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Abstract Colloids are ubiquitous in soils, and it has been reported that colloids can act as carriers to increase the mobility of poorly soluble contaminants in subsurface environments. Addition of sulfur (S) fertilizer greatly influences on heavy metal behavior in paddy soil, while the influence of S fertilizer on Cu migration and transformation in colloids of soil pore water has not yet been studied. The influence of S fertilizer (S0 and Na 2 SO 4) applied in paddy soils on Cu migration and transformation in colloids of soil pore water from the rice rhizosphere region was explored in this study. The speciation of Cu in colloids of soil pore water from the rice rhizosphere region was explored by advanced synchrotron-based X-ray absorption near-edge spectroscopy (XANES) techniques. The morphology of colloids was characterized by field emission scanning electron microscopy coupled to energy dispersive X-ray spectroscopy (SEM-EDX). At a depth of 20 cm, the concentration of Cu in colloids of the rhizosphere soil pore water in the control was 2.4- and 6.5- fold higher than that in treatments of S0 and Na 2 SO 4 , respectively. The colloids in soil pore water were all positively charged, ranging from 2.4 to 7.8 mV, and the size of colloids was 440–740 nm. The proportion of Fe in colloids in the rhizosphere region decreased with S fertilizer application, while the proportions of C and O increased. Sulfur fertilizer application, increased the proportion of Cu-Cysteine, while the proportion of Cu 2 S decreased in soil colloids. In conclusion, application of sulfur fertilizer in paddy soil decreased the Cu concentration in soil pore water and colloids of the rhizosphere region, thereby decreasing the vertical migration of Cu in soil pore water. Graphical abstract The effect of sulfur fertilizer on Cu migration and transformation in colloids of soil pore water from the rice rhizosphere region. Image 1 Highlights • Sulfur fertilization decreased the concentration of Cu in pore water colloids from the rice rhizosphere region. • The proportion of Fe in pore water colloids in the rhizosphere region decreased with S fertilizer application while C and O increased. • Sulfur fertilization increased the proportion of Cu-Cysteine in pore water colloids from the rice rhizosphere region, while Cu 2 S decreased. [ABSTRACT FROM AUTHOR]

Abstract Particulate organic matter (POM) acts as a metals sink in soil, but only a few studies focused on the interaction of POM and heavy metals in paddy soil. The aim of this study is to investigate the interaction between POM and Copper (Cu)/Zinc (Zn). Two levels of Cu (100, 400 mg kg−1) and Zn (250, 500 mg kg−1) were used in a soil culture experiment. Our results showed that POM was porous structure and varied in size. Hydroxyl and carboxyl involved in POM adsorption of Cu and Zn. Rhizosphere effects roughen the surface of POM and enhanced the capacity of POM on heavy metals absorption. Cu-humic (26.2–33.9%) and Cu-citrate (38.5–42.4%) were dominated in POM, and Cu-goethite (41.7–57.7%), Cu-sulphide (6.6–27.6%) was dominated in soil. Rhizosphere effects decreased the proportion of organic-bond Cu along with the increasing the proportion of Cu-sulphide in POM. Addition of Cu and Zn inhibited the degradation of POM but rhizosphere effects promoted. Carbon content was increased in POM by heavy metal and rhizosphere effects. Our findings indicated that POM tended to retain the heavy metals in soil and heavy metals inhibited the degradation of POM, however, rhizosphere effects decreased the stability of POM-metals interactions. Graphical abstract Image 1 Highlights • Hydroxyl and carboxyl were involved in POM adsorption of heavy metals. • Cu was mostly bonded to organic acids in POM, whereas most of Cu was combined with goethite and S in soil. • Rhizosphere effects decreased contents of Cu-organic acids and increased contents of Cu 2 S in POM. • Cu and Zn inhibited the degradation of POM but rhizosphere effects stimulated. • Heavy metals and rhizosphere effects changed the components of POM. [ABSTRACT FROM AUTHOR]

Metabolism of sulfur (S) is suggested to be an important factor for the homeostasis and detoxification of Cu in plants. We investigated the effects of S fertilizers (S 0 , Na 2 SO 4 ) on Cu translocation and biotransformation in rice plants by using multiple synchrotron-based techniques. Fertilization of S increased the biomass and yield of rice plants, as well as the translocation factor of Cu from root to shoot and shoot to grain, resulting in enhanced Cu in grain. Sulfur K-edge X-ray near edge structure (XANES) analysis showed that fertilization of S increased the concentration of glutathione in different rice tissues, especially in rice stem and leaf. Copper K-edge XANES results indicated that a much higher proportion of Cu (I) species existed in rice grain than husk and leaf, which was further confirmed by soft X-ray scanning transmission microscopy results. Sulfur increased the proportion of Cu (I) species in rice grain, husk and leaf, suggesting the inducing of Cu (II) reduction in rice tissues by S fertilization. These results suggested that fertilization of S in paddy soils increased the accumulation of Cu in rice grain, possibly due to the reduction of Cu (II) to Cu (I) by enhancing glutathione synthesis and increasing the translocation of Cu from shoot to grain. [ABSTRACT FROM AUTHOR]

CuO nanoparticles (CuO-NP) were synthesized in a hydrogen diffusion flame. Particle size and morphology were characterized using scanning mobility particle sizing, Brunauer–Emmett–Teller analysis, dynamic light scattering, and transmission electron microscopy. The solubility of CuO-NP varied with both pH and presence of other ions. CuO-NP and comparable doses of soluble Cu were applied to duckweeds, Landoltia punctata. Growth was inhibited 50% by either 0.6mgL−1 soluble copper or by 1.0mgL−1 CuO-NP that released only 0.16mgL−1 soluble Cu into growth medium. A significant decrease of chlorophyll was observed in plants stressed by 1.0mgL−1 CuO-NP, but not in the comparable 0.2mgL−1 soluble Cu treatment. The Cu content of fronds exposed to CuO-NP is four times higher than in fronds exposed to an equivalent dose of soluble copper, and this is enough to explain the inhibitory effects on growth and chlorophyll content. [Copyright &y& Elsevier]

Abstract: Microbe–mineral interactions play an important role in affecting geochemical transformations of heavy metals in the soil environment. The formation of metal sulfide, which is mediated by sulfate-reducing bacteria (SRB) through contributing to sulfate reduction is an important pathway for heavy metal stabilization in anoxic soil. In oxic rice rhizospheres, there are abundant sulfur oxidizing bacteria (SOB) which can enhance sulfur oxidation and hence the availability of heavy metals, resulting in the uptake of such metals by the plant and a potential risk to human health. In this study, the potential existence of SRB in oxic rice rhizospheres, their contribution to sulfate reduction, and potential to reduce the availability of heavy metal was investigated. PCR-DGGE fingerprinting and real-time PCR results showed increasing numbers of SRB with Pb addition, which corresponded with increases in soil pH and reduction in Eh, suggesting the enhancement of sulfur reduction and SRB activity. Sulfur K-edge XANES, which characterized sulfur speciation in situ, revealed reduced states of sulfur. The SRB mediated the sulfate reduction and contributed to the formation of reduced sulfur which interacted with Pb, leading to the formation of stable metal sulfide and reduction of Pb availability. In return, acclimated SRB populations developed in Pb-polluted conditions. Hence stabilization of reduced sulfur by Pb enhanced the activity of SRB and sulfate reduction in rice rhizosphere. [Copyright &y& Elsevier]

Tissue concentrations of some mineral elements appeared to be influenced by plant Fe status. The influence of Fe deficiency on Cu uptake and accumulation in Commelina communis, and the relationship between Cu uptake and root Fe(III) chelate reductase (FCR) activity were investigated in this study. The results showed that Cu accumulation in C. communis was increased with the drop of Fe concentration in nutrient solution. Cu uptake in C. communis was significantly enhanced by Fe deficiency. Cu uptake in Fe-deficient plants were still higher than that of Fe-sufficient plants when P-type ATPase inhibitor Na3VO4 was added in the solution, which demonstrated that Fe deficiency induced stimulation of the plasma membrane H+-ATPase did not play a role in the enhanced Cu uptake. Fe and Cu deficiency could induced root Fe(III) chelate reductase activity in C. communis. Both Fe(III) chelate reductase activity aud Cu concentration in roots inhibited distinctly by cycloheximide, a kind of protein synthesis inhibitor. In the time course of Fe deficiency, there simultaneously appeared Cu concentration and FCR activity peaks in roots at day 9. All above evidences demonstrated Cu uptake aud accumulation in C. communis were probably related to the root FCR activity. [Copyright &y& Elsevier]

Lead contamination in soil has become a worldwide threat on food security and human health. To assess the Pb bioavailability and evaluate the safe use of low Pb polluted soil for food production, the speciation of Pb in 19 types of paddy soil were investigated by chemical extraction and X-ray absorption near-edge structure (XANES), and the uptake and accumulation characteristics of Pb in different soil-rice systems were investigated. Moreover, an empirical model was established to predict the content of Pb in rice grain, and field validation was conduct to evaluate model performance. Results showed that the proportion of available Pb in different soil satisfied normal distribution N (0.47, 0.23). Pb(CH 3 COO) 2 , GSH-Pb, PbO, PbHPO 4 and Pb 3 (PO 4) 2 performed well in characterizing the speciation of Pb in different rhizosphere soils, and PbHPO 4 accounted for more than 70%. The exceedance of Pb in grain in CK, 0.5X and 1X treatment were 10.5%, 36.1% and 42.1%, respectively, and the accumulation of Pb in grain was significantly related with Pb content in root. Carbonate and organic bound Pb in rhizosphere soil were two major Pb species that influenced the accumulation of Pb in rice. Moreover, content of total Pb, clay and SOM performed well in predicting the Pb content in grain, both for pot and field samples. Above all, our predicting model worked well in evaluating Pb accumulation in rice grain among low polluted paddy farmland (Total Pb < 300 mg/kg). Image 1 • Edible Pb content was positively related to the carbonate and organic bounded Pb in rhizosphere soil. • The specific speciation of Pb in different rhizosphere soils was clarified using XANES. • The content of total Pb, clay and SOM performed well in predicting the Pb content in rice grain. • Our model worked well in evaluating Pb content in rice grain among low polluted farmland. [ABSTRACT FROM AUTHOR]

Though the interaction between humic acid (HA) and heavy metals has been widely reported, the effects of HA on the toxicity of heavy metals to plants are still in debate. In this study, the regulation mechanisms of HA on Pb stress in tea plant (Camellia sinensis L.) was investigated through hydroponic experiments, and the experimental results were explained by using transmission electron microscope (TEM), scanning transmission X-ray microscopes (STXM) and isobaric tags for relative and absolute quantitation (iTRAQ) differential proteomics. Significant alleviation of Pb stress was found with HA coexistence. TEM results showed that HA greatly mitigated the damage of cells caused by Pb stress. Compared with sole Pb treatment, the addition of HA increased the contents of pectin and pectic acid in the cell wall by 10.5% and 30.5%, while arabinose (Ara) and galactose (Gal) decreased by 20.5% and 15.9%, respectively, which were beneficial for increasing Pb adsorption capacity of the cell wall and promoting cell elongation. Moreover, iTRAQ differential proteomics analysis proved that HA strengthened the antioxidant system, promoted the synthesis of cell wall, and stabilized protein and sulfur-containing substance metabolism in molecular level. Notably, the concentration of calcium (Ca) in the cell wall of HA coexistence treatment was 47.4% higher than Pb treatment. STXM results also indicated that the distribution of Ca in the cell wall was restored with the presence of HA. This might promote the formation of the egg-box model, thus alleviating Pb stress in cells. Our results reveal the regulation mechanisms of HA on Pb detoxification in plants and provide useful information for improving the safety of agricultural products. Image 1 • HA greatly strengthened the antioxidant system and mitigated the damage of the cells caused by Pb stress. • The regulation of carbohydrate components and calcium enhanced the accumulation of Pb in cell wall. • HA stabilized protein and sulfur-containing substance metabolism to resist Pb stress. HA mainly alleviated Pb stress in tea plant by strengthening the antioxidant system, promoting the synthesis of cell wall, and stabilizing protein metabolism. [ABSTRACT FROM AUTHOR]

Arsenic (As) has been recognized as one of the most toxic metalloids present in the surface soil contaminating food chain and posing threat to human life. Sulfur (S) fertilizer is often supplied in paddy soil for rice growth, but its impact on As mobility and related bacteria remains poorly understood. In this study, a pot experiment was set up with two different types of sulfur treatments (element sulfur and Na 2 SO 4) to evaluate the effect of sulfur fertilizers on As speciation in porewater, As fractions in soil, As accumulation in rice plants. Besides, rhizosphere bacterial composition and functional genes that might influence As mobility were also studied. The results revealed that the addition of 150 mg/kg Na 2 SO 4 decreased As(III) and As(V) concentrations in soil porewater at maturation stage by 77% and 64%, respectively. With the same sulfur content, Na 2 SO 4 was more effective than element sulfur. The addition of sulfur fertilizers promoted rice growth and reduced As accumulation in shoots, further reduced As translocation from root to above-ground parts by 39–59%. The addition of sulfur fertilizers had little effect on genes involved in As metabolism. However, the relative abundance of Fe(III) and sulfate reduction related genera increased with the addition of 150 mg/kg Na 2 SO 4 , consistent with the increase of Fe(III) reducing bacteria Geobacteraceae and sulfate reducing gene dsrA. The phenomenon likely influenced the decrease of As concentrations in soil porewater and rice uptake. The outcomes indicate that promoting Fe- and S- reducing bacteria in the rhizosphere by sulfur fertilizers may be one way to reduce As risk in the soil-rice system. Image 1 • Addition of sulfur fertilizers decreased As(III) in soil solution and reduced the mobility of As. • Addition of sulfur fertilizers decreased As accumulation in rice shoots. • Application of Na 2 SO 4 increased the relative abundance of Fe(III) and sulfate reducing related bacteria. • Application of Na 2 SO 4 did not affect the relative abundance of as functional genes significantly. Sulfur fertilizers decreases As bioavailability likely via increasing the rhizospheric Fe(III) and sulfate reducing bacteria. [ABSTRACT FROM AUTHOR]

• Five elution methods and optimal elution conditions of cyanide tailings were investigated. • Four reagents were screened to promote the elution of cyanide tailings, and the optimal proportion of these four reagents was determined as 5:2:2:1. • The combination of reagent elution and positive pressure filtration for synergistic elution improved the elution efficiency of cyanide. • The combined elution strategy was applied to engineering and achieved desired results. At present, the cyanide gold extraction process is still the main technology for gold production. Generated cyanide tailings containing highly toxic substances exhibit potential environmental risks. These tailings are in urgent need of purification treatment, especially after being classified as hazardous waste. In this study, the impacts of elution methods, operating time, tailings/water ratios, reagent types on the elution rates of cyanide were investigated. Furthermore, the composite elution method developed in this research was extended for engineering. Results showed that the optimum elution conditions were determined to be: stirring elution, tailings/water ratio (M/V ; 1:1) and operating time (10-20 min). Besides, 4 reagents (sodium dodecyl benzene sulfonate, cyclodextrin, sodium silicate and calcium hydroxide) were selected from four categories of 21 reagents for further composite elution. The cyanide elution rate was the highest (90.7%±0.1%) while the molar ratio of these 4 reagents was 5:2:2:1. Moreover, the combination of reagent elution and positive pressure filtration improved the elution efficiency of cyanide (92.6%±0.8%). And the cyanide content in the toxic leaching solution was lower than the standard value (5.0 mg/L). Furthermore, the composite elution method developed in this study was also extended for engineering. The concentration of cyanide in the leachate was < 5.0 mg/L, and was stable during 189 days of detection. Notably, the effluent can be reused directly, or reused after further treatment. The zero discharge of effluents and solid wastes was realized in the processes. The above results provided supports for the engineering treatment of cyanide tailings. [Display omitted] [ABSTRACT FROM AUTHOR]

The biogeochemical cycling of sulfur in soil is closely associated with the mobility and bioavailability of heavy metals; however the influence of sulfur on the behavior of metal-based nanoparticles has not yet been studied. The influence of S fertilizer (S0 and Na 2 SO 4) applied in paddy soils on CuO NPs behavior in soil pore water was explored in the present study. Synchrotron-based techniques were applied to investigate the migration and speciation transformation of CuO NPs in soil pore water colloids. The application of sulfur fertilizer increased the zeta potential of soil colloids from the rice rhizosphere region and reduced the size of the colloids. Sulfur fertilization decreased the concentration of Cu in soil pore water in the rice rhizosphere region. S0 fertilizer reduced the Cu concentration in soil colloids (by 55.8%–73.5%), while Na 2 SO 4 increased the Cu concentration in soil colloids (by 173.8%–265.1%). Sulfur fertilization changed the spatial distribution of Fe3+ and Cu2+ in colloids, making these ions more likely to be aggregated on the edges of soil colloids. Speciation transformation of CuO NPs happened during the process of migration. The main Cu speciation in the soil colloids were CuO NPs, Cu-Cysteine, Cu 2 S and Cu-Citrate. Sulfur fertilization increased the proportion of Cu 2 S (by 40.5%) in soil pore water colloids from the rice rhizosphere region, while the proportion of CuO NPs was reduced (by 18.4%). Sulfur fertilization changed the morphology and elementary composition of colloids in soil pore water, thus influencing the migration of CuO NPs in the soil column through soil colloids. Image 1 • Sulfur fertilization decreased the concentration of Cu soil pore water. • CuO NPs could migrate with pore water colloids. • Sulfur fertilization increased the proportion of Cu 2 S in colloids of soil pore water. Sulfur fertilization changed the morphology and elementary composition of colloids in soil pore water, thus influencing the migration of CuO NPs in the soil column through soil colloids. [ABSTRACT FROM AUTHOR]

Currently, copper oxide nanoparticles (CuO NPs) have been widely used in industry, manufacturing and agriculture. The transport and retention of CuO NPs are vital to understanding the fate as well as the life cycle of CuO NPs in the environment. This study systematically investigates the transport and retention of CuO NPs in saturated porous media, and the experimental results were explained by the CFT and DLVO theory. The van der Waals force between CuO NPs and collector was repulsive, resulting in the unfavorable deposition condition. Column experiments were conducted with saturated quartz sand under environmentally relevant pH (6, 8, 9), ionic strength (IS, 1, 10, 50 mM), and humic acid (HA, 0.1–10 mg-C/mL). Experimental results show that the breakthrough curves (BCTs) were affected by different pH and IS. Under pH 6 and 9, the mobility of CuO NPs was enhanced by high IS while the mobility was inhibited by high IS under pH 8. The mobility of CuO NPs was enhanced by humic acid and the effect was best at 0.5 mg-C/mL HA. The experimental results were successfully explained by CFT and DLVO theory, the main mechanisms were aggregation of CuO NPs, interaction energy and collision between CuO NPs and collector. In general, these findings can improve our understanding of the transport and retention of CuO NPs in subsurface environments, and suggest pH, IS, HA may be key factors governing mobility and stability of CuO NPs in natural environment. Image 1 • Unfavorable deposition condition of CuO NPs was caused by the repulsive van der Waals force between CuO NPs and collector. • Different patterns of DLVO energy curve were observed under different pH. • Enhanced transport ability of CuO NPs was observed under the presence of natural organic matter. • Experimental results were explained by the CFT and DLVO theory. Repulsive van der Waals force make the transport and retention of CuO NPs unique in saturated porous media. [ABSTRACT FROM AUTHOR]

The immobilization effectiveness between Pb and phosphorus in soil varies with soil types. To clarify the effect of phosphate on the availability of Pb in agricultural soil, a culture experiment with three types of paddy soil was performed with potassium dihydrogen phosphate (KDP) added. EDTA, DGT and in-situ solution extraction methods were used to represent different available Pb content. Results showed that the concentration of EDTA-Pb in HN soil was slightly elevated after exogenous KDP added. The supplement of 300 mg/kg KDP significantly increased the content of soluble Pb in both acid silty clay loam soil and neutral silty loam soil (increased by 104.65% and 65.12%, respectively). However, there was no significant influence of KDP on the concentration of DGT extracted Pb. XANES results showed that Pb(OH) 2 , PbHPO 4 , humic acid-Pb and GSH-Pb were the major speciation of Pb in soil colloids. The proportion of Pb(OH) 2 and humic acid-bounded Pb in soil colloids were elevated after exogenous KDP added. Our results indicated that there was a mobilization effect of KDP on Pb by increasing the amount of colloidal Pb in soil solution, especially in acid silty clay loam paddy soil. Such colloid-facilitated transport might promote the uptake of Pb in rice and pose a potential threat to human health. Image 1 • Exogenous KDP could increase the amount of colloidal Pb in soil solution. • There was a mobilization effect of KDP on Pb by increasing the amount of colloidal Pb in soil solution. • The addition of KDP as well as submergence were conducive to the formation of soil colloids. • The proportion of Pb(OH) 2 and humic acid-Pb in soil colloids were elevated after KDP added. [ABSTRACT FROM AUTHOR]

Cyanide tailings are the major hazardous wastes generated in the production process of the gold industry, which not only contain highly toxic cyanide, but also contain heavy metals with recycling value and other substances suitable for building materials or filling. These tailings are in urgent need of purification treatment and safe utilization. In this study, the impacts of treatment methods, types and combinations of reagents on decyanation effect were researched. Gold in cyanide tailings was recovered by flotation, and flotation tailings were used for filling after identifying the properties of solid waste. Results are as follows: (1) INCO method and 5 reagents (sodium sulfite, sodium persulfate, copper sulfate, ferrous sulfate and zinc sulfate) were selected for synergistic decyanation treatment, and cyanide concents in slurry and leaching solution were decreased to the minimum. (2) The gold recovery rate of the tailings through flotation was increased by 27.8% than without detoxification. (3) Flotation tailings were identified as general industrial solid wastes by leaching toxicity and toxic substance content analysis. (4) As filling aggregate, under the conditions of slurry concentration of 63% and cement-sand ratio of 1:6, the strength filling body of flotation tailings reached 1.32 Mpa after 28 days of maintenance. (5) This process and combined reagents were applied to engineering. The cyanide content in the leaching solution and the flotation recovery rate of gold were kept below 0.2 mg/L and above 60% respectively, and the strength of the filling body was stable to meet the requirements of underground filling. [Display omitted] • Different decyanation methods and reagents of cyanide tailings were researched. • Five reagents were screened for decyanation and their interaction mechanism was expounded. • Gold was extracted by flotation after detoxification and the gold recovery rate was much higher than that of non-detoxification. • Flotation tailings were identified as general industrial solid wastes for filling, and filling parameters were explored. • Efficient detoxification and full resource utilization of cyanide tailings were realized and applied to industry. [ABSTRACT FROM AUTHOR]

Penicillium oxalicum SL2 (SL2) is a previously screened Pb-tolerant fungus that can promote crops growth. The relationship between SL2 colonization and Pb immobilization was studied to provide a theoretical basis for microbial remediation of Pb-contaminated paddy soil. In this study, green fluorescent protein (GFP) labeled SL2 was inoculated into different Pb-contaminated paddy soils (S1-S6). The Pb extracted from the soil by HNO 3 , EDTA and CaCl 2 were used to characterize the available Pb. The results showed that the colonization of SL2 was divided into lag phase (0-7 days), growth phase (7-30 days), and mortality phase (30-90 days). SL2 colonized well in sandy soils rich in clay and total phosphorus with initial pH of 4.5-7.0. In addition, SL2 increased soil pH and decreased soil Eh, which was beneficial to immobilize Pb. In different soils, the highest percentages of CaCl 2 -Pb, EDTA-Pb, and HNO 3 -Pb immobilized by SL2 were 34.34%-40.53%, 17.05%-20.11%, and 7.39%-15.62%, respectively. Pearson correlation analysis showed that the percentages of CaCl 2 -Pb and EDTA-Pb immobilized by SL2 were significantly positively correlated with the number of SL2 during the growth phase. SL2 mainly immobilized Pb in the growth phase and a higher peak number of SL2 was beneficial to the immobilization of Pb. [Display omitted] [ABSTRACT FROM AUTHOR]

Oxidation remediation is a commonly used technology for PAHs contaminated soil presently, but the overestimate of efficiency due to ongoing remediation by residual oxidants during extraction and testing has not been paid enough attention. In this study, persulfate was activated by Fe(II) to investigate the effects of residual oxidants on PAHs removal during detection process and the elimination effects of adding Na 2 SO 3 and extending sampling time on residual oxidants. Results verified that the residual oxidants removed PAHs in extraction process, making the results lower than the actual values: the detection recovery rate η of ∑PAHs and 3-6 ring PAHs ranged from 24.3% (25% Na 2 S 2 O 8 treatment) to 87.4% (5% Na 2 S 2 O 8 +4/4Fe2+ treatment), 20.1%-99.0%, 28.9%-87.9%, 20.8%-89.4%, and 18.6%-76.9%, respectively. After adding Na 2 SO 3 , the accuracy of detection results increased significantly: the η of ∑PAHs and 3-6 ring PAHs increased to 64.1%-96.5%, 58.8%-95.5%, 73.8%-114.4%, 60.6%-95.6%, and 45.4%-77.1%, respectively. After 49 days of adding oxidants, residual oxidants had no considerable effect on the detection of PAHs, indicating it was appropriate to start soil remediation verification sampling49 days after the remediation was completed. The observed results will help scientific evaluation of the remediation effects of chemical oxidation on organic contaminated soil. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: Soil microorganisms may play an important role in the uptake of heavy metals from soils. However, assessments of bacterial activity and community composition in the rhizosphere of accumulators have been largely ignored. We studied potential effects of a copper (Cu)-accumulator, Elsholtzia splendens, and a non-Cu-accumulator plant, Trifolium repens, on soil microbial activity and community composition with increasing Cu addition. The results showed that concentrations of Cu in the shoots of E. splendens were 2.1, 2.2 and 2.4 times those of T. repens under the treatment of different Cu concentrations. Soil microbial biomass and phosphatase activity in the rhizosphere of E. splendens were higher than those of T.repens. PCR-denaturing gradient gel electrophoresis (PCR-DGGE) fingerprint analysis revealed that addition of Cu decreased the number of bands in bare soil and soil with T. repens. However, there was a significant increase in the number of bands in soil with E. splendens incorporated with either 200 or 500mgkg−1 Cu. The abundances of five phylogenetic groups related most closely to α-, β-, γ-proteobacteria, Gram-positive bacteria and CFB group, respectively, were determined in the rhizosphere of plants. Some specific clone such as E13 (metal-contaminated soil clone K20-64) was found in the rhizosphere of E. splendens. Results indicated that E. splendens, as a Cu-accumulator, played an important role in governing soil microbial activity and bacterial community composition in the rhizosphere in response to Cu stress. [Copyright &y& Elsevier]

Cadmium (Cd) contamination in paddy soil has become a worldwide concern and severely endangered human health. Nano hydroxyapatite (n-HAP) is a practical material to manage paddy Cd pollution, but its dosage should not be excessive. Based on previous studies, we validated the effect of n-HAP pre-treatment on rice Cd uptake in pot and field experiments. The results indicated that n-HAP pre-treatment effectively restricted Cd translocation in the soil-rice system. In pot experiment, when soil n-HAP concentration was 5000 mg/kg, the Cd content in the grains of n-HAP pre-treated rice was 0.171 mg/kg, decreased by 29.3% compared with normal rice (0.242 mg/kg). In field experiment, when soil n-HAP concentration was 20,000 mg/kg, the Cd content in the grains of n-HAP pre-treated rice was 0.156 mg/kg, decreased by 35.3% compared with normal rice (0.241 mg/kg). The primary mechanism was that n-HAP pre-treatment altered the formation and composition of iron plaque and therefore enhanced the Cd binding ability of iron plaque. The available N and P content and urease activity in paddy field were increased. We further investigated the impact of n-HAP on the diversity and structure of paddy microbial communities. The Chao1 and Shannon diversity indices showed no significant difference. The relative abundance of Actinobacteria and Proteobacteria was significantly decreased by n-HAP, indicating that Cd pollution might be alleviated. Desulfobacterota , Gemmatimonadota , and Geobacteraceae were significantly enriched by n-HAP. The declining relative abundance of Basidiomycota and the increasing relative abundance of other fungal taxa also suggested that n-HAP could alleviate Cd toxicity in soil. [Display omitted] • n-HAP pre-treatment reduced Cd accumulation in rice grains effectively. • n-HAP pre-treatment restricted Cd translocation from root to stem by regulating iron plaque formation and composition. • n-HAP significantly increased available N, P content and urease activity in paddy field. • n-HAP did not significantly affect the abundance and diversity of paddy microbial communities but altered their structure. [ABSTRACT FROM AUTHOR]

Fungi Penicillium oxalicum SL2 was applied for Pb 2+ bioremediation in aqueous solution in this study. After 7 days of incubation at different initial concentrations of Pb 2+ (0, 100, 500 and 2500 mg L −1 ), most of Pb 2+ were removed (90, 98.3, and 86.2%), the maximum Pb content in mycelium reached about 155.6 mg g −1  dw. Meanwhile, the formation of extracellular secondary minerals and intracellular Pb-complex were observed and identified, the speciation of Pb in mycelium was also detected by X-ray absorption near-edge structure (XANES) spectroscopy, i.e., Pb-oxalate, Pb-citrate, Pb-hydrogen phosphate and Pb-glutathione analogues. In addition, content of glutathione and oxidized glutathione was increased under the exposure of Pb 2+ , which implied that glutathione might play a key role in Pb immobilization and detoxification in P. oxalicum SL2. This study elucidated partial mechanisms of Pb immobilization and speciation transformation of this strain, providing an alternative biomaterial in the bioremediation of Pb-contaminated wastewater. [ABSTRACT FROM AUTHOR]

Nowadays, Lead (Pb) and Cadmium (Cd) contamination in rice is an important worldwide environmental concern. Fe 3 O 4 nanoparticles (Fe 3 O 4 NPs) and Nano hydroxyapatite (n-HAP) are promising materials to manage Pb and Cd contamination. This study systematically investigated the effect of Fe 3 O 4 NPs and n-HAP on Pb and Cd stressed rice seedlings' growth, oxidative stress, Pb and Cd uptake and subcellular distribution in roots. Furthermore, we clarified the immobilization mechanism of Pb and Cd in the hydroponic system. Fe 3 O 4 NPs and n-HAP could reduce Pb and Cd uptake of rice mainly through decreasing Pb and Cd concentrations in culture solution and combining with Pb and Cd in root tissues. Pb and Cd were immobilized by Fe 3 O 4 NPs through complex sorption processes and by n-HAP through dissolution-precipitation and cation exchange, respectively. On the 7th day, 1000 mg/L Fe 3 O 4 NPs reduced the contents of Pb and Cd in shoots by 90.4% and 95.8%, in roots by 23.6% and 12.6%, 2000 mg/L n-HAP reduced the contents of Pb and Cd in shoots by 94.7% and 97.3%, in roots by 93.7% and 77.6%, respectively. Both NPs enhanced the growth of rice seedlings by alleviating oxidative stress and upregulating glutathione secretion and antioxidant enzymes activity. However, Cd uptake of rice was promoted at certain concentrations of NPs. The subcellular distribution of Pb and Cd in roots indicated that both NPs decreased the percentage of Pb and Cd in the cell wall, which was unfavorable for Pb and Cd immobilization in roots. Cautious choice was needed when using these NPs to manage rice Pb and Cd contamination. [Display omitted] • Fe 3 O 4 NPs immobilized Pb and Cd through complex sorption processes. • n-HAP immobilized Pb and Cd through dissolution-precipitation and cation exchange. • Cd accumulation in rice roots could increase due to using Fe 3 O 4 NPs and n-HAP. • Fe 3 O 4 NPs and n-HAP decreased the percentage of Pb and Cd in the cell wall. [ABSTRACT FROM AUTHOR]

[Display omitted] • 10 μM Erythrosine reduced the coronavirus titer by more than 99.999% within 30 min. • Erythrosine inactivated the virus by producing singlet oxygen induced by light. • The color loss of erythrosine can indicate the complete inactivation of the virus. • The filtration efficiency of the mask remained at > 95% after erythrosine treatment. The global health crisis caused by the COVID-19 pandemic has led to a surge in demand and use of personal protective equipment (PPE) such as masks, putting great pressure on social production and the environment. It is urgent to find an efficient and non-destructive disinfection method for the safe reuse of PPE. This study proposes a PPE disinfection method that uses erythrosine, a U.S. Food and Drug Administration-approved food dye, as photosensitizer to produce singlet oxygen for virus inactivation, and indicates the completion of disinfection by its photobleaching color change. After spraying 100 μL of 10 μM erythrosine on the surface of the mask for 3 times and light exposure for 25 min, the titer of coronavirus decreased by more than 99.999%, and the color of erythrosine on the mask surface disappeared. In addition, the structure of the mask was intact and the filtration efficiency was maintained at > 95% after 10 cycles of erythrosine treatment. Therefore, this disinfection method can provide at least 10 cycles of reuse with the advantages of high safety and convenient, and the completion of disinfection can be indicated by its photobleaching, which is suitable for hospitals and daily life to reduce the consumption of PPE. [ABSTRACT FROM AUTHOR]

Harmful algal blooms frequently occur globally, and forecasting could constitute an essential proactive strategy for bloom control. To decrease the cost of aquatic environmental monitoring and increase the accuracy of bloom forecasting, a novel single-parameter approach combining wavelet analysis with artificial neural networks (WNN) was developed and verified based on daily online monitoring datasets of algal density in the Siling Reservoir, China and Lake Winnebago, U.S.A. Firstly, a detailed modeling process was illustrated using the forecasting of cyanobacterial cell density in the Chinese reservoir as an example. Three WNN models occupying various prediction time intervals were optimized through model training using an early stopped training approach. All models performed well in fitting historical data and predicting the dynamics of cyanobacterial cell density, with the best model predicting cyanobacteria density one-day ahead ( r = 0.986 and mean absolute error = 0.103 × 10 4 cells mL −1 ). Secondly, the potential of this novel approach was further confirmed by the precise predictions of algal biomass dynamics measured as chl a in both study sites, demonstrating its high performance in forecasting algal blooms, including cyanobacteria as well as other blooming species. Thirdly, the WNN model was compared to current algal forecasting methods (i.e. artificial neural networks, autoregressive integrated moving average model), and was found to be more accurate. In addition, the application of this novel single-parameter approach is cost effective as it requires only a buoy-mounted fluorescent probe, which is merely a fraction (∼15%) of the cost of a typical auto-monitoring system. As such, the newly developed approach presents a promising and cost-effective tool for the future prediction and management of harmful algal blooms. [ABSTRACT FROM AUTHOR]

Oxalic acid is the most abundant low molecular weight organic acid (LMWOA) in many environments and offers enormous prospects for treating Cr(VI) contamination. In this study, laboratory batch experiments were conducted to estimate the roles of oxalic acid in Cr(VI) removal by Penicillium oxalicum SL2. Oxalic acid changed the initial pH and provided a suitable condition for the growth of strain SL2 when the penicillium was applied to bioremediation of Cr(VI) contamination in alkaline soil. Gompertz model analysis indicated that initial pH affected the lag time of the growth curve of strain SL2. Scanning electron microscopy and scanning transmission X-ray microscopy analysis showed strain SL2 sufficiently contacted with contaminated soil and reduced Cr(VI) to Cr(III) in the hyphae. The results suggested that oxalic acid could enhance the bioremediation efficiency of strain SL2 though improving chromium bioleaching from the contaminated soil and strengthening Cr(VI) removal in the leaching solution. This study provided oxalic acid as a green reagent for stimulating Cr(VI) removal by strain SL2 and would expand knowledge on the roles of LMWOA in Cr(VI) bioremediation. [Display omitted] • Gompertz model could simulate the growth curve of strain SL2 under initial pH5 to pH9. • Growth of strain SL2 had a strong correlation with Cr(VI) removal. • Oxalic acid improved chromium bioleaching by strain SL2 from contaminated soil. • Oxalic acid enhanced Cr(VI) removal by strain SL2 in the leaching solution. [ABSTRACT FROM AUTHOR]

The toxic chemical element cadmium (Cd) in paddy fields triggered increasing problems of growth inhibition and food security in rice consistently. In this study, we found Metarhizium robertsii , which is widely used as a bioinsecticide and biofertilizer in agriculture and recently found to be resistant to Cd, developed intraradical and extraradical symbiotic hyphae in rice seedlings, and successfully colonized in the rice rhizosphere soil to more than 103 CFUs g−1 soil at harvesting. M. robertsii colonization significantly reduced Cd accumulations in both hydroponically cultured seedlings and the matured rice cultured in Cd contaminated potting soil (2 ppm). Notably, Cd accumulation reduction of the roots, stems, leaves, husks and grains of the matured rice induced by the fungus were 44.3%, 32.1%, 35.3%, 31.9% and 24.7%, respectively. It was caused by the M. robertsii -induced suppression of Cd intake transporter gene osNramp5 in the rice roots, and the chemical stabilizing of Cd to the residual fraction in the rhizosphere soil. In addition, the colonization of M. robertsii significantly promoted the growth characters and the photosynthesis of the rice plants. This is achieved by the increase of endogenous hormone levels of indole-3-acetic, gibberellin A 3 and brassinolide induced by M. robertsii. Furthermore, the fungus enhanced the antioxidative capacities via increasing enzyme activities of catalase, peroxidase and the production of glutathione, ascorbic acid, proline in the rice plants. Our work provides theoretical basis for expanding the use of M. robertsii as in situ Cd accumulation reduction and detoxification agents for rice in contaminated paddy fields. [Display omitted] • M. robertsii colonized well in the rice roots and the rhizosphere soil. • M. robertsii reduced Cd accumulation and promoted plant growth of rice. • Rice osNramp5 was suppressed and soil Cd ions were stabilized by the fungus. • Endogenous phytohormones IAA, GA 3 and BL were elevated by the fungus. • M. robertsii stimulated antioxidative capacities of rice. [ABSTRACT FROM AUTHOR]

Microbial remediation is preferred as a clean and cost-effective method for restoring environments polluted by organics. But the biodegradation rates of hydrophobic organic contaminants (HOCs) are usually extremely restricted by their low bioavailability, especially in soil. Here, a physical method (mechanical mixing) and a chemical method (randomly methylated- β -cyclodextrins, RAMEB) were adopted to improve the bioavailability and biodegradation of polychlorinated biphenyls (PCBs) of an aged soil. The bioavailability of tri-CBs was increased by adding RAMEB in soil/slurry or assisting mechanical mixing in slurry, but these methods had no effects on the bioavailability of tetra-CBs and high chlorinated PCBs (Cl > 4). The degradation rate of tri-CBs could be obviously enhanced by adding RAMEB in soil or assisting mechanical mixing in slurry. The highest removal amount of tri-CBs reached 43.8% in 100 d with a first-order decay kinetics constant of 0.0059 d −1 . But the removal of tetra-CBs and high chlorinated PCBs (Cl > 4) were not significant in all mesocosms, possibly due to the lack or weakness of the native degrading microflora. Based on the analysis of the richness and diversity of bacterial communities, the characteristics of the heatmap and the variation of bphC copy numbers in the soil/slurry mesocosms, it could be inferred that there was no obvious corresponding relationship between the variation of the bacterial communities and the physical/chemical measures. [ABSTRACT FROM AUTHOR]

Abstract: The effects of allelochemicals on cyanobacterial blooms have been observed for more than 20 years; however, the use of these compounds, usually involving a “direct-added” mode, has clear disadvantages, such as a short activity period or temporarily excessive localized concentration. Here, a simulated-allelopathy mode to facilitate the application of allelochemicals was proposed and tested on Microcystis aeruginosa . The continuous-release beads of 5,4′-dihydroxyflavone (DHF) were constitutive of a polymer matrix and showed a high drug-loading rate (47.18%) and encapsulation efficiency (67.65%) with a theoretical release time of approximately 120 d. Cyanobacterial growth tests showed that the DHF beads had long-term inhibition effects (>30 d), whereas those of “direct-added” DHF to cells lasted a maximum of 10 d. The beads also continuously affected the superoxide dismutase, catalase, and lipid peroxidation of M. aeruginosa . The inhibitory effects of DHF beads on cyanobacterial growth increased as initial cell densities of M. aeruginosa decreased, suggesting that the beads inhibit cyanobacterial activity more effectively in the early bloom phase. Consequently, the anti-cyanobacterial beads represent a novel application mode of allelochemicals with long-term inhibitory effects on cyanobacterial growth. Our study demonstrates that the successful application of allelochemicals offers great potential to control harmful cyanobacterial blooms, especially at the initial stage of development. [ABSTRACT FROM AUTHOR]

Using manure-derived-biochar as an alternative phosphorus (P) source has bright future prospects to improve soil P status. A 98-day microcosm incubation experiment was set up for two soils which were amended with manure biochar at proportions of 0, 0.5% and 1.5%. Swine manure samples were air-dried and manure biochar was prepared by pyrolysis at 400 °C for 4 h. As determined by P-31 nuclear magnetic resonance ( 31 P NMR) spectroscopy, manure biochar mainly increased the contents and fractions of orthophosphate and pyrophosphate in two soils, while decreased those of monoesters ( P < 0.05). At the end of incubation, 1.5% of manure biochar raised soil pH by 0.5 and 0.6 units, cation exchange capacity by 16.9% and 32.2%, and soil total P by 82.1% and 81.1% for silt loam and clay loam soils, respectively, as compared with those soils without biochar. Simultaneously, 1.5% of manure biochar decreased acid phosphomonoesterase activities by 18.6% and 34.0% for clay loam and silt loam, respectively; while it increased alkaline phosphomonoesterase activities by 28.5% and 95.1% for clay loam and silt loam, respectively. The enhancement of soil P availability after manure biochar addition was firstly due to the orthophosphate and pyrophosphate as the major P species in manure biochar which directly increased contents of soil inorganic P, and also attributed to the decomposition of some organic P like monoesters by enhanced alkaline phosphomonoesterase activities from manure biochar addition. [ABSTRACT FROM AUTHOR]

Programmed cell death (PCD) in root border cells (RBCs) induced by Copper (Cu) has been little studied. This study explored whether Cu induced PCD in RBCs of cucumber or not and investigated the possible mechanisms. The results showed that the percentage of apoptotic and necrotic RBCs increased with increasing concentration of Cu treatment. A quick burst of ROS in RBCs was detected, while mitochondrial membrane potential (Δ Ψ m ) decreased sharply with Cu treatment. Caspase-3 like protease activity showed a tendency of increase with Cu treatment. The potential of Cu to induce PCD in RBCs of cucumber was first proved. Our results showed that ROS generation and mitochondrial membrane potential loss played important roles in Cu-induced caspase-3-like activation and PCD in RBCs of cucumber, which provided new insight into the signaling cascades that modulate Cu phytotoxicity mechanism. [ABSTRACT FROM AUTHOR]

Abstract: A pot experiment was carried out to study the sulfur (S) and lead (Pb) interaction and its impact on soil microbial community composition in rice rhizosphere soil under flooded conditions. Paddy soil was treated with a Pb gradient with and without thiosulfate addition and then planted with rice. The increasing addition of Pb resulted in plant yield reduction and high, phytotoxic concentrations of Pb in roots with relatively low concentration of Pb in shoots. Under the impact of thiosulfate, Pb uptake in plants and NH4OAc extractable Pb did not increase dramatically. PCR-DGGE experiment suggested that S action led to new bands. Specific clones (T3 and T6) found in S addition soils had high similarity to Thiobacillus, which indicated relatively high rates of potential S oxidation. S addition did not affect the availability Pb and the composition of soil microbial community. S addition is not a suitable amendatory tool of phytoremediation for Pb polluted soil. [Copyright &y& Elsevier]

Abstract: To further understand the hyperaccumulation of Mn, the present study investigated the accumulation of Ca and Mn and their interaction in Mn hyperaccumulator pokeweed (Phytolacca americana Linn.). Exogenous Ca was observed to have a distinctive impact on the Mn phytotoxicity and accumulation in pokeweed, but exogenous Mn had little influence on the accumulation of Ca. Both Ca and Mn accumulated in pokeweed were detected to be mainly in the form of oxalate. Investigation with SEM and TEM found there were two kinds of crystals in the leaves, Ca oxalate crystals and Mn-containing crystals. Further detection showed that there was no inclusion of Mn inside the Ca oxalate crystals, and that other elements, such as C, O and P, were present in the Mn-containing crystals. These results suggest that Ca oxalate crystals in pokeweed have no direct effect on the detoxification of Mn. In addition, the finding of element P and O in the Mn-containing crystals indicates that excess Mn could be deposited by phosphate, which could contribute to Mn accumulation and detoxification in pokeweed. [Copyright &y& Elsevier]

The present study was conducted to determine the abilities of the living and nonliving Pseudomonas putida CZ1 cells, clays (goethite, kaolinite, smectite and manganite) and their composites to accumulate copper and zinc from a liquid medium, and elucidate the role of microbes on the mobility of heavy metals. Various mixtures of bacteria and clays were exposed to solutions of 0.025mM or 0.5mM Cu(II) and Zn(II) in 0.01M KNO3 to differentiate between so-called “high-affinity” sites and “low-affinity” sites. Clays associated in an edge-on orientation to the cells was observed by electron microscope (EM) examination of these metal-treated bacteria–clay aggregates. Adsorption experiments and desorption with 1.0M CH3COOK solution indicated that clays contain more high-affinity copper binding sites and less high-affinity zinc binding sites than that of bacteria, however, bacteria are involved in more low-affinity heavy-metal-binding sites. Carboxyl group activity is more important at weak-binding sites than at strong-binding sites. TEM-EDS analysis confirmed that most of Zn removed from solution was associated with P. putida CZ1 in the composites. These results suggest that bacteria play an important role in regulating the mobility of heavy metals in the soil environment. [Copyright &y& Elsevier]

Lead (Pb) and arsenic (As) exist in soil with different ionic forms, and it is difficult to immobilize simultaneously Pb and As in soil. The objective of this study is to determine the effects of water management including flooding (FL), alternate wetting and drying (AWD) and dry farming (DF) combined with addition of phosphate (P) on the accumulation of Pb and As in rice. Our results showed that Pb accumulated in root during vegetative stage, and most of As in root was transported to the above ground parts during the reproductive stage. Pb was evenly distributed in grains, and As was mostly accumulated in bran and aleurone layer. Water management had a reverse effect on the accumulation of Pb and As in rice. However, the effects of P on arid soil environment and Pb, As accumulation in rice were stronger than that in flooded soil. Application of P under AWD treatment could maintain a similar quantity of Fe plaque with flooding, decrease the availability of Pb in rhizosphere soil, reduce Pb and As accumulation in root, and result in the reduction of Pb and As accumulation in grains by 86% and 66% respectively. Besides, our study also found that flooding or AWD during vegetative stage facilitated the formation of iron plaque. In conclusion, AWD combined with P application could maintain a relatively lower concentrations of Pb and As in grains. [Display omitted] • Lead accumulated in root primarily during the vegetative stage. • Arsenic in root was transported to aboveground parts during the reproductive stage. • Flooding or AWD during the vegetative stage in soil would help to form iron plaque. • AWD combined with application of P could decrease simultaneously lead and arsenic in grains. • Lead was distributed evenly in grains, and arsenic was mostly accumulated in bran and aleurone layer. [ABSTRACT FROM AUTHOR]

Abstract: Successful phytoremediation depends mainly on the bioavailability of copper (Cu) and zinc (Zn) in the soil. We studied the potential effects of sulphur (S) amendment on mobility of copper, zinc and microbial community composition in soil under laboratory conditions. The results showed that with S application at 20gSkg−1, soil pH decreased about 3 units and the solubility of the Cu and Zn significantly increased after 64 days of incubation. The concentration of Cu in Cu-accumulator Elsholtzia splendens shoots and roots increased with S treatment. Concentration of Cu in the shoots was 156.5mgkg−1 under S treatment. It was 2.5 times of without application of S. PCR-denaturing gradient gel electrophoresis (PCR-DGGE) fingerprint analysis revealed that there were certain groups of acidophilic soil bacteria in the soil after addition of S. We found specific clones such as 1 (from biofilter-treating hydrogen sulfide and methanol) and 4 (from metal-rich and acidic River Tinto) in the soil with S treatment. The above results indicated that S facilitated the mobility of Cu and Zn by soil microorganism and provided a basis for further studies of S-assisted phytoremediation. [Copyright &y& Elsevier]