Justin E. Birdwell

Desorption kinetics of hydrophobic organic chemicals from sediment to water: a review of data and models.

Resuspension of contaminated sediment can lead to the release of toxic compounds to surface waters where they are more bioavailable and mobile. Because the timeframe of particle resettling during such events is shorter than that needed to reach equilibrium, a kinetic approach is required for modeling the release process. Due to the current inability of common theoretical approaches to predict site-specific release rates, empirical algorithms incorporating the phenomenological assumption of biphasic, or fast and slow, release dominate the descriptions of nonpolar organic chemical release in the literature. Two first-order rate constants and one fraction are sufficient to characterize practically all of the data sets studied. These rate constants were compared to theoretical model parameters and functionalities, including chemical properties of the contaminants and physical properties of the sorbents, to determine if the trends incorporated into the hindered diffusion model are consistent with the parameters used in curve fitting. The results did not correspond to the parameter dependence of the hindered diffusion model. No trend in desorption rate constants, for either fast or slow release, was observed to be dependent on K(OC) or aqueous solubility for six and seven orders of magnitude, respectively. The same was observed for aqueous diffusivity and sediment fraction organic carbon. The distribution of kinetic rate constant values was approximately log-normal, ranging from 0.1 to 50 d(-1) for the fast release (average approximately 5 d(-1)) and 0.0001 to 0.1 d(-1) for the slow release (average approximately 0.03 d(-1)). The implications of these findings with regard to laboratory studies, theoretical desorption process mechanisms, and water quality modeling needs are presented and discussed.

A Multi-method Comparison of Atchafalaya Basin Surface Water Organic Matter Samples

Surface water organic matter (OM) was isolated from two distinct sites within the Atchafalaya Basin using a combination of XAD-8 and XAD-4 non-ionic macroporous resins and characterized by a suite of analytical methods, including elemental analysis, (13)C cross polarization magic angle spinning nuclear magnetic resonance, attenuated total reflectance Fourier transform infrared, luminescence spectroscopy including parallel factor analysis, and ultraviolet-visible spectroscopy. The major findings of the study are (i) despite the large differences in hydrology, optical properties, iron content, dissolved oxygen, and degree of human exploitation, the spectral and elemental signatures of the hydrophobic acids and transphilic acids fractions of the isolated OM for the different sites were remarkably similar; (ii) the luminescence characteristics of the four studied fractions provided information on the relative contributions from terrestrial and microbial input sources, as well as the degree of humification; and (iii) a detailed analysis of the total luminescence data led to a new dual excitation model based on quinone exciplexes for long wavelength emissions.

Studying organic matter molecular assemblage within a whole organic soil by nuclear magnetic resonance.

This work shows the applicability of two-dimensional (2D) (1)H-(13)C heteronuclear correlation (HETCOR) nuclear magnetic resonance (NMR) spectroscopy to the characterization of whole soils. A combination of different mixing times and cross polarization (CP) methods, namely Lee-Goldberg (LG)-CP and Ramp-CP are shown to afford, for the first time, intra- and inter- molecular connectivities, allowing for molecular assemblage information to be obtained on a whole soil. Our results show that, for the brackish marsh histosol under study, two isolated domains could be detected. The first domain consists of O-alkyl and aromatic moieties (lignocellulose material), while the second domain is comprised of alkyl type moieties (cuticular material). The role of these domains is discussed in terms of hydrophobic organic compound sorption within soil organic matter (SOM), including the possible effects of wetting and drying cycles.

PAH repartitioning in field-contaminated sediment following removal of the labile chemical fraction.

The effect of removing the labile chemical fraction associated with sediment particles followed by internal chemical redistribution was examined in a field-contaminated sediment. Using data from desorption equilibrium (organic carbon-water partition coefficients, K(OC)) and kinetic (rate of release) experiments, estimates of polynuclear aromatic hydrocarbon biphasic partitioning and desorption rates for both the labile and nonlabile chemical fractions or organic matter compartments were obtained. Sediment K(OC) values increased between 50 and 150% after removal of the labile chemical fraction. Following depletion of the labile chemical fraction during desorption experiments, sediment was stored 30 and 90 days to allow for chemical redistribution between the labile and nonlabile compartments. The subsequent desorption data indicated repartitioning had occurred with the nonlabile chemical fraction recharging the labile compartment. The results provide evidence that chemical transfer between organic matter compartments, either through interparticle porewater or via direct intraparticle compartmental exchange, is a real phenomenon that occurs over relatively short times (weeks to months). This calls into question the idea that hydrophobic organic pollutants in the nonlabile chemical fraction are sequestered or less bioavailable over the long-term and has implications for water quality impacts during contaminated sediment resuspension events, risk assessment of polluted sites, and selection of sediment remediation strategies.