Importance of structural makeup of biopolymers for organic contaminant sorption

Sorption of pyrene, phenanthrene, naphthalene, and 1-naphthol by original (lignin, chitin, and cellulose) and coated biopolymers was examined. Organic carbon normalized distribution coefficients (Koc) of all compounds by the original biopolymers followed the order lignin > chitin > cellulose, in line with the order of their hydrophobicity. Hydrophobicity of structurally similar organic compounds is the main factor determining their ability to occupy sorption sites in biopolymers. Specific interactions (e.g., H-bonding) between 1-naphthol and chitin or cellulose increased its ability to occupy sorption sites. Lignin coating resulted in an increased Koc for phenanthrene (13.6 times for chitin and 6.9 times for cellulose) and 1-naphthol (6.0 times for chitin and 3.7 times for cellulose) relative to the acetone-treated chitin and cellulose. Also, these coated biopolymers had increased isotherm nonlinearity, due to the newly formed condensed domains. An increase in phenanthrene and 1-naphthol sorption by lignin-coated biopolymers as compared to chitin and cellulose was contributed by the newly created high-energy sites in condensed domains and coated lignin. Results of this study highlight the importance of the structural makeup of biopolymers in controlling the sorption of hydrophobic organic compounds.     

Roles of acetone-conditioning and lipid in sorption of organic contaminants

Sorption of phenanthrene and 1-naphthol by a peat soil (PS) and its humic acid fractions (HAs) and humin (HM) was examined. Both phenanthrene and 1-naphthol consistently had decreased isotherm nonlinearity in the order PS > HA1 (first fraction) > HA7 (seventh fraction), due to decreased heterogeneity of soil organic matter (SOM). High isotherm nonlinearity of HM was attributed to the condensed structure of SOM in it. Acetone-conditioning increased sorption affinity and isotherm nonlinearity of HAs and HM for phenanthrene, and the conditioning effect was more pronounced at low solute concentrations. However, sorption of 1-naphthol by PS, HAs, and HM was insignificantly affected by acetone-conditioning, suggesting that 1-naphthol could have disparate distribution of sorbed sites from phenanthrene due to their structure and hydrophobicity difference. Lipid removal further increased sorption of phenanthrene and 1-naphthol by acetone-conditioned PS, HAs, and HM, due to increased accessibility of high-energy sites in SOM. Nonlinearity of phenanthrene and 1-naphthol also increased after lipid removal from the acetone-conditioned sorbents. In 1-naphthol- and phenanthrene-lipid competitive sorption systems, lipid had strong competition with phenanthrene, whereas 1-naphthol exhibited cooperative sorption with lipid on lipid-free PS, HAs, and HM, again showing the different sorption characteristics between phenanthrene and 1-naphthol.     

Sorption and displacement of pyrene in soils and sediments

Sorption isotherms of pyrene on soils and sediments were examined to understand its sorption behavior. All systems examined exhibited nonlinear sorption. Sorption nonlinearity was found to be a function of the polarity index of soil/sediment organic matter (SOM), suggesting that the degree of condensation of SOM, characterized by its polarity index, was correlated with the sorption behavior of pyrene. The polarity index of SOM could be a new factor for explaining the sorption nonlinearity. The sorption affinity of two soils and two sediments for pyrene increased with decreasing SOM polarity. A higher sorption affinity in the two soils was associated with a higher degree of condensation of SOM compared to that of the two sediments. A displacement test was performed after pyrene sorption using phenanthrene as a displacer. Pyrene was displaced in all systems examined, and nonlinearity became less pronounced after displacement. Such an increase in isotherm linearity implied that sorption site energies became more homogeneous after displacement. Furthermore, the site energy distribution IE*) derived from the Freundlich model parameters showed that energy reduction of high-energy sites was more significant than that of low-energy sites after displacement. In addition, a decrease in sorption capacity after displacement could be ascribed to the partial depletion of sorption sites by the displacer. The displacement data indicated that the cocontaminant can have potential effects on the fate and bioavailability of anthropogenic organic pollutants sorbed in soils and sediments, thus affecting their exposure risks.     

Sorption of organic contaminants by biopolymer-derived chars

Sorption of phenanthrene and naphthalene by chitin and cellulose, as well as these biopolymer-derived chars, was examined. Carbon contents were much higher in the chars than their respective biopolymers, and nitrogen was dramatically accumulated in the chitin-derived chars. After charring, sorption of these two compounds was greatly increased, which was attributed to the newly created surface area, porosity, and aromatic components. The aromatic carbon content of the biopolymer chars increased with an increase in the charring temperature. Sorption of phenanthrene and naphthalene to chitin and cellulose was dominated by partitioning. However, after charring, sorption of these two compounds became much more of an adsorption process, because of the newly created surfaces and micropores. The maximum mass sorption capacity of phenanthrene and naphthalene by the original biopolymers and their chars was positively correlated with their surface areas, suggesting that active sorption sites were largely on the surfaces of chars. At low solute concentrations, sorption of phenanthrene and naphthalene by biopolymer chars was dominated by the micropore-filling mechanism; with an increase in the solute concentration, sorption of these two compounds by biopolymer chars shifted to a surface-sorption-dominant process.The maximum mass sorption capacity and K(ow)-normalized sorption amount of phenanthrene were lower than those of naphthalene by the biopolymers and their chars, showing the influence of molecular dimension on sorption. This study demonstrates the significantly enhanced sorption of hydrophobic organic compounds by highly polar biopolymers through charring and the joint roles of surface area, porosity, and surface functionalities of biopolymer-derived chars in governing sorption.     

Pyrene and phenanthrene sorption to model and natural geosorbents in single- and binary-solute systems

Sorption of pyrene and phenanthrene to model (illite and charcoal) and natural (Yangtze sediment) geosorbents were investigated by batch techniques using fluorescence spectroscopy. A higher adsorption of phenanthrene was observed with all sorbents, which is related to the better accessibility of smaller molecules to micropores in the molecular sieve sorbents. In addition, pyrene sorption in binary-solute systems with a constant initial concentration of phenanthrene (0.1 μmol L(-1) or 2 μmol L(-1)) was studied. A 0.1 μmol L(-1) concentration of phenanthrene causes no competitive effect on the pyrene sorption. A 2 μmol L(-1) concentration of phenanthrene significantly suppresses the sorption of pyrene, especially in the low concentration range; nonlinearity of the pyrene sorption isotherms thus decreases. The competitive effect of 2 μmol L(-1) phenanthrene on the pyrene sorption is overestimated by the ideal adsorbed solution theory (IAST) using the fitted single sorption results of both solutes. An adjustment of the IAST application by taking into account the molecular sieve effect is proposed, which notably improves the IAST prediction for the competitive effect.     

Competitive sorption of pyrene on wood chars

Sorption isotherms of pyrene on original and heat-treated wood chars were examined to understand its sorption behavior. Pyrene in single-solute systems had nonlinear isotherms. Polanyi-based dual-domain model fit sorption data well, and the model results showed that the adsorption component dominated pyrene sorption by original char at all aqueous concentrations. In contrast, this adsorption component contributed a much lower fraction to the total sorption by the heat-treated char, and dominated only at low solute concentrations; with increasing concentration, partitioning became a predominant contributor to the total sorption. Competitive effect of four cosolutes, phenanthrene (Phen), benzo[a]anthracene (BaA), 2,2-methylene-bis (4-methyl-6-tert-butylphenol) (MMBP), and phenol on pyrene sorption by original and treated chars was examined to understand the underlying mechanism of competition. Hydrophobicity (adsorbability) and molecular size of competitors played an important role in competition with pyrene by both chars, suggesting the direct competition for sorption sites and pore blockage mechanism. Competitive sorption results indicated that the fate and transport of hydrophobic organic chemicals (e.g., pyrene) could be strongly affected in the presence of coexisting organic contaminants with high hydrophobicity and large molecularsize,thereby, enhancing the mobility and leachability of these chemicals.     

Sorption of organic contaminants by carbon nanotubes: influence of adsorbed organic matter

Sorption of three types of dissolved organic matter (DOM; i.e., humic acid, peptone and alpha-phenylalanine) by a mutiwalled carbon nanotube (MWNT40) and sorption of phenanthrene (Phen), naphthalene (Naph), and 1-naphthol (1-Naph) by the original and DOM-coated MWNT40 were examined. Sorption data of Phen, Naph, and 1-Naph by all sorbents were fitted with Freundlich and Polanyi models. MWNT40 had nonlinear isotherms for all DOMs examined. Sorption of DOMs by MWNT40 followed the order peptone > humic acid > alpha-phenylalanine. The humic acid used in this study had much lower sorption for Phen, Naph, and 1-Naph than MWNT40, but its coating did not make striking changes on sorption of these compounds by MWNT40, suggesting that humic acid coating dramatically altered the physical form and surface properties of MWNT40. Peptone coating made the strongest suppression on sorption of Phen, Naph, and 1-Naph by MWNT40 among the three DOMs used, due to its highest sorption on MWNT40, thus causing a great reduction in accessibility of sorption sites. Polanyi modeling results showed that reduction in the maximum volume sorption capacity (Q0) of MWNT40 induced by DOM coating followed the order Phen < Naph < 1-Naph. 1-Naph was less hydrophobic than Phen and Naph but it had much higher sorbed volume (V(m)) than Phen and Naph at individual RT In(S(w)/C(e))/V(s)points for all sorbents. The correlation curve for the Polanyi model was applicable for sorption of aromatic compounds of similar structure by the original and DOM-coated carbon nanotubes.     

Dispersion state and humic acids concentration-dependent sorption of pyrene to carbon nanotubes

Sonication and humic acids (HA) are known to disperse carbon nanotube (CNT) suspensions, but potential effects on sorption of chemicals to CNTs remain poorly understood. We applied a passive sampling method to investigate the influence of dispersion/aggregation on sorption of pyrene to CNTs. Sonication broke down CNT aggregates and increased pyrene sorption affinity by up to 1.39 orders of magnitude. Sorption surfaces newly exposed by sonication remained available to pyrene even after reaggregation occurred, suggesting an irreversible effect of sonication. The presence of HA decreased sorption of pyrene to CNTs, but at the highest HA concentration investigated (200 mg/L), sorption affinity was still 1.90 orders of magnitude larger than sorption of pyrene to HA alone. Specific interactions between pyrene and CNTs were thus still taking place, in spite of the presence of a HA coating on the CNTs' surface. A greater suppression of sorption by CNTs occurred when the HA addition was combined with a sonication pretreatment. Sorption isotherm fitting indicated that the maximum sorption capacity, sorption affinity, and heterogeneity of the CNT surface were all affected by sonication and the presence of HA at a concentration as low as 1 mg/L. The present results contribute to an improved understanding of the sorption behavior of CNTs in both natural and wastewater systems.     

Evidence for a pore-filling mechanism in the adsorption of aromatic hydrocarbons to a natural wood char

Sorption isotherms for five aromatic hydrocarbons were obtained with a natural wood char (NC1) and its residue after solvent extraction (ENC1). Substantial isotherm nonlinearity was observed in all cases. ENC1 showed higher BET surface area, higher nitrogen-accessible micropore volume, and lower mass of extractable organic chemicals, including quantifiable polycyclic aromatic hydrocarbons (PAHs),while the two chars showed identical surface oxygen/ carbon (O/C) ratio. For two chlorinated benzenes that normally condense as liquids at the temperatures used, sorption isotherms with NC1 and ENC1 were found to be statistically identical. For the solid-phase compounds (1,4-dichlorobenzene (1,4-DCB) and two PAHs), sorption was statistically higher with ENC1, thus demonstrating sorption effects due to both (1) authigenic organic content in the sorbentand (2)the sorbate's condensed state. Polanyi-based isotherm modeling, pore size measurements, and comparisons with activated carbon showthe relative importance of adsorptive pore filling and help explain results. With both chars, maximum sorption increased in the order of decreasing molecular diameter: phenanthrene < naphthalene < 1,2-dichlorobenzene/1,2,4-trichlorobenzene < 1,4-DCB. Comparison of 1,4- and 1,2-DCB shows that the critical molecular diameter was apparently more important than the condensed state, suggesting that 1,4-DCB sorbed in the liquid state for ENC1.     

Sorption/desorption reversibility of phenanthrene in soils and carbonaceous materials

Sorption/desorption of phenanthrene in two soil samples and carbonaceous materials was found to yield co-incident equilibrium isotherms and no significant hysteresis was observed. Additionally, release of native phenanthrene was investigated. Equilibrium sorption and desorption isotherms were determined using pulverized samples of Pahokee peat, lignite, and high-volatile bituminous coal, a mineral soil, and an anthropogenic soil. Instead of the conventional decant-and-refill batch method, sorption/desorption was driven by temperature changes using consistent samples. Sorption started at 77 degrees C and was increased by reducing the temperature stepwise to 46, 20, and finally 4 degrees C. For desorption the temperature was increased stepwise again until 77 degrees C was reached. Besides the co-incident sorption and desorption isotherms at each temperature step, the solubility-normalized sorption/desorption isotherms of all different temperatures collapseto unique overall isotherms. Leaching of native phenanthrene occurred at much lower concentrations but was well predicted by extrapolation of the spiked sorption isotherms indicating that the release of native phenanthrene involves the same sorption/desorption mechanisms as those for newly added phenanthrene.     

Sorption of PAHs by aspen wood fibers as affected by chemical alterations

Sorption and desorption experiments for phenanthrene and pyrene, using untreated (UTR) and treated (bleaching and hydrolysis) aspen wood fibers, were examined to understand their sorption mechanisms. The wood was characterized by elemental and porosity analysis, solid-state 13C NMR, and diffuse reflectance infrared Fourier transform spectroscopy. Bleaching removed aromatic components, yielding the highest polarity and increased porosity, whereas hydrolysis removed a large percentage of hemicellulose and parts of amorphous cellulose, producing a matrix with more aromatic moieties, lower polarity, and higher porosity than that of the UTR wood fibers. All isotherms fitted well to the Freundlich equation and the N values had a decreasing trend from bleached (BL), UTR, low-temperature hydrolyzed to high-temperature hydrolyzed (HHY) wood fibers. BL fibers had the lowest sorption capacity (Koc) for both phenanthrene and pyrene. HHY had the highest Koc because of its high aromatic carbon content and low polarity. The results suggest that aromatic moieties and polarity of wood fibers play significant roles in polycyclic aromatic hydrocarbon (PAHs) sorption and desorption. Thus, both aromatic components and polarity should be considered when predicting the PAHs sorption/desorption by aspen wood fibers. This study demonstrated that aspen wood fibers are a potential sorbentfor PAHs and that chemical modifications of the wood matrix can effectively increase its sorption efficiency. These results may have implications for the treatment of stormwater runoff and other PAH-contaminated liquids.     

Competitive sorption of pyrene, phenanthrene, and naphthalene on multiwalled carbon nanotubes

Knowledge of toxic chemical sorption by carbon nanotubes (CNTs) is critical for environmental application of CNTs as superior sorbents and for environmental risk assessment of both CNTs and toxic chemicals. Single-solute sorption results were reported in the literature, however, they cannot be used for predicting pollutant sorption by CNTs in wastewater and natural water systems where multiple organic contaminants are present. In this study, competitive sorption of pyrene, phenanthrene, and naphthalene on a multiwalled CNT material was investigated. All isotherms in single-, bi-, and tri-solute systems were fitted well by the Dubinin-Ashtakhov (DA) model. The isotherm of a given primary solute changed from being significantly nonlinear to nearly linear when competitors were added. The observed competitive sorption depended on the relative equilibrium concentrations of both primary and cosolutes. Significant competition was observed at relatively low concentrations of primary solute and high concentrations of competitors, while competition was much weaker in the case of relatively high concentrations of primary solute and low competitor concentrations. When the relative concentration of primary solute (Ce/Cs) approached 1, competition by other solutes seemed to disappear. Sorption and competition of three polycyclic aromatic hydrocarbons (PAHs) on CNTs could not be explained with either pore-filling or partition-adsorption mechanisms. A Polanyi-based surface adsorption mechanism was proposed to interpret the observed sorption and competition.     

Black carbon and kerogen in soils and sediments. 2. Their roles in equilibrium sorption of less-polar organic pollutants

The first paper of this series reported that soil/sediment organic matter (SOM) can be fractionated into four fractions with a combined wet chemical procedure and that kerogen and black carbon (BC) are major SOM components in soil/sediment samples collected from the industrialized suburban areas of Guangzhou, China. The goal of this study was to determine the sorptive properties forthe four SOM fractions for organic contaminants. Sorption isotherms were measured with a batch technique using phenanthrene and naphthalene as the sorbates and four original and four Soxhlet-extracted soil/sediment samples, 15 isolated SOM fractions, and a char as the sorbents. The results showed that the sorption isotherms measured for all the sorbents were variously nonlinear. The isolated humic acid (HA) exhibited significantly nonlinear sorption, but its contribution to the overall isotherm nonlinearity and sorption capacity of the original soil was insignificant because of its low content in the tested soils and sediments. The particulate kerogen and black carbon (KB) fractions exhibited more nonlinear sorption with much higher organic carbon-normalized capacities for both sorbates. They dominate the observed overall sorption by the tested soils and sediments and are expected to be the most important soil components affecting bioavailability and ultimate fate of hydrophobic organic contaminants (HOCs). The fact that the isolated KB fractions exhibited much higher sorption capacities than when they were associated with soil/sediment matrixes suggested that a large fraction of the particulate kerogen and BC was not accessible to sorbing HOCs. Encapsulation within soil aggregates and surface coverage by inorganic and organic coatings may have caused large variations in the accessibility of fine kerogen and BC particles to HOCs and hence lowered the sorption capacity of the soil. This variability posts an ultimate challenge for precisely predicting HOC sorption by soils from the contents of different types of SOM.     

Dyestuffs and metal ions absorbents based on UV-coated Nylon-6 fabric

Hydrophilicity of Nylon-6 fabrics has been modified by surface coating with aqueous solution of carboxymethyl cellulose and acrylic acid (AAc) using UV irradiation. The effect of AAc concentration and UV irradiation time (minute) on the hydrophilic properties of the coated nylon fabric was studied. Water absorption (%) increased with increasing AAc concentration up to 20% at 20 min. Morphology of coated fabrics was examined by scanning electron microscope, which indicated compatibility between coating layer and fabrics. Moreover, mechanical properties in terms of tensile strength and elongation at break were studied. The sorption of dyestuffs such as basic, and reactive and also, sorption of metal ions by coated fabrics was measured using UV Spectrophotometer. The results showed that the coated fabrics have a high affinity for basic rather than reactive dye. Also, coated fabrics show good efficiency toward metal ions such as Cu²⁺, Ni²⁺, and Co²⁺. The results obtained show that the coated nylon fabrics have good sorption ability toward heavy metal ions and dyes.     

Insights into the sorption properties of cutin and cutan biopolymers

Plant cuticles have been reported as highly efficient sorbents for organic compounds. The objective of this study was to elucidate the sorption and desorption behavior of polar and nonpolar organic compounds with the major structural components of the plant cuticle: the biopolymers cutin and cutan. The sorption affinity values of the studied compounds followed the order: phenanthrene > atrazine > chlorotoluron > carbamazepine. A higher sorption affinity of phenanthrene and atrazine to cutin was probably due to the higher level of amorphous paraffinic carbon in this biopolymer. Phenanthrene exhibited reversible sorption behavior and a high ratio of organic-carbon-normalized distribution coefficient (Koc) to carbon-normalized octanol-water partitioning coefficients (Kowc) with both biopolymers. This suggests that both biopolymers provide phenanthrene with a partition medium for hydrophobic interactions with the flexible long alkyl-chain moieties of the biopolymers. The low Koc/Kowc ratios obtained for the polar sorbates suggest that the polar sites in the biopolymers are not accessible for sorption interactions. Atrazine and carbamazepine exhibited sorption-desorption hysteresis with both sorbents, indicating that both sorbates interact with cutin and cutan via both hydrophobic and specific interactions. In general, the sorptive properties of the studied biopolymers were similar, signifying that the active sorption sites are similar even though the biopolymers exhibit different properties.     

Effect of cellulose/hemicellulose and lignin on the bioavailability of toluene sorbed to waste paper

Paper constitutes about 38% of municipal solid waste, much of which is disposed of in landfills. Sorption to such lignocellulosic materials may limit the bioavailability of organic contaminants in landfills. The objective of this study was to identify the effect of individual biopolymers in paper on toluene sorption and bioavailability by subjecting fresh and anaerobically degraded office paper and newsprint to enzymatic hydrolysis and acid hydrolysis. Enzymatic degradation of cellulose and hemicellulose had no effect on toluene bioavailability. In contrast, acid-insoluble lignin controlled toluene sorption and bioavailability for both fresh and degraded newsprint. Acid-insoluble lignin could explain only 54% of the toluene sorption capacity of degraded office paper however, suggesting that crude protein and/or lipophilic organic matter were also important sorbent phases. Toluene sorbed to degraded office paper was also less bioavailable than toluene sorbed to an equivalent mass of lignin extracted from this sorbent. The latter result suggests that a fraction of toluene sorbed to degraded office paper may have been sequestered by lipophilic organic matter. The sorption and bioavailability data indicate that the preferential decomposition of cellulose and hemicellulose relative to lignin in landfills should not decrease the overall toluene sorption capacity of paperwaste or increase the bioavailability of sorbed toluene.     

Sorption mechanisms of phenanthrene, lindane, and atrazine with various humic acid fractions from a single soil sample

The sorption behavior of organic compounds (phenanthrene, lindane, and atrazine) to sequentially extracted humic acids and humin from a peat soil was examined. The elemental composition, XPS and (13)C NMR data of sorbents combined with sorption isotherm data of the tested compounds show that nonspecific interactions govern sorption of phenanthrene and lindane by humic substances. Their sorption is dependent on surface and bulk alkyl carbon contents of the sorbents, rather than aromatic carbon. Sorption of atrazine by these sorbents, however, is regulated by polar interactions (e.g., hydrogen bonding). Carboxylic and phenolic moieties are key components for H-bonding formation. Thermal analysis reveals that sorption of apolar (i.e., phenanthrene and lindane) and polar (i.e., atrazine) compounds by humic substances exhibit dissimilar relationships with condensation and thermal stability of sorption domains, emphasizing the major influence of domain spatial arrangement on sorption of organic compounds with distinct polarity. Results of pH-dependent sorption indicate that reduction in sorption of atrazine by the tested sorbents is more evident than phenanthrene with increasing pH, supporting the dependence of organic compound sorption on its polarity and structure. This study highlights the different interaction mechanisms of apolar and polar organic compounds with humic substances.     

Solubility-normalized combined adsorption-partitioning sorption isotherms for organic pollutants

Equilibrium sorption isotherms were measured for five different low-polarity organic compounds (benzene, trichloroethene, 1,2- and 1,4-dichlorobenzene, and phenanthrene) over a wide concentration range. The investigated sorbents can be grouped into the following three classes: (1) humic soil organic matter, which shows linear sorption isotherms (solely partitioning, as observed in the peat sample); (2) carbon materials, which were thermally altered (due to their natural history or industrial production) and thus contain a high specific surface area and exhibit nonlinear isotherms, and (3) pure engineered microporous materials (e.g., zeolites and activated carbon), where adsorption is solely due to a pore-filling process. Sorption of all compounds was fitted very well by the Polanyi-Dubinin-Manes (PDM) model, which for sorbents containing humic organic matter (e.g., peat) was combined with linear partitioning. Both the partitioning and the Polanyi-Dubinin-Manes model predict unique sorption isotherms of similar compounds if the solubility-normalized aqueous concentration is used. In addition, an inverse linear relationship between the distribution coefficient (Kd) and water solubility, which was very well confirmed by the data, is obtained. This also leads to unit-equivalent Freundlich sorption isotherms and explains the often observed apparent correlation between sorption capacity at a given concentration (e.g., Freundlich coefficient) and sorption nonlinearity (Freundlich exponent).     

Sorption of polar and nonpolar aromatic organic contaminants by plant cuticular materials: role of polarity and accessibility

In both forest and agricultural soils, plant derived cuticular materials can constitute a significant part of soil organic matter. In this study, the sorption of nonpolar (naphthalene and phenanthrene) and polar (phenol and 1-naphthol) aromatic organic pollutants to aliphatic-rich cuticularfractions of green pepper (Capsicum annuum) (i.e., bulk (PC1), dewaxed (PC2), nonsaponifiable (PC3), nonsaponifiable-nonhydrolyzable (PC4), and dewaxed-hydrolyzed residue (PC5)) were examined to better understand the influence of polarity and accessibility on their sorption behavior. The polarity and structures of cuticular fractions were characterized by elemental analysis, Fourier transform infrared spectroscopy, and solid-state 13C NMR. The sorption isotherms fit well to the Freundlich equation. Sorption of the tested organic compounds to PC4, which had more condensed domains, was nonlinear (Freundlich N(s) values of 0.766-0.966). For naphthalene and phenanthrene, the largest sorption capacity (K(oc)) occurred in PC5, which contained the highest paraffinic carbons (63%) and the lowest polarity: approximately 2 and aproximately 3 times higher than the respective carbon-normalized octanol-water partition coefficient (K(owc)), indicating that PC5 was a powerful sorption medium. For phenol and 1-naphthol, the largest K(oc) values occurred in PC4 with polar aromatic cores: approximattely 17 and approximately 7 times higher than the respective K(owc), suggesting that PC4 was much more accessible and compatible to polar aromatic pollutants than nonpolar aromatic pollutants. There was little or no correlation of K(oc) with either aliphatic or aromatic components of the tested aliphatic-rich sorbents because the polarity and accessibility apparently played a regulating role in the sorption of organic contaminants.     

Phenanthrene and pyrene sorption and intraparticle diffusion in polyoxymethylene, coke, and activated carbon

We report sorption isotherms and uptake kinetics for phenanthrene and pyrene with three organic model sorbents: polyoxymethylene (POM), coke, and activated carbon. We combine batch equilibration and kinetic experiments with the direct observation of the long-term diffusion of phenanthrene and pyrene as measured within cross-sectioned particles using microprobe laser-desorption laser-ionization mass spectroscopy (muL2MS). For POM pellets, the intraparticle concentration profiles predicted from kinetic batch experiments and a polymer diffusion model with spherical geometry are in agreement with the independent muL2MS measurements. For coke particles, the apparent diffusivities decreased with smaller particle size. These trends in diffusivities were described by a sorption-retarded pore diffusion model with a particle-size-dependent solid-water partitioning coefficient obtained from apparent equilibrium observed in the kinetic batch studies. For activated carbon, the muL2MS measurements showed faster radial diffusion of phenanthrene and pyrene into the particle interior than predicted from diffusion models based on a single sorption domain and diffusivity. A branched pore kinetic model, comprising polycyclic aromatic hydrocarbon (PAH) macropore diffusion with kinetic exchange of PAH between macroporous and microporous domains, fits the experimental observations better. Because of parallel macro- and microdiffusion processes, nonlinear sorption isotherms, and a concentration-dependent diffusivity, it is not possible to make independent parameter estimations for intraparticle diffusion in activated carbon using our present procedures.