液相色谱-原子荧光光谱联用法测定土壤砷铬锑硒元素价态
福建省地质测试研究中心, 福建 福州 350003 |
Determination of Valence States of Water-soluble and Exchangeable As, Cr, Sb and Se in Soil Using HPLC-HG-AFS
Fujian Research Center of Geological Analysis and Testing, Fuzhou 350003, China |
摘要：土壤重金属污染物的环境效应与其无机价态有密切的关系。As、Cr、Sb和Se元素的价态测定意义重大，但由于价态之间易发生转化使测定工作存在较大难度，标准化程度较低。由于早期实验条件的限制，大型仪器的联用尚未普及，地质行业标准DD2005-3推荐使用离子交换树脂分离，原子荧光光谱差减法测定As、Sb、Se价态及石墨炉原子吸收光谱法（GFAAS）测定Cr价态。这些方法前处理操作繁琐，测定次数多，工作量大，其他元素形态的存在还会导致结果出现误差。为满足地质调查和评价的需要，本文建立了一套适用于测定土壤水溶态和离子交换态提取液中As、Cr、Sb、Se价态的方法。样品在50℃水浴振荡加热浸提30min，采用液相色谱-原子荧光光谱法（LC-AFS）分离并测定As、Sb、Se价态，一次进样元素的两种无机价态按顺序出峰，同时测定，简便易行，结果更可靠。为了避免了某些离子交换提取剂的屏蔽和干扰，作为补充建立了AFS选择性测定Sb、Se价态的方法，设备成本较低。对于Cr价态的测定，建立了阳离子交换树脂分离-电感耦合等离子体质谱（ICP-MS）的方法，比推荐的GFAAS测定法灵敏度高。As、Cr、Sb和Se的检出限均可达到0.02μg/g，RSD为3.8%~10.7%，加标回收率为91.0%~106.0%。应用色谱方法对采集的土壤样品进行检测，各项指标满足规范DD2005-3质量要求，与非色谱法相比，实现多组分同时测定。同时初步研究表明，土壤中元素价态含量不高，与土壤总量不存在相关性，采用价态含量作为环境风险评估指标更为合适。
Determination of Valence States of Water-soluble and Exchangeable As, Cr, Sb and Se in Soil Using HPLC-HG-AFS
ABSTRACT BACKGROUND: The environmental effects of heavy metal pollutants in soil are closely related to their inorganic valence. So far there are no standard operating procedures for the detection of the valence states of water-soluble and exchangeable As, Cr, Sb and Se elements in soil samples. Only some reference methods were provided.
OBJECTIVES: Search for the optimum methods for the determination of valence states of water-soluble and exchangeable As, Cr, Sb and Se in soil samples.
METHODS: The valence states of As, Sb and Se were separated and determined by HLPC-HG-AFS after 30 min extraction in a water bath of 50℃. The processes are simpler and more accurate than the recommended subtraction ones by AFS. To avoid the masking action of some extracting agent, the methods of selective determination of Sb(Ⅲ), Sb(Ⅴ), Se(Ⅳ) and Se(Ⅵ) by AFS were introduced, which has the advantage of low instrument cost. As for Cr(Ⅲ) and Cr(Ⅵ), after separated by ion-exchange resin, they were determined by ICP-MS, which is of higher sensitivity than the recommended GFAAS.
RESULTS: The detection limits of As(Ⅲ), As(Ⅴ), Cr(Ⅲ), Cr(Ⅵ), Sb(Ⅲ), Sb(Ⅴ), Se(Ⅳ) and Se(Ⅵ) can meet 0.02μg/g, with the RSD of 3.8%-10.7% and the recovery of 91.0%-106.0%. These methods have been successfully applied to the analysis of geological samples, and all indexes meet the quality requirements of DD2005-3.
CONCLUSIONS: Compared with non-chromatographic methods, newly established ones by HPLC-HG-AFS have obvious advantages. By experiment, the valence state of an element was found to be at low levels in its soil extract, and there is no correlation with its gross in soil.
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