Submitted to: Journal of Agricultural and Food Chemistry
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 4/14/2010
Publication Date: 4/19/2010
Citation: Uchimiya, M., Lima, I.M., Klasson, K.T., Chang, S., Wartelle, L.H., Rodgers, J.E. 2010. Immobilization of heavy metal ions (CuII, CdII, NiII, and PbII) by broiler litter-derived biochars in water and soil. Journal of Agricultural and Food Chemistry. 58(9):5538-5544.
Interpretive Summary: Biochar and steam-activated carbons made from broiler litter manure, a major agricultural byproduct, were evaluated for the ability to immobilize toxic metals, cadmium, copper, nickel, and lead. The purpose of this study was to determine the specific interactions between biochar and heavy metals that lead to immobilization of heavy metals in water and in soils. In water, the extent of removal increased from nickel, cadmium, copper, to lead, in agreement with higher affinity of phosphorus and nitrogen-donor ligands on the surface of biochars for softer metal ions. In addition to metal-ligand complex formation, pH increase by the addition of basic chars, surface adsorption were key mechanisms for the immobilization of heavy metal contaminants in water and soils.
Technical Abstract: Chars, a form of environmental black carbon resulting from incomplete burning of biomass, can immobilize organic contaminants by both surface adsorption and partitioning mechanisms. The predominance of each sorption mechanism depends upon the proportion of organic to carbonized fractions comprising the sorbent. Information is currently lacking in the effectiveness of char amendment for heavy metal immobilization in contaminated (e.g., urban and arms range) soils where several metal contaminants coexist. The present study employed sorbents of a common biomass origin (broiler litter manure) that underwent varying degrees of carbonization (chars formed by pyrolysis at 350 and 700 degrees C and steam-activated analogues) for heavy metal (CdII, CuII, NiII, PbII) immobilization in water and soil. ATR-FTIR, 1H NMR, and Boehm titration results suggested that higher pyrolysis temperature and activation lead to the disappearance (e.g., aliphatic –CH2 and –CH3) and the formation (e.g., C-O) of certain surface functional groups, portions of which are leachable. Both in water and soil, pH increase by the addition of basic char enhanced the immobilization of heavy metals. Heavy metal immobilization resulted in nonstoichiometric release of protons, i.e., several orders of magnitude greater total metal concentration immobilized than the protons released. Our results suggest that with higher carbonized fractions and loading of chars, heavy metal immobilization by cation exchange becomes increasingly outweighed by other controlling factors such as the coordination by pie electrons (C=C) of carbon and precipitation.