工作场所空气中双氰胺的高效液相色谱法测定

目的 建立工作场所空气中双氰胺的滤膜采集高效液相色谱测定方法.方法 滤膜采集空气中双氰胺,用水洗脱,甲醇:水(1:99)为流动相,1 mL/min的流速经C18柱(250.0 mm×4.6 mm×5.0 μm,柱温30℃)分离,于213 nm处检测.结果 标准曲线线性范围0～10 mg/L,回归方程γ=411 805x+14 573,相关系数(r)=0.999 9,检出限36 μg/L,以采集75 L空气样品计,最低检出浓度4.8 μg/m3.方法 的相对标准偏差小于5%,洗脱效率为96.5%～103.1%,样品在室温下至少可稳定14 d.结论 本法可应用于工作场所空气中双氰胺浓度的检测.     

高效液相色谱法测定工作场所空气中的阿昔洛韦

目的 建立空气中阿昔洛韦的高效液相色谱检测方法。方法 空气中阿昔洛韦经滤膜采集后,用0.4%氢氧化钠溶液洗脱溶解,洗脱液经C₁₈色谱柱(250 mm×4.6 mm, 5μm)分离,采用甲醇-水流动相洗脱,紫外检测器(254 nm)检测,标准曲线法定量。结果 方法线性关系良好,相关系数为0.999 9,方法检出限为0.1μg/ml;定量限为0.3μg/ml;最低检出浓度(以采集150 L空气样品计)为6.6μg/m³。结论 本法简便,灵敏度高,重现性好,检测结果可靠,检测效率高,适用于工作场所空气中阿昔洛韦含量的测定。     

溶剂解吸-气相色谱法测定工作场所空气中二亚乙基三胺

目的建立工作场所空气中二亚乙基三胺的溶剂解吸-气相色谱检测方法。方法使用碱性硅胶管采样,用0.2 mol/L盐酸甲醇溶液解吸,离心后取上清液与0.3 mol/L氢氧化钾甲醇溶液中和,经5%-苯基-甲基聚硅氧烷(HP-5)毛细管色谱柱(25 m×0.32 mm×0.52 mm)分离,氢火焰离子化检测器测定。结果该方法检出限为0.49μg/mL,定量限为1.64μg/mL,定量测定范围为1.64~233.80μg/mL,最低定量检出浓度为0.22 mg/m^3(以采集7.5 L空气样品计);方法的重现性好,相对标准偏差为1.4%~3.3%,平均解吸效率为90.8%,平均采样效率为93.2%;200 mg碱性硅胶的穿透容量大于7.1 mg,样品在室温下至少可保存15 d;空气中共存的乙二胺、三亚乙基四胺、四亚乙基五胺在本法条件下不干扰测定。结论该方法检出浓度低、准确度高、精密度好,适用于工作场所空气中二亚乙基三胺的测定。     

气相色谱法测定工作场所空气中正丁基硫醇

目的 建立工作场所空气中正丁基硫醇的气相色谱测定方法.方法 工作场所空气中的正丁基硫醇用Tenax采样管采集,样品经甲醇解吸,毛细管气相色谱柱分离(30.00 m×0.32 mm ×3.00 μm),火焰离子化检测器检测,以保留时间定性,峰面积定量.结果 本法正丁基硫醇质量浓度在1.70 ～ 100.40 mg/L呈线性关系,相关系数为0.999 96,最低检出浓度为0.10 mg/m3(以采集3.0L空气样品计),精密度相对标准偏差为2.0％ ～2.8％,采样效率为98.7％ ～100.0％,平均解吸效率为91.9％,样品在-10℃冰箱中至少可保存7d.结论 本方法灵敏度高,精密度和准确度好、操作简便、易普及,可作为工作场所空气中正丁基硫醇的标准检测方法.     

液相色谱-原子荧光联用法测定全血中砷形态化合物

采用液相色谱-原子荧光联用法测定全血中亚砷酸盐(As^Ⅲ)、二甲基砷酸(DMA)、一甲基砷酸(MMA)和砷酸盐(As^Ⅴ)。萃取后的上清液经阴离子交换色谱柱分离，原子荧光检测定量。四种砷形态化合物的线性范围为0～500μg/L,检出限为10.0μg/L,低、中、高三个浓度加标样品平均回收率为78.4%～105.0%,相对标准偏差(RSD)为3.20%～9.12%。本文所建立的全血中四种砷形态化合物的检测方法简单、灵敏、准确，可应用于实际接触人群中砷形态化合物的检测。     

动物性海产品中砷形态分析方法的研究

目的 建立动物性海产品中砷甜菜碱(AsB)、亚砷酸盐(AsⅢ)、砷酸盐(AsⅤ)、二甲基砷酸(DMA)和一甲基砷酸(MMA)的液相色谱-在线紫外消解-氢化物发生-原子荧光光谱联用的测定方法(LC-UV-HG-AFS).方法 以90%甲醇为提取溶液,超声振荡提取后,提取液以N2浓缩至近干,加水溶解残渣后以正己烷萃取除去脂质成分,取下层清液,以超纯水定容至10 ml,过滤后进样分析;以0.2 mmol/L磷酸二氢铵(pH9.0)和20 mmol/L磷酸二氢铵(pH6.0)为流动相,梯度洗脱,以Hamilton PRPX-100柱分离,LC-UV-HG-AFS检测.结果 在给定的色谱条件下,AsB、AsⅢ、AsⅤ、DMA和MMA达到基线分离;各组分的检出限在0.0025～0.0032 mg/L之间,重复性和再现性＜10%,0.2 mg/kg添加水平的回收率＞85%;鱼、虾、贝样品中所含有的主要砷形态化合物为AsB,仅在某些贝类样品中检出微量AsⅢ和DMA;分别以定值参考物NBS 1566牡蛎组织和BCR 627金枪鱼考察总砷测定和砷形态分析的准确性,结果符合定值要求.结论 建立的LC-UV-HG-AFS方法适合于动物性海产品中砷形态化合物的特异性检测,测定结果准确可靠.     

工作场所空气中双氯甲醚气相色谱-质谱测定方法

目的建立工作场所空气中双氯甲醚(BCME)的气相色谱-质谱测定方法。方法空气中的BCME用活性炭管采集,乙酸乙酯解吸,经60.00 m×0.32 mm×1.00μm的DB-5MS色谱柱分离,质谱检测器检测,外标法定量。结果BCME在0.013 2～0.132 0 mg/L呈线性关系,相关系数为0.999 8,最低检出质量浓度为0.000 8 mg/m3(以采样7.5 L计),相对标准偏差(RSD)为3.4%～6.5%,采样效率为100.0%,100.0 mg的活性炭对BCME的穿透容量大于0.002 4 mg,不同质量浓度的平均解吸效率为89.73%～95.43%。样品在-8℃冰箱中至少可保存3 d。结论该方法各项指标均达到《工作场所有害物质监测方法》的要求,适用于工作场所空气中BCME的检测。     

大气颗粒物PM_(2.5)中16种多环芳烃的超高效液相色谱测定法

目的建立大气颗粒物PM_(2.5)中16种多环芳烃(PAHs)的超高效液相色谱-二极管阵列检测器测定法。方法空气样品滤膜经乙腈密封超声提取,以乙腈-水为流动相进行梯度洗脱,过Waters ACQUITY UPLC~BEH Shield RP18色谱柱(2.1 mm×150 mm,1.7μm),超高效液相色谱法测定,反相色谱法梯度淋洗分离后,二极管阵列检测器检测。结果在10~1 000μg/L的范围内,所得16种PAHs的回归方程均呈良好的线性关系良好(r0.999 9)。方法的检出限为0.5~6.0μg/L,平均回收率为88.9%~119.4%,RSD为0.3%~4.9%。结论该方法操作简单,灵敏高,分析速度快,适用于空气中16种PAHs的监测。     

工作场所空气中3,4-二硝基呋咱基氧化呋咱的高效液相色谱测定方法

目的建立工作场所空气中3,4-二硝基呋咱基氧化呋咱(DNTF)的高效液相色谱测定方法。方法采用ODSC18柱(4.6 mm×200 mm×5μm)仪器为美国HP1100型高效液相色谱仪,紫外检测器,波长为216 nm,流动相为甲醇∶水=60∶40,流速为1.0 ml/min。结果检测限为0.012μg/ml(进样10μl洗脱液),最低检出浓度为0.000 2 mg/m3(以采集150 L空气样品计)。回归方程为y=22.74x-56.05,相关系数r=0.999 5,高、中、低3个浓度的样品,6次重复测定,RSD为0.71%~1.28%,洗脱效率为94.08%~104.75%,方法的回收率为96.80%~100.11%;样品在室温至少可保存7 d;在该条件下与DNTF可能共存的三硝基甲苯、黑索今、奥克托今等不干扰测定。结论该方法各项指标均达到《工作场所空气中毒物检测方法的研制规范》的要求,适用于工作场所空气中3,4-二硝基呋咱基氧化呋咱的样品纯度的检测。     

中毒样品中敌鼠钠盐气相色谱-质谱联用法分析

目的建立气相色谱-质谱联用法(GC-MS)快速测定中毒样品中敌鼠钠盐的分析方法。方法样品经酸化处理后用乙酸乙酯提取,用HP-5MS交联弹性毛细管石英柱(30.00m×0.25mm×0.25μm)分离测定。结果方法测定敌鼠钠盐的线性范围为25.0～150.0mg/L,相关系数(r)=0.9994。按3倍信噪比计算,最低检出浓度全扫描模式下为0.40 mg/L,选择离子检测模式下为0.10 mg/L。结论本方法操作简单,分析速度快,灵敏度和准确度高,还可同时测定其他鼠药成分,完全能满足应急中毒样品的检测要求。     

地下水中无机砷的高效液相色谱-氢化物发生-原子荧光测定法

目的 建立地下水中无机砷(iAs~(3+)、iAs~(5+))的高效液相色谱.氢化物发生-原子荧光(HPLC-HG-AFs)测定法.方法 以磷酸氢二铵为流动相,在Hamilton PRP-X100阴离子交换柱上有效分离出水中iAs~(3+)和iAs~(5+),通过氢化物发生-原子荧光光谱仪测定iAs~(3+)和iA5+的含量.结果 在2～150μg/L线性范围内,iAs~(3+)的线性回归方程为y=159 280x-9515.9,r=0.9998,检出限为0.22μg/L;iAs~(5+)的线性回归方程为y=78 901x+53 737,r=0.999 2,检出限为0.75 μg/L.该方法所得iAs~(3+)的平均回收率为100.49%～102.05%,RSD为1.59%～3.69%;iAs~(3+)的平均回收率为99.08%～101.06%,RSD为1.83%～4.12%.该方法和氢化物发生.冷阱捕获.原子吸收法(HG-cold trap-AAS)测定地下水无机砷含量的结果比较,差异无统计学意义(P>0.05).结论 该方法线性范围宽、精密度高、稳定性好,适用于地下水样品中无机砷的测定.     

干法消化-原子荧光光谱法同时测定螺旋藻粉中砷和锑

目的建立干法消化和氢化物发生—原子荧光光谱法同时测定螺旋藻粉中砷和锑的方法。方法将螺旋藻粉干法消化后,利用氢化物发生—原子荧光光谱法同时测定砷和锑。对仪器条件进行了优化,比较了不同还原剂的增敏效果,考察了常见干扰离子对测定的影响。结果采用本方法测定,砷的线性范围为0～10μg/L,γ=0.9992,DL=0.16μg/L,回收率为96.0%～111.2%,精密度(RSD%)为2.37;锑的线性范围为0～10μg/L,γ=0.9998,DL=0.11μg/L,回收率为90.2%～109.0%,精密度(RSD%)为5.91。结论测定方法简单快捷,省时省力省试剂,结果准确,满足测定要求。     

氢化物发生—原子荧光光谱法(HG-AFS)测定食品中不同价态的无机砷

应用氢化物发生——原子荧光分析技术建立了食品中总无机砷、三价砷［Ａｓ（Ⅲ）］和五价砷［Ａｓ（Ⅴ）］的测定方法。用６ｍ ｏｌ／ＬＨＣｌ提取食品中无机砷,在２ｍ ｏｌ／ＬＨＣｌ条件下测定总无机砷,再利用三价砷、五价砷氢化物发生酸度条件的不同对三价砷进行选择测定。本方法标准曲线线性范围：总无机砷为０～４００μｇ／Ｌ,Ａｓ（Ⅲ）为０～３００μｇ／Ｌ;检出限：总无机砷１．６μｇ／Ｌ,Ａｓ（Ⅲ）１．１μｇ／Ｌ;相对标准偏差：总无机砷为１．９３％ ,Ａｓ（Ⅲ）为２．４９％ ;样品回收率：总无机砷为８５％ ～１０５％ ,Ａｓ（Ⅲ）为８０％ ～１１５％ ;一般食品样品的测定无干扰。     

氢化物发生—原子荧光光谱法测定中药中不同形态的砷

建立了一种氢化物发生—原子荧光光谱法测定中药中As(Ⅲ)、As(V)的方法。研究了仪器的工作条件、试剂浓度对砷原子荧光强度的影响以及五价砷的还原条件,探讨了共存离子对砷测定的干扰和消除方法。在最佳工作条件下,砷的检出限为0.0903μg/L,相对标准偏差为2.01%。将该法成功应用于3种中药样品中砷的形态分析,As(Ⅲ)和As(V)的回收率分别为90.8%～98.2%和89.2%～102.0%。建立的方法简便可行,可用于多种样品中砷的形态分析。     

大米中砷和汞的微波消解-原子荧光光谱测定法

目的建立双道原子荧光光谱法同时测定大米中的砷和汞的方法。方法采用微波消解法处理大米样品,以原子荧光光谱法同时测定其中的砷和汞。结果砷和汞的检出限分别为0.004 4、0.039μg/L;砷、汞标准溶液分别在1.0～20.0和0.10～1.20μg/L范围内线性良好,其相关系数分别为0.999 5、0.999 2;精密度RSD:测定含2.0μg/L砷和0.4μg/L汞的混合标准溶液的RSD分别为2.12%、4.59%。样品加标回收率:砷92.2%～96.8%,汞90.3%～92.1%。结论该方法灵敏度、准确度高,操作方便快速,具有较低的检出限,能满足同时测定大米中砷和汞含量的测定工作。     

Occurrence,speciation analysis and health risk assessment of arsenic in Chinese mitten crabs (Eriocheir sinensis) collected from China

Arsenic (As) is a major hazardous element in natural environments, and arsenic pollution is becoming an issue of concern worldwide. The more toxic inorganic arsenic, such as trivalent arsenite As(Ⅲ) and pentavalent arsenate As(Ⅴ), which normally can transform to organic arsenic compounds, such as arsenobetaine (AsB), arsenocholine (AsC), monomethyl arsenic acid (MMA), dimethyl arsenic acid (DMA), trimethyl arsenic acid (TMA), arsenosugars and arsenolipids. In this study, a total of 2130 individuals of Chinese mitten crabs were collected from seven locations and mixed to 71 samples. Total arsenic and six major species (AsC, AsB, DMA, MMA, As (Ⅲ), and As (Ⅴ)) were determined by inductively coupled plasma mass spectrometry (ICP-MS) and high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS), respectively. The target hazard quotient (THQ) was utilized to evaluate the human health risk. The total arsenic concentration and totals for the six arsenic forms are 0.25–1.66 mg/kg and 0.05–1.19 mg/kg wet mass, respectively. Except for HH and LH, the six arsenic species concentrations accounted for more than 50.0 % of the total arsenic. The less toxic AsB is the most predominant in crabs, comprising 50.0 %–90.0 % of the sum of six types of arsenic. The more toxic inorganic arsenic only range from 0.01 to 0.21 mg/kg wet mass, much less than the limit content of 0.50 mg/kg inorganic As in crustacea. The THQ values of inorganic arsenic through the consumption of Chinese mitten crabs are estimated, and the values are all less than 1, indicating that intaking Chinese mitten crabs collected from China will not cause an appreciable hazard risk to human health.     

工作场所空气中二苯胺的紫外分光光度测定法

目的 建立工作场所空气中二苯胺的紫外分光光度测定法.方法 用硫酸处理过的玻璃纤维滤膜采集空气中二苯胺,无水乙醇解吸后紫外分光光度法测定.结果 该方法的线性范围为0.19～60 mg/m~3(以采集15 L空气计算),回归方程y=0.13x-0.016,相关系数为0.9999,检出限0.28μg/ml(以吸光度为0.02计算),精密度为1.9%～8.4%,平均采样效率99%,平均洗脱效率为98%,穿透容量大于2.2 mg,样品在室温或冷藏条件均至少可保存10 d.结论 该方法适用于工作场所空气中二苯胺的测定.

Abstract：

Objective To establish a UV spectrophotometry method for determination of diphenylamine in air of workplaces.Methods The air samples were collected by glass fiber filter treated with sulfuric acid,desorbed with alcohol by ultrasonic for 10min,determined by UV spectrophotometry.Results The detection range of the method was 0.19-60 mg/m~3 (the air volume was15L).The regression equation:y=0.13x-0.016.The correlation coefficients was 0.999 9.The detection limit was 0.28μg/ml.The relative standard deviations was 1.9%-8.4%.Sample-collected efficiency was 99%,desorotion efficiency was 98%and the penetration capacitv was more than 2.2 mg.Sample stability was 10 days at least by being stored in a refrigerator at 4℃or by ambient storage.Conclusion This method is applicable to the determination of diphenylamine in air of workplaces.     

Assessment of occupational exposure to inorganic arsenic based on urinary concentrations and speciation of arsenic

An analytical speciation method, capable of separating inorganic arsenic (As (V), As (III] and its methylated metabolites (MMAA, DMAA) from common, inert, dietary organoarsenicals, was applied to the determination of arsenic in urine from a variety of workers occupationally exposed to inorganic arsenic compounds. Mean urinary arsenic (As (V) + As (III) + MMAA + DMAA) concentrations ranged from 4.4 micrograms/g creatinine for controls to less than 10 micrograms/g for those in the electronics industry, 47.9 micrograms/g for timber treatment workers applying arsenical wood preservatives, 79.4 micrograms/g for a group of glassworkers using arsenic trioxide, and 245 micrograms/g for chemical workers engaged in manufacturing and handling inorganic arsenicals. The maximum recorded concentration was 956 micrograms/g. For the most exposed groups, the ranges in the average urinary arsenic speciation pattern were 1-6% As (V), 11-14% As (III), 14-18% MMAA, and 63-70% DMAA. The highly raised urinary arsenic concentrations for the chemical workers, in particular, and some glassworkers are shown to correspond to possible atmospheric concentrations in the workplace and intakes in excess of, or close to, recommended and statutory limits and those associated with inorganic arsenic related diseases.     

Assessment of occupational exposure to inorganic arsenic based on urinary concentrations and speciation of arsenic.

An analytical speciation method, capable of separating inorganic arsenic (As (V), As (III] and its methylated metabolites (MMAA, DMAA) from common, inert, dietary organoarsenicals, was applied to the determination of arsenic in urine from a variety of workers occupationally exposed to inorganic arsenic compounds. Mean urinary arsenic (As (V) + As (III) + MMAA + DMAA) concentrations ranged from 4.4 micrograms/g creatinine for controls to less than 10 micrograms/g for those in the electronics industry, 47.9 micrograms/g for timber treatment workers applying arsenical wood preservatives, 79.4 micrograms/g for a group of glassworkers using arsenic trioxide, and 245 micrograms/g for chemical workers engaged in manufacturing and handling inorganic arsenicals. The maximum recorded concentration was 956 micrograms/g. For the most exposed groups, the ranges in the average urinary arsenic speciation pattern were 1-6% As (V), 11-14% As (III), 14-18% MMAA, and 63-70% DMAA. The highly raised urinary arsenic concentrations for the chemical workers, in particular, and some glassworkers are shown to correspond to possible atmospheric concentrations in the workplace and intakes in excess of, or close to, recommended and statutory limits and those associated with inorganic arsenic related diseases.     

工作场所空气中正丙醇测定方法研究

目的 研究并建立适用于工作场所空气中正丙醇的定量检测方法。
方法 工作场所空气中正丙醇由活性炭管采集, 经体积比为1:100的异丙醇-二硫化碳混合溶剂解吸后, 经石英弹性毛细管柱HP-INNOWAX (30.0 m×0.53 mm×1.0μm)分离, 氢焰离子化检测器检测, 标准曲线法定量。
结果 正丙醇浓度在10~500 μg/mL范围内和峰面积呈线性关系, 回归方程y=2.12 x+1.96, 相关系数r=0.999 9(P < 0.05)。以3.0 L采样量计, 方法最低检出浓度0.09 mg/m3, 最低定量浓度0.30 mg/m3; 不同浓度加标样品测定结果的相对标准偏差为1.7%~3.6%, 解吸效率89.3%~94.7%, 采样效率> 96%, 100 mg活性炭对正丙醇的穿透容量为16 mg; 采样后的活性炭管在室温条件下至少可放置7 d。
结论 建立的工作场所空气中正丙醇溶剂解吸-气相色谱测定方法准确可靠、灵敏度高、稳定性良好, 适用于工作场所空气中正丙醇的现场检测。