M. Coreen Hamilton

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.

Risk-based consumption advice for farmed Atlantic and wild Pacific salmon contaminated with dioxins and dioxin-like compounds

We reported recently that several organic contaminants occurred at elevated concentrations in farmed Atlantic salmon compared with concentrations of the same contaminants in wild Pacific salmon [Hites et al. Science 303:226–229 (2004)]. We also found that polychlorinated biphenyls (PCBs), toxaphene, dieldrin, dioxins, and polybrominated diphenyl ethers occurred at higher concentrations in European farm-raised salmon than in farmed salmon from North and South America. Health risks (based on a quantitative cancer risk assessment) associated with consumption of farmed salmon contaminated with PCBs, toxaphene, and dieldrin were higher than risks associated with exposure to the same contaminants in wild salmon. Here we present information on cancer and noncancer health risks of exposure to dioxins in farmed and wild salmon. The analysis is based on a tolerable intake level for dioxin-like compounds established by the World Health Organization and on risk estimates for human exposure to dioxins developed by the U.S. Environmental Protection Agency. Consumption of farmed salmon at relatively low frequencies results in elevated exposure to dioxins and dioxin-like compounds with commensurate elevation in estimates of health risk.

A survey of metals in tissues of farmed Atlantic and wild Pacific salmon

Contamination of fish tissues with organic and inorganic contaminants has been a pervasive environmental and public health problem. The present study reports the concentrations of nine metals in tissues of farmed Atlantic salmon (Salmo salar) and two species of wild-caught salmon (chum [Oncorhynchus keta] and coho [O. kisutch]) analyzed as part of a global survey of contaminants in these fish. Of the nine metals, organic arsenic was significantly higher in farmed than in wild salmon, whereas cobalt, copper, and cadmium were significantly higher in wild salmon. None of the contaminants exceeded federal standards or guidance levels.

PCB, PCDD and PCDF congener profiles in two types of Aroclor 1254.

Monsanto produced two distinct variants of Aroclor 1254. The late-production variant resulted from a change in Monsantos manufacturing process in the early 1970s. Previous literature had reported that the late-production variant was produced from 1974 to 1976, but subsequent work has identified a sample known to be obtained in 1972. In this paper, we present congener-specific PCB and PCDD/F data for this 1972 late-production sample, and a brief historical record of late-production Aroclor 1254.

Quantitative determination of 13 organophosphorous flame retardants and plasticizers in a wastewater treatment system by high performance liquid chromatography tandem mass spectrometry

A method for quantitative determination of 13 organophosphorous compounds (OPs) was developed and applied to influent, primary sludge, activated sludge, biosolids, primary effluent and final effluent from a wastewater treatment plant (WWTP). The method involved solvent extraction followed by solid phase clean-up and analysis by high performance liquid chromatography positive electrospray ionization-tandem mass spectrometry (HPLC(+ESI)MS/MS). Replicate spike/recovery experiments revealed the method to have good accuracy (70-132%) and precision (<19% RSD) in all matrices. Detection limits of 0.1-5 ng/L for aqueous samples and 0.01-0.5 ng/g for solid samples were achieved. In the liquid waste stream ∑OP concentrations were highest in influent (5764 ng/L) followed by primary effluent (4642 ng/L), and final effluent (2328 ng/L). In the solid waste stream, the highest ∑OP concentrations were observed in biosolids (3167 ng/g dw), followed by waste activated sludge (2294 ng/g dw), and primary sludge (2128 ng/g dw). These concentrations are nearly 30-fold higher than ∑polybrominated diphenyl ether (BDE) concentrations in influents and nearly 200-fold higher than ∑BDE concentrations in effluents from other sites in Canada. Tetrekis(2-chlorethyl)dichloroisopentyldiphosphate (V6), tripropylphosphate (TnPrP), and Tris(2,3-dibromopropyl)phosphate (TDBPP) are investigated for the first time in a WWTP. While TnPrP and TDBB were not detected, V6 was observed at concentrations up to 7.9 ng/g in solid waste streams and up to 40.7 ng/L in liquid waste streams. The lack of removal of OPs during wastewater treatment is a concern due to their release into the aquatic environment.

Sorption of per- and polyfluoroalkyl substances (PFASs) on filter media: implications for phase partitioning studies.

Per- and polyfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are ubiquitous in the environment. Investigations into their fate and potential phase-partitioning behavior require separating solid from aqueous phases via filtration. However, sorption of aqueous-phase PFASs on filtration media may lead to underestimation of PFAS concentrations in the aqueous phase. The authors investigated the sorption of perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids (PFPiAs), polyfluoroalkyl phosphate monoesters, polyfluoroalkyl phosphate diesters (diPAPs), fluorotelomer sulfonates, and perfluorooctane sulfonamide on filtration media. The effects of concentration (3 spiking levels), filter media (4 types), matrix (4 matrices), and compound structure on sorption are reported. Glass fiber filtration resulted in the least sorption, whereas polytetrafluoroethylene filters resulted in the most sorption (up to 98%). Analyte concentration had no significant effect. Sorption was generally consistent across matrix types except for samples affected by aqueous film forming foam deployment, which displayed high sorption of PFOS on nylon filters. Sorption usually increased with an increasing number of carbon or fluorine atoms and was most pronounced for PFPiAs and diPAPs (30–75% sorption). Overall, glass fiber filters are more recommended than nylon filters in environmental samples when phase separation is required. Use of filtration media for PFAS must be preceded by matrix-specific testing to account for unpredictable effects.

The quantification of toxaphene in environmental samples

Abstract A simplified analytical method is described for the determination of toxaphene in environmental samples by electron capture negative ion GC/MS using internal standards. The method allows toxaphene to be determined at the low ppb level in the presence of PCBs for a variety of sample matrices including sediment and biological tissue. Toxaphene is quantified from the total peak area response for 21 prominent components using mass chromatograms of the characteristic polychlorobornane [M-Cl] − ions. The quantitation method shows minimal interference from PCB congeners, or from compounds in the chlordane group. Performance was evaluated using a cod liver oil NIST 1588 standard reference material. The effect of oxygen pressure on PCB interference and toxaphene quantitation is discussed.

Pharmaceuticals and other anthropogenic tracers in surface water: A randomized survey of 50 Minnesota lakes

Water from 50 randomly selected lakes across Minnesota, USA, was analyzed for pharmaceuticals, personal care products, hormones, and other commercial or industrial chemicals in conjunction with the US Environmental Protection Agencys 2012 National Lakes Assessment. Thirty-eight of the 125 chemicals analyzed were detected at least once, all at parts per trillion concentrations. The most widely detected was N,N-diethyl-m-toluamide, present in 48% of the lakes sampled. Amitriptyline, a widely used antidepressant, was found in 28% of the lakes. The endocrine active chemicals bisphenol A, androstenedione, and nonylphenol were found in 42%, 30%, and 10% of the lakes, respectively. Cocaine was found in 32% of the lakes, and its degradation product, benzoylecgonine, was detected at 28% of the locations. Carbadox, an antibiotic used solely in the production of swine, was also present in 28% of the lakes sampled. The means by which these and other chemicals were transported to several of the remote lakes is unclear but may involve atmospheric transport.

Pharmaceuticals and other anthropogenic chemicals in atmospheric particulates and precipitation

Air and precipitation samples were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) and gas chromatography mass spectrometry (GC-MS) for pharmaceuticals, personal care products, and other commercial chemicals within the St. Paul/Minneapolis metropolitan area of Minnesota, U.S. Of the 126 chemicals analyzed, 17 were detected at least once. Bisphenol A, N,N-diethyl-meta-toluamide (DEET), and cocaine were the most frequently detected; their maximum concentrations in snow were 3.80, 9.49, and 0.171ng/L and in air were 0.137, 0.370, and 0.033ng/m3, respectively. DEET and cocaine were present in samples of rain up to 14.5 and 0.806ng/L, respectively. Four antibiotics - ofloxacin, ciprofloxacin, enrofloxacin, and sulfamethoxazole - were detected at concentrations up to 10.3ng/L in precipitation, while ofloxacin was the sole antibiotic detected in air at 0.013ng/m3. The X-ray contrast agent iopamidol and the non-steroidal anti-inflammatory drug naproxen were detected in snow up to 228ng/L and 3.74ng/L, respectively, while caffeine was detected only in air at 0.069 and 0.111ng/m3. Benzothiazole was present in rain up to 70ng/L, while derivatives of benzotriazole - 4-methylbenzotriazole, 5-methylbenzotriazole, and 5-chlorobenzotriazole - were detected at concentrations up to 1.5ng/L in rain and 3.4ng/L in snow. Nonylphenol and nonylphenol monoethoxylate were detected once in air at 0.165 and 0.032ng/m3, respectively. Although the sources of these chemicals to atmosphere are not known, fugacity analysis suggests that wastewater may be a source of nonylphenol, nonylphenol monoethoxylate, DEET, and caffeine to atmosphere. The land-spreading of biosolids is known to generate PM10 that could also account for the presence of these contaminants in air. Micro-pollutant detections in air and precipitation are similar to the profile of contaminants reported previously for surface water. This proof of concept study suggests that atmospheric transport of these chemicals may partially explain the ubiquity of these contaminants in the aquatic environment.

Quantitative determination of hydroxy polycylic aromatic hydrocarbons as a biomarker of exposure to carcinogenic polycyclic aromatic hydrocarbons.

A high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) method was developed for quantitative analysis of hydroxy polycyclic aromatic hydrocarbons (OH-PAHs). Four hydroxy metabolites of known and suspected carcinogenic PAHs (benzo[a]pyrene (B[a]P), benz[a]anthracene (B[a]A), and chrysene (CRY)) were selected as suitable biomarkers of PAH exposure and associated risks to human health. The analytical method included enzymatic deconjugation, liquid - liquid extraction, followed by derivatization with methyl-N-(trimethylsilyl) trifluoroacetamide and instrumental analysis. Photo-induced oxidation of target analytes - which has plagued previously published methods - was controlled by a combination of minimizing exposure to light, employing an antioxidant (2-mercaptoethanol) and utilizing a nitrogen atmosphere. Stability investigations also indicated that conjugated forms of the analytes are more stable than the non-conjugated forms. Accuracy and precision of the method were 77.4-101% (<4.9% RSD) in synthetic urine and 92.3-117% (<15% RSD) in human urine, respectively. Method detection limits, determined using eight replicates of low-level spiked human urine, ranged from 13 to 24pg/mL. The method was successfully applied for analysis of a pooled human urine sample and 78 mouse urine samples collected from mice fed with PAH-contaminated diets. In mouse urine, greater than 94% of each analyte was present in its conjugated form.