Cristian P. Schulthess

Equilibrium-Based Modeling of Chemical Sorption on Soils and Soil Constituents

Models are tools used to describe any phenomena in nature. One should not be misled to believe that if a given set of data can be accurately described or predicted, then the model used must therefore be correct. This conclusion, though it is often made, should be questioned as several different models often predict a given set of data equally well. A model that is always correct, however, eventually becomes recognized as a law of nature. The research emphasis, therefore, should be in testing models (or hypotheses) with various data sets from independent experiments. The more accurate the model, the broader the range of data it will predict.

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 (21360 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.

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 channels 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 sodiums general designation as a weak electrolyte.

An electron paramagnetic resonance spectroscopy investigation of the retention mechanisms of Mn and Cu in the nanopore channels of three zeolite minerals

The adsorption mechanisms of divalent cations in zeolite nanopore channels can vary as a function of their pore dimensions. The nanopore inner-sphere enhancement (NISE) theory predicts that ions may dehydrate inside small nanopore channels in order to adsorb more closely to the mineral surface if the nanopore channel is sufficiently small. The results of an electron paramagnetic resonance (EPR) spectroscopy study of Mn and Cu adsorption on the zeolite minerals zeolite Y (large nanopores), ZSM-5 (intermediate nanopores), and mordenite (small nanopores) are presented. The Cu and Mn cations both adsorbed via an outer-sphere mechanism on zeolite Y based on the similarity between the adsorbed spectra and the aqueous spectra. Conversely, Mn and Cu adsorbed via an inner-sphere mechanism on mordenite based on spectrum asymmetry and peak broadening of the adsorbed spectra. However, Mn adsorbed via an outer-sphere mechanism on ZSM-5, whereas Cu adsorbed on ZSM-5 shows a high degree of surface interaction that indicates that it is adsorbed closer to the mineral surface. Evidence of dehydration and immobility was more readily evident in the spectrum of mordenite than in that of ZSM-5, indicating that Cu was not as close to the surface on ZSM-5 as it was when adsorbed on mordenite. Divalent Mn cations are strongly hydrated and are held strongly only in zeolites with small nanopore channels. Divalent Cu cations are also strongly hydrated, but can dehydrate more easily, presumably due to the Jahn-Teller effect, and are held strongly in zeolites with medium-sized nanopore channels or smaller.

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

ABSTRACT 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

ABSTRACT 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 CFUs 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.

A comparative study of neural network and mechanistic models for surface complexation

Abstract This paper demonstrates the use of a feed-forward neural network model to quantify the partitioning of phosphate onto water treatment residual (WTR) as a function of pH. Reasonably good results were obtained with a limited amount of experimental data. The neural network models were essentially as good as the specific mechanistic model used. Comparison of the neural network models with simple models obtained from statistical regression shows the neural network models to be superior. Quantification of the distribution of phosphate in this system may allow accurate prediction of available phosphate in a land application scenario. In surface complexation studies where mechanistic models are not available, it is recommended that neural network models be used.

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.