Quantitation of Total PFAS Including Trifluoroacetic Acid with Fluorine Nuclear Magnetic Resonance Spectroscopy.

Fluorine nuclear magnetic resonance (19F-NMR) spectroscopy has been shown to be a powerful tool capable of quantifying the total per- and polyfluoroalkyl substances (PFAS) in a complex sample. The technique relies on the characteristic terminal -CF3 shift (-82.4 ppm) in the alkyl chain for quantification and does not introduce bias due to sample preparation or matrix effects. Traditional quantitative analytical techniques for PFAS, such as liquid chromatography-mass spectrometry (LC-MS) and combustion ion chromatography (CIC), contain inherent limitations that make total fluorine analysis challenging. Here, we report a sensitive 19F-NMR method for the analysis of total PFAS, with a limit of detection of 99.97 nM, or 50 µg/L perfluorosulfonic acid. To demonstrate the capabilities of 19F-NMR, the technique was compared to two commonly used methods for PFAS analysis: total oxidizable precursor (TOP) assay and LC-high resolution MS analysis for targeted quantification and suspect screening. In both cases, the 19F-NMR analyses detected higher total PFAS quantities than either the TOP assay (63%) or LC-MS analyses (65%), suggesting that LC-MS and TOP assays can lead to underreporting of PFAS. Importantly, the 19F-NMR detected trifluoroacetic acid at a concentration more than five times the total PFAS concentration quantified using LC-MS in the wastewater sample. Therefore, the use of 19F-NMR to quantify the total PFAS in highly complex samples can be used to complement classic TOP or LC-MS approaches for more accurate reporting of PFAS contamination in the environment.

How Many Chemicals in Commerce Have Been Analyzed in Environmental Media? A 50 Year Bibliometric Analysis.

Over the past 50 years, there has been a tremendous expansion in the measurement of chemical contaminants in environmental media. But how many chemicals have actually been determined, and do they represent a significant fraction of substances in commerce or of chemicals of concern? To address these questions, we conducted a bibliometric survey to identify what individual chemicals have been determined in environmental media and their trends over the past 50 years. The CAplus database of CAS, a Division of the American Chemical Society, was searched for indexing roles "analytical study" and "pollutant" yielding a final list of 19,776 CAS Registry Numbers (CASRNs). That list was then used to link the CASRNs to biological studies, yielding a data set of 9.251 × 106 total counts of the CASRNs over a 55 year period. About 14,150 CASRNs were substances on various priority lists or their close analogs and transformation products. The top 100 most reported CASRNs accounted for 34% of the data set, confirming previous studies showing a significant bias toward repeated measurements of the same substances due to regulatory needs and the challenges of determining new, previously unmeasured, compounds. Substances listed in the industrial chemical inventories of Europe, China, and the United States accounted for only about 5% of measured substances. However, pharmaceuticals and current use pesticides were widely measured accounting for 50-60% of total CASRN counts for the period 2000-2015.

Characterization of Per- and Polyfluorinated Alkyl Substances Present in Commercial Anti-fog Products and Their In Vitro Adipogenic Activity.

Anti-fog sprays and solutions are used on eyeglasses to minimize the condensation of water vapor, particularly while wearing a mask. Given their water-repellent properties, we sought to characterize per- and polyfluorinated alkyl substance (PFAS) compounds in four anti-fog spray products, five anti-fog cloth products, and two commercial fluorosurfactant formulations suspected to be used in preparing anti-fog products. Fluorotelomer alcohols (FTOHs) and fluorotelomer ethoxylates (FTEOs) were detected in all products and formulations. While 6:2 FTOH and the 6:2 FTEO polymeric series were predominant, one anti-fog cloth and one formulation contained 8:2, 10:2, 12:2, 14:2, and 16:2 FTOH and FTEO polymeric series. PFAS concentrations varied in samples and were detected at levels up to 25,000 µg/mL in anti-fog sprays and 185,000 µg (g cloth)-1 in anti-fog cloth products. The total organic fluorine (TOF) measurements of anti-fog products ranged from 190 to 20,700 µg/mL in sprays and 44,200 to 131,500 µg (g cloth)-1 in cloths. Quantified FTOHs and FTEOs accounted for 1-99% of TOF mass. In addition, all four anti-fog sprays and both commercial formulations exhibited significant cytotoxicity and adipogenic activity (either triglyceride accumulation and/or pre-adipocyte proliferation) in murine 3T3-L1 cells. Results suggest that FTEOs are a significant contributor to the adipogenic activity exhibited by the anti-fog sprays. Altogether, these results suggest that FTEOs are present in commercial products at toxicologically relevant levels, and more research is needed to fully understand the health risks from using these PFAS-containing products.

Structure Database and In Silico Spectral Library for Comprehensive Suspect Screening of Per- and Polyfluoroalkyl Substances (PFASs) in Environmental Media by High-resolution Mass Spectrometry.

Per and polyfluoroalkyl substances (PFASs) are an important class of organic pollutants. Many diverse PFASs are used in commerce and most are not amenable to conventional targeted chemical analysis due to lack of reference standards. Therefore, methods for elucidating the chemical structure of previously unreported or unexpected PFASs in the environment rely extensively on high-resolution mass spectrometry (HRMS). High-throughput structure identification by HRMS is hindered by a lack of PFAS molecular databases and tandem mass spectral libraries. Here, we report a new approach for generating an environmentally relevant PFAS molecular database constructed from curated structure lists and biotic/abiotic in silico predicted transformation products. Further, we have generated a predicted tandem mass spectral library using computational mass spectrometry tools. Results demonstrate the utility of the generated database and approach for identifying PFASs in HRMS-enabled suspect- and nontarget screening studies.

Analysis of Single-Walled Carbon Nanotubes in Estuarine Sediments by Density Gradient Ultracentrifugation Coupled to Near-Infrared Fluorescence Spectroscopy Reveals Disassociation of Residual Metal Catalyst Nanoparticles.

The continued growth of the nanotechnology industry and the incorporation of nanomaterials into consumer applications will inevitably lead to their release into environmental systems. Single-walled carbon nanotubes (SWCNTs) in particular have exhibited many attractive optical, mechanical, and electrical properties that lend themselves to new and exciting applications. Assessing their environmental impact upon release into the environment is contingent upon quantifying and characterizing SWCNTs in environmental matrixes. In this study, SWCNTs were isolated from estuarine sediments using density gradient ultracentrifugation (DGU), followed by online flow-through analysis of the density fractions via near-infrared spectroscopy. This approach yielded significant improvements in the quantitative detection limit, from 62 to 1.5 µg g-1. In addition, fractions of the density gradient were also obtained for further analysis by bulk inductively coupled plasma mass spectrometry (ICP-MS) and single-particle ICP-MS. Using fluorescent, semiconductive SWCNTs, the primary fluorescent nanotube fraction was found to be separated from the sediment matrix during DGU; however, the residual metal catalyst particles that had been assumed to be physically bound to the SWCNTs were found to form a separate band in the density gradient apart from the fluorescent SWCNTs. This result was repeated for a number of SWCNT types regardless of the metal catalyst and synthesis method, with a 0.1 g cm-3 density difference between most fractions. The apparent disconnect between the fluorescent fraction of SWCNTs and their metal-containing constituents potentially complicates CNT risk assessment as analysis techniques focusing solely on either CNT fluorescence or metal fingerprints may misrepresent exposure concentrations and their toxicological implications.

Development of a sensitive direct injection LC-MS/MS method for the detection of glyphosate and aminomethylphosphonic acid (AMPA) in hard waters.

Glyphosate is currently the most widely used herbicide in the world; however, the zwitterionic and highly polar properties of glyphosate make current pesticide analysis methods unsuitable for its trace analysis in natural waters. Additionally, current glyphosate analysis methods do not account for waters of varying hardness, which is vital as glyphosate can complex with cationic species such as Ca2+ and Mg2+ in the environment. We detail here a robust LC-MS/MS method for the quantitation of glyphosate and its primary transformation product aminomethylphosphonic acid (AMPA) in environmental waters of varying water hardness. Chromatographic separation was achieved with a reversed-phase and weak anion-exchange mixed-mode column. We found that the addition of EDTA into hard water samples increases the response of both glyphosate and AMPA in the mass spectrometer. Limits of detection of 0.23 and 0.30 µg L-1 for glyphosate and AMPA in EDTA-amended hard water were achieved, respectively. We have demonstrated that the accuracy of the method was consistent over a wide range of water hardness levels up to a maximum of ~340 mg mL-1 CaCO3 hardness. We validated the method using matrix fortification of uncontaminated environmental samples from US river water. We then demonstrated that the method was successful at quantifying glyphosate and AMPA across surface and drinking water samples of varying water hardness from North Carolina and Sri Lanka. Measured concentrations of glyphosate and AMPA ranged from 1.6 to 13 µg L-1 and 0.50 to 2.5 µg L-1, respectively. This study represents a significant increase in sensitivity for LC-MS/MS analysis of glyphosate in hard water systems. Graphical abstract.

In Vitro Metabolism of Isopropylated and tert-Butylated Triarylphosphate Esters Using Human Liver Subcellular Fractions.

Isopropylated and tert-butylated triarylphosphate esters (ITPs and TBPPs, respectively) are plasticizers and flame retardants that are ubiquitous in indoor environments; however, no studies to date have characterized their metabolism. Using human liver subcellular S9 fractions, phase I and II in vitro metabolism of triphenyl phosphate (TPHP), 4-tert-butylphenyl diphenyl phosphate (4tBPDPP), 2-isopropylphenyl diphenyl phosphate (2IPPDPP), and 4-isopropylphenyl diphenyl phosphate (4IPPDPP) was investigated at 1 and 10 µM doses. Parent depletion and the formation of known or suspected metabolites (e.g., likely hydrolysis or hydroxylated products), including diphenyl phosphate (DPHP), hydroxyl-triphenyl phosphate (OH-TPHP), isopropylphenyl phenyl phosphate (ip-PPP), and tert-butylphenyl phenyl phosphate (tb-PPP), were monitored and quantified via GC/MS or LC-MS/MS. tb-PPP and its conjugates were identified as the major in vitro metabolites of 4tBPDPP and accounted for 71% and 49%, respectively, of the parent molecule that was metabolized during the incubation. While the mass balance between parents and metabolites was conserved for TPHP and 4tBPDPP, approximately 20% of the initial parent mass was unaccounted for after quantifying suspected metabolites of 2IPPDPP and 4IPPDPP that had authentic standards available. Two novel ITP metabolites, mono-isopropenylphenyl diphenyl phosphate and hydroxy-isopropylphenyl diphenyl phosphate, were tentatively identified by high-resolution mass spectrometry and screened for in recently collected human urine where mono-isopropenylphenyl diphenyl phosphate was detected in one of nine samples analyzed. This study provides insight into the biological fate of ITP and TBPP isomers in human tissues and is useful in identifying appropriate biomarkers of exposure to monitor, particularly in support of epidemiological studies.

Bioaccumulation of Novel Per- and Polyfluoroalkyl Substances in Mice Dosed with an Aqueous Film-Forming Foam.

Per- and polyfluoroalkyl substances (PFASs) are widespread in the blood of the general human population, and their bioaccumulation is of considerable scientific and regulatory interest. PFAS exposure resulting from aqueous film-forming foam (AFFF) ingestion is poorly understood due to the complexity of AFFF mixtures and the presence of polyfluorinated substances that may undergo metabolic transformation. C57BL/6 mice were dosed with an AFFF primarily containing electrochemically fluorinated PFASs for 10 days, followed by a 6 day depuration. Urine was collected throughout the study and serum was collected post-depuration. Samples were analyzed via high-resolution mass spectrometry. Relative to the dosing solution, C6 and C7 perfluoroalkyl sulfonates (PFSAs) were enriched in dosed mouse serum, suggesting in vivo transformation of sulfonamide precursors. Some substituted C8 PFSAs [keto-perfluorooctane sulfonate (PFOS), hydrogen-PFOS, and unsaturated PFOS] appeared to be more bioaccumulative than linear PFOS, or were formed in vivo from unidentified precursors. A series of seven peaks in dosed mouse serum was tentatively identified as sulfonimide dimers that were either a minor component of the AFFF or were formed via metabolism of other AFFF components. This work highlights the importance of sulfonamide precursors in contributing to bioaccumulation of AFFF-associated PFSAs and identifies several classes of potentially bioaccumulative novel PFASs that warrant further investigation.

Molecular characterization of nonionic surfactant components of the Corexit® 9500 oil spill dispersant by high-resolution mass spectrometry.

RATIONALE: Approximately 7 million liters of Corexit® dispersants were applied during the 2010 Deepwater Horizon oil spill to facilitate the dispersion of crude oil. At the time of application, the exact chemical composition of Corexit® was relatively unknown. Characterization of Corexit® 9500 was performed using high-resolution mass spectrometry to further understand the complexity of the nonionic surfactant components of this mixture. METHODS: Corexit®9500 was analyzed by ultra-high-performance liquid chromatography (UHPLC) coupled to a high resolution Orbitrap Fusion Lumos mass spectrometer operated in positive electrospray ionization mode and a charged aerosol detector. Chromatographic conditions were optimized to efficiently separate isobaric and isomeric compounds. Polyethoxylated nonionic surfactants in Corexit® 9500 were identified using the following criteria: accurate mass (<3 ppm), retention time, and homologue series; in addition, interpretation of high-resolution tandem mass spectra was used to annotate tentative component structures. RESULTS: More than 2000 polysorbate nonionic surfactants in 87 homologue series were detected. Polysorbate surfactants were characterized by the type of molecular basis group (sorbitan, isosorbide, or fatty acid), degree of esterification (n = 0-4), ester chain length (C6-C24), and ester saturation, in addition to polydispersion by ethoxylation. Isomeric compounds were differentiated by LC/HRMS/MS analysis with product ion assignment. Results from the charged aerosol detector showed that the diesters (23.9 ± 0.78%) were the most abundant component in Corexit® 9500 followed by dioctyl sodium sulfosuccinate (DOSS) (19.2 ± 1.5%), triesters (17.3 ± 1.5%), and monoesters (15.7 ± 2.3%). CONCLUSIONS: Our analytical approach facilitated the characterization of polysorbate surfactants within Corexit® 9500 and allowed a systematic study to differentiate isomeric and isobaric compounds, when standards were not available. The characterized composition of Corexit® 9500 will facilitate future studies to determine the chemical and biological transformation kinetics and byproducts of Corexit® 9500 under environmental conditions.

Chemical Mixtures Isolated from House Dust Disrupt Thyroid Receptor ß Signaling.

House dust is a source of exposure to chemicals that can impact hormone regulation. This study was designed to evaluate the potential of house dust mixtures ( n = 137) to disrupt thyroid hormone nuclear receptor signaling in a cell-based reporter assay and to examine associations with thyroid hormones (TH) measured in residents of the homes. Approximately 41% of the extracts (ranging from 10.5 to 4.097 µg of dust/mL) significantly antagonized thyroid receptor ß (TRß) signaling by 20-67% relative to the hormone control. The concentrations of 12 flame retardants (FRs) quantified in the mixtures were significantly correlated with TRß antagonism; however, they were inactive when tested individually. We hypothesize that the observed antagonism is due to mixture effects or unidentified compounds that co-occur with FRs. Dust extract potency was significantly associated with free thyroxine (FT4, rs = -0.64, p < 0.001), suggesting that more potent dust samples are associated with higher FT4 levels in residents. Overall, these results suggest that house dust is a significant source of exposure to TH-disrupting chemicals, and TRß may have a role in mediating effects of exposure on TH levels. Additional studies are needed to identify the chemical(s) driving the observed effects on TRß and to determine if these changes lead to any adverse outcomes.

Electrochemical Transformations of Perfluoroalkyl Acid (PFAA) Precursors and PFAAs in Groundwater Impacted with Aqueous Film Forming Foams.

While oxidative technologies have been proposed for treatment of waters impacted by aqueous film forming foams (AFFFs), information is lacking regarding the transformation pathways for the chemical precursors to the perfluoroalkyl acids (PFAAs) typically present in such waters. This study examined the oxidative electrochemical treatment of poly- and perfluoroalkyl substances (PFASs) for two AFFF-impacted groundwaters. The bulk pseudo first order rate constant for PFOA removal was 0.23 L h-1 A-1; for PFOS, this value ranged from 0.084 to 0.23 L h-1 A-1. Results from the first groundwater studied suggested a transformation pathway where sulfonamide-based PFASs transformed to primarily perfluorinated sulfonamides and perfluorinated carboxylic acids (PFCAs), with subsequent defluorination of the PFCAs. Transient increases in the perfluorinated sulfonamides and PFCAs were observed. For the second groundwater studied, no transient increases in PFAAs were measured, despite the presence of similarly structured suspected PFAA precursors and substantial defluorination. For both waters, suspected precursors were the primary sources of the generated fluoride. Assessment of precursor compound transformation noted the formation of keto-perfluoroalkanesulfonates only in the second groundwater. These results confirm that oxidation and defluorination of suspected PFAA precursors in the second groundwater underwent transformation via a pathway different than that of the first groundwater, which was not captured by total oxidizable precursor assay.

Size-Based Differential Transport, Uptake, and Mass Distribution of Ceria (CeO2) Nanoparticles in Wetland Mesocosms.

Trace metals associated with nanoparticles are known to possess reactivities that are different from their larger-size counterparts. However, the relative importance of small relative to large particles for the overall distribution and biouptake of these metals is not as well studied in complex environmental systems. Here, we have examined differences in the long term fate and transport of ceria (CeO2) nanoparticles of two different sizes (3.8 vs 185 nm), dosed weekly to freshwater wetland mesocosms over 9 months. While the majority of CeO2 particles were detected in soils and sediments at the end of nine months, there were significant differences observed in fate, distribution, and transport mechanisms between the two materials. Small nanoparticles were removed from the water column primarily through heteroaggregation with suspended solids and plants, while large nanoparticles were removed primarily by sedimentation. A greater fraction of small particles remained in the upper floc layers of sediment relative to the large particles (31% vs 7%). Cerium from the small particles were also significantly more bioavailable to aquatic plants (2% vs 0.5%), snails (44 vs 2.6 ng), and insects (8 vs 0.07 µg). Small CeO2 particles were also significantly reduced from Ce(IV) to Ce(III), while aquatic sediments were a sink for untransformed large nanoparticles. These results demonstrate that trace metals originating from nanoscale materials have much greater potential than their larger counterparts to distribute throughout multiple compartments of a complex aquatic ecosystem and contribute to the overall bioavailable pool of the metal for biouptake and trophic transfer.

Evaluating the mycostimulation potential of select carbon amendments for the degradation of a model PAH by an ascomycete strain enriched from a superfund site.

Although ecological flexibility has been well documented in fungi, it remains unclear how this flexibility can be exploited for pollutant degradation, especially in the Ascomycota phylum. In this work, we assess three mycostimulation amendments for their ability to induce degradation in Trichoderma harzanium, a model fungus previously isolated from a Superfund site contaminated with polycyclic aromatic hydrocarbons. The amendments used in the present study were selected based on the documented ecological roles of ascomycetes. Chitin was selected to simulate the parasitic ecological role while cellulose and wood were selected to mimic bulk soil and wood saprobic conditions, respectively. Each amendment was tested in liquid basal medium in 0.1 and 1% (w/v) suspensions. Both chitin and cellulose amendments were shown to promote anthracene degradation in T. harzanium with the 0.1% chitin amendment resulting in over 90% removal of anthracene. None of the targets monitored for gene expression were found to be upregulated suggesting alternate pathways may be used in T. harzanium. Overall, our data suggest that mycostimulation amendments can be improved by understanding the ecological roles of indigenous fungi. However, further research is needed to better estimate specific amendment requirements for a broader group of target fungi and follow up studies are needed to determine whether the trends observed herein translate to more realistic soil systems.

Nontarget Screening with High Resolution Mass Spectrometry in the Environment: Ready to Go?

The vast, diverse universe of organic pollutants is a formidable challenge for environmental sciences, engineering, and regulation. Nontarget screening (NTS) based on high resolution mass spectrometry (HRMS) has enormous potential to help characterize this universe, but is it ready to go for real world applications? In this Feature article we argue that development of mass spectrometers with increasingly high resolution and novel couplings to both liquid and gas chromatography, combined with the integration of high performance computing, have significantly widened our analytical window and have enabled increasingly sophisticated data processing strategies, indicating a bright future for NTS. NTS has great potential for treatment assessment and pollutant prioritization within regulatory applications, as highlighted here by the case of real-time pollutant monitoring on the River Rhine. We discuss challenges for the future, including the transition from research toward solution-centered and robust, harmonized applications.

Discovery of 40 Classes of Per- and Polyfluoroalkyl Substances in Historical Aqueous Film-Forming Foams (AFFFs) and AFFF-Impacted Groundwater.

Aqueous film-forming foams (AFFFs), containing per- and polyfluoroalkyl substances (PFASs), are released into the environment during response to fire-related emergencies. Repeated historical applications of AFFF at military sites were a result of fire-fighter training exercises and equipment testing. Recent data on AFFF-impacted groundwater indicates that ∼25% of the PFASs remain unidentified. In an attempt to close the mass balance, a systematic evaluation of 3M and fluorotelomer-based AFFFs, commercial products, and AFFF-impacted groundwaters from 15 U.S. military bases was conducted to identify the remaining PFASs. Liquid chromatography quadrupole time-of-flight mass spectrometry was used for compound discovery. Nontarget analysis utilized Kendrick mass defect plots and a "nontarget" R script. Suspect screening compared masses with those of previously reported PFASs. Forty classes of novel anionic, zwitterionic, and cationic PFASs were discovered, and an additional 17 previously reported classes were observed for the first time in AFFF and/or AFFF-impacted groundwater. All 57 classes received an acronym and IUPAC-like name derived from collective author knowledge. Thirty-four of the 40 newly identified PFAS classes derive from electrochemical fluorination (ECF) processes, most of which have the same base structure. Of the newly discovered PFASs found only in AFFF-impacted groundwater, 11 of the 13 classes are ECF-derived, and the remaining two classes are fluorotelomer-derived, which suggests that both ECF- and fluorotelomer-based PFASs are persistent in the environment.

Influence of the Gastrointestinal Environment on the Bioavailability of Ethinyl Estradiol Sorbed to Single-Walled Carbon Nanotubes.

Recent evidence suggests that, because of their sorptive nature, if single-walled carbon nanotubes (SWCNTs) make their way into aquatic environments, they may reduce the toxicity of other waterborne contaminants. However, few studies have examined whether contaminants remain adsorbed following ingestion by aquatic organisms. The objective of this study was to examine the bioavailability and bioactivity of ethinyl estradiol (EE2) sorbed onto SWCNTs in a fish gastrointestinal (GI) tract. Sorption experiments indicated that SWCNTs effectively adsorbed EE2, but the chemical was still able to bind and activate soluble estrogen receptors (ERs) in vitro. However, centrifugation to remove SWCNTs and adsorbed EE2 significantly reduced ER activity compared to that of EE2 alone. Additionally, the presence of SWCNTs did not reduce the extent of EE2-driven induction of vitellogenin 1 in vivo compared to the levels in organisms exposed to EE2 alone. These results suggest that while SWCNTs adsorb EE2 from aqueous solutions, under biological conditions EE2 can desorb and retain bioactivity. Additional results indicate that interactions with gastrointestinal proteins may decrease the level of adsorption of estrogen to SWCNTs by 5%. This study presents valuable data for elucidating how SWCNTs interact with chemicals that are already present in our aquatic environments, which is essential for determining their potential health risk.

Effects of Toxic Leachate from Commercial Plastics on Larval Survival and Settlement of the Barnacle Amphibalanus amphitrite.

Plastic pollution represents a major and growing global problem. It is well-known that plastics are a source of chemical contaminants to the aquatic environment and provide novel habitats for marine organisms. The present study quantified the impacts of plastic leachates from the seven categories of recyclable plastics on larval survival and settlement of barnacle Amphibalanus (=Balanus) amphitrite. Leachates from plastics significantly increased barnacle nauplii mortality at the highest tested concentrations (0.10 and 0.50 m(2)/L). Hydrophobicity (measured as surface energy) was positively correlated with mortality indicating that plastic surface chemistry may be an important factor in the effects of plastics on sessile organisms. Plastic leachates significantly inhibited barnacle cyprids settlement on glass at all tested concentrations. Settlement on plastic surfaces was significantly inhibited after 24 and 48 h, but settlement was not significantly inhibited compared to the controls for some plastics after 72-96 h. In 24 h exposure to seawater, we found larval toxicity and inhibition of settlement with all seven categories of recyclable commercial plastics. Chemical analysis revealed a complex mixture of substances released in plastic leachates. Leaching of toxic compounds from all plastics should be considered when assessing the risks of plastic pollution.

Results from Screening Polyurethane Foam Based Consumer Products for Flame Retardant Chemicals: Assessing Impacts on the Change in the Furniture Flammability Standards.

Flame retardant (FR) chemicals have often been added to polyurethane foam to meet required state and federal flammability standards. However, some FRs (e.g., PBDEs and TDCIPP) are associated with health hazards and are now restricted from use in some regions. In addition, California's residential furniture flammability standard (TB-117) has undergone significant amendments over the past few years, and TDCIPP has been added to California's Proposition 65 list. These events have likely led to shifts in the types of FRs used, and the products to which they are applied. To provide more information on the use of FRs in products containing polyurethane foam (PUF), we established a screening service for the general public. Participants residing in the US were allowed to submit up to 5 samples from their household for analysis, free of charge, and supplied information on the product category, labeling, and year and state of purchase. Between February 2014 and June 2016, we received 1141 PUF samples for analysis from various products including sofas, chairs, mattresses, car seats and pillows. Of these samples tested, 52% contained a FR at levels greater than 1% by weight. Tris(1,3-dichloroisopropyl)phosphate (TDCIPP) was the most common FR detected in PUF samples, and was the most common FR detected in all product categories. Analysis of the data by purchasing date suggests that the use of TDCIPP decreased in recent years, paralleled with an increase in the use of TCIPP and a nonhalogenated aryl phosphate mixture we call "TBPP." In addition, we observed significant decreases in FR applications in furniture products and child car seats, suggesting the use of additive FRs in PUF may be declining, perhaps as a reflection of recent changes to TB-117 and Proposition 65. More studies are needed to determine how these changes in FR use relate to changes in exposure among the general population.

Indications of Transformation Products from Hydraulic Fracturing Additives in Shale-Gas Wastewater.

Unconventional natural gas development (UNGD) generates large volumes of wastewater, the detailed composition of which must be known for adequate risk assessment and treatment. In particular, transformation products of geogenic compounds and disclosed additives have not been described. This study investigated six Fayetteville Shale wastewater samples for organic composition using a suite of one- and two-dimensional gas chromatographic techniques to capture a broad distribution of chemical structures. Following the application of strict compound-identification-confidence criteria, we classified compounds according to their putative origin. Samples displayed distinct chemical distributions composed of typical geogenic substances (hydrocarbons and hopane biomarkers), disclosed UNGD additives (e.g., hydrocarbons, phthalates such as diisobutyl phthalate, and radical initiators such as azobis(isobutyronitrile)), and undisclosed compounds (e.g., halogenated hydrocarbons, such as 2-bromohexane or 4-bromoheptane). Undisclosed chloromethyl alkanoates (chloromethyl propanoate, pentanoate, and octanoate) were identified as potential delayed acids (i.e., those that release acidic moieties only after hydrolytic cleavage, the rate of which could be potentially controlled), suggesting they were deliberately introduced to react in the subsurface. In contrast, the identification of halogenated methanes and acetones suggested that those compounds were formed as unintended byproducts. Our study highlights the possibility that UNGD operations generate transformation products and underscores the value of disclosing additives injected into the subsurface.

Considerations of Environmentally Relevant Test Conditions for Improved Evaluation of Ecological Hazards of Engineered Nanomaterials.

Engineered nanomaterials (ENMs) are increasingly entering the environment with uncertain consequences including potential ecological effects. Various research communities view differently whether ecotoxicological testing of ENMs should be conducted using environmentally relevant concentrations-where observing outcomes is difficult-versus higher ENM doses, where responses are observable. What exposure conditions are typically used in assessing ENM hazards to populations? What conditions are used to test ecosystem-scale hazards? What is known regarding actual ENMs in the environment, via measurements or modeling simulations? How should exposure conditions, ENM transformation, dose, and body burden be used in interpreting biological and computational findings for assessing risks? These questions were addressed in the context of this critical review. As a result, three main recommendations emerged. First, researchers should improve ecotoxicology of ENMs by choosing test end points, duration, and study conditions-including ENM test concentrations-that align with realistic exposure scenarios. Second, testing should proceed via tiers with iterative feedback that informs experiments at other levels of biological organization. Finally, environmental realism in ENM hazard assessments should involve greater coordination among ENM quantitative analysts, exposure modelers, and ecotoxicologists, across government, industry, and academia.