PBAT biodegradable microplastics enhanced organic matter decomposition capacity and CO2 emission in soils with and without straw residue.

Recent studies show that biodegradable microplastics (BMPs) could increase soil CO2 emission, but whether altered carbon emission results from modified soil organic matter (SOM) decomposition remains underexplored. In this study, the effect and mechanisms of BMPs on CO2 emission from soil were investigated, using poly(butylene adipate-co-terephthalate) (PBAT, the main component of agricultural film) as an example. Considering that straw returning is a common agronomic measure which may interact with microplastics through affecting microbial activity, both soils with and without wheat straw were included. After 120 d, 1 % (w/w) PBAT BMPs ificantly increased cumulative CO2 emission by 1605.6 and 1827.7 mg C kg-1 in soils without and with straw, respectively. Cracks occurred on the surface of microplastics, indicating that CO2 was partly originated from plastic degradation. Soil dissolved organic matter (DOM) content, carbon degradation gene abundance (such as abfA, xylA and manB for hemicellulose, mnp, glx and lig for lignin, and chiA for chitin) and enzyme activities increased, which significantly positively correlated with CO2 emission rate (p < 0.05), suggesting that PBAT enhanced carbon emission by stimulating the decomposition of SOM (and possibly the newly added straw) via co-metabolism and nitrogen mining. This is supported by DOM molecular composition analysis which also demonstrated stimulated turnover of carbohydrates, amino sugars and lignin following PBAT addition. The findings highlight the potential of BMPs to affect SOM stability and carbon emission.

Centennial Records of Microplastics in Lake Cores in Huguangyan Maar Lake, China.

Microplastic records from lake cores can reconstruct the plastic pollution history. However, the associations between anthropogenic activities and microplastic accumulation are not well understood. Huguangyan Maar Lake (HML) is a deep-enclosed lake without inlets and outlets, where the sedimentary environment is ideal for preserving a stable and historical microplastic record. Microplastic (size: 10-500 µm) characteristics in the HML core were identified using the Laser Direct Infrared Imaging system. The earliest detectable microplastics appeared unit in 1955 (1.1 items g-1). The microplastic abundance ranged from n.d. to 615.2 items g-1 in 1955-2019 with an average of 134.9 items g-1. The abundance declined slightly during the 1970s and then increased rapidly after China's Reform and Opening Up in 1978. Sixteen polymer types were detectable, with polyethylene and polypropylene dominating, accounting for 23.5 and 23.3% of the total abundance, and the size at 10-100 µm accounted for 80%. Socioeconomic factors dominated the microplastic accumulation based on the random forest modeling, and the contributions of GDP per capita, plastic-related industry yield, and total crop yield were, respectively, 13.9, 35.1, and 9.3% between 1955-2019. The total crop yield contribution further increased by 1.7% after 1978. Coarse sediment particles increased with soil erosion exacerbated microplastics discharging into the sediment.

Strong Substance Exchange at Paddy Soil-Water Interface Promotes Nonphotochemical Formation of Reactive Oxygen Species in Overlying Water.

Photochemically generated reactive oxygen species (ROS) are widespread on the earth's surface under sunlight irradiation. However, the nonphotochemical ROS generation in surface water (e.g., paddy overlying water) has been largely neglected. This work elucidated the drivers of nonphotochemical ROS generation and its spatial distribution in undisturbed paddy overlying water, by combining ROS imaging technology with in situ ROS monitoring. It was found that H2O2 concentrations formed in three paddy overlying waters could reach 0.03-16.9 µM, and the ROS profiles exhibited spatial heterogeneity. The O2 planar-optode indicated that redox interfaces were not always generated at the soil-water interface but also possibly in the water layer, depending on the soil properties. The formed redox interface facilitated a rapid turnover of reducing and oxidizing substances, creating an ideal environment for the generation of ROS. Additionally, the electron-donating capacities of water at soil-water interfaces increased by 4.5-8.4 times compared to that of the top water layers. Importantly, field investigation results confirmed that sustainable •OH generation through nonphotochemical pathways constituted of a significant proportion of total daily production (>50%), suggesting a comparable or even greater role than photochemical ROS generation. In summary, the nonphotochemical ROS generation process reported in this study greatly enhances the understanding of natural ROS production processes in paddy soils.

Key role of hydrogen atoms in the preparation of sulfidated zero valent iron.

Sulfidated zero valent iron (ZVI) is a popular material for the reductive degradation of halogenated organic pollutants. Simple and economic synthesis of this material is highly demanded. In this study, sulfidated micro/nanostructured ZVI (MNZVI) particles were prepared by simply heating MNZVI particles and sulfur elements (S0) in pure water (50℃). The iron oxides on the surface of MNZVI particles were conducive to sulfidation reaction, indicating the formation of iron-sulphide minerals (FeSx) on the surface of MNZVI particles might not be from the direct reaction of Fe0 with S0 (Fe0 and S0 acted as reductant and oxidant, respectively). As an important reductant, hydrogen atom (H•) can be generated from the reduction of H+ by MNZVI particles and participate in the formation of FeSx. Quenching experiment and cyclic voltammetry analysis proved the existence of H• on the surface of MNZVI particles. DFT calculation found that the potential barrier of H•/S0 and Fe0/S0 were 1.91 and 7.24 eV, respectively, indicating that S0 would preferentially react with H• instead of Fe0. The formed H• can quickly react with S0 to generate hydrogen sulfide (H2S), which can further react with iron oxides such as α-Fe2O3 on the surface of MNZVI particles to form FeSx. In addition, the H2 partial pressure in water significantly affected the amount of H• generated, thereby affecting the sulfidation efficiency. For TCE degradation, as the sulfur loading of sulfidated MNZVI particles increased, the contribution of H• significantly decreased while the contribution of direct electron transfer increased. This study provided new insights into the synthesis mechanism of sulfidated ZVI in water.

Insight into the adsorption behaviors and bioaccessibility of three altered microplastics through three types of advanced oxidation processes.

Advanced oxidation processes (AOPs) can significantly alter the structural properties, environmental behaviors and human exposure level of microplastics in aquatic environments. Three typical microplastics (Polyethylene (PE), polypropylene (PP), and polystyrene (PS)) and three AOPs (Heat-K2S2O8 (PDS), UV-H2O2, UV-peracetic acid (PAA)) were adopted to simulate the process when microplastics exposed to the sewage disposal system. 2-Nitrofluorene (2-NFlu) adsorption experiments found the equilibrium time decreased to 24 hours and the capacity increased up to 610 µg g-1, which means the adsorption efficiency has been greatly improved. The fitting results indicate the adsorption mechanism shifted from the partition dominant on pristine microplastic to the physical adsorption (pore filling) dominant. The alteration of specific surface area (21 to 152 m2 g-1), pore volume (0.003 to 0.148 cm3 g-1) and the particle size (123 to 16 µm) of microplastics after AOPs are implying the improvement for pore filling. Besides, the investigation of bioaccessibility is more complex, AOPs alter microplastic with more oxygen-containing functional groups and lower hydrophobicity detected by XPS and water contact angle, those modifications have increased the sorption concentration, especially in the human intestinal tract. Therefore, this indicates the actual exposure of organic compounds loaded in microplastic may be higher than in the pristine microplastic. This study can help to assess the human health risk of microplastic pollution in actual environments.

Preparation of Fe/Cu bimetals by ball milling iron powder and copper sulfate for trichloroethylene degradation: Combined effect of FeSx and Fe/Cu alloy.

The addition of a secondary metal (such as Cu, Co, Ni and Pd) to form iron-based bimetallic particles could enhance the reactivity of zero valent iron (ZVI). This study proposed a new synthesis method for preparing Cu-Fe bimetals (Cu-Febm (CuSO4)) by ball milling mZVI and CuSO4. During ball-milling process, 40% of Cu2+ can be reduced to Cu0, which formed galvanic couple with Fe0 in a way of Fe/Cu alloy structure. Part Cu2+ was only reduced to Cu+ (corresponding to Cu2O), while 29% of SO42- was reduced to Sx2- (corresponding to FeSx). The appearance of Cu2O was not conducive to the activity of Cu-Febm (CuSO4) particles, the formation of Fe0/FeSx structure compensated for the partial loss of Fe/Cu alloy. H•abs was identified as the main active species for TCE degradation by Cu-Febm (CuSO4) bimetals. The Cu-Febm (CuSO4) bimetals has great potential for the removal of chlorinated hydrocarbons in water.

Insights into adsorption mechanisms of nitro polycyclic aromatic hydrocarbons on common microplastic particles: Experimental studies and modeling.

Nitro polycyclic aromatic hydrocarbons (NPAHs) and microplastics (MPs) are emerging contaminants that pose a threat to the aquatic ecosystem. Knowledge of the NPAHs and MPs interaction will help the understanding of their fate and risks in natural environment. Here, the adsorption behavior and mechanism of typical NPAHs on microplastics were investigated. The adsorption kinetic and isotherm data showed that the adsorption of NPAHs was controlled by chemical adsorption and hydrophobic partition, because of excellent fit of kinetic and isothermal equations (R2 > 0.9). The adsorption capacity (587-744 µg g-1) was largely dependent on the hydrophobicity of NPAHs. The experiment of environmental factors confirmed the important role of pollutant hydrophobicity, with 1-Npyr of the highest hydrophobicity having the greatest adsorption on MPs (adsorption rate >90%) and less affected by solution pH and ionic strength (changer <5%). In the mixture system, MPs displayed high adsorption capacity for each compound; Interestingly, because compounds with smaller size were easy to occupy the adsorption sites in the pores of MPs, the adsorption of 2-Nflu (724 µg g-1) was even greater than that of 9-Nant (713 µg g-1) and 1-Npyr (703 µg g-1). The model calculation of adsorption also shows that there is surface adsorption and hydrophobic distribution in the adsorption process. The findings provide new insights into the interactions of MPs with organic pollutants in complex environments.

Bioaccessibility and bioavailability of NPAHs in soils using in vitro-in vivo assays: Comparison of laboratory and outdoor environmental aging effect.

Aging process is one of the most important factors that markedly reduces bioaccessibility and bioavailability (bioac-bioav) of organic contaminants. However, only few data on comparison of the effects of laboratory artificial aging (LAA) and outdoor environmental aging (OEA) processes on nitrated polycyclic aromatic hydrocarbons (NPAHs) bioac-bioav are available. In the current study, oral bioac-bioav of NPAHs in LAA and OEA soils (aging time intervals: 0, 45, 90, 120 and 150 d) were measured by in vitro traditional Fed ORganic Estimation human Simulation Test (FOREhST) and Tenax improved FOREhST (TI-FOREhST) methods, and in vivo mouse model. Tenax significantly increased the bioaccessibility of NPAHs in freshly spiked and aging soils from 0.3-40.9 % to 15.6-95.3 %, and 0.3-40.9 % to 1.0-84.5 %, respectively. Aging significantly reduced the NPAHs bioaccessibility (from 36.5 % to 10.7 %, and 12.1 % to 5.1 % as measured by FOREhST and TI-FOREhST, respectively) and bioavailability (from 27.7 % to 9.9 %, as measured by mouse model). The changes in bioac-bioav were mainly observed within the first 120 d of aging. The statistical analyses of NPAHs bioac-bioav showed no significant difference (p > 0.05) among the aging time intervals in LAA and OEA soils, which demonstrated that the LAA can relatively represent the OEA. Determination of TOC content in LAA and OEA soil can intuitively reflect whether the difference of NPAHs bioac-bioav between two aging treatment groups is significant. The mean bioaccessibility of NPAHs in soil measured by TI-FOREhST (mean 20.6 %) is closer to the bioavailability measured by mouse model (mean 19.4 %), indicating that Tenax improved in vitro method is more reliable than traditional methods, to predict the bioavailability of NPAHs.

Photocatalysis Combined with Microalgae to Promote the Degradation and Detoxification of Tetracycline Hydrochloride.

The continuous discharge of antibiotics into the environment poses a serious threat to the ecological environment and human health. In this study, photocatalysis and microalgae were combined to study the removal of tetracycline hydrochloride (TCH) and its photodegradation intermediates in water. The results showed that after photocatalytic treatment, the removal rate of TCH reached 80%, but the mineralization rate was only 17.7%. While Chlorella sp. alone had poor tolerance to high concentrations of TCH, the combined treatment of photocatalysis and microalgae completely removed TCH and increased the mineralization efficiency to 35.0%. Increased cell density was observed, indicating that TCH and the intermediates produced in the photocatalysis process could be utilized by algae for growth. Meanwhile, TCH degradation pathways were proposed based on Liquid Chromatograph Mass Spectrometer analysis, and the toxicity of intermediates detected was predicted using ECOSAR software, which showed that the type and quantity of highly toxic intermediates decreased significantly after subsequent algal treatment. The results demonstrate that photocatalysis and microalgae combined treatment is an efficient and eco-friendly method for the removal of antibiotics in water.

Anti-passivation ability of sulfidated microscale zero valent iron and its application for 1,1,2,2-tetrachloroethane degradation.

The performance of sulfidated zero valent iron (ZVI) for the degradation of chlorinated hydrocarbons under aerobic conditions remains unclear. In this study, sulfidated microscale ZVI (S-mZVI) was prepared for 1,1,2,2-tetrachloroethane (TeCA) degradation under aerobic conditions. Compared with mZVI, S-mZVI showed excellent passivation resistance during the degradation of TeCA and its hydrolysis/reduction products. This was probably because the existence of FeSx shell (FeS/FeS2/FeSn) protected the internal ZVI core from passivation. Though the outer layer of FeSx shell could be oxidized to FeSn and Fe2(SO4)3 as the reaction proceeded, the inner layer remained stable, which maintained the fast electron transfer capability of S-mZVI. The high temperature could enhance the degradation of TeCA, without compromising the anti-passivation and reusability of S-mZVI. Even after the fifth cycle, S-mZVI could still efficiently degrade 90% of TeCA within 24 h. Furthermore, it was found that the degradation of TeCA and its reduction products (e.g., dichloroethylene (DCE)) by S-mZVI relied on direct electron transfer and hydrogen radical (H•), respectively, which might explain the lower levels of toxic DCE in the S-mZVI system. This study provides valuable information for the practical application of S-mZVI in the treatment of wastewater containing halogenated hydrocarbons under ambient conditions.

Occurrence, partition behavior, source and ecological risk assessment of nitro-PAHs in the sediment and water of Taige Canal, China.

Nitrated polycyclic aromatic hydrocarbons (NPAHs) are widespread organic pollutants that possess carcinogenic and mutagenic properties, so they may pose a risk to the environment and human health. In this study, the concentrations of 15 NPAHs and 16 polycyclic aromatic hydrocarbons (PAHs) in 30 surface water samples and 26 sediment samples were measured in 2018 from the Taige Canal, one of the main rivers flowing into Taihu Lake, China. The total NPAH concentrations in water and sediment ranged from 14.7 to 235 ng/L and 22.9 to 96.5 ng/g dw, respectively. 9-nitrophenanthrene (nd-76.3 ng/L) was the dominant compound in surface water, while 2+3-nitrofluoranthene (1.73-18.1 ng/g dw) dominated in sediment. Among PAHs, concentration ranging from 1,097 to 2,981 ng/L and 1,089 to 4,489 ng/g dw in surface water and sediment, respectively. There was a strong positive correlation between the log octanol-water partition coefficient (Kow) and log sediment-water partition coefficient due to hydrophobic interaction. The fugacity fraction value increased with the decrease of log Kow, and chrysene was transferred from water into sediment. The residual NPAHs in surface water and sediment of the Taige Canal have partial correlation. Diesel engine and coal combustion emissions were probably the principal sources of NPAHs in surface water and sediment. The results of ecological risk assessment showed that some NPAHs in water (e.g, 1-nitropyrene and 6-nitrochrysene) and sediment (e.g., 2-nitrobiphenyl, 5-nitroacenaphthene, 9-nitrophenanthrene and 2+3-nitrofluoranthene) had moderate ecological risks, which should be of concern.

Efficient chlorinated alkanes degradation in soil by combining alkali hydrolysis with thermally activated persulfate.

Alkali activation is the most commonly used activation method for persulfate (PS) in in-situ remediation. However, the role of alkali in pollutant degradation is still elusive, limiting the optimization of relevant remediation strategies. In this study, we found that chlorinated alkanes (e.g., tetrachloroethane (TeCA)) could be efficiently degraded by thermal-alkali activation of PS. The main role of alkali was not activating PS but hydrolyzing the chlorinated alkanes, which was evidenced by the immediate conversion of TeCA into trichloroethylene (TCE) with NaOH and PS or with sole NaOH solution. Electron paramagnetic resonance analysis also showed that with a high NaOH/PS molar ratio (4:1) the intensity of oxidative radicals decreased, implying that high levels of alkali did not favor the formation of free radicals. Interestingly, better degradation of TeCA and its product TCE was observed by the combination of alkaline hydrolysis and thermal activation of PS (where alkali was added 6 h before PS rather than simultaneously) in comparison to thermal-alkali activation of PS. This study provides new insights into the remediation of chlorinated alkane-contaminated soils by in-situ chemical oxidation.

Community structure and co-occurrence network analysis of bacteria and fungi in wheat fields vs fruit orchards.

Soil microorganisms play a vital role in biogeochemical processes and nutrient turnover in agricultural ecosystems. However, the information on how the structure and co-occurrence patterns of microbial communities response to the change of planting methods is still limited. In this study, a total of 34 soil samples were collected from 17 different fields of 2 planting types (wheat and orchards) along the Taige Canal in Yangtze River Delta. The structure of bacterial and fungal communities in soil were determined by 16S rRNA gene and ITS gene, respectively. The dominated bacteria were Proteobacteria, Acidobacteriota, Actinobacteriota, Chloroflexi, Bacteroidota, and Firmicutes. The relative abundances of Actinobacteriota and Firmicutes were higher in the orchards, while Chloroflexi and Nitrospirota were more abundant in wheat fields. Ascomycota, Mortierellomycota, and Basidiomycota were the predominant fungus in both soil types. Diversity of bacterial and fungal communities were greater in the wheat fields than in orchards. Statistical analyses showed that pH was the main factor shaping the community structure, and parameters of water content (WC), total organic carbon (TOC) and total nitrogen (TN) had great influences on community structure. Moreover, high co-occurrence patterns of bacterial and fungal were confirmed in both wheat fields and orchards. Network analyses showed that both wheat fields and orchards occurred modular structure, including nodes of Acidobacteriota, Chloroflexi, Gemmatimonadota, Nitrospirota and Ascomycota. In summary, our work showed the co-occurrence network and the convergence/divergence of microbial community structure in wheat fields and orchards, giving a comprehensive understanding of the microbe-microbe interaction during planting methods' changes.

Inactivation Mechanism of Algal Chlorophyll by Allelochemical Quercetin.

Cyanobacteria harmful algal blooms (CyanoHABs) are a global concern. Application of allelochemicals is a promising solution for cyanobacteria control, due to its high efficiency, low cost and ecological safety. Flavonoids (natural polyphenols produced by aquatic plants) are reported capable of effectively inhibiting the growth of algae; however, the molecular mechanism of algae chlorophyll inactivation is still unclear. In this study, quercetin was used as a typical flavonoid, to investigate the inactivation effect of allelochemical on Microcystis aeruginosa chlorophyll a. The absorption and fluorescence spectra showed that chlorophyll reacted with quercetin to form pheophytin, and the formation rate of pheophytin increased with increasing quercetin concentration (1 × 10-5-1 × 10-2 M). FTIR spectra and DFT calculation showed that Mg2+ complexed with the 3-OH and 4-C = O groups in the quercetin ring C so that chlorophyll was inactivated due to the loss of Mg2+ ions. Overall, this study revealed that quercetin inactivated chlorophyll a of cyanobacteria by capturing Mg2+ ions, providing insights into the molecular mechanisms of algal bloom control by allelochemicals.

Rapid As(III) oxidation mediated by activated carbons: Reactive species vs. direct oxidation.

Activated carbon (AC) is widely used in pollutant removal, due to its adsorption capacity, conductivity and catalytic performance. However, few studies focus on the redox activity of AC and its role in pollutant transformation. In this study, we found that AC could efficiently mediate the oxidation of As(III) and the process of As(III) oxidation was pH and oxygen concentration dependent. In general, the presence of O2 promoted As(III) oxidation at pH 3.0-9.5. Acidic and alkaline conditions favored As(III) oxidation regardless of whether there was oxygen, but the mechanisms involved were quite different when there was oxygen. At pH 3.0, reactive species (H2O2 and ·OH) were generated and accounted for As(III) oxidation; at pH 9.5, As(III) was directly oxidized by O2 (electron transfer from As(III) to O2 mediated by carbon matrix) under aerobic conditions. Pre-oxidation and cyclic experiments results indicated the ability of AC to oxidize As(III) at pH 9.5 was sustainable and recyclable. This study provided a new insight in pollutant oxidation by AC in the environment.

Biotic Process Dominated the Uptake and Transformation of Ag+ by Shewanella oneidensis MR-1.

Silver ions (Ag+) directly emitted from industrial sources or released from manufactured Ag nanoparticles (AgNPs) in biosolid-amended soils have raised concern about the risk to ecosystems. However, our knowledge of Ag+ toxicity, internalization, and transformation mechanisms to bacteria is still insufficient. Here, we combine the advanced technologies of hyperspectral imaging (HSI) and single-particle inductively coupled plasma mass spectrometry to visualize the potential formed AgNPs inside the bacteria and evaluate the contributions of biological and non-biological processes in the uptake and transformation of Ag+ by Shewanella oneidensis MR-1. The results showed a dose-dependent toxicity of Ag+ to S. oneidensis MR-1 in the ferrihydrite bioreduction process, which was primarily induced by the actively internalized Ag. Moreover, both HSI and cross-section high-resolution transmission electron microscopy results confirmed that Ag inside the bacteria existed in the form of particulate. The Ag mass distribution in and around live and inactivated cells demonstrated that the uptake and transformation of Ag+ by S. oneidensis MR-1 were mainly via biological process. The bioaccumulation of Ag+ may be lethal to bacteria. A better understanding of the uptake and transformation of Ag+ in bacteria is central to predict and monitor the key factors that control Ag partitioning dynamics at the biointerface, which is critical to develop practical risk assessment and mitigation strategies.

Microplastics altered soil microbiome and nitrogen cycling: The role of phthalate plasticizer.

Microplastics are emerging contaminants that are increasingly detected in soil environment, but their impact on soil microbiota and related biogeochemical processes remains poorly understood. In particular, the mechanisms involved (e.g., the role of chemical additives) are still elusive. In this study, we found that plasticizer-containing polyvinyl chloride (PVC) microplastics at 0.5% (w/w) significantly increased soil NH4+-N content and decreased NO3--N content by up to 91%, and shaped soil microbiota into a microbial system with more nitrogen-fixing microorganisms (as indicated by nifDHK gene abundance), urea decomposers (ureABC genes and urease activity) and nitrate reducers (nasA, NR, NIT-6 and napAB genes), and less nitrifiers (amoC gene and potential nitrification rate). Exposure to plasticizer alone had a similar effect on soil nitrogen parameters but microplastics of pure PVC polymer (either granule or film) had little effect over 60 days, indicating that phthalate plasticizer released from microplastics was the main driver of effects observed. Furthermore, a direct link between phthalate plasticizer, microbial taxonomic changes and altered nitrogen metabolism was established by the isolation of phthalate-degrading bacteria involved in nitrogen cycling. This study highlights the importance of chemical additives in determining the interplay of microplastics with microbes and nutrient cycling, which needs to be considered in future studies.

Dibutyl phthalate release from polyvinyl chloride microplastics: Influence of plastic properties and environmental factors.

In recent years, great efforts have been made to understand the capacity of microplastics to adsorb environmental pollutants; however, relatively little is known about the ability of microplastics to release inherent additives into peripheral environments. In this study, we investigated the leaching behavior of phthalate plasticizer from polyvinyl chloride (PVC) microplastics, in aqueous solutions relevant to aquatic and soil environments. It was found that plastic properties, such as particle size, plasticizer content and aging of plastics had a great effect on the leaching of dibutyl phthalate (DnBP). Phthalate release was generally higher in smaller particles and particles with higher phthalate content. Whereas, plastic aging caused by solar irradiation could either enhance phthalate release by increasing plastic hydrophilicity or decrease the leaching by reducing readily available fractions of phthalate. Regarding environmental factors, solution pH (3-9) and ionic strength (0-0.2 M NaCl) were found to have minor effect on phthalate release, while fulvic acid (0-200 mg/L) greatly promoted the release by improving phthalate solubility and solution-plastic affinity. Interestingly, we found that more DnBP was leached out when fulvic acid and NaCl coexisted, and the results from dissolved organic carbon (DOC) and three-dimensional fluorescence spectroscopy analyzes suggested that the leaching of other fulvic acid-like additives might have played a role. These findings would be helpful for predicting the potential of microplastics to release toxic additives under different environmental conditions.

Distribution Characteristics and Relevance of Heavy Metals in Soils and Colloids Around a Mining Area in Nanjing, China.

Heavy metal pollution in agricultural soils poses a direct threat to food safety and human health. It has been shown that the colloids is the carrier of heavy metal transport in the polluted soil by heavy metals, but the sources of heavy metals in the soil and colloids and their interrelations are not transparent at present. This study aims to investigate the distribution characteristics of heavy metals in agricultural soils near mining areas, and reveal the relevance of heavy metal content in colloids with total content in soils and their chemical species in soils. Results showed that the concentrations of Mn, Zn, and Pb in agricultural soils and colloids were higher than those of other heavy metals. The content of heavy metals in colloids was positively correlated with the total content of heavy metals in soil. Heavy metals in soil could be easily combined by humus-like substances and tryptophan-like protein in the colloids. The primary source of heavy metals in soil and colloids was mining activities. This study provides theoretical support for revealing the pollution characteristics and migration of heavy metals in agricultural soils and colloids around mining areas.

Pyrogenic Carbon Initiated the Generation of Hydroxyl Radicals from the Oxidation of Sulfide.

Sulfide is one of the most abundant reductants in the subsurface environment, while pyrogenic carbon is a redox medium that widely exists in sulfide environment. Previous studies have found pyrogenic carbon can mediate the reductive degradation of organic pollutants under anoxic sulfide conditions; however, the scenario under oxic sulfide conditions has rarely been reported. In this study, we found that pyrogenic carbon can mediate hydroxyl radicals (•OH) generation from sulfide oxidation under dark oxic conditions. The accumulated •OH ranged from 2.07 to 101.90 µM in the presence of 5 mM Na2S and 100 mg L-1 pyrogenic carbon at pH 7.0 within 240 min. The Raman spectra and electrochemical cell experiments revealed that the carbon defects were the possible chemisorption sites for oxygen, while the graphite crystallites were responsible for the electron transfer from sulfide to O2 to generate H2O2 and •OH. Quenching experiments and degradation product identification showed that As(III) and sulfanilamide can be oxidized by the generated •OH. This research provides a new insight into the important role of pyrogenic carbon in redox reactions and dark •OH production.