Ferrihydrite-organo composites are a suitable analog for predicting Cd(II)- As(V) coexistence behaviors at the soil solid-liquid interfaces*

Organomineral assemblages are building units of soil micro-aggregates and exert their essential roles in immobilizing toxic elements. Currently, our knowledge of the adsorption and partitioning behaviors of coexisting Cd-As onto organomineral composites is limited. Herein, we carefully studied Cd-As cosorption onto ferrihydrite organomineral composites made with either living or non-living organics, i.e., bacteria (Delftia sp.) or humic acid (HA), using batch adsorption and various spectroscopies. Batch results show that As(V) only enhances Cd(II) sorption on pure Fh at pH 6 but cannot promote Cd(II) sorption to Fh-organo composites. However, Cd(II) noticeably promotes As(V) sorption at pH -5-6. Synchrotron micro X-ray fluorescence indicates that Cd(II) adsorbs predominately to the bacterial fraction (Cd versus P, r = 0.924), whereas As(V) binds mainly to the Fh fraction (As versus Fe, r = 0.844) of the Fh-bacteria composite. On Fh-HA composite, however, Cd(II) and As(V) are both primarily sorbed by the Fh fraction (Cd/As versus P, r > 0.8), based on the scanning transmission electron microscopy-energy disperse spectroscopy analyses. Elemental distribution characterization also manifests the co-localization of Cd(II) and As(V) within the organomineral composite, particular in Fh-HA composite (Cd versus As, r = 0.8), which is further identified as the Fh-As-Cd ternary complex based on the observations (higher frequencies at -753-761 cm-1) of attenuated total reflection Fourier-transform infrared spectroscopy. Moreover, this ternary interaction is more pronounced in Fh-HA than in Fh-bacteria. In summary, our results suggest that Cd-As coadsorption behaviors on Fh-organo composites are different from those on pure minerals, and the presence of bacteria/HA can significantly affect metal (loid)s speciation, distribution, and ternary interaction. Therefore organomineral composites are a more suitable analog than pure mineral phases to predict the mobility and fate of Cd-As in natural environments.