Community-level risk assessments on organophosphate esters in the sediments from the Bohai Sea of China based on multimodal species sensitivity distributions coupled with the equilibrium partitioning method.

Organophosphate esters (OPEs), increasingly used as alternatives to brominated flame retardants, are ubiquitous in the global aquatic environment. Despite their potential toxicological impact on ecosystems, community-level risk assessments for OPEs in sediments remain scarce. This study investigated OPE occurrences and composition characteristics in the Bohai Sea's sediments and appraised both individual and joint ecological risks posed by characteristic OPE homologs using ten commonly used species sensitivity distribution (SSD) models, integrating acute-to-chronic conversion and phase equilibrium partitioning. OPEs were detected across all sediment samples, with total concentrations ranging from 0.213 ng/g dry weight (dw) to 91.1 ng/g dw. The predominant congeners included tri-n-butyl phosphate (TnBP), triisobutyl phosphate (TiBP), tri(2-ethylhexyl) phosphate, tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(1, 3-dichloro-2-propyl) phosphate (TDCIPP), and triphenylphosphine oxide. Best-fit SSD models varied among TnBP, TiBP, TCEP, TCPP, and TDCIPP, demonstrating Sigmoid, Burr III, Sigmoid, Burr III, and Burr III, respectively. The same parametric model demonstrated variability in the fitting process for different OPE congeners, which also happened to the fitting results of ten parametric models for the same specific characteristic congener, underscoring the necessity of employing multiple models for precise community-level risk assessments. Hazard concentrations for a 5% cumulative probability were 0.116 mg/L, 2.88 mg/L, 1.30 mg/L, 1.44 mg/L, and 1.85 mg/L for each respective congener. The resulting risk quotients (RQ) and overall hazard index (HI) were selected as criteria to assess the individual and joint ecological risks of OPEs in sediments from the Bohai Sea, respectively. RQ and HI were both below 0.1, indicating a low risk to the local ecosystems. Multi-model SSD analysis could provide refined data for community-level risk evaluation, offering valuable insights for the development of evidence-based environmental standards and pollution control strategies.

Equilibrium partitioning approach for metal toxicity assessment in tropical estuarine sediment of Bandon Bay, Thailand.

An equilibrium partitioning approach (EqPA) was employed to evaluate the metal toxicity and define sediment quality guidelines (SQGs) for arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), zinc (Zn), and mercury (Hg) in the cockle cultivated areas located in Bandon Bay, Thailand. An assessment of metal toxicity using the [∑SEM]-[AVS] and [∑SEM]-[AVS]/foc models indicated no adverse effect on benthic organisms. The normalized total metal concentrations in this area were below the established SQG values for As, Cd, Cu, Ni, Pb, Zn, and Hg, namely respectively 21.3, 0.8, 84.6, 36.0, 34.6, 440.9 mg/kg dry weight, and 49.3 µg/kg dry weight on sand and calcium carbonate free with 1 % total organic carbon basis, suggesting low metal toxicity. This study provides locality adapted SQG values for supporting sediment quality management specifically in Bandon Bay, potentially serving as a model for other coastal areas.

Derivation of aquatic predicted no-effect concentration and ecological risk assessment for triphenyl phosphate and tris(1,3-dichloro-2-propyl) phosphate.

Triphenyl phosphate (TPhP) and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) are common organophosphate esters (OPEs), which are used as additives in various industries. These compounds have been widely detected in aquatic environment, raising concerns about their adverse effects on aquatic organisms. In order to protect aquatic ecosystems, a total of 7 species were selected for acute and chronic toxicity tests in this study. The results indicated that TPhP and TDCIPP exhibited varying degrees of toxicity to aquatic organisms. The 96-h LC50 values ranged from 1.088 mg/L to 1.574 mg/L for TPhP and from 2.027 mg/L to 17.855 mg/L for TDCIPP. The 28-d LC10 values ranged from 0.023 mg/L to 0.177 mg/L for TPhP and from 0.300 mg/L to 1.102 mg/L for TDCIPP. The tested toxicity data, combined with collected toxicity data, were used to investigate the predicted no-effect concentration in water (PNECwater) of TPhP and TDCIPP by species sensitivity distribution (SSD) method. The results revealed PNECwater values of 6.35 and 38.0 µg/L for TPhP and TDCIPP, respectively. Furthermore, the predicted no-effect concentrations in sediment (PNECsed) were derived as 110 µg/kg dry weight (dw) for TPhP and 424 µg/kg dw for TDCIPP using the equilibrium partitioning (EqP) approach. Based on the toxicity data and PNECs, the ecological risk of these two chemicals in surface waters and sediments worldwide over the last decade were evaluated. The results indicated that TDCIPP posed negligible risk in aquatic ecosystems. However, TPhP showed potential risk in sediments, as indicated by the hazard quotients (HQs) exceeding 0.1. The results of joint probability curves (JPC) indicated that the probabilities of exceeding hazardous concentration for 1 % of species for TPhP in water and sediment were 0.33 % and 5.2 %, respectively. Overall, these findings highlight the need for continued monitoring and assessment of the presence and potential impacts of TPhP and TDCIPP in aquatic ecosystems.

Chemical Activity-Based Loading of Artificial Sediments with Organic Pollutants for Bioassays: A Proof of Concept.

Persistent organic pollutants (POPs) pose a risk in aquatic environments. In sediment, this risk is frequently evaluated using total or organic carbon-normalized concentrations. However, complex physicochemical sediment characteristics affect POP bioavailability in sediment, making its prediction a challenging task. This task can be addressed using chemical activity, which describes a compound's environmentally effective concentration and can generally be approximated by the degree of saturation for each POP in its matrix. We present a proof of concept to load artificial sediments with POPs to reach a target chemical activity. This approach is envisioned to make laboratory ecotoxicological bioassays more reproducible and reduce the impact of sediment characteristics on the risk assessment. The approach uses a constantly replenished, saturated, aqueous POP solution to equilibrate the organic carbon fraction (e.g., peat) of an artificial sediment, which can be further adjusted to target chemical activities by mixing with clean peat. We demonstrate the applicability of this approach using four polycyclic aromatic hydrocarbons (acenaphthene, fluorene, phenanthrene, and fluoranthene). Within 5 to 17 weeks, the peat slurry reached a chemical equilibrium with the saturated loading solution. We used two different peat batches (subsamples from the same source) to evaluate the approach. Variations in loading kinetics and eventual equilibrium concentrations were evident between the batches, which highlights the impact of even minor disparities in organic carbon properties within two samples of peat originating from the same source. This finding underlines the importance of moving away from sediment risk assessments based on total concentrations. The value of the chemical activity-based loading approach lies in its ability to anticipate similar environmental impacts, even with varying contaminant concentrations. Environ Toxicol Chem 2024;43:279-287. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Nonequilibrium Behavior in Isoprene Secondary Organic Aerosol.

Recent studies have shown that instantaneous gas-particle equilibrium partitioning assumptions fail to predict SOA formation, even at high relative humidity (∼85%), and photochemical aging seems to be one driving factor. In this study, we probe the minimum aging time scale required to observe nonequilibrium partitioning of semivolatile organic compounds (SVOCs) between the gas and aerosol phase at ∼50% RH. Seed isoprene SOA is generated by photo-oxidation in the presence of effloresced ammonium sulfate seeds at <1 ppbv NOx, aged photochemically or in the dark for 0.3-6 h, and subsequently exposed to fresh isoprene SVOCs. Our results show that the equilibrium partitioning assumption is accurate for fresh isoprene SOA but breaks down after isoprene SOA has been aged for as short as 20 min even in the dark. Modeling results show that a semisolid SOA phase state is necessary to reproduce the observed particle size distribution evolution. The observed nonequilibrium partitioning behavior and inferred semisolid phase state are corroborated by offline mass spectrometric analysis on the bulk aerosol particles showing the formation of organosulfates and oligomers. The unexpected short time scale for the phase transition within isoprene SOA has important implications for the growth of atmospheric ultrafine particles to climate-relevant sizes.

Risk Threshold and Assessment of Chloramphenicol Antibiotics in Sediment in the Fenhe River Basin, China.

Chloramphenicol antibiotics (CAs) are broad-spectrum antibiotics which are widely used in the prevention and treatment of infectious diseases in livestock and poultry breeding. However, overused CAs can enter the watershed and eventually enter the sediment. Antibiotics in sediment can cause secondary pollution through disturbance and suspension. In this study, taking the Fenhe River Basin as the research area, the risk of CAs in sediment were assessed by collecting sediment samples. The results showed that CAs were detected in all sediment samples of the Fenhe River Basin. The mean concentration of CAs was 79.1 µg/kg, and the concentration of thiamphenicol (THI) was dominant, which was up to 58.3 µg/kg. Temporally, there are great differences in different seasons; the concentration of CAs was higher in winter than that in summer, up to 4.79-174 times. Spatially, the mean concentration of CAs in midstream was 83.5 µg/kg, which was higher than that in the upstream and downstream. The concentration of CAs in tributaries were generally higher than that in the main stream, and the mean concentration of tributaries was 1.1 times that of the main stream. CAs in S2 (Lanhe River) was the most prominent among all sample sites; the concentration of CAs was 190.8 µg/kg. The risk threshold of CAs in the sediment was calculated using the Equilibrium Partitioning approach (EqP), based on the distribution coefficient (Kp) and the predicted no-effect concentration (PNEC) in the water, and the values were 0.091-1.44 mg/kg. Based on the risk threshold, the ecological risk of the CAs in sediment was assessed using risk quotients (RQ). The results showed that the Chloramphenicol (CHL) was the most prominent in the Fenhe River Basin, and the proportion of medium-risk areas reached 21.7%, while all the other areas showed low risk. Secondly, the proportion of medium-risk areas was 17.4% for THI, and all the other areas showed low risk. The risk for Florfenicol (FF) was least among all CAs, and the proportion of low-risk areas was only 8.7%, while all the other areas were of insignificant risk.

Environmental exposure and ecological risk of perfluorinated substances (PFASs) in the Shaying River Basin, China.

There have been concerns raised about the environmental effects of perfluoroalkyl substances (PFASs) because of their toxicity, widespread distribution, and persistence. Understanding the occurrences and ecological risk posed by PFASs is essential, especially for the short-chain replacements perfluorobutanoic acid (PFBA) and perfluorobutane sulfonic acid (PFBS), which are now becoming predominant PFASs. The lack of aquatic life criteria (ALC), however, prevents an accurate assessment of the ecological risks of PFBA and PFBS. This study thus investigated the occurrence of 15 PFASs at 29 sampling sites in Shaying River Basin (in China) systematically, conducted the toxicity tests of PFBA and PFBS on eight resident aquatic organisms in China, and derived the predicted non-effect concentration (PNEC) values for PFBA and PFBS for two environmental media in China. The results showed that the total PFASs concentrations (ΣPFASs) ranged from 5.07 to 20.32 ng/L (average of 10.95 ng/L) in surface water, whereas in sediment, ΣPFASs ranged from 6.46 to 20.05 ng/g (dw) (average of 11.51 ng/g). The presence of PFBS was the most prominent PFASs in both water (0.372-8.194 ng/L) and sediment (4.54-15.72 ng/g), demonstrating that short-chain substitution effects can be observed in watersheds. The PNEC values for freshwater and sediment were 6.60 mg/L and 8.30 mg/kg (ww), respectively, for PFBA, and 14.04 mg/L, 37.08 mg/kg (ww), respectively, for PFBS. Ecological risk assessment of two long-chain PFASs, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), and two short-chain PFASs, PFBA and PFBS, using the hazard quotient method revealed that Shaying River and other major River Basins in China were at risk of PFOS contamination. This study contributes to a better understanding of the presence and risk of PFASs in the Shaying River and first proposes the ALCs for PFBA and PFBS in China, which could provide important reference information for water quality standards.

Abnormal fluoride distribution, human health risk assessment, predicted no-effect concentration (PNEC) and environmental hazards in an Egyptian lake connected to the Mediterranean Sea.

Fluoride can affect the metabolism and physiological functioning of humans and aquatic organisms like any hazardous substance when it exceeds its permissible limits and PNEC values. The fluoride content of the lake water and sediment samples collected from different locations was determined to assess its risks to humans and its ecological toxicity in Lake Burullus. Statistical analyses show that the proximity of the supplying drains had an impact on the fluoride content. Fluoride ingestion and skin contact in lake water and sediment during swimming for child, female and male were evaluated at 95, 90, and 50%. The values of hazard quotient (HQ) and total hazard quotient (THQ) for children, females and males were less than one, reflecting that exposure to fluoride through ingestion and skin-to-skin contact while swimming poses no risks to human health. PNEC values for fluoride in lake water and sediment were estimated using the equilibrium partitioning method (EPM). The ecological risk assessment of fluoride for acute and chronic toxicity was performed for the three trophic levels based on the PNEC, the half-maximal effective concentration (EC50), the median lethal dose (LC50), the no-observed effect concentration (NOEC), and the 5% lethal concentration (EC05). The risk quotient (RQ), mixture risk characterization ratios (RCRmix), relative contribution (RC), toxic unit (TU), and sum of toxic units (STU) were estimated. The acute and chronic RCRmix(STU) and RCRmix(MEC/PNEC) produced similar values for the three trophic levels in lake water and sediment, indicating that invertebrates are the most sensitive species to fluoride. These results of evaluating the environmental risks of fluoride in lake water and sediments reflected its significant impact on aquatic organisms living in the lake area in the long term.

Passive sampling of diverse pesticides in water by hydrophilic-lipophilic balance sorbent-embedded cellulose acetate membrane: Kinetics, equilibrium partitioning and field application.

Pesticides are useful products for agriculture and human life, but they are often released into surface waters and are hazardous to aquatic ecosystems. Pesticides monitoring in surface waters is challenging due to the great variety, ultratrace levels and nonpoint source pollution of pesticides; however, continuous passive sampling may be conducive to solving these problems. This work evaluated the performance of a newly developed passive sampler (hydrophilic-lipophilic balance sorbent-embedded cellulose acetate membrane, HECAM) for six types of currently used/present pesticides. The uptake kinetics and equilibrium partitioning of nineteen pesticides in different dissolved concentrations were studied by dynamic accumulation and equilibrium partitioning experiments, respectively. In the dynamic accumulation experiments, pesticides gradually accumulated in the HECAM and followed a first-order kinetic model. The same type of pesticides had roughly comparable accumulation concentrations. The estimated uptake rate constants ranged from 1.04 to 13.5 L g-1 d-1, and sampling rates ranged from 0.02 to 0.31 L d-1 for the pesticides in the HECAM (size of 2 cm × 3 cm). Pesticide accumulation concentrations in the HECAM increased linearly with increasing dissolved concentrations, which means that varying concentrations can also be monitored by the HECAM. In the equilibrium partitioning experiments, the pesticide partitioning behavior at varying dissolved concentrations can be described by the Freundlich model. The calculated equilibrium partition coefficients (log KD) for pesticides ranged from 3.32 to 4.54, and different pesticide types showed different changes with log Kow. Comparable results were found when estimating chemical equilibrium partition coefficients by the dynamic accumulation and equilibrium partitioning methods. Field deployment of the HECAM in river waters resulted in the detection of four pesticides, and the measured results were comparable to those of active sampling coupled with liquid-liquid extraction. These results suggest that the HECAM would be a promising strategy for simultaneously monitoring diverse pesticides in waters.

A Guideline Value for Dioxin-Like Compounds in Marine Sediments.

Sediments to be dredged as part of the installation of a harbor crossing in Sydney, Australia, contained measurable concentrations of dioxin-like compounds. To assess the suitability of these sediments for ocean disposal, a defensible sediment quality guideline value (SQGV) for dioxin-like compounds, expressed as pg toxic equivalent (TEQ)fish /g dry weight, was required. There were deemed to be too many uncertainties associated with a value derived using effects data from field studies. A similar issue was associated with values based on equilibrium partitioning from sediment to pore water, largely associated with the wide range of reported sediment:water partition coefficients. Greater certainty was associated with the use of a tissue residue approach based on equilibrium partitioning between sediment and organisms determined using tissue concentrations in fish, the most sensitive aquatic biota, and biota:sediment accumulation factors. The calculation of an appropriate SQGV used data for dioxin-like compounds in both fish and sediments from Sydney Harbor. A conservative SQGV for dioxin-like compounds of 70 pg TEQ/g dry weight was deemed to be adequately protective of biota that might be exposed to these contaminants in sediments at the ocean spoil ground. The approach is transferable to similar situations internationally. Environ Toxicol Chem 2023;42:257-271. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Exploring the nonlinear partitioning mechanism of volatile organic contaminants between soil and soil vapor using machine learning.

Traditional phase equilibrium models usually depend on simplified assumptions and empirical parameters, which are difficult to obtain during regular site investigations. As a result, they often under- or over-estimate soil vapor concentrations for assessing the risks of volatile organic compound (VOC)-contaminated sites. In this study, we develop several machine learning models to predict soil vapor concentrations using 2225 soil-soil vapor data pairs collected from seven contaminated sites in northern China. Compared to the classic dual equilibrium desorption model, the random forest (RF) model can provide more accurate predictions of soil vapor concentrations by at least 1-2 orders of magnitude. Among the employed covariates, soil concentration and organic carbon-water partition coefficient are two of the most significant explanatory covariates affecting soil vapor concentrations. Further examination of the developed RF model reveals the phase equilibrium behavior of VOCs in soil is that: the soil vapor concentration increases with soil concentration at different rates in the first two intervals but remains almost unchanged in the last interval; the solid-vapor partitioning interface may still exist at up to 15% mass water content in our simulations. These findings can help site investigators perform more accurate risk assessments at VOC-contaminated sites.

A novel antibody-based biosensor method for the rapid measurement of PAH contamination in oysters.

Conventional PAH analytical methods are time-consuming and expensive, limiting their utility in time sensitive events (i.e. oil spills and floods) or for widespread environmental monitoring. Unreliable and inefficient screening methods intended to prioritize samples for more extensive analyses exacerbate the issue. Antibody-based biosensor technology was implemented as a quantitative screening method to measure total PAH concentration in adult oysters (Crassostrea virginica) - a well-known bioindicator species with ecological and commercial significance. Individual oysters were analyzed throughout the historically polluted Elizabeth River watershed (Virginia, USA). Significant positive association was observed between biosensor and GC-MS measurements that persisted when the method was calibrated for different regulatory subsets of PAHs. Mapping of PAH concentrations in oysters throughout the watershed demonstrates the utility of this technology for environmental monitoring. Through a novel extension of equilibrium partitioning, biosensor technology shows promise as a cost-effective analysis to rapidly predict whole animal exposure to better assess human health risk as well as improve monitoring efforts.

Modelling polycyclic aromatic hydrocarbon bioavailability in historically contaminated soils with six in-vitro chemical extractions and three earthworm ecotypes.

Accurate prediction of organic contaminant bioavailability for risk assessment in ecological applications is hindered by limited validation on relevant bioassay species. Here, six in-vitro chemical extraction methods (butanol, non-buffered and buffered hydroxypropyl-ß-cyclodextrin (HPCD, Buf-HPCD), Tenax, potassium persulfate oxidation, polyoxymethylene solid phase extraction (POM)) were tested for PAH bioaccumulation prediction in three earthworm ecotypes with dissimilar exposures, Amynthas sp., Eisenia fetida, and Lumbricus terrestris, in historically contaminated soils from manufactured gas plant (MGP) sites. Extractions were compared directly and modelled in a calculation approach using equilibrium partitioning theory (EqPT) with a novel combination of different organic carbon/octanol-water partitioning parameters (KOC and KOW). In the direct comparison approach Buf-HPCD showed the closest prediction of accumulation for burrowing Amynthas sp. and L. terrestris (within 1.5 and 3.1, respectively), but Tenax and POM showed the closest approximation for E. fetida (within 1.1 and 0.9, respectively). The optimum method for predicting PAH bioaccumulation in the calculation approach depended on earthworm species and the partitioning parameters used in equations of the four models, but overall POM, which was independent of KOC, showed the closest approximation of accumulation, within a factor of 2.5 across all species. This work effectively identifies the optimum in-vitro based approaches for PAH bioavailability prediction in earthworms as a model soil health indicator for ecological risk assessment within regulatory and remediation decision frameworks.

Henry's Law Constants and Indoor Partitioning of Microbial Volatile Organic Compounds.

Microbial volatile organic compounds (MVOCs) play an essential role in many environmental fields, such as indoor air quality. Long-term exposure to odorous and toxic MVOCs can negatively affect the health of occupants. Recently, the involvement of surface reservoirs in indoor chemistry has been realized, which signifies the importance of the phase partitioning of volatile organic pollutants. However, reliable partition coefficients of many MVOCs are currently lacking. Equilibrium partition coefficients, such as Henry's law constant, H, are crucial for understanding the environmental behavior of chemicals. This study aims to experimentally determine the H values and their temperature dependence for key MVOCs under temperature relevant to the indoor environment. The H values were determined with the inert gas-stripping (IGS) method and variable phase ratio headspace (VPR-HS) technique. A two-dimensional partitioning model was applied to predict the indoor phase distribution of MVOCs and potential exposure pathways to the residences. The findings show that the MVOCs are likely distributed between the gas and weakly polar (e.g., organic-rich) reservoirs indoors. Temperature and the volume of reservoirs can sensitively affect indoor partitioning. Our results give a more comprehensive view of indoor chemical partitioning and exposure.

Derivation of predicted no effect concentration and ecological risk assessment of polycyclic musks tonalide and galaxolide in sediment.

Polycyclic musks (PMs) have drawn increased attention in recent years because of their persistence, bioaccumulation and toxicity. As two typical PMs contaminants, tonalide (AHTN) and galaxolide (HHCB) are widely detected in sediment worldwide. Acute and chronic toxicity data of AHTN and HHCB to freshwater and seawater organisms in water and sediments are collected and screened. The predicted no effect concentrations (PNECsediment) for AHTN and HHCB is derived according to the equilibrium partitioning method recommended by the EU technical guidance document (TGD) and the species sensitivity distribution (SSD) method based on the measured sediment toxicity data. The concentration levels of AHTN and HHCB are investigated and evaluated in freshwater and seawater sediments. Results show the difference between native and non-native freshwater species is not statistically significant. AHTN is more toxic to freshwater and seawater organisms than HHCB, and seawater organisms are more sensitive to 2 musks than freshwater organisms. The chronic PNECsediment values of AHTN and HHCB are 194.48 and 416.47 ng/g in freshwater sediment, 88.93 and 128.34 ng/g in seawater sediment respectively. The AHTN and HHCB linear correlation analysis exhibited a strong positive linear correlation in both domestic (R2=0.9054) and foreign (R2 = 0.9645) sediment. Preliminary risk assessment shows that the risks posed by AHTN and HHCB in sediment based on individual or combined concentrations of two musks are at medium to high levels in some regions. Further risk assessment results indicate that, for HHCB, 1.72% of foreign freshwater sediment may pose an ecological risk to 5% species; for AHTN, 8.06% of foreign freshwater sediment and 1.02% of domestic freshwater sediment may pose an ecological risk to 5% species, and 5.86% of seawater sediment may pose an ecological risk to 5% species. The above results indicate that there are some negligible risks in domestic and foreign sediments posed by these two musks, we should continue to pay attention to the toxic effects and pollution level of both musks in environment.

Refining our understanding of metal bioavailability in sediments using information from porewater: Application of a multimetal biotic ligand model as an extension of the equilibrium partitioning sediment benchmarks.

The equilibrium partitioning sediment benchmarks (ESBs) derived by the US Environmental Protection Agency (USEPA) in 2005 provide a mechanistic framework for understanding metal bioavailability in sediments by considering equilibrium partitioning (EqP) theory, which predicts that metal bioavailability in sediments is determined largely by partitioning to sediment particles. Factors that favor the partitioning of metals to sediment particles, such as the presence of acid volatile sulfide (AVS) and sediment organic matter, reduce metal bioavailability to benthic organisms. Because ESBs link metal bioavailability to partitioning to particles, they also predict that measuring metals in porewater can lead to a more accurate assessment of bioavailability and toxicity to benthic organisms. At the time of their development, sediment ESBs based on the analysis of porewater metal concentrations were limited to comparison with hardness-dependent metals criteria for the calculation of interstitial water benchmark units (IWBUs). However, the multimetal biotic ligand model (mBLM) provides a more comprehensive assessment of porewater metal concentrations, because it considers factors in addition to hardness, such as pH and dissolved organic carbon, and allows for interactions between metals. To evaluate the utility of the various sediment and porewater ESBs, four Hyalella azteca bioassay studies were identified that included sediment and porewater measurements of metals and porewater bioavailability parameters. Evaluations of excess simultaneously extracted metals, IWBUs, and mBLM toxic units (TUs) were compared among the bioassay studies. For porewater, IWBUs and mBLM TUs were calculated using porewater metal concentrations from samples collected using centrifugation and peepers. The percentage of correct predictions of toxicity was calculated for each benchmark comparison. The mBLM-based assessment using peeper data provided the most accurate predictions for the greatest number of samples among the evaluation methods considered. This evaluation demonstrates the value of porewater-based evaluations in conjunction with sediment chemistry in understanding toxicity observed in bioassay studies. Integr Environ Assess Manag 2022;18:1335-1347. © 2021 SETAC.

Comparison of Species Sensitivity Distributions for Sediment-Associated Nonionic Organic Chemicals Through Equilibrium Partitioning Theory and Spiked-Sediment Toxicity Tests with Invertebrates.

Equilibrium partitioning (EqP) theory and spiked-sediment toxicity tests are useful methods to develop sediment quality benchmarks. However, neither approach has been directly compared based on species sensitivity distributions (SSDs) to date. In the present study, we compared SSDs for 10 nonionic hydrophobic chemicals (e.g., pyrethroid insecticides, other insecticides, and polycyclic aromatic hydrocarbons) based on 10-14-day spiked-sediment toxicity test data with those based on EqP theory using acute water-only tests. Because the exposure periods were different between the two tests, effective concentrations (i.e., median effective/lethal concentration) were corrected to compare SSDs. Accordingly, we found that hazardous concentrations for 50% and 5% of species (HC50 and HC5, respectively) differed by up to a factor of 100 and 129 between the two approaches, respectively. However, when five or more species were used for SSD estimation, their differences were reduced to a factor of 1.7 and 5.1 for HC50 and HC5, respectively, and the 95% confidence intervals of HC50 values overlapped considerably between the two approaches. These results suggest that when the number of test species is adequate, SSDs based on EqP theory and spiked-sediment tests are comparable in sediment risk assessments. Environ Toxicol Chem 2022;41:462-473. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Sediment toxicity data and excess simultaneously extracted metals from field-collected samples: Comparison to United States Environmental Protection Agency benchmarks.

US Environmental Protection Agency (USEPA) Procedures for the Derivation of Equilibrium Partitioning Sediment Benchmarks (ESBs) for the Protection of Benthic Organisms: Metal Mixtures are based on the principle that metals toxicity to benthic organisms is determined by bioavailable metals concentrations in porewater. One ESB is based on the difference between simultaneously extracted metal (SEM) and acid volatile sulfide (AVS) concentrations in sediment (excess SEM). The excess SEM ESBs include a lower uncertainty bound, below which most samples (95%) are expected to be "nontoxic" (defined as a bioassay mortality rate ≤24%), and an upper uncertainty bound, above which most samples (95%) are expected to be "toxic" (defined as a mortality rate >24%). Samples that fall between the upper and lower bounds are classified as "uncertain." Excess SEM ESBs can, in principle, be improved by normalizing for organic carbon (OC). OC is a binding phase that reduces metals bioavailability. OC normalization should improve the accuracy of bioavailable metal concentration estimates, thus tightening uncertainty bounds. We evaluated field-collected sediments from 13 studies with excess SEM, OC, and bioassay data (n = 740). Use of the OC-normalized excess SEM benchmarks did not improve prediction accuracy. The ESB model predicts OC-normalized excess SEM exceeding the upper benchmark even when toxicity is not observed, because error in the OC normalization model increases at low OC concentrations. To minimize the likelihood of incorrectly identifying nontoxic samples as toxic, we recommend that OC normalization of excess SEM should not be considered for sediments with an OC concentration <1% and is questionable for sediments with an OC concentration of 1%-4%. Additional focused studies are needed to confirm or refine the minimum sediment OC concentrations that are applicable for reducing uncertainty in toxicity predictions due to excess SEM. Integr Environ Assess Manag 2022;18:174-186. © 2021 SETAC.

Probing the contamination characteristics, mobility, and risk assessments of typical plastic additive-phthalate esters from a typical coastal aquaculture area, China.

Contamination characteristics, equilibrium partitioning and risk assessment of phthalate esters (PAEs) were investigated in seawater, sediment and biological samples collected from the Xiangshan Bay area during an annual investigation between January and November 2019. PAE concentrations detected in the mariculture environment in surface seawater, sediment, and biological samples were 172-3365 ng/L, 190-2430 µg/kg (dry weight [dw]), and 820-4926 µg/kg (dw), respectively. The dominant congeners in different media included di-n-butyl phthalate (DnBP), diisobutyl phthalate (DiBP), and di(2-ethylhexyl) phthalate (DEHP). The inner bay and the bay mouth were the gathering area of PAEs and heavily influenced by the mariculture activities, river inputs, and anthropogenic activities. The bioaccumulation of PAEs demonstrated benthic feeding fishes with relatively high trophic levels concentrated high levels of phthalates. The mobility of PAEs in sediment-seawater showed that the transfer tendency of low-molecular weight species was from the sediment to the water, which was in contrast with those of high-molecular weight PAEs. DEHP, DiBP and DnBP had various degrees of ecological risks in the aquatic environment, whereas only the DiBP posed potential risks in sediments. The current assessment of carcinogenic and noncarcinogenic risks posed by fish consumption were within acceptable limits for humans.

Sources and Fate of the Antiandrogenic Fluorescent Dye 4-Methyl-7-Diethylaminocoumarin in Small River Systems.

Recently, the potent antiandrogen 4-methyl-7-diethylaminocoumarin (C47) and its potential transformation products 4-methyl-7-ethylaminocoumarin (C47T1) and 4-methyl-7-aminocoumarin (C47T2) were identified as novel environmental contaminants. We assessed for the first time the sources, distribution, and fate of these compounds in aquatic systems using the Holtemme River (Saxony-Anhalt, Germany), which is a hotspot for these contaminants. To this end, wastewater-treatment plant (WWTP) influent and effluent samples, surface water samples over 3 years, and the longitudinal profiles in water, sediment, and gammarids were analyzed. From the longitudinal profile of the river stretch, the WWTP of Silstedt was identified as the sole point source for these compounds in the River Holtemme, and exposure concentrations in the low micrograms per liter range could be recorded continuously over 3 years. Analysis of WWTP influent and effluent showed a transformation of approximately half of the C47 into C47T1 and C47T2 but no complete removal. A further attenuation of the three coumarins after discharge into the river could be largely attributed to dilution, while transformation was only approximately 20%, thus suggesting a significant persistence in aquatic systems. Experimentally derived partitioning coefficients between water and sediment organic carbon exceeded those predicted using the OPERA quantitative structure-activity relationship tools and polyparameter linear free-energy relationships by up to 93-fold, suggesting cation binding as a significant factor for their sorption behavior. Near-equilibrium conditions between water and sediment were not observed close to the emitting WWTP but farther downstream in the river. Experimental and predicted bioaccumulation factors for gammarids were closely matching, and the concentrations in field-sampled gammarids were close to steady state with exposure concentrations in the water phase of the river. Environ Toxicol Chem 2021;40:3078-3091. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.