Screening of Extractable Reagents for Heavy Metal Elements in the Detailed Survey of Soil Pollution in China
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摘要:
土壤重金属元素可提取态是衡量其生物有效性的重要指标,但其含量随着土壤酸碱性等环境条件的变化而改变,在提取土壤重金属元素可提取态时,不可避免地面临着提取剂与提取方法的选择。中国有关土壤重金属元素可提取态的标准分析方法或技术规范涉及的提取剂多达7种(pH=5.8盐酸溶液、0.1mol/L盐酸溶液、0.43±0.02mol/L硝酸溶液、0.11mol/L乙酸溶液、1mol/L硝酸铵溶液、0.005mol/L DTPA浸提剂、0.01mol/L氯化钙溶液),不同学者对不同提取剂有不同的研究结论,对于通用提取剂的系统研究未见报道。本文选择代表性农耕土壤样品,采用以上7种提取剂提取其中8种重金属元素(镉镍铜锌铬铅砷汞),电感耦合等离子体质谱法(ICP-MS)测定镉铬铜铅锌镍含量,原子荧光光谱法(AFS)测定砷和汞含量,对比了7种提取剂对各重金属元素的提取率,并研究了土壤酸碱性质对重金属元素提取率的影响。结果表明:①稀酸溶液对土壤重金属元素的提取率较高,且与土壤的酸碱性无关;② 1mol/L硝酸铵溶液虽然对镉的提取能力表征了镉在酸性土壤中的活性远大于碱性土壤的特点,但其对碱性土壤中铅的提取率大于镉;③DTPA提取剂对各重金属元素(尤其是铅、铜、锌)的提取率均显著高于0.01mol/L氯化钙溶液,且提取率随土壤酸碱性质的变化不显著;④0.01mol/L氯化钙溶液对镉的提取率最高,且与土壤酸碱性质密切相关,是土壤重金属元素可提取态较为理想的通用提取剂。
Abstract:BACKGROUND The extractable state of soil heavy metal elements is an important index to measure their bioavailability, but its content changes with soil acid-base properties and other environmental conditions. When determining which method to use for the extractable state of soil heavy metal elements, there are more than 7 kinds of extraction reagents involved in relevant standard methods or technical specifications. These include hydrochloric acid of pH=5.8, 0.1mol/L hydrochloric acid, 0.43±0.02mol/L nitric acid, 0.11mol/L acetic acid, 1mol/L ammonium nitrate solution, 0.005mol/L DTPA leaching agent, 0.01mol/L calcium chloride solution. Different scholars have different research conclusions on different extractants. There is no systematic research report on extractants suitable for different soil types.
OBJECTIVES To select and determine the general extractant suitable for the extractable state of heavy metal elements in soil with different acid-base properties.
METHODS Using typical farming soil samples as the research objective, 7 kinds of extracting agent were used to extract 8 heavy metals (Cd, Ni, Cu, Zn, Cr, Pb, As and Hg). Inductively coupled plasma-mass spectrometry (ICP-MS) was used to determine Cd, Cr, Cu, Pb, Zn, Ni, whereas atomic fluorescence spectrometry (AFS) was used to determine As and Hg. The extraction rates of 7 kinds of extractants were compared, and the effects of soil acid and alkali properties on the extraction rate of heavy metal elements were studied.
RESULTS Dilute acid solution had a strong ability of leaching heavy metals from soil, and it was not related to the acidity and alkalinity of the soil. Although the extraction ability of 1mol/L ammonium nitrate solution for cadmium indicated that the activity of cadmium in acidic soil was much higher than that in alkaline soil, its extraction rate of lead in alkaline soil was higher than that of cadmium. The extraction rate of DTPA extractant for soil heavy metal elements was significantly higher than that of 0.01mol/L calcium chloride solution, especially for lead, copper and zinc. Moreover, the extraction rate of DTPA extractant for soil heavy metal elements did not change significantly with soil acid-base properties. 0.01mol/L calcium chloride solution had the highest extraction rate of cadmium in soil, which was closely related to the acid-base properties of soil.
CONCLUSIONS 0.01mol/L calcium chloride solution is an ideal general extractant for the extractable state of soil heavy metal elements.
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表 1 不同稀酸溶液对土壤重金属元素的提取率
Table 1. Extraction rate of heavy metal elements in soil by different dilute acid solutions
样品编号 pH Cr提取率(%) Ni提取率(%) Cu提取率(%) Zn提取率数(%) 提取液① 提取液② 提取液③ 提取液① 提取液② 提取液③ 提取液① 提取液② 提取液③ 提取液① 提取液② 提取液③ GBW07943 8.37 0.48 5.37 3.85 1.09 27.0 18.2 4.46 29.3 29.3 1.37 35.6 21.4 GBW07944 8.18 0.37 6.41 5.34 0.27 25.0 16.7 2.56 29.8 29.8 0.39 31.8 15.3 GBW07945 8.34 0.17 6.56 4.87 2.25 29.4 19.1 9.93 30.3 30.3 1.61 39.6 18.0 GBW07946 8.50 0.20 5.91 4.42 0.58 26.8 19.5 5.20 40.8 40.8 0.61 34.5 16.9 GBW07947 8.24 0.39 7.75 5.64 1.16 30.2 22.1 3.89 29.6 29.6 1.91 38.6 21.2 GBW07412a 6.80 0.20 7.64 5.48 0.68 27.4 20.1 1.52 37.5 33.9 2.27 40.2 20.9 GBW07461 8.18 0.10 3.76 2.51 0.16 14.6 9.74 2.15 25.7 21.3 0.93 303 14.1 GBW07458 6.14 0.18 5.05 3.39 1.26 28.7 24.1 2.27 37.4 31.5 3.47 34.3 17.4 GBW07415a 6.18 0.11 3.19 2.71 0.40 9.03 5.25 1.52 32.0 31.9 1.87 23.1 11.8 GBW07416a 4.71 0.00 0.77 0.42 0.06 3.73 0.50 0.08 0.08 2.6 0.93 17.3 6.91 平均生物有效系数(%) - 0.22 5.24 3.86 0.79 22.18 15.52 3.36 29.2 28.1 1.54 32.5 16.4 样品编号 pH Cd提取率(%) Pb提取率(%) As提取率(%) Hg提取率数(%) 提取液① 提取液② 提取液③ 提取液① 提取液② 提取液③ 提取液① 提取液② 提取液③ 提取液① 提取液② 提取液③ HTSB-1 8.37 1.46 98.3 88.3 0.22 52.3 44.7 0.81 24.9 9.41 0.21 20.0 3.75 HTSB-2 8.18 2.47 50.0 60.0 0.05 41.4 28.3 0.37 17.2 11.6 0.26 28.2 0.95 HTSB-3 8.34 2.47 80.0 82.6 0.11 47.3 38.8 1.48 46.5 18.7 0.20 26.6 3.48 HTSB-4 8.50 2.11 85.9 78.9 0.12 47.3 35.4 0.67 29.4 9.26 0.33 19.5 2.09 HTSB-5 8.24 1.14 78.2 77.3 0.13 42.6 27.4 0.81 29.5 4.63 0.23 10.5 1.30 GBW07412a 6.80 4.82 46.4 52.7 0.42 55.7 35.4 0.26 21.0 10.6 0.72 100 1.50 GBW07461 8.18 3.40 66.0 73.1 0.11 65.5 52.6 0.16 20.7 6.38 0.42 26.8 0.79 GBW07458 6.14 21.18 54.6 63.6 0.33 55.2 32.8 0.10 14.4 2.83 0.48 41.0 1.43 GBW07415a 6.18 7.96 76.0 77.6 0.20 71.3 57.4 0.07 22.8 5.51 0.31 22.6 3.08 GBW07416a 4.71 16.36 42.4 49.4 0.02 40.8 35.6 0.01 1.39 0.24 0.08 40.5 27.3 平均生物有效系数(%) - 6.34 67.8 70.4 0.17 51.9 38.8 0.48 22.8 7.92 0.32 33.6 4.56 表 2 硝酸铵溶液和DTPA提取液对土壤重金属元素的提取率
Table 2. Extraction rate of heavy metal elements in soil by ammonium nitrate solution and DTPA
样品编号 pH Cr提取率(%) Ni提取率(%) Cu提取率(%) Zn提取率数(%) 提取液⑤ 提取液⑥ 提取液⑤ 提取液⑥ 提取液⑤ 提取液⑥ 提取液⑤ 提取液⑥ GBW07493 8.37 0.015 0.059 0.064 2.33 0.17 6.84 0.21 3.11 GBW07494 8.18 0.014 0.042 0.060 1.23 0.13 8.14 0.14 1.44 GBW07495 8.34 0.017 0.050 0.337 2.81 1.09 12.5 0.60 2.92 GBW07496 8.50 0.014 0.043 0.086 2.33 0.46 12.1 0.28 2.13 GBW07497 8.24 0.014 0.042 0.123 2.67 0.24 6.87 0.38 2.95 GBW07458 6.14 0.016 0.016 0.633 8.80 0.14 12.7 0.35 3.45 GBW07416a 4.71 0.028 0.009 0.334 0.28 0.13 0.85 1.43 0.77 平均生物有效系数(%) - 0.017 0.037 0.234 2.92 0.34 8.57 0.49 2.40 样品编号 pH Cd提取率(%) Pb提取率(%) As提取率(%) Hg提取率数(%) 提取液⑤ 提取液⑥ 提取液⑤ 提取液⑥ 提取液⑤ 提取液⑥ 提取液⑤ 提取液⑥ GBW07493 8.37 0.42 27.9 26.7 17.9 0.370 0.30 0.025 0.013 GBW07494 8.18 0.27 16.0 23.9 36.1 0.216 0.14 0.048 0.024 GBW07495 8.34 0.53 21.1 22.2 32.4 1.204 1.30 0.065 0.065 GBW07496 8.50 0.56 19.4 23.7 19.9 0.432 0.37 0.047 0.023 GBW07497 8.24 0.45 27.3 29.4 17.3 0.441 0.37 0.029 0.014 GBW07458 6.14 70.9 41.8 20.6 8.98 0.088 5.13 0.714 2.38 GBW07416a 4.71 46.9 21.0 17.9 11.5 0.773 1.06 1.455 0.91 平均生物有效系数(%) - 17.2 24.9 23.5 20.6 0.50 1.24 0.34 0.49 表 3 乙酸和氯化钙溶液对土壤重金属元素的提取率
Table 3. Extraction rate of heavy metal elements in soil by acetic acid and calcium chloride solution
样品编号 pH Cd生物有效系数(%) Cd生物有效系数(%) Ni生物有效系数(%) Pb生物有效系数(%) 提取液④ 提取液⑦ 提取液④ 提取液⑦ 提取液④ 提取液⑦ 提取液④ 提取液⑦ GXLZ-003 4.15 32.1 24.2 0.14 0.01 3.44 1.91 2.24 0.22 GXNN-020 6.05 33.1 29.3 0.14 0.01 2.84 1.4 0.45 0.035 GDSG-023 6.36 39.0 0.32 0.24 0.003 6.44 0.16 1.66 0.009 GZGY-002 6.53 20.5 0.20 0.04 0.02 1.14 0.54 1.05 0.014 SCMZ-004 6.53 28.9 8.25 0.05 0.01 2.74 0.76 0.2 0.034 SCSF-013 6.65 32.4 0.29 0.05 0.01 2.74 0.22 1.71 0.01 GZDF-024 7.41 28.9 0.60 0.06 0.02 1.28 0.44 2.15 0.017 SCMZ-002 7.48 51.7 37.0 0.06 0.02 2.52 7.94 4.23 0.36 SCSF-008 7.68 48.6 0.27 0.13 0.01 3.09 0.25 3.42 0.009 HNAY-003 7.75 50.6 0.21 0.15 0.00 3.68 0.83 3.35 0.018 HBBD-019 7.95 46.5 0.74 0.14 0.01 4.42 0.33 3.33 0.011 HBSJZ-002 8.02 24.8 3.37 0.11 0.003 2.06 0.63 9.22 0.007 平均生物有效系数(%) - 36.4 8.70 0.11 0.01 3.03 1.28 2.75 0.06 样品编号 pH Cu生物有效系数(%) Zn生物有效系数(%) As生物有效系数(%) Hg生物有效系数(%) 提取液④ 提取液⑦ 提取液④ 提取液⑦ 提取液④ 提取液⑦ 提取液④ 提取液⑦ GXLZ-003 4.15 6.46 0.48 5.4 0.06 1.27 0.06 0.38 0.02 GXNN-020 6.05 4.10 0.41 6.6 0.02 1.17 0.05 0.43 0.18 GDSG-023 6.36 4.89 0.69 20.4 0.04 1.15 0.07 0.29 0.07 GZGY-002 6.53 0.22 0.23 5.4 0.10 0.73 0.32 0.27 2.52 SCMZ-004 6.53 1.35 0.11 14.9 0.05 4.19 0.04 0.93 5.87 SCSF-013 6.65 2.35 0.14 24.1 0.02 2.57 0.11 0.16 0.003 GZDF-024 7.41 0.51 0.14 5.3 0.11 0.37 0.0006 0.66 0.02 SCMZ-002 7.48 1.38 0.28 15.6 0.16 2.24 0.74 0.1 0.02 SCSF-008 7.68 3.32 0.23 38.4 0.13 1.42 0.04 0.05 0.002 HNAY-003 7.75 2.40 0.2 9.4 0.18 13.3 0.6 0.59 0.06 HBBD-019 7.95 4.92 0.03 20.5 0.18 17.3 0.54 0.35 0.1 HBSJZ-002 8.02 7.11 0.02 5.3 0.04 3.27 0.11 1.82 0.34 平均生物有效系数(%) - 3.25 0.25 14.3 0.09 4.09 0.22 0.5 0.77 -
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