Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques

Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L_3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L_3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L_3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu₂S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.     

铁基合金脱除磷化氢中的砷化氢

为了脱除磷化氢中的砷化氢,合成了Fe-B非晶态合金和Fe(Cu)P合金,实验了它们对磷化氢中砷化氢的脱除作用,并与锌粉和Co-B非晶态合金进行了比较。结果表明,Fe(Cu)P效果最佳,脱砷温度低、脱砷容量大,而且合成原料价廉易得;而Fe-B非晶态合金优于Co-B非晶态合金以及锌粉。     

The impact of sequestration on the bioaccessibility of arsenic in long-term contaminated soils

Arsenic (As) contamination of soil poses a potential threat to human health, particularly for small children, through the incidental ingestion of soil from hand-to-mouth activity. In this study, we examined the relationship between As bioaccessibility using the simplified bioaccessibility extraction test (SBET) and the soil fractions that contribute to bioaccessible As in 12 long-term contaminated soils. Sequential fractionation of soils prior to As bioaccessibility assessment found that As was primarily associated with the specifically sorbed (3-26%), amorphous and poorly crystalline (12-82%), and the well crystalline (3-25%) oxyhydroxide Fe/Al phases with proportions varying depending on the mode of As input. Arsenic bioaccessibility in these soils ranged from less than 1% in the gossan soil to 48% in railway corridor soils. Soil fractions contributing to As bioaccessibility were found to be from the non-specifically (<1-11%), the specifically (<1-29%) sorbed and the amorphous and poorly-crystalline (30-93%) oxyhydroxide Fe/Al fractions. Significant correlations (p<0.05) were found between the As bioaccessible fraction and the amorphous and poorly-crystalline oxyhydroxide Fe/Al fractions indicating that this fraction is a key factor influencing As bioaccessibility in many anthropogenically contaminated soils.     

Effects of high dose copper on plant growth and mineral nutrient (Zn,Fe, Mg,K, Ca) uptake in spinach

Loessal soil is one of the main cultivated soils in northwest China. Part of its distribution area was irrigated with industrial wastewater in past three decades. This caused heavy metal contamination in the soil. It had induced toxicity on crops and also threatened local human health for now. Based on a field plot experiment, effects of different Cu concentrations (from 45 to 2000 mg kg^?1) in loessal soil on spinach plant growth and uptake of mineral nutrients (Zn, Fe, Mg, K, and Ca) by spinach were investigated. The Cu addition increased available concentrations of mineral nutrients in loessal soil and concentrations of Cu, Zn, Mg, and Ca in roots. The translocation of mineral nutrients from roots to leaves was inhibited under Cu addition, inducing their decrease in leaves. The EC₁₀ and EC₅₀ of soil Cu in relative dry weights of leaves were 240.33 mg kg^?1 and 1205.04 mg kg^?1, respectively. The PLS-PM analysis showed that available concentrations of nutrients in soil were only affected by Cu in soil positively, nutrients in roots were mainly affected by Cu in soil and Cu in leaves positively, nutrients in leaves were mainly affected by Cu in roots negatively, translocation of nutrients in spinach and plant growth were principally affected by Cu in leaves negatively, and the total effect of Cu in leaves on nutrients in roots and leaves, translocation of nutrients in spinach, and plant growth was the highest. Our results indicated that the phytotoxicity of Cu including spinach growth inhibition and mineral disorder in spinach was mainly affected by the Cu concentrations in leaves.

     

Sorption of alpha and beta hydrophobic endosulfan in a Vertisol from southeast region of Turkey

Endosulfan has been applied to control numerous insects in a variety of food and non-food crops. Limited information is available on dynamics of this pesticide in the soil. The objective of this research was to determine the adsorption–desorption behavior of the alpha (α) and beta (β) endosulfan in a Vertisol from the southeast region of Turkey, where cotton is the main crop in the large irrigated lowlands. The α and β endosulfan were adsorbed considerably and Freundlich adsorption–desorption isotherms fitted the α and β endosulfan data (R² > 0.98). Freundlich adsorption coefficients (K_f) for the α endosulfan ranged between 21.63 and 16.33 while for the β endosulfan they were between 14.01 and 17.98 for the Ap and Bw2 horizons. The difference of K_f values of α and β endosulfan for two horizons were explained with the slight difference in the amount of organic matter and clay, but considerable difference in Fe contents of the two horizons. Alpha and β endosulfan K_fd values were 118.03 and 45.81 for the Ap and 48.08 and 68.71 for the Bw2 horizons. Higher adsorption and desorption behavior of the endosulfan isomers for the same horizon was attributed to poor physical bonding between the endosulfan molecule and the surfaces of fundamental soil particles. This fact is thought to increase the effective use of endosulfan in agriculture with a possibility of its movement to the surface and groundwater in the Vertisol studied.     

Solubility products of six metal‐glyphosate complexes in water and forestry soils,and their influence on glyphosate toxicity to plants

Abstract

The solubility products (K_sp) of 1:1 complexes of glyphosate, [N‐(phosphonomethyl)glycine], with Mg²⁺, Ca²⁺, Mn²⁺, Zn²⁺, Cu²⁺ and Fe³⁺, were determined in buffered (pH 7.0) distilled water, moist Ottawa sand, sandy loam and clay loam soils, each adjusted to 0.02 M with respect to KNO₃. The K_sp values decreased in the order of Mg ? Ca > Mn > Zn > Cu > Fe, regardless of the medium in which they were determined. The constants measured in Ottawa sand were similar to those in water, but those in the forestry soils depended upon the type of metal ion involved. The values for the Mg, Ca, Mn and Zn complexes were about 2 to 3 times lower in sandy loam soil than those in water, but those in clay loam were about 3 to 10 times lower. The K_sp of the Cu and Fe complexes were similar to those in water regardless of the soil type used.

In a bioassay experiment using tomato plants, immersed in the saturated solutions of the complexes or planted in the sand and soils containing saturated solutions of the complexes, no mortality occurred although slight inhibition in growth was observed in all cases. The most soluble complexes of Mg and Ca caused the most reduction in plant height, while the least soluble complex of Fe caused little growth inhibition. The Zn, Cu and Mn complexes caused some growth inhibition depending on their K_sp values. The larger the solubility product, the greater the concentration of glyphosate ion in solution, and the greater the growth inhibition. In a similar experiment using white spruce seedlings, growth inhibition was insignificant over the 12‐d bioassay period.     

复合纳米材料对土壤重金属离子吸持固化的模拟研究

土壤中过量重金属离子可通过食物链和地表水系统危害人群健康。通过土柱淋溶模拟实验,研究了SiO2-Al2O3-Fe2O3等复合纳米材料对土壤溶液中Cu2+、Cd2+、Pb2+、Zn2+和Ni2+的吸持与固化特征。分别向重金属含量4倍于土壤二级标准(GB15618-1995)的土壤中添加0%、4%、6%和10%的复合纳米材料,分析不同深度土壤渗滤液以及土柱上栽培植物不同部位中重金属的含量。结果表明,碱性壤质土壤中重金属向下的迁移量很少;在含4%复合纳米材料土柱中,其吸持固化土壤溶液中63%的Cu、79%的Cd、68%的Pb、89%的Zn和76%的Ni;在含6%复合纳米材料土柱中,其吸持固化土壤溶液中82%的Cu、92%的Cd、76%的Pb、91%的Zn和88%的Ni;再增加土柱中复合纳米材料的含量,其吸持固化效果并不再显著增加。     

Arsenic release from flooded paddy soils is influenced by speciation, Eh, pH, and iron dissolution

Arsenic (As) is highly mobilized when paddy soil is flooded, causing increased uptake of As by rice. We investigated factors controlling soil-to-solution partitioning of As under anaerobic conditions. Changes in As and iron (Fe) speciation due to flooded incubation of two paddy soils (soils A and B) were investigated by HPLC/ICP-MS and XANES. The flooded incubation resulted in a decrease in Eh, a rise in pH, and an increase in the As(III) fraction in the soil solid phase up to 80% of the total As in the soils. The solution-to-soil ratio of As(III) and As(V) (R_L/S) increased with pH due to the flooded incubation. The R_L/S for As(III) was higher than that for As(V), indicating that As(III) was more readily released from soil to solution than was As(V). Despite the small differences in As concentrations between the two soils, the amount of As dissolved by anaerobic incubation was lower in soil A. With the development of anaerobic conditions, Fe(II) remained in the soil solid phase as the secondary mineral siderite, and a smaller amount of Fe was dissolved from soil A than from soil B. The dissolution of Fe minerals rather than redox reaction of As(V) to As(III) explained the different dissolution amounts of As in the two paddy soils. Anaerobic incubation for 30 d after the incomplete suppression of microbial activity caused a drop in Eh. However, this decline in Eh did not induce the transformation of As(V) to As(III) in either the soil solid or solution phases, and the dissolution of As was limited. Microbial activity was necessary for the reductive reaction of As(V) to As(III) even when Eh reached the condition necessary for the dominance of As(III). Ratios of released As to Fe from the soils were decreased with incubation time during both anaerobic incubation and abiotic dissolution by sodium ascorbate, suggesting that a larger amount of As was associated with an easily soluble fraction of Fe (hydr) oxide in amorphous phase and/or smaller particles.     

Sorption of 1,2,4-trichlorobenzene and tetrachloroethene within an authigenic soil profile: Changes in Koc with soil depth

The sorption of 1,2,4-trichlorobenzene and tetrachloroethene was investigated in a series of well-controlled batch experiments, using authigenic soil materials from a profile extending to 2.5 m below ground surface. Batch experiment techniques were verified by study with both pulverized and unpulverized soil at different times of equilibration, using two widely different soil:water ratios, and at a wide range of aqueous concentration. Sorption isotherms were approximately linear, with sorption distribution coefficients (K_d) found to decrease roughly 100-fold down the soil profile. K_d decreased with depth to an extent greater than could be predicted on the basis of the only 10-fold decrease in natural solid organic matter (SOM) content and despite significantly higher specific surface area in the lower horizons. All base-extractable SOM in these deeper soil horizons was operationally defined as fulvic acid (FA), although there was also a significant fraction that was not extracted by the standard base technique. The lower K_d of the deeper soil horizons is believed to reflect a complex combination of (1) lower SOM content; (2) a more hydrophilic form of SOM; and (3) a more intimate association of the SOM with the mineral fraction, affecting its accessibility, sorptivity, or both. For the deeper horizons, an increase in overall K_d by more than 4-fold was observed on solids treated by either base extraction or H₂O₂ treatment, demonstrating that sorption to remaining soil components could be dramatically increased by fractional SOM removal and/or chemical alteration of the soil. A simple regression model that divides SOM into only two types (shallow and deep SOM) provides a reasonably good explanation of sorption in all seven horizons and suggests an order-of-magnitude variability in K_oc among surface soil and deeper horizons.     

Evaluation of an approach for the characterization of reactive and available pools of twenty potentially toxic elements in soils: Part I – The role of key soil properties in the variation of contaminants’ reactivity

Harmful effects of potentially toxic elements (PTE’s) in soils relate to their geochemically reactive fraction. To assess the degree of the reactivity, specific extractions or models are needed. Here we applied a 0.43 M HNO₃ chemical extraction to assess reactive pools of a broad range of PTE’s in 136 contaminated and non-contaminated soils. Furthermore we derived Freundlich-type models based on commonly available soil properties (pH, organic carbon and clay) as well as extended models that used other properties such as amorphous Al and Fe oxides and evaluated their possible use in risk assessment.The approach allowed to predict the reactivity of As, Hg, Co, U, Ba, Se, Sb, Mo, Li, Be (r²: 0.55–0.90) elements not previously included in such studies, as well as that of Cd, Zn, Cu, Pb, Ni and Cr (r²: 0.73–0.90). The inclusion of pH, organic carbon and clay improved the performance of all models except for Be and Mo, although the role of clay is not completely clear and requires further investigation. The ability of amorphous metal oxides to affect the reactivity of As, Hg, Cu, Ni, Cr, Sb, Mo and Li was expressed by the models in agreement with known geochemical processes leading to the retention of PTE’s by the solid matrix. Hence, such approach can be a useful tool to account for regional differences in soil properties during the identification of risk areas and constitute a significantly more powerful tool than the analysis of total pools of PTE’s in soils.     

高岭土模拟铜污染土壤电动力学修复

采用电动力学方法修复重金属污染土壤。研究中采用高岭土模拟铜污染土壤，结合电动力学修复理论，考察了不同电压、添加络合剂条件下铜的修复效果。结果表明，当电压强度为0．5V／cm时，最靠近阴极部分的土壤中Cu^2＋的C／C。为1．596，当电压强度为1V／cm时，C／C0为2．245，说明适当提高电压强度能够有效的增加Cu^2＋的迁移效果；土壤中未加入络合剂时，Cu^2＋大部分集中在第5段土壤中，C／C0为1．339，在土壤中加入络合剂以后Cu^2＋大部分集中在靠近阴极部分的土壤中，C／C。为1．716，说明在污染土壤中加入一定量的络合剂可以与Cu^2＋结合生成螯合物，提高Cu^2＋的迁移效果。     

Mobilization of arsenic in aquifers from the Datong Basin,China: Evidence from geochemical and iron isotopic data

Iron isotope compositions of various Fe pools in aquifer sediments were measured at a known As-contaminated site in the Datong Basin, China. The δ⁵⁶Fe values of HCl-extracted poor-crystalline Fe(III) range widely from ?0.41‰ to 0.36‰. We interpret the low Fe(II)/Fe_Extractable ratios (<50%) and the negative correlation between Fe(II)/Fe_Extractable and δ⁵⁶Fe values in HCl-extracted poor-crystalline Fe to be best explained by redox cycling of Fe induced by microbial Fe(III) reduction. However, the high Fe(II)/Fe_Extractable ratios (?70%) and positive correlation between Fe(II)/Fe_Extractable and δ⁵⁶Fe values for HCl-extracted poor-crystalline Fe indicates production of sulfides (FeSs). The δ⁵⁶Fe values of crystalline Fe(III) extracted by reductant appears to be comparatively small varying from ?0.01‰ to 0.24‰, which is consistent with the δ⁵⁶Fe values for ferric oxides/hydroxides having undergone microbial Fe(III) reduction. The Fe isotope composition of various Fe pools shows the transformation between crystalline Fe(III) and poor-crystalline crystalline Fe(III) and the secondary Fe(II) phases has already occurred or is occurring in aquifer sediments. More importantly, there is a significant difference in the As concentrations in crystalline Fe(III) oxides/hydroxides and HCl-extracted Fe phases. The concentrations of As range from 1.6 to 29.9 mg kg^?1 and from 0.6 to 3.0 mg kg^?1, for crystalline Fe(III) and HCl-extracted Fe phases respectively. Accordingly, the transformation of Fe minerals induced by microbial Fe(III) reduction can contribute to the mobilization of As. This study is the first to examine the Fe isotope compositions in high As aquifer sediments; the results show that the Fe isotope would be an important tool in demonstrating the enrichment of As in groundwater.     

Assessment of aided phytostabilization of copper-contaminated soil by X-ray absorption spectroscopy and chemical extractions

Field plots were established at a timber treatment site to evaluate remediation of Cu contaminated topsoils with aided phytostabilization. Soil containing 2600 mg kg⁻¹ Cu was amended with a combination of 5 wt% compost and 2 wt% iron grit, and vegetated. Sequential extraction was combined with extended X-ray absorption fine structure (EXAFS) spectroscopy to correlate changes in Cu distribution across five fractions with changes in the predominant Cu compounds two years after treatment in parallel treated and untreated field plots. Exchangeable Cu dominated untreated soil, most likely as Cu(II) species non-specifically bound to natural organic matter. The EXAFS spectroscopic results are consistent with the sequential extraction results, which show a major shift in Cu distribution as a result of soil treatment to the fraction bound to poorly crystalline Fe oxyhydroxides forming binuclear inner-sphere complexes.     

Encapsulation Behaviors of Metals in Slags Containing Various Amorphous Volume Fractions

Abstract

In this study, a melting process with addition of SiO₂was applied to treat incinerator fly ash. To describe the encapsulation behaviors of metals quantitatively, the amorphous volume fraction (AVF) of slags was initially determined. Vitrification appeared to reduce the mobility of Cr, Cu, Mn, and Ni instead of significantly immobilizing Cd, Pb, and Zn. It was verified that SiO₂enhanced the formation of an amorphous glassy structure. With the increase of SiO₂, the crystalline phases would gradually diminish and transform into a higher silica-connected species. During the formation of slag matrix, Al, Ca, and Mg could modify the glass network, and consequently the encapsulation behaviors of these species would noticeably affect the chemical stability of slags. Significant immobilization of crust metals could be achieved only when a more compact and interconnected amorphous glass network was formed. Hence, it indicated that a higher AVF silica-based slag had a better potential to resist acid attack. In conclusion, for environmental protection, it is important to investigate the correlation between the encapsulation behaviors of metals and the crystalline characteristics of slag structure.     

Influence of organic amendments on copper distribution among particle-size and density fractions in Champagne vineyard soils

The intensive use for over 100 years of copper sulfate (Bordeaux mixture) to fight against mildew in vineyard soils has led to an important, widespread accumulation of Cu (100 to 1500 mg Cu kg-1 soil). In Champagne vineyards, organic amendments are used currently to increase soil fertility and to limit soil erosion. Organic amendments may have a direct effect on the retention of Cu in the soil. To assess the influence of the organic management on the fate of Cu in calcareous Champagne vineyard soils, we studied Cu distribution (1) in the soil profile and (2) among primary soil particles, in vineyard parcels with different amendments. Amendments were oak-bark, vine-shoots and urban compost. The results were compared with the amount and the distribution of Cu in an unamended calcareous soil. Physical soil fractionations were carried out to separate soil primary particles according to their size and density. Cu has a heterogeneous distribution among soil particle fractions. Two fractions were mainly responsible for Cu retention in soils: the organic debris larger than 50 microns or coarse particulate organic matter (POM) issued from the organic amendments, and the clay-sized fraction < 2 microns. The POM contained up to 2000 mg Cu kg-1 fraction and the clay fraction contained up to 500 mg Cu kg-1 fraction. The clay-sized fraction was responsible for almost 40% of the total amount of Cu in the four parcels. POM was predominantly responsible for the differences in Cu contents between the unamended and the three amended parcels. Our results attested that methods of soil particle-size fractionation can be successfully used to assess the distribution of metal elements in soils.     

Solving mercury (Hg) speciation in soil samples by synchrotron X-ray microspectroscopic techniques

Direct mercury (Hg) speciation was assessed for soil samples with a Hg concentration ranging from 7 up to 240 mg kg⁻¹. Hg chemical forms were identified and quantified by sequential extractions and bulk- and micro-analytical techniques exploiting synchrotron generated X-rays. In particular, microspectroscopic techniques such as μ-XRF, μ-XRD and μ-XANES were necessary to solve bulk Hg speciation, in both soil fractions <2 mm and <2 μm. The main Hg-species found in the soil samples were metacinnabar (β-HgS), cinnabar (α-HgS), corderoite (Hg₃S₂Cl₂), and an amorphous phase containing Hg bound to chlorine and sulfur. The amount of metacinnabar and amorphous phases increased in the fraction <2 μm. No interaction among Hg-species and soil components was observed. All the observed Hg-species originated from the slow weathering of an inert Hg-containing waste material (K106, U.S. EPA) dumped in the area several years ago, which is changing into a relatively more dangerous source of pollution.     

Distribution and Fractionation of Copper in Soils of Apple Orchards (5 pp)

Background Frequent application of Bordeaux mixture, which includes copper, as a fungicide in fruit and grape orchards may lead to copper accumulation in the soil, especially when orchard age and application times increase. The objectives of this study were: (i) to investigate the copper content and its spatial distribution in orchard soils; (ii) to identify the copper fractionation in soil and its relationship with plant uptake; (iii) to understand the characteristics of copper contamination in orchard soils. Materials and Methods Soil profile samples were taken in apple orchards with ages of 0, 5, 10, 20, 30 years and pot experiments were also carried out to study the effects of external copper input on copper fractionation. All soil samples were air-dried, ground and extracted with 0.43 mol L–1 HNO3 for the total absorbed copper. Fractionation determination was conducted following Tessier and Shuman sequential extraction methods, and copper was measured with AAS. Plant samples were first dry ashed, dissolved with 6 mol L–1 HCl and then copper and other elements were measured with ICP-MS.Results and Discussion Soil total Cu was higher in the apple orchards than that in non-orchard fields and was seen to have increased with orchard age. Soil Cu increased substantially with the average annual copper increase, ranging from 2.5 to 9 mg Cu kg–1. The distribution of copper in the soil profile was uneven, decreasing from surface to deeper layers, and the differences were significant, but the contents in every layer were also significantly correlated with those in the next layers. For all copper fractions, the organically bound, crystalline Mn oxide bound, and amorphous Fe bound fractions extracted with the Shuman method were much higher than the exchangeable and residual fractions. Using the Tessier method, organically bound, carbonate bound and Fe-Mn oxide bound fractions were much higher. With an increase in external copper input, the organically bound, crystalline Mn oxide bound and amorphous Fe bound fractions in the Shuman method and organically bound, carbonate bound and Fe-Mn oxide bound fractions in the Tessier method all increased significantly, while the changes in other fractions were not significant. Soil total copper and copper fractions were found to have good correlations with apple tree uptake. Copper in fruit flesh had significant correlations with soil total content in the 0–10 cm layer, all the copper fractions in the 0–5 cm layer, and some fractions in the deeper layers. Conclusion Copper content in orchard soils increased significantly with intensive application of Bordeaux mixtures and orchard age. Copper content decreased sharply from the topsoil to deeper soil layers. The copper contents in different layers also significantly correlated with those in the next layers. Dominant fractions of the copper in soil were mainly associated with organic matter, iron and manganese oxides and carbonates. A close relationship was found between the copper content in soils and in apple tree organs (which contained 8.9 to 66mg kg–1 Cu). Recommendation and Perspective Though most copper in the soil was specifically adsorbed or immobilized, and copper was mainly distributed in topsoil, which was essentially devoid of roots, the copper concentration of fruit still had significantly positive correlations with soil copper and most copper fractions. Therefore, measures must be taken to control copper accumulation in orchard soils and to make the apple fruit production sustainable.     

Spatial variability of arsenic concentration in soils and plants, and its relationship with iron, manganese and phosphorus

Spatial distribution of arsenic (As) concentrations of irrigation water, soil and plant (rice) in a shallow tube-well (STW) command area (8 ha), and their relationship with Fe, Mn and P were studied. Arsenic concentrations of water in the 110 m long irrigation channel clearly decreased with distance from the STW point, the range being 68-136 μg L⁻¹. Such decreasing trend was also noticed with Fe and P concentrations, but the trend for Mn concentrations was not remarkable. Concerning soil As, the concentration showed a decreasing tendency with distance from the pump. The NH₄-oxalate extractable As contributed 36% of total As and this amount of As was associated with poorly crystalline Fe-oxides. Furthermore only 22% of total As was phosphate extractable so that most of the As was tightly retained by soil constituents and was not readily exchangeable by phosphate. Soil As (both total and extractable As) was significantly and positively correlated with rice grain As (0.296 ± 0.063 μg g⁻¹, n = 56). Next to drinking water, rice could be a potential source of As exposure of the people living in the As affected areas of Bangladesh.     

Comparative effects on arsenic uptake between iron (hydro)oxides on root surface and rhizosphere of rice in an alkaline paddy soil

The iron (Fe) (hydro)oxides deposited around rice roots play an important role in arsenic (As) sequestration in paddy soils, but there is no systematic study on the relative importance of Fe (hydro)oxides on root surface and in rhizosphere soil in limiting As bioavailability. Twenty-seven rice genotypes were selected to investigate effects of Fe (hydro)oxides on As uptake by rice in an alkaline paddy soil. Results indicated that the As content was positively correlated with the Fe content on root surface, and most of As (88–97%) was sequestered by poorly crystalline and crystalline Fe (hydro)oxides in the alkaline paddy soil. The As sequestration by Fe (hydro)oxides on root surface (IAS_root 16.8–25.0 mg As/(g Fe)) was much higher than that in rhizosphere (IAS_rhizo 1.4–2.0 mg As/(g Fe)); therefore, in terms of As immobilization, the Fe (hydro)oxides on root surface were more important than that in rhizosphere. However, the As content in brown rice did not have significant correlation with the As content on root surface but was significantly correlated (R²?=?0.43, P?<?0.05) with the partition ratio (PR_As?=?IAS_root/IAS_rhizo) of As sequestration on root surface and in rhizosphere, which suggested that Fe (hydro)oxides on root surface did not play the controlling role in lowering As uptake, and the partition ratio PR_As would be a better indicator to evaluate effects of Fe (hydro)oxides around roots on As uptake by rice.