Abstract Zero liquid discharge (ZLD) enables water and salt recovery while preventing secondary pollution, yet it is often energy-intensive and costly. Electrodialysis (ED), a widely employed technology for brine concentration in ZLD, is still in progress to overcome its insufficient concentrating ability due to unrestricted water transport through ion-exchange membranes. In this study, a tailored subnano-confined membrane (SCM) was prepared using a commercially available nanofiltration membrane and an ion exchange polymer. The ED system equipped with the SCM achieved a high concentration difference of 185 g L–1 NaCl in a single-stage operation and further produced crystallized NaCl at the third stage, offering a much simplified and effective concentrating process. The SCM featured ultralow water permeance, and the hydration number of ions passing through it was substantially reduced, which contributed to its superior salt-concentrating ability. Further analysis recognized that the unique structure of SCM that comprised subnano channels was the major contributor to its strong ion dehydration effect. This research is expected to advance ZLD toward enhanced energy efficiency, streamlined processes, and cost-effectiveness.
Abstract Nitrous acid (HONO) is a vital precursor for hydroxyl (OH) radicals in wildfire plumes, yet chemical transport models often underrepresent observed in-plume HONO levels. We implemented wildfire HONO emissions and literature-based secondary formation pathways in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) and evaluated simulations against airborne measurements from the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign during 2019 summer wildfires in the northwestern United States. The revised model substantially improves in-plume HONO representation. Source attribution revealed that emissions contributed up to 40% of HONO in near-source smoke, while heterogeneous NO2 uptake on aerosol surfaces acted as the dominant pathway (47%–74%) due to the dense reactive surface area of smoke aerosols. HONO photolysis accounted for approximately 80% of the primary OH production in the near-field smoke, identifying HONO as the leading primary radical-initiation pathway during this stage of plume evolution. HONO-initiated radical production further accelerated radical cycling, yielding a net increase in O3 concentrations both near the surface and at the plume transport altitude. Our findings underscore the pivotal role of HONO in driving smoke-plume chemical evolution and highlight its importance for assessing regional air pollution and tropospheric O3 burdens.
Abstract Building lifetime is a foundational parameter for modeling stock dynamics, informing environmental impact assessment and urban development, yet current lifetime assumptions frequently lack empirical grounding. Although well-established in medicine and demography, survival analysis concepts have not penetrated building stock research to the same extent. This study bridges this gap through a systematic review and meta-analysis of 258 median building lifetime estimates across 46 global studies. Central to our analysis is right-censoring, when a building’s demolition remains unobserved at the end of the observation period, which, if unaccounted for in estimation, leads to underestimated lifetimes. We systematize five estimation approaches based on data type and the capacity to account for right-censoring, describe the currently available empirical evidence, and apply a meta-regression to identify significant predictors of median lifetimes: world region, use class, structural material, and right-censoring bias, the latter underestimating building lifetimes by 50% (95% CI: 49–51%). Of the five estimation approaches identified, three inherently consider right-censoring, one inherently cannot correct for it, and one requires an active correction step that is frequently omitted. Our work identifies critical data gaps and offers targeted recommendations for users and producers of lifetime estimates to improve transparency, reproducibility, and methodological rigor.
Abstract The interaction between organic carbon (OC) and reactive iron (FeR) plays a critical role in suppressing OC mineralization, with the resulting FeR-bound OC (FeR-OC) constituting an important carbon sink in marine sediments. Traditional views suggest that under anoxic conditions, associations between FeR and OC not only enhance the OC accumulation and persistence but also inhibit the reductive dissolution of FeR. However, this framework leaves unresolved uncertainties regarding how FeR and OC mutually promote their costabilization under anoxic conditions. In this study, sequential chemical extraction was employed to distinguish organically complexed iron-bound OC (Fep-OC) from iron-oxide-bound OC (Feox-OC). Our results reveal that Fep represents a previously underrecognized iron-associated OC pool that contributes to the OC preservation in marine sediments. Under anoxic conditions, Fep promotes OC retention and offsets the decline in Feox-OC. Despite its lower abundance, Fep accounts for the stabilization of an average of 20.59% of the sedimentary OC. Fourier transform infrared spectroscopy (FTIR) analyses further indicate that Feox-OC is relatively enriched in aromatic and alcohol/phenol functional groups compared with bulk OC, whereas Fep-OC exhibits no distinct enrichment of specific functional groups. Collectively, this study provides field-based evidence for the redistribution of OC among different FeR-bound fractions and highlights the potentially important contribution of Fep to OC preservation under anoxic conditions.
Abstract Antibiotic resistance genes (ARGs) have profoundly exacerbated environmental risks to public health, evolving into a pressing ecological dilemma. Distinct from traditional pathways, outer membrane vesicles (OMVs) are emerging as important vectors for horizontal gene transfer (HGT) in aquatic environments, yet their role in inter-phylum ARG dissemination remains unclear. In this study, we demonstrate that OMVs mediate bidirectional HGT of ARGs between the cyanobacterium Synechocystis sp. PCC 6803 and Escherichia coli DH5α. Co-incubation experiments confirmed that OMVs derived from either strain could associate with the other, accompanied by successful functional expression of transferred resistance genes. In simulated aquatic environmental conditions, OMVs supplementation increased HGT frequency by 1.49–2.27 folds compared to the control group on day 5. Metagenomic analysis further revealed that OMVs carrying resistance genes induced subtle shifts in coastal microbial community composition. Our findings establish OMVs as mobile genetic packages that enable ARGs exchange between cyanobacteria and heterotrophic bacteria, highlighting a previously overlooked pathway for environmental dissemination of ARGs and providing a theoretical basis for mitigating antibiotic resistance risks in aquatic ecosystems.
Abstract 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.
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.
Ammonia toxicity represents a primary biochemical bottleneck governing microbial community structure and performance during the anaerobic digestion of the organic fraction of municipal solid waste. However, the mechanistic basis of microbial adaptation to chronic ammonia levels remains poorly characterized. In this study, a long-term sequential enrichment strategy under progressively increasing ammonia concentrations (350-1500 mgN L-1), integrated with genome-centric metagenomics and metatranscriptomics, was employed to resolve the response of an organic waste-degrading microbiome over a 240 day period. Increasing ammonia pressure induced a progressive decline in methanogenesis and accumulation of volatile fatty acids, particularly acetate. Despite these inhibitory pressures, methane production was only halved relative to the initial baseline reflecting a resilient methanogenic community. This stability was driven by a restructuring of the microbiome, where functional redundancy across divergent taxa preserved core metabolic functions. Key adaptive responses included the reconfiguration of carbon fixation pathways, specifically via a variant of the Wood-Ljungdahl pathway coupled with the glycine cleavage system acting as an alternative acetate oxidation route, as well as sustained osmoprotectant biosynthesis. Cellular homeostasis was preserved through H+ replenishment via multiple energy-converting complexes and K+ influx to maintain cation-proton balance. Collectively, these findings demonstrate that metabolic plasticity and the preservation of core metabolic functions are the primary determinants of ammonia resilience, sustaining methane production under inhibitory conditions.
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.
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.
Seagrass- and macroalgae-vegetated coastal sediments are critical carbon sinks but also methane (CH4) sources. Vegetation shifts between seagrasses and macroalgae modulate sediment biogeochemistry, yet their impacts on CH4 production and microbial controls remain poorly resolved. We conducted 106 day incubations of coastal sediments amended with graded loadings of seagrass, macroalgae, and their mixtures. Integrated CH4 monitoring, Gompertz modeling, 16S rRNA gene amplicon sequencing, PCR amplification of mcrA genes and mcrA transcript demonstrated that macroalgae amendment resulted in more rapid dissolved organic carbon release, earlier CH4 accumulation, higher CH4 yields, and stronger methanogen enrichment. Conversely, seagrass decomposition proceeded more gradually and was associated with comparatively weaker methanogenic responses. Mixed organic matter inputs enhanced CH4 production relative to single-source amendments, although this positive priming effect weakened with increasing macroalgae proportions. SHAP analysis further suggested that organic carbon availability and nutrient stoichiometry jointly influenced microbial carbon utilization and priming responses. Microbial succession closely tracked changes in sediment geochemistry and CH4 accumulation. These findings suggest that shifts in coastal vegetation composition may substantially alter CH4 production potential by modifying organic matter decomposition dynamics and microbial succession. This study establishes a quantitative framework for predicting CH4 emissions under scenarios of expanding, mixed seagrass-macroalgae ecosystems.
Air pollution control has lowered major criteria pollutants, yet airborne organic pollutants remain understudied, particularly regarding biomarkers and risks in pregnancy. We characterized 20 urinary biomarkers of airborne organic pollutants, including p-phenylenediamines, nitrated polycyclic aromatic hydrocarbons, phenylguanidines, benzothiazoles/benzotriazoles, and cotinine, in pregnant women from the prospective Towards Improved Maternal and Fetal health via Multipoint Exposure Monitoring (TIMFEM) study in China. Morning urine samples were analyzed by LC-MS/MS. Epidemiologic associations were integrated with in vitro screening in human trophoblast cells using a leave-one-out approach at human-exposure-guided doses. Among 1425 mother-infant pairs, 18 biomarkers were detected in >40% of participants. Each natural log-unit increase in N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) and its quinone (6PPD-Q) was associated with 27% and 23% higher risk of small-for-gestational-age (SGA), respectively. Mixture models identified 1,2,3-triphenylguanidine (TPG), cotinine, and 1-aminopyrene as additional key contributors. Although seven priority pollutants showed minimal effects on cell proliferation, they reduced pyruvate entry into the tricarboxylic acid cycle and limited isocitrate-to-α-ketoglutarate conversion, indicating impaired placental energy metabolism. Overall risk ranking highlighted cotinine, TPG, and 6PPD-Q. Maternal coexposure to airborne organic pollutants was associated with elevated SGA risk, with metabolic disruption, rather than acute cytotoxicity, suggesting a plausible mechanistic pathway.
Biodegradable plastics like polybutylene adipate terephthalate (PBAT) are increasingly marketed as alternatives to conventional plastics, yet how soil properties regulate degradation kinetics, how intact films and microplastic fragments differentially affect microbial communities, and which metabolic pathways and functional genes govern mineralization remain unclear. The present study investigated PBAT degradation mechanisms in 10 distinct agricultural soils by integrating metagenomics, microbial community analysis, and strain isolation. The results revealed that the environmental fate of PBAT is critically modulated by soil properties. Neutral-alkaline powdery loam soils exhibited the highest degradation efficiency. Soil physicochemical properties indirectly modulate PBAT weight loss by altering the gene abundance of hydrolases and aromatic-degrading enzymes, with soil nitrogen content serving as a key regulatory factor. Metagenomic correlation analysis suggests that PBAT degradation is associated with specific microbial consortia, including Hydrogenophaga and Ascomycota fungi. Microplastic particles of PBAT induced greater disturbances than intact films, as evidenced by significant reductions in microbial diversity, altered community structure, and shifts in functional gene composition. A complete degradation pathway, including initial polymer cleavage followed by terephthalic acid assimilation via the β-ketoadipate pathway, was elucidated. These results provide mechanistic insights into soil-specific PBAT degradation and facilitate risk assessment and sustainable management of biodegradable plastics.
Soilization of bauxite residues offers a scalable route for long-term carbon management and ecological restoration. However, the microbial processes that transform exogenous organic inputs into stable soil-like carbon pools remain poorly resolved. Here, we combined cross-ecosystem meta-analysis, machine-learning prediction, native synthetic community (SynCom) construction, 13C-labeled straw microcosms, field validation, Fourier transform ion cyclotron resonance mass spectrometry, and genome-resolved metagenomics to unravel microbiome-mediated carbon transformation at the dissolved organic matter (DOM) molecular scale. Our meta-analysis revealed that alkaline industrial wastes retained soil-like DOM signatures but were enriched in microbial humic- and protein-like components, indicating active yet incomplete carbon processing. Guided by these patterns, native SynCom inoculation increased 13C incorporation into total organic carbon (TOC) and dissolved organic carbon (DOC), enlarged biodegradable and adsorbable DOC fractions, and shifted DOM from recalcitrant aromatic pools toward oxygenated carbohydrate-, tannin-, and phenolic-like molecular classes. Genome-resolved analyses linked this transformation to complementary polymer degradation and nutrient-cycling functions across fungal and bacterial guilds, including enriched carbohydrate-active enzymes in straw-carbon-utilizing metagenome-assembled genomes. Null model and thermodynamic analyses further showed that microbial communities were constrained by homogeneous selection, whereas DOM molecules were diversified through variable selection and redox-dependent transformation. Field-scale validation confirmed that SynCom promoted TOC and DOC accumulation and humic-like, high-density DOM fractions under alkaline conditions. Together, these findings establish a mechanistic framework in which functional microbiomes couple plant carbon depolymerization, DOM molecular diversification, and mineral-interactive carbon stabilization, providing a microbiome-guided strategy for carbon sequestration and soilization in the bauxite residue.
The challenge in enhancing the room-temperature catalytic oxidation (RTCO) performance of formaldehyde (HCHO) lies in strengthening the ability to activate oxygen. This study synthesized a NiFe/Mn-MOF-74 composite with abundant oxygen vacancies (OVs) and surface hydroxyl groups through an in situ growth strategy. This composite material not only inherits the strong capture capacity of the layered double hydroxides (LDHs) surface hydroxyl groups for HCHO but also generates reactive oxygen species such as O2- and O- by introducing high-density OVs to activate oxygen molecules. Density functional theory (DFT) calculations indicate that the synergistic interaction between OVs and surface hydroxyl groups significantly promotes the adsorption of O2 (-2.93 eV) and HCHO (-3.31 eV). In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results further reveal the reaction pathway, in which HCHO is converted via intermediates such as formate and carbonate and is ultimately mineralized into CO2 and H2O. In a 35 L reactor simulating an indoor environment, the optimized 0.25 NiFe/Mn catalyst achieved 93.30% HCHO mineralization, retaining good stability throughout 1800 min of cyclic operation. This study elucidates the synergistic mechanism between OVs and surface hydroxyl groups in the composite material during RTCO of HCHO and advances the fundamental understanding of this reaction process.
Methane production by a biogas digester is a promising alternative to the use of fossil fuels as an energy source. One major substrate for methanogenesis is acetate, which is directly used by acetoclastic methanogens. At high pH and high ammonium concentrations, acetoclastic methanogenesis is inhibited, and acetate is oxidized to H2 + CO2, which are used by hydrogenotrophic methanogens. From such a digester, an ammonium-tolerant syntrophic acetate-oxidizing bacterium, Tepidanaerobacter acetatoxydans, was isolated in 2011 by Westerholm and colleagues, but its physiology and role in a biogas digester are still relatively unknown. We demonstrate that T. acetatoxydans is an acetogenic bacterium using an unusual Wood-Ljungdahl pathway (WLP) lacking a formate dehydrogenase. Therefore, T. acetatoxydans cannot ferment glucose, H2 + CO2, or CO + CO2, but the addition of formate restored acetogenesis. T. acetatoxydans could also grow on methyl groups that were oxidized in the WLP, but due to the absence of a formate dehydrogenase, methyl groups were incompletely oxidized to formate instead of CO2 as an end product. This study gives new insights into the physiology of acetogens that lack formate dehydrogenases and sheds new light on the role of T. acetatoxydans in the food web of a biogas digester.
Geological carbon storage performance depends not only on how much CO2 is emplaced but also on how CO2 is organized at the pore scale. Here, we use synchrotron micro-CT imaging under reservoir conditions to quantify CO2 saturation, cluster connectivity, and interfacial geometry during steady-state fractional-flow drainage and imbibition in a sandstone core. Measurements compared a surfactant-free reference case with an interfacially tuned case using dilute, water-soluble nonionic surfactant in the brine. Interfacial tuning increases CO2 occupancy during co-injection, raising drainage saturation at high CO2 fractional flow from 5.8% to 14.9% and the CO2-only end point saturation from 18.9% to 26.2%. Importantly, topology responds in a regime-dependent, nonmonotonic manner: connectivity dominance increases during co-injection, whereas at the CO2-only end point, additional CO2 distributes among multiple clusters rather than reinforcing a single backbone, demonstrating decoupling between occupancy and connectivity dominance. Upon flow reversal, the two conditions exhibit contrasting connectivity-hysteresis pathways, indicating distinct CO2 reorganization during imbibition. Interfacial metrics support this interpretation, with the tuned case showing 90% larger CO2-brine interfacial area and 44% lower mean curvature. These results show that interfacial tuning can increase CO2 saturation while producing different connectivity outcomes, underscoring the need for topology-resolved metrics to assess storage efficiency and security.
Growing demand for electric vehicles has intensified the need for sustainable recovery of critical metals from end-of-life lithium-ion batteries (LIBs). A specific challenge is the separation of Ni and Co due to nearly identical coordination chemistry and redox potentials. Here, we report a bipolar pulsed electrodeposition strategy in reline deep eutectic solvent (DES) that enables selective separation of Ni and Co without the use of aqueous acids or organic extractants. Spectroscopic analyses reveal that Ni2+ and Co2+ exist predominantly as tetrahedral [NiCl4]2- and [CoCl4]2- complexes in reline, while cyclic voltammetry shows distinct redox kinetics that can be temporally modulated through alternating cathodic and anodic pulses. This dynamic control drives preferential Ni deposition and rapid Co stripping, producing progressively Ni-enriched films with tunable morphologies. COMSOL simulations reproduce the periodic current response and confirm that selectivity arises from kinetic asymmetry rather than equilibrium speciation. These findings establish the use of bipolar pulsed electrodeposition for targeted separation of Ni and Co, offering a green perspective for green electrochemical metal recovery and circular battery resource management.
The destruction of per- and polyfluoroalkyl substances (PFAS) poses a formidable global environmental challenge owing to their extreme persistence and resistance to degradation. Here, we report that commercial granular activated carbon (GAC) significantly accelerates the degradation kinetics of perfluorocarboxylic acids (PFCAs) in dimethyl sulfoxide (DMSO), enhancing the degradation rate by 70% and the defluorination efficiency by 153% compared to GAC-free controls. In contrast, other adsorbents such as molecular sieves with varied pore structures showed no catalytic activity. Comparative experiments using modified carbon materials and resins functionalized with different groups identified oxygen-containing surface functional groups, specifically carboxyl moieties, as the key catalytic sites. Density functional theory (DFT) calculations showed that hydrogen-bonding interactions between surface carboxyl groups and pentadecafluorooctanoic acid (PFOA) lower the activation Gibbs free energy for decarboxylation by approximately 5.3-fold relative to the uncatalyzed pathway. This work reveals a new catalytic role of commercial GAC and suggests a practical pathway for simultaneous PFAS destruction and adsorbent regeneration under substantially milder conditions than conventional thermal treatment.
