Tris(2-chloroethyl) phosphate (TCEP) is a widely found emerging pollutant due to its heavy usage as a flame retardant. It is chemically stable and is very difficult to removal from water. The goal of this study was to explore whether iron monosulfide (FeS) can be used for reductive transformation of TCEP as FeS can react with a variety of halogenated organic contaminants. We used batch reactor systems to quantify the transformation reactions in the absence and presence of cetyltrimethylammonium bromide (CTAB, a common surfactant in aquatic environments). The results showed that, in the presence of CTAB (100 mg L⁻¹), FeS exhibited much greater reactivity towards TCEP as 93% of initial TCEP had been transformed within 14 d of reaction. In the absence of CTAB, it required 710 d of reaction to achieve 97.3% reduction of initial TCEP. The enhancement of CTAB on TCEP transformation rate could be due to the facts that CTAB could stabilize FeS suspension against aggregation, protect FeS from rapid oxidation, and increase surface adsorption of TCEP on FeS. XPS analysis showed that both Fe(II) and S(-II) species on the FeS surface were involved in the reductive transformation of TCEP. Analysis of transformation products revealed that TCEP was reductively transformed into bis(2-chloroethyl) phosphate (BCEP), Cl⁻ and C₂H₄. These findings showed that FeS may play an important role in the reductive transformation of TCEP when TCEP coexisting with CTAB in aquatic environments.

Southwestern China contains the largest and most well-developed karst region in the world, and the potentially toxic elements (PTEs) content in the soils of the region is remarkably high. To explore the internal and external control factors and sources of soil PTEs enrichment in this area and to provide a basis for the treatment of PTE pollution, 113 soil samples were collected from Hengxian County, a karst region in Guangxi Province, southwestern China. The importance of eighteen influencing factors including parent material, weathering, physicochemical properties, topography and human activities were quantitatively analyzed by (partial) redundancy analysis. The sources of PTEs were identified using the Pb isotope ratio and absolute principal component score/multiple linear regression (APCS-MLR) model. The contents of all soil PTEs were higher than the corresponding background values of Guangxi soils. The contents in Cu, Zn, Cd, Hg and Pb were the highest in the soil from carbonate rock. The factor group of geological background and weathering explained 26.5% for the accumulation and distribution of soil PTEs and the influence of physicochemical properties was less than 2% but increased to 25.6% through interaction with weathering. Fe (47.1%), Al (42.1%), Mn (22%), chemical index of alteration (12.8%) and clay (11.9%) were the key factors affecting the soil PTEs, while the influence of human activities was weak. Pb isotope ratio and APCS-MLR classified 62.8–74% of soil PTEs as derived from natural sources, whereas 18.23% and 18.95% were derived from industrial activities and agricultural practice/traffic emissions, respectively. The Pb isotope ratio showed that the natural sources account for up to 90% of the Pb in the soil from carbonate rock, the highest contribution among the studied soils. The results of the study can provide background information on the soil PTEs contamination in the karst areas of China and other areas worldwide.

Nano-magnetite supported by biochar (nFe₃O₄/BC) pyrolyzed at temperatures of 300 °C–600 °C was developed to activate hydrogen peroxide (H₂O₂) for the efficient degradation of ethylbenzene in aqueous solution. It was revealed that the degradation efficiency of ethylbenzene and TOC removal were 96.9% and 36.2% respectively after the reaction for 40 min in the presence of initial concentration of 0.1 mmol L⁻¹ ethylbenzene, 2.76 g L⁻¹ nFe₃O₄/BC₅₀₀ with the mass ratio of nFe₃O₄ to BC₅₀₀ of 4:1 and 2.0 mmol L⁻¹ H₂O₂ at pH 7.0. Based on electron paramagnetic resonance (EPR), quenching experiment and X-ray photoelectron spectroscopy (XPS) data, both OH and O₂⁻ radicals were generated in the nFe₃O₄/BC₅₀₀ activated H₂O₂ system, and the OH radicals were the predominant species for the degradation of ethylbenzene. Through electron transfer process, mechanisms of Fe(II), phenolic hydroxyl group and persistent free radicals (PFRs) on BC surfaces accounted for the generation of OH radicals, and Fe(III) in nFe₃O₄ and formed from Fe(II) oxidation responsible for the generation of O₂⁻ radicals in the nFe₃O₄/BC activated H₂O₂ system were proposed.

Hexavalent chromium and nitrate co-contaminated groundwater remediation are attracting extensive attention worldwide. However, the transformation pathways of chromium and nitrate and the interplay mechanism between them remain unclear. In this work, zeolite-supported nanoscale zero-valent iron/palladium (Z-Fe/Pd) was synthesized and used for the first time to simultaneously remediate Cr(VI) and nitrate. Transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses confirmed that nanoscale zero-valent iron/palladium was successfully loaded onto zeolite and it exhibited good dispersibility and oxidation resistance. Results of batch experiments showed that the Cr(VI) and nitrate removal efficiencies decreased from 95.5% to 91.5% to 45% and 73%, respectively, with the initial solution pH increasing from 3.0 to 8.0. The removal rates and efficiencies of Cr(VI) and nitrate under anoxic conditions were higher than those under open atmosphere because the dissolved oxygen diminished the electron selectivity toward the target pollutants. Moreover, the presence of Cr(VI) inhibited nitrate reduction by forming Fe(III)-Cr(III) hydroxide to impede electron transfer. Cr(VI) removal was promoted by nitrate, within limits, by balancing the consumption and generation rate of Fe₃O₄, which enhanced electron migration from the Fe(0) core to the external surface. The removal capacities of Cr(VI) and nitrate reached 121 and 95.5 mg g⁻¹, respectively, which were superior to the removal capacities of similar materials. Results of product identification, XRD, and XPS analyses of spent Z-Fe/Pd indicated that the reduction of Cr(VI) was accompanied by adsorption and co-precipitation, whereas the reduction of nitrate was catalyzed by the synergism of Fe(0) and Pd(0). An alternative to the simultaneous remediation of Cr(VI) and nitrate from groundwater under anoxic conditions is provided.

Soluble iron (FeS) in aerosols contributes to free oxygen radical generation with implications for human health, and potentially catalyzes sulfur dioxide oxidation. It is also an important external source of micronutrients for ocean ecosystems. However, factors controlling FeS concentration and its contribution to total iron (FeT) in aerosols remain poorly understand. Here, FeS and FeT in PM₂.₅ was studied at four urban sites in eastern China from 21 to 31 December, 2017. Average FeT (869–1490 ng m⁻³) and FeS (24–68 ng m⁻³) concentrations were higher in northern than southern China cities, but Fe solubility (%FeS, 2.7–5.0%) showed no spatial pattern. Correlation analyses suggested %FeS was strongly correlated with FeS and PM₂.₅ instead of FeT concentrations. Individual particle observations confirmed that more than 65% of nano-sized Fe-containing particles were internally mixed with sulfates and nitrates. Furthermore, there was a high correlation between sulfates or nitrates/FeT molar ratio and %FeS. We also found that the sulfates/nitrates had weaker effects on %FeS at RH < 50% than at RH > 50%, suggesting RH as indirect factor can influence %FeS in PM₂.₅. These results suggest an important role of chemical processing in enhancing %FeS in the polluted atmosphere.

Coal-Gas replacement project has been implemented to decrease haze pollution in China in recent years. Airborne arsenic (As) mostly originates from coal burning processes. It is noteworthy to compare the distribution of arsenic fraction in PM₂.₅ before and after coal-gas replacement. Eighty PM₂.₅ samples were collected in Baoding in December 2016 (coal dominated year) and December 2017 (gas dominated year) at different functional areas including residential area (RA), industrial area (IA), suburb (SB), roadside (ST) and Botanical Garden Park (BG). The fraction, bioavailability and health risk of As in the PM₂.₅ samples were investigated and compared between these two years. Arsenic was mainly distributed in the non-specifically sorbed fraction (F1) and the residual fraction (F5). However, the proportion of F1 to the total As in 2017 was higher than that in 2016, while the proportion of As in the amorphous and poorly-crystalline hydrous oxides of Fe and Al fraction (F3) in 2017 was lower. The distributions of fraction and bioavailability showed temporal and spatial characteristics. The total concentration and bioavailability of As in SB and IA were significantly higher than those in RA, ST and BG. The BF (Bioavailability Factor) values of As ranged from 0.30 to 0.61. Health risk assessment indicated that the hazard quotient (HQ) and carcinogenic risk (CR) of As in PM₂.₅ significantly decreased after coal-gas replacement.

Achieving large pore size, high catalytic performance with stable structure is critical for metal–organic frameworks (MOFs) to have more hopeful prospects in catalytic applications. Herein, we had reported a method to synthesize highly reactive yet stable defective iron-based Metal organic frameworks by using different monocarboxylic acids with varying lengths as a modulator. The physical−chemical characterization illustrating that modulators could improve the crystallinity, enlarge pore size and enhance catalytic performance and octanoic acid (OA) was screened to be the suitable choice. The catalytic performance of catalysts was detected through persulfate (PS) activation for degrading Tetrabromobisphenol A (TBBPA). The study demonstrated that the highest degradation efficiency for 0.018 mmol L−1 TBBPA was that 97.79% in the conditions of the 1.0 g L−1 Fe(BDC)(DMF,F)-OA-30 dosage and TBBPA:PS = 200:1. In addition, there was observed that no obvious change of the crystal structure, little the leachable iron concentration in the solutions and no significant loss of catalytic activities of Fe(BDC)(DMF,F)-OA-30 after 5th cycles. The iron valence state of Fe(BDC)(DMF,F)-OA-30 before and after degradation and electrochemical properties reveal that the partial substitution of organic ligands by octanoic acid, when removing OA and forming defects by heat and vacuum treatment to generate coordinatively unsaturated metal sites and accelerate the original transmission of electronic, leading to enhance the activity of persulfate activation for efficient removal TBBPA.

Supported carbon quantum dots (CQDs), used as fluorescent sensors for the detection of metal ions, have rarely been used to remove heavy metals from water. Nitrogen-doped CQDs immobilized in hydrophilic silica hydrogels exhibited a more superior sensitivity and selectivity for the detection of Re(VII) and Cr(VI) than other metal ions, including Fe(III), Fe(II), Zn(II), Cu(II) and Mn(II). For the first time, low limits of detection (LOD) of 2.3 μM for Re(VII) detection and 65 nM for Cr(VI) detection were reported by a facile method. Based on the high selectivity of fluorescent silica hydrogels for Re(VII) and Cr(VI) detection, the removal of Re(VII) and Cr(VI) by graphene oxide (GO) in water was monitored with the hydrogels used as a turn-off fluorescent sensing platform. The consistent results of the sorption isotherms of each metal on GO, which were obtained from the fluorescence spectra and by UV absorption, further verified the possibility of monitoring metal removal by fluorescence detection. Remarkably, GO removed 1186 mg/g of Re(VII) but only 178 mg/g of Cr(VI). The density functional theory (DFT) calculations indicated that both Re(VII) and Cr(VI) formed stable bonds with silica hydrogels, confirming that the interactions between the metal ions and the substrate would promote the fluorescence quenching of the supported CQDs. On the other hand, Re(VII) interacted more strongly with the carboxyl groups of GO than Cr(VI). In addition, a real-time detection system was designed to alarm the service life of a GO filter used for Re(VII) removal.

Antibiotic resistance genes (ARGs) and mobile gene elements (MGEs), the emerging genetic contaminants, are regarded as severe risks to public health for impairing the inactivation efficacy of antibiotics. Secondary effluents from wastewater treatment plants are the hotspots for spreading these menaces. Herein, sulfidated nanoscale zero-valent iron (S-nZVI) was occupied to remove ARGs and MGEs in secondary effluents and weaken the regrowth capacity of their bacterial carriers. The effects of S/Fe molar ratios (S/Fe), initial pH and dosages on 16S rRNA and ARGs removal were also investigated. Characterization, mass balance and scavenging experiments were conducted to explore the mechanisms of the gene removal. Quantitative PCR (qPCR) and high throughput fluorescence qPCR showed more than 3 log unit of 16S rRNA and seven out of 10 ARGs existed in secondary effluent could be removed after S-nZVI treatment. The mechanisms might be that DNA accepted the electron provided by the Fe⁰ core of S-nZVI after being adsorbed onto S-nZVI surface, causing the decrease of 16S rRNA, ARGs and lost their regrowth capacity, especially for typical MGE (intI1) and further inhibiting the vertical gene transfer (VGT) and intI1-induced horizontal gene transfer (HGT). Fe⁰ core was oxidized to iron oxides and hydroxides at the same time. High throughput sequencing, network analysis and variation partitioning analysis revealed the complex correlations between bacteria and ARGs in secondary effluent, S/Fe could directly influence ARGs variations, and bacterial genera made the greatest contribution to ARGs variations, followed by MGEs and operational parameters. As a result, S-nZVI could be an available reductive approach to deal with bacteria and ARGs.

Odontarrhena muralis is one of the most promissing plant species for Ni phytomining, and soil amendments can further increase its Ni phytoextraction ability. Here we investigated whether Ni phytomining/phytoremediation using this Ni hyperaccumulator can benefit from applying citric acid to a serpentine soil that is naturally enriched in Ni (>1000 mg kg⁻¹). Synchrotron micro X-ray fluorescence (μ-SXRF) was used to image Ni and other metal distributions in whole fresh leaves of O. muralis. Leaf Ni accumulation in plants grown on citric acid-amended soil increased up to 55% while Co, Cr, Fe, Mn, and Zn concentrations were 4-, 14-, 6-, 7- and 1.3-fold higher than the control treatment. O. muralis presented high bioconcentration factors (leaf to soil concentration ratio) to Ni and Zn whereas Cr was seemingly excluded from uptake. The μ-SXRF images showed a uniform distribution of Ni, preferential localization of Co in the leaf tip, and clear concentration of Mn in the base of trichomes. The citric acid treatments strongly increased the Co fluoerescence intensity in the leaf tip and altered the spatial distribution of Mn across the leaf, but there was no difference in Ni fluorescence counts between the trichome-base region and the bulk leaf. Our data from a serpentine soil suggests that citrate treatment enhances Ni uptake, but Co is excreted from leaves even in low leaf concentrations, which can make Co phytoming using O. muralis unfeasible in natural serpentine soils.