Brinckman F E, Parris G E, Blair W R, Jewett K L, Iverson W P, Bellama J M
Environ Health Perspect. 1977 Aug;19:11-24. doi: 10.1289/ehp.771911.
Biomethylation of metals, including arsenic, apparently occurs as a global process. Health control strategies therefore depend on accurate analysis of arsenic's environmental mobility. Determining to what extent biotransformations occur and how resultant organometal(loids) are sequestered in food chains requires sophistication beyond present-day total element determinations. Rather, active molecular forms of arsenic must be speciated for each environmental compartment, and it is necessary to quantify the dynamics of arsenic's mobility. Thus, new chemical facts are needed yielding rates of methylation or demethylation of arsenic; partition coefficients of organoarsenicals between air, water, and organic phases; and arsenic redox chemistry in polar media. NBS research in this context is reviewed with examples of recent results emphasizing speciation methodology. Topic areas discussed are: the nature of aquated methylarsenic species (NMR and laser-Raman spectroscopy); transport of methylarsenicals from aqueous media (gas chromatography-graphic furnace AA detection applied to metabolic Me3As formation); and speciation of involatile organoarsenicals in aqueous media (demonstration of HPLC utilizing element-specific AA detection and appraisal of electrochemical detectors).
包括砷在内的金属生物甲基化显然是一个全球性过程。因此,健康控制策略依赖于对砷在环境中迁移性的准确分析。确定生物转化发生的程度以及由此产生的有机金属(类金属)如何在食物链中被隔离,需要比当今的总元素测定更为复杂的技术。相反,必须针对每个环境区域对砷的活性分子形式进行形态分析,并且有必要量化砷迁移的动态过程。因此,需要新的化学事实来得出砷的甲基化或去甲基化速率、有机砷化合物在空气、水和有机相之间的分配系数以及极性介质中的砷氧化还原化学。本文结合近期强调形态分析方法的研究成果实例,对美国国家标准局(NBS)在这方面的研究进行了综述。讨论的主题领域包括:水合甲基砷物种的性质(核磁共振和激光拉曼光谱);甲基砷化合物从水介质中的迁移(应用于代谢性甲基胂形成的气相色谱 - 石墨炉原子吸收检测);以及水介质中难挥发有机砷化合物的形态分析(利用元素特异性原子吸收检测的高效液相色谱法的演示以及电化学检测器的评估)。