Keith Maruya - Academia.edu (original) (raw)

Papers by Keith Maruya

Marine Pollution Bulletin, 2011

To investigate the potential for enantioselective transformation and accumulation, the enantiomer... more To investigate the potential for enantioselective transformation and accumulation, the enantiomer distributions of seven polychlorinated biphenyl (PCB) atropisomers were measured in the sediment and biota from a sub-tropical estuary heavily contaminated with Aroclor 1268, a technical mixture of highly chlorinated PCB congeners. Enantiomer fractions (EFs) of PCBs 91, 95, 136, 149, 174, 176, and 183 in marsh sediment, invertebrate, forage

Environmental Science & Technology, 2001

Although reports of nonracemic proportions of chiral organochlorine pollutants in the environment... more Although reports of nonracemic proportions of chiral organochlorine pollutants in the environment are widespread, the interpretation of such data is not well developed. Using GC/MS and a chiral stationary phase consisting of 25% tert-butyldimethylsilylated beta-cyclodextrin in PS086 (beta-BSCD), we followed the change in the enantiomeric signature of 2-exo,3-endo,6-exo,8,9,10-hexachlorobornane (B6-923) in naturally contaminated fish maintained under toxaphene-free conditions. Whereas the enantiomeric ratio (ER) of B6-923 was near racemic at the start of the elimination experiment, it had increased severalfold by the end of 60 d. On the basis of first-order kinetics, one enantiomer of B6-923 was eliminated twice as fast as its mirror image, resulting in half-lives of 7 and 13 d, respectively. Enantioselective elimination by our test fish (Fundulus sp.) strongly suggests active biotransformation of B6-923; however, bioprocessing throughput estimates suggest a very low in situ rate of natural attenuation. These results confirm that the relatively constant ERs observed for chiral organochlorines in a given species are the result of competing processes, e.g., uptake vs elimination. Our experiments also further illustrate the utility of enantioselective analysis in characterizing the biotransformation of persistent organochlorine pollutants.

Environmental Science & Technology, 2005

Recent advances in enantioselective separation techniques have enabled scientists to investigate ... more Recent advances in enantioselective separation techniques have enabled scientists to investigate environmental fate processes of chiral pollutants. In this study, congenerand enantiomer-specific toxaphene residues were monitored in captive, naturally contaminated fish (Fundulus heteroclitus) to characterize the effect of temperature and compound structure on the enantioselectivity of the elimination process. A previous study performed under warm water conditions (T mean ) 25°C) demonstrated relatively rapid (t 1/2 ≈ 7-14 d) and enantioselective elimination of the reductive dechlorination metabolites 2-exo,3-endo,6-exo,8,9,-10-hexachlorobornane (B6-923 or Hx-Sed) and 2-endo,3exo,5-endo,6-exo,8,9,10-heptachlorobornane (B7-1001 or Hp-Sed). As expected, repetition of this experiment at cooler water temperatures (T mean ) 15°C) resulted in a decrease in overall (i.e., both enantiomers) first-order elimination rate constants. Enantiomer fractions or ratios (EFs/ ERs) during elimination, however, varied by congener, ranging from racemic for very rapidly eliminated Cl 5 homologues to increasingly nonracemic for selected Cl 6 -Cl 8 homologues (including B6-923, several unknown Cl 7 compounds, B8-1414, and B8-1945). As a result, we propose a classification to describe the environmental persistence of chiral toxaphene pollutants based on congenerspecific elimination kinetics and susceptibility to biotransformation as measured by EFs/ERs.

Chemosphere, 2015

Low-density polyethylene (PE) passive samplers containing performance reference compounds (PRCs) ... more Low-density polyethylene (PE) passive samplers containing performance reference compounds (PRCs) were deployed at multiple depths in two urban coastal marine locations to estimate dissolved concentrations of hydrophobic organic contaminants (HOCs), including dichlorodiphenyltrichloroethane (DDT) and its metabolites, polychlorinated biphenyl (PCB) congeners, and polybrominated flame retardants. PE samplers pre-loaded with PRCs were deployed at the surface, mid-column, and near bottom at sites representing the nearshore continental shelf off southern California (Santa Monica Bay, USA) and a mega commercial port (Los Angeles Harbor). After correcting for fractional equilibration using PRCs, concentrations ranged up to 100pgL(-1) for PCBs and polybrominated diphenyl ethers (PBDEs), 500pgL(-1) for DDMU and 300pgL(-1) for DDNU, and to 1000pgL(-1) for p,p'-DDE. Seawater concentrations of DDTs and PCBs increased with depth, suggesting that bed sediments serve as the source of water column HOCs in Santa Monica Bay. In contrast, no discernable pattern between surface and near-bottom concentrations in Los Angeles Harbor was observed, which were also several-fold lower (DDTs: 45-300pgL(-1), PCBs: 5-50pgL(-1)) than those in Santa Monica Bay (DDTs: 2-1100pgL(-1), PCBs: 2-250pgL(-1)). Accumulation by mussels co-deployed with the PE samplers at select sites was strongly correlated with PE-estimated seawater concentrations, providing further evidence that these samplers are a viable alternative for monitoring of HOC exposure. Fractional equilibration observed with the PRCs increased with decreasing PRC molar volume indicating the importance of target compound physicochemical properties when estimating water column concentrations using passive samplers in situ.

Estuaries, 2001

To better characterize human health risks associated with potentially contaminated seafood, 56 co... more To better characterize human health risks associated with potentially contaminated seafood, 56 composite samples of edible tissue of several finfish and shellfish species were analyzed for residues of toxaphene using gas chromatography with electron capture and negative ion mass spectrometric detection (GC-ECD and GC-ECNI-MS). Toxaphene in these samples, collected in 1997 near a former toxaphene plant in Brunswick, Georgia, were

Marine Pollution Bulletin, 1999

Sixty-six sediment samples were collected from Kyeonggi Bay, Korea, in December 1995 and analysed... more Sixty-six sediment samples were collected from Kyeonggi Bay, Korea, in December 1995 and analysed for a suite of 2–6 ring polycyclic aromatic hydrocarbons (PAHs). Sediments were collected in the Han River estuary, Incheon Harbour, from nearshore locations adjacent to large industrial complexes south of Incheon, and along transects toward the open sea. Concentrations of PAHs (9.1–1400 ng g−1 dry wt

Science of The Total Environment, 2008

Coastal marine resources are at risk from anthropogenic contaminants, including legacy persistent... more Coastal marine resources are at risk from anthropogenic contaminants, including legacy persistent organic pollutants (POPs) with half-lives of decades or more. To determine if polychlorinated biphenyl (PCB) signatures can be used to distinguish among local populations of inshore bottlenose dolphins (Tursiops truncatus) along the southeastern U.S. coast, blubber from free-ranging and stranded animals were collected along the Georgia coast in 2004 and analyzed for PCB congeners using gas chromatography with electron capture and negative chemical ionization mass spectrometric detection (GC-ECD and GC-NCI-MS). Mean total PCB concentrations (77 ± 34 μg/g lipid) were more than 10 fold higher and congener distributions were highly enriched in Cl 7 -Cl 10 homologs in free-ranging animals from the Turtle/Brunswick River estuary (TBRE) compared with strandings samples from Savannah area estuaries 90 km to the north. Using principal components analysis (PCA), the Aroclor 1268 signature associated with TBRE animals was distinct from that observed in Savannah area animals, and also from those in animals biopsied in other southeastern U.S estuaries. Moreover, PCB signatures in dolphin blubber closely resembled those in local preferred prey fish species, strengthening the hypothesis that inshore T. truncatus populations exhibit long-term fidelity to specific estuaries and making them excellent sentinels for assessing the impact of stressors on coastal ecosystem health. ava i l a b l e a t w w w. s c i e n c e d i r e c t . c o m w w w. e l s ev i e r. c o m / l o c a t e / s c i t o t e n v

Marine Pollution Bulletin, 2014

Marine Pollution Bulletin, 2004

Coastal urbanization supplies surrounding estuarine environments with urban-related contaminants ... more Coastal urbanization supplies surrounding estuarine environments with urban-related contaminants such as polycyclic aromatic hydrocarbons (PAHs), metals and pesticide mixtures. In our study, adult female and male copepods (Amphiascus tenuiremis) were chronically exposed to 18 sediment samples collected from sites influenced by different land-uses. Sediment samples were collected from three major suburban areas (Hilton Head, Kiawah Island and the Okatee River watershed) and a pristine site (North Inlet) in coastal South Carolina. Three-sediment bioassays (six sites per bioassay) were conducted by culturing copepods for 14 days in quadruplicate test sediments under flow-through conditions at 20°C and 12:12 LD cycles. Adult survival and copepod reproductive output were quantified. Sediment samples were also analyzed by GC-MS for low and high molecular weight PAHs. Minimal adult mortality was observed in most sediment samples. However, sediments from Hilton Head Island and the Okatee River showed significant effects on copepod reproductive output (i.e., nauplii, copepodites and clutch size). Thus, we determined that reproductive endpoints rather than adult copepod survivorship were more sensitive to effects of contaminated sediments on A. tenuiremis. Furthermore, six (33%) of the 18 sites had a >25% reduction in copepod bioassay endpoints relative to controls, suggesting a high risk to long term A. tenuiremis population maintenance.

Marine Pollution Bulletin, 2014

Marine Pollution Bulletin, 2014

Three passive sampling devices (PSDs), polar organic chemical integrative samplers (POCIS), polye... more Three passive sampling devices (PSDs), polar organic chemical integrative samplers (POCIS), polyethylene devices (PEDs), and solid-phase microextraction (SPME) samplers were used to sample a diverse set of chemicals in the coastal waters of San Francisco Bay and the Southern California Bight. Seventy one chemicals (including fragrances, phosphate flame retardants, pharmaceuticals, PAHs, PCBs, PBDEs, and pesticides) were measured in at least 50% of the sites. The chemical profile from the San Francisco Bay sites was distinct from profiles from the sites in the Southern California Bight. This distinction was not due to a single compound or class, but by the relative abundances/concentrations of the chemicals. Comparing the PSDs to mussel (Mytilus spp.) tissues, a positive correlation exists for the 25 and 26 chemicals in common for the PEDs and SPME, respectively. Diphenhydramine was the only common chemical out of 40 analyzed in both POCIS and tissues detected at a common site.

Marine Environmental Research, 2004

A grass shrimp bioassay was carried out on sediments from three estuarine stations which were dif... more A grass shrimp bioassay was carried out on sediments from three estuarine stations which were different distances from a highway storm drain. Total polycyclic aromatic hydrocarbon (PAH) concentrations were 29, 1.5 and 0.1 lg/g sediment at stations A (next to drain), B (100 m from drain) and C (500 m from drain), respectively. Lower embryo production and embryo hatching rates and a higher level of DNA strand breaks (comet assay) were observed in grass shrimp exposed to stations A and B sediments. There appeared to be an association between reproduction abnormalities and increased DNA strand breaks as a result of grass shrimp exposure to estuarine sediments receiving highway runoff.

Journal of Separation Science, 2001

Residues of toxaphene, a persistent organochlorine biocide, are difficult to characterize in the ... more Residues of toxaphene, a persistent organochlorine biocide, are difficult to characterize in the environment due to their complex composition, selective recalcitrance, and lack of a comprehensive standards set. No single gas chromatographic column stationary phase completely separates toxaphene on a congener specific basis. Using GC-ECD and GC-MS, the performance of a slightly polar stationary phase (DB-XLB) was compared with that of a widely used nonpolar phase (DB-5). Commercially available standard mixtures and tissue samples from a toxaphene-contaminated coastal marsh were analyzed. Both DB-5 and DB-XLB fully resolved a similar number of target congeners (18 of 22). The XLB phase, however, better resolved congener pairs P31/32, P40/ 41, and several others (e.g. P26/-1, Hx-Sed, and Hp-Sed). Compared with DB-5 and several recently evaluated, slightly polar phases, DB-XLB offers excellent overall performance for single column analysis of environmentally relevant toxaphene residues.

Journal of Chromatography A, 2007

Aqueous solutions of 14 C-labeled analogs of seven hydrophobic organic chemicals (HOCs) were subj... more Aqueous solutions of 14 C-labeled analogs of seven hydrophobic organic chemicals (HOCs) were subject to solid-phase microextraction (SPME) under static conditions to assess their multi-compartment distribution and to compare poly(dimethyl)siloxane (PDMS)-water partition coefficients (K f values) with previously reported values. To accomplish this, a protocol for quantitative desorption of radiolabelled HOCs from SPME fibers using hexane was developed. Time series extractions indicated that loading of SPME fibers had reached steady-state by day 8 for PCBs 52, 77 and 153, phenanthrene, benzo[a]pyrene, p,p -DDT and p,p -DDE. The recovery of spiked radioactivity among the (residual) aqueous phase, the PDMS coating, and all remaining wetted experimental surfaces ranged between 80 and 120%. K f values based on 14 C-labeled analogs were in good agreement with previously published values that were determined at (or closely approaching) equilibrium conditions and without significant chemical depletion and/or uncorrected system losses. Because it allows for the direct determination of HOCs associated with the residual aqueous and experimental surface compartments, the use of radiolabelled HOC analogs is a powerful tool in discriminating among competing sorptive compartments encountered in most SPME fiber calibration methodologies employed to date.

Journal of Chromatography A, 2006

A static solid-phase microextraction (SPME) procedure combined with liquid-liquid extraction (LLE... more A static solid-phase microextraction (SPME) procedure combined with liquid-liquid extraction (LLE) was used to determine the poly(dimethyl)siloxane (PDMS)-water partition coefficients (K(f)) for selected polychlorinated biphenyl congeners (PCBs), including PCB 1, 15, 28, 47, 101, 153, 180, 202, 206, and 209. The accuracy for the measurements of analyte concentrations in the aqueous phase was ensured with a one-to-one recovery correction strategy employing one 13C-labeled PCB congener as a surrogate standard for each unlabeled PCB counterpart. The effects of coating thickness (7, 30, and 100 microm) and sample volume (130 mL and 2 L) on the K(f) values were examined experimentally and confirmed with paired t-tests. Significant dependence of K(f) values on coating thickness was found for a few heavily chlorinated congeners only, and was tentatively attributed to the use of the inaccurate effective coating volumes and the structural variation with these PDMS coatings. In addition, no significant differences in the log K(f) values of all analytes except for PCB 206 were found between the sample sizes of 130 mL and 2 L for both the 7- and 100-microm coatings. Overall, K(f) values obtained with 2-L sample containers were consistently higher than those reported in the literature, which is attributable to the selection of appropriate equilibrium times for SPME and direct measurements of aqueous analyte concentrations with LLE in the present study.

Journal of Agricultural and Food Chemistry, 2001

Integrated Environmental Assessment and Management, 2014

Integrated Environmental Assessment and Management, 2014

A scientific advisory panel was convened by the State of California to recommend monitoring for c... more A scientific advisory panel was convened by the State of California to recommend monitoring for chemicals of emerging concern (CECs) in aquatic systems that receive discharge of municipal wastewater treatment plant (WWTP) effluent and stormwater runoff. The panel developed a risk-based screening framework that considered environmental sources and fate of CECs observed in receiving waters across the State. Using existing occurrence and risk threshold data in water, sediment, and biological tissue, the panel applied the framework to identify a priority list of CECs for initial monitoring in three representative receiving water scenarios. The initial screening list of 16 CECs identified by the panel included consumer and commercial chemicals, flame retardants, pesticides, pharmaceuticals and personal care products, and natural hormones. The panel designed an iterative, phased strategy with interpretive guidelines that direct and update management actions commensurate with potential risk identified using the risk-based framework and monitoring data. Because of the everchanging nature of chemical use, technology, and management practices, the panel offered recommendations to improve CEC monitoring, including development of bioanalytical screening methods whose responses integrate exposure to complex mixtures and that can be linked to higher-order effects; development or refinement of models that predict the input, fate, and effects of future chemicals; and filling of key data gaps on CEC occurrence and toxicity. Finally, the panel stressed the need for adaptive management, allowing for future review of, and if warranted, modifications to the strategy to incorporate the latest science available to the water resources community. Integr Environ Assess Manag 2014;10:69-77. © 2013 SETAC

Environmental Toxicology and Chemistry, 2010

The present study investigated cross-media transport between both the sediment and the water colu... more The present study investigated cross-media transport between both the sediment and the water column and between the water column and the atmosphere, to understand the role of each compartment as a source or a sink of polycyclic aromatic hydrocarbons (PAH) in southern California, USA, coastal waters. Concentrations of PAH were measured in the atmosphere, water column, and sediment at four water-quality-impaired sites in southern California: Ballona Creek Estuary, Los Angeles Harbor, Upper Newport Bay, and San Diego Bay. These concentrations were used to calculate site-specific sediment-water and atmosphere-water exchange fluxes. The net sediment-water exchange of total PAH (t-PAH) was positive, indicating that sediments were a source to the overlying water column. Furthermore, the net atmosphere-water exchange (gas exchange þ dry particle deposition) of t-PAH was typically positive also, indicating the water column was a net source of PAH to the surrounding atmosphere through gas exchange. However, in all cases, the magnitude of the diffusive flux of PAH out of the sediments and into the water column far exceeded input or output of PAH through air/ water exchange processes. These results demonstrate the potential importance of contaminated sediments as a source of PAH to the water column in coastal waters of southern California.

Marine Pollution Bulletin, 2011

To investigate the potential for enantioselective transformation and accumulation, the enantiomer... more To investigate the potential for enantioselective transformation and accumulation, the enantiomer distributions of seven polychlorinated biphenyl (PCB) atropisomers were measured in the sediment and biota from a sub-tropical estuary heavily contaminated with Aroclor 1268, a technical mixture of highly chlorinated PCB congeners. Enantiomer fractions (EFs) of PCBs 91, 95, 136, 149, 174, 176, and 183 in marsh sediment, invertebrate, forage

Environmental Science & Technology, 2001

Although reports of nonracemic proportions of chiral organochlorine pollutants in the environment... more Although reports of nonracemic proportions of chiral organochlorine pollutants in the environment are widespread, the interpretation of such data is not well developed. Using GC/MS and a chiral stationary phase consisting of 25% tert-butyldimethylsilylated beta-cyclodextrin in PS086 (beta-BSCD), we followed the change in the enantiomeric signature of 2-exo,3-endo,6-exo,8,9,10-hexachlorobornane (B6-923) in naturally contaminated fish maintained under toxaphene-free conditions. Whereas the enantiomeric ratio (ER) of B6-923 was near racemic at the start of the elimination experiment, it had increased severalfold by the end of 60 d. On the basis of first-order kinetics, one enantiomer of B6-923 was eliminated twice as fast as its mirror image, resulting in half-lives of 7 and 13 d, respectively. Enantioselective elimination by our test fish (Fundulus sp.) strongly suggests active biotransformation of B6-923; however, bioprocessing throughput estimates suggest a very low in situ rate of natural attenuation. These results confirm that the relatively constant ERs observed for chiral organochlorines in a given species are the result of competing processes, e.g., uptake vs elimination. Our experiments also further illustrate the utility of enantioselective analysis in characterizing the biotransformation of persistent organochlorine pollutants.

Environmental Science & Technology, 2005

Recent advances in enantioselective separation techniques have enabled scientists to investigate ... more Recent advances in enantioselective separation techniques have enabled scientists to investigate environmental fate processes of chiral pollutants. In this study, congenerand enantiomer-specific toxaphene residues were monitored in captive, naturally contaminated fish (Fundulus heteroclitus) to characterize the effect of temperature and compound structure on the enantioselectivity of the elimination process. A previous study performed under warm water conditions (T mean ) 25°C) demonstrated relatively rapid (t 1/2 ≈ 7-14 d) and enantioselective elimination of the reductive dechlorination metabolites 2-exo,3-endo,6-exo,8,9,-10-hexachlorobornane (B6-923 or Hx-Sed) and 2-endo,3exo,5-endo,6-exo,8,9,10-heptachlorobornane (B7-1001 or Hp-Sed). As expected, repetition of this experiment at cooler water temperatures (T mean ) 15°C) resulted in a decrease in overall (i.e., both enantiomers) first-order elimination rate constants. Enantiomer fractions or ratios (EFs/ ERs) during elimination, however, varied by congener, ranging from racemic for very rapidly eliminated Cl 5 homologues to increasingly nonracemic for selected Cl 6 -Cl 8 homologues (including B6-923, several unknown Cl 7 compounds, B8-1414, and B8-1945). As a result, we propose a classification to describe the environmental persistence of chiral toxaphene pollutants based on congenerspecific elimination kinetics and susceptibility to biotransformation as measured by EFs/ERs.

Chemosphere, 2015

Low-density polyethylene (PE) passive samplers containing performance reference compounds (PRCs) ... more Low-density polyethylene (PE) passive samplers containing performance reference compounds (PRCs) were deployed at multiple depths in two urban coastal marine locations to estimate dissolved concentrations of hydrophobic organic contaminants (HOCs), including dichlorodiphenyltrichloroethane (DDT) and its metabolites, polychlorinated biphenyl (PCB) congeners, and polybrominated flame retardants. PE samplers pre-loaded with PRCs were deployed at the surface, mid-column, and near bottom at sites representing the nearshore continental shelf off southern California (Santa Monica Bay, USA) and a mega commercial port (Los Angeles Harbor). After correcting for fractional equilibration using PRCs, concentrations ranged up to 100pgL(-1) for PCBs and polybrominated diphenyl ethers (PBDEs), 500pgL(-1) for DDMU and 300pgL(-1) for DDNU, and to 1000pgL(-1) for p,p'-DDE. Seawater concentrations of DDTs and PCBs increased with depth, suggesting that bed sediments serve as the source of water column HOCs in Santa Monica Bay. In contrast, no discernable pattern between surface and near-bottom concentrations in Los Angeles Harbor was observed, which were also several-fold lower (DDTs: 45-300pgL(-1), PCBs: 5-50pgL(-1)) than those in Santa Monica Bay (DDTs: 2-1100pgL(-1), PCBs: 2-250pgL(-1)). Accumulation by mussels co-deployed with the PE samplers at select sites was strongly correlated with PE-estimated seawater concentrations, providing further evidence that these samplers are a viable alternative for monitoring of HOC exposure. Fractional equilibration observed with the PRCs increased with decreasing PRC molar volume indicating the importance of target compound physicochemical properties when estimating water column concentrations using passive samplers in situ.

Estuaries, 2001

To better characterize human health risks associated with potentially contaminated seafood, 56 co... more To better characterize human health risks associated with potentially contaminated seafood, 56 composite samples of edible tissue of several finfish and shellfish species were analyzed for residues of toxaphene using gas chromatography with electron capture and negative ion mass spectrometric detection (GC-ECD and GC-ECNI-MS). Toxaphene in these samples, collected in 1997 near a former toxaphene plant in Brunswick, Georgia, were

Marine Pollution Bulletin, 1999

Sixty-six sediment samples were collected from Kyeonggi Bay, Korea, in December 1995 and analysed... more Sixty-six sediment samples were collected from Kyeonggi Bay, Korea, in December 1995 and analysed for a suite of 2–6 ring polycyclic aromatic hydrocarbons (PAHs). Sediments were collected in the Han River estuary, Incheon Harbour, from nearshore locations adjacent to large industrial complexes south of Incheon, and along transects toward the open sea. Concentrations of PAHs (9.1–1400 ng g−1 dry wt

Science of The Total Environment, 2008

Coastal marine resources are at risk from anthropogenic contaminants, including legacy persistent... more Coastal marine resources are at risk from anthropogenic contaminants, including legacy persistent organic pollutants (POPs) with half-lives of decades or more. To determine if polychlorinated biphenyl (PCB) signatures can be used to distinguish among local populations of inshore bottlenose dolphins (Tursiops truncatus) along the southeastern U.S. coast, blubber from free-ranging and stranded animals were collected along the Georgia coast in 2004 and analyzed for PCB congeners using gas chromatography with electron capture and negative chemical ionization mass spectrometric detection (GC-ECD and GC-NCI-MS). Mean total PCB concentrations (77 ± 34 μg/g lipid) were more than 10 fold higher and congener distributions were highly enriched in Cl 7 -Cl 10 homologs in free-ranging animals from the Turtle/Brunswick River estuary (TBRE) compared with strandings samples from Savannah area estuaries 90 km to the north. Using principal components analysis (PCA), the Aroclor 1268 signature associated with TBRE animals was distinct from that observed in Savannah area animals, and also from those in animals biopsied in other southeastern U.S estuaries. Moreover, PCB signatures in dolphin blubber closely resembled those in local preferred prey fish species, strengthening the hypothesis that inshore T. truncatus populations exhibit long-term fidelity to specific estuaries and making them excellent sentinels for assessing the impact of stressors on coastal ecosystem health. ava i l a b l e a t w w w. s c i e n c e d i r e c t . c o m w w w. e l s ev i e r. c o m / l o c a t e / s c i t o t e n v

Marine Pollution Bulletin, 2014

Marine Pollution Bulletin, 2004

Coastal urbanization supplies surrounding estuarine environments with urban-related contaminants ... more Coastal urbanization supplies surrounding estuarine environments with urban-related contaminants such as polycyclic aromatic hydrocarbons (PAHs), metals and pesticide mixtures. In our study, adult female and male copepods (Amphiascus tenuiremis) were chronically exposed to 18 sediment samples collected from sites influenced by different land-uses. Sediment samples were collected from three major suburban areas (Hilton Head, Kiawah Island and the Okatee River watershed) and a pristine site (North Inlet) in coastal South Carolina. Three-sediment bioassays (six sites per bioassay) were conducted by culturing copepods for 14 days in quadruplicate test sediments under flow-through conditions at 20°C and 12:12 LD cycles. Adult survival and copepod reproductive output were quantified. Sediment samples were also analyzed by GC-MS for low and high molecular weight PAHs. Minimal adult mortality was observed in most sediment samples. However, sediments from Hilton Head Island and the Okatee River showed significant effects on copepod reproductive output (i.e., nauplii, copepodites and clutch size). Thus, we determined that reproductive endpoints rather than adult copepod survivorship were more sensitive to effects of contaminated sediments on A. tenuiremis. Furthermore, six (33%) of the 18 sites had a >25% reduction in copepod bioassay endpoints relative to controls, suggesting a high risk to long term A. tenuiremis population maintenance.

Marine Pollution Bulletin, 2014

Marine Pollution Bulletin, 2014

Three passive sampling devices (PSDs), polar organic chemical integrative samplers (POCIS), polye... more Three passive sampling devices (PSDs), polar organic chemical integrative samplers (POCIS), polyethylene devices (PEDs), and solid-phase microextraction (SPME) samplers were used to sample a diverse set of chemicals in the coastal waters of San Francisco Bay and the Southern California Bight. Seventy one chemicals (including fragrances, phosphate flame retardants, pharmaceuticals, PAHs, PCBs, PBDEs, and pesticides) were measured in at least 50% of the sites. The chemical profile from the San Francisco Bay sites was distinct from profiles from the sites in the Southern California Bight. This distinction was not due to a single compound or class, but by the relative abundances/concentrations of the chemicals. Comparing the PSDs to mussel (Mytilus spp.) tissues, a positive correlation exists for the 25 and 26 chemicals in common for the PEDs and SPME, respectively. Diphenhydramine was the only common chemical out of 40 analyzed in both POCIS and tissues detected at a common site.

Marine Environmental Research, 2004

A grass shrimp bioassay was carried out on sediments from three estuarine stations which were dif... more A grass shrimp bioassay was carried out on sediments from three estuarine stations which were different distances from a highway storm drain. Total polycyclic aromatic hydrocarbon (PAH) concentrations were 29, 1.5 and 0.1 lg/g sediment at stations A (next to drain), B (100 m from drain) and C (500 m from drain), respectively. Lower embryo production and embryo hatching rates and a higher level of DNA strand breaks (comet assay) were observed in grass shrimp exposed to stations A and B sediments. There appeared to be an association between reproduction abnormalities and increased DNA strand breaks as a result of grass shrimp exposure to estuarine sediments receiving highway runoff.

Journal of Separation Science, 2001

Residues of toxaphene, a persistent organochlorine biocide, are difficult to characterize in the ... more Residues of toxaphene, a persistent organochlorine biocide, are difficult to characterize in the environment due to their complex composition, selective recalcitrance, and lack of a comprehensive standards set. No single gas chromatographic column stationary phase completely separates toxaphene on a congener specific basis. Using GC-ECD and GC-MS, the performance of a slightly polar stationary phase (DB-XLB) was compared with that of a widely used nonpolar phase (DB-5). Commercially available standard mixtures and tissue samples from a toxaphene-contaminated coastal marsh were analyzed. Both DB-5 and DB-XLB fully resolved a similar number of target congeners (18 of 22). The XLB phase, however, better resolved congener pairs P31/32, P40/ 41, and several others (e.g. P26/-1, Hx-Sed, and Hp-Sed). Compared with DB-5 and several recently evaluated, slightly polar phases, DB-XLB offers excellent overall performance for single column analysis of environmentally relevant toxaphene residues.

Journal of Chromatography A, 2007

Aqueous solutions of 14 C-labeled analogs of seven hydrophobic organic chemicals (HOCs) were subj... more Aqueous solutions of 14 C-labeled analogs of seven hydrophobic organic chemicals (HOCs) were subject to solid-phase microextraction (SPME) under static conditions to assess their multi-compartment distribution and to compare poly(dimethyl)siloxane (PDMS)-water partition coefficients (K f values) with previously reported values. To accomplish this, a protocol for quantitative desorption of radiolabelled HOCs from SPME fibers using hexane was developed. Time series extractions indicated that loading of SPME fibers had reached steady-state by day 8 for PCBs 52, 77 and 153, phenanthrene, benzo[a]pyrene, p,p -DDT and p,p -DDE. The recovery of spiked radioactivity among the (residual) aqueous phase, the PDMS coating, and all remaining wetted experimental surfaces ranged between 80 and 120%. K f values based on 14 C-labeled analogs were in good agreement with previously published values that were determined at (or closely approaching) equilibrium conditions and without significant chemical depletion and/or uncorrected system losses. Because it allows for the direct determination of HOCs associated with the residual aqueous and experimental surface compartments, the use of radiolabelled HOC analogs is a powerful tool in discriminating among competing sorptive compartments encountered in most SPME fiber calibration methodologies employed to date.

Journal of Chromatography A, 2006

A static solid-phase microextraction (SPME) procedure combined with liquid-liquid extraction (LLE... more A static solid-phase microextraction (SPME) procedure combined with liquid-liquid extraction (LLE) was used to determine the poly(dimethyl)siloxane (PDMS)-water partition coefficients (K(f)) for selected polychlorinated biphenyl congeners (PCBs), including PCB 1, 15, 28, 47, 101, 153, 180, 202, 206, and 209. The accuracy for the measurements of analyte concentrations in the aqueous phase was ensured with a one-to-one recovery correction strategy employing one 13C-labeled PCB congener as a surrogate standard for each unlabeled PCB counterpart. The effects of coating thickness (7, 30, and 100 microm) and sample volume (130 mL and 2 L) on the K(f) values were examined experimentally and confirmed with paired t-tests. Significant dependence of K(f) values on coating thickness was found for a few heavily chlorinated congeners only, and was tentatively attributed to the use of the inaccurate effective coating volumes and the structural variation with these PDMS coatings. In addition, no significant differences in the log K(f) values of all analytes except for PCB 206 were found between the sample sizes of 130 mL and 2 L for both the 7- and 100-microm coatings. Overall, K(f) values obtained with 2-L sample containers were consistently higher than those reported in the literature, which is attributable to the selection of appropriate equilibrium times for SPME and direct measurements of aqueous analyte concentrations with LLE in the present study.

Journal of Agricultural and Food Chemistry, 2001

Integrated Environmental Assessment and Management, 2014

Integrated Environmental Assessment and Management, 2014

A scientific advisory panel was convened by the State of California to recommend monitoring for c... more A scientific advisory panel was convened by the State of California to recommend monitoring for chemicals of emerging concern (CECs) in aquatic systems that receive discharge of municipal wastewater treatment plant (WWTP) effluent and stormwater runoff. The panel developed a risk-based screening framework that considered environmental sources and fate of CECs observed in receiving waters across the State. Using existing occurrence and risk threshold data in water, sediment, and biological tissue, the panel applied the framework to identify a priority list of CECs for initial monitoring in three representative receiving water scenarios. The initial screening list of 16 CECs identified by the panel included consumer and commercial chemicals, flame retardants, pesticides, pharmaceuticals and personal care products, and natural hormones. The panel designed an iterative, phased strategy with interpretive guidelines that direct and update management actions commensurate with potential risk identified using the risk-based framework and monitoring data. Because of the everchanging nature of chemical use, technology, and management practices, the panel offered recommendations to improve CEC monitoring, including development of bioanalytical screening methods whose responses integrate exposure to complex mixtures and that can be linked to higher-order effects; development or refinement of models that predict the input, fate, and effects of future chemicals; and filling of key data gaps on CEC occurrence and toxicity. Finally, the panel stressed the need for adaptive management, allowing for future review of, and if warranted, modifications to the strategy to incorporate the latest science available to the water resources community. Integr Environ Assess Manag 2014;10:69-77. © 2013 SETAC

Environmental Toxicology and Chemistry, 2010

The present study investigated cross-media transport between both the sediment and the water colu... more The present study investigated cross-media transport between both the sediment and the water column and between the water column and the atmosphere, to understand the role of each compartment as a source or a sink of polycyclic aromatic hydrocarbons (PAH) in southern California, USA, coastal waters. Concentrations of PAH were measured in the atmosphere, water column, and sediment at four water-quality-impaired sites in southern California: Ballona Creek Estuary, Los Angeles Harbor, Upper Newport Bay, and San Diego Bay. These concentrations were used to calculate site-specific sediment-water and atmosphere-water exchange fluxes. The net sediment-water exchange of total PAH (t-PAH) was positive, indicating that sediments were a source to the overlying water column. Furthermore, the net atmosphere-water exchange (gas exchange þ dry particle deposition) of t-PAH was typically positive also, indicating the water column was a net source of PAH to the surrounding atmosphere through gas exchange. However, in all cases, the magnitude of the diffusive flux of PAH out of the sediments and into the water column far exceeded input or output of PAH through air/ water exchange processes. These results demonstrate the potential importance of contaminated sediments as a source of PAH to the water column in coastal waters of southern California.