Measuring hydrophobic micropore volumes in geosorbents from trichloroethylene desorption data

Hydrophobic micropores can play a significant role in controlling the long-term release of organic contaminants from geosorbents. We describe a technique for quantifying the total and the hydrophobic mineral micropore volumes based on the mass of trichloroethylene (TCE) sorbed in the slow-releasing pores under dry and wet conditions, respectively. Micropore desorption models were used to differentiate the fast- and slow-desorbing fractions in desorption profiles. The micropore environment in which organic molecules were sorbed in the presence of water was probed by studying the transformation of a water-reactive compound (2,2-dichloropropane or 2,2-DCP). For sediment from an alluvial aquifer, the total and hydrophobic micropore volumes estimated using this technique were 4.65 microL/g and 0.027 microL/g (0.58% of total), respectively. In microporous silica gel A, a hydrophobic micropore volume of 0.038 microL/g (0.035% of reported total) was measured. The dehydrohalogenation rate of 2,2-DCP sorbed in hydrophobic micropores of the sediment was slower than that reported in bulk water, indicating an environment of low water activity. The results suggest that hydrolyzable organic contaminants sorbed in hydrophobic micropores react slower than in bulk water, consistent with the reported persistence of reactive contaminants in natural soils.     

Sorption and inhibited dehydrohalogenation of 2,2-dichloropropane in micropores of dealuminated Y zeolites

Contaminant transformation rates in the subsurface can be slowed by sorption onto geosorbents. We evaluated the effect of micropore sorption on contaminant transformation in a model system consisting of dealuminated Y zeolites and 2,2-dichloropropane (2,2-DCP). 2,2-DCP dehydrochlorinates in water to 2-chloropropene (2-CP) at a rate of 2.93 x 10(-4) min(-1) at 24 degrees C. The Y zeolites used range from hydrophilic (CBV-300) to hydrophobic (CBV-720 and CBV-780). Wet zeolite samples were loaded with 2,2-DCP at 24 degrees C and reacted at 50 degrees C for 10 h. Results show that the hydrophobic zeolites (CBV-720 and CBV-780) sorbed nearly 900 times more 2,2-DCP than the hydrophilic CBV-300 under wet conditions. 2,2-DCP transformed less when sorbed in micropores of CBV-720 (6.3%) and CBV-780 (5.0%) than in micropores of CBV-300 (81.5%), and significantly less than in water (> 99.85%). Inhibition in hydrophobic micropores is interpreted as lack of water solvating the transition state of 2,2-DCP dehydrohalogenation and the H+ and Cl- formed. Near the micropore openings, the transformation was relatively fast, consistent with greater abundance of water associated with the hydrophilic edge sites. These results indicate that in the subsurface the half-lives of reactive organic contaminants may be longer than predicted from bulk water data.     

Evaluating competitive sorption mechanisms of volatile organic compounds in soils and sediments using polymers and zeolites

The competitive sorption of trichloroethene (TCE) and tetrachloroethene (PCE) was investigated in three natural solids, two polymers, and four zeolites. Competition was observed in natural solids with high contents of recalcitrant organic carbon, in the glassy polymer, and in zeolites with strongly and moderately hydrophobic micropores of large (7.5 x 10 A) and small pore widths (approximately 5.4 A), respectively. Isotherm results and recalcitrant OC% values for natural solids indicate that the extent of competition between TCE and PCE is related to the amount of hard organic carbon. Gas adsorption results and the variability in C/H values suggest that natural organic matter contains micropores with varying width and polarity. Isotherm results for zeolites indicate that competition between TCE and PCE increases with increasing hydrophobicity and decreasing micropore width. We suggest that competition between volatile organic contaminants in the subsurface is controlled by competition for hydrophobic micropores in hard organic matter and that smaller more hydrophobic micropores result in stronger competition.     

Slow desorption mechanisms of volatile organic chemical mixtures in soil and sediment micropores

Desorption profiles of trichloroethylene (TCE), tetrachloroethylene (PCE), and a TCE-PCE mixture were measured for three natural solids and four zeolites. Initial sorbed mass (Mi) in slow desorbing sites of natural solids and in micropores of zeolites were obtained from desorption profiles. In natural solids, Mi increases with recalcitrant organic matter content. In zeolites, Mi generally increases with decreasing micropore width and increasing micropore hydrophobicity, but the effect of hydrophobicity is stronger. In both natural solids and zeolites, competition between TCE and PCE causes Mi for each sorbate in the mixture to be less than or similar to that for each sorbate alone. Zeolite results indicate that micropore width affects this competition more than micropore hydrophobicity for the solids examined. Desorption in all solids was simulated with the radial diffusion model, either alone or coupled with the advection-dispersion equation when necessary; diffusion rate constants (D/R2) were obtained. In natural solids, mean values of D/R2 increase with decreasing recalcitrant organic matter content. In zeolites, values of D/R2 generally increase with increasing micropore width, while they are a weak function of hydrophobicity. In both natural solids and zeolites, competition between TCE and PCE causes D/R2 for each sorbate in the mixture to generally be larger than that for each sorbate alone. Zeolite results indicate that the effects of competition on D/R2 generally decrease with decreasing micropore width for the solids examined; a trend with micropore hydrophobicity is not apparent. For the three natural solids and four zeolites examined in this study, the similar effects of competition between TCE and PCE on values of Mi and D/R2 and the overlapping range of D/R2 values support the hypothesis that diffusion through hydrophobic micropores affects and may control slow mass transfer processes in the recalcitrant organic matter of natural solids. These results contribute to the fundamental understanding of slow mass transfer processes in natural solids, and they indicate that characterization of micropore width and polarity may be necessary to predict organic chemical transport and fate.     

Engineered polymeric nanoparticles for bioremediation of hydrophobic contaminants

Sorption of hydrophobic organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), to soil has been shown to limit their solubilization rate and mobility. In addition, sequestration of contaminants by sorption to soil and by partitioning in nonaqueous phase liquids (NAPLs) reduces their bioavailability. Polymeric nano-network particles have been demonstrated to increase the "effective" solubility of a representative hydrophobic organic contaminant, phenanthrene (PHEN) and to enhance the release of PHEN from contaminated aquifer material. In this study, we investigate the usefulness of nanoparticles made from a poly(ethylene) glycol modified urethane acrylate (PMUA) precursor chain, in enhancing the bioavailability of PHEN. PMUA nanoparticles are shown to increase the mineralization rate of PHEN crystal in water, PHEN sorbed on aquifer material, and PHEN dissolved in a model NAPL (hexadecane) in the presence of aquifer media. These results show that PMUA particles not only enhance the release of sorbed and NAPL-sequestered PHEN but also increase its mineralization rate. The accessibility of contaminants in PMUA particles to bacteria also suggests that particle application may be an effective means to enhance the in-situ biodegradation rate in remediation through natural attenuation of contaminants. In pump-and-treat or soil washing remediation schemes, bioreactors could be used to recycle extracted nanoparticles. The properties of PMUA nanoparticles are shown to be stable in the presence of a heterogeneous active bacterial population, enabling them to be reused after PHEN bound to the particles has been degraded by bacteria.     

Sorption of trichloroethylene in hydrophobic micropores of dealuminated Y zeolites and natural minerals

Sorption of volatile organic compounds (VOCs) in low organic carbon (<0.1%) geosorbents is difficult to predict because the sorption capacity of the mineral matrix is poorly understood. This research demonstrates hydrophobic micropores can be important sorption sites for VOCs. We studied the sorption of water and TCE on three dealuminated Y zeolites ranging from hydrophilic (CBV-300) to hydrophobic (CBV-720 and CBV-780), with the surface cation density decreasing from 2.07 to 0.42 and 0.16 sites/ nm2, respectively. Water sorption and dehydration data indicate water affinity of the zeolite micropores decreases with micropore hydrophobicity. TCE sorption on the wet zeolites decreased with increasing surface cation density. At a relative pressure (P/P0) of 0.136, TCE filled only 0.034% of the micropore volume in wet CBV-300, but 16.9% and 18.6% in wet CBV-720 and CBV-780, respectively. TCE desorption data from dry and wet silica sand (Min-U-Sil 30), kaolinite (KGa-1), and smectite (SWy-1) confirmed VOC sorption in wet microporous minerals is controlled by both the micropore volume and hydrophobicity. Results suggestTCE adsorbs in hydrophobic micropores by displacing loosely bound water, consistent with the theoretical considerations indicating the process of transferring loosely bound water from hydrophobic micropores to the bulk phase is energetically favorable.     

Microwave-induced degradation of atrazine sorbed in mineral micropores

The herbicide atrazine is a common pollutant in reservoirs and other sources of drinking water worldwide. The adsorption of atrazine from water onto zeolites CBV-720 and 4A, mesoporous silica MCM-41, quartz sand, and diatomite, and its microwave-induced degradation when sorbed on these minerals, were studied. Dealuminated HY zeolite CBV-720 exhibited the highest atrazine sorption capacity among the mineral sorbents because of its high micropore volume, suitable pore sizes, and surface hydrophobicity. Atrazine sorbed on the minerals degraded under microwave irradiation due to interfacial selective heating by the microwave, while atrazine in aqueous solution and associated with PTFE powder was not affected. Atrazine degraded rapidly in the micropores of CBV-720 under microwave irradiation and its degradation intermediates also decomposed with further irradiation, suggesting atrazine could be fully mineralized. Two new degradation intermediates of atrazine, 3,5-diamino-1,2,4-triazole and guanidine, were first identified in this study. The evolution of degradation intermediates and changes in infrared spectra of CBV-720 after microwave irradiation consistently indicate the creation of microscale hot spots in the micropores and the degradation of atrazine following a pyrolysis mechanism. These results indicate that microporous mineral sorption coupled with microwave-induced degradation could serve as an efficient treatment technology for removing atrazine from drinking water.     

Effects of linear alkylbenzene sulfonate on the sorption of Brij 30 and Brij 35 onto aquifer sand

Surfactant sorption is of considerable importance to environmental applications, including surfactant flushing to mobilize hydrophobic contaminants; effects of surfactants on the transport of dissolved contaminants, microorganisms, and colloids through porous media; and bioremediation of hydrophobic organic compounds, as well as understanding the fate and transport of surfactants as environmental contaminants themselves. Although most sorption studies consider pure surfactants, commercial detergent formulations typically consist of mixtures of nonionic and anionic surfactants. In this study, the effects of varying concentrations of the anionic surfactant linear alkylbenzene sulfonate (LAS) on micelle formation and sorption behavior of the two commonly used nonionic surfactants Brij 30 and Brij 35 onto aquifer sand were examined. A strong linear relationship was observed between the critical micelle concentration (CMC) of the Brij surfactants and the concentration of LAS in the mixture, with the CMC decreasing with increasing concentration of LAS. The relative change in CMC as a function of the LAS concentration was identical forthe two Brij surfactants, indicating that LAS interacted with their common alkyl chains. Sorption isotherms were developed for Brij 30 and Brij 35 present as single surfactants in an aqueous solution as well as when present with LAS. Although LAS had minor effects on the maximum sorption plateaus of the Brij surfactants, Brij sorption at was significantly enhanced as a function of the LAS concentration for Brij aqueous concentrations below the CMC. Application of a multi-interaction isotherm model indicated that the formation of surface aggregates (e.g., hemimicelles) decreased with increasing LAS concentration. Overall, these results provide insight into the complex sorption behavior of surfactant mixtures.     

Pore-scale redistribution of water during wetting of air-dried soils as studied by low-field NMR relaxometry

The kinetics of water uptake and redistribution in several soils and their components are studied using NMR relaxometry. Unlike the normal behavior observed in stable porous media, entry into micropores in the soil is a slow process as compared to entry into macro- and mesopores. This indicates that soils air-dried at ambient temperature include gel phases that have collapsed or reoriented, closing micropores, during drying. Wetting must then include the swelling processes that re-open micropores. This can even exhibit temperature dependence giving an "apparent activation energy" comparable to that of a chemical reaction, for example, ester hydrolysis. The processes of micropore opening may play a role in slow uptake of contaminants into soils.     

Influence of dissolved organic matter and Fe(II) on the abiotic reduction of pentachloronitrobenzene

Nitroaromatic pesticides (NAPs) are hydrophobic contaminants that can accumulate in sediments by the deposition of suspended solids from surface waters. Fe(II) and dissolved organic matter (DOM), present in suboxic and anoxic zones of freshwater sediments, can transform NAPs in natural systems. We studied the reduction of pentachloronitrobenzene (PCNB) to pentachloroaniline (PCA) in controlled studies using Fe(II) and surface water DOM isolates from Pony Lake, Antarctica, and Suwannee River, GA, in unfiltered and 0.45 microm filtered solutions. We observed rapid reduction of PCNB to PCA in the presence of Fe(II) and DOM (t(1/2) approximately = 30 min to 4 h) and very limited reduction in DOM-only systems. DOM in unfiltered systems inhibited iron colloid formation and potentially limited the formation of reactive Fe(ll)-iron colloid surface complexes, causing reductive transformation in Fe(II)-DOM media to be slower in some cases relative to Fe(ll)-only controls. Conversely, in 0.45 microm filtered solutions, PCNB reduction in Fe(III)-DOM media was faster than the Fe(II)-only controls, suggesting that DOM enhances the reductive capacity of Fe(ll) in the absence of iron colloids. This work shows that DOM may significantly affect the reactivity of Fe(ll) toward NAPs under suboxic and anoxic conditions in natural wetland sediments.     

Interactions of organic contaminants with mineral-adsorbed surfactants

Sorption of organic contaminants (phenol, p-nitrophenol, and naphthalene) to natural solids (soils and bentonite) with and without myristylpyridinium bromide (MPB) cationic surfactant was studied to provide novel insightto interactions of contaminants with the mineral-adsorbed surfactant. Contaminant sorption coefficients with mineral-adsorbed surfactants, Kss, show a strong dependence on surfactant loading in the solid. At low surfactant levels, the Kss values increased with increasing sorbed surfactant mass, reached a maximum, and then decreased with increasing surfactant loading. The Kss values for contaminants were always higher than respective partition coefficients with surfactant micelles (Kmc) and natural organic matter (Koc). At examined MPB concentrations in water the three organic contaminants showed little solubility enhancement by MPB. At low sorbed-surfactant levels, the resulting mineral-adsorbed surfactant via the cation-exchange process appears to form a thin organic film, which effectively "adsorbs" the contaminants, resulting in very high Kss values. At high surfactant levels, the sorbed surfactant on minerals appears to form a bulklike medium that behaves essentially as a partition phase (rather than an adsorptive surface), with the resulting Kss being significantly decreased and less dependent on the MPB loading. The results provide a reference to the use of surfactants for remediation of contaminated soils/sediments or groundwater in engineered surfactant-enhanced washing.     

Trichloroethylene adsorption by fibrous and granular activated carbons: aqueous phase, gas phase, and water vapor adsorption studies

The important adsorption components involved in the removal of trichloroethylene (TCE) by fibrous and granular activated carbons from aqueous solutions were systematically examined. Namely, adsorption of TCE itself (i.e., TCE vapor isotherms), water molecules (i.e., water vapor isotherms), and TCE in water (i.e., TCE aqueous phase isotherms) were studied, side-by-side, using 20 well-characterized surface-modified activated carbons. The results showed that TCE molecular size and geometry, activated carbon surface hydrophilicity, pore volume, and pore size distribution in micropores control adsorption of TCE at relatively dilute aqueous solutions. TCE adsorption increased as the carbon surface hydrophilicity decreased and the pore volume in micropores of less than 10 A, especially in the 5-8 A range, increased. TCE molecules appeared to access deep regions of carbon micropores due to their flat geometry. The results indicated that characteristics of both adsorbate (i.e., the molecular structure, size, and geometry) and activated carbon (surface hydrophilicity, pore volume, and pore size distribution of micropores) control adsorption of synthetic organic compounds from water and wastewaters. The important micropore size region for a target compound adsorption depends on its size and geometry.     

Experimental and molecular mechanics and ab initio investigation of activated adsorption and desorption of trichloroethylene in mineral micropores

This research investigated activated adsorption of a hydrophobic organic contaminant(HOC) in mineral micropores using experimental and molecular modeling techniques. Adsorption of trichloroethylene (TCE) on a silica gel adsorbent was measured using a frontal analysis chromatography technique at atmospheric and elevated fluid pressures. Increasing the fluid pressure yielded increased TCE uptake that was not released upon lowering the pressure back to atmospheric conditions. This showed that the increase in pressure was able to rapidly induce the formation of a desorption-resistant fraction that previous investigations have shown requires months to develop at atmospheric pressure. Grand Canonical Monte Carlo (GCMC) modeling was then used to elucidate the nature of water and TCE behavior within silica micropores. The GCMC modeling showed that molecular scale packing restrictions resulted in pore fluid densities that ranged from 0.28 to 0.78 of those in the bulk solution. The modeling also showed that TCE was able to displace water from hydrophilic mineral pores due to molecular scale packing restrictions. Exothermic isosteric heats for TCE adsorption up to -27 kJ/mol were observed and were greatest in pores of 7 and 8 A. This indicated that TCE adsorption was energetically most favorable in pores that were minimally large enough to accommodate a TCE molecule. The pressure-induced uptake appeared to result primarily from an increase in the packing density in the smallest pores. Ab initio calculations showed that small distortions of a TCE molecule from its low energy conformation require high activation energies. Results from this study indicate that activated adsorption requiring bond angle distortions in the adsorbate may be responsible forthe slow attainment of adsorptive equilibrium of HOCs on microporous solids. Likewise, activated desorption from molecular-sized adsorption sites may contribute to the slow release of HOCs from aquifer sediments.     

Activity of Desulfitobacterium sp. strain Viet1 demonstrates bioavailability of 2,4-dichlorophenol previously sequestered by the aquatic plant Lemna minor

Aquatic plants take up and sequester organic contaminants such as chlorophenols through incorporation in cell wall materials and storage in vacuoles. The ultimate fate of plant-sequestered chlorophenols, however, remains unclear. This research investigated 2,4-dichlorophenol (2,4-DCP) sequestration by the aquatic plant Lemna minor and evaluated contaminant release and bioavailability after plant death and cellular disruption. 14C-labeled 2,4-DCP was used to establish that contaminant removed from the aqueous phase was retained internal to L. minor. An assay with Desulfitobacterium sp. strain Viet1 was used to assess the readily bioavailable fraction of plant-sequestered 2,4-DCP and plant metabolites of 2,4-DCP. In plant-free systems, strain Viet1 dechlorinated 2,4-DCP to stoichiometric amounts of 4-chlorophenol (4-CP) as a stable and quantifiable end product. Anaerobic microcosms containing inactivated L. minor, which had accumulated 3.8 micromol of 2,4-DCP equivalents/g of plant material (fresh weight) during a preceding aerobic exposure, were inoculated with strain Viet1. After 118 d of incubation with strain Viet1, 43.5% (+/-1.4%) of the contaminant was recovered as 4-CP, indicating a large portion of plant-sequestered 2,4-DCP was bioavailable for dechlorination by strain Viet1. In contrast, 4-CP formation was not observed in autoclaved microcosms, and only 26.1% (+/-1.0%) of plant-sequestered 2,4-DCP was recovered in the aqueous phase. These findings demonstrate contaminant cycling between plants and microorganisms, and emphasize that understanding the mechanisms and pathways of contaminant sequestration by plants is critical for predicting long-term contaminant fate.     

Potential for plastics to transport hydrophobic contaminants

Plastic debris litters marine and terrestrial habitats worldwide. It is ingested by numerous species of animals, causing deleterious physical effects. High concentrations of hydrophobic organic contaminants have also been measured on plastic debris collected from the environment, but the fate of these contaminants is poorly understood. Here, we examine the uptake and subsequent release of phenanthrene by three plastics. Equilibrium distribution coefficients for sorption of phenanthrene from seawater onto the plastics varied by more than an order of magnitude (polyethylene > polypropylene > polyvinyl chloride (PVC)). In all cases, sorption to plastics greatly exceeded sorption to two natural sediments. Desorption rates of phenanthrene from the plastics or sediments back into solution spanned several orders of magnitude. As expected, desorption occurred more rapidly from the sediments than from the plastics. Using the equilibrium partitioning method, the effects of adding very small quantities of plastic with sorbed phenanthrene to sediment inhabited by the lugworm (Arenicola marina) were evaluated. We estimate that the addition of as little as 1 microg of contaminated polyethylene to a gram of sediment would give a significant increase in phenanthrene accumulation by A. marina. Thus, plastics may be important agents in the transport of hydrophobic contaminants to sediment-dwelling organisms.     

Photosensitized oxidation of substituted phenols on aluminum phthalocyanine-intercalated organoclay

Bentonite modified with cationic surfactant, cetyltri-methylammonium bromide (CTMA), was an effective sorbent for organic pollutants in water. To make the sorbent recyclable, aluminum phthalocyanine (AIPc), a representative photosensitizer for generation of singlet oxygen, was inserted successfully into the interlamellar space of CTMA-modified bentonite. Under visible light (lambda > 450 nm) irradiation, the composite catalyst exhibited a remarkable activity for degradation of the recalcitrant pollutants phenol, 4-chlorophenol, 4-nitrophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol in an aerated aqueous medium. The initial rate of the heterogeneous photoreaction was found to increase with the initial amount of the substrate sorption onto the catalyst, the kinetics following the Langmuir-Hinshelwood equation. Loading of AIPc into the organoclay led to slight expansion of the clay basal spacings from 1.82 to 2.15 nm, but the sorption capacity was decreased notably. The optimal loading of AIPc was about 0.25 wt %. The result demonstrates thatthe surfactant-modified bentonite not only offers a hydrophobic zone for enrichment of organic contaminants but also provides a flexible environment for destruction of the sorbed pollutants by singlet oxygen generated in situ. It was noted, however, that during four repeated experiments, both the sorption and the degradation rate of 2,4,6-trichlorophenol were gradually decreased, due to some intermediates formed and sorbed onto the catalyst surface.     

Distribution and reactivity of O2-reducing components in sediments from a layered aquifer

The redox status of subsurface aqueous systems is controlled by the reactivity of solid redox-sensitive species and by the inflow of such species dissolved in groundwater. The reactivity toward molecular oxygen (O2) of solid reductants present in three particle size fractions of sediments from a pristine aquifer was characterized during 54 days. The stoichiometric relationships between carbon dioxide (CO2) production and O2 consumption was used in combination with sulfate production to discriminate between the contributions of sedimentary organic matter (0-87%), pyrite (6-100%), and siderite (0-43%) as the dominant reductants. The observed simultaneous oxidation of these reductants indicates that they are reactive on the same time scales. The measured reduction capacity 18-84 micromol O2/g) ranged from 8 to 42% of the total reduction capacity present as pyrite and organic carbon in the total sediment fraction (<2 mm). Fine fractions (<63 microm) were 10-250 times more reactive than their corresponding total fractions. Oxygen consumption rates decreased continuously during carbonate buffered conditions, due to a decreasing reactivity of reductants. Acidification accelerated pyrite oxidation but impeded SOM respiration. Our findings indicate that the geological history of aquifer sediments affects the amounts of organic matter, pyrite and siderite present, while environmental conditions, such as pH and microbial activity, are important in controlling the reactivity of these reductants. These controls should be considered when assessing the natural reduction activity of aquifer sediments in either natural or polluted systems.     

Enhanced sorption of trichloroethene by smectite clay exchanged with Cs+

Trichloroethene (TCE) is one of the most common pollutants in groundwater, and Cs+ can be a cocontaminant at nuclear facilities. Smectite clays have large surface areas, are common in soils, have high affinities for some organic contaminants, and hence can potentially influence the transport of organic pollutants entering soils and sediments. The exchangeable cations present near smectite clay surfaces can radically influence the sorption of organic pollutants by soil clays. This research was undertaken to determine the effect of Cs+, and other common interlayer cations, such as K+ and Ca2+, on the sorption of TCE by a reference smectite clay saponite. Cs-saturated clay sorbed the most TCE, up to 3500 mg/kg, while Ca-saturated smectite sorbed the least. We hypothesize that the stronger sorption of TCE by the Cs-smectite can be attributed to the lower hydration energy and hence smaller hydrated radius of Cs+, which expands the lateral clay surface domains available for sorption. Also, Cs-smectite interlayers are only one or two water layers thick, which may drive capillary condensation of TCE. Our results implicate enhanced retention of TCE in aquifer materials containing smectites accompanied by Cs+ cocontamination.     

Mechanistic characterization of adsorption and slow desorption of phenanthrene aged in soils

Long-term adsorption of phenanthrene to soils was characterized in a silt-loam (LHS), a sandy soil (SBS), and a podzolized soil (CNS) by use of the Polanyi-Manes model, a Langmuir-type model, and a black carbon-water distribution coefficient (K(BC)) at a relative aqueous concentration (C(e)/S(w)) of 0.002-0.32. Aqueous desorption kinetic tests and temperature-programmed desorption (TPD) were also used to evaluate phenanthrene diffusivities and desorption activation energies. Adsorption contribution in soils was 48-70% after 30 days and 64-95% after 270 days. Significant increases in adsorption capacity with aging suggest that accessibility of phenanthrene to fractions of SBS soil matrix was controlled by sorptive diffusion at narrow meso- and micropore constrictions. Similar trends were not significant for LHS silt-loam or CNS podzol. Analysis of TPD profiles reveal desorption activation energies of 35-53 kJ/mol and diffusivities of 1.6 x 10(-7-)9.7 x 10(-8) cm2/s. TPD tests also indicate that the fraction of phenanthrene mass not diffusing from soils was located within micropores and narrow width mesopores with a corresponding volume of 1.83 x 10(-5-)6.37 x 10(-5) cm3/g. These values were consistent with the modeled adsorption contributions, thus demonstrating the need for such complimentary analytical approach in the risk assessment of organic contaminants.     

Effects of competitor and natural organic matter characteristics on the equilibrium sorption of 1,2-dichlorobenzene in soil and shale

The competitive sorption behaviors of 1,2-DCB in binary solute systems in four natural sorbents having natural organic matter (NOM) matrixes of different physicochemical characters were investigated in batch reactors. Specifically, the study focused on investigating how the extent of 1,2-DCB competitive sorption depends on (i) the rigidity of NOM matrixes as assessed by the efficiency of chemical oxidation and (ii) the closeness of competitor structure to that of the primary solute. The chemical oxidation and elemental composition results suggest that the shale NOM is the most reduced and condensed, the peat was the most oxidized and amorphous, and two surface soils had intermediate NOM structures. Four chlorinated benzenes and phenanthrene were used as competing solutes. All five chemicals exhibited competition against 1,2-DCB in all sorbents, including the peat, but the extent of competition varied significantly. Little difference in the extent of competition with 1,2-DCB was observed for the various chlorinated benzenes even though some were liquids and some were solids at the experimental temperature. All of the chlorobenzenes were more effective competitors than phenanthrene. The shale showed markedly different competition features from the other sorbents, with a much smaller competitive effect at a given sorbed volume of competitor. However, normalizing sorbed competitor volumes by the capacity of the adsorption domain in the Polanyi-Manes single-solute partition-adsorption model (V0) produced qualitatively similar competitive behavior for each solute; displacement of 1,2-DCB increased with increasing sorbed competitor volumes up to V0, and little additional competition occurred beyond that point. The extent of competition was positively correlated with the maximum adsorption capacity and the fraction of "hard" and "soot" carbon contents as assessed by chemical and thermal oxidation methods. These findings indicate that competition is associated with voids in the NOM structure, that these voids are likely present within the condensed ("hard" plus "soot") carbon domain, and therefore that diagenetic alteration of NOM plays a central role in determining competitive sorption characteristics for hydrophobic contaminants.