Arsenic is the focus of public attention because of its wider prevalence and toxicity. Proper sampling is important in characterizing toxic water contaminants in the groundwater. The present paper studies aspects of sampling, preservation artifacts, analytical issues etc. in a natural arsenic contaminated groundwater. The samples were collected from arsenic contaminated groundwater at three locations of village Kaudikasa in Rajnandgaon (Chhattisgarh). The standard method of sampling and preservation of arsenic was examined.