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This study investigated different cleanup procedures to eliminate sulfur interference from sediments from a reclaimed mining site in Sparta, Illinois. Sonication extraction with activated copper powder was the most effective method to eliminate elemental sulfur. Extracts were then cleaned with a Florisil column before pyrethroid, organophosphate, and organochlorine pesticides were determined using gas chromatography with electron-capture detection. The method detection limits ranged from 0.03 to 0.68 µg/kg dry sediment. Recoveries for spiked samples were from 82.2% to 132.7% with relative standard deviations < 15%. Fifty-four sediment samples collected from 15 lakes and 1 stream in the proposed Illinois National Guard Armory were analyzed using the desulfuration procedure. Of the 26 target pesticides analyzed in sediment, 20 were detected above the detection threshold of 1 µg/kg. DDT was detected most frequently (found at 50% of the sampling sites), whereas permethrin was found at the greatest concentration. [ABSTRACT FROM AUTHOR]

Whole-sediment toxicity identification evaluation (TIE) techniques were employed on the Illinois River Complex (IRC), USA to identify the sources of sediment toxicity that may have contributed to the decline in benthic invertebrate populations. The TIE focused on three classes of contaminants: ammonia, metals, and organics. Sediment toxicity was assessed using the amphipod Hyalella azteca, and the focus of the TIE was on assessing spatial and temporal patterns of contamination. Past studies suggested that ammonia was the major source of contamination in IRC sediments. However, the present study suggested that polycyclic aromatic hydrocarbons (PAHs) were the primary contributor to sediment toxicity. Phase I testing showed 46% of the site trials (12 of 26) exhibited increased H. azteca survival (p < 0.05) with the addition of powdered coconut charcoal (organic amendment), whereas zeolite (ammonia amendment) and Resin Tech SIR 300 (cationic metals amendment) did not increase H. azteca survival. Phase II testing revealed PAH concentrations were high enough to cause the observed toxicity, confirming phase I results. Spatially, sediment toxicity as well as pore-water ammonia concentrations declined with distance downstream from suspected contaminant sources, indicating a potential dilution or remedial effect. Temporally, pore-water ammonia, metals, and PAH concentrations varied among sampling periods over an annual cycle for some sites near urbanized areas, while remaining temporally consistent at others. The results of the present study provide new information on the sources of toxicity within the IRC, and demonstrate the importance of evaluating spatial and temporal aspects in sediment TIEs. This is particularly important for evaluations in riverine systems in which hydrologic processes can result in large variation in sediment toxicity on temporal and spatial scales.

Two chemical approaches, Tenax extraction and matrix solid phase microextraction (matrix-SPME), were evaluated for their potential to improve the prediction of bioavailability by equilibrium partitioning theory (EPT) across sediments with various characteristics. Biota-sediment accumulation factors (BSAFs) and body residues were quantified by exposing Lumbriculus variegatus to three PCB-contaminated field sediments. The concentration of PCBs in biota was positively correlated to the total PCB sediment concentration, the PCB concentration in the rapidly desorbing fraction estimated using Tenax extraction, and the PCB concentration on the SPME fibers. Results showed EPT was acceptable for estimating bioavailability from the tested sediments with sum PCB BSAFs of 1.18-2.47; however, it overestimated PCB bioavailability from sandy sediment. Both Tenax extraction and matrix-SPME, which take sequestration into account, reduced variability in prediction of PCB bioavailability across sediments, including the sandy sediment, and could be used as cost- and time-efficient alternatives for bioassay. Matrix-SPME was considered the better technique due to its ability to directly predict PCB body residues in the exposed biota and its potential use with in situ applications in the field.

Organochlorine compounds (OCs), including polychlorinated biphenyls and organochlorine pesticides, were used on lands adjacent to the Middle Mississippi River (MMR; USA) from 1930 through 1988, and they continue to occur in MMR fish. These compounds are estrogenic and/or antiandrogenic, and they alter hormone production and reception within the brain and gonads of male fish, resulting in intersexuality and/or suppressed gonadal development. To assess how OCs affect reproduction of MMR fish, we quantified OC accumulation, intersexuality, and gonadal development in male shovelnose sturgeon (Scaphirhynchus platorynchus) throughout the MMR during the spring of 2003. Gonads were observed for intersexual characteristics, weighed to calculate the gonadosomatic index (GSI), and examined histologically. Tissue accumulation of OCs was quantified in gonads, brain-hypothalamic-pituitary (BHP) complex, and fillets. Four of 48 mature males were identified macroscopically as intersexuals, and a fifth was found through histology (a 10.4% incidence). Intersexuals accumulated higher concentrations of OCs in the BHP complex compared with those of mature males. In addition, GSI and OC accumulation within the BHP complex, gonads, and fillets of mature males were negatively related. Exposure to OCs before or during sexual differentiation likely induces intersexuality in MMR shovelnose sturgeon, and exposure throughout gonadal maturation inhibits gonadal development.