Abstract--Interactions with bentonite are important in the chemical speciation and fate of heavy metals in soils and other ecosystems. The interactions of Zn with bentonite were studied using X-ray diffraction (XRD), dehydration, kinetic and sequential extraction procedures. The species and activity of Zn retained by bentonite were affected markedly by pH. The Zn(OH) + was retained by bentonite prepared at pH --> 6.9. The extent of dehydration of Zn(OH)+-bentonite was higher than that for Zn-bentonite. At a relative humidity of 55.5%, the basal spacing of the Zn(OH)*-bentonite was from 1.21 to 1.26 nm with 1 water sheet and that of the Zn-bentonite was 1.51 nm with 2 water sheets. The greater affinity of Zn(OH) + for bentonite than Zn was associated with a lower degree of hydration. When an aqueous suspension of Cabentonite was incubated with soluble Zn, the concentration of Zn retained by the Ca-bentonite was linearly related to the square root of time. The rate of the interaction was controlled probably by the interlayer diffusion and subsequently by the diffusion into the ditrigonal cavities in bentonite. The Zn retained by bentonite was dehydrated in situ so as to increase the bonding of Zn with surfaces of bentonite. With hydrothermal treatment the retained Zn could diffuse easily into the cavities and transform increasingly to the residual forms that are associated with the entrapped form.
Sorption of zinc (Zn) in a calcareous soil was studied using a miscible displacement procedure. Sorption of Zn in soil can be described by a secondorder equation and by a diffusion equation based on the overall higher value of correlation coefficient and the lower value of standard error. The results show that the sorption of Zn in soil was increased by elevated temperature and pH. The maximum of Zn sorbed in soil increased, but the rate coefficient decreased with increasing pH. The maximum of sorbed Zn and rate coefficient tended to increase with elevated temperature. The value of activation energy (E a ) estimated with different kinetic equations was found to be variable and in the range of 5.0-17 kJ.mol -1 . The relative diffusion rate coefficient (D/r 2 ), estimated using a diffusion equation, was found to be in the order of 10 -6 sec -1 . The intra-aggregate diffusion and/or film diffusion of Zn may be a rate-limiting process in the sorption of Zn in soils.
The effects of cropping corn on the decrease in the extractability of Zn added to a calcareous soil were studied by a pot experiment and chemical extractions. The results show that the concentrations of Zn exchangeable with MgCI2 (EXC-Zn) and extractable with DTPA (DTPA-Zn) in the soils with added Zn decreased with time. The processes associated with the decrease in extractability in DTPA of Zn added to soil can be described aptly by a diffusion equation which gives the proportion of added Zn in the non-DTPA fraction as a function of the square root of incubation time. This result suggests that the diffusion of Zn cations into microporous solids is a rate-limiting reaction. The relative diffusion rate coefficients (D/r 2) were found to be 1.95x 10 -I° and 3.34x 10 -~° sec -l in the soils with added Zn of 20 and 60 mg kg-z, respectively. Compared with uncropped soil, the concentrations of DTPA-Zn in the soils with added Zn were decreased by cropping. The decrease of DTPA-Zn in the soils in the presence of corn can be attributed to both its acquisition by corn and other processes associated with the growing of corn. The activity of plant roots would appear to enhance the process of decrease in the extractability in DTPA of Zn added to the soil. The source of Zn uptake by corn was affected by the loading or activity of Zn in soil. In the soil with low available Zn, the DTPA non-extractable Zn (non-DTPA-Zn) was mobilized and taken up by corn. In the soils with high available Zn, e.g. the recently added Zn, only EXC-Zn and a part of the DTPA-Zn were taken up by corn.
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