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In this study, sulfur-containing iron carbon nanocomposites (S@Fe-CN) were synthesized by calcining iron-loaded biomass and utilized to activate persulfate (PS) for the combined chemical oxidation and microbial remediation of petroleum-polluted soil. The highest removal efficiency of total petroleum hydrocarbons (TPHs) was achieved at 0.2% of activator, 1% of PS and 1:1 soil-water ratio. The EPR and quenching experiments demonstrated that the degradation of TPHs was caused by the combination of 1 O 2, ·OH, SO 4 · - , and O 2 · - . In the S@Fe-CN activated PS (S@Fe-CN/PS) system, the degradation of TPHs underwent two phases: chemical oxidation (days 0 to 3) and microbial degradation (days 3 to 28), with kinetic constants consistent with the pseudo-first-order kinetics of chemical and microbial remediation, respectively. In the S@Fe-CN/PS system, soil enzyme activities decreased and then increased, indicating that microbial activities were restored after chemical oxidation under the protection of the activators. The microbial community analysis showed that the S@Fe-CN/PS group affected the abundance and structure of microorganisms, with the relative abundance of TPH-degrading bacteria increased after 28 days. Moreover, S@Fe-CN/PS enhanced the microbial interactions and mitigated microbial competition, thereby improving the ability of indigenous microorganisms to degrade TPHs., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Soils co-contaminated by organic and inorganic pollutants usually pose major ecological risks to soil ecosystems including plants. Thus, effective strategies are needed to alleviate the phytotoxicity caused by such co-contamination. In this study, microbial agents (a mixture of Bacillus subtilis, Sphingobacterium multivorum, and a commercial microbial product named OBT) and soil amendments (β-cyclodextrin, rice husk, biochar, calcium magnesium phosphate fertilizer, and organic fertilizer) were evaluated to determine their applicability in alleviating toxicity to crops (maize and soybean) posed by polycyclic aromatic hydrocarbon (PAHs) and potentially toxic metals co-contaminated soils. The results showed that peroxidase, catalase, and superoxide dismutase activity levels in maize or soybean grown in severely or mildly contaminated soils were significantly enhanced by the integrative effects of amendments and microbial agents, compared with those in single plant treatments. The removal rates of Zn, Pb, and Cd in severely contaminated soils were 49 %, 47 %, and 51 % and 46 %, 45 %, and 48 %, for soybean and maize, respectively. The total contents of Cd, Pb, Zn, and PAHs in soil decreased by day 90. Soil organic matter content, levels of nutrient elements, and enzyme activity (catalase, urease, and dehydrogenase) increased after the amendments and application of microbial agents. Moreover, the amendments and microbial agents also increased the diversity and distribution of bacterial species in the soil. These results suggest that the amendments and microbial agents were beneficial for pollutant purification, improving the soil environment and enhancing both plant resistance to pollutants and immune systems of plants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

This study aimed to investigate the combined ecotoxicological effects of Cd, Pb, Zn, Hg and regulation mechanisms in Solanum nigrum L. In this work, the co-exposure of these four heavy metals hindered the transformation of Cd, Zn, and Hg (except Pb) from available to non-available chemical forms. Individual Cd, Pb, Zn and Hg induced the oxidative damages to S. nigrum L., while their combination further enhanced this ecological toxicity. By internal regulation, the ecological toxicity of metals to S. nigrum L. could be alleviated to a certain extent. Specifically, S. nigrum L. was a hyperaccumulator of Cd with BCF ＞1. Moreover, since BCFroot of Pb, Zn and Hg were all greater than BCFshoot, S. nigrum L. could accumulate Pb, Hg and Zn mainly in plant roots, which was beneficial for the detoxification of plants. Meanwhile, the immobilization by cell wall (the proportions of Cd, Pb, Zn and Hg in the cell wall were 54.46-84.92%, 38.33-49.25%, 48.38-56.19% and 45.97-63.47% in low metal concentration treatments) and the sequestration in vacuole (the proportions of Cd, Pb, Zn, and Hg in the soluble fractions are 50.99-59.00%, 41.05-45.46%, 37.54-61.04% and 33.47-61.35% in high metal concentration treatments) also act as important detoxification pathways. The external regulation was mainly the changes of soil microbial communities influenced by plants. Specifically, the richness and diversity of bacteria in rhizosphere soil were increased, and roots of S. nigrum L. recruited some potentially beneficial microbials. This study provided a theoretical basis and guidance for S. nigrum L. as a phytoremediation plant under combined heavy metal pollution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Perfluorooctanoic acid (PFOA) and arsenic are widely distributed pollutants and can coexist in the environment. However, no study has been reported about the effects of different arsenic species on the joint toxicity of arsenic and PFOA to soil invertebrates. In this study, four arsenic species were selected, including arsenite (As(III)), arsenate (As(V)), monomethylarsonate (MMA), and dimethylarsinate (DMA). Earthworms Eisenia fetida were exposed to soils spiked with sublethal concentrations of PFOA, different arsenic species, and their binary mixtures for 56 days. The bioaccumulation and biotransformation of pollutants, as well as eight biomarkers in organisms, were assayed. The results indicated that the coexistence of PFOA and different arsenic species in soils could enhance the bioavailability of arsenic species while reducing the bioavailability of PFOA, and inhibit the arsenic biotransformation process in earthworms. Responses of most biomarkers in joint treatments of PFOA and As(III)/As(V) showed more significant variations compared with those in single treatments, indicating higher toxicity to the earthworms. The Integrated Biomarker Response (IBR) index was used to integrate the multi-biomarker responses, and the results also exhibited enhanced toxic effects in combined treatments of inorganic arsenic and PFOA. In comparison, both the biomarker variations and IBR values were lower in joint treatments of PFOA and MMA/DMA. Then the toxic interactions in the binary mixture systems were characterized by using a combined method of IBR and Effect Addition Index. The results revealed that the toxic interactions of the PFOA/arsenic mixture in earthworms depended on the different species of arsenic. The combined exposure of PFOA with inorganic arsenic led to a synergistic interaction, while that with organic arsenic resulted in an antagonistic response. Overall, this study provides new insights into the assessment of the joint toxicity of perfluoroalkyl substances and arsenic in soil ecosystems., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Co-existence of polycyclic aromatic hydrocarbons (PAHs) and multi-metals challenges the decontamination of large-scale contaminated sites. This study aims to comprehensively evaluate the remediation potential of intensified phytoremediation in coping with complex co-contaminated soils. Results showed that the removal of PAHs and heavy metals is time-dependent, pollution-relevant, and plant-specific. Removal of sixteen PAHs by Medicago sativa L. (37.3%) was significantly higher than that of Solanum nigrum L. (20.7%) after 30 days. S. nigrum L. removed higher amounts of Cd than Zn and Pb, while M. sativa L. uptake more Zn. Nevertheless, amendments and microbial agents significantly increased the phytoremediation efficiency of pollutants and shortened the gap between plants. Cd removal and PAHs dissipation reached up to 80% and 90% after 90 days for both plants. Heavy metal stability in soil was promoted after the intensified phytoremediation. Plant lipid peroxidation was alleviated, regulated by changed antioxidant defense systems (superoxide dismutase, peroxidase, catalase). Soil enzyme activities including dehydrogenase, urease, and catalase increased up to 5-fold. Soil bacterial diversity and structure were changed, being largely composed of Proteobacteria, Actinobacteria, Patescibacteria, Bacteroidetes, and Firmicutes. These findings provide a green and sustainable approach to decontaminating complex-polluted environments with comprehensive improvement of soil health., (Copyright © 2021 Elsevier B.V. All rights reserved.)

A new type of binder was developed by grafting casein and β-glucan to investigate its effect on tailings erosion and plant growth. 6% casein and 2% β-glucan were recommended as the best ratio of the new biopolymer binder, which had the best effect on the soil utilization of iron tailings. The infrared analysis of the new binder demonstrated that casein and β-glucan reacted adequately as raw materials. The results of physichemical properties and loss prevention of iron tailings showed that the binder-treated soils demonstrated lower erodibility compared with untreated iron tailings. The particle size of the tailings was increased after the addition of the binder. In treated soil, the content of soil organic matter increased significantly, which provided sufficient nutrients for the plants growing. Compared with natural tailings without binder, plant height, fresh weight, chlorophyll content, and enzyme activity (POD and SOD) were also significantly increased. This study overcame the current defects of biopolymer in soil improvement and provided an environmentally friendly method to prevent the loss of iron tailings and promote its soil utilization efficiency., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Both potentially toxic elements (PTEs) and polycyclic aromatic hydrocarbons (PAHs) are widely present in soil contaminated by steel industries. This study assessed the vertical variation (at 20 cm, 40 cm, 60 cm, 80 cm, 120 cm, and 150 cm depth) of bacterial abundance, community structure, functional genes related to PAHs degradation, and community co-occurrence patterns in an old steel plant soils which contaminated by PTEs and PAHs for 60 years. The excessive PAHs and PTEs in steel plant soils were benzo (a) pyrene, benzo (b) fluoranthene, dibenzo (a, h) anthracene, indeno (1,2,3-c, d) pyrene, and lead (Pb). The abundance and composition of bacterial community considerably changed with soil depth in two study areas with different pollution degrees. The results of co-occurrence network analysis indicated that the top genera in blast furnace zone identified as the potential keystone taxa were Haliangium, Blastococcus, Nitrospira, and Sulfurifustis. And in coking zone, the top genera were Gaiella. The predictions of bacterial metabolism function using PICRUSt showed that the PAHs-PTEs contaminated soil still had the potential for PAHs degradation, but most PTEs negatively correlated with PAHs degradation genes. The total sulfur (TS), acenaphthene (ANA), and Zinc (Zn) were the key factors to drive development of bacterial communities in the steel plant soils. As far as we know, this is the first investigation of vertical distribution and interaction of the bacterial microbiota in the aging soils of steel plant contaminated with PTEs and PAHs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

To meet the goal of sustainable development, many large steel enterprises in China have been relocated, leaving serious polycyclic aromatic hydrocarbon (PAH) pollution problems at the abandoned sites. In this study, the spatial distribution and potential health risks of PAHs in soils of a large steel enterprise in East China were studied. The total concentrations of 16 PAHs ranged from 93.96 to2.61E + 05 μg/kg. A total of 54.84% of the samples reached the level of severe pollution, with coking plants and iron works showing much more serious problems than other areas. The contribution levels of PAHs with high molecular weights were high, especially those of 4-ring PAHs. The toxic equivalent concentrations exceeded the values recommended by the Canadian guide. The average carcinogenic risk value of the whole region was greater than 10 -6 , indicating high carcinogenic risk. The above assessment indicates that the area must be remediated before further development occurs.

The biosorption and bioaugmentation performances of Mucor circinelloides were investigated under different contact time, initial metal(loid) concentration and species. The microbe-plant interaction appeared synergistic with enhancing plant growth and alleviating oxidative damages induced by lead, cadmium and arsenic. The bioaugmentation with M. circinelloides led to significant immobilization on lead, cadmium and arsenic as indicated by the decreases of metal(loid) transfer and bioavailability in plant-microbe aqueous system. Lead, cadmium and arsenic were mainly allocated on cell wall and a few parts entered into intercellular system, suggesting cell wall adsorption and intracellular bioaccumulation served as the main mechanisms of M. circinelloides. The adsorption kinetics and isotherms on lead, cadmium and arsenic were fitted well with the pseudo-second-order and Langmuir models, with the maximum adsorption capacities of 500, 15.4 and 29.4 mg·g -1 fungal biomass at pH 6.0 and 25 ℃. The optimum initial concentration and contact time were 300-10-20 mg·L -1 and 2 h. This study provides a basis for M. circinelloides as a promising adsorbent and bioaugmented agent for the cleanup of soil/aqueous environment contaminated with lead, cadmium and arsenic., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

The toxicity characteristics of HBCD and resistance mechanism of flavonols are investigated based on physiological and metagenomic analysis. Toxicology research of HBCD on Arabidopsis thaliana (Col and fls1-3) not only shows the toxic effect of HBCD on plants, but also indicates that flavonols could improve plant resistance to HBCD, including root length, shoot biomass and chlorophyll content. Analysis of eggNOG and GO enrichment demonstrates that HBCD has toxic effect on both gene expression and protein function, which concentrates on energy production - conversion and amino acid transport - metabolism. Differential expressed genes in flavonols-treated groups indicates that flavonols regulate the metabolism of amino acids, cofactors and vitamins, which is involved in plant defense system against oxidative damage caused by HBCD stress. HBCD is believed to affect the synthesis of proteins via genes expression of ribosome biogenesis process. Flavonols could strengthen the plant resistance and alleviate toxic effect under HBCD stress., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Lead (Pb) is a typical hazardous element of high concern in species characteristics involving toxicity, migration and transformation. A greenhouse experiment was conducted using Solanum nigrum L. grown in soils treated by divalent (Pb 2+ ), tetravalent (Pb 4+ ), trimethyl (TML) and triethyl (TEL) lead for 60 days. Results of physio-biochemical parameters indicated Pb toxicity was ranked as TEL > TML > Pb 2+ > Pb 4+ in a dose-dependent manner, and the correlation levels of organic species were higher than inorganic species. S. nigrum L. adopted phytostabilization strategy through fixing Pb in roots and restricting its transfer to shoots. More phytotoxic Pb was absorbed from soils treated by Pb 2+ than Pb 4+ as well as TEL than TML. In soils, inorganic Pb species were mainly present in residues while organic Pb species in Fe/Mn oxide and exchangeable fractions. Although most of Pb species in plant existed in the low-bioavailable extractions of 1 M NaCl and 2% HAC, the water-soluble Pb extracted by d-H 2 O and 80 % ethanol were increased to a large extent under high-level exposure. The occurrence of reduction and (de)alkylation were considered as the major pathways in the biotransformation of Pb species. This study will conduce to the ecological risk management for Pb-contaminated soils., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A greenhouse experiment was conducted to investigate an enhanced phytoremediation technique for multi-metal contaminated mine tailings by Solanum nigrum L. and using biochar/attapulgite as soil amendments. The 10% attapulgite (MA 2 ) and 10% biochar (MB 2 ) were recommended as the optimum chemical proportions for amendment materials. Plant length and fresh weight in the MA 2 /MB 2 -applied treatments were significantly higher than that in the non-amended treatment, indicating MA 2 and MB 2 amendments could alleviate metal phytotoxicity. Metal uptake in plant leaves was lower with MA 2 and MB 2 application than that in the non-amended treatment. However, metal uptake in plant roots was significantly increased with MA 2 and MB 2 application from the fifth month, suggesting that MA 2 and MB 2 had significant enhancement on metal stabilization. Temporal variation of metal translocation in soil-to-plant system showed that the function of MA 2 and MB 2 reached the plateau nearly in the seventh month. The removal rates of metals were higher after the application of MA 2 than MB 2 , and by the following order: Cu (39.6%) > Zn (35.0%) > Cd (34.1%) > Hg (32.1%) > Pb (31.8%) > Mn (19.1%). The synergistic effect between S. nigrum L. and MA 2 /MB 2 appeared to be particularly effective in terms of metal phytostabilization, and MA 2 was superior to MB 2., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The combined application of plant, microorganism, and amendment on the phytoremediation of heavy metals was optimized as a remediation technique for mine tailings by a field-scale orthogonal (L 16 ) experiment, aimed to achieve the maximum of phytoremediation effect. Soybean, M. Circinelloides, and A3 amendment (organic fertilizer: rice husk: biochar: ceramsite = 1:1:2:1) were recommended as the best plant, microorganism, and amendment materials, respectively. With the combined plant, microorganism, amendment application, effective fractions of Cu, Zn, Pb, Cd, Mn were immobilized for decreased bioavailability, indicating the phytostabilization served as a major repair pathway. Plant length and biomass in the treatments were significantly higher than that in the control, indicating their phytoremediation potentials were enhanced. The final contents of heavy metals in soil were decreased, and the removal rates of soil heavy metals were in the order of Pb＞Cd＞Cu＞Zn＞Mn. Temporal variations of soil microorganism populations indicated that the abundance of soil microorganism in the treatments was significantly higher than that in the control, and bacteria became the dominant microbial species. Results showed that the soil organic matter and catalase, urease, phosphatase activities of the treatments were all significantly higher than that of the control. This study provided optimized combined plant, microorganism, amendment materials in the enhanced phytoremediation field to make up the deficiencies of the long-term phytoremediation for heavy metals., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The soil ecosystem is critical for agricultural production, affecting many aspects of human health. Soil has more unknown biodiversity and edaphic parameters than any other ecosystem especially when polluted. Metagenomics and metatranscriptomics were applied to research on toxicological characteristics of Pb and resistance mechanism of flavonols. Rhizosphere microorganisms-plants system, a unified system closely related to soil environment was taken as research object. Results emphasize gene expression changes in different test groups. Gene ontology enrichment and eggNOG showed that Pb has a toxic effect on gene and protein function which concentrated on ATPase and ATP-dependent activity. Differentially expressed genes in the flavonols group indicated that flavonols regulate amino acid transport and other transportation process related to Pb stress. Kegg analysis represents that Pb interferences energy production process via not only the upstream like glycolysis and tricarboxylic acid (TCA) circle but also oxidative phosphorylation process, which can also produce reactive oxygen species and impact the eliminating process. Flavonols have shown the ability in alleviating toxic effect of Pb and improving the resistance of plants. Flavonols can recover the electronic transmission and other process in TCA and oxidative phosphorylation via ascorbic acid-glutathione metabolism. Flavonols activated antioxidative process and non-specific immunity via vitamins B 2 -B 6 metabolism.

The negative effects of heavy metals have aroused much attention due to their high toxicity to human beings. Migration and transformation trend of heavy metals have a close relationship with soil safety. Researching on migration and transformation of heavy metals in tailings can provide a reliable basis for pollution management and ecosystem restoration. Heavy metal speciation plays an important role in risk assessment. We chose Anshan tailings for our study, including field investigations and laboratory research. Four typical heavy metal elements of mine tailings {Fe (373.89 g/kg), Mn (2,303.80 mg/kg), Pb (40.99 mg/kg) and Cr (199.92 mg/kg)} were studied via Tessier test in vertical and horizontal direction. The main speciation of heavy metals in Anshan tailings was the residual. However, heavy metals have a strong ability for migration and transformation in vertical and horizontal directions. Its tendency to change from stable to unstable speciation results in increasing bioavailability and potential bioavailability. Fe, Mn, Pb and Cr showed different ability in the migration and transformation process (Mn > Pb > Fe > Cr) depending on the characteristics of heavy metals and physicochemical properties of the environment.

Arsenic is a pollutant that can be detected in different chemical forms in soil. However, the toxicological effects of different arsenic species on organisms have received little attention. In this study, we exposed earthworms Eisenia fetida to artificial soils contaminated by arsenite [As(III)], arsenate [As(V)], monomethylarsonate (MMA) and dimethylarsinate (DMA) for 28 and 56 days. Three biomarkers including lipid peroxidation (LPO), metallothioneins (MTs) and lysosomal membrane stability (LMS) were analyzed in the organisms. In addition, the contents of total arsenic and arsenic species in earthworms were also determined to investigate the effects of bioaccumulation and biotransformation of arsenic on biomarkers and to evaluate the dose-response relationships. The results showed that the relationship between the three biomarkers and the two inorganic arsenic species were dose dependent, and the correlation levels between the biomarkers and As(III) were higher than that between the biomarkers and As(V). Trivalent arsenic species shows more toxicity than pentavalent arsenic on the earthworms at molecular and subcellular level, including oxidative damage, MTs induction and lysosomal membrane damage. The toxicity of MMA and DMA was lower than inorganic arsenic species. However, the occurrence of demethylation of organic arsenics could lead to the generation of highly toxic inorganic arsenics and induce adverse effects on organisms. The biotransformation of highly toxic inorganic arsenics to the less toxic organic species in the earthworms was also validated in this study. The biomarker responses of the earthworm to different arsenic species found in this study could be helpful in future environment monitoring programs., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Heavy metals are among the major pollutants in the worldwide soil environment. In oilfields, the crude oil extraction process results in the simultaneous contamination of the soil with petroleum and heavy metals. In this work, we investigated the influence of oil extraction on the migration, speciation, and temporal distribution of heavy metals (Cu, Zn, Pb, Cd, Cr, Mn, Ni, V, and Mn) in soils of an oil region of Shengli Oilfield, China. The results showed that oil-polluted soils were contaminated with Cu, Zn, Cd and Ni, with mean concentrations of 27.63, 67.12, 0.185 and 33.80 mg kg(-1), respectively (greater than the background values of local surface soils). Compared with the control profile, the vertical distributions of Cu, Zn, Pb, Cd, Ni, and V were affected in oil-polluted soils, particularly those of Cd and Ni. The concentrations of Zn, Cd, Ni, V, and Mn in oil-polluted soils increased with the duration of oil well development, which indicated the levels of these metals in the oil field were enhanced by human activities. Fractionation analysis revealed that the mobility potential of heavy metals in oil polluted soil decreased in the sequence Cd > Mn > Zn > Ni > Pb > Cu > Cr > V. The most important proportion of Cd is ion exchangeable and acid soluble, which indicates that Cd is the most labile, available, and harmful heavy metal among the elements that damage the soil environment in oil-polluted soil.