Despite stringent SO2 emission reductions, particulate sulfate (SO42-) concentrations often exhibit a nonlinear response. To reconcile this discrepancy, this study utilized synchronous sulfur isotope (δ34S) observations of precursor SO2 and product sulfate in Nanjing across a decade (winter 2015 vs 2024). Sulfate reductions are observed to lag behind SO2, declining together with elevated δ34S values in ambient sulfate (5.7 ± 1.1‰ vs 6.2 ± 1.3‰) and significantly in SO2 (1.4 ± 1.2‰ vs 6.5 ± 1.6‰), which indicates a shift in emission structure and sulfate formation chemistry. Unexpectedly, while SO2 source apportionment demonstrates a significant decline in contribution of coal combustion to regional SO2 emissions, coal combustion remains the predominant contributor to secondary sulfate, maintaining a stable relative share. This discrepancy implies enhanced conversion efficiency for coal-emitted SO2. We attribute this to the increased contribution of co-emitted transition metal ion (TMI)-catalyzed oxidation (rising from 35.6% to 59.0%), with kinetic calculations underscoring the dominance of the Mn-surface catalysis pathway. Ultimately, these findings suggest that intensified TMI-catalyzed oxidation sustains high sulfate production from coal-emitted SO2 even under low-SO2 conditions, providing a mechanistic explanation for the nonlinear response. These results also highlight the necessity for synergistic co-control strategies within coal-dependent industries.

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.

Urban airborne spores and pollen serve as valuable bioindicators for assessing biodiversity and ecosystem health. Traditional monitoring approaches predominantly correlate spore-pollen dispersal dynamics with meteorological variables, largely overlooking their intrinsic biological attributes and evolutionary context. This study adopted an evolutionary ecology framework to investigate the temporal dynamics of airborne spores and pollen in Kunming, a subtropical plateau city in China. Integrating one-year gravimetric sampling with eDNA metabarcoding, we analyzed how regional phylogenetic history, local vegetation structure, seasonal climate, and basin topography jointly shape urban spore-pollen spectra, assessed the relative contributions of biotic drivers versus abiotic factors in governing dispersal patterns, and evaluated whether phylogenetic diversity reflects biotic homogenization in airborne spore-pollen communities. Our findings demonstrated that biotic factors, especially spore-pollen grain morphology and floral traits, possessed greater explanatory power for dispersal dynamics than meteorological variables. The airborne spore-pollen assemblage exhibited remarkably high phylogenetic diversity, with a significant phylogenetic signal detected in key functional traits, suggesting limited community similarity and apparent evolutionary constraints. These results challenge the prevailing abiotic-centric perspective, repositioning airborne spores and pollen as evolutionarily constrained biological entities rather than passive atmospheric particles. This framework advances spore-pollen monitoring from descriptive abundance records to process-based evolutionary indicators, offering novel tools for urban biodiversity assessment and for forecasting plant community responses to ongoing climate and land use change.

Advanced oxidation processes are indispensable for water remediation yet face a fundamental activity-selectivity trade-off, where reactive species are competitively quenched by complex aqueous matrices. While surface-confined chemistry, specifically utilizing surface-adsorbed hydroxyl radicals (•OHads), provides an appealing kinetic strategy to shield reactions from bulk-phase scavengers, its generation typically requires substantial energy inputs. Here, we report the spontaneous evolution of •OHads via a lattice-engineered 2D CeO2/βC3N4, comprising bilayer CeO2 and monolayer β carbon nitride (βC3N4). Unlike conventional CeO2, where surface Ce4+ sites are blocked by stable oxygen terminations (i.e., Ce4+═O), the unique architecture of CeO2/βC3N4 stabilizes reactive Ce4+ sites via a surface superoxide layer (i.e., Ce4+-•O2-). Upon dispersion into an aqueous system, this superoxide layer undergoes rapid protonation, exposing accessible Ce4+ sites for water oxidation to generate •OHads. Complementary in situ characterizations, isotope-labeled mass spectrometry, and theoretical calculations reveal thermodynamically favorable and stoichiometrically balanced one-electron oxygen reduction and water oxidation pathways, enabling self-sustaining Ce4+/Ce3+ redox cycling and continuous •OHads generation. This work establishes a pollutant-triggered paradigm for matrix-resilient water remediation by leveraging •OHads, eliminating the need for chemical additives or external energy inputs.

The plastisphere is an emerging anthropogenic ecosystem hosting complex microbial assemblages. While heterotrophic colonizers are well studied, the role of primary producers such as cyanobacteria remains underexplored. Here, we reanalyzed 16S rRNA gene amplicon data from 3160 plastisphere samples across 62 aquatic studies to assess their role in community assembly at a global scale. Substrate type explained a significant but relatively small fraction of variation (R2 = 0.048), whereas β-diversity showed clear separation between marine and freshwater communities. Among all substrate types (plastic, microplastic, natural polymer, and nonplastic), plastic-associated communities exhibited the highest estimated contribution of deterministic assembly processes in both freshwater and marine ecosystems. Co-occurrence networks showed low modularity and high clustering, revealing recurrent community association patterns across plastisphere data sets, while several topologically central taxa exhibited frequent associations with cyanobacteria. Notably, Xenococcaceae and Phormidesmiaceae were consistently enriched on plastics relative to surrounding environments. Independent metagenomic analyses corroborate enrichment of Phormidesmiaceae. These results demonstrate recurrent cyanobacterial enrichment in plastisphere communities and identify co-occurrence patterns between cyanobacteria and heterotrophic taxa. These associations generate hypotheses regarding possible phototroph-heterotroph linkages on plastic surfaces that warrant experimental investigation.

The global demand for critical minerals and materials (CMM) is rapidly outpacing conventional supply chains. This Perspective presents a paradigm shift by demonstrating that mature U.S. sedimentary basins are not merely depleting fuel reservoirs but are vast, accessible repositories of mineral wealth. By integrating in-situ mining (ISM) chemistries into existing oil and gas infrastructure, we can leverage billions of dollars in sunk capital to address modern supply chain bottlenecks while simultaneously enhancing energy recovery. Our analysis of 13 U.S. hydrocarbon reservoirs identifies 15 critical elements, including titanium, vanadium, nickel, cobalt, etc., ubiquitous within the sedimentary matrix. We highlight that 1% enhanced recovery rate of hydrocarbon from the existing reservoirs and 1% recovery rate of CMM from 5% of these accessible formation volumes could yield over 530 million barrels of oil, 6 Tcf natural gas, and 500 million metric tons of CMM, providing scale context for the potential energy and material significance of sedimentary coproduction. Future research should focus on optimizing selective lixiviants that maintain reservoir integrity while maximizing yields of CMM and hydrocarbons within a closed-loop system. Redefining the Earth as a Reactor offers a pragmatic and low-footprint pathway to secure national industrial competitiveness and advance technological leadership.

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.

Birnessite (δ-MnO2) is a redox-active mineral that mediates the abiotic oxidation of organic contaminants, yet how freezing alters its structure and reactivity remains unclear. Here, we show that freezing induces the formation of Mn vacancies (VMn) in δ-MnO2 and markedly enhances its oxidative reactivity. δ-MnO2 after freezing exhibited a 9.5-fold higher oxidation rate toward bisphenol A (BPA) than pristine δ-MnO2, and the reactivity increased further with freeze-thaw cycles. During freezing, δ-MnO2 particles concentrate in liquid-like regions between ice crystals, creating conditions favorable for defect formation. In situ XAS reveals that freezing increases the average Mn oxidation state while decreasing local Mn coordination, with ex situ XAS, XPS, Raman, and EPR analyses further supporting VMn formation. Accordingly, VMn formation decreases the proportion of Mn(III) and increases that of Mn(IV), which strengthens Mn-O bonding and enhances the oxidative capacity of δ-MnO2. Electrochemical analysis and theoretical calculations further show that VMn tunes the electronic structure of δ-MnO2 and promotes interfacial electron transfer. These findings offer new insight into freezing as a previously overlooked driver of manganese oxide reactivity, with implications for contaminant transformation and natural self-purification in cold regions.

With around 9600 biogas plants, Germany has the largest biogas sector in Europe, where methane (CH4) losses can substantially counterbalance the climate benefits of this renewable energy source. Nevertheless, comprehensive empirical data on CH4 emissions and loss rates across different plant sizes and configurations in Germany remain limited. In this study, we quantified CH4 emissions at 65 biogas production sites using mobile measurement surveys combined with Gaussian plume dispersion modeling. Observed emission rates varied between 0.3 and 255 kg CH4 h-1, corresponding to size-dependent CH4 loss rates. Small plants averaged substantially higher losses of the produced CH4 (∼8.8%), whereas medium and large plants as well as upgrading facilities showed lower, more consistent loss rates of 2.9-4.3%. Using two different upscaling approaches, we estimate that German biogas plants emit approximately 360-370 kt CH4 yr-1, contributing ∼23% of Germany's total CH4 emissions. These sector-wide emissions exceed bottom-up estimates, highlighting a systematic underestimation in current inventories. Our results represent one of the most comprehensive measurement-based assessments of CH4 emissions from German biogas infrastructure to date, showing that this method could improve national CH4 budgets, and develop and verify mitigation strategies. The observed emissions further underscore the need for leak reduction and mitigation measures to preserve the climate benefits of biogas plants.

The iron and steel industry is central to industrial decarbonization and air-quality improvement, yet the energy-industrial conditions shaping these outcomes remain insufficiently understood. We develop a unit-level emission database for China's steel industry, covering 2866 enterprises and ∼4030 units, to relate regional energy-industrial configurations to historical driving mechanisms and future mitigation priorities. The sector's CO2 emissions peaked at 1.99 gigatonnes in 2019, while SO2 and PM declined by more than 80% during 2011-2022. Over 2023-2050, production restraint provides the largest projected cumulative CO2 reductions (22.1%), whereas obsolete capacity retirement dominates air pollutant (AP) reductions (22.3%). These priorities vary across regional configurations, exemplified by the greater relevance of process upgrading and capacity restructuring in high-intensity regions. Combined mitigation could lower CO2 intensity to below 1.5 t/t by 2030 and ∼0.6 t/t by 2050. Regionally differentiated pathways may also induce spatial emission leakage, more strongly for CO2 than for APs, although the CO2 leakage ratio declines from 17.39% in 2030 to 2.38% in 2050. Air-quality responses are similarly uneven, with national mean AP concentrations in 2030 decreasing by 5.4-12.3% relative to 2022. The findings suggest that long-process-dependent steel economies require sequenced, regionally differentiated transitions beyond uniform short-process substitution.

Enhanced weathering has gained attention as a promising CO2 removal (CDR) practice, but previous life cycle analyses rely on theoretical assumptions that differ substantially from experimental observations and overlook the risks of heavy metal emissions. Here, we draw on data from existing empirical studies to conduct a prospective life cycle assessment of multiple enhanced weathering scenarios. Our results indicate that experimental weathering rates lead to delayed climate benefits, with a median 11 year lag between rock application and the onset of net CDR for inland scenarios starting in 2030. This carbon payback period results from the initial peak in greenhouse gas emissions associated with the rock supply chain and processing activities. Furthermore, our probabilistic analysis indicates that basalt-derived zinc emissions to agricultural soil could pose a greater toxicological risk than nickel release from dunite in the long term, potentially offsetting the health cobenefits of CDR and challenging the prevailing assumption that basalt is a safer feedstock-both on a per-mass-of-rock and a per-CDR basis. These findings suggest that the commercialization of CDR credits should be preceded by a thorough evaluation of near-term net climate benefits, and deployment should prioritize nonagricultural areas until the risks of food chain contamination are better understood.

Surface ozone is a persistent air pollutant in China, threatening crop production and public health, while existing controls on industry and transportation cannot effectively curb its increasing trends. Here, we show that mitigating nitrogen oxides (NOx) emissions from agricultural machinery is as effective as cropland soil nitrogen management in reducing ozone pollution, but is largely overlooked. Using a new machinery emission accounting model and meta-analysis, we estimate that agricultural machinery and cropland soils emitted approximately 0.55 Tg N yr-1 of NOx in 2020. By 2050, in a clean scenario, these emissions are projected to be 0.51 (0.40-0.71) Tg N yr-1 of NOx, contributing >30% of total NOx emissions from both anthropogenic and natural sources during the crop-growing season. The transition of agricultural machinery toward renewable energy could reduce emissions by 0.18 Tg N yr-1, exceeding the mitigation potential from nitrogen management (0.11 Tg N yr-1). Under a stringent emission control scenario aligned with the carbon neutrality goal, these interventions reduce mitigable ozone (MO3; the fraction of surface ozone attributable to domestic anthropogenic emissions) by 15-30% and episode days (>61 ppbv) by 20-50% in eastern China, preventing ∼12.7 Mt of crop losses and ∼59,800 premature deaths annually, valued at $82.4 ± 17.5 billion. With an implementation cost estimated at $36.7 ± 20.8 billion, net societal benefits reach $45.8 ± 38.3 billion, underscoring agricultural NOx control as a feasible multibenefit strategy for air quality, food security, and public health.

Pyrolytic remediation of petroleum-contaminated soil (PCS) often requires high temperatures, which increase energy demand, limit resource recovery, and impair post-treatment soil functionality. This high-temperature dependence reflects not only the cracking resistance of heavy hydrocarbons, but also strong oil-soil interfacial locking that restricts their release and conversion. Here, we tested whether targeted interfacial regulation could lower remediation severity in PCS by using functionalized artificial humic acid (FAHA) as an interface-active mediator. Potassium citrate and lignin directed the molecular evolution of artificial humic acid, while Fe complexation introduced additional reactivity during pyrolysis. Under optimal conditions, FAHA2 at 0.5 wt % lowered the remediation threshold from 480 to 390 °C. Multiscale analyses suggested that FAHA reorganized the oil-mineral interface, weakened direct mineral-petroleum interactions, and facilitated lower-temperature release of interfacially constrained petroleum fractions. During pyrolysis, FAHA-bound Fe likely evolved from Fe-S-associated with Fe-O-rich coordination environments that could further facilitate hydrocarbon conversion. Compared with direct high-temperature pyrolysis, the FAHA-assisted pathway better preserved soil functionality and showed a lower estimated gross process-carbon burden under the defined accounting boundary. These results highlight sequential interfacial-thermochemical coupling as a design principle for more sustainable remediation of interface-dominated contaminated matrices.

High-throughput in vitro cell assays are promising tools for predicting chemical-induced health effects in humans. Quantifying freely dissolved medium (Cfree,medium) and cellular concentrations is essential for robust quantitative in vitro-in vivo extrapolation (QIVIVE), but the miniaturized format of 384- and 1536-well plates makes these metrics challenging to measure directly. We developed DYNAMEX (dynamic NAM exposure), a time-resolved kinetic model simulating chemical fate in cell assays, accounting for volatilization, medium binding, well-plate sorption, and cellular uptake, including growth dilution. The model accurately captured uptake kinetics for neutral compounds and newly measured PFAS cellular uptake kinetics, reproduced empirical thresholds for volatilization losses, and predicted free fractions in medium across 51 compounds (RMSE = 0.49 log10 units) and cellular-to-nominal concentration ratios across 17 compounds (RMSE = 0.56 log10 units) under different bioassay conditions. Simulations across 113 chemicals and varying assay setups showed that, under standard assay conditions using 10% FBS, equilibrium mass balance modeling predicted Cfree,medium within 10% for 83 of 113 compounds and is sufficient for most applications. Kinetic modeling is required when volatilization or well-plate sorption causes substantial mass losses, particularly under serum-free conditions and in miniaturized formats, or when low membrane permeability limits cellular uptake within the assay duration, as observed for several hydrophobic ionizable organic chemicals. The model provides a mechanistic framework to improve in vitro dosimetry, guide assay design, and support integration of time-resolved exposure metrics into QIVIVE and in vivo modeling workflows.

Seaweed farming is increasingly recognized for its potential role in ocean carbon dioxide removal, yet the fate of small suspended particulate organic carbon (sPOC, 0.7-20 μm) released during macroalgal growth remains poorly constrained. Here, we investigated sPOC production, transformation, and microbial persistence in Sanggou Bay, China, one of the world's most intensive Saccharina japonica cultivation systems. During the farming season, sPOC concentrations increased by 103.4% and 117.0% in surface and bottom waters, respectively, relative to the nonfarming period, accompanied by shifts in sPOC molecular composition toward kelp-derived signatures. In situ mesocosm experiments showed increasing sPOC release with kelp development, reaching 13.4-63.5 μmol L-1 over 64 h across growth stages. The 180-day microbial incubations revealed that 18.1-55.6% of kelp-derived sPOC was retained in three microbially persistent carbon pools: recalcitrant sPOC (R-sPOC; 7.6-27.3%), recalcitrant dissolved organic carbon (4.6-9.7%), and bicarbonate-associated inorganic carbon (5.9-18.6%). Residual R-sPOC exhibited molecular characteristics associated with enhanced microbial resistance, with formula-level evidence of direct kelp release and microbial transformation (48.2% and 51.8%, respectively). These findings identify sPOC as a neglected, mechanistically distinct carbon-retention pathway in seaweed farming and provide a basis for assessing its potential contribution to longer-term blue carbon sequestration.