Impact of anthropogenic geochemical change and aquifer geology on groundwater phosphorus concentrations

Geologic and geochemical variations across a 4200 km² area of south-central Wisconsin (USA) were used to examine their relationship to phosphorus concentrations in groundwater from more than four hundred private water supply wells. Surficial geology in the study area ranged from Cambrian sandstones to Ordovician dolomites. Groundwater phosphorus concentrations were higher in aquifers of older Cambrian age compared to the concentrations in aquifers of younger Cambrian and Ordovician age. Because iron concentrations were relatively low in these waters and agricultural land use was similar in all geologic regions, we propose that the differences in bedrock phosphorus and anthropogenic geochemical impacts explain the differences in phosphorus concentrations between aquifers. Within the older Cambrian aquifers, groundwater phosphorus concentrations were elevated in groundwater with higher nitrate-nitrogen concentrations. This finding is consistent with the presence of phosphorus within sediment in these strata and geologic conditions that weakly buffered pH reduction from anthropogenic acidification. In contrast, groundwater phosphorus concentrations in younger Cambrian and Ordovician aquifers were not elevated in samples with higher nitrate. Anthropogenic acidification in these carbonate-rich aquifers was neutralized through increased carbonate weathering, which led to higher groundwater calcium and alkalinity and would limit the dissolution of phosphate-rich minerals, such as apatite, where present. Low iron concentrations observed in most samples suggest that the phosphorus release in the Cambrian strata occurs beyond the zone of secondary mineral retention in the soil. These results have important implications for the eutrophication of inland surface waters in areas with bedrock phosphorus and anthropogenic acidity that is not neutralized before it contacts phosphatic rock.