采矿和冶炼活动以及产品使用显著增加了陆地环境中锑(Sb)和砷(As)的浓度。 由于其类似的地球化学行为，在自然环境中 Sb 和 As 常共存。有关中国农田土壤中 Sb 的 分布、存在形态及生物有效性缺乏系统研究。本研究旨在调查从中国 21 个省份采集的不 同类型土壤中 Sb 和 As 的分布，比较单一提取方法和 BCR 逐级提取浓度，评估土壤样品 中 Sb 与 As 的生物有效态浓度;探讨了老化过程对 Sb 形态变化的影响以及生长的小麦作 物中 Sb 的生物利用度;并添加不同的土壤改良剂修复 Sb 污染土壤，评估其修复效果。该 研究为农田土壤 Sb 风险评估提供基础数据，也为 Sb 污染土壤修复提供技术支持。论文主 要研究结果如下:
(1) 比较了 21 种中国农田土壤中 Sb 和 As 的浓度分布和生物可利用。Sb 的浓度范 围在 0.091 和 0.521mg/kg 之间。采自安徽土壤中 Sb 的浓度最高(0.521mg/kg)，广东土壤 中Sb的浓度最低。而As的浓度在7.31和25.42 mg/kg之间。与其他选择的萃取剂相比， EDTA 和 DTPA 的提取率明显更高。在所有 21 个土壤样品中，EDTA 对 Sb 和 NH4NO3 对 As 的提取率最高。生物可利用 Sb 的平均浓度为 0.01-0.65 mg/kg，而 As 含量的平均值高 得多，为 0.20-4.30 mg/kg。
(2)利用逐级提取方法研究了老化过程对土壤中添加的 Sb 形态的影响。将加标土壤 与对照土壤样品进行比较时，土壤样品中总 Sb 浓度随着老化时间延长，呈现出随时间而 降低的趋势。在老化开始时，可溶性和可交换态量为 0.09-0.43 mg/kg，占土壤中总 Sb 浓 度的 5.17-13.7%。土壤中可还原态的含量为 0.20-0.88 mg/kg，占总 Sb 含量的 11.6-29.7%。 可氧化态的浓度为 0.68-1.60 mg/kg。占总 Sb 的 37.9-55.1%。土壤样品中残渣态的量为 1.79-2.98 mg/kg，占总Sb的60.3-85%。将这一趋势与老化时间进行比较时，在第15天和 第 30 天，每个分级中的 Sb 浓度按 F1>F2>F3>F4 的顺序降低。小麦盆栽实验结果表明， 在高浓度(1200 mg/kg)Sb 处理的样品中，Sb 的生物浓缩因子(BCF)值最低(0.005)。 未加标土壤样品的数据表明，Sb 最高 BCF 为 0.10。
(3) 研究了几种堆肥处理受污染土壤中 Sb 的稳定化效果和对植物有效性的影响。 农艺参数的数据揭示了改良土壤和未改良土壤之间的显著差异。生物可利用性结果表明，两种提取剂(0.43 M HNO3 和 EDTA)对土壤中 Sb 的提取都非常有效。尽管对于某些土壤 样品，HNO3 比 EDTA 更具活性。化学物质的添加有助于显著降低 Sb 的生物可利用性，但 其效果不如堆肥肥料。通过 EDTA 和 HNO3 提取的家禽堆肥改良土壤 Sb 的最低生物利用 率分别为 1.099 和 1.109。在所有土壤样品中添加堆肥和化学物质可显著降低有效态 Sb 浓 度，使其对植物的利用率降低。与对照处理相比，家禽堆肥改良土壤中有效态 Sb 含量最 低。
(4)使用三种单一提取技术(0.05M EDTA、0.005M DTPA 和 0.043M HNO3)评估了 四种添加不同Sb浓度(0、80和1200 mg/kg)的土壤中老化对Sb生物有效性的影响。老 化严重影响土壤中 Sb 的生物可利用性，从而影响暴露于受 Sb 污染的土壤中可能带来的健 康风险。老化过程中 Sb 浓度的变化主要由土壤特性和提取溶液的类型来解释。生物累积 因子有助于确定受不同浓度影响的植物 Sb 的摄入量。本研究评估了老化对不同土壤中 Sb 生物利用度的影响，并调查了 Sb 在加标土壤中的生物累积与其有效性之间的关系。在所 有使用的提取剂中，0.43M HNO3 似乎是评估土壤 Sb 生物可利用性的最佳选择。

The mining and smelting activities and product uses have significantly increased the concentrations of antimony (Sb) and arsenic (As) in terrestrial environments. Due to their comparable geochemical behavior, Sb frequently coexists with As in the natural environment. To assess the heavy metal in Chinese farmland soils, the ecological risk assessment methods are to be addressed, as there is a current lack of knowledge status because of a difficulty in soil characterization. The purpose of this study is to provide insight into the distribution of Sb and As in various types of soils collected from 21 provinces of China, to evaluate the bioavailability of Sb and As in soil samples by comparing the single extraction methods and the fractions of BCR sequential extraction, to study the effect of aging on speciation, fractionation, and bioavailability of Sb in a wheat crop grown on Chinese farmland soils, and to study the remediation of phytotoxicity of antimony in contaminated soil using different soil amendments and immobilization techniques. This study encouraged the development of soil heavy metal risk assessment methods, which will contribute to soil conservation and food safety in farmland soils of China. It has important social value and can provide technical guidance for soil restoration. It delivers basic information about the existence of toxic metals in different types of soils across China. The main results are as follows: (1) The concentrations of Sb for 21 Chinese farmland soils are in the range of 0.091 and 0.521 mg/kg. The highest Sb concentration was found in Anhui soil (0.521 mg/kg). The soil of Guangdong showed the minimum concentration of Sb. While the concentrations of As are in the range of 7.31 and 25.42 mg/kg. It was obvious that higher extractability with EDTA and DTPA compared to the other selected extractants. The highest extractability for Sb by EDTA and As by NH4NO3 was observed for all 21 soil samples. The average bioavailable Sb concentrations in the iv samples were 20-25% of the total Sb, while the mean values of As contents were much higher and were found as 0.20-4.30 mg/kg. (2) In the present research, while comparing the spiked soil with controlled soil samples, the total Sb concentration in overall samples reduced with aging, showing a reduction trend with time. At the beginning of the aging study, the amount of soluble and exchangeable fractions was 0.09- 0.43 mg/kg, representing 5.17-13.7% of the total Sb concentration in soil. The results of the reducible fraction were 0.20-0.88 mg/kg in the soil, contributing 11.6-29.7% of the total Sb. The concentration of oxidizable fraction was 0.68-1.60 mg/kg showing 37.9-55.1% of total Sb contents. The amount of residual fraction was 1.79-2.98 mg/kg in soil samples, representing 60.3-85% of the total Sb on day 0. While comparing this trend with aging time, the concentration of Sb in each fraction is decreasing at day 15 followed by day 30 in order of F1 > F2 > F3 > F4. Evaluation of the research study pointed out that BCF for Sb was observed lowest (0.005) in the samples treated with high levels (1200 mg/kg) of Sb. Data regarding samples with non-spiked soils indicated the highest BCF for Sb as 0.10. This indicates that most of the spiked Sb remain in the residual fraction of the soil. (3) The agronomic parameter’s data reveals a significant difference between the amended and non-amended soils. The bioavailability results indicate that both reagents were significantly effective in extracting almost the same amount of Sb. Although for some soil samples, HNO3 was more active than EDTA. The addition of chemicals also helped to reduce the metal bioavailability significantly, but it was not as effective as composted manures. Poultry compost-amended soils showing the minimum bioavailable Sb: 1.099 and 1.109 as extracted by EDTA and HNO3 respectively. Sb decreased remarkably with the addition of compost and chemicals into all soil samples. Although composts were most effective to bound Sb in other fractions than the chemical additions, therefore making it less available to the plants. Sb content in all fractions was lowest in poultry-amended soil as compared to control treatments. (4) The four types of different soils were spiked with varying Sb concentrations (0, 80, and 1200 mg/kg) to investigate the impact of aging on the bioavailability of Sb, by using three single v extraction techniques (0.05M EDTA, 0.005M DTPA, and, 0.043M HNO3). Aging considerably impacts soil Sb bioavailability, and hence the potential health risk caused by prolonged contact with Sb-polluted soils. The change of Sb concentration during aging is mainly explained by soil characteristics and the type of extracted solution. Bioaccumulation factors help determine the intake of plant Sb affected by different concentrations. This research examines the relationship between bioaccumulated Sb and its availability in spiked soils, as well as the influence of aging on Sb bioavailability in different soils. The fact that Sb distribution and availability in spiked soils varied significantly from control soils implies that consideration should be applied when incorporating spiked soils for research. Our experiment involved spiking soils with Sb, which caused the available Sb in different types of soil to decline sharply at the initial stage followed by a relatively increasing over the aging time of two weeks. Moreover, 0.43M HNO3 seems to be the best to evaluate bioavailability changes among all the other extractants used.