Abstract Biointegrated carbon capture and utilization (BICCU) represents a promising alternative to conventional carbon capture technologies, combining microbial methanogenesis with CO2 capture agents, such as methyl diethanolamine (MDEA), to produce renewable methane from dilute CO2 sources. However, the biotoxicity of these solvents poses a major challenge to the viability of the BICCU approach. This study investigates the biocompatibility and physiological responses ofMethanococcus maripaludis and Methanosarcina barkeri to MDEA, through batch experiments and transcriptomic analysis. Both methanogens exhibited inhibited methane production when exposed to MDEA, with M. barkeri displaying higher sensitivity. M. maripaludis maintained the highest CH4 production rate at 30 mmol/L MDEA, while M. barkeri was almost fully inhibited at this concentration. Transcriptomic analysis revealed upregulation of genes associated with S-layer formation, cell envelope biogenesis, glycosyltransferase activity, and ion transport, alongside downregulation of lysine biosynthesis and secretion system genes. These findings suggest a metabolic trade-off, where cellular energy is reallocated toward stress response mechanisms. Results demonstrate that, while MDEA can be integrated with microorganisms, the exact response will depend on the methanogenic strain. Future research should focus on more biocompatible solvents and the selection of resilient methanogenic strains.
Abstract Unplanned wastewater reuse, or de facto reuse (DFR), improves surface water supply resiliency but can introduce nutrients and emerging contaminants into drinking water sources. Previous national DFR assessments excluded thousands of smaller drinking water systems that serve ≤10,000 people. By expanding the De Facto Reuse Incidence in our Nation’s Consumable Supply (DRINCS) model into DRINCS2.0 to include all 6,881 U.S. surface water intakes serving ∼232 million people, we identify a previously unrecognized national infrastructure gap. DRINCS2.0 uses updated high-resolution hydrography data and post-2020 water and wastewater facility details. Although large systems serving >10,000 people experience higher DFR frequency (41% versus 34%) and magnitude (medians of 2.0% versus 1.2%), 71% of impacted small systems (≤10,000 people) lack advanced treatment (i.e., activated carbon, ozone, and reverse osmosis) capable of treating pollutants of wastewater origin, compared with 43% of large systems. Higher DFR was associated with increased PFAS occurrence in treated drinking water obtained from EPA UCMR5 data sets. Sociodemographic analysis further showed that populations with greater socioeconomic vulnerability were more likely to receive drinking water from systems impacted by DFR without advanced treatment. This study provides the most comprehensive national assessment of DFR to date and offers a screening framework to prioritize monitoring and treatment upgrades for emerging contaminants.
Abstract Lynestrenol (LYN), a fourth-generation synthetic progestin whose active metabolite norethisterone is frequently detected in aquatic environments, poses potential risks to fish. Using integrated multi-omics, enzymology, and histopathology, we investigated the organ-specific toxicity of chronic LYN exposure (0.01, 1 μg/L for 60 days) in female mandarin fish (Siniperca chuatsi). LYN induced severe, dose-dependent hepatic necrosis, driven by concurrent blockade of the 2-oxocarboxylic acid metabolism pathway (via idh1 suppression) and ammonia detoxification failure. Additionally, LYN triggered a multi-node blockade of the ubiquinoid antioxidant system through coordinated downregulation of hpda, nqo1, and ggcx, resulting in oxidative collapse (increased ROS, MDA, ALT; decreased T-AOC, NQO1, IDH1). In contrast, ovaries remained histologically intact with no masculinization. Ovarian resilience involved dual adaptation: recalibration of steroidogenesis (downregulation of cyp19a, hsd11b2, and cpeb2 coupled with esr1 upregulation) and, for the first time in teleost gonads under progestin exposure, upregulation of ABCC efflux transporters (abcc2/3), via l-arginine/Nrf2 signaling. These findings reveal that LYN causes catastrophic hepatic metabolic collapse while ovarian tissue maintains homeostasis through active detoxification and steroidogenic reprogramming, providing a mechanistic basis for multi-organ risk assessment of progestins.
Abstract Ultrafine particles (UFP) and black carbon (BC) are key markers of combustion-related air pollution, yet disentangling their sources remains a challenge in complex urban environments. Using a hybrid mobile and fixed-site monitoring campaign, we investigated a marginalized northwest Toronto neighbourhood downwind of Toronto Pearson International Airport and a freight distribution corridor. Results reveal a divergent spatial footprint for the two pollutants. UFP concentrations correlated strongly with flight activity (r = 0.58, p < 0.05 at 3.5 km), with 1.7- to 3.3-fold enrichment downwind of the airport, measured as the ratio of the IQR of UFP concentrations under downwind versus other wind conditions, reaching 3.2-fold at residential sites ∼8 km away. BC was instead driven by roadway proximity and freight activity, with weak correlations with flight counts. BC–UFP correlations were strong during northerly winds (Mean r = 0.62), but weak downwind of the airport (Mean r = 0.1), indicating shared traffic and industrial sources versus independent sources downwind. Random Forest models (R2 = 0.79 for UFP, R2 = 0.87 for BC) identified industrial land-use and a highway as dominant drivers for both pollutants, airport proximity as a UFP-specific driver, and freight trucking as a BC-specific driver. These findings demonstrate that airport emissions can contribute to increased community UFP exposure several kilometers downwind, while local freight activity drives elevated BC concentrations.
Abstract Biofouling poses a substantial challenge to advanced wastewater treatment and reuse via nanofiltration (NF) membranes, while current strategies for enhancing antibiofouling performance often compromise membrane perm-selectivity. Herein, quaternized NF (QPIP-NF) membranes were fabricated via piperazine (PIP) quaternization to simultaneously enhance antibiofouling performance and perm-selectivity. Compared with PIP-NF membranes, QPIP-NF membranes exhibited 1.4-fold higher pure water permeance, slightly increased Na2SO4 rejection, and 1.4-fold higher water/Na2SO4 selectivity, owing to increased surface roughness, reduced polyamide thickness, and improved size-sieving. Furthermore, QPIP-NF membranes also exhibited a 91% improvement in antibacterial efficiency against Escherichia coli and a 48% enhancement in dynamic antibiofouling performance. Kit-based measurements of key bacterial enzyme activities and reactive-species levels, postfouling antibacterial evaluations, and confocal laser scanning microscopy analyses of live/dead cell distributions and biofilm thickness on the membrane surface collectively revealed the antibiofouling mechanism of the QPIP-NF membrane through inhibition of biofilm formation via surface bactericidal activity. Specifically, QPIP-NF membranes inhibited catalase, superoxide dismutase, DNA gyrase, and Na+/K+-ATPase activities while inducing excessive intracellular generation of H2O2 and superoxide anions, thereby ensuring lasting antibacterial activity in the near-membrane region and achieving excellent antibiofouling performance. Our study provides a new avenue for the design of antibiofouling NF membranes with improved perm-selectivity.
Abstract The February 2023 train derailment and subsequent vent and burn of 129,000 gallons of vinyl chloride in East Palestine, Ohio, raised a high level of concern about exposure to hazardous chemicals such as volatile organic compounds (VOCs) among residents. In this study, we measured urine metabolite levels of eight (8) VOCs collected five (5) months after the incident from 19 (19) nonsmoking East Palestine residents living within approximately one mile from the derailment site and compared them with levels from a comparison community and 2015–2016 National Health and Nutrition Examination Survey (NHANES) data. The samples were analyzed with a Thermo Altis LC–MS–MS system. Nearly 75% of East Palestine participants had detectable levels of a vinyl chloride metabolite, 2-hydroxyethylmercapturate (HEMA), whereas none of the comparison community participants had detectable levels and only 5% of NHANES participants had levels above the 3.0 ng/mL limit of detection (LOD). One East Palestine participant had a quantifiable level of the butyl acrylate metabolite, whereas none of the Marietta residents was above the LOD. The metabolite was not measured in the NHANES. The detection of metabolites of derailment-related chemicals supports the need for long-term follow-up of residents of this community and its surrounding area.
Abstract The growing use of biochar is increasing the release of biochar-derived dissolved organic matter (BDOM) in surface waters. Concurrently, remediation of persistent per- and polyfluoroalkyl substances (PFAS) remains challenging. Although natural DOM can both photosensitize and scavenge reactive species, how BDOM modulates PFAS transformation in waters is unclear. Here, we show that low-level BDOM (1 mgC L–1) unexpectedly promotes PFAS defluorination in the UV/sulfite (UV/S) system by simultaneously boosting hydrated electron (eaq–) production and generating oxidizing radicals via triplet states (3BDOM*). The hydrophilic, moderately condensed aromatic, fulvic/humic-like fraction of BDOM is most effective across all tested feedstocks and pyrolysis temperatures. BDOM derived at 500 °C raises eaq– yield 2.6-fold over UV/S alone while co-producing •OH. Crucially, BDOM appears to reroute the eaq–-mediated decarboxylation–hydroxylation–elimination–hydrolysis pathway: instead of water addition, •OH may directly attack perfluorinated radical, making key steps more thermodynamically favorable and accelerating C–F cleavage. Leveraging naturally derived BDOM in waters, this eaq–/•OH-mediated reduction-oxidation coupling may reduce reliance on externally added chemicals while achieving complete degradation of perfluorocarboxylic acids and GenX within 1 h and ∼80% defluorination within 6 h. The findings establish BDOM as an intrinsic photosensitizer and electron ejector that reshapes radical chemistry and PFAS reaction pathways, supporting more efficient and sustainable UV/S-based remediation.
Combined contamination of soils with thallium (Tl) and cadmium (Cd) is widespread. Despite comparable accumulation of Tl and Cd by rice plants, the mechanisms underlying significantly lower Tl concentrations than Cd in grains remain unclear. Here, pot experiments, rhizotron observations and field sampling were combined to investigate the fate of Tl/Cd across the soil-rice system. Sequential extraction shows that flooding decreased Tl/Cd mobility in bulk soil, with Cd enriched in the oxidizable fraction and Tl in the residual fraction. In the rhizosphere, planar optode and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) reveals that flooding induced iron-plaque formation, restricting rice Tl/Cd uptake compared with continuous drainage. Tissue- and microscale-level (LA-ICP-MS) analyses show that Tl transfer from node-to-leaf was 3.00-8.85 times that of Cd which exhibited greater upward translocation. In brown rice, 66.0-86.0% of Cd transported to grains was allocated to the endosperm. In contrast, Tl was preferentially enriched in the embryo, which represented only 1.78-2.66% of the biomass but contained 42.9-60.8% of Tl, potentially associated with high K demand and K-related transport pathways. Thus, contrasting shoot translocation and brown rice partitioning patterns of Tl/Cd explain differential grain concentrations, offering mechanistic insights for safe rice production.
Abstract Sunscreens are an important protection measure against harmful effects of ultraviolet radiation. However, potential health effects of several commonly used UV filters are currently being discussed. We conducted a human biomonitoring (HBM)-based exposure and risk assessment for octocrylene (OC), 2-ethylhexyl salicylate (EHS), and homosalate (HMS; a mixture of cis- and trans-HMS) in urine samples collected in Queensland and across Australia from 2012 to 2023, pooled by age, sex, and collection period (187 pools representing approximately 18,700 individuals). The pooled urines were analyzed by LC–MS/MS for specific exposure biomarkers of these UV filters. Determinants of exposure were investigated using Tobit regression. Biomarker concentrations increased over time, and clear age trends were observed, with children showing roughly one order of magnitude higher concentrations than adolescents/adults. Concentrations of the EHS biomarker 5cx-EPS exceeded the health-based guidance value (HBM-I) in 23% of children’s pooled urines. For the cis-HMS biomarker HMS-CA5, most pooled urines of children exceeded HBM-I (80%) and 53% even HBM-II. These findings indicate the need to reduce HMS exposure in at least some individuals, confirming the necessity for stricter regulations for homosalate in Australia, as recently enforced in the European Union and recommended by Australian authorities, to ensure sunscreen safety.
Abstract Triclosan (TCS) is a ubiquitous environmental contaminant known for its endocrine-disrupting and immunotoxic effects, yet its role in autoimmune diseases, including rheumatoid arthritis (RA), remains poorly understood. Here, we observed that serum TCS levels were significantly elevated in RA patients compared to healthy controls. In vivo, TCS dose-dependently aggravated collagen-induced arthritis in mice, with KEAP1 upregulation, synovial hyperplasia, and elevated serum TNF-α, IL-6, and IL-1β. In rheumatoid arthritis fibroblast-like synoviocytes (RA-FLS), TCS promoted a pro-inflammatory and aggressive phenotype with enhanced cytokine production, proliferation, migration, and invasion. Mechanistically, surface plasmon resonance (SPR) and cellular thermal shift assay (CETSA) confirmed direct TCS-KEAP1 binding (KD = 4.5 μM), supported by molecular docking (binding energy: −7.93 kcal/mol) and molecular dynamics (MD) simulations. This interaction led to KEAP1 upregulation, enhanced KEAP1-NRF2 binding, and NRF2 sequestration in the cytoplasm via a degradation-independent mechanism, impairing its nuclear translocation and transcriptional activity. Consequently, NRF2 blockade led to sustained oxidative stress and IL-17/MAPK/NF-κB cascade activation, which NAC rescue experiments validated as oxidative stress-driven. Critically, restoring NRF2 nuclear entry via KEAP1 silencing or NRF2 activation effectively reversed these pro-arthritic effects. These findings identify TCS as an environmental risk factor for RA that subverts the KEAP1/NRF2 redox checkpoint to perpetuate IL-17-mediated joint destruction.
Abstract Regulatory initiatives to mitigate plastic pollution face challenges in identifying microplastics and their sources. Recent advances in computational fingerprinting offer opportunities for the forensic investigation of plastic pollution sources. Here, we present an open-source computational workflow integrating multi-instrumental, nontargeted (organic and inorganic) data from three distinct mass spectrometry methods to evaluate two approaches for potential plastic pollution source tracking. The workflow includes a novel data imputation, normalization, and feature selection strategy with a Random Forest classifier applied to data sets of 42 pristine (store-bought) and 21 weathered (environmentally collected) plastics from U.S. retail products and California beaches. To develop a workflow for source identification, we first, evaluated an “Universal Fingerprint” approach, which tested whether chemical profiles from pristine, store-bought plastic products could be used to identify weathered environmental counterparts based on their chemical additive patterns. This approach yielded low classification accuracy due to high geographic and manufacturer-specific formulation variability for plastic products that the random forest model could not sufficiently resolve. Second, we evaluated a “Suspect–Source Comparison” approach that simulated a scenario where the chemical fingerprint of an environmentally sampled plastic was matched to the fingerprint of a suspect source. Under this paradigm, the workflow achieved a high classification accuracy across all platforms (up to 1.00 MCC for ICP-MS/MS and 0.79 for HPLC-QToF-MS). Additionally, we found that the different analytical techniques functioned best as complementary data sets to distinguish product categories, while combining all raw data sets prior to classification introduced excessive variability that hindered the classification. Our results demonstrate the feasibility of using relative chemical similarity to connect environmental plastics to potential local pollution sources. The presented workflow establishes a methodological foundation for localized source tracking, environmental litigation, and targeted regulatory monitoring.
Abstract Chemical compounds released from plastics are of great concern as some of them could be hazardous to the environment and human health. Recently, a hazard-based assessment was applied to an extensive data set of 16 325 known plastic chemicals (the PlastChem database). Using this approach, 4219 chemicals of concern were identified on the basis that they are persistent, bioaccumulative, mobile, or toxic. A small portion of the chemicals of concern (568) is already regulated globally; the rest of them (3651 chemicals) constitute the so-called Red List. Because of the enormous importance of the chemicals of concern, several articles published in high-impact scientific journals called for immediate action. They insist that the chemicals from the Red List should be regulated and curtailed within the scope of the forthcoming Plastic Treaty currently being developed under UNEA Resolution 5/14. Here, we report a critical overview of the Red List and show that about 30% of its entries appear questionable, which calls for further in-depth analysis and comprehensive revision of the list. Furthermore, we argue that the hazard-based assessment should serve only as an initial screening tool. The Red List of plastic chemicals of concern should also be subjected to risk-based assessment through tiered exposure filtering before adoption by any global regulatory framework.
Abstract Conventional membrane separation mechanisms based on size, charge, and valency cannot effectively differentiate between nearly identical transition metal ions such as cobalt, nickel, and manganese. To circumvent these fundamental limitations, we develop a cobalt-selective membrane that facilitates ion transport through specific ion–ligand coordination geometry, an underutilized separation mechanism in membranes. First, we fabricate and characterize a phosphonate-functionalized polyelectrolyte multilayer membrane designed to provide a sterically constrained coordination environment. Next, we evaluate ion flux and membrane selectivity in multisalt diffusion cell transport experiments, achieving Co2+/Ni2+ selectivity of ∼2.3, Mn2+/Co2+ of 1.9, and Zn2+/Co2+ of 17.3, and reversing selectivity expectations of the classical Irving–Williams stability series (Mn2+ < Co2+ < Ni2+ > Zn2+). Through isothermal titration calorimetry and density functional theory simulations, we demonstrate that the thermodynamically favorable binding of Co2+ over Ni2+ drives a coordinative “hopping” mechanism. Transport is governed by the ion’s ability to partially dehydrate and accommodate a distorted pseudo-octahedral geometry imposed by the rigid ligand matrix. These results establish coordination geometry as a promising driving force for the design of high-precision, ion-selective materials for critical mineral recovery.
Abstract Urban green space (UGS) is a promising nature-based solution for cardiovascular health, yet its associative pathways in pollution-saturated, high-density environments remain contested. We applied a two-stage framework combining gradient boosting decision trees and structural equation modeling to a clinical cohort of 23,312 patients in Nanjing, China. Air-quality-related pathways accounted for more than 75% of the relative statistical contribution to model variance, exceeding psychological restoration proxies. At the macroscale, the aggregated air-quality pathway showed a marginal positive coefficient; although this may conceptually resemble aerodynamic interference, the interpretation remains speculative because no morphological or fluid-dynamics data were available. Stage 2 models identified distinct protective associative networks. For chronic ischemic heart disease, vegetation vitality was inversely associated with NO2 and SO2 and was linked to more favorable metabolic markers. For heart failure, the vegetation condition was associated with mixed pollutants and hemodynamic-metabolic indicators. Age-stratified analyses suggested heterogeneity in canopy density-PM2.5 associations, but subgroup slopes were nonsignificant, and effect sizes were extremely small, indicating fragile relative fluctuations rather than structural reversal. These findings characterize UGS primarily as a biophysical modulator and support targeted ecological strategies in traffic corridors and aging communities.
Abstract Urban subway systems represent important yet understudied environments for human exposure to airborne microorganisms. Therefore, we conducted an investigation of air microbiome across 43 underground stations spanning 13 lines of the Shanghai subway. Using stratified cluster sampling, we simultaneously collected total suspended particles (TSP, aerodynamic diameter ≤ 100 μm) and fine particulate matter (PM2.5, aerodynamic diameter ≤ 2.5 μm) at station entrances, halls, and platforms, integrating microbial taxonomy, transcriptional potential, PM2.5 chemical composition, microclimate, and network topology. We found bacteria dominated both particle-size fractions and accounted for the majority of transcriptional signals, whereas eukaryotic taxa were strongly enriched in TSP, reflecting pronounced particle-size filtering. Although transcriptional potential generally increased with abundance, dominant taxa such as Staphylococcus and Bacillus exhibited weak abundance–transcription coupling, indicating functional decoupling between numerical dominance and transcriptional contribution in subway air microbiomes. Microbial diversity and community composition remained broadly homogeneous across the subway network, consistent with extensive passenger mobility and high network connectivity. In contrast, finer-scale heterogeneity emerged within stations, particularly for eukaryotic communities, which declined from entrances to enclosed platform environments. Environmental associated factors exhibited kingdom-specific patterns: bacterial and viral diversity were primarily associated with local microclimatic conditions, especially temperature, whereas eukaryotic diversity was more strongly linked to urbanization and externally derived aerosol inputs. Overall, these findings demonstrate that subway airborne microbiomes are shaped by interacting effects of particle-size filtering, environmental selection, and network-driven microbial mixing.
Abstract Biofouling is a persistent challenge in reverse osmosis (RO) desalination and water reuse because it accelerates flux decline, increases energy consumption, and drives chemical cleaning requirements. Developing durable antibiofouling interfaces is therefore critical for improving the sustainability of membrane-based water treatment. Here, we show that covalent installation of quaternary phosphonium functionality on polyamide thin-film composite (TFC) membranes provides a promising route to enhanced biofouling resistance while largely preserving desalination performance. Using a mild surface-grafting strategy, we immobilized quaternary phosphonium salts (QPS) on RO membrane surfaces and directly compared their behavior with that of structurally analogous quaternary ammonium salts (QAS). Surface analyses confirmed successful functionalization while preserving the characteristic morphology of the polyamide selective layer. Under optimized conditions, the QPS-modified membrane maintained NaCl rejection of ∼99% with only a limited permeance penalty. More importantly, QPS outperformed QAS in suppressing Escherichia coli, achieving 72.6% antibacterial efficiency versus 51.2%, and reduced surface-associated biomass more effectively under static conditions. In 24 h cross-flow filtration, the QPS-modified membrane retained ∼95–97% of its initial flux, compared with ∼66–68% for the pristine membrane. Comparative transcriptomic profiling revealed distinct bacterial response states on QPS- and QAS-functionalized membranes, with QPS eliciting a stress-responsive, membrane-adaptive program and QAS promoting a low-activity, translation-repressed state. These results identify phosphonium-based interfaces as an effective design strategy for reducing RO biofouling and advancing more energy-efficient, chemically resilient water treatment systems.
Abstract Although the link between seasonal influenza and environment has been established, the heterogeneous impacts of climate extreme events with their interactions remain poorly understood. Based on 630,120 influenza-positive cases from hospitals in 335 Chinese cities (2005–2019), this case-crossover study adopted distributed lag nonlinear models to quantify exposure-lag-response relationships between environmental exposures and influenza, applied machine learning to rank dominant variables, and performed a Long Short-Term Memory (LSTM) model using Beijing as proof of concept to test the forecasting utility of extreme events. Meteorological variables, air pollution, and extreme events are significantly associated with influenza risk. Machine learning models indicate that atmospheric temperature, humidity, and particulate matter may be the primary contributors. Co-exposure to extreme events showed a higher joint risk than single exposure, with a significant submultiplicative interaction on the multiplicative scale and no evidence of additive interaction. Based on the Beijing-specific LSTM proof-of-concept framework, integrating extreme events significantly enhanced daily influenza forecasting performance. Climate factors, air pollution, and extreme events potentially shape influenza risk, with heterogeneous effects across subtypes, demographics, and geography. These findings underscore the potential benefits of integrating extreme climate events into influenza forecasting and precise public health responses in the era of climate change.
Abstract Vehicle-to-grid (V2G) is an important flexibility management technology for lower-carbon transport and the electricity grid. However, its effectiveness relies on the temporal alignment between the price incentives and grid dynamics. To overcome the challenge of coordinating electricity pricing with V2G deployment, we integrated a Bayesian optimization framework into a unit commitment model of the 2030 Jing–Jin–Tang power grid. Results demonstrate that current static time-of-use tariffs incentivize EV fleets to discharge during midday solar peak hours. This behavior displaces zero-marginal-cost renewable generation and forces pumped storage hydropower units to absorb excess fleet discharge. Optimizing tariffs could reduce average net load, operating costs, and CO2 emissions. In summary, the synergistic interaction between V2G and dynamic pricing shows a dual effect: it reduces costs for both the grid and EV owners but, conversely, can increase CO2 emissions due to excessive EV participation. Our results demonstrate that a shift toward dynamic, carbon-aware pricing mechanisms is essential to ensure that widespread V2G deployment effectively supports decarbonization goals.
