Institute of Analytical Chemistry of the Czech Academy of Sciences, v. v. i. , Veveří 97, Brno 602 00, Czech Republic.
Department of Nutrition, Gillings School of Global Public Health, University of North Carolina at Chapel Hill , 2302 MHRC, Chapel Hill, North Carolina 27599-7461, United States.
Anal Chem. 2017 Sep 19;89(18):9633-9637. doi: 10.1021/acs.analchem.7b01868. Epub 2017 Aug 28.
A method for analysis of toxicologically important arsenic species in blood plasma and whole blood by selective hydride generation with cryotrapping (HG-CT) coupled either to atomic absorption spectrometry (AAS) with a quartz multiatomizer or to inductively coupled plasma mass spectrometry (ICPMS) has been validated. Sample preparation, which involved only 5 times dilution with addition of Triton X-100, Antifoam B, and l-cysteine, suppressed excessive foaming in a hydride generator. Calibration slopes for whole blood and blood plasma spiked with arsenate, monomethylarsonate, and dimethylarsinate at 0.25-1 μg L As and 0.025-0.1 μg L As for AAS and ICPMS detection, respectively, did not differ from slopes in aqueous solutions. HG-CT-AAS was used to analyze samples with elevated levels of arsenic species-blood plasma from patients treated with arsenic trioxide for acute promyelocytic leukemia and whole blood from mice fed an arsenic-containing diet. A good agreement between results of the direct analysis and analysis after mild digestion in phosphoric acid proved the good efficiency of the direct HG-CT procedure for the arsenic species in these types of biological samples. In the next step, plasma and whole blood from healthy donors that were spiked with the plasma from leukemia patients at levels of 0.15-0.4 μg L As were analyzed by direct HG-CT-ICPMS. Good recoveries for all species even at these low levels (88-104%) were obtained. Limits of detection in blood and plasma were 0.014 μg L for inorganic arsenic and below 0.002 μg L As for methylated arsenic species. Thus, the ultrasensitive direct HG-CT-ICPMS method is uniquely suited for analyses of blood plasma and whole blood from individuals at low exposure levels.
一种通过选择性氢化物发生与冷阱捕集（HG-CT）联用，分析血浆和全血中毒理学上重要的砷形态的方法，已被验证。样品制备只需要用 Triton X-100、消泡剂 B 和 L-半胱氨酸稀释 5 倍，就可以抑制氢化物发生器中过度的泡沫。用砷酸盐、单甲基砷酸和二甲基砷酸对全血和血浆进行加标，加标水平分别为 0.25-1μg L As 和 0.025-0.1μg L As，用原子吸收光谱法（AAS）和电感耦合等离子体质谱法（ICPMS）检测时，校准斜率与水溶液中的斜率没有差异。HG-CT-AAS 用于分析三氧化二砷治疗急性早幼粒细胞白血病患者的血浆和用含砷饮食喂养的小鼠全血等砷形态含量较高的样本。直接分析和在磷酸中轻度消化后分析结果之间的良好一致性证明了直接 HG-CT 程序对这些类型生物样本中砷形态的良好效率。在下一步中，用白血病患者血浆以 0.15-0.4μg L As 的水平对健康供体的血浆和全血进行直接 HG-CT-ICPMS 分析。即使在这些低水平下，所有形态的回收率都很好（88-104%）。血液和血浆中的检测限为无机砷 0.014μg L 以下，甲基化砷形态为 0.002μg L As 以下。因此，超灵敏的直接 HG-CT-ICPMS 方法非常适合分析低暴露水平个体的血浆和全血。
