冬虫夏草及产区土壤中5种重金属及有害元素污染评价

目的：建立冬虫夏草及产区土壤中重金属及有害元素残留量的测定方法，并对污染水平进行评价。方法：采用电感耦合等离子体质谱（ICP-MS）法测定不同产地冬虫夏草及周围土壤中铅（Pb）、镉（Cd）、砷（As）、汞（Hg）、铜（Cu）的含量。射频功率为1 550 W，载气（高纯氩气）流速为1.05 L·min^-1，等离子气体流速为15.0 L·min^-1，蠕动泵转速0.2 r·s^-1，采样深度8 mm，积分时间为0.1 s。通过在线加入内标锗（Ge）、铟（In）、铋（Bi）元素的方法来校正基体效应和干扰。结果：冬虫夏草及土壤中5种重金属及有害元素的线性关系良好（r>0.99），回收率为80%~120%。采用单项污染指数法和内梅罗综合污染指数法对药材及产区土壤进行评价。根据GB15618-1995土壤环境质量标准一级规定，冬虫夏草产区土壤中5种重金属及有害元素平均单项污染指数由大至小顺序为Cd、As、Pb、Hg、Cu，其中Cd、As、Pb是主要的重金属及有害元素污染物，而Hg和Cu则基本不存在污染情况，8批土壤As、Cd、Pb存在超标的情况，其不合格率分别为88%、50%、25%；根据现行《中华人民共和国药典》2015年版植物药重金属及有害元素的限量标准，冬虫夏草药材5种重金属及有害元素平均单项污染指数由大至小顺序为As、Cu、Cd、Pb、Hg，其中As是主要的药材有害元素污染物，而Cu、Cd、Hg和Pb则不存在污染情况，5批次虫草As不合格率为100%；同时考察冬虫夏草不同部位As污染情况，发现As含量大部分集中在虫体，子座较少。结论：冬虫夏草及产区土壤中总砷含量水平较高，因此冬虫夏草总砷含量较高可能与其专属性富集砷特性密切相关；其他元素含量水平较低。

Objective:To establish a method for the determination of heavy metals and harmful element in Cordyceps and and its habitat's soil, and to evaluate the level of contamination.Methods:The contents of Pb, Cd, As, Hg and Cu in Cordyceps and the surrounding soil from different habitats were determined by ICP-MS.The RF power was 1 550 W and the flow rate of carrier gas was 1.05 L·min^-1.Plasma gas flow rate was 15.0 L·min^-1.Peristaltic pump speed was 0.2 r·s^-1 and the sampling depth was 8 mm.The integration time was 0.1 s.The real-time injection of internal standard solution with Ge, In and Bi was used to help calibration of matrix effects and interference.Results:5 heavy metals and harmful element in Cordyceps and soil showed good linear relationship (r>0.99), and the recovery rates were in the range of 80% to 120%.The result was evaluated by using the method of single factor pollution index and comprehensive pollution index.According to degree Ⅰ limit of the standard for soil environment (GB15618-1995), the average single pollution index order of 5 heavy metals and harmful element in producing soil was Cd > As > Pb > Hg > Cu, with Cd, As and Pb as the major contaminants.And there was almost no contamination of Hg or Cu.As, Cd and Pb in 8 batches of soil exceed the limits with failure rates of 88%, 50% and 25% separately.According to the limits of heavy metals and harmful elements in herbal medicine (Chinese Pharmacopoeia, 2015 edition), the average single pollution index order of 5 elements in medicinal Cordyceps was As > Cu > Cd > Pb > Hg, where As was the main contaminant.And there was almost no contamination of Cu, Cd, Hg and Pb.The failure rates of As in 5 batches of Cordyceps were 100%.At the same time, As pollution in different parts of Cordyceps was investigated.The result indicated that As was abundant in the parasites, but less in the sub-seat.Conclusion:The residue of total arsenic in Cordyceps and its habitat's soil was high.Total arsenic contamination in Cordyceps may be closely related to its enrichment characteristics.Residues of other elements were low in Cordyceps.

[1] 康帅,张继,林瑞超.冬虫夏草的性状和显微鉴定研究[J].药学学报,2013,48(3):428 KANG S,ZHANG J,LIN RC.Macroscopic and microscopic characteristics of Chinese caterpillar fungus[J].Acta Pharm Sin,2013,48(3):428
[2] 中华人民共和国药典2015年版.一部[S].2015:115 ChP 2015.Vol Ⅰ[S].2015:115
[3] 张家春,张珍明,刘涟,等.不同利用方式下贵州玄参产地土壤重金属含量与评价[J].耕作与栽培,2017,2(3):4 ZHANG JC,ZHANG ZM,LIU L,et al.The content and evaluation of soil heavy metal of Scrophulariaceae in Guizhou under different land use patterns[J].Till Cultivat,2017,2(3):4
[4] 颜慧,冯会,黄玮,等.丹参主要产地的土壤及药材重金属污染评价[J].中国农学通报,2012,28(4):288 YAN H,FENG H,HUANG W,et al.Evaluation for heavy metal pollution of soil and herb from the main producing area of Salvia miltiorrhiza Bge.in China[J].Chin Agric Sci Bull,2012,28(4):288
[5] 郭兰萍,黄璐琦,蒋有绪,等.药用植物栽培种植中的土壤环境恶化及防治策略[J].中国中药杂志,2006,31(9):714 GUO LP,HUANG LQ,JIANG YX,et al.Soil deterioration during cultivation of medicinal plants and ways to prevent it[J].China J Chin Mater Med,2006,31(9):714
[6] 魏春雁,刘笑笑,宋志峰,等.不同产地中药材及其栽培土壤中重金属含量比较研究[J].东北农业科学,2017,42(4):39 WEI CY,LIU XX,SONG ZF,et al.Comparison of heavy metal contents in Chinese herbal medicine and their cultivated soils from different habitats[J].J Northeast Agric Sci,2017,42(4):39
[7] RONKART SN,LAURENT V,CARBONNELLE P,et al.Speciation of five arsenic species(arsenite,arsenate,MMAAV,DMAAV and As-Bet) in different kind of water by HPLC-ICP-MS[J].Chemosphere,2007,66(4):738
[8] ZHAO R,ZHAO MX,WANG H,et al.Arsenic speciation in moso bamboo shoot-a terrestrial plant that contains organoarsenic spcies[J].Sci Total Environ,2006,371(1-3):293
[9] HE B,YUN ZJ,SHI JB,et al.Research progress of heavy metal pollution in China:sources,analytical methods,status,and toxicity[J].Chin Sci Bull,2013,58(2):134
[10] TURKEZ H,GEYIKOGLU F,TATAR A,et al.The effects of some boron compounds against heavy metal toxicity in human blood[J].Exp Toxicol Pathol,2012,64(1/2):93
[11] 段桂兰,王利红,陈玉,等.植物超富集砷机制研究的最新进展[J].环境科学学报,2007,27(5):714 DUAN GL,WANG LH,CHEN Y,et al.Recent developments in understanding the mechanisms of arsenic hyperaccumulation in plants[J].Acta Sci Circum,2007,27(5):714
[12] 饶宝娇.豆类植物中镉的测定及其对土壤镉的富集研究[J].广东化工,2017,14(44):110 RAO BJ.Determination of cadmium in legumes and research on the enrichment of cadmium in soil by leguminous plants[J].Guangdong Chem Ind,2017,14(44):110
[13] 罗文敏,林昌虎,杨万云,等.何首乌和种植土壤重金属含量特征及其相关性研究[J].湖北农业科学,2014,53(18):4354 LUO WM,LIN CH,YANG WY,et al.Assessment of heavy metals and correlation between polygonum and soils[J].Hubei Agric Sci,2014,53(18):4354
[14] 高安勤,何娇,何冠谛等.贵州土地整治项目区耕地土壤重金属含量特征及评价-以六枝特区岩脚镇为例[J].广东农业科学,2016,43(11):70 GAO AQ,HE J,HE GD,et al.Characteristics and contamination evaluation on cultivated soil heavy metals in consolidation project areas in Guizhou province:a case study on Yanjiao Town in Liuzhi District[J].Guangdong Agric Sci,2016,43(11):70
[15] 李彩虹,王彩艳,王晓静,等.宁夏道地黄芪重金属残留特征及污染评价[J].北方园艺,2016,40(21):171 LI CH,WANG CY,WANG XJ,et al.Residual characteristics and pollutional risk assessment of heavy metal in ningxia original Radix Astragali[J].Northern Horticult,2016,40(21):171
[16] 杜丽娟,米艳华,陈璐,等.药用植物三七对土壤中砷的吸收运转及形态转化[J].生态与农村环境学报,2016,32(6):997 DU LJ,MI YH,CHEN L,et al.Absorption,translocation and transformation of arsenic in medicinal herb Panax notoginseng-soil system[J].J Ecol Rural Environ,2016,32(6):997
[17] 张冬雪,丰来,罗志威,等.土壤重金属污染的微生物修复研究进展[J].江西农业学报,2017,29(8):62 ZHANG DX,FENG L,LUO ZW,et al.Research progress in microbial remediation of heavy metal pollution in soil[J].Acta Agric Jiangxi,2017,29(8):62
[18] 罗珍,刘元元,徐晓飞,等.铅砷在虫草菌丝体发酵中的迁移规律研究[J].现代食品科技,2012,28(8):936 LUO Z,LIU YY,XU XF,et al.Migiation behaviour of plumbum and arsenic on Cordyceps sinsesis fermentation[J].Mod Food Sci Technol,2012,28(8):936
[19] 孙鹏飞,李龙囡,丁晴.电感耦合等离子质谱法测定虫草及其制品的总砷及可吸收砷含量[J].中国药业,2017,26(7):27 SUN PF,LI LN,DING Q.Content determination of total and absorbable arsenic in Cordyceps sinensis and relevant products by ICP-MS[J].China Pharm,2017,26(7):27
[20] 曹晓钢,王君,李建民,等.HPLC-HG-AFS法分析西藏冬虫夏草中的砷形态化合物[J].中成药,2015,37(9):1985 CAO XG,WANG J,LI JM,et al.Analysis of arsenic speciations in Cordyceps sinensis in Tibet by HPLC-HG-AFS[J].Chin Tradit Pat Med,2015,37(9):1985