Several biologically important arsenic compounds including methylarsonate, trimethylarsine oxide, tetramethylarsonium ion, arsenobetaine and arsenocholine were prepared, in good yields, from sodium arsenite, or dimethylarsinic acid. These organoarsenic compounds together with arsenite, arsenate and dimethylarsinic acid were used as standards for the development of analytical methods for determining the levels of individual arsenic compounds (arsenic speciation) present in natural matrices. / Arsenobetaine, arsenocholine and tetramethylarsonium ion were separated by high performance liquid chromatography (HPLC) with on-line detection by thermochemical hydride generation (THG)-AAS. The analytes were eluted from the cyanopropyl bonded phase HPLC column with a 1% acetic acid methanolic mobile phase which also contained diethyl ether triethylamine, and trimethylsulfonium iodide or picrylsulfonic acid. A surface response methodology and a univariate optimization procedure were used to determine the optimum concentration of solvent modifiers in the methanolic mobile phase. Limits of detection in the range 4-5 ng (as As) were obtained for the arsonium analytes under optimum chromatographic conditions. / A simple phenol extraction procedure was developed to isolate arsonium analytes from edible marine tissues (lobster tail muscle, peeled and deveined shrimp, and cod fillet), cod liver oil and human urine. The crude extracts were separated on the cyanopropyl column using a methanolic mobile phase and detected on-line by THG-AAS. Recoveries from tissues or from urine which had been spiked at 0.1-3.4 $ mu$g of As cation/g of fresh weight were 80% or greater for each of five sample types. / An improved HPLC-AAS interface which was compatible with either aqueous or organic mobile phases was also developed. The interface provided approximately equivalent responses to different arsenic oxidation states which resulted in low to subnanogram chromatographic limits of detection for arsenic oxyanions and arsonium cations in an aqueous or methanolic mobile phase. Nascent As anions and As cations were conveniently coextracted from aqueous solution or from fish muscle by phenol extraction and quantified in the same chromatographic run. This method has been applied to a standard reference sample of dogfish muscle (DORM-1), a marine reference sediment sample (PACS-1) and to sediment porewaters (SAG-15) from the Saguenay Fjord.

Thesis (MS)--Texas A & M University, 2002. / Includes bibliographical references (p. 68-75). Also available via the Internet.

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High concentrations of arsenic are found near gold-mine tailings. The most common form of arsenic found in soil is arsenate, which is a known toxicant. We used the standardised earthworm reproduction test for the species Eisenia andrei (E. andrei) to study the toxicity and bioavailability of arsenic-contaminated soil. Arsenic is toxic to earthworms as indicated by the decrease in survival and reproduction. Arsenic-spiked artificial soil was more toxic than arsenic-spiked field soil based on total arsenic concentration in soil. Moreover, soil from near mine tailings showed a reduced toxic effect despite its high soil arsenic concentration as compared to spiked field soil. Measurements of arsenic tissue concentrations in the earthworm indicated that uptake of arsenic into earthworm tissue was higher in spiked artificial soil as compared to spiked field soil and that the maximal body burden was 396 mug As/g dry tissue weight. However, when considering tissue arsenic concentration, spiked field soil is more toxic than spiked artificial soil. Therefore the tissue rather than soil content may better reflect the magnitude of arsenic toxicity to E. andrei.

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