电感耦合等离子体质谱法分析海蟹中的砷元素分布特征
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摘要
分别采用电感耦合等离子体质谱(inductively coupled plasma mass spectrometry,ICP-MS)法和高效液相色谱-ICP-MS测定4种海蟹(青蟹、三疣梭子蟹、日本鲟和细点圆趾蟹)及其不同部位(胸肌肉、钳肉、肝胰腺、性腺(雌)和鳃)中总砷及砷形态分布特征。样品加酸、微波消解后采用ICP-MS法测定总砷;样品经稀硝酸溶液提取、正已烷脱脂净化后,采用Dionex IonPac AS19保护柱(50 mm×4 mm)及AS19阴离子交换柱(250 mm×4 mm,10μm)作为分析柱、pH 9.5的50 mmol/L碳酸铵溶液作为流动相等度洗脱的液相分离条件和优化后的ICP-MS条件,测定砷甜菜碱(arsenobetaine,AsB)、一甲基砷、二甲基砷、三价砷(As(Ⅲ))、五价砷(As(Ⅴ))5种砷形态含量。经方法优化后,5种砷化合物的标准溶液在0～300μg/L质量浓度范围内,呈现良好的线性关系(r2>0.998),检出限为0.008～0.014 mg/kg,定量限为0.025～0.055 mg/kg;在样品中添加0.4、1.0 mg/kg和2.0 mg/kg的水平下,加标回收率为70.0%～105.0%,相对标准偏差低于5%;158个海蟹类样品中总砷含量范围为0.37～35.81 mg/kg,整蟹及分部位的砷形态物测定数据表明海蟹体内均以毒性较低的AsB为主,AsB占其总砷含量的60.9%～99.4%,无机砷含量均值在0～0.12 mg/kg之间,无机砷含量均未超过国家标准限量值;总砷和AsB的含量基本都呈现出细点圆趾蟹<青蟹<三疣梭子蟹<日本鲟、同一品种下性腺(雌)>肝胰腺>蟹胸肌肉>蟹钳肉>蟹鳃的变化趋势,说明海蟹富集砷能力较强,性腺和肝胰腺是其砷富集的主要器官。
The distribution characteristics of total arsenic and arsenic species in four sea crabs(Scylla serrata, Portunus trituberculatus, Charybdis japonica and Ovalipes punctatus) and their different tissues(chest muscle, clamp meat, hepatopancreas and female gonad and gill) were studied by inductively coupled plasma mass spectrometry(ICP-MS) and high performance liquid chromatography-inductively coupled plasma mass spectrometry(HPLC-ICP-MS). Samples were acidified, digested in microwave and tested by ICP-MS for total arsenic. After samples were extracted with dilute nitric acid solution and degreased with n-hexane, an HPLC-ICP-MS method using a Dionex IonPac AS19 guard column(50 mm × 4 mm) and an AS19 anion exchange analytical column(250 mm × 4 mm, 10 μm) with 50 mmol/L carbon acid ammonium(pH 9.5) in isocratic elution as the mobile phase was used to analyze 5 arsenic species(AsB, MMA, DMA, As(III), and As(V)). The optimized method showed a good linear relationship over the concentration range of 0–300 μg/L(r2 > 0.998). The limits of detection(LOD) and the limits of quantity(LOQ) were 0.008–0.014 mg/kg and 0.025–0.055 mg/kg, respectively. The recovery rates at spiked levels of 0.4–2.0 mg/kg were 70.0%–105.0% with relative standard deviations(RSDs) smaller than 5%. Total arsenic contents in 158 sea crab samples were 0.37–35.81 mg/kg, and the analytical data of arsenic species in whole crabs and crab tissues showed that AsB, with low toxicity, was the main form of arsenic in sea crab, accounting for 60.9%–99.4% of the total arsenic. Additionally, average inorganic arsenic content was only 0–0.12 mg/kg in all samples, below the national standard limit. The contents of total arsenic and AsB in different sea crab species were in the ascending order of O. punctatus < S. serrata < P. trituberculatus < C. japonica, and those in different crab tissues were in the descending order of female gonad > hepatopancreas > chest muscle > clamp meat > gill. This research suggested that sea crabs have strong As accumulation ability, mainly in gonad and hepatopancreas.
The distribution characteristics of total arsenic and arsenic species in four sea crabs(Scylla serrata, Portunus trituberculatus, Charybdis japonica and Ovalipes punctatus) and their different tissues(chest muscle, clamp meat, hepatopancreas and female gonad and gill) were studied by inductively coupled plasma mass spectrometry(ICP-MS) and high performance liquid chromatography-inductively coupled plasma mass spectrometry(HPLC-ICP-MS). Samples were acidified, digested in microwave and tested by ICP-MS for total arsenic. After samples were extracted with dilute nitric acid solution and degreased with n-hexane, an HPLC-ICP-MS method using a Dionex IonPac AS19 guard column(50 mm × 4 mm) and an AS19 anion exchange analytical column(250 mm × 4 mm, 10 μm) with 50 mmol/L carbon acid ammonium(pH 9.5) in isocratic elution as the mobile phase was used to analyze 5 arsenic species(AsB, MMA, DMA, As(III), and As(V)). The optimized method showed a good linear relationship over the concentration range of 0–300 μg/L(r2 > 0.998). The limits of detection(LOD) and the limits of quantity(LOQ) were 0.008–0.014 mg/kg and 0.025–0.055 mg/kg, respectively. The recovery rates at spiked levels of 0.4–2.0 mg/kg were 70.0%–105.0% with relative standard deviations(RSDs) smaller than 5%. Total arsenic contents in 158 sea crab samples were 0.37–35.81 mg/kg, and the analytical data of arsenic species in whole crabs and crab tissues showed that AsB, with low toxicity, was the main form of arsenic in sea crab, accounting for 60.9%–99.4% of the total arsenic. Additionally, average inorganic arsenic content was only 0–0.12 mg/kg in all samples, below the national standard limit. The contents of total arsenic and AsB in different sea crab species were in the ascending order of O. punctatus < S. serrata < P. trituberculatus < C. japonica, and those in different crab tissues were in the descending order of female gonad > hepatopancreas > chest muscle > clamp meat > gill. This research suggested that sea crabs have strong As accumulation ability, mainly in gonad and hepatopancreas.
引文
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[20]陈绍占,刘丽萍,杜宏举,等.高效液相色谱-电感耦合等离子体质谱法分析经牛黄解毒片暴露后大鼠血清中砷形态[J].质谱学报,2017,38(2):177-186.
[21]ZHU M L,ZENG X C,JIANG Y X,et al.Determination of arsenic speciation and the possible source of methylated arsenic in Panax notoginseng[J].Chemosphere,2017,168:1677-1683.DOI:10.1016/j.chemosphere.2016.10.093.
[22]DUAN Y,GAN Y,WANG Y,et al.Arsenic speciation in aquifer sediment under varying groundwater regime and redox conditions at Jianghan Plain of Central China[J].Science of The Total Environment,2017,607:992-1000.DOI:10.1016/j.scitotenv.2017.07.011.
[23]KOMOROWICZ I,BARALKIEWICZ D.Determination of total arsenic and arsenic species in drinking water,surface water,wastewater,and snow from Wielkopolska,Kujawy-Pomerania,and Lower Silesia provinces,Poland[J].Environmental Monitoring and Assessment,2016,188(9):504.DOI:10.1007/s10661-016-5477-y.
[24]国家卫生和计划生育委员会.食品中总砷及无机砷的测定:GB 5009.11-2014[S].北京:中国标准出版社,2014.
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[27]吕超,刘丽萍,董慧茹,等.高效液相色谱-电感耦合等离子体质谱联用技术测定水产类膳食中5种砷形态的方法研究[J].分析测试学报,2010,29(5):465-468.
[28]张文德.海产品中砷的形态分析现状[J].中国食品卫生杂志,2007,19(4):345-350.
[29]陆奕娜,魏建华,许慨,等.高效液相色谱-电感耦合等离子体质谱法同时测定海产品中9种砷形态化合物[J].理化检验:化学分册,2017,53(9):1087-1093.
[30]MATHEWS V V,PAUL M V S,ABHILASH M,et al.Mitigation of hepatotoxic effects of arsenic trioxide through omega-3 fatty acid in rats[J].Toxicology and Industrial Health,2014,30(9):806-813.DOI:10.1177/0748233712463778.
[31]FRANCESCONI K A.Arsenic species in seafood:origin and human health implications[J].Pure and Applied Chemistry,2010,82(2):373-381.DOI:10.1351/PAC-CON-09-07-01.
[2]KALANTZI I,MYLONA K,SOFOULAKI K,et al.Arsenic speciation in fish from Greek coastal areas[J].Journal of Environmental Sciences,2017,56:300-312.DOI:10.1016/j.jes.2017.03.033.
[3]JIA Y,WANG L,MA L,et al.Speciation analysis of six arsenic species in marketed shellfish:extraction optimization and health risk assessment[J].Food Chemistry,2018,244:311-316.DOI:10.1016/j.foodchem.2017.10.064.
[4]胥佳佳,冯鑫,汤静,等.超声辅助提取-高相液相色谱-电感耦合等离子体质谱法测定香菇中6种形态砷化合物[J].食品科学,2016,37(24):216-221.DOI:10.7506/spkx1002-6630-201624034.
[5]陈保卫,CHRIS L X.中国关于砷的研究进展[J].环境化学,2011,30(11):1936-1943.
[6]王松,崔鹤,王境堂,等.南极磷虾油中总砷含量及砷形态分析[J].分析化学,2016,44(5):767-772.
[7]SUN M,LIU G,WU Q,et al.Speciation analysis of inorganic arsenic in coal samples by microwave-assisted extraction and high performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry[J].Talanta,2013,106:8-13.DOI:10.1016/j.talanta.2012.12.012.
[8]SAUCEDO-VElEZ A A,HINOJOSA-REYES L,VILLANUEVA-RODRIGUEZ M,et al.Speciation analysis of organoarsenic compounds in livestock feed by microwave-assisted extraction and high performance liquid chromatography coupled to atomic fluorescence spectrometry[J].Food Chemistry,2017,232:493-500.DOI:10.1016/j.foodchem.2017.04.012.
[9]徐章,胡红云,陈敦奎,等.磷酸提取-高效液相色谱-氢化物发生原子荧光光谱法分析垃圾焚烧飞灰中无机砷形态[J].分析化学,2015,43(4):490-494.
[10]王素芬,陈芳,王鹏,等.HPLC-HG-AFS联用技术检测蜂花粉中砷形态[J].食品科学,2013,34(12):189-193.DOI:10.7506/spkx1002-6630-201312039.
[11]ZHANG W,CHEN L,ZHOU Y,et al.Biotransformation of inorganic arsenic in a marine herbivorous fish Siganus fuscescens after dietborne exposure[J].Chemosphere,2016,147:297-304.DOI:10.1016/j.chemosphere.2015.12.121.
[12]WOLLE M M,CONKLIN S D.Speciation analysis of arsenic in seafood and seaweed:part II:single laboratory validation of method[J].Analytical and Bioanalytical Chemistry,2018,410(22):5689-5702.DOI:10.1007/s00216-018-0910-4.
[13]NAN K,HE M,CHEN B,et al.Arsenic speciation in tree moss by mass spectrometry based hyphenated techniques[J].Talanta,2018,183:48-54.DOI:10.1016/j.talanta.2018.02.055.
[14]KHAN N,RYU K Y,CHOI J Y,et al.Determination of toxic heavy metals and speciation of arsenic in seaweeds from South Korea[J].Food Chemistry,2015,169(1):464-470.DOI:10.1016/j.foodchem.2014.08.020.
[15]韩梅,赵国兴,李淑珍,等.毛细管电泳-电感耦合等离子体质谱法测定地下水中不同形态的砷[J].分析化学,2013,41(11):1780-1781.
[16]YANG G D,XU X Q,WANG W,et al.A new interface used to couple capillary electrophoresis with an inductively coupled plasma mass spectrometry for speciation analysis[J].Electrophoresis,2008,29(13):2862-2868.DOI:10.1002/elps.200700849.
[17]陈发荣,郑立,王志广,等.毛细管电泳-电感耦合等离子体质谱测定蓝点马鲛中砷化学形态[J].光谱学与光谱分析,2014,34(6):1675-1678.
[18]WOLLE M M,CONKLIN S D.Speciation analysis of arsenic in seafood and seaweed:part I:evaluation and optimization of methods[J].Analytical and Bioanalytical Chemistry,2018,410(22):5675-5687.DOI:10.1007/s00216-018-0906-0.
[19]NARUKAWA T,SUZUKI T,INAGAKI K,et al.Extraction techniques for arsenic species in rice flour and their speciation by HPLC-ICP-MS[J].Talanta,2014,130(2):213-220.DOI:10.1016/j.talanta.2014.07.001.
[20]陈绍占,刘丽萍,杜宏举,等.高效液相色谱-电感耦合等离子体质谱法分析经牛黄解毒片暴露后大鼠血清中砷形态[J].质谱学报,2017,38(2):177-186.
[21]ZHU M L,ZENG X C,JIANG Y X,et al.Determination of arsenic speciation and the possible source of methylated arsenic in Panax notoginseng[J].Chemosphere,2017,168:1677-1683.DOI:10.1016/j.chemosphere.2016.10.093.
[22]DUAN Y,GAN Y,WANG Y,et al.Arsenic speciation in aquifer sediment under varying groundwater regime and redox conditions at Jianghan Plain of Central China[J].Science of The Total Environment,2017,607:992-1000.DOI:10.1016/j.scitotenv.2017.07.011.
[23]KOMOROWICZ I,BARALKIEWICZ D.Determination of total arsenic and arsenic species in drinking water,surface water,wastewater,and snow from Wielkopolska,Kujawy-Pomerania,and Lower Silesia provinces,Poland[J].Environmental Monitoring and Assessment,2016,188(9):504.DOI:10.1007/s10661-016-5477-y.
[24]国家卫生和计划生育委员会.食品中总砷及无机砷的测定:GB 5009.11-2014[S].北京:中国标准出版社,2014.
[25]国家卫生和计划生育委员会.水产品抽样规范:GB/T 30891-2014[S].北京:中国标准出版社,2014.
[26]国家卫生和计划生育委员会.食品中污染物限量:GB 2762-2017[S].北京:中国标准出版社,2017.
[27]吕超,刘丽萍,董慧茹,等.高效液相色谱-电感耦合等离子体质谱联用技术测定水产类膳食中5种砷形态的方法研究[J].分析测试学报,2010,29(5):465-468.
[28]张文德.海产品中砷的形态分析现状[J].中国食品卫生杂志,2007,19(4):345-350.
[29]陆奕娜,魏建华,许慨,等.高效液相色谱-电感耦合等离子体质谱法同时测定海产品中9种砷形态化合物[J].理化检验:化学分册,2017,53(9):1087-1093.
[30]MATHEWS V V,PAUL M V S,ABHILASH M,et al.Mitigation of hepatotoxic effects of arsenic trioxide through omega-3 fatty acid in rats[J].Toxicology and Industrial Health,2014,30(9):806-813.DOI:10.1177/0748233712463778.
[31]FRANCESCONI K A.Arsenic species in seafood:origin and human health implications[J].Pure and Applied Chemistry,2010,82(2):373-381.DOI:10.1351/PAC-CON-09-07-01.