Sorption and desorption hysteresis of organic contaminants by kerogen in a sandy aquifer material

Sorption and desorption hysteresis of 1,2-dichlorobenzene, 1,3,5-trichlorobenzene, naphthalene, and phenanthrene were investigated for the Borden aquifer material with total organic carbon of 0.021% and the isolated natural organic matter (NOM). The isolated NOM is a kerogen type of organic matter with relatively low maturation degree and contained many different types of organic matters including vitrinite particles. The modified Freundlich sorption capacities (logK^′_f and logK^′_foc) are very close for the sorption of the four solutes by the isolated NOM and the original sand, respectively. Isotherm non-linearity (n value) and hysteric behaviors are related to solute molecular properties (e.g. K_ow and molecular size). Kerogen encapsulated by inorganic matrices in the original aquifer may not be accessed fully by solutes. The larger the hydrophobic organic chemical (HOC) (hydrophobic organic contaminant) molecule is, the lower accessibility of the HOC to kerogen. This study disputes widely held hypothesis that sorption to mineral surfaces may play a major role in the overall sorption by low TOC (e.g. 0.1% by mass) geomaterials such as Borden sand. It also demonstrates the importance of the condensed NOM domain, even at very low contents, in the sorption and desorption hysteresis of HOCs in groundwater systems.     

Reduced analytical availability of polychlorinated biphenyls (PCB's) in colored surface water

It has been generally accepted, during the last few decades, that the dissolved natural organic matter in water [DNOM] appearing as yellow brownish color, has become more and more "polluted" by inorganic and organic micro-pollutants. Due to the complexing properties of NOM, lipophilic organic micro-pollutants, such as, PCBs will be mobilized into water together with the DNOM. A mixture of eight PCBs, with Cl-content from tri-Cl to hepta-Cl, was added to solutions of ten different DNOMs. The DNOMs were aqua's solutions of RO-(reverse osmosis)-isolated material, having approximately the same concentration of carbon. After a contact time of three days, standard analytical PCB-method was used to determine the recovery of the added PCBs. The results show that the analytical availability of the added PCB was significantly reduced in the presence DNOM, compared to distilled water. The percentage loss in recovery of PCB increased with the content of Cl, in mean, from 3%/mg C for tri-Cl to 9%/mg C for hepta-Cl. The results also suggest that the analytical recovery of PCB was affected by the quality and the nature of the organic matter. For example the longer the DNOMs had been in the aquatic phase, the less efficient they are attached to the PCBs.     

Impacts of microbial redox conditions on the phase distribution of pyrene in soil-water systems

Variations in the soil/sediment organic matter (SOM)-hydrophobic organic contaminant (HOC) bindings upon microbially mediated redox conditions were examined. While the extractability of pyrene associated with soil declined after its biodegradation began during aerobic incubation, its variations were almost constant (±3.0-4.4%) during anoxic/anaerobic incubations. The dissolved organic matter released from the soil incubated under highly reduced conditions became more humified and aromatic, had a higher average molecular weight, and was more polydispersed compared to that obtained from oxic incubation, similar to the SOM alterations in the early stage of diagenesis (humification). The concentrations of pyrene in the aqueous phase increased significantly during the soil incubations under highly reduced conditions due to its favorable interaction with the altered DOM. Our results suggest that the microbially mediated redox conditions have significant impacts on SOM and should be considered for the transport, fate, bioavailability, and exposure risk of HOCs in the geo-environments.     

PCE solubilization and mobilization by commercial humic acid

In this paper, comparison is made of terms describing solubilization of hydrophobic organic compounds (HOC) by dissolved humic substances (DHS) and commercial non-ionic surfactants. This paper examines the ability of a commercial humic acid (Aldrich humic acid) to solubilize and mobilize tetrachlorothene (PCE) residual in porous media. The constant for solubilization of PCE by Aldrich humic acid is shown to be a factor of two to thirty times less than that published for dodecyl alcohol ethoxylate surfactants, showing that Aldrich humic acid is less capable than some non-ionic surfactants at solubilizing residual PCE. The depression of PCE–water interfacial tension in the presence of DHS is shown to be significantly less than published values for a non-ionic surfactant, and surfactant mixtures, indicating that the DHS used in this study is less prone to cause mobilization of non-aqueous phase liquids relative to surfactants. Several possible advantages of DHS use in the remediation of subsurface media contaminated with HOC are described, including the ability of DHS to solubilize HOC irrespective of the DHS concentration, and potential lesser tendency of DHS to depress the interfacial tension between non-aqueous phases and water relative to surfactants (an advantage when mobilization is undesired).     

Application of ultrasonic assisted extraction of chemically diverse organic compounds from soils and sediments

The objective of this research was the development, optimization, and demonstration of an ultrasonic assisted extraction (UAE) based method for organic anthropogenic waste indicators (AWIs) with a range of physicochemical properties from soil and sediment samples. The optimized method was designed to be cost effective compared to existing extraction methods, which may require large quantities of consumables, produce substantial volumes of organic waste, or require costly instrumentation or equipment. Reagent grade sand, soil collected from the native grassland in proximity to Eastern Washington University (EWU), and sediment samples collected from the Spokane river were used as sample matrices during method development. These matrices were fortified with eight AWIs of varying chemical properties that are representative of a variety of household, industrial, and agricultural sources. The recoveries of the AWIs spiked onto these matrices were determined in the extracts using gas chromatography/mass spectrometry (GC/MS). These values reflect the efficiency of the method for extraction of these analytes from representative environmental matrices. Recoveries ranged from 46.1% to 110% in the fortified soil and from 49.2% to 118.6% in the fortified sediment samples, which is comparable with existing methods for the study analytes. The optimized method was then used to quantify AWIs in a biosolid-amended soil. Indole and p-cresol were detected in the biosolid-amended soil.     

Bioavailability of HOC depending on the colloidal state of humic substances: a case study with PCB-77 and Daphnia magna

Condensed organic matter with higher affinity for hydrophobic organic compounds (HOC) is currently held responsible for slow desorption and concomitant lower bioavailabilities of HOC in sediments and soils. In an experiment with Daphnia magna and IHSS Peat Humic Acid (PHA), we showed that the bioconcentration factor (BCF) of 3,3',4,4'-tetrachlorobiphenyl (PCB-77) was directly related to the charge of the humic colloid, as predicted by the metal-humic binding model WHAM. Consistent with the type of binding to the humic acid (counter-ion accumulation vs. specific binding), increasing the concentration of Na+ and Ca2+ ions generated opposite effects on colloid charge and HOC binding by the humic acid. Condensation as a colloidal phenomenon in solution as well as on surfaces needs to be addressed as a contributor to lower bioavailabilities and, possibly, to slower desorption kinetics.     

Part V—sorption of pharmaceuticals and personal care products

Background, aim, and scope  Pharmaceuticals and personal care products (PPCPs) including antibiotics, endocrine-disrupting chemicals, and veterinary pharmaceuticals are emerging pollutants, and their environmental risk was not emphasized until a decade ago. These compounds have been reported to cause adverse impacts on wildlife and human. However, compared to the studies on hydrophobic organic contaminants (HOCs) whose sorption characteristics is reviewed in Part IV of this review series, information on PPCPs is very limited. Thus, a summary of recent research progress on PPCP sorption in soils or sediments is necessary to clarify research requirements and directions. Main features  We reviewed the research progress on PPCP sorption in soils or sediments highlighting PPCP sorption different from that of HOCs. Special function of humic substances (HSs) on PPCP behavior is summarized according to several features of PPCP–soil or sediment interaction. In addition, we discussed the behavior of xenobiotic chemicals in a three-phase system (dissolved organic matter (DOM)–mineral–water). The complexity of three-phase systems was also discussed. Results  Nonideal sorption of PPCPs in soils or sediments is generally reported, and PPCP sorption behavior is relatively a more complicated process compared to HOC sorption, such as the contribution of inorganic fractions, fast degradation and metabolite sorption, and species-specific sorption mechanism. Thus, mechanistic studies are urgently needed for a better understanding of their environmental risk and for pollution control. Discussion  Recent research progress on nonideal sorption has not been incorporated into fate modeling of xenobiotic chemicals. A major reason is the complexity of the three-phase system. First of all, lack of knowledge in describing DOM fractionation after adsorption by mineral particles is one of the major restrictions for an accurate prediction of xenobiotic chemical behavior in the presence of DOM. Secondly, no explicit mathematical relationship between HS chemical–physical properties, and their sorption characteristics has been proposed. Last but not least, nonlinear interactions could exponentially increase the complexity and uncertainties of environmental fate models for xenobiotics. Discussion on proper simplification of fate modeling in the framework of nonlinear interactions is still unavailable. Conclusions  Although the methodologies and concepts for studying HOC environmental fate could be adopted for PPCP study, their differences should be highly understood. Prediction of PPCP environmental behavior needs to combine contributions from various fractions of soils or sediments and the sorption of their metabolites and different species. Recommendations and perspectives  More detailed studies on PPCP sorption in separated soil or sediment fractions are needed in order to propose a model predicting PPCP sorption in soils or sediments based on soil or sediment properties. The information on sorption of PPCP metabolites and species and the competition between them is still not enough to be incorporated into any predictive models.     

Sorption of hydrophobic organic compounds onto organoclays

The behavior and fate of nonionic hydrophobic organic compounds (HOCs) in the environment are mainly controlled by their interactions with various components of soils and sediments. Due to their large surface area and abundance in many soils, smectites may greatly influence the fate and transport of the contaminants in the environment. In our experiments, HOC sorption by hexadecyltrimethylammonium (HDTMA)-modified smectite linearly increased with the amount of HDTMA added to the clay. However, tetramethylammonium (TMA)- and dodecyltrimethylammonium (DTMA)-modified smectites showed not only inferiority in their sorption of HOC compared with the HDTMA-smectite, but also a partially decreased HOC sorption at specific surfactant loading levels. This means that the sorption of organoclays for organic contaminants was significantly influenced by the amount and size of the surfactants added on the clay. In addition, it seems that the interlayer structure (e.g., pore size) formed at each surfactant loading level plays an important role to adsorb HOC in different amount.     

Halogenated organic contaminants and mercury in northern fulmars (Fulmarus glacialis): levels, relationships to dietary descriptors and blood to liver comparison

The northern fulmar (Fulmarus glacialis) is an interesting candidate for the study of patterns and levels of halogenated organic contaminants (HOCs) since they accumulate high levels of certain HOCs. In the present study we characterized a suite of established and novel HOCs in northern fulmars breeding on Bj?rn?ya in the Norwegian Arctic. A comparison between blood and liver HOC levels was made, and the levels were related to the ratios of heavier to lighter stable isotopes of nitrogen (15)N/(14)N (delta(15)N) and carbon (13)C/(12)C (delta(13)C) in muscle. A significant difference in congener patterns between blood and liver was found. The delta(13)C was not related to HOCs, neither in liver nor in blood. Weak correlations were found between delta(15)N and liver HOC levels. The 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) in northern fulmars were well above thresholds for reproductive effects in seabirds.     

Cell bioassays for detection of aryl hydrocarbon (AhR) and estrogen receptor (ER) mediated activity in environmental samples

In vitro cell bioassays are useful techniques for the determination of receptor-mediated activities in environmental samples containing complex mixtures of contaminants. The cell bioassays determine contamination by pollutants that act through specific modes of action. This article presents strategies for the evaluation of aryl hydrocarbon receptor (AhR)-(hereafter referred as dioxin-like) or estrogen receptor (ER)-mediated activities of potential endocrine disrupting compounds (EDCs) in complex environmental mixtures. Extracts from various types of environmental or food matrices can be tested by this technique to evaluate their 2,3,7,8-tetrachlorodibenzop-dioxin equivalents (TCDD-EQs) or estrogenic equivalents (E₂-EQs) and to identify contaminated samples that need further investigation using resource-intensive instrumental analyses. Fractionation of sample extracts exhibiting significant activities, and subsequent reanalysis with the bioassays can identify important classes of contaminants that are responsible for the observed activity. Effect-directed chemical analysis is performed only for the active fractions to determine the responsible compounds. Mass-balance estimates of all major compounds contributing to the observed effects can be calculated to determine if all of the activity has been identified, and to assess the potential for interactions such as synergism or antagonism among contaminants present in the complex mixtures. The bioassay approach is an efficient (fast and cost effective) screening system to identify the samples of interest and to provide basic information for further analysis and risk evaluation.     

Matrix effect on the performance of headspace solid phase microextraction method for the analysis of target volatile organic compounds (VOCs) in environmental samples

Solid phase microextraction (SPME) is a fast, cheap and solvent free methodology widely used for environmental analysis. A SPME methodology has been optimized for the analysis of VOCs in a range of matrices covering different soils of varying textures, organic matrices from manures and composts from different origins, and biochars. The performance of the technique was compared for the different matrices spiked with a multicomponent VOC mixture, selected to cover different VOC groups of environmental relevance (ketone, terpene, alcohol, aliphatic hydrocarbons and alkylbenzenes). VOC recovery was dependent on the nature itself of the VOC and the matrix characteristics. The SPME analysis of non-polar compounds, such as alkylbenzenes, terpenes and aliphatic hydrocarbons, was markedly affected by the type of matrix as a consequence of the competition for the adsorption sites in the SPME fiber. These non-polar compounds were strongly retained in the biochar surfaces limiting the use of SPME for this type of matrices. However, this adsorption capacity was not evident when biochar had undergone a weathering/aging process through composting. Polar compounds (alcohol and ketone) showed a similar behavior in all matrices, as a consequence of the hydrophilic characteristics, affected by water content in the matrix. SPME showed a good performance for soils and organic matrices especially for non-polar compounds, achieving a limit of detection (LD) and limit of quantification (LQ) of 0.02 and 0.03 ng g⁻¹ for non-polar compounds and poor extraction for more hydrophilic and polar compounds (LD and LQ higher 310 and 490 ng g⁻¹). The characteristics of the matrix, especially pH and organic matter, had a marked impact on SPME, due to the competition of the analytes for active sites in the fiber, but VOC biodegradation should not be discarded in matrices with active microbial biomass.     

Breast cancer and persistent organic pollutants (excluding DDT): a systematic literature review

Persistent organic pollutants (POPs) are a group of heterogeneous compounds of both natural and anthropogenic origin with highly persistent and bioaccumulative properties. They cause a range of adverse effects to human health and the environment around the world. There is growing concern that POPs may increase breast cancer risk due to their xenoestrogenic properties. The aim of this systematic literature review is to summarize and integrate the risks of breast cancer following environmental exposure to POPs (other than DDT) from primary epidemiological studies published between 2006 and 2015. After searching various databases, 14 case-control studies and one cohort study were included. Evidence of an association between increased breast cancer risk and environmental exposure to these chemicals is inconsistent and inadequate to conclude with certainty. However, most of the studies have examined exposure to the pollutants after diagnosis of breast cancer, overlooking exposure during critical windows of vulnerability. They have also largely focused on individual chemicals but ignored the combined effects of different chemicals. Therefore, major data gaps remain in examining exposure during critical windows of vulnerability and assessing combined effects of multiple chemicals. Development of better exposure assessment methods addressing these gaps is required for future research.     

Solvophobic approach for predicting sorption of hydrophobic organic chemicals on synthetic sorbents and soils

The application of a solvophobic approach for predicting the sorption of hydrophobic organic compounds (HOC) was evaluated with data collected using synthetic sorbents and soils. The experimental data consisted of batch equilibrium sorption coefficients (K_D), as well as soil-TLC and reversed-phase liquid chromatographic (RPLC) retention factors (κ′). All data were collected using aqueous solutions and binary or ternary solvent mixtures of water, methanol, acetone, and acetonitrile. As predicted by the theory, the chromatographic retention factors and sorption coefficients for HOC decreased log-linearly with increasing fraction of organic cosolvent in binary solvents. Model parameters estimated from the binary solvent data could be used to predict sorption (or retention) from ternary solvents. Reasonable agreement was found between model parameters reported in the literature and those estimated using the data from batch sorption, soil-TLC, and RPLC studies.     

Elaboration of new formulations to remove micropollutants in MSWI flue gas

This study consists in identifying and testing potential inorganic substitutes to carbon based materials commonly used as adsorbents for the removal of organic pollutants such as dioxins and furans released from Municipal Solid Waste Incinerators (MSWI). Although carbon materials enable to reach the current regulation in terms of dioxins and furans emissions, they exhibit a potential auto ignition risk when present in hot flue gases. Here, the adsorption potential of carbon based products is compared to the one of some inorganic materials. Chlorobenzene was chosen as a reference molecule to compare the removal performance of the different adsorbents. This comparison was based on the determination of the adsorption energies derived from temperature programmed desorption (TPD) experiments. In the first part of this study, five inorganic materials were selected according to their chlorobenzene adsorption performance compared to those of carbon based products currently used to remove micropollutants from MSWI flue gases. In the second part of the study, the influence of the inlet concentration of adsorbate on the adsorption potential of sorbents is investigated. Actually, the organic compound concentration was decreased in order to be closer to those met in MSWI. Furthermore, the adsorption experiments were performed with other adsorbates whose molecular mass or chlorine content are higher. Thanks to these adsorption results a new organic free formulation has been proposed for the removal of micropollutants. Tests carried out on an industrial scale, demonstrated that this product enables to reach the current norm concerning dioxins and furans emissions.     

Influence of redox potential (Eh) on the availability of arsenic species in soils and soils amended with biosolid

A study was done on the influence of redox potential on the mobility and availability of the various arsenic chemical forms in a Mollisol soil from central Chile amended with biosolid. Arsenic availability was strongly dependent on the applied redox potential. As expected, under reducing conditions (-200 mV vs Hg/Hg(2)Cl(2)) arsenic availability increased significantly, and arsenic was found mainly as arsenite. On the contrary under oxidizing conditions (200 mV vs Hg/Hg(2)Cl(2)) arsenic solubility decreased markedly and was governed by the presence of arsenate. The greatest concentration of organic arsenic species was found under reducing conditions, which would indicate that methylated species may participate in the transformation of arsenate to arsenite. In biosolid-amended soils the concentrations of methylated species increased as a function of time under reducing conditions, which can be attributed to the greater microbial activity resulting from the organic matter supply from the biosolid to soil. In all the systems, a high concentration of As(V) was found under reducing conditions, indicating that the chemical kinetics for the conversion of arsenate to arsenite is slow. Along time, the content of As(V) increased in the control soils, which may be attributed to the possible dissolution of iron oxides and hydroxides under reducing conditions.     

Tidal influence on the distribution of hydrophobic organic contaminants in the Seine Estuary and biomarker responses on the copepod Eurytemora affinis

To elucidate tidally related variations of hydrophobic organic contaminant (HOC) bioavailability and the impact of these contaminants on estuarine ecosystems, both PCB and PAH concentrations were investigated in the dissolved phase and in the suspended particulate material (SPM) of the Seine Estuary. Both PAH and PCB highest levels were observed in surface and bottom water when SPM remobilizations were maximum, in relation to higher speed currents. In parallel, acetylcholinesterase (AChE) and glutathione-S-transferase (GST) activities were investigated in the copepod Eurytemora affinis. Significant decreasing AChE levels were measured during the tidal cycle and between surface and bottom copepods related to salinity and to HOC concentration variations. Significant increasing GST levels were also observed when HOC concentrations in the water column were the highest. This study underlined the need to standardize sampling procedures for biomonitoring studies in order to avoid interfering factors that could modify biomarker responses to chemical exposure.     

Concentrations and distribution of 3,3'-dichlorobenzidine and its congeners in environmental samples from Lake Macatawa

Release of 3,3'-dichlorobenzidine (DCB), an intermediate in dye manufacturing processes, is of environmental concern due to its carcinogenic nature. An 11-year field study has been conducted to elucidate the fate and behavior of DCB and its congeners in the Lake Macatawa (Holland, MI, USA) sediment-water system. The sediments were variable in composition, ranging from sandy sediments with 1-8.7% total organic carbon (OC) to silty-clay sediments with 7.5-20.6% total OC. The pH ranged from 6.3 to 7.4. The findings from this field study confirmed that DCB and its congener, benzidine, are transported over long distances. The concentration of DCB in the water phase was found to be from non-detectable to approximately 1300 times greater than the water quality criteria established for DCB (0.021 microg/l). Its congener, benzidine, which is substantially more toxic for humans than its parent compound has been found up to approximately 12300 times higher levels than the EPA guidelines suggest (0.000086 microg/l). Both DCB and benzidine were found in the sediment phase. DCB was observed at almost 70 mg/kg in a sample collected in 1993. The concentrations in both phases have declined in recent years. To assess the threat of the released pollutants, it is necessary to understand how pollutants tend to behave in various media. Therefore, it is crucial to identify and quantify all sources of the chemical and its congeners in order to meaningfully predict the fate (and transport) of a hydrophobic organic compound (HOC) in the environment.     

Predicting organic contaminant concentrations in sediment porewater using solid-phase microextraction

Because of its cost and time saving features, solid-phase microextraction (SPME) is a leading candidate as a biomimic technique in assessing the bioavailable fraction of hydrophobic organic contaminants (HOCs) in sediment porewater. However, no predictive modeling framework in which to systematically address the effect of key parameters on SPME performance for this application exists. In this study, we derived two governing equations to predict (1) the minimum sediment volume (V(s)min) required to achieve non-depletive conditions, and (2) dissolved phase HOC porewater concentrations (C(pw)) as functions of HOC- and sediment specific characteristics in a conceptual three compartment system. The resulting model predicted that V(s)min was independent of HOC concentrations both in sediment and porewater, but did vary with hydrophobicity (characterized by logK(ow)), the fraction of sediment porewater (f(pw)), and the volume (V(f)) of the SPME sorbent phase. Moreover, the effects of these parameters were minimized (i.e., V(s)min reached plateaus) as logK(ow) approached 4-5. Model predictions of C(pw), a surrogate for SPME-based detection limits in porewater, decreased with increasing sediment volume (V(s)) at low V(s) values, but rapidly leveled off as V(s) increased. A third result suggested that the sediment HOC concentration required for SPME is completely independent of K(ow). These results suggest that relatively small sediment volumes participate in exchange equilibria among sediment, porewater and the SPME fiber, and that large sediment HOC reservoirs are not needed to improve the detection sensitivity of SPME-based porewater samplers. The ultimate utility of this modeling framework will be to assist future experimental designs and help predict in situ bioavailability of sediment-associated HOCs.