In-situ measurement of labile Cr(III) and Cr(VI) in water using diffusive gradients in thin-films (DGT)

The toxicity and bioavailability of Cr depends on its speciation in the aquatic environment. Here, we developed a new method for simultaneously obtaining in-situ data on labile Cr(III) and Cr(VI) using diffusive gradients in thin films (DGT) and high-performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A Zr-oxide DGT was applied to accumulate both labile Cr(III) and Cr(VI). The elution of Cr species was carried out with 50 mM EDTA-2Na at pH 9.5 for 1.5 h. Agilent Bio WAX anion-exchange chromatography was used to separate Cr species in the slightly alkaline mobile phase containing 40 mM NH₄NO₃ at pH 7.4. An ICP-MS was used to quantitatively measure Cr within 4.5 min. Method detection limits were 0.05 μg/L for Cr(III) and 0.02 μg/L for Cr(VI). Labile Cr(III) and Cr(VI) was accurately quantified in synthetic solutions for pH in the range of 5-8 and ionic strength ranging from 10 to 100 mmol L^-1. The method allows quantification of labile Cr(III) and Cr(VI) in natural water and was consistent with results of when a separate measurement method based on DGT was used. This study was an attempt at simultaneous in-situ quantification of labile Cr(III) and Cr(VI), and will facilitate in-situ labile Cr speciation analysis in the environment.