published_or_final_version / Environmental Management / Master / Master of Science in Environmental Management

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published_or_final_version / Botany / Master / Master of Philosophy

A variety of extractants were used to fractionate the trace metals Cd, Cu, Mn, Ni, Pb, and Zn in contaminated urban soils. The metals were mostly held in soil solid phases but not in soluble and exchangeable forms. Except for Mn, extractability of metals by selective chemicals was mainly a function of the contamination level. The speciation of these elements in water, 0.01 M CaCl2, and pH-adjusted water extra was calculated using the chemical equilibrium model MINEQL+. The free ions of Cd, Ni, and Zn were the predominant species in most of the water and 0.01 M CaCl2 extracts while PbCO30 was the main form of Pb. Organically complexed Cu accounted for over of the total dissolved Cu. The solubility of trace metals increased as solution pH was decreased. Metals Cd, Ni, Pb and Zn combined with Cl- at low pH (<5). Organically complexed Cu was shifted to Cu2+ when pH was decreased. / Except for Mn, the activities of the other metals in water, 0.01 M CaCl 2 extracts, and pH-adjusted water extracts were undersaturated with respect to established minerals in soils. MnHPO4 seems to be controlling the solubility of Mn in these extracts.

The work in this thesis demonstrates whether resins are better than conventional soil extractants at predicting plant metal concentrations, and whether low-cost soil treatments can effectively reduce metal content and concentrations in lettuce leaves. / Researchers have shown that ion exchange resins can simulate root metal uptake behaviour by acting as ion sinks. Chemical extractants on the other hand, generally do not behave in this manner. Thus, we would expect resins (in either bead or membrane form) to predict plant metal concentrations better than conventional extractants. For the first study, a procedure using anion exchange resin membranes (AEM) treated with either EDTA or DTPA chelators was chosen, since previous studies showed this method to be effective at predicting plant metal uptake, and practical for routine laboratory use. In addition, several conventional extractants were selected for comparison. / For the second part of the thesis, a study was undertaken to test the effectiveness of various food processing byproducts to stabilize metal contaminants in soils, and compare the results with those of a Na-based aluminosilicate (zeolite). (Abstract shortened by UMI.)

Urban soils are often contaminated with trace metals and the toxicity of the metals depends, in part, on their speciation in soil solutions. The objectives of this project were to estimate the metal speciation in urban soils and to evaluate the predictability of soil metal pools on plant uptake. The chemical speciation of Cd, Cu, Ni, Pb and Zn was estimated by using the Windermere Humic Aqueous Model (WHAM). In soil solutions, Cd, Ni and Zn were present mainly as free ions when the solutions were acidic and their organic complexes were dominant as the pH was over 7.5. The other two metals mostly formed complexes with organic ligands. The activities of Cd2+, Cu2+, Ni2+, Pb2+ and Zn 2+ were affected by soil pH and total soil metal burdens. All five metals were under-saturated with respect to the minerals which could potentially control the metal solubility. / Metal uptake by plants in the contaminated railway yards was generally not correlated with free, dissolved and total soil metal pools. A pot experiment demonstrated better correlations between the metal pools and the metal content in wild chicory. Multiple regression analysis showed that the metals in the leaves and roots of wild chicory could be adequately predicted by the soil total metals and soil properties such as pH and exchangeable Ca.

Trace metal contamination of the air-soil-tree system was examined in southern Quebec, where acid deposition and tree dieback have been recorded in high elevation forests. Mn pollution was emphasized due to its large emission from gasoline combustion in Canada. Airborne Cu, Mn, V, and Zn showed higher concentrations than those reported for other remote locations. Significant fluctuation in Mn concentrations during the winter-spring season was explored by air mass back trajectory analysis. The study suggested that high Mn concentrations resulted from the atmospheric long-range transport from Canadian industrialized and metropolitan regions. Metal concentrations in podzolic topsoils were generally higher than their world-wide average values. Concentrations of trace metals in balsam fir (Abies balsamea (L.) Mill) needles were below their suggested potential phytotoxic levels, except for Mn, which also increased with elevation. The scanning of needles with micro-PIXE showed no significant correlation between metal accumulation and epistomatal distribution on foliar surfaces. / Pathways of trace metals deposited in the soil-tree system were elucidated through application of $ sp{54}$Mn and $ sp{65}$Zn on shoot, bark, and soil surfaces in growth-chamber experiments with balsam fir seedlings. Uptake and accumulation by seedlings 70 days after application on the shoot surface was about 25-30% of the remaining activities for $ sp{54}$Mn and $ sp{65}$Zn. Less than 1% of absorbed isotopes was translocated from the bark surface to other plant organs, whereas more than 50% of the radioisotopes absorbed at the shoot moved to the rest of the seedling. Acidic wetness facilitated the metal absorption through tree surfaces. Downward movement of the radioisotopes in podzolic soils was documented, and accumulation in seedlings by root uptake was 5% of the remaining activity for $ sp{54}$Mn and 3% for $ sp{65}$Zn 70 days after application. No appreciable elemental migration from internal tissues to epicuticular wax layers was found, and the leaching ratio was below 0.5 and 1.0% for $ sp{54}$Mn and $ sp{65}$Zn, respectively. This study helps to understand the links between atmospheric deposition and the elevated levels of Mn in trees, and potential effects of acid deposition on the bioaccumulation of toxic metal pollutants in high elevation forests in southern Quebec.

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