Per- and polyfluoroalkyl substances (PFAS) in river discharge: Modeling loads upstream and downstream of a PFAS manufacturing plant in the Cape Fear watershed, North Carolina.

The Cape Fear River is an important source of drinking water in North Carolina, and many drinking water intakes in the watershed are affected by per- and polyfluoroalkyl substances (PFAS). We quantified PFAS concentrations and loads in river water upstream and downstream of a PFAS manufacturing plant that has been producing PFAS since 1980. River samples collected from September 2018 to February 2021 were analyzed for 13 PFAS at the upstream station and 43-57 PFAS downstream near Wilmington. Frequent PFAS sampling (daily to weekly) was conducted close to gauging stations (critical to load estimation), and near major drinking water intakes (relevant to human exposure). Perfluoroalkyl acids dominated upstream while fluoroethers associated with the plant made up about 47% on average of the detected PFAS downstream. Near Wilmington, Σ43PFAS concentration averaged 143 ng/L (range 40-377) and Σ43PFAS load averaged 3440 g/day (range 459-17,300), with 17-88% originating from the PFAS plant. LOADEST was a useful tool in quantifying individual and total quantified PFAS loads downstream, however, its use was limited at the upstream station where PFAS levels in the river were affected by variable inputs from a wastewater treatment plant. Long-term monitoring of PFAS concentrations is warranted, especially at the downstream station. Results suggest a slight downward trend in PFAS levels downstream, as indicated by a decrease in flow-weighted mean concentrations and the best-fitting LOADEST model. However, despite the cessation of PFAS process wastewater discharge from the plant in November 2017, and the phase-out of perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in North America, both fluoroethers and legacy PFAS continue to reach the river in significant quantities, reflecting groundwater discharge to the river and other continuing inputs. Persistence of PFAS in surface water and drinking water supplies suggests that up to 1.5 million people in the Cape Fear watershed might be exposed.

Demographic and dietary risk factors in relation to urinary metabolites of organophosphate flame retardants in toddlers.

Organophosphate flame retardants (OPFRs), including Tris (1,3-dichloro-isopropyl) phosphate (TDCPP), triphenyl phosphate (TPP), and isopropylated triphenyl phosphate (ITP), are increasingly used in consumer products because of the recent phase out of polybrominated diphenyl ether (PBDE) flame retardants. OPFRs have been widely detected in adults and have been linked to reproductive and endocrine changes in adult males. Carcinogenicity and damage to immunologic, neurologic and developmental systems have been observed in human cell lines. Young children are especially vulnerable to OPFR exposure, but little is known about exposure levels or exposure risk factors in this population. We examined parent-reported demographic and dietary survey data in relation to OPFR urinary metabolite concentrations in 15- to 18-month old toddlers (n = 41). OPFR metabolites were detected in 100% of subjects. The metabolite of TPP, diphenyl phosphate (DPP) was detected most commonly (100%), with TDCPP metabolite, bis(1,3-dichloro-2-propyl) phosphate (BDCPP), detected in 85-95% of samples, and ITP metabolite, monoisopropylphenyl phenyl phosphate (ip-DPP), detected in 81% of samples (n = 21). Toddlers of mothers earning <$10,000 annually had geometric mean DPP concentrations 66% higher (p = 0.05) than toddlers of mothers earning >$10,000/year (7.8 ng/mL, 95% CI 5.03, 12.11 and 4.69 ng/mL, 95% CI 3.65-6.04, respectively). While no dietary factors were significantly associated with OPFR metabolite concentrations, results suggested meat and fish consumption may be associated with higher DPP and BDCPP levels while increased dairy and fresh food consumption may be associated with lower DPP, BDCPP, and ip-DPP levels. Research with larger sample sizes and more detailed dietary data is required to confirm these preliminary findings.

A New Perspective on Sustainable Soil Remediation-Case Study Suggests Novel Fungal Genera Could Facilitate in situ Biodegradation of Hazardous Contaminants.

Deciding upon a cost effective and sustainable method to address soil pollution is a challenge for many remedial project managers. High pressure to quickly achieve cleanup goals pushes for energy-intensive remedies that rapidly address the contaminants of concern with established technologies, often leaving little room for research and development especially for slower treatment technologies, such as bioremediation, for the more heavily polluted sites. In the present case study, new genomic approaches have been leveraged to assess fungal biostimulation potential in soils polluted with particularly persistent hydrophobic contaminants. This new approach provides insights into the genetic functions available at a given site in a way never before possible. In particular, this article presents a case study where next generation sequencing (NGS) has been used to categorize fungi in soils from the Atlantic Wood Industries Superfund site in Portsmouth, Virginia. Data suggest that original attempts to harness fungi for bioremediation may have focused on fungal genera poorly suited to survive under heavily polluted site conditions, and that more targeted approaches relying on native indigenous fungi which are better equipped to survive under site specific conditions may be more appropriate.

Determining the ecological impacts of organic contaminants in biosolids using a high-throughput colorimetric denitrification assay: a case study with antimicrobial agents.

Land application accounts for ∼ 50% of wastewater solid disposal in the United States. Still, little is known regarding the ecological impacts of nonregulated contaminants found in biosolids. Because of the myriad of contaminants, there is a need for a rapid, high-throughput method to evaluate their ecotoxicity. Herein, we developed a novel assay that measures denitrification inhibition in a model denitrifier, Paracoccus denitrificans Pd1222. Two common (triclosan and triclocarban) and four emerging (2,4,5 trichlorophenol, 2-benzyl-4-chlorophenol, 2-chloro-4-phenylphenol, and bis(5-chloro-2-hydroxyphenyl)methane) antimicrobial agents found in biosolids were analyzed. Overall, the assay was reproducible and measured impacts on denitrification over 3 orders of magnitude exposure. The lowest observable adverse effect concentrations (LOAECs) were 1.04 µM for triclosan, 3.17 µM for triclocarban, 0.372 µM for bis-(5-chloro-2-hydroxyphenyl)methane, 4.89 µM for 2-chloro-4-phenyl phenol, 45.7 µM for 2-benzyl-4-chorophenol, and 50.6 µM for 2,4,5-trichlorophenol. Compared with gene expression and cell viability based methods, the denitrification assay was more sensitive and resulted in lower LOAECs. The increased sensitivity, low cost, and high-throughput adaptability make this method an attractive alternative for meeting the initial testing regulatory framework for the Federal Insecticide, Fungicide, and Rodenticide Act, and recommended for the Toxic Substances Control Act, in determining the ecotoxicity of biosolids-derived emerging contaminants.

Analysis of the flame retardant metabolites bis(1,3-dichloro-2-propyl) phosphate (BDCPP) and diphenyl phosphate (DPP) in urine using liquid chromatography-tandem mass spectrometry.

Organophosphate triesters tris(1,3-dichloro-2-propyl) phosphate (TDCPP) and triphenyl phosphate are widely used flame retardants (FRs) present in many products common to human environments, yet understanding of human exposure and health effects of these compounds is limited. Monitoring urinary metabolites as biomarkers of exposure can be a valuable aid for improving this understanding; however, no previously published method exists for the analysis of the primary TDCPP metabolite, bis(1,3-dichloro-2-propyl) phosphate (BDCPP), in human urine. Here, we present a method to extract the metabolites BDCPP and diphenyl phosphate (DPP) in human urine using mixed-mode anion exchange solid phase extraction and mass-labeled internal standards with analysis by atmospheric pressure chemical ionization liquid chromatography tandem mass spectrometry. The method detection limit was 8 pg mL(-1) urine for BDCPP and 204 pg mL(-1) for DPP. Recoveries of analytes spiked into urine ranged from 82 ± 10% to 91 ± 4% for BDCPP and from 72 ± 12% to 76 ± 8% for DPP. Analysis of a small number of urine samples (n=9) randomly collected from non-occupationally exposed adults revealed the presence of both BDCPP and DPP in all samples. Non-normalized urinary concentrations ranged from 46-1,662 pg BDCPP mL(-1) to 287-7,443 pg DPP mL(-1), with geometric means of 147 pg BDCPP mL(-1) and 1,074 pg DPP mL(-1). Levels of DPP were higher than those of BDCPP in 89% of samples. The presented method is simple and sufficiently sensitive to detect these FR metabolites in humans and may be applied to future studies to increase our understanding of exposure to and potential health effects from FRs.

Evaluating daily exposure to polychlorinated biphenyls and polybrominated diphenyl ethers in fish oil supplements.

Fish oil supplements have become a popular means of increasing one's dietary intake of essential polyunsaturated fatty acids. However, there is growing concern that the levels and potential health effects of lipophilic organic contaminants such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) may diminish some of the health benefits associated with the daily consumption of fish oil supplements. In this study, ten over-the-counter fish oil supplements available in the United States were analysed for PCBs and PBDEs and daily exposures calculated. Based on manufacturers' recommended dosages, daily intakes of PCBs and PBDEs ranged from 5 to 686 ng day(-1) and from 1 to 13 ng day(-1), respectively. Daily consumption of fish oil supplements expose consumers to PCBs and PBDEs. However, in comparison with fish ingestion, fish supplements may decrease daily PCB exposure and provide a safer pathway for individuals seeking to maintain daily recommended levels of polyunsaturated fatty acids.

Determination of HBCD, PBDEs and MeO-BDEs in California sea lions (Zalophus californianus) stranded between 1993 and 2003.

Blubber samples from male California sea lions (Zalphophus californianus) stranded between 1993 and 2003 were analyzed for 27 polybrominated diphenyl ether (PBDE) congeners, three isomers of hexabromocyclododecane (HBCD) and 14 methoxylated polybrominated diphenyl ether (MeO-BDE) congeners. Total PBDEs ranged from 450 ng/g to 4740 ng/g wet mass and total HBCD ranged from < 0.3 ng/g to 12 ng/g wet mass. The concentration of HBCD increased from 0.7 ng/g to12.0 ng/g wet mass in sea lion blubber between 1993 and 2003. However, no significant temporal trend was observed for any of the other brominated compounds over this 10 year period. Only one of the 14 MeO-BDE congeners was detected in the blubber samples, 6-methoxy-2,2',4,4'-tetrabromodiphenyl ether (6-MeO-BDE 47), and concentrations ranged from < 0.2 ng/g to 12 ng/g wet mass. A bromo-, chloro-heterocyclic compound, 1,1'-dimethyl-tetrabromo-dichloro-2,2'-bipyrrole (DBP-Br4Cl2), previously reported in marine species along the Pacific coast, was also identified in the sea lion blubber. DBP-Br4Cl2 ranged from 44 ng/g wet mass to 660 ng/g wet mass and was present at concentrations rivaling the dominant PBDE congener, BDE 47 (2,2',4,4'-tetrabromodiphenyl ether). Concentrations of DBP-Br4Cl2 were positively correlated with 6-MeO-BDE 47 (r = 0.7; p < 0.05). Both of these compounds have been identified in marine algae and sponges, and studies suggest they are both produced from natural sources. This study demonstrates that brominated compounds from both anthropogenic and biogenic sources can accumulate to similar levels in marine mammals. In addition, HBCD concentrations appear to be increasing in California sea lion populations, whereas PBDE concentrations, between 1993 and 2003, were highly variable.

Comparing polybrominated diphenyl ether and polychlorinated biphenyl bioaccumulation in a food web in Grand Traverse Bay, Lake Michigan.

Levels of polybrominated diphenyl ethers (BDEs) in Great Lakes salmonids and ambient air have been recently reported, but few studies worldwide have examined the accumulation of BDEs within aquatic food webs. Here we report some of the first measurements of six BDE congeners that are common components of the pentaBDE commercial mixture within an entire Lake Michigan food web. BDEs were detected in all samples and the dominant BDE congener was 2,2',4,4'-tetrabromodiphenyl ether (BDE 47). BDE 47 levels were consistently greater than those of the 2,2',4,4',5-pentabromodiphenyl ether (BDE 99), despite similar levels of these two compounds in commercial mixtures, suggesting differences in the bioavailability of the BDE congeners or differences in their ability to be metabolized. Additionally, congener composition was significantly different among deepwater sculpin, bloater chub, and lake trout, indicating differences in exposure or differences in biotransformation capacities. Total BDE concentrations in this food web were positively correlated (r = 0.94) with levels of PCBs previously measured in these samples (Stapleton et al. 2001a). Levels of BDE 47 and PCB 153, compounds with similar physicochemical properties, were compared to examine the relative exposure and bioaccumulation of these two classes of chemicals that have different environmental loading histories. Food web magnification factors calculated for these two congeners were 3.2 and 4.0 for BDE 47 and PCB 153, respectively, indicating a comparable potential for biomagnification in food webs.

Recent declines in PAH, PCB, and toxaphene levels in the northern Great Lakes as determined from high resolution sediment cores.

Sediment cores were collected from two sites in Grand Traverse Bay, Lake Michigan in May 1998, dated using 210Pb geochronology, and analyzed for polychlorinated biphenyl (PCB) congeners, polycyclic aromatic hydrocarbons (PAHs), and toxaphene. The extraordinarily high sediment focusing and accumulation rates in these cores relative to other Great Lakes sediments allowed quantification of high-resolution temporal trends in the burial of hydrophobic organic contaminants. The focus-corrected accumulation rate of total PCBs (sum of 105 congeners) in 1998 was 0.50 ng/cm2-year at both sites. Toxaphene and total PAH (t-PAH; sum of 33 compounds) surficial accumulations varied at each site and ranged from 0.08 to 0.41 ng/cm2-year for toxaphene and 25 to 52 ng/cm2-yr for t-PAHs at the two sites. The maximum t-PAH accumulation rate was in sediment dated from 1942, and PAH accumulation decreased from 1942 to 1980 with a first-order rate of decline 0.017 yr(-1). Both toxaphene and t-PCB accumulations peaked in sediment deposited in 1972, afterwhich their accumulations decreased with nearly identical rates of decline (0.027 yr(-1) and 0.028 yr(-1), respectively).

Accumulation of atmospheric and sedimentary PCBs and toxaphene in a Lake Michigan food web.

Seston, sediment, settling organic matter, and food web members were collected from Grand Traverse Bay, Lake Michigan, between April 1997 and September 1998 to examine PCB and toxaphene biomagnification. Stable isotopes of nitrogen and carbon were analyzed in samples and used to establish trophic structure of the food web and to determine the importance of atmospheric versus sedimentary sources in delivering PCBs to the food web. Nitrogen isotopes were confounded by multiple variables in this system, particularly seasonal variation, and did not display a simple pattern of enrichment among trophic levels. However, delta13C displayed little seasonal variation and was positively correlated with PCB concentrations among food web members (r2 = 0.69). Plots of delta13C vs PCBs separate food web members into three distinct groupings comprised of invertebrates, primary forage fish, and predatory fish. Stable isotope values of the primary organic sources indicate that the atmosphere, and not the sediment, is the most likely source of PCBs to the food web of Lake Michigan. Additionally, we suggest that seston may be important in delivering PCBs to pelagic food web members and species that receive a majority of their nutrition through pelagic sources. In contrast, settling particles are implicated in delivering PCBs to benthic organisms and Mysis relicta.

Metabolism of PCBs by the deepwater sculpin (Myoxocephalus thompsoni).

Methylsulfonyl-PCBs (MeSO2-PCBs) are hydrophobic organic contaminants that bioaccumulate in the environment similar to their parent molecules, PCBs. Previously, MeSO2-PCBs have primarily been identified in tissues of birds, humans, and other mammals. However, evidence now supports formation of these metabolites in deepwater sculpin, Myoxocephalus thompsoni, a benthic forage fish predominant in the Great Lakes. The ability of deepwater sculpin to form MeSO2-PCBs is unprecedented for a freshwater fish species and presents a novel biochemical pathway for organochlorine metabolism. Additionally, this appears to be a unique PCB metabolic pathway resulting in a reduction of as much as 10% in the sculpin PCB burden, which is further transformed into another class of organic contaminants in the Great Lakes ecosystem.