Field study of dispersion in a heterogeneous aquifer: 4. Investigation of adsorption and sampling bias

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Abstract
The declining mass balance trend observed for bromide and three fluorobenzoate tracers during a natural gradient experiment at a site near Columbus, Mississippi, prompted investigations related to the reactivity of the tracers and the representativeness of the tracer samples obtained from multilevel samplers. A laboratory soil column study indicated that adsorption of bromide during the field experiment was of the order of 20% and that up to 10% of the three fluorobenzoates was adsorbed. The presence of iron oxides and kaolinite in the alluvial aquifer combined with the low ground water pH of 4.8 produced geochemical conditions conducive to adsorption of the anionic tracers. Multilevel samplers (MLS) used in the field experiment were evaluated by comparing bromide concentrations from the MLS with water samples extracted from adjacent soil cores. Vertically averaged bromide concentrations for the MLS were 21% lower than those for the cores. A matrix diffusion process in conjunction with a natural tendency for preferential sampling from permeable regions in the heterogeneous alluvial sediments is proposed as an explanation for the apparent bias in the MLS sample concentrations. This process is shown to be qualitatively consistent with the tracer mass balance observed during the natural gradient experiment.