Adsorption of 17alpha-ethinyl estradiol (EE2) and bisphenol A (BPA) on carbon nanomaterials (CNMs) was investigated. Single point adsorption coefficients (K) showed significant relationship with specific surface areas of CNMs for both chemicals, indicating surface area is a major factor for EDC adsorption on CNMs. BPA adsorption capacity is higher than EE2 on fullerene and single-walled carbon nanotubes (SWCNT). Our molecular conformation simulation indicated that BPA has a unique ability to adsorb on the curvature surface of CNMs because of its "butterfly" structure of two benzene rings. The higher adsorption capacity of BPA over EE2 is well explained by considering helical (diagonal) coverage of BPA on the CNMs surface and wedging of BPA into the groove and interstitial region of CNM bundles or aggregates. The comparison of K(HW) (hexadecane-water partition coefficient) normalized adsorption coefficients between EDCs and several polyaromatic hydrocarbons indicates that pi-pi electron donor--acceptor system is an important mechanism forthe adsorption of benzene-containing chemicals on CNMs. The high adsorption capacity and strong desorption hysteresis of both chemicals on SWCNT indicate that SWCNT is a potential adsorbent for water treatment.
The colloidal behavior of aluminum oxide nanoparticles (NPs) was investigated as a function of pH and in the presence of two structurally different humic acids (HAs), Aldrich HA (AHA) and the seventh HA fraction extracted from Amherst peat soil (HA7). Dynamic light scattering (DLS) and atomic force microscopy (AFM) were employed to determine the colloidal behavior of the NPs. Influence of pH and HAs on the surface charges of the NPs was determined. zeta-Potential data clearly showed that the surface charge of the NPs decreased with increasing pH and reached the point of zero charge (ZPC) at pH 7.9. Surface charge of the NPs also decreased with the addition of HAs. The NPs tend to aggregate as the pH of the suspension approaches ZPC, where van der Waals attraction forces dominate over electrostatic repulsion. However, the NP colloidal suspension was stable in the pHs far from ZPC. Colloidal stability was strongly enhanced in the presence of HAs at the pH of ZPC or above it, but in acidic conditions NPs showed strong aggregation in the presence of HAs. AFM imaging revealed the presence of long-chain fractions in HA7, which entangled with the NPs to form large aggregates. The association of HA with the NP surface can be assumed to follow a two-step process, possibly the polar fractions of the HA7 sorbed on the NP surface followed by entanglement with the long-chain fractions. Thus, our study demonstrated that the hydrophobic nature of the HA molecules strongly influenced the aggregation of colloidal NPs, possibly through their conformational behavior in a particular solution condition. Therefore, various organic matter samples will result in different colloidal behavior of NPs, subsequently their environmental fate and transport.
Adsorption of phenanthrene on carbon nanotubes (CNTs) and bioaccessibility of adsorbed phenanthrene were studied in simulated gastrointestinal fluids. Adsorption of phenanthrene on CNTs was suppressed in pepsin (800 mg/L) solution (gastric) and bile salt (500 and 5000 mg/L) fluids (intestinal). In addition to competitive sorption, pepsin and high-concentration bile salt (5000 mg/L, above critical micelle concentration) solubilized phenanthrene (3 and 30 times of the water solubility, respectively), thus substantially reduced phenanthrene adsorption on CNTs. Pepsin and bile salts also increased the rapidly desorbing phenanthrene fraction from CNTs. The rapidly desorbing phase lasted less than 1 h for all CNTs. Further, 43-69% of phenanthrene was released from CNTs after desorption in the simulated gastric and intestinal fluid at low bile salt concentration while 53-86% was released in the gastric and intestinal fluid at high bile salt concentration. These findings suggest that the release of residual hydrophobic organic compounds from CNTs could be enhanced by biomolecules such as pepsin and bile salts in the digestive tract, thus increasing the bioaccessibility of adsorbed phenanthrene and possibly the overall toxicity of phenanthrene associated CNTs.
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