Arsenic is an ubiquitous and potentially toxic element in the environment. Present in soils [1,2] and in waters [3], both naturally and as the result of human activities -agriculture, industry or coal burning plants for example [4,5] -it undergoes many physical, chemical and biological changes in the different ecosystems [6][7][8]. Biological reactions occurring in terrestrial [9,10] and marine organisms [11][12][13][14] convert inorganic arsenate (AsV) and arsenite (AsIII) to monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA) and trimethylarsine oxyde (TMAO). Moreover, microorganisms are able to reduce arsenate in arsenite previously released into solution prior to methylation [15,16].In order to understand these biochemical processes and since arsenic toxicity depends on its speciation [17], several techniques have been developed to determine the concentrations of the different arsenic compounds [18][19][20][21][22]. Methods based on HPLC separation are more and more often used in arsenic speciation and a review of the main techniques using this separation has been recently published by Guerin et al. [23]. AAS [24,25] [36][37][38] are now well described. However, chromatographic dilution reduces sensitivity that may be then not sufficient for the analysis of environmental samples. Moreover, the development of these methods requires important investing and high running costs limiting their use in most laboratories. Reported by several authors, the hyphenated HG/GC/AAS method with cryogenic trapping offers an excellent sensitivity owing to the separation of matrix and analytes during hydride generation, the preconcentration by trapping in liquid nitrogen associated to the selectivity and sensitivity of AAS detection. It is simple to operate with a fully automated system suitable for routine analyse and requires little investing. It has already widely used for the study of biochemical processes or the determination of AsIII, AsV, MMAA and DMAA in environmental samples [39,[41][42][43][44][45][46][47][48][49][50][51][52].Since the first system presented by Andreae in 1977 [39], some modifications have improved the performances of the HG/GC/AAS method [49][50][51][52]. However, few papers deal with the effects of analytical parameters in the development of such a method.The aim of this paper was to systematically examine each of adjustable parameters in the whole experimental process using standard solutions in order to improve the cryogenic trap HG/QFAAS procedure before using it to the determi- Abstract. Analytical parameters of hydride generation, trapping, gas chromatography and atomic absorption spectrometry detection in a quartz cell furnace (HG/GC/QFAAS) device have been optimized in order to develop an efficient and sensitive method for arsenic compounds speciation. Good performances were obtained with absolute detection limits in the range of 0.1 -0.5 ng for arsenite, arsenate, monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA) and trimethylarsine oxide (TMAO). A pH selective reduction for...