A Comparative Biodegradation Study to Assess the Ultimate Fate of Novel Highly Functionalized Hydrofluoroether Alcohols in Wastewater Treatment Plant Microcosms and Surface Waters.

Per- and polyfluoroalkyl substances (PFAS) are a class of chemicals present in a wide range of commercial and consumer products due to their water-repellency, nonstick, or surfactant properties, resulting from their chemical and thermal stability. This stability, however, often leads to persistence in the environment when they are inevitability released. We utilized microbial microcosms from wastewater treatment plant (WWTP) sludge to determine how employing different functional groups such as heteroatom linkages, varying chain lengths, and hydrofluoroethers (HFEs) will impact the ultimate fate of these novel PFAS structures. A suite of five novel fluorosurfactant building blocks (F7 C3 OCHFCF2 SCH2 CH2 OH (FESOH), F3 COCHFCF2 SCH2 CH2 OH (MeFESOH), F7 C3 OCHFCF2 OCH2 CH2 OH (ProFdiEOH), F7 C3 OCHFCF2 CH2 OH (ProFEOH), and F3 COCHFCF2 OCH2 CH2 OH (MeFdiEOH)) and their select transformation products, were incubated in WWTP aerobic microcosms to determine structure-activity relationships. The HFE alcohol congeners with a thioether (FESOH and MeFESOH) were observed to transform faster than the ether congeners, while also producing second-generation HFE acid products (F7 C3 OCHFC(O)OH (2H-3:2 polyfluoroalkyl ether carboxylic acid [PFECA]) and F3 COCHFC(O)OH (2H-1:2 PFECA). Subsequent biodegradation experiments with 2H-1:2 PFESA and 2H-1:2 PFECA displayed no further transformation over 74 days. Surface water Photofate experiments compared 2H-1:2 PFECA, and 2H-1:2 polyfluorinated ether sulfonate (PFESA) with their fully fluorinated ether acid counterparts, and demonstrated the potential for both HFE acid species to completely mineralize over extended periods of time, a fate that highlights the value of studying novel PFAS functionalization. Environ Toxicol Chem 2024;00:1-9. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Avoiding Regrettable Replacements: Can the Introduction of Novel Functional Groups Move PFAS from Recalcitrant to Reactive?

Per- and polyfluoroalkyl substances (PFASs) are present in a range of commercial and consumer products. These chemicals are often high-performance surfactants or nonstick/water-repellant coatings due to their chemical stability; however, this stability leads to select PFAS being environmentally persistent. To facilitate degradation, new fluorosurfactant building blocks (F7C3-O-CHF-CF2-S-CH2-CH2-OH (FESOH), F3C-O-CHF-CF2-S-CH2-CH2-OH (MeFESOH), F7C3-O-CHF-CF2-O-CH2-CH2-OH (ProFdiEOH), F7C3-O-CHF-CF2-CH2-OH (ProFEOH), and F3C-O-CHF-CF2-O-CH2-CH2-OH (MeFdiEOH)) have been systematically developed with heteroatom linkages such as ethers, thioethers, and polyfluorinated carbons. The room temperature, gas-phase OH oxidation rate constants, and products of these chemicals were monitored in an atmospheric chamber to investigate their fate in the atmosphere. Analysis was performed using online high-resolution chemical ionization mass spectrometry (CIMS) using the iodide reagent ion and via offline UPLC-MS/MS. FESOH and MeFESOH, the thioether congeners, were observed to have the largest rate constants of kFESOH = 2.82 (±0.33) and kMeFESOH = 2.17 (±0.17) (×10-12 cm3 molecules-1 s-1, respectively). First-, second-, and third-generation products of OH oxidation were observed as a function of time, while product quantification yielded ultrashort perfluoropropionic acid (PFPrA) and short polyfluoroether acid species as the terminal products for FESOH and ProFdiEOH. There was evidence for MeFESOH being fully mineralized, demonstrating the potential benign chemical architecture.

Occurrence, Fate, Human Exposure, and Toxicity of Commercial Photoinitiators.

Photoinitiators (PIs) are a family of anthropogenic chemicals used in polymerization systems that generate active substances to initiate polymerization reactions under certain radiations. Although polymerization is considered a green method, its wide application in various commercial products, such as UV-curable inks, paints, and varnishes, has led to ubiquitous environmental issues caused by PIs. In this study, we present an overview of the current knowledge on the environmental occurrence, human exposure, and toxicity of PIs and provide suggestions for future research based on numerous available studies. The residual concentrations of PIs in commercial products, such as food packaging materials, are at microgram per gram levels. The migration of PIs from food packaging materials to foodstuffs has been confirmed by more than 100 reports of food contamination caused by PIs. Furthermore, more than 20 PIs have been detected in water, sediment, sewage sludge, and indoor dust collected from Asia, the United States, and Europe. Human internal exposure was also confirmed by the detection of PIs in serum. In addition, PIs were present in human breast milk, indicating that breastfeeding is an exposure pathway for infants. Among the most available studies, benzophenone is the dominant congener detected in the environment and humans. Toxicity studies of PIs reveal multiple toxic end points, such as carcinogenicity and endocrine-disrupting effects. Future investigations should focus on synergistic/antagonistic toxicity effects caused by PIs coexposure and metabolism/transformation pathways of newly identified PIs. Furthermore, future research should aim to develop "greener" PIs with high efficiency, low migration, and low toxicity.

A field-validated equilibrium passive sampler for the monitoring of per- and polyfluoroalkyl substances (PFAS) in sediment pore water and surface water.

A simple equilibrium passive sampler, consisting of water in an inert container capped with a rate-limiting barrier, for the monitoring of per- and polyfluoroalkyl substances (PFAS) in sediment pore water and surface water was developed and tested through a series of laboratory and field experiments. The objectives of the laboratory experiments were to determine (1) the membrane type that could serve as the sampler's rate-limiting barrier, (2) the mass transfer coefficient of environmentally relevant PFAS through the selected membrane, and (3) the performance reference compounds (PRCs) that could be used to infer the kinetics of PFAS diffusing into the sampler. Of the membranes tested, the polycarbonate (PC) membrane was deemed the most suitable rate-limiting barrier, given that it did not appreciably adsorb the studied PFAS (which have ≤8 carbons), and that the migration of these compounds through this membrane could be described by Fick's law of diffusion. When employed as the PRC, the isotopically labelled PFAS M2PFOA and M4PFOS were able to predict the mass transfer coefficients of the studied PFAS analytes. In contrast, the mass transfer coefficients were underpredicted by Br- and M3PFPeA. For validation, the PC-based passive samplers consisting of these four PRCs, as well as two other PRCs (i.e., M8PFOA and C8H17SO3-), were deployed in the sediment and water at a PFAS-impacted field site. The concentration-time profiles of the PRCs indicated that the samplers deployed in the sediment required at least 6 to 7 weeks to reach 90% equilibrium. If the deployment times are shorter (e.g., 2 to 4 weeks), PFAS concentrations at equilibrium could be estimated based on the concentrations of the PRCs remaining in the sampler at retrieval. All PFAS concentrations determined via this approach were within a factor of two compared to those measured in the mechanically extracted sediment pore water and surface water samples obtained adjacent to the sampler deployment locations. Neither biofouling of the rate-limiting barrier nor any physical change to it was observed on the sampler after retrieval. The passive sampler developed in this study could be a promising tool for the monitoring of PFAS in pore water and surface water.

Noise-Reduced Quantitative Fluorine NMR Spectroscopy Reveals the Presence of Additional Per- and Polyfluorinated Alkyl Substances in Environmental and Biological Samples When Compared with Routine Mass Spectrometry Methods.

Per- and polyfluorinated alkyl substances (PFAS) are ubiquitous throughout the environment. Analysis of PFAS is commonly performed using both targeted and nontargeted mass spectrometry methods. However, it has been demonstrated that measurements of fluorinated compounds in the environment by mass spectrometry often fall short of the total fluorine concentration. In the present study, we employ a 19F NMR technique, which is capable of detailing fluorinated compounds in a sample while providing both quantitative and structural information. Inclusion of a noise-reduction strategy involving the acquisition of arrays of spectra with an increasing number of transients addresses the sensitivity challenges of environmental nuclear magnetic resonance (NMR), improving signal to noise. When this technique is applied to environmental and biological samples including rainwater, lake water, wastewater effluent, serum, and urine, the presence of PFAS, which may have been missed by routine mass spectrometric methods, is revealed. Important resonances in the 19F NMR spectrum such as that of trifluoroacetic acid are brought above the limit of quantification in all samples, allowing detection limits as low as 389 pg/L in rainwater. A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method, which was used to analyze 47 PFAS compounds, accounts for only 3.7-27% of the total fluorine concentration as determined by the NMR strategy in the present study.

Anaerobic Microbial Dechlorination of 6:2 Chlorinated Polyfluorooctane Ether Sulfonate and the Underlying Mechanisms.

The microbial transformation potential of 6:2 chlorinated polyfluorooctane ether sulfonate (6:2 Cl-PFESA) was explored in anaerobic microbial systems. Microbial communities from anaerobic wastewater sludge, an anaerobic digester, and anaerobic dechlorinating cultures enriched from aquifer materials reductively dechlorinated 6:2 Cl-PFESA to 6:2 hydrogen-substituted polyfluorooctane ether sulfonate (6:2 H-PFESA), which was identified as the sole metabolite by non-target analysis. Rapid and complete reductive dechlorination of 6:2 Cl-PFESA was achieved by the anaerobic dechlorinating cultures. The microbial community of the anaerobic dechlorinating cultures was impacted by 6:2 Cl-PFESA exposure. Organohalide-respiring bacteria originally present in the anaerobic dechlorinating cultures, including Geobacter, Dehalobacter, and Dehalococcoides, decreased in relative abundance over time. As the relative abundance of organohalide-respiring bacteria decreased, the rates of 6:2 Cl-PFESA dechlorination decreased, suggesting that the most likely mechanism for reductive dechlorination of 6:2 Cl-PFESA was co-metabolism rather than organohalide respiration. Reductive defluorination of 6:2 Cl-PFESA was not observed. Furthermore, 6:2 H-PFESA exhibited 5.5 times lower sorption affinity to the suspended biosolids than 6:2 Cl-PFESA, with the prospect of increased mobility in the environment. These results show the susceptibility of 6:2 Cl-PFESA to microbially mediated reductive dechlorination and the likely persistence of the product, 6:2 H-PFESA, in anaerobic environments.

Aerobic biotransformation of a novel highly functionalized polyfluoroether-based surfactant using activated sludge from a wastewater treatment plant.

A replacement fluorosurfactant has been recently introduced to the European market as an alternative to other per- and polyfluoroalkyl substances (PFAS) that have been phased-out or banned. Here, we incubated this novel fluorosurfactant (diFESOS, [F7C3OCHFCF2SCH2CH2OC(O)]2C2H3SO3-) which contains ether and thioether insertions, and its known polyfluoroalkyl degradation products, an alcohol (FESOH) and carboxylic acid (FESCA), with activated sludge from a wastewater treatment plant under sulfur-limited conditions. Dosed chemicals and their transformation products were monitored using ultra-high performance liquid chromatography-tandem mass spectrometry, and gas chromatography-mass spectrometry. In addition to FESOH and FESCA, two smaller metabolites were identified: C3F7OCHFCOO- (2H-3:2 PFECA) and perfluoropropanoic acid (PFPrA). 2H-3:2 PFECA presumably was a result of S-dealkylation of FESCA, which then resulted in the abiotic cleavage of two C-F bonds; no S-oxygenation was observed. Overall, the terminal products of this biotransformation likely have lower bioaccumulation potential than the parent fluorosurfactant based on comparison to other similar PFAS.

Atmospheric Fate of a New Polyfluoroalkyl Building Block, C3F7OCHFCF2SCH2CH2OH.

Many per- and polyfluoroalkyl substances (PFAS) have been regulated or phased-out of usage due to concerns about persistence, bioaccumulation potential, and toxicity. We investigated the atmospheric fate of a new polyfluorinated alcohol 2-(1,1,2-trifluoro-2-heptafluoropropyloxy-ethylsulfanyl)-ethanol (C3F7OCHFCF2SCH2CH2OH, abbreviated FESOH) by assessing the kinetics and products of the gas-phase reaction of FESOH with chlorine atoms and hydroxyl radicals. Experiments performed in a stainless-steel chamber interfaced to an FTIR were used to determine reaction kinetics and gas-phase products. We report reaction rate constants of k(Cl + FESOH) = (1.5 ± 0.6) × 10-11 cm3 molecule-1 s-1 and k(OH + FESOH) = (4.2 ± 2.0) × 10-12 cm3 molecule-1 s-1. This leads to a calculated FESOH gas-phase lifetime of 2.8 ± 1.3 days with respect to reaction with OH, assuming [OH] = 106 molecule1 cm-3. Gas-phase products of FESOH oxidation included at least two aldehydes, likely C3F7OCHFCF2SCH2C(O)H and C3F7OCHFCF2SC(O)H, and secondary products including COF2, SO2 and C3F7OC(O)F. Additional gas-phase experiments performed in a Teflon chamber were used to assess aqueous products by collecting gaseous samples offline into an aqueous sink prior to analysis with ultrahigh performance liquid chromatography-tandem mass spectrometry, resulting in four acidic products: C3F7OCHFCF2SCH2C(O)OH, C3F7OCHFCF2S(O)(O)OH, C3F7OCHFC(O)OH, and perfluoropropanoic acid (C2F5C(O)OH).

Significant Reductive Transformation of 6:2 Chlorinated Polyfluorooctane Ether Sulfonate to Form Hydrogen-Substituted Polyfluorooctane Ether Sulfonate and Their Toxicokinetics in Male Sprague-Dawley Rats.

6:2 chlorinated polyfluorooctane ether sulfonate (6:2 Cl-PFESA) was previously shown to undergo limited dechlorination in rainbow trout to yield 6:2 hydrogen-substituted polyfluorooctane ether sulfonate (6:2 H-PFESA) as the sole metabolite. However, the biotransformation susceptibility of 6:2 Cl-PFESA has not been investigated in mammals and the biological behavior of 6:2 H-PFESA has not been defined in any species. We investigated the respective transformation products of 6:2 Cl-PFESA and 6:2 H-PFESA and their toxicokinetic properties in male Sprague-Dawley rats as a mammalian model. 6:2 H-PFESA was the sole detectable metabolite of 6:2 Cl-PFESA, with a transformation percentage of 13.6% in rat liver, but it resisted further degradation. 6:2 Cl-PFESA also transformed to 6:2 H-PFESA in reductive rat liver S9 incubations but remained stable under oxidative conditions, suggesting a reductive enzyme-dependent transformation pathway. 6:2 Cl-PFESA was more enriched in lipid-rich tissues, while 6:2 H-PFESA was more prone to cumulative urinary excretion. From this perspective, it may suggest a detoxification mechanism for organisms to form the less hydrophobic 6:2 H-PFESA to alleviate total burdens. To date, 6:2 Cl-PFESA was the second perfluoroalkyl acid reported to undergo biotransformation in mammals. The toxicokinetic properties determined for 6:2 Cl-PFESA and 6:2 H-PFESA in blood and urine were found to be structure and dose dependent.

In Vivo Transformation of a Novel Polyfluoroether Surfactant.

Per- and polyfluoroalkyl substances are a class of fluorochemicals that can degrade into perfluoroalkyl acids, which are well known to be persistent in the environment. It is thus important that novel fluorinated surfactants be designed to degrade into small, nonbioaccumulative products. We report the biotransformation and elimination kinetics of one such novel polyfluorinated surfactant, di(polyfluoroether thioether(S)-oate) sulfonate (diFESOS), and its metabolites. Biotransformation was investigated in vitro using S9 liver fractions and in vivo in Sprague-Dawley rats. Rats dosed by oral gavage with diFESOS were found to have relatively fast elimination kinetics, with half-lives on the order of hours, compared with legacy fluorinated surfactants such as the disubstituted polyfluoroalkyl phosphates that have half-lives on the order of days. To interrogate degradation of the polyfluorinated chain, rats were then dosed with a polyfluoroether thioether alcohol (a suspected product of carboxylate cleavage of diFESOS) either orally or intravenously, and the novel metabolite 2H-3:2 polyfluoroether sulfonic acid (2H-3:2 PFESA) was identified. Perfluoropropionic acid was detected in rat urine and is likely a terminal product. The blood of orally dosed rats contained higher levels of metabolites than the blood of intravenously dosed rats, suggesting the importance of metabolism in the gut and liver. Elimination kinetics of all the novel metabolites were faster than their fully fluorinated counterparts. Environ Toxicol Chem 2021;40:3328-3336. © 2021 SETAC.

Rat Metabolism Study Suggests 3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionic Acid as a Potential Urinary Biomarker of Human Exposure to Representative 3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionate Antioxidants.

3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionate antioxidants, a family of synthetic phenolic antioxidants (SPAs) widely used in polymers, have recently been identified in indoor and outdoor environments. However, limited information is available concerning human exposure to these novel contaminants. In the present study, seven 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate antioxidants were analyzed in human urine samples of donors from the United States. None of the target SPAs were initially detected in the urine samples either before or after hydrolysis by ß-glucuronidase, prompting us to probe the major metabolites of these SPAs. We conducted rat metabolism studies with two representative congeners, tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (AO1010) and N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine (AO1024). Neither AO1010 nor AO1024 was detected in rat urine, while 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid (fenozan acid) was identified as a urinary biomarker for these 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate antioxidants. Surprisingly, fenozan acid was detected in 88% of the human urine samples before hydrolysis (geometric mean: 0.69 ng/mL) and 98% of the samples after hydrolysis (geometric mean: 10.2 ng/mL), indicating prevalent human exposure to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate antioxidants. To our knowledge, this is the first study reporting the occurrence of fenozan acid in urine, where it can act as a potential biomarker of human exposure to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate antioxidants.

The Sulfoximine Insecticide Sulfoxaflor and Its Photodegradate Demonstrate Acute Toxicity to the Nontarget Invertebrate Species Daphnia magna.

The environmental fate and persistence of sulfoxaflor is of significant interest given the potential for the insecticide to impact nontarget organisms, particularly pollinating and aquatic species. In the present study we examine the potential for sulfoxaflor, a new sulfoximine insecticide, to undergo degradation and transformation in sediments and the aquatic environment. Following application of the active substance as a foliar spray or seed coating, sulfoxaflor can be found in the soil at a mass percentage of up to 61% of the total applied concentration. The low soil sorption coefficient (KD ) of sulfoxaflor of 0.103 signifies the potential for sulfoxaflor to undergo transport into nearby surface waters via groundwater run-off. In soils and sediments sulfoxaflor produces a sulfoxaflor-urea analog with a varying half-life of 5.0 to 8.5 d depending on the sediment type. Once in surface waters, sulfoxaflor can undergo photolysis to a sulfoxaflor alcohol derivative with a half-life of 35 h. The photodegradate demonstrates reduced aquatic toxicity to Daphnia magna, but the photolytic half-life may be too long to mitigate the acute toxicity of the parent substance sulfoxaflor to D. magna, which was found to have a 48-h median effect concentration of 361 µg/L. Environ Toxicol Chem 2021;40:2156-2164. © 2021 SETAC.

Printing ink related chemicals, including synthetic phenolic antioxidants, organophosphite antioxidants, and photoinitiators, in printing paper products and implications for human exposure.

Although synthetic antioxidants (AOs) and photoinitiators (PIs) are known to be used in printing inks, there are little data on residual concentrations in printing paper products. In the present study, twenty-five PIs, ten AOs, and six transformation products were analyzed in two types of printing paper products, magazines and paperboard food packaging materials, both of which are unavoidable everyday products in our life. Nine AOs and six transformation products can be detected in food packaging materials with total concentrations (geometric mean, GM) of 1.16 × 104 ng/dm2. Twenty-two PIs were detected in food packaging materials with total concentrations (GM) of 1.76 × 104 ng/dm2. These chemicals were also detected in magazines, albeit at low concentrations (GM of AOs: 466 ng/dm2, GM of PIs: 1.17 × 103 ng/dm2). Magazine front covers were found to have much higher concentrations of the target compounds than magazine inside pages. Tris(2,4-di-tert-butylphenyl) phosphate (AO168O), 2,6-di-tert-butyl-4-methylphenol (BHT), bisphenol A (BPA), and benzophenone (BP) were among the predominant chemicals in those printing paper products. Preliminary calculations suggest that dermal exposure to AOs (GM: 6.25 ng/day) and PIs (GM: 17.0 ng/day) via contact with printing paper products is a minor exposure pathway compared to food intake/dust ingestion and is exceedingly unlikely to cause adverse health effects.

Synthetic Phenolic Antioxidants: A Review of Environmental Occurrence, Fate, Human Exposure, and Toxicity.

Synthetic phenolic antioxidants (SPAs) are widely used in various industrial and commercial products to retard oxidative reactions and lengthen product shelf life. In recent years, numerous studies have been conducted on the environmental occurrence, human exposure, and toxicity of SPAs. Here, we summarize the current understanding of these issues and provide recommendations for future research directions. SPAs have been detected in various environmental matrices including indoor dust, outdoor air particulates, sea sediment, and river water. Recent studies have also observed the occurrence of SPAs, such as 2,6-di-tert-butyl-4-methylphenol (BHT) and 2,4-di-tert-butyl-phenol (DBP), in humans (fat tissues, serum, urine, breast milk, and fingernails). In addition to these parent compounds, some transformation products have also been detected both in the environment and in humans. Human exposure pathways include food intake, dust ingestion, and use of personal care products. For breastfeeding infants, breast milk may be an important exposure pathway. Toxicity studies suggest some SPAs may cause hepatic toxicity, have endocrine disrupting effects, or even be carcinogenic. The toxicity effects of some transformation products are likely worse than those of the parent compound. For example, 2,6-di-tert-butyl-p-benzoquinone (BHT-Q) can cause DNA damage at low concentrations. Future studies should investigate the contamination and environmental behaviors of novel high molecular weight SPAs, toxicity effects of coexposure to several SPAs, and toxicity effects on infants. Future studies should also develop novel SPAs with low toxicity and low migration ability, decreasing the potential for environmental pollution.

The Environmental Degradation and Distribution of Saflufenacil, a Fluorinated Protoporphyrinogen IX Oxidase-Inhibiting Herbicide, on a Canadian Winter Wheat Field.

Saflufenacil when applied to a field is susceptible to transport, degradation, and transformation. We used a laboratory-based approach to model the fate of saflufenacil in the environment, the results of which are compared directly with those observed in a field study where saflufenacil was applied to a crop of winter wheat at a standard rate of 63 g of active ingredient/hectare. The water solubility of 2.1 g/L for saflufenacil allows for vertical transport through soil at a rate of 4.3 cm/mL of rainwater, and a soil adsorption coefficient KOC of 28.8 suggests that some of the herbicide will absorb to the soil. Of the saflufenacil in the soil, 78 ± 2.1% (n = 18) partitioned into plants, including nontargeted crop species, where it was found primarily in leaves (78 ± 2.1%, n = 18) and roots (22 ± 1.7%, n = 18). The saflufenacil that does not partition into plants or undergo vertical transport followed a degradation pathway into 3 metabolites: a uracil-ring N-demethylated metabolite (Saf-µCH3 ), a doubly N-demethylated metabolite (Saf-2CH3 ), and a ring-cleavage metabolite (Saf-RC), identified using nontargeted mass spectrometry. In the field, saflufenacil was observed to degrade over 212 d to the persistent metabolite Saf-RC. This metabolite was found at a concentration that was 1/10th of that applied to the field, suggesting that the majority of saflufenacil had undergone transport through the soil, or uptake into the winter wheat crop. Field samples were further examined using F-19 nuclear magnetic resonance and nontargeted mass spectrometry to rule out the potential of other degradation products. Environ Toxicol Chem 2020;39:1918-1928. © 2020 SETAC.

First Report on In Vivo Pharmacokinetics and Biotransformation of Chlorinated Polyfluoroalkyl Ether Sulfonates in Rainbow Trout.

This study provides the first in vivo pharmacokinetic data for chlorinated perfluorooctanesulfonate (Cl-PFOS), 6:2 and 8:2 chlorinated polyfluoroalkyl ether sulfonates (Cl-PFESAs), upon a 30 day dietary exposure and 34 day depuration phase in rainbow trout (Oncorhynchus mykiss). Biological handling of these three novel molecules and legacy PFOS were investigated via cross-comparison. PFOS and Cl-PFOS displayed comparable bioaccumulative potencies and similar distribution tendencies in tissues (blood > liver > kidneys), despite the presence of a terminal chlorine atom in Cl-PFOS molecule. The Cl-PFESAs, especially 8:2 Cl-PFESA, were predominantly assimilated from the bloodstream by liver and kidneys and resisted elimination, leading to higher bioaccumulation factors in liver than in blood (0.576 and 0.254, respectively, for 8:2 Cl-PFESA) and longer half-lives in liver and kidneys than PFOS, suggesting these alternatives may pose greater risks in terms of the great accumulation potentials in fish tissues. The present study provides the first report of the in vivo transformation of 6:2 and 8:2 Cl-PFESAs and identifies 6:2 and 8:2 H-PFESAs as their respective sole metabolites. This provides the first line of evidence suggesting that the transformation susceptibility of Cl-PFESAs in organisms is distinct from their environmental persistence.

Synthetic Phenolic Antioxidants in Personal Care Products in Toronto, Canada: Occurrence, Human Exposure, and Discharge via Greywater.

Although synthetic phenolic antioxidants (SPAs) are widely used in various personal care products (PCPs), little is known about their levels, composition profiles, human exposure, or environmental emissions. In this study, the occurrence of SPAs was evaluated in 15 categories of 214 PCPs collected in Toronto, Canada. Nine SPAs were detected in the PCPs, of which only 2,6-di-tert-butyl-4-methylphenol (BHT, < method quantification limit (MQL)-827 900 ng/g, mean: 35 602 ng/g, median: 249 ng/g) was observed with a detection frequency of >50%. When the 214 PCPs were separated into products labeled as containing BHT and those labeled as not containing BHT, the BHT-labeled PCPs (mean: 369 253 ng//g, median: 382 560 ng/g) contained significantly higher concentrations of BHT than the BHT-unlabeled PCPs (mean: 4960 ng/g, median: 199 ng/g) did (p < 0.01). Five transformation products (TPs) of BHT were also detected in the PCPs at low concentrations (∑TPs: < MQL to 19 014 ng/g, mean: 730 ng/g, median: < MQL) and detection frequencies (12.6-37.4%). Preliminary calculations found that dermal absorption via PCP use may be an important exposure pathway for BHT (mean: 565 879 ng/day median: 2988 ng/day), although this is a negligible exposure pathway for other SPAs. In addition, the estimated discharges of BHT (mean: 7852 g/day, median: 88 g/day) via greywater after PCP use were calculated, which represents a nonignorable source of BHT loading into wastewater treatment plants in Toronto (contributing 10%). To our knowledge, this is the first evaluation of human exposure to and discharge of SPAs via PCP use.

Unexpectedly high concentrations of 2,4-di-tert-butylphenol in human urine.

Synthetic phenolic antioxidants (SPAs) have received increasing attention due to the reports of toxicity and environmental contamination. Nevertheless, limited information was available on human burdens of these SPAs, with the exception of 2,6-di-tert-butyl-4-methylphenol (BHT). In our study, BHT as well as six other SPAs were analyzed in human urine samples from United States donors. Three SPA congeners were detected in human urine: BHT, 2,4-di-tert-butylphenol (DBP), and 3-tert-butyl-4-hydroxyanisole (BHA). BHT, which is the congener received most concerns, was detected at low concentrations [geometric mean (GM): 0.06 ng/mL], whereas four of its metabolites were detected at relatively high concentrations (GM: 1.68 ng/mL). Surprisingly, DBP was detected at extremely high concentrations (GM: 18.3 ng/mL). The concentrations of DBP (GM: 25.8 ng/mL), BHT (0.853 ng/mL), and metabolites (GM: 10.5 ng/mL) increased significantly after the urine samples were hydrolyzed by ß-glucuronidase (p < 0.01), indicating the prevalence of the conjugated forms of SPAs and their metabolites in human urine. DBP, which has previously received little attention, was the predominant congener, contributing 88.2% and 63.6% to total target concentrations in the urine samples before and after ß-glucuronidase hydrolysis, respectively. Thus, previous studies have vastly underestimated the burdens of SPAs to humans. To our knowledge, this is the first study revealing the presence of DBP in human urine.

Identification of Photoinitiators, Including Novel Phosphine Oxides, and Their Transformation Products in Food Packaging Materials and Indoor Dust in Canada.

Although photopolymerization is generally considered a green technology, the contamination of foodstuffs by photoinitiators (PIs), an essential component of photopolymerization systems, has recently attracted notice. Despite this interest, little attention has been paid to PI contamination in the environment. To date, only one study, performed in China, has reported the occurrence of PIs in the environment. In the present study, the occurrence of 25 PI additives with discrete molecular structures was investigated in food packaging materials and indoor dust. The PIs studied here include benzophenones (BZPs), thioxanthones (TXs), amine co-initiators (ACIs), and novel phosphine oxides (POs). Twenty-four PIs were detected in food packaging materials. Total concentrations of PIs (∑PIs) ranged between 122 and 44 113 ng/g, with a geometric mean (GM) of 3375 ng/g. The photodegradation of PIs in food packaging materials was investigated for the first time, and the half-lives of PIs in these materials were found to range from 32 to 289 h. These 24 PIs were also detected in indoor dust samples (GM of ∑PIs = 1483 ng/g). The relative abundances of different PIs were found to vary between the packaging materials and the indoor dust, which is attributed in part to the different stabilities of different PIs under simulated sunlight. Using standards synthesized in our lab, four TX transformation products (GM: 34.8 ng/g) were also detected in indoor dust. The concentrations of the transformation products were higher than the concentrations of the parent chemicals in indoor dust. Thus, further studies exploring human exposure to TXs should include these transformation products to avoid underestimation. This is the first report of PIs and relevant transformation products in the indoor environment in North America.