Metal-Binding Protein TaGlo1 Improves Fungal Resistance to Arsenite (AsIII) and Methylarsenite (MAsIII) in Paddy Soil.

Trivalent arsenicals such as arsenite (AsIII) and methylarsenite (MAsIII) are thought to be ubiquitous in flooded paddy soils and have higher toxicity than pentavalent forms. Fungi are widely prevalent in the rice rhizosphere, and the latter is considered a hotspot for As uptake. However, few studies have focused on alleviating As toxicity in paddy soils using fungi. In this study, we investigated the mechanism by which the protein TaGlo1, derived from the As-resistant fungal strain Trichoderma asperellum SM-12F1, mitigates AsIII and MAsIII toxicity in paddy soils. Taglo1 gene expression in Escherichia coli BL21 conferred strong resistance to AsIII and MAsIII, while purified TaGlo1 showed a high affinity for AsIII and MAsIII. Three cysteine residues (Cys13, Cys18, and Cys71) play crucial roles in binding with AsIII, while only two (Cys13 and Cys18) play crucial roles for MAsIII binding. TaGlo1 had a stronger binding strength for MAsIII than AsIII. Importantly, up to 90.2% of the homologous TaGlo1 proteins originate from fungi by GenBank searching. In the rhizospheres of 14 Chinese paddy soils, Taglo1 was widely distributed and its gene abundance increased with porewater As. This study highlights the potential of fungi to mitigate As toxicity and availability in the soil-rice continuum and suggests future microbial strategies for bioremediation.

Soil ridging combined with biochar or calcium-magnesium-phosphorus fertilizer application: Enhanced interaction with Ca, Fe and Mn in new soil habitat reduces uptake of As and Cd in rice.

Reducing the bioavailability of both cadmium (Cd) and arsenic (As) in paddy fields is a worldwide challenge. The authors investigated whether ridge cultivation combined with biochar or calcium-magnesium-phosphorus (CMP) fertilizer effectively reduces the accumulation of Cd and As in rice grains. Field trial showed that applying biochar or CMP on the ridges was similar to the continuous flooding, which maintained grain Cd at a low level, but grain As was reduced by 55.6%, 46.8% (IIyou28) and 61.9%, 59.3% (Ruiyou 399). Compared with ridging alone, the application of biochar or CMP decreased grain Cd by 38.7%, 37.8% (IIyou28) and 67.58%, 60.98% (Ruiyou399), and reduced grain As by 38.9%, 26.9% (IIyou28) and 39.7%, 35.5% (Ruiyou 399). Microcosm experiment showed that applying biochar and CMP on the ridges decreased As in soil solution by 75.6% and 82.5%, respectively, and kept Cd at a comparably low level at 0.13-0.15 µg L-1. Aggregated boosted tree (ABT) analysis revealed that ridge cultivation combined with soil amendments altered soil pH, redox state (Eh) and enhanced the interaction of Ca, Fe, Mn with As and Cd, which promoted the concerted reduction of As and Cd bioavailability. Application of biochar on the ridges enhanced the effects of Ca and Mn to maintain a low level of Cd, and enhanced the effects of pH to reduce As in soil solution. Similar to ridging alone, applying CMP on the ridges enhanced the effects of Mn to reduce As in soil solution, and enhanced the effects of pH and Mn to maintain Cd at a low level. Ridging also promoted the association of As with poorly/well-crystalline Fe/Al and the association of Cd on Mn-oxides. This study provides an effective and environmentally friendly method to decrease Cd and As bioavailability in paddy fields and mitigate Cd and As accumulation in rice grain.

Differential responses of canonical nitrifiers and comammox Nitrospira to long-term fertilization in an Alfisol of Northeast China.

The newly identified complete ammonia oxidizer (comammox) that converts ammonia directly into nitrate has redefined the long-held paradigm of two-step nitrification mediated by two distinct groups of nitrifiers. However, exploration of the niche differentiation of canonical nitrifiers and comammox Nitrospira and their ecological importance in agroecosystems is still limited. Here, we adopted quantitative PCR (qPCR) and Illumina MiSeq sequencing to investigate the effects of five long-term fertilization regimes in the variations of ammonia-oxidizing bacteria (AOB), ammonia-oxidizing archaea (AOA), nitrite-oxidizing bacteria (NOB), and comammox Nitrospira abundances and comammox community composition in two soil layers (0-20 cm, topsoil; 20-40 cm, subsoil) in an Alfisol in Northeast China. The fertilization treatments included no fertilizer (CK); chemical nitrogen (N) fertilizer; chemical N; phosphorus (P) and potassium (K) fertilizers (NPK); recycled organic manure (M) and chemical N, P, K plus recycled manure (MNPK). Compared with CK, manure and/or chemical fertilizer significantly increased the AOB amoA gene abundance. Long-term recycled manure increased soil organic matter (SOM) contents and maintained the soil pH, but decreased the NH4 +-N concentrations, which markedly promoted the nxrA and nxrB gene abundances of NOB and the amoA gene abundances of comammox Nitrospira clade A and AOA. Although the comammox Nitrospira clade B abundance tended to decrease after fertilization, the structural equation modeling analysis showed that comammox clade B had direct positive impacts on soil potential ammonia oxidation (PAO; λ = 0.59, p < 0.001). The long-term fertilization regime altered the community composition of comammox Nitrospira. Additionally, comammox Nitrospira clades A and B had individual response patterns to the soil layer. The relative abundance of clade A was predominant in the topsoil in the N (86.5%) and MNPK (76.4%) treatments, while clade B appeared to be dominant in the subsoil (from 78.7 to 88.1%) with lower ammonium contents, implying niche separation between these clades. Soil pH, NH4 +-N and SOM content were crucial factors shaping the soil nitrifying microbial abundances and the comammox Nitrospira community. Together, these findings expand the current understanding of the niche specialization and the important role of comammox Nitrospira in terrestrial ecosystems.

Responses of potential ammonia oxidation and ammonia oxidizers community to arsenic stress in seven types of soil.

Soil arsenic contamination is of great concern because of its toxicity to human, crops, and soil microorganisms. However, the impacts of arsenic on soil ammonia oxidizers communities remain unclear. Seven types of soil spiked with 0 or 100 mg arsenic per kg soil were incubated for 180 days and sampled at days 1, 15, 30, 90 and 180. The changes in the community composition and abundance of ammonia oxidizing bacteria (AOB) and ammonia oxidizing archaea (AOA) were analyzed by terminal restriction fragment length polymorphism (T-RFLP) analysis, clone library sequencing, and quantitative PCR (qPCR) targeting amoA gene. Results revealed considerable variations in the potential ammonia oxidation (PAO) rates in different soils, but soil PAO was not consistently significantly inhibited by arsenic, probably due to the low bioavailable arsenic contents or the existence of functional redundancy between AOB and AOA. The variations in AOB and AOA communities were closely associated with the changes in arsenic fractionations. The amoA gene abundances of AOA increased after arsenic addition, whereas AOB decreased, which corroborated the notion that AOA and AOB might occupy different niches in arsenic-contaminated soils. Phylogenetic analysis of amoA gene-encoded proteins revealed that all AOB clone sequences belonged to the genus Nitrosospira, among which those belonging to Nitrosospira cluster 3a were dominant. The main AOA sequence detected belonged to Thaumarchaeal Group 1.1b, which was considered to have a high ability to adapt to environmental changes. Our results provide new insights into the impacts of arsenic on the soil nitrogen cycling.

[Arsenic Methylation Efficiency Changes During Paddy Soil Drying and Its Key Influencing Factors Analysis].

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.

Thermodynamics, Kinetics, and Mechanisms of the Co-Removal of Arsenate and Arsenite by Sepiolite-Supported Nanoscale Zero-Valent Iron in Aqueous Solution.

In this study, a newly synthesized sepiolite-supported nanoscale zero-valent iron (S-nZVI) adsorbent was tested for the efficient removal of As(III) and As(V) in aqueous solution. Compared with ZVI nanoparticles, the As(III) and As(V) adsorption abilities of S-nZVI were substantially enhanced to 165.86 mg/g and 95.76 mg/g, respectively, owing to the good dispersion of nZVI on sepiolite. The results showed that the adsorption kinetics were well fitted with the pseudo-second-order model, and the adsorption isotherms were fitted with the Freundlich model, denoting a multilayer chemical adsorption process. The increase in the initial solution pH of the solution inhibited As(III) and As(V) adsorption, but a weaker influence on As(III) than As(V) adsorption was observed with increasing pH. Additionally, the presence of SO42- and NO3- ions had no pronounced effect on As(III) and As(V) removal, while PO43- and humic acid (HA) significantly restrained the As(III) and As(V) adsorption ability, and Mg2+/Ca2+ promoted the As(V) adsorption efficiency. Spectral analysis showed that As(III) and As(V) formed inner-sphere complexes on S-nZVI. As(III) oxidation and As(V) reduction occurred with the adsorption process on S-nZVI. Overall, the study demonstrated a potential adsorbent, S-nZVI, for the efficient removal of As(III) and As(V) from contaminated water.

Synergistic removal of As(III) and Cd(II) by sepiolite-modified nanoscale zero-valent iron and a related mechanistic study.

Arsenic (As) and cadmium (Cd) are two highly toxic elements. In recent years, many newly synthesized chemical materials have been used widely for treatments of As- and Cd-contaminated effluents. However, most materials do not exhibit high efficiencies for simultaneous removal of As and Cd from water systems. Our study established a simple scheme for synthesizing a sepiolite (SEP)-modified nanoscale zero-valent iron (S-nZVI) for simultaneous removal of coexisting As and Cd from water and illuminated a possible underlying mechanism. Batch experiments showed that the maximum capacities for adsorption of As(III) and Cd(II) by S-nZVI were 230.29 mg/g and 11.37 mg/g, respectively, which represented better effects than those of other materials, as reported previously. Removal of Cd(II) depended on pH, but As(III) removal showed little dependence on pH. Coexisting ions such as phosphate (PO43-) and the conjugate base of humic acid (HA) significantly inhibited simultaneous removal of As(III) and Cd(II). In the mixed As(III)-Cd(II) system, the presence of As(III)-pretreated S-nZVI significantly enhanced Cd(II) adsorption by a factor of four over that seen for aqueous solution without As(III). XRD and XPS results showed that CdFe2O4 (Fe-O-Cd), Fe2As2O14 or FeAsO4 (Fe-O-As) were formed after As(III) and Cd(II) were captured by S-nZVI. However, a further zeta (ζ) potential analysis showed that the mechanism for As(III) and Cd(II) adsorption by S-nZVI is not just simple formation of the above chemicals, since the adsorbed As(III) increased the negative charge of S-nZVI; this suggested an electrostatic attraction between S-nZVI and Cd(II) and indicated that adsorbed As(III) created new sorption sites for Cd(II), which enhanced Cd(II) sorption via formation of ternary complexes (Fe-As-Cd). These results suggested that S-nZVI is a promising material for in situ remediation of heavy metal-contaminated groundwaters or paddy soils.

Influence of straw-derived humic acid-like substance on the availability of Cd/As in paddy soil and their accumulation in rice grain.

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 CaCl2-extractable Cd decreased and the KH2PO4-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.

The performance and mechanism of cadmium availability mitigation by biochars differ among soils with different pH: Hints for the reasonable choice of passivators.

The performances of passivation materials mitigating Cadmium (Cd) bioavailability considerably vary with the pH condition of Cd-contaminated soils. However, less information was available for the method of improving Cd passivation efficiency taking into account the pH of the targeted soil. Furthermore, the underlying mechanism of Cd availability mitigation in soils with different pH has not been clearly explored. In this study, cotton straw biochar (CSB) and its modified products using NaOH (CSB-NaOH) were prepared and applied in two kinds of Cd-contaminated soils with different pH. It was found that CSB-NaOH was more effective than CSB in regulating the Cd bioavailability in the acid soil, while the opposite tendency was observed in alkaline soil. The difference of the Cd passivation efficiency is correlated with contributions of various Cd-biochar binding mechanisms, which cation exchange mechanism is largely eliminated for CSB-NaOH. The interaction of Cd with CSB/CSB-NaOH was further evidenced through characterization results of Scan Electron Microscopy (SEM), X-Ray Diffraction (XRD), Fourier-transformed infrared spectroscopy (FTIR) and X-ray Photoelectron spectroscopy (XPS). Characterization results proved that carboxyl, hydroxyl and ethyl groups were the key functional groups involved in Cd passivation. XPS results showed that Cd binding methods varied between CSB and CSB-NaOH, which Cd2+ and Cd-O were the main form of Cd binding to CSB while Cd-O was the main form on CSB-NaOH. In this work, it was demonstrated that in acid soil, pH change caused by biochar plays a more significant role in controlling the Cd bioavailability, while in alkaline soil, the strength of the Cd-biochar interaction is more decisive for the Cd passivation efficiency. This work provides information on how to select the suitable passivator to decrease the Cd bioavailability in terms of different soil pH and property.

Soil ridge cultivation maintains grain As and Cd at low levels and inhibits As methylation by changing arsM-harboring bacterial communities in paddy soils.

The simultaneous mitigation of toxic arsenic (As) and cadmium (Cd) in rice grain remains a global challenge. The over-accumulation of husk dimethylarsinic acid (DMAs) induces the rice straight-head disease, which threatens rice production worldwide. In this study, we investigated various soil ridge height treatments with Eh ranging from - 225-87 mV and pH ranging from 6.3 to 4.1. Soil ridge cultivation can maintain grain As and Cd at low levels for slightly co-contaminated paddy soils, especially when the ridge height is 11 cm (Eh of 43 mV and pH of 4.6), where grain inorganic As decreased-at maximum-by 48% and DMAs by 55%. Grain Cd (0.14 mg kg-1) increased but was still below the limit (0.2 mg kg-1) in China, and the cost of ridging is acceptable. There were definite correlations among porewater As, Cd, Fe, S, and Mn contents across various Eh and pH values. Soil ridge cultivation significantly (P < 0.05) diminished the copy number of As-reducing (harboring arsC and arrA), As-methylating (harboring arsM), and sulfate-reducing (harboring dsrA) bacteria. Moreover, soil ridge cultivation shifted the arsM-harboring microbiota. In response to ridge height increase, the abundance of the bacterial biomarker phylum Euryachaeota declined and the families Halorubrum and Planctomyces were gradually replaced by Sandaracinus in paddy soil.

Effect of humic and calcareous substance amendments on the availability of cadmium in paddy soil and its accumulation in rice.

Humic substances (HS) are widely known as important components in soil and significantly affect the mobility of metals due to their large surface area and abundant organic functional groups. Calcareous substances (CSs) are also commonly used as robust and cost-effective amendments for increasing the pH of acidic soils and decreasing the mobility of metals in soils. In this study, we developed a new remediation scheme for cadmium (Cd)-contaminated soil remediation by coupling HS and CS. The results showed that regardless of the addition of fulvic acid (FA), all the CS-containing treatments significantly increased the soil pH by 0.32-0.60, and the concentration of bioavailable Cd decreased in the moderately (field experiment soil, maximum 62%) and highly (pot experiment soil, maximum 57%) Cd-contaminated soils. The Cd content in rice (Oryza sativa L.) tissues significantly decreased after all the treatments. The bioaccumulation factors (BAFs) decreased by over 50% in the roots, stems, leaves and husks in all treatments, while the translocation factors (TFs) only significantly decreased in the highly contaminated soil. Among all treatments, the two HS+CS treatments (FA+CaCO3 and FA+CaO) had the greatest effect on decreasing the concentration of bioavailable Cd in soil and Cd in brown rice grains. The suggested mechanism for the effectiveness of coupled HS and CS was that CS first mitigated the pH and precipitated Cd, followed by a complexation effect between HS and Cd. Although the Cd in rice grains in both cases was higher than the standard limit, HS+CS remediation can be advocated as a robust, simple and cost-effective scheme for Cd remediation if the additive dose is slightly increased, as this approach can simultaneously improve the pH of acidic soil and adsorb Cd in soil.

Contradictory tendency of As(V) releasing from Fe-As complexes: Influence of organic and inorganic anions.

The strong ability of ferrihydrite and its aged minerals for fixing arsenate is a key factor in remediating arsenate-polluted environments. It is therefore crucial to clarify the stability of Fe-As complexes and the release conditions for As(V). The As(V) release amount was evaluated and compared in the presence of six representative anions, namely, phosphate, silicate, sulfate, inositol hexaphosphate, citrate, and oxalate. It was found that the As(V) release amount changed with the aging time of ferrihydrite and that this tendency generally followed two rules. These are, longer aging time leads to lower As(V) release (Rule 1), and longer aging time leads to higher As(V) release (Rule 2). Whether Rule 1 or Rule 2 dominated As release depended on the number of surface groups, size of competing anions, and contribution of As(V) re-adsorption. Characterization results using X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) provided evidence for the predicted mechanisms of As(V) release under various circumstances. In this work, it was demonstrated that when inorganic anions such as sulfate and silicate are present, ferrihydrite with longer aging time led to decreased As(V) release. When organic anions are present, ferrihydrite with less aging time results in reduced As(V) leaching. For anions such as phosphate, the As(V) release amount in relation to the ferrihydrite aging time depends on the concentration of phosphate ions. Nevertheless, the ligand concentration and As(V) loading rate on ferrihydrite should be simultaneously considered for the rule governing As(V) releasing.

Exogenous fulvic acid enhances stability of mineral-associated soil organic matter better than manure.

Mineral-associated soil organic matter (MAOM) is seen as the key to soil carbon sequestration, but its stability often varies with types of exogenous organic materials. Fulvic acid and manure are ones of the exogenous organic materials used for the improvement of degraded soil. However, little is known about if and how fulvic acid and manure affect the stability of MAOM. Using a field experiment of four fertilization treatments (no fertilization, mineral fertilizers, fulvic acid, and manure) and a comprehensive meta-analysis using relevant studies published prior to January 2020, we investigated effects of exogenous fulvic acid and manure applications on four MAOM stability indexes: association intensity, humus stabilization index, iron oxide complex coefficient, and aluminum oxide complex coefficient. Exogenous fulvic acid and manure applications increased soil organic carbon fractions by 26.04-48.47%, MAOM stability by 12.26-387.41%, and complexed iron/aluminum contents by 16.12-20.01%. Fulvic acid application increased MAOM stability by promoting mineral oxide complexation by 20.33% and manure application improved MAOM stability via increasing humus stabilization by 21-25%. Association intensity was positively correlated with contents of soil carbon fractions and the metal oxide complex coefficients were positively correlated with iron/aluminum oxide contents. Moreover, stable-humus exerted significantly positive direct and indirect effects on association intensity and humus stabilization index, while amorphous iron/aluminum content had significantly negative influences on metal oxide complex coefficients. The meta-analysis verified that long-term fulvic acid application improved MAOM stability more so than manure application in acidic soils. We recommend that strategies aiming to prevent land degradation should focus on the potential of fulvic acid as a soil amendment because it can significantly increase MAOM stability.

The stability of poorly crystalline arsenical ferrihydrite after long-term soil suspension incubation.

2- Line ferrihydrite (Fh) is widely used as a robust amendment for rapid arsenic removal or remediation in water or soil. However, the poorly crystalline phase of Fh is unstable and leads to arsenic leaching after long-term submergence in reductive aquatic and soil environments. In this study, the synthesized As(V)-bound Fh was characterized by various spectral approaches to investigate the factors that may affect the variation in As(V)-Fh in long-term continuously submerged soil suspensions. The X-ray diffraction (XRD) results showed that hematite was the main product and that goethite was the byproduct after 360 d of incubation. Approximately 12-17% and 4-5% Fh were transformed at As/Fe mole ratios of 0.005 and 0.05, respectively. After 360 d of incubation, the hematite morphology was clearly observed by scanning electron microscopy (SEM), and the As(V)-Fh surface areas were also decreased by 17.3-27.6% and 11.9-16.6% for As/Fe mole ratios of 0.005 and 0.05, respectively. In a comparison of the two tested soils (soils sampled in Sichuan Province (SC) and Hunan Province (HN)), As(V)-Fh transformed faster in HN soil suspensions, and more hematite and goethite were formed. Furthermore, during the incubation period, As(V) was transformed to As(III), and both species were released into the suspension from the As(V)-Fh surface. It was suggested that soil pH and Fe(II) concentration were key factors controlling the As(V)-Fh transformation process, and the differences between the two soils were due to the different soil pH values and contents of available Fe. Arsenic release was mainly caused by Fh transformation and ligand competition with soil organic matter (SOM).

Simultaneous mitigation of Cd and As availability in soil-rice continuum via the addition of an Fe-based desulfurization material.

The simultaneous mitigation of toxic arsenic (As) and cadmium (Cd) in rice grain remains a global challenge. Passivation with natural or artificially modified materials has shown great potential to simultaneously reduce the bioavailability of As and Cd in paddy soils. To date, however, limited materials have are available, with unclear underling mechanisms. Here, a natural iron-based desulfurization material is hypothesized to simultaneously mitigate As and Cd availability in paddy soil-rice continuum, since it is rich in calcium (Ca), iron (Fe), Silicon (Si), manganese (Mn), and sulfur (S). The addition of the proposed material promoted rice growth and reduced soil availability of Cd (extracted with 0.01 mg·L-1 of CaCl2) by 88.0-89.6% and As (extracted with 0.5 mg·L-1 of KH2PO4) by 37.9-69.9%. Grain Cd was reduced by 26.4-51.6%, whereas that of inorganic As (iAs) by 33.3-42.7%. The increased Fe (by 44.2%) and Mn (by 178.6%) in iron plaque on the root surface were conducive to the reduction of grain Cd and iAs after application. Furthermore, the maximum adsorption capacities of the proposed material for Cd and As(III) reached 526.31 and 2.67 mg·g-1, respectively. The coprecipitation with Cd(OH)2 as a product, Fe-As and Ca-As complexation, and ion exchange of Fe2+ released by the material with Cd2+ are involved in the mechanisms underlying the available As and Cd reduction. Combining the safety, low-cost, and high accessibility, Fe-based desulfurization material showed great potential for future safe-utilization of As-Cd contaminated paddy soil via passivation.

Cadmium and arsenic availability in soil under submerged incubation: The influence of humic substances on iron speciation.

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 CaCl2-extractable Cd by 12.66-93.13%, and increased the KH2PO4-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.

Effects of green manure planted in winter and straw returning on soil aggregates and organic matter functional groups in double cropping rice area.

To explore the mechanism of exogenous organic materials enhancing soil organic carbon and soil fertility, based on a long-term experiment located in Hengyang Red Soil Experimental Station, we examined the effects of winter green manure and straw returning patterns (CK, winter fallow; MV, winter Chinese milk vetch; S, early-season rice straw total returning; DS, early-season and late-season rice straw total returning; SMV, winter Chinese milk vetch + early-season rice straw total returning; DSMV, winter Chinese milk vetch + early-season and late-season rice straw total returning) on soil aggregates and organic functional groups. The results showed that the proportion of super aggregates (>2 mm) and macroaggregates (0.25-2 mm) in double cropping rice soil was the highest with a ratio of about 72.1%-81.8%, and the organic carbon content in the two kinds of aggregates was as high as 12.1-20.7 g·kg-1, accounting for 22.7%-59.0% of the total organic carbon. The main organic functional group in paddy soil was polysaccharides, followed by aliphatic carbon and aromatic carbon. The abundance of all those groups was affected by winter Chinese milk vetch growing and straw returning. Compared with other treatments, DSMV significantly increased the proportion of super aggregates (>2 mm) and macroaggregates (0.25-2 mm) and favored the accumulation of inert carbon such as aromatic carbon in the two kinds of aggregates. DSMV could enhance the stability of soil aggregates and organic matter, which had high potential in the real agricultural production.

Seeking for an optimal strategy to avoid arsenic and cadmium over-accumulation in crops: Soil management vs cultivar selection in a case study with maize.

Soil management and cultivar selection are two strategies to reduce the accumulation risk of heavy metals in crops. However, it is still an open question which of these two strategies is more efficient for the safe utilization of contaminated soil. In this study, the available bio-concentration factors (aBCF) of arsenic (As) and cadmium (Cd) among 39 maize cultivars were determined through a field experiment. The effect of soil management was mimicked by choosing diverse sampling sites having different soil available contents of As and Cd. The aBCF of As and Cd in grain ranged from 0.02 to 0.13 and 1.17 to 42.2, respectively. The accumulation ability of As and Cd was classified among different maize cultivars. Soil pH and total As controlled the level of available As in soils, while soil pH dominated available Cd in soil. A soil pH of 6.5 was recommended to simultaneously minimize soil available As and Cd by managing soil conditions. The quantitative effects of cultivar and soil management on grain As and Cd were expressed as Q [Grain As] = 0.746Q [Cultivar]-0.126Q [pH]+0.276Q [Asavailable] (R2 = 0.648, P = 1.00 × 10-37) and Q [Grain Cd] = 0.913Q [Cultivar]-0.192Q [pH]+0.071Q [SOC] (R2 = 0.782, P = 1.00 × 10-37), respectively. Cultivar selection contributed stronger than soil management to decrease the As and Cd levels in maize grains. A feasible method to seek for a more efficient strategy was proposed for the safe utilization of contaminated soil.

Stability of Fe-As composites formed with As(V) and aged ferrihydrite.

During the aging process, ferrihydrite was transformed into mineral mixtures composed of different proportions of ferrihydrite, goethite, lepidocrocite and hematite. Such a transformation may affect the fixed ability of arsenic. In this study, the stability of Fe-As composites formed with As(V) and the minerals aged for 0, 1, 4, 10 and 30 days of ferrihydrite were systematically examined, and the effects of molar of ratios Fe/As were also clarified using kinetic methods combined with multiple spectroscopic techniques. The results indicated that As(V) was rapidly adsorbed on minerals during the initial polymerization process, which delayed both the ferrihydrite conversion and the hematite formation. When the Fe/As molar ratio was 1.875 and 5.66, the As(V) adsorbed by ferrihydrite began to release after 6 hr and 12 hr, respectively. The corresponding release amounts of As(V) were 0.55 g/L and 0.07 g/L, and the adsorption rates were 92.43% and 97.50% at 60 days, respectively. However, the As(V) adsorbed by the transformation products aged for 30 days of ferrihydrite began to release after adsorbed 30 days. The corresponding release amounts of As(V) were 0.25 g/L and 0.03 g/L, and the adsorption rates were 84.23% and 92.18% after adsorbed 60 days, for the Fe/As=1.875 and 5.66, respectively. Overall, the combination of As(V) with ferrihydrite and aged products transformed from a thermodynamically metastable phase to a dynamically stable state within a certain duration. Moreover, the aging process of ferrihydrite reduced the sorption ability of arsenate by iron (hydr)oxide but enhanced the stability of the Fe-As composites.

Effects of composited organic mobilizing agents and their application periods on cadmium absorption of Sorghum bicolor L. in a Cd-contaminated soil.

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.