Year of Publication

2014

Degree Name

Doctor of Philosophy (PhD)

Document Type

Doctoral Dissertation

College

Agriculture, Food and Environment

Department

Plant and Soil Sciences

First Advisor

Dr. A.D. Karathanasis

Abstract

Despite indications that they are potential contaminant transport systems and threats to groundwater quality, very little effort has been invested in comparing contaminant transport behavior of natural environmental nanocolloids and their corresponding macrocolloid fractions in the presence of As, Se, Pb, and Cu contaminants. This study involved physico-chemical, mineralogical, stability and contaminant-transport characterizations of nano- (< 100 nm) and macro-colloids (100-2000 nm) fractionated from three Kentucky soils and one biosolid waste. Particle size was investigated with SEM/TEM and dynamic light scattering. Surface reactivity was estimated using CEC and zeta potential. Mineralogical composition was determined by XRD, FTIR, and thermogravimetric analyses. Sorption isotherms assessed affinities for Cu2+, Pb2+, AsO3-, and SeO4-2 contaminants, while settling kinetics experiments of suspensions at 0, 2 and 10 mg/L contaminants determined stability and transportability potential. Undisturbed 18x30 cm KY Ashton Loam soil monoliths were also used for transport experiments, involving infusion of 50 mg L-1 colloid suspensions spiked with 2 mg L-1 mixed contaminant loads in unsaturated, steady state, unit gradient downward percolation experiments. Overall, nanocolloids exhibited greater stability over corresponding macrocolloids in the presence and absence of contaminants following specific mineralogy trends. Physicochemical characterizations indicated that extensive organic carbon surface coatings and higher Al/Fe:Si ratios may have induced higher stability in the nanocolloid fractions, in spite of some hindrance by nano-aggregation phenomena. In the transport experiments, nanocolloids eluted significantly higher concentrations of colloids, total, and colloid-bound metals than corresponding macrocolloids. Contaminant elutions varied by colloid type, mineralogy and contaminant, with the following sequences: soil-colloids>bio-colloids, smectitic>mixed≥kaolinitic>biosolid, and Se>Pb/Cu≥As. Our findings demonstrate that even though they behave more like nano-aggregates rather than individual nano-particles, nanocolloids may exhibit significantly higher mobility and contaminant transport potential over great distances in subsoil environments than their corresponding macrocolloid fractions.

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