Sorption of organic contaminants in a fractured chalk formation

Sorption capability of bedrock components from a fractured chalk province was evaluated using ametryn, phenanthrene, m-xylene, 2,4,6-tribromophenol, and 1,2-dichloroethane. Sorption isotherms for the four aromatic compounds were nonlinear on gray (unoxidized) chalk. Over the studied solution ranges, the distribution coefficient decreased by factor of 3 for phenanthrene and m-xylene, a factor 4 for ametryn, and by an order of magnitude for 2,4,6-tribromophenol. In contrast, 1,2-dichloroethane displayed a linear isotherm. The importance of polar interactions for ametryn sorption was evaluated by normalizing sorption to an "inert" solvent, n-hexane. n-Hexane-normalized sorption of ametryn was much greater than that of phenanthrene, presumably due to ametryn participation in hydrogen bonding interactions. In sharp contrast to sorption to gray chalk, sorption to white (oxidized) chalk is 100- to 1000-fold lower at any given solution concentration. The much greater sorption on gray chalk cannot be explained by specific surface area, clay content, or organic matter content; thus, the nature of the organic matter is considered to control sorption in the chalk samples. Gray chalk sorption capacity estimates for ametryn and 2,4,6-tribromophenol are similar, which, together with evidence of competition for sorption sites, suggests that the limited capacity sorption domain for both compounds is similar.     

Sorption of polar and nonpolar organic contaminants by oil-contaminated soil

Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (K_oil). The resulting oil-contaminated soil–water distribution coefficients (K_d) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C_oil) but sorption-reducing (competitive) effects at intermediate C_oil (approximately 1 g kg⁻¹). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K_d at C_oil above approximately 1 g kg⁻¹ were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.     

Sorption of polar and nonpolar organic contaminants by oil-contaminated soil

Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (K_oil). The resulting oil-contaminated soil–water distribution coefficients (K_d) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C_oil) but sorption-reducing (competitive) effects at intermediate C_oil (approximately 1 g kg⁻¹). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K_d at C_oil above approximately 1 g kg⁻¹ were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.     

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.     

Sorption of organic contaminants by biopolymers: role of polarity, structure and domain spatial arrangement

Sorption behavior of hydrophobic organic contaminants (HOCs) (i.e., pyrene, phenanthrene and naphthalene) by native and chemically modified biopolymers (lignin, chitin and cellulose) was examined. Lignins (native and treated) showed nonlinear sorption for all compounds studied, emphasizing their glassy character. Chitins and celluloses had linear isotherms for phenanthrene and naphthalene, illustrating the dominance of partitioning, while pyrene yielded nonlinear isotherms. Sorption capacity (K(oc)) of HOCs was negatively correlated with the polarity [(O+N)/C] of the biopolymers. Aromatic and alkyl+aromatic C percentages, rather than alkyl C content, demonstrated a better correlation with K(oc) values, indicating the importance of aromatic structures for HOC affinity. Hydrophobicity (K(ow))-normalized K(oc) values decreased sharply with increasing percentage of O-alkyl C versus total aliphatic C (O-alkyl C/total aliphatic C) or with polar C/(alkyl+aromatic C) ratio of the biopolymers until their values reached 80% and 4, respectively, illustrating the effect of surrounding polar groups on reducing affinity for HOCs. Overall, the results of this study highlight the role of spatial arrangement of domains within biopolymers in sorption of HOCs, and point to sorbent properties, such as functionality, polarity and structure, jointly regulating the sorption of HOCs in biopolymers.     

No enhancement in bioconcentration of organic contaminants by low levels of DOM.

The aim of the present work was to systematically study the effect of low concentrations of dissolved organic matter (DOM) on the bioconcentration of organic contaminants, in order to show whether the phenomenon of enhanced bioconcentration factors (BCFs), that has been reported in the literature, is generally found at low levels of DOM or if BCF enhancements are more likely due to a random scatter in the experimental data. The first part of the study tested the hypothesis that low levels of DOM affect the uptake kinetics of organic contaminants, leading to transient enhancements of BCFs, relative to DOM-free controls, which could have been reported as BCF enhancements in short-term studies. We found that the presence of low concentrations of two different types of DOM consistently decreased the bioconcentration of benzo[a]pyrene (BaP) in the water flea Daphnia magna at all exposure times (1-24 h), and that no transient BCF enhancements occurred. The second part of the study systematically investigated if low concentrations of DOM from a wide range of different aquatic systems can cause enhancements in the bioconcentration of organic contaminants. Water fleas were exposed to combinations of four different organic contaminants (BaP, tetrachlorobiphenyl, pentachlorophenol and naphthalene) with low concentrations of 12 different types of DOM that had been collected from various regions throughout Europe. In several of the DOM treatments, we found mean BCFs being higher than mean BCFs in the controls (especially for naphthalene). This shows that the experimental setup used in this study (and similarly in previous studies) can produce seeming BCF enhancements at low concentrations of DOM. However, statistical analyses showed that treatment means were not significantly different from control means. Thus, this systematic study suggests that the BCF enhancements that have been reported in the literature are more likely the result of random, experimental variations than the result of a systematic enhancement of bioconcentration.     

Removal of organic contaminants in bioretention medium amended with activated carbon from sewage sludge

Bioretention, also known as rain garden, allows stormwater to soak into the ground through a soil-based medium, leading to removal of particulate and dissolved pollutants and reduced peak flows. Although soil organic matter (SOM) is efficient at sorbing many pollutants, amending the bioretention medium with highly effective adsorbents has been proposed to optimize pollutant removal and extend bioretention lifetime. The aim of this research was to investigate whether soil amended with activated carbon produced from sewage sludge increases the efficiency to remove hydrophobic organic compounds frequently detected in stormwater, compared to non-amended soil. Three lab-scale columns (520 cm³) were packed with soil (bulk density 1.22 g/cm³); activated carbon (0.5% w/w) was added to two of the columns. During 28 days, synthetic stormwater—ultrapure water spiked with seven hydrophobic organic pollutants and dissolved organic matter in the form of humic acids—was passed through the column beds using upward flow (45 mm/h). Pollutant concentrations in effluent water (collected every 12 h) and polluted soils, as well as desorbed amounts of pollutants from soils were determined using GC-MS. Compared to SOM, the activated carbon exhibited a significantly higher adsorption capacity for tested pollutants. The amended soil was most efficient for removing moderately hydrophobic compounds (log K _ow 4.0–4.4): as little as 0.5% (w/w), carbon addition may extend bioretention medium lifetime by approximately 10–20 years before saturation of these pollutants occurs. The column tests also indicated that released SOM sorb onto activated carbon, which may lead to early saturation of sorption sites on the carbon surface. The desorption test revealed that the pollutants are generally strongly sorbed to the soil particles, indicating low bioavailability and limited biodegradation.

     

Sorption of apolar and polar organic contaminants by waste tire rubber and its chars in single- and bi-solute systems

Single- and bi-solute sorption of organic compounds [1,3-dichlorbenzene (DCB), 1,3-dinitrobenzene (DNB) and 2,4-dichlorophenol (DCP)] on ground tire rubber and its chars was studied. The chars were prepared by pyrolyzing tire rubber at different temperatures (200-800 °C). Their surface area, aromaticity and hydrophobicity increase greatly with pyrolytic temperature, and the polymeric phase is partly converted into a condensed phase. The sorption of DNB and DCP increases with pyrolytic temperature and is characterized by a transition from a partition dominant to an adsorption dominant process. However, the sorption of DCB linearly decreases with the pyrolytic temperature. The enhanced adsorption of DNB and DCP on carbonized phase is primarily attributed to nonhydrophobic interactions such as π-π electron-donor-acceptor interactions and/or H bonding. The higher partition of DCB to polymeric phase is attributed to its high hydrophobicity. Competitive sorption between DCB and DCP on the tire chars is highly dependent on dissociation of the latter.     

Sorption isotherms of brominated diphenyl ethers on natural soils with different organic carbon fractions

Sorption isotherms of BDE-28 and BDE-47 on natural soils with different contents of soil organic matter (SOM) were investigated. Due to low water solubility of BDEs and resulted narrow ranges of aqueous equilibrium concentration, the linear distribution model showed similar and good fitting efficiency to the linear portion of nonlinear Freundlich curve. For the same sample, the linear and nonlinear model fitting sorption coefficients were close. At the statistically significant level of 0.05 or 0.1, significant relationships of total organic carbon fraction (fOC) with the fitting sorption coefficients can be observed. As for BDE-28, the relationships of fOC and SOM fractions with the single point partition coefficients at different aqueous concentrations of BDEs were significant; while for BDE-47, the relationships became less significant or insignificant, especially at higher aqueous concentrations. The findings in this study may facilitate more understanding on transport and fate of studied BDEs in soil systems.     

Optimal conditions for chlorothalonil and dissolved organic carbon in horizontal subsurface flow constructed wetlands

The most efficient system of horizontal subsurface flow constructed wetlands (HSSFCW) for removing dissolved organic carbon (DOC) in the presence of chlorothalonil pesticide (CLT) present in synthetic domestic wastewater was determined using the macrophyte Phragmites australis. Two concentrations of CLT (85 and 385 μg L^?1) and one concentration of glucose (20 mg L^?1) were evaluated in four pilot scale horizontal surface flow constructed wetlands coupled with two sizes of silica gravel, igneous gravel, fine chalky gravel (3.18–6.35 mm), coarse gravel (12.70–25.40 mm) and two water surface heights (20 and 40 cm). For a month, wetlands were acclimated with domestic wastewater. Some groups of bacteria were also identified in the biofilm attached to the gravel. In each treatment periodic samplings were conducted in the influent and effluent. Chlorothalonil was quantified by gas chromatography (GC-ECD m), DOC by an organic carbon analyzer and bacterial groups using conventional microbiology in accordance with Standard Methods. The largest removals of DOC (85.82%–85.31%) were found when using fine gravel (3.18–6.35 mm) and the lower layer of water (20 cm). The bacterial groups quantified in the biofilm were total heterotrophic, revivable heterotrophic, Pseudomonas and total coliforms. The results of this study indicate that fine grain gravel (3.18–6.35 mm) and both water levels (20 to 40 cm) can be used in the removal of organic matter and for the treatment of agricultural effluents contaminated with organo-chloride pesticides like CLT in HSSFCW.     

Diversity of active microbial communities subjected to long-term exposure to chemical contaminants along a 40-year-old sediment core

In estuarine ecosystems, metallic and organic contaminants are mainly associated with fine grain sediments which settle on mudflats. Over time, the layers of sediment accumulate and are then transformed by diagenetic processes mainly controlled by microbial activity, recording the history of the estuary’s chemical contamination. In an environment of this specific type, we investigated the evolution of the chemical contamination and the structure of both total and active microbial communities, based on PhyloChip analysis of a 4.6-m core corresponding to a 40-year sedimentary record. While the archaeal abundance remained constant along the core, a decrease by one order of magnitude in the bacterial abundance was observed with depth. Both total and active microbial communities were dominated by Proteobacteria, Actinobacteria, and Firmicutes in all sediment samples. Among Proteobacteria, alpha-Proteobacteria dominated both total (from 37 to 60 %) and metabolically active (from 19.7 to 34.6 %) communities, including the Rhizobiales, Rhodobacter, Caulobacterales, and Sphingomonadales orders. Co-inertia analysis revealed a relationship between polycyclic aromatic hydrocarbons, zinc and some polychlorobiphenyls concentrations, and the structure of total and active microbial communities in the oldest and most contaminated sediments (from 1970 to 1975), suggesting that long-term exposure to chemicals shaped the structure of the microbial community.     

Competitive sorption of organic contaminants in chalk

In the Negev desert, Israel, a chemical industrial complex is located over fractured Eocene chalk formations where transfer of water and solutes between fracture voids and matrix pores affects migration of contaminants in the fractures due to diffusion into the chalk matrix. This study tests sorption and sorption competition between contaminants in the chalk matrix to make it possible to evaluate the potential for contaminant attenuation during transport in fractures. Single solute sorption isotherms on chalk matrix material for five common contaminants (m-xylene, ametryn, 1,2-dichloroethane, phenanthrene, and 2,4,6-tribromophenol) were found to be nonlinear, as confirmed in plots of Kd versus initial solution concentration. Over the studied concentration ranges, m-xylene Kd varied by more than a factor of 100, ametryn Kd by a factor of 4, 1,2-dichloroethane Kd by more than a factor of 3, phenanthrene Kd by about a factor of 2, and 2,4,6-tribromophenol Kd by a factor of 10. It was earlier found that sorption is to the organic matter component of the chalk matrix and not to the mineral phases (Chemosphere 44 (2001) 1121). Nonlinear sorption isotherms indicate that there is at least some finite sorption domain. Bi-solute competition experiments with 2,4,6-tribromophenol as the competitor were designed to explore the nature of the finite sorption domain. All of the isotherms in the bi-solute experiments are more linear than in the single solute experiments, as confirmed by smaller variations in Kd as a function of initial solution concentration. For both m-xylene and ametryn, there is a small nonlinear component or domain that was apparently not susceptible to competition by 2,4,6-tribromophenol. The nonlinear sorption domain(s) is best expressed at low solution concentrations. Inert-solvent-normalized single and bi-solute sorption isotherms demonstrate that ametryn undergoes specific force interactions with the chalk sorbent. The volume percent of phenanthrene sorbed at the liquid solubility limit is calculated to be 13% v:v in both the single and bi-solute experiments. This value exceeds what may be reasonably interpreted as partitioning of phenanthrene into organic matter, despite the relative linearity of the phenanthrene sorption isotherm (compared with other compounds) in both single and bi-solute systems.     

Sorption of perfluorooctane sulfonate to carbon nanotubes in aquatic sediments

To date, sorption of organic compounds to nanomaterials has mainly been studied for the nanomaterial in its pristine state. However, sorption may be different when nanomaterials are buried in sediments. Here, we studied sorption of Perfluorooctane sulfonate (PFOS) to sediment and to sediment with 4% multiwalled carbon nanotubes (MWCNTs), as a function of factors affecting PFOS sorption; aqueous concentration, pH and Ca²⁺ concentration. Sorption to MWCNT in the sediment–MWCNT mixtures was assessed by subtracting the contribution of PFOS sorption to sediment-only from PFOS sorption to the total sediment–MWCNT mixture. PFOS Log K_D values ranged 0.52–1.62 L kg^?1 for sediment and 1.91–2.90 L kg^?1 for MWCNT present in the sediment. The latter values are relatively low, which is attributed to fouling of MWCNT by sediment organic matter. PFOS sorption was near-linear for sediment (Freundlich exponent of 0.92 ± 0.063) but non-linear for MWCNT (Freundlich exponent of 0.66 ± 0.03). Consequently, the impact of MWCNT on sorption in the mixture was larger at low PFOS aqueous concentration. Effects of pH and Ca²⁺ on PFOS sorption to MWCNT were statistically significant. We conclude that MWCNT fouling and PFOS concentration dependency are important factors affecting PFOS–MWCNT interactions in sediments.     

Sorption kinetics of chlorinated hydrophobic organic chemicals

This is the second of a two-part series describing the sorption kinetics of hydrophobic organic chemicals. Part I “The Use of First-Order Kinetic Multi-Compartment Models” is published in issue 1 of this journal, pp. 21–28. Sorption kinetics of chlorinated benzenes from a natural lake sediment have been investigated in gas-purge desorption experiments. Biphasic desorption curves, with an initial “fast” part and a subsequent “slow” part, were found for all tested chlorobenzenes. From these results first-order sorption uptake and desorption rate constants were calculated with a two-sediment compartment model, which is presented in the first paper. In three sets of experiments the sorption uptake period and sediment/water ratio were varied. Rate constants are not influenced by these experimental conditions, which supports the partitioning concept for the sorption of hydrophobic organic chemicals in sediments.     

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.     

Sorption of organic gases in residential rooms

Experiments were conducted to characterize organic gas sorption in residential rooms studied “as-is” with furnishings and material surfaces unaltered and in a furnished chamber designed to simulate a residential room. Results are presented for 10 rooms (five bedrooms, two bathrooms, a home office, and two multi-function spaces) and the chamber. Exposed materials were characterized and areas quantified. A mixture of volatile organic compounds (VOCs) was rapidly volatilized within each room as it was closed and sealed for a 5-h Adsorb phase; this was followed by 30-min Flush and 2-h closed-room Desorb phases. Included were alkane, aromatic, and oxygenated VOCs representing a range of ambient and indoor air pollutants. Three organophosphorus compounds served as surrogates for Sarin-like nerve agents. Measured gas-phase concentrations were fit to three variations of a mathematical model that considers sorption occurring at a surface sink and potentially a second, embedded sink. The 3-parameter sink–diffusion model provided acceptable fits for most compounds and the 4-parameter two-sink model provided acceptable fits for the others. Initial adsorption rates and sorptive partitioning increased with decreasing vapor pressure for the alkanes, aromatics and oxygenated VOCs. Best-fit sorption parameters obtained from experimental data from the chamber produced best-fit sorption parameters similar to those obtained from the residential rooms.     

Sorption of organic compounds to activated carbons. Evaluation of isotherm models

Sorption to ‘hard carbon’ (black carbon, coal, kerogen) in soils and sediments is of major importance for risk assessment of organic pollutants. We argue that activated carbon (AC) may be considered a model sorbent for hard carbon. Here, we evaluate six sorption models on a literature dataset for sorption of 12 compounds onto 12 ACs and one charcoal, at different temperatures (79 isotherms in total). A statistical analysis, accounting for differences in the number of fitting parameters, demonstrates that the dual Langmuir equation is in general superior and/or preferable to the single and triple Langmuir equation, the Freundlich equation, a Polanyi–Dubinin–Manes equation, and the Toth equation. Consequently, the analysis suggests the presence of two types of adsorption sites: a high-energy (HE) type of site and a low-energy (LE) type of site. Maximum adsorption capacities for the HE domain decreased with temperature while those for the LE domain increased. Average Gibbs free energies for adsorption from the hypothetical pure liquid state at 298 K were fairly constant at −15 ± 4 and −5 ± 4 kJ mol⁻¹ for the HE and LE domain, respectively.     

Complexation-flocculation of organic contaminants by the application of oxyhumolite-based humic organic matter

Control of hazardous organic micropollutants is a challenging water quality issue. Dissolved humic organic matter (DOM) isolated from oxyhumolite coal mined in Bohemia was investigated as a complexation agent to remove polycyclic aromatic hydrocarbons (PAHs) and functionalized phenols from water by a two-stage process involving complexation and flocculation. After the formation of humic-contaminant complexes, ferric salts were added resulting in the precipitation and flocculation of the DOM and the associated pollutants. Flocculation experiments with ferric ion coagulants indicated that precipitation of oxyhumolite DOM together with the complexed contaminants occurred at lower ferric ion concentrations than with the reference DOM in acidic environments (pH approximately 3.5). The complexation-flocculation removal rates for non-reactive PAHs characterized by small localization energies of pi-electrons correlated well with the complexation constants. On the other hand, the combined complexation-flocculation removal rates for activated PAHs including trans-stilbene, anthracene and 9-methyl anthracene, as well as functionalized polar phenols, were higher than predicted from the complexation coefficients. Methodological studies revealed for the first time that the ferric ion coagulant contributed to enhanced removal rates, most probably due to ferric ion-catalyzed pollutant degradation resulting in oxidized products.