Organic petrographic evaluation of carbonaceous material in sediments of the Kinnickinnic River, Milwaukee, WI, U.S.A

Highlights: • Distinguished and quantified coal and coke present in fluvial sediment cores • Other OM found were inert, coal tar pitch, plant material, and cenospheres. • The results of wet vs. dry sieving sample preparations produced similar results. • The highest vol% OM typically corresponded to the highest bulk PAH content. This study examines the use of organic petrology techniques to quantify the amount of coal and carbonaceous combustion by-products (i.e., coke, coal tar/pitch, cenospheres) in sediments taken from the Kinnickinnic River adjacent to the former site of the Milwaukee Solvay Coke and Gas Company. These materials are of concern as contaminants like polycyclic aromatic hydrocarbons (PAHs) are known to readily adsorb to coal and combustion byproducts. Kinnickinnic River sediment samples (n = 36) ranging in depth (1–11 ft.) were collected from eight core locations to quantify and characterize carbonaceous material in the sediments. To determine the amount (vol%) of organic particulates, U.S. Geological Survey (USGS) modified the existing ASTM D2799 using the following categories: coal, coke, coal tar/pitch, inertinite organics, plant material, cenospheres, and mineral matter. Coal fragments were subdivided by rank using vitrinite reflectance (R_o, %) and organic components were further subdivided into the size fractions of coarse (250–1000 μm), fine (63–250 μm), and very fine (<63 μm). Of the 36 samples analyzed, concentrations of coal, coke, and coal tar/pitch ranged from 0 to 18.2 vol%, 0 to 32.0 vol%, and 0 to 2.6 vol%, respectively, with the highest concentrations occurring near point sources (e.g. discharge pipe and coal unloading operations). Samples that were furthest upstream and downstream from the Solvay site exhibited a marked decrease in particulate organics, with exception of one upstream location which had 19.8 vol% coke. Overall, the modified ASTM method provided a means to quantify the abundance of carbonaceous material present in the sediments. Petrography and total PAH concentrations did not provide a clear correlation to organic matter type or size fraction but the samples with the highest vol% organic matter in each core generally corresponded to the sample with the highest bulk PAH content.