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The straight head disease of rice is one of the main problems limiting rice production. Arsenic (As) methylation in paddy soils is considered to be highly related to the occurrence of the straight head disease. As a typical field practice, rice fields are usually drained during the late tillering stage and the mid-late grain filling stage. Nevertheless, the key influencing factors on the As methylation efficiency during paddy soil drying remain unclear. In this study, an indoor cultivation experiment was set up to simulate the drying process of paddy soil. Two As-contaminated soils collected from Xingren (XR) in Guizhou province and Nandan (ND) in Guangxi province were used as test soils. Each soil was treated with the addition of rice straw (RS) and without rice straw (CK). With the drying of paddy soil (0, 24, 36, 48, and 60 h), the changes in soil Eh, pH, total organic carbon (TOC), and As chemical species in the porewater were determined. The abundance of the As methylation functional gene ( arsM ), sulfate-reducing bacteria (harboring dsrA , As methylation-related microorganism), and methanogens (harboring mcrA , As demethylation-related microorganism), as well as the diversity of arsM -harboring microorganisms, were also observed. The results showed that during the process of drying paddy soil, soil Eh changed from -300--200 mV under complete flooding to -150--50 mV after drying; however, the change in soil pH was not obvious. The concentrations of inorganic As (iAs) and dimethylarsenic (DMAs) in porewater significantly increased ( P <0.05) with the drying process. Additionally, the concentration of DMAs in the RS treatment was prominently higher than that in CK. Compared with XR soil, the concentration of DMAs in ND soil was higher. As a function of soil drying time, the As methylation efficiency of XR soil (XR-CK and XR-RS) slightly increased but was not significant ( P >0.05), whereas the As methylation efficiency of ND soil (ND-CK and ND-RS) increased significantly ( P <0.05). After the drying time reached 60 h, the As methylation efficiency of ND-CK and ND-RS increased by 61.8% and 23.2%, respectively, compared with those at the early stage of drying (0 hours). The copy numbers of the arsM and dsrA genes greatly increased with the extension of drying time, whereas an opposite trend was observed for the copy number of the mcrA gene. Furthermore, the addition of straw obviously increased the gene abundance of whole bacteria and arsM -, dsrA -, and mcrA -harboring bacteria. Based on the multi-factor analysis of variance and the redundancy analysis, it was found that the test soil type, straw addition, drying time, and their interaction had a critical influence on the changes in As species, As methylation efficiency, and the gene abundance in soils. TOC, Eh, and the functional genes associated with As methylation were positively linked with the methylated As content in soil porewater but negatively correlated with that of iAs. According to the sequence of the arsM -harboring microbe, it was clearly demonstrated that a community shift of As-methylating microbe occurred with the soil drying. Here, the following conclusions were derived:① the drying process did not lower the As methylation efficiency in paddy soil. On the contrary, in this study, the As methylation efficiency, especially that for ND soil, remarkably improved. The addition of straw notably promoted the As methylation efficiency and the content of DMAs in porewater. ② An increasing tendency was observed for the abundance of microbes related to As methylation, whereas a reverse trend was indicated for microbes related to As demethylation. The community shift of arsM -harboring microbes might be the crucial reason for the improved As methylation efficiency during the soil drying. These observations contribute to a better understanding of the As methylation process during paddy soil drying and will shed light on the future mitigation of rice straight head disease in paddy soils.

Humic acid amendments have been widely advocated for the remediation of heavy metal-contaminated soil. However, the impacts of straw-derived humic acid-like substances on the remediation of cadmium (Cd) and arsenic (As) co-contaminated paddy soil remain unclear and the potential mechanism required clarification. In this study, we employed a pot experiment and chose a straw-derived humic acid-like substance (BFA) as the amendment with four doses to investigate how BFA affects the availability of Cd and As in soil and their accumulation in rice. The results showed that grain Cd decreased by 25.65-36.03%, while there was no significant change in total As (TAs) with the addition of BFA. The contents of DCB-Fe, DCB-As and DCB-Cd on the root surface decreased by 6.07-40.54% during the whole growth stage. The addition of BFA significantly decreased the pe + pH and enhanced the transformation of crystalline iron oxides (Fed) into amorphous forms (Feo) in the soil. The CaCl 2 -extractable Cd decreased and the KH 2 PO 4 -extractable As increased with the decrease in pe + pH and Fed and the relative increase in Feo. The correlation analysis showed that the decrease in availability of Cd and translocation factor of Cd effectively decreased the grain Cd and the decrease in DCB-Cd may also contribute to decreasing the uptake of Cd by rice. However, the increase in As of roots and shoots might play key roles in restricting the transport of As to rice grains. Consequently, the addition of BFA could effectively reduce the Cd accumulation in rice under flooding conditions, while no risk of As accumulation in rice grain was observed. The present work provides a new perspective for the application of straw-derived humic acid-like substances as amendments on Cd-As co-contaminated soils, which should be advocated as an eco-friendly, economical and effective soil amendment in the future., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Humic substances (HSs), as electron shuttles, are associated with iron oxide transformation, yet the manner by which HSs affect Cd/As availabilities during this process under anaerobic conditions remains unclear. Two HSs (humic sodium, HA-Na, and biochemical fulvic acid, BFA) were applied at 0, 1, 2, and 4 gCkg -1 in a submerged incubation experiment. The dissolved, extractable and fractions of Cd/As and different iron oxides in soils were monitored. The addition of both HA-Na and BFA decreased the CaCl 2 -extractable Cd by 12.66-93.13%, and increased the KH 2 PO 4 -extractable As by 18.81-71.38% on the 60th day of incubation. The soil Eh and crystalline iron oxides (Fed) decreased, while amorphous iron oxides (Feo) and dissolved As increased after addition of both HSs. However, the two HSs had opposite effects on soil pH and dissolved Cd at the end of the incubation. HA-Na immobilized 19.47-85.99% more available Cd than did BFA over the incubation, although the extent of immobilization was similar with the maximum application rate on the 60th day. BFA mobilized 5.22-26.12% more available As than did HA-Na. XPS data showed that FeOOH decreased while the FeO component increased over the incubation. Correlation analysis and SEM showed that the reduction in the soil Eh and Fed and relative increase in Feo increased the available Cd, while decreased the available As. Consequently, the addition of HA-Na and BFA, particularly combined with flooding irrigation management, could effectively reduce the available Cd in Cd-contaminated soil. However, this method should be used with caution in As-contaminated soil., (Copyright © 2021. Published by Elsevier Inc.)

Organic mobilizing agents have been advocated for phytoremediation of heavy metals contaminated soils, while the effects of application period of such agents remain unclear. A pot experiment was conducted, with two composited organic agents (oxalic acid or citric acid + dissolved organic fertilizer (OA + DOF and CA + DOF)) and four application periods (seeding, jointing, flag leaf and heading stages) of sorghum (Sorghum bicolor L.), to investigate their impacts on Cd bioavailability in soil. Results indicated that application of the two composited agents increased soil dissolved organic carbon (DOC) and DTPA extractable Cd by 7.31-49.13%, Cd contents in roots and shoots by 21.49-72.10%, bioaccumulation factor (BCF) and translocation factor (TF) of shoots by 4.44-71.99%, while reduced soil pH by 0.25-0.53 units, respectively. Most of these indices increased with the application periods, and largely peaked with their application during the flag leaf to heading stages. Meanwhile, the maximum sorghum biomass (132.84 g pot -1 ) and Cd bioaccumulation quantity (BCQ, 0.71 mg pot -1 ) in shoots were obtained for the CA + DOF applied at the heading. The DTPA extractable Cd was closely related to soil pH and DOC. Similar close relationships were observed between the Cd contents in shoots and soil DTPA extractable Cd, pH and DOC. The BCQ of Cd was positively related to the shoots biomass rather than their Cd contents. Therefore, the sorghum combined with the CA + DOF may be advocated as an alternative phytoremediation mode in Cd-contaminated soils, and the mobilizing agent should be primarily applied at the heading stage., Competing Interests: Declaration of competing interest The authors declare that they have no competing financial interests and personal relationships that can influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

To acquire a feasible method for a rapid comparison of the cadmium (Cd) accumulation capacities of different leafy vegetables, using substrate cultivation with different contents of Cd and cultivation time, we compared the observed Cd accumulation capacity with these obtained in the field. The results showed that the Cd content and bio-concentration factors (BCFs) value in the aboveground tissue of leafy vegetable varied significantly with Cd content and cultivation time. Multi-factor analysis of variance showed that vegetable variety, cultivation time, Cd content in substrate and their interaction had significant effects on BCFs of Cd in leafy vegetable. Leafy vegetable variety was the dominant factor affecting BCFs of Cd in leafy vegetable and controlled its absolute level. When Cd content in the substrate reached 1.0 mg·kg -1 with a cultivation of 10 days, the correlation coefficient of Cd BCFs between the substrate cultivation and field experiments was the highest, with a R 2 value of 0.90. The results of cluster analysis and one-way ANOVA had the highest consistence with the field results. Comparatively, the substrate cultivation with Cd content of 1.0 mg·kg -1 and a cultivation of 10 days showed a good reproducibility and stability in reflecting the difference in Cd accumulation capacities of different leafy vegetable varieties. The Cd-rich substrate cultivation could be used to screen the vegetables with low Cd accumulation and also would promote the field application of the vegetables with low Cd accumulation in the Cd-contaminated area of China.

Based on the typical greenhouse vegetable production system in Siping City, Jilin Province, 124 soil samples were collected from greenhouse soils growing vegetables (GSGV), fields growing maize (FGM), and forest soil (FS) under different land utilization patterns. In addition, other samples including greenhouse vegetables (81), fertilizers (50), and irrigation water (10) were also collected in the studied region. To illustrate the accumulation characteristics of heavy metals in GSGV and greenhouse vegetables, the heavy metal content of different samples was measured using inductively coupled plasma mass spectrometry (ICP-MS) technology. The results indicated that the heavy metal content in GSGV was much higher than that in FGM and FS except for lead (Pb). Heavy metals including cadmium (Cd), copper (Cu), chromium (Cr), nickel (Ni), and zinc (Zn) in GSGV presented with various degrees of accumulation. The mean value of Cd content in the soils in the investigation region was 0.45 mg·kg -1 , with about 42.8% of all the soil samples exceeding the Cd content criterion of the Environmental Quality Evaluation Standard for Farmland in Greenhouse Vegetable Production (HJ 333-2006). The content of the other heavy metals was in the normal range, and all met the regulations of the standard. In comparison with different vegetable categories, leafy vegetables showed much higher heavy metal concentrations (Cd 0.033 mg·kg -1 fresh weight) than did fruity ones. In total, about 2.5% and 1.2% of vegetable samples exceeded the regulated values of Cd and Pb recommended by the Standard of Food limits, respectively. With the cultivation time prolonged, heavy metal concentration in soils and vegetables all increased synchronously as the pH value decreased. The content of heavy metals in greenhouse vegetables was significantly influenced by soil pH and organic matter. It can be concluded that the health risk of greenhouse vegetables increased with GSGV accumulating more heavy metals due to the substantial application of chemical fertilizer and manure containing high level of heavy metals.

An incubation test was conducted to study the bioavailability and fractionations of exogenous arsenite [As(3)] during the aging period in three soils originated from different parent materials, including quaternary red clay, purple sandy shale and granite. The results indicated that the exogenous arsenite As(3) were totally transformed into As(V) after 120 d aging. The available As content in soils derived from the three soils generally decreased sequentially throughout the aging period in the order of purple sandy shale, granite and quaternary red clay. The pseudo-second-order model well fitted the change of available As content with aging time (P＜0.05). Soil pH, organic matter (SOM) content and the concentrations of Fe, Al and Mn oxides were the main factors influencing the red soil arsenic in aging, especially, Mn oxides played a more crucial role than Fe and Al oxides in As aging (P＜0.05). Correlation analysis revealed that the non-specially and specially absorbed As constituted the primary forms of available As.

A pot experiment was conducted to study the effects of exogenous dimethylarsinic acid (DMA) on the growth of Brassica campestris and the bioavailability of soil arsenic (As). With the increasing concentration of applied DMA, the emergence rate and biomass of B. campestris increased at low concentration DMA, but decreased at high concentration DMA. When the DMA concentration reached 90 mg x kg(-1), the emergence rate and biomass of B. campestris in the second cropping decreased by 9.5% and 57.0%, respectively, compared with those in the control, indicating that exogenous DMA had longer-term effects on the growth of B. campestris. The soil available As and the As uptake by B. campestris all increased with increasing concentration of exogenous DMA, and there existed significant correlations among them. After applied into soil, the exogenous DMA demethylated, with As(V) as the main product and lesser amount of As (III), and the concentrations of soil As(V) and As(III) increased with increasing application rate of exogenous DMA.

A pot experiment with arsenic-contaminated red soil was conducted to study the effects of applying pig dung and chicken manure on the growth and arsenic absorption of pakchoi (Brassica chinensis), and on soil available arsenic. Applying pig dung and chicken manure to the arsenic-contaminated red soil increased the biomass of pakchoi to some extent. Comparing with the control, applying pig dung increased the pakchoi biomass significantly (P < 0.05). The soil available arsenic content after applying pig dung increased by 394.9%-1033.6% (P < 0.05), and that after applying chicken manure increased by 30.4%-94.1%. Organic fertilization promoted the arsenic absorption of pakchoi, with the arsenic uptake after applying pig dung increased by 20.7%-53.9%. The application of pig dung and chicken manure to arsenic-contaminated red soil could somewhat increase the soil available arsenic content and the arsenic uptake by crops, and thus, increase the risks of agricultural product quality and environment.

A sampling survey was conducted in the typical areas in Shouguang County of Shandong Province to study the characteristics of arsenic (As) concentration and speciation in greenhouse vegetable soil. The total As concentration in the surface (0-20 cm) and subsurface (20-40 cm) soil was averagely 8.27 and 7.93 mg x kg(-1), being 19% and 23% higher than that of the control (open field soil), and the soluble As (AE-As) concentration was 0.13 and 0.06 mg x kg(-1), 63% and 200% higher than that of the control, respectively. The ratio of residual As (O-As) to total arsenic reached more than 63.0%, and the concentrations of different As speciation decreased in the order of O-As > iron-bound As (Fe-As) > calcium bound As (Ca-As) > aluminum bound As (AlAs) > AE-As. With the increasing planting years, the AE-As concentration enhanced significantly, and the Al-As concentration also increased to some degree. After 15 years planting, the AE-As concentration in surface and subsurface soil increased by 75.0% and 150.0%, and Al-As concentration increased by 51.6% and 190.4%, respectively, while the concentrations of Fe-As and Ca-As all decreased to some degree.

A pot experiment was conducted to study the speciation transformation of exogenous dimethyl arsenic (DMA) in soil. The added DMA was mainly transformed into arsenate [As(V)], accompanied with a small amount of monomethyl arsenic (MMA). When the concentration of added DMA was 30 mg x kg(-1), the transformation rate was the highest, being 6.71%, 8.11%, 11.33%, and 19.32% when the cultivation time was 10, 15, 30, and 40 days, respectively. With increasing concentration of added DMA, soil soluble arsenic (AE-As) had an increasing trend, but decreased as the cultivation time increased. Comparing with CK, the addition of DMA increased the concentrations of soil arsenic bounded to aluminum (Al-As), iron (Fe-As), calcium (Ca-As), which was possibly due to the adsorption or fixation of added DMA and its transformation products by the oxides or hydroxides of soil aluminum, iron, and calcium.

An incubation test was conducted to study the transformation of exogenous dimethylarsenic acid (DMA), monomethylarsenic acid (MMA), and arsenate [As(V)] in soil under the condition of 35% of water-holding capacity. After added into soil, the concentrations of test arsenic forms all showed a decreasing trend with time. The DMA and MMA were mainly demethylated, and after 120 days incubation at constant temperature and humidity, transformed into As(V). A small amount of MMA was detected in the treatment with added DMA on the 120th day of incubation, and a small amount of DMA was detected in the treatment with added MMA during the period of 7-60 days incubation. By the end of the incubation test, the concentrations of added DMA and MMA in soil decreased significantly (P < 0.01), with the decrement being 99.5% and 94.3% and the concentration of transformed As(V) increased by 4.61 and 5.15 times, respectively. Comparing with DMA and MMA, the As(V) after added into soil had less form transformation.

A total of thirteen fungal strains with higher arsenic (As)-tolerance ability were isolated from six As-contaminated soil samples collected from the mining areas of Shimen County and Chenz-hou City in Hunan Province. Among the strains isolated, Penicillin janthinellum, Fusarium oxysporum, and Trichoderma asperellum had the highest As-tolerance ability, based on the morphological identification and phylogenetic analysis. Culture experiment showed that on the solid plates with 30,000, 30,000, and 20,000 mg x L(-1) of As, P. janthinellum, F. oxysporum, and T. asperellum had a better colony growth, and after cultured in the liquid medium with 0-50, 0-50, and 0-80 mg x L(-1) of As for 2 days, respectively, the dry mycelia masses of the three strains all increased with increasing As concentration. When the As concentration reached 50, 50, and 80 mg x L(-1), respectively, the fungal biomass of F. oxysporum, T. asperellum, and P. janthinellum increased significantly, compared with CK. High concentration As had no significant effects on the sporalation of the three fungal strains.

A systematic investigation was carried out on the arsenic content in the soils and plants surrounding Shimen arsenic sulphide mine. The arsenic content in top soils (0-20 cm) was averagely 99.51 mg x kg(-1), being 5.34 times higher than that of the background value in Hunan Province and 8.70 times higher than that of local farmland soil. The topsoil arsenic content in paddy field and dry land was 43.51 and 115.1 mg x kg(-1), respectively, being 0.45 and 1.87 times higher than that of the grade II level (paddy field 30 mg x kg(-1); dry land 40 mg x kg(-1)) commended by the National Soil Quality (GB 15618-1995), and the corresponding arsenic exceeding rate was 62.5% and 50.0%, respectively. The arsenic content in edible parts of foodstuff, vegetables, and fruits was 0.16, 0.06, and 0.01 mg x kg(-1), respectively, and the arsenic exceeding rate of crop samples compared to food security standard ranked in the order of foodstuff > vegetables > fruits. Rice and sweet potato were relatively seriously contaminated by arsenic. The highest arsenic content of rice was up to 0.84 mg x kg(-1), which was 4.6 times higher than that of the National Standard, with the exceeding rate of 62.5%. Statistical analysis demonstrated that there was a positive correlation between the arsenic contents of soil and plant. The average daily intake of arsenic by local people through the consumption of the crops was 6.416 microg x kg(-1) x d(-1), which was much higher than the standard commended by WHO, and the related health risk index was 21.39, which was 14.39 times higher than that in the control region.

An incubation test was conducted to study the dynamics of exogenously supplied dimethylarsenic acid (DMA), monomethylarsonic acid (MMA), and As(V) in soil under flooding. With the increasing time of incubation, the exogenously supplied DMA and MMA were mainly transformed into As(V), and the As(V) concentration increased, being significantly higher after incubated for 150 days, compared with that after incubated for 1 day. The exogenously supplied DMA was demethylated into As(V) within 30 days, accompanied by a little As(III), while the transformation rate of exogenously supplied MMA was rather slow within 60 days, accompanied by a little As(III) and DMA. The exogenously supplied As(V) decreased with increasing time of incubation, and its form had less change except that a little As(III) occurred.

This paper analyzed the current situation of heavy metal contamination in cropland soils in China, and discussed the input, output, and balance of heavy metals in cropland ecosystems. It was considered that heavy metals had definite accumulation in cropland ecosystems, but overall speaking, this accumulation had relatively small environmental risk, and only some plants, especially vegetables, accumulated heavy metals over the standards. In mining areas, adjacent areas of smelting plants, and the farming areas using larger amounts of related wastes, the heavy metals content in plants and soils was at least ten times higher than that in normal croplands, existing larger environmental risk. Aiming at the current situation of heavy metal contamination of farmland soils in China, some effective regulation measures for the heavy metal cycling in the cropland ecosystems were proposed, and the further research prospects in related fields were discussed.

Taking the facility vegetable fields having been planted for 1-12 years and the adjacent wheat land in Shouguang City of Shandong Province as test objects, this paper studied the distribution characteristics of arsenic (As), cadmium (Cd), copper (Cu), zinc (Zn), chromium (Cr), and nickel (Ni) in their soil profiles (0-150 cm). With the increase of soil depth, the test heavy metals contents in the soil profiles all had a decreasing trend, and in the same soil layers, the contents were obviously higher in facility vegetable fields than in wheat land. Comparing with those in the same soil layers of wheat land, the average contents of As, Cd, Cu, Zn, Cr, and Ni in 0-20 and 120-150 cm soil layers of facility vegetable fields were 35.0%, 146.2%, 65.6%, 36.4%, and 21.5%, and 10.6%, 178.5%, 19.4%, 20.2%, 15.2%, and 9.3% higher, respectively, and the average contents of the heavy metals in 20-120 cm soil layer of facility vegetable fields were also higher in some degree. In the 0-20 cm soil layer of facility vegetable fields, the Cd, Cu, and Zn contents had significant positive correlations with planting years (P < 0.05), with the accumulation rates of Cd, Cu, and Zn being 0.027, 1.153, and 2.830 mg x kg(-1) x a(-1), respectively. In facility vegetable fields, the test six heavy metals contents were significantly positively correlated with the contents of soil organic carbon and total nitrogen, and the Cd, Cu, Zn, and Cr contents were significantly correlated with the content of soil total phosphorus (P < 0.01). Applying organic fertilizer could induce the heavy metals accumulation in the soils of facility vegetable fields to some extent.

Based on the analysis of the sources and existing forms of soil arsenic, this paper approached the inter-transformationr of different arsenic forms in soil. In the meanwhile, the extraction and determination methods of different soil arsenic forms were also compared. It was considered that HPLC-HG-AFS had the advantages of high sensitivity, low detection limit, better selectivity, low operation cost, and less inter-transformation of different arsenic forms, being able to be used as the prior method for the detection of different arsenic forms. Combining with previous research results, the form transformation of arsenic in soil and the promising research aspects were also discussed.

Amendments are widely applied in agricultural soils to improve soil quality and crop yield. Effects of three amendments, lime, manure, and sepiolite on cadmium (Cd) and zinc (Zn) bioavailability in contaminated paddy soils were studied by pot experiment with cultivating rape. There were eight treatments, including lime, manure, and sepiolite separately applied and combined with others in contaminated soil. The biomass yield of rape was investigated after harvest. The amounts of absorbed Cd and Zn in harvested rape with application amendments were determined. Besides soil pH, different forms of Cd and Zn in the conducted soils were also measured. Results showed that the yield of rape increased after amendments application. The treatment of lime and manure co-application showed the highest increasing yield by more than 170% comparing with no amendments application in the eight treatments. The amount of absorbed Cd and Zn in rape decreased after the three amendments application. Lime application showed the best effect to decrease the heavy metal content in rape when amendments were separately applied. However, sepiolite could hardly decrease the content in rape after separately applied in contaminated soil. It was mainly due to the decrease of exchangeable Cd and Zn, which was available for rape, after lime application. Soil pH in these treatments increased in response. Accordingly, the carbonate combined and the Fe-Mn oxide fractions, which were unavailable in soil for rape, increased greatly. The uptake coefficient of Cd was higher than that of Zn. It indicated that Cd was more movable in soil and lime application could obviously decrease the uptake coefficient. The remediation efficiency was significantly improved in the treatment of co-application with lime and manure in Cd-Zn contaminated paddy soil. Compared with control (CK), it increased 13.5 times for Cd and 2.4 times for Zn, respectively.

The study on the soil arsenic (As) accumulation under different types of agricultural use in Shouguang of Shandong Province showed that farmland soils had an average As content of 9. 63 mg x kg(-1) , with the highest being 15. 15 mg x kg(-1) . Compared with the local background value (9. 3 mg As x kg(-1)) , 53. 1% of soil samples was detected as As enrichment. The soil As content was high in the west, east and north parts of Shouguang, relatively lower in the middle part, and the lowest in the south part. Different agricultural use had an obvious effect on the soil As content, which was decreased in the order of wheat/maize land > cotton field > protected vegetable land > uncovered vegetable land. Such a difference in soil As content was mainly affected by agricultural activities. With the increasing year of vegetable planting, soil As content had an increasing trend, because the As input from pig dung and chicken feces was the main source of soil As in protected vegetable land. Soil As enrichment could be reduced to some degree by applying soybean cake fertiliz-