Should Transformation Products Change the Way We Manage Chemicals?

When chemical pollutants enter the environment, they can undergo diverse transformation processes, forming a wide range of transformation products (TPs), some of them benign and others more harmful than their precursors. To date, the majority of TPs remain largely unrecognized and unregulated, particularly as TPs are generally not part of routine chemical risk or hazard assessment. Since many TPs formed from oxidative processes are more polar than their precursors, they may be especially relevant in the context of persistent, mobile, and toxic (PMT) and very persistent and very mobile (vPvM) substances, which are two new hazard classes that have recently been established on a European level. We highlight herein that as a result, TPs deserve more attention in research, chemicals regulation, and chemicals management. This perspective summarizes the main challenges preventing a better integration of TPs in these areas: (1) the lack of reliable high-throughput TP identification methods, (2) uncertainties in TP prediction, (3) inadequately considered TP formation during (advanced) water treatment, and (4) insufficient integration and harmonization of TPs in most regulatory frameworks. A way forward to tackle these challenges and integrate TPs into chemical management is proposed.

Ultra-Short-Chain PFASs in the Sources of German Drinking Water: Prevalent, Overlooked, Difficult to Remove, and Unregulated.

Per- and polyfluoroalkyl substances (PFASs) have been a focal point of environmental chemistry and chemical regulation in recent years, culminating in a shift from individual PFAS regulation toward a PFAS group regulatory approach in Europe. PFASs are a highly diverse group of substances, and knowledge about this group is still scarce beyond the well-studied, legacy long-chain, and short-chain perfluorocarboxylates (PFCAs) and perfluorosulfonates (PFSAs). Herein, quantitative and semiquantitative data for 43 legacy short-chain and ultra-short-chain PFASs (≤2 perfluorocarbon atoms for PFCAs, ≤3 for PFSAs and other PFASs) in 46 water samples collected from 13 different sources of German drinking water are presented. The PFASs considered include novel compounds like hexafluoroisopropanol, bis(trifluoromethylsulfonyl)imide, and tris(pentafluoroethyl)trifluorophosphate. The ultra-short-chain PFASs trifluoroacetate, perfluoropropanoate, and trifluoromethanesulfonate were ubiquitous and present at the highest concentrations (98% of sum target PFAS concentrations). "PFAS total" parameters like the adsorbable organic fluorine (AOF) and total oxidizable precursor (TOP) assay were found to provide only an incomplete picture of PFAS contamination in these water samples by not capturing these highly prevalent ultra-short-chain PFASs. These ultra-short-chain PFASs represent a major challenge for drinking water production and show that regulation in the form of preventive measures is required to manage them.

Occurrence, Distribution, and Environmental Behavior of Persistent, Mobile, and Toxic (PMT) and Very Persistent and Very Mobile (vPvM) Substances in the Sources of German Drinking Water.

Persistent, mobile, and toxic (PMT) and very persistent and very mobile (vPvM) substances have been recognized as a threat to both the aquatic environment and to drinking water resources. These substances are currently prioritized for regulatory action by the European Commission, whereby a proposal for the inclusion of hazard classes for PMT and vPvM substances has been put forward. Comprehensive monitoring data for many PMT/vPvM substances in drinking water sources are scarce. Herein, we analyze 34 PMT/vPvM substances in 46 surface water, groundwater, bank filtrate, and raw water samples taken throughout Germany. Results of the sampling campaign demonstrated that known PMT/vPvM substances such as 1H-benzotriazole, melamine, cyanuric acid, and 1,4-dioxane are responsible for substantial contamination in the sources of German drinking water. In addition, the results revealed the widespread presence of the emerging substances 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and diphenylguanidine (DPG). A correlation analysis showed a pronounced co-occurrence of PMT/vPvM substances associated predominantly with consumer or professional uses and also demonstrated an inhomogeneous co-occurrence for substances associated mainly with industrial use. These data were used to test the hypothesis that most PMT/vPvM substances pass bank filtration without significant concentration reduction, which is one of the main reasons for introducing PMT/vPvM as a hazard class within Europe.

Sorption and Mobility of Charged Organic Compounds: How to Confront and Overcome Limitations in Their Assessment.

Permanently charged and ionizable organic compounds (IOC) are a large and diverse group of compounds belonging to many contaminant classes, including pharmaceuticals, pesticides, industrial chemicals, and natural toxins. Sorption and mobility of IOCs are distinctively different from those of neutral compounds. Due to electrostatic interactions with natural sorbents, existing concepts for describing neutral organic contaminant sorption, and by extension mobility, are inadequate for IOC. Predictive models developed for neutral compounds are based on octanol-water partitioning of compounds (Kow) and organic-carbon content of soil/sediment, which is used to normalize sorption measurements (KOC). We revisit those concepts and their translation to IOC (Dow and DOC) and discuss compound and soil properties determining sorption of IOC under water saturated conditions. Highlighting possible complementary and/or alternative approaches to better assess IOC mobility, we discuss implications on their regulation and risk assessment. The development of better models for IOC mobility needs consistent and reliable sorption measurements at well-defined chemical conditions in natural porewater, better IOC-, as well as sorbent characterization. Such models should be complemented by monitoring data from the natural environment. The state of knowledge presented here may guide urgently needed future investigations in this field for researchers, engineers, and regulators.

The effects of soil organic matter on leaching of hexavalent chromium from concrete waste: Batch and column experiments.

Concrete is one of the most common building materials in the world and in accordance with the world's shift to a circular economy, there is a need of an increase in concrete reuse and recycling. One of the environmental concerns linked to concrete recycling is the leaching and spread of hexavalent chromium (Cr(VI)). In the present study the Cr(VI) leaching from crushed concrete waste and the effects of soil organic matter (SOM) on chromium (Cr) speciation has been investigated in realistic reuse scenarios by the means of batch shale tests and layered column tests. The effects of concrete properties (pH, grain size and age) on Cr(VI) leaching was also studied. Cr leaching from concrete alone is mainly in the form of Cr(VI), with the pH of the leachate being >10. The smaller the grainsize of the concrete, the higher the Cr(VI) concentration is in the leachate. There was no correlation between the age of the concrete and concrete leaching. When exposed to SOM the Total-Cr concentration in the leachate was reduced. The reduction increased with higher TOC level, with a 99% reduction at very high TOC (25%). The results indicate that Cr(VI) leaching from recycled concrete waste can be mitigated by exposing it to SOM in the desired recycling scenario.

Fluorinated Precursor Compounds in Sediments as a Source of Perfluorinated Alkyl Acids (PFAA) to Biota.

The environmental behavior of perfluorinated alkyl acids (PFAA) and their precursors was investigated in lake Tyrifjorden, downstream a factory producing paper products coated with per- and polyfluorinated alkyl substances (PFAS). Low water concentrations (max 0.18 ng L-1 linear perfluorooctanesulfonic acid, L-PFOS) compared to biota (mean 149 µg kg-1 L-PFOS in perch livers) resulted in high bioaccumulation factors (L-PFOS BAFPerch liver: 8.05 × 105-5.14 × 106). Sediment concentrations were high, particularly for the PFOS precursor SAmPAP diester (max 1 872 µg kg-1). Biota-sediment accumulation factors (L-PFOS BSAFPerch liver: 22-559) were comparable to elsewhere, and concentrations of PFAA precursors and long chained PFAA in biota were positively correlated to the ratio of carbon isotopes (13C/12C), indicating positive correlations to dietary intake of benthic organisms. The sum fluorine from targeted analyses accounted for 54% of the extractable organic fluorine in sediment, and 9-108% in biota. This, and high trophic magnification factors (TMF, 3.7-9.3 for L-PFOS), suggests that hydrophobic precursors in sediments undergo transformation and are a main source of PFAA accumulation in top predator fish. Due to the combination of water exchange and dilution, transformation of larger hydrophobic precursors in sediments can be a source to PFAA, some of which are normally associated with uptake from water.

Bioaccumulation of Fluorotelomer Sulfonates and Perfluoroalkyl Acids in Marine Organisms Living in Aqueous Film-Forming Foam Impacted Waters.

The use of aqueous film-forming foams (AFFFs) has resulted in hot spots polluted with poly- and perfluorinated alkyl substances (PFASs). The phase out of long-chained perfluoroalkyl acids (PFAAs) from AFFFs resulted in the necessity for alternatives, and short-chained PFAAs and fluorotelomer-based surfactants have been used. Here, the distribution of PFAS contamination in the marine environment surrounding a military site in Norway was investigated. Up to 30 PFASs were analyzed in storm, leachate, and fjord water; marine sediments; marine invertebrates (snails, green shore crab, great spider crab, and edible crab); and teleost fish (Atlantic cod, European place, and Lemon sole). Perfluorooctanesulfonic acid (PFOS) was the most abundantly detected PFAS. Differences in PFAS accumulation levels were observed among species, likely reflecting different exposure routes among trophic levels and different capabilities for depuration and/or enzymatic degradation. In agreement with previous literature, almost no 6:2 fluorotelomer sulfonate (6:2 FTS) was detected in teleost fish. However, this study is one of the first to report considerable concentrations of 6:2 FTS in marine invertebrates, suggesting bioaccumulation. Biota monitoring and risk assessments of sites contaminated with fluorotelomer sulfonates (FTSs) and related compounds should not be limited to fish, but should also include invertebrates.

Advancing the Use of Passive Sampling in Risk Assessment and Management of Sediments Contaminated with Hydrophobic Organic Chemicals: Results of an International Ex Situ Passive Sampling Interlaboratory Comparison.

This work presents the results of an international interlaboratory comparison on ex situ passive sampling in sediments. The main objectives were to map the state of the science in passively sampling sediments, identify sources of variability, provide recommendations and practical guidance for standardized passive sampling, and advance the use of passive sampling in regulatory decision making by increasing confidence in the use of the technique. The study was performed by a consortium of 11 laboratories and included experiments with 14 passive sampling formats on 3 sediments for 25 target chemicals (PAHs and PCBs). The resulting overall interlaboratory variability was large (a factor of ∼10), but standardization of methods halved this variability. The remaining variability was primarily due to factors not related to passive sampling itself, i.e., sediment heterogeneity and analytical chemistry. Excluding the latter source of variability, by performing all analyses in one laboratory, showed that passive sampling results can have a high precision and a very low intermethod variability (

The presence and partitioning behavior of flame retardants in waste, leachate, and air particles from Norwegian waste-handling facilities.

Flame retardants in commercial products eventually make their way into the waste stream. Herein the presence of flame retardants in Norwegian landfills, incineration facilities and recycling sorting/defragmenting facilities is investigated. These facilities handled waste electrical and electronic equipment (WEEE), vehicles, digestate, glass, combustibles, bottom ash and fly ash. The flame retardants considered included polybrominated diphenyl ethers (∑BDE-10) as well as dechlorane plus, polybrominated biphenyls, hexabromobenzene, pentabromotoluene and pentabromoethylbenzene (collectively referred to as ∑FR-7). Plastic, WEEE and vehicles contained the largest amount of flame retardants (∑BDE-10: 45,000-210,000µg/kg; ∑FR-7: 300-13,000µg/kg). It was hypothesized leachate and air concentrations from facilities that sort/defragment WEEE and vehicles would be the highest. This was supported for total air phase concentrations (∑BDE-10: 9000-195,000pg/m3 WEEE/vehicle facilities, 80-900pg/m3 in incineration/sorting and landfill sites), but not for water leachate concentrations (e.g., ∑BDE-10: 15-3500ng/L in WEEE/Vehicle facilities and 1-250ng/L in landfill sites). Landfill leachate exhibited similar concentrations as WEEE/vehicle sorting and defragmenting facility leachate. To better account for concentrations in leachates at the different facilities, waste-water partitioning coefficients, Kwaste were measured (for the first time to our knowledge for flame retardants). WEEE and plastic waste had elevated Kwaste compared to other wastes, likely because flame retardants are directly added to these materials. The results of this study have implications for the development of strategies to reduce exposure and environmental emissions of flame retardants in waste and recycled products through improved waste management practices.

How to Determine the Environmental Exposure of PAHs Originating from Biochar.

Biochars are obtained by pyrolyzing biomass materials and are increasingly used within the agricultural sector. Owing to the production process, biochars can contain polycyclic aromatic hydrocarbons (PAHs) in the high mg/kg range, which makes the determination of the environmental exposure of PAHs originating from biochars relevant. However, PAH sorption to biochar is characterized by very high (10(4)-10(6) L/kg) or extreme distribution coefficients (KD) (>10(6) L/kg), which makes the determination of exposure scientifically and technically challenging. Cyclodextrin extractions, sorptive bioaccessibility extractions, Tenax extractions, contaminant traps, and equilibrium sampling were assessed and selected methods used for the determination of bioavailability parameters for PAHs in two model biochars. Results showed that: (1) the KD values of typically 10(6)-10(9) L/kg made the biochars often act as sinks, rather than sources, of PAHs. (2) Equilibrium sampling yielded freely dissolved concentrations (pg-ng/L range) that were below or near environmental background levels. (3) None of the methods were found to be suitable for the direct measurement of the readily desorbing fractions of PAHs (i.e., bioacessibility) in the two biochars. (4) The contaminant-trap method yielded desorption-resistant PAH fractions of typically 90-100%, implying bioaccessibility in the high µg/kg to low mg/kg range.

Bisphenol A in Solid Waste Materials, Leachate Water, and Air Particles from Norwegian Waste-Handling Facilities: Presence and Partitioning Behavior.

The plastic additive bisphenol A (BPA) is commonly found in landfill leachate at levels exceeding acute toxicity benchmarks. To gain insight into the mechanisms controlling BPA emissions from waste and waste-handling facilities, a comprehensive field and laboratory campaign was conducted to quantify BPA in solid waste materials (glass, combustibles, vehicle fluff, waste electric and electronic equipment (WEEE), plastics, fly ash, bottom ash, and digestate), leachate water, and atmospheric dust from Norwegian sorting, incineration, and landfill facilities. Solid waste concentrations varied from below 0.002 mg/kg (fly ash) to 188 ± 125 mg/kg (plastics). A novel passive sampling method was developed to, for the first time, establish a set of waste-water partition coefficients, KD,waste, for BPA, and to quantify differences between total and freely dissolved concentrations in waste-facility leachate. Log-normalized KD,waste (L/kg) values were similar for all solid waste materials (from 2.4 to 3.1), excluding glass and metals, indicating BPA is readily leachable. Leachate concentrations were similar for landfills and WEEE/vehicle sorting facilities (from 0.7 to 200 µg/L) and dominated by the freely dissolved fraction, not bound to (plastic) colloids (agreeing with measured KD,waste values). Dust concentrations ranged from 2.3 to 50.7 mg/kgdust. Incineration appears to be an effective way to reduce BPA concentrations in solid waste, dust, and leachate.

Per- and polyfluoroalkyl substance (PFAS) removal from soil washing water by coagulation and flocculation.

Soil washing is currently attracting attention as a promising remediation strategy for land contaminated with per- and polyfluoroalkyl substances (PFAS). In the soil washing process, the contaminant is transferred from the soil into the liquid phase, producing a PFAS contaminated process water. One way to treat such process water is to use coagulation and flocculation; however, few studies are available on the performance of coagulation and flocculation for removing PFAS from such process water. This study evaluated 6 coagulants and flocculants (polyaluminium chloride (PACl), zirconium oxychloride octahydrate, cationic and anionic polyacrylamide, Polyclay 685 and Perfluor Ad®), for the treatment of a proxy PFAS contaminated washing water, spiked with PFAS concentrations found at typical Aqueous Film Forming Foam (AFFF) contaminated sites. PFAS removal efficiencies (at constant pH) varied greatly depending on the coagulants and flocculants, as well as the dosage used and the targeted PFAS. All tested coagulants and flocculants reduced the turbidity by >95%, depending on the dosage. Perfluor Ad®, a specially designed coagulant, showed the highest removal efficiency for all longer chain (>99%) and shorter chain PFAS (>68%). The cationic polyacrylamide polymer removed longer chain PFAS up to an average of 80%, whereas average shorter chain PFAS removal was lower (<30%). The two metal-based coagulants tested, PACl and zirconium, removed longer chain PFAS by up to an average of 61% and shorter chain PFAS up to 48%. Polyclay 685, a mixture of powdered activated carbon (PAC) and aluminium sulphate, removed longer chain PFAS by 90% and shorter chain PFAS on average by 76%, when very high dosages of the coagulant were used (2,000 mg/L). PFAS removal efficiencies correlated with chain length and headgroup. Shorter chain PFAS removal was dependent on electrostatic interaction with the precipitating flocs, whereas for longer chain PFAS, hydrophobic interactions between apolar functional groups and flocs created by the coagulant/flocculant, dissolved organic matter and suspended solids played a major role. The results of this study showed that by selecting the most efficient coagulant and aqueous conditions, a greater amount of PFAS can be removed from process waters in soil washing facilities, and thus included as part of various treatment trains.

Grouping strategies for assessing and managing persistent and mobile substances.

Background: Persistent, mobile and toxic (PMT), or very persistent and very mobile (vPvM) substances are a wide class of chemicals that are recalcitrant to degradation, easily transported, and potentially harmful to humans and the environment. Due to their persistence and mobility, these substances are often widespread in the environment once emitted, particularly in water resources, causing increased challenges during water treatment processes. Some PMT/vPvM substances such as GenX and perfluorobutane sulfonic acid have been identified as substances of very high concern (SVHCs) under the European Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) regulation. With hundreds to thousands of potential PMT/vPvM substances yet to be assessed and managed, effective and efficient approaches that avoid a case-by-case assessment and prevent regrettable substitution are necessary to achieve the European Union's zero-pollution goal for a non-toxic environment by 2050. Main: Substance grouping has helped global regulation of some highly hazardous chemicals, e.g., through the Montreal Protocol and the Stockholm Convention. This article explores the potential of grouping strategies for identifying, assessing and managing PMT/vPvM substances. The aim is to facilitate early identification of lesser-known or new substances that potentially meet PMT/vPvM criteria, prompt additional testing, avoid regrettable use or substitution, and integrate into existing risk management strategies. Thus, this article provides an overview of PMT/vPvM substances and reviews the definition of PMT/vPvM criteria and various lists of PMT/vPvM substances available. It covers the current definition of groups, compares the use of substance grouping for hazard assessment and regulation, and discusses the advantages and disadvantages of grouping substances for regulation. The article then explores strategies for grouping PMT/vPvM substances, including read-across, structural similarity and commonly retained moieties, as well as the potential application of these strategies using cheminformatics to predict P, M and T properties for selected examples. Conclusions: Effective substance grouping can accelerate the assessment and management of PMT/vPvM substances, especially for substances that lack information. Advances to read-across methods and cheminformatics tools are needed to support efficient and effective chemical management, preventing broad entry of hazardous chemicals into the global market and favouring safer and more sustainable alternatives.

Effect-Directed Analysis Based on Transthyretin Binding Activity of Per- and Polyfluoroalkyl Substances in a Contaminated Sediment Extract.

Only a fraction of the total number of per- and polyfluoroalkyl substances (PFAS) are monitored on a routine basis using targeted chemical analyses. We report on an approach toward identifying bioactive substances in environmental samples using effect-directed analysis by combining toxicity testing, targeted chemical analyses, and suspect screening. PFAS compete with the thyroid hormone thyroxin (T4 ) for binding to its distributor protein transthyretin (TTR). Therefore, a TTR-binding bioassay was used to prioritize unknown features for chemical identification in a PFAS-contaminated sediment sample collected downstream of a factory producing PFAS-coated paper. First, the TTR-binding potencies of 31 analytical PFAS standards were determined. Potencies varied between PFAS depending on carbon chain length, functional group, and, for precursors to perfluoroalkyl sulfonic acids (PFSA), the size or number of atoms in the group(s) attached to the nitrogen. The most potent PFAS were the seven- and eight-carbon PFSA, perfluoroheptane sulfonic acid (PFHpS) and perfluorooctane sulfonic acid (PFOS), and the eight-carbon perfluoroalkyl carboxylic acid (PFCA), perfluorooctanoic acid (PFOA), which showed approximately four- and five-times weaker potencies, respectively, compared with the native ligand T4 . For some of the other PFAS tested, TTR-binding potencies were weak or not observed at all. For the environmental sediment sample, not all of the bioactivity observed in the TTR-binding assay could be assigned to the PFAS quantified using targeted chemical analyses. Therefore, suspect screening was applied to the retention times corresponding to observed TTR binding, and five candidates were identified. Targeted analyses showed that the sediment was dominated by the di-substituted phosphate ester of N-ethyl perfluorooctane sulfonamido ethanol (SAmPAP diester), whereas it was not bioactive in the assay. SAmPAP diester has the potential for (bio)transformation into smaller PFAS, including PFOS. Therefore, when it comes to TTR binding, the hazard associated with this substance is likely through (bio)transformation into more potent transformation products. Environ Toxicol Chem 2024;43:245-258. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Human exposure to per- and polyfluoroalkyl substances (PFAS) via the consumption of fish leads to exceedance of safety thresholds.

Per- and polyfluoroalkyl substances (PFAS) receive global attention due to their adverse effects on human health and the environment. Fish consumption is a major source of human PFAS exposure. The aim of this work was to address the lack of harmonization within legislations (in the EU and the USA) and highlight the level of PFAS in fish exposed to pollution from diffuse sources in the context of current safety thresholds. A non-exhaustive literature review was carried out to obtain PFAS concentrations in wild fish from the Norwegian mainland, Svalbard, the Netherlands, the USA, as well as sea regions (North Sea, English Channel, Atlantic Ocean), and farmed fish on the Dutch market. Median sum wet weight concentrations of PFOA, PFNA, PFHxS, and PFOS ranged between 0.1 µg kg-1 (farmed fish) and 22 µg kg-1 (Netherlands eel). Most concentrations fell below the EU environmental quality standard (EQSbiota) for PFOS (9.1 µg kg-1) and would not be defined as polluted in the EU. However, using recent tolerable intake or reference dose values in the EU and the USA revealed that even limited fish consumption would lead to exceedance of these thresholds - possibly posing a challenge for risk communication.

Study on the fate of per- and polyfluoroalkyl substances during thermophilic anaerobic digestion of sewage sludge and the role of granular activated carbon addition.

Limited information is available on the removal of per- and polyfluoroalkyl substances (PFAS) in anaerobic digestion (AD). Τhe fate of six PFAS was studied in thermophilic bioreactors in the presence of granular activated carbon (GAC) and voltage application. Reactors with GAC exhibited lower concentrations of volatile fatty acids and higher methane production compared to those with and without the application of voltage. Analysis of PFAS in dissolved and solid phase showed that their distribution was dependent on perfluorocarbon chain length and functional group. Mass balances showed that PFAS were not removed during conventional AD or after applying voltage; however, significant removal (up to 61 ± 8 %) was observed in bioreactors with GAC for perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonate (PFOS). Biomass characterization showed that in these bioreactors, the relative abundance of Acinetobacter and Pseudomonas was higher, indicating their potential role in PFAS biotransformation.