Volatile Analytes Formed from Arsenosugars:  Determination by HPLC−HG-ICPMS and Implications for Arsenic Speciation Analyses

Abstract

It is generally accepted that the use of the hydride generation method to produce volatile analytes from arsenic compounds is restricted to the two inorganic forms (As(III) and As(V)) and the three simple methylated species methylarsonate (MA), dimethylarsinate (DMA), and trimethylarsine oxide. We report here that arsenosugars, major arsenic compounds in marine organisms, produce volatile analytes by the hydride generation (HG) method without a prior mineralization/oxidation step and that they can be quantitatively determined using HPLC-HG-ICPMS. The hydride generation efficiency depends on the type of hydride generation system and is influenced by the concentration of HCl and NaBH(4). For the four arsenosugars investigated, the hydride generation efficiencies were approximately 21-28% (or 4-6%, depending on the HG system) that obtained for As(III) under conditions optimized for As(III). This hydride efficiency was less than that shown by MA ( approximately 68% relative to As(III)) and DMA ( approximately 75%) but greater than that displayed by As(V) ( approximately 18%). Analysis of two species of brown algae, Fucus serratus and Hizikia fusiforme, by HPLC-HG-ICPMS produced results comparable with those obtained from other techniques used in our laboratory (HPLC-ICPMS and LC-ESMS for F. serratus) and with results from other laboratories taking part in a round robin exercise (H. fusiforme). This study shows for the first time the quantitative determination of arsenosugars using the hydride generation method without a decomposition step and has considerable implications for analytical methods for determining inorganic arsenic based on the formation of volatile hydrides.

A comparison of arsenic mobility in Phaseolus vulgaris, Mentha aquatica, and Pteris cretica rhizosphere

“…An aqueous 0.02 mol L -1 NH 4 H 2 PO 4 solution (pH 6.0) at a flow rate of 1.5 mL min -1 served as mobile phase. The column effluent was introduced into the plasma of the ICPMS (Agilent 4500) for As selective-detection [22]. [7] in liquid cultivation medium, was not confirmed.…”

Speciation Analysis of Arsenics in Commercial Hijiki by High Performance Liquid Chromatography-tandem-mass Spectrometry and High Performance Liquid Chromatography-inductively Coupled Plasma Mass Spectrometry

“…The speciation analysis of arsenic in seaweeds has made progress recently, 17,28) and consequently some AsSugs (dimethylarsinoyl ribose derivatives) have been identified as major organic arsenics in seaweeds. [29][30][31] Shibata et al 29) reported that AsSug 408 was the major, AsSug 392 was the minor, and AsSug 482 and 391 were the trace constituents in Hijiki fusiforme. AsSug 482 was not determined in our samples of #8.…”

“…Almela 8) and Raab et al 9) reported the concentrations of AsSug 328, 392, 408 and 482 in water extracts of hijiki products. Schmeisser et al 30) reported the detection of the four AsSugs in hijiki and that the content of As-Sug 408 was the highest at 11.3 mg As/kg. This value is very similar to our samples (samples #6-9) produced in the Boso area.…”

The contents of risk elements, arsenic speciation, and possible interactions of elements and betalains in beetroot (Beta vulgaris, L.) growing in contaminated soil

“…An aqueous 0.02 mol L -1 NH 4 H 2 PO 4 solution pH 6.0 at a flow rate of 1.5 mL min -1 served as mobile phase. The column effluent was introduced into the plasma of the ICPMS (Agilent 7500) for arsenic selective-detection [36].…”