Bioremediation and phytoremediation of total petroleum hydrocarbons (TPH) under various conditions.

Remediation of contaminated soils is often studied using fine-textured soils rather than low-fertility sandy soils, and few studies focus on recontamination events. This study compared aerobic and anaerobic treatments for remediation of freshly introduced used motor oil on a sandy soil previously phytoremediated and bioacclimated (microorganisms already adapted in the soil environment) with some residual total petroleum hydrocarbon (TPH) contamination. Vegetated and unvegetated conditions to remediate anthropogenic fill containing residual TPH that was spiked with nonaqueous phase liquids (NAPLs) were evaluated in a 90-day greenhouse pot study. Vegetated treatments used switchgrass (Panicum virgatum). The concentration of aerobic bacteria were orders of magnitude higher in vegetated treatments compared to unvegetated. Nevertheless, final TPH concentrations were low in all saturated soil treatments, and high in the presence of switchgrass. Concentrations were also low in unvegetated pots with fertilizer. Acclimated indigenous microbial communities were shown to be more effective in breaking down hydrocarbons than introducing microbes from the addition of plant treatments in sandy soils. Remediation of fresh introduced NAPLs on pre-phytoremediated and bioacclimated soil was most efficient in saturated, anaerobic environments, probably due to the already pre-established microbial associations, easily bioavailable contaminants, and optimized soil conditions for microbial establishment and survival.

Breakdown of low-level total petroleum hydrocarbons (TPH) in contaminated soil using grasses and willows.

A phytoremediation study targeting low-level total petroleum hydrocarbons (TPH) was conducted using cool- and warm-season grasses and willows (Salix species) grown in pots filled with contaminated sandy soil from the New Haven Rail Yard, CT. Efficiencies of the TPH degradation were assessed in a 90-day experiment using 20-8.7-16.6 N-P-K water-soluble fertilizer and fertilizer with molasses amendments to enhance phytoremediation. Plant biomass, TPH concentrations, and indigenous microbes quantified with colony-forming units (CFU), were assessed at the end of the study. Switchgrass grown with soil amendments produced the highest aboveground biomass. Bacterial CFU's were in orders of magnitude significantly higher in willows with soil amendments compared to vegetated treatments with no amendments. The greatest reduction in TPH occurred in all vegetated treatments with fertilizer (66-75%) and fertilizer/molasses (65-74%), followed sequentially by vegetated treatments without amendments, unvegetated treatments with amendments, and unvegetated treatments with no amendment. Phytoremediation of low-level TPH contamination was most efficient where fertilization was in combination with plant species. The same level of remediation was achievable through the addition of grasses and/or willow combinations without amendment, or by fertilization of sandy soil.

An investigation of strong sodium retention mechanisms in nanopore environments using nuclear magnetic resonance spectroscopy.

Recent experimental research into the adsorption of various cations on zeolite minerals has shown that nanopore channels of approximately 0.5 nm or less can create an effect whereby the adsorption of ions, especially those that are weakly hydrated, can be significantly enhanced. This enhanced adsorption occurs due to the removal of hydrating water molecules which in turn is caused by the nanopore channel's small size. A new adsorption model, called the nanopore inner-sphere enhancement (NISE) effect, has been proposed that explains this unusual adsorption mechanism. To further validate this model a series of nuclear magnetic resonance (NMR) spectroscopy studies is presented here. NMR spectra were gathered for Na adsorbed on three zeolite minerals of similar chemical composition but differing nanoporosities: zeolite Y with a limiting dimension of 0.76 nm, ZSM-5 with a limiting dimension of 0.51 nm, and mordenite with a limiting dimension of 0.26 nm. The NMR experiments validated the predictions of the NISE model whereby Na adsorbed via outer-sphere on zeolite Y, inner-sphere on ZSM-5, and a combination of both mechanisms on mordenite. The strong Na adsorption observed in these nanoporous minerals conflicts with sodium's general designation as a weak electrolyte.

Modeling the adsorption of hydrogen, sodium, chloride and phthalate on goethite using a strict charge-neutral ion-exchange theory.

Simultaneous adsorption modeling of four ions was predicted with a strict net charge-neutral ion-exchange theory and its corresponding equilibrium and mass balance equations. An important key to the success of this approach was the proper collection of all the data, particularly the proton adsorption data, and the inclusion of variable concentrations of conjugate ions from the experimental pH adjustments. Using IExFit software, the ion-exchange model used here predicted the competitive retention of several ions on goethite by assuming that the co-adsorption or desorption of all ions occurred in the correct stoichiometries needed to maintain electroneutrality. This approach also revealed that the retention strength of Cl- ions on goethite increases in the presence of phthalate ions. That is, an anion-anion enhancement effect was observed. The retention of Cl- ions was much weaker than phthalate ions, and this also resulted in a higher sensitivity of the Cl- ions toward minor variations in the surface reactivity. The proposed model uses four goethite surface sites. The drop in retention of phthalate ions at low pH was fully described here as resulting from competitive Cl- reactions, which were introduced in increasing concentrations into the matrix as the conjugate base to the acid added to lower the pH.

Lead uptake and translocation by willows in pot and field experiments.

Plant growth and lead (Pb) uptake by seven willow varieties were investigated in pot and field experiments to assess the suitability of willows for phytoremediation of Pb at heavily contaminated sites such as skeet ranges. Differences in uptake and translocation of Pb in Salix were observed between pot and field experiments. In the pot experiment, willows grown in Pb-contaminated field soil for 6 months showed tolerance to very high soil Pb concentration (21,360 mg kg(-1)), and with the addition of EDTA were able to take up and translocate more than 1000 mg kg(-1) Pb into above-ground tissues. In the field experiment, all willow varieties showed tolerance to heterogeneously high soil Pb concentrations. Plants were also able to take up and translocate Pb into above-ground tissues. However, after 4.5 months, the lead concentration in the above-ground tissues of willows grown in soil amended with EDTA was less than 200 mg kg(-1). The results from the pot experiment suggest that Salix varieties have the potential to take up and translocate significant amounts of Pb into above-ground tissues using EDTA. However, to verify the phytoextraction abilities of Salix in the field, additional research is needed.

Hydroponic screening of willows (Salix L.) for lead tolerance and accumulation.

Lead tolerance and accumulation in five willow clones were investigated using a nutrient film technique. Plants were exposed to 0, 48, 121, 169, or 241 microM Pb for 14 days. Tolerance indices (TI) and critical toxicity thresholds (EC50) were determined for five willow clones. SX61 had the highest TI values (92%) in the 48 and 121 microM Pb treatments, as well as the highest EC50 threshold values (70.5 microM for roots, 155.9 microM for aboveground tissue), indications of a high degree of tolerance to Pb. This clone also developed the highest biomass of all the clones tested. We found significant variation in willows' lead accumulation. The highest Pb content in roots (24 mg plant(-1)) and aboveground tissue (7.6 mg plant(-1)) was recorded in the 48 microM Pb treatment in SX61. Based on high biomass, TI, ECso, and Pb content in plant tissues, SX61 holds promise for phytoextraction of lead.

X-ray absorption near edge structure study of lead sorption on phosphate-treated kaolinite.

Presorbed phosphate significantly increases Pb sorption on the phyllosilicate kaolinite in the pH range from 4to 8. The sorbed Pb-to-P molar ratios over this pH range stray little from the molar ratio found in the mineral pyromorphite, suggesting sorbed phosphate reacts with soluble Pb to form a surface precipitate similar to pyromorphite. X-ray absorption near edge structure (XANES) studies at the Pb L3-edge support this interpretation. In particular, the fine structure of first-derivative Pb L3-edge XANES spectra of Pb species sorbed to phosphate-treated kaolinite samples covering a pH range extending from 4 to 10 match the fine structure of the spectrum of pyromorphite. Although the productis structurally and compositionally similarto pyromorphite, the ion activity product in the pH range 4-6 was undersaturated with respect to the solubility product of pyromorphite.