Discussion on the precision for determination of extractable heavy metals in soil by calcium chloride method
TIAN Kan, WANG Yao, WANG Wei, FENG Yuepeng, MA Xiaoshuang*
State Environmental Protection Key Laboratory of Pollutant Metrology and Reference Materials, Institute of Environmental Reference Materials of Ministry of Ecology and Environment, Beijing 100029, China
Abstract：The precision was the main technical index for quality control in laboratory test. Until now, the precision control indexes for the determination of extractable heavy metals in soil by calcium chloride method have not been established. The soil samples with five levels were prepared. The homogeneity test was performed from 15 bottles selected by stratified random sampling. The analysis results were evaluated by single-factor analysis of variance (ANOVA) method, and it was indicated that the homogeneity of five batches of soil samples was good. Eight laboratories were organized to participate in precision tests in determination of four extractable heavy metals (Cd, Cu, Ni and Zn) in soil by calcium chloride method. Statistical analysis was carried out according to the national standard method of GB/T 6379.2-2004 for Accuracy (trueness and precision) of measurement methods and results-Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method. Cochran criterion and Grubbs criterion were used to verify the consistency of precision and average of test data between units. The precision indexes such as reproducibility limit (r) and reproducibility limit (R) were evaluated. When the content of Cd, Cu, Ni and Zn was in range of 0.143-7.69, 0.40-24.7, 0.32-2.55 and 3.09-181 mg/kg, the repeatability limit was 0.013-0.32, 0.04-1.4, 0.02-0.11 and 0.18-7.8 mg/kg, and the reproducibility limit was 0.032-0.64, 0.10-5.8, 0.08-0.61 and 0.31-20 mg/kg, respectively. The repeatability limit, reproducibility limit and the content were analyzed by iterative regression statistics to obtain the function relationship between repeatability limit, reproducibility limit of analytical method and the content, and the preliminary experimental verification was conducted. The study provided scientific basis for laboratory quality control in analysis of extractable heavy metals in soil, and also provided data supports for the development of standard method.
田衎, 王尧, 王伟, 封跃鹏, 马小爽. 氯化钙法分析土壤中重金属可提取态的精密度探讨[J]. 冶金分析, 2021, 41(6): 62-70.
TIAN Kan, WANG Yao, WANG Wei, FENG Yuepeng, MA Xiaoshuang. Discussion on the precision for determination of extractable heavy metals in soil by calcium chloride method. , 2021, 41(6): 62-70.
[1] 王静,王斌,孙韧. TCLP法对天津市农田重金属生态风险评价[J].中国环境监测,2015,31(5):93-97. WANG Jing,WANG Bin,SUN Ren.Ecological risk assessment of heavy metals in farmland with toxicity characteristic leaching procedure[J].Environmental Monitoring in China,2015,31(5):93-97. [2] 熊婕,朱奇宏,黄道友,等.南方稻田土壤有效态镉提取方法研究[J].农业现代化研究,2018,39(1):170-177. XIONG Jie,ZHU Qihong,HUANG Daoyou,et al.Comparison of single extraction methods for assessing Cd availability in paddy soils in south China[J].Research of Agricultural Modernization,2018,39(1):170-177. [3] 谢飞,谷子欣,严妍.二乙三胺五乙酸-三乙醇胺-硝酸钙体系浸取土壤中8种重金属有效态[J].冶金分析,2020,40(2):12-17. XIE Fei,GU Zixin,YAN Yan.Extraction of eight available-state heavy metals in soil with diethyltriamine pentaacetic acid-triethanolamine-calcium nitrate system[J].Metallurgical Analysis,2020,40(2):12-17. [4] 章海波,骆永明,李远,等.中国土壤环境质量标准中重金属指标的筛选研究[J].土壤学报,2014,51(3):429-438. ZHANG Haibo,LUO Yongming,LI Yuan,et al.Screening of criteria for heavy metals for revision of the national standard for soil environmental quality of China[J].Acta Pedologica Sinica,2014,51(3):429-438. [5] 陈平,李曌,李俊龙.日本海洋环境质量标准体系现状及启示[J].环境与可持续发展,2012,37(6):69-76. CHEN Ping,LI Zhao,LI Junlong.Overview on the formation process and current situation of soil environmental quality standard system of Japan[J].Envionment and Sustainable Development,2012,37(6):69-76. [6] 杨梦丽,叶明亮,马友华,等.基于重金属有效态的农田土壤重金属污染评价研究[J].环境监测管理与技术,2019,31(1):10-13. YANG Mengli,YE Mingliang,MA Youhua,et al.Review on heavy metal pollution evaluation in farmland soil based on bioavailable form of heavy metal[J].The Administration and Technique of Environmental Monitoring,2019,31(1):10-13. [7] 朱维晃,杨元根,毕华,等.海南土壤中Zn、Pb、Cu、Cd四种重金属含量及其生物有效性的研究[J].矿物学报,2004,24(3):239-244. ZHU Weihuang,YANG Yuangen,BI Hua,et al.Research on the total bioavailable concentrations and bioavailable of Zn, Pb, Cu and Cd in soils in Hainan province[J].Acta Mineralogica Sinica,2004,24(3):239-244. [8] 张红振,骆永明,章海波,等.土壤环境质量指导值与标准研究 Ⅴ.镉在土壤-作物系统中的富集规律与农产品质量安全[J].土壤学报,2010,47(4):628-638. ZHANG Hongzhen,LUO Yongming,ZHANG Haibo,et al.Study on soil environmental quality guidelines and standards V. modeling of cadmium uptake in soil-crop systems for human food safety in China[J]. Acta Pedologica Sinica,2010,47(4):628-638. [9] 环境保护部. HJ 804—2016土壤 8种有效态元素的测定 二乙烯三胺五乙酸浸提-电感耦合等离子体发射光谱法[S].北京:中国环境科学出版社,2016. [10] 环境保护部. HJ 803—2016土壤和沉积物 12种金属元素的测定 王水提取-电感耦合等离子体质谱法[S].北京:中国环境科学出版社,2016. [11] ZHU Q H,HUANG D Y,LIU S L,et al.Assessment of single extraction methods for evaluating the immobilization effect of amendments on cadmium in contaminated acidic paddy soil[J].Plant Soil and Environment,2012,58(2):98-103. [12] 颜世红,吴春发,胡友彪,等.典型土壤中有效态镉CaCl2提取条件优化研究[J].中国农学通报,2013,29(9):99-104. YAN Shihong,WU Chunfa,HU Youbiao,et al.Optimization of CaCl2 extraction of available cadmium in typical soils[J].Chinese Agricultural Science Bulletin,2013,29(9):99-104. [13] 闻向东,邵梅,曹宏燕.测量方法精密度共同试验测量数据的统计分析[J].中国无机分析化学,2014,4(1):69-75. WEN Xiangdong,SHAO Mei,CAO Hongyan.Statistic analysis of measurement data from cooperative experiments on method precision[J]. Chinese Journal of Inorganic Analytical Chemistry,2014,4(1):69-75. [14] 熊英,董亚妮,裴若会,等.锑矿石化学物相分析方法精密度的确定与评估[J].冶金分析,2017,37(3):13-20. XIONG Ying,DONG Yani,PEI Ruohui,et al.Precision determination and evaluation of antimony ore chemical phase analysis method[J]. Metallurgical Analysis,2017,37(3):13-20. [15] 张玉盛,蒋承琮,肖欢,等.一种土壤改良剂对土壤有效态镉及糙米镉含量的影响初探[J].中国稻米,2019,25(5):53-57. ZHANG Yusheng,JIANG Chengcong,XIAO Huan,et al.Preliminary study on the effects of soil modifier on available Cd in soil and cadmium content in brown rice[J].China Rice,2019,25(5):53-57. [16] 国家质量监督检验检疫总局,国家标准化管理委员会.GB/T 15000.3—2008 标准样品工作导则(3)标准样品定值的一般原则和统计方法[S].北京:中国标准出版社,2008. [17] 徐本平.精密度试验中的数据处理[J].冶金分析,2013,33(11):74-80. XU Benping.Data processing in the precision test[J].Metallurgical Analysis,2013,33(11):74-80. [18] 国家质量监督检验检疫总局,国家标准化管理委员会.GB/T 6379.2—2004/ISO 5725-2:1994 测量方法与结果的准确度(正确度与精密度)第2部分:确定标准测量方法重复性与再现性的基本方法[S].北京:中国标准出版社,2004. [19] 国家质量监督检验检疫总局,国家标准化管理委员会.GB/T 6379.6—2009/ISO 5725-6:1994 测量方法与结果的准确度(正确度与精密度)第6部分:准确度值的实际应用[S].北京:中国标准出版社,2009.
