Analysis of hydroponic fertilizer matrixes for perchlorate: comparison of analytical techniques

Seven retail hydroponic nitrate fertilizer products, two liquid and five solid, were comparatively analyzed for the perchlorate anion (ClO4-) by ion chromatography (IC) with suppressed conductivity detection, complexation electrospray ionization mass spectrometry (cESI-MS), normal Raman spectroscopy, and infrared spectroscopy using an attenuated total reflectance crystal (ATR-FTIR) coated with a thin film of an organometallic ion-exchange compound. Three of the five solid products were found by all techniques to contain perchlorate at the level of approximately 100-350 mg kg(-1). The remaining products did not contain perchlorate above the detection level of any of the techniques. Comparative analysis using several analytical techniques that depend on different properties of perchlorate allow for a high degree of certainty in both the qualitative and quantitative determinations. This proved particularly useful for these samples, due to the complexity of the matrix. Analyses of this type, including multiple spectroscopic confirmations, may also be useful for other complicated matrixes (e.g., biological samples) or in forensic/regulatory frameworks where data are likely to be challenged. While the source of perchlorate in these hydroponic products is not known, the perchlorate-to-nitrate concentration ratio (w/w) in the aqueous extracts is generally consistent with the historical weight percent of water soluble components in caliche, a nitrate-bearing ore found predominantly in Chile. This ore, which is the only well-established natural source of perchlorate, is mined and used, albeit minimally, as a nitrogen source in some fertilizer products.