Geogenic arsenic (As) adversely affects drinking water quality in geologically diverse aquifers across the globe. Although the species of As significantly affects its fate, transport, toxicity, and As treatment technology efficacy, reported effectiveness of As species preservation methods varies widely with preservation methods and natural water geochemistry. Our study 1) evaluates the shelf life of As(III), As(V), dimethylarsinate (DMA), and monomethylarsonate (MMA) in standards prepared with ultrapure water; 2) establishes a hold time for these As species in low-iron (Fe) groundwater and surface water samples preserved with a concentration of EDTA that exceeded the sum of the molar concentrations of Al, Fe, Mn, Ca, Mg, and Sr (molar excess of EDTA); and 3) evaluates As(III) species stability in groundwater samples with detectable SO₄ and up to 6.5 mg/L Fe concentrations preserved in 3 ways: less than molar excess EDTA, molar excess EDTA, and Vacuette® tubes with an unknown (proprietary) amount of EDTA. Arsenic species standards prepared with 2.5 mM EDTA in ultrapure water and stored at 4 °C had a shelf life of at least 180 days. As(III) was stable for at least 15 days and DMA and MMA were stable for at least 90 days in environmental samples with Fe less than 1 mg/L that were preserved with a molar excess of EDTA and stored in opaque containers at 4 °C. As(III) species were not stable for any holding time in samples with Fe greater than 1 mg/L and detectable SO₄ when preserved with a molar excess of EDTA and stored in white high density polyethylene bottles at room temperature, or when preserved by storage in EDTA containing Vacuette® tubes at 4 °C. For geochemical or water quality studies where the distribution of As(III) and As(V) is a critical factor, an understanding of the sample chemistry, rapid As speciation analysis after sample collection, and collecting a field spike with the sample can be helpful for collecting accurate inorganic As species data.