WorldWideScience

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. Bromoform formation in ozonated groundwater containing bromide and humic substances

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, W.J.; Amy, G.L.; Moore, C.A.; Zika, R.G.

    1986-01-01

    The effect of bromide ion, organic carbon concentration (natural aquatic humic substances), pH, and solar irradiation on the formation of bromoform in ozonated groundwater has been studied. The studies were conducted on four unique samples of groundwater taken from different regions of the Biscayne Aquifer in southern Florida. All other conditions being equal, increases in bromide ion concentrations resulted in increases in CHBr/sub 3/ formation. In three of the four samples, CHBr/sub 3/ formation decreased as the pH level increased from 5 to 9. The fourth sample exhibited an opposite trend whereby the CHBr/sub 3/ concentration increased with increasing pH. Bromoform concentration increased with increased O/sub 3/ concentration over an ozone dosage range of 3.4 to 6.7 mg/L. Ozonated samples placed in sunlight immediately after ozone addition showed a decrease in the formation of CHBr/sub 3/ presumably due to the photodecomposition of HOBr/OBr.

  3. Bromoform formation in ozonated groundwater containing bromide and humic substances

    Energy Technology Data Exchange (ETDEWEB)

    Copper, W.J. (Florida International Univ., Miami (United States)); Amy, G.L. (Univ. of Arizona, Tucson (United States)); Moore, C.A.; Zika, R.G. (Univ. of Miami, FL (United States))

    The effect of bromide ion, organic carbon concentration (natural aquatic humic substances), pH, and solar irradiation on the formation of bromoform in ozonated groundwater has been studied. The studies were conducted on four unique samples of groundwater taken from different regions of the Biscayne Aquifer in southern Florida. All other conditions being equal, increases in bromide ion concentrations resulted in increases in CHBr{sub 3} formation. In three of the four samples, CHBr{sub 3} formation decreased as the pH level increased from 5 to 9. The fourth sample exhibited an opposite trend whereby the CHBr{sub 3} concentration increased with increasing pH. Bromoform concentration increased with increased O{sub 3} concentration over an ozone dosage range of 3.4 to 6.7 mg/L. Ozonated samples placed in sunlight immediately after ozone addition showed a decrease in the formation of CHBr{sub 3}, presumably due to the photodecomposition of HOBr/OBr.

  4. Marine sources of bromoform in the global open ocean - global patterns and emissions

    Science.gov (United States)

    Stemmler, I.; Hense, I.; Quack, B.

    2015-03-01

    Bromoform (CHBr3) is one important precursor of atmospheric reactive bromine species that are involved in ozone depletion in the troposphere and stratosphere. In the open ocean bromoform production is linked to phytoplankton that contains the enzyme bromoperoxidase. Coastal sources of bromoform are higher than open ocean sources. However, open ocean emissions are important because the transfer of tracers into higher altitude in the air, i.e. into the ozone layer, strongly depends on the location of emissions. For example, emissions in the tropics are more rapidly transported into the upper atmosphere than emissions from higher latitudes. Global spatio-temporal features of bromoform emissions are poorly constrained. Here, a global three-dimensional ocean biogeochemistry model (MPIOM-HAMOCC) is used to simulate bromoform cycling in the ocean and emissions into the atmosphere using recently published data of global atmospheric concentrations (Ziska et al., 2013) as upper boundary conditions. Our simulated surface concentrations of CHBr3 match the observations well. Simulated global annual emissions based on monthly mean model output are lower than previous estimates, including the estimate by Ziska et al. (2013), because the gas exchange reverses when less bromoform is produced in non-blooming seasons. This is the case for higher latitudes, i.e. the polar regions and northern North Atlantic. Further model experiments show that future model studies may need to distinguish different bromoform-producing phytoplankton species and reveal that the transport of CHBr3 from the coast considerably alters open ocean bromoform concentrations, in particular in the northern sub-polar and polar regions.

  5. Marine sources of bromoform in the global open ocean – global patterns and emissions

    Directory of Open Access Journals (Sweden)

    I. Stemmler

    2015-03-01

    Full Text Available Bromoform (CHBr3 is one important precursor of atmospheric reactive bromine species that are involved in ozone depletion in the troposphere and stratosphere. In the open ocean bromoform production is linked to phytoplankton that contains the enzyme bromoperoxidase. Coastal sources of bromoform are higher than open ocean sources. However, open ocean emissions are important because the transfer of tracers into higher altitude in the air, i.e. into the ozone layer, strongly depends on the location of emissions. For example, emissions in the tropics are more rapidly transported into the upper atmosphere than emissions from higher latitudes. Global spatio-temporal features of bromoform emissions are poorly constrained. Here, a global three-dimensional ocean biogeochemistry model (MPIOM-HAMOCC is used to simulate bromoform cycling in the ocean and emissions into the atmosphere using recently published data of global atmospheric concentrations (Ziska et al., 2013 as upper boundary conditions. Our simulated surface concentrations of CHBr3 match the observations well. Simulated global annual emissions based on monthly mean model output are lower than previous estimates, including the estimate by Ziska et al. (2013, because the gas exchange reverses when less bromoform is produced in non-blooming seasons. This is the case for higher latitudes, i.e. the polar regions and northern North Atlantic. Further model experiments show that future model studies may need to distinguish different bromoform-producing phytoplankton species and reveal that the transport of CHBr3 from the coast considerably alters open ocean bromoform concentrations, in particular in the northern sub-polar and polar regions.

  6. 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.

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

    Directory of Open Access Journals (Sweden)

    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

  8. Contrasting the surface ocean distribution of bromoform and methyl iodide; implications for boundary layer physics, chemistry and climate

    Energy Technology Data Exchange (ETDEWEB)

    Palmer, C J, E-mail: carl.j.palmer@gmail.co [Department of Oceanography, University of Cape Town, 7701 (South Africa)

    2010-08-15

    Bromoform and methyl iodide are both methane-like hydrocarbons with a halogen atom replacing one or more of the hydrogen atoms. Both of these compounds occur naturally in the environment as a result of their production from seaweed and kelp. They are of interest to climate science as a result of their catalytic destruction of boundary layer ozone (a potent greenhouse gas) and, specifically for methyl iodide, the proposed role in the formation of new cloud condensation nuclei with implications for climate. In this paper, the currently available data on the distribution of bromoform and methyl iodide are analysed and contrasted to show that the concentrations of bromoform and methyl iodide do not correlate, that, in contrast to bromoform, the parameterization of sea surface methyl iodide concentrations demands only the sea surface temperature, and that the pelagic distribution of methyl iodide appears to follow the solar zenith angle. These three observations together suggest that, while the pelagic source of bromoform is mostly biogenic, the source of methyl iodide is photochemical. This has implications for the understanding of planetary boundary layer chemistry and potential organohalogen mediated feedbacks to climate.

  9. Contrasting the surface ocean distribution of bromoform and methyl iodide; implications for boundary layer physics, chemistry and climate

    International Nuclear Information System (INIS)

    Bromoform and methyl iodide are both methane-like hydrocarbons with a halogen atom replacing one or more of the hydrogen atoms. Both of these compounds occur naturally in the environment as a result of their production from seaweed and kelp. They are of interest to climate science as a result of their catalytic destruction of boundary layer ozone (a potent greenhouse gas) and, specifically for methyl iodide, the proposed role in the formation of new cloud condensation nuclei with implications for climate. In this paper, the currently available data on the distribution of bromoform and methyl iodide are analysed and contrasted to show that the concentrations of bromoform and methyl iodide do not correlate, that, in contrast to bromoform, the parameterization of sea surface methyl iodide concentrations demands only the sea surface temperature, and that the pelagic distribution of methyl iodide appears to follow the solar zenith angle. These three observations together suggest that, while the pelagic source of bromoform is mostly biogenic, the source of methyl iodide is photochemical. This has implications for the understanding of planetary boundary layer chemistry and potential organohalogen mediated feedbacks to climate.

  10. 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.

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

    Directory of Open Access Journals (Sweden)

    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

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

    Directory of Open Access Journals (Sweden)

    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

  13. On the emissions and transport of bromoform: sensitivity to model resolution and emission location

    Directory of Open Access Journals (Sweden)

    M. R. Russo

    2015-07-01

    Full Text Available Bromoform (CHBr3 is a short-lived species with an important but poorly quantified ocean source. It can be transported to the Tropical Tropopause Layer (TTL, in part by rapid, deep convective lifting, from where it can influence the global stratospheric ozone budget. In a modelling study, we investigate the importance of the regional distribution of the emissions and of model resolution for the transport of bromoform to the TTL. We use two idealised CHBr3 emission fields (one coastal, one uniformly distributed across the oceans implemented in high and coarse resolution (HR and CR versions of the same global model and focus on February as the period of peak convection in the West Pacific. Using outgoing long-wave radiation and precipitation as metrics, the HR version of the model is found to represent convection better. In the more realistic HR model version, the coastal emission scenario leads to 15–20 % more CHBr3 in the global TTL, and up to three times more CHBr3 in the TTL over the Maritime Continent, than when uniform emissions of the same tropical magnitude are employed. Using the uniform emission scenario in both model versions, the distribution of CHBr3 at 15.7 km (approximately the level of zero net radiative heating is qualitatively consistent with the differing geographic distributions of convection. However, averaged over the whole tropics, the amount of CHBr3 in the TTL in the two model versions is similar. Using the coastal scenario, in which emissions are particularly high in the Maritime Continent because of its long coastlines, the mixing ratio of CHBr3 in the TTL is enhanced over the Maritime Continent in both model versions. The enhancement is larger, and the peak in CHBr3 mixing ratio occurs at a higher altitude, in the HR model version. Our regional-scale results indicate that using aircraft measurements and coarse global models to infer CHBr3 emissions will be very difficult, particularly if (as is possible emissions are

  14. Development of a Simplified, Cost Effective GC-ECD Methodology for the Sensitive Detection of Bromoform in the Troposphere

    Science.gov (United States)

    Kuyper, Brett; Labuschagne, Casper; Philibert, Raïssa; Moyo, Nicholas; Waldron, Howard; Reason, Chris; Palmer, Carl

    2012-01-01

    Wherever measurements have been made bromoform was found to be ubiquitous in the surface ocean in pmolar-nmolar concentrations. These measurements show concentrations in coastal regions orders of magnitude higher than in the pelagic oceans. Its atmospheric presence is primarily due to its release from algae and rapid transport to the marine boundary troposphere where it is known to participate in ozone chemistry via photochemical and catalytic pathways. Until quite recently, a limited number of studies existed (compared to other marine volatile organic compounds (VOCs)), mainly due to the analytical challenge(s) presented by the low environmental mixing ratios. In this work we detail the development of a simplified, cost effective method to detect and quantify bromoform in environmental air samples. Air samples (1.5 L) were preconcentrated onto a precooled adsorbent (Carbopack X/Carboxen 1016) trap. These samples were injected by means of rapid thermal desorption for separation and detection by GC-ECD. The system was calibrated by means of a custom-built permeation oven. A linear system response was achieved, having a detection limit of 0.73 ± 0.09 ppt. A range of environmental samples was analysed to demonstrate the ability of the technique to separate and identify bromoform from air samples. The results showed that bromoform concentrations typically averaged 24.7 ± 17.3 ppt in marine air samples, 68.5 ± 26.3 ppt in Cape Town urban air samples and 33.9 ± 40.5 ppt in simulated biomass burning plumes (SBBP). PMID:23202011

  15. Development of a Simplified, Cost Effective GC-ECD Methodology for the Sensitive Detection of Bromoform in the Troposphere

    Directory of Open Access Journals (Sweden)

    Chris Reason

    2012-10-01

    Full Text Available Wherever measurements have been made bromoform was found to be ubiquitous in the surface ocean in pmolar-nmolar concentrations. These measurements show concentrations in coastal regions orders of magnitude higher than in the pelagic oceans. Its atmospheric presence is primarily due to its release from algae and rapid transport to the marine boundary troposphere where it is known to participate in ozone chemistry via photochemical and catalytic pathways. Until quite recently, a limited number of studies existed (compared to other marine volatile organic compounds (VOCs, mainly due to the analytical challenge(s presented by the low environmental mixing ratios. In this work we detail the development of a simplified, cost effective method to detect and quantify bromoform in environmental air samples. Air samples (1.5 L were preconcentrated onto a precooled adsorbent (Carbopack X/Carboxen 1016 trap. These samples were injected by means of rapid thermal desorption for separation and detection by GC-ECD. The system was calibrated by means of a custom-built permeation oven. A linear system response was achieved, having a detection limit of 0.73 ± 0.09 ppt. A range of environmental samples was analysed to demonstrate the ability of the technique to separate and identify bromoform from air samples. The results showed that bromoform concentrations typically averaged 24.7 ± 17.3 ppt in marine air samples, 68.5 ± 26.3 ppt in Cape Town urban air samples and 33.9 ± 40.5 ppt in simulated biomass burning plumes (SBBP.

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

    Directory of Open Access Journals (Sweden)

    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

  17. Fusion curves and thermodynamic properties of carbon tetrachloride, chloroform, bromoform and silicon tetrachloride at pressure up to 3500 Mpa

    Institute of Scientific and Technical Information of China (English)

    Zhu Rong-Jiao; Xu Wei; Tian Yi-Ling; Hao Ji-Shuang

    2008-01-01

    The fusion temperature as a function of pressure for carbon tetrachloride, chloroform, bromoform and silicon tetrachloride at pressures up to 3500MPa has been determined. The experimental data were fitted by the equation Tfus = T0(1 + Ap/a1)a2 exp(-a3△p) and the changes of the molar enthalpy and molar internal energy on fusion were calculated using the parameters of the fitted equation. Comparisons with the data from the literature show that the experimental data, parameters of fitted equations, changes of the molar enthalpy and molar internal energy are reliable.

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

    Directory of Open Access Journals (Sweden)

    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

  19. Spectroscopic and computational studies of matrix-isolated iso-CHBr3: Structure, properties, and photochemistry of iso-bromoform

    International Nuclear Information System (INIS)

    Iso-polyhalomethanes are known reactive intermediates that play a pivotal role in the photochemistry of halomethanes in condensed phases. In this work, iso-bromoform (iso-CHBr3) and its deuterated isotopomer were characterized by matrix isolation infrared and UV/visible spectroscopy, supported by ab initio and density functional theory calculations, to further probe the structure, spectroscopy, and photochemistry of this important intermediate. Selected wavelength laser irradiation of CHBr3 isolated in Ar or Ne matrices at ∼5 K yielded iso-CHBr3; the observed infrared and UV/visible absorptions are in excellent agreement with computational predictions, and the energies of various stationary points on the CHBr3 potential energy surface were characterized computationally using high-level methods in combination with correlation consistent basis sets. These calculations show that, while the corresponding minima lie ∼200 kJ/mol above the global CHBr3 minimum, the isomer is bound by some 60 kJ/mol in the gas phase with respect to the CHBr2+ Br asymptote. The photochemistry of iso-CHBr3 was investigated by selected wavelength laser irradiation into the intense S0→ S3 transition, which resulted in back photoisomerization to CHBr3. Intrinsic reaction coordinate calculations confirmed the existence of a first-order saddle point connecting the two isomers, which lies energetically below the threshold of the radical channel. Subsequently, natural bond orbital analysis and natural resonance theory were used to characterize the important resonance structures of the isomer and related stationary points, which demonstrate that the isomerization transition state represents a crossover from dominantly covalent to dominantly ionic bonding. In condensed phases, the ion-pair dominated isomerization transition state structure is preferentially stabilized, so that the barrier to isomerization is lowered.

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

    Science.gov (United States)

    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.

  1. Modeling 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

    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)

  2. 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

  3. The measurement of dangerous organic materials in water by gas chromatographic methods

    International Nuclear Information System (INIS)

    The measurements were confined only to drinking water in order to investigate the effect of disinfection by chloronation. The results obtained revealed that all the values for carbon tetrachlorides and bromoform in drinking water are much less than the acceptable values

  4. 40 CFR Table 2 to Subpart Jj of... - List of Volatile Hazardous Air Pollutants

    Science.gov (United States)

    2010-07-01

    ... (Aroclors) 1336363 Polycyclic Organic Matter b 1,3-Propane sultone 1120714 beta-Propiolactone 57578... Bromoform 75252 1,3-Butadiene 106990 Carbon disulfide 75150 Carbon tetrachloride 56235 Carbonyl sulfide...-Dichloropropene 542756 Diethanolamine 111422 N,N-Dimethylaniline 121697 Diethyl sulfate 64675...

  5. Chloroform in a pristine aquifer system: Toward an evidence of biogenic origin

    DEFF Research Database (Denmark)

    Laturnus, F.; Lauritsen, F.R.; Grøn, C.

    2000-01-01

    Ambient air, soil air, and groundwater were monitored for volatile halogenated organic compounds in a pristine spruce forest at Klosterhede, Denmark. Although this location is remote from industrial areas and free of any point sources of either soil or groundwater contamination, several volatile......, only bromoform was found and only in the upper soil layer. For chloroform a formation in the spruce forest soil is suggested, leading to concentrations in the groundwater in the micrograms per liter range....

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

    Science.gov (United States)

    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.

  7. Detailed modeling of the atmospheric degradation mechanism of very-short lived brominated species

    OpenAIRE

    G. Krysztofiak; Catoire, Valéry; Poulet, G.; Marécal, V.; Pirre, Michel; Louis, F.; Canneaux, S.; B. Josse

    2012-01-01

    International audience Detailed chemical reaction schemes for the atmospheric degradations of the very short-lived species (VSLS) bromoform (CHBr3) and dibromomethane (CH2Br2) have been established. These degradation schemes have been implemented in the meteorological/tracer transport model CATT-BRAMS used in the present case as pseudo one-dimensional model with chemistry of CH4, CO, HOx, NOx, NOy and Ox. They include the main possible reactions of the intermediate brominated peroxy radica...

  8. Transport of very short-lived halocarbons from the Indian Ocean to the stratosphere through the Asian monsoon circulation

    Science.gov (United States)

    Fiehn, Alina; Hepach, Helmke; Atlas, Elliot; Quack, Birgit; Tegtmeier, Susann; Krüger, Kirstin

    2016-04-01

    Halogenated organic compounds are naturally produced in the ocean and emitted to the atmosphere. The halogenated very short-lived substances (VSLS), such as bromoform, have atmospheric lifetimes of less than half a year. When VSLS reach the stratosphere, they enhance ozone depletion and thus impact the climate. During boreal summer, the Asian monsoon circulation transfers air masses from the Asian troposphere to the global stratosphere. Still, the extent to which VSLS from the Indian Ocean contribute to the stratospheric halogen burden and their exact origin is unclear. Here we show that the monsoon circulation transports VSLS from the Indian Ocean to the stratosphere. During the research cruises SO234-2 and SO235 in July-August 2014 onboard RV SONNE, we measured oceanic and atmospheric concentrations of bromoform (tropical lifetime at 10 km = 17 days), dibromomethane (150 days) and methyl iodide (3.5 days) in the subtropical and tropical West Indian Ocean and calculated their emission strengths. We use the Langrangian transport model FLEXPART driven by ERA-Interim meteorological fields to investigate the transport of oceanic emissions in the atmosphere. We analyze the direct contribution of observed bromoform emissions to the stratospheric halogen budget with forward trajectories. Furthermore, we investigate the connection between the Asian monsoon anticyclone and the oceanic source regions using backward trajectories. The West Indian Ocean is a strong source region of VSLS to the atmosphere and the monsoon transport is fast enough for bromoform to reach the stratosphere. However, the main source regions for the entrainment of oceanic air masses through the Asian monsoon anticyclone are the West Pacific and Bay of Bengal as well as the Arabian Sea. Our findings indicate that changes in emission or circulation in this area due to climate change can directly affect the stratospheric halogen burden and thus the ozone layer.

  9. 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.

  10. Chlorination byproducts in drinking water produced from thermal desalination in United Arab Emirates.

    Science.gov (United States)

    Elshorbagy, Walid; Abdulkarim, Mohamed

    2006-12-01

    Oil activities in the Arabian Gulf can potentially affect the quality of the intake water available for coastal desalination plants. This paper addresses such situation by investigating the quality of intake water and desalinated water produced by a desalination plant located near a coastal industrial complex in United Arab Emirates (UAE). Analyses of the organic compounds on the intake seawater reported non-detected levels in most samples for the three tested organic groups; namely Polyaromatic Hydrocarbons (PAHs), Phenols, and Polychlorinated Biphenyls (PCBs). Trihalomethanes (THMs) and Haloacetic Acids (HAAs) were also tracked in the intake sea water, throughout the desalination processes, and in the final produced drinking water, to evaluate the undertaken pre- and post chlorination practices. The levels of considered Chlorination Byproducts (CBPs) were mostly found below the permissible international limits with few exceptions showing tangible levels of bromoform in the intake seawater and in the final produced drinking water as well. Lab-controlled experiments on the final produced distillate showed little contribution of its blending with small percentage of seawater upon the formation of trihalomethane and in particular, bromoform. Such results indicate that the organic precursors originated in the seawater are responsible for bromoform formation in the final distillate. PMID:16738754

  11. 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

  12. Production and distribution of chlorination by-products in the cooling water system of a coastal power station

    International Nuclear Information System (INIS)

    Employing chlorination as antifouling agent in cooling water circuits of coastal power plants can lead to the production of chlorination by-products (CBP), mainly due to chlorine's reactions with the organic compounds present in natural seawater. Important among the by products are trihalomethane, haloacetonitriles, halo acetic acids, halo phenols etc., with trihalomethanes (THM) generally being the predominant compounds. The THM species that are commonly observed are chloroform, mono bromodichloromethane, dibromochloro-methane and bromoform. The present work was carried out to understand the production and distribution of chlorination by products (mainly trihalomethanes) in the cooling water systems of Madras Atomic Power Station (MAPS). Field studies were carried out in which samples collected from the intake, forebay pump house, out fall point and mixing point were analysed for THM using gas chromatograph with electron capture detector. The results showed that bromoform was the dominant THM formed as a result of chlorination, followed by dibromochloromethane. Mono bromodichloromethane and chloroform were not observed in seawater throughout the study period. Moreover, no THM could be detected at the intake point. The total THM values at other stations ranged between 25-250 μgL-1, the highest values were observed at the process seawater pump outlet and the lowest at the mixing point. The concentrations of CBP's formed were found to be related to the chlorine residuals measured. In addition, laboratory experiments were carried out to understand CBP formation as a function of chlorine dose and contact time. Chlorine doses ranging from 1 to 10 mgL-1 were added to unfiltered seawater and the various THMs formed were analysed after different time intervals. The results confirmed that bromoform was the dominant THM species, followed by dibromochloromethane, as observed in the field studies. As the chlorine doses increased, the other THMs, namely, mono

  13. 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

  14. [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).

  15. Heavy mineral placers off Kalbadevi Bay, Ratnagiri, Maharashtra

    Digital Repository Service at National Institute of Oceanography (India)

    Valsangkar, A.B.

    by using bromoform of 2.89 sp. gr. and following the standard procedures of Milner (1962). Fig. 1. Pre- and post-monsoon sample locations in Kalbadevi Bay, Ratnagiri. 4 Results and discussions A) Sand-silt-clay content: Variations in sand.... 126, D.G.M., Nagpur, Govt. of Maharashtra, Unbubl. Rep. Milner, H.B. (1962). Sedimentary Petrography. George Allen & Unwin Ltd., London, Part 1, 643. Rajamanickam, G.V. and Gujar, A.R. (1984). Sediment depositional environment in some bays...

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

    International Nuclear Information System (INIS)

    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, 216 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. Presage

  17. Reaction products from the chlorination of seawater. Final report 15 Jul 75-14 Jul 80

    Energy Technology Data Exchange (ETDEWEB)

    Carpenter, J.H.; Smith, C.A.; Zika, R.G.

    1981-03-01

    Chemical treatment of natural waters, in particular the use of chlorine as a biocide, modifies the chemistry of these waters in ways that are not fully understood. The research described in this report examined both inorganic and organic reaction products from the chlorination of seawater using a variety of analytical approaches. Some analytical methods in widespread current use underestimate the residual oxidants in chlorinated seawater by as much as 70% depending upon the detail of the procedures. The chlorination of seawater in the presence of light produces substantial quantities of bromate ions which can influence standard analytical procedures and represents an unknown factor in estuarine and coastal waters. The copper complexing capacity of Biscayne Bay, Florida water was found to be substantially reduced with the addition of chlorine. Analysis was made by anodic stripping voltammetry on water samples after successive additions of copper sulfate solution. Laboratory chlorination of water from the intake of the Port Everglades, Florida power plant produces bromoform levels comparable to that found in the plant discharge. These results are in contrast to results reported in the literature for a power plant on the Patuxent estuary in Maryland, so that bromoform production appears to be site-specific. Chloroform extracts of chlorinated Biscayne Bay water are found to contain halogenated compounds which are new and different, and which pose unusual analytical problems. Studies using GC/ECD, GC/MS, HPLC, H NMR, differential pulsed polarography and other techniques on natural extracts and synthesized compounds are reported.

  18. 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.

  19. Covalent Carbene Functionalization of Graphene: Toward Chemical Band-Gap Manipulation.

    Science.gov (United States)

    Sainsbury, Toby; Passarelli, Melissa; Naftaly, Mira; Gnaniah, Sam; Spencer, Steve J; Pollard, Andrew J

    2016-02-01

    In this work, we employ dibromocarbene (DBC) radicals to covalently functionalize solution exfoliated graphene via the formation of dibromocyclopropyl adducts. This is achieved using a basic aqueous/organic biphasic reaction mixture to decompose the DBC precursor, bromoform, in conjunction with a phase-transfer catalyst to facilitate ylide formation and carbene migration to graphene substrates. DBC-functionalized graphene (DBC-graphene) was characterized using a range of spectroscopic and analytical techniques to confirm the covalent nature of functionalization. Modified optical and electronic properties of DBC-graphene were investigated using UV-vis spectroscopy, analysis of electrical I-V transport properties, and noncontact terahertz time-domain spectroscopy. The implications of carbene functionalization of graphene are considered in the context of scalable radical functionalization methodologies for bulk-scale graphene processing and controlled band-gap manipulation of graphene. PMID:26824127

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

    DEFF Research Database (Denmark)

    Hansen, Kamilla Marie Speht; Zortea, R.; Piketty, A.;

    2013-01-01

    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...... 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...

  1. 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%.

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. Long term puzzles of the CH and CD energetics and related phenomena revisited; solutions sought through REMPI-photofragmentations of bromomethanes.

    Science.gov (United States)

    Hafliðason, Arnar; Wang, Huasheng; Kvaran, Ágúst

    2016-01-21

    Ever since the pioneering work by Herzberg and Johns in 1969 (The Astrophysical Journal, 1969, 158, 399) the spectral assignment and the energetics of the fundamental molecular fragment CH, in the region of 63 000-65 000 cm(-1) (7.81-8.06 eV), have remained a puzzle to a large extent. The dissociation of bromoform and deuterated bromoform following two-photon resonance excitations to molecular Rydberg states forms the fragment species CH* and CD* in the excited state A(2)Δ(v' =0) as well as carbon and bromine atoms in the ground and first excited states, C/C* and Br/Br*. Further (1r + 1i)REMPI of CH* and CD* resonance excites the fragments to the energy region of concern, whereas the atom fragments were identified by further (2r + 1i)REMPI. Analysis based on spectral simulations, isotope shifts and comparison with other data allowed spectral identifications, assignments and partial characterization of four highly excited bound states for each of the molecular fragments (CH**/CD**); including the (3)(2)Π valence state and the (4)(2)Π Rydberg state, for the first time. Perturbations, shown as line-shifts, line-intensity and/or line-width alterations, due to the level-to-level state interactions between the bound states and predissociations by a repulsive state are recognized. Recording of C(+) signals in REMPI of several bromomethanes for a one-photon energy of about 40 333 cm(-1) allows the clarification of a mystery concerning a broad C(+) band frequently observed. This work, presented, demonstrates the usefulness of molecular REMPI for fragment analysis. PMID:26674135

  7. 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)).

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

    International Nuclear Information System (INIS)

    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−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−1, on average). The estimated concentration of micropollutants in crops ranged from −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 μg per person and week (Σ 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.

  9. Brominating activity of the seaweed Ascophyllum nodosum: Impact on the biosphere

    Energy Technology Data Exchange (ETDEWEB)

    Wever, R.; Tromp, M.G.M.; Krenn, B.E.; Marjani, A.; Van Tol, M. (Univ. of Amsterdam (Netherlands))

    1991-03-01

    Macroalgae are an important source of volatile halogenated organic compounds, such as bromoform and dibromomethane. The mechanism by which these compounds are formed is still elusive. The authors report that the brown seaweeds Laminaria saccharina, Laminaria digitata, Fucus vesiculosis, Pelvetia canaliculata, and Ascophyllum nodosum and the red seaweeds Chondrus crispus and Plocamium hamatum contain bromoperoxidases. The intact plants are able to brominate exogeneous organic compounds when H{sub 2}O{sub 2} and Br{sup {minus}} are added to seawater. Further, the authors show that the brominating activity of the brown macroalga A. nodosum, which contains a vanadium bromoperoxidase located on the thallus surface, occurs when the plant is exposed to light and not in the dark. The rate of bromination of exogenous organic compounds in seawater by this plant is 68 nmol (g of wet alga){sup {minus}1} h{sup {minus}1}. HOBr is a strong biocidal agent and the authors propose that the formation of HOBr by this seaweed is part of a host defense system.

  10. Different speciation for bromine in brown and red algae, revealed by in vivo X-ray absorption spectroscopic studies.

    Science.gov (United States)

    Küpper, Frithjof C; Leblanc, Catherine; Meyer-Klaucke, Wolfram; Potin, Philippe; Feiters, Martin C

    2014-08-01

    Members of various algal lineages are known to be strong producers of atmospherically relevant halogen emissions, that is a consequence of their capability to store and metabolize halogens. This study uses a noninvasive, synchrotron-based technique, X-ray absorption spectroscopy, for addressing in vivo bromine speciation in the brown algae Ectocarpus siliculosus, Ascophyllum nodosum, and Fucus serratus, the red algae Gracilaria dura, G. gracilis, Chondrus crispus, Osmundea pinnatifida, Asparagopsis armata, Polysiphonia elongata, and Corallina officinalis, the diatom Thalassiosira rotula, the dinoflagellate Lingulodinium polyedrum and a natural phytoplankton sample. The results highlight a diversity of fundamentally different bromine storage modes: while most of the stramenopile representatives and the dinoflagellate store mostly bromide, there is evidence for Br incorporated in nonaromatic hydrocarbons in Thalassiosira. Red algae operate various organic bromine stores - including a possible precursor (by the haloform reaction) for bromoform in Asparagopsis and aromatically bound Br in Polysiphonia and Corallina. Large fractions of the bromine in the red algae G. dura and C. crispus and the brown alga F. serratus are present as Br(-) defects in solid KCl, similar to what was reported earlier for Laminaria parts. These results are discussed according to different defensive strategies that are used within algal taxa to cope with biotic or abiotic stresses. PMID:26988449

  11. Determination of elemental affinities by density fractionation of bulk coal samples

    Energy Technology Data Exchange (ETDEWEB)

    Querol, X.; Alastuey, A.; Juan, R.; Huerta, A.; Lopez- Soler, A.; Plana, F.; Chenery, S.R.N.; Robinson, J. [Consejo Superior de Investigaciones Cientificas, Barcelona (Spain). Institute of Earth Sciences ' Jaume Almera'

    2000-06-01

    In order to determine the trace elements affinities in the coal studied, density separations were carried out. Seven density fractions between {lt}1.3 and {gt}2.8 g/cc were obtained from the bulk coal samples by using heavy liquid mixtures of bromoform, tetrachlorethylene and xylene. For each density fraction the concentrations of the different mineral phases and major and trace elements were determined. After the correlation of the mineral and trace element contents, the affinity of each trace element was inferred. The mineral varieties and their contents in the bulk coal and density fractions were determined by X-ray diffraction analysis. If the method of density separation is used for the determination of the trace element affinities in coal, it is possible to determine the trace element associations by means of the simple correlation between major constituents (Al for the aluminium-silicate group, Fe for the sulphide group, and C for the organic matter) and the trace element contents for each density fraction. The results obtained by this method have lower resolution due to the fact that the high concentrations of some elements shown by the heaviest density fractions (rich in sulphides) obscure the correlation with other organic or mineral phases. 2 refs., 11 tabs.

  12. A novel process for preparation of ultra-clean micronized coal by high pressure water jet comminution technique

    Energy Technology Data Exchange (ETDEWEB)

    Longlian Cui; Liqian An; Weili Gong; Hejin Jiang [China University of Mining and Technology, Beijing (China). School of Mechanics, Architecture and Civil Engineering

    2007-03-15

    A novel process for the preparation of ultra-clean micronized coal is presented in this paper. High pressure water jet mill replacing the ball mill is employed for coal comminution in the new preparation process, which is the essential difference from the traditional one. To compare the new preparation process with the traditional one, the comparison experiments were performed, with froth flotation tests of the fine particles ground by both mills using diesel oil and n-dodecane as collector, 2-octanol as frother, and sink-float separation tests using mixtures of carbon tetrachloride-benzene and carbon tetrachloride-bromoform as dense liquid. Different parameters including combustible recovery, ash content of the clean coal, separation efficiency, and energy consumption were investigated based on the two different preparation processes. The results show that the new preparation process has high combustible recovery, low ash content of the product, high separation efficiency, and low energy consumption compared with the traditional one. The comminution mechanism of high pressure water jet mill is introduced in this paper. The high pressure water jet comminution technique has great potential in coal pulverization, having the advantages of low energy consumption, low iron content, and low equipment wear. 35 refs., 4 figs., 7 tabs.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Distributions and sources of volatile chlorocarbons and bromocarbons in the Yellow Sea and East China Sea

    International Nuclear Information System (INIS)

    Highlights: • Concentrations of the six VHOC were determined in the Yellow Sea and East China Sea. • VHOC distributions were affected by anthropogenic, biologic and hydrographic factors. • Diurnal variations of the six VHOC were observed. • Relationships between VHOC and related parameters were discussed. • Sources of the six VHOC were identified by principal component analysis. - Abstract: Six volatile halogenated organic compounds (VHOC), namely, chloroform, carbon tetrachloride, trichloroethylene, bromodichloromethane, dibromochloromethane, and bromoform, were studied in the Yellow Sea and East China Sea from April to May, 2009. The spatial variability of these VHOC was influenced by various factors, including anthropogenic inputs, biogenic production and complicated hydrographic features such as Changjiang Diluted Water, Yellow Sea Cold Water Mass, and Kuroshio Current. Diurnal study results showed that factors such as solar irradiation, biological activity, and tide affected the abundance of these VHOC. Correlation analyses revealed that bromodichloromethane was positively correlated with chlorophyll a in surface seawater. Principal component analysis suggested that chlorinated compounds like carbon tetrachloride originated from anthropogenic sources whereas brominated compounds such as bromodichloromethane originated from biogenic sources. Sources of other chlorinated and brominated compounds may not be governed by biological processes in the marine environment

  20. Heavy mineral distribution in stream sediment of Tapah area, Perak, Malaysia

    Science.gov (United States)

    Sibon, Mahat Hj; Jamil, Habibah; Umor, Mohd Rozi; Hassan, Wan Fuad Wan

    2013-11-01

    This paper aims to provide the overview of occurrence, distribution and origin of the heavy minerals in the study area. A total of 45 selected stream sediment heavy mineral concentrate samples were panned using standard dulangs, dried and separated from other light minerals using bromoform. The heavy minerals were separated into different fractions at different amperes using Frantz Isodynamic magnetic separator. Mineral identification was done using binocular microscope augmented by X-ray diffraction analyses. Mineral abundance data were analysed graphically using triangular diagrams to show their origin. Dominant minerals present in the heavy mineral samples collected are ilmenite, cassiterite, tourmaline, zircon, topaz, and magnetite. The less common minerals, present in trace amounts are hematite, xenotime, allanite, monazite, rutile, anatase, leucoxene, chromite, garnet and olivine. Examination of the heavy mineral assemblage shows that they originated from granite batholiths of the Main Range, Changkat Rembian as well as from the metasedimentary rock in the area. The gold flakes present are found together with cassiterite and topaz indicating that gold originates from the mineralized veins contact-metamorphosed metasedimentary rocks. Almost all samples collected contain cassiterite grains in various amounts. From the mineral assemblage, the source of cassiterite originates from the mineralized quartz veins that cut granitic rocks of Main Range, Changkat Rembian as well as the metasedimentary rock in the area. Greisenized veins containing quartz, mica and tourmaline with the presence of wolframite and arsenopyrite also contribute to the presence of cassiterite in this study area.

  1. Fibre selection based on an overall analytical feature comparison for the solid-phase microextraction of trihalomethanes from drinking water.

    Science.gov (United States)

    San Juan, Pedro Manuel; Carrillo, José David; Tena, María Teresa

    2007-01-12

    This paper describes the optimization of solid-phase microextraction (SPME) conditions for three different fibres (Carboxen-polydimethylsiloxane (CAR-PDMS), divinylbenzene-Carboxen-polydimethylsiloxane (DVB-CAR-PDMS) and polydimethylsiloxane-divinylbenzene (PDMS-DVB)) used to determine trihalomethanes (THMs) in water by headspace solid-phase microextraction and gas chromatography (HS-SPME-GC). The influence of temperature and salting-out effect was examined using a central composite design for each fibre. Extraction time was studied separately at the optimum values found for temperature and sodium chloride concentration (40 degrees C and 0.36g mL-1). The HS-SPME-GC-MS method for each fibre was characterised in terms of linearity, detection (LOD) and quantification (LOQ) limits and repeatability. The fibre PDMS-DVB was selected as it provided a broader linear range, better repeatability and lower detection and quantification limits than the others, particularly CAR-PDMS fibre. The accuracy of the proposed method using the PDMS-DVB fibre was checked by a recovery study in both ultrapure and tap water. A blank analysis study showed the absence of memory effects for this fibre. The reproducibility (expressed as a percentage of relative standard deviation) was 6-11% and the detection limits were between 0.078 and 0.52microgL-1 for bromoform and chloroform, respectively. Finally, the method was applied to determine THM concentration in two drinking water samples. PMID:17109874

  2. New method for determination of trihalomethanes in exhaled breath: Applications to swimming pool and bath environments

    International Nuclear Information System (INIS)

    A method for the estimation of the human intake of trihalomethanes (THMs), namely chloroform, bromodichloromethane, dibromochloromethane and bromoform, during showering and bathing is reported. The method is based on the determination of these compounds in exhaled breath that is collected by solid adsorption on Tenax using a device specifically designed for this purpose. Instrumental measurements were performed by automatic thermal desorption coupled to gas chromatography with electron capture detection. THMs in exhaled breath samples were determined during showering and swimming pool attendance. The levels of these compounds in indoor air and water were also determined as reference for interpretation of the exhaled breath results. The THM concentrations in exhaled breath of the volunteers measured before the exposure experiments showed a close correspondence with the THMs levels in indoor air where the sampler was located. Limits of detection in exhaled breath were dependent on THM analytes and experimental sites. They ranged between 170 and 710 ng m-3 in the swimming pool studies and between 97 and 460 ng m-3 in the showering studies. Application of this method to THMs determination during showering and swimming pool activities revealed statistically significant increases in THMs concentrations when comparing exhaled breath before and after exposure.

  3. 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

    2016-01-01

    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. PMID:27353292

  4. Predictors of Third Trimester Blood Trihalomethanes and Urinary Trichloroacetic Acid Concentrations among Pregnant Women.

    Science.gov (United States)

    Zeng, Qiang; Cao, Wen-Cheng; Zhou, Bin; Yang, Pan; Wang, Yi-Xin; Huang, Zhen; Li, Jin; Lu, Wen-Qing

    2016-05-17

    Prenatal exposure to disinfection byproducts (DBPs) has been associated with a variety of adverse birth outcomes. However, little is known about predictors of prenatal biomarkers of exposure to DBPs among pregnant women. We aimed to identify predictors of third trimester blood trihalomethanes (THMs) and urinary trichloroacetic acid (TCAA) concentrations, two biomarkers of exposure to DBPs, among pregnant women. Blood samples, urine samples, and questionnaires on individual characteristics and water-use activities were collected from 893 pregnant women in a Chinese cohort study. Maternal blood THM [chloroform (TCM), bromodichloromethane (BDCM), dibromochloromethane (DBCM), and bromoform (TBM)] and urinary TCAA concentrations were measured. We used multivariable linear regression to identify the predictors of third trimester blood THM and creatinine-adjusted urinary TCAA concentrations. The geometric mean of blood TTHM (sum of TCM, BDCM, DBCM, and TBM) and creatinine-adjusted urinary TCAA concentrations were 51.90 ng/L and 9.66 μg/g creatinine, respectively. Study city was the strongest significant predictors of blood THM and creatinine-adjusted urinary TCAA concentrations. Prenatal body mass index (BMI) was associated with decreased blood THM and decreased creatinine-adjusted urinary TCAA concentrations. Age was associated with increased blood Br-THM (sum of BDCM, DBCM, and TBM) concentrations. Intake of boiled water and passive smoking were associated with lower blood THM concentrations. The predictors of blood THM and urinary TCAA concentrations identified in this study provide potential health implications on how to reduce DBP exposure during pregnancy. PMID:27095243

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

    Science.gov (United States)

    Calderón-Preciado, Diana; Matamoros, Víctor; Bayona, Josep M

    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(-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(-1), on average). The estimated concentration of micropollutants in crops ranged from micropollutants through fruit and vegetable consumption was estimated to be 9.8 μg per person and week (Σ 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. PMID:22030249

  6. 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

    2016-01-01

    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. PMID:27353292

  7. 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.

  8. Springtime surface ozone fluctuations at high Arctic latitudes and their possible relationship to atmospheric bromine

    Science.gov (United States)

    Oltmans, Samuel J.; Sheridan, Patrick J.; Schnell, Russell C.; Winchester, John W.

    1988-01-01

    At high Arctic stations such as Barrow, Alaska, springtime near-surface ozone amounts fluctuate between the highest and lowest values seen during the course of the year. Episodes when the surface ozone concentration is essentially zero last up to several days during this time of year. In the Arctic Gas and Aerosol Sampling Program (AGASP-I and AGASP-II) in 1983 and 1986, it was found that ozone concentrations often showed a very steep gradient in altitude with very low values near the surface. The cold temperatures, and snow-covered ground make it unlikely that the surface itself would rapidly destroy significant amounts of ozone. The AGASP aircraft measurements that found low ozone concentrations in the lowest layers of the troposphere also found that filterable excess bromine (the amount of bromine in excess of the sea salt component) in samples collected wholly or partially beneath the temperature inversion had higher bromine concentrations than other tropospheric samples. Of the four lowest ozone minimum concentrations, three of them were associated with the highest bromine enrichments. Surface measurements of excess filterable bromine at Barrow show a strong seasonal dependence with values rising dramatically early in March, then declining in May. The concentration of organic bromine gases such as bromoform rise sharply during the winter and then begin to decline after March with winter and early spring values at least three times greater than the summer minimum.

  9. 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.

  10. Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products.

    Science.gov (United States)

    Ji, Yuefei; Kong, Deyang; Lu, Junhe; Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo

    2016-08-01

    Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO4(-)) with TBBPA was determined to be 5.27×10(10)M(-1)s(-1). Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO4(-). Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including β-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6-10h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health. PMID:27107323

  11. Behaviour of zirconium in the weathering of granulites from Salvador-BA/Brazil

    International Nuclear Information System (INIS)

    The weathering related to mineralogy with chemical analysis of Zr in granulites and their weathered equivalents in Salvador - Brazil, is studied. The mineralogical and petrographical characteristics were correlated with analyses for K,Al and Zr. The fresh rocks are quartz-rich pyroxene granulites, the weathered samples were submitted to bromoform and electromagnetic separations to recovery nearly pure zircon from the fraction coarser than 50 micros. These zircons were classified by color, size and shape. Proportions between different colors of zircon were correlated with petrography of fresh granulites. Studies of zircons resistent to acid attack indicated, that the darker colors were due to iron oxide staining. Chemical analyses for Zr in fresh rocks presented values higher than the values corresponding to zircon observed in thin sections, sugesting the presence of Zr as a trace element in ferromagnesian silicates. In the weathered rocks, Zr values are much higher than those corresponding to recovered zircon. Comparisons of K2O, Al2O3 and Zr values in fresh and weathered rocks indicated a loss of K2O, and a gain of Zr by weathering. However, maximum losses of K2O do not coincide with maximum gains of Zr. (author)

  12. Removal and transformation of organic matter during soil-aquifer treatment

    Institute of Scientific and Technical Information of China (English)

    ZHAO Qing-liang; XUE Shuang; YOU Shi-jie; WANG Li-na

    2007-01-01

    This study investigated the removal and transformation of organic matter through laboratory-scale soil-aquifer treatment (SAT) soil columns over a 110-day period. Reductions in total organic carbon (TOC), dissolved organic carbon (DOC),biodegradable dissolved organic carbon (BDOC), nonbiodegradable dissolved organic carbon (NBDOC) and absorbance of ultraviolet light at 254 mn (UV-254) averaged 71.46%, 68.05% , 99.31%, 33.27% and 38.96% across the soil columns, respectively.DOC/TOC ratios increased slightly with depth while BDOC/DOC ratios showed a converse trend. DOC exiting the soil-column system contained only a very small biodegradable fraction. SAT decreased the concentration of DOC present in feed water but increased its aromaticity, as indicated by specific ultraviolet light absorbance (SUVA), which increased by 50%~115% across the soil columns, indicating preferential removal of non-aromatic DOC during SAT. Overall, laboratory-scale SAT reduced trihalomethane formation potential (THMFP), although specific THMFP increased. THMFP reduction was dominated by removal in chloroform. All samples exhibited a common general relationship with respect to weight: chloroform>dichlorobromomethane >dibromochloromethane>bromoform.

  13. Measurement of unscheduled DNA synthesis and S-phase synthesis in rodent hepatocytes following in vivo treatment: Testing of 24 compounds

    International Nuclear Information System (INIS)

    The in vivo-in vitro hepatocyte DNA repair assay has been shown to be useful for studying genotoxic hepatocarcinogens. In addition, measurement of S-phase synthesis (SPS) provides an indirect indicator of hepatocellular proliferation, which may be an important mechanism in rodent carcinogenesis. This assay was used to examine 24 chemicals for their ability to induce unscheduled DNA synthesis (UDS) or SPS in Fischer-344 rats or B6C3F1 mice following in vivo treatment. Hepatocytes were isolated by liver perfusion and incubated with 3H-thymidine following in vivo treatment by gavage. Chemicals chosen for testing were from the National Toxicology Program (NTP) genetic toxicology testing program and most were also evaluated in long-term animal studies conducted by the NTP. Dinitrotoluene and Michler's Ketone induced positive UDS response in rat, while N-nitrosodiethanolamine and selenium sulfide induced equivocal UDS results in mouse and rat, respectively. BCMEE, bromoform, chloroform, PBB, 1,1,2-trichloroethane, and trichloroethylene were all potent inducers of SPS in mouse liver, while C.I. Solvent Yellow 14, and 1,1,2,2-tetrachloroethane yielded equivocal SPS results in rat and mouse, respectively. These results indicate that most of the test compounds do not induced UDS in the liver; however, the significant S-phase response induced by many of these compounds, especially the halogenated solvents, may be an important mechanism in their hepatocarinogenicity

  14. Cometabolism of trihalomethanes by mixed culture nitrifiers.

    Science.gov (United States)

    Wahman, David G; Henry, Andrea E; Katz, Lynn E; Speitel, Gerald E

    2006-10-01

    Three mixed-culture nitrifier sources degraded low concentrations (25-450 microg/L) of four trihalomethanes (THMs) (trichloromethane (TCM) or chloroform, bromodichloromethane (BDCM), dibromochloromethane (DBCM), tribromomethane (TBM) or bromoform) commonly found in treated drinking water. Individual THM rate constants (k1THM) increased with increasing THM bromine-substitution with TBM>DBCM>BDCM>TCM and were comparable to previous studies with the pure culture nitrifier, Nitrosomonas europaea. A decrease in temperature resulted in a decrease in both ammonia and THM degradation rates with ammonia rates affected to a greater extent than THM degradation rates. The significant effect of temperature indicates that seasonal variations in water temperature should be a consideration for technology implementation. Product toxicity, measured by transformation capacity (T(c)), was similar to that observed with N. europaea. Because both rate constants and product toxicities increase with increasing THM bromine-substitution, a water's THM speciation is an important consideration for process implementation during drinking water treatment. Even though a given water is kinetically favored, the resulting THM product toxicity may not allow stable treatment process performance. PMID:16970971

  15. 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.

  16. 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 (Pdisinfection method. TOC showed a good correlation with the concentrations of DBPs in all swimming pools (chlorine; r=0.82, Pchlorine; r=0.52, Pdisinfected 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.

  17. 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.

  18. 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.

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

    Science.gov (United States)

    Calderón-Preciado, Diana; Matamoros, Víctor; Bayona, Josep M

    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(-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(-1), on average). The estimated concentration of micropollutants in crops ranged from <1 to 7677 ng kg(-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 μg per person and week (Σ 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.

  20. 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.

  1. 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.)

  2. 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

  3. 4-氨基苯甲酸的合成工艺研究%Synthesis techniques of 4-amino benzoic acid

    Institute of Scientific and Technical Information of China (English)

    周石洋; 陈玲; 冯豫川

    2013-01-01

    以苯胺为原料,经酰基化、溴仿两步反应合成得到了目标产物,并采用IR、1HNMR和13CNMR对产物结构进行了表征.探讨了酰基化反应时催化剂AlCl3用量、反应温度及反应时间对4-氨基苯乙酮产率的影响,以及溴仿反应中反应温度、反应时间和滴加4-氨基苯乙酮速率对产物产率的影响.在最佳合成条件下,标题化合物的产率可达94.0%.本合成方法降低了工艺要求,减少合成步骤,提高了产率.%With aniline as raw material,through acylation,bromoform reactions,the target compound 4-amino benzoic acid was synthesized and confirmed by IR,1HNMR and 13CNMR.In the acylation reaction,the influence of dosage of catalyst AlCl3,reaction temperature and reaction time on the yield of intermediate 4-amino acetophenone was investigated.In the iodoformation reaction,the influence of reaction temperature,reaction time and adding rate of 4-amino acetophenone on the yield of 4-amino benzoic acid was investigated.Under the optimal conditions,the yield of 4-amino benzoic acid was 94.0%.This synthetic method has reduced process requirement and synthetic steps to improve the yield.

  4. 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.

  5. 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.

  6. 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.

  7. Optical properties of flyash. Quarterly report, 1 April--30 June 1989

    Energy Technology Data Exchange (ETDEWEB)

    Self, S.A.

    1989-07-01

    The purpose of this task is to validate the whole approach adopted in this program. Specifically, this bench-scale experiment is intended to compare the measured optical/radiative properties of a dispersion of well characterized ash with those calculated on the basis of the known size/composition distribution using the correlation formulae relating the composition and complex refractive index resulting from measurements on bulk samples of synthetic slag. Considerable thought has been given to the various possible approaches to satisfying the objectives of this task. Several experiments were done to guide our design of an apparatus for measuring the scattering and absorption properties of dispersions of flyash. As a result of these experiments, and from extensive prior experience in connection with research on electrostatic precipitation, it has been determined that there is no satisfactory way to satisfy the aims of this task using a gaseous dispersion of flyash because it is not possible to adequately disperse and deagglomerate flyash into a gas stream. Unless the ash is adequately dispersed, as it exists in the radiant boiler of a pulverized coal-fired combustion system, one cannot expect calculations, based on Mie calculations for a dispersion of spheres to properly agree with laboratory measurements. For these reasons, our design efforts are based on making measurements on a dispersion of flyash in liquid, for which our experience shows we can obtain stable, well-deagglomerated dispersions of ash. Because there is not single liquid which is adequately transparent over the wavelength range 1--12 {mu}m, we plan to use a combination of three liquids, C Cl{sub 4}, C S{sub 2} and bromoform to cover the full range. Windows of BaF{sub 2} will be used to contain the liquid suspension in an absorption/scattering cell.

  8. Optical properties of flyash

    Energy Technology Data Exchange (ETDEWEB)

    Self, S.A.

    1989-07-01

    The purpose of this task is to validate the whole approach adopted in this program. Specifically, this bench-scale experiment is intended to compare the measured optical/radiative properties of a dispersion of well characterized ash with those calculated on the basis of the known size/composition distribution using the correlation formulae relating the composition and complex refractive index resulting from measurements on bulk samples of synthetic slag. Considerable thought has been given to the various possible approaches to satisfying the objectives of this task. Several experiments were done to guide our design of an apparatus for measuring the scattering and absorption properties of dispersions of flyash. As a result of these experiments, and from extensive prior experience in connection with research on electrostatic precipitation, it has been determined that there is no satisfactory way to satisfy the aims of this task using a gaseous dispersion of flyash because it is not possible to adequately disperse and deagglomerate flyash into a gas stream. Unless the ash is adequately dispersed, as it exists in the radiant boiler of a pulverized coal-fired combustion system, one cannot expect calculations, based on Mie calculations for a dispersion of spheres to properly agree with laboratory measurements. For these reasons, our design efforts are based on making measurements on a dispersion of flyash in liquid, for which our experience shows we can obtain stable, well-deagglomerated dispersions of ash. Because there is not single liquid which is adequately transparent over the wavelength range 1--12 {mu}m, we plan to use a combination of three liquids, C Cl{sub 4}, C S{sub 2} and bromoform to cover the full range. Windows of BaF{sub 2} will be used to contain the liquid suspension in an absorption/scattering cell.

  9. 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.

  10. 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.

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

    International Nuclear Information System (INIS)

    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. - 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

  12. 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.

  13. Formation of halogenated disinfection by-products in cobalt-catalyzed peroxymonosulfate oxidation processes in the presence of halides.

    Science.gov (United States)

    Xie, Weiping; Dong, Wei; Kong, Deyang; Ji, Yuefei; Lu, Junhe; Yin, Xiaoming

    2016-07-01

    Sulfate radicals (SO4(-)) generated by activation of peroxymonosulfate (PMS) and persulfate (PS) are highly oxidative and applied to degrade various organic pollutants. This research was designed to investigate formation of halogenated by-products in Co(2+) activated PMS process in the presence of halides and natural organic matter (NOM). It was revealed that no halogenated by-products were detected in the presence of Cl(-) while 189 μg/L bromoform and 100.7 μg/L dibromoacetic acid (DBAA) were found after 120 h when 2 mg/L NOM, 0.1 mM Br(-), 1.0 mM PMS, and 5 μL Co(2+) were present initially. These products are known as disinfection by-products (DBPs) since they are formed in water disinfection processes. Formation of DBPs was even more significant in the absence of Co(2+). The data indicate that both PMS and SO4(-) can transform Br(-) to reactive bromine species which react with NOM to form halogenated by-products. Less DBP formation in Co(2+)-PMS systems was due to the further destruction of DBPs by SO4(-). More DBPs species including chlorinated ones were detected in the presence of both Cl(-) and Br(-). However, more brominated species produced than chlorinate ones generally. The total DBP yield decreased with the increase of Cl(-) content when total halides kept constant. This is one of the few studies that demonstrate the formation of halogenated DBPs in Co(2+)/PMS reaction systems, which should be taken into consideration in the application of SO4(-) based oxidation technologies. PMID:27093695

  14. 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.

  15. 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.

  16. 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.

  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. Identifying emission source regions and transport pathways of very short-lived halogens over the Western Pacific

    Science.gov (United States)

    Butler, Robyn; Palmer, Paul; Feng, Liang; Harris, Neil; Carpenter, Lucy; Andrews, Steve; Atlas, Elliot; Salawitch, Ross; Pan, Laura; Donets, Valeria; Schauffler, Sue

    2016-04-01

    Deep, tropical convective systems lead to the rapid transport of very short-lived halogenated substances (VSLS) to the tropical tropopause layer (TTL). They are then subsequently transported to the lower stratosphere and chemically broken down to release the constituent halogens that catalytically destroy ozone. Although the oceans are known to represent the largest VSLS source, the relative contribution of geographical regions through emission and transport is poorly understood. We present a study on the origin and variability of VSLS over the Western Pacific using data collected during the CAST and CONTRAST measurement campaigns, January/February 2014. We have developed a version of the GEOS-Chem atmospheric chemistry transport model that tags emissions of bromoform (CHBr3) and dibromomethane (CH2Br2) from different geographical regions. We focus the source regions on land and (coastal and open) oceanic emissions. We have also developed a similar tagged method to calculate the physical age of air parcels from these source regions to quantify the speed of vertical transport. Using this approach we have quantified relative contributions of source regions and show that open oceanic emission regions are the dominant source of VSLS gases during the measurement campaigns. By looking at variability over the region, we see that this is caused by direct convection of marine emissions over the open ocean leading to increased contribution to CHBr3 and CH2Br2 mixing ratios from this source region. Open oceanic emissions are transported to the TTL within the average atmospheric lifetime of CHBr3, the shorter lived species, whereas emissions from coastal ocean and land source regions have an older physical age at the TTL. The relative contribution from island land masses in the campaign region have no impact over the vertical profile but does impact local mixing ratios.

  19. AN EVALUATION OF THMs IN DRINKING WATER AND A METHOD OF ITS REMOVAL

    Directory of Open Access Journals (Sweden)

    A.Torabian

    1998-03-01

    Full Text Available Chlorination of natural water containing humic compounds, produce significant amount of disinfectant by - products. The most important of such compounds are THlvIs and halo acetic acids, suspected to cause cancer in animals and human. Studies showed that under usual processes of water treatment plants, THMs can not be removed effectively. Since chlorination is the final process of treatment, it is necessary to suggest a method for removing such compounds. The primary goal of this research was to study the possibility of the presence of THMs in the drinking water and the procedures for its removal. In the first phase of this study which was done in 1996, the quality of raw and fmished water in the case of total THMs were studied for Ahwaz, Isfahan, Bandar- Abbas, Shiraz, Mashhad and Tehran. The THMs determination was done for three months in all cities, but for Tehran, fulfilled ten months for raw and seven months for the tap waters. Total THM concentrations were determined by liquid-liquid extraction and gas chromatography. Results varied from less than 5µgr/lit (the lowest concentration detectable by the method to 732 µgr/lit (THM.F.P. In for BandarAbbass tap water. Four samples out of 185, showed that total THM concentrations were above the 100 µgr/lit (MCL. In the second phase of the study, Granular Activated Carbon was used to determine its ability to remove the THM, from the water. Tap water was spiked to 500 µgr/lit using bromoform and chloroform, and then passed through the activated carbon filter. The effluent and influent of the filter were analyzed periodically to determine the concentration of THMs. After 1360 liter of spiked water was passed through, breakthrough was measured. GAC absorption follows Frendlich isotherm. K and n parameters were determined.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Formation and chemical reactivity of carbon fibers prepared by defluorination of graphite fluoride

    Science.gov (United States)

    Hung, Ching-Cheh

    1994-01-01

    Defluorination of graphite fluoride (CFX) by heating to temperatures of 250 to 450 C in chemically reactive environments was studied. This is a new and possibly inexpensive process to produce new carbon-based materials. For example, CF 0.68 fibers, made from P-100 carbon fibers, can be defluorinated in BrH2C-CH = CH-CH2Br (1,4-dibromo-2butene) heated to 370 C, and graphitized to produce fibers with an unusually high modulus and a graphite layer structure that is healed and cross-linked. Conversely, a sulfur-doped, visibly soft carbon fiber was produced by defluorinating CF 0.9 fibers, made from P-25, in sulfur (S) vapor at 370 C and then heating to 660 C in nitrogen (N2). Furthermore, defluorination of the CF 0.68 fibers in bromine (Br2) produced fragile, structurally damaged carbon fibers. Heating these fragile fibers to 1100 C in N2 caused further structural damage, whereas heating to 150 C in bromoform (CHBr3) and then to 1100 C in N2 healed the structural defects. The defluorination product of CFX, tentatively called activated graphite, has the composition and molecular structure of graphite, but is chemically more reactive. Activated graphite is a scavenger of manganese (Mn), and can be intercalated with magnesium (Mg). Also, it can easily collect large amounts of an alloy made from copper (Cu) and type 304 stainless steel to form a composite. Finally, there are indications that activated graphite can wet metals or ceramics, thereby forming stronger composites with them than the pristine carbon fibers can form.

  5. Exhaust constituent emission factors of printed circuit board pyrolysis processes and its exhaust control

    International Nuclear Information System (INIS)

    Highlights: • Recycling of waste printed circuit boards is an important issue. • Pyrolysis is an emerging technology for PCB treatment. • Emission factors of VOCs are determined for PCB pyrolysis exhaust. • Iron-Al2O3 catalyst was employed for the exhaust control. -- Abstract: The printed circuit board (PCB) is an important part of electrical and electronic equipment, and its disposal and the recovery of useful materials from waste PCBs (WPCBs) are key issues for waste electrical and electronic equipment. Waste PCB compositions and their pyrolysis characteristics were analyzed in this study. In addition, the volatile organic compound (VOC) exhaust was controlled by an iron-impregnated alumina oxide catalyst. Results indicated that carbon and oxygen were the dominant components (hundreds mg/g) of the raw materials, and other elements such as nitrogen, bromine, and copper were several decades mg/g. Exhaust constituents of CO, H2, CH4, CO2, and NOx, were 60–115, 0.4–4.0, 1.1–10, 30–95, and 0–0.7 mg/g, corresponding to temperatures ranging from 200 to 500 °C. When the pyrolysis temperature was lower than 300 °C, aromatics and paraffins were the major species, contributing 90% of ozone precursor VOCs, and an increase in the pyrolysis temperature corresponded to a decrease in the fraction of aromatic emission factors. Methanol, ethylacetate, acetone, dichloromethane, tetrachloromethane and acrylonitrile were the main species of oxygenated and chlorinated VOCs. The emission factors of some brominated compounds, i.e., bromoform, bromophenol, and dibromophenol, were higher at temperatures over 400 °C. When VOC exhaust was flowed through the bed of Fe-impregnated Al2O3, the emission of ozone precursor VOCs could be reduced by 70–80%

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. The recovery of rare earth elements (REE) from beach sands

    International Nuclear Information System (INIS)

    This preliminary study describes a metallurgical process that will extract, recover and produce REE oxides from beach sands obtained from Ombo, San Vicente, northern Palawan. The beach sands contain REE minerals of allanite and small amounts of monazite. Allanite is a sorosilicate mineral containing rare earths, thorium and uranium. Monazite is the anhydrous phosphate of cerium and the lanthanum group of rare earths with thorium commonly present in replacement for cerium and lanthanum. Collected beach sand were first pan-concentrated in-situ to produce heavy mineral concentrates. Screening using a 32 mesh (0.500 mm) sieve was done at the Nuclear Materials Research Laboratory to remove oversize sand particles. The -32 mesh fraction was treated with bromoform (sp. gr. 2.89) to separate the heavy minerals from siliceous gangue. Grinding to -325 mesh size (0.044mm) followed to liberate the minerals prior to leaching. Two acids leachants were used - concentrated HCl for the first trial and a mixture of concentrated HCl and HNO3 (10:1 volume ratio) for the second trial. Both leaching trials were carried out at 180oC for 7 hours or until dry. The resulting leached residues were re-dissolved in concentrated HCl and filtered. IonquestR 801, an organophosphorous extractant, was added to the filtrate to separate the radioactive thorium from REE. Sodium hydroxide was added to the aqueous phase to precipitate the REE. After filtering the precipitate, it was dissolved in HCl. The acid solution was repeatedly extracted three (3) times with IonquestR 801 to remove iron and other contaminants. Ammonium hydroxide was added to the final solution to precipitate the REE, which was then dried in the oven. The precipitate was calcined/roasted in the furnace at two different temperatures for different periods of time to burn off the organic matter and to form oxides. Results of the XRD analysis showed peaks of the calcined precipitate matching with the peaks of lanthanum oxide standard

  13. 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

  14. Dating of zircons by the fission track method

    International Nuclear Information System (INIS)

    This work describes the methodology to date zircons by the Fission Track Method. A brief discussion is made of the physical principles of the method, physical properties of zircons and the geochemical properties of uranium. When starting with a hand sample, a mineral separation is required; to do this the following steps are needed: crushing and sieving of the sample, washing and drying, magnetic separation, heavy liquid separation (Bromoform 2.89 g/cm3, Diyodomethane = 3.31 g/cm3), and manual separation on a stereoscopic microscope. Once the zircon concentrate is obtained, these are mounted on a FEP teflon mount, then polished and etched on an eutectic mix of 10 g. of KOH + 7.2 g. of NaOH, heated to 210 Centigrade degrees. Afterwards the mounts are prepared for irradiation, sterilizing and putting on top of them an external detector (a thin sheet of muscovite poor in uranium content). The package is then wrapped in plastic and sent to the reactor together with standard zircons of known age (Fish Canyon Tuff: Naeser et.al., 1981), mounted in the same way, plus standard glasses of known uranium content. The package was irradiated in a site known as SIRCA (Rotatory Capsules Irradiation System). Then the package is left to decay for several days, and then the external detectors are etched in a 48% concentrated hydrofluoric acid for 5 minutes. Once the samples are processed through the mentioned steps, spontaneous tracks appear in the zircons and induced tracks appear in the external detectors. On counting the tracks one obtains ρs (spontaneous track density) and ρ1 (induced track density). These two parameters together with another one called '#zeta #' (obtained from the standard zircons and glasses), are used to obtain the age of the sample. Zircons from Cerro de Mercado, Durango were dated and the age obtained was 30 ±5 Ma. This date is in agreement with similar results obtained by Fleisher and Naeser (1975) for zircons of the same locality and dated by the same

  15. Transport of NMHCs and halocarbons observed by CARIBIC: A case study

    Science.gov (United States)

    Baker, A. K.; Brenninkmeijer, C. A. M.; Oram, D. E.; O'Sullivan, D. A.; Schuck, T. J.; Slemr, F.

    2009-04-01

    The CARIBIC project (Civil Aircraft for the Regular Investigation of the Atmosphere Based on an Instrument Container) involves the monthly deployment of an instrument container equipped to make atmospheric measurements from onboard a long-range commercial airliner. Since December 2004, flights for the second phase of CARIBIC have been aboard a Lufthansa Airbus A340-600 traveling between Frankfurt, Germany and destinations in Asia, North America and South America. The instrument package housed in the container is fully automated and during each flight carries out a variety of real-time trace gas and aerosol measurements, and also collects 28 air samples, which are analyzed upon return to the laboratory. Routine measurements made from the sampling flasks include greenhouse gases, nonmethane hydrocarbons (NMHCs), and halocarbons; results of air sample analysis form the basis for the data discussed here. While the majority of CARIBIC samples represent background free tropospheric air and air representative of the upper troposphere/lower stratosphere, the aircraft also, less frequently, encounters air parcels influenced by more recent emissions. Here we present a case study of a round-trip flight between Frankfurt and Toronto, Canada during September 2007. During this flight, different air masses of unique origin were encountered; a number of samples were influenced by transport from the Gulf of Mexico, while others had source regions in Central and Southeast Asia. Samples from the Gulf of Mexico exhibited enhancements in C3-C6 alkanes, as well as a number of halogenated compounds with oceanic sources, such as methyl iodide and bromoform, while Asian samples had enhanced levels of combustion products (CO, acetylene, benzene) and anthropogenic halocarbons (methlyene chloride, chloroform, perchloroethylene). Additionally, a number of samples also showed stratospheric influence, and these samples were characterized by relatively depleted levels of many of the compounds

  16. 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

  17. Contamination of sediments and water of a wet dune slack (SW Portugal)

    Science.gov (United States)

    Conceição Freitas, Maria; Rosário Carvalho, Maria; Andrade, César; Cruces, Aanabela; Moreira, Sandra

    2015-04-01

    Lagoa da Sancha (LS), located in the Portuguese SW coast, is a small (0.12km2) wet dune slack with a shallow (<1m) open-water body, which occasionally dries out in summer. This environment is part of a Natural Reserve since 2000. It collects inputs from a 35km2 watershed essentially draining Cenozoic sandy materials. The main anthropogenic activities in the catchment area are related to agriculture and hog raising; however, an industrial waste disposal located proximal to LS, infilling an abandoned quarry, has been recently discovered. Field surveys have been conducted in March 2014 in order to collect sediment and water samples in LS as well as in the industrial waste disposal (TW3); riverine water and sediments and underground water have also been collected. Sedimentological (texture, pH, calcium carbonate and organic matter content) and geochemical (major elements, metals and organic compounds) analysis have been performed. Results show that riverine and groundwater have neutral pH and low to medium mineralization of NaCl to CaHCO3 types. The only metal found in high concentrations is iron, with a maximum value of 1200 ug/L. The texture and composition of alluvial sediments are compatible with the geologic background. LS bottom sediments areCaCO3-free organic muds, hyperacid and low organic; they present high contents of heavy metals, organic compounds (101 to 102 mg/kg) and S (2700 mg/kg). Also, the LS hydrosome presents pH values < 3, electric conductivity up to ≈ 8 mS/cm and very high concentrations of dissolved metals (iron attains 20000 ug/L and the heavy metals content is up to 3 orders of magnitude higher than in both the surface and groundwater). Dissolved hydrocarbon species (fraction C4-C10) reach 11 ug/L and bromoform 17 ug/L. Chemical analysis to TW3 revealed the presence of a large diversity of organic compounds in concentrations of up to 105 mg/kg. Hydrocarbon species and very high S content were only found in the soil and water of the waste

  18. Modelling marine emissions and atmospheric distributions of halocarbons and DMS: the influence of prescribed water concentration vs. prescribed emissions

    Directory of Open Access Journals (Sweden)

    S. T. Lennartz

    2015-06-01

    Full Text Available Marine produced short-lived trace gases such as dibromomethane (CH2Br2, bromoform (CHBr3, methyliodide (CH3I and dimethylsulfide (DMS significantly impact tropospheric and stratospheric chemistry. Describing their marine emissions in atmospheric chemistry models as accurately as possible is necessary to quantify their impact on ozone depletion and the Earth's radiative budget. So far, marine emissions of trace gases have mainly been prescribed from emission climatologies, thus lacking the interaction between the actual state of the atmosphere and the ocean. Here we present simulations with the chemistry climate model EMAC with online calculation of emissions based on surface water concentrations, in contrast to directly prescribed emissions. Considering the actual state of the model atmosphere results in a concentration gradient consistent with model real-time conditions at ocean surface and atmosphere, which determine the direction and magnitude of the computed flux. This method has a number of conceptual and practical benefits, as the modelled emission can respond consistently to changes in sea surface temperature, surface wind speed, sea ice cover and especially atmospheric mixing ratio. This online calculation could enhance, dampen or even invert the fluxes (i.e. deposition instead of emissions of VSLS. We show that differences between prescribing emissions and prescribing concentrations (−28 % for CH2Br2 to +11 % for CHBr3 result mainly from consideration of the actual, time-varying state of the atmosphere. The absolute magnitude of the differences depends mainly on the surface ocean saturation of each particular gas. Comparison to observations from aircraft, ships and ground stations reveals that computing the air–sea flux interactively leads in most of the cases to more accurate atmospheric mixing ratios in the model compared to the computation from prescribed emissions. Calculating emissions online also enables effective testing of

  19. Molecular symmetry and isostructural relations in crystal phases of trihalomethanes CHCl3, CHBrCl2, CHBr2Cl, and CHBr3.

    Science.gov (United States)

    Dziubek, Kamil; Podsiadło, Marcin; Katrusiak, Andrzej

    2009-10-01

    Bromodichloromethane (CHBrCl(2)), dibromochloromethane (CHBr(2)Cl), and their parent trihalomethanes, chloroform (CHCl(3)) and bromoform (CHBr(3)), form an intriguing series of isostructural crystal phases, the sequence of which depends on the Br/Cl substitution and thermodynamic conditions. The phase behavior of these compounds has been studied by isobaric calorimetry and isothermal compression, and the crystal structure of CHBrCl(2) has been determined at 0.10 MPa/200 K, 0.73, 1.26, 2.53 GPa (all at 295 K), and that of CHBr(2)Cl at 0.43, 1.24 GPa (all at 295 K). CHBrCl(2) frozen by isobaric cooling at 0.10 MPa crystallizes in space group P1 with Z = 2, while its high-pressure polymorph in space group Pnma (Z = 4) is stable at 295 K from its freezing pressure at 0.48 to at least 2.53 GPa. At the freezing pressure of 0.29 GPa, CHBr(2)Cl crystallizes in space group P6(3), with Z = 2, and at 1.27 GPa, it transforms to the orthorhombic structure, space group Pnma (Z = 4); CHCl(3) has the identical symmetries, but their reverse sequence was observed. A subtle isostructural phase transition has been observed at 0.10 MPa and 214.9 K in CHBr(2)Cl. The relations between isostructural phases, their symmetry, and site occupation factors of halogen atoms observed in the low-temperature and high-pressure phases of trihalomethanes (CHCl(3), CHBrCl(2), CHBr(2)Cl, and CHBr(3)) have been explained by the directional character of electrostatic interactions between the molecules. A gradual ordering of the disordered Br and Cl atoms has been achieved in the compressed crystals, where the narrower volume of the atomic sites correlates with the increased occupancy of the smaller atom (chlorine). The molecular symmetry has been shown to control the molecular aggregation in the crystalline state, consistent with the crystal site-symmetry and the balance of electrostatic matching and dispersion forces between molecules. PMID:19743834

  20. Tropical deep convection and its impact on composition in global and mesoscale models – Part 2: Tracer transport

    Directory of Open Access Journals (Sweden)

    C. R. Hoyle

    2010-08-01

    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, chemistry transport, and climate chemistry 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 hours 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 differ 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 the modelling of the halogen burden of the lowermost stratosphere through species such as bromoform, or for the transport of short lived hydrocarbons into the lowermost stratosphere. The modelled tracer profiles are found to be strongly influenced by the convective transport parameterisations, and boundary layer mixing parameterisations of the models. The location of rapid transport into the upper troposphere is similar among the models, and is mostly concentrated over the western Pacific, the Maritime Continent and the Indian Ocean. In contrast, none of the models indicates significant enhancement in upward transport over western Africa. The mean mixing ratios of an idealised CO like tracer in the upper tropical troposphere are found to be sensitive to the surface CO mixing ratios in the regions with the

  1. 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

  2. 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

  3. [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.

  4. 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.

  5. 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

  6. Occurrence of Selected Organic Compounds in Groundwater Used for Public Supply in the Plio-Pleistocene Deposits in East-Central Nebraska and the Dawson and Denver Aquifers near Denver, Colorado, 2002-2004

    Science.gov (United States)

    Bails, Jeffrey B.; Dietsch, Benjamin J.; Landon, Matthew K.; Paschke, Suzanne S.

    2009-01-01

    ), which were detected in 9 of the 15 wells (60 percent of the samples). The second most frequently detected organic compound was tetrachloroethylene, detected in 4 of the 15 wells (27 percent of the samples), followed by chloroform, trichloroethylene, and 2-hydroxyatrazine (2-hydroxy-4-isopropylamino-6-ethylamino-s-triazine, or OIET), present in 3 of the 15 wells (20 percent of the samples). The pesticide compounds deisopropylatrazine (2-chloro-6-ethylamino-4-amino-s-triazine, or CEAT), metolachlor, and simazine and the volatile organic compound cis-1,2-dichloroethylene were detected in 2 of the 15 wells, and the compounds diuron and 1,2-dichloroethane were detected in only 1 of the 15 wells during the first-year sampling. Most detections of these compounds were at or near the minimum reporting levels, and none were greater than their regulatory maximum contaminant level. There were few detections of organic compounds during the first year of sampling groundwater wells in the South Platte study area. The compounds atrazine, deethylatrazine, picloram, tetrachloroethylene, methyl-tert-butyl-ether (MTBE), tris(2-butoxyethyl)phosphate, and bromoform were detected only once in all the samples from the 12 wells. Most detections of these compounds were at or near the minimum reporting levels, and none were greater than their regulatory maximum contaminant level. Second-year sampling, which included the addition of paired source- and finished-water samples, was completed at two sites in the High Plains study area. Source-water samples from the second-year sampling had detections of atrazine and deethylatrazine; at one site deisopropylatrazine and chloroform also were detected. The finished-water samples, which represent the source water after blending with water from other wells and treatment, indicated a decrease in the concentrations of the pesticides at one site, whereas concentrations remained nearly constant at a second site. The trihalomethanes (THMs or disinfec

  7. 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.

  8. 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

  9. 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

  10. 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

  11. 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

  12. 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.

  13. Chernozem aggregate waterstability loss investigation in a long-term bare fallow experiment

    Science.gov (United States)

    Vasilyeva, N. A.; Milanovskiy, E. Y.

    2009-04-01

    The research is focused on mechanisms of aggregate waterstability controlled by soil organic matter (SOM). The objects of the research are two contrast variants of typical chernozem - under native grassland and under a 60-year bare fallow experimental plot (100 m2) on the territory of Central Chernozem Biosphere Reserve, Russia. Seasonal plowing and deficiency of fresh plant residues (due to weeding out) resulted in a rapid mineralization of SOM. The Corg content in the 0-20 cm topsoil under native grassland is 6-4.5 %. For the last two decades Corg content under bare fallow has stabilized on the 2.6% level and is therefore assumed to represent stable SOM pool. However excellent aggregate waterstability of chernozem is completely lost under bare fallow. Therefore the aim of our study is to reveal the role of different SOM pools spatial and functional organization in aggregate waterstability formation. Bulk soil samples were collected from 2 m grassland profile and 1.5 m bare fallow profile with 10 cm interval and simultaneous measurements of soil field density and moisture. Following samples were analysed: bulk samples, dry and wet-sieving aggregates, undisturbed and pulverized aggregates, granule-densimetric fractions obtained by sedimentation of bulk samples (clay 5 mkm) with following densimetric fractionation in bromoform (light ? 2.4 g/cm3), and above mentioned samples after removal of SOM by hydrogen peroxide. Isolation of aggregates and granule-densimetric fractionation were carried out for bulk soils at 0-20, 40-50 and 80-90 cm depth. We use elemental analysis (C, H, N), size exclusion and hydrophobic interaction chromatography of humic substances (HS), laser diffraction particle size analysis, specific surface area (SSA) measurements by nitrogen adsorption and micromorphological examination of thin sections. Detailed characteristics obtained for aggregates and granule-densimetric fractions from a typical chernozem soil under native grassland and under 60

  14. 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

  15. 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

  16. 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.