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.     

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).     

Impact of de-ashing humic Acid and humin on organic matter structural properties and sorption mechanisms of phenanthrene

Organic matter-mineral interactions greatly affect the fate of hydrophobic organic compounds (HOCs) in the environment. In the present study, the impact of organic matter-mineral interaction on sorption of phenanthrene (PHE) by the original and de-ashed humic acids (HAs) and humin (HM) was examined. After de-ashing treatment, the overall polarity of organic matter in HAs and HM consistently decreased. Differently, the surface polarity of HAs increased but that of HM decreased. No correlation between K(oc) values of PHE by all tested sorbents and their bulk polarity was observed due to inaccessibility of a portion of interior sorption domains. The inaccessibility of interior sorption domains in HAs and HM was partly due to the crystalline structure in organic matter as indicated by differential scanning calorimetric (DSC) and 13C NMR data and the interference from minerals. A good correlation between surface polarity of the original and de-ashed HAs and HMs and their K(oc) values for PHE indicated its importance in HOC sorption. Dissimilar changes in surface polarity of HAs and HM after de-ashing treatment can be ascribed to the distinct interactions between organic matter and minerals. The solid-state 13C NMR, XPS, and elemental composition data of all tested sorbents revealed that a larger fraction of O atoms in HAs were involved in organic matter-mineral interaction as compared to HM. Results of this work highlight the importance of soil organic matter (SOM)-mineral interactions, surface polarity, and microscaled domain arrangement of SOM in HOC sorption.     

Sorption of four hydrophobic organic compounds by three chemically distinct polymers: role of chemical and physical composition

The sorption behavior of four hydrophobic organic contaminants (HOCs) (i.e., phenanthrene, naphthalene, lindane, and 1-naphthol) by three types of polymers namely polyethylene (PE), polystyrene (PS), and polyphenyleneoxide (PPO) was examined in this work. The organic carbon content-normalized sorption coefficients (K(oc)) of phenanthrene, lindane, and naphthalene by PEs of same composition but distinct physical makeup of domains increased with their crystallinity reduction (from 58.7 to 25.5%), suggesting that mobility and abundance of rubbery domains in polymers regulated HOC sorption. Cross-linking in styrene-divinylbenzene copolymer (PS2) created substantial surface area and porosity, thus, K(oc) values of phenanthrene, lindane, naphthalene, and 1-naphthol by PS2 were as high as 274.8, 212.3, 27.4, and 1.5 times of those by the linear polystyrene (PS1). The K(oc) values of lindane, naphthalene, and 1-naphthol by polar PPO were approximately 1-3 orders of magnitude higher than those by PS1, and PPO had comparable sorption for phenanthrene but higher sorption for naphthalene and 1-naphthol than PS2. This can be a result that a portion of O-containing moieties in PPO were masked in the interior part, while leaving the hydrophobic domains exposed outside, therefore demonstrating the great influence of the spatial arrangement of domains in polymers on HOC sorption.     

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 sorption to sequentially extracted soil humic acids and humins

Humic substances strongly influence the environmental fate of hydrophobic organic chemicals in soils and sediments. In this study, the sorption of phenanthrene by humic acids (HAs) and humins was examined. HAs were obtained from progressively extracting a soil, eight times with 0.1 M Na4P207 and two times with 0.1 M NaOH solution, and then the residue was separated into two humin fractions by their organic carbon contents. The chemical and structural heterogeneity of the HAs and humins were characterized by elemental analysis, ultraviolet-visible spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and solid-state 13C NMR. There were significant chemical and structural differences among the HA fractions and humins; the later extracted HAs had relatively high aliphatic carbons content. All sorption data were fitted to a Freundlich equation, S = K(F)C(N), where S and C are the sorbed and solution-phase concentrations, respectively, and K(F) and N are constants. All of the phenanthrene sorptions were nonlinear, and the nonlinearity decreased with further extractions from 0.90 (first extracted HA) to 0.96 (ninth HA) and was the lowest (0.88) for the higher organic carbon content humin. Phenanthrene sorption coefficient by HAs significantly increased with progressive extractions, being the highest for the humins. For HAs isotherms, a positive trend was observed between the sorption coefficient and the aliphaticity, but a negative relation was shown between the nonlinearity and the aliphaticity and between the sorption capacity and polarity of HAs. Phenanthrene sorption was greatly affected by chemical structure and composition of humic substances, even from a same soil. In addition, polarity of humic substances seems to mainly regulate the magnitude of phenanthrene sorption rather than structure.     

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.     

A concentration-dependent multi-term linear free energy relationship for sorption of organic compounds to soils based on the hexadecane dilute-solution reference state

A LFER of the type in the title is applied to sorption of numerous compounds to polyethylene and three soils for which sorption to natural organic matter (NOM) is presumed dominant. It provides fractional contributions to the Gibbs free energy of sorption corresponding to hydrophobic effects, dipolar/polarizability (D/P) effects in excess of the reference state, and the sum of possible specific forces such as H-bonding and pi-pi electron donor-acceptor (pi-pi EDA) interactions in excess of the reference state. Minimal inputs are the isotherm, the n-hexadecane-water partition coefficient and the Abraham pi parameter representing D/P effects. Sorption of all compounds to polyethylene can be described by considering only hydrophobic effects. Sorption of a calibration set of apolar compounds (aromatic and aliphatic hydrocarbons and chlorinated hydrocarbons) to the natural sorbents is well-described by a combination of hydrophobic and D/P effects. For the apolar set, D/P contributes approximately 15-40% (2-8% for cyclohexane) of sorption free energy. D/P effects increase with the degree of chlorination for aliphatic compounds. For aromatic compounds D/P effects increase with fused ring size but do not vary with degree of chlorination and chlorine substitution pattern. H-bonding contributes substantially to sorption of alcohols, and similarly for 2-nonanol and 2,4-dichlorophenol (33-44%). pi-pi EDA forces contribute to phenanthrene sorption in one case. The effects of concentration, sorbent aromaticity (literature NMR), and sorbent polarity [(O + N)/C] on hydrophobic and D/P contributions for all compounds indicate that (a) molecules fill sites of progressively greater hydrophilic character; (b) the energy penalty for cavity formation in the solid decreases with concentration due to plasticization and greater intermolecular contact; (c) sorbent aromatic content more than sorbent polarity controls D/P interactions. Basing free energy on an inert electrostatic chemical environment afforded by n-hexadecane permits evaluation of direct electrostatic forces in NOM that contribute to sorption.     

Hydration of natural organic matter: effect on sorption of organic compounds by humin and humic acid fractions vs original peat material

Natural organic matter (NOM) hydration is found to change activity-based sorption of test organic compounds by as much as 2-3 orders of magnitude, depending on the compound and the specific NOM sorbent. This is demonstrated for sorption on humin, humic acid, and the NOM source material. Hydration assistance in organic compound sorption correlates with the ability of the sorbate to interact strongly with hydrated sorbents, demonstrating the important role of noncovalent polar links in organizing the sorbent structure. Differences in hydration effect between the sorbents are caused mainly by differences in compound-sorbent interactions in the dry state. For a given compound, hydration of the sorbent tends to equalize the sorption capability of the three sorbents. No correlation was found between the strength of sorbate-sorbent interactions or the type of sorbate functional groups and the extent of sorption nonlinearity. Sorption nonlinearity compared over the same sorbed concentration range is greater on the original NOM than on either of the two extracted fractions. In elucidating sorption mechanisms on hydrated NOM, it is important to explicitly consider the participation of water molecules in organic compound interactions in the NOM phase.     

Sorption equilibrium of a wide spectrum of organic vapors in Leonardite humic acid: experimental setup and experimental data

The environmental fate of volatile and semivolatile organic compounds is determined by their partitioning between air and soil constituents, in particular soil organic matter (SOM). While there are many studies on the partitioning of nonpolar compounds between water and SOM, data on sorption of polar compounds and data for sorption from the gas phase are rather limited. In this study, Leonardite humic acid/air partition coefficients for 188 polar and nonpolar organic compounds at temperatures between 5 and 75 degrees C and relative humidities between < 0.01% and 98% have been determined using a dynamic flow-through technique. To the best of our knowledge, this is by far the largest and most diverse and consistent data set for sorption into humic material published so far. The major results are as follows: the relative humidity affected the experimental partition coefficients by up to a factor of 3; polar compounds generally sorbed more strongly than nonpolar compounds due to H-bonding (electron donor/ acceptor interactions) with the humic acid; no glass transitions in the range of 5-75 degrees C that would be relevant with respect to the sorption behavior of hydrated Leonardite humic acid were observed; our experimental data agree well with experimental partition coefficients from various literature sources.     

Influence of surface oxidation of multiwalled carbon nanotubes on the adsorption affinity and capacity of polar and nonpolar organic compounds in aqueous phase

Adsorption of organic contaminants on carbon nanotubes (CNTs) is a critical behavior in the environmental application of CNTs as sorbents and in the environmental risk assessment of both organic contaminants and CNTs. Oxidation of CNTs may introduce oxygen-containing groups on CNTs' surface and then alter the adsorption of organic contaminants. In this study, adsorption of polar and nonpolar organic compounds on four multiwalled carbon nanotubes (MWCNTs) containing varied amounts of surface oxygen-containing groups were investigated to examine the influence of CNTs' surface oxidation on adsorption. We observed that surface oxidation of MWCNTs reduced the surface area-normalized adsorption capacity of organic compounds significantly because of the competition of water molecules but did not alter the adsorption affinity. The interactions (i.e., hydrophobic effect, π-π bonds, and hydrogen bonds) and the interaction strength for adsorption of organic molecules on MWCNTs could not be altered by the surface oxidation of MWCNTs and thus were responsible for the unaltered adsorption affinity. In addition, the decrease of surface area-normalized adsorption capacity of the organic compound with more polarity and higher adsorption affinity by surface oxidation was less because of the heterogeneous nature of hydrophilic sites of MWCNTs' surface.     

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.     

Sorption of aromatic organic contaminants by biopolymers: effects of pH, copper (II) complexation, and cellulose coating

Sorption of hydrophobic organic compounds (HOCs) (i.e., pyrene, phenanthrene, naphthalene, and 1-naphthol) by original and coated biopolymers was examined. Lignin yielded nonlinear isotherms due to its glassy character. Except for pyrene, cellulose showed linear isotherms for other compounds, indicating a partitioning dominant mechanism. Sorption of 1-naphthol by lignin decreased with increasing pH, attributed to both the increased pi e theta-pi e theta repulsion and weakened hydrogen bonds, while the affinity reduction of cellulose for 1-naphthol with increasing pH resulted from only the decrease in H-bonding due to its absence of benzene ring. Complexation of lignin with Cu2+ increased the sorption affinity for phenanthrene (2.6 times) and slightly enhanced its isotherm nonlinearity. For 1-naphthol, lignin-Cu2+ complex had a much higher sorption capacity (7 times)than the original lignin, accompanied bythe increased isotherm nonlinearity. Cellulose-coated lignin showed increased sorption affinity and more pronounced nonlinearity for 1-naphthol than the lignin-Cu2+ complex. In comparison, cellulose coating exhibited little effect on sorption affinity for phenanthrene relative to the lignin-Cu2+ complex. Isotherm nonlinearity of coated lignins increased with increasing cellulose coating, indicating more condensed domains produced, supported by an increase (from 68.9 degrees C for the original lignin to 82.4 degrees C for the highest cellulose coating level) in glass transition temperature (Tg). Results of this study highlightthe importance of structure, polarity, surface O-containing functional groups, and surface charges of biopolymers in controlling HOC sorption.     

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.     

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.     

Sorption of the veterinary antimicrobial sulfathiazole to organic materials of different origin

Sulfonamides (SA), ionizable, polar antimicrobial compounds, may reach the environment in substantial amounts by the spreading of manure. The environmental behavior of SA is still difficult to predict. We investigated the influence of the main factors supposed to control SA sorption to organic materials: composition of sorbent, solute chemistry, and contact time. For that purpose, sulfathiazole (STA) sorption to compost, manure, and humic acid after 1 and 14 d was studied under sterile conditions. The experiments demonstrated that sorption was most strongly affected by contact time and pH. Irrespective of sorbent and pH, sorption continued substantially after the fast initial sorption within 1 d. For all sorbents and both contact times, STA sorption exhibited a pronounced pH dependence. Species-specific Koc values decreased in the order KoccatiOn> Kocneutral > Kocanion. Differences in sorbent composition influenced STA sorption weaker. Forthe neutral STA species, NMR chemical shift regions assignable to ketonic, carboxylic, and phenolic C as well as aromatic C-H and methoxyl/N-alkyl C seemed to control sorption. Forthe cations, sorption followed the cation exchange capacities of the sorbents. STA sorption to manure and humic acid increased with higher ionic strength (0.31 M compared to 0.06 M) at pH 7.5.     

Kinetics of desorption of organic compounds from dissolved organic matter

This study presents a new experimental technique for measuring rates of desorption of organic compounds from dissolved organic matter (DOM) such as humic substances. The method is based on a fast solid-phase extraction of the freely dissolved fraction of a solute when the solution is flushed through a polymer-coated capillary. The extraction interferes with the solute-DOM sorption equilibrium and drives the desorption process. Solutes which remain sorbed to DOM pass through the extraction capillary and can be analyzed afterward. This technique allows a time resolution for the desorption kinetics from subseconds up to minutes. It is applicable to the study of interaction kinetics between a wide variety of hydrophobic solutes and polyelectrolytes. Due to its simplicity it is accessible for many environmental laboratories. The time-resolved in-tube solid-phase microextraction (TR-IT-SPME) was applied to two humic acids and a surfactant as sorbents together with pyrene, phenanthrene and 1,2-dimethylcyclohexane as solutes. The results give evidence for a two-phase desorption kinetics: a fast desorption step with a half-life of less than 1 s and a slow desorption step with a half-life of more than 1 min. For aliphatic solutes, the fast-desorbing fraction largely dominates, whereas for polycyclic aromatic hydrocarbons such as pyrene, the slowly desorbing, stronger-bound fraction is also important.     

Adsorption of single-ring organic compounds to wood charcoals prepared under different thermochemical conditions

Environmental black carbon (BC) is believed to be an important adsorbent of organic pollutants. In this study, we examined the effects of changes in surface properties and adsorbate structure. A series of apolar compounds (cyclohexane, 1,2-dichlorobenzene, 1,4-xylene, 1,2,3,5-tetramethylbenzene, 1,3,5-triethylbenzene) and a series of polar compounds (o-cresol, 4-nitrotoluene, 2,4-dinitrotoluene, and 2,4,6-trinitrotoluene) were sorbed from aqueous solution to maple wood char prepared under five thermochemical conditions. Two chars were prepared in air at 340 degrees C (C340) and 400 degrees C (C400). A subsample of C400 was treated with H2 in the presence of a supported Pt catalyst at 500 degrees C (C400-H) to remove surface O. Another was treated under N2 at 500 degrees C (C400-N) to serve as a control for C400-H. The reduced C400-H was further oxidized in air at 340 degrees C to reintroduce O (C400-H-A). The five chars vary in O content (26.1, 22.3, 4.2, 20.8, and 18.6 wt %, respectively) but show only minor differences in surface area and pore size distribution on the basis of N2 and CO2 adsorption analysis. These chars provide a basis for rationalizing sorption intensity as a function of sorbate molecular structure and surface chemistry. The following conclusions were drawn. (1) Polar interactions with surface O functional groups are not a significant driving force for adsorption. (2) When isotherms are adjusted for solute hydrophobicity (n-hexdecane-water partition coefficient), sorption intensity of the polar compounds is greater than that of the apolar compounds, possibly because of pi-pi EDA interactions of the polar compounds with the basal plane of the graphene sheets. (3) The largest test compounds show steric exclusion from a portion of the adsorption space available to the other compounds. (4) Removal of O functionality by hydrogenation enhances sorption intensity of polar and apolar compounds, alike by reducing competitive adsorption by water molecules.     

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.