Sorption and degradation of steroid hormones in soils during transport: column studies and model evaluation

Natural and synthetic analogues of steroid hormones and their metabolites have emerged as contaminants of concern. Characterizing sorption and degradation processes is essential to assess the environmental distribution, persistence, and ecological significance of steroid hormones in terrestrial and aquatic systems. We examined the fate and transport of testosterone and 17beta-estradiol by conducting a series of fast-flow-velocity transport experiments under pulse-type and flow-interruption boundary conditions in columns packed with a surface soil, freshwater sediment, and two sands. Flow-interruption experiments provided independent estimates of degradation coefficients for the parent hormones and their metabolites, while pulse-input type experiments were used to identify transport mechanisms for hormones by employing forward modeling approaches. Estimated degradation rate coefficients (k) for the hormones from flow-interruption experiments ranged from 0.003 to 0.015 h(-1) for testosterone and from 0.0003 to 0.075 h(-1) for estradiol, similar to those observed in batch studies. Degradation rate coefficients for the two primary metabolites were 1-2 orders of magnitude larger than those for the parent chemicals. Estimated k values decreased with column life as a result of nutrient depletion. Large sorption by soils of the parent and metabolites (log Koc approximately 2.77-3.69) did not appear to hinder degradation; k values were an order of magnitude smaller than the estimated sorption mass-transfer constants. Differences in hormone breakthrough curves from a single-pulse displacement and those predicted using independently estimated parameters suggest that modeling hormone degradation as a simple first-order kinetic process may be sufficient, but not accurate.     

Sorption and dissipation of testosterone, estrogens, and their primary transformation products in soils and sediment

Concern over the potential negative ecological effects of steroid hormones from human- and animal-derived wastes has resulted in an increased interest regarding the mobility and persistence of these compounds in the environment. Batch experiments were conducted to examine the simultaneous sorption and dissipation of three reproductive hormones (testosterone, 17beta-estradiol, and 17alpha-ethynyl estradiol) in four midwestern U.S. soils and one freshwater sediment. Sorption isotherms were generated by measuring aqueous concentrations and by extracting the sorbed parent chemical or transformation products (e.g., estrone, androstenedione). Apparent sorption equilibrium is reached within a few hours. Measured sorption isotherms for the three parent chemicals and their principal transformation products were generally linear. Average organic carbon normalized sorption coefficients (K(oc)) resulted in standard deviations of less than 0.2 log units and were consistent with reported aqueous solubilites and octanol-water partition coefficients, indicating hydrophobic partitioning as the dominant sorption mechanism. Large log K(oc) values (approximately 3-4) suggest that leaching from soils will be limited, runoff of soil- and land-applied biosolids are the most likely inputs into surface waters, and that a significant fraction of these compounds will be associated with sediments. Half-lives for hormone dissipation in the aerobic soil and sediment slurries estimated assuming pseudo first-order processes ranged from a few hours to a few days with testosterone having the shortest half-life.     

Competitive sorption between 17alpha-ethinyl estradiol and naphthalene/phenanthrene by sediments

Steroid hormones such as 17alpha-ethinyl estradiol (EE2) have been frequently detected at various levels in surface waters downstream of many municipal wastewater treatment facilities. Their fate, transport, and environmental risk are currently not well characterized. This study examined the competitive sorption between EE2 and two aromatic hydrocarbon compounds, phenanthrene and naphthalene, by three sediments. The sorption isotherms of phenanthrene and naphthalene were measured at 22 +/- 0.5 degrees C using a batch technique with initial aqueous concentrations (Co) of EE2 at 0, 100, 500, and 2000 microg/L. Competitive sorption varied between EE2 and phenanthrene or naphthalene on the sediments. The linearity of the naphthalene sorption isotherm was found to increase as a function of the cosorbate EE2 concentration from 0 to 2000 microg/L. The single-point naphthalene KD value at equilibrium aqueous-phase naphthalene concentration (Ce) of 25 microg/L was reduced by 19-26% and 27-48% at Co (EE2) = 100 and 500 microg/L, respectively. The sorption of phenanthrene at its low Ce range was similarly affected by EE2, but to a much less extent, possibly because phenanthrene is more hydrophobic than EE2. At high phenanthrene Ce, no measurable change was observed even at CO (EE2) = 2000 microg/L. While the effect of naphthalene on EE2 sorption was insignificant, the competitive effect on the sorption of EE2 by phenanthrene was very significant at low EE2 concentrations. The measured single-point EE2 KD values decreased as much as 35% as the phenanthrene Ce increases from below 10 microg/L to slightly above 100 microg/L. This study suggests that the fate and transport of emerging pollutants such as EE2 could be affected in the presence of more hydrophobic pollutants in aquatic systems.     

Sorption and degradation of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine in soil

The sorption/desorption and long-term fate of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) was examined using sterilized and nonsterilized soils. Two soils were used that differ mainly by the amount of total organic carbon (TOC): an agricultural topsoil (VT, 8.4% TOC) and a sandy soil (SSL, 0.33% TOC). The adsorption isotherms performed at room temperature were well-described by a linear model, which led to sorption distribution coefficients of 2.5 and 0.7 L kg(-1) for VT and SSL soils, respectively. The organic content of soil did not significantly affect HMX sorption. Over a period of 20 weeks, HMX degraded (60% disappearance) in static anaerobic nonsterile VT soil preparations. In separate experiments using UL-[14C]-HMX, 19% mineralization (liberated 14CO2) was obtained in 30 weeks. In addition, four nitroso derivatives of HMX were detected. Knowing the sorption/desorption behavior and the long-term fate of HMX in soil will help assess the effectiveness of natural attenuation for HMX removal.     

Manure-borne estrogens as potential environmental contaminants: a review

Livestock wastes are potential sources of endocrine disrupting compounds to the environment. Steroidal estrogen hormones such as estradiol, estrone, and estriol are a particular concern because there is evidence that low nanogram per liter concentrations of estrogens in water can adversely affect the reproductive biology of fish and other aquatic vertebrate species. We performed a literature review to assess the current state of science regarding estrogen physicochemical properties, livestock excretion, and the fate of manure-borne estrogens in the environment. Unconjugated steroidal estrogens have low solubility in water (0.8-13.3 mg L(-1)) and are moderately hydrophobic (log Kow 2.6-4.0). Cattle excrete mostly 17alpha-estradiol, 17beta-estradiol, estrone, and respective sulfated and glucuronidated counterparts, whereas swine and poultry excrete mostly 17beta-estradiol, estrone, estriol, and respective sulfated and glucuronidated counterparts. The environmental fate of estrogens is not clearly known. Laboratory-based studies have found that the biological activity of these compounds is greatly reduced or eliminated within several hours to days due to degradation and sorption. On the other hand, field studies have demonstrated that estrogens are sufficiently mobile and persistent to impact surface and groundwater quality. Future research should use standardized methods for the analysis of manure, soil, and water. More information is needed about the types and amounts of estrogens that exist in livestock wastes and the fate of manure-borne estrogens applied to agricultural lands. Field and laboratory studies should work toward revealing the mechanisms of estrogen degradation, sorption, and transport so that the risk of estrogen contamination of waterways can be minimized.     

Transport of testosterone and estrogen from dairy-farm waste lagoons to groundwater

Although concentrated animal feeding operations constantly generate physiologically active steroidal hormones, little is known of their environmental fate. Estrogen and testosterone concentrations in groundwater and their distribution in sediments below a dairy-farm wastewater lagoon were therefore determined and compared to a reference site located upgradient of the farm. Forward simulations of flow as well as estrogen and testosterone transport were conducted based on data from the sediment profile obtained during drilling of a monitoring well belowthe dairy-farm waste lagoon. Testosterone and estrogen were detected in sediments to depths of 45 and 32 m, respectively. Groundwater samples were directly impacted by the dairy farm, as evidenced by elevated concentrations of nitrate, chloride, testosterone, and estrogen as compared to the reference site. Modeling potential transport of hormones in the vadose zone via advection, dispersion, and sorption could not explain the depths at which estrogen and testosterone were found, suggesting that other transport mechanisms influence hormone transport under field conditions. These mechanisms may involve interactions between hormones and manure as well as preferential flow paths, leading to enhanced transport rates. These types of interactions should be further investigated to understand the processes regulating hormone transport in the subsurface environment and parametrized to forecast long-term fate and transport of steroidal hormones.     

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 of two naphthoic acids to goethite surface under flow through conditions

While the transport of low molecular weight organic acids was widely investigated, little is known about the mobility of the carboxylated aromatic compounds containing double rings in natural porous media. This study combines macroscopic (batch and column), microscopic (vibration spectroscopy), and surface complexation modeling to evaluate the mobility of two PAH degradation products: naphthoic acid (1-naphthoic acid (NA) and 1-hydroxy-2-naphthoic acid (HNA)), in porous media consisting of goethite-coated sand. The loss of ligands from aqueous solution was attributed to (1) a hydrogen-bonded surface complex present over the entire 3-10 pH range as well as protonated (2) surface and (3) bulk precipitates below pH 5. Mobility in column experiments was strongly affected by ligand functionality. Adsorption breakthrough predictions that make use of surface complexation parameters accurately predicted NA mobility. Those for HNA however predicted much less adsorption reactions than in the batch sorption experiments. Additional breakthrough experiments and test calculations confirmed that these differences were not related to sorption kinetics. HNA adsorption breakthrough data could only be predicted by lowering intrinsic complexation constant of the formation of hydrogen-bonded species, thereby suggesting modifications of the diffuse layer properties under flow conditions. These findings have strong implications in the assessment and prediction of contaminant transport and environmental remediation.     

Sorption behavior of nonylphenol in terrestrial soils

Nonylphenol (NP) as an intermediate from anaerobic degradation of widely used nonionic surfactants occurs widespread in the environment. Partition behavior of this toxic and endocrine-disrupting chemical between soil and water was not examined until yet. The objective of this investigation was to quantify sorption and desorption behavior of 4-nonyl[14C]phenol in a set of 51 soils using the batch equilibrium approach. Kinetic studies indicated apparent equilibrium within 20 h. Sorption was influenced by sorbate structure as could be shown with branched 4-nonyl[14C]phenol and the linear 4-n-NP, respectively. Linear 4-n-NP behaves differently from the branched isomers of 4-NP. Sorption of 4-nonyl[14C]phenol tested with five different initial concentrations resulted in linearly fitted isotherms that provided calculation of sorption partition coefficients (KP). Desorption partition coefficients (KP-des) revealed hysteresis independent of soil properties but decreasing with decreasing initial NP concentrations. KP values were correlated with organic carbon content of the soils yielding a log KOC of 3.97.     

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 oxytetracycline to iron oxides and iron oxide-rich soils

The sorption interactions of oxytetracycline with goethite, hematite, and two iron oxide-rich soils were investigated using batch sorption experiments. Oxytetracycline sorption coefficients for goethite and hematite increased with pH to maximum values at pH approximately 8. The sorption edge shape and desorption treatments were consistent with a surface complexation mechanism and could be described by the interaction of divalent anion species with the oxide surface. Oxytetracycline sorption to Georgeville and Orangeburg Ultisol soils decreased with pH. Chemical digestion treatments were used to deduce that soil sorption occurred by complexation to oxide coatings on clay and quartz grains. These results indicate that sorption models must consider the interaction of oxytetracycline, and other similar ionogenic compounds, with soil oxide components in addition to clays and organic matter when predicting sorption in whole soils.     

The sorption of iodide by soils as influenced by equilibrium conditions and soil properties

The sorption of iodide was reduced when soil was dried before equilibration with an iodide solution. With undried soils, sorption continued for > 48 h, maximum sorption occurred at pH values < 5 but a secondary sorption peak occurred at pH 8.5 to 9.0, particularly with a soil containing a high level of organic matter. Temperature had only a small effect on sorption over the range 10 to 35 °C. Maximum values for the sorption of iodide by two surface soils (0 to 10cm) at pH 6.6 to 6.8, assessed with a soil: solution ratio of 1:10, an equilibrium time of 40 h and at room temperature, were 25 and 6 fig I/g soil, respectively. The amounts of iodide sorbed by these soils, and by soils taken from successive 10 cm layers to a depth of 40 cm at the same two sites, were closely related to the contents of organic matter in the soils but not to contents of iron or aluminium oxides or of clay. Treatment of the surface soils with hydrogen peroxide to destroy organic matter greatly reduced the sorption of iodide at the pH of about 5.5 that resulted from the treatment. The removal of iron and aluminium oxides with Tamm reagent also resulted in a marked reduction in sorption at pH < 5. The results indicate that sorption was due in part to soil organic matter and in part to iron and/or aluminium oxides. At pH > 6, organic matter appeared to be the major sorbing constituent but under more acid conditions the oxides appeared to be increasingly important.     

Hexavalent uranium diffusion into soils from concentrated acidic and alkaline solutions

Uranium contamination of soils and sediments often originates from acidic or alkaline waste sources, with diffusion being a major transport mechanism. Measurements of U(VI) diffusion from initially pH 2 and pH 11 solutions into a slightly alkaline Altamont soil and a neutral Oak Ridge soil were obtained through monitoring uptake from boundary reservoirs and from U concentration profiles within soil columns. The soils provided pH buffering, resulting in diffusion at nearly constant pH. Micro X-ray absorption near edge structure spectra confirmed that U remained in U(VI) forms in all soils. Time trends of U(VI) depletion from reservoirs and U(VI) concentration profiles within soil columns yielded Kdvalues consistent with those determined in batch tests at similar concentrations (approximately 1 mM) and much lower than values for sorption at much lower concentrations (nM to microM). These results show that U(VI) transport at high concentrations can be relatively fast at non-neutral pH, with negligible surface diffusion, because of weak sorption.     

Sorption-desorption of ionogenic compounds at the mineral-water interface: study of metal oxide-rich soils and pure-phase minerals

Sorption of the ionic compounds 2,4-D and quinmerac onto iron oxide-rich, variable charged soils was strongly influenced by mineralogy, particularly soil iron and aluminum oxides, whereas sorption of the neutral norflurazon was only related to total soil C. An appreciable fraction of the mass sorbed in stirred-flow studies was easily desorbed by deionized water, and desorption of ionic compounds was initially more rapid than sorption. This sorption-desorption behavior, although contrary to desorption hysteresis commonly observed in batch studies, suggests that the reversibly sorbed fraction is weakly bound to the soil surface. 2,4-D sorption to iron oxide-rich soils and pure-phase metal oxides appears to be driven by nonspecific electrostatic attraction, with specific electrostatic attraction and van der Waals interactions being secondary. Both the carboxylate and the heterocyclic N groups may participate in sorption of quinmerac, facilitated by specific and nonspecific electrostatic attraction and surface complexation. The heterocyclic N, amine, and carbonyl groups of norflurazon do not appear to interact with soil minerals.     

Polybrominated diphenyl ethers in watershed soils of the Pearl River Delta, China: occurrence, inventory, and fate

Soils play an important role in the distribution and biogeochemical cycling of polybrominated diphenyl ethers (PBDEs) as they are a major reservoir and sink for PBDEs due to their large sorption capacity. In this study, concentrations, compositional profiles, mass inventories, and fate of sigma9PBDEs (28, 47, 66, 100, 99, 154, 153, 138, 183) and BDE 209 were investigated in 33 surface soils, six profile soils, and three point-source polluted soils (close to e-waste dismantling sites) from the Pearl River Delta (PRD), China. The concentrations of sigma9PBDEs and BDE 209 in the surface soils ranged from 0.13 to 3.81 ng/g with an average of 1.02 ng/g and from 2.38 to 66.6 ng/g with an average of 13.8 ng/g, respectively, and ranged from 1.93 to 19.5 ng/g and from 25.7 to 102 ng/g, respectively, in the point-source contaminated soils. The PBDE compositional patterns in the surface soils indicated deca-BDE, penta-BDE, and octa-BDE products as the main sources, but those in the point-source samples suggested deca-BDE and octa-BDE technical mixtures as the dominant sources. The mass inventories of PBDEs in soils of the PRD were estimated at 3.98 and 44.4 t for sigma9PBDEs and BDE 209, respectively. The average loading of PBDEs in the soils was comparable to that in the sediments of the Pearl River Estuary, suggesting that soil erosion and surface runoff are an important mode to transport PBDEs from terrestrial sources to oceans in the PRD. Individual BDE congeners, sigma9PBDEs, and PBDE 209, were significantly correlated with total organic carbon (TOC), and a good regression (except for BDE 47) between the logarithms of TOC-normalized BDE average concentrations and their log K(ow) was also obtained, indicating that sorption of PBDEs on soil organic matter governed their spatial distribution, transportation, and fate in the soils. Predicted aqueous and gaseous concentrations of PBDEs were derived from the soil-water and soil-air partitioning models, respectively, and good agreements were obtained between the predicted and previously reported values. BDE 47 and/or 28 did not appear to follow the same trend for these models, an indication that an portion of them was likely the biodegradation byproducts in soils.     

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.     

Sorption of heterocyclic organic compounds to reference soils: column studies for process identification

In this study, the sorption behavior of a wide variety of N-, S-, and O-heterocyclic compounds (NSOs) to reference soils (Eurosoils 1-5) was characterized by a soil column chromatography (SCC) approach. The major goal was to identify the compound specific and environmental factors influencing sorption processes. The sorption of S- and O-heterocyclic compounds (thiophene, benzothiophene, 5-methylbenzo[b]thiophene, benzofuran, 2-methylbenzofuran, and 2,3-dimethylbenzofuran) was generally controlled by nonspecific interactions with soil organic carbon (OC). With regard to non-ionizable N-heterocyclic compounds, pyrrole, 1-methylpyrrole, and pyrimidine were hardly retarded in any soil. The sorption of indole, 2-hydroxyquinoline, and benzotriazole was dominated by specific interaction (e.g., complexation of surface-bound cations) rather than partition to soil OC. The sorption of ionizable N-heterocyclic compounds (quinoline, isoquinoline, quinaldine, 2-methylpyridine, and pyridine) can be described by a conceptual model including partitioning to soil OC, cation exchange, and an additional sorption process (probably surface complexation of the neutral species). Cation exchange was usually the dominant mechanism in the sorption of ionizable compounds if the protonated fraction of the compound exceeded 5%. Otherwise, surface complexation became dominant. Soil pH was the most important factor influencing the sorption of ionizable NSOs. Our study suggests that a fairly precise assessment of sorption in most soils can be expected for N-, S-, and O-heterocyclic compounds if the three sorption mechanisms are taken into accountwhere appropriate. Deviations from this behavior indicated special cases where additional soil specific properties (e.g., accessible surface, CEC, charge density) need to be considered such as for 2-methylpyridine and pyridine sorption to Eurosoil 1.     

Effect of fluorotelomer alcohol chain length on aqueous solubility and sorption by soils

Fluorotelomer alcohols (FTOHs) are a group of polyfluorinated alkyl chemicals that have been widely studied as precursorsto perfluorocarboxylates such as perfluorooctanoic acid and for which knowledge on their fate in soils is sparse. The solubility and sorption by soil of the homologous 4:2 to 10:2 FTOHs were measured in water or cosolvent/ water solutions. For the smaller 4:2 and 6:2 FTOHs, solubility and sorption could be measured adequately in aqueous systems although transformation was apparent even in gamma-irradiated and autoclaved systems. Sorption coefficients estimated by measuring both sorbed and solution-phase concentrations were not significantly affected by the biotransformation process. The use of cosolvents was employed for probing the behavior of the longer-chain FTOHs with limited aqueous solubility. A single log-linear correlation between aqueous solubility and modified McGowan molar volumes resulted for the n-alkanols and FTOHs. Soil organic carbon (OC) consistently appeared to be the key soil property influencing sorption of the FTOHs while the perfluorocarbon chain length was the dominant structural feature influencing solubility and sorption. Each CF2 moiety decreased the aqueous solubility by -0.78 log units (compared to 0.60 log units for each CH2 addition in hydrogenated primary alcohols), and increased OC-normalized sorption coefficients (Koc) by -0.87 log units. Good log-log linear correlations between Koc and both octanol-water partition coefficients and solubility were observed for the FTOHs.     

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.