The dechlorination of chlorophenols (CPs) in anaerobic
estuarine sediment was studied. The sediment used
was fairly contaminated with various anthropogenic
chemicals from the surrounding industries. The
sulfate
content of the interstitial and overlying waters was
approximately 20 mmol/L, and the sediment was
apparently sulfidogenic. All 13 CPs tested
transformed
following a first-order reaction kinetics. The rate
constants for CP disappearance ranged between 0.010
and 0.38 day-1 or had half-lives between 1.8
and
70 days. The intermediates detected in the experiment
indicated that the ortho-dechlorination was the
preferred pathway. The disappearance of the parent
compound and the accumulation and disappearance
of dechlorinated intermediates were simulated using
a branched chain first-order irreversible reaction
kinetics, and the contributions of different pathways
were estimated. A comparison of the estimated
rate constants with the redox potential of the reaction
showed that the hypothesis of microbial selection
of most thermodynamically favorable pathways observed
for chlorobenzene dechlorination was not applicable
for CPs.
Oxygenated nonpolar organic contaminants (NOCs) are underrepresented in studies of the partitioning and bioavailability of NOCs, including nonylphenol. In this investigation, we evaluated the toxicity, partitioning, and bioavailability of nonylphenol as affected by different forms of organic carbon. Along with organic carbon content, the role of organic carbon polarity was assessed. Toxicity of nonylphenol to a mysid and amphipod was comparable to results reported in the literature for marine organisms with median lethal concentrations (LC50s) of 82.3 and 236 microg/L, respectively. The presence of the different forms of organic carbon in every instance altered, often statistically significantly, the toxicity and bioavailability of the nonylphenol and increased the LC50 by approximately a factor of two. Partition coefficients (KPs) for nonylphenol ranged from 21.3 for cellulose to 9,770 for humic acid; log organic carbon-normalized partition coefficients (KOCs) ranged from 1.71 for cellulose to 4.71 for sediment. An exercise to predict nonylphenol effects using our toxicity data and normalized partition coefficients indicated organic carbon content was most protective and also highlighted the need for further research to better understand nonylphenol bioavailability. These data suggested that with regard to partitioning and bioavailability, the oxygenated NOC nonylphenol behaves like conventional NOCs. The data also suggest that, with refinements, polarity may have some advantages in predicting nonylphenol bioavailability.
Coal fly ash has a very high sorption capacity for a variety of anthropogenic contaminants and has been used to cleanse wastewater of pollutants for approximately 40 years. Like other black carbons, the planar structure of the residual carbon in fly ash results in elevated affinities for planar organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs) and some polychlorinated biphenyls (PCBs). The present study was performed to understand better the mechanisms affecting the strong interaction between planar contaminants and coal fly ash. The removal of 10 PCBs and 10 PAHs by several fly ashes and other sorbents was evaluated under different experimental conditions to highlight the intermolecular forces influencing adsorption. Varying fly ash concentration and solvent system composition indicated that dispersive interactions were most prevalent. For the PCBs, empirical results also were compared to molecular modeling estimates of the energy necessary for the PCB molecule to assume a planar conformation (PCe). The PCe levels ranged from 8 to 25 kcal/mol, depending on the degree of ortho-substituted chlorination of the PCB. A significant correlation between PCe and PCB removal from solution was observed for the fly ashes and activated carbon, whereas the nonplanar sorbent octadecyl (C18) indicated no relationship. These findings demonstrate the strong interaction between black carbon fly ash and planar organic contaminants. Furthermore, as exemplified by the PCBs, these results show how this interaction is a function of a contaminant's ability to assume a planar conformation.
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