Metal mobility during in situ chemical oxidation of TCE by KMnO4

The potential for trace-metal contamination of aquifers as a side effect of In Situ Chemical Oxidation (ISCO) of chlorinated solvent contamination by KMnO(4) is investigated with column experiments. The experiments investigate metal mobility during in situ chemical oxidation of TCE by KMnO(4) under conditions where pH, flow rate, KMnO(4), TCE, and trace-metal concentrations were controlled. During ISCO, the injection of MnO(4) creates oxidizing conditions, and acidity released by the reactions causes a tendency toward low pH in aquifers. In order to evaluate the role of pH buffering on metal mobility, duplicate columns were constructed, one packed with pure silica sand, and one with a mixture of silica sand and calcite. Aqueous solutions of TCE and KMnO(4) (with 1 mg/L Cu, Pb, Zn, Mo, Ni, and Cr(VI)) were allowed to mix at the inlet to the columns. After the completion of the experiments, samples of Mn oxide were removed from the columns and analyzed by analytical scanning and transmission electron microscopy. In order to relate the results of the laboratory experiments to field settings, the analyses of Mn-oxide samples from the lab experiments were compared to samples of Mn oxide collected from a field-scale chemical-oxidation experiment that were also analyzed by analytical electron microscopy as well as time-of-flight secondary-ion mass spectroscopy. The pH ranged from 2.40 in the silica sand column to 6.25 in the calcite-containing column. The data indicate that aqueous Mo, Pb, Cu and Ni concentrations are attenuated almost completely within the columns. In contrast, Zn concentrations are not significantly attenuated and Cr(VI) is transported conservatively. The results indicate that within the range 2.40 to 6.25, metal mobility is not affected by pH. Comparison of analyses of Mn-oxide from the lab and field demonstrate that a variety of metals are sequestered from solution by Mn oxide.     

An evaluation of mixed species in-situ and ex-situ feeding assays: the altered response of Asellus aquaticus and Gammarus pulex

Mixed species feeding assays were undertaken with pollution sensitive (Gammarus pulex) and tolerant (Asellus aquaticus) macro-invertebrates during August 2003 and April 2004. The purpose of this study was to establish if a test animals' response is comparable during in-situ and ex-situ toxicity tests. Seven test sites were established along an undisclosed stream, which received leachate discharge from an unlined, disused UK landfill site. Sampling points A-B were upstream of the contamination, C was adjacent to the influx and D-G were downstream of the leachate discharge (at 100 m intervals). During the in-situ and ex-situ tests, 2-week-old male laboratory bred A. aquaticus and G. pulex were used as test animals. The animals were transplanted to the seven sampling points for the duration of the in-situ tests, whilst water samples from each site were returned to the laboratory for ex-situ testing. The results show that the animals' mortality and feeding rates followed similar trends during the in-situ and ex-situ tests, however, the animals' response was amplified during the in-situ tests. It was also observed that the effects were greater in April, compared to August that may be attributed to a higher frequency of rainfall during spring, which could have flushed a greater proportion of the contaminant load from the waste mass and as a consequence, higher levels of pollution may have leached into the stream from the landfill site. The study, therefore, concludes that in-situ toxicity tests are a more precise monitoring technique, in comparison to ex-situ assays.     

Dissipation of PAHs in saturated, dredged sediments: a field trial

Sediments dredged from navigable rivers often contain elevated concentrations of recalcitrant, potentially toxic organic compounds such as polychlorinated biphenyls (PCBs) and polyaromatic hydrocarbons (PAHs). The presence of these compounds often requires that the sediments be stored in fully contained disposal facilities. A 3-year field study was conducted at the Jones Island disposal facility in Milwaukee, Wisconsin, to compare bioremediation of PAHs in contaminated dredged sediments in the absence of plants to phytoremediation with Salix nigra (black willow) (SX61), Spartina pectinata (prairie cord grass), Carex aquatalis (lake sedge), Lolium multiflorum (annual rye), and Scirpus fluviatilis (bulrush). Nine PAHs were detected initially in the sediments. Over the 3-year experiment, acenaphthene dissipation ranged from 94% to 100%, whereas anthracene, benzo[a]pyrene and indo[1,2,3-cd]pyrene generally had modest decreases in concentration (0-30% decrease). The remaining five PAHs ranged in degree of disappearance from 23% to 82%. Planted treatments did not enhance PAH dissipation relative to those without plants, but treatments with high biomass yield and high transpiration plant species had significantly less removal of PAHs than unplanted controls. Significant, negative correlations between nitrogen removal and decreases in PAH concentration suggest that competition for nutrients between plants and microorganisms may have impeded the microbial degradation of PAHs in the rhizosphere of the more rapidly growing plant species.     

Removal of Prussian blue from contaminated soil in the rhizosphere of cyanogenic plants

The fate of radiolabeled cyanide in soil was investigated during exposure to cyanogenic plant species, sorghum (Sorghum bicolor var. P721) and flax (Linum usitassimum var. Omega-Gold), in fully-contained growth chambers. Labeled cyanide was subject to microbial transformation, assimilation by plant roots, incorporation and biodegradation in plant tissue. For this study, (14)C-labeled cyanide was added to soil, and distribution of (14)C activity was assessed before plant establishment and after harvest. After 3 months of plant growth, 7% of the (14)C-labeled cyanide was converted to (14)CO(2) with sorghum and 6% with flax, compared with only 2% conversion in unplanted soil. A small amount of unaltered cyanide was shown to be accumulated by the plants (approximately 140 mg cyanide/kg plant or <0.1% of the total). Results from this experiment demonstrate the potential of cyanogenic plants for use in phytoremediation of cyanide-contaminated soil.     

Acute and sub-lethal toxicity of landfill leachate towards two aquatic macro-invertebrates: demonstrating the remediation potential of air stripping

A specific leachate that contained 1.036 mg l(-1) of 2-chlorobiphenyl was used in the study (255 mg l(-1) COD and 133 mg l(-1) BOD5). Bench scale (20 l) air stripping trials were used to simulate on a small-scale the treatment potential of this method. Air stripping effectively reduced the leachates COD concentration. Regardless of the volume of air supplied (1-5 l of air per minute) the leachates COD reached a <50 mg l(-1) equilibrium after 96-h exposure, however, increasing the volume of air accelerated the process. In untreated leachate, the LC50 for Asellus aquaticus was 57% v/v leachate in deionised water and 5% for Gammarus pulex (96-h, static LC50 tests without nutrition and oxygen depleting conditions). After being exposed to air stripping, these values rose from 90% to below the LC50 threshold for Asellus when 1-5 l of air per minute were applied and 30-90% for Gammarus. Furthermore, in sub-lethal concentrations of air stripped leachate (leachate that had been exposed to 5-l of air per minute for 96-h) the population dynamics of both test species remained unaltered.     

Phytoremediation of aged petroleum sludge: effect of inorganic fertilizer

Phytoremediation is a promising new technology that uses higher plants to enhance biodegradation. Nutrient availability is an important factor governing the success of phytoremediation and can be regulated through the addition of fertilizer. A greenhouse study was conducted to assess the importance of nitrogen and phosphorus for the phytoremediation of petroleum sludge. Degradation of total petroleum hydrocarbons (TPH) was quantified for six fertilization rates and three vegetation treatments: bermuda grass [Cynodon dactylon (L.) Pers.], tall fescue (Festuca arundinacea Schreb.), and an unvegetated control. During the first 6 mo of the experiment, TPH declined by an average of 49% with no significant differences between treatments. After 1 yr, TPH degradation was significantly greater in both vegetated treatments with a mean TPH reduction of 68% for bermuda, 62% for fescue, and 57% for the unvegetated control. Degradation of TPH in the fescue and bermuda treatments was significantly lower in the treatments in which no fertilizer was added or N and P were added simply to maintain plant growth compared with the higher rates of fertilization. For this short-term, greenhouse experiment, optimal remediation was obtained by fertilization that produced a C to N to P ratio of 100:2:0.2.