Beth E. Porter

Surfactive stabilization of multi-walled carbon nanotube dispersions with dissolved humic substances

Soil humic substances (HS) stabilize carbon nanotube (CNT) dispersions, a mechanism we hypothesized arose from the surfactive nature of HS. Experiments dispersing multi-walled CNT in solutions of dissolved Aldrich humic acid (HA) or water-extractable Catlin soil HS demonstrated enhanced stability at 150 and 300 mg L(-1) added Aldrich HA and Catlin HS, respectively, corresponding with decreased CNT mean particle diameter (MPD) and polydispersivity (PD) of 250 nm and 0.3 for Aldrich HA and 450 nm and 0.35 for Catlin HS. Analogous trends in MPD and PD were observed with addition of the surfactants Brij 35, Triton X-405, and SDS, corresponding to surfactant sorption maximum. NEXAFS characterization showed that Aldrich HA contained highly surfactive domains while Catlin soil possessed a mostly carbohydrate-based structure. This work demonstrates that the chemical structure of humic materials in natural waters is directly linked to their surfactive ability to disperse CNT released into the environment.

Simultaneous dispersion-dissolution behavior of concentrated silver nanoparticle suspensions in the presence of model organic solutes.

The premise of the nanotechnology revolution is based on the increased surface reactivity of nanometer-sized particles. Thus, these newly realized applications of noble metal nanoparticles introduce new concerns about the environmental fate of these materials if released during use or product disposal. In this paper, the focus is on silver nanoparticles, a known biocidal agent. In particular, this work explores the effect of model solutes chosen for their simple chemical structure yet their ability to simulate chemical attributes common to soil humic material: a chelating molecule, EDTA; a nonionic surfactant, Brij 35; and a large polysaccharide, alginic acid. Batch systems containing concentrated (1600 mg L(-1)) silver nanoparticle (nAg) suspensions were equilibrated with varying additions of EDTA, Brij 35, or alginic acid to solutions containing 1 or 100 mM NaNO3 background electrolyte. In general, both EDTA and alginate were shown to exhibit poor control over nAg dispersion stability, while Brij 35 served as a good dispersant of nAg particles, showing little difference in particle size with respect to electrolyte concentration. The data also show that loading of the model organic compounds resulted in the supersaturation of dissolved Ag for most of the systems. Mechanisms by which these occurred are discussed in more detail. The evidence suggests that regardless of the effect of humics on the stability of nAg dispersions in aqueous systems, polymer loading may enhance the dissolution and release of dissolved Ag into the environment.

Sorption of high explosives to water-dispersible clay: influence of organic carbon, aluminosilicate clay, and extractable iron.

Explosives in soils can present environmental problems for military installations. Fine, mobile particles represent the most reactive fraction of the soil and, therefore, are expected to adsorb explosives and potentially facilitate their transport. The objective of this study was to determine the relative significance of phyllosilicate clay, organic matter, and two forms of extractable iron in adsorption of 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by the colloidal water-dispersible clay (WDC) fraction of the soil. The WDC fraction of two mineral and one organic soil was separated and then treated to remove organic carbon (OC) and several forms of iron (Fe(o), oxalate extractable, and Fe(d), dithionite-citrate extractable). Adsorption coefficients were determined for whole soils, untreated, and treated WDC. For mineral soils, adsorption of TNT and RDX on the WDC was greater than on the whole soil. The presence of OC increased explosives sorption by WDC. When OC was removed, iron interfered with TNT sorption. In the presence of OC, removal of Fe(o) decreased RDX adsorption and increased TNT adsorption indicating different adsorption mechanisms. Organic carbon was a more significant indicator of explosives adsorption by WDC than clays or iron oxides and hydroxides. Therefore, OC is the most likely medium for facilitated transport of TNT and RDX.

Differential kinetics and temperature dependence of abiotic and biotic processes controlling the environmental fate of TNT in simulated marine systems.

This work seeks to understand how the balance of abiotic and biotic kinetic processes in sediments control the residual concentration of TNT in marine systems after release from ocean-dumped source. Kinetics of TNT disappearance were followed using marine sediments at different temperatures and under both biotic and presumably abiotic conditions (through sodium azide addition). Sediments exhibiting the highest rate of TNT disappearance under biotic conditions also exhibited the highest sorption affinity for TNT under abiotic conditions. Significant temperature dependence in the abiotic processes was observed in the diffusion coefficient of TNT and not sediment sorption affinity. At higher temperature, kinetics of biotic processes outpaced abiotic processes, but at low temperature, kinetics of abiotic processes were much more significant. We concluded that the differential influence of temperature on the kinetics of abiotic and biotic processes could provide distinguishing predictions for the potential residual concentration of TNT contamination in marine-sediment systems.

Multivariate functions for predicting the sorption of 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitro-1,3,5-tricyclohexane (RDX) among taxonomically distinct soils.

After nearly a century of use in numerous munition platforms, TNT and RDX contamination has turned up largely in the environment due to ammunition manufacturing or as part of releases from low-order detonations during training activities. Although the basic knowledge governing the environmental fate of TNT and RDX are known, accurate predictions of TNT and RDX persistence in soil remain elusive, particularly given the universal heterogeneity of pedomorphic soil types. In this work, we proposed a new solution for modeling the sorption and persistence of these munition constituents as multivariate mathematical functions correlating soil attribute data over a variety of taxonomically distinct soil types to contaminant behavior, instead of a single constant or parameter of a specific absolute value. To test this idea, we conducted experiments measuring the sorption of TNT and RDX on taxonomically different soil types that were extensively physical and chemically characterized. Statistical decomposition of the log-transformed, and auto-scaled soil characterization data using the dimension-reduction technique PCA (principal component analysis) revealed a strong latent structure based in the multiple pairwise correlations among the soil properties. TNT and RDX sorption partitioning coefficients (KD-TNT and KD-RDX) were regressed against this latent structure using partial least squares regression (PLSR), generating a 3-factor, multivariate linear functions. Here, PLSR models predicted KD-TNT and KD-RDX values based on attributes contributing to endogenous alkaline/calcareous and soil fertility criteria, respectively, exhibited among the different soil types: We hypothesized that the latent structure arising from the strong covariance of full multivariate geochemical matrix describing taxonomically distinguished soil types may provide the means for potentially predicting complex phenomena in soils. The development of predictive multivariate models tuned to a local soils taxonomic designation would have direct benefit to military range managers seeking to anticipate the environmental risks of training activities on impact sites.