Manganese and Mn/Ca ratios in soil and vegetation in forests across the northeastern US: Insights on spatial Mn enrichment.

Manganese (Mn) cycling in the Critical Zone is important because of its role as an essential nutrient and potential toxicity to plants and organisms. Quantifying Mn enrichment in terrestrial environments has been limited since Mn is monoisotopic. However, elemental ratios of Mn/Ca ratios may be used to determine spatial Mn enrichment and in aboveground and belowground pools. The objectives of this study were to quantify the spatial variation in Mn concentrations and Mn/Ca ratios in foliage, bolewood, forest floor, and mineral soil horizons across the northeastern United States and compare Mn/Ca ratios to estimate enrichment. Forest floor and mineral soil samples were collected from 26 study sites across the northeastern United States and analyzed by strong acid digestion. Foliage and bolewood was collected from 12 of the 26 sites and analyzed for total Mn and Ca. Our results show forest floor and mineral soil horizon Mn concentrations and Mn/Ca ratios were higher at Pennsylvania and New York sites than New Hampshire and Vermont sites. Using a modified isotope equation, enrichment factors (EF) for Mn/Ca ratios were calculated to be ~3.6 in the forest floor, upper and lower mineral soil horizons at sites in New York and Pennsylvania compared to reference sites in New Hampshire and Vermont. Foliar and bolewood Mn concentrations also decreased from Pennsylvania towards New Hampshire. Moreover, foliar and bolewood Mn concentrations were strongly correlated to forest floor, upper, and lower mineral soil Mn concentrations. It was hypothesized that internal cycling (uptake, throughfall, and litterfall) of Mn controls retention of enriched Mn in forests. Geologic influences from a lithologic gradient and soil pH gradient could also influence Mn enrichment in addition to Mn pollution. Ratios of Mn/Ca and other elemental ratios hold promise as geochemical tracers but require further development.