Perfluorooctanoic acid dominates the molecular-level effects of a mixture of equal masses of perfluorooctanoic acid and perfluorooctane sulfonic acid in earthworm.

Per- and polyfluoroalkyl substances (PFAS) are an important class of emerging contaminants in the environment. Most studies on the impact of PFAS mixtures considered phenotypic endpoints, which may not adequately reflect the sublethal effects on organisms. To fill this knowledge gap, we investigated the subchronic impact of environmentally relevant concentrations of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS)-as individual compounds and a mixture (PFOS+PFOA)-on earthworm (Eisenia fetida), using phenotypic and molecular endpoints. PFAS decreased the survival (12.2-16.3%), biomass (9.0-9.8%), and reproduction (15.6-19.8%) of E. fetida after 28 d of exposure. The bioaccumulation of PFOS after 28 d increased (from 2790.7 ng/g-dw to 5224.9 ng/g-dw) while that of PFOA decreased (from 780.2 ng/g-dw to 280.5 ng/g-dw) when E. fetida was exposed to the mixture compared to the individual compounds. These bioaccumulation trends were partly attributed to changes in the soil distribution coefficient (Kd) of PFOS and PFOA when present in the mixture. Eighty percent of the (p and FDR < 0.05) altered metabolites after 28 d were similarly perturbed by both PFOA and PFOS+PFOA. The pathways dysregulated are related to the metabolism of amino acids, energy, and sulfur. We showed that PFOA dominates the molecular-level impact of the binary PFAS mixture.

Perfluoroalkyl acid transformation and mitigation by nNiFe-activated carbon nanocomposites in steady-state flow column studies.

The ongoing contamination of groundwater with per- and polyfluoroalkyl substances (PFAS) has resulted in a global and rapidly growing interest in PFAS groundwater remediation. Preferred technologies that lead to PFAS destruction are often limited by not addressing all PFAS, being energy-intensive or not being suited for in-situ application. We developed nNiFe-activated carbon (AC) nanocomposites and demonstrated varying degrees of PFAS reduction and fluoride generation with these nanocomposites in batch reactors for several PFAS. Here we explore nNiFe-AC's effectiveness to transform perfluoroalkyl acid acids (PFAAs) under steady-state flow (0.0044 to 0.15 mL/min) in nNiFe-AC:sand packed columns. Column experiments included, two perfluorooctane sulfonate (PFOS) in deionized water and two PFAA mixtures in deionized water or bicarbonate buffer containing five perfluoroalkyl carboxylates (PFCAs, C5-C9) and three perfluoroalkyl sulfonates (PFSAs, C4, C6 and C8) at temperatures of 50 or 60°C were evaluated. PFOS transformation was similar in PFOS-only and PFAA mixture column experiments. Overall, % PFAA transformation under flow conditions exceeded what we observed previously in batch reactors with up to 53% transformation of a PFAA mixture with ∼ 8% defluorination. Longer chain PFAS dominated the PFAAs transformed and a bicarbonate matrix appeared to reduce overall transformation. PFAA breakthrough was slower than predicted from only sorption due to transformation; some longer chain PFAS like PFOS did not breakthrough. Here, nNiFe-AC technology with both in-situ and ex-situ potential application was shown to be a plausible part of a treatment train needed to address the ongoing challenge for cleaning up PFAS-contaminated waters.

Abundance, fate, and effects of pharmaceuticals and personal care products in aquatic environments.

Pharmaceuticals and personal care products (PPCPs) are found in wastewater, and thus, the environment. In this study, current knowledge about the occurrence and fate of PPCPs in aquatic systems-including wastewater treatment plants (WWTPs) and natural waters around the world-is critically reviewed to inform the state of the science and highlight existing knowledge gaps. Excretion by humans is the primary route of PPCPs entry into municipal wastewater systems, but significant contributions also occur through emissions from hospitals, PPCPs manufacturers, and agriculture. Abundance of PPCPs in raw wastewater is influenced by several factors, including the population density and demography served by WWTPs, presence of hospitals and drugs manufacturers in the sewershed, disease burden of the population served, local regulations, and climatic conditions. Based on the data obtained from WWTPs, analgesics, antibiotics, and stimulants (e.g., caffeine) are the most abundant PPCPs in raw wastewater. In conventional WWTPs, most removal of PPCPs occurs during secondary treatment, and overall removal exceeds 90% for treatable PPCPs. Regardless, the total PPCP mass discharged with effluent by an average WWTP into receiving waters (7.35-20,160 g/day) is still considerable, because potential adverse effects of some PPCPs (such as ibuprofen) on aquatic organisms occur within measured concentrations found in surface waters.

Reductive transformation of perfluorooctanesulfonate by nNiFe0-Activated carbon.

Degradation of linear (L) and branched (Br) perfluorooctanesulfonate (PFOS) using nNiFe° particles supported on activated carbon (AC) and heat is demonstrated for the first time and with several lines of evidence. At 60 °C, PFOS degradation plateaued at 50 ± 6%, while at 50 °C, 94 ± 4.1 % PFOS transformed. The accelerated iron corrosion at the higher temperature is attributed to the lower PFOS transformation at 60 °C. However, at both temperatures, ≥ 97 % of the PFOS transformed was accounted for by the moles of fluoride generated. At 60 °C, PFOS degradation rates were estimated at 0.028 ± 0.003 h-1 and fluoride and sulfite generation rates of 0.70 ± 0.165 h-1 and 0.62 ± 0.157 h-1, respectively, with no differences between L-PFOS and total Br-PFOS. Using time-of-flight mass spectrometry, some organic products were identified in the particle extracts from the 60 °C reaction. Products included single-bonded C8 polyfluoroalkyl sulfonates (F16 to F7) and alkyl acids (PFCAs, C4-C8) and one perfluorinated C8 desulfonated product supporting both defluorination and desulfonation pathways. Most of the organic products were gone after the first 25 h. High PFOS mineralization using nNiFe°-AC technology warrants further investigation for its use in permeable reactive barriers.

How Do We Measure Poly- and Perfluoroalkyl Substances (PFASs) at the Surface of Consumer Products?: Environmental Science and Technology LETTERS.

Exposures to poly- and perfluoroalkyl substances (PFASs) have been linked to metabolic disruption, immunotoxicity and cancer in humans. PFASs are known to be present in diverse consumer products including textiles and food packaging. Here we present a new method for quantifying the atomic percent fluorine (% F) in the surficial 0.01 µm of consumer products using X-ray photoelectron spectroscopy (XPS). The surface of food contact materials and textiles measured in this study contained up to 28% F and 45% F, respectively. PTFE tape was measured to demonstrate XPS accuracy and precision. Depth profiles of fluorine content in consumer products measured using XPS showed highest levels at the upper-most surface in contact with the surrounding environment and a decrease below the surface. PFASs released in methanol extracts and quantified using traditional liquid chromatography-tandem mass spectrometry typically accounted for <1% of the fluorine measured with XPS in consumer products. We conclude that XPS is a useful technique for characterizing PFASs in consumer products because it can precisely quantify the surficial fluorine content of materials. XPS also allows identification of CF2 and CF3 groups in materials and can elucidate the depth dependent distribution of fluorine in products.

Perfluorooctane sulfonate (PFOS) removal with Pd0/nFe0 nanoparticles: Adsorption or aqueous Fe-complexation, not transformation?

PFOS removal at 6 and 21days (d) when reacted with palladium coated zero valent iron nanoparticles (Pd0/nFe0 NPs) was quantified as a function of pH (3.6, 5.5, and 8.7) and temperature (22, 45 and 70°C). PFOS concentrations were measured in aqueous phases and NP extracts. The greatest PFOS removal occurred at 6 d with the lowest pH and highest temperature; however, recovered PFOS increased at 21 d. Furthermore, neither F- nor SO42- (from SO32- cleavage) generation was observed indicating the absence of PFOS transformation. X-ray diffraction analysis of PFOS-reacted NPs at 45°C revealed generation of FeO(OH) on the NPs at 21 d, which was concomitant with subsequent increases in PFOS recovery. Under anaerobic conditions, strongly adsorbing Fe(OH)3 is formed which can then transform to less sorptive FeO(OH) via Fe2+ catalyzed transformation. In the process of exploring causes for apparent PFOS removal with Pd0/nFe0 NPs, PFOS as well as other perfluoroalkyl acids (PFAAs) were found to form aqueous-phase complexes with Fe(II/III) which can reduce their quantifiable levels. PFOS-Fe complexation was greater with Fe(III) and increased with Fe concentration and decreasing pH. Complexation was also greater for longer chain perfluoroalkyl acids and complexation of PFNA was greater than for PFOS.

Presence and effects of pharmaceutical and personal care products on the Baca National Wildlife Refuge, Colorado.

Pharmaceuticals and personal care products (PPCPs) have raised concerns due to their potential effects to aquatic organisms. These chemicals appear in mixtures at very low concentrations thus making their detection and quantification difficult. Polar organic chemical integrative samplers (POCIS) concentrate trace levels of chemicals over time increasing method sensitivity and thus represent a cost-effective screening tool for biomonitoring studies. The Baca National Wildlife Refuge (BNWR), Colorado, is home for several endemic fish species, including Rio Grande chub (Gila pandora). The objectives of this study were to (1) determine the types and concentrations of PPCPs in the Refuge, (2) compare and contrast two methods (grab and POCIS) for the quantification of PPCPs from surface water, and (3) determine effects due to PPCP exposure in fish. Between 2011 and 2013, 141 PPCPs were quantified using a combination of grab samples and POCIS. Although no PPCPs were detected from the grab samples, high concentrations of N,N-Diethyl-meta-toluamide (DEET) and triclosan were detected in all fish sampling sites with POCIS. Fathead minnows (Pimephales promelas) and Rio Grande chubs of both sexes were collected in 2011 and 2012. Several biological responses were observed in both species from creeks contaminated with PPCPs; however the presence of PPCPs in the reference site did not allow for valid data comparison and interpretation. We conclude that POCIS is a sensitive method for the detection and quantification of PPCPs and for identification of reference sites and that appropriate "reference" sites need to be identified at the BNWR for follow-up studies with native fish.

Effects of triclocarban, N,N-diethyl-meta-toluamide, and a mixture of pharmaceuticals and personal care products on fathead minnows (Pimephales promelas).

Pharmaceuticals and personal care products (PPCPs) have been detected widely in aquatic ecosystems, but little is known about their mechanisms of toxicity. We exposed adult fathead minnows (Pimephales promelas) for 48 h to triclocarban (1.4 µg/L), N,N-diethyl-meta-toluamide (DEET; 0.6 µg/L), or a mixture of PPCPs consisting of atenolol (1.5 µg/L), caffeine (0.25 µg/L), diphenhydramine (0.1 µg/L), gemfibrozil (1.5 µg/L), ibuprofen (0.4 µg/L), naproxen (1.6 µg/L), triclosan (2.3 µg/L), progesterone (0.2 µg/L), triclocarban (1.4 µg/L), and DEET (0.6 µg/L). Quantitative real-time polymerase chain reaction revealed an upregulation in vitellogenin (vtg) in livers of females and males exposed to triclocarban. Also, an upregulation of hepatic lipoprotein lipase (lpl) and a downregulation of androgen receptor (ar) and steroidogenic acute regulatory protein (star) were observed in testes. The group treated with DEET only showed a significant decrease in ar in females. In contrast, the PPCP mixture downregulated vtg in females and males and expression of estrogen receptor alpha (erα), star, and thyroid hormone receptor alpha 1 (thra1) in testes. The authors' results show that the molecular estrogenic effects of triclocarban are eliminated (males) or reversed (females) when dosed in conjunction with several other PPCP, once again demonstrating that results from single exposures could be vastly different from those observed with mixtures. Environ Toxicol Chem 2014;33:910-919. © 2013 SETAC.