A quantitative structure-activity relationship to predict efficacy of granular activated carbon adsorption to control emerging contaminants.

A quantitative structure-activity relationship was developed to predict the efficacy of carbon adsorption as a control technology for endocrine-disrupting compounds, pharmaceuticals, and components of personal care products, as a tool for water quality professionals to protect public health. Here, we expand previous work to investigate a broad spectrum of molecular descriptors including subdivided surface areas, adjacency and distance matrix descriptors, electrostatic partial charges, potential energy descriptors, conformation-dependent charge descriptors, and Transferable Atom Equivalent (TAE) descriptors that characterize the regional electronic properties of molecules. We compare the efficacy of linear (Partial Least Squares) and non-linear (Support Vector Machine) machine learning methods to describe a broad chemical space and produce a user-friendly model. We employ cross-validation, y-scrambling, and external validation for quality control. The recommended Support Vector Machine model trained on 95 compounds having 23 descriptors offered a good balance between good performance statistics, low error, and low probability of over-fitting while describing a wide range of chemical features. The cross-validated model using a log-uptake (qe) response calculated at an aqueous equilibrium concentration (Ce) of 1 µM described the training dataset with an r(2) of 0.932, had a cross-validated r(2) of 0.833, and an average residual of 0.14 log units.

Isolation of dissolved organic matter (DOM) from surface waters using reverse osmosis and its impact on the reactivity of DOM to formation and speciation of disinfection by-products.

Dissolved organic matter (DOM) from three low-hardness surface waters was isolated and concentrated using a reverse osmosis (RO) membrane system. The efficacy of the RO isolation method and its impact on the subsequent reactivity between DOM and chlorine were examined. DOM mass balances (quantified as dissolved organic carbon) ranged from 96.1 to 102.1% for the three waters tested, and DOM mass recoveries of 93.9 to 98.2% indicated successful isolation, minimal fractionation. and negligible loss of organic matter. RO isolates were diluted using distilled and deionized water in the laboratory to reconstitute the source waters. Both source water (collected at the time of isolation) and reconstituted source water samples were chlorinated. Formation of several disinfection by-products (DBPs: e.g., THMs, HAA9, HANs, and HKs) were measured. For all waters tested, DBP formation of source and corresponding reconstituted source water agreed within 95% confidence intervals. Therefore, RO isolation had no impact on the DOM reactivity of the three low-hardness surface waters tested in this study. In addition, the degree of bromine substitution, as expressed by the bromine incorporation factor, was calculated. Comparison of bromine incorporation factors for source and reconstituted source waters further indicated that, as with the total DBP formations, bromine speciation and the relative occurrence of individual species in THMs and HAA9 did not change as a result of the isolation. Overall, in terms of DBP formation, RO isolation appears to maintain the integrity and reactivity of DOM.

The reactivity of natural organic matter to disinfection by-products formation and its relation to specific ultraviolet absorbance.

Five natural waters with a broad range of DOC concentrations were fractionated using various coal- and wood-based granular activated carbons (GAC) and alum coagulation. Adsorption and alum coagulation fractionated NOM solutions by preferentially removing components having high specific ultraviolet absorbance (SUVA). UV absorbing fractions of NOM were found to be the major contributors to DBP formation. SUVA appears to be an accurate predictor of reactivity with chlorine in terms of DBP yield; however, it was also found that low-SUVA components of NOM have higher bromine incorporation. SUVA has promise as a parameter for on-line monitoring and control of DBP formation in practical applications; however, the effects of bromide concentration may also need to be considered. Understanding how reactivity is correlated to SUVA may allow utilities to optimize the degree of treatment required to comply with DBP regulations. The reactive components that require removal, and the degree of treatment necessary to accomplish this removal, may be directly obtained from the relationship between SUVA removal and the degree of treatment (e.g., alum dose).

Histamine release by esterase inhibitors. The regulation of histamine release from human leukocytes of allergic and non-allergic individuals by the serine esterase inhibitors diisopropyl fluorophosphate and pinacolyl methylphosphorofluoridate.

The serine esterase inhibitor diisopropyl fluorophosphate (DFP) has been shown to inhibit IgE-dependent histamine release. Recently, it has been demonstrated that lower concentrations of DFP enhanced IgE-dependent histamine release and inhibited desensitization. This manuscript describes the ability of another esterase inhibitor, pinacolyl methylphosphorofluoridate (soman), to directly cause release of histamine from human leukocytes (basophils) by a process that is IgE-independent. This release process requires calcium and is also temperature-dependent but occurs over a longer period of time than IgE-dependent release. These data suggest that there is a serine esterase which controls histamine release, and inhibition of this esterase causes histamine release.