Sorption behaviour of metal contaminants in clay minerals, soils and matrices: understanding the influence of organic matter, pH, ionic strength and mineralogy
thesisposted on 15.05.2015 by Olanrewaju Anjolaiya
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Many chemical and physical factors govern the mobility of metal contaminants in soils and clay systems; some of these chemical factors include mineralogical composition, cation exchange capacity, organic matter content, pH and the ionic strength of soil water. This makes understanding and therefore predicting the fate of metal contaminants in soils a complex undertaking. There were two broad objectives in this study. The first was to investigate binary and ternary sorption systems, with the aim to understand the effects that factors such as pH, ionic strength, organic matter and metal concentrations, have on sorption of simple clay minerals (bentonite and kaolinite) with metals (cadmium, caesium, nickel and strontium). The second was to investigate the retention of heavy metals and radionuclides by well characterised organic-rich and organic-poor clay soils, breaking them down to their individual components to help understand the effects of each component separately, the study also tested to see if the additivity principle holds for these heavy metals and radionuclides, the additivity principle presumes that the overall sorption behaviour of a complex mixture is a summation of the weighted individual sorption behaviours of its constituents. The study also determined the relationship between the natural organic matter (NOM) content and cation exchange capacity (CEC) of the soils and how these affect the mobility of the metals, while also considering the relative importance of the speciation of the metals. Two British clay soils (Mercia Mudstone and London Clay) and two Nigerian soils (an organic-rich Ikeja Loam and the other organic-poor Magodo Laterite) were characterised by X-ray diffraction (XRD) analysis. Batch techniques were employed for the sorption studies, and radiometric techniques, ICP-OES and ICP-MS were used to quantify metal distribution between phases. The sorption of dissolved organic matter to clay minerals is very dependent on pH; this dependence is greater with increasing concentration of organic matter. The formation of metal-humate complexes is dependent on the nature of the metal and pH. Caesium exhibits no discernible sorption to humic acid, cadmium sorption is enhanced by increasing alkalinity but this enhancement is slightly reduced in higher concentrations of humic acid, nickel sorption is mostly unaffected by pH except in higher concentrations of humic acid and enhanced only under very low concentrations of humic acid, while strontium sorption to humic acid is reduced with increasing alkalinity. The nature and preference of humic acid sorption for these metals are vital to understanding the role played by humic acid in the ternary sorption studies of metals, humic acid and clay minerals. Strongly acidic conditions dominate other factors affecting sorption such as ionic strength in sorption of metals to clay minerals. Caesium sorption to bentonite at pH 4 is poor and almost unaffected by ionic strength of the electrolyte solution; saturation of sorption sites is reached with low amounts of adsorbed caesium. Strontium also binds poorly to bentonite at pH 4, more so than caesium, but an ionic strength effect on sorption still exists and is discernible even under these conditions. Increasing alkalinity has the expected effect of increasing sorption capacity of bentonite for both metals. Bentonite has poor sorption properties, having low affinity for caesium and strontium, but has greater affinity for caesium than strontium. The presence of humic acid can enhance or suppresses sorption, this varies from metal to metal and from solid to solid, the degree of enhancement or suppression also depends on humic acid concentration. Kaolinite has better sorption properties than bentonie. Cadmium has greater sorption affinity for kaolinite in the absence of humic acid, but nickel sorption is more enhanced in the presence of humic acid. Although the presence of humic acid enhances cadmium and nickel sorption to kaolinite, low humic acid concentration provides the best conditions for maximum sorption of both metals. High concentrations of humic acid lead to colloid formation which block access of metals with larger hydration radii to sorption sites while also encouraging the formation of humic acid-metal complexes. As with bentonite, caesium and strontium are both poorly sorbed by kaolinite. Unlike with cadmium and nickel however, the enhancement of strontium sorption is supported by higher concentrations of humic acid, these confirm a greater preference for the formation of S-HA-Sr ternary and lower preference for the formation HA-Sr binary complexes. The presence of humic acid inhibits caesium binding, and retention but this reduces with increasing alkalinity, while the reverse is the case with strontium whose retention is very poor and improved in the presence of humic acid and increasing alkalinity. Both caesium and strontium are poorly sorbed and retained by kaolinite but their retention improves with increasing humic acid concentration and pH. Cadmium and nickel also exhibit poor retention to kaolinite but their retentions are more improved under alkaline conditions and higher humic acid concentrations, nickel more so than cadmium. Similar sorption affinities were exhibited by the British (London Clay and Mercia Mudstone) and Nigerian soils (Magodo Laterite and Ikeja Loam) for the metals studied, showing the significance of soil constituent contribution to sorption behaviour. Both British clay matrices have affinity for the metals in the order Cs >> Cd ≈ Ni >> Sr, London Clay has the greater sorption capacity for all the metals, the clay mineral content of Mercia Mudstone is almost entirely made up of Illite while London Clay contains a mixture of smectite, illite and kaolinite with smectite being the most prevalent clay mineral phase. These confirm that smectite-rich clay systems will exhibit better sorption and retention capacities for metal contaminants. Both Nigerian soils showed the same order of affinity for all the metals Cd >> Ni >> Cs >> Sr, cadmium s preferential sorption to kaolinite was observed in its greater sorption and retention by the Nigerian soils which are kaolinite-rich. This preferential sorption of cadmium by kaolinite is confirmed by the Standard Addition experiment where its contribution to cadmium sorption is clearly evident, a trend not replicated with nickel as the sorbing metal. The presence of organic matter in soils or clay systems improves their metal sorption capacity significantly, especially true for insoluble organic matter, however its significance is reduced as pH increases. The contribution of organic matter also depends on the sorption affinity of the metal for organic matter; metals such like strontium are more affected by organic matter presence. The overall sorption behaviour of complex systems such as soils is difficult to attribute to their individual constituents. The laterite soils can be considered a relatively simple soil system containing only four constituents in significant quantities, yet it is difficult to replicate its sorption behaviour using a replicate proportioned mixture of its constituent phases. The additively calculated sorption profiles for the synthetic laterite were different from those obtained experimentally, the reason for this is that the existence of significant particle size differences between the natural and synthetic soils give rise to differences in the availability of sorption sites which is evident from the different CEC values measured for both systems.