Preferential Partitioning of Per- and Polyfluoroalkyl Substances in Freshwater Ice.

Millions of lakes worldwide freeze, yet the fate of per- and polyfluoroalkyl substances (PFAS) in ice in freshwater systems is poorly understood. We quantified concentrations of 36 PFAS, dissolved organic carbon (DOC), and inorganic ions in ice and water in seven freshwater lakes to investigate the preferential exclusion of ions during freezing. PFAS concentrations in ice are typically lower than in the water column, demonstrating that these chemicals are excluded from ice as it freezes. However, there is preferential partitioning of both PFAS and DOC relative to cations with average sodium-normalized enrichment factors (EF) ranging from 2.74 for perfluorobutanoate (PFBA; a C4 perfluorocarboxylic acid) to 4.01 for perfluorooctanesulfonate (PFOS; a C8 perfluorosulfonic acid), with a similar EF value of 4.14 for DOC. Laboratory experiments and seasonal measurements of PFAS in the water column indicate that PFAS concentrations in ice are a function of aqueous PFAS concentrations, with lower EF values observed in waters with higher PFAS concentrations. Understanding PFAS behavior in freshwater ice is important for predicting contaminant fate during winter and spring periods, with implications for exposure to PFAS during the winter and release of PFAS when ice melts in freshwater systems.

Heterogeneous Photodegradation Behavior of Liquid Crystal Monomers in Dust: Quantitative Structure-Activity Relationship and Product Identification.

The heterogeneous photodegradation behavior of liquid crystal monomers (LCMs) in standard dust (standard reference material, SRM 2583) and environmental dust was investigated. The measured photodegradation ratios for 23 LCMs in SRM and environmental dust in 12 h were 11.1 ± 1.8 to 23.2 ± 1.1% and 8.7 ± 0.5 to 24.0 ± 2.8%, respectively. The degradation behavior of different LCM compounds varied depending on their structural properties. A quantitative structure-activity relationship model for predicting the degradation ratio of LCMs in SRM dust was established, which revealed that the molecular descriptors related to molecular polarizability, electronegativity, and molecular mass were closely associated with LCMs' photodegradation. The photodegradation products of the LCM compound 4'-propoxy-4-biphenylcarbonitrile (PBIPHCN) in dust, including •OH oxidation, C-O bond cleavage, and ring-opening products, were identified by nontarget analysis, and the corresponding degradation pathways were suggested. Some of the identified products, such as 4'-hydroxyethoxy-4-biphenylcarbonitrile, showed predicted toxicity (with an oral rat lethal dose of 50%) comparable to that of PBIPHCN. The half-lives of the studied LCMs in SRM dust were estimated at 32.2-82.5 h by fitting an exponential decay curve to the observed photodegradation data. The photodegradation mechanisms of LCMs in dust were revealed for the first time, enhancing the understanding of LCMs' environmental behavior and risks.

Multidirectional Fate Path Model to Connect Phosphorus Emissions with Freshwater Eutrophication Potential.

Excessive anthropogenic phosphorus (P) emissions put constant pressure on aquatic ecosystems. This pressure can be quantified as the freshwater eutrophication potential (FEP) by linking P emissions, P fate in environmental compartments, and the potentially disappeared fraction of species due to increase of P concentrations in freshwater. However, previous fate modeling on global and regional scales is mainly based on the eight-direction algorithm without distinguishing pollution sources. The algorithm fails to characterize the fate paths of point-source emissions via subsurface pipelines and wastewater treatment infrastructure, and exhibits suboptimal performance in accounting for multidirectional paths caused by river bifurcations, especially in flat terrains. Here we aim to improve the fate modeling by incorporating various fate paths and addressing multidirectional scenarios. We also update the P estimates by complementing potential untreated point-source emissions (PSu). The improved method is examined in a rapidly urbanizing area in Taihu Lake Basin, China in 2017 at a spatial resolution of 100 m × 100 m. Results show that the contribution of PSu on FEP (62.6%) is greater than that on P emissions (58.5%). The FEP is more spatially widely distributed with the improved fate modeling, facilitating targeted regulatory strategies tailored to local conditions.

Photodegradation Processes and Weathering Products of Microfibers in Aquatic Environments.

Microplastics, particularly microfibers (MFs), pose a significant threat to the environment. Despite their widespread presence, the photochemical reactivity, weathering products, and environmental fate of MFs remain poorly understood. To address this knowledge gap, photodegradation experiments were conducted on three prevalent MFs: polyester (POL), nylon (NYL), and acrylic (ACR), to elucidate their degradation pathways, changes in surface morphology and polymer structure, and chemical and colloidal characterization of weathering products during photochemical degradation of MFs. The results showed that concentrations of dissolved organic carbon, chromophoric dissolved organic matter (DOM), and fluorescent components consistently increased during weathering, exhibiting a continuous release of DOM. Scanning electron microscopy and Raman spectroscopy revealed changes in the surface morphology and polymer spectra of the MFs. During the weathering experiments, DOM aromaticity (SUVA254) decreased, while spectral slope increased, indicating concurrent DOM release and degradation of aromatic components. The released DOM or nanoplastics were negatively charged with sizes between 128 and 374 nm. The production rate constants of DOM or the photochemical reactivity of MFs followed the order ACR > NYL ≥ POL, consistent with their differences in chemical structures. These findings provide an improved understanding of the photochemical reactivity, degradation pathways, weathering products, and environmental fate of microfibers in the environment.

Maize (Zea mays L.) Plants Alter the Fate and Accumulate Nonextractable Residues of Sulfamethoxazole in Farmland Soil.

The fate of sulfonamide antibiotics in farmlands is crucial for food and ecological safety, yet it remains unclear. We used [phenyl-U-14C]-labeled sulfamethoxazole (14C-SMX) to quantitatively investigate the fate of SMX in a soil-maize system for 60 days, based on a six-pool fate model. Formation of nonextractable residues (NERs) was the predominant fate for SMX in unplanted soil, accompanied by minor mineralization. Notably, maize plants significantly increased SMX dissipation (kinetic constant kd = 0.30 day-1 vs 0.17 day-1), while substantially reducing the NER formation (92% vs 58% of initially applied SMX) and accumulating SMX (40%, mostly bound to roots). Significant NERs (maximal 29-42%) were formed via physicochemical entrapment (determined using silylation), which could partially be released and taken up by maize plants. The NERs consisted of a considerable amount of SMX formed via entrapment (1-8%) and alkali-hydrolyzable covalent bonds (2-12%, possibly amide linkage). Six and 10 transformation products were quantified in soil extracts and NERs, respectively, including products of hydroxyl substitution, deamination, and N-acylation, among which N-lactylated SMX was found for the first time. Our findings reveal the composition and instability of SMX-derived NERs in the soil-plant system and underscore the need to study the long-term impacts of reversible NERs.

Insights into the occurrence, distribution and dissipation of widespread agrochemicals in celery agrosystems for joint risk assessment.

Elucidating exposure risks associated with the most widely used agrochemicals and their metabolites in celery agrosystems are vital for food safety and human health. The occurrence, distribution, dissipation and metabolism of imidacloprid (IMI), acetamiprid (ACE), thiamethoxam (THM) and difenoconazole (DIF) in celery tissues reflected by initial depositions, uptake characteristics, half-lives, concentration variations. DIF exhibited unacceptable ecological risk to soil organisms under multi-risk evaluation models, including toxicity exposure ratio, risk quotient, and BITSSD model. The joint dietary risks of target pesticides were 37.273-647.454% and 0.400-2522.016% based on deterministic and probabilistic models, with non-carcinogenic risks of 30.207-85.522% and 1.229-2524.662%, respectively. Children aged 1-6 years suffered the highest exposure, with the leaves posing higher risk than other tissues. Long-term exposure risks should be continuously assessed for ecological sustainability and human health, given the widespread usage and cumulative effects of target pesticides, especially for rural children.

Manganese reductive dissolution coupled to Sb mobilization in contaminated shooting range soil.

A "redox-stat" RMnR bioreactor was employed to simulate moderately reducing conditions (+ 420 mV) in Sb-contaminated shooting range soils for approximately 3 months, thermodynamically favoring Mn(IV) reduction. The impact of moderately reducing conditions on elemental mobilization (Mn, Sb, Fe) and speciation [Sb(III) versus Sb(V); Fe2+/Fe3+] was compared to a control bioreactor RCTRL without a fixed redox potential. In both bioreactors, reducing conditions were accompanied by an increase in effluent Sb(V) and Mn(II) concentrations, suggesting that Sb(V) was released through microbial reduction of Mn oxyhydroxide minerals. This was underlined by multiple linear regression analysis showing a significant (p < 0.05) relationship between Mn and Sb effluent concentrations. Mn concentration was the sole variable exhibiting a statistically significant effect on Sb in RMnR, while under the more reducing conditions in RCTRL, pH and redox potential were also significant. Analysis of the bacterial community composition revealed an increase in the genera Azoarcus, Flavisolibacter, Luteimonas, and Mesorhizobium concerning the initial soil, some of which are possible key players in the process of Sb mobilization. The overall amount of Sb released in the RMnR (10.40%) was virtually the same as in the RCTRL (10.37%), which underlines a subordinate role of anoxic processes, such as Fe-reductive dissolution, in Sb mobilization. This research underscores the central role of relatively low concentrations of Mn oxyhydroxides in influencing the fate of trace elements. Our study also demonstrates that bioreactors operated as redox-stats represent versatile tools that allow quantifying the contribution of specific mechanisms determining the fate of trace elements in contaminated soils. KEY POINTS: • "Redox-stat" reactors elucidate Sb mobilization mechanisms • Mn oxyhydroxides microbial reductive dissolution has a major role in Sb mobilization in soils under moderately reducing conditions • Despite aging the soil exhibited significant Sb mobilization potential, emphasizing persistent environmental effects.

Mechanisms of adsorption and functionalization of biochar for pesticides: A review.

Agricultural production relies heavily on pesticides. However, factors like inefficient application, pesticide resistance, and environmental conditions reduce their effective utilization in agriculture. Subsequently, pesticides transfer into the soil, adversely affecting its physicochemical properties, microbial populations, and enzyme activities. Different pesticides interacting can lead to combined toxicity, posing risks to non-target organisms, biodiversity, and organism-environment interactions. Pesticide exposure may cause both acute and chronic effects on human health. Biochar, with its high specific surface area and porosity, offers numerous adsorption sites. Its stability, eco-friendliness, and superior adsorption capabilities render it an excellent choice. As a versatile material, biochar finds use in agriculture, environmental management, industry, energy, and medicine. Added to soil, biochar helps absorb or degrade pesticides in contaminated areas, enhancing soil microbial activity. Current research primarily focuses on biochar produced via direct pyrolysis for pesticide adsorption. Studies on functionalized biochar for this purpose are relatively scarce. This review examines biochar's pesticide absorption properties, its characteristics, formation mechanisms, environmental impact, and delves into adsorption mechanisms, functionalization methods, and their prospects and limitations.

Radiometric approaches with carbon-14-labeled molecules for determining herbicide fate in plant systems.

Weeds cause economic losses in cropping systems, leading to the use of 1.7 million tons of herbicides worldwide for weed control annually. Once in the environment, herbicides can reach non-target organisms, causing negative impacts on the ecosystem. Herbicide retention, transport, and degradation processes determine their environmental fate and are essential to assure the safety of these molecules. Radiometric strategies using carbon-14 herbicides (14C) are suitable approaches for determining herbicide absorption, translocation, degradation, retention, and transport in soil, plants, and water. In this work, we demonstrate how 14C-herbicides can be used from different perspectives. Our work focused on herbicide-plant-environment interactions when the herbicide is applied (a) through the leaf, (b) in the soil, and (c) in the water. We also quantified the mass balance in each experiment. 14C-mesotrione foliar absorption increased with oil and adjuvant addition (5-6 % to 25-46 %), and translocation increased only with adjuvant. More than 80 % of 14C-quinclorac and 14C-indaziflam remained in the soil and cover crops species absorbed less than 20 % of the total herbicides applied. In water systems, Salvinia spp. plants removed 10-18 % of atrazine from the water. Atrazine metabolism was not influenced by the presence of the plants. The radiometric strategies used were able to quantify the fate of the herbicide in different plant systems and the mass balance varied from 70 % to 130 %. Importantly, we highlight a critical and practical view of tracking herbicides in different matrices. This technique can aid scientists to explore other pesticides as environmental contaminants.

Fate characteristics and risk identification of thifluzamide in buckwheat across China: Analytical method development, occurrence, and health assessment.

Elaborating on the fate tendency of thifluzamide (thiazole-amide fungicide) in buckwheat based on nationwide application is vital for grain security and human health based on nationwide application. A rapid and sensitive analytical method was developed to trace thifluzamide in buckwheat matrices using an ultrahigh-performance liquid chromatography-tandem triple quadrupole mass spectrometer (UHPLC-MS/MS), with a retention time of 2.90 min and limit of quantitation (LOQ) of 0.001 mg/kg. Thifluzamide could be stably stored for 84 d in buckwheat matrices under -20 °C under dark condition. The occurrence, dissipation and terminal magnitudes of thifluzamide were reflected by the primary deposition of 0.02-0.55 mg/kg, half-lives of 12-14 d, and highest residues of 0.41 mg/kg. The long-term risks (ADI%) of thifluzamide were 37.268 %-131.658 % in registered crops, and the risks for the rural population were significantly higher than those of the urban population. The unacceptable dietary risks of thifluzamide should be continuously emphasized for children aged 2-7 with an ADI% values of 100.750 %-131.658 %. A probabilistic model was further introduced to evaluate the risk discrepancy of thifluzamide in buckwheat, showing the risks in Tartary buckwheat (Fagopyrum tararicum Gaerth) were 1.5-75.4 times than that in sweet buckwheat (Fagopyrum esculentum Moench). Despite the low risks for dietary buckwheat, the high-potential health hazards of thifluzamide should be pay more attention given the increasing applications and cumulative effects.

Insecticidal potential and risk assessment of diamide pesticides against Spodoptera frugiperda in maize crops.

The effectiveness, tolerance, and safety of pesticides must be established before their scientific or rational. This study evaluates the field control efficacy of broflanilide, tetraniliprole, and chlorantraniliprole in combating Spodoptera frugiperda in maize crops, as well as the resistance of S. frugiperda to these three diamide pesticides after exposure. By assessing field control efficiency, toxicity, effects on development and reproduction, and detoxification enzyme activity of these diamide pesticides on S. frugiperda, highlights broflanilide's significant insecticidal potential. A highly sensitive and efficient method using QuEChERS/HPLCMS/MS was developed to simultaneously detect residues of these three pesticides on maize. Initial concentrations of broflanilide, tetraniliprole, and chlorantraniliprole ranged from 2.13 to 4.02 mg/kg, with their respective half-lives varying between 1.23 and 1.51 days. Following foliar application, by the time of harvest, the terminal residue concentrations of these pesticides were all under 0.01 mg/kg. Chronic dietary intake risk assessments and cumulative chronic dietary exposure for three pesticides indicated that the general population's terminal residue concentration was within acceptable limits. Not only does this research provide valuable insights into field control efficiency, insecticidal effects, resistance, residues, and risk assessment results of broflanilide, tetraniliprole, and chlorantraniliprole on maize, but additionally, it also paves the way for setting suitable Maximum Residue Limits (MRLs) values based on pre-harvest interval values, rational dosage, and application frequency.

The adsorption and its mechanism of venlafaxine by original and aged polypropylene microplastic and the changes of joint toxicity.

Conjugation with the increment of consumption of polypropylene (PP) masks and antidepressants during pandemic, PP microplastics (MPs) and Venlafaxine (VEN) widely co-existed in surface waters. However, their environmental fate and the combined toxicity were unclear. Hence, we investigated the adsorption behaviors, and associated mechanisms of PP MPs for VEN. The impact factors including pH, salinity, and MPs aging were estimated. The results indicated PP MPs could adsorb amount of VEN within 24 h. The pseudo second-order kinetic model (R2 = 0.97) and Dubinin-Radushkevich model (R2 = 0.89) fitted well with the adsorption capacity of PP MPs for VEN, implying that chemical adsorption accompanied by electrostatic interaction might be the predominant mode for the interactions between PP MPs and VEN. Meanwhile, the adsorption capacity of PP MPs declined from pH of 2.5-4.5 and then increased from 4.5 to 9.5. The increased salinity (5-35 ppt) significantly suppressed the adsorption capacity. Aging by sunlight and UV triggered the formation of new functional group (carbonyl) on MPs, and then enhanced the adsorption capacity for VEN. Gaussian Model analysis further evidenced the electrostatic adsorption occurring in PP MPs and VEN. The combined exposure to PP MPs and VEN showed significantly antagonistic toxicity on Daphnia magna. The adsorption of VEN by PP MPs mitigated the lethal effects and behavioral function impairment posed by VEN on animals, implying the potential protective effects on zooplankton by PP MPs. This study for the first time provides perspective for assessing the environmental fate of MPs and antidepressants in aquatic system.

Investigating the impact of soil properties, application rates and environmental conditions on pyroxasulfone dissipation and its ecotoxicological effects on soil health in aridisols of Punjab.

This study is to understand the fate and ecological consequences of pyroxasulfone in aridisols of Punjab, a detailed dissipation study in soil, its influence on soil enzymes, microbial count and succeeding crops was evaluated. Half-lives (DT50) increased with an increase in the application rate of pyroxasulfone. Dissipation of pyroxasulfone decreased with increase in organic matter content of soil and was slower in clay loam soil (DT50 12.50 to 24.89) followed by sandy loam (DT50 8.91 to 17.78) and loamy sand soil (DT50 6.45 to 14.89). Faster dissipation was observed under submerged conditions (DT50 2.9 to 20.99 days) than under field capacity conditions (DT50 6.45 to 24.89 days). Dissipation increased with increase in temperature with DT50 varying from 6.46 to 24.88, 4.87 to 22.89 and 2.97 to 20.99 days at 25 ± 2, 35 ± 2 and 45 ± 2 °C, respectively. Dissipation was slower under sterile conditions and about 23.87- to 33.74-fold increase in DT50 was observed under sterile conditions as compared to non-sterile conditions. The application of pyroxasulfone showed short-lived transitory effect on dehydrogenase, alkaline phosphatase and soil microbial activity while herbicide has non-significant effect on soil urease activity. PCA suggested that dehydrogenase and bacteria were most sensitive among enzymatic and microbial activities. In efficacy study, pyroxasulfone effectively controlled Phalaris minor germination, with higher efficacy in loamy sand soil (GR50 2.46 µg mL-1) as compared to clay loam soil (GR50 5.19 µg mL-1).

Hydroxyl Radical Transformations of Perfluoroalkyl Acid (PFAA) Precursors in Aqueous Film Forming Foams (AFFFs).

Historical releases of aqueous film forming foam (AFFF) are significant sources of poly- and perfluoroalkyl substances (PFASs), including perfluoroalkyl acids (PFAAs) and their precursors, to the environment. While several studies have focused on microbial biotransformation of polyfluorinated precursors to PFAAs, the role of abiotic transformations at AFFF-impacted sites is less clear. Herein, we use photochemically generated hydroxyl radical to demonstrate that environmentally relevant concentrations of hydroxyl radical (•OH) can play a significant role in these transformations. High-resolution mass spectrometry (HRMS) was used to perform targeted analysis, suspect screening, and nontargeted analyses, which were used to identify the major products of AFFF-derived PFASs as perfluorocarboxylic acids, though several potentially semi-stable intermediates were also observed. Using competition kinetics in a UV/H2O2 system, hydroxyl radical rate constants (kOH) for 24 AFFF-derived polyfluoroalkyl precursors were measured to be 0.28 to 3.4 × 109 M-1 s-1. Differences in kOH were observed for compounds with differing headgroups and perfluoroalkyl chain lengths. Also, differences in kOH measured for the only relevant precursor standard available, n-[3-propyl]tridecafluorohexanesulphonamide (AmPr-FHxSA), as compared to AmPr-FHxSA present in AFFF suggest that intermolecular associations in the AFFF matrix may affect kOH. Considering environmentally relevant [•OH]ss, polyfluoroalkyl precursors are expected to exhibit half-lives of ∼8 days in sunlit surface waters and possibly as short as ∼2 h during oxygenation of Fe(II)-rich subsurface systems.

Multiomics Sequencing and AlphaFold2 Analysis of the Stereoselective Behavior of Mefentrifluconazole for Bioactivity Improvement and Risk Reduction.

As the first isopropanol chiral triazole fungicide, mefentrifluconazole has broad prospects for application. In this study, the stereoselective stability, bioactivity, fate, and biotoxicity were systematically investigated. Our results indicated that the stability of mefentrifluconazole enantiomers differed between environmental media, and they were stable in water and sediment in the dark. The bactericidal activity of R-mefentrifluconazole against the four target pathogens was 4.6-43 times higher than that of S-mefentrifluconazole. In the water-sediment system, S-mefentrifluconazole dissipated faster than R-mefentrifluconazole in water; however, its accumulation capacity was higher than that of R-mefentrifluconazole in sediment and zebrafish. S-Mefentrifluconazole induced more differentially expressed genes (DEGs) and differentially expressed proteins (DEPs) in zebrafish than did R-mefentrifluconazole. Multiomics sequencing results showed that S-mefentrifluconazole enhanced the antioxidant, detoxification, immune, and metabolic functions of zebrafish by interacting with related proteins. Based on AlphaFold2 modeling and molecular docking, mefentrifluconazole enantiomers had different binding modes with key target proteins in pathogens and zebrafish, which may be the main reason for the stereoselective differences in bioactivity and biotoxicity. Based on its excellent bioactivity and low biotoxicity, the R-enantiomer can be developed to improve the bioactivity and reduce the risk of mefentrifluconazole.

Indirect Emissions from Organophosphite Antioxidants Result in Significant Organophosphate Ester Contamination in China.

Organophosphite antioxidants (OPAs) have been seriously neglected as potential sources of organophosphate esters (OPEs) in environments. This study utilizes a modeling approach to quantify for the first time national emissions and multimedia distributions of triphenyl phosphate (TPHP)─a well-known flame retardant─and three novel OPEs: tris(2,4-ditert-butylphenyl) phosphate (AO168═O), bis(2,4-ditert-butylphenyl) pentaerythritol diphosphate (AO626═O2), and trisnonylphenol phosphate (TNPP). Emphasis is on the quantitative assessment of OPA source in China. TPHP has 1.1-9.7 times higher emission (300 Mg/year in 2019 with half from OPA sources) than AO168═O (278 Mg/year), AO626═O2 (53 Mg/year), and TNPP (32 Mg/year), but AO168═O is predominant in environments (63-79%) except freshwaters. About 72-99% of the studied OPEs are emitted via air, with 88-99% ultimately distributed into soils as the major sink. OPA-source emissions contribute 9.5-57% and 4.7-56% of TPHP masses and concentrations (except in sediments) in different media, respectively. Both AO168═O and AO626═O2 exhibit high overall persistence ranging between 2 and 11 years. Source emissions and environmental concentrations are elevated in economically developed areas, while persistence is higher in northern areas, where precipitation and temperature are lower. This study shows the significance of the sources of OPA to OPE contamination, which supports chemical management of these substances.

Extracellular Vesicles and Bacteriophages: New Directions in Environmental Biocolloid Research.

There is a long-standing appreciation among environmental engineers and scientists regarding the importance of biologically derived colloidal particles and their environmental fate. This interest has been recently renewed in considering bacteriophages and extracellular vesicles, which are each poised to offer engineers unique insights into fundamental aspects of environmental microbiology and novel approaches for engineering applications, including advances in wastewater treatment and sustainable agricultural practices. Challenges persist due to our limited understanding of interactions between these nanoscale particles with unique surface properties and their local environments. This review considers these biological particles through the lens of colloid science with attention given to their environmental impact and surface properties. We discuss methods developed for the study of inert (nonbiological) particle-particle interactions and the potential to use these to advance our understanding of the environmental fate and transport of extracellular vesicles and bacteriophages.

Environmental Impacts of Coal Combustion Residuals: Current Understanding and Future Perspectives.

On-site solid-waste impoundments, landfills, and receiving water bodies have served as long-term disposal sites for coal combustion residuals (CCRs) across the United States for decades and collectively contain billions of tons of CCR material. CCR components include fine particulate material, minerals, and trace elements such as mercury, arsenic, selenium, lead, etc., which can have deleterious effects on ecosystem functioning and public health. Effects on communities can occur through consumption of drinking water, fish, and other aquatic organisms. The structural failure of impoundments, water infiltration, leakage from impoundments due to poor construction and monitoring, and CCR effluent discharges to water bodies have in the past resulted in harmful environmental impacts. Moreover, the risks posed by CCRs are present to this day, as coal continues to account for 11% of the energy production in the United States. In this Critical Review, the legacy of CCR disposal and the concomitant risks posed to public health and ecosystems are assessed. The resiliency of CCR disposal sites in the context of increased frequency and intensity of storm events and other hazards, such as floods and earthquakes, is also evaluated. We discuss the current state of knowledge on the environmental fate of CCR-derived elements, as well as advances in and limitations of analytical tools, which can improve the current understanding of CCR environmental impacts in order to mitigate the associated risks. An assessment of the 2015 Coal Ash Final Rule is also presented, along with needs to improve monitoring of CCR disposal sites and regulatory enforcement.

Applicability Domains Based on Molecular Graph Contrastive Learning Enable Graph Attention Network Models to Accurately Predict 15 Environmental End Points.

In silico models for predicting physicochemical properties and environmental fate parameters are necessary for the sound management of chemicals. This study employed graph attention network (GAT) algorithms to construct such models on 15 end points. The results showed that the GAT models outperformed the previous state-of-the-art models, and their performance was not influenced by the presence or absence of compounds with certain structures. Molecular similarity density (ρs) was found to be a key metrics characterizing data set modelability, in addition to the proportion of compounds at activity cliffs. By introducing molecular graph (MG) contrastive learning, MG-based ρs and molecular inconsistency in activities (IA) were calculated and employed for characterizing the structure-activity landscape (SAL)-based applicability domain ADSAL{ρs, IA}. The GAT models coupled with ADSAL{ρs, IA} significantly improved the prediction coefficient of determination (R2) on all the end points by an average of 14.4% and enabled all the end points to have R2 > 0.9, which could hardly be achieved previously. The models were employed to screen persistent, mobile, and/or bioaccumulative chemicals from inventories consisting of about 106 chemicals. Given the current state-of-the-art model performance and coverage of the various environmental end points, the constructed models with ADSAL{ρs, IA} may serve as benchmarks for future efforts to improve modeling efficacy.

Aquatic toxicity and fate of styrene oligomers in the environment.

Styrene oligomers (SOs) are ubiquitous contaminants that appear in the environment, sometimes to significant extent (see section 3.1). Despite the ongoing international debate on the human health risks posed by SOs, to the best of my knowledge, there are no studies on the aquatic toxicity and environmental fates (biodegradation and atmospheric degradation) of SOs in the environment. This study is to predict the aquatic toxicity and environmental fate of SOs by using the US EPA EPI suite program as an in-silico method. For better understanding, the risks and fates of SOs are compared with those of the well-known bisphenol A (BPA) and styrene monomer (SM or styrene). As a result of this study, SOs are predicted to be relatively more toxic than BPA and SM to aquatic and terrestrial organisms in the freshwater, marine, and terrestrial environments. In particular, the biodegradability of SOs is predicted to be relatively very slow in the environment, and most SOs are more likely to be effectively decomposed by hydroxyl radicals than by ozone in the atmosphere. As a result, this study can contribute to motivating understanding of the aquatic toxicity and fate of ubiquitous SOs in the environment.