Joris J.-H. Haftka

Adsorption of polar, nonpolar, and substituted aromatics to colloidal graphene oxide nanoparticles

We conducted batch adsorption experiments to understand the adsorptive properties of colloidal graphene oxide nanoparticles (GONPs) for a range of environmentally relevant aromatics and substituted aromatics, including model nonpolar compounds (pyrene, phenanthrene, naphthalene, and 1,3-dichlorobenzene) and model polar compounds (1-naphthol, 1-naphthylamine, 2,4-dichlorophenol, and 2,4-dinitrotoluene). GONPs exhibited strong adsorption affinities for all the test compounds, with distribution coefficients on the order of 10(3)-10(6) L/kg. Adsorption to GONPs is much more linear than to carbon nanotubes (CNTs) and C60, likely because GO nanoflakes are essentially individually dispersed (rendering adsorption sites of similar adsorption energy) whereas CNT/C60 are prone to bundling/aggregation. For a given compound GONPs and CNTs often exhibit different adsorption affinities, which is attributable to the differences in both the morphology and surface chemistry between the two nanomaterials. Particularly, the high surface O-content of GONPs enables strong H-bonding and Lewis acid-base interactions with hydroxyl- and amino-substituted aromatics.

Perfluorinated compounds in infiltrated river Rhine water and infiltrated rainwater in coastal dunes

Different studies have shown that surface waters contain perfluorinated compounds (PFCs) in the low ng/L range. Surface waters are used to produce drinking water and PFCs have been shown to travel through the purification system and form a potential threat to human health. The specific physicochemical properties of PFCs cause them to be persistent and some of them to be bioaccumulative and toxic in the environment. This study investigates the evolvement of PFC concentrations in Rhine water and rainwater during dune water infiltration processes over a transect in the dune area of the western part of The Netherlands. The difference between infiltrated river water and rainwater in terms of PFC composition was investigated. Furthermore, isomer profiles were investigated. The compound perfluorobutanesulfonate (PFBS) was found at the highest concentrations of all PFCs investigated, up to 37 ng/L in infiltrated river water (71 ± 13% of ΣPFCs). This is in contrast with the predominant occurrence of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) reported in literature. The concentrations of PFBS found in infiltrated river Rhine water were significantly higher than those in infiltrated rainwater. For perfluorohexanesulfonate (PFHxS) the opposite was found: infiltrated rainwater contained more than infiltrated river water. The concentrations of PFOA, perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), PFBS, PFOS, and PFHxS in infiltrated river water showed an increasing trend with decreasing age of the water. The relative contribution of the branched PFOA and PFOS isomers to total concentrations of PFOA and PFOS showed a decreasing trend with decreasing age of the water.

Using polyacrylate-coated SPME fibers to quantify sorption of polar and ionic organic contaminants to dissolved organic carbon.

A passive sampling method using polyacrylate-coated solid-phase microextraction (SPME) fibers was applied to determine sorption of polar and ionic organic contaminants to dissolved organic carbon (DOC). The tested contaminants included pharmaceuticals, industrial chemicals, hormones, and pesticides and represented neutral, anionic, and cationic structures. Prior to the passive sampler application, sorption of the chemicals to the fibers was characterized. This was needed in order to accurately translate concentrations measured in fibers to freely dissolved aqueous concentrations during the sorption tests with DOC. Sorption isotherms of neutral compounds to the fiber were linear, whereas isotherms of basic chemicals covered a nonlinear and a linear range. Sorption of acidic and basic compounds to the fiber was pH-dependent and was dominated by sorption of the neutral sorbate species. Fiber- and DOC-water partition coefficients of neutral compounds were both linearly related to octanol-water partition coefficients (log Kow). The results of this study show that polyacrylate fibers can be used to quantify sorption to DOC of neutral and ionic contaminants, having multiple functional groups and spanning a wide hydrophobicity range (log Kow = 2.5-7.5).

Mechanisms of Neutral and Anionic Surfactant Sorption to Solid-Phase Microextraction Fibers

Octanol-water partitioning (Kow) is considered a key parameter for hydrophobicity and is often applied in the prediction of the environmental fate and exposure of neutral organic compounds. However, surfactants can create difficulties in the determination of Kow because of emulsification of both water and octanol phases. Moreover, not only is sorption behavior of ionic surfactants related to hydrophobicity, but also other interactions are relevant in sorption processes. A different approach to develop parameters that can be applied in predictive modeling of the fate of surfactants in the environment is therefore required. Distribution between solid-phase microextraction (SPME) fibers and water was used in this study to measure the affinity of surfactants to a hydrophobic phase. Fiber-water sorption coefficients of alcohol ethoxylates, alkyl carboxylates, alkyl sulfates, and alkyl sulfonates were determined at pH 7 by equilibration of the test analytes between fiber and water. Distribution between fiber and water of anionic compounds with pKa ∼ 5 (i.e., alkyl carboxylates) was dominated by the neutral fraction. Anionic surfactants with pKa ≤ 2 (i.e., alkyl sulfates and alkyl sulfonates) showed strong nonlinear distribution to the fiber. The fiber-water sorption coefficients for alcohol ethoxylates and alkyl sulfates showed a linear trend with bioconcentration factors from the literature. Fiber-water sorption coefficients are promising as a parameter to study the effects of hydrophobicity and other potential interactions on sorption behavior of neutral and anionic surfactants.

A Decision Support System for Drinking Water Production Integrating Health Risks Assessment

The issue of drinking water quality compliance in small and medium scale water services is of paramount importance in relation to the 98/83/CE European Drinking Water Directive (DWD). Additionally, concerns are being expressed over the implementation of the DWD with respect to possible impacts on water quality from forecast changes in European climate with global warming and further anticipated reductions in north European acid emissions. Consequently, we have developed a decision support system (DSS) named ARTEM-WQ (AwaReness Tool for the Evaluation and Mitigation of drinking Water Quality issues resulting from environmental changes) to support decision making by small and medium plant operators and other water stakeholders. ARTEM-WQ is based on a sequential risk analysis approach that includes consideration of catchment characteristics, climatic conditions and treatment operations. It provides a holistic evaluation of the water system, while also assessing human health risks of organic contaminants potentially present in treated waters (steroids, pharmaceuticals, pesticides, bisphenol-a, polychlorobiphenyls, polycyclic aromatic hydrocarbons, petrochemical hydrocarbons and disinfection by-products; n = 109). Moreover, the system provides recommendations for improvement while supporting decision making in its widest context. The tool has been tested on various European catchments and shows a promising potential to inform water managers of risks and appropriate mitigative actions. Further improvements should include toxicological knowledge advancement, environmental background pollutant concentrations and the assessment of the impact of distribution systems on water quality variation.

Critical micelle concentration values for different surfactants measured with solid-phase microextraction fibers

The amphiphilic nature of surfactants drives the formation of micelles at the critical micelle concentration (CMC). Solid-phase microextraction (SPME) fibers were used in the present study to measure CMC values of 12 nonionic, anionic, cationic, and zwitterionic surfactants. The SPME-derived CMC values were compared to values determined using a traditional surface tension method. At the CMC of a surfactant, a break in the relationship between the concentration in SPME fibers and the concentration in water is observed. The CMC values determined with SPME fibers deviated by less than a factor of 3 from values determined with a surface tension method for 7 out of 12 compounds. In addition, the fiber-water sorption isotherms gave information about the sorption mechanism to polyacrylate-coated SPME fibers. A limitation of the SPME method is that CMCs for very hydrophobic cationic surfactants cannot be determined when the cation exchange capacity of the SPME fibers is lower than the CMC value. The advantage of the SPME method over other methods is that CMC values of individual compounds in a mixture can be determined with this method. However, CMC values may be affected by the presence of compounds with other chain lengths in the mixture because of possible mixed micelle formation. Environ Toxicol Chem 2016;35:2173-2181.

Colloidal stability of (functionalised) fullerenes in the presence of dissolved organic carbon and electrolytes

Carbon-based nanoparticles such as fullerenes have been widely applied in personal care products, drug delivery systems, and solar cells. The properties of nanoparticles have been increasingly studied because of their applications and their potential risks to the environment and human health. Many studies have focused on the environmental fate and properties of C60. However, there is limited information available on the environmental properties of functionalised fullerenes. This study focuses on the colloidal stability of two fullerenes (C60 and [6,6]-diphenyl-C62-bis(butyric acid methyl ester)) in water in the presence of dissolved organic carbon (DOC) and different electrolytes (NaCl and CaCl2). Suspended fullerene concentrations were determined with high resolution Orbitrap mass spectrometry. The size was determined by multi-angle light scattering, dynamic light scattering and for the first time by flow cytometry. The suspended concentrations of the fullerenes were stabilised by low concentrations of DOC (2 mg C per L) in the presence of NaCl. However, sedimentation of DOC occurred at low concentrations of CaCl2 (>~2 mM) which caused removal of (functionalised) fullerenes. The results show that (functionalised) fullerenes can be rapidly removed in natural aqueous systems in the presence of low concentrations of DOC and multivalent inorganic electrolytes.