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Groundwater aquifers worldwide experience unsustainable depletion, compounded by population growth, economic development, and climate forcing. Managed aquifer recharge provides one tool to alleviate flood risk and replenish groundwater. However, concerns grow that intentional flooding of farmland for groundwater recharge, a practice known as Ag-MAR, may increase the leaching of pesticides and other chemicals into groundwater. This study employs a physically based unsaturated flow model to determine the fate and transport of residues of four pesticide in three vadose zone profiles characterized by differing fractions of sand (41 %, 61 %, and 84 %) in California's Central Valley. Here, we show that the complex heterogeneity of alternating coarse and fine-grain hydrogeologic units controls the transit times of pesticides and their adsorption and degradation rates. Unsaturated zones that contain a higher fraction of sand are more prone to support preferential flow, higher recharge rates (+8 %), and faster (42 %) water flow and pesticide transport, more flooding-induced pesticide leaching (about 22 %), as well as more salt leaching correlating with increased risks of groundwater contamination. Interestingly, considering preferential flow predicted higher degradation and retention rates despite shorter travel times, attributed to the trapping of pesticides in immobile zones where they degrade more effectively. The findings underscore the importance of considering soil texture and structure in Ag-MAR practices to minimize environmental risks while enhancing groundwater recharge. The study also highlights that selecting less mobile pesticides can reduce leaching risks in sandy areas.

The production and uptake of toxic methylmercury (MeHg) impacts aquatic ecosystems globally. Rivers can be dynamic and difficult systems to study for MeHg production and bioaccumulation, hence identifying sources of MeHg to these systems is both challenging and important for resource management within rivers and main-stem reservoirs. Riparian zones, which are known biogeochemical hotspots for MeHg production, are understudied as potential sources of MeHg to rivers. Here, we present a comprehensive quantification of the hydrologic and biogeochemical processes governing MeHg concentrations, loads, and bioaccumulation at 16 locations along 164 km of the agriculturally intensive Snake River (Idaho, Oregon USA) during summer baseflow conditions, with emphasis on riparian production of MeHg. Approximately one-third of the MeHg load of the Snake River could not be attributed to inflowing waters (upgradient, tributaries, or irrigation drains). Across the study reach, increases in MeHg loads in surface waters were significantly correlated with MeHg concentrations in riparian porewaters, suggesting riparian zones were likely an important source of MeHg to the Snake River. Across all locations, MeHg concentrations in surface waters positively correlated with MeHg concentrations in benthic snails and clams, supporting that riparian produced MeHg was assimilated into local aquatic food webs. This study contributes new insights into riparian MeHg production within rivers which can inform mitigation efforts to reduce MeHg bioaccumulation in fish.

Globally, ocean dumping of chemical waste is a common method of disposal and relies on the assumption that dilution, diffusion, and dispersion at ocean scales will mitigate human exposure and ecosystem impacts. In southern California, extensive dumping of agrochemical waste, particularly chlorinated hydrocarbon contaminants such as DDT, via sewage outfalls and permitted offshore barging occurred for most of the last century. This study compiled a database of existing sediment and fish DDT measurements to examine how this unique legacy of regional ocean disposal translates into the contemporary contamination of the coastal ocean. We used spatiotemporal modeling to derive continuous estimates of sediment DDT contamination and show that the spatial signature of disposal (i.e., high loadings near historic dumping sites) is highly conserved in sediments. Moreover, we demonstrate that the proximity of fish to areas of high sediment loadings explained over half of the variation in fish DDT concentrations. The relationship between sediment and fish contamination was mediated by ecological predictors (e.g., species, trophic ecology, habitat use), and the relative influence of each predictor was context-dependent, with habitat exhibiting greater importance in heavily contaminated areas. Thus, despite more than half a century since the cessation of industrial dumping in the region, local ecosystem contamination continues to mirror the spatial legacy of dumping, suggesting that sediment can serve as a robust predictor of fish contamination, and general ecological characteristics offer a predictive framework for unmeasured species or locations.

Pericardial edema - fluid accumulation within the pericardium - is a frequently observed malformation in zebrafish embryo-based chemical toxicity screens. We recently discovered that the severity of triphenyl phosphate (TPHP)-induced pericardial edema was dependent on the ionic strength of exposure media. TPHP is an aryl phosphate ester (APE) widely used as a plasticizer and flame retardant. APEs are characterized by having one or more aryl groups bound to a phosphate center, with TPHP containing only unsubstituted aryl groups. Therefore, the objective of this study was to begin investigating whether, similar to TPHP, pericardial edema induced by other structurally related APEs is dependent on the ionic composition of exposure media. We first mined the peer-reviewed literature to identify other APEs that 1) induced pericardial edema in zebrafish embryos within a minimum of three peer-reviewed publications, and 2) demonstrated a statistically significant induction of pericardial edema in at least 70 % of the studies evaluated. Based on this meta-analysis, we identified four other APEs that caused pericardial edema in zebrafish embryos: isopropylated triphenyl phosphate (IPTPP), cresyl diphenyl phosphate (CDP), tricresyl phosphate (TMPP), and 2-ethylhexyl diphenyl phosphate (EDHPHP). Using TPHP as a positive control and pericardial edema as a readout, we developed concentration-response curves for all four APEs based on static exposure from 24 to 72 h post-fertilization (hpf). We then conducted co-exposures with D-Mannitol (an osmotic diuretic) and exposures within reverse osmosis (RO) water determine whether the ionic composition of exposure media mitigated APE-induced pericardial edema at 72 hpf. Using pericardial edema as an endpoint, the approximate EC50s for TPHP (positive control), IPTPP, CDP, TMPP, and EDHPHP were 6.25, 3.125, 3.125, 25, and 100 µM, respectively, based on exposure from 24 to 72 hpf. Interestingly, similar to our findings with TPHP, co-exposure with D-Mannitol and exposure within ion-deficient water significantly mitigated IPTPP- CDP-, TMPP-, and EDHPHP-induced pericardial edema in zebrafish embryos, suggesting that chemically-induced pericardial edema may be 1) dependent on the ionic composition of exposure media and 2) driven by a disruption in osmoregulation across the embryonic epidermis. Therefore, similar to other assay parameters, our findings underscore the need to standardize the osmolarity of exposure media in order to minimize the potential for false positive/negative hits in zebrafish embryo-based chemical toxicity screens conducted around the world.

Per- and polyfluoroalkyl substances (PFAS) are persistent chemicals of increasing concern to human health. PFAS contamination in water systems has been linked to a variety of sources including hydrocarbon fire suppression activities, industrial and military land uses, agricultural applications of biosolids, and consumer products. To assess PFAS in California tap water, we collected 60 water samples from inside homes in four different geographic regions, both urban and rural. We selected mostly small water systems with known history of industrial chemical or pesticide contamination and that served socioeconomically disadvantaged communities. Thirty percent of the tap water samples (18) had a detection of at least one of the 32 targeted PFAS and most detections (89 %) occurred in heavily industrialized Southeast Los Angeles (SELA). The residents of SELA are predominately Latino and low-income. Concentrations of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) ranged from 6.8 to 13.6 ng/L and 9.4-17.8 ng/L, respectively in SELA and were higher than State (PFOA: 0.007 ng/L; PFOS: 1.0 ng/L) and national health-based goals (zero). To look for geographic patterns, we mapped potential sources of PFAS contamination, such as chrome plating facilities, airports, landfills, and refineries, located near the SELA water systems; consistent with the multiple potential sources in the area, no clear spatial associations were observed. The results indicate the importance of systematic testing of PFAS in tap water, continued development of PFAS regulatory standards and advisories for a greater number of compounds, improved drinking-water treatments to mitigate potential health threats to communities, especially in socioeconomically disadvantaged and industrialized areas.

Harmful cyanobacteria blooms are a growing threat in estuarine waters as upstream blooms are exported into coastal environments. Cyanobacteria can produce potent toxins, one of which-hepatotoxic microcystins (MCs)-can persist and accumulate within the food web. Filter-feeding invertebrates may biomagnify toxins up to 100× ambient concentrations. As such, bivalves can be used as an environmentally relevant and highly sensitive sentinel for MC monitoring. To date there has been little research on cyanotoxin bioaccumulation in estuaries. The Sacramento-San Joaquin Delta (Delta) aquatic food web has undergone a profound change in response to widespread colonization of aquatic invasive species such as Asian clams (Corbicula fluminea) in the freshwater portion of the Delta. These clams are prolific-blanketing areas of the Delta at densities up to 1000 clams/m2 and are directly implicated in the pelagic organism decline of threatened and endangered fishes. We hypothesized that Asian clams accumulate MCs which may act as an additional stressor to the food web and MCs would seasonally be in exceedance of public health advisory levels. MCs accumulation in Delta Asian clams and signal crayfish (Pacifastacus leniusculus) were studied over a two-year period. ELISA and LC-MS analytical methods were used to measure free and protein-bound MCs in clam and crayfish tissues. We describe an improved MC extraction method for use when analyzing these taxa by LC-MS. MCs were found to accumulate in Asian clams across all months and at all study sites, with seasonal maxima occurring during the summer. Although MC concentrations rarely exceeded public health advisory levels, the persistence of MCs year-round still poses a chronic risk to consumers. Crayfish at times also accumulated high concentrations of MCs. Our results highlight the utility of shellfish as sentinel organisms for monitoring in estuarine areas.

Coastal upwelling supplies nutrients supporting primary production while also adding the toxic trace metal mercury (Hg) to the mixed layer of the ocean. This could be a concern for human and environmental health if it results in the enhanced bioaccumulation of monomethylmercury (MMHg). Here, we explore how upwelling influences Hg cycling in the California Current System (CCS) biome through particle scavenging and sea-air exchange. We collected suspended and sinking particle samples from a coastal upwelled water parcel and an offshore non-upwelled water parcel and observed higher total particulate Hg and sinking flux in the upwelling region compared to open ocean. To further investigate the full dynamics of Hg cycling, we modeled Hg inventories and fluxes in the upper ocean under upwelling and non-upwelling scenarios. The model simulations confirmed and quantified that upwelling enhances sinking fluxes of Hg by 41% through elevated primary production. Such an enhanced sinking flux of Hg is biogeochemically important to understand in upwelling regions, as it increases the delivery of Hg to the deep ocean where net conversion to MMHg may take place.

Oil spills are a frequent perturbation to the marine environment that has rapid and significant impacts on the local microbiome. Previous studies have shown that exposure to synthetic dispersant alone did not enhance heterotrophic microbial activity or oxidation rates of specific hydrocarbon components but increased the abundance of some taxa (e.g., Colwellia). In contrast, exposure to oil, but not dispersants, increased the abundance of other taxa (e.g., Marinobacter) and stimulated hydrocarbon oxidation rates. Here, we advance these findings by interpreting metatranscriptomic data from this experiment to explore how and why specific components of the microbial community responded to distinct organic carbon exposure regimes. Dispersant alone was selected for a unique community and for dominant organisms that reflected treatment- and time-dependent responses. Dispersant amendment also led to diverging functional profiles among the different treatments. Similarly, oil alone was selected for a community that was distinct from treatments amended with dispersants. The presence of oil and dispersants with added nutrients led to substantial differences in microbial responses, likely suggesting increased fitness driven by the presence of additional inorganic nutrients. The oil-only additions led to a marked increase in the expression of phages, prophages, transposable elements, and plasmids (PPTEPs), suggesting that aspects of microbial community response to oil are driven by the mobilome, potentially through viral-associated regulation of metabolic pathways in ciliates and flagellates that would otherwise throttle the microbial community through grazing.IMPORTANCEMicrocosm experiments simulated the April 2010 Deepwater Horizon oil spill by applying oil and synthetic dispersants (Corexit EC9500A and EC9527A) to deep ocean water samples. The exposure regime revealed severe negative alterations in the treatments heterotrophic microbial activity and hydrocarbon oxidation rates. We expanded these findings by exploring metatranscriptomic signatures of the microbial communities during the chemical amendments in the microcosm experiments. Here we report how dominant organisms were uniquely associated with treatment- and time-dependent trajectories during the exposure regimes; nutrient availability was a significant factor in driving changes in metatranscriptomic responses. Remarkable signals associated with PPTEPs showed the potential role of mobilome and viral-associated survival responses. These insights underscore the time-dependent environmental perturbations of fragile marine environments under oil and anthropogenic stress.

To oxidize trace concentrations of organic contaminants under conditions relevant to surface- and groundwater, air-diffusion cathodes were coupled to stainless-steel cathodes that convert atmospheric O2 into hydrogen peroxide (H2O2), which then was activated to produce hydroxyl radicals (·OH). By separating H2O2 generation from its activation and employing a flow-through electrode consisting of stainless-steel fibers, the two processes could be operated efficiently in a manner that overcame mass-transfer limitations for O2, H2O2, and trace organic contaminants. The flexibility resulting from separate control of the two processes made it possible to avoid both the accumulation of excess H2O2 and the energy losses that take place after H2O2 has been depleted. The decrease in treatment efficacy occurring in the presence of natural organic matter was substantially lower than that typically observed in homogeneous advanced oxidation processes. Experiments conducted with ionized and neutral compounds indicated that electrostatic repulsion prevented negatively charged ·OH scavengers from interfering with the oxidation of neutral contaminants. Energy consumption by the dual-cathode system was lower than values reported for other technologies intended for small-scale drinking water treatment systems. The coordinated operation of these two cathodes has the potential to provide a practical, inexpensive way for point-of-use drinking water treatment.

Dichloramine (NHCl2) naturally exists in reverse osmosis (RO) permeate due to its application as an antifouling chemical in membrane-based potable reuse treatment. This study investigated mechanisms of background NHCl2 hydrolysis associated with the generation of oxidative radical species in RO permeate, established a kinetic model to predict the oxidative capacity, and examined its removal efficiency on trace organic contaminants in potable reuse. Results showed that NHCl2 hydrolysis generated transient peroxynitrite (ONOO-) and subsequently dissociated into hydroxyl radical (HO•). The maximal HO• exposure was observed at an RO permeate pH of 8.4, higher than that from typical ultraviolet (UV)-based advanced oxidation processes. The HO• exposure during NHCl2 hydrolysis also peaked at a NH2Cl-to-NHCl2 molar ratio of 1:1. The oxidative capacity rapidly degraded 1,4-dioxane, carbamazepine, atenolol, and sulfamethoxazole in RO permeate. Furthermore, background elevated carbonate in fresh RO permeate can convert HO• to carbonate radical (CO3•-). Aeration of the RO permeate removed total carbonate, significantly increased HO• exposure, and enhanced the degradation kinetics of trace organic contaminants. The kinetic model of NHCl2 hydrolysis predicted well the degradation of contaminants in RO permeate. This study provides new mechanistic insights into NHCl2 hydrolysis that contributes to the oxidative degradation of trace organic contaminants in potable reuse systems.

The intensifying global opioid crisis, majorly attributed to fentanyl (FT) and its analogs, has necessitated the development of rapid and ultrasensitive remote/on-site FT sensing modalities. However, current approaches for tracking FT exposure through wastewater-based epidemiology (WBE) are unadaptable, time-consuming, and require trained professionals. Toward developing an extended in situ wastewater opioid monitoring system, we have developed a screen-printed electrochemical FT sensor and integrated it with a customized submersible remote sensing probe. The sensor composition and design have been optimized to address the challenges for extended in situ FT monitoring. Specifically, ZIF-8 metal-organic framework (MOF)-derived mesoporous carbon (MPC) nanoparticles (NPs) are incorporated in the screen-printed carbon electrode (SPCE) transducer to improve FT accumulation and its electrocatalytic oxidation. A rapid (10 s) and sensitive square wave voltammetric (SWV) FT detection down to 9.9 µgL-1 is thus achieved in aqueous buffer solution. A protective mixed-matrix membrane (MMM) has been optimized as the anti-fouling sensor coating to mitigate electrode passivation by FT oxidation products and enable long-term, intermittent FT monitoring. The unique MMM, comprising an insulating polyvinyl chloride (PVC) matrix and carboxyl-functionalized multi-walled carbon nanotubes (CNT-COOH) as semiconductive fillers, yielded highly stable FT sensor operation (> 95% normalized response) up to 10 h in domestic wastewater, and up to 4 h in untreated river water. This sensing platform enables wireless data acquisition on a smartphone via Bluetooth. Such effective remote operation of submersible opioid sensing probes could enable stricter surveillance of community water systems toward timely alerts, countermeasures, and legal enforcement.

Monomethylmercury (MMHg) is a neurotoxicant that biomagnifies in marine food webs, reaching high concentrations in apex predators. To predict changes in oceanic MMHg concentrations, it is important to quantify the sources and sinks of MMHg. Here, we study mercury speciation in the California Current System through cruise sampling and modeling. Previous work in the California Current System has found that upwelling transports mercury-enriched deep waters to productive surface waters. These upwelled waters originate within the California Undercurrent water mass and are subsequently advected as a surface water parcel to the California Current. Between the two major water masses, we find that compared to the California Current, the California Undercurrent contains elevated dissolved total mercury (THg) and dimethylmercury (DMHg) concentrations by 59 and 69%, respectively. We explain that these differences result from losses during advection, specifically scavenging of THg and DMHg demethylation. We calculate a net DMHg demethylation rate of 2.0 ± 1.1% d-1 and build an empirically constrained mass budget model to demonstrate that net DMHg demethylation accounts for 61% of surface MMHg sources. These findings illustrate that DMHg is a significant source of MMHg in this region, challenging the current understanding of the major sources of marine MMHg.

Bottlenose dolphins (Tursiops truncatus) are keystone and sentinel species in the world's oceans. We studied correlations between per- and polyfluoroalkyl substances (PFAS) and their stress axis. We investigated associations between plasma biomarkers of 12 different PFAS variants and three cortisol pools (total, bound, and free) in wild T. truncatus from estuarine waters of Charleston, South Carolina (n = 115) and Indian River Lagoon, Florida (n = 178) from 2003 to 2006, 2010-2013, and 2015. All PFAS and total cortisol levels for these dolphins were previously reported; bound cortisol levels and free cortisol calculations have not been previously reported. We tested null hypotheses that levels of each PFAS were not correlated with those of each cortisol pool. Free cortisol levels were lower when PFOS, PFOA, and PFHxS biomarker levels were higher, but free cortisol levels were higher when PFTriA was higher. Bound cortisol levels were higher when there were higher PFDA, PFDoDA, PFDS, PFTeA, and PFUnDA biomarkers. Total cortisol was higher when PFOA was lower, but total cortisol was higher when PFDA, PFDoDA, PFTeA, and PFTriA were higher. Additional analyses indicated sex and age trends, as well as heterogeneity of effects from the covariates carbon chain length and PFAS class. Although this is a cross-sectional observational study and, therefore, could reflect cortisol impacts on PFAS toxicokinetics, these correlations are suggestive that PFAS impacts the stress axis in T. truncatus. However, if PFAS do impact the stress axis of dolphins, it is specific to the chemical structure, and could affect the individual pools of cortisol differently. It is critical to conduct long-term studies on these dolphins and to compare them to populations that have no or little expose to PFAS.

The total oxidizable precursor (TOP) assay has been extensively used for detecting PFAS pollutants that do not have analytical standards. It uses hydroxyl radicals (HO•) from the heat activation of persulfate under alkaline pH to convert H-containing precursors to perfluoroalkyl carboxylates (PFCAs) for target analysis. However, the current TOP assay oxidation method does not apply to emerging PFAS because (i) many structures do not contain C-H bonds for HO• attack and (ii) the transformation products are not necessarily PFCAs. In this study, we explored the use of classic acidic persulfate digestion, which generates sulfate radicals (SO4-•), to extend the capability of the TOP assay. We examined the oxidation of Nafion-related ether sulfonates that contain C-H or -COO-, characterized the oxidation products, and quantified the F atom balance. The SO4-• oxidation greatly expanded the scope of oxidizable precursors. The transformation was initiated by decarboxylation, followed by various spontaneous steps, such as HF elimination and ester hydrolysis. We further compared the oxidation of legacy fluorotelomers using SO4-• versus HO•. The results suggest novel product distribution patterns, depending on the functional group and oxidant dose. The general trends and strategies were also validated by analyzing a mixture of 100000- or 10000-fold diluted aqueous film-forming foam (containing various fluorotelomer surfactants and organics) and a spiked Nafion precursor. Therefore, (1) the combined use of SO4-• and HO• oxidation, (2) the expanded list of standard chemicals, and (3) further elucidation of SO4-• oxidation mechanisms will provide more critical information to probe emerging PFAS pollutants.

Mercury is a hazardous pollutant of global concern. While advances have been made in identifying the detrimental effects caused by Hg species in phytoplankton, knowledge gaps remain regarding the metabolomic perturbations induced by inorganic mercury (Hg(II)) and monomethylmercury (MeHg) in these organisms. Diatoms represent a major phytoplankton group essential in various global biogeochemical cycles. The current study combined targeted metabolomics, bioaccumulation, and physiological response assays to investigate metabolic perturbations in diatom Cyclotella meneghiniana exposed for 2 h to nanomolar concentrations of Hg(II) and MeHg. Our findings highlight that such exposures induce reprogramming of the metabolism of amino acids, nucleotides, fatty acids, carboxylic acids and antioxidants. These alterations were primarily mercury-species dependent. MeHg exposure induced more pronounced reprogramming of the metabolism of diatoms than Hg(II), which led to less pronounced effects on ROS generation, membrane permeability and chlorophyll concentrations. Hg(II) treatments presented distinct physiological responses, with more robust metabolic perturbations at higher exposures. The present study provides first-time insights into the main metabolic alterations in diatom C. meneghiniana during short-term exposure to Hg species, deepening our understanding of the molecular basis of these perturbations.

Neonicotinoid insecticides are among the most used insecticides and their residues are frequently found in surface water due to their persistence and mobility. Neonicotinoid insecticides exhibit toxicity to a wide range of aquatic invertebrates at environmentally relevant levels, and therefore their contamination in surface water is of significant concern. In this study, we investigated the spatiotemporal distribution of six neonicotinoids in a large wetland system, the Prado Wetlands, in Southern California, and further evaluated the wetlands' efficiency at removing these insecticides. Total neonicotinoid concentrations in water ranged from 3.17 to 46.9 ng L-1 at different locations within the wetlands, with imidacloprid and dinotefuran among the most detected. Removal was calculated based on concentrations as well as mass flux. The concentration-based removal values for a shallow pond (vegetation-free), moderately vegetated cells, densely vegetated cells, and the entire wetland train were 16.9%, 34.2%, 90.2%, and 61.3%, respectively. Principal component analysis revealed that pH and temperature were the primary factors affecting neonicotinoids removal. Results from this study demonstrated the ubiquitous presence of neonicotinoids in surface water impacted by urban runoff and wastewater effluent and highlighted the efficiency of wetlands in removing these trace contaminants due to concerted effects of uptake by wetland plants, photolysis, and microbial degradation.

In situ chemical oxidation (ISCO) using peroxydisulfate has become more popular in the remediation of soils and shallow groundwater contaminated with organic chemicals. Researchers have studied the chemistry of peroxydisulfate and the oxidative species produced upon its decomposition (i.e., sulfate radical and hydroxyl radical) for over five decades, describing reaction kinetics, mechanisms, and product formation in great detail. However, if this information is to be useful to practitioners seeking to optimize the use of peroxydisulfate in the remediation of hazardous waste sites, the relevant conditions of high oxidant concentrations and the presence of minerals and solutes that affect radical chain reactions must be considered. The objectives of this Review are to provide insights into the chemistry of peroxydisulfate-based ISCO that can enable more efficient operation of these systems and to identify research needed to improve understanding of system performance. By gaining a deeper understanding of the underlying chemistry of these complex systems, it may be possible to improve the design and operation of peroxydisulfate-based ISCO remediation systems.

The biological early warning system with fish behavior as the detection index is an efficient and rapid early warning technology for the ecological damage caused by water pollutants. However, the attempt to apply the scototaxis (dark preference) behavior of fish to biological early warning is still relatively lacking. In this study, we delved into the dark and light preferences of the rare minnows (Gobiocypris rarus), employing three distinct tank configurations. Additionally, we systematically examined the modulating effects of environmental illumination, nutritional status, and the number of test subjects on this behavior, aiming to establish optimal experimental parameters for its observation. Furthermore, cadmium ions [Cd2+], tricaine methanesulfonate [MS222], and p-chloroaniline were employed as representative heavy metal ions, neuroactive agents, and organic toxicants, respectively, to test the impact of chemicals on scototaxis in gradient concentrations. The results demonstrated that the rare minnow exhibited a clear scototaxis (dark preference), and this behavior was not affected by the nutritional status of the test fish, the illumination, or the number of subjects. While the dark chamber was consistently the preferred location of rare minnows during the chemical exposure tests, the degree of scototaxis by the rare minnow significantly decreased at Cd2+ ≥ 3 mg/L, MS222 ≥ 11 mg/L, and p-chloroaniline ≥ 29 mg/L, suggesting a potential disruption of their innate behavioral patterns by these chemicals. These findings underscore the sensitivity of rare minnows to water pollutants. Therefore, the scototaxis behavior of rare minnows can be a potential and useful behavioral indicator for biological early warning, which can be used for early biological warning of sudden water pollution caused by chemicals such as Cd2+, MS222, and p-chloroaniline. [ABSTRACT FROM AUTHOR]

Advances in green engineering and technology have revealed a number of environmentally acceptable alternatives for water purification. In line with this, recent advances in biosorption of pollutants from aqueous solutions using animal biowaste-based activated carbon (AC) are reported herein. Apart from the fish scale-derived AC which is extensively documented, animal bones, among the rest others, have been studied most widely, followed by hair and feathers. Out of the various target water pollutants, removal of heavy metals has been mostly studied. Majority of the reports showed the Freundlich isotherm and pseudo second order as the best fit. Few investigations on the thermodynamics of the adsorption studies and reports on the Gibbs free energy change (ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) have also been discussed in this report. It has been concluded that while plant-based AC has gained wide interest, the same is not true for the animal-based counterpart albeit the latter's potential for high sorption efficiency as seen in the present report. [ABSTRACT FROM AUTHOR]

The photochemical degradation pathways of 6PPD-quinone (6PPDQ, 6PPD-Q), a toxic transformation product of the tire antiozonant 6PPD, were determined under simulated sunlight conditions typical of high-latitude surface waters. Direct photochemical degradation resulted in 6PPDQ half-lives ranging from 17.5 h at 20 °C to no observable degradation over 48 h at 4 °C. Sensitization of excited triplet-state pathways using Cs+ and Ar purging demonstrated that 6PPDQ does not decompose significantly from a triplet state relative to a singlet state. However, assessment of processes involving reactive oxygen species (ROS) quenchers and sensitizers indicated that singlet oxygen and hydroxyl radical do significantly contribute to the degradation of 6PPDQ. Investigation of these processes in natural lake waters indicated no difference in attenuation rates for direct photochemical processes at 20 °C. This suggests that direct photochemical degradation will dominate in warm waters, while indirect photochemical pathways will dominate in cold waters, involving ROS mediated by chromophoric dissolved organic matter (CDOM). Overall, the aquatic photodegradation rate of 6PPDQ will be strongly influenced by the compounding effects of environmental factors such as light screening and temperature on both direct and indirect photochemical processes. Transformation products were identified via UHPLC-Orbitrap mass spectrometry, revealing four major processes: (1) oxidation and cleavage of the quinone ring in the presence of ROS, (2) dealkylation, (3) rearrangement, and (4) deamination. These data indicate that 6PPDQ can photodegrade in cool, sunlit waters under the appropriate conditions: t1/2 = 17.4 h tono observable decrease (direct); t1/2 = 5.2-11.2 h (indirect, CDOM).

Environmental contamination constrains microbial communities impacting diversity and total metabolic activity. The former S-3 Ponds contamination site at Oak Ridge Reservation (ORR), TN, has elevated concentrations of nitric acid and multiple metals from decades of processing nuclear material. To determine the nature of the metal contamination in the sediment, a three-step sequential chemical extraction (BCR) was performed on sediment segments from a core located upgradient (EB271, non-contaminated) and one downgradient (EB106, contaminated) of the S-3 Ponds. The resulting exchangeable, reducing, and oxidizing fractions were analyzed for 18 different elements. Comparison of the two cores revealed changes in operational speciation for several elements caused by the contamination. Those present from the S-3 Ponds, including Al, U, Co, Cu, Ni, and Cd, were not only elevated in concentration in the EB106 core but were also operationally more available with increased mobility in the acidic environment. Other elements, including Mg, Ca, P, V, As, and Mo, were less operationally available in EB106 having decreased concentrations in the exchangeable fraction. The bioavailability of essential macro nutrients Mg, Ca, and P from the two types of sediment was determined using three metal-tolerant bacteria previously isolated from ORR. Mg and Ca were available from both sediments for all three strains; however, P was not bioavailable from either sediment for any strain. The decreased operational speciation of P in contaminated ORR sediment may increase the dependence of the microbial community on other pools of P or select for microorganisms with increased P scavenging capabilities. Hence, the microbial community at the former S-3 Ponds contamination site may be constrained not only by increased toxic metal concentrations but also by the availability of essential elements, including P.

In drinking water distribution systems, the oxidation of zerovalent chromium, Cr(0), in iron corrosion scales by chlorine residual disinfectant is the dominant reaction to form carcinogenic hexavalent chromium, Cr(VI). This study investigates inhibitive corrosion control strategies through adjustments of chemical water parameters (i.e., pH, silicate, phosphate, calcium, and alkalinity) on Cr(VI) formation through oxidation of Cr(0)(s) by free chlorine under drinking water conditions. The results show that an increase in pH, silicate, alkalinity, and calcium suppressed Cr(VI) formation that was mainly attributed to in situ surface precipitation of new Cr(III) solids on the surface of Cr(0)(s), including Cr(OH)3(s), Cr2(SiO3)3(s), CrPO4(s), Cr2(CO3)3(s), and Cr10Ca(CO3)16(s). The Cr(III) surface precipitates were much less reactive with chlorine than Cr(0)(s) and suppressed the Cr redox reactivity. The concentration of surface Cr(III) solids was inversely correlated with the rate constant of Cr(VI) formation. Adding phosphate either promoted or inhibited the Cr(VI) formation, depending on the phosphate concentration. This study provides fundamental insight into the Cr(VI) formation mechanisms via Cr(0) oxidation by chlorine and the importance of surface precipitation of Cr(III) solids with different corrosion control strategies and suggests that increasing the pH/alkalinity and addition of phosphate or silicate can be effective control strategies to minimize Cr(VI) formation.

Low-cost stainless-steel electrodes can activate hydrogen peroxide (H2O2) by converting it into a hydroxyl radical (•OH) and other reactive oxidants. At an applied potential of +0.020 V, the stainless-steel electrode produced •OH with a yield that was over an order of magnitude higher than that reported for other systems that employ iron oxides as catalysts under circumneutral pH conditions. Decreasing the applied potential at pH 8 and 9 enhanced the rate of H2O2 loss by shifting the process to a reaction mechanism that resulted in the formation of an Fe(IV) species. Significant metal leaching was only observed under acidic pH conditions (i.e., at pH

Subsurface treatment systems, such as constructed wetlands, riverbank filtration systems, and managed aquifer recharge systems, offer a low-cost means of removing trace organic contaminants from treated municipal wastewater. To assess the processes through which trace organic contaminants are removed in subsurface treatment systems, pharmaceuticals and several major metabolites were measured in porewater, sediment, and plants within a horizontal levee (i.e., a subsurface flow wetland that receives treated municipal wastewater). Concentrations of trace organic contaminants in each wetland compartment rapidly declined along the flow path. Mass balance calculations, analysis of transformation products, microcosm experiments, and one-dimensional transport modeling demonstrated that more than 60% of the contaminant removal could be attributed to transformation. Monitoring of the system with and without nitrate in the wetland inflow indicated that relatively biodegradable trace organic contaminants, such as acyclovir and metoprolol, were rapidly transformed under both operating conditions. Trace organic contaminants that are normally persistent in biological treatment systems (e.g., sulfamethoxazole and carbamazepine) were removed only when Fe(III)- and sulfate-reducing conditions were observed. Minor structural modifications to trace organic contaminants (e.g., hydroxylation) altered the pathways and extents of trace organic contaminant transformation under different redox conditions. These findings indicate that subsurface treatment systems can be designed to remove both labile and persistent trace organic contaminants via transformation if they are designed and operated in a manner that results in sulfate-and Fe(III)-reducing conditions.

Triphenyl phosphate (TPHP) - a widely used organophosphate-based flame retardant - blocks cardiac looping during zebrafish development in a concentration-dependent manner, a phenotype that is dependent on disruption of embryonic osmoregulation and pericardial edema formation. However, its currently unclear whether (1) TPHP-induced effects on osmoregulation are driven by direct TPHP-induced injury to the embryonic epidermis and (2) whether TPHP-induced pericardial edema is reversible or irreversible following cessation of exposure. Therefore, the objectives of this study were to determine whether TPHP-induced pericardial edema is reversible and whether TPHP causes injury to the embryonic epidermis by quantifying the number of DAPI-positive epidermal cells and analyzing the morphology of the yolk sac epithelium using scanning electron microscopy. First, we found that exposure to 5 μM TPHP from 24-72 h post-fertilization (hpf) did not increase prolactin - a hormone that regulates ions and water levels - in embryonic zebrafish, whereas high ionic strength exposure media was associated with elevated levels of prolactin. Second, we found that exposure to 5 μM TPHP from 24-72 hpf did not decrease DAPI-positive epidermal cells within the embryonic epithelium, and that co-exposure with 2.14 μM fenretinide - a synthetic retinoid that promotes epithelial wound repair - from 24-72 hpf did not mitigate the prevalence of TPHP-induced epidermal folds within the yolk sac epithelium when embryos were exposed within high ionic strength exposure media. Finally, we found that the pericardial area and body length of embryos exposed to 5 μM TPHP from 24-72 hpf were similar to vehicle-treated embryos at 120 hpf following transfer to clean water and depuration of TPHP from 72-120 hpf. Overall, our findings suggest that (1) the ionic strength of exposure media may influence the baseline physiology of zebrafish embryos; (2) TPHP does not cause direct injury to the embryonic epidermis; and (3) TPHP-induced effects on pericardial area and body length are reversible 48 h after transferring embryos to clean water.

Brownlee Reservoir is a mercury (Hg)-impaired hydroelectric reservoir that exhibits dynamic hydrological and geochemical conditions and is located within the Hells Canyon Complex in Idaho, USA. Methylmercury (MeHg) contamination in fish is a concern in the reservoir. While MeHg production has historically been attributed to sulfate-reducing bacteria and methanogenic archaea, microorganisms carrying the hgcA gene are taxonomically and metabolically diverse and the major biogeochemical cycles driving mercury (Hg) methylation are not well understood. In this study, Hg speciation and redox-active compounds were measured throughout Brownlee Reservoir across the stratified period in four consecutive years (2016-2019) to identify the location where and redox conditions under which MeHg is produced. Metagenomic sequencing was performed on a subset of samples to characterize the microbial community with hgcA and identify possible links between biogeochemical cycles and MeHg production. Biogeochemical profiles suggested in situ water column Hg methylation was the major source of MeHg. These profiles, combined with genome-resolved metagenomics focused on hgcA-carrying microbes, indicated that MeHg production occurs in this system under nitrate- or manganese-reducing conditions, which were previously thought to preclude Hg-methylation. Using this multidisciplinary approach, we identified the cascading effects of interannual variability in hydrology on the redox status, microbial metabolic strategies, abundance and metabolic diversity of Hg methylators, and ultimately MeHg concentrations throughout the reservoir. This work expands the known conditions conducive to producing MeHg and suggests that the Hg-methylation mitigation efforts by nitrate or manganese amendment may be unsuccessful in some locations.

Indonesia primarily exports coal, with an average annual quantity of over 421 million tonnes in the past decades (2011-2020), reaching its peak at 616 million tonnes in 2019. Despite its economic benefits, coal production carries hidden costs. This research delves into using life cycle assessment (LCA) to gauge the environmental impact of coal production and estimate external cost (EC) related to Greenhouse gases (GHG) and air pollutants (AP). The study applied the benefit transfer method to make these estimations, focusing on coal mining and international transport processes. The findings revealed that over the past decades, per tonne coal mining contributed an estimated EC of $12.54-15.26 for GHG and $3,439-5,250 for AP, while transport abroad per-tonne-km coal incurred an EC of $19.98-23.94 for GHG and $19.58-23.30 for AP. Moreover, coal mining contributes to water pollution and substantial water depletion. Despite the coal production in Indonesia generating around $40 billion in revenue in 2020, the study shows that the total EC from GHG and AP is up to $2,131 billion, which is 53 times the revenue, posing serious health and ecological risks to Indonesians and exacerbating global climate change. Notably, these estimates exclude EC from water pollution (WP) and water depletion. With the global push towards ‘net zero emissions’, the coal industry as a whole faces an urgent need to curb its GHG and AP emissions from its.

Groundwater contamination poses a severe public health risk in Lahore, Pakistan's second-largest city, where over-exploited aquifers are the primary municipal and domestic water supply source. This study presents the first comprehensive district-wide assessment of groundwater quality across Lahore using an innovative integrated approach combining geographic information systems (GIS), multi-criteria decision analysis (MCDA), and water quality indexing techniques. The core objectives were to map the spatial distributions of critical pollutants like arsenic, model their impacts on overall potability, and evaluate targeted remediation scenarios. The analytic hierarchy process (AHP) methodology was applied to derive weights for the relative importance of diverse water quality parameters based on expert judgments. Arsenic received the highest priority weight (0.28), followed by total dissolved solids (0.22) and hardness (0.15), reflecting their significance as health hazards. Weighted overlay analysis in GIS delineated localized quality hotspots, unveiling severely degraded areas with very poor index values (>150) in urban industrial zones like Lahore Cantt, Model Town, and parts of Lahore City. This corroborates reports of unregulated industrial effluent discharges contributing to aquifer pollution. Prospective improvement scenarios projected that reducing heavy metals like arsenic by 30% could enhance quality indices by up to 20.71% in critically degraded localities like Shalimar. Simulating advanced multi-barrier water treatment processes showcased an over 95% potential reduction in arsenic levels, indicating the requirement for deploying advanced oxidation and filtration infrastructure aligned with local contaminant profiles. The integrated decision support tool enables the visualization of complex contamination patterns, evaluation of remediation options, and prioritizing risk-mitigation investments based on the spatial distribution of hazard exposures. This framework equips urban planners and utilities with critical insights for developing targeted groundwater quality restoration policies through strategic interventions encompassing treatment facilities, drainage infrastructure improvements, and pollutant discharge regulations. Its replicability across other regions allows for tackling widespread groundwater contamination challenges through robust data synthesis and quantitative scenario modeling capabilities. [ABSTRACT FROM AUTHOR]

Water pollution greatly impacts humans and ecosystems, so a series of policies have been enacted to control it. The first step in performing pollution control is to detect contaminants in the water. Various methods have been proposed for water quality testing, such as spectroscopy, chromatography, and electrochemical techniques. However, traditional testing methods require the utilization of laboratory equipment, which is large and not suitable for real-time testing in the field. Microfluidic devices can overcome the limitations of traditional testing instruments and have become an efficient and convenient tool for water quality analysis. At the same time, artificial intelligence is an ideal means of recognizing, classifying, and predicting data obtained from microfluidic systems. Microfluidic devices based on artificial intelligence and machine learning are being developed with great significance for the next generation of water quality monitoring systems. This review begins with a brief introduction to the algorithms involved in artificial intelligence and the materials used in the fabrication and detection techniques of microfluidic platforms. Then, the latest research development of combining the two for pollutant detection in water bodies, including heavy metals, pesticides, micro- and nanoplastics, and microalgae, is mainly introduced. Finally, the challenges encountered and the future directions of detection methods based on industrial intelligence and microfluidic chips are discussed. [ABSTRACT FROM AUTHOR]

In this research, the efficiency of degradation of different organic contaminant classes, including pesticides (tembotrione, clomazone), pharmaceuticals (ciprofloxacin, 17α-ethinyl estradiol) and mycotoxins (zearalenone, deoxynivalenol, fumonisin B1) with subcritical water treatment was studied in model systems. All experiments were conducted in a house-made batch-type pilot reactor. The research was focused on the optimization of the treatment parameters using moderate treatment conditions. Optimization of the remediation processes of water contaminated with 17α-ethinyl estradiol, tembotrione, clomazone, and ciprofloxacin, was conducted through testing with different homogeneous and heterogeneous catalysts, as well as different gas atmospheres (nitrogen and carbon dioxide) for pressurization of the process system. Mycotoxins in water were degraded without catalysts and all experiments were conducted in nitrogen atmosphere. Optimization was conducted through defining the optimal combination of the treatment temperature and time, oriented towards energy saving and minimization of the technical requirements. The degradation efficiency in all tested samples was determined via HPLC analysis. Study showed the full degradation of tembotrione and all tested mycotoxins at 200 °C without a need for a catalyst. The efficiency of degradation of other tested pollutants at 200 °C was satisfying and within the range of 89.5% (clomazone) to 98.7% (17α-ethinyl estradiol). [ABSTRACT FROM AUTHOR]

Indonesia primarily exports coal, with an average annual quantity of over 421 million tonnes in the past decades (2011-2020), reaching its peak at 616 million tonnes in 2019. Despite its economic benefits, coal production carries hidden costs. This research delves into using life cycle assessment (LCA) to gauge the environmental impact of coal production and estimate external cost (EC) related to Greenhouse gases (GHG) and air pollutants (AP). The study applied the benefit transfer method to make these estimations, focusing on coal mining and international transport processes. The findings revealed that over the past decades, per tonne coal mining contributed an estimated EC of $12.54-15.26 for GHG and $3,439-5,250 for AP, while transport abroad per-tonne-km coal incurred an EC of $19.98-23.94 for GHG and $19.58-23.30 for AP. Moreover, coal mining contributes to water pollution and substantial water depletion. Despite the coal production in Indonesia generating around $40 billion in revenue in 2020, the study shows that the total EC from GHG and AP is up to $2,131 billion, which is 53 times the revenue, posing serious health and ecological risks to Indonesians and exacerbating global climate change. Notably, these estimates exclude EC from water pollution (WP) and water depletion. With the global push towards 'net zero emissions', the coal industry as a whole faces an urgent need to curb its GHG and AP emissions from its. [ABSTRACT FROM AUTHOR]

Previous studies have evaluated method performance for quantifying and characterizing microplastics in clean water, but little is known about the efficacy of procedures used to extract microplastics from complex matrices. Here we provided 15 laboratories with samples representing four matrices (i.e., drinking water, fish tissue, sediment, and surface water) each spiked with a known number of microplastic particles spanning a variety of polymers, morphologies, colors, and sizes. Percent recovery (i.e., accuracy) in complex matrices was particle size dependent, with ∼60-70% recovery for particles >212 μm, but as little as 2% recovery for particles

Quality assurance and quality control (QA/QC) techniques are critical to analytical chemistry, and thus the analysis of microplastics. Procedural blanks are a key component of QA/QC for quantifying and characterizing background contamination. Although procedural blanks are becoming increasingly common in microplastics research, how researchers acquire a blank and report and/or use blank contamination data varies. Here, we use the results of laboratory procedural blanks from a method evaluation study to inform QA/QC procedures for microplastics quantification and characterization. Suspected microplastic contamination in the procedural blanks, collected by 12 participating laboratories, had between 7 and 511 particles, with a mean of 80 particles per sample (±SD 134). The most common color and morphology reported were black fibers, and the most common size fraction reported was 20-212 μm. The lack of even smaller particles is likely due to limits of detection versus lack of contamination, as very few labs reported particles

Methylmercury (MeHg) production is controlled by the bioavailability of inorganic divalent mercury (Hg(II)i ) and Hg-methylation capacity of the microbial community (conferred by the hgcAB gene cluster). However, the relative importance of these factors and their interaction in the environment remain poorly understood. Here, metagenomic sequencing and a full-factorial MeHg formation experiment were conducted across a wetland sulfate gradient with different microbial communities and pore water chemistries. From this experiment, the relative importance of each factor on MeHg formation was isolated. Hg(II)i bioavailability correlated with the dissolved organic matter composition, while the microbial Hg-methylation capacity correlated with the abundance of hgcA genes. MeHg formation responded synergistically to both factors. Notably, hgcA sequences were from diverse taxonomic groups, none of which contained genes for dissimilatory sulfate reduction. This work expands our understanding of the geochemical and microbial constraints on MeHg formation in situ and provides an experimental framework for further mechanistic studies.

One of the major and abundant environmental elements is water, which life existence on earth is depending on. However, degradation of water quality arising from natural occurrences due to anthropogenic that resulted in eutrophication needs to be guided. Indiscriminate harmful waste discharge and dispersion into the water bodies leads to water pollution. As such, constant management and monitoring of water resources for an enhanced quality and quantity is essential. Therefore, this study employed a coupled derivative mathematical model to investigate soluble and insoluble water pollutants. The insoluble pollutants are converted to soluble pollutants through an applied control or treatment. To optimize the water quality, parametric sensitivities in relation to reproduction number are examined. From the computational analysis carried out, it was revealed that treatment still remains the only remedy for safe water.

This study presents an innovative approach for assessing water quality in agricultural irrigation networks, integrating stable isotope analysis, in vivo zebrafish screening, and comprehensive chemical profiling to investigate the occurrence, transformation, and potential toxicity of organic contaminants. Stable isotope analysis was used to measure evaporation as a proxy for water residence time in the canal, while liquid chromatography-high resolution mass spectrometry (LC-HRMS) identified a range of organic compounds in water samples collected from both the irrigation canal and its source river. Results indicated a reduction in contaminant levels in the canal compared to the river, with the most significant evaporation and concentration changes occurring at a holding reservoir, suggesting that managing residence time could help reduce water loss in arid irrigation networks. The data also highlighted how evaporation, particularly during the dry, hot season, influences contaminant dynamics. Hierarchical clustering of LC-HRMS results showed notable differences between the chemical profiles of canal and river samples, indicating that irrigation systems may contribute to the degradation or removal of certain compounds. Over 60 % of detected compounds were naturally derived, with anthropogenic contaminants like pesticides and personal care products further highlighting human impacts. Priority contaminants, including DEET and 2-naphthalene sulfonic acid, likely originated from urban activities upstream. Initial screening using zebrafish embryos showed bioactivity across sites, confirming the presence of contaminants needing further examination. Correlation analysis linked natural compounds to evaporation rates, suggesting that flora and fauna play significant roles in the chemical makeup of canal water. Overall, this approach provides a comprehensive framework for monitoring irrigation water, offering insights into contaminant behavior and supporting the development of standardized methods for assessing chemical fate and ecological risks in agricultural irrigation systems.

Carbonaceous materials are often proposed for use in restoring soils or sediments contaminated with hydrophobic organic contaminants (HOCs). However, the contamination of most sites is a result of historical events, where HOCs have resided in the solid compartment for many years or decades. The prolonged contact time, or aging, leads to reduced contaminant availability and likely diminished effectiveness of using sorbents. In this study, three different carbonaceous sorbents, i.e., biochars, powdered activated carbon, and granular activated carbon, were amended to a Superfund site marine sediment contaminated with DDT residues from decades ago. The amended sediments were incubated in seawater for up to 1 year, and the freely dissolved concentration (Cfree) and the biota-sediment accumulation factors (BSAFs) for a native polychaete (Neanthes arenaceodentata) were measured. Even though the bulk sediment concentrations were very high (6.4-154.9 μg/g OC), both Cfree and BSAFs were very small, ranging from nd to 1.34 ng/L and from nd to 0.024, respectively. The addition of carbonaceous sorbents, even at 2% (w/w), did not consistently lead to reduced DDT bioaccumulation. The limited effectiveness of carbonaceous sorbents was attributed to the low DDT availability due to prolonged aging, highlighting the need for considering contaminant aging when using sorbents for remediation.

Pesticides have been reported in treated wastewater effluent at concentrations that exceed aquatic toxicity thresholds, indicating that treatment may be insufficient to adequately address potential pesticide impacts on aquatic life. Gaining a better understanding of the relative contribution from specific use patterns, transport pathways, and flow characteristics is an essential first step to informing source control measures. The results of this study are the first of their kind, reporting pesticide concentrations at sub-sewershed sites within a single sewer catchment to provide information on the relative contribution from various urban sources. Seven monitoring events were collected from influent, effluent, and seven sub-sewershed sites to capture seasonal variability. In addition, samples were collected from sites with the potential for relatively large mass fluxes of pesticides (pet grooming operations, pest control operators, and laundromats). Fipronil and imidacloprid were detected in most samples (>70%). Pyrethroids were detected in >50% of all influent and lateral samples. There were significant removals of pyrethroids from the aqueous process stream within the facility to below reporting limits. Imidacloprid and fiproles were the only pesticides that were detected above reporting limits in effluent, highlighting the importance of source identification and control for the more hydrophilic compounds. Single source monitoring revealed large contributions of fipronil, imidacloprid, and permethrin originating from a pet groomer, with elevated levels of cypermethrin at a commercial laundry location. The results provide important information needed to prioritize future monitoring efforts, calibrate down-the-drain models, and identify potential mitigation strategies at the site of pesticide use to prevent introduction to sewersheds.

The discovery that the commercial rubber antidegradant 6PPD reacts with ozone (O3) to produce a highly toxic quinone (6PPDQ) spurred a significant research effort into nontoxic alternatives. This work has been hampered by lack of a detailed understanding of the mechanism of protection that 6PPD affords rubber compounds against ozone. Herein, we report high-level density functional theory studies into early steps of rubber and PPD (p-phenylenediamine) ozonation, identifying key steps that contribute to the antiozonant activity of PPDs. In this, we establish that our density functional theory approach can achieve chemical accuracy for many ozonation reactions, which are notoriously difficult to model. Using adiabatic energy decomposition analysis, we examine and dispel the notion that one-electron charge transfer initiates ozonation in these systems, as is sometimes argued. Instead, we find direct interaction between O3 and the PPD aromatic ring is kinetically accessible and that this motif is more significant than interactions with PPD nitrogens. The former pathway results in a hydroxylated PPD intermediate, which reacts further with O3 to afford 6PPD hydroquinone and, ultimately, 6PPDQ. This mechanism directly links the toxicity of 6PPDQ to the antiozonant function of 6PPD. These results have significant implications for development of alternative antiozonants, which are discussed.

In this modern era, pollution of water resources due to industrial waste effluents is an alarming problem as it can cause various health problems in aquatic animals as well as in humans. Among the industrial pollutants, organic dyes are one of the leading chemicals that cause severe damage to the aquatic environment. These harmful organic dyes are practically omnipresent in various types of industries such as textile, tannery, cosmetic, food industries, etc. Photodegradation of these organic dyes is regarded as a promising technology for industrial waste treatment as it is a cost-effective and environment-friendly process. In this study, a nanostructured material of iron has been synthesized using the Alstonia scholaris (L.) R. Br. extract in an easy and eco-friendly way. The potential of this synthesized nanostructured material to act as a photocatalyst, for the degradation of organic dyes, has been explored. Due to its small size and high dispersion, more than 72 % degradation has been achieved within 90 min. A comparative study of its photocatalytic efficiency in different degradation processes has also been performed.

Hexafluoropropylene oxide-dimer acid (HFPO-DA) is one of the emerging replacements for the "forever" carcinogenic and toxic long-chain PFAS. HFPO-DA is a polymerization aid used for manufacturing fluoropolymers, whose global distribution and undetermined toxic properties are a concern regarding human and ecological health. To assess embryotoxic potential, zebrafish embryos were exposed to HFPO-DA at concentrations of 0.5-20,000 mg/L at 24-, 48-, and 72-h post-fertilization (hpf). Heart rate increased significantly in embryos exposed to 2 mg/L and 10 mg/L HFPO-DA across all time points. Spinal deformities and edema phenotypes were evident among embryos exposed to 1000-16,000 mg/L HFPO-DA at 72 hpf. A median lethal concentration (LC50) was derived as 7651 mg/L at 72 hpf. Shallow RNA sequencing analysis of 9465 transcripts identified 38 consistently differentially expressed genes at 0.5 mg/L, 1 mg/L, 2 mg/L, and 10 mg/L HFPO-DA exposures. Notably, seven downregulated genes were associated with visual response, and seven upregulated genes were expressed in or regulated the cardiovascular system. This study identifies biological targets and molecular pathways affected during animal development by an emerging, potentially problematic, and ubiquitous industrial chemical.

Heavy metal contamination due to industrial and agricultural waste represents a growing threat to water supplies. Frequent and widespread monitoring for toxic metals in drinking and agricultural water sources is necessary to prevent their accumulation in humans, plants, and animals, which results in disease and environmental damage. Here, the metabolic stress response of bacteria is used to report the presence of heavy metal ions in water by transducing ions into chemical signals that can be fingerprinted using machine learning analysis of vibrational spectra. Surface-enhanced Raman scattering surfaces amplify chemical signals from bacterial lysate and rapidly generate large, reproducible datasets needed for machine learning algorithms to decode the complex spectral data. Classification and regression algorithms achieve limits of detection of 0.5 pM for As3+ and 6.8 pM for Cr6+, 100,000 times lower than the World Health Organization recommended limits, and accurately quantify concentrations of analytes across six orders of magnitude, enabling early warning of rising contaminant levels. Trained algorithms are generalizable across water samples with different impurities; water quality of tap water and wastewater was evaluated with 92% accuracy.

Over 1.3 million Californians rely on unmonitored domestic wells. Existing probability estimates of groundwater Mn concentrations, population estimates, and sociodemographic data were integrated with spatial data delineating domestic well communities (DWCs) to predict the probability of high Mn concentrations in extracted groundwater within DWCs in California's Central Valley. Additional Mn concentration data of water delivered by community water systems (CWSs) were used to estimate Mn in public water supply. We estimate that 0.4% of the DWC population (2342 users) rely on groundwater with predicted Mn > 300 μg L-1. In CWSs, 2.4% of the population (904 users) served by small CWSs and 0.4% of the population (3072 users) served by medium CWS relied on drinking water with mean point-of-entry Mn concentration >300 μg L-1. Small CWSs were less likely to report Mn concentrations relative to large CWSs, yet a higher percentage of small CWSs exceed regulatory standards relative to larger systems. Modeled calculations do not reveal differences in estimated Mn concentration between groundwater from current regional domestic well depth and 33 m deeper. These analyses demonstrate the need for additional well-monitoring programs that evaluate Mn and increased access to point-of-use treatment for domestic well users disproportionately burdened by associated costs of water treatment.

The correct detection and quantification of pollutants in water is key to regulating their presence in the environment. Biosensors offer several advantages, such as minimal sample preparation, short measurement times, high specificity and sensibility and low detection limits. The purpose of this review is to explore the different types of optical biosensors, focusing on their biological elements and their principle of operation, as well as recent applications in the detection of pollutants in water. According to our literature review, 33% of the publications used fluorescence-based biosensors, followed by surface plasmon resonance (SPR) with 28%. So far, SPR biosensors have achieved the best results in terms of detection limits. Although less common (22%), interferometers and resonators (4%) are also highly promising due to the low detection limits that can be reached using these techniques. In terms of biological recognition elements, 43% of the published works focused on antibodies due to their high affinity and stability, although they could be replaced with molecularly imprinted polymers. This review offers a unique compilation of the most recent work in the specific area of optical biosensing for water monitoring, focusing on both the biological element and the transducer used, as well as the type of target contaminant. Recent technological advances are discussed.

Due to chronic exposure to elevated levels of arsenic in drinking water, thousands of Californians have increased risk for internal cancers and other adverse health effects. The mortality risk of cancer is 1 in 400 people exposed to above 10 μg/L of arsenic in their drinking water. The purpose of this community assessment was to understand the perceptions and awareness of the residents and public water representatives in rural, unincorporated farming communities of color in San Joaquin Valley, California. In our research, we asked 27 community informants about their (1) available water sources, (2) knowledge about the health impacts of arsenic, and (3) preferences for risk communication and education regarding the health impacts of arsenic-contaminated drinking water. Through our qualitative coding and analysis, we found that most community informants indicated that there was limited community awareness about the health effects of drinking water with elevated arsenic levels. Preferences for risk communication included using in-language, culturally relevant, and health literate health promotion strategies and teaching these topics through the local K-8 schools' science curriculum with a language brokerage approach to transfer student knowledge to family members. Key recommendations include implementing these communication preferences to increase community-wide knowledge about safe drinking water.

Exposure to persistent organic pollutants (POPs) can significantly impact marine mammal health, reproduction, and fitness. This study addresses a significant 20-year gap in gray whale contaminant monitoring through analysis of POPs in 120 blubber biopsies. The scope of this substantial sample set is noteworthy in its range and diversity with collection between 2003 and 2017 along North Americas west coast and across diverse sex, age, and reproductive parameters, including paired mothers and calves. Mean blubber concentrations of polychlorinated biphenyls (∑PCBs), dichlorodiphenyltrichloroethanes (∑DDTs), and chlordanes (∑CHLs) generally decreased since previous reports (1968-1999). This is the first report of polybrominated diphenyl ethers (PBDEs) and select hexachlorocyclohexanes (HCHs) in this species. Statistical modeling of the 19 most frequently detected compounds in this dataset revealed sex-, age-, and reproductive status-related patterns, predominantly attributed to maternal offloading. Mean POP concentrations differed significantly by sex in adults (17 compounds, up to 3-fold higher in males) but not in immatures (all 19 compounds). Mean POP concentrations were significantly greater in adults versus immatures in both males (17 compounds, up to 12-fold) and females (13 compounds, up to 3-fold). POP concentrations were detected with compound-specific patterns in nursing calves, confirming maternal offloading for the first time in this species.

Microscopy is often the first step in microplastic analysis and is generally followed by spectroscopy to confirm material type. The value of microscopy lies in its ability to provide count, size, color, and morphological information to inform toxicity and source apportionment. To assess the accuracy and precision of microscopy, we conducted a method evaluation study. Twenty-two laboratories from six countries were provided three blind spiked clean water samples and asked to follow a standard operating procedure. The samples contained a known number of microplastics with different morphologies (fiber, fragment, sphere), colors (clear, white, green, blue, red, and orange), polymer types (PE, PS, PVC, and PET), and sizes (ranging from roughly 3-2000 μm), and natural materials (natural hair, fibers, and shells; 100-7000 μm) that could be mistaken for microplastics (i.e., false positives). Particle recovery was poor for the smallest size fraction (3-20 μm). Average recovery (±StDev) for all reported particles >50 μm was 94.5 ± 56.3%. After quality checks, recovery for >50 μm spiked particles was 51.3 ± 21.7%. Recovery varied based on morphology and color, with poorest recovery for fibers and the largest deviations for clear and white particles. Experience mattered; less experienced laboratories tended to report higher concentration and had a higher variance among replicates. Participants identified opportunity for increased accuracy and precision through training, improved color and morphology keys, and method alterations relevant to size fractionation. The resulting data informs future work, constraining and highlighting the value of microscopy for microplastics.

Real-time chemical sensing is crucial for applications in environmental and health monitoring1. Biosensors can detect a variety of molecules through genetic circuits that use these chemicals to trigger the synthesis of a coloured protein, thereby producing an optical signal2-4. However, the process of protein expression limits the speed of this sensing to approximately half an hour, and optical signals are often difficult to detect in situ5-8. Here we combine synthetic biology and materials engineering to develop biosensors that produce electrical readouts and have detection times of minutes. We programmed Escherichia coli to produce an electrical current in response to specific chemicals using a modular, eight-component, synthetic electron transport chain. As designed, this strain produced current following exposure to thiosulfate, an anion that causes microbial blooms, within 2 min. This amperometric sensor was then modified to detect an endocrine disruptor. The incorporation of a protein switch into the synthetic pathway and encapsulation of the bacteria with conductive nanomaterials enabled the detection of the endocrine disruptor in urban waterway samples within 3 min. Our results provide design rules to sense various chemicals with mass-transport-limited detection times and a new platform for miniature, low-power bioelectronic sensors that safeguard ecological and human health.

Microparticles, such as microplastics and microfibers, are ubiquitous in marine food webs. Filter-feeding megafauna may be at extreme risk of exposure to microplastics, but neither the amount nor pathway of microplastic ingestion are well understood. Here, we combine depth-integrated microplastic data from the California Current Ecosystem with high-resolution foraging measurements from 191 tag deployments on blue, fin, and humpback whales to quantify plastic ingestion rates and routes of exposure. We find that baleen whales predominantly feed at depths of 50-250 m, coinciding with the highest measured microplastic concentrations in the pelagic ecosystem. Nearly all (99%) microplastic ingestion is predicted to occur via trophic transfer. We predict that fish-feeding whales are less exposed to microplastic ingestion than krill-feeding whales. Per day, a krill-obligate blue whale may ingest 10 million pieces of microplastic, while a fish-feeding humpback whale likely ingests 200,000 pieces of microplastic. For species struggling to recover from historical whaling alongside other anthropogenic pressures, our findings suggest that the cumulative impacts of multiple stressors require further attention.

Anoxic conditions within reservoirs related to thermal stratification and oxygen depletion lead to methylmercury (MeHg) production, a key process governing the uptake of mercury in aquatic food webs. Once formed within a reservoir, the timing and magnitude of the biological uptake of MeHg and the relative importance of MeHg export in water versus biological compartments remain poorly understood. We examined the relations between the reservoir stratification state, anoxia, and the concentrations and export loads of MeHg in aqueous and biological compartments at the outflow locations of two reservoirs of the Hells Canyon Complex (Snake River, Idaho-Oregon). Results show that (1) MeHg concentrations in filter-passing water, zooplankton, suspended particles, and detritus increased in response to reservoir destratification; (2) zooplankton MeHg strongly correlated with MeHg in filter-passing water during destratification; (3) reservoir anoxia appeared to be a key control on MeHg export; and (4) biological MeHg, primarily in zooplankton, accounted for only 5% of total MeHg export from the reservoirs (the remainder being aqueous compartments). These results improve our understanding of the role of biological incorporation of MeHg and the subsequent downstream release from seasonally stratified reservoirs and demonstrate that in-reservoir physical processes strongly influence MeHg incorporation at the base of the aquatic food web.