This paper addresses the contamination of groundwater by arsenic, a naturally occurring phenomenon that has caused serious cases of arsenic poisoning around the world. While a number of chemical processes are known to be capable of mobilizing arsenic, the extent to which different processes are active in actual geological settings is much less clear. In this work, the El Paso, Texas region is analyzed as a case study to better understand the factors associated with high arsenic levels in groundwater. This study includes two basins that supply drinking water to approximately 2.5 million people. The average arsenic was 8.5 ppb, which is below the current American and WHO Maximum Contaminant Level of 10 ppb. However, arsenic concentrations reached approximately 80 ppb in three different locations. Governmental archival information was combined with field water sampling, and with leaching and analysis of solid phase materials from well cuttings (sediments of the aquifers). The study identifies evidence for both competitive desorption and reductive dissolution operating to mobilize arsenic, with the importance of different mechanisms likely varying throughout the aquifers. A mean of 21% of the solid arsenic content was leached out to solution at pH 9, and mean solid phase arsenic concentration was 4.3 ppm, solid phase iron 7000 ppm, and solid carbon 0.6%, consistent with arsenic desorption out of sediments into the aqueous phase. A potential role of geothermal waters was also identified at a southern hot spot. This information is important to better understand the basic science of the arsenic geochemical cycle and may also provide a rough guide as to where low arsenic waters may be found: groundwater with high potentiometric head and short flow paths, groundwater under the influence of surface water, and lower pH groundwater.