Quantitative analysis of arsenic containing hydrocarbons in marine samples by GC-MS

Environmental context: The marine ecosystem is highly elevated in arsenic in comparison to the terrestrial environment. More than 100 different naturally occurring organoarsenic compounds have been found in different marine organisms. In order to understand how highly toxic AsHCs are formed and bioaccumulate in different marine organisms, large scale monitoring of AsHCs from a range of different laboratories is necessary. Despite their toxicity, AsHCs have not been extensively studied due in part to the lack of low-cost analytical methods and the lack of commercially available standards.Rational: This study aims to develop a new analytical method for the quantitative determination of arsenic-containing hydrocarbons (AsHCs) with gas chromatography-mass spectrometry (GC-MS). The new method is an alternative approach to determine these compounds in environmental samples.Methodology: AsHCs were extracted and purified from fish oil and seaweed samples. Due to the thermal conversion of oxo-AsHCs to their trivalent forms in the injection port of the GC, the conversion is incomplete resulting in low signal intensities and large carry overs. We therefore chemically reduced AsHCs to their trivalent forms and analysed them with GC-MS, gas chromatography-tandem mass spectrometry (GC-MS/MS) and high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICPMS). The possibility for compound independent quantification with commercially available standards was investigated.Results: After optimisation of conditions for reduction of AsHCs, these compounds could be determined in marine samples using authentic standards with the new method. Results showed good agreement with results from HPLC-ICPMS. The novel GC-MS method showed compound independent quantification using triphenylarsine (TPA) as a commercially available standard.DiscussionWith the developed method we could demonstrate the applicability of GC-MS for the quantitative determination of AsHCs in marine samples for the first time. The compound independent quantification with TPA opens up a quantification for AsHCs species for which no standards are commercially available. The broad applicability might enhance screening for these toxic compounds in the environment.

Automated summary

A new analytical method using gas chromatography-mass spectrometry (GC-MS) was developed for the quantitative determination of arsenic-containing hydrocarbons (AsHCs) in marine samples. The novel method allows for compound independent quantification using triphenylarsine (TPA) as a commercially available standard, expanding the screening application for these toxic compounds in the environment.