their similarity to mapped spring conduits, many of the caves in the ONSR are fossil conduit segments. Therefore, geologic control on the evolution of the springs also applies to speleogenesis in this part of the southern Missouri Ozarks.Large springs occur in the ONSR area because: (1) the Ozark aquifer, from which they rise, is chiefly dolomite affected by solution via various processes over a long time period, (2) Paleozoic hypogenic fluid migration through these rocks exploited and enhanced flow-paths, (3) a consistent and low regional dip of the rocks off of the Salem Plateau (less than 2° to the southeast) allows integration of flow into large groundwater basins with a few discreet outlets, (4) the springs are located where the rivers have cut down into structural highs, allowing access to water from stratigraphic units deeper in the aquifer thus allowing development of springsheds that have volumetrically larger storage than smaller springs higher in the section, and (5) quartz sandstone and bedded chert in the carbonate stratigraphic succession that are locally to regionally continuous, serve as aquitards that locally confine groundwater up dip of the springs creating artesian conditions. This subhorizontal partitioning of the Ozark aquifer allows contributing areas for different springs to overlap, as evidenced by dye traces that cross adjacent groundwater basin boundaries, and possibly contributes to alternate flow routes

Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

Science.gov (United States)

Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for...

Selection of tree roosts by male Indiana bats during the autumn swarm in the Ozark Highlands, USA

Science.gov (United States)

Roger W. Perry; Stephen C. Brandebura; Thomas S. Risch

2016-01-01

We identified 162 roosts for 36 male Indiana bats (Myotis sodalis) across 3 study areas in the Ozarks of northern Arkansas, USA, during the autumn swarm (late Aug to late Oct, 2005 and 2006). Bats utilized 14 tree species; snags of shortleaf pine (Pinus echinata) were the most utilized (30% of roosts) and pines were selected over hardwoods. Diameter of trees and snags...

Influence of urban pollution on the production of organic particulate matter from isoprene epoxydiols in central Amazonia

Directory of Open Access Journals (Sweden)

S. S. de Sá

2017-06-01

Full Text Available The atmospheric chemistry of isoprene contributes to the production of a substantial mass fraction of the particulate matter (PM over tropical forests. Isoprene epoxydiols (IEPOX produced in the gas phase by the oxidation of isoprene under HO2-dominant conditions are subsequently taken up by particles, thereby leading to production of secondary organic PM. The present study investigates possible perturbations to this pathway by urban pollution. The measurement site in central Amazonia was located 4 to 6 h downwind of Manaus, Brazil. Measurements took place from February through March 2014 of the wet season, as part of the GoAmazon2014/5 experiment. Mass spectra of organic PM collected with an Aerodyne Aerosol Mass Spectrometer were analyzed by positive-matrix factorization. One resolved statistical factor (IEPOX-SOA factor was associated with PM production by the IEPOX pathway. The IEPOX-SOA factor loadings correlated with independently measured mass concentrations of tracers of IEPOX-derived PM, namely C5-alkene triols and 2-methyltetrols (R = 0. 96 and 0.78, respectively. The factor loading, as well as the ratio f of the loading to organic PM mass concentration, decreased under polluted compared to background conditions. For an increase in NOy concentration from 0.5 to 2 ppb, the factor loading and f decreased by two to three fold. Overall, sulfate concentration explained 37 % of the variability in the factor loading. After segregation of factor loading into subsets based on NOy concentration, the sulfate concentration explained up to 75 % of the variability. Considering both factors, the data sets show that the suppressing effects of increased NO concentrations dominated over the enhancing effects of higher sulfate concentrations. The pollution from Manaus elevated NOy concentrations more significantly than sulfate concentrations relative to background conditions. In this light, increased emissions of nitrogen oxides, as

Ionic fragmentation of the isoprene molecule in the VUV energy range (12 to 310 eV)

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Bernini, R.B., E-mail: rafael.bernini@ifrj.edu.br [Instituto Federal de Ciência e Tecnologia do Rio de Janeiro (IFRJ), 25050-100 Duque de Caxias, RJ (Brazil); Coutinho, L.H. [Instituto de Física, Universidade Federal do Rio De Janeiro (UFRJ), 21941-972 Rio de Janeiro, RJ (Brazil); Nunez, C.V. [Laboratório de Bioprospecção e Biotecnologia, Coordenação de Tecnologia e Inovação, Instituto Nacional de Pesquisas da Amazônia (INPA), 69060-001 Manaus, AM (Brazil); Castilho, R.B. de [Departamento de Química, Instituto de Ciências Exatas, Universidade Federal do Amazonas (UFAM), 69077-000 Manaus, AM (Brazil); Souza, G.G.B. de [Instituto de Química, Universidade Federal do Rio de Janeiro (UFRJ), 21949-900 Rio de Janeiro, RJ (Brazil)

2015-07-15

Highlights: • Ionic fragmentation of isoprene following valence-shell and C 1s excitation. • Experimental observation of single and double ionization processes. • Large increase in fragmentation following core excitation. • Similar dissociation pattern bellow (270 eV) and above (310 eV) core edge. • Stable molecular ion observed at all photon energies. - Abstract: Isoprene, C{sub 5}H{sub 8}, is a biogenic volatile compound emitted from plants and animals, playing an important role in atmospheric chemistry. In this work, we have studied the ionic fragmentation of the isoprene molecule induced by high energy photons (synchrotron radiation), both at the valence (12.0, 14.0, 16.0, 18.0, and 21.0 eV) and carbon 1s edge (270 and 310 eV, respectively, below and above edge) energies. The ionic fragments were mass-analyzed using a Wiley–McLaren time-of-flight spectrometer (TOF) and single (PEPICO) and double ionization coincidence (PEPIPICO) spectra were obtained. As expected, the fragmentation degree increases with increasing energy. Below and above the carbon 1s edge, the fragmentation patterns are quite similar, and basically the same fragments are observed as compared to the spectra following valence-shell ionization. Stable doubly-charged ions were not observed. A PEPIPICO spectrum has shown that the main dissociation route for doubly-ionized species corresponds to the [CH{sub 3}]{sup +}/[C{sub 4}H{sub 2–5}]{sup +} ion pair. Intense fragmentation of the isoprene molecule has been observed following valence shell and core electron ionization. The observance of basically the same fragments when moving from valence to inner-shell suggests that basically the same fragmentation routes are present in both cases. All doubly (or multiply)-charged cations are unstable, at least on a microsecond scale.

Measurements of the Weak UV Absorptions of Isoprene and Acetone at 261–275 nm Using Cavity Ringdown Spectroscopy for Evaluation of a Potential Portable Ringdown Breath Analyzer

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Sahay, Peeyush; Scherrer, Susan T.; Wang, Chuji

2013-01-01

The weak absorption spectra of isoprene and acetone have been measured in the wavelength range of 261–275 nm using cavity ringdown spectroscopy. The measured absorption cross-sections of isoprene in the wavelength region of 261–266 nm range from 3.65 × 10−21 cm2·molecule−1 at 261 nm to 1.42 × 10−21 cm2·molecule−1 at 266 nm; these numbers are in good agreement with the values reported in the literature. In the longer wavelength range of 270–275 nm, however, where attractive applications using a single wavelength compact diode laser operating at 274 nm is located, isoprene has been reported in the literature to have no absorption (too weak to be detected). Small absorption cross-sections of isoprene in this longer wavelength region are measured using cavity ringdown spectroscopy for the first time in this work, i.e., 6.20 × 10−23 cm2·molecule−1 at 275 nm. With the same experimental system, wavelength-dependent absorption cross-sections of acetone have also been measured. Theoretical detection limits of isoprene and comparisons of absorbance of isoprene, acetone, and healthy breath gas in this wavelength region are also discussed. PMID:23803787

A remote sensing-assisted risk rating study to predict oak decline and recovery in the Missouri Ozark Highlands, USA

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Cuizhen Wang; Hong S. He; John M. Kabrick

2008-01-01

Forests in the Ozark Highlands underwent widespread oak decline affected by severe droughts in 1999-2000. In this study, the differential normalized difference water index was calculated to detect crown dieback. A multi-factor risk rating system was built to map risk levels of stands. As a quick response to drought, decline in 2000 mostly occurred in stands at low to...

TEAM Science Advances STEM through Experiential Learning about Karst Geology at the Ozark Underground Laboratory.

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Haskins, M. F.; Patterson, J. D.; Ruckman, B.; Keith, N.; Aley, C.; Aley, T.

2017-12-01

Carbonate karst represents approximately 14% of the world's land area and 20-25% of the land area in the United States. Most people do not understand this three dimensional landscape because they lack direct experience with this complicated geology. For the last 50 years, Ozark Underground Laboratory (OUL), located in Protem, MO, has been a pioneer in the research of karst geology and its influence on groundwater. OUL has also provided surface and sub-surface immersion experiences to over 40,000 individuals including students, educators, and Department of Transportation officials helping those individuals better understand the challenges associated with karst. Rockhurst University has incorporated OUL field trips into their educational programming for the last 30 years, thus facilitating individual understanding of karst geology which comprises approximately 60% of the state. Technology and Educators Advancing Missouri Science (TEAM Science) is a grant-funded professional development institute offered through Rockhurst University. The institute includes an immersion experience at OUL enabling in-service teachers to better understand natural systems, the interplay between the surface, sub-surface, and cave fauna, as well as groundwater and energy dynamics of karst ecosystems. Educating elementary teachers about land formations is especially important because elementary teachers play a foundational role in developing students' interest and aptitude in STEM content areas. (Funding provided by the U.S. Department of Education's Math-Science Partnership Program through the Missouri Department of Elementary and Secondary Education.)

Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields

Energy Technology Data Exchange (ETDEWEB)

D’Ambro, Emma L.; Møller, Kristian H.; Lopez-Hilfiker, Felipe D.; Schobesberger, Siegfried; Liu, Jiumeng; Shilling, John E.; Lee, Ben Hwan; Kjaergaard, Henrik G.; Thornton, Joel A.

2017-04-11

We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1. Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.

Observations of biogenic isoprene emissions and atmospheric chemistry components at the Savé super site in Benin, West Africa, during the DACCIWA field campaign.

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Jambert, Corinne; Pacifico, Federica; Delon, Claire; Lohou, Fabienne; Reinares Martinez, Irene; Brilouet, Pierre-Etienne; Derrien, Solene; Dione, Cheikh; Brosse, Fabien; Gabella, Omar; Pedruzzo Bagazgoitia, Xavier; Durand, Pierre

2017-04-01

Tropospheric oxidation of VOCs (Volatile Organic Compounds), including isoprene, in the presence of NOx and sunlight leads to the formation of O3 and Secondary Organic Aerosols (SOA). Changes in NO or VOCs sources will consequently modify their atmospheric concentrations and thus, the rate of O3 production and SOA formation. NOx have also an impact on the abundance of the hydroxyl radical (OH) which determines the lifetime of some pollutants and greenhouse gases. Anthropogenic emissions of pollutants from mega cities located on the Guinean coast in South West Africa are likely to increase in the next decades due to a strong anthropogenic pressure and to land use changes at the regional or continental scale. The consequences on regional air quality and on pollutant deposition onto surfaces may have some harmful effects on human and ecosystem health. Furthermore, the regional climate and water cycle are affected by changes in atmospheric chemistry. When transported northward on the African continent, polluted air masses meet biogenic emissions from rural areas which contributes to increase ozone and SOA production, in high temperature and solar radiation conditions, highly favourable to enhanced photochemistry. During the Dynamics-aerosol-chemistry-cloud interactions in West Africa (DACCIWA) field campaign, we measured the atmospheric chemical composition and the exchanges of trace components in a hinterland area of Benin, at the Savé super-site (8°02'03" N, 2°29'11″ E). The observations, monitored in June and July 2016, in a rural mixed agricultural area, include near surface concentrations of ozone (O3), carbon monoxide (CO), nitrogen oxides (NOx) and isoprene, isoprene fluxes and meteorological parameters. We observed hourly average concentrations of O3 up to 50 ppb, low NOx concentrations (ca. 1 ppb and CO concentrations between 75 and 300 ppb. An 8 m tower was equipped with a Fast Isoprene Sensor and sonic anemometer to measure isoprene concentrations and

Differential cardiac effects in rats exposed to atmospheric smog generated from isoprene versus toluene

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The results of this study demonstrate that atmospheric smog generated from both isoprene and toluene cause cardiac effects in rats. In addition, it appears that smog from toluene is more toxic in terms of cardiac arrhythmogenicity. Smog, which is a comple...

Probabilistic estimation of future emissions of isoprene and surface oxidant chemistry associated with land-use change in response to growing food needs

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C. J. Hardacre

2013-06-01

Full Text Available We quantify the impact of land-use change, determined by our growing demand for food and biofuel production, on isoprene emissions and subsequent atmospheric oxidant chemistry in 2015 and 2030, relative to 1990, ignoring compound climate change effects over that period. We estimate isoprene emissions from an ensemble (n = 1000 of land-use change realizations from 1990–2050, broadly guided by the IPCC AR4/SRES scenarios A1 and B1. We also superimpose land-use change required to address projected biofuel usage using two scenarios: (1 assuming that world governments make no changes to biofuel policy after 2009, and (2 assuming that world governments develop biofuel policy with the aim of keeping equivalent atmospheric CO2 at 450 ppm. We present the median and interquartile range (IQR statistics of the ensemble and show that land-use change between −1.50 × 1012 m2 to +6.06 × 1012 m2 was found to drive changes in the global isoprene burden of −3.5 to +2.8 Tg yr−1 in 2015 and −7.7 to +6.4 Tg yr−1 in 2030. We use land-use change realizations corresponding to the median and IQR of these emission estimates to drive the GEOS-Chem global 3-D chemistry transport model to investigate the perturbation to global and regional surface concentrations of isoprene, nitrogen oxides (NO+NO2, and the atmospheric concentration and deposition of ozone (O3. We show that across subcontinental regions the monthly surface O3 increases by 0.1–0.8 ppb, relative to a zero land-use change calculation, driven by increases (decreases in surface isoprene in high (low NOx environments. At the local scale (4° × 5° we find that surface O3 increases by 5–12 ppb over temperate North America, China and boreal Eurasia, driven by large increases in isoprene emissions from short-rotation coppice crop cultivation for biofuel production.

Assessing the impact of anthropogenic pollution on isoprene-derived secondary organic aerosol formation in PM2.5 collected from the Birmingham, Alabama, ground site during the 2013 Southern Oxidant and Aerosol Study

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W. Rattanavaraha

2016-04-01

Full Text Available In the southeastern US, substantial emissions of isoprene from deciduous trees undergo atmospheric oxidation to form secondary organic aerosol (SOA that contributes to fine particulate matter (PM2.5. Laboratory studies have revealed that anthropogenic pollutants, such as sulfur dioxide (SO2, oxides of nitrogen (NOx, and aerosol acidity, can enhance SOA formation from the hydroxyl radical (OH-initiated oxidation of isoprene; however, the mechanisms by which specific pollutants enhance isoprene SOA in ambient PM2.5 remain unclear. As one aspect of an investigation to examine how anthropogenic pollutants influence isoprene-derived SOA formation, high-volume PM2.5 filter samples were collected at the Birmingham, Alabama (BHM, ground site during the 2013 Southern Oxidant and Aerosol Study (SOAS. Sample extracts were analyzed by gas chromatography–electron ionization-mass spectrometry (GC/EI-MS with prior trimethylsilylation and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS to identify known isoprene SOA tracers. Tracers quantified using both surrogate and authentic standards were compared with collocated gas- and particle-phase data as well as meteorological data provided by the Southeastern Aerosol Research and Characterization (SEARCH network to assess the impact of anthropogenic pollution on isoprene-derived SOA formation. Results of this study reveal that isoprene-derived SOA tracers contribute a substantial mass fraction of organic matter (OM ( ∼  7 to  ∼  20 %. Isoprene-derived SOA tracers correlated with sulfate (SO42− (r2 = 0.34, n = 117 but not with NOx. Moderate correlations between methacrylic acid epoxide and hydroxymethyl-methyl-α-lactone (together abbreviated MAE/HMML-derived SOA tracers with nitrate radical production (P[NO3] (r2 = 0.57, n = 40 were observed during nighttime, suggesting a

Oak woodland restoration in the Missouri Ozarks: two case studies examining responses of ground flora vegetation to prescribed fire

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Aaron P. Stevenson

2016-01-01

Prescribed fire and thinning are two primary tools for restoring overgrown oak and oak-pine woodlands in Missouri. We wanted to examine woodland restoration efforts and determine if we were meeting our goals of promoting herbaceous ground flora cover and richness. We examined herbaceous responses to fire at two restoration sites in the Missouri Ozarks. At the first...

Selective Production of Toluene from Biomass-Derived Isoprene and Acrolein.

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Dai, Tao; Li, Changzhi; Zhang, Bo; Guo, Haiwei; Pan, Xiaoli; Li, Lin; Wang, Aiqin; Zhang, Tao

2016-12-20

Toluene is a basic chemical that is currently produced from petroleum resources. In this paper, we report a new route for the effective synthesis of toluene from isoprene and acrolein, two reactants readily available from biomass, through a simple two-step reaction. The process includes Diels-Alder cycloaddition of isoprene and acrolein in a Zn-containing ionic liquid at room temperature to produce methylcyclohex-3-enecarbaldehydes (MCHCAs) as intermediates, followed by M (M=Pt, Pd, Rh)/Al 2 O 3 -catalyzed consecutive dehydrogenation-decarbonylation of the MCHCAs at 573 K to generate toluene with an overall yield up to 90.7 %. Model reactions indicated that a synergistic inductive effect of the C=C double bond and the aldehyde group in MCHCA plays a key role in initiating the consecutive dehydrogenation-decarbonylation, and that methyl benzaldehydes are the key intermediates in the gas-phase transformation of MCHCAs. Microcalorimetric adsorption of CO on different catalysts showed that decarbonylation of the substrate occurs more likely on the strong adsorption sites. To the best of our knowledge, it is the first report of Pt/Al 2 O 3 -catalyzed consecutive dehydrogenation-decarbonylation of a given compound in one reactor. This work provides a highly efficient and environmental friendly route to toluene by utilizing two compounds that can be prepared from biomass. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sensitivity to grid resolution in the ability of a chemical transport model to simulate observed oxidant chemistry under high-isoprene conditions

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K. Yu

2016-04-01

Full Text Available Formation of ozone and organic aerosol in continental atmospheres depends on whether isoprene emitted by vegetation is oxidized by the high-NOx pathway (where peroxy radicals react with NO or by low-NOx pathways (where peroxy radicals react by alternate channels, mostly with HO2. We used mixed layer observations from the SEAC4RS aircraft campaign over the Southeast US to test the ability of the GEOS-Chem chemical transport model at different grid resolutions (0.25°  ×  0.3125°, 2°  ×  2.5°, 4°  ×  5° to simulate this chemistry under high-isoprene, variable-NOx conditions. Observations of isoprene and NOx over the Southeast US show a negative correlation, reflecting the spatial segregation of emissions; this negative correlation is captured in the model at 0.25°  ×  0.3125° resolution but not at coarser resolutions. As a result, less isoprene oxidation takes place by the high-NOx pathway in the model at 0.25°  ×  0.3125° resolution (54 % than at coarser resolution (59 %. The cumulative probability distribution functions (CDFs of NOx, isoprene, and ozone concentrations show little difference across model resolutions and good agreement with observations, while formaldehyde is overestimated at coarse resolution because excessive isoprene oxidation takes place by the high-NOx pathway with high formaldehyde yield. The good agreement of simulated and observed concentration variances implies that smaller-scale non-linearities (urban and power plant plumes are not important on the regional scale. Correlations of simulated vs. observed concentrations do not improve with grid resolution because finer modes of variability are intrinsically more difficult to capture. Higher model resolution leads to decreased conversion of NOx to organic nitrates and increased conversion to nitric acid, with total reactive nitrogen oxides (NOy changing little across model resolutions. Model concentrations in the

Spatio-Temporal Trends of Oak Decline and Mortality under Periodic Regional Drought in the Ozark Highlands of Arkansas and Missouri

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Zhaofei Fan; Xiuli Fan; Michael K. Crosby; W. Keith Moser; Hong He; Martin A. Spetich; Stephen R. Shifley

2012-01-01

At the forest landscape/region level, based on annual Forest Inventory and Analysis plot data from 1999 to 2010, oak decline and mortality trends for major oak species (groups) were examined in the Ozark Highlands of Arkansas and Missouri. Oak decline has elevated cumulative mortality of red oak species to between 11 and 15 percent in terms of relative density and...

Effect of gamma irradiation conditions on the radiation-induced degradation of isobutylene-isoprene rubber

Energy Technology Data Exchange (ETDEWEB)

Sen, M. E-mail: msen@hacettepe.edu.tr; Uzun, C.; Kantoglu, Oe.; Erdogan, S.M.; Deniz, V.; Gueven, O

2003-08-01

The effect of gamma irradiation conditions on the radiation-induced degradation of uncrosslinked, commercial isobutylene-isoprene rubbers has been investigated in this study. Influence of dose rate and irradiation atmosphere on the degradation of butyl rubber has been followed by viscosimetric and chromatographic analyses. Limiting viscosity number of all butyl rubbers decreased sharply up to 100 kGy and leveled off at around the same molecular weight, independent of dose rate. Slightly higher decrease in viscosity was observed for samples irradiated in air than in nitrogen especially at low dose rate irradiation. Cross-linking G(X), and chain scission G(S) yields of butyl rubbers were calculated by using weight- and number-average molecular weights of irradiated rubber determined by Size Exclusion Chromatography analyses. G-value results showed that chain scission reactions in isobutylene-isoprene rubber in air atmosphere are more favorable than in nitrogen atmosphere, and that lower dose rate enhances chain scission over cross-linking.

Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere

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Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry

2011-12-01

Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8

Cloud Processing of Secondary Organic Aerosol from Isoprene and Methacrolein Photooxidation.

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Giorio, Chiara; Monod, Anne; Brégonzio-Rozier, Lola; DeWitt, Helen Langley; Cazaunau, Mathieu; Temime-Roussel, Brice; Gratien, Aline; Michoud, Vincent; Pangui, Edouard; Ravier, Sylvain; Zielinski, Arthur T; Tapparo, Andrea; Vermeylen, Reinhilde; Claeys, Magda; Voisin, Didier; Kalberer, Markus; Doussin, Jean-François

2017-10-12

Aerosol-cloud interaction contributes to the largest uncertainties in the estimation and interpretation of the Earth's changing energy budget. The present study explores experimentally the impacts of water condensation-evaporation events, mimicking processes occurring in atmospheric clouds, on the molecular composition of secondary organic aerosol (SOA) from the photooxidation of methacrolein. A range of on- and off-line mass spectrometry techniques were used to obtain a detailed chemical characterization of SOA formed in control experiments in dry conditions, in triphasic experiments simulating gas-particle-cloud droplet interactions (starting from dry conditions and from 60% relative humidity (RH)), and in bulk aqueous-phase experiments. We observed that cloud events trigger fast SOA formation accompanied by evaporative losses. These evaporative losses decreased SOA concentration in the simulation chamber by 25-32% upon RH increase, while aqueous SOA was found to be metastable and slowly evaporated after cloud dissipation. In the simulation chamber, SOA composition measured with a high-resolution time-of-flight aerosol mass spectrometer, did not change during cloud events compared with high RH conditions (RH > 80%). In all experiments, off-line mass spectrometry techniques emphasize the critical role of 2-methylglyceric acid as a major product of isoprene chemistry, as an important contributor to the total SOA mass (15-20%) and as a key building block of oligomers found in the particulate phase. Interestingly, the comparison between the series of oligomers obtained from experiments performed under different conditions show a markedly different reactivity. In particular, long reaction times at high RH seem to create the conditions for aqueous-phase processing to occur in a more efficient manner than during two relatively short cloud events.

Atmospheric fates of Criegee intermediates in the ozonolysis of isoprene.

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Nguyen, Tran B; Tyndall, Geoffrey S; Crounse, John D; Teng, Alexander P; Bates, Kelvin H; Schwantes, Rebecca H; Coggon, Matthew M; Zhang, Li; Feiner, Philip; Milller, David O; Skog, Kate M; Rivera-Rios, Jean C; Dorris, Matthew; Olson, Kevin F; Koss, Abigail; Wild, Robert J; Brown, Steven S; Goldstein, Allen H; de Gouw, Joost A; Brune, William H; Keutsch, Frank N; Seinfeld, John H; Wennberg, Paul O

2016-04-21

We use a large laboratory, modeling, and field dataset to investigate the isoprene + O3 reaction, with the goal of better understanding the fates of the C1 and C4 Criegee intermediates in the atmosphere. Although ozonolysis can produce several distinct Criegee intermediates, the C1 stabilized Criegee (CH2OO, 61 ± 9%) is the only one observed to react bimolecularly. We suggest that the C4 Criegees have a low stabilization fraction and propose pathways for their decomposition. Both prompt and non-prompt reactions are important in the production of OH (28% ± 5%) and formaldehyde (81% ± 16%). The yields of unimolecular products (OH, formaldehyde, methacrolein (42 ± 6%) and methyl vinyl ketone (18 ± 6%)) are fairly insensitive to water, i.e., changes in yields in response to water vapor (≤4% absolute) are within the error of the analysis. We propose a comprehensive reaction mechanism that can be incorporated into atmospheric models, which reproduces laboratory data over a wide range of relative humidities. The mechanism proposes that CH2OO + H2O (k(H2O)∼ 1 × 10(-15) cm(3) molec(-1) s(-1)) yields 73% hydroxymethyl hydroperoxide (HMHP), 6% formaldehyde + H2O2, and 21% formic acid + H2O; and CH2OO + (H2O)2 (k(H2O)2∼ 1 × 10(-12) cm(3) molec(-1) s(-1)) yields 40% HMHP, 6% formaldehyde + H2O2, and 54% formic acid + H2O. Competitive rate determinations (kSO2/k(H2O)n=1,2∼ 2.2 (±0.3) × 10(4)) and field observations suggest that water vapor is a sink for greater than 98% of CH2OO in a Southeastern US forest, even during pollution episodes ([SO2] ∼ 10 ppb). The importance of the CH2OO + (H2O)n reaction is demonstrated by high HMHP mixing ratios observed over the forest canopy. We find that CH2OO does not substantially affect the lifetime of SO2 or HCOOH in the Southeast US, e.g., CH2OO + SO2 reaction is a minor contribution (production by stabilized Criegees is likely unimportant in regions dominated by the reactivity of ozone with isoprene. In contrast

Ethene, propene, butene and isoprene emissions from a ponderosa pine forest measured by relaxed eddy accumulation

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Rhew, Robert C.; Deventer, Malte Julian; Turnipseed, Andrew A.; Warneke, Carsten; Ortega, John; Shen, Steve; Martinez, Luis; Koss, Abigail; Lerner, Brian M.; Gilman, Jessica B.; Smith, James N.; Guenther, Alex B.; de Gouw, Joost A.

2017-11-01

Alkenes are reactive hydrocarbons that influence local and regional atmospheric chemistry by playing important roles in the photochemical production of tropospheric ozone and in the formation of secondary organic aerosols. The simplest alkene, ethene (ethylene), is a major plant hormone and ripening agent for agricultural commodities. The group of light alkenes (C2-C4) originates from both biogenic and anthropogenic sources, but their biogenic sources are poorly characterized, with limited field-based flux observations. Here we report net ecosystem fluxes of light alkenes and isoprene from a semiarid ponderosa pine forest in the Rocky Mountains of Colorado, USA using the relaxed eddy accumulation (REA) technique during the summer of 2014. Ethene, propene, butene and isoprene emissions have strong diurnal cycles, with median daytime fluxes of 123, 95, 39 and 17 µg m-2 h-1, respectively. The fluxes were correlated with each other, followed general ecosystem trends of CO2 and water vapor, and showed similar sunlight and temperature response curves as other biogenic VOCs. The May through October flux, based on measurements and modeling, averaged 62, 52, 24 and 18 µg m-2 h-1 for ethene, propene, butene and isoprene, respectively. The light alkenes contribute significantly to the overall biogenic source of reactive hydrocarbons: roughly 18 % of the dominant biogenic VOC, 2-methyl-3-buten-2-ol. The measured ecosystem scale fluxes are 40-80 % larger than estimates used for global emissions models for this type of ecosystem.

Influence of Incomplete Mixing on the OH-Isoprene Reaction in the Lower Troposphere - Measurements Above the Amazon Rain Forest and General Considerations

Science.gov (United States)

Sörgel, M.; Dlugi, R. J. W.; Berger, M.; Mallik, C.; Tsokankunku, A.; Zelger, M.; Acevedo, O. C.; Dias, N. L.; Hofzumahaus, A.; Kesselmeier, J.; Kramm, G.; Marno, D. R.; Martinez, M.; Nölscher, A.; H G, O.; Pfannerstill, E.; Bourtsoukidis, E.; Rohrer, F.; Tauer, S.; Williams, J.; Yanez Serrano, A. M.; Andreae, M. O.; Harder, H.

2017-12-01

Incomplete mixing of reactants in the atmosphere (segregation) causes reduced reaction rates compared to laboratory values derived for well mixed conditions. To adequately determine the actual reaction rates in a variety of natural environments where the distribution of sources and sinks leads to inhomogeneous distribution of reactants, the intensity of segregation (IS) has to be taken into account. Although, there has been considerable progress in modeling IS in the boundary layer within the last 30 years, calculations from direct observations are still sparse as high time resolution and time synchronization are required. OH-radicals are the most important oxidizing agent in the atmosphere, and are therefore regarded as the detergent of the atmosphere, reacting with the majority of atmospheric pollutants and therefore accelerating their removal from the atmosphere. Hence, to understand atmospheric self-cleansing, we need to quantify and understand the budgets (sources and sinks) of OH. As it is a fast reacting compound, for some of its reactants mixing will limit the reaction rate. The reaction of isoprene and OH radicals has gained considerable interest in recent years since large discrepancies between modeled and measured OH have been found mainly in high isoprene environments. This motivated not only laboratory studies on unknown recycling mechanisms for OH in this reaction, but also modeling work and field studies on the effect of segregation on this reaction. We measured OH radicals, isoprene and other species that are either precursors of OH or promote OH recycling (e.g. O3, NOx, HO2, H2O) with high time resolution (1-10 Hz) closely above a rain forest canopy (at 41 m above ground level) at the ATTO (Amazon Tall Tower Observatory) site (02°08'38.8''S, 58°59'59.5''W). The site is characterized by high isoprene (up to 20 ppb) and low NO (50 -500 ppt). Simultaneous measurements of OH and isoprene with high time resolution so far have been sparse. To our

Predicting probability of occurrence and factors affecting distribution and abundance of three Ozark endemic crayfish species at multiple spatial scales

Science.gov (United States)

Nolen, Matthew S.; Magoulick, Daniel D.; DiStefano, Robert J.; Imhoff, Emily M.; Wagner, Brian K.

2014-01-01

Crayfishes and other freshwater aquatic fauna are particularly at risk globally due to anthropogenic demand, manipulation and exploitation of freshwater resources and yet are often understudied. The Ozark faunal region of Missouri and Arkansas harbours a high level of aquatic biological diversity, especially in regard to endemic crayfishes. Three such endemics, Orconectes eupunctus,Orconectes marchandi and Cambarus hubbsi, are threatened by limited natural distribution and the invasions of Orconectes neglectus.

Biogenic isoprene emissions driven by regional weather predictions using different initialization methods: case studies during the SEAC4RS and DISCOVER-AQ airborne campaigns

Science.gov (United States)

Huang, Min; Carmichael, Gregory R.; Crawford, James H.; Wisthaler, Armin; Zhan, Xiwu; Hain, Christopher R.; Lee, Pius; Guenther, Alex B.

2017-08-01

Land and atmospheric initial conditions of the Weather Research and Forecasting (WRF) model are often interpolated from a different model output. We perform case studies during NASA's SEAC4RS and DISCOVER-AQ Houston airborne campaigns, demonstrating that using land initial conditions directly downscaled from a coarser resolution dataset led to significant positive biases in the coupled NASA-Unified WRF (NUWRF, version 7) surface and near-surface air temperature and planetary boundary layer height (PBLH) around the Missouri Ozarks and Houston, Texas, as well as poorly partitioned latent and sensible heat fluxes. Replacing land initial conditions with the output from a long-term offline Land Information System (LIS) simulation can effectively reduce the positive biases in NUWRF surface air temperature by ˜ 2 °C. We also show that the LIS land initialization can modify surface air temperature errors almost 10 times as effectively as applying a different atmospheric initialization method. The LIS-NUWRF-based isoprene emission calculations by the Model of Emissions of Gases and Aerosols from Nature (MEGAN, version 2.1) are at least 20 % lower than those computed using the coarser resolution data-initialized NUWRF run, and are closer to aircraft-observation-derived emissions. Higher resolution MEGAN calculations are prone to amplified discrepancies with aircraft-observation-derived emissions on small scales. This is possibly a result of some limitations of MEGAN's parameterization and uncertainty in its inputs on small scales, as well as the representation error and the neglect of horizontal transport in deriving emissions from aircraft data. This study emphasizes the importance of proper land initialization to the coupled atmospheric weather modeling and the follow-on emission modeling. We anticipate it to also be critical to accurately representing other processes included in air quality modeling and chemical data assimilation. Having more confidence in the weather

Barrierless Reactions with Loose Transition States Govern the Yields and Lifetimes of Organic Nitrates Derived from Isoprene

Science.gov (United States)

The chemical reaction mechanism of NO addition to two β and δ isoprene hydroxy–peroxy radical isomers is examined in detail using density functional theory, coupled cluster methods, and the energy resolved master equation formalism to provide estimates of rate co...

Bis(phenolate)amine-supported lanthanide borohydride complexes for styrene and trans-1,4-isoprene (co-)polymerisations

NARCIS (Netherlands)

Bonnet, Fanny; Dyer, Hellen E.; El Kinani, Yassine; Dietz, Carin; Roussel, Pascal; Bria, Marc; Visseaux, Marc; Zinck, Philippe; Mountford, Philip

2015-01-01

New bis(phenolate)amine-supported neodymium borohydride complexes and their previously reported samarium analogues were tested as catalysts for the polymerisation of styrene and isoprene. Reaction of Na2O2NL (L = py, OMe, NMe2) with Nd(BH4)3(THF)3 afforded the borohydride complexes

OCO-2 chlorophyll fluorescence tracks late-summer photosynthesis decrease due to water stress at Missouri Ozark site

Science.gov (United States)

He, L.; Frankenberg, C.; Wood, J. D.; Sun, Y.

2017-12-01

Accurate estimate of the photosynthetic uptake of CO2, denoted gross primary productivity (GPP), is important to understand and quantify the carbon cycles at regional to global scales, and has implications in crop and forest management. Solar-induced chlorophyll fluorescence (SIF) retrieved from space was found to be strongly correlated with GPP and is now being used as a potential new technique to estimate photosynthetic rates at large scale. We selected the Missouri Ozark Site as a test bed, a well-characterized Eddy Covariance site in deciduous broadleaf forests, to explore the relationships of vegetation indices (VIs) and SIF with GPP and their response to environmental conditions. We find that both GPP fluxes and OCO-2 SIF decreased in late summer at the Ozark Site, directly related to water stress, evidenced by a progressive decrease in soil moisture and concomitant changer in leaf water potential. However, VIs (both NDVI and EVI) stayed stable during the same period. With a focus on this wet-dry transition period, we analyze driving factors of changes in GPP and SIF, which appear to be linearly related even in this period with little reflectance changes. We also used the Soil Canopy Observation, Photochemistry and Energy fluxes (SCOPE) model to compare observations of SIF and GPP against measurement. The primary motivation is not only to quantify the expected correlations between the GPP and SIF but also to validate performance of SCOPE in reproducing such correlations, which have not been tested against independent observations. This study clearly underlines the potential of SIF measurements to study moderate water stress and its impact on photosynthesis.

Thermal Effect on the phosphoric Acid Impregnated Activated Carbon Fiber and Adsorption Properties Toward Isoprene

Energy Technology Data Exchange (ETDEWEB)

Hwang, Taek Sung; Lee, Jin Hyok; Kang, Kyung suk [Department of Chemical Engineering, College of Engineering, Chungnam National University, Taejon (Korea); Kim, Kwang Young [Ace Lab. Co. Ltd. Taejon (Korea); Rhee, Moon Soo [Korea Ginseng and Tobacoo Research Institute, Taejon (Korea)

2001-05-01

To introduce chemisorption property and improve adsorption capacities for isoprene, ACF (Activated Carbon Fiber) was impregnated by phosphoric acid. As the impregnated ACF was dried by programmed temperature from 300 degree C to 500 degree C, degree of impregnation, surface area, thermal stability and adsorption properties for isoprene were observed. The degree of impregnation of the ACF, dried at the 400 degree C, was 12.7 w/w% and surface area was 1148 m{sup 2}/g. Over the temperature range of 450 degree C to 700 degree C, there was one-step thermal degradation by the thermal decomposition of phosphonyl group. The adsorption rate of phosphoric acid on the impregnated ACF, which was dried at 400 degree C, was the fastest. The breakthrough time of ACF that was dried at 400 degree C was 18 min., and its adsorption capacity improved roughly 7.2 times in comparison to the pure ACF. In addition, it was observed the adsorption properties persisted even after the regeneration. The adsorption efficiency of regenerated ACF was 66 percent compared to the unused impregnated ACF. 21 refs., 7 figs., 3 tabs.

Trachymolgus purpureus sp. n., an armored snout mite (Acari, Bdellidae) from the Ozark highlands: morphology, development, and key to Trachymolgus Berlese

Science.gov (United States)

Fisher, J. Ray; Skvarla, Michael J.; Bauchan, Gary R.; Ochoa, Ronald; Dowling, Ashley P.G.

2011-01-01

Abstract Trachymolgus purpureus Fisher & Dowling sp. n. is described from the Ozark highlands of North America. A diversity of imaging techniques are used to illustrate the species including low-temperature scanning electron microscopy (LT-SEM), stereomicrography, compound light micrography, and digitally created line drawings. Developmental stages (larva, nymphs, and adult) and morphology are illustrated and discussed, and terminological corrections are suggested. Trachymolgus recki Gomelauri, 1961 is regarded as being described from tritonymphs. A key to Trachymolgus is presented. PMID:21998535

Contributions of primary and secondary biogenic VOC tototal OH reactivity during the CABINEX (Community Atmosphere-Biosphere INteractions Experiments-09 field campaign

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S. Kim

2011-08-01

Full Text Available We present OH reactivity measurements using the comparative reactivity method with a branch enclosure technique for four different tree species (red oak, white pine, beech and red maple in the UMBS PROPHET tower footprint during the Community Atmosphere Biosphere INteraction EXperiment (CABINEX field campaign in July of 2009. Proton Transfer Reaction-Mass Spectrometry (PTR-MS was sequentially used as a detector for OH reactivity and BVOC concentrations including isoprene and monoterpenes (MT for enclosure air. Therefore, the measurement dataset contains both measured and calculated OH reactivity from well-known BVOC. The results indicate that isoprene and MT, and in one case a sesquiterpene, can account for the measured OH reactivity. Significant discrepancy between measured OH reactivity and calculated OH reactivity from isoprene and MT is found for the red maple enclosure dataset but it can be reconciled by adding reactivity from emission of a sesquiterpene, α-farnesene, detected by GC-MS. This leads us to conclude that no significant unknown BVOC emission contributed to ambient OH reactivity from these trees at least during the study period. However, this conclusion should be followed up by more comprehensive side-by-side intercomparison between measured and calculated OH reactivity and laboratory experiments with controlled temperature and light environments to verify effects of those essential parameters towards unknown/unmeasured reactive BVOC emissions. This conclusion leads us to explore the contribution towards ambient OH reactivity (the dominant OH sink in this ecosystem oxidation products such as hydroxyacetone, glyoxal, methylglyoxal and C4 and C5-hydroxycarbonyl using recently published isoprene oxidation mechanisms (Mainz Isoprene Mechanism II and Leuven Isoprene Mechanism. Evaluation of conventionally unmeasured first generation oxidation products of isoprene and their possible contribution to ambient missing OH reactivity

Receiver function and gravity constraints on crustal structure and vertical movements of the Upper Mississippi Embayment and Ozark Uplift

Science.gov (United States)

Liu, Lin; Gao, Stephen S.; Liu, Kelly H.; Mickus, Kevin

2017-06-01

The Upper Mississippi Embayment (UME), where the seismically active New Madrid Seismic Zone resides, experienced two phases of subsidence commencing in the Late Precambrian and Cretaceous, respectively. To provide new constraints on models proposed for the mechanisms responsible for the subsidence, we computed and stacked P-to-S receiver functions recorded by 49 USArray and other seismic stations located in the UME and the adjacent Ozark Uplift and modeled Bouguer gravity anomaly data. The inferred thickness, density, and Vp/Vs of the upper and lower crustal layers suggest that the UME is characterized by a mafic and high-density upper crustal layer of ˜30 km thickness, which is underlain by a higher-density lower crustal layer of up to ˜15 km. Those measurements, in the background of previously published geological observations on the subsidence and uplift history of the UME, are in agreement with the model that the Cretaceous subsidence, which was suggested to be preceded by an approximately 2 km uplift, was the consequence of the passage of a previously proposed thermal plume. The thermoelastic effects of the plume would have induced wide-spread intrusion of mafic mantle material into the weak UME crust fractured by Precambrian rifting and increased its density, resulting in renewed subsidence after the thermal source was removed. In contrast, the Ozark Uplift has crustal density, thickness, and Vp/Vs measurements that are comparable to those observed on cratonic areas, suggesting an overall normal crust without significant modification by the proposed plume, probably owing to the relatively strong and thick lithosphere.

Soil respiration as affected by long-term broiler litter application to a udult in the ozark highlands.

Science.gov (United States)

McMullen, Richard L; Brye, Kristofor R; Gbur, Edward E

2015-01-01

The United States produced 8.4 billion broiler chickens () and an estimated 10.1 to 14.3 million Mg of broiler litter (BL) in 2012. Arkansas' production of 1 billion broilers in 2012 produced an estimated 1.2 to 1.7 million Mg of BL, most of which was concentrated in the Ozark Highlands region of northwest Arkansas. Increased CO release from soils associated with agricultural practices has generated concerns regarding the contribution of certain agricultural management practices to global warming. The objectives of this study were to evaluate the effects of long-term (>6 yr) BL application to a Udult on soil respiration and annual C emissions and to determine the predictability of soil respiration based on soil temperature and moisture in the Ozark Highlands region of northwest Arkansas. Soil respiration was measured routinely between May 2009 and May 2012 in response to annual BL application rates of 0, 5.6, and 11.2 Mg dry litter ha that began in 2003. Soil respiration varied ( 0.05) by BL application rate but differed ( < 0.01) among study years. Multiple regression indicated that soil respiration could be reasonably predicted using 2-cm-depth soil temperature (T) and the product of T and VWC as predictors ( = 0.52; < 0.01). Results indicate that organic amendments, such as BL, can stimulate release of CO from the soil to the atmosphere, potentially negatively affecting atmospheric greenhouse gas concentrations; thus, there may be application rates above which the benefits of organic amendments may be diminished by adverse environmental effects. Improved BL management strategies are needed to lessen the loss of CO from BL-amended soils. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Analysis of Poly(Lactic-co-Glycolic Acid/Poly(Isoprene Polymeric Blend for application as biomaterial

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Douglas Ramos Marques

2013-01-01

Full Text Available The application of renewable raw materials encourages research in the biopolymers area. The Poly(Lactic-co-Glycolic Acid/Poly(Isoprene (PLGA/IR blend combines biocompatibility for application in the health field with excellent mechanical properties. The blend was obtained by solubilization of polymers in organic solvents. To investigate the polymer thermochemical properties, FTIR and DSC were applied. To investigate the composition's influence over polymer mechanical properties, tensile and hardness test were applied. To analyze the blends response in the cell environment, a stent was produced by injection molding process, and Cell Viability Test and Previous Implantability were used. The Infrared spectra show that chemical composition is related only with polymers proportion in the blend. The calorimetry shows a partial miscibility in the blend. The tensile test shows that adding Poly(Isoprene to Poly(Lactic-co-Glycolic Acid induced a relevant reduction in the Young modulus, tensile stress and tenacity of the material, which was altered from the fragile raw PLGA to a ductile material. The composition did not affect the blend hardness. The cell viability test shows that the blend has potential application as biomaterial, while the first results of implantability indicate that the polymeric stent kept its original position and caused low fibrosis.

Isoprene levels in the exhaled breath of 200 healthy pupils within the age range 7-18 years studied using SIFT-MS

Czech Academy of Sciences Publication Activity Database

Smith, D.; Španěl, Patrik; Enderby, B.; Lenney, W.; Turner, C.; Davies, S. J.

2010-01-01

Roč. 4, č. 1 (2010), 017101 ISSN 1752-7155 Institutional research plan: CEZ:AV0Z40400503 Keywords : SIFT-MS * mass spectroscopy * isoprene Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.828, year: 2010

Living catalyzed-chain-growth polymerization and block copolymerization of isoprene by rare-earth metal allyl precursors bearing a constrained-geometry-conformation ligand.

Science.gov (United States)

Jian, Zhongbao; Cui, Dongmei; Hou, Zhaomin; Li, Xiaofang

2010-05-07

Aminophenyl functionalized cyclopentadienyl ligated rare-earth metal allyl mediated cationic systems display high cis-1,4 selectivity for the polymerization of isoprene, and living reversible and rapid chain transfer to aluminium additives.

Using graphene/styrene-isoprene-styrene copolymer composite thin film as a flexible microstrip antenna for the detection of heptane vapors

Science.gov (United States)

Olejnik, Robert; Matyas, Jiri; Slobodian, Petr; Riha, Pavel

2018-03-01

Most portable devices, such as mobile phones or tablets, use antennas made of copper. This paper demonstrates the possible use of antenna constructed from electrically conductive polymer composite materials for use in those applications. The method of preparation and the properties of the graphene/styrene-isoprene-styrene copolymer as flexible microstrip antenna are described in this contribution. Graphene/styrene-isoprene-styrene copolymer toluene solution was prepared by means of ultrasound and the PET substrate was dip coated to reach a fine thin film. The main advantages of using PET as a substrate are low weight and flexibility. The final size of the flexible microstrip antenna was 10 × 25 mm with thickness of 0.48 mm (PET substrate 0.25 mm) with a weight of 0.110 g. The resulting antenna operates at a frequency of 1.8 GHz and gain ‑40.02 dB.

USGS geologic Mapping and karst research in the Ozark National Scenic Riverways, Missouri, USA

Science.gov (United States)

Weary, David J.; Grant, Victoria M

2014-01-01

The Ozark National Scenic Riverways (ONSR) was created in 1964 to protect 134 miles of the Current River and its major tributary, the Jacks Fork, that are located in south-central Missouri (fig. 1). The park includes numerous large karst springs including Big Spring, by flow volume this is the largest spring in the National Park system. The National Park Service (NPS) administers a narrow, nearly continuous corridor of land adjacent to the two rivers. Base flow for the rivers is chiefly supplied by groundwater that has traveled through the karst landscape from as far as 38 miles away from the spring (Imes and Frederick, 2002). The watershed is vulnerable to pollution, but the area remains largely rural with few industries. The springs and rivers provide habitat for numerous aquatic species as well as recreational resources for floaters, fishermen, and campers. The ONSR is a major cave park with hundreds of known caves and diverse in-cave resources.

Luminescent Lanthanide Metal Organic Frameworks for cis-Selective Isoprene Polymerization Catalysis

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Samantha Russell

2015-11-01

Full Text Available In this study, we are combining two areas of chemistry; solid-state coordination polymers (or Metal-Organic Framework—MOF and polymerization catalysis. MOF compounds combining two sets of different lanthanide elements (Nd3+, Eu3+/Tb3+ were used for that purpose: the use of neodymium was required due to its well-known catalytic properties in dienes polymerization. A second lanthanide, europium or terbium, was included in the MOF structure with the aim to provide luminescent properties. Several lanthanides-based MOF meeting these criteria were prepared according to different approaches, and they were further used as catalysts for the polymerization of isoprene. Stereoregular cis-polyisoprene was received, which in some cases exhibited luminescent properties in the UV-visible range.

Radiation-induced deterioration of natural rubber and isoprene rubber vulcanizates

International Nuclear Information System (INIS)

Kohjiya, Shinzo; Matsumura, Yasushige; Yamashita, Shinzo; Matsuyama, Tomochika; Yamaoka, Hitoshi.

1984-01-01

Natural rubber (NR) and isoprene rubber (IR) were cured by sulfur and accelerator to give rubber vulcanizates. Both vulcanizates were subject to solvent extraction to purify them, followed by the γ-ray irradiation in air at room temperature. The deterioration by γ-ray (0-20 Mrad) was investigated by the changes of tensile properties, hardness, swelling, and ATR-IR spectra. The tensile strength decreased much by a few Mrad irradiation, which is elucidated due to the difficulty of stretch-induced crystallization of polyisoprene after the irradiation. Modulus at 50 % elongation, network-chain density, and hardness did not show significant variation with the γ-ray dose. These irradiation results suggest both degradation and crosslinking occur comparably in the rubber vulcanizates and the regularity of polyisoprene chains may be somewhat randomized to prevent them from crystallizing on stretching. (author)

In situ emulsion cationic polymerization of isoprene onto the surface of graphite oxide sheets

Energy Technology Data Exchange (ETDEWEB)

Pazat, Alice [Ingénierie des Matériaux Polymères, IMP, CNRS UMR 5223, Université Claude Bernard Lyon 1 and INSA de Lyon, 15 boulevard Latarjet, 69122 Villeurbanne cedex (France); Laboratoire de Recherches et de Contrôle du Caoutchouc et des Plastiques, LRCCP, 60 rue Auber, 94408 Vitry-sur-Seine cedex (France); Beyou, Emmanuel, E-mail: beyou@univ-lyon1.fr [Ingénierie des Matériaux Polymères, IMP, CNRS UMR 5223, Université Claude Bernard Lyon 1 and INSA de Lyon, 15 boulevard Latarjet, 69122 Villeurbanne cedex (France); Barrès, Claire [Ingénierie des Matériaux Polymères, IMP, CNRS UMR 5223, Université Claude Bernard Lyon 1 and INSA de Lyon, 15 boulevard Latarjet, 69122 Villeurbanne cedex (France); Bruno, Florence; Janin, Claude [Laboratoire de Recherches et de Contrôle du Caoutchouc et des Plastiques, LRCCP, 60 rue Auber, 94408 Vitry-sur-Seine cedex (France)

2017-02-28

Highlights: • Graphite oxide sheets were functionalized by polyisoprene in a two steps procedure. • The polyisoprene chains were grafted onto functionalized GO sheets by the grafting through technique. • A polyisoprene weight content of 50% was calculated from TGA measurements. • A decrease of the air permeability coefficient of 27% for the vulcanized PI composites has been reached. - Abstract: Grafting of polymers onto graphite oxide sheets (GO) has been widely studied in recent years due to the numerous applications of GO-based composites. Herein, polyisoprene (PI) chains were anchored on the surface of GO by in situ cationic polymerization using a “grafting through” approach with allyltrimethoxysilane-modified GO (GO-ATMS). First, the functionalization of GO sheets through the hydrolysis-condensation of allyltrimethoxysilane (ATMS) molecules was qualitatively evidenced by infra-red spectroscopy and X-ray photoelectron spectrometry and a weight content of 4% grafted ATMS was calculated from thermogravimetric analysis. Then, isoprene was in situ polymerized through a one-pot cationic mechanism by using a highly water-dispersible Lewis acid surfactant combined catalyst. For comparison, it was shown that the cationic polymerization of isoprene in presence of un-functionalized GO sheets led to a polyisoprene weight content on the solid filler divided by 3 compared to GO-ATMS. Finally, the compounding of the modified GO/PI composites was performed at a processing temperature of 80 °C with 2 phr and 15 phr loadings and it was shown a decrease of the air permeability coefficient of 27% for the vulcanizates with 15 phr loading.

In situ emulsion cationic polymerization of isoprene onto the surface of graphite oxide sheets

International Nuclear Information System (INIS)

Pazat, Alice; Beyou, Emmanuel; Barrès, Claire; Bruno, Florence; Janin, Claude

2017-01-01

Highlights: • Graphite oxide sheets were functionalized by polyisoprene in a two steps procedure. • The polyisoprene chains were grafted onto functionalized GO sheets by the grafting through technique. • A polyisoprene weight content of 50% was calculated from TGA measurements. • A decrease of the air permeability coefficient of 27% for the vulcanized PI composites has been reached. - Abstract: Grafting of polymers onto graphite oxide sheets (GO) has been widely studied in recent years due to the numerous applications of GO-based composites. Herein, polyisoprene (PI) chains were anchored on the surface of GO by in situ cationic polymerization using a “grafting through” approach with allyltrimethoxysilane-modified GO (GO-ATMS). First, the functionalization of GO sheets through the hydrolysis-condensation of allyltrimethoxysilane (ATMS) molecules was qualitatively evidenced by infra-red spectroscopy and X-ray photoelectron spectrometry and a weight content of 4% grafted ATMS was calculated from thermogravimetric analysis. Then, isoprene was in situ polymerized through a one-pot cationic mechanism by using a highly water-dispersible Lewis acid surfactant combined catalyst. For comparison, it was shown that the cationic polymerization of isoprene in presence of un-functionalized GO sheets led to a polyisoprene weight content on the solid filler divided by 3 compared to GO-ATMS. Finally, the compounding of the modified GO/PI composites was performed at a processing temperature of 80 °C with 2 phr and 15 phr loadings and it was shown a decrease of the air permeability coefficient of 27% for the vulcanizates with 15 phr loading.

Mapping vegetation communities using statistical data fusion in the Ozark National Scenic Riverways, Missouri, USA

Science.gov (United States)

Chastain, R.A.; Struckhoff, M.A.; He, H.S.; Larsen, D.R.

2008-01-01

A vegetation community map was produced for the Ozark National Scenic Riverways consistent with the association level of the National Vegetation Classification System. Vegetation communities were differentiated using a large array of variables derived from remote sensing and topographic data, which were fused into independent mathematical functions using a discriminant analysis classification approach. Remote sensing data provided variables that discriminated vegetation communities based on differences in color, spectral reflectance, greenness, brightness, and texture. Topographic data facilitated differentiation of vegetation communities based on indirect gradients (e.g., landform position, slope, aspect), which relate to variations in resource and disturbance gradients. Variables derived from these data sources represent both actual and potential vegetation community patterns on the landscape. A hybrid combination of statistical and photointerpretation methods was used to obtain an overall accuracy of 63 percent for a map with 49 vegetation community and land-cover classes, and 78 percent for a 33-class map of the study area. ?? 2008 American Society for Photogrammetry and Remote Sensing.

On rates and mechanisms of OH and O3 reactions with isoprene-derived hydroxy nitrates.

Science.gov (United States)

Lee, Lance; Teng, Alex P; Wennberg, Paul O; Crounse, John D; Cohen, Ronald C

2014-03-06

Eight distinct hydroxy nitrates are stable products of the first step in the atmospheric oxidation of isoprene by OH. The subsequent chemical fate of these molecules affects global and regional production of ozone and aerosol as well as the location of nitrogen deposition. We synthesized and purified 3 of the 8 isoprene hydroxy nitrate isomers: (E/Z)-2-methyl-4-nitrooxybut-2-ene-1-ol and 3-methyl-2-nitrooxybut-3-ene-1-ol. Oxidation of these molecules by OH and ozone was studied using both chemical ionization mass spectrometry and thermo-dissociation laser induced fluorescence. The OH reaction rate constants at 300 K measured relative to propene at 745 Torr are (1.1 ± 0.2) × 10(-10) cm(3) molecule(-1) s(-1) for both the E and Z isomers and (4.2 ± 0.7) × 10(-11) cm(3) molecule(-1) s(-1) for the third isomer. The ozone reaction rate constants for (E/Z)-2-methyl-4-nitrooxybut-2-ene-1-ol are (2.7 ± 0.5) × 10(-17) and (2.9 ± 0.5) × 10(-17) cm(3) molecule(-1) s(-1), respectively. 3-Methyl-2-nitrooxybut-3-ene-1-ol reacts with ozone very slowly, within the range of (2.5-5) × 10(-19) cm(3) molecule(-1) s(-1). Reaction pathways, product yields, and implications for atmospheric chemistry are discussed. A condensed mechanism suitable for use in atmospheric chemistry models is presented.

Biosynthetic origin of the isoprene units in chromenes of Piper aduncum (Piperaceae)

International Nuclear Information System (INIS)

Leite, Ana C.; Lopes, Adriana A.; Bolzani, Vanderlan da S.; Furlan, Maysa; Kato, Massuo J.

2007-01-01

Metabolic studies involving the incorporation of [1- 13 C]-D-glucose into intact leaves of Piper aduncum (Piperaceae) have indicated that both the mevalonate (MVA) and the pyruvate-triose (MEP) non-mevalonate pathways are implicated in the biosynthesis of isoprene moieties present in methyl 2,2-dimethyl-2H-1-chromene-6-carboxylate (1) and methyl 2,2-dimethyl-8-(3'-methyl- 2'-butenyl)-2H-1-chromene-6-carboxylate (2). The pattern of incorporation of label from [1- 13 C]-D-glucose into these chromenes was determined by quantitative 13 C NMR spectroscopy. The results confirmed that biosynthetic compartment of 1 and 2 could either be the plastid and/ or the cytosol or, possibly, an additional compartment such as the plastid inter-membrane space. (author)

Surface ozone seasonality under global change: Influence from dry deposition and isoprene emissions at northern mid-latitudes

Science.gov (United States)

Clifton, O.; Paulot, F.; Fiore, A. M.; Horowitz, L. W.; Malyshev, S.; Shevliakova, E.; Correa, G. J. P.; Lin, M.

2017-12-01

Identifying the contributions of nonlinear chemistry and transport to observed surface ozone seasonal cycles over land using global models relies on an accurate representation of ozone uptake by vegetation (dry deposition). It is well established that in the absence of ozone precursor emission changes, a warming climate will increase surface ozone in polluted regions, and that a rise in temperature-dependent isoprene emissions would exacerbate this "climate penalty". However, the influence of changes in ozone dry deposition, expected to evolve with climate and land use, is often overlooked in air quality projections. With a new scheme that represents dry deposition within the NOAA GFDL dynamic vegetation land model (LM3) coupled to the NOAA GFDL atmospheric chemistry-climate model (AM3), we simulate the impact of 21st century climate and land use on ozone dry deposition and isoprene emissions. This dry deposition parameterization is a version of the Wesely scheme, but uses parameters explicitly calculated by LM3 that respond to climate and land use (e.g., stomatal conductance, canopy interception of water, leaf area index). The parameterization includes a nonstomatal deposition dependence on humidity. We evaluate climatological present-day seasonal cycles of ozone deposition velocities and abundances with those observed at northern mid-latitude sites. With a set of 2010s and 2090s decadal simulations under a high climate warming scenario (RCP8.5) and a sensitivity simulation with well-mixed greenhouse gases following RCP8.5 but air pollutants held at 2010 levels (RCP8.5_WMGG), we examine changes in surface ozone seasonal cycles. We build on our previous findings, which indicate that strong reductions in anthropogenic NOx emissions under RCP8.5 cause the surface ozone seasonal cycle over the NE USA to reverse, shifting from a summer peak at present to a winter peak by 2100. Under RCP8.5_WMGG, we parse the separate effects of climate and land use on ozone dry

Behavioral and Physiological Responses of Ozark Zigzag Salamanders to Stimuli from an Invasive Predator: The Armadillo

Directory of Open Access Journals (Sweden)

Adam L. Crane

2012-01-01

Full Text Available When new predators invade a habitat, either through range extensions or introductions, prey may be at a high risk because they do not recognize the predators as dangerous. The nine-banded armadillo (Dasypus novemcinctus has recently expanded its range in North America. Armadillos forage by searching soil and leaf litter, consuming invertebrates and small vertebrates, including salamanders. We tested whether Ozark zigzag salamanders (Plethodon angusticlavius from a population coexisting with armadillos for about 30 years exhibit antipredator behavior in the presence of armadillo chemical cues and whether they can discriminate between stimuli from armadillos and a nonpredatory sympatric mammal (white-tailed deer, Odocoileus virginianus. Salamanders appeared to recognize substrate cues from armadillos as a threat because they increased escape behaviors and oxygen consumption. When exposed to airborne cues from armadillos, salamanders also exhibited an antipredator response by spending more time in an inconspicuous posture. Additionally, individually consistent behaviors across treatments for some response variables suggest the potential for a behavioral syndrome in this species.

Tectonic Evolution of an Intracratonic Plateau: The Ups and Downs of the Ozark Dome, Midcontinent United States

Science.gov (United States)

DeLucia, M. S.; Marshak, S.; Guenthner, W.

2017-12-01

Though intracratonic platforms have been affected both by epeirogenic movements (producing regional-scale basins and domes) and by local faulting, they typically have low relief. The Ozark Plateau (OP) of Missouri, a region underlain by the structural Ozark Dome (OD), is an exception for it rises to elevations of up to 0.7 km above the surface of the adjacent Illinois Basin (IB). Structural and geomorphic analysis, and low-temperature thermochronology, provide insight into vertical movements of the OD relative to the IB. The basement top of both the IB and OP exposes 1.47 Ga extrusive rhyolite. Therefore, basement of both the IB and OD sat at the Earth's surface then. Rifting after emplacement established a rectilinear array of steep faults, which delineated what would become the OD, and set the stage for IB subsidence. Zircon (U-Th)/He thermochronology indicates that exhumation of the Midcontinent to form the Great Unconformity (GU) happened from 0.85 to 0.68 Ga. To reset the zircon system, the region must have been buried >4 km prior to 0.85 Ga, perhaps by Grenville foreland deposits. Deposition began on the GU at 0.5 Ga, burying paleotopography of the OD and IB. Differential vertical motion between these regions initiated in the Paleozoic. Strata thin towards the apex of the dome, emphasizing that the OD remained high during IB subsidence. Eventually, as much as 7.5 km of structural relief accumulated across the boundary between the OD and IB. Some of the movement was accommodated by fault slip that was coeval with Appalachian orogenies, emphasizing that orogenic stress penetrated into the continental interior. Faulting contributed to tilting the OD crustal block. Apatite (U-Th)/He and fission-track thermochronology suggests that Mesozoic exhumation removed post-Pennsylvanian cover. Both Proterozoic and Mesozoic exhumation events took place just before supercontinent breakup, suggesting a link between mantle phenomena and intracratonic elevation. Contemporary

Biosynthetic origin of the isoprene units in chromenes of Piper aduncum (Piperaceae)

Energy Technology Data Exchange (ETDEWEB)

Leite, Ana C.; Lopes, Adriana A.; Bolzani, Vanderlan da S.; Furlan, Maysa [UNESP, Araraquara, SP (Brazil). Inst. de Quimica]. E-mail: maysaf@iq.unesp.br; Kato, Massuo J. [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica

2007-07-01

Metabolic studies involving the incorporation of [1-{sup 13}C]-D-glucose into intact leaves of Piper aduncum (Piperaceae) have indicated that both the mevalonate (MVA) and the pyruvate-triose (MEP) non-mevalonate pathways are implicated in the biosynthesis of isoprene moieties present in methyl 2,2-dimethyl-2H-1-chromene-6-carboxylate (1) and methyl 2,2-dimethyl-8-(3'-methyl- 2'-butenyl)-2H-1-chromene-6-carboxylate (2). The pattern of incorporation of label from [1- {sup 13}C]-D-glucose into these chromenes was determined by quantitative {sup 13}C NMR spectroscopy. The results confirmed that biosynthetic compartment of 1 and 2 could either be the plastid and/ or the cytosol or, possibly, an additional compartment such as the plastid inter-membrane space. (author)

A simple modeling approach to study the regional impact of a Mediterranean forest isoprene emission on anthropogenic plumes

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J. Cortinovis

2005-01-01

Full Text Available Research during the past decades has outlined the importance of biogenic isoprene emission in tropospheric chemistry and regional ozone photo-oxidant pollution. The first part of this article focuses on the development and validation of a simple biogenic emission scheme designed for regional studies. Experimental data sets relative to Boreal, Tropical, Temperate and Mediterranean ecosystems are used to estimate the robustness of the scheme at the canopy scale, and over contrasted climatic and ecological conditions. A good agreement is generally found when comparing field measurements and simulated emission fluxes, encouraging us to consider the model suitable for regional application. Limitations of the scheme are nevertheless outlined as well as further on-going improvements. In the second part of the article, the emission scheme is used on line in the broader context of a meso-scale atmospheric chemistry model. Dynamically idealized simulations are carried out to study the chemical interactions of pollutant plumes with realistic isoprene emissions coming from a Mediterranean oak forest. Two types of anthropogenic sources, respectively representative of the Marseille (urban and Martigues (industrial French Mediterranean sites, and both characterized by different VOC/NOx are considered. For the Marseille scenario, the impact of biogenic emission on ozone production is larger when the forest is situated in a sub-urban configuration (i.e. downwind distance TOWN-FOREST -1. In this case the enhancement of ozone production due to isoprene can reach +37% in term of maximum surface concentrations and +11% in term of total ozone production. The impact of biogenic emission decreases quite rapidly when the TOWN-FOREST distance increases. For the Martigues scenario, the biogenic impact on the plume is significant up to TOWN-FOREST distance of 90km where the ozone maximum surface concentration enhancement can still reach +30%. For both cases, the

Overview of VOC emissions and chemistry from PTR-TOF-MS measurements during the SusKat-ABC campaign: high acetaldehyde, isoprene and isocyanic acid in wintertime air of the Kathmandu Valley

Science.gov (United States)

Sarkar, Chinmoy; Sinha, Vinayak; Kumar, Vinod; Rupakheti, Maheswar; Panday, Arnico; Mahata, Khadak S.; Rupakheti, Dipesh; Kathayat, Bhogendra; Lawrence, Mark G.

2016-03-01

The Kathmandu Valley in Nepal suffers from severe wintertime air pollution. Volatile organic compounds (VOCs) are key constituents of air pollution, though their specific role in the valley is poorly understood due to insufficient data. During the SusKat-ABC (Sustainable Atmosphere for the Kathmandu Valley-Atmospheric Brown Clouds) field campaign conducted in Nepal in the winter of 2012-2013, a comprehensive study was carried out to characterise the chemical composition of ambient Kathmandu air, including the determination of speciated VOCs, by deploying a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) - the first such deployment in South Asia. In the study, 71 ion peaks (for which measured ambient concentrations exceeded the 2σ detection limit) were detected in the PTR-TOF-MS mass scan data, highlighting the chemical complexity of ambient air in the valley. Of the 71 species, 37 were found to have campaign average concentrations greater than 200 ppt and were identified based on their spectral characteristics, ambient diel profiles and correlation with specific emission tracers as a result of the high mass resolution (m / Δm > 4200) and temporal resolution (1 min) of the PTR-TOF-MS. The concentration ranking in the average VOC mixing ratios during our wintertime deployment was acetaldehyde (8.8 ppb) > methanol (7.4 ppb) > acetone + propanal (4.2 ppb) > benzene (2.7 ppb) > toluene (1.5 ppb) > isoprene (1.1 ppb) > acetonitrile (1.1 ppb) > C8-aromatics ( ˜ 1 ppb) > furan ( ˜ 0.5 ppb) > C9-aromatics (0.4 ppb). Distinct diel profiles were observed for the nominal isobaric compounds isoprene (m / z = 69.070) and furan (m / z = 69.033). Comparison with wintertime measurements from several locations elsewhere in the world showed mixing ratios of acetaldehyde ( ˜ 9 ppb), acetonitrile ( ˜ 1 ppb) and isoprene ( ˜ 1 ppb) to be among the highest reported to date. Two "new" ambient compounds, namely formamide (m / z = 46.029) and acetamide (m / z

Pd(OAc)2/Ph3P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles.

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Kellner, Dominik; Weger, Maximilian; Gini, Andrea; Mancheño, Olga García

2017-01-01

The palladium-catalyzed dimerization of isoprene is a practical approach of synthesizing monoterpenes. Though several highly selective methods have been reported, most of them still required pressure or costly ligands for attaining the active system and desired selectivity. Herein, we present a simple and economical procedure towards the tail-to-tail dimer using readily available Pd(OAc) 2 and inexpensive triphenylphosphine as ligand. Furthermore, simple screw cap vials are employed, allowing carrying out the reaction at low pressure. In addition, the potential of the dimer as a chemical platform for the preparation of heterocyclic terpenes by subsequent (hetero)-Diels-Alder or [4 + 1]-cycloadditions with nitrenes is also depicted.

Multilayer Graphene/Carbon Black/Chlorine Isobutyl Isoprene Rubber Nanocomposites

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Daniele Frasca

2016-03-01

Full Text Available High loadings of carbon black (CB are usually used to achieve the properties demanded of rubber compounds. In recent years, distinct nanoparticles have been investigated to replace CB in whole or in part, in order to reduce the necessary filler content or to improve performance. Multilayer graphene (MLG is a nanoparticle made of just 10 graphene sheets and has recently become commercially available for mass-product nanocomposites. Three phr (part for hundred rubbers of MLG are added to chlorine isobutyl isoprene rubber (CIIR/CB composites in order to replace part of the CB. The incorporation of just 3 phr MLG triples the Young’s modulus of CIIR; the same effect is obtained with 20 phr CB. The simultaneous presence of three MLG and CB also delivers remarkable properties, e.g. adding three MLG and 20 phr CB increased the hardness as much as adding 40 phr CB. A comprehensive study is presented, showing the influence on a variety of mechanical properties. The potential of the MLG/CB combination is illustrated to reduce the filler content or to boost performance, respectively. Apart from the remarkable mechanical properties, the CIIR/CB/MLG nanocomposites showed an increase in weathering resistance.

Pd(OAc2/Ph3P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles

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Dominik Kellner

2017-08-01

Full Text Available The palladium-catalyzed dimerization of isoprene is a practical approach of synthesizing monoterpenes. Though several highly selective methods have been reported, most of them still required pressure or costly ligands for attaining the active system and desired selectivity. Herein, we present a simple and economical procedure towards the tail-to-tail dimer using readily available Pd(OAc2 and inexpensive triphenylphosphine as ligand. Furthermore, simple screw cap vials are employed, allowing carrying out the reaction at low pressure. In addition, the potential of the dimer as a chemical platform for the preparation of heterocyclic terpenes by subsequent (hetero-Diels–Alder or [4 + 1]-cycloadditions with nitrenes is also depicted.

Challenges in modelling isoprene and monoterpene emission dynamics of Arctic plants: a case study from a subarctic tundra heath

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Tang, Jing; Schurgers, Guy; Valolahti, Hanna; Faubert, Patrick; Tiiva, Päivi; Michelsen, Anders; Rinnan, Riikka

2016-12-01

The Arctic is warming at twice the global average speed, and the warming-induced increases in biogenic volatile organic compounds (BVOCs) emissions from Arctic plants are expected to be drastic. The current global models' estimations of minimal BVOC emissions from the Arctic are based on very few observations and have been challenged increasingly by field data. This study applied a dynamic ecosystem model, LPJ-GUESS, as a platform to investigate short-term and long-term BVOC emission responses to Arctic climate warming. Field observations in a subarctic tundra heath with long-term (13-year) warming treatments were extensively used for parameterizing and evaluating BVOC-related processes (photosynthesis, emission responses to temperature and vegetation composition). We propose an adjusted temperature (T) response curve for Arctic plants with much stronger T sensitivity than the commonly used algorithms for large-scale modelling. The simulated emission responses to 2 °C warming between the adjusted and original T response curves were evaluated against the observed warming responses (WRs) at short-term scales. Moreover, the model responses to warming by 4 and 8 °C were also investigated as a sensitivity test. The model showed reasonable agreement to the observed vegetation CO2 fluxes in the main growing season as well as day-to-day variability of isoprene and monoterpene emissions. The observed relatively high WRs were better captured by the adjusted T response curve than by the common one. During 1999-2012, the modelled annual mean isoprene and monoterpene emissions were 20 and 8 mg C m-2 yr-1, with an increase by 55 and 57 % for 2 °C summertime warming, respectively. Warming by 4 and 8 °C for the same period further elevated isoprene emission for all years, but the impacts on monoterpene emissions levelled off during the last few years. At hour-day scale, the WRs seem to be strongly impacted by canopy air T, while at the day-year scale, the WRs are a combined

Synthesis of styrene/isoprene/butadiene integrated rubber with wide glass transition temperature by reactive extrusion

Science.gov (United States)

Huang, Tianhua; Zheng, Anna; Zhan, Pengfei; Shi, Han; Li, Xiang; Guan, Yong; Wei, Dafu

2018-05-01

In this work, styrene/isoprene/butadiene integrated rubber (SIBR) was synthesized with n-butyllithium as the initiator and tetrahydrofuran as structure modifier in a co-rotating intermeshing twin-screw extruder. The content of diene in these terpolymers reached a surprising 70 wt% by feeding the monomers in two different sites of the twin-screw extruder. 1H-NMR, GPC and TEM results showed that the molecular structures of terpolymers changed with the variation of feeding site. Dynamic mechanical analysis of the vulcanized SIBR showed that the terpolymer had a wide glass transition region, which assured an excellent combination of high antiskid properties and low rolling resistance. Different from traditional solution polymerization, the present work provides a green approach to prepare the SIBR via bulk polymerization without solvent.

Small-angle neutron scattering investigation of the chain conformation of lamellar polystyrene/isoprene phase in solid state

International Nuclear Information System (INIS)

Constantinescu, L.M.

1994-01-01

Small-angle neutron scattering has been used in the study of chain conformation of lamellar styrene/isoprene block copolymers oriented in large single crystals. The radius of gyration of deuterated polystyrene chains around the normal to the interface has been measured. By comparing this direct evolution of the lateral dimension of the chains with the average chain separation given by the molecular area (the surface available at the interface for each covalent bond linking the blocks together) we characterized the transverse interpenetration degree of the chains. The polystyrene chains are displayed in simple strata own micro-domains, without an important interpenetration. (Author) 9 Figs., 2 Tabs., 25 Refs

Particle growth in an isoprene-rich forest: Influences of urban, wildfire, and biogenic air masses

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Gunsch, Matthew J.; Schmidt, Stephanie A.; Gardner, Daniel J.; Bondy, Amy L.; May, Nathaniel W.; Bertman, Steven B.; Pratt, Kerri A.; Ault, Andrew P.

2018-04-01

Growth of freshly nucleated particles is an important source of cloud condensation nuclei (CCN) and has been studied within a variety of environments around the world. However, there remains uncertainty regarding the sources of the precursor gases leading to particle growth, particularly in isoprene-rich forests. In this study, particle growth events were observed from the 14 total events (31% of days) during summer measurements (June 24 - August 2, 2014) at the Program for Research on Oxidants PHotochemistry, Emissions, and Transport (PROPHET) tower within the forested University of Michigan Biological Station located in northern Michigan. Growth events were observed within long-range transported air masses from urban areas, air masses impacted by wildfires, as well as stagnant, forested/regional air masses. Growth events observed during urban-influenced air masses were prevalent, with presumably high oxidant levels, and began midday during periods of high solar radiation. This suggests that increased oxidation of biogenic volatile organic compounds (BVOCs) likely contributed to the highest observed particle growth in this study (8 ± 2 nm h-1). Growth events during wildfire-influenced air masses were observed primarily at night and had slower growth rates (3 ± 1 nm h-1). These events were likely influenced by increased SO2, O3, and NO2 transported within the smoke plumes, suggesting a role of NO3 oxidation in the production of semi-volatile compounds. Forested/regional air mass growth events likely occurred due to the oxidation of regionally emitted BVOCs, including isoprene, monoterpenes, and sesquiterpenes, which facilitated multiday growth events also with slower rates (3 ± 2 nm h-1). Intense sulfur, carbon, and oxygen signals in individual particles down to 20 nm, analyzed by transmission electron microscopy with energy dispersive X-ray spectroscopy (TEM-EDX), suggest that H2SO4 and secondary organic aerosol contributed to particle growth. Overall, aerosol

Overview of VOC emissions and chemistry from PTR-TOF-MS measurements during the SusKat-ABC campaign: high acetaldehyde, isoprene and isocyanic acid in wintertime air of the Kathmandu Valley

Directory of Open Access Journals (Sweden)

C. Sarkar

2016-03-01

Full Text Available The Kathmandu Valley in Nepal suffers from severe wintertime air pollution. Volatile organic compounds (VOCs are key constituents of air pollution, though their specific role in the valley is poorly understood due to insufficient data. During the SusKat-ABC (Sustainable Atmosphere for the Kathmandu Valley–Atmospheric Brown Clouds field campaign conducted in Nepal in the winter of 2012–2013, a comprehensive study was carried out to characterise the chemical composition of ambient Kathmandu air, including the determination of speciated VOCs, by deploying a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS – the first such deployment in South Asia. In the study, 71 ion peaks (for which measured ambient concentrations exceeded the 2σ detection limit were detected in the PTR-TOF-MS mass scan data, highlighting the chemical complexity of ambient air in the valley. Of the 71 species, 37 were found to have campaign average concentrations greater than 200 ppt and were identified based on their spectral characteristics, ambient diel profiles and correlation with specific emission tracers as a result of the high mass resolution (m ∕ Δm  >  4200 and temporal resolution (1 min of the PTR-TOF-MS. The concentration ranking in the average VOC mixing ratios during our wintertime deployment was acetaldehyde (8.8 ppb  >  methanol (7.4 ppb  >  acetone + propanal (4.2 ppb  >  benzene (2.7 ppb  >  toluene (1.5 ppb  >  isoprene (1.1 ppb  >  acetonitrile (1.1 ppb  >  C8-aromatics ( ∼ 1 ppb  >  furan ( ∼ 0.5 ppb  >  C9-aromatics (0.4 ppb. Distinct diel profiles were observed for the nominal isobaric compounds isoprene (m ∕ z  =  69.070 and furan (m ∕ z  =  69.033. Comparison with wintertime measurements from several locations elsewhere in the world showed mixing ratios of acetaldehyde ( ∼  9 ppb, acetonitrile ( ∼  1 ppb and isoprene

Long-term measurements of biogenic VOCs in an Austrian valley - discussion of seasonal fluctuations of isoprene and monoterpene concentrations

International Nuclear Information System (INIS)

Dunkl, J.; Schnitzhofer, R.; Beauchamp, J.; Wisthaler, A; Hansel, A.

2006-01-01

Full text: A proton-transfer-reaction mass spectrometer (PTR-MS) was set up at a monitoring station in the river Inn valley (Vomp, Tirol, Austria) for a year-long measurement (February 2004-May 2005) of volatile organic compounds (VOCs) in the local valley air. Measurements of PM 10 , NO x and CO, and certain meteorological parameters were additionally made. Together, these data-sets enabled relationships between VOC abundances, meteorological conditions and anthropogenic emissions (primarily from automobile emissions) to be examined. The work presented here focuses on the biogenic VOCs measured under these real-world outdoor conditions. Initially, data needed to be separated between VOCs of anthropogenic and of biogenic origin. This was achieved by generating a model for the PTR-MS VOC data-set. A clear correlation between benzene and CO concentrations - indicating benzene's predominance from anthropogenic sources - allowed benzene to be used as a tracer for anthropogenic compounds. The model thus allowed a regression to be made whereby the maximum anthropogenic contributions of almost all VOCs could be established relative to benzene. The maximum contribution from biogenic emissions to each VOC could thus be determined as the difference between the total individual VOC signal and the corresponding maximum anthropogenic share. The two biogenic VOCs of principle interest here were isoprene and the monoterpenes (detected by PTR-MS at masses 69 amu and 137 amu, respectively). As expected, abundances of isoprene and the monoterpenes displayed a late-summer maximum (despite good vertical valley air dilution that acts to reduce VOC levels) when temperatures were high and sunlight hours long. Preliminary results will be presented and discussed. (author)

Effects of Isoprene- and Toluene-Generated Smog on Allergic ...

Science.gov (United States)

Reactions of organic compounds with nitric oxide (NO) and sunlight produce complex mixtures of pollutants including secondary organic aerosol (SOA), ozone (O3), nitrogen dioxide (NO2), and reactive aldehydes. The health effects of these photochemical smog mixtures in susceptible populations including asthmatics are unclear. We assessed effects of smog generated from mixtures of NO with isoprene (IS) or toluene (TL) on allergic inflammatory responses in Balb/cJ mice. House dust mite (HDM)-sensitized or control mice were all challenged with HDM intranasally 1 d prior to whole-body inhalation exposure to IS (chamber average 509 ppb NO2, 246 ppb O3, and 160 g/m3 SOA), TL (217 ppb NO2, 129 ppb O3, and 376 g/m3 SOA), or HEPA-filtered air (4 h/d for 2 days). Mice were necropsied within 3 h after the second exposure (2 d post-HDM challenge). Assessment of breathing parameters during exposure with double-chamber plethysmography showed a trend for increased specific airway resistance and decreased minute volume during the second day of TL exposure in both non-allergic and HDM-allergic mice. HDM-allergic air-exposed mice had significant increases in numbers of bronchoalveolar lavage (BAL) alveolar macrophages (AM) and eosinophils (EO), and trends for increases in BAL indices of lung injury in comparison with non-allergic air-exposed mice. Exposure to either IS or TL attenuated the increases in AM, EO, and lung injury markers in HDM-allergic mice. The results of this

The influence of drought on flow‐ecology relationships in Ozark Highland streams

Science.gov (United States)

Lynch, Dustin T.; Leasure, D. R.; Magoulick, Daniel D.

2018-01-01

Drought and summer drying can have strong effects on abiotic and biotic components of stream ecosystems. Environmental flow‐ecology relationships may be affected by drought and drying, adding further uncertainty to the already complex interaction of flow with other environmental variables, including geomorphology and water quality.Environment–ecology relationships in stream communities in Ozark Highland streams, USA, were examined over two years with contrasting environmental conditions, a drought year (2012) and a flood year (2013). We analysed fish, crayfish and benthic macroinvertebrate assemblages using two different approaches: (1) a multiple regression analysis incorporating predictor variables related to habitat, water quality, geomorphology and hydrology and (2) a canonical ordination procedure using only hydrologic variables in which forward selection was used to select predictors that were most related to our response variables.Reach‐scale habitat quality and geomorphology were found to be the most important influences on community structure, but hydrology was also important, particularly during the flood year. We also found substantial between‐year variation in environment–ecology relationships. Some ecological responses differed significantly between drought and flood years, while others remained consistent. We found that magnitude was the most important flow component overall, but that there was a shift in relative importance from low flow metrics during the drought year to average flow metrics during the flood year, and the specific metrics of importance varied markedly between assemblages and years.Findings suggest that understanding temporal variation in flow‐ecology relationships may be crucial for resource planning. While some relationships show temporal variation, others are consistent between years. Additionally, different kinds of hydrologic variables can differ greatly in terms of which assemblages they affect and how they affect

Stream permanence influences crayfish occupancy and abundance in the Ozark Highlands, USA

Science.gov (United States)

Yarra, Allyson N.; Magoulick, Daniel D.

2018-01-01

Crayfish use of intermittent streams is especially important to understand in the face of global climate change. We examined the influence of stream permanence and local habitat on crayfish occupancy and species densities in the Ozark Highlands, USA. We sampled in June and July 2014 and 2015. We used a quantitative kick–seine method to sample crayfish presence and abundance at 20 stream sites with 32 surveys/site in the Upper White River drainage, and we measured associated local environmental variables each year. We modeled site occupancy and detection probabilities with the software PRESENCE, and we used multiple linear regressions to identify relationships between crayfish species densities and environmental variables. Occupancy of all crayfish species was related to stream permanence. Faxonius meeki was found exclusively in intermittent streams, whereas Faxonius neglectus and Faxonius luteushad higher occupancy and detection probability in permanent than in intermittent streams, and Faxonius williamsi was associated with intermittent streams. Estimates of detection probability ranged from 0.56 to 1, which is high relative to values found by other investigators. With the exception of F. williamsi, species densities were largely related to stream permanence rather than local habitat. Species densities did not differ by year, but total crayfish densities were significantly lower in 2015 than 2014. Increased precipitation and discharge in 2015 probably led to the lower crayfish densities observed during this year. Our study demonstrates that crayfish distribution and abundance is strongly influenced by stream permanence. Some species, including those of conservation concern (i.e., F. williamsi, F. meeki), appear dependent on intermittent streams, and conservation efforts should include consideration of intermittent streams as an important component of freshwater biodiversity.

75 FR 3455 - Union Electric Company dba Ameren/UE; Notice of Application for Amendment of License and...

Science.gov (United States)

2010-01-21

... located at the Ozark Yacht Club near mile marker 0.8+0.6 in Jennings Branch Cove on the Lake of the Ozarks... of Request: The licensee requests approval to permit Ozark Yacht Club to construct a new 4-slip boat... for use by patrons of the Ozark Yacht Club. l. Locations of the Application: A copy of the application...

Organic Nitrate Chemistry and Its Implications for Nitrogen Budgets in an Isoprene- and Monoterpene-Rich Atmosphere: Constraints From Aircraft (SEAC4RS) and Ground-Based (SOAS) Observations in the Southeast US

Science.gov (United States)

Fisher, Jenny; Jacob, D. J.; Travis, K. R.; Kim, P. S.; Marais, E. A.; Miller, C. Chan; Yu, K.; Zhu, L.; Yantosca, R. M.; Sulprizio, M. P.;

Monitoring oak-hickory forest change during an unprecedented red oak borer outbreak in the Ozark Mountains: 1990 to 2006

Science.gov (United States)

Jones, Joshua S.; Tullis, Jason A.; Haavik, Laurel J.; Guldin, James M.; Stephen, Fred M.

2014-01-01

Upland oak-hickory forests in Arkansas, Missouri, and Oklahoma experienced oak decline in the late 1990s and early 2000s during an unprecedented outbreak of a native beetle, the red oak borer (ROB), Enaphalodes rufulus (Haldeman). Although remote sensing supports frequent monitoring of continuously changing forests, comparable in situ observations are critical for developing an understanding of past and potential ROB damage in the Ozark Mountains. We categorized forest change using a normalized difference water index (NDWI) applied to multitemporal Landsat TM and ETM+ imagery (1990, 2001, and 2006). Levels of decline or growth were categorized using simple statistical thresholds of change in the NDWI over time. Corresponding decline and growth areas were then observed in situ where tree diameter, age, crown condition, and species composition were measured within variable radius plots. Using a machine learning decision tree classifier, remote sensing-derived decline and growth was characterized in terms of in situ observation. Plots with tree quadratic mean diameter at breast height ≥21.5 cm were categorized remotely as in severe decline. Landsat TM/ETM+-based NDWI derivatives reveal forest decline and regrowth in post-ROB outbreak surveys. Historical and future Landsat-based canopy change detection should be incorporated with existing landscape-based prediction of ROB hazard.

76 FR 56425 - Union Electric Company, dba Ameren Missouri; Notice of Application for Amendment of License and...

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2011-09-13

... proposed non-project use would be located at the Ozark Yacht Club marina which is located at mile marker 0... for the Osage Hydroelectric Project, requests Commission authorization to permit the Ozark Yacht Club... patrons of the Ozark Yacht Club. No dredging activities, shoreline stabilization, or fueling facilities...

Influence of future cropland expansion on regional and global tropospheric ozone

Science.gov (United States)

Squire, Oliver; Archibald, Alex; Telford, Paul; Pyle, John

2013-04-01

. It was found that the effect of transplanting these isoprene schemes into the base CheT chemistry scheme lead, in both cases, to higher ozone over isoprene rich regions by up to ~40 ppb. Furthermore, upon repeating the land use change experiment with these other isoprene schemes, it was found that the AQUM scheme produced more ozone (up to ~20 ppb more) in isoprene rich regions due to crop expansion than CheT. However the CESM Superfast scheme showed the opposite effect, producing less ozone than the CheT scheme in isoprene-rich regions. These varied responses highlight the sensitivity of future trends in surface ozone to isoprene chemistry within the range of some currently used chemical schemes, and suggest that further research is needed in order to most effectively parameterise this complex chemistry.

Isoprene and monoterpene emissions in south-east Australia: comparison of a multi-layer canopy model with MEGAN and with atmospheric observations

Directory of Open Access Journals (Sweden)

K. M. Emmerson

2018-05-01

Full Text Available One of the key challenges in atmospheric chemistry is to reduce the uncertainty of biogenic volatile organic compound (BVOC emission estimates from vegetation to the atmosphere. In Australia, eucalypt trees are a primary source of biogenic emissions, but their contribution to Australian air sheds is poorly quantified. The Model of Emissions of Gases and Aerosols from Nature (MEGAN has performed poorly against Australian isoprene and monoterpene observations. Finding reasons for the MEGAN discrepancies and strengthening our understanding of biogenic emissions in this region is our focus. We compare MEGAN to the locally produced Australian Biogenic Canopy and Grass Emissions Model (ABCGEM, to identify the uncertainties associated with the emission estimates and the data requirements necessary to improve isoprene and monoterpene emissions estimates for the application of MEGAN in Australia. Previously unpublished, ABCGEM is applied as an online biogenic emissions inventory to model BVOCs in the air shed overlaying Sydney, Australia. The two models use the same meteorological inputs and chemical mechanism, but independent inputs of leaf area index (LAI, plant functional type (PFT and emission factors. We find that LAI, a proxy for leaf biomass, has a small role in spatial, temporal and inter-model biogenic emission variability, particularly in urban areas for ABCGEM. After removing LAI as the source of the differences, we found large differences in the emission activity function for monoterpenes. In MEGAN monoterpenes are partially light dependent, reducing their dependence on temperature. In ABCGEM monoterpenes are not light dependent, meaning they continue to be emitted at high rates during hot summer days, and at night. When the light dependence of monoterpenes is switched off in MEGAN, night-time emissions increase by 90–100 % improving the comparison with observations, suggesting the possibility that monoterpenes emitted from Australian

Enhanced Oxidation of Isoprene and Monoterpenes in High and Low NOx Conditions

Science.gov (United States)

Tokarek, T. W.; Gilman, J.; Lerner, B. M.; Koss, A.; Yuan, B.; Taha, Y. M.; Osthoff, H. D.; Warneke, C.; De Gouw, J. A.

2015-12-01

In the troposphere, the photochemical oxidation of volatile organic compounds (VOCs) is primarily initiated by their reactions with the hydroxyl radical (OH) which yields peroxy radicals (HO2 and RO2). Concentrations of OH and the rates of VOC oxidation depend on the efficiency of peroxy radical recycling to OH. Radical recycling mainly occurs through reaction of HO2 with NO to produce NO2 and, ultimately, ozone (O3). Hence, the rate of VOC oxidation is dependent on NOx (=NO+NO2) concentration. The Shale Oil and Natural Gas Nexus (SONGNEX) campaign was conducted from March 17 to April 29, 2015 with the main goal of identifying and quantifying industrial sources of pollutants throughout the United States, in particular those associated with the production of oil and natural gas. In this work, a case study of biogenic VOC oxidation within and outside a power plant plume in the Haynesville basin near the border of Texas and Louisiana is presented. Isoprene, monoterpenes and their oxides were measured by H3O+ chemical ionization mass spectrometry (H3O+ CIMS) in high time resolution (1 s). Further, an improved Whole Air Sampler (iWAS) was used to collect samples for post-flight analysis by gas chromatography mass spectrometric detection (GC-MS) and yielded speciated quantification of biogenic VOCs. The monoterpene oxide to monoterpene ratio follows the spatial extent of the plume as judged by another tracer (NOx), tracking the enhancement of oxidation rates by NOx. The observations are rationalized with the aid of box modeling using the Master Chemical Mechanism (MCM).

Emissions of hydrocarbons from marine phytoplankton—Some results from controlled laboratory experiments

Science.gov (United States)

McKay, W. A.; Turner, M. F.; Jones, B. M. R.; Halliwell, C. M.

Laboratory experiments have been carried out to help assess and quantify the role of marine phytoplankton in the production of non-methane hydrocarbons. Evidence is presented here that supports the hypothesis that some short-chain hydrocarbons are produced during diatom and dinoflagellate lifecycles. The pattern of their emissions to the air above axenic unicultures of diatoms and dinoflagellates has been followed. The results suggest that ethane, ethene, propane and propene are produced during the autolysis of some phytoplankton, possibly by the oxidation of polyunsaturated lipids released into their culture medium. In contrast, isoprene and hexane appear during phytoplankton growth and are thus most likely produced either directly by the plankton or through the oxidation of exuded dissolved organic carbon.

Vegetation history since the last glacial maximum in the Ozark highlands (USA): A new record from Cupola Pond, Missouri

Science.gov (United States)

Jones, Rachel A.; Williams, John W.; Jackson, Stephen T.

2017-08-01

The timing and drivers of vegetation dynamics and formation of no-analog plant communities during the last deglaciation in the unglaciated southeastern US are poorly understood. We present a multi-proxy record spanning the past 19,800 years from Cupola Pond in the Ozarks Mountains, consisting of replicate high-resolution pollen records, 25 AMS radiocarbon dates, and macrofossil, charcoal, and coprophilous spore analyses. Full-glacial Pinus and Picea forests gave way to no-analog vegetation after 17,400 yr BP, followed by development of Quercus-dominated Holocene forests, with late Holocene rises in Pinus and Nyssa. Vegetation transitions, replicated in different cores, are closely linked to hemispheric climate events. Rising Quercus abundances coincide with increasing Northern Hemisphere temperatures and CO2 at 17,500 yr BP, declining Pinus and Picea at 14,500 yr BP are near the Bølling-Allerød onset, and rapid decline of Fraxinus and rise of Ostrya/Carpinus occur 12,700 yr BP during the Younger Dryas. The Cupola no-analog vegetation record is unusual for its early initiation (17,000 yr BP) and for its three vegetation zones, representing distinct rises of Fraxinus and Ostrya/Carpinus. Sporormiella was absent and sedimentary charcoal abundances were low throughout, suggesting that fire and megaherbivores were not locally important agents of disturbance and turnover. The Cupola record thus highlights the complexity of the late-glacial no-analog communities and suggests direct climatic regulation of their formation and disassembly.

Nanostructuration of self-assembled poly(styrene-b-isoprene-b-styrene) block copolymer thin films in a highly oriented pyrolytic graphite substrate

Energy Technology Data Exchange (ETDEWEB)

Zalakain, Inaki; Ramos, Jose Angel; Fernandez, Raquel; Etxeberria, Haritz; Mondragon, Inaki, E-mail: inaki.mondragon@ehu.e

2011-01-03

Highly oriented pyrolitic graphite (HOPG) is a useful substrate to visualize epitaxial formation due to its crystallographic structure. The morphology of a poly(styrene-b-isoprene-b-styrene) block copolymer thin film on a HOPG substrate was investigated by atomic force microscopy. Block copolymer domains generated a morphology with triangular regularity. This arrangement was induced by the HOPG substrate structure due to van der Waals attraction between the HOPG {pi}-conjugated system and aromatic ring of polystyrene domains. However, increasing the film thickness, the substrate effect on the surface morphology decreased. As a consequence, film surfaces showed the coexistence of different structures such as highly aligned cylinders and perforated lamellae. When film thickness exceeded a threshold value, the substrate did not have effect in the surface arrangements and the surface showed a similar morphology to that existing in bulk.

Production of terpenes in the culture of Chlorophyceae and Rhodophyta

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Abe, M.; Hashimoto, S.

2014-12-01

Terpenes show high reactivity in the troposphere, contributing to organic aerosol reactions with OH radicals. One of the main sources of terpenes in the atmosphere is terrestrial plants. It has been recently reported that marine phytoplankton also produce monoterpenes (Yassaa et al: 2008). Because aerosol production of natural origin affects the cloud cover over the open ocean, it is important to investigate the origin of aerosol generation in the open ocean. In this study, we investigated the production of terpenes and isoprene with a focus on Chlamydomonas (Chlorophyceae) and Rhodella maculata (Rhodophyta). Concentrations of terpenes and isoprene were measured using a dynamic headspace (GERSTEL DHS)—gas chromatograph (Agilent 6890N)—mass spectrometer (Agilent 5975C). In addition, chlorophyll a was measured using a fluorometer (Turner TD-700). The results showed that isoprene, α-pinene, and β-pinene were produced by Chlamydomonas sp. and that isoprene, limonene, and camphene were produced by Rhodella maculata. Chlamydomonas sp. produced α-pinene and β-pinene, similar to land plants. The ratio of the pinene/isoprene concentrations in the atmosphere over seawater where phytoplankton are blooming has been reported as approximately 0.7 (Yassaa et al: 2008). In this experiment, the pinene/isoprene concentration ratios in the cultures were approximately 0.1. This result indicates that marine phytoplankton may not be ignored in the marine atmosphere chemistry of terpenes.

Evaluation of Isoprene Chain Extension from PEO Macromolecular Chain Transfer Agents for the Preparation of Dual, Invertible Block Copolymer Nanoassemblies.

Science.gov (United States)

Bartels, Jeremy W; Cauët, Solène I; Billings, Peter L; Lin, Lily Yun; Zhu, Jiahua; Fidge, Christopher; Pochan, Darrin J; Wooley, Karen L

2010-09-14

Two RAFT-capable PEO macro-CTAs, 2 and 5 kDa, were prepared and used for the polymerization of isoprene which yielded well-defined block copolymers of varied lengths and compositions. GPC analysis of the PEO macro-CTAs and block copolymers showed remaining unreacted PEO macro-CTA. Mathematical deconvolution of the GPC chromatograms allowed for the estimation of the blocking efficiency, about 50% for the 5 kDa PEO macro-CTA and 64% for the 2 kDa CTA. Self assembly of the block copolymers in both water and decane was investigated and the resulting regular and inverse assemblies, respectively, were analyzed with DLS, AFM, and TEM to ascertain their dimensions and properties. Assembly of PEO-b-PIp block copolymers in aqueous solution resulted in well-defined micelles of varying sizes while the assembly in hydrophobic, organic solvent resulted in the formation of different morphologies including large aggregates and well-defined cylindrical and spherical structures.

Secondary organic aerosol from VOC mixtures in an oxidation flow reactor

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Ahlberg, Erik; Falk, John; Eriksson, Axel; Holst, Thomas; Brune, William H.; Kristensson, Adam; Roldin, Pontus; Svenningsson, Birgitta

2017-07-01

The atmospheric organic aerosol is a tremendously complex system in terms of chemical content. Models generally treat the mixtures as ideal, something which has been questioned owing to model-measurement discrepancies. We used an oxidation flow reactor to produce secondary organic aerosol (SOA) mixtures containing oxidation products of biogenic (α-pinene, myrcene and isoprene) and anthropogenic (m-xylene) volatile organic compounds (VOCs). The resulting volume concentration and chemical composition was measured using a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), respectively. The SOA mass yield of the mixtures was compared to a partitioning model constructed from single VOC experiments. The single VOC SOA mass yields with no wall-loss correction applied are comparable to previous experiments. In the mixtures containing myrcene a higher yield than expected was produced. We attribute this to an increased condensation sink, arising from myrcene producing a significantly higher number of nucleation particles compared to the other precursors. Isoprene did not produce much mass in single VOC experiments but contributed to the mass of the mixtures. The effect of high concentrations of isoprene on the OH exposure was found to be small, even at OH reactivities that previously have been reported to significantly suppress OH exposures in oxidation flow reactors. Furthermore, isoprene shifted the particle size distribution of mixtures towards larger sizes, which could be due to a change in oxidant dynamics inside the reactor.

Parameterized isoprene and monoterpene emissions from the boreal forest floor: Implementation into a 1D chemistry-transport model and investigation of the influence on atmospheric chemistry

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Mogensen, Ditte; Aaltonen, Hermanni; Aalto, Juho; Bäck, Jaana; Kieloaho, Antti-Jussi; Gierens, Rosa; Smolander, Sampo; Kulmala, Markku; Boy, Michael

2015-04-01

Volatile organic compounds (VOCs) are emitted from the biosphere and can work as precursor gases for aerosol particles that can affect the climate (e.g. Makkonen et al., ACP, 2012). VOC emissions from needles and leaves have gained the most attention, however other parts of the ecosystem also have the ability to emit a vast amount of VOCs. This, often neglected, source can be important e.g. at periods where leaves are absent. Both sources and drivers related to forest floor emission of VOCs are currently limited. It is thought that the sources are mainly due to degradation of organic matter (Isidorov and Jdanova, Chemosphere, 2002), living roots (Asensio et al., Soil Biol. Biochem., 2008) and ground vegetation. The drivers are biotic (e.g. microbes) and abiotic (e.g. temperature and moisture). However, the relative importance of the sources and the drivers individually are currently poorly understood. Further, the relative importance of these factors is highly dependent on the tree species occupying the area of interest. The emission of isoprene and monoterpenes where measured from the boreal forest floor at the SMEAR II station in Southern Finland (Hari and Kulmala, Boreal Env. Res., 2005) during the snow-free period in 2010-2012. We used a dynamic method with 3 automated chambers analyzed by Proton Transfer Reaction - Mass Spectrometer (Aaltonen et al., Plant Soil, 2013). Using this data, we have developed empirical parameterizations for the emission of isoprene and monoterpenes from the forest floor. These parameterizations depends on abiotic factors, however, since the parameterizations are based on field measurements, biotic features are captured. Further, we have used the 1D chemistry-transport model SOSAA (Boy et al., ACP, 2011) to test the seasonal relative importance of inclusion of these parameterizations of the forest floor compared to the canopy crown emissions, on the atmospheric reactivity throughout the canopy.

Shuttle imaging radar-A (SIR-A) data analysis. [geology of the Ozark Plateau of southern Missouri, land use in western Illinois, and vegetation types at Koonamore Station, Australia

Science.gov (United States)

Arvidson, R. E.

1983-01-01

The utility of shuttle imaging radar (SIR-A) data was evaluated in several geological and environmental contexts. For the Ozark Plateau of southern Missouri, SIR-A data were of little use in mapping structural features, because of generally uniform returns. For western Illinois, little was to be gained in terms of identifying land use categories by examining differences between overlapping passes. For southern Australia (Koonamore Station), information ion vegetation types that was not obtainable from LANDSAT MSS data alone was obtained. Specifically, high SIR-A returns in the Australian site were found to correlate with locations where shrubs increase surface roughness appreciably. The Australian study site results demonstrate the synergy of acquiring spectral reflectance and radar data over the same location and time. Such data are especially important in that region, since grazing animals have substantially altered and are continuing to alter the distribution of shrublands, grasslands, and soil exposures. Periodic, synoptic acquisition of MSS and SAR data would be of use in monitoring the dynamics of land-cover change in this environment.

Challenges for creating a site-specific groundwater-use record for the Ozark Plateaus aquifer system (central USA) from 1900 to 2010

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Knierim, Katherine J.; Nottmeier, Anna M.; Worland, Scott; Westerman, Drew A.; Clark, Brian R.

2017-09-01

Hydrologic budgets to determine groundwater availability are important tools for water-resource managers. One challenging component for developing hydrologic budgets is quantifying water use through time because historical and site-specific water-use data can be sparse or poorly documented. This research developed a groundwater-use record for the Ozark Plateaus aquifer system (central USA) from 1900 to 2010 that related county-level aggregated water-use data to site-specific well locations and aquifer units. A simple population-based linear model, constrained to 0 million liters per day in 1900, provided the best means to extrapolate groundwater-withdrawal rates pre-1950s when there was a paucity of water-use data. To disaggregate county-level data to individual wells across a regional aquifer system, a programmatic hierarchical process was developed, based on the level of confidence that a well pumped groundwater for a specific use during a specific year. Statistical models tested on a subset of the best-available site-specific water-use data provided a mechanism to bracket historic groundwater use, such that groundwater-withdrawal rates ranged, on average, plus or minus 38% from modeled values. Groundwater withdrawn for public supply and domestic use accounted for between 48 and 74% of total groundwater use since 1901, highlighting that groundwater provides an important drinking-water resource. The compilation, analysis, and spatial and temporal extrapolation of water-use data remain a challenging task for water scientists, but is of paramount importance to better quantify groundwater use and availability.

Vegetation history since the last glacial maximum in the Ozark highlands (USA): A new record from Cupola Pond, Missouri

Science.gov (United States)

Jones, Rachel A.; Williams, John W.; Jackson, Stephen T.

2017-01-01

The timing and drivers of vegetation dynamics and formation of no-analog plant communities during the last deglaciation in the unglaciated southeastern US are poorly understood. We present a multi-proxy record spanning the past 19,800 years from Cupola Pond in the Ozarks Mountains, consisting of replicate high-resolution pollen records, 25 AMS radiocarbon dates, and macrofossil, charcoal, and coprophilous spore analyses. Full-glacial Pinus and Picea forests gave way to no-analog vegetation after 17,400 yr BP, followed by development of Quercus-dominated Holocene forests, with late Holocene rises in Pinus and Nyssa. Vegetation transitions, replicated in different cores, are closely linked to hemispheric climate events. Rising Quercus abundances coincide with increasing Northern Hemisphere temperatures and CO2 at 17,500 yr BP, declining Pinus and Picea at 14,500 yr BP are near the Bølling-Allerød onset, and rapid decline of Fraxinus and rise of Ostrya/Carpinus occur 12,700 yr BP during the Younger Dryas. The Cupola no-analog vegetation record is unusual for its early initiation (17,000 yr BP) and for its three vegetation zones, representing distinct rises of Fraxinus and Ostrya/Carpinus. Sporormiella was absent and sedimentary charcoal abundances were low throughout, suggesting that fire and megaherbivores were not locally important agents of disturbance and turnover. The Cupola record thus highlights the complexity of the late-glacial no-analog communities and suggests direct climatic regulation of their formation and disassembly.

Evaluation of microorganisms cultured from injured and repressed tissue regeneration sites in endangered giant aquatic Ozark Hellbender salamanders.

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Cheryl A Nickerson

Full Text Available Investigation into the causes underlying the rapid, global amphibian decline provides critical insight into the effects of changing ecosystems. Hypothesized and confirmed links between amphibian declines, disease, and environmental changes are increasingly represented in published literature. However, there are few long-term amphibian studies that include data on population size, abnormality/injury rates, disease, and habitat variables to adequately assess changes through time. We cultured and identified microorganisms isolated from abnormal/injured and repressed tissue regeneration sites of the endangered Ozark Hellbender, Cryptobranchus alleganiensis bishopi, to discover potential causative agents responsible for their significant decline in health and population. This organism and our study site were chosen because the population and habitat of C. a. bishopi have been intensively studied from 1969-2009, and the abnormality/injury rate and apparent lack of regeneration were established. Although many bacterial and fungal isolates recovered were common environmental organisms, several opportunistic pathogens were identified in association with only the injured tissues of C.a. bishopi. Bacterial isolates included Aeromonas hydrophila, a known amphibian pathogen, Granulicetella adiacens, Gordonai terrae, Stenotrophomonas maltophilia, Aerococcus viridans, Streptococcus pneumoniae and a variety of Pseudomonads, including Pseudomonas aeruginosa, P. stutzeri, and P. alcaligenes. Fungal isolates included species in the genera Penicillium, Acremonium, Cladosporium, Curvularia, Fusarium, Streptomycetes, and the Class Hyphomycetes. Many of the opportunistic pathogens identified are known to form biofilms. Lack of isolation of the same organism from all wounds suggests that the etiological agent responsible for the damage to C. a. bishopi may not be a single organism. To our knowledge, this is the first study to profile the external microbial consortia

Evaluation of the MOCAGE Chemistry Transport Model during the ICARTT/ITOP Experiment

Science.gov (United States)

Bousserez, N.; Attie, J. L.; Peuch, V. H.; Michou, M.; Pfister, G.; Edwards, D.; Emmons, L.; Arnold, S.; Heckel, A.; Richter, A.;

Emissions of biogenic volatile organic compounds and subsequent photochemical production of secondary organic aerosol in mesocosm studies of temperate and tropical plant species

Science.gov (United States)

Wyche, K. P.; Ryan, A. C.; Hewitt, C. N.; Alfarra, M. R.; McFiggans, G.; Carr, T.; Monks, P. S.; Smallbone, K. L.; Capes, G.; Hamilton, J. F.; Pugh, T. A. M.; MacKenzie, A. R.

2014-12-01

Silver birch (Betula pendula) and three Southeast Asian tropical plant species (Ficus cyathistipula, Ficus benjamina and Caryota millis) from the pantropical fig and palm genera were grown in a purpose-built and environment-controlled whole-tree chamber. The volatile organic compounds emitted from these trees were characterised and fed into a linked photochemical reaction chamber where they underwent photo-oxidation under a range of controlled conditions (relative humidity or RH ~65-89%, volatile organic compound-to-NOx or VOC / NOx ~3-9 and NOx ~2 ppbV). Both the gas phase and the aerosol phase of the reaction chamber were monitored in detail using a comprehensive suite of on-line and off-line chemical and physical measurement techniques. Silver birch was found to be a high monoterpene and sesquiterpene but low isoprene emitter, and its emissions were observed to produce measurable amounts of secondary organic aerosol (SOA) via both nucleation and condensation onto pre-existing seed aerosol (YSOA 26-39%). In contrast, all three tropical species were found to be high isoprene emitters with trace emissions of monoterpenes and sesquiterpenes. In tropical plant experiments without seed aerosol there was no measurable SOA nucleation, but aerosol mass was shown to increase when seed aerosol was present. Although principally isoprene emitting, the aerosol mass produced from tropical fig was mostly consistent (i.e. in 78 out of 120 aerosol mass calculations using plausible parameter sets of various precursor specific yields) with condensation of photo-oxidation products of the minor volatile organic compounds (VOCs) co-emitted; no significant aerosol yield from condensation of isoprene oxidation products was required in the interpretations of the experimental results. This finding is in line with previous reports of organic aerosol loadings consistent with production from minor biogenic VOCs co-emitted with isoprene in principally isoprene-emitting landscapes in Southeast

In Situ Dark Adaptation Enhances the Efficiency of DNA Extraction from Mature Pin Oak (Quercus palustris Leaves, Facilitating the Identification of Partial Sequences of the 18S rRNA and Isoprene Synthase (IspS Genes

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Csengele E. Barta

2017-10-01

Full Text Available Mature oak (Quercus spp. leaves, although abundantly available during the plants’ developmental cycle, are rarely exploited as viable sources of genomic DNA. These leaves are rich in metabolites difficult to remove during standard DNA purification, interfering with downstream molecular genetics applications. The current work assessed whether in situ dark adaptation, to deplete sugar reserves and inhibit secondary metabolite synthesis could compensate for the difficulties encountered when isolating DNA from mature leaves rich in secondary metabolites. We optimized a rapid, commercial kit based method to extract genomic DNA from dark- and light-adapted leaves. We demonstrated that in situ dark adaptation increases the yield and quality of genomic DNA obtained from mature oak leaves, yielding templates of sufficiently high quality for direct downstream applications, such as PCR amplification and gene identification. The quality of templates isolated from dark-adapted pin oak leaves particularly improved the amplification of larger fragments in our experiments. From DNA extracts prepared with our optimized method, we identified for the first time partial segments of the genes encoding 18S rRNA and isoprene synthase (IspS from pin oak (Quercus palustris, whose full genome has not yet been sequenced.

Two new species of freshwater crayfish of the genus Faxonius (Decapoda: Cambaridae) from the Ozark Highlands of Arkansas and Missouri.

Science.gov (United States)

Fetzner, James W Jr; Taylor, Christopher A

2018-03-22

Two new species of freshwater crayfish are described from the Ozarks Plateau of northern Arkansas and southern Missouri. Both species are restricted to the mainstem of rocky streams that are at least fourth-order or greater in size. Recent genetic and morphological investigations of the coldwater crayfish, Faxonius eupunctus Williams, 1952, indicated that it was actually composed of several undescribed species. Faxonius eupunctus is herein restricted to just the Eleven Point River system. Faxonius roberti, new species is found in the mainstem of the Spring and Strawberry river systems in northern Arkansas. It differs from F. eupunctus by lacking a male Form-I gonopod with a distal spatulate mesial process, and presence of two spines on the dorsal side of the merus, where F. eupunctus typically has 1 spine. Faxonius wagneri, new species is known from a 54 mile (86 km) stretch of the Eleven Point River mainstem, ranging from just southeast of Greer, Missouri to just north of Birdell, Arkansas. Faxonius wagneri can be differentiated from both F. eupunctus and Faxonius roberti sp. nov. by using the male Form-I and Form-II gonopods, the shape of the chelae, and the female annulus ventralis. In F. wagneri, the terminal elements of the first pleopod are almost twice as long as those in F. eupunctus and F. roberti, with the tips of the appendage reaching the posterior base of the first perieopod when the abdomen is flexed forward, whereas, in the other two species, these elements only reach the base of the second pereiopod. The species also possesses two spines on the dorsal side of the merus of the first pereiopod, which helps distinguish it from F. eupunctus.

Aquatic conditions

Science.gov (United States)

Warren E. Heilman

1999-01-01

This publication provides citizens, private and public organizations, scientists, and others with information about the aquatic conditions in or near national forests in the Ozark-Ouachita Highlands: the Mark Twain in Missouri, the Ouachita in Arkansas and Oklahoma, and the Ozark-St. Francis National Forests in Arkansas. This report includes water quality analyses...

Protein farnesyltransferase isoprenoid substrate discrimination is dependent on isoprene double bonds and branched methyl groups.

Science.gov (United States)

Micali, E; Chehade, K A; Isaacs, R J; Andres, D A; Spielmann, H P

2001-10-16

Farnesylation is a posttranslational lipid modification in which a 15-carbon farnesyl isoprenoid is linked via a thioether bond to specific cysteine residues of proteins in a reaction catalyzed by protein farnesyltransferase (FTase). We synthesized the benzyloxyisoprenyl pyrophosphate (BnPP) series of transferable farnesyl pyrophosphate (FPP) analogues (1a-e) to test the length dependence of the isoprenoid substrate on the FTase-catalyzed transfer of lipid to protein substrate. Kinetic analyses show that pyrophosphates 1a-e and geranyl pyrophosphate (GPP) transfer with a lower efficiency than FPP whereas geranylgeranyl pyrophosphate (GGPP) does not transfer at all. While a correlation was found between K(m) and analogue hydrophobicity and length, there was no correlation between k(cat) and these properties. Potential binding geometries of FPP, GPP, GGPP, and analogues 1a-e were examined by modeling the molecules into the active site of the FTase crystal structure. We found that analogue 1d displaces approximately the same volume of the active site as does FPP, whereas GPP and analogues 1a-c occupy lesser volumes and 1e occupies a slightly larger volume. Modeling also indicated that GGPP adopts a different conformation than the farnesyl chain of FPP, partially occluding the space occupied by the Ca(1)a(2)X peptide in the ternary X-ray crystal structure. Within the confines of the FTase pocket, the double bonds and branched methyl groups of the geranylgeranyl chain significantly restrict the number of possible conformations relative to the more flexible lipid chain of analogues 1a-e. The modeling results also provide a molecular explanation for the observation that an aromatic ring is a good isostere for the terminal isoprene of FPP.

Comparison of OH concentration measurements by DOAS and LIF during SAPHIR chamber experiments at high OH reactivity and low NO concentration

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H. Fuchs

2012-07-01

Full Text Available During recent field campaigns, hydroxyl radical (OH concentrations that were measured by laser-induced fluorescence (LIF were up to a factor of ten larger than predicted by current chemical models for conditions of high OH reactivity and low NO concentration. These discrepancies, which were observed in forests and urban-influenced rural environments, are so far not entirely understood. In summer 2011, a series of experiments was carried out in the atmosphere simulation chamber SAPHIR in Jülich, Germany, in order to investigate the photochemical degradation of isoprene, methyl-vinyl ketone (MVK, methacrolein (MACR and aromatic compounds by OH. Conditions were similar to those experienced during the PRIDE-PRD2006 campaign in the Pearl River Delta (PRD, China, in 2006, where a large difference between OH measurements and model predictions was found. During experiments in SAPHIR, OH was simultaneously detected by two independent instruments: LIF and differential optical absorption spectroscopy (DOAS. Because DOAS is an inherently calibration-free technique, DOAS measurements are regarded as a reference standard. The comparison of the two techniques was used to investigate potential artifacts in the LIF measurements for PRD-like conditions of OH reactivities of 10 to 30 s⁻¹ and NO mixing ratios of 0.1 to 0.3 ppbv. The analysis of twenty experiment days shows good agreement. The linear regression of the combined data set (averaged to the DOAS time resolution, 2495 data points yields a slope of 1.02 ± 0.01 with an intercept of (0.10 ± 0.03 × 10⁶ cm⁻³ and a linear correlation coefficient of R² = 0.86. This indicates that the sensitivity of the LIF instrument is well-defined by its calibration procedure. No hints for artifacts are observed for isoprene, MACR, and different aromatic compounds. LIF measurements were approximately 30–40% (median larger than those by DOAS after MVK (20 ppbv and

Photochemistry of biogenic emissions over the Amazon forest

Science.gov (United States)

Jacob, Daniel J.; Wofsy, Steven C.

1988-01-01

The boundary layer chemistry over the Amazon forest during the dry season is simulated with a photochemical model. Results are in good agreement with measurements of isoprene, NO, ozone, and organic acids. Photochemical reactions of biogenic isoprene and NOx can supply most of the ozone observed in the boundary layer. Production of ozone is very sensitive to the availability of NOx, but is insensitive to the isoprene source strength. High concentrations of total odd nitrogen (NOy) are predicted for the planetary boundary layer, about 1 ppb in the mixed layer and 0.75 ppb in the convective cloud layer. Most of the odd nitrogen is present as PAN-type species, which are removed by dry deposition to the forest. The observed daytime variations of isoprene are explained by a strong dependence of the isoprene emission flux on sun angle. Nighttime losses of isoprene exceed rates of reaction with NO3 and O3 and appear to reflect dry-deposition processes. The 24-hour averaged isoprene emission flux is calculated to be 38 mg/sq m per day. Photooxidation of isoprene could account for a large fraction of the CO enrichment observed in the boundary layer under unpolluted conditions and could constitute an important atmospheric source of formic acid, methacrylic acid, and pyruvic acid.

Fast and robust method for the determination of microstructure and composition in butadiene, styrene-butadiene, and isoprene rubber by near-infrared spectroscopy.

Science.gov (United States)

Vilmin, Franck; Dussap, Claude; Coste, Nathalie

2006-06-01

In the tire industry, synthetic styrene-butadiene rubber (SBR), butadiene rubber (BR), and isoprene rubber (IR) elastomers are essential for conferring to the product its properties of grip and rolling resistance. Their physical properties depend on their chemical composition, i. e., their microstructure and styrene content, which must be accurately controlled. This paper describes a fast, robust, and highly reproducible near-infrared analytical method for the quantitative determination of the microstructure and styrene content. The quantitative models are calculated with the help of pure spectral profiles estimated from a partial least squares (PLS) regression, using (13)C nuclear magnetic resonance (NMR) as the reference method. This versatile approach allows the models to be applied over a large range of compositions, from a single BR to an SBR-IR blend. The resulting quantitative predictions are independent of the sample path length. As a consequence, the sample preparation is solvent free and simplified with a very fast (five minutes) hot filming step of a bulk polymer piece. No precise thickness control is required. Thus, the operator effect becomes negligible and the method is easily transferable. The root mean square error of prediction, depending on the rubber composition, is between 0.7% and 1.3%. The reproducibility standard error is less than 0.2% in every case.

Isoprenoids emission in Stipa tenacissima L.: Photosynthetic control and the effect of UV light

International Nuclear Information System (INIS)

Guidolotti, Gabriele; Rey, Ana; Medori, Mauro; Calfapietra, Carlo

2016-01-01

Fluxes of CO_2 and isoprenoids were measured for the first time in Stipa tenacissima L (alfa grass), a perennial tussock grass dominant in the driest areas of Europe. In addition, we studied how those fluxes were influenced by environmental conditions, leaf ontogeny and UV radiation and compared emission rates in two contrasting seasons: summer when plants are mostly inactive and autumn, the growing season in this region. Leaf ontogeny significantly affected both photosynthesis and isoprenoids emission. Isoprene emission was positively correlated with photosynthesis, although a low isoprene emission was detected in brown leaves with a net carbon loss. Moreover, leaves with a significant lower photosynthesis emitted only monoterpenes, while at higher photosynthetic rates also isoprene was produced. Ambient UV radiation uncoupled photosynthesis and isoprene emission. It is speculated that alfa grass represent an exception from the general rules governing plant isoprenoid emitters. - Highlights: • Stipa tenacissima L. is a grass emitting either monoterpenes and isoprene. • The emission has reasonable rates even in senescent leaves. • Isoprene emission is positively correlated with CO_2 assimilation. • Ambient UV radiation uncouples photosynthesis and isoprene emission. • Leaves with lower photosynthetic rates emit only monoterpenes. - We proved for the first time that alfa grass emit both isoprene and monoterpene, and we provide some innovative aspects about the UV effect and the behavior of Stipa tenacissima.

Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications.

Science.gov (United States)

Jokinen, Tuija; Berndt, Torsten; Makkonen, Risto; Kerminen, Veli-Matti; Junninen, Heikki; Paasonen, Pauli; Stratmann, Frank; Herrmann, Hartmut; Guenther, Alex B; Worsnop, Douglas R; Kulmala, Markku; Ehn, Mikael; Sipilä, Mikko

2015-06-09

Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O3 and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget.

Field observations of volatile organic compound (VOC) exchange in red oaks

Science.gov (United States)

Cappellin, Luca; Algarra Alarcon, Alberto; Herdlinger-Blatt, Irina; Sanchez, Juaquin; Biasioli, Franco; Martin, Scot T.; Loreto, Francesco; McKinney, Karena A.

2017-03-01

Volatile organic compounds (VOCs) emitted by forests strongly affect the chemical composition of the atmosphere. While the emission of isoprenoids has been largely characterized, forests also exchange many oxygenated VOCs (oVOCs), including methanol, acetone, methyl ethyl ketone (MEK), and acetaldehyde, which are less well understood. We monitored total branch-level exchange of VOCs of a strong isoprene emitter (Quercus rubra L.) in a mixed forest in New England, where canopy-level fluxes of VOCs had been previously measured. We report daily exchange of several oVOCs and investigated unknown sources and sinks, finding several novel insights. In particular, we found that emission of MEK is linked to uptake of methyl vinyl ketone (MVK), a product of isoprene oxidation. The link was confirmed by corollary experiments proving in vivo detoxification of MVK, which is harmful to plants. Comparison of MEK, MVK, and isoprene fluxes provided an indirect indication of within-plant isoprene oxidation. Furthermore, besides confirming bidirectional exchange of acetaldehyde, we also report for the first time direct evidence of benzaldehyde bidirectional exchange in forest plants. Net emission or deposition of benzaldehyde was found in different periods of measurements, indicating an unknown foliar sink that may influence atmospheric concentrations. Other VOCs, including methanol, acetone, and monoterpenes, showed clear daily emission trends but no deposition. Measured VOC emission and deposition rates were generally consistent with their ecosystem-scale flux measurements at a nearby site.

Variability of BVOC emissions from a Mediterranean mixed forest in southern France with a focus on Quercus pubescens

Science.gov (United States)

Genard-Zielinski, A.-C.; Boissard, C.; Fernandez, C.; Kalogridis, C.; Lathière, J.; Gros, V.; Bonnaire, N.; Ormeño, E.

2015-01-01

We aimed at quantifying biogenic volatile organic compound (BVOC) emissions in June from three Mediterranean species located at the O3HP site (southern France): Quercus pubescens, Acer monspessulanum and C. coggygria (for isoprene only). As Q. pubescens was shown to be the main BVOC emitter with isoprene representing ≈ 99% of the carbon emitted as BVOC, we mainly focused on this species. C. coggygria was found to be a non-isoprene emitter (no other BVOCs were investigated). To fully understand both the canopy effect on Q. pubescens isoprene emissions and the inter-individual variability (tree to tree and within canopy), diurnal variations of isoprene were investigated from nine branches (seven branches located to the top of canopy at ≈ 4 m above ground level (a.g.l.), and two inside the canopy at ≈ 2 m a.g.l.). The Q. pubescens daily mean isoprene emission rate (ERd) fluctuated between 23 and 98 μgC gDM-1 h-1. Q. pubescens daily mean net assimilation (Pn) ranged between 5.4 and 13.8, and 2.8 and 6.4 μmol CO2 m-2 s-1 for sunlit and shaded branches respectively. Both ERd and isoprene emission factors (Is), assessed according to Guenther et al. (1993) algorithm, varied by a factor of 4.3 among the sunlit branches. While sunlit branches ERd was clearly higher than for shaded branches, there was a non-significant variability of Is (59 to 77 μgC gDM-1 h-1). Diurnal variations of isoprene emission rates (ERs) for sunlit branches were also investigated. ERs were detected at dawn 2 h after Pn became positive and were mostly exponentially dependent on Pn. Diurnal variations of ERs were not equally well described throughout the day by temperature (CT) and light (CL) parameters according to G93 algorithm. Temperature had more impact than photosynthetically active radiation (PAR) on the morning emissions increase, and ER was no longer correlated to CL × CT between solar noon (maximum ER) and mid-afternoon, possibly due to thermal stress of the plant. A comparison

Non-methane biogenic volatile organic compound emissions from boreal peatland microcosms under warming and water table drawdown

DEFF Research Database (Denmark)

Faubert, P; Tiiva, P; Nakam, TA

2011-01-01

assessed the combined effect of warming and water table drawdown on the BVOC emissions from boreal peatland microcosms. We also assessed the treatment effects on the BVOC emissions from the peat soil after the 7-week long experiment. Emissions of isoprene, monoterpenes, sesquiterpenes, other reactive VOCs...

Biogenic emissions of volatile organic compounds from gorse (Ulex europaeus): Diurnal emission fluxes at Kelling Heath, England

Science.gov (United States)

Cao, X.-L.; Boissard, C.; Juan, A. J.; Hewitt, C. N.; Gallagher, M.

1997-08-01

Volatile organic compound (VOC) emission fluxes from Gorse (Ulex europaeus) were measured during May 30-31, 1995 at Kelling Heath in eastern England by using bag enclosure and gradient methods simultaneously. The enclosure measurements were made from branches at different stages of physiological development (flowering, after flowering, and mixed). Isoprene was found to represent 90% of the total VOC emissions, and its emission rates fluctuated from 6 ng (g dwt)-1 h-1 in the early morning to about 9700 ng(g dwt)-1 h-1 at midday. Averaged emission rates standardized to 20°C were 1625, 2120, and 3700 ng (g dwt)-1 h-1 for the new grown, "mixed," and flowering branch, respectively. Trans-ocimene and α-pinene were the main monoterpenes emitted and represented, on average, 47.6% and 36.9% of the total monoterpenes. Other monoterpenes, camphene, sabinene, β-pinene, myrcene, limonene and γ-terpinene, were positively identified but together represented less than 1.5% of the total VOC emissions from gorse. Maximum isoprene concentrations in air at the site were measured around midday at 2 m (174 parts per trillion by volume, or pptv) and 6 m (149 pptv), and minimum concentrations were measured during the night (8 pptv at both heights). Mean daytime α-pinene air concentrations of 141 and 60 pptv at 2 and 6 m height were determined, but trans-ocimene concentrations were less than the analytical detection limit (4 pptv), suggesting rapid chemical removal of this compound from air. The isoprene fluxes calculated by the micrometeorological gradient method showed a pattern similar to that of those calculated by the enclosure method, with isoprene emission rates maximum at midday (100 μg m-2 h-1) and not detectable during the nighttime. Assessment of the fraction of the site covered by gorse plants enabled an extrapolation of emission fluxes from the enclosure measurements. When averaged over the 2 day experiment, isoprene fluxes of 29.8 and 27.8 μg m-2 h-1 were obtained from

Síntese de copolímeros em bloco de p-acetoxiestireno com isopreno através de polimerização "viva" via radical livre Synthesis of block copolymers from p-acetoxystyrene and isoprene by "living" free radical polymerization

Directory of Open Access Journals (Sweden)

José Carlos Moreira

2004-09-01

Full Text Available Neste trabalho, é mostrada a síntese de homopolímeros de p-acetoxiestireno e copolímeros diblocos de p-acetoxiestireno com isopreno, utilizando um iniciador TEMPO-modificado, por um processo de polimerização "viva" via radical livre. As análises de GPC indicaram a formação de copolímeros em bloco com massas molares e polidispersão mais altas quando comparadas aos dos homopolímeros correspondentes. Os copolímeros em bloco poli(p-acetoxiestireno-b-isopreno foram preparados com controle de composição e massa molar até 94500 u.m.a. As análises de DSC mostraram que a transição vítrea do bloco de p-acetoxiestireno foi de 5 a 18 °C mais baixa que aquelas obtidas para os homopolímeros correspondentes. A transição vítrea do bloco de isopreno apresentou valores similares àqueles dos homopolímeros de poliisopreno (-67 a -55 °C.In this work we show the synthesis of homopolymers and diblock copolymers of p-acetoxystyrene and isoprene by using TEMPO-modified free radical initiator. The GPC analyses have shown an increase in the molar masses and in the polydispersity of the copolymers in comparison with their corresponding homopolymer. Poly(p-acetoxystyrene-b-isoprene were prepared with good control of composition and molar mass up to 94,500 a.m.u. DSC analyses have shown a glass transition temperature decrease of 5-18 °C for the poly(p-acetoxystyrene segment in copolymers compared to that observed for the parent homopolymer. The glass transition temperature of polyisoprene segment in copolymers remained similar to those observed for the homopolymers (-67 to -55 °C.

The biogenic volatile organic compounds emission inventory in France: application to plant ecosystems in the Berre-Marseilles area (France).

Science.gov (United States)

Simon, Valérie; Dumergues, Laurent; Ponche, Jean-Luc; Torres, Liberto

2006-12-15

An inventory describing the fluxes of volatile organic compounds (VOCs), isoprene and monoterpenes, and other VOCs (OVOCs) from the biosphere to the atmosphere, has been constructed within the framework of the ESCOMPTE project (fiEld experimentS to COnstrain Models of atmospheric Pollution and Transport of Emissions). The area concerned, located around Berre-Marseilles, is a Mediterranean region frequently subject to high ozone concentrations. The inventory has been developed using a fine scale land use database for the year 1999, forest composition statistics, emission potentials from individual plant species, biomass distribution, temperature and light intensity. The seasonal variations in emission potentials and biomass were also taken into account. Hourly meteorological data for 1999 were calculated from ALADIN data and these were used to predict the hourly isoprene, monoterpene and OVOC fluxes for the area on a 1 kmx1 km spatial grid. Estimates of annual biogenic isoprene, monoterpene and OVOC fluxes for the reference year 1999 were 20.6, 38.9 and 13.3 kt, respectively, Quercus pubescens, Quercus ilex, Pinus halepensis and garrigue vegetation are the dominant emitting species of the area. VOC emissions from vegetation in this region contribute approximately 94% to the NMVOC (non-methane volatile organic compounds) of natural origin and are of the same order of magnitude as NMVOC emissions from anthropogenic sources. These results complete the global ESCOMPTE database needed to make an efficient strategy for tropospheric ozone reduction policy.

Photodissociation of van der Waals clusters of isoprene with oxygen, C{sub 5}H{sub 8}-O{sub 2}, in the wavelength range 213-277 nm

Energy Technology Data Exchange (ETDEWEB)

Vidma, Konstantin V.; Frederix, Pim W. J. M.; Parker, David H. [Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 ED Nijmegen (Netherlands); Baklanov, Alexey V. [Institute of Chemical Kinetics and Combustion, Institutskaja Street 3, Novosibirsk 630090 (Russian Federation) and Novosibirsk State University, Pirogova street 2, Novosibirsk 630090 (Russian Federation)

2012-08-07

The speed and angular distribution of O atoms arising from the photofragmentation of C{sub 5}H{sub 8}-O{sub 2}, the isoprene-oxygen van der Waals complex, in the wavelength region of 213-277 nm has been studied with the use of a two-color dissociation-probe method and the velocity map imaging technique. Dramatic enhancement in the O atoms photo-generation cross section in comparison with the photodissociation of individual O{sub 2} molecules has been observed. Velocity map images of these 'enhanced' O atoms consisted of five channels, different in their kinetic energy, angular distribution, and wavelength dependence. Three channels are deduced to be due to the one-quantum excitation of the C{sub 5}H{sub 8}-O{sub 2} complex into the perturbed Herzberg III state ({sup 3}{Delta}{sub u}) of O{sub 2}. This excitation results in the prompt dissociation of the complex giving rise to products C{sub 5}H{sub 8}+O+O when the energy of exciting quantum is higher than the complex photodissociation threshold, which is found to be 41740 {+-} 200 cm{sup -1} (239.6{+-}1.2 nm). This last threshold corresponds to the photodissociation giving rise to an unexcited isoprene molecule. The second channel, with threshold shifted to the blue by 1480 {+-} 280 cm{sup -1}, corresponds to dissociation with formation of rovibrationally excited isoprene. A third channel was observed at wavelengths up to 243 nm with excitation below the upper photodissociation threshold. This channel is attributed to dissociation with the formation of a bound O atom C{sub 5}H{sub 8}-O{sub 2}+hv{yields} C{sub 5}H{sub 8}-O{sub 2}({sup 3}{Delta}{sub u}) {yields} C{sub 5}H{sub 8}O + O and/or to dissociation of O{sub 2} with borrowing of the lacking energy from incompletely cooled complex internal degrees of freedom C{sub 5}H{sub 8}{sup *}-O{sub 2}+hv{yields} C{sub 5}H{sub 8}{sup *}-O{sub 2}({sup 3}{Delta}{sub u}) {yields} C{sub 5}H{sub 8}+ O + O. The kinetic energy of the O atoms arising in two other

A highly spatially resolved GIS-based model to assess the isoprenoid emissions from key Italian ecosystems

Science.gov (United States)

Pacheco, Claudia Kemper; Fares, Silvano; Ciccioli, Paolo

2014-10-01

The amount of Biogenic Volatile Organic Compounds (BVOC) emitted from terrestrial vegetation is of great importance in atmospheric reactivity, particularly for ozone-forming reactions and as condensation nuclei in aerosol formation and growth. This work presents a detailed inventory of isoprenoid emissions from vegetation in Italy using an original approach which combines state of the art models to estimate the species-specific isoprenoid emissions and a Geographic Information System (GIS) where emissions are spatially represented. Isoprenoid species and basal emission factors were obtained by combining results from laboratory experiments with those published in literature. For the first time, our investigation was not only restricted to isoprene and total monoterpenes, but our goal was to provide maps of isoprene and individual monoterpenes at a high-spatial (∼1 km2) and temporal resolution (daily runs, monthly trends in emissions are discussed in the text). Another novelty in our research was the inclusion of the effects of phenology on plant emissions. Our results show that: a) isoprene, a-pinene, sabinene and b-pinene are the most important compounds emitted from vegetation in Italy; b) annual biogenic isoprene and monoterpene fluxes for the year 2006 were ∼31.30 Gg and ∼37.70 Gg, respectively; and c) Quercus pubescens + Quercus petrea + Quercus robur, Quercus ilex, Quercus suber and Fagus sylvatica are the principal isoprenoid emitting species in the country. The high spatial and temporal resolution, combined with the species-specific emission output, makes the model particularly suitable for assessing local budgets, and for modeling photochemical pollution in Italy.

Intercomparison of OH and OH reactivity measurements in a high isoprene and low NO environment during the Southern Oxidant and Aerosol Study (SOAS)

Science.gov (United States)

Sanchez, Dianne; Jeong, Daun; Seco, Roger; Wrangham, Ian; Park, Jeong-Hoo; Brune, William H.; Koss, Abigail; Gilman, Jessica; de Gouw, Joost; Misztal, Pawel; Goldstein, Allen; Baumann, Karsten; Wennberg, Paul O.; Keutsch, Frank N.; Guenther, Alex; Kim, Saewung

2018-02-01

We intercompare OH and OH reactivity datasets from two different techniques, chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF) in a high isoprene and low NO environment in a southeastern US forest during the Southern Oxidant and Aerosol Study (SOAS). An LIF instrument measured OH and OH reactivity at the top of a tower, a CIMS instrument measured OH at the top of the tower, and a CIMS based comparative reactivity method (CRM-CIMS) instrument deployed at the base of the tower measured OH reactivity. Averaged diel variations of OH and OH reactivity from these datasets agree within analytical uncertainty and correlations of LIF versus CIMS for OH and OH reactivity have slopes of 0.65 and 0.97, respectively. However, there are systematic differences between the measurement datasets. The CRM-CIMS measurements of OH reactivity were ∼16% lower than those by the LIF technique in the late afternoon. We speculate that it is caused by losses in the sampling line down to the CRM-CIMS instrument. On the other hand, we could not come up with a reasonable explanation for the difference in the LIF and CIMS OH datasets for early morning and late afternoon when OH is below 1 × 106 molecules cm-3. Nonetheless, results of this intercomparison exercise strengthen previous publications from the field site on OH concentrations and atmospheric reactivity.

The continental source of glyoxal estimated by the synergistic use of spaceborne measurements and inverse modelling

Directory of Open Access Journals (Sweden)

A. Richter

2009-11-01

Full Text Available Tropospheric glyoxal and formaldehyde columns retrieved from the SCIAMACHY satellite instrument in 2005 are used with the IMAGESv2 global chemistry-transport model and its adjoint in a two-compound inversion scheme designed to estimate the continental source of glyoxal. The formaldehyde observations provide an important constraint on the production of glyoxal from isoprene in the model, since the degradation of isoprene constitutes an important source of both glyoxal and formaldehyde. Current modelling studies underestimate largely the observed glyoxal satellite columns, pointing to the existence of an additional land glyoxal source of biogenic origin. We include an extra glyoxal source in the model and we explore its possible distribution and magnitude through two inversion experiments. In the first case, the additional source is represented as a direct glyoxal emission, and in the second, as a secondary formation through the oxidation of an unspecified glyoxal precursor. Besides this extra source, the inversion scheme optimizes the primary glyoxal and formaldehyde emissions, as well as their secondary production from other identified non-methane volatile organic precursors of anthropogenic, pyrogenic and biogenic origin.

In the first inversion experiment, the additional direct source, estimated at 36 Tg/yr, represents 38% of the global continental source, whereas the contribution of isoprene is equally important (30%, the remainder being accounted for by anthropogenic (20% and pyrogenic fluxes. The inversion succeeds in reducing the underestimation of the glyoxal columns by the model, but it leads to a severe overestimation of glyoxal surface concentrations in comparison with in situ measurements. In the second scenario, the inferred total global continental glyoxal source is estimated at 108 Tg/yr, almost two times higher than the global a priori source. The extra secondary source is the largest contribution to the global glyoxal

Differential response of aspen and birch trees to heat stress under elevated carbon dioxide

Energy Technology Data Exchange (ETDEWEB)

Darbah, Joseph N.T., E-mail: darbah@ohio.ed [School of Forest Resources and Environmental Science, Michigan Technological University, Houghton, MI 49931 (United States); Department of Environmental and Plant Biology, Ohio University, 315 Porter Hall, Athens, OH 45701 (United States); Sharkey, Thomas D. [Department of Biochemistry and Molecular Biology, Michigan State University, East Lansing, MI 48824 (United States); Calfapietra, Carlo [Institute of Agro-Environmental and Forest Biology (IBAF), National Research Council (CNR), Via Salaria km 29300, 00016 Monterotondo Scalo, Roma (Italy); Karnosky, David F. [School of Forest Resources and Environmental Science, Michigan Technological University, Houghton, MI 49931 (United States)

2010-04-15

The effect of high temperature on photosynthesis of isoprene-emitting (aspen) and non-isoprene-emitting (birch) trees were measured under elevated CO{sub 2} and ambient conditions. Aspen trees tolerated heat better than birch trees and elevated CO{sub 2} protected photosynthesis of both species against moderate heat stress. Elevated CO{sub 2} increased carboxylation capacity, photosynthetic electron transport capacity, and triose phosphate use in both birch and aspen trees. High temperature (36-39 deg. C) decreased all of these parameters in birch regardless of CO{sub 2} treatment, but only photosynthetic electron transport and triose phosphate use at ambient CO{sub 2} were reduced in aspen. Among the two aspen clones tested, 271 showed higher thermotolerance than 42E possibly because of the higher isoprene-emission, especially under elevated CO{sub 2}. Our results indicate that isoprene-emitting trees may have a competitive advantage over non-isoprene emitting ones as temperatures rise, indicating that biological diversity may be affected in some ecosystems because of heat tolerance mechanisms. - We report that elevated CO{sub 2} confers increased thermotolerance on both aspen and birch trees while isoprene production in aspen confers further thermotolerance in aspen.

Differential response of aspen and birch trees to heat stress under elevated carbon dioxide

International Nuclear Information System (INIS)

Darbah, Joseph N.T.; Sharkey, Thomas D.; Calfapietra, Carlo; Karnosky, David F.

2010-01-01

The effect of high temperature on photosynthesis of isoprene-emitting (aspen) and non-isoprene-emitting (birch) trees were measured under elevated CO 2 and ambient conditions. Aspen trees tolerated heat better than birch trees and elevated CO 2 protected photosynthesis of both species against moderate heat stress. Elevated CO 2 increased carboxylation capacity, photosynthetic electron transport capacity, and triose phosphate use in both birch and aspen trees. High temperature (36-39 deg. C) decreased all of these parameters in birch regardless of CO 2 treatment, but only photosynthetic electron transport and triose phosphate use at ambient CO 2 were reduced in aspen. Among the two aspen clones tested, 271 showed higher thermotolerance than 42E possibly because of the higher isoprene-emission, especially under elevated CO 2 . Our results indicate that isoprene-emitting trees may have a competitive advantage over non-isoprene emitting ones as temperatures rise, indicating that biological diversity may be affected in some ecosystems because of heat tolerance mechanisms. - We report that elevated CO 2 confers increased thermotolerance on both aspen and birch trees while isoprene production in aspen confers further thermotolerance in aspen.

UFVA, A Combined Linear and Nonlinear Factor Analysis Program Package for Chemical Data Evaluation.

Science.gov (United States)

1980-11-01

that one cluster consists of the monoterpenes and Isoprene; the second is of the sesquiterpenes. Compound 8 (Caryophyllene) should therefore belong to...two clusters very clearly (Fig. 6). Figure 6 The very similar fragmentation pattern of Isoprene and the monoterpenes is reflected by their close...13 of another set of 13 terpene components. These are Isoprene, four monoterpenes (Myrcene, Menthol, Camphene, Umbellulone), four sesquiterpenes

Engineering Robust Yeasts for Biorefinery Applications

Energy Technology Data Exchange (ETDEWEB)

Lee, Taek Soon [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint BioEnergy Institute (JBEI); Niles, Brad [Afingen, Inc., Emeryville, CA (United States); Chow, Ruthie [Afingen, Inc., Emeryville, CA (United States); Oikawa, Ai [Afingen, Inc., Emeryville, CA (United States)

2016-06-22

Isoprene is highly-valued terpene based-chemical feedstock and can be derived from either petroleum or from fermentation of plant biomass. This project enabled more efficient isoprene fermentation using renewable resources and at yields that can compete economically with non-renewable sources. This Phase I project applied a novel synthetic biology approach, the Artificial Positive Feedback Loop (APFL) technology, to improve production yields of isoprene.

Air-Sea exchange of biogenic volatile organic compounds and the impact on aerosol particle size distributions

Science.gov (United States)

Kim, Michelle J.; Novak, Gordon A.; Zoerb, Matthew C.; Yang, Mingxi; Blomquist, Byron W.; Huebert, Barry J.; Cappa, Christopher D.; Bertram, Timothy H.

2017-04-01

We report simultaneous, underway eddy covariance measurements of the vertical flux of isoprene, total monoterpenes, and dimethyl sulfide (DMS) over the Northern Atlantic Ocean during fall. Mean isoprene and monoterpene sea-to-air vertical fluxes were significantly lower than mean DMS fluxes. While rare, intense monoterpene sea-to-air fluxes were observed, coincident with elevated monoterpene mixing ratios. A statistically significant correlation between isoprene vertical flux and short wave radiation was not observed, suggesting that photochemical processes in the surface microlayer did not enhance isoprene emissions in this study region. Calculations of secondary organic aerosol production rates (PSOA) for mean isoprene and monoterpene emission rates sampled here indicate that PSOA is on average <0.1 μg m-3 d-1. Despite modest PSOA, low particle number concentrations permit a sizable role for condensational growth of monoterpene oxidation products in altering particle size distributions and the concentration of cloud condensation nuclei during episodic monoterpene emission events from the ocean.

Biogenic nonmethane hydrocarbon emissions estimated from tethered balloon observations

Science.gov (United States)

Davis, K. J.; Lenschow, D. H.; Zimmerman, P. R.

1994-01-01

A new technique for estimating surface fluxes of trace gases, the mixed-layer gradient technique, is used to calculate isoprene and terpene emissions from forests. The technique is applied to tethered balloon measurements made over the Amazon forest and a pine-oak forest in Alabama at altitudes up to 300 m. The observations were made during the dry season Amazon Boundary Layer Experiment (ABLE 2A) and the Rural Oxidants in the Southern Environment 1990 experiment (ROSE I). Results from large eddy simulations of scalar transport in the clear convective boundary layer are used to infer fluxes from the balloon profiles. Profiles from the Amazon give a mean daytime emission of 3630 +/- 1400 micrograms isoprene sq m/h, where the uncertainty represents the standard deviation of the mean of eight flux estimates. Twenty profiles from Alabama give emissions of 4470 +/- 3300 micrograms isoprene sq m/h, 1740 +/- 1060 micrograms alpha-pinene sq m/h, and 790 +/- 560 micrograms beta-pinene sq m/h, respectively. These results are in agreement with emissions derived from chemical budgets. The emissions may be overestimated because of uncertainty about how to incorporate the effects of the canopy on the mixed-layer gradients. The large variability in these emission estimates is probably due to the relatively short sampling times of the balloon profiles, though spatially heterogeneous emissions may also play a role. Fluxes derived using this technique are representative of an upwind footprint of several kilometers and are independent of hydrocarbon oxidation rate and mean advection.

Long-term study of VOCs measured with PTR-MS at a rural site in New Hampshire with urban influences

Directory of Open Access Journals (Sweden)

R. Talbot

2009-07-01

Full Text Available A long-term, high time-resolution volatile organic compound (VOC data set from a ground site that experiences urban, rural, and marine influences in the Northeastern United States is presented. A proton-transfer-reaction mass spectrometer (PTR-MS was used to quantify 15 VOCs: a marine tracer dimethyl sulfide (DMS, a biomass burning tracer acetonitrile, biogenic compounds (monoterpenes, isoprene, oxygenated VOCs (OVOCs: methyl vinyl ketone (MVK plus methacrolein (MACR, methanol, acetone, methyl ethyl ketone (MEK, acetaldehyde, and acetic acid, and aromatic compounds (benzene, toluene, C₈ and C₉ aromatics. Time series, overall and seasonal medians, with 10th and 90th percentiles, seasonal mean diurnal profiles, and inter-annual comparisons of mean summer and winter diurnal profiles are shown. Methanol and acetone exhibit the highest overall median mixing ratios 1.44 and 1.02 ppbv, respectively. Comparing the mean diurnal profiles of less well understood compounds (e.g., MEK with better known compounds (e.g., isoprene, monoterpenes, and MVK + MACR that undergo various controls on their atmospheric mixing ratios provides insight into possible sources of the lesser known compounds. The constant diurnal value of ~0.7 for the toluene:benzene ratio in winter, may possibly indicate the influence of wood-based heating systems in this region. Methanol exhibits an initial early morning release in summer unlike any other OVOC (or isoprene and a dramatic late afternoon mixing ratio increase in spring. Although several of the OVOCs appear to have biogenic sources, differences in features observed between isoprene, methanol, acetone, acetaldehyde, and MEK suggest they are produced or emitted in unique ways.

the Underestimation of Isorene in Houston during the Texas 2013 DISCOVER-AQ Campaign

Science.gov (United States)

Choi, Y.; Diao, L.; Czader, B.; Li, X.; Estes, M. J.

2014-12-01

This study applies principal component analysis to aircraft data from the Texas 2013 DISCOVER-AQ (Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality) field campaign to characterize isoprene sources over Houston during September 2013. The biogenic isoprene signature appears in the third principal component and anthropogenic signals in the following two. Evaluations of the Community Multiscale Air Quality (CMAQ) model simulations of isoprene with airborne measurements are more accurate for suburban areas than for industrial areas. This study also compares model outputs to eight surface automated gas chromatograph (Auto-GC) measurements near the Houston ship channel industrial area during the nighttime and shows that modeled anthropogenic isoprene is underestimated by a factor of 10.60. This study employs a new simulation with a modified anthropogenic emissions inventory (constraining using the ratios of observed values versus simulated ones) that yields closer isoprene predictions at night with a reduction in the mean bias by 56.93%, implying that model-estimated isoprene emissions from the 2008 National Emission Inventory are underestimated in the city of Houston and that other climate models or chemistry and transport models using the same emissions inventory might also be underestimated in other Houston-like areas in the United States.

Polar organic marker compounds in atmospheric aerosols during the LBA-SMOCC 2002 biomass burning experiment in Rondônia, Brazil: sources and source processes, time series, diel variations and size distributions

Directory of Open Access Journals (Sweden)

M. Claeys

2010-10-01

Full Text Available Measurements of polar organic marker compounds were performed on aerosols that were collected at a pasture site in the Amazon basin (Rondônia, Brazil using a high-volume dichotomous sampler (HVDS and a Micro-Orifice Uniform Deposit Impactor (MOUDI within the framework of the 2002 LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazônia – Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate campaign. The campaign spanned the late dry season (biomass burning, a transition period, and the onset of the wet season (clean conditions. In the present study a more detailed discussion is presented compared to previous reports on the behavior of selected polar marker compounds, including levoglucosan, malic acid, isoprene secondary organic aerosol (SOA tracers and tracers for fungal spores. The tracer data are discussed taking into account new insights that recently became available into their stability and/or aerosol formation processes. During all three periods, levoglucosan was the most dominant identified organic species in the PM_2.5 size fraction of the HVDS samples. In the dry period levoglucosan reached concentrations of up to 7.5 μg m⁻³ and exhibited diel variations with a nighttime prevalence. It was closely associated with the PM mass in the size-segregated samples and was mainly present in the fine mode, except during the wet period where it peaked in the coarse mode. Isoprene SOA tracers showed an average concentration of 250 ng m⁻³ during the dry period versus 157 ng m⁻³ during the transition period and 52 ng m⁻³ during the wet period. Malic acid and the 2-methyltetrols exhibited a different size distribution pattern, which is consistent with different aerosol formation processes (i.e., gas-to-particle partitioning in the case of malic acid and heterogeneous formation from gas-phase precursors in the case of

Global Emissions of Terpenoid VOCs from Terrestrial Vegetation in the Last Millennium

Energy Technology Data Exchange (ETDEWEB)

Acosta Navarro, J. C.; Smolander, S.; Struthers, H.; Zorita, E.; Ekman, A. M.; Kaplan, J. O.; Guenther, Alex B.; Arneth, A.; Riipinen, I.

2014-06-16

We investigated the millennial variability of global BVOC emissions by using two independent numerical models: The Model of Emissions of Gases and Aerosols from Nature (MEGAN), for isoprene, monoterpene and sesquiterpene and Lund-Potsdam-Jena General Ecosystem Simulator (LPJ8 GUESS), for isoprene and monoterpenes. We found the millennial trends of global isoprene emissions to be mostly affected by land cover and atmospheric carbon dioxide changes, whereas monoterpene and sesquiterpene emission were dominated by temperature change. Isoprene emissions declined substantially in regions with large and rapid land cover change. In addition, isoprene emission sensitivity to drought proved to have signicant short term global effects. By the end of the past millennium MEGAN isoprene emissions were 634 TgC yr-1 (13% and 19% less than during during 1750-1850 and 1000- 15 1200, respectively) and LPJ-GUESS emissions were 323 TgC yr-1 (15% and 20% less than during 1750-1850 and 1000-1200, respectively). Monoterpene emissions were 89 TgC yr-1 (10% and 6% higher than during 1750-1850 and 1000-1200, respectively) in MEGAN, and 24 TgC yr-1 (2% higher and 5% 19 20 less than during 1750-1850 and 1000-1200, respectively) in LPJ-GUESS. MEGAN sesquiterpene emissions were 36 TgC yr-1 (10% and 4% higher than during1750-1850 and 1000-1200, respectively). Although both models capture similar We investigated the millennial variability of global BVOC emissions by using two independent numerical models: The Model of Emissions of Gases and Aerosols from Nature (MEGAN), for isoprene, monoterpene and sesquiterpene and Lund-Potsdam-Jena General Ecosystem Simulator (LPJ8GUESS), for isoprene and monoterpenes. We found the millennial trends ofglobal isoprene emissions to be mostly a*ected by land cover and atmospheric carbon dioxide changes, whereas monoterpene and sesquiterpene emission were dominated by temperature change. Isoprene emissions declined substantially in regions with large and rapid

Geochemistry of the Springfield Plateau aquifer of the Ozark Plateaus Province in Arkansas, Kansas, Missouri and Oklahoma, USA

Science.gov (United States)

Adamski, J.C.

2000-01-01

Geochemical data indicate that the Springfield Plateau aquifer, a carbonate aquifer of the Ozark Plateaus Province in central USA, has two distinct hydrochemical zones. Within each hydrochemical zone, water from springs is geochemically and isotopically different than water from wells. Geochemical data indicate that spring water generally interacts less with the surrounding rock and has a shorter residence time, probably as a result of flowing along discrete fractures and solution openings, than water from wells. Water type throughout most of the aquifer was calcium bicarbonate, indicating that carbonate-rock dissolution is the primary geochemical process occurring in the aquifer. Concentrations of calcium, bicarbonate, dissolved oxygen and tritium indicate that most ground water in the aquifer recharged rapidly and is relatively young (less than 40 years). In general, field-measured properties, concentrations of many chemical constituents, and calcite saturation indices were greater in samples from the northern part of the aquifer (hydrochemical zone A) than in samples from the southern part of the aquifer (hydrochemical zone B). Factors affecting differences in the geochemical composition of ground water between the two zones are difficult to identify, but could be related to differences in chert content and possibly primary porosity, solubility of the limestone, and amount and type of cementation between zone A than in zone B. In addition, specific conductance, pH, alkalinity, concentrations of many chemical constituents and calcite saturation indices were greater in samples from wells than in samples from springs in each hydrochemical zone. In contrast, concentrations of dissolved oxygen, nitrite plus nitrate, and chloride generally were greater in samples from springs than in samples from wells. Water from springs generally flows rapidly through large conduits with minimum water-rock interactions. Water from wells flow through small fractures, which restrict

Seasonal variations in VOC emission rates from gorse (Ulex europaeus)

Science.gov (United States)

Boissard, C.; Cao, X.-L.; Juan, C.-Y.; Hewitt, C. N.; Gallagher, M.

Seasonal variations of biogenic volatile organic compound (VOC) emission rates and standardised emission factors from gorse (Ulex europaeus) have been measured at two sites in the United Kingdom, from October 1994 to September 1995, within temperature and PAR conditions ranging from 3 to 34°C and 10-1300 μmol m-2 s-1, respectively. Isoprene was the dominant emitted compound with a relative composition fluctuating from 7% of the total VOC (winter) to 97% (late summer). The monoterpenes α-pinene, camphene, sabinene, β-pinene, myrcene, limonene, trans-ocimene and γ-terpinene were also emitted, with α-pinene being the dominant monoterpene during most the year. Trans-ocimene represented 33-66% of the total monoterpene during the hottest months from June to September. VOC emissions were found to be accurately predicted using existing algorithms. Standard (normalised) emission factors of VOCs from gorse were calculated using experimental parameters measured during the experiment and found to fluctuate with season, from 13.3±2.1 to 0.1±0.1 μg C (g dwt)-1 h-1 in August 1995 and January 1995, respectively, for isoprene, and from 2.5±0.2 to 0.4±0.2 μg C (g dwt)-1 h-1 in July and November 1995, respectively, for total monoterpenes. No simple clear relation was found to allow prediction of these seasonal variations with respect to temperature and light intensity. The effects of using inappropriate algorithms to derive VOC fluxes from gorse were assessed for isoprene and monoterpenes. Although on an annual basis the discrepancies are not significant, monthly estimation of isoprene were found to be overestimated by more than a factor of 50 during wintertime when the seasonality of emission factors is not considered.

Deployment of the FIGAERO Iodide Time of flight (ToF)-Chemical ionisation mass spectrometer (CIMS) using X-ray ionisation in Manaus

Science.gov (United States)

Bannan, T.; Bacak, A.; Priestley, M.; Adelstein, E.; Worrall, S.; Artaxo, P.; Carbone, S.; Topping, D. O.; Allan, J. D.; Coe, H.; Percival, C.

2017-12-01

Here the deployment of the The Filter Inlet for Gases and AEROsols (FIGAERO) coupled with the Aerodyne High Resolution (HR)-Time of flight (ToF)-Chemical ionisation mass spectrometer (CIMS) in Manaus is presented. This project utilised the Tofwerk X-ray ionisation source in the tropical rainforest in close proximity to Manaus, Brazil, at the ZF2 measurement site. The FIGAERO is a filter based technique that provides simultaneous molecular information of both the gas and particle phase. When analysing particles that have been collected the evolution of the MS signals from different compounds change independently as a function of temperature; creating a thermogram that is m/z specific. The temperature for which the desorbed signal shows a maximum for each compound has been used previously to extract vapour pressure information in laboratory characterisatio. Krieger et al. (2017) defined the homologous series of polyethylene glycols as a series of compounds that showed a very good agreement over a wide range of atmospherically relevant vapour pressures between different experimental setups. PEG samples therefore provide an ideal bench mark for characterising individual FIGAERO inlets to give vapour pressure information essential for partitioning characterisation. The PEG calibration curve has been used to validate vapour pressure measurements in a well-defined single component bases and in simple chamber experiments, results of which are presented. With a high reactivity and large ubiquitous global source, isoprene has a profound effect upon atmospheric chemistry and composition. Despite this there are still significant gaps in the understanding of the processes that lead to isoprene derived secondary organic aerosol (SOA). This project aims to provide insights into the role of isoprene in the mechanisms of production of SOA and its importance in the particulate mass budgets in the tropics and the fundamental chemical processes. The volatility and composition of

Biomass Burning and Natural Emissions in the Brazilian Amazon Rainforest: Chemical Composition and Impact on the Oxidative Capacity of the Atmosphere

Science.gov (United States)

dos Santos, F. C.; Longo, K.; Guenther, A. B.; Gu, D.; Kim, S.; Freitas, S.; Moreira, D. S.; Flávio, L.; Braz, R.; Brito, J.; Oram, D.; Foster, G.; Lee, J. D.

2017-12-01

Emitted by vegetation, isoprene (2-methyl-1,3-butadiene) is the most abundant non-methane hydrocarbons, with an annual global emission calculated ranging from 440 to 660Tg carbon, depending on the driving variables like temperature, solar radiation, LAI and PFT. The natural compounds like isoprene and terpenes present in the troposphere are about 90% and 50%, respectively, removed from the atmosphere by oxidation performed by hydroxyl radical (OH). Considering the importance of these emissions and the hydroxyl radical reaction in the atmosphere, the SAMBBA (South American Biomass Burning Analysis) experiment, which occurred during the dry season (September 2012) in the Brazilian Amazon Rainforest, provided information about the chemical composition of the atmosphere through airborne observations. Although primarily focused on biomass burning flights, the SAMBBA project carried out flights in pristine environment. In this study, we determine the ambient distribution of CO, NOx and O3, and evaluate the oxidative capacity of the Amazon rainforest in different chemical regimes, using the ratio [MVK + MACR]/[Isoprene]. Beyond that, we proposed an improvement on the formulation of indirect OH density calculation, using the photochemical aging [O3]/[CO] as a parameter. Balancing numerical modeling and direct observations, the numerical model BRAMS was coupled to MEGAN emission model to get a better result for isoprene and OH in the atmosphere, representing the observations during SAMBBA field campaign. In relation to OH estimation, we observed an improvement in the concentration values using the modified sequential reaction model, for both biomass burning regimes and background environment. We also detected a long-range transport events of O3, considering the high levels of O3 in aged plumes at high altitudes (5,500 - 6,500 m), and the detection of an O3 inflow in the Amazon basin from Africa. These findings support the importance of long-range transport events as a

Canopy-scale flux measurements and bottom-up emission estimates of volatile organic compounds from a mixed oak and hornbeam forest in northern Italy

Science.gov (United States)

Acton, W. Joe F.; Schallhart, Simon; Langford, Ben; Valach, Amy; Rantala, Pekka; Fares, Silvano; Carriero, Giulia; Tillmann, Ralf; Tomlinson, Sam J.; Dragosits, Ulrike; Gianelle, Damiano; Hewitt, C. Nicholas; Nemitz, Eiko

2016-06-01

This paper reports the fluxes and mixing ratios of biogenically emitted volatile organic compounds (BVOCs) 4 m above a mixed oak and hornbeam forest in northern Italy. Fluxes of methanol, acetaldehyde, isoprene, methyl vinyl ketone + methacrolein, methyl ethyl ketone and monoterpenes were obtained using both a proton-transfer-reaction mass spectrometer (PTR-MS) and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) together with the methods of virtual disjunct eddy covariance (using PTR-MS) and eddy covariance (using PTR-ToF-MS). Isoprene was the dominant emitted compound with a mean daytime flux of 1.9 mg m-2 h-1. Mixing ratios, recorded 4 m above the canopy, were dominated by methanol with a mean value of 6.2 ppbv over the 28-day measurement period. Comparison of isoprene fluxes calculated using the PTR-MS and PTR-ToF-MS showed very good agreement while comparison of the monoterpene fluxes suggested a slight over estimation of the flux by the PTR-MS. A basal isoprene emission rate for the forest of 1.7 mg m-2 h-1 was calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN) isoprene emission algorithms (Guenther et al., 2006). A detailed tree-species distribution map for the site enabled the leaf-level emission of isoprene and monoterpenes recorded using gas-chromatography mass spectrometry (GC-MS) to be scaled up to produce a bottom-up canopy-scale flux. This was compared with the top-down canopy-scale flux obtained by measurements. For monoterpenes, the two estimates were closely correlated and this correlation improved when the plant-species composition in the individual flux footprint was taken into account. However, the bottom-up approach significantly underestimated the isoprene flux, compared with the top-down measurements, suggesting that the leaf-level measurements were not representative of actual emission rates.

Ecoregions and stream morphology in eastern Oklahoma

Science.gov (United States)

Splinter, D.K.; Dauwalter, D.C.; Marston, R.A.; Fisher, W.L.

2010-01-01

Broad-scale variables (i.e., geology, topography, climate, land use, vegetation, and soils) influence channel morphology. How and to what extent the longitudinal pattern of channel morphology is influenced by broad-scale variables is important to fluvial geomorphologists and stream ecologists. In the last couple of decades, there has been an increase in the amount of interdisciplinary research between fluvial geomorphologists and stream ecologists. In a historical context, fluvial geomorphologists are more apt to use physiographic regions to distinguish broad-scale variables, while stream ecologists are more apt to use the concept of an ecosystem to address the broad-scale variables that influence stream habitat. For this reason, we designed a study using ecoregions, which uses physical and biological variables to understand how landscapes influence channel processes. Ecoregions are delineated by similarities in geology, climate, soils, land use, and potential natural vegetation. In the fluvial system, stream form and function are dictated by processes observed throughout the fluvial hierarchy. Recognizing that stream form and function should differ by ecoregion, a study was designed to evaluate how the characteristics of stream channels differed longitudinally among three ecoregions in eastern Oklahoma, USA: Boston Mountains, Ozark Highlands, and Ouachita Mountains. Channel morphology of 149 stream reaches was surveyed in 1st- through 4th-order streams, and effects of drainage area and ecoregion on channel morphology was evaluated using multiple regressions. Differences existed (?????0.05) among ecoregions for particle size, bankfull width, and width/depth ratio. No differences existed among ecoregions for gradient or sinuosity. Particle size was smallest in the Ozark Highlands and largest in the Ouachita Mountains. Bankfull width was larger in the Ozark Highlands than in the Boston Mountains and Ouachita Mountains in larger streams. Width/depth ratios of the

Impact of elevated CO2 and O3 concentrations on biogenic volatile organic compounds emissions from Ginkgo biloba.

Science.gov (United States)

Li, Dewen; Chen, Ying; Shi, Yi; He, Xingyuan; Chen, Xin

2009-04-01

In natural environment with ambient air, ginkgo trees emitted volatile organic compounds 0.18 microg g(-1) h(-1) in July, and 0.92 microg g(-1) h(-1) in September. Isoprene and limonene were the most abundant detected compounds. In September, alpha-pinene accounted for 22.5% of the total. Elevated CO(2) concentration in OTCs increased isoprene emission significantly in July (pemission was enhanced in July and decreased in September by elevated CO(2). Exposed to elevated O(3) increased the isoprene and monoterpenes emissions in July and September, and the total volatile organic compounds emission rates were 0.48 microg g(-1) h(-1) (in July) and 2.24 microg g(-1) h(-1) (in September), respectively. The combination of elevated CO(2) and O(3) did not have any effect on biogenic volatile organic compounds emissions, except increases of isoprene and Delta3-carene in September.

Measurements of atmospheric hydrocarbons and biogenic emission fluxes in the Amazon boundary layer

Science.gov (United States)

Zimmerman, P. R.; Greenberg, J. P.; Westberg, C. E.

1988-01-01

Tropospheric mixing ratios of methane, C2-C10 hydrocarbons, and carbon monoxide were measured over the Amazon tropical forest near Manaus, Amazonas, Brazil, in July and August 1985. The measurements, consisting mostly of altitude profiles of these gases, were all made within the atmospheric boundary layer up to an altitude of 1000 m above ground level. Data characterize the diurnal hydrocarbon composition of the boundary layer. Biogenic emissions of isoprene control hydroxyl radical concentrations over the forest. Biogenic emission fluxes of isoprene and terpenes are estimated to be 25,000 micrograms/sq m per day and 5600 micrograms/sq m per day, respectively. This isoprene emission is equivalent to 2 percent of the net primary productivity of the tropical forest. Atmospheric oxidation of biogenic isoprene and terpenes emissions from the Amazon forest may account for daily increases of 8-13 ppb for carbon monoxide in the planetary boundary layer.

Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)

Energy Technology Data Exchange (ETDEWEB)

Hu, Weiwei; Palm, Brett B.; Day, Douglas A.; Campuzano-Jost, Pedro; Krechmer, Jordan E.; Peng, Zhe; de Sá, Suzane S.; Martin, Scot T.; Alexander, M. Lizabeth; Baumann, Karsten; Hacker, Lina; Kiendler-Scharr, Astrid; Koss, Abigail R.; de Gouw, Joost A.; Goldstein, Allen H.; Seco, Roger; Sjostedt, Steven J.; Park, Jeong-Hoo; Guenther, Alex B.; Kim, Saewung; Canonaco, Francesco; Prévôt, André S. H.; Brune, William H.; Jimenez, Jose L.

2016-01-01

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ~100 µg m^-3 of pure H₂SO₄ to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (k_OH) was estimated as 4.0 ± 2.0 ×10^-13 cm³ molec^-1 s^-1, which is equivalent to more than a 2-week lifetime. A similar k_OH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 10¹² molec cm^-3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γ_OH = 0.59±0.33 in SE US and γ_OH = 0.68±0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of k_OH and γ_OH was observed, consistent with surface-area-limited OH uptake

Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA

Directory of Open Access Journals (Sweden)

W. Hu

2016-09-01

Full Text Available Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA can contribute substantially to organic aerosol (OA concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR. New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding  ∼  100 µg m−3 of pure H2SO4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (kOH was estimated as 4.0 ± 2.0  ×  10−13 cm3 molec−1 s−1, which is equivalent to more than a 2-week lifetime. A similar kOH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (>  1  ×  1012 molec cm−3 s, the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γOH =  0.59 ± 0.33 in SE US and γOH =  0.68 ± 0.38 in Amazon for SOA under ambient conditions. A relative humidity dependence of kOH and γOH was observed, consistent with surface-area-limited OH uptake. No decrease of kOH was observed as OH concentrations increased. These observations of physicochemical

The impact of large scale biomass production on ozone air pollution in Europe

NARCIS (Netherlands)

Beltman, J.B.; Hendriks, C.; Tum, M.; Schaap, M.

2013-01-01

Tropospheric ozone contributes to the removal of air pollutants from the atmosphere but is itself a pollutant that is harmful to human health and vegetation. Biogenic isoprene emissions are important ozone precursors, and therefore future changes in land use that change isoprene emissions are likely

Elemental analysis of chamber organic aerosol using an aerodyne high-resolution aerosol mass spectrometer

Directory of Open Access Journals (Sweden)

P. S. Chhabra

2010-05-01

Full Text Available The elemental composition of laboratory chamber secondary organic aerosol (SOA from glyoxal uptake, α-pinene ozonolysis, isoprene photooxidation, single-ring aromatic photooxidation, and naphthalene photooxidation is evaluated using Aerodyne high-resolution time-of-flight mass spectrometer data. SOA O/C ratios range from 1.13 for glyoxal uptake experiments to 0.30–0.43 for α-pinene ozonolysis. The elemental composition of α-pinene and naphthalene SOA is also confirmed by offline mass spectrometry. The fraction of organic signal at m/z 44 is generally a good measure of SOA oxygenation for α-pinene/O₃, isoprene/high-NO_x, and naphthalene SOA systems. The agreement between measured and estimated O/C ratios tends to get closer as the fraction of organic signal at m/z 44 increases. This is in contrast to the glyoxal uptake system, in which m/z 44 substantially underpredicts O/C. Although chamber SOA has generally been considered less oxygenated than ambient SOA, single-ring aromatic- and naphthalene-derived SOA can reach O/C ratios upward of 0.7, well within the range of ambient PMF component OOA, though still not as high as some ambient measurements. The spectra of aromatic and isoprene-high-NO_x SOA resemble that of OOA, but the spectrum of glyoxal uptake does not resemble that of any ambient organic aerosol PMF component.

Rare earth metal bis(amide) complexes bearing amidinate ancillary ligands: synthesis, characterization, and performance as catalyst precursors for cis-1,4 selective polymerization of isoprene.

Science.gov (United States)

Luo, Yunjie; Fan, Shimin; Yang, Jianping; Fang, Jianghua; Xu, Ping

2011-03-28

A family of rare earth metal bis(amide) complexes bearing monoanionic amidinate [RC(N-2,6-Me(2)C(6)H(3))(2)](-) (R = cyclohexyl (Cy), phenyl (Ph)) as ancillary ligands were synthesized and characterized. One-pot salt metathesis reaction of anhydrous LnCl(3) with one equivalent of amidinate lithium [RC(N-2,6-Me(2)C(6)H(3))(2)]Li, following the introduction of two equivalents of NaN(SiMe(3))(2) in THF at room temperature afforded the neutral and unsolvated mono(amidinate) rare earth metal bis(amide) complexes [RC(N-2,6-Me(2)C(6)H(3))(2)]Y[N(SiMe(3))(2)](2) (R = Cy (1); R = Ph (2)), and the "ate" mono(amidinate) rare earth metal bis(amide) complex [CyC(N-2,6-Me(2)C(6)H(3))(2)]Lu[N(SiMe(3))(2)](2)(μ-Cl)Li(THF)(3) (3) in 61-72% isolated yields. These complexes were characterized by elemental analysis, NMR spectroscopy, FT-IR spectroscopy, and X-ray single crystal diffraction. Single crystal structural determination revealed that the central metal in complexes 1 and 2 adopts a distorted tetrahedral geometry, and in complex 3 forms a distorted trigonal bipyramidal geometry. In the presence of AlMe(3), and in combination with one equimolar amount of [Ph(3)C][B(C(6)F(5))(4)], complexes 1 and 2 showed high activity towards isoprene polymerization to give high molecular weight polyisoprene (M(n) > 10(4)) with good cis-1,4 selectivity (>90%).

Canopy-scale flux measurements and bottom-up emission estimates of volatile organic compounds from a mixed oak and hornbeam forest in northern Italy

Directory of Open Access Journals (Sweden)

W. J. F. Acton

2016-06-01

Full Text Available This paper reports the fluxes and mixing ratios of biogenically emitted volatile organic compounds (BVOCs 4 m above a mixed oak and hornbeam forest in northern Italy. Fluxes of methanol, acetaldehyde, isoprene, methyl vinyl ketone + methacrolein, methyl ethyl ketone and monoterpenes were obtained using both a proton-transfer-reaction mass spectrometer (PTR-MS and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS together with the methods of virtual disjunct eddy covariance (using PTR-MS and eddy covariance (using PTR-ToF-MS. Isoprene was the dominant emitted compound with a mean daytime flux of 1.9 mg m−2 h−1. Mixing ratios, recorded 4 m above the canopy, were dominated by methanol with a mean value of 6.2 ppbv over the 28-day measurement period. Comparison of isoprene fluxes calculated using the PTR-MS and PTR-ToF-MS showed very good agreement while comparison of the monoterpene fluxes suggested a slight over estimation of the flux by the PTR-MS. A basal isoprene emission rate for the forest of 1.7 mg m−2 h−1 was calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN isoprene emission algorithms (Guenther et al., 2006. A detailed tree-species distribution map for the site enabled the leaf-level emission of isoprene and monoterpenes recorded using gas-chromatography mass spectrometry (GC–MS to be scaled up to produce a bottom-up canopy-scale flux. This was compared with the top-down canopy-scale flux obtained by measurements. For monoterpenes, the two estimates were closely correlated and this correlation improved when the plant-species composition in the individual flux footprint was taken into account. However, the bottom-up approach significantly underestimated the isoprene flux, compared with the top-down measurements, suggesting that the leaf-level measurements were not representative of actual emission rates.

Differential response of Aspen and Birch trees to heat stress under elevated carbon dioxide

Science.gov (United States)

Joseph N.T. Darbah; Thomas D. Sharkey; Carlo Calfapietra; David F. Karnosky

2010-01-01

The effect of high temperature on photosynthesis of isoprene-emitting (aspen) and non-isoprene-emitting (birch) trees were measured under elevated CO2 and ambient conditions. Aspen trees tolerated heat better than birch trees and elevated CO2 protected photosynthesis of both species against moderate heat stress. Elevated CO...

Synthesis of 4-tert-butyl-1,1-dimethylindan and 7-tert-Butyl-3,3-dimethyl-1-indanone and a comparison of isomers

International Nuclear Information System (INIS)

Eisenbraun, E.J.; Harms, W.M.; Paraniswamy, V.A.; Chen, H.H.; Porcaro, P.J.; Wood, T.F.; Chien, M.

1982-01-01

4-tert-Butyl-1,1-dimethylindan was synthesized to help establish the identity of products (5- and 6-tert-butyl-1,1-dimethylindan as minor and major products, respectively) from the sulfuric acid catalyzed condensation of tert-butylbenzene and isoprene. NMR ( 1 H and 13 C) studies of these hydrocarbons and their corresponding indanones, obtained through chromic acid oxidation, provided structural proof. Gated decoupling experiments were crucial to complete assignment

Biogenic volatile organic compound emissions from a lowland tropical wet forest in Costa Rica

Energy Technology Data Exchange (ETDEWEB)

Geron, C. [United States Environmental Protection Agency, Research Triangle Park, NC (United States). National Risk Management Research Lab.; Guenther, A.; Greenberg, J. [National Center for Atmospheric Research, Boulder, CO (United States); Loescher, H.W. [University of Florida, Gainesville, FL (United States). School of Forest Resources and Conservation; Clark, D. [University of Missouri-St. Louis, MS (United States). Dept. of Biology; Baker, B. [South Dakota School of Mines and Technology, Rapid City, SD (United States)

2002-08-01

Twenty common plant species were screened for emissions of biogenic volatile organic compounds (BVOCs) at a lowland tropical wet forest site in Costa Rica. Ten of the species examined emitted substantial quantities of isoprene. These species accounted for 35-50% of the total basal area of old-growth forest on the major edaphic site types, indicating that a high proportion of the canopy leaf area is a source of isoprene. A limited number of canopy-level BVOC flux measurements were also collected by relaxed eddy accumulation (REA). These measurements verify that the forest canopy in this region is indeed a significant source of isoprene. In addition, REA fluxes of methanol and especially acetone were also significant, exceeding model estimates and warranting future investigation at this site. Leaf monoterpene emissions were non-detectable or very low from the species surveyed, and ambient concentrations and REA fluxes likewise were very low. Although the isoprene emission rates reported here are largely consistent with phylogenetic relations found in other studies (at the family, genus, and species levels), two species in the family Mimosaceae, a group previously found to consist largely of non-isoprene emitters, emitted significant quantities of isoprene. One of these, Pentaclethra macroloba (Willd.) Kuntze, is by far the most abundant canopy tree species in the forests of this area, composing 30-40% of the total basal area. The other, Zygia longifolia (Humb. and Bonpl.) Britton and Rose is a common riparian species. Our results suggest that the source strength of BVOCs is important not only to tropical atmospheric chemistry, but also may be important in determining net ecosystem carbon exchange.(author)

Global emissions of terpenoid VOCs from terrestrial vegetation in the last millennium

Science.gov (United States)

Acosta Navarro, J C; Smolander, S; Struthers, H; Zorita, E; Ekman, A M L; Kaplan, J O; Guenther, A; Arneth, A; Riipinen, I

2014-01-01

We investigated the millennial variability (1000 A.D.–2000 A.D.) of global biogenic volatile organic compound (BVOC) emissions by using two independent numerical models: The Model of Emissions of Gases and Aerosols from Nature (MEGAN), for isoprene, monoterpene, and sesquiterpene, and Lund-Potsdam-Jena-General Ecosystem Simulator (LPJ-GUESS), for isoprene and monoterpenes. We found the millennial trends of global isoprene emissions to be mostly affected by land cover and atmospheric carbon dioxide changes, whereas monoterpene and sesquiterpene emission trends were dominated by temperature change. Isoprene emissions declined substantially in regions with large and rapid land cover change. In addition, isoprene emission sensitivity to drought proved to have significant short-term global effects. By the end of the past millennium MEGAN isoprene emissions were 634 TgC yr−1 (13% and 19% less than during 1750–1850 and 1000–1200, respectively), and LPJ-GUESS emissions were 323 TgC yr−1(15% and 20% less than during 1750–1850 and 1000–1200, respectively). Monoterpene emissions were 89 TgC yr−1(10% and 6% higher than during 1750–1850 and 1000–1200, respectively) in MEGAN, and 24 TgC yr−1 (2% higher and 5% less than during 1750–1850 and 1000–1200, respectively) in LPJ-GUESS. MEGAN sesquiterpene emissions were 36 TgC yr−1(10% and 4% higher than during 1750–1850 and 1000–1200, respectively). Although both models capture similar emission trends, the magnitude of the emissions are different. This highlights the importance of building better constraints on VOC emissions from terrestrial vegetation. PMID:25866703

Analysis of expiration gas in intensive care patients with SIRS/sepsis using proton-transfer-reaction-mass-spectrometry

International Nuclear Information System (INIS)

Bodrogi, F.B.M.

2003-11-01

In 1971, Pauling and co-workers were the first to detect volatile organic compounds (VOC) in human breath. Since then, a number of technical applications for breath gas analyses have been designed and processed, among them gas chromatography and proton transfer reaction-mass spectrometry (PTR-MS). Due to this technical progress it is meanwhile possible to correlate different kinds and stages of diseases with measurable changes in the patient's VOC profile. The aim of the present study was to investigate the composition of VOC in exhaled air of patients with sepsis via PTR-MS. To isolate distinct volatile organic compounds that may serve as clinical markers for the onset, the progress, as well as the outcome of the disease, the results obtained from septic patients were compared with two different control groups: 25 healthy, non-smoking volunteers enrolled in the day-case-surgery and 25 post-operative in-patients residing in post-anaesthetic care units (PACU). PTR-MS is capable to analyze VOC according to their molecular weight with a range between 21-230 Da. A total of 210 different masses has been detected in the present study. 54 masses were significantly different in exhaled air of septic patients as compared to healthy controls as well as post-operative patients. Among them, mass 69 representing isoprene might be of special interest for the diagnosis of sepsis. Although no exact biochemical properties of isoprene have been described to date, it is known that isoprene synthesis is increased in plants following exposure to oxidative stress. Chronic, systemic infectious diseases like sepsis are accompanied by the production of reactive oxygen species, indicating that isoprene might be increased in the course of sepsis, too. In the present study, isoprene values were markedly higher in septic patients as compared to PACU residents (3.3-fold increase in mean value) and to healthy volunteers (2.2-fold increase in mean value). In addition (and in contrast to other VOC

Oxidative Capacity Predicted Using Photochemical Age Approximation from SAMBBA Airborne Observations in the Amazon Rainforest

Science.gov (United States)

dos Santos, F. C.; Longo, K.; Guenther, A. B.; Freitas, S. R.; Moreira, D. S.; Flávio, L.; Braz, R.; Oram, D.; Lee, J. D.; Bauguitte, S.

2016-12-01

Emitted by vegetation, isoprene (2-methyl-1,3-butadiene) is the most abundant non-methane hydrocarbons, with an annual global emission calculated ranging from 440 to 660Tg carbon, depending on the driving variables like temperature, solar radiation, leaf area index and plant functional type. It is estimated, for example, that the natural compounds like isoprene and terpenes present in the troposphere are about 90% and 50%, respectively, removed from the atmosphere by oxidation performed by hydroxyl radical (OH). Furthermore, the oxidation products of isoprene may contribute to secondary organic aerosol (SOA) formation, affecting the climate and altering the properties and lifetimes of clouds. Considering the importance of these emissions and the hydroxyl radical reaction in the atmosphere, the SAMBBA (South American Biomass Burning Analysis) experiment, which occurred during the dry season (September 2012) in the Amazon Rainforest, provided information about the chemical composition of the atmosphere through airborne observations. Although primarily focused on biomass burning flights, the SAMBBA project carried out other flights providing indirect oxidative capacity data in different environments: natural emission dominated flights and biomass-burning flights with fresh plumes and aged plumes. In this study, we evaluate the oxidative capacity of the Amazon rainforest in different environments, both for the unpolluted and biomass-burning disturbed atmosphere using the ratio [MVK + MACR]/[Isoprene]. Beyond that, we propose an improvement on the formulation of indirect OH density calculation, using the photochemical aging [O3]/[CO] as a parameter. During the day (11am-8pm - local time), the [OH] values for natural emission flights (8.1 x 106 molecules/cm3) and biomass-burning (9.4 x 106 molecules/cm3) are comparable with GABRIEL-2015 field campaign along Guyanas tropical rainforest and suggest that biomass-burning increase the oxidative capacity around 18% in average

Differential cardiac effects in rats exposed to atmospheric ...

Science.gov (United States)

The results of this study demonstrate that atmospheric smog generated from both isoprene and toluene cause cardiac effects in rats. In addition, it appears that smog from toluene is more toxic in terms of cardiac arrhythmogenicity. Smog, which is a complex mixture of particulate matter and gaseous irritants (ozone, sulfur dioxide, reactive aldehydes), as well as components which react with sunlight to form secondary pollutants, has recently been linked to increased risk of adverse cardiac responses. The components, and therefore health effects, of atmospheric smog are determined by the fuel used to generate them. In this study we examined the difference between isoprene- and toluene-generated smog in causing cardiac effects in rats and hypothesized that both atmospheres would cause cardiac electrical and functional changes in rats. Male Wistar-Kyoto rats were exposed to either atmospheric smog generated by the USEPA’s mobile reaction chamber using either isoprene or toluene, or filtered air for four hours. One day later, rats were anesthetized and left ventricular functional responses to dobutamine were measured using a Millar probe and arrhythmia sensitivity to aconitine. Baseline left ventricular pressure (LVP) was lower in toluene-exposed animals but not isoprene when compared to air. Increases in LVP with increasing doses of dobutamine were impaired only in toluene-exposed rats. Both isoprene and toluene impaired the rate of ventri

Processes Controlling CH2O Over the Baltimore/Washington DC Metropolitan Region: A Box Model Analysis Using Data from DISCOVER-AQ

Science.gov (United States)

Olson, J. R.; Crawford, J. H.; Fried, A.; Wisthaler, A.; Weinheimer, A. J.; Barrick, J. D.; Diskin, G. S.; Duncan, B. N.; Mikoviny, T.

2012-12-01

The first deployment for NASA's Earth Venture campaign DISCOVER-AQ (Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality) took place over the Baltimore/Washington DC region during July of 2011. Observations of CH2O in the lowest kilometer (pressure-altitude) indicate that median concentrations can vary day to day by as much as 5 ppbv. Further, variability within a single day can correlate with a number of species, including H2O, temperature, isoprene, and/or CO. The NASA Langley photochemical box model is used to examine the dominant budget terms for CH2O during DISCOVER-AQ and to diagnose the drivers of the CH2O variability. Modeling results show that the source of CH2O is largely dominated by isoprene. However, the variability of CH2O within single flight days is rarely directly correlated to isoprene. Rather, most often, CH2O variability is correlated to the oxidative capacity of the atmosphere, defined by OH and driven by OH precursors such as H2O, O3 photolysis rates, and NO. Sensitivity model runs where isoprene is held constant to daily medians show excellent ability to predict both the overall CH2O concentration (dominated by isoprene) and the variability of CH2O throughout a day (driven by variations in oxidative capacity).

Biochemical, physiological and climatic influence on the emission of isoprenoides from Grey Poplar (Populus x canescens (Aiton) Sm.) and Holm Oak (Quercus ilex L.); Biochemische, physiologische und klimatische Einfluesse auf die Isoprenoidemission der Graupappel (Populus x canescens (Aiton) Sm.) und der Steineiche (Quercus ilex L.)

Energy Technology Data Exchange (ETDEWEB)

Mayrhofer, S.

2007-05-15

Because of their important role for the atmospheric chemistry, global daily and seasonal emission rates of isoprene and monoterpenes have to be estimated with accuracy. Therefore, detailed knowledge of biochemical and physiological processes within the plant metabolism has to be gathered. Afterwards the gained cognitions are used as information for process-based model calculations. The major scope of the work was therefore to enlarge basic knowledge of the regulation of isoprenoid emission, which is known to be dependent on several environmental factors, especially light and temperature. Measurements of diurnal isoprene emission have been performed in parallel on physiological, translational and transcriptional level on leaves of Grey Poplar (Populus x canescens), a strong isoprene emitting species. Additionally, examinations of diurnal monoterpene emission in connection to physiologic and enzymatic processes was conducted in leaves of Holm Oak (Quercus ilex), which emits a large spectrum of monoterpenes. Furthermore a hypothesis was tested, whether isoprene emission may serve the plant as antioxidative protection mechanism in order to overcome oxidative stress. In main parts, the following results have been reached: 1. In the first part of this work, isolation of PcDXR (DXR of Grey Poplar) from a cDNA-Genbank and heterologous expression of the isolated gene was accomplished. 2. Daytime variation of physiological and biochemical parameters of the isoprene emission of Grey Poplar was measured twice on 2 following days in 2 years. All together, measurements have been performed on 8 representative plants. 3. Quantitative RT-PCR elucidated the gene expression pattern of PcDXR and PcISPS in parallel to diurnal gas exchange measurements. Gene expression of PcISPS showed distinct diurnal courses with maximum values on the late morning, whereas PcDXR transcript levels stayed consistent over the day. No short-term influence of PPFD and leaf temperature has been observed on

Applying photosynthesis research to increase crop yields

Science.gov (United States)

Clayton C. Black; Shi-Jean S. Sung; Kristina Toderich; Pavel Yu Voronin

2010-01-01

This account is dedicated to Dr. Guivi Sanadze for his career long devotion to science and in recognition of his discovery of isoprene emission by trees during photosynthesis. Investigations on the emission of isoprene and other monoterpenes now have been extended globally to encompass other terrestrial vegetation, algae, waters, and marine life in the world's...

Biogenic volatile organic compound (VOC) emissions from forests in Finland

International Nuclear Information System (INIS)

Lindfors, V.; Laurila, T.

2000-01-01

We present model estimates of biogenic volatile organic compound (VOC) emissions from the forests in Finland. The emissions were calculated for the years 1995-1997 using the measured isoprene and monoterpene emission factors of boreal tree species together with detailed satellite land cover information and meteorological data. The three-year average emission is 319 kilotonnes per annum, which is significantly higher than the estimated annual anthropogenic VOC emissions of 193 kilotonnes. The biogenic emissions of the Finnish forests are dominated by monoterpenes, which contribute approximately 45% of the annual total. The main isoprene emitter is the Norway spruce (Picea abies) due to its high foliar biomass density. Compared to the monoterpenes, however, the total isoprene emissions are very low, contributing only about 7% of the annual forest VOC emissions. The isoprene emissions are more sensitive to the meteorological conditions than the monoterpene emissions, but the progress of the thermal growing season is clearly reflected in all biogenic emission fluxes. The biogenic emission densities in northern Finland are approximately half of the emissions in the southern parts of the country. (orig.)

C2-C10 hydrocarbon emissions from a boreal wetland and forest floor

Directory of Open Access Journals (Sweden)

H. Hellén

2006-01-01

Full Text Available Emissions of various C2-C10 hydrocarbons (VOCs and halogenated hydrocarbons (VHOCs from a boreal wetland and a Scots pine forest floor in south-western Finland were measured by the static chamber technique. Isoprene was the main non-methane hydrocarbon emitted by the wetland, but small emissions of ethene, propane, propene, 1-butene, 2-methylpropene, butane, pentane and hexane were also detected. The isoprene emission from the wetland was observed to follow the commonly-used isoprene emission algorithm. The mean emission potential of isoprene was 224 µg m-2 h-1 for the whole season. This is lower than the emission potentials published earlier; that is probably at least partly due to the cold and cloudy weather during the measurements. No emissions were detected of monoterpenes or halogenated hydrocarbons from the wetland. The highest hydrocarbon emissions from the Scots pine forest floor were measured in spring and autumn. However, only a few measurements were conducted during summer. The main compounds emitted were monoterpenes. Isoprene emissions were negligible. The total monoterpene emission rates varied from zero to 373 µg m-2 h-1. The results indicated that decaying plant litter may be the source for these emissions. Small emissions of chloroform (100-800 ng m-2 h-1, ethene, propane, propene, 2-methylpropene, cis-2-butene, pentane, hexane and heptane were detected. Comparison with Scots pine emissions showed that the forest floor may be an important monoterpene source, especially in spring.

Performance of BATAN-SANS instrument

Energy Technology Data Exchange (ETDEWEB)

Ikram, Abarrul; Insani, Andon [National Nuclear Energy Agency, P and D Centre for Materials Science and Technology, Serpong (Indonesia)

2003-03-01

SANS data from some standard samples have been obtained using BATAN-SANS instrument in Serpong. The experiments were performed for various experimental set-ups that involve different detector positions and collimator lengths. This paper describes the BATAN-SANS instrument briefly as well as the data taken from those experiments and followed with discussion of the results concerning the performance and calibration of the instrument. The standard samples utilized in these experiments include porous silica, polystyrene-poly isoprene, silver behenate, poly ball and polystyrene-poly (ethylene-alt-propylene). Even though the results show that BATAN-SANS instrument is in good shape, but rooms for improvements are still widely open especially for the velocity selector and its control system. (author)

Quantifying Forested Riparian Buffer Ability to Ameliorate Stream Temperature in a Missouri Ozark Border Stream of the Central U.S

Science.gov (United States)

Bulliner, E. A.; Hubbart, J. A.

2009-12-01

Riparian buffers play an important role in modulating stream water quality, including temperature. There is a need to better understand riparian form and function to validate and improve contemporary management practices. Further studies are warranted to characterize energy attenuation by forested riparian canopy layers that normally buffer stream temperature, particularly in the central hardwood forest regions of the United States where relationships between canopy density and stream temperature are unknown. To quantify these complex processes, two intensively instrumented hydroclimate stations were installed along two stream reaches of a riparian stream in central Missouri, USA in the winter of 2008. Hydroclimate stations are located along stream reaches oriented in both cardinal directions, which will allow interpolation of results to other orientations. Each station consists of an array of instrumentation that senses the flux of water and energy into and out of the riparian zone. Reference data are supplied from a nearby flux tower (US DOE) located on top of a forested ridge. The study sites are located within a University of Missouri preserved wildland area on the border of the southern Missouri’s Ozark region, an ecologically distinct region in the central United States. Limestone underlies the study area, resulting in a distinct semi-Karst hydrologic system. Vegetation forms a complex, multi-layered canopy extending from the stream edge through the riparian zone and into surrounding hills. Climate is classified as humid continental, with approximate average annual temperature and precipitation of 13.2°C and 970mm, respectively. Preliminary results (summer 2009 data) indicate incoming short-wave radiation is 24.9% higher at the N-S oriented stream reach relative to the E-W oriented reach. Maximum incoming short wave radiation during the period was 64.5% lower at the N-S reach relative to E-W reach. Average air temperature for the E-W reach was 0.3°C lower

Importance of biogenic precursors to the budget of organic nitrates: observations of multifunctional organic nitrates by CIMS and TD-LIF during BEARPEX 2009

Directory of Open Access Journals (Sweden)

M. R. Beaver

2012-07-01

Full Text Available Alkyl and multifunctional organic nitrates, molecules of the chemical form RONO₂, are products of chain terminating reactions in the tropospheric HO_x and NO_x catalytic cycles and thereby impact ozone formation locally. Many of the molecules in the class have lifetimes that are long enough that they can be transported over large distances. If the RONO₂ then decompose to deliver NO_x to remote regions they affect ozone production rates in locations distant from the original NO_x source. While measurements of total RONO₂ (ΣANs and small straight chain alkyl nitrates are routine, measurements of the specific multifunctional RONO₂ molecules that are believed to dominate the total have rarely been reported and never reported in coincidence with ambient ΣANs measurements. Here we describe observations obtained during the BEARPEX 2009 experiment including ΣANs and a suite of multifunctional nitrates including isoprene derived hydroxynitrates, oxidation products of those nitrates, 2-methyl-3-buten-2-ol (MBO derived hydroxynitrates, and monoterpene nitrates. At the BEARPEX field site, the sum of the individual biogenically derived nitrates account for two-thirds of the ΣANs, confirming predictions of the importance of biogenic nitrates to the NO_y budget. Isoprene derived nitrates, transported to the site, are a much larger fraction of the ΣANs at the site than the nitrates derived from the locally emitted MBO. Evidence for additional nitrates, possibly from nocturnal chemistry of isoprene and α-pinene, is presented.

Geologic map of the west-central Buffalo National River region, northern Arkansas

Science.gov (United States)

Hudson, Mark R.; Turner, Kenzie J.

2014-01-01

This map summarizes the geology of the west-central Buffalo National River region in the Ozark Plateaus region of northern Arkansas. Geologically, the region lies on the southern flank of the Ozark dome, an uplift that exposes oldest rocks at its center in Missouri. Physiographically, the map area spans the Springfield Plateau, a topographic surface generally held up by Mississippian cherty limestone and the higher Boston Mountains to the south, held up by Pennsylvanian rocks. The Buffalo River flows eastward through the map area, enhancing bedrock erosion of an approximately 1,600-ft- (490-m-) thick sequence of Ordovician, Mississippian, and Pennsylvanian carbonate and clastic sedimentary rocks that have been mildly deformed by a series of faults and folds. Quaternary surficial units are present as alluvial deposits along major streams, including a series of terrace deposits from the Buffalo River, as well as colluvium and landslide deposits mantling bedrock on hillslopes.

The C2H3O+ chemi-ion acetyl cation or O-protonated ketene

DEFF Research Database (Denmark)

Egsgaard, H.; Carlsen, L.

1995-01-01

The C2H3O+ chemi-ion sampled from a premixed methane/oxygen flame has been demonstrated to be the acetyl cation based on ion-molecule reactions with isoprene and 1,3-dioxolane.......The C2H3O+ chemi-ion sampled from a premixed methane/oxygen flame has been demonstrated to be the acetyl cation based on ion-molecule reactions with isoprene and 1,3-dioxolane....

Geographic range and morphological and chromosomal variability of Carex molestiformis (Cyperaceae) east of the Mississippi River

Science.gov (United States)

Carex molestiformis (frightful sedge), described in 1997 as an endemic to the Ozark and Ouachita Mountain regions, is newly collected from Georgia, Mississippi, and Ohio. Herbarium records have also confirmed this species from North Carolina, Virginia, and West Virginia bringing the overall range of...

78 FR 67187 - Notice of Availability of the Draft General Management Plan/Wilderness Study/Environmental Impact...

Science.gov (United States)

2013-11-08

... focus on protecting natural resources and systems. Under this alternative, most of the Big Spring... Availability of the Draft General Management Plan/ Wilderness Study/Environmental Impact Statement for the... Management Plan/Wilderness Study/Environmental Impact Statement (GMP/WS/EIS) for the Ozark National Scenic...

Simulated changes in biogenic VOC emissions and ozone formation from habitat expansion of Acer Rubrum (red maple)

International Nuclear Information System (INIS)

Drewniak, Beth A; Snyder, Peter K; Twine, Tracy E; Steiner, Allison L; Wuebbles, Donald J

2014-01-01

A new vegetation trend is emerging in northeastern forests of the United States, characterized by an expansion of red maple at the expense of oak. This has changed emissions of biogenic volatile organic compounds (BVOCs), primarily isoprene and monoterpenes. Oaks strongly emit isoprene while red maple emits a negligible amount. This species shift may impact nearby urban centers because the interaction of isoprene with anthropogenic nitrogen oxides can lead to tropospheric ozone formation and monoterpenes can lead to the formation of particulate matter. In this study the Global Biosphere Emissions and Interactions System was used to estimate the spatial changes in BVOC emission fluxes resulting from a shift in forest composition between oak and maple. A 70% reduction in isoprene emissions occurred when oak was replaced with maple. Ozone simulations with a chemical box model at two rural and two urban sites showed modest reductions in ozone concentrations of up to 5–6 ppb resulting from a transition from oak to red maple, thus suggesting that the observed change in forest composition may benefit urban air quality. This study illustrates the importance of monitoring and representing changes in forest composition and the impacts to human health indirectly through changes in BVOCs. (paper)

Microbial monoterpene transformations—a review

OpenAIRE

Marmulla, Robert; Harder, Jens

2014-01-01

Isoprene and monoterpenes constitute a significant fraction of new plant biomass. Emission rates into the atmosphere alone are estimated to be over 500 Tg per year. These natural hydrocarbons are mineralized annually in similar quantities. In the atmosphere, abiotic photochemical processes cause lifetimes of minutes to hours. Microorganisms encounter isoprene, monoterpenes, and other volatiles of plant origin while living in and on plants, in the soil and in aquatic habitats. Below toxic conc...

Design and Synthesis of Network-Forming Triblock Copolymers Using Tapered Block Interfaces

OpenAIRE

Kuan, Wei-Fan; Roy, Raghunath; Rong, Lixia; Hsiao, Benjamin S.; Epps, Thomas H.

2012-01-01

We report a strategy for generating novel dual-tapered poly(isoprene-b-isoprene/styrene-b-styrene-b-styrene/methyl methacrylate-b-methyl methacrylate) [P(I-IS-S-SM-M)] triblock copolymers that combines anionic polymerization, atom transfer radical polymerization (ATRP), and Huisgen 1,3-dipolar cycloaddition click chemistry. The tapered interfaces between blocks were synthesized via a semi-batch feed using programmable syringe pumps. This strategy allows us to manipulate the transition region ...

CURING AND MECHANICAL PROPERTIES OF CHLOROSULPHONATED POLYETHYLENE RUBBER BLEND

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Jaroslava Budinski-Simendić

2011-09-01

Full Text Available In this paper, the curing and mechanical properties of two series of prepared blends, i.e., chlorosulphonated polyethylene (CSM/isobutylene-co-isoprene (IIR rubber blends and chlorosulphonated polyethylene (CSM/chlorinated isobutylene-co-isoprene (CIIR rubber blends were carried out. Blends were prepared using a two-roll mill at a temperature of 40-50 °C. The curing was assessed using a Monsanto oscillating disc rheometer R-100. The process of vulcanization accelerated sulfur of pure rubbers and their blends was carried out in an electrically heated laboratory hydraulic press under a pressure of about 4 MPa and 160 °C. The stress-strain experiments were performed using a tensile tester machine (Zwick 1425. Results indicate that the scorch time, ts2, and optimum cure time, tc90, increase with increasing CSM content in both blends. The value of modulus at 100 and 300% elongation and tensile strength increases with increasing CSM content, whereas elongation at break shows a decreasing trend. The enhancement in mechanical properties was supported by data of crosslink density in these samples obtained from swelling measurement and scanning electron microscopy studies of the rubber blends fractured surfaces

77 FR 23273 - Endangered and Threatened Wildlife and Plants; Permit Applications

Science.gov (United States)

2012-04-18

.... Submit your written data, comments, or request for a copy of the complete application to the address... to avoid mortality of listed bats through curtailment of turbines and (2) the relationship between... to take (capture and release) Indiana bats, gray bats, Ozark big-eared bats (Corynorhinus townsendii...

76 FR 81987 - Notice of Determinations Regarding Eligibility To Apply for Worker Adjustment Assistance

Science.gov (United States)

2011-12-29

...) and Ozark Motor Lines, Working On- Site at Sanyo Manufacturing Corporation. 81,099 Brake Parts, Inc.... Automotive Coatings, Belcan and Aerotek, Working On-Site at General Motors. 81,008 Lintelle Engineering.... 80,352 Penske Logistics, LLC,, El Paso, TX. General Electric/Penske, El Paso Distribution, Warehouse...

Interactive chemistry in the Laboratoire de Météorologie Dynamique general circulation model: model description and impact analysis of biogenic hydrocarbons on tropospheric chemistry

Directory of Open Access Journals (Sweden)

G. A. Folberth

2006-01-01

Full Text Available We present a description and evaluation of LMDz-INCA, a global three-dimensional chemistry-climate model, pertaining to its recently developed NMHC version. In this substantially extended version of the model a comprehensive representation of the photochemistry of non-methane hydrocarbons (NMHC and volatile organic compounds (VOC from biogenic, anthropogenic, and biomass-burning sources has been included. The tropospheric annual mean methane (9.2 years and methylchloroform (5.5 years chemical lifetimes are well within the range of previous modelling studies and are in excellent agreement with estimates established by means of global observations. The model provides a reasonable simulation of the horizontal and vertical distribution and seasonal cycle of CO and key non-methane VOC, such as acetone, methanol, and formaldehyde as compared to observational data from several ground stations and aircraft campaigns. LMDz-INCA in the NMHC version reproduces tropospheric ozone concentrations fairly well throughout most of the troposphere. The model is applied in several sensitivity studies of the biosphere-atmosphere photochemical feedback. The impact of surface emissions of isoprene, acetone, and methanol is studied. These experiments show a substantial impact of isoprene on tropospheric ozone and carbon monoxide concentrations revealing an increase in surface O3 and CO levels of up to 30 ppbv and 60 ppbv, respectively. Isoprene also appears to significantly impact the global OH distribution resulting in a decrease of the global mean tropospheric OH concentration by approximately 0.7×105 molecules cm-3 or roughly 8% and an increase in the global mean tropospheric methane lifetime by approximately seven months. A global mean ozone net radiative forcing due to the isoprene induced increase in the tropospheric ozone burden of 0.09 W m-2 is found. The key role of isoprene photooxidation in the global tropospheric redistribution of NOx is demonstrated. LMDz

Biogenic volatile organic compound (BVOC) emissions from forested areas in Turkey: Determination of specific emission rates for thirty-one tree species

International Nuclear Information System (INIS)

Aydin, Yagmur Meltem; Yaman, Baris; Koca, Husnu; Dasdemir, Okan; Kara, Melik; Altiok, Hasan; Dumanoglu, Yetkin; Bayram, Abdurrahman; Tolunay, Doganay; Odabasi, Mustafa; Elbir, Tolga

2014-01-01

Normalized biogenic volatile organic compound (BVOC) emission rates for thirty one tree species that cover the 98% of national forested areas in Turkey were determined. Field samplings were performed at fourteen different forested areas in Turkey using a specific dynamic enclosure system. The selected branches of tree species were enclosed in a chamber consisted of a transparent Nalofan bag. The air-flows were sampled from both inlet and outlet of the chamber by Tenax-filled sorbent tubes during photosynthesis of trees under the presence of sunlight. Several environmental parameters (temperature, humidity, photosynthetically active radiation-PAR, and CO 2 ) were continuously monitored inside and outside the enclosure chamber during the samplings. Collected samples were analyzed using a gas chromatography mass spectrometry (GC/MS) system equipped with a thermal desorber (TD). Sixty five BVOCs classified in five major groups (isoprene, monoterpenes, sesquiterpenes, oxygenated sesquiterpenes, and other oxygenated compounds) were analyzed. Emission rates were determined by normalization to standard conditions (1000 μmol/m 2 s PAR and 30 °C temperature for isoprene and 30 °C temperature for the remaining compounds). In agreement with the literature, isoprene was mostly emitted by broad-leaved trees while coniferous species mainly emitted monoterpenes. Several tree species such as Sweet Chestnut, Silver Lime, and European Alder had higher monoterpene emissions although they are broad-leaved species. High isoprene emissions were also observed for a few coniferous species such as Nordmann Fir and Oriental Spruce. The highest normalized total BVOC emission rate of 27.1 μg/g h was observed for Oriental Plane while South European Flowering Ash was the weakest BVOC emitter with a total normalized emission rate of 0.031 μg/g h. Monoterpene emissions of broad-leaved species mainly consisted of sabinene, limonene and trans-beta-ocimene, while alpha-pinene, beta-pinene and

Biogenic volatile organic compound (BVOC) emissions from forested areas in Turkey: Determination of specific emission rates for thirty-one tree species

Energy Technology Data Exchange (ETDEWEB)

Aydin, Yagmur Meltem; Yaman, Baris; Koca, Husnu; Dasdemir, Okan; Kara, Melik; Altiok, Hasan; Dumanoglu, Yetkin; Bayram, Abdurrahman [Department of Environmental Engineering, Faculty of Engineering, Dokuz Eylul University, Tinaztepe Campus, Buca, Izmir (Turkey); Tolunay, Doganay [Department of Soil Science and Ecology, Faculty of Forestry, Istanbul University, Bahcekoy, Istanbul (Turkey); Odabasi, Mustafa [Department of Environmental Engineering, Faculty of Engineering, Dokuz Eylul University, Tinaztepe Campus, Buca, Izmir (Turkey); Elbir, Tolga, E-mail: tolga.elbir@deu.edu.tr [Department of Environmental Engineering, Faculty of Engineering, Dokuz Eylul University, Tinaztepe Campus, Buca, Izmir (Turkey)

2014-08-15

Normalized biogenic volatile organic compound (BVOC) emission rates for thirty one tree species that cover the 98% of national forested areas in Turkey were determined. Field samplings were performed at fourteen different forested areas in Turkey using a specific dynamic enclosure system. The selected branches of tree species were enclosed in a chamber consisted of a transparent Nalofan bag. The air-flows were sampled from both inlet and outlet of the chamber by Tenax-filled sorbent tubes during photosynthesis of trees under the presence of sunlight. Several environmental parameters (temperature, humidity, photosynthetically active radiation-PAR, and CO{sub 2}) were continuously monitored inside and outside the enclosure chamber during the samplings. Collected samples were analyzed using a gas chromatography mass spectrometry (GC/MS) system equipped with a thermal desorber (TD). Sixty five BVOCs classified in five major groups (isoprene, monoterpenes, sesquiterpenes, oxygenated sesquiterpenes, and other oxygenated compounds) were analyzed. Emission rates were determined by normalization to standard conditions (1000 μmol/m{sup 2} s PAR and 30 °C temperature for isoprene and 30 °C temperature for the remaining compounds). In agreement with the literature, isoprene was mostly emitted by broad-leaved trees while coniferous species mainly emitted monoterpenes. Several tree species such as Sweet Chestnut, Silver Lime, and European Alder had higher monoterpene emissions although they are broad-leaved species. High isoprene emissions were also observed for a few coniferous species such as Nordmann Fir and Oriental Spruce. The highest normalized total BVOC emission rate of 27.1 μg/g h was observed for Oriental Plane while South European Flowering Ash was the weakest BVOC emitter with a total normalized emission rate of 0.031 μg/g h. Monoterpene emissions of broad-leaved species mainly consisted of sabinene, limonene and trans-beta-ocimene, while alpha-pinene, beta

Simulating atmospheric composition over a South-East Asian tropical rainforest: performance of a chemistry box model

Directory of Open Access Journals (Sweden)

T. A. M. Pugh

2010-01-01

Full Text Available Atmospheric composition and chemistry above tropical rainforests is currently not well established, particularly for south-east Asia. In order to examine our understanding of chemical processes in this region, the performance of a box model of atmospheric boundary layer chemistry is tested against measurements made at the top of the rainforest canopy near Danum Valley, Malaysian Borneo. Multi-variate optimisation against ambient concentration measurements was used to estimate average canopy-scale emissions for isoprene, total monoterpenes and nitric oxide. The excellent agreement between estimated values and measured fluxes of isoprene and total monoterpenes provides confidence in the overall modelling strategy, and suggests that this method may be applied where measured fluxes are not available, assuming that the local chemistry and mixing are adequately understood. The largest contributors to the optimisation cost function at the point of best-fit are OH (29%, NO (22% and total peroxy radicals (27%. Several factors affect the modelled VOC chemistry. In particular concentrations of methacrolein (MACR and methyl-vinyl ketone (MVK are substantially overestimated, and the hydroxyl radical (OH concentration is substantially underestimated; as has been seen before in tropical rainforest studies. It is shown that inclusion of dry deposition of MACR and MVK and wet deposition of species with high Henry's Law values substantially improves the fit of these oxidised species, whilst also substantially decreasing the OH sink. Increasing OH production arbitrarily, through a simple OH recycling mechanism , adversely affects the model fit for volatile organic compounds (VOCs. Given the constraints on isoprene flux provided by measurements, a substantial decrease in the rate of reaction of VOCs with OH is the only remaining option to explain the measurement/model discrepancy for OH. A reduction in the isoprene+OH rate constant of 50%, in conjunction with

The impact of large scale biomass production on ozone air pollution in Europe

OpenAIRE

Beltman, Joost B.; Hendriks, Carlijn; Tum, Markus; Schaap, Martijn

2013-01-01

Tropospheric ozone contributes to the removal of air pollutants from the atmosphere but is itself a pollutant that is harmful to human health and vegetation. Biogenic isoprene emissions are important ozone precursors, and therefore future changes in land use that change isoprene emissions are likely to affect atmospheric ozone concentrations. Here, we use the chemical transport model LOTOS-EUROS (dedicated to the regional modeling of trace gases in Europe) to study a scenario in which 5% of t...

Integrating Biodiversity into Biosphere-Atmosphere Interactions Using Individual-Based Models (IBM)

Science.gov (United States)

Wang, B.; Shugart, H. H., Jr.; Lerdau, M.

2017-12-01

A key component regulating complex, nonlinear, and dynamic biosphere-atmosphere interactions is the inherent diversity of biological systems. The model frameworks currently widely used, i.e., Plant Functional Type models) do not even begin to capture the metabolic and taxonomic diversity found in many terrestrial systems. We propose that a transition from PFT-based to individual-based modeling approaches (hereafter referred to as IBM) is essential for integrating biodiversity into research on biosphere-atmosphere interactions. The proposal emerges from our studying the interactions of forests with atmospheric processes in the context of climate change using an individual-based forest volatile organic compounds model, UVAFME-VOC. This individual-based model can explicitly simulate VOC emissions based on an explicit modelling of forest dynamics by computing the growth, death, and regeneration of each individual tree of different species and their competition for light, moisture, and nutrient, from which system-level VOC emissions are simulated by explicitly computing and summing up each individual's emissions. We found that elevated O3 significantly altered the forest dynamics by favoring species that are O3-resistant, which, meanwhile, are producers of isoprene. Such compositional changes, on the one hand, resulted in unsuppressed forest productivity and carbon stock because of the compensation by O3-resistant species. On the other hand, with more isoprene produced arising from increased producers, a possible positive feedback loop between tropospheric O3 and forest thereby emerged. We also found that climate warming will not always stimulate isoprene emissions because warming simultaneously reduces isoprene emissions by causing a decline in the abundance of isoprene-emitting species. These results suggest that species diversity is of great significance and that individual-based modelling strategies should be applied in studying biosphere-atmosphere interactions.

Submicron particle mass concentrations and sources in the Amazonian wet season (AMAZE-08)

Energy Technology Data Exchange (ETDEWEB)

Chen, Q.; Farmer, D. K.; Rizzo, L. V.; Pauliqueivis, T.; Kuwata, Mikinori; Karl, Thomas G.; Guenther, Alex B.; Allan, James D.; Coe, H.; Andreae, M. O.; Poeschl, U.; Jiminez, J. L.; Artaxo, Paulo; Martin, Scot T.

2015-01-01

Real-time mass spectra of non-refractory component of submicron aerosol particles were recorded in a tropical rainforest in the central Amazon basin during the wet season of 2008, as a part of the Amazonian Aerosol Characterization Experiment (AMAZE-08). Organic components accounted on average for more than 80% of the non-refractory submicron particle mass concentrations during the period of measurements. Ammonium was present in sufficient quantities to halfway neutralize sulfate. In this acidic, isoprene-dominated, low-NOx environment the high-resolution mass spectra as well as mass closures with ion chromatography measurements did not provide evidence for significant contributions of organosulfate species, at least at concentrations above uncertainty levels. Positive-matrix factorization of the time series of particle mass spectra identified four statistical factors to account for the variance of the signal intensities of the organic constituents: a factor HOA having a hydrocarbon-like signature and identified as regional emissions of primary organic material, a factor OOA-1 associated with fresh production of secondary organic material by a mechanism of BVOC oxidation followed by gas-to-particle conversion, a factor OOA-2 consistent with reactive uptake of isoprene oxidation products, especially epoxydiols by acidic particles, and a factor OOA-3 associated with long range transport and atmospheric aging. The OOA-1, -2, and -3 factors had progressively more oxidized signatures. Diameter-resolved mass spectral markers also suggested enhanced reactive uptake of isoprene oxidation products to the accumulation mode for the OOA-2 factor, and such size partitioning can be indicative of in-cloud process. The campaign-average factor loadings were in a ratio of 1.1:1.0 for the OOA-1 compared to the OOA-2 pathway, suggesting the comparable importance of gas-phase compared to particle-phase (including cloud waters) production pathways of secondary organic material during

Prioritizing Historical Archaeological Sites at Fort Leonard Wood, Pulaski County, Missouri

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2012-04-01

report are not to be used for advertising , publication, or promotional purposes. Citation of trade names does not constitute an official endorsement or...though this farmstead was nestled deep in the Missouri Ozarks, it was by no means isolated from the global trade networks of the period. The

Exploring Blueberry Aroma Complexity by Chromatographic and Direct-Injection Spectrometric Techniques.

Science.gov (United States)

Farneti, Brian; Khomenko, Iuliia; Grisenti, Marcella; Ajelli, Matteo; Betta, Emanuela; Algarra, Alberto Alarcon; Cappellin, Luca; Aprea, Eugenio; Gasperi, Flavia; Biasioli, Franco; Giongo, Lara

2017-01-01

Blueberry ( Vaccinium spp.) fruit consumption has increased over the last 5 years, becoming the second most important soft fruit species after strawberry. Despite the possible economic and sensory impact, the blueberry volatile organic compound (VOC) composition has been poorly investigated. Thus, the great impact of the aroma on fruit marketability stimulates the need to step forward in the understanding of this quality trait. Beside the strong effect of ripening, blueberry aroma profile also varies due to the broad genetic differences among Vaccinium species that have been differently introgressed in modern commercial cultivars through breeding activity. In the present study, divided into two different activities, the complexity of blueberry aroma was explored by an exhaustive untargeted VOC analysis, performed by two complementary methods: SPME-GC-MS (solid phase microextraction- gas chromatography-mass spectrometry) and PTR-ToF-MS (proton transfer reaction-time of flight-mass spectrometry). The first experiment was aimed at determining the VOC modifications during blueberry ripening for five commercially representative cultivars ("Biloxi," "Brigitta Blue," "Centurion," "Chandler," and "Ozark Blue") harvested at four ripening stages (green, pink, ripe, and over-ripe) to outline VOCs dynamic during fruit development. The objective of the second experiment was to confirm the analytical capability of PTR-ToF-MS to profile blueberry genotypes and to identify the most characterizing VOCs. In this case, 11 accessions belonging to different Vaccinium species were employed: V . corymbosum L. ("Brigitta," "Chandler," "Liberty," and "Ozark Blue"), V. virgatum Aiton ("Centurion," "Powder Blue," and "Sky Blue"), V. myrtillus L. (three wild genotypes of different mountain locations), and one accession of V. cylindraceum Smith. This comprehensive characterization of blueberry aroma allowed the identification of a wide pull of VOCs, for the most aldehydes, alcohols, terpenoids

Linking experiment and theory for three-dimensional networked binary metal nanoparticle–triblock terpolymer superstructures

KAUST Repository

Li, Zihui

2014-02-21

© 2014 Macmillan Publishers Limited. Controlling superstructure of binary nanoparticle mixtures in three dimensions from self-assembly opens enormous opportunities for the design of materials with unique properties. Here we report on how the intimate coupling of synthesis, in-depth electron tomographic characterization and theory enables exquisite control of superstructure in highly ordered porous three-dimensional continuous networks from single and binary mixtures of metal nanoparticles with a triblock terpolymer. Poly(isoprene-block-styrene-block-(N,N-dimethylamino)ethyl methacrylate) is synthesized and used as structure-directing agent for ligand-stabilized platinum and gold nanoparticles. Quantitative analysis provides insights into short-and long-range nanoparticle-nanoparticle correlations, and local and global contributions to structural chirality in the networks. Results provide synthesis criteria for next-generation mesoporous network superstructures from binary nanoparticle mixtures for potential applications in areas including catalysis.

Gravel sediment routing from widespread, low-intensity landscape disturbance, Current River basin, Missouri

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Jacobson, Robert B.; Gran, K.B.

1999-01-01

During the last 160 years, land-use changes in the Ozarks have had the potential to cause widespread, low-intensity delivery of excess amounts of gravel-sized sediment to stream channels. Previous studies have indicated that this excess gravel bedload is moving in wave-like forms through Ozarks drainage basins. The longitudinal, areal distribution of gravel bars along 160 km of the Current River, Missouri, was evaluated to determine the relative effects of valley-scale controls, tributary basin characteristics, and lagged sediment transport in creating areas of gravel accumulations. The longitudinal distribution of gravel-bar area shows a broad scale wave-like form with increases in gravel-bar area weakly associated with tributary junctions. Secondary peaks of gravel area with 1·8–4·1 km spacing (disturbance reaches) are superimposed on the broad form. Variations in valley width explain some, but not all, of the short-spacing variation in gravel-bar area. Among variables describing tributary drainage basin morphometry, present-day land use and geologic characteristics, only drainage area and road density relate even weakly to gravel-bar areal inventories. A simple, channel network-based sediment routing model shows that many of the features of the observed longitudinal gravel distribution can be replicated by uniform transport of sediment from widespread disturbances through a channel network. These results indicate that lagged sediment transport may have a dominant effect on the synoptic spatial distribution of gravel in Ozarks streams; present-day land uses are only weakly associated with present-day gravel inventories; and valley-scale characteristics have secondary controls on gravel accumulations in disturbance reaches.

Geologic map of the Montauk quadrangle, Dent, Texas, and Shannon Counties, Missouri

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Weary, David J.

2015-04-30

The Montauk 7.5-minute quadrangle is located in south-central Missouri within the Salem Plateau region of the Ozark Plateaus physiographic province. About 2,000 feet (ft) of flat-lying to gently dipping lower Paleozoic sedimentary rocks, mostly dolomite, chert, sandstone, and orthoquartzite, overlie Mesoproterozoic igneous basement rocks. Unconsolidated residuum, colluvium, terrace deposits, and alluvium overlie the sedimentary rocks. Numerous karst features, such as caves, springs, and sinkholes, have formed in the carbonate rocks. Many streams are spring fed. The topography is a dissected karst plain with elevations ranging from approximately 830 ft where the Current River exits the middle-eastern edge of the quadrangle to about 1,320 ft in sec. 16, T. 31 N., R. 7 W., in the southwestern part of the quadrangle. The most prominent physiographic features within the quadrangle are the deeply incised valleys of the Current River and its major tributaries located in the center of the map area. The Montauk quadrangle is named for Montauk Springs, a cluster of several springs that resurge in sec. 22, T. 32 N., R. 7 W. These springs supply clean, cold water for the Montauk Fish Hatchery, and the addition of their flow to that of Pigeon Creek produces the headwaters of the Current River, the centerpiece of the Ozark National Scenic Riverways park. Most of the land in the quadrangle is privately owned and used primarily for grazing cattle and horses and growing timber. A smaller portion of the land within the quadrangle is publicly owned by either Montauk State Park or the Ozark National Scenic Riverways (National Park Service). Geologic mapping for this investigation was conducted in 2007 and 2009.

Influence of drift and admixture on population structure of American black bears (Ursus americanus) in the Central Interior Highlands, USA, 50 years after translocation.

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Puckett, Emily E; Kristensen, Thea V; Wilton, Clay M; Lyda, Sara B; Noyce, Karen V; Holahan, Paula M; Leslie, David M; Beringer, Jeff; Belant, Jerrold L; White, Don; Eggert, Lori S

2014-05-01

Bottlenecks, founder events, and genetic drift often result in decreased genetic diversity and increased population differentiation. These events may follow abundance declines due to natural or anthropogenic perturbations, where translocations may be an effective conservation strategy to increase population size. American black bears (Ursus americanus) were nearly extirpated from the Central Interior Highlands, USA by 1920. In an effort to restore bears, 254 individuals were translocated from Minnesota, USA, and Manitoba, Canada, into the Ouachita and Ozark Mountains from 1958 to 1968. Using 15 microsatellites and mitochondrial haplotypes, we observed contemporary genetic diversity and differentiation between the source and supplemented populations. We inferred four genetic clusters: Source, Ouachitas, Ozarks, and a cluster in Missouri where no individuals were translocated. Coalescent models using approximate Bayesian computation identified an admixture model as having the highest posterior probability (0.942) over models where the translocation was unsuccessful or acted as a founder event. Nuclear genetic diversity was highest in the source (AR = 9.11) and significantly lower in the translocated populations (AR = 7.07-7.34; P = 0.004). The Missouri cluster had the lowest genetic diversity (AR = 5.48) and served as a natural experiment showing the utility of translocations to increase genetic diversity following demographic bottlenecks. Differentiation was greater between the two admixed populations than either compared to the source, suggesting that genetic drift acted strongly over the eight generations since the translocation. The Ouachitas and Missouri were previously hypothesized to be remnant lineages. We observed a pretranslocation remnant signature in Missouri but not in the Ouachitas. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.

In situ and real-time small-angle neutron scattering studies of living anionic polymerization process and polymerization-induced self-assembly of block copolymers

International Nuclear Information System (INIS)

Tanaka, H.; Yamauchi, K.; Hasegawa, H.; Miyamoto, N.; Koizumi, S.; Hashimoto, T.

2006-01-01

We have studied a simultaneous living anionic polymerization process of isoprene and deuterated styrene in deuterated benzene with sec-buthyl lithium as an initiator into polyisoprene-block-poly(styrene-d 8 ) and the polymerization-induced self-assembling process. This polymerization-induced self-assembling process was directly observed by an in situ and real-time small-angle neutron scattering (SANS) experiment. The time-resolved SANS studies enabled us to explore a time evolution of hierarchical structures induced by a time evolution of the primary structure (linear sequential connection of two monomers)

The Atmospheric Chemistry and Canopy Exchange Simulation System (ACCESS: model description and application to a temperate deciduous forest canopy

Directory of Open Access Journals (Sweden)

R. D. Saylor

2013-01-01

Full Text Available Forest canopies are primary emission sources of biogenic volatile organic compounds (BVOCs and have the potential to significantly influence the formation and distribution of secondary organic aerosol (SOA mass. Biogenically-derived SOA formed as a result of emissions from the widespread forests across the globe may affect air quality in populated areas, degrade atmospheric visibility, and affect climate through direct and indirect forcings. In an effort to better understand the formation of SOA mass from forest emissions, a 1-D column model of the multiphase physical and chemical processes occurring within and just above a vegetative canopy is being developed. An initial, gas-phase-only version of this model, the Atmospheric Chemistry and Canopy Exchange Simulation System (ACCESS, includes processes accounting for the emission of BVOCs from the canopy, turbulent vertical transport within and above the canopy and throughout the height of the planetary boundary layer (PBL, near-explicit representation of chemical transformations, mixing with the background atmosphere and bi-directional exchange between the atmosphere and canopy and the atmosphere and forest floor. The model formulation of ACCESS is described in detail and results are presented for an initial application of the modeling system to Walker Branch Watershed, an isoprene-emission-dominated forest canopy in the southeastern United States which has been the focal point for previous chemical and micrometeorological studies. Model results of isoprene profiles and fluxes are found to be consistent with previous measurements made at the simulated site and with other measurements made in and above mixed deciduous forests in the southeastern United States. Sensitivity experiments are presented which explore how canopy concentrations and fluxes of gas-phase precursors of SOA are affected by background anthropogenic nitrogen oxides (NO_x. Results from these experiments suggest that the

Hygroscopic influence on the semisolid-to-liquid transition of secondary organic materials.

Science.gov (United States)

Bateman, Adam P; Bertram, Allan K; Martin, Scot T

2015-05-14

The effect of relative humidity (RH) on the rebound of particles composed of isoprene, α-pinene, and toluene secondary organic materials (SOMs) was studied. A three-arm impaction apparatus was used to study rebound from 5 to 95% RH at 298 K. Calibration experiments using sucrose particles of variable but known viscosities showed that the transition from rebounding to adhering particles occurred for a change in viscosity from 100 to 1 Pa s, corresponding to a transition from semisolid to liquid material. The experimentally determined rebound fractions of the studied SOMs were compared with results from a model of the rebound processes of hard particles, taking into account the particle kinetic energy, van der Waals forces, and RH-dependent capillary forces. For low RH values, the hard-particle model explained the diameter-dependent rebound behavior for all studied SOMs. For elevated RH, however, the experimental observations deviated from the model predictions. On the basis of the calibration experiments using sucrose particles as well as a comparison between the observations and the predictions of the hard-particle model, the interpretation is made that a semisolid-to-liquid transition occurred at elevated RH. Material softening, increased adhesion, or a combination of the two implied the action of additional modes of energy relaxation that were not included in the hard-particle model. The RH threshold for the semisolid-to-liquid phase transition was 40% RH for isoprene SOM, 70% for toluene SOM, and 70% for α-pinene SOM. A correlation between the rebound fraction and the hygroscopic growth factor G was demonstrated, implying that absorbed water volume was a dominant governing factor of the semisolid-to-liquid transition for the studied classes of SOM. Simple heuristic rules based on G of 1.15 for the semisolid-to-liquid phase transition could be used for prognostication of the SOM phase in modeling applications at 298 K. With respect to atmospheric processes, the

Biogeography of Missouri. Instructional Unit. Conservation Education Series.

Science.gov (United States)

Castillon, David A.

This unit is designed to help social studies or science teachers incorporate ecological concepts into the teaching of science and Missouri geography. The unit includes: (1) a topic outline; (2) general unit objectives; (3) an introduction to basic biogeographical concepts; (4) descriptions of the glaciated prairie, unglaciated prairie, ozark, and…

Forests and ozone: productivity, carbon storage, and feedbacks.

Science.gov (United States)

Wang, Bin; Shugart, Herman H; Shuman, Jacquelyn K; Lerdau, Manuel T

2016-02-22

Tropospheric ozone is a serious air-pollutant, with large impacts on plant function. This study demonstrates that tropospheric ozone, although it damages plant metabolism, does not necessarily reduce ecosystem processes such as productivity or carbon sequestration because of diversity change and compensatory processes at the community scale ameliorate negative impacts at the individual level. This study assesses the impact of ozone on forest composition and ecosystem dynamics with an individual-based gap model that includes basic physiology as well as species-specific metabolic properties. Elevated tropospheric ozone leads to no reduction of forest productivity and carbon stock and to increased isoprene emissions, which result from enhanced dominance by isoprene-emitting species (which tolerate ozone stress better than non-emitters). This study suggests that tropospheric ozone may not diminish forest carbon sequestration capacity. This study also suggests that, because of the often positive relationship between isoprene emission and ozone formation, there is a positive feedback loop between forest communities and ozone, which further aggravates ozone pollution.

Leaf ontogeny dominates the seasonal exchange of volatile organic compounds (VOC) in a SRC-poplar plantation during an entire growing season

Science.gov (United States)

Brilli, Federico; Gioli, Beniamino; Fares, Silvano; Zenone, Terenzio; Zona, Donatella; Gielen, Bert; Loreto, Francesco; Janssens, Ivan; Ceulemans, Reinhart

2015-04-01

The declining cost of many renewable energy technologies and changes in the prices of fossil fuels have recently encouraged governments policies to subsidize the use of biomass as a sustainable source of energy. Deciduous poplars (Populus spp.) trees are often selected for biomass production in short rotation coppiced (SRC) for their high CO2 photosynthetic assimilation rates and their capacity to develop dense canopies with high values of leaf area index (LAI). So far, observations and projections of seasonal variations of many VOC fluxes has been limited to strong isoprenoids emitting evergreen ecosystems such tropical and Mediterranean forests as well as Citrus and oil palm plantation, all having constant values of LAI. We run a long-term field campaign where the exchange of VOC, together with CO2 and water vapor was monitored during an entire growing season (June - November, 2012) above a SRC-based poplar plantation. Our results confirmed that isoprene and methanol were the most abundant fluxes emitted, accounting for more than 90% of the total carbon released in form of VOC. However, Northern climates characterized by fresh summertime temperatures and recurring precipitations favored poplar growth while inhibiting the development of isoprene emission that resulted in only 0.7% of the net ecosystem carbon exchange (NEE). Besides, measurements of a multitude of VOC fluxes by PTR-TOF-MS showed bi-directional exchange of oxygenated-VOC (OVOC) such as: formaldehyde, acetaldehyde, acetone, isoprene oxidation products (iox, namely MVK, MAC and MEK) as well as ethanol and formic acid. The application of Self Organizing Maps to visualize the relationship between the full time-series of many VOC fluxes and the observed seasonal variations of environmental, physiological and structural parameters proved the most abundant isoprene ad methanol fluxes to occur mainly on the hottest days under mid-high light intensities when also NEE and evapotraspiration reached the highest

Seasonal and interannual variations in whole-ecosystem BVOC emissions from a subtropical plantation in China

Science.gov (United States)

Bai, Jianhui; Guenther, Alex; Turnipseed, Andrew; Duhl, Tiffany; Greenberg, James

2017-07-01

Measurements of BVOC emissions, ozone concentration and environmental parameters were carried out from May 2013 to January 2016 in a subtropical Pinus plantation in China. Isoprene and monoterpene emissions were measured using a relaxed eddy accumulation (REA) system and a gradient technique on an above-canopy tower. In 2013, isoprene comprised 21.2% of total terpenoid emissions, while α-pinene, camphene, β-pinene and limonene constituting 51.5%, 2.4%, 9.1%, and 13.0% of total emissions, respectively. Monoterpenes together were the dominant VOCs measured contributing 71.6%. α-pinene, camphene, β-pinene and limonene constituted 67.7%, 3.2%, 11.9%, 17.2% of total monoterpene emissions. Isoprene and monoterpene emissions displayed strong diurnal variations, with lower emissions in the morning and late evening, and the highest emissions around noon. BVOC peak emissions typically occurred a few hours after the noon PAR peak. Isoprene and monoterpene emissions varied with season and were the highest in summer, contributing more than half of the total annual emission, and the lowest emissions were in winter. Evident interannual variations of isoprene, monoterpenes and total BVOCs were observed. Compared to 2013, annual BVOC emissions decreased in 2015, associated with decreases of PAR, Temperature, water vapor, and an increase of all substances in gas, liquid and solid phases in the atmospheric column (e.g., S/Q, the ratio of solar scattered radiation to global radiation). Ozone concentration showed clear diurnal variation with PAR, higher around noon and lower in the early morning and late evening. Generally, there were no evident correlations between ozone concentrations and BVOC emissions, or the vertical gradients of ozone concentrations and BVOC concentrations. Under all sky conditions (including cloudy skies), no strong correlations at a high confidence level or very similar variation patterns were observed between any two following parameters, BVOC emissions

Eddy covariance flux measurements of biogenic VOCs during ECHO 2003 using proton transfer reaction mass spectrometry

Directory of Open Access Journals (Sweden)

C. Spirig

2005-01-01

Full Text Available Within the framework of the AFO 2000 project ECHO, two PTR-MS instruments were operated in combination with sonic anemometers to determine biogenic VOC fluxes from a mixed deciduous forest site in North-Western Germany. The measurement site was characterised by a forest of inhomogeneous composition, complex canopy structure, limited extension in certain wind directions and frequent calm wind conditions during night time. The eddy covariance (EC technique was applied since it represents the most direct flux measurement approach on the canopy scale and is, therefore, least susceptible to these non-ideal conditions. A specific flux calculation method was used to account for the sequential multi-component PTR-MS measurements and allowing an individual delay time adjustment as well as a rigorous quality control based on cospectral analysis. The validated flux results are consistent with light and temperature dependent emissions of isoprene and monoterpenes from this forest, with average daytime emissions of 0.94 and 0.3µg m-2s-1, respectively. Emissions of methanol reached on average 0.087µg m-2s-1 during daytime, but fluxes were too small to be detected during night time. Upward fluxes of the isoprene oxidation products methyl vinyl ketone (MVK and methacrolein (MACR were also found, being two orders of magnitude lower than those of isoprene. Calculations with an analytical footprint model indicate that the observed isoprene fluxes correlate with the fraction of oaks within the footprints of the flux measurement.

Hydroxyl radical and ozone initiated photochemical reactions of 1,3-butadiene

Science.gov (United States)

Liu, Xiaoyu; Jeffries, Harvey E.; Sexton, Kenneth G.

1,3-Butadiene, classified as hazardous in the 1990 Clean Air Act Amendments, is an important ambient air pollutant. Understanding its atmospheric transformation is useful for its own sake, and is also helpful for eliciting isoprene's fate in the atmosphere (isoprene dominates the biogenic emissions in US). In this paper, samples from both hydroxyl- and ozone-initiated photooxidation of 1,3-butadiene were analyzed by derivatization with O- (2,3,4,5,6-pentafluorobenzyl)-hydroxylamine followed by separation and detection by gas chromatography/ion trap mass spectrometry to detect and identify carbonyl compounds. The following carbonyls were observed: formaldehyde, acrolein, glycolaldehyde, glycidaldehyde, 3-hydroxy-propanaldehyde, hydroxy acetone, and malonaldehyde, which can be classified into three categories: epoxy carbonyls, hydroxyl carbonyls, and di-carbonyls. Three non-carbonyls, furan, 1,3-buatdiene monoxide, and 1,3-butadiene diepoxide, were also found. To confirm their identities, both commercially available and synthesized standards were used. To investigate the mechanism of 1,3-butadiene, separate batch reactor experiments for acrolein and 1,3-butadiene monoxide were carried out. Time series samples for several products were also taken. When necessary, computational chemistry methods were also employed. Based on these results, various schemes for the reaction mechanism are proposed.

Regime shifts and weakened environmental gradients in open oak and pine ecosystems.

Science.gov (United States)

Hanberry, Brice B; Dey, Dan C; He, Hong S

2012-01-01

Fire suppression allows tree species that are intolerant of fire stress to increase their distribution, potentially resulting in disruption of historical species-environmental relationships. To measure changes between historical General Land Office surveys (1815 to 1850) and current USDA Forest Inventory and Assessment surveys (2004 to 2008), we compared composition, distribution, and site factors of 21 tree species or species groups in the Missouri Ozarks. We used 24 environmental variables and random forests as a classification method to model distributions. Eastern redcedar, elms, maples, and other fire-sensitive species have increased in dominance in oak forests, with concurrent reductions by oak species; specific changes varied by ecological subsection. Ordinations displayed loss of separation between formerly distinctive oak and fire-sensitive tree species groups. Distribution maps showed decreased presence of disturbance-dependent oak and pine species and increased presence of fire-sensitive species that generally expanded from subsections protected from fire along rivers to upland areas, except for eastern redcedar, which expanded into these subsections. Large scale differences in spatial gradients between past and present communities paralleled reduced influence of local topographic gradients in the varied relief of the Missouri Ozarks, as fire-sensitive species have moved to higher, drier, and sunnier sites away from riverine corridors. Due to changes in land use, landscapes in the Missouri Ozarks, eastern United States, and world-wide are changing from open oak and pine-dominated ecosystems to novel oak-mixed species forests, although at fine scales, forests are becoming more diverse in tree species today. Fire suppression weakened the influence by environmental gradients over species dominance, allowing succession from disturbance-dependent oaks to an alternative state of fire-sensitive species. Current and future research and conservation that rely on

Economics of Coharvesting Smallwood by Chainsaw and Skidder for Crop Tree Management in Missouri

Science.gov (United States)

Peter Becker; E.M.(Ted) Bilek; Terry Cunningham; Michael Bill; Marty Calvert; Jason Jensen; Michael Norris; Terry Thompson

2011-01-01

Forest improvement harvests using individual-tree and group selection were conducted in four oak or oak-hickory stands in the Missouri Ozarks with conventional equipment (chainsaw and skidder). Volumes (and revenues) for different timber classes (sawlogs and smallwood from topwood and small trees) and hours of machine use were recorded to calculate production rates....

Biogenic volatile organic compound and respiratory CO2 emissions after 13C-labeling: online tracing of C translocation dynamics in poplar plants.

Science.gov (United States)

Ghirardo, Andrea; Gutknecht, Jessica; Zimmer, Ina; Brüggemann, Nicolas; Schnitzler, Jörg-Peter

2011-02-28

Globally plants are the primary sink of atmospheric CO(2), but are also the major contributor of a large spectrum of atmospheric reactive hydrocarbons such as terpenes (e.g. isoprene) and other biogenic volatile organic compounds (BVOC). The prediction of plant carbon (C) uptake and atmospheric oxidation capacity are crucial to define the trajectory and consequences of global environmental changes. To achieve this, the biosynthesis of BVOC and the dynamics of C allocation and translocation in both plants and ecosystems are important. We combined tunable diode laser absorption spectrometry (TDLAS) and proton transfer reaction mass spectrometry (PTR-MS) for studying isoprene biosynthesis and following C fluxes within grey poplar (Populus x canescens) saplings. This was achieved by feeding either (13)CO(2) to leaves or (13)C-glucose to shoots via xylem uptake. The translocation of (13)CO(2) from the source to other plant parts could be traced by (13)C-labeled isoprene and respiratory (13)CO(2) emission. In intact plants, assimilated (13)CO(2) was rapidly translocated via the phloem to the roots within 1 hour, with an average phloem transport velocity of 20.3±2.5 cm h(-1). (13)C label was stored in the roots and partially reallocated to the plants' apical part one day after labeling, particularly in the absence of photosynthesis. The daily C loss as BVOC ranged between 1.6% in mature leaves and 7.0% in young leaves. Non-isoprene BVOC accounted under light conditions for half of the BVOC C loss in young leaves and one-third in mature leaves. The C loss as isoprene originated mainly (76-78%) from recently fixed CO(2), to a minor extent from xylem-transported sugars (7-11%) and from photosynthetic intermediates with slower turnover rates (8-11%). We quantified the plants' C loss as respiratory CO(2) and BVOC emissions, allowing in tandem with metabolic analysis to deepen our understanding of ecosystem C flux.

Polar organic compounds in rural PM2.5 aerosols from K-puszta, Hungary, during a 2003 summer field campaign: Sources and diel variations

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A. C. Ion

2005-01-01

Full Text Available In the present study, we examined PM2.5 continental rural background aerosols, which were collected during a summer field campaign at K-puszta, Hungary (4 June-10 July 2003, a mixed coniferous/deciduous forest site characterized by intense solar radiation during summer. Emphasis was placed on polar oxygenated organic compounds that provide information on aerosol sources and source processes. The major components detected at significant atmospheric concentrations were: (a photo-oxidation products of isoprene including the 2-methyltetrols (2-methylthreitol and 2-methylerythritol and 2-methylglyceric acid, (b levoglucosan, a marker for biomass burning, (c malic acid, an intermediate in the oxidation of unsaturated fatty acids, and (d the sugar alcohols, arabitol and mannitol, markers for fungal spores. Diel patterns with highest concentrations during day-time were observed for the 2-methyltetrols, which can be regarded as supporting evidence for their fast photochemical formation from locally emitted isoprene. In addition, a diel pattern with highest concentrations during day-time was observed for the fungal markers, suggesting that the release of fungal fragments that are associated with the PM2.5 aerosol is enhanced during that time. Furthermore, a diel pattern was also found for levoglucosan with the highest concentrations at night when wood burning may take place in the settlements around the sampling site. In contrast, malic acid did not show day/night differences but was found to follow quite closely the particulate and organic carbon mass. This is interpreted as an indication that malic acid is formed in photochemical reactions which have a much longer overall time-scale than that of isoprene photo-oxidation, and the sources of its precursors are manifold, including both anthropogenic and natural emissions. On the basis of the high concentrations found for the isoprene oxidation products during day-time, it can be concluded that rapid photo

Organic aerosol in the summertime southeastern United States: components and their link to volatility distribution, oxidation state and hygroscopicity

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E. Kostenidou

2018-04-01

Full Text Available The volatility distribution of the organic aerosol (OA and its sources during the Southern Oxidant and Aerosol Study (SOAS; Centreville, Alabama was constrained using measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS and a thermodenuder (TD. Positive matrix factorization (PMF analysis was applied on both the ambient and thermodenuded high-resolution mass spectra, leading to four factors: more oxidized oxygenated OA (MO-OOA, less oxidized oxygenated OA (LO-OOA, an isoprene epoxydiol (IEPOX-related factor (isoprene-OA and biomass burning OA (BBOA. BBOA had the highest mass fraction remaining (MFR at 100 °C, followed by the isoprene-OA, and the LO-OOA. Surprisingly the MO-OOA evaporated the most in the TD. The estimated effective vaporization enthalpies assuming an evaporation coefficient equal to unity were 58 ± 13 kJ mol−1 for the LO-OOA, 89 ± 10 kJ mol−1 for the MO-OOA, 55 ± 11 kJ mol−1 for the BBOA, and 63 ± 15 kJ mol−1 for the isoprene-OA. The estimated volatility distribution of all factors covered a wide range including both semi-volatile and low-volatility components. BBOA had the lowest average volatility of all factors, even though it had the lowest O  :  C ratio among all factors. LO-OOA was the more volatile factor and its high MFR was due to its low enthalpy of vaporization according to the model. The isoprene-OA factor had intermediate volatility, quite higher than suggested by a few other studies. The analysis suggests that deducing the volatility of a factor only from its MFR could lead to erroneous conclusions. The oxygen content of the factors can be combined with their estimated volatility and hygroscopicity to provide a better view of their physical properties.

Filters and templates: stonefly (Plecoptera) richness in Ouachita Mountains streams, U.S.A

Science.gov (United States)

Andrew L. Sheldon; Melvin L. Warren

2009-01-01

1. We collected adult stoneflies periodically over a 1-year period at 38 sites in twoheadwater catchments in the Ouachita Mountains, Arkansas, U.S.A. The 43 speciescollected were a subset of the Ozark-Ouachita fauna and the much larger fauna of theeastern U.S.A. We estimated 78–91% species coverage in...

Esthetics evaluation

Science.gov (United States)

Victor A. Rudis; James H. Gramann; Theresa A. Herrick

1994-01-01

An analysis of summer visual attributes and an overview of ongoing scenic quality research within selected shortleaf pine-hardwood stands in the Ouachita and Ozark National forests are presented.Within-stand visual attributes were reported prior to even-aged stand-level (Phase II) treatment for twelve 40-acre stands in the north, east, and south regions and for plot-...

Climate change vulnerabilities within the forestry sector for the Midwestern United States

Science.gov (United States)

Stephen D. Handler; Chris W. Swanston; Patricia R. Butler; Leslie A. Brandt; Maria K. Janowiak; Matthew D. Powers; P. Danielle. Shannon

2014-01-01

Forests are a defining landscape feature for much of the Midwest, from boreal forests surrounding the northern Great Lakes to oak-hickory forests blanketing the Ozarks. Savannas and open woodlands within this region mark a major transition zone between forest and grassland biomes within the U.S. Forests help sustain human communities in the region, ecologically,...

Edge Effects and Ecological Traps: Effects on Shrubland Birds in Missouri

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April A. Woodward; Alix D. Fink; Frank R. Thompson III

2001-01-01

The effect of habitat edge on avian nesting success has been the focus of considerable debate. We studied relationships between habitat edges, locations of nests, and predation. We tested the ecological trap hypothesis for 5 shrubland bird species in the Missouri Ozarks. We compared habitat selection and daily nest predation rates among 3 distance-to-edge categories....

Occurrence and origin of Escherichia coli in water and sediments at two public swimming beaches at Lake of the Ozarks State Park, Camden County, Missouri, 2011-13

Science.gov (United States)

Wilson, Jordan L.; Schumacher, John G.; Burken, Joel G.

2014-01-01

In the past several years, the Missouri Department of Natural Resources has closed two popular public beaches, Grand Glaize Beach and Public Beach 1, at Lake of the Ozarks State Park in Osage Beach, Missouri when monitoring results exceeded the established Escherichia coli (E. coli) standard. As a result of the beach closures, the U.S. Geological Survey and Missouri University of Science and Technology, in cooperation with the Missouri Department of Natural Resources, led an investigation into the occurrence and origins of E. coli at Grand Glaize Beach and Public Beach 1. The study included the collection of more than 1,300 water, sediment, and fecal source samples between August 2011 and February 2013 from the two beaches and vicinity. Spatial and temporal patterns of E. coli concentrations in water and sediments combined with measurements of environmental variables, beach-use patterns, and Missouri Department of Natural Resources water-tracing results were used to identify possible sources of E. coli contamination at the two beaches and to corroborate microbial source tracking (MST) sampling efforts. Results from a 2011 reconnaissance sampling indicate that water samples from Grand Glaize Beach cove contained significantly larger E. coli concentrations than adjacent coves and were largest at sites at the upper end of Grand Glaize Beach cove, indicating a probable local source of E. coli contamination within the upper end of the cove. Results from an intensive sampling effort during 2012 indicated that E. coli concentrations in water samples at Grand Glaize Beach cove were significantly larger in ankle-deep water than waist-deep water, trended downward during the recreational season, significantly increased with an increase in the total number of bathers at the beach, and were largest during the middle of the day. Concentrations of E. coli in nearshore sediment (sediment near the shoreline) at Grand Glaize Beach were significantly larger in foreshore samples

Isoprene emission rates and fluxes measured above a Mediterranean oak ( Quercus pubescens) forest

Science.gov (United States)

Simon, V.; Dumergues, L.; Bouchou, P.; Torres, L.; Lopez, A.

2005-03-01

The present work, carried out as part of the European fiEld experimentS to COnstrain Models of atmospheric Pollution and Transport of Emissions project (ESCOMPTE), brings a new contribution to the inventory of the main natural hydrocarbons sources that are liable to participate in the production of ozone. The measurement campaign was conducted in Montmeyan, a site close to Marseilles (France), with the aim of quantifying the terpenic emission pattern and the behaviour of Quercus pubescens, an important Mediterranean tree species. Biogenic emissions by Q. pubescens were determined by the enclosure of an intact branch of this tree in a Teflon cuvette. The total monoterpenic emission rates thus recorded were found to reach maximum values ranged between 40 and 350 μg g Dry Weight-1 h -1. Emissions were correlated strongly with leaf temperature and Photosynthetic Active Radiation (PAR). The fluxes were also determined by extrapolating the results of the enclosure method and by using aerodynamic gradient method. They reach around 73 mg m -2 h -1 with the first method and 55 mg m -2 h -1 with the second one. The obtained values fit with a maximal ratio of 2.

Electron impact ionization technique on the study of terpenes and related species in French Guiana tropical forest

International Nuclear Information System (INIS)

Lopes, Paula Regina Corain; Bustillos, Oscar W.V.; Guenther, Alex B.; Turnipseed, Andrew A.; Emmons, Louisa; Bonal, Damien; Burban, Benoit; Siebicke, Lukas; Serca, Dominique

2013-01-01

The electron impact ionization is, originally, a mass spectrometry ionization method and still the most widely used of all ionization methods.In this technique, a beam of electrons passes through the gas phase sample. An electron that collides with a neutral analyte molecule can knock off another electron, resulting in a positively charged ion. The fragmentation process dependent sup on many qualities including primary structure, electron energy and ion source temperature. This paper presents a study on the seasonal variation of isoprene and some other significant biogenic volatile organic compounds (BVOC) such as α-pinene, β-pinene, limonene, e-βocimene and longifolene, measured at the Guyaflux Tower located in a wet tropical forest in French Guiana using the Relaxed Eddy Accumulation technique and analyzed by a mass spectrometer coupled to a gas chromatograph, a thermo desorption unit and a flame ionization detector (TD-GC-MS-FID). The results showed that isoprene was by far the biogenic volatile organic compound with the highest concentration and flux, followed by alpha-pinene. Previous limited studies in Amazonia and the Congo suggested that a higher concentration and flux rate of isoprene and alpha-pinene should be expected during the dry season with lower emissions during the wet season, which is in relative agreement with what was observed at this tropical forest site in French Guiana. The exceptions were observed in a long wet period in which the concentration of isoprene and alpha-pinene increased more than it was expected to, for this time of the year. (author)

Electron impact ionization technique on the study of terpenes and related species in French Guiana tropical forest

Energy Technology Data Exchange (ETDEWEB)

Lopes, Paula Regina Corain; Bustillos, Oscar W.V., E-mail: paulinhacorain@usp.br, E-mail: ovega@ipen.br [Instituto de Pesquisa Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Guenther, Alex B.; Turnipseed, Andrew A.; Emmons, Louisa, E-mail: guenther@ucar.edu [Biosphere Atmosphere Interaction Group, Atmosphere Chemistry Division of National Center for Atmospheric Research (NCAR), Boulder, CO (United States); Bonal, Damien; Burban, Benoit; Siebicke, Lukas, E-mail: lukas.siebicke@ecofog.gf [Institut National de la Recherche Agronomique (INRA-UMR EEF), Nancy (France); Serca, Dominique, E-mail: dominique.serca@aero.obs-mip.fr [Universite Paul Sabatier (UPS), Toulouse (France). Laboratoire d' Aerologie

2013-07-01

The electron impact ionization is, originally, a mass spectrometry ionization method and still the most widely used of all ionization methods.In this technique, a beam of electrons passes through the gas phase sample. An electron that collides with a neutral analyte molecule can knock off another electron, resulting in a positively charged ion. The fragmentation process dependent sup on many qualities including primary structure, electron energy and ion source temperature. This paper presents a study on the seasonal variation of isoprene and some other significant biogenic volatile organic compounds (BVOC) such as α-pinene, β-pinene, limonene, e-βocimene and longifolene, measured at the Guyaflux Tower located in a wet tropical forest in French Guiana using the Relaxed Eddy Accumulation technique and analyzed by a mass spectrometer coupled to a gas chromatograph, a thermo desorption unit and a flame ionization detector (TD-GC-MS-FID). The results showed that isoprene was by far the biogenic volatile organic compound with the highest concentration and flux, followed by alpha-pinene. Previous limited studies in Amazonia and the Congo suggested that a higher concentration and flux rate of isoprene and alpha-pinene should be expected during the dry season with lower emissions during the wet season, which is in relative agreement with what was observed at this tropical forest site in French Guiana. The exceptions were observed in a long wet period in which the concentration of isoprene and alpha-pinene increased more than it was expected to, for this time of the year. (author)

Loss of aboveground forest biomass and landscape biomass variability in Missouri, US

Science.gov (United States)

Brice B. Hanberry; Hong S. He; Stephen R. Shifley

2016-01-01

Disturbance regimes and forests have changed over time in the eastern United States. We examined effects of historical disturbance (circa 1813 to 1850) compared to current disturbance (circa 2004 to 2008) on aboveground, live tree biomass (for trees with diameters ≥13 cm) and landscape variation of biomass in forests of the Ozarks and Plains landscapes in Missouri, USA...

Impacts of Potential Oak Forest Change on Breeding Birds in Northwestern Arkansas

Science.gov (United States)

Douglas A. James

2004-01-01

Birds found on existing census routes in the Ozark region of northwestern Arkansas were used to predict avifaunal changes that could occur in the area due to oak-hickory forest degradation caused by red oak borer beetle infestations. The two census routes used passed through high elevation forests where red oaks thrive the best. Analysis showed that 21 bird species...

Understory vegetation composition and abundance in relation to light, water, and nutrient supply gradients in upland oak woodlands

Science.gov (United States)

Elizabeth K. Olson; John M. Kabrick

2014-01-01

The Ozark Highlands of Missouri have experienced a complicated series of exploitive events (Flader 2004). The area was heavily cut over for timber at the turn of the last century and was overgrazed by privately owned livestock through the early 1900s. Decades of fire suppression since the 1940s further altered plant composition and structure. The current state of...

On the use of plant emitted volatile organic compounds for atmospheric chemistry simulation experiments

Science.gov (United States)

Kiendler-Scharr, A.; Hohaus, T.; Yu, Z.; Tillmann, R.; Kuhn, U.; Andres, S.; Kaminski, M.; Wegener, R.; Novelli, A.; Fuchs, H.; Wahner, A.

2015-12-01

Biogenic volatile organic compounds (BVOC) contribute to about 90% of the emitted VOC globally with isoprene being one of the most abundant BVOC (Guenther 2002). Intensive efforts in studying and understanding the impact of BVOC on atmospheric chemistry were undertaken in the recent years. However many uncertainties remain, e.g. field studies have shown that in wooded areas measured OH reactivity can often not be explained by measured BVOC and their oxidation products (e.g. Noelscher et al. 2012). This discrepancy may be explained by either a lack of understanding of BVOC sources or insufficient understanding of BVOC oxidation mechanisms. Plants emit a complex VOC mixture containing likely many compounds which have not yet been measured or identified (Goldstein and Galbally 2007). A lack of understanding BVOC sources limits bottom-up estimates of secondary products of BVOC oxidation such as SOA. Similarly, the widespread oversimplification of atmospheric chemistry in simulation experiments, using single compound or simple BVOC mixtures to study atmospheric chemistry processes limit our ability to assess air quality and climate impacts of BVOC. We will present applications of the new extension PLUS (PLant chamber Unit for Simulation) to our atmosphere simulation chamber SAPHIR. PLUS is used to produce representative BVOC mixtures from direct plant emissions. We will report on the performance and characterization of the newly developed chamber. As an exemplary application, trees typical of a Boreal forest environment were used to compare OH reactivity as directly measured by LIF to the OH reactivity calculated from BVOC measured by GC-MS and PTRMS. The comparison was performed for both, primary emissions of trees without any influence of oxidizing agents and using different oxidation schemes. For the monoterpene emitters investigated here, we show that discrepancies between measured and calculated total OH reactivity increase with increasing degree of oxidation

Exploring Blueberry Aroma Complexity by Chromatographic and Direct-Injection Spectrometric Techniques

Science.gov (United States)

Farneti, Brian; Khomenko, Iuliia; Grisenti, Marcella; Ajelli, Matteo; Betta, Emanuela; Algarra, Alberto Alarcon; Cappellin, Luca; Aprea, Eugenio; Gasperi, Flavia; Biasioli, Franco; Giongo, Lara

2017-01-01

Blueberry (Vaccinium spp.) fruit consumption has increased over the last 5 years, becoming the second most important soft fruit species after strawberry. Despite the possible economic and sensory impact, the blueberry volatile organic compound (VOC) composition has been poorly investigated. Thus, the great impact of the aroma on fruit marketability stimulates the need to step forward in the understanding of this quality trait. Beside the strong effect of ripening, blueberry aroma profile also varies due to the broad genetic differences among Vaccinium species that have been differently introgressed in modern commercial cultivars through breeding activity. In the present study, divided into two different activities, the complexity of blueberry aroma was explored by an exhaustive untargeted VOC analysis, performed by two complementary methods: SPME-GC-MS (solid phase microextraction- gas chromatography-mass spectrometry) and PTR-ToF-MS (proton transfer reaction-time of flight-mass spectrometry). The first experiment was aimed at determining the VOC modifications during blueberry ripening for five commercially representative cultivars (“Biloxi,” “Brigitta Blue,” “Centurion,” “Chandler,” and “Ozark Blue”) harvested at four ripening stages (green, pink, ripe, and over-ripe) to outline VOCs dynamic during fruit development. The objective of the second experiment was to confirm the analytical capability of PTR-ToF-MS to profile blueberry genotypes and to identify the most characterizing VOCs. In this case, 11 accessions belonging to different Vaccinium species were employed: V. corymbosum L. (“Brigitta,” “Chandler,” “Liberty,” and “Ozark Blue”), V. virgatum Aiton (“Centurion,” “Powder Blue,” and “Sky Blue”), V. myrtillus L. (three wild genotypes of different mountain locations), and one accession of V. cylindraceum Smith. This comprehensive characterization of blueberry aroma allowed the identification of a wide pull of VOCs

Exploring Blueberry Aroma Complexity by Chromatographic and Direct-Injection Spectrometric Techniques

Directory of Open Access Journals (Sweden)

Brian Farneti

2017-04-01

Full Text Available Blueberry (Vaccinium spp. fruit consumption has increased over the last 5 years, becoming the second most important soft fruit species after strawberry. Despite the possible economic and sensory impact, the blueberry volatile organic compound (VOC composition has been poorly investigated. Thus, the great impact of the aroma on fruit marketability stimulates the need to step forward in the understanding of this quality trait. Beside the strong effect of ripening, blueberry aroma profile also varies due to the broad genetic differences among Vaccinium species that have been differently introgressed in modern commercial cultivars through breeding activity. In the present study, divided into two different activities, the complexity of blueberry aroma was explored by an exhaustive untargeted VOC analysis, performed by two complementary methods: SPME-GC-MS (solid phase microextraction- gas chromatography-mass spectrometry and PTR-ToF-MS (proton transfer reaction-time of flight-mass spectrometry. The first experiment was aimed at determining the VOC modifications during blueberry ripening for five commercially representative cultivars (“Biloxi,” “Brigitta Blue,” “Centurion,” “Chandler,” and “Ozark Blue” harvested at four ripening stages (green, pink, ripe, and over-ripe to outline VOCs dynamic during fruit development. The objective of the second experiment was to confirm the analytical capability of PTR-ToF-MS to profile blueberry genotypes and to identify the most characterizing VOCs. In this case, 11 accessions belonging to different Vaccinium species were employed: V. corymbosum L. (“Brigitta,” “Chandler,” “Liberty,” and “Ozark Blue”, V. virgatum Aiton (“Centurion,” “Powder Blue,” and “Sky Blue”, V. myrtillus L. (three wild genotypes of different mountain locations, and one accession of V. cylindraceum Smith. This comprehensive characterization of blueberry aroma allowed the identification of a wide

Effect of NOx level on secondary organic aerosol (SOA formation from the photooxidation of terpenes

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R. C. Flagan

2007-10-01

Full Text Available Secondary organic aerosol (SOA formation from the photooxidation of one monoterpene (α-pinene and two sesquiterpenes (longifolene and aromadendrene is investigated in the Caltech environmental chambers. The effect of NOx on SOA formation for these biogenic hydrocarbons is evaluated by performing photooxidation experiments under varying NOx conditions. The NOx dependence of α-pinene SOA formation follows the same trend as that observed previously for a number of SOA precursors, including isoprene, in which SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted decreases as NOx level increases. The NOx dependence of SOA yield for the sesquiterpenes, longifolene and aromadendrene, however, differs from that determined for isoprene and α-pinene; the aerosol yield under high-NOx conditions substantially exceeds that under low-NOx conditions. The reversal of the NOx dependence of SOA formation for the sesquiterpenes is consistent with formation of relatively low-volatility organic nitrates, and/or the isomerization of large alkoxy radicals leading to less volatile products. Analysis of the aerosol chemical composition for longifolene confirms the presence of organic nitrates under high-NOx conditions. Consequently the formation of SOA from certain biogenic hydrocarbons such as sesquiterpenes (and possibly large anthropogenic hydrocarbons as well may be more efficient in polluted air.

Global sensitivity analysis of GEOS-Chem modeled ozone and hydrogen oxides during the INTEX campaigns

Directory of Open Access Journals (Sweden)

K. E. Christian

2018-02-01

Full Text Available Making sense of modeled atmospheric composition requires not only comparison to in situ measurements but also knowing and quantifying the sensitivity of the model to its input factors. Using a global sensitivity method involving the simultaneous perturbation of many chemical transport model input factors, we find the model uncertainty for ozone (O3, hydroxyl radical (OH, and hydroperoxyl radical (HO2 mixing ratios, and apportion this uncertainty to specific model inputs for the DC-8 flight tracks corresponding to the NASA Intercontinental Chemical Transport Experiment (INTEX campaigns of 2004 and 2006. In general, when uncertainties in modeled and measured quantities are accounted for, we find agreement between modeled and measured oxidant mixing ratios with the exception of ozone during the Houston flights of the INTEX-B campaign and HO2 for the flights over the northernmost Pacific Ocean during INTEX-B. For ozone and OH, modeled mixing ratios were most sensitive to a bevy of emissions, notably lightning NOx, various surface NOx sources, and isoprene. HO2 mixing ratios were most sensitive to CO and isoprene emissions as well as the aerosol uptake of HO2. With ozone and OH being generally overpredicted by the model, we find better agreement between modeled and measured vertical profiles when reducing NOx emissions from surface as well as lightning sources.

Characteristics of Biogenic VOCs Emission and its High-Resolution Emission Inventory in China

Science.gov (United States)

Li, L.; Li, Y.; Xie, S.

2017-12-01

Biogenic volatile organic compounds (BVOCs), with high emission and reactivity, can have substantial impacts on the haze and photochemical pollution. It is essential to establish an accurate high-resolution BVOC emission inventory in China for air quality simulation and decision making. Firstly, a semi-static enclosure technique is developed for the field measurements of BVOC emission rates from 50 plant species in China. Using the GC-MS/FID system, 103 VOC species for each plant species are measured. Based on the field measurements in our study and the reported emission rates at home and abroad, a methodology for determining the emission categories of BVOCs is developed using statistical analysis. The isoprene and monoterpene emission rates of 192 plant species/genera in China are determined based on the above emission categories. Secondly, a new vegetation classification with 82 plant functional types (PFTs) is developed based on the most detailed and latest vegetation investigations, China's official statistical data and Vegetation Atlas of China (1:1,000,000). The leaf biomass is estimated based on provincial vegetation volume and production with biomass-apportion models. The WRF model is used to determine meteorological variables at a high spatio-temporal resolution. Using MEAGNv2.1 and the determined emission rates in our study, the high-resolution emission inventories of isoprene, 37 monoterpene species, 32 sesquiterpene species, and other VOCs (OVOCs) from 82 PFTs in China for 1981-2013 are established. The total annual BVOC emissions in 2013 are 55.88 Tg, including 33.87 Tg isoprene, 6.36 Tg monoterpene, 1.29 Tg sesquiterpene, and 14.37 Tg OVOCs. The distribution of isoprene emission fluxes is consistent with the distribution of broadleaf trees, especially tree species with high or higher emission potential. During 1981-2013, China's BVOC emissions have increased by 47.48% at an average rate of 1.80% yr-1. Emissions of isoprene have the largest enhancement

Biogenic volatile organic compounds (BVOCs) emissions from Abies alba in a French forest.

Science.gov (United States)

Moukhtar, S; Couret, C; Rouil, L; Simon, V

2006-02-01

Air quality studies need to be based on accurate and reliable data, particularly in the field of the emissions. Biogenic emissions from forests, crops, and grasslands are now considered as major compounds in photochemical processes. Unfortunately, depending on the type of vegetation, these emissions are not so often reliably defined. As an example, although the silver fir (Abies alba) is a very widespread conifer tree in the French and European areas, its standard emission rate is not available in the literature. This study investigates the isoprene and monoterpenes emission from A. alba in France measured during the fieldwork organised in the Fossé Rhénan, from May to June 2003. A dynamic cuvette method was used. Limonene was the predominant monoterpene emitted, followed by camphene, alpha-pinene and eucalyptol. No isoprene emission was detected. The four monoterpenes measured showed different behaviours according to micrometeorological conditions. In fact, emissions of limonene, alpha-pinene and camphene were temperature-dependant while eucalyptol emissions were temperature and light dependant. Biogenic volatile organic compounds emissions were modeled using information gathered during the field study. Emissions of the three monoterpenes previously quoted were achieved using the monoterpenes algorithm developed by Tingey et al. (1980) [Tingey D, Manning M, Grothaus L, Burns W. Influence of light and temperature on monoterpene emission rates from slash pine. Plant Physiol 1980;65: 797-801.] and the isoprene algorithm [Guenther, A., Monson, R., Fall, R., 1991. Isoprene and monoterpene emission rate variability: observations with eucalyptus and emission rate algorithm development. J Geophys Res 26A: 10799-10808.]; [Guenther, A., Zimmerman, P., Harley, P., Monson, R., Fall, R., 1993. Isoprene and monoterpene emission rate variability: model evaluation and sensitivity analysis. J Geophys Res 98D: 12609-12617.]) was used for the eucalyptol emission. With these

Dithiothreitol activity by particulate oxidizers of SOA produced from photooxidation of hydrocarbons under varied NOx levels

Science.gov (United States)

Jiang, Huanhuan; Jang, Myoseon; Yu, Zechen

2017-08-01

When hydrocarbons (HCs) are atmospherically oxidized, they form particulate oxidizers, including quinones, organic hydroperoxides, and peroxyacyl nitrates (PANs). These particulate oxidizers can modify cellular materials (e.g., proteins and enzymes) and adversely modulate cell functions. In this study, the contribution of particulate oxidizers in secondary organic aerosols (SOAs) to the oxidative potential was investigated. SOAs were generated from the photooxidation of toluene, 1,3,5-trimethylbenzene, isoprene, and α-pinene under varied NOx levels. Oxidative potential was determined from the typical mass-normalized consumption rate (reaction time t = 30 min) of dithiothreitol (DTTt), a surrogate for biological reducing agents. Under high-NOx conditions, the DTTt of toluene SOA was 2-5 times higher than that of the other types of SOA. Isoprene DTTt significantly decreased with increasing NOx (up to 69 % reduction by changing the HC / NOx ratio from 30 to 5). The DTTt of 1,3,5-trimethylbenzene and α-pinene SOA was insensitive to NOx under the experimental conditions of this study. The significance of quinones to the oxidative potential of SOA was tested through the enhancement of DTT consumption in the presence of 2,4-dimethylimidazole, a co-catalyst for the redox cycling of quinones; however, no significant effect of 2,4-dimethylimidazole on modulation of DTT consumption was observed for all SOA, suggesting that a negligible amount of quinones was present in the SOA of this study. For toluene and isoprene, mass-normalized DTT consumption (DTTm) was determined over an extended period of reaction time (t = 2 h) to quantify their maximum capacity to consume DTT. The total quantities of PANs and organic hydroperoxides in toluene SOA and isoprene SOA were also measured using the Griess assay and the 4-nitrophenylboronic acid assay, respectively. Under the NOx conditions (HC / NOx ratio: 5-36 ppbC ppb-1) applied in this study, the amount of organic hydroperoxides was

Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol

Energy Technology Data Exchange (ETDEWEB)

Zaveri, Rahul A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Atmospheric Science and Global Change Div. (ASGC); Shilling, John E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Atmospheric Science and Global Change Div. (ASGC); Zelenyuk, Alla [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Div.; Liu, Jiumeng [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Atmospheric Science and Global Change Div. (ASGC); Bell, David M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Div.; Paul Scherrer Inst. (PSI), Villigen (Switzerland). Lab. of Atmospheric Chemistry; D’Ambro, Emma L. [Univ. of Washington, Seattle, WA (United States). Dept. of Atmospheric Sciences and Dept. of Chemistry; Gaston, Cassandra J. [Univ. of Washington, Seattle, WA (United States). Dept. of Atmospheric Sciences; Univ. of Miami, Miami, FL (United States). Rosenstiel School of Marine and Atmospheric Science; Thornton, Joel A. [Univ. of Washington, Seattle, WA (United States). Dept. of Atmospheric Sciences and Dept. of Chemistry; Laskin, Alexander [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry; Lin, Peng [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry; Wilson, Jacqueline [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Div.; Easter, Richard C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Atmospheric Science and Global Change Div. (ASGC); Wang, Jian [Brookhaven National Lab. (BNL), Upton, NY (United States). Environmental & Climate Sciences Dept.; Bertram, Allan K. [Univ. of British Columbia, Vancouver, BC (Canada). Dept. of Chemistry; Martin, Scot T. [Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Sciences (SEAS) and Dept. of Earth and Planetary Sciences; Seinfeld, John H. [California Inst. of Technology (CalTech), Pasadena, CA (United States). Div. of Chemistry and Chemical Engineering and Div. of Engineering and Applied Science; Worsnop, Douglas R. [Aerodyne Research, Billerica, MA (United States). Center for Aerosol and Cloud Chemistry

2017-12-15

Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. In this article, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversibly reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.

A demographic comparison of two black bear populations in the Interior Highlands of Arkansas

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Clark, Joseph D.; Smith, Kimberly G.

1994-01-01

The Ozark and Ouachita mountain regions of western Arkansas, collectively known as the Interior Highlands, historically supported large numbers of black bears (Ursus americanus). Indiscriminate killing of bears by early settlers and subsequent habitat reductions due to extensive logging and changes in land use resulted in their decline (Smith et al. 1991). By the late 1940's, bears had been extirpated from both regions (Holder 1951).

Regime shifts and weakened environmental gradients in open oak and pine ecosystems.

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Brice B Hanberry

Full Text Available Fire suppression allows tree species that are intolerant of fire stress to increase their distribution, potentially resulting in disruption of historical species-environmental relationships. To measure changes between historical General Land Office surveys (1815 to 1850 and current USDA Forest Inventory and Assessment surveys (2004 to 2008, we compared composition, distribution, and site factors of 21 tree species or species groups in the Missouri Ozarks. We used 24 environmental variables and random forests as a classification method to model distributions. Eastern redcedar, elms, maples, and other fire-sensitive species have increased in dominance in oak forests, with concurrent reductions by oak species; specific changes varied by ecological subsection. Ordinations displayed loss of separation between formerly distinctive oak and fire-sensitive tree species groups. Distribution maps showed decreased presence of disturbance-dependent oak and pine species and increased presence of fire-sensitive species that generally expanded from subsections protected from fire along rivers to upland areas, except for eastern redcedar, which expanded into these subsections. Large scale differences in spatial gradients between past and present communities paralleled reduced influence of local topographic gradients in the varied relief of the Missouri Ozarks, as fire-sensitive species have moved to higher, drier, and sunnier sites away from riverine corridors. Due to changes in land use, landscapes in the Missouri Ozarks, eastern United States, and world-wide are changing from open oak and pine-dominated ecosystems to novel oak-mixed species forests, although at fine scales, forests are becoming more diverse in tree species today. Fire suppression weakened the influence by environmental gradients over species dominance, allowing succession from disturbance-dependent oaks to an alternative state of fire-sensitive species. Current and future research and

Determining contributions of biomass burning and other sources to fine particle contemporary carbon in the western United States

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Holden, Amanda S.; Sullivan, Amy P.; Munchak, Leigh A.; Kreidenweis, Sonia M.; Schichtel, Bret A.; Malm, William C.; Collett, Jeffrey L., Jr.

2011-02-01

Six-day integrated fine particle samples were collected at urban and rural sampling sites using Hi-Volume samplers during winter and summer 2004-2005 as part of the IMPROVE (Interagency Monitoring of PROtected Visual Environments) Radiocarbon Study. Filter samples from six sites (Grand Canyon, Mount Rainier, Phoenix, Puget Sound, Rocky Mountain National Park, and Tonto National Monument) were analyzed for levoglucosan, a tracer for biomass combustion, and other species by High-Performance Anion-Exchange Chromatography with Pulsed Amperometric Detection (HPAEC-PAD). Contemporary carbon concentrations were available from previous carbon isotope measurements at Lawrence Livermore National Laboratory. Primary contributions of biomass burning to measured fine particle contemporary carbon were estimated for residential wood burning (winter) and wild/prescribed fires (summer). Calculated contributions ranged from below detection limit to more than 100% and were typically higher at rural sites and during winter. Mannitol, a sugar alcohol emitted by fungal spores, was analyzed and used to determine contributions of fungal spores to fine particle contemporary carbon. Contributions reached up to 13% in summer samples, with higher contributions at rural sites. Concentrations of methyltetrols, oxidation products of isoprene, were also measured by HPAEC-PAD. Secondary organic aerosol (SOA) from isoprene oxidation was estimated to contribute up to 22% of measured contemporary carbon. For each sampling site, a substantial portion of the contemporary carbon was unexplained by primary biomass combustion, fungal spores, or SOA from isoprene oxidation. This unexplained fraction likely contains contributions from other SOA sources, including oxidation products of primary smoke emissions and plant emissions other than isoprene, as well as other primary particle emissions from meat cooking, plant debris, other biological aerosol particles, bio-diesel combustion, and other sources. Loss

Nine years of global hydrocarbon emissions based on source inversion of OMI formaldehyde observations

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M. Bauwens

2016-08-01

Full Text Available As formaldehyde (HCHO is a high-yield product in the oxidation of most volatile organic compounds (VOCs emitted by fires, vegetation, and anthropogenic activities, satellite observations of HCHO are well-suited to inform us on the spatial and temporal variability of the underlying VOC sources. The long record of space-based HCHO column observations from the Ozone Monitoring Instrument (OMI is used to infer emission flux estimates from pyrogenic and biogenic volatile organic compounds (VOCs on the global scale over 2005–2013. This is realized through the method of source inverse modeling, which consists in the optimization of emissions in a chemistry-transport model (CTM in order to minimize the discrepancy between the observed and modeled HCHO columns. The top–down fluxes are derived in the global CTM IMAGESv2 by an iterative minimization algorithm based on the full adjoint of IMAGESv2, starting from a priori emission estimates provided by the newly released GFED4s (Global Fire Emission Database, version 4s inventory for fires, and by the MEGAN-MOHYCAN inventory for isoprene emissions. The top–down fluxes are compared to two independent inventories for fire (GFAS and FINNv1.5 and isoprene emissions (MEGAN-MACC and GUESS-ES. The inversion indicates a moderate decrease (ca. 20 % in the average annual global fire and isoprene emissions, from 2028 Tg C in the a priori to 1653 Tg C for burned biomass, and from 343 to 272 Tg for isoprene fluxes. Those estimates are acknowledged to depend on the accuracy of formaldehyde data, as well as on the assumed fire emission factors and the oxidation mechanisms leading to HCHO production. Strongly decreased top–down fire fluxes (30–50 % are inferred in the peak fire season in Africa and during years with strong a priori fluxes associated with forest fires in Amazonia (in 2005, 2007, and 2010, bushfires in Australia (in 2006 and 2011, and peat burning in Indonesia (in 2006 and 2009, whereas

Medical tourism in the backcountry: alternative health and healing in the Arkansas Ozarks.

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Nolan, Justin M; Schneider, Mary Jo

2011-01-01

Tourists travel to Arkansas' mountain regions to experience, appreciate, and consume multiple aspects of otherness, including sacred sites and pristine and authentic peoples and environments. A largely unexplored aspect of this consumption of authenticity is alternative medicine, provided to tourists and day travelers in search of physical and emotional restoration. Traditional forms of medicine are deeply rooted in women's social roles as community healers in the region and are perpetuated in part because of the lack of readily accessible forms of so-called modern medicine. Contemporary medical tourism in Arkansas has promoted access to folk health systems, preserving them by incorporating them into tourists' health care services, and also has attracted new and dynamic alternative medical practices while encouraging the transformation of existing forms of traditional medicine. Ultimately, the blend of alternative, folk, and conventional medicine in the Arkansas highlands is evidence of globalizing forces at work in a regional culture. It also serves to highlight a renewed appreciation for the historic continuity and the efficacy of traditional knowledge in the upper South.

Radiation treatment of polymers containing isobutylene

International Nuclear Information System (INIS)

Shurpik, A.

1976-01-01

Homopolymers of isobutylene and copolymers thereof with isoprene (butyl rubber) are subjected to high energy ionizing radiation in the presence of halogenated hydrocarbon radiation catalysts. 5 claims

Contribution of biogenic and photochemical sources to ambient VOCs during winter to summer transition at a semi-arid urban site in India.

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Sahu, L K; Tripathi, Nidhi; Yadav, Ravi

2017-10-01

This paper presents the sources and characteristics of ambient volatile organic compounds (VOCs) measured using PTR-TOF-MS instrument in a metropolitan city of India during winter to summer transition period. Mixing ratios of VOCs exhibited strong diurnal, day-to-day and episodic variations. Methanol was the most dominant species with monthly mean values of 18-22 pbbv. The emission ratios of VOCs relative to benzene calculated from nighttime data were used to estimate the relative contributions of vehicle exhaust and other sources. The increasing daytime ratios of oxygenated-VOCs (OVOCs)/benzene and isoprene/benzene from February to March indicates increasing contribution of photo-oxidation and biogenic sources. Daytime fractions of acetone (18%), acetaldehyde (15%) and isoprene (4.5%) to the sum of measured VOCs in March were higher than those in February. Variations of VOCs at lower temperatures (biogenic emissions. The emissions of OVOCs from vehicle exhaust were estimated to be smaller (20-40%) than those from other sources. The contributions of biogenic and secondary sources to OVOCs and isoprene increased by 10-15% from winter to summer. This study provides evidence that the winter-to-summer transition has an impact on sources and composition of VOCs in tropical urban areas. Copyright © 2017 Elsevier Ltd. All rights reserved.

Impacts of Interannual Variability in Biogenic VOC Emissions near Transitional Ozone Production Regimes

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Geddes, J.

2017-12-01

Due to successful NOx emission controls, summertime ozone production chemistry in urban areas across North America is transitioning from VOC-limited to increasingly NOx-limited. In some regions where ozone production sensitivity is in transition, interannual variability in surrounding biogenic VOC emissions could drive fluctuations in the prevailing chemical regime and modify the impact of anthropogenic emission changes. I use satellite observations of HCHO and NO2 column density, along with a long-term simulation of atmospheric chemistry, to investigate the impact of interannual variability in biogenic isoprene sources near large metro areas. Peak emissions of isoprene in the model can vary by up to 20-60% in any given year compared to the long term mean, and this variability drives the majority of the variability in simulated local HCHO:NO2 ratios (a common proxy for ozone production sensitivity). The satellite observations confirm increasingly NOx-limited chemical regimes with large interannual variability. In several instances, the model and satellite observations suggest that variability in biogenic isoprene emissions could shift summertime ozone production from generally VOC- to generally NOx- sensitive (or vice versa). This would have implications for predicting the air quality impacts of anthropogenic emission changes in any given year, and suggests that drivers of biogenic emissions need to be well understood.

Volatile Organic Compounds and Oxidation Capacity of the Atmosphere in the Brazilian Amazon during the GoAmazon2014/5 Campaign

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Seco, R.; Jeong, D.; Kim, S.; Park, J. H.; Sjostedt, S. J.; Guenther, A. B.; Smith, J. N.; Liu, Y.; Gu, D.; Bustillos, J. O. V.; Tota, J.; Souza, R. A. F. D.; Martin, S. T.

2015-12-01

Atmospheric volatile organic compounds (VOCs) have key environmental and biological roles, and can influence atmospheric chemistry, secondary aerosol formation, and also regional climate. The GoAmazon2014/5 campaign included measurements of VOCs in pristine to polluted air of the Amazon basin, depending upon the influences from the pollution plumes originating in the city of Manaus, Brazil. Observations at the T3 site in Manacapuru during the second Intensive Operating Period (dry season, August-October 2014) using a Switchable Reagent Ion (SRI)-ToF-MS will be presented to investigate isoprene oxidation processes in a wide spectrum of anthropogenic influences. The SRI capability was utilized to quantify ratios of Methyl Vinyl Ketone (MVK) to Methacrolein (MACR) in order to assess photochemical age of air masses at T3 and examine isoprene peroxy radical reaction pathways as a function of NO levels. Given recently identified ISOPOOH interference to MVK and MACR measurements, the current analysis focus on high NOx conditions when the contribution of ISOPOOH was small. In addition, the results will be critically compared with previously reported relationships between MVK, MACR and isoprene to explore potential systematic analytical interferences that may affect regional OH level estimations. These OH estimates will be evaluated using in-situ OH observations.

FEV manoeuvre induced changes in breath VOC compositions: an unconventional view on lung function tests

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Sukul, Pritam; Schubert, Jochen K.; Oertel, Peter; Kamysek, Svend; Taunk, Khushman; Trefz, Phillip; Miekisch, Wolfram

2016-06-01

Breath volatile organic compound (VOC) analysis can open a non-invasive window onto pathological and metabolic processes in the body. Decades of clinical breath-gas analysis have revealed that changes in exhaled VOC concentrations are important rather than disease specific biomarkers. As physiological parameters, such as respiratory rate or cardiac output, have profound effects on exhaled VOCs, here we investigated VOC exhalation under respiratory manoeuvres. Breath VOCs were monitored by means of real-time mass-spectrometry during conventional FEV manoeuvres in 50 healthy humans. Simultaneously, we measured respiratory and hemodynamic parameters noninvasively. Tidal volume and minute ventilation increased by 292 and 171% during the manoeuvre. FEV manoeuvre induced substance specific changes in VOC concentrations. pET-CO2 and alveolar isoprene increased by 6 and 21% during maximum exhalation. Then they decreased by 18 and 37% at forced expiration mirroring cardiac output. Acetone concentrations rose by 4.5% despite increasing minute ventilation. Blood-borne furan and dimethyl-sulphide mimicked isoprene profile. Exogenous acetonitrile, sulphides, and most aliphatic and aromatic VOCs changed minimally. Reliable breath tests must avoid forced breathing. As isoprene exhalations mirrored FEV performances, endogenous VOCs might assure quality of lung function tests. Analysis of exhaled VOC concentrations can provide additional information on physiology of respiration and gas exchange.

Dithiothreitol activity by particulate oxidizers of SOA produced from photooxidation of hydrocarbons under varied NOx levels

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H. Jiang

2017-08-01

Full Text Available When hydrocarbons (HCs are atmospherically oxidized, they form particulate oxidizers, including quinones, organic hydroperoxides, and peroxyacyl nitrates (PANs. These particulate oxidizers can modify cellular materials (e.g., proteins and enzymes and adversely modulate cell functions. In this study, the contribution of particulate oxidizers in secondary organic aerosols (SOAs to the oxidative potential was investigated. SOAs were generated from the photooxidation of toluene, 1,3,5-trimethylbenzene, isoprene, and α-pinene under varied NOx levels. Oxidative potential was determined from the typical mass-normalized consumption rate (reaction time t =  30 min of dithiothreitol (DTTt, a surrogate for biological reducing agents. Under high-NOx conditions, the DTTt of toluene SOA was 2–5 times higher than that of the other types of SOA. Isoprene DTTt significantly decreased with increasing NOx (up to 69 % reduction by changing the HC ∕ NOx ratio from 30 to 5. The DTTt of 1,3,5-trimethylbenzene and α-pinene SOA was insensitive to NOx under the experimental conditions of this study. The significance of quinones to the oxidative potential of SOA was tested through the enhancement of DTT consumption in the presence of 2,4-dimethylimidazole, a co-catalyst for the redox cycling of quinones; however, no significant effect of 2,4-dimethylimidazole on modulation of DTT consumption was observed for all SOA, suggesting that a negligible amount of quinones was present in the SOA of this study. For toluene and isoprene, mass-normalized DTT consumption (DTTm was determined over an extended period of reaction time (t =  2 h to quantify their maximum capacity to consume DTT. The total quantities of PANs and organic hydroperoxides in toluene SOA and isoprene SOA were also measured using the Griess assay and the 4-nitrophenylboronic acid assay, respectively. Under the NOx conditions (HC ∕ NOx ratio: 5–36 ppbC ppb−1 applied in

A comprehensive emission inventory of biogenic volatile organic compounds in Europe: improved seasonality and land-cover

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D. C. Oderbolz

2013-02-01

Full Text Available Biogenic volatile organic compounds (BVOC emitted from vegetation are important for the formation of secondary pollutants such as ozone and secondary organic aerosols (SOA in the atmosphere. Therefore, BVOC emission are an important input for air quality models. To model these emissions with high spatial resolution, the accuracy of the underlying vegetation inventory is crucial. We present a BVOC emission model that accommodates different vegetation inventories and uses satellite-based measurements of greenness instead of pre-defined vegetation periods. This approach to seasonality implicitly treats effects caused by water or nutrient availability, altitude and latitude on a plant stand. Additionally, we test the influence of proposed seasonal variability in enzyme activity on BVOC emissions. In its present setup, the emission model calculates hourly emissions of isoprene, monoterpenes, sesquiterpenes and the oxygenated volatile organic compounds (OVOC methanol, formaldehyde, formic acid, ethanol, acetaldehyde, acetone and acetic acid. In this study, emissions based on three different vegetation inventories are compared with each other and diurnal and seasonal variations in Europe are investigated for the year 2006. Two of these vegetation inventories require information on tree-cover as an input. We compare three different land-cover inventories (USGS GLCC, GLC2000 and Globcover 2.2 with respect to tree-cover. The often-used USGS GLCC land-cover inventory leads to a severe reduction of BVOC emissions due to a potential miss-attribution of broad-leaved trees and reduced tree-cover compared to the two other land-cover inventories. To account for uncertainties in the land-cover classification, we introduce land-cover correction factors for each relevant land-use category to adjust the tree-cover. The results are very sensitive to these factors within the plausible range. For June 2006, total monthly BVOC emissions decreased up to −27% with

Differences found in the macroinvertebrate community composition in the presence or absence of the invasive alien crayfish, Orconectes hylas

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Freeland-Riggert, Brandye T.; Cairns, Stefan H.; Poulton, Barry C.; Riggert, Chris M.

2016-01-01

Introductions of alien species into aquatic ecosystems have been well documented, including invasions of crayfish species; however, little is known about the effects of these introductions on macroinvertebrate communities. The woodland crayfish (Orconectes hylas (Faxon)) has been introduced into the St. Francis River watershed in southeast Missouri and has displaced populations of native crayfish. The effects of O. hylas on macroinvertebrate community composition were investigated in a fourth-order Ozark stream at two locations, one with the presence of O. hylas and one without. Significant differences between sites and across four sampling periods and two habitats were found in five categories of benthic macroinvertebrate metrics: species richness, percent/composition, dominance/diversity, functional feeding groups, and biotic indices. In most seasons and habitat combinations, the invaded site had significantly higher relative abundance of riffle beetles (Coleoptera: Elmidae), and significantly lower Missouri biotic index values, total taxa richness, and both richness and relative abundance of midges (Diptera: Chironomidae). Overall study results indicate that some macroinvertebrate community differences due to the O. hylas invasion were not consistent between seasons and habitats, suggesting that further research on spatial and temporal habitat use and feeding ecology of Ozark crayfish species is needed to improve our understanding of the effects of these invasions on aquatic communities.

Updated aerosol module and its application to simulate secondary organic aerosols during IMPACT campaign May 2008

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Y. P. Li

2013-07-01

Full Text Available The formation of Secondary organic aerosol (SOA was simulated with the Secondary ORGanic Aerosol Model (SORGAM by a classical gas-particle partitioning concept, using the two-product model approach, which is widely used in chemical transport models. In this study, we extensively updated SORGAM including three major modifications: firstly, we derived temperature dependence functions of the SOA yields for aromatics and biogenic VOCs (volatile organic compounds, based on recent chamber studies within a sophisticated mathematic optimization framework; secondly, we implemented the SOA formation pathways from photo oxidation (OH initiated of isoprene; thirdly, we implemented the SOA formation channel from NO3-initiated oxidation of reactive biogenic hydrocarbons (isoprene and monoterpenes. The temperature dependence functions of the SOA yields were validated against available chamber experiments, and the updated SORGAM with temperature dependence functions was evaluated with the chamber data. Good performance was found with the normalized mean error of less than 30%. Moreover, the whole updated SORGAM module was validated against ambient SOA observations represented by the summed oxygenated organic aerosol (OOA concentrations abstracted from aerosol mass spectrometer (AMS measurements at a rural site near Rotterdam, the Netherlands, performed during the IMPACT campaign in May 2008. In this case, we embedded both the original and the updated SORGAM module into the EURopean Air pollution and Dispersion-Inverse Model (EURAD-IM, which showed general good agreements with the observed meteorological parameters and several secondary products such as O3, sulfate and nitrate. With the updated SORGAM module, the EURAD-IM model also captured the observed SOA concentrations reasonably well especially those during nighttime. In contrast, the EURAD-IM model before update underestimated the observations by a factor of up to 5. The large improvements of the modeled

Geohydrologic Investigations and Landscape Characteristics of Areas Contributing Water to Springs, the Current River, and Jacks Fork, Ozark National Scenic Riverways, Missouri

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Mugel, Douglas N.; Richards, Joseph M.; Schumacher, John G.

2009-01-01

The Ozark National Scenic Riverways (ONSR) is a narrow corridor that stretches for approximately 134 miles along the Current River and Jacks Fork in southern Missouri. Most of the water flowing in the Current River and Jacks Fork is discharged to the rivers from springs within the ONSR, and most of the recharge area of these springs is outside the ONSR. This report describes geohydrologic investigations and landscape characteristics of areas contributing water to springs and the Current River and Jacks Fork in the ONSR. The potentiometric-surface map of the study area for 2000-07 shows that the groundwater divide extends beyond the surface-water divide in some places, notably along Logan Creek and the northeastern part of the study area, indicating interbasin transfer of groundwater between surface-water basins. A low hydraulic gradient occurs in much of the upland area west of the Current River associated with areas of high sinkhole density, which indicates the presence of a network of subsurface karst conduits. The results of a low base-flow seepage run indicate that most of the discharge in the Current River and Jacks Fork was from identified springs, and a smaller amount was from tributaries whose discharge probably originated as spring discharge, or from springs or diffuse groundwater discharge in the streambed. Results of a temperature profile conducted on an 85-mile reach of the Current River indicate that the lowest average temperatures were within or downstream from inflows of springs. A mass-balance on heat calculation of the discharge of Bass Rock Spring, a previously undescribed spring, resulted in an estimated discharge of 34.1 cubic feet per second (ft3/s), making it the sixth largest spring in the Current River Basin. The 13 springs in the study area for which recharge areas have been estimated accounted for 82 percent (867 ft3/s of 1,060 ft3/s) of the discharge of the Current River at Big Spring during the 2006 seepage run. Including discharge from

Design and Synthesis of Network-Forming Triblock Copolymers Using Tapered Block Interfaces

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Kuan, Wei-Fan; Roy, Raghunath; Rong, Lixia; Hsiao, Benjamin S.; Epps, Thomas H.

2012-01-01

We report a strategy for generating novel dual-tapered poly(isoprene-b-isoprene/styrene-b-styrene-b-styrene/methyl methacrylate-b-methyl methacrylate) [P(I-IS-S-SM-M)] triblock copolymers that combines anionic polymerization, atom transfer radical polymerization (ATRP), and Huisgen 1,3-dipolar cycloaddition click chemistry. The tapered interfaces between blocks were synthesized via a semi-batch feed using programmable syringe pumps. This strategy allows us to manipulate the transition region between copolymer blocks in triblock copolymers providing control over the interfacial interactions in our nanoscale phase-separated materials independent of molecular weight and block constituents. Additionally, we show the ability to retain a desirous and complex multiply-continuous network structure (alternating gyroid) in our dual-tapered triblock material. PMID:23066522

Physical stream habitat dynamics in Lower Bear Creek, northern Arkansas

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Reuter, Joanna M.; Jacobson, Robert B.; Elliott, Caroline M.

2003-01-01

We evaluated the roles of geomorphic and hydrologic dynamics in determining physical stream habitat in Bear Creek, a stream with a 239 km2 drainage basin in the Ozark Plateaus (Ozarks) in northern Arkansas. During a relatively wet 12-month monitoring period, the geomorphology of Bear Creek was altered by a series of floods, including at least four floods with peak discharges exceeding a 1-year recurrence interval and another flood with an estimated 2- to 4-year recurrence interval. These floods resulted in a net erosion of sediment from the study reach at Crane Bottom at rates far in excess of other sites previously studied in the Ozarks. The riffle-pool framework of the study reach at Crane Bottom was not substantially altered by these floods, but volumes of habitat in riffles and pools changed. The 2- to 4-year flood scoured gravel from pools and deposited it in riffles, increasing the diversity of available stream habitat. In contract, the smaller floods eroded gravel from the riffles and deposited it in pools, possibly flushing fine sediment from the substrate but also decreasing habitat diversity. Channel geometry measured at the beginning of the study was use to develop a two-dimensional, finite-element hydraulic model at assess how habitat varies with hydrologic dynamics. Distributions of depth and velocity simulated over the range of discharges observed during the study (0.1 to 556 cubic meters per second, cms) were classified into habitat units based on limiting depths and Froude number criteria. The results indicate that the areas of habitats are especially sensitive to change to low to medium flows. Races (areas of swift, relatively deep water downstream from riffles) disappear completely at the lowest flows, and riffles (areas of swift, relatively shallow water) contract substantially in area. Pools also contract in area during low flow, but deep scours associated with bedrock outcrops sustain some pool area even at the lowest modeled flows. Modeled

Sustainable bioenergy production from Missouri's Ozark forests

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Henry E. Stelzer; Chris Barnett; Verel W. Bensen

2008-01-01

The main source of wood fiber for energy resides in Missouri's forests. Alternative bioenergy systems that can use forest thinning residues are electrical energy, thermal energy, and liquid bio-fuel. By applying a thinning rule and accounting for wood fiber that could go into higher value wood products to all live biomass data extracted from the U.S. Forest...

Well-Defined Cyclic Triblock Terpolymers: A Missing Piece of the Morphology Puzzle

KAUST Repository

Polymeropoulos, George; Bilalis, Panayiotis; Hadjichristidis, Nikolaos

2016-01-01

Two well-defined cyclic triblock terpolymers, missing pieces of the terpolymer morphology puzzle, consisting of poly(isoprene), polystyrene, and poly(2-vinylpyridine), were synthesized by combining the Glaser coupling reaction with anionic

Long-term measurement of terpenoid flux above a Larix kaempferi forest using a relaxed eddy accumulation method

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Mochizuki, Tomoki; Tani, Akira; Takahashi, Yoshiyuki; Saigusa, Nobuko; Ueyama, Masahito

2014-02-01

Terpenoids emitted from forests contribute to the formation of secondary organic aerosols and affect the carbon budgets of forest ecosystems. To investigate seasonal variation in terpenoid flux involved in the aerosol formation and carbon budget, we measured the terpenoid flux of a Larix kaempferi forest between May 2011 and May 2012 by using a relaxed eddy accumulation method. Isoprene was emitted from a fern plant species Dryopteris crassirhizoma on the forest floor and monoterpenes from the L. kaempferi. α-Pinene was the dominant compound, but seasonal variation of the monoterpene composition was observed. High isoprene and monoterpene fluxes were observed in July and August. The total monoterpene flux was dependent on temperature, but several unusual high positive fluxes were observed after rain fall events. We found a good correlation between total monoterpene flux and volumetric soil water content (r = 0.88), and used this correlation to estimate monoterpene flux after rain events and calculate annual terpenoid emissions. Annual carbon emission in the form of total monoterpenes plus isoprene was determined to be 0.93% of the net ecosystem exchange. If we do not consider the effect of rain fall, carbon emissions may be underestimated by about 50%. Our results suggest that moisture conditions in the forest soil is a key factor controlling the monoterpene emissions from the forest ecosystem.

Oxidative potential of secondary organic aerosols produced from photooxidation of different hydrocarbons using outdoor chamber under ambient sunlight

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Jiang, Huanhuan; Jang, Myoseon; Sabo-Attwood, Tara; Robinson, Sarah E.

2016-04-01

The oxidative potential of various secondary organic aerosols (SOA) was measured using dithiothreitol (DTT) assay to understand how organic aerosols react with cellular materials. SOA was produced via the photooxidation of four different hydrocarbons (toluene, 1,3,5-trimethylbenzene, isoprene and α-pinene) in the presence of NOx using a large outdoor photochemical smog chamber. The DTT consumption rate was normalized by the aerosol mass, which is expressed as DTTmass. Toluene SOA and isoprene SOA yielded higher DTTmass than 1,3,5-trimethylbenzene SOA or α-pinene SOA. In order to discover the correlation between the molecular structure and oxidative potential, the DTT responses of selected model compounds were also measured. Among them, conjugated aldehydes, quinones, and H2O2 showed considerable DTT response. To investigate the correlation between DTT response and cell responses in vitro, the expression of biological markers, i.e. IL-6, IL-8, and HMOX-1 were studied using small airway epithelial cells. Higher cellular expression of IL-8 was observed with toluene SOA exposure compared to 1,3,5-trimethylbenzene SOA exposure, which aligned with the results from DTT assay. Our study also suggests that within the urban atmosphere, the contribution of toluene SOA and isoprene SOA to the oxidative potential of ambient SOA will be more significant than that of α-pinene SOA.

Continuation of the Resource Conservation and Development Program Raises Questions.

Science.gov (United States)

1981-08-11

almost any measure proposed to be counted toward helping accomplish the plan’s objectives and furthering its goals. SOME PLANS ARE NOT UP TO DATE...FUNDS THEY HAD RECEIVED AS OF SEPTEMBER 1980 Year Project project Amount area (State) authorized received (000 omitted) Sangre de Cristo (Colo.) 1968...Minn.) 1975 711 Northeast (miss.) 1967 4,605 Southeast (Miss.) 1971 1,868 Top of the Ozarks (Mo.) 1965 1,954 Bitter Root Valley ( Mont .) 1965 2,605

Simulation of the interannual variations of biogenic emissions of volatile organic compounds in China: Impacts on tropospheric ozone and secondary organic aerosol

Science.gov (United States)

Fu, Y.; Liao, H.

2012-12-01

We use the MEGAN (Model of emissions of Gases and Aerosols from Nature) module embedded within the global three-dimensional Goddard Earth Observing System chemical transport model (GEOS-Chem) to simulate the interannual variations in biogenic volatile organic compound (BVOC) emissions and concentrations of ozone and secondary organic aerosols (SOA) in China over years 2001-2006. To have better representation of biogenic emissions, we have updated in the model the land cover and leaf area index in China using Moderate Resolution Imaging Spectroradiometer (MODIS) satellite measurements, and we have developed a new classification of vegetation with 21 plant functional types. Estimated annual BVOC emission in China averaged over 2001-2006 is 18.85 Tg C yr-1, in which emissions of isoprene, monoterpenes, and other reactive volatile organic compounds account for 50.9%, 15.0%, and 34.1%, respectively. The simulated BVOC emissions in China have large interannual variations. The values of regionally averaged absolute percent departure from the mean (APDM) of isoprene emissions are in the range of 21-42% in January and 15-28% in July. The APDM values of monoterpene emissions are 14-32% in January and 10-21% in July, which are generally smaller than those of isoprene emissions. Model results indicate that the interannual variations in isoprene emissions are more dependent on variations in meteorological fields, whereas the interannual variations in monoterpene emissions are more sensitive to changes in vegetation parameters. With fixed anthropogenic emissions, as a result of the variations in both meteorological parameters and vegetation, simulated O3 concentrations show interannual variations of 0.8-5 ppbv (or largest APDM values of 4-15%), and simulated SOA shows APDM values of 5-15% in southwestern China in January as well as 10-25% in southeastern and 20-35% in northeastern China in July. On a regional mean basis, the interannual variations in BVOCs alone can lead to 2

Biogenic volatile organic compound (BVOC) emissions from forested areas in Turkey: determination of specific emission rates for thirty-one tree species.

Science.gov (United States)

Aydin, Yagmur Meltem; Yaman, Baris; Koca, Husnu; Dasdemir, Okan; Kara, Melik; Altiok, Hasan; Dumanoglu, Yetkin; Bayram, Abdurrahman; Tolunay, Doganay; Odabasi, Mustafa; Elbir, Tolga

2014-08-15

Normalized biogenic volatile organic compound (BVOC) emission rates for thirty one tree species that cover the 98% of national forested areas in Turkey were determined. Field samplings were performed at fourteen different forested areas in Turkey using a specific dynamic enclosure system. The selected branches of tree species were enclosed in a chamber consisted of a transparent Nalofan bag. The air-flows were sampled from both inlet and outlet of the chamber by Tenax-filled sorbent tubes during photosynthesis of trees under the presence of sunlight. Several environmental parameters (temperature, humidity, photosynthetically active radiation-PAR, and CO2) were continuously monitored inside and outside the enclosure chamber during the samplings. Collected samples were analyzed using a gas chromatography mass spectrometry (GC/MS) system equipped with a thermal desorber (TD). Sixty five BVOCs classified in five major groups (isoprene, monoterpenes, sesquiterpenes, oxygenated sesquiterpenes, and other oxygenated compounds) were analyzed. Emission rates were determined by normalization to standard conditions (1000 μmol/m(2)s PAR and 30 °C temperature for isoprene and 30 °C temperature for the remaining compounds). In agreement with the literature, isoprene was mostly emitted by broad-leaved trees while coniferous species mainly emitted monoterpenes. Several tree species such as Sweet Chestnut, Silver Lime, and European Alder had higher monoterpene emissions although they are broad-leaved species. High isoprene emissions were also observed for a few coniferous species such as Nordmann Fir and Oriental Spruce. The highest normalized total BVOC emission rate of 27.1 μg/gh was observed for Oriental Plane while South European Flowering Ash was the weakest BVOC emitter with a total normalized emission rate of 0.031 μg/gh. Monoterpene emissions of broad-leaved species mainly consisted of sabinene, limonene and trans-beta-ocimene, while alpha-pinene, beta-pinene and beta

Comparison of regional and global land cover products and the implications for biogenic emission modeling.

Science.gov (United States)

Huang, Ling; McDonald-Buller, Elena; McGaughey, Gary; Kimura, Yosuke; Allen, David T

2015-10-01

Accurate estimates of biogenic emissions are required for air quality models that support the development of air quality management plans and attainment demonstrations. Land cover characterization is an essential driving input for most biogenic emissions models. This work contrasted the global Moderate Resolution Imaging Spectroradiometer (MODIS) land cover product against a regional land cover product developed for the Texas Commissions on Environmental Quality (TCEQ) over four climate regions in eastern Texas, where biogenic emissions comprise a large fraction of the total inventory of volatile organic compounds (VOCs) and land cover is highly diverse. The Model of Emissions of Gases and Aerosols from Nature (MEGAN) was utilized to investigate the influences of land cover characterization on modeled isoprene and monoterpene emissions through changes in the standard emission potential and emission activity factor, both separately and simultaneously. In Central Texas, forest coverage was significantly lower in the MODIS land cover product relative to the TCEQ data, which resulted in substantially lower estimates of isoprene and monoterpene emissions by as much as 90%. Differences in predicted isoprene and monoterpene emissions associated with variability in land cover characterization were primarily caused by differences in the standard emission potential, which is dependent on plant functional type. Photochemical modeling was conducted to investigate the effects of differences in estimated biogenic emissions associated with land cover characterization on predicted ozone concentrations using the Comprehensive Air Quality Model with Extensions (CAMx). Mean differences in maximum daily average 8-hour (MDA8) ozone concentrations were 2 to 6 ppb with maximum differences exceeding 20 ppb. Continued focus should be on reducing uncertainties in the representation of land cover through field validation. Uncertainties in the estimation of biogenic emissions associated with

Concentrations and fluxes of biogenic volatile organic compounds above a Mediterranean macchia ecosystem in western Italy

Directory of Open Access Journals (Sweden)

B. Davison

2009-08-01

Full Text Available Emission rates and concentrations of biogenic volatile organic compounds (BVOCs were measured at a Mediterranean coastal site at Castelporziano, approximately 25 km south-west of Rome, between 7 May and 3 June 2007, as part of the ACCENT-VOCBAS field campaign on biosphere–atmosphere interactions. Concentrations and emission rates were measured using the disjunct eddy covariance (DEC method utilizing three different proton transfer reaction mass spectrometers (PTR-MS so allowing a comparison between the instruments. The high resolution data from the PTR-MS instruments considerably enhances the original BEMA measurements of the mid 1990s.

Depending on the measurement period, the volume mixing ratios were in the range 1.6–3.5 ppbv for methanol, 0.44–1.3 ppbv for acetaldehyde, 0.96–2.1 ppbv for acetone, 0.10–0.14 ppbv for isoprene, and 0.13–0.30 ppbv for monoterpenes. A diurnal cycle in mixing ratios was apparent with daytime maxima for methanol, acetaldehyde, acetone, and isoprene. The fluxes ranged from 370–440 μg m⁻² h⁻¹ for methanol, 180–360 μg m⁻² h⁻¹ for acetaldehyde, 180–450 μg m⁻² h⁻¹ for acetone, 71–290 μg m⁻² h⁻¹ for isoprene, and 240–860 μg m⁻² h⁻¹ for monoterpenes. From the measured flux data (7 May–3 June an average basal emission rate for the Macchia vegetation was calculated of 430 μg m⁻² h⁻¹ for isoprene and 1100 μg m⁻² h⁻¹ for monoterpenes.

Designing block copolymer architectures for targeted membrane performance

KAUST Repository

Dorin, Rachel Mika; Phillip, William A.; Sai, Hiroaki; Werner, Jö rg; Elimelech, Menachem; Wiesner, Ulrich

2014-01-01

Using a combination of block copolymer self-assembly and non-solvent induced phase separation, isoporous ultrafiltration membranes were fabricated from four poly(isoprene-b-styrene-b-4-vinylpyridine) triblock terpolymers with similar block volume

Volatile organic compounds from vegetation in southern Yunnan Province, China: Emission rates and some potential regional implications

Science.gov (United States)

Geron, Chris; Owen, Sue; Guenther, Alex; Greenberg, Jim; Rasmussen, Rei; Hui Bai, Jian; Li, Qing-Jun; Baker, Brad

Little information is currently available regarding emissions of biogenic volatile organic compounds (BVOCs) in southern Asia. To address the need for BVOC emission estimates in regional atmospheric chemistry simulations, 95 common plant species were screened for emissions of BVOC in and near the Xishuangbanna Tropical Biological Gardens in southern Yunnan Province, Peoples' Republic of China in February 2003. In situ measurements with leaf cuvettes and branch bag enclosures were used in combination with portable gas chromatography, flame ionization, photoionization, and mass spectral detection to identify and quantify BVOC emissions. Forty-four of the species examined emitted isoprene at rates exceeding 20 μg C g -1 (leaf dry weight) h -1. An emphasis was placed on the genus Ficus, which is important in the region and occupies a wide range of ecological niches. Several species in the footprint of a nearby flux tower were also examined. Several palm species and an abundant fern ( Cyclosorus parasiticus) emitted substantial amounts of isoprene, and probably accounted for observed daytime mean isoprene fluxes from the understory of a Hevea brasiliensis plantation of 1.0 and 0.15 mg C m -2 h -1 during the wet and dry seasons, respectively. These measurements verify that both the forest floor and canopy in this region can be sources of isoprene. Monoterpene emissions exceeded 1.0 μg-C g -1 (leaf dry weight) h -1 from only 4 of 38 species surveyed, including some Ficus species and H. brasiliensis. However most of the trees of the latter species were sparsely foliated due to dry season senescence, and emission factors are approximately an order of magnitude lower than those reported during the wet season. BVOC emission rates and physiology of many species are impacted by reduced moisture availability, especially Mangifera indica. South Asia is a region undergoing rapid landuse change and forest plantation establishment, with large increases in area of high BVOC

Direct observations of Biogenic Volatile Organic Compound (BVOC) Air-Sea Exchange in the remote North Atlantic from the High-Wind Gas-Exchange Study (HiWinGS)

Science.gov (United States)

Kim, M.; Yang, M. X.; Blomquist, B.; Huebert, B. J.; Bertram, T. H.

2014-12-01

Biogenic Volatile Organic Compounds (BVOCs) are reactive trace gases that impact both chemistry and climate by regulating oxidant loadings, determining secondary organic aerosol production rates as well as altering particle hygroscopicity. While continental BVOC exchange rates are well studied, global marine flux estimates are poorly constrained. In Fall 2013, a chemical-ionization time-of-flight mass spectrometer (CI-ToF-MS) utilizing benzene cations was deployed as part of the High Wind Gas Exchange Study (HiWinGs) to quantify monoterpenes, isoprene and dimethylsulfide fluxes in the remote North Atlantic. Dimethylsulfide measurements are in strong agreement with those determined by the University of Hawaii's atmospheric pressure ionization mass-spectrometer. In the remote marine boundary layer, positive monoterpene fluxes (i.e. emissions) were observed while isoprene levels rarely exceeded the detection limit.

Biogenic VOC Emissions from Tropical Landscapes

Science.gov (United States)

Guenther, A.; Greenberg, J.; Harley, P.; Otter, L.; Vanni Gatti, L.; Baker, B.

2003-04-01

Biogenic VOC have an important role in determining the chemical composition of atmosphere. As a result, these compounds are important for visibility, biogeochemical cycling, climate and radiative forcing, and the health of the biosphere. Tropical landscapes are estimated to release about 80% of total global biogenic VOC emissions but have been investigated to lesser extent than temperate regions. Tropical VOC emissions are particularly important due to the strong vertical transport and the rapid landuse change that is occurring there. This presentation will provide an overview of field measurements of biogenic VOC emissions from tropical landscapes in Amazonia (Large-scale Biosphere-atmosphere experiment in Amazonia, LBA) Central (EXPRESSO) and Southern (SAFARI 2000) Africa, Asia and Central America. Flux measurement methods include leaf-scale (enclosure measurements), canopy-scale (above canopy tower measurements), landscape-scale (tethered balloon), and regional-scale (aircraft measurements) observations. Typical midday isoprene emission rates for different landscapes vary by more than a factor of 20 with the lowest emissions observed from degraded forests. Emissions of alpha-pinene vary by a similar amount with the highest emissions associated with landscapes dominated by light dependent monoterpene emitting plants. Isoprene emissions tend to be higher for neotropical forests (Amazon and Costa Rica) in comparison to Africa and Asian tropical forests but considerable differences are observed within regions. Strong seasonal variations were observed in both the Congo and the Amazon rainforests with peak emissions during the dry seasons. Substantial emissions of light dependent monoterpenes, methanol and acetone are characteristic of at least some tropical landscapes.

Comparing two periphyton collection methods commonly used for stream bioassessment and the development of numeric nutrient standards.

Science.gov (United States)

Rodman, Ashley R; Scott, J Thad

2017-07-01

Periphyton is an important component of stream bioassessment, yet methods for quantifying periphyton biomass can differ substantially. A case study within the Arkansas Ozarks is presented to demonstrate the potential for linking chlorophyll-a (chl-a) and ash-free dry mass (AFDM) data sets amassed using two frequently used periphyton sampling protocols. Method A involved collecting periphyton from a known area on the top surface of variably sized rocks gathered from relatively swift-velocity riffles without discerning canopy cover. Method B involved collecting periphyton from the entire top surface of cobbles systematically gathered from riffle-run habitat where canopy cover was intentionally avoided. Chl-a and AFDM measurements were not different between methods (p = 0.123 and p = 0.550, respectively), and there was no interaction between method and time in the repeated measures structure of the study. However, significantly different seasonal distinctions were observed for chl-a and AFDM from all streams when data from the methods were combined (p methods may effectively be used together with some minor considerations due to potential confounding factors. This study provides motivation for the continued investigation of combining data sets derived from multiple methods of data collection, which could be useful in stream bioassessment and particularly important for the development of regional stream nutrient criteria for the southern Ozarks.

Production of volatile organic compounds by cyanobacteria Synechococcus sp.

Science.gov (United States)

Hiraiwa, M.; Abe, M.; Hashimoto, S.

2014-12-01

Phytoplankton are known to produce volatile organic compounds (VOCs), which contribute to environmental problems such as global warming and decomposition of stratospheric ozone. For example, picophytoplankton, such as Prochlorococcus and Synechococcus, are distributed in freshwater and oceans worldwide, accounting for a large proportion of biomass and primary production in the open ocean. However, to date, little is known about the production of VOCs by picophytoplankton. In this study, VOCs production by cyanobacteria Synechococcus sp. (NIES-981) was investigated. Synechococcus sp. was obtained from the National Institute for Environmental Studies (NIES), Japan, and cultured at 24°C in autoclaved f/2-Si medium under 54 ± 3 µE m-2 s-1 (1 E = 1 mol of photons) with a 12-h light and 12-h dark cycle. VOCs concentrations were determined using a purge-and-trap gas chromatograph-mass spectrometer (Agilent 5973). The concentrations of chlorophyll a (Chl a) were also determined using a fluorometer (Turner TD-700). Bromomethane (CH3Br) and isoprene were produced by Synechococcus sp. Isoprene production was similar to those of other phytoplankton species reported earlier. Isoprene was produced when Chl a was increasing in the early stage of the incubation period (5-15 days of incubation time, exponential phase), but CH3Br was produced when Chl a was reduced in the late stage of the incubation period (30-40 days of incubation time, death phase).

Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

Directory of Open Access Journals (Sweden)

C. Mouchel-Vallon

2013-01-01

Full Text Available The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene is investigated for various NO_x conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (yield less than 2% on carbon atom basis under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation to 70% (octane oxidation of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NO_x conditions. For high NO_x conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively. Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

Fluxes and concentrations of volatile organic compounds above central London, UK

Directory of Open Access Journals (Sweden)

B. Langford

2010-01-01

Full Text Available Concentrations and fluxes of eight volatile organic compounds (VOCs were measured during October 2006 from a high telecom tower above central London, as part of the CityFlux contribution to the REPARTEE I campaign. A continuous flow disjunct eddy covariance technique with analysis by proton transfer reaction mass spectrometry was used. Daily averaged VOC mixing ratios were within the range 1–19 ppb for the oxygenated compounds (methanol, acetaldehyde and acetone and 0.2–1.3 ppb for the aromatics (benzene, toluene and C₂-benzenes. Typical VOC fluxes were in the range 0.1–1.0 mg m⁻² h⁻¹. There was a non-linear relationship between VOC fluxes and traffic density for most of the measured compounds. Traffic activity was estimated to account for approximately 70% of the aromatic compound fluxes, whereas non-traffic related sources were found to be more important for methanol and isoprene fluxes. The measured fluxes were comparable to the estimates of the UK national atmospheric emission inventory for the aromatic VOCs and CO. In contrast, fluxes of the oxygenated compounds were about three times larger than inventory estimates. For isoprene and acetonitrile this difference was many times larger. At temperatures over 25° C it is estimated that more than half the isoprene observed in central London is of biogenic origin.

Simultaneous determination of the styrene unit content and assessment of molecular weight of triblock copolymers in adhesives by a size exclusion chromatography method.

Science.gov (United States)

Wang, Mingfang; Wang, Yuerong; Luo, Pei; Zhang, Hongyang; Zhang, Min; Hu, Ping

2017-10-01

The content of styrene units in nonhydrogenated and hydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers significantly influences product performance. A size exclusion chromatography method was developed to determine the average styrene content of triblock copolymers blended with tackifier in adhesives. A complete separation of the triblock copolymer from the other additives was realized with size exclusion chromatography. The peak area ratio of the UV and refraction index signals of the copolymers at the same effective elution volume was correlated to the average styrene unit content using nuclear magnetic resonance spectroscopy with commercial copolymers as standards. The obtained calibration curves showed good linearity for both the hydrogenated and nonhydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers (r = 0.974 for styrene contents of 19.3-46.3% for nonhydrogenated ones and r = 0.970 for the styrene contents of 23-58.2% for hydrogenated ones). For copolymer blends, the developed method provided more accurate average styrene unit contents than nuclear magnetic resonance spectroscopy provided. These results were validated using two known copolymer blends consisting of either styrene-isoprene-styrene or hydrogenated styrene-butadiene-styrene and a hydrocarbon tackifying resin as well as an unknown adhesive with styrene-butadiene-styrene and an aromatic tackifying resin. The methodology can be readily applied to styrene-containing polymers in blends such as poly(acrylonitrile-butadiene styrene). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The LEGO toolbox: Supramolecular building blocks by nitroxide-mediated controlled radical polymerization

NARCIS (Netherlands)

Lohmeijer, B.G.G.; Schubert, U.S.

2005-01-01

A terpyridine-functionalized alkoxyamine unimolecular initiator was used for the nitroxide-mediated controlled living radical polymerization of n-butylacrylate, N,N-dimethylacrylamide, 4-vinylpyridine, 2-vinylpyridine, and isoprene. For the former three monomers, the kinetics were studied. All

Estimate of biogenic VOC emissions in Japan and their effects on photochemical formation of ambient ozone and secondary organic aerosol

Science.gov (United States)

Chatani, Satoru; Matsunaga, Sou N.; Nakatsuka, Seiji

2015-11-01

A new gridded database has been developed to estimate the amount of isoprene, monoterpene, and sesquiterpene emitted from all the broadleaf and coniferous trees in Japan with the Model of Emissions of Gases and Aerosols from Nature (MEGAN). This database reflects the vegetation specific to Japan more accurately than existing ones. It estimates much lower isoprene emitted from other vegetation than trees, and higher sesquiterpene emissions mainly emitted from Cryptomeria japonica, which is the most abundant plant type in Japan. Changes in biogenic emissions result in the decrease in ambient ozone and increase in organic aerosol simulated by the air quality simulation over the Tokyo Metropolitan Area in Japan. Although newly estimated biogenic emissions contribute to a better model performance on overestimated ozone and underestimated organic aerosol, they are not a single solution to solve problems associated with the air quality simulation.

Kinetics of disorder-to-fcc phase transition via an intermediate bcc state

International Nuclear Information System (INIS)

Liu Yongsheng; Nie Huifen; Bansil, Rama; Steinhart, Milos; Bang, Joona; Lodge, Timothy P.

2006-01-01

Time-resolved small-angle x-ray scattering measurements reveal that a long-lived intermediate bcc state forms when a poly(styrene-b-isoprene) diblock copolymer solution in an isoprene selective solvent is rapidly cooled from the disordered micellar fluid at high temperature to an equilibrium fcc state. The kinetics of the epitaxial growth of the [111] fcc peak from the [110] bcc peak was obtained by fitting the scattering data to a simple model of the transformation. The growth of the [111] fcc peak agrees with the Avrami model of nucleation and growth kinetics with an exponent n=1.4, as does the initial decay of the [110] bcc peak, with an exponent n=1.3. The data were also found to be in good agreement with the Cahn model of grain boundary nucleation and growth

Increases to Biogenic Secondary Organic Aerosols from SO2 and NOx in the Southeastern US

Science.gov (United States)

Russell, L. M.; Liu, J.; Ruggeri, G.; Takahama, S.; Claflin, M. S.; Ziemann, P. J.; Lee, A.; Murphy, B.; Pye, H. O. T.; Ng, N. L.; McKinney, K. A.; Surratt, J. D.

2017-12-01

, one of which was Biological Organic Aerosols. The FTIR spectrum for this factor is similar (cosine similarity > 0.6) to that of lab-generated particle mass from both isoprene and monoterpene with high NOx conditions from chamber experiments, providing verification of the reactions relevant to atmospheric conditions.

Isoprenoid emission in hygrophyte and xerophyte European woody flora: ecological and evolutionary implications

Czech Academy of Sciences Publication Activity Database

Loreto, F.; Bagnoli, F.; Calfapietra, Carlo; Cafasso, D.; De Lillis, M.; Filibeck, G.; Finsechi, S.; Guidolotti, G.; Sramko, G.; Tökölyi, J.; Ricotta, C.

2014-01-01

Roč. 23, č. 3 (2014), s. 334-345 ISSN 1466-822X Institutional support: RVO:67179843 Keywords : Adaptation * chemo-taxonomy * hygrophytes * isoprene * monoterpenes * phylogenies * salicaceae * xerophytes * water stress Subject RIV: EH - Ecology, Behaviour Impact factor: 6.531, year: 2014

Thermal processing of diblock copolymer melts mimics metallurgy

Science.gov (United States)

Kim, Kyungtae; Schulze, Morgan W.; Arora, Akash; Lewis, Ronald M.; Hillmyer, Marc A.; Dorfman, Kevin D.; Bates, Frank S.

2017-05-01

Small-angle x-ray scattering experiments conducted with compositionally asymmetric low molar mass poly(isoprene)-b-poly(lactide) diblock copolymers reveal an extraordinary thermal history dependence. The development of distinct periodic crystalline or aperiodic quasicrystalline states depends on how specimens are cooled from the disordered state to temperatures below the order-disorder transition temperature. Whereas direct cooling leads to the formation of documented morphologies, rapidly quenched samples that are then heated from low temperature form the hexagonal C14 and cubic C15 Laves phases commonly found in metal alloys. Self-consistent mean-field theory calculations show that these, and other associated Frank-Kasper phases, have nearly degenerate free energies, suggesting that processing history drives the material into long-lived metastable states defined by self-assembled particles with discrete populations of volumes and polyhedral shapes.

Polymersomes with asymmetric membranes and self-assembled superstructures using pentablock quintopolymers resolved by electron tomography

KAUST Repository

Haataja, J. S.; Houbenov, N.; Aseyev, V.; Fragouli, P.; Iatrou, H.; Sougrat, Rachid; Hadjichristidis, Nikolaos; Ikkala, O.

2018-01-01

Polystyrene-block-poly(1,4-isoprene)-block-poly(dimethyl siloxane)-block-poly(tert-butyl methacrylate)-block-poly(2-vinyl pyridine), PS-b-PI-b-PDMS-b-PtBMA-b-P2VP, self-assembles in acetone into polymersomes with asymmetric (directional) PI

Synthesis, characterization and self-assembly of well-defined linear heptablock quaterpolymers

KAUST Repository

Ntaras, Christos; Polymeropoulos, George; Zapsas, George; Ntetsikas, Konstantinos; Liontos, George; Karanastasis, Apostolos; Moschovas, Dimitrios; Rangou, Sofia; Stewart-Sloan, Charlotte; Hadjichristidis, Nikolaos; Thomas, Edwin L.; Avgeropoulos, Apostolos

2016-01-01

Two well-defined heptablock quaterpolymers of the ABCDCBA type [Α: polystyrene (PS), B: poly(butadiene) with ∼90% 1,4-microstructure (PB1,4), C: poly(isoprene) with ∼55% 3,4-microstructure (PI3,4) and D: poly(dimethylsiloxane) (PDMS)] were

Molecular size evolution of oligomers in organic aerosols collected in urban atmospheres and generated in a smog chamber.

Science.gov (United States)

Kalberer, Markus; Sax, Mirjam; Samburova, Vera

2006-10-01

Only a minor fraction of the total organic aerosol mass can be resolved on a molecular level. High molecular weight compounds in organic aerosols have recently gained much attention because this class of compound potentially explains a major fraction of the unexplained organic aerosol mass. These compounds have been identified with different mass spectrometric methods, and compounds with molecular masses up to 1000 Da are found in secondary organic aerosols (SOA) generated from aromatic and terpene precursors in smog chamber experiments. Here, we apply matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) to SOA particles from two biogenic precursors, alpha-pinene and isoprene. Similar oligomer patterns are found in these two SOA systems, but also in SOA from trimethylbenzene, an anthropogenic SOA precursor. However, different maxima molecular sizes were measured for these three SOA systems. While oligomers in alpha-pinene and isoprene have sizes mostly below 600-700 Da, they grow up to about 1000 Da in trimethylbenzene-SOA. The final molecular size of the oligomers is reached early during the particle aging process, whereas other particle properties related to aging, such as the overall acid concentration or the oligomer concentration, increase continuously over a much longer time scale. This kinetic behavior of the oligomer molecular size growth can be explained by a chain growth kinetic regime. Similar oligomer mass patterns were measured in aqueous extracts of ambient aerosol samples (measured with the same technique). Distinct differences between summer and winter were observed. In summer a few single mass peaks were measured with much higher intensity than in winter, pointing to a possible difference in the formation processes of these compounds in winter and summer.

Anthropology of fire in the Ozark Highland region

Science.gov (United States)

David H. Jurney

2012-01-01

Native Americans are often considered to have exploited available natural resources rather than modifying their environments to maximize yields. As simpler societies evolved into more complex ones, there is a consensus that intensification of habitat modifications also increased. However, landscape scale archeological inventories now show relatively intensive...

Chlorophyll a with a farnesyl tail in thermophilic cyanobacteria.

Science.gov (United States)

Wiwczar, Jessica M; LaFountain, Amy M; Wang, Jimin; Frank, Harry A; Brudvig, Gary W

2017-11-01

Photosystem II (PSII) of oxygenic photosynthetic organisms normally contains exclusively chlorophyll a (Chl a) as its major light-harvesting pigment. Chl a canonically consists of the chlorin headgroup with a 20-carbon, 4-isoprene unit, phytyl tail. We have examined the 1.9 Å crystal structure of PSII from thermophilic cyanobacteria reported by Shen and coworkers in 2012 (PDB accession of 3ARC/3WU2). A newly refined electron density map from this structure, presented here, reveals that some assignments of the cofactors may be different from those modeled in the 3ARC/3WU2 structure, including a specific Chl a that appears to have a truncated tail by one isoprene unit. We provide experimental evidence using high-performance liquid chromatography and mass spectrometry for a small population of Chl a esterified to a 15-carbon farnesyl tail in PSII of thermophilic cyanobacteria.

Polar Diels-Alder reactions using electrophilic nitrobenzothiophenes. A combined experimental and DFT study

Science.gov (United States)

Della Rosa, Claudia D.; Mancini, Pedro M. E.; Kneeteman, Maria N.; Lopez Baena, Anna F.; Suligoy, Melisa A.; Domingo, Luis R.

2015-01-01

The reactions between 2- and 3-nitrobenzothiophenes with three dienes of different nucleophilicity, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 1-trimethylsilyloxy-1,3-butadiene and isoprene developed in anhydrous benzene and alternative under microwave irradiation with molecular solvents or in free solvent conditions, respectively, for produce dibenzothiophenes permit to conclude that both nitroheterocycles act as electrophile with the cited dienes. In the cases of the dienes 1-methoxy-3-trimethylsilyloxy-1,3-butadiene and 1-trimethylsilyloxy-1,3-butadiene which posses major nucleophilicity the observed product is the normal cycloaddition one. However when the diene is isoprene the product with both electrophiles follow the hetero Diels-Alder way. These reactions are considered polar cycloaddition reactions and the yields are reasonables. Moreover the polar Diels-Alder reactions of nitrobenzothiophenes with electron rich dienes 1-trimethylsilyloxy-1,3-butadiene have been theoretically studied using DFT methods.

Changes in photosynthesis, mesophyll conductance to CO2, and isoprenoid emissions in Populus nigra plants exposed to excess nickel

International Nuclear Information System (INIS)

Velikova, Violeta; Tsonev, Tsonko; Loreto, Francesco; Centritto, Mauro

2011-01-01

Poplar (Populus nigra) plants were grown hydroponically with 30 and 200 μM Ni (Ni 30 and Ni 200 ). Photosynthesis limitations and isoprenoid emissions were investigated in two leaf types (mature and developing). Ni stress significantly decreased photosynthesis, and this effect depended on the leaf Ni content, which was lower in mature than in developing leaves. The main limitations to photosynthesis were attributed to mesophyll conductance and metabolism impairment. In Ni-stressed developing leaves, isoprene emission was significantly stimulated. We attribute such stimulation to the lower chloroplastic [CO 2 ] than in control leaves. However chloroplastic [CO 2 ] did not control isoprene emission in mature leaves. Ni stress induced the emission of cis-β-ocimene in mature leaves, and of linalool in both leaf types. Induced biosynthesis and emission of isoprenoids reveal the onset of antioxidant processes that may also contribute to reduce Ni stress, especially in mature poplar leaves. - Graphical abstract: Visible damage caused by Ni treatment. 1 - Ni 0 (control plants); 2 - Ni 200 ; M = mature and D = developing Populus nigra leaves. Display Omitted Highlights: → We study the effect of Ni pollution on photosynthesis and isoprenoid emissions. → Ni stress significantly decreases photosynthesis. The main limitations are attributed to mesophyll conductance and metabolism impairment. → Constitutive isoprene emission was significantly stimulated in Ni-stressed leaves. Exposure to enhanced Ni concentration induces cis-beta-ocimene and linalool emissions. - The study reveals consequences of Ni stress on plant physiology, namely increasing diffusional limitation to photosynthesis and isoprenoid emissions.

Radiation-induced cationic polymerization of isobutylene-isopene systems: advantages and disadvantages compared to catalytic initiation

International Nuclear Information System (INIS)

Williams, F.; Shinkawa, A.; Kennedy, J.P.

1976-01-01

The cationic copolymerization of isobutylene (1) with isoprene (2) has been induced by γ-irradiation of dry comonomer systems in bulk. Although the polymer conversion per unit dose is reduced about a thousand-fold by the addition of 3 mole % isoprene to isobutylene, the molecular weight of the copolymer is comparable to that of the homopolymer of isobutylene prepared at the same polymerization temperature. The copolymer composition corresponds closely to that of the monomer feed up to 7.1 mole % isoprene. The results are consistently accounted for by postulating that the slow step in the kinetic chain is the cross-propagation reaction described by the rate constant k/sub p21/ with an estimated value of 3 x 10 8 M -1 sec -1 at 0 0 C, this constant being much less than k/sub p12/ similarly ordered k/sub p11/ = 1.5 x 10 8 M -1 sec -1 . The viscosity-average molecular weights of the radiation-induced copolymers are about a factor of ten higher than those produced by BF 3 , AlEtCl 2 , and AlCl 3 at the same polymerization temperature. This effect is similar to that observed previously for the homopolymers of isobutylene and is attributed to the free-ion character of the radiation-induced polymerization. Despite this advantage enjoyed by the γ-irradiation method, it is subject to various practical limitations, of which the foremost is the inability to tolerate suitable solvents such as methyl chloride without sacrificing a large reduction in polymerization rate

Incorporating GOES Satellite Photosynthetically Active Radiation (PAR) Retrievals to Improve Biogenic Emission Estimates in Texas

Science.gov (United States)

Zhang, Rui; White, Andrew T.; Pour Biazar, Arastoo; McNider, Richard T.; Cohan, Daniel S.

2018-01-01

This study examines the influence of insolation and cloud retrieval products from the Geostationary Operational Environmental Satellite (GOES) system on biogenic emission estimates and ozone simulations in Texas. Compared to surface pyranometer observations, satellite-retrieved insolation and photosynthetically active radiation (PAR) values tend to systematically correct the overestimation of downwelling shortwave radiation in the Weather Research and Forecasting (WRF) model. The correlation coefficient increases from 0.93 to 0.97, and the normalized mean error decreases from 36% to 21%. The isoprene and monoterpene emissions estimated by the Model of Emissions of Gases and Aerosols from Nature are on average 20% and 5% less, respectively, when PAR from the direct satellite retrieval is used rather than the control WRF run. The reduction in biogenic emission rates using satellite PAR reduced the predicted maximum daily 8 h ozone concentration by up to 5.3 ppbV over the Dallas-Fort Worth (DFW) region on some days. However, episode average ozone response is less sensitive, with a 0.6 ppbV decrease near DFW and 0.3 ppbV increase over East Texas. The systematic overestimation of isoprene concentrations in a WRF control case is partially corrected by using satellite PAR, which observes more clouds than are simulated by WRF. Further, assimilation of GOES-derived cloud fields in WRF improved CAMx model performance for ground-level ozone over Texas. Additionally, it was found that using satellite PAR improved the model's ability to replicate the spatial pattern of satellite-derived formaldehyde columns and aircraft-observed vertical profiles of isoprene.

Changes in photosynthesis, mesophyll conductance to CO{sub 2}, and isoprenoid emissions in Populus nigra plants exposed to excess nickel

Energy Technology Data Exchange (ETDEWEB)

Velikova, Violeta, E-mail: violet@obzor.bio21.bas.bg [Bulgarian Academy of Sciences, Acad. M. Popov Institute of Plant Physiology, Acad. G. Bonchev, Bl. 21, 1113 Sofia (Bulgaria); Tsonev, Tsonko [Bulgarian Academy of Sciences, Acad. M. Popov Institute of Plant Physiology, Acad. G. Bonchev, Bl. 21, 1113 Sofia (Bulgaria); Loreto, Francesco [Consiglio Nazionale delle Ricerche, Istituto per la Protezione delle Piante, Via Madonna del Piano 10, 50019 Sesto Fiorentino, Firenze (Italy); Centritto, Mauro [Consiglio Nazionale delle Ricerche, Istituto di Biologia Agroambientale e Forestale, 00015 Monterotondo Scalo (RM) (Italy)

2011-05-15

Poplar (Populus nigra) plants were grown hydroponically with 30 and 200 {mu}M Ni (Ni{sub 30} and Ni{sub 200}). Photosynthesis limitations and isoprenoid emissions were investigated in two leaf types (mature and developing). Ni stress significantly decreased photosynthesis, and this effect depended on the leaf Ni content, which was lower in mature than in developing leaves. The main limitations to photosynthesis were attributed to mesophyll conductance and metabolism impairment. In Ni-stressed developing leaves, isoprene emission was significantly stimulated. We attribute such stimulation to the lower chloroplastic [CO{sub 2}] than in control leaves. However chloroplastic [CO{sub 2}] did not control isoprene emission in mature leaves. Ni stress induced the emission of cis-{beta}-ocimene in mature leaves, and of linalool in both leaf types. Induced biosynthesis and emission of isoprenoids reveal the onset of antioxidant processes that may also contribute to reduce Ni stress, especially in mature poplar leaves. - Graphical abstract: Visible damage caused by Ni treatment. 1 - Ni{sub 0} (control plants); 2 - Ni{sub 200}; M = mature and D = developing Populus nigra leaves. Display Omitted Highlights: > We study the effect of Ni pollution on photosynthesis and isoprenoid emissions. > Ni stress significantly decreases photosynthesis. The main limitations are attributed to mesophyll conductance and metabolism impairment. > Constitutive isoprene emission was significantly stimulated in Ni-stressed leaves. Exposure to enhanced Ni concentration induces cis-beta-ocimene and linalool emissions. - The study reveals consequences of Ni stress on plant physiology, namely increasing diffusional limitation to photosynthesis and isoprenoid emissions.

Biogenic volatile organic compound emissions along a high arctic soil moisture gradient

DEFF Research Database (Denmark)

Svendsen, Sarah Hagel; Lindwall, Frida; Michelsen, Anders

2016-01-01

emissions of BVOCs were found from vegetation communities dominated by Salix arctica and Cassiope tetragona, which had emission profiles dominated by isoprene and monoterpenes, respectively. These results show that emissions of BVOCs are highly dependent on the plant cover supported by the varying soil...

Modelling atmospheric OH-reactivity in a boreal forest ecosystem

DEFF Research Database (Denmark)

Mogensen, D.; Smolander, S.; Sogachev, Andrey

2011-01-01

We have modelled the total atmospheric OH-reactivity in a boreal forest and investigated the individual contributions from gas phase inorganic species, isoprene, monoterpenes, and methane along with other important VOCs. Daily and seasonal variation in OH-reactivity for the year 2008 was examined...

Lignocellulosic fiber reinforced rubber composites

CSIR Research Space (South Africa)

Jacob John, Maya

2009-04-01

Full Text Available Natural Rubber (NR) is a naturally occurring elastomeric polymer of isoprene (2-methyl-1,3-butadiene). It can be extracted from latex of only one kind of tree, the Hevea braziliensis. Hevea rubber is produced in many tropical regions of Southeast...

ISOTOPIC (14C) AND CHEMICAL COMPOSITION OF ATMOSPHERIC VOLATILE ORGANIC COMPOUND FRACTIONS - PRECURSORS TO OZONE FORMATION

Science.gov (United States)

Atmospheric volatile organic compounds (VOCs) are an important factor in the production of ozone near ground level [3]. Many hydrocarbons originate from auto exhaust. However, a number of VOCs, e.g., isoprene, are known to be natural in origin. To develop reliable models for un...

An improved method for fast and selective separation of carotenoids by UPLC-MS

Science.gov (United States)

Carotenoids are a large class of compounds that are biosynthesized by condensation of isoprene units in plants, fungi, bacteria, and some animals. They are characteristically highly conjugated through double bonds, which lead to many isomers as well susceptibility to oxidation and other chemical mod...

75 FR 72727 - Addition of National Toxicology Program Carcinogens; Community Right-to-Know Toxic Chemical...

Science.gov (United States)

2010-11-26

...; nitromethane; phenolphthalein; tetrafluoroethylene; tetranitromethane; and vinyl fluoride. In addition, the... chemicals, glycidol and vinyl fluoride out of the 16 at issue in this action. EPA notes that the commenter... included in the record. The IISRP noted that the proposed rule refers to similarities between isoprene and...

Structural characterization of rubber from jackfruit and euphorbia as a model of natural rubber.

Science.gov (United States)

Mekkriengkrai, Dararat; Ute, Koiichi; Swiezewska, Ewa; Chojnacki, Tadeusz; Tanaka, Yasuyuki; Sakdapipanich, Jitladda T

2004-01-01

A structural study of low molecular weight rubbers from Jackfruit (Artocarpus heterophyllus) and Painted spurge (Euphorbia heterophylla) was carried out as model compounds of natural rubber from Hevea brasiliensis. The rubber content of latex from Jackfruit was 0.4-0.7%, which is very low compared with that of 30-35% in the latex from Hevea tree. The rubber from Jackfruit latex was low molecular weight with narrow unimodal molecular weight distribution (MWD), whereas that obtained from E. heterophylla showed very broad MWD. The 1H and 13C NMR analyses showed that Jackfruit rubber consists of a dimethylallyl group and two trans-isoprene units connected to a long sequence of cis-isoprene units. The alpha-terminal group of Jackfruit rubber was presumed to be composed of a phosphate group based on the presence of 1H NMR signal at 4.08 ppm corresponding to the terminal =CH-CH2OP group.

Leaf, branch, stand and landscape scale measurements of volatile organic compound fluxes from U. S. woodlands

Energy Technology Data Exchange (ETDEWEB)

Guenther, A.; Greenberg, J.; Harley, P.; Helmig, D.; Klinger, L.; Vierling, L.; Zimmerman, P. [National Center for Atmospheric Research, Boulder, CO (United States). Atmospheric Chemistry Div.; Geron, C. [Environmental Protection Agency, Research Triangle Park, NC (United States)

1996-01-01

Natural volatile organic compound (VOC) fluxes were measured in three U.S. woodlands. Fluxes from individual leaves and branches were estimated with enclosure techniques and used to initialize and evaluate VOC emission model estimates. Ambient measurements were used to estimate above canopy fluxes for entire stands. A total of 78 VOCs were identified, with hexenol derivatives being the most commonly observed oxygenated compounds. There was also evidence of high rates of isoprene emission and high rates of monoterpenes in some genera of trees. Model predictions of diurnal variations were within + or - 35 per cent of observed flux variations. Fluxes predicted by a recent version of a biogenic emission model were within 10 per cent to 50 per cent of observed fluxes, leading to the conclusion that existing databases can provide isoprene and monoterpene emission rate potentials within acceptable limits for the dominant plant species at these three woodland sites. 21 refs., 5 tabs., 2 figs.

SOA precursors at the T0 site during the 2010 CARES campaign

Science.gov (United States)

Wallace, H. W.; Jobson, B. T.; Erickson, M. H.

2010-12-01

Continuous measurements of C5 to C12 Volatile Organic Compounds (VOC) have been made using the Washington State University Mobile Atmospheric Chemistry Laboratory (MACL), at the T0 site during the month of June 2010 Carbonaceous Aerosol Carbonaceous Aerosols and Radiative Effects Study (CARES). These measurements were made to better understand aerosol formation and growth in Sacramento, CA and the surrounding areas. Using a sorbent based preconcentration sampling technique for our quadrupole ion trap gas chromatography mass spectrometer (GCMS), we have measured anthropogenic and biogenic secondary organic aerosol (SOA) precursors. Major biogenic VOCs identified include: α-pinene, limonene, isoprene, phellanderene and β-pinene. Diurnal profiles of the concentrations will be presented. Monoterpenes were highest in the mornings while isoprene was highest in the afternoon. In addition to understanding the diurnal profiles the SOA precursors at the T0 site, the relative contributions of biogenic and anthropogenic compounds to SOA formation will be presented.

Climate/chemistry feedbacks and biogenic emissions.

Science.gov (United States)

Pyle, John A; Warwick, Nicola; Yang, Xin; Young, Paul J; Zeng, Guang

2007-07-15

The oxidizing capacity of the atmosphere is affected by anthropogenic emissions and is projected to change in the future. Model calculations indicate that the change in surface ozone at some locations could be large and have significant implications for human health. The calculations depend on the precise scenarios used for the anthropogenic emissions and on the details of the feedback processes included in the model. One important factor is how natural biogenic emissions will change in the future. We carry out a sensitivity calculation to address the possible increase in isoprene emissions consequent on increased surface temperature in a future climate. The changes in ozone are significant but depend crucially on the background chemical regime. In these calculations, we find that increased isoprene will increase ozone in the Northern Hemisphere but decrease ozone in the tropics. We also consider the role of bromine compounds in tropospheric chemistry and consider cases where, in a future climate, the impact of bromine could change.

Degrading radiation effects on properties of bromobutyl rubber compounds

Energy Technology Data Exchange (ETDEWEB)

Scagliusi, Sandra R.; Cardoso, Elisabeth C.L.; Pozenato, Cristina A.; Lugao, Ademar B., E-mail: srscagliusi@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2013-07-01

The understanding of chemistry involved in degradation induced radiation is becoming more and more relevant in the re-use of polymeric materials, as well in beneficial radiation uses. Degrading radiation effects have been considered from viewpoint of controlled degradation for isoprene/isobutene in rubbers for recycling purposes. Bromobutyl rubber (BIIR) is an isobutylene/isoprene copolymer comprising 1.9 to 2.1% bromine and has a lot of applications including in tires air-chambers. In this work there were evaluated gamma-irradiation effects for re-use or recycling objectives in elastomeric bromobutyl compositions irradiated at 5, 15, 25, 50, 100,150 and 200 kGy. Mechanical properties, hardness and swelling were assessed in non-vulcanized and vulcanized rubber, non-irradiated and irradiated at different doses. The major gamma radiation effect in butyl rubber is the generation of free radicals along changes in mechanical properties. Irradiation effects in bromobutyl rubber compounds were comprehensively investigated, demonstrated and discussed. (author)

Volatile Organic Compounds in the Atmosphere of the Botanical Garden of the City of Rio de Janeiro: A Preliminary Study.

Science.gov (United States)

da Silva, Cleyton Martins; Souza, Elaine Cesar C A; da Silva, Luane Lima; Oliveira, Rafael Lopes; Corrêa, Sergio Machado; Arbilla, Graciela

2016-11-01

Volatile organic compounds (VOCs) play a central role in atmospheric chemistry. In this work, VOCs in the Botanical Garden of Rio de Janeiro were determined using the TO-15 Method. The park occupies 1,370,000 m 2 in the southern area of the city and is next to the Tijuca Forest, which is considered the largest secondary urban forest in the world. The total VOC concentrations ranged from 43.52 to 168.75 µg m -3 , depending on the sampling site and dates. In terms of concentration isoprene represented 4 %-14 % of the total VOC masses. The results suggested that the differences in biomass, distance from the street and activities within the park affected the concentrations of VOCs. The ratios of isoprene/aromatic compounds were higher than those determined in other areas of the city, confirming that the atmosphere of this green area has the contribution of other sources. Kinetic and mechanistic reactivities were also evaluated.

Degrading radiation effects on properties of bromobutyl rubber compounds

International Nuclear Information System (INIS)

Scagliusi, Sandra R.; Cardoso, Elisabeth C.L.; Pozenato, Cristina A.; Lugao, Ademar B.

2013-01-01

The understanding of chemistry involved in degradation induced radiation is becoming more and more relevant in the re-use of polymeric materials, as well in beneficial radiation uses. Degrading radiation effects have been considered from viewpoint of controlled degradation for isoprene/isobutene in rubbers for recycling purposes. Bromobutyl rubber (BIIR) is an isobutylene/isoprene copolymer comprising 1.9 to 2.1% bromine and has a lot of applications including in tires air-chambers. In this work there were evaluated gamma-irradiation effects for re-use or recycling objectives in elastomeric bromobutyl compositions irradiated at 5, 15, 25, 50, 100,150 and 200 kGy. Mechanical properties, hardness and swelling were assessed in non-vulcanized and vulcanized rubber, non-irradiated and irradiated at different doses. The major gamma radiation effect in butyl rubber is the generation of free radicals along changes in mechanical properties. Irradiation effects in bromobutyl rubber compounds were comprehensively investigated, demonstrated and discussed. (author)

Temperature Scanning Stress Relaxation of an Autonomous Self-Healing Elastomer Containing Non-Covalent Reversible Network Junctions

Directory of Open Access Journals (Sweden)

Amit Das

2018-01-01

Full Text Available In this work, we report about the mechanical relaxation characteristics of an intrinsically self-healable imidazole modified commercial rubber. This kind of self-healing rubber was prepared by melt mixing of 1-butyl imidazole with bromo-butyl rubber (bromine modified isoprene-isobutylene copolymer, BIIR. By this melt mixing process, the reactive allylic bromine of bromo-butyl rubber was converted into imidazole bromide salt. The resulting development of an ionic character to the polymer backbone leads to an ionic association of the groups which ultimately results to the formation of a network structure of the rubber chains. The modified BIIR thus behaves like a robust crosslinked rubber and shows unusual self-healing properties. The non-covalent reversible network has been studied in detail with respect to stress relaxation experiments, scanning electron microscopic and X-ray scattering.

Seasonality of isoprenoid emissions from a primary rainforest in central Amazonia

Science.gov (United States)

Alves, Eliane G.; Jardine, Kolby; Tota, Julio; Jardine, Angela; Yãnez-Serrano, Ana Maria; Karl, Thomas; Tavares, Julia; Nelson, Bruce; Gu, Dasa; Stavrakou, Trissevgeni; Martin, Scot; Artaxo, Paulo; Manzi, Antonio; Guenther, Alex

2016-03-01

Tropical rainforests are an important source of isoprenoid and other volatile organic compound (VOC) emissions to the atmosphere. The seasonal variation of these compounds is however still poorly understood. In this study, vertical profiles of mixing ratios of isoprene, total monoterpenes and total sesquiterpenes, were measured within and above the canopy, in a primary rainforest in central Amazonia, using a proton transfer reaction - mass spectrometer (PTR-MS). Fluxes of these compounds from the canopy into the atmosphere were estimated from PTR-MS measurements by using an inverse Lagrangian transport model. Measurements were carried out continuously from September 2010 to January 2011, encompassing the dry and wet seasons. Mixing ratios were higher during the dry (isoprene - 2.68 ± 0.9 ppbv, total monoterpenes - 0.67 ± 0.3 ppbv; total sesquiterpenes - 0.09 ± 0.07 ppbv) than the wet season (isoprene - 1.66 ± 0.9 ppbv, total monoterpenes - 0.47 ± 0.2 ppbv; total sesquiterpenes - 0.03 ± 0.02 ppbv) for all compounds. Ambient air temperature and photosynthetically active radiation (PAR) behaved similarly. Daytime isoprene and total monoterpene mixing ratios were highest within the canopy, rather than near the ground or above the canopy. By comparison, daytime total sesquiterpene mixing ratios were highest near the ground. Daytime fluxes varied significantly between seasons for all compounds. The maximums for isoprene (2.53 ± 0.5 µmol m-2 h-1) and total monoterpenes (1.77 ± 0.05 µmol m-2 h-1) were observed in the late dry season, whereas the maximum for total sesquiterpenes was found during the dry-to-wet transition season (0.77 ± 0.1 µmol m-2 h-1). These flux estimates suggest that the canopy is the main source of isoprenoids emitted into the atmosphere for all seasons. However, uncertainties in turbulence parameterization near the ground could affect estimates of fluxes that come from the ground. Leaf phenology seemed to be an important driver of seasonal

Development of biogenic VOC emission inventories for the boreal forest

Energy Technology Data Exchange (ETDEWEB)

Tarvainen, V.

2008-07-01

The volatile organic compounds (VOCs) emitted by vegetation, especially forests, can affect local and regional atmospheric photochemistry through their reactions with atmospheric oxidants. Their reaction products may also participate in the formation and growth of new particles which affect the radiation balance of the atmosphere, and thus climate, by scattering and absorbing shortwave and longwave radiation and by modifying the radiative properties, amount and lifetime of clouds. Globally, anthropogenic VOC emissions are far surpassed by the biogenic ones, making biogenic emission inventories an integral element in the development of efficient air quality and climate strategies. The inventories are typically constructed based on landcover information, measured emissions of different plants or vegetation types, and empirical dependencies of the emissions on environmental variables such as temperature and light. This thesis is focused on the VOC emissions from the boreal forest, the largest terrestrial biome with characteristic vegetation patterns and strong seasonality. The isoprene, monoterpene and sesquiterpene emissions of the most prevalent boreal tree species in Finland, Scots pine, have been measured and their seasonal variation and dependence on temperature and light have been studied. The measured emission data and other available observations of the emissions of the principal boreal trees have been used in a biogenic emission model developed for the boreal forests in Finland. The model utilizes satellite landcover information, Finnish forest classification and hourly meteorological data to calculate isoprene, monoterpene, sesquiterpene and other VOC emissions over the growing season. The principal compounds emitted by Scots pine are DELTA3-carene and alpha-pinene in the south boreal zone and alpha- and beta-pinene in the north boreal zone. The monoterpene emissions are dependent on temperature and have a clear seasonal cycle with high emissions in spring

Reconnaissance of the hydrology, water quality, and sources of bacterial and nutrient contamination in the Ozark Plateaus aquifer system and Cave Springs Branch of Honey Creek, Delaware County, Oklahoma, March 1999-March 2000

Science.gov (United States)

Schlottmann, Jamie L.; Tanner, Ralph S.; Samadpour, Mansour

2000-01-01

A reconnaissance investigation of hydrology and water quality was conducted to evaluate possible sources of bacteria and nutrient contamination in the Cave Springs Branch basin and the underlying karstic Ozark Plateau aquifer system. Objectives were to: (1) determine the directions of ground-water flow in the basin and determine whether Cave Springs Branch interacts with ground water, (2) compare water quality in Cave Springs Branch with water quality in nearby wells to determine whether the stream is contaminating nearby wells, and (3) determine sources of fecal coliform bacteria and nitrate contamination in Cave Springs Branch and ground water. Potential sources of bacteria and nitrate in the area include cultivated agriculture, cow and horse on pasture, poultry production, households, and wildlife. Presence of fecal coliform and fecal streptococcal bacteria directly indicate fecal contamination and the potential for the presence of other pathogenic organisms in a water supply. Nitrate in drinking water poses health risks and may indicate the presence of additional contaminants. Fecal coliform bacteria colony counts were least in wells, intermediate in the poultry-processing plant wastewater outfall and Honey Creek above the confluence with Cave Springs Branch, and greatest in Cave Springs Branch. Bacteria strains and resistance to antibiotics by some bacteria indicate that livestock may have been sources of some bacteria in the water samples. Multiple antibiotic resistances were not present in the isolates from the water samples, indicating that the bacteria may not be from human or poultry sources. Ribotyping indicates that Escherichia coli bacteria in water samples from the basin were from bird, cow, horse, dog, deer, and human sources. The presence of multiple ribotypes from each type of animal source except bird indicates that most of the bacteria are from multiple populations of source animals. Identifiable sources of bacteria in Cave Springs Branch at the

Brosimacutins A-I, nine new flavonoids from Brosimum acutifolium.

Science.gov (United States)

Takashima, Junko; Ohsaki, Ayumi

2002-12-01

Nine new flavonoids, brosimacutins A-I (1-9), and four known flavonoids were isolated from the bark of Brosimum acutifolium, a Brazilian folk medicine ("Mururé"). Their structures were elucidated by spectroscopic methods, including 2D NMR. Brosimacutins A-I possess differentially functionalized isoprene units at C-8.

Volatile organic compound emission profiles of four common arctic plants

DEFF Research Database (Denmark)

Vedel-Petersen, Ida; Schollert, Michelle; Nymand, Josephine

2015-01-01

emitted the least BVOCs, dominated by sesquiterpenes (SQTs) and non-isoprenoid BVOCs. The Salix spp. emitted the most, dominated by isoprene. The emissions of B. nana were composed of about two-thirds non-isoprenoid BVOCs, with moderate amounts of monoterpenes (MTs) and SQTs. The total B. nana emissions...

The role of linked phospholipids in the rubber-filler interaction in carbon nanotube (CNT) filler natural rubber (NR) composites

NARCIS (Netherlands)

Le, H.H.; Abhijeet, S.; Ilish, S.; Klehm, J.; Henning, S.; Beiner, M.; Sarkawi, S.S.; Dierkes, Wilma K.; Das, A.; Fischer, D.; Stöckelhuber, K.-W.; Wiessner, S.; Khatiwada, S.P.; Adhikari, R.; Pham, T.; Heinrich, G.; Radusch, H.-J.

2014-01-01

The aim of the present work is to evidence the role of the linked phospholipids of natural rubber (NR) in the rubber-carbon nanotube (CNT) interactions in rubber composites. Three rubbers namely NR, deproteinized NR (DPNR) and a synthetic rubber isoprene (IR) were used as matrix for CNTs. The

Functional traits of urban trees: air pollution mitigation potential

Czech Academy of Sciences Publication Activity Database

Grote, R.; Samson, R.; Alonso, R.; Amorim, J. H.; Cariňanos, P.; Churkina, S.; Fares, S.; Thiec, D. L.; Niinemets, Ü.; Mikkelsen, T. N.; Paoletti, E.; Tiwary, A.; Calfapietra, Carlo

2016-01-01

Roč. 14, č. 10 (2016), s. 543-550 ISSN 1540-9295 EU Projects: European Commission(XE) FP1204 Institutional support: RVO:67179843 Keywords : volatile organic compounds * particulare matter * isoprene emission * ozone deposition * climate change * global change Subject RIV: EH - Ecology, Behaviour Impact factor: 8.039, year: 2016

Mechanisms for formation of organic acids in gas-phase reactions of ozone and hydroxyl radical with dialkenes and unsaturated carbonyls

Science.gov (United States)

Chien, Chao-Jung

2001-07-01

Carboxylic acids are ubiquitous throughout the troposphere and may contribute significant fractions of the free acidity in some remote areas. One of the important sources of these carboxylic acids is thought to be photochemical transformation of biogenic hydrocarbons such as isoprene. For the work reported here, atmospheric samples from University of North Carolina dual outdoor environmental chamber under simulated urban atmospheric conditions were analyzed for carboxylic acids. Both OH radicals and O3 initiated photooxidation reaction experiments were performed for isoprene, along with its structural analogs, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene, and their primary photooxidation products, methacrolein, acrolein, and methyl vinyl ketone. Among the detected carboxylic acids were formic, acetic, and several multifunctional carboxylic acids, including methacrylic, acrylic, glyoxylic, and glycolic acids. Quantification of most carboxylic acid products was also established. Formation yields of carboxylic acids from the reactions of O3 with studied compounds were determined, and time-concentration series of the reactants and carboxylic acid products were measured to facilitate mechanism formulation. While the reaction mechanisms of Criegee biradicals arising from decomposition of primary ozonides are proposed to account for the observed carboxylic acid products in the ozonolysis of unsaturated hydrocarbons, reactions of peroxy acyl radicals with HO2 and/or other peroxy radicals are thought to be responsible for the formation of carboxylic acids during the OH-initiated reactions in the presence of NOx. In this study, smog chamber simulations have also been performed for selected compounds using Morpho, a photochemical kinetic simulation software package. Explicit photochemical mechanisms with O 3 and OH radicals that lead to formation of carboxylic acids were elaborated and implemented, and the simulation results were compared with those from other chemical

Evaluation of Global Photosynthesis and BVOC Emission Covariance with Climate in NASA ModelE2-Y

Science.gov (United States)

Unger, N.

2012-12-01

Terrestrial gross primary productivity (GPP), a measure of the total amount of CO2 removed from the atmosphere every year to fuel photosynthesis, is the largest global carbon flux. GPP is vital for human welfare as the basis for food and fiber, and provides the crucial ecosystem service of reducing the accumulation of fossil fuel CO2 in the atmosphere. Land plants emit a significant fraction of the assimilated carbon back to the atmosphere in the form of biogenic volatile organic compounds (BVOCs). Isoprene is the dominant BVOC emission with an estimated global source of 200-660 TgC/yr. Global monoterpene emission estimates range from 30-130 TgC/yr. BVOC photochemical oxidation exerts a profound impact on the distribution and variability of the short-lived climate forcers: ozone, biogenic secondary organic aerosol and methane. Here, we apply multiple observational datasets from a suite of platforms to evaluate an updated global chemistry-climate model that is coupled to a new vegetation biophysics scheme incorporating photosynthesis-dependent BVOC emissions (NASA ModelE2-Y). A fixed vegetation structure dataset based on 8 plant functional types and prescribed phenology including crop planting and harvesting gives GPP of 128 PgC/yr and a global isoprene source of 200TgC/yr. The model GPP captures 85% of the annual average zonal mean variability in a FLUXNET-derived global dataset that was generated by data orientated diagnostic upscaling. We assess model BVOC emission climatology against a comprehensive database of campaign-average above canopy flux measurements and surface concentrations of isoprene and monoterpene collected between 1995-2010 across a wide range of ecosystem types, regions and seasons (> 25 flux estimates; > 22 surface concentration values). We evaluate the diurnal, seasonal and interannual integrity of the model BVOC variability against 9 sites for isoprene and 4 sites for monoterpene. The model captures ~60% of the variability in the time

Observations and Modeling of the Green Ocean Amazon 2014/15: Hydroxyl Radical (OH) Chemical Ionization Mass Spectrometer (CIMS) Field Campaign Report

Energy Technology Data Exchange (ETDEWEB)

Kim, Saewung [Univ. of California, Irvine, CA (United States)

2016-05-01

The University of California, Irvine, science team (Dr. Saewung Kim, Dr. Roger Seco, Dr. Alex Guenther, and Dr. Jim Smith) deployed a chemical ionization mass spectrometer system for hydroxyl radical (OH) and sulfuric acid quantifications. As part of the GoAmazon 2014/15 field campaign. Hydroxyl radical determines tropospheric oxidation capacity and had been expected to be very low in the pristine rain forest region such as the Brazilian Amazon because of the presence of significant levels of highly reactive biogenic volatile organic compounds and very low levels of NO, which is an OH recycling agent. However, several recent in situ OH observations provided by a laser-induced fluorescence system reported unaccountably high OH concentrations. To address this discrepancy, a series of laboratory and theoretical studies has postulated chemical reaction mechanisms of isoprene that may regenerate OH in photo-oxidation processes. Along with these efforts, potential artifacts on the laser induced fluorescence system from isoprene and its oxidation products also have been explored. Therefore, the first chemical ionization mass spectrometer observations at the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility’s T3 site in Manacapuru, Brazil, are expected to provide a critical experimental constraint to address uncertainty in constraining oxidation capacity over pristine rain forest environments. In addition, we deployed a National Center for Atmospheric Research (NCAR) proton transfer reaction time-of-flight mass spectrometer to characterize atmospheric volatile organic compound levels, especially isoprene and its oxidation products, which are critical input parameters for box modeling to simulate OH with different isoprene photo-oxidation schemes. As there has been no report on noticeable new particle formation events, our first in situ sulfuric acid observations in the Amazon rain forest were expected to constrain the

Impact of climate change on tropospheric ozone and its global budgets

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G. Zeng

2008-01-01

Full Text Available We present the chemistry-climate model UM_CAM in which a relatively detailed tropospheric chemical module has been incorporated into the UK Met Office's Unified Model version 4.5. We obtain good agreements between the modelled ozone/nitrogen species and a range of observations including surface ozone measurements, ozone sonde data, and some aircraft campaigns.

Four 2100 calculations assess model responses to projected changes of anthropogenic emissions (SRES A2, climate change (due to doubling CO₂, and idealised climate change-associated changes in biogenic emissions (i.e. 50% increase of isoprene emission and doubling emissions of soil-NO_x. The global tropospheric ozone burden increases significantly for all the 2100 A2 simulations, with the largest response caused by the increase of anthropogenic emissions. Climate change has diverse impacts on O₃ and its budgets through changes in circulation and meteorological variables. Increased water vapour causes a substantial ozone reduction especially in the tropical lower troposphere (>10 ppbv reduction over the tropical ocean. On the other hand, an enhanced stratosphere-troposphere exchange of ozone, which increases by 80% due to doubling CO₂, contributes to ozone increases in the extratropical free troposphere which subsequently propagate to the surface. Projected higher temperatures favour ozone chemical production and PAN decomposition which lead to high surface ozone levels in certain regions. Enhanced convection transports ozone precursors more rapidly out of the boundary layer resulting in an increase of ozone production in the free troposphere. Lightning-produced NO_x increases by about 22% in the doubled CO₂ climate and contributes to ozone production.

The response to the increase of isoprene emissions shows that the change of ozone is largely determined by background NO_x levels: high

Isoprenoids emission in Stipa tenacissima L.: Photosynthetic control and the effect of UV light

Czech Academy of Sciences Publication Activity Database

Guidolotti, G.; Rey, A.; Medori, M.; Calfapietra, Carlo

2016-01-01

Roč. 208, B (2016), s. 336-344 ISSN 0269-7491 R&D Projects: GA MŠk(CZ) LO1415; GA MŠk(CZ) LD13031 Institutional support: RVO:67179843 Keywords : Isoprene * Monoterpene * Alfa grass * UV radiation * Semiarid ecosystems Subject RIV: EH - Ecology, Behaviour Impact factor: 5.099, year: 2016

Aerial gamma ray and magnetic survey, Jefferson City Quadrangle, Missouri. Final report

International Nuclear Information System (INIS)

1980-11-01

The Jefferson City quadrangle covers approximately 7500 square miles at the Northwestern end of the Ozark uplift. Lithified material exposed, ranges in age from Cambrian through Pennsylvanian, but Pennsylvanian sediments dominate the surface as mapped. Some alluvium is mapped in river flood plain areas. A search of available literature revealed no known uranium deposits. A total of 95 uranium anomalies were detected and are discussed briefly in this report. All anomalies are related to cultural features, but those associated with coal mine tailings appear to have some significance. Magnetic data appear to relate to complexities in the underlying Precambrian rocks

Aerial gama ray and magnetic survey: Lawrence Quadrangle of Kansas and Missouri. Final report

International Nuclear Information System (INIS)

1980-11-01

The Lawrence quadrangle covers approximately 7500 square miles in Kansas and Missouri over the western edge of the Ozark Uplift. Sediments in this area are mostly Pennsylvanian and Permian sandstone, shale, limestone, and coal. As mapped, these are the dominant units in the quadrangle. A search of available literature revealed no known uranium deposits. A total of 94 uranium anomalies were detected and are discussed briefly. Most appear to be related to cultural features. Those associated with coal mine tailings appear to be most significant. Magnetic data appears to relate to complexities in the Precambrian basement

Mapping gas-phase organic reactivity and concomitant secondary organic aerosol formation: chemometric dimension reduction techniques for the deconvolution of complex atmospheric data sets

Science.gov (United States)

Wyche, K. P.; Monks, P. S.; Smallbone, K. L.; Hamilton, J. F.; Alfarra, M. R.; Rickard, A. R.; McFiggans, G. B.; Jenkin, M. E.; Bloss, W. J.; Ryan, A. C.; Hewitt, C. N.; MacKenzie, A. R.

2015-07-01

Highly non-linear dynamical systems, such as those found in atmospheric chemistry, necessitate hierarchical approaches to both experiment and modelling in order to ultimately identify and achieve fundamental process-understanding in the full open system. Atmospheric simulation chambers comprise an intermediate in complexity, between a classical laboratory experiment and the full, ambient system. As such, they can generate large volumes of difficult-to-interpret data. Here we describe and implement a chemometric dimension reduction methodology for the deconvolution and interpretation of complex gas- and particle-phase composition spectra. The methodology comprises principal component analysis (PCA), hierarchical cluster analysis (HCA) and positive least-squares discriminant analysis (PLS-DA). These methods are, for the first time, applied to simultaneous gas- and particle-phase composition data obtained from a comprehensive series of environmental simulation chamber experiments focused on biogenic volatile organic compound (BVOC) photooxidation and associated secondary organic aerosol (SOA) formation. We primarily investigated the biogenic SOA precursors isoprene, α-pinene, limonene, myrcene, linalool and β-caryophyllene. The chemometric analysis is used to classify the oxidation systems and resultant SOA according to the controlling chemistry and the products formed. Results show that "model" biogenic oxidative systems can be successfully separated and classified according to their oxidation products. Furthermore, a holistic view of results obtained across both the gas- and particle-phases shows the different SOA formation chemistry, initiating in the gas-phase, proceeding to govern the differences between the various BVOC SOA compositions. The results obtained are used to describe the particle composition in the context of the oxidised gas-phase matrix. An extension of the technique, which incorporates into the statistical models data from anthropogenic (i

Oak regeneration and overstory density in the Missouri Ozarks

Science.gov (United States)

David R. Larsen; Monte A. Metzger

1997-01-01

Reducing overstory density is a commonly recommended method of increasing the regeneration potential of oak (Quercus) forests. However, recommendations seldom specify the probable increase in density or the size of reproduction associated with a given residual overstory density. This paper presents logistic regression models that describe this...

Land-cover change in the Ozark Highlands, 1973-2000

Science.gov (United States)

Karstensen, Krista A.

2010-01-01

Led by the Geographic Analysis and Monitoring Program of the U.S. Geological Survey (USGS) in collaboration with the U.S. Environmental Protection Agency (EPA) and the National Aeronautics and Space Administration (NASA), the Land-Cover Trends Project was initiated in 1999 and aims to document the types, geographic distributions, and rates of land-cover change on a region by region basis for the conterminous United States, and to determine some of the key drivers and consequences of the change (Loveland and others, 2002). For 1973, 1980, 1986, 1992, and 2000 land-cover maps derived from the Landsat series are classified by visual interpretation, inspection of historical aerial photography and ground survey, into 11 land-cover classes. The classes are defined to capture land cover that is discernable in Landsat data. A stratified probability-based sampling methodology undertaken within the 84 Omernik Level III Ecoregions (Omernik, 1987) was used to locate the blocks, with 9 to 48 blocks per ecoregion. The sampling was designed to enable a statistically robust 'scaling up' of the sample-classification data to estimate areal land-cover change within each ecoregion (Loveland and others, 2002; Stehman and others, 2005). At the time of writing, approximately 90 percent of the 84 conterminous United States ecoregions have been processed by the Land-Cover Trends Project. Results from these completed ecoregions illustrate that across the conterminous United States there is no single profile of land-cover/land-use change, rather, there are varying pulses affected by clusters of change agents (Loveland and others, 2002). Land-Cover Trends Project results for the conterminous United States to-date are being used for collaborative environmental change research with partners such as; the National Science Foundation, the National Oceanic and Atmospheric Administration, and the U.S. Fish and Wildlife Service. The strategy has also been adapted for use in a NASA global deforestation initiative, and elements of the project design are being used in the North American Carbon Program's assessment of forest disturbance.

Light hydrocarbons vertical profiles and fluxes in a french rural area

Science.gov (United States)

Kanakidou, M.; Bonsang, B.; Lambert, G.

By means of manned hot air balloon flights, in July 1986, an experiment was conducted in a rural area of southwest France in order to determine the production at ground level of non-methane hydrocarbons in the C 2-C 6 range. Flux determinations were based on vertical profiles before and after the development of a temperature inversion layer which allowed the measurement of the NMHC accumulation close to ground level. The main species produced in the late afternoon were acetylene, propane, ethene, propene and ethane with production rates of the order of 0.5 to 2 × 10 -4g of C m -2 h -1. Isoprene was found to be the main other unsaturated species also produced. The fluxes and the atmospheric content of the air column before the inversion are consistent with an average OH radical concentration of 2 × 10 6 cm -3.

Seasonality of isoprenoid emissions from a primary rainforest in central Amazonia

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E. G. Alves

2016-03-01

Full Text Available Tropical rainforests are an important source of isoprenoid and other volatile organic compound (VOC emissions to the atmosphere. The seasonal variation of these compounds is however still poorly understood. In this study, vertical profiles of mixing ratios of isoprene, total monoterpenes and total sesquiterpenes, were measured within and above the canopy, in a primary rainforest in central Amazonia, using a proton transfer reaction – mass spectrometer (PTR-MS. Fluxes of these compounds from the canopy into the atmosphere were estimated from PTR-MS measurements by using an inverse Lagrangian transport model. Measurements were carried out continuously from September 2010 to January 2011, encompassing the dry and wet seasons. Mixing ratios were higher during the dry (isoprene – 2.68 ± 0.9 ppbv, total monoterpenes – 0.67 ± 0.3 ppbv; total sesquiterpenes – 0.09 ± 0.07 ppbv than the wet season (isoprene – 1.66 ± 0.9 ppbv, total monoterpenes – 0.47 ± 0.2 ppbv; total sesquiterpenes – 0.03 ± 0.02 ppbv for all compounds. Ambient air temperature and photosynthetically active radiation (PAR behaved similarly. Daytime isoprene and total monoterpene mixing ratios were highest within the canopy, rather than near the ground or above the canopy. By comparison, daytime total sesquiterpene mixing ratios were highest near the ground. Daytime fluxes varied significantly between seasons for all compounds. The maximums for isoprene (2.53 ± 0.5 µmol m−2 h−1 and total monoterpenes (1.77 ± 0.05 µmol m−2 h−1 were observed in the late dry season, whereas the maximum for total sesquiterpenes was found during the dry-to-wet transition season (0.77 ± 0.1 µmol m−2 h−1. These flux estimates suggest that the canopy is the main source of isoprenoids emitted into the atmosphere for all seasons. However, uncertainties in turbulence parameterization near the ground could affect estimates of fluxes that come from the ground. Leaf

Which processes drive observed variations of HCHO columns over India?

Science.gov (United States)

Surl, Luke; Palmer, Paul I.; González Abad, Gonzalo

2018-04-01

We interpret HCHO column variations observed by the Ozone Monitoring Instrument (OMI), aboard the NASA Aura satellite, over India during 2014 using the GEOS-Chem atmospheric chemistry and transport model. We use a nested version of the model with a horizontal resolution of approximately 25 km. HCHO columns are related to local emissions of volatile organic compounds (VOCs) with a spatial smearing that increases with the VOC lifetime. Over India, HCHO has biogenic, pyrogenic, and anthropogenic VOC sources. Using a 0-D photochemistry model, we find that isoprene has the largest molar yield of HCHO which is typically realized within a few hours. We also find that forested regions that neighbour major urban conurbations are exposed to high levels of nitrogen oxides. This results in depleted hydroxyl radical concentrations and a delay in the production of HCHO from isoprene oxidation. We find that propene is the only anthropogenic VOC emitted in major Indian cities that produces HCHO at a comparable (but slower) rate to isoprene. The GEOS-Chem model reproduces the broad-scale annual mean HCHO column distribution observed by OMI (r = 0.6), which is dominated by a distinctive meridional gradient in the northern half of the country, and by localized regions of high columns that coincide with forests. Major discrepancies are noted over the Indo-Gangetic Plain (IGP) and Delhi. We find that the model has more skill at reproducing observations during winter (JF) and pre-monsoon (MAM) months with Pearson correlations r > 0.5 but with a positive model bias of x≃1×1015 molec cm-2. During the monsoon season (JJAS) we reproduce only a diffuse version of the observed meridional gradient (r = 0.4). We find that on a continental scale most of the HCHO column seasonal cycle is explained by monthly variations in surface temperature (r = 0.9), suggesting a role for biogenic VOCs, in agreement with the 0-D and GEOS-Chem model calculations. We also find that the seasonal cycle during

Data acquisition. GRAAL experiment. Hybrid reactor experiment. AMS experiment

International Nuclear Information System (INIS)

Barancourt, D.; Barbier, G.; Bosson, G.; Bouvier, J.; Gallin-Martel, L.; Meillon, B.; Stassi, P.; Tournier, M.

1997-01-01

The main activity of the data acquisition team has consisted in hardware and software developments for the GRAAL experiment with the trigger board, for the 'Reacteurs Hybrides' group with an acquisition board ADCVME8V and for the AMS experiment with the monitoring of the aerogel detector. (authors)

Secondary organic aerosol importance in the future atmosphere

International Nuclear Information System (INIS)

Tsigaridis, K.; Kanakidou, M.

2007-01-01

In order to investigate the secondary organic aerosol (SOA) response to changes in biogenic volatile organic compounds (VOC) emissions in the future atmosphere and how important will SOA be relative to the major anthropogenic aerosol component (sulfate), the global three-dimensional chemistry/transport model TM3 has been used. Emission estimates of biogenic VOC (BVOC) and anthropogenic gases and particles from the literature for the year 2100 have been adopted. According to our present-day model simulations, isoprene oxidation produces 4.6 Tg SOA yr -1 , that is less than half of the 12.2 Tg SOA yr -1 formed by the oxidation of other BVOC. In the future, nitrate radicals and ozone become more important than nowadays, but remain minor oxidants for both isoprene and aromatics. SOA produced by isoprene is estimated to almost triple, whereas the production from other BVOC more than triples. The calculated future SOA burden change, from 0.8 Tg at present to 2.0 Tg in the future, is driven by changes in emissions, oxidant levels and pre-existing particles. The non-linearity in SOA formation and the involved chemical and physical feedbacks prohibit the quantitative attribution of the computed changes to the above-mentioned individual factors. In 2100, SOA burden is calculated to exceed that of sulfate, indicating that SOA might become more important than nowadays. These results critically depend on the biogenic emissions and thus are subject to the high uncertainty associated with these emissions estimated due to the insufficient knowledge on plant response to carbon dioxide changes. Nevertheless, they clearly indicate that the change in oxidants and primary aerosol caused by human activities can contribute as much as the change in BVOC emissions to the increase of the biogenic SOA production in the future atmosphere. (authors)

Secondary formation of oxalic acid and related organic species from biogenic sources in a larch forest at the northern slope of Mt. Fuji

Science.gov (United States)

Mochizuki, Tomoki; Kawamura, Kimitaka; Miyazaki, Yuzo; Wada, Ryuichi; Takahashi, Yoshiyuki; Saigusa, Nobuko; Tani, Akira

2017-10-01

To better understand the formation of water-soluble organic aerosols in the forest atmosphere, we measured low molecular weight (LMW) dicarboxylic acids, oxocarboxylic acids, α-dicarbonyls, unsaturated fatty acids (UFAs), and water-soluble organic carbon (WSOC) in aerosols from a Larix kaempferi forest located at the northern slope of Mt. Fuji, Japan, in summer 2012. Concentrations of dicarboxylic acids, oxocarboxylic acids, α-dicarbonyls, and WSOC showed maxima in daytime. Relative abundance of oxalic acid in LMW dicarboxylic acids was on average 52% and its average concentration was 214 ng m-3. We found that diurnal and temporal variations of oxalic acid are different from those of isoprene and α-pinene, whereas biogenic secondary organic aerosols (BSOAs) derived from isoprene and α-pinene showed similar variations with oxalic acid. The mass concentration ratios of oxalic acid/BSOAs were relatively constant, although a large variation in the concentrations of toluene that is an anthropogenic volatile organic compound was observed. These results suggest that formation of oxalic acid is associated with the oxidation of isoprene and α-pinene with O3 and other oxidants in the forest atmosphere. In addition, concentrations of UFAs were observed, for the first time, to decrease dramatically during daytime in the forest. Mass concentration ratios of azelaic acid to UFAs showed a positive correlation with O3, suggesting that UFAs are oxidized to yield azelaic acid, which may be further decomposed to oxalic acid in the forest atmosphere. We found that contributions of oxalic acid to WSOC are significantly high ranging from 3.7 to 9.7% (average 6.0%). This study demonstrates that forest ecosystem is an important source of oxalic acid and other dicarboxylic acids in the atmosphere.

Contrasting organic aerosol particles from boreal and tropical forests during HUMPPA-COPEC-2010 and AMAZE-08 using coherent vibrational spectroscopy

Directory of Open Access Journals (Sweden)

C. J. Ebben

2011-10-01

Full Text Available We present the vibrational sum frequency generation spectra of organic particles collected in a boreal forest in Finland and a tropical forest in Brazil. These spectra are compared to those of secondary organic material produced in the Harvard Environmental Chamber. By comparing coherent vibrational spectra of a variety of terpene and olefin reference compounds, along with the secondary organic material synthesized in the environmental chamber, we show that submicron aerosol particles sampled in Southern Finland during HUMPPA-COPEC-2010 are composed to a large degree of material similar in chemical composition to synthetic α-pinene-derived material. For material collected in Brazil as part of AMAZE-08, the organic component is found to be chemically complex in the coarse mode but highly uniform in the fine mode. When combined with histogram analyses of the isoprene and monoterpene abundance recorded during the HUMPPA-COPEC-2010 and AMAZE-08 campaigns, the findings presented here indicate that if air is rich in monoterpenes, submicron-sized secondary aerosol particles that form under normal OH and O₃ concentration levels can be described in terms of their hydrocarbon content as being similar to α-pinene-derived model secondary organic aerosol particles. If the isoprene concentration dominates the chemical composition of organic compounds in forest air, then the hydrocarbon component of secondary organic material in the submicron size range is not simply well-represented by that of isoprene-derived model secondary organic aerosol particles but is more complex. Throughout the climate-relevant size range of the fine mode, however, we find that the chemical composition of the secondary organic particle material from such air is invariant with size, suggesting that the particle growth does not change the chemical composition of the hydrocarbon component of the particles in a significant way.

Observations of vegetation induced breezes and their impact on convection

Science.gov (United States)

Garcia-Carreras, Luis; Parker, Douglas J.; Taylor, Christopher M.; Reeves, Claire; Murphy, Jennifer

2010-05-01

Aircraft observations over Benin during the early afternoon of 17 August 2006 are used to look at the impact of heterogeneities in vegetation cover, primarily between crop and forest/shrub, on the thermodynamic and dynamical properties of the planetary boundary layer (PBL). Isoprene, a biogenic organic compound emitted primarily by woody vegetation species, was measured and is used to link the vegetation patterns to the PBL properties. The aircraft observations show the presence of a persistent mesoscale organization of the winds persisting over two hours, controlling the pattern of cumulus congestus cloud in the area. The mesoscale flows are closely linked to temperature anomalies that mirror the vegetation patterns at the surface. These results are consistent with the presence of higher Bowen ratios over forested areas, associated with higher evapotranspiration and isoprene emissions, producing negative PBL temperature anomalies over the forested area compared to adjacent cropland. The temperature gradients that thus arise at vegetation boundaries are then sufficient to initiate vegetation breezes. The relationships between PBL temperatures and isoprene, linking the land-surface to the PBL, and PBL temperatures and winds are very significant for length-scales above 10 and 8km respectively. The convergence zones, and therefore clouds, associated with the land-induced mesoscale flows tend to occur on the southern edge of the warm temperature anomalies. This is attributed to the presence of a northerly synoptic flow, which strengthens the southerly parts of the mesoscale flow, as well as displacing the convergence zones southward. A visible satellite climatology for the whole season shows an enhancement of cloud over the cropland during the early afternoon, consistent with the presence of land-induced flows. These results suggest that the presence of these flows have a climatological impact on the initiation of convection in the region.

Fluxes and concentrations of volatile organic compounds from a South-East Asian tropical rainforest

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B. Langford

2010-09-01

Full Text Available As part of the OP3 field study of rainforest atmospheric chemistry, above-canopy fluxes of isoprene, monoterpenes and oxygenated volatile organic compounds were made by virtual disjunct eddy covariance from a South-East Asian tropical rainforest in Malaysia. Approximately 500 hours of flux data were collected over 48 days in April–May and June–July 2008. Isoprene was the dominant non-methane hydrocarbon emitted from the forest, accounting for 80% (as carbon of the measured emission of reactive carbon fluxes. Total monoterpene emissions accounted for 18% of the measured reactive carbon flux. There was no evidence for nocturnal monoterpene emissions and during the day their flux rate was dependent on both light and temperature. The oxygenated compounds, including methanol, acetone and acetaldehyde, contributed less than 2% of the total measured reactive carbon flux. The sum of the VOC fluxes measured represents a 0.4% loss of daytime assimilated carbon by the canopy, but atmospheric chemistry box modelling suggests that most (90% of this reactive carbon is returned back to the canopy by wet and dry deposition following chemical transformation. The emission rates of isoprene and monoterpenes, normalised to 30 °C and 1000 μmol m⁻² s⁻¹ PAR, were 1.6 mg m⁻² h⁻¹ and 0.46mg m⁻² h⁻¹ respectively, which was 4 and 1.8 times lower respectively than the default value for tropical forests in the widely-used MEGAN model of biogenic VOC emissions. This highlights the need for more direct canopy-scale flux measurements of VOCs from the world's tropical forests.

Role of aldehyde chemistry and NOx concentrations in secondary organic aerosol formation

Directory of Open Access Journals (Sweden)

P. O. Wennberg

2010-08-01

Full Text Available Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene, the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA via methacrolein (a C4-unsaturated aldehyde under urban high-NOx conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN as the important intermediate to isoprene and methacrolein SOA in this NOx regime. Here we show that as a result of this chemistry, NO2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NOx effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232 is insignificant, even under high-NO2 conditions, as PAN (peroxy acyl nitrate, RC(OOONO2 formation is structurally unfavorable. At atmospherically relevant NO2/NO ratios (3–8, the SOA yields from isoprene high-NOx photooxidation are 3 times greater than previously measured at lower NO2/NO ratios. At sufficiently high NO2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO2 can exceed that from RO2+HO2 reactions under the same inorganic seed conditions, making RO2+NO2 an important channel for SOA formation.

Role of aldehyde chemistry and NOx concentrations in secondary organic aerosol formation

Science.gov (United States)

Chan, A. W. H.; Chan, M. N.; Surratt, J. D.; Chhabra, P. S.; Loza, C. L.; Crounse, J. D.; Yee, L. D.; Flagan, R. C.; Wennberg, P. O.; Seinfeld, J. H.

2010-08-01

Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene), the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA) via methacrolein (a C4-unsaturated aldehyde) under urban high-NOx conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NOx regime. Here we show that as a result of this chemistry, NO2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NOx effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232) is insignificant, even under high-NO2 conditions, as PAN (peroxy acyl nitrate, RC(O)OONO2) formation is structurally unfavorable. At atmospherically relevant NO2/NO ratios (3-8), the SOA yields from isoprene high-NOx photooxidation are 3 times greater than previously measured at lower NO2/NO ratios. At sufficiently high NO2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO2 can exceed that from RO2+HO2 reactions under the same inorganic seed conditions, making RO2+NO2 an important channel for SOA formation.

Classifying organic materials by oxygen-to-carbon elemental ratio to predict the activation regime of Cloud Condensation Nuclei (CCN

Directory of Open Access Journals (Sweden)

M. Kuwata

2013-05-01

Full Text Available The governing highly soluble, slightly soluble, or insoluble activation regime of organic compounds as cloud condensation nuclei (CCN was examined as a function of oxygen-to-carbon elemental ratio (O : C. New data were collected for adipic, pimelic, suberic, azelaic, and pinonic acids. Secondary organic materials (SOMs produced by α-pinene ozonolysis and isoprene photo-oxidation were also included in the analysis. The saturation concentrations C of the organic compounds in aqueous solutions served as the key parameter for delineating regimes of CCN activation, and the values of C were tightly correlated to the O : C ratios. The highly soluble, slightly soluble, and insoluble regimes of CCN activation were found to correspond to ranges of [O : C] > 0.6, 0.2 < [O : C] < 0.6, and [O : C] < 0.2, respectively. These classifications were evaluated against CCN activation data of isoprene-derived SOM (O : C = 0.69–0.72 and α-pinene-derived SOM (O : C = 0.38–0.48. Isoprene-derived SOM had highly soluble activation behavior, consistent with its high O : C ratio. For α-pinene-derived SOM, although CCN activation can be modeled as a highly soluble mechanism, this behavior was not predicted by the O : C ratio, for which a slightly soluble mechanism was anticipated. Complexity in chemical composition, resulting in continuous water uptake and the absence of a deliquescence transition that can thermodynamically limit CCN activation, might explain the difference in the behavior of α-pinene-derived SOM compared to that of pure organic compounds. The present results suggest that atmospheric particles dominated by hydrocarbon-like organic components do not activate (i.e., insoluble regime whereas those dominated by oxygenated organic components activate (i.e., highly soluble regime for typical atmospheric cloud life cycles.

Direct ecosystem fluxes of volatile organic compounds from oil palms in South-East Asia

Directory of Open Access Journals (Sweden)

P. K. Misztal

2011-09-01

Full Text Available This paper reports the first direct eddy covariance fluxes of reactive biogenic volatile organic compounds (BVOCs from oil palms to the atmosphere using proton-transfer-reaction mass spectrometry (PTR-MS, measured at a plantation in Malaysian Borneo. At midday, net isoprene flux constituted the largest fraction (84 % of all emitted BVOCs measured, at up to 30 mg m⁻² h⁻¹ over 12 days. By contrast, the sum of its oxidation products methyl vinyl ketone (MVK and methacrolein (MACR exhibited clear deposition of 1 mg m⁻² h⁻¹, with a small average canopy resistance of 230 s m⁻¹. Approximately 15 % of the resolved BVOC flux from oil palm trees could be attributed to floral emissions, which are thought to be the largest reported biogenic source of estragole and possibly also toluene. Although on average the midday volume mixing ratio of estragole exceeded that of toluene by almost a factor of two, the corresponding fluxes of these two compounds were nearly the same, amounting to 0.81 and 0.76 mg m⁻² h⁻¹, respectively. By fitting the canopy temperature and PAR response of the MEGAN emissions algorithm for isoprene and other emitted BVOCs a basal emission rate of isoprene of 7.8 mg m⁻² h⁻¹ was derived. We parameterise fluxes of depositing compounds using a resistance approach using direct canopy measurements of deposition. Consistent with Karl et al. (2010, we also propose that it is important to include deposition in flux models, especially for secondary oxidation products, in order to improve flux predictions.

Determination of Selected Volatiles in Cigarette Mainstream Smoke. The CORESTA 2009 Collaborative Study and Recommended Method

Directory of Open Access Journals (Sweden)

Intorp M

2014-12-01

Full Text Available A recommended method has been developed and published by CORESTA, applicable to the quantification of selected volatiles (1,3-butadiene, isoprene, acrylonitrile, benzene, and toluene in the gas phase of cigarette mainstream smoke. The method involved smoke collection in impinger traps and detection and measurement using gas chromatography/mass spectrometry techniques.

Regional modeling of carbonaceous aerosols over Europe-focus on secondary organic aerosols

International Nuclear Information System (INIS)

Bessagnet, B.; Menut, L.; Curci, G.; Hodzic, A.; Guillaume, B.; Liousse, C.; Moukhtar, S.; Pun, B.; Seigneur, C.; Schulz, M.

2008-01-01

In this study, an improved and complete secondary organic aerosols (SOA) chemistry scheme was implemented in the CHIMERE model. The implementation of isoprene chemistry for SOA significantly improves agreement between long series of simulated and observed particulate matter concentrations. While simulated organic carbon concentrations are clearly improved at elevated sites by adding the SOA scheme, time correlation are impaired at low level sites in Portugal, Italy and Slovakia. At several sites a clear underestimation by the CHIMERE model is noticed in wintertime possibly due to missing wood burning emissions as shown in previous modeling studies. In Europe, the CHIMERE model gives yearly average SOA concentrations ranging from 0.5 μg m -3 in the Northern Europe to 4 μg m -3 over forested regions in Spain, France, Germany and Italy. In addition, our work suggests that during the highest fire emission periods, fires can be the dominant source of primary organic carbon over the Mediterranean Basin, but the SOA contribution from fire emissions is low. Isoprene chemistry has a strong impact on SOA formation when using current available kinetic schemes. (authors)

Boundary layer concentrations and landscape scale emissions of volatile organic compounds in early spring

Directory of Open Access Journals (Sweden)

S. Haapanala

2007-01-01

Full Text Available Boundary layer concentrations of several volatile organic compounds (VOC were measured during two campaigns in springs of 2003 and 2006. The measurements were conducted over boreal landscapes near SMEAR II measurement station in Hyytiälä, Southern Finland. In 2003 the measuremens were performed using a light aircraft and in 2006 using a hot air balloon. Isoprene concentrations were low, usually below detection limit. This can be explained by low biogenic production due to cold weather, phenological stage of the isoprene emitting plants, and snow cover. Monoterpenes were observed frequently. The average total monoterpene concentration in the boundary layer was 33 pptv. Many anthropogenic compounds such as benzene, xylene and toluene, were observed in high amounts. Ecosystem scale surface emissions were estimated using a simple mixed box budget methodology. Total monoterpene emissions varied up to 80 μg m−2 h−1, α-pinene contributing typically more than two thirds of that. These emissions were somewhat higher that those calculated using emission algorithm. The highest emissions of anthropogenic compounds were those of p/m xylene.

Design, engineering, and construction of photosynthetic microbial cell factories for renewable solar fuel production.

Science.gov (United States)

Lindblad, Peter; Lindberg, Pia; Oliveira, Paulo; Stensjö, Karin; Heidorn, Thorsten

2012-01-01

There is an urgent need to develop sustainable solutions to convert solar energy into energy carriers used in the society. In addition to solar cells generating electricity, there are several options to generate solar fuels. This paper outlines and discusses the design and engineering of photosynthetic microbial systems for the generation of renewable solar fuels, with a focus on cyanobacteria. Cyanobacteria are prokaryotic microorganisms with the same type of photosynthesis as higher plants. Native and engineered cyanobacteria have been used by us and others as model systems to examine, demonstrate, and develop photobiological H(2) production. More recently, the production of carbon-containing solar fuels like ethanol, butanol, and isoprene have been demonstrated. We are using a synthetic biology approach to develop efficient photosynthetic microbial cell factories for direct generation of biofuels from solar energy. Present progress and advances in the design, engineering, and construction of such cyanobacterial cells for the generation of a portfolio of solar fuels, e.g., hydrogen, alcohols, and isoprene, are presented and discussed. Possibilities and challenges when introducing and using synthetic biology are highlighted.

Design, Engineering, and Construction of Photosynthetic Microbial Cell Factories for Renewable Solar Fuel Production

Energy Technology Data Exchange (ETDEWEB)

Lindblad, Peter; Lindberg, Pia; Stensjoe, Karin (Photochemistry and Molecular Science, Dept. of Chemistry-Aangstroem Laboratory, Uppsala Univ., Uppsala (Sweden)), E-mail: Peter.Lindblad@kemi.uu.se; Oliveira, Paulo (Instituto de Biologia Molecular e Celular, Porto (Portugal)); Heidorn, Thorsten (Bioforsk-Norwegian Inst. for Agricultural and Environmental Research, Aas Oslo, (Norway))

2012-03-15

There is an urgent need to develop sustainable solutions to convert solar energy into energy carriers used in the society. In addition to solar cells generating electricity, there are several options to generate solar fuels. This paper outlines and discusses the design and engineering of photosynthetic microbial systems for the generation of renewable solar fuels, with a focus on cyanobacteria. Cyanobacteria are prokaryotic microorganisms with the same type of photosynthesis as higher plants. Native and engineered cyanobacteria have been used by us and others as model systems to examine, demonstrate, and develop photobiological H{sub 2} production. More recently, the production of carbon-containing solar fuels like ethanol, butanol, and isoprene have been demonstrated. We are using a synthetic biology approach to develop efficient photosynthetic microbial cell factories for direct generation of biofuels from solar energy. Present progress and advances in the design, engineering, and construction of such cyanobacterial cells for the generation of a portfolio of solar fuels, e.g., hydrogen, alcohols, and isoprene, are presented and discussed. Possibilities and challenges when introducing and using synthetic biology are highlighted

Boundary layer concentrations and landscape scale emissions of volatile organic compounds in early spring

Science.gov (United States)

Haapanala, S.; Rinne, J.; Hakola, H.; Hellén, H.; Laakso, L.; Lihavainen, H.; Janson, R.; O'Dowd, C.; Kulmala, M.

2007-04-01

Boundary layer concentrations of several volatile organic compounds (VOC) were measured during two campaigns in springs of 2003 and 2006. The measurements were conducted over boreal landscapes near SMEAR II measurement station in Hyytiälä, Southern Finland. In 2003 the measuremens were performed using a light aircraft and in 2006 using a hot air balloon. Isoprene concentrations were low, usually below detection limit. This can be explained by low biogenic production due to cold weather, phenological stage of the isoprene emitting plants, and snow cover. Monoterpenes were observed frequently. The average total monoterpene concentration in the boundary layer was 33 pptv. Many anthropogenic compounds such as benzene, xylene and toluene, were observed in high amounts. Ecosystem scale surface emissions were estimated using a simple mixed box budget methodology. Total monoterpene emissions varied up to 80 μg m-2 h-1, α-pinene contributing typically more than two thirds of that. These emissions were somewhat higher that those calculated using emission algorithm. The highest emissions of anthropogenic compounds were those of p/m xylene.

Laboratory and field studies of biogenic volatile organic compound emissions from Sitka spruce (Picea sitchensis Bong.) in the United Kingdom

Science.gov (United States)

Street, Rachel A.; Duckham, S. Craig; Hewitt, C. Nicholas

1996-10-01

Isoprene and monoterpene emission rates were measured from Sitka spruce (Picea sitchensis Bong.) with a dynamic flow-through branch enclosure, both in the laboratory and in the field in the United Kingdom. In the laboratory, emission rates of isoprene comprised over 94% of the identified VOC species, and were exponentially related to temperature over a period of 1 day. This exponential relationship broke down at ˜33°C. Field measurements were taken on five sampling days in 1992 and 1993, in Grizedale Forest, Cumbria. Total emission rates were in the range 36-3771 ng g-1 h-1. Relative emissions were more variable than suggested by laboratory measurements, with monoterpenes contributing at least 64% to the total emissions in most cases. There was a significant variation in the basal emission rate both across the growing season and between different ages of vegetation, the causes of which are as yet unknown. Total emission rates, in July 1993, were estimated to be between 0.01 and 0.27% of assimilated carbon.

The Influence of Air-Sea Fluxes on Atmospheric Aerosols During the Summer Monsoon Over the Tropical Indian Ocean

Science.gov (United States)

Zavarsky, Alex; Booge, Dennis; Fiehn, Alina; Krüger, Kirstin; Atlas, Elliot; Marandino, Christa

2018-01-01

During the summer monsoon, the western tropical Indian Ocean is predicted to be a hot spot for dimethylsulfide emissions, the major marine sulfur source to the atmosphere, and an important aerosol precursor. Other aerosol relevant fluxes, such as isoprene and sea spray, should also be enhanced, due to the steady strong winds during the monsoon. Marine air masses dominate the area during the summer monsoon, excluding the influence of continentally derived pollutants. During the SO234-2/235 cruise in the western tropical Indian Ocean from July to August 2014, directly measured eddy covariance DMS fluxes confirm that the area is a large source of sulfur to the atmosphere (cruise average 9.1 μmol m-2 d-1). The directly measured fluxes, as well as computed isoprene and sea spray fluxes, were combined with FLEXPART backward and forward trajectories to track the emissions in space and time. The fluxes show a significant positive correlation with aerosol data from the Terra and Suomi-NPP satellites, indicating a local influence of marine emissions on atmospheric aerosol numbers.

Measuring Atmospheric Free Radicals Using Chemical Amplification

Science.gov (United States)

1988-05-01

CH 3Br, H2S, and SO2 [Logan et al., 1981]. Recently, the OH radical has been determined as the dominant loss mechanism for isoprene and monoterpenes ...W. Heaps, D. Philen, and T. McGee, Bondary Layer Measurements of the OH Radical in the Vicinity of an Isolated Power Plant Plume: SO2 and NO2

Geologic map of the Maumee quadrangle, Searcy and Marion Counties, Arkansas

Science.gov (United States)

Turner, Kenzie J.; Hudson, Mark R.

2010-01-01

This map summarizes the geology of the Maumee 7.5-minute quadrangle in northern Arkansas. The map area is in the Ozark plateaus region on the southern flank of the Ozark dome. The Springfield Plateau, composed of Mississippian cherty limestone, overlies the Salem Plateau, composed of Ordovician carbonate and clastic rocks, with areas of Silurian rocks in between. Erosion related to the Buffalo River and its tributaries, Tomahawk, Water, and Dry Creeks, has exposed a 1,200-ft-thick section of Mississippian, Silurian, and Ordovician rocks mildly deformed by faults and folds. An approximately 130-mile-long corridor along the Buffalo River forms the Buffalo National River that is administered by the National Park Service. McKnight (1935) mapped the geology of the Maumee quadrangle as part of a larger 1:125,000-scale map focused on understanding the lead and zinc deposits common in the area. Detailed new mapping for this study was compiled using a Geographic Information System (GIS) at 1:24,000 scale. Site location and elevation were obtained by using a Global Positioning Satellite (GPS) receiver in conjunction with a U.S. Geological Survey 7.5-minute topographic map and barometric altimeter. U.S. Geological Survey 10-m digital elevation model data were used to derive a hill-shade-relief map used along with digital orthophotographs to map ledge-forming units between field sites. Bedding attitudes were measured in drainage bottoms and on well-exposed ledges. Bedding measured at less than 2 degree dip is indicated as horizontal. Structure contours constructed for the base of the Boone Formation are constrained by field-determined elevations on both upper and lower formation contacts.

The Experiment Factory: standardizing behavioral experiments

Directory of Open Access Journals (Sweden)

Vanessa V Sochat

2016-04-01

Full Text Available The administration of behavioral and experimental paradigms for psychology research is hindered by lack of a coordinated effort to develop and deploy standardized paradigms. While several frameworks (de Leeuw (2015; McDonnell et al. (2012; Mason and Suri (2011; Lange et al. (2015 have provided infrastructure and methods for individual research groups to develop paradigms, missing is a coordinated effort to develop paradigms linked with a system to easily deploy them. This disorganization leads to redundancy in development, divergent implementations of conceptually identical tasks, disorganized and error-prone code lacking documentation, and difficulty in replication. The ongoing reproducibility crisis in psychology and neuroscience research (Baker (2015; Open Science Collaboration (2015 highlights the urgency of this challenge: reproducible research in behavioral psychology is conditional on deployment of equivalent experiments. A large, accessible repository of experiments for researchers to develop collaboratively is most efficiently accomplished through an open source framework. Here we present the Experiment Factory, an open source framework for the development and deployment of web-based experiments. The modular infrastructure includes experiments, virtual machines for local or cloud deployment, and an application to drive these components and provide developers with functions and tools for further extension. We release this infrastructure with a deployment (http://www.expfactory.org that researchers are currently using to run a set of over 80 standardized web-based experiments on Amazon Mechanical Turk. By providing open source tools for both deployment and development, this novel infrastructure holds promise to bring reproducibility to the administration of experiments, and accelerate scientific progress by providing a shared community resource of psychological paradigms.

A deeper look at the response of oxygenated and non oxygenated VOC to mid-term drought over the seasonal cycle: the case study of a drought-resistant species

Science.gov (United States)

Saunier, Amelie; Ormeño Lafuente, Elena; Wortham, Henri; Temime-Roussel, Brice; Fernandez, Catherine

2015-04-01

At the end of this century, climatic models plan an intensification of summer drought in the Mediterranean area due to a 30% rain reduction and a temperature rise of 3.4 °C. Plants respond to drought by modifying their primary (growth) and their secondary metabolism, the later being partly represented by volatile organic compound (VOC) emissions, such as terpenes. With drought, oxygenated and non oxygenated terpene emissions have been observed to increase, decrease or remain unchanged according to drought severity and vegetal model. By contrast, the response of non-terpenic oxygenated compounds to drought has been poorly studied. The aim of this study is to determine the potential impact of a two-year drought period on the full screen of VOC released by Q. pubescens, with a focus on both isoprene and methanol, issued from plant anabolism , and the numerous highly volatile oxygenated VOC, issued from plant catabolism (i.e. issued from oxidation of isoprene or methanol). A 70 years-old Downy oak forest (Quercus pubescens), highly resistant to drought stress, was selected as model ecosystem since it is well widespread in Southern France occupying 321 000 ha. Downy oak also represents the major source of isoprene emissions in the Mediterranean area and, unlike the other major Quercus sp. of the region (i.e. Quercus ilex, a monoterpene emitter) the impact of watering withholding over years has never been tackled. The study was performed at the experimental platform of O3HP (Oak Observatory at Observatoire de Haute Provence) in Southern France which is equipped with both a rain exclusion (by 30 %) and a rain addition structure (simulating the rainiest years of the region), allowing for comparison with naturally watered trees. Using dynamic enclosure chambers at the branch level and PTR-MS-Q-ToF, we screened the anabolic VOC (isoprene, methanol) and the catabolic VOC (e.g. methacrolein, methyl vinyl ketone, C6 aldehydes and carboxylic acids) of trees located under the

Origins and composition of fine atmospheric carbonaceous aerosol in the Sierra Nevada Mountains, California

Directory of Open Access Journals (Sweden)

D. R. Worton

2011-10-01

Full Text Available In this paper we report chemically resolved measurements of organic aerosol (OA and related tracers during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX at the Blodgett Forest Research Station, California from 15 August–10 October 2007. OA contributed the majority of the mass to the fine atmospheric particles and was predominately oxygenated (OOA. The highest concentrations of OA were during sporadic wildfire influence when aged plumes were impacting the site. In situ measurements of particle phase molecular markers were dominated by secondary compounds and along with gas phase compounds could be categorized into six factors or sources: (1 aged biomass burning emissions and oxidized urban emissions, (2 oxidized urban emissions (3 oxidation products of monoterpene emissions, (4 monoterpene emissions, (5 anthropogenic emissions and (6 local methyl chavicol emissions and oxidation products. There were multiple biogenic components that contributed to OA at this site whose contributions varied diurnally, seasonally and in response to changing meteorological conditions, e.g. temperature and precipitation events. Concentrations of isoprene oxidation products were larger when temperatures were higher during the first half of the campaign (15 August–12 September due to more substantial emissions of isoprene and enhanced photochemistry. The oxidation of methyl chavicol, an oxygenated terpene emitted by ponderosa pine trees, contributed similarly to OA throughout the campaign. In contrast, the abundances of monoterpene oxidation products in the particle phase were greater during the cooler conditions in the latter half of the campaign (13 September–10 October, even though emissions of the precursors were lower, although the mechanism is not known. OA was correlated with the anthropogenic tracers 2-propyl nitrate and carbon monoxide (CO, consistent with previous observations, while being comprised of mostly non-fossil carbon

Effects of Running Shoes with Abrasion Resistant Rubber Sole on the Exercise Capacity of the Human Body

Directory of Open Access Journals (Sweden)

Bo Wang

2017-10-01

Full Text Available With the development of industrialization, rubber has been gradually used in the manufacture of sports equipment for its favourable properties. This study involved the addition of C5 petroleum resin into brominated isobutylene-isoprene rubber (BIIR and butadiene rubber (BR while manufacturing the sole of running shoes. The effects of running shoes with abrasion resistant rubber sole on the exercise capacity of the human body were investigated by analysing the skid resistance and abrasion resistance of the running shoes, and conducting biomechanical study on naked feet and feet wearing the shoes. The results demonstrated that the rubber sole had favourable slip resistance property and mechanical properties such as stretching, abrasion resistance, and hardness. Compared to naked feet, the peak pressure intensity of the whole step of feet wearing the newly developed shoes, was significantly lower than that of feet wearing ordinary shoes. In the future, rubber can bring more comfortable experience because of its favourable properties.

Petrochemistry on process, goods and market

International Nuclear Information System (INIS)

Kim, Jong Deuk; Kim, Hwa Yong; Seo, Gon

1995-12-01

This book indicates petrochemistry with summary, importance and economic consideration of organic chemistry industry, synthetic gas ; ammonia, urea, nitric acid, oxo chemicals, phosgene, formic acid and neo-acids, methane ; hydrogen cyanide, HCN and chlorinated methanes, acetylene ; vinyl acetate, neoprene, acrylates and Reppe chemicals, ethylene ; polyethylene and ethanol, propylene ; allyl chloride and isoprene, hydrocarbon: butadiene, isobutylene, aromatic hydrocarbon and other petrochemistry productions.

Customer experience

OpenAIRE

Koperdáková, Zuzana

2016-01-01

Bachelor thesis deals with the theme of customer experience and terms related to this topic. The thesis consists of three parts. The first part explains the terms generally, as the experience or customer loyalty. The second part is dedicated to medotology used for Customer Experience Management. In the third part is described application of Customer Experience Management in practice, particularly in the context Touch Point Analyses in GE Money Bank.

1200 nt rat liver mRNA identified by differential hybridization exhibits coordinate regulation with 3-hydroxy-3-methylglutaryl coenzyme A (HMG CoA) reductase

International Nuclear Information System (INIS)

Tanaka, R.D.; Clarke, C.F.; Fogelman, A.M.; Edwards, P.A.

1986-01-01

Differential hybridization has been used to identify genes in rat liver that encode transcripts which are increased by the drugs cholestyramine and mevinolin and are decreased by dietary cholesterol. This approach should prove useful in isolating and identifying coordinately regulated genes involved in the isoprene biosynthetic pathway. Rat liver poly (A) + RNA was isolated from animals fed diets supplemented with either cholestyramine and mevinolin or with cholesterol. Radiolabeled cDNAs generated from these two RNA preparations were used to screen a rat cDNAs library. A preliminary screen of 10,000 recombinants has led to the identification of a clone with an insert of 1200 bp that hybridizes to a mRNA species of about 1200 nt. The level of this RNA species in rat liver is elevated by the drugs cholestyramine and mevinolin and is decreased by cholesterol feeding. This RNA species is also decreased by mevalonate administration to rats. The regulation of this 1200 nt mRNA species mirrors that of HMG CoA reductase and HMG CoA synthase. It seems very likely that this 1200 nt mRNA encodes a polypeptide which is involved in the isoprene biosynthetic pathway

Influence of acetone extract from natural rubber on the structure and interface interaction in NR/silica composites

Science.gov (United States)

Xu, Tiwen; Jia, Zhixin; Wu, Lianghui; Chen, Yongjun; Luo, Yuanfang; Jia, Demin; Peng, Zheng

2017-11-01

It is well known that the coupling reagents as the additional modifiers were often used to improve the reinforcement effect of silica filled natural rubber. Actually, the commercial raw NR is a mixture consisting of polyisoprene and non-isoprene, where the latter one might have impact on the properties of NR/silica composites as an inartificial modifier inside. Thus, investigating the effect of non-isoprene compounds on the structure and properties of NR/silica composites is a novel approach to disclose the peculiarity of NR, which is meaningful to the assessment of NR quality. In this paper, the influences of acetone extract (AE) from natural rubber on the structure and mechanical properties of NR/silica composites were studied. Then the interfacial interactions between AE and silica were also illustrated through Fourier transform infrared spectroscopy (FTIR), thermogravimetic analysis (TGA), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Results demonstrated the existence of hydrogen bond between silica and AE, also the covalent bond induced by esterification reaction between sbnd COOH and Sisbnd OH, which resulted in an increase of constrained regions around silica surface leading to the promotions on mechanical and dynamical properties of NR/silica composites significantly.

Regional modeling of carbonaceous aerosols over Europe-focus on secondary organic aerosols

Energy Technology Data Exchange (ETDEWEB)

Bessagnet, B. [INERIS, Inst Nat Env Indust Risques, F-60550 Verneuil en Halatte, (France); Menut, L. [Ecole Poltechnique, Inst Pierre Simon Laplace, Lab Meteorol Dyn, F-91128 Palaiseau, (France); Curci, G. [Univ degli Studi dell' Aquila, CETEMPS, 67010 Coppito - L' Aquila, (Italy); Hodzic, A. [NCAR, Nat Center for Atmosph Research, Boulder, 80301, CO, (United States); Guillaume, B.; Liousse, C. [LA/OMP, Lab Aerol/Observ Midi-Pyrenees, F-31400 Toulouse, (France); Moukhtar, S. [York Univ, Centre Atmosph Chem, Toronto, (Italy); Pun, B.; Seigneur, C. [Atmosph and Environ Research, San Ramon, CA 94583, (United States); Schulz, M. [CEA-CNRS-UVSQ, IPSL, Lab Sciences Climat et Environm, F-91191 Gif sur Yvette, (France)

2008-07-01

In this study, an improved and complete secondary organic aerosols (SOA) chemistry scheme was implemented in the CHIMERE model. The implementation of isoprene chemistry for SOA significantly improves agreement between long series of simulated and observed particulate matter concentrations. While simulated organic carbon concentrations are clearly improved at elevated sites by adding the SOA scheme, time correlation are impaired at low level sites in Portugal, Italy and Slovakia. At several sites a clear underestimation by the CHIMERE model is noticed in wintertime possibly due to missing wood burning emissions as shown in previous modeling studies. In Europe, the CHIMERE model gives yearly average SOA concentrations ranging from 0.5 {mu}g m{sup -3} in the Northern Europe to 4 {mu}g m{sup -3} over forested regions in Spain, France, Germany and Italy. In addition, our work suggests that during the highest fire emission periods, fires can be the dominant source of primary organic carbon over the Mediterranean Basin, but the SOA contribution from fire emissions is low. Isoprene chemistry has a strong impact on SOA formation when using current available kinetic schemes. (authors)

Estimating the Biogenic Non-Methane Hydrocarbon Emissions over Greece

Directory of Open Access Journals (Sweden)

Ermioni Dimitropoulou

2018-01-01

Full Text Available Biogenic emissions affect the urban air quality as they are ozone and secondary organic aerosol (SOA precursors and should be taken into account when applying photochemical pollution models. The present study presents an estimation of the magnitude of non-methane volatile organic compounds (BNMVOCs emitted by vegetation over Greece. The methodology is based on computation developed with the aid of a Geographic Information System (GIS and theoretical equations in order to produce an emission inventory on a 6 × 6 km2 spatial resolution, in a temporal resolution of 1 h covering one year (2016. For this purpose, a variety of input data was used: updated satellite land-use data, land-use specific emission potentials, foliar biomass densities, temperature, and solar radiation data. Hourly, daily, and annual isoprene, monoterpenes, and other volatile organic compounds (OVOCs were estimated. In the area under study, the annual biogenic emissions were estimated up to 472 kt, consisting of 46.6% isoprene, 28% monoterpenes, and 25.4% OVOCs. Results delineate an annual cycle with increasing values from March to April, while maximum emissions were observed from May to September, followed by a decrease from October to January.

Assessing the sensitivity of benzene cluster cation chemical ionization mass spectrometry toward a wide array of biogenic volatile organic compounds

Science.gov (United States)

Lavi, Avi; Vermeuel, Michael; Novak, Gordon; Bertram, Timothy

2017-04-01

Chemical ionization mass spectrometry is a real-time, sensitive and selective measurement technique for the detection of volatile organic compounds (VOCs). The benefits of CIMS technology make it highly suitable for field measurements that requires fast (10Hz and higher) response rates, such as the study of surface-atmosphere exchange processes by the eddy covariance method. The use of benzene cluster cations as a regent ion was previously demonstrated as a sensitive and selective method for the detection of select biogenic VOCs (e.g. isoprene, monoterpenes and sesquiterpenes) [Kim et al., 2016; Leibrock and Huey, 2000]. Quantitative analysis of atmospheric trace gases necessitates calibration for each analyte as a function of atmospheric conditions. We describe a custom designed calibration system, based on liquid evaporation, for determination of the sensitivity of the benzene-CIMS to a wide range of organic compounds at atmospherically relevant mixing ratios (volatile organic compounds, Atmos Meas Tech, 9(4), 1473-1484, doi:10.5194/amt-9-1473-2016. Leibrock, E., and L. G. Huey (2000), Ion chemistry for the detection of isoprene and other volatile organic compounds in ambient air, Geophys Res Lett, 27(12), 1719-1722, doi:Doi 10.1029/1999gl010804.

Simulator experiments: effects of NPP operator experience on performance

International Nuclear Information System (INIS)

Beare, A.N.; Gray, L.H.

1984-01-01

During the FY83 research, a simulator experiment was conducted at the control room simulator for a GE Boiling Water Reactor (BWR) NPP. The research subjects were licensed operators undergoing requalification training and shift technical advisors (STAs). This experiment was designed to investigate the effects of senior reactor operator (SRO) experience, operating crew augmentation with an STA and practice, as a crew, upon crew and individual operator performance, in response to anticipated plant transients. Sixteen two-man crews of licensed operators were employed in a 2 x 2 factorial design. The SROs leading the crews were split into high and low experience groups on the basis of their years of experience as an SRO. One half of the high- and low-SRO experience groups were assisted by an STA. The crews responded to four simulated plant casualties. A five-variable set of content-referenced performance measures was derived from task analyses of the procedurally correct responses to the four casualties. System parameters and control manipulations were recorded by the computer controlling the simulator. Data on communications and procedure use were obtained from analysis of videotapes of the exercises. Questionnaires were used to collect subject biographical information and data on subjective workload during each simulated casualty. For four of the five performance measures, no significant differences were found between groups led by high (25 to 114 months) and low (1 to 17 months as an SRO) experience SROs. However, crews led by low experience SROs tended to have significantly shorter task performance times than crews led by high experience SROs. The presence of the STA had no significant effect on overall team performance in responding to the four simulated casualties. The FY84 experiments are a partial replication and extension of the FY83 experiment, but with PWR operators and simulator

Future heat waves and surface ozone

Science.gov (United States)

Meehl, Gerald A.; Tebaldi, Claudia; Tilmes, Simone; Lamarque, Jean-Francois; Bates, Susan; Pendergrass, Angeline; Lombardozzi, Danica

2018-06-01

A global Earth system model is used to study the relationship between heat waves and surface ozone levels over land areas around the world that could experience either large decreases or little change in future ozone precursor emissions. The model is driven by emissions of greenhouse gases and ozone precursors from a medium-high emission scenario (Representative Concentration Pathway 6.0–RCP6.0) and is compared to an experiment with anthropogenic ozone precursor emissions fixed at 2005 levels. With ongoing increases in greenhouse gases and corresponding increases in average temperature in both experiments, heat waves are projected to become more intense over most global land areas (greater maximum temperatures during heat waves). However, surface ozone concentrations on future heat wave days decrease proportionately more than on non-heat wave days in areas where ozone precursors are prescribed to decrease in RCP6.0 (e.g. most of North America and Europe), while surface ozone concentrations in heat waves increase in areas where ozone precursors either increase or have little change (e.g. central Asia, the Mideast, northern Africa). In the stabilized ozone precursor experiment, surface ozone concentrations increase on future heat wave days compared to non-heat wave days in most regions except in areas where there is ozone suppression that contributes to decreases in ozone in future heat waves. This is likely associated with effects of changes in isoprene emissions at high temperatures (e.g. west coast and southeastern North America, eastern Europe).

Intoxication of sheep exposed to ozark milkweed (Asclepias viridis Walter).

Science.gov (United States)

Smith, R A; Scharko, P; Bolin, D; Hong, C B

2000-12-01

Some 20 sheep died 1 at a time on a farm in Fleming County, KY, in late July of 1999 after consumption of Asclepias viridis Walter. Major histological lesions were mild multifocal nonsuppurative myocarditis. Gross pathology revealed wet and heavy lungs. Many affected animals had a hunched appearance, and marked posterior paresis was also observed.

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A: tropospheric degradation of non-aromatic volatile organic compounds

Directory of Open Access Journals (Sweden)

S. M. Saunders

2003-01-01

Full Text Available Kinetic and mechanistic data relevant to the tropospheric degradation of volatile organic compounds (VOC, and the production of secondary pollutants, have previously been used to define a protocol which underpinned the construction of a near-explicit Master Chemical Mechanism. In this paper, an update to the previous protocol is presented, which has been used to define degradation schemes for 107 non-aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3. The treatment of 18 aromatic VOC is described in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the reactions of the radical intermediates and the further degradation of first and subsequent generation products. Emphasis is placed on updating the previous information, and outlining the methodology which is specifically applicable to VOC not considered previously (e.g. a- and b-pinene. The present protocol aims to take into consideration work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Application of MCM v3 in appropriate box models indicates that the representation of isoprene degradation provides a good description of the speciated distribution of oxygenated organic products observed in reported field studies where isoprene was the dominant emitted hydrocarbon, and that the a-pinene degradation chemistry provides a good description of the time dependence of key gas phase species in a-pinene/NOX photo-oxidation experiments carried out in the European Photoreactor (EUPHORE. Photochemical Ozone Creation Potentials (POCP have been calculated for the 106 non-aromatic non-methane VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. Where applicable, the values are compared with

Geologic map of the Murray Quadrangle, Newton County, Arkansas

Science.gov (United States)

Hudson, Mark R.; Turner, Kenzie J.

2016-07-06

This map summarizes the geology of the Murray quadrangle in the Ozark Plateaus region of northern Arkansas. Geologically, the area is on the southern flank of the Ozark dome, an uplift that has the oldest rocks exposed at its center, in Missouri. Physiographically, the Murray quadrangle is within the Boston Mountains, a high plateau region underlain by Pennsylvanian sandstones and shales. Valleys of the Buffalo River and Little Buffalo River and their tributaries expose an approximately 1,600-ft-thick (488-meter-thick) sequence of Ordovician, Mississippian, and Pennsylvanian carbonate and clastic sedimentary rocks that have been mildly deformed by a series of faults and folds. The Buffalo National River, a park that encompasses the Buffalo River and adjacent land that is administered by the National Park Service is present at the northwestern edge of the quadrangle.Mapping for this study was carried out by field inspection of numerous sites and was compiled as a 1:24,000 geographic information system (GIS) database. Locations and elevation of sites were determined with the aid of a global positioning satellite receiver and a hand-held barometric altimeter that was frequently recalibrated at points of known elevation. Hill-shade relief and slope maps derived from a U.S. Geological Survey 10-meter digital elevation model as well as orthophotographs were used to help trace ledge-forming units between field traverses within the Upper Mississippian and Pennsylvanian part of the stratigraphic sequence. Strike and dip of beds were typically measured along stream drainages or at well-exposed ledges. Structure contours, constructed on the top of the Boone Formation and the base of a prominent sandstone unit within the Bloyd Formation, were drawn based on the elevations of field sites on these contacts well as other limiting information for their minimum elevations above hilltops or their maximum elevations below valley bottoms.

Geologic Map of the Boxley Quadrangle, Newton and Madison Counties, Arkansas

Science.gov (United States)

Hudson, Mark R.; Turner, Kenzie J.

2007-01-01

This map summarizes the geology of the Boxley 7.5-minute quadrangle in the Ozark Plateaus region of northern Arkansas. Geologically, the area lies on the southern flank of the Ozark dome, an uplift that exposes oldest rocks at its center in Missouri. Physiographically, the Boxley quadrangle lies within the Boston Mountains, a high plateau region underlain by Pennsylvanian sandstones and shales. Valleys of the Buffalo River and its tributaries expose an approximately 1,600-ft-(490-m-)thick sequence of Ordovician, Mississippian, and Pennsylvanian carbonate and clastic sedimentary rocks that have been mildly deformed by a series of faults and folds. Part of Buffalo National River, a park encompassing the Buffalo River and adjacent land that is administered by the National Park Service, extends through the eastern part of the quadrangle. Mapping for this study was conducted by field inspection of numerous sites and was compiled as a 1:24,000-scale geographic information system (GIS) database. Locations and elevation sites were determined with the aid of a global positioning satellite receiver and a hand-held barometric altimeter. Hill-shade-relief and slope maps derived from a U.S. Geological Survey 10-m digital elevation model as well as orthophotos were used to help trace ledge-forming units between field traverses within the Upper Mississippian and Pennsylvanian part of the stratigraphic sequence. Strike and dip of beds were typically measured along stream drainages or at well-exposed ledges. Structure contours were constructed on the top of the Boone Formation and the base of a prominent sandstone unit within the Bloyd Formation based on elevations of control points as well as other limiting information on their maximum or minimum elevations.

Mary SIDA y otras agresoras fatales en el folclore internáutico: enfermedad, miedo y mito

Directory of Open Access Journals (Sweden)

Ángel J. GONZALO TOBAJAS

2015-04-01

Full Text Available ABSTRACT: Although the urban legend's versions of «Mary AIDS» and its sequels are mainly transmitted through the new molds for the digital era (blogs, social networks, applications crossplatform messaging as WhatsApp and websites like YouTube, if it deepens in the territories of the oral and written literature, myth, History and the press notes that its content is much more traditional than we might imagine. Between parallels mentioned here, among others, an episode of the Gesta Romanorum, a Breton ballad of the Middle Ages, a popular tale of the Ozarks and a tale by Guy de Maupassant. Furthermore, it's linked here the protagonists of these stories with characters like the serranas of Spanish popular ballads and creatures as lamias, nymphs and succubi of different traditions, cultures and periods of time. RESUMEN: Aunque las versiones de las leyendas urbanas de «Mary SIDA» y sus secuelas se transmitan fundamentalmente a través de los nuevos moldes de la era digital (blogs, redes sociales, aplicaciones de mensajería multiplataforma como WhatsApp y sitios web como YouTube, si se profundiza en los territorios de la literatura oral y escrita, el mito, el cuento, la historia y la prensa se observa que su contenido es mucho más tradicional de lo que a priori se podría imaginar. Entre los paralelos mencionados en este artículo destaca, por ejemplo, un episodio de la Gesta Romanorum, una balada bretona de la Edad Media, un cuento popular de los Ozark y un conocido relato de Guy de Maupassant; asimismo, se vincula aquí a las protagonistas de estas leyendas con personajes como las serranas del Romancero popular y criaturas como las lamias, ninfas y súcubos de distintas tradiciones, culturas y épocas.

Extracting Insights from Experience Designers to Enhance User Experience Design

OpenAIRE

Kremer, Simon; Lindemann, Udo

2016-01-01

User Experience (UX) summarizes how a user expects, perceives and assesses an encounter with a product. User Experience Design (UXD) aims at creating meaningful experiences. While UXD is a rather young discipline with-in product development and traditional processes predominate, other disciplines traditionally focus on creating experiences. We engaged with experience de-signers from the fields of arts, movies, sports, music and event management. By analyzing their working processes via interv...

Moho Depth and Geometry in the Illinois Basin Region Based on Gravity and Seismic Data from an EarthScope FlexArray Experiment

Science.gov (United States)

Curcio, D. D.; Pavlis, G. L.; Yang, X.; Hamburger, M. W.; Zhang, H.; Ravat, D.

2017-12-01

We present results from a combined analysis of seismic and gravity in the Illinois Basin region that demonstrate the presence of an unusually deep and highly variable Moho discontinuity. We construct a new, high-resolution image of the Earth's crust beneath the Illinois Basin using teleseismic P-wave receiver functions from the EarthScope OIINK (Ozarks, Illinois, INdiana, Kentucky) Flexible Array and the USArray Transportable Array. Our seismic analyses involved data from 143 OIINK stations and 80 USArray stations, using 3D plane-wave migration and common conversion point (CCP) stacking of P-to-S conversion data. Seismic interpretation has been done using the seismic exploration software package Petrel. One of the most surprising results is the anomalous depth of the Moho in this area, ranging from 41 to 63 km, with an average depth of 50 km. This thickened crust is unexpected in the Illinois Basin area, which has not been subject to convergence and mountain building processes in the last 900 Ma. This anomalously thick crust in combination with the minimal topography requires abnormally dense lower crust or unusually light upper mantle in order to retain gravitational equilibrium. Combining gravity modeling with the seismically identified Moho and a ubiquitous lower crustal boundary, we solve for the density variation of the middle and lower crust. We test the hypothesis that the anomalously thick crust and its high lower crustal layer observed in most of the central and southeastern Illinois Basin predates the formation and development of the current Illinois Basin. Post-formation tectonic activity, such as late Precambrian rifting or underplating are inferred to have modified the crustal thickness as well. The combination of high-resolution seismic data analysis and gravity modeling promises to provide additional insight into the geometry and composition of the lower crust in the Illinois Basin area.

Estimating Biogenic Non-Methane Hydrocarbon Emissions for the Wasatch Front Through a High-Resolution. Gridded, Biogenic Vola Tile Organic Compound Emissions Inventory

Science.gov (United States)

2002-01-01

1-hour and proposed 8-hour National Ambient Air Quality Standards. Reactive biogenic (natural) volatile organic compounds emitted from plants have...uncertainty in predicting plant species composition and frequency. Isoprene emissions computed for the study area from the project’s high-resolution...Landcover Database (BELD 2), while monoterpene and other reactive volatile organic compound emission rates were almost 26% and 28% lower, respectively

Polymer Based Molecular Composites. Volume 171. Materials Research Society Symposium Proceedings Held in Boston, Massachusetts on 27-30 November 1989

Science.gov (United States)

1990-09-01

reactivity features promoted by the polymeric sulfonic acid moiety in contrast to HCI. Further work is being undertaken utilizing para toluene 21 sulfonic...styrene and isoprene block and homo- polymers were synthesized by anionic polymerization. Cyclohexane (Burdick and Jackson HPLC Grade) was degassed and...terephthalic acid and 21 mole-% 4 aminophenol , was purchased from Hoechst Celanese. Blends containing 70 weight-% PPE and 30 weight-% PS were kindly

Living Polymerization for the Introduction of Tailored Hydrogen Bonding

OpenAIRE

Elkins, Casey Lynn

2005-01-01

In an effort to synthesize macromolecules comprising both covalent and non-covalent bonding to tune ultimate physical properties, a variety of methodologies and functionalization strategies were employed. First, protected functional initiation, namely 3-[(N-benzyl-N-methyl)amino]-1-propyllithium and 3-(t-butyldimethylsilyloxy)-1-propyllithium, in living anionic polymerization of isoprene was used to yield well-defined chain end functional macromolecules. Using both initiating systems, polym...

Interaction of α,β-unsaturated aldehydes with dienes in the presence of boron trifluoride etherate

International Nuclear Information System (INIS)

Gramenitskaya, V.N.; Golovkina, L.S.; Orach, V.S.

1975-01-01

The products of the acrolein reaction with divinyl, isoprene and chloroprene catalized by BF 3 xEt 2 O are corresponding 3-cyclohexenaldehydes trimerized under the catalyst influence. Mixtures of substituted 3-cyclohexealdehydes and Δ 3 -dihydropirines were produced as results of the reaction of croton aldehyde with 1,1,3-trimethilbutadiene at high temperature as well as at 20 deg C in presence of catalyst