Per- and polyfluoroalkyl substances (PFAS) are a resilient class of anthropogenic contaminants of emerging concern with over 12 000 individual compounds that have been noted for industrial applications, consumer goods, and food packaging materials. In general, the most common contributors to PFAS environmental pollution are aviation facilities, specifically those that use aqueous film forming foams (, at military bases and airports). In this study, we examined the presence of PFAS across Okinawa Island (Japan) due to its large-scale U.S. military presence throughout the island. Surface water was collected at 61 sites across the island to achieve maximum geographical coverage of the island while also collecting near suspected PFAS sources; 31 PFAS were monitored using a 12 min HPLC-MS/MS method. A total of 15 PFAS were detected and quantified around the island with a mean ΣPFAS of 16.3 ng L and a maximum site concentration of 164.3 ng L. Region-specific PFAS profiles were observed across the island, including the overwhelming presence of PFHpA in the northern region of the island, revealing the possibility of multiple PFAS source points in Okinawa. The resultant data herein provides the first island-wide examination of PFAS "hotspots" across Okinawa and is a critical first step toward increasing PFAS awareness and action.

This study uses mobile monitoring to gain a better understanding of particulate matter (PM) sources in two areas of Central and Outer London, UK. We find that, unlike emissions of nitrogen oxides (NO + NO = NO), which are elevated in Central London due to the high number of diesel vehicles and congestion, fine particulate matter (PM) emissions are well-controlled. This finding provides evidence for the effectiveness of vehicle particulate filters, supporting the view that their widespread adoption has mitigated PM emissions, even in the highly dieselized area of Central London. However, mobile monitoring also reveals infrequent elevated PM concentrations caused by malfunctioning vehicles. These events were confirmed through simultaneous measurements of PM and sulfur dioxide (SO), the latter being a strong tracer of engine lubricant combustion. A single event from a gasoline car, representing just 0.15% of the driving distance in Outer London, was responsible for 7.4% of the ΔPM concentration above background levels, highlighting the ongoing importance of addressing high-emission vehicles. In a novel application of mobile monitoring, we demonstrate the ability to identify and quantify non-vehicular sources of PM. Among the sources unambiguously identified are construction activities, which result in elevated concentrations of coarse particulate matter (PM = PM - PM). The mobile measurements clearly highlight the spatial extent of the influence of such sources, which would otherwise be difficult to determine. Furthermore, these sources are shown to be weather-dependent, with PM concentrations reduced by 62.1% during wet conditions compared to dry ones.

The interaction between dissolved organic matter (DOM) and iron minerals has a significant effect on its stabilization and preservation in the environment. In this study, iron minerals with different crystal forms (crystalline goethite and amorphous ferrihydrite) were selected to investigate the photochemical transformation process for DOM immobilized on iron minerals under simulated sunlight irradiation at the molecular scale with the help of Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The results showed that a total of 7148 molecules were detected in alkaline-extractable sedimentary DOM, of which 38.8% and 36.2% were adsorbed by ferrihydrite and goethite, respectively, while there was no selectivity difference between the two iron minerals in terms of DOM adsorption. After simulated sunlight irradiation, the DOM adsorbed by goethite was significantly degraded (58.3%), in which the H/C ratio of the mineral-immobilized DOM increased and the O/C ratio decreased, and the photodegradation primarily involved DOM molecules with high Kendrick mass defect (KMD) values. The results confirmed that the iron mineral types play an important role in the transportation and transformation of DOM, which adds to the understanding of the fate of DOM in natural environments.

Correction for 'How do ecosystem service functions affect ecological health? Evidence from the Yangtze River Economic Belt in China' by Wei Wang , , 2024, https://doi.org/10.1039/D4EM00296B.

Quantifying source contributions to indoor PM levels by indoor PM sources has been limited by the costs associated with chemical speciation analyses of indoor PM samples. Here, we propose a new methodology to estimate this contribution. We applied FUzzy SpatioTemporal Apportionment (FUSTA) to a database of indoor and outdoor PM concentrations in school classrooms plus surface meteorological data to determine the main spatiotemporal patterns (STPs) of PM. We found four dominant STPs in outdoor PM, and we denoted them as regional, overnight mix, traffic, and secondary PM. For indoor PM we found the same four outdoor STPs plus another STP with a distinctive temporal evolution characteristic of indoor-generated PM. Concentration peaks were evident for this indoor STP due to children's activities and classroom housekeeping, and there were minimum contributions on sundays when schools were closed. The average indoor-generated estimated contribution to PM was 5.7 μg m, which contributed to 17% of the total PM, and if we consider only school hours, the respective figures are 8.1 μg m and 22%. A cluster-wise indoor-outdoor PM regression was applied to estimate STP-specific infiltration factors () per school. The median and interquartile range (IQR) values for are 0.83 [0.7-0.89], 0.76 [0.68-0.84], 0.72 [0.64-0.81], and 0.7 [0.62-0.9], for overnight mix, secondary, traffic, and regional sources, respectively. This cost-effective methodology can identify the indoor-generated contributions to indoor PM, including their temporal variability.

Urinary hydroxylated-polycyclic aromatic hydrocarbons (PAHs), with half-life less than 2 days, are established biomarkers of short-term exposure to PAHs, a ubiquitous constituent of air pollution mixture. In this study, we explore the use of PAHs-hemoglobin adducts as biomarkers of longer-term exposure to air pollution by leveraging an extant resource of blood samples collected from 235 pregnant women residing in Rochester, NY. We measured red blood cells for benzo[]pyrene-tetrols (BaPT) and phenanthrene-tetrols (PHET), both of which are hydrolysis products of PAH-hemoglobin adduct. We utilized previously estimated PM and NO concentrations within the 1 km grid surrounding each participant's residence, calculated for up to 20 weeks before the blood collection date. Associations between PAHs tetrols and cumulative exposures to ambient PM or NO over different time periods were examined using a linear mixed-effects model with participant-specific random intercepts adjusting for season, gestation age, maternal age, maternal income level, and pre-pregnancy BMI. We observed positive associations between PHET concentration and cumulative PM exposure over gestational weeks 12-17, and between BaPT concentration and cumulative PM exposure over gestational weeks 3-16 prior to sample collection. Each interquartile range (IQR) increase in 14 week PM exposure (1.26 μg m) was associated with a 9.02% (95% CI: 0.30%, 17.7%) increase in PHET and a 12.8% (95% CI: 1.09%, 23.5%) increase in BaPT levels. In contrast, no associations were observed between either biomarker and cumulative NO exposures. These findings underscore the potential of PAH-hemoglobin adducts as longer-term (weeks to 4 months) exposure biomarkers of ambient PM.

Millions of tons of coal fly ashes (CFAs) are produced annually during coal combustion in the U.S., which are commonly beneficially used in the concrete industry or disposed of in ash ponds. CFAs contain trace amounts of a range of toxic heavy metals including selenium (Se). Because the toxicity of Se is dependent on its speciation, investigating Se speciation in CFAs as affected by coal source and combustion conditions can help understand the related environmental and human health impacts during disposal or beneficial reuse. In this study, a set of representative CFA samples were characterized for Se speciation using synchrotron X-ray absorption spectroscopy (XAS) and micro-X-ray fluorescence spectromicroscopy (μ-XRF/XAS). Se-containing particles were highly heterogeneous, and individual particles might contain multiple oxidation states including Se(0), Se(IV), and Se(VI). Principal component analysis was performed for sample characteristics including AlO, SiO, CaO, FeO, loss on ignition, average particle size, Se concentration, and Se oxidation state. Selective catalytic reduction (SCR), which is used to limit nitrogen oxide (NO) emissions during coal combustion, was found to be associated with the presence of reduced Se oxidation states, with up to 90% Se(0) observed in samples with SCR. Alongside SCR, FeO content may also influence Se speciation.

Dissolved organic matter (DOM) released from biochar may impact antibiotic mobility and environmental fate in subsurface environments. Here, DOM samples derived from biochars (BDOM) generated by pyrolyzing corn straw at 300, 450, and 600 °C were employed to elucidate the mobility characteristics of these organic substances and their influences on the transport of sulfamerazine (SMZ, a typical sulfonamide antibiotic) in soil porous media. The results demonstrated that BDOM produced at a lower pyrolysis temperature exhibited greater mobility owing to the weaker hydrophobic and H-bonding interactions between BDOM and soil particles. Additionally and importantly, BDOM facilitated the promotion of SMZ mobility owing to the increased electrostatic repulsion between SMZ forms and soil grains, the steric hindrance effect induced by the deposition of organic matter, and the competitive retention between SMZ molecules and BDOM. Meanwhile, the promotion effects of BDOM enhanced with improving pyrolysis temperature owing to the promoted deposition of organic matter on soil surfaces and the strengthened electrostatic repulsion. Moreover, the facilitated effects of BDOM on SMZ mobility declined as the solution pH values were raised from 5.0 to 9.0 or the flow rate increased from 0.18 to 0.51 cm min. This trend was due to decreased deposition competition and the steric effect caused by decreased retention of BDOM on soil particles. Furthermore, the cation-bridging effect emerged as an important mechanism contributing to the promotion effects of BDOM when the solution contained divalent cations (Cu or Ca). Moreover, a two-site non-equilibrium model was used to interpret the controlling mechanisms for the effects of BDOM on the transport of SMZ. Findings from this work highlight that biochar-derived dissolved organic matter can remarkably affect the environmental behaviors of antibiotics in aquatic environments.

Isocyanates are well-known irritants and sensitizers, and measuring their occupational airborne exposure is challenging due to their high chemical reactivity and semi-volatile nature. This study builds on a previous publication by our team that focused on comparing evaluation methods for isocyanates. The current research aims at developing, validating, and applying a laboratory generation system designed to replicate real-world conditions for spraying clear coats in autobody shops using hexamethylene diisocyanate (HDI)-based products. The system involved a spray gun connected to two chambers in series, enabling sample collection and analysis. The system successfully generated HDI and isocyanurate concentrations ranging from 0.008 to 0.040 mg m and 0.351 to 3.45 mg m, respectively, with spatial homogeneity (RSD) of 5.8% and 16.5%. The particle-size distribution (MMAD) of 4 μm was measured using a cascade impactor and an electrical low-pressure impactor. The samples generated were used to correlate the amount of isocyanates collected with scanning electron microscope images of droplets on a filter. Three methods were compared to the reference method-an impinger with a backup glass fibre filter (GFF) and 1,2-methoxyphenylpiperazine (MP) based on ISO 16702/MDHS 25-in six generation experiments: (1) Swinnex cassette 13 mm GFF MP (MP-Swin); (2) closed-face cassette 37 mm GFF (end filter and inner walls) MP (MP-37); and (3) denuder and GFF dibutylamine (DBA) (ISO 17334-1 Asset). The analysis revealed clear trends regarding which sampler sections collected HDI (mainly in the vapor phase) or isocyanurate (exclusively in the particulate phase). The study found no significant bias between the tested methods (MP-Swin, MP-37, and Asset) and the reference method (impinger) for both HDI monomer and isocyanurate. The three tested methods showed limits of agreement beyond the acceptable range of ±30% (95% confidence interval), largely due to data variability, though MP-Swin and MP-37 exhibited lower variability than Asset. The results will be further evaluated in a real-world environment where similar clear coats are used.

Correction for 'Exploring the variability of PFAS in urban sewage: a comparison of emissions in commercial municipal urban areas' by N. Krlovic , , 2024, , 1868-1878, https://doi.org/10.1039/D4EM00415A.

As microplastic (MP) particles continue to spread globally, their pervasive presence is increasingly problematic. Analyzing MPs in matrices as varied as soil, river water, and biosolid fertilizers is critical, as these matrices directly impact the food sources of plants, animals, and humans. Current analytical methods for quantifying and identifying MPs are limited due to labor-intensive extraction processes and the time and effort required for counting and analysis. Recently, Machine Learning (ML) has been introduced to the analysis of MPs in complex matrices, significantly reducing the need for extensive extraction and increasing analysis speeds. This work aims to illuminate various ML techniques for new researchers entering this field. It highlights numerous examples in the application of these models, with a particular focus on spectroscopic techniques such as infrared and Raman spectroscopy; tools which are used to quantify and identify MPs in complex matrices. By demonstrating the effectiveness of these computer-based tools alongside the hands-on techniques currently used in the field, we are confident that these ML methodologies will soon become integral to all aspects of microplastic analysis in the environmental sciences.

: Coke oven emissions (COEs) are formed in the process of coking production, mainly composed of polycyclic aromatic hydrocarbons (PAHs) and benzene; however, the health impacts of COE exposure in coking workers are not fully clear so far. We aimed to explore the associations of occupational COE exposure with pulmonary function, blood pressure, blood cell parameters, and blood biochemical indices, and to bolster health surveillance and disease prevention and control in coking workers. : We investigated 566 coking workers at a large state-owned enterprise coking plant in Taiyuan, Shanxi, China, measured the concentrations of plasma 16 PAHs and urinary phenol, assessed the health outcomes including pulmonary function, blood pressure, the levels of peripheral hematologic parameters and biochemical indices, and examined the associations of PAH and phenol concentrations with the health outcomes using multiple linear regressions, least absolute shrinkage and selection operator regression (LASSO), and Bayesian kernel machine regression (BKMR). : After adjustment for confounders, plasma ∑PAH concentration was significantly associated with increases in hemoglobin (HGB) and triglyceride (TG) levels in coking workers, and urinary phenol concentration was significantly associated with increases in the diastolic blood pressure (DBP) level, and decreases in platelet (PLT) count. When phenol concentration and PAH concentration were simultaneously included in the multiple linear regression model, both of them were associated with the level of HGB. LASSO and BKMR indicated that the PAHs with four rings and above contributed to the HGB level. : PAH exposure could damage hematological parameters and blood lipids, and benzene exposure could increase blood pressure and decrease PLT count.

In shallow lakes, mobilization of legacy phosphorus (P) from the sediments can be the main cause for persisting eutrophication after reduction of external P input. In-lake remediation measures can be applied to reduce internal P loading and to achieve ecosystem recovery. The eutrophic shallow peat lake Terra Nova (The Netherlands) was treated with iron (Fe) to enhance P retention in the sediment. This treatment, however, intensified seasonal internal P loading. An earlier study suggested that Fe addition led to increased P binding by easily-reducible Fe(III) associated with organic matter (OM), which readily releases P when bottom waters turn hypoxic. In this complementary study, bulk and micro Fe K-edge and P K-edge X-ray absorption spectroscopy and micro-focused X-ray fluorescence spectroscopy were applied to characterize the P hosting Fe(III) pool. Combined with sequential extraction data, the synchrotron X-ray analyses revealed that a continuum of co-precipitates of Fe(III) with calcium, phosphate, manganese and organic carbon within the OM matrix constitutes the reducible Fe(III) pool. The complementary analyses also shed new light on the interpretation of sequential extraction results, demonstrating that pyrite was not quantitatively extracted by nitric acid (HNO) and that most of the Fe(II) extracted by hydrochloric acid (HCl) originated from phyllosilicate minerals. Formation of an amorphous inorganic-organic co-precipitate upon Fe addition constitutes an effective P sink in the studied peaty sediments. However, the high intrinsic reactivity of this nanoscale co-precipitate and its fine distribution in the OM matrix makes it very susceptible to reductive dissolution, leading to P remobilization under reducing conditions.

Siderite (FeCO) is an important reservoir of mineral-bound ferrous iron in non-sulfidic, reducing soils and sediments. It is redox sensitive, and its oxidation may facilitate the reduction of a range of pollutants, produce reactive oxygen species, or induce the formation of oxidation products with large surface areas for contaminant sorption. However, there is currently a limited understanding of the stability of siderite in complex environments such as soils and sediments. Here, we use a series of batch experiments complemented with thorough characterisation of mineral oxidation products to investigate the oxidation of siderite in the presence and absence of the low molecular weight organic acids (LMWOAs) citrate, tiron, salicylate, and EDTA as analogues for naturally occurring compounds or functional groups of natural organic matter that ubiquitously coexist with siderite. Our results show that siderite alone at pH 7.5 was completely oxidised to form ferrihydrite, nanocrystalline lepidocrocite, and nanocrystalline goethite in less than 6 hours. However, in the presence of LMWOAs, up to 48% of the siderite was preserved for more than 500 hours and the formation of goethite was inhibited in favour of ferrihydrite and lepidocrocite. Using experimental data from electron microscopy and chemical speciation modelling, we hypothesise that the siderite may be preserved through the formation of an Fe(III)-passivation layer at the siderite surface.

Per and polyfluoroalkyl substances (PFAS) are ubiquitous in the indoor environment, resulting in indoor exposure. However, a dearth of concurrent indoor multi-compartment PFAS measurements, including air, has limited our understanding of the contributions of each exposure pathway to residential PFAS exposure. As part of the Indoor PFAS Assessment (IPA) Campaign, we measured 35 neutral and ionic PFAS in air, settled dust, drinking water, clothing, and on surfaces in 11 North Carolina homes. Ionic and neutral PFAS measurements reported previously and ionic PFAS measurements reported herein for drinking water (1.4-34.1 ng L), dust (202-1036 ng g), and surfaces (4.1 × 10-1.7 × 10 ng cm) were used to conduct a residential indoor PFAS exposure assessment. We considered inhalation of air, ingestion of drinking water and dust, mouthing of clothing (children only), and transdermal uptake from contact with dust, air, and surfaces. Average intake rates were estimated to be 3.6 ng kg per day (adults) and 12.4 ng kg per day (2 year-old), with neutral PFAS contributing over 80% total PFAS intake. Excluding dietary ingestion, which was not measured, inhalation contributed over 65% of PFAS intake and was dominated by neutral PFAS because fluorotelomer alcohol (FTOH) concentrations in air were several orders of magnitude greater than ionic PFAS concentrations. Perfluorooctanoic acid (PFOA) intake was 6.1 × 10 ng kg per day (adults) and 1.5 × 10 ng kg per day (2 year-old), and biotransformation of 8 : 2 FTOH to PFOA increased this PFOA body burden by 14% (adults) and 17% (2 year-old), suggesting inhalation may also be a meaningful contributor to ionic PFAS exposure through biotransformation.

Multiphase interactions and chemical reactions at indoor surfaces are of particular importance due to their impact on air quality in indoor environments with high surface to volume ratios. Kinetic multilayer models are a powerful tool to simulate various gas-surface interactions including partitioning, diffusion and multiphase chemistry of indoor compounds by treating mass transport and chemical reactions in a number of model layers in the gas and condensed phases with a flux-based approach. We have developed a series of kinetic multilayer models that have been applied to describe multiphase chemistry and interactions indoors. They include the K2-SURF model treating the reversible adsorption of volatile organic compounds on surfaces, the KM-BL model treating diffusion through an indoor surface boundary layer, the KM-FILM model treating organic film formation by multi-layer adsorption and film growth by absorption of indoor compounds, and the KM-SUB-Skin-Clothing model treating reactions of ozone with skin lipids in skin and clothing. We also developed the effective mass accommodation coefficient that can treat surface partitioning by effectively taking into account kinetic limitations of bulk diffusion. In this study we provide detailed instructions and code annotations of these models for the model user. Example sensitivity simulations that investigate the impact of input parameters are presented to help with familiarization to the codes. The user can adapt the codes as required to model experimental and indoor field campaign measurements, can use the codes to gain insights into important reactions and processes, and can extrapolate to new conditions that may not be accessible by measurements.

This study investigated microplastic polyester fibres representative of those shed during laundering as sorbents for metal ions. During sewage distribution and treatment, microplastics are exposed to elevated concentrations of metal ions, typically for several days. Cryogenic milling was used to generate polyethylene terephthalate (PET) fibres. Characterisation using optical microscopy and Raman spectroscopy revealed that milling did not cause significant chemical alteration to the fibres. Milled fibres were subsequently assessed in screening tests for their capacity to retain 12 metal ions-Sb(III), As(III), Cd(II), Cr(VI), Cu(II), Co(II), Pb(II), Hg(II), Mo(VI), Ni(II), V(V) and Zn(II)-at pH 8. All metal ions were sorbed onto PET fibres. The highest distribution coefficient () was observed for Pb (939 mL g), followed by Cd (898 mL g), Cu (507 mL g), Hg (403 mL g), and Zn (235 mL g). The extent of sorption is largely explicable by electrostatic interactions between the PET surface (1.95 point of zero net charge) and the predicted metal ion species. The sorption behaviour of Cd and Hg was examined in more detail since both showed high sorption capacity and are highly toxic. Kinetic experiments revealed that the sorption of both elements was relatively fast, with a steady state reached within six hours. Experimental data from isotherm tests fitted well to the Langmuir sorption model and demonstrated that PET fibres had a much greater sorption capacity for Hg (17.3-23.1 μg g) than for Cd (4.3-5.3 μg g). Overall, the results indicate that retention of metal ions onto PET fibres originating from laundry is expected during full-scale sewage treatment, which facilitates the subsequent transfer of metals into the terrestrial environment, given that sewage sludge is commonly applied to agricultural land.

Lack of water quality data for private drinking water sources prevents robust evaluation of exposure risk for communities co-located with historically contaminated sites and ongoing industrial activity. Areas of the Appalachian region of the United States (, Pennsylvania, Ohio and West Virginia) contain extensive hydraulic fracturing activity, as well as other extractive and industrial technologies, in close proximity to communities reliant on private drinking water sources, creating concern over potential groundwater contamination. In this study, we characterized volatile organic compound (VOC) occurrence at 307 private groundwater well sites within Pennsylvania, Ohio, and West Virginia. The majority (97%) of water samples contained at least one VOC, while the average number of VOCs detected at a given site was 5 ± 3. The majority of individual VOC concentrations fell below applicable U.S. Environmental Protection Agency (EPA) Maximum Contamination Levels (MCLs), except for chloroform (MCL of 80 μg L; = 1 at 98 μg L), 1,2-dibromoethane (MCL of 0.05 μg L; = 3 ranging from 0.05 to 0.35 μg L), and 1,2-dibromo-3-chloropropane (MCL of 0.2 μg L; = 7 ranging from 0.20 to 0.58 μg L). To evaluate well susceptibility to VOCs from industrial activity, distance to hydraulic fracturing site was used to assess correlations with contaminant occurrences. Proximity to closest hydraulic fracturing well-site revealed no statistically significant linear relationships with either individual VOC concentrations, or frequency of VOC detections. Evaluation of other known industrial contamination sites (, US EPA Superfund sites) revealed elevated levels of three VOCs (chloroform, toluene, benzene) in groundwaters within 10 km of those Superfund sites in West Virginia and Ohio, illuminating possible point source influence. Lack of correlation between VOC concentrations and proximity to specific point sources indicates complex geochemical processes governing trace VOC contamination of private drinking water sources. While individual concentrations of VOCs fell well below recommended human health levels, the low dose exposure to multiple VOCs occurring in drinking supplies for Appalachian communities was noted, highlighting the importance of groundwater well monitoring.

Per- and polyfluoroalkyl substances (PFAS) are reported in residential and commercial paints, but there are no data for paints used in the transportation sector. From 2023 to 2024, 16 traffic paints and 10 bridge paints were collected from Pacific Northwest regional transportation facilities or purchased and analyzed for total fluorine by F-nuclear magnetic resonance (NMR) spectroscopy, volatile PFAS by gas chromatography-mass spectrometry (GC-MS), and ionic target and suspect PFAS by liquid chromatography-quadrupole time-of-flight mass spectrometry. The only target PFAS identified was 6:2 fluorotelomer phosphate diester (diPAP) which ranged in concentrations from 0.065 to 13 μg g. While 6:2 diPAP is not regulated in paints, it can undergo environmental transformation to act as a source of perfluoroalkyl carboxylic acids. A combination of F-NMR and GC-MS was used to quantify and identify the fluorinated aromatic PFAS, parachlorobenzotrifluoride (PCBTF), at concentrations from 440 to 16 000 μg g in bridge paints, thus PCBTF may contribute to work exposure and levels in urban air. Additionally, evolved gas analysis with mass spectrometry and pyrolysis-GC-MS established that the insoluble fraction of paints is not comprised of fluoropolymers. Based on the amount of paint required per kilometer, we estimate up to 0.20-2.30 g 6:2 diPAP per kilometer depending on marking type. Therefore, traffic paint may be a potential source of the PFAS detected in urban runoff.

The historical use and storage of aqueous film-forming foams (AFFF) containing per- and poly-fluoroalkyl substances (PFAS) at a range of sites including airports, defence, and port facilities have resulted in a legacy of contaminated infrastructure such as concrete. Contaminated concrete constitutes an ongoing source of PFAS contamination requiring management to ensure the protection of human health and the environment. In this study, modified Leaching Environmental Assessment Framework (LEAF) and Australian Standard Leaching Procedure (ASLP) were used to examine the leachability of PFAS, specifically, perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorohexanesulfonate (PFHxS) and perfluorohexanoic acid (PFHxA) from AFFF-contaminated concrete collected from an Australian Defence Fire Training Area (FTA). In general, PFAS readily leached from intact contaminated concrete monoliths with the cumulative proportion (%) decreasing in the order: PFHxA (>95%) > PFOS (26-84%) ≈ PFHxS (14-78%) > PFOA (<1-54%). Higher leachability for PFHxA from concrete is consistent with previous findings for solids, however, inconsistent for PFOA with higher retention (lower leachability) in concrete as compared to PFOS. Duration of exposure to water (0.5-48 h) and temperature (25 °C and 50 °C) had little influence on the proportion of PFAS leachability from powdered concrete. A higher proportion of PFAS leached from a <2 mm concrete powder size fraction as compared to 2-20 mm and 20 mm size fractions. This behavior reflects an increase in surface area with decreasing concrete particle size. Reducing the particle size could enhance PFAS removal from waste concrete.

Compost-derived dissolved organic matter (DOM) is a heterogeneous assemblage of different redox-active organic molecules. We hypothesize that DOM can interact with Cr(VI) and reduce it to Cr(III), thereby influencing the dynamics of Cr(VI) in soil and aquatic environments. Here, DOM, along with soil humic substances isolated from red soil and black soil, were fractionated into humic acid fractions (, HA, HA, and HA) and fulvic acid fractions (, FA, FA, and FA), respectively. The reduction and interaction between Cr(VI) and the six organic matter fractions were investigated. The results showed that the total Cr(VI) reduction capacity (TRC) of the six organic matter fractions was 26.77-49.34 μM Cr(VI) per mg OM. The TRC of HA fractions was 35.54-49.34 μM Cr(VI) per mg OM, which exceeded that of FA fractions (26.77-31.29 μM Cr(VI) per mg OM). DOM had a HA/FA ratio of 0.64, which was higher than that of black soil humic substance (0.59) and red soil humic substance (0.20). The sum of the TRC of DOM was 35.57 μM Cr(VI) per mg OM, which was larger than that of black soil humic substance (32.87 μM Cr(VI) per mg OM) and red soil humic substance (33.01 μM Cr(VI) per mg OM). The TRC was positively correlated with TOC, TN, phenol C, alkyl C, and aromatic C contents and negatively correlated with E/E, O-alkyl C, and carboxyl C contents. The reduction of Cr(VI) at pH 6 was negligible, whereas 32-67% Cr(VI) was reduced at pH 2. The Cr(VI) reduction capacities (RC2, RC2, and RC6) at pH 2-6 were positively correlated ( > 0.71) with phenol C. Spectral analysis showed that there was no obvious complexation between Cr(VI) and the six organic matter fractions at pH 6, and thus the reduction of Cr(VI) was negligible, but solution pH could affect the accessibility of organic molecules to Cr(VI) and thus influence Cr(VI) reduction.