Method validation and reconnaissance of pharmaceuticals, personal care products, and alkylphenols in surface waters, sediments, and mussels in an urban estuary.

Novel methods utilizing liquid chromatography-tandem mass spectrometry and gas chromatography-mass spectrometry were validated for low-level detection of 104 pharmaceuticals and personal care products ingredients (PPCPs) and four alkylphenols (APs) in environmental samples. The methods were applied to surface water, sediment, and mussel tissue samples collected from San Francisco Bay, CA, USA, an urban estuary that receives direct discharge from over forty municipal and industrial wastewater outfalls. Among the target PPCPs, 35% were detected in at least one sample, with 31, 10, and 17 compounds detected in water, sediment, and mussels, respectively. Maximum concentrations were 92 ng/L in water (valsartan), 33 ng/g dry weight (dw) in sediments (triclocarban), and 14 ng/g wet weight (ww) in mussels (N,N-diethyl-m-toluamide). Nonylphenol was detected in water (<2-73 ng/L), sediments (22-86 ng/g dw), and mussels (<0.04-95 ng/g ww), and nonylphenol mono- and diethoxylates were detected in sediments (<1-40 ng/g dw) and mussels (<5-192 ng/g ww). The concentrations of PPCPs and APs detected in the San Francisco Bay samples were generally at least an order of magnitude below concentrations expected to elicit toxic effects in aquatic organisms. This study represents the first reconnaissance of PPCPs in mussels living in an urban estuary and provides the first field-derived bioaccumulation factors (BAFs) for select compounds in aquatic organisms.

Brominated and chlorinated flame retardants in San Francisco Bay sediments and wildlife.

Restrictions on the use of polybrominated diphenyl ethers (PBDEs) have resulted in the use of alternative flame retardants in consumer products to comply with flammability standards. In contrast to PBDEs, information on the occurrence and fate of these alternative compounds in the environment is limited, particularly in the United States. In this study, a survey of flame retardants in San Francisco Bay was conducted to evaluate whether PBDE replacement chemicals and other current use flame retardants were accumulating in the Bay food web. In addition to PBDEs, brominated and chlorinated flame retardants (hexabromocyclododecane (HBCD) and Dechlorane Plus (DP)) were detected in Bay sediments and wildlife. Median concentrations of PBDEs, HBCD, and DP, respectively, were 4.3, 0.3, and 0.2 ng g⁻¹ dry weight (dw) in sediments; 1670, <6.0, and 0.5 ng g⁻¹ lipid weight (lw) in white croaker (Genyonemus lineatus); 1860, 6.5, and 1.3 ng g⁻¹ lw in shiner surfperch (Cymatogaster aggregata); 5500, 37.4, and 0.9 ng g⁻¹ lw in eggs of double-crested cormorant (Phalacrocorax auritus); 770, 7.1, and 0.9 ng g⁻¹ lw in harbor seal (Phoca vitulina) adults; and 330, 3.5, and <0.1 ng g⁻¹ lw in harbor seal (P. vitulina) pups. Two additional flame retardants, pentabromoethylbenzene (PBEB) and 1,2-bis(2,4,6 tribromophenoxy)ethane (BTBPE) were detected in sediments but with less frequency and at lower concentrations (median concentrations of 0.01 and 0.02 ng g⁻¹ dw, respectively) compared to the other flame retardants. PBEB was also detected in each of the adult harbor seals and in 83% of the pups (median concentrations 0.2 and 0.07 ng g⁻¹ lw, respectively). The flame retardants hexabromobenzene (HBB), decabromodiphenyl ethane (DBDPE), bis(2-ethylhexyl) tetrabromophthalate (TBPH), and 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), were not detected in sediments and BTBPE, HBB and TBB were not detected in wildlife samples. Elevated concentrations of some flame retardants were likely associated with urbanization and Bay hydrodynamics. Compared to other locations, concentrations of PBDEs in Bay wildlife were comparable or higher, while concentrations of the alternatives were generally lower. This study is the first to determine concentrations of PBDE replacement products and other flame retardants in San Francisco Bay, providing some of the first data on the food web occurrence of these flame retardants in a North American urbanized estuary.

Measurement of flame retardants and triclosan in municipal sewage sludge and biosolids.

As polybrominated diphenyl ethers (PBDEs) face increasing restrictions worldwide, several alternate flame retardants are expected to see increased use as replacement compounds in consumer products. Chemical analysis of biosolids collected from wastewater treatment plants (WWTPs) can help determine whether these flame retardants are migrating from the indoor environment to the outdoor environment, where little is known about their ultimate fate and effects. The objective of this study was to measure concentrations of a suite of flame retardants, and the antimicrobial compound triclosan, in opportunistic samples of municipal biosolids and the domestic sludge Standard Reference Material (SRM) 2781. Grab samples of biosolids were collected from two WWTPs in North Carolina and two in California. Biosolids samples were also obtained during three subsequent collection events at one of the North Carolina WWTPs to evaluate fluctuations in contaminant levels within a given facility over a period of three years. The biosolids and SRM 2781 were analyzed for PBDEs, hexabromobenzene (HBB), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), di(2-ethylhexyl)-2,3,4,5-tetrabromophthalate (TBPH), the chlorinated flame retardant Dechlorane Plus (syn- and anti-isomers), and the antimicrobial agent 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan). PBDEs were detected in every sample analyzed, and ΣPBDE concentrations ranged from 1750 to 6358ng/g dry weight. Additionally, the PBDE replacement chemicals TBB and TBPH were detected at concentrations ranging from 120 to 3749 ng/g dry weight and from 206 to 1631 ng/g dry weight, respectively. Triclosan concentrations ranged from 490 to 13,866 ng/g dry weight. The detection of these contaminants of emerging concern in biosolids suggests that these chemicals have the potential to migrate out of consumer products and enter the outdoor environment.

Bioaccumulation kinetics of polybrominated diphenyl ethers from estuarine sediments to the marine polychaete, Nereis virens.

Polybrominated diphenyl ethers (PBDEs) are flame-retardant chemicals that have become ubiquitous environmental contaminants. Polybrominated diphenyl ether no-uptake rates from estuarine or marine sediments to deposit-feeding organisms have not yet been reported. In the present study, the marine polychaete worm Nereis virens was exposed to field-contaminated and spiked sediments containing the penta- and deca-BDE commercial mixtures in a 28-d experiment to characterize the relative bioavailability of PBDE congeners from estuarine sediments. A time series sampling regimen was conducted to estimate uptake rate constants. In both field-collected and laboratory-spiked sediment exposures, worms selectively accumulated congeners in the penta-BDE mixture over BDE 209 and other components of the deca-BDE mixture, supporting the prevalence of these congeners in higher trophic level species. Brominated diphenyl ether 209 was not bioavailable to N. virens from field sediment and was only minimally detected in worms exposed to spiked sediments in which bioavailability was maximized. Chemical hydrophobicity was not a good predictor of bioavailability for congeners in the penta-BDE mixture. Direct comparison of bioavailability from the spiked and field sediments for the predominant congeners in the penta-BDE mixture was confounded by the considerable difference in exposure concentration between treatments. Biota-sediment accumulation factors (BSAFs) for N. virens after 28 d of exposure to the field sediment were lower than the BSAFs for Nereis succinea collected from the field site, indicating that 28-d bioaccumulation tests using N. virens may underestimate the in situ concentration of PBDEs in deposit-feeding species. The bioavailability of PBDEs to N. virens indicates that these chemicals can be remobilized from estuarine sediments and transferred to aquatic food webs.

Bioavailability of decabromodiphenyl ether to the marine polychaete Nereis virens.

The flame retardant decabromodiphenyl ether (BDE 209) accumulates in humans and terrestrial food webs, but few studies have reported the accumulation of BDE 209 in aquatic biota. To investigate the mechanisms controlling the bioavailability of BDE 209, a 28-d bioaccumulation experiment was conducted in which the marine polychaete worm Nereis virens was exposed to a decabromodiphenyl ether (deca-BDE) commercial mixture (>85% BDE 209) in spiked sediments, in spiked food, or in field sediments. Bioaccumulation from spiked substrate with maximum bioavailability demonstrated that BDE 209 accumulates in this species. Bioavailability depends on the exposure conditions, however, because BDE 209 in field sediments did not accumulate (<0.3 ng/g wet weight; 28-d biota-sediment accumulation factors [BSAFs] <0.001). When exposed to deca-BDE in spiked sediments also containing lower brominated congeners (a penta-BDE mixture), bioaccumulation of BDE 209 was 30 times lower than when exposed to deca-BDE alone. Selective accumulation of the lower brominated congeners supports their prevalence in higher trophic level species. The mechanisms responsible for limited accumulation of BDE 209 may involve characteristics of the sediment matrix and low transfer efficiency in the digestive fluid.

Fipronil effects on estuarine copepod (Amphiascus tenuiremis) development, fertility, and reproduction: a rapid life-cycle assay in 96-well microplate format.

Fipronil is a novel gamma-aminobutyric acid receptor-specific phenylpyrazole insecticide commonly used near estuarine environments for rice production, turf-grass management, and residential insect control. In this study, we evaluated the acute, developmental, and reproductive toxicity of fipronil to the estuarine harpacticoid copepod Amphiascus tenuiremis. Fipronil was highly toxic to A. tenuiremis (adult 96-h median lethal concentration [LC50] = 6.8 microg/L) and was more toxic to male copepods (96-h LC50 = 3.5 microg/L) than to nongravid female copepods (96-h LC50 = 13.0 microg/L). By using a newly developed 96-well microplate-based life-cycle toxicity test, we successfully reared single individuals of A. tenuiremis to adulthood in 200-microl microwells and concurrently assessed developmental and reproductive effects (after paired virginal matings) of environmentally relevant aqueous fipronil concentrations (0.16, 0.22, and 0.42 microg/L measured). Throughout the entire life cycle, copepod survival in all treatments was >90%. However, fipronil at 0.22 microg/L and higher significantly delayed male and female development from stage 1 copepodite to adult by approximately 2 d. More importantly, fipronil significantly halted female egg extrusion by 71% in the 0.22-microg/L fipronil treatment, and nearly eliminated reproduction (94% failure) in the 0.42-microg/L fipronil treatment. A three-generation Leslie matrix-based population growth model of fipronil reproductive and life-cycle impacts predicted a 62% decline in population size of A. tenuiremis relative to controls at only 0.16 microg/L.

A comparative assessment of azinphosmethyl bioaccumulation and toxicity in two estuarine meiobenthic harpacticoid copepods.

Aqueous, pore-water, and whole-sediment bioassays were conducted with meiobenthic copepods with different infaunal lifestyles to assess the acute and chronic toxicity of the organophosphorous pesticide azinphosmethyl (APM) and its bioaccumulation potential in sediments. Biota sediment accumulation factors were an order of magnitude higher for the deeper burrowing Amphiascus tenuiremis (26.6) than the epibenthic Microarthridion littorale (2.2). The female A. tenuiremis APM median lethal concentration (LC50; 3.6 microg/L) was twice the male LC50 (1.8 microg/L), in straight seawater exposures, and nearly 20% higher than males in whole-sediment exposures (540 vs 456 ng/g dry weight). Amphiascus tenuiremis were 17 times more sensitive to sediment-associated APM than M. littorale. In pore-water-only exposures, the adult mixed-sex A. tenuiremis LC50 (5.0 microg/L) was nearly twice the seawater mixed-sex LC50 (2.7 microg/L). Dissolved organic carbon in pore water was five times higher (20 mg/L) than in seawater-only exposures (4 mg/L). Differences in acute toxicity within exposure media were driven by species- and sex-specific differences in lipid content. Amphiascus tenuiremis likely experienced greater exposure to sediment-associated toxicants via longer periods of direct contact with pore water than M. littorale and, therefore, exhibited correspondingly higher bioaccumulation and acute toxicity. Copepod reproduction was significantly reduced (>60%) in 14-d sediment culture exposures at sublethal APM levels, suggesting that chronic field exposure to sediment-associated APM would result in sharp declines in copepod population growth.

Polycyclic aromatic hydrocarbon bioaccumulation by meiobenthic copepods inhabiting a superfund site: techniques for micromass body burden and total lipid analysis.

Microtechniques for polycyclic aromatic hydrocarbon (PAH) body burden and total lipid analysis were developed and applied to determine the first lipid-normalized bioaccumulation factors for a hydrophobic organic toxicant in a meiobenthic organism (0.063-0.500 mm) living in field-contaminated sediments. The total lipid microtechnique combines the standard Bligh-Dyer extraction method with a colorimetric quantification method for analysis of samples containing I to 50 microg lipid. The microtechnique for body burden analysis quantifies PAHs from tissue samples containing as little as 10 pg PAH. Fluoranthene, benz[a]anthracene, and benzo[a]pyrene biota-sediment accumulation factors (BSAFs) were determined for the meiobenthic copepod Microarthridion littorale living in an estuarine U.S. Environmental Protection Agency Superfund site. Gravid female, nongravid female, and male BSAFs were 0.82, 0.54, and 0.36, respectively, for fluoranthene; 0.50, 0.44, and 0.40, respectively, for benz[a]anthracene; and 0.09, 0.12, and 0.15, respectively, for benzo[a]pyrene. Comparison of nonlipid-normalized bioaccumulation factors (BAFs) to BSAFs indicates that M. littorale bioaccumulated PAHs on a gram lipid basis. The BSAFs declined consistently with increasing PAH log K(ow) for all copepod sex and reproductive stages. Sex- and stage-specific comparisons of BSAFs suggest that differences in lipid content and quality may lead to differences in BSAF values depending on PAH molecular weight and/or hydrophobicity.