Objective To establish a method for the detection of formaldehyde in workplace air by the automatic discrete analyzer.Methods The discontinuous chemical analyzer was used instead of the manual method for the determination of formaldehyde.The detection steps and test working conditions were determined;the linear range,detection limit,accuracy,precision,and other indicators of the method were observed and compared with the GBZ/T 300.99-2017 method.Results There was a linear relationship between formaldehyde concentration ranging from 0 to 0.4 mg/L and absorbance,with a correlation coefficient of 0.999 9.The detection limit was 0.000 9 mg/L,and the minimum detection concentration was 0.001 5 mg/m3(calculated by collecting 3 L of air sample).The intra-assay precision was 2.39％-4.75％,and the inter-assay precision was 2.91％-9.30％.The results of the standard samples were within the calibration range.When this method was used for the determination of formaldehyde in the air of the workplaces,the relative error between the measured value and the value derived by the national standard method was within 10％,and the two groups of results had a good linear correlation(r=0.998,P＜0.001).Conclusions The automatic discrete analyzer had a high degree of automation,sensitivity,linear relationship,precision,and accuracy in determining formaldehyde in the air of the workplaces.It can replace the manual method and is suitable for efficient detection of formaldehyde in the air of the workplaces.

乙酸甲酯为具有芳香气味的无色透明液体,具有刺激和麻醉作用,在体内可被水解成甲醇和乙酸[1],可导致急性、亚急性及慢性中毒[2-3].乙酸甲酯在工业上使用广泛[4-5],且被认为是低毒物质,常用来代替丙酮、丁酮、乙酸乙酯等,其导致的健康危害常被忽视[6].本文拟通过对2022年8月广东省某地复合布厂发生的一起职业性急性乙酸甲酯中毒事件的分析,探讨应对乙酸甲酯中毒的卫生应急现场处置、患者临床救治等措施,为防范此类职业中毒提供参考.

Objective To compare the measured results of arsenic in urine by atomic fluorescence spectrometry（AFS） and inductively coupled plasma-mass spectroscopy（ICP-MS）, and analyze the reasons of the difference. Methods The samples were pretreated according to WS/T 474-2015 Determination of Arsenic in Urine by Hydride Generation Atomic Fluorescence Spectrometry, and digested with mixed acid（nitric acid∶sulfuric acid∶ perchloric acid=3∶1∶1,V/V/V） and then determined by AFS and ICP-MS. The samples were diluted with 0.50% nitric acid and determined by ICP-MS. The samples included urine arsenic quality control samples, inorganic arsenic supplemented samples, and organic arsenic（arsenic choline and arsenic betaine） supplemented samples. Standard curve method was used to compare the results of AFS method and ICP-MS method.Results The results of quality control samples by AFS method（digestion） and ICP-MS method（without digestion） were within the range of reference values, but the values obtained by AFS method were lower than those obtained by ICP-MS method.The recovery of AFS and ICP-MS was 97.79%-100.82% and 99.55%-99.98%, respectively. In the middle and high concentration groups, the measured values of inorganic arsenic by AFS were lower than that by ICP-MS（all P＜0.01）. The recovery of arsenic betaine and arsenic choline by AFS method（digestion） was only 2.17%-2.63%. The values of arsenic betaine and arsenic choline measured by AFS method（digestion） were lower than those measured by ICP-MS method（without digestion） and ICP-MS method（digestion）（all P＜0.01）. Conclusion The result of urine arsenic measured by AFS method was lower than that measured by ICP-MS method, which may be related to the mixed acid digestion of AFS method.

backgroundThe lead isotope ratios (LIR) differ among different sourced samples. Previous domestic and oversea studies on source tracing by LIR in human blood or urine mainly focused on the comparison of blood or urine samples from the same or different individuals, while few comparisons between biological and environmental samples, and the reported relative standard deviations (RSDs) of the main LIR (207/206Pb and 208/206Pb) fluctuate widely from 0.3% to 1%. ObjectiveTo optimize inductively coupled plasma mass spectrometry (ICP-MS), obtain a better RSD, and determine LIRs of human blood, urine, and related environmental samples. MethodsThe ICP-MS was optimized for operating conditions and parameters according to the sensitivity and RSD of LIR. The study subjects were 40 lead-exposed workers in a lead-acid battery factory and 2 lead poisoned children in a hospital. The samples included 40 blood and 40 urine samples from the workers before shift, 4 dust samples and 2 water samples in the workplace on the same day before shift, 2 blood and 3 urine samples from the children before hospital admission due to lead-poisoning, and 4 urine samples after medical treatment. After heating and acid digestion, the LIR (207/206Pb and 208/206Pb) of biological and environmental samples were determined by the optimized ICP-MS method. t-test and two-dimensional traceability graphics were adopted to analyze the detection results. ResultsThe calibrated RSDs of the LIR (207/206Pb and 208/206Pb) of lead isotope standard solution were 0.11% and 0.08% respectively, and the NIST-SRM-981 actual values were 0.91531±0.00097 and 2.1670±0.0017, respectively. When the total concentration of lead was greater than 5 μg·L−1, the RSD of each isotope ratio was stable gradually; when the total concentration of lead was between 10-80 μg·L−1, the RSD was below 0.20%. There were statistically significant differences in the blood and urine LIR (207/206Pb and 208/206Pb) of the lead-exposed workers (t=5.831, P<0.001; t=21.021, P<0.001), the LIR (207/206Pb and 208/206Pb) between workplace dust samples and workers’ urine samples (t=−6.879, P=0.038; t=12.521, P<0.001), and the 208/206Pb between workplace dust samples and workers’ blood samples (t=−10.46, P<0.001), except the 207/206Pb between workplace dust samples and workers’ blood samples (t=−0.12, P=0.912). In the patients afflicted with lead poisoning, the projection points of LIR of blood and urine samples from the same individual were not at the same level in the two-dimensional model, nor was the LIR of urine samples before and after medical treatment of the same individual. ConclusionThe optimized ICP-MS can control the RSD of main LIR (207/206Pb and 208/206Pb) below 0.20%. There are differences in the LIR distributions of different samples.

Objective: To establish a GDH-3 air sample tube for simultaneous determination of twelve kinds of chlorobenzene compounds (CBs) in workplace air by gas chromatography. And to established a matching determination method. Methods: In October 2020, the vapor and aerosol CBs in workplace air were collected by GDH-3 air sampling tube, and desorption and elution with 3.00 ml toluene for 15 min, then the solution separated by DB-23 capillary column, and finally detected with microcell electron capture detector. Results: The quantitative determination ranges of twelve isomers of CBs were 0.71×10(-3)-2000.00 mg/L, with the correlative coefficients were 0.99967-0.99998. The minimum detectable concentrations were 0.04-112.63 μg/m(3), and the minimum quantification concentrations were 0.14-375.42 μg/m(3) (15.00 L sample, 3.00 ml sample solution) . The average elution efficiencies were 96.00%-104.00%. The within-run relative standard deviations (RSDs) were 2.54%-6.12%, and the between-run RSDs were 3.85%-7.87%. Sealed samples could be stable at room temperature for at least 15 days. Conclusion: GDH-3 air sample tube can be used for simultaneous determination of twelve kinds of CBs in workplace air by gas chromatography. The established supporting measurement method meets the measurement requirements of the occupational health standard detection method, and the it's suitable for the simultaneous determination of 12 kinds of CBS in the air.

目的 通过比对和评估不同模式和内标条件下的尿砷测定结果,建立和优化电感耦合等离子体质谱法(ICP-MS)测定尿中砷含量的分析方法.方法 在标准模式、碰撞反应池模式和动态反应池模式条件下,应用6Li、45Sc、74Ge、89Y、103Rh、115In、159Tb和209Bi等8种内标元素建立标准曲线并测定加标样品和质控样品,比对其相关系数、检出限、准确性和精密度.结果 不同模式和内标条件下相关系数基本一致(0.998 5～0.999 9),应用45Sc、74Ge、89Y、115In等4种内标的尿砷检出限优于6Li、10eRh、159Tb、209Bi,与此同时45Sc、74Ge、89Y、115In等4种内标碰撞模式和反应模式的检出限(分别为 0.003 9、0.003 3、0.004 8、0.003 3 μg/L 和 0.003 1、0.002 7、0.003 8、0.002 7 μg/L)低于标准模式(0.044 4、0.040 4、0.046 9、0.038 6 μg/L).在3种模式下,使用74Ge和89Y作为内标,尿砷测定结果均符合《化学试剂电感耦合等离子体质谱分析方法通则》的推荐要求.结论 在碰撞或反应模式下,使用74Ge和89Y作为内标,可有效消除尿的基体效应,该方法的曲线相关系数、检出限、精密度和准确性均符合要求,可应用于ICP-MS法测定尿中砷.

[背景]我国尿砷检测的卫生行业标准未明确消化温度和电热板性能,导致不同实验室尿砷前处理方式存在较大差异.[目的]分析湿式消解-原子荧光法测定尿中砷结果偏低的原因,并对标准方法进行优化?[方法]以WS/T 474—2015《尿中砷的测定氢化物发生原子荧光法》推荐的步骤为基础,使用标准方法(150℃消解、220℃消解)和梯度升温方法(150℃消解1 h,220℃消解1 h,320℃消解30 min,消解赶酸至白烟散尽)对样品进行前处理,比对原子荧光法和ICP-MS法对尿液(高砷暴露的正常人群、服用砷剂病人和砒霜中毒病人)总砷和无机砷(亚砷酸根和砷酸根)、有机砷(砷甜菜碱和砷胆碱)标准品的测定结果.优化尿中砷测定的湿式消解-原子荧光法,并对其线性、检出限、定量下限、精密度、准确度和抗干扰能力等性能指标进行验证?[结果]150℃和220℃湿式消解原子荧光光谱法测定的结果回收率均低于90％,而梯度升温到320℃的湿式消解荧光光谱法测定结果与ICP-MS法接近,回收率为97.92％～101.16％.经过150℃和220℃的湿式消解,砷甜菜碱和砷胆碱几乎无法测出,回收率极低;梯度升温到320℃的湿式消解荧光光谱法测定砷甜菜碱和砷胆碱的回收率分别为97.59％和99.96％.该方法在尿砷含量为5.0～40.0μg·L-1时,线性关系良好,相关系数为0.9997,最低检出限为0.06μg·L-1,定量下限为0.18μg·L-1,相对标准偏差为0.95％～3.24％,加标回收率为95.95％～103.10％.200倍于砷水平的铅、锌、镉、铜、硒、汞、锑、铁、铝和锰等金属离子干扰物对测定结果所造成的偏差

OBJECTIVE:To optimize the methanol extraction technology of tripterine in the fruit of Celastrus monospermus. METHODS:HPLC was adopted to determine the content of tripterine. Using extraction time,extraction times,solid-liquid ratio as investigation factors,extraction rate of tripterine as investigation index,orthogonal test was designed,and verification test was con-ducted. RESULTS:The optimal methanol extraction technology was as follow as 45% methanol extracting 2 h each time with sol-id-liquid ratio of 1:8 for 3 times. In the verification test,the average extraction rate of tripterine was 0.917 mg/g(RSD=2.85%, n=3). CONCLUSIONS:The optimized methanol extraction technology is stable and feasible with high extraction rate,and is suit-able for the extraction of tripterine in the fruit of C. monospermus.

Objective To establish a detection method for 1-bromopropane in human urine by headspace gas chromatography-mass spectrometry ( GC-MS) .Methods A 4.00 mL portion of the urine sample was placed in a 15.00 mL headspace vial and 20.00μL of 1-bromobutane internal standard solution (204.200 mg/L mass concentration) was added. The bottle cap was immediately sealed .The sample was heated to 80 ℃ with an equilibrium time of 20 minutes in the headspace device .The vapor in the headspace vial was separated by GSBP-FFAP ( 30.00 m ×0.25 mm ×0.25 μm ) capillary chromatography column and the ion was used to carry out quantitative determination of 1-bromopropane in human urine.Results The good linearity range of 1-bromopropan mass concentration was 0.025-1.012 mg/L, and the correlation coefficient was 0.999 8.The detection limit was 7.5 μg/L (urine sample volume, 4.00 mL) and the limit of quantitation was 25.0 μg/L (urine sample volume, 4.00 mL).The relative standard deviation (RSD) of within-run precision was 2.61%-4.08%, and the RSD of between-run precision was 2.79%-6.25%.The average recovery rate was 99.34%-105.94%.Conclusion The method of determining 1-bromopropane in human urine by headspace GC-MS has the features of high sensitivity , good linear relationship , low interference , good precision and easy operation , which is suitable for detecting 1-bromopropane mass concentration in human urine .

目的 建立尿液中百草枯的离子色谱检测方法,观察百草枯中毒患者尿液中百草枯浓度的动态变化趋势,为临床救治提供参考依据.方法 样品处理:将尿液离心5 min(3 000 r/min),取上清液用微孔滤膜过滤,弃掉初滤液进样.淋洗液10％(体积分数)乙腈与0.05 mol/L七氟丁酸的混合液.结果 尿液中百草枯线性范围在0.5 ～8 mg/L(r =0.999 7),回收率为95.3％ ～ 102.1％,RSD为2.6％ ～ 3.4％,检出下限为2.3μg/L.结论 该方法快速、准确、无干扰,适合于中毒患者尿样中百草枯浓度的监测.

OBJECTIVE To investigate the forms of carbamazepine and its metabolites in the gastric juice,blood and urine samples from a poisoned patient and its metabolic pathways. METHODS The gastric juice,blood and urine samples were obtained from a patient who was rushed to the Hospital of Prevention and Treatment for Occupational Diseases to be treated for an overdose of carbamazepine for about six hours. The samples were analyzed by gas chromatography-mass spectrometry. The metabolites were identified from their mass spectra by comparison with spectra in NIST 98 libraries. The metabolic pathways were inferred by fragmentation regularities of mass spectra and the published data. RESULTS The results showed that only M1 was found in the gastric juice sample. Four metabo?lites,such as iminostilbene(M1),9-methyl-acridine(M2),9-propyl-acridan(M4)and M3,were found in the blood sample and thirteen metabolites,including M1,M2,M4,acridine(M5),acridone(M6), 9,10-dihydro Acridine (M7), 1a,10b-dihydro-6H-dibenz[b,f]oxireno[d]azepine-6-carboxamide (M8),9-acridinemethanol (M9),10,11-dihydrodiol-carbamazepine (M10),2-methyl-acridone (M12),4-methyl-acridone(M13),undetermined M3 and M11,were found in the urine from the poi?soned patient. The forms of carbamazepine metabolites in the gastric juice ,blood and urine were different. Little carbamazepine was found in the urine after metabolism. CONCLUSION Based on the analysis by gas chromatography-mass spectrometry and identification of NIST 98 libraries,the metabolites could be identified accurately,which can help analyze the metabolic mechanism and pathways of carbam?azepine.

锡及其无机化合物是工作、生活中经常接触到的物质,不同锡化合物的毒性迥然不同.本文对锡及其无机化合物的接触机会、代谢途径、毒性作用、职业接触限值及参考值分别做了概述,并对国内外检测方法作了介绍.

目的 对《工作场所空气有毒物质测定锡及其化合物》(GBZ./T 160.22-2004)所使用的前处理方法进行调整改进,建立简便、准确的试验方法.方法 参照GBZ/T 160.22-2004方法,测定、计算滤膜中锡的质量;取1.0 mL浓盐酸(优级纯)和采样后的滤膜置于具塞比色管中,置50℃水浴中消解滤膜,测定、计算滤膜中锡的质量.对两种试验方法进行对比.结果 改进前,滤膜样品锡的回收率在50.0％以下,改进后回收率均在99.0％以上.结论 经调整改良后的前处理方法操作简便,回收率高,同时能减少对试验人员的伤害和酸污染的形成.

OBJECTIVETo establish the method of graphite furnace atomic absorption spectrometry for the measurement of stannum in urine with calcium nitrate as the matrix modifier.METHODSGraphite tube was pretreated with calcium nitrate as the matrix modifier, the urine sample was diluted with 1% nitric acid and then direct injection was performed for these samples, and graphite furnace atomic absorption spectrometry was applied for measurement.RESULTSThe concentration of stannum in urine showed a good linear relationship within the range of 8.0~40.0 μg/L, with a correlation coefficient of 0.9981. The minimum detectable concentration was 0.72 μg/L, the degree of precision was 1.54%~6.69%, and the recovery rate was 99.23%~107.63%.CONCLUSIONThis method can determine the content of stannum in urine accurately and rapidly, with a high sensitivity and a low cost.

OBJECTIVE:To establish the method of high-performance liquid chromatography HPLC for the determination of N-acetyl-S-(2-carbamoylethyl)-cysteine (AAMA) in urine.METHODS:After acid hydrolysis, AAMA in urine was converted into S-2-carboxyethyl cysteine (CEC). CEC reacted with the derivative reagent ophthalaldehyde and formed the derivative with strong fluorescence absorption. The HPLC-fluorescence detector was applied, with an excitation wavelength of 340 nm and an emission wavelength of 450 nm.RESULTS:Urinary AAMA demonstrated an excellent linearity in the range of 5.3~123.5 μmol/L, with a correlation coefficient of 0.9994. The minimum detectable concentration was 0.1 μmol/L (the volume of urine sample was 1.0 ml), the recovery of standard addition was 97.4%~104.2%, and the between-run precision was 2.3%~4.3%. The sample could be stored in the refrigerator for at least 7 days at a temperature of 4℃.CONCLUSION:The method is simple, with a low cost, a high sensitivity, and good precision and accuracy, and the instrument and equipment commonly seen in laboratories are applied. Therefore, this method is worthy of wide application.

目的 建立血液和胃液中啶虫脒的快速定性测定方法.方法 血液和胃液中的啶虫脒经二氯甲烷萃取,冷氮吹干后,残留物用二氯甲烷溶解,再用气质联用仪进行定性分析.结果 血液和胃液中的啶虫脒可以在90 min内完成检测,得到的总离子流图显示啶虫脒能与血液中杂质很好地分离;样品质谱图与标准质谱图的匹配度达99％,可得到准确可靠的定性分析结果.结论 该方法能快速准确地定性分析血液和胃液中的啶虫脒成分,值得推广.

Objective: To test formaldehyde concentration in blood plasma of normal pregnant women in first trimester.Methods: Pregnant women without complication and adverse gestation outcomes were randomized sampling according to their antenatal care numbers and their blood samples were stored in the first trimester.Tested blood formaldehyde concentration in blood plasma by high-per-formance gas chromatography.Results: By high-performance gas chromatography,the lowest limitation can be tested was 0.007 μg/ml.Blood formaldehyde concentration in blood plasma was skewed distribution.The range of blood formaldehyde concentration in blood plasma of 130 cases was less than 0.007 μg/ml to 0.152 μg/ml.The median(P50) was 0.014 μg/ml,P90 was 0.066 μg/ml,P95 was 0.099 μg/ml.Conclusion: Blood formaldehyde concentration in blood plasma could be tested by high-performance gas chromatography.

[Objective]To establish a rapid qualitative method for detecting dichlorvos and omethoate in biomaterials.[Methods]Dichlorvos and omethoate in gastric juice and blood samples were extracted by dichloromethane and evaporated using nitrogen stream.The residues were dissolved with dichloromethane and detected by gas chromatography-mass spectrometry(GC/MS).Indicators of sample pre-treatments and GC/MS conditions were described.[Results]The detection of dichlorvos and omethoate in biomaterials could be finished in 60min.A qualitative conclusion was drawn by comparing the total ion chromatograms and the mass spectrums of the samples with the standard mass spectra.[Conclusion]The method can rapidly and accurately identify dichlorvos and omethoate in gastric juice and blood samples.

目的建立塑料稳定剂中三甲基氯化锡(TSC)的测定方法。着重研究气相色谱-质谱联用(GC-MS)条件的选择、方法的回收率、线性范围、检出限及精密度等指标。方法样品中的TSC经硼氢化钾衍生氢化、正己烷提取后,再用GC-MS法进行检测。结果TSC含量在4.8~1 207.0 mg/kg范围内呈线性关系,相关系数(r)=0.999 9,最低检出限为1.2 mg/kg。方法的相对标准偏差(RSD)=2.7%~9.0%。回收率为95.4%~96.6%。结论该方法能准确测定各种塑料稳定剂中TSC的浓度,各项指标符合《工作场所空气中毒物检测方法的研制规范》的要求,值得推广应用。