Search

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.

Super hydrophobic porous silicon surface is prepared using a wet chemical synthesis route. Scanning electron microscopic investigation confirms a correlation between pore size and reaction time. SERS substrates are prepared by silver nanoparticle deposition on porous silicon surface. They exhibit excellent characteristics in terms of sensitivity, reproducibility, stability, and uniformity. They could detect rhodamine 6G in femtomolar range with SERS enhancement factor of ~ 6.1 × 1012, which is best ever reported for these substrates. Molecule-specific sensing of water pollutants such as methylene blue, glyphosate, and chlorpyrifos, is demonstrated for concentrations well below their permissible limits along with excellent enhancement factors. Porous silicon substrate functionalized with Ag nanoparticles demonstrates to be a promising candidate for low-cost, long-life, reliable sensors for environmental conservation applications. [ABSTRACT FROM AUTHOR]

The most essential task in the twenty‐first century is to fight the alarming growing pollution in the aquatic body in which effluent of one of the most colouring dye categories called maxilon dye is a major contributor. This review thus specifically focuses on the use of nanoparticles (NPs) for photocatalytic degradation of maxilon dye contaminants in water bodies. The work empirically presented the performance evaluation of NPs in degrading maxilon dyes under light irradiation alongside the underlying operational photocatalytic degradation mechanism. The stability of NPs was also critically analyzed by looking at the regenerability and reusability of expended NPs. From the study, it was discovered that ⋅OH and O2⋅ played a vital role in the genesis of the oxidizing capacity of NPs for the photocatalytic breakdown of maxilon dye. Moreover, it was found that the degradation performance of most NPs is greater than 80 % and the shortest degradation period is < 1 hour with pseudo‐first‐order (PFO) being the most common kinetic best‐fit to describe the adsorption process that occurred shortly before and during the degradation operation. At the end, knowledge gaps were identified in the area of regenerability, the lifecycle analyses of nano‐photocatalyst fabrication and utilization, cost analysis for industrial scale‐up, maxilon dye ecotoxicological study, and degradation pathways. The findings of this study can open up insightful innovation for readers and industries that are interested in pursuing zero water insecurity. [ABSTRACT FROM AUTHOR]

The adsorption effects of the crystal structure and morphological features of ferric hydroxyl oxide (hereinafter referred to as FeOOH) on different types of pollutants in water are briefly described, the preparation methods of FeOOH with different morphologies as well as the domestic and international research advances and achievements of this type of adsorbent in adsorption of heavy metals, organic pollutants, and inorganic pollutants in water are summarized, and the adsorption mechanisms of this type of adsorbent on different pollutants are further described, and the adsorption mechanism of FeOOH in the aqueous phase is explored in conjunction with the literature, and the direction of development for the adsorbent materials of FeOOH is finally envisioned. [ABSTRACT FROM AUTHOR]

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.

Iron (Fe)-based groundwater treatment removes carcinogenic arsenic (As) effectively but generates toxic As-rich Fe oxide water treatment residuals (As WTRs) that must be managed appropriately to prevent environmental contamination. In this study, we apply life cycle assessment (LCA) to compare the toxicity impacts of four common As WTR disposal strategies that have different infrastructure requirements and waste control: (i) landfilling, (ii) brick stabilization, (iii) mixture with organic waste, and (iv) open disposal. The As disposal toxicity impacts (functional unit = 1.0 kg As) are compared and benchmarked against impacts of current methods to produce marketable As compounds via As mining and concentrate processing. Landfilling had the lowest non-carcinogen toxicity (2.0 × 10-3 CTUh), carcinogen toxicity (3.8 × 10-5 CTUh), and ecotoxicity (4.6 × 103 CTUe) impacts of the four disposal strategies, with the largest toxicity source being As emission via sewer discharge of treated landfill leachate. Although landfilling had the lowest toxicity impacts, the stored toxicity of this strategy was substantial (ratio of stored toxicity/emitted As = 13), suggesting that landfill disposal simply converts direct As emissions to an impending As toxicity problem for future generations. The remaining disposal strategies, which are frequently practiced in low-income rural As-affected areas, performed poorly. These strategies yielded ∼3-10 times greater human toxicity and ecotoxicity impacts than landfilling. The significant drawbacks of each disposal strategy indicated by the LCA highlight the urgent need for new methods to recover As from WTRs and convert it into valuable As compounds. Such advanced As recovery technologies, which have not been documented previously, would decrease the stored As toxicity and As emissions from both WTR disposal and from mining As ore.

Microplastics in agricultural soils have become the research hotspot in recent years, however, the quantitative methods based on the traditional visual inspection may have a high false detection rate. Here we combined the laser direct infrared (LDIR) and Fourier-transform infrared (FTIR) methods to investigate the microplastics in farmland with long-term agricultural activities. The results showed that the total abundance of microplastics reached 1.98 ± 0.41 × 105, 1.57 ± 0.28 × 105, 1.78 ± 0.27 × 105, and 3.20 ± 0.41 × 105 particles/kg soil in cotton fields with film mulching of 5, 10, 20, and >30 years, respectively. LDIR results indicated that microplastics ranging from 10 to 500 μm accounted for 96.5-99.9 % of the total microplastic amounts in the soils. Additionally, a total of 26 polymer types of microplastics were detected, among which polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyamide (PA), and polytetrafluoroethylene (PTFE) were dominantly observed. For the microplastics detected by FTIR (500 μm-5 mm), PE polymer was majorly observed (88.0-98.9 %). Most microplastics were films (88.2 %), while fibers and pellets were also found. The reclaimed water from sewage treatment plants, the drip irrigation utilities, and the residual plastic film are the potential sources of microplastics in the farmland soils. By using the automated quantitative and identifiable approaches, this study suggested that the commonly used visual counting method may underestimate the microplastic contamination in agricultural soils.

INTRODUCTION: Perfluorooctanoic acid (PFOA) has been associated with kidney cancer in human studies. METHODS: We conducted a pooled analysis of two large studies of PFOA and renal cell carcinoma (RCC, the most common type of kidney cancer); one from the National Cancer Institute (NCI) (324 cases and controls), and a second from the C8 Science Panel (103 cases and 511 controls). Serum PFOA levels were estimated a median of 8 years before diagnosis. Analyses were conducted via conditional logistic regression. Lifetime risk of kidney cancer per unit serum PFOA concentration and per unit dose were calculated. RESULTS: The 25th, 50th and 75th percentiles of serum PFOA levels were 4.8, 7.3, and 23.9 ng/ml for the pooled analysis. The preferred model for the pooled datawas a two-piece linear spline model (knot at 12.5 ng/ml serum PFOA); the log odds of RCC increased 0.1349 per 1 ng/ml increase in serum PFOA up to the knot (eg, an OR of 2.02 (1.45-2.80) from the median to the knot), and was flat thereafter. The estimated lifetime excess risk (cancer slope factor) with an exposure of 1 ng/ml was 0.0018, similar to the excess risk of 0.0026 recently reported by CalEPA based on different methods. Assuming a serum half-life of 2.3 years and a distribution volume of 170 ml/kg for PFOA, our results are equivalent to 0.0128 per ng/kg/d of PFOA intake. To limit excess lifetime kidney cancer risk to 1/1,000,000, our data suggest a limit of 0.0015 ng/L (0.0015 ppt) for PFOA in drinking water, similar to CalEPAs proposed Public Health Goal and the new US EPA Drinking Water Health Advisory. CONCLUSIONS: Our results correspond reasonably well with cancer slope factors developed by other investigators using published summary data, and suggest drinking water limits similar to new recommendations by the US EPA.

Nitrate pollution is of considerable global concern as a threat to human health and aquatic ecosystems. Nowadays, δ15N/δ18O-NO3- combined with a Bayesian-based SIAR model are widely used to identify riverine nitrate sources. However, little is known regarding the effect of variations in pollution source isotopic composition on nitrate source contributions. Herein, we used δ15N/δ18O-NO3-, SIAR modeling, probability statistical analysis and a perturbing method to quantify the contributions and uncertainties of riverine nitrate sources in the Wen-Rui Tang River of China and to further investigate the model sensitivity of each nitrate source. The SIAR model confirmed municipal sewage (MS) as the major nitrate source (58.5-75.7%). Nitrogen fertilizer (NF, 8.6-20.9%) and soil nitrogen (SN, 7.8-20.1%) were also identified as secondary nitrate sources, while atmospheric deposition (AD,

Due to the detection frequencies and measured concentrations in surface water, the type I pyrethroid insecticide, bifenthrin, has been of particular concern within the Sacramento-San Joaquin Delta in California. Concentrations have been detected above levels previously reported to impair neuroendocrine function and induce neurotoxicity to several species of salmonids. Metabolomic and transcriptomic studies indicated impairment of cellular signaling within the brain of exposed animals and potential alteration of lipid metabolism. To better understand the potential impacts of bifenthrin on brain lipids, juvenile rainbow trout (Oncorhynchus mykiss) were exposed to mean bifenthrin concentrations of 28 or 48 ng/L for 14 days, and non-targeted lipidomic profiling in the brain was conducted. Brain tissue sections were also assessed for histopathological insult following bifenthrin treatment. Bifenthrin-exposed trout had a concentration-dependent decrease in the relative abundance of triglycerides (TGs) with levels of phosphatidylcholines (PCs) and phosphatidylethanolamines (PEs) significantly altered following 48 ng/L bifenthrin exposure. An increased incidence of histopathological lesions, such as focal hemorrhages and congestion of blood vessels, was noted in the brains of bifenthrin-treated animals, suggesting an association between altered lipid metabolism and neuronal cell structure and integrity.

Mercury (Hg) is a ubiquitous contaminant in the environment and its methylated form, methylmercury (MeHg), poses a worldwide health concern for humans and wildlife, primarily through fish consumption. Global production of forest fire ash, derived from wildfires and prescribed burns, is rapidly increasing due to a warming climate, but their interactions with aqueous and sedimentary Hg are poorly understood. Herein, we compared the differences of wildfire ash with activated carbon and biochar on the sorption of aqueous inorganic Hg and sedimentary Hg methylation. Sorption of aqueous inorganic Hg was greatest for wildfire ash materials (up to 0.21 μg g-1 or 2.2 μg g-1 C) among all of the solid sorbents evaluated. A similar Hg adsorption mechanism for activated carbon, biochar made of walnut, and wildfire ash was found that involves the formation of complexes between Hg and oxygen-containing functional groups, especially the -COO group. Notably, increasing dissolved organic matter from 2.4 to 70 mg C L-1 remarkably reduced Hg sorption (up to 40% reduction) and increased the time required to reach Hg-sorbent pseudo-equilibrium. Surprisingly, biochar and wildfire ash, but not activated carbon, stimulated MeHg production during anoxic sediment incubation, possibly due to the release of labile organic matter. Overall, our study indicates that while wildfire ash can sequester aqueous Hg, the leaching of its labile organic matter may promote production of toxic MeHg in anoxic sediments, which has an important implication for potential MeHg contamination in downstream aquatic ecosystems after wildfires.

Monitoring mercury (Hg) levels in biota is considered an important objective for the effectiveness evaluation of the Minamata Convention. While many studies have characterized Hg levels in organisms at multiple spatiotemporal scales, concentration analyses alone often cannot provide sufficient information on the Hg exposure sources and internal processes occurring within biota. Here, we review the decadal scientific progress of using Hg isotopes to understand internal processes that modify the speciation, transport, and fate of Hg within biota. Mercury stable isotopes have emerged as a powerful tool for assessing Hg sources and biogeochemical processes in natural environments. A better understanding of the tissue location and internal mechanisms leading to Hg isotope change is key to assessing its use for biomonitoring. We synthesize the current understanding and uncertainties of internal processes leading to Hg isotope fractionation in a variety of biota, in a sequence of better to less studied organisms (i.e., birds, marine mammals, humans, fish, plankton, and invertebrates). This review discusses the opportunities and challenges of using certain forms of biota for Hg source monitoring and the need to further elucidate the physiological mechanisms that control the accumulation, distribution, and toxicity of Hg in biota by coupling new techniques with Hg stable isotopes.

Sinking of microplastics (MPs) after biofouling is considered an important mechanisms responsible for the downward transport/sedimentation of MPs in the ocean and freshwaters. Previous studies demonstrated MP sinking caused by an increase in the composite density of MPs after biofouling, while MPs with smaller size or shapes with higher surface area to volume ratios (SA:V), such as films, are speculated to sink faster. In this study, we designed an in situ microcosm to simulate the ambient environmental conditions experienced by floating MPs to elucidate the biofouling and sinking of polyethylene (PE), polypropylene (PP), and expanded-polystyrene (EPS) MPs of various sizes and shapes. Our results showed smaller PE and PP MP granules sank faster than large ones. Even EPS granules of 100 μm diameter, having a much lower density (0.02 mg/mm3) than water, started to sink after 2 weeks of biofouling. Moreover, PE film and fiber MPs with higher SA:V did not sink faster than PE MP granules of the same mass, implying that mechanisms other than SA:V, such as fouling contact area and drag coefficient, play a role in the regulation of biofouling and sinking of MPs.

Water pollution poses a significant threat to both human health and ecosystem integrity. Chemical pollutants such as dyes and pesticides affect the water quality and endanger aquatic life. Among the methods for water purification from organic pollutants, photodegradation is certainly a valid technique to decrease such contaminants. In this work, pristine NiO, ZnO, and NiO-ZnO photocatalysts were synthesized by the homogeneous co-precipitation method. X-ray diffraction confirms the formation of a photocatalyst consisting of ZnO (Hexagonal) and NiO (Cubic) structures. The crystalline size was calculated by the Scherrer formula, which is 19 nm for the NiO-ZnO photocatalyst. The band gap measurements of the prepared samples were obtained using the Tauc Plot, equation which is 2.93 eV, 3.35 eV and 2.63 eV for NiO, ZnO, and NiO-ZnO photocatalysts, respectively. The photocatalytic performance of NiO-ZnO nanocomposite was evaluated through the degradation of Methylene Blue and Nile Blue dyes under sunlight, and Bentazon herbicide under a UV light. Photocatalyst degradation efficiency was 95% and 97% for Methylene Blue and Nile Blue in 220 min under sunlight while a degradation of 70% for Bentazon after 100 min under UV light source was found. [ABSTRACT FROM AUTHOR]

In India, rivers are the primary source of water for millions of people. However, inadequate wastewater management and excessive dumping of pollutants have led to the pollution of these rivers. In the present study, quality of complexly contaminated Yamuna water was analyzed during and after COVID-19 and concluded that water quality improved during COVID-19 but deteriorated significantly after the pandemic, becoming highly contaminated with both organic and inorganic pollutants. For this study, water samples were collected during and post-COVID from 11 different locations in Delhi, Uttar Pradesh, and Haryana, spanning three different seasons (winter, summer, and monsoon) from 2020 to 2022. The results showed significant changes in pH, conductivity, and salinity during the study. Chemical Oxygen Demand (COD) reached its highest recorded value of 388±3.4 mg/L during the monsoon of 2022 at Tronica City. Biochemical Oxygen Demand (BOD) peaked at 27.6±1.18 mg/L at ITO during the monsoon of 2021. Total hardness was highest, measuring 806±21.4 mg/L, during the summer of 2022 at Katha. Additionally, ammonia content was found to be at its highest, measuring 21.23±0.51 PPM, during the summer of 2021 at ISBT Old Bridge. The study also explored the use of various microalgae, including Scenedesmus sp., Klebsormidium sp., Nephrocytium sp., Oocystis sp., Monoraphidium sp., Chlorococcum sp., and filamentous alga Hydrodictyon reticulatum for phycoremediation. These algae were found to efficiently remove pollutants, with Monoraphidium sp. removing 81.81±0.82% of COD, and Chlorococcum sp. effectively removing 78.38±1.02% of ammonia from the complexly contaminated Yamuna water. This study clearly demonstrates that the concentration of pollutants significantly decreased during COVID-19 but increased afterward. The water quality of the Yamuna River in the study area was found to be hazardous for both humans and animals and statistical methods such as ANOVA (Analysis of Variance) and Principal Component Analysis (PCA) validate the significance of the data, correlations, and variances between different pollutants and the effectiveness of phycoremediating algae. [ABSTRACT FROM AUTHOR]

The human population has massively increased throughout the world. This has created various serious challenges, especially water pollution issues. Heavy metals, dyes, textile industries, microorganisms, organic and chemical pollutants can be included as main sources of water pollution. There are various methods for contaminant disposal. In this regard, the adsorption technique can be considered the most common method. In this technique, alum and polyaluminum chloride are widely used chemicals. However, they have harmful side effects on the environment, due to their chemical nature. One of the best solutions to overcome this issue is the use of natural materials and polysaccharides, which are abundant materials, biocompatible, biodegradable, non-toxic and functional groups with low processing costs. These materials include Guar Gum (GG), derivatives such as Al2O3 (GG-AO), GG nanocomposites, acrylic gum-based hydrogels, GG-hydrogel, gum nano-hydrogels, magnetic nano-GG, agaric GG, itaconic (Aldehyde GG), Galacyl-Hydrazine modified GG (GG-GH), depolymerized GG (oxidized GG), Guar-Graft Poly(Methylacrylate) (GG-g PMA), poly(acrylamide) GG-silica nanocomposites, GG Sulphonic Acid (g-GG/SiO2), GG Nitrilotriacetic Acid (GNTA) resin, etc. Different factors such as pH, adsorbent amount and contact retention time have significant impacts on adsorbent efficiency. Various studies have reported that pH values of 4–8 resulted in efficiency higher than 90%. The concentration of the adsorbent and the contact time are varied, depending on the type of the considered derivative. The use of GG and its derivatives can be an effective strategy to greatly reduce the cost of water treatment. In addition to being cost-effective, the proposed strategy is biocompatible and eco-friendly. [ABSTRACT FROM AUTHOR]

This study investigates the viability of developing chitosan-based hydrogels derived from waste shrimp shells for the removal of methylene blue and methyl orange, thereby transforming food waste into advanced materials for environmental remediation. Despite chitosan-based adsorbents being conventionally considered ideal for the removal of negative pollutants, through targeted functionalization with poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) at varying concentrations, we successfully enhance the hydrogels' efficacy in also adsorbing positively charged adsorbates. Specifically, the incorporation of PEDOT:PSS at a concentration of 10% v/v emerges as a critical factor in facilitating the robust adsorption of dyes. In the case of the anionic dye methyl orange (MO, 10−5 M), the percentage of removed dye passed from 47% (for beads made of only chitosan) to 66% (for beads made of chitosan-PEDOT:PSS 10%), while, in the case of the cationic dye methylene blue (MB, 10−5 M), the percentage of removed dye passed from 52 to 100%. At the basis of this enhancement, there is an adsorption mechanism resulting from the interplay between electrostatic forces and π–π interactions. Furthermore, the synthesized functionalized hydrogels exhibit remarkable stability and reusability (at least five consecutive cycles) in the case of MB, paving the way for the development of cost-effective and sustainable adsorbents. This study highlights the potential of repurposing waste materials for environmental benefits, introducing an innovative approach to address the challenges regarding water pollution. [ABSTRACT FROM AUTHOR]

This study undertook an assessment of 24 physiochemical parameters at over 1094 sites to compute the water quality index (WQI) across the upper and central Punjab regions of Pakistan. Prior to the WQI calculation, an analytical hierarchy process (AHP) was employed to assign specific weights to each water quality parameter. The categorization of WQI into distinct classes was achieved by constructing a pairwise matrix based on their relative importance utilizing Saaty's scale. Additionally, the groundwater quality status for irrigation and drinking purposes across various zones in the study area was delineated through the integration of WQI and geostatistical methodologies. The findings revealed discernible heavy metal issues in the Lahore division, with emerging microbiological contamination across the entire study region, potentially attributed to untreated industrial effluent discharge and inadequately managed sewerage systems. The computed indices for the Lahore, Sargodha, and Rawalpindi divisions fell within the marginal to unfit categories, indicating water quality concerns. In contrast, the indices for other divisions were in the medium class, suggesting suitability for drinking purposes. Scenario analysis for developing mitigation strategies indicated that primary treatment before wastewater disposal could rehabilitate 9% of the study area, followed by secondary (35%) and tertiary (41%) treatments. Microbiological contamination (27%) emerged as the predominant challenge for water supply agencies. Given the current trajectory of water quality deterioration, access to potable water is poised to become a significant public concern. Consequently, government agencies are urged to implement appropriate measures to enhance overall groundwater quality for sustainable development. [ABSTRACT FROM AUTHOR]

Vanillic acid (4-hydroxy-3-methoxybenzoic acid) (VA) is a natural benzoic acid derivative commonly found in herbs, rice, maize, and some fruits and vegetables. However, due to the wide use of VA in various industrial sectors, its presence in the environment might harm living organisms. This study evaluated the toxicity of VA and its isomers, iso-VA and orto-VA. Firstly, the antimicrobial effect of VA and its isomers iso-VA and orto-VA (in doses of 1000; 100, 10, 1; 0.1; 0.01 mg/L) against Escherichia coli, Sarcina spp., Enterobacter homaechei, Staphylococcus aureus and Candida albicans were identified. The toxic effect and protein degradation potential of VA and its isomers were determined using E. coli grpE:luxCDABE and lac:luxCDABE biosensor strains. However, the genotoxicity and oxidative stress generation were assessed with the E. coli recA:luxCDABE biosensor and E. coli strain. The results showed that VA, iso-VA, and orto-VA exhibited antimicrobial activity against all tested bacterial strains. However, VA's antimicrobial effect differed from iso-VA and orto-VA. Similar toxic, genotoxic, and oxidative stress-inducing effects were observed for VA and its isomers. Each compound exhibited toxicity, cellular protein degradation, and genotoxic activity against E. coli grpE:luxCDABE, E. coli lac:luxCDABE, and E. coli recA:luxCDABE strains. Analysis of reactive oxygen species (ROS) generation within E. coli cells highlighted oxidative stress as a contributing factor to the toxicity and genotoxicity of VA and its isomers. While the findings suggest potential applications of VA compounds as food preservatives, their presence in the environment raises concerns regarding the risks posed to living organisms due to their toxic and genotoxic characteristics.

Per- and polyfluoroalkyl substances (PFASs) are synthetic contaminants found in drinking groundwater sources and a wide variety of consumer products. Because of their adverse environmental and human health effects, remediation of these persistent compounds has attracted significant recent attention. To gain mechanistic insight into their remediation, we present the first ab initio study of PFAS degradation via hydrated electrons─a configuration that has not been correctly considered in previous computational studies up to this point. To capture these complex dynamical effects, we harness ab initio molecular dynamics (AIMD) simulations to probe the reactivities of perfluorooctanoic (PFOA) and perfluorooctane sulfonic acid (PFOS) with hydrated electrons in explicit water. We complement our AIMD calculations with advanced metadynamics sampling techniques to compute free energy profiles and detailed statistical analyses of PFOA/PFOS dynamics. Although our calculations show that the activation barrier for C-F bond dissociation in PFOS is three times larger than that in PFOA, all the computed free energy barriers are still relatively low, resulting in a diffusion-limited process. We discuss our results in the context of recent studies on PFAS degradation with hydrated electrons to give insight into the most efficient remediation strategies for these contaminants. Most importantly, we show that the degradation of PFASs with hydrated electrons is markedly different from that with excess electrons/charges, a common (but largely incomplete) approach used in several earlier computational studies.

Human-health risks from microplastics have attracted considerable attention, but little is known about human-exposure pathways and intensities. Recent studies posited that inhalation of atmospheric microplastics was the dominant human-exposure pathway. Herein, our study identified that atmospheric microplastics ingested from deposition during routine dining/drinking activities represent another important exposure pathway. We measured abundances of atmospheric-deposited microplastics of up to 105 items m-2 d-1 in dining/drinking venues, with 90% smaller than 100 µm and a dominance of amorphous fragments rather than fibers. Typical work-life scenarios projected an annual ingestion of 1.9 × 105 to 1.3 × 106 microplastics through atmospheric deposition on diet, with higher exposure rates for indoor versus outdoor dining/drinking settings. Ingestion of atmospheric-deposited microplastics through diet was similar in magnitude to presumed inhalation exposure, but 2-3 orders of magnitude greater than direct ingestion from food sources. Simple mitigation strategies (e.g., covering and rinsing dishware) can substantially reduce the exposure of atmospheric deposition microplastics through diet.

Determining health risks associated with per-/polyfluoroalkyl substances (PFASs) is a highly complex problem requiring massive efforts for scientists, risk assessors, and regulators. Among the most poorly understood pressing questions is the relative importance of pre-PFAAs, which are PFASs that degrade to highly persistent perfluoroalkyl acids. How many of the vast number of existing pre-PFAAs are relevant for direct human exposure, and what are the predominant exposure pathways? What evidence of direct exposure to pre-PFAAs is provided by human biomonitoring studies? How important are pre-PFAAs and their biotransformation products for human health risk assessment? This article outlines recent progress and recommendations toward widening the lens on human PFAS exposure to include the pre-PFAA subclass.

In this study, we have developed a comprehensive machine learning (ML) framework for long-term groundwater contamination monitoring as the Python package PyLEnM (Python for Long-term Environmental Monitoring). PyLEnM aims to establish the seamless data-to-ML pipeline with various utility functions, such as quality assurance and quality control (QA/QC), coincident/colocated data identification, the automated ingestion and processing of publicly available spatial data layers, and novel data summarization/visualization. The key ML innovations include (1) time series/multianalyte clustering to find the well groups that have similar groundwater dynamics and to inform spatial interpolation and well optimization, (2) the automated model selection and parameter tuning, comparing multiple regression models for spatial interpolation, (3) the proxy-based spatial interpolation method by including spatial data layers or in situ measurable variables as predictors for contaminant concentrations and groundwater levels, and (4) the new well optimization algorithm to identify the most effective subset of wells for maintaining the spatial interpolation ability for long-term monitoring. We demonstrate our methodology using the monitoring data at the Savannah River Site F-Area. Through this open-source PyLEnM package, we aim to improve the transparency of data analytics at contaminated sites, empowering concerned citizens as well as improving public relations.

BackgroundPrenatal exposure to drinking water with arsenic concentrations >50 μg/L is associated with adverse birth outcomes, with inconclusive evidence for concentrations ≤50 μg/L. In a collaborative effort by public health experts, hydrologists, and geologists, we used published machine learning model estimates to characterize arsenic concentrations in private wells-federally unregulated for drinking water contaminants-and evaluated associations with birth outcomes throughout the conterminous U.S.MethodsUsing several machine learning models, including boosted regression trees (BRT) and random forest classification (RFC), developed from measured groundwater arsenic concentrations of ∼20,000 private wells, we characterized the probability that arsenic concentrations occurred within specific ranges in groundwater. Probabilistic model estimates and private well usage data were linked by county to all live birth certificates from 2016 (n = 3.6 million). We evaluated associations with gestational age and term birth weight using mixed-effects models, adjusted for potential confounders and incorporated random intercepts for spatial clustering.ResultsWe generally observed inverse associations with term birth weight. For instance, when using BRT estimates, a 10-percentage point increase in the probability that private well arsenic concentrations exceeded 5 μg/L was associated with a -1.83 g (95% CI: -3.30, -0.38) lower term birth weight after adjusting for covariates. Similarly, a 10-percentage point increase in the probability that private well arsenic concentrations exceeded 10 μg/L was associated with a -2.79 g (95% CI: -4.99, -0.58) lower term birth weight. Associations with gestational age were null.ConclusionIn this largest epidemiologic study of arsenic and birth outcomes to date, we did not observe associations of modeled arsenic estimates in private wells with gestational age and found modest inverse associations with term birth weight. Study limitations may have obscured true associations, including measurement error stemming from a lack of individual-level information on primary water sources, water arsenic concentrations, and water consumption patterns.

Organism tolerance thresholds for emerging contaminants are vital to the development of water quality criteria. Acute (96-h) and chronic (10-day) effects thresholds for neonicotinoid pesticides clothianidin and thiamethoxam, and the carbamate pesticide methomyl were developed for the midge Chironomus dilutus to support criteria development using the UC Davis Method. Median lethal concentrations (LC50s) were calculated for acute and chronic exposures, and the 25% inhibition concentrations (IC25) were calculated for the chronic exposures based on confirmed chemical concentrations. Clothianidin effect concentrations were 4.89 µg/L, 2.11 µg/L and 1.15 µg/L for 96-h LC50, 10-day LC50 and 10-day IC25, respectively. Similarly, thiamethoxam concentrations were 56.4 µg/L, 32.3 µg/L and 19.6 µg/L, and methomyl concentrations were 244 µg/L, 266 µg/L and 92.1 µg/L. Neonicotinoid effect concentrations compared favorably to previously published 96-h and 14-day LC50 concentrations, and methomyl effect concentrations were within the acute survival range reported for Chironomus species and other organisms.

Several classes of pesticides have been shown to impair water quality in California, including organophosphates, pyrethroids and neonicotinoids. Vegetative treatment systems (VTS) can reduce pesticide loads and associated toxicity in agricultural runoff, but many water-soluble pesticides such as neonicotinoids are not effectively treated by VTS, and VTS installation is not always an option for growers required to remove non-crop vegetation for food safety concerns. Recent studies have shown that biochar filtration can be used to remove soluble contaminants, especially when coupled with other VTS components. We evaluated a mobile carbon filter system consisting of a trailer-mounted tank containing approximately 600L (~ 180 kg) of biochar. Input water from a 437-hectare agricultural drainage was pre-filtered and treated with biochar during two multi-week study periods. Laboratory toxicity tests and chemical and nutrient analyses were conducted on input and output water. Pesticide concentrations were initially reduced by greater than 99%. Treatment efficacy declined linearly and was expected to remain at least 50% effective for up to 34 weeks. Toxicity was assessed with Ceriodaphnia dubia, Hyalella azteca and Chironomus dilutus. Significant input toxicity was reduced to non-toxic levels in 6 of 16 samples. Some input concentrations of the neonicotinoid imidacloprid and the pyrethroid cypermethrin exceeded organism-specific toxicity thresholds and benchmarks, but the overall causes of toxicity were complex mixtures of agricultural chemicals. Nutrients were not reduced by the biochar. Results demonstrate the utility of biochar in treating agricultural runoff and provide measures of the longevity of biochar under field conditions.

Most stored groundwater is fossil in its age, having been under the ground for more than ~12 thousand years. Mapping where wells tap fossil aquifers is relevant for water quality and quantity management. Nevertheless, the prevalence of wells that tap fossil aquifers is not known. Here we show that wells that are sufficiently deep to tap fossil aquifers are widespread, though they remain outnumbered by shallower wells in most areas. Moreover, the proportion of newly drilled wells that are deep enough to tap fossil aquifers has increased over recent decades. However, this widespread and increased drilling of wells into fossil aquifers is not necessarily associated with groundwater depletion, emphasizing that the presence of fossil groundwater does not necessarily indicate a non-renewable water supply. Our results highlight the importance of safeguarding fossil groundwater quality and quantity to meet present and future water demands.

The dissolution of sulfide minerals can lead to hazardous arsenic levels in groundwater. This study investigates the oxidative dissolution of natural As-bearing sulfide minerals and the related release of arsenic under flow-through conditions. Column experiments were performed using reactive As-bearing sulfide minerals (arsenopyrite and löllingite) embedded in a sandy matrix and injecting oxic solutions into the initially anoxic porous media to trigger the mineral dissolution. Noninvasive oxygen measurements, analyses of ionic species at the outlet, and scanning electron microscopy allowed tracking the propagation of the oxidative dissolution fronts, the mineral dissolution progress, and the change in mineral surface composition. Process-based reactive transport simulations were performed to quantitatively interpret the geochemical processes. The experimental and modeling outcomes show that pore-water acidity exerts a key control on the dissolution of sulfide minerals and arsenic release since it determines the precipitation of secondary mineral phases causing the sequestration of arsenic and the passivation of the reactive mineral surfaces. The impact of surface passivation strongly depends on the flow velocity and on the spatial distribution of the reactive minerals. These results highlight the fundamental interplay of reactive mineral distribution and hydrochemical and hydrodynamic conditions on the mobilization of arsenic from sulfide minerals in flow-through systems.

The Salinas Valley in Monterey County, California, USA, is a highly productive agricultural region. Irrigation runoff containing pesticides at concentrations toxic to aquatic organisms poses a threat to aquatic ecosystems within local watersheds. This study monitored the effectiveness of a constructed wetland treatment system with a granulated activated carbon (GAC) filter installation at reducing pesticide concentrations and associated toxicity to Ceriodaphnia dubia, Hyalella azteca, and Chironomus dilutus. The wetland was supplied with water pumped from an impaired agricultural and urban drainage. Across five monitoring trials, the integrated system's average pesticide concentration reduction was 52%. The wetland channel and GAC filtration components individually provided significant treatment, and within each, pesticide solubility had a significant effect on changes in pesticide concentrations. The integrated treatment system also reduced nitrate by 61%, phosphate by 73%, and turbidity by 90%. Input water was significantly toxic to C. dubia and H. azteca in the first trial. Toxicity to C. dubia persisted throughout the system, whereas toxicity to H. azteca was removed by the channel, but there was residual toxicity post-GAC. The final trial had significant input toxicity to H. azteca and C. dilutus. The channel reduced toxicity to H. azteca and removed toxicity to C. dilutus. GAC filtration reduced H. azteca toxicity to an insignificant level. There was no input toxicity in the other three trials. The results demonstrate that a wetland treatment system coupled with GAC filtration can reduce pesticide concentrations, nutrients, suspended particles, and aquatic toxicity associated with agricultural runoff.

Plastics are widely recognized as a pervasive marine pollutant. Microplastics have been garnering increasing attention due to reports documenting their ingestion by animals, including those intended for human consumption. Their accumulation in the marine food chain may also pose a threat to wildlife that consume species that can accumulate microplastic particles. Microplastic contamination in marine ecosystems has thus raised concerns for both human and wildlife health. Our study addresses an unexplored area of research targeting the interaction between plastic and pathogen pollution of coastal waters. We investigated the association of the zoonotic protozoan parasites Toxoplasma gondii, Cryptosporidium parvum, and Giardia enterica with polyethylene microbeads and polyester microfibers. These pathogens were chosen because they have been recognized by the World Health Organization as underestimated causes of illness from shellfish consumption, and due to their persistence in the marine environment. We show that pathogens are capable of associating with microplastics in contaminated seawater, with more parasites adhering to microfiber surfaces as compared with microbeads. Given the global presence of microplastics in fish and shellfish, this study demonstrates a novel pathway by which anthropogenic pollutants may be mediating pathogen transmission in the marine environment, with important ramifications for wildlife and human health.

Dry wells (gravity-fed infiltration wells) have frequently been used to recharge aquifers with stormwater, especially in urban areas, as well as manage flood risk and reduce surface water body contamination from stormwater pollutants. However, only limited assessment of their potential adverse impacts on groundwater quality exists. Dry well recharge can bypass significant portions of the filtering-capacity of the vadose zone. Stormwater and groundwater monitoring data and analysis of transport of a wide range of historic and current-use stormwater chemicals of concern is lacking. To address these gaps, two dry wells were constructed with vegetated and structural pretreatment features to assess the likelihood of stormwater contaminants reaching the aquifer. We monitored, assessed, and compared the presence of contaminants in stormwater to water quality in the vadose zone and shallow groundwater after it passed through the dry well. The dry wells were installed at a suburban residential and at a suburban commercial site. The selected sites were overlying a regional, unconsolidated, and highly heterogeneous alluvial aquifer system. Stormwater, vadose zone, and groundwater samples were collected during five storms and analyzed for over 200 contaminants of concern. Relatively few contaminants were detected in stormwater, generally at low concentrations. Prior to stormwater entering the dry well, 50-65% of contaminants were removed by vegetated pretreatment. In groundwater, metals such as aluminum and iron were detected at similar concentrations in both upgradient and downgradient wells, suggesting the source of these metals was not dry well effluent. Naturally occurring metals such as chromium and arsenic were not detected in stormwater but were found at elevated concentrations in groundwater. A modeling assessment suggests that the travel time of metals and hydrophobic organic contaminants to the water table at these sites ranges from years to centuries, whereas water soluble pesticides would likely reach the water table within days to months. The modeling assessment also showed that more vulnerable sites with higher fraction of alluvial sands would have much shorter contaminant travel times. However, none of the contaminants assessed reached concentrations that pose a risk to human health across the scenarios considered. No evidence was found, either through direct measurements or vadose zone modeling, that contaminants present in suburban stormwater degraded or would degrade groundwater quality at the studied sites and site conditions. Future work is needed to address emerging contaminants of concern.

Maximizing water reuse requires addressing legal and regulatory frameworks, but growers’ understanding of water as a vehicle for pollutants and safe practices is vital in this process. A cross-sectional survey of 85 growers in Lebanon, Jordan, and Tunisia explored these factors. Results showed that 70.6% of growers had limited knowledge about the transmission of pathogens, pesticides, and pharmaceuticals to food crops via treated wastewater (TWW). Additionally, 55% of farmers used TWW for irrigation, while 65.9% believed that it poses health risks to consumers when applied to crops eaten raw. A positive attitude toward TWW was a determining factor for maximizing water reuse applications. However, the limited access and unavailability of treatment plants were the primary reasons for not using TWW (32.9%). More concerning, less than half controlled the quality of irrigation water using microbiological tests (32.9%), chemical tests (37.6%), and turbidity tests (29.4%). Meanwhile, only 40% trusted local authorities’ control of TWW quality and 69.4% had no access to regulatory information. The present study showed the importance of prioritizing growers’ awareness of potential risks and establishing the practice of monitoring of water quality indicators and contaminants. These should be at the forefront of water reuse expansion strategies to mitigate associated risks. HIGHLIGHTS The majority of growers lacked training in good agricultural practices.; Less than half of the growers monitored the quality of water.; Only 40% trusted local authorities' control of treated wastewater (TWW) quality.; For some growers, TWW poses health risks if applied to crops eaten raw.; Positive attitude toward TWW maximizes water reuse.;

Species Sensitivity Distribution (SSD) is a key metric for understanding the potential ecotoxicological impacts of chemicals. However, SSDs have been developed to estimate for only handful of chemicals due to the scarcity of experimental toxicity data. Here we present a novel approach to expand the chemical coverage of SSDs using Artificial Neural Network (ANN). We collected over 2000 experimental toxicity data in Lethal Concentration 50 (LC50) for 8 aquatic species and trained an ANN model for each of the 8 aquatic species based on molecular structure. The R2 values of resulting ANN models range from 0.54 to 0.75 (median R2 = 0.69). We applied the predicted LC50 values to fit SSD curves using bootstrapping method, generating SSDs for 8424 chemicals in the ToX21 database. The dataset is expected to serve as a screening-level reference SSD database for understanding potential ecotoxicological impacts of chemicals.

Rhodanobacter species dominate in the Oak Ridge Reservation (ORR) subsurface environments contaminated with acids, nitrate, metal radionuclides, and other heavy metals. To uncover the genomic features underlying adaptations to these mixed-waste environments and to guide genetic tool development, we sequenced the whole genomes of eight Rhodanobacter strains isolated from the ORR site. The genome sizes ranged from 3.9 to 4.2 Mb harboring 3,695 to 4,035 protein-coding genes and GC contents approximately 67%. Seven strains were classified as R. denitrificans and one strain, FW510-R12, as R. thiooxydans based on full length 16S rRNA sequences. According to gene annotation, the top two Cluster of Orthologous Groups (COGs) with high pan-genome expansion rates (Pan/Core gene ratio) were "replication, recombination and repair" and "defense mechanisms." The denitrifying genes had high DNA homologies except the predicted protein structure variances in NosZ. In contrast, heavy metal resistance genes were diverse with between 7 to 34% of them were located in genomic islands, and these results suggested origins from horizontal gene transfer. Analysis of the methylation patterns in four strains revealed the unique 5mC methylation motifs. Most orthologs (78%) had ratios of nonsynonymous to synonymous substitutions (dN/dS) less than one when compared to the type strain 2APBS1, suggesting the prevalence of negative selection. Overall, the results provide evidence for the important roles of horizontal gene transfer and negative selection in genomic adaptation at the contaminated field site. The complex restriction-modification system genes and the unique methylation motifs in Rhodanobacter strains suggest the potential recalcitrance to genetic manipulation. IMPORTANCE Despite the dominance of Rhodanobacter species in the subsurface of the contaminated Oak Ridge Reservation (ORR) site, very little is known about the mechanisms underlying their adaptions to the various stressors present at ORR. Recently, multiple Rhodanobacter strains have been isolated from the ORR groundwater samples from several wells with varying geochemical properties. Using Illumina, PacBio, and Oxford Nanopore sequencing platforms, we obtained the whole genome sequences of eight Rhodanobacter strains. Comparison of the whole genomes demonstrated the genetic diversity, and analysis of the long nanopore reads revealed the heterogeneity of methylation patterns in strains isolated from the same well. Although all strains contained a complete set of denitrifying genes, the predicted tertiary structures of NosZ differed. The sequence comparison results demonstrate the important roles of horizontal gene transfer and negative selection in adaptation. In addition, these strains may be recalcitrant to genetic manipulation due to the complex restriction-modification systems and methylations.

The toxicity of single pesticides is likely underestimated when considering complex pesticide mixtures found in agricultural runoff and this is especially true for newer pesticides with little toxicity data on non-target species. The goal of our study was to compare the toxicity of two newer pesticides, imidacloprid (IMI) and chlorantraniliprole (CHL), when an invertebrate and fish were exposed to single compounds, binary mixtures or surface water collected near agricultural fields. A secondary goal was to determine whether changes in select subcellular molecular pathways correspond to the insecticides' mechanisms of activity in aquatic organisms. We conducted acute (96 h) exposures using a dilution series of field water and environmentally relevant concentrations of single and binary mixtures of IMI and CHL. We then evaluated survival, gene expression and the activity of IMI toward the n-acetylcholine receptor (nAChR) and CHL activity toward the ryanodine receptor (RyR). Both IMI and CHL were detected at all sampling locations for May 2019 and September 2019 sampling dates and exposure to field water led to high invertebrate but not fish mortality. Fish exposed to field collected water had significant changes in the relative expression of genes involved with detoxification and neuromuscular function. Exposure of fish to single compounds or binary mixtures of IMI and CHL led to increased relative gene expression of RyR in fish. Furthermore, we found that IMI targets the nAChR in aquatic invertebrates and that CHL can cause overactivation of the RyR in invertebrates and fish. Overall, our finding suggests that IMI and CHL may impact neuromuscular health in fish. Expanding monitoring efforts to include sublethal and molecular assays would allow the detection of subcellular level effects due to complex mixtures present in surface water near agricultural areas.

Pharmaceuticals and personal care products (PPCPs) are found in wastewater, and thus, the environment. In this study, current knowledge about the occurrence and fate of PPCPs in aquatic systems-including wastewater treatment plants (WWTPs) and natural waters around the world-is critically reviewed to inform the state of the science and highlight existing knowledge gaps. Excretion by humans is the primary route of PPCPs entry into municipal wastewater systems, but significant contributions also occur through emissions from hospitals, PPCPs manufacturers, and agriculture. Abundance of PPCPs in raw wastewater is influenced by several factors, including the population density and demography served by WWTPs, presence of hospitals and drugs manufacturers in the sewershed, disease burden of the population served, local regulations, and climatic conditions. Based on the data obtained from WWTPs, analgesics, antibiotics, and stimulants (e.g., caffeine) are the most abundant PPCPs in raw wastewater. In conventional WWTPs, most removal of PPCPs occurs during secondary treatment, and overall removal exceeds 90% for treatable PPCPs. Regardless, the total PPCP mass discharged with effluent by an average WWTP into receiving waters (7.35-20,160 g/day) is still considerable, because potential adverse effects of some PPCPs (such as ibuprofen) on aquatic organisms occur within measured concentrations found in surface waters.