Kathleen Caroline Holt

Formation of hydroxyapatite in soils using calcium citrate and sodium phosphate for control of strontium migration

Summary 90Sr contamination is a major problem at several U.S. sites. At some sites, 90Sr has migrated deep underground making site remediation difficult. In this paper, we describe a novel method for precipitation of hydroxyapatite, a strong sorbent for 90Sr, in soil. The method is based on mixing a solution of calcium citrate and sodium phosphate in soil. As the indigenous soil microorganisms mineralize the citrate, the calcium is released and forms hydroxyapatite. Soil, taken from the Albuquerque desert, was treated with a sodium phosphate solution or a sodium phosphate/calcium citrate solution. TEM and EDS were used to identify hydroxyapatite with CO32- substitutions, with a formula of (Ca4.8Na0.2)[(PO4)2.8(CO3)0.2](OH), in the soil treated with the sodium phosphate/calcium citrate solution. Untreated and treated soils were used in batch sorption experiments for Sr uptake. Average Sr uptake was 19.5, 77.0 and 94.7% for the untreated soil, soil treated with sodium phosphate, and soil with apatite, respectively. In desorption experiments, the untreated soil, phosphate treated soil and apatite treated soil released an average of 34.2, 28.8 and 4.8% respectively. The results indicate the potential of forming apatite in soil using soluble reagents for retardation of radionuclide migration.

Sorption of Np(V) by synthetic hydroxyapatite

Abstract The sorption of Np(V) to synthetic hydroxyapatite was determined in batch experiments in a 0.1M NaClO4 solution. The hydroxyapatite used was of high purity as determined by SEM, EDS, XRD, FT-IR and ICP-MS analysis. Results from kinetic experiments with an initial Np(V) concentration of 1×10-7 to 1×10-6M indicate the sorption process is relatively fast with more than 90 of the Np(V) being sorbed in approximately 3 hours. Equilibrium experiments performed over the pH range of 6 to 11 indicated sorption is strongly pH dependent with distribution coefficients, Kd values (mL/g), increasing from 123L/mole at pH 6 to 69200L/mole at pH 8.5. Kd values are observed to decrease as pH further increases. Data points over a range of Np(V) concentrations were collected at pH 8 and fitted to the Langmuir isotherm model for simple adsorption. The Langmuir equation gave an excellent representation of the data. Langmuir parameters were determined to be Ca=0.032mole/mole and K=1.22×106L/mole, indicating the high affinity of hydroxyapatite for Np(V) adsorption.