The potential occurrence of endocrine-disrupting compounds (EDCs) as well as pharmaceuticals and personal care products (PPCPs) in drinking water supplies raises concern over the removal of these compounds by common drinking water treatment processes. Three drinking water supplies were spiked with 10 to 250 ng/L of 62 different EDC/PPCPs; one model water containing an NOM isolate was spiked with 49 different EDC/PPCPs. Compounds were detected by LC/MS/MS or GC/MS/MS. These test waters were subjected to bench-scale experimentation to simulate individual treatment processes in a water treatment plant (WTP). Aluminum sulfate and ferric chloride coagulants or chemical lime softening removed some polyaromatic hydrocarbons (PAHs) but removed 98% of GC/MS/MS compounds (more volatile) and 10% to >95% of LC/MS/MS compounds (more polar); higher PAC dosages improved EDC/PPCP removal. EDC/PPCP per...

Fate of endocrine-disruptor, pharmaceutical, and personal care product chemicals during simulated drinking water treatment processes.

Carbon nanotubes (CNTs) have drawn special research attention because of their unique properties and potential applications. This review summarizes the research progress of organic chemical adsorption on CNTs, and will provide useful information for CNT application and risk assessment. Adsorption heterogeneity and hysteresis are two widely recognized features of organic chemical−CNT interactions. However, because different mechanisms may act simultaneously, mainly hydrophobic interactions, π−π bonds, electrostatic interactions, and hydrogen bonds, the prediction of organic chemical adsorption on CNTs is not straightforward. The dominant adsorption mechanism is different for different types of organic chemicals (such as polar and nonpolar), thus different models may be needed to predict organic chemical−CNT interaction. Adsorption mechanisms will be better understood by investigating the effects of properties of both CNTs and organic chemicals along with environmental conditions. Another major factor affec...

Adsorption Mechanisms of Organic Chemicals on Carbon Nanotubes

Existing field data indicate that soot may significantly affect the environmental speciation of polycyclic aromatic hydrocarbons (PAHs). To expand hydrophobic partition models to include soot partitioning, we need to quantify fsc, the soot fraction of the solid matrix, and Ksc, the soot-carbon-normalized partition coefficient. To this end, we have developed a method that allows quantification of soot carbon in dilute and complex sedimentary matrices. Non-soot organic carbon is removed by thermal oxidation, and inorganic carbonates are removed by acidification, fol lowed by CHN elemental analysis of the residual soot carbon. The selectivity of the soot carbon method was confirmed in tests with matrices of known compostion. The soot quantification technique was applied to two sets of natural sediments, both previously analyzed for PAHs. The input histories of PAHs and soot recorded in a lacustrine sediment core followed the same general trends, and we thus infer a coupling between the two. Our measures of f...

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Quantification of the dilute sedimentary soot phase : Implications for PAH speciation and bioavailability

11. Conclusions and Perspectives 6005 12. Acknowledgments 6006 13. References 6006

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Adsorption of Organic Compounds by Carbon Nanomaterials in Aqueous Phase: Polanyi Theory and Its Application

Recent studies have shown that sorption of polycyclic aromatic hydrocarbons (PAHs) in soot-water systems is exceptionally strong. As a consequence, soot may fully control the actual fate of PAHs in the aquatic environment. However, sorption has only been characterized for a limited number of PAHs to diesel soot, and the mechanism is poorly understood. In this paper, we present an extensive data set of sorbent-water distribution coefficients (K(S), n = 236) for a series of PAHs (both native and added) and polychlorinated biphenyls (PCBs) to five different types of soot and five soot-like materials. Both Ks values and physicochemical properties of the sorbents show large variation. In general, sorption is very strong, with K(S) values up to 10(10), showing the highest distribution coefficients on a mass basis ever reported. Sorption of in particular PAHs is often over 1000 times as strong as sorption to amorphous sedimentary organic carbon. The variation in K(S) values cannot be explained by "soot carbon fractions" or specific surface areas of the sorbents. Instead, values for native PAHs are mostly determined by the sorbates' molar volume, and values for added PAHs and PCBs are determined by the sorbents' average pore diameter. From differences in K(S) values between native and added PAH analogues, it can be deduced that generally more than 50% (with values up to 97%) of the native PAH concentration in soot is not available for distribution to the aqueous phase. We conclude that this is caused by physical entrapment of the chemicals within the solid matrix. Furthermore, most sorbents appear to preferentially sorb PCBs with planar configurations, a phenomenon most likely driven by sorption in molecular-sized pores. Pore sorption is also concluded to be the most important sorption mechanism for added PAHs together with pi-pi interaction processes with flat aromatic sorbent surfaces. Frequently observed, slowly desorbing, resistant contaminant fractions in sediments may very well be explained on the basis of these results.

Sorption of polycyclic aromatic hydrocarbons and polychlorinated biphenyls to soot and soot-like materials in the aqueous environment: Mechanistic considerations

For the linear solvation energy relationship (LSER), values are listed for each of the variables (V{sub i}/100, {pi}{sup *}, {beta}{sub m}, {alpha}{sub m}) for fundamental organic structures and functional groups. The authors give the guidelines to estimate LSER variable values quickly for a vast array of possible organic compounds such as those found in the environment. The difficulty in generating these variables has greatly discouraged the application of this quantitative structure-activity relationship (QSAR) method. This paper presents the first compilation of molecular functional group values together with a utilitarian set of the LSER variable estimation rules. The availability of these variable values and rules should facilitate widespread application of LSER for hazard evaluation of environmental contaminants.

Linear solvation energy relationships: "rule of thumb" for estimation of variable values

A critically evaluated set of 94 soil water partition coefficients normalized to soil organic carbon content (K oc ) is presented for 11 classes of organic chemicals. This data set is used to develop and evaluate K oc estimation methods using three different descriptors. The three types of descriptors used in predicting K oc were octanol/ water partition coefficient (K ow ), molecular connectivity ( m X t ), and linear solvation energy relationships (LSERs). The best results were obtained estimating K oc from K ow , though a slight improvement in the correlation coefficient was obtained by using a two-parameter regression with K ow and the third order difference term from m X t , Molecular connectivity correlations seemed to be best suited for use with specific chemical classes. The LSER provided a better fit than m X t , but not as good as the correlation with K ow . The correlation to predict K oc from K ow was developed for 72 chemicals; log K oc = 0.903 log K ow + 0.094. This correlation accounts for 91% of the variability in the data for chemicals with log K ow ranging from 1.7 to 7.0. The expression to determine the 95% confidence interval on the estimated K oc is provided along with an example for two chemicals of different hydrophobicity showing the confidence interval of the retardation factor determined from the estimated K oc . The data showed that K oc is not likely to be applicable for chemicals with log K ow < 1.7. Finally, the K oc correlation developed using K ow as a descriptor was compared with three nonclass-specific correlations and two commonly used class-specific correlations to determine which method(s) are most suitable.

Evaluation of estimation methods for organic carbon normalized sorption coefficients

A linear solvation energy relationship has been found for 353 values of the limiting adsorption coefficients of diverse chemicals:  log K = −0.37 + 0.0341Vi − 1.07β + D + 0.65P with R = 0.951, s = 0.51, n = 353, and F = 818.0, where Vi is the intrinsic molar volume; β is a measure of the hydrogen bond acceptor strength of the solute; D is an index parameter for the research group which includes the effects of the different types of carbon used, the temperature, and the length of time allowed for the adsorption equilibrium to be established; and P is an index parameter for the flatness of the molecule. P is defined to be unity if there is an aromatic system in the molecule or if there is a double bond or series of conjugated double bonds with no more that one non-hydrogen atom beyond the double bond and zero otherwise. A slightly better fit is obtained if the two-thirds power of Vi is used as a measure of the surface area in place of the volume term:  log K = −1.75 + 0.227V2/3 − 1.10β + D + 0.60P with R = ...

James P. Hickey

Papers

Linear solvation energy relationships: "rule of thumb" for estimation of variable values

Evaluation of estimation methods for organic carbon normalized sorption coefficients

Linear Solvation Energy Relationship of the Limiting Partition Coefficient of Organic Solutes between Water and Activated Carbon

Baseline risk assessment for aquatic life for the Buffalo River, New York, Area of Concern

Estimation of octanol/water partition coefficients using LSER parameters