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Sample records for bromoform

  1. Bromoform

    Integrated Risk Information System (IRIS)

    Bromoform ; CASRN 75 - 25 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effects

  2. Measurements of atmospheric methyl bromide and bromoform

    SciTech Connect

    Cicerone, R.J.; Heidt, L.E.; Pollock, W.H.

    1988-04-20

    We have measured gaseous methyl bromide (CH/sub 3/Br) and bromoform (CHBr/sub 3/) in air samples that were gathered approximately weekly from five ground-level sites: Point Barrow, Alaska; Mauna Loa Observatory and Cape Kumukahi, Hawaii; Matatula, Samoa; and Kaitorete Spit, New Zealand. Approximately 750 samples have been analyzed for CH/sub 3/Br between January 1985 and October 1987 and 990 samples have been analyzed for CHBr/sub 3/ between early 1984 and September 1987, all by gas chromatography/mass spectroscopy. Methyl bromide concentrations are typically 10--11 parts per trillion (ppt) by volume; there are no clear indications of temporal increases. Bromoform concentrations are typically 2--3 ppt, but large seasonal variations are seen at Point Barrow. copyright American Geophysical Union 1988

  3. Reductive dehalogenation of bromoform in aqueous solution.

    PubMed

    Betterton, E A; Arnold, R G; Kuhler, R J; Santo, G A

    1995-06-01

    The hybrid semiconducter-macrocycle catalyst TiO2-cobalt phthalocyanine promotes the solar photolysis of aqueous bromoform under anaerobic conditions. The major decomposition products are dibromoethane and HBr. Bromomethane and methane were produced only after prolonged photolysis (30 hr). Acetone, derived from added 2-propanol, was the only observed oxidation product. Preliminary experiments showed that electrolytic reduction of aqueous carbon tetrachloride at a vitamin B12-modified silver electrode produced the expected lower homologues but with surprisingly high yields of methane.

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

    SciTech Connect

    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.

  5. Toxicity, Bioaccumulation and Depuration of Bromoform in Five Marine Species

    SciTech Connect

    Gibson, C. I.; Tone, F. C.; Wilkinson, P.; Blaylock, J. W.; Schirmer, R. E.

    1981-01-01

    Bromoform has been identified as the single most abundant halogenated organic compound produced by the chlorination of marine waters. To determine the potential biological effects of its release into marine waters, short-term toxicity bioassays and 28-day uptake/28-day depuration studies were conducted with five marine species: Protothaca staminea, Mercenaria mercenaria, Crassostrea virginica, Penaeus aztecus, and Brevoortia tyrannus. The bioassay studies indicate that 96-hr LC50s ranged from approximately 7 ppm for B. tyrannus to greater than 40 ppm for P. staminea. Behavioral changes were noted in P. aztecus and B. tyrannus exposed to sublethal concentrations of bromoform. In all species tested, the uptake and depuration of bromoform was rapid. Bromoform was present in all exposed animal tissues within 24 hours and was depurated within 48 hours. In the mollusk species, there was bioaccumulation above water concentrations in the first week of exposure, and then the tissue concentrations fell to levels approximately equal to the water concentrations. The shrimp and menhaden also bioaccumulated bromoform above water concentrations in the first week of exposure, but then the tissue concentrations fell to approximately 0.4 {micro}g/g and remained at this level independent of water concentrations.

  6. Reaction Dynamics of the Bromine-Bromoform Complex in Solution

    NASA Astrophysics Data System (ADS)

    Preston, Thomas J.; Dutta, Maitreya; Crim, F. Fleming

    2010-06-01

    We have followed the evolution of the bromine species that arise from the photolysis of bromoform in the condensed phase. Solvent caging promotes the formation of iso-bromoform (CHBr_2-Br), which can then release a Br atom by breaking the newly formed Br-Br bond. This ejected Br can form a van der Waals complex (Br-CHBr_3) with a nearby un-photolyzed bromoform molecule, which is stable during our 1 ns time-window. Using the van der Waals complex as a reservoir for Br atoms, we now proceed to drive hydrogen abstraction from CHBr_3 by Br. Estimates indicate that the barrier to this reaction is a few thousand wavenumbers. Our goal is to introduce excitation into the C-H stretching motion of a nearby solvent CHBr_3 to access the activated complex region of the bimolecular potential energy surface.

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

    SciTech Connect

    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.

  8. Radical telomerization of vinyltrimethylsilane by bromoform and partial chain-transfer constants

    SciTech Connect

    Vasil'eva, T.T.; Kochetkova, V.A.; Nelyubin, B.V.; Freidlina, R.Kh.

    1986-12-20

    The telomerization of vinyltrimethylsilane by bromoform initiated by benzoyl peroxide occurs because of scission of the C-Br bond in bromoform and gives telomers of structure CHBr/sub 2/(CH/sub 2/CHSiMe/sub 3/)/sub n/Br, where n = 1, 2. The first partial chain-transfer constant C/sub 1/ approx. = 120. When the vinyltrimethylsilane/bromoform ratio is less than or equal to 5, by-product tetrabromo derivatives CBr/sub 3/CH/sub 2/CHBrSiMe/sub 3/ and CBr/sub 2/(CH/sub 2/CHBrSiMe/sub 3/)/sub 2/ are formed.

  9. Evolution of Bromoform in a Global Chemistry and Transport Model

    NASA Technical Reports Server (NTRS)

    Douglass, Anne R.; Pierson, J. M.; Douglass, Anne R.; Einaudi, Franco (Technical Monitor)

    2000-01-01

    It is well known that many chlorine and bromine compounds that are inert in the troposphere are destroyed in the stratosphere and contribute to the stratospheric burden of reactive chlorine and bromine species. But the contribution from those chlorine and bromine compounds which are reactive in the troposphere is less certain because it is not known whether convection can transport these gases to the upper troposphere rapidly enough to overcome their short tropospheric lifetimes. We examine this issue using a three-dimensional chemistry and transport model to simulate the evolution of three gases which have surface sources, bromoform (CHBr3), methyl chloroform (CH3CCl3), and carbon dioxide (CO2). Our objective is to determine if CHBr3 might enhance the lower stratospheric burden of reactive bromine. The other two gases provide tests of the quality of the simulation. Both CHBr3 and CH3CCl3 are destroyed in the troposphere by reaction with hydroxyl (OH), whose latitudinal and monthly variation is provided by a two-dimensional model and upon which a diurnal variation is imposed. Comparison of the lifetime of CH3CCl3 computed from observations (5 years) with the lifetime computed from the simulation provides an integrated test of the model's transport and photochemistry. Observations also show that CO2 exhibits a strong seasonal cycle in the northern hemisphere troposphere that is not propagated directly across the tropopause into the lower stratosphere. Thus, maintenance of the observed troposphere-stratosphere distinctness of CO2 in the presence of convection is a critical benchmark for meeting our objective.

  10. Estimates of tropical bromoform emissions using an inversion method

    NASA Astrophysics Data System (ADS)

    Ashfold, M. J.; Harris, N. R. P.; Manning, A. J.; Robinson, A. D.; Warwick, N. J.; Pyle, J. A.

    2014-01-01

    Bromine plays an important role in ozone chemistry in both the troposphere and stratosphere. When measured by mass, bromoform (CHBr3) is thought to be the largest organic source of bromine to the atmosphere. While seaweed and phytoplankton are known to be dominant sources, the size and the geographical distribution of CHBr3 emissions remains uncertain. Particularly little is known about emissions from the Maritime Continent, which have usually been assumed to be large, and which appear to be especially likely to reach the stratosphere. In this study we aim to reduce this uncertainty by combining the first multi-annual set of CHBr3 measurements from this region, and an inversion process, to investigate systematically the distribution and magnitude of CHBr3 emissions. The novelty of our approach lies in the application of the inversion method to CHBr3. We find that local measurements of a short-lived gas like CHBr3 can be used to constrain emissions from only a relatively small, sub-regional domain. We then obtain detailed estimates of CHBr3 emissions within this area, which appear to be relatively insensitive to the assumptions inherent in the inversion process. We extrapolate this information to produce estimated emissions for the entire tropics (defined as 20° S-20° N) of 225 Gg CHBr3 yr-1. The ocean in the area we base our extrapolations upon is typically somewhat shallower, and more biologically productive, than the tropical average. Despite this, our tropical estimate is lower than most other recent studies, and suggests that CHBr3 emissions in the coastline-rich Maritime Continent may not be stronger than emissions in other parts of the tropics.

  11. The Air-sea Flux of Bromoform: Controls, Rates and Implications

    NASA Astrophysics Data System (ADS)

    Quack, B.; Wallace, D. W. R.

    Bromoform (CHBr3) is the largest single source of organic bromine for the atmosphere and of importance for the reactive halogen budgets in troposphere and lower stratosphere. Its photochemical products may contribute 10-20% to inorganic bromine in the troposphere and >50% in the lower stratosphere. The sea-to-air flux, originating with macroalgae and plankton, is the main source for atmospheric bromoform. We address the relevance of bromoform to atmospheric chemistry, as well as oceanic source and sink processes. We have performed a reassessment of oceanic emissions, based on published aqueous and airborne concentration data, global climatological parameters, and incorporation of knowledge about bromoforms coastal and biogenic sources. The goal is partly to estimate the global source strength and partly to identify key regions that may contribute bromoform to the atmosphere and hence require further investigation. We have therefore calculated annual integrated fluxes of bromoform for different latitudes and oceanic biogeochemical provinces. We obtain a global flux in the order of 9-13 Gmol Br yr-1 (as CHBr3), which is still associated with significant uncertainties. Coastal, shelf and open ocean regions contribute 13-17%, 44-48% and 34-43% to our calculated total respectively. Anthropogenic sources of ~0.3 Gmol Br yr-1 (as CHBr3) are negligible globally. Our estimate of the global oceanic source is >3x higher than recent estimates based on the modelling of atmospheric sinks. Reasons for the discrepancy could lie with the limited regional and temporal data available and broad assumptions that underlie our flux calculations. Alternatively, atmospheric sink calculations, often calculated on the basis of background CHBr3 levels, may neglect the influence of strong but highly localised sources (e.g. from some coastal regions). We believe that our approach is useful for attempting a first approximation of the flux based on known factors affecting the oceanic bromoform

  12. Measurements of Bromoform and Dibromomethane in the Seacoast Region of NH, 2002-2004

    NASA Astrophysics Data System (ADS)

    Zhou, Y.; Russo, R.; Varner, R.; Wingenter, O.; Blake, D.; Talbot, R.; Sive, B.

    2005-12-01

    Relatively short-lived halocarbons, such as bromoform and dibromomethane, have been shown to be sources of the halogen oxide radical BrO to the atmosphere which can influence tropospheric oxidation processes in both polar and temperate regions. Under strong convective conditions, which are predominate in the tropics, relatively short lived gases can be transported to the stratosphere or reach it as inorganic bromine, thus contributing to ozone depletion. In addition, short-lived marine halocarbons have been frequently used as tracers to investigate the marine influence on air masses. Measurements of these marine tracers are important for improving our understanding of the atmospheric processes that control the production and distribution of air pollutants along coastal marine regions. Halocarbons were measured at two AIRMAP monitoring sites, Thompson Farm (TF), 25 km inland in Durham, NH from 2002-2004 and Appledore Island (AI), 10 km off the coast of NH during the ICARTT 2004 campaign. For this work, we present measurements of bromoform and dibromomethane made at TF, NH (June 1-August 31, 2002, July 3-September 17, 2003, and July 1-August 15, 2004) and at AI, ME (July 2-August 13, 2004). Additionally, results from measurements of these two gases onboard the NASA DC-8 as part of INTEX-A as well as surface seawater measurements of bromoform made onboard the NOAA ship Ronald H. Brown as part of the NEAQS 2002 campaign are presented. Average mixing ratios of bromoform and dibromomethane at AI (14 and 3 pptv, respectively) were higher than at TF in 2002, 2003, and 2004 (5-9 pptv for bromoform and 1-2 pptv for dibromomethane). Mixing ratios of bromoform and dibromomethane at Appledore Island were significantly higher and more variable than those observed at Thompson Farm, indicating the influence of the local marine sources. Thompson Farm and Appledore Island were significantly impacted by coastal sources of marine halocarbons. At both sites, higher mixing ratios of

  13. A Simulation of Bromoform's Contribution to Stratospheric Bromine

    NASA Technical Reports Server (NTRS)

    Nielsen, J. Eric; Douglass, Anne R.; Einaudi, Franco (Technical Monitor)

    2000-01-01

    Many chlorinated and brominated compounds that are inert in the troposphere are destroyed in the stratosphere and act as an in-situ source of stratospheric reactive chlorine and bromine. Other halogenated compounds that are reactive in the troposphere might contribute to the stratosphere's halogen budget in two ways. First, like their unreactive companions, rapid convective transport might carry them to the upper troposphere and make them available for subsequent advection by the mean circulation into the stratosphere before they are oxidized or photolyzed. Second, it is more likely that they are destroyed in the troposphere, and the chlorine and bromine that is released might then be transported to the stratosphere. We evaluate the relative influence of these processes on stratospheric bromine in a three-dimensional chemistry and transport model which simulates the distribution of bromoform (CHBr3). CHBr3 is parameterized as a short-lived, ocean-surface source gas whose destruction by photolysis and reaction with hydroxyl (OH) in the troposphere and stratosphere yields inorganic bromine (Br(sub y)). Many of the observed features of CHBr3 are simulated well, and comparisons with observations are used to show that the model represents aspects of transport in the upper troposphere and lower stratosphere that are critical to the evaluation. In particular, the model maintains the observed troposphere-stratosphere distinctness in transport pathways and reproduces the observed seasonal dependence of the mixture of air in the middle- and high-latitude lowermost stratosphere. We estimate that adding CHBr3 to models which already include the long-lived organic brominated compounds (halons and methyl bromide) will increase the simulated stratospheric mass of Br(sub y) by about 15 percent. In-situ stratospheric destruction of CHBr3 produces Br(sub y) in amounts which are comparable to that transported into the stratosphere after photolysis and oxidation of CHBr3 in the

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

    NASA Astrophysics Data System (ADS)

    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.

  15. HEPATOTOXIC EVALUATION OF THE BINARY INTERACTIONS OF BROMODICHLOROMETHANE WITH CHLOROFORM, CHLORODIBROMOMETHANE AND BROMOFORM

    EPA Science Inventory

    HEPATOTOXIC EVALUATION OF THE BINARY INTERACTIONS OF BROMODICHLOROMETHANE (BDCM) WITH CHLOROFORM (CHC13), CHLORODIBROMOMETHANE (CDBM) AND BROMOFORM (CHBr3). Y M Se'', C Gennings2, A McDonald', L K Teuschler3, A Hamm2and J E Simmons .'NHEERL, ORD, U.S. EPA, RTP, NC; 2MCV, VCU, Ric...

  16. REDUCTIVE DEHALOGENATION OF HEXACHLOROETHANE, CARBON TETRACHLORIDE, AND BROMOFORM BY ANTHRAHYDROQUINONE DISULFONATE AND HUMIC ACID

    EPA Science Inventory

    The reductive dehalogenation of hexachloroethane (CzCLj), carbon tetrachloride (CC14), and bromoform (CHBr3) was examined at 50 “C in aqueous solutions containing ei- ther (1) 500 pM of 2,6-anthrahydroquinone disulfonate (AHQDS), (2) 250 pM Fe2+, or (3) 250 pM HS-. The pH ranged ...

  17. Clathrate formation and phase equilibria in the thiourea-bromoform system

    NASA Astrophysics Data System (ADS)

    Chekhova, G. N.; Shubin, Yu. V.; Pinakov, D. V.; Alferova, N. I.

    2008-07-01

    Phase equilibria in the thiourea (host)-bromoform (guest) binary system were studied by physicochemical analysis methods over the temperature range 270 455 K. The stoichiometry and stability region were determined for the channel-type compound CHBr3 · 2.40(2)(NH2)2CS; the compound was observed for the first time. When heated, the clathrate incongruently decomposed at 424.0 ± 0.8 K to rhombic thiourea and the guest component. The solubility isotherm of the thiourea-bromoform-acetic acid system was studied to find that the compound was thermodynamically stable at 293 K over the range of guest component concentrations 100 35 wt %. A decrease in its content in an equilibrium mother liquor resulted in the appearance of X-ray diffraction reflections of the initial host α polymorph. Rhombohedral cell parameters were determined (space group R-3 c, a = 15.89(1) Å, c = 12.40(1) Å, V = 2711(6) Å3, d calcd = 2.000 g/cm3, and d expt = 1.98(2) g/cm3). The mode of packing of bromoform molecules was compared with the organization of the guest subsystem in inclusion compounds formed by the substances studied.

  18. 2D THz-THz-Raman Photon-Echo Spectroscopy of Molecular Vibrations in Liquid Bromoform.

    PubMed

    Finneran, Ian A; Welsch, Ralph; Allodi, Marco A; Miller, Thomas F; Blake, Geoffrey A

    2017-09-13

    Fundamental properties of molecular liquids are governed by long-range interactions that most prominently manifest at terahertz (THz) frequencies. Here we report the detection of nonlinear THz photon-echo (rephasing) signals in liquid bromoform using THz-THz-Raman spectroscopy. Together, the many observed signatures span frequencies from 0.5 to 8.5 THz and result from couplings between thermally populated ladders of vibrational states. The strongest peaks in the spectrum are found to be multiquantum dipole and 1-quantum polarizability transitions and may arise from nonlinearities in the intramolecular dipole moment surface driven by intermolecular interactions.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    Russo, M. R.; Ashfold, M. J.; Harris, N. R. P.; Pyle, J. A.

    2015-12-01

    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 idealized 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 distributed

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

    NASA Astrophysics Data System (ADS)

    Russo, M. R.; Ashfold, M. J.; Harris, N. R. P.; Pyle, J. A.

    2015-07-01

    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 distributed

  2. Genotoxicity of drinking water disinfection by-products (bromoform and chloroform) by using both Allium anaphase-telophase and comet tests.

    PubMed

    Khallef, Messaouda; Liman, Recep; Konuk, Muhsin; Ciğerci, İbrahim Hakkı; Benouareth, Djameleddine; Tabet, Mouna; Abda, Ahlem

    2015-03-01

    Genotoxic effects of bromoform and chloroform, disinfection by-products of the chlorination of drinking water, were examined by using mitotic index (MI), mitotic phase, chromosome aberrations (CAs) and comet assay on root meristematic cells of Allium cepa. Different concentrations of bromoform (25, 50, 75 and 100 μg/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 by using one-way analysis of variance were employed and p < 0.05 was accepted as significant value. Exposure of both chemicals (except 25 μg/mL applications of bromoform) significantly decreased MI. Bromoform and chloroform (except 25 μg/mL applications) increased total CAs in Allium anaphase-telophase test. A significant increase in DNA damage was also observed at all concentrations of both bromoform and chloroform examined by comet assay. The damages were higher than that of positive control especially at 75-100 μg/mL for bromoform and 100-200 μg/mL for chloroform.

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

    PubMed Central

    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

  4. Development of a simplified, cost effective GC-ECD methodology for the sensitive detection of bromoform in the troposphere.

    PubMed

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

    2012-10-10

    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).

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

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

    NASA Astrophysics Data System (ADS)

    Mantle, Hannah; Hossaini, Ryan; Chipperfield, Martyn

    2013-04-01

    Halogenated very short-lived species (VSLS) with atmospheric lifetimes of <6 months can be transported to the stratosphere, particularly in regions experiencing rapid vertical transport due to deep convection. Once in the stratosphere bromine released from VSLS contributes to ozone depletion. While the Montreal Protocol has controlled the emission of longer-lived anthropogenic halogenated species, the quantitative impact of naturally sourced VSLS remains unclear and requires further investigation. We have used the TOMCAT offline global 3-D chemical transport model (CTM) to test different VSLS emission scenarios. In this study, TOMCAT is forced using 6-hourly European Centre for Medium-Range Weather Forecasts analyses, has 60 vertical levels from the surface to ~60 km and a horizontal resolution of 2.8°x2.8°. Previous work using TOMCAT into halogenated VSLS emission and transport has involved the use of fixed surface mixing ratios of 1.2 pptv bromoform and dibromomethane in the bottom two layers of the model surface in the Tropics (Hossaini et al., 2010). Although an accurate representation of surface mixing ratios of these VSLS, the use of spatially varying emission fluxes should allow for improved accuracy in model predictions. The EU-funded SHIVA Malaysia 2011 field campaign provided a comprehensive VSLS dataset obtained in a region where these source gases have the potential to reach the stratosphere and deplete ozone. Observations of VSLS were collected during November and December 2011 on board the DLR Falcon aircraft during sixteen local flights. Fourteen of these flights have been used in this study due to technical difficulties experienced on the remaining two flights. Four emission scenarios, including both top-down and bottom-up approaches derived from airborne measurements and ocean fluxes of VSLS, were used in TOMCAT and each scenario was compared to observations of bromoform and dibromomethane collected during the SHIVA campaign. The mean bias of

  7. Monitoring and factors affecting levels of airborne and water bromoform in chlorinated seawater swimming pools.

    PubMed

    Boudenne, Jean-Luc; Parinet, Julien; Demelas, Carine; Manasfi, Tarek; Coulomb, Bruno

    2017-08-01

    Water and air quality of eight seawater swimming pools using chlorine disinfection was measured during four sampling campaigns, spread on one full-year, and in four thalassotherapy centers located in Southeast of France. Concentrations of trihalomethanes (THMs) in air and in water as well as concentrations of parameters, including nonpurgeable organic carbon (NPOC), free residual chlorine (Clf), pH, Kjeldhal Nitrogen (KN), salinity, conductivity, bromide ions and, water and air temperature, were measured. Water and air samples were collected in triplicates morning - at the opening of the pools -, noon and night - at the closing of the pools -, in summer and winter. Data analysis was performed by Principal Component Analysis (PCA) and rotated component matrix, from both data quality and other parameters such as TOC, aromaticity (UV254), pH, hygrometry, and free residual chlorine (Clf). This statistical analysis demonstrates a high correlation between TOC, Clf and UV254 and THM levels found in air and water, particularly for the major ones (CHBr3 in water: 300.0μg/L mean, 1029.0μg/L maximum; CHBr3 in air: 266.1μg/m(3) mean, 1600.0μg/m(3) maximum, and CHClBr2 in water: 18.9μg/L mean, 81.0μg/L maximum; CHClBr2 in air: 13.6μg/m(3) mean, 150.0μg/m(3) maximum). These high levels of bromoform (CHBr3) are particularly worrisome in such health institutions, even these levels do not exceed the Permissible Exposure Limit (PEL) of 5mg/m(3) as an 8hour time-weighted average currently fixed by various administrations, such as Occupational Safety and Health Administration (OSHA). Copyright © 2017. Published by Elsevier B.V.

  8. Reductive dehalogenation of hexachloroethane, carbon tetrachloride, and bromoform by anthrahydroquinone disulfonate and humic acid

    USGS Publications Warehouse

    Curtis, G.P.; Reinhard, M.

    1994-01-01

    The reductive dehalogenation of hexachloroethane (C2Cl6), carbon tetrachloride (CCl4), and bromoform (CHBr3) was examined at 50??C in aqueous solutions containing either (1) 500 ??M of 2,6-anthrahydroquinone disulfonate (AHQDS), (2) 250 ??M Fe2+, or (3) 250 ??M HS-. The pH ranged from 4.5 to 11.5 for AHQDS solutions and was 7.2 in the Fe2+ solutions and 7.8 in the HS- solutions. The observed disappearance of C2Cl6 in the presence of AHQDS was pseudo-first-order and fit k??ccl4 = k0[A(OH)2] + k1[A(OH)O-] + k2[A(O)22-] where A(OH)2, A(OH)O-, and A(O)22- represent the concentrations of the three forms of the AHQDS in solution. The values of k0, k1, and k2 were ???0,0.031, and 0.24 M-1 s-1, respectively. The addition of 25 mg of C/L of humic acid or organic matter extracted from Borden aquifer solids to aqueous solutions containing 250 ??M HS- or Fe2+ increased the reduction rate by factors of up to 10. The logarithms of the rate constants for the disappearance of C2Cl6 and CCl4 in seven different experimental systems were significantly correlated; log k???ccl4 = 0-64 log k??? c2cl6 - 0.83 with r2 = 0.80. The observed trend in reaction rates of C2Cl6 > CCl4 > CHBr3 is consistent with a decreasing trend in one-electron reduction potentials. ?? 1994 American Chemical Society.

  9. Laboratory production of bromoform, methylene bromide, and methyl iodide by macroalgae and distribution in nearshore southern California waters

    SciTech Connect

    Manley, S.L. ); Goodwin, K.; North, W.J. )

    1992-12-01

    Production rates of bromoform (CHBr[sub 3]), methylene bromide (CH[sub 2]Br[sub 2]), and methyl iodide (CH[sub 3]I) were measured in the laboratory for 11 species of marine macroalgae. Production rates of the volatile bromomethanes extrapolated to a global scale suggest that marine macroalgae produce 2 [times] 10[sup 11] g Br yr[sup [minus]1] (1 [times] 10[sup 9] mol Br yr[sup [minus]1]), 98% of which is bromoform. Laminarians (kelps) produce 61% of this organic Br. These calculations suggest that marine macroalgae are important in the biogeochemical cycling of Br. Seawater concentrations of CHBr[sub 3], CH[sub 2]Br[sub 2], and CH[sub 3]I were determined from various southern California coastal locales. High concentrations were measured in seawater from the canopy and the bottom of a dense bed of Macrocystis as compared to other sites. Surface seawater concentrations of these halomethanes showed a strong cross-shore gradient with the highest concentration in the kelp canopy and the lowest at 5 km offshore. Seawater adjacent to decaying macroalgae on the bottom of a submarine canyon was not enriched in halomethanes relative to surface water. Water exiting a productive estuary was enriched only with CH[sub 2]Br[sub 2], although two algal species that are abundant there (Ulva and Enteromorpha) showed high laboratory production rates of both CHBr[sub 3] and CH[sub 2]Br[sub 2]. 21 refs., 2 figs., 2 tabs.

  10. Spatial and temporal distributions of bromoform and dibromomethane in the Atlantic Ocean and their relationship with photosynthetic biomass

    NASA Astrophysics Data System (ADS)

    Liu, Yina; Yvon-Lewis, Shari A.; Thornton, Daniel C. O.; Butler, James H.; Bianchi, Thomas S.; Campbell, Lisa; Hu, Lei; Smith, Richard W.

    2013-08-01

    Atmospheric mixing ratios and seawater concentrations of bromoform (CHBr3), dibromomethane (CH2Br2), and other brominated very short-lived substances (BrVSLS) were measured during five cruises from 1994 to 2010. These cruises were conducted over large latitudinal (62°N-60°S) and longitudinal transects (11°W-86°W) in the Atlantic Ocean. Elevated seawater concentrations of CHBr3 and CH2Br2 were often observed in regions where chlorophyll a concentrations were also elevated, which suggests biogeochemical processes associated with photosynthetic biomass may be related to CHBr3 and CH2Br2 production. Our results suggest that, at least in the open ocean, several phytoplankton taxa may contribute to the production of these trace gases. While observed correlations between CHBr3 and CH2Br2 in different regions are usually interpreted as common sources for these compounds, results in this study suggest different biogeochemical processes may contribute separately to the production of these trace gases. Heterotrophic bacterial abundance was significantly correlated with CH2Br2, but not with CHBr3, which suggests the biogeochemical processes associated with heterotrophic bacteria may be related to CH2Br2 in seawater but probably not to CHBr3. In general, the Atlantic Ocean is a net source for CHBr3 and CH2Br2, except for a few locations where these trace gases were undersaturated in seawater. Assuming fluxes measured in the Atlantic open ocean are globally representative, the resulting extrapolated, global open-ocean annual net sea-to-air fluxes calculated from data from the five cruises was estimated at 0.24-3.80 Gmol Br yr-1 for CHBr3 and 0.11-0.77 Gmol Br yr-1 for CH2Br2.

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

    PubMed

    George, Lisa; Kalume, Aimable; Esselman, Brian J; Wagner, James; McMahon, Robert J; Reid, Scott A

    2011-09-28

    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-CHBr(3)) 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 CHBr(3) isolated in Ar or Ne matrices at ~5 K yielded iso-CHBr(3); the observed infrared and UV/visible absorptions are in excellent agreement with computational predictions, and the energies of various stationary points on the CHBr(3) 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 CHBr(3) minimum, the isomer is bound by some 60 kJ/mol in the gas phase with respect to the CHBr(2) + Br asymptote. The photochemistry of iso-CHBr(3) was investigated by selected wavelength laser irradiation into the intense S(0) → S(3) transition, which resulted in back photoisomerization to CHBr(3). 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. © 2011 American Institute of Physics

  12. Physiological function of bromoperoxidase in the red marine alga, Corallina pilulifera: production of bromoform as an allelochemical and the simultaneous elimination of hydrogen peroxide.

    PubMed

    Ohsawa, N; Ogata, Y; Okada, N; Itoh, N

    2001-11-01

    The physiological function of vanadium-bromoperoxidase (BPO) in the marine red alga, Corallina pilulifera, has been characterized from the viewpoint of allelochemical formation. The algae emit bromoform (CHBr3) depending on the enzyme activity level in vivo (Itoh, N., Shinya, M., 1994. Seasonal evolution of bromomethanes from coralline algae and its effect on atmospheric ozone. Marine Chemistry 45, 95-103). We demonstrated that bromoform produced by C. pilulifera played an important role in eliminating epiphytic organisms, especially microalgae on the surface. Such data suggest a strong relationship between the coralline algae and the coralline flat (deforested area in the marine environment: called isoyake in Japanese). Lithophyllum yessoense, the main inhabitant of coralline flats in Japan, produced a lower level of CHBr3 than C. pilulifera, and showed BPO activity. On the other hand, the seasonal change of BPO activity in C. pilulifera in vivo was in proportion to superoxide dismutase (SOD) activity and in inverse proportion to catalase activity. The phenomenon implies that BPO could be a potential substitute for catalase, because the enzyme catalyzes an efficient Br(-)-dependent catalase reaction.

  13. Spectroscopic and computational studies of matrix-isolated iso-CHBr{sub 3}: Structure, properties, and photochemistry of iso-bromoform

    SciTech Connect

    George, Lisa; Kalume, Aimable; Wagner, James; Reid, Scott A.; Esselman, Brian J.; McMahon, Robert J.

    2011-09-28

    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-CHBr{sub 3}) 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 CHBr{sub 3} isolated in Ar or Ne matrices at {approx}5 K yielded iso-CHBr{sub 3}; the observed infrared and UV/visible absorptions are in excellent agreement with computational predictions, and the energies of various stationary points on the CHBr{sub 3} 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 {approx}200 kJ/mol above the global CHBr{sub 3} minimum, the isomer is bound by some 60 kJ/mol in the gas phase with respect to the CHBr{sub 2}+ Br asymptote. The photochemistry of iso-CHBr{sub 3} was investigated by selected wavelength laser irradiation into the intense S{sub 0}{yields} S{sub 3} transition, which resulted in back photoisomerization to CHBr{sub 3}. 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.

  14. Global sampling of the photochemical reaction paths of bromoform by ultrafast deep-UV through near-IR transient absorption and ab initio multiconfigurational calculations

    NASA Astrophysics Data System (ADS)

    Pal, S. K.; Mereshchenko, A. S.; Butaeva, E. V.; El-Khoury, P. Z.; Tarnovsky, A. N.

    2013-03-01

    Ultrafast deep-ultraviolet through near infrared (210-950 nm) transient absorption spectroscopy complemented by ab initio multiconfigurational calculations offers a global description of the photochemical reaction pathways of bromoform following 255-nm excitation in methylcyclohexane and acetonitrile solutions. Photoexcitation of CHBr3 leads to the ground-state iso-CHBr3 product in a large quantum yield (˜35%), formed through two different mechanisms: concerted excited-state isomerization and cage-induced isomerization through the recombination of the nascent radical pair. These two processes take place on different time scales of tens of femtoseconds and several picoseconds, respectively. The novel ultrafast direct isomerization pathway proposed herein is consistent with the occurrence of a conical intersection between the first excited singlet state of CHBr3 and the ground electronic state of iso-CHBr3. Complete active space self-consistent field calculations characterize this singularity in the vicinity of a second order saddle point on the ground state which connects the two isomer forms. For cage-induced isomerization, both the formation of the nascent radical pair and its subsequent collapse into ground-state iso-CHBr3 are directly monitored through the deep-ultraviolet absorption signatures of the radical species. In both mechanisms, the optically active (i.e., those with largest Franck-Condon factors) C-Br-Br bending and Br-Br stretching modes of ground-state iso-CHBr3 have the largest projection on the reaction coordinate, enabling us to trace the structural changes accompanying vibrational relaxation of the non-equilibrated isomers through transient absorption dynamics. The iso-CHBr3 photoproduct is stable in methylcyclohexane, but undergoes either facile thermal isomerization to the parent CHBr3 structure through a cyclic transition state stabilized by the polar acetonitrile medium (˜300-ps lifetime), and hydrolysis in the presence of water.

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  16. Production of bromoform and dibromomethane by Giant Kelp: Factors affecting release and comparison to anthropogenic bromine sources

    USGS Publications Warehouse

    Goodwin, K.D.; North, W.J.; Lidstrom, M.E.

    1998-01-01

    Macrocystis pyrifera (Giant Kelp), a dominant macroalgal species in southern California, produced 171 ng per g fresh wt (gfwt) per day of CHBr3 and 48 ng gfwt-1 d-1 of CH2Br2 during laboratory incubations of whole blades. Comparable rates were measured during in situ incubations of intact fronds. Release of CHBr3 and CH2Br2 by M. pyrifera was affected by light and algal photosynthetic activity, suggesting that environmental factors influencing kelp physiology can affect halomethane release to the atmosphere. Data from H2O2 additions suggest that brominated methane production during darkness is limited by bromide oxidant supply. A bromine budget constructed for a region of southern California indicated that bromine emitted from the use of CH3Br as a fumigant (1 x 108 g Br yr-1) dominates macroalgal sources (3 x 106 g Br yr-1). Global projections, however, suggest that combined emissions of marine algae (including microalgae) contribute substantial amounts of bromine to the global cycle, perhaps on the same order of magnitude as anthropogenic sources.

  17. Pregnancy loss and eye malformations in offspring of F344 rats following gestational exposure to mixtures of regulated trihalomethanes and haloacetic acids

    EPA Science Inventory

    Chlorination of drinking water results in the formation of hundreds of disinfection byproducts (DBPs), the most prevalent are trihalomethanes (THMs) and haloacetic acids (HAAs). Four THMs (chloroform, bromodichloromethane, chlorodibromomethane, bromoform) and five HAAs (chloroac...

  18. The Impact of Mixture Composition, Mixing Ratio and Dose on the Interactions among the Four Trihalomethanes (THMs) Regulated in Drinking Water

    EPA Science Inventory

    Oxidizing disinfectants reduce microbial contamination but react with inorganic and organic materials in water forming disinfection byproducts (DBPs). The U.S. EPA regulates 4 THM DBPs (chloroform, CHCI3; bromodichloromethane, BDCM; chlorodibromomethane, CDBM; bromoform, CHBr3) a...

  19. The Impact of Mixture Composition, Mixing Ratio and Dose on the Interactions among the Four Trihalomethanes (THMs) Regulated in Drinking Water

    EPA Science Inventory

    Oxidizing disinfectants reduce microbial contamination but react with inorganic and organic materials in water forming disinfection byproducts (DBPs). The U.S. EPA regulates 4 THM DBPs (chloroform, CHCI3; bromodichloromethane, BDCM; chlorodibromomethane, CDBM; bromoform, CHBr3) a...

  20. Pregnancy loss and eye malformations in offspring of F344 rats following gestational exposure to mixtures of regulated trihalomethanes and haloacetic acids

    EPA Science Inventory

    Chlorination of drinking water results in the formation of hundreds of disinfection byproducts (DBPs), the most prevalent are trihalomethanes (THMs) and haloacetic acids (HAAs). Four THMs (chloroform, bromodichloromethane, chlorodibromomethane, bromoform) and five HAAs (chloroac...

  1. Bromoalkane production by Antarctic ice algae

    NASA Technical Reports Server (NTRS)

    Sturges, W. T.; Sullivan, C. W.; Schnell, R. C.; Heidt, L. E.; Pollock, W. H.

    1993-01-01

    Ice microalgae, collected from the underside of annual sea ice in McMurdo Sound, Antarctica, were found to contain and release to seawater a number of brominated hydrocarbons. These included bromoform, dibromomethane, mixed bromochloromethanes, and methyl bromide. Atmospheric measurements in the McMurdo Sound vicinity revealed the presence of bromoform and methyl bromide in the lower atmosphere, with lowest concentrations inland, further indicating that biogenic activity in the Sound is a source of organic bromine gases to the Antarctic atmosphere. This may have important implications for boundary layer chemistry in Antarctica. In the Arctic, the presence of bromoform has been linked to loss of surface ozone in the spring. We report here preliminary evidence for similar surface ozone loss at McMurdo Station.

  2. THE INDUCTION OF ABERRANT CRYPT FOCI IN THE COLONS OF MALE F344/N RATS EXPOSED TO THIHALOMETHANE MIXTURES IN THE DRINKING WATER

    EPA Science Inventory


    THE INDUCTION OF ABERRANT CRYPT FOCI IN THE COLONS OF MALE F344/N
    RATS EXPOSED TO TRIHALOMETHANE MIXTURES IN THE DRINKING WATER

    The trihalomethanes (THM), bromoform (TBM) and bromodichloromethane (BDCM), administered by corn oil gavage were found to increase large...

  3. Trihalomethanes in chlorine and bromine disinfected swimming pools: air-water distributions and human exposure.

    PubMed

    Lourencetti, Carolina; Grimalt, Joan O; Marco, Esther; Fernandez, Pilar; Font-Ribera, Laia; Villanueva, Cristina M; Kogevinas, Manolis

    2012-09-15

    This first study of trihalomethanes (THMs) in swimming pools using bromine agents for water disinfection under real conditions shows that the mixtures of these compounds are largely dominated by bromoform in a similar process as chloroform becomes the dominant THM in pools disinfected with chlorine agents. Bromoform largely predominates in air and water of the pool installations whose concentration changes are linearly correlated. However, the air concentrations of bromoform account for about 6-11% of the expected concentrations according to theoretical partitioning defined by the Henry law. Bromoform in exhaled air of swimmers is correlated with the air concentrations of this disinfectant by-product in the pool building. Comparison of the THM exhaled air concentrations between swimmers and volunteers bathing in the water without swimming or standing in the building outside the water suggest that physical activity enhance exposure to these disinfectant by-products. They also indicate that in swimming pools, besides inhalation, dermal absorption is a relevant route for the incorporation of THMs, particularly those with lower degree of bromination.

  4. THE INDUCTION OF ABERRANT CRYPT FOCI (ACF) IN THE COLONS OF RATS BY TRIHALOMETHANES ADMINISTERED IN THE DRINKING WATER

    EPA Science Inventory

    Bromodichloromethane (BDCM) and bromoform (TBM) had been demonstrated to be colon carcinogens in male and female F344/N rats following administration by corn oil gavage. Our chronic bioassay of BDCM administered in the drinking water failed to demonstrate an enhanced colon cance...

  5. THE INDUCTION OF ABERRANT CRYPT FOCI IN THE COLONS OF MALE F344/N RATS EXPOSED TO THIHALOMETHANE MIXTURES IN THE DRINKING WATER

    EPA Science Inventory


    THE INDUCTION OF ABERRANT CRYPT FOCI IN THE COLONS OF MALE F344/N
    RATS EXPOSED TO TRIHALOMETHANE MIXTURES IN THE DRINKING WATER

    The trihalomethanes (THM), bromoform (TBM) and bromodichloromethane (BDCM), administered by corn oil gavage were found to increase large...

  6. THE INDUCTION OF ABERRANT CRYPT FOCI (ACF) IN THE COLONS OF RATS BY TRIHALOMETHANES ADMINISTERED IN THE DRINKING WATER

    EPA Science Inventory

    Bromodichloromethane (BDCM) and bromoform (TBM) had been demonstrated to be colon carcinogens in male and female F344/N rats following administration by corn oil gavage. Our chronic bioassay of BDCM administered in the drinking water failed to demonstrate an enhanced colon cance...

  7. 40 CFR Table 4 to Subpart F of... - Organic Hazardous Air Pollutants Subject to Cooling Tower Monitoring Requirements in § 63.104

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... glycol dimethyl ether 111966 Diethyl sulfate 64675 Dimethylaniline (N,N-) 121697 Dimethylhydrazine (1,1...-) 90040 Benzene 71432 Benzyl chloride 100447 Biphenyl 92524 Bromoform 75252 Butadiene (1,3-) 106990 Carbon disulfide 75150 Carbon tetrachloride 56235 Chloroacetophenone (2-) 532274 Chlorobenzene 108907...

  8. 40 CFR Table 2 to Subpart Jj of... - List of Volatile Hazardous Air Pollutants

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 79447 N,N-Dimethylformamide 68122 1,1-Dimethylhydrazine 57147 Dimethyl phthalate 131113 Dimethyl sulfate... Bromoform 75252 1,3-Butadiene 106990 Carbon disulfide 75150 Carbon tetrachloride 56235 Carbonyl sulfide..., including salts and esters) 94757 DDE (1,1-Dichloro-2,2-bis(p-chlorophenyl)ethylene) 72559...

  9. 40 CFR Table 4 to Subpart F of... - Organic Hazardous Air Pollutants Subject to Cooling Tower Monitoring Requirements in § 63.104

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... glycol dimethyl ether 111966 Diethyl sulfate 64675 Dimethylaniline (N,N-) 121697 Dimethylhydrazine (1,1...-) 90040 Benzene 71432 Benzyl chloride 100447 Biphenyl 92524 Bromoform 75252 Butadiene (1,3-) 106990 Carbon disulfide 75150 Carbon tetrachloride 56235 Chloroacetophenone (2-) 532274 Chlorobenzene 108907...

  10. 40 CFR Table 4 to Subpart F of... - Organic Hazardous Air Pollutants Subject to Cooling Tower Monitoring Requirements in § 63.104

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... glycol dimethyl ether 111966 Diethyl sulfate 64675 Dimethylaniline (N,N-) 121697 Dimethylhydrazine (1,1...-) 90040 Benzene 71432 Benzyl chloride 100447 Biphenyl 92524 Bromoform 75252 Butadiene (1,3-) 106990 Carbon disulfide 75150 Carbon tetrachloride 56235 Chloroacetophenone (2-) 532274 Chlorobenzene 108907...

  11. 40 CFR Table 4 to Subpart F of... - Organic Hazardous Air Pollutants Subject to Cooling Tower Monitoring Requirements in § 63.104

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... glycol dimethyl ether 111966 Diethyl sulfate 64675 Dimethylaniline (N,N-) 121697 Dimethylhydrazine (1,1...-) 90040 Benzene 71432 Benzyl chloride 100447 Biphenyl 92524 Bromoform 75252 Butadiene (1,3-) 106990 Carbon disulfide 75150 Carbon tetrachloride 56235 Chloroacetophenone (2-) 532274 Chlorobenzene 108907...

  12. 40 CFR Table 4 to Subpart F of... - Organic Hazardous Air Pollutants Subject to Cooling Tower Monitoring Requirements in § 63.104

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... glycol dimethyl ether 111966 Diethyl sulfate 64675 Dimethylaniline (N,N-) 121697 Dimethylhydrazine (1,1...-) 90040 Benzene 71432 Benzyl chloride 100447 Biphenyl 92524 Bromoform 75252 Butadiene (1,3-) 106990 Carbon disulfide 75150 Carbon tetrachloride 56235 Chloroacetophenone (2-) 532274 Chlorobenzene 108907...

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

    PubMed

    Adachi, Eiki

    2007-09-01

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

  14. Episodic trihalomethane species and levels in tap water at a start of operation of advanced treatment in Osaka Prefectural water supplies.

    PubMed

    Yamamoto, Kohji; Mori, Yoshiaki

    2009-11-01

    Dramatic changes in trihalomethanes of tap water caused by decreasing the chlorine dose from to break-point to zero at a pre-chlorination could be found during several years from starting the advanced treatment in Osaka Prefectural water utilities (from 1998 to 2002). In 1998 (break-point chlorination), chloroform was predominant (an average of 14.3 microg/L) and bromodichloromethane (5.96 microg/L), dibromochloromethane (4.19 microg/L) and bromoform (1.06 microg/L) were in the decreasing order. In contrast, in 1999 (chloramination), dibromochloromethane and bromodichloromethane were abundant trihalomethanes (6.61 and 5.72 microg/L) and followed by chloroform (4.14 microg/L) and bromoform (1.41 microg/L). Trihalomethane distribution in 2002 (non-chlorination) was almost the same as that in 1999.

  15. Seasonal surface ozone and filterable bromine relationship in the high Arctic

    NASA Astrophysics Data System (ADS)

    Oltmans, S. J.; Schnell, R. C.; Sheridan, P. J.; Peterson, R. E.; Li, S.-M.; Winchester, J. W.; Tans, P. P.; Sturges, W. T.; Kahl, J. D.; Barrie, L. A.

    Ozone and filterable bromine measurements in the high Arctic during the spring return of solar radiation suggest a rapid concurrent destruction of O 3 and conversion of gaseous to particulate Br. Multiyear observations show that this pattern is an annual feature of O 3 measured near the surface at Barrow, Alaska, and other Arctic locations. Aircraft measurements show low O 3 amounts and high filterable Br concentrations beneath the surface temperature inversion over ice throughout the Arctic in the spring. A wintertime build-up of the gaseous organic compound bromoform and a rapid depletion of bromoform in the spring may be a link between the episodic O 3 depletion events and the accompanying rise in filterable Br.

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

    NASA Astrophysics Data System (ADS)

    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.

  17. The Effect of Trihalomethane and Haloacetic Acid Exposure on Fetal Growth in a Maryland County

    DTIC Science & Technology

    2005-03-29

    the four trihalomethanes (bromoform, chloro- form, bromodichloromethane, and dibromochloromethane) and five of the haloacetic acids ( chloroacetic acid ...correlation in the second trimester (bro- moacetic acid and chloroacetic acid : r ¼ 0.66, bromoacetic acid and dibromochloromethane: r ¼ 0.60, and... chloroacetic acid and dibromochloromethane: r ¼ 0.67) and a strong correlation in the third trimester (dichloroacetic acid and trichloroacetic acid : r

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

  20. Disinfection By-Product Exposures and the Risk of Specific Cardiac Birth Defects

    PubMed Central

    Wright, J. Michael; Evans, Amanda; Kaufman, John A.; Rivera-Núñez, Zorimar; Narotsky, Michael G.

    2016-01-01

    Background: Epidemiological studies suggest that women exposed to disinfection by-products (DBPs) have an increased risk of delivering babies with cardiovascular defects (CVDs). Objective: We examined nine CVDs in relation to categorical DBP exposures including bromoform, chloroform, dibromochloromethane (DBCM), bromodichloromethane (BDCM), monobromoacetic acid (MBAA), dichloroacetic acid (DCAA), trichloroacetic acid (TCAA), and summary DBP measures (HAA5, THMBr, THM4, and DBP9). Methods: We calculated adjusted odds ratios (aORs) in a case–control study of birth defects in Massachusetts with complete quarterly 1999–2004 trihalomethane (THM) and haloacetic acid (HAA) data. We randomly matched 10 controls each to 904 CVD cases based on week of conception. Weight-averaged aggregate first-trimester DBP exposures were assigned to individuals based on residence at birth. Results: We detected associations for tetralogy of Fallot and the upper exposure categories for TCAA, DCAA, and HAA5 (aOR range, 3.34–6.51) including positive exposure–response relationships for DCAA and HAA5. aORs consistent in magnitude were detected between atrial septal defects and bromoform (aOR = 1.56; 95% CI: 1.01, 2.43), as well as DBCM, chloroform, and THM4 (aOR range, 1.26–1.67). Ventricular septal defects (VSDs) were associated with the highest bromoform (aOR = 1.85; 95% CI: 1.20, 2.83), MBAA (aOR = 1.81; 95% CI: 0.85, 3.84), and DBCM (aOR = 1.54; 95% CI: 1.00, 2.37) exposure categories. Conclusions: To our knowledge, this is the first birth defect study to develop multi-DBP adjusted regression models as well as the first CVD study to evaluate HAA exposures and the second to evaluate bromoform exposures. Our findings, therefore, inform exposure specificity for the consistent associations previously reported between THM4 and CVDs including VSDs. Citation: Wright JM, Evans A, Kaufman JA, Rivera-Núñez Z, Narotsky MG. 2017. Disinfection by-product exposures and the risk of specific

  1. Measurements of bromine containing organic compounds at the tropical tropopause

    NASA Astrophysics Data System (ADS)

    Schauffler, S. M.; Atlas, E. L.; Flocke, F.; Lueb, R. A.; Stroud, V.; Travnicek, W.

    The amount of bromine entering the stratosphere from organic source gases is a primary factor involved in determining the magnitude of bromine catalyzed loss of ozone. Thirty two whole air samples were collected at the tropical tropopause during the NASA STRAT Campaign in Feb., Aug., and Dec., 1996 and were analyzed for brominated organic compounds. Total organic bromine was 17.4±0.9 ppt with 55% from methyl bromide, 38% from the Halons, 6% from dibromomethane, and 0.8% from bromochloromethane and dichlorobromomethane. One flight showed the presence of 0.42 ppt of additional organic bromine from bromoform and dibromochloromethane.

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

    SciTech Connect

    Dumas, Michael; Rakowski, Joseph T.

    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

  3. 40 CFR Appendix Vii to Part 266 - Health-Based Limits for Exclusion of Waste-Derived Residues*

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... alcohol 107-18-6 2xE−01 Aluminum phosphide 20859-73-8 1xE−02 Aniline 62-53-3 6xE−02 Barium cyanide 542-62...-7 3xE+01 Bromoform 75-25-2 7xE−01 Calcium cyanide 592-01-8 1xE−06 Carbon disulfide 75-15-0 4xE+00...-66-3 6xE−02 Copper cyanide 544-92-3 2xE−01 Cresols (Cresylic acid) 1319-77-3 2xE+00 Cyanogen...

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

    PubMed

    Dumas, Michael; Rakowski, Joseph T

    2015-12-01

    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. 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(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. 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. 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 dosimeter in this form was sensitive

  5. 40 CFR Appendix Vii to Part 266 - Health-Based Limits for Exclusion of Waste-Derived Residues*

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...−08 Hexachloroethane 67-72-1 3xE−02 Hydrazine 302-01-1 1xE−04 Hydrogen cyanide 74-90-8 7xE−05 Hydrogen... alcohol 107-18-6 2xE−01 Aluminum phosphide 20859-73-8 1xE−02 Aniline 62-53-3 6xE−02 Barium cyanide 542-62...-7 3xE+01 Bromoform 75-25-2 7xE−01 Calcium cyanide 592-01-8 1xE−06 Carbon disulfide 75-15-0 4xE+00...

  6. Isolation and microscopic characterization of nuclear fuel particles from contaminated soil of ChernobylSéparation et caractérisation microscopique des particules de combustible nucléaire présentes dans les sols contaminés de Tchernobyl

    NASA Astrophysics Data System (ADS)

    Ahamdach, Noureddine; Stammose, Denise

    2000-03-01

    Nuclear fuel particles were separated from Chernobyl contaminated soil sample by sedimentation in bromoform. Their physicochemical characteristics were studied using the scanning electron microscope. One part of the particles contained U and O and the other part contained U, Zr and O. The size of the particles containing Zr was greater than that of the pure fuel particles. The structure and the surface morphology of the studied particles were variable and characterized the conditions of their formation. Thus, the source term is heterogeneous. This heterogeneity has direct consequences on the dissolution of the fuel particles.

  7. METHOD AND MEANS FOR RADIATION DOSIMETRY

    DOEpatents

    Shulte, J.W.; Suttle, J.F.

    1958-02-18

    This patent relates to a method and device for determining quantities of gamma radiation and x radiation by exposing to such radiation a mature of a purified halogenated hydrocarbon chosen from the class consisting of chloroform, bromoform, tetrachloroethane and 1,1,2trichloroethane, and a minor quantity of a sensitizer chosen from the class consisting of oxygen, benzoyl peroxide, sodium peroxide, and nitrobenzene, the proportion of the sensitizer being at least about 10/sup -5/ moles per cubic centimeter of halogenated hydrocarbon, the total amount of sensitizer depending upon the range of radiation to be measured, and chemically measuring the amount of decomposition generated by the irradiation of the sensitized halogenated hydrocarbon.

  8. Formation and speciation characteristics of brominated trihalomethanes in seawater chlorination.

    PubMed

    Padhi, R K; Sowmya, M; Mohanty, A K; Bramha, S N; Satpathy, K K

    2012-11-01

    Formation character of brominated-trihalomethanes (Br-THMs) in chlorinated seawater and its dependence on applied chlorine dose, reaction time, and temperature were investigated in the laboratory. Seawater was collected from the east coast of India and a chlorine dose of 1, 3, 5, and 10 ppm was each applied at a temperature of 20, 30, and 40 degrees C to investigate the yield and kinetics of Br-THMs formation. Qualitative and quantitative estimation of THM formation at various intervals of time ranging from 5 min to 168 h was determined by a gas chromatograph equipped with an electron capture detector (GC-ECD). Chlorine dose, chlorine contact time, and reaction temperature positively affected the load of THMs. The ratio of chlorine dose to halogen incorporation decreased from 12% to 5% with increasing applied chlorine dose from 1 to 10 ppm. Significant levels of THMs were found to be formed within 0.5 h of reaction, followed by a very slow rate of formation. Elevated temperature favored both increased rate of formation and overall THM yield. The formation order of different trihalomethane species at all studied temperatures was observed to be bromodichloromethane (CHCl2Br) < dibromochloromethane (CHClBr2) < bromoform (CHBr3). Formation of chloroform was not observed, and bromoform was the dominant (96% to 98%) among the three THM species formed.

  9. Degradation Products of Benzophenone-3 in Chlorinated Seawater Swimming Pools.

    PubMed

    Manasfi, Tarek; Storck, Veronika; Ravier, Sylvain; Demelas, Carine; Coulomb, Bruno; Boudenne, Jean-Luc

    2015-08-04

    Oxybenzone (2-hydroxy-4-methoxyphenone, benzophenone-3) is one of the UV filters commonly found in sunscreens. Its presence in swimming pools and its reactivity with chlorine has already been demonstrated but never in seawater swimming pools. In these pools, chlorine added for disinfection results in the formation of bromine, due to the high levels of bromide in seawater, and leads to the formation of brominated disinfection byproducts, known to be more toxic than chlorinated ones. Therefore, it seems important to determine the transformation products of oxybenzone in chlorinated seawater swimming pools; especially that users of seawater swimming pools may apply sunscreens and other personal-care products containing oxybenzone before going to pools. This leads to the introduction of oxybenzone to pools, where it reacts with bromine. For this purpose, the reactivity of oxybenzone has been examined as a function of chlorine dose and temperature in artificial seawater to assess its potential to produce trihalomethanes and to determine the byproducts generated following chlorination. Increasing doses of chlorine and increasing temperatures enhanced the formation of bromoform. Experiments carried out with excess doses of chlorine resulted in the degradation of oxybenzone and allowed the determination of the degradation mechanisms leading to the formation of bromoform. In total, ten transformation products were identified, based on which the transformation pathway was proposed.

  10. Multi-route risk assessment from trihalomethanes in drinking water supplies.

    PubMed

    Basu, Mrittika; Gupta, Sunil Kumar; Singh, Gurdeep; Mukhopadhyay, Ujjal

    2011-07-01

    The main objectives of this study were to investigate the concentration and lifetime cancer risk and hazard index of trihalomethanes (THMs) through multiple routes like oral ingestion, dermal absorption, and inhalation exposure in the water samples collected at water treatment plant endpoints. Bromoform has been found in highest concentration followed by chloroform. A lesser concentration of dibromochloromethane has been found than dichlorobromomethane in most of the studied water, which is an unusual scenario, in spite of the high concentration of bromide in the water which can be attributed to the formation, speciation, and distribution of THMs in the breakpoint chlorination curve. Among the three pathways studied, inhalation contributed 80-90% of the total risk followed by oral exposure and dermal contact. Chloroform was found to be the major THM which is having cancer risk in its gaseous form whereas bromoform contributed highest cancer risk through oral ingestion. The average hazard index of total THMs through oral route was higher than unity, indicating high noncarcinogenic risk. The discrepancy between the three exposure pathways may be attributed to different concentration and speciation of THMs present in the waters. The sensitivity analysis by tornado diagram confirmed the highest positive impact of chloroform to the total cancer risk and, indirectly, confirmed inhalation as the major pathway of exposure. This study suggests the modification of the regulatory issues related to THMs based on the health risk associated with each THM and exposure pathway.

  11. Formation of hazardous by-products resulting from the irradiation of natural organic matter: comparison between UV and VUV irradiation.

    PubMed

    Buchanan, W; Roddick, F; Porter, N

    2006-05-01

    The use of ultraviolet (UV) or vacuum ultraviolet (VUV) photo-oxidation followed by biological treatment for the removal of natural organic matter (NOM) in drinking water is a potential water treatment technique under investigation. This paper reports on the trihalomethane formation potential (THMFP), the haloacetic acid formation potential (HAAFP), and formation of nitrite and peroxide following both UV and VUV irradiation of NOM prior to biological treatment. The total THMFP was found to decrease with increasing UV and VUV irradiation dose, although there was a linear increase in bromoform formation. Determination of the THMFP of NOM fractions obtained after irradiation, showed that the hydrophobic fraction was dominated by chlorinated species which accounted for the majority of the total THMFP, while bromoform was observed only in the hydrophilic fraction of NOM. VUV irradiation reduced the HAAFP with increasing dose, in contrast, UV irradiation had a limited effect on the overall HAAFP. Following UV or VUV irradiation, the chlorinated species accounted for the majority of HAAFP; however, significant formation of brominated haloacetic acid (HAA) was observed. The nitrate concentration of the untreated water directly influenced the concentration of nitrite produced as a consequence of UV and VUV irradiation. Hydrogen peroxide formation was greater during VUV irradiation than during UV irradiation. Samples exposed to various doses of UV or VUV irradiation (up to 138 J cm(-2)) were deemed non-cytotoxic (African green monkey kidney cells) and non-mutagenic (Ames test).

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

    USGS Publications Warehouse

    Ferrell, G.M.

    2009-01-01

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

  13. Distribution, transport, and production of volatile halocarbons in the upper waters of the ice-covered high Arctic Ocean

    NASA Astrophysics Data System (ADS)

    Karlsson, A.; Theorin, M.; Abrahamsson, K.

    2013-12-01

    halogenated compounds (CHBr3, CH2Br2, CHBr2Cl, and CH2ClI) were measured in the water column and in sea ice brine across the Arctic Ocean, from Barrow, Alaska, to Svalbard, during the Beringia 2005 expedition (August-September) with RV/IB Oden. High concentrations of brominated compounds (up to 42 pmol kg-1 of bromoform) were found under multiyear ice in the surface waters over the Makarov Basin and the Lomonosov Ridge, near the North Pole. Even higher concentrations (bromoform up to 160 pmol kg-1) were found in sea ice brine. We propose that the high load of riverine dissolved organic matter that is transported in the Transpolar Drift is a main factor responsible for the high concentration of brominated volatile compounds found in sea ice brine and upper waters and that cycles of freezing and thawing during the transport enhance the transfer of halocarbons to the seawater. The iodinated compound (CH2ClI) showed a completely different distribution with highest concentrations in water of Pacific origin in the mixed layer and upper halocline of the northern Canada Basin and over the Alpha Ridge. In the southern Canada Basin, low concentrations of halocarbons were found in upper waters. Higher concentrations in water of Pacific origin, especially on the continental shelf, indicate production in the shelf regions, likely in the Chukchi Sea and the East Siberian Sea.

  14. Plan of study for selected toxic substances in the Calcasieu River, Louisiana

    SciTech Connect

    Demcheck, D.K.; Demas, C.R.; Curwick, P.B.

    1990-01-01

    In 1984 the US Geological Survey established the Toxic Substances Hydrology, Surface-Water Contamination Program. As part of this program, an investigation of the lower Calcasieu River, Louisiana, began in 1985 to define the magnitude and distribution of selected toxic substances in the Calcasieu River and the physical and chemical processes that govern their fate. The major elements of the investigation are: (1) a compilation of previous studies of the Calcasieu River by various Federal, State, and local agencies; (2) reconnaissance surveys of chemical constituents in the water column and bottom material; (3) a remobilization study; (4) a study of microbial degradation; (5) studies of the presence of synthetic organic compounds in the tissues of fish, clams, and crabs; (6) volatilization studies of compounds such as bromoform and chloroform; (7) sediment-water interface studies; and (8) the development of a streamflow model to provide a hydrologic framework for water quality analysis. Preliminary results were used to select for intensive study of the following substances in water, bottom material, and biota: ammonia, nitrite plus nitrate, chromium, iron, mercury, bromoform, chloroform, 1,2-dichloroethane, hexachlorobenzene, hexachlorobutadiene, naphthalene, octachloronaphthalene, benzopyrene, and benzoperylene. 11 refs., 5 figs., 5 tabs.

  15. Detecting trihalomethanes using nanoporous-carbon coated surface-acoustic-wave sensors

    SciTech Connect

    Siegal, Michael P.; Mowry, Curtis D.; Pfeifer, Kent B.; Gallis, Dorina F. S.

    2015-03-07

    We study nanoporous-carbon (NPC) grown via pulsed laser deposition (PLD) as a sorbent coating on 96.5-MHz surface-acoustic-wave (SAW) devices to detect trihalomethanes (THMs), regulated byproducts from the chemical treatment of drinking water. Using both insertion-loss and isothermal-response measurements from known quantities of chloroform, the highest vapor pressure THM, we optimize the NPC mass-density at 1.05 ± 0.08 g/cm3 by controlling the background argon pressure during PLD. Precise THM quantities in a chlorobenzene solvent are directly injected into a separation column and detected as the phase-angle shift of the SAW device output compared to the drive signal. Using optimized NPC-coated SAWs, we study the chloroform response as a function of operating temperatures ranging from 10–50°C. Finally, we demonstrate individual responses from complex mixtures of all four THMs, with masses ranging from 10–2000 ng, after gas chromatography separation. As a result, estimates for each THM detection limit using a simple peak-height response evaluation are 4.4 ng for chloroform and 1 ng for bromoform; using an integrated-peak area response analysis improves the detection limits to 0.73 ng for chloroform and 0.003 ng bromoform.

  16. Detecting trihalomethanes using nanoporous-carbon coated surface-acoustic-wave sensors

    DOE PAGES

    Siegal, Michael P.; Mowry, Curtis D.; Pfeifer, Kent B.; ...

    2015-03-07

    We study nanoporous-carbon (NPC) grown via pulsed laser deposition (PLD) as a sorbent coating on 96.5-MHz surface-acoustic-wave (SAW) devices to detect trihalomethanes (THMs), regulated byproducts from the chemical treatment of drinking water. Using both insertion-loss and isothermal-response measurements from known quantities of chloroform, the highest vapor pressure THM, we optimize the NPC mass-density at 1.05 ± 0.08 g/cm3 by controlling the background argon pressure during PLD. Precise THM quantities in a chlorobenzene solvent are directly injected into a separation column and detected as the phase-angle shift of the SAW device output compared to the drive signal. Using optimized NPC-coated SAWs,more » we study the chloroform response as a function of operating temperatures ranging from 10–50°C. Finally, we demonstrate individual responses from complex mixtures of all four THMs, with masses ranging from 10–2000 ng, after gas chromatography separation. As a result, estimates for each THM detection limit using a simple peak-height response evaluation are 4.4 ng for chloroform and 1 ng for bromoform; using an integrated-peak area response analysis improves the detection limits to 0.73 ng for chloroform and 0.003 ng bromoform.« less

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

    SciTech Connect

    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. Cancer and non-cancer risk assessment of trihalomethanes in urban drinking water supplies of Pakistan.

    PubMed

    Amjad, Hira; Hashmi, Imran; Rehman, Muhammad Saif Ur; Ali Awan, M; Ghaffar, Sajeela; Khan, Zahiruddin

    2013-05-01

    This study aims at monitoring and risk assessment of trihalomethanes (THMs) such as chloroform, bromodichloromethane, dibromochloromethane and bromoform, in the drinking water supplies of Rawalpindi and Islamabad. THMs were monitored at twenty locations in these twin cities using solid phase micro extraction-gas chromatography (SPME-GC). Total concentration of THMs was ranged between 21 and 373μg/L, whereas both cities had an average total THMs concentration of 142 and 260μg/L, respectively. Chloroform was found as one the major contributor to the THMs concentration (>85%). The occurrence of THMs followed the given order: chloroform, bromodichloromethane>dibromochloromethane>bromoform. Lifetime cancer risk assessment of THMs was carried out using prediction models via different exposure routes (ingestion, inhalation and dermal). An average lifetime cancer risk was found to be 0.74×10(-4) and 1.24×10(-4) for Rawalpindi and Islamabad, respectively. The number of expected cancer cases per year could reach two cases for each city. Hazard index values were found below unity for both the cities implying that there would be no considerable non-cancer risk. Oral ingestion was found to be one of the main routes of exposure for both types of risk which was followed by inhalation and dermal routes.

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

    SciTech Connect

    Dumas, M; Rakowski, J

    2014-06-01

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

  20. Predictors of Blood Trihalomethane Concentrations in NHANES 1999–2006

    PubMed Central

    Dhingra, Radhika; Blount, Benjamin C.; Steenland, Kyle

    2014-01-01

    Background: Trihalomethanes (THMs) are water disinfection by-products that have been associated with bladder cancer and adverse birth outcomes. Four THMs (bromoform, chloroform, bromodichloromethane, dibromochloromethane) were measured in blood and tap water of U.S. adults in the National Health and Nutrition Examination Survey (NHANES) 1999–2006. THMs are metabolized to potentially toxic/mutagenic intermediates by cytochrome p450 (CYP) 2D6 and CYP2E1 enzymes. Objectives: We conducted exploratory analyses of blood THMs, including factors affecting CYP2D6 and CYP2E1 activity. Methods: We used weighted multivariable regressions to evaluate associations between blood THMs and water concentrations, survey year, and other factors potentially affecting THM exposure or metabolism (e.g., prescription medications, cruciferous vegetables, diabetes, fasting, pregnancy, swimming). Results: From 1999 to 2006, geometric mean blood and water THM levels dropped in parallel, with decreases of 32%–76% in blood and 38%–52% in water, likely resulting, in part, from the lowering of the total THM drinking water standard in 2002–2004. The strongest predictors of blood THM levels were survey year and water concentration (n = 4,232 total THM; n = 4,080 bromoform; n = 4,582 chloroform; n = 4,374 bromodichloromethane; n = 4,464 dibromochloromethane). We detected statistically significant inverse associations with diabetes and eating cruciferous vegetables in all but the bromoform model. Medications did not consistently predict blood levels. Afternoon/evening blood samples had lower THM concentrations than morning samples. In a subsample (n = 230), air chloroform better predicted blood chloroform than water chloroform, suggesting showering/bathing was a more important source than drinking. Conclusions: We identified several factors associated with blood THMs that may affect their metabolism. The potential health implications require further study. Citation: Riederer AM, Dhingra R

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

    NASA Astrophysics Data System (ADS)

    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 < DBCM < BDCM < chloroform. Results of the MSD showed a significant correlation between NOM of high molecular size (peak I) and TTHM formation specifically during the summer months (R2= 0.971, p < 0.05). High molecular weight (HMW) NOM also related well to chloroform formation (R2 = 0.963, p < 0.05) however, the formation of BDCM was not due to HWM fraction as indicated by weak regression coefficient. A positive correlation existed between

  2. Formation and modeling of disinfection by-products in drinking water of six cities in China.

    PubMed

    Ye, Bixiong; Wang, Wuyi; Yang, Linsheng; Wei, Jianrong; E, Xueli

    2011-05-01

    Water quality parameters including TOC, UV(254), pH, chlorine dosage, bromide concentration and disinfection by-products were measured in water samples from 41 water treatment plants of six selected cities in China. Chloroform, bromodichloromethane, dibromochloromethane, dichloroacetic acid and trichloroacetic acid were the major disinfection by-products in the drinking water of China. Bromoform and dibromoacetic acid were also detected in many water samples. Higher concentrations of trihalomethanes and haloacetic acids were measured in summer compared to winter. The geographical variations in DBPs showed that TTHM levels were higher in Zhengzhou and Tianjin than other selected cities. And the HAA5 levels were highest in Changsha and Tianjin. The modeling procedure that predicts disinfection by-products formation was studied and developed using artificial neural networks. The performance of the artificial neural networks model was excellent (r > 0.84).

  3. Modeling of trihalomethane cometabolism in nitrifying biofilters.

    PubMed

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

    2007-01-01

    The computer program AQUASIM was used to model biofilter experiments seeded with Lake Austin, Texas mixed-culture nitrifiers. These biofilters degraded four trihalomethanes (THMs) (trichloromethane (TCM) or chloroform, bromodichloromethane (BDCM), dibromochloromethane (DBCM), tribromomethane (TBM) or bromoform) commonly found in treated drinking water. Apparent steady-state data from the biofilter experiments and supporting batch experiments were used to estimate kinetic parameters for TCM, DBCM and ammonia degradation. Subsequently, the model was verified against other experimental biofilter data. To allow for full-scale simulations, BDCM and TBM rate constants were estimated using data from batch kinetic studies. Finally, the model was used to simulate full-scale filter performance under different filter surface loading rates and THM speciation seen in practice. Overall, total THM removals ranged from 16% to 54% in these simulations with influent total THM concentrations of 75-82microg/L, which illustrates the potential of THM cometabolism to have a significant impact on treated water quality.

  4. Coherent two-dimensional terahertz-terahertz-Raman spectroscopy.

    PubMed

    Finneran, Ian A; Welsch, Ralph; Allodi, Marco A; Miller, Thomas F; Blake, Geoffrey A

    2016-06-21

    We present 2D terahertz-terahertz-Raman (2D TTR) spectroscopy, the first technique, to our knowledge, to interrogate a liquid with multiple pulses of terahertz (THz) light. This hybrid approach isolates nonlinear signatures in isotropic media, and is sensitive to the coupling and anharmonicity of thermally activated THz modes that play a central role in liquid-phase chemistry. Specifically, by varying the timing between two intense THz pulses, we control the orientational alignment of molecules in a liquid, and nonlinearly excite vibrational coherences. A comparison of experimental and simulated 2D TTR spectra of bromoform (CHBr3), carbon tetrachloride (CCl4), and dibromodichloromethane (CBr2Cl2) shows previously unobserved off-diagonal anharmonic coupling between thermally populated vibrational modes.

  5. Laser-sheet imaging of HE-driven interfaces

    SciTech Connect

    Benjamin, R.F.; Rightley, P.M.; Kinkead, S.; Martin, R.A.; Critchfield, R.; Sandoval, D.L.; Holmes, R.; Gorman, T.

    1998-12-31

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The authors made substantial progress in developing the MILSI (Multiple Imaging of Laser-Sheet Illumination) technique for high explosive (HE)-driven fluid interfaces. They observed the instability, but have not yet measured the instability growth rate. They developed suitable sample containers and optical systems for studying the Rightmyer-Meshkov instability of perturbed water/bromoform interfaces and they successfully fielded the new MILSI diagnostic at two firing-site facilities. The problem continues to be of central importance to the inertial confinement fusion (ICF) and weapons physics communities.

  6. Towards an automated and efficient calculation of resonating vibrational states based on state-averaged multiconfigurational approaches

    SciTech Connect

    Meier, Patrick; Oschetzki, Dominik; Pfeiffer, Florian; Rauhut, Guntram

    2015-12-28

    Resonating vibrational states cannot consistently be described by single-reference vibrational self-consistent field methods but request the use of multiconfigurational approaches. Strategies are presented to accelerate vibrational multiconfiguration self-consistent field theory and subsequent multireference configuration interaction calculations in order to allow for routine calculations at this enhanced level of theory. State-averaged vibrational complete active space self-consistent field calculations using mode-specific and state-tailored active spaces were found to be very fast and superior to state-specific calculations or calculations with a uniform active space. Benchmark calculations are presented for trans-diazene and bromoform, which show strong resonances in their vibrational spectra.

  7. Absorption, distribution, and excretion of /sup 14/C-trihalomethanes in mice and rats

    SciTech Connect

    Mink, F.L.; Brown, T.J.; Rickabaugh, J.

    1986-11-01

    Chloroform and other trihalomethanes have been shown to originate from reactions between chlorine and naturally-occurring organic precursors in water. Chloroform (TCM) has been shown, at high dose levels, to increase the tumor incidence in mice and rats. Studies by lardiff demonstrated chloroform was not mutagenic in the Ames bioassay using Salmonella typhimurium strains TA100 and TA1535. Bromodichloromethane, dibromochloromethane and bromoform demonstrated a dose-related mutagenic response. Differences in biological responses between mice and rats have been attributed to differences in their relative rates of TCM metabolism. Several predictive studies estimate that the mouse metabolizes TCM at a significantly different rate than the rat. This study was initiated to determine the absorption, distribution and excretion characteristics of four trihalomethanes (TCM, TBM, DBCM and BDCM) using the carbon 14 labeled compounds under identical experimental conditions in both the mouse and rat.

  8. Vibrational relaxation pathways of amide I and amide II modes in N-methylacetamide.

    PubMed

    Piatkowski, L; Bakker, H J

    2012-04-28

    We studied the vibrational energy relaxation mechanisms of the amide I and amide II modes of N-methylacetamide (NMA) monomers dissolved in bromoform using polarization-resolved femtosecond two-color vibrational spectroscopy. The results show that the excited amide I vibration transfers its excitation energy to the amide II vibration with a time constant of 8.3 ± 1 ps. In addition to this energy exchange process, we observe that the excited amide I and amide II vibrations both relax to a final thermal state. For the amide I mode this latter process dominates the vibrational relaxation of this mode. We find that the vibrational relaxation of the amide I mode depends on frequency which can be well explained from the presence of two subbands with different vibrational lifetimes (~1.1 ps on the low frequency side and ~2.7 ps on the high frequency side) in the amide I absorption spectrum.

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

    PubMed

    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.

  10. Study on control of micro-pollutants by BAC filtration.

    PubMed

    Zhang, Z H; Shao, L

    2008-01-01

    The objective of this research was to evaluate removal efficiency of micro-pollutants in a BAC filter that followed ozonation for long term operation. The experimental results showed that after continuous operation for one year BAC filter still maintained a removal of 15 approximately 20% for COD(Mn) and 20 approximately 30% of removal for UV(254). Correlative analysis based on lots of data found that empty bed contact time (EBCT) instead of flow rate could obviously impact on removal effect of micro-pollutants in BAC filter. And the optimal relationship between EBCT and removal effect of micro-pollutants for BAC filter was logarithm. On the other hand, long term running of BAC filter proved that there was a good removal of chloroform formation potential, but the removal of brominated trihalomethane formation potential decline with further bromization, even there appeared to be formation of bromoform in BAC filter. (c) IWA Publishing 2008.

  11. VOC concentration in Taiwan's household drinking water.

    PubMed

    Kuo, H W; Chiang, T F; Lo, I I; Lai, J S; Chan, C C; Wang, J D

    1997-12-03

    The objective of this study is to analyze volatile organic compound (VOC) concentrations in Taiwan's drinking water supply. Focusing on Taiwan's three major metropolitan areas--Taipei, Taichung and Kaohsiung (in the north, middle and south, respectively)--171 samples were taken from tap water and 68 from boiled water. Tests showed VOC concentrations were highest in Kaohsiung. This is due to different water sources and methods of treatment. Except for bromoform, trihalomethane (THM) concentrations were highest. Detection rates of toluene and 1,2-dichloroethane were slightly higher than other VOC compounds. VOC concentrations decreased significantly after water was boiled. THMs had a removal rate from 61% to 82%. The authors conclude that the three metropolitan areas contain significantly different levels of VOCs and that boiling can significantly reduce the presence of VOCs. Other sources of pollution that contaminate drinking water such as industrial plants and gas stations must be further investigated.

  12. Review of fundamentals and specific aspects of oxidation technologies in marine waters.

    PubMed

    Kornmueller, A

    2007-01-01

    This review is based on the existing literature and on our experiences in the application of different oxidation processes in brackish water and seawater. The oxidation reactions of advanced oxidation processes (AOPs) and the formation of disinfection byproducts (DBPs) are considerably different in marine waters from well-known drinking, process and wastewater applications. In contrast, the major secondary oxidants are bromine species in marine waters, which might form the DBPs of concern bromate and bromoform. An efficient AOP application needs knowledge of the source water constitutions and the oxidant demand. Besides changes in the oxidants chemistry compared to fresh water, the great and seasonal variation of marine waters has to be considered in the process design. The complexity of oxidant reactions and formation of byproducts are only partially researched and known as yet. Hence, it is advisable to determine the characteristic and variation of the water source as well as its influence on each AOP in experiments prior to the process design.

  13. The handling, hazards, and maintenance of heavy liquids in the geologic laboratory

    USGS Publications Warehouse

    Hauff, Phoebe L.; Airey, Joseph

    1980-01-01

    In geologic laboratories the organic heavy liquids bromoform, methylene iodide, tetrabromoethane, and clerici compounds have been used for years in mineral separation processes. Because the volume of use of these compounds is low, insufficient data is available on their toxic properties. This report is an attempt to summarize the known data from published and industry sources. The physical properties, hazards of handling,proper storage facilities, and adequate protective Clothing are discussed for each compound as well as for their common and less-common solvents. Toxicity data for these materials is listed along with exposure symptoms and suggested first aid treatments. Safety for the worker is emphasized. Three reclamation methods which recover the solvent used as a dilutant and purify the heavy liquid are discussed and illustrated. These include: the water cascade, re fluxing-distillation-condensation, and flash evaporation methods. Various techniques for restoration and stabilization of these heavy liquids are also included.

  14. Measurement of trihalomethanes and methyl tertiary-butyl ether in tap water using solid-phase microextraction GC-MS.

    PubMed

    Cardinali, Frederick L; Ashley, David L; Morrow, John C; Moll, Deborah M; Blount, Benjamin C

    2004-04-01

    The prevalence of water disinfection byproducts in drinking water supplies has raised concerns about possible health effects from chronic exposure to these compounds. To support studies exploring the relation between exposure to trihalomethanes (THMs) and health effects, we have developed an automated analytical method using headspace solid-phase microextraction coupled with capillary gas chromatography and mass spectrometry. This method quantitates trace levels of THMs (chloroform, bromodichloromethane, dibromochloromethane, and bromoform) and methyl tertiary-butyl ether in tap water. Detection limits of less than 100 ng/L for all analytes and linear ranges of three orders of magnitude are adequate for measuring the THMs in tap water samples tested from across the United States. THMs are stable for extended periods in tap water samples after quenching of residual chlorine and buffering to pH 6.5, thus enabling larger epidemiologic field studies with simplified sample collection protocols.

  15. Public health assessment for 57th and North Broadway Streets Site, Wichita, Sedgwick County, Kansas, Region 7. Cerclis No. KDS981710247. Final report

    SciTech Connect

    Not Available

    1994-08-31

    The 57th and North Broadway Streets Site is a residential/commercial area in the vicinity of 53rd Street and North Broadway Street, in Wichita Heights between Wichita and Park City, Kansas. Based on information reviewed, the 57th and North Broadway Streets Site poses a public health hazard because residents and workers are likely to have been exposed to arsenic, benzene, cadmium, and vinyl chloride in well water at levels that could cause adverse health effects. Moreover, some residents and workers at business facilities on site likely are exposed or are likely to have been exposed to benzene, bromoform, dibromochloromethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1-dichloroethene, tetrachloroethene, trichloroethene, dichlormethane, 1,1,1-trichloroethane and lead in well water and or soils and wastes. However, adverse health effects are unlikely to occur because of the low levels of exposure

  16. Hot bands in the Ã← X˜ spectrum of HCBr

    NASA Astrophysics Data System (ADS)

    Chang, Bor-Chen; Guss, Joseph; Sears, Trevor J.

    2003-05-01

    Spectra of both the Ã(0, 0, 0)- X˜(0, 1, 0) and Ã(0, 0, 0)- X˜(0, 0, 1) bands in the Ö X˜ band system of HCBr have been recorded and rotationally assigned. The HCBr radical was formed by 193 nm excimer laser photolysis of bromoform. We found no signals from HCBr when the photolysis laser wavelength was changed to 248 nm, although strong CH product emission was observed by eye at both wavelengths. Most of the spectra were recorded in absorption at ambient temperature in a long-path absorption cell using a single frequency Ti:sapphire laser as the light source, but some congested sections were recorded under jet-cooled conditions. Analysis yielded accurate values for the vibrational fundamentals and rotational constants for the vibrationally excited ground state levels determined. A combination of experimental measurements and ab initio vibration-rotation constants was used to estimate equilibrium parameters and a ground state structure for HCBr.

  17. Liquid sound speeds at pressure from the optical analyzer technique

    SciTech Connect

    Fritz, J.N.; Morris, C.E.; Hixson, R.S.; McQueen, R.G.

    1993-08-01

    The optical analyzer technique has proved to be a useful means of obtaining wave velocities at high pressures. Stepped wedges of the investigated material emit shock, and later, rarefaction waves into a transparent analyzer covering the material. The time interval between shock and rarefaction plotted versus wedge thickness gives a linear plot whose intercept fixes the target/driver thickness ratio for exact wave overtake, and thus gives a relation between the shock velocity and overtaking wave velocity at pressure. The slope of this line is intimately related to the wave velocity at pressure of the analyzer in front of the wedge. This aspect of the technique has not yet been exploited. We present the appropriate analysis, some data on bromoform (one of the analyzers used), and discuss some possible applications of this technique.

  18. The natural production of organobromine compounds.

    PubMed

    Gribble, G W

    2000-03-01

    Organobromine chemicals are produced naturally by an array of biological and other chemical processes in our environment. Some of these compounds are identical to man-made organobromine compounds, such as methyl bromide, bromoform, and bromophenols, but many others are entirely new moleclar entities, often possessing extraordinary and important biological properties. Although only a few natural organobromine compounds had been discovered up to 1968, this number as of early 1999 is more than 1,600, and new examples are being discovered continually. Organobromine compounds are produced naturally by marine creatures (sponges, corals, sea slugs, tunicates, sea fans) and seaweed, plants, fungi, lichen, algae, bacteria, microbes, and some mammals. Many of these organobromine compounds are used in chemical defense, to facilitate food gathering, or as hormones.

  19. Coherent two-dimensional terahertz-terahertz-Raman spectroscopy

    PubMed Central

    Finneran, Ian A.; Welsch, Ralph; Allodi, Marco A.; Miller, Thomas F.; Blake, Geoffrey A.

    2016-01-01

    We present 2D terahertz-terahertz-Raman (2D TTR) spectroscopy, the first technique, to our knowledge, to interrogate a liquid with multiple pulses of terahertz (THz) light. This hybrid approach isolates nonlinear signatures in isotropic media, and is sensitive to the coupling and anharmonicity of thermally activated THz modes that play a central role in liquid-phase chemistry. Specifically, by varying the timing between two intense THz pulses, we control the orientational alignment of molecules in a liquid, and nonlinearly excite vibrational coherences. A comparison of experimental and simulated 2D TTR spectra of bromoform (CHBr3), carbon tetrachloride (CCl4), and dibromodichloromethane (CBr2Cl2) shows previously unobserved off-diagonal anharmonic coupling between thermally populated vibrational modes. PMID:27274067

  20. Chlorination Disinfection By-Products and Risk of Congenital Anomalies in England and Wales

    PubMed Central

    Nieuwenhuijsen, Mark J.; Toledano, Mireille B.; Bennett, James; Best, Nicky; Hambly, Peter; de Hoogh, Cornelis; Wellesley, Diana; Boyd, Patricia A.; Abramsky, Lenore; Dattani, Nirupa; Fawell, John; Briggs, David; Jarup, Lars; Elliott, Paul

    2008-01-01

    Background Increased risk of various congenital anomalies has been reported to be associated with trihalomethane (THM) exposure in the water supply. Objectives We conducted a registry-based study to determine the relationship between THM concentrations and the risk of congenital anomalies in England and Wales. Methods We obtained congenital anomaly data from the National Congenital Anomalies System, regional registries, and the national terminations registry; THM data were obtained from water companies. Total THM (< 30, 30 to < 60, ≥60 μg/L), total brominated exposure (< 10, 10 to < 20, ≥20 μg/L), and bromoform exposure (< 2, 2 to < 4, ≥4 μg/L) were modeled at the place of residence for the first trimester of pregnancy. We included 2,605,226 live births, stillbirths, and terminations with 22,828 cases of congenital anomalies. Analyses using fixed- and random-effects models were performed for broadly defined groups of anomalies (cleft palate/lip, abdominal wall, major cardiac, neural tube, urinary and respiratory defects), a more restricted set of anomalies with better ascertainment, and for isolated and multiple anomalies. Data were adjusted for sex, maternal age, and socioeconomic status. Results We found no statistically significant trends across exposure categories for either the broadly defined or more restricted sets of anomalies. For the restricted set of anomalies with isolated defects, there were significant (p < 0.05) excess risks in the high-exposure categories of total THMs for ventricular septal defects [odds ratio (OR) = 1.43; 95% confidence interval (CI), 1.00–2.04] and of bromoform for major cardiovascular defects and gastroschisis (OR = 1.18; 95% CI, 1.00–1.39; and OR = 1.38; 95% CI, 1.00–1.92, respectively). Conclusion In this large national study we found little evidence for a relationship between THM concentrations in drinking water and risk of congenital anomalies. PMID:18288321

  1. Occurrence of brominated disinfection byproducts in the air and water of chlorinated seawater swimming pools.

    PubMed

    Manasfi, Tarek; Temime-Roussel, Brice; Coulomb, Bruno; Vassalo, Laurent; Boudenne, Jean-Luc

    2017-05-01

    An undesirable consequence of disinfection is the formation of chemical contaminants known as disinfection byproducts (DBPs). Chronic exposure to DBPs has been linked to adverse health effects. The occurrence of DBPs in chlorinated pools filled with seawater (such as thalassotherapy pools and pools in spas) has received little attention so far. The present study evaluated the speciation and levels of disinfection byproducts in indoor swimming pools filled with seawater and treated with chlorine. Water and air samples were collected from three indoor swimming pools located in Southern France. Several classes of DBPs including trihalomethanes, haloacetic acids, haloacetonitriles, and trihaloacetaldehydes were analyzed in water. Halogenated volatile organic compounds were analyzed in air. Extractable organic halides (EOX) contents were determined using combustion/micro-coulometry system. The speciation of DBPs identified in the three pools was predominantly brominated. The mean (arithmetic) concentration of bromoform, dibromoacetic acid, tribromoacetic acid, dibromoacetonitrile and bromal hydrate in the three pools was 79.2, 72.9, 59.9, 26.9 and 10.0μg/L, respectively. By weight, HAAs represented the most abundant chemical class followed by THMs. In air, bromoform was the most abundant THM occurring at a mean concentration of 133.2μg/m(3) in the three pools. The mean EOX level was 706μgCl(-)/L for the three pools. In average, the quantified DBPs accounted for only 14% of EOX, thus 86% of EOX remained unknown. Further research is warranted to identify the unknown DBPs. Copyright © 2017 Elsevier GmbH. All rights reserved.

  2. In-Situ Investigation of Tomato Plants as Methyl Halide Sources

    NASA Astrophysics Data System (ADS)

    King, D. B.; Butler, J. H.; Mondeel, D. J.

    2002-05-01

    Natural halocarbons contribute significantly to the destruction of stratospheric ozone. Methyl bromide and methyl chloride, both of which come primarily from natural sources, supply about one-quarter of the equivalent chlorine to the stratosphere. Other halogenated compounds, such as dibromomethane, bromoform, and methyl iodide, might be significant halogen sources to the stratosphere as well. The budgets of these compounds, and the mechanisms responsible for their production and destruction, generally are poorly understood. For example, known sources of both methyl bromide and methyl chloride outweigh their known sinks by 50-100%, making it difficult to predict future atmospheric concentrations of these compounds. As the global climate changes, atmospheric halocarbon concentrations are likely to respond to changes in sea surface temperature, biological productivity on land and in water, and global wind patterns. Terrestrial plants are a potentially significant source of many light halocarbons. As a first cut to assess this potential, we measured the production of about 20 halocarbons by tomato plants in a hydroponic greenhouse in Northern California. This enabled us to investigate production directly from the plants, without the interference of soils, which have been shown to remove some of these compounds from the atmosphere. Results differed for the methyl halides and the polyhalogenated compounds. Methyl halide production was small or zero during initial experiments. However, the addition of a halide ion solution (KBr, KCl, and KI) to the plants' nutrient mixture appeared to increase production of methyl bromide (by a factor of three) and methyl iodide (by a factor of seven) significantly. In contrast, several polyhalogenated compounds (e.g., bromoform and bromochloromethane) were produced during all experiments, with increases on the order of 50% to 600%. The addition of the halide solution did not affect the production of these compounds. The results from

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

    PubMed Central

    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

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

    PubMed

    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.

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

    PubMed Central

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Leedham Elvidge, E. C.; Phang, S.-M.; Sturges, W. T.; Malin, G.

    2014-07-01

    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.

  7. Ozone Destruction in the Upper Troposphere/Lower Stratosphere from Short-Lived Halogens and Climate Impacts

    NASA Astrophysics Data System (ADS)

    Hossaini, Ryan; Chipperfield, Martyn; Montzka, Stephen; Rap, Alex; Dhomse, Sandip; Feng, Wuhu

    2014-05-01

    Halogens released from very short-lived substances (VSLS) can deplete ozone in the upper-troposphere and lower stratosphere where the perturbation can exert a large climate impact. In addition to the known ozone loss from natural biogenic bromine VSLS, such as bromoform (CHBr3), using a global atmospheric model we show that anthropogenic chlorine VSLS such as dichloromethane (CH2Cl2) - not regulated by the Montreal Protocol - also contribute. Although this impact is small compared to bromine VSLS at present, CH2Cl2 has industrial sources and observations show its atmospheric loading is increasing rapidly. We estimate a significant radiative effect of the bromine and chlorine VSLS-driven lower stratospheric ozone destruction of -0.11 Wm-2. The largest impact comes from ozone loss at high latitudes, where column ozone decreases due to VSLS are up to 6%. The trend in anthropogenic chlorine VSLS could cause a significant radiative forcing, especially if augmented by any trend in natural bromine VSLS. We also used the model to study the impact of iodine-containing VSLS such as methyl iodide (CH3I). Of the three halogens iodine has the largest leverage to destroy lower stratospheric ozone, but current limits based on IO observations indicate only a minor impact at present.

  8. Chlorination byproducts induce gender specific autistic-like behaviors in CD-1 mice.

    PubMed

    Guariglia, Sara Rose; Jenkins, Edmund C; Chadman, Kathryn K; Wen, Guang Y

    2011-10-01

    In 2000, the Agency for Toxic Substances and Disease Registry (ATSDR) released a report concerning elevated autism prevalence and the presence water chlorination byproducts in the municipal drinking water supply in Brick Township, New Jersey. The ATSDR concluded that it was unlikely that these chemicals, specifically chloroform, bromoform (Trihalomethanes; THMs) and tetrachloroethylene (Perchloroethylene; PCE) had contributed to the prevalence of autism in this community based upon correlations between timing of exposure and/or concentration of exposure. The ATSDR conclusion may have been premature, as there is no conclusive data evidencing a correlation between a particular developmental time point that would render an individual most susceptible to toxicological insult with the development of autism. Therefore, it was our aim to determine if these chemicals could contribute to autistic like behaviors. We found that males treated with THMs and PCE have a significant reduction in the number of ultrasonic vocalizations (USVs) emitted in response to maternal separation, which are not attributed to deficits in vocal ability to or to lesser maternal care. These same males also show significantly elevated anxiety, an increase in perseverance behavior and a significant reduction in sociability. The sum of our data suggests that male, but not female mice, develop autistic like behaviors after gestational and postnatal exposure to the aforementioned chemical triad via drinking water. We believe development of such aberrant behaviors likely involves GABAergic system development. Published by Elsevier B.V.

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

    NASA Astrophysics Data System (ADS)

    Leedham Elvidge, E. C.; Phang, S.-M.; Sturges, W. T.; Malin, G.

    2015-01-01

    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.

  10. Detection of Brominated By-Products Using a Sensor Array Based on Nanostructured Thin Films of Conducting Polymers

    PubMed Central

    Carvalho, Eduarda Regina; Filho, Nelson Consolin; Venancio, Everaldo Carlos; Osvaldo, N. O.; Mattoso, Luiz H. C.; Martin-Neto, Ladislau

    2007-01-01

    The detection of the carcinogenic trihalomethanes (THM) in public water supply systems using low-cost equipment has become an essential feature, since these compounds may be generated as by-products of water-treatment processes. Here we report on a sensor array that extends the concept of an “electronic tongue” to detect small amounts of bromoform, bromodichloromethane and dibromochloromethane, with detection limits as low as 0.02 mg L-1. The sensor array was made up of 10 sensing units, in which nanostructured films of conducting and natural polymers were deposited onto gold interdigitated electrodes. The principle of detection was impedance spectroscopy, with measurements carried out in the range between 1 Hz to 1 MHz. Using data at 1 kHz, at which the electrical response varied considerably by changing the analyte, we demonstrated with principal component analysis (PCA) that samples with the 3 brominated trihalomethanes can be distinguished from each other and for various concentrations. PMID:28903292

  11. Some Rearrangements of Free Alkyl Radicals and Alkyl Cations in Solutions

    NASA Astrophysics Data System (ADS)

    Reutov, Oleg A.

    1984-03-01

    The results of studies of rearrangement reactions by the author and his co-workers during the last 20 years are described. A rearrangement of the n-propyl free radical in solutions as a result of the hydrogen 1,3-shift has been discovered and its characteristic features have been investigated (using carbon-14, deuterium, and tritium). The reaction involving the formation of organomercury compounds from mercury salts of carboxylic acids and peroxides has been studied and a mechanism has been proposed for it. New skeletal rearrangements in the thermal decomposition of cycloalkyl peroxides in benzene and bromoform have been discovered. It has been shown by the method of double 13C NMR that some of the reactions involve the formation of species which manifest properties intermediate between those of free radicals and carbonium ions. The mechanism of the thermolysis of peroxides is considered. The skeletal rearrangements and hydride shifts in the deamination and solvolysis of alicyclic compounds have been studied and a number of rearrangements with 1,2-migration of the halogen and in particular the isomerisation of acyloxybromopropanes in organic solvents, which takes place particularly readily, have been observed. The bibliography includes 103 references.

  12. Water-quality assessment of south-central Texas: Occurrence and distribution of volatile organic compounds in surface water and ground water, 1983-94, and implications for future monitoring

    USGS Publications Warehouse

    Ging, P.B.; Judd, L.J.; Wynn, K.H.

    1997-01-01

    The study area of the South-Central Texas study unit of the National Water-Quality Assessment Program comprises the Edwards aquifer in the San Antonio region and its catchment area. The first phase of the assessment includes evaluation of existing water-quality data for surface water and ground water, including volatile organic compounds, to determine the scope of planned monitoring. Most analyses of volatile organic compounds in surface water are from the National Pollutant Discharge Elimination System sites in San Antonio, Texas. Nine volatile organic compounds were detected at the six sites. The three compounds with the most detections at National Pollutant Discharge Elimination System sites are 1,2,4-trimethylbenzene, toluene, and xylene. Analysis of volatile organic compounds in ground water was limited to Edwards aquifer wells. Twenty-eight volatile organic compounds were detected in samples from 89 wells. The five most commonly detected compounds in samples from wells, in descending order, are tetrachloroethene, trichloroethene, bromoform, chloroform, and dibromochloromethane. Detections of volatile organic compounds in surface water and ground water within the South-Central Texas study area are limited to site-specific sources associated with development; therefore, planned monitoring for possible detections of volatile organic compounds as part of the National Water-Quality Assessment Program will emphasize areas of expanding population and development. Monitoring of volatile organic compounds is planned at National Pollutant Discharge Elimination System sites, at basic fixed surface-water sites, and in the ground-water study-unit surveys.

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

    PubMed

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

    2009-01-26

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

  14. Bacterial Cellular Materials as Precursors of Chloroform

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

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

    2016-05-05

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

  16. Occurrence of Organic Compounds in Source and Finished Samples from Seven Drinking-Water Treatment Facilities in Miami-Dade County, Florida, 2008

    USGS Publications Warehouse

    Foster, Adam L.; Katz, Brian G.

    2010-01-01

    The U.S. Geological Survey, in cooperation with the Miami-Dade Water and Sewer Department, conducted a reconnaissance study in 2008 to determine the occurrence of 228 organic compounds in raw, source (untreated) and finished (treated) drinking water at seven municipal water-treatment facilities in Miami-Dade County. Results of this sampling study showed that 25 (about 11 percent) of the 228 organic compounds were detected in at least one source water sample and 22 (about 10 percent) were detected in at least one finished water sample. The concentrations of organic compounds in source water samples were less than or equal to 0.2 (u or mu)g/L (micrograms per liter). The concentrations of organic compounds in finished water samples were generally less than or equal to 0.5 (u or mu)g/L, with the exception of bromoform (a possible disinfection byproduct) at estimated concentrations ranging from 0.7 to 2.8 (u or mu)g/L and diethyl phthalate (a plasticizer compound) at 2 (u or mu)g/L.

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

    SciTech Connect

    Wever, R.; Tromp, M.G.M.; Krenn, B.E.; Marjani, A.; Van Tol, M. )

    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.

  18. Spatial distribution of brominated very short-lived substances in the eastern Pacific

    NASA Astrophysics Data System (ADS)

    Liu, Yina; Yvon-Lewis, Shari A.; Thornton, Daniel C. O.; Campbell, Lisa; Bianchi, Thomas S.

    2013-05-01

    Seawater concentrations and distributions of brominated very short-lived substances (BrVSLS), including bromoform (CHBr3), dibromomethane (CH2Br2), bromodichloromethane (CHBrCl2), chlorodibromomethane (CHClBr2), were measured in the upper water column (5-750 m) in the eastern Pacific. Inorganic nutrient, pigment concentrations, and picoplankton cell counts were measured to determine biogeochemical factors that affect the production and distribution of these BrVSLS. Elevated concentrations of BrVSLS were observed in coastal and tropical seawater. Concentration maxima for CHBr3, CH2Br2, and CHClBr2 were observed below the mixed layer, near the subsurface chlorophyll a maxima, which suggest BrVSLS production may be related to photosynthetic biomass production. Our results also suggest that heterotrophic bacteria may also contribute to CH2Br2 and CHBrCl2 production in the water column. The maximum CHBrCl2 concentration was observed at a depth much deeper than the euphotic zone, which suggests sources other than photosynthetic biomass. Elevated CHBrCl2 concentrations in deeper waters were coincident with elevated CHCl3 concentrations, which may be an evidence for successive chlorine substitution of CHBr3 in deeper and older water masses.

  19. Very Short-lived Bromomethanes in the Upper Troposphere/Lower Stratosphere during CARIBIC May 2009 to May 2011

    NASA Astrophysics Data System (ADS)

    Wisher, Adam; Oram, Dave; Laube, Johannes; van Velthoven, Peter; Brenninkmeijer, Carl

    2013-04-01

    Reactive halogenated compounds including brominated very short-lived substances (VSLS) play an important role both in the stratosphere, where they impact on stratospheric ozone, and in the troposphere, where they participate in catalytic ozone destruction and aerosol formation. According to the latest WMO figures, brominated VSLS could be responsible for 1-8 ppt contribution to the stratospheric bromine burden. However, observations of brominated VSLS in the upper troposphere/lower stratosphere are relatively sparse. In this study we present measurements made during the CARIBIC project from May 2009 to May 2011 using a negative ion chemical ionisation (NICI) mass spectrometer instrument. NICI is a "soft" ionisation technique that gives enhanced detection limits for electronegative species such as halocarbons. The CARIBIC project deploys a large range of automated instruments in an airfreight container aboard a Lufthansa A340-600 passenger aircraft. The container system also houses two automated bottle samplers which are analysed for various compounds. As part of the project we measure a range of halogenated compounds in the bottle samples. We will present profiles of bromoform (CHBr3), dibromomethane (CH2Br2), dibromochloromethane (CHBr2Cl), bromodichloromethane (CHBrCl2) and bromochloromethane (CH2BrCl) and compare results with previous measurements of brominated VSLS.

  20. Electrochemical determination of trihalomethanes in water by means of stripping analysis.

    PubMed

    Peverly, Angela A; Peters, Dennis G

    2012-07-17

    A protocol has been developed and evaluated for the determination of trihalomethanes (THMs) at the submicromolar concentration level in water. This method is based on a three-step stripping analysis that utilizes a single electrochemical cell and that entails (a) direct electrochemical reduction of a trihalomethane at a silver cathode to form halide ions in an aqueous sample containing tetraethylammonium benzoate, (b) capture of the released halide ions as a silver halide film on the surface of a silver gauze anode, and (c) cathodic reduction and quantitation of the silver halide film by means of differential pulse voltammetry. Using this procedure, we have determined THMs individually; bromoform and chloroform have been successfully quantitated in 30 min and with a detection limit of 3.0 μg L(-1) (12 nM) and 6.0 μg L(-1) (50 nM), respectively. In addition, we have employed our methodology to determine the total trihalomethane (TTHM) content in a prepared water sample at a level commensurate with the maximum allowable annual average of 80 μg L(-1) mandated by the United States Environmental Protection Agency. We have compared our TTHM results to those obtained by an independent testing laboratory.

  1. Removal of trihalomethane from chlorinated seawater using gamma radiation.

    PubMed

    Rajamohan, R; Natesan, Usha; Venugopalan, V P; Rajesh, Puspalata; Rangarajan, S

    2015-12-01

    Chlorine addition as a biocide in seawater results in the formation of chlorination by-products such as trihalomethanes (THMs). Removal of THMs is of importance as they are potential mutagenic and carcinogenic agents. In this context, a study was conducted that used ionizing radiation to remove THMs from chlorinated (1, 3, and 5 mg/L) seawater by applying various dosages (0.4-5.0 kGy) of gamma radiation. Bromoform (BF) showed a faster rate of degradation as compared to other halocarbons such as bromodichloromethane (BDCM) and dibromochloromethane (DBCM). In chlorine-dosed seawater, total irradiation dose of 0.4 to 5 kGy caused percentage reduction in the range of 6.9 to 76.7%, 2.3 to 99.6%, and 45.7 to 98.3% for BDCM, DBCM, and BF, respectively. During the irradiation process, pH of the chlorinated seawater decreased with increase in the absorbed dose; however, no change in total organic carbon (TOC) was observed. The results show that gamma dose of 2.5 kGy was adequate for maximum degradation of THM; but for complete mineralization, higher dose would be required.

  2. Identification of disinfection by-products in freshwater and seawater swimming pools and evaluation of genotoxicity.

    PubMed

    Manasfi, Tarek; De Méo, Michel; Coulomb, Bruno; Di Giorgio, Carole; Boudenne, Jean-Luc

    2016-03-01

    Exposure to disinfection byproducts (DBPs) in swimming pools has been linked to adverse health effects. Numerous DBPs that occur in swimming pools are genotoxic and carcinogenic. This toxicity is of a greater concern in the case of brominated DBPs that have been shown to have substantially greater toxicities than their chlorinated analogs. In chlorinated seawater swimming pools, brominated DBPs are formed due to the high content of bromide. Nevertheless, very little data is reported about DBP occurrence and mutagenicity of water in these pools. In the present study, three seawater and one freshwater swimming pools located in Southeastern France were investigated to determine qualitatively and quantitatively their DBP contents. An evaluation of the genotoxic properties of water samples of the freshwater pool and a seawater pool was conducted through the Salmonella assay (Ames test). The predominant DBPs identified in the freshwater pool were chlorinated species and included trichloroacetic acid, chloral hydrate, dichloroacetonitrile, 1,1,1-trichloropropanone and chloroform. In the seawater pools, brominated DBPs were the predominant species and included dibromoacetic acid, bromoform and dibromoacetonitile. Bromal hydrate levels were also reported. In both types of pools, haloacetic acids were the most prevalent chemical class among the analyzed DBP classes. The distribution of other DBP classes varied depending on the type of pool. As to genotoxicity, the results of Ames test showed higher mutagenicity in the freshwater pool as a consequence of its considerably higher DBP contents in comparison to the tested seawater pool. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Dissolved organic matter composition drives the marine production of brominated very short-lived substances.

    PubMed

    Liu, Yina; Thornton, Daniel C O; Bianchi, Thomas S; Arnold, William A; Shields, Michael R; Chen, Jie; Yvon-Lewis, Shari A

    2015-03-17

    Brominated very short-lived substances (BrVSLS), such as bromoform, are important trace gases for stratospheric ozone chemistry. These naturally derived trace gases are formed via bromoperoxidase-mediated halogenation of dissolved organic matter (DOM) in seawater. Information on DOM type in relation to the observed BrVSLS concentrations in seawater, however, is scarce. We examined the sensitivity of BrVSLS production in relation to the presence of specific DOM moieties. A total of 28 model DOM compounds in artificial seawater were treated with vanadium bromoperoxidase (V-BrPO). Our results show a clear dependence of BrVSLS production on DOM type. In general, molecules that comprise a large fraction of the bulk DOM pool did not noticeably affect BrVSLS production. Only specific cell metabolites and humic acid appeared to significantly enhance BrVSLS production. Amino acids and lignin phenols suppressed enzyme-mediated BrVSLS production and may instead have formed halogenated nonvolatile molecules. Dibromomethane production was not observed in any experiments, suggesting it is not produced by the same pathway as the other BrVSLS. Our results suggest that regional differences in DOM composition may explain the observed BrVSLS concentration variability in the global ocean. Ultimately, BrVSLS production and concentrations are likely affected by DOM composition, reactivity, and cycling in the ocean.

  4. [A pilot study on trihalomethane formation in water treated by chlorine dioxide].

    PubMed

    Li, J; Yu, Z; Gao, M

    1996-01-01

    Trihalomethane (THM) formation was determined by gas chromatography in water disinfected with chlorine dioxide (ClO2) only or ClO2 combined with chlorine (Cl2), to lay a basis for water disinfected with ClO2. Results showed no THM was produced in water disinfected with ClO2 only if without existence of bromine (Br) ion in it; certain amount of bromoform could be formed with existence of bromine ion, and THM formation could be inhibited by ClO2 and Cl2, with a ratio of greater than 1 between them. Light irradiation could decrease the amount of THM produced whether in disinfection with ClO2 or combination with ClO2 and Cl2. No significant effect of pH value of water on THM formation was observed, but pH should be controlled under neutral or slightly acidic to ensure the concentration of ClO2 in water.

  5. Maps showing mineralogical data for nonmagnetic heavy-mineral concentrates in the Talkeetna Quadrangle, Alaska

    USGS Publications Warehouse

    Tripp, R.B.; Karlson, R.C.; Curtin, G.C.

    1978-01-01

    Reconnaissance geochemical and mineralogical sampling was done in the Talkeetna Quadrangle during 1975 and 1976 as part of the Alaska Mineral Resource Assessment Program (AMRAP). These maps show the distribution of gold, scheelite, chalcopyrite, arsenopyrite, galena, fluorite, cinnabar, and malachite in the nonmagnetic fraction of heavy-mineral concentrates. Heavy-mineral concentrate samples were collected at 812 sites from active stream channels. The heavy-mineral concentrates were obtained by panning stream sediment in the field to remove most of the light minerals. The panned samples were then sieved through a 20-mesh (0.8 mm) sieve in the laboratory, and the minus-20-mesh fraction was further separated with bromoform (specific gravity, 2.86) to remove any remaining light-mineral grains. Magnetite and other strongly magnetic heavy minerals were removed from the heavy-mineral fraction by use of a hand magnet. The remaining sample was passed through a Frantz Isodynamic Separator and a nonmagnetic fraction was examined for its mineralogical content with the aid of a binocular microscope and an x-ray diffractometer. The nonmagnetic concentrates primarily contain phyllite fragments, muscovite, sphene, zircon, apatite, tourmaline, rutile, and anatase. Most ore and ore-related minerals also occur in this fraction.

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

    SciTech Connect

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

    2013-11-27

    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.

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

    PubMed

    Chiang, Hung-Lung; Lin, Kuo-Hsiung

    2014-01-15

    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 0-0.7mg/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%.

  8. Occurrence of disinfection by-products in tap water distribution systems and their associated health risk.

    PubMed

    Lee, Jin; Kim, Eun-Sook; Roh, Bang-Sik; Eom, Seog-Won; Zoh, Kyung-Duk

    2013-09-01

    The concentrations of trihalomethanes (THMs), including chloroform, bromodichloromethane, dibromochloromethane, and bromoform, and haloacetic acids (HAAs; monochloroacetic acid, monobromoacetic acid, dibromoacetic acid, dichloroacetic acid, and trichloroacetic acid) were measured in tap waters passing through water distribution systems of six water treatment plants in Seoul, Korea, and their associated health risks from exposure to THMs through ingestion, dermal contact, and inhalation were estimated using a probabilistic approach. The concentration ranges for total THMs and HAA5 were 3.9-53.5 and

  9. Analysis of trihalomethanes in drinking water using headspace-SPME technique with gas chromatography.

    PubMed

    Cho, Deok-Hee; Kong, Sung-Ho; Oh, Seong-Geun

    2003-01-01

    In many drinking water treatment plants, the chlorination process is one of the main techniques used for the disinfection of water. This disinfecting treatment leads to the formation of trihalomethanes (THMs) such as chloroform, dichlorobromomethane, chlorodibromomethane and bromoform. In this study, headspace-solid-phase microextraction (HS-SPME, 85 microm carboxen/polydimethylsiloxane fiber) technique was applied for the analysis of THMs in drinking water. The effects of experimental parameters such as kinds of SPME fiber, the volume ratio of sample to headspace, the addition of salts, magnetic stirring, extraction temperature, extraction time and desorption time on the analysis were investigated. Analytical parameters such as linearity, repeatability and limit of detection were also evaluated. The results of THMs from the survey of Seongnam (Korea) drinking water samples showed that the highest total trihalomethane and chloroform were 24.03 and 13.34 microg/l, which were well within the Korean drinking water quality standard of 100 and 80 microg/l, respectively.

  10. The advanced EctoSys electrolysis as an integral part of a ballast water treatment system.

    PubMed

    Echardt, J; Kornmueller, A

    2009-01-01

    A full-scale 500 m(3)/h ballast water treatment system was tested according to the landbased type approval procedure of the International Maritime Organization (IMO). The system consists of disc filters followed by the advanced EctoSys electrolysis as an integral part for disinfection. The test water quality exceeded by far the minimum requirements for type approval testing. Due to the properties of the special electrodes used together with the striking disinfection effect, the disinfectants assumed to be produced inline by the EctoSys cell in river water were hydroxyl radicals, while in brackish water additionally chlorine and consequently the more stable bromine were formed. In river water, no residual oxidants could be detected in accordance with the assumed production of not responding, highly-reactive and short-living hydroxyl radicals. Accordingly, disinfection byproduct (DBP) formation was very low and close to the limit of quantification in river water. While in brackish water, initial residual oxidant concentrations were maximum 2 mg/L as chlorine and mostly brominated DBP (especially bromoform and bromate) were found. Overall considering this worst case test approach, the DBP concentrations of the treated effluents were below or in the range of the WHO Drinking Water Guideline values and therefore evaluated as acceptable for discharge to the environment. The stringent discharge standard by IMO concerning viable organisms was fully met in river and brackish water, proving the disinfection efficiency of the EctoSys electrolysis against smaller plankton and bacteria.

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

    PubMed Central

    2011-01-01

    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. PMID:21975145

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

    USGS Publications Warehouse

    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.

  13. Nanodetection of the disinfection by-products on GC-MS techniques

    NASA Astrophysics Data System (ADS)

    Ristoiu, Dumitru; Haydee, Melinda; Ristoiu, Tania

    2009-01-01

    Exposures to disinfection by-products (DBPs) in residential drinking water occur through multiple routes and vary across the population because of differences in the amount and ways people use water. Municipal water in the Romania is disinfected, with chlorine being the most common disinfectant agent. Disinfection of water, in additional to having the benefit of destroying microbes that can transmit diseases, has the drawback of producing a series of compounds known as disinfection by-products (DBPs). Chlorination produces many compounds containing chlorine and/or bromine, some of which have been shown to be carcinogenic, mutagenic, and/or teratogenic in animal studies. The most abundant class of DBPs that result from chlorination of drinking water are trihalomethanes (THMs) - chloroform (CHCl3), dichlorobromomethane (CHCl2Br), dibromochloromethane (CHBr2Cl) and bromoform (CHBr3). The most predominant THM species was CHCl3 and it highest concentration was 85•106 ng/m3. The others THMs compounds concentration were lower, between 65•104 ng/m3 and 12•106 ng/m3. THMs compounds were analyzed on gas chromatography coupled with mass spectrometer detector (GC-MS) and head space technique (HS) was used for all analysis.

  14. Comparison of volatile organic levels between sites and seasons for the total exposure assessment methodology (TEAM) study

    NASA Astrophysics Data System (ADS)

    Hartwell, T. D.; Pellizzari, E. D.; Perritt, R. L.; Whitmore, R. W.; Zelon, H. S.; Wallace, L.

    Comparisons were made between volatile organic compounds (VOCs) in breath, personal air, fixed-site outdoor air and water samples from a probability (random) sample of individuals in Bayonne/Elizabeth, New Jersey; Los Angeles and Pittsburg/Antioch, California; Greensboro, North Carolina; and Devils Lake, North Dakota. In addition, comparisons were made between seasons in the Bayonne/Elizabeth and Los Angeles sites where the same individuals were sampled in two seasons. The most striking differences between sites and seasons were in outdoor air samples. For this medium the concentrations in Los Angeles in the winter season were much higher than in Bayonne/Elizabeth, New Jersey in the winter. However, in the summer season this difference was not evident due to a dramatic decrease in VOC levels in Los Angeles in the summer. Outdoor VOC levels in Greensboro and Devils Lake were usually dramatically lower than both Bayonne/Elizabeth and the California sites. Concentration levels for the breath and personal air samples were usually higher in the winter than the spring or summer. This was particularly true in Los Angeles for personal air samples. For the breath samples, this pattern was not clearcut and, in fact, Bayonne/Elizabeth tended to have higher concentrations in the summer. For water samples, Devils Lake had particularly low VOC levels. Bromoform, which was found in California samples, was almost never present in Bayonne/Elizabeth, Greensboro and Devils Lake samples.

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

    PubMed

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

    2006-03-28

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

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

    PubMed

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

    2011-03-09

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

  17. EPA (Environmental Protection Agency) method study 23a, method 501. 1, trihalomethanes by purge and trap (reannouncement of PB84-169994 - see notes field for explanation)

    SciTech Connect

    Warner, B.J.; Cheng, S.C.; Friedman, C.S.; Mitrosky, S.; Snyder, A.D.

    1984-03-01

    The experimental design and the results of an interlaboratory study of U.S. Environmental Protection Agency (USEPA) method 501.1 to detect trihalomethanes in drinking water are described herein. In the method, trihalomethanes are extracted by an inert gas which is bubbled through the aqueous sample. The vapors are then trapped on a short column containing a suitable sorbent. The trapped compounds are subsequently thermally desorbed onto the head of a gas chromatographic column. An electrolytic conductivity detector is used to measure the compounds. The six concentrations of spiking solutions contained chloroform, bromodichloromethane, chlorodibromomethane and bromoform. The two waters used in the study were distilled and drinking water, both supplied by the individual laboratories. Statistical analyses and conclusions in this report are based on analytical data obtained by twenty collaborating laboratories. This report was submitted in partial fulfillment of contract 68-03-2856 by Monsanto Research Corporation under the sponsorship of the U.S. Environmental Protection Agency. The report covers a period from September 1979 to December 1982.

  18. Halocarbons, alkyl nitrates, and nonmethane hydrocarbons quantified from surface air and water samples in the Gulf of Maine during NEAQS

    NASA Astrophysics Data System (ADS)

    Haase, K. B.; Harlow, A.; Sive, B. C.; Wingenter, O. W.

    2003-12-01

    During the New England Air Quality Study (NEAQS) campaign, July-August 2002, natural and anthropogenic halocarbons, alkyl nitrates, and nonmethane hydrocarbons (NMHCs) in surface air and water samples were quantified in situ using gas chromatography with flame ionization and electron capture detection aboard the NOAA R/V Ronald H. Brown. The cruise focused on an area in the Gulf of Maine, south of Portsmouth Harbor, near the Isle of Shoals, and in the Boston Harbor area. Between Cape Ann and Newburyport, saturation anomalies for anthropogenic halocarbons of 100% for CFC-113, 140% for H-1211, 40% for methyl chloroform, and 15% for carbon tetrachloride were observed. Throughout the cruise, subsequent high levels of these compounds were found in the area. The findings suggest that there are local anthropogenic sources of these gases, which are draining into the Gulf of Maine from local rivers, harbors, or estuaries. Elevated level of methyl bromide, methyl iodide, bromoform, and chloroform were measured near the coast, and decreased with increasing distance. The distributions of the NMHCs were similar to the naturally produced marine halocarbons, suggesting similar sources. Supersaturation of alkyl nitrates were observed indicating an oceanic source of methyl nitrate, i-propyl nitrate, n-propyl nitrate, and 2-butyl nitrate, with the later three compounds reported here in ocean water samples for the first time.

  19. Hollow-fiber solvent bar microextraction with gas chromatography and electron capture detection determination of disinfection byproducts in water samples.

    PubMed

    Correa, Liliana; Fiscal, Jhon Alex; Ceballos, Sandra; de la Ossa, Alberto; Taborda, Gonzalo; Nerin, Cristina; Rosero-Moreano, Milton

    2015-09-10

    A liquid-phase microextraction method that uses a hollow-fiber solvent bar microextraction technique was developed by combining gas chromatography with electron capture detection for the analysis of four trihalomethanes (chloroform, dichlorobromomethane, chlorodibromomethane, and bromoform) in drinking water. In the microextraction process, 1-octanol was used as the solvent. The technique operates in a two-phase mode with a 5 min extraction time, a 700 rpm stirring speed, a 30°C extraction temperature, and NaCl concentration of 20%. After microextraction, one edge of the membrane was cut, and 1 μL of solvent was collected from the membrane using a 10 μL syringe. The solvent sample was directly injected into the gas chromatograph. The analytical characteristics of the developed method were as follows: detection limits, 0.017-0.037 ng mL(-1) ; linear working range, 10-900 ng mL(-1) ; recovery, 74 ± 9-91 ± 2; relative standard deviation, 5.7-10.3; and enrichment factor, 330-455. A simple, fast, economic, selective, and efficient method with big possibilities for automation was developed with a potential use to apply with other matrices and analytes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Nonideal transport of contaminants in heterogeneous porous media: 10. Impact of co-solutes on sorption by porous media with low organic-carbon contents

    PubMed Central

    Brusseau, M.L.; Schnaar, G.; Johnson, G.R.; Russo, A.E.

    2013-01-01

    The impact of co-solutes on sorption of tetrachloroethene (PCE) by two porous media with low organic-carbon contents was examined by conducting batch experiments. The two media (Borden and Eustis) have similar physical properties, but significantly different organic-carbon (OC) contents. Sorption of PCE was nonlinear for both media, and well-described by the Freundlich equation. For the Borden aquifer material (OC = 0.03%), the isotherms measured with a suite of co-solutes present (1,2-dichlorobenzene, bromoform, carbon tetrachloride, and hexachloroethane) were identical to the isotherms measured for PCE alone. These results indicate that there was no measurable impact of the co-solutes on PCE sorption for this system. In contrast to the Borden results, there was a measureable reduction in sorption of PCE by the Eustis soil (OC = 0.38%) in the presence of the co-solutes. The organic-carbon fractions of both media contain hard-carbon components, which have been associated with the manifestation of nonideal sorption phenomena. The disparity in results observed for the two media may relate to relative differences in the magnitude and geochemical nature of these hard-carbon components. PMID:22717163

  1. Volatile organic compounds in Arctic snow: concentrations and implications for atmospheric processes.

    PubMed

    Kos, Gregor; Kanthasami, Visahini; Adechina, Nafissa; Ariya, Parisa A

    2014-11-01

    The role of volatile organic compounds (VOC) in the snowpack for atmospheric oxidation, gas-particle transfer and aerosol formation remains poorly understood, partly due to a lack of methodology and unavailable data. We deployed solid phase micro-extraction (SPME) gas chromatography with flame ionization detection for measurement of halogenated, aromatic and oxygenated VOC in the snow pack in Alert, NU, Canada, a High Arctic site. Maximum concentrations in snow were 39 ± 6 μg L(-1) (styrene), indicating a potential VOC contribution to atmospheric oxidation and aerosol formation. Concurrently sampled air had concentrations of up to 1.0 ± 0.3 ng L(-1) (trichloroethene). Back trajectory data showed a change of air mass source region during a depletion event of several VOC in snow (e.g., trichloroethene and benzene). Snow profiles showed an enrichment of most compounds close to the surface. During a second study in Barrow, AK, USA VOC were quantified in snow and frost flowers in the Montreal lab. In Barrow work was carried out as part of the extensive OASIS (Ocean-Atmosphere-Sea Ice-Snowpack) field campaign. Maximum VOC concentrations were up to 1.3 ± 0.1 μg L(-1) (acetophenone). Bromoform in frost flowers averaged 0.19 ± 0.04 μg L(-1), indicating the potential to contribute to bromine generation through photolysis.

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

    PubMed

    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.

  3. Monitoring of chlorination disinfection by-products and their associated health risks in drinking water of Pakistan.

    PubMed

    Abbas, Sidra; Hashmi, Imran; Rehman, Muhammad Saif Ur; Qazi, Ishtiaq A; Awan, Mohammad A; Nasir, Habib

    2015-03-01

    This study reports the baseline data of chlorination disinfection by-products such as trihalomethanes (THMs) and their associated health risks in the water distribution network of Islamabad and Rawalpindi, Pakistan. THM monitoring was carried out at 30 different sampling sites across the twin cities for 6 months. The average concentration of total trihalomethanes (TTHMs) and chloroform ranged between 575 and 595 μg/L which exceeded the permissible US (80 μg/L) and EU (100 μg/L) limits. Chloroform was one of the major contributors to the TTHMs concentration (>85%). The occurrence of THMs was found in the following order: chloroform, bromodichloromethane > dibromochloromethane > bromoform. Lifetime cancer risk assessment of THMs for both males and females was carried out using prediction models via different exposure routes (ingestion, inhalation, and dermal). Total lifetime cancer risk assessment for different exposure routes (ingestion, inhalation, and skin) was carried out. The highest cancer risk expected from THMs seems to be from the inhalation route followed by ingestion and dermal contacts. The average lifetime cancer risk for males and females was found to be 0.51 × 10⁻³ and 1.22 × 10⁻³, respectively. The expected number of cancer risks per year could reach two to three cases for each city.

  4. Assessment of disinfection by-products in drinking water in Korea.

    PubMed

    Shin, D; Chung, Y; Choi, Y; Kim, J; Park, Y; Kum, H

    1999-01-01

    The main purpose of applying the chlorination process during water treatment is for disinfection. Research results, however, indicate that disinfection byproducts (DBPs) including trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), haloketones (HKs), and chloropicrin (CP) can be produced by the chlorination process. Some of these DBPs are known to be potential human carcinogens. This 3-year project is designed to establish a standard analysis procedure for DBPs in drinking water of this country and investigate the distribution and sources of specific DBPs. The occurrence level of DBPs in drinking water was below 50 micrograms/l in most cases. THMs in plant effluent accounted for 60% of all DBPs measured, whereas HAAs accounted for 20%, HANs 12%, HKs 5% and CP 3%. Chloroform was found to be the major THMs compound (77%), followed by bromodichloromethane (BDCM, 18%) and bromoform (BF, 3%). The concentration of DBPs formed in distribution systems increased from those detected in plant effluent. Comparison of humic acid and sewage as precursors for THMs formation showed that humic acid was the major THMs precursor. Results would play an important role in exposure assessment as a part of the risk assessment process, and would give basic information for establishment of DBPs reduction and management procedures.

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

    PubMed Central

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

    2013-01-01

    Disinfection by-products (DBPs) are ubiquitous contaminants in tap drinking water with the potential to produce adverse health effects. Filtering and boiling tap water can lead to changes in the DBP concentrations and modify the exposure through ingestion. Changes in the concentration of 4 individual trihalomethanes (THM4) (chloroform (TCM), bromodichloromethane (BDCM), dibromochloromethane (DBCM), and bromoform (TBM)), MX, and bromate were tested when boiling and filtering high bromine-containing tap water from Barcelona. For filtering, we used a pitcher-type filter and a household reverse osmosis filter; for boiling, an electric kettle, a saucepan, and a microwave were used. Samples were taken before and after each treatment to determine the change in the DBP concentration. pH, conductivity, and free/total chlorine were also measured. A large decrease of THM4 (from 48% to 97%) and MX concentrations was observed for all experiments. Bromine-containing trihalomethanes were mostly eliminated when filtering while chloroform when boiling. There was a large decrease in the concentration of bromate with reverse osmosis, but there was a little effect in the other experiments. These findings suggest that the exposure to THM4 and MX through ingestion is reduced when using these household appliances, while the decrease of bromate is device dependent. This needs to be considered in the exposure assessment of the epidemiological studies. PMID:23476675

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

    PubMed

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

    2012-08-07

    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.

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

    NASA Technical Reports Server (NTRS)

    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.

  8. Ultraviolet radiation affects emission of ozone-depleting substances by marine macroalgae: results from a laboratory incubation study.

    PubMed

    Laturnus, Frank; Svensson, Teresia; Wiencke, Christian; Oberg, Gunilla

    2004-12-15

    The depletion of stratospheric ozone due to the effects of ozone-depleting substances, such as volatile organohalogens, emitted into the atmosphere from industrial and natural sources has increased the amount of ultraviolet radiation reaching the earth's surface. Especially in the subpolar and polar regions, where stratospheric ozone destruction is the highest, individual organisms and whole ecosystems can be affected. In a laboratory study, several species of marine macroalgae occurring in the polar and northern temperate regions were exposed to elevated levels of ultraviolet radiation. Most of the macroalgae released significantly more chloroform, bromoform, dibromomethane, and methyl iodide-all volatile organohalogens. Calculating on the basis of the release of total chlorine, bromine, and iodine revealed that, except for two macroalgae emitting chlorine and one alga emitting iodine, exposure to ultraviolet radiation caused macroalgae to emit significantly more total chlorine, bromine, and iodine. Increasing levels of ultraviolet radiation due to possible further destruction of the stratospheric ozone layer as a result of ongoing global atmospheric warming may thus increase the future importance of marine macroalgae as a source for the global occurrence of reactive halogen-containing compounds.

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

    PubMed

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

    2013-01-01

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

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

    PubMed

    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. Copyright © 2011 Elsevier B.V. All rights reserved.

  11. Brominated organic species in the arctic atmosphere

    NASA Technical Reports Server (NTRS)

    Berg, W. W.; Heidt, L. E.; Pollock, W.; Sperry, P. D.; Cicerone, R. J.; Gladney, E. S.

    1984-01-01

    Measurements are reported of four gas-phase, brominated organic species found in the Arctic atmosphere during March and April 1983. Volume mixing ratios for CH3Br, CH2BrCH2Br, CHBr3, and CH2Br2 were determined by gas chromatography/mass spectrometry analysis from samples taken Arctic wide, including at the geographic North Pole and during a tropopause folding event over Baffin Bay near Thule, Greenland. Methyl bromide mixing ratios were reasonably constant at 11 plus or minus 4 pptv, while the other three brominated organics showed a high degree of variability. Bromoform (2 to 46 pptv) was found to be the dominant contributor to gaseous organic bromine to the Arctic troposphere at 38 plus or minus 10 percent followed by CH2Br2 (3 to 60 pptv) at 29 plus or minus 6 percent. Both CH3Br and CH2BrCH2Br (1 to 37 pptv) reservoirs contained less than 20 percent of the organically bound bromine. Stratospheric samples, taken during a tropopause folding event, showed mixing ratios for all four species at levels high enough to support a stratospheric total volume mixing ratio of 249 pptv Br (888 ngBr/SCM).

  12. A New Method for the Fast Analysis of Trihalomethanes in Tap and Recycled Waters Using Headspace Gas Chromatography with Micro-Electron Capture Detection.

    PubMed

    Alexandrou, Lydon D; Meehan, Barry J; Morrison, Paul D; Jones, Oliver A H

    2017-05-15

    Chemical disinfection of water supplies brings significant public health benefits by reducing microbial contamination. The process can however, result in the formation of toxic compounds through interactions between disinfectants and organic material in the source water. These new compounds are termed disinfection by-products (DBPs). The most common are the trihalomethanes (THMs) such as trichloromethane (chloroform), dichlorobromomethane, chlorodibromomethane and tribromomethane (bromoform); these are commonly reported as a single value for total trihalomethanes (TTHMs). Analysis of DBPs is commonly performed via time- and solvent-intensive sample preparation techniques such as liquid-liquid and solid phase extraction. In this study, a method using headspace gas chromatography with micro-electron capture detection was developed and applied for the analysis of THMs in drinking and recycled waters from across Melbourne (Victoria, Australia). The method allowed almost complete removal of the sample preparation step whilst maintaining trace level detection limits (>1 ppb). All drinking water samples had TTHM concentrations below the Australian regulatory limit of 250 µg/L but some were above the U.S. EPA limit of 60 µg/L. The highest TTHM concentration was 67.2 µg/L and lowest 22.9 µg/L. For recycled water, samples taken directly from treatment plants held significantly higher concentrations (153.2 µg/L TTHM) compared to samples from final use locations (4.9-9.3 µg/L).

  13. Impact of biogas digesters on cookhouse volatile organic compound exposure for rural Kenyan farmwomen.

    PubMed

    Dohoo, Carolyn; Read Guernsey, Judith; Gibson, Mark D; VanLeeuwen, John

    2015-01-01

    Women living on rural Kenyan smallholder dairy farms burn wood as biofuel in family cookhouses. Unventilated biofuel combustion produces harmful levels of respirable particles and volatile organic compound (VOC) emissions in indoor environments. Biogas digesters, which can generate high methane-content biogas from livestock manure composting were recently installed on 31 farms. The study objectives were to compare VOC exposure profiles for women cooking on farms with and without biogas digesters, and to compare seasonal variations in VOC exposures for those women cooking with biogas. Participants (n=31 biogas farms, n=31 referent farms) wore passive thermal desorption VOC sampling tubes and recorded cookhouse fuel use on time activity sheets for 7 days. Women using biogas spent significantly less time (mean=509 min/week) exposed to cookhouse wood smoke compared with the referent group (mean=1122 min/week) (P<0.01). Total VOC exposure did not differ between farm groups (P=0.14), though concentrations of trans-1,3-dichloropropene, bromoform, and 1,4-dichlorobenzene in biogas cookhouses were significantly lower than in referent cookhouses, even after Bonferroni correction. The composition of VOC species was also significantly different, reflecting the different fuel sources. Biogas digester technologies have great potential for reducing exposure to wood smoke VOCs in low-income countries.

  14. Meteorological constraints on oceanic halocarbons above the Peruvian Upwelling

    NASA Astrophysics Data System (ADS)

    Fuhlbrügge, S.; Quack, B.; Atlas, E.; Fiehn, A.; Hepach, H.; Krüger, K.

    2015-07-01

    Halogenated very short lived substances (VSLS) are naturally produced in the ocean and emitted to the atmosphere. Recently, oceanic upwelling regions in the tropical East Atlantic were identified as strong sources of brominated halocarbons to the 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.

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

    PubMed Central

    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

  16. Volatile disinfection by-product analysis from chlorinated indoor swimming pools.

    PubMed

    Weaver, William A; Li, Jing; Wen, Yuli; Johnston, Jessica; Blatchley, Michael R; Blatchley, Ernest R

    2009-07-01

    Chlorination of indoor swimming pools is practiced for disinfection and oxidation of reduced compounds that are introduced to water by swimmers. However, there is growing concern associated with formation for chlorinated disinfection by-products (DBPs) in these settings. Volatile DBPs are of particular concern because they may promote respiratory ailments and other adverse health effects among swimmers and patrons of indoor pool facilities. To examine the scope of this issue, water samples were collected from 11 pools over a 6month period and analyzed for free chlorine and their volatile DBP content. Eleven volatile DBPs were identified: monochloramine (NH(2)Cl), dichloramine (NHCl(2)), trichloramine (NCl(3)), chloroform (CHCl(3)), bromoform (CHBr(3)), dichlorobromomethane (CHBrCl(2)), dibromochloromethane (CHBr(2)Cl), cyanogen chloride (CNCl), cyanogen bromide (CNBr), dichloroacetonitrile (CNCHCl(2)), and dichloromethylamine (CH(3)NCl(2)). Of these 11 DBPs, 10 were identified as regularly occurring, with CHBrCl(2) only appearing sporadically. Pool water samples were analyzed for residual chlorine compounds using the DPD colorimetric method and by membrane introduction mass spectrometry (MIMS). These two methods were chosen as complementary measures of residual chlorine, and to allow for comparisons between the methods. The DPD method was demonstrated to consistently overestimate inorganic chloramine content in swimming pools. Pairwise correlations among the measured volatile DBPs allowed identification of dichloromethylamine and dichloroacetonitrile as potential swimming pool water quality indicator compounds.

  17. Exposure levels to brominated compounds in seawater swimming pools treated with chlorine.

    PubMed

    Parinet, Julien; Tabaries, Sophie; Coulomb, Bruno; Vassalo, Laurent; Boudenne, Jean-Luc

    2012-03-01

    Despite evidence of formation of brominated compounds in seawater swimming pools treated with chlorine, no data about exposure levels to these compounds have been reported. To address this issue, a survey has been carried out in four establishments (representing 8 pools) fed with seawater and devoted to relaxing and cure treatments (thalassotherapy centres located in Southeast of France). Carcinogenic and mutagenic brominated disinfection byproducts (trihalomethanes -THM- and halogenated acetic acids -HAA-) were quantified at varying levels, statistically related to organic loadings brought by bathers, and not from marine organic matter, and also linked to activities carried out in the pools (watergym vs swimming). Bromoform and dibromoacetic acid, the most abundant THM and HAA detected, were measured at levels up to 18-fold greater than the maximum contaminant levels of 60 and 80 μg/L fixed by US.EPA in drinking waters. The correlations between these disinfection byproducts and other environmental factors such as nitrogen, pH, temperature, free residual chlorine, UV(254), chloride and bromide concentrations, and daily frequentation were examined. Because thalassotherapy and seawater swimming pools (hotels, cruise ships,…) are increasing in use around the world and because carcinogenic and mutagenic brominated byproducts may be produced in chlorinated seawater swimming pools, specific care should be taken to assure cleanliness of users (swimmers and patients taking the waters) and to increase water circulation through media filters to reduce levels of brominated byproducts.

  18. Disinfection by-product formation and mitigation strategies in point-of-use chlorination of turbid and non-turbid waters in western Kenya.

    PubMed

    Lantagne, D S; Blount, B C; Cardinali, F; Quick, R

    2008-03-01

    Over 1.1 billion people in the world lack access to improved drinking water. Diarrheal and other waterborne diseases cause an estimated 2.2 million deaths per year. The Safe Water System (SWS) is a proven household water treatment intervention that reduces diarrheal disease incidence in users in developing countries. Because the SWS recommends the addition of sodium hypochlorite to unfiltered water sources, concerns have been raised about the potential long-term health effects of disinfection by-products to SWS users. This study investigated the production of trihalomethanes (THMs) in water treated with sodium hypochlorite from six sources used for drinking water in western Kenya. The turbidity values of these sources ranged from 4.23 NTU to 305 NTU. THM concentrations were analysed at 1, 8, and 24 hours after addition of sodium hypochlorite. No sample exceeded the World Health Organization (WHO) guideline values for any of the four THMs: chloroform, bromodichloromethane, dibromochloromethane, or bromoform. In addition, no sample exceeded the WHO additive total THM guideline value. These results clearly show that point-of-use chlorination of a variety of realistic source waters used for drinking did not lead to THM concentrations that pose a significant health risk to SWS users.

  19. Membrane inlet mass spectrometry of volatile organohalogen compounds in drinking water.

    PubMed

    Bocchini, P; Pozzi, R; Andalò, C; Galletti, G C

    1999-01-01

    The analysis of organic pollutants in drinking water is a topic of wide interest, reflecting on public health and life quality. Many different methodologies have been developed and are currently employed in this context, but they often require a time-consuming sample pre-treatment. This step affects the recovery of the highly volatile compounds. Trace analysis of volatile organic pollutants in water can be performed 'on-line' by membrane inlet mass spectrometry (MIMS). In MIMS, the sample is separated from the vacuum of the mass spectrometer by a thin polymeric hollow-fibre membrane. Gases and organic volatile compounds diffuse and concentrate from the sample into the hollow-fibre membrane, and from there into the mass spectrometer. The main advantages of the technique are that no pre-treatment of samples before analysis is needed and that it has fast response times and on-line monitoring capabilities. This paper reports the set-up of the analytical conditions for the analysis of volatile organohalogen compounds (chloroform, bromoform, bromodichloromethane, chlorodibromomethane, tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane, and carbon tetrachloride). Linearity of response, repeatability, detection limits, and spectra quality are evaluated. Copyright 1999 John Wiley & Sons, Ltd.

  20. Source regions of stratospheric VSLS in the Indian Ocean

    NASA Astrophysics Data System (ADS)

    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.

  1. Measurement of sound velocities in shock-compressed tin under pressures up to 150 GPa

    NASA Astrophysics Data System (ADS)

    Zhernokletov, Mikhail; Kovalev, Alexey; Komissarov, Vladimir; Zocher, Marvin; Cherne, Frank

    2009-06-01

    Tin has a complex phase diagram, which can be explained by presence of structural phase transitions. The fracture in the dependence of sound velocity on pressure is caused by structural transitions in shock-compressed substance. Therefore, basing on measurement of sound velocities, it is possible to reveal phase transitions of substance along shock adiabat, including its melting. The results of different authors give the melting range of tin from 35 up to 93 GPa. In this work tin samples with initial density of 7.28 g/cm^3 were loaded with use of HE-based generators of shock waves. In the pressure range of 30-150 GPa, sound velocity in tin was measured by the method of overtaking release with use of the optical gauges and the indicator liquids: carbogal, tetrachlormethane, and bromoform. Up to shock compression pressures of about 35 GPa, sound velocity was measured by the method of oncoming release with use of piezoresistive manganin-based gauges. The obtained data testifies that the melting range of tin is ˜6390 GPa.

  2. Transformation kinetics of trace-level halogenated organic contaminants in a biologically active zone (BAZ) induced by nitrate injection

    NASA Astrophysics Data System (ADS)

    Bae, Wookeun; Odencrantz, Joseph E.; Rittmann, Bruce E.; Valocchi, Albert J.

    1990-07-01

    Laboratory experiments and numerical modeling were conducted to evaluate the secondary utilization of eight trace-concentration halogenated solvents in a denitrifying biologically active zone (BAZ) induced by nitrate injection into an acetate-fed porous-medium column. Results of column experiments indicated that carbon tetrachloride was removed most completely by the denitrifying BAZ, while bromoform, dibromoethane, tetrachloroethene, trichloroethene, and 1,2- and 1,3-dichlorobenzenes were removed, but to lesser degrees. 1,1,1-trichloroethane removal was slight. Compounds were removed to higher degrees when the BAZ contact time was increased. The steady-state, one-dimensional solute-transport equation was solved using an iterative finite-difference scheme and by employing a quasilinearization technique for the biofilm-reaction term. The model solved directly for the steady-state profiles of secondary substrates. One set of experimental results was used to obtain best-fit values of kinetic parameteres, which were then used to predict the removal at different liquid velocities. The model predictions correctly described all experimental trends: removal of the halogenated compounds in the BAZ, greater removal with increased BAZ contact time, and reduced specific removal rates caused by diffusion limitation in the biofilm.

  3. Human health risk assessment of chlorinated disinfection by-products in drinking water using a probabilistic approach.

    PubMed

    Hamidin, Nasrul; Yu, Qiming Jimmy; Connell, Des W

    2008-07-01

    The presence of chlorinated disinfection by-products (DBPs) in drinking water is a public health issue, due to their possible adverse health effects on humans. To gauge the risk of chlorinated DBPs on human health, a risk assessment of chloroform (trichloromethane (TCM)), bromodichloromethane (BDCM), dibromochloromethane (DBCM), bromoform (tribromomethane (TBM)), dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) in drinking water was carried out using probabilistic techniques. Literature data on exposure concentrations from more than 15 different countries and adverse health effects on test animals as well as human epidemiological studies were used. The risk assessment showed no overlap between the highest human exposure dose (EXP(D)) and the lowest human equivalent dose (HED) from animal test data, for TCM, BDCM, DBCM, TBM, DCAA and TCAA. All the HED values were approximately 10(4)-10(5) times higher than the 95th percentiles of EXP(D). However, from the human epidemiology data, there was a positive overlap between the highest EXP(D) and the lifetime average daily doses (LADD(H)) for TCM, BDCM, DCAA and TCAA. This suggests that there are possible adverse health risks such as a small increased incidence of cancers in males and developmental effects on infants. However, the epidemiological data comprised several risk factors and exposure classification levels which may affect the overall results.

  4. Photolytic dehalogenation of disinfection byproducts in water by natural sunlight irradiation.

    PubMed

    Abusallout, Ibrahim; Hua, Guanghui

    2016-09-01

    The aqueous photolysis of halogenated disinfection byproducts (DBPs) by natural sunlight irradiation was studied to determine their photolytic dehalogenation kinetics. Total organic halogen analysis was used to quantify the dehalogenation extents of DBPs during outdoor photolysis experiments. Dichloroacetamide, chloral hydrate, chloroform, dichloroacetonitrile, monochloro-, monobromo-, dichloro-, dibromo-, and trichloroacetic acids were generally resistant to photolytic dehalogenation and showed less than 10% reduction after 6 h sunlight irradiation. Monoiodoacetic acid, tribromoacetic acid, bromoform, dibromoacetonitrile, and trichloronitromethane showed moderate to high dehalogenation degrees with half-lives of 4.0-19.3 h. Diiodoacetic acid, triiodoacetic acid, and iodoform degraded rapidly under the sunlight irradiation and exhibited half-lives of 5.3-10.2 min. In general, the photosensitive cleavage of carbon-halogen bonds of DBPs increased with increasing number of halogens (tri- > di- > mono-halogenated) and size of the substituted halogens (I > Br > Cl). Nitrate, nitrite, and pH had little impact on the photodehalogenation of DBPs under typical levels in surface waters. The presence of natural organic matter (NOM) inhibited the photodehalogenation of DBPs by light screening. The NOM inhibiting effects were more pronounced for the fast degrading iodinated DBPs. The results of this study improve our understanding about the photolytic dehalogenation of wastewater-derived DBPs in surface waters during water reuse.

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

    PubMed

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

    2008-05-01

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

  6. Characterization of the metabolic interaction between trihalomethanes and chloroacetic acids using rat liver microsomes.

    PubMed

    St-Pierre, Annie; Krishnan, Kannan; Tardif, Robert

    2005-02-27

    The aim of this study was to investigate the in vitro metabolism of trihalomethanes (THMs) in the presence of trichloroacetic acid (TCA), dichloracetic acid (DCA), monochloroacetic acid (MCA), and 4-methylpyrazole (4-MP) using liver microsomes from male Sprague-Dawley rats. Using the vial equilibration technique, initial experiments were carried out with starting concentrations of approximately 40 ppm THMs and 12-22 mM chloroacetic acids. The results indicated a mutual metabolic inhibition between THMs present as binary or quaternary mixtures. Although DCA and MCA had no influence on THMs, TCA produced a marked inhibition of the metabolism of all THMs: chloroform (CHCl3) (55%), bromodichloromethane (BDCM) (34%), dibromochloromethane (DBCM) (30%), and bromoform (TBM) (23%). The presence of 4-MP also reduced THM metabolism, the importance of which decreased in the following order: CHCl3 > BDCM > DBCM = TBM. In further vial equilibration experiments, using 9-140 ppm as starting concentrations of THMs, enzyme kinetic parameters (i.e., Michaelis constant, K(m), and maximum velocity, V(max)) were determined both in the absence and in the presence of TCA (12.2 mM). Results are consistent with a competitive inhibition between TCA and CHCl3, whereas the metabolic inhibition of BDCM and TMB by TCA was non-competitive. As for DBCM, results suggest a more complex pattern of inhibition. These results suggest that CYP2E1 is involved in the metabolism of THMs as well as in the metabolic interaction between THMs and TCA.

  7. Pregnancy loss and eye malformations in offspring of F344 rats following gestational exposure to mixtures of regulated trihalomethanes and haloacetic acids.

    PubMed

    Narotsky, Michael G; Best, Deborah S; McDonald, Anthony; Godin, Elizabeth A; Hunter, E Sidney; Simmons, Jane Ellen

    2011-01-01

    Chlorination of drinking water yields hundreds of disinfection by-products (DBPs). Among the DBPs, four trihalomethanes (THMs; chloroform, bromodichloromethane, chlorodibromomethane, bromoform) and five haloacetic acids (HAAs; chloroacetic, dichloroacetic, trichloroacetic, bromoacetic, and dibromoacetic acid) are U.S. EPA regulated. We assessed the combined toxicity of these DBPs. F344 rats were treated with mixtures of the four THMs (THM4), the five HAAs (HAA5), or nine DBPs (DBP9; THM4+HAA5). Mixtures were administered in 10% Alkamuls(®) EL-620 daily by gavage on gestation days 6-20. Litters were examined postnatally. All three mixtures caused pregnancy loss at ≥ 613 μmol/kg/day. In surviving litters, resorption rates were increased in groups receiving HAA5 at 615 μmol/kg/day and DBP9 at 307 μmol/kg/day. HAA5 caused eye malformations (anophthalmia, microphthalmia) at ≥ 308 μmol/kg/day. Thus, both HAAs and THMs contributed to DBP9-induced pregnancy loss. The presence of THMs in the full mixture, however, appeared to reduce the incidence of HAA-induced eye defects.

  8. Speciation of trihalomethane mixtures for the Mississippi, Missouri, and Ohio Rivers

    USGS Publications Warehouse

    Rathbun, R.E.

    1996-01-01

    Trihalomethane formation potentials were determined for the chlorination of water samples from the Mississippi, Missouri, and Ohio Rivers. Samples were collected during the summer and fall of 1991 and the spring of 1992 at 12 locations on the Mississippi from New Orleans, LA, to Minneapolis, MN, and on the Missouri and Ohio 1.6 km upstream from their confluences with the Mississippi. Formation potentials were determined as a function of pH and initial free-chlorine concentration. Chloroform concentrations decreased with distance downstream and approximately paralleled the decrease of the dissolved organic-carbon concentration. Bromide concentrations were 3.7-5.7 times higher for the Missouri and 1.4-1.6 times higher for the Ohio than for the Mississippi above their confluences, resulting in an overall increase of the bromide concentration with distance downstream. Variations of the concentrations of the brominated trihalomethanes with distance downstream approximately paralleled the variation of the bromide concentration. Concentrations of all four trihalomethanes increased as the pH increased. Concentrations of chloroform and bromodichloromethane increased slightly and the concentration of bromoform decreased as the initial free-chlorine concentration increased; the chlorodibromomethane concentration had little dependence on the free-chlorine concentration.

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

    PubMed

    Wang, Yuru; Le Roux, Julien; Zhang, Tao; Croué, Jean-Philippe

    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.

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

    PubMed

    Lourencetti, Carolina; Ballester, Clara; Fernández, Pilar; Marco, Esther; Prado, Celia; Periago, Juan F; Grimalt, Joan O

    2010-03-03

    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.

  11. Estimating surface fluxes of very short-lived halogens from aircraft measurements over the tropical Western Pacific

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    We use an inverse model approach to quantitatively understand the ocean flux and atmospheric transport of very short-lived halogenated species (VSLS) measured during the coordinated NERC CAST and NCAR CONTRAST aircraft campaigns over the Western Pacific during January/February 2014. To achieve this we have developed a nested GEOS-Chem chemistry transport model simulation of bromoform (CHBr3) and dibromomethane (CH2Br2), which has a spatial resolution of 0.25° (latitude) × 0.3125° (longitude) over the tropical Western Pacific region, and fed by boundary conditions from a coarser version of the model. We use archived 3-hourly 3-D fields of OH and j-values for CHBr3 photolysis, allowing us to linearly decompose these gases into tagged contributions from different geographical regions. Using these tagged tracers, we are able to use the maximum a posteriori probability (MAP) approach to estimate the VSLS sources by fitting the model to observations. We find that the resulting VSLS fluxes are significantly different from some previous studies. To interpret the results, we describe several observation system simulation experiments to understand the sensitivity of these flux estimates to observation errors as well as to the uncertainty in the boundary condition imposed around the nested grid.

  12. Quantifying Sulfur-Containing Compounds Over the Santa Barbara Channel

    NASA Astrophysics Data System (ADS)

    Black, J.; Hughes, S.; Blake, D. R.

    2016-12-01

    Carbonyl sulfide (OCS) is emitted to the atmosphere through the outgassing of ocean surface waters. OCS is also the primary source of sulfur-containing compounds in the stratosphere and contributes to the formation of the stratospheric sulfate layer. During the 2016 Student Airborne Research Program (SARP), whole air samples were collected on the NASA DC-8 aircraft over the Santa Barbara Channel. Five additional surface samples were taken at various locations along the Santa Barbara Channel. The samples were analyzed using gas chromatography in the Rowland-Blake lab at UC Irvine, and compounds such as OCS, dimethyl sulfide (DMS), carbon disulfide (CS2), bromoform (CHBr3), and methyl iodide (CH3I) associated with ocean emissions and stratospheric aerosols were analyzed. These marine sourced compounds, excluding OCS, showed expected trends of dilution with increasing altitude. The surface samples from the Santa Barbara Channel all exhibited elevated concentrations of OCS in comparison to samples taken from the aircraft, with an average of 666 ± 12 pptv, whereas the average background concentration of OCS was 587 ± 19 pptv. SARP flights from 2009-2015 over the Santa Barbara Channel saw an average OCS concentration of 548 ± 26 pptv. Elevated levels of OCS have never been detected from the aircraft during SARP flights, indicating that OCS emissions must be measured using surface sampling if emission estimates from the ocean are to be evaluated.

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

    SciTech Connect

    Mirsalis, J.C.; Tyson, C.K.; Steinmetz, K.L.; Loh, E.K.; Hamilton, C.M.; Bakke, J.P. ); Spalding, J.W. )

    1989-01-01

    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 {sup 3}H-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. Heavy mineral distribution in stream sediment of Tapah area, Perak, Malaysia

    NASA Astrophysics Data System (ADS)

    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.

  15. The risks of drinking water

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

  17. Streamflow and Water-Quality Characteristics for Wind Cave National Park, South Dakota, 2002-03

    USGS Publications Warehouse

    Heakin, Allen J.

    2004-01-01

    permanent fisheries criterion in numerous samples from all three streams. Two samples from Highland Creek also exceeded the coldwater marginal fisheries criterion for water temperature. Mean concentrations of ammonia, orthophosphate, and phosphorous were higher for the upstream site on Beaver Creek than for other water-quality sampling sites. Concentrations of E. coli, fecal coliform, and total coliform bacteria also were higher at the upstream site on Beaver Creek than for any other site. Samples for the analysis of benthic macroinvertebrates were collected from one site on each of the three streams during July 2002 and May 2003. The benthic macroinvertebrate data showed that Beaver Creek had lower species diversity and a higher percentage of tolerant species than the other two streams during 2002, but just the opposite was found during 2003. However, examination of the complete data set indicates that the quality of water at the upstream site was generally poorer than the quality of water at the downstream site. Furthermore, the quality of water at the upstream site on Beaver Creek is somewhat degraded when compared to the quality of water from Highland and Cold Spring Creeks, indicating that anthropogenic activities outside the park probably are affecting the quality of water in Beaver Creek. Samples for the analysis of wastewater compounds were collected at least twice from four of the five water-quality sampling sites. Bromoform, phenol, caffeine, and cholesterol were detected in samples from Cold Spring Creek, but only phenol was detected at concentrations greater than the minimum reporting level. Concentrations of several wastewater compounds were estimated in samples collected from sites on Beaver Creek, including phenol, para-cresol, and para-nonylphenol-total. Phenol was detected at both sites on Beaver Creek at concentrations greater than the minimum reporting level. Bromoform; para-cresol; ethanol,2-butoxy-phosphate; and cholesterol were detected

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

    USGS Publications Warehouse

    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

  19. Oceanic contributions from tropical upwelling systems to atmospheric halogens

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  20. C{sub 1}-C{sub 15} alkyl nitrates, benzyl nitrate, and bifunctional nitrates: Measurements in California and South Atlantic air and global comparison using C{sub 2}Cl{sub 4} and CHBr{sub 3} as marker molecules

    SciTech Connect

    Schneider, M.; Luxenhofer, O.; Deissler, A.; Ballschmiter, K. |

    1998-10-15

    Measurements of C{sub 1}--C{sub 15} alkyl nitrates, perchloroethylene, and bromoform at two different sampling sites near Santa Cruz, CA, were conducted in 1995. The halocarbons were used as marker molecules to differentiate the air parcels collected into marine and continental groups. The average concentration of {Sigma}n/i-C{sub 3}--C{sub 12} alkyl nitrates at the California Coast was lower than the levels obtained in the coastal mountains. This difference was shown to be most significant for the long chain n/i-C{sub 6}--C{sub 12} alkyl nitrates. It is concluded that the {ge}C{sub 6} alkyl nitrates in continental air can contribute 1--2% to the total NO{sub y}. The results are summarized together with earlier data sets to give a picture of contemporary levels and of the global occurrence of C{sub 3}--C{sub 12} alkyl nitrates. In comparison with South Atlantic air, pattern analysis of n-alkyl nitrates suggests a marine source of primary n-alkyl nitrates. It is also shown that liquid chromatographic preseparation of the air sample extracts leads to a fraction that contains more polar organic nitrates. Several alkyl dinitrates and benzyl nitrate are detected in air samples from California, the South Atlantic region, and Europe. The vicinal alkyl dinitrates show increased abundance in a nighttime sample. The relative abundance of benzyl nitrate compared to alkyl (mono) nitrates is used as a tool for global air mass characterization.

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

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

    NASA Technical Reports Server (NTRS)

    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.

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

    PubMed

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

    2010-11-01

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

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

    PubMed

    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.

  5. Cascade air-stripping system for removal of low and semi-volatile organic contaminants

    SciTech Connect

    Jang, Won.

    1989-01-01

    Many hazardous waste sites have been known to have groundwaters contaminated with low volatile, hazardous compounds such as bromoform 1,1,2,2-tetrachloroethane, 1,2-dibromo-3-chloropropane (DBCP), napthalene, and polychlorinated biphenyls (PCBs). In addition, a large number of public water supplies have been reported to have taste and odor problems in drinking water, which are attributed primarily to naturally occurring compounds, such as 2-methylisoborneol (MIB), geosmin, etc. These classes of compounds have very low Henry's Constant, H{sub c}, in the range of 1 to 50 atm. Air-stripping in countercurrent packed towers is a well accepted treatment process for removing volatile organic chemicals (VOCs) from water. The USEPA has identified packed countercurrent air-stripping as not only the least-cost, but also one of the best available technologies for the removal of VOCs. However, the economic viability of this process is limited to volatile compounds of H{sub c} value greater than SO atm. A novel modification of the conventional countercurrent air-stripping process, introduced as cascade air-stripping was proposed for cost effective removal of these classes of compounds from water and at hazardous waste spill-sites. The main objectives of this study were to demonstrate the concept of cascade air-stripping; to compare cascade air-stripping with conventional air-stripping under identical conditions; and to verify the hypothesis that the cascade system is superior to the conventional system at the pilot and prototype scales. Results of the pilot and prototype study showed that the cascade airstrip ping system was a viable and economical approach to remove low and semi-volatile organic compounds from water. The cascade system consistently showed higher removals than the conventional system for both pilot and prototype scale study.

  6. Environmental and personal determinants of the uptake of disinfection by-products during swimming.

    PubMed

    Font-Ribera, Laia; Kogevinas, Manolis; Schmalz, Christina; Zwiener, Christian; Marco, Esther; Grimalt, Joan O; Liu, Jiaqi; Zhang, Xiangru; Mitch, William; Critelli, Rossana; Naccarati, Alessio; Heederik, Dick; Spithoven, Jack; Arjona, Lourdes; de Bont, Jeroen; Gracia-Lavedan, Esther; Villanueva, Cristina M

    2016-08-01

    Trihalomethanes (THMs) in exhaled breath and trichloroacetic acid (TCAA) in urine are internal dose biomarkers of exposure to disinfection by-products (DBPs) in swimming pools. We assessed how these biomarkers reflect the levels of a battery of DBPs in pool water and trichloramine in air, and evaluated personal determinants. A total of 116 adults swam during 40min in a chlorinated indoor pool. We measured chloroform, bromodichloromethane, dibromochloromethane and bromoform in exhaled breath and TCAA in urine before and after swimming, trichloramine in air and several DBPs in water. Personal determinants included sex, age, body mass index (BMI), distance swum, energy expenditure, heart rate and 12 polymorphisms in GSTT1, GSTZ1 and CYP2E1 genes. Median level of exhaled total THMs and creatinine adjusted urine TCAA increased from 0.5 to 14.4µg/m(3) and from 2.5 to 5.8µmol/mol after swimming, respectively. The increase in exhaled brominated THMs was correlated with brominated THMs, haloacetic acids, haloacetonitriles, haloketones, chloramines, total organic carbon and total organic halogen in water and trichloramine in air. Such correlations were not detected for exhaled chloroform, total THMs or urine TCAA. Exhaled THM increased more in men, urine TCAA increased more in women, and both were affected by exercise intensity. Genetic variants were associated with differential increases in exposure biomarkers. Our findings suggest that, although affected by sex, physical activity and polymorphisms in key metabolizing enzymes, brominated THMs in exhaled breath could be used as a non-invasive DBP exposure biomarker in swimming pools with bromide-containing source waters. This warrants confirmation with new studies. Copyright © 2016 Elsevier Inc. All rights reserved.

  7. Gene expression changes in blood RNA after swimming in a chlorinated pool.

    PubMed

    Salas, Lucas A; Font-Ribera, Laia; Bustamante, Mariona; Sumoy, Lauro; Grimalt, Joan O; Bonnin, Sarah; Aguilar, Maria; Mattlin, Heidi; Hummel, Manuela; Ferrer, Anna; Kogevinas, Manolis; Villanueva, Cristina M

    2017-08-01

    Exposure to disinfection by-products (DBP) such as trihalomethanes (THM) in swimming pools has been linked to adverse health effects in humans, but their biological mechanisms are unclear. We evaluated short-term changes in blood gene expression of adult recreational swimmers after swimming in a chlorinated pool. Volunteers swam 40min in an indoor chlorinated pool. Blood samples were drawn and four THM (chloroform, bromodichloromethane, dibromochloromethane and bromoform) were measured in exhaled breath before and after swimming. Intensity of physical activity was measured as metabolic equivalents (METs). Gene expression in whole blood mRNA was evaluated using IlluminaHumanHT-12v3 Expression-BeadChip. Linear mixed models were used to evaluate the relationship between gene expression changes and THM exposure. Thirty-seven before-after pairs were analyzed. The median increase from baseline to after swimming were: 0.7 to 2.3 for MET, and 1.4 to 7.1μg/m(3) for exhaled total THM (sum of the four THM). Exhaled THM increased on average 0.94μg/m(3) per 1 MET. While 1643 probes were differentially expressed post-exposure. Of them, 189 were also associated with exhaled levels of individual/total THM or MET after False Discovery Rate. The observed associations with the exhaled THM were low to moderate (Log-fold change range: -0.17 to 0.15). In conclusion, we identified short-term gene expression changes associated with swimming in a pool that were minor in magnitude and their biological meaning was unspecific. The high collinearity between exhaled THM levels and intensity of physical activity precluded mutually adjusted models with both covariates. These exploratory results should be validated in future studies. Copyright © 2017. Published by Elsevier B.V.

  8. Formation of dimethylketene and methacrolein by reaction of the CH radical with acetone.

    PubMed

    Goulay, Fabien; Derakhshan, Adeeb; Maher, Eamonn; Trevitt, Adam J; Savee, John D; Scheer, Adam M; Osborn, David L; Taatjes, Craig A

    2013-03-21

    The reaction of the methylidyne radical (CH) with acetone ((CH(3))(2)C[double bond, length as m-dash]O) is studied at room temperature and at a pressure of 4 Torr (533.3 Pa) using a multiplexed photoionization mass spectrometer coupled to the tunable vacuum ultraviolet synchrotron radiation of the Advanced Light Source at Lawrence Berkeley National Laboratory. The CH radicals are generated by 248 nm multiphoton photolysis of bromoform and react with acetone in an excess of helium and nitrogen gas flow. The main observed reaction exit channel is elimination of a hydrogen atom to form C(4)H(6)O isomers. Analysis of photoionization spectra identifies dimethylketene and methacrolein as the only H-elimination products. The best fit to the data gives branching ratios of 0.68 ± 0.14 for methacrolein and 0.32 ± 0.07 for dimethylketene. A methylketene spectrum measured here is used to reanalyze the photoionization spectrum obtained at m/z = 56 for the CH + acetaldehyde reaction, (Goulay et al., J. Phys. Chem. A, 2012, 116, 6091) yielding new H-loss branching ratios of 0.61 ± 0.12 for acrolein and 0.39 ± 0.08 for methylketene. The contribution from methyleneoxirane to the reaction product distribution is revised to be negligible. Coupled with additional product detection for the CD + acetone reaction, these observations pave the way for development of general set of reaction mechanisms for the addition of CH to compounds containing an acetyl subgroup.

  9. Airborne measurements of tropospheric ozone destruction and particulate bromide formation in the Arctic

    NASA Technical Reports Server (NTRS)

    Schnell, Russell C.; Sheridan, Patrick J.; Peterson, Richard E.; Oltmans, S. J.

    1988-01-01

    Aircraft profiles of O3 concentrations over the Arctic ice pack in spring exhibit a depletion of O3 beneath the surface temperature inversion. One such profile from the NOAA WP-3D Arctic Gas and Aerosol Sampling Program (AGASP) flights in April, 1986 north of Alert, NWT (YLT, 82.5 N) is shown. The gradient of O3 across the temperature inversion, which is essentially a step function from tropospheric values (35 to 40 ppbv) to 0, is somewhat masked by a 1-min running mean applied to the data. Evidence is presented that O3 destruction beneath the Arctic temperature inversion is the result of a photochemical reaction between gaseous Br compounds and O3 to produce particulate Br aerosol. It is noted that in springtime, O3 at the Alert Baseline Station regularly decreases from 30 to 40 ppbv to near 0 over the period of a few hours to a day. At the same time, there is a production of particulate Br with a near 1.0 anti-correlation to O3 concentration. Surface concentrations of bromoform in the Arctic exhibit a rapid decrease following polar sunrise. AGASP aircraft measurements of filterable bromine particulates in the Arctic (March-April, 1983 and 1986) are shown. The greatest concentrations of Br aerosol (shown as enrichment factors relative to to Na in seawater, EFBR (Na)) were observed in samples collected beneath the surface temperature inversion over ice. Samples collected at the same altitude over open ocean (off Spitzbergen) labeled Marine did not exhibit similar Br enrichments. A second region of particulate Br enrichment was observed in the lower stratosphere, which regularly descends to below 500 mb (5.5 km) in the high Arctic. The NOAA WP-3D flew in the stratosphere on all AGASP flights and occasionally measured O3 concentrations in excess of 300 ppbv.

  10. Comparison of Trihalomethanes in Tap Water and Blood: A Case Study in the United States

    PubMed Central

    Rivera-Núñez, Zorimar; Blount, Benjamin C.; Silva, Lalith K.; Jones, Elizabeth; Chan, Ronna L.; Pegram, Rex A.; Singer, Philip C.; Savitz, David A.

    2012-01-01

    Background: Epidemiological studies have used various measures to characterize trihalomethane (THM) exposures, but the relationship of these indicators to exposure biomarkers remains unclear. Objectives: We examined temporal and spatial variability in baseline blood THM concentrations and assessed the relationship between these concentrations and several exposure indicators (tap water concentration, water-use activities, multiroute exposure metrics). Methods: We measured water-use activity and THM concentrations in blood and residential tap water from 150 postpartum women from three U.S. locations. Results: Blood ΣTHM [sum of chloroform (TCM), bromodichloromethane (BDCM), dibromo-chloromethane (DBCM), and bromoform (TBM)] concentrations varied by site and season. As expected based on variable tap water concentrations and toxicokinetic properties, the proportion of brominated species (BDCM, DBCM, and TBM) in blood varied by site (site 1, 24%; site 2, 29%; site 3, 57%) but varied less markedly than in tap water (site 1, 35%; site 2, 75%; site 3, 68%). The blood–water ΣTHM Spearman rank correlation coefficient was 0.36, with correlations higher for individual brominated species (BDCM, 0.62; DBCM, 0.53; TBM, 0.54) than for TCM (0.37). Noningestion water activities contributed more to the total exposure metric than did ingestion, but tap water THM concentrations were more predictive of blood THM levels than were metrics that incorporated water use. Conclusions: Spatial and temporal variability in THM concentrations was greater in water than in blood. We found consistent blood–water correlations across season and site for BDCM and DBCM, and multivariate regression results suggest that water THM concentrations may be an adequate surro-gate for baseline blood levels. PMID:22281753

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

    NASA Astrophysics Data System (ADS)

    Hoyle, C. R.; Marécal, V.; Russo, M. R.; Allen, G.; Arteta, J.; Chemel, C.; Chipperfield, M. P.; D'Amato, F.; Dessens, O.; Feng, W.; Hamilton, J. F.; Harris, N. R. P.; Hosking, J. S.; Lewis, A. C.; Morgenstern, O.; Peter, T.; Pyle, J. A.; Reddmann, T.; Richards, N. A. D.; Telford, P. J.; Tian, W.; Viciani, S.; Volz-Thomas, A.; Wild, O.; Yang, X.; Zeng, G.

    2011-08-01

    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.

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

    NASA Astrophysics Data System (ADS)

    Hoyle, C. R.; Marécal, V.; Russo, M. R.; Arteta, J.; Chemel, C.; Chipperfield, M. P.; D'Amato, F.; Dessens, O.; Feng, W.; Harris, N. R. P.; Hosking, J. S.; Morgenstern, O.; Peter, T.; Pyle, J. A.; Reddmann, T.; Richards, N. A. D.; Telford, P. J.; Tian, W.; Viciani, S.; Wild, O.; Yang, X.; Zeng, G.

    2010-08-01

    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 most active

  13. Multi-route trihalomethane exposure in households using municipal tap water treated with chlorine or ozone-chlorine.

    PubMed

    Jo, Wan-Kuen; Kwon, Ki-Dong; Dong, Jong-In; Chung, Yong

    2005-03-01

    In Korea, data for multi-route trihalomethane (THM) exposure in households using municipal tap water treated with ozone-chlorine or chlorine are unavailable or very limited. Accordingly, the present study was designed to obtain those data by measurements of the THM concentrations in the tap water and indoor and outdoor air in the two types of households, along with an estimation of THM exposure from water ingestion, showering, and the inhalation of indoor air. Chloroform was the most abundant THM in all three media, yet no bromoform was detected in any sample. Similar to previous findings, the winter chloroform concentration in tap water treated with chlorine (22.1 microg/l, median) was significantly higher than that in the tap water treated with ozone-chlorine (16.8 microg/l, median). However, the summer water chloroform concentrations and summer and winter water concentrations of the other two THMs (bromodichloromethane and dibromochloromethane) exhibited no significant difference between the chlorine and ozone-chlorine-treated water. It was suggested that the effects of the water parameters including biochemical oxygen demand of raw water entering water treatment plants should be considered when evaluating the advantage of ozone-chlorine disinfection for THM formation over chlorine disinfection. The indoor air THM concentration trend was also consistent with the water concentration trend. The indoor to outdoor air concentration ratios were comparable with previous studies. The THM exposure estimates from water ingestion, showering, and the inhalation of apartment indoor air when not in the shower suggested that, for residents living in the surveyed households, their exposure to THMs in the home was mostly associated with their household water uses. The THM exposure estimates from tap water ingestion were similar to those from showering.

  14. Chlorination by-product concentration levels in seawater and fish of an industrialised bay (Gulf of Fos, France) exposed to multiple chlorinated effluents.

    PubMed

    Boudjellaba, D; Dron, J; Revenko, G; Démelas, C; Boudenne, J-L

    2016-01-15

    Chlorination is one of the most widely used techniques for biofouling control in large industrial units, leading to the formation of halogenated chlorination by-products (CBPs). This study was carried out to evaluate the distribution and the dispersion of these compounds within an industrialised bay hosting multiple chlorination discharges issued from various industrial processes. The water column was sampled at the surface and at 7 m depth (or bottom) in 24 stations for the analysis of CBPs, and muscle samples from 15 conger eel (Conger conger) were also investigated. Temperature and salinity profiles supported the identification of the chlorination releases, with potentially complex patterns. Chemical analyses showed that bromoform was the most abundant CBP, ranging from 0.5 to 2.2 μg L(-1) away from outlets (up to 10 km distance), and up to 18.6 μg L(-1) in a liquefied natural gas (LNG) regasification plume. However, CBP distributions were not homogeneous, halophenols being prominent in a power station outlet and dibromoacetonitrile in more remote stations. A seasonal effect was identified as fewer stations revealed CBPs in summer, probably due to the air and water temperatures increases favouring volatilisation and reactivity. A simple risk assessment of the 11 identified CBPs showed that 7 compounds concentrations were above the potential risk levels to the local marine environment. Finally, conger eel muscles presented relatively high levels of 2,4,6-tribromophenol, traducing a generalised impregnation of the Gulf of Fos to CBPs and a global bioconcentration factor of 25 was determined for this compound. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    PubMed

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

    2015-10-01

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

  16. Comparative developmental toxicity of new aromatic halogenated DBPs in a chlorinated saline sewage effluent to the marine polychaete Platynereis dumerilii.

    PubMed

    Yang, Mengting; Zhang, Xiangru

    2013-10-01

    Using seawater for toilet flushing may introduce high levels of bromide and iodide into a city's sewage treatment works, and result in the formation of brominated and iodinated disinfection byproducts (DBPs) during chlorination to disinfect sewage effluents. In a previous study, the authors' group has detected the presence of many brominated DBPs and identified five new aromatic brominated DBPs in chlorinated saline sewage effluents. The presence of brominated DBPs in chlorinated saline effluents may pose adverse implications for marine ecology. In this study, besides the detection and identification of another seven new aromatic halogenated DBPs in a chlorinated saline sewage effluent, their developmental toxicity was evaluated using the marine polychaete Platynereis dumerilii. For comparison, the developmental toxicity of some commonly known halogenated DBPs was also examined. The rank order of the developmental toxicity of 20 halogenated DBPs was 2,5-dibromohydroquinone > 2,6-diiodo-4-nitrophenol ≥ 2,4,6-triiodophenol > 4-bromo-2-chlorophenol ≥ 4-bromophenol > 2,4-dibromophenol ≥ 2,6-dibromo-4-nitrophenol > 2-bromo-4-chlorophenol > 2,6-dichloro-4-nitrophenol > 2,4-dichlorophenol > 2,4,6-tribromophenol > 3,5-dibromo-4-hydroxybenzaldehyde > bromoform ≥ 2,4,6-trichlorophenol > 2,6-dibromophenol > 2,6-dichlorophenol > iodoacetic acid ≥ tribromoacetic acid > bromoacetic acid > chloroacetic acid. On the basis of developmental toxicity data, a quantitative structure-activity relationship (QSAR) was established. The QSAR involved two physical-chemical property descriptors (log P and pKa) and two electronic descriptors (the lowest unoccupied molecular orbital energy and the highest occupied molecular orbital energy) to indicate the transport, biouptake, and biointeraction of these DBPs. It can well predict the developmental toxicity of most of the DBPs tested.

  17. Brominated VSLSs in and over the East Pacific During the Halocarbon Air-Sea Transect - Pacific Cruise (HalocAST-P)

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Yvon-Lewis, S. A.; Hu, L.; Smith, R. W.; Shen, L.; Bianchi, T. S.; Campbell, L.

    2010-12-01

    Brominated very short lived substances (VSLSs), such as bromoform (CHBr3), dibromomethane (CH2Br2), dibromochloromethane (CHClBr2), and dichlorobromomethane (CHBrCl2) can potentially supply a significant amount of inorganic bromine (Bry) to the troposphere and lower stratosphere. Bromine radicals are 50 - 100 times more efficient in depleting ozone (O3) than chlorine radicals; therefore, these compounds are important to the ozone chemistry in the atmosphere. CHBr3, CH2Br2, CHClBr2 and CHBrCl2 are thought to be produced mainly by phytoplankton in the open ocean. During the Halocarbon Air-Sea Transect - Pacific (HalocAST - P) cruise we examined the distributions of halocarbons in the East Pacific Ocean and in the overlying atmosphere. The cruise started from Punta Arenas, Chile on March 29, and finished at Seattle, WA, United States on April 29 2010. Continuous underway measurements of the atmospheric and surface seawater concentrations along with depth profiles of CHBr3, CH2Br2, CHClBr2, CHBrCl2, and a suite of other halogenated compounds were measured over a large cross latitudinal transect. The brominated VSLS measured during this cruise generally exhibit a correlation with chlorophyll a, supporting biogenic production as the predominate source for these compounds in the open ocean. Here, we will be discussing air and seawater concentrations, saturation anomalies, fluxes, and depth profiles for CHBr3, CH2Br2, CHClBr2, and CHBrCl2. Cyanobacteria counts, pigment compositions, nutrient and dissolved organic carbon (DOC) concentrations in the water column were also measured and serve as useful tools for understanding the biological production of these brominated VSLSs.

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

    NASA Technical Reports Server (NTRS)

    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.

  19. Release of Oxidized Bromine Species From Diatoms: Implication for the Polar Troposphere and Oceanic Polyhalomethane Production

    NASA Astrophysics Data System (ADS)

    Manley, S. L.; Hill, V. L.

    2006-12-01

    Marine and ice diatoms are known producers of polybromomethanes. These trace gases produced from ice algae have been implicated as a source of photochemically active bromine involved in polar surface ozone depletion events. A more dominant source of reactive bromine, however, has been attributed to the reaction on ice particles and in sea spray aerosols of atmospherically derived HOBr with bromide and chloride to produce the dihalogens Br2 and BrCl. We have measured the release of oxidized bromine species (Brox = HOBr, Br2, Br3-1) from polar and temperate diatoms. The highest rates were measured from Porosira glaciales (CCMP 651). Release rates are range from 0.84 to 180 fmoles bromine/hour/cell depending on the species or an approximate maximum of 950 nmoles bromine/mg chl a/hr (P. glaciales). The flux from the diatoms is 0.1 to 7.5 nmoles bromine/cm2 diatom surface/hr. This release occurs from an extracellular bromoperoxidase when a suitable organic substrate is absent. At 0.84 mM bromide (average seawater concentration), the optimal pH for Brox release is 6.5, which is the putative pH of the apoplastic space, and the optimal H2O2 concentration is 250 nM. Based on these results, it is estimated that the amount of bromine released from ice algae as Brox is 10 to 200 times greater than the release of bromine as bromoform from ice algae. The Brox so produced could participate in the abiotic formation of dihalogens in sea ice. Also, Brox released from diatoms may react with specific components of DOC, if present, to indirectly produce polybromomethanes both in sea ice and seawater. The amount of polyhalomethanes produced is not only dependent on the algal species present but also on the composition of DOC.

  20. Do Climate Feedbacks in the Tropical East Pacific Impact Emissions of Biogenic Halocarbons?

    NASA Astrophysics Data System (ADS)

    Hepach, H.; Quack, B.; Atlas, E. L.; Fiehn, A.; Bracher, A.; Tegtmeier, S.; Krüger, K.

    2016-02-01

    Natural emissions of marine halogenated compounds (halocarbons) are of large interest since they strongly influence the oxidative capacity of the troposphere, are involved in aerosol and ultrafine particle formation, and take part in tropospheric ozone depletion. In regions of strong tropical deep convection they can even be transported into the stratosphere, where the released halogens take also part in ozone destruction. Recent studies identified oceanic upwelling systems, where cold, nutrient rich deep waters foster enhanced biological activity in the surface, as important source regions for brominated compounds such as bromoform and dibromomethane, as well as the iodinated compounds such as methyl iodide, chloroiodomethane and diiodomethane. The tropical Pacific is subject to strong variations in atmospheric and oceanographic conditions known as the El Niño - Southern Oscillation (ENSO). During regular conditions, a strong upwelling band is observed at the western coast of South America especially close to Peru. In contrast, the upwelling ceases during the anomalous warm phase known as El Niño with severe consequences for biogeochemical cycles in the tropical East Pacific. We identified the Peruvian upwelling as a strong source for iodinated and only as a moderate source for brominated halocarbons during the M91 cruise in December 2012 during regular ENSO conditions. We demonstrate that the organoiodine emissions contribute most of the tropospheric iodine found during this season. During the onset of the ENSO-warm phase, the biological activity and thus the emissions may change drastically. Such changes and their impact on tropospheric halogen budgets are investigated for the ASTRA-OMZ SONNE cruise taking place in the same region in October 2015 as M91 but during a strong El Niño event.

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

    PubMed

    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.

  2. Fate of disinfection by-products in groundwater during aquifer storage and recovery with reclaimed water.

    PubMed

    Pavelic, Paul; Nicholson, Brenton C; Dillon, Peter J; Barry, Karen E

    2005-03-01

    Knowledge on the behaviour of disinfection by-products (DBPs) during aquifer storage and recovery (ASR) is limited even though this can be an important consideration where recovered waters are used for potable purposes. A reclaimed water ASR trial in an anoxic aquifer in South Australia has provided some of the first quantitative information at field-scale on the fate and transport of trihalomethanes (THMs) and haloacetic acids (HAAs). The results revealed that THM half-lives varied from <1 to 65 days, with persistence of chloroform being highest and bromoform lowest. HAA attenuation was rapid (<1 day). Rates of THM attenuation were shown to be highly dependent on the geochemical environment as evidenced by the 2-5 fold reduction in half-lives at the ASR well which became methanogenic during the storage phase of the trial, as compared to an observation well situated 4 m away, which remained nitrate-reducing. These findings agree with previous laboratory-based studies which also show persistence declining with increased bromination of THMs and reducing redox conditions. Modelling suggests that the chlorinated injectant has sufficient residual chlorine and natural organic matter for substantial increases in THMs to occur within the aquifer, however this is masked in some of the field observations due to concurrent attenuation, particularly for the more rapidly attenuated brominated compounds. The model is based on data taken from water distribution systems and may not be representative for ASR since bromide and ammonia concentrations in the injected water and the possible role of organic carbon in the aquifer were not taken into consideration. During the storage phase DBP formation potentials were reduced as a result of the removal of precursor material despite an increase in the THM formation potential per unit weight of total organic carbon. This suggests that water quality improvements with respect to THMs and HAAs can be achieved through ASR in anoxic aquifers.

  3. Fate of disinfection by-products in groundwater during aquifer storage and recovery with reclaimed water.

    PubMed

    Pavelic, Paul; Nicholson, Brenton C; Dillon, Peter J; Barry, Karen E

    2005-05-01

    Knowledge on the behaviour of disinfection by-products (DBPs) during aquifer storage and recovery (ASR) is limited even though this can be an important consideration where recovered waters are used for potable purposes. A reclaimed water ASR trial in an anoxic aquifer in South Australia has provided some of the first quantitative information at field-scale on the fate and transport of trihalomethanes (THMs) and haloacetic acids (HAAs). The results revealed that THM half-lives varied from <1 to 65 days, with persistence of chloroform being highest and bromoform lowest. HAA attenuation was rapid (<1 day). Rates of THM attenuation were shown to be highly dependent on the geochemical environment as evidenced by the 2-5 fold reduction in half-lives at the ASR well which became methanogenic during the storage phase of the trial, as compared to an observation well situated 4 m away, which remained nitrate-reducing. These findings agree with previous laboratory-based studies which also show persistence declining with increased bromination of THMs and reducing redox conditions. Modelling suggests that the chlorinated injectant has sufficient residual chlorine and natural organic matter for substantial increases in THMs to occur within the aquifer, however this is masked in some of the field observations due to concurrent attenuation, particularly for the more rapidly attenuated brominated compounds. The model is based on data taken from water distribution systems and may not be representative for ASR since bromide and ammonia concentrations in the injected water and the possible role of organic carbon in the aquifer were not taken into consideration. During the storage phase DBP formation potentials were reduced as a result of the removal of precursor material despite an increase in the THM formation potential per unit weight of total organic carbon. This suggests that water quality improvements with respect to THMs and HAAs can be achieved through ASR in anoxic aquifers.

  4. Exposure to inhaled THM: comparison of continuous and event-specific exposure assessment for epidemiologic purposes.

    PubMed

    Thiriat, N; Paulus, H; Le Bot, B; Glorennec, P

    2009-10-01

    Trihalomethanes (THMs) (chloroform, bromoform, dibromochloromethane, and bromodichloromethane) are the most abundant by-products of chlorination. People are exposed to THMs through ingestion, dermal contact and inhalation. The objective of this study was to compare two methods for assessing THM inhalation: a direct method with personal monitors assessing continuous exposure and an indirect one with microenvironmental sampling and collection of time-activity data during the main event exposures: bathing, showering and swimming. This comparison was conducted to help plan a future epidemiologic study of the effects of THMs on the upper airways of children. 30 children aged from 4 to 10 years were included. They wore a 3M 3520 organic vapor monitor for 7 days. We sampled air in their bathrooms (during baths or showers) and in the indoor swimming pools they visited and recorded their time-activity patterns. We used stainless steel tubes full of Tenax to collect air samples. All analyses were performed with Gas Chromatography and Mass Spectrometry (GC-MS). Chloroform was the THM with the highest concentrations in the air of both bathrooms and indoor swimming pools. Its continuous and event exposure measurements were significantly correlated (r(s)=0.69 p<0.001). Continuous exposures were higher than event exposures, suggesting that the event exposure method does not take into account some influential microenvironments. In an epidemiologic study, this might lead to random exposure misclassification, thus underestimation of the risk, and reduced statistical power. The continuous exposure method was difficult to implement because of its poor acceptability and the fragility of the personal monitors. These two points may also reduce the statistical power of an epidemiologic study. It would be useful to test the advantages and disadvantages of a second sample in the home or of modeling the baseline concentration of THM in the home to improve the event exposure method.

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

    NASA Astrophysics Data System (ADS)

    Hughes, Claire; Sun, Shuo

    2015-04-01

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

  6. Abundances and variability of tropospheric volatile organic compounds at the South Pole and other Antarctic locations

    NASA Astrophysics Data System (ADS)

    Beyersdorf, Andreas J.; Blake, Donald R.; Swanson, Aaron; Meinardi, Simone; Rowland, F. S.; Davis, Douglas

    2010-11-01

    Multiyear (2000-2006) seasonal measurements of carbon monoxide, hydrocarbons, halogenated species, dimethyl sulfide, carbonyl sulfide and C 1-C 4 alkyl nitrates at the South Pole are presented for the first time. At the South Pole, short-lived species (such as the alkenes) typically were not observed above their limits of detection because of long transit times from source regions. Peak mixing ratios of the longer lived species with anthropogenic sources were measured in late winter (August and September) with decreasing mixing ratios throughout the spring. In comparison, compounds with a strong oceanic source, such as bromoform and methyl iodide, had peak mixing ratios earlier in the winter (June and July) because of decreased oceanic production during the winter months. Dimethyl sulfide (DMS), which is also oceanically emitted but has a short lifetime, was rarely measured above 5 pptv. This is in contrast to high DMS mixing ratios at coastal locations and shows the importance of photochemical removal during transport to the pole. Alkyl nitrate mixing ratios peaked during April and then decreased throughout the winter. The dominant source of the alkyl nitrates in the region is believed to be oceanic emissions rather than photochemical production due to low alkane levels. Sampling of other tropospheric environments via a Twin Otter aircraft included the west coast of the Ross Sea and large stretches of the Antarctic Plateau. In the coastal atmosphere, a vertical gradient was found with the highest mixing ratios of marine emitted compounds at low altitudes. Conversely, for anthropogenically produced species the highest mixing ratios were measured at the highest altitudes, suggesting long-range transport to the continent. Flights flown through the plume of Mount Erebus, an active volcano, revealed that both carbon monoxide and carbonyl sulfide are emitted with an OCS/CO molar ratio of 3.3 × 10 -3 consistent with direct observations by other investigators within the

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  8. Oceanic Emissions of Organic Very Short Lived Substances from the Indian Ocean and their Transport to the Stratosphere

    NASA Astrophysics Data System (ADS)

    Marandino, C. A.; Quack, B.; Hepach, H.; Atlas, E. L.; Fiehn, A.; Lennartz, S. T.; Bracher, A.; Krüger, K.; Waersted, E.

    2016-02-01

    Within the frame work of the German project OASIS, research cruises SO234-2 (Durban- Port Louis, 08-20 July, 2014) and SO235 (Port Louis - Male, July 23 to August 07, 2014) of the German research vessel SONNE were conducted by the University of Oslo, Norway (www.uio.no) together with the GEOMAR Helmholtz Centre for Ocean Research Kiel, Germany (www.geomar.de) in the subtropical and tropical West Indian Ocean. The research covered the sources and air- sea gas exchange of a suite of natural and anthropogenic short- and long lived trace gases as well as atmospheric composition and transport. Among the gases investigated were very short lived halocarbons such as bromoform, dibromomethane and methyl iodide, which are naturally produced in the oceans and influence stratospheric ozone and climate. The Asian monsoon circulation provides an effective pathway for air masses from the atmospheric boundary layer containing these and other compounds to enter the global stratosphere during boreal summer especially above India and the Bay of Bengal. During the cruises biological, chemical and physical parameters were analyzed in the surface waters and the deep ocean, the atmospheric conditions were determined, the oceanic trace gas emissions calculated and their transport and contribution to the stratospheric halogen budget, deduced from radiosonde launchings and high resolution transport modelling, was determined. The measurements were conducted in various marine biogeochemical regimes close to coasts, near coral reefs and sea banks, in high chlorophyll and oligotrophic regimes. We present novel results from the cruises, including biogeochemical responses to physical forcing and their contribution to the atmosphere.

  9. Mechanistic Aspects of the Formation of Adsorbable Organic Bromine during Chlorination of Bromide-containing Synthetic Waters.

    PubMed

    Langsa, Markus; Heitz, Anna; Joll, Cynthia A; von Gunten, Urs; Allard, Sebastien

    2017-05-02

    During chlorination of bromide-containing waters, a significant formation of brominated disinfection byproducts is expected. This is of concern because Br-DBPs are generally more toxic than their chlorinated analogues. In this study, synthetic water samples containing dissolved organic matter (DOM) extracts and bromide were treated under various disinfection scenarios to elucidate the mechanisms of Br-DBP formation. The total concentration of Br-DBPs was measured as adsorbable organic bromine (AOBr). A portion of the bromine (HOBr) was found to react with DOM via electrophilic substitution (≤40%), forming AOBr, and the remaining HOBr reacted with DOM via electron transfer with a reduction of HOBr to bromide (≥60%). During chlorination, the released bromide is reoxidized (recycled) by chlorine to HOBr, leading to further electrophilic substitution of unaltered DOM sites and chlorinated DOM moieties. This leads to an almost complete bromine incorporation to DOM (≥87%). The type of DOM (3.06 ≤ SUVA254 ≤ 4.85) is not affecting this process, as long as the bromine-reactive DOM sites are in excess and a sufficient chlorine exposure is achieved. When most reactive sites were consumed by chlorine, Cl-substituted functional groups (Cl-DOM) are reacting with HOBr by direct bromination leading to Br-Cl-DOM and by bromine substitution of chlorine leading to Br-DOM. The latter finding was supported by hexachlorobenzene as a model compound from which bromoform was formed during HOBr treatment. To better understand the experimental findings, a conceptual kinetic model allowing to assess the contribution of each AOBr pathway was developed. A simulation of distribution system conditions with a disinfectant residual of 1 mgC2 L(-1) showed complete conversion of Br(-) to AOBr, with about 10% of the AOBr formed through chlorine substitution by bromine.

  10. Changes in breath trihalomethane levels resulting from household water-use activities.

    PubMed

    Gordon, Sydney M; Brinkman, Marielle C; Ashley, David L; Blount, Benjamin C; Lyu, Christopher; Masters, John; Singer, Philip C

    2006-04-01

    Common household water-use activities such as showering, bathing, drinking, and washing clothes or dishes are potentially important contributors to individual exposure to trihalomethanes (THMs), the major class of disinfection by-products of water treated with chlorine. Previous studies have focused on showering or bathing activities. In this study, we selected 12 common water-use activities and determined which may lead to the greatest THM exposures and result in the greatest increase in the internal dose. Seven subjects performed the various water-use activities in two residences served by water utilities with relatively high and moderate total THM levels. To maintain a consistent exposure environment, the activities, exposure times, air exchange rates, water flows, water temperatures, and extraneous THM emissions to the indoor air were carefully controlled. Water, indoor air, blood, and exhaled-breath samples were collected during each exposure session for each activity, in accordance with a strict, well-defined protocol. Although showering (for 10 min) and bathing (for 14 min), as well as machine washing of clothes and opening mechanical dishwashers at the end of the cycle, resulted in substantial increases in indoor air chloroform concentrations, only showering and bathing caused significant increases in the breath chloroform levels. In the case of bromodichloromethane (BDCM), only bathing yielded a significantly higher air level in relation to the preexposure concentration. For chloroform from showering, strong correlations were observed for indoor air and exhaled breath, blood and exhaled breath, indoor air and blood, and tap water and blood. Only water and breath, and blood and breath were significantly associated for chloroform from bathing. For BDCM, significant correlations were obtained for blood and air, and blood and water from showering. Neither dibromochloromethane nor bromoform gave measurable breath concentrations for any of the activities

  11. Intercalation of Lithium in Pitch-Based Graphitized Carbon Fibers Chemically Modified by Fluorine: Soft Carbon With or Without an Oxide Surface

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Chen; Prisko, Aniko

    1999-01-01

    The effects of carbon structure and surface oxygen on the carbon's performance as the anode in lithium-ion battery were studied. Two carbon materials were used for the electrochemical tests: soft carbon made from defluorination of graphite fluoride, and the carbon precursor from which the graphite fluoride was made. In this research the precursor was graphitized carbon fiber P-100. It was first fluorinated to form CF(0.68), then defluorinated slowly at 350 to 450 C in bromoform, and finally heated in 1000 C nitrogen before exposed to room temperature air, producing disordered soft carbon having basic surface oxides. This process caused very little carbon loss. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) EC and DMC/Li half cell. The cycling test had four major results. (1) The presence of a basic oxide surface may prevent solvent from entering the carbon structure and therefore prolong the carbon's cycle life for lithium intercalation-deintercalation. (2) The disordered soft carbon can store lithium through two different mechanisms. One of them is lithium intercalation. which gives the disordered carbon an electrochemical behavior similar to its more ordered graphitic precursor. The other is unknown in its chemistry, but is responsible for the high-N,oltage portion (less than 0.3V) of the charge-discharge curve. (3) Under certain conditions, the disordered carbon can store more lithium than its precursor. (4) These sample and its precursor can intercalate at 200 mA/g. and deintercalate at a rate of 2000 mA/g without significant capacity loss.

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

    SciTech Connect

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  14. Blood Biomarkers of Late Pregnancy Exposure to Trihalomethanes in Drinking Water and Fetal Growth Measures and Gestational Age in a Chinese Cohort.

    PubMed

    Cao, Wen-Cheng; Zeng, Qiang; Luo, Yan; Chen, Hai-Xia; Miao, Dong-Yue; Li, Li; Cheng, Ying-Hui; Li, Min; Wang, Fan; You, Ling; Wang, Yi-Xin; Yang, Pan; Lu, Wen-Qing

    2016-04-01

    Previous studies have suggested that elevated exposure to disinfection by-products (DBPs) in drinking water during gestation may result in adverse birth outcomes. However, the findings of these studies remain inconclusive. The purpose of our study was to examine the association between blood biomarkers of late pregnancy exposure to trihalomethanes (THMs) in drinking water and fetal growth and gestational age. We recruited 1,184 pregnant women between 2011 and 2013 in Wuhan and Xiaogan City, Hubei, China. Maternal blood THM concentrations, including chloroform (TCM), bromodichloromethane (BDCM), dibromochloromethane (DBCM), and bromoform (TBM), were measured as exposure biomarkers during late pregnancy. We estimated associations with gestational age and fetal growth indicators [birth weight, birth length, and small for gestational age (SGA)]. Total THMs (TTHMs; sum of TCM, BDCM, DBCM, and TBM) were associated with lower mean birth weight (-60.9 g; 95% CI: -116.2, -5.6 for the highest vs. lowest tertile; p for trend = 0.03), and BDCM and DBCM exposures were associated with smaller birth length (e.g., -0.20 cm; 95% CI: -0.37, -0.04 for the highest vs. lowest tertile of DBCM; p for trend = 0.02). SGA was increased in association with the second and third tertiles of TTHMs (OR = 2.91; 95% CI: 1.32, 6.42 and OR = 2.25; 95% CI: 1.01, 5.03; p for trend = 0.08). Our results suggested that elevated maternal THM exposure may adversely affect fetal growth. Cao WC, Zeng Q, Luo Y, Chen HX, Miao DY, Li L, Cheng YH, Li M, Wang F, You L, Wang YX, Yang P, Lu WQ. 2016. Blood biomarkers of late pregnancy exposure to trihalomethanes in drinking water and fetal growth measures and gestational age in a Chinese cohort. Environ Health Perspect 124:536-541; http://dx.doi.org/10.1289/ehp.1409234.

  15. What’s in the Pool? A Comprehensive Identification of Disinfection By-products and Assessment of Mutagenicity of Chlorinated and Brominated Swimming Pool Water

    PubMed Central

    Richardson, Susan D.; DeMarini, David M.; Kogevinas, Manolis; Fernandez, Pilar; Marco, Esther; Lourencetti, Carolina; Ballesté, Clara; Heederik, Dick; Meliefste, Kees; McKague, A. Bruce; Marcos, Ricard; Font-Ribera, Laia; Grimalt, Joan O.; Villanueva, Cristina M.

    2010-01-01

    Background Swimming pool disinfectants and disinfection by-products (DBPs) have been linked to human health effects, including asthma and bladder cancer, but no studies have provided a comprehensive identification of DBPs in the water and related that to mutagenicity. Objectives We performed a comprehensive identification of DBPs and disinfectant species in waters from public swimming pools in Barcelona, Catalonia, Spain, that disinfect with either chlorine or bromine and we determined the mutagenicity of the waters to compare with the analytical results. Methods We used gas chromatography/mass spectrometry (GC/MS) to measure trihalomethanes in water, GC with electron capture detection for air, low- and high-resolution GC/MS to comprehensively identify DBPs, photometry to measure disinfectant species (free chlorine, monochloroamine, dichloramine, and trichloramine) in the waters, and an ion chromatography method to measure trichloramine in air. We assessed mutagenicity with the Salmonella mutagenicity assay. Results We identified > 100 DBPs, including many nitrogen-containing DBPs that were likely formed from nitrogen-containing precursors from human inputs, such as urine, sweat, and skin cells. Many DBPs were new and have not been reported previously in either swimming pool or drinking waters. Bromoform levels were greater in brominated than in chlorinated pool waters, but we also identified many brominated DBPs in the chlorinated waters. The pool waters were mutagenic at levels similar to that of drinking water (~ 1,200 revertants/L-equivalents in strain TA100–S9 mix). Conclusions This study identified many new DBPs not identified previously in swimming pool or drinking water and found that swimming pool waters are as mutagenic as typical drinking waters. PMID:20833605

  16. What's in the pool? A comprehensive identification of disinfection by-products and assessment of mutagenicity of chlorinated and brominated swimming pool water.

    PubMed

    Richardson, Susan D; DeMarini, David M; Kogevinas, Manolis; Fernandez, Pilar; Marco, Esther; Lourencetti, Carolina; Ballesté, Clara; Heederik, Dick; Meliefste, Kees; McKague, A Bruce; Marcos, Ricard; Font-Ribera, Laia; Grimalt, Joan O; Villanueva, Cristina M

    2010-11-01

    Swimming pool disinfectants and disinfection by-products (DBPs) have been linked to human health effects, including asthma and bladder cancer, but no studies have provided a comprehensive identification of DBPs in the water and related that to mutagenicity. We performed a comprehensive identification of DBPs and disinfectant species in waters from public swimming pools in Barcelona, Catalonia, Spain, that disinfect with either chlorine or bromine and we determined the mutagenicity of the waters to compare with the analytical results. We used gas chromatography/mass spectrometry (GC/MS) to measure trihalomethanes in water, GC with electron capture detection for air, low- and high-resolution GC/MS to comprehensively identify DBPs, photometry to measure disinfectant species (free chlorine, monochloroamine, dichloramine, and trichloramine) in the waters, and an ion chromatography method to measure trichloramine in air. We assessed mutagenicity with the Salmonella mutagenicity assay. We identified > 100 DBPs, including many nitrogen-containing DBPs that were likely formed from nitrogen-containing precursors from human inputs, such as urine, sweat, and skin cells. Many DBPs were new and have not been reported previously in either swimming pool or drinking waters. Bromoform levels were greater in brominated than in chlorinated pool waters, but we also identified many brominated DBPs in the chlorinated waters. The pool waters were mutagenic at levels similar to that of drinking water (approximately 1,200 revertants/L-equivalents in strain TA100-S9 mix). This study identified many new DBPs not identified previously in swimming pool or drinking water and found that swimming pool waters are as mutagenic as typical drinking waters.

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

    PubMed

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

    2013-01-15

    Medium pressure UV is used for controlling the concentration of combined chlorine (chloramines) in many public swimming pools. Little is known about the fate of other disinfection by-products (DBPs) in UV treatment. Photolysis by medium pressure UV treatment was investigated for 12 DBPs reported to be found in swimming pool water: chloroform, bromodichloromethane, dibromochloromethane, bromoform, dichloroacetonitrile, bromochloroacetonitrile, dibromoacetronitrile, trichloroacetonitrile, trichloronitromethane, dichloropropanone, trichloropropanone, and chloral hydrate. First order photolysis constants ranged 26-fold from 0.020 min(-1) for chloroform to 0.523 min(-1) for trichloronitromethane. The rate constants generally increased with bromine substitution. Using the UV removal of combined chlorine as an actinometer, the rate constants were recalculated to actual treatment doses of UV applied in a swimming pool. In an investigated public pool the UV dose was equivalent to an applied electrical energy of 1.34 kWh m(-3) d(-1) and the UV dose required to removed 90% of trichloronitromethane was 0.4 kWh m(-3) d(-1), while 2.6 kWh m(-3) d(-1) was required for chloral hydrate and the bromine containing haloacetonitriles and trihalomethanes ranged from 0.6 to 3.1 kWh m(-3) d(-1). It was predicted thus that a beneficial side-effect of applying UV for removing combined chlorine from the pool water could be a significant removal of trichloronitromethane, chloral hydrate and the bromine containing haloacetonitriles and trihalomethanes. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    SciTech Connect

    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.

  19. Optical properties of flyash

    SciTech Connect

    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.

  20. Convective transport of very short lived bromocarbons to the stratosphere

    NASA Astrophysics Data System (ADS)

    Liang, Q.; Atlas, E.; Blake, D.; Dorf, M.; Pfeilsticker, K.; Schauffler, S.

    2014-06-01

    We use the NASA Goddard Earth Observing System (GEOS) Chemistry Climate Model (GEOSCCM) to quantify the contribution of the two most important brominated very short lived substances (VSLSs), bromoform (CHBr3) and dibromomethane (CH2Br2), to stratospheric bromine and its sensitivity to convection strength. Model simulations suggest that the most active transport of VSLSs from the marine boundary layer through the tropopause occurs over the tropical Indian Ocean, the tropical western Pacific, 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 active convective lofting regions mentioned above. Of the total ~8 ppt VSLS bromine that enters the base of the TTL at ~150 hPa, half is in the form of organic source gases and half in the form of inorganic product gases. Only a small portion (<10%) of the VSLS-originated bromine is removed via wet scavenging in the TTL before reaching the lower stratosphere. On average, globally, 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 (strongest) and minimum (weakest) convection conditions can introduce a ~2.6 pptv uncertainty in the contribution of VSLSs to inorganic bromine in the stratosphere (BryVSLS). Contrary to conventional wisdom, the minimum convection condition leads to a larger BryVSLS as the reduced scavenging in soluble product gases, and thus a significant increase in product gas injection (2-3 ppt), greatly exceeds the relatively minor decrease in source gas injection (a few 10ths ppt).

  1. Convective transport of very-short-lived bromocarbons to the stratosphere

    NASA Astrophysics Data System (ADS)

    Liang, Q.; Atlas, E.; Blake, D.; Dorf, M.; Pfeilsticker, K.; Schauffler, S.

    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).

  2. Fate of disinfection by-products in groundwater during aquifer storage and recovery with reclaimed water

    NASA Astrophysics Data System (ADS)

    Pavelic, Paul; Nicholson, Brenton C.; Dillon, Peter J.; Barry, Karen E.

    2005-05-01

    Knowledge on the behaviour of disinfection by-products (DBPs) during aquifer storage and recovery (ASR) is limited even though this can be an important consideration where recovered waters are used for potable purposes. A reclaimed water ASR trial in an anoxic aquifer in South Australia has provided some of the first quantitative information at field-scale on the fate and transport of trihalomethanes (THMs) and haloacetic acids (HAAs). The results revealed that THM half-lives varied from <1 to 65 days, with persistence of chloroform being highest and bromoform lowest. HAA attenuation was rapid (<1 day). Rates of THM attenuation were shown to be highly dependent on the geochemical environment as evidenced by the 2-5 fold reduction in half-lives at the ASR well which became methanogenic during the storage phase of the trial, as compared to an observation well situated 4 m away, which remained nitrate-reducing. These findings agree with previous laboratory-based studies which also show persistence declining with increased bromination of THMs and reducing redox conditions. Modelling suggests that the chlorinated injectant has sufficient residual chlorine and natural organic matter for substantial increases in THMs to occur within the aquifer, however this is masked in some of the field observations due to concurrent attenuation, particularly for the more rapidly attenuated brominated compounds. The model is based on data taken from water distribution systems and may not be representative for ASR since bromide and ammonia concentrations in the injected water and the possible role of organic carbon in the aquifer were not taken into consideration. During the storage phase DBP formation potentials were reduced as a result of the removal of precursor material despite an increase in the THM formation potential per unit weight of total organic carbon. This suggests that water quality improvements with respect to THMs and HAAs can be achieved through ASR in anoxic aquifers.

  3. Fate of disinfection by-products in groundwater during aquifer storage and recovery with reclaimed water

    NASA Astrophysics Data System (ADS)

    Pavelic, Paul; Nicholson, Brenton C.; Dillon, Peter J.; Barry, Karen E.

    2005-03-01

    Knowledge on the behaviour of disinfection by-products (DBPs) during aquifer storage and recovery (ASR) is limited even though this can be an important consideration where recovered waters are used for potable purposes. A reclaimed water ASR trial in an anoxic aquifer in South Australia has provided some of the first quantitative information at field-scale on the fate and transport of trihalomethanes (THMs) and haloacetic acids (HAAs). The results revealed that THM half-lives varied from <1 to 65 days, with persistence of chloroform being highest and bromoform lowest. HAA attenuation was rapid (<1 day). Rates of THM attenuation were shown to be highly dependent on the geochemical environment as evidenced by the 2-5 fold reduction in half-lives at the ASR well which became methanogenic during the storage phase of the trial, as compared to an observation well situated 4 m away, which remained nitrate-reducing. These findings agree with previous laboratory-based studies which also show persistence declining with increased bromination of THMs and reducing redox conditions. Modelling suggests that the chlorinated injectant has sufficient residual chlorine and natural organic matter for substantial increases in THMs to occur within the aquifer, however this is masked in some of the field observations due to concurrent attenuation, particularly for the more rapidly attenuated brominated compounds. The model is based on data taken from water distribution systems and may not be representative for ASR since bromide and ammonia concentrations in the injected water and the possible role of organic carbon in the aquifer were not taken into consideration. During the storage phase DBP formation potentials were reduced as a result of the removal of precursor material despite an increase in the THM formation potential per unit weight of total organic carbon. This suggests that water quality improvements with respect to THMs and HAAs can be achieved through ASR in anoxic aquifers.

  4. Formation of Bromate and Halogenated Disinfection Byproducts during Chlorination of Bromide-Containing Waters in the Presence of Dissolved Organic Matter and CuO.

    PubMed

    Liu, Chao; Croué, Jean-Philippe

    2016-01-05

    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 tricarboxylic 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.

  5. Polyhalogenated Very Short Live Substances in the Atlantic Ocean, and their Linkages with Ocean Primary Production

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Yvon-Lewis, S. A.; Hu, L.; Bianchi, T. S.; Campbell, L.; Smith, R. W.

    2011-12-01

    The Halocarbon Air-Sea Transect - Atlantic (HalocAST-A) cruise was conducted aboard FS Polarstern during the ANT-XXVII/1 expedition. The ship departed from Bremerhaven, Germany on October 25th and arrived in Cape Town, South Africa on November 24th in 2010. The HalocAST-A cruise was devoted to studying air-sea fluxes of a suite of halocarbon compounds. Atmospheric mixing ratios and seawater concentrations of the halocarbons were continuously measured with the gas chromatograph - mass spectrometer (GC-MS). This study focuses on the polyhalogenated very short lived substances (VSLSs) such as bromoform (CHBr3), dibromomethane (CH2Br2), chlorodibromomethane (CHClBr2), and bromodichloromethane (CHBrCl2). The goal of this study is to examine the distributions of these compounds and possible relationship between their emissions and oceanic primary production. Therefore, along with the halocarbon concentrations, parameters like dissolved organic carbon concentrations, nutrient concentrations, pigment concentrations, and picoplankton and heterotrophic bacteria counts were also determined. The observed saturation anomalies indicated these VSLSs were supersaturated for almost the entire duration of the cruise. The highest seawater concentrations for these compounds were observed near the Canary Islands. Air mixing ratios were also elevated in this region. The net fluxes for CHBr3, CH2Br2, CHClBr2, and CHBrCl2 were 13.8 nmol m-2 d-1, 4.5 nmol m-2 d-1, 4.5 nmol m-2 d-1 and 1.2 nmol m-2 d-1, respectively. During the HalocAST-A cruise, these compounds exhibit similar trends with total chlorophyll a. Contributions from selected phytoplankton group will be further assessed through the use of individual pigment biomarkers.

  6. Percutaneous absorption of trihalomethanes, haloacetic acids, and haloketones.

    PubMed

    Xu, Xu; Mariano, Thomas M; Laskin, Jeffrey D; Weisel, Clifford P

    2002-10-01

    Bathing in chlorinated drinking water causes significant exposure to potentially toxic disinfection by-products (DBPs). In the present studies, we measured the permeation coefficients (K(p)) of three important classes of DBPs, trihalomethanes (THMs), haloketones (HKs), and haloacetic acids (HAAs), in aqueous solution across human skin using in vitro diffusion chambers. Linear mixed-effects model was utilized to calculate the steady-state permeability coefficients. The permeability coefficients of THMs ranged from 0.16 to 0.21 cm/h when the donor solution was at 25 degrees C. Bromoform had the highest K(p) value, while chloroform was the least permeable through the skin. THMs were approximately 10 times more permeable than HKs, while the permeability of HAAs through the skin was very low (1 to 3 x 10(-3) cm/h, pH 7). The permeability of HKs tripled as the temperature was increased from room temperature (20 degrees C) to bathing temperature (40 degrees C). A direct relationship was found between the permeability of THMs, but not HKs and HAAs, and their octanol/water partition coefficients. The dermal dose from daily bathing activities was approximated for an average adult using U.S. EPA recommended methods and found to be 40-70% of the daily ingestion dose for the THMs, 10% of the ingestion dose for HKs, and an insignificant percentage of the ingestion dose for the HAAs. In addition to ingestion, dermal absorption is an important route of exposure to THMs and HKs and must be considered in models of risk assessment.

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

    SciTech Connect

    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.

  8. Peracetic acid oxidation of saline waters in the absence and presence of H ₂O ₂: secondary oxidant and disinfection byproduct formation.

    PubMed

    Shah, Amisha D; Liu, Zheng-Qian; Salhi, Elisabeth; Höfer, Thomas; von Gunten, Urs

    2015-02-03

    Peracetic acid (PAA) is a disinfectant considered for use in ballast water treatment, but its chemical behavior in such systems (i.e., saline waters) is largely unknown. In this study, the reactivity of PAA with halide ions (chloride and bromide) to form secondary oxidants (HOCl, HOBr) was investigated. For the PAA-chloride and PAA-bromide reactions, second-order rate constants of (1.47 ± 0.58) × 10(-5) and 0.24 ± 0.02 M(-1) s(-1) were determined for the formation of HOCl or HOBr, respectively. Hydrogen peroxide (H2O2), which is always present in PAA solutions, reduced HOCl or HOBr to chloride or bromide, respectively. As a consequence, in PAA-treated solutions with [H2O2] > [PAA], the HOBr (HOCl) steady-state concentrations were low with a limited formation of brominated (chlorinated) disinfection byproducts (DBPs). HOI (formed from the PAA-iodide reaction) affected this process because it can react with H2O2 back to iodide. H2O2 is thus consumed in a catalytic cycle and leads to less efficient HOBr scavenging at even low iodide concentrations (<1 μM). In PAA-treated solutions with [H2O2] < [PAA] and high bromide levels, mostly brominated DBPs are formed. In synthetic water, bromate was formed from the oxidation of bromide. In natural brackish waters, bromoform (CHBr3), bromoacetic acid (MBAA), dibromoacetic acid (DBAA), and tribromoacetic acid (TBAA) formed at up to 260, 106, 230, and 89 μg/L, respectively for doses of 2 mM (ca. 150 mg/L) PAA and [H2O2] < [PAA]. The same brackish waters, treated with PAA with [H2O2] ≫ [PAA], similar to conditions found in commercial PAA solutions, resulted in no trihalomethanes and only low haloacetic acid concentrations.

  9. Halogen species in the marine boundary layer between Singapore and Wellington, New Zealand

    NASA Astrophysics Data System (ADS)

    Harris, N. R.; Johnston, P. V.; Kreher, K.; Harvey, M.; Hay, T.; Robinson, A.; Ashfold, M.; Archibald, A.; Pyle, J. A.; Huang, R.; Hoffmann, T.

    2011-12-01

    We report measurements of organic and inorganic short-lived halogen species made during a cruise of the NIWA research vessel Tangaroa as it sailed from Singapore to Wellington, New Zealand in November and December 2010. The organic species measured with the Dirac gas chromatograph include CHBr3, CH2Br2, CHBr2Cl, CHBrCl2, CH2BrCl, CH3I and CHClI. The inorganic species include I2 (measured with denuder tubes), and IO and BrO were measured with a MAX-DOAS as were O3 and NO2. A cloud nuclei counter worked successfully for the first half of the cruise. In general the halocarbon concentrations declined with increasing latitude, with values for bromoform and dibromomethane of 1.5 to 2 ppt at the equator and 0.5 to 1 ppt in the Tasman Sea off Wellington. Higher values and higher variability were observed near coastlines, most dramatically in and near the Torres Strait when they reached as high as 30 ppt and 5 ppt respectively. Similar behaviour was seen in the other bromocarbons. Molecular iodine levels typically varied between 10 and 50 ppt, similar to those observed at northern mid-latitudes (Mace Head, Ireland). Significantly elevated values of I2 (60 to 100 ppt) were seen near the Torres Strait. Greater variability of I2 was observed in shallower waters. In contrast, BrO levels were below the detection limit of about 0.5-1 ppt for the whole cruise. IO was observed in with peak values of around 1 ppt in the Torres Strait, and with higher values in the tropical seas than in the Tasman Sea. The occurrence of such low IO values in the presence of high I2 values is currently a mystery and is being investigated with a photochemical box model.

  10. Ozonation of iodide-containing waters: selective oxidation of iodide to iodate with simultaneous minimization of bromate and I-THMs.

    PubMed

    Allard, S; Nottle, C E; Chan, A; Joll, C; von Gunten, U

    2013-04-15

    The presence of iodinated disinfection by-products (I-DBPs) in drinking water poses a potential health concern since it has been shown that I-DBPs are generally more genotoxic and cytotoxic than their chlorinated and brominated analogs. I-DBPs are formed during oxidation/disinfection of iodide-containing waters by reaction of the transient hypoiodous acid (HOI) with natural organic matter (NOM). In this study, we demonstrate that ozone pre-treatment selectively oxidizes iodide to iodate and avoids the formation of I-DBPs. Iodate is non-toxic and is therefore a desired sink of iodine in drinking water. Complete conversion of iodide to iodate while minimizing the bromate formation to below the guideline value of 10 μg L⁻¹ was achieved for a wide range of ozone doses in five raw waters with DOC and bromide concentrations of 1.1-20 mg L⁻¹ and 170-940 μg L⁻¹, respectively. Lowering the pH effectively further reduced bromate formation but had no impact on the extent of iodate and bromoform formation (the main trihalomethane (THM) formed during ozonation). Experiments carried out with pre-chlorinated/post-clarified samples already containing I-DBPs, showed that ozonation effectively oxidized I-THMs. Therefore, in iodide-containing waters, in which I-DBPs can be produced upon chlorination or especially chloramination, a pre-ozonation step to oxidize iodide to iodate is an efficient process to mitigate I-DBP formation.

  11. A halocarbon survey from a seagrass dominated subtropical lagoon, Ria Formosa (Portugal): flux pattern and isotopic composition

    NASA Astrophysics Data System (ADS)

    Weinberg, I.; Bahlmann, E.; Eckhardt, T.; Michaelis, W.; Seifert, R.

    2014-07-01

    Here we report fluxes of chloromethane (CH3Cl), bromomethane (CH3Br), iodomethane (CH3Cl), and bromoform (CHBr3) from two sampling campaigns (summer and spring) in the seagrass dominated subtropical lagoon Ria Formosa, Portugal. Dynamic flux chamber measurements were performed when seagrass patches were air-exposed and submerged. Overall, we observed highly variable fluxes from the seagrass meadows and attributed them to diurnal cycles, tidal effects, and the variety of possible sources and sinks in the seagrass meadows. Highest emissions with up to 130 nmol m-2 h-1 for CH3Br were observed during tidal changes from air exposure to submergence and conversely. Furthermore, at least during the spring campaign, the emissions of halocarbons were significantly elevated during tidal inundation as compared to air exposure. Accompanying water sampling during both campaigns revealed elevated concentrations of CH3Cl and CH3Br indicating productive sources within the lagoon. Stable carbon isotopes of halocarbons from the air and water phase along with source signatures were used to allocate the distinctive sources and sinks in the lagoon. Results suggest CH3Cl rather originating from seagrass meadows and water column than from salt marshes. Aqueous and atmospheric CH3Br was substantially enriched in 13C in comparison to source signatures for seagrass meadows and salt marshes. This suggests a significant contribution of the water column to the atmospheric CH3Br in the lagoon. A rough global upscaling yields annual productions from seagrass meadows of 2.3-4.5 Gg yr-1, 0.5-1.0 Gg yr-1, 0.6-1.2 Gg yr-1, and 1.9-3.7 Gg yr-1 for CH3Cl, CH3Br, CH3I, and CHBr3 respectively. This suggests a minor contribution from seagrass meadows to the global production of these halocarbons with about 0.1% for CH3Cl and about 0.7% for CH3Br.

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

    PubMed

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

    2017-01-01

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

  13. Application of chemical, physical and chemometric analytical techniques to the study of ancient ceramic oil lamps.

    PubMed

    García Giménez, R; Vigil de la Villa, R; Petit Domínguez, M D; Rucandio, M I

    2006-02-15

    A chemical, mineralogical and morphological characterization of 54 fragments of oil lamps found in two Spanish archaeological sites (Cordoba and Herrera de Pisuerga (Palencia)) has been performed. Flame atomic absorption and emission spectrometry were used for the determination of Al(2)O(3), CaO, Fe(2)O(3), K(2)O, MgO, MnO, Na(2)O and TiO(2) as major constituents and Cu, Cr, Ni, Pb and Zn as minor and trace selected elements. Physical, mineralogical and morphological analyses were made by using dilatometry at constant heating rate for the thermal behaviour, X-ray diffraction spectrometry for the mineralogical composition and, in a group of selected samples, scanning electron microscopy and polarizing petrographic microscopy for the observation of thin layers and mineral identification. Separations of light and heavy minerals were carried out with bromoform and X-ray diffraction analysis was applied to both fractions. Multivariate statistical analysis was used to establish correlations between variables and to deduce factors which allow the gathering of oil lamp samples in groups as a function of their composition. The results of these analyses allow the comparison among pieces and the establishment of conclusions about several aspects of their manufacture, the origin of the raw materials and the provenance of the oil lamps (local or imported). They provide information supporting certain archaeological hypothesis. For example, some oil lamps found in Herrera de Pisuerga showed a clearly different physicochemical composition. They were probably brought from Italy by the Roman Legions together with their initial furniture household.

  14. ICON-ART 1.0 - a new online-coupled model system from the global to regional scale

    NASA Astrophysics Data System (ADS)

    Rieger, D.; Bangert, M.; Bischoff-Gauss, I.; Förstner, J.; Lundgren, K.; Reinert, D.; Schröter, J.; Vogel, H.; Zängl, G.; Ruhnke, R.; Vogel, B.

    2015-06-01

    We present the first stage of a new online-coupled global to regional-scale modeling framework for the simulation of the spatiotemporal evolution of aerosols and trace gases. The underlying meteorological model is the new nonhydrostatic model system ICON (ICOsahedral Nonhydrostatic) which allows a local grid refinement with two-way interactions between the grids. We develop the extension ART (Aerosol and Reactive Trace gases) with the goal of simulating interactions between trace substances and the state of the atmosphere. Within this paper, we present the basic equations and give an overview of the physical parameterizations as well as numerical methods we use. First applications of the new model system for trace gases, monodisperse particles and polydisperse particles are shown. The simulated distribution of two very short-lived substances (VSLS), bromoform (CHBr3) and dibromomethane (CH2Br2) reflecting the fast upward transport shows a good agreement with observations and previous model studies. Also, the shape of the simulated tropical profiles is well reproduced. As an example for the treatment of monodisperse particles we present the simulated ash plume of the Eyjafjallajökull eruption in April 2010. Here, a novel approach for the source function is applied. The pattern of the simulated distribution of volcanic ash particles shows a good agreement with previous studies. As an example for the treatment of a polydisperse aerosol, where number densities and mass concentrations are accounted for, we simulated the annual emissions of sea salt. We obtain a total emission flux of 26.0 Pg yr-1 and an emission flux of particles with diameter less than 10 μm of 7.36 Pg yr-1.

  15. ICON-ART 1.0 - a new online-coupled model system from the global to regional scale

    NASA Astrophysics Data System (ADS)

    Rieger, D.; Bangert, M.; Bischoff-Gauss, I.; Förstner, J.; Lundgren, K.; Reinert, D.; Schröter, J.; Vogel, H.; Zängl, G.; Ruhnke, R.; Vogel, B.

    2015-01-01

    We present the first stage of a new online-coupled global to regional scale modelling framework for the simulation of the spatiotemporal evolution of aerosols and trace gases. The underlying meteorological model is the new nonhydrostatic model system ICON (ICOsahedral Nonhydrostatic) which allows a local grid refinement with two-way interactions between the grids. We develop the extension ART (Aerosol and Reactive Trace gases) with the goal to simulate interactions between trace substances and the state of the atmosphere. Within this paper, we present the basic equations and give an overview of the physical parameterizations as well as numerical methods we use. First applications of the new model system for trace gases, monodisperse particles and polydisperse particles are shown. The simulated distribution of two very short-lived substances, Bromoform (CHBr3) and Dibrommethane (CH2Br2) reflecting the fast upward transport shows a good agreement with observations and previous model studies. Also, the shape of the simulated tropical profiles is well reproduced. As an example for the treatment of monodisperse particles we present the simulated ash plume of the Eyjafjallajökull eruption in April 2010. Here, a novel approach for the source function is applied. The pattern of the simulated distribution of volcanic ash particles shows an agreement with previous studies. As an example for the treatment of a polydisperse aerosol, where number densities and mass concentrations are accounted for, we simulated the annual emissions of sea salt. We obtain a total emission flux of 26.0 Pg yr-1 and an emission flux of particles with diameter less than 10 μm of 7.36 Pg yr-1.

  16. Occurrence of trihalomethanes in the nation's ground water and drinking-water supply wells, 1985-2002

    USGS Publications Warehouse

    Schaap, Bryan D.; Zogorski, John S.

    2006-01-01

    This report describes the occurrence of trihalomethanes (THMs) in the Nation's ground water and drinking-water supply wells based on analysis of 5,642 samples of untreated ground water and source water collected or compiled during 1985-2002 by the U.S. Geological Survey National Water-Quality Assessment (NAWQA) Program. THMs are a group of volatile organic compounds (VOCs) with natural and anthropogenic sources that are of interest because they are associated with acute and chronic health problems in humans. THMs occur in water primarily from chlorination and are classified as disinfection by-products. In this report, the four THMs are discussed in the order of chloroform, bromodichloromethane, dibromochloromethane, and then bromoform; this sequence corresponds to largest to smallest chlorine content and smallest to largest bromine content. Four trihalomethanes were detected in less than 20 percent of samples from studies of (1) aquifers, (2) shallow ground water in agricultural areas, (3) shallow ground water in urban areas, (4) domestic wells, and (5) public wells. Detection frequencies for individual THMs in the five studies ranged from zero for shallow ground water in agricultural areas to 19.5 percent for shallow ground water in urban areas. None of the samples from aquifer studies, domestic wells, or public wells had total THM concentrations (the sum of the concentrations of chloroform, bromodichloromethane, dibromochloromethane, and bromoform) greater than or equal to the U.S. Environmental Protection Agency Maximum Contaminant Level of 80 micrograms per liter (?g/L). Comparisons of results among studies of aquifers, shallow ground water in agricultural areas, and shallow ground water in urban areas were used to describe the occurrence of the four THMs in ground water for three different land-use settings-mixed, agricultural, and urban, respectively. At the 0.2-?g/L assessment level, one or more of the four THMs were detected in 7.9 percent of the samples

  17. Finding the missing stratospheric Bry: A global modeling study of CHBr3 and CH2Br2

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

    Recent in situ and satellite measurements suggest a contribution of ~5 (3-8) pptv to the stratospheric inorganic bromine from short-lived bromocarbons. We perform a modeling study of two most important short-lived bromocarbons, bromoform (CHBr3) and dibromomethane (CH2Br2), with a global chemistry climate model, GEOS CCM, to account for this missing stratospheric bromine. We conduct a 10-year GEOS CCM bromine chemistry simulation that includes a detailed representation of oceanic emissions of CHBr3 and CH2Br2, their chemical losses through photolysis and reaction with OH, surface dry deposition of their degradation product, inorganic bromine (Bry), as well as wet scavenging of Bry in large-scale precipitation and convective updrafts. We derive a “top-down” emission estimate of CHBr3 and CH2Br2, using airborne measurements in the troposphere and lower stratosphere (LS) in the Pacific and North America region from nine NASA aircraft campaigns, including PEM-tropics, TRACE-P, INTEX-A, INTEX-B, TC4, STRAT, Pre-AVE, AVE, as well as the most recent mission, ARCTAS. The global oceanic emission of CHBr3 and CH2Br2 are 450 Gg/yr and 62 Gg/yr, respectively, with 60% from open ocean and 40% along coastlines. Our global emission estimate of CHBr3 is likely a low limit due to model’s inadequacy in reproducing the very high surface concentrations near coastlines. An accurate estimate of CH2Br2 emission is largely dependent on the model’s ability in reproducing the OH field. The model simulates well the observed horizontal distribution and vertical gradient of CHBr3 and CH2Br2 from the surface to the LS. Albeit a simple emission scheme assuming no seasonal variations, the model reproduces well the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss. At steady state, the inclusion

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

    NASA Astrophysics Data System (ADS)

    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

  19. Measurements of Halocarbons at the Boulder Atmospheric Observatory during NACHTT 2011

    NASA Astrophysics Data System (ADS)

    Zhou, Y.; Swarthout, R.; Hart, A.; Russo, R.; Young, A.; Sive, B. C.

    2011-12-01

    Halocarbons including trichloroethylene (C2HCl3), tetrochlorocarbon (C2Cl4), chloroform (CHCl3), dibromomethane (CH2Br2), bromoform (CHBr3), and methyl iodide (CH3I) were measured at the Boulder Atmospheric Observatory (BAO) in Erie, CO from February 18 - March 13, 2011. Whole air samples were collected in canisters from 20 m above the ground and analyzed using a five channel gas chromatographic analytical system. Vertical profiles of these compounds were also determined from canister samples collected at heights of 50, 100, 150, 200, and 250 meters. For the anthropogenic halocarbons, mixing ratios ranged from 3.0 to 75.9 pptv (average=9.6 pptv) for C2Cl4, from 0.3 to 65.8 pptv (average=2.8 pptv) for C2HCl3, and from 9.8 to 43.9 pptv (average=14.8 pptv) for CHCl3. These three gases tracked each other indicating their common urban/industrial sources. Mixing ratios of C2Cl4, C2HCl3, and CHCl3 decreased with height suggesting that there were local surface sources of these gases. For the marine derived halocarbons, mixing ratios ranged from 0.27 to 1.30 pptv (average=0.59 pptv) for CHBr3 and from 0.64 to 1.23 pptv (average=0.96 pptv) for CH2Br2. These values were much lower compared to those (CHBr3: from 1.4 to 8.4 pptv (average: 2.6 pptv) and CH2Br2: from 1.2 to 2.4 pptv (average: 1.6 pptv)) measured at Thompson Farm, NH, a monitoring site near the New Hampshire seacoast during January - March, 2002. The CH2Br2/CHBr3 ratios at BAO ranged from ~0.8 to 3.0, significantly higher than previously reported emission ratios of these two gases in source regions (CH2Br2 /CHBr3 ~0.15), consistent with their remote oceanic sources. There was no obvious gradient existing from ground up to 250 m height revealing their even mixing in the troposphere. However, CH3I mixing ratios ranged from 0.07 to 0.45 pptv with the average value of 0.22 pptv. In contrast to CH2Br2 and CHBr3, CH3I mixing ratios at 50 m were higher than those measured at 100, 150, 200, and 250 m heights, indicating

  20. Drivers of diel and regional variations of halocarbon emissions from the tropical North East Atlantic

    NASA Astrophysics Data System (ADS)

    Hepach, H.; Quack, B.; Ziska, F.; Fuhlbrügge, S.; Atlas, E. L.; Peeken, I.; Krüger, K.; Wallace, D. W. R.

    2013-07-01

    Methyl iodide (CH3I}, bromoform (CHBr3) and dibromomethane (CH2Br2), which are produced naturally in the oceans, take part in ozone chemistry both in the troposphere and the stratosphere. The significance of oceanic upwelling regions for emissions of these trace gases in the global context is still uncertain although they have been identified as important source regions. To better quantify the role of upwelling areas in current and future climate, this paper analyzes major factors that influenced halocarbon emissions from the tropical North East Atlantic including the Mauritanian upwelling during the DRIVE expedition. Diel and regional variability of oceanic and atmospheric CH3I, CHBr3 and CH2Br2 was determined along with biological and meteorological parameters at six 24 h-stations. Low oceanic concentrations of CH3I from 0.1-5.4 pmol L-1 were equally distributed throughout the investigation area. CHBr3 of 1.0-42.4 pmol L-1 and CH2Br2 of 1.0-9.4 pmol L-1 were measured with maximum concentrations close to the Mauritanian coast. Atmospheric mixing rations of CH3I of up to 3.3, CHBr3 to 8.9 and CH2Br2 to 3.1 ppt above the upwelling and 1.8, 12.8, respectively 2.2 ppt at a Cape Verdean coast were detected during the campaign. While diel variability in CH3I emissions could be mainly ascribed to oceanic non-biological production, no main driver was identified for its emissions in the entire study region. In contrast, oceanic bromocarbons resulted from biogenic sources which were identified as regional drivers of their sea-to-air fluxes. The diel impact of wind speed on bromocarbon emissions increased with decreasing distance to the coast. The height of the marine atmospheric boundary layer (MABL) was determined as an additional factor influencing halocarbon emissions. Oceanic and atmospheric halocarbons correlated well in the study region and in combination with high oceanic CH3I, CHBr3 and CH2Br2 concentrations, local hot spots of atmospheric halocarbons could solely

  1. Ozone observations and a model of marine boundary layer photochemistry during SAGA 3

    NASA Astrophysics Data System (ADS)

    Thompson, A. M.; Johnson, J. E.; Torres, A. L.; Bates, T. S.; Kelly, K. C.; Atlas, E.; Greenberg, J. P.; Donahue, N. M.; Yvon, S. A.; Saltzman, E. S.; Heikes, B. G.; Mosher, B. W.; Shashkov, A. A.; Yegorov, V. I.

    1993-01-01

    , suggesting a largely continental source for these species. However, maxima in isopropyl nitrate and bromoform near the equator (Atlas et al., this issue) as well as for nitric oxide (Torres and Thompson, this issue) may signify photochemical and biological sources of these species.

  2. Ozone observations and a model of marine boundary layer photochemistry during SAGA 3

    SciTech Connect

    Thompson, A.M.; Johnson, J.E.; Bates, T.S.; Kelly, K.C.; Torres, A.L.; Atlas, E.; Greenberg, J.P.; Donahue, N.M.; Yvon, S.A.; Saltzman, E.S.

    1993-09-20

    A major purpose of the third joint Soviet-American Gases and Aerosols (SAGA 3) oceanographic cruise was to examine remote tropical marine O{sub 3} and photochemical cycles in detail. On leg 1, which took place between Hilo, Hawaii, and Pago-Pago, American Samoa, in February and March 1990, shipboard measurements were made of O{sub 3}, CO, CH{sub 4}, nonmethane hydrocarbons (NMHC), NO, dimethyl sulfide (DMS), H{sub 2}S, H{sub 2}O{sub 2}, organic peroxides, and total column O{sub 3}. Postcruise analysis was performed for alkyl nitrates and a set of nonmethane hydrocarbons. A latitudinal gradient in O{sub 3} was observed on SAGA 3, with O{sub 3} north of the intertropical convergence zone (ITCZ) at 15-20 parts per billion by volume (ppbv) and less than 12 ppbv south of the ITCZ but never {le} 3 ppbv as observed on some previous equatorial Pacific cruises. Total column O{sub 3} (230--250 Dobson units (DU)) measured from the Akademik Korolev was within 8% of the corresponding total ozone mapping spectrometer (TOMS) satellite observations and confirmed the equatorial Pacific as a low O{sub 3} region. A one-dimensional photochemical model gives a self-consistent picture of O{sub 3}-NO-CO-hydrocarbon interactions taking place during SAGA 3. At typical equatorial conditions, mean O{sub 3} is 10 ppbv with a 10-15% diurnal variation and maximum near sunrise. Measurements of O{sub 3}, CO, CH{sub 4}, NMHC, and H{sub 2}O constrain model-calculated OH to 9 x 10{sup 5} cm{sup {minus}3} for 10 ppbv O{sub 3} at the equator. The concentrations of alkyl nitrates on SAGA 3 (5-15 pptv total alkyl nitrates) were up to 6 times higher than expected from currently accepted kinetics, suggesting a largely continental source for these species. However, maxima in isopropyl nitrate and bromoform near the equator as well as for nitric oxide may signify photochemical and biological sources of these species. 43 refs., 11 figs., 6 tabs.

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

    NASA Astrophysics Data System (ADS)

    Lennartz, S. T.; Krysztofiak-Tong, G.; Marandino, C. A.; Sinnhuber, B.-M.; Tegtmeier, S.; Ziska, F.; Hossaini, R.; Krüger, K.; Montzka, S. A.; Atlas, E.; Oram, D.; Keber, T.; Bönisch, H.; Quack, B.

    2015-06-01

    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 different air

  4. Modelling marine emissions and atmospheric distributions of halocarbons and dimethyl sulfide: the influence of prescribed water concentration vs. prescribed emissions

    NASA Astrophysics Data System (ADS)

    Lennartz, S. T.; Krysztofiak, G.; Marandino, C. A.; Sinnhuber, B.-M.; Tegtmeier, S.; Ziska, F.; Hossaini, R.; Krüger, K.; Montzka, S. A.; Atlas, E.; Oram, D. E.; Keber, T.; Bönisch, H.; Quack, B.

    2015-10-01

    Marine-produced short-lived trace gases such as dibromomethane (CH2Br2), bromoform (CHBr3), methyliodide (CH3I) and dimethyl sulfide (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 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 (ECHAM5/MESSy Atmospheric Chemistry) 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 the ocean surface and in the 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 very short-lived substances (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

  5. Blood Biomarkers of Late Pregnancy Exposure to Trihalomethanes in Drinking Water and Fetal Growth Measures and Gestational Age in a Chinese Cohort

    PubMed Central

    Cao, Wen-Cheng; Zeng, Qiang; Luo, Yan; Chen, Hai-Xia; Miao, Dong-Yue; Li, Li; Cheng, Ying-Hui; Li, Min; Wang, Fan; You, Ling; Wang, Yi-Xin; Yang, Pan; Lu, Wen-Qing

    2015-01-01

    Background: Previous studies have suggested that elevated exposure to disinfection by-products (DBPs) in drinking water during gestation may result in adverse birth outcomes. However, the findings of these studies remain inconclusive. Objective: The purpose of our study was to examine the association between blood biomarkers of late pregnancy exposure to trihalomethanes (THMs) in drinking water and fetal growth and gestational age. Methods: We recruited 1,184 pregnant women between 2011 and 2013 in Wuhan and Xiaogan City, Hubei, China. Maternal blood THM concentrations, including chloroform (TCM), bromodichloromethane (BDCM), dibromochloromethane (DBCM), and bromoform (TBM), were measured as exposure biomarkers during late pregnancy. We estimated associations with gestational age and fetal growth indicators [birth weight, birth length, and small for gestational age (SGA)]. Results: Total THMs (TTHMs; sum of TCM, BDCM, DBCM, and TBM) were associated with lower mean birth weight (–60.9 g; 95% CI: –116.2, –5.6 for the highest vs. lowest tertile; p for trend = 0.03), and BDCM and DBCM exposures were associated with smaller birth length (e.g., –0.20 cm; 95% CI: –0.37, –0.04 for the highest vs. lowest tertile of DBCM; p for trend = 0.02). SGA was increased in association with the second and third tertiles of TTHMs (OR = 2.91; 95% CI: 1.32, 6.42 and OR = 2.25; 95% CI: 1.01, 5.03; p for trend = 0.08). Conclusions: Our results suggested that elevated maternal THM exposure may adversely affect fetal growth. Citation: Cao WC, Zeng Q, Luo Y, Chen HX, Miao DY, Li L, Cheng YH, Li M, Wang F, You L, Wang YX, Yang P, Lu WQ. 2016. Blood biomarkers of late pregnancy exposure to trihalomethanes in drinking water and fetal growth measures and gestational age in a Chinese cohort. Environ Health Perspect 124:536–541; http://dx.doi.org/10.1289/ehp.1409234 PMID:26340795

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

    NASA Technical Reports Server (NTRS)

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

    2010-01-01

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

  7. Factors affecting the formation of disinfection by-products during chlorination and chloramination of secondary effluent for the production of high quality recycled water.

    PubMed

    Doederer, Katrin; Gernjak, Wolfgang; Weinberg, Howard S; Farré, Maria José

    2014-01-01

    trihalomethanes while the opposite effect was observed for the other targeted DBPs. Temperature was identified as the least influencing parameter compared to pH and reaction time for all DBPs in all the disinfection strategies, except for the formation of chloral hydrate where pH and temperature had a similar significance and bromoform that was similarly affected by temperature and reaction time. Chloramines employed at pH 8.5 reduced the concentration of all studied DBPs compared to pH 5.5. Furthermore, reaction time was the most significant factor for trichloronitromethane, chloroform, trichloroacetonitrile, dichloroacetonitrile and bromochloroacetonitrile formation while pH was the most influencing factor affecting the formation of the remaining DBPs. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. A halocarbon survey from a seagrass dominated subtropical lagoon, Ria Formosa (Portugal): flux pattern and isotopic composition

    NASA Astrophysics Data System (ADS)

    Weinberg, I.; Bahlmann, E.; Eckhardt, T.; Michaelis, W.; Seifert, R.

    2015-03-01

    In this study we report fluxes of chloromethane (CH3Cl), bromomethane (CH3Br), iodomethane (CH3I), and bromoform (CHBr3) from two sampling campaigns (summer and spring) in the seagrass dominated subtropical lagoon Ria Formosa, Portugal. Dynamic flux chamber measurements were performed when seagrass patches were either air-exposed or submerged. Overall, we observed highly variable fluxes from the seagrass meadows and attributed them to diurnal cycles, tidal effects, and the variety of possible sources and sinks in the seagrass meadows. The highest emissions with up to 130 nmol m-2 h-1 for CH3Br were observed during tidal changes, from air exposure to submergence and conversely. Furthermore, during the spring campaign, the emissions of halocarbons were significantly elevated during tidal inundation as compared to air exposure. Accompanying water sampling performed during both campaigns revealed elevated concentrations of CH3Cl and CH3Br, indicating productive sources within the lagoon. Stable carbon isotopes of halocarbons from the air and water phase along with source signatures were used to allocate the distinctive sources and sinks in the lagoon. Results suggest that CH3Cl was rather originating from seagrass meadows and water column than from salt marshes. Aqueous and atmospheric CH3Br was substantially enriched in 13C in comparison to source signatures for seagrass meadows and salt marshes. This suggests a significant contribution from the water phase on the atmospheric CH3Br in the lagoon. A rough global upscaling yields annual productions from seagrass meadows of 2.3-4.5 Gg yr-1, 0.5-1.0 Gg yr-1, 0.6-1.2 Gg yr-1, and 1.9-3.7 Gg yr-1 for CH3Cl, CH3Br, CH3I, and CHBr3 respectively. This suggests a minor contribution from seagrass meadows to the global production of CH3Cl and CH3Br with about 0.1 and 0.7%, respectively. In comparison to the known marine sources for CH3I and CHBr3, seagrass meadows are rather small sources.

  9. Trace Gas Distributions and Correlations Observed In The Southern Ocean Atmosphere During the ORCAS Mission

    NASA Astrophysics Data System (ADS)

    Atlas, E. L.; Schauffler, S.; Donets, V.; Apel, E. C.; Hornbrook, R. S.; Hills, A. J.; Stephens, B. B.; Kort, E. A.; Sweeney, C.; Gierach, M.

    2016-12-01

    The biologically productive waters of the Southern Ocean are potentially a significant source and sink for trace gases that impact atmospheric chemistry and climate. However, relatively little is known about the variations and atmospheric vertical structures of trace gases in this region. During January/February, 2016, we participated in the O2/N2 Ratio and CO2 Airborne Southern Ocean (ORCAS) Study, an airborne mission that included the measurement of a wide range of trace gases. This presentation will focus on a selection of gases measured from the Whole Air Sampler and from an in-situ GC/MS system (TOGA). The gases measured by these instruments included a range of reactive halocarbons produced by marine organisms in the surface ocean (e.g., dimethyl sulfide, bromoform, methyl iodide), produced from marine surface photochemistry (e.g., methyl nitrate), and introduced to the region from long-range transport (e.g., chlorinated solvents, CFCs and HCFCs, non-methane hydrocarbons). Distributions of these gases should reflect the biological productivity of the region, the surface flux rates, and the rates of atmospheric transport and mixing. The concentrations of biogenic trace gases that we measured in the marine boundary layer showed significant regional differences in concentrations and different seasonal changes over the course of the experiment. Vertical profiles of biogenic trace gases could be related to the surface sources, exchange with the free troposphere, and the photochemical lifetime of the different gases. Because of the potential relationship of biogenic trace gases to biological productivity in the surface ocean, the measurements will be compared to distributions of chlorophyll a, as observed remotely from the GV aircraft and from satellites. For trace gases with a large interhemispheric gradient and primarily northern hemisphere source (e.g. mainly anthropogenic sources), atmospheric vertical profiles showed an average increase in mixing ratio with

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

    PubMed

    Zhong, Hui-zhou; Wei, Chao-hai

    2015-04-01

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

  11. Production and air-sea flux of halomethanes in the western subarctic Pacific in relation to phytoplankton pigment concentrations during the iron fertilization experiment (SEEDS II)

    NASA Astrophysics Data System (ADS)

    Hashimoto, Shinya; Toda, Shuji; Suzuki, Koji; Kato, Shungo; Narita, Yasusi; Kurihara, Michiko K.; Akatsuka, Yoko; Oda, Hiroshi; Nagai, Takahiro; Nagao, Ippei; Kudo, Isao; Uematsu, Mitsuo

    2009-12-01

    Iron could play a key role in controlling phytoplankton biomass and productivity in high-nutrient, low-chlorophyll regions. As a part of the iron fertilization experiment carried out in the western subarctic Pacific from July to August 2004 (Subarctic Pacific iron Experiment for Ecosystem Dynamics Study II—SEEDS II), we analysed the concentrations of trace gases in the seawater for 12 d following iron fertilization. The mean concentrations of chlorophyll a in the mixed layer (5-30 m depth) increased from 0.94 to 2.81 μg L -1 for 8 d in the iron patch. The mean concentrations of methyl bromide (CH 3Br; 5-30 m depth) increased from 6.4 to 13.4 pmol L -1 for 11 d; the in-patch concentration increased relative to the out-patch concentration. A linear correlation was observed between the concentrations of 19'-hexanoyloxyfucoxanthin, which is a biomarker of several prymnesiophytes, and CH 3Br in the seawater. After fertilization, the air-sea flux of CH 3Br inside the patch changed from influx to efflux from the ocean. There was no clear evidence for the increase in saturation anomaly of methyl chloride (CH 3Cl) due to iron fertilization. Furthermore, CH 3Cl fluxes did not show a tendency to increase after fertilization of the patch. In contrast to CH 3Br, no change was observed in the concentrations of bromoform (in-patch day 11 and out-patch day 11: 1.7 and 1.7 pmol L -1), dibromomethane (2.1 and 2.2 pmol L -1), and dibromochloromethane (1.0 and 1.2 pmol L -1, respectively). The concentration of isoprene, which is known to have a relationship with chlorophyll a, did not change in this study. The responses of trace gases during SEEDS II differed from the previous findings ( in situ iron enrichment experiment—EisenEx, Southern Ocean iron experiment—SOFeX, and Subarctic Ecosystem Response to Iron Enrichment Study—SERIES). Thus, in order to estimate the concomitant effect of iron fertilization on the climate, it is important to assess the induction of biological

  12. Evaluating Global Emission Inventories of Biogenic Bromocarbons

    NASA Technical Reports Server (NTRS)

    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

  13. Evaluation of the influence of chloroacetic acids on the pharmacokinetics of trihalomethanes in the rat.

    PubMed

    St-Pierre, Annie; Krishnan, Kannan; Tardif, Robert

    2003-12-12

    Chloroacetic acids (monochloroacetic acid [MCA], dichloroacetic acid [DCA], and trichloroacetic acid [TCA]) and trihalomethanes (THMs: chloroform [CHCl(3)], bromodichloromethane [BDCM], dibromochloromethane [DBCM], and bromoform [TBM]) are common by-products of the chlorination of drinking water. The purpose of this study was to evaluate the influence of chloroacetic acids on the pharmacokinetics of trihalomethanes in the male Sprague-Dawley rat. In the first series of studies, groups of 5 animals were given, by intravenous injections, a single dose of 0.125 mmol/kg of one of the four THMs. Additional groups received a binary mixture containing 0.125 mmol/kg of a THM plus 0.125 mmol/kg of a chloroacetic acid. The venous blood concentrations of unchanged THMs were measured by headspace gas chromatography from 5 min to 6 h postadministration. The areas under the blood concentration versus time curves (AUCs) of CHCl(3), BDCM, and DBCM were increased by a factor of 3.5, 1.6, and 2, respectively, by coadministration of TCA. DCA coadministration resulted in an increase in the AUC of DBCM (x2.5) and TBM (x1.3), whereas MCA modified the Cmax (x1.5) and AUC (x1.8) of BDCM and the AUC of DBCM (x2.5). In the second series of experiments, animals received either a single dose of 0.03125 mmol/kg of one of the four THMs, a mixture containing 0.03125 mmol/kg of each of the four THMs (total dose = 0.125 mmol/kg), or a mixture containing 0.03125 mmol/kg of each of the four THMs plus 0.125 mmol/kg of either TCA or DCA. Results indicated that the AUCs of CHCl(3), BDCM, DBCM, and TBM were increased during coadministration compared to single administrations (+2.5-fold). Combined administration of the four THMs with TCA, and not DCA, resulted in an increase of the AUCs of THMs (CHCl(3): x11.7; BDCM, DBCM, and TBM: x3.9) and an increase in the Cmax of CHCl(3) (x1.9). Overall, these results indicate that, at the dose levels tested in this study, TCA alters the blood concentration profiles

  14. Sea Level Rise Enhanced Halocarbon Production in Low-lying Coastal Ecosystem in the Southeastern US

    NASA Astrophysics Data System (ADS)

    Chow, A. T.; Conner, W.; Williams, T.; Song, B.

    2010-12-01

    Saltwater tides bring high concentrations of chloride and bromide inland where it mixes with terrestrial humic substances from surrounding forested watersheds and ferric/ferrous ions from shallow groundwater. With all the essential precursors (i.e., chloride, bromide, and humic substances) and catalysts (ferric/ferrous ions with sunlight), low-lying coastal ecosystems could be a hotspot for halocarbon formation. Fluctuating water levels and salinity due to the tidal cycle alter both redox reactions and water chemistry, influencing the formation and fate of halocarbons. A controlled study was conducted to confirm the abiotic formation of trihalomethanes (THMs) by the photo-Fenton reaction and the effects of the precursors on their formation. Four THM species, including chloroform (CHCl3), bromodichloromethane (CHBrCl2), dibromochloromethane (CHBr2Cl), and bromoform (CHBr3), were examined. Sets of aqueous solutions were prepared using filtered Waccamaw River samples and synthesized NaCl / NaBr, and Fe2(SO4)3 and H2O2 solutions. Solutions were enclosed in quartz tubes and exposed for 7 days to natural sunlight. Although total THM formation increased with DOC concentration, the reactivity of C in forming THM was relatively consistent across DOC concentrations, with an average of 2.6 nmol-THM mmol-C-1. The reactivity in forming THMs through the photo-Fenton reaction was significantly lower than that in chlorinated water. Reactivity generally ranged from 3-20 mmol-THM mol-C-1. The differences in reactivity suggested that greater yield of THMs could be produced under the right reaction condition. In particular, the study showed that bromide increases the reactivity of DOC in forming THMs and enhances the formation of brominated THMs. The bromine substitution factor in the NaCl treatment ranged from 19 to 24% but increased to 43 and 46% when NaBr was added. Results suggest that increased salinity and bromide concentration in saltwater-impacted coastal ecosystems could

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

    PubMed

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

    2010-10-01

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

  16. Delivery of halogenated very short-lived substances from the west Indian Ocean to the stratosphere during the Asian summer monsoon

    NASA Astrophysics Data System (ADS)

    Fiehn, Alina; Quack, Birgit; Hepach, Helmke; Fuhlbrügge, Steffen; Tegtmeier, Susann; Toohey, Matthew; Atlas, Elliot; Krüger, Kirstin

    2017-06-01

    Halogenated very short-lived substances (VSLSs) are naturally produced in the ocean and emitted to the atmosphere. When transported to the stratosphere, these compounds can have a significant influence on the ozone layer and climate. During a research cruise on RV Sonne in the subtropical and tropical west Indian Ocean in July and August 2014, we measured the VSLSs, methyl iodide (CH3I) and for the first time bromoform (CHBr3) and dibromomethane (CH2Br2), in surface seawater and the marine atmosphere to derive their emission strengths. Using the Lagrangian particle dispersion model FLEXPART with ERA-Interim meteorological fields, we calculated the direct contribution of observed VSLS emissions to the stratospheric halogen burden during the Asian summer monsoon. Furthermore, we compare the in situ calculations with the interannual variability of transport from a larger area of the west Indian Ocean surface to the stratosphere for July 2000-2015. We found that the west Indian Ocean is a strong source for CHBr3 (910 pmol m-2 h-1), very strong source for CH2Br2 (930 pmol m-2 h-1), and an average source for CH3I (460 pmol m-2 h-1). The atmospheric transport from the tropical west Indian Ocean surface to the stratosphere experiences two main pathways. On very short timescales, especially relevant for the shortest-lived compound CH3I (3.5 days lifetime), convection above the Indian Ocean lifts oceanic air masses and VSLSs towards the tropopause. On a longer timescale, the Asian summer monsoon circulation transports oceanic VSLSs towards India and the Bay of Bengal, where they are lifted with the monsoon convection and reach stratospheric levels in the southeastern part of the Asian monsoon anticyclone. This transport pathway is more important for the longer-lived brominated compounds (17 and 150 days lifetime for CHBr3 and CH2Br2). The entrainment of CHBr3 and CH3I from the west Indian Ocean to the stratosphere during the Asian summer monsoon is lower than from previous

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

    USGS Publications Warehouse

    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

  18. Occurrence of selected pharmaceutical and non-pharmaceutical compounds, and stable hydrogen and oxygen isotope ratios, in a riverbank filtration study, Platte River, Nebraska, 2001 to 2003, Volume 1

    USGS Publications Warehouse

    Vogel, J.R.; Verstraeten, Ingrid M.; Coplen, T.B.; Furlong, E.T.; Meyer, M.T.; Barber, L.B.

    2005-01-01

    caffeine. Antibiotics were found in some of the wastewater samples and twice in Salt Creek. Antibiotics were not detected in any samples from the Platte River or the well field. Surface-water samples were analyzed for total organic carbon and ground-water samples were analyzed for dissolved organic carbon. Samples from all sites were analyzed for major ions. Herbicides commonly detected in surface, ground, and drinking water included acetachlor, alachlor, atrazine, and metolachlor as well as degradates of these compounds. Most of the samples from wastewater sites were found to contain predominantly acetamide degradates. High concentrations of several organic wastewater indicator compounds were detected at the wastewater sites and in Salt Creek. Several organic wastewater indicator compounds were detected multiple times in samples from the Platte River. Bromoform, a by-product of disinfection in the treatment plant, was found in samples from the finished drinking water. Stable hydrogen isotope ratios show a range in seasonal variation of -73.6 per mill to -38.1 per mill relative to Vienna Standard Mean Ocean Water (VSMOW) reference water and -69.2 per mill to -46.5 per mill for surface water and ground water, respectively. Oxygen isotope ratios for surface-water samples varied between -9.86 per mill and -5.05 per mill. Stable oxygen isotope ratios of ground waters varied between -9.62 per mill and -5.81 per mill.

  19. Sediment transport mechanisms inferred from heavy mineral assemblages on the 2010 Chilean tsunami deposit

    NASA Astrophysics Data System (ADS)

    Cascalho, João; Costa, Pedro; Lario, Javier

    2017-04-01

    Characterization of heavy mineral (HM) assemblages in tsunami deposits has been applied to infer inundation and backwash phases and to establish sediment sources. In ideal conditions and due to their specific density (>2.9 g/cm3), heavy minerals are the most suitable component of a sediment assemblage that can provide information regarding flow competence. Having these features in consideration, sandy tsunamigenic samples from Arauco and Mataquito areas (central Chile) were retrieved after the 27th of February 2010 tsunami that affected the Chilean coastline. Twenty seven samples (a total of 54 thin sections) tsunamigenic and beach samples were prepared to observe HM under the petrographic microscope. After dividing the samples in 4 fractions (<63 µm, 63- 125 µm, 125-500µm and >500 µm), HM were separated using bromoform and two fractions (63- 125 µm and 125-500µm) were individually mounted using Canada balsam resin on glass slides. About 300 heavy minerals per slide were identified and counted. Both assemblages were mainly composed of magnetite, pyrrhotite, amphiboles, pyroxenes, olivine, micas and zircon (this specie particularly abundant in the finer fraction analyzed). In Arauco (Ar), average HM percentages in the 125-500 µm fraction was 17.9% while in Mataquito (Ma) it was 25.7%. In the 63-125 µm fraction HM average percentages were 36.9% and 56.1%, for Ar and Ma respectively. In the 125-500 µm fraction the percentage of magnetic minerals (the densest of the denser HM) correspond to 13.2% in Ar and 2.7% in Ma. While in the finer fraction these percentages are of 0.24% and 0.1% In Ar it was possible to perceive that the highest concentration in HM and magnetic minerals was observed in the NE sector (Llico) of the embayment, where the highest run-up was observed. In this specific sector an inland decrease of HM and magnetic minerals was detected along a 300m profile, with HM percentages varying from 27% to 9% and magnetic minerals from 16% to 5%, thus

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

    PubMed Central

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

    2017-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2000-06-01

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

  2. Chloroform in the hydrologic system--sources, transport, fate, occurrence, and effects on human health and aquatic organisms

    USGS Publications Warehouse

    Ivahnenko, Tamara; Barbash, Jack E.

    2004-01-01

    Chloroform is one of the volatile organic compounds (VOCs) detected most frequently in both ground and surface water. Because it is also one of the four trihalomethanes (THMs) produced in the highest concentrations during the chlorination of drinking water and wastewater, the frequent detection of this compound in ground and surface water of the United States is presumed to be caused primarily by the input of chlorinated water to the hydrologic system. Although anthropogenic sources of the compound are substantial, they are currently estimated to constitute only 10 percent of the total global input to the hydrologic system. Natural sources of the compound include volcanic gases, biomass burning, marine algae, and soil microorganisms. Under most conditions (except in the presence of unusually high bromide concentrations), chloroform is the THM produced in the highest concentrations during chlorination. Furthermore, in most cases where more than one THM is produced from chlorination, the relative concentrations among the different compounds usually decrease with increasing bromination (chloroform > dichlorobromomethane > chlorodibromomethane > bromoform). This phenomenon is presumed to be responsible for the common observation that when more than one THM is detected during investigations of the occurrence of these compounds in the hydrologic system, this same trend is typically observed among their relative concentrations or, for a uniform reporting limit, their relative frequencies of detection. This pattern could provide a valuable means for distinguishing between chlorinated water and other potential sources of chloroform in the environment. Chloroform has been widely detected in national, regional, and local studies of VOCs in ground, surface, source, and drinking waters. Total THM (TTHM) concentrations of the compound, however, were typically less than the Maximum Contaminant Level (MCL) of 80 ?g/L (micrograms per liter) established by the U.S. Environmental

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

    SciTech Connect

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

    2012-01-01

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

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

    PubMed

    Mithoo-Singh, Paramjeet Kaur; Keng, Fiona S-L; Phang, Siew-Moi; Leedham Elvidge, Emma C; Sturges, William T; Malin, Gill; Abd Rahman, Noorsaadah

    2017-01-01

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

  5. Photochemical production of CH3Br: Possibly the unknown source

    NASA Astrophysics Data System (ADS)

    Wingenter, O. W.; Gorham, K. A.; Blake, N. J.; Meinardi, S.; Blake, D. R.; Rowland, F. S.

    2009-12-01

    fractions of the initial reactions. During ARCTAS we also observed spikes of bromoform (CHBr3) associated with ODEs. This gas has a marine source. Some spikes occurred without a corresponding ODE. Our data support the hypothesis that CHBr3 may initiate “bromine explosions". We have shown previously that CH3Br is produced in snow and is known to have a marine source. These two sources cannot be ruled out entirely as explanations for our observations. However, CH3Br production in snow at Summit does not appear to be strong enough to support our aircraft observations. Also at Summit, CHBr3 does not correlate with benzene/ethyne ratios, seeming to rule out the influence of a marine source. Reactions involving mercury (Hg) or another metal may also be producing CH3Br. During ARCTAS, the Hg depletion episodes corresponded well with the ODEs and elevated CH3Br. If our photochemical hypothesis is correct and background BrO is in the 1-2 pptv range, then the photochemical production of CH3Br would provide much of the missing source of CH3Br required to balance its budget and satisfies the requirement that the missing source be nearly equally distributed in both hemispheres.

  6. 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

    NASA Astrophysics Data System (ADS)

    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

  7. Factorial analysis of the trihalomethane formation in the reaction of colloidal, hydrophobic, and transphilic fractions of DOM with free chlorine.

    PubMed

    Platikanov, Stefan; Tauler, Roma; Rodrigues, Pedro M S M; Antunes, Maria Cristina G; Pereira, Dilson; Esteves da Silva, Joaquim C G

    2010-09-01

    This study focuses on the factors that affect trihalomethane (THMs) formation when dissolved organic matter (DOM) fractions (colloidal, hydrophobic, and transphilic fractions) in aqueous solutions were disinfected with chlorine. DOM fractions were isolated and fractionated from filtered lake water and were characterized by elemental analysis. The investigation involved a screening Placket-Burman factorial analysis design of five factors (DOM concentration, chlorine dose, temperature, pH, and bromide concentration) and a Box-Behnken design for a detailed assessment of the three most important factor effects (DOM concentration, chlorine dose, and temperature). The results showed that colloidal fraction has a relatively low contribution to THM formation; transphilic fraction was responsible for about 50% of the chloroform generation, and the hydrophobic fraction was the most important to the brominated THM formation. When colloidal and hydrophobic fraction solutions were disinfected, the most significant factors were the following: higher DOM fraction concentration led to higher THM concentration, an increase of pH corresponded to higher concentration levels of chloroform and reduced bromoform, higher levels of chlorine dose and temperature produced a rise in the total THM formation, especially of the chlorinated THMs; higher bromide concentration generates higher concentrations of brominated THMs. Moreover, linear models were implemented and response surface plots were obtained for the four THM concentrations and their total sum in the disinfection solution as a function of the DOM concentration, chlorine dose, and temperature. Overall, results indicated that THM formation models were very complex due to individual factor effects and significant interactions among the factors. In order to reduce the concentration of THMs in drinking water, DOM concentrations must be reduced in the water prior to the disinfection. Fractionation of DOM, together with an elemental

  8. Development of an analytical technique for the detection of alteration minerals formed in bentonite by reaction with alkaline solutions

    NASA Astrophysics Data System (ADS)

    Sakamoto, H.; Shibata, M.; Owada, H.; Kaneko, M.; Kuno, Y.; Asano, H.

    A multibarrier system consisting of cement-based backfill, structures and support materials, and a bentonite-based buffer material has been studied for the TRU waste disposal concept being developed in Japan, the aim being to restrict the migration of radionuclides. Concern regarding bentonite-based materials in this disposal environment relates to long-term alteration under hyper-alkaline conditions due to the presence of cementitious materials. In tests simulating the interaction between bentonite and cement, formation of secondary minerals due to alteration reactions under the conditions expected for geological disposal of TRU waste (equilibrated water with cement at low liquid/solid ratio) has not been observed, although alteration was observed under extremely hyper-alkaline conditions with high temperatures. This was considered to be due to the fact that analysis of C-S-H gel formed at the interface as a secondary mineral was difficult using XRD, because of its low crystallinity and low content. This paper describes an analytical technique for the characterization of C-S-H gel using a heavy liquid separation method which separates C-S-H gel from Kunigel V1 bentonite (bentonite produced in Japan) based on the difference in specific gravity between the crystalline minerals constituting Kunigel V1 and the secondary C-S-H gel. For development of C-S-H gel separation methods, simulated alteration samples were prepared by mixing 990 mg of unaltered Kunigel V1 and 10 mg of C-S-H gel synthesized using pure chemicals at a ratio of Ca/Si = 1.2. The simulated alteration samples were dispersed in bromoform-methanol mixtures with specific gravities ranging from 2.00 to 2.57 g/cm 3 and subjected to centrifuge separation to recover the light density fraction. Subsequent XRD analysis to identify the minerals was complemented by dissolution in 0.6 N hydrochloric acid to measure the Ca and Si contents. The primary peak (2 θ = 29.4°, Cu Kα) and secondary peaks (2 θ = 32.1

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

    NASA Astrophysics Data System (ADS)

    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

  10. 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

    USGS Publications Warehouse

    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

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

    NASA Astrophysics Data System (ADS)

    Aschmann, J.; Sinnhuber, B.-M.

    2013-02-01

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

  12. Assessing the vulnerability of public-supply wells to contamination—Edwards aquifer near San Antonio, Texas

    USGS Publications Warehouse

    Jagucki, Martha L.; Musgrove, MaryLynn; Lindgren, Richard J.; Fahlquist, Lynne; Eberts, Sandra M.

    2011-01-01

    This fact sheet highlights findings from the vulnerability study of a public-supply well field in San Antonio, Texas. The well field consists of six production wells that tap the Edwards aquifer. Typically, one or two wells are pumped at a time, yielding an average total of 20-21 million gallons per day. Water samples were collected from public-supply wells in the well field and from monitoring wells installed along general directions of flow to the well field. Samples from the well field contained some constituents of concern for drinking-water quality, including nitrate; the pesticide compounds atrazine, deethylatrazine, and simazine; and the volatile organic compounds tetrachloroethene (also called perchloroethene, or PCE), chloroform, bromoform, and dibromochloromethane. These constituents were detected in untreated water at concentrations much less than established drinking-water standards, where such standards exist. Overall, the study findings point to four primary factors that affect the movement and fate of contaminants and the vulnerability of the public-supply well field in San Antonio, Texas: (1) groundwater age (how long ago water entered, or recharged, the aquifer), (2) fast pathways for flow of groundwater through features formed or enlarged by dissolution of bedrock, (3) recharge characteristics of the aquifer, and (4) natural geochemical processes within the aquifer. A computer-model simulation of groundwater flow and transport was used to estimate the traveltime (or age) of water particles entering public-supply well W4 in the well field. Modeled findings show that almost half of the water reaching the public-supply well is less than 2 years old. Such a large percentage of very young water indicates that (1) contaminants entering the aquifer may be transported rapidly to the well, (2) there is limited time for chemical reactions to occur in the aquifer that may attenuate contaminants, and (3) should recharge water become contaminated with

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

    NASA Astrophysics Data System (ADS)

    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. Status and understanding of groundwater quality in the central-eastside San Joaquin Basin, 2006: California GAMA Priority Basin Project

    USGS Publications Warehouse

    Landon, Matthew K.; Belitz, Kenneth; Jurgens, Bryant C.; Kulongoski, Justin T.; Johnson, Tyler D.

    2010-01-01

    were detected frequently (detected in greater than 10 percent of samples): the trihalomethanes chloroform, bromoform, bromodichloromethane, and dibromochloromethane; the solvent PCE; the herbicides atrazine, simazine, and metolachlor, and special-interest constituent perchlorate.An assessment of understanding of the groundwater quality included sampling of understanding wells, some of which were perforated in shallower or deeper portions of the aquifer system than the primary aquifer, and analysis of correlations of groundwater quality with land use, depth, age classification, and other potential explanatory factors.The understanding assessment indicated that the concentrations of many constituents were related to depth and groundwater age. However, concentrations of individual constituents or constituent classes also were sometimes related to geochemical conditions, lateral position in the flow system, or land use.High and moderate relative-concentrations of uranium, nitrate, and total dissolved solids (TDS) were detected in some wells where the tops of perforations are within the upper 200 feet of the aquifer system. In wells with the depth to the top of perforations below this depth, concentrations were low. A similar pattern occurred for the sum of herbicide concentrations. These vertical water-chemistry patterns are consistent with the hydrogeologic setting, in which return flows from agricultural and urban land use are the major source of recharge, and withdrawals for irrigation and urban supply are the major source of discharge, resulting in substantial vertical components of groundwater flow.The decrease in concentrations of many constituents with depth reflects in part that groundwater gets older with depth. Tritium, helium-isotopes, and carbon-14 data were used to classify the predominant age of groundwater samples into three categories: modern (water that has entered the aquifer in the last 50 years), pre-modern (water that entered the aquifer more than 50