How magnetism-based fractional spinels contribute to the bioavailability of geogenic chromium in serpentine soils of Taiwan

Serpentine soils are highly rich in geogenic chromium (Cr), typically associated with spinel minerals. The high resistance of these minerals to weathering has raised concerns regarding their contribution to Cr bioavailability in serpentine soils. This study collected soil horizon samples from two pedons (Entisol and Ultisol) in eastern Taiwan and applied a two-step magnetic separation method to divide the bulk soils into strongly magnetic (SM), weakly magnetic (WM), and nonmagnetic (NM) fractions. The basic characteristics of the bulk soils were examined. To characterize the mineralogy and geochemistry of the fractions and determine their quantitative contribution of bioavailable Cr in serpentine soils, we analyzed their mineral composition, magnetic properties, and elemental composition and valence by using various spectrometric techniques, such as X-ray diffraction, electron probe microanalysis, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy, as well as vibrating sample magnetometry. The results indicated the main Cr-bearing minerals were magnetite and chromite in the SM and WM fractions, with minor occurrences in layer silicates, such as serpentine and chlorite, in the NM fraction. The total Cr content decreased in the following order: SM > WM > NM. The SM fraction had the lowest weight proportion, and this proportion was lower for the Ultisol than the Entisol. This observation indicated that the weathering of Cr spinels is associated with the substantial cation substitution of Al, Ca, Mn, and Ni for Fe and Cr in broken mineral grains and increases in the Fe(III) and Cr(VI) concentrations in magnetite. The SM fraction, mainly consists of magnetite and chromite, exhibited the highest concentration of bioavailable Cr extracted by 0.1 M HCl. However, the Cr-bearing layer silicates represented the largest potential pool of bioavailable Cr in the bulk soils because the weight proportion of the NM fraction was higher than those of the other fractions and increased during pedogenesis.