Variation in river multi-element chemistry related to bedrock buffering: an example from the Adirondack region of northern New York, USA

Water from four north-flowing rivers (Oswegatchie, Grasse, Raquette, and West Branch of the St. Regis) traversing three distinct geologic terranes (Adirondack Highlands, Adirondack Lowlands, St. Lawrence Valley), originating in the acidified northern Adirondack region, display rapid spatial changes in downriver multi-element chemistry and physical parameters. Downriver, most soluble elements increase (Ba, Ca, Cu, K, Mg, Na, Rb, S, and Sr) while statistically significant decreases in insoluble elements (Al, Ce, Dy, Er, Fe, Gd, La, Mn, Nd, Pr, and Y) also occur. Lithium, Si, and Zr did not show a consistent increasing or decreasing trend. Concentrations of most elements measured on June 5, 2008 were greater than 7?weeks later; however, greater discharge and lower pH enhanced Al concentrations occurred during the later sampling date. Elemental ratios track changes in lithology, anthropogenic influence, and pH. The Raquette River shows the least variation in elemental concentrations because of storage in numerous hydropower reservoirs and has non-detectable concentrations of some redox sensitive elements such as Co, Ni, and V. Oswegatchie tributaries display similar geochemical trends dependent upon their location and local bedrock and show geochemical trends along the trunks of major rivers that are also evident in smaller drainage basins. Comparison with analytical results from the Western Adirondack Stream Survey also indicates acidification is prevalent in the Adirondack Highlands, particularly in the Oswegatchie headwaters during periods of high flow, but acidity is rapidly buffered downriver due to interaction with marble in the Adirondack Lowlands.