Environmental Fate of Cl-PFPECAs: Predicting the Formation of PFAS Transformation Products in New Jersey Soils.

Although next-generation per- and polyfluorinated substances (PFAS) were designed and implemented as safer and environmentally degradable alternatives to "forever" legacy PFAS, there is little evidence to support the actual transformation of these compounds and less evidence of the safety of transformed products in the environment. Multiple congeners of one such PFAS alternative, the chloro-perfluoropolyether carboxylates (Cl-PFPECAs), have been found in New Jersey soils surrounding a manufacturing facility. These compounds are ideal candidates for investigating environmental transformation due to the existence of potential reaction centers including a chlorinated carbon and ether linkages. Transformation products of the chemical structures of this class of compounds were predicted based on analogous PFAS transformation pathways documented in peer-reviewed literature. Potential reaction products were used as the basis for high-resolution mass-spectrometric suspect screening of the soils. Suspected transformation products of multiple congeners, the Cl-PFPECAs, including H-PFPECAs, epox-PFPECAs, and diOH-PFPECAs, were tentatively observed in these screenings. Although ether linkages have been hypothesized as potential reaction centers under environmental conditions, to date, no documentation of ether scission has been identified. Despite exhaustive scrutiny of the high-resolution data for our Cl-PFPECA-laden soils, we found no evidence of ether scission.

Modeling framework for simulating concentrations of solute chemicals, nanoparticles, and solids in surface waters and sediments: WASP8 Advanced Toxicant Module.

Toxicant concentrations in surface waters are of environmental concern due to their potential impacts to humans and wildlife. Numerical models provide system insight, support management decisions, and provide scenario testing on the impacts of toxicants. The Water Quality Analysis Simulation Program (WASP) is a widely used framework for developing site-specific models for simulating toxicant concentrations in surface waters and sediments over a range of complexities and temporal and spatial scales. WASP8, with the Advanced Toxicant module, has been recently released, incorporating a complete architecture redesign for an increased number of state variables and different state variable types. WASP8 incorporates a new structure for simulating light intensity and photoreactions in the water column, including the distinction of 10 different wavelength bands, and nanoparticle heteroaggregation to solids. We present a hypothetical case study, using the Cape Fear River, North Carolina as a representative example for simulating solute chemicals, nanoparticles, and solids to demonstrate the new and updated capabilities of WASP8.

Biological Weighting Functions for Evaluating the Role of Sunlight-Induced Inactivation of Coliphages at Selected Beaches and Nearby Tributaries.

Coliphages can indicate contamination of recreational waters and previous studies show that sunlight is important in altering densities of coliphages, other indicator microorganisms, and pathogens in aquatic environments. Here, we report on laboratory studies of light-induced inactivation of two coliphage groups-male-specific (F+) and somatic coliphage-under various conditions in phosphate-buffered water (PBW). Strains isolated from wastewater treatment facilities and laboratory strains (MS2 and phiX174 coliphages) were evaluated. Inactivation rates were determined in a series of irradiations using simulated solar radiation passed through light filters that blocked different parts of the ultraviolet spectral region. Inactivation rates and spectral irradiance from these experiments were then analyzed to develop biological weighting functions (BWFs) for the light-induced inactivation. BWFs were used to model the inactivation of coliphages over a range of conditions in aquatic environments that included two beach sites in Lake Michigan and one in Lake Erie. For example, modeled effects of sunlight attenuation, using UV absorption data from the three Great Lakes beach sites, inferred that direct photoinactivation rate constants, averaged over a one-meter water column in swimmable areas, were reduced 2- to 5-fold, compared to near-surface rate constants.

NanoRelease: Pilot interlaboratory comparison of a weathering protocol applied to resilient and labile polymers with and without embedded carbon nanotubes.

A major use of multi-walled carbon nanotubes (MWCNTs) is as functional fillers embedded in a solid matrix, such as plastics or coatings. Weathering and abrasion of the solid matrix during use can lead to environmental releases of the MWCNTs. Here we focus on a protocol to identify and quantify the primary release induced by weathering, and assess reproducibility, transferability, and sensitivity towards different materials and uses. We prepared 132 specimens of two polymer-MWCNT composites containing the same grade of MWCNTs used in earlier OECD hazard assessments but without UV stabilizer. We report on a pilot inter-laboratory comparison (ILC) with four labs (two US and two EU) aging by UV and rain, then shipping for analysis. Two labs (one US and one EU) conducted the release sampling and analysis by Transmission Electron Microscopy (TEM), Inductively Coupled Plasma- Mass Spectrometry (ICP-MS), UltravioleteVisible Spectroscopy (UVeVis), Analytical Ultracentrifugation (AUC), and Asymmetric Flow Field Flow Fractionation (AF4). We compare results between aging labs, between analysis labs and between materials. Surprisingly, we found quantitative agreement between analysis labs for TEM, ICP-MS, UVeVis; low variation between aging labs by all methods; and consistent rankings of release between TEM, ICP-MS, UVeVis, AUC. Significant disagreement was related primarily to differences in aging, but even these cases remained within a factor of two.

Fragmentation and release of pristine and functionalized carbon nanotubes from epoxy-nanocomposites during accelerated weathering.

There is an increasing volume of nano-enabled materials in the market. Once composites containing nano-additives are disposed of, weathering could deteriorate their structures, releasing nanoparticles and risking exposure of humans and aquatic organisms. Composite degradation due to environmental aging continues, including structural deterioration resulting in cracking, fragmentation, and release of microplastics and nano-additives to the environment. This research aims to study the degradation and release of initially embedded nanomaterials (NMs) from composites and their toxicity. The molecular interaction of carbon nanotube (CNT)/polymer composites is critical for modifying the polymer properties. This study investigated the interactions of functional multiwalled carbon nanotube (MWCNT) composites which affect their release during accelerated weathering processes. Different epoxy-MWCNT composites were prepared by filling a polymer with pure MWCNTs and MWCNTs functionalized with acid (-COOH) and amine (-NH2) groups. The physical and chemical changes of aged composites were characterized by gravimetric analysis, contact angle measurements, FTIR, SEM, and laser confocal microscopy. A loss of hydrophobicity was observed for composite surfaces long before surface cracks materialized. Released polymer fragments and nanoparticles were analyzed in wash water using TEM, FTIR and Raman spectroscopy. The environmental risks for long-term use of CNT-polymer composites and the influence of fillers on the extent of chemical photodegradation depended on the combination of polymer and fillers. If nanoparticles are released from the matrix, the high surface-to-volume ratio and reactivity of NMs make them highly dynamic in environmental systems. Exposure to these released NMs could negatively affect human health and the environment. This study provides fragmentation and CNT particle release data that could describe how molecular-level interactions between functionalized CNTs and epoxy polymers affect the aging and release of CNTs. A toxicity assessment based on a reactive oxygen species (ROS) formation assay and MTS assay for cell viability and activity of the released polymer and CNT fragments and leachate showed moderate levels of cytotoxicity of released materials as compared to pristine epoxy plates.

Weathering Effects on Degradation of Low-Density Polyethylene-Nanosilica Composite with Added Pro-oxidant.

Nanomaterials are increasingly used in polymer composites to enhance their properties, such as mechanical performance and durability, increased electrical conductivity, and improved optical clarity. Here results are presented of a study simulating effects of weathering on degradation of a nanosilica-low-density polyethylene (LDPE) composite. Release of nanosilica from LDPE composites is a potential source of toxic SiO2. Nanosilica based LDPE composites were weathered under carefully controlled conditions by exposure to simulated sunlight. The effects of an added pro-oxidant on weathering was examined. Weathering of the composites with pro-oxidant was determined by quantifying changes in infrared spectroscopic properties (Fourier transform infrared spectroscopy / FTIR); mechanical properties, atomic force microscopy (AFM), scanning electron microscopy and other procedures. Wavelength effects on weathering rates were determined in a series of irradiations using simulated solar radiation passed through light filters that blocked different parts of the ultraviolet spectral region. Rates and spectral irradiance were then analyzed to develop spectral weighting functions (SWFs) that quantify wavelength effects on the sunlight-induced weathering of the pro-oxidant amended composites.

Effect of UV-light exposure duration, light source, and aging on nitroguanidine (NQ) degradation product profile and toxicity.

Previous studies have reported increased aquatic toxicity of UV-degraded nitroguanidine (NQ), but many details underlying the dynamics of NQ degradation and toxicity remain unknown. These data gaps represent critical barriers to assessing the environmental relevance of laboratory-generated UV-degradation results and extrapolation to environmental risk. In the present study, the toxicity of NQ increased with increasing proportional degradation of the parent compound. Specifically, while the LC50 of undegraded NQ was 1485 mg/L, the toxicity at the lowest degradation level examined (7% parent compound degraded) increased by nearly two-orders of magnitude (LC50 = 17.3 mg/L) and increased by nearly three-orders of magnitude (LC50 = 6.23 mg/L) in the highest percent NQ degradation (90%) treatment. Similar LC50 values between immediately tested and aged (8-13 days) NQ degradation products suggested the degradation product(s) causing the toxicity were stable, although concentrations of nitrite and nitrate increased after aging. Finally, experiments where NQ was degraded in natural sunlight confirmed increased toxicity in environmentally relevant D. pulex exposures; however, the two-order of magnitude increase in toxicity (LC50 = 21.3 mg/L) at 53% degradation was less than NQ degraded by a laboratory photoreactor by a similar percentage (46% degraded). Identification of principal toxic agents in the UV-degraded NQ product mixture remains a critical data gap. Mass balance calculations were generated for our experimental results and literature values revealing difficulty in accounting for all NQ degradation products. Products with suspected high potency in D. pulex were identified which require further testing including: nitrosoguanidine, nitrosourea, and hydroxylamine. SYNOPSIS: The toxicity of NQ increased with increasing UV-degradation where toxicity-inducing degradation products were stable over 1-2 weeks; increased toxicity was validated from natural-sunlight degradation of NQ, however toxicity was lower than UV-photoreactor degraded NQ; and the identity of specific toxic UV-degradation products remains elusive where carefully-designed mass-balance experiments and toxicity testing are needed to provide definitive identification.

Per- and polyfluoroalkyl substances in the environment.

Over the past several years, the term PFAS (per- and polyfluoroalkyl substances) has grown to be emblematic of environmental contamination, garnering public, scientific, and regulatory concern. PFAS are synthesized by two processes, direct fluorination (e.g., electrochemical fluorination) and oligomerization (e.g., fluorotelomerization). More than a megatonne of PFAS is produced yearly, and thousands of PFAS wind up in end-use products. Atmospheric and aqueous fugitive releases during manufacturing, use, and disposal have resulted in the global distribution of these compounds. Volatile PFAS facilitate long-range transport, commonly followed by complex transformation schemes to recalcitrant terminal PFAS, which do not degrade under environmental conditions and thus migrate through the environment and accumulate in biota through multiple pathways. Efforts to remediate PFAS-contaminated matrices still are in their infancy, with much current research targeting drinking water.

Using metabolomic profiling to inform use of surrogate species in ecological risk assessment practices.

The U.S. EPA frequently uses avian or fish toxicity data to set protective standards for amphibians in ecological risk assessments. However, this approach does not always adequately represent aquatic-dwelling and terrestrial-phase amphibian exposure data. For instance, it is accepted that early life stage tests for fish are typically sensitive enough to protect larval amphibians, however, metamorphosis from tadpole to a terrestrial-phase adult relies on endocrine cues that are less prevalent in fish but essential for amphibian life stage transitions. These differences suggest that more robust approaches are needed to adequately elucidate the impacts of pesticide exposure in amphibians across critical life stages. Therefore, in the current study, methodology is presented that can be applied to link the perturbations in the metabolomic response of larval zebrafish (Danio rerio), a surrogate species frequently used in ecotoxicological studies, to those of African clawed frog (Xenopus laevis) tadpoles following exposure to three high-use pesticides, bifenthrin, chlorothalonil, or trifluralin. Generally, D. rerio exhibited greater metabolic perturbations in both number and magnitude across the pesticide exposures as opposed to X. laevis. This suggests that screening ecological risk assessment surrogate toxicity data would sufficiently protect amphibians at the single life stage studied but care needs to be taken to understand the suite of metabolic requirements of each developing species. Ultimately, methodology presented, and data gathered herein will help inform the applicability of metabolomic profiling in establishing the risk pesticide exposure poses to amphibians and potentially other non-target species.

Fragmentation of polymer nanocomposites: modulation by dry and wet weathering, fractionation, and nanomaterial filler.

In recent years, an increasing number of polymeric composites incorporating engineered nanomaterials (ENMs) have reached the market. Such nano-enabled products (NEPs) present enhanced performance through improved mechanical, thermal, UV protection, electrical, and gas barrier properties. However, little is known about how environmental weathering impacts ENM release, especially for high-tonnage NEPs like kaolin products, which have not been extensively examined by the scientific community. Here we study the simulated environmental weathering of different polymeric nanocomposites (epoxy, polyamide, polypropylene) filled with organic (multiwalled carbon nanotube, graphene, carbon black) and inorganic (WS2, SiO2, kaolin, Fe2O3, Cu-phthalocyanines) ENMs. Multiple techniques were employed by researchers at three laboratories to extensively evaluate the effect of weathering: ultraviolet-visible spectroscopy (UV-vis), Fourier transform infrared spectroscopy (FTIR), optical microscopy, contact angle measurements, gravimetric analysis, analytical ultracentrifugation (AUC), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Raman spectroscopy. This work aimed to elucidate the extent to which weathering protocol (i.e. wet vs. dry) and diverse filler characteristics modulate fragment release and polymer matrix degradation. In doing so, it expanded the established NanoRelease protocol, previously used for analyzing fragment emission, by evaluating two significant additions: (1) simulated weathering with rain events and (2) fractionation of sample leachate prior to analysis. Comparing different composite materials and protocols demonstrated that the polymer matrix is the most significant factor in NEP aging. Wet weathering is more realistic than dry weathering, but dry weathering seems to provide a more controlled release of material over wet. Wet weathering studies could be complicated by leaching, and the addition of a fractionation step can improve the quality of UV-vis measurements.

Modeling the photoinactivation and transport of somatic and F-specific coliphages at a Great Lakes beach.

Fecal indicator organisms (FIOs), such as Escherichia coli and enterococci, are often used as surrogates of contamination in the context of beach management; however, bacteriophages may be more reliable indicators than FIO due to their similarity to viral pathogens in terms of size and persistence in the environment. In the past, mechanistic modeling of environmental contamination has focused on FIOs, with virus and bacteriophage modeling efforts remaining limited. In this paper, we describe the development and application of a fate and transport model of somatic and F-specific coliphages for the Washington Park beach in Lake Michigan, which is affected by riverine outputs from the nearby Trail Creek. A three-dimensional model of coliphage transport and photoinactivation was tested and compared with a previously reported E. coli fate and transport model. The light-based inactivation of the phages was modeled using organism-specific action spectra. Results indicate that the coliphage models outperformed the E. coli model in terms of reliably predicting observed E. coli/coliphage concentrations at the beach. This is possibly due to the presence of additional E. coli sources that were not accounted for in the modeling. The coliphage models can be used to test hypotheses about potential sources and their behavior and for predictive modeling.

Environmental fate of multiwalled carbon nanotubes and graphene oxide across different aquatic ecosystems.

The industrial use and widespread application of carbon-based nanomaterials have caused a rapid increase in their production over the last decades. However, toxicity of these materials is not fully known and is still being investigated for potential human and ecological health risks. Detecting carbon-based nanomaterials in the environment using current analytical methods is problematic, making environmental fate and transport modeling a practical way to estimate environmental concentrations and assess potential ecological risks. The Water Quality Analysis Simulation Program 8 (WASP8) is a dynamic, spatially resolved fate and transport model for simulating exposure concentrations in surface waters and sediments. Recently, WASP has been updated to incorporate processes for simulating the fate and transport of nanomaterials including heteroaggregation and phototransformation. This study examines the fate and transport of multiwalled carbon nanotubes (MWCNT), graphene oxide (GO) and reduced graphene oxide (rGO) in four aquatic ecosystems in the southeastern United States. Sites include a seepage lake, a coastal plains river, a piedmont river and an unstratified, wetland lake. A hypothetical 50-year release is simulated for each site-nanomaterial pair to analyze nanomaterial distribution between the water column and sediments. For all nanomaterials, 99% of the mass loaded moves though systems of high and low residence times without being heteroaggregated and deposited in the sediments. However, significant accumulation in the sediments does occur over longer periods of time. Results show that GO and rGO had the highest mass fraction in the water column of all four sites. MWCNT were found predominantly in the sediments of the piedmont river and seepage lake but were almost entirely contained in the water column of the coastal plains river and wetland lake. Simulated recovery periods following the release estimate 37+ years for lakes and 1-4 years for rivers to reduce sediment nanomaterial concentrations by 50% suggesting that carbon-based nanomaterials have the potential for long-term ecological effects.

Simulating graphene oxide nanomaterial phototransformation and transport in surface water.

The production of graphene-family nanomaterials (GFNs) has increased appreciably in recent years. Graphene oxide (GO) has been found to be the most toxic nanomaterial among GFNs and, to our knowledge, no studies have been conducted to model its fate and transport in the environment. Lab studies show that GO undergoes phototransformation in surface waters under sunlight radiation resulting in formation of photoreduced GO (rGO). In this study, the recently updated Water Quality Analysis Simulation Program (WASP8) is used to simulate time-dependent environmental exposure concentrations of GO and its major phototransformation product, rGO, for Brier Creek, GA, USA at two flow scenarios under a constant loading of GO to the river for a period of 20 years. Analysis shows that the degree of phototransformation is closely associated with river flow condition: up to of 40% of GO undergoes phototransformation at low flow condition, whereas only 2.5% of GO phototransformation occurs at mean flow condition. River flow and heteroaggregation exhibit a 'competing' effect in determining the formation of rGO heteroagglomerates. Mass fraction analysis indicates that the vast majority of rGO heteroagglomerates settle to the sediment layers due to the settling of suspended solids. Simulation of natural recovery after removal of the GO source suggests that free GO and rGO are the immediate contaminants of concern in the studied surface water system, while rGO heteroaggregated with suspended solids can have a long-term ecological impact on both the water column and sediments.

Incidence of somatic and F+ coliphage in Great Lake Basin recreational waters.

There is a growing interest for the use of coliphage as an alternative indicator to assess fecal pollution in recreational waters. Coliphage are a group of viruses that infect Escherichia coli and are considered as potential surrogates to infer the likely presence of enteric viral pathogens. We report the use of a dead-end hollow fiber ultrafiltration single agar layer method to enumerate F+ and somatic coliphage from surface waters collected from three Great Lake areas. At each location, three sites (two beaches; one river) were sampled five days a week over the 2015 beach season (n = 609 total samples). In addition, culturable E. coli and enterococci concentrations, as well as 16 water quality and recreational area parameters were assessed such as rainfall, turbidity, dissolved oxygen, pH, and ultra violet absorbance. Overall, somatic coliphage levels ranged from non-detectable to 4.39 log10 plaque forming units per liter and were consistently higher compared to F+ (non-detectable to 3.15 log10 PFU/L), regardless of sampling site. Coliphage concentrations weakly correlated with cultivated fecal indicator bacteria levels (E. coli and enterococci) at 75% of beach sites tested in study (r = 0.28 to 0.40). In addition, ultraviolet light absorption and water temperature were closely associated with coliphage concentrations, but not fecal indicator bacteria levels suggesting different persistence trends in Great Lake waters between indicator types (bacteria versus virus). Finally, implications for coliphage water quality management and future research directions are discussed.