Black carbon and kerogen in soils and sediments. 1. Quantification and characterization

A comprehensive wet chemical procedure was developed by combining acid demineralization, base extraction, and dichromate oxidation for fractionation and quantitative isolation of soil/sediment organic matter (SOM) into four fractions: (1) humic acids + kerogen + BC (HKB); (2) kerogen + BC (KB); (3) humic acid (HA); and (4) BC. The soil/sediment samples tested were collected from the suburban areas of Guangzhou, a rapidly developing city of China. The results show that BC and kerogen constitute 57.8-80.6% of the total organic carbon (TOC) and that the relative content of BC ranges from 18.3% to 41.0% of the TOC, indicating that both BC and kerogen are major organic components in soils and sediments from this industrialized region. Systematic characterization of the isolated SOMs shows that both BC and kerogen have sizes ranging from a few microns to above 100 microm, relatively low O/C and H/C atomic ratios, and low contents of oxygen-containing functional groups. The isolated BC has unique fusinite and semifusinite macerals, highly porous nature, and structures indicative of its possible origins. The study indicates that SOM is highly heterogeneous and that humin, the nonextractable humus fraction, consists mainly of kerogen and BC materials in the tested soil/sediment samples. The presence of these materials in soils and sediments may have significant impacts on pollutant mass transfer and transformation processes such as desorption and bioavailability of less polar organic chemicals in surface aquatic and groundwater environments.     

Intercorrelations among degree of geochemical alterations, physicochemical properties, and organic sorption equilibria of kerogen

Recent studies reported that kerogen is an important natural organic material dominating sorption of relatively hydrophobic organic contaminants (HOCs) by topsoils and river sediments collected from industrialized regions. Due to its chemical and structural heterogeneity, kerogen is expected to exhibit a spectrum of sorptive phenomena for HOCs. The goal of this study is to establish correlations between heterogeneous physicochemical properties of kerogen and its sorptive characteristics for HOCs. In this study, we simulated diagenetic alterations under laboratory conditions by thermally treating a low-grade lignite at 200, 250, 300, 350, 400, 450, and 500 degrees C, yielding a series of type III kerogen samples having the same parental material but different maturations and physicochemical properties. The treated samples and the original lignite were systematically characterized using different methods and were used as the sorbents for sorption equilibrium study. The results of characterization revealed that black carbon or charwas formed at 450 degrees C or above and that, as the treatment temperature (T) increases, both O/C and H/C atomic ratios decrease whereas aromaticity and reflectance index increase. The sorption and desorption isotherms measured for 1,3,5-trichlorobenzene and phenanthrene are nonlinear and hysteretic. The nonlinearity and apparent desorption hysteresis increase as a function of Tand correlate well with rigidity and aromaticity of the organic matrix. The sorption capacity for each sorbate increases initially as T increases, reaches a maximum at 300-350 degrees C, and then decreases rapidly as Tincreases beyond 350 degrees C. This study suggests that the highly heterogeneous kerogen-based coal materials may have varied elemental compositions, functionalities, and matrix rigidity and that they could play major roles in the isotherm nonlinearity and the apparent sorption-desorption hysteresis exhibited by soils and sediments.     

Sorption of phenanthrene to environmental black carbon in sediment with and without organic matter and native sorbates

Strong sorption to soot- and charcoal-like material (collectively termed black carbon or BC) in soils and sediments is possibly the reason for recent observations of elevated geosorbent-water distribution ratios, slow desorption, limited uptake, and restricted bioremediation. We evaluated the role of environmental BC in the sorption of phenanthrene (PHE) to a polluted lake sediment from a Rhine River sedimentation area. Sorption isotherms were determined over a wide concentration range (0.0005-6 microg/ L) for the original sediment (with organic matter or OM, native sorbates, and BC), sediment from which we had stripped > 90% of the native sorbates (only OM and BC), and sediment combusted at 375 degrees C (only BC). The sorption isotherms of the original and stripped sediments were almost linear (Freundlich coefficient or n(F) > 0.9), whereas the isotherm of the BC remaining after the sediment combustion was highly nonlinear (n(F) = 0.54). At low concentrations (ng/L range), PHE sorption to BC in the combusted sediment was found to exceed the total PHE sorption in the original and stripped sediments. This implies that it may not be possible to use a BC-water sorption coefficient measured in combusted sediment to estimate total sorption to the original sediment. This "intrinsic" BC-water sorption coefficient after combustion was calculated to be 9 times larger than the "environmental" one in the untreated sediment. Competition between the added PHE and the native PAHs and/or OM may explain this difference. It appears that, at low aqueous PHE concentrations (ng/L and below), BC is the most important geosorbent constituent with respect to sorption. At higher concentrations (microg/L), BC sorption sites become saturated and BC sorption is overwhelmed by sorption to the other OM constituents. Because sorption is a central process affecting contaminant behavior and ecotoxicity, understanding this process can strongly contribute to risk assessment and fate modeling.     

Sorption of phenanthrene by reference smectites

Fate and behavior of nonionic hydrophobic organic compounds (HOCs) in the environment is mainly controlled by their interactions with various components of soils and sediments. Due to their large surface area and abundance in many soils, smectites may greatly influence the fate and transport of HOCs in the environment. We used phenanthrene as a probe to explore the potential of reference smectites to sorb HOCs from aqueous solution. Batch experiments were used to construct phenanthrene sorption isotherms, and possible sorption mechanisms were inferred from the shape of the isotherms. Our results demonstrate that smectites can retain large amounts of phenanthrene from water. Phenanthrene sorption capacities of the reference smectites investigated in this study were comparable to those of soil clays containing a considerable amount of organic matter. Hectorite exhibited the highest sorption affinity and capacity followed by Panther Creek montmorillonite. The lack of correlation between Freundlich sorption constants (K'f) and indices of charge or hydrophobicity suggests that sorption of phenanthrene by smectites is primarily a physical phenomenon. Capillary condensation into a network of nanoor micropores created by quasicrystals is likely to be a dominant mechanism of phenanthrene retention by smectites.     

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.     

Enhanced pesticide sorption by soils containing particulate matter from crop residue burns

Lack of proper techniques to isolate black carbon (BC) from soils has hindered the understanding of their roles in the sorption and environmental fate of organic contaminants in soils and sediments. The burning of crop residues may be the primary source of BC in agricultural soils. In this study, wheat (Triticum aestivum L.) and rice (Oryza sativa L.) residues were burned, and the resulting particulate matter (ashes) along with a soil were used to sorb diuron from water. Calculations indicated that the burning of crop residues may result in an appreciable level of ashes in soils. The diuron sorption isotherms on ashes were curvilinear Langmuir type, suggestive of surface adsorption and similar to that with activated carbon. Ashes were 400-2500 times more effective than soil in sorbing diuron over the concentration range of 0-6 mg/L. Sorption by wheat ash-amended soils and the degree of isotherm nonlinearity increased with increasing ash content from 0% to 1% (weight), indicating the significant contribution of wheat ash to the sorption. Calculations show that wheat ash and soil independently contributed to the sorption. Above the wheat ash content of 0.05%, the sorption was largely controlled by the ash. Density-based fractionation and repeated HCI-HF washing of wheat ash yielded carbon-enriched fractions and enhanced diuron sorption by these fractions. BC appeared primarily responsible for the high adsorptivity of ashes. Ashes arising from the burning of crop residues may be an important determinant of pesticide immobilization and environmental fate in soils.     

Extensive sorption of organic compounds to black carbon, coal, and kerogen in sediments and soils: mechanisms and consequences for distribution, bioaccumulation, and biodegradation

Evidence is accumulating that sorption of organic chemicals to soils and sediments can be described by "dual-mode sorption": absorption in amorphous organic matter (AOM) and adsorption to carbonaceous materials such as black carbon (BC), coal, and kerogen, collectively termed "carbonaceous geosorbents" (CG). Median BC contents as a fraction of total organic carbon are 9% for sediments (number of sediments, n approximately 300) and 4% for soils (n = 90). Adsorption of organic compounds to CG is nonlinear and generally exceeds absorption in AOM by a factor of 10-100. Sorption to CG is particularly extensive for organic compounds that can attain a more planar molecular configuration. The CG adsorption domain probably consists of surface sites and nanopores. In this review it is shown that nonlinear sorption to CG can completely dominate total sorption at low aqueous concentrations (<10(-6) of maximum solid solubility). Therefore, the presence of CG can explain (i) sorption to soils and sediments being up to 2 orders of magnitude higher than expected on the basis of sorption to AOM only (i.e., "AOM equilibrium partitioning"), (ii) low and variable biota to sediment accumulation factors, and (iii) limited potential for microbial degradation. On the basis of these consequences of sorption to CG, it is advocated that the use of generic organic carbon-water distribution coefficients in the risk assessment of organic compounds is not warranted and that bioremediation endpoints could be evaluated on the basis of freely dissolved concentrations instead of total concentrations in sediment/soil.     

The role of condensed carbonaceous materials on the sorption of hydrophobic organic contaminants in subsurface sediments

The identification and characterization of carbonaceous materials (CMs) that control hydrophobic organic chemical (HOC) sorption is essential to predict the fate and transport of HOCs in soils and sediments. The objectives of this paper are to determine the types of CMs that control HOC sorption in the oxidized and reduced zones of a glacially deposited groundwater sediment in central Illinois, with a special emphasis on the roles of kerogen and black carbon. After collection, the sediments were treated to obtain fractions of the sediment samples enriched in different types of CMs (e.g., humic acid, kerogen, black carbon), and selected fractions were subject to quantitative petrographic analysis. The original sediments and their enrichment fractions were evaluated for their ability to sorb trichloroethene (TCE), a common groundwater pollutant. Isotherm results and mass fractions of CM enrichments were used to calculate sorption contributions of different CMs. The results indicate that CMs in the heavy fractions dominate sorption because of their greater mass. Black carbon mass fractions of total CMs in the reduced sediments were calculated and used to estimate the sorption contribution of these materials. Results indicate that in the reduced sediments, black carbon may sequester as much as 32% of the sorbed TCE mass, butthat kerogen and humin are the dominant sorption environments. Organic carbon normalized sorption coefficients (K(oc)) were compared to literature values. Values for the central Illinois sediments are relatively large and in the range of values determined for materials high in kerogen and humin. This work demonstrates the advantage of using both sequential chemical treatment and petrographic analysis to analyze the sorption contributions of different CMs in natural soils and sediments, and the importance of sorption to natural geopolymers in groundwater sediments not impacted by anthropogenic sources of black carbon.     

Sorption kinetics of organic contaminants by sandy aquifer and its kerogen isolate

Long-term sorption behaviors of phenanthrene (Phen) on the Borden sand from 1 min to 365 days and of Phen and 1,2-dichlorobenzene (DCB) on the isolated kerogen from 1 to 120 days were characterized by examining the time dependence of solute phase distribution relationships (PDRs) and compared with the prior reported sorption of tetrachlorobenzene (TeCB) and tetrachloroethene (PCE) on the pulverized and/or acid-treated bulk sand and size fractions. The sorption kinetics for Phen on the bulk sand and its kerogen isolate can well be described by the fractional power kinetics equation (q(e) = kt(b)). The similar rate parameter b for q(e)(t) vs t at 5-7 levels of initial concentrations of Phen on the two sorbents, respectively, ranging from 0.077 to 0.099 and from 0.072 to 0.086, indicates the similar sorption kinetics rate. The modified-Freundlich parameters of TeCB on the pulverized or acid-treated 0.3-mm size fraction match those of Phen on the isolated kerogen, suggesting the same natural organic matter (NOM) property of the two sorbents. As the prior investigation underestimated the Koc value for the TeCB sorption on the acid-treated 0.3-mm size fraction by a factor of 1.76, the estimated time to reach 95% of sorption equilibrium is much longer than the prior estimation (over 10 years vs about 2.5 years). The estimated times to reach 95% of sorption equilibrium at three levels of relative solubility for Phen on the bulk sand and its isolated kerogen are, respectively, longer than one decade, demonstrating the similar diffusion length for Phen on the two sorbents. The observed slow sorption kinetics is related to nanometer-pore diffusion within kerogen matrix. The investigation supplies new clues for explaining the often observed much longer persistence of organic contaminants in soils and sediments than the prediction based on the short-term laboratory experiment.     

Strong sorption of phenanthrene by condensed organic matter in soils and sediments

The nonhydrolyzable carbon (NHC) and black carbon (BC) in three contaminated soils and seven sediments from the Pearl River Delta and Estuary, China, were isolated upon treatments with an acid hydrolysis method and with a combustion method at 375 degrees C, respectively, and their sorption isotherms for phenanthrene (Phen) were established. It was found that NHC is chemically and structurally different from the biopolymer and humic substances and consists mainly of aliphatic and aromatic carbon using elemental analysis, 13C nuclear magnetic resonance spectroscopy (13C NMR), and Fourier transformed infrared spectroscopy (FTIR). All the sorption isotherms are nonlinear and are well fitted by the Freundlich model. The single-point organic carbon-normalized distribution coefficient (K(oc)) measured for the isolated NHC is 1.3-7.7 times higher than that for the bulk samples at the same aqueous concentration of Phen. The NHC fractions play a dominant role to the overall sorption in the bulk samples. The bulk soils and their NHC fractions have lower sorption capacity than the bulk sediments and their NHC fractions, relating to the different source of organic matter between soils and sediments. The Phen sorption capacity in the NHC samples is related significantlyto H/C ratios and aliphatic carbon, but negatively to aromatic carbon, demonstrating the important role of aliphatic carbon to the Phen sorption and the fate in the investigated soils and sediments.     

Sorption to black carbon of organic compounds with varying polarity and planarity

It is becoming increasingly clear that the products of incomplete combustion (soot and charcoal, collectively termed black carbon or BC) can be responsible for as much as 80 - 90% of the total sorption to sediments of aromatic, planar, and hydrophobic compounds such as polycyclic aromatic hydrocarbons or planar polychlorinated biphenyls. In the present study, it was investigated whether a nonpolar aliphatic compound (hexachloroethane) and three nonplanar bipolar compounds with different functional groups [free electron pairs but no aromatic ring (butylate) or free electron pairs and an aromatic ring (diuron, atrazine)] would also show strong and nonlinear sorption to a BC-enriched sediment. At a concentration of 1 ng/L, the extent of elevated BC sorption compared to total organic carbon (TOC) sorption increased in the order atrazine < hexachloroethane < butylate < diuron. Rationalization of the differences between the sorbates was attempted in terms of dispersive and steric effects. This study shows that the effects of strong BC sorption apply to a broader range of organic contaminants than previously thought, and the results will aid in a better understanding of BC sorption mechanisms and improved fate modeling of contaminants in the environment.     

Variation in phenanthrene sorption coefficients with soil organic matter fractionation: the result of structure or conformation?

Sorption of phenanthrene to varying soil types was investigated to better understand sorption processes. Humic acid and humin fractions were isolated from each soil sample, and sorption coefficients were measured by batch equilibration. Samples were characterized by carbon analysis and 13C cross polarization magic angle spinning (CP/ MAS) nuclear magnetic resonance (NMR) spectroscopy. Measured organic carbon-normalized sorption coefficients (Koc) of the fractions were greater in all cases when compared to the soils. The humin fractions exhibited greater Koc values than did source samples, suggesting that fractionation may reorganize organic matter in humin resulting in an increased availability of and/or more favorable sorption domains. Mass balance calculations revealed that the sum of sorption to the fractions is greater than sorption to the whole sample. The greatest difference between sorption values was found to occur with the mineral soils, suggesting that clay minerals influence the physical conformation of soil organic matter (SOM) and availability of sorption domains. The mass balance, sorption data, and a lack of consistent trends between observed Kco values and solid-state 13C NMR data suggest that the physical conformation of SOM and chemical characteristics both play important roles in sorption processes.     

Sorption of phenanthrene by nonhydrolyzable organic matter from different size sediments

Nonhydrolyzable organic carbon (NHC) and sorption isotherms of phenanthrene (Phen) on six size-fractionated NHC fractions in two sediments from the Pearl River and Estuary, South China, were investigated. It was found that NHC including ancient organic carbon, black carbon, resistant aquatic organic carbon, and aged soil organic carbon consists mainly of aliphatic and aromatic carbon using 13C nuclear magnetic resonance spectroscopy. The sorption isotherms of Phen by the size-fractionated NHC fractions are nonlinear and are well-fitted to the Freundlich model. For the estuary sediment, the NHC contents and the organic carbon-normalized distribution coefficients (Koc) in the size fractions increase with decreasing particle size. The clay NHC fraction contributes to 70% of the Phen sorption by the bulk NHC isolate. However, for the contaminated river sediment, the NHC contents and the Koc values exhibit no regular variations among the size fractions. The Phen sorption capacities on the size-fractionated NHC fractions of the two sediments are significantly related to their H/C ratios and aliphatic carbon, but negatively to aromatic carbon. The fine-particle NHC fractions with high aliphatic carbon and H/C ratio play a very important role in the sorption, transport, and fate of Phen by the investigated sediments.     

Thermal analytical investigation of biopolymers and humic- and carbonaceous-based soil and sediment organic matter

Improved understanding of the physical, chemical, and thermodynamic properties of soil and sediment organic matter (SOM) is crucial in elucidating sorption mechanisms of hydrophobic organic compounds (HOCs) in soils and sediments. In this study, several thermoanalytical techniques, including thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), temperature-modulated differential scanning calorimetry (TMDSC), and thermal mechanical analysis (TMA) were applied to 13 different organic materials (three woods, two humic acids, three kerogens, and five black carbons) representing a spectrum of diagenetic and/or thermal histories. Second-order thermal transition temperatures (T(t)) were identified in most materials, where the highest observed T(t) values (typically characterized as glass transition temperatures (T(g were shown to closely relate to chemical characteristics of the organic samples as influenced by diagenetic or thermal alteration. Results further suggest a positive correlation between glass transition temperature and a defined diagenetic/thermal index, where humic-based SOM (e.g., humic and fulvic acids) possess lowertransition temperatures than more "mature" carbonaceous-based SOM (i.e., kerogens and black carbons). The observed higher thermal transition temperature of aliphatic-rich Green River shale kerogen (approximately 120 degrees C) relative to that of aromatic-rich humic acids suggests that a sole correlation of aromaticity to thermal transition temperature may be inappropriate.     

Sorption of organic compounds to fresh and field-aged activated carbons in soils and sediments

Activated carbon (AC) amendment to polluted sediment or soil is an emerging in situ treatment technique that reduces freely dissolved porewater concentrations and subsequently reduces the ecological and human health risk of hydrophobic organic compounds (HOCs). An important question is the capacity of the amended AC after prolonged exposure in the field. To address this issue, sorption of freshly spiked and native HOCs to AC aged under natural field conditions and fresh AC amendments was compared for one soil and two sediments. After 12-32 months of field aging, all AC amendments demonstrated effectiveness for reducing pore water concentrations of both native (30-95%) and spiked (10-90%) HOCs compared to unamended sediment or soil. Values of K(AC) for field-aged AC were lower than freshly added AC for spiked HOCs up to a factor of 10, while the effect was less for native HOCs. The different behavior in sorbing native HOCs compared to freshly spiked HOCs was attributed to differences in the sorption kinetics and degree of competition for sorption sites between the contaminants and pore-clogging natural organic matter. The implications of these findings are that amended AC can still be effective in sorbing additional HOCs some years following amendment in the field. Thus, a certain level of long-term sustainability of this remediation approach is observed, but conclusions for decade-long periods cannot be drawn solely based on the present study.     

Compound-specific factors influencing sorption nonlinearity in natural organic matter

Nonlinear sorption by natural organic matter may have a significant impact on the behavior of organic contaminants in soils and sediments. This study presents a molecular probe approach based on linear solvation energy relationships (LSERs) to identify and quantify the molecular interactions causing concentration-dependent sorption and proposes estimation methods for sorption nonlinearities. Sorption isotherms ranging over concentrations of more than 4 orders of magnitude were determined in batch systems for 23 and 16 chemically diverse probe compounds in a lignite sample and a peat soil, respectively. Each sorbent showed characteristic nonlinear sorption with Freundlich exponents (1/n) being 0.7-1. The LSER-based analysis revealed that the strength of nonspecific interactions did not vary with concentration for both sorbents. In lignite, specific interactions did not affect sorption nonlinearity either, suggesting that compound-independent factors of lignite were responsible for the nonlinear sorption. In the peat soil, by contrast, the specific interactions related to the solute polarizability/dipolarity parameter (S) decreased with increasing concentration. Consequently, compounds of higher S values were more susceptible to nonlinear sorption in the peat soil. Phenol probes have shown that hydrogen bond donating properties of sorbate compounds have a substantial impact on the overall strength of sorption with organic matter, but no significant influence on sorption nonlinearity. Heterocyclic aromatic compounds appear to undergo additional interactions that are not accounted for by the LSER. These additional interactions considerably enhance both sorption capacity and nonlinearity.     

Importance of adsorption (hole-filling) mechanism for hydrophobic organic contaminants on an aquifer kerogen isolate

Sorption and desorption behaviors of four hydrophobic organic compounds (HOCs) were investigated for an isolated kerogen material from Borden aquifer material with total organic carbon of 0.021%. The solubility-normalized modified Freundlich equation and the combined linear and Polanyi-Dubinin (PD) equation can quite well describe the sorption or desorption isotherms. The partition component is estimated and compared using desorption data, dual-mode modeling, and the reported partition coefficients. The result suggests that the dual-mode modeling and the combined linear and PD modeling may overestimate the partitioning component. The partition component is not so important as assumed before in sorption of HOCs for the studied sorbent. As the fitted PD equation has an exponent parameter b' approaching 1, it is equivalent to the modified Freundlich equation. The small molecules 1,2-dichlorobenzene (DCB) and naphthalene (Naph) have higher adsorption volumes. The lower adsorption volumes for 1,3,5-trichlorobenzene (TCB) and phenanthrene (Phen) suggest that accessibility to the holes of kerogen by large HOC molecules is reduced. The desorption hysteresis is approximately constant for DCB when the relative aqueous concentration ranges from 0.0007 to 0.6, but for Phen is only obvious at higher relative aqueous concentrations. The varied sorption and desorption behaviors for DCB and Phen are satisfactorily explained by an adsorption/ hole filling mechanism and entrapment of some adsorbates in the kerogen matrix and by possible pore deformation mechanism at high concentrations.     

Phenanthrene sorption to soil humic acid and different humin fractions

This study was undertaken to provide an insight into the effect of heterogeneous soil organic matter (SOM) on the sorption of phenanthrene. Humic acid (HA) and humin were extracted from a peat soil. Humin was further fractionated into bound-humic acid (BHA), lipid, and insoluble residue (IR) fractions. Heterogeneous natures of these fractions were characterized by elemental analysis, ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, and solid-state 13C NMR. Aliphaticity of the fractions followed the order lipid >BHA > HA > IR, while the polarity order was IR > BHA> HA > lipid. Sorption of phenanthrene on these fractions fitted the Freundlich equation, suggesting that phenanthrene sorption isotherms of lipid were almost linear (N = 0.993), while those of HA, BHA, and IR were nonlinear, with N values ranging from 0.723 to 0.910. The N values followed the order lipid > HA > BHA > IR and were significantly correlated inversely with their polarities (p < 0.05). Organic carbon-normalized sorption coefficients (K(FOC)) were independent of aliphatic or aromatic contents of the SOM fractions. The results suggested that SOM, especially for the humin fractions, was highly heterogeneous in terms of elemental composition, structure, and polarity. Such heterogeneity was considered to be responsible forthe nonlinear sorption of phenanthrene.     

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 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.