Trivalent chromium solubility and its influence on quantification of hexavalent chromium in ambient particulate matter using EPA method 6800

Abstract

Measurement of carcinogenic Cr(VI) in ambient PM is challenging due to potential errors associated with conversion between Cr (VI) (a carcinogen) and Cr(III) (an essential nutrient). Cr(III) conversion is a particular concern due to its > 80% atomic abundance in total Cr. US. Environmental Protection Agency (EPA) method 6800 that uses water-soluble isotope spikes can be used to correct the interconversion. However, whether the enriched Cr(III) isotope spikes can adequately mimic the Cr(III) species originally in ambient PM is unknown. This study examined the water solubility of Cr(III) in ambient PM and discussed its influence on Cr(VI) measurement. Ambient PM10 samples were collected on Teflon filters at four sites in New Jersey that may have different Cr emission sources. The samples were ultrasonically extracted with 5 mL DI-H2O (pH 5.7) at room temperature for 40 min, and then analyzed by ion chromatography-inductively coupled plasma mass spectrometry (IC-ICPMS). Cr(III) was below detection limit (0.06 ng/m3) for all samples, suggesting water-soluble Cr(III) species, such as CrCl3, Cr(NO3)3, and amorphous Cr(OH)3, in the ambient PM were negligible. Therefore, the enriched 50Cr(III) isotope spike (in the form of Cr(NO3)3) could not mimic the original ambient Cr(III). Only the conversion of 53Cr(VI) (in the form of K2CrO4) was taken into account when correcting the interconversion. We then used NaHCO3-pretreated MCE filters (prespiked with enriched isotope species) to measure Cr(VI) in the ambient PM10. The samples were ultrasonically extracted at 60 C pH 9 solutions for 40 min followed by IC-ICPMS analysis. Due to the correction of Cr(VI) reduction, the Cr(VI) concentrations determined by EPA method 6800, 0.26 ± 0.16 (summer) and 0.16 ± 0.11(winter) ng/m3 (n = 64), were significantly greater than those by the external standard curve, 0.21 ± 0.17 (summer) and 0.10 ± 0.07 (winter) ng/m3 (n = 56) (p < 0.01, Student's t-test). Our study revealed that appropriate application of EPA method 6800 is important because it only applies to soluble fraction of Cr species in ambient PM. Implications: Accurate measurement of carcinogenic Cr(VI) in ambient PM is challenging due to conversion between Cr(VI) (a human carcinogen) and Cr(III) (a human essential nutrient). The conversion of CR(III) is of particular concern due to its dominant presence in total Cr (>80%). This study examined the water solubility of Cr(III) in ambient PM that was collected at four locations in New Jersey. Then we discussed the influence of Cr(III) solubility on the application of EPA method 6800, which utilizes enriched isotope spikes to correct the interconversion. Our results suggested that appropriate application of EPA method 6800 is important because it only applies to soluble fraction of Cr species.