WP6 Emerging Pollutants|
Wednesday, 16 November 2005: 8:00 AM - 6:30 PM in Exhibit Hall
WP067 (BAC-1117-643192) Spatial and temporal distributions of brominated flame retardants (BFRs) in wet-only precipitation collected in the Great Lakes Basin.
Start time: 8:00 AM
Backus, S.1, Archer, M.1, Harrison, B.1, Williams, D.1, Muir, D.C.G. 1, Alaee, M.1, 1 Environment Canada, Burlington, ON, Canada
Spatial and temporal distributions of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in wet-only precipitation collected at nine IADN sites in the Great Lakes Basin were examined. A total of 118 samples were collected and analyzed for fifteen PBDE congeners (BDE-17, -28/33, -47, -66, -100, -99, -85, -154, -153, -138, -183, -190, and -209) and HBCD. The concentrations of BDE-209 and PBDE (defined as the sum of all targeted PBDE congeners except for BDE-209) ranged from non-detect (n.d.) to 44 ng/L and from 0.021 to 4.2 ng/L respectively. Congener compositions were dominated by BDE-209 followed by BDE-99, -47, -183, -100, -153 and -154. Average annual wet deposition of BDE-209 and PBDE for the nine sites ranged from 2.8 to 5.3 ng/m2/day and from 0.39 to 1.3 ng/m2/day respectively. The concentration of HBCD ranged from n.d. to 35 ng/L and annual wet deposition ranged from 0.36 to 10 ng/m2/day. Annual variations were observed with peaks in the winter, which are likely the result of the increased scavenging efficiency of snow compared to rain and higher concentrations in the particle phase during the winter. There is no consistent pattern in the spatial distribution of BFRs in the basin.
WP068 (WAN-1117-231323) Assessment of Human Exposure to Microcystin–LR.
Start time: 8:00 AM
Wang, P 1, Billam, M1, Tang, L1, Cai, Q1, Xu, M2, Jiao, J2, Lin, Y2, Wang, J-S1, 1 Department of Toxicology & The Institute of Environmental and Human Health, Texas Tech University, Lubbock, Texas, USA2 Wuxi City Center for Disease Control, Wuxi, Jiangsu, China
Microcystin–LR (MCLR) is a common hepatotoxic cyanotoxin frequently found in fresh water sources. Its ecotoxic effects were widely reported. MCLR is extremely stable in natural waters, which makes it an emerging pollutant for human exposure through drinking water or recreation activities. To assess the exposure level of human to MCLR, water samples were collected repeatedly in August 2004 from 5 sites along the flowing line of a water treatment plant in Nanquan, located at south of Wuxi City, Jiangsu, China, where heavily cyanobacterial contamination was reported for years. MCLR in water samples was determined with HPLC method. Higher levels of MCLR were found in water samples collected from different sampling sites: averaged 7.13±1.21ppb in sample from nearby the pumping site in Taihu Lake; averaged 5.24±1.66 ppb in samples from the reservoir of the water treatment plant; averaged 1.53±0.14 ppb in water samples collected after the precipitation and filtration in the plant, averaged 1.87±1.40 ppb in water samples collected at output tube post chlorination in the plant, and averaged 2.33±1.92 ppb in tubes distributed water to each household. In addition, averaged 23.90±30.56 ppb MCLR were found in water samples collected from Sanshan, a local water quality monitoring site, and averaged 7.01±4.75 ppb MCLR in water samples from Yutang, a site where fishermen resided. All sampling sites had MCLR levels greater than WHO guideline limit (1ppb). Based on the averaged MCLR level in household water and the daily water consumption recorded from 60 local residents (Male: 3397.02±1391.72 ml/day; Female: 2505.73±801.75 ml/day), a daily exposure to MCLR was estimated: Male, 7.92 g/day and Female, 5.84 g/day. These data provide useful information for future risk assessment, especially for high MCLR contamination sites in the world. (Supported by the research grant, CA94683, from NCI/NIH).
WP069 (SCH-1117-741727) Evaluation of the removal of estrogens through the coagulation process.
Start time: 8:00 AM
Schenck, K1, Dugan, N1, Williams, D1, Merriman, B1, Rosenblum, L2, Krishnan, E2, Wiese, T3, 1 U.S. Environmental Protection Agency, Cincinnati, OH, USA2 Shaw Environmental and Infrastruture, Inc., Cincinnati, OH, USA3 Xavier University of Louisiana, New Orleans, LA, USA
A number of estrogenic compounds have been shown to be present in surface waters in the U.S. These compounds have the potential to act as potent endocrine disrupting chemicals (EDCs), leading to a growing concern over the possible presence of EDCs in finished drinking waters. Consequently, it is prudent to explore if strategies already employed to manage other drinking water risks can also control risks associated with EDCs. Coagulation is a unit process used by the majority of surface water treatment plants in the U.S. Adsorbents such as powdered activated carbon (PAC) are commonly added during coagulation to enhance the removal of organic contaminants. Bench-scale studies (jar tests) were conducted to evaluate the ability of coagulation, with and without PAC, to remove three estrogens (estradiol, ethynylestradiol, and estriol) from Ohio River water. The estrogen to be evaluated was added to the river water prior to treatment with either aluminum sulfate (alum) or ferric chloride, with and without PAC. In order to simulate full-scale treatment practice, the coagulants were added at the lowest concentration necessary to achieve a settled turbidity between 1 and 5 nephelometric turbidity units (NTU). Control jars (no treatment) were sampled at the beginning and the end of treatment and verified the absence of biodegradation during the time course of the coagulation study. Removal of the estrogens was evaluated by comparing the concentrations in the control and treatment jars. The estrogen concentrations were determined analytically using solid phase extraction followed by liquid chromatography/mass spectroscopy. None of the estrogens were removed following coagulation with either alum or ferric chloride. The addition of PAC resulted in removals ranging from approximately 20 to 80 percent. Variations in observed removals were due either to variations in water quality, or variations in the molecular weight, charge and hydrophobicity of the tested estrogens. Some of the samples were also assayed in the MVLN assay, an estrogen-responsive reporter gene assay. The results of the MVLN assay were consistent with the analytical results for both the treated and untreated samples, indicating that removal of the estrogens was not due to chemical transformation into an alternate estrogenic compound.
WP070 (BAC-1117-722482) Determination of nine sulfonamides in natural waters by high performance liquid chromatography/atmospheric pressure photoionization tandem mass spectrometry.
Start time: 8:00 AM
Backus, S.1, Struger, J.1, Bennie, D.1, Palabrica, V.1, Hewitt, M.1, 1 Environment Canada, Burlington, ON, Canada
A robust and sensitive, high performance liquid chromatography/atmospheric pressure photoionization tandem mass spectrometry (HPLC/APPI) method for the determination of residues of sulfonamides in natural waters is described. The sulfonamides are extracted from filtered water using graphitized non-porous carbon. Detection of the analytes was achieved by positive photoionization (APPI) followed by multiple reaction monitoring. For each sulfonamide the collisional decomposition of the protonated molecule to a common, abundant fragment ion was monitored. The method has been validated for sulfisoxazole, sulfathiazole, sulfapyridine, sulfamethoxazole, sulfamethiazole, sulfamethazine, sulfachloropyridazine, sulfacetamide, and sulfamethoxypyridazine. The method was applied to the determination of sulfonamides in natural waters collected in a number of watersheds in southern Ontario. Preliminary data show that six of the sulfonamides were detected regularly above the analytical detection limit. The procedure provides a rapid, reliable and sensitive method for the determination of residues of sulfonamides in natural waters.
WP071 (REI-1117-765343) Determination of Polycyclic Musks Compounds in Selected Consumer Products.
Start time: 8:00 AM
Reiner, J1, 2, Kannan, K1, 2, 1 Wadsworth Center, New York State Department of Health, Albany, NY, USA2 SUNY at Albany, Albany, NY, USA
Studies from Europe have reported the widespread occurrence of polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronapthalene (AHTN) in wastewater influent and effluent, as well as surface waters. In recent studies the metabolite of HHCB, HHCB-lactone, was detected in wastewater and surface waters. The major sources for HHCB and AHTN to wastewater are thought to be from consumer products such as shampoos, deodorants, laundry detergents, and surface cleaners. As a consequence of putting HHCB and AHTN in many consumer products is that users are constantly exposed to these compounds and these compounds have been shown to bioaccumulate in fish and other aquatic organisms. In this study, we measured concentrations of HHCB, AHTN, and HHCB-lactone from a variety of consumer products. Concentrations ranged from <5 ng/g to over 2000 g/g, <5 ng/g to 400 g/g, and <5 ng/g to 100 g/g, for HHCB, AHTN, and HHCB-lactone, respectively. Highest concentrations were found in deodorants and perfumes. The results suggest a variety of consumer items that are sources of exposure to these compounds, which include many products used on a daily basis.
WP072 (CON-1117-763143) Uptake of perchlorate by garden crops in perchlorate-impacted soil: Implications for risk assessment.
Start time: 8:00 AM
Conder, J1, Haroun, L2, Scofield, R2, 1 ENVIRON International Corporation, Irvine, CA, USA2 ENVIRON International Corporation, Emeryville, CA, USA
Nearly all perchlorate uptake studies in garden crops have been conducted with plants grown in soil or water receiving multiple additions of perchlorate via irrigation with water containing perchlorate. Bioconcentration factor (BCF) values, based on concentration in plant tissue divided by concentration in water, are as high as 10,000. These values may be inappropriate for prediction of perchlorate uptake from perchlorate-impacted soils that do not receive additional inputs of perchlorate, as BCF values based on soil concentrations for inedible agricultural plants and native plants are 1-2 orders of magnitude lower. The differences in water-based and soil-based BCF values may be due to a number of factors, including lower availability in soils (especially at soil concentrations of less than 2-5 ppm) and the possible depletion of available perchlorate by plants from soil. For garden crops, the addition of organic matter amendments and fertilizer may also inhibit uptake and/or increase biodegradation, resulting in lower observed soil-based BCF values. BCF values vary by orders of magnitude among plant tissues, as perchlorate is accumulated in tissues that have high water permeation due to evapotranspirational flux. In general, differences in tissue-specific BCF values can be an order of magnitude or more, with Leaf BCF > Fruit BCF > Root BCF. Risk-based cleanup levels in soil can be below 40 ppb, the reporting limit using the standard analytical method, based on assumptions that water-based BCF values represent perchlorate uptake and consumers of garden produce consume only leaf produce. Risk-based cleanup levels for perchlorate in soil should be calculated using soil-based BCF values and dietary assumptions that consider consumption of representative dietary portions of leaf, fruit, and root produce.
WP073 (KAN-1117-747440) Polycyclic musk compounds in higher trophic level aquatic organisms and humans from the United States.
Start time: 8:00 AM
Kannan, K.1, Reiner, J.1, Yun, S.1, Perrotta, E.1, Tao, L.1, Johnson, B.1, Rodan, B.2, 1 Wadsworth Center, New York State Department of Health, Empire State Plaza, PO Box 509, Albany, NY 12201-0509, USA2 US EPA, Washington, DC, USA
Polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta [g]-2-benzopyran (HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN), are used as fragrance ingredients in numerous consumer products such as cleaning agents and personal care products. Studies have reported the widespread occurrence of these musks in surface waters and fish from western European countries. Nevertheless, little is known about their accumulation in humans and wildlife in the United States. In this study, we measured concentrations of HHCB and AHTN in human adipose fat collected from New York City. Furthermore, tissues from marine mammals, water birds, and fish collected from US waters were analyzed to determine the concentrations of HHCB and AHTN. Concentrations of HHCB and AHTN in human adipose fat samples ranged from 12 to 798 and from <5 to 134 ng/g, on a lipid weight basis, respectively. A significant correlation existed between the concentrations of HHCB and AHTN in human adipose fat. Concentrations of HHCB and AHTN were not positively correlated with age or gender of the donors. HHCB was found in tissues of several wildlife species, but not in the livers of polar bear from the Alaskan Arctic. Among wildlife species analyzed, spinner and bottlenose dolphins collected from Florida coastal waters contained measurable concentrations of HHCB.
WP074 (MAX-1117-816546) Distribution of Irgarol 1051 and M1 in biotic and abiotic samples around the Florida coast.
Start time: 8:00 AM
Maxey, C1, Zamora, I2, Gardinali, P1, 3, 1 Department of Chemistry, Florida International University, Miami, Florida, USA2 Department of Environmental Sciences, Florida International University, Miami, Florida, USA3 Southeastern Environmental Research Center, Florida International University, Miami, Florida, USA
Antifouling booster biocides used in copper based marine paints are becoming a topic of increasing environmental importance due to the recent 2003 ban on tributyltin compounds. Surface water samples were collected during 2002 through early 2005 from large marinas (greater than 80 wet slips) along the majority of the Florida coast and the Florida Keys to determine the distribution of Irgarol 1051 and M1, its major degradation product. Beginning in 2004, seagrass and sediment samples were collected in conjunction with the surface water from Key Largo Harbor. In addition to the marina studies, surface water samples were taken from various coral reef habitats around the Florida Keys. Two study areas (Key Largo Harbor and Biscayne Bay) were frequently visited to determine if there were any temporal trends of the analytes. Concentrations of the target compounds ranged from non-detect (less than 1 ppt) to 1238 ppt for Irgarol and 428 ppt for M1. Concentrations in surface waters from marinas were considerably higher (average of 134.9 ± 21.0 ppt for Irgarol and 59.96 ± 10.65 ppt for M1) than in open water reef sites (all of which were non-detects). Seagrass samples had an average concentration of 8.680 ± 1.367 ppt for Irgarol, while M1 concentrations were below the method detection limits. Bioconcentration factors of Irgarol for seagrasses were calculated to be an average of 897 ± 183. Concentrations of analytes in sediments were minimal in all samples (less than 10 ppt). Although Irgarol is present 75% of the samples (269/359), the concentrations are less than those found along the coast of Europe and Asia.
WP075 (LET-1117-814447) Brominated flame retardants and methoxylated and hydroxylated PBDEs in two Norwegian arctic top-predators: glaucous gulls and polar bears.
Start time: 8:00 AM
Verreault, J.1, 2, Gabrielsen, G.1, Chu, S.3, Muir, D.4, Andersen, M.1, Letcher, R.2, 3, 1 Norwegian Polar Institute, Tromso, Norway2 Environment Canada, Canadian Wildlife Service, National Wildlife Research Centre, Ottawa, Ontario, Canada3 University of Windsor, Great Lakes Institute for Environmental Research, Windsor, Ontario, Canada4 Environment Canada, Canada Centre for Inland Waters, National Water Research Institute, Burlington, Ontario, Canada
Brominated flame retardants (BFRs) have been subject of a particular environmental focus in the Arctic. The present study investigated the congener patterns and levels of total- hexabromocyclododecane (HBCD), polybrominated biphenyls (PBBs), polybrominated diphenyl ethers (PBDEs), as well as structural analogues to PBDEs, i.e. the methoxylated (MeO) and hydroxylated (OH) PBDEs, in plasma samples of glaucous gulls (Larus hyperboreus) and polar bears (Ursus maritimus) from the Norwegian Arctic. The analyses revealed the presence of total-HBCD and BB101 in glaucous gull samples, but generally found infrequently (14% of samples) in samples at low or non-detectable in polar bears. Sum concentrations of 12 PBDE congeners (12PBDE) monitored in glaucous gulls (range: 8.23 - 67.5 ng/g wet wt) largely surpassed those of polar bears (range: 2.65 - 9.72 ng/g wet wt). Two higher brominated PBDEs, BDE183 and BDE209, were detected at low levels, and thus are bioaccumulating to a limited degree in glaucous gulls. In polar bear plasma, BDE183 was below the detection limit for all animals, and BDE209 was only detected in 7% of the samples. Of the 15 MeO-PBDEs analyzed, 3-MeO-BDE47 was consistently dominant in glaucous gulls and polar bears, followed by 4'-MeO-BDE49 and 6-MeO-BDE47. The 3-OH-BDE47, 4'-OH-BDE49 and 6-OH-BDE47 congeners were also detected in glaucous gulls, although in polar bears 4'-OH-BDE49 was the only congener quantifiable in 13% of the samples. The presence of MeO- and OH-PBDEs in plasma of both species suggests possible dietary uptake from naturally-occurring sources (e.g., marine sponges and green algae), but also metabolically-derived biotransformation of PBDEs such as BDE47 could be a contributing factor. Our findings suggest that there are dissimilar biochemical mechanisms involved in PCB and PBDE metabolism and accumulation/elimination, and/or OH-PBDE accumulation and retention in Norwegian glaucous gulls and polar bears.
WP076 (BEN-1117-831129) HPLC-ToF-MS based detection of polymers and polyethoxylated surfactants.
Start time: 8:00 AM
Benotti, Mark1, Casey, Andrew1, Brownawell, Bruce1, 1 Stony Brook University, Stony Brook, NY, USA
Investigation of emerging wastewater contaminants has been primarily focused on targeted suites of chemicals that are often pharmacologically active. However, the occurrence in wastewaters and the environment of many high volume polymers and selected surfactants remain relatively unexplored. Such compounds find widespread uses in foods, personal care products, and industrial applications. The high concentrations and water solubility, and inherent stability of some polymers make them attractive candidates for use as wastewater tracers in receiving waters. Due to full spectral sensitivity, accurate mass estimate capability, and moderately high mass resolution that allows for detection of multiply charged species, liquid chromatography, coupled with time-of-flight mass spectrometry (LC-ToF-MS) offers several advantages for detecting water-soluble polymers and homologous series of surfactants under 10,000Da. To illustrate some general approaches that may prove useful for polymer identification, we present here a novel application of LC-ToF-MS for the detection of over 20 homologous series of compounds containing polyoxyethylene and/or polyoxypropylene moieties. Mass chromatograms were obtained using electrospray ionization in positive ion mode. Several of these homologous series can be identified from three-dimensional visualizations of the full spectral mass chromatograms; homologous series are often seen as the dominant ions in most samples and elute 44 or 58Da apart. With accurate mass estimation, we have also tentatively identified for the first several homologous series, including series of polyethoxylated sorbitan ester derivatives (major constituents of TweenTM surfactants). Putative structures of other PEG derivatives await further assessment and confirmation with standards. The application of LC-ToF-MS for the detection of other classes of water-soluble polymers will be also be considered.
WP077 (GOU-1117-830910) Emissions of volatile organic compounds from brominated flame retardant oligomers.
Start time: 8:00 AM
Gouteux, Bruno1, Alaee, Mehran1, Mabury, Scott2, Muir, Derek1, 1 National Water Research Institute Environment Canada, Burlington, On, Canada2 Dept of Chemistry University of Toronto, Toronto, On, Canada
Brominated flame retardants (BFR) oligomers are predicted to gain increasing market shares in the next future due mainly to their technical advantages such as heat-resistance or processing flexibility. From an environmental perspective, BFR oligomers are not likely to be released out of products like additive lower molecular weight BFR monomers since their larger structure will become more entangled in the final material. However, low molecular weight residuals, which can be monomers, by products, and/or impurities may be present in commercial BFR oligomers. Degradation products may also be formed during the complete life cycle of BFR oligomer. These compounds may have a high potential for blooming, especially under thermal stress. An experimental approach was developed to investigate this possibility for PBS-64, a brominated polystyrene oligomer; PPB-BA, a poly(pentabromobenzyl acrylate) oligomer, and BC-58, a phenoxy-terminated carbonate oligomer of tetrabromobisphenol A. BFR oligomers were heated up from ambient temperature to 100 °C in a glass flask under an inert atmosphere. The glass flask was then cooled down and rinsed with dichloromethane to collect organic compounds released by BFR oligomers. Several brominated compounds were shown to be present in sample extracts by monitoring bromide ions (m/z=79+81) using mass spectrometry in electron capture negative- ionization mode. To identify these unknown compounds, full-scan mass spectra using mass spectrometry in electron ionization mode were obtained and compared to reference mass spectra found either in the NIST MS library or in literature. For example, among the identified brominated organic compounds, di and tribromostyrene monomers were shown to be released from the PBS-64 oligomer.
WP078 (CHE-1117-830803) Investigating the fate and persistence of residual Chemical Warfare Agent in soil.
Start time: 8:00 AM
Checkai, Ronald1, Haley, Mark1, Simini, Michael1, Phillips, Carlton1, Crouse, Charles2, Matson, Kathy 2, 1 U.S. Army Edgewood Chemical Biological Center, Aberdeen Proving Ground, Maryland, USA2 Geo-Centers, Inc., Aberdeen Proving Ground, Maryland, USA
Why all clear following a terrorist chemical attack may mean future danger: Surface-controlled reactions affecting hydrolysis of organic compounds in the environment can predominate over bulk solution hydrolysis, especially in soil environments. Unpredicted residual levels of chemical warfare agents (CWA) at threat levels in the field necessitated development of new methods for investigating the fate of CWA delivered onto soil. Design and fabrication of Soil System Units now allows determination of the fate of CWA in soil, as well as investigation of the soil chemical and physical characteristics affecting the persistence of threat from continuing presence of CWA in soil, under conditions that represent those in the field. Initial results show that the Soil System Unit approach is highly effective for investigating the fate of CWA in the soil environment. Using the Soil System Unit approach we were able to replicate and investigate under controlled laboratory conditions residual levels of the nerve agent Soman (GD) in soil, such as those that might occur in the field from terrorist or wartime activities. Results of our initial experiments showed that persistence of GD in soil can be expected for days following contamination. Furthermore, we established that life threatening atmospheric levels of GD may be expected to successively reoccur in response to increasing moisture in soils contaminated with GD; this result had not been previously documented.