Penrose W R, Conacher H B, Black R, Méranger J C, Miles W, Cunningham H M, Squires W R
Environ Health Perspect. 1977 Aug;19:53-9. doi: 10.1289/ehp.771953.
An organic form of arsenic is commonly encountered in marine organisms; in greysole and shrimp, it accounted for all arsenic found in muscle tissue. It has been isolated from flounder tissue by two independent procedures; it was hydrophilic, cationic, and was not decomposed to inorganic arsenic by hot nitric and sulfuric acids. NMR spectroscopy indicated all nonexchangeable protons to be equivalent; they behaved more like N-methyl protons than As-methyl protons. High-resolution mass spectroscopy from a heated probe yielded a spectrum corresponding to tetramethylarsonium (AsMe4+); the authentic ion, however, had TLC and ion-exchange behavior different from that of the natural product. Infrared spectrometry likewise produced conflicting or uninterpretable data. Decomposition of the compound for analytical purposes was accomplished by dry ashing under oxidizing conditions. Sea urchins, like trout, converted arsenic to an organic form, but to a more limited degree. Arsenic found naturally in sea urchins and in a species of macroalga was also organic. In individual containers, sea urchins were fed on the alga for 7 weeks. During this time they consumed 0.203 +/- 0.075 mg total As and excreted only 0.036 +/- 0.015 mg as feces. Measurement of inorganic As in the seawater did not account for the discrepancy, but measurements of total As did (0.202 +/- 0.095 mg). Sea urchins, like humans, appear to be able to rapidly excrete these organic forms of arsenic.
砷的有机形态在海洋生物中很常见;在北美大比目鱼和虾中,它占肌肉组织中发现的所有砷。它已通过两种独立的方法从比目鱼组织中分离出来;它具有亲水性、阳离子性,并且不会被热硝酸和硫酸分解为无机砷。核磁共振光谱表明所有不可交换的质子都是等效的;它们的行为更像N - 甲基质子而不是砷 - 甲基质子。来自加热探针的高分辨率质谱产生了与四甲基砷鎓(AsMe4+)相对应的光谱;然而,真实离子的薄层色谱和离子交换行为与天然产物不同。红外光谱同样产生了相互矛盾或无法解释的数据。为了分析目的,该化合物的分解是通过在氧化条件下干灰化完成的。海胆和鳟鱼一样,会将砷转化为有机形态,但程度更有限。在海胆和一种大型藻类中天然发现的砷也是有机的。在单独的容器中,给海胆喂食这种藻类7周。在此期间,它们总共消耗了0.203±0.075毫克的总砷,而作为粪便仅排出了0.036±0.015毫克。海水中无机砷的测量并不能解释这种差异,但总砷的测量可以(0.202±0.095毫克)。海胆和人类一样,似乎能够快速排出这些有机形态的砷。