Analysis of heavy metal and polycyclic aromatic hydrocarbon pollution characteristics of a typical metal rolling industrial site based on data mining.

With the transformation and upgrading of industries, the environmental problems caused by industrial residual contaminated sites are becoming increasingly prominent. Based on actual investigation cases, this study analyzed the soil pollution status of a remaining sites of the copper and zinc rolling industry, and found that the pollutants exceeding the screening values included Cu, Ni, Zn, Pb, total petroleum hydrocarbons and 6 polycyclic aromatic hydrocarbon monomers. Based on traditional analysis methods such as the correlation coefficient and spatial distribution, combined with machine learning methods such as SOM + K-means, it is inferred that the heavy metal Zn/Pb may be mainly related to the production history of zinc rolling. Cu/Ni may be mainly originated from the production history of copper rolling. PAHs are mainly due to the incomplete combustion of fossil fuels in the melting equipment. TPH pollution is speculated to be related to oil leakage during the industrial use period and later period of vehicle parking. The results showed that traditional analysis methods can quickly identify the correlation between site pollutants, while SOM + K-means machine learning methods can further effectively extract complex hidden relationships in data and achieve in-depth mining of site monitoring data.

Aquatic photolysis of high-risk fluorinated liquid crystal monomers: Kinetics, toxicity evaluation, and mechanisms.

Despite the frequent detection of fluorinated liquid-crystal monomers (FLCMs) in the environment, the level of understanding of their fate, toxicity, and transformation remains insufficient. Herein, we investigated the degradation kinetics and mechanism of an FLCM (4-cyano-3-fluorophenyl 4-ethylbenzoate, CEB-F) under ultraviolet (UV) photolysis in aquatic environment. Our findings demonstrated that the UV photolysis of CEB-F followed first-order kinetics. Photodegradation products were identified using liquid chromatography with mass spectrometry, and detailed reaction pathways were proposed. It is postulated that through the attack of reactive oxygen species, hydroxylation, and CO/C-F bond cleavage, CEB-F gradually degraded into small molecular compounds, releasing fluorine ions. Acute immobilization tests with Daphnia magna (D. magna) revealed significant acute toxicity of CEB-F, with LC50 values ranging from 1.023 to 0.0536 µM over 24 to 96 h, emphasizing the potential high risk of FLCMs in aquatic ecosystems if inadvertently discharged. Interestingly, we found that the toxicity of CEB-F photolysis reaction solutions was effectively reduced. Through catalase and acetylcholinesterase activities analysis along with molecular docking simulation, we proposed differences in the underlying toxicity mechanisms of CEB-F and its photolysis products to D. magna. These findings highlight the potential harmful effects of FLCMs on aquatic ecosystems and enrich our understanding of the photolysis behavior of FLCMs.

New dechlorination products and mechanisms of tris(2-chloroethyl) phosphate by an anaerobic enrichment culture from a vehicle dismantling site.

End-of-life vehicles (ELVs) dismantling sites are the notorious hotspots of chlorinated organophosphate esters (Cl-OPEs). However, the microbial-mediated dechlorination of Cl-OPEs at such sites has not yet been explored. Herein, the dechlorination products, pathways and mechanisms of tris(2-chloroethyl) phosphate (TCEP, a representative Cl-OPE) by an anaerobic enrichment culture (ZNE) from an ELVs dismantling plant were investigated. Our results showed that dechlorination of TCEP can be triggered by reductive transformation to form bis(2-chloroethyl) phosphate (BCEP), mono-chloroethyl phosphate (MCEP) and by hydrolytic dechlorination to form bis(2-chloroethyl) 2-hydroxyethyl phosphate (TCEP-OH), 2-chloroethyl bis(2-hydroxyethyl) phosphate (TCEP-2OH), 2-chloroethyl (2-hydroxyethyl) hydrogen phosphate (BCEP-OH). The combination of 16S rRNA gene amplicon sequencing, quantitative real-time PCR (qPCR) and metagenomics revealed that the Dehalococcoides played an important role in the reductive transformation of TCEP to BCEP and MCEP. A high-quality metagenome-assembled genome (completeness >99% and contamination <1%) of Dehalococcoides was obtained. The sulfate-reducing bacteria harboring haloacid dehalogenase genes (had) may be responsible for the hydrolytic dechlorination of TCEP. These findings provide insights into microbial-mediated anaerobic transformation products and mechanisms of TCEP at ELVs dismantling sites, having implications for the environmental fate and risk assessment of Cl-OPEs at those sites.

[Spatial Distribution of Soil Heavy Metals and Regional Control Strategies in China at Province Level].

It is important to understand the spatial distribution characteristics and health risks of soil heavy metals for the implementation of soil pollution control measures in different levels and regions. Based on the data of 706 core studies in the last 20 years, the spatial distribution characteristics, accumulation degree, and health risks of soil heavy metals in China were analyzed at the provincial level. The results showed that the soil heavy metals had obvious spatial differences on the provincial scale, with an overall trend of "high in the south and low in the north and high in the east and low in the west." The content of heavy metals in the soil of agricultural land and construction land was high, and the rate of exceeding the standard was higher than that of other land types. Soil heavy metal concentrations in most areas of China were higher than the regional background values and were highly cumulative. The accumulation indices were:Cd(1.80)>Pb(0.23)>Cu(0.17)>Zn(-0.05)>As(-0.56)>Cr(-0.69), with more than 85% of the provincial soils reaching moderate levels of Cd pollution. Non-ferrous metal resource-based provinces such as Yunnan, Guizhou, Guangxi, Hunan, and Jiangxi generally had higher soil heavy metal levels than those in other provinces, and local children faced higher cancer risks. Soil pollution in coastal areas such as Fujian, Zhejiang, Jiangsu, and Tianjin mainly originated from industrial production and urbanization construction. High intensity agricultural utilization was an important cause of soil heavy metal accumulation in Henan, Shandong, and Anhui.

Cleaner production of Chinese cabbage by intercropping from Cd contaminated soil: Effects of hyperaccumulator variety and planting strip width.

The utilization of Cd-contaminated soil in vegetable crop production can lighten the food crisis and improve the soil environmental resilience. Intercropping is a reliable technology in safety production from contaminated soil. A field-scale experiment was carried out to unravel how plant species and pattern affect the growth and Cd uptake of Chinese cabbage from Cd contaminated land. Among all the intercropping systems designed in this study, one row of Chinese cabbage intercropping with one row of Solanum nigrum L. is the best planting mode (high yields (2.78 kg/m2) and low Cd accumulation (0.02 mg/kg) of Chinese cabbage). Combined with the in-depth joint analysis of diverse soil physicochemical features (soil nutrient characteristics and microbial community structure), biomass yield and quality, and soil microbiological properties, we elaborated that two measures (screening hyperaccumulation types and controlling planting strip width) were the major factors in determining the growth of the aboveground and underground parts of Chinese cabbage respectively, thus directly regulating the application effectiveness of intercropping technology. The intertwined mechanisms (interspecific and intraspecific relationship) of different intercropping systems are summarized, which include better utilization of space, light and other resources in the aboveground part, bioavailability of nutrient, drive of soil bacteria and alleviated soil Cd stress in the underground part, etc. Our research outputs indicate the effectiveness and feasibility of intercropping can be improved by optimizing the streamline configuration and plant mode, which provide theory of reference and practical evidence for warranting the food safety and agricultural soil remediation simultaneously.

A new method for assessment of electro-osmotic permeability through the integration of theoretical and experimental ion flux in electrokinetic processes.

Electrokinetic (EK) technology is promising for removing heavy metals from contaminated unsaturated soils. It is crucial to accurately determine the unsaturated electro-osmotic permeability for predicting the efficiency of EK treatment, optimizing treatment strategies, and accurately predicting the distribution of contaminant concentrations. However, the current approach of estimating unsaturated electro-osmotic permeability, which involves measuring effective voltage, drainage volume, and performing exponential fitting, fails to address the issue of uneven voltage gradient distribution during EK treatment. Herein, a novel method was presented for estimating the electro-osmotic permeability of unsaturated porous media. This method quantifies the electro-osmotic flow in an unsaturated porous medium by considering the difference in mass-transfer efficiency (MTE) between real (with electro-osmotic flow) and hypothetical cases (without electro-osmotic flow). This difference serves as a metric for estimating the electro-osmotic permeability. Results revealed a linear relationship between the electro-osmotic permeability and the product of volumetric moisture content and tortuosity, with the slope related to the ionic mobility of target ions, hypothetical and actual MTE. To validate this method, hexavalent Cr (Cr(VI)) was selected as the target contaminant and six EK experiments were conducted with varying initial volumetric moisture content. The feasibility of the method was evaluated by fitting the results of these experiments to obtain the specific slope of the porous medium used. Compared to the existing effective voltage-drainage volume-exponential fitting method, the proposed method offers several advantages. First, it effectively addressed the issue of nonuniform voltage distribution during EK treatment in the unsaturated porous medium. Second, it overcame the problem of a nonzero electro-osmotic permeability at zero volumetric moisture content in the exponential empirical formula. Third, the proposed method was based on theoretical derivations instead of relying solely on empirical fitting. Finally, the proposed method does not require a prior estimate of the saturated electro-osmotic permeability of the porous medium.

Cytotoxicity and hemolysis of rare earth ions and nanoscale/bulk oxides (La, Gd, and Yb): Interaction with lipid membranes and protein corona formation.

The widespread application of rare earth elements (REEs) has raised concerns about their potential release into the environment and subsequent ingestion by humans. Therefore, it is essential to evaluate the cytotoxicity of REEs. Here, we investigated the interactions between three typical REEs (La, Gd, and Yb) ions as well as their nanometer/µm-sized oxides and red blood cells (RBCs), a plausible contact target for nanoparticles when they enter the bloodstream. Hemolysis of REEs at 50-2000 µmol L-1 was examined to simulate their cytotoxicity under medical or occupational exposure. We found that the hemolysis due to the exposure of REEs was highly dependent on their concentration, and the cytotoxicity followed the order of La3+ > Gd3+ > Yb3+. The cytotoxicity of REE ions (REIs) is higher than REE oxides (REOs), while nanometer-sized REO caused more hemolysis than that µm-sized REO. The production of reactive oxygen species (ROS), ROS quenching experiment, as well as the detection of lipid peroxidation, confirmed that REEs causes cell membrane rupture by ROS-related chemical oxidation. In addition, we found that the formation of a protein corona on REEs increased the steric repulsion between REEs and cell membranes, hence mitigating the cytotoxicity of REEs. The theoretical simulation indicated the favorable interaction of REEs with phospholipids and proteins. Therefore, our findings provide a mechanistic explanation for the cytotoxicity of REEs to RBCs once they have entered the blood circulation system of organisms.

The spatial distribution, health risk, and cytotoxicity of metal(loid)s in contaminated field soils: The role of Cd in human gastric cells damage.

The spatial distribution and pollution level of heavy metal(loid)s in soil (0-6 m) from a typical industrial region in Jiangmen City, Southeast China was investigated. Their bioaccessibility, health risk, and human gastric cytotoxicity in topsoil were also evaluated using an in vitro digestion/human cell model. The average concentrations of Cd (87.52 mg/kg), Co (106.9 mg/kg), and Ni (1007 mg/kg) exceeded the risk screening values. The distribution profiles of metal(loid)s showed a downward migration trend to reach a depth of 2 m. The highest contamination was found in topsoil (0-0.5 m), with the concentrations of As, Cd, Co, and Ni being 46.98, 348.28, 317.44, and 2395.60 mg/kg, respectively, while Cd showed the highest bioaccessibility in the gastric phase (72.80 %), followed by Co (21.08 %), Ni (18.27 %), and As (5.26 %) and unacceptable carcinogenic risk. Moreover, the gastric digesta of topsoil suppressed the cell viability and triggered cell apoptosis, evidenced by disruption of mitochondrial transmembrane potential and increase of Cytochrome c (Cyt c) and Caspases 3/9 mRNA expression. Bioaccessible Cd in topsoil was responsible for those adverse effects. Our data suggest the importance to reduce Cd in the soil to decrease its adverse impacts on the human stomach.

Quantitative source apportionment and driver identification of soil heavy metals using advanced machine learning techniques.

The accurate identification of pollution sources is essential for the prevention and control of possible pollution from soil heavy metals (SHMs). However, the positive matrix factorisation (PMF) model has been widely used as a conventional method for pollution source apportionment, and the classification of source apportionment results mainly relies on existing research and expert experience, which can result in high subjectivity in the source interpretation. To address this limitation, a comprehensive source apportionment framework was developed based on advanced machine learning techniques that combine self-organizing mapping and PMF with a gradient boosting decision tree (GBDT) model. Analysis of Cd, Pb, Zn, Cu, Cr, and Ni in 272 topsoils showed that the average contents of six heavy metals were 1.72-13.79 times greater than corresponding background values, among which Cd pollution was relatively serious, with 66.91 % of the sites having higher values than the specified soil risk screening values. The PMF results revealed that 79.43 % of Pb was related to vehicle emissions and atmospheric deposition, 79.32 % of Cd and 38.84 % of Zn were related to sewage irrigation, and 85.97 % of Cr and 85.50 % of Ni were from natural sources. Moreover, the GBDT detected that industrial network density, water network density, and Fe2O3 content were the major drivers influencing each pollution source. Overall, the novelty of this study lies in the development of an improved framework based on advanced machine learning techniques that led to the accurate identification of the sources of SHM pollution, which can provide more detailed support for environmental protection departments to propose targeted control measures for soil pollution.

Stable Isotopic and Metagenomic Analyses Reveal Microbial-Mediated Effects of Microplastics on Sulfur Cycling in Coastal Sediments.

Microplastics are readily accumulated in coastal sediments, where active sulfur (S) cycling takes place. However, the effects of microplastics on S cycling in coastal sediments and their underlying mechanisms remain poorly understood. In this study, the transformation patterns of different S species in mangrove sediments amended with different microplastics and their associated microbial communities were investigated using stable isotopic analysis and metagenomic sequencing. Biodegradable poly(lactic acid) (PLA) microplastics treatment increased sulfate (SO42-) reduction to yield more acid-volatile S and elementary S, which were subsequently transformed to chromium-reducible S (CRS). The S isotope fractionation between SO42- and CRS in PLA treatment increased by 9.1‰ from days 0 to 20, which was greater than 6.8‰ in the control. In contrast, recalcitrant petroleum-based poly(ethylene terephthalate) (PET) and polyvinyl chloride (PVC) microplastics had less impact on the sulfate reduction, resulting in 7.6 and 7.7‰ of S isotope fractionation between SO42- and CRS from days 0 to 20, respectively. The pronounced S isotope fractionation in PLA treatment was associated with increased relative abundance of Desulfovibrio-related sulfate-reducing bacteria, which contributed a large proportion of the microbial genes responsible for dissimilatory sulfate reduction. Overall, these findings provide insights into the potential impacts of microplastics exposure on the biogeochemical S cycle in coastal sediments.

A comprehensive framework for identifying contributing factors of soil trace metal pollution using Geodetector and spatial bivariate analysis.

The accurate identification of pollution sources is important for controlling soil pollution. However, the widely used Positive matrix factorization (PMF) model generally relies on knowledge and experience to accurately identify pollution sources; thus, this method faces significant challenges in objectively identifying soil pollution sources. Herein, we established a comprehensive source analysis framework using factor identification and geospatial analysis, and revealed the factors contributing to trace metal(loid) (TM) pollution in soil in the Pearl River Delta (PRD), China. Using the PMF model, we initially considered that the PRD may be affected by natural, atmospheric, traffic and industrial, and agricultural sources. Moreover, Geodetector model detected the relationship between TMs and 12 environmental variables based on the strong spatial "source-sink" relationship of pollutants. The parent material and digital elevation model were the key factors predicting the accumulation of Cr, Ni, and Cu. Industries and roads were the most important determinants of Pb, Zn, and Cd, whereas atmospheric deposition was more important for Hg accumulation. The accumulation of As was found to be closely related to agricultural activities such as the application of chemical fertilizers and pesticides. The spatial autocorrelation between soil TM pollution and environmental variables further supports this hypothesis. Overall, the obtained results showed that proposed approach improved the accuracy of source apportionment and provided a basis for soil pollution control.

Construction and application of the knowledge graph method in management of soil pollution in contaminated sites: A case study in South China.

Contaminated sites are a main cause of urban soil problems and have led to increasing pollution and public risk in China as a result of the rapid growth of industrial and urban land use. Because land pollution involves extensive multi-source heterogeneous information, identifying the risk of urban soil pollution efficiently and predicting pollution-related events are important for urban environmental management. Knowledge graphs (KGs) have unique advantages in dealing with massive amounts of information. This study attempts to construct a KG of contaminated sites in South China to explore its feasibility and effectiveness in urban soil environmental management. The results demonstrate that KGs have a favorable effect in information retrieval, knowledge reasoning, and visualization. Studied cases in this article demonstrate that the KG model can achieve many functions, including the display of global information of polluted sites, and discovery of regional distribution of characteristic pollutants and main pollutants of specific industries, based on special query syntax. However, this approach is limited by some technical difficulties, such as knowledge mining of natural resources, which must be overcome in future studies to improve the operability of KG technologies.

Suspect and nontarget screening of known and unknown organophosphate esters (OPEs) in soil samples.

Ninety-five soil samples (n = 95) were analyzed using an integrated suspect and non-target organophosphate ester (OPE) screening strategy. This suspect and non-target screening strategy allowed us to fully or tentatively identify 26 OPEs or OPE-like substances. Among these 26 newly identified contaminants, bisphenol A bis(diphenylphosphate) (BPABDP) exhibited the highest detection frequency of 83.2 %, with a concentration range of ND - 385 ng/g dry weight (dw). We also observed that BPABDP was significantly correlated with all other OPEs (p < 0.001 in all pairs), suggesting that BPABDP is widely used as a plasticizer and flame retardant in various commercial products. Another interesting finding was the discovery of four novel OPE structures with tentatively proposed chemical structures. Among these four non-target OPEs, (tert-butyl) phenyl bis(2,4-di-tert-butylphenyl) phosphate (TBPBDTBPP) shared a backbone structure very similar to that of the well-known OPE, tris(2,4-di-tert-butylphenyl) phosphate (TDTBPP). Detection frequency of this newly discovered OPE was high, up to 69.5 %, and it was significantly correlated with isodecyl diphenyl phosphate (IDDP), BPABDP, diphenyl 2-isopropylphenyl phosphate (2IPPDPP), and tricresyl phosphate (TCrP, p < 0.05 in all pairs), respectively. This study reported the most comprehensive suite of OPEs in soil samples, and 16 out of them were recognized in soil for the first time.

Potential application of Fusarium fungal strains (Fusarium sp. FP, Arthrinium sp. FB, and Phoma sp. FR) for removal of Tl (I) ions from water.

Water pollution caused by heavy metals poses a serious threat to the ecosystem and human health. Among the various treatment techniques for water remediation, adsorption is an efficient method due to its high capacity, low cost, and simplicity. Thallium (Tl) is highly toxic to mammals and its removal from water is gaining increasingly prominent attention. In this study, three fungal strains (Fusarium sp. FP, Arthrinium sp. FB, and Phoma sp. FR) were tested for removal of Tl (I) from aqueous solutions and showed excellent removal performance. The prepared inactive fungal strains were characterized by XRD, FT-IR, SEM, and XPS analyses. The effects of pH, contact time, biomass dosage, and reaction temperature on the removal efficiency of Tl (I) were systematically investigated. The results indicated that the adsorption isotherm data fit well with the Langmuir model, and the pseudo-second-order model was more consistent with the kinetic data description. The maximum adsorption capacity of the fungal strain (Fusarium sp. FP, Arthrinium sp. FB, and Phoma sp. FR) for Tl (I) was found to be 94.69 mg/g, 66.97 mg/g, and 52.98 mg/g, respectively. The thermodynamic data showed that the sorption process was spontaneous and endothermic. The present study showed that the inactive fungal strains could be a promising adsorbent material for Tl (I) removal.

A comprehensive evaluation of factors affecting the reactivity of FeS towards hexabromocyclododecane diastereoisomers.

Reactivity of iron sulfide (FeS) towards hexabromocyclododecane (HBCD) was explored under conditions of varying temperature, pH, inorganic ion and dissolved organic matter (DOM) in this study. Results show that the reduction of HBCD by FeS has an activation energy of 29.2 kJ mol-1, suggesting that the rate-limiting step in the reduction was a surface-mediated reaction. The reduction of HBCD by FeS was a highly pH-dependent process. The optimal rate for HBCD reduction by FeS was observed at a pH of 6.2. All the tested inorganic ions suppressed the reduction of HBCD by FeS. XPS analysis confirmed that both Fe(II)-S and bulk S(-II) on FeS surface could be impacted by solution pH and inorganic ions and were responsible for the regulation of HBCD reduction. Some DOMs (i.e., fulvic acid, humic acid, salicylic acid, catechol and sodium dodecyl sulfate) were found to hinder the reduction via competing with HBCD for active sites on FeS surface. However, the presence of 2,2'-bipyridine, triton X-100 and cetyltrimethyl ammonium bromide was able to significantly enhance the rate of HBCD reduction by 5.8, 9.0 and 20 times, respectively. Different factors could influence the reduction efficiency of HBCD diastereoisomers to different extent, but not the reaction orders of HBCD diastereoisomers (α-HBCD < γ-HBCD < ß-HBCD). Moreover, FeS could completely remove HBCD diastereoisomers in sediments with multiple factors within 9 d reaction. Our results contribute to give a better understanding on the performance of FeS towards HBCD under real and complex conditions and facilitate the application of FeS in remediation sites.

Polycyclic aromatic hydrocarbons (PAHs) and their derivatives (oxygenated PAHs, azaarenes, and sulfur / oxygen-containing heterocyclic PAHs) in surface soils from a typical city, south China.

Polycyclic aromatic hydrocarbons derivatives (dPAHs) were reported to be more mutagenic than parent analogues, however, studies that involving dPAHs in environmental samples are still limited. Thirty-six polycyclic aromatic compounds (PACs; 17 parent PAHs, 1 alkyl-PAH, 6 oxygenated PAHs, 6 azaarenes, 3 sulfur-containing heterocyclic PAHs, and 3 oxygen-containing heterocyclic PAHs) were analyzed in n = 100 surface soil samples collected from a prefecture-level city (hereafter referred to as D city) in South China, in the year 2019. Total concentrations of 36 PACs ranged from 3.61 to 4930 ng g-1 with a median concentration of 86.1 ng g-1. Regardless of functional zones, parent PAHs were the most abundant with the proportion of 78.9%, followed by oxygenated PAHs accounting for 16.8%, whereas contents of heterocyclic PAHs were far below the formers. Besides, PAHs with 4-6 rings were the most prevalent components. Among the five functional zones, industrial zone was contaminated most severely with a mean sum PAC concentration of 485 ng g-1, implying effects of long-term industrial emission. Total PAC concentrations in scenic and agricultural zones were significantly lower than those in industrial and residential zones. On the basis of PMF calculation, we proposed that traffic emission and biomass combustion could be responsible for PAC contamination. According to total lifetime cancer risk index, it suggested that there could be slightly health risks for children following exposure to PACs in some places.

A Combined Remediation Strategy of Arsenic and Cadmium in the Paddy Soil of Polymetallic Mining Areas.

The combined pollution of arsenic (As) and cadmium (Cd) are quite common in the polymetallic mining areas located in southern China. In the present study, field experiments were established for the purpose of exploring a simultaneous remediation strategy of rice variety-water management-contaminant immobilization on the As and Cd contamination in paddy soil. The obtained results revealed that the Maba Yinzhan was the best low-accumulation rice variety, with As and Cd concentrations of 0.54 and 0.16 mg kg-1, respectively, in the rice grains. On the basis of water management during heading stage, the treatment using 0.15 wt% lime plus 0.5 wt% ferro-ferric oxide (FO) decreased the As and Cd concentrations by 64.02% and 34.78%, respectively, in the grains. The results of this study potentially provide an effective remediation solution for the As/Cd contaminated soils in polymetallic mining areas.

Newly discovered bis-(2-ethylhexyl)-phenyl phosphate (BEHPP) was a ubiquitous contaminant in surface soils from a typical region, South China.

The organophosphate ester (OPE), bis-(2-ethylhexyl)-phenyl phosphate (BEHPP), was recently identified as an abundant contaminant in indoor dust samples; however, its pollution status in other matrices remains unknown. Here, n = 95 surface soil samples were collected from a prefecture-level city (hereafter referred to as D city) in South China during 2019, and further analyzed to accurately determine the concentrations of BEHPP and eight other OPEs, including tris(2-chloroethyl) phosphate (TCEP), tris(1,3-dichloro-isopropyl) phosphate (TDCIPP), triphenyl phosphate (TPHP), tris(2-butoxyethyl) phosphatetris (TBOEP), 2-ethylhexyl diphenyl phosphate (EHDPP), tris(2-ethylhexyl) phosphate (TEHP), 4-biphenylol diphenyl phosphate (BPDPP), and tris(2-biphenyl) phosphate (TBPHP). BEHPP was detected in all six functional areas (agricultural, scenic, commercial, industrial, and residential areas) of this region, and exhibited a high detection frequency of 67.4%, with a median concentration of 0.455 ng/g dry weight (DW range: nd-7.05 ng/g dw), regardless of the functional area. Samples from commercial, industrial, and residential areas contained significantly greater BEHPP concentrations than those from agricultural and scenic areas. Furthermore, strong and statistically significant correlations were observed between BEHPP and other OPE congeners, particularly for TEHP (r = 0.764, p < 0.001), TBOEP (r = 0.687, p < 0.001), and TPHP (r = 0.709, p < 0.001), indicating that BEHPP may have similar commercial applications and sources to these compounds in surface soil. Collectively, this study provides the first evidence of the presence of BEHPP in soil samples, and indicates that this emerging contaminant is widely distributed across all five functional areas of a typical region (South China).

Reductive degradation of chlorinated organophosphate esters by nanoscale zerovalent iron/cetyltrimethylammonium bromide composites: Reactivity, mechanism and new pathways.

Chlorinated organophosphate esters (Cl-OPEs), e.g., tris(2-chloroethyl) phosphate (TCEP), tris(2-chloro-2-propyl) phosphate (TCPP) and tris(1,3-dichloro-2-propyl) phosphate (TDCPP), are widely used as additive flame retardants in commercial and building products. They have potential persistent organic pollutant properties and are frequently detected in various waters, especially in wastewaters. Nanoscale zerovalent iron (nZVI)-based method is an efficient reductive technology for treating waters polluted by halogenated organic pollutants (HOCs). Cetyltrimethylammonium bromide (CTAB) is a ubiquitous surfactant in wastewaters and can favorably affect the interaction between HOCs and nZVI. However, its effect on the Cl-OPEs removal by nZVI-based materials still remains unknown. Herein, the adsorption and degradation efficiencies of Cl-OPEs by nZVI and sulfidated nZVI (S-nZVI) in the presence or absence of CTAB were quantified based on the decreasing concentrations of Cl-OPEs in reaction systems. Our results showed that TDCPP and TCPP were adsorbed onto the nZVI or S-nZVI surface and subsequently degraded. In contrast, TCEP was just adsorbed onto the particle surface without further degradation. The addition of CTAB significantly enhanced the hydrophobic adsorption between Cl-OPEs and nZVI or S-nZVI, leading to increased degradation of Cl-OPEs (especially TCEP). CTAB adsorption isotherms indicated that S-nZVI had a higher adsorption capacity for CTAB than nZVI. The S-nZVI/CTAB composite exhibited a better performance than nZVI/CTAB composite. When S-nZVI was combined with 100.0 mg L-1 CTAB, 100% of TDCPP, TCPP and TCEP was degraded within 3 hours, 5 and 14 days, respectively. As the concentration of CTAB was increased up to 335.0 mg L-1, TCEP could be completely degraded within 3 days by S-nZVI. Five degradation products of TCEP were identified, of which O,O-di-(2-chloroethyl) O-ethyl phosphate (DCEEP) and ethane were reported for the first time. We propose that TCEP is dechlorinated by nZVI or S-nZVI through the electron attack at the ethyl-chlorine group to form bis(2-chloroethyl) phosphate, DCEEP, chloride, ethene and ethane, representing previously unknown degradation pathways.

Enhanced tetrabromobisphenol A debromination by nanoscale zero valent iron particles sulfidated with S0 dissolved in ethanol.

Modification of nanoscale zero-valent iron (nZVI) with reducing sulfur compounds has proven to improve the reactivity of nZVI towards recalcitrant halogenated organic contaminants. In this study, we develop a novel method for the preparation of sulfidated nZVI (S-nZVI) with S0 (a low cost and available reducing sulfur agent) dissolved in ethanol under mild conditions and apply it for the transformation of tetrabromobisphenol A (TBBPA), a potential persistent organic pollutant. Surface analysis shows that S0 dissolved in ethanol has been successfully doped into nZVI via a reaction with Fe0 to form a relatively homogeneous layer of FeS/FeS2 on the nZVI surface. The H2 production test and the electrochemical analysis show that the FeS/FeS2 layer not only slows the H2 evolution reaction but also enhances the electron transfer. Debromination kinetics indicate that the resulting S-nZVI with a S/Fe ratio of 0.015-0.05 possesses higher debromination activity for TBBPA and its debromination products (i.e., tri-BBPA, di-BBPA, mono-BBPA and BPA) in comparison with nZVI. Among them, S-nZVI at a S/Fe of 0.025 (S-nZVIS-0.025) has the greatest debromination rate constant (kobs) of 1.19 ± 0.071 h-1 for TBBPA. It debrominates TBBPA at a faster rate than other conventional S-nZVI made from Na2S and Na2S2O4 and has been successfully applied in the treatment of TBBPA-spiked environmental water samples (including river water, groundwater, and tap water). The results suggest that the modification of nZVI with S0 dissolved in ethanol is a simple, safe, inexpensive, and effective sulfidation technique, which can be applied for the large-scale production of S-nZVI for treating contaminated water.