Nanosized iron hydroxides and organic matter (OM) are important scavengers of nutrient elements and dissolved trace-metals in geologic systems. Despite this, little is known about the sorption characteristics of metals to the iron–OM nanocomposites formed by adsorption (adsorption of OM on presynthesis ferrihydrite) versus coprecipitation (formation of ferrihydrite in the presence of OM). This study investigates lead (Pb) sorption behaviors on ferrihydrite–humic acid (Fh–HA) composites through batch sorption coupled with Pb-LIII EXAFS. We report that composites formed by coprecipitation have a higher carbon content, smaller specific surface area, and faster Pb sorption rate compared to the equivalent composites formed by adsorption of HA to preformed Fh. Pb sorption on the composites is enhanced at pH < 5 than that on pure Fh, and coprecipitated and adsorbed composites sorb almost equivalent amount of Pb. We identify a bidentate edge-sharing Pb complex on the ferrihydrite surface with a PbFe bond length of 3.33 Å and a bidentate inner-sphere Pb complex on the HA fraction of the composite. More Pb ions are associated with the HA fraction of the composites with the increases of pH from 4 to 6.5. More Pb ions are sequestrated by the organic fraction in the adsorbed than in the coprecipitated composites. This research therefore has important implications for predicting the mobility and fate of Pb in iron and organic rich soils and sediments.

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Adsorption and coprecipitation of organic matter with iron (hydr)oxides can alter iron (hydr)oxide surface properties and their reactivity towards nutrient elements and heavy metals. Organo-mineral composites were synthesized using humic acid (HA) and iron oxide, during coprecipitation with ferrihydrite (Fh) and adsorption to pre-formed Fh with two C loadings. The Fh-HA coprecipitated composites have a higher C content and smaller surface area compared to the equivalent adsorbed composites. NanoSIMS shows there is a high degree of spatial correlation between Fe and C for both composites, but C distribution is more uniform in the coprecipitated composites. The C 1s NEXAFS reveals a similar C composition between the Fh-HA coprecipitated and adsorbed composites. However composites at high carbon loading are more enriched in aromatic C, likely due to preferential binding of carboxyl functional groups on aromatic rings in the HA. The amount of Cd sorbed is independent of the composite type, either coprecipitated or adsorbed, but is a function of the C loading. Composites with low C loading show Cd sorption that is almost identical to pure Fh, while composites with high C loading show Cd sorption that is intermediate between pure Fh and pure HA, with sorption significantly enhanced over pure Fh at pH < 6.5. A bidentate edge-sharing binding was identified for Cd on pure Fh and Cd-carboxyl binding on pure HA. These findings have significant implications not only for the sequestration of Cd in contaminated environments but also the coupled biogeochemical cycling of Cd, Fe and C in the critical zone.

Soil components (e.g., clays, bacteria and humic substances) are known to produce mineral-organic composites in natural systems. Herein, batch sorption isotherms, isothermal titration calorimetry (ITC), and Cd K-edge EXAFS spectroscopy were applied to investigate the binding characteristics of Cd on montmorillonite(Mont)-humic acid(HA)-bacteria composites. Additive sorption and non-additive Cd(II) sorption behaviour is observed for the binary Mont-bacteria and ternary Mont-HA-bacteria composite, respectively. Specifically, in the ternary composite, the coexistence of HA and bacteria inhibits Cd adsorption, suggesting a “blocking effect” between humic acid and bacterial cells. Large positive entropies (68.1 ~ 114.4 J/mol/K), and linear combination fitting of the EXAFS spectra for Cd adsorbed onto Mont-bacteria and Mont-HA-bacteria composites, demonstrate that Cd is mostly bound to bacterial surface functional groups by forming inner-sphere complexes. All our results together support the assertion that there is a degree of site masking in the ternary clay mineral-humic acid-bacteria composite. Because of this, in the ternary composite, Cd preferentially binds to the higher affinity components-i.e., the bacteria.

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