GasBench/isotope ratio mass spectrometry: a carbon isotope approach to detect exogenous CO(2) in sparkling drinks.

Science.gov (United States)

Cabañero, Ana I; San-Hipólito, Tamar; Rupérez, Mercedes

2007-01-01

A new procedure for the determination of carbon dioxide (CO(2)) (13)C/(12)C isotope ratios, using direct injection into a GasBench/isotope ratio mass spectrometry (GasBench/IRMS) system, has been developed to improve isotopic methods devoted to the study of the authenticity of sparkling drinks. Thirty-nine commercial sparkling drink samples from various origins were analyzed. Values of delta(13)C(cava) ranged from -20.30 per thousand to -23.63 per thousand, when C3 sugar addition was performed for a second alcoholic fermentation. Values of delta(13)C(water) ranged from -5.59 per thousand to -6.87 per thousand in the case of naturally carbonated water or water fortified with gas from the spring, and delta(13)C(water) ranged from -29.36 per thousand to -42.09 per thousand when industrial CO(2) was added. It has been demonstrated that the addition of C4 sugar to semi-sparkling wine (aguja) and industrial CO(2) addition to sparkling wine (cava) or water can be detected. The new procedure has advantages over existing methods in terms of analysis time and sample treatment. In addition, it is the first isotopic method developed that allows (13)C/(12)C determination directly from a liquid sample without previous CO(2) extraction. No significant isotopic fractionation was observed nor any influence by secondary compounds present in the liquid phase. Copyright (c) 2007 John Wiley & Sons, Ltd.

Compiled records of carbon isotopes in atmospheric CO2 for historical simulations in CMIP6

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H. Graven

2017-12-01

Full Text Available The isotopic composition of carbon (Δ14C and δ13C in atmospheric CO2 and in oceanic and terrestrial carbon reservoirs is influenced by anthropogenic emissions and by natural carbon exchanges, which can respond to and drive changes in climate. Simulations of 14C and 13C in the ocean and terrestrial components of Earth system models (ESMs present opportunities for model evaluation and for investigation of carbon cycling, including anthropogenic CO2 emissions and uptake. The use of carbon isotopes in novel evaluation of the ESMs' component ocean and terrestrial biosphere models and in new analyses of historical changes may improve predictions of future changes in the carbon cycle and climate system. We compile existing data to produce records of Δ14C and δ13C in atmospheric CO2 for the historical period 1850–2015. The primary motivation for this compilation is to provide the atmospheric boundary condition for historical simulations in the Coupled Model Intercomparison Project 6 (CMIP6 for models simulating carbon isotopes in the ocean or terrestrial biosphere. The data may also be useful for other carbon cycle modelling activities.

Compiled records of carbon isotopes in atmospheric CO2 for historical simulations in CMIP6

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Graven, Heather; Allison, Colin E.; Etheridge, David M.; Hammer, Samuel; Keeling, Ralph F.; Levin, Ingeborg; Meijer, Harro A. J.; Rubino, Mauro; Tans, Pieter P.; Trudinger, Cathy M.; Vaughn, Bruce H.; White, James W. C.

2017-12-01

The isotopic composition of carbon (Δ14C and δ13C) in atmospheric CO2 and in oceanic and terrestrial carbon reservoirs is influenced by anthropogenic emissions and by natural carbon exchanges, which can respond to and drive changes in climate. Simulations of 14C and 13C in the ocean and terrestrial components of Earth system models (ESMs) present opportunities for model evaluation and for investigation of carbon cycling, including anthropogenic CO2 emissions and uptake. The use of carbon isotopes in novel evaluation of the ESMs' component ocean and terrestrial biosphere models and in new analyses of historical changes may improve predictions of future changes in the carbon cycle and climate system. We compile existing data to produce records of Δ14C and δ13C in atmospheric CO2 for the historical period 1850-2015. The primary motivation for this compilation is to provide the atmospheric boundary condition for historical simulations in the Coupled Model Intercomparison Project 6 (CMIP6) for models simulating carbon isotopes in the ocean or terrestrial biosphere. The data may also be useful for other carbon cycle modelling activities.

Deglacial Western Equatorial Pacific pCO2 Reconstruction Using Boron Isotopes of Planktonic Foraminiferas

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Kubota, K.; Yokoyama, Y.; Ishikawa, T.; Sagawa, T.; Ikehara, M.; Yamazaki, T.

2017-12-01

During the last deglaciation (ca. 19 - 11 ka), partial pressure of CO2 (pCO2) of the atmosphere increased by 80 μatm. Many paleoceanographers point out that the ocean had played an important role in atmospheric CO2 rise, since the ocean have 60 times larger capacity to store carbon compared to the atmosphere. However, evidence on where carbon was transferred from the ocean to the atmosphere is still lacking, hampering our understanding of global carbon cycles in glacial-interglacial timescales. Boron isotope of skeletons of marine calcifying organisms such as corals and foraminiferas can pin down where CO2 source/sink existed, because boron isotopes of marine calcium carbonates is dependent on seawater pH, from which pCO2 of the past seawater can be reconstructed. In previous studies using the boron isotope teqnique, Martinez-Boti et al. (2015, Nature) and Kubota et al. (2014, Scientific Reports) revealed that central and eastern parts of the equatorial Pacific acted as a CO2 source (i.e., CO2 emission) during the last deglaciation, suggesting the equatorial Pacific's contribution to atmospheric CO2 rise. However, some conflicting results have been confirmed in a marine sediment record from the western part of the equatorial Pacific (Palmer & Pearson, 2003, Science), making the conclusion elusive. In this presentation, we will show new results of Mg/Ca, oxygen isotope, and boron isotope measurements during the last 35 ka on two species of surface dwelling foraminiferas (Globigerinoides ruber and G. sacculifer) which was hand-picked separatedly from a well-dated marine sediment core recovered from the West Caroline Basin (KR05-15 PC01) (Yamazaki et al., 2008, GRL). From the new records, we will discuss how the equatorial Pacific behaved during the last deglaciation and how it related to the global carbon cycles.

Calculation of radiation production of high specific activity isotopes 192Ir and 60Co

International Nuclear Information System (INIS)

Zhou Quan; Zhong Wenfa; Xu Xiaolin

1997-01-01

The high specific activity isotopes: 192 Ir and 60 Co in the high neutron flux reactor are calculated with the method of reactor physics. The results of calculation are analyzed in two aspects: the production of isotopes and the influence to parameters of the reactor, and hence a better case is proposed as a reference to the production

A STUDY ON CARBON ISOTOPE OF CO2 AND CH4 IN WESTERN DIENG PLATEU BY GAS CHROMATOGRAPHY- ISOTOPE RATIO MASS SPECTROMETER (GC-IRMS

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Hanik Humaida

2010-06-01

Full Text Available The carbon isotope can be used to evaluate volcanism phenomenon of volcano. The study of carbon isotope of CO2 and CH4 was carried out in western Dieng Plateau by mass-spectrometer. Before analysis, sampel was separated by gas chromatography using a Porapak-Q column and a FID (Flame Ionization Detector detector. The gas was oxidized by copper oxide at 850oC before being ionized in mass-spectrometer for isotope analysis. The CO2 content in Candradimuka crater (-4.10 O/OO, indicated that the gas may be as volcanic gas. The other CO2 from Sumber and western Gua Jimat, had isotope value  of -10.05 and -12.07 O/OO, respectively, indicating contamination from crustal and subduction material. The carbon isotope of CH4 gas from Pancasan village was -63.42 O/OO, that may be categorized as biogenic gas.   Keywords: isotope, CO2, CH4, Dieng.

Cross-continental triple oxygen isotope analysis of tropospheric CO2

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Liang, M. C.; Rangarajan, R.; Newman, S.; Laskar, A. H.

2016-12-01

The abundance variations of near surface atmospheric CO2 isotopologues (primarily 16O12C16O, 16O13C16O, 17O12C16O, and 18O12C16O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, and stratospheric photochemistry. Oxygen isotopes, in particular, are affected by the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO2 biogeochemical cycles, D17O (= ln(1+d17O) - 0.516´ln(1+d18O)) provides an alternative constraint on the strengths of the associated cycles involving CO2. Here, we report more than one year of data obtained from Taiwan (Taipei), South China Sea, and USA (Pasadena, CA and Palos Verdes, CA). On average, the D17O values from these locations are similar and show no significant influence from the 2014-2016 El Nino event, in contrast to what has been reported for the 1997-1998 El Nino from the CO2 data collected from La Jolla, CA. Implications for utilizing the new tracer D17O for carbon cycling studies will be made.

Climatic significance of stable isotope characteristics of air-CO2 and rainfall in Delhi area water-plant-air system

International Nuclear Information System (INIS)

Datta, P.S.; Tyagi, S.K.

2002-01-01

In recent years, there is a global concern on the role of carbon dioxide in atmosphere in affecting the climate. The present models of global atmospheric circulation suggest that oceans sequester about one-third of the CO 2 released by anthropogenic activities, and biospheric productivity is the primary cause of the interannual fluctuations in the atmospheric CO 2 . However, most of the times, the excess of CO 2 in air is associated with the presence of anthropogenic pollutants from urbanised centres. Therefore, the studies on the pattern of local variations in the isotopic composition of air CO 2 and rainfall in urban areas are expected to provide important information on the atmospheric circulation processes which affect the climate on a regional scale. Internationally, aspects of climate change have been so far demonstrated using isotopic data mainly from temperate climates, and there is limited understanding of the factors controlling stable isotopic composition of air-CO 2 and rainfall in tropical regions. In this context, to assess the magnitude of the above mentioned effects, analysis of the data on the variations in the 13 C/ 12 C and 18 O/ 16 O signatures of air-CO 2 in Delhi area water-plant-air system is presented here

CO and H2 uptake and emissions by soil: variability of fluxes and their isotopic signatures

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Popa, Maria Elena; Chen, Qianjie; Ferrero Lopez, Noelia; Röckmann, Thomas

2017-04-01

In order to study the uptake and release of H2 and CO by soil, we performed long term, high frequency measurements with an automatic soil chamber at two sites in the Netherlands (Cabauw - grassland, and Speuld - forest). The measurements were performed over different seasons and cover in total a cumulated interval of about one year. These measurements allow determining separately, for each species, the two distinct fluxes i.e. uptake and release, and investigating their temporal variability and dependencies on environmental variables. Additional experiments were performed for determining the isotopic signatures of the H2 and CO uptake and release by soil. Flask samples were filled from the soil chamber, and then analyzed in the laboratory for the stable isotopic composition of H2 (δD) and CO (δ13C and δ18O). We find that both uptake and release are present at all times, regardless of the direction of the net flux. The emissions are significant for both species and at Cabauw, there are times and places where emissions outweigh the soil uptake. For each species, the two fluxes have different behavior and dependence on external variables, which indicates that they have different origins. The isotope results also support that, for both H2 and CO, uptake and emission occur simultaneously. We were able to determine separately the isotopic effects of the two fluxes. For both H2 and CO, soil uptake is associated with a small positive fractionation (the lighter molecule is taken up faster). The soil uptake fractionation (α = kheavy/klight) was 0.945 ± 0.004 for H2; for CO, the fractionation was 0.992 for 13C and 0.985 for 18O. The isotopic composition of the H2 emitted from the grassland was -530 ± 40 ‰, less depleted that what is expected from the isotopic equilibrium of H2 with water. For CO, the isotopic composition of the soil emission is depleted in 13C compared to atmospheric CO, and lower than the average isotopic composition of plant or soil organic matter.

Isotopic tracers of sources, wells and of CO2 reactivity in geological reservoirs

International Nuclear Information System (INIS)

Assayag, N.

2006-12-01

The aim of this research works consisted in studying the behaviour of the carbonate system (dissolved inorganic carbon: DIC) following a CO 2 injection (artificial or natural), in geological reservoirs. One part of the study consisted in improving an analytical protocol for the measurement of δ 13 C DIC and DIC, using a continuous flow mass spectrometer. As a first study, we have focused our attention on the Pavin Lake (Massif Central, France). Owing to its limnologic characteristics (meromictic lake) and a deep volcanic CO 2 contribution, it can be viewed as a natural analogue of reservoir storing important quantities of CO 2 in the bottom part. Isotopic measurements (δ 18 O, δ 13 C DIC) allowed to better constrain the dynamics of the lake (stratification, seasonal variations), the magnitudes of biological activities (photosynthesis, organic matter decay, methane oxidation, methano-genesis), carbon sources (magmatic, methano-genetic), and the hydrological budgets (sub-lacustrine inputs). The second study was conducted on the Lamont-Doherty test well site (NY, USA). It includes an instrumental borehole which cuts through most of the section of the Palisades sill and into the Newark Basin sediments. Single well push-pull tests were performed: a test solution containing conservative tracers and a reactive tracer (CO 2 ) was injected at a permeable depth interval located in basaltic and meta sedimentary rocks. After an incubation period, the test solution/groundwater mixture was extracted from the hydraulically isolated zone. Isotopic measurements (δ 18 O, δ 13 C DIC) confronted to chemical data (major elements) allowed to investigate the extent of in-situ CO 2 -water-rock interactions: essentially calcite dissolution and at a lesser extend silicate dissolution...and for one of the test, CO 2 degassing. (author)

On the relations between the oceanic uptake of CO2 and its carbon isotopes

International Nuclear Information System (INIS)

Heimann, M.; Maier-Reimer, E.

1994-01-01

The recent proposals to estimate the oceanic uptake of CO 2 by monitoring the oceanic change in 13 C/ 12 C isotope ratio or the air-sea 13 C/ 12 C isotopic disequilibrium is reviewed. Because the history of atmospheric CO 2 and 13 CO 2 since preindustrial times is almost the same, the oceanic penetration depth of both tracers must be the same. This dynamic constraint permits the establishment of yet a third method to estimate the global ocean uptake of CO 2 from 13 C measurements. Using available observations in conjunction with canonical values for the global carbon cycle parameters the three methods yield inconsistent oceanic CO 2 uptake rates for the time period 1970-1990, ranging from 0 to over 3 GtC year -1 . However, uncertainties in the available carbon cycle data must be taken into account. Using a non-linear estimation procedure, a consistent scenario with an oceanic CO 2 uptake rate of 2.2±0.8 GtC year -1 can be established. The method also permits an investigation of the sensitivities of the different approaches. An analysis of the results of two three-dimensional simulations with the Hamburg Model of the Oceanic Carbon Cycle shows that the 13 C isotope indeed tracks the oceanic penetration of anthropogenic CO 2 . Because of its different time history, bomb produced radiocarbon, as measured at the time of GEOSECS, correlates much less well to excess carbon. (orig.)

High-precision dual-inlet IRMS measurements of the stable isotopes of CO2 and the N2O / CO2 ratio from polar ice core samples

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T. K. Bauska

2014-11-01

Full Text Available An important constraint on mechanisms of past carbon cycle variability is provided by the stable isotopic composition of carbon in atmospheric carbon dioxide (δ13C-CO2 trapped in polar ice cores, but obtaining very precise measurements has proven to be a significant analytical challenge. Here we describe a new technique to determine the δ13C of CO2 at very high precision, as well as measuring the CO2 and N2O mixing ratios. In this method, ancient air is extracted from relatively large ice samples (~400 g with a dry-extraction "ice grater" device. The liberated air is cryogenically purified to a CO2 and N2O mixture and analyzed with a microvolume-equipped dual-inlet IRMS (Thermo MAT 253. The reproducibility of the method, based on replicate analysis of ice core samples, is 0.02‰ for δ13C-CO2 and 2 ppm and 4 ppb for the CO2 and N2O mixing ratios, respectively (1σ pooled standard deviation. Our experiments show that minimizing water vapor pressure in the extraction vessel by housing the grating apparatus in a ultralow-temperature freezer (−60 °C improves the precision and decreases the experimental blank of the method to −0.07 ± 0.04‰. We describe techniques for accurate calibration of small samples and the application of a mass-spectrometric method based on source fragmentation for reconstructing the N2O history of the atmosphere. The oxygen isotopic composition of CO2 is also investigated, confirming previous observations of oxygen exchange between gaseous CO2 and solid H2O within the ice archive. These data offer a possible constraint on oxygen isotopic fractionation during H2O and CO2 exchange below the H2O bulk melting temperature.

Improved repetition rate mixed isotope CO{sub 2} TEA laser

Energy Technology Data Exchange (ETDEWEB)

Cohn, D. B., E-mail: dbctechnology@earthlink.net [DBC Technology Corp., 4221 Mesa St, Torrance, California 90505 (United States)

2014-09-15

A compact CO{sub 2} TEA laser has been developed for remote chemical detection that operates at a repetition rate of 250 Hz. It emits 700 mJ/pulse at 10.6 μm in a multimode beam with the {sup 12}C{sup 16}O{sub 2} isotope. With mixed {sup 12}C{sup 16}O{sub 2} plus {sup 13}C{sup 16}O{sub 2} isotopes it emits multiple lines in both isotope manifolds to improve detection of a broad range of chemicals. In particular, output pulse energies are 110 mJ/pulse at 9.77 μm, 250 mJ/pulse at 10 μm, and 550 mJ/pulse at 11.15 μm, useful for detection of the chemical agents Sarin, Tabun, and VX. Related work shows capability for long term sealed operation with a catalyst and an agile tuner at a wavelength shift rate of 200 Hz.

Quantitative measurement of carbon isotopic composition in CO2 gas reservoir by Micro-Laser Raman spectroscopy

Science.gov (United States)

Li, Jiajia; Li, Rongxi; Zhao, Bangsheng; Guo, Hui; Zhang, Shuan; Cheng, Jinghua; Wu, Xiaoli

2018-04-01

The use of Micro-Laser Raman spectroscopy technology for quantitatively determining gas carbon isotope composition is presented. In this study, 12CO2 and 13CO2 were mixed with N2 at various molar fraction ratios to obtain Raman quantification factors (F12CO2 and F13CO2), which provide a theoretical basis for calculating the δ13C value. And the corresponding values were 0.523 (0 Laser Raman analysis were carried out on natural CO2 gas from Shengli Oil-field at room temperature under different pressures. The δ13C values obtained by Micro-Laser Raman spectroscopy technology and Isotope Ratio Mass Spectrometry (IRMS) technology are in good agreement with each other, and the relative errors range of δ13C values is 1.232%-6.964%. This research provides a fundamental analysis tool for determining gas carbon isotope composition (δ13C values) quantitatively by using Micro-Laser Raman spectroscopy. Experiment of results demonstrates that this method has the potential for obtaining δ13C values in natural CO2 gas reservoirs.

BASIN TCP Stable Isotope Composition of CO2 in Terrestrial Ecosystems

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National Aeronautics and Space Administration — ABSTRACT: This data set reports stable isotope ratio data of CO2 (13C/12C and 18O/16O) associated with photosynthetic and respiratory exchanges across the...

BASIN TCP Stable Isotope Composition of CO2 in Terrestrial Ecosystems

Data.gov (United States)

National Aeronautics and Space Administration — This data set reports stable isotope ratio data of CO2 (13C/12C and 18O/16O) associated with photosynthetic and respiratory exchanges across the biosphere-atmosphere...

Concentration and stable carbon isotopic composition of CO2 in cave air of Postojnska jama, Slovenia

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Magda Mandic

2013-09-01

Full Text Available Partial pressure of CO2 (pCO2 and its isotopic composition (δ13CairCO2 were measured in Postojnska jama, Slovenia, at 10 locations inside the cave and outside the cave during a one-year period. At all interior locations the pCO2 was higher and δ13CairCO2 lower than in the outside atmosphere. Strong seasonal fluctuations in both parameters were observed at locations deeper in the cave, which are isolated from the cave air circulation. By using a binary mixing model of two sources of CO2, one of them being the atmospheric CO2, we show that the excess of CO2 in the cave air has a δ13C value of -23.3 ± 0.7 ‰, in reasonable agreement with the previously measured soil-CO2 δ13C values. The stable isotope data suggest that soil CO2 is brought to the cave by drip water.

Relation between separation factor of carbon isotope and chemical reaction of CO2 with amine in nonaqueous solvent

International Nuclear Information System (INIS)

Takeshita, Kenji; Kitamoto, Asashi

1989-01-01

The separation factor for carbon isotope exchange reaction between CO 2 and amine in nonaqueous solvent was related to absorption reaction of CO 2 in a solution. The test solutions were mixtures of primary amine (such as butylamine and tert-butylamine) or secondary amine (such as diethylamine, dipropylamine and dibutylamine) diluted with nonpolar solvent (octane or triethyalmine) or polar solvent (methanol), respectively. The isotope exchange reaction consists of three steps related to chemical reaction of CO 2 in amine and nonaqueous solvent mixture, namely the reaction between CO 2 and carbamic acid, that between CO 2 and amine carbamate, and that between CO 2 and carbamic ion. Above all, the isotope separation factor between CO 2 and carbamic acid had the highest value. The overall separation factor can be higher in amine-nonaqueous solvent mixture where the concentration of carbamic acid becomes higher. (author)

Conditional CO2 flux analysis of a managed grassland with the aid of stable isotopes

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Zeeman, M. J.; Tuzson, B.; Emmenegger, L.; Knohl, A.; Buchmann, N.; Eugster, W.

2009-04-01

Short statured managed ecosystems, such as agricultural grasslands, exhibit high temporal changes in carbon dioxide assimilation and respiration fluxes for which measurements of the net CO2 flux, e.g. by using the eddy covariance (EC) method, give only limited insight. We have therefore adopted a recently proposed concept for conditional EC flux analysis of forest to grasslands, in order to identify and quantify daytime sub-canopy respiration fluxes. To validate the concept, high frequency (≈5 Hz) stable carbon isotope analyis of CO2 was used. We made eddy covariance measurements of CO2 and its isotopologues during four days in August 2007, using a novel quantum cascade laser absorption spectrometer, capable of high time resolution stable isotope analysis. The effects of a grass cut during the measurement period could be detected and resulted in a sub-canopy source conditional flux classification, for which the isotope composition of the CO2 could be confirmed to be of a respiration source. However, the conditional flux method did not work for an undisturbed grassland canopy. We attribute this to the flux measurement height that was chosen well above the roughness sublayer, where the natural isotopic tracer (δ13C) of respiration was too well mixed with background air.

Declining Atmospheric pCO2 During the Late Miocene and Early Pliocene: New Insights from Paired Alkenone and Coccolith Stable Isotope Barometry

Science.gov (United States)

Phelps, S. R.; Polissar, P. J.; deMenocal, P. B.; Swann, J. P.; Guo, M. Y.; Stoll, H. M.

2015-12-01

The relationship between atmospheric CO2 concentrations and climate is broadly understood for the Cenozoic era: warmer periods are associated with higher atmospheric carbon dioxide. This understanding is supported by atmospheric samples of the past 800,000 years from ice cores, which suggest CO2 levels play a key role in regulating global climate on glacial interglacial timescales as well. In this context, the late Miocene poses a challenge: sea-surface temperatures indicate substantial global warmth, though existing data suggest atmospheric CO2 concentrations were lower than pre-industrial values. Recent work using the stable carbon and oxygen isotopic composition of coccolith calcite has demonstrated these organisms began actively diverting inorganic carbon away from calcification and to the site of photosynthesis during the late Miocene. This process occurs in culture experiments in response to low aqueous CO2 concentrations, and suggests decreasing atmospheric pCO2 values during the late Miocene. Here we present new data from ODP Site 806 in the western equatorial Pacific Ocean that supports declining atmospheric CO2 across the late Miocene. Carbon isotope values of coccolith calcite from Site 806 demonstrate carbon limitation and re-allocation of inorganic carbon to photosynthesis starting between ~8 and 6 Ma. The timing of this limitation at Site 806 precedes shifts at other ODP sites, reflecting the higher mixed layer temperature and resultant lower CO2 solubility at Site 806. New measurements of carbon isotope values from alkenones at Site 806 show an increase in photosynthetic carbon fractionation (ɛp) accompanied the carbon limitation evident from coccolith calcite stable isotope data. While higher ɛp is typically interpreted as higher CO2 concentrations, at Site 806, our data suggest it reflects enhancement of chloroplast CO2 from active carbon transport by the coccolithophore algae in response to lower CO2 concentrations. Our new data from ODP Site

Quantitative measurement of carbon isotopic composition in CO2 gas reservoir by Micro-Laser Raman spectroscopy.

Science.gov (United States)

Li, Jiajia; Li, Rongxi; Zhao, Bangsheng; Guo, Hui; Zhang, Shuan; Cheng, Jinghua; Wu, Xiaoli

2018-04-15

The use of Micro-Laser Raman spectroscopy technology for quantitatively determining gas carbon isotope composition is presented. In this study, 12 CO 2 and 13 CO 2 were mixed with N 2 at various molar fraction ratios to obtain Raman quantification factors (F 12CO2 and F 13CO2 ), which provide a theoretical basis for calculating the δ 13 C value. And the corresponding values were 0.523 (0Raman peak area can be used for the determination of δ 13 C values within the relative errors range of 0.076% to 1.154% in 13 CO 2 / 12 CO 2 binary mixtures when F 12CO2 /F 13CO2 is 0.466972625. In addition, measurement of δ 13 C values by Micro-Laser Raman analysis were carried out on natural CO 2 gas from Shengli Oil-field at room temperature under different pressures. The δ 13 C values obtained by Micro-Laser Raman spectroscopy technology and Isotope Ratio Mass Spectrometry (IRMS) technology are in good agreement with each other, and the relative errors range of δ 13 C values is 1.232%-6.964%. This research provides a fundamental analysis tool for determining gas carbon isotope composition (δ 13 C values) quantitatively by using Micro-Laser Raman spectroscopy. Experiment of results demonstrates that this method has the potential for obtaining δ 13 C values in natural CO 2 gas reservoirs. Copyright © 2018. Published by Elsevier B.V.

Oxygen isotope anomaly in tropospheric CO2 and implications for CO2 residence time in the atmosphere and gross primary productivity.

Science.gov (United States)

Liang, Mao-Chang; Mahata, Sasadhar; Laskar, Amzad H; Thiemens, Mark H; Newman, Sally

2017-10-13

The abundance variations of near surface atmospheric CO 2 isotopologues (primarily 16 O 12 C 16 O, 16 O 13 C 16 O, 17 O 12 C 16 O, and 18 O 12 C 16 O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, and stratospheric photochemistry. Oxygen isotopes, in particular, are affected by the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO 2 biogeochemical cycles, Δ 17 O (=ln(1 + δ 17 O) - 0.516 × ln(1 + δ 18 O)) provides an alternative constraint on the strengths of the associated cycles involving CO 2 . Here, we analyze Δ 17 O data from four places (Taipei, Taiwan; South China Sea; La Jolla, United States; Jerusalem, Israel) in the northern hemisphere (with a total of 455 measurements) and find a rather narrow range (0.326 ± 0.005‰). A conservative estimate places a lower limit of 345 ± 70 PgC year -1 on the cycling flux between the terrestrial biosphere and atmosphere and infers a residence time of CO 2 of 1.9 ± 0.3 years (upper limit) in the atmosphere. A Monte Carlo simulation that takes various plant uptake scenarios into account yields a terrestrial gross primary productivity of 120 ± 30 PgC year -1 and soil invasion of 110 ± 30 PgC year -1 , providing a quantitative assessment utilizing the oxygen isotope anomaly for quantifying CO 2 cycling.

A quantum cascade laser infrared spectrometer for CO2 stable isotope analysis: Field implementation at a hydrocarbon contaminated site under bio-remediation.

Science.gov (United States)

Guimbaud, Christophe; Noel, Cécile; Chartier, Michel; Catoire, Valéry; Blessing, Michaela; Gourry, Jean Christophe; Robert, Claude

2016-02-01

Real-time methods to monitor stable isotope ratios of CO2 are needed to identify biogeochemical origins of CO2 emissions from the soil-air interface. An isotope ratio infra-red spectrometer (IRIS) has been developed to measure CO2 mixing ratio with δ(13)C isotopic signature, in addition to mixing ratios of other greenhouse gases (CH4, N2O). The original aspects of the instrument as well as its precision and accuracy for the determination of the isotopic signature δ(13)C of CO2 are discussed. A first application to biodegradation of hydrocarbons is presented, tested on a hydrocarbon contaminated site under aerobic bio-treatment. CO2 flux measurements using closed chamber method is combined with the determination of the isotopic signature δ(13)C of the CO2 emission to propose a non-intrusive method to monitor in situ biodegradation of hydrocarbons. In the contaminated area, high CO2 emissions have been measured with an isotopic signature δ(13)C suggesting that CO2 comes from petroleum hydrocarbon biodegradation. This first field implementation shows that rapid and accurate measurement of isotopic signature of CO2 emissions is particularly useful in assessing the contribution of contaminant degradation to the measured CO2 efflux and is promising as a monitoring tool for aerobic bio-treatment. Copyright © 2016. Published by Elsevier B.V.

Stable isotope ratios of the atmospheric CH4, CO2 and N2O in Tokai-mura

International Nuclear Information System (INIS)

Porntepkasemsan, Boonsom; Andoh, Mariko A.; Amano, Hikaru

2000-11-01

This report presents the results and interpretation of stable isotope ratios of the atmospheric CH 4 , CO 2 and N 2 O from a variety of sources in Tokai-mura. The seasonal changes of δ 13 CH 4 , δ 13 CO 2 and δ 15 N 2 O were determined under in-situ conditions in four sampling sites and one control site. Such measurements are expected to provide a useful means of estimating the transport mechanisms of the three trace gases in the environment. These isotopic signatures were analyzed by Isotope Ratio Mass Spectrometer (IRMS, Micromass Isoprime). Our data showed the significant seasonal fluctuation in the Hosoura rice paddy during the entire growing season in 1999. Possible causes for the variation are postulated. Additional measurements on soil properties and on organic δ 13 C in rice plant are suggested. Cited outstanding original papers are summarized in the references. (author)

The effects of atmospheric [CO2] on carbon isotope fractionation and magnesium incorporation into biogenic marine calcite

Science.gov (United States)

Vieira, Veronica

1997-01-01

The influences of atmospheric carbon dioxide on the fractionation of carbon isotopes and the magnesium incorporation into biogenic marine calcite were investigated using samples of the calcareous alga Amphiroa and benthic foraminifer Sorites grown in the Biosphere 2 Ocean system under variable atmospheric CO2 concentrations (approximately 500 to 1200 ppm). Carbon isotope fractionation was studied in both the organic matter and the skeletal carbonate. Magnesium analysis was to be performed on the carbonate removed during decalcification. These data have not been collected due to technical problems. Carbon isotope data from Amphiroa yields a linear relation between [CO2] and Delta(sup 13)C(sub Corg)values suggesting that the fractionation of carbon isotopes during photosynthesis is positively correlated with atmospheric [CO2]. [CO2] and Delta(sup 13)C(sub Corg) values for Sorites produce a relation that is best described by a hyperbolic function where Delta(sup 13)C(sub Corg) values increase between 300 and 700 ppm and decrease from 700 to 1200 ppm. Further investigation of this relation and Sorites physiology is needed.

The isotopic composition of CO in vehicle exhaust

Science.gov (United States)

Naus, S.; Röckmann, T.; Popa, M. E.

2018-03-01

We investigated the isotopic composition of CO in the exhaust of individual vehicles. Additionally, the CO2 isotopes, and the CO:CO2, CH4:CO2 and H2:CO gas ratios were measured. This was done under idling and revving conditions, and for three vehicles in a full driving cycle on a testbench. The spread in the results, even for a single vehicle, was large: for δ13 C in CO ∼ -60 to 0‰, for δ18 O in CO ∼ +10 to +35‰, and for all gas ratios several orders of magnitude. The results show an increase in the spread of isotopic values for CO compared to previous studies, suggesting that increasing complexity of emission control in vehicles might be reflected in the isotopic composition. When including all samples, we find a weighted mean for the δ13 C and δ18 O in CO of -28.7 ± 0.5‰ and +24.8 ± 0.3‰ respectively. This result is dominated by cold petrol vehicles. Diesel vehicles behaved as a distinct group, with CO enriched in 13C and depleted in 18O, compared to petrol vehicles. For the H2:CO ratio of all vehicles, we found a value of 0.71 ± 0.31 ppb:ppb. The CO:CO2 ratio, with a mean of 19.4 ± 6.8 ppb:ppm, and the CH4:CO2 ratio, with a mean of 0.26 ± 0.05 ppb:ppm, are both higher than recent literature indicates. This is likely because our sampling distribution was biased towards cold vehicles, and therefore towards higher emission situations. The CH4:CO2 ratio was found to behave similarly to the CO:CO2 ratio, suggesting that the processes affecting CO and CH4 are similar. The δ13 C values in CO2 were close to the expected δ13 C in fuel, with no significant difference between petrol and diesel vehicles. The δ18 O values in CO2 for petrol vehicles covered a range of 20-35‰, similar to the δ18 O of CO. The δ18 O values in CO2 for diesel vehicles were close to the δ18 O in atmospheric oxygen. A set of polluted atmospheric samples, taken near a highway and inside parking garages, showed an isotopic signature of CO and a H2:CO ratio that were

A Practical Cryogen-Free CO2 Purification and Freezing Technique for Stable Isotope Analysis.

Science.gov (United States)

Sakai, Saburo; Matsuda, Shinichi

2017-04-18

Since isotopic analysis by mass spectrometry began in the early 1900s, sample gas for light-element isotopic measurements has been purified by the use of cryogens and vacuum-line systems. However, this conventional purification technique can achieve only certain temperatures that depend on the cryogens and can be sustained only as long as there is a continuous cryogen supply. Here, we demonstrate a practical cryogen-free CO 2 purification technique using an electrical operated cryocooler for stable isotope analysis. This approach is based on portable free-piston Stirling cooling technology and controls the temperature to an accuracy of 0.1 °C in a range from room temperature to -196 °C (liquid-nitrogen temperature). The lowest temperature can be achieved in as little as 10 min. We successfully purified CO 2 gas generated by carbonates and phosphoric acid reaction and found its sublimation point to be -155.6 °C at 0.1 Torr in the vacuum line. This means that the temperature required for CO 2 trapping is much higher than the liquid-nitrogen temperature. Our portable cooling system offers the ability to be free from the inconvenience of cryogen use for stable isotope analysis. It also offers a new cooling method applicable to a number of fields that use gas measurements.

Genesis of fumarolic emissions as inferred by isotope mass balances: CO 2 and water at Vulcano Island, Italy

Science.gov (United States)

Paonita, A.; Favara, R.; Nuccio, P. M.; Sortino, F.

2002-03-01

We have developed a quantitative model of CO2 and H2O isotopic mixing between magmatic and hydrothermal gases for the fumarolic emissions of the La Fossa crater (Vulcano Island, Italy). On the basis of isotope balance equations, the model takes into account the isotope equilibrium between H2O and CO2 and extends the recent model of chemical and energy two-end-member mixing by Nuccio et al. (1999). As a result, the H2O and CO2 content and the δD, δ18O, and δ13C isotope compositions for both magmatic and hydrothermal end-members have been assessed. Low contributions of meteoric steam, added at a shallow depth, have been also recognized and quantified in the fumaroles throughout the period from 1988 to 1998. Nonequilibrium oxygen isotope exchange also seems to be occurring between ascending gases and wall rocks along some fumarolic conduits. The δ13CCO2 of the magmatic gases varies around -3 to 1‰ vs. Peedee belemnite (PDB), following a perfect synchronism with the variations of the CO2 concentration in the magmatic gases. This suggests a process of isotope fractionation because of vapor exsolution caused by magma depressurization. The hydrogen isotopes in the magmatic gases (-1 to -‰ vs. standard mean ocean water [SMOW]), as well as the above δ13CCO2 value, are coherent with a convergent tectonic setting of magma generation, where the local mantle is widely contaminated by fluids released from the subducted slab. Magma contamination in the crust probably amplifies this effect. The computed isotope composition of carbon and hydrogen in the hydrothermal vapors has been used to calculate the δD and δ13C of the entire hydrothermal system, including mixed H2O-CO2 vapor, liquid water, and dissolved carbon. We have computed values of about 10‰ vs. SMOW for water and -2 to -6.5‰ vs. PDB for CO2. On these grounds, we think that Mediterranean marine water (δDH2O ≈ 10‰) feeds the hydrothermal system. It infiltrates at depth throughout the local rocks

Automated CO2 extraction from air for clumped isotope analysis in the atmo- and biosphere

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Hofmann, Magdalena; Ziegler, Martin; Pons, Thijs; Lourens, Lucas; Röckmann, Thomas

2015-04-01

The conventional stable isotope ratios 13C/12C and 18O/16O in atmospheric CO2 are a powerful tool for unraveling the global carbon cycle. In recent years, it has been suggested that the abundance of the very rare isotopologue 13C18O16O on m/z 47 might be a promising tracer to complement conventional stable isotope analysis of atmospheric CO2 [Affek and Eiler, 2006; Affek et al. 2007; Eiler and Schauble, 2004; Yeung et al., 2009]. Here we present an automated analytical system that is designed for clumped isotope analysis of atmo- and biospheric CO2. The carbon dioxide gas is quantitatively extracted from about 1.5L of air (ATP). The automated stainless steel extraction and purification line consists of three main components: (i) a drying unit (a magnesium perchlorate unit and a cryogenic water trap), (ii) two CO2 traps cooled with liquid nitrogen [Werner et al., 2001] and (iii) a GC column packed with Porapak Q that can be cooled with liquid nitrogen to -30°C during purification and heated up to 230°C in-between two extraction runs. After CO2 extraction and purification, the CO2 is automatically transferred to the mass spectrometer. Mass spectrometric analysis of the 13C18O16O abundance is carried out in dual inlet mode on a MAT 253 mass spectrometer. Each analysis generally consists of 80 change-over-cycles. Three additional Faraday cups were added to the mass spectrometer for simultaneous analysis of the mass-to-charge ratios 44, 45, 46, 47, 48 and 49. The reproducibility for δ13C, δ18O and Δ47 for repeated CO2 extractions from air is in the range of 0.11o (SD), 0.18o (SD) and 0.02 (SD)o respectively. This automated CO2 extraction and purification system will be used to analyse the clumped isotopic signature in atmospheric CO2 (tall tower, Cabauw, Netherlands) and to study the clumped isotopic fractionation during photosynthesis (leaf chamber experiments) and soil respiration. References Affek, H. P., Xu, X. & Eiler, J. M., Geochim. Cosmochim. Acta 71, 5033

CO2 and 12C:13C Isotopic Ratios on Phoebe and Iapetus

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Clark, R. N.; Brown, R. H.; Cruikshank, D. P.

2016-12-01

Cassini VIMS has obtained spatially resolved 0.35 to 5.1 micron reflectance spectra of Saturn's satellites beginning with the Phoebe fly-by in 2004 and a close fly-by of Iapetus in 2007. Both surfaces contain relatively abundant CO2. The new (2016 RC19) calibration of VIMS has provided a significant increase in the data quality, such that isotopic absorption bands in CO2 are now well defined. CO2 on Saturn's icy satellites is trapped (Cruikshank et al., 2010, Icarus v206 p561; Pinilla-Alonso et al. 2011, Icarus v211, p75i), predominantly in the dark material (Clark et al. 2012, Icarus v218 p831). Clark et al. modeled the CO2 abundance as 2.8% on Iapetus and 3.7% on Phoebe. The main 12CO2 band in VIMS spectra on Iapetus occurs at 4.253 microns and Phoebe at 4.266 microns. The 13CO2 absorption is strong on Phoebe at 4.367 microns and weak on Iapetus at 4.387 microns. Converting the Phoebe, Iapetus, and a lab reflectance spectrum (of trace H2O-CO2 mixture on a diffuse substrate), we derive preliminary values for the ratio of the equivalent widths of the 12C and 13C absorptions as 19±2 on Phoebe, 82±8 on Iapetus, and 98±10 for the laboratory spectrum. These ratios are related to the 12C/13C ratio, but there may be effects due to intra-molecular and inter-molecular coupling that will contribute to systematic errors in the isotopic abundances derived using equivalent-width measurements that we've yet to quantify. We Believe the effects are small, and will be attempting to quantify them in the future. For comparison, the terrestrial value of the 12C/13C ratio is 90.17, and vibrational coupling may explain the slightly high lab mixture result. The local interstellar medium is 69±15 (Boogert et al., 2000, A&A). Because the CO2 bands on Phoebe and Iapetus dark material have different positions, and because the observed 13C absorption strengths are so different, the surface evolutions must be different. The large enrichment in 13C on Phoebe argues for significant

Validation of 13CO2 breath analysis as a measurement of demethylation of stable isotope labeled aminopyrine in man

International Nuclear Information System (INIS)

Schneider, J.F.; Schoeller, D.A.; Nemchausky, B.; Bayer, J.L.; Klein, P.

1978-01-01

Interval sampling of expired breath as a simple, non-invasive assessment of the effect of liver disease upon hepatic microsomal drug metabolism, has been demonstrated with [ 14 C] dimethylaminoantipyrine (aminopyrine). In order to eliminate radiation risk the authors have validated the use of aminopyrine labeled with the stable, non-radioactive isotope 13 C. Simultaneous oral administration of both [ 14 C]- and [ 13 C] aminopyrine to five adult subjects without liver disease as well as five patients with known liver disease, resulted in the excretion of label at nearly identical rates in both individual time collections (r=0.94) as well as cumulative excretion for three hours (r=0.97). An oral dose of 2-mg/kg of [ 13 C) aminopyrine resulted in rates of production of 13 CO 2 significantly greater than baseline variations in 13 CO 2 production in the fasting, resting subject. Measurements of a single peak value at one half hour correlated closely with the determination of cumulative appearance over three hours (r=0.96). A consistent reproducible increase in the peak production of 13 CO 2 was observed when five patients received phenobarbital. Stable isotope labeled aminopyrine may be used to detect the effects of disease and treatment upon hepatic N-demethylation activity in human subjects without incurring any risk from radiation. Furthermore, the availability of another isotopic carbon label should make possible the study of direct drug-drug interaction utilizing CO 2 analysis. (Auth.)

Groundwater data improve modelling of headwater stream CO2 outgassing with a stable DIC isotope approach

Science.gov (United States)

Marx, Anne; Conrad, Marcus; Aizinger, Vadym; Prechtel, Alexander; van Geldern, Robert; Barth, Johannes A. C.

2018-05-01

A large portion of terrestrially derived carbon outgasses as carbon dioxide (CO2) from streams and rivers to the atmosphere. Particularly, the amount of CO2 outgassing from small headwater streams is highly uncertain. Conservative estimates suggest that they contribute 36 % (i.e. 0.93 petagrams (Pg) C yr-1) of total CO2 outgassing from all fluvial ecosystems on the globe. In this study, stream pCO2, dissolved inorganic carbon (DIC), and δ13CDIC data were used to determine CO2 outgassing from an acidic headwater stream in the Uhlířská catchment (Czech Republic). This stream drains a catchment with silicate bedrock. The applied stable isotope model is based on the principle that the 13C / 12C ratio of its sources and the intensity of CO2 outgassing control the isotope ratio of DIC in stream water. It avoids the use of the gas transfer velocity parameter (k), which is highly variable and mostly difficult to constrain. Model results indicate that CO2 outgassing contributed more than 80 % to the annual stream inorganic carbon loss in the Uhlířská catchment. This translated to a CO2 outgassing rate from the stream of 34.9 kg C m-2 yr-1 when normalised to the stream surface area. Large temporal variations with maximum values shortly before spring snowmelt and in summer emphasise the need for investigations at higher temporal resolution. We improved the model uncertainty by incorporating groundwater data to better constrain the isotope compositions of initial DIC. Due to the large global abundance of acidic, humic-rich headwaters, we underline the importance of this integral approach for global applications.

Photodissociation spectroscopy of the Mg + -CO2 complex and its isotopic analogs

Science.gov (United States)

Yeh, C. S.; Willey, K. F.; Robbins, D. L.; Pilgrim, J. S.; Duncan, M. A.

1993-02-01

Mg+-CO2 ion-molecule cluster complexes are produced by laser vaporization in a pulsed nozzle cluster source. The vibronic spectroscopy in these complexes is studied with mass-selected photodissociation spectroscopy in a reflectron time-of-flight mass spectrometer. Two excited electronic states are observed (2) 2Σ+ and 2Π. The 2Π state has a vibrational progression in the metal-CO2 stretching mode (ωe'=381.8 cm-1). The complexes are linear (Mg+-OCO) and are bound by the charge-quadrupole interaction. The dissociation energy (D0`) is 14.7 kcal/mol. Corresponding spectra are measured for each of the 24, 25, and 26 isotopes of magnesium. These results are compared to theoretical predictions made by Bauschlicher and co-workers.

Preferential flow pathways revealed by field based stable isotope analysis of CO2 by mid-infrared laser spectroscopy

Science.gov (United States)

van Geldern, Robert; Nowak, Martin; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A. C.; Jost, Hj

2016-04-01

A newly developed and commercially available isotope ratio laser spectrometer for CO2 analyses has been tested during a 10-day field monitoring campaign at the Ketzin pilot site for CO2 storage in northern Germany. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10-day carbon stable isotope data set with 30 minutes resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within 2σ analytical precision (<0.3 ‰). This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time table isotope data directly in the field. The injected CO2 tracer had a distinct δ13C value that was largely different from the reservoir background value. The laser spectroscopy data revealed a prior to this study unknown, intensive dynamic with fast changing δ13C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The new technique might contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long-term integrity of the reservoir.

Oxygen isotope systematics of chondrules in the Murchison CM2 chondrite and implications for the CO-CM relationship

Science.gov (United States)

Chaumard, Noël; Defouilloy, Céline; Kita, Noriko T.

2018-05-01

High-precision oxygen three-isotope measurements of olivine and pyroxene were performed on 29 chondrules in the Murchison CM2 chondrite by secondary ion mass spectrometry (SIMS). The oxygen isotope ratios of analyzed chondrules all plot very close to the primitive chondrule minerals (PCM) line. In each of 24 chondrules, the olivine and/or pyroxene grains analyzed show indistinguishable oxygen isotope ratios. Exceptions are minor occurrences of isotopically distinguished relict olivine grains, which were found in nine chondrules. The isotope homogeneity of these phenocrysts is consistent with a co-magmatic crystallization of olivine and pyroxene from the final chondrule melts and a significant oxygen isotope exchange between the ambient gas and the melts. Homogeneous type I chondrules with Mg#'s of 98.9-99.5 have host chondrule Δ17O values ranging from -6.0‰ to -4.1‰, with one exception (Δ17O: -1.2‰; Mg#: 99.6). Homogeneous chondrules with Mg#'s poor H2O ice (∼0.3-0.4× the CI dust; Δ17O > 0‰) and at dust enrichments of ∼300-2000×. Regarding the Mg# and oxygen isotope ratios, the chondrule populations sampled by CM and CO chondrites are similar and indistinguishable. The similarity of these 16O-rich components in CO and CM chondrites is also supported by the common Fe/Mn ratio of olivine in type II chondrules. Although they accreted similar high-temperature silicates, CO chondrites are anhydrous compared to CM chondrites, suggesting they derived from different parent bodies formed inside and outside the snow line, respectively. If chondrules in CO and CM chondrites formed at the same disk locations but the CM parent body accreted later than the CO parent body, the snow line might have crossed the common chondrule-forming region towards the Sun between the time of the CO and CM parent bodies accretion.

Seasonal variability of soil CO2 flux and its carbon isotope composition in Krakow urban area, Southern Poland.

Science.gov (United States)

Jasek, Alina; Zimnoch, Miroslaw; Gorczyca, Zbigniew; Smula, Ewa; Rozanski, Kazimierz

2014-06-01

As urban atmosphere is depleted of (13)CO2, its imprint should be detectable in the local vegetation and therefore in its CO2 respiratory emissions. This work was aimed at characterising strength and isotope signature of CO2 fluxes from soil in urban areas with varying distances from anthropogenic CO2 emissions. The soil CO2 flux and its δ(13)C isotope signature were measured using a chamber method on a monthly basis from July 2009 to May 2012 within the metropolitan area of Krakow, Southern Poland, at two locations representing different levels of anthropogenic influence: a lawn adjacent to a busy street (A) and an urban meadow (B). The small-scale spatial variability of the soil CO2 flux was also investigated at site B. Site B revealed significantly higher summer CO2 fluxes (by approximately 46 %) than site A, but no significant differences were found between their δ(13)CO2 signatures.

Groundwater data improve modelling of headwater stream CO2 outgassing with a stable DIC isotope approach

Directory of Open Access Journals (Sweden)

A. Marx

2018-05-01

Full Text Available A large portion of terrestrially derived carbon outgasses as carbon dioxide (CO2 from streams and rivers to the atmosphere. Particularly, the amount of CO2 outgassing from small headwater streams is highly uncertain. Conservative estimates suggest that they contribute 36 % (i.e. 0.93 petagrams (Pg C yr−1 of total CO2 outgassing from all fluvial ecosystems on the globe. In this study, stream pCO2, dissolved inorganic carbon (DIC, and δ13CDIC data were used to determine CO2 outgassing from an acidic headwater stream in the Uhlířská catchment (Czech Republic. This stream drains a catchment with silicate bedrock. The applied stable isotope model is based on the principle that the 13C ∕ 12C ratio of its sources and the intensity of CO2 outgassing control the isotope ratio of DIC in stream water. It avoids the use of the gas transfer velocity parameter (k, which is highly variable and mostly difficult to constrain. Model results indicate that CO2 outgassing contributed more than 80 % to the annual stream inorganic carbon loss in the Uhlířská catchment. This translated to a CO2 outgassing rate from the stream of 34.9 kg C m−2 yr−1 when normalised to the stream surface area. Large temporal variations with maximum values shortly before spring snowmelt and in summer emphasise the need for investigations at higher temporal resolution. We improved the model uncertainty by incorporating groundwater data to better constrain the isotope compositions of initial DIC. Due to the large global abundance of acidic, humic-rich headwaters, we underline the importance of this integral approach for global applications.

Fingerprinting captured CO2 using natural tracers: Determining CO2 fate and proving ownership

Science.gov (United States)

Flude, Stephanie; Gilfillan, Stuart; Johnston, Gareth; Stuart, Finlay; Haszeldine, Stuart

2016-04-01

In the long term, captured CO2 will most likely be stored in large saline formations and it is highly likely that CO2 from multiple operators will be injected into a single saline formation. Understanding CO2 behavior within the reservoir is vital for making operational decisions and often uses geochemical techniques. Furthermore, in the event of a CO2 leak, being able to identify the owner of the CO2 is of vital importance in terms of liability and remediation. Addition of geochemical tracers to the CO2 stream is an effective way of tagging the CO2 from different power stations, but may become prohibitively expensive at large scale storage sites. Here we present results from a project assessing whether the natural isotopic composition (C, O and noble gas isotopes) of captured CO2 is sufficient to distinguish CO2 captured using different technologies and from different fuel sources, from likely baseline conditions. Results include analytical measurements of CO2 captured from a number of different CO2 capture plants and a comprehensive literature review of the known and hypothetical isotopic compositions of captured CO2 and baseline conditions. Key findings from the literature review suggest that the carbon isotope composition will be most strongly controlled by that of the feedstock, but significant fractionation is possible during the capture process; oxygen isotopes are likely to be controlled by the isotopic composition of any water used in either the industrial process or the capture technology; and noble gases concentrations will likely be controlled by the capture technique employed. Preliminary analytical results are in agreement with these predictions. Comparison with summaries of likely storage reservoir baseline and shallow or surface leakage reservoir baseline data suggests that C-isotopes are likely to be valuable tracers of CO2 in the storage reservoir, while noble gases may be particularly valuable as tracers of potential leakage.

Stable carbon isotope fractionation of organic cyst-forming dinoflagellates: Evaluating the potential for a CO2 proxy

Science.gov (United States)

Hoins, Mirja; Van de Waal, Dedmer B.; Eberlein, Tim; Reichart, Gert-Jan; Rost, Björn; Sluijs, Appy

2015-07-01

Over the past decades, significant progress has been made regarding the quantification and mechanistic understanding of stable carbon isotope fractionation (13C fractionation) in photosynthetic unicellular organisms in response to changes in the partial pressure of atmospheric CO2 (pCO2). However, hardly any data is available for organic cyst-forming dinoflagellates while this is an ecologically important group with a unique fossil record. We performed dilute batch experiments with four harmful dinoflagellate species known for their ability to form organic cysts: Alexandrium tamarense, Scrippsiella trochoidea, Gonyaulax spinifera and Protoceratium reticulatum. Cells were grown at a range of dissolved CO2 concentrations characterizing past, modern and projected future values (∼5-50 μmol L-1), representing atmospheric pCO2 of 180, 380, 800 and 1200 μatm. In all tested species, 13C fractionation depends on CO2 with a slope of up to 0.17‰ (μmol L)-1. Even more consistent correlations were found between 13C fractionation and the combined effects of particulate organic carbon quota (POC quota; pg C cell-1) and CO2. Carbon isotope fractionation as well as its response to CO2 is species-specific. These results may be interpreted as a first step towards a proxy for past pCO2 based on carbon isotope ratios of fossil organic dinoflagellate cysts. However, additional culture experiments focusing on environmental variables other than pCO2, physiological underpinning of the recorded response, testing for possible offsets in 13C values between cells and cysts, as well as field calibration studies are required to establish a reliable proxy.

Near-IR laser-based spectrophotometer for comparative analysis of isotope content of CO2 in exhale air samples

International Nuclear Information System (INIS)

Stepanov, E V; Glushko, A N; Kasoev, S G; Koval', A V; Lapshin, D A

2011-01-01

We present a laser spectrophotometer aimed at high-accuracy comparative analysis of content of 12 CO 2 and 13 CO 2 isotope modifications in the exhale air samples and based on a tunable near-IR diode laser (2.05 μm). The two-channel optical scheme of the spectrophotometer and the special digital system for its control are described. An algorithm of spectral data processing aimed at determining the difference in the isotope composition of gas mixtures is proposed. A few spectral regions (near 4880 cm -1 ) are determined to be optimal for analysis of relative content of 12 CO 2 and 13 CO 2 in the exhale air. The use of the proposed spectrophotometer scheme and the developed algorithm makes the results of the analysis less susceptible to the influence of the interference in optical elements, to the absorption in the open atmosphere, to the slow drift of the laser pulse envelope, and to the offset of optical channels. The sensitivity of the comparative analysis of the isotope content of CO 2 in exhale air samples, achieved using the proposed scheme, is estimated to be nearly 0.1‰.

Oxygen isotope partitioning between rhyolitic glass/melt and CO2: An experimental study at 550-950 degrees C and 1 bar

International Nuclear Information System (INIS)

Palin, J.M.; Epstein, S.; Stolper, E.M.

1996-01-01

Oxygen isotope partitioning between gaseous CO 2 and a natural rhyolitic glass and melt (77.7 wt% SiO 2 , 0.16 wt% H 2 O total ) has been measured at 550-950 degrees C and approximately 1 bar. Equilibrium oxygen isotope fractionation factors (α CO2-rhyolite = ( 18 O/ 16 O) rhyolite ) determined in exchange experiments of 100-255 day duration. These values agree well with predictions based on experimentally determined oxygen isotope fractionation factors for CO 2 -silica glass and CO 2 -albitic glass/melt, if the rhyolitic glass is taken to be a simple mixture of normative silica and alkali feldspar components. The results indicate that oxygen isotope partitioning in felsic glasses and melts can be modeled by linear combinations of endmember silicate constituents. Rates of oxygen isotope exchange observed in the partitioning experiments are consistent with control by diffusion of molecular H 2 O dissolved in the glass/melt and are three orders of magnitude faster than predicted for rate control solely by diffusion of dissolved molecular CO 2 under the experimental conditions. Additional experiments using untreated and dehydrated (0.09 wt% H 2 O total ) rhyolitic glass quantatively support these interpretations. We conclude that diffusive oxygen isotope exchange in rhyolitic glass/melt, and probably other polymerized silicate materials, it controlled by the concentrations and diffusivities of dissolved oxygen-bearing volatile species rather than diffusion of network oxygen under all but the most volatile-poor conditions. 25 refs., 6 figs., 1 tab

Shell-model results in fp and fpg9/2 spaces for 61,63,65Co isotopes

International Nuclear Information System (INIS)

Srivastava, P. C.; Kota, V. K. B.

2011-01-01

Low-lying spectra and several high-spin states of odd-even 61,63,65 Co isotopes are calculated in two different shell-model spaces. First set of calculations have been carried out in fp-shell valence space (full fp space for 63,65 Co and a truncated one for 61 Co) using two recently derived fp-shell interactions, namely GXPF1A and KB3G, with 40 Ca as core. Similarly, the second set of calculations have been performed in fpg 9/2 valence space using an fpg effective interaction due to Sorlin et al., with 48 Ca as core and imposing a truncation. It is seen that the results of GXPF1A and KB3G are reasonable for 61,63 Co. For 65 Co, shell-model results show that the fpg interaction adopted in the study is inadequate and also points out that it is necessary to include orbitals higher than 1g 9/2 for neutron-rich Co isotopes.

Trace gases and CO sub(2) isotope records from Cabo de Rama, India

Digital Repository Service at National Institute of Oceanography (India)

Bhattacharya, S.K.; Borole, D.V.; Francey, R.J.; Allison, C.E.; Steele, L.P.; Krummel, P.; Langenfelds, R.; Masarie, K.A.; Tiwari, Y.K.; Patra, P.K.

to avoid dan- gerous climate change due to GHG forced warming. Con- centrations of CO 2 , CH 4 and N 2 O have increased at alarming rates, from preindustrial values of 280 ppm, 715 ppb and 270 ppb (circa. 1750) to 379 ppm, 1732 ppb and 319 ppb... an important effect on the con- centration and isotopic composition of atmospheric CO 2 , and the concentrations of other trace gases. Air sampling at CRI contributes to the global atmospheric composition study 10,11 . Given the potential for global impacts...

Near Surface CO2 Triple Oxygen Isotope Composition

Directory of Open Access Journals (Sweden)

Sasadhar Mahata

2016-02-01

Full Text Available The isotopic composition of carbon dioxide in the atmosphere is a powerful tool for constraining its sources and sinks. In particular, the 17O oxygen anomaly [Δ17O = 1000 × ln(1 + δ17O/1000 - 0.516 × 1000 × ln(1 + δ18O/1000], with a value > 0.5‰ produced in the middle atmosphere, provides an ideal tool for probing the exchange of carbon dioxide between the biosphere/hydrosphere and atmosphere. The biosphere/hydrosphere and anthropogenic emissions give values ≤ 0.3‰. Therefore, any anomaly in near surface CO2 would reflect the balance between stratospheric input and exchange with the aforementioned surface sources. We have analyzed Δ17O values of CO2 separated from air samples collected in Taipei, Taiwan, located in the western Pacific region. The obtained mean anomaly is 0.42 ± 0.14‰ (1-σ standard deviation, in good agreement with model prediction and a published decadal record. Apart from typically used δ13C and δ18O values, the Δ17O value could provide an additional tracer for constraining the carbon cycle.

Equilibration of metabolic CO2 with preformed CO2 and bicarbonate

International Nuclear Information System (INIS)

Hems, R.; Saez, G.T.

1983-01-01

Entry of metabolic 14 CO 2 into urea is shown to occur more readily than it equilibrates with the general pool of cellular plus extracellular bicarbonate plus CO 2 . Since the sites of CO 2 production (pyruvate dehydrogenase and oxoglutarate dehydrogenase) and of fixation (carbamoylphosphate synthetase) are intramitochondrial, it is likely that the fixation of CO 2 is also more rapid than its equilibration with the cytoplasmic pool of bicarbonate plus CO 2 . This observation may point to a more general problem concerning the interpretation of isotope data, with compartmentation or proximity of sites of production and utilisation of metabolites may result in the isotope following a preferred pathway. (Auth.)

Isotopic and Geochemical Signatures of Melgaco CO{sub 2} Rich Cold Mineralwaters, NW Portugal

Energy Technology Data Exchange (ETDEWEB)

Carreira, P. M.; Nunes, D. [Instituto Tecnologico e Nuclear, Unidade de Ciencias Quimicas e Radiofarmaceuticas, Sacavem (Portugal); Marques, J. M. [Instituto Superior Tecnico, Universidade Tecnica de Lisboa, Lisbon (Portugal); Carvalho, M. R. [Universidade de Lisboa, Faculdade de Ciencias, Departamento de Geologia, Lisbon (Portugal); Antunes da Silva, M. [UNICER Bebidas, S.A, S. Mamede de Infesta (Portugal)

2013-07-15

The isotopic and chemical compositions of CO{sub 2} rich mineral waters found in the NW of Portugal were investigated. These mineral waters are mainly related to granitic and granodioritic rocks. Based on their chemical composition, two water types are distinguished (Ca-HCO{sub 3} and Ca-Na-HCO{sub 3}), indicating different underground flow paths. Through comparison with local shallow groundwaters, water chemistry indicates that the Melgaco mineral waters evolved through water-rock interaction with the hosted rocks. Stable isotope data indicates the meteoric origin of these CO{sub 2} rich mineral waters, being recharged from about 480 up to 730 m a.s.l. Considering the {delta}{sup 18}O, {delta}{sup 2}H and the hydrochemical data, no indication of mixing seems to occur between the shallow and deep groundwater systems. The {delta}{sup 13}C determinations carried out on TDIC of the CO{sub 2} rich mineral waters point to the hypothesis of methanogenesis (upper mantle CH{sub 4} source) within the system, leading to {sup 13}C enrichment. The negligible {sup 14}C content ({approx} 2 pMC) also indicates a mantle derived carbon source for the groundwater system. (author)

Hydrogen isotope storage behavior of Zr1-xTixCo alloys

International Nuclear Information System (INIS)

Jat, Ram Avtar; Pati, Subhasis; Parida, S.C.; Agarwal, Renu; Mukerjee, S.K.

2016-01-01

Tritium storage properties similar to uranium make ZrCo as a suitable candidate material for storage, supply and recovery of hydrogen isotopes in various tritium facilities. Beside non-radioactive, nonpyrophoric at room temperature and higher storage capacity (H/f.u. up to 3, f.u. = ZrCo), it has been reported that upon repeated hydriding-dehydriding cycles, ZrCo undergoes dis-proportionation as per the reaction; ZrCo + H 2 ↔ ZrH 2 + ZrCo 2 . The present study is aimed to investigate the effect of Ti content on the hydrogen storage behavior of Zr 1-x Ti x Co alloys and the hydrogen isotope effect

Tracing the link between plant volatile organic compound emissions and CO2 fluxes and by stable isotopes

Science.gov (United States)

Werner, Christiane; Wegener, Frederik; Jardine, Kolby

2015-04-01

The vegetation exerts a large influence on the atmosphere through the emission of volatile organic compounds (VOCs) and the emission and uptake of the greenhouse gas CO2. Despite the enormous importance, processes controlling plant carbon allocation into primary and secondary metabolism, such as photosynthetic carbon uptake, respiratory CO2 emission and VOC synthesis, remains unclear. Moreover, vegetation-atmosphere CO2 exchange is associated with a large isotopic imprint due to photosynthetic carbon isotope discrimination and 13C-fractionation during respiratory CO2 release1. The latter has been proposed to be related to carbon partitioning in the metabolic branching points of the respiratory pathways and secondary metabolism, which are linked via a number of interfaces including the central metabolite pyruvate. Notably, it is a known substrate in a large array of secondary pathways leading to the biosynthesis of many volatile organic compounds (VOCs), such as volatile isoprenoids, oxygenated VOCs, aromatics, fatty acid oxidation products, which can be emitted by plants. Here we investigate the linkage between VOC emissions, CO2 fluxes and associated isotope effects based on simultaneous real-time measurements of stable carbon isotope composition of branch respired CO2 (CRDS) and VOC fluxes (PTR-MS). We utilized positionally specific 13C-labeled pyruvate branch feeding experiments in the mediterranean shrub (Halimium halimifolium) to trace the partitioning of C1, C2, and C3 carbon atoms of pyruvate into VOCs versus CO2 emissions in the light and in the dark. In the light, we found high emission rates of a large array of VOC including volatile isoprenoids, oxygenated VOCs, green leaf volatiles, aromatics, sulfides, and nitrogen containing VOCs. These observations suggest that in the light, H. halimifolium dedicates a high carbon flux through secondary biosynthetic pathways including the pyruvate dehydrogenase bypass, mevalonic acid, MEP/DOXP, shikimic acid, and

Carbon isotope exchange between gaseous CO2 and thin solution films: Artificial cave experiments and a complete diffusion-reaction model

Science.gov (United States)

Hansen, Maximilian; Scholz, Denis; Froeschmann, Marie-Louise; Schöne, Bernd R.; Spötl, Christoph

2017-08-01

Speleothem stable carbon isotope (δ13C) records provide important paleoclimate and paleo-environmental information. However, the interpretation of these records in terms of past climate or environmental change remains challenging because of various processes affecting the δ13C signals. A process that has only been sparsely discussed so far is carbon isotope exchange between the gaseous CO2 of the cave atmosphere and the dissolved inorganic carbon (DIC) contained in the thin solution film on the speleothem, which may be particularly important for strongly ventilated caves. Here we present a novel, complete reaction diffusion model describing carbon isotope exchange between gaseous CO2 and the DIC in thin solution films. The model considers all parameters affecting carbon isotope exchange, such as diffusion into, out of and within the film, the chemical reactions occurring within the film as well as the dependence of diffusion and the reaction rates on isotopic mass and temperature. To verify the model, we conducted laboratory experiments under completely controlled, cave-analogue conditions at three different temperatures (10, 20, 30 °C). We exposed thin (≈0.1 mm) films of a NaHCO3 solution with four different concentrations (1, 2, 5 and 10 mmol/l, respectively) to a nitrogen atmosphere containing a specific amount of CO2 (1000 and 3000 ppmV). The experimentally observed temporal evolution of the pH and δ13C values of the DIC is in good agreement with the model predictions. The carbon isotope exchange times in our experiments range from ca. 200 to ca. 16,000 s and strongly depend on temperature, film thickness, atmospheric pCO2 and the concentration of DIC. For low pCO2 (between 500 and 1000 ppmV, as for strongly ventilated caves), our time constants are substantially lower than those derived in a previous study, suggesting a potentially stronger influence of carbon isotope exchange on speleothem δ13C values. However, this process should only have an

High Precision Stable Isotope Measurements of Caribic Aircraft CO{sub 2} Samples: Global Distribution and Exchange with the Biosphere

Energy Technology Data Exchange (ETDEWEB)

Assonov, S. S. [Max Planck Institute for Chemistry, Mainz (Germany); Joint Research Centre, Institute for Reference Materials and Measurements (JRC-IRMM), European Commission, Geel (Belgium); Brenninkmeijer, C. A.M.; Schuck, T. J. [Max Planck Institute for Chemistry, Mainz (Germany); Taylor, P. [Joint Research Centre, Institute for Reference Materials and Measurements (JRC-IRMM), European Commission, Geel (Belgium)

2013-07-15

In 2007-2009 JRC-IRMM, in collaboration with the project CARIBIC (Civil Aircraft for Regular Investigation of the atmosphere Based on an Instrument Container, www.caribicatmospheric. com), conducted systematic measurements aimed to study the global distribution of CO{sub 2} isotopic composition. A large data set for the upper troposphere-lowermost stratosphere and free troposphere was obtained. For the first time it is demonstrated how CO{sub 2} isotope signals reflect global scale variability in air mass origin. Tight correlations observed arise either from stratosphere/troposphere mixing or from mixing of background air and air masses affected by CO{sub 2} sources and sinks, over long distances and throughout the seasons. The high quality {delta}{sup 18}O(CO{sub 2}) data prove to be a useful tracer reflecting long range CO{sub 2} transport and also CO{sub 2} exchange with land biosphere and soils. The data provide a benchmark for future comparisons and are available for modelling studies. (author)

Correction for the 17O interference in δ(13C) measurements when analyzing CO2 with stable isotope mass spectrometry

Science.gov (United States)

Coplen, Tyler B.; Brand, Willi A.; Assonov, Sergey S.

2010-01-01

Measurements of δ(13C) determined on CO2 with an isotope-ratio mass spectrometer (IRMS) must be corrected for the amount of 17O in the CO2. For data consistency, this must be done using identical methods by different laboratories. This report aims at unifying data treatment for CO2 IRMS by proposing (i) a unified set of numerical values, and (ii) a unified correction algorithm, based on a simple, linear approximation formula. Because the oxygen of natural CO2 is derived mostly from the global water pool, it is recommended that a value of 0.528 be employed for the factor λ, which relates differences in 17O and 18O abundances. With the currently accepted N(13C)/N(12C) of 0.011 180(28) in VPDB (Vienna Peedee belemnite) reevaluation of data yields a value of 0.000 393(1) for the oxygen isotope ratio N(17O)/N(16O) of the evolved CO2. The ratio of these quantities, a ratio of isotope ratios, is essential for the 17O abundance correction: [N(17O)/N(16O)]/[N(13C)/N(12C)] = 0.035 16(8). The equation [δ(13C) ≈ 45δVPDB-CO2 + 2 17R/13R (45δVPDB-CO2 – λ46δVPDB-CO2)] closely approximates δ(13C) values with less than 0.010 ‰ deviation for normal oxygen-bearing materials and no more than 0.026 ‰ in extreme cases. Other materials containing oxygen of non-mass-dependent isotope composition require a more specific data treatment. A similar linear approximation is also suggested for δ(18O). The linear approximations are easy to implement in a data spreadsheet, and also help in generating a simplified uncertainty budget.

Catalytic recombination of dissociation products with Pt/SnO2 for rare and common isotope long-life, closed-cycle CO2 lasers

Science.gov (United States)

Brown, Kenneth G.; Sidney, B. D.; Schryer, D. R.; Upchurch, B. T.; Miller, I. M.

1986-01-01

This paper reports results on recombination of pulsed CO2 laser dissociation products with Pt/SnO2 catalysts, and supporting studies in a surrogate laboratory catalyst reactor. The closed-cycle, pulsed CO2 laser has been continuously operated for one million pulses with an overall power degradation of less than 5 percent by flowing the laser gas mixture through a 2-percent Pt/SnO2 catalyst bed. In the surrogate laboratory reactor, experiments have been conducted to determine isotopic exchange with the catalyst when using rare-isotope gases. The effects of catalyst pretreatment, sample weight, composition, and temperature on catalyst efficiency have also been determined.

Reconciling the Differences between the Measurements of CO2 Isotopes by the Phoenix and MSL Landers

Science.gov (United States)

Niles, P. B.; Mahaffy, P. R.; Atreya, S.; Pavlov, A. A.; Trainer, M.; Webster, C. R.; Wong, M.

2014-01-01

Precise stable isotope measurements of the CO2 in the martian atmosphere have the potential to provide important constraints for our understanding of the history of volatiles, the carbon cycle, current atmospheric processes, and the degree of water/rock interaction on Mars. There have been several different measurements by landers and Earth based systems performed in recent years that have not been in agreement. In particular, measurements of the isotopic composition of martian atmospheric CO2 by the Thermal and Evolved Gas Analyzer (TEGA) instrument on the Mars Phoenix Lander and the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) are in stark disagreement. This work attempts to use measurements of mass 45 and mass 46 of martian atmospheric CO2 by the SAM and TEGA instruments to search for agreement as a first step towards reaching a consensus measurement that might be supported by data from both instruments.

Well-based stable carbon isotope leakage monitoring of an aquifer overlying the CO2 storage reservoir at the Ketzin pilot site, Germany

Science.gov (United States)

Nowak, Martin; Myrttinen, Anssi; Zimmer, Martin; van Geldern, Robert; Barth, Johannes A. C.

2014-05-01

At the pilot site for CO2 storage in Ketzin, a new well-based leakage-monitoring concept was established, comprising geochemical and hydraulic observations of the aquifer directly above the CO2 reservoir (Wiese et al., 2013, Nowak et al. 2013). Its purpose was to allow early detection of un-trapped CO2. Within this monitoring concept, we established a stable carbon isotope monitoring of dissolved inorganic carbon (DIC). If baseline isotope values of aquifer DIC (δ13CDIC) and reservoir CO2 (δ13CCO2) are known and distinct from each other, the δ13CDIC has the potential to serve as an an early indicator for an impact of leaked CO2 on the aquifer brine. The observation well of the overlying aquifer was equipped with an U-tube sampling system that allowed sampling of unaltered brine. The high alkaline drilling mud that was used during well drilling masked δ13CDIC values at the beginning of the monitoring campaign. However, subsequent monitoring allowed observing on-going re-equilibration of the brine, indicated by changing δ13CDIC and other geochemical values, until values ranging around -23 ‰ were reached. The latter were close to baseline values before drilling. Baselineδ13CDIC and δ13CCO2 values were used to derive a geochemical and isotope model that predicts evolution of δ13CDIC, if CO2 from the reservoir would leak into the aquifer. The model shows that equilibrium isotope fractionation would have to be considered if CO2 dissolves in the brine. The model suggests that stable carbon isotope monitoring is a suitable tool to assess the impact of injected CO2 in overlying groundwater aquifers. However, more data are required to close gaps of knowledge about fractionation behaviour within the CO2(g) - DIC system under elevated pressures and temperatures. Nowak, M., Myrttinen, A., Zimmer, M., Wiese, B., van Geldern, R., Barth, J.A.C., 2013. Well-based, Geochemical Leakage Monitoring of an Aquifer Immediately Above a CO2 Storage Reservoir by Stable Carbon

Multi-isotope tracing of CO2 leakage and water-rock interaction in a natural CCS analogue.

Science.gov (United States)

Kloppmann, Wolfram; Gemeni, Vasiliki; Lions, Julie; Koukouzas, Nikolaos; Humez, Pauline; Vasilatos, Charalampos; Millot, Romain; Pauwels, Hélène

2015-04-01

Natural analogues of CO2 accumulation and, potentially, leakage, provide a highly valuable opportunity to study (1) geochemical processes within a CO2-reservoir and the overlying aquifers or aquicludes, i.e. gas-water-rock interactions, (2) geology and tightness of reservoirs over geological timescales, (3) potential or real leakage pathways, (3) impact of leakage on shallow groundwater resources quality, and (4) direct and indirect geochemical indicators of gas leakage (Lions et al., 2014, Humez et al., 2014). The Florina Basin in NW Macedonia, Greece, contains a deep CO2-rich aquifer within a graben structure. The graben filling consists of highly heterogeneous Neogene clastic sediments constituted by components from the adjacent massifs including carbonates, schists, gneiss as well as some ultramafic volcanic rocks. Clay layers are observed that isolate hydraulically the deep, partly artesian aquifer. Organic matter, in form of lignite accumulations, is abundant in the Neogene series. The underlying bedrocks are metamorphic carbonates and silicate rocks. The origin of the CO2 accumulation is controversial (deep, partially mantle-derived D'Allessandro et al., 2008 or resulting from thermal decomposition of carbonates, Hatziyannis and Arvanitis, 2011). Groundwaters have been sampled from springs and borewells over 3 years at different depths. First results on major, minor and trace elements give evidence of water-rock interaction, mainly with carbonates but also with ultramafic components but do not indicate that CO2-seepage is the principal driver of those processes (Gemeni et al., submitted). Here we present isotope data on a selection of groundwaters (δ2H , δ18O, δ13CTDIC, 87Sr/86Sr, δ11B, δ7Li). Stable isotopes of water indicate paleo-recharge for some of the groundwaters, limited exchange with gaseous CO2 and, in one case, possibly thermal exchange processes with silicates. Sr isotope ratios vary between marine ratios and radiogenic values indicating

Isotopic separation of carbon by dissociation of CF2HCl irradiated by a Q-modulated CO2 laser

International Nuclear Information System (INIS)

Ezubchenko, A.N.; Ilyukhin, A.I.; Karchevskii, A.I.; Krasnikov, N.S.; Merzylakov, A.V.; Soloukhin, A.B.

1993-01-01

Isotopic separation of carbon by selective dissociation of CF 2 HCl by radiation from a CO 2 laser with mechanical Q-modulation has been studied experimentally. The modulation frequency was 10 4 sec -1 with a 20 W output. The peak radiation intensity is increased by a factor of 20-100 when modulated, while the average power is 0.5-0.9 that of the laser when operating in continuous mode. The authors show that under these conditions, a separation coefficient on the order of 40-50 is achieved as well as a high degree of the target isotope extraction (70%)

Isotopic tracers of sources, wells and of CO{sub 2} reactivity in geological reservoirs; Tracage isotopique des sources, puits et de la reactivite du CO{sub 2} dans les reservoirs geologiques

Energy Technology Data Exchange (ETDEWEB)

Assayag, N

2006-12-15

The aim of this research works consisted in studying the behaviour of the carbonate system (dissolved inorganic carbon: DIC) following a CO{sub 2} injection (artificial or natural), in geological reservoirs. One part of the study consisted in improving an analytical protocol for the measurement of {delta} {sup 13}C DIC and DIC, using a continuous flow mass spectrometer. As a first study, we have focused our attention on the Pavin Lake (Massif Central, France). Owing to its limnologic characteristics (meromictic lake) and a deep volcanic CO{sub 2} contribution, it can be viewed as a natural analogue of reservoir storing important quantities of CO{sub 2} in the bottom part. Isotopic measurements ({delta} {sup 18}O, {delta} {sup 13}C DIC) allowed to better constrain the dynamics of the lake (stratification, seasonal variations), the magnitudes of biological activities (photosynthesis, organic matter decay, methane oxidation, methano-genesis), carbon sources (magmatic, methano-genetic), and the hydrological budgets (sub-lacustrine inputs). The second study was conducted on the Lamont-Doherty test well site (NY, USA). It includes an instrumental borehole which cuts through most of the section of the Palisades sill and into the Newark Basin sediments. Single well push-pull tests were performed: a test solution containing conservative tracers and a reactive tracer (CO{sub 2}) was injected at a permeable depth interval located in basaltic and meta sedimentary rocks. After an incubation period, the test solution/groundwater mixture was extracted from the hydraulically isolated zone. Isotopic measurements ({delta} {sup 18}O, {delta} {sup 13}C DIC) confronted to chemical data (major elements) allowed to investigate the extent of in-situ CO{sub 2}-water-rock interactions: essentially calcite dissolution and at a lesser extend silicate dissolution...and for one of the test, CO{sub 2} degassing. (author)

Metrology for stable isotope reference materials: 13C/12C and 18O/16O isotope ratio value assignment of pure carbon dioxide gas samples on the Vienna PeeDee Belemnite-CO2 scale using dual-inlet mass spectrometry.

Science.gov (United States)

Srivastava, Abneesh; Michael Verkouteren, R

2018-05-25

Isotope ratio measurements have been conducted on a series of isotopically distinct pure CO 2 gas samples using the technique of dual-inlet isotope ratio mass spectrometry (DI-IRMS). The influence of instrumental parameters, data normalization schemes on the metrological traceability and uncertainty of the sample isotope composition have been characterized. Traceability to the Vienna PeeDee Belemnite(VPDB)-CO 2 scale was realized using the pure CO 2 isotope reference materials(IRMs) 8562, 8563, and 8564. The uncertainty analyses include contributions associated with the values of iRMs and the repeatability and reproducibility of our measurements. Our DI-IRMS measurement system is demonstrated to have high long-term stability, approaching a precision of 0.001 parts-per-thousand for the 45/44 and 46/44 ion signal ratios. The single- and two-point normalization bias for the iRMs were found to be within their published standard uncertainty values. The values of 13 C/ 12 C and 18 O/ 16 O isotope ratios are expressed relative to VPDB-CO 2 using the [Formula: see text] and [Formula: see text] notation, respectively, in parts-per-thousand (‰ or per mil). For the samples, value assignments between (-25 to +2) ‰ and (-33 to -1) ‰ with nominal combined standard uncertainties of (0.05, 0.3) ‰ for [Formula: see text] and [Formula: see text], respectively were obtained. These samples are used as laboratory reference to provide anchor points for value assignment of isotope ratios (with VPDB traceability) to pure CO 2 samples. Additionally, they serve as potential parent isotopic source material required for the development of gravimetric based iRMs of CO 2 in CO 2 -free dry air in high pressure gas cylinder packages at desired abundance levels and isotopic composition values. Graphical abstract CO 2 gas isotope ratio metrology.

Using stable isotopes in tree rings to evaluate the impact of urban pollution on CO2 uptake by forests

International Nuclear Information System (INIS)

Savard, M.M.; Begin, Ch.; Marion, J.

2004-01-01

Contributions addressing the impact of industrial activities on tree growth are scarce; likewise, only a few studies document δ 13 C values in growth rings of natural specimens subjected to potentially toxic industrial emissions. These last studies suggest that the SO 2 emissions affect the physiology of trees and induce changes in their carbon isotope ratios. It has been reported that copper-smelter emissions reduce the C uptake of exposed trees by 35 % to 6 % relatively to unexposed trees, in growth stands located between 9 and 120 km from the smelter. In the context of the globally increasing concentrations of CO 2 in the atmosphere, what is the net impact of the large-scale annual reduction of CO 2 uptake induced by phyto-toxic pollutants? What should we expect for trees growing in regions submitted to urban diffuse pollution? It has been recently suggested on the basis of plant biomass measurements in the New York region that urban pollution can relatively reduce plant growth, but the effect is apparently greater in distant rural sites than in peri-urban and urban ones. Is this representative of numerous urban settings? If the answer to this question is yes, the pollution-effect parameter should be considered in the global annual forest C budget, particularly for the highly industrialized northern hemisphere. The specific objectives of this study are to: (1) measure the tissue increments of the stems and determine the C isotopic ratios in tree-ring cellulose of selected trees undergoing pollution stress in selected peri-urban stands; (2) present a secular time series of the CO 2 uptake by forests peripheral to a large urban region; and (3) evaluate stable isotope dendro-geochemistry as a proxy for past changes of air quality in urban and peri-urban settings. (authors)

Deep ocean ventilation, carbon isotopes, marine sedimentation and the deglacial CO2 rise

Directory of Open Access Journals (Sweden)

C. Heinze

2011-07-01

Full Text Available The link between the atmospheric CO2 level and the ventilation state of the deep ocean is an important building block of the key hypotheses put forth to explain glacial-interglacial CO2 fluctuations. In this study, we systematically examine the sensitivity of atmospheric CO2 and its carbon isotope composition to changes in deep ocean ventilation, the ocean carbon pumps, and sediment formation in a global 3-D ocean-sediment carbon cycle model. Our results provide support for the hypothesis that a break up of Southern Ocean stratification and invigorated deep ocean ventilation were the dominant drivers for the early deglacial CO2 rise of ~35 ppm between the Last Glacial Maximum and 14.6 ka BP. Another rise of 10 ppm until the end of the Holocene is attributed to carbonate compensation responding to the early deglacial change in ocean circulation. Our reasoning is based on a multi-proxy analysis which indicates that an acceleration of deep ocean ventilation during early deglaciation is not only consistent with recorded atmospheric CO2 but also with the reconstructed opal sedimentation peak in the Southern Ocean at around 16 ka BP, the record of atmospheric δ13CCO2, and the reconstructed changes in the Pacific CaCO3 saturation horizon.

Interannual variability in the oxygen isotopes of atmospheric CO2 driven by El Nino

NARCIS (Netherlands)

Welp, Lisa R.; Keeling, Ralph F.; Meijer, Harro A. J.; Bollenbacher, Alane F.; Piper, Stephen C.; Yoshimura, Kei; Francey, Roger J.; Allison, Colin E.; Wahlen, Martin

2011-01-01

The stable isotope ratios of atmospheric CO2 (O-18/O-16 and C-13/C-12) have been monitored since 1977 to improve our understanding of the global carbon cycle, because biosphere-atmosphere exchange fluxes affect the different atomic masses in a measurable way(1). Interpreting the O-18/O-16

Isotope labelling study of CO oxidation-assisted epoxidation of propene. Implications for oxygen activation on Au catalysts.

Science.gov (United States)

Jiang, Jian; Oxford, Sean M; Fu, Baosong; Kung, Mayfair C; Kung, Harold H; Ma, Jiantai

2010-06-07

(18)O isotope labelling studies of the CO oxidation-assisted epoxidation of propene, catalyzed by a mixture of Au/TiO(2) and TS-1, using a methanol-H(2)O solvent showed the O in the epoxide was exclusively from O(2) and not H(2)O or methanol.

Seasonal Variations of Isotope Ratios and CO2 Concentrations in Firn Air

OpenAIRE

Weiler, Karin; Schwander, Jakob; Leuenberger, Markus; Blunier, Thomas; Mulvaney, Robert; Anderson, Philip S.; Salmon, Rhian; Sturges, William T.

2009-01-01

A first year-round firn air sampling carried out at the British Antarctic station Halley in 2003 shows isotope and CO2 changes owing to diffusive mixing driven by seasonal variations of surface temperature, and gas composition of the atmosphere. Seasonal firn temperatures are well reproduced from the atmospheric temperature history. Based on these profiles thermal diffusion is forced with thermal diffusion factors αT with respect to air. Application of the available literature data for αT (15...

Unusual isotopic composition of C-CO2 from sterilized soil microcosms: a new way to separate intracellular from extracellular respiratory metabolisms.

Science.gov (United States)

Kéraval, Benoit; Alvarez, Gaël; Lehours, Anne Catherine; Amblard, Christian; Fontaine, Sebastien

2015-04-01

The mineralization of organic C requires two main steps. First, microorganisms secrete exoenzymes in soil in order to depolymerize plant and microbial cell walls and release soluble substrates for microbial assimilation. The second step of mineralization, during which C is released as CO2, implies the absorption and utilization of solubilized substrates by microbial cells with the aim to produce energy (ATP). In cells, soluble substrates are carried out by a cascade of respiratory enzymes, along which protons and electrons are transferred from a substrate to oxygen. Given the complexity of this oxidative metabolism and the typical fragility of respiratory enzymes, it is traditionally considered that respiration (second step of C mineralization process) is strictly an intracellular metabolism process. The recurrent observations of substantial CO2 emissions in soil microcosms where microbial cells have been reduced to extremely low levels challenges this paradigm. In a recent study where some respiratory enzymes have shown to function in an extracellular context in soils, Maire et al. (2013) suggested that an extracellular oxidative metabolism (EXOMET) substantially contributes to CO2 emission from soils. This idea is supported by the recent publication of Blankinship et al., 2014 who showed the presence of active enzymes involved in the Krebs cycle on soil particles. Many controversies subsist in the scientific community due to the presence of non-proliferating but morphologically intact cells after irradiation that could substantially contribute to those soil CO2 emissions. To test whether a purely extracellular oxidative metabolism contribute to soil CO2 emissions, we combined high doses of gamma irradiations to different time of soil autoclaving. The presence of active and non-active cells in soil was checked by DNA and RNA extraction and by electronic microscopy. None active cells (RNA-containing cells) were detectable after irradiation, but some morphological

Solid state synthesis of stoichiometric LiCoO2 from mechanically activated Co-Li2CO3 mixtures

International Nuclear Information System (INIS)

Berbenni, Vittorio; Milanese, Chiara; Bruni, Giovanna; Marini, Amedeo

2006-01-01

Stoichiometric lithium cobalt oxide (LiCoO 2 ) has been synthesized by solid state reaction of mixtures of the system Co-0.5Li 2 CO 3 after mechanical activation by high energy milling. The differences in the reaction mechanism and in product stoichiometry with respect to what happens when starting from the non activated (physical) system have been brought into evidence by TG analysis. Furthermore it has been shown that stoichiometric LiCoO 2 is obtained by a 200 h annealing of the activated mixture at temperatures as low as 400 deg. C. Finally, it has been revealed that longer activation times (150 h) result in Co oxidation to Co 3 O 4 that, in turn, hampers the formation of stoichiometric LiCoO 2

Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

Science.gov (United States)

Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

2017-12-01

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr

The influence of CO2 proceding from plant residue decomposition in the soil on isotopic ratio 13C/12c and plant development

International Nuclear Information System (INIS)

Martins, D.

1987-01-01

To determine the effect of plant incorporated in the soil on the microclimate of plant growth, an experiment was carried out in greenhouse and then under field conditions. Plant residue of C-3 crops δ 13 C = - 27.6 0 /00, was incorporated in the soil. This altered the isotopic composition of the CO 2 in soil air and in atmospheric air of soil layers adjacent to the surface. The soil air CO 2 isotopic composition showed that approximately 79% carbon was from the incorporated organic matter and 50% to 3% in O to 30 cm layers, respectively, in the atmospheric air adjacent to the surface. The isotopic ratio 13 C/ 12 C of plants cultivated in soil with incorporated organic matter was determined and it was noted that the envolved CO 2 was photosynthetically absorved by the plants during growth. CO 2 contribution from organic matter to the isotopic composition of C-4 plants varied from 33% to 13% during growth. Plants cultivated in soil with organic matter had a better development than those cultivated in natural soil. Productivity was on average 50% greater than the control plants. (author) [pt

Long-term field performance of a tunable diode laser absorption spectrometer for analysis of carbon isotopes of CO2 in forest air

Directory of Open Access Journals (Sweden)

D. R. Bowling

2008-09-01

Full Text Available Tunable diode laser absorption spectrometry (TDLAS is gaining in popularity for measuring the mole fraction [CO2] and stable isotopic composition (δ13C of carbon dioxide (CO2 in air in studies of biosphere-atmosphere gas exchange. Here we present a detailed examination of the performance of a commercially-available TDLAS located in a high-altitude subalpine coniferous forest (the Niwot Ridge AmeriFlux site, providing the first multi-year analysis of TDLAS instrument performance for measuring CO2 isotopes in the field. Air was sampled from five to nine vertical locations in and above the forest canopy every ten minutes for 2.4 years. A variety of methods were used to assess instrument performance. Measurement of two compressed air cylinders that were in place over the entire study establish the long-term field precision of 0.2 μmol mol−1 for [CO2] and 0.35‰ for δ13C, but after fixing several problems the isotope precision improved to 0.2permil (over the last several months. The TDLAS provided detail on variability of δ13C of atmospheric CO2 that was not represented in weekly flask samples, as well as information regarding the influence of large-scale (regional seasonal cycle and local forest processes on [CO2] and δ13C of CO2. There were also clear growing season and winter differences in the relative contributions of photosynthesis and respiration on the [CO2] and δ13C of forest air.

Frequency stabilization of quantum cascade laser for spectroscopic CO2 isotope analysis

Science.gov (United States)

Han, Luo; Xia, Hua; Pang, Tao; Zhang, Zhirong; Wu, Bian; Liu, Shuo; Sun, Pengshuai; Cui, Xiaojuan; Wang, Yu; Sigrist, Markus W.; Dong, Fengzhong

2018-06-01

Using off-axis integrated cavity output spectroscopy, named OA-ICOS, the absorption spectrum of CO2 at 4.32 μm is recorded by using a quantum cascade laser (QCL). The concentration of the three isotopologues 16O12C16O, 16O13C16O and 16O12C18O is detected simultaneously. The isotope abundance ratio of 13C and 18O in CO2 gas can be obtained, which is most useful for ecological research. Since the ambient temperature has a serious influence on the output wavelength of the laser, even small temperature variations seriously affect the stability and sensitivity of the system. In this paper, a wavelength locking technique for QCL is proposed. The output of a digital potentiometer integrated in the laser current driver control is modified by software, resulting in a correction of the driving current of the laser and thus of its wavelength. This method strongly reduces the influence of external factors on the wavelength drift of lasers and thus substantially improves the stability and performance of OA-ICOS as is demonstrated with long-time measurements on CO2 in laboratory air.

The CO2nnect activities

Science.gov (United States)

Eugenia, Marcu

2014-05-01

Climate change is one of the biggest challenges we face today. A first step is the understanding the problem, more exactly what is the challenge and the differences people can make. Pupils need a wide competencies to meet the challenges of sustainable development - including climate change. The CO2nnect activities are designed to support learning which can provide pupils the abilities, skills, attitudes and awareness as well as knowledge and understanding of the issues. The project "Together for a clean and healthy world" is part of "The Global Educational Campaign CO2nnect- CO2 on the way to school" and it was held in our school in the period between February and October 2009. It contained a variety of curricular and extra-curricular activities, adapted to students aged from 11 to 15. These activities aimed to develop in students the necessary skills to understanding man's active role in improving the quality of the environment, putting an end to its degrading process and to reducing the effects of climate changes caused by the human intervention in nature, including transport- a source of CO2 pollution. The activity which I propose can be easily adapted to a wide range of age groups and linked to the curricula of many subjects: - Investigate CO2 emissions from travel to school -Share the findings using an international database -Compare and discuss CO2 emissions -Submit questions to a climate- and transport expert -Partner with other schools -Meet with people in your community to discuss emissions from transport Intended learning outcomes for pupils who participate in the CO2nnect campaign are: Understanding of the interconnected mobility- and climate change issue climate change, its causes and consequences greenhouse-gas emissions from transport and mobility the interlinking of social, environmental, cultural and economic aspects of the local transport system how individual choices and participation can contribute to creating a more sustainable development

Barium isotope fractionation during experimental formation of the double carbonate BaMn[CO3](2) at ambient temperature.

Science.gov (United States)

Böttcher, Michael E; Geprägs, Patrizia; Neubert, Nadja; von Allmen, Katja; Pretet, Chloé; Samankassou, Elias; Nägler, Thomas F

2012-09-01

In this study, we present the first experimental results for stable barium (Ba) isotope ((137)Ba/(134)Ba) fractionation during low-temperature formation of the anhydrous double carbonate BaMn[CO(3)](2). This investigation is part of an ongoing work on Ba fractionation in the natural barium cycle. Precipitation at a temperature of 21±1°C leads to an enrichment of the lighter Ba isotope described by an enrichment factor of-0.11±0.06‰ in the double carbonate than in an aqueous barium-manganese(II) chloride/sodium bicarbonate solution, which is within the range of previous reports for synthetic pure BaCO (3) (witherite) formation.

Carbon isotope composition of CO2-rich inclusions in cumulate-forming mantle minerals from Stromboli volcano (Italy)

Science.gov (United States)

Gennaro, Mimma Emanuela; Grassa, Fausto; Martelli, Mauro; Renzulli, Alberto; Rizzo, Andrea Luca

2017-10-01

We report on measurements of concentration and carbon isotope composition (δ13CCO2) of CO2 trapped in fluid inclusions of olivine and clinopyroxene crystals separated from San Bartolo ultramafic cumulate Xenoliths (SBX) formed at mantle depth (i.e., beneath a shallow Moho supposed to be at 14.8 km). These cumulates, erupted about 2 ka ago at Stromboli volcano (Italy), have been already investigated by Martelli et al. (2014) mainly for Sr-Nd isotopes and for their noble gases geochemistry. The concentration of CO2 varies of one order of magnitude from 3.8·10- 8 mol g- 1 to 4.8·10- 7 mol g- 1, with δ13C values between - 2.8‰ and - 1.5‰ vs V-PDB. These values overlap the range of measurements performed in the crater gases emitted at Stromboli (- 2.5‰ residence within the volcano plumbing system. Such δ13C values are higher than those commonly reported for MORB-like upper mantle (- 8 ÷ - 4‰) and likely reflect the source contamination of the local mantle wedge by CO2 coming from the decarbonation of the sediments carried by the subducting Ionian slab with a contribution of organic carbon up to 7%.

Carbon isotope fractionation of chlorinated ethenes during oxidation by Fe{sup 2+} activated persulfate

Energy Technology Data Exchange (ETDEWEB)

Marchesi, Massimo, E-mail: m2marche@uwaterloo.ca [Departament de Cristallografia, Mineralogia i Diposits Minerals, Universitat de Barcelona, Barcelona, Catalunya 08028 (Spain); Earth and Environmental Department, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Aravena, Ramon [Earth and Environmental Department, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Sra, Kanwartej S. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Golder Associates Inc, Toronto, Ontario, Canada L5N 5Z7 (Canada); Thomson, Neil R. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Otero, Neus; Soler, Albert [Departament de Cristallografia, Mineralogia i Diposits Minerals, Universitat de Barcelona, Barcelona, Catalunya 08028 (Spain); Mancini, Silvia [Golder Associates Inc, Toronto, Ontario, Canada L5N 5Z7 (Canada)

2012-09-01

The increased use of persulfate (S{sub 2}O{sub 8}{sup 2-}) for in situ chemical oxidation to treat groundwater and soils contaminated by chlorinated hydrocarbon compounds (CHCs) requires unbiased methods to assess treatment performance. Stable carbon isotope analysis offers a potential tool for assessing the in situ treatment performance of persulfate at sites contaminated with CHCs. This study investigated the extent of C isotope fractionation during oxidation of tetrachloroethene (PCE), trichloroethene (TCE) and cis-dichloroethene (cis-DCE) by persulfate activated by ferrous ion (Fe{sup 2+}). An average carbon isotope enrichment factor {epsilon}{sub bulk} of - 4.9 Per-Mille-Sign for PCE, - 3.6 Per-Mille-Sign for TCE and - 7.6 Per-Mille-Sign for cis-DCE were obtained in batch experiments. Variations in the initial S{sub 2}O{sub 8}{sup 2-}/Fe{sup 2+}/CHC molar ratios did not result in any significant differences in carbon isotope fractionation. The occurrence of carbon isotope fractionation during oxidation and the lack of dependence of enrichment factors upon the S{sub 2}O{sub 8}{sup 2-}/Fe{sup 2+}/CHC molar ratio demonstrate that carbon isotope analysis can potentially be used at contaminated sites as an additional technique to estimate treatment efficacy during oxidation of CHCs by Fe{sup 2+} activated persulfate. Highlights: Black-Right-Pointing-Pointer The performance of in situ chemical oxidation (ISCO) is still difficult to assess. Black-Right-Pointing-Pointer We investigated the potential of carbon isotope analysis as a new assessing tool. Black-Right-Pointing-Pointer C isotope of PCE, TCE and DCE oxidized by persulfate activated by Fe{sup 2+} was measured. Black-Right-Pointing-Pointer Enrichment factors of - 4.9 Per-Mille-Sign for PCE, - 3.6 Per-Mille-Sign for TCE and - 7.6 Per-Mille-Sign for cisDCE were obtained. Black-Right-Pointing-Pointer Carbon isotope can potentially be used to estimate the ISCO treatment efficacy.

Continuous-flow IRMS technique for determining the 17O excess of CO2 using complete oxygen isotope exchange with cerium oxide

NARCIS (Netherlands)

Mrozek, D. J.; Van Der Veen, C.; Kliphuis, M.; Kaiser, J.; Wiegel, A. A.; Röckmann, T.

2015-01-01

This paper presents an analytical system for analysis of all single substituted isotopologues (12C16O17O, 12C16O18O, 13C16O16O) in nanomolar quantities of CO2 extracted from atmospheric air samples. CO2 is separated from bulk air by gas chromatography and CO2 isotope ratio measurements (ion masses

C4 plant isotopic composition ((delta)13C) evidence for urban CO2 pollution in the city of Cotonou, Benin (West Africa)

International Nuclear Information System (INIS)

Kelome, Nelly C.; Leveque, Jean; Andreux, Francis; Milloux, Marie-Jeanne; Oyede, Lucien-Marc

2006-01-01

The carbon isotopic composition ((delta) 13 C) of plants can reveal the isotopic carbon content of the atmosphere in which they develop. The (delta) 13 C values of air and plants depend on the amount of atmospheric fossil fuel CO 2 , which is chiefly emitted in urban areas. A new indicator of CO 2 pollution is tested using the (delta) 13 C variation in a C 4 grass: Eleusine indica. A range of about 4%% delta units was observed at different sites in Cotonou, the largest city in the Republic of Benin. The highest (delta) 13 C values, from -12%% to -14%%, were found in low traffic zones; low (delta) 13 C values, from -14%% to -16%%, were found in high traffic zones. The amount of fossil fuel carbon assimilated by plants represented about 20% of the total plant carbon content. An overall decrease in plant (delta) 13 C values was observed over a four-year monitoring period. This decrease was correlated with increasing vehicle traffic. The (delta) 13 C dataset and the corresponding geographical database were used to map and define zones of high and low 13 C-depleted CO 2 emissions in urban and sub-urban areas. The spatial distribution follows dominant wind directions, with the lowest emission zones found in the southwest of Cotonou. High CO 2 emissions occurred in the north, the east and the center, providing evidence of intense anthropogenic activity related to industry and transportation. (author)

Catalysts for long-life closed-cycle CO2 lasers

Science.gov (United States)

Schryer, David R.; Sidney, Barry D.; Miller, Irvin M.; Hess, Robert V.; Wood, George M.; Batten, Carmen E.; Burney, Lewis G.; Hoyt, Ronald F.; Paulin, Patricia A.; Brown, Kenneth G.

1987-01-01

Long-life, closed-cycle operation of pulsed CO2 lasers requires catalytic CO-O2 recombination both to remove O2, which is formed by discharge-induced CO2 decomposition, and to regenerate CO2. Platinum metal on a tin (IV) oxide substrate (Pt/SnO2) has been found to be an effective catalyst for such recombination in the desired temperature range of 25 to 100 C. This paper presents a description of ongoing research at NASA-LaRC on Pt/SnO2 catalyzed CO-O2 recombination. Included are studies with rare-isotope gases since rare-isotope CO2 is desirable as a laser gas for enhanced atmospheric transmission. Results presented include: (1) achievement of 98% to 100% conversion of a stoichiometric mixture of CO and O2 to CO2 for 318 hours (greater than 1 x 10 to the 6th power seconds), continuous, at a catalyst temperature of 60 C, and (2) development of a technique verified in a 30-hour test, to prevent isotopic scrambling when CO-18 and O-18(2) are reacted in the presence of a common-isotope Pt/Sn O-16(2) catalyst.

Monitoring the bio-stimulation of hydrocarbon-contaminated soils by measurements of soil electrical properties, and CO2 content and its 13C/12C isotopic signature

Science.gov (United States)

Noel, C.; Gourry, J.; Ignatiadis, I.; Colombano, S.; Dictor, M.; Guimbaud, C.; Chartier, M.; Dumestre, A.; Dehez, S.; Naudet, V.

2013-12-01

Hydrocarbon contaminated soils represent an environmental issue as it impacts on ecosystems and aquifers. Where significant subsurface heterogeneity exists, conventional intrusive investigations and groundwater sampling can be insufficient to obtain a robust monitoring of hydrocarbon contaminants, as the information they provide is restricted to vertical profiles at discrete locations, with no information between sampling points. In order to obtain wider information in space volume on subsurface modifications, complementary methods can be used like geophysics. Among geophysical methods, geoelectrical techniques such as electrical resistivity (ER) and induced polarization (IP) seem the more promising, especially to study the effects of biodegradation processes. Laboratory and field geoelectrical experiments to characterize soils contaminated by oil products have shown that mature hydrocarbon-contaminated soils are characterized by enhanced electrical conductivity although hydrocarbons are electrically resistive. This high bulk conductivity is due to bacterial impacts on geological media, resulting in changes in the chemical and physical properties and thus, to the geophysical properties of the ground. Moreover, microbial activity induced CO2 production and isotopic deviation of carbon. Indeed, produced CO2 will reflect the pollutant isotopic signature. Thus, the ratio δ13C(CO2) will come closer to δ13C(hydrocarbon). BIOPHY, project supported by the French National Research Agency (ANR), proposes to use electrical methods and gas analyses to develop an operational and non-destructive method for monitoring in situ biodegradation of hydrocarbons in order to optimize soil treatment. Demonstration field is located in the South of Paris (France), where liquid fuels (gasoline and diesel) leaked from some tanks in 1997. In order to stimulate biodegradation, a trench has been dug to supply oxygen to the water table and thus stimulate aerobic metabolic bioprocesses. ER and

Hydrogeochemical and stable isotopic investigations on CO2-rich mineral waters from Harghita Mts. (Eastern Carpathians, Romania)

Science.gov (United States)

Kis, Boglárka-Mercedesz; Baciu, Călin; Kármán, Krisztina; Kékedy-Nagy, Ladislau; Francesco, Italiano

2013-04-01

There is a worldwide interest on geothermal, mineral and groundwater as a resource for energy, drinking water supply and therapeutic needs. The increasing trend in replacing tap water with commercial bottled mineral water for drinking purposes has become an economic, hydrogeologic and medical concern in the last decades. Several investigations have been carried out worldwide on different topics related to geothermal and mineral waters, dealing with mineral water quality assessment, origin of geothermal and mineral waters, geochemical processes that influence water chemistry and water-rock interaction In Romania, the Călimani-Gurghiu-Harghita Neogene to Quaternary volcanic chain (Eastern Carpathians) is one of the most important areas from the point of view of CO2-rich mineral waters. These mineral water springs occur within other post-volcanic phenomena like dry CO2 emissions, moffettes, bubbling pools, H2S gas emissions etc. Mineral waters from this area are used for bottling, local spas and drinking purposes for local people. The number of springs, around 2000 according to literature data, shows that there is still a significant unexploited potential for good quality drinking water in this area. Within the youngest segment of the volcanic chain, the Harghita Mts., its volcaniclastic aprons and its boundary with the Transylvanian Basin, we have carried out an investigation on 23 CO2-rich mineral water springs from a hydrogeochemical and stable isotopic point of view. The mineral waters are Ca-Mg-HCO3 to Na-Cl type. Sometimes mixing between the two types can be observed. We have detected a great influence of water-rock interaction on the stable isotopic composition of the mineral waters, shown by isotopic shifts to the heavier oxygen isotope, mixing processes between shallow and deeper aquifers and local thermal anomalies. Acknowledgements: The present work was financially supported by the Romanian National Research Council, Project PN-II-ID-PCE-2011-3-0537 and by

Study of the Role of Terrestrial Processes in the Carbon Cycle Based on Measurements of the Abundance and Isotopic Composition of Atmospheric CO2

Energy Technology Data Exchange (ETDEWEB)

Piper, Stephen C; Keeling, Ralph F

2012-01-03

The main objective of this project was to continue research to develop carbon cycle relationships related to the land biosphere based on remote measurements of atmospheric CO2 concentration and its isotopic ratios 13C/12C, 18O/16O, and 14C/12C. The project continued time-series observations of atmospheric carbon dioxide and isotopic composition begun by Charles D. Keeling at remote sites, including Mauna Loa, the South Pole, and eight other sites. Using models of varying complexity, the concentration and isotopic measurements were used to study long-term change in the interhemispheric gradients in CO2 and 13C/12C to assess the magnitude and evolution of the northern terrestrial carbon sink, to study the increase in amplitude of the seasonal cycle of CO2, to use isotopic data to refine constraints on large scale changes in isotopic fractionation which may be related to changes in stomatal conductance, and to motivate improvements in terrestrial carbon cycle models. The original proposal called for a continuation of the new time series of 14C measurements but subsequent descoping to meet budgetary constraints required termination of measurements in 2007.

Estimation of the efficiency of hydrocarbon mineralization in soil by measuring CO2-emission and variations in the isotope composition of carbon dioxide

Science.gov (United States)

Dubrovskaya, Ekaterina; Turkovskaya, Olga

2010-05-01

Estimation of the efficiency of hydrocarbon mineralization in soil by measuring CO2-emission and variations in the isotope composition of carbon dioxide E. Dubrovskaya1, O. Turkovskaya1, A. Tiunov2, N. Pozdnyakova1, A. Muratova1 1 - Institute of Biochemistry and Physiology of Plants and Microorganisms, RAS, Saratov, 2 - A.N. Severtsov Institute of Ecology and Evolution, RAS, Moscow, Russian Federation Hydrocarbon mineralization in soil undergoing phytoremediation was investigated in a laboratory experiment by estimating the variation in the 13С/12С ratio in the respired СО2. Hexadecane (HD) was used as a model hydrocarbon pollutant. The polluted soil was planted with winter rye (Secale cereale) inoculated with Azospirillum brasilense strain SR80, which combines the abilities to promote plant growth and to degrade oil hydrocarbon. Each vegetated treatment was accompanied with a corresponding nonvegetated one, and uncontaminated treatments were used as controls. Emission of carbon dioxide, its isotopic composition, and the residual concentration of HD in the soil were examined after two and four weeks. At the beginning of the experiment, the CO2-emission level was higher in the uncontaminated than in the contaminated soil. After two weeks, the quantity of emitted carbon dioxide decreased by about three times and did not change significantly in all uncontaminated treatments. The presence of HD in the soil initially increased CO2 emission, but later the respiration was reduced. During the first two weeks, nonvegetated soil had the highest CO2-emission level. Subsequently, the maximum increase in respiration was recorded in the vegetated contaminated treatments. The isotope composition of plant material determines the isotope composition of soil. The soil used in our experiment had an isotopic signature typical of soils formed by C3 plants (δ13C,-22.4‰). Generally, there was no significant fractionation of the carbon isotopes of the substrates metabolized by the

Interactive Effects of CO2 Concentration and Water Regime on Stable Isotope Signatures, Nitrogen Assimilation and Growth in Sweet Pepper

Directory of Open Access Journals (Sweden)

María D. Serret

2018-01-01

Full Text Available Sweet pepper is among the most widely cultivated horticultural crops in the Mediterranean basin, being frequently grown hydroponically under cover in combination with CO2 fertilization and water conditions ranging from optimal to suboptimal. The aim of this study is to develop a simple model, based on the analysis of plant stable isotopes in their natural abundance, gas exchange traits and N concentration, to assess sweet pepper growth. Plants were grown in a growth chamber for near 6 weeks. Two [CO2] (400 and 800 μmol mol−1, three water regimes (control and mild and moderate water stress and four genotypes were assayed. For each combination of genotype, [CO2] and water regime five plants were evaluated. Water stress applied caused significant decreases in water potential, net assimilation, stomatal conductance, intercellular to atmospheric [CO2], and significant increases in water use efficiency, leaf chlorophyll content and carbon isotope composition, while the relative water content, the osmotic potential and the content of anthocyanins did change not under stress compared to control conditions support this statement. Nevertheless, water regime affects plant growth via nitrogen assimilation, which is associated with the transpiration stream, particularly at high [CO2], while the lower N concentration caused by rising [CO2] is not associated with stomatal closure. The stable isotope composition of carbon, oxygen, and nitrogen (δ13C, δ18O, and δ15N in plant matter are affected not only by water regime but also by rising [CO2]. Thus, δ18O increased probably as response to decreases in transpiration, while the increase in δ15N may reflect not only a lower stomatal conductance but a higher nitrogen demand in leaves or shifts in nitrogen metabolism associated with decreases in photorespiration. The way that δ13C explains differences in plant growth across water regimes within a given [CO2], seems to be mediated through its direct

Non-destructive estimates of soil carbonic anhydrase activity and associated soil water oxygen isotope composition

Science.gov (United States)

Jones, Sam P.; Ogée, Jérôme; Sauze, Joana; Wohl, Steven; Saavedra, Noelia; Fernández-Prado, Noelia; Maire, Juliette; Launois, Thomas; Bosc, Alexandre; Wingate, Lisa

2017-12-01

The contribution of photosynthesis and soil respiration to net land-atmosphere carbon dioxide (CO2) exchange can be estimated based on the differential influence of leaves and soils on budgets of the oxygen isotope composition (δ18O) of atmospheric CO2. To do so, the activity of carbonic anhydrases (CAs), a group of enzymes that catalyse the hydration of CO2 in soils and plants, needs to be understood. Measurements of soil CA activity typically involve the inversion of models describing the δ18O of CO2 fluxes to solve for the apparent, potentially catalysed, rate of CO2 hydration. This requires information about the δ18O of CO2 in isotopic equilibrium with soil water, typically obtained from destructive, depth-resolved sampling and extraction of soil water. In doing so, an assumption is made about the soil water pool that CO2 interacts with, which may bias estimates of CA activity if incorrect. Furthermore, this can represent a significant challenge in data collection given the potential for spatial and temporal variability in the δ18O of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by inferring the rate of CO2 hydration and the δ18O of soil water from the relationship between the δ18O of CO2 fluxes and the δ18O of CO2 at the soil surface measured at different ambient CO2 conditions. This approach was tested through laboratory incubations of air-dried soils that were re-wetted with three waters of different δ18O. Gas exchange measurements were made on these soils to estimate the rate of hydration and the δ18O of soil water, followed by soil water extraction to allow for comparison. Estimated rates of CO2 hydration were 6.8-14.6 times greater than the theoretical uncatalysed rate of hydration, indicating that CA were active in these soils. Importantly, these estimates were not significantly different among water treatments, suggesting

Carbon and oxygen isotope analysis of leaf biomass reveals contrasting photosynthetic responses to elevated CO2 near geologic vents in Yellowstone National Park

Directory of Open Access Journals (Sweden)

D. G. Williams

2009-01-01

Full Text Available In this study we explore the use of natural CO2 emissions in Yellowstone National Park (YNP in Wyoming, USA to study responses of natural vegetation to elevated CO2 levels. Radiocarbon (14C analysis of leaf biomass from a conifer (Pinus contortus; lodgepole pine and an invasive, non-native herb (Linaria dalmatica; Dalmation toadflax was used to trace the inputs of vent CO2 and quantify assimilation-weighted CO2 concentrations experienced by individual plants near vents and in comparable locations with no geologic CO2 exposure. The carbon and oxygen isotopic composition and nitrogen percent of leaf biomass from the same plants was used to investigate photosynthetic responses of these plants to naturally elevated atmospheric CO2 concentrations. The coupled shifts in carbon and oxygen isotope values suggest that dalmation toadflax responded to elevated CO2 exposure by increasing stomatal conductance with no change in photosynthetic capacity and lodgepole pine apparently responded by decreasing stomatal conductance and photosynthetic capacity. Lodgepole pine saplings exposed to elevated levels of CO2 likewise had reduced leaf nitrogen concentrations compared to plants with no enhanced CO2 exposure, further suggesting widespread and dominant conifer down-regulated photosynthetic capacity under elevated CO2 levels near geologic vents.

Stable isotope signatures reflect competitiveness between trees under changed CO2/O3 regimes

International Nuclear Information System (INIS)

Grams, T.E.E.; Matyssek, R.

2010-01-01

Here we synthesize key findings from a series of experiments to gain new insight on inter-plant competition between juvenile beech (Fagus sylvatica) and spruce (Picea abies) under the influence of increased O 3 and CO 2 concentrations. Competitiveness of plants was quantified and mechanistically interpreted as space-related resource investments and gains. Stable isotopes were addressed as temporal integrators of plant performance, such as photosynthesis and its relation to water use and nitrogen uptake. In the weaker competitor, beech, efficiency in space-related aboveground resource investment was decreased in competition with spruce and positively related to Δ 13 C, as well as stomatal conductance, but negatively related to δ 18 O. Likewise, our synthesis revealed that strong belowground competition for water in spruce was paralleled in this species by high N assimilation capacity. We suggest combining the time-integrative potential of stable isotopes with space-related investigations of competitiveness to accomplish mechanistic understanding of plant competition for resources. - Combination of space-related concepts of competitiveness with stable isotopes has potential to clarify mechanisms of competition.

A system for high-quality CO2 isotope analyses of air samples collected by the CARIBIC Airbus A340-600.

Science.gov (United States)

Assonov, S; Taylor, P; Brenninkmeijer, C A M

2009-05-01

In 2007, JRC-IRMM began a series of atmospheric CO2 isotope measurements, with the focus on understanding instrumental effects, corrections as well as metrological aspects. The calibration approach at JRC-IRMM is based on use of a plain CO2 sample (working reference CO2) as a calibration carrier and CO2-air mixtures (in high-pressure cylinders) to determine the method-related correction under actual analytical conditions (another calibration carrier, in the same form as the samples). Although this approach differs from that in other laboratories, it does give a direct link to the primary reference NBS-19-CO2. It also helps to investigate the magnitude and nature for each of the instrumental corrections and allows for the quantification of the uncertainty introduced. Critical tests were focused on the instrumental corrections. It was confirmed that the use of non-symmetrical capillary crimping (an approach used here to deal with small samples) systematically modifies delta13C(CO2) and delta18O(CO2), with a clear dependence on the amount of extracted CO2. However, the calibration of CO2-air mixtures required the use of the symmetrical dual-inlet mode. As a proof of our approach, we found that delta13C(CO2) on extracts from mixtures agreed (within 0.010 per thousand) with values obtained from the 'mother' CO2 used for the mixtures. It was further found that very low levels of hydrocarbons in the pumping systems and the isotope ratio mass spectrometry (IRMS) instrument itself were critical. The m/z 46 values (consequently the calculated delta18O(CO2) values) are affected by several other effects with traces of air co-trapped with frozen CO2 being the most critical. A careful cryo-distillation of the extracted CO2 is recommended. After extensive testing, optimisation, and routine automated use, the system was found to give precise data on air samples that can be traced with confidence to the primary standards. The typical total combined uncertainty in delta13C(CO2) and

In situ Determination of CO2 and N2O Emissions and Isotopic Composition in Agricultural Soils Following a Precipitation Pulse - The Use of Real-Time CO2 and N2O Isotope Analysers

International Nuclear Information System (INIS)

Chen, Janet; Resch, Christian; Mayr, Leopold; Heiling, Maria; Dercon, Gerd

2016-01-01

Agricultural soils cover 12.6% of the Earth's surface and are essential in food production. Agricultural land can either serve as a reservoir of greenhouse gases (GHGs) in the soil, or release them into the atmosphere. Accurately estimating GHG fluxes from agricultural soils is difficult, however, due to the dynamic pattern of emissions that are largely driven by environmental factors such as water availability. Farming practices, such as mulch application, also influence soil GHG emissions. We measured effects of mulch application on emissions and isotopic composition of two GHGs, CO 2 and N 2 O, in agricultural soils by using greenhouse “mesocosms” (soil sample columns 70 cm deep and 50 cm diameter that have been subjected to a soybean-maize crop rotation since 2012).

C4 plant isotopic composition (delta13C) evidence for urban CO2 pollution in the city of Cotonou, Benin (West Africa).

Science.gov (United States)

Kèlomé, Nelly C; Lévêque, Jean; Andreux, Francis; Milloux, Marie-Jeanne; Oyédé, Lucien-Marc

2006-08-01

The carbon isotopic composition (delta13C) of plants can reveal the isotopic carbon content of the atmosphere in which they develop. The delta13C values of air and plants depend on the amount of atmospheric fossil fuel CO2, which is chiefly emitted in urban areas. A new indicator of CO2 pollution is tested using the delta13C variation in a C4 grass: Eleusine indica. A range of about 4 per thousand delta units was observed at different sites in Cotonou, the largest city in the Republic of Benin. The highest delta13C values, from -12 per thousand to -14 per thousand, were found in low traffic zones; low delta13C values, from -14 per thousand to -16 per thousand, were found in high traffic zones. The amount of fossil fuel carbon assimilated by plants represented about 20% of the total plant carbon content. An overall decrease in plant delta13C values was observed over a four-year monitoring period. This decrease was correlated with increasing vehicle traffic. The delta13C dataset and the corresponding geographical database were used to map and define zones of high and low 13C-depleted CO2 emissions in urban and sub-urban areas. The spatial distribution follows dominant wind directions, with the lowest emission zones found in the southwest of Cotonou. High CO2 emissions occurred in the north, the east and the center, providing evidence of intense anthropogenic activity related to industry and transportation.

Subsurface Water as Natural CO{sub 2} Sink

Energy Technology Data Exchange (ETDEWEB)

Gillon, M. [Centre National de la Recherche Scientifique (UMR CNRS 8148-IDES), Interaction et Dynamique des Environnements de Surface, Universite Paris 11 and Centre National de la Recherche Scientifique (UMR UAPV-INRA EMMAH), Environnement Mediterraneen et Modelisation des Agro-Hydrosystemes, Universite d' Avignon et des Pays de Vaucluse, Avignon, (France); Barbecot, F.; Gibert, E.; Massault, M. [Centre National de La Recherche Scientifique (UMR CNRS 8148-IDES), Interaction et Dynamique des Environnements de Surface, Universite Paris 11 (France)

2013-07-15

In aquifer recharge areas, groundwater mineralization acts as an important sink for CO{sub 2} (assessed at 100 Mt{sub co2}/a on a European scale). An isotopic study of C fluxes in the unsaturated zone of a sand carbonate aquifer shows that the physical and geochemical processes controlling CO{sub 2} abstraction induce changes in the isotopic composition of both dissolved and matrix carbonates. An integrated record of these fluxes toward the aquifers is evidenced through isotopic investigation of the recharge areas. It is evidenced that the unsaturated zone represents an archive of pristine conditions, and would help to quantify downward C fluxes and environmental changes related to this CO{sub 2} abstraction process. (author)

Natural high pCO2 increases autotrophy in Anemonia viridis (Anthozoa) as revealed from stable isotope (C, N) analysis

OpenAIRE

Horwitz, Rael; Borell, Esther M.; Yam, Ruth; Shemesh, Aldo; Fine, Maoz

2015-01-01

Contemporary cnidarian-algae symbioses are challenged by increasing CO2 concentrations (ocean warming and acidification) affecting organisms' biological performance. We examined the natural variability of carbon and nitrogen isotopes in the symbiotic sea anemone Anemonia viridis to investigate dietary shifts (autotrophy/heterotrophy) along a natural pCO2 gradient at the island of Vulcano, Italy. ?13C values for both algal symbionts (Symbiodinium) and host tissue of A. viridis became significa...

Effect of Co crystallinity on Co/CNT catalytic activity in CO/CO{sub 2} hydrogenation and CO disproportionation

Energy Technology Data Exchange (ETDEWEB)

Chernyak, Sergei A., E-mail: chernyak.msu@gmail.com [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation); Suslova, Evgeniya V.; Egorov, Alexander V.; Maslakov, Konstantin I. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Savilov, Serguei V.; Lunin, Valery V. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation)

2016-05-30

Highlights: • Amorphous and crystalline Co supported on CNTs were obtained by tuning of CNT surface. • CO and CO{sub 2} hydrogenation does not occur on amorphous Co particles. • Thermal activation of amorphous Co led to crystallization of metal. • Amorphous Co promotes CO disproportionation. • Carbon shells around the amorphous metal particles after the CO hydrogenation. - Abstract: Carbon nanotubes (CNTs) with different degree of surface oxidation were used as supports for 5 wt.% Co catalysts. CNTs and Co/CNT catalysts were analyzed by XPS, nitrogen adsorption, TEM and electron diffraction to reveal their structure. High oxidation degree of CNT surface (8.6 at.% of O) and low Co loading led to predominantly amorphous Co species. This resulted in the absence of catalytic activity in both CO and CO{sub 2} hydrogenation in opposite to the catalyst supported on less oxidized CNTs (5.4 at.% of O) where Co species were found to be crystalline. Thermal treatment of inactive catalyst in H{sub 2} and He led to the formation of Co crystal phase which was active in catalysis. Co particle size in catalyst supported on strongly oxidized CNTs was unchanged during CO hydrogenation in opposite to Co supported on less oxidized CNTs. Carbon shell formation on the surface of amorphous Co particles during CO hydrogenation was revealed, which testified CO disproportionation. Qualitative mechanism of CO hydrogenation on small Co particles was proposed.

Stable carbon isotopes to monitor the CO2 source mix in the urban environment

Science.gov (United States)

Vogel, F. R.; Wu, L.; Ramonet, M.; Broquet, G.; Worthy, D. E. J.

2014-12-01

Urban areas are said to be responsible for approximately 71% of fossil fuel CO2 emissions while comprising only two percent of the land area [IEA, 2008]. This limited spatial expansion could facility a monitoring of anthropogenic GHGs from atmospheric observations. As major sources of emissions, cities also have a huge potential to drive emissions reductions. To effectively manage emissions, cities must however, first establish techniques to validate their reported emission statistics. A pilot study which includes continues 13CO2 data from calibrated cavity ring-down spectrometers [Vogel et al. 2013] of two "sister sites" in the vicinity of Toronto, Canada is contrasted to recent observations of 13CO2 observations in Paris during significant pollution events. Using Miller-Tans plots [Miller and Tans, 2003] for our multi-season observations reveals significant changes of the source signatures of night time CO2 emissions which reflect the importance of natural gas burning in Megacities (up to 80% of fossil fuel sources) and show-case the potential of future isotope studies to determine source sectors. Especially the winter data this approach seems suitable to determine the source contribution of different fuel types (natural gas, liquid fuels and coal) which can inform the interpretation of other Greenhouse Gases and air pollution levels.

CO2 isotope analyses using large air samples collected on intercontinental flights by the CARIBIC Boeing 767

NARCIS (Netherlands)

Assonov, S.S.; Brenninkmeijer, C.A.M.; Koeppel, C.; Röckmann, T.

2009-01-01

Analytical details for 13C and 18O isotope analyses of atmospheric CO2 in large air samples are given. The large air samples of nominally 300 L were collected during the passenger aircraft-based atmospheric chemistry research project CARIBIC and analyzed for a large number of trace gases and

Autotrophic fixation of geogenic CO2 by microorganisms contributes to soil organic matter formation and alters isotope signatures in a wetland mofette

DEFF Research Database (Denmark)

Beulig, Felix

2015-01-01

of radiocarbon and enriched in 13C compared to atmospheric CO2. Together, these isotopic signals allow us to distinguish C fixed by plants from C fixed by autotrophic microorganisms using their differences in 13C discrimination. We can then estimate that up to 27 % of soil organic matter in the 0–10 cm layer...... geogenic CO2 was fixed by plants or by CO2 assimilating microorganisms, we first used the proportional differences in radiocarbon and δ13C values to indicate the magnitude of discrimination of the stable isotopes in living plants. Deviation from this relationship was taken to indicate the presence...... can recycle significant amounts of carbon in wetland soils and might contribute to observed radiocarbon reservoir effects influencing Δ14C signatures in peat deposits....

CO2 activation on bimetallic CuNi nanoparticles

Directory of Open Access Journals (Sweden)

Natalie Austin

2016-10-01

Full Text Available Density functional theory calculations have been performed to investigate the structural, electronic, and CO2 adsorption properties of 55-atom bimetallic CuNi nanoparticles (NPs in core-shell and decorated architectures, as well as of their monometallic counterparts. Our results revealed that with respect to the monometallic Cu55 and Ni55 parents, the formation of decorated Cu12Ni43 and core-shell Cu42Ni13 are energetically favorable. We found that CO2 chemisorbs on monometallic Ni55, core-shell Cu13Ni42, and decorated Cu12Ni43 and Cu43Ni12, whereas, it physisorbs on monometallic Cu55 and core-shell Cu42Ni13. The presence of surface Ni on the NPs is key in strongly adsorbing and activating the CO2 molecule (linear to bent transition and elongation of C˭O bonds. This activation occurs through a charge transfer from the NPs to the CO2 molecule, where the local metal d-orbital density localization on surface Ni plays a pivotal role. This work identifies insightful structure-property relationships for CO2 activation and highlights the importance of keeping a balance between NP stability and CO2 adsorption behavior in designing catalytic bimetallic NPs that activate CO2.

Land-use change effects on fluxes and isotopic composition of CO2 and CH4 in Panama, and possible insights into the atmospheric H2 cycle

Science.gov (United States)

Pendall, E.; Schwendenmann, L.; Potvin, C.

2003-12-01

Land-use changes in tropical regions are believed to release a quantity of C to the atmosphere which is similar in magnitude to the entire "missing" sink for anthropogenic CO2. Our research attempts to evaluate carbon cycling in three land-cover systems in central Panama: cow pasture, native tree plantation, and undisturbed moist forest. In this ongoing project, we are collecting samples of air from profiles in the stable, nocturnal boundary layer, which is dominated by ecosystem respiration. Samples are analyzed for CO2 and its isotopes, CH4 and its C isotopic composition, N2O, H2, CO, and SF6. We use a flux-gradient method to estimate ecosystem-scale fluxes of trace gases from soil to the atmosphere. Keeling plot intercepts reflect the respiratory contribution of C3 and C4 biomass under contrasting land cover systems, and how this varies with pronounced wet-dry seasonal cycles. C isotopes of methane and gradients of molecular hydrogen provide insight into the source of methane production from pasture and plantation soils. Rainforest soils, in contrast, are sinks for both atmospheric methane and hydrogen. The process oriented nature of this field experiment will contribute to parameterization of carbon cycle models at a variety of spatial scales.

Sealing process with calcite in the Nojima active fault zone revealed from isotope analysis of calcite

International Nuclear Information System (INIS)

Arai, Takashi; Tsukahara, Hiroaki; Morikiyo, Toshiro

2003-01-01

The Nojima fault appeared on the surface in the northern part of Awaji Island, central Japan as a result of the Hyogo-ken Nanbu earthquake (1995, M=7.2). Active fault drilling was performed by the Disaster Prevention Research Institute (DPRI), Kyoto University, and core samples were retrieved from 1410 to 1710 m, which were composed of intact and fractured granodiorites. We obtained calcite samples and gas samples from the vein in marginal fracture and non-fracture zones. We analyzed the carbon and oxygen isotope ratios of calcite and carbon dioxide to investigate the characteristic isotope ratios of fluids in the active fault zone, to estimate the origins of fluids, and to determine the sealing process of fractures. The analyzed values of carbon and oxygen isotope ratios of calcite were -10.3 to -7.2 per mille, 18 to 23 per mille, respectively, and carbon isotope ratios of CO 2 were -21 to -17 per mille. If carbon isotope ratios of calcite were at equilibrium with those of CO 2 , the precipitation temperature of calcite is calculated to be 30 to 50 deg C. This temperature is consistent with the present temperature of the depth where drilling cores were retrieved. Oxygen isotope ratios of H 2 O that, precipitated calcite were calculated to be -1.8 to -5.5 per mille. These values indicate calcite were precipitated from mixed fluids of sea water and meteoric water. Therefore, the marginal fracture zone of the Nojima fault was sealed with calcite, which was generated from mixing of sea water and meteoric water in situ. (author)

Isotope ratios of H, C, and O in CO2 and H2O of the martian atmosphere.

Science.gov (United States)

Webster, Chris R; Mahaffy, Paul R; Flesch, Gregory J; Niles, Paul B; Jones, John H; Leshin, Laurie A; Atreya, Sushil K; Stern, Jennifer C; Christensen, Lance E; Owen, Tobias; Franz, Heather; Pepin, Robert O; Steele, Andrew; Achilles, Cherie; Agard, Christophe; Alves Verdasca, José Alexandre; Anderson, Robert; Anderson, Ryan; Archer, Doug; Armiens-Aparicio, Carlos; Arvidson, Ray; Atlaskin, Evgeny; Aubrey, Andrew; Baker, Burt; Baker, Michael; Balic-Zunic, Tonci; Baratoux, David; Baroukh, Julien; Barraclough, Bruce; Bean, Keri; Beegle, Luther; Behar, Alberto; Bell, James; Bender, Steve; Benna, Mehdi; Bentz, Jennifer; Berger, Gilles; Berger, Jeff; Berman, Daniel; Bish, David; Blake, David F; Blanco Avalos, Juan J; Blaney, Diana; Blank, Jen; Blau, Hannah; Bleacher, Lora; Boehm, Eckart; Botta, Oliver; Böttcher, Stephan; Boucher, Thomas; Bower, Hannah; Boyd, Nick; Boynton, Bill; Breves, Elly; Bridges, John; Bridges, Nathan; Brinckerhoff, William; Brinza, David; Bristow, Thomas; Brunet, Claude; Brunner, Anna; Brunner, Will; Buch, Arnaud; Bullock, Mark; Burmeister, Sönke; Cabane, Michel; Calef, Fred; Cameron, James; Campbell, John; Cantor, Bruce; Caplinger, Michael; Caride Rodríguez, Javier; Carmosino, Marco; Carrasco Blázquez, Isaías; Charpentier, Antoine; Chipera, Steve; Choi, David; Clark, Benton; Clegg, Sam; Cleghorn, Timothy; Cloutis, Ed; Cody, George; Coll, Patrice; Conrad, Pamela; Coscia, David; Cousin, Agnès; Cremers, David; Crisp, Joy; Cros, Alain; Cucinotta, Frank; d'Uston, Claude; Davis, Scott; Day, Mackenzie; de la Torre Juarez, Manuel; DeFlores, Lauren; DeLapp, Dorothea; DeMarines, Julia; DesMarais, David; Dietrich, William; Dingler, Robert; Donny, Christophe; Downs, Bob; Drake, Darrell; Dromart, Gilles; Dupont, Audrey; Duston, Brian; Dworkin, Jason; Dyar, M Darby; Edgar, Lauren; Edgett, Kenneth; Edwards, Christopher; Edwards, Laurence; Ehlmann, Bethany; Ehresmann, Bent; Eigenbrode, Jen; Elliott, Beverley; Elliott, Harvey; Ewing, Ryan; Fabre, Cécile; Fairén, Alberto; Farley, Ken; Farmer, Jack; Fassett, Caleb; Favot, Laurent; Fay, Donald; Fedosov, Fedor; Feldman, Jason; Feldman, Sabrina; Fisk, Marty; Fitzgibbon, Mike; Floyd, Melissa; Flückiger, Lorenzo; Forni, Olivier; Fraeman, Abby; Francis, Raymond; François, Pascaline; Freissinet, Caroline; French, Katherine Louise; Frydenvang, Jens; Gaboriaud, Alain; Gailhanou, Marc; Garvin, James; Gasnault, Olivier; Geffroy, Claude; Gellert, Ralf; Genzer, Maria; Glavin, Daniel; Godber, Austin; Goesmann, Fred; Goetz, Walter; Golovin, Dmitry; Gómez Gómez, Felipe; Gómez-Elvira, Javier; Gondet, Brigitte; Gordon, Suzanne; Gorevan, Stephen; Grant, John; Griffes, Jennifer; Grinspoon, David; Grotzinger, John; Guillemot, Philippe; Guo, Jingnan; Gupta, Sanjeev; Guzewich, Scott; Haberle, Robert; Halleaux, Douglas; Hallet, Bernard; Hamilton, Vicky; Hardgrove, Craig; Harker, David; Harpold, Daniel; Harri, Ari-Matti; Harshman, Karl; Hassler, Donald; Haukka, Harri; Hayes, Alex; Herkenhoff, Ken; Herrera, Paul; Hettrich, Sebastian; Heydari, Ezat; Hipkin, Victoria; Hoehler, Tori; Hollingsworth, Jeff; Hudgins, Judy; Huntress, Wesley; Hurowitz, Joel; Hviid, Stubbe; Iagnemma, Karl; Indyk, Steve; Israël, Guy; Jackson, Ryan; Jacob, Samantha; Jakosky, Bruce; Jensen, Elsa; Jensen, Jaqueline Kløvgaard; Johnson, Jeffrey; Johnson, Micah; Johnstone, Steve; Jones, Andrea; Joseph, Jonathan; Jun, Insoo; Kah, Linda; Kahanpää, Henrik; Kahre, Melinda; Karpushkina, Natalya; Kasprzak, Wayne; Kauhanen, Janne; Keely, Leslie; Kemppinen, Osku; Keymeulen, Didier; Kim, Myung-Hee; Kinch, Kjartan; King, Penny; Kirkland, Laurel; Kocurek, Gary; Koefoed, Asmus; Köhler, Jan; Kortmann, Onno; Kozyrev, Alexander; Krezoski, Jill; Krysak, Daniel; Kuzmin, Ruslan; Lacour, Jean Luc; Lafaille, Vivian; Langevin, Yves; Lanza, Nina; Lasue, Jeremie; Le Mouélic, Stéphane; Lee, Ella Mae; Lee, Qiu-Mei; Lees, David; Lefavor, Matthew; Lemmon, Mark; Lepinette Malvitte, Alain; Léveillé, Richard; Lewin-Carpintier, Éric; Lewis, Kevin; Li, Shuai; Lipkaman, Leslie; Little, Cynthia; Litvak, Maxim; Lorigny, Eric; Lugmair, Guenter; Lundberg, Angela; Lyness, Eric; Madsen, Morten; Maki, Justin; Malakhov, Alexey; Malespin, Charles; Malin, Michael; Mangold, Nicolas; Manhes, Gérard; Manning, Heidi; Marchand, Geneviève; Marín Jiménez, Mercedes; Martín García, César; Martin, Dave; Martin, Mildred; Martínez-Frías, Jesús; Martín-Soler, Javier; Martín-Torres, F Javier; Mauchien, Patrick; Maurice, Sylvestre; McAdam, Amy; McCartney, Elaina; McConnochie, Timothy; McCullough, Emily; McEwan, Ian; McKay, Christopher; McLennan, Scott; McNair, Sean; Melikechi, Noureddine; Meslin, Pierre-Yves; Meyer, Michael; Mezzacappa, Alissa; Miller, Hayden; Miller, Kristen; Milliken, Ralph; Ming, Douglas; Minitti, Michelle; Mischna, Michael; Mitrofanov, Igor; Moersch, Jeff; Mokrousov, Maxim; Molina Jurado, Antonio; Moores, John; Mora-Sotomayor, Luis; Morookian, John Michael; Morris, Richard; Morrison, Shaunna; Mueller-Mellin, Reinhold; Muller, Jan-Peter; Muñoz Caro, Guillermo; Nachon, Marion; Navarro López, Sara; Navarro-González, Rafael; Nealson, Kenneth; Nefian, Ara; Nelson, Tony; Newcombe, Megan; Newman, Claire; Newsom, Horton; Nikiforov, Sergey; Nixon, Brian; Noe Dobrea, Eldar; Nolan, Thomas; Oehler, Dorothy; Ollila, Ann; Olson, Timothy; de Pablo Hernández, Miguel Ángel; Paillet, Alexis; Pallier, Etienne; Palucis, Marisa; Parker, Timothy; Parot, Yann; Patel, Kiran; Paton, Mark; Paulsen, Gale; Pavlov, Alex; Pavri, Betina; Peinado-González, Verónica; Peret, Laurent; Perez, Rene; Perrett, Glynis; Peterson, Joe; Pilorget, Cedric; Pinet, Patrick; Pla-García, Jorge; Plante, Ianik; Poitrasson, Franck; Polkko, Jouni; Popa, Radu; Posiolova, Liliya; Posner, Arik; Pradler, Irina; Prats, Benito; Prokhorov, Vasily; Purdy, Sharon Wilson; Raaen, Eric; Radziemski, Leon; Rafkin, Scot; Ramos, Miguel; Rampe, Elizabeth; Raulin, François; Ravine, Michael; Reitz, Günther; Rennó, Nilton; Rice, Melissa; Richardson, Mark; Robert, François; Robertson, Kevin; Rodriguez Manfredi, José Antonio; Romeral-Planelló, Julio J; Rowland, Scott; Rubin, David; Saccoccio, Muriel; Salamon, Andrew; Sandoval, Jennifer; Sanin, Anton; Sans Fuentes, Sara Alejandra; Saper, Lee; Sarrazin, Philippe; Sautter, Violaine; Savijärvi, Hannu; Schieber, Juergen; Schmidt, Mariek; Schmidt, Walter; Scholes, Daniel; Schoppers, Marcel; Schröder, Susanne; Schwenzer, Susanne; Sebastian Martinez, Eduardo; Sengstacken, Aaron; Shterts, Ruslan; Siebach, Kirsten; Siili, Tero; Simmonds, Jeff; Sirven, Jean-Baptiste; Slavney, Susie; Sletten, Ronald; Smith, Michael; Sobrón Sánchez, Pablo; Spanovich, Nicole; Spray, John; Squyres, Steven; Stack, Katie; Stalport, Fabien; Stein, Thomas; Stewart, Noel; Stipp, Susan Louise Svane; Stoiber, Kevin; Stolper, Ed; Sucharski, Bob; Sullivan, Rob; Summons, Roger; Sumner, Dawn; Sun, Vivian; Supulver, Kimberley; Sutter, Brad; Szopa, Cyril; Tan, Florence; Tate, Christopher; Teinturier, Samuel; ten Kate, Inge; Thomas, Peter; Thompson, Lucy; Tokar, Robert; Toplis, Mike; Torres Redondo, Josefina; Trainer, Melissa; Treiman, Allan; Tretyakov, Vladislav; Urqui-O'Callaghan, Roser; Van Beek, Jason; Van Beek, Tessa; VanBommel, Scott; Vaniman, David; Varenikov, Alexey; Vasavada, Ashwin; Vasconcelos, Paulo; Vicenzi, Edward; Vostrukhin, Andrey; Voytek, Mary; Wadhwa, Meenakshi; Ward, Jennifer; Weigle, Eddie; Wellington, Danika; Westall, Frances; Wiens, Roger Craig; Wilhelm, Mary Beth; Williams, Amy; Williams, Joshua; Williams, Rebecca; Williams, Richard B; Wilson, Mike; Wimmer-Schweingruber, Robert; Wolff, Mike; Wong, Mike; Wray, James; Wu, Megan; Yana, Charles; Yen, Albert; Yingst, Aileen; Zeitlin, Cary; Zimdar, Robert; Zorzano Mier, María-Paz

2013-07-19

Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ratios of D/H and (18)O/(16)O in water and (13)C/(12)C, (18)O/(16)O, (17)O/(16)O, and (13)C(18)O/(12)C(16)O in carbon dioxide, made in the martian atmosphere at Gale Crater from the Curiosity rover using the Sample Analysis at Mars (SAM)'s tunable laser spectrometer (TLS). Comparison between our measurements in the modern atmosphere and those of martian meteorites such as ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established ~4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing.

Hydrogen and oxygen isotope exchange reactions over illuminated and nonilluminated TiO2

International Nuclear Information System (INIS)

Sato, S.

1987-01-01

Hydrogen isotope exchange between H 2 , gaseous H 2 O, and the surface hydroxyls of TiO 2 , and oxygen isotope exchange between O 2 , CO 2 , CO, H 2 O vapor, and the hydroxyls over TiO 3 were studied at room temperature in the dark and under illumination. Hydrogen isotope exchange between H 2 O and the hydroxyls occurred rapidly in the dark, but the exchange involving H 2 did not occur at all even under illumination. Oxygen isotope exchange among H 2 O vapor, CO 2 , and the hydroxyls easily took place in the dark, but the exchange involving O 2 required band-gap illumination. Dioxygen isotope equilibration was much faster than the other photoexchange reactions. Although the oxygen exchange between O 2 and illuminated TiO 2 has been considered to involve lattice-oxygen exchange, the present experiments revealed that the hydroxyls of TiO 2 mainly participate in the exchange reaction. The oxygen exchange between O 2 and H 2 O vapor was strongly inhibited by H 2 O vapor itself probably because oxygen adsorption was retarded by adsorbed water. Oxygen in CO was not exchanged with the other substrates under any conditions tested

Carbon isotopic evidence for the associations of decreasing atmospheric CO2 level with the Frasnian-Famennian mass extinction

Science.gov (United States)

Xu, Bing; Gu, Zhaoyan; Wang, Chengyuan; Hao, Qingzhen; Han, Jingtai; Liu, Qiang; Wang, Luo; Lu, Yanwu

2012-03-01

A perturbation of the global carbon cycle has often been used for interpreting the Frasnian-Famennian (F-F) mass extinction. However, the changes of atmospheric CO2 level (pCO2) during this interval are much debatable. To illustrate the carbon cycle during F-F transition, paired inorganic (δ13Ccarb) and organic (δ13Corg) carbon isotope analyses were carried out on two late Devonian carbonate sequences (Dongcun and Yangdi) from south China. The larger amplitude shift of δ13Corg compared to δ13Ccarb and its resultant Δ13C (Δ13C = δ13Ccarb - δ13Corg) decrease indicate decreased atmospheric CO2level around the F-F boundary. The onset ofpCO2 level decrease predates that of marine regressions, which coincide with the beginning of conodont extinctions, suggesting that temperature decrease induced by decreased greenhouse effect of atmospheric CO2might have contributed to the F-F mass extinction.

Direct gas injection method: A simple modification to an elemental analyzer/isotope ratio mass spectrometer for stable isotope analysis of N and C from N2O and CO2 gases in nanomolar concentrations

Science.gov (United States)

A simple modification to the Elemental Analyzer coupled to Isotope Ratio Mass-Spectrometer (EA-IRMS) setup is described. This modification allows the users to measure nitrous oxide (N2O) and carbon dioxide (CO2) by injecting the gases directly into an online injector placed befor...

Does Short-term Litter Input Manipulation Affect Soil Respiration and the Carbon-isotopic Signature of Soil Respired CO2

Science.gov (United States)

Cheng, X.; Wu, J.

2016-12-01

Global change greatly alters the quality and quantity of plant litter inputs to soils, and further impacts soil organic matter (SOM) dynamics and soil respiration. However, the process-based understanding of how soil respiration may change with future shift in litter input is not fully understood. The Detritus Input and Removal Treatment (DIRT) experiment was conducted in coniferous forest (Platycladus orientalis (Linn.) Franco) ecosystem of central China to investigate the impact of above- and belowground litter input on soil respiration and the carbon-isotopic signature of soil respired CO2. Short-term (1-2 years) litter input manipulation significantly affected soil respiration, based on annual flux values, soil respiration was 31.9%, 20.5% and 37.2% lower in no litter (NL), no root (NR) and no input (NRNL), respectively, compared to control (CK). Whereas double litter (DL) treatment increased soil respiration by 9.1% compared to CK. The recalcitrance index of carbon (RIC) and the relative abundance of fungi increased under litter removal or root exclusion treatment (NL, NR and NRNL) compared to CK. Basal soil respiration was positively related to liable C and microbial biomass and negatively related to RIC and fungi to bacteria (F: B) ratio. The carbon-isotopic signature of soil respired CO2 enriched under litter removal and no input treatment, and slightly depleted under litter addition treatment compared to CK. Our results suggest that short-term litter input manipulation can affect the soil respiration by altering substrate availability and microbial community structure, and also impact the carbon-isotopic signature of soil respired CO2 possibly duo to change in the component of soil respiration and soil microclimate.

Pulsed CO laser for isotope separation of uranium

Energy Technology Data Exchange (ETDEWEB)

Baranov, Igor Y.; Koptev, Andrey V. [Rocket-Space Technics Department, Baltic State Technical University, 1, 1st Krasnoarmeyskaya st.,St. Petersburg, 190005 (Russian Federation)

2012-07-30

This article proposes a technical solution for using a CO laser facility for the industrial separation of uranium used in the production of fuel for nuclear power plants, employing a method of laser isotope separation of uranium with condensation repression in a free jet. The laser operation with nanosecond pulse irradiation can provide an acceptable efficiency in the separating unit and a high efficiency of the laser with the wavelength of 5.3 {mu}m. In the present work we also introduce a calculation model and define the parameters of a mode-locked CO laser with a RF discharge in the supersonic stream. The average pulsed CO laser power of 3 kW is sufficient for efficient industrial isotope separation of uranium in one stage.

Development of indirect indicators for CO2 intrusion into freshwater

International Nuclear Information System (INIS)

Humez, P.

2012-01-01

This study deals with the impact of CO 2 leakages out of geological storage into overlying freshwater aquifers. Compared to other existing studies, the major added value of this study lies, on the one hand, in the research of new monitoring tools and isotopic approach in the context of CCS aiming at early and sensitive detection of CO 2 leakage and, on the other hand, in the application of these tools at the (limited) laboratory scale as well as at field scale. In order to test these tools, solid and liquid materials were sampled out of the major strategic drinking water Albian aquifer in the Paris Basin (France). We have then precisely characterized and used them within a batch experiment. This experiment yields interesting results which help understanding and constraining precisely the water-rock-CO 2 interactions as well as the isotopic responses. A real scale application of the method was then performed in Norway. It was an opportunity to develop this isotopic program and to track the isotopic evolution composition, while differentiating the natural processes and the system response to the CO 2 injection. When applied to the detection of CO 2 leakage context, the two case studies open the way for choosing the 'best' isotopic tools as indirect indicators of CO 2 presence in these specific systems. The efficiency of these isotopic tools comes from the recording of the CO 2 footprint all along the water-rock-CO 2 interactions. Using such tools imposes a rigorous methodology, which is tackled in this manuscript. Furthermore, future application will require adapting to the specifics of a proposed site. (author)

Autotrophic fixation of geogenic CO2 by microorganisms contributes to soil organic matter formation and alters isotope signatures in a wetland mofette

DEFF Research Database (Denmark)

Beulig, Felix

2015-01-01

To quantify the contribution of autotrophic microorganisms to organic matter (OM) formation in soils, we investigated natural CO2 vents (mofettes) situated in a wetland in northwest Bohemia (Czech Republic). Mofette soils had higher soil organic matter (SOM) concentrations than reference soils due...... of radiocarbon and enriched in 13C compared to atmospheric CO2. Together, these isotopic signals allow us to distinguish C fixed by plants from C fixed by autotrophic microorganisms using their differences in 13C discrimination. We can then estimate that up to 27 % of soil organic matter in the 0–10 cm layer...... ranged up to 1.59 ± 0.16 μg gdw−1 d−1. We inferred that the negative δ13C shift was caused by the activity of autotrophic microorganisms using the Calvin–Benson–Bassham (CBB) cycle, as indicated from quantification of cbbL/cbbM marker genes encoding for RubisCO by quantitative polymerase chain reaction...

Eddy Covariance measurements of stable CO2 and H2O isotopologues

Science.gov (United States)

Braden-Behrens, Jelka; Knohl, Alexander

2015-04-01

The analysis of the stable isotope composition of CO2 and H2O fluxes (such as 13C, 18O and 2H in H2O and CO2) has provided valuable insights into ecosystem gas exchange. The approach builds on differences in the isotope signature of different ecosystem components that are primarily caused by the preference for or the discrimination against respective isotope species by important processes within the ecosystem (e.g. photosynthesis or leaf water diffusion). With the ongoing development of laser spectrometric methods, fast and precise measurements of isotopologue mixing ratios became possible, hence also enabling Eddy Covariance (EC) based approaches to directly measure the isotopic composition of CO2 and H2Ov net fluxes on ecosystem scale. During an eight month long measurement campaign in 2015, we plan to simultaneously measure CO2 and H2Ov isotopologue fluxes using an EC approach in a managed beech forest in Thuringia, Germany. For this purpose, we will use two different laser spectrometers for high frequency measurements of isotopic compositions: For H2Ov measurements, we will use an off axis cavity output water vapour isotope analyser (WVIA, Los Gatos Research Inc.) with 5 Hz response; and for CO2 measurements, we will use a quantum cascade laser-based system (QCLAS, Aerodyne Research Inc.) with thermoelectrically cooled detectors and up to 10 Hz measurement capability. The resulting continuous isotopologue flux measurements will be accompanied by intensive sampling campaigns on the leaf scale: Water from leaf, twig, soil and precipitation samples will be analysed in the lab using isotope ratio mass spectrometry. During data analysis we will put a focus on (i) the influence of carbon and oxygen discrimination on the isotopic signature of respective net ecosystem exchange, (ii) on the relationship between evapotranspiration and leaf water enrichment, and (iii) on the 18O exchange between carbon dioxide and water. At present, we already carried out extensive

Stable Carbon Isotope Characterization of CO2 Loss in Acid Mine Drainage Impacted Stream Water: Observations from a Laboratory Experiment

Science.gov (United States)

Ali, H. N.; Atekwana, E. A.

2007-05-01

Water from an acid mine drainage spring, ground water from a mine tailings pile, stream water and tap water were acidified to simulate acid mine drainage (AMD) contamination. The objective was to determine how acidification of stream water by AMD affected DIC loss and carbon isotope fraction. Two 20 L HDP containers (reactors) containing samples from each source were left un-acidified and allowed to evolve under ambient conditions for several weeks in the laboratory and two others were acidified. Acidification was carried out progressively with sulfuric acid to pH <3. For acidified samples, one reactor was acidified open to the atmosphere and the other closed from contact with atmosphere and CO2(g) was collected under vacuum. The un-acidified samples did not show significant alkalinity and DIC loss, and the 13C of DIC was enriched with time. The acidified samples showed decrease in alkalinity and DIC and increase in the 13C of DIC and CO2(g) with progressive acidification. The enrichment of 13C of DIC for un-acidified samples was due to exchange with atmospheric CO2. On the other hand, the 13C enrichment in the acidified samples was due to fractionation during dehydration of HCO3- and diffusive loss of CO2(g) from the aqueous phase. The actual values measured depended on the amount of CO2 lost from the aqueous phase during acidification. Samples with greater CO2 loss (closed acidification) had greater 13C enrichment. Beyond the HCO3- titration end point, the δ13C of DIC and CO2(g) was similar and nearly constant. The result of this study suggests that AMD effects on DIC can be modeled as a first order kinetic reaction and the isotope enrichment modeled using Rayleigh distillation.

Effect of isotopic substitution on the collisional quenching of vibronically excited CO+

International Nuclear Information System (INIS)

Katayama, D.H.; Welsh, J.A.

1983-01-01

Rovibronic levels of the A 2 Pi/sub i/ state for 12 C 16 O + and 13 C 16 O + have been selectively excited by a pulsed, tunable dye laser and their time resolved fluorescence obtained as a function of helium pressure. These ions are formed by reaction of neutral carbon monoxide with helium metastable atoms created in a dc discharge. Since 13 CO + has essentially the same potential energy curves as 12 CO + , but differs primarily in its vibrational energy spacings, this experiment accentuates the role, in the collisional deactivation process, of the high lying ground state vibrational levels which are adjacent to the laser populated vibronic levels of the A 2 Pi/sub i/ state. Quenching rates are determined for the v' = 0, 1, and 2 levels which have relatively insignificant isotope shifts of a few wave numbers for the two isotopes. The difference in rates for the two isotopic ions demonstrates the importance of the positions for the high lying v'' = 10 and 11 ground state levels which have large isotope shifts of hundreds of wave numbers. A discussion of the deactivation process is given in terms of perturbations, Franck--Condon factors, energy gaps, and other considerations

The effect of carbonic anhydrase on the kinetics and equilibrium of the oxygen isotope exchange in the CO2-H2O system: Implications for δ18O vital effects in biogenic carbonates

Science.gov (United States)

Uchikawa, Joji; Zeebe, Richard E.

2012-10-01

equilibrium is nearly halved by the presence of 3.7 × 10-9 M of CA used for the experiments. Despite its significant influence on the oxygen isotope exchange kinetics, the equilibrium oxygen isotope fractionation between individual DIC species and H2O is unaffected by CA. Because many CaCO3-secreting organisms possess active CA, our findings imply that 18O equilibration of the CO2-H2O system is possible within realistic timescales of biogenic calcification.

Ruthenium and osmium carbonyl nitrosyl complexes: Matrix infrared spectra and density functional calculations for M(CO){sub 2}(NO){sub 2} and M(CO)(NO) (M = Ru, Os)

Energy Technology Data Exchange (ETDEWEB)

Song, Zhenjun [Department of Chemistry, Tongji University, Shanghai 200092 (China); Wang, Xuefeng, E-mail: xfwang@tongji.edu.cn [Department of Chemistry, Tongji University, Shanghai 200092 (China); Key Laboratory of Yangtze River Water Environment, Ministry of Education, Tongji University (China)

2012-10-15

Highlights: Black-Right-Pointing-Pointer Laser-ablated ruthenium or osmium atom reactions with CO and NO mixtures in solid argon. Black-Right-Pointing-Pointer Metal carbonyl nitrosyls including M(CO)(NO) and 18-electron configuration M(CO){sub 2}(NO){sub 2} molecules (M = Ru, Os). Black-Right-Pointing-Pointer The observed absorption bands of reaction products are identified by isotopic substitution and DFT calculations. Black-Right-Pointing-Pointer The bonding and reaction mechanism are discussed in detail. -- Abstract: Laser-ablated ruthenium or osmium atom reactions with CO and NO mixtures in solid argon produce unsaturated metal carbonyl nitrosyls including M(CO)(NO) and 18-electron configuration M(CO){sub 2}(NO){sub 2} molecules (M = Ru, Os). The observed absorption bands of reaction products are identified by isotopic substitution, isotopic ratios and isotopic distributions ({sup 13}CO, {sup 15}NO, and mixtures). DFT (B3LYP and BP86) vibrational fundamental calculations reproduce observed frequencies and isotopic shifts very well. The bonding and reaction mechanism are discussed.

Enhancement of CO Evolution by Modification of Ga2O3 with Rare-Earth Elements for the Photocatalytic Conversion of CO2 by H2O.

Science.gov (United States)

Tatsumi, Hiroyuki; Teramura, Kentaro; Huang, Zeai; Wang, Zheng; Asakura, Hiroyuki; Hosokawa, Saburo; Tanaka, Tsunehiro

2017-12-12

Modification of the surface of Ga 2 O 3 with rare-earth elements enhanced the evolution of CO as a reduction product in the photocatalytic conversion of CO 2 using H 2 O as an electron donor under UV irradiation in aqueous NaHCO 3 as a pH buffer, with the rare-earth species functioning as a CO 2 capture and storage material. Isotope experiments using 13 CO 2 as a substrate clearly revealed that CO was generated from the introduced gaseous CO 2 . In the presence of the NaHCO 3 additive, the rare-earth (RE) species on the Ga 2 O 3 surface are transformed into carbonate hydrates (RE 2 (CO 3 ) 3 ·nH 2 O) and/or hydroxycarbonates (RE 2 (OH) 2(3-x) (CO 3 ) x ) which are decomposed upon photoirradiation. Consequently, Ag-loaded Yb-modified Ga 2 O 3 exhibits much higher activity (209 μmol h -1 of CO) than the pristine Ag-loaded Ga 2 O 3 . The further modification of the surface of the Yb-modified Ga 2 O 3 with Zn afforded a selectivity toward CO evolution of 80%. Thus, we successfully achieved an efficient Ag-loaded Yb- and Zn-modified Ga 2 O 3 photocatalyst with high activity and controllable selectivity, suitable for use in artificial photosynthesis.

Isotopic mixing in carbon monoxide catalyzed by zinc oxide

International Nuclear Information System (INIS)

Carnisio, G.; Garbassi, F.; Petrini, G.; Parravano, G.

1978-01-01

The rate of the isotopic mixing in CO has been studied at 300 0 C, for CO partial pressures from 6 to 100 Torr and a total pressure of 250 Torr on ZnO catalysts. Significant deviations from a first-order rate in p/sub co/ were found. The rate of oxygen exchange between ZnO and gas-phase CO was also measured and the results were employed to calculate the fraction of surface sites active for the CO isotopic mixing. Values on the order of 0.001 were found. The turnover rate and surface collision efficiency varied between 0.7 and 107 min -1 and 0.13 and 2.24 x 10 -8 , respectively. H 2 additions to CO increased the rate of isotopic mixing, whereas the rate of H 2 + D 2 was decreased by the presence of CO. The H 2 + D 2 rate was faster than that of isotopic mixing in CO, but as the ratio p/sub H 2 //p/sub co/ decreased the rates became about equal. It is argued that on ZnO samples, in which the rate of CO isotopic mixing and the rate of ZnO--CO oxygen exchange were influenced in a similar manner by the CO pressure, the isotopic mixing in CO took place via the ZnO oxygen, while oxide oxygen participation was not kinetically significant for ZnO samples in which the two reactions had different kinetics. The crucial factor controlling the path followed by the isotopic mixing in CO seems to be the surface Zn/O ratio, since a close correlation was found between the former and the reaction kinetics of the CO isotopic mixing reaction. Solid-state conditions which may vary the Zn/O surface ratio (foreign additions) are indicated. The implications of these findings to the problem of product selectivity from CO-H 2 mixtures reacting on metal oxide surfaces are discussed

The interaction of soil phototrophs and fungi with pH and their impact on soil CO2, CO18O and OCS exchange.

Science.gov (United States)

Sauze, Joana; Ogée, Jérôme; Maron, Pierre-Alain; Crouzet, Olivier; Nowak, Virginie; Wohl, Steven; Kaisermann, Aurore; Jones, Sam P; Wingate, Lisa

2017-12-01

The stable oxygen isotope composition of atmospheric CO 2 and the mixing ratio of carbonyl sulphide (OCS) are potential tracers of biospheric CO 2 fluxes at large scales. However, the use of these tracers hinges on our ability to understand and better predict the activity of the enzyme carbonic anhydrase (CA) in different soil microbial groups, including phototrophs. Because different classes of the CA family (α, β and γ) may have different affinities to CO 2 and OCS and their expression should also vary between different microbial groups, differences in the community structure could impact the 'community-integrated' CA activity differently for CO 2 and OCS. Four soils of different pH were incubated in the dark or with a diurnal cycle for forty days to vary the abundance of native phototrophs. Fluxes of CO 2 , CO 18 O and OCS were measured to estimate CA activity alongside the abundance of bacteria, fungi and phototrophs. The abundance of soil phototrophs increased most at higher soil pH. In the light, the strength of the soil CO 2 sink and the CA-driven CO 2 -H 2 O isotopic exchange rates correlated with phototrophs abundance. OCS uptake rates were attributed to fungi whose abundance was positively enhanced in alkaline soils but only in the presence of increased phototrophs. Our findings demonstrate that soil-atmosphere CO 2 , OCS and CO 18 O fluxes are strongly regulated by the microbial community structure in response to changes in soil pH and light availability and supports the idea that different members of the microbial community express different classes of CA, with different affinities to CO 2 and OCS.

Research on catalysts for long-life closed-cycle CO2 laser oaperation

Science.gov (United States)

Sidney, Barry D.; Schryer, David R.; Upchurch, Billy T.; Hess, Robert V.; Wood, George M.

1987-01-01

Long-life, closed-cycle operation of pulsed CO2 lasers requires catalytic CO-O2 recombination both to remove O2, which is formed by discharge-induced CO2 decomposition, and to regenerate CO2. Platinum metal on a tin-oxide substrate (Pt/SnO2) has been found to be an effective catalyst for such recombination in the desired temperature range of 25 to 100 C. This paper presents a description of ongoing research at NASA-Langley on Pt/SnO2 catalyzed CO-O2 recombination. Included are studies with rare-isotope gases since rare-isotope CO2 is desirable as a laser gas for enhanced atmospheric transmission. Results presented include: (1) the effects of various catalyst pretreatment techniques on catalyst efficiency; (2) development of a technique, verified in a 30-hour test, to prevent isotopic scrambling when C(O-18) and (O-18)2 are reacted in the presence of a common-isotope Pt/Sn(O-16)2 catalyst; and (3) development of a mathematical model of a laser discharge prior to catalyst introduction.

Assessing methane oxidation under landfill covers and its contribution to the above atmospheric CO2 levels: The added value of the isotope (δ13C and δ18O CO2; δ13C and δD CH4) approach

International Nuclear Information System (INIS)

Widory, D.; Proust, E.; Bellenfant, G.; Bour, O.

2012-01-01

Highlights: ► Comparison of the isotope and mass balance approaches to evaluate the level of methane oxidation within a landfill. ► The level of methane oxidation is not homogenous under the landfill cover and is strongly correlated to the methane flux. ► Isotope tracking of the contribution of the methane oxidation to the CO 2 concentrations in the ambient air. - Abstract: We are presenting here a multi-isotope approach (δ 13 C and δ 18 O of CO 2 ; δ 13 C and δD of CH 4 ) to assess (i) the level(s) of methane oxidation during waste biodegradation and its migration through a landfill cover in Sonzay (France), and (ii) its contribution to the atmospheric CO 2 levels above the surface. The isotope approach is compared to the more conventional mass balance approach. Results from the two techniques are comparable and show that the CH 4 oxidation under the landfill cover is heterogenous, with low oxidation percentages in samples showing high biogas fluxes, which was expected in clay covers presenting fissures, through which CH 4 is rapidly transported. At shallow depth, more immobile biogas pockets show a higher level of CH 4 oxidation by the methanotrophic bacteria. δ 13 C of CO 2 samples taken at different heights (from below the cover up to 8 m above the ground level) were also used to identify and assess the relative contributions of its main sources both under the landfill cover and in the surrounding atmosphere.

C{sub 4} plant isotopic composition ({delta}{sup 13}C) evidence for urban CO{sub 2} pollution in the city of Cotonou, Benin (West Africa)

Energy Technology Data Exchange (ETDEWEB)

Kelome, Nelly C.; Leveque, Jean; Andreux, Francis; Milloux, Marie-Jeanne [UMR Microbiologie et Geochimie des Sols INRA, Universite de Bourgogne, Centre des Sciences de la Terre, 6 Bd Gabriel, 21000 Dijon (France); Oyede, Lucien-Marc [Departement des Sciences de la Terre, Universite d' Abomey-Calavi, 01 B.P. 526, Cotonou (Benin)

2006-08-01

The carbon isotopic composition ({delta}{sup 13}C) of plants can reveal the isotopic carbon content of the atmosphere in which they develop. The {delta}{sup 13}C values of air and plants depend on the amount of atmospheric fossil fuel CO{sub 2}, which is chiefly emitted in urban areas. A new indicator of CO{sub 2} pollution is tested using the {delta}{sup 13}C variation in a C{sub 4} grass: Eleusine indica. A range of about 4%% delta units was observed at different sites in Cotonou, the largest city in the Republic of Benin. The highest {delta}{sup 13}C values, from -12%% to -14%%, were found in low traffic zones; low {delta}{sup 13}C values, from -14%% to -16%%, were found in high traffic zones. The amount of fossil fuel carbon assimilated by plants represented about 20% of the total plant carbon content. An overall decrease in plant {delta}{sup 13}C values was observed over a four-year monitoring period. This decrease was correlated with increasing vehicle traffic. The {delta}{sup 13}C dataset and the corresponding geographical database were used to map and define zones of high and low {sup 13}C-depleted CO{sub 2} emissions in urban and sub-urban areas. The spatial distribution follows dominant wind directions, with the lowest emission zones found in the southwest of Cotonou. High CO{sub 2} emissions occurred in the north, the east and the center, providing evidence of intense anthropogenic activity related to industry and transportation. (author)

C{sub 4} plant isotopic composition ((delta){sup 13}C) evidence for urban CO{sub 2} pollution in the city of Cotonou, Benin (West Africa)

Energy Technology Data Exchange (ETDEWEB)

Kelome, Nelly C.; Leveque, Jean; Andreux, Francis; Milloux, Marie-Jeanne [UMR Microbiologie et Geochimie des Sols INRA, Universite de Bourgogne, Centre des Sciences de la Terre, 6 Bd Gabriel, 21000 Dijon (France); Oyede, Lucien-Marc [Departement des Sciences de la Terre, Universite d' Abomey-Calavi, 01 B.P. 526, Cotonou (Benin)

2006-08-01

The carbon isotopic composition ((delta){sup 13}C) of plants can reveal the isotopic carbon content of the atmosphere in which they develop. The (delta){sup 13}C values of air and plants depend on the amount of atmospheric fossil fuel CO{sub 2}, which is chiefly emitted in urban areas. A new indicator of CO{sub 2} pollution is tested using the (delta){sup 13}C variation in a C{sub 4} grass: Eleusine indica. A range of about 4%% delta units was observed at different sites in Cotonou, the largest city in the Republic of Benin. The highest (delta){sup 13}C values, from -12%% to -14%%, were found in low traffic zones; low (delta){sup 13}C values, from -14%% to -16%%, were found in high traffic zones. The amount of fossil fuel carbon assimilated by plants represented about 20% of the total plant carbon content. An overall decrease in plant (delta){sup 13}C values was observed over a four-year monitoring period. This decrease was correlated with increasing vehicle traffic. The (delta){sup 13}C dataset and the corresponding geographical database were used to map and define zones of high and low {sup 13}C-depleted CO{sub 2} emissions in urban and sub-urban areas. The spatial distribution follows dominant wind directions, with the lowest emission zones found in the southwest of Cotonou. High CO{sub 2} emissions occurred in the north, the east and the center, providing evidence of intense anthropogenic activity related to industry and transportation. (author)

Isotope exchange of molecular oxygen with oxygen of La0,7Sr0,3CoO3-δ

International Nuclear Information System (INIS)

Vdovin, G.K.; Kuzin, B.L.; Kurumchin, Eh.Kh.

1991-01-01

The exchange rate of the oxygen in La 0,7 Sr 0,3 CoO 3-δ has been measured by an isotopic exchange method at temperatures 620-1250 K and pressures 1.6-10 torr. The activation energy and the dependence of the exchange rate on pressures in gas have been defined. It is suggested that the knees on the temperature dependences of the exchange rate are attributed to the appearance of Co 2+ ions on the surface of the sample at elevated temperature as new centres of the exchange reaction. The activation energies of the adsorption and desorption processes on the La 0,7 Sr 0,3 CoO 3-δ surface have been estimated

Geochemical Study of Natural CO{sub 2} Emissions in the French Massif Central: How to Predict Origin, Processes and Evolution of CO{sub 2} Leakage; Etude geochimique des emissions naturelles de CO{sub 2} du Massif Central: origine et processus de migration du gaz

Energy Technology Data Exchange (ETDEWEB)

Battani, A.; Deville, E.; Faure, J.L.; Jeandel, E.; Noirez, S.; Tocque, E.; Benoit, Y.; Schmitz, J.; Parlouar, D. [Institut francais du petrole, IFP, 92 - Rueil-Malmaison (France); Sarda, P. [Paris-11 Univ., 91 - Orsay (France); Gal, F.; Le Pierres, K.; Brach, M.; Braibant, G.; Beny, C. [Bureau de Recherches Geologiques et Minieres (BRGM), 45 - Orleans (France); Pokryszka, Z.; Charmoille, A.; Bentivegna, G. [Institut National de l' Environnement Industriel et des Risques (INERIS), Parc Technologique ALATA, 60 - Verneuil-en-Halatte (France); Pironon, J.; De Donato, P.; Garnier, C.; Cailteau, C.; Barres, O.; Radilla, G.; Bauer, A. [Institut National Polytechnique de Lorraine (INPL), 54 - Vandoeuvre-les-Nancy (France)

2010-07-15

This study presents an overview of some results obtained within the French ANR (National Agency of Research) supported Geocarbone-Monitoring research program. The measurements were performed in Sainte-Marguerite, located in the French Massif Central. This site represents a natural laboratory for CO{sub 2}/fluid/rock interactions studies, as well as CO{sub 2} migration mechanisms towards the surface. The CO{sub 2} leaking character of the studied area also allows to test and validate measurements methods and verifications for the future CO{sub 2} geological storage sites. During these surveys, we analyzed soil CO{sub 2} fluxes and concentrations. We sampled and analyzed soil gases, and gas from carbo-gaseous bubbling springs. A one-month continuous monitoring was also tested, to record the concentration of CO{sub 2} both in atmosphere and in the soil at a single point. We also developed a new methodology to collect soil gas samples for noble gas abundances and isotopic analyses, as well as carbon isotopic ratios. Our geochemical results, combined with structural geology, show that the leaking CO{sub 2} has a very deep origin, partially mantle derived. The gas rises rapidly along normal and strike-slip active faults. CO{sub 2} soil concentrations (also showing a mantle derived component) and CO{sub 2} fluxes are spatially variable, and reach high values. The recorded atmospheric CO{sub 2} is not very high, despite the important CO{sub 2} degassing throughout the whole area. (authors)

Supercritical CO2 Compressor with Active Magnetic Bearing

International Nuclear Information System (INIS)

Cha, Jae Eun; Cho, Seong Kuk; Lee, JeKyoung; Lee, Jeong Ik

2016-01-01

For the stable operation of the sCO 2 integral test facility SCIEL, KAERI prepared Active Magnetic Bearing sCO 2 compressor for the 70,000RPM operation. Power generation test with AMB compressor will be finished within first half year of 2016 under supercritical state. The principal advantages of the sCO 2 Cycle are high efficiency at moderate temperature range, compact components size, simple cycle configuration, and compatibility with various heat sources. The Supercritical CO 2 Brayton Cycle Integral Experiment Loop (SCIEL) has been installed in Korea Atomic Energy Research Institute (KAERI) to develop the base technologies for the sCO 2 cycle power generation system. The operation of the SCIEL has mainly focused on sCO 2 compressor development and establishing sCO 2 system control logic

Isotope Exchange in Oxide Catalyst

Science.gov (United States)

Hess, Robert V.; Miller, Irvin M.; Schryer, David R.; Sidney, Barry D.; Wood, George M., Jr.; Hoyt, Ronald F.; Upchurch, Billy T.; Brown, Kenneth G.

1987-01-01

Replacement technique maintains level of CO2/18 in closed-cycle CO2 lasers. High-energy, pulsed CO2 lasers using rare chemical isotopes must be operated in closed cycles to conserve gas. Rare isotopes operated in closed cycles to conserve gas. Rare isotopes as CO2/18 used for improved transmission of laser beam in atmosphere. To maintain laser power, CO2 must be regenerated, and O2 concentration kept below few tenths of percent. Conditions achieved by recombining CO and O2.

A diatom record of CO2 decline since the late Miocene

Science.gov (United States)

Mejía, Luz María; Méndez-Vicente, Ana; Abrevaya, Lorena; Lawrence, Kira T.; Ladlow, Caroline; Bolton, Clara; Cacho, Isabel; Stoll, Heather

2017-12-01

Extratropical sea surface temperature records from alkenones record a dramatic cooling of up to 17 °C over the last ∼14 Ma, but the relationship between this cooling and greenhouse gas forcing has been elusive due to sparse and contrasting reconstructions of atmospheric CO2 for the time period. Alkenone carbon isotopic fractionation during photosynthesis has previously been used to estimate changes in pCO2 over this interval, but is complicated by significant changes in cell size of the alkenone-producing coccolithophorids over this time period. In this study, we reconstruct carbon isotopic fractionation during photosynthesis (εp) using organic compounds trapped within the frustules of pennate diatoms in sediments from the Eastern Equatorial Pacific Ocean at Ocean Drilling Program Site 846 over the last ∼13 Ma. Physical separation of pennate diatoms prior to measuring carbon isotopic fractionation enables us to obtain a record with constant cell geometry, eliminating this factor of uncertainty in our pCO2 reconstruction. In the past ∼11 Ma, εp declines from 15.5 to 10.3‰. Using the classic diffusive model and taking into account variations in opal content, alkenone concentration and coccolith Sr/Ca as indicators of past productivity and growth rate, and sea surface temperature records from the site, we estimate a decline in pCO2 from 454 (+ / - 41) to 250 (+ / - 15) ppmv between ∼11 and 6 Ma. Models accounting for changing the significance of active carbon uptake for photosynthesis, which likely produce more accurate CO2 estimates, suggest a significant larger pCO2 decline of up to twice that shown by the classic diffusive model (in average from 794 (+ / - 233) ppmv at ∼11 Ma to 288 (+/-25) ppmv at ∼6 Ma, considering growth rates varying between 0.5 and 1.7 day-1). Large uncertainties in the pCO2 estimated between ∼8 and 11 Ma using the active uptake model are related to the growth rate used for calculations. Together, these results suggest CO2

Application of stable isotope measurements and microbiological analysis for detecting methanogenic activity in a temperate forest wetland

Science.gov (United States)

Itoh, M.; Katsuyama, C.; Kondo, N.; Ohte, N.; Kato, K.

2009-12-01

Generally, forest soils act as a sink for methane (CH4). However, wetlands in riparian zones are recently reported to be “hot spots” of CH4 emissions, especially in forests under a humid climate. To understand how environmental conditions (i.e. hydrological and/or geomorphic condition) control on CH4 production, we investigated both methanogenic pathways (CO2/H2 reduction and acetate fermentation) and metahanogenic microbial communities in a wetland in a temperate forest catchment, central Japan. We used stable carbon isotopic analysis for detecting change in methanogenic pathways, and applied microbiological analysis for understanding the structure of methanogenic community. CH4 emission rates in wetland were strongly dependent on soil temperatures, and were highest in summer and lowest in winter. δ13CO2 increased with CH4 production in every summer, suggesting preferential use of 12CO2 as substrate for CO2/H2 reduction methanogenesis during high CH4 production period. δ13CH4 also increased in summer with δ13CO2. δ13CH4 changed more wildly than δ13CO2 did in summer with normal precipitation when CH4 production was strongly activated under high temperature and high groundwater table condition. This indicates increase in acetoclastic methanogenesis under hot and wet condition, considering that acetclastic methnogens produce heavier CH4 than that from CO2/H2 reducing pathway. Methanogen community composition estimated by cloning and sequence analyses implied that both acetoclastic and CO2/H2 reducing methanogens prevailed in wetland soil sampled in summer. This was consistent with the results of isotope measuremaents. Our results contribute to understand fully how the CH4 production changes with environmental conditions, with considering the activities of both main methanogenic pathway (from CO2 and acetate).

Millennial-scale changes in atmospheric CO2 levels linked to the Southern Ocean carbon isotope gradient and dust flux

Science.gov (United States)

Ziegler, Martin; Diz, Paula; Hall, Ian R.; Zahn, Rainer

2013-06-01

The rise in atmospheric CO2 concentrations observed at the end of glacial periods has, at least in part, been attributed to the upwelling of carbon-rich deep water in the Southern Ocean. The magnitude of outgassing of dissolved CO2, however, is influenced by the biological fixation of upwelled inorganic carbon and its transfer back to the deep sea as organic carbon. The efficiency of this biological pump is controlled by the extent of nutrient utilization, which can be stimulated by the delivery of iron by atmospheric dust particles. Changes in nutrient utilization should be reflected in the δ13C gradient between intermediate and deep waters. Here we use the δ13C values of intermediate- and bottom-dwelling foraminifera to reconstruct the carbon isotope gradient between thermocline and abyssal water in the subantarctic zone of the South Atlantic Ocean over the past 360,000 years. We find millennial-scale oscillations of the carbon isotope gradient that correspond to changes in dust flux and atmospheric CO2 concentrations as reported from Antarctic ice cores. We interpret this correlation as a relationship between the efficiency of the biological pump and fertilization by dust-borne iron. As the correlation is exponential, we suggest that the sensitivity of the biological pump to dust-borne iron fertilization may be increased when the background dust flux is low.

Recycling CO 2 ? Computational Considerations of the Activation of CO 2 with Homogeneous Transition Metal Catalysts

KAUST Repository

Drees, Markus

2012-08-10

Faced with depleting fossil carbon sources, the search for alternative energy carriers and energy storage possibilities has become an important issue. Nature utilizes carbon dioxide as starting material for storing sun energy in plant hydrocarbons. A similar approach, storing energy from renewable sources in chemical bonds with CO 2 as starting material, may lead to partial recycling of CO 2 created by human industrial activities. Unfortunately, currently available routes for the transformation of CO 2 involve high temperatures and are often not selective. With the development of more sophisticated methods and better software, theoretical studies have become both increasingly widespread and useful. This concept article summarizes theoretical investigations of the current state of the feasibility of CO 2 activation with molecular transition metal catalysts, highlighting the most promising reactions of CO 2 with olefins to industrially relevant acrylic acid/acrylates, and the insertion of CO 2 into metal-element bonds, particularly for the synthesis of cyclic carbonates and polymers. Rapidly improving computational power and methods help to increase the importance and accuracy of calculations continuously and make computational chemistry a useful tool helping to solve some of the most important questions for the future. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recycling CO 2 ? Computational Considerations of the Activation of CO 2 with Homogeneous Transition Metal Catalysts

KAUST Repository

Drees, Markus; Cokoja, Mirza; Kü hn, Fritz E.

2012-01-01

. A similar approach, storing energy from renewable sources in chemical bonds with CO 2 as starting material, may lead to partial recycling of CO 2 created by human industrial activities. Unfortunately, currently available routes for the transformation

CO{sub 2}-recycling by plants: how reliable is the carbon isotope estimation?

Energy Technology Data Exchange (ETDEWEB)

Siegwolf, R T.W.; Saurer, M [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Koerner, C [Basel Univ., Basel (Switzerland)

1997-06-01

In the study of plant carbon relations, the amount of the respiratory losses from the soil was estimated, determining the gradient of the stable isotope {sup 13}C with increasing plant canopy height. According to the literature 8-26% of the CO{sub 2} released in the forests by soil and plant respiratory processes are reassimilated (recycled) by photosynthesis during the day. Our own measurements however, which we conducted in grass land showed diverging results from no indicating of carbon recycling, to a considerable {delta}{sup 13}C gradient suggesting a high carbon recycling rate. The role of other factors, such as air humidity and irradiation which influence the {delta}{sup 13}C in a canopy as well, are discussed. (author) 3 figs., 4 refs.

Graphene and TiO_2 co-modified flower-like Bi_2O_2CO_3: A novel multi-heterojunction photocatalyst with enhanced photocatalytic activity

International Nuclear Information System (INIS)

Ao, Yanhui; Xu, Liya; Wang, Peifang; Wang, Chao; Hou, Jun; Qian, Jin; Li, Yi

2015-01-01

Graphical abstract: A novel multi-heterojunction photocatalyst (graphene and TiO_2 co-modified flower-like Bi_2O_2CO_3) was prepared for the first time. The as-obtained samples showed much higher activity compared to pure Bi_2O_2CO_3, TiO_2 and GR–Bi_2O_2CO_3 for dye degradation, which is almost 14 times higher than that of pure Bi_2O_2CO_3 and also much higher than the sum of graphene–Bi_2O_2CO_3 and TiO_2. - Highlights: • Graphene and TiO_2 co-modified flower-like Bi_2O_2CO_3 was prepared for the first time. • The sample shows enhanced photocatalytic activity due to the formation of multi-heterojunction. • The sample also exhibits a synergetic effect of graphene and TiO_2. • The composite photocatalyst shows a good stability for dye degradation. - Abstract: In this paper, graphene (GR) and titania co-modified flower-like Bi_2O_2CO_3 multi-heterojunction composite photocatalysts were prepared by a simple and feasible two step hydrothermal process. The prepared samples were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM), transmission electron microscopy (TEM), UV–vis diffuse reflectance spectrometry (DRS), photoluminescence (PL), N_2 adsorption–desorption isotherm, and photo-induced current. The photocatalytic activity was investigated by the degradation of MO under UV light irradiation. The as prepared multi-heterojunction GR/Bi_2O_2CO_3/TiO_2 composites exhibited much higher photocatalytic activity than pure Bi_2O_2CO_3, TiO_2 and GR–Bi_2O_2CO_3. The higher performance of GR/Bi_2O_2CO_3/TiO_2 can be ascribed to the formation of multi-heterojunctions, which promote the effective separation of photo-induced electron–hole pairs. Moreover, the higher photocatalytic activity can also be ascribed to the high surface area of GR and TiO_2, which offers more active sites for the photodegradation reaction. Furthermore, the photocatalytic activity of GR/Bi_2O_2CO_3/TiO_2 remained without striking decrease after five cycles

Current Travertines Precipitation from CO2-rich Groundwaters as an alert of CO2 Leakages from a Natural CO2 Storage at Ganuelas-Mazarron Tertiary Basin (Murcia, Spain)

International Nuclear Information System (INIS)

Rodrigo-Naharro, J.; Delgado, A.; Herrero, M. J.; Granados, A.; Perez del Villar, L.

2013-01-01

Carbon capture and storage technologies represent the most suitable solutions related to the high anthropogenic CO 2 emissions to the atmosphere. As a consequence, monitoring of the possible CO 2 leakages from an artificial deep geological CO 2 storage is indispensable to guarantee its safety. Fast surficial travertine precipitation related to these CO 2 leakages can be used as an alert for these escapes. Since few studies exist focusing on the long-term behaviour of an artificial CO 2 DGS, natural CO 2 storage affected by natural or artificial escapes must be studied as natural analogues for predicting the long-term behaviour of an artificial CO 2 storage. In this context, a natural CO 2 reservoir affected by artificial CO 2 escapes has been studied in this work. This study has mainly focused on the current travertines precipitation associated with the upwelling CO 2 -rich waters from several hydrogeological wells drilled in the Ganuelas-Mazarron Tertiary basin (SE Spain), and consists of a comprehensive characterisation of parent-waters and their associated carbonates, including elemental and isotopic geochemistry, mineralogy and petrography. Geochemical characterisation of groundwaters has led to recognise 4 hydrofacies from 3 different aquifers. These groundwaters have very high salinity and electrical conductivity; are slightly acid; present high dissolved inorganic carbon (DIC) and free CO 2 ; are oversaturated in both aragonite and calcite; and dissolve, mobilize and transport low quantities of heavy and/or toxic elements. Isotopic values indicate that: i) the origin of parent-waters is related to rainfalls from clouds originated in the Mediterranean Sea or continental areas; ii) the origin of C is mainly inorganic; and iii) sulphate anions come mainly from the dissolution of the Messinian gypsum from the Tertiary Basin sediments. Current travertines precipitation seems to be controlled by a combination of several factors, such as: i) a fast decrease of the

Interactive effects of elevated CO2 and nitrogen deposition on fatty acid molecular and isotope composition of above- and belowground tree biomass and forest soil fractions.

Science.gov (United States)

Griepentrog, Marco; Eglinton, Timothy I; Hagedorn, Frank; Schmidt, Michael W I; Wiesenberg, Guido L B

2015-01-01

Atmospheric carbon dioxide (CO2) and reactive nitrogen (N) concentrations have been increasing due to human activities and impact the global carbon (C) cycle by affecting plant photosynthesis and decomposition processes in soil. Large amounts of C are stored in plants and soils, but the mechanisms behind the stabilization of plant- and microbial-derived organic matter (OM) in soils are still under debate and it is not clear how N deposition affects soil OM dynamics. Here, we studied the effects of 4 years of elevated (13C-depleted) CO2 and N deposition in forest ecosystems established in open-top chambers on composition and turnover of fatty acids (FAs) in plants and soils. FAs served as biomarkers for plant- and microbial-derived OM in soil density fractions. We analyzed above- and belowground plant biomass of beech and spruce trees as well as soil density fractions for the total organic C and FA molecular and isotope (δ13C) composition. FAs did not accumulate relative to total organic C in fine mineral fractions, showing that FAs are not effectively stabilized by association with soil minerals. The δ13C values of FAs in plant biomass increased under high N deposition. However, the N effect was only apparent under elevated CO2 suggesting a N limitation of the system. In soil fractions, only isotope compositions of short-chain FAs (C16+18) were affected. Fractions of 'new' (experimental-derived) FAs were calculated using isotope depletion in elevated CO2 plots and decreased from free light to fine mineral fractions. 'New' FAs were higher in short-chain compared to long-chain FAs (C20-30), indicating a faster turnover of short-chain compared to long-chain FAs. Increased N deposition did not significantly affect the quantity of 'new' FAs in soil fractions, but showed a tendency of increased amounts of 'old' (pre-experimental) C suggesting that decomposition of 'old' C is retarded by high N inputs. © 2014 John Wiley & Sons Ltd.

C{sub 4} plant isotopic composition ({delta} {sup 13}C) evidence for urban CO{sub 2} pollution in the city of Cotonou, Benin (West Africa)

Energy Technology Data Exchange (ETDEWEB)

Kelome, Nelly C. [UMR Microbiologie et Geochimie des Sols INRA, Universite de Bourgogne, Centre des Sciences de la Terre, 6 Bd Gabriel, 21000 Dijon (France); Departement des Sciences de la Terre, Universite d' Abomey-Calavi, 01 B.P. 526, Cotonou (Benin); Leveque, Jean [UMR Microbiologie et Geochimie des Sols INRA, Universite de Bourgogne, Centre des Sciences de la Terre, 6 Bd Gabriel, 21000 Dijon (France)]. E-mail: jleveque@ubourgogne.fr; Andreux, Francis [UMR Microbiologie et Geochimie des Sols INRA, Universite de Bourgogne, Centre des Sciences de la Terre, 6 Bd Gabriel, 21000 Dijon (France); Milloux, Marie-Jeanne [UMR Microbiologie et Geochimie des Sols INRA, Universite de Bourgogne, Centre des Sciences de la Terre, 6 Bd Gabriel, 21000 Dijon (France); Oyede, Lucien-Marc [Departement des Sciences de la Terre, Universite d' Abomey-Calavi, 01 B.P. 526, Cotonou (Benin)

2006-08-01

The carbon isotopic composition ({delta} {sup 13}C) of plants can reveal the isotopic carbon content of the atmosphere in which they develop. The {delta} {sup 13}C values of air and plants depend on the amount of atmospheric fossil fuel CO{sub 2}, which is chiefly emitted in urban areas. A new indicator of CO{sub 2} pollution is tested using the {delta} {sup 13}C variation in a C{sub 4} grass: Eleusine indica. A range of about 4 per mille delta units was observed at different sites in Cotonou, the largest city in the Republic of Benin. The highest {delta} {sup 13}C values, from - 12 per mille to - 14 per mille , were found in low traffic zones; low {delta} {sup 13}C values, from - 14 per mille to - 16 per mille , were found in high traffic zones. The amount of fossil fuel carbon assimilated by plants represented about 20% of the total plant carbon content. An overall decrease in plant {delta} {sup 13}C values was observed over a four-year monitoring period. This decrease was correlated with increasing vehicle traffic. The {delta} {sup 13}C dataset and the corresponding geographical database were used to map and define zones of high and low {sup 13}C-depleted CO{sub 2} emissions in urban and sub-urban areas. The spatial distribution follows dominant wind directions, with the lowest emission zones found in the southwest of Cotonou. High CO{sub 2} emissions occurred in the north, the east and the center, providing evidence of intense anthropogenic activity related to industry and transportation.

Natural high pCO2 increases autotrophy in Anemonia viridis (Anthozoa) as revealed from stable isotope (C, N) analysis.

Science.gov (United States)

Horwitz, Rael; Borell, Esther M; Yam, Ruth; Shemesh, Aldo; Fine, Maoz

2015-03-05

Contemporary cnidarian-algae symbioses are challenged by increasing CO2 concentrations (ocean warming and acidification) affecting organisms' biological performance. We examined the natural variability of carbon and nitrogen isotopes in the symbiotic sea anemone Anemonia viridis to investigate dietary shifts (autotrophy/heterotrophy) along a natural pCO2 gradient at the island of Vulcano, Italy. δ(13)C values for both algal symbionts (Symbiodinium) and host tissue of A. viridis became significantly lighter with increasing seawater pCO2. Together with a decrease in the difference between δ(13)C values of both fractions at the higher pCO2 sites, these results indicate there is a greater net autotrophic input to the A. viridis carbon budget under high pCO2 conditions. δ(15)N values and C/N ratios did not change in Symbiodinium and host tissue along the pCO2 gradient. Additional physiological parameters revealed anemone protein and Symbiodinium chlorophyll a remained unaltered among sites. Symbiodinium density was similar among sites yet their mitotic index increased in anemones under elevated pCO2. Overall, our findings show that A. viridis is characterized by a higher autotrophic/heterotrophic ratio as pCO2 increases. The unique trophic flexibility of this species may give it a competitive advantage and enable its potential acclimation and ecological success in the future under increased ocean acidification.

Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

Energy Technology Data Exchange (ETDEWEB)

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.; Jennings, Ryan deM.; Beam, Jacob P.; Kreuzer, Helen W.; Inskeep, William P.

2017-07-01

Volcanism and post-magmatism contribute both significant annual CH₄ fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit methane in addition to other greenhouse gases (e.g. carbon dioxide) but the ultimate source of this methane flux has not been elucidated. Here we use dual stable isotope analysis (δ²H and δ¹³C) of CH₄(g) sampled from ten high-temperature geothermal pools in Yellowstone National Park to show that the predominant flux of CH4(g) is abiotic. The average δ¹³C and δ²H values of CH₄(g) emitted from hot springs (-26.7 (±2.4) and -236.9 (±12.0) ‰, respectively) are not consistent with biotic (microbial or thermogenic) methane sources, but are within previously reported ranges for abiotic methane production. Correlation between δ¹³C_CH4 and δ¹³C-dissolved inorganic C (DIC) also suggests that CO₂ is a parent C source for the observed CH₄(g). Moreover, CH₄-CO₂ isotopic geothermometry was used to estimate CH₄(g) formation temperatures ranging from ~ 250 - 350°C, which is just below the temperature estimated for the hydrothermal reservoir and consistent with the hypothesis that subsurface, rock-water interactions are responsible for large methane fluxes from this volcanic system. An understanding of conditions leading to the abiotic production of methane and associated isotopic signatures are central to understanding the evolutionary history of deep carbon sources on Earth.

Comparison of Surface and Column Variations of CO2 Over Urban Areas for Future Active Remote CO2 Sensors

Science.gov (United States)

Choi, Yonghoon; Yang, Melissa; Kooi, Susan; Browell, Edward

2015-01-01

High resolution in-situ CO2 measurements were recorded onboard the NASA P-3B during the DISCOVER-AQ (Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality) Field Campaign, to investigate the ability of space-based observations to accurately assess near surface conditions related to air quality. This campaign includes, Washington DC/Baltimore, MD (July 2011), San Joaquin Valley, CA (January - February 2013), Houston, TX (September 2013), and Denver, CO (July-August 2014). Each of these campaigns consisted of missed approaches and approximately two hundred vertical soundings of CO2 within the lower troposphere (surface to about 5 km). In this study, surface (0 - 1 km) and column-averaged (0 - 3.5 km) CO2 mixing ratio values from the vertical soundings in the four geographically different urban areas are used to investigate the temporal and spatial variability of CO2 within the different urban atmospheric emission environments. Tracers such as CO, CH2O, NOx, and NMHCs are used to identify the source of CO2 variations in the urban sites. Additionally, we apply nominal CO2 column weighting functions for potential future active remote CO2 sensors operating in the 1.57-microns and 2.05-microns measurement regions to convert the in situ CO2 vertical mixing ratio profiles to variations in CO2 column optical depths, which is what the active remote sensors actually measure. Using statistics calculated from the optical depths at each urban site measured during the DISCOVER-AQ field campaign and for each nominal weighting function, we investigate the natural variability of CO2 columns in the lower troposphere; relate the CO2 column variability to the urban surface emissions; and show the measurement requirements for the future ASCENDS (Active Sensing of CO2 Emissions over Nights, Days, and Seasons) in the continental U.S. urban areas.

Exogenous CO2 in South American sparkling wine

Directory of Open Access Journals (Sweden)

Leonardelli Susiane

2016-01-01

Full Text Available The sparkling wine production and consumption have increased significantly in the last years. With the increased demand appear the necessity to check the sparkling wine authenticity, because the practice of adding CO2 in sparkling wine is not allow. A way to control the carbonation process is through the determination of CO2 δ13C, because the sugar added during the second fermentation define the CO2 isotopic value, according to elaboration process. For this reason, the aim of this study was to evaluate the relationship between values of δ13C from still wines and sparkling wines, in order to set up limit values to exogenous carbonation control. Thirty-eight still wines elaborated by microvinification and 59 samples of commercial sparkling wines were analyzed, using an isotope ratio mass spectrometer (IRMS. The most negative value of natural δ13C from still wine found was − 24.7‰, it can be to estimate that lowest values are an indicative of industrial CO2 addition. Among the commercial sparkling wine from South America evaluated in this study, 10% from the samples showed signs of carbonation. Through this research was possible to establish limits of isotopic values to determine the presence of exogenous CO2.

Early deglacial Atlantic overturning decline and its role in atmospheric CO2 rise inferred from carbon isotopes (δ13C

Directory of Open Access Journals (Sweden)

A. Schmittner

2015-02-01

Full Text Available The reason for the initial rise in atmospheric CO2 during the last deglaciation remains unknown. Most recent hypotheses invoke Southern Hemisphere processes such as shifts in midlatitude westerly winds. Coeval changes in the Atlantic meridional overturning circulation (AMOC are poorly quantified, and their relation to the CO2 increase is not understood. Here we compare simulations from a global, coupled climate–biogeochemistry model that includes a detailed representation of stable carbon isotopes (δ13C with a synthesis of high-resolution δ13C reconstructions from deep-sea sediments and ice core data. In response to a prolonged AMOC shutdown initialized from a preindustrial state, modeled δ13C of dissolved inorganic carbon (δ13CDIC decreases in most of the surface ocean and the subsurface Atlantic, with largest amplitudes (more than 1.5‰ in the intermediate-depth North Atlantic. It increases in the intermediate and abyssal South Atlantic, as well as in the subsurface Southern, Indian, and Pacific oceans. The modeled pattern is similar and highly correlated with the available foraminiferal δ13C reconstructions spanning from the late Last Glacial Maximum (LGM, ~19.5–18.5 ka BP to the late Heinrich stadial event 1 (HS1, ~16.5–15.5 ka BP, but the model overestimates δ13CDIC reductions in the North Atlantic. Possible reasons for the model–sediment-data differences are discussed. Changes in remineralized δ13CDIC dominate the total δ13CDIC variations in the model but preformed contributions are not negligible. Simulated changes in atmospheric CO2 and its isotopic composition (δ13CCO2 agree well with ice core data. Modeled effects of AMOC-induced wind changes on the carbon and isotope cycles are small, suggesting that Southern Hemisphere westerly wind effects may have been less important for the global carbon cycle response during HS1 than previously thought. Our results indicate that during the early deglaciation the AMOC decreased

System for δ13C-CO2 and xCO2 analysis of discrete gas samples by cavity ring-down spectroscopy

Science.gov (United States)

Dickinson, Dane; Bodé, Samuel; Boeckx, Pascal

2017-11-01

A method was devised for analysing small discrete gas samples (50 mL syringe) by cavity ring-down spectroscopy (CRDS). Measurements were accomplished by inletting 50 mL syringed samples into an isotopic-CO2 CRDS analyser (Picarro G2131-i) between baseline readings of a reference air standard, which produced sharp peaks in the CRDS data feed. A custom software script was developed to manage the measurement process and aggregate sample data in real time. The method was successfully tested with CO2 mole fractions (xCO2) ranging from 20 000 ppm and δ13C-CO2 values from -100 up to +30 000 ‰ in comparison to VPDB (Vienna Pee Dee Belemnite). Throughput was typically 10 samples h-1, with 13 h-1 possible under ideal conditions. The measurement failure rate in routine use was ca. 1 %. Calibration to correct for memory effects was performed with gravimetric gas standards ranging from 0.05 to 2109 ppm xCO2 and δ13C-CO2 levels varying from -27.3 to +21 740 ‰. Repeatability tests demonstrated that method precision for 50 mL samples was ca. 0.05 % in xCO2 and 0.15 ‰ in δ13C-CO2 for CO2 compositions from 300 to 2000 ppm with natural abundance 13C. Long-term method consistency was tested over a 9-month period, with results showing no systematic measurement drift over time. Standardised analysis of discrete gas samples expands the scope of application for isotopic-CO2 CRDS and enhances its potential for replacing conventional isotope ratio measurement techniques. Our method involves minimal set-up costs and can be readily implemented in Picarro G2131-i and G2201-i analysers or tailored for use with other CRDS instruments and trace gases.

Influence of local emissions on concentration and isotopic composition of trace gases (CO2 and CH4) under strong anthropopression: A case study from Krakow, southern Poland

International Nuclear Information System (INIS)

Florkowski, T.; Korus, A.; Kuc, T.; Lasa, J.; Necki, J.M.; Zimnoch, M.

2002-01-01

Full text: Measurements of the isotopic composition of carbon dioxide and methane together with their concentrations in the atmosphere, yield useful information on the contribution of anthropogenic sources to regional budgets of these gases and their seasonal changes. Observed correlation between isotopic composition and inverse concentration of these gases is used for estimation of mean isotopic composition of the local source. Monitoring of atmospheric CO 2 has been initiated in Krakow in 1982. The sampling point is located in a polluted urban area with strong contribution of anthropogenic gases originating both from local sources (coal burning, car traffic, leakages from city gas network, landfills) and large distant emitters - industrial district located ca. 80 km to the west from Krakow (Silesia district). Quasi-continuous measurements of CO 2 , and CH 4 concentrations in the low atmosphere are performed using gas chromatographic method. For isotope measurements, the atmospheric CO 2 is continuously sampled by sorption on molecular sieve in be-weekly intervals and radiocarbon concentration is measured by liquid scintillation spectrometer, while δ 13 C is determined by isotope ratio mass spectrometer. Measurement error (1σ for single measurement) is in the order of 0.1 ppm for CO 2 concentration, ±8 per mille for δ 14 C, and ± 0.1 per mille for δ 13 C. In 1994, a new station for regular observations of greenhouse gases in lower atmosphere was set up in the High Tatra mountains, at Kasprowy Wierch (49 deg. N, 20 deg. E, 1980 m a.s.l., 300 m above the tree line). Kasprowy Wierch, with only small influences from local sources of trace gases can be considered as a reference station for this region of Poland. The record of CO 2 and CH 4 concentration and their isotope composition obtained at Kasprowy Wierch is considered as a background level for Krakow observations. The presented study was aimed at better characterisation and quantification of the local

13C analyses on CO2 in air using the multiflow: Application for the monitoring of atmospheric 13CO2 over hydro-electric reservoir in Quebec's Boreal region - Canada

International Nuclear Information System (INIS)

Bilodeau, G.; Hillaire-Marcel, C.; Helie, J.-F.; Fourel, F.; Varfalvy, L.

2002-01-01

The Multiflow TM preparation system is a headspace sampling device allowing extraction, purification and introduction of a gas sample into a gas-source Isotopic Ratio Mass Spectrometer for isotopic analysis. The original device was designed for 13 C measurements on CO 2 from breath tests. It has been adapted here for 13 CO 2 analysis in atmospheric low pCO 2 -samples

Silicon isotope separation utilizing infrared multiphoton dissociation of Si2F6 irradiated with two-color CO2 laser light

International Nuclear Information System (INIS)

Yokoyama, Atsushi; Ohba, Hironori; Hashimoto, Masashi; Arai, Shigeyoshi

2002-01-01

Silicon isotope separation has been done by utilizing the Infrared Multiphoton Dissociation (IRMPD) of Si 2 F 6 irradiated with two-color CO 2 laser lights. The two-color excitation method improved the separation efficiency keeping the high enrichment factors. For example, 99.74% of 28 Si was obtained at 49.63% dissociation of Si 2 F 6 after the simultaneous irradiation of 200 pulses with 966.23 cm -1 photons (0.084 J/cm 2 ) and 954.55 cm -1 photons (0.658 J/cm 2 ), while 2000 pulses were needed to obtain 99.35% of 28 Si at 35.6% dissociation in the case of only one-color irradiation at 954.55 cm -1 (0.97 J/cm 2 ). (author)

Isotopic evidence for the infiltration of mantle and metamorphic CO2-H2O fluids from below in faulted rocks from the San Andreas Fault System

Energy Technology Data Exchange (ETDEWEB)

Pili, E.; Kennedy, B.M.; Conrad, M.E.; Gratier, J.-P.

2010-12-15

To characterize the origin of the fluids involved in the San Andreas Fault (SAF) system, we carried out an isotope study of exhumed faulted rocks from deformation zones, vein fillings and their hosts and the fluid inclusions associated with these materials. Samples were collected from segments along the SAF system selected to provide a depth profile from upper to lower crust. In all, 75 samples from various structures and lithologies from 13 localities were analyzed for noble gas, carbon, and oxygen isotope compositions. Fluid inclusions exhibit helium isotope ratios ({sup 3}He/{sup 4}He) of 0.1-2.5 times the ratio in air, indicating that past fluids percolating through the SAF system contained mantle helium contributions of at least 35%, similar to what has been measured in present-day ground waters associated with the fault (Kennedy et al., 1997). Calcite is the predominant vein mineral and is a common accessory mineral in deformation zones. A systematic variation of C- and O-isotope compositions of carbonates from veins, deformation zones and their hosts suggests percolation by external fluids of similar compositions and origin with the amount of fluid infiltration increasing from host rocks to vein to deformation zones. The isotopic trend observed for carbonates in veins and deformation zones follows that shown by carbonates in host limestones, marbles, and other host rocks, increasing with increasing contribution of deep metamorphic crustal volatiles. At each crustal level, the composition of the infiltrating fluids is thus buffered by deeper metamorphic sources. A negative correlation between calcite {delta}{sup 13}C and fluid inclusion {sup 3}He/{sup 4}He is consistent with a mantle origin for a fraction of the infiltrating CO{sub 2}. Noble gas and stable isotope systematics show consistent evidence for the involvement of mantle-derived fluids combined with infiltration of deep metamorphic H{sub 2}O and CO{sub 2} in faulting, supporting the involvement of

Cavity Ring-down Spectroscopy for Carbon Isotope Analysis with 2 μm Diode Laser

International Nuclear Information System (INIS)

Hiromoto, K.; Tomita, H.; Watanabe, K.; Kawarabayashi, J.; Iguchi, T.

2009-01-01

We have made a prototype based on CRDS with 2 μm diode laser for carbon isotope analysis of CO 2 in air. The carbon isotope ratio was obtained to be (1.085±0.012)x10 -2 which shows good agreement with the isotope ratio measured by the magnetic sector-type mass spectrometer within uncertainty. Hence, we demonstrated the carbon isotope analysis based on CRDS with 2 μm tunable diode laser.

A new set-up for simultaneous high-precision measurements of CO2, δ13C-CO2 and δ18O-CO2 on small ice core samples

Science.gov (United States)

Jenk, Theo Manuel; Rubino, Mauro; Etheridge, David; Ciobanu, Viorela Gabriela; Blunier, Thomas

2016-08-01

Palaeoatmospheric records of carbon dioxide and its stable carbon isotope composition (δ13C) obtained from polar ice cores provide important constraints on the natural variability of the carbon cycle. However, the measurements are both analytically challenging and time-consuming; thus only data exist from a limited number of sampling sites and time periods. Additional analytical resources with high analytical precision and throughput are thus desirable to extend the existing datasets. Moreover, consistent measurements derived by independent laboratories and a variety of analytical systems help to further increase confidence in the global CO2 palaeo-reconstructions. Here, we describe our new set-up for simultaneous measurements of atmospheric CO2 mixing ratios and atmospheric δ13C and δ18O-CO2 in air extracted from ice core samples. The centrepiece of the system is a newly designed needle cracker for the mechanical release of air entrapped in ice core samples of 8-13 g operated at -45 °C. The small sample size allows for high resolution and replicate sampling schemes. In our method, CO2 is cryogenically and chromatographically separated from the bulk air and its isotopic composition subsequently determined by continuous flow isotope ratio mass spectrometry (IRMS). In combination with thermal conductivity measurement of the bulk air, the CO2 mixing ratio is calculated. The analytical precision determined from standard air sample measurements over ice is ±1.9 ppm for CO2 and ±0.09 ‰ for δ13C. In a laboratory intercomparison study with CSIRO (Aspendale, Australia), good agreement between CO2 and δ13C results is found for Law Dome ice core samples. Replicate analysis of these samples resulted in a pooled standard deviation of 2.0 ppm for CO2 and 0.11 ‰ for δ13C. These numbers are good, though they are rather conservative estimates of the overall analytical precision achieved for single ice sample measurements. Facilitated by the small sample requirement

Current Travertines Precipitation from CO{sub 2}-rich Groundwaters as an alert of CO{sub 2} Leakages from a Natural CO{sub 2} Storage at Ganuelas-Mazarron Tertiary Basin (Murcia, Spain)

Energy Technology Data Exchange (ETDEWEB)

Rodrigo-Naharro, J.; Delgado, A.; Herrero, M. J.; Granados, A.; Perez del Villar, L.

2013-02-01

Carbon capture and storage technologies (CCS) represent the most suitable solutions related to the high anthropogenic CO{sub 2} emissions to the atmosphere. As a consequence, monitoring of the possible CO{sub 2} leakages from an artificial deep geological CO{sub 2} storage (DGS) is indispensable to guarantee its safety. Fast surficial travertine precipitation related to these CO{sub 2} leakages can be used as an alert for these escapes. Since few studies exist focusing on the long-term behaviour of an artificial CO{sub 2} DGS, natural CO{sub 2} storage affected by natural or artificial escapes must be studied as natural analogues for predicting the long-term behaviour of an artificial CO{sub 2} storage. In this context, a natural CO{sub 2} reservoir affected by artificial CO{sub 2} escapes has been studied in this work. This study has mainly focused on the current travertines precipitation associated with the upwelling CO{sub 2}-rich waters from several hydrogeological wells drilled in the Ganuelas-Mazarron Tertiary basin (SE Spain), and consists of a comprehensive characterisation of parent-waters and their associated carbonates, including elemental and isotopic geochemistry, mineralogy and petrography. Geochemical characterisation of groundwaters has led to recognise 4 hydrofacies from 3 different aquifers. These groundwaters have very high salinity and electrical conductivity; are slightly acid; present high dissolved inorganic carbon (DIC) and free CO{sub 2}; are oversaturated in both aragonite and calcite; and dissolve, mobilize and transport low quantities of heavy and/or toxic elements. Isotopic values indicate that: i) the origin of parent-waters is related to rainfalls from clouds originated in the Mediterranean Sea or continental areas; ii) the origin of C is mainly inorganic; and iii) sulphate anions come mainly from the dissolution of the Messinian gypsum from the Tertiary Basin sediments. Current travertines precipitation seems to be controlled by a

Catalytic activity in reactions of isotopic exchange of carbon monoxide and adsorption properties of catalysts on zinc oxide base

International Nuclear Information System (INIS)

Mikheeva, T.M.; Kasatkina, L.A.; Volynkina, A.Ya.

1987-01-01

Activity of different zinc oxide samples in reaction of CO homomolecular isotopic exchnge (HMIE) ( 13 C 18 O+ 12 C 16 O= 13 C 16 O+ 12 C 18 O), CO adsorption on ZnO and isotopic exchange between adsorbed and gaseous CO are investigated. The most active is ZnO sample prepared from ZnCO 3 . Quantitative ratio between different with respect to surface strength molecules of adsorbed CO are experimentally determined. It is shown that by increase of ZnO time contact with CO the quantity of adsorbed CO(N σ/0 ), capable of fast exchange with a gaseous phase, is reduced and the quantity of slowly exchanged adsorbed CO is increased. Correlation between decrease of N σ/0 and decrease of CO HMIE with the catalyst holding time in CO medium is stated

Supercritical CO{sub 2} Compressor with Active Magnetic Bearing

Energy Technology Data Exchange (ETDEWEB)

Cha, Jae Eun [KAERI, Daejeon (Korea, Republic of); Cho, Seong Kuk; Lee, JeKyoung; Lee, Jeong Ik [KAIST, Daejeon (Korea, Republic of)

2016-05-15

For the stable operation of the sCO{sub 2} integral test facility SCIEL, KAERI prepared Active Magnetic Bearing sCO{sub 2} compressor for the 70,000RPM operation. Power generation test with AMB compressor will be finished within first half year of 2016 under supercritical state. The principal advantages of the sCO{sub 2} Cycle are high efficiency at moderate temperature range, compact components size, simple cycle configuration, and compatibility with various heat sources. The Supercritical CO{sub 2} Brayton Cycle Integral Experiment Loop (SCIEL) has been installed in Korea Atomic Energy Research Institute (KAERI) to develop the base technologies for the sCO{sub 2} cycle power generation system. The operation of the SCIEL has mainly focused on sCO{sub 2} compressor development and establishing sCO{sub 2} system control logic.

Measurements and modeling of CO₂ concentration and isotopes to improve process-level understanding of Arctic and boreal carbon cycling. Final Report

Energy Technology Data Exchange (ETDEWEB)

Keeling, Ralph F. [Univ. of California, San Diego, CA (United States). Scripps Inst. of Oceanography

2017-09-29

The major goal of this project was to improve understanding of processes that control the exchanges of CO₂ between the atmosphere and the land biosphere on decadal and longer time scales. The approach involves measuring the changes in atmospheric CO₂ concentration and the isotopes of CO₂ (¹³C/¹²C and ¹⁸O/¹⁶O) at background stations and uses these and other datasets to challenge and improve numerical models of the earth system. The project particularly emphasized the use of these data to improve understanding of changes occurring in boreal and arctic ecosystems over the past 50 years and to seek from these data improved understanding of large-scale processes impacting carbon cycling, such as the responses to warming, CO₂ fertilization, and disturbance. The project also led to advances in the understanding of changes in water-use efficiency of land ecosystems globally based on trends in ¹³C/¹²C. The core element of this project was providing partial support for continuing measurements of CO₂ concentrations and isotopes from the Scripps CO₂ program, initiated by C. D. Keeling in the 1960s. The measurements included analysis of flasks collected at an array of ten stations distributed from the Arctic to the Antarctic. The project also supported modeling studies and interpretive work to help understand the origins of the large ~50% increase in the amplitude of the atmospheric CO₂ cycle detected at high northern latitudes between 1960 and present and to understand the long-term trend in carbon ¹³C/¹²C of CO₂. The seasonal cycle work was advanced through collaborations with colleagues at MPI Jena and Imperial College

Use of the isotope flux ratio approach to investigate the C18O16O and 13CO2 exchange near the floor of a temperate deciduous forest

Directory of Open Access Journals (Sweden)

P. Bartlett

2012-07-01

Full Text Available Stable isotopologues of CO2, such as 13CO2 and C18OO, have been used to study the CO2 exchange between land and atmosphere. The advent of new measuring techniques has allowed near-continuous measurements of stable isotopes in the air. These measurements can be used with micrometeorological techniques, providing new tools to investigate the isotope exchange in ecosystems. The objectives of this study were to evaluate the use of the isotope flux ratio method (IFR near the forest floor of a temperate deciduous forest and to study the temporal dynamics of δ18O of CO2 flux near the forest floor by comparing IFR estimates with estimates of δ18O of net soil CO2 flux provided by an analytical model. Mixing ratios of 12C16O2, 13CO2 and C16O18O were measured within and above a temperate deciduous forest, using the tunable diode laser spectroscopy technique. The half-hourly compositions of the CO2 flux near the forest floor (δ13CF and δ18OF were calculated by IFR and compared with estimates provided by a modified Keeling plot technique (mKP and by a Lagrangian dispersion analysis (WT analysis. The mKP and IFR δ18OF estimates showed good agreement (slope = 1.03 and correlation, R2 = 0.80. The δ13CF estimates from the two methods varied in a narrow range of −32.7 and −23‰; the mean (± SE mKP and IFR δ13CF values were −27.5‰ (±0.2 and −27.3‰ (±0.1, respectively, and were statistically identical (p>0.05. WT analysis and IFR δ18OF estimates showed better correlation (R2 = 0.37 when only turbulent periods (u*>0.6 m s−1 were included in the analysis. The large amount of data captured (~95 % of half-hour periods evaluated for the IFR in comparison with mKP (27 % shows that the former provides new opportunities for studying δ18OF dynamics within forest canopies. Values of δ18OF showed large temporal variation, with values ranging from −31.4‰ (DOY 208 to −11.2‰ (DOY 221. Precipitation events caused substantial variation (~8�

Table of specific activities of selected isotopes

International Nuclear Information System (INIS)

Shipley, G.

The bulk of this publication consists of a table of the half-lives, decay modes, and specific activities of isotopes selected for their particular interest to the Environmental Health and Safety Department, LBL. The specific activities were calculated with a PDP 9/15 computer. Also included in the report is a table of stable isotopes, the Th and U decay chains, a chart of the nuclides for elements 101 through 106, the heavy element region of the periodic table, and a specific activity monograph. 5 figures, 2 tables

The Interrelationship of pCO2, Soil Moisture Content, and Biomass Fertilization Expressed in the Carbon Isotope Signature of C3 Plant Tissue

Science.gov (United States)

Schubert, B.; Jahren, A. H.

2017-12-01

Hundreds of chamber and field experiments have shown an increase in C3 plant biomass in response to elevated atmospheric carbon dioxide (pCO2); however, secondary water and nutrient deficits are thought to limit this response. Some have hypothesized that secondary limitation might be self-alleviating under elevated pCO2 as greater root biomass imparts enhanced access to water and nutrients. Here we present results of growth chamber experiments designed to test this hypothesis: we grew 206 Arabidopsis thaliana plants within 5 growth chambers, each set at a different level of pCO2: 390, 685, 1075, 1585, and 2175 ppmv. Within each growth chamber, soil moisture content (θm) was maintained across a spectrum: 1.50, 0.83, 0.44, and 0.38 g g-1. After 3 weeks of total growth, tissues were analyzed for both biomass and net carbon isotope discrimination (Δ13C) value. From these values, we calculated Δresidual, which represents the residual effect of water stress after subtraction of the effect of pCO2 due to photorespiration. Across the full range of moisture content, Δresidual displayed a significant 2.5‰ increase with increasing pCO2. This further implies a 0.1 unit increase in ci/ca, consistent with decreased water stress at elevated pCO2. The influence of CO2 fertilization on the alleviation of water stress was further evidenced in a positive correlation between percent biomass change and Δresidual, such that a doubling of plant biomass yielded a 1.85‰ increase in carbon isotope discrimination. In addition to providing new insight into water uptake in plants growing under elevated carbon dioxide, these data underscore the importance of separating the effects of increased pCO2 (via photorespiration) and altered ci/ca (via stomatal conductance) when considering changes in the Δ13C value of C3 land plants during the Anthropocene, or across any geological period that includes a marked change in global carbon cycling.

System for δ13C–CO2 and xCO2 analysis of discrete gas samples by cavity ring-down spectroscopy

Directory of Open Access Journals (Sweden)

D. Dickinson

2017-11-01

Full Text Available A method was devised for analysing small discrete gas samples (50 mL syringe by cavity ring-down spectroscopy (CRDS. Measurements were accomplished by inletting 50 mL syringed samples into an isotopic-CO2 CRDS analyser (Picarro G2131-i between baseline readings of a reference air standard, which produced sharp peaks in the CRDS data feed. A custom software script was developed to manage the measurement process and aggregate sample data in real time. The method was successfully tested with CO2 mole fractions (xCO2 ranging from  <  0.1 to  >  20 000 ppm and δ13C–CO2 values from −100 up to +30 000 ‰ in comparison to VPDB (Vienna Pee Dee Belemnite. Throughput was typically 10 samples h−1, with 13 h−1 possible under ideal conditions. The measurement failure rate in routine use was ca. 1 %. Calibration to correct for memory effects was performed with gravimetric gas standards ranging from 0.05 to 2109 ppm xCO2 and δ13C–CO2 levels varying from −27.3 to +21 740 ‰. Repeatability tests demonstrated that method precision for 50 mL samples was ca. 0.05 % in xCO2 and 0.15 ‰ in δ13C–CO2 for CO2 compositions from 300 to 2000 ppm with natural abundance 13C. Long-term method consistency was tested over a 9-month period, with results showing no systematic measurement drift over time. Standardised analysis of discrete gas samples expands the scope of application for isotopic-CO2 CRDS and enhances its potential for replacing conventional isotope ratio measurement techniques. Our method involves minimal set-up costs and can be readily implemented in Picarro G2131-i and G2201-i analysers or tailored for use with other CRDS instruments and trace gases.

Magnetic properties of iron-based catalysts activated by various CO{sub 2} concentrations

Energy Technology Data Exchange (ETDEWEB)

Lim, Jung Tae; Kim, Chul Sung [Kookmin University, Seoul (Korea, Republic of); Chun, Dong Hyun; Park, Ji Chan [Korea Institute of Energy Research, Daejeon (Korea, Republic of)

2014-12-15

Fresh catalyst samples of 100Fe/5.26Cu/4.76K/18.2SiO{sub 2} in part per weight were synthesized by using a combination of a co-precipitation technique and spray-drying method and were activated in situ by using syngas (H{sub 2}/CO/xCO{sub 2}) with different amounts of CO{sub 2} (x = 0.0, 0.5, 1.0, and 2.0). All activated catalyst samples showed similar XRD patterns, a combination of ferrihydrite, magnetite, χ-carbide, and ε'-carbide, regardless of the CO{sub 2} contents. From the Moessbauer spectra, we also observed a combination of ferrihydrite, magnetite, χ-carbide, and ε'-carbide in all activated catalyst samples. The main compound of the activated catalyst sample activated by using CO{sub 2}-free syngas (H{sub 2}/CO) was magnetic χ-carbide, and the main compound changed from χ-carbide to ferrihydrite with increasing CO{sub 2} concentration, confirmed by both, Moessbauer spectra and XRD pattern.

Faults as Windows to Monitor Gas Seepage: Application to CO2 Sequestration and CO2-EOR

Directory of Open Access Journals (Sweden)

Ronald W. Klusman

2018-03-01

Full Text Available Monitoring of potential gas seepage for CO2 sequestration and CO2-EOR (Enhanced Oil Recovery in geologic storage will involve geophysical and geochemical measurements of parameters at depth and at, or near the surface. The appropriate methods for MVA (Monitoring, Verification, Accounting are needed for both cost and technical effectiveness. This work provides an overview of some of the geochemical methods that have been demonstrated to be effective for an existing CO2-EOR (Rangely, CA, USA and a proposed project at Teapot Dome, WY, USA. Carbon dioxide and CH4 fluxes and shallow soil gas concentrations were measured, followed by nested completions of 10-m deep holes to obtain concentration gradients. The focus at Teapot Dome was the evaluation of faults as pathways for gas seepage in an under-pressured reservoir system. The measurements were supplemented by stable carbon and oxygen isotopic measurements, carbon-14, and limited use of inert gases. The work clearly demonstrates the superiority of CH4 over measurements of CO2 in early detection and quantification of gas seepage. Stable carbon isotopes, carbon-14, and inert gas measurements add to the verification of the deep source. A preliminary accounting at Rangely confirms the importance of CH4 measurements in the MVA application.

Paired carbon stable-isotope records for the Cenomanian Stage (100.5 -93.9 Ma): correlation tool and Late Cretaceous pCO2 record?

Science.gov (United States)

Jarvis, Ian; Gröcke, Darren; Laurin, Jiří; Selby, David; Roest-Ellis, Sascha; Miles, Andrew; Lignum, John; Gale, Andrew; Kennedy, Jim

2016-04-01

- and long-term trends. Potential causes of the similarities and differences are examined, and it is concluded that major deviations of the paired isotope trends offer insights into long-term atmospheric pCO2 variation. The osmium 187Os/188Os isotope stratigraphy of the MCEI and OAE2 intervals provides evidence of varying volcanic CO2 input, in-part driving climate change. Spectral analyses of the δ13Corg time series reveals a strong ~100 kyr short eccentricity signal throughout the Cenomanian, with well-expressed ~40 kyr obliquity and ~20 kyr precession cycles in some intervals. A 400 kyr long eccentricity cycle is recorded in sedimentation rate changes and amplitude modulation of the 100 kyr cycle. The relative spacing of events, and comparison with the latest orbital solution La2011, further suggest that MCE I and OAE2 coincided with nodes in the ~2.2-Myr eccentricity modulation.

Active sites of ligand-protected Au25 nanoparticle catalysts for CO2 electroreduction to CO

Science.gov (United States)

Alfonso, Dominic R.; Kauffman, Douglas; Matranga, Christopher

2016-05-01

Recent experimental studies have reported the electrochemical reduction of carbon dioxide (CO2) into CO at atomically precise negatively charged Au25- nanoclusters. The studies showed CO2 conversion at remarkably low overpotentials, but the exact mechanisms and nature of the active sites remain unclear. We used first-principles density functional theory and continuum solvation models to examine the role of the cluster during electrochemical CO2 reduction and analyze the free energies of proposed intermediate species. Contrary to previous assumptions, our results show that the fully ligand protected cluster is not an active CO2 reduction catalyst because formation of the crucial carboxyl intermediate required very high electrochemical potentials. Instead, our calculations suggest that the reduction process likely occurs on a dethiolated gold site, and adsorbed carboxyl intermediate formation was significantly stabilized at dethiolated gold sites. These findings point to the crucial role of exposed metal sites during electrochemical CO2 reduction at gold nanocluster catalysts.

The isotopic record of Northern Hemisphere atmospheric carbon monoxide since 1950: implications for the CO budget

Directory of Open Access Journals (Sweden)

Z. Wang

2012-05-01

Full Text Available We present a 60-year record of the stable isotopes of atmospheric carbon monoxide (CO from firn air samples collected under the framework of the North Greenland Eemian Ice Drilling (NEEM project. CO concentration, δ¹³C, and δ¹⁸O of CO were measured by gas chromatography/isotope ratio mass spectrometry (gc-IRMS from trapped gases in the firn. We applied LGGE-GIPSA firn air models (Witrant et al., 2011 to correlate gas age with firn air depth and then reconstructed the trend of atmospheric CO and its stable isotopic composition at high northern latitudes since 1950. The most probable firn air model scenarios show that δ¹³C decreased slightly from −25.8‰ in 1950 to −26.4‰ in 2000, then decreased more significantly to −27.2‰ in 2008. δ¹⁸O decreased more regularly from 9.8‰ in 1950 to 7.1‰ in 2008. Those same scenarios show CO concentration increased gradually from 1950 and peaked in the late 1970s, followed by a gradual decrease to present day values (Petrenko et al., 2012. Results from an isotope mass balance model indicate that a slight increase, followed by a large reduction, in CO derived from fossil fuel combustion has occurred since 1950. The reduction of CO emission from fossil fuel combustion after the mid-1970s is the most plausible mechanism for the drop of CO concentration during this time. Fossil fuel CO emissions decreased as a result of the implementation of catalytic converters and the relative growth of diesel engines, in spite of the global vehicle fleet size having grown several fold over the same time period.

Catalytic activity of Co/SiO2 and Co/TiO2 nanosized systems in the oxidation of carbon monoxide

Science.gov (United States)

Kelyp, A. A.; Smirnova, N. P.; Oleksenko, L. P.; Lutsenko, L. V.; Oranskaya, E. I.; Ripko, A. P.

2013-06-01

The effects of the preparation procedure, active component concentration, and conditions of formation of nanosized cobalt-containing systems based on TiO2 and SiO2 mesoporous powders on their catalytic activity in the oxidation of carbon monoxide were studied. The active phase in the systems was cobalt spinel CoCo2O4 found in all samples. High catalytic activity was found in the samples characterized by relatively high contents of surface active centers (cobalt cations with octahedral surroundings).

Co-deposition of palladium with hydrogen isotopes

International Nuclear Information System (INIS)

Dash, J.; Ambadkar, A.

2006-01-01

Palladium was co-deposited with hydrogen isotopes on a Pd cathode. This resulted in enhanced production of excess thermal power. After electrolysis the Pd Lβ/ Lα ratio was found to be increased in characteristic X-ray spectra from localized, microscopic areas on the surface of the Pd cathode. This suggests the possibility that appreciable amounts of silver are present in these areas. (authors)

CO self-shielding as the origin of oxygen isotope anomalies in the early solar nebula.

Science.gov (United States)

Lyons, J R; Young, E D

2005-05-19

The abundances of oxygen isotopes in the most refractory mineral phases (calcium-aluminium-rich inclusions, CAIs) in meteorites have hitherto defied explanation. Most processes fractionate isotopes by nuclear mass; that is, 18O is twice as fractionated as 17O, relative to 16O. In CAIs 17O and 18O are nearly equally fractionated, implying a fundamentally different mechanism. The CAI data were originally interpreted as evidence for supernova input of pure 16O into the solar nebula, but the lack of a similar isotope trend in other elements argues against this explanation. A symmetry-dependent fractionation mechanism may have occurred in the inner solar nebula, but experimental evidence is lacking. Isotope-selective photodissociation of CO in the innermost solar nebula might explain the CAI data, but the high temperatures in this region would have rapidly erased the signature. Here we report time-dependent calculations of CO photodissociation in the cooler surface region of a turbulent nebula. If the surface were irradiated by a far-ultraviolet flux approximately 10(3) times that of the local interstellar medium (for example, owing to an O or B star within approximately 1 pc of the protosun), then substantial fractionation of the oxygen isotopes was possible on a timescale of approximately 10(5) years. We predict that similarly irradiated protoplanetary disks will have H2O enriched in 17O and 18O by several tens of per cent relative to CO.

Chemical engineering design of CO oxidation catalysts

Science.gov (United States)

Herz, Richard K.

1987-01-01

How a chemical reaction engineer would approach the challenge of designing a CO oxidation catalyst for pulsed CO2 lasers is described. CO oxidation catalysts have a long history of application, of course, so it is instructive to first consider the special requirements of the laser application and then to compare them to the characteristics of existing processes which utilize CO oxidation catalysts. All CO2 laser applications require a CO oxidation catalyst with the following characteristics: (1) active at stoichiometric ratios of O2 and CO, (2) no inhibition by CO2 or other components of the laser environment, (3) releases no particulates during vibration or thermal cycling, and (4) long lifetime with a stable activity. In all applications, low consumption of power is desirable, a characteristic especially critical in aerospace applications and, thus, catalyst activity at low temperatures is highly desirable. High power lasers with high pulse repetition rates inherently require circulation of the gas mixture and this forced circulation is available for moving gas past the catalyst. Low repetition rate lasers, however, do not inherently require gas circulation, so a catalyst that did not require such circulation would be favorable from the standpoint of minimum power consumption. Lasers designed for atmospheric penetration of their infrared radiation utilize CO2 formed from rare isotopes of oxygen and this application has the additional constraint that normal abundance oxygen isotopes in the catalyst must not exchange with rare isotopes in the gas mixture.

13CO2/12CO2 ratio analysis in exhaled air by lead-salt tunable diode lasers for noninvasive diagnostics in gastroenterology

Science.gov (United States)

Stepanov, Eugene V.; Zyrianov, Pavel V.; Miliaev, Valerii A.; Selivanov, Yurii G.; Chizhevskii, Eugene G.; Os'kina, Svetlana; Ivashkin, Vladimir T.; Nikitina, Elena I.

1999-07-01

An analyzer of 13CO2/12CO2 ratio in exhaled air based on lead-salt tunable diode lasers is presented. High accuracy of the carbon isotope ratio detection in exhaled carbon dioxide was achieved with help of very simple optical schematics. It was based on the use of MBE laser diodes operating in pulse mode and on recording the resonance CO2 absorption at 4.2 micrometers . Special fast acquisition electronics and software were applied for spectral data collection and processing. Developed laser system was tested in a clinical train aimed to assessment eradication efficiency in therapy of gastritis associated with Helicobacter pylori infection. Data on the 13C-urea breath test used for P.pylori detection and obtained with tunable diode lasers in the course of the trail was compared with the results of Mass-Spectroscopy analysis and histology observations. The analyzer can be used also for 13CO2/12CO2 ratio detection in exhalation to perform gastroenterology breath test based on using other compounds labeled with stable isotopes.

Porous carbon from local coconut shell char by CO2 and H2O activation in the presence of K2CO3

Science.gov (United States)

Vi, Nguyen Ngoc Thuy; Truyen, Dang Hai; Trung, Bien Cong; An, Ngo Thanh; Van Dung, Nguyen; Long, Nguyen Quang

2017-09-01

Vietnamese coconut shell char was activated by steam and carbon dioxide at low temperatures with the presence of K2CO3 as a catalyst. The effects of process parameters on adsorption capability of the product including different ratio of impregnation of activation agents, activation temperature, activation time were investigated in this study. Iodine number, methylene blue adsorption capacity, specific surface area and pore size distribution were measured to assess the properties of the activated carbon. Accordingly, the porous carbon was applied for toluene removal by adsorption technology. Significant increases in specific surface area and the toluene adsorption capacity were observed when the coconut shell char was activated in CO2 flow at 720 °C for 150 minutes and the K2CO3/char weight ratio of 0.5.

Calcium and titanium isotopes in refractory inclusions from CM, CO, and CR chondrites

Science.gov (United States)

Kööp, Levke; Davis, Andrew M.; Krot, Alexander N.; Nagashima, Kazuhide; Simon, Steven B.

2018-05-01

Previous studies have shown that CV and CM chondrites incorporated Ca, Al-rich inclusions (CAIs) with different isotopic characteristics, which may represent different snapshots in the isotopic evolution of the early Solar System. To better understand how the isotopic characteristics of CAIs vary between different chondrite groups, we have studied calcium and titanium isotopes in CAIs from CM, CO, and CR chondrites. We show that all three chondrite groups contain CAIs with large anomalies in 48Ca and/or 50Ti (10s of ‰ or 100s of ε-units) as well as CAIs with no anomalies resolved beyond measurement uncertainties. Isotopically, the anomalous CO and CR chondrite CAIs resemble the platy hibonite crystals (PLACs) from CM chondrites, but they are more mineralogically complex. The new data are consistent with the well-established mutual exclusivity relationship between incorporation of 26Al and the presence of large anomalies in 48Ca and 50Ti. The two highly anomalous CO chondrite CAIs have correlated anomalies in 46Ti and 50Ti, while most other highly anomalous CAIs do not. This result could indicate that the reservoir with coupled 46Ti and 50Ti that was sampled by bulk meteorites and CV chondrite CAIs already existed before arrival and/or homogeneous distribution of 26Al in the protoplanetary disk. Among the studied CM chondrite CAIs are ten spinel-hibonite inclusions (SHIBs) with known oxygen isotopic compositions. Our results show that these objects sampled a reservoir that was well-mixed in oxygen, calcium, and titanium isotopes. We further show that SHIBs tend to be slightly enriched in the heavy calcium isotopes, suggesting that their formation history was different from CV chondrite CAIs.

Co-ordinated research programme on applications of stable isotope tracers in human nutrition research

International Nuclear Information System (INIS)

1992-01-01

This document provides a very brief report on the final Research Co-ordination Meeting of this Co-ordinated Research Project (CRP): the final report on the CRP will be published by the IAEA in the IAEA-TECDOC series. The present document contains a detailed proposal for a new Co-ordinated Research Programme on ''Stable Isotope Tracer Techniques for Studies on Protein-Energy Interactions'', and a brief series of notes on stable isotopic methods for investigating protein and amino-acid metabolism in man. Refs

Isotopic fractionation of gases during its migration: experiments and 2D numerical simulation

Science.gov (United States)

Kara, S.; Prinzhofer, A.

2003-04-01

Several works have been developed in the last decade on the experimental isotope fractionation of gases during migration (Prinzhofer et al., 1997 and Zhang &Krooss, 2001 among others). We add to these results new experiments on diffusion of CO_2, which becomes currently a crucial subject for environmental purpose. Our experiments showed that transport by diffusion of CO_2 through a water saturated shale induces a significant and systematic carbon isotopic fractionation with heavier (13C enriched) CO_2 migrating first. In all experiments, significant isotope fractionation was found but still remains without quantitative interpretation. To interpret these data, we developed a 2D numerical model at the pore scale. The general principle of this model is the study of transport by water solubilization/diffusion of gas in a capillary saturated with water with two different media : a mobile zone representing free water and a immobile zone representing bounded water. The model takes also into account solubilization coefficients of gas in water, as well as the migration distance and the volume of upstream and downstream reservoirs. Using our numerical model, we could reproduce the evolution of isotopic fractionations and the velocity of CO_2 migration versus the production factor F (proportion of diffused gas). We determined some physical parameters of the porous medium (bentonite) which are not directly measurable at the present time. Furthermore, we used these parameters to reproduce the curves of isotopic fractionation obtained by Pernaton (1998) on methane migration with the same porous rock. We used also a modified version of this model with infinite reservoirs to reproduce the curves of isotopic fractionation of Zhang &Krooss (2001). Application of this model to geological scale is under progress, in order to implement it into sedimentary basins modelling. REFERENCES: Zhang T. and Krooss M. (2001). Geochim. Cosmochim. Acta, Vol. 65, No.16, pp. 2723-2742. Pernaton E

Plants increase laccase activity in soil with long-term elevated CO2 legacy

DEFF Research Database (Denmark)

Partavian, Asrin; Mikkelsen, Teis Nørgaard; Vestergård, Mette

2015-01-01

[CO2] stimulate laccase activity. We incubated soil exposed to seven years of elevated or ambient field [CO2] in ambient or elevated [CO2] chambers for six months either with or without plants (Deschampsia flexuosa). Elevated chamber [CO2] increased D. flexuosa production and belowground respiration....... Interestingly, plants also grew larger in soil with an elevated [CO2] legacy. Plants stimulated soil microbial biomass, belowground respiration and laccase activity, and the plant-induced laccase stimulation was particularly apparent in soil exposed to long-term elevated [CO2] in the field, whereas laccase......Actively growing plants can stimulate mineralization of recalcitrant soil organic matter (SOM), and increased atmospheric [CO2] can further enhance such plant-mediated SOM degradation. Laccases are central for recalcitrant SOM decomposition, and we therefore hypothesized that plants and elevated...

Atmospheric inversion of the surface CO2 flux with 13CO2 constraint

Science.gov (United States)

Chen, J. M.; Mo, G.; Deng, F.

2013-10-01

Observations of 13CO2 at 73 sites compiled in the GLOBALVIEW database are used for an additional constraint in a global atmospheric inversion of the surface CO2 flux using CO2 observations at 210 sites for the 2002-2004 period for 39 land regions and 11 ocean regions. This constraint is implemented using the 13CO2/CO2 flux ratio modeled with a terrestrial ecosystem model and an ocean model. These models simulate 13CO2 discrimination rates of terrestrial photosynthesis and respiration and ocean-atmosphere diffusion processes. In both models, the 13CO2 disequilibrium between fluxes to and from the atmosphere is considered due to the historical change in atmospheric 13CO2 concentration. For the 2002-2004 period, the 13CO2 constraint on the inversion increases the total land carbon sink from 3.40 to 3.70 Pg C yr-1 and decreases the total oceanic carbon sink from 1.48 to 1.12 Pg C yr-1. The largest changes occur in tropical areas: a considerable decrease in the carbon source in the Amazon forest, and this decrease is mostly compensated by increases in the ocean region immediately west of the Amazon and the southeast Asian land region. Our further investigation through different treatments of the 13CO2/CO2 flux ratio used in the inversion suggests that variable spatial distributions of the 13CO2 isotopic discrimination rate simulated by the models over land and ocean have considerable impacts on the spatial distribution of the inverted CO2 flux over land and the inversion results are not sensitive to errors in the estimated disequilibria over land and ocean.

CO2 production in animals: analysis of potential errors in the doubly labeled water method

International Nuclear Information System (INIS)

Nagy, K.A.

1979-03-01

Laboratory validation studies indicate that doubly labeled water ( 3 HH 18 O and 2 HH 18 O) measurements of CO 2 production are accurate to within +-9% in nine species of mammals and reptiles, a bird, and an insect. However, in field studies, errors can be much larger under certain circumstances. Isotopic fraction of labeled water can cause large errors in animals whose evaporative water loss comprises a major proportion of total water efflux. Input of CO 2 across lungs and skin caused errors exceeding +80% in kangaroo rats exposed to air containing 3.4% unlabeled CO 2 . Analytical errors of +-1% in isotope concentrations can cause calculated rates of CO 2 production to contain errors exceeding +-70% in some circumstances. These occur: 1) when little decline in isotope concentractions has occured during the measurement period; 2) when final isotope concentrations closely approach background levels; and 3) when the rate of water flux in an animal is high relative to its rate of CO 2 production. The following sources of error are probably negligible in most situations: 1) use of an inappropriate equation for calculating CO 2 production, 2) variations in rates of water or CO 2 flux through time, 3) use of H 2 O-18 dilution space as a measure of body water volume, 4) exchange of 0-18 between water and nonaqueous compounds in animals (including excrement), 5) incomplete mixing of isotopes in the animal, and 6) input of unlabeled water via lungs and skin. Errors in field measurements of CO 2 production can be reduced to acceptable levels (< 10%) by appropriate selection of study subjects and recapture intervals

Hydrogen/deuterium fractionation factors of the aqueous ligand of cobalt in Co(H2O)62+ and Co(II)-substituted carbonic anhydrase

International Nuclear Information System (INIS)

Kassebaum, J.W.

1988-01-01

The author has measured the hydrogen/deuterium fractionation factor for the rapidly exchanging aqueous ligands of cobalt in Co(H 2 O) 6 2+ and in three Co(II)-substituted isozymes of carbonic anhydrase. The fractionation factor was determined from NMR relaxation rates at 300 MHz of the protons of water in mixed solutions of H 2 O and D 2 O containing these complexes. In each case, the paramagnetic contribution to 1/T 2 was greater than to 1/T 1 , consistent with a chemical shift mechanism affecting 1/T 2 . The fractionation factors obtained from T 2 were 0.73 ± 0.02 for Co(H 2 O) 6 2+ , 0.72 ± 0.02 for Co(II)-substituted carbonic anhydrase I, 0.77 ± 0.01 for Co(II)-substituted carbonic anhydrase II, and 1.00 ± 0.07 for Co(Il)-substituted carbonic anhydrase III. He concluded that fractionation factors in these cases determined from T 1 and T 2 measured isotope preferences for different populations of ligand sites. Since T 2 has a large contribution from a chemical shift mechanism, the fractionation factor determined from T 2 has a large contribution of the fractionation of inner shell ligands. The fractionation factor of Co(H 2 O) 6 2+ was used to interpret the solvent hydrogen isotope effects on the formation of complexes of cobalt with the bidentate ligands glycine, N,N-dimethylglycine, and acetylacetone. The contribution of the fractionation factor of the inner water shell in Co(H 2 O) 6 2+ did not account completely for the measured isotope effect, and that the hydrogen/deuterium fractionation of outer shell water makes a large contribution to the isotope effect on the formation of these complexes

Isotopic versus micrometeorologic ocean CO2 fluxes: A serious conflict

International Nuclear Information System (INIS)

Broecker, W.S.; Ledwell, J.R.; Takahashi, T.; Weiss, R.; Merlivat, L.; Memery, L.; Tsung-Hung Peng; Jahne, B.; Otto Munnich, K.

1986-01-01

Eddy correlation measurements over the ocean give CO 2 fluxes an order of magnitude or more larger than expected from mass balance or more larger than expected from mass balance measurements using radiocarbon and radon 222. In particular, Smith and Jones (1985) reported large upward and downward fluxes in a surf zone at supersaturations of 15% and attributed them to the equilibration of bubbles at elevated pressures. They argue that even on the open ocean such bubble injection may create steady state CO 2 supersaturations and that inferences of fluxes based on air-sea pCO 2 differences and radon exchange velocities must be made with caution. We defend the global average CO 2 exchange rate determined by three independent radioisotopic means: prebomb radiocarbon inventories; global surveys of mixed layer radon deficits; and oceanic uptake of bomb-produced radiocarbon. We argue that laboratory and lake data do not lead one to expect fluxes as large as reported from the eddy correlation technique; that the radon method of determining exchange velocities is indeed useful for estimating CO 2 fluxes; that supersaturations of CO 2 due to bubble injection on the open ocean are negligible; that the hypothesis that Smith and Jones advance cannot account for the fluxes that they report; and that the pCO 2 values reported by Smith and Jones are likely to be systematically much too high. The CO 2 fluxes for the ocean measured to data by the micrometeorological method can be reconciled with neither the observed concentrations of radioisotopes of radon and carbon in the oceans nor the tracer experiments carried out in lakes and in wind/wave tunnels

Chemisorption of CO and mechanism of CO oxidation on supported platinum nanoclusters

KAUST Repository

Allian, Ayman Daoud

2011-03-30

Kinetic, isotopic, and infrared studies on well-defined dispersed Pt clusters are combined here with first-principle theoretical methods on model cluster surfaces to probe the mechanism and structural requirements for CO oxidation catalysis at conditions typical of its industrial practice. CO oxidation turnover rates and the dynamics and thermodynamics of adsorption-desorption processes on cluster surfaces saturated with chemisorbed CO were measured on 1-20 nm Pt clusters under conditions of strict kinetic control. Turnover rates are proportional to O2 pressure and inversely proportional to CO pressure, consistent with kinetically relevant irreversible O2 activation steps on vacant sites present within saturated CO monolayers. These conclusions are consistent with the lack of isotopic scrambling in C16O-18O2-16O 2 reactions, and with infrared bands for chemisorbed CO that did not change within a CO pressure range that strongly influenced CO oxidation turnover rates. Density functional theory estimates of rate and equilibrium constants show that the kinetically relevant O2 activation steps involve direct O2* (or O2) reactions with CO* to form reactive O*-O-C*=O intermediates that decompose to form CO 2 and chemisorbed O*, instead of unassisted activation steps involving molecular adsorption and subsequent dissociation of O2. These CO-assisted O2 dissociation pathways avoid the higher barriers imposed by the spin-forbidden transitions required for unassisted O2 dissociation on surfaces saturated with chemisorbed CO. Measured rate parameters for CO oxidation were independent of Pt cluster size; these parameters depend on the ratio of rate constants for O2 reactions with CO* and CO adsorption equilibrium constants, which reflect the respective activation barriers and reaction enthalpies for these two steps. Infrared spectra during isotopic displacement and thermal desorption with 12CO- 13CO mixtures showed that the binding, dynamics, and thermodynamics of CO

Multiple Nebular Gas Reservoirs Recorded by Oxygen Isotope Variation in a Spinel-rich CAI in CO3 MIL 090019

Science.gov (United States)

Simon, J. I.; Simon, S. B.; Nguyen, A. N.; Ross, D. K.; Messenger, S.

2017-01-01

We conducted NanoSIMS O-isotopic imaging of a primitive spinel-rich CAI spherule (27-2) from the MIL 090019 CO3 chondrite. Inclusions such as 27-2 are proposed to record inner nebula processes during an epoch of rapid solar nebula evolution. Mineralogical and textural analyses suggest that this CAI formed by high temperature reactions, partial melting, and condensation. This CAI exhibits radial O-isotopic heterogeneity among multiple occurrences of the same mineral, reflecting interactions with distinct nebular O-isotopic reservoirs.

Chemistry of fluids from a natural analogue for a geological CO{sub 2} storage site (Montmiral, France): Lessons for CO{sub 2}-water-rock interaction assessment and monitoring

Energy Technology Data Exchange (ETDEWEB)

Pauwels, Helene [BRGM - Water Division, 3, av Claude Guillemin, 45060 Orleans Cedex (France)], E-mail: h.pauwels@brgm.fr; Gaus, Irina; Le Nindre, Yves Michel [BRGM - Water Division, 3, av Claude Guillemin, 45060 Orleans Cedex (France); Pearce, Jonathan [British Geological Survey, Kingsley Dunham Centre, Keyworth, Nottingham NG125GG (United Kingdom); Czernichowski-Lauriol, Isabelle [BRGM - Water Division, 3, av Claude Guillemin, 45060 Orleans Cedex (France)

2007-12-15

Chemical and isotope studies of natural CO{sub 2} accumulations aid in assessing the chemical effects of CO{sub 2} on rock and thus provide a potential for understanding the long-term geochemical processes involved in CO{sub 2} geological storage. Several natural CO{sub 2} accumulations were discovered during gas and oil exploration in France's carbogaseous peri-Alpine province (south-eastern France) in the 1960s. One of these, the Montmiral accumulation at a depth of more than 2400 m, is currently being exploited. The chemical composition of the water collected at the wellhead has changed in time and the final salinity exceeds 75 g/L. These changes in time can be explained by assuming that the fraction of the reservoir brine in the recovered brine-CO{sub 2}-H{sub 2}O mixture varies, resulting in variable proportions of H{sub 2}O and brine in the sampled water. The proportions can be estimated in selected samples due to the availability of gas and water flowrate data. These data enabled the reconstruction of the chemical and isotope composition of the brine. The proportions of H{sub 2}O and brine can also be estimated from isotope ({delta}{sup 2}H, {delta}{sup 18}O) composition of collected water and {delta}{sup 18}O of the sulfates or CO{sub 2}. The reconstituted brine has a salinity of more than 85 g/L and, according to its Br{sup -} content and isotope ({delta}{sup 2}H, {delta}{sup 18}O, {delta}{sup 34}S) composition, originates from an evaporated Triassic seawater that underwent dilution by meteoric water. The reconstitution of the brine's chemical composition enabled an evaluation of the CO{sub 2}-water-rock interactions based on: (1) mineral saturation indices; and (2) comparison with initial evaporated Triassic seawater. Dissolution of K- and SO{sub 4}-containing minerals such as K-feldspar and anhydrite, and precipitation of Ca and Mg containing minerals that are able to trap CO{sub 2} (carbonates) are highlighted. The changes in concentration of

Production of activated carbons from coffee endocarp by CO2 and steam activation

International Nuclear Information System (INIS)

Nabais, Joao M. Valente; Nunes, Pedro; Carrott, Peter J.M.; Ribeiro Carrott, M. Manuela L.; Garcia, A. Macias; Diaz-Diez, M.A.

2008-01-01

In this work the use of coffee endocarp as precursor for the production of activated carbons by steam and CO 2 was studied. Activation by both methods produces activated carbons with small external areas and microporous structures having very similar mean pore widths. The activation produces mainly primary micropores and only a small volume of larger micropores. The CO 2 activation leads to samples with higher BET surface areas and pore volumes when compared with samples produced by steam activation and with similar burn-off value. All the activated carbons produced have basic characteristics with point of zero charge between 10 and 12. By FTIR it was possible to identify the formation on the activated carbon's surface of several functional groups, namely ether, quinones, lactones, ketones, hydroxyls (free and phenol); pyrones and Si-H bonds. (author)

Comparative study of CO2 and H2O activation in the synthesis of carbon electrode for supercapacitors

Science.gov (United States)

Taer, E.; Apriwandi, Yusriwandi, Mustika, W. S.; Zulkifli, Taslim, R.; Sugianto, Kurniasih, B.; Agustino, Dewi, P.

2018-02-01

The physical activation for the comparative study of carbon electrode synthesized for supercapacitor applications made from rubber wood sawdust has been performed successfully. Comparison of physical activation used in this research is based on the different gas activation such as CO2 and H2O. The CO2 and H2O activation are made by using an integrated carbonization and activation system. The carbonization process is performed in N2 atmosphere followed by CO2 and H2O activation process. The carbonization process at temperature of 600°C, the CO2 and H2O activation process at a temperature of 900°C and maintained at this condition for 2 h and 3 h. The electrochemical properties were analyzed using cyclic voltammetric (CV) method. The CV results show that the carbon electrode with CO2 activation has better capacitive properties than H2O, the highest specific capacitance obtained is 93.22 F/g for 3 h of activation time. In addition, the analysis of physical properties such as surface morphology and degree of crystallinity was also performed.

High-power CO laser with RF discharge for isotope separation employing condensation repression

Science.gov (United States)

Baranov, I. Ya.; Koptev, A. V.

2008-10-01

High-power CO laser can be the effective tool in such applications as isotope separation using the free-jet CRISLA method. The way of transfer from CO small-scale experimental installation to industrial high-power CO lasers is proposed through the use of a low-current radio-frequency (RF) electric discharge in a supersonic stream without an electron gun. The calculation model of scaling CO laser with RF discharge in supersonic stream was developed. The developed model allows to calculate parameters of laser installation and optimize them with the purpose of reception of high efficiency and low cost of installation as a whole. The technical decision of industrial CO laser for isotope separation employing condensation repression is considered. The estimated cost of laser is some hundred thousand dollars USA and small sizes of laser head give possibility to install it in any place.

The Effect of CO2 Activation on the Electrochemical Performance of Coke-Based Activated Carbons for Supercapacitors.

Science.gov (United States)

Lee, Hye-Min; Kim, Hong-Gun; An, Kay-Hyeok; Kim, Byung-Joo

2015-11-01

The present study developed electrode materials for supercapacitors by activating coke-based activated carbons with CO2. For the activation reaction, after setting the temperature at 1,000 degrees C, four types of activated carbons were produced, over an activation time of 0-90 minutes and with an interval of 30 minutes as the unit. The electrochemical performance of the activated carbons produced was evaluated to examine the effect of CO2 activation. The surface structure of the porous carbons activated through CO2 activation was observed using a scanning electron microscope (SEM). To determine the N2/77 K isothermal adsorption characteristics, the Brunauer-Emmett-Teller (BET) equation and the Barrett-Joyner-Halenda (BJH) equation were used to analyze the pore characteristics. In addition, charge and discharge tests and cyclic voltammetry (CV) were used to analyze the electrochemical characteristics of the changed pore structure. According to the results of the experiments, the N2 adsorption isotherm curves of the porous carbons produced belonged to Type IV in the International Union of Pore and Applied Chemistry (IUPAC) classification and consisted of micropores and mesopores, and, as the activation of CO2 progressed, micropores decreased and mesopores developed. The specific surface area of the porous carbons activated by CO2 was 1,090-1,180 m2/g and thus showed little change, but those of mesopores were 0.43-0.85 cm3/g, thus increasing considerably. In addition, when the electrochemical characteristics were analyzed, the specific capacity was confirmed to have increased from 13.9 F/g to 18.3 F/g. From these results, the pore characteristics of coke-based activated carbons changed considerably because of CO2 activation, and it was therefore possible to increase the electrochemical characteristics.

Porous carbon derived via KOH activation of a hypercrosslinked porous organic polymer for efficient CO_2, CH_4, H_2 adsorptions and high CO_2/N_2 selectivity

International Nuclear Information System (INIS)

Modak, Arindam; Bhaumik, Asim

2015-01-01

Microporous carbon having Brunauer-Emmett-Teller (BET) surface area of 2186 m"2 g"−"1 and micropore volume of 0.85 cm"3 g"−"1 has been synthesized via KOH induced high temperature carbonization of a non-conjugated hypercrosslinked organic polymer. Owing to the templating and activation by KOH, we have succeeded in making a microporous carbon from this porous polymer and the resultant carbon material showed high uptake for CO_2 (7.6 mmol g"−"1) and CH_4 (2.4 mmol g"−"1) at 1 atm, 273 K together with very good selectivity for the CO_2/N_2 (30.2) separation. Furthermore, low pressure (1 atm) H_2 (2.6 wt%, 77 K) and water uptake (57.4 wt%, 298 K) ability of this polymer derived porous activated carbon is noteworthy. - Graphical abstract: Microporous carbon with BET surface area of 2186 m"2 g"−"1 has been synthesized via KOH activation of a porous organic polymer and it showed high uptake for CO_2 (7.6 mmol g"−"1), CH_4 (2.4 mmol g"−"1) and H_2 (2.6 wt%) at 1 atm together with very good selectivity for CO_2. - Highlights: • Porous carbon from hypercrosslinked organic polymer. • KOH activated carbon with BET surface area 2186 m"2 g"−"1. • High CO2 uptake (7.6 mmol g"−"1) and CO_2/N_2 selectivity (30.2). • Porous carbon also showed high H_2 (2.6 wt%) and H_2O (57.4 wt%) uptakes.

Enrichment: CRISLA [chemical reaction by isotope selective activation] aims to reduce costs

International Nuclear Information System (INIS)

Eerkens, J.W.

1989-01-01

Every year, more than $3 billion is spent on enriching uranium. CRISLA (Chemical Reaction by Isotope Selective Activation) uses a laser-catalyzed chemical reaction which, its proponents claim, could substantially reduce these costs. In CRISLA, an infrared CO laser illuminates the intracavity reaction cell (IC) at a frequency tuned to excite primarily UF 6 . When UF 6 and co-reactant RX are passed through the IC, the tuned laser photons preferentially enhance the reaction of UF 6 with RX ten-thousand-fold over the thermal reaction rate. Thus the laser serves as an activator and the chemical energy for separation is largely chemical. (author)

Environmental controls on the carbon isotope composition of ecosystem-respired CO{sub 2} in contrasting forest ecosystems in Canada and the USA

Energy Technology Data Exchange (ETDEWEB)

Alstad, K.P. [Lethbridge Univ., Lethbridge, AB (Canada). Dept. of Biological Sciences; Toledo Univ., Toledo, OH (United States). Dept. of Environmental Sciences; Flanagan, L.B. [Lethbridge Univ., Lethbridge, AB (Canada). Dept. of Biological Sciences; Lai, C.T. [Utah Univ., Salt Lake City, UT (United States); San Diego State Univ., San Diego, CA (United States); Ehleringer, J.R. [Utah Univ., Salt Lake City, UT (United States)

2007-10-15

Eleven forest ecosystems in Canada and the United States were compared in order to test for differences among forest {delta}{sup 13} carbon (C) responses to seasonal variations in environmental conditions from May to October 2004. Carbon isotope composition of ecosystem-respired carbon dioxide (CO{sub 2}) was considered as a proxy for short-term changes in photosynthetic discrimination. The study compared coniferous and deciduous forests, as well as forests in boreal and coastal environments. It was hypothesized that the carbon isotope composition of ecosystem-respired CO{sub 2} varied in a manner consistent with results obtained in leaf-level studies. Results of the study showed that higher R{sup 2} values were obtained for coastal ecosystems. The relationships between {delta}{sup 13}C{sub R} and environmental conditions were consistent with results obtained from leaf-level studies. Vapour pressure deficits and soil temperatures were significant determinants of variations in {delta}{sup 13}C{sub R} in the boreal forest ecosystem. Variations in {delta}{sup 13}C{sub R} in the coastal forest ecosystem correlated with changes in photosynthetic photon flux (PPF). It was concluded that {delta}{sup 13}C{sub R} measurements can be used to assess yearly variations in ecosystem physiological responses to changing environmental conditions. 59 refs., 7 tabs., 6 figs.

Cyanobacterial carbon concentrating mechanisms facilitate sustained CO2 depletion in eutrophic lakes

Science.gov (United States)

Morales-Williams, Ana M.; Wanamaker, Alan D., Jr.; Downing, John A.

2017-06-01

Phytoplankton blooms are increasing in frequency, intensity, and duration in aquatic ecosystems worldwide. In many eutrophic lakes, these high levels of primary productivity correspond to periods of CO2 depletion in surface waters. Cyanobacteria and other groups of phytoplankton have the ability to actively transport bicarbonate (HCO3-) across their cell membrane when CO2 concentrations are limiting, possibly giving them a competitive advantage over algae not using carbon concentrating mechanisms (CCMs). To investigate whether CCMs can maintain phytoplankton bloom biomass under CO2 depletion, we measured the δ13C signatures of dissolved inorganic carbon (δ13CDIC) and phytoplankton particulate organic carbon (δ13Cphyto) in 16 mesotrophic to hypereutrophic lakes during the ice-free season of 2012. We used mass-balance relationships to determine the dominant inorganic carbon species used by phytoplankton under CO2 stress. We found a significant positive relationship between phytoplankton biomass and phytoplankton δ13C signatures as well as a significant nonlinear negative relationship between water column ρCO2 and isotopic composition of phytoplankton, indicating a shift from diffusive uptake to active uptake by phytoplankton of CO2 or HCO3- during blooms. Calculated photosynthetic fractionation factors indicated that this shift occurs specifically when surface water CO2 drops below atmospheric equilibrium. Our results indicate that active HCO3- uptake via CCMs may be an important mechanism in maintaining phytoplankton blooms when CO2 is depleted. Further increases in anthropogenic pressure, eutrophication, and cyanobacteria blooms are therefore expected to contribute to increased bicarbonate uptake to sustain primary production.

Cyanobacterial carbon concentrating mechanisms facilitate sustained CO2 depletion in eutrophic lakes

Directory of Open Access Journals (Sweden)

A. M. Morales-Williams

2017-06-01

Full Text Available Phytoplankton blooms are increasing in frequency, intensity, and duration in aquatic ecosystems worldwide. In many eutrophic lakes, these high levels of primary productivity correspond to periods of CO2 depletion in surface waters. Cyanobacteria and other groups of phytoplankton have the ability to actively transport bicarbonate (HCO3− across their cell membrane when CO2 concentrations are limiting, possibly giving them a competitive advantage over algae not using carbon concentrating mechanisms (CCMs. To investigate whether CCMs can maintain phytoplankton bloom biomass under CO2 depletion, we measured the δ13C signatures of dissolved inorganic carbon (δ13CDIC and phytoplankton particulate organic carbon (δ13Cphyto in 16 mesotrophic to hypereutrophic lakes during the ice-free season of 2012. We used mass–balance relationships to determine the dominant inorganic carbon species used by phytoplankton under CO2 stress. We found a significant positive relationship between phytoplankton biomass and phytoplankton δ13C signatures as well as a significant nonlinear negative relationship between water column ρCO2 and isotopic composition of phytoplankton, indicating a shift from diffusive uptake to active uptake by phytoplankton of CO2 or HCO3− during blooms. Calculated photosynthetic fractionation factors indicated that this shift occurs specifically when surface water CO2 drops below atmospheric equilibrium. Our results indicate that active HCO3− uptake via CCMs may be an important mechanism in maintaining phytoplankton blooms when CO2 is depleted. Further increases in anthropogenic pressure, eutrophication, and cyanobacteria blooms are therefore expected to contribute to increased bicarbonate uptake to sustain primary production.

Impact of elevated CO_2 concentrations on carbonate mineral precipitation ability of sulfate-reducing bacteria and implications for CO_2 sequestration

International Nuclear Information System (INIS)

Paul, Varun G.; Wronkiewicz, David J.; Mormile, Melanie R.

2017-01-01

Interest in anthropogenic CO_2 release and associated global climatic change has prompted numerous laboratory-scale and commercial efforts focused on capturing, sequestering or utilizing CO_2 in the subsurface. Known carbonate mineral precipitating microorganisms, such as the anaerobic sulfate-reducing bacteria (SRB), could enhance the rate of conversion of CO_2 into solid minerals and thereby improve long-term storage of captured gasses. The ability of SRB to induce carbonate mineral precipitation, when exposed to atmospheric and elevated pCO_2, was investigated in laboratory scale tests with bacteria from organic-rich sediments collected from hypersaline Lake Estancia, New Mexico. The enriched SRB culture was inoculated in continuous gas flow and batch reactors under variable headspace pCO_2 (0.0059 psi to 20 psi). Solution pH, redox conditions, sulfide, calcium and magnesium concentrations were monitored in the reactors. Those reactors containing SRB that were exposed to pCO_2 of 14.7 psi or less showed Mg-calcite precipitation. Reactors exposed to 20 psi pCO_2 did not exhibit any carbonate mineralization, likely due to the inhibition of bacterial metabolism caused by the high levels of CO_2. Hydrogen, lactate and formate served as suitable electron donors for the SRB metabolism and related carbonate mineralization. Carbon isotopic studies confirmed that ∼53% of carbon in the precipitated carbonate minerals was derived from the CO_2 headspace, with the remaining carbon being derived from the organic electron donors, and the bicarbonate ions available in the liquid medium. The ability of halotolerant SRB to induce the precipitation of carbonate minerals can potentially be applied to the long-term storage of anthropogenic CO_2 in saline aquifers and other ideal subsurface rock units by converting the gas into solid immobile phases. - Highlights: • SRB under study are capable of precipitating calcite up to 14.7 psi pCO_2. • At 20 psi pCO_2, bacterial activity

Evidence for H2/D2 isotope effects on Fischer-Tropsch synthesis over supported ruthenium catalysts

International Nuclear Information System (INIS)

Kellner, C.S.; Bell, A.T.

1981-01-01

The effects of using D 2 rather than H 2 during Fischer-Tropsch synthesis were investigated using alumina- and silica-supported Ru catalysts. For the alumina-supported catalysts, the rate of CD 4 formation was 1.4 to 1.6 times faster than the formation of CH 4 . A noticeable isotope effect was also observed for higher molecular weight products. The magnitude of the isotope effects observed using the silica-supported catalyst was much smaller than that found using the alumina-supported catalysts. The formation of olefins relative to paraffins was found to be higher when H 2 rather than D 2 was used, independent of the catalyst support. The observed isotope effects are explained in terms of a mechanism for CO hydrogenation and are shown to arise from a complex combination of the kinetic and equilibrium isotope effects associated with elementary processes occurring on the catalyst surface

Highly Surface-Active Ca(OH)2 Monolayer as a CO2 Capture Material.

Science.gov (United States)

Özçelik, V Ongun; Gong, Kai; White, Claire E

2018-03-14

Greenhouse gas emissions originating from fossil fuel combustion contribute significantly to global warming, and therefore the design of novel materials that efficiently capture CO 2 can play a crucial role in solving this challenge. Here, we show that reducing the dimensionality of bulk crystalline portlandite results in a stable monolayer material, named portlandene, that is highly effective at capturing CO 2 . On the basis of theoretical analysis comprised of ab initio quantum mechanical calculations and force-field molecular dynamics simulations, we show that this single-layer phase is robust and maintains its stability even at high temperatures. The chemical activity of portlandene is seen to further increase upon defect engineering of its surface using vacancy sites. Defect-containing portlandene is capable of separating CO and CO 2 from a syngas (CO/CO 2 /H 2 ) stream, yet is inert to water vapor. This selective behavior and the associated mechanisms have been elucidated by examining the electronic structure, local charge distribution, and bonding orbitals of portlandene. Additionally, unlike conventional CO 2 capturing technologies, the regeneration process of portlandene does not require high temperature heat treatment because it can release the captured CO 2 by application of a mild external electric field, making portlandene an ideal CO 2 capturing material for both pre- and postcombustion processes.

Application of environmental isotopes to characterize landfill gases and leachate

International Nuclear Information System (INIS)

Liu, C.L.; Hackley, K.C.; Baker, J.

1992-01-01

Environmental isotopes have been used to help characterize landfill gases and leachate for the purpose of identifying leachate and/or gas contamination in surrounding monitoring wells. Carbon isotopes (C-13/C-12 and C-14), hydrogen isotopes (H-3 and H-2/H-1) and oxygen isotopes (O-18/O-16) were used to characterize methane, carbon dioxide and leachate produced from two municipal landfills in northeastern Illinois. The isotopic results from the landfill-derived gases and leachate are compared to isotopic compositions of groundwater and gases from nearby monitoring wells. C-14 activity of landfill CH 4 is high compared to CH 4 normally found in subsurface sediments. For this study C-14 activities of the landfill methane range from 129--140 PMC. The C-14 of the dissolved inorganic carbon (DIC) of the leachate samples also have relatively high activities, ranging from 126--141 PMC. The δC-13 and δD values for CH 4 from the landfills fall within a range of values representative of microbial methane produced by acetate-fermentation. The δC-13 of the CO 2 and the DIC are very positive, ranging from 8--14 per-thousand for CO 2 and 13--22 per-thousand for DIC. The δO-18 values of the leachates are similar to current meteoric water values, however, two of the leachate samples are significantly enriched in deuterium by approximately 65 per-thousand. Tritium values of the leachate water are generally higher than expected. For one landfill the tritium activity ranges from 227--338 TU, for the second landfill the tritium activity is approximately 1,300 TU. Compared to tritium levels in normal groundwater, these higher tritium values in the leachates indicate that this isotope has the potential to be an effective tracer for detecting leachate migration

The Activity Check of Brachytherapy Isotope

International Nuclear Information System (INIS)

Kim, Gun Oh; Lee, Byung Koo; Kwon, Young Ho

2004-01-01

An isotope Ir-192, which is used in brachytherapy depends on import in whole quantities. There are a few ways for its activity. measurement using Welltype chamber or the way to rely on authentic decay table of manufacturer. In-air dosimetry using Farmer Chamber, etc. In this paper, let me introduce the way using Farmer chamber which is easier and simple. With the Farmer chamber and source calibration jig, take a measurement the activity of an isotope Ir-192 and compare the value with the value from decay table of manufacturer and check the activity of source. The result of measurement, compared the value from decay table, by ±2.1. (which belongs to recommendable value for AAPM ±5% as difference of error range). It is possible to use on clinical medicine. With the increase in use of brachytherapy, the increase of import is essential. And an accurate activity check of source is compulsory. For the activity check of source, it was possible to use Farmer chamber and source calibration jig without additional purchase of Well type chamber.

Soil CO2 efflux measurement network by means of closed static chambers to monitor volcanic activity at Tenerife, Canary Islands

Science.gov (United States)

Amonte, Cecilia; García-Merino, Marta; Asensio-Ramos, María; Melián, Gladys; García-Hernández, Rubén; Pérez, Aaron; Hernández, Pedro A.; Pérez, Nemesio M.

2017-04-01

Tenerife (2304 km2) is the largest of the Canary Islands and has developed a central volcanic complex (Cañadas edifice), that started to grow about 3.5 My ago. Coeval with the construction of the Cañadas edifice, shield basaltic volcanism continued until the present along three rift zones oriented NW-SE, NE-SW and NS (hereinafter referred as NW, NE and NS respectively). Main volcanic historical activity has occurred along de NW and NE rift-zones, although summit cone of Teide volcano, in central volcanic complex, is the only area of the island where surface geothermal manifestations are visible. Uprising of deep-seated gases occurs along the aforementioned volcanic structures causing diffuse emissions at the surface environment of the rift-zones. In the last 20 years, there has been considerable interest in the study of diffuse degassing as a powerful tool in volcano monitoring programs. Diffuse degassing studies are even more important volcanic surveillance tool at those volcanic areas where visible manifestations of volcanic gases are absent. Historically, soil gas and diffuse degassing surveys in volcanic environments have focused mainly on CO2 because it is, after water vapor, the most abundant gas dissolved in magma. One of the most popular methods used to determine CO2 fluxes in soil sciences is based on the absorption of CO2 through an alkaline medium, in its solid or liquid form, followed by gravimetric, conductivity, or titration analyses. In the summer of 2016, a network of 31 closed static chambers was installed, covering the three main structural zones of Tenerife (NE, NW and NS) as well as Cañadas Caldera with volcanic surveillance porpoises. 50 cc of 0.1N KOH solution is placed inside the chamber to absorb the CO2 released from the soil. The solution is replaced weekly and the trapped CO2 is then analyzed at the laboratory by titration. The are expressed as weekly integrated CO2 efflux values. The CO2 efflux values ranged from 3.2 to 12.9 gṡm-2�

Heterologous Expression of the Clostridium carboxidivorans CO Dehydrogenase Alone or Together with the Acetyl Coenzyme A Synthase Enables both Reduction of CO2 and Oxidation of CO by Clostridium acetobutylicum.

Science.gov (United States)

Carlson, Ellinor D; Papoutsakis, Eleftherios T

2017-08-15

With recent advances in synthetic biology, CO 2 could be utilized as a carbon feedstock by native or engineered organisms, assuming the availability of electrons. Two key enzymes used in autotrophic CO 2 fixation are the CO dehydrogenase (CODH) and acetyl coenzyme A (acetyl-CoA) synthase (ACS), which form a bifunctional heterotetrameric complex. The CODH/ACS complex can reversibly catalyze CO 2 to CO, effectively enabling a biological water-gas shift reaction at ambient temperatures and pressures. The CODH/ACS complex is part of the Wood-Ljungdahl pathway (WLP) used by acetogens to fix CO 2 , and it has been well characterized in native hosts. So far, only a few recombinant CODH/ACS complexes have been expressed in heterologous hosts, none of which demonstrated in vivo CO 2 reduction. Here, functional expression of the Clostridium carboxidivorans CODH/ACS complex is demonstrated in the solventogen Clostridium acetobutylicum , which was engineered to express CODH alone or together with the ACS. Both strains exhibited CO 2 reduction and CO oxidation activities. The CODH reactions were interrogated using isotopic labeling, thus verifying that CO was a direct product of CO 2 reduction, and vice versa. CODH apparently uses a native C. acetobutylicum ferredoxin as an electron carrier for CO 2 reduction. Heterologous CODH activity depended on actively growing cells and required the addition of nickel, which is inserted into CODH without the need to express the native Ni insertase protein. Increasing CO concentrations in the gas phase inhibited CODH activity and altered the metabolite profile of the CODH-expressing cells. This work provides the foundation for engineering a complete and functional WLP in nonnative host organisms. IMPORTANCE Functional expression of CO dehydrogenase (CODH) from Clostridium carboxidivorans was demonstrated in C. acetobutylicum , which is natively incapable of CO 2 fixation. The expression of CODH, alone or together with the C. carboxidivorans

A study on the isotope effects in the reduction of carbon dioxide by zinc

International Nuclear Information System (INIS)

Senegacnik, M.

1957-06-01

We have determined the isotope effects which occur in the reduction of carbon dioxide by zinc. It has been shown that in the case of irreversible surface reactions, Bernstein's equation which permits the calculation of the fractionation factor is still valid. These experimental factors are in good agreement with those obtained by calculating the partition functions of the adsorbed activated complexes. In the reaction mechanism used, the model of the activated complex corresponds to the dissociation of one of the carbon oxygen bonds CO 2 → CO + O. Perturbations arising from the slight reversibility of the reaction Zn + CO 2 ↔ ZnO + CO on the isotope effects on the carbon and oxygen atoms have also been calculated. (author) [fr

Carbon isotopes in mollusk shell carbonates

Science.gov (United States)

McConnaughey, Ted A.; Gillikin, David Paul

2008-10-01

Mollusk shells contain many isotopic clues about calcification physiology and environmental conditions at the time of shell formation. In this review, we use both published and unpublished data to discuss carbon isotopes in both bivalve and gastropod shell carbonates. Land snails construct their shells mainly from respired CO2, and shell δ13C reflects the local mix of C3 and C4 plants consumed. Shell δ13C is typically >10‰ heavier than diet, probably because respiratory gas exchange discards CO2, and retains the isotopically heavier HCO3 -. Respired CO2 contributes less to the shells of aquatic mollusks, because CO2/O2 ratios are usually higher in water than in air, leading to more replacement of respired CO2 by environmental CO2. Fluid exchange with the environment also brings additional dissolved inorganic carbon (DIC) into the calcification site. Shell δ13C is typically a few ‰ lower than ambient DIC, and often decreases with age. Shell δ13C retains clues about processes such as ecosystem metabolism and estuarine mixing. Ca2+ ATPase-based models of calcification physiology developed for corals and algae likely apply to mollusks, too, but lower pH and carbonic anhydrase at the calcification site probably suppress kinetic isotope effects. Carbon isotopes in biogenic carbonates are clearly complex, but cautious interpretation can provide a wealth of information, especially after vital effects are better understood.

A Tale of Two Gases: Isotope Effects Associated with the Enzymatic Production of H2 and N2O

Science.gov (United States)

Yang, H.; Gandhi, H.; Kreuzer, H. W.; Moran, J.; Hill, E. A.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.; Hegg, E. L.

2014-12-01

Stable isotopes can provide considerable insight into enzymatic mechanisms and fluxes in various biological processes. In our studies, we used stable isotopes to characterize both enzyme-catalyzed H2 and N2O production. H2 is a potential alternative clean energy source and also a key metabolite in many microbial communities. Biological H2 production is generally catalyzed by hydrogenases, enzymes that combine protons and electrons to produce H2 under anaerobic conditions. In our study, H isotopes and fractionation factors (α) were used to characterize two types of hydrogenases: [FeFe]- and [NiFe]-hydrogenases. Due to differences in the active site, the α associated with H2 production for [FeFe]- and [NiFe]-hydrogenases separated into two distinct clusters (αFeFe > αNiFe). The calculated kinetic isotope effects indicate that hydrogenase-catalyzed H2 production has a preference for light isotopes, consistent with the relative bond strengths of O-H and H-H bonds. Interestingly, the isotope effects associated with H2 consumption and H2-H2O exchange reactions were also characterized, but in this case no specific difference was observed between the different enzymes. N2O is a potent greenhouse gas with a global warming potential 300 times that of CO2, and the concentration of N2O is currently increasing at a rate of ~0.25% per year. Thus far, bacterial and fungal denitrification processes have been identified as two of the major sources of biologically generated N2O. In this study, we measured the δ15N, δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom in N2O) of N2O generated by purified fungal P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum. We observed normal isotope effects for δ18O and δ15Nα, and inverse isotope effects for bulk δ15N (the average of Nα and Nβ) and δ15Nβ. The observed isotope effects have been used in conjunction with DFT calculations to provide important insight into the mechanism of P450nor. Similar

The influence of clouds and diffuse radiation on ecosystem-atmosphere CO2 and CO18O exhanges

Energy Technology Data Exchange (ETDEWEB)

Still, C.J.; Riley, W.J.; Biraud, S.C.; Noone, D.C.; Buenning, N.H.; Randerson, J.T.; Torn, M.S.; Welker, J.; White, J.W.C.; Vachon, R.; Farquhar, G.D.; Berry, J.A.

2009-05-01

This study evaluates the potential impact of clouds on ecosystem CO{sub 2} and CO{sub 2} isotope fluxes ('isofluxes') in two contrasting ecosystems (a broadleaf deciduous forest and a C{sub 4} grassland), in a region for which cloud cover, meteorological, and isotope data are available for driving the isotope-enabled land surface model, ISOLSM. Our model results indicate a large impact of clouds on ecosystem CO{sub 2} fluxes and isofluxes. Despite lower irradiance on partly cloudy and cloudy days, predicted forest canopy photosynthesis was substantially higher than on clear, sunny days, and the highest carbon uptake was achieved on the cloudiest day. This effect was driven by a large increase in light-limited shade leaf photosynthesis following an increase in the diffuse fraction of irradiance. Photosynthetic isofluxes, by contrast, were largest on partly cloudy days, as leaf water isotopic composition was only slightly depleted and photosynthesis was enhanced, as compared to adjacent clear sky days. On the cloudiest day, the forest exhibited intermediate isofluxes: although photosynthesis was highest on this day, leaf-to-atmosphere isofluxes were reduced from a feedback of transpiration on canopy relative humidity and leaf water. Photosynthesis and isofluxes were both reduced in the C{sub 4} grass canopy with increasing cloud cover and diffuse fraction as a result of near-constant light limitation of photosynthesis. These results suggest that some of the unexplained variation in global mean {delta}{sup 18}O of CO{sub 2} may be driven by large-scale changes in clouds and aerosols and their impacts on diffuse radiation, photosynthesis, and relative humidity.

Silicon isotope separation utilizing infrared multiphoton dissociation of Si{sub 2}F{sub 6} irradiated with two-color CO{sub 2} laser light

Energy Technology Data Exchange (ETDEWEB)

Yokoyama, Atsushi; Ohba, Hironori; Hashimoto, Masashi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Ishii, Takeshi; Ohya, Akio [Nuclear Development Corp., Tokai, Ibaraki (Japan); Arai, Shigeyoshi [Hill Research Co. Ltd., Tokyo (Japan)

2002-08-01

Silicon isotope separation has been done by utilizing the Infrared Multiphoton Dissociation (IRMPD) of Si{sub 2}F{sub 6} irradiated with two-color CO{sub 2} laser lights. The two-color excitation method improved the separation efficiency keeping the high enrichment factors. For example, 99.74% of {sup 28}Si was obtained at 49.63% dissociation of Si{sub 2}F{sub 6} after the simultaneous irradiation of 200 pulses with 966.23 cm{sup -1} photons (0.084 J/cm{sup 2}) and 954.55 cm{sup -1} photons (0.658 J/cm{sup 2}), while 2000 pulses were needed to obtain 99.35% of {sup 28}Si at 35.6% dissociation in the case of only one-color irradiation at 954.55 cm{sup -1} (0.97 J/cm{sup 2}). (author)

Elevated atmospheric CO2 increases microbial growth rates and enzymes activity in soil

Science.gov (United States)

Blagodatskaya, Evgenia; Blagodatsky, Sergey; Dorodnikov, Maxim; Kuzyakov, Yakov

2010-05-01

Increasing the belowground translocation of assimilated carbon by plants grown under elevated CO2 can cause a shift in the structure and activity of the microbial community responsible for the turnover of organic matter in soil. We investigated the long-term effect of elevated CO2 in the atmosphere on microbial biomass and specific growth rates in root-free and rhizosphere soil. The experiments were conducted under two free air carbon dioxide enrichment (FACE) systems: in Hohenheim and Braunschweig, as well as in the intensively managed forest mesocosm of the Biosphere 2 Laboratory (B2L) in Oracle, AZ. Specific microbial growth rates (μ) were determined using the substrate-induced respiration response after glucose and/or yeast extract addition to the soil. We evaluated the effect of elevated CO2 on b-glucosidase, chitinase, phosphatase, and sulfatase to estimate the potential enzyme activity after soil amendment with glucose and nutrients. For B2L and both FACE systems, up to 58% higher μ were observed under elevated vs. ambient CO2, depending on site, plant species and N fertilization. The μ-values increased linearly with atmospheric CO2 concentration at all three sites. The effect of elevated CO2 on rhizosphere microorganisms was plant dependent and increased for: Brassica napus=Triticum aestivumyeast extract then for those growing on glucose, i.e. the effect of elevated CO2 was smoothed on rich vs. simple substrate. So, the r/K strategies ratio can be better revealed by studying growth on simple (glucose) than on rich substrate mixtures (yeast extract). After adding glucose, enzyme activities under elevated CO2 were 1.2-1.9-fold higher than under ambient CO2. This indicates the increased activity of microorganisms, which leads to accelerated C turnover in soil under elevated CO2. Our results clearly showed that the functional characteristics of the soil microbial community (i.e. specific growth rates and enzymes activity) rather than total microbial biomass

Water Isotope framework for lake water balance monitoring and modelling in the Nam Co Basin, Tibetan Plateau

Directory of Open Access Journals (Sweden)

Shichang Kang

2017-08-01

New hydrological insights: A water isotope framework for the Nam Co basin, including the Local Meteoric Water Line, limiting isotopic composition of evaporation and two hypothetical evaporation trajectories, is established. We further applied the isotope mass balance model to estimate the overall isotopic composition of input water to the Nam Co, the evaporation over inputs ratios (E/I for three consecutive years, and the water yields (Wy, depth equivalent runoff at a basin scale. Our results clearly suggest a positive water budget (i.e., E/I < 1, providing another line of evidence that the subsurface leakage from Nam Co is likely. The discrepancy between isotope-based water yields estimations and field-based runoff observations suggest that, compared to the well-studied Nyainqentanglha Mountains and southwestern mountains, the ridge-and-valley landscape in the western highlands and northwestern hogbacks are possibly low yields area, which should draw more research attentions in future hydrological investigations.

Preparation and Characterization of K2CO3-Activated Kraft Lignin Carbon

Directory of Open Access Journals (Sweden)

Xian-fa Li

2016-01-01

Full Text Available A series of activated carbons (ACs were prepared by K2CO3 activation from kraft lignin (KL that was recovered from papermaking black liquor. The effects of process parameters such as the activation temperature (AT, activated period, K2CO3 to KL mass ratio, and N2 flow rate on the characteristics of the final product were determined. The ACs were characterized using nitrogen adsorption, morphology, and fractal dimension analyses. The results showed that the AT was the main factor influencing the yield, surface area, and pore structure. The yield of ACs obviously decreased from 50.6% to 20.5% with increasing AT from 600 °C to 1000 °C, and decreased with increasing K2CO3/KL mass ratio. Activation time and N2 flow rate had slight effect on the yield of ACs. The surface area and total pore volume increased as the AT rose to 900 °C and then decreased with further increases in temperature. The maximum surface area and total pore volume were 1816.3 m2/g and 1.26 cm3/g, respectively, at a K2CO3 to KL mass ratio of 3:1, AT of 900 °C, activation time of 2 h, and N2 flow rate of 70 cm3/min. The pore structure of the ACs could be tailored by controlling the AT. As the AT was increased from 700 to 1000 °C, the mesoporosity increased from 11.6% to 95.9%. SEM images indicated that the morphology of ACs was modified by the AT. The K2CO3 was partially recycled.

Alteration of fault rocks by CO2-bearing fluids with implications for sequestration

Science.gov (United States)

Luetkemeyer, P. B.; Kirschner, D. L.; Solum, J. G.; Naruk, S.

2011-12-01

Carbonates and sulfates commonly occur as primary (diagenetic) pore cements and secondary fluid-mobilized veins within fault zones. Stable isotope analyses of calcite, formation fluid, and fault zone fluids can help elucidate the carbon sources and the extent of fluid-rock interaction within a particular reservoir. Introduction of CO2 bearing fluids into a reservoir/fault system can profoundly affect the overall fluid chemistry of the reservoir/fault system and may lead to the enhancement or degradation of porosity within the fault zone. The extent of precipitation and/or dissolution of minerals within a fault zone can ultimately influence the sealing properties of a fault. The Colorado Plateau contains a number of large carbon dioxide reservoirs some of which leak and some of which do not. Several normal faults within the Paradox Basin (SE Utah) dissect the Green River anticline giving rise to a series of footwall reservoirs with fault-dependent columns. Numerous CO2-charged springs and geysers are associated with these faults. This study seeks to identify regional sources and subsurface migration of CO2 to these reservoirs and the effect(s) faults have on trap performance. Data provided in this study include mineralogical, elemental, and stable isotope data for fault rocks, host rocks, and carbonate veins that come from two localities along one fault that locally sealed CO2. This fault is just tens of meters away from another normal fault that has leaked CO2-charged waters to the land surface for thousands of years. These analyses have been used to determine the source of carbon isotopes from sedimentary derived carbon and deeply sourced CO2. XRF and XRD data taken from several transects across the normal faults are consistent with mechanical mixing and fluid-assisted mass transfer processes within the fault zone. δ13C range from -6% to +10% (PDB); δ18O values range from +15% to +24% (VSMOW). Geochemical modeling software is used to model the alteration

Atmospheric pCO2 reconstructed across five early Eocene global warming events

Science.gov (United States)

Cui, Ying; Schubert, Brian A.

2017-11-01

Multiple short-lived global warming events, known as hyperthermals, occurred during the early Eocene (56-52 Ma). Five of these events - the Paleocene-Eocene Thermal Maximum (PETM or ETM1), H1 (or ETM2), H2, I1, and I2 - are marked by a carbon isotope excursion (CIE) within both marine and terrestrial sediments. The magnitude of CIE, which is a function of the amount and isotopic composition of carbon added to the ocean-atmosphere system, varies significantly between marine versus terrestrial substrates. Here we use the increase in carbon isotope fractionation by C3 land plants in response to increased pCO2 to reconcile this difference and reconstruct a range of background pCO2 and peak pCO2 for each CIE, provided two potential carbon sources: methane hydrate destabilization and permafrost-thawing/organic matter oxidation. Although the uncertainty on each pCO2 estimate using this approach is low (e.g., median uncertainty = + 23% / - 18%), this work highlights the potential for significant systematic bias in the pCO2 estimate resulting from sampling resolution, substrate type, diagenesis, and environmental change. Careful consideration of each of these factors is required especially when applying this approach to a single marine-terrestrial CIE pair. Given these limitations, we provide an upper estimate for background early Eocene pCO2 of 463 +248/-131 ppmv (methane hydrate scenario) to 806 +127/-104 ppmv (permafrost-thawing/organic matter oxidation scenario). These results, which represent the first pCO2 proxy estimates directly tied to the Eocene hyperthermals, demonstrate that early Eocene warmth was supported by background pCO2 less than ∼3.5× preindustrial levels and that pCO2 > 1000 ppmv may have occurred only briefly, during hyperthermal events.

Stable isotope and modelling evidence for CO2 as a driver of glacial–interglacial vegetation shifts in southern Africa

Directory of Open Access Journals (Sweden)

F. J. Bragg

2013-03-01

Full Text Available Atmospheric CO2 concentration is hypothesized to influence vegetation distribution via tree–grass competition, with higher CO2 concentrations favouring trees. The stable carbon isotope (δ13C signature of vegetation is influenced by the relative importance of C4 plants (including most tropical grasses and C3 plants (including nearly all trees, and the degree of stomatal closure – a response to aridity – in C3 plants. Compound-specific δ13C analyses of leaf-wax biomarkers in sediment cores of an offshore South Atlantic transect are used here as a record of vegetation changes in subequatorial Africa. These data suggest a large increase in C3 relative to C4 plant dominance after the Last Glacial Maximum. Using a process-based biogeography model that explicitly simulates 13C discrimination, it is shown that precipitation and temperature changes cannot explain the observed shift in δ13C values. The physiological effect of increasing CO2 concentration is decisive, altering the C3/C4 balance and bringing the simulated and observed δ13C values into line. It is concluded that CO2 concentration itself was a key agent of vegetation change in tropical southern Africa during the last glacial–interglacial transition. Two additional inferences follow. First, long-term variations in terrestrial δ13Cvalues are not simply a proxy for regional rainfall, as has sometimes been assumed. Although precipitation and temperature changes have had major effects on vegetation in many regions of the world during the period between the Last Glacial Maximum and recent times, CO2 effects must also be taken into account, especially when reconstructing changes in climate between glacial and interglacial states. Second, rising CO2 concentration today is likely to be influencing tree–grass competition in a similar way, and thus contributing to the "woody thickening" observed in savannas worldwide. This second inference points to the importance of experiments to

Switchable CO2 electroreduction via engineering active phases of Pd nanoparticles

Institute of Scientific and Technical Information of China (English)

Dunfeng Gao; Fan Yang; Shu Miao; Jianguo Wang; Guoxiong Wang; Xinhe Bao; Hu Zhou; Fan Cai; Dongniu Wang; Yongfeng Hu; Bei Jiang; Wen-Bin Cai; Xiaoqi Chen; Rui Si

2017-01-01

Active-phase engineering is regularly utilized to tune the selectivity of metal nanoparticles (NPs) in heterogeneous catalysis.However,the lack of understanding of the active phase in electrocatalysis has hampered the development of efficient catalysts for CO2 electroreduction.Herein,we report the systematic engineering of active phases of Pd NPs,which are exploited to select reaction pathways for CO2 electroreduction.In situ X-ray absorption spectroscopy,in situ attenuated total reflection-infrared spectroscopy,and density functional theory calculations suggest that the formation of a hydrogen-adsorbed Pd surface on a mixture of the α-and β-phases of a palladium-hydride core (α+β PdHx@PdHx) above-0.2 V (vs.a reversible hydrogen electrode) facilitates formate production via the HCOO* intermediate,whereas the formation of a metallic Pd surface on the β-phase Pd hydride core (β PdHx@Pd) below-0.5 V promotes CO production via the COOH* intermediate.The main product,which is either formate or CO,can be selectively produced with high Faradaic efficiencies (＞90％) and mass activities in the potential window of 0.05 to-0.9 V with scalable application demonstration.

Ancient and modern sites of natural CO2 leakage: Geochemistry and geochronology of Quaternary and modern travertine deposits on the Colorado Plateau, USA, and implications for CO2 sequestration

Science.gov (United States)

Priewisch, A.; Crossey, L. J.; Karlstrom, K. E.; McPherson, B. J.; Mozley, P.

2013-12-01

Travertine-precipitating springs and travertine deposits of the Colorado Plateau serve as natural analogues for evaluating potential leakage associated with geologic sequestration of carbon dioxide (CO2). Extensive Quaternary and modern travertine deposits occur along the Jemez lineament and Rio Grande rift in New Mexico and Arizona, and in the Paradox Basin in Utah, along the Little Grand Wash Fault and the Salt Wash Graben. These groundwater discharge deposits are interpreted to be sites of persistent and significant CO2 degassing along faults and above magmatic systems. Analysis of the geochemical and isotopic composition of U-series dated travertine deposits and modern travertine-precipitating waters allows evaluation of the flow paths of CO2-charged waters. Initial results from New Mexico and Arizona travertine deposits show characteristic rare earth element (REE) signatures for individual travertine deposits and yet generally overlap in concentrations of other trace elements such as Al, As, B, Ba, K, and Si. We report stable oxygen and carbon isotopes of the travertines in New Mexico, Arizona, and Utah. Different travertine deposits have different carbon-oxygen isotope variation patterns suggesting that these stable isotopes are tracers that have the ability to identify distinctive groundwater sources within and between spring groups based on the travertine record. Stable isotope analyses of travertine deposits in New Mexico and Arizona overlap substantially between deposits and cluster around -10‰ to -6‰ for δ18O and around 3.5‰ to 6.5‰ for δ13C. Travertine deposits in Utah show a distinctly different range of stable isotope values: δ18O values cluster around -14‰ to -10.5‰ and δ13C around 4.5‰ to 6.5‰. U-series dating of travertine deposits shows episodic travertine formation in New Mexico and Arizona over the last 700,000 years, and travertine accumulation over the last 400,000 years in Utah. We use U-series dating and volumetric

Co-ordinated research programme on applications of stable isotope tracers in human nutrition research

International Nuclear Information System (INIS)

1989-01-01

This Co-ordinated Research Programme (CRP) was formally established by the Agency in October 1988, and has since then expanded to encompass 13 participants in 13 countries. Its general objective is to help establish competence in the use of stable isotope techniques, particularly in developing countries, and particularly with reference to applications of 2 H, 13 C, 15 N, and 18 O. This report summarizes the discussions that took place during the first Research Co-ordination Meeting (RCM). Working papers (progress reports) presented by the participants are included as annexes together with a preliminary report on the results of a series of intercomparison exercises involving enriched stable isotope reference materials containing 2 H, 13 C, 15 N and 18 O. For the future it was agreed that more work needs to be done to harmonize the analytical techniques being used, and to obtain support for new CRPs relating to human energy expenditure studies in pregnancy, lactation, growth and other conditions, and to studies of nitrogen turnover in relation to malnutrition and liver function. Refs, figs and tabs

Preparation of granular activated carbons from yellow mombin fruit stones for CO2 adsorption.

Science.gov (United States)

Fiuza, Raildo Alves; Medeiros de Jesus Neto, Raimundo; Correia, Laise Bacelar; Carvalho Andrade, Heloysa Martins

2015-09-15

Stones of yellow mombin, a native fruit of the tropical America and West Indies, were used as starting materials to produce activated carbons, subsequently used as adsorbent for CO2 capture. The carbonaceous materials were either chemically activated with HNO3, H3PO4 and KOH or physically activated with CO2. The carbon samples were characterized by SEM, EDX, TG/DTA, Raman spectroscopy, physical adsorption for textural analysis and by acid-base titrations. The CO2 adsorption capacity and adsorption cycles were investigated by TG. The results indicate that the capacity of CO2 adsorption may be maximized on highly basic surfaces of micropores smaller than 1 nm. The KOH activated carbon showed high and stable capacity of CO2 adsorption after 10 cycles. Copyright © 2015 Elsevier Ltd. All rights reserved.

Continuous measurements of stable isotopes of carbon dioxide and water vapour in an urban atmosphere: isotopic variations associated with meteorological conditions.

Science.gov (United States)

Wada, Ryuichi; Matsumi, Yutaka; Nakayama, Tomoki; Hiyama, Tetsuya; Fujiyoshi, Yasushi; Kurita, Naoyuki; Muramoto, Kenichiro; Takanashi, Satoru; Kodama, Naomi; Takahashi, Yoshiyuki

2017-12-01

Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO 2 and water vapour were observed. The isotope ratios of both CO 2 and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ 13 C-CO 2 and δ 18 O-CO 2 increased, while δ 2 H-H 2 Ov and δ 18 O-H 2 Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO 2 and water vapour and the meteorological phenomena. Therefore, isotopic information of CO 2 and H 2 Ov could be used as a tracer of meteorological information.

Highly active Ni/Y-doped ZrO{sub 2} catalysts for CO{sub 2} methanation

Energy Technology Data Exchange (ETDEWEB)

Takano, H., E-mail: takano_hi@hitachizosen.co.jp [Hitachi Zosen Corporation, Kashiwa, 277-8515 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Kirihata, Y.; Izumiya, K.; Kumagai, N. [Hitachi Zosen Corporation, Kashiwa, 277-8515 (Japan); Habazaki, H., E-mail: habazaki@eng.hokudai.ac.jp [Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Division of Applied Chemistry & Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo, 060-8628 (Japan); Hashimoto, K. [Tohoku Institute of Technology, Sendai, 277-8515 (Japan)

2016-12-01

Highlights: • The Ni/Y-doped ZrO{sub 2} catalysts show highly catalytic activity for CO{sub 2} methanation. • Bidentate carbonate is a major adsorption spice on the Ni/Y-doped ZrO{sub 2} catalysts. • The oxide support of t-ZrO{sub 2} and/or c-ZrO{sub 2} with oxygen vacancies plays a key role. - Abstract: The catalytic methanation of CO{sub 2} was carried out on Ni catalysts supported on Y-doped ZrO{sub 2} with various Y{sup 3+} concentrations and Ni/(Zr + Y) molar ratio = 1. The catalysts were characterized by X-ray diffraction, scanning transmission electron microscopy, specific surface area, temperature-programmed desorption of CO{sub 2}, and temperature-programmed reaction. In addition, operando diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFT) was used to identify the adsorbed reaction intermediate. Catalysts supported on Y-doped ZrO{sub 2} show higher catalytic activity than the catalyst on Y-free ZrO{sub 2} with a monoclinic ZrO{sub 2} phase. The catalytic activity is also dependent upon the Y{sup 3+} concentration, and the highest activity was obtained for the catalyst with a Y/(Zr + Y) molar ratio of 0.333, which consists mainly of fcc Ni and cubic ZrO{sub 2} phase. Y{sup 3+} doping into ZrO{sub 2} introduces oxygen vacancies, which play an important role in enhancing the catalytic activity. The operando DRIFT study reveals that a CO adsorption intermediate is absent, and bidentate carbonate is an important intermediate for CH{sub 4} formation.

Development of a cost-effective CO2 adsorbent from petroleum coke via KOH activation

Science.gov (United States)

Jang, Eunji; Choi, Seung Wan; Hong, Seok-Min; Shin, Sangcheol; Lee, Ki Bong

2018-01-01

The capture of CO2 via adsorption is considered an effective technology for decreasing global warming issues; hence, adsorbents for CO2 capture have been actively developed. Taking into account cost-effectiveness and environmental concerns, the development of CO2 adsorbents from waste materials is attracting considerable attention. In this study, petroleum coke (PC), which is the carbon residue remaining after heavy oil upgrading, was used to produce high-value-added porous carbon for CO2 capture. Porous carbon materials were prepared by KOH activation using different weight ratios of KOH/PC (1:1, 2:1, 3:1, and 4:1) and activation temperatures (600, 700, and 800 °C). The specific surface area and total pore volume of resulting porous carbon materials increased with KOH amount, reaching up to 2433 m2/g and 1.11 cm3/g, respectively. The sample prepared under moderate conditions with a KOH/PC weight ratio of 2:1 and activation temperature of 700 °C exhibited the highest CO2 adsorption uptake of 3.68 mmol/g at 25 °C and 1 bar. Interestingly, CO2 adsorption uptake was linearly correlated with the volume of micropores less than 0.8 nm, indicating that narrow micropore volume is crucial for CO2 adsorption. The prepared porous carbon materials also exhibited good selectivity for CO2 over N2, rapid adsorption, facile regeneration, and stable adsorption-desorption cyclic performance, demonstrating potential as a candidate for CO2 capture.

Ni-Nanocluster Modified Black TiO2 with Dual Active Sites for Selective Photocatalytic CO2 Reduction.

Science.gov (United States)

Billo, Tadesse; Fu, Fang-Yu; Raghunath, Putikam; Shown, Indrajit; Chen, Wei-Fu; Lien, Hsiang-Ting; Shen, Tzu-Hsien; Lee, Jyh-Fu; Chan, Ting-Shan; Huang, Kuo-You; Wu, Chih-I; Lin, M C; Hwang, Jih-Shang; Lee, Chih-Hao; Chen, Li-Chyong; Chen, Kuei-Hsien

2018-01-01

One of the key challenges in artificial photosynthesis is to design a photocatalyst that can bind and activate the CO 2 molecule with the smallest possible activation energy and produce selective hydrocarbon products. In this contribution, a combined experimental and computational study on Ni-nanocluster loaded black TiO 2 (Ni/TiO 2[Vo] ) with built-in dual active sites for selective photocatalytic CO 2 conversion is reported. The findings reveal that the synergistic effects of deliberately induced Ni nanoclusters and oxygen vacancies provide (1) energetically stable CO 2 binding sites with the lowest activation energy (0.08 eV), (2) highly reactive sites, (3) a fast electron transfer pathway, and (4) enhanced light harvesting by lowering the bandgap. The Ni/TiO 2[Vo] photocatalyst has demonstrated highly selective and enhanced photocatalytic activity of more than 18 times higher solar fuel production than the commercial TiO 2 (P-25). An insight into the mechanisms of interfacial charge transfer and product formation is explored. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Predictive value of 14CO2 breath tests for clinical use of 13CO2 breath tests

International Nuclear Information System (INIS)

Glaubitt, D.M.H.

1975-01-01

The knowledge of the efficiency of 14 CO 2 breath tests makes possible the comparison of the efficiency of analogous tests using the stable isotope 13 C. 14 CO 2 exhalation studies render overall information. After parenteral administration of a 14 C labeled substrate, 14 CO 2 breath tests permit insight into the metabolism of the 14 C substrate and the associated intermediary metabolism. If the 14 C substrate is given orally or by intraduodenal instillation, 14 CO 2 breath tests supply information not only about gastrointenstinal absorption and digestion but also about the intermediary metabolism yielding 14 CO 2 , after the administered substrate or its degradation products have been absorbed in the gastrointestinal tract. The fraction of 14 CO 2 arising from absorption, digestion and intermediary metabolism can be estimated only by additional methods. 14 CO 2 breath tests are unable to delineate single metabolic reactions involved in the formation of carbon dioxide. Under these considerations the clinical application of 14 CO 2 breath tests may provide diagnostically useful results, especially in internal medicine and surgery. The tests are suitable for intraindividual assessment of the course of a disease and of therapeutic effects. They may be important in the research of the metabolism of 14 C labeled substrates

Gas geochemistry and preliminary CO2 output estimation from the island of Kos (Greece)

Science.gov (United States)

D'Alessandro, Walter; Daskalopoulou, Kyriaki; Calabrese, Sergio; Longo, Manfredi; Kyriakopoulos, Konstantinos; Gagliano, Antonina Lisa

2017-04-01

Several gas samples have been collected from natural gas manifestations at the island of Kos. Most of them are found underwater along the southern coast of the island. On land two anomalous degassing areas have been recognized. These are characterised by lack of vegetation and after long dry periods by the presence of sulfate salts efflorescences. Almost all the gases are CO2-dominated (CO2 ranging from 88 to 99%) with minor amounts of N2 (up to 7%) and CH4 (up to 2.6%). Only the on-land manifestations have also significant contents of H2 (up to 0.2%) and H2S (up to 0.3%). Only one underwater manifestation is N2-dominated (61-99%) with CH4 (0.6-11%) and low CO2 (0.1-26%). The isotopic composition of He shows values ranging from 0.84 to 6.72 R/RA indicating a sometimes strong mantle contribution with the highest values measured in two of the most strongly degassing areas (Paradise Beach and Volcania). C-isotopic composition of CO2 is in the range from -3.6 to 0.6 ‰ vs V-PDB with most of the values around -1‰ indicating a mixed mantle - limestones origin. Isotopic composition of CH4, ranging from -21.5 to 2.8‰ for C and from -143 to 36‰ for H, points to a geothermal origin with sometimes evident secondary oxidation processes. CO2-flux measurements showed values up to about 10,000 g/m2/day in the areas of Volcania and Kokkino Nero and up to about 50,000 g/m2/day at Paradise beach. Preliminary CO2 output estimations gave values of 8.8 and 4 tons/day for the first two areas respectively and of 2.7 tons/day for the latter. The total output of the island (15.5 tons/day) should be considered a minimum estimation because of the incomplete coverage of the area and is comparable to the other active volcanic/geothermal systems of Greece (Nisyros, Nea Kameni and Methana).

Carbon isotopes in biological carbonates: Respiration and photosynthesis

Science.gov (United States)

McConnaughey, Ted A.; Burdett, Jim; Whelan, Joseph F.; Paull, Charles K.

1997-02-01

Respired carbon dioxide is an important constituent in the carbonates of most air breathing animals but is much less important in the carbonates of most aquatic animals. This difference is illustrated using carbon isotope data from freshwater and terrestrial snails, ahermatypic corals, and chemoautotrophic and methanotrophic pelecypods. Literature data from fish otoliths and bird and mammal shell and bone carbonates are also considered. Environmental CO 2/O 2 ratios appear to be the major controlling variable. Atmospheric CO 2/O 2 ratios are about thirty times lower than in most natural waters, hence air breathing animals absorb less environmental CO 2 in the course of obtaining 0 2. Tissue CO 2 therefore, does not isotopically equilibrate with environmental CO 2 as thoroughly in air breathers as in aquatic animals, and this is reflected in skeletal carbonates. Animals having efficient oxygen transport systems, such as vertebrates, also accumulate more respired CO 2 in their tissues. Photosynthetic corals calcify mainly during the daytime when photosynthetic CO 2 uptake is several times faster than respiratory CO 2 release. Photosynthesis, therefore, affects skeletal δ13C more strongly than does respiration. Corals also illustrate how "metabolic" effects on skeletal isotopic composition can be estimated, despite the presence of much larger "kinetic" isotope effects.

Isotopic labeling as a tool to establish intramolecular vibrational coupling: The reaction of 2-propanol on Mo(110)

International Nuclear Information System (INIS)

Uvdal, P.; Wiegand, B.C.; Serafin, J.G.; Friend, C.M.

1992-01-01

The reactions of 2-propanol on Mo(110) were investigated using temperature programmed reaction, high resolution electron energy loss, and x-ray photoelectron spectroscopies. 2-Propanol forms 2-propoxide upon adsorption at 120 K on Mo(110). The 2-propoxide intermediate deoxygenates via selective γ C--H bond scission to eliminate propene as well as C--O bond hydrogenolysis to form trace amounts of propane. The C--O bond of 2-propoxide is estimated to be nearly perpendicular to the surface. Selective isotopic labeling was used to establish the coupling between the C--O stretch and modes associated with the hydrocarbon framework. The degree of coupling was strongly affected by bonding to the surface, primarily due to weakening of the C--O bond when 2-propoxide is bound to Mo(110). Selective isotopic labeling was, therefore, essential in making vibrational assignments and in identifying key reaction steps. Only a small kinetic isotope effect was observed during reaction of (CD 3 )(CH 3 )CHOH, consistent with a substantial component of C--O bond breaking in the transition state for propene elimination. Coupling of the C--O stretch to motion of the methyl group is also suggested to be important in the transition state for propene elimination

A three-dimensional synthesis study of delta O-18 in atmospheric CO2 .1. Surface fluxes

NARCIS (Netherlands)

Ciais, P; Denning, AS; Tans, PP; Berry, JA; Randall, DA; Collatz, GJ; Sellers, PJ; White, JWC; Trolier, M; Meijer, HAJ; Francey, RJ; Monfray, P; Heimann, M

1997-01-01

The isotope O-18 in CO2 is of particular interest in studying the global carbon cycle because it is sensitive to the processes by which the global land biosphere absorbs and respires CO2. Carbon dioxide and water exchange isotopically both in leaves and in soils, and the O-18 character of

Study on CO{sub 2} absorption enhancement by adding active carbon particles into MEA solution

Energy Technology Data Exchange (ETDEWEB)

Qian, Juan; Sun, Rui; Ma, Lian; Sun, Shaozeng [Harbin Institute of Technology, Harbin (China). School of Energy Science and Engineering

2013-07-01

The chemical absorption of CO{sub 2} is generally recognized as the most efficient post-combustion technology of CO{sub 2} separation at present. A study on CO{sub 2} absorption enhancement by adding small particles of active carbon into MEA solution is investigated within a self-designed glass stirring tank. Experiments of different particle loadings and different particle sizes have been conducted. When active carbon particle concentration is fewer, compared to the absorption rate of CO{sub 2} gas absorbed by MEA aqueous solution, the role of active carbon adsorption CO{sub 2} gas is negligible. The enhancement efficiency of CO{sub 2} absorption could be improved by 10% to the upmost in this liquid-particle system.

Granular bamboo-derived activated carbon for high CO(2) adsorption: the dominant role of narrow micropores.

Science.gov (United States)

Wei, Haoran; Deng, Shubo; Hu, Bingyin; Chen, Zhenhe; Wang, Bin; Huang, Jun; Yu, Gang

2012-12-01

Cost-effective biomass-derived activated carbons with a high CO(2) adsorption capacity are attractive for carbon capture. Bamboo was found to be a suitable precursor for activated carbon preparation through KOH activation. The bamboo size in the range of 10-200 mesh had little effect on CO(2) adsorption, whereas the KOH/C mass ratio and activation temperature had a significant impact on CO(2) adsorption. The bamboo-derived activated carbon had a high adsorption capacity and excellent selectivity for CO(2) , and also the adsorption process was highly reversible. The adsorbed amount of CO(2) on the granular activated carbon was up to 7.0 mmol g(-1) at 273 K and 1 bar, which was higher than almost all carbon materials. The pore characteristics of activated carbons responsible for high CO(2) adsorption were fully investigated. Based on the analysis of narrow micropore size distribution of several activated carbons prepared under different conditions, a more accurate micropore range contributing to CO(2) adsorption was proposed. The volume of micropores in the range of 0.33-0.82 nm had a good linear relationship with CO(2) adsorption at 273 K and 1 bar, and the narrow micropores of about 0.55 nm produced the major contribution, which could be used to evaluate CO(2) adsorption on activated carbons. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On-line stable isotope measurements during plant and soil gas exchange

International Nuclear Information System (INIS)

Yakir, D.

2001-01-01

Recent techniques for on-line stable isotope measurements during plant and soil exchange of CO 2 and/or water vapor are briefly reviewed. For CO 2 , these techniques provide means for on-line measurements of isotopic discrimination during CO 2 exchange by leaves in the laboratory and in the field, of isotopic discrimination during soil respiration and during soil-atmosphere CO 2 exchange, and of isotopic discrimination in O 2 during plant respiration. For water vapor, these techniques provide means to measure oxygen isotopic composition of water vapor during leaf transpiration and for the analysis of sub microliter condensed water vapor samples. Most of these techniques involve on-line sampling of CO 2 and water vapor from a dynamic, intact soil or plant system. In the laboratory, these systems also allow on-line isotopic analysis by continuous-flow isotope ratio mass spectrometry. The information obtained with these on-line techniques is becoming increasingly valuable, and often critical, for ecophysiologial research and in the study of biosphere-atmosphere interactions. (author)

On the isotope effects of ZrCoX3 (X = H, D and T): a first-principles study

International Nuclear Information System (INIS)

Chattaraj, D.; Parida, S.C.; Dash, Smruti; Majumder, C.

2013-01-01

In the ITER project, the ZrCo-X (X= H, D and T) systems have gained considerable attention because of its use in the hydrogen isotope storage. The isotopic effects on the ZrCoX 3 (X= H, D and T) compounds have been studied in terms of the variation of the thermodynamic parameters using the DFT and frozen phonon approach. A significant difference between the ZrCoH 3 and its isotopic analogues has been noticed in terms of zero point energy (ZPE) and phonon frequencies. The zero point energies are 65.47 kJ/mol, 48.07 kJ/mol and 39.32 kJ/mol for ZrCoH 3 , ZrCoD 3 and ZrCoT 3 , respectively. The enthalpy of formation of ZrCoX 3 compounds, including the ZPE contributions, are -124.84, -142.24 and -150.99 kJ/(mole of compound) for X = H, D and T, respectively. (author)

Isotopic Discrimination During Leaf Litter Decomposition

Science.gov (United States)

Ngao, J.; Rubino, M.

2006-12-01

Methods involving stable isotopes have been successfully applied since decades in various research fields. Tracing 13C natural abundance in ecosystem compartments greatly enhanced the understanding of the C fluxes in the plant-soil-atmosphere C exchanges when compartments present different C isotopic signatures (i.e. atmospheric CO2 vs photosynthetic leaves, C3 vs C4; etc.). However, the assumption that no isotopic discrimination occurs during respiration is commonly made in numbers of C isotope-based ecological studies. Furthermore, verifications of such assumption are sparse and not enough reliable. The aim of our study is to assess the potential isotopic discrimination that may occur during litter decomposition. Leaf litter from an Arbutus unedo (L.) stand (Tolfa, Italy) was incubated in 1L jars, under constant laboratory conditions (i.e. 25 ° C and 135% WC). During the entire incubation period, gravimetric mass loss, litter respiration rates and the isotopic composition of respired CO2 are monitored at regular intervals. Data from 7 months of incubation will be presented and discussed. After two months, the litter mass loss averaged 16% of initial dry mass. During the same time-period, the respiration rate decreased significantly by 58% of the initial respiration rate. Isotopic compositions of respired CO2 ranged between -27.95‰ and - 25.69‰. Mean values did not differ significantly among the sampling days, in spite of an apparent enrichment in 13C of respired CO2 with time. The significance of these isotopic enrichment will be determined at a longer time scale. They may reveal both/either a direct microbial discrimination during respiration processes and/or a use of different litter compounds as C source along time. Further chemical and compound-specific isotopic analysis of dry matter will be performed in order to clarify these hypotheses. This work is part of the "ALICE" project, funded by the European Union's Marie Curie Fellowship Actions that aims to

Utilization of stable isotopes for characterizing an underground gas generator; Utilisation des isotopes stables pour caracteriser un gazogene souterrain

Energy Technology Data Exchange (ETDEWEB)

Pirard, J P; Antenucci, D; Renard, X [Liege Univ. (Belgium); Letolle, R [Paris-6 Univ., 75 (France)

1994-12-31

The principles of isotopic exchange and isotope ratio result interpretation are first reviewed; then, in the framework of an underground coal gasification project in Belgium, experiments and modelling of the underground gas generator have been carried out: isotopic abundances of carbon, hydrogen and oxygen have been measured in the gasifying agent (O{sub 2}, H{sub 2}O) and in the effluent (CO{sub 2}, CO, H{sub 2}, H{sub 2}O, CH{sub 4}, O{sub 2}, heavy oils and various organic and mineral substances). Gasification kinetics and temperatures have been evaluated and isotope application to thermometry is discussed. 1 fig., 9 refs.

MIR hollow waveguide (HWG) isotope ratio analyzer for environmental applications

Science.gov (United States)

Wang, Zhenyou; Zhuang, Yan; Deev, Andrei; Wu, Sheng

2017-05-01

An advanced commercial Mid-InfraRed Isotope Ratio (IR2) analyzer was developed in Arrow Grand Technologies based on hollow waveguide (HWG) as the sample tube. The stable carbon isotope ratio, i.e. δ13C, was obtained by measuring the selected CO2 absorption peaks in the MIR. Combined with a GC and a combustor, it has been successfully employed to measure compound specific δ13C isotope ratios in the field. By using both the 1- pass HWG and 5-path HWG, we are able to measure δ13C isotope ratio at a broad CO2 concentration of 300 ppm-37,500 ppm. Here, we demonstrate its applications in environmental studies. The δ13C isotope ratio and concentration of CO2 exhaled by soil samples was measured in real time with the isotope analyzer. The concentration was found to change with the time. We also convert the Dissolved Inorganic Carbon (DIC) into CO2, and then measure the δ13C isotope ratio with an accuracy of better than 0.3 ‰ (1 σ) with a 6 min test time and 1 ml sample usage. Tap water, NaHCO3 solvent, coca, and even beer were tested. Lastly, the 13C isotope ratio of CO2 exhaled by human beings was obtained <10 seconds after simply blowing the exhaled CO2 into a tube with an accuracy of 0.5‰ (1 σ) without sample preconditioning. In summary, a commercial HWG isotope analyzer was demonstrated to be able to perform environmental and health studies with a high accuracy ( 0.3 ‰/Hz1/2 1 σ), fast sampling rate (up to 10 Hz), low sample consumption ( 1 ml), and broad CO2 concentration range (300 ppm-37,500 ppm).

Abiotic and seasonal control of soil-produced CO2 efflux in karstic ecosystems located in Oceanic and Mediterranean climates

Science.gov (United States)

Garcia-Anton, Elena; Cuezva, Soledad; Fernandez-Cortes, Angel; Alvarez-Gallego, Miriam; Pla, Concepcion; Benavente, David; Cañaveras, Juan Carlos; Sanchez-Moral, Sergio

2017-09-01

This study characterizes the processes involved in seasonal CO2 exchange between soils and shallow underground systems and explores the contribution of the different biotic and abiotic sources as a function of changing weather conditions. We spatially and temporally investigated five karstic caves across the Iberian Peninsula, which presented different microclimatic, geologic and geomorphologic features. The locations present Mediterranean and Oceanic climates. Spot air sampling of CO2 (g) and δ13CO2 in the caves, soils and outside atmospheric air was periodically conducted. The isotopic ratio of the source contribution enhancing the CO2 concentration was calculated using the Keeling model. We compared the isotopic ratio of the source in the soil (δ13Cs-soil) with that in the soil-underground system (δ13Cs-system). Although the studied field sites have different features, we found common seasonal trends in their values, which suggests a climatic control over the soil air CO2 and the δ13CO2 of the sources of CO2 in the soil (δ13Cs-soil) and the system (δ13Cs-system). The roots respiration and soil organic matter degradation are the main source of CO2 in underground environments, and the inlet of the gas is mainly driven by diffusion and advection. Drier and warmer conditions enhance soil-exterior CO2 interchange, reducing the CO2 concentration and increasing the δ13CO2 of the soil air. Moreover, the isotopic ratio of the source of CO2 in both the soil and the system tends to heavier values throughout the dry and warm season. We conclude that seasonal variations of soil CO2 concentration and its 13C/12C isotopic ratio are mainly regulated by thermo-hygrometric conditions. In cold and wet seasons, the increase of soil moisture reduces soil diffusivity and allows the storage of CO2 in the subsoil. During dry and warm seasons, the evaporation of soil water favours diffusive and advective transport of soil-derived CO2 to the atmosphere. The soil CO2 diffusion is

Calculation of Site-specific Carbon-isotope Fractionation in Pedogenic Oxide Minerals

Energy Technology Data Exchange (ETDEWEB)

Rustad, James R.; Zarzycki, Piotr

2008-07-29

Ab initio molecular dynamics and quantum chemistry techniques are used to calculate the structure, vibrational frequencies, and carbon-isotope fractionation factors of the carbon dioxide component [CO2(m)] of soil (oxy)hydroxide minerals goethite, diaspore, and gibbsite. We have identified two possible pathways of incorporation of CO2(m) into (oxy)hydroxide crystal structures: one in which the C4+ substitutes for four H+ [CO2(m)A] and another in which C4+ substitutes for (Al3+,Fe3+) + H+ [CO2(m)B]. Calculations of isotope fractionation factors give large differences between the two structures, with the CO2(m)A being isotopically lighter than CO2(m)B by ≈10 per mil in the case of gibbsite and nearly 20 per mil in the case of goethite. The reduced partition function ratio of CO2(m)B structure in goethite differs from CO2(g) by <1 per mil. The predicted fractionation for gibbsite is >10 per mil higher, close to those measured for calcite and aragonite. The surprisingly large difference in the carbon-isotope fractionation factor between the CO2(m)A and CO2(m)B structures within a given mineral suggests that the isotopic signatures of soil (oxy)hydroxide could be heterogeneous.

Pressure dependent isotopic fractionation in the photolysis of formaldehyde-d2

DEFF Research Database (Denmark)

Nilsson, E.J.K.; Schmidt, Johan Albrecht; Johnson, Matthew Stanley

2014-01-01

role in the observed pressure dependent photolytic fractionation of deuterium. The model shows that part of the fractionation is a result of competition between the isotopologue dependent rates of unimolecular dissociation and collisional relaxation. We suggest that the remaining fractionation is due......The isotope effects in formaldehyde photolysis are the key link between the δD of methane emissions and the δD of atmospheric in situ hydrogen production. A few recent studies have suggested that a pressure dependence in the isotopic fractionation can partly explain enrichment of deuterium...... with altitude in the atmosphere. The mechanism and the extent of this pressure dependency is, however, not adequately described. In the present work D2CO and H2CO were photolyzed in a static reaction chamber at bath gas pressures of 50, 200, 400, 600 and 1000 mbar; these experiments compliment and extend our...

Deuterium isotope differences in 2-propanone (CH3)2CO/(CD3)2CO: a high-pressure sound-speed, density, and heat capacities study

International Nuclear Information System (INIS)

Szydlowski, J.; Gomes de Azevedo, R.; Rebelo, L.P.N.; Esperanca, J.M.S.S.; Guedes, H.J.R.

2005-01-01

A new high-pressure, non-intrusive ultrasonic microcell [J. Chem. Thermodyn. 36 (2004) 211-222] was used to carry out sound-speed measurements in deuteriated 2-propanone (acetone-d 6 ) in broad ranges of temperature (288 6 . (p, ρ, T) data for acetone-d 6 were also determined but in a narrower T, p range (298 to 333 K; 0.1 to 60 MPa). In this interval, several thermodynamic properties were thus determined, such as: isentropic (κ s ) and isothermal (κ T ) compressibility, isobaric thermal expansivity (α p ), isobaric (c p ) and isochoric (c v ) specific heat capacity, and the thermal pressure coefficient (γ v ). Comparisons with our data for acetone-h 6 enabled us to establish the magnitude and sign of deuterium isotope effects for identical properties. These effects are a consequence of distinct vibrational mode frequencies in an isotope-invariant force constants' field. Molar heat capacities and their isotope effects were theoretically determined by employing an Einstein-like model for the vibrational frequencies of acetone-h 6 and acetone-d 6

History of CO/sub 2/

Energy Technology Data Exchange (ETDEWEB)

Degens, E T

1979-01-01

Upon arrival on earth, the reduced carbon pool split into a series of compartments: core, mantle, crust, hydrosphere, atmosphere, and biosphere. This distribution pattern is caused by the ability of carbon to adjust structurally to a wide range of pressure and temperature, and to form simple and complex molecules with oxygen, hydrogen and nitrogen. Transformation also involved oxidation of carbon to CO/sub 2/ which is mediated at depth by minerals, such as magnetite, and by water vapor above critical temperature. Guided by mineral-organic interactions, simple carbon compounds evolved in near surface environments towards physiologically interesting biochemicals. Life, as an autocatalytic system, is considered an outgrowth of such a development. This article discusses environmental parameters that control the CO/sub 2/ system, past and present. Mantle and crustal evolution is the dynamo recharging the CO/sub 2/ in sea and air; the present rate of CO/sub 2/ release from the magma is 0.05 x 10/sup 15/ g C per year. Due to the enormous buffer capacity of the chemical system ocean, such rates are too small to seriously effect the level of CO/sub 2/ in our atmosphere. In the light of geological field data and stable isotope work, it is concluded that the CO/sub 2/ content in the atmosphere has remained fairly uniform since early Precambrian time; CO/sub 2/ should thus have had little impact on paleoclimate. In contrast, the massive discharge of man-made CO/sub 2/ into our atmosphere may have serious consequences for climate, environment and society in the years to come.

Activity of carbon supported Pt3Ru2 nanocatalyst in CO oxidation

Directory of Open Access Journals (Sweden)

KSENIJA DJ. POPOVIĆ

2009-08-01

Full Text Available The electrocatalytic activity of Pt3Ru2/C nanocatalyst toward the electro-oxidation of bulk CO was examined in acid and alkaline solution at ambient temperature using the thin-film, rotating disk electrode (RDE method. The catalyst was characterized by XRD analysis. The XRD pattern revealed that the Pt3Ru2/C catalyst consisted of two structures, i.e., Pt–Ru-fcc and Ru-hcp (a solid solution of Ru in Pt and a small amount of Ru or a solid solution of Pt in Ru. Electrocatalytic activities were measured by applying potentiodynamic and steady state techniques. The oxidation of CO on the Pt3Ru2/C catalyst was influenced by pH and anions from the supporting electrolytes. The Pt3Ru2/C was more active in alkaline than in acid solution, as well as in perchloric than in sulfuric acid. Comparison of CO oxidation on Pt3Ru2/C and Pt/C revealed that the Pt3Ru2/C was more active than Pt/C in acid solution, while both catalysts had a similar activity in alkaline solution.

Gasification under CO2–Steam Mixture: Kinetic Model Study Based on Shared Active Sites

Directory of Open Access Journals (Sweden)

Xia Liu

2017-11-01

Full Text Available In this work, char gasification of two coals (i.e., Shenfu bituminous coal and Zunyi anthracite and a petroleum coke under a steam and CO2 mixture (steam/CO2 partial pressures, 0.025–0.075 MPa; total pressures, 0.100 MPa and CO2/steam chemisorption of char samples were conducted in a Thermogravimetric Analyzer (TGA. Two conventional kinetic models exhibited difficulties in exactly fitting the experimental data of char–steam–CO2 gasification. Hence, a modified model based on Langmuir–Hinshelwood model and assuming that char–CO2 and char–steam reactions partially shared active sites was proposed and had indicated high accuracy for estimating the interactions in char–steam–CO2 reaction. Moreover, it was found that two new model parameters (respectively characterized as the amount ratio of shared active sites to total active sites in char–CO2 and char–steam reactions in the modified model hardly varied with gasification conditions, and the results of chemisorption indicate that these two new model parameters mainly depended on the carbon active sites in char samples.

Boron isotopes in geothermal systems

International Nuclear Information System (INIS)

Aggarwal, J.

1997-01-01

Boron is a highly mobile element and during water-rock reactions, boron is leached out of rocks with no apparent fractionation. In geothermal systems where the water recharging the systems are meteoric in origin, the B isotope ratio of the geothermal fluid reflects the B isotope ratio of the rocks. Seawater has a distinctive B isotope ratio and where seawater recharges the geothermal system, the B isotope ratio of the geothermal system reflects the mixing of rock derived B and seawater derived B. Any deviations of the actual B isotope ratio of a mixture reflects subtle differences in the water-rock ratios in the cold downwelling limb of the hydrothermal system. This paper will present data from a variety of different geothermal systems, including New Zealand; Iceland; Yellowston, USA; Ibusuki, Japan to show the range in B isotope ratios in active geothermal systems. Some of these systems show well defined mixing trends between seawater and the host rocks, whilst others show the boron isotope ratios of the host rock only. In geothermal systems containing high amounts of CO 2 boron isotope ratios from a volatile B source can also be inferred. (auth)

Fossil fuel CO2 estimation by atmospheric 14C measurement and CO2 mixing ratios in the city of Debrecen, Hungary

International Nuclear Information System (INIS)

Molnar, M.; Svingor, E.; Haszpra, L.; Ivo Svetlik; Veres, M.

2010-01-01

A field unit was installed in the city of Debrecen (East Hungary) during the summer of 2008 to monitor urban atmospheric fossil fuel CO 2 . To establish a reference level simultaneous CO 2 sampling has been carried out at a rural site (Hegyhatsal) in Western Hungary. Using the Hungarian background 14 CO 2 observations from the rural site atmospheric fossil fuel CO 2 component for the city of Debrecen was reported in a regional 'Hungarian' scale. A well visible fossil fuel CO 2 peak (10-15 ppm) with a maximum in the middle of winter 2008 (January) was observed in Debrecen air. Significant local maximum (∼20 ppm) in fossil fuel CO 2 during Octobers of 2008 and 2009 was also detected. Stable isotope results are in agreement with the 14 C based fossil fuel CO 2 observations as the winter of 2008 and 2009 was different in atmospheric δ 13 C variations too. The more negative δ 13 C of atmospheric CO 2 in the winter of 2008 means more fossil carbon in the atmosphere than during the winter of 2009. (author)

High efficiency of CO2-activated graphite felt as electrode for vanadium redox flow battery application

Science.gov (United States)

Chang, Yu-Chung; Chen, Jian-Yu; Kabtamu, Daniel Manaye; Lin, Guan-Yi; Hsu, Ning-Yih; Chou, Yi-Sin; Wei, Hwa-Jou; Wang, Chen-Hao

2017-10-01

A simple method for preparing CO2-activated graphite felt as an electrode in a vanadium redox flow battery (VRFB) was employed by the direct treatment in a CO2 atmosphere at a high temperature for a short period. The CO2-activated graphite felt demonstrates excellent electrochemical activity and reversibility. The VRFB using the CO2-activated graphite felts in the electrodes has coulombic, voltage, and energy efficiencies of 94.52%, 88.97%, and 84.15%, respectively, which is much higher than VRFBs using the electrodes of untreated graphite felt and N2-activated graphite felt. The efficiency enhancement was attributed to the higher number of oxygen-containing functional groups on the graphite felt that are formed during the CO2-activation, leading to improving the electrochemical behaviour of the resultant VRFB.

Whole-body CO2 production as an index of the metabolic response to sepsis

Science.gov (United States)

Whole-body carbon dioxide (CO2) production (RaCO2) is an index of substrate oxidation and energy expenditure; therefore, it may provide information about the metabolic response to sepsis. Using stable isotope techniques, we determined RaCO2 and its relationship to protein and glucose metabolism in m...

Atmospheric pCO2 Reconstructed across the Early Eocene Hyperthermals

Science.gov (United States)

Cui, Y.; Schubert, B.

2015-12-01

Negative carbon isotope excursions (CIEs) are commonly associated with extreme global warming. The Early Eocene is punctuated by five such CIEs, the Paleocene-Eocene thermal maximum (PETM, ca. 55.8 Ma), H1 (ca. 53.6 Ma), H2 (ca. 53.5 Ma), I1 (ca. 53.3 Ma), and I2 (ca. 53.2 Ma), each characterized by global warming. The negative CIEs are recognized in both marine and terrestrial substrates, but the terrestrial substrates exhibit a larger absolute magnitude CIE than the marine substrates. Here we reconcile the difference in CIE magnitude between the terrestrial and marine substrates for each of these events by accounting for the additional carbon isotope fractionation by C3 land plants in response to increased atmospheric pCO2. Our analysis yields background and peak pCO2 values for each of the events. Assuming a common mechanism for each event, we calculate that background pCO2 was not static across the Early Eocene, with the highest background pCO2 immediately prior to I2, the last of the five CIEs. Background pCO2 is dependent on the source used in our analysis with values ranging from 300 to 720 ppmv provided an injection of 13C-depleted carbon with δ13C value of -60‰ (e.g. biogenic methane). The peak pCO2 during each event scales according to the magnitude of CIE, and is therefore greatest during the PETM and smallest during H2. Both background and peak pCO2 are higher if we assume a mechanism of permafrost thawing (δ13C = -25‰). Our reconstruction of pCO2 across these events is consistent with trends in the δ18O value of deep-sea benthic foraminifera, suggesting a strong link between pCO2 and temperature during the Early Eocene.

Can a sponge fractionate isotopes?

Science.gov (United States)

Patel, B; Patel, S; Balani, M C

1985-03-22

The study has unequivocally demonstrated that siliceous sponges Spirastrella cuspidifera and Prostylyssa foetida from the same microecological niche exhibit a high degree of species specificity, while accumulating a host of heavy metal ions (Ni, Cr, Cd, Sn, Ti, Mo, Zr). S. cuspidifera accumulated, in addition, 60Co and 63Ni, showing discrimination against other radionuclides, 137Cs and 131I, present in the ambient waters receiving controlled low level waste discharges from a B.W.R. nuclear power station. P. foetida, on the other hand, accumulated only 131I and showed discrimination against other radionuclides including 60Co, although the stable iodine concentrations in both the sponges were the same. The specific activity of 60Co (in becquerels per gram of 59Co) in S. cuspidifera and 131I (in becquerels per gram of 127I) in P. foetida were at least two orders of magnitude greater than in the ambient sea water. That of 63Ni (in becquerels per gram of 62Ni) in S. cuspidifera, on the other hand, was lower by two orders of magnitude than in either abiotic matrices from the same environment. Thus, not only did both the species show bioaccumulation of a specific element, but also preferential uptake of isotopes of the same element, though they were equally available for intake. Such differential uptake of isotopes can possibly be explained in terms of two quite different mechanisms operating, each applicable in a particular case. One is that the xenobiotic isotope enters the environment in a physicochemical form or as a complex different from that of its natural counterpart. If equilibration with the latter is slow, so that the organism acquires the xenobiotic in an unfamiliar chemical context, it may treat it as a chemically distinct entity so that its concentration factor differs from that of stable isotope, thus changing the specific activity. Alternatively, if the xenobiotic is present in the same chemical form as the stable isotope, the only way in which specific

NAC, Neutron Activation Analysis and Isotope Inventory

International Nuclear Information System (INIS)

1995-01-01

1 - Description of program or function: NAC was designed to predict the neutron-induced gamma-ray radioactivity for a wide variety of composite materials. The NAC output includes the input data, a list of all reactions for each constituent element, and the end-of-irradiation disintegration rates for each reaction. NAC also compiles a product isotope inventory containing the isotope name, the disintegration rate, the gamma-ray source strength and the absorbed dose rate at 1 meter from an unshielded point source. The induced activity is calculated as a function of irradiation and decay times; the effect of cyclic irradiation can also be calculated. 2 - Method of solution: The standard neutron activation and decay equations are programmed. A data library is supplied which contains target element names, atomic densities, reaction indices, individual reactions and reaction parameters, and product isotopes and gamma energy yields. 3 - Restrictions on the complexity of the problem: Each composite material may consist of up to 20 different elements and up to 20 different decay times may be included. Both limits may be increased by the user by increasing the appropriate items in the dimension statement

Geochemical Study of Natural CO2 Emissions in the French Massif Central: How to Predict Origin, Processes and Evolution of CO2 Leakage Étude géochimique des émissions naturelles de CO2 du Massif Central : origine et processus de migration du gaz

Directory of Open Access Journals (Sweden)

Battani A.

2010-05-01

Full Text Available This study presents an overview of some results obtained within the French ANR (National Agency of Research supported Géocarbone-Monitoring research program. The measurements were performed in Sainte-Marguerite, located in the French Massif Central. This site represents a natural laboratory for CO2/fluid/rock interactions studies, as well as CO2 migration mechanisms towards the surface. The CO2 leaking character of the studied area also allows to test and validate measurements methods and verifications for the future CO2 geological storage sites. During these surveys, we analyzed soil CO2 fluxes and concentrations. We sampled and analyzed soil gases, and gas from carbo-gaseous bubbling springs. A one-month continuous monitoring was also tested, to record the concentration of CO2 both in atmosphere and in the soil at a single point. We also developed a new methodology to collect soil gas samples for noble gas abundances and isotopic analyses, as well as carbon isotopic ratios. Our geochemical results, combined with structural geology, show that the leaking CO2 has a very deep origin, partially mantle derived. The gas rises rapidly along normal and strike-slip active faults. CO2 soil concentrations (also showing a mantle derived component and CO2 fluxes are spatially variable, and reach high values. The recorded atmospheric CO2 is not very high, despite the important CO2 degassing throughout the whole area. Cette étude présente les principaux résultats de campagnes de monitoring géochimique menées en 2006 et 2007 dans le cadre du projet Géocarbone-Monitoring, sur le site de Sainte-Marguerite, situé dans le Massif Central. Ce site constitue un « laboratoire naturel » pour l’étude des interactions CO2/fluides/roches et des mécanismes de migration du CO2 vers la surface, à l’échelle des temps géologiques. Le caractère particulièrement émissif de cet « analogue » permet également de tester et valider des méthodes de mesure et

Concomitant carboxylate and oxalate formation from the activation of CO{sub 2} by a thorium(III) complex

Energy Technology Data Exchange (ETDEWEB)

Formanuik, Alasdair; Ortu, Fabrizio; Mills, David P. [School of Chemistry, The University of Manchester (United Kingdom); Inman, Christopher J. [Department of Chemistry and Biochemistry, School of Life Sciences, University of Sussex, Brighton (United Kingdom); Kerridge, Andrew [Department of Chemistry, Lancaster University (United Kingdom); Castro, Ludovic; Maron, Laurent [LPCNO, CNRA et INSA, Universite Paul Sabatier, Toulouse (France)

2016-12-12

Improving our comprehension of diverse CO{sub 2} activation pathways is of vital importance for the widespread future utilization of this abundant greenhouse gas. CO{sub 2} activation by uranium(III) complexes is now relatively well understood, with oxo/carbonate formation predominating as CO{sub 2} is readily reduced to CO, but isolated thorium(III) CO{sub 2} activation is unprecedented. We show that the thorium(III) complex, [Th(Cp''){sub 3}] (1, Cp''={C_5H_3(SiMe_3)_2-1,3}), reacts with CO{sub 2} to give the mixed oxalate-carboxylate thorium(IV) complex [{Th(Cp'')_2[κ"2-O_2C{C_5H_3-3,3'-(SiMe_3)_2}]}{sub 2}(μ-κ{sup 2}:κ{sup 2}-C{sub 2}O{sub 4})] (3). The concomitant formation of oxalate and carboxylate is unique for CO{sub 2} activation, as in previous examples either reduction or insertion is favored to yield a single product. Therefore, thorium(III) CO{sub 2} activation can differ from better understood uranium(III) chemistry. (copyright 2016 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

A sublimation technique for high-precision measurements of δ13CO2 and mixing ratios of CO2 and N2O from air trapped in ice cores

Directory of Open Access Journals (Sweden)

H. Fischer

2011-07-01

Full Text Available In order to provide high precision stable carbon isotope ratios (δ13CO2 or δ13C of CO2 from small bubbly, partially and fully clathrated ice core samples we developed a new method based on sublimation coupled to gas chromatography-isotope ratio mass spectrometry (GC-IRMS. In a first step the trapped air is quantitatively released from ~30 g of ice and CO2 together with N2O are separated from the bulk air components and stored in a miniature glass tube. In an off-line step, the extracted sample is introduced into a helium carrier flow using a minimised tube cracker device. Prior to measurement, N2O and organic sample contaminants are gas chromatographically separated from CO2. Pulses of a CO2/N2O mixture are admitted to the tube cracker and follow the path of the sample through the system. This allows an identical treatment and comparison of sample and standard peaks. The ability of the method to reproduce δ13C from bubble and clathrate ice is verified on different ice cores. We achieve reproducibilities for bubble ice between 0.05 ‰ and 0.07 ‰ and for clathrate ice between 0.05 ‰ and 0.09 ‰ (dependent on the ice core used. A comparison of our data with measurements on bubble ice from the same ice core but using a mechanical extraction device shows no significant systematic offset. In addition to δ13C, the CO2 and N2O mixing ratios can be volumetrically derived with a precision of 2 ppmv and 8 ppbv, respectively.

Oxygen isotopic signature of CO2 from combustion processes

NARCIS (Netherlands)

Schumacher, M.; Werner, R. A.; Meijer, H. A. J.; Brand, W. A.; Geilmann, H.; Neubert, R. E. M.; Kaiser, J.; Jansen, Henk G.

2011-01-01

For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (C-13 and O-18) abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the delta O-18

Co-ordinated research programme applications of stable isotope tracers in human nutrition research

International Nuclear Information System (INIS)

1992-01-01

The objective of this Co-ordinated Research Programme is to help establish competence in the use of stable isotope techniques, particularly in developing countries. This report summarizes the discussions that took, place during the Second Research Co-ordination Meeting, held in Bangalore in November 1990. Working papers presented by the participants are included as annexes. Refs, figs and tabs

Root activity evaluation in tree crops using isotopic techniques

International Nuclear Information System (INIS)

Calvache, Marcelo

1991-01-01

This paper discusses the methdology used to evalute root activity of the crops utilizing the technique of soil injection with solutions marked with isotopes. Some of the experimental data obtained with coffee, citrus and oil palm are also presented. Ovel all, these tree crops present a higher root activity in soil layers close to the surface (0-20 cm) and to a distance from the trunk which varies with age, season and variety. The most important conclusions are: 1. The isotope injection technique using 3 2 P , 1 5 N , or 8 5 R b, allow direct and reliable determination of root activity in these tree crops. 2. Root activity of three crops depends on age of the tree, variety, moisture content of the soil and soil type. 3. Soil moisture is the most influencial factor affecting root activity. This is turn depends on the irrigation method employed. 4. From the practical view point, the best distance from the trunk to apply fertilizer in the one wich has highest root activity closest to the soil surface

A study of structure–activity relationships of commercial tertiary amines for post-combustion CO_2 capture

International Nuclear Information System (INIS)

Xiao, Min; Liu, Helei; Idem, Raphael; Tontiwachwuthikul, Paitoon; Liang, Zhiwu

2016-01-01

Highlights: • Ethyl group is beneficial for tertiary amines of CO_2 absorption. • The existence of side carbon chain may promote the activity of tertiary amine. • Hydroxyl group reduces the equilibrium CO_2 solubility, k_2 and pKa. • Heterocyclic structure decrease the equilibrium CO_2 solubility, k_2 and pKa. • Hydroxyl group results in higher CO_2 absorption heat. - Abstract: This work examined the relationship between the structure of various commercial tertiary amines and their activity in CO_2 absorption/desorption in terms of rate of CO_2 absorption, equilibrium CO_2 loading, pKa and heat of CO_2 absorption in order to establish possible guidelines for selection of tertiary amine components for amine blends. Results show that any electron donating group linked directly to the nitrogen atom increases their reactivity with CO_2. In addition, the presence of steric hindrance effect and good water solubility also show enhancements in activity. In contrast, the existence of a hydroxyl group leads to a decrease in all the activity of the tertiary amine. The heat of CO_2 absorption of tertiary amines, which is closely related to the regeneration energy, can be reduced by decreasing the number of hydroxyethyl groups or by positing the hydroxyl group at the proper carbon relative to the nitrogen atom.

Characterization of methane oxidation in a simulated landfill cover system by comparing molecular and stable isotope mass balances.

Science.gov (United States)

Schulte, Marcel; Jochmann, Maik A; Gehrke, Tobias; Thom, Andrea; Ricken, Tim; Denecke, Martin; Schmidt, Torsten C

2017-11-01

Biological methane oxidation may be regarded as a method of aftercare treatment for landfills to reduce climate relevant methane emissions. It is of social and economic interest to estimate the behavior of bacterial methane oxidation in aged landfill covers due to an adequate long-term treatment of the gas emissions. Different approaches assessing methane oxidation in laboratory column studies have been investigated by other authors recently. However, this work represents the first study in which three independent approaches, ((i) mass balance, (ii) stable isotope analysis, and (iii) stoichiometric balance of product (CO 2 ) and reactant (CH 4 ) by CO 2 /CH 4 -ratio) have been compared for the estimation of the biodegradation by a robust statistical validation on a rectangular, wide soil column. Additionally, an evaluation by thermal imaging as a potential technique for the localization of the active zone of bacterial methane oxidation has been addressed in connection with stable isotope analysis and CO 2 /CH 4 -ratios. Although landfills can be considered as open systems the results for stable isotope analysis based on a closed system correlated better with the mass balance than calculations based on an open system. CO 2 /CH 4 -ratios were also in good agreement with mass balance. In general, highest values for biodegradation were determined from mass balance, followed by CO 2 /CH 4 -ratio, and stable isotope analysis. The investigated topsoil proved to be very suitable as a potential cover layer by removing up to 99% of methane for CH 4 loads of 35-65gm -2 d -1 that are typical in the aftercare phase of landfills. Finally, data from stable isotope analysis and the CO 2 /CH 4 -ratios were used to trace microbial activity within the reactor system. It was shown that methane consumption and temperature increase, as a cause of high microbial activity, correlated very well. Copyright © 2017 Elsevier Ltd. All rights reserved.

CO2 and circulation in the deglacial North Pacific

Science.gov (United States)

Taylor, B.; Rae, J. W. B.; Gray, W. R.; Rees-Owen, R. L.; Burke, A.

2017-12-01

The North Pacific is the largest carbon reservoir in the global ocean, but has not typically been thought to play an active role in deglacial CO2 rise based on its modern stratified state. Recent studies (Okazaki et al., 2010; Rae et al., 2014; Max et al., 2017), however, have suggested that a more dynamic circulation regime operated in the glacial and deglacial North Pacific and, as such, the role of the North Pacific in deglacial CO2 rise may have been underestimated. We present two new high-resolution boron isotope records of surface water pCO2 from the North West and North East Pacific spanning the last 22 kyrs. The two records show remarkable coherence over key intervals during the last deglaciation and highlight major changes over a number of abrupt climate events. At both sites, following the LGM, pCO2(sw) rises, coincident with a younging of North Pacific intermediate and deep waters. This suggests that increased local overturning mixed CO2-rich deep waters throughout the water column, likely contributing to CO2 outgassing during Heinrich Stadial 1 (HS1). Both records exhibit decreases in pCO2(sw) during the latter stages of HS1, which are immediately followed by a rapid increase in pCO2(sw) at the onset of the Bølling-Allerød (B/A). Radiocarbon and δ13C data indicate a collapse in North Pacific Intermediate Water formation at the onset of the B/A, which, combined with enhanced wind stress curl, would have allowed CO2-rich waters to mix into the surface ocean from intermediate-depths. The combination of high nutrient availability and a seasonally well-stratified mixed layer likely led to the abrupt increase in export productivity across the region; the excess surface water CO2 shows that alleviation of iron or light limitation could not have been its primary cause. Our new records highlight the importance of overturning circulation in the North Pacific in controlling productivity and CO2 release on glacial/interglacial timescales.

Enrichment of 13C by chemical exchange between CO2 and amine carbamate in nonaqueous solvent