The Occurrences of Hg and Cd in Soils around Cities and Rivers and Their Ecological Risk Assessment
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摘要: 受人类活动和自然作用双重影响，土壤中重金属元素异常普遍存在，其中尤以城镇周边的Hg异常和大江河沿岸区域Cd异常最为典型。近年来，通常采用化学分步提取的方式，探讨土壤水溶态、离子交换态、有机态、铁锰氧化物态等形态中Hg、Cd等重金属元素含量的状况，进而分析其生态效应，但对土壤中Hg、Cd等重金属元素的自然存在形式缺乏深入探讨。本文以Hg、Cd两元素为重点，选择我国代表性城市和地区，采集城镇周边Hg异常区和江河沿岸Cd异常区的土壤样品，采用王水溶样原子荧光光谱法（AFS）测定Hg含量，采用盐酸-硝酸-氢氟酸-高氯酸溶样电感耦合等离子体质谱法（ICP-MS）测定Cd含量，同时配合其他相关实验手段，对Hg、Cd的自然存在形式进行解析；并以水稻中Hg、Cd含量为依据对Hg、Cd的生态效应进行了评价。结果表明：长春、南京、漳州和广州等城镇周边土壤Hg异常区Hg主体以硫化物形式存在，而且至少有一部分是以辰砂矿物形式存在，由此决定了土壤中Hg有效态在Hg全量中所占比例较小，土壤中Hg平均含量达到500μg/kg时，水稻籽实中Hg含量超过无公害食品标准的比例为3.4%，生态效应不甚敏感；长江、珠江等江河沿岸区域Cd异常区内Cd主要呈黏土吸附形式存在，由此导致50%左右的Cd以有效态形式存在，在土壤Cd全量中所占比例较大，当土壤中Cd平均含量达到1000μg/kg时，水稻籽实中Cd含量超过无公害食品标准的比例为43%，生态效应敏感。由此揭示出土壤中Hg、Cd等重金属元素生态效应敏感程度更直接地受到自然存在形式的影响。以辰砂矿物形式存在的Hg呈现“惰性”，不容易被农作物吸收，故生态效应不敏感；以黏土矿物吸附形式存在的Cd活动性更强，容易被农作物吸收，故生态效应敏感。Hg、Cd等重金属元素被农作物乃至人体吸收后，其存在形式及其转化特性是评估该元素是否存在生态风险的关键。Abstract:
BACKGROUNDThe ecological risk of heavy metal anomaly in soil is widespread due to human activities and natural processes. Hg anomaly in urban soil and Cd anomaly along rivers are the typical cases. Recently, the chemical sequential extraction method is widely used for Hg, Cd and other heavy metals to analyze the content of water-soluble fraction, exchangeable fraction, organic bound fraction, and ferric-manganese oxidation in soil. Normally the contents of different heavy metals at the above different chemical extraction forms constitute the basis for ecological effect evaluation. However, no further discussion has been conducted on the natural occurrences of Hg and Cd in soil. OBJECTIVESTo provide basis for studies on the key factors of ecological risk assessment. METHODSThe content of Hg was determined by atomic fluorescence spectrometry (AFS) after dissolution by aqua regia. The content of Cd was determined by inductively coupled plasma-mass spectrometry (ICP-MS) after digestion by hydrochloric acid-nitric acid-hydrofluoric acid-perchloric acid complexes. The existence forms of Hg were determined by chemical analysis, pyrolytic Hg method, heavy mineral identification, electronic probe and Raman spectrum. The existing forms of Cd were determined by AB-DTPA extraction, X-ray diffractometer and laser particle sizer analyzer. The ecological effects of Hg and Cd were evaluated based on the content of these elements in rice. RESULTSThe results show that sulfide was the main natural existence form of Hg in Hg anomaly soil around Changchun, Nanjing, Zhangzhou and Guangzhou. At least a part of Hg was in the form of cinnabar, which resulted in the relatively low percentage of bio-availability content to total content of Hg in soil. The proportion of rice grain with Hg content exceeding the standard of pollution-free food was only 3.4% when the average total content of Hg in soil was up to 500μg/kg. Cd in Cd anomaly area along the Yangtze River and the Pearl River presented as clay adsorption, resulting in about 50% Cd was bio-availability. The ratio of rice grain with Cd content exceeding the standard of pollution-free food was up to 43% when the average content of Cd in soil was 1000μg/kg. CONCLUSIONSThis reveals that the sensitivity of the ecological effects of heavy metal elements such as Hg and Cd in soil is more directly affected by naturally occurring forms. Hg in the form of cinnabar is 'inert' and is not easily absorbed by crops, so it is not sensitive to ecological effects. Cd in the form of clay mineral adsorption is more active and easily absorbed by crops, resulting in sensitive ecological effects. After the heavy metal elements such as Hg and Cd are absorbed by crops and even the human, their existence forms and their transformation characteristics are the keys to assess whether there is an ecological risk. -
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表 1 土壤样品测试项目及测试方法
Table 1. Analytical items and methods of soil samples
测试项目 测试方法 测试单位 土壤中Hg、Cd含量 Hg：原子荧光光谱法
Cd：电感耦合等离子体质谱法中国地质科学院地球物理地球化学勘查研究所中心实验室 土壤中Hg存在形态 离子交换态、有机物结合态、硫化物态 中国地质科学院地球物理地球化学勘查研究所中心实验室 土壤热释谱法 中国地质科学院地球物理地球化学勘查研究所项目组 辰砂矿物鉴定 电子探针、拉曼光谱法 中国地质科学院矿产资源研究所 土壤中Cd、Hg有效态 AB-DTPA法 中国地质科学院地球物理地球化学勘查研究所中心实验室 土壤矿物组成 X射线衍射法 国家建筑材料工业地质工程勘查研究院测试中心 土壤粒级组成 激光粒度仪 石油工业油田化学剂质量监督检验中心 水稻籽实中Hg、Cd含量 Hg：原子荧光光谱法
Cd：电感耦合等离子体质谱法中国地质科学院地球物理地球化学勘查研究所中心实验室 
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表 2 水稻根系土中Hg和Cd含量统计
Table 2. Hg and Cd content in rice root soils
试验区 Hg全量(μg/kg) 有效态Hg含量(μg/kg) 有效态Hg在Hg全量中的占比(%) Cd全量(μg/kg) 有效态Cd含量(μg/kg) 有效态Cd在Cd全量中的占比(%) 黑龙江—吉林 53(N=340) 0.23 0.4 122(N=340) 82 66.8 江苏 538(N=198) 0.82 0.15 234(N=198) 105 44.7 浙江—湖南 483(N=248) 0.72 0.15 1008(N=248) 475 47.1
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表 3 水稻中Hg和Cd食品卫生质量统计
Table 3. Food hygienic quality of Hg and Cd in rices
试验区 水稻中Hg含量(μg/kg) 所占比例(%) 水稻中Cd含量(mg/kg) 所占比例(%) Hg含量≤GS GS < Hg含量≤NS Hg含量>NS Cd含量≤GS GS < Cd含量≤NS Cd含量>NS 黑龙江—吉林 5.7(N=90) 92.2 6.7 1.1 0.011(N=90) 98.9 1.1 0 江苏 8.7(N=86) 71.6 25.0 3.4 0.035(N=86) 98.3 1.7 0 浙江—湖南 5.5(N=248) 94.0 6.0 0 0.47(N=248) 42.2 13.7 44.1 注：GS—绿色食品卫生标准，在此标准中，Hg限量为0.01mg/kg，Cd限量为0.1mg/kg；NS—无公害食品卫生标准，在此标准中，Hg限量为0.02mg/kg，Cd限量为0.2mg/kg。
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