Quantum Chemical Modeling of the Effects of Hydrated Lime (Calcium Hydroxide) as a Filler in Bituminous Materials.

Hydrated lime is widely used as a mineral filler to improve several properties of bituminous materials such as reducing the susceptibility of the composite to moisture-induced damage. Although experimental evidence supports the efficacy of using hydrated lime as a mineral filler, the molecular scale mechanism of reactivity of hydrated lime within the bitumen to reduce moisture damage is not understood. This is important when considering the durability of structural applications of bituminous materials such as asphalt concrete pavements subjected to both environmental and loading extremes. In this study, the interaction between hydrated lime and the key molecular building blocks of bitumen is modeled using density functional theory and compared against analogues of other common fillers such as calcite and quartz. Free energies of dissociation (ΔG dissoc) are calculated, and the nature of the bonds is characterized with contour maps of the Laplacian of the electron density. Hydrated lime is capable of reacting with specific functional groups in bitumen moieties and developing strong, water-resistant complexes. Among the functional groups investigated, carboxylic acids are the preferential reaction sites between hydrated lime and the bitumen moieties. Values as high as ΔG dissoc = +49.42 kcal/mol are reported for hydrated lime with water as the surrounding solvent. In contrast, analogues of calcite (ΔG dissoc = +15.84 kcal/mol) and quartz (ΔG dissoc = +4.76 kcal/mol) are unable to chemically react as strongly as hydrated lime in the presence of water. Contour maps of the Laplacian of the electron density indicate that the bonds between hydrated lime and model asphalt moieties are of an ionic nature. The atomistic modeling results correlate with thermodynamic calculations derived from experimental constants and are consistent with infrared spectrometric data.

Adsorption of iron cyanide complexes onto clay minerals, manganese oxide, and soil.

The adsorption characteristics of an iron cyanide complex, soluble Prussian blue KFe(III)[Fe(II)(CN)(6)], were evaluated for representative soil minerals and soil at pH 3.7, 6.4 and 9.7. Three specimen clay minerals (kaolinite, montmorillonite, and illite), two synthesized manganese oxides (birnessite and cryptomelane), and a Drummer soil from Indiana were used as the adsorbents. Surface protonation of variable charge sites increased with decreasing pH yielding positively charged sites on crystal edges and enhancing the attractive force between minerals and iron cyanide complexes. Anion adsorption on clays often is correlated to the metal content of the adsorbent, and a positive relationship was observed between iron or aluminum content and Prussian blue adsorption. Illite had high extractable iron and adsorbed more ferro-ferricyande anion, while kaolinite and montmorillonite had lower extractable iron and adsorbed less. However, less pH effect was observed on the adsorption of iron cyanide to manganese oxides. This may due to the manganese oxide mediated oxidation of ferrocyanide [Fe(II)(CN)(6)(4-)], to ferricyanide [Fe(III)(CN)(6)(3-)], which has a low affinity for manganese oxides.

Plant germination and growth after exposure to iron cyanide complexes.

Phytoremediation has been proposed for treatment of cyanide-contaminated soil. This study was conducted to identify plants with the highest potential for phytoremediation of iron cyanide contaminated soil. Multiple cultivars of two cyanogenic species, sorghum (Sorghum bicolor) and flax (Linum usitatissimum), and one non-cyanogenic species, switchgrass (Panicum virgatum L), were selected for evaluation. The cultivars were screened by quantifying germination and root elongation. Differences in germination emerged among the cultivars (P < 0.05), but these differences appeared to be unrelated to cyanide concentration. The presence of 1000 mg/kg Prussian blue tended to suppress root growth parameters of flax and switchgrass but did not affect sorghum similarly.

Lability of polycyclic aromatic hydrocarbons in the rhizosphere.

Remediation of soils containing high concentrations of polycyclic aromatic hydrocarbons (PAHs) seldom results in complete removal of contaminants, but residual toxicity often is reduced. In this study, soil from a former manufactured gas plant site was treated for 12 months by phytoremediation and then tested for total PAHs, Tenax-TA extractable ("labile") PAHs, aqueous soluble PAHs (PAH(wp)) , and biotoxicity assessed by earthworms survival, nematode mortality, emergence of lettuce seedlings, and microbial respiration. Prior to phytoremediation, the soil had toxic impacts on all bioassays (except the nematodes), and 12 months of remediation decreased this response. Change in labile PAHs was a predictor for change in total PAH for 3- and 4-ring compounds but not for the 5- and 6-ring. Decreases in labile PAHs were correlated (r(2)>or=0.80) with toxicity in the bioassays except microbial respiration. PAH(wp) was correlated only with nematode toxicity prior to remediation but with none of the tests after remediation. Total PAHs were not correlated with any of the bioassay tests. Tenax-TA appears to have potential for predicting residual toxicity in remediated soils and is superior to total concentrations for that application.

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.

Evaluation of hydrophobicity in PAH-contaminated soils during phytoremediation.

The impact of recalcitrant organic compounds on soil hydrophobicity was evaluated in contaminated soil from a manufactured gas plant site following 12 months of phytoremediation. Significant reduction in soil wetting and water retention was observed in contaminated soil compared to an uncontaminated control. Phytoremediation was effective at reducing total PAHs by 69% with corresponding changes in soil classification from extremely hydrophobic (initial sample) to moderately-strongly hydrophobic (planted) and hydrophilic-very hydrophilic (unplanted) after 12 months. The greatest reduction in soil hydrophobicity was observed in the unplanted, unfertilized treatments that had the lowest removal rate of PAHs. The presence of plants may contribute to hydrophobicity in contaminated soil.

Phytoremediation of polycyclic aromatic hydrocarbons in soil: part I. Dissipation of target contaminants.

Phytoremediation has been demonstrated to be a viable cleanup alternative for soils contaminated with petroleum products. This study evaluated the application of phytoremediation to soil from a manufactured gas plant (MGP) site with high concentrations of recalcitrant, polycyclic aromatic hydrocarbons (PAHs). Two greenhouse studies investigated the potential dissipation and plant translocation of PAHs by fescue (Festuca arundinacea) and switchgrass (Panicum virgatum) in the first experiment and zucchini (Curcubita pepo Raven) in the second. The MGP soil was highly hydrophobic and initially inhibited plant growth. Two unplanted controls were established with and without fertilization. In the first experiment, concentrations of PAHs decreased significantly in all treatments after 12 mo. Plant biomass and microbial numbers were statistically equivalent among plant species. PAH concentrations in plant biomass were negligible for fescue and switchgrass. In the second experiment, zucchini enhanced the dissipation of several PAHs after 90 d of treatment when compared to the unvegetated soil. Plant tissue concentrations of PAHs were not elevated in the zucchini roots and shoots, and PAHs were not detectable in the fruit.

Phytoremediation of polycyclic hydrocarbon contaminated soil: part II. Impact on ecotoxicity.

Several biological assays were used to evaluate the toxic effects of contaminants in soil after phytoremediation. During the treatment process, significant decreases in overall toxicity were observed. Specifically, earthworm survivability and lettuce germination increased over the study period. Microbial respiration improved, but only in planted treatments. Toxicity and total polycyclic aromatic hydrocarbon concentrations showed some correlation, but the relationships generally were not significant. Soil moisture was less of a predictor for biological responses. The presence of plants did not provide a clear advantage for improving toxicity compared to unplanted treatments.

Assessment of contaminant lability during phytoremediation of polycyclic aromatic hydrocarbon impacted soil.

Polycyclic aromatic hydrocarbons (PAHs) are recalcitrant compounds, some of which are known carcinogens, often found in high residual soil concentrations at industrial sites. Recent research has confirmed that phytoremediation holds promise as a low-cost treatment method for PAH contaminated soil. In this study, the lability of soil bound PAHs in the rhizosphere was estimated using solid phase extraction resin. An extraction time of 14 days was determined to be appropriate for this study. Resin-extractable PAHs, which are assumed to be more bioavailable, decreased during plant treatments. Significant reductions in the labile concentrations of several PAH compounds occurred over 12 months of plant growth. The differences in concentration between the unplanted and the planted soil indicate that the presence of plant roots, in addition to the passage of time, contributes to reduction in the bioavailability of target PAHs.

Effect of root death and decay on dissipation of polycyclic aromatic hydrocarbons in the rhizosphere of yellow sweet clover and tall fescue.

A 12-mo greenhouse study was conducted to evaluate the contribution of root death and decay on the dissipation of polycyclic aromatic hydrocarbons (PAHs) in rhizosphere soil. The contaminated soil was previously treated by land-farming, but residual PAHs remained after treatment. Tall fescue (Festuca arundinacea Schreb.) and yellow sweet clover (Melilotus officinalis Lam.) were the target plants. To specifically evaluate the effect of root decay on contaminant dissipation, plants were treated with glyphosate, a broad spectrum herbicide, to induce root decay. Although tall fescue treatments had the highest root and shoot biomass and root surface area, this plant did not result in the highest contaminant degradation rates. Significant differences were noted between treatments for seven PAHs, with the active yellow sweet clover resulting in 60 to 75% degradation of these compounds. Induced root death and decay did not produce a significant enhancement of PAH degradation. The PAH microbial degrader populations in the vegetated treatments were more than 100 times greater than those in the unvegetated control. The phospholipid fatty acid (PLFA) structural group profile shifted over the growing period, indicating a change in the community structure. In conclusion, phytoremediation was shown to be an effective polishing tool for PAH-affected soil previously subjected to biological treatment.

Effectiveness of phytoremediation as a secondary treatment for polycyclic aromatic hydrocarbons (PAHs) in composted soil.

A greenhouse study was conducted over a 12-month period to investigate the fate of polycyclic aromatic hydrocarbons (PAHs) in soil using phytoremediation as a secondary treatment. The soil was pretreated by composting for 12 weeks, then planted with tall fescue (Festuca arundinacea), annual ryegrass (Lolium multiflorum), and yellow sweet clover (Melilotus officinalis). Two sets of unvegetated controls also were evaluated, one fertilized and one unfertilized. Total PAH concentrations decreased in the tall fescue, annual ryegrass, and yellow sweet clover treatments by 23.9%, 15.3%, and 9.1%, respectively, whereas the control was reduced by less than 5%. The smaller two- and most of the three-ringed compounds--naphthalene, acenaphthylene, acenaphthene, fluorene, and anthracene--were not found in detectable concentrations in any of the treatments. The most probable number analysis for microbial PAH degraders did not show any statistically significant differences among treatments. There were significant differences among treatments (p < 0.05) for the residual concentrations of five of the target PAHs. Root surface area measurements indicated that tall fescue and annual ryegrass both had significantly higher root surface area than yellow sweet clover, although the two species were not significantly different from each other. The tall fescue treatment resulted in the highest root and shoot biomass, followed by annual ryegrass and yellow sweet clover, and also had the highest percent of contaminant removal after 12 months. These results imply a positive relationship between plant biomass development and PAH biodegradation.

Pyrene degradation in the rhizosphere of tall fescue (Festuca arundinacea) and switchgrass (Panicum virgatum L.).

A growth chamber study was conducted to investigate the fate of pyrene in the rhizosphere of tall fescue (Festuca arundinacea) and switchgrass (Panicum virgatum L.). For this study, 14C-labeled pyrene was used, and distribution of 14C activity was assessed after plant establishment. After 190 days of incubation, 37.7 and 30.4% of 14C-pyrene was mineralized in the soil planted with tall fescue and switchgrass, respectively, while 4.3% mineralization was observed for the unplanted control. Only 7.6 and 8.7% of pyrene was recovered from the soil in the two planted treatments, while 31.5% of pyrene remained in the unplanted control. Significant amounts of 14C were observed for all treatments and controls in the humic/fulvic fraction of soil at the end of the experiment. This research indicates the potential for pyrene mineralization in planted systems, although the ultimate fate of degradation byproducts is uncertain.