Large-scale soil application of hydrochar: Reducing its polycyclic aromatic hydrocarbon content and toxicity by heating.

The beneficial roles of hydrochar in carbon sequestration and soil improvement are widely accepted. Despite few available reports regarding polycyclic aromatic hydrocarbons (PAHs) generated during preparation, their potential negative impacts on ecosystems remain a concern. A heating treatment method was employed in this study for rapidly removing PAHs and reducing the toxicity of corn stover-based hydrochar (CHC). The result showed total PAHs content (∑PAH) decreased and then sharply increased within the temperature range from 150 °C to 400 °C. The ∑PAH and related toxicity in CHC decreased by more than 80% under 200 °C heating temperature, compared with those in the untreated sample, representing the lowest microbial toxicity. Benzo(a)pyrene produced a significant influence on the ecological toxicity of the hydrochar among the 16 types of PAHs. The impact of thermal treatment on the composition, content, and toxicity of PAHs was significantly influenced by the adsorption, migration, and desorption of PAHs within hydrochar pores, as well as the disintegration and aggregation of large molecular polymers. The combination of hydrochar with carbonized waste heat and exhaust gas collection could be a promising method to efficiently and affordably reduce hydrochar ecological toxicity.

Biochar-derived dissolved organic matter enhanced the release of residual ciprofloxacin from the soil solid phase.

Biochar has been utilized to reduce ciprofloxacin (CIP) residues in soil. However, little is known about the effect of biochar-derived dissolved organic matter (DOM) on residual CIP transformation. Thus, we analyzed the residual soil CIP as influenced by biochar generated from rice straw (RS3 and RS6), pig manure (PM3 and PM6), and cockroach shell (CS3 and CS6) at 300 °C and 600 °C. The three-dimensional excitation-emission matrix (3D-EEM), parallel factor analysis (PARAFAC) and two-dimensional correlation spectral analysis (2D-COS) were used to describe the potential variation in the DOM-CIP interaction. Compared with CK, biochar amendment increased the water-soluble CIP content by 160.7% (RS3), 55.2% (RS6), 534.1% (PM3), 277.5% (PM6), 1160.6% (CS3) and 703.9% (CS6), indicating that the biochar feedstock controlled the soil CIP release. The content of water-soluble CIP was positively correlated with the content of dissolved organic carbon (r = 0.922, p < 0.01) and dissolved organic nitrogen (r = 0.898, p < 0.01), suggesting that the major influence of the water-soluble CIP increase was DOM. The fluorescence quenching experiment showed that the interaction between DOM and CIP triggered static quenching and the creation of a DOM complex. The mean log K of protein-like material (4.977) was higher than that of terrestrial humus-like material (3.491), suggesting that the protein-like material complexed CIP was more stable than the humus-like material. Compared with pyrolysis at 300 °C, pyrolysis at 600 °C decreased the stability of the complex of protein-like material and CIP by 0.44 (RS), 1.689 (PM) and 0.548 (CS). This result suggested that the influence of temperature change was more profound on PM biochar-derived DOM than on RS and CS. These insights are essential for understanding CIP transportation in soil and controlling CIP contamination with biochar.

Bioaccessibility and human health risks of arsenic from geological origin in lateritic red soil on construction land.

Current human health risk assessments of soil arsenic (As) contamination rarely consider bioaccessibility (IVBA), which may overestimate the health risks of soil As. The IVBA of As (As-IVBA) may differ among various soil types. This investigation of As-IVBA focused As from geological origin in a typical subtropical soil, lateritic red soil, and its risk control values. The study used the SBRC gastric phase in vitro digestion method and As speciation sequential extraction based upon phosphorus speciation extraction method. Two construction land sites (CH and HD sites) in the Pearl River Delta region were surveyed. The results revealed a high content of residual As (including scorodite, mansfieldite, orpiment, realgar, and aluminum arsenite) in the lateritic red soils at both sites (CH: 84.9%, HD: 91.7%). The content of adsorbed aluminum arsenate (CH: 3.24%, HD: 0.228%), adsorbed ferrum arsenate (CH: 8.55%, HD: 5.01%), and calcium arsenate (CH: 7.33%, HD: 3.01%) were found to be low. The bioaccessible As content was significantly positively correlated with the As content in adsorbed aluminum arsenate, adsorbed ferrum arsenate, and calcium arsenate. A small portion of these sequential extractable As speciation could be absorbed by the human body (CH: 14.9%, HD: 3.16%), posing a certain health risk. Adsorbed aluminum arsenate had the highest IVBA, followed by calcium arsenate, and adsorbed ferrum arsenate had the lowest IVBA. The aforementioned speciation characteristics of As from geological origin in lateritic red soil contributed to its lower IVBA compared to other soils. The oxidation state of As did not significantly affect As-IVBA. Based on As-IVBA, the carcinogenic and non-carcinogenic risks of soil As in the CH and HD sites decreased greatly in human health risk assessment. The results suggest that As-IVBA in lateritic red soil should be considered when assessing human health risks on construction land.

Oxidation of chromium(â ¢): A potential risk of using chemical oxidation processes for the remediation of 2-chlorophenol contaminated soils.

Chemical oxidation processes are widely used for the remediation of organically contaminated soils, but their potential impact on variable-valence and toxic metals such as chromium (Cr) is often overlooked. In this study, we investigated the risk of Cr(Ⅲ) oxidation in soils during the remediation of 2-chlorophenol (2-CP) contaminated soils using four different processes: Potassium permanganate (KMnO4), Modified Fenton (Fe2+/H2O2), Alkali-activated persulfate (S2O82-/OH-), and Fe2+-activated persulfate (S2O82-/Fe2+). Our results indicated that the KMnO4, Fe2+/H2O2, and S2O82-/Fe2+ processes progressively oxidized Cr(III) to Cr(Ⅵ) during the 2-CP degradation. The KMnO4 process likely involved direct electron transfer, while the Fe2+/H2O2 and S2O82-/Fe2+ processes primarily relied on HO• and/or SO4•- for the Cr(III) oxidation. Notably, after 4 h of 2-CP degradation, the Cr(VI) content in the KMnO4 process surpassed China's 3.0 mg kg-1 risk screening threshold for Class I construction sites, and further exceeded the 5.7 mg kg-1 limit for Class II construction sites after 8 h. Conversely, the S2O82-/OH- process exhibited negligible oxidation of Cr(III), maintaining a low oxidation ratio of 0.13%, as highly alkaline conditions induced Cr(III) precipitation, reducing its exposure to free radicals. Cr(III) oxidation ratio was directly proportional to oxidant dosage, whereas the Fe2+/H2O2 process showed a different trend, influenced by the concentration of reductants. This study provides insights into the selection and optimization of chemical oxidation processes for soil remediation, emphasizing the imperative for thorough risk evaluation of Cr(III) oxidation before their application.

Effect of humic substances on the fraction of heavy metal and microbial response.

Contamination of soils by Molybdenum (Mo) has raised increasing concern worldwide. Both fulvic acid (FA) and humic acid (HA) possess numerous positive properties, such as large specific surface areas and microporous structure that facilitates the immobilization of the heavy metal in soils. Despite these characteristics, there have been few studies on the microbiology effects of FA and HA. Therefore, this study aimed to assess the Mo immobilization effects of FA and HA, as well as the associated changes in microbial community in Mo-contaminated soils (with application rates of 0%, 0.5% and 1.0%). The result of the incubation demonstrated a decrease in soil pH (from 8.23 ~ 8.94 to 8.05 ~ 8.77). Importantly, both FA and HA reduced the exchangeable fraction and reducible fraction of Mo in the soil, thereby transforming Mo into a more stable form. Furthermore, the application of FA and HA led to an increase in the relative abundance of Actinobacteriota and Firmicutes, resulting in alterations to the microbial community structure. However, it is worth noting that due to the differing structures and properties of FA and HA, these outcomes were not entirely consistent. In summary, the aging of FA and HA in soil enhanced their capacity to immobilization Mo as a soil amendment. This suggests that they have the potential to serve as effective amendments for the remediation of Mo-contaminated soils.

Chicken manure-derived biochar enhanced the potential of Comamonas testosteroni ZG2 to remediate Cd contaminated soil.

The combined remediation of Cd-contaminated soil using biochar and microorganisms has a good application value. In this study, the effect of chicken manure-derived biochar on CdCO3 precipitation induced by Comamonas testosteroni ZG2 was investigated. The results showed that biochar could be used as the carrier of strain ZG2, enhance the resistance of strain ZG2 to Cd, and reduce the toxicity of Cd to bacterial cells. Cd adsorbed by biochar could be induced by strain ZG2 to form CdCO3 precipitation. Strain ZG2 could also induce CdCO3 precipitation when biochar was added during precipitation formation and fermentation broth formation. The CdCO3 precipitation could enter the pores of the biochar and attach to the surface of the biochar. The single and combined effects of strain ZG2 and biochar could realize the remediation of Cd-contaminated soil to a certain extent. The overall effect was in the order of strain ZG2 with biochar > biochar > strain ZG2. The combination of strain ZG2 and biochar reduced soil available Cd by 48.2%, the aboveground biomass of pakchoi increased by 72.1%, and the aboveground Cd content decreased by 73.3%. At the same time, it promoted the growth and development of the root system and improved the microbial community structure of the rhizosphere soil. The results indicated that chicken manure-derived biochar could enhance the stability of CdCO3 precipitation induced by strain ZG2, and strain ZG2 combined with biochar could achieve a more stable remediation effect on Cd-contaminated soil.

Manganese exposure from spring and well waters in the Shenandoah Valley: interplay of aquifer lithology, soil composition, and redox conditions.

Manganese (Mn) is of particular concern in groundwater, as low-level chronic exposure to aqueous Mn concentrations in drinking water can result in a variety of health and neurodevelopmental effects. Much of the global population relies on drinking water sourced from karst aquifers. Thus, we seek to assess the relative risk of Mn contamination in karst by investigating the Shenandoah Valley, VA region, as it is underlain by both karst and non-karst aquifers and much of the population relies on water wells and spring water. Water and soil samples were collected throughout the Shenandoah Valley, to supplement pre-existing well water and spring data from the National Water Information System and the Virginia Household Water Quality Program, totaling 1815 wells and 119 springs. Soils were analyzed using X-ray fluorescence and Mn K-Edge X-ray absorption near-edge structure spectroscopy. Factors such as soil type, soil geochemistry, and aquifer lithology were linked with each location to determine if correlations exist with aqueous Mn concentrations. Analyzing the distribution of Mn in drinking water sources suggests that water wells and springs within karst aquifers are preferable with respect to chronic Mn exposure, with < 4.9% of wells and springs in dolostone and limestone aquifers exceeding 100 ppb Mn, while sandstone and shale aquifers have a heightened risk, with > 20% of wells exceeding 100 ppb Mn. The geochemistry of associated soils and spatial relationships to various hydrologic and geologic features indicates that water interactions with aquifer lithology and soils contribute to aqueous Mn concentrations. Relationships between aqueous Mn in spring waters and Mn in soils indicate that increasing aqueous Mn is correlated with decreasing soil Mn(IV). These results point to redox conditions exerting a dominant control on Mn in this region.

Effects of swine manure and straw biochars on fluorine adsorption-desorption in soils.

With increasing global awareness of soil health, attention must be paid to fluorine exposure in soils, which poses a threat to human health. Therefore, this study aimed to study the fluorine adsorption characteristics of swine manure and straw biochars and their impact on fluorine adsorption-desorption in soil with batch experiments. The biochar samples originated from high-temperature anaerobic cracking of swine manure (350°C, 500°C, and 650°C) and straw (500°C). Results indicated that the adsorption of soil fluorine reached adsorption equilibrium at around 4 h after the mixing of swine manure and straw biochar. Fluorine adsorption kinetics using these biochars conformed to the quasi-two-stage kinetic model. The fluorine adsorption kinetics for biochar-treated soils conformed to the double-constant equation and the Elovich equation, and the soil treated with straw biochar showed the fastest fluorine adsorption rate. The adsorption isotherms of fluorine for biochars and biochar-treated soils could be fitted by the isothermal adsorption model of Langmuir and Freundlich. The maximal equilibrium quantity of fluorine was 73.66 mg/g for swine manure biochar. The soil, adding with 2% of swine manure biochar achieved with showed at 650°C had the smallest adsorption. This study also shows that the adsorption of fluorine by biochar gradually decreased with the increase of pH. Comparing with other factors, the mixture pH with biochars added had a significant effect on fluorine adsorption. The decreased fluorine adsorption capacities for soils treated with swine manure and straw biochars were closely related to the increased pH in soils after adding biochars. Considering the fluorine threat in soil, this study provides a theoretical basis for the application of biochars on soil fluorine adsorption.

Impact of different sterilisation techniques on sorption and NER formation of test chemicals in soil.

Standard OECD tests are used to generate data on biodegradation (OECD 307) and sorption (OECD 106) of test chemicals in soil. In such tests, data on abiotic degradation using sterile samples are utilised to investigate any losses due to abiotic processes. The data from sterile samples are also used to interpret results and findings of non-sterile samples, especially in the context of sorption and non-extractable residue (NER) formation. However, to ensure the comparability of the data obtained from sterile and non-sterile experiments, effects of sterilisation on the soil matrix should be minimal. The objective of this study was to investigate the efficiencies of different sterilisation techniques and the impact of the sterilisation on sorption and NER formation in soil. In this study, experiments in accordance with OECD 307 and OECD 106 guidelines were performed with two soils covering wide range of soil characteristics and treated with the three sterilisation techniques autoclaving, gamma(γ)-radiation and adding 1% (w/w) sodium azide. As a test item, 14C-labelled phenanthrene and bromoxynil was used for OECD 307 test, whereas non-labelled phenanthrene and atrazine was used for OECD 106. The sterilisation efficiencies were investigated using traditional viable plate count and molecular approaches (RNA extraction method). The results suggest that none of the tested techniques resulted in completely sterilised soil with autoclaving being the most efficient technique. Adding sodium azide led to most inefficient sterilisation and a significant increase (0.56 units) in soil pH. OECD 307 results showed differences in NER formation of the test chemicals, especially for soil poisoning and γ-radiation, which could be due to inefficient sterilisation and/or change in soil physico-chemical properties. OECD 106 results suggest that none of the sterilisation techniques considerably affected sorption behaviour of the test chemicals. Based on our results, we recommend autoclaving as most suitable sterilisation technique.

Tracing anthropogenic mercury in soils from Fe-Hg mining/smelting area: Isotopic and speciation insights.

Mercury (Hg) stable isotope ratios supplemented by Hg solid speciation data were determined in soils in a former Fe-Hg mining/smelting area (Jedová hora, Czech Republic, Central Europe). The dominant Hg phase in the studied soils was found to be cinnabar (HgS). A secondary form of soil Hg(II) was represented by Hg weakly and strongly bound to mineral (micro)particles, as revealed by thermo-desorption analysis. These Hg species probably play a key role in local soil Hg processes and biogeochemical cycling. The Hg isotopic data generally showed small differences between HgS (-1.1 to -0.8‰; δ202Hg) and the soil samples (-1.4 to -0.9‰; δ202Hg), as well as limited isotopic variability within the two studied soil profiles. On the other hand, the detected negative δ202Hg shift (∼0.4‰) in organic horizons compared to mineral soils in the highly contaminated profile suggests the presence of secondary post-depositional Hg processes, such as sorption or redox changes. For the less contaminated profile, the observed Hg isotopic variation (∼0.3‰; δ202Hg) in the subsurface mineral soil compared to both overlying and underlying horizons is likely due to cyclic redox reactions associated with Hg isotopic fractionation. We assume that the adsorption of Hg(II) to secondary Fe(III)/Mn(III,IV)-oxides could be of major importance in such cases.

Mechanism of tartaric acid mediated dissipation and biotransformation of tetrabromobisphenol A and its derivatives in soil.

Biotransformation is a major dissipation process of tetrabromobisphenol A and its derivatives (TBBPAs) in soil. The biotransformation and ultimate environmental fate of TBBPAs have been widely studied, yet the effect of root exudates (especially low-molecular weight organic acids (LMWOAs)) on the fate of TBBPAs is poorly documented. Herein, the biotransformation behavior and mechanism of TBBPAs in bacteriome driven by LMWOAs were comprehensively investigated. Tartaric acid (TTA) was found to be the main component of LMWOAs in root exudates of Helianthus annus in the presence of TBBPAs, and was identified to play a key role in driving shaping bacteriome. TTA promoted shift of the dominant genus in soil bacteriome from Saccharibacteria_genera_incertae_sedis to Gemmatimonas, with a noteworthy increase of 24.90-34.65% in relative abundance of Gemmatimonas. A total of 28 conversion products were successfully identified, and ß-scission was the principal biotransformation pathway for TBBPAs. TTA facilitated the emergence of novel conversion products, including 2,4-dibromophenol, 3,5-dibromo-4-hydroxyacetophenone, para-hydroxyacetophenone, and tribromobisphenol A. These products were formed via oxidative skeletal cleavage and debromination pathways. Additionally, bisphenol A was observed during the conversion of derivatives. This study provides a comprehensive understanding about biotransformation of TBBPAs driven by TTA in soil bacteriome, offering new insights into LMWOAs-driven biotransformation mechanisms.

Redox conditions and biochar pyrolysis temperature affecting As and Pb biogeochemical cycles and bacterial community of sediment from mining tailings.

Despite the widespread use of biochar for soil and sediment remediation, little is known about the impact of pyrolysis temperature on the biogeochemistry of arsenic (As) and lead (Pb) and microorganisms in sediment under reducing conditions. In this study, we investigated the effects of pyrolysis temperature and the addition of glucose on the release and transformation of As and Pb, as well as their potential effects on the bacterial community in contaminated sediments. The addition of biochar altered the geochemical cycle of As, as it favors specific bacterial groups capable of changing species from As(V) to As(III) through fermentation, sulfate respiration and nitrate reduction. The carbon quality and content of N and S in solution shaped the pH and redox potential in a way that changed the microbial community, favoring Firmicutes and reducing Proteobacteria. This change played a fundamental role in the reductive dissolution of As and Pb minerals. The addition of biochar was the only efficient way to remove Pb, possibly as a function of its sorption and precipitation mechanisms. Such insights could contribute to the production or choice of high-efficiency biochar for the remediation of sediments subjected to redox conditions.

Fabrication of engineered biochar for remediation of toxic contaminants in soil matrices and soil valorization.

Biochar has emerged as an efficacious green material for remediation of a wide spectrum of environmental pollutants. Biochar has excellent characteristics and can be used to reduce the bioavailability and leachability of emerging pollutants in soil through adsorption and other physico-chemical reactions. This paper systematically reviewed previous researches on application of biochar/engineered biochar for removal of soil contaminants, and underlying adsorption mechanism. Engineered biochar are derivatives of pristine biochar that are modified by various physico-chemical and biological procedures to improve their adsorption capacities for contaminants. This review will promote the possibility to expand the application of biochar for restoration of degraded lands in the industrial area or saline soil, and further increase the useable area. This review shows that application of biochar is a win-win strategy for recycling and utilization of waste biomass and environmental remediation. Application of biochar for remediation of contaminated soils may provide a new solution to the problem of soil pollution. However, these studies were performed mainly in a laboratory or a small scale, hence, further investigations are required to fill the research gaps and to check real-time applicability of engineered biochar on the industrial contaminated sites for its large-scale application.

Peroxydisulfate-Driven Reductive Dechlorination as Affected by Soil Constituents: Free Radical Formation and Conversion.

We report a previously unrecognized but efficient reductive degradation pathway in peroxydisulfate (PDS)-driven soil remediation. With supplements of naturally occurring low-molecular-weight organic acids (LMWOAs) in anaerobic biochar-activated PDS systems, degradation rates of 12 γ-hexachlorocyclohexanes (HCH)-spiked soils boosted from 40% without LMWOAs to a maximum of 99% with 1 mM malic acid. Structural analysis revealed that an increase in α-hydroxyl groups and a diminution in pKa1 values of LMWOAs facilitated the formation of reductive carboxyl anion radicals (COO•-) via electrophilic attack by SO4•-/•OH. Furthermore, degradation kinetics were strongly correlated with soil organic matter (SOM) contents than iron minerals. Combining a newly developed in situ fluorescence detector of reductive radicals with quenching experiments, we showed that for soils with high, medium, and low SOM contents, dominant reactive species switched from singlet oxygen/semiquinone radicals to SO4•-/•OH and then to COO•- (contribution increased from 30.8 to 66.7%), yielding superior HCH degradation. Validation experiments using SOM model compounds highlighted critical roles of redox-active moieties, such as phenolic - OH and quinones, in radical formation and conversion. Our study provides insights into environmental behaviors related to radical activation of persulfate in a broader soil horizon and inspiration for more advanced reduction technologies.

Electrokinetically-delivered persulfate coupled with thermal conductive heating for remediation of petroleum hydrocarbons contaminated low permeability soil.

In this study, electrokinetically-delivered persulfate (PS) coupled with thermal conductive heating (TCH) method was proposed for the remediation of petroleum hydrocarbons (PHs) contaminated low-permeability soil, based on the investigation of PS injection and activation by different electric field form, effective heating radius of TCH to activate PS, and their influencing factors. The uniform delivery and effective activation of PS were unrealizable by one-dimensional electric field (1 V/cm) with the operation of cathode injection, anode injection, bipolar injection, polarity-reversal, or bipolar injection coupled polarity-reversal, which would result in large spatial difference of soil pH and PHs residual. Similar results were obtained under the two-dimensional symmetric electric field (TEF) due to the large spatial difference in electric field intensity. Superimposed electric field (SEF, 1 V/cm) that based on the intermittent worked electrode groups coupled with polarity-reversal (every 3 h) and bipolar injection (10% PS solution) operation could achieve homogenized mass transfer of PS (53.8-65.7 g/kg, average 60.0 g/kg) in 15 days, due to the positive correlation between electric field intensity and transport of ionic substance. Meanwhile, the difference in decontamination efficiency caused by difference in PS activation efficiency could be reduced, since the heating rod was placed at the position where the concentrations of PS was the lowest, whereat the removal of PHs could not rely on alkali activated PS (cathode), anodic oxidation (anode), and electrochemical activated PS (cathode and anode). The residual concentration of PHs in soil remediated by SEF/PS-TCH was in the range of 640.7-763.8 mg/kg (average 701.5 mg/kg), and the corresponding removal efficiency was 73.3%-77.6% (average75.4%). The research can provide an in-situ remediation method for organic contaminants in low permeability soil featured with more uniform PS injection and activation, and small spatial differences in remediation efficiency.

Enhanced surfactant remediation of diesel-contaminated soil using O3 nanobubbles.

Currently, nanobubbles are widely discussed in environmental research due to their unique properties, including significant specific surface area, transfer efficiency, and free radical generation. In this study, O2 and O3 nanobubbles (diameters ranging from 0 to 500 nm) were combined with conventional surfactant technology to investigate their enhanced efficacy in removing diesel contaminants from soil. The impact of various factors such as surfactant concentration, temperature, and soil aging duration on pollutant removal rates was examined across different experimental approaches (stirring/flushing). Soil samples subjected to different treatments were characterized using TG-DTG and FTIR analysis, while GC/MS was employed to assess the degradation products of diesel constituents in the soil. The results indicated that the elution efficiencies of the three surfactants (SDS, SDBS, and TX-100) for diesel in soil correlated positively with concentration (0.3-1.4 CMC) and temperature (18-60 °C), and inversely with aging time (10-300 days), with the elution capacity was SDS > SDBS > TX-100. Mechanical stirring (500 rpm) and temperature variations (18-60 °C) did not affect the stability of the nanobubbles. Upon the introduction of O3 nanobubbles to the surfactant solution, there was a consistent increase in both the removal (degraded and removed) efficiency and rate of diesel under varying experimental conditions, resulting in an enhancement of removal rates by approximately 8-15%. FTIR spectroscopy showed that surfactants containing O3 nanobubbles mitigated the impact on the primary functional groups of soil organic matter. GC/MS analyses indicated that residual pollutants were predominantly alkanes, with degradation difficulty ranking as: alkanes < alkenes < cycloalkanes < aromatic compounds. TG-DTG coupled with GC/MS analysis demonstrated that O3 nanobubbles contributed to a reduction in surfactant residues. This study significantly advances our understanding of how nanobubbles facilitate and optimize surfactant-assisted remediation of contaminated soil, thereby advancing the precise application of nanobubble technology in soil remediation.

Hypochlorite-mediated degradation and detoxification of sulfathiazole in aqueous solution and soil slurry.

Although various activated sodium hypochlorite (NaClO) systems were proven to be promising strategies for recalcitrant organics treatment, the direct interaction between NaClO and pollutants without explicit activation is quite limited. In this work, a revolutionary approach to degrade sulfathiazole (STZ) in aqueous and soil slurry by single NaClO without any activator was proposed. The results demonstrated that 100% and 94.11% of STZ could be degraded by 0.025 mM and 5 mM NaClO in water and soil slurry, respectively. The elimination of STZ was shown to involve superoxide anion (O2•-), chlorine oxygen radical (ClO•), and hydroxyl radical (•OH), according to quenching experiments and the analysis of electron paramagnetic resonance. The addition of Cl-, HCO3-, SO42-, and humic acid (HA) marginally impeded the decomposition of STZ, while NO3-, Fe3+, and Mn2+ facilitated the process. The NaClO process exhibited significant removal effectiveness at a neutral initial pH. Moreover, the NaClO facilitated application in various soil samples and water matrices, and the procedure was also successful in effectively eliminating a range of sulfonamides. The suggested NaClO degradation mechanism of STZ was based on the observed intermediates, and the majority of the products exhibited lower ecotoxicity than STZ. Besides, the experiment results by using X-ray diffraction (XRD) and a fourier transform infrared spectrometer (FTIR) indicated the negligible effects on the composition and structure of soil by the treatment of NaClO. Simultaneously, the experimental results also illustrated that the bioavailability of heavy metals and the physiochemical characteristics of the soil before and after the remediation did not change to a significant extent. Following the remediation of NaClO, the phytotoxicity tests showed reduced toxicity to wheat and cucumber seeds. As a result, treating soil and water contaminated with STZ by using NaClO was a reasonably practical and eco-friendly method.

Degradation and humification of steroidal estrogens in the soil environment: A review.

Emerging pollutants are toxic and harmful chemical substances characterized by environmental persistence, bioaccumulation and biotoxicity, which can harm the ecological environment and even threaten human health. There are four categories of emerging pollutants that are causing widespread concern, namely, persistent organic pollutants, endocrine disruptors, antibiotics, and microplastics. The distribution of emerging pollutants has spatial and temporal heterogeneity, which is influenced by factors such as geographical location, climatic conditions, population density, emission amount, etc. Steroidal estrogens (SEs) discussed in this paper belong to the category of endocrine disruptors. There are generally three types of fate for SEs in the soil environment: sorption, degradation and humification. Humification is a promising pathway for the removal of SEs, especially for those that are difficult to degrade. Through humification, these difficult-to-degrade SEs can be effectively transferred or fixed, thus reducing their impact on the environment and organisms. Contrary to the well-studied process of sorption and degradation, the role and promise of the humification process for the removal of SEs has been underestimated. Based on the existing research, this paper reviews the sources, classification, properties, hazards and environmental behaviors of SEs in soil, and focuses on the degradation and humification processes of SEs and the environmental factors affecting their processes, such as temperature, pH, etc. It aims to provide references for the follow-up research of SEs, and advocates further research on the humification of organic pollutants in future studies.

Prediction of atrazine degradation in soil based on XGBoost model.

We established the optimal model by using the automatic machine learning method to predict the degradation efficiency of herbicide atrazine in soil, which could be used to assess the residual risk of atrazine in soil. We collected 494 pairs of data from 49 published articles, and selected seven factors as input features, including soil pH, organic matter content, saturated hydraulic conductivity, soil moisture, initial concentration of atrazine, incubation time, and inoculation dose. Using the first-order reaction rate constant of atrazine in soil as the output feature, we established six models to predict the degradation efficiency of atrazine in soil, and conducted comprehensive analysis of model performance through linear regression and related evaluation indicators. The results showed that the XGBoost model had the best performance in predicting the first-order reaction rate constant (k). Based on the prediction model, the feature importance ranking of each factor was in an order of soil moisture > incubation time > pH > organic matter > initial concentration of atrazine > saturated hydraulic conductivity > inoculation dose. We used SHAP to explain the potential relationship between each feature and the degradation ability of atrazine in soil, as well as the relative contribution of each feature. Results of SHAP showed that time had a negative contribution and saturated hydraulic conductivity had a positive contribution. High values of soil moisture, initial concentration of atrazine, pH, inoculation dose and organic matter content were generally distributed on both sides of SHAP=0, indicating their complex contributions to the degradation of atrazine in soil. The XGBoost model method combined with the SHAP method had high accuracy in predicting the performance and interpretability of the k model. By using machine learning method to fully explore the value of historical experimental data and predict the degradation efficiency of atrazine using environmental parameters, it is of great significance to set the threshold for atrazine application, reduce the residual and diffusion risks of atrazine in soil, and ensure the safety of soil environment.

Divergent redistribution behavior of divalent metal cations associated with Fe(II)-mediated jarosite phase transformation.

The Fe(II)/Fe(III) cycle is an important driving force for dissolution and transformation of jarosite. Divalent heavy metals usually coexist with jarosite; however, their effects on Fe(II)-induced jarosite transformation and different repartitioning behavior during mineral dissolution-recrystallization are still unclear. Here, we investigated Fe(II)-induced (1 mM Fe(II)) jarosite conversion in the presence of Cd(II), Mn(II), Co(II), Ni(II) and Pb(II) (denoted as Me(II), 1 mM), respectively, under anaerobic condition at neutral pH. The results showed that all co-existing Me(II) retarded Fe(II)-induced jarosite dissolution. In the Fe(II)-only system, jarosite first rapidly transformed to lepidocrocite (an intermediate product) and then slowly to goethite; lepidocrocite was the main product. In Fe(II)-Cd(II), -Mn(II), and -Pb(II) systems, coexisting Cd(II), Mn(II) and Pb(II) retarded the above process and lepidocrocite was still the dominant conversion product. In Fe(II)-Co(II) system, coexisting Co(II) promoted lepidocrocite transformation into goethite. In Fe(II)-Ni(II) system, jarosite appeared to be directly converted into goethite, although small amounts of lepidocrocite were detected in the final product. In all treatments, the appearance or accumulation of lepidocrocite may be also related to the re-adsorption of released sulfate. By the end of reaction, 6.0 %, 4.0 %, 76.0 % 11.3 % and 19.2 % of total Cd(II), Mn(II), Pb(II) Co(II) and Ni(II) were adsorbed on the surface of solid products. Up to 49.6 %, 44.3 %, and 21.6 % of Co(II), Ni(II), and Pb(II) incorporated into solid product, with the reaction indicating that the dynamic process of Fe(II) interaction with goethite may promote the continuous incorporation of Co(II), Ni(II), and Pb(II).