Despite the importance of accurately determining inorganic arsenic speciation in natural waters to predicting bioavailability and environmental and health impacts, there remains considerable debate about the most appropriate species preservation strategies to adopt. In particular, the high-iron, low-Eh (redox potential) shallow groundwaters in West Bengal, Bangladesh and SE Asia, the use of which for drinking and irrigation purposes has led to massive international concerns for human health, are particularly prone to changes in arsenic speciation after sampling. The effectiveness of HCl and EDTA preservation strategies has been compared and used on variably arsenic-rich West Bengali groundwater samples, analysed by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS). Immediate filtration and acidification with HCl followed by refrigerated storage was found to be the most effective strategy for minimizing the oxidation of inorganic As(III) during storage. The use of a PRP-X100 (Hamilton) column with a 20 mmol L(-1) NH4H2PO4 as mobile phase enabled the separation of Cl- from As(III), monomethylarsonic acid, dimethylarsinic acid and As(V), thereby eliminating any isobaric interference between 40Ar35Cl+ and 75As+. The use of EDTA as a preservative, whose action is impaired by the high calcium concentrations typical of these types of groundwater, resulted in marked oxidation during storage. The use of HCl is therefore indicated for analytical methods in which chloride-rich matrices are not problematical. The groundwaters analysed by IC-ICP-MS were found to contain between 5 and 770 ng As mL(-1) exclusively as inorganic arsenic species. As(III)/total-As varied between 0 and 0.94.