Embryonic Exposure to Benzotriazole Ultraviolet Stabilizer 327 Alters Behavior of Rainbow Trout Alevin.

Benzotriazole ultraviolet (UV) stabilizers (BUVSs) are used in great quantities during industrial production of a variety of consumer and industrial goods. As a result of leaching and spill, BUVSs are detectable ubiquitously in the environment. As of May 2023, citing concerns related to bioaccumulation, biomagnification, and environmental persistence, (B)UV(S)-328 was recommended to be listed under Annex A of the Stockholm Convention on Persistent Organic Pollutants. However, a phaseout of UV-328 could result in a regrettable substitution because the replacement chemical(s) could cause similar or unpredicted toxicity in vivo, relative to UV-328. Therefore, the influence of UV-327, a potential replacement of UV-328, was investigated with respect to early life development of newly fertilized rainbow trout embryos (Oncorhynchus mykiss), microinjected with environmentally relevant concentrations of UV-327. Developmental parameters (standard length), energy consumption (yolk area), heart function, blue sac disease, mortality, and behavior were investigated. Alevins at 14 days posthatching, exposed to 107 ng UV-327 g-1 egg, presented significant signs of hyperactivity; they moved on average 1.8-fold the distance and at 1.5-fold the velocity of controls. Although a substantial reduction in body burden of UV-327 was observed at hatching, it is postulated that UV-327, due to its lipophilic properties, interfered with neurological development and signaling from the onset of neurogenesis. If these results hold true across multiple taxa and species, a potential contributor to neurodevelopmental disorders might have been identified. These findings suggest that UV-327 poses an unknown hazard to rainbow trout embryos and alevins, rendering UV-327 a potential regrettable substitution to UV-328. However, a qualified statement on a regrettable substitution requires a comparative investigation on the teratogenic effects between the two BUVSs. Environ Toxicol Chem 2024;43:762-771. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

First Record of Malformation in Seahorses Attributed to the Oil Spill off the Brazilian Coast in 2019.

In 2019, there was an environmental catastrophe in Brazil, when more than 5000 tons of unknown origin crude oil invaded beaches and mangroves. Two years later, two monitoring areas were selected to study seahorses' offspring: Massangana River estuary (apparently healthy area) and Cocaia Island (affected area). Thirty-six reproductive events of Hippocampus reidi (Syngnathidae) couples from these two areas were monitored to analyze the offspring. At the apparently healthy area, no newborns with malformations were found. However, the offspring from Cocaia Island showed a mean of 19.73% (±5.23) malformations in newborns. It is argued that the toxic/teratogenic effects of polycyclic aromatic hydrocarbons have affected the population in two ways: directly through the induction of mutations in the germ cells of the species and through a drastic reduction of the population (bottleneck effect) whose density observed today recovered through consanguineous couplings, potentiating deleterious genotypes in the offspring. Environ Toxicol Chem 2024;43:1996-2004. © 2024 SETAC.

Comprehensive target analysis and TOP assay of per- and polyfluoroalkyl substances (PFAS) in wild boar livers indicate contamination hot-spots in the environment.

The suitability of wild boar liver as a bioindicator of per- and polyfluoroalkyl substances (PFAS) in the terrestrial environment was investigated. Samples from 50 animals in three different areas associated with (1) contaminated paper sludges distributed on arable land (PS), (2) industrial emissions of PFAS (IE) and (3) background contamination (BC) were analyzed for 66 PFAS, including legacy PFAS, novel substitutes and precursors of perfluoroalkyl acids (PFAAs). Additionally, the Total Oxidizable Precursor (TOP) assay was performed to determine the formation potential of PFAAs from precursors. In total, 31 PFAS were detected with site-specific contamination profiles. PFAS concentrations in livers from area PS and IE (567 and 944 µg kg-1 wet weight, respectively) were multiple times higher than from area BC (120 µg kg-1). The dominating PFAS were the legacy compounds perfluorooctane sulfonic acid (PFOS) in areas PS and BC (426 and 82 µg kg-1, respectively) and perfluorooctanoic acid (PFOA) in area IE (650 µg kg-1). In area IE, the compounds 4,8-dioxa-3H-perfluorononanoic acid (DONA) and hexafluoropropylene oxide dimer acid (HFPO-DA) - which are used as substitutes for PFOA - were determined at 15 and 0.29 µg kg-1, respectively. The formation potential of PFAAs was highest in area PS, but generally lower than the contamination with PFAAs. The pattern of perfluoroalkyl carboxylic acids (PFCAs) in wild boar liver reflects the contamination of the local soil at the two hot-spot areas IE and PS. This first comparison of PFAS contamination between wild boars and soil suggests that wild boar livers are suitable bioindicators for PFAS contamination in the terrestrial environment. Moreover, in terrestrial samples from area IE, legacy PFAS were found to be retained for a longer period as compared to riverine samples (suspended particulate matter and chub filet).

Maternal Transfer and Apical and Physiological Effects of Dietary Hexabromocyclododecane Exposure in Parental Fathead Minnows (Pimephales promelas).

Hexabromocyclododecane (HBCD) is a persistent organic pollutant that has been characterized as an endocrine disruptor, undergoes maternal transfer, and hinders development and growth in oviparous organisms. The present study examined the apical effects of dietary HBCD (11.5, 36.4, 106 mg/kg, wet wt) on adult fathead minnow exposed for 49 days and the subsequent accumulation and maternal transfer kinetics in adult tissue and eggs, respectively. Exposed adults displayed a significant increase in egg production in the medium treatment group, but no other significant effects were noted. Maternal transfer of dietary HBCD had a similar egg-to-muscle ratios (EMR) in the low and medium treatment groups (1.65 and 1.27 [wet wt], respectively). However, the high treatment group deviated from other treatments with an EMR of 4.2 (wet wt), potentially due to differences in total lipid content in food and/or reaching diffusion/lipid saturation limits in adult tissue, resulting in lower accumulation in the adult muscle tissue. A positive correlation was observed between egg HBCD concentration and time of exposure, which indicates that maternal transfer of HBCD is of concern in fish, and further studies should be conducted to fully elucidate the potential adverse effects that may be observed in the early life stage of oviparous organisms. Environ Toxicol Chem 2023;42:143-153. © 2022 SETAC.

From data to reliable conclusions: Identification and comparison of persistent micropollutants and transformation products in 37 wastewater samples by non-target screening prioritization.

In this study, micropollutants in wastewater effluents were prioritized by monitoring the composition of influent and effluent wastewater by liquid chromatography - high-resolution mass spectrometry (LCHRMS) non-target screening (NTS) analysis. The study shows how important data pre-processing and filtering of raw data is to produce reliable NTS data for comparison of compounds between many samples (37 wastewater samples) analyzed at different times. Triplicate injections were critical for reducing the number of false-positive detections. Intensity drift corrections within and between batches analyzed months apart made peak intensities comparable across samples. Adjustment of the feature detection threshold was shown to be important, due to large intensity variations for low abundance compounds across batches. When the threshold correction cut-offs, or the filtering of relevant compounds by the occurrence frequency, were too stringent, a high number of false positive transformation products (TPs) were reported. We also showed that matrix effect correction by internal standards can over- or under-correct the intensity for unknown compounds, thus the TIC matrix effect correction was shown as an additional tool for a retention time dependent matrix effect correction. After these preprocessing and filtering steps, we identified 78 prioritized compounds, of which 36 were persistent compounds, defined as compounds with a reduction in peak intensity between influent and effluent wastewater <50%, and 13 compounds were defined as TPs because they occurred solely in the effluent samples. Some examples of persistent compounds are 1,3-diphenylguanidine, amisulpride and the human metabolites from losartan, verapamil and methadone. To our knowledge, nine of the identified TPs have not been previously described in effluent wastewater. The TPs were derived from metoprolol, fexofenadine, DEET and losartan. The screening of all identified compounds in effluent samples from eight wastewater treatment plants (WWTPs) showed that potential drugs of abuse, anti-psychotic and anti-depressant drugs were predominant in the capital city region, whereas the anti-epileptic agents and agricultural pesticides were dominant in more rural areas.

Predicting Primary Biodegradation of Petroleum Hydrocarbons in Aquatic Systems: Integrating System and Molecular Structure Parameters using a Novel Machine-Learning Framework.

Quantitative structure-property relationship (QSPR) models for predicting primary biodegradation of petroleum hydrocarbons have been previously developed. These models use experimental data generated under widely varied conditions, the effects of which are not captured adequately within model formalisms. As a result, they exhibit variable predictive performance and are unable to incorporate the role of study design and test conditions on the assessment of environmental persistence. To address these limitations, a novel machine-learning System-Integrated Model (HC-BioSIM) is presented, which integrates chemical structure and test system variability, leading to improved prediction of primary disappearance time (DT50) values for petroleum hydrocarbons in fresh and marine water. An expanded, highly curated database of 728 experimental DT50 values (181 unique hydrocarbon structures compiled from 13 primary sources) was used to develop and validate a supervised model tree machine-learning model. Using relatively few parameters (6 system and 25 structural parameters), the model demonstrated significant improvement in predictive performance (root mean square error = 0.26, R2 = 0.67) over existing QSPR models. The model also demonstrated improved accuracy of persistence (P) categorization (i.e., "Not P/P/vP"), with an accuracy of 96.8%, and false-positive and -negative categorization rates of 0.4% and 2.7%, respectively. This significant improvement in DT50 prediction, and subsequent persistence categorization, validates the need for models that integrate experimental design and environmental system parameters into biodegradation and persistence assessment. Environ Toxicol Chem 2022;41:1359-1369. © 2022 ExxonMobil Biomedical Sciences, Inc. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Per- and Polyfluoroalkyl Substances (PFAS) in Fish from European Lakes: Current Contamination Status, Sources, and Perspectives for Monitoring.

Concentrations in fish of per- and polyfluoroalkyl substances (PFAS) were reported for 7 deep lakes in the European subalpine area: Lakes Geneva, Lugano, Maggiore, Iseo, Como, Garda, and Mergozzo; one shallow lowland lake (Varese); and 2 high-altitude alpine lakes (>2000 m a.s.l). Fillets and, in selected cases, other body fractions (viscera, liver, and residual carcass) from 8 fish species were analyzed. The possibility of harmonizing the monitoring protocols was tested. Results suggest that the sampling season is not critical for PFASs and the total protein content cannot be used for normalization of tissue concentrations because PFASs bind to specific proteins. Moreover, the polar lipid content could be used to reduce the variability of PFAS concentrations in phospholipid rich fractions of fish such as viscera and carcass. The data comparison and analysis show that the PFAS contamination in lake fish is generally correlated with the degree of urbanization of the lake catchment; however, it is sometimes difficult to compare absolute concentrations in lake fish because the lake hydro-morphological characteristics play a substantial role in determining the chemical concentrations of persistent and mobile contaminants. Environ Toxicol Chem 2021;40:658-676. © 2020 SETAC.

Impact assessment of a large panel of organic and inorganic micropollutants released by wastewater treatment plants at the scale of France.

Micropollutants emitted by Human activities represent a potential threat to our health and aquatic environment. Thousands of active substances are used and go to WWTP through wastewaters. During water treatment, incomplete elimination occurs. Effluents released to the environment still contain part of the micropollutants present in the influents. Here, we studied the potential impacts on Human health and aquatic environment of the release of 261 organic micropollutants and 25 inorganic micropollutants at the scale of France. Data were gathered from national surveys, reports, papers and PhD works. The USEtox ® model was used to assess potential impacts. The impacts on Human health were estimated for 94 organic and 15 inorganic micropollutants and on aquatic environment for 88 organic and 19 inorganic micropollutants highlighting lack of concentration and toxicological data in literature. Some Polycyclic Aromatic Hydrocarbons and pesticides as well as As and Zn showed highest potential impacts on Human health. Some pesticides, PCB 101, ßE2, Al, Fe and Cu showed highest potential impacts on aquatic environment.

Per- and Polyfluoroalkyl Substance Toxicity and Human Health Review: Current State of Knowledge and Strategies for Informing Future Research.

Reports of environmental and human health impacts of per- and polyfluoroalkyl substances (PFAS) have greatly increased in the peer-reviewed literature. The goals of the present review are to assess the state of the science regarding toxicological effects of PFAS and to develop strategies for advancing knowledge on the health effects of this large family of chemicals. Currently, much of the toxicity data available for PFAS are for a handful of chemicals, primarily legacy PFAS such as perfluorooctanoic acid and perfluorooctane sulfonate. Epidemiological studies have revealed associations between exposure to specific PFAS and a variety of health effects, including altered immune and thyroid function, liver disease, lipid and insulin dysregulation, kidney disease, adverse reproductive and developmental outcomes, and cancer. Concordance with experimental animal data exists for many of these effects. However, information on modes of action and adverse outcome pathways must be expanded, and profound differences in PFAS toxicokinetic properties must be considered in understanding differences in responses between the sexes and among species and life stages. With many health effects noted for a relatively few example compounds and hundreds of other PFAS in commerce lacking toxicity data, more contemporary and high-throughput approaches such as read-across, molecular dynamics, and protein modeling are proposed to accelerate the development of toxicity information on emerging and legacy PFAS, individually and as mixtures. In addition, an appropriate degree of precaution, given what is already known from the PFAS examples noted, may be needed to protect human health. Environ Toxicol Chem 2021;40:606-630. © 2020 SETAC.

Target and suspect screening analysis reveals persistent emerging organic contaminants in soils and sediments.

An approach to identifying persistent organic contaminants in the environment was developed and executed for Switzerland as an example of an industrialized country. First, samples were screened with an in-house list using liquid chromatography high-resolution mass spectrometry (LC-HRMS/MS) and gas chromatography tandem mass spectrometry (GC-MS/MS) in 13 samples from the Swiss National Soil Monitoring Network and three sediment cores of an urban and agricultural contaminated lake. To capture a broader range of organic contaminants, the analysis was extended with a suspect screening analysis by LC-HRMS/MS of >500 halogenated compounds obtained from a Swiss database that includes industrial and household chemicals identified, by means of fugacity modeling, as persistent substances in the selected matrices. In total, the confirmation of 96 compounds with an overlap of 34 in soil and sediment was achieved. The identified compounds consist generally of esters, tertiary amines, trifluoromethyls, organophosphates, azoles and aromatic azines, with azoles and triazines being the most common groups. Newly identified compounds include transformation products, pharmaceuticals such as the flukicide niclofolan, the antimicrobial cloflucarban, and the fungicide mandipropamid. The results indicate that agricultural and urban soils as well as sediments impacted by agriculture and wastewater treatment plants (WWTPs) are the most contaminated sites. The plausibility of this outcome confirms the combination of chemical inventory, modeling of partitioning and persistence, and HRMS-based screening as a successful approach to shed light on less frequently or not yet investigated environmental contaminants and emphasizes the need for more soil and sediment monitoring in the future.

Micro-pollutants in sediment samples in the middle Danube region, Serbia: occurrence and risk assessment.

This is the first comprehensive study on the occurrence of 940 semi-volatile organic compounds including sterols, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), pesticides, plasticizers, and other emerging compounds in 10 river and canal sediments collected in northern Serbia. For quantification of investigated compounds GC-MS-MS (selected reaction monitoring) and GC-MS (using both selected ion monitoring and total ion monitoring) methods were used. The number of detected compounds was in the range of 85-117, while the sum of the concentrations varied from 959 µg/kg dry-wt to 84,445 µg/kg dry-wt. Sterols were quantified with high frequency in nearly 100% of investigated samples suggesting that the studied rivers and canals have been contaminated by sewage. Regarding persistent organic compounds, p,p'-DDE, p,p'-DDD, and o,p'-DDT were the dominant members of organochlorine pesticides (OCPs). The concentration range of 11 quantified pesticides of 452 analyzed was from 0.564 to 61.6 µg/kg dry-wt, while the concentration range of 47 quantified PCBs of 90 analyzed was from 0.928 to 32.1 µg/kg dry-wt. OCPs (DDE, DDD, and γ-HCH) and several PAHs (fluoranthene, pyrene, phenanthrene, chrysene, benzo(a)anthracene, benzo(a)pyrene) exceeded the maximum values of the sediment quality guidelines. Contents of domestic compounds comprise a large proportion of the total contaminant concentration. Overall, the study reveals that river sediments in Vojvodina Province were moderately polluted mainly by domestic wastewater. The toxic equivalent quantity (TEQ) relative to benzo(a)pyrene and 2,3,7,8-tetrachlorodibenzodioxin for seven carcinogenic PAHs and six quantified dioxin-like PCBs ranged from 3.59 to 103 µg TEQ/kg and from 0.001 × 10-3 to 2.10 × 10-3 µg TEQ/kg, respectively, and were in the range or lower than the literature published data.

Development and application of screening tools for biodegradation in water-sediment systems and soil.

Two new screening-test systems for biodegradation in water-sediment systems (WSST; Water-Sediment Screening Tool) and soil (SST; Soil Screening Tool) were developed in analogy with the water-only test system OECD 301C (MITI-test). The test systems could be applied successfully to determine reproducible experimental mineralization rates and kinetics on the screening-test level for fifteen organic chemicals in water (MITI), water-sediment (WSST) and soil (SST). Substance-specific differences were observed for mineralization compared among the three test systems. Based on mineralization rate and mineralization half-life, the fifteen compounds could be grouped into four biodegradation categories: substances with high mineralization and a half-life <28 days in (1) all three test systems, (2) only in the MITI test and in the WSST, (3) only in the SST, and (4) none of the test systems. The observed differences between the MITI results and the WSST and SST biodegradation rates of the compounds do not reflect their (reversible) sorption into organic matter in terms of experimental K(oc) values and log D values for the relevant pH range. Regarding mineralization kinetics we recommend to determine the lag-phase, mineralization half-life and mineralization rate using a 5-parameter logistic regression for degradation curves with and without lag-phase. Experimental data obtained with the WSST and the SST could be verified by showing good agreement with biodegradation data from databases and literature for the majority of compounds tested. Thus, these new screening-tools for water-sediment and soil are considered suitable to determine sound and reliable quantitative mineralization data including mineralization kinetics in addition to the water-only ready biodegradability tests according to OECD 301.

Fugacity and activity analysis of the bioaccumulation and environmental risks of decamethylcyclopentasiloxane (D5).

As part of an initiative to evaluate commercial chemicals for their effects on human and environmental health, Canada recently evaluated decamethylcyclopentasiloxane (D5; CAS no. 541-02-06), a high-volume production chemical used in many personal care products. The evaluation illustrated the challenges encountered in environmental risk assessments and the need for the development of better tools to increase the weight of evidence in environmental risk assessments. The present study presents a new risk analysis method that applies thermodynamic principles of fugacity and activity to express the results of field monitoring and laboratory bioaccumulation and toxicity studies in a comprehensive risk analysis that can support risk assessments. Fugacity and activity ratios of D5 derived from bioaccumulation measures indicate that D5 does not biomagnify in food webs, likely because of biotransformation. The fugacity and activity analysis further demonstrates that reported no-observed-effect concentrations of D5 normally cannot occur in the environment. Observed fugacities and activities in the environment are, without exception, far below those corresponding with no observed effects, in many cases by several orders of magnitude. This analysis supports the conclusion of the Canadian Board of Review and the Minister of the Environment that D5 does not pose a danger to the environment. The present study further illustrates some of the limitations of a persistence-bioaccumulation-toxicity-type criteria-based risk assessment approach and discusses the merits of the fugacity and activity approach to increase the weight of evidence and consistency in environmental risk assessments of commercial chemicals.