Variations of common riverine contaminants in reservoir sediments

Organic molecules in reservoir sediments can be used as tracers of contaminant inputs into rivers. Vertical variations in the molecular records can be ascribed to pre-depositional alteration within the water column, or in situ post-depositional alteration. We report the molecular stratigraphy of four common riverine contaminant groups in sediment of the largest reservoir on the Danube River, the Iron Gate I Reservoir. Sediments were rapidly deposited, with little variation in texture and, as revealed by analytical pyrolysis, in the concentration and composition of natural sedimentary organic matter. However, a detailed molecular inspection did reveal differences in distribution and organic carbon (OC)-normalized concentrations of contaminants. The OC-normalized concentrations of nonylphenol increased by one order of magnitude with depth down the 70 cm sediment core. There is a strong correlation between sediment depth and the ratio of nonylphenol to its precursor (nonylphenol monoethoxylate). This indicated that nonylphenol was produced in situ. While the relative proportions of C10-C14 linear alkylbenzenes remained constant with increasing depth, they exhibited variations in isomer distribution. These variations, which are due to different degrees of degradation, appear to have occurred within the water column prior to sedimentation of suspended solids. The distribution of 40 polycyclic aromatic hydrocarbons revealed origins from both pyrogenic and petrogenic sources. The differences in their compositions were not depth-related, but rather were associated with variations in the sorption capacities of texturally different sediments. Perylene showed slightly higher concentrations at greater depths, while the OC-normalized concentration of retene systematically increased with sediment depth. This is consistent with formation of retene and perylene via very early diagenetic transformation. The presence of petroleum biomarkers indicated minor contamination by fossil fuels.