Arsenic and chromium speciation in an urban contaminated soil

The distribution and speciation of As and Cr in a contaminated soil were studied by synchrotron-based X-ray microfluorescence (μ-XRF), microfocused X-ray absorption spectroscopy (μ-XAS), and bulk extended X-ray absorption fine structure spectroscopy (EXAFS). The soil was taken from a park in Wilmington, DE, which had been an important center for the leather tanning industry along the Atlantic seaboard of the United States, until the early 20th century. Soil concentrations of As, Cr, and Pb measured at certain locations in the park greatly exceeded the background levels of these heavy metals in the State of Delaware. Results show that Cr(III) and As(V) species are mainly present in the soil, with insignificant amounts of Cr(VI) and As(III). Micro-XRF maps show that Cr and Fe are distributed together in regions where their concentrations are diffuse, and at local spots where their concentrations are high. Iron oxides, which can reduce Cr(VI) to Cr(III), are present at some of these hot spots where Cr and Fe are highly concentrated. Arsenic is mainly associated with Al in the soil, and to a minor extent with Fe. Arsenate may be sorbed to aluminum oxides, which might have transformed after a long period of time into an As–Al precipitate phase, having a structure and chemical composition similar to mansfieldite (AlAsO4⋅2H2O). The latter hypothesis is supported by the fact that only a small amount of As present in the soil was desorbed using the characteristic toxicity leaching procedure tests. This suggests that As is immobilized in the soil.

► Concentrations of As, Cr, and Pb in the park exceeded their background levels in DE.
► μ-XANES and bulk EXAFS results show that Cr(III) and As(V) species are mainly present.
► μ-XRF and XRD results show that Fe and Cr are distributed together at some hot spots.
► Bulk EXAFS and μ-XRD results suggest that As is mainly associated with Al.
► As(V) sorbed to Al oxides might have transformed to a more stable form with time.