Nonpolar Organic Contaminants Research Articles

Investigating the Change Pattern in Adsorption Properties of Soil Media for Non-Polar Organic Contaminants under the Impact of Freezing and Thawing

The adsorption of petroleum hydrocarbons by soils in the unsaturated zone determines the amount that goes into the groundwater. However, the intricate behavior of petroleum hydrocarbon adsorption in soil media under the influence of freeze–thaw conditions in globally prevalent seasonally frozen regions remains unclear. Alkanes as a non-polar compound are an important part of petroleum hydrocarbons. We conducted field-scale seasonal freeze-thaw experiments using n-dodecane to quantify the dynamic patterns and influencing factors of the physicochemical properties of soil media and their adsorption capacity for petroleum hydrocarbons during different freeze–thaw cycles. Our findings demonstrated that, as the number of natural freeze–thaw cycles increased, the proportion of soil micro-agglomerates rose rapidly, thereby expanding the available adsorption sites and enhancing the adsorption capacity for non-polar organic pollutants. The rise in sorption capacity for the outdoor freeze–thaw experimental group surpassed that of the indoor room-temperature control group by an impressive 75.57%, showing the enhancement of the adsorption capacity for non-polar organic pollutants. Conversely, the decline in soil organic matter content during the later stages of the freeze–thaw process hampered its adsorption performance for non-polar organic pollutants. The decrease in sorption capacity for the outdoor freeze–thaw experimental group surpassed that of the indoor room temperature control group by 77.97%. By shedding light on the adsorption mechanisms of non-polar organic pollutants in soils subjected to freeze–thaw conditions, our research facilitated a comprehensive understanding and predictive modeling of this process. Furthermore, our study provided a scientific foundation for exploring the convergence and migration transformation patterns of other organic compounds in petroleum-contaminated areas within seasonally frozen regions.

Broad-range extraction of highly polar to non-polar organic contaminants for inclusive target analysis and suspect screening of environmental samples

The lack of carefully optimized extraction techniques for the analysis of compounds with diverse polarities limits the identification of toxic pollutants in aqueous environmental matrices, particularly those that are considered persistent and mobile organic compounds (PMOCs). Tailored extraction techniques for specific classes of chemicals often result in very low to no extraction of either very polar or relatively non-polar chemicals, depending on the sorbent used. Hence, it is crucial to develop a balanced extraction for a wider range of polarity, especially for non-target analysis of chemical residues, in order to capture the occurrence of the full profile of micropollutants. Herein, a tandem solid-phase extraction (SPE) technique incorporating both hydrophilic-lipophilic balance (HLB) and mixed-mode cation exchange (MCX) sorbents was developed to extract and analyze 60 model compounds with a wide range of polarities (log Kow from ‐1.9 to 5.5) from untreated sewage matrices. Extraction efficiencies were assessed in NanoPure™ water and untreated sewage samples; 51 compounds in NanoPure™ water and 44 compounds in untreated sewage had ≥60 % extraction recoveries using the developed tandem SPE method. The method limits of detection ranged from 0.25 to 88 ng/L in untreated sewage matrix. The applicability of the extraction method was demonstrated in untreated wastewater samples; using the tandem SPE for suspect screening analysis captured an additional 22 compounds that were not extracted when using the HLB sorbent only. The optimized SPE method was also evaluated for the extraction of per- and polyfluoroalkyl substances (PFAS) by analyzing the same sample extracts under negative electrospray ionization liquid chromatography-tandem mass spectrometry (LC-MS/MS). The wastewater samples revealed the presence of sulfonamide-, sulfonic-, carboxylic-, and fluorotelomer sulfonic- PFAS with chain lengths 8, 4–8, 4–9, and 8, respectively, indicating that the tandem SPE procedure provides an efficient one-step extraction for the analysis of PMOCs that include pharmaceuticals, pesticides, and PFAS.

Use of Toxicity Identification Evaluation Procedures to Clarify the Relationship Between Ammonium Concentrations and Phytoplankton Blooms in the San Francisco Bay Estuary, California, USA.

Phytoplankton blooms in the northern San Francisco Bay Estuary have historically supported much of the larval fish production in the estuary. In the past, blooms were limited largely by reduced light intensities and net outflows through the system, as well as dense populations of introduced clams that continuously filter the water column. Conversely, the estuary is exposed to a wide variety of contaminants that may also impact phytoplankton growth. Interestingly, previous investigations have suggested that relatively low concentrations of ammonium may inhibit development of bloom conditions by interfering with nitrate assimilation. Given the complex dynamics of the system, with multiple factors that could potentially affect algal growth, additional data to validate this hypothesis are important to identify appropriate management options. Consequently, toxicity identification evaluation (TIE) procedures were applied to ambient water samples and monitored for 72-96 h under controlled conditions to evaluate their effects on algal growth and utilization of dissolved inorganic nitrogen. The TIE treatments specifically targeted ammonium, as well as the potential contributions of metals and nonpolar organic contaminants. Notably, all samples exhibited positive growth over the exposure period with no evidence of toxicity, and TIE treatments did not further improve growth. A subsequent 72-h study evaluated the effect of ammonium up to 12 µM at a fixed concentration of nitrate was monitored at 24-h intervals and showed no inhibition of the development of bloom conditions. Collectively, there was no evidence that ammonium interfered with growth, even at concentrations well above the range of postulated effect levels. Of additional interest, the lack of increased growth in TIE treatments targeting chelatable metals and nonpolar organics suggested that these contaminant classes were not present at inhibitory concentrations. These results demonstrate the importance of validation of cause in multistressor environments, and further clarify the roles of different factors that may limit development of bloom conditions in the estuary. Environ Toxicol Chem 2023;42:178-190. © 2022 SETAC.

Zinc cyanide removal by precipitation with quaternary ammonium salts

In gold-processing plants, the final tailing containing metal cyanide species is typically treated using various oxidation methods to produce the main source of process water, which is subsequently recycled to the upstream units, such as flotation units. In some gold-processing plants, a considerable amount of metal cyanide species such as zinc cyanide remains in process water, despite the cyanide destruction process. Because residual zinc cyanide complexes can depress gold flotation, the amount of process water must be decreased such that it can be recycled to a flotation circuit. Previous studies report that the critical concentration of zinc cyanide, measured based on the total cyanide concentration during flotation depression, is 0.4 mmol/L. In the present study, the feasibility of using quaternary ammonium salts to precipitate zinc cyanide complexes to less than the critical concentration was studied. The results showed that 92.17% of 60 mg/L of cyanide and 88.86% of 50 mg/L of zinc (molar ratio Zn/CN = 1:3) can be removed using 0.4 g/L of octadecyl trimethyl ammonium bromide at a pH of 10. The concentration of the residual CN cyanide was less than the critical concentration. This indicates that the abovementioned process is effective when nonpolar organic contaminants and moderate amounts of salt (<50 mmol/L) are present. This work revealed that the precipitation process can be used as an advanced treatment method for process water subjected to oxidation treatment.

Screening of legacy and emerging substances in surface water, sediment, biota and groundwater samples collected in the Siverskyi Donets River Basin employing wide-scope target and suspect screening

Siverskyi Donets is the fourth longest river in Ukraine and its ecosystem is heavily affected by numerous agricultural and industrial activities. An impact of the on-going armed military conflicts in the Eastern Ukraine to the overall pollution by the chemicals has been studied. Considering the uncontrolled activities in the catchment due to the conflict, there is a high demand to assess the contamination status of the Siverskyi Donets basin. In this study, the occurrence of the EU Water Framework Directive priority substances, selected physicochemical parameters and wide-range emerging contaminants were investigated in surface water, groundwater, biota and river sediments samples from 13 sampling sites in the river basin. The study included metals, inorganic, non-polar and polar organic contaminants. The wide-scope target screening of 2316 substances and suspect screening of 2219 substances revealed occurrence of 83 compounds in the studied samples. A few industrial chemicals such as plasticizers bisphenol A and DEHP, as well as flame retardant brominated diphenylethers were found to be potentially hazardous to the ecosystem, exceeding the established legacy environmental quality standards (EQS) or the provisional no-effect concentration (PNEC) values. River sediment samples contained traces of long-term banned chemicals such as polychlorinated biphenyls (PCBs) and degradation products of DDT (p,p'-DDD and p,p'-DDE). A simplified risk assessment based on comparison of measured concentration of the detected compounds against their (eco)toxicity threshold values from the NORMAN Ecotoxicology Database has been performed to aid their prioritization in future monitoring and, eventually, establishing the list of Siverskyi Donets River Basin Specific Pollutants. A comparison with the recent similar studies in the Dniester and Dnieper river basins in Ukraine has shown that the overall pollution by chemicals in the Siverskyi Donets basin is significantly lower.

Characterization of the accumulation of metals and organic contaminants on a novel active-passive sampling device under controlled water flow conditions

Recently, a new sampling device combining active and passive sampling (APS) was developed for the measurement of time-averaged concentrations of metal species and both polar and non-polar organic contaminants in water. By coupling a diffusion cell (loaded with a set of sorbents selective for different substances) with a small pump and a flow meter, the APS device is able to perform in situ measurements that are independent of the hydrodynamic conditions in the exposure medium. In the present study, the diffusion layer thickness (δ) at the sorbent/solution interface within the diffusion cell was characterised under controlled flow conditions. Laboratory tests indicated that, in the range of flow rates investigated, the average diffusion layer thickness (δ¯) varied from ∼60 to ∼110 μm, depending on the type of substance measured and the position of the sorbent with respect to the flow direction. Due to its ability to maintain an approximately constant δ¯, good to excellent agreement was found between measurements performed with the APS device in non-complexing media and concentrations measured in discrete water samples for all the substances investigated. These results suggest that the APS device could overcome issues affecting the quantitative interpretation of measurements by conventional passive sampling devices and serve as a useful tool for simultaneously monitoring a wide range of contaminants in water.

One-Single Extraction Procedure for the Simultaneous Determination of a Wide Range of Polar and Nonpolar Organic Contaminants in Seawater

A rapid analytical method including one-single solid-phase extraction procedure followed by gas and liquid chromatography coupled with high resolution mass spectrometry detection (GC–MS and LC–HRMS respectively) was developed for the quantification of 40 polar and nonpolar organic compounds (1.6 < log Kow < 9.5) in seawater including both legacy and emerging contaminants, with a focus on the most common plastic organic additives. This new method allowed for the analyses of nine organophosphate esters (OPEs), seven phthalates (PAEs), six bisphenols (BPs), five perfluorinated compounds (PFCs), and thirteen legacy organochorinated compounds (OCs, including polychlorobiphenyles and pesticides) with recoveries in the ranges of 57–124 % for OPEs, 52–163 % for PAEs, 64–118 % for BPs, 63–124 % for PFCs, and 40–95 % for OCs. As a result of i) strict cleanup protocols, ii) material and solvent selection, and iii) the use of an ISO 6 cleanroom for sample treatment, the procedural blank levels were always lower than 5 ng L−1, even for the most abundant and ubiquitous compounds like tris-(2-chloro, 1-methylethyl) phosphate (TCPP) and diethylhexyl phthalate (DEHP). The quantification limits were in the ranges of 0.03–0.75 ng L−1 for OPEs, 0.03–0.25 ng L−1 for PAEs, 0.1–5 ng L−1 for BPs, 0.1–8 ng L−1 for PFCs, and 0.02–1.1 ng L−1 for OCs, matching seawater analysis requirements. Dissolved water phase samples collected in Marseille Bay (NW Mediterranean Sea) were analyzed using the developed method reveling the concentration of PAEs up to 140 ng L−1 (DEHP) and that of OCs up to 70 ng L−1 (α-endosulfan). For the first time, we also provided the concentrations of OPEs (TCPP up to 450 ng L−1), BPs (bisphenol S up to 123 ng L−1), and PFCs (PFOS up to 5 ng L−1) in this area. A sampling station close to the municipal waste water treatment plant outfall exhibited the highest concentration levels for all compounds.

Application of an immobilized ionic liquid for the passive sampling of perfluorinated substances in water

Ionic liquids have been used to efficiently extract a wide range of polar and nonpolar organic contaminants from water. In this study, imidazole ionic liquids immobilized on silica gel were synthesized through a chemical bonding method, and the immobilized dodecylimidazolium ionic liquid was selected as the receiving phase material in a POCIS (polar organic chemical integrative sampler) like passive sampler to monitor five perfluoroalkyl substances (PFASs) in water. Twenty-one days of integrative accumulation was conducted in laboratory scale experiments, and the accumulated PFASs in the samplers were eluted and analyzed by high performance liquid chromatography coupled with tandem mass spectrometry (HPLC–MS/MS). The partitioning coefficients of most PFASs between sampler sorbents and water in the immobilized ionic liquid (IIL)-sampler were higher than those in the HLB-sampler, especially for compounds with shorter alkyl chains. The effects of flow velocity, temperature, dissolved organic matter (DOM) and pH on the uptake of these analytes were also evaluated. Under the experimental conditions, the uptake of PFASs in the IIL-sampler slightly increased with the flow velocity and temperature, while different influences of DOM and pH on the uptake of PFAS homologues with short or long chains were observed. The designed IIL-samplers were applied in the influent and effluent of a wastewater treatment plant. All five PFASs could be accumulated in the samplers, with concentrations ranging from 6.5×10−3–3.6×10−1nmol/L in the influent and from 1.3×10−2–2.2×10−1nmol/L in the effluent. The calculated time-weighted average concentrations of most PFASs fit well with the detected concentrations of the active sampling, indicating the applicability of the IIL-sampler in monitoring these compounds in water.

Review of the fundamental geochemical and physical behaviors of organoclays in barrier applications

Organoclays are organic-rich clay minerals, synthesized under controlled laboratory conditions, with engineering properties enhanced for use in containment applications. Organoclays can be formed using a variety of clay minerals as the base material; however, montmorillonite is used most commonly due to its high cation exchange capacity. The cationic organic phase is exchanged onto the mineral surface through ion exchange, with the organic cations displacing the clay's naturally occurring inorganic cations (e.g., Na+, Ca2+). Most commonly, quaternary ammonium cations are used as the organic phase, and organoclay behavior can be engineered through careful selection of the organic cation structure, size, and density of loading.Organoclays are promising materials for geoenvironmental applications due to their high sorption affinity for nonpolar organic contaminants. Sorption mechanisms can be engineered to be competitive or non-competitive, linear or non-linear, depending on the organic cation that is exchanged into the clay interlayer. Exchange of an organic phase for the naturally occurring inorganic interlayer cations also allows control of engineering properties, and clays can be synthesized with increased strength and decreased compressibility. This review of organoclays examines the fundamental behavior of organoclays, with an emphasis on geochemical properties including electrokinetic potential, hydrophobicity, sorptivity, attenuation of nonpolar compounds and electrical conductivity; physical properties including hydraulic conductivity, strength, dynamic properties and thermal stability and thermal conductivity. Relevance of organoclays to different barriers is discussed. Emerging polymer-clay hybrid barrier materials are also summarized.

Advection and retardation of non-polar contaminants in compacted clay barrier material with organoclay amendment

Compacted clay liners (CCLs) are widely used as hydraulic barriers in landfills, underground storage tanks, vertical cutoff walls and surface impoundments. Most commonly, the breakthrough of contaminant flows in CCLs takes a long time due to the reduced advection rate; however, the attenuation of non-polar fluid or organic contaminants in CCLs is relatively low because of the non-reactive nature of most CCL materials. Surfactant-modified bentonites are promising barrier amendments as they are coated with organic surfactant and are capable of uptaking the non-polar species from the aqueous phase. In this study, laboratory tests were carried out to evaluate the swelling, permeability and contaminant retention of compacted silty clay amended with an organoclay (hexadecyltrimethylammonium (HDTMA) modified bentonite) against both gasoline and organic solution. The swelling properties and the hydraulic conductivities of compacted soils with varying liquids were evaluated and the transport of naphthalene, a representative of polycyclic aromatic hydrocarbons (PAHs) and a possible component of NAPLs, in organobentonite-amended silty clay was examined through batch sorption and column tests. The results indicated that the addition of 10% HDTMA bentonite to compacted silty clay slightly increased the permeability of the mixture to water. However, higher swelling tendency and lower permeability to gasoline were also observed. With 5% of HDTMA bentonite amendment, the compacted silty clay soil had a much stronger retardation capacity for naphthalene.

Regeneration of HDTMA-modified minerals after sorption with chromate anions

Surfactant-modified minerals have been widely used for the sorption of anionic and non-polar organic contaminants. This paper investigates the regeneration of various hexadecyltrimethylammonium bromide (HDTMA)-modified natural minerals saturated with chromate anions using different solutions for the extraction of chromates that has been sorbed at optimum conditions. The examined minerals include HDTMA-modified zeolite (clinoptilolite), exfoliated vermiculite, bentonite and attapulgite (palygorskite). Deionized water and sodium chloride, potassium chloride and sodium cyanide solutions at different concentrations (0.1–3 M) were employed as chromate desorption solutions. The HDTMA/Cr(VI)-mineral type, the desorbing solution type and its concentration and the mineral–solution contact time are key parameters that affect the process. From our results it was deduced that regeneration and reuse of HDTMA-modified minerals saturated with chromate is feasible. Bentonite exhibited greater stability than the other minerals studied in adsorption/desorption processes, maintaining 73% of its initial adsorption capacity after 14 successive regeneration cycles. The regeneration performance of the examined minerals follows the order: Bentonite > Attapulgite > Zeolite > Vermiculite. Kinetic study revealed that desorption was faster than adsorption, while the pseudo-second-order equation simulated better the experimental data.

Uptake calibration of polymer-based passive samplers for monitoring priority and emerging organic non-polar pollutants in WWTP effluents.

The uptake calibration of more than 12 non-polar organic contaminants by 3 polymeric materials is shown: bare polydimetilsiloxane (PDMS, stir-bars), polyethersulfone tubes and membranes (PES) and polyoxymethylene membranes (POM), both in their free form and membrane-enclosed sorptive coating (MESCO). The calibration process was carried out exposing the samplers to a continuous flow of contaminated water at 100 ng mL(-1) for up to 28 days, and, consequently, the sampling rates (Rs, mL day(-1)) of several organic microcontaminants were provided for the first time. In situ Rs values were also determined disposing the samplers in the effluent of a wastewater treatment plant. Finally, these passive samplers were applied to monitor the effluents of two wastewater treatment plants. This application lead to the confirmation of the presence of galaxolide, tonalide and 4-tert-octylphenol at high ng mL(-1) levels, as well as the identification of compounds like some phthalates and alkylphenols at levels below the detection limits for active sampling methods.

Influence of Uniform Electric Field in Bioremediation of Oil-Contaminated Soils

Electrokinetic remediation is an effective technology to enhance bioremediation of oil-contaminated soil as the transport process of non-polar organic contaminants in soil was promoted under low-power direct current electric fields. In this study three treatments including the application of electric field treatment alone, inoculation treatment alone, and combination of the application of electric field and inoculation treatment were carried out. The results indicated that highest removal efficiency was 83% in couple of the application of electric field and inoculation treatment. TPH concentration decreased from 6000 mg.kg-1 to 2000 mg.kg-1 when a 30 voltage direct current electric field was applied to oil-contaminated soil for 10 min after 4 days. It was observed that dehydrogenase activity had no increase after application direct current electric field. However, the TPH degradation efficiency was 52% higher than the control treatment. GC analysis showed that n-alkanes (C14-C31) were preferentially degraded, and soil remaindered more low quality compounds after the application of electric field treatment applied 52 days. These results indicated that the application of electric field improved degradation of inoculated bacteria through promoting the transport of nutrients, such as nitrogen and phosphorous and electron acceptors.

Interaction mechanism of benzene and phenanthrene in condensed organic matter: Importance of adsorption (nanopore-filling)

Although microporosity and surface area of natural organic matter (NOM) are crucial to mechanistic evaluation of the sorption process for nonpolar organic contaminants (NOCs), they have wrongly been estimated by the N2 adsorption technique. Nuclear magnetic resonance spectroscopy (13C NMR), and benzene, carbon dioxide, and nitrogen adsorption techniques were used to characterize structural and surface properties for different condensed NOM samples, which were related to the sorption behavior of phenanthrene (Phen). It was found that the revised Freundlich model by taking the chemical activity into account can well describe the isotherms for benzene and Phen. The benzene and Phen adsorption volumes for the coal samples are similar to or lower than the CO2-nanopore volumes. Adsorption volumes of both benzene and Phen are significantly related to the aliphatic carbon structure, and their correlation lines are nearly overlapped, suggesting that the nanopore filling for Phen and benzene on the investigated samples is the dominating mechanism, and also is not affected by water molecules. The entrapment of benzene and/or the pore deformation in the NOM nanopore are likely responsible for the observed hysteresis of benzene. The above results demonstrate that Phen and benzene adsorption on the condensed NOM is closely associated with the aliphatic carbon structure of the investigated samples.

Evidence of Micropore Filling for Sorption of Nonpolar Organic Contaminants by Condensed Organic Matter

Although microporosity and surface area of natural organic matter (NOM) are crucial for mechanistic evaluation of the sorption process for nonpolar organic contaminants (NOCs), they have been underestimated by the N adsorption technique. We investigated the CO-derived internal hydrophobic microporosity () and specific surface area (SSA) obtained on dry samples and related them to sorption behaviors of NOCs in water for a wide range of condensed NOM samples. The is obtained from the total CO-derived microporosity by subtracting out the contribution of the outer surfaces of minerals and NOM using N adsorption-derived parameters. The correlation between or CO-SSA and fractional organic carbon content () is very significant, demonstrating that much of the microporosity is associated with internal NOM matrices. The average and CO-SSA are, respectively, 75.1 μL g organic carbon (OC) and 185 m g OC from the correlation analysis. The rigid aliphatic carbon significantly contributes to the microporosity of the Pahokee peat. A strong linear correlation is demonstrated between / and the OC-normalized sorption capacity at the liquid or subcooled liquid-state water solubility calculated via the Freundlich equation for each of four NOCs (phenanthrene, naphthalene, 1,3,5-trichlorobenzene, and 1,2-dichlorobenzene). We concluded that micropore filling ("adsorption") contributes to NOC sorption by condensed NOM, but the exact contribution requires knowing the relationship between the dry-state, CO-determined microporosity and the wet-state, NOC-available microporosity of the organic matter. The findings offer new clues for explaining the nonideal sorption behaviors of NOCs.

Contaminants assessment in the coral reefs of Virgin Islands National Park and Virgin Islands Coral Reef National Monument

Coral, fish, plankton, and detritus samples were collected from coral reefs in Virgin Islands National Park (VIIS) and Virgin Islands Coral Reef National Monument (VICR) to assess existing contamination levels. Passive water sampling using polar organic chemical integrative samplers (POCIS) and semi-permeable membrane devices found a few emerging pollutants of concern (DEET and galaxolide) and polynuclear aromatic hydrocarbons. Very little persistent organic chemical contamination was detected in the tissue or detritus samples. Detected contaminants were at concentrations below those reported to be harmful to aquatic organisms. Extracts from the POCIS were subjected to the yeast estrogen screen (YES) to assess potential estrogenicity of the contaminant mixture. Results of the YES (estrogen equivalency of 0.17–0.31ng/L 17-β-estradiol) indicated a low estrogenicity likelihood for contaminants extracted from water. Findings point to low levels of polar and non-polar organic contaminants in the bays sampled within VICR and VIIS.

Modeling Sorption and Diffusion of Organic Sorbate in Hexadecyltrimethylammonium-Modified Clay Nanopores – A Molecular Dynamics Simulation Study

Organoclays are highly sorptive engineered materials that can be used as amendments in barrier systems or geosynthetic liners. The performance of confining and isolating the nonpolar organic contaminants by those barrier/lining systems is essentially controlled by the process of organic contaminant mass transport in nanopores of organoclays. In this article, we use molecular dynamics (MD) simulations to study the sorption and diffusion of organic sorbates in interlayers of sodium montmorillonite and hexadecyltrimethylammonium (HDTMA(+))-modified montmorillonite clays. Simulated system consisted of the clay framework, interlayer organic cation, water, and organic sorbate. Their interactions were addressed by the combined force field of ClayFF, constant-valence force field, and SPC water model. Simulation results indicated that in HDTMA coated clay nanopores, diffusion of nonpolar species benzene was slowed because they were subjected to influence of both the pore wall and the HDTMA surfactant. This suggested the nonpolar organic compound diffusion in organophilic clays can be affected by molecular size of diffusive species, clay pore size, and organic surfactant loading. Additionally, a model that connected the diffusion rate of organic compounds in the bulk organoclay matrix with macropores and nanopores was established. The impact of intercalated organic cations on the diffusion dominated mass transport of organic compounds yielded insight into the prediction of the apparent diffusion behavior of organic compounds in organic-modified clays.

Use of passive sampling devices for monitoring and compliance checking of POP concentrations in water

The state of the art of passive water sampling of (nonpolar) organic contaminants is presented. Its suitability for regulatory monitoring is discussed, with an emphasis on the information yielded by passive sampling devices (PSDs), their relevance and associated uncertainties. Almost all persistent organic pollutants (POPs) targeted by the Stockholm Convention are nonpolar or weakly polar, hydrophobic substances, making them ideal targets for sampling in water using PSDs. Widely used nonpolar PSDs include semi-permeable membrane devices, low-density polyethylene and silicone rubber. The inter-laboratory variation of equilibrium partition constants between PSD and water is mostly 0.2-0.5 log units, depending on the exact matrix used. The sampling rate of PSDs is best determined by using performance reference compounds during field deployment. The major advantage of PSDs over alternative matrices applicable in trend monitoring (e.g. sediments or biota) is that the various sources of variance including analytical variance and natural environmental variance can be much better controlled, which in turn results in a reduction of the number of analysed samples required to obtain results with comparable statistical power. Compliance checking with regulatory limits and analysis of temporal and spatial contaminant trends are two possible fields of application. In contrast to the established use of nonpolar PSDs, polar samplers are insufficiently understood, but research is in progress to develop PSDs for the quantitative assessment of polar waterborne contaminants. In summary, PSD-based monitoring is a mature technique for the measurement of aqueous concentrations of apolar POPs, with a well-defined accuracy and precision.

In situ electro-osmotic cleanup of tar contaminated soil—Removal of polycyclic aromatic hydrocarbons

An in situ electro-osmosis experiment was set up in a tar contaminated clay soil in Olst, the Netherlands, at the site of a former asphalt factory. The main goal of this experiment was to remove polycyclic aromatic hydrocarbons (PAHs) from the contaminated clay layer by applying an electric gradient of 12Vm−1 across the soil over an electrode distance of 1m. With the movement of water by electro-osmosis and the addition of a non-ionic surfactant (Tween 80), the non-polar PAHs were dragged along by convection and removed from the fine soil fraction. Soil samples were taken at the start and after 159 days at the end of the experiment. Water at the electrode wells was sampled regularly during the course of the experiment. The results reflect the heterogeneity of the soil characteristics and show the PAH concentrations within the experimental set up. After first having been released into the anolyte solution due to extraction by Tween 80 and subsequent diffusion, PAH concentrations increased significantly in the electrode reservoirs at the cathode side after 90 days of experiment. Although more detailed statistical analysis is necessary to quantify the efficiency of the remediation, it can be concluded that the use of electro-osmosis together with a non-ionic surfactant is a feasible technique to mobilize non-polar organic contaminants in clayey soils.

Sorption of bisphenol A, 17α-ethinyl estradiol and phenanthrene on thermally and hydrothermally produced biochars

Thermal and hydrothermal biochars were characterized, and adsorption of bisphenol A (BPA), 17α-ethinyl estradiol (EE2) and phenanthrene (Phen) was determined to investigate the sorption characteristic difference between the two types of biochars. Thermal biochars were composed mostly of aromatic moieties, with low H/C and O/C ratios as compared to hydrothermal ones having diverse functional groups. Single-point organic carbon-normalized distribution coefficients (log K OC) of EE2 and BPA of hydrothermal biochars were higher than thermal biochars, while Phen log K OC values were comparable among them. X-ray diffraction and solid state nuclear magnetic resonance results suggested that hydrothermal biochars consisted of more amorphous aliphatic-C, possibly being responsible for their high sorption capacity of Phen. This study demonstrated that hydrothermal biochars could adsorb a wider spectrum of both polar and nonpolar organic contaminants than thermally produced biochars, suggesting that hydrothermal biochar derived from poultry and animal waste is a potential sorbent for agricultural and environmental applications.