Metals sorption in soils is influenced by several factors, including pH, ionic strength, the presence of ionic composition or organic ligands, total amount of metals, and adsorbent loading. These conditions should be considered when evaluating metal sorption capacity of soil material or when applying laboratory results to field conditions. Metal sorption experiments were conducted on Bertie sandy and Starr-Dyke clay loam soils from long-term field studies in which soils received annual applications of copper-rich pig manure for 16 years. Adsorption of Cd, Cu, Pb, and Zn as affected by different background electrolytes at various concentrations was investigated. Electrolytes were Na+, Ca2+, or Al3+ in perchlorate solution, and their concentrations ranged from 0.001 to 0.5 molc L-1. Increasing ionic strength decreased metal adsorption capacity. Electrolyte cation composition had a greater effect on adsorption than did electrolyte concentration. The order of sensitivity to cation composition of the electrolyte was Zn > Cd > Cu > Pb, and this effect was greater in Bertie sandy loam than Starr-Dyke clay loam soils. Little difference in Cu and Pb adsorption was observed between Na+ and Ca2+ in background solution. Most added Cu was adsorbed at low concentrations regardless of pH, but at high concentrations Cu sorption was strongly related to solution pH. Increases in pH resulted in greater Cu sorption due to pH-dependent negative charges and precipitation. The USEPA recommends that soil systems receiving high metal loading rates be maintained at pH 6.5 or above because of the increased metal adsorption. However, pig manure applications to the Bertie soil resulted in greater Cu in soil solution than in control (no manure) soil at pH > 6.5 due to soluble organic matter. Using the Langmuir equation to determine adsorption maxima for soil systems does not always give adequate estimates of adsorption and values from the equations are highly dependent upon soil environmental parameters. Given the limitations in prediction of adsorption maxima, and given that the amount of nonsorbed metal is as important as the adsorbed amount, the isolines of metal remaining in soil solution were provided with a given set of soil environmental factors. / Ph. D.

Poly-γ-glutamic acid (γ-PGA) is a biopolymer made up of repeating units of L-glutamic acid, D-glutamic acid or both. γ-PGA is water soluble, non-toxic and biodegradable, and can be used safely in a variety of applications that are increasing rapidly. This study investigated the production of HMW γ-PGA by five Bacillus species (B. licheniformis 1525, B. licheniformis NCTC 6816, B. licheniformis ATCC 9945a, B. licheniformis ATCC 9945a and B. subtilis (natto) ATCC 15245) in GS, C and E media for the removal of heavy metals in wastewaters. The highest γ-PGA yields of 11.69 g/l and 11.59 g/l were produced by Bacillus subtilis (natto) ATCC 15245 in GS medium and medium C respectively. Upon characterization, γ- PGAs with different properties (crystallinity, acid/salt form and molecular weights ranging from 2.56 × 105 Da to 1.65 × 106 Da) were produced. The water soluble, non-toxic, HMW (Mw 1.65 × 106 Da) γ-PGA produced by B. subtilis (natto) ATCC 15245 in medium C was investigated as a sorbent for the removal of heavy metal ions including Cu2+, Zn2+, Ni2+, Cd2+ and Ag+. The results showed that the removal of metals by γ-PGA was more dependent on the concentration of γ-PGA than the solution pH. The highest metal ions removal of 93.50%, 88.13%, 90.21%, 90.56% and 86.34% by HMW γ-PGA were obtained for Cu2+, Zn2+, Ni2+, Cd2+ and Ag+ respectively. The presence of interfering metal ions could hinder the adsorption of individual metal ions by γ-PGA. The affinities of heavy metal ions for γ-PGA followed the order: Cu2+ > Zn2+ > Ni2+ > Cd2+. The effect of molecular weight of γ-PGA on metal removal was also investigated, and it was found that metal ion adsorption capacity of γ-PGA strongly depended on its molecular weight. The maximum amount (93.50%) of Cu2+ sorbed by HMW γ-PGA was higher compared to that (59.48%) sorbed by LMW γ-PGA. Isotherm models showed that the Redlich-Peterson best described the metal adsorption capacity of γ-PGA. It was also found that a multisite adsorption mechanism occurred via the complexation of metal ions with the free α-carboxyl and possibly the amide functional groups in γ-PGA.