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Sample records for bromoform

  1. Bromoform production in tropical open-ocean waters: OTEC chlorination

    Energy Technology Data Exchange (ETDEWEB)

    Hartwig, E.O.; Valentine, R.

    1981-09-01

    The bromoform, and other volatile organics produced while chlorinating both the evaporator and condenser seawater during operation of the one megawatt (1 MW) OTEC-1 test facility are reported. Although many halogenated compounds might be produced as a result of chlorination, the quantitative analyses in this study focused on volatile EPA priority pollutants. Bromoform is the compound specifically recognized as a potential pollutant. Its concentration may be indicative of other halogenated species.

  2. Modelling the vertical distribution of bromoform in the upper water column of the tropical Atlantic Ocean

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    I. Hense

    2008-12-01

    Full Text Available The relative importance of potential source and sink terms for bromoform (CHBr3 in the tropical Atlantic Ocean is investigated with a coupled physical-biogeochemical water column model. Bromoform production is either assumed to be linked to primary production or to phytoplankton losses; bromoform decay is treated as light dependent (photolysis, and in addition either vertically uniform, proportional to remineralisation or to nitrification. All experiments lead to the observed subsurface maximum of bromoform, corresponding to the subsurface phytoplankton biomass maximum. In the surface mixed layer, the concentration is set by entrainment from below, photolysis in the upper few meters and the outgassing to the atmosphere. The assumed bromoform production mechanism has only minor effects on the solution, but the various loss terms lead to significantly different bromoform concentrations below 200 m depth. The best agreement with observations is obtained when the bromoform decay is coupled to nitrification (parameterised by an inverse proportionality to the light field. Our model results reveal a pronounced seasonal cycle of bromoform outgassing, with a minimum in summer and a maximum in early winter, when the deepening surface mixed layer reaches down into the bromoform production layer.

  3. Modelling the vertical distribution of bromoform in the upper water column of the tropical Atlantic Ocean

    Directory of Open Access Journals (Sweden)

    I. Hense

    2009-04-01

    Full Text Available The relative importance of potential source and sink terms for bromoform (CHBr3 in the tropical Atlantic Ocean is investigated with a coupled physical-biogeochemical water column model. Bromoform production is either assumed to be linked to primary production or to phytoplankton losses; bromoform decay is treated as light dependent (photolysis, and in addition either vertically uniform, proportional to remineralisation or to nitrification. All experiments lead to the observed subsurface maximum of bromoform, corresponding to the subsurface phytoplankton biomass maximum. In the surface mixed layer, the concentration is set by entrainment from below, photolysis in the upper few meters and the outgassing to the atmosphere. The assumed bromoform production mechanism has only minor effects on the solution, but the various loss terms lead to significantly different bromoform concentrations below 200 m depth. The best agreement with observations is obtained when the bromoform decay is coupled to nitrification (parameterised by an inverse proportionality to the light field. Our model results reveal a pronounced seasonal cycle of bromoform outgassing, with a minimum in summer and a maximum in early winter, when the deepening surface mixed layer reaches down into the bromoform production layer.

  4. Modeling the interaction of ozone with chloroform and bromoform under conditions close to stratospheric

    Science.gov (United States)

    Strokova, N. E.; Yagodovskaya, T. V.; Savilov, S. V.; Lukhovitskaya, E. E.; Vasil'ev, E. S.; Morozov, I. I.; Lunin, V. V.

    2013-02-01

    The reactions of ozone with chloroform and bromoform are studied using a flow gas discharge vacuum unit under conditions close to stratospheric (temperature range, 77-250 K; pressure, 10-3-0.1 Torr in the presence of nitrate ice). It is shown that the reaction with bromoform begins at 160 K; the reaction with chloroform, at 190 K. The reaction products are chlorine and bromine oxides of different composition, identified by low-temperature FTIR spectroscopy. The presence of nitrate ice raises the temperature of reaction onset to 210 K.

  5. What do we learn on bromoform transport and chemistry in deep convection from fine scale modelling?

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    V. Marécal

    2011-11-01

    Full Text Available Bromoform is one of the main sources of halogenated Very Short-Lived Species (VSLS that possibly contributes when degradated to the inorganic halogen loading in the stratosphere. Because of its short lifetime of about four weeks, its pathway to the stratosphere is mainly the transport by convection up to the tropical tropopause layer (TTL and then by radiative ascent in the low stratosphere. Some of its degradation product gases (PGs that are soluble can be scavenged and not reach the TTL.

    In this paper we present a detailed modelling study of the transport and the degradation of bromoform and its PGs in convection. We use a 3-D-cloud resolving model coupled with a chemistry model including gaseous and aqueous chemistry. We run idealised simulations up to 10 days, initialised using a tropical radiosounding for atmospheric conditions and using outputs from a global chemistry-transport model for chemical species. Bromoform is initialised only in the low levels. The first simulation is run with stable atmospheric conditions. It shows that the sum of the bromoform and its PGs significantly decreases with time because of dry deposition and that PGs are mainly in the form of HBr after 2 days of simulation. The other simulation is similar to the first simulation but includes perturbations of temperature and of moisture leading to the development of a convective cloud reaching the TTL. Results of this simulation show an efficient vertical transport of the bromoform from the boundary layer in the upper troposphere and TTL (mixing ratio up to 45% of the initial boundary layer mixing ratio. The organic PGs, which are for the most abundant of them not very soluble, are also uplifted efficiently. For the inorganic PGs, which are more abundant than organic PGs, their mixing ratios in the upper troposphere and in the TTL depend on the partitioning between inorganic soluble and inorganic non soluble species in the convective cloud. Important soluble

  6. Carbenic vs. ionic mechanistic pathway in reaction of cyclohexanone with bromoform.

    Science.gov (United States)

    Vitnik, Vesna D; Vitnik, Zeljko J; Juranić, Ivan O

    2012-10-01

    The extensive computation study was done to elucidate the mechanism of formation dibromoepoxide from cyclohexanone and bromoform. In this reaction, the formation of dihaloepoxide 2 is postulated as a key step that determines the distribution and stereochemistry of products. Two mechanistic paths of reaction were investigated: the addition of dibromocarbene to carbonyl group of ketone, and the addition of tribromomethyl carbanion to the same (C=O) group. The mechanisms for the addition reactions of dibromocarbenes and tribromomethyl carbanions with cyclohexanone have been investigated using ab initio HF/6-311++G** and MP2/6-311+G* level of theory. Solvent effects on these reactions have been explored by calculations which included a continuum polarizable conductor model (CPCM) for the solvent (H₂O). The calculations showed that both mechanisms are possible and are exothermic, but have markedly different activation energies.

  7. Bromoform and Dibromomethane Emission During the SHIVA Western Pacific 2011 Field Campaign: A 3-D Model Case Study

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    Mantle, Hannah; Hossaini, Ryan; Chipperfield, Martyn

    2013-04-01

    Halogenated very short-lived species (VSLS) with atmospheric lifetimes of SHIVA Malaysia 2011 field campaign provided a comprehensive VSLS dataset obtained in a region where these source gases have the potential to reach the stratosphere and deplete ozone. Observations of VSLS were collected during November and December 2011 on board the DLR Falcon aircraft during sixteen local flights. Fourteen of these flights have been used in this study due to technical difficulties experienced on the remaining two flights. Four emission scenarios, including both top-down and bottom-up approaches derived from airborne measurements and ocean fluxes of VSLS, were used in TOMCAT and each scenario was compared to observations of bromoform and dibromomethane collected during the SHIVA campaign. The mean bias of each emission scenario against the SHIVA observations was calculated for all fourteen flights considered. Results indicate that the bottom-up emission scenario, derived from measured oceanic fluxes of bromoform and dibromomethane, matches the SHIVA observed values of both major VSLS source gases more closely than that of the top-down emission scenarios (0.16 pptv total mean bias for both bromoform and dibromomethane for all fourteen flights considered). Although slightly underestimating the SHIVA observed values, all other emission scenarios overestimate the observations of bromoform by a greater magnitude. Dibromomethane is underestimated by two emission scenarios and overestimated by one, all by a greater extent than that of the bottom-up emission scenario derived from measured VSLS oceanic fluxes. Global mixing ratio maps highlight the difference in global distribution of VSLS emissions between each emission scenario. Our work suggests that bottom-up derived emission estimates may be more accurate than those derived from airborne measurements, but that all methods produce surface level values within the WMO ranges given for MBL bromoform and dibromomethane. A truly global

  8. Global sea-to-air flux climatology for bromoform, dibromomethane and methyl iodide

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    F. Ziska

    2013-02-01

    Full Text Available Volatile halogenated organic compounds containing bromine and iodine, which are naturally produced in the ocean, are involved in ozone depletion in both the troposphere and stratosphere. Three prominent compounds transporting large amounts of marine halogens into the atmosphere are bromoform (CHBr3, dibromomethane (CH2Br2 and methyl iodide (CH3I. The input of marine halogens to the stratosphere is based on observations and modeling studies using low resolution oceanic emission scenarios derived from top down approaches. In order to improve emission inventory estimates, we calculate data-based high resolution global sea-to-air flux estimates of these compounds from surface observations within the HalOcAt database (https://halocat.geomar.de/. Global maps of marine and atmospheric surface concentrations are derived from the data which are divided into coastal, shelf and open ocean regions. Considering physical and biogeochemical characteristics of ocean and atmosphere, the open ocean water and atmosphere data are classified into 21 regions. The available data are interpolated onto a 1° × 1° grid while missing grid values are interpolated with latitudinal and longitudinal dependent regression techniques reflecting the compounds' distributions. With the generated surface concentration climatologies for the ocean and atmosphere, global concentration gradients and sea-to-air fluxes are calculated. Based on these calculations we estimate a total global flux of 1.5/2.5 Gmol Br yr−1 for CHBr3, 0.78/0.98 Gmol Br yr−1 for CH2Br2 and 1.24/1.45 Gmol I yr−1 for CH3I (Robust Fit/Ordinary Least Square regression technique. Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic region. "Hot spots" for global

  9. Global sea-to-air flux climatology for bromoform, dibromomethane and methyl iodide

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    F. Ziska

    2013-09-01

    Full Text Available Volatile halogenated organic compounds containing bromine and iodine, which are naturally produced in the ocean, are involved in ozone depletion in both the troposphere and stratosphere. Three prominent compounds transporting large amounts of marine halogens into the atmosphere are bromoform (CHBr3, dibromomethane (CH2Br2 and methyl iodide (CH3I. The input of marine halogens to the stratosphere has been estimated from observations and modelling studies using low-resolution oceanic emission scenarios derived from top-down approaches. In order to improve emission inventory estimates, we calculate data-based high resolution global sea-to-air flux estimates of these compounds from surface observations within the HalOcAt (Halocarbons in the Ocean and Atmosphere database (https://halocat.geomar.de/. Global maps of marine and atmospheric surface concentrations are derived from the data which are divided into coastal, shelf and open ocean regions. Considering physical and biogeochemical characteristics of ocean and atmosphere, the open ocean water and atmosphere data are classified into 21 regions. The available data are interpolated onto a 1°×1° grid while missing grid values are interpolated with latitudinal and longitudinal dependent regression techniques reflecting the compounds' distributions. With the generated surface concentration climatologies for the ocean and atmosphere, global sea-to-air concentration gradients and sea-to-air fluxes are calculated. Based on these calculations we estimate a total global flux of 1.5/2.5 Gmol Br yr−1 for CHBr3, 0.78/0.98 Gmol Br yr−1 for CH2Br2 and 1.24/1.45 Gmol Br yr−1 for CH3I (robust fit/ordinary least squares regression techniques. Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic regions. "Hot spots" for global polybromomethane emissions are located in the equatorial region, whereas methyl iodide emissions are enhanced in the

  10. CHBr3 (bromoform): Revised UV Absorption Spectrum and Atmospheric Photolysis Rates

    Science.gov (United States)

    Burkholder, J. B.; Papanastasiou, D.; McKeen, S. A.

    2013-12-01

    CHBr3 (bromoform) is a short-lived atmospheric trace compound primarily of natural origin that is a source of reactive bromine in both the troposphere and stratosphere. Estimating the impact of CHBr3 on the environment and its transport to the stratosphere requires a thorough understanding of its atmospheric loss processes, which are primarily UV photolysis and reaction with the OH radical. In this presentation, new measurements of the UV absorption spectrum of CHBr3 will be presented. Spectra were measured at wavelengths between 300 and 345 nm at temperatures between 260 and 330 K using cavity ring-down spectroscopy. The present results will be compared with currently recommended values for use in atmospheric modeling taken from Moortgat et al. [The tropospheric chemistry of ozone in the polar regions, edited by H. Niki and K. H. Becker, Springer-Verlag Berlin Heidelberg, 1993]. The discrepancies and impact on CHBr3 photolysis lifetime will be discussed. A parameterization of the CHBr3 UV spectrum for use in atmospheric models will be presented and local photolysis rate calculations used to highlight the impact of the revised cross section data on local lifetimes and the relative importance of photolysis loss versus reaction with the OH radical. The results from the present study will contribute to a better understanding (and accuracy) of estimates of stratospheric ozone loss due to very short-lived brominated substances.

  11. The alkaline comet assay used in evaluation of genotoxic damage of drinking water disinfection by-products (bromoform and chloroform

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    Messaouda Khallef

    2015-06-01

    Full Text Available The alkaline comet assay (pH 12.3 is a useful method for monitoring genotoxic effects of environmental pollutants in the root nuclei of Allium cepa and various plants; it allows the detection of single- and double-strand breaks, incomplete excision-repair sites and cross-links. It has been introduced to detect even small changes in DNA structure. It is a technically simple, highly sensitive, fast and economic test which detects in vitro and in vivo genotoxicity (DNA integrity and packing mode in any cell types examined, and requires just a few cells for its execution (Liman et al., 2011; Yıldız et al., 2009. Chloroform and bromoform are the most important trihalomethanes found in drinking water. Different concentrations of bromoform (25, 50, 75and 100µg/ml and chloroform (25, 50, 100 and 200 µg/ml were introduced to onion tuber roots. Distilled water was used as a negative control and methyl methansulfonate (MMS-10 µg/ml as positive control. All obtained data were subjected to statistical analyses by using SPSS 15.0 for Windows software. For comparison purposes, Duncan multiple range tests using one-way analysis of variance (ANOVA were employed and p<0.05 was accepted as the test of significance. Comet assay results showed that DNA damage was significant at p <0.05 for the different concentrations of chloroform and bromoform compared to the negative control which has a damage rate equal to 3.5 ± 0.7 and the positive control which has damage rate equal to 13.5 ± 2.12. The exposure of root tip cells to these disinfection by-products increases DNA damage. All concentrations examined in this study of bromoform and chloroform cause significant harm, which could be due to DNA damage induced by oxidative stress. The measurement of DNA damage in the nuclei of higher plant tissues is a new area of study with SCGE. This assay could be incorporated into in situ monitoring of atmosphere, water and soil: the comet assay allows a fast detection without

  12. Atmospheric bromoform at Mace Head, Ireland: seasonality and evidence for a peatland source

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    L. J. Carpenter

    2005-01-01

    Full Text Available In situ atmospheric observations of bromoform (CHBr3 made over a 2.5 year period at Mace Head, Ireland from May 2001- Dec 2003, including during the NAMBLEX (North Atlantic Marine Boundary Layer Experiment campaign, show broad maxima from spring until autumn and winter minima, with mixing ratios of 5.3+1.0 pptv (mid March - mid October and 1.8+0.8 pptv (December-February. This indicates that, unlike CHCl3, which has a summer minimum and winter maximum at Mace Head, local biological sources of CHBr3 have a greater influence on the atmospheric data than photochemical decay during long-range transport. The emission sources are predominantly macroalgal, but we find evidence for a small terrestrial flux from peatland ecosystems, which so far has not been accounted for in the CHBr3 budget. Sharp increases in CHCl3 and CHBr3 concentrations and decreases in O3 concentrations occurred at night when the wind direction switched from an ocean- to a land-based sector (land breeze and the wind speed dropped to below 5 ms-1. These observations infer a shallow atmospheric boundary layer with increased O3 deposition and concentration of local emissions of both CHCl3 and CHBr3. The ratio of ΔCHCl3/ΔCHBr3 varied strongly according to the prevailing wind direction; from 0.60+0.15 in south-easterly (100-170° and northerly (340-20° air to 2.5+0.4 in north-easterly (40-70° air. Of these land-sectors, the south-easterly air masses are likely to be strongly influenced by macroalgal beds along the coast and the emission ratios probably reflect those from seaweeds in addition to land sources. The north-easterly airmasses however had an immediate fetch inland, which locally is comprised of coastal peatland ecosystems (peat bogs and coastal conifer plantations, previously identified as being strong sources of atmospheric CHCl3 under these conditions. Although we cannot entirely rule out other local land or coastal sources, our observations also suggest peatland

  13. Modelling the chemistry and transport of bromoform within a sea breeze driven convective system during the SHIVA Campaign

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    Hamer, P. D.; Marécal, V.; Hossaini, R.; Pirre, M.; Warwick, N.; Chipperfield, M.; Samah, A. A.; Harris, N.; Robinson, A.; Quack, B.; Engel, A.; Krüger, K.; Atlas, E.; Subramaniam, K.; Oram, D.; Leedham, E.; Mills, G.; Pfeilsticker, K.; Sala, S.; Keber, T.; Bönisch, H.; Peng, L. K.; Nadzir, M. S. M.; Lim, P. T.; Mujahid, A.; Anton, A.; Schlager, H.; Catoire, V.; Krysztofiak, G.; Fühlbrügge, S.; Dorf, M.; Sturges, W. T.

    2013-08-01

    We carry out a case study of the transport and chemistry of bromoform and its product gases (PGs) in a sea breeze driven convective episode on 19 November 2011 along the North West coast of Borneo during the "Stratospheric ozone: Halogen Impacts in a Varying Atmosphere" (SHIVA) campaign. We use ground based, ship, aircraft and balloon sonde observations made during the campaign, and a 3-D regional online transport and chemistry model capable of resolving clouds and convection explicitly that includes detailed bromine chemistry. The model simulates the temperature, wind speed, wind direction fairly well for the most part, and adequately captures the convection location, timing, and intensity. The simulated transport of bromoform from the boundary layer up to 12 km compares well to aircraft observations to support our conclusions. The model makes several predictions regarding bromine transport from the boundary layer to the level of convective detrainment (11 to 12 km). First, the majority of bromine undergoes this transport as bromoform. Second, insoluble organic bromine carbonyl species are transported to between 11 and 12 km, but only form a small proportion of the transported bromine. Third, soluble bromine species, which include bromine organic peroxides, hydrobromic acid (HBr), and hypobromous acid (HOBr), are washed out efficiently within the core of the convective column. Fourth, insoluble inorganic bromine species (principally Br2) are not washed out of the convective column, but are also not transported to the altitude of detrainment in large quantities. We expect that Br2 will make a larger relative contribution to the total vertical transport of bromine atoms in scenarios with higher CHBr3 mixing ratios in the boundary layer, which have been observed in other regions. Finally, given the highly detailed description of the chemistry, transport and washout of bromine compounds within our simulations, we make a series of recommendations about the physical and

  14. Modelling the chemistry and transport of bromoform within a sea breeze driven convective system during the SHIVA Campaign

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    P. D. Hamer

    2013-08-01

    Full Text Available We carry out a case study of the transport and chemistry of bromoform and its product gases (PGs in a sea breeze driven convective episode on 19 November 2011 along the North West coast of Borneo during the "Stratospheric ozone: Halogen Impacts in a Varying Atmosphere" (SHIVA campaign. We use ground based, ship, aircraft and balloon sonde observations made during the campaign, and a 3-D regional online transport and chemistry model capable of resolving clouds and convection explicitly that includes detailed bromine chemistry. The model simulates the temperature, wind speed, wind direction fairly well for the most part, and adequately captures the convection location, timing, and intensity. The simulated transport of bromoform from the boundary layer up to 12 km compares well to aircraft observations to support our conclusions. The model makes several predictions regarding bromine transport from the boundary layer to the level of convective detrainment (11 to 12 km. First, the majority of bromine undergoes this transport as bromoform. Second, insoluble organic bromine carbonyl species are transported to between 11 and 12 km, but only form a small proportion of the transported bromine. Third, soluble bromine species, which include bromine organic peroxides, hydrobromic acid (HBr, and hypobromous acid (HOBr, are washed out efficiently within the core of the convective column. Fourth, insoluble inorganic bromine species (principally Br2 are not washed out of the convective column, but are also not transported to the altitude of detrainment in large quantities. We expect that Br2 will make a larger relative contribution to the total vertical transport of bromine atoms in scenarios with higher CHBr3 mixing ratios in the boundary layer, which have been observed in other regions. Finally, given the highly detailed description of the chemistry, transport and washout of bromine compounds within our simulations, we make a series of recommendations about

  15. Distributions and sea-to-air fluxes of chloroform, trichloroethylene, tetrachloroethylene, chlorodibromomethane and bromoform in the Yellow Sea and the East China Sea during spring.

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    He, Zhen; Yang, Gui-Peng; Lu, Xiao-Lan; Zhang, Hong-Hai

    2013-06-01

    Halocarbons including chloroform (CHCl3), trichloroethylene (C2HCl3), tetrachloroethylene (C2Cl4), chlorodibromomethane (CHBr2Cl) and bromoform (CHBr3) were measured in the Yellow Sea (YS) and the East China Sea (ECS) during spring 2011. The influences of chlorophyll a, salinity and nutrients on the distributions of these gases were examined. Elevated levels of these gases in the coastal waters were attributed to anthropogenic inputs and biological release by phytoplankton. The vertical distributions of these gases in the water column were controlled by different source strengths and water masses. Using atmospheric concentrations measured in spring 2012 and seawater concentrations obtained from this study, the sea-to-air fluxes of these gases were estimated. Our results showed that the emissions of C2HCl3, C2Cl4, CHBr2Cl, and CHBr3 from the study area could account for 16.5%, 10.5%, 14.6%, and 3.5% of global oceanic emissions, respectively, indicating that the coastal shelf may contribute significantly to the global oceanic emissions of these gases.

  16. The very short-lived ozone depleting substance CHBr3 (bromoform): Revised UV absorption spectrum, atmospheric lifetime and ozone depletion potential

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    Papanastasiou, Dimitrios K.; McKeen, Stuart A.; Burkholder, James B.

    2014-05-01

    CHBr3 (bromoform) is a short-lived atmospheric trace gas primarily of natural origin that represents a source of reactive bromine (Bry; Br + BrO) in the troposphere as well as the stratosphere. The transport of short-lived brominated species, and their brominated degradation products, to the stratosphere is known to be particularly impactful to stratospheric ozone due to the high efficiency of ozone destruction cycles involving bromine. Evaluating the impact of CHBr3 on stratospheric ozone requires not only a thorough understanding of its emissions, but also its atmospheric loss processes, which are primarily UV photolysis and reaction with the OH radical. The total global lifetime of CHBr3 is ~24 days and is mostly governed by its photolytic loss. Therefore, accurate CHBr3 UV absorption cross section data for wavelengths (Λ) in the actinic region, greater than 290 nm, are needed to calculate its photolysis loss rate. Currently, there is a single study (Moortgat et al., Springer-Verlag Berlin Heidelberg, 1993; Vol. 17) that reports CHBr3 UV absorption cross sections and their temperature dependence in a wavelength and temperature range applicable for atmospheric photolysis rate calculations. However, there are indications that the reported longer wavelength cross section data, in the Moortgrat et al. study, might be subject to systematic errors which possibly lead to erroneous CHBr3 atmospheric photolysis rate calculations and a misleading picture of its impact on stratospheric ozone. In this study, UV absorption cross sections, σ(Λ,T), for CHBr3 were measured at wavelengths between 300 and 345 nm at temperatures between 260 and 330 K using cavity ring-down spectroscopy. A thorough investigation of possible sources of systematic error in the measurements is presented. The present UV absorption cross sections at longer wavelength (>310 nm) are systematically lower compared to currently recommended values for use in atmospheric models, with the deviation being

  17. Prediction of RO/NF membrane rejections of PhACs and organic compounds: a statistical analysis

    NARCIS (Netherlands)

    Yangali-Quintanilla, V.; Kim, T.U.; Kennedy, M.; Amy, G.

    2008-01-01

    OA fund TU Delft Rejections of pharmaceutical compounds (Ibuprofen, Diclofenac, Clofibric acid, Naproxen, Primidone, Phenacetin) and organic compounds (Dichloroacetic acid, Trichloroacetic acid, Chloroform, Bromoform, Trichloroethene, Perchloroethene, Car-bontetrachloride, Carbontetrabromide) by NF

  18. Investigations into the photochemical degradation of biogenic and anthropogeneous halogenated hydrocarbons in seawater; Untersuchungen zum photochemischen Abbau von biogenen und anthropogenen halogenierten Kohlenwasserstoffen im Meerwasser

    Energy Technology Data Exchange (ETDEWEB)

    Faller, J.T.

    1992-05-20

    Bromoform and hexachloro-cyclohexane in seawater were studied for their possible degradation. Bromoform is demonstrably degraded through the effect of sunlight. Hydrogen peroxide present in seawater contributes to the acceleration of this effect. The second compound investigated is also photochemically degraded in seawater. This degradation mechanism is described in the paper. Increased temperature and the presence of hydrogen peroxide accelerate the degradation. (VT) [Deutsch] Bromoform und Hexachlorcyclohexan im Meerwasser sollten auf ihren moeglichen Abbau untersucht werden. Bromoform wird nachweisbar durch Einwirkung von Sonnenlicht abgebaut. Zur Beschleunigung der Reaktion traegt das im Seewasser anwesende Wasserstoffperoxid bei. Die zweite untersuchte Verbindung wird im Meer ebenfalls photochemisch abgebaut. Der Mechanismus des Abbaus ist in der Arbeit beschrieben. Die Temperaturerhoehung und die Anwesenheit des Wasserstoffperoxids beschleunigen den Abbau. (VT)

  19. Unexpected variability of millennium green: structural color of Japanese jewel beetle resulted from thermosensitive porous organic multilayer.

    Science.gov (United States)

    Adachi, Eiki

    2007-09-01

    The Japanese jewel beetle (Chrysochroa fulgidissima) is one of the beautiful beetles showing metallic green color that is kept over a millennium. This is a typical structural color resulting from a multilayer, frequently seen in insects. It was found that the elytra unexpectedly change the color from original green to blue or red by heating at 200 degrees C or by immersing in bromoform for over 1 month. This variability implies that the multilayer consists of a thermosensitive porous material. The color change induced by heating was accompanied with elytron shrinkage; the sensitivity of the reflection peak was -0.6 nm/ degrees C in 30-65 degrees C. The porous structure was determined by positron annihilation lifetime spectroscopy; the averaged pore radius was around 0.25-0.30 nm, which is close to the size of the bromoform molecule. These features prove the thermosensitivity and porous structure of the multilayer although in unusual environments.

  20. A multi-model intercomparison of halogenated very short-lived substances (TransCom-VSLS): linking oceanic emissions and tropospheric transport for a reconciled estimate of the stratospheric source gas injection of bromine

    OpenAIRE

    R. Hossaini; Patra, P. K.; Leeson, A.A.; Krysztofiak, G.; Abraham, N.L.; Andrews, S. J.; Archibald, A.T.; Aschmann, J.; E. L. Atlas; Belikov, D. A.; Bonisch, H.; Carpenter, L. J.; Dhomse, S.; Dorf, M.; Engel, A

    2016-01-01

    The first concerted multi-model intercomparison of halogenated very short-lived substances (VSLS) has been performed, within the framework of the ongoing Atmospheric Tracer Transport Model Intercomparison Project (TransCom). Eleven global models or model variants participated (nine chemical transport models and two chemistry– climate models) by simulating the major natural bromine VSLS, bromoform (CHBr3) and dibromomethane (CH2Br2), over a 20-year period (1993–2012). Except for three model si...

  1. The contribution of oceanic halocarbons to marine and free tropospheric air over the tropical West Pacific

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    Fuhlbrügge, Steffen; Quack, Birgit; Tegtmeier, Susann; Atlas, Elliot; Hepach, Helmke; Shi, Qiang; Raimund, Stefan; Krüger, Kirstin

    2016-06-01

    Emissions of halogenated very-short-lived substances (VSLSs) from the oceans contribute to the atmospheric halogen budget and affect tropospheric and stratospheric ozone. Here, we investigate the contribution of natural oceanic VSLS emissions to the marine atmospheric boundary layer (MABL) and their transport into the free troposphere (FT) over the tropical West Pacific. The study concentrates on bromoform, dibromomethane and methyl iodide measured on ship and aircraft during the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere) campaign in the South China and Sulu seas in November 2011. Elevated oceanic concentrations for bromoform, dibromomethane and methyl iodide of on average 19.9, 5.0 and 3.8 pmol L-1, in particular close to Singapore and to the coast of Borneo, with high corresponding oceanic emissions of 1486, 405 and 433 pmol m-2 h-1 respectively, characterise this tropical region as a strong source of these compounds. Atmospheric mixing ratios in the MABL were unexpectedly relatively low with 2.08, 1.17 and 0.39 ppt for bromoform, dibromomethane and methyl iodide. We use meteorological and chemical ship and aircraft observations, FLEXPART trajectory calculations and source-loss estimates to identify the oceanic VSLS contribution to the MABL and to the FT. Our results show that the well-ventilated MABL and intense convection led to the low atmospheric mixing ratios in the MABL despite the high oceanic emissions. Up to 45 % of the accumulated bromoform in the FT above the region originates from the local South China Sea area, while dibromomethane is largely advected from distant source regions and the local ocean only contributes 20 %. The accumulated methyl iodide in the FT is higher than can be explained with local contributions. Possible reasons, uncertainties and consequences of our observations and model estimates are discussed.

  2. The Effect of Different Boiling and Filtering Devices on the Concentration of Disinfection By-Products in Tap Water

    OpenAIRE

    Glòria Carrasco-Turigas; Villanueva, Cristina M.; Fernando Goñi; Panu Rantakokko; Nieuwenhuijsen, Mark J.

    2013-01-01

    Disinfection by-products (DBPs) are ubiquitous contaminants in tap drinking water with the potential to produce adverse health effects. Filtering and boiling tap water can lead to changes in the DBP concentrations and modify the exposure through ingestion. Changes in the concentration of 4 individual trihalomethanes (THM4) (chloroform (TCM), bromodichloromethane (BDCM), dibromochloromethane (DBCM), and bromoform (TBM)), MX, and bromate were tested when boiling and filtering high bromine-conta...

  3. 循環式浴槽におけるトリハロメタンに関する研究

    OpenAIRE

    長谷川, 駿||ハセガワ, シュン||Hasegawa, Shun; 鎌田, 素之; 野知, 啓子

    2007-01-01

    The circulation type bathtub is widely used because of economical efficiency. Chlorination is obligated to circulation type bathtub to prevent infection disease such as legionaires' disease. Though, chlorination can prevent infection disease, cause carcinogenic disinfection by product(DBPs). The major DBPs are chloroform, bromodichloromethane, dibromochloromethane and bromoform, so called trihalomethanes(THM)which are volatile compound. We conduct our research to reveal concentration level of...

  4. Modeling the transport of very short-lived substances into the tropical upper troposphere and lower stratosphere

    Directory of Open Access Journals (Sweden)

    J. Aschmann

    2009-09-01

    Full Text Available The transport of very short-lived substances into the tropical upper troposphere and lower stratosphere is investigated by a three-dimensional chemical transport model using archived convective updraft mass fluxes (or detrainment rates from the European Centre for Medium-Range Weather Forecast's ERA-Interim reanalysis. Large-scale vertical velocities are calculated from diabatic heating rates. With this approach we explicitly model the large scale subsidence in the tropical troposphere with convection taking place in fast and isolated updraft events. The model calculations agree generally well with observations of bromoform and methyl iodide from aircraft campaigns and with ozone and water vapor from sonde and satellite observations. Using a simplified treatment of dehydration and bromine product gas washout we give a range of 1.6 to 3 ppt for the contribution of bromoform to stratospheric bromine, assuming a uniform source in the boundary layer of 1 ppt. We show that the most effective region for VSLS transport into the stratosphere is the West Pacific, accounting for about 55% of the bromine from bromoform transported into the stratosphere under the supposition of a uniformly distributed source.

  5. Influence of Natural Organic Matter (NOM) Character on the Distribution of Chlorinated and Chloraminated Disinfection By-Products (DBPs) at Rand Water

    Science.gov (United States)

    Marais, Savia S.; Ncube, Esper J.; Haarhoff, Johannes; Msagati, Titus AM; Mamba, Bhekie B.; Nkambule, Thabo I.

    2016-04-01

    Certain disinfection by-products (DBPs) are likely human carcinogens or present mutagenic effects while many DBPs are unidentified. Considering the possibility of DBPs being harmful to human health and the fact that trihalomethanes (THMs) are the only regulated DBP in the South African National Standard (SANS:241) for drinking water, special interest in the precursors to these DBPs' formation is created. It is essential to understand the reactivity and character of the precursors responsible for the formation of DBPs in order to enhance precursor removal strategies during the treatment of drinking water. In this study the character of NOM within surface water and the subsequent distribution of THMs formed in the drinking water from Rand Waters' full scale treatment plant were investigated. Molecular size distribution (MSD) of NOM within the surface water was determined by high performance size exclusion chromatography (HPSEC). Specific ultraviolet absorbance (SUVA) and UV254 measurements formed part of the NOM character study as they provide an indication of the aromaticity of organic matter. The four THMs; bromoform, chloroform, dibromochloromethane (DBCM) and bromodichloromethane (BDCM)were measured by gas chromatography. The sum of these four THMs was expressed as total trihalomethane (TTHM). On average the chloroform constituted 76.2% of the total TTHM, BDCM 22.5% while DBCM and bromoform measured below the detection limit. THM speciation after chlorination and chloramination concentrations increased in the sequence bromoform water in summer when high temperatures and rainfall occurred. The results displayed are an indication that aromatic NOM were the main precursor to TTHM formation, more prominently during summer. Keywords: disinfection by-products, molecular size distribution, natural organic matter, UV254

  6. [Human exposure to trihalomethanes in drinking water].

    Science.gov (United States)

    Tominaga, M Y; Midio, A F

    1999-08-01

    Halogenated hydrocarbon compounds, some of them recognized as carcinogenic to different animal species can be found in drinking water. Chloroform, bromodichloromethane, dibromochloromethane and bromoform are the most important trihalomethanes found in potable water. They are produced in natural waters during chlorinated desinfection by the halogenation of precursors, specially humic and fulvic compounds. The review, in the MEDLINE covers the period from 1974 to 1998, presents the general aspects of the formation of trihalomethanes, sources of human exposure and their toxicological meaning for exposed organisms: toxicokinetic disposition and spectrum of toxic effects (carcinogenic, mutagenic and teratogenic).

  7. 40 CFR Table 1 to Subpart Dd of... - List of Hazardous Air Pollutants (HAP) for Subpart DD

    Science.gov (United States)

    2010-07-01

    ...-05-8 Acetonitrile 0.989 98-86-2 Acetophenone 0.314 107-02-8 Acrolein 1.000 107-13-1 Acrylonitrile 0.999 107-05-1 Allyl chloride 1.000 71-43-2 Benzene (includes benzene in gasoline) 1.000 98-07-7...(chloromethyl)ether b 0.999 75-25-2 Bromoform 0.998 106-99-0 1,3-Butadiene 1.000 75-15-0 Carbon disulfide...

  8. Sensitivity and variability of Presage dosimeter formulations in sheet form with application to SBRT and SRS QA

    Energy Technology Data Exchange (ETDEWEB)

    Dumas, Michael, E-mail: mdumas1127@gmail.com [Department of Radiation Oncology, Wayne State University School of Medicine and Karmanos Cancer Institute Detroit, Detroit, Michigan 48201 and Department of Radiation Oncology, Henry Ford Hospital, Detroit, Michigan 48202 (United States); Rakowski, Joseph T. [Department of Radiation Oncology, Wayne State University School of Medicine and Karmanos Cancer Institute Detroit, Detroit, Michigan 48201 (United States)

    2015-12-15

    Purpose: To measure sensitivity and stability of the Presage dosimeter in sheet form for various chemical concentrations over a range of clinical photon energies and examine its use for stereotactic body radiation therapy (SBRT) and stereotactic radiosurgery (SRS) QA. Methods: Presage polymer dosimeters were formulated to investigate and optimize their sensitivity and stability. The dosimeter is composed of clear polyurethane base, leucomalachite green (LMG) reporting dye, and bromoform radical initiator in 0.9–1.0 mm thick sheets. The chemicals are mixed together for 2 min, cast in an aluminum mold, and left to cure at 60 psi for a minimum of two days. Dosimeter response was characterized at energies Co-60, 6 MV, 10 MV flattening-filter free, 15 MV, 50 kVp (mean 19.2 keV), and Ir-192. The dosimeters were scanned by a Microtek Scanmaker i800 at 300 dpi, 2{sup 16} bit depth per color channel. Red component images were analyzed with ImageJ and RIT. SBRT QA was done with gamma analysis tolerances of 2% and 2 mm DTA. Results: The sensitivity of the Presage dosimeter increased with increasing concentration of bromoform. Addition of tin catalyst decreased curing time and had negligible effect on sensitivity. LMG concentration should be at least as high as the bromoform, with ideal concentration being 2% wt. Gamma Knife SRS QA measurements of relative output and profile widths were within 2% of manufacturer’s values validated at commissioning, except the 4 mm collimator relative output which was within 3%. The gamma pass rate of Presage with SBRT was 73.7%, compared to 93.1% for EBT2 Gafchromic film. Conclusions: The Presage dosimeter in sheet form was capable of detecting radiation over all tested photon energies and chemical concentrations. The best sensitivity and photostability of the dosimeter were achieved with 2.5% wt. LMG and 8.2% wt. bromoform. Scanner used should not emit any UV radiation as it will expose the dosimeter, as with the Epson 10000 XL scanner

  9. SU-E-T-265: Presage Thin Sheet Dosimeter Characterization

    Energy Technology Data Exchange (ETDEWEB)

    Dumas, M; Rakowski, J [Wayne State University/Karmanos Cancer Institute, Detroit, MI (United States)

    2014-06-01

    Purpose: To quantify the sensitivity and stability of the Presage dosimeter in sheet form for different concentrations of chemicals and for a diverse range of clinical photon energies. Methods: Presage polymer dosimeters are formulated to investigate and optimize their sensitivity and stability. The dosimeter is composed of clear polyurethane base, leucomalachite green reporting dye, and bromoform radical initiator in 1mm thick sheets. The chemicals are well mixed together, cast in an aluminum mold, and left to cure at 60 psi for a minimum of 2 days. Dosimeter response will be characterized at multiple energies including Co-60, 6 MV, 15 MV, 50 kVp, and 250 kVp. The dosimeters are read by an Epson 10000 XL scanner at 800 dpi, 2{sup 16} bit depth. Red component images are analyzed with ImageJ. Results: Analysis of optical density verse dose for Co-60 energies indicates that the bromoform containing Presage was able to quantify dose from 0 to 300 Gy, with saturation beyond 300 Gy. Initial results show two regions of linear response, 0–100 Gy and 150–300 Gy. The 150–300 Gy region has a sensitivity of 0.0024 net OD/Gy. Further results on other energies are still in progress. Conclusions: This work shows the potential for use of thin sheets of Presage dosimeter as a dosimeter capable of being analyzed with a flatbed scanner.

  10. Occurrence of Selected Pharmaceutical and Organic Wastewater Compounds in Effluent and Water Samples from Municipal Wastewater and Drinking-Water Treatment Facilities in the Tar and Cape Fear River Basins, North Carolina, 2003-2005

    Science.gov (United States)

    Ferrell, G.M.

    2009-01-01

    Samples of treated effluent and treated and untreated water were collected at 20 municipal wastewater and drinkingwater treatment facilities in the Tar and Cape Fear River basins of North Carolina during 2003 and 2005. The samples were analyzed for a variety of prescription and nonprescription pharmaceutical compounds and a suite of organic compounds considered indicative of wastewater. Concentrations of these compounds generally were less than or near the detection limits of the analytical methods used during this investigation. None of these compounds were detected at concentrations that exceeded drinking-water standards established by the U.S. Environmental Protection Agency. Bromoform, a disinfection byproduct, was the only compound detected at a concentration that exceeded regulatory guidelines. The concentration of bromoform in one finished drinking-water sample, 26 micrograms per liter, exceeded North Carolina water-quality criteria. Drinking-water treatment practices were effective at removing many of the compounds detected in untreated water. Disinfection processes used in wastewater treatment - chlorination or irradiation with ultraviolet light - did not seem to substantially degrade the organic compounds evaluated during this study.

  11. Modeling of RO/NF membrane rejections of PhACs and organic compounds: a statistical analysis

    Directory of Open Access Journals (Sweden)

    G. Amy

    2008-07-01

    Full Text Available Rejections of pharmaceutical compounds (Ibuprofen, Diclofenac, Clofibric acid, Naproxen, Primidone, Phenacetin and organic compounds (Dichloroacetic acid, Trichloroacetic acid, Chloroform, Bromoform, Trichloroethene, Perchloroethene, Carbontetrachloride, Carbontetrabromide by NF (Filmtec, Saehan and RO (Filmtec, Saehan, Toray, Koch membranes were studied. Chloroform presented the lowest rejection due to small molar volume, equivalent width and length. Diclofenac and Primidone showed high rejections related to high molar volume and length. Dichloroacetic acid and Trichloroacetic acid presented good rejections caused by charge exclusion instead of steric hindrance mechanism influencing rejection. Bromoform and Trichloroethene showed low rejections due to small length and equivalent width. Carbontetrabromide, Perchloroethene and Carbontetrachloride with higher equivalent width than BF and TCE presented better rejections. A qualitative analysis of variables using Principal Component Analysis was successfully implemented for reduction of physical-chemical compound properties that influence membrane rejection of PhACs and organic compounds. Properties such as dipole moment, molar volume, hydrophobicity/hydrophilicity, molecular length and equivalent width were found to be important descriptors for simulation of membrane rejection. For membranes used in the experiments, we may conclude that charge repulsion was an important mechanism of rejection for ionic compounds. After analysis with Multiple Linear Regression, we also may conclude that membrane rejection of neutral compounds was well predicted by molar volume, length, equivalent width, hydrophobicity/hydrophilicity and dipole moment. Molecular weight was a poor descriptor variable for rejection modelling. We were able to provide acceptable statistical significance for important results.

  12. Reaction of CH radical with O2 by time-resolved FTIR spectroscopy

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The reaction of CH radical with O2 has been experimentally investigated by time-resolved Fourier transform IR emission spectroscopy. CH radicals were generated by multi-photon UV laser photolysis of bromoform (CHBr3) in gaseous phase. Highly vibrationally excited product CO (v =1-12) with a near Boltzmann distribution was observed after the reaction. The vibrational temperature of CO is estimated as high as 14400(1400 K and the averaged vibrational energy is about 25.8 kcal(mol-1. The emission intensity of CO is not sensitive to the quenching gas, which indicates that there is no early barrier in the reaction of CH+O2. However, the theoretically predicted product CO2 has not been found in the experiment.

  13. Development of aquarium fish models for environmental carcinogenesis: an intermittent-flow exposure system for volatile, hydrophobic chemicals

    Energy Technology Data Exchange (ETDEWEB)

    Walker, W.W.; Manning, C.S.; Overstreet, R.M.; Hawkins, W.E.

    1985-08-01

    An intermittent-flow exposure system was designed to provide stable and manipulative concentrations of volatile and hydrophobic compounds to small aquatic animals for uninterrupted long periods. Test species for 28-day experiments included two aquarium fishes, the Japanese medaka (Oryzias latipes) and the king cobra guppy (Poecilia reticulata). Test chemicals included trichloroethylene, vinylidene chloride, bis(2-chloroethyl)ether, ethylene dichloride, and a mixture of carbon tetrachloride, trichloroethylene, chloroform, bromodichloromethane, chlorodibromomethane and bromoform. These compounds are drinking water biorefractories and are potentially carcinogenic. Concentrated aqueous toxicant solutions, delivered from a remote triple carboy dispensing system, were mixed with diluent water within an isolated chamber containing exposure aquaria and test fish. Toxicant concentrations measured throughout each exposure period proved to be stable within acceptable variability ranges as indicated by coefficients of variation generally less than 15%.

  14. Genotoxic Effects in Swimmers Exposed to Disinfection By-products in Indoor Swimming Pools

    Science.gov (United States)

    Kogevinas, Manolis; Villanueva, Cristina M.; Font-Ribera, Laia; Liviac, Danae; Bustamante, Mariona; Espinoza, Felicidad; Nieuwenhuijsen, Mark J.; Espinosa, Aina; Fernandez, Pilar; DeMarini, David M.; Grimalt, Joan O.; Grummt, Tamara; Marcos, Ricard

    2010-01-01

    Background Exposure to disinfection by-products (DBPs) in drinking water has been associated with cancer risk. A recent study (Villanueva et al. 2007; Am J Epidemiol 165:148–156) found an increased bladder cancer risk among subjects attending swimming pools relative to those not attending. Objectives We evaluated adults who swam in chlorinated pools to determine whether exposure to DBPs in pool water is associated with biomarkers of genotoxicity. Methods We collected blood, urine, and exhaled air samples from 49 nonsmoking adult volunteers before and after they swam for 40 min in an indoor chlorinated pool. We estimated associations between the concentrations of four trihalomethanes (THMs) in exhaled breath and changes in micronuclei (MN) and DNA damage (comet assay) in peripheral blood lymphocytes before and 1 hr after swimming; urine mutagenicity (Ames assay) before and 2 hr after swimming; and MN in exfoliated urothelial cells before and 2 weeks after swimming. We also estimated associations and interactions with polymorphisms in genes related to DNA repair or to DBP metabolism. Results After swimming, the total concentration of the four THMs in exhaled breath was seven times higher than before swimming. The change in the frequency of micronucleated lymphocytes after swimming increased in association with higher exhaled concentrations of the brominated THMs (p = 0.03 for bromodichloromethane, p = 0.05 for chlorodibromomethane, p = 0.01 for bromoform) but not chloroform. Swimming was not associated with DNA damage detectable by the comet assay. Urine mutagenicity increased significantly after swimming, in association with the higher concentration of exhaled bromoform (p = 0.004). We found no significant associations with changes in micronucleated urothelial cells. Conclusions Our findings support potential genotoxic effects of exposure to DBPs from swimming pools. The positive health effects gained by swimming could be increased by reducing the potential health

  15. Preferential expression of a bromoperoxidase in sporophytes of a red alga, Pyropia yezoensis.

    Science.gov (United States)

    Matsuda, Ryuya; Ozgur, Rengin; Higashi, Yuya; Takechi, Katsuaki; Takano, Hiroyoshi; Takio, Susumu

    2015-04-01

    A 2,158 bp cDNA (PyBPO1) encoding a bromoperoxidase (BPO) of 625 amino acids was isolated from Pyropia yezoensis. Phylogenetic analysis using amino acid sequences of BPOs suggested that P. yezoensis and cyanobacteria were grouped in the same clade and separated from brown algae. Genomic Southern blot analysis suggested that PyBPO1 existed as a single copy per haploid genome. RT-PCR revealed that PyBPO1 was actively expressed in filamentous sporophytes but repressed in leafy gametophytes under normal growth conditions. High expression levels of PyBPO1 in sporophytes were observed when sporophytes were grown under gametophyte conditions, suggesting that preferential expression of PyBPO1 occurs during the sporophyte phase. BPO activity of cell-free extracts from sporophytes and gametophytes was examined by activity staining on native PAGE gel using o-dianisidine. One activity band was detected in sporophyte sample, but not in gametophyte sample. In addition, we found that bromide and iodide were effective substrate, but chloride was not. BPO activity was observed-likely in chloroplasts-when sporophyte cells were incubated with o-dianisidine and hydrogen peroxide. Cellular BPO staining showed the same halogen preference identified by in-gel BPO staining. Based on GS-MS analysis, bromoform was detected in medium containing sporophytes. Bromoform was not detected under dark culture conditions but was detected in the culture exposed to low light intensity (5 μmol m(-2) s(-1)) and increased under a moderate light intensity (30 μmol m(-2) s(-1)).

  16. Disinfection by-products in ballast water treatment: an evaluation of regulatory data.

    Science.gov (United States)

    Werschkun, Barbara; Sommer, Yasmin; Banerji, Sangeeta

    2012-10-15

    To reduce the global spread of invasive aquatic species, international regulations will soon require reductions of the number of organisms in ballast water discharged by ships. For this purpose, ballast water treatment systems were developed and approved by an international procedure. These systems rely on established water treatment principles which, to different degrees, have been proven to generate disinfection by-products with hazardous properties but have only scarcely been investigated in marine environments. Our study evaluates the publicly available documentation about approved ballast water treatment systems with regard to by-product formation. The most commonly employed methods are chlorination, ozonation, and ultraviolet (UV) irradiation. Chlorination systems generate trihalomethanes, halogenated acetic acids, and bromate in substantially larger quantities than reported for other areas of application. Levels are highest in brackish water, and brominated species predominate, in particular bromoform and dibromoacetic acid. Ozonation, which is less frequently utilized, produces bromoform in lower concentrations but forms higher levels of bromate, both of which were effectively reduced by active carbon treatment. In systems based on UV radiation, medium pressure lamps are employed as well as UV-induced advanced oxidation. For all UV systems, by-product formation is reported only occasionally. The most notable observations were small increases in nitrite, hydrogen peroxide, halogenated methanes and acetic acids. The assessment of by-product formation during ballast water treatment is limited by the lacking completeness and quality of available information. This concerns the extent and statistical characterisation of chemical analysis as well as the documentation of the test water parameters.

  17. Meteorological constraints on oceanic halocarbons above the Peruvian upwelling

    Science.gov (United States)

    Fuhlbrügge, Steffen; Quack, Birgit; Atlas, Elliot; Fiehn, Alina; Hepach, Helmke; Krüger, Kirstin

    2016-09-01

    During a cruise of R/V METEOR in December 2012 the oceanic sources and emissions of various halogenated trace gases and their mixing ratios in the marine atmospheric boundary layer (MABL) were investigated above the Peruvian upwelling. This study presents novel observations of the three very short lived substances (VSLSs) - bromoform, dibromomethane and methyl iodide - together with high-resolution meteorological measurements, Lagrangian transport and source-loss calculations. Oceanic emissions of bromoform and dibromomethane were relatively low compared to other upwelling regions, while those for methyl iodide were very high. Radiosonde launches during the cruise revealed a low, stable MABL and a distinct trade inversion above acting as strong barriers for convection and vertical transport of trace gases in this region. Observed atmospheric VSLS abundances, sea surface temperature, relative humidity and MABL height correlated well during the cruise. We used a simple source-loss estimate to quantify the contribution of oceanic emissions along the cruise track to the observed atmospheric concentrations. This analysis showed that averaged, instantaneous emissions could not support the observed atmospheric mixing ratios of VSLSs and that the marine background abundances below the trade inversion were significantly influenced by advection of regional sources. Adding to this background, the observed maximum emissions of halocarbons in the coastal upwelling could explain the high atmospheric VSLS concentrations in combination with their accumulation under the distinct MABL and trade inversions. Stronger emissions along the nearshore coastline likely added to the elevated abundances under the steady atmospheric conditions. This study underscores the importance of oceanic upwelling and trade wind systems on the atmospheric distribution of marine VSLS emissions.

  18. Trihalomethane exposure and biomonitoring for the liver injury indicator, alanine aminotransferase, in the United States population (NHANES 1999–2006)

    Science.gov (United States)

    Burch, James B.; Everson, Todd M.; Seth, Ratanesh K.; Wirth, Michael D.; Chatterjee, Saurabh

    2015-01-01

    Exposure to trihalomethanes (or THMs: chloroform, bromoform, bromodichloromethane, and dibromochloromethane [DBCM]) formed via drinking water disinfection has been associated with adverse reproductive outcomes and cancers of the digestive or genitourinary organs. However, few studies have examined potential associations between THMs and liver injury in humans, even though experimental studies suggest that these agents exert hepatotoxic effects, particularly among obese individuals. This study examined participants in the National Health and Nutrition Examination Survey (1999–2006, N = 2781) to test the hypothesis that THMs are associated with liver injury as assessed by alanine aminotransferase (ALT) activity in circulation. Effect modification by body mass index (BMI) or alcohol consumption also was examined. Associations between blood THM concentrations and ALT activity were assessed using unconditional multiple logistic regression to calculate prevalence odds ratios (ORs) with 95% confidence intervals (CIs) for exposure among cases with elevated ALT activity (men: >40 IU/L, women: >30 IU/L) relative to those with normal ALT, after adjustment for variables that may confound the relationship between ALT and THMs. Compared to controls, cases were 1.35 times more likely (95% CI: 1.02, 1.79) to have circulating DBCM concentrations exceeding median values in the population. There was little evidence for effect modification by BMI, although the association varied by alcohol consumption. Among non-drinkers, cases were more likely than controls to be exposed to DBCM (OR: 3.30, 95% CI: 1.37–7.90), bromoform (OR: 2.88, 95% CI: 1.21–6.81), or brominated THMs (OR: 4.00, 95% CI: 1.31–12.1), but no association was observed among participants with low, or moderate to heavy alcohol consumption. Total THM levels exceeding benchmark exposure limits continue to be reported both in the United States and globally. Results from this study suggest a need for further

  19. The relationship between volatile halocarbons and phytoplankton pigments during a Trichodesmium bloom in the coastal eastern Arabian Sea

    Science.gov (United States)

    Roy, Rajdeep; Pratihary, Anil; Narvenkar, Gayatree; Mochemadkar, Sunita; Gauns, Mangesh; Naqvi, S. W. A.

    2011-11-01

    Eukaryotic phytoplankton such as diatoms and prymnesiophytes produce biogenic halocarbons in the ocean that serve as important sources of chlorine and bromine to the atmosphere, but the role of cyanobacteria in halocarbon production is not well established. We studied distributions of chloroform (CHCl 3), carbon tetrachloride (CCl 4), methylene bromide (CH 2Br 2) and bromoform (CHBr 3) in relation to phytoplankton composition, determined from pigment analysis complemented by microscopic examination, for one month in coastal waters of the eastern Arabian that experienced a Trichodesmium bloom that typically occurs during the Spring Intermonsoon season. High concentrations of zeaxanthin (23 μg l -1), alpha beta betacarotene (6 μg l -1) and chlorophyll a (67 μg l -1) were found within the bloom whereas the marker pigment concentrations were low outside the bloom. CHCl 3 and CCl 4 occurred in relatively high concentrations in surface waters whereas CH 2Br 2 and CHBr 3 were restricted to the subsurface layer. Chlorinated halocarbons were positively inter-correlated and with CHBr 3. The observed spatial and temporal trends in brominated compounds appear to be related to the abundance of Trichodesmium although correlations between concentrations of brominated compounds with various marker pigments were poor and statistically non-significant. The results support the existence of multiple sources and sinks of halogenated compounds, which might obscure the relationship between halocarbons and phytoplankton composition.

  20. Purge efficiency in the determination of trihalomethanes in water by purge-and-trap gas chromatography.

    Science.gov (United States)

    Ruiz-Bevia, Francisco; Fernandez-Torres, Maria J; Blasco-Alemany, Maria P

    2009-01-26

    Purge-and-trap gas chromatography-mass spectrometry (PT-GC-MS) has become an accepted method for the analysis of trihalomethanes (THMs) in water. The purge-and-trap technique is based on an efficient transfer of volatile organic compounds from the liquid (contained in the purge chamber) to the gaseous phase by bubbling with an inert gas. The aim of this work was to study the purge system's efficiency by means of several consecutive purge cycles lasting 11 min each of the same liquid sample. The concentration range chosen of THMs was very wide [5-200 microg L(-1)]. The inert gas flow rate was 40 mL min(-1), and experiments were performed at temperatures of 25, 35 and 50 degrees C. Bromoform (CHBr(3)), the least volatile compound, needed 19 cycles to be purged quantitatively at a concentration of 200 microg L(-1) and only 7 cycles at 5 microg L(-1) for a 25 mL sample at 25 degrees C. Chloroform (CHCl(3)), the most volatile compound, required 4 cycles to be fully extracted at 200 microg L(-1) and 2 at 5 microg L(-1). Finally, Novak's theoretical model, based on the distribution constant between gas and liquid phases, was used to correlate the THMs purging extraction data.

  1. A simplified Quick, Easy, Cheap, Effective, Rugged and Safe approach for the determination of trihalomethanes and benzene, toluene, ethylbenzene and xylenes in soil matrices by fast gas chromatography with mass spectrometry detection.

    Science.gov (United States)

    García Pinto, Carmelo; Herrero Martín, Sara; Pérez Pavón, José Luis; Moreno Cordero, Bernardo

    2011-03-09

    A method based on simplified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction followed by large-injection volume-fast gas chromatography and mass spectrometry detection has been developed for the determination of trihalomethanes (chloroform, bromodichloromethane, dibromochloromethane and bromoform) and BTEX (benzene, toluene, ethylbenzene and xylenes) in soil samples. The simplified version of QuEChERS used meets the requirements of the "green chemistry" and provides reliable results with high sample throughput, low solvent consumption, little labour and the use of materials commonly employed in laboratories. The GC device used is equipped with a programmable temperature vaporizer (PTV), with a liner packed with Tenax-TA(®). Using the solvent-vent mode, the PTV allows the injection of large volumes of sample, affording an improvement in the sensitivity of the method. The chromatographic conditions used here allowed the separation of the compounds in less than 5.50 min. Good linearity was obtained for all the target compounds, with highly satisfactory repeatability and reproducibility values. The limits of detection were in the 0.2 to 15 μg kg(-1) range. The method was validated by the analysis of two certified reference materials.

  2. Characterization of dissolved organic matter for prediction of trihalomethane formation potential in surface and sub-surface waters.

    Science.gov (United States)

    Awad, John; van Leeuwen, John; Chow, Christopher; Drikas, Mary; Smernik, Ronald J; Chittleborough, David J; Bestland, Erick

    2016-05-05

    Dissolved organic matter (DOM) in surface waters used for drinking purposes can vary markedly in character dependent on their sources within catchments. The character of DOM further influences the formation of disinfection by products when precursor DOM present in drinking water reacts with chlorine during disinfection. Here we report the development of models that describe the formation potential of trihalomethanes (THMFP) dependent on the character of DOM in waters from discrete catchments with specific land-use and soil textures. DOM was characterized based on UV absorbance at 254 nm, apparent molecular weight and relative abundances of protein-like and humic-like compounds. DOM character and Br concentration (up to 0.5 mg/L) were used as variables in models (R(2)>0.93) of THMFP, which ranged from 19 to 649 μg/L. Chloroform concentration (12-594 μg/L) and relative abundance (27-99%) were first modeled (R(2)>0.85) and from these, the abundances of bromodichloromethane and chlorodibromomethane estimated using power and exponential functions, respectively (R(2)>0.98). From these, the abundance of bromoform is calculated. The proposed model may be used in risk assessment of catchment factors on formation of trihalomethanes in drinking water, in context of treatment efficiency for removal of organic matter.

  3. Effects of medium-pressure UV lamps radiation on water quality in a chlorinated indoor swimming pool.

    Science.gov (United States)

    Cassan, Delphine; Mercier, Béatrice; Castex, Françoise; Rambaud, André

    2006-03-01

    The aim of our study was to determine the impact of medium-pressure UV lamps radiation on water quality in a chlorinated indoor swimming pool. An indoor swimming pool was equipped with two medium-pressure UV lamps. We collected eight samples of water daily over a four-weeks period and measured total and free chlorine, pH, water temperature, bacteriological parameters, total organic carbon and trihalomethanes. During the first week, which served as control, medium-pressure UV lamps were turned off. During the next three weeks, medium-pressure UV lamps were kept on 24 h per day. The third week, we reduced the level of the injected chlorine into water, and the last week we also reduced the water renewal volume by 27%. Our results showed that bacteriological parameters remained within allowable french limits. When medium-pressure UV lamps were kept on, total, free and active chlorine levels were significantly increased (P<0.001), whereas combined chlorine level were significantly decreased (P<0.001 and P<0.05, respectively). The levels of chloroform and bromodichloromethane were significantly increased when medium-pressure UV lamps were kept on (P<0.001), whereas chlorodibromomethane and bromoform levels significantly decreased (P<0.05 and P<0.001, respectively). The additional formation of chloroform and bromodichloromethane may be explained by the increase in active chlorine and by radicalizing mechanisms initiated by UV radiation.

  4. Magnetic Study of the Heated and Unheated Sedimentary Fillings of Sebkha Mhabeul, Southeast Tunisia: A Geophysical Method for Paleoclimatic Investigation and Tephrochronological Dating

    Directory of Open Access Journals (Sweden)

    Elhoucine Essefi

    2014-01-01

    Full Text Available This paper is meant to investigate the climatic and volcanic signals within the sedimentary filling of sebkha Mhabeul through a thermomagnetic study of a 37 cm length core. Values of the magnetic susceptibility at ambient temperature show that the core encompasses four climatic stages: the Warming Present (WP, the Little Ice Age (Late LIA, Early Little Ice Age (ELIA, and the Medieval Climate Anomalies (MCA. Added to the subcycles, the spectral analysis shows the individualization of an 888 yr cycle probably related to solar activity. The heating at 250°C is good-for-nothing since it was useful neither for climatic investigation nor for tephras layers detection. Heating at 700°C generated the complete loss of the climatic signal. On the other hand, it allowed the detection of the previously identified tephras layers. Further, it highlighted the presence of other tephras layers. The extraction by the bromoform confirms the presence of these tephras. The use of the same methodology may allow the detection of tephras layers within other sebkhas.

  5. Photolytic removal of DBPs by medium pressure UV in swimming pool water.

    Science.gov (United States)

    Hansen, Kamilla M S; Zortea, Raissa; Piketty, Aurelia; Vega, Sergio Rodriguez; Andersen, Henrik Rasmus

    2013-01-15

    Medium pressure UV is used for controlling the concentration of combined chlorine (chloramines) in many public swimming pools. Little is known about the fate of other disinfection by-products (DBPs) in UV treatment. Photolysis by medium pressure UV treatment was investigated for 12 DBPs reported to be found in swimming pool water: chloroform, bromodichloromethane, dibromochloromethane, bromoform, dichloroacetonitrile, bromochloroacetonitrile, dibromoacetronitrile, trichloroacetonitrile, trichloronitromethane, dichloropropanone, trichloropropanone, and chloral hydrate. First order photolysis constants ranged 26-fold from 0.020 min(-1) for chloroform to 0.523 min(-1) for trichloronitromethane. The rate constants generally increased with bromine substitution. Using the UV removal of combined chlorine as an actinometer, the rate constants were recalculated to actual treatment doses of UV applied in a swimming pool. In an investigated public pool the UV dose was equivalent to an applied electrical energy of 1.34 kWh m(-3) d(-1) and the UV dose required to removed 90% of trichloronitromethane was 0.4 kWh m(-3) d(-1), while 2.6 kWh m(-3) d(-1) was required for chloral hydrate and the bromine containing haloacetonitriles and trihalomethanes ranged from 0.6 to 3.1 kWh m(-3) d(-1). It was predicted thus that a beneficial side-effect of applying UV for removing combined chlorine from the pool water could be a significant removal of trichloronitromethane, chloral hydrate and the bromine containing haloacetonitriles and trihalomethanes.

  6. The risks of drinking water

    Science.gov (United States)

    Reichhardt, Tony

    1984-04-01

    Three researchers from the Energy and Environmental Policy Center at Harvard University have come up with a new method of calculating the risk from contaminants in drinking water, one that they believe takes into account some of the uncertainties in pronouncing water safe or dangerous to drink. The new method concentrates on the risk of cancer, which authors Edmund Crouch, Richard Wilson, and Lauren Zeise believe has not been properly considered in establishing drinking water standards.Writing in the December 1983 issue of Water Resources Research, the authors state that “current [drinking water] standards for a given chemical or class of chemicals do not account for the presence of other pollutants” that could combine to create dangerous substances. According to Wilson, “Over a hundred industrial pollutants and chlorination byproducts have been found in various samples of drinking water, some of which are known carcinogens, others suspected carcinogens.” The same chlorine that solves one major health problem—the threat of bacterial disease—can thus contribute to another, according to the authors, by increasing the long-term risk of cancer. The largest risks are due to halomethanes such as chloroform and bromoform, produced as chlorine reacts with organic matter in drinking water.

  7. Halocarbon distributions and emissions in the western tropical Pacific during the SHIVA SONNE expedition in November 2011

    Science.gov (United States)

    Quack, B.; Atlas, E.; Shi, Q.; Hepach, H.; Raimund, S.; Kinzel, J.; Leedham, E.; Fuhlbrügge, S.; Wiegmann, S.; Chea, W.; Wittke, F.; Robinson, A.; Harris, N.; Kreher, K.; Sturges, B.; Bracher, A.; Wallace, D.; Krüger, K.

    2012-04-01

    Marine brominated and iodinated halocarbons participate in catalytic ozone destruction and aerosol formation in the troposphere and they also have a significant impact on stratospheric ozone. While the tropical oceans are a known source of these very short lived substances (VSLS), including e.g. bromoform (CHBr3) and methyliodide (CH3I), the tropical Western Pacific waters are largely uncharacterized for these compounds. Coastal macro algae, regionally enhanced phytoplankton abundance, photochemical reactions and local anthropogenic sources are expected to contribute to strong marine emissions. As high convective activity with fast efficient uplift takes place throughout the year, the western Pacific is projected to be a hot spot for oceanic VSLS supply to the stratosphere. In this study, we present first results from the SHIVA Sonne expedition to the South China Sea during November 2011. The research cruise was embedded within the framework of the EU-project SHIVA (Stratospheric ozone: Halogen Impacts in a Varying Atmosphere). During the cruise we investigated the large variability of the VSLS concentrations in both ocean and atmosphere using several methods, including in-situ atmospheric measurements, air canister sampling, purge and trap gas chromatography with electron capture and mass spectrometric detection. We will intercompare the results from various methods and present highlights from the expedition including atmospheric and oceanic VSLS data, as well as first estimates of emissions.

  8. First results from the SHIVA SONNE expedition to the tropical Western Pacific during November 2011

    Science.gov (United States)

    Krüger, K.; Quack, B.; Fuhlbrügge, S.; Tegtmeier, S.; Shiva Sonne Team

    2012-04-01

    The tropical oceans are a known source of reactive bromine and iodine to the atmosphere in the form of short-lived brominated and iodinated methanes as e.g. bromoform (CHBr3) and methyliodide (CH3I). These very short lived substances (VSLS) are expected to reach the stratosphere and deplete stratospheric ozone in the tropics especially if they have strong emissions over the tropical oceans, where high convective activity with fast efficient uplifts exists. Thus, the tropical Western Pacific is of special interest since the oceanic VSLS are largely uncharacterized and are projected to have hot spots for both their emissions and fast transport pathways to the stratosphere throughout the year. In this study, we present first results from the SHIVA Sonne expedition to the tropical Western Pacific during November 2011. The ship cruise was embedded within the frame work of the EU-project SHIVA (Stratospheric ozone: Halogen Impacts in a Varying Atmosphere). To investigate the large variability of VSLS sources in more detail the expedition cruised through Malaysian and Philippine coastal and open waters of various biogeochemical regimes. The ship expedition will be introduced to the audience, presenting the atmospheric and hydrographic setting. We will show highlights from the cruise including frequent meteorological profile soundings, characterizing the atmosphere from the marine boundary layer to the stratosphere in more detail, together with VSLS measurements both from the atmosphere and the ocean. First estimates of the VSLS transport into the stratosphere will be presented.

  9. Trihalomethane formation potential of shrimp farm effluents in Chachoengsao Province, Thailand

    Directory of Open Access Journals (Sweden)

    Aweewan Mangmeechai

    2004-02-01

    Full Text Available Shrimp farm effluents along Bangpakong River in Chachoengsao Province, Thailand, were evaluated for their trihalomethane formation potential (THMFP, which were shown to be in the range of 810-3,100 µg/L. Samples from river locations, both upstream and downstream from these selected farms, were also tested for their existing THMFP. These river samples were illustrated to have notably lower level of THMFP than the shrimp farm effluents. The downstream concentration was, however, found to be significantly higher than the upstream (as much as 5 times. This indicated that the contamination of shrimp farm effluents could have increased the formation potential of THMs in the natural water source. The experimental results showed a positive correlation between salinity and THMFP. The formation of various THM species depended significantly on the level of salinity in the water sample. Low salinity (0-5 ppt often led to a high formation of chloroform and bromodichloromethane while high salinity (5-15 ppt resulted in a great quantity of dibromochloromethane and bromoform. FTIR spectra of the samples before and after chlorination suggested that the functional groups involved in the reaction were hydroxyl group, amines group, aromatic ring, aliphatic chloro compounds and aliphatic bromo compounds, whereas C-O was the product from the reaction.

  10. The effect of desiccation on the emission of volatile bromocarbons from two common temperate macroalgae

    Directory of Open Access Journals (Sweden)

    E. C. Leedham Elvidge

    2014-07-01

    Full Text Available Exposure of intertidal macroalgae during low tide has been linked to the emission of a variety of atmospherically-important trace gases into the coastal atmosphere. In recent years, several studies have investigated the role of inorganic iodine and organoiodides as antioxidants and their emission during exposure to combat oxidative stress, yet the role of organic bromine species during desiccation is less well understood. In this study the emission of dibromomethane (CH2Br2 and bromoform (CHBr3 during exposure and desiccation of two common temperate macroalgae, Fucus vesiculosus and Ulva intestinalis, is reported. Determination of the impact exposure may have on algal physiological processes is difficult as intertidal species are adapted to desiccation and may undergo varying degrees of desiccation before their physiology is affected. For this reason we include comparisons between photosynthetic capacity (Fv / Fm and halocarbon emissions during a desiccation time series. In addition, the role of rewetting with freshwater to simulate exposure to rain was also investigated. Our results show that an immediate flux of bromocarbons occurs upon exposure, followed by a decline in bromocarbon emissions. We suggest that this immediate bromocarbon pulse may be linked to volatilisation or emissions of existing bromocarbon stores from the algal surface rather than the production of bromocarbons as an antioxidant response.

  11. Formation of brominated disinfection byproducts from natural organic matter isolates and model compounds in a sulfate radical-based oxidation process

    KAUST Repository

    Wang, Yuru

    2014-12-16

    A sulfate radical-based advanced oxidation process (SR-AOP) has received increasing application interest for the removal of water/wastewater contaminants. However, limited knowledge is available on its side effects. This study investigated the side effects in terms of the production of total organic bromine (TOBr) and brominated disinfection byproducts (Br-DBPs) in the presence of bromide ion and organic matter in water. Sulfate radical was generated by heterogeneous catalytic activation of peroxymonosulfate. Isolated natural organic matter (NOM) fractions as well as low molecular weight (LMW) compounds were used as model organic matter. Considerable amounts of TOBr were produced by SR-AOP, where bromoform (TBM) and dibromoacetic acid (DBAA) were identified as dominant Br-DBPs. In general, SR-AOP favored the formation of DBAA, which is quite distinct from bromination with HOBr/OBr- (more TBM production). SR-AOP experimental results indicate that bromine incorporation is distributed among both hydrophobic and hydrophilic NOM fractions. Studies on model precursors reveal that LMW acids are reactive TBM precursors (citric acid > succinic acid > pyruvic acid > maleic acid). High DBAA formation from citric acid, aspartic acid, and asparagine was observed; meanwhile aspartic acid and asparagine were the major precursors of dibromoacetonitrile and dibromoacetamide, respectively.

  12. Determination of trihalomethanes in soil matrices by simplified quick, easy, cheap, effective, rugged and safe extraction and fast gas chromatography with electron capture detection.

    Science.gov (United States)

    Herrero Martín, Sara; García Pinto, Carmelo; Pérez Pavón, José Luis; Moreno Cordero, Bernardo

    2010-07-23

    A method based on QuEChERS extraction is proposed for the determination of trihalomethanes (chloroform, bromodichloromethane, dibromocloromethane and bromoform) in soil samples. The new version of QuEChERS adapted to soil samples consists of liquid extraction with ethyl acetate, the addition of water to moisten the samples, salting-out partitioning of the water with anhydrous MgSO4, and direct injection of the organic extract, obtained after the centrifugation step, into the gas chromatograph. This simplified extraction procedure maintains the advantages of the original method and avoids some steps, making the final procedure simpler, faster, and cheaper, with the consequent reduction in errors associated with sample manipulation. The experimental conditions of the analytical method, based on fast gas chromatography (FGC) and micro-electron capture detection (microECD), were optimized. The column and oven program used allowed fast separation of the compounds in less than 4 min and the total analysis cycle time was as short as 10 min. The existence of a matrix effect was checked and the analytical conditions of the method were studied in a fortified garden soil sample. The highly sensitive and selective detector used afforded to detection limits in the order of ng/kg for the target compounds. To validate the proposed method two certified reference materials (CRMs) were analyzed.

  13. Synthesis of hollow ZnO microspheres by an integrated autoclave and pyrolysis process.

    Science.gov (United States)

    Duan, Jinxia; Huang, Xintang; Wang, Enke; Ai, Hanhua

    2006-03-28

    Hollow zinc oxide microspheres have been synthesized from a micro ZnBr2·2H2O precursor obtained by an autoclave process in bromoform steam at 220 °C /2.5 MPa. Field-emission scanning electron microscropy (FE-SEM) and transmission electron microscopy (TEM) show that the products are about 1.0 µm single crystal spherical particles with hollow interiors, partly open surfaces and walls self-assembled by ZnO nanoparticles. X-ray diffraction (XRD) analysis shows that the as-prepared ZnO hollow spheres are of a hexagonal phase structure. A possible formation mechanism is suggested on the basis of the shape evolution of ZnO nanostructures observed by SEM and TEM. The room-temperature photoluminescence (PL) spectrum shows UV emission around 386 nm and weak green emission peaks indicating that there are few defects in the single crystal grains of the ZnO microspheres.

  14. Occurrence and potential crop uptake of emerging contaminants and related compounds in an agricultural irrigation network

    Energy Technology Data Exchange (ETDEWEB)

    Calderon-Preciado, Diana [IDAEA-CSIC, Jordi Girona, 18, E-08034 Barcelona (Spain); Matamoros, Victor, E-mail: victor.matamoros@udg.edu [Department of Chemistry, University of Girona, Campus Montilivi, 17071 Girona (Spain); Bayona, Josep M. [IDAEA-CSIC, Jordi Girona, 18, E-08034 Barcelona (Spain)

    2011-12-15

    Emerging contaminants have received much attention in recent years due to their presence in surface waters, but little attention has been paid to their occurrence in agricultural irrigation waters. This study investigated the occurrence of these compounds in an agricultural irrigation network in northeastern Spain and, for the first time, using two plant uptake models, estimated the concentration of selected micropollutants in crops. The concentration of micropollutants in agricultural irrigation waters ranged from 10 to 5130 ng L{sup -1} and exhibited some attenuation over the course of the irrigation network. Bromoform, chloroform, diclofenac, caffeine, ibuprofen, naproxen, methyl dihydrojasmonate, galaxolide, butylated hydroxytoluene, and butylated hydroxyanisole were the most abundant contaminants (> 200 ng L{sup -1}, on average). The estimated concentration of micropollutants in crops ranged from < 1 to 7677 ng kg{sup -1}, with the neutral compounds being the most abundant. Moreover, the predicted data obtained by fate models generally agreed with experimental data. Finally, human exposure to micropollutants through fruit and vegetable consumption was estimated to be 9.8 {mu}g per person and week ({Sigma} 27 contaminants detected). Further studies are needed to determine the health implications that the presence of these compounds in fruit and vegetables may have for consumers.

  15. Plasma brominated polymer particles as grafting substrate for thiol-terminated telomers.

    Science.gov (United States)

    Byström, Emil; Nordborg, Anna; Limé, Fredrik; Dinh, Ngoc Phuoc; Irgum, Knut

    2010-06-01

    A combined surface activation and "grafting to" strategy was developed to convert divinylbenzene particles into weak cation exchangers suitable for protein separation. The initial activation step was based on plasma modification with bromoform, which rendered the particles amenable to further reaction with nucleophiles by introducing Br to a surface content of 11.2 atom-%, as determined by X-ray photoelectron spectroscopy. Grafting of thiol-terminated glydicyl methacrylate telomers to freshly plasma activated surfaces was accomplished without the use of added initiator, and the grafting was verified both by reduction in bromine content and the appearance of sulfur-carbon linkages, showing that the surface grafts were covalently bonded. Following grafting the attached glydicyl methacrylate telomer tentacles were further modified by a two-step procedure involving hydrolysis to 2,3-hydroxypropyl groups and conversion of hydroxyl groups to carboxylate functionality by succinic anhydride. The final material was capable of baseline separating four model proteins in 3 min by gradient cation exchange chromatography in a fully aqueous eluent.

  16. Heated indoor swimming pools, infants, and the pathogenesis of adolescent idiopathic scoliosis: a neurogenic hypothesis

    Directory of Open Access Journals (Sweden)

    McMaster Marianne E

    2011-10-01

    Full Text Available Abstract Background In a case-control study a statistically significant association was recorded between the introduction of infants to heated indoor swimming pools and the development of adolescent idiopathic scoliosis (AIS. In this paper, a neurogenic hypothesis is formulated to explain how toxins produced by chlorine in such pools may act deleteriously on the infant's immature central nervous system, comprising brain and spinal cord, to produce the deformity of AIS. Presentation of the hypothesis Through vulnerability of the developing central nervous system to circulating toxins, and because of delayed epigenetic effects, the trunk deformity of AIS does not become evident until adolescence. In mature healthy swimmers using such pools, the circulating neurotoxins detected are chloroform, bromodichloromethane, dibromochloromethane, and bromoform. Cyanogen chloride and dichloroacetonitrile have also been detected. Testing the hypothesis In infants, the putative portals of entry to the blood could be dermal, oral, or respiratory; and entry of such circulating small molecules to the brain are via the blood-brain barrier, blood-cerebrospinal fluid barrier, and circumventricular organs. Barrier mechanisms of the developing brain differ from those of adult brain and have been linked to brain development. During the first 6 months of life cerebrospinal fluid contains higher concentrations of specific proteins relative to plasma, attributed to mechanisms continued from fetal brain development rather than immaturity. Implications of the hypothesis The hypothesis can be tested. If confirmed, there is potential to prevent some children from developing AIS.

  17. Haloacetic acid and trihalomethane formation from the chlorination and bromination of aliphatic beta-dicarbonyl acid model compounds.

    Science.gov (United States)

    Dickenson, Eric R V; Summers, R Scott; Croué, Jean-Philippe; Gallard, Hervé

    2008-05-01

    While it is known that resorcinol- and phenol-type aromatic structures within natural organic matter (NOM) react during drinking water chlorination to form trihalomethanes (THMs), limited studies have examined aliphatic-type structures as THM and haloacetic acid (HAA) precursors. A suite of aliphatic acid model compounds were chlorinated and brominated separately in controlled laboratory-scale batch experiments. Four and two beta-dicarbonyl acid compounds were found to be important precursors for the formation of THMs (chloroform and bromoform (71-91% mol/mol)), and dihaloacetic acids (DXAAs) (dichloroacetic acid and dibromoacetic acid (5-68% mol/mol)), respectively, after 24 h at pH 8. Based upon adsorbable organic halide formation, THMs and DXAAs, and to a lesser extent mono and trihaloacetic acids, were the majority (> 80%) of the byproducts produced for most of the aliphatic beta-dicarbonyl acid compounds. Aliphatic beta-diketone-acid-type and beta-keto-acid-type structures could be possible fast- and slow-reacting THM precursors, respectively, and aliphatic beta-keto-acid-type structures are possible slow-reacting DXAA precursors. Aliphatic beta-dicarbonyl acid moieties in natural organic matter, particularly in the hydrophilic fraction, could contribute to the significant formation of THMs and DXAAs observed after chlorination of natural waters.

  18. A metagenomic-based survey of microbial (de)halogenation potential in a German forest soil.

    Science.gov (United States)

    Weigold, Pascal; El-Hadidi, Mohamed; Ruecker, Alexander; Huson, Daniel H; Scholten, Thomas; Jochmann, Maik; Kappler, Andreas; Behrens, Sebastian

    2016-06-29

    In soils halogens (fluorine, chlorine, bromine, iodine) are cycled through the transformation of inorganic halides into organohalogen compounds and vice versa. There is evidence that these reactions are microbially driven but the key enzymes and groups of microorganisms involved are largely unknown. Our aim was to uncover the diversity, abundance and distribution of genes encoding for halogenating and dehalogenating enzymes in a German forest soil by shotgun metagenomic sequencing. Metagenomic libraries of three soil horizons revealed the presence of genera known to be involved in halogenation and dehalogenation processes such as Bradyrhizobium or Pseudomonas. We detected a so far unknown diversity of genes encoding for (de)halogenating enzymes in the soil metagenome including specific and unspecific halogenases as well as metabolic and cometabolic dehalogenases. Genes for non-heme, no-metal chloroperoxidases and haloalkane dehalogenases were the most abundant halogenase and dehalogenase genes, respectively. The high diversity and abundance of (de)halogenating enzymes suggests a strong microbial contribution to natural halogen cycling. This was also confirmed in microcosm experiments in which we quantified the biotic formation of chloroform and bromoform. Knowledge on microorganisms and genes that catalyze (de)halogenation reactions is critical because they are highly relevant to industrial biotechnologies and bioremediation applications.

  19. Emission of iodine containing volatiles by selected microalgae species

    Directory of Open Access Journals (Sweden)

    U. R. Thorenz

    2014-06-01

    Full Text Available In this study we present the results of an incubation study of different phytoplankton samples in F/2 aqueous media treated with elevated ozone levels. Halocarbon measurements show that the samples tested released bromoform and different iodocarbons including iodomethane, iodochloromethane and diiodomethane. Iodide and iodate levels in the liquid phase were representative of concentrations of surface water in a natural environment. Measurement of volatile iodine (I2 emissions from two diatom samples (Mediopyxis helysia and Porosira glacialis and the background sample (F/2-medium from locally seawater, showed that the quantity of I2 evolved depends on the ozone concentration in the air. This behaviour was assumed to be caused by the oxidation reaction mechanism of iodine with ozone. The I2 emission flux agrees with model calculations at different iodide concentrations. The I2 emission of a natural plankton concentrate sample was, however, very low compared to other samples and showed no dependence on ozone. The reason for this was shown to be the low iodide concentration in the algae suspension, which seems to be the limiting factor in the oxidative formation of I2.

  20. Emission of iodine containing volatiles by selected microalgae species

    Science.gov (United States)

    Thorenz, U. R.; Carpenter, L. J.; Huang, R.-J.; Kundel, M.; Bosle, J.; Hoffmann, T.

    2014-06-01

    In this study we present the results of an incubation study of different phytoplankton samples in F/2 aqueous media treated with elevated ozone levels. Halocarbon measurements show that the samples tested released bromoform and different iodocarbons including iodomethane, iodochloromethane and diiodomethane. Iodide and iodate levels in the liquid phase were representative of concentrations of surface water in a natural environment. Measurement of volatile iodine (I2) emissions from two diatom samples (Mediopyxis helysia and Porosira glacialis) and the background sample (F/2-medium from locally seawater), showed that the quantity of I2 evolved depends on the ozone concentration in the air. This behaviour was assumed to be caused by the oxidation reaction mechanism of iodine with ozone. The I2 emission flux agrees with model calculations at different iodide concentrations. The I2 emission of a natural plankton concentrate sample was, however, very low compared to other samples and showed no dependence on ozone. The reason for this was shown to be the low iodide concentration in the algae suspension, which seems to be the limiting factor in the oxidative formation of I2.

  1. Source regions of stratospheric VSLS in the Indian Ocean

    Science.gov (United States)

    Quack, Birgit; Hepach, Helmke; Atlas, Elliot; Bracher, Astrid; Endres, Sonja; Arevalo-Martinez, Damian; Bange, Hermann; Lennartz, Sinikka; Steinhoff, Tobias; Booge, Dennis; Zarvasky, Alexander; Marandino, Christa; Patey, Matt; Achterberg, Eric; Dengler, Markus; Fiehn, Alina; Tegtmeier, Susann; Krüger, Kirstin

    2016-04-01

    Halogenated very-short-lived substances (VSLS), which are naturally produced in the ocean, play a significant role in present day ozone depletion, in particular in combination with enhanced stratospheric sulfate aerosol, which is also partly derived from oceanic VSLS. The decline of anthropogenic chlorine in the stratosphere within the 21st century will increase the relative importance of the natural emissions on stratospheric ozone destruction. Especially, oceanic sources and source regions of the compounds need to be better constrained, in order to improve the future prediction. During boreal summer the Asian monsoon circulation transports air masses from the Indian Ocean to the stratosphere, while the contribution of VSLS from this ocean to stratospheric halogen and sulfur is unknown. During the research cruises SO 234/2 and SO 235 in July-August 2014 onboard RV SONNE oceanic and atmospheric halogenated VSLS such as bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I) were measured in the subtropical and tropical West Indian Ocean for the first time. Here we present the oceanic sources of the halogenated compounds and their relation to other biogeochemical parameters (short- and longlived trace gases, phytoplankton and nutrients) along the cruise track, which covered coastal, upwelling and open ocean regimes and the Seychelles-Chagos thermocline ridge as important source region for stratospheric bromine.

  2. The effect of different boiling and filtering devices on the concentration of disinfection by-products in tap water.

    Science.gov (United States)

    Carrasco-Turigas, Glòria; Villanueva, Cristina M; Goñi, Fernando; Rantakokko, Panu; Nieuwenhuijsen, Mark J

    2013-01-01

    Disinfection by-products (DBPs) are ubiquitous contaminants in tap drinking water with the potential to produce adverse health effects. Filtering and boiling tap water can lead to changes in the DBP concentrations and modify the exposure through ingestion. Changes in the concentration of 4 individual trihalomethanes (THM4) (chloroform (TCM), bromodichloromethane (BDCM), dibromochloromethane (DBCM), and bromoform (TBM)), MX, and bromate were tested when boiling and filtering high bromine-containing tap water from Barcelona. For filtering, we used a pitcher-type filter and a household reverse osmosis filter; for boiling, an electric kettle, a saucepan, and a microwave were used. Samples were taken before and after each treatment to determine the change in the DBP concentration. pH, conductivity, and free/total chlorine were also measured. A large decrease of THM4 (from 48% to 97%) and MX concentrations was observed for all experiments. Bromine-containing trihalomethanes were mostly eliminated when filtering while chloroform when boiling. There was a large decrease in the concentration of bromate with reverse osmosis, but there was a little effect in the other experiments. These findings suggest that the exposure to THM4 and MX through ingestion is reduced when using these household appliances, while the decrease of bromate is device dependent. This needs to be considered in the exposure assessment of the epidemiological studies.

  3. The Effect of Different Boiling and Filtering Devices on the Concentration of Disinfection By-Products in Tap Water

    Directory of Open Access Journals (Sweden)

    Glòria Carrasco-Turigas

    2013-01-01

    Full Text Available Disinfection by-products (DBPs are ubiquitous contaminants in tap drinking water with the potential to produce adverse health effects. Filtering and boiling tap water can lead to changes in the DBP concentrations and modify the exposure through ingestion. Changes in the concentration of 4 individual trihalomethanes (THM4 (chloroform (TCM, bromodichloromethane (BDCM, dibromochloromethane (DBCM, and bromoform (TBM, MX, and bromate were tested when boiling and filtering high bromine-containing tap water from Barcelona. For filtering, we used a pitcher-type filter and a household reverse osmosis filter; for boiling, an electric kettle, a saucepan, and a microwave were used. Samples were taken before and after each treatment to determine the change in the DBP concentration. pH, conductivity, and free/total chlorine were also measured. A large decrease of THM4 (from 48% to 97% and MX concentrations was observed for all experiments. Bromine-containing trihalomethanes were mostly eliminated when filtering while chloroform when boiling. There was a large decrease in the concentration of bromate with reverse osmosis, but there was a little effect in the other experiments. These findings suggest that the exposure to THM4 and MX through ingestion is reduced when using these household appliances, while the decrease of bromate is device dependent. This needs to be considered in the exposure assessment of the epidemiological studies.

  4. Factors associated with sources, transport, and fate of chloroform and three other trihalomethanes in untreated groundwater used for drinking water

    Science.gov (United States)

    Carter, Janet M.; Moran, Michael J.; Zogorski, John S.; Price, Curtis V.

    2012-01-01

    Multiple lines of evidence for indicating factors associated with the sources, transport, and fate of chloroform and three other trihalomethanes (THMs) in untreated groundwater were revealed by evaluating low-level analytical results and logistic regression results for THMs. Samples of untreated groundwater from wells used for drinking water were collected from 1996-2007 from 2492 wells across the United States and analyzed for chloroform, bromodichloromethane, dibromochloromethane, and bromoform by a low-level analytical method implemented in April 1996. Using an assessment level of 0.02 μg/L, chloroform was detected in 36.5% of public-well samples and 17.6% of domestic-well samples, with most concentrations less than 1 μg/L. Brominated THMs occurred less frequently than chloroform but more frequently in public-well samples than domestic-well samples. For both public and domestic wells, THMs occurred most frequently in urban areas. Logistic regression analyses showed that the occurrence of THMs was related to nonpoint sources such as urban land use and to point sources like septic systems. The frequent occurrence and concentration distribution pattern of THMs, as well as their frequent co-occurrence with other organic compounds and nitrate, all known to have anthropogenic sources, and the positive associations between THM occurrence and dissolved oxygen and recharge indicate the recycling of water that contains THMs and other anthropogenic contaminants.

  5. Formation and distribution of disinfection by-products during chlorine disinfection in the presence of bromide ion

    Institute of Scientific and Technical Information of China (English)

    LI Bo; QU JiuHui; LIU HuiJuan; ZHAO Xu

    2008-01-01

    The influences of contact time and pH value on the formation and distribution of four species of triha-lomethanes and five species of haloacetic acids during chlorination in the presence of bromine were investigated. Results showed that the distribution of molar fraction of trihalomethanes varied with contact time due to the change of bromide ion concentration during chlorination. Most of the triha-lomethanes comprising bromine-containing species and the favored products of the haloacetic acids were chlorine-containing species after 24 h of chlorination. The extent of bromine incorporation in tri-halomethanes and haloacetic acids both decreased with time. The contact time also had influence on the formation rate of different species of haloacetic acids. The formation and distribution of triha-lomethanes and haloacetic acids strongly depended on the chlorination pH value. All of the triha-lomethanes species formation increased with the increase of pH value except the bromoform that had not been detected. The molar fraction of bromodichloromethane and dibromochloromethane contain-ing bromine increased with pH value while chloroform without bromine decreased. Under the pH range studied in this experiment, the predominant haloacetic acids species were trichloroacetic acid and dichloroacetic acid which all decreased with the increase of pH value and the level of TCAA was higher than that of DCAA.

  6. Bacterial Cellular Materials as Precursors of Chloroform

    Science.gov (United States)

    Wang, J.; Ng, T.; Zhang, Q.; Chow, A. T.; Wong, P.

    2011-12-01

    The environmental sources of chloroform and other halocarbons have been intensively investigated because their effects of stratospheric ozone destruction and environmental toxicity. It has been demonstrated that microorganisms could facilitate the biotic generation of chloroform from natural organic matters in soil, but whether the cellular materials itself also serves as an important precursor due to photo-disinfection is poorly known. Herein, seven common pure bacterial cultures (Acinetobacter junii, Aeromonas hydrophila, Bacillus cereus, Bacillus substilis, Escherichia coli, Shigella sonnei, Staphylococcus sciuri) were chlorinated to evaluate the yields of chloroform, dibromochloromethane, dichlorobromomethane, and bromoform. The effects of bromide on these chemical productions and speciations were also investigated. Results showed that, on average, 5.64-36.42 μg-chloroform /mg-C were generated during the bacterial chlorination, in similar order of magnitude to that generated by humic acid (previously reported as 78 μg-chloroform/mg-C). However, unlike humic acid in water chlorination, chloroform concentration did not simply increase with the total organic carbon in water mixture. In the presence of bromide, the yield of brominated species responded linearly to the bromide concentration. This study provides useful information to understand the contributions of chloroform from photodisinfection processes in coastal environments.

  7. In-situ BrO measurements in the upper troposphere / lower stratosphere. Validation of the ENVISAT satellite measurements and photochemical model studies

    Energy Technology Data Exchange (ETDEWEB)

    Hrechanyy, S.

    2007-04-15

    and SCOUT-O3 in the 15-20 km altitude regime are at the low side of comparable DOAS measurements a CLaMS study of the evolution of Bry from the source gases has been carried out. For this purpose an ensemble of trajectories rising from the lower troposphere to the TTL within 6 to more than 90 days were initialized with observed mixing ratios in the boundary layer of all important organic bromine source gases and the free-up of Bry by chemical and photochemical reactions was simulated. Bromoform, CHBr3, was found to be the main source of inorganic bromine at the tropopause. The derived tropospheric lifetime of bromoform is 33 days. The modelled BrO mixing ratio at the tropopause (less than 2.5 pptv) is consistent with HALOX measurements which do not detect significant amounts of BrO there (<1-2 pptv). Therefore measurements of more than 4 pptv (as retrieved from SCIAMACHY) can only be explained trough processes not included in the model. (orig.)

  8. Oceanic contributions from tropical upwelling systems to atmospheric halogens

    Science.gov (United States)

    Ziska, Franziska; Hepach, Helmke; Stemmler, Irene; Quack, Birgit; Atlas, Elliot; Fuhlbrügge, Steffen; Bracher, Astrid; Tegtmeier, Susann; Krüger, Kirstin

    2014-05-01

    Short lived halogenated substances (halocarbons) from the oceans contribute to atmospheric halogens, where they are involved in ozone depletion and aerosol formation. Oceanic regions that are characterized by high biological activity are often associated with increased halocarbon abundance of e.g. bromoform (CHBr3) and dibromomethane (CH2Br2), representing the main contributors to atmospheric organic bromine. Apart from biological production, photochemical pathways play an important role in the formation of methyl iodide (CH3I), the most abundant organoiodine in the marine atmosphere. Recently, the contribution of biogenic diiodomethane (CH2I2) and chloroiodomethane (CH2ClI) to atmospheric organic iodine has been estimated to be similarly significant as CH3I. In the tropics, rapid uplift of surface air can transport these short-lived compounds into the upper troposphere and into the stratosphere. Oceanic upwelling systems off Mauritania, Peru and in the equatorial Atlantic might therefore potentially contribute large amounts of halocarbons to the stratosphere. Concentrations and emissions of iodo- and bromocarbons from several SOPRAN campaigns in different tropical upwelling systems, the Mauritanian and the equatorial upwelling in the Atlantic, as well as the Peruvian upwelling in the Pacific, will be presented. Processes contributing to halocarbon occurrence in the water column, as well as biological and physical factors influencing their emission into the atmosphere are investigated (Fuhlbrügge, et al. 2013; Hepach et al., 2013). We will present the relative contribution of the upwelling systems to global air-sea fluxes from different modelling studies. The data based bottom-up emissions from Ziska et al. (2013) will be compared to model simulated halocarbons. The model is a global three-dimensional ocean general circulation model with an ecosystem model and halocarbon module embedded (MPIOM/HAMOCC). It resolves CH3I and CHBr3 production, degradation, and

  9. Sources and occurrence of chloroform and other trihalomethanes in drinking-water supply wells in the United States, 1986-2001

    Science.gov (United States)

    Ivahnenko, Tamara; Zogorski, J.S.

    2006-01-01

    Chloroform and three other trihalomethanes (THMs)--bromodichloromethane, dibromochloromethane, and bromoform--are disinfection by-products commonly produced during the chlorination of water and wastewater. Samples of untreated ground water from drinking-water supply wells (1,096 public and 2,400 domestic wells) were analyzed for THMs and other volatile organic compounds (VOCs) during 1986-2001, or compiled, as part of the U.S. Geological Survey's National Water-Quality Assessment Program. This report provides a summary of potential sources of THMs and of the occurrence and geographical distribution of THMs in samples from public and domestic wells. Evidence for an anthropogenic source of THMs and implications for future research also are presented. Potential sources of THMs to both public and domestic wells include the discharge of chlorinated drinking water and wastewater that may be intentional or inadvertent. Intentional discharge includes the use of municipally supplied chlorinated water to irrigate lawns, golf courses, parks, gardens, and other areas; the use of septic systems; or the regulated discharge of chlorinated wastewater to surface waters or ground-water recharge facilities. Inadvertent discharge includes leakage of chlorinated water from swimming pools, spas, or distribution systems for drinking water or wastewater sewers. Statistical analyses indicate that population density, the percentage of urban land, and the number of Resource Conservation and Recovery Act hazardous-waste facilities near sampled wells are significantly associated with the probability of detection of chloroform, especially for public wells. Domestic wells may have several other sources of THMs, including the practice of well disinfection through shock chlorination, laundry wastewater containing bleach, and septic system effluent. Chloroform was the most frequently detected VOC in samples from drinking-water supply wells (public and domestic wells) in the United States. Although

  10. Name Modelling Activities for the CAST/Contrast/Attrex Very Short Lived Species Measurements

    Science.gov (United States)

    Harris, N. R. P.; Filus, M. T.; Ashfold, M.; Pyle, J. A.; Atlas, E. L.; Manning, A.; Meneguz, E.

    2014-12-01

    The UK Met Office Numerical Atmospheric dispersion Modeling Environment (NAME) is used to assess the spatial and temporal variability of transport of very short-lived halogenated organic species (VSLS), in particular bromoform, dibromomethane and methyl iodide, within the West Pacific tropical region. The NAME modelling results are compared with airborne measurements of VSLS taken during NASA ATTREX, NCAR CONTRAST and NERC CAST campaigns in January-March, 2014. In this work, the NAME model is used to link the aircraft measurements to examine the vertical distribution of VSLS in the West Pacific troposphere. The major focus will be on assessing vertical transport in deep convection which is one of the crucial factors in redistributing chemicals within the tropical troposphere. The work presented shows the analysis of NAME runs made from the ATTREX flights over the East Pacific in January-February, 2013 and the ATTREX and CONTRAST flight tracks over the West Pacific in January-March, 2014. Each ATTREX 2013 and 2014 flight track is divided into segments, from which particles are released and followed backward to identify the low-level sources of air. Particles (10,000 per single point along the flight track) are released from the flight tracks and followed 12-days backwards. Fractions of trajectories are calculated according to particles which crossed below 5 and 1 km (corresponding to low troposphere and oceanic boundary layer, respectively). Then, initial concentrations for VSLS are assigned to particles which originated from below 5/1 km and final concentrations at flight altitudes are determined based on e-folding equations. Results, obtained by running NAME, are compared with ATTREX VSLS flight measurements.

  11. NAME modelling activities for the CAST-CONTRAST-ATTREX VSLS measurements

    Science.gov (United States)

    Filus, Michal; Harris, Neil; Pyle, John; Ashfold, Matt; Atlas, Eliott; Navarro, Maria; Meneguz, Elena; Manning, Alistair

    2015-04-01

    The Numerical Atmospheric dispersion Modeling Environment (NAME) model is used to assess the spatial and temporal variability of transport of very short-lived halogenated organic species (VSLS), in particular bromoform, dibromomethane and methyl iodide, within the West Pacific tropical region. The NAME modelling results are compared with airborne measurements of VSLS taken during NASA ATTREX, NCAR CONTRAST and NERC CAST campaigns in January-March, 2014. NAME model aims to link the aircraft measurements to examine the vertical distribution of VSLS in the West Pacific troposphere. The major focus will be on assessing vertical transport in deep convection which is one of the crucial factors in redistributing chemicals within the tropical troposphere. The work presented shows the analysis of NAME runs made from the ATTREX flights over the East Pacific in January-February, 2013 and the ATTREX and CONTRAST flight tracks over the West Pacific in January-March, 2014. Each ATTREX 2013 and 2014 flight track is divided into segments, from which particles are released and followed backward to identify the low-level sources of air. Particles (15,000 per single point along the flight track) are released from the flight altitudes tracks and followed 12-days backwards. Fractions of trajectories are calculated according to particles which crossed below 5 and 1 km (corresponding to low troposphere and oceanic boundary layer, respectively). Then, initial concentrations for VSLS are assigned to particles which originated from below 5/1 km and final concentrations at flight altitudes are determined. NAME modeled results are compared with ATTREX VSLS flight measurements. Interannual variability of atmospheric transport of VSLS in the Tropics is studied by performing mock ATTREX-flight NAME runs for years: 2005-2014, with emphasis put on strong ENSO phase years.

  12. Organic matter from benthic foraminifera (Ammonia beccarii) shells by FT-IR spectroscopy: A study on Tupilipalem, South east coast of India.

    Science.gov (United States)

    Sreenivasulu, G; Jayaraju, N; Sundara Raja Reddy, B C; Lakshmi Prasad, T; Nagalakshmi, K; Lakshmanna, B

    2017-01-01

    Fourier Transform Infrared Spectroscopy (FTIR) was used to study the variations in organic matters of benthic foraminifera (Ammonia beccarii) from four samples collected from beach environments from brackish environments along Tupilipalem coast (South east coast of India). Common absorption bands were observed as peaks in the range of 3600-3400 cm(-1), 3000-2850 cm(-1), 1750-1740 cm(-1), 1640-1600 cm(-1), 1450-1350 cm(-1), 885-870 cm(-1) and 725-675 cm(-1) in all the shells of Ammonia beccarii. The FTIR spectrum of station-1 represents the presence of alkanes (CH3) and alkyl halide (C-F stretching) with absorptions at the range 1385-1255 and 1350-1150 cm(-1) were observed and ether (C-O stretching) absorption band was observed at stations 1 and 3 with wavenumber of 1115 cm(-1) and 1117 cm(-1) respectively. Alkynes C-H bend was observed at station-1 with the wavenumber of 667.43 cm(-1). The shifting of peak positions in all the samples is could be due to presence of organic matter in the samples. Satellite remote sensing and field observation data revealed that the river mouth at Tupilipalem coast was closed by a sand bar. Consequentially, this waterbody may affect the species diversity. •Positions of the sampling locations were identified using a hand-held Garmin Global Positioning System (GPS).•Foraminifera from the sediment were obtained using a mixture of Bromoform and Acetone.•The functional groups present in the benthic foraminifera shells were recorded in the spectral range of 4000-400 cm(-1) using an FT-IR Spectrophotometer.

  13. Exposição humana a trialometanos presentes em água tratada Human exposure to trihalomethanes in drinking water

    Directory of Open Access Journals (Sweden)

    Maria Y Tominaga

    1999-08-01

    Full Text Available Realizou-se uma revisão bibliográfica do período de 1974-1998, no MEDLINE, sobre compostos orgânicos halogenados derivados de hidrocarbonetos denominados de trialometanos. Muitos deles, reconhecidamente carcinogênicos para diferentes espécies animais, podem ser encontrados freqüentemente, inclusive entre nós, em águas tratadas e enviadas à população urbana. É o caso de compostos como o clorofórmio, bromodiclorometano, clorodibromometano e bromofórmio, resultantes da halogenação de precursores, principalmente substâncias húmicas e fúlvicas presentes na água que será tratada (clorada. Assim, descreve-se sua formação, fontes de exposição humana bem como os aspectos toxicológicos de maior importância: disposição cinética e espectro dos efeitos tóxicos (carcinogênicos, mutagênicos e teratogênicos decorrentes de exposições a longo prazo e baixas concentrações. Níveis seguros de exposição propostos são também fornecidos.Halogenated hydrocarbon compounds, some of them recognized as carcinogenic to different animal species can be found in drinking water. Chloroform, bromodichloromethane, dibromochloromethane and bromoform are the most important trihalomethanes found in potable water. They are produced in natural waters during chlorinated desinfection by the halogenation of precursors, specially humic and fulvic compounds. The review, in the MEDLINE covers the period from 1974 to 1998, presents the general aspects of the formation of trihalomethanes, sources of human exposure and their toxicological meaning for exposed organisms: toxicokinetic disposition and spectrum of toxic effects (carcinogenic, mutagenic and teratogenic.

  14. Transformation of bromide in thermo activated persulfate oxidation processes.

    Science.gov (United States)

    Lu, Junhe; Wu, Jinwei; Ji, Yuefei; Kong, Deyang

    2015-07-01

    Sulfate radicals ( [Formula: see text] ) are applied to degrade various organic pollutants. Due to its high oxidative potential, [Formula: see text] is presumed to be able to transform bromide to reactive bromine species that can react with natural organic matter subsequently to form brominated products including brominated disinfection by-products (Br-DBPs). This research was designed to investigate the transformation of bromide in thermo activated persulfate oxidation process in the presence of humic acid (HA). Significant formation of bromoform and bromoacetic acids was verified. Their formation was attributed to the reactions of HA and reactive bromine species including Br·, [Formula: see text] HOBr(-), and free bromine resulted from the oxidation of bromide by [Formula: see text] . Yields of Br-DBPs increased monotonically at persulfate concentration of 1.0 mM and working temperature of 70 °C. However, the time-depended formation exhibited an increasing and the decreasing profile when persulfate was 5.0 mM, suggesting further degradation of organic bromine. HPLC/ICP-MS analysis demonstrated that the organic bromine was eventually transformed to bromate at this condition. Thus, a transformation scheme was proposed in which the bromine could be recycled multiple times between inorganic bromide and organic bromine before being finally transformed to bromate. This is the first study that reveals the comprehensive transformation map of bromine in [Formula: see text] based reaction systems, which should be taken into consideration when such technologies are used to eliminate contamination in real practice.

  15. Production of various disinfection byproducts in indoor swimming pool waters treated with different disinfection methods.

    Science.gov (United States)

    Lee, Jin; Jun, Myung-Jin; Lee, Man-Ho; Lee, Min-Hwan; Eom, Seog-Won; Zoh, Kyung-Duk

    2010-11-01

    In this study, the concentrations of disinfection byproducts (DBPs), including trihalomethanes (THMs; chloroform, bromodichloromethane, dibromochloromethane, and bromoform), haloacetic acids (HAAs; dichloroacetic acid and trichloroacetic acid), haloacetonitriles (HANs; dichloroacetonitrile, trichloroacetonitrile, bromochloroacetonitrile, and dibromoacetonitrile), and chloral hydrate (CH) were measured in 86 indoor swimming pools in Seoul, Korea, treated using different disinfection methods, such as chlorine, ozone and chlorine, and a technique that uses electrochemically generated mixed oxidants (EGMOs). The correlations between DBPs and other environmental factors such as with total organic carbon (TOC), KMnO(4) consumption, free residual chlorine, pH, and nitrate (NO(3)(-)) in the pools were examined. The geometric mean concentrations of total DBPs in swimming pool waters were 183.1±2.5μg/L, 32.6±2.1μg/L, and 139.9±2.4μg/L in pools disinfected with chlorine, ozone/chlorine, and EGMO, respectively. The mean concentrations of total THMs (TTHMs), total HAAs (THAAs), total HANs (THANs), and CH differed significantly depending on the disinfection method used (P<0.01). Interestingly, THAAs concentrations were the highest, followed by TTHMs, CH, and THANs in all swimming pools regardless of disinfection method. TOC showed a good correlation with the concentrations of DBPs in all swimming pools (chlorine; r=0.82, P<0.01; ozone/chlorine; r=0.52, P<0.01, EGMO; r=0.39, P<0.05). In addition, nitrate was positively correlated with the concentrations of total DBPs in swimming pools disinfected with chlorine and ozone/chlorine (chlorine; r=0.58; ozone/chlorine; r=0.60, P<0.01), whereas was negative correlated with the concentrations of total DBPs (r=-0.53, P<0.01) in the EGMO-treated pools.

  16. Determination of volatile organic compounds in water by headspace solid-phase microextraction gas chromatography coupled to tandem mass spectrometry with triple quadrupole analyzer.

    Science.gov (United States)

    Cervera, M I; Beltran, J; Lopez, F J; Hernandez, F

    2011-10-17

    In the present work, a rapid method with little sample handling has been developed for determination of 23 selected volatile organic compounds in environmental and wastewater samples. The method is based on headspace solid-phase microextraction (SPME) followed by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) determination using triple quadrupole analyzer (QqQ) in electron ionization mode. The best conditions for extraction were optimised with a factorial design taking into account the interaction between different parameters and not only individual effects of variables. In the optimized procedure, 4 mL of water sample were extracted using a 10 mL vial and adding 0.4 g NaCl (final NaCl content of 10%). An SPME extraction with carboxen/polydimethylsiloxane 75 μm fiber for 30 min at 50°C (with 5 min of previous equilibration time) with magnetic stirring was applied. Chromatographic determination was carried out by GC-MS/MS working in Selected Reaction Monitoring (SRM) mode. For most analytes, two MS/MS transitions were acquired, although for a few compounds it was difficult to obtain characteristic abundant fragments. In those cases, a pseudo selected reaction monitoring (pseudo-SRM) with three ions was used instead. The intensity ratio between quantitation (Q) and confirmation (q) signals was used as a confirmatory parameter. The method was validated by means of recovery experiments (n=6) spiking mineral water samples at three concentration levels (0.1, 5 and 50 μg L(-1)). Recoveries between 70% and 120% were generally obtained with relative standard deviations (RSDs) lower than 20%. The developed method was applied to surface water and wastewater from a wastewater treatment plant and from a municipal solid-waste treatment plant. Several compounds, like chloroform, benzene, trichloroethylene, toluene, tetrachloroethylene, dibromochloromethane, xylenes and bromoform were detected and confirmed in all the samples analyzed.

  17. CONCENTRATION OF TRIHALOMETHANES (THM AND PRECURSORS IN DRINKING WATER WITHIN DISTRIBUTION NETWORKS

    Directory of Open Access Journals (Sweden)

    CORNELIA DIANA ROMAN

    2012-03-01

    Full Text Available Concentration of trihalomethanes (THM and precursors in drinking water within distribution networks. Water chlorination is the disinfection method most widely used, having however the disadvantage of producing trihalomethanes (THM as secondary compounds, which are included in the list of priority hazardous substances in water. THM formation is influenced by the raw water composition and chlorine from the disinfection process. This paper intends to highlight the individual values of the chemical compounds precursors of THM in the water network in order to correlate them with the evolution of THM concentration. The cities of Targu Mures and Zalau were chosen as the study area having surface waters with different degrees of contamination as the water source. Pre-treatment with potassium permanganate is used at the water treatment plant in Targu Mures, while pre-chlorination is used at the water treatment plant in Zalau. Water sampling was performed weekly between March-May, 2011 in three sampling points of each city, maintained during the period of study. Total THM and their compounds as well as THM precursors (oxidability, ammonium content, nitrites and nitrates were measured. The water supplied in the distribution network corresponded integrally to the quality standards in terms of the analyzed indicators, including THM concentrations. The higher average THM concentrations in Zalau (52.01±14 μg/L compared to Targu Mures (36.43±9.14 μg/L were expected as a result of precursors concentration. In terms of THM compounds, they had similar proportions in the two localities, chloroform being clearly predominant, followed by dichlorobromoform and dibromochloroform, while bromoform was not identified. Statistical data analysis showed that the presence of THM precursors is correlated with the THM levels but not sufficient for their generation, even if they can be considered in general the basis of a valid prediction.

  18. Meteorological constraints on oceanic halocarbons above the Peruvian Upwelling

    Directory of Open Access Journals (Sweden)

    S. Fuhlbrügge

    2015-07-01

    Full Text Available Halogenated very short lived substances (VSLS are naturally produced in the ocean and emitted to the atmosphere. Recently, oceanic upwelling regions in the tropical East Atlantic were identified as strong sources of brominated halocarbons to the atmosphere. During a cruise of R/V METEOR in December 2012 the oceanic sources and emissions of various halogenated trace gases and their mixing ratios in the marine atmospheric boundary layer (MABL were investigated above the Peruvian Upwelling for the first time. This study presents novel observations of the three VSLS bromoform, dibromomethane and methyl iodide together with high resolution meteorological measurements and Lagrangian transport modelling. Although relatively low oceanic emissions were observed, except for methyl iodide, surface atmospheric abundances were elevated. Radiosonde launches during the cruise revealed a low, stable MABL and a distinct trade inversion above acting both as strong barriers for convection and trace gas transport in this region. Significant correlations between observed atmospheric VSLS abundances, sea surface temperature, relative humidity and MABL height were found. We used a simple source-loss estimate to identify the contribution of oceanic emissions to observed atmospheric concentrations which revealed that the observed marine VSLS abundances were dominated by horizontal advection below the trade inversion. The observed VSLS variations can be explained by the low emissions and their accumulation under different MABL and trade inversion conditions. This study confirms the importance of oceanic upwelling and trade wind systems on creating effective transport barriers in the lower atmosphere controlling the distribution of VSLS abundances above ocean upwelling regions.

  19. [Formation and Variation of Brominated Disinfection By-products in A Combined Ultrafiltration and Reverse Osmosis Process for Seawater Desalination].

    Science.gov (United States)

    Yang, Zhe; Sun, Ying-xue; Shi, Na; Hu, Hong-ying

    2015-10-01

    The characteristics of dissolved organic matter (DOM) and brominated disinfection by-products ( Br-DBPs ) during a seawater desalination ultrafiltration (UF) combined reverse osmosis (RO) process were studied. The seawater contained high level of bromide ion (45.6-50.9 mg x L(-1)) and aromatic compounds with specific ultraviolet absorbance ( SUVA) of 3.6-6.0 L x (mg x m)(-1). The tryptophan-like aromatic protein, fulvic acid-like and soluble microbial by-product-like were the main fluorescent DOM in the seawater. After pre-chlorination of the seawater, the concentrations of DBPs was significantly increased in the influent of UF, which was dominantly the Br-DBPs. Bromoform (CHBr3) accounted for 70.48% - 91.50% of total trihalomethanes (THMs), dibromoacetic acid (Br2CHCO2H) occupied 81.14% - 100% of total haloacetic acids (HAAs) and dibromoacetonitrile (C2HBr2N) occupied 83.77% - 87.45% of total haloacetonitriles ( HANs). The removal efficiency of THMs, HAAs and HANs by the UF membrane was 36.63% - 40.39%, 73.83% - 95.38% and 100%, respectively. The RO membrane could completely remove the HAAs, while a little of the THMs was penetrated. The antiestrogenic activity in the seawater was 0.35 - 0.44 mg x L(-1), which was increased 32% - 69% after the pre-chlorination. The DBPs and other bio-toxic organics which formed during the UF-RO process were finally concentrated in the UF concentrate and RO concentrate.

  20. Global sensitivity analysis of the GEOS-Chem chemical transport model: ozone and hydrogen oxides during ARCTAS (2008)

    Science.gov (United States)

    Christian, Kenneth E.; Brune, William H.; Mao, Jingqiu

    2017-03-01

    Developing predictive capability for future atmospheric oxidation capacity requires a detailed analysis of model uncertainties and sensitivity of the modeled oxidation capacity to model input variables. Using oxidant mixing ratios modeled by the GEOS-Chem chemical transport model and measured on the NASA DC-8 aircraft, uncertainty and global sensitivity analyses were performed on the GEOS-Chem chemical transport model for the modeled oxidants hydroxyl (OH), hydroperoxyl (HO2), and ozone (O3). The sensitivity of modeled OH, HO2, and ozone to model inputs perturbed simultaneously within their respective uncertainties were found for the flight tracks of NASA's Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) A and B campaigns (2008) in the North American Arctic. For the spring deployment (ARCTAS-A), ozone was most sensitive to the photolysis rate of NO2, the NO2 + OH reaction rate, and various emissions, including methyl bromoform (CHBr3). OH and HO2 were overwhelmingly sensitive to aerosol particle uptake of HO2 with this one factor contributing upwards of 75 % of the uncertainty in HO2. For the summer deployment (ARCTAS-B), ozone was most sensitive to emission factors, such as soil NOx and isoprene. OH and HO2 were most sensitive to biomass emissions and aerosol particle uptake of HO2. With modeled HO2 showing a factor of 2 underestimation compared to measurements in the lowest 2 km of the troposphere, lower uptake rates (γHO2 < 0. 055), regardless of whether or not the product of the uptake is H2O or H2O2, produced better agreement between modeled and measured HO2.

  1. Formation of bromate and halogenated disinfection byproducts during chlorination of bromide-containing waters in the presence of dissolved organic matter and CuO

    KAUST Repository

    Liu, Chao

    2015-12-02

    Previous studies showed that significant bromate (BrO3-) can be formed via the CuO-catalyzed disproportionation of hypobromous acid (HOBr) pathway. In this study, the influence of CuO on the formation of BrO3- and halogenated disinfection byproducts (DBPs) (e.g., trihalomethanes, THMs and haloacetic acids, HAAs) during chlorination of six dissolved organic matter (DOM) isolates was investigated. Only in the presence of slow reacting DOM (from treated Colorado River water, i.e., CRW-BF-HPO), significant BrO3- formation is observed, which competes with bromination of DOM (i.e., THM and HAA formation). Reactions between HOBr and 12 model compounds in the presence of CuO indicates that CuO-catalyzed HOBr disproportionation is completely inhibited by fast reacting phenols, while it predominates in the presence of practically unreactive compounds (acetone, butanol, propionic, and butyric acids). In the presence of slow reacting di- and tri-carboxylic acids (oxalic, malonic, succinic, and citric acids), BrO3- formation varies, depending on its competition with bromoform and dibromoacetic acid formation (i.e., bromination pathway). The latter pathway can be enhanced by CuO due to the activation of HOBr. Therefore, increasing CuO dose (0-0.2 g L-1) in a reaction system containing chlorine, bromide, and CRW-BF-HPO enhances the formation of BrO3-, total THMs and HAAs. Factors including pH and initial reactant concentrations influence the DBP formation. These novel findings have implications for elevated DBP formation during transportation of chlorinated waters in copper-containing distribution systems.

  2. Representation of tropical deep convection in atmospheric models – Part 2: Tracer transport

    Directory of Open Access Journals (Sweden)

    C. R. Hoyle

    2011-08-01

    Full Text Available The tropical transport processes of 14 different models or model versions were compared, within the framework of the SCOUT-O3 (Stratospheric-Climate Links with Emphasis on the Upper Troposphere and Lower Stratosphere project. The tested models range from the regional to the global scale, and include numerical weather prediction (NWP, chemical transport, and chemistry-climate models. Idealised tracers were used in order to prevent the model's chemistry schemes from influencing the results substantially, so that the effects of modelled transport could be isolated. We find large differences in the vertical transport of very short-lived tracers (with a lifetime of 6 h within the tropical troposphere. Peak convective outflow altitudes range from around 300 hPa to almost 100 hPa among the different models, and the upper tropospheric tracer mixing ratios differ by up to an order of magnitude. The timing of convective events is found to be different between the models, even among those which source their forcing data from the same NWP model (ECMWF. The differences are less pronounced for longer lived tracers, however they could have implications for modelling the halogen burden of the lowermost stratosphere through transport of species such as bromoform, or short-lived hydrocarbons into the lowermost stratosphere. The modelled tracer profiles are strongly influenced by the convective transport parameterisations, and different boundary layer mixing parameterisations also have a large impact on the modelled tracer profiles. Preferential locations for rapid transport from the surface into the upper troposphere are similar in all models, and are mostly concentrated over the western Pacific, the Maritime Continent and the Indian Ocean. In contrast, models do not indicate that upward transport is highest over western Africa.

  3. Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction

    Energy Technology Data Exchange (ETDEWEB)

    Soorkia, Satchin; Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Trevitt, Adam J.; Wilson, Kevin R.; Leone, Stephen R.

    2010-03-16

    The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and the result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.

  4. Rejection of emerging organic micropollutants in nanofiltration-reverse osmosis membrane applications.

    Science.gov (United States)

    Xu, Pei; Drewes, Jörg E; Bellona, Christopher; Amy, Gary; Kim, Tae-Uk; Adam, Marc; Heberer, Thomas

    2005-01-01

    The rejection of emerging trace organics by a variety of commercial reverse osmosis (RO), nanofiltration (NF), and ultra-low-pressure RO (ULPRO) membranes was investigated using TFC-HR, NF-90, NF-200, TFC-SR2, and XLE spiral membrane elements (Koch Membrane Systems, Wilmington, Massachusetts) to simulate operational conditions for drinking-water treatment and wastewater reclamation. In general, the presence of effluent organic matter (EfOM) improved the rejection of ionic organics by tight NF and RO membranes, as compared to a type-II water matrix (adjusted by ionic strength and hardness), likely as a result of a decreased negatively charged membrane surface. Rejection of ionic pharmaceutical residues and pesticides exceeded 95% by NF-90, XLE, and TFC-HR membranes and was above 89% for the NF-200 membrane. Hydrophobic nonionic compounds, such as bromoform and chloroform, exhibited a high initial rejection, as a result of both hydrophobic-hydrophobic solute-membrane interactions and steric exclusion, but rejection decreased significantly after 10 hours of operation because of partitioning of solutes through the membranes. This resulted in a partial removal of disinfection byproducts by the RO membrane TFC-HR. In a type-II water matrix, the effect of increasing feed water recoveries on rejection of hydrophilic ionic and nonionic compounds was compound-dependent and not consistent for different membranes. The presence of EfOM, however, could neutralize the effect of hydrodynamic operating condition on rejection performance. The ULPRO and tight NF membranes were operated at lower feed pressure, as compared to the TFC-HR, and provided a product water quality similar to a conventional RO membrane, regarding trace organics of interest.

  5. The physiological and ecological roles of volatile halogen production by marine diatoms

    Science.gov (United States)

    Hughes, Claire; Sun, Shuo

    2015-04-01

    Sea-to-air halogen flux is known to have a major impact on catalytic ozone cycling and aerosol formation in the troposphere. The biological production of volatile organic (e.g. bromoform, diiodomethane) and reactive inorganic halogens (e.g. molecular iodine) is believed to play an important role in mediating halogen emissions from the marine environment. Marine diatoms in particular are known to produce the organic and inorganic volatile halogens at high rates in pelagic waters and sea-ice systems. The climate-induced changes in diatom communities that have already been observed and are expected to occur throughout the world's oceans as warming progresses are likely to alter sea-to-air halogen flux. However, we currently have insufficient understanding of the physiological and ecological functions of volatile halogen production to develop modelling tools that can predict the nature and magnitude of the impact. The results of a series of laboratory studies aimed at establishing the physiological and ecological role of volatile halogen production in two marine polar diatoms (Thalassiosira antarctica and Porosira glacialis) will be described in this presentation. We will focus on our work investigating how the activity of the haloperoxidases, a group of enzymes known to be involved in halogenation reactions in marine organisms, is altered by environmental conditions. This will involve exploring the antioxidative defence role proposed for marine haloperoxidases by showing specifically how halogenating activity varies with photosynthetic rate and changes in the ambient light conditions in the two model marine diatoms. We will also present results from our experiments designed to investigate how volatile halogen production is impacted by and influences diatom-bacterial interactions. We will discuss how improved mechanistic understanding like this could pave the way for future volatile halogen-ecosystem model development.

  6. Modeling daily variation of trihalomethane compounds in drinking water system, Houston, Texas.

    Science.gov (United States)

    Chaib, Embarka; Moschandreas, Demetrios

    2008-03-01

    Total trihalomethanes (TTHM) concentrations vary widely and periodically between 70 and 130 ppb. Data from the National Environmental Services Laboratory, Houston, Texas indicate that pH and free residual chlorine contribute minimally to the wide variability of TTHM levels. Temperature variation in drinking fluctuates from 11 to 27 degrees C. The objective of this research is to formulate a model that delineates more clearly the daily variations of the most prevalent volatile trihalomethane by-products: chloroform (CHCl3), bromodichloromethane (CHBr2Cl), and bromoform (CHBr3) levels from drinking water. This model simulates the daily fluctuation of THM at a single location and at any time during the day as a function of the water temperature and the average concentration of TTHM, which can be estimated. The hypothesis of this study is that observed daily fluctuations of TTHM, CHCl3, CHCl2Br, CHClBr2, and CHBr3 are periodic. This hypothesis is tested using autocorrelation functions and it is shown that for the series of pH the correlation coefficient is maximal at zero lags, rapidly decreases to zero, and increases again between 4- and 6-h period. Such pattern suggests random fluctuation unrelated to time. However, the series of free residual chlorine, temperature, TTHM, CHCl3, CHCl2Br, CHClBr2, and CHBr3 suggest a different pattern. The correlation coefficient increases when the time-shift approaches 24 h. These repetitions in fluctuation of content over a 24-h period are statistically significant. The model formulated in this study provides insights in TTHM variation and is a necessary tool to reduce the error when estimating potential risk from exposure to trihalomethane compounds in drinking water system. In general, calculation of potential risk by using a value measured early morning or late afternoon concentrations were found minimal lead to an underestimation of the population risk.

  7. Comparison of Spot and Time Weighted Averaging (TWA Sampling with SPME-GC/MS Methods for Trihalomethane (THM Analysis

    Directory of Open Access Journals (Sweden)

    Don-Roger Parkinson

    2016-02-01

    Full Text Available Water samples were collected and analyzed for conductivity, pH, temperature and trihalomethanes (THMs during the fall of 2014 at two monitored municipal drinking water source ponds. Both spot (or grab and time weighted average (TWA sampling methods were assessed over the same two day sampling time period. For spot sampling, replicate samples were taken at each site and analyzed within 12 h of sampling by both Headspace (HS- and direct (DI- solid phase microextraction (SPME sampling/extraction methods followed by Gas Chromatography/Mass Spectrometry (GC/MS. For TWA, a two day passive on-site TWA sampling was carried out at the same sampling points in the ponds. All SPME sampling methods undertaken used a 65-µm PDMS/DVB SPME fiber, which was found optimal for THM sampling. Sampling conditions were optimized in the laboratory using calibration standards of chloroform, bromoform, bromodichloromethane, dibromochloromethane, 1,2-dibromoethane and 1,2-dichloroethane, prepared in aqueous solutions from analytical grade samples. Calibration curves for all methods with R2 values ranging from 0.985–0.998 (N = 5 over the quantitation linear range of 3–800 ppb were achieved. The different sampling methods were compared for quantification of the water samples, and results showed that DI- and TWA- sampling methods gave better data and analytical metrics. Addition of 10% wt./vol. of (NH42SO4 salt to the sampling vial was found to aid extraction of THMs by increasing GC peaks areas by about 10%, which resulted in lower detection limits for all techniques studied. However, for on-site TWA analysis of THMs in natural waters, the calibration standard(s ionic strength conditions, must be carefully matched to natural water conditions to properly quantitate THM concentrations. The data obtained from the TWA method may better reflect actual natural water conditions.

  8. Groundwater contamination by microbiological and chemical substances released from hospital wastewater: health risk assessment for drinking water consumers.

    Science.gov (United States)

    Emmanuel, Evens; Pierre, Marie Gisèle; Perrodin, Yves

    2009-05-01

    Contamination of natural aquatic ecosystems by hospital wastewater is a major environmental and human health issue. Disinfectants, pharmaceuticals, radionuclides and solvents are widely used in hospitals for medical purposes and research. After application, some of these substances combine with hospital effluents and, in industrialised countries, reach the municipal sewer network. In certain developing countries, hospitals usually discharge their wastewater into septic tanks equipped with diffusion wells. The discharge of chemical compounds from hospital activities into the natural environment can lead to the pollution of water resources and risks for human health. The aim of this article is to present: (i) the steps of a procedure intended to evaluate risks to human health linked to hospital effluents discharged into a septic tank equipped with a diffusion well; and (ii) the results of its application on the effluents of a hospital in Port-au-Prince. The procedure is based on a scenario that describes the discharge of hospital effluents, via septic tanks, into a karstic formation where water resources are used for human consumption. COD, Chloroform, dichlomethane, dibromochloromethane, dichlorobromomethane and bromoform contents were measured. Furthermore, the presence of heavy metals (chrome, nickel and lead) and faecal coliforms were studied. Maximum concentrations were 700 NPP/100 ml for faecal coliforms and 112 mg/L for COD. A risk of infection of 10(-5) infection per year was calculated. Major chemical risks, particularly for children, relating to Pb(II), Cr(III), Cr(VI) and Ni(II) contained in the ground water were also characterised. Certain aspects of the scenario studied require improvement, especially those relating to the characterisation of drugs in groundwater and the detection of other microbiological indicators such as protozoa, enterococcus and viruses.

  9. Effects of temperature and chemical addition on the formation of bromoorganic DBPs during ozonation.

    Science.gov (United States)

    Zhang, Xiangru; Echigo, Shinya; Lei, Hongxia; Smith, Michael E; Minear, Roger A; Talley, Jeffrey W

    2005-01-01

    The effects of temperature and addition of OH radical scavengers/enhancers or HOBr scavenger on the formation of bromoorganic disinfection byproducts (DBPs) from ozonation of six raw waters were studied in true batch reactors. The formation of bromoorganic DBPs during ozonation generally increased with the increase of temperature, but might also decrease for the waters with somewhat higher values of specific UV absorbance (SUVA). The addition of hydrogen peroxide, ethanol, or ammonium dramatically decreased the formation of bromoorganic DBPs; t-butanol addition significantly increased the formation of bromoorganic DBPs; bicarbonate addition might increase or decrease bromoorganic DBP formation depending on the water source. For all the waters treated with the chemical addition, the level of total organic bromine (TOBr) varied with the same pace as that of ozone exposure (CT), which suggests that TOBr formed during ozonation may be used to estimate the CT, a measure for the achieved degree of disinfection. The results demonstrate that for each water, the correlation between TOBr and CT was less affected by the change of chemical composition of the water than that between BrO(3)(-) and CT; for a given chemical composition and temperature of a water, there generally were well-defined relationships between TOBr and CT, and bromoform and CT just as that between BrO(3)(-) and CT. The possible mechanisms behind the linear functions of TOBr or BrO(3)(-) versus CT were given. Further study is needed to examine whether the trends found in this research can be applicable for the high SUVA waters.

  10. Formation of THMs and HANs during bromination of Microcystis aeruginosa

    Institute of Scientific and Technical Information of China (English)

    Yunzhu Pu; Lingzhao Kong; Xin Huang; Guoji Ding; Naiyun Gao

    2013-01-01

    Bromine-contained disinfectants and biocides are widely used in swimming pools,recreational waters and cooling towers.The objective of this study was to evaluate the formation of thrihalomethanes (THMs) and haloacetonitriles (HANs) and their cytotoxicity in algae solutions during free bromine disinfection.Disinfection by-products formation potential experiments were conducted using modelsolutions containing 7mg/L (as total organic carbon) Microcystis aeruginosa cells.Effects of free bromine dosage,pH and ammonia were investigated.The results showed that brominated disinfection by-products were the major products when free bromine was applied.The total THMs formed during bromination was much as that formed during chlorination,whereas HANs were elevated by using bromination instead of chlorination.Dibromoacetonitrice (C2H2NBr2) and bromoform (CHBr3) were the only detected species during free bromine disinfection.The production of C2H2NBr2 and CHBr3 increased with disinfectant dosage but decreased with dosing ammonia.CHBr3 increased with the pH changing from 5 to 9.However,C2H2NBr2 achieved the highest production at neutral pH,which was due to a joint effect of variation in hydrolysis rate and free bromine reactivity.The hydrolysis of C2H2NBr2 was basecatalytic and nearly unaffected by disinfectant.Finally,estimation of cytotoxicity of the disinfected algae solutions showed that HANs formation was responsible for the majority of toxicity.Considering its highest toxicity among the measured disinfection by-products,the elevated C2H2NBr2 should be considered when using bromine-related algaecide.

  11. Response of halocarbons to ocean acidification in the Arctic

    Directory of Open Access Journals (Sweden)

    F. E. Hopkins

    2013-04-01

    Full Text Available The potential effect of ocean acidification (OA on seawater halocarbons in the Arctic was investigated during a mesocosm experiment in Spitsbergen in June–July 2010. Over a period of 5 weeks, natural phytoplankton communities in nine ~ 50 m3 mesocosms were studied under a range of pCO2 treatments from ~ 185 μatm to ~ 1420 μatm. In general, the response of halocarbons to pCO2 was subtle, or undetectable. A large number of significant correlations with a range of biological parameters (chlorophyll a, microbial plankton community, phytoplankton pigments were identified, indicating a biological control on the concentrations of halocarbons within the mesocosms. The temporal dynamics of iodomethane (CH3I alluded to active turnover of this halocarbon in the mesocosms and strong significant correlations with biological parameters suggested a biological source. However, despite a pCO2 effect on various components of the plankton community, and a strong association between CH3I and biological parameters, no effect of pCO2 was seen in CH3I. Diiodomethane (CH2I2 displayed a number of strong relationships with biological parameters. Furthermore, the concentrations, the rate of net production and the sea-to-air flux of CH2I2 showed a significant positive response to pCO2. There was no clear effect of pCO2 on bromocarbon concentrations or dynamics. However, periods of significant net loss of bromoform (CHBr3 were found to be concentration-dependent, and closely correlated with total bacteria, suggesting a degree of biological consumption of this halocarbon in Arctic waters. Although the effects of OA on halocarbon concentrations were marginal, this study provides invaluable information on the production and cycling of halocarbons in a region of the world's oceans likely to experience rapid environmental change in the coming decades.

  12. Biogenic halocarbons from coastal oceanic upwelling regions as tropospheric halogen source

    Science.gov (United States)

    Krüger, Kirstin; Fuhlbrügge, Steffen; Hepach, Helmke; Fiehn, Alina; Atlas, Elliot; Quack, Birgit

    2016-04-01

    Halogenated very short lived substances (VSLS) are naturally produced in the ocean and emitted to the atmosphere. Recently, oceanic upwelling regions in the tropical East Atlantic were identified as strong sources of brominated halocarbons to the troposphere. During a cruise of R/V METEOR in December 2012 the oceanic sources and emissions of various halogenated trace gases and their mixing ratios in the marine atmospheric boundary layer (MABL) were investigated above the Peruvian Upwelling for the first time. This study presents novel observations of the three VSLS bromoform, dibromomethane and methyl iodide together with high resolution meteorological measurements and Lagrangian transport modelling. Although relatively low oceanic emissions were observed, except for methyl iodide, surface atmospheric abundances were elevated. Radiosonde launches during the cruise revealed a low, stable MABL and a distinct trade inversion above acting both as strong barriers for convection and trace gas transport in this region. Significant correlations between observed atmospheric VSLS abundances, sea surface temperature, relative humidity and MABL height were found. We used a simple source-loss estimate to identify the contribution of oceanic emissions to observed atmospheric concentrations which revealed that the observed marine VSLS abundances were dominated by horizontal advection below the trade inversion. The observed VSLS variations can be explained by the low emissions and their accumulation under different MABL and trade inversion conditions. Finally, observations from a second Peruvian Upwelling cruise with R/V SONNE during El Nino in October 2015 will be compared to highlight the role of different El Nino Southern Oscillation conditions. This study confirms the importance of coastal oceanic upwelling and trade wind systems on creating effective transport barriers in the lowermost atmosphere controlling the distribution of VSLS abundances above coastal ocean upwelling

  13. Free Radical Chemistry of Disinfection Byproducts 1: Kinetics of Hydrated Electron and Hydroxyl Radical Reactions with Halonitromethanes in Water

    Energy Technology Data Exchange (ETDEWEB)

    B. J. Mincher; R. V. Fox; S. P. Mezyk; T. Helgeson; S. K. Cole; W. J. Cooper; P. R. Gardinali

    2006-01-01

    Halonitromethanes are disinfection-byproducts formed during ozonation and chlorine/chloramine treatment of waters that contain bromide ion and natural organic matter. In this study, the chemical kinetics of the free-radical-induced degradations of a series of halonitromethanes were determined. Absolute rate constants for hydroxyl radical, OH, and hydrated electron, eaq-, reaction with both chlorinated and brominated halonitromethanes were measured using the techniques of electron pulse radiolysis and transient absorption spectroscopy. The bimolecular rate constants obtained, k (M-1 s-1), for eaq-/OH, respectively, were the following: chloronitromethane (3.01 ± 0.40) × 1010/(1.94 ± 0.32) × 108; dichloronitromethane (3.21 ± 0.17) × 1010/(5.12 ± 0.77) × 108; bromonitromethane (3.13 ± 0.06) × 1010/(8.36 ± 0.57) × 107; dibromonitromethane (3.07 ± 0.40) × 1010/(4.75 ± 0.98) × 108; tribromonitromethane (2.29 ± 0.39) × 1010/(3.25 ± 0.67) × 108; bromochloronitromethane (2.93 ± 0.47) × 1010/(4.2 ± 1.1) × 108; bromodichloronitromethane (2.68 ± 0.13) × 1010/(1.02 ± 0.15) × 108; and dibromochloronitromethane (2.95 ± 0.43) × 1010 / (1.80 ± 0.31) × 108 at room temperature and pH ~7. Comparison data were also obtained for hydroxyl radical reaction with bromoform (1.50 ± 0.05) × 108, bromodichloromethane (7.11 ± 0.26) × 107, and chlorodibromomethane (8.31 ± 0.25) × 107 M-1 s-1, respectively. These rate constants are compared to recently obtained data for trichloronitromethane and bromonitromethane, as well as to other established literature data for analogous compounds.

  14. Biogenic halocarbons from the Peruvian upwelling region as tropospheric halogen source

    Science.gov (United States)

    Hepach, Helmke; Quack, Birgit; Tegtmeier, Susann; Engel, Anja; Bracher, Astrid; Fuhlbrügge, Steffen; Galgani, Luisa; Atlas, Elliot L.; Lampel, Johannes; Frieß, Udo; Krüger, Kirstin

    2016-09-01

    Halocarbons are produced naturally in the oceans by biological and chemical processes. They are emitted from surface seawater into the atmosphere, where they take part in numerous chemical processes such as ozone destruction and the oxidation of mercury and dimethyl sulfide. Here we present oceanic and atmospheric halocarbon data for the Peruvian upwelling zone obtained during the M91 cruise onboard the research vessel METEOR in December 2012. Surface waters during the cruise were characterized by moderate concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) correlating with diatom biomass derived from marker pigment concentrations, which suggests this phytoplankton group is a likely source. Concentrations measured for the iodinated compounds methyl iodide (CH3I) of up to 35.4 pmol L-1, chloroiodomethane (CH2ClI) of up to 58.1 pmol L-1 and diiodomethane (CH2I2) of up to 32.4 pmol L-1 in water samples were much higher than previously reported for the tropical Atlantic upwelling systems. Iodocarbons also correlated with the diatom biomass and even more significantly with dissolved organic matter (DOM) components measured in the surface water. Our results suggest a biological source of these compounds as a significant driving factor for the observed large iodocarbon concentrations. Elevated atmospheric mixing ratios of CH3I (up to 3.2 ppt), CH2ClI (up to 2.5 ppt) and CH2I2 (3.3 ppt) above the upwelling were correlated with seawater concentrations and high sea-to-air fluxes. During the first part of the cruise, the enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels, while this contribution was considerably smaller during the second part.

  15. 4-烷基苯甲酸液晶中间体的合成及其液晶性能%The synthesis and properties of liquid crystal intermediates 4-alkyl benzoic acids

    Institute of Scientific and Technical Information of China (English)

    郑敏燕; 杨杰; 武永刚

    2012-01-01

    以苯、C2 ~ C5的酰氯为原料,经傅-克酰基化、黄鸣龙还原、乙酰化反应和溴仿反应合成了4个端基为C2~C5的单环芳香酸.以气相色谱-质谱联用仪、红外光谱仪、紫外光谱仪对芳香酸结构进行了表征.利用差热扫描量热仪、热台偏光显微镜对化合物的液晶性能进行了测试.结果表明,对于分子的长径比小于4的这类化合物,通过分子间氢键缔合的形式,亦可产生液晶相;其液晶相温度范围为9 ~20 ℃,呈现出向列相纹影织构.%4 Single ring aromatic acids with terminal alkyls from C2 to C5 were synthesized with benzene and acyl chloride from C2 to C5 as raw materials by reactions of F-C,Huang Minglong.acylation,reduction of acetyktion and bromoform. Their stnictures were characterized by gas chromatography-mass spectrome-try,infrared spectrophotometer and UV spectrophotometer.Their property of liquid crystal was also detected by using differential scanning calorimeter and thermal platform polarized microscope. The results showed molecules whose ratios of length to width were less than 4 can also form mesophases by hydrogen boding between double molecules. The temperature ranges of mesophase of the series of liquid crystals were between 9℃ and 20℃, showing a nematic schlieren textures.

  16. Finding the missing stratospheric Bry: a global modeling study of CHBr3 and CH2Br2

    Directory of Open Access Journals (Sweden)

    L. Ott

    2009-11-01

    Full Text Available Recent in situ and satellite measurements suggest a contribution of ~5 pptv to stratospheric inorganic bromine from short-lived bromocarbons. We conduct a modeling study of the two most important short-lived bromocarbons, bromoform (CHBr3 and dibromomethane (CH2Br2, with the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM to account for this missing stratospheric bromine. We derive a "top-down" emission estimate of CHBr3 and CH2Br2 using airborne measurements in the Pacific and North American troposphere and lower stratosphere (LS obtained during previous NASA aircraft campaigns. Our emission estimate suggests that to reproduce the observed concentrations in the free troposphere, a global oceanic emission of 425 Gg Br yr−1 for CHBr3 and 57 Gg Br yr−1 for CH2Br2 is needed, with 60% of emissions from open ocean and 40% from coastal regions. Although our simple emission scheme assumes no seasonal variations, the model reproduces the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss and transport. The inclusion of CHBr3 and CH2Br2 contributes ~5 pptv bromine throughout the stratosphere. Both the source gases and inorganic bromine produced from the source gas degradation (BryVSLS in the troposphere are transported into the stratosphere, and are equally important. Inorganic bromine accounts for half (2.5 pptv of the bromine from the inclusion of CHBr3 and CH2Br2 near the tropical tropopause and its contribution rapidly increases to ~100% as altitude increases. More than 85% of the wet scavenging of BryVSLS occurs in large-scale precipitation below 500 hPa and BryVSLS in the stratosphere is not sensitive to convection.

  17. Convective Transport of Very-short-lived Bromocarbons to the Stratosphere

    Science.gov (United States)

    Liang, Qing; Atlas, Elliot Leonard; Blake, Donald Ray; Dorf, Marcel; Pfeilsticker, Klaus August; Schauffler, Sue Myhre

    2014-01-01

    We use the NASA GEOS Chemistry Climate Model (GEOSCCM) to quantify the contribution of two most important brominated very short-lived substances (VSLS), bromoform (CHBr3) and dibromomethane (CH2Br2), to stratospheric bromine and its sensitivity to convection strength. Model simulations suggest that the most active transport of VSLS from the marine boundary layer through the tropopause occurs over the tropical Indian Ocean, the Western Pacific warm pool, and off the Pacific coast of Mexico. Together, convective lofting of CHBr3 and CH2Br2 and their degradation products supplies 8 ppt total bromine to the base of the Tropical Tropopause Layer (TTL, 150 hPa), similar to the amount of VSLS organic bromine available in the marine boundary layer (7.8-8.4 ppt) in the above active convective lofting regions. Of the total 8 ppt VSLS-originated bromine that enters the base of TTL at 150 hPa, half is in the form of source gas injection (SGI) and half as product gas injection (PGI). Only a small portion (< 10%) the VSLS-originated bromine is removed via wet scavenging in the TTL before reaching the lower stratosphere. On global and annual average, CHBr3 and CH2Br2, together, contribute 7.7 pptv to the present-day inorganic bromine in the stratosphere. However, varying model deep convection strength between maximum and minimum convection conditions can introduce a 2.6 pptv uncertainty in the contribution of VSLS to inorganic bromine in the stratosphere (BryVSLS). Contrary to the conventional wisdom, minimum convection condition leads to a larger BryVSLS as the reduced scavenging in soluble product gases, thus a significant increase in PGI (2-3 ppt), greatly exceeds the relative minor decrease in SGI (a few 10ths ppt.

  18. Photolytic removal of DBPs by medium pressure UV in swimming pool water

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, Kamilla M.S. [Department of Environmental Engineering, Technical University of Denmark (Denmark); Zortea, Raissa [Department of Land, Environment and Geotechnology Engineering, Polytechnic University of Turin (Italy); Piketty, Aurelia [Institute of Chemistry, Industrial and Chemical Engineering and Technology (INP-ENCIACET), National Polytechnic Institute of Toulouse (France); Vega, Sergio Rodriguez [Chemical Engineering, Complutense University of Madrid (Spain); Andersen, Henrik Rasmus, E-mail: Henrik@ndersen.net [Department of Environmental Engineering, Technical University of Denmark (Denmark)

    2013-01-15

    Medium pressure UV is used for controlling the concentration of combined chlorine (chloramines) in many public swimming pools. Little is known about the fate of other disinfection by-products (DBPs) in UV treatment. Photolysis by medium pressure UV treatment was investigated for 12 DBPs reported to be found in swimming pool water: chloroform, bromodichloromethane, dibromochloromethane, bromoform, dichloroacetonitrile, bromochloroacetonitrile, dibromoacetronitrile, trichloroacetonitrile, trichloronitromethane, dichloropropanone, trichloropropanone, and chloral hydrate. First order photolysis constants ranged 26-fold from 0.020 min{sup −1} for chloroform to 0.523 min{sup −1} for trichloronitromethane. The rate constants generally increased with bromine substitution. Using the UV removal of combined chlorine as an actinometer, the rate constants were recalculated to actual treatment doses of UV applied in a swimming pool. In an investigated public pool the UV dose was equivalent to an applied electrical energy of 1.34 kWh m{sup −3} d{sup −1} and the UV dose required to removed 90% of trichloronitromethane was 0.4 kWh m{sup −3} d{sup −1}, while 2.6 kWh m{sup −3} d{sup −1} was required for chloral hydrate and the bromine containing haloacetonitriles and trihalomethanes ranged from 0.6 to 3.1 kWh m{sup −3} d{sup −1}. It was predicted thus that a beneficial side-effect of applying UV for removing combined chlorine from the pool water could be a significant removal of trichloronitromethane, chloral hydrate and the bromine containing haloacetonitriles and trihalomethanes. - Highlights: ► UV irradiation is able to degrade all 12 investigated disinfection by-products. ► Bromine species are easier to remove than their chlorinated analogues. ► UV dose used for combined chlorine was comparable with doses required for DBP removal. ► Significant removal of some disinfection by-products in swimming pools is indicated.

  19. Finding the Missing Stratospheric Br(sub y): A Global Modeling Study of CHBr3 and CH2Br2

    Science.gov (United States)

    Liang, Q.; Stolarski, R. S.; Kawa, S. R.; Nielsen, J. E.; Douglass, A. R.; Rodriguez, J. M.; Blake, D. R.; Atlas, E. L.; Ott, L. E.

    2010-01-01

    Recent in situ and satellite measurements suggest a contribution of 5 pptv to stratospheric inorganic bromine from short-lived bromocarbons. We conduct a modeling study of the two most important short-lived bromocarbons, bromoform (CHBr3) and dibromomethane (CH2Br2), with the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM) to account for this missing stratospheric bromine. We derive a "top-down" emission estimate of CHBr3 and CH2Br2 using airborne measurements in the Pacific and North American troposphere and lower stratosphere obtained during previous NASA aircraft campaigns. Our emission estimate suggests that to reproduce the observed concentrations in the free troposphere, a global oceanic emission of 425 Gg Br yr(exp -1) for CHBr3 and 57 Gg Br yr(exp -l) for CH2Br2 is needed, with 60% of emissions from open ocean and 40% from coastal regions. Although our simple emission scheme assumes no seasonal variations, the model reproduces the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss and transport. The inclusion of CHBr3 and CH2Br2 contributes 5 pptv bromine throughout the stratosphere. Both the source gases and inorganic bromine produced from source gas degradation (BrSLS) in the troposphere are transported into the stratosphere, and are equally important. Inorganic bromine accounts for half (2.5 pptv) of the bromine from the inclusion of CHBr3 and CHzBr2 near the tropical tropopause and its contribution rapidly increases to 100% as altitude increases. More than 85% of the wet scavenging of Br(sub y)(sup VSLS) occurs in large-scale precipitation below 500 hPa. Our sensitivity study with wet scavenging in convective updrafts switched off suggests that Br(sub y)(sup SLS) in the stratosphere is not sensitive to convection. Convective scavenging only

  20. Atmospheric volatile organic compound measurements: Distributions and effects on air quality in coastal marine, rural and remote continental environments

    Science.gov (United States)

    Zhou, Yong

    A detailed description of the analytical methods employed for whole air sampling and analysis of atmospheric volatile organic compounds is presented. The system described in this thesis produced high precision measurements for a large suite of nonmethane hydrocarbons, halocarbons, and alkyl nitrates, from part per billion by volume (ppbv) to part per trillion by volume (pptv) levels. The measurement precision for most gases ranged from 1-10%. Results from two subsequent field campaigns (2002 and 2003) conducted in Yellowstone National Park (YNP) are presented. The findings indicate that 2-stroke snowmobile engine emissions furnish large quantities of air toxics to the YNP air shed. Air toxics, which are major components of 2stroke engine exhaust, show large enhancements between the high traffic and low traffic sampling periods. Evaluation of the photochemical history of air masses sampled in the Park reveals that the air toxic emissions were recent and persistent throughout the region and consistent with the 2-stroke exhaust sample fingerprints. Using a box model, the emission fluxes from snowmobile usage in the Park are estimated to be 0.35, 1.12, 0.24, 1.45, and 0.36 Gg/yr for benzene, toluene, ethyl benzene, xylenes, and hexane, respectively. The U.S. annual emissions from snowmobile usage are significant (˜14-21%) with respect to EPA estimates. Results of the atmospheric measurements of short-lived halocarbons are presented from the New England Air Quality Study 2002 campaign, summer 2003 at Thompson Farm (TF) and Great Bay, and the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) 2004 campaign. Elevated levels of bromoform (CHBr3) were frequently observed, with maxima of 37.9 pptv and 47.4 pptv for TF and Appledore Island (AI), respectively. During the ICARTT 2004 campaign, the average levels of CHBr3 and dibromomethane (CH2Br2) were higher at AI (CHBr3 = 14.3 pptv, CH2Br2 = 3.2 pptv) compared to Thompson Farm (CHBr3

  1. Evaluating Global Emission Inventories of Biogenic Bromocarbons

    Science.gov (United States)

    Hossaini, Ryan; Mantle, H.; Chipperfield, M. P.; Montzka, S. A.; Hamer, P.; Ziska, F.; Quack, B.; Kruger, K.; Tegtmeier, S.; Atlas, E.; Sala, S.; Engel, A.; Bonisch, H.; Keber, T.; Oram, D.; Mills, G.; Ordonez, C.; Saiz-Lopez, A.; Warwick, N.; Liang, Q.; Feng, W.; Moore, F.; Miller, F.; Marecal, V.; Richards, N. A. D.; Dorf, M.; Pfeilsticker, K.

    2013-01-01

    Emissions of halogenated very short-lived substances (VSLS) are poorly constrained. However, their inclusion in global models is required to simulate a realistic inorganic bromine (Bry) loading in both the troposphere, where bromine chemistry perturbs global oxidizing capacity, and in the stratosphere, where it is a major sink for ozone (O3). We have performed simulations using a 3-D chemical transport model (CTM) including three top-down and a single bottom-up derived emission inventory of the major brominated VSLS bromoform (CHBr3) and dibromomethane (CH2Br2). We perform the first concerted evaluation of these inventories, comparing both the magnitude and spatial distribution of emissions. For a quantitative evaluation of each inventory, model output is compared with independent long-term observations at National Oceanic and Atmospheric Administration (NOAA) ground-based stations and with aircraft observations made during the NSF (National Science Foundation) HIAPER Pole-to-Pole Observations (HIPPO) project. For CHBr3, the mean absolute deviation between model and surface observation ranges from 0.22 (38 %) to 0.78 (115 %) parts per trillion (ppt) in the tropics, depending on emission inventory. For CH2Br2, the range is 0.17 (24 %) to 1.25 (167 %) ppt. We also use aircraft observations made during the 2011 Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere (SHIVA) campaign, in the tropical western Pacific. Here, the performance of the various inventories also varies significantly, but overall the CTM is able to reproduce observed CHBr3 well in the free troposphere using an inventory based on observed sea-to-air fluxes. Finally, we identify the range of uncertainty associated with these VSLS emission inventories on stratospheric bromine loading due to VSLS (Br(VSLS/y)). Our simulations show Br(VSLS/y) ranges from approximately 4.0 to 8.0 ppt depending on the inventory. We report an optimized estimate at the lower end of this range (approximately 4 ppt

  2. Determination of volatile halohydrocarbons in drinking water by capillary column gas chromatography%毛细管柱气相色谱法测定生活饮用水中挥发性卤代烃

    Institute of Scientific and Technical Information of China (English)

    董玉英; 张瑞雨; 欧利华

    2013-01-01

    Objective: To establish a method for determination of seven volatile halohydrocarbons in drinking water. Methods: The seven volatile halohydrocarbons (chlorofrom, tetrachloromethane, trichloroethylene, bromodi-chloromethane, tetrachloroethylene, dibromochloromethane, bromoform) in drinking water were determined by head-space Gas Chromatography with DB - 624 capillary column. Results: Under the optimal experimental conditions, the recoveries of the seven volatile halohydrocarbons were in the range of 92.5% -102%, the relative standard deviation was between 1.20% ~4.61%, and the determination limit was between 0.01 μg/L ~ 1.00 μg/L. Conclusion: The developed methjod is sensitive, simple, rapid and accurate, and seven volatile halohydrocarbons in drinking water can be determined simultaneously.%目的:建立一种快速、准确测定生活饮用水中7种挥发性卤代烃的方法.方法:采用DB-624毛细管柱、顶空气相色谱法测定生活饮用水中三氯甲烷、四氯化碳、三氯乙烯、二氯一溴甲烷、四氯乙烯、一氯二溴甲烷及三溴甲烷.结果:在所选择的实验条件下,7种挥发性卤代烃的平均回收率在92.5%~102%之间,相对标准偏差(RSD)为1.20% ~4.61%,检出限为0.01 μg/L ~1.00 μg/L.结论:所建立的分析方法灵敏、简便、快速、准确,可同时测定生活饮用水中的7种挥发性卤代烃.

  3. 吹扫捕集- GC/MS法测定水中卤代烃的质量控制指标研究%Research of Quality Control Index for Halogenated Hydrocarbons in Water Determined by Purge and Trap-GC/MS

    Institute of Scientific and Technical Information of China (English)

    胡冠九; 李娟; 袁力; 夏新; 王荟; 史啸勇

    2011-01-01

    采用吹扫捕集-气相色谱/质谱联用法,通过实际样品测试及全国多家实验室测定数据统计两种方法,针对水中三氯甲烷、四氯化碳、溴仿、二氯甲烷、1,2-二氯乙烷、1,1-二氯乙烯、三氯乙烯、四氯乙烯等8种卤代烃的平行样测定相对偏差、空白加标回收率及实际样品加标回收率等3个指标,研究了每种卤代烃的质控指标评价标准,提出其平行样测定允许最大相对偏差应控制为11.6% ~20.8%;当空白加标质量浓度为0μg/L~100μg/L时,回收率的控制范围为60%~123%;当样品质量浓度为0μg/L~20μg/L时,实际样品加标回收率的控制范围为46%~164%.%Three quality control indexes of eight kinds of halogenated hydrocarbons (Chloroform, Carbon tet-rachloride, Bromoform, Methylene chloride, 1, 2-Dichloroethane, 1, 1 -Dichloroethylene, Trichloroethylene, Tetrachloroethylene ) , including relative bias of duplicates, recovery of blank spike and sample spike, were studied by sample test using purge and trap-gas chromatography-mass spectroscopy, and also by evaluating data collected from many labs national-widely. The quality control index was produced according to every target. The results showed that the maximum relative bias should be within 11.6% ~20. 8% ; the blank recovery should be within 60% -123% when the spiking concentration was 0 μg/L ~ 100 μg/L; the sample recovery should be within 46% ~ 164% when the sample concentration was 0 μg/L ~20 μg/L.

  4. Determination of volatile organic compounds in water by headspace solid-phase microextraction gas chromatography coupled to tandem mass spectrometry with triple quadrupole analyzer

    Energy Technology Data Exchange (ETDEWEB)

    Cervera, M.I. [Research Institute for Pesticides and Water, University Jaume I, Avda. Sos Baynat, E-12071 Castellon (Spain); Beltran, J., E-mail: joaquim.beltran@uji.es [Research Institute for Pesticides and Water, University Jaume I, Avda. Sos Baynat, E-12071 Castellon (Spain); Lopez, F.J.; Hernandez, F. [Research Institute for Pesticides and Water, University Jaume I, Avda. Sos Baynat, E-12071 Castellon (Spain)

    2011-10-17

    relative standard deviations (RSDs) lower than 20%. The developed method was applied to surface water and wastewater from a wastewater treatment plant and from a municipal solid-waste treatment plant. Several compounds, like chloroform, benzene, trichloroethylene, toluene, tetrachloroethylene, dibromochloromethane, xylenes and bromoform were detected and confirmed in all the samples analyzed.

  5. Variations in trihalomethane levels in three French water distribution systems and the development of a predictive model.

    Science.gov (United States)

    Mouly, Damien; Joulin, Eric; Rosin, Christophe; Beaudeau, Pascal; Zeghnoun, Abdelkrim; Olszewski-Ortar, Agnès; Munoz, Jean François; Welté, Bénédicte; Joyeux, Michel; Seux, René; Montiel, Antoine; Rodriguez, M J

    2010-10-01

    Epidemiological studies have demonstrated that chlorination by-products in drinking water may cause some types of cancer in humans. However, due to differences in methodology between the various studies, it is not possible to establish a dose-response relationship. This shortcoming is due primarily to uncertainties about how exposure is measured-made difficult by the great number of compounds present-the exposure routes involved and the variation in concentrations in water distribution systems. This is especially true for trihalomethanes for which concentrations can double between the water treatment plant and the consumer tap. The aim of this study is to describe the behaviour of trihalomethanes in three French water distribution systems and develop a mathematical model to predict concentrations in the water distribution system using data collected from treated water at the plant (i.e. the entrance of the distribution system). In 2006 and 2007, samples were taken successively from treated water at the plant and at several points in the water distribution system in three French cities. In addition to the concentrations of the four trihalomethanes (chloroform, dichlorobromomethane, chlorodibromomethane, bromoform), many other parameters involved in their formation that affect their concentration were also measured. The average trihalomethane concentration in the three water distribution systems ranged from 21.6 μg/L to 59.9 μg/L. The increase in trihalomethanes between the treated water at the plant and a given point in the water distribution system varied by a factor of 1.1-5.7 over all of the samples. A log-log linear regression model was constructed to predict THM concentrations in the water distribution system. The five variables used were trihalomethane concentration and free residual chlorine for treated water at the plant, two variables that characterize the reactivity of organic matter (specific UV absorbance (SUVA), an indicator developed for the free

  6. Subproductos halogenados de la cloración en el agua de consumo público Halogenated by-products of chlorination in tap water

    Directory of Open Access Journals (Sweden)

    J. Calderón

    2002-06-01

    Full Text Available Objetivo: La presencia de trihalometanos en el agua de diversas ciudades españolas está demostrada. Este estudio pretende analizar sus concentraciones en el agua de la ciudad de Barcelona. Métodos: Se analizan 151 muestras de agua recogidas durante el año 1998. Los análisis se realizaron en el laboratorio municipal mediante purge and trap y posterior determinación por cromatografía de gases acoplada a espectrofotometría de masas. Los resultados se presentan según el origen del agua: ríos Llobregat, Ter o mezcla. Resultados: En aguas del Ter los valores son relativamente bajos y predominan cloroformo y bromodiclorometano, mientras que en las del Llobregat son más elevados y predominan bromoformo y dibromoclorometano. Las aguas de mezcla presentan valores intermedios. Los valores totales alcanzados en las muestras procedentes del Llobregat superan los 100 µg/l. Conclusiones: Estos resultados muestran la necesidad de seguir corrigiendo la contaminación orgánica y los compuestos halogenados en el agua captada para el consumo humano en Barcelona.Objective: The presence of trihalomethanes in the water systems of several Spanish cities has been demonstrated. The aim of this study was to analyze trihalomethane concentrations in the water provided for human consumption in the city of Barcelona. Methods: We analyzed 151 water samples collected in 1998. The analyses were performed in the Public Health Laboratory of Barcelona using the purge-and-trap method and subsequent determination by gas chromatography and mass spectrometry. The results are presented according to the source of the water: the rivers of Llobregat or Ter, or a mixture of these. Results: Thrihalomethane concentrations in the water from Ter were relatively low, with a predominance of chloroform and bromodichloromethane, while concentrations in the water from Llobregat were much higher, with a predominance of bromoform and dibromochloromethane. Mixed water showed intermediate

  7. Exchange of VSLS in the marine boundary layer with the free troposphere during SHIVA-SONNE

    Science.gov (United States)

    Fuhlbrügge, Steffen; Quack, Birgit; Tegtmeier, Susann; Atlas, Elliot; Sala, Stephan; Boenisch, Harald; Hepach, Helmke; Raimund, Stefan; Shi, Qiang; Krüger, Kirstin

    2013-04-01

    Significant contributions from short lived brominated and iodinated compounds to the stratospheric ozone budget are suspected especially from the tropical oceans particularly from coastal regions, where strong VSLS emissions are observed, caused by local biology (phytoplankton and macro algae). Due to the fast uplift of surface air by deep convection in the tropics, the ocean derived substances are expected to be transported to the stratosphere. Results from the SHIVA-SONNE ship campaign in the tropical West Pacific during 15 to 29 November 2011 revealed that the South China and Sulu seas comprise strong source regions of halocarbons for the atmosphere. Especially the bromoform fluxes were very high along the whole cruise and were in agreement with coastal fluxes from previous campaigns. Measurements of low air and high water concentrations of CH3I, CH2Br2, and CHBr3 support the derived air sea fluxes together with the high surface water temperatures and elevated wind speeds. The three airborne VSLS showed correlations and anti-correlations with some meteorological parameters (i.e. wind speed), while the mixing ratios of all compounds generally increased from the South China Sea towards the Sulu Sea region. A comparison of collocated VSLS measurements in the marine atmospheric boundary layer (MABL) between the research vessel SONNE and the aircraft FALCON revealed a good agreement. With a simple box-model we calculated the importance of the compounds sea-air flux related to their MABL-concentrations and lifetimes assuming a mean loss of 20% per day due to transport out of boundary layer into the free troposphere during the campaign. While the CH3I-flux approximately equaled its chemical loss, the fluxes of the brominated compounds were roughly ten times larger than needed to maintain the MABL mixing ratio, suggesting this region to be a very important oceanic source region for the atmosphere. Finally, we will compare the box-model loss from the MABL to the free

  8. Halocarbon emissions and sources in the equatorial Atlantic Cold Tongue

    Directory of Open Access Journals (Sweden)

    H. Hepach

    2015-04-01

    Full Text Available Halocarbons from oceanic sources contribute to halogens in the troposphere, and can be transported into the stratosphere where they take part in ozone depletion. This paper presents distribution and sources in the equatorial Atlantic from June and July 2011 of the four compounds bromoform (CHBr3, dibromomethane (CH2Br2, methyl iodide (CH3I and diiodomethane (CH2I2. Enhanced biological production during the Atlantic Cold Tongue (ACT season, indicated by phytoplankton pigment concentrations, led to elevated concentrations of CHBr3 of up to 44.7 pmol L−1 and up to 9.2 pmol L−1 for CH2Br2 in surface water, which is comparable to other tropical upwelling systems. While both compounds correlated very well with each other in the surface water,CH2Br2 was often more elevated in greater depth than CHBr3, which showed maxima in the vicinity of the deep chlorophyll maximum. The deeper maximum of CH2Br2 indicates an additional source in comparison to CHBr3 or a slower degradation of CH2Br2. Concentrations of CH3I of up to 12.8 pmol L−1 in the surface water were measured. In contrary to expectations of a predominantly photochemical source in the tropical ocean, its distribution was mostly in agreement with biological parameters, indicating a~biological source. CH2I2 was very low in the near surface water with maximum concentrations of only 3.7 pmol L−1, and the observed anticorrelation with global radiation was likely due to its strong photolysis. CH2I2 showed distinct maxima in deeper waters similar to CH2Br2. For the first time, diapycnal fluxes of the four halocarbons from the upper thermocline into and out of the mixed layer were determined. These fluxes were low in comparison to the halocarbon sea-to-air fluxes. This indicates that despite the observed maximum concentrations at depth, production in the surface mixed layer is the main oceanic source for all four compounds and has an influence on emissions into the atmosphere. The calculated

  9. Response of halocarbons to ocean acidification in the Arctic

    Directory of Open Access Journals (Sweden)

    F. E. Hopkins

    2012-07-01

    Full Text Available The potential effect of ocean acidification (OA on seawater halocarbons in the Arctic was investigated during a~mesocosm experiment in Spitsbergen in June–July 2010. Over a period of 5 weeks, natural phytoplankton communities in nine ~50 m3 mesocosms were studied under a range of pCO2 treatments from ~185 μatm to ~1420 μatm. In general, the response of halocarbons to pCO2 was subtle, or undetectable. A large number of significant correlations with a range of biological parameters (chlorophyll a, microbial plankton community, phytoplankton pigments were identified, indicating a biological control on the concentrations of halocarbons within the mesocosms. The temporal dynamics of iodomethane (CH3I alluded to active turnover of this halocarbon in the mesocosms and strong significant correlations with biological parameters suggested a biological source. However, despite a pCO2 effect on various components of the plankton community, and a strong association between CH3I and biological parameters, no effect of pCO2 was seen in CH3I. Diiodomethane (CH2I2 displayed a number of strong relationships with biological parameters. Furthermore, the concentrations, the rate of net production and the sea-to-air flux of CH2I2 showed a significant positive response to pCO2. There was no clear effect of pCO2 on bromocarbon concentrations or dynamics. However, periods of significant net loss of bromoform (CHBr3 were found to be concentration-dependent, and closely correlated with total bacteria, suggesting a degree of biological consumption of this halocarbon in Arctic waters. Although the effects of OA on halocarbon concentrations were marginal, this study provides invaluable information on the production and cycling of halocarbons in a region of the world

  10. [Risk Assessment of Trihalomethane Production Using the Beijiang River and the Pearl River, Guangzhou as Drinking Water Sources].

    Science.gov (United States)

    Zhong, Hui-zhou; Wei, Chao-hai

    2015-04-01

    In order to investigate the risk of trihalomethane formation potential (THMFP) in finished waters as drinking water sources, 70 samples, 114 samples, and 70 samples were collected in November 2013, April 2014 and July 2014, respectively from different locations in the Beijiang River and the Pearl River. After filtration by 0.45 μm filter membrane, a total of 254 samples were chlorinated using Uniform Formation Condition (UFC) method for determining their THM Formation Potential (THMFP). The cancer risk and non-cancer risk of THMs were estimated using USEPA risk assessment model while dominant factors for total risk potential were estimated using sensitivity analysis. Among four THM species, chloroform( CF) was the highest ranging from 101.92-2 590.85 μg x L(-1), followed by bromodichloromethane (BDCM), dibromochloromethane (DBCM) and bromoform (BF). Chloroform, the major THMs speciation, accounted for 96.17% of total THMs. Non-cancer and cancer risk from ingesting THMs was estimated. The result indicated that non-cancer risk of THMs level ranged from 2.03 x 10(-7) to 1.00 x 10(-5) and was not more than 1.0 x 10(-5), the minimum or negligible non-cancer risk level defined by the USEPA. The average cancer risk of THMs was 2.91 x 10(-4) for male and 3.30 x 10(-4) for female in the two rivers, respectively, exceeding the minimum or negligible risk level defined by the USEPA (1. 0 x 10 ~6). The difference of cancer risk between the two rivers was that BDCM ranging from 2.50 x 10(-5) to 6.37 x 10(-4) was approximately twice that of CF in Beijing River. BDCM played an important role in the total risk in the Beijiang River while CF played an important role in the total risk in the Pearl River, Guangzhou. Sensitivity analysis showed that CF played an important role in the estimation of total risk potential, and that the direct utilization of water sources from Beijiang River and the Pearl River Guangzhou is dangerous, thus pretreatment is necessary before chlorination.

  11. Investigation of Amount and Effective Factors on Trihalomethane Production in PotableWater of Yazd

    Directory of Open Access Journals (Sweden)

    Andalib A.H.

    2011-06-01

    Full Text Available Background and Objectives:Yazd province is located in the central desert part of Iran in which water scarcity was one of the most important problems. This has been recently solved to some extent, due to the approved channel project of water transferring from Isfahan to Yazd. Chlorination is usually used in the last stage of water treatment for disinfection in the networks, treatment plants, storages and channel stations. The possibility of carcinogen lateral composites formation is expected by tri-halo-methanes (THMs due to the reactions occurs between the natural organic materials and free chlorine available in water. Based on the established standard by the country, the permissible limit of THMs in water is 200 mg/L. In this research, in addition to the amount of THMs and their distribution in Yazd water transferring channel and the city water network system, the important parameters and their correlations with THMs formation were discussed.Materials and Methods: In a year of sampling period, the concentrations of THMs including the four major components of chloroform, bromoform, bromo di-chloro methane and di-bromo chloro methane during all seasons were measured using gas chromatograph and analyzed. This was done for 11 stations including Zayande-rood Basin River and Isfahan water treatment plant up to Yazd Shehneh storage, stations and inline equalization tanks and also five regions of Yazd city network.Results: According to the results, the maximum rate of THMs (51.14 mg/L during the sampling period in summer for Yazd city network and in ancient context of Jamea Mosque district was found. In addition, the minimum concentration of THMs was 1.60 mg/L in winter for the domestic network of the city which was related to Azad Shahr district. The Average total amount of THMs during sampling periods in all stations was 12.26 mg/L. Conclusion: SPSS and Excel softwares were used to analyze the research data in the descriptive and inferential manner

  12. Formation of emerging DBPs from the chlorination and chloramination of seawater algal organic matter and related model compounds

    KAUST Repository

    Nihemaiti, Maolida

    2014-05-01

    Limited studies focused on reactions occurring during disinfection and oxidation processes of seawater. The aim of this work was to investigate disinfection by-products (DBPs) formation from the chlorination and chloramination of seawater algal organic matter and related model compounds. Simulated algal blooms directly growing in Red Sea, red tide samples collected during an algal bloom event and Hymenomonas sp. monoculture were studied as algal organic matter sources. Experiments were conducted in synthetic seawater containing bromide ion. A variety of DBPs was formed from the chlorination and chloramination of algal organic matter. Brominated DBPs (bromoform, DBAA, DBAN and DBAcAm) were the dominant species. Iodinated DBPs (CIAcAm and iodinated THMs) were detected, which are known to be highly toxic compared to their chlorinated or brominated analogues. Algal organic matter was found to incorporate important precursors of nitrogenous DBPs (N-DBPs), which have been reported to be more toxic than regulated THMs and HAAs. Isotopically-labeled monochloramine (15N- NH2Cl) was used in order to investigate the nitrogen source in N-DBPs. High formation of N-DBPs was found from Hymenomonas sp. sample in exponential growth phase, which was enriched in nitrogen-containing organic compounds. High inorganic nitrogen incorporation was found from the algal samples enriched in humic-like compounds. HAcAms formation was studied from chlorination and chloramination of amino acids. Asparagine, aspartic acid and other amino acids with an aromatic structure were found to be important precursors of HAcAms and DCAN. Factors affecting HAcAms formation (Cl2/ amino acid molar ratio and pH) were evaluated. Studies on the formation kinetics of DCAcAm and DCAN from asparagine suggested a rapid formation of DCAcAm from organic nitrogen (amide group) and a slower incorporation of inorganic nitrogen coming from monochloramine to form DCAN. High amounts of DCAN and DCAcAm were detected from the

  13. Finding the missing stratospheric Bry: a global modeling study of CHBr3 and CH2Br2

    Directory of Open Access Journals (Sweden)

    D. R. Blake

    2010-03-01

    Full Text Available Recent in situ and satellite measurements suggest a contribution of ~5 pptv to stratospheric inorganic bromine from short-lived bromocarbons. We conduct a modeling study of the two most important short-lived bromocarbons, bromoform (CHBr3 and dibromomethane (CH2Br2, with the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM to account for this missing stratospheric bromine. We derive a "top-down" emission estimate of CHBr3 and CH2Br2 using airborne measurements in the Pacific and North American troposphere and lower stratosphere obtained during previous NASA aircraft campaigns. Our emission estimate suggests that to reproduce the observed concentrations in the free troposphere, a global oceanic emission of 425 Gg Br yr−1 for CHBr3 and 57 Gg Br yr−1 for CH2Br2 is needed, with 60% of emissions from open ocean and 40% from coastal regions. Although our simple emission scheme assumes no seasonal variations, the model reproduces the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss and transport. The inclusion of CHBr3 and CH2Br2 contributes ~5 pptv bromine throughout the stratosphere. Both the source gases and inorganic bromine produced from source gas degradation (BryVSLS in the troposphere are transported into the stratosphere, and are equally important. Inorganic bromine accounts for half (2.5 pptv of the bromine from the inclusion of CHBr3 and CH2Br2 near the tropical tropopause and its contribution rapidly increases to ~100% as altitude increases. More than 85% of the wet scavenging of BryVSLS occurs in large-scale precipitation below 500 hPa. Our sensitivity study with wet scavenging in convective updrafts switched off suggests that BryVSLS in the stratosphere is not sensitive to convection. Convective scavenging only accounts for

  14. Cancer risk assessment from exposure to trihalomethanes in tap water and swimming pool water

    Institute of Scientific and Technical Information of China (English)

    PANYAKAPO Mallika; SOONTORNCHAI Sarisak; PAOPUREE Pongsri

    2008-01-01

    We investigated the concentration of trihalomethanes (THMs) in tap water and swimming pool water in the area of the Nakhon Path-om Municipality during the period April 2005-March 2006.The concentrations of total THMs,chloroform,bromodichloromethane,dibromochloromethane and bromoform in tap water were 12.70-41.74,6.72-29.19,1.12-11.75,0.63-3.55 and 0.08-3.40 μg/L,respectively,whereas those in swimming pool water were 26.15-65.09,9.50-36.97,8.90-18.01,5.19-22.78 and ND-6.56 μg/L,respectively.It implied that the concentration of THMs in swimming pool water was higher than those in tap water,particularly,brominated-THMs.Both tap water and swimming pool water contained concentrations of total THMs below the standards of the World Health Organization (WHO),European Union (EU) and the United States Environmental Protection Agency (USEPA) phase Ⅰ,but 1 out of 60 tap water samples and 60 out of 72 swimming pool water samples contained those over the Standard of the USEPA phase Ⅱ.From the two cases of cancer risk assessment including Case Ⅰ Non-Swimmer and Case Ⅱ Swimmer,assessment of cancer risk of non-swimmers from exposure to THMs at the highest and the average concentrations was 4.43×10-5 and 2.19×10-5,respectively,which can be classified as acceptable risk according to the Standard of USEPA.Assessment of cancer risk of swimmers from exposure to THMs at the highest and the average concentrations was 1.47×10-3 and 7.99×10-4,respectively,which can be classified as unacceptable risk and needs to be improved.Risk of THMs exposure from swimming was 93.9%-94.2% of the total risk.Cancer risk of THMs concluded from various routes in descending order was:skin exposure while swimming,gastro-intestinal exposure from tap water intake,and skin exposure to tap water and gastro-intestinal exposure while swimming.Cancer risk from skin exposure while swimming was 94.18% of the total cancer risk.

  15. Levels and pattern of alkyl nitrates, multifunctional alkyl nitrates, and halocarbons in the air over the Atlantic Ocean

    Science.gov (United States)

    Fischer, Ralf G.; Kastler, Jürgen; Ballschmiter, Karlheinz

    2000-06-01

    The Albatross Campaign was a research cruise of the German research vessel RV Polarstern (cruise ANT XFV/1) in October and November 1996 across the Atlantic Ocean. The cruise started in Bremerhaven, Germany, reached the polar region at 67°N, followed the 30°W meridian longitude, crossed the equatorial region, and ended at 50°S at Punta Quilla, Argentina. A second cruise leg closer to the African continent started from Capetown, South Africa, passed the Canary Island, and ended through the English Channel at Bremerhaven, Germany, in May/June 1998. Measurements of atmospheric levels of C1-C13 alkyl mononitrates, 24 alkyl dinitrates (C3-C6), 19 hydroxy alkyl nitrates (C2-C6), and benzyl nitrate, as well as the halocarbons tetrachloroethene, hexachloroethane, and bromoform are presented in this work. The halocarbons are used to assess the origin of the air parcels analyzed. Levels and patterns of multifunctional alkyl nitrates in the marine air are described here for the first time. The air masses include polluted air from the northern Europe, as well as highly degraded air masses of the South Atlantic trade wind region that represent global baseline levels. Two independent analytical methods were used in combination to cover the whole range of organic nitrates. First, the low-volume adsorptive enrichment of organic traces on Tenax, followed by thermodesorption cold trap HRGC-ECD and thermodesorption cold trap HRGC-(EI)MSD was used. Second, high-volume adsorptive enrichment of organic traces on silica gel was applied followed by solvent desorption, NP-HPLC group separation, and HRGC-(EI)-MSD. Short-chain alkyl nitrates (C4-C6) showed mixing ratios in the range of 0.2-2.5 parts per trillion by volume (pptv), with a local minimum for the tropical regions and significantly lower ratios for the Southern Hemisphere. The mixing ratio of the sum of 36 long-chain alkyl mononitrates (C7-C13) ranged from 0.02-0.43 pptv, the mixing ratio of the sum of 23 alkyl dinitrates (C3-C

  16. A multi-model intercomparison of halogenated very short-lived substances (TransCom-VSLS): linking oceanic emissions and tropospheric transport for a reconciled estimate of the stratospheric source gas injection of bromine

    Science.gov (United States)

    Hossaini, R.; Patra, P. K.; Leeson, A. A.; Krysztofiak, G.; Abraham, N. L.; Andrews, S. J.; Archibald, A. T.; Aschmann, J.; Atlas, E. L.; Belikov, D. A.; Bönisch, H.; Carpenter, L. J.; Dhomse, S.; Dorf, M.; Engel, A.; Feng, W.; Fuhlbrügge, S.; Griffiths, P. T.; Harris, N. R. P.; Hommel, R.; Keber, T.; Krüger, K.; Lennartz, S. T.; Maksyutov, S.; Mantle, H.; Mills, G. P.; Miller, B.; Montzka, S. A.; Moore, F.; Navarro, M. A.; Oram, D. E.; Pfeilsticker, K.; Pyle, J. A.; Quack, B.; Robinson, A. D.; Saikawa, E.; Saiz-Lopez, A.; Sala, S.; Sinnhuber, B.-M.; Taguchi, S.; Tegtmeier, S.; Lidster, R. T.; Wilson, C.; Ziska, F.

    2016-07-01

    The first concerted multi-model intercomparison of halogenated very short-lived substances (VSLS) has been performed, within the framework of the ongoing Atmospheric Tracer Transport Model Intercomparison Project (TransCom). Eleven global models or model variants participated (nine chemical transport models and two chemistry-climate models) by simulating the major natural bromine VSLS, bromoform (CHBr3) and dibromomethane (CH2Br2), over a 20-year period (1993-2012). Except for three model simulations, all others were driven offline by (or nudged to) reanalysed meteorology. The overarching goal of TransCom-VSLS was to provide a reconciled model estimate of the stratospheric source gas injection (SGI) of bromine from these gases, to constrain the current measurement-derived range, and to investigate inter-model differences due to emissions and transport processes. Models ran with standardised idealised chemistry, to isolate differences due to transport, and we investigated the sensitivity of results to a range of VSLS emission inventories. Models were tested in their ability to reproduce the observed seasonal and spatial distribution of VSLS at the surface, using measurements from NOAA's long-term global monitoring network, and in the tropical troposphere, using recent aircraft measurements - including high-altitude observations from the NASA Global Hawk platform. The models generally capture the observed seasonal cycle of surface CHBr3 and CH2Br2 well, with a strong model-measurement correlation (r ≥ 0.7) at most sites. In a given model, the absolute model-measurement agreement at the surface is highly sensitive to the choice of emissions. Large inter-model differences are apparent when using the same emission inventory, highlighting the challenges faced in evaluating such inventories at the global scale. Across the ensemble, most consistency is found within the tropics where most of the models (8 out of 11) achieve best agreement to surface CHBr3 observations

  17. Valores de trihalometanos en agua de consumo de la provincia de Granada, España Trihalomethane levels in drinking water in the province of Granada (Spain

    Directory of Open Access Journals (Sweden)

    Carmen Freire

    2008-12-01

    -two tap water samples were collected in two campaigns during the winter and summer of 2006. An optimized procedure based on gas chromatography and mass spectrometry was used to determine concentrations of chloroform, bromodichloromethane, dibromochloromethane, and bromoform in the samples. Results: Total trihalomethane concentrations ranged from 0.14 to 18.75 μg/l in winter samples and from 0.01 to 31.87 μg/l in summer samples. The most abundant compound was chloroform. Mean trihalomethane concentrations were 10.13 in surface waters and 1.41 μg/l in ground waters. Conclusions: The trihalomethane levels found were considerably below the maximum permitted level of 100 μg/l in the European Union. The values obtained varied widely according to the type of water source: the highest concentrations were found in urban and sub-urban areas, where the water is largely of surface origin. The presence of trihalomethanes was lower than that reported in other Spanish regions.

  18. Investigación de trihalometanos en agua potable del Estado Carabobo, Venezuela Trihalomethanes in the drinking water of Carabobo State, Venezuela

    Directory of Open Access Journals (Sweden)

    A. Sarmiento

    2003-04-01

    and 2001. THM concentrations were determined by gas chromatography using the headspace technique. The concentrations of the following THMs were measured: chloroform (CHCl3, bromoform (CHBr3, chlorodibromomethane (CHBr2Cl and bromodichloromethane (CHCl2Br. Results: The concentration of total THMs was between 47.84 µg/l and 94.23 µg/l. CHCl3 was the most commonly formed compound representing 83% of all THMs in the CRS I and 82% in the CRS II. The concentrations of total THMs in the CRS I, specifically in the Baja and San Diego networks, were significantly higher (p < 0.05 than permissible levels set by the American Environmental Protection Agency (80 µg/l for the sum of all four THMs. Conclusions: The results show that in the area studied there is a risk of adverse health effects due to THMs in drinking water, especially in the Baja and San Diego networks.

  19. Contribution of very short-lived substances to stratospheric bromine loading: uncertainties and constraints

    Directory of Open Access Journals (Sweden)

    J. Aschmann

    2013-02-01

    Full Text Available Very short-lived substances (VSLS still represent a major factor of uncertainty in the quantification of stratospheric bromine loading. One of the major obstacles for short-lived source gases in contributing to the stratosphere is generally thought to be loss of inorganic bromine (Bry in the tropical tropopause layer (TTL due to dehydration. We use sensitivity calculations with a three-dimensional chemistry transport model comprising a consistent parametrization of convective transport and a comprehensive chemistry scheme to investigate the associated processes. The model considers the two most important bromine VSLS, bromoform (CHBr3 and dibromomethane (CH2Br2. The organic bromine source gases as well as the resulting profile of inorganic bromine in the model are consistent with available observations. In contrast to its organic precursors, Bry is assumed to have a significant sorption capacity regarding sedimenting liquid or frozen particles thus the fraction of intact source gases during their ascent through the TTL is a critical factor. We find that source gas injection is the dominant pathway into the stratosphere, about 50% of CHBr3 and 94% of CH2Br2 is able to overcome the cold point tropopause at approximately 17 km altitude, modulated by the interannual variability of the vertical transport efficiency. In fact, our sensitivity calculations indicate that the extent of source gas injection of CHBr3 is highly sensitive to the strength of convection and large-scale ascent; in contrast, modifying the photolysis or the destruction via OH yields a significantly smaller response. In principle, the same applies as well to CH2Br2, though it is considerably less responsive due to its longer lifetime. The next important aspect we identified is that the partitioning of available Bry from short-lived sources is clearly

  20. Contribution of very short-lived substances to stratospheric bromine loading: uncertainties and constraints

    Directory of Open Access Journals (Sweden)

    J. Aschmann

    2012-11-01

    Full Text Available Very short-lived substances (VSLS still represent a major factor of uncertainty in the quantification of stratospheric bromine loading. One of the major obstacles for short-lived source gases in contributing to the stratosphere is generally thought to be loss of inorganic bromine (Bry in the tropical tropopause layer (TTL due to dehydration. We use sensitivity calculations with a~three-dimensional chemistry transport model comprising a consistent parametrization of convective transport and a comprehensive chemistry scheme to investigate the associated processes. The model considers the two most important bromine VSLS, bromoform (CHBr3 and dibromomethane (CH2Br2. The organic bromine source gases as well as the resulting profile of inorganic bromine in the model are consistent with available observations. In contrast to its organic precursors, Bry is assumed to have a~significant sorption capacity regarding sedimenting liquid or frozen particles thus the fraction of intact source gases during their ascent through the TTL is a critical factor. We find that source gas injection is the dominant pathway into the stratosphere, about 50% of CHBr3 and 93% of CH2Br2 is able to overcome the cold point tropopause at approximately 17 km altitude, modulated by the interannual variability of the vertical transport efficiency. In fact, our sensitivity calculations indicate that the extent of source gas injection of CHBr3 is highly sensitive to the strength of convection and large-scale ascent; in contrast, modifying the photolysis or the destruction via OH yields a significantly smaller response. In principal, the same applies as well to CH2Br2, though it is considerably less responsive due to its longer lifetime. The next important aspect we identified is that the partitioning of available Bry from short-lived sources is clearly

  1. Processes Affecting the Trihalomethane Concentrations Associated with the Third Injection, Storage, and Recovery Test at Lancaster, Antelope Valley, California, March 1998 through April 1999

    Science.gov (United States)

    Fram, Miranda S.; Bergamaschi, Brian A.; Goodwin, Kelly D.; Fujii, Roger; Clark, Jordan F.

    2003-01-01

    The formation and fate of trihalomethanes (THM) during the third injection, storage, and recovery test at Lancaster, Antelope Valley, California, were investigated as part of a program to assess the long-term feasibility of using injection, storage, and recovery as a water-supply method and as a way to reduce water-level declines and land-subsidence in the Antelope Valley. The program was conducted by the U.S. Geological Survey in cooperation with the Los Angeles County Department of Public Works and the Antelope Valley-East Kern Water Agency. The water used for injection, storage, and recovery must be disinfected before injection and thus contains THMs and other disinfection by-products. THMs (chloroform, CHCl3, bromodichloromethane, CHCl2Br, dibromochloromethane, CHClBr2, and bromoform, CHBr3) are formed by reaction between natural dissolved organic carbon that is present in water and chlorine that is added during the disinfection step of the drinking water treatment process. THMs are carcinogenic compounds, and their concentrations in drinking water are regulated by the U.S. Environmental Protection Agency. During previous cycles of the Lancaster program, extracted water still contained measurable concentrations of THMs long after continuous pumping had extracted a greater volume of water than had been injected. This raised concerns about the potential long-term effect of injection, storage, and recovery cycles on ground-water quality in Antelope Valley aquifers. The primary objectives of this investigation were to determine (1) what controlled continued THM formation in the aquifer after injection, (2) what caused of the persistence of THMs in the extracted water, even after long periods of pumping, (3) what controlled the decrease of THM concentrations during the extraction period, and (4) the potential for natural attenuation of THMs in the aquifer. Laboratory experiments on biodegradation of THMs in microcosms of aquifer materials indicate that aquifer

  2. Effect of ocean acidification and elevated fCO2 on trace gas production by a Baltic Sea summer phytoplankton community

    Science.gov (United States)

    Webb, Alison L.; Leedham-Elvidge, Emma; Hughes, Claire; Hopkins, Frances E.; Malin, Gill; Bach, Lennart T.; Schulz, Kai; Crawfurd, Kate; Brussaard, Corina P. D.; Stuhr, Annegret; Riebesell, Ulf; Liss, Peter S.

    2016-08-01

    The Baltic Sea is a unique environment as the largest body of brackish water in the world. Acidification of the surface oceans due to absorption of anthropogenic CO2 emissions is an additional stressor facing the pelagic community of the already challenging Baltic Sea. To investigate its impact on trace gas biogeochemistry, a large-scale mesocosm experiment was performed off Tvärminne Research Station, Finland, in summer 2012. During the second half of the experiment, dimethylsulfide (DMS) concentrations in the highest-fCO2 mesocosms (1075-1333 µatm) were 34 % lower than at ambient CO2 (350 µatm). However, the net production (as measured by concentration change) of seven halocarbons analysed was not significantly affected by even the highest CO2 levels after 5 weeks' exposure. Methyl iodide (CH3I) and diiodomethane (CH2I2) showed 15 and 57 % increases in mean mesocosm concentration (3.8 ± 0.6 increasing to 4.3 ± 0.4 pmol L-1 and 87.4 ± 14.9 increasing to 134.4 ± 24.1 pmol L-1 respectively) during Phase II of the experiment, which were unrelated to CO2 and corresponded to 30 % lower Chl a concentrations compared to Phase I. No other iodocarbons increased or showed a peak, with mean chloroiodomethane (CH2ClI) concentrations measured at 5.3 (±0.9) pmol L-1 and iodoethane (C2H5I) at 0.5 (±0.1) pmol L-1. Of the concentrations of bromoform (CHBr3; mean 88.1 ± 13.2 pmol L-1), dibromomethane (CH2Br2; mean 5.3 ± 0.8 pmol L-1), and dibromochloromethane (CHBr2Cl, mean 3.0 ± 0.5 pmol L-1), only CH2Br2 showed a decrease of 17 % between Phases I and II, with CHBr3 and CHBr2Cl showing similar mean concentrations in both phases. Outside the mesocosms, an upwelling event was responsible for bringing colder, high-CO2, low-pH water to the surface starting on day t16 of the experiment; this variable CO2 system with frequent upwelling events implies that the community of the Baltic Sea is acclimated to regular significant declines in pH caused by up to 800 µatm fCO2. After

  3. Halocarbon emissions by selected tropical seaweeds: species-specific and compound-specific responses under changing pH

    Science.gov (United States)

    Leedham Elvidge, Emma C.; Sturges, William T.; Malin, Gill; Abd Rahman, Noorsaadah

    2017-01-01

    Five tropical seaweeds, Kappaphycus alvarezii (Doty) Doty ex P.C. Silva, Padina australis Hauck, Sargassum binderi Sonder ex J. Agardh (syn. S. aquifolium (Turner) C. Agardh), Sargassum siliquosum J. Agardh and Turbinaria conoides (J. Agardh) Kützing, were incubated in seawater of pH 8.0, 7.8 (ambient), 7.6, 7.4 and 7.2, to study the effects of changing seawater pH on halocarbon emissions. Eight halocarbon species known to be emitted by seaweeds were investigated: bromoform (CHBr3), dibro­momethane (CH2Br2), iodomethane (CH3I), diiodomethane (CH2I2), bromoiodomethane (CH2BrI), bromochlorometh­ane (CH2BrCl), bromodichloromethane (CHBrCl2), and dibro­mochloromethane (CHBr2Cl). These very short-lived halocarbon gases are believed to contribute to stratospheric halogen concentrations if released in the tropics. It was observed that the seaweeds emit all eight halocarbons assayed, with the exception of K. alvarezii and S. binderi for CH2I2 and CH3I respectively, which were not measurable at the achievable limit of detection. The effect of pH on halocarbon emission by the seaweeds was shown to be species-specific and compound specific. The highest percentage changes in emissions for the halocarbons of interest were observed at the lower pH levels of 7.2 and 7.4 especially in Padina australis and Sargassum spp., showing that lower seawater pH causes elevated emissions of some halocarbon compounds. In general the seaweed least affected by pH change in terms of types of halocarbon emission, was P. australis. The commercially farmed seaweed K. alvarezii was very sensitive to pH change as shown by the high increases in most of the compounds in all pH levels relative to ambient. In terms of percentage decrease in maximum quantum yield of photosynthesis (Fv∕Fm) prior to and after incubation, there were no significant correlations with the various pH levels tested for all seaweeds. The correlation between percentage decrease in the maximum quantum yield of photosynthesis

  4. 高压下典型小分子晶体的结构和行为%Structures and Properties in Typical Small-Molecule Crystals under High Pressure

    Institute of Scientific and Technical Information of China (English)

    靳锡联; 崔田

    2013-01-01

    高压能够引起凝聚态物质中原子微观结构的重新排列,形成新的电子分布状态,从而产生新材料和新特性.高压下典型分子体系呈现出了丰富的物理现象和物理性质,探索和发现这些高压下典型分子体系中的新结构及其行为,是高压物理研究重要且有意义的课题.通过对单质和小分子化合物两类体系的研究,说明了高压下典型分子单质I2、N2的结构和金属化行为;高压下典型分子化合物中碘仿、溴仿晶体的氢键和卤键的键合行为,以及氨硼烷晶体中存在的双氢键对分子集团转动动力学行为的影响等.高压下典型分子体系不同于常压下所表现出来的解离、重构和金属化等行为,为新结构的产生、新材料的探索以及新物理性质的发现提供了重要源泉.%High pressure can cause rearrangement of atoms in microstructure,and arouses reconfigurations of electronic states,which often brings new materials and new properties.The rich and colorful new phenomena and properties in the typical molecule system have been observed under high pressure.Studies of these new phases and behaviors in typical molecular system under high pressure are very important and significative.Two types of substance,i.e.elementary crystals and small-molecule compounds,are investigated thoroughly on structures and properties under high pressure,and demonstrate various features.In the elementary crystals,such as pressure-induced phase transition and metallization in I2 (solid iodine) and N2 (polymeric nitrogen),and in the small-molecule compounds,such as the hydrogen-bond and halogen-bond interactions in crystalline iodoform and bromoform under high pressure,the effects from dihydrogen bonds in ammonia borane which determining the complex dynamics behavior of rotations of the NH3 and BH3 groups under high pressure,etc.are discussed deeply.The distinct behaviors of molecular dissociation,reconstruction of crystal structures

  5. Understanding the Mechanism of Solvent-Mediated Adhesion of Vacuum Deposited Au and Pt Thin Films onto PMMA Substrates

    Energy Technology Data Exchange (ETDEWEB)

    Mo, Alan K [ORNL; Brown, Victoria L. [James Madison University; Rugg, Brandon K. [James Madison University; Devore, Prof. Thomas C. [James Madison University; Meyer III, Harry M [ORNL; Hu, Dr. Xiaofeng [James Madison University; Hughes, Prof. W. Christopher [James Madison University; Augustine, Prof. Brian H. [James Madison University

    2012-01-01

    The adhesion of 100 nm thick electron-beam deposited Au and Pt and magnetron sputtered Au thin films onto poly(methyl methacrylate) (PMMA) substrates can be significantly enhanced to over 90% adhesion by either spin-casting or vapor-exposure to hydrohalocarbon solvents prior to metal deposition compared to samples that are either cleaned in isopropyl alcohol or pre-treated with a remote O2 plasma. X-ray photoelectron spectroscopy (XPS) and evolved gas Fourier transform infrared spectroscopy (EGA-FTIR) reveal the presence of residual halogenated solvent molecules at the PMMA surface which chemically activates the surface to produce a stable chemical interaction between the noble metal film and the PMMA. Density functional theory (DFT) calculations show that the halogenated solvent molecules preferentially form a Lewis acid-base adduct with the oxygen atoms in the ester group in PMMA which is consistent with the measured enthalpy of desorption of chloroform (CHCl3) on PMMA determined by EGA-FTIR to be 36 kJ mol-1. The DFT model also supports the experimentally observed change in the high resolution XPS O 1s peak at 533.77 eV after metallization attributed to a change in the local bonding environment of the bridging O in the PMMA ester group. DFT also predicts that the deposited metal atom (M) inserts into the C-X bond where X is the halogen atom on either CHCl3 or bromoform (CHBr3) to form a O M X interaction that is observed by a M-X bond in the high resolution XPS Cl 2p3/2 peak at 198.03 eV and Br 3p3/2 peak at 182.06 eV. A range of solvents with differing polarities for PMMA pre-treatment have been used and it is proposed that non-complexing solvents result in significant metal adhesion improvement. The Gutmann acceptor number can be used to predict the effectiveness of solvent treatment for noble metal adhesion. A model is proposed in which the bond energy of the C-X bond of the solvent must be sufficiently low so that the C-X bond can be cleaved to form the M

  6. Halocarbon emissions by selected tropical seaweeds: species-specific and compound-specific responses under changing pH

    Directory of Open Access Journals (Sweden)

    Paramjeet Kaur Mithoo-Singh

    2017-01-01

    Full Text Available Five tropical seaweeds, Kappaphycus alvarezii (Doty Doty ex P.C. Silva, Padina australis Hauck, Sargassum binderi Sonder ex J. Agardh (syn. S. aquifolium (Turner C. Agardh, Sargassum siliquosum J. Agardh and Turbinaria conoides (J. Agardh Kützing, were incubated in seawater of pH 8.0, 7.8 (ambient, 7.6, 7.4 and 7.2, to study the effects of changing seawater pH on halocarbon emissions. Eight halocarbon species known to be emitted by seaweeds were investigated: bromoform (CHBr3, dibro­momethane (CH2Br2, iodomethane (CH3I, diiodomethane (CH2I2, bromoiodomethane (CH2BrI, bromochlorometh­ane (CH2BrCl, bromodichloromethane (CHBrCl2, and dibro­mochloromethane (CHBr2Cl. These very short-lived halocarbon gases are believed to contribute to stratospheric halogen concentrations if released in the tropics. It was observed that the seaweeds emit all eight halocarbons assayed, with the exception of K. alvarezii and S. binderi for CH2I2 and CH3I respectively, which were not measurable at the achievable limit of detection. The effect of pH on halocarbon emission by the seaweeds was shown to be species-specific and compound specific. The highest percentage changes in emissions for the halocarbons of interest were observed at the lower pH levels of 7.2 and 7.4 especially in Padina australis and Sargassum spp., showing that lower seawater pH causes elevated emissions of some halocarbon compounds. In general the seaweed least affected by pH change in terms of types of halocarbon emission, was P. australis. The commercially farmed seaweed K. alvarezii was very sensitive to pH change as shown by the high increases in most of the compounds in all pH levels relative to ambient. In terms of percentage decrease in maximum quantum yield of photosynthesis (Fv∕Fm prior to and after incubation, there were no significant correlations with the various pH levels tested for all seaweeds. The correlation between percentage decrease in the maximum quantum yield of

  7. Research of VOCs in drinking water of Guangzhou%广州市饮用水中挥发性有机物的研究

    Institute of Scientific and Technical Information of China (English)

    刘祖发; 刘嘉仪; 张骏鹏; 邓哲; 卓文珊; 张洲; 王新明

    2014-01-01

    The existence of volatile organic compounds (VOCs) in drinking water, which may create adverse health effects on human beings, is due to the organic pollution of the water sources and/or the formation of disinfection by-products (DBPs) during the drinking water treatment and supply processes. Since the reform and opening up, Guangzhou has been undergoing a rapid increase and development of population and economy, which is accompanied by many serious social and environmental problems, such as the safety of drinking water. Although the VOCs in drinking water has received increased attention in the world, the research on this issue in Guangzhou is still scarce. In this study, 15 tap water samples were collected at different sampling sites in center city district of Guangzhou. The VOCs species and trihalomethanes (THMs) mass concentrations in the samples were analyzed with purge&trap preconcentrator coupled with a gas chromatography-mass selective detector (GC-MSD).20 VOCs species were detected in the tap water in Guangzhou, and above 78%of these species were aromatic hydrocarbons and trihalomethanes. THMs, which include four species:chloroform (CF), bromodichloromethane (BDCM), dibromochloromethane (DBCM) and bromoform (BF), were found in all samples. The mass concentration of Total THMs was 46.46μg·L-1, ranged from 39.91μg·L-1 to 53.31μg·L-1. Compared to the national standards for drinking water in 2006, THMs mass concentrations in Guangzhou tap water is under the corresponding standard limits. As for bottled water which is widely sold in the market, the THMs mass concentration was fairly low, and the total THMs in bottled water was 1.47μg·L-1 in average, which is about 30 times lower than the tap water’s mass concentration. In this research, we also designed experiments to study the influence of temperature and boiling on the THMs mass concentration in drinking water. It was found that before boiling, the concentration of THMs increased with the increasing

  8. Cáncer gástrico en Costa Rica: ¿existe o no relación con la cloración del agua para consumo humano?

    Directory of Open Access Journals (Sweden)

    Darner A Mora Alvarado

    2007-07-01

    que no existe relación entre la incidencia de CG y la cloración del ACH, incluida la antigüedad de la misma y el tipo de fuente de agua usada (subterránea y superficial. Por último se recomienda realizar una campaña de divulgación por parte del Instituto Costarricense de Acueductos y Alcantarillados como entidad rectora en el suministro de agua potable, con el propósito de eliminar la desconfianza de los usuarios en el consumo de ACH sometida a la cloración. Además, se debe promover la elaboración de estudios semejantes a éste con otro tipo de cánceres como el de vejiga y el colorrectal.Gastric cancer (GC is the leading cause of cancer-related mortality in Costa Rican males. After breast cancer, it is the second highest cause of cancer mortality in women in Costa Rica. From a histological point-of-view, GC is divided into two types: the first is the "diffuse" type and it has been related etiologically to genetic factors; the second type is the "intestinal" type and it has been linked to such environmental carcinogenic factors as: toxic chemical substances, geographic altitude and age. Along these lines, some researchers have studied possible relationships bet-tween epidemiological and ecological factors such as, for example, physico-chemical traits of water for human consumption (ACH, soils, pesticide use as well as carcinogen intake in milk such as Pteridium aquilinum (the so-called male fern. Regarding ACH, since 1974, water chlorination has been causally linked to formation of byproducts of disinfection like chloroform and bromoform, so-called trihalomethanes, which have a propensity for causing a higher incidence of GC in the population. These facts, along with media hype, have provoked uncertainty and doubts regarding the safety of chlorinated water among the public. With this background in mind, an exploratory-ecological epidemiological study was carried out with the explicit purpose of analyzing if there is or if there isn´t a statistically

  9. Investigation of Tap Water Quality in Some Areas of Beijing%北京部分地区末梢水卫生现状调查

    Institute of Scientific and Technical Information of China (English)

    赵金辉; 叶研; 魏建荣; 刘飞; 陶晶; 韩志宇; 田佩瑶; 张雅洁; 刘玉敏

    2012-01-01

    ,nickel,barium,beryllium,molybdenum,sodium,thallium,dichloride methyl bromide,methyl chloride dibromochloromethane, bromoform, trihalomethane, BHC, DDT, heptachlor, hexachlorobenzene, lindane were detected. Results Among 270 investigated families,the qualified rates of all indexes were more than 88%. Compared with the summer, the qualified rate of barium,sodium,selenium,iron among tap water was lower in winter (P <0.05) .The concentration of the total number in the colonies,aluminum,barium,sodium,selenium,zinc,iron,manganese were higher in winter than those in summer. The lead and nickel concentrations were lower in winter than those in summer. Compared with the household well supply,the qualified rate of total coli forms,manganese and the concentration of aluminum,zinc were higher on municipal water supply;On the country,the concentration of barium,sodium were lower. All the differences were statistically significant (P<0.05). The concentration of manganese of tap water was relatively higher in suburbs of the northeast region. The concentration of sodium, iron,selenium,barium of tap water was relatively higher in urban and suburban southwest region. All of chemical indicators measured were qualified in city. The qualified rate of total coli forms was relatively lower in southwest suburbs and.the southwest suburbs. Conclusion The tap water was in good condition in the investigated area of Beijing, and the water quality may be influenced in seasons.