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- Arsenic species (2)
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- Arsenic species analysis (1)
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The present study was focused on the determination and identification of arsenic species in methanolic extracts of cod liver. Arsenic species were fractionated and the fractions analysed by RP-HPLC-ICP-MS coupled with ESI-Q-TOF-MS. The total concentration of arsenic in the fresh cod liver was analysed by ICP-MS to be 1.53 ± 0.02 mg As kg-1 w.w. and the extraction recovery was ca. 100% and the column recovery >93%. Besides polar inorganic and methylated arsenic species (>70%) more hydrophobic arsenic-containing fatty acids and hydrocarbons occurred. Based on the mass spectrometric data proposals for molecular structures were elaborated for 20 of the organic As species included 10 arsenic-containing fatty acids (AsFA) and an arsenic-containing hydrocarbon (AsHC) mentioned for the first time in fresh cod liver. Arsenobetaine was found as main water-soluble arsenic compound in cod liver followed by higher molecular mass arsenic-containing fatty acids and hydrocarbons.
The derivatization of organoarsenic compounds by different reagents like thioglycolates or dithiols and the subsequent analysis by GC–MS as a molecular specific technique was investigated and described. The possible derivatization reagents methyl- and ethylthioglycolate (TGM and TGE), 1,3-propane- and 1,5-pentanedithiol (PDT and PeDT), which transfer the polar and nonvolatile analytes dimethylarsenate (DMA), monomethylarsonate (MMA), arsenite and arsenate into volatile compounds, were evaluated. The application for real samples like fish material was also studied.
In addition the gas chromatographic separation and resolution was optimized and experiments were carried out to determine the highest derivatization rates. Derivatization reagents were evaluated in terms of quantity and stability of the formed chemical species.
All derivatization products were characterized by mass spectrometry in order to identify the separated arsenic species.
The most efficient conversion of DMA and MMA was observed by using ethylthioglycolate as derivatization agent. Finally, the derivatization procedure and the GC–MS-method were validated to determine linearity, precision, selectivity, analytical limiting values and recoveries. For the proposed method a limit of detection (LOD) of 5.8 pg for DMA and 14.0 pg for MMA was found. The accuracy was established by comparing the mean value measured for DMA in the certified reference material BCR-627 (tuna fish) with the certified one.
MMA was not quantified in marine samples due to its low content. In shrimp samples DMA was not detectable. For codfish a DMA-content of 0.20±0.004 mg kg-1, for 'Surströmming' an amount of 0.38±0.02 mg kg-1 and for herring, which showed the highest amount of DMA, a content of 1.15±0.03 mg kg-1 was determined.
A procedure has been developed for the determination of arsenobetaine in fish matrix by HPLC–ESI-MS/MS. Hereby (trimethylarsonium)-1,2-13C-acetate (arsenobetaine) is used as internal calibration standard. Arsenobetaine was determined in a fish material (Sea Bass) with an expanded uncertainty of 3.8%.
Arsenolipids represent a relevant step in the biosynthesis of organoarsenicals from inorganic arsenic compounds. Their fate after human consumption is still uncertain.
By means of a HPLC-ICP-MS/ESI-Q-TOF-MS method, 16 lipid soluble arsenic compounds, including seven formerly unknown organoarsenicals, have been identified in commercial herring fillet.
The structural assignment was done by exact mass and high resolution MS/MS data. This is the first identification of arsenolipids in herring (Clupea harengus). They contribute with (3.6±0.2) mg kg-1 arsenic to 62.3% of the total arsenic content of (5.7±0.3) mg of arsenic per kg dry mass. Current studies indicate that a metabolization by humans to cancerous dimethylarsinic acid is very likely. The presented results are highly relevant as herring is a very popular food fish species in Europe. Moreover, the screening of different fish species revealed that arsenolipids are more widespread than previously assumed.