高效液相色谱-电感耦合等离子体质谱法分析生猪粪便中7种砷形态
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摘要
为了建立了高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)法测定生猪粪便中亚砷酸盐As(Ⅲ)、砷酸盐As(Ⅴ)、一甲基砷(MMA)、二甲基砷(DMA)、对氨基苯胂酸(p-ASA)、硝羟苯胂酸(ROX)和卡巴胂(carbarsone)7种砷形态,采用1 mmol/L K_2CO_3溶液:甲醇(90∶10,V/V)作为提取剂超声水浴提取样品,以DionexIonPac AS7作为分析柱,(NH_4)_2CO_3溶液作为流动相梯度洗脱,对生猪粪便中的砷形态化合物进行分析测定。结果显示:7种砷形态化合物在19 min以内达到基线分离,标准曲线线性相关系数(R~2)均大于0.999,方法的检出限为0.004～0.014 mg/kg,RSD均小于5%,平均回收率为81.6%～107.0%。通过对实际样品的分析,生猪粪便中砷主要以As(Ⅲ)、As(Ⅴ)和DMA等形态存在,常用的有机砷制剂检测出了p-ASA。
A sensitive and rapid method using high performance liquid chromatography-inductively coupled plasma mass spectrometry(HPLC-ICP-MS) was developed here for simultaneous determination of seven kinds of arsenic types, As(Ⅲ), As(Ⅴ), MMA, DMA, p-ASA, ROX and carbarsone in swine waste. Ultrasonic water bath was used to pretreat the samples with 1 mmol/L K_2CO_3-methanol(90:10,V/V) as the extraction agent. DionexIonPac AS7 anion exchange column and(NH_4)_2CO_3 solution were used to analyze the arsenic species in swine waste. The results showed that the seven arsenic species reached baseline separation within 19 minutes. The linear ranges were all between 1 and 300 μg/L with linear coefficients of over 0.999, and the detection limits were between 0.004 and 0.014 mg/kg. The relative standard deviations(RSD) for the determination of the seven species were less than 5% and the recoveries were between 81.6% and 107.0%. Analysis of the actual samples indicated that As(Ⅲ), As(Ⅴ) and DMA were detected in feed, the arsenic species in swine wastes existed mainly in the form of As(Ⅲ), As(Ⅴ) and DMA, and p-ASA was detected in commonly used organic arsenic preparations.
A sensitive and rapid method using high performance liquid chromatography-inductively coupled plasma mass spectrometry(HPLC-ICP-MS) was developed here for simultaneous determination of seven kinds of arsenic types, As(Ⅲ), As(Ⅴ), MMA, DMA, p-ASA, ROX and carbarsone in swine waste. Ultrasonic water bath was used to pretreat the samples with 1 mmol/L K_2CO_3-methanol(90:10,V/V) as the extraction agent. DionexIonPac AS7 anion exchange column and(NH_4)_2CO_3 solution were used to analyze the arsenic species in swine waste. The results showed that the seven arsenic species reached baseline separation within 19 minutes. The linear ranges were all between 1 and 300 μg/L with linear coefficients of over 0.999, and the detection limits were between 0.004 and 0.014 mg/kg. The relative standard deviations(RSD) for the determination of the seven species were less than 5% and the recoveries were between 81.6% and 107.0%. Analysis of the actual samples indicated that As(Ⅲ), As(Ⅴ) and DMA were detected in feed, the arsenic species in swine wastes existed mainly in the form of As(Ⅲ), As(Ⅴ) and DMA, and p-ASA was detected in commonly used organic arsenic preparations.
引文
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[11] 潘寻,韩哲,贲伟伟.山东省规模化猪场猪粪及配合饲料中重金属含量研究[J].农业环境科学学报,2013,32(1):160-165.
[12] 茹淑华,苏德纯,张永志,等.河北省集约化养殖场畜禽粪便中重金属含量及变化特征[J].农业资源与环境学报,2016,33(6):533-539.
[13] Styblo M,Yamauchi H,Thomas D J.Comparative in vitro methylation of trivalent and pentavalent arsenicals[J].Toxicol Appl Pharmacol,1995,135:172-178.
[2] 吴永梅,彭海燕.中山市畜禽粪便污染负荷及风险评价研究[J].家畜生态学报,2013,34(2):63-68.
[3] 张树清,张夫道,刘秀梅,等.规模化养殖畜禽粪便主要有害成分测定分析研究[J].植物营养与肥料学报,2005,11(6):822-829.
[4] 陈保卫,那仁满都拉,吕美玲,等.砷的代谢机制、毒性和生物监测[J].化学进展,2009,21(2/3):474-482.
[5] 肖亚兵,张曼,温华蔚.加速溶剂萃取-液相色谱-原子荧光法同时测定动物源性食品中阿散酸、硝苯砷酸与洛克沙胂的残留量[J].光谱学与光谱分析,2014,34(4):1100-1103.
[6] 刘崴,杨红霞,胡俊栋,等.高效液相色谱-电感耦合等离子体质谱法测定土壤中砷形态[J].分析试验室,2015,34(5):529-532.
[7] 刘成新,肖志明,贾铮,等.液相色谱-氢化物发生原子荧光光谱法测定饲料中砷的形态[J].分析化学,2018,46(4):537-542.
[8] 中华人民共和国卫生部.GB/T 5009.11-2014食品中总砷及无机砷的测定[S].北京:中国标准出版社,2014.
[9] Li Y,Chen T.Concentration of additive arsenic in Beijing pig feeds and the residues on pig manures[J].Resour Conserv Recy,2005,45(4):356-367.
[10] 董占荣,陈一定,林咸永,等.杭州市郊规模化养殖场猪粪的重金属含量及形态[J].浙江农业学报,2008,20(1):35-39.
[11] 潘寻,韩哲,贲伟伟.山东省规模化猪场猪粪及配合饲料中重金属含量研究[J].农业环境科学学报,2013,32(1):160-165.
[12] 茹淑华,苏德纯,张永志,等.河北省集约化养殖场畜禽粪便中重金属含量及变化特征[J].农业资源与环境学报,2016,33(6):533-539.
[13] Styblo M,Yamauchi H,Thomas D J.Comparative in vitro methylation of trivalent and pentavalent arsenicals[J].Toxicol Appl Pharmacol,1995,135:172-178.