Geochemical stability of chromium in sediments from the lower Hackensack River, New Jersey.

Elevated levels of chromium, partly attributable to historical disposal of chromite ore processing residue, are present in sediment along the eastern shore of the lower Hackensack River near the confluence with Newark Bay. Due to anaerobic conditions in the sediment, the chromium is in the form of Cr(III), which poses no unacceptable risks to human health or to the river ecology. However, as water quality conditions have improved since the 1970s, aerobic conditions have become increasingly prevalent in the overlying water column. If these conditions result in oxidation of Cr(III) to Cr(VI), either under quiescent conditions or during severe weather or anthropogenic scouring events, the potential for adverse ecological effects due to biological exposures to Cr(VI) is possible, though the reaction kinetics associated with oxidation of Cr(III) to Cr(VI) are unfavorable. To investigate the stability of Cr(III) in Hackensack River sediments exposed to oxic conditions, sediment suspension and oxidation experiments and intertidal sediment exposure experiments that exposed the sediments to oxic conditions were conducted. Results revealed no detectable concentrations of Cr(VI), and thus no measurable potential for total chromium oxidation to Cr(VI). Furthermore, total chromium released from sediment to elutriate water in the oxidation and suspension experiments ranged from below detection (<0.01 mg/L) to 0.18 mg/L, below the freshwater National Recommended Water Quality Criteria (NRWQC) of 0.57 mg/L for Cr(III). These results support conclusions of a stable, in situ geochemical environment in sediments in the lower Hackensack River with respect to chromium. Results showed that chemicals other than Cr(VI), including copper, lead, mercury, zinc, and PCBs, were released at levels that may pose a potential for adverse ecological effects.

Hydroxyl radical production via the photo-Fenton reaction in the presence of fulvic acid.

The photo-Fenton reaction, the reaction of photoproduced Fe(II) with H2O2 to form the highly reactive hydroxyl radical (OH*), could be an important source of OH* in sunlit natural waters. To determine if the photo-Fenton reaction is significant in mildly acidic surface waters, we conducted experiments simulating conditions representative of natural freshwaters using solutions of standard fulvic acid and amorphous iron oxide at pH 6.0. A probe method measuring 14CO2 produced by the reaction of 14C-labeled formate with OH* was used to detect small OH* production rates without otherwise influencing the chemical reactions occurring in the experiments. Net H2O2 accumulation was simultaneously measured using an acridinium ester chemiluminescence method. Measured losses of H2O2 by reaction with Fe(II) in dark experiments produced approximately the expected quantities of OH*. The difference between H2O2 accumulation in the presence and absence of Fe(III) in fulvic acid solutions exposed to light was interpreted as the loss of H2O2 by reaction with photoproduced Fe(II), consistent with measured OH* production rates. The Fe ligand desferrioxamine mesylate eliminated both OH* production and H2O2 photoloss induced by Fe. Our results imply that when Fe is a major sink of H2O2, the photo-Fenton reaction is likely to be the most important source of OH*, leading to a significant sink of organic compounds in a wide variety of sunlit freshwaters.