高效液相色谱-电感耦合等离子体质谱法测定海鱼中无机砷

目的建立测定海鱼中无机砷含量的高效液相色谱-电感耦合等离子体质谱法。方法海鱼样品经稀硝酸超声热水浴提取后,AS7阴离子交换色谱柱分离,3.5 mmol/L(NH4)2CO3+1%甲醇与100 mmol/L(NH4)2CO3+1%甲醇流动相梯度洗脱,电感耦合等离子体质谱仪测定,以保留时间定性,外标法定量。结果在1~100μg/L的线性范围,6种砷形态化合物的回归方程均呈良好的线性关系,相关系数均优于0.9996,检出限为0.05~0.25μg/L,定量限为0.17~0.84μg/L,3个浓度加标回收率为88.5%~106.4%,相对标准偏差为2.5%~4.9%。结论本方法满足海鱼中无机砷含量的测定要求,提取快速,稳定,操作简单,检出限低,方法的重现性好,灵敏度高。     

高效液相色谱-电感耦合等离子体质谱法同时测定PM2.5中5种形态砷浓度

[背景]慢性吸入性低浓度砷暴露可能产生远期健康效应.砷化物慢性吸入的危害与其形态及浓度有关,需要建立一种高效、灵敏、准确的多种形态砷的浓度检测方法.[目的]通过优化色谱条件和提取条件,采用高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)联用技术建立同时测定PM2.5中砷甜菜碱(AsB)、二甲基胂酸(DMA)...     

尿液中6种砷形态化合物测定的高效液相色谱-电感耦合等离子体质谱法

目的建立高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)法检测尿液中亚砷酸盐、砷酸盐、一甲基砷、二甲基砷、砷胆碱和砷甜菜碱6种砷形态化合物的方法, 为职业性砷中毒患者的健康评估提供依据。方法采用Hamilton PRP-X100阴离子分析柱, 以磷酸铵溶液为流动相, 梯度洗脱分离, 进行HPLC-ICP-MS分析。结果本方法6种砷形态化合物线性关系良好, 相关系数均大于0.999, 方法检出限为0.46～0.57 μg/L, 方法定量下限为1.52～1.91 μg/L, 加标回收率为96.5%～106.4%, 批内相对标准偏差为2.9%～6.2%, 批间相对标准偏差为3.8%～8.7%。结论所建立方法灵敏度和准确度高, 检测速度快, 可用于职业接触人群尿液中砷形态的测定。     

微波辅助提取-高效液相色谱-电感耦合等离子体质谱法测定干食用菌中6种砷形态

目的 建立干食用菌中砷胆碱（AsC）、砷甜菜碱（AsB）、亚砷酸根[As(III)]、二甲基砷（DMA）、一甲基砷（MMA）和砷酸根[As(V)]的微波辅助提取-高效液相色谱-电感耦合等离子体质谱测定方法。方法 经粉碎的干食用菌样品经1%硝酸为提取液,于100℃微波提取20 min,提取液离心、上清液经0.22 μm滤膜过滤后测定。采用Hamilton PRP - X100为分离柱,以0.1 mol/L碳酸铵(含2%甲醇）- 2%甲醇为流动相梯度洗脱。结果 方法检出限均低于0.3 μg/L,在0.5-100 μg/L范围内,线性相关系数（r）均大于0.999 5,加标回收率在97.4%～105%之间,RSD小于5%。结论 本法方法简便、快速,适用于食用菌中6种砷形态的分析。     

高效液相色谱-动态反应池-电感耦合等离子体质谱法测定海产品中砷形态

目的 建立HPLC-DRC-ICP-MS法准确测定海产品中砷甜菜碱(AsB)、二甲基砷(DMA)、一甲基砷(MMA)和无机砷[As(Ⅲ)和As(V)]等砷形态的含量.方法 海产品经1％硝酸溶液提取和HLB固相萃取柱净化后,经HPLC-DRC-ICP-MS法测定海产品中的砷形态.结果 以Dionex IonPak AS1...     

基于液相色谱-电感耦合等离子体质谱法测定食品中无机砷方法的改进

目的改进GB 5009.11—2014《食品中总砷及无机砷的测定》中基于HPLC-ICP-MS测定无机砷液相色谱流动相条件和程序。方法采用多种流动相及程序对比法,确定最佳流动相条件。结果采用国标法等度洗脱流动相条件,在分离度不高的离子色谱柱上无法实现二甲基砷(DMA)和三价无机砷(AsO_2~-)分离。采用切换流动相方法可实现AsO_2~-、五价无机砷(AsO_3~-)、一甲基砷(MMA)、DMA、砷甜菜碱(AsB)分离,并在900s内完成无机砷分离检测。结论使用切换不同流动相方法分离检测无机砷,分离度高,分析时间短,易于在基层工作中普及。     

高效液相色谱-电感耦合等离子体质谱法测定鱼肉中的3种汞形态

目的利用高效液相色谱与电感耦合等离子体质谱联用技术的高灵敏度和低检出限,建立鱼肉中3种汞形态的高效液相色谱(HPLC)-电感耦合等离子体质谱(ICP-MS)法。方法样品用25%四甲基氢氧化铵溶液微波提取法,流动相定容,C18反相色谱柱分离,电感耦合等离子体质谱检测。结果在600 s内可成功分离3种形态的汞化合物,甲基汞(Me Hg+)、无机汞(Hg2+)和乙基汞(Et Hg+)的浓度为0.05μg/L~1.00μg/L时,线性关系良好,相关系数(r)≥0.999 7,方法的检出限为0.002 5μg/L~0.005 0μg/L。在低、中、高3种浓度下,方法回收率为93.0%~103.3%。结论该方法操作简便、实用性强、结果可靠,可以用于鱼肉中低含量汞形态的检测。     

电感耦合等离子体质谱法测定尿中砷分析质量控制

目的 了解实验室砷检测能力和质量控制水平,提高实验室检测结果的准确性和可比性.方法 参照水质分析质量控制程序,用电感耦合等离子体质谱法对尿中砷的测定进行分析误差预测.结果 各种溶液测定的总标准差(st)均小于其水平的5％(W),总平均回收率可信限(R/d =0.97)在允许范围内,质量控制考核结果为满意.结论 用电感耦合等离子体质谱法测定尿中砷,实验室分析误差可控制在容许值内.     

电感耦合等离子体质谱法测定人体唾液中的砷

目的:建立操作简便、快速的测定唾液中总砷含量的方法。方法:用1.0%的硝酸将唾液样品稀释处理,利用ICP-MS在CCT模式下,检测唾液中的总砷。结果:砷浓度在0.048μg/L～80μg/L范围内呈现良好的线性,回归方程为Y=244.88X+0.5449,相关系数r=0.9998,检出限为0.048μg/L,相对标准偏差为2.86%～5.03%,回收率93.7%～109.2%。结论:该法具有检出限低、灵敏度高、精密度好等优点,为砷暴露的无创检测提供了可能。     

谷类食品中硒形态超声酶提取-高效液相色谱-电感耦合等离子体质谱法测定

目的采用高效液相色谱–电感耦合等离子体质谱法研究谷类食品中的硒形态。方法采用Hamilton PRP-X100阴离子交换柱作为分析柱,40 mmol/L磷酸氢二铵[(NH₄)₂HPO₄](pH=5.0)和60 mmol/L[(NH₄)₂HPO₄](pH=6.0)为流动相,梯度洗脱,硒代胱氨酸(SeCys₂)、甲基硒代半胱氨酸(MeSeCys)、亚硒酸盐[Se(Ⅳ)]、硒代蛋氨酸(SeMet)和硒酸盐[Se(Ⅵ)]可在16 min内实现基线分离。采用超声辅助酶提取法对谷类食品进行预处理。结果 SeCys₂、MeSeCys、Se(Ⅳ)、SeMet和Se(Ⅵ)的方法检出限分别为2.5、5.0、2.5、10.0和5.0μg/kg;0.5～200.0μg/L范围内,线性相关系数(r)均> 0.999,线性关系良好。结论谷类食品中的硒形态主要以硒代蛋氨酸为主,同时含有少量硒代胱氨酸、无机硒及一些未知的硒化合物。     

离子色谱-氢化物发生原子荧光法测定尿中形态砷

目的:建立离子色谱-氢化物发生原子荧光法测定尿中形态砷的方法。方法:尿样经0.45μm滤膜过滤,以(NH4)2HPO4为流动相,采用离子色谱-氢化物发生原子荧光联机测定不同形态砷的含量。结果:实验结果相关性好,线性范围宽,精密度RSD为2.60%～4.30%,方法检出限为As(Ⅲ)2.0μg/L,DMA4.0μg/L,MMA4.0μg/L,As(Ⅴ)8.0μg/L,该方法所得回收率为90.48%～102.90%。结论:方法简便、快速、无需化学预处理、干扰少、灵敏度高,有较高的实用价值。     

HPLC-ICP-MS speciation analysis of arsenic in urine of Japanese subjects without occupational exposure

The toxicity and carcinogenicity of arsenic depend on its species. Individuals living in Japan consume much seafood that contains high levels of organoarsenics. Speciation analysis of urinary arsenic is required to clarify the health risks of arsenic intake. There has been no report of urinary arsenic analysis in Japan using high performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). We performed speciation analysis of urinary arsenic for 210 Japanese male subjects without occupational exposure using HPLC-ICP-MS. The median values of urinary arsenics were as follows: sodium arsenite (AsIII), 3.5; sodium arsenate (AsV), 0.1; monomethylarsonic acid (MMA), 3.1; dimethylarsinic acid (DMA), 42.6; arsenobetaine (AsBe), 61.3; arsenocholine, trimethylarsine oxide, and unidentified arsenics (others), 5.2; and total arsenic (total As), 141.3 microgAs/l. The median creatinine-adjusted values were as follows: AsIII, 3.0; AsV, 0.1; MMA, 2.6; DMA, 35.9; AsBe, 52.1; others 3.5; and total As, 114.9 microgAs/g creatinine. Our findings indicate that DMA and AsBe levels in Japan are much higher than those found in Italian and American studies. It appears that the high levels of DMA and AsBe observed in Japan may be due in part to seafood intake. ACGIH and DFG set the BEI and BAT values for occupational arsenic exposure as 35 microgAs/l and 50 microgAs/l, respectively, using the sum of inorganic arsenic (iAs), MMA, and DMA. In the general Japanese population, the sums of these were above 50 microgAs/l in 115 (55%) samples. We therefore recommend excluding DMA concentration in monitoring of iAs exposure.     

尿中砷原子荧光法测定的研究

目的　建立尿中砷的氢化物原子荧光测定方法。方法　按照《生物材料分析方法的研制准则》的要求进行实验室实验及现场实验 ,研究了酸度、硼氢化钾浓度、载气及屏蔽气流速等因素对测定的影响。结果　尿砷含量在 0 .0～ 16 0 .0 μg L范围内呈线性关系 ,线性相关系数大于 0 .9990 ,本法检出限为 0 .32 1μg L(取尿样 5ml)。对尿砷含量为 10 .0、4 0 .0、80 .0、16 0 .0 μg L的配制样 ,测得方法相对标准偏差 (RSD )为 0 .87%～ 1.75 % ,标准加入回收率为 95 %～ 10 5 % ,样品在 4℃下可保存 2周。结论　该方法各项指标均达到《生物材料分析方法的研制准则》的要求 ,适用于职业接触的劳动者尿中砷的检测。     

测定尿中砷的微机消解-原子荧光光谱法

目的为开展正常人群尿砷水平调查和职业接触人群的接触水平调查建立快速、准确的检验方法。方法尿样经微机消解仪批量消解,原子荧光光谱法测定尿中砷。结果溶液浓度在0—40μg/L范围内标准曲线线性良好,r=0．9991,样品RSD％为2．26％-2．99％,样品的加标回收率为95．65％-102．5％,方法的检出限为0．046μg/L。结论采用常用设备微机消解仪一次能消解60份样品,样品前处理简单快捷,且具有较好的准确度、灵敏度,适合大批样品的普查检验。     

血液和尿液中砷的原子荧光光度测定法

目的探讨血液和尿液中砷的最佳测定方法。方法采用微波消解氢化物发生原子荧光光度法测定血液和尿液中的砷。结果在最佳条件下砷的最低检出限为0.076 8μg/L,砷回收率为89.0%～103.7%,RSD为2.4～5.1%。结论该方法具有简便,快速,灵敏度高,干扰少,线性范围宽等优点。     

Comparison of different medical cases in urinary arsenic speciation by fast HPLC-ICP-MS

The inorganic arsenic species As(III), As(V) and the organic species methylarsonate (MMA(V)), dimethylarsinate (DMA(V)) and arsenobetaine (AsB) were determined in human urine by a fast anion exchange HPLC-ICP-MS method, which was developed for clinical laboratories with high sample throughput. This paper compares typical chromatograms of the arsenic species in urine samples collected in different medical cases, for example, for the non-exposed population, for environmentally (plant protectants) and occupationally (glass manufacture) exposed persons, for a person after a failed suicide attempt with As2O3 and for persons before and after administration of the antidot sodium 2,3-dimercapto-1-propane-sulfonate (DMPS). Concentration data of the urinary As species for the non-exposed German population (n=82) are compared with the concentrations before and after administration of DMPS (n=37). For the non-exposed group the toxicologically relevant As in urine consists of 81% DMA(V), 10% MMA(V) and 9% inorganic As. However, a few hours after an acute intoxication with inorganic As this distribution changes dramatically and As(III) and As(V) are predominantly found in urine. After treatment with DMPS the total As concentration increases significantly and mainly MMA(V) and As(III) were found in urine samples.     

湿法消化—氢化物原子荧光法测定尿中砷

目的:建立一种准确简单易于普及的测定尿中砷的检测方法。方法:样品用混合酸在电热板上加热消解后,用硫脲抗坏血酸将五价砷预还原为三价砷,再用硼氢化钾作还原剂,以5%HNO3为介质,用AFS-230E原子荧光光度计直接测定。结果:在最佳实验条件下,砷的浓度在0.0μg/L~20.0μg/L之间线性关系良好,相关系数r=0.9999,方法的最低检出限为0.164μg/L,RSD为0.4%~1.2%,加标回收率为98.6%~103.5%。结论:该方法操作简单,精密度好,回收率高,是测定尿砷含量的可靠方法。     

Determination of monomethylarsonous acid, a key arsenic methylation intermediate, in human urine

In this study we report on the finding of monomethylarsonous acid [MMA(III)] in human urine. This newly identified arsenic species is a key intermediate in the metabolic pathway of arsenic biomethylation, which involves stepwise reduction of pentavalent to trivalent arsenic species followed by oxidative addition of a methyl group. Arsenic speciation was carried out using ion-pair chromatographic separation of arsenic compounds with hydride generation atomic fluorescence spectrometry detection. Speciation of the inorganic arsenite [As(III)], inorganic arsenate [As(V)], monomethylarsonic acid [MMA(V)], dimethylarsinic acid [DMA(V)], and MMA(III) in a urine sample was complete in 5 min. Urine samples collected from humans before and after a single oral administration of 300 mg sodium 2,3-dimercapto-1-propane sulfonate (DMPS) were analyzed for arsenic species. MMA(III) was found in 51 out of 123 urine samples collected from 41 people in inner Mongolia 0-6 hr after the administration of DMPS. MMA(III )in urine samples did not arise from the reduction of MMA(V) by DMPS. DMPS probably assisted the release of MMA(III) that was formed in the body. Along with the presence of MMA(III), there was an increase in the relative concentration of MMA(V) and a decrease in DMA(V) in the urine samples collected after the DMPS ingestion.