Influence of soil organic matter on the leaching of polycyclic aromatic hydrocarbons in soil

Polycyclic aromatic hydrocarbons (PAHs) are one of the main classes of contaminants in the terrestrial environment. Aside from total organic carbon, the ratio among the different organic matter fractions [dissolved organic matter, fulvic acid (FA), humic acid (HA) and humin] can also affect the mobility of these hydrocarbons in soils. In this study the effect of the whole organic carbon pool has been compared with that of HA and FA on the translocation of four PAHs (biphenyl, fluorene, phenanthrene and pyrene) in soil columns. Oxidized and untreated soil columns with and without HA or FA, were prepared, spilled with hydrocarbons and leached with a 0.01 M CaCl2 solution. The influence of HA and FA on PAH translocation was investigated through determinations of the PAH contents and total organic carbon (TOC) in the layers of the columns. All molecules were moved vertically by the percolating solutions, their concentrations decreasing with depths. The nonoxidized soil tended to retain more PAHs (96%) than the oxidized one (60%), confirming that organic matter plays an important role in controlling PAH leaching. The whole organic matter pool reduced the translocation of pollutants downward the profile. The addition of HA enhanced this behaviour by increasing the PAH retention in the top layers (7.55 mg and 4.00 mg in the top two layers, respectively) while FA increased their mobility (only 2.30 and 2.90 mg of PAHs were found in the top layers) and favoured leaching. In fact, in the presence of HA alone, the higher amounts of PAHs retained at the surface and the good correlation (r2=0.936) between TOC and hydrocarbon distribution can be attributed to a parallel distribution of PAHs and HA, while in the presence of FA, the higher mobility of PAHs can be attributed to the high mobility of the humic material, as expected by its extensive hydrophilic characteristics.     

Effect of Pinus radiata derived biochars on soil sorption and desorption of phenanthrene

Biochars are anthropogenic carbonaceous sorbent and their influences on the sorption of environmental contaminants need to be characterized. Here we evaluated the effect of Pinus radiata derived biochars on soil sorption and desorption of phenanthrene. Two biochars separately produced at 350 °C and 700 °C and three soils were tested. Biochar amendment generally enhanced the soil sorption of phenanthrene. The biochar produced at 700 °C generally showed a greater ability at enhancing a soil’s sorption ability than that prepared at 350 °C. The single-step desorption measurement showed an apparent hysteresis in biochar-amended soils. After 28 d equilibration, the sorptive capacity of biochar-amended soil (with an organic carbon content of 0.16%) significantly decreased. This study clearly suggested that biochar application enhanced soil sorption of hydrophobic organic compounds, but the magnitude of enhancement depended on the preparation of biochars, the indigenous soil organic carbon levels, and the contact time between soil and biochar.     

Sorption of atrazine and phenanthrene by organic matter fractions in soil and sediment

Atrazine and phenanthrene (Phen) sorption by nonhydrolyzable carbon (NHC), black carbon (BC), humic acid (HA) and whole sediment and soil samples was examined. Atrazine sorption isotherms were nearly linear. The single-point organic carbon (OC)-normalized distribution coefficients (K_OC) of atrazine for the isolated HA1, NHC1 and BC1 from sediment 1 (ST1) were 36, 550, and 1470 times greater than that of ST1, respectively, indicating the importance of sediment organic matter, particularly the condensed fractions (NHC and BC). Similar sorption capacity of atrazine and Phen by NHC but different isotherm nonlinearity indicated different sorption domains due to their different structure and hydrophobicity. The positive relationship between (O + N)/C ratios of NHC and atrazine log K_OC at low concentration suggests H-bonding interactions. This study shows that sediment is probably a less effective sorbent for atrazine than Phen, implying that atrazine applied in sediments or soils may be likely to leach into groundwater.     

INFLUENCE OF SOIL ORGANIC MATTER ON THE LEACHING OF POLYCYCLIC AROMATIC HYDROCARBONS IN SOIL

Polycyclic aromatic hydrocarbons (PAHs) are one of the main classes of contaminants in the terrestrial environment. Aside from total organic carbon, the ratio among the different organic matter fractions [dissolved organic matter, fulvic acid (FA), humic acid (HA) and humin] can also affect the mobility of these hydrocarbons in soils. In this study the effect of the whole organic carbon pool has been compared with that of HA and FA on the translocation of four PAHs (biphenyl, fluorene, phenanthrene and pyrene) in soil columns. Oxidized and untreated soil columns with and without HA or FA, were prepared, spilled with hydrocarbons and leached with a 0.01 M CaCl₂ solution. The influence of HA and FA on PAH translocation was investigated through determinations of the PAH contents and total organic carbon (TOC) in the layers of the columns. All molecules were moved vertically by the percolating solutions, their concentrations decreasing with depths. The non-oxidized soil tended to retain more PAHs (96%) than the oxidized one (60%), confirming that organic matter plays an important role in controlling PAH leaching. The whole organic matter pool reduced the translocation of pollutants downward the profile. The addition of HA enhanced this behaviour, by increasing the PAH retention in the top layers (7.55 mg and 4.00 mg in the top two layers, respectively) while FA increased their mobility (only 2.30 and 2.90 mg of PAHs were found in the top layers) and favoured leaching. In fact, in the presence of HA alone, the higher amounts of PAHs retained at the surface and the good correlation (r²=0.936) between TOC and hydrocarbon distribution can be attributed to a parallel distribution of PAHs and HA, while in the presence of FA, the higher mobility of PAHs can be attributed to the high mobility of the humic material, as expected by its extensive hydrophilic characteristics.     

Equilibrium sorption of phenanthrene by soil humic acids

This study investigated the effect of chemical heterogeneity of humic acids (HAs) on the equilibrium sorption of phenanthrene by HA extracts. Six HA samples were extracted from three different soils with 0.5 M NaOH and 0.1 M Na₄P₂O₇ and were characterized with elemental analysis, infrared spectrometry, and solid-state ¹³C nuclear magnetic resonance (NMR) spectrometry. The equilibrium sorption measurements were carried out with a batch technique and using the six HA solids as the sorbents and phenanthrene as the sorbate. The measured sorption isotherm data were fitted to the Freundlich equation. The results showed that, for the same soil, (i) the total HA mass extracted with Na₄P₂O₇ was 13.7–22.6% less than that extracted with NaOH, (ii) the Na₄P₂O₇-extracted HA had higher O/C atomic ratio, greater content of polar organic carbons (POC), and lower aliphatic carbon content than the NaOH-extracted HA, and (iii) the Na₄P₂O₇-extracted HA exhibited greater sorption isotherm linearity and but not dramatic difference in sorption capacities than the NaOH extracted HA. The differences in the HA properties resulting from the two different extraction methods may be because NaOH can hydrolyze insoluble HA fractions such as fatty acid like macromolecules bound on soils whereas Na₄P₂O₇ could not. As a result, the HAs extracted with the two different methods had different polarity and functionality which affected their sorption property for phenanthrene.     

Sorption of naphthalene and phenanthrene by soil humic acids

Humic acids are a major fraction of soil organic matter (SOM), and sorption of hydrophobic organic chemicals by humic acids influences their behavior and fate in soil. A clear understanding of the sorption of organic chemicals by humic acids will help to determine their sorptive mechanisms in SOM and soil. In this paper, we determined the sorption of two hydrophobic organic compounds, naphthalene and phenanthrene by six pedogenetically related humic acids. These humic acids were extracted from different depths of a single soil profile and characterized by solid-state CP/MAS 13C nuclear magnetic resonance (NMR). Aromaticity of the humic acids increased with soil depth. Similarly, atomic ratios of C/H and C/O also increased with depth (from organic to mineral horizons). All isotherms were nonlinear. Freundlich exponents (N) ranged from 0.87 to 0.95 for naphthalene and from 0.86 to 0.92 for phenanthrene. The N values of phenanthrene were consistently lower than naphthalene for a given humic acid. For both compounds, N values decreased with increasing aromaticity of the humic acids, such an inverse relationship was never reported before. These results support the dual-mode sorption model where partitioning occurs in both expanded (flexible) and condensed (rigid) domains while nonlinear sorption only in condensed domains of SOM. Sorption in the condensed domains may be a cause for slow desorption, and reduced availability and toxicity with aging.     

Evaluation of impacts of soil fractions on phenanthrene sorption

Phenanthrene sorption to soils and soil fractions was investigated using two contrasting soils with different clay mineral and organic carbon (OC) contents in an attempt to evaluate the contribution of each soil fraction to phenanthrene sorption and the applicability of the carbon-normalized distribution constant (K(OC)) in soils. Sorbents were characterized using surface analysis, solid-state (13)C NMR analysis, and glass transition temperature (T(g)) analysis to gain a insight into the chemical nature of OC in soils. Dissolved organic carbon (DOC) in the soil solution impeded the phenanthrene sorption, while humins accounted for the predominant phenanthrene sorption in soils. The contribution of OC to phenanthrene sorption in soil would be overestimated if only a K(OC)-approach was adopted, since clay minerals could account for much of the sorption, especially when OC was low in soils. Nitrogen gas was shown to be inappropriate for probing non-polar sorption capacity. The results obtained highlight the importance of clay minerals in governing the sorption of phenanthrene in soil, and emphasize the inapplicability of the carbon-normalized distribution coefficient K(OC) in soils.     

Sorption of polar and nonpolar organic contaminants by oil-contaminated soil

Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (K_oil). The resulting oil-contaminated soil–water distribution coefficients (K_d) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C_oil) but sorption-reducing (competitive) effects at intermediate C_oil (approximately 1 g kg⁻¹). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K_d at C_oil above approximately 1 g kg⁻¹ were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.     

On the use of a freeze-dried versus an air-dried soil humic acid as a surrogate of soil organic matter for contaminant sorption

The sorption of phenanthrene (PHN) to relatively pure soil humic acids (HAs) was investigated to assess the suitability of the soil HA as a surrogate sorbent for the soil organic matter (SOM). The HAs were prepared in both freeze-dried and air-dried forms. The two forms of HAs from the same source are similar in composition but the freeze-dried HAs exhibit a significantly higher initial surface area (SA) (3.86-4.59 m(2)/g); the SAs of air-dried HAs are below 0.1 m(2)/g. However, the SAs of freeze-dried HAs are not stable upon contact with water; the samples lose practically all the SA after 4 days of immersion in water. The PHN sorption to both forms of HAs is practically linear, whether a co-solute is present or not. The sorption linearity observed with the present freeze-dried HAs is in sharp contrast with the allegedly nonlinear PHN sorption on similar freeze-dried HAs as presented by others.     

Sorption of polar and nonpolar organic contaminants by oil-contaminated soil

Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (K_oil). The resulting oil-contaminated soil–water distribution coefficients (K_d) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C_oil) but sorption-reducing (competitive) effects at intermediate C_oil (approximately 1 g kg⁻¹). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K_d at C_oil above approximately 1 g kg⁻¹ were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.     

Long-term tillage effects on soil metolachlor sorption and desorption behavior

Sorption and desorption are two important processes that influence the amount of pesticides retained by soils. However, the detailed sorption mechanisms as influenced by soil tillage management are unclear. This study examined the sorption and desorption characteristics of metolachlor [2-chloro-N-(2-ethyl-6-methyphenyl)-N-(2-methoxy-1-methylethyl)-acetamide] using the soil samples collected from the long-term conservation tillage (CnT) and conventional tillage (CT) research plots established in 1979 in Darlinton, SC. Humic acid (HA) and humin were extracted from the soils and used in the sorption experiments along with the whole soil samples. The sorption experiments were conducted using a batch-equilibration method. Three sequential desorption rinses were carried out following the sorption experiments. By comparing metolachlor sorption and desorption results we observed hysteresis for all soil samples and their organic matter fractions. Sorption nonlinearity (N) and hysteresis were dependent on the structure and composition of soil organic matter (SOM), e.g., Freundlich isotherm exponents (N) of HA and humin from CnT were higher than those of CT treatment, which may be related to high aromaticity of SOM fractions in CT treatment. Sorption capacity (K'f) was positively correlated with soil organic carbon (SOC) content. These results show that long-term tillage management can greatly affect metolachlor sorption and desorption behavior probably by qualitative differences in the structural characteristics of the humic substances.     

Effect of physical forms of soil organic matter on phenanthrene sorption

The sorption coefficient, K(OC), of phenanthrene (PHE) has been reported to vary with different types of organic matter, leading to uncertainties in predicting the environmental behavior of PHE. Among the studies that relate organic matter properties to their sorption characteristics, physical conformation of organic matter is often neglected. In this work, organic matter samples of different physical forms were examined for their sorption characteristics. Dissolved humic acids (DHA) showed significantly higher K(OC) than the corresponding solid humic acids (SHA) from which the DHAs were made. The K(OC) of DHAs was found to be related to polarity, whereas K(OC) of SHAs increased with aliphatic carbon content. Soil particles were treated with H(2)O(2) to remove organic matter, and humic acid was coated on H(2)O(2)-treated soil particles to make organo-mineral complexes at pH 4, 7 and 10. Although the nonlinear sorption was apparent for SHAs and H(2)O(2)-treated soil particles, the organo-mineral complexes formed using these two components at pH 4, 7 and 10 exhibited relatively linear sorption at organic carbon content, f(OC)>0.5%. These results indicate that organic matter of the same composition may have different sorption properties due to different physical forms (or conformations). Nonlinear sorption for the complexes formed at pH 4 with lower f(OC) (<0.5%) was also discussed.     

Hydroxypropyl-β-cyclodextrin extractability and bioavailability of phenanthrene in humin and humic acid fractions from different soils and sediments

Organic matter (OM) plays a vital role in controlling polycyclic aromatic hydrocarbon (PAH) bioavailability in soils and sediments. In this study, both a hydroxypropyl-β-cyclodextrin (HPCD) extraction test and a biodegradation test were performed to evaluate the bioavailability of phenanthrene in seven different bulk soil/sediment samples and two OM components (humin fractions and humic acid (HA) fractions) separated from these soils/sediments. Results showed that both the extent of HPCD-extractable phenanthrene and the extent of biodegradable phenanthrene in humin fraction were lower than those in the respective HA fraction and source soil/sediment, demonstrating the limited bioavailability of phenanthrene in the humin fraction. For the source soils/sediments and the humin fractions, significant inverse relationships were observed between the sorption capacities for phenanthrene and the amounts of HPCD-extractable or biodegradable phenanthrene (p?<?0.05), suggesting the importance of the sorption capacity in affecting desorption and biodegradation of phenanthrene. Strong linear relationships were observed between the amount of HPCD-extractable phenanthrene and the amount degraded in both the bulk soils/sediments and the humin fractions, with both slopes close to 1. On the other hand, in the case of phenanthrene contained in HA, a poor relationship was observed between the amount of phenanthrene extracted by HPCD and the amount degraded, with the former being much less than the latter. The results revealed the importance of humin fraction in affecting the bioavailability of phenanthrene in the bulk soils/sediments, which would deepen our understanding of the organic matter fractions in affecting desorption and biodegradation of organic pollutants and provide theoretical support for remediation and risk assessment of contaminated soils and sediments.     

Sorption of 17α-ethinyl estradiol, bisphenol A and phenanthrene to different size fractions of soil and sediment

The potential for negative effects caused by endocrine disrupting chemicals (EDCs) release into the environment is a prominent concern and numerous research projects have investigated possible environmental fate and toxicity. However, their sorption behavior by size fractions of soil and sediment has not been systematically represented. The sorption of bisphenol A (BPA), 17α-ethinyl estradiol (EE2) and phenanthrene (Phen) by different size fractions of soil and sediment were investigated. Sorption isotherms of EE2, BPA, and Phen by size fractions of soil (SL) and sediment (ST) were well fitted to the Freundlich model. The positive correlation between EE2, BPA and Phen sorption capacity (log K_d) of size fractions and their organic carbon (OC) content suggests that OC of size fractions in SL and ST should regulate sorption, while the surface area (SA) of size fractions may not account for sorption of EE2, BPA and Phen. Each size fraction of ST had higher sorption capacity (K_d or K_OC) of EE2 and BPA than that of SL due to their difference in the polarity of organic matter (OM) between terrestrial and aquatic sources. Sorption capacity logK_d for size fractions of SL and ST did not follow the order: clay > silt > sand due to the difference in OM abundance and composition between the size fractions. Large particle fractions of ST contributed about 80% to the overall sorption for any EE2, BPA, and Phen. This study was significant to evaluate size fractions of soil and sediment as well as their associated OM affecting EE2 and BPA sorption processes.     

天然溶解性有机质对黑炭吸附萘和菲的抑制作用

研究了土壤天然溶解性有机质(富里酸或腐殖酸)对黑炭吸附萘和菲的影响.结果表明:增加天然溶解性有机质的负载量能够减弱黑炭对萘和菲的吸附能力；而同在100mg的负载量条件下,不同分子量的富里酸或腐殖酸的负载对黑炭吸附萘和菲的抑制作用没有明显差别；相对于富里酸或腐殖酸单独负载,金属离子(Al3+或Fe3+)和富里酸或腐殖酸联...     

H NMR metabolomics of earthworm exposure to sub-lethal concentrations of phenanthrene in soil

¹H NMR metabolomics was used to monitor earthworm responses to sub-lethal (50-1500 mg/kg) phenanthrene exposure in soil. Total phenanthrene was analyzed via soxhlet extraction, bioavailable phenanthrene was estimated by hydroxypropyl-β-cyclodextrin (HPCD) and 1-butanol extractions and sorption to soil was assessed by batch equilibration. Bioavailable phenanthrene (HPCD-extracted) comprised ∼65-97% of total phenanthrene added to the soil. Principal component analysis (PCA) showed differences in responses between exposed earthworms and controls after 48 h exposure. The metabolites that varied with exposure included amino acids (isoleucine, alanine and glutamine) and maltose. PLS models indicated that earthworm response is positively correlated to both total phenanthrene concentration and bioavailable (HPCD-extracted) phenanthrene in a freshly spiked, unaged soil. These results show that metabolomics is a powerful, direct technique that may be used to monitor contaminant bioavailability and toxicity of sub-lethal concentrations of contaminants in the environment. These initial findings warrant further metabolomic studies with aged contaminated soils.     

Correlations of nonlinear sorption of organic solutes with soil/sediment physicochemical properties

The estimation of solute sorptive behaviors is essential when direct sorption data are unavailable and will provide a convenient way to assess the fate and the biological activity of organic solutes in soil/sediment environments. In this study, the sorption of 2,4-dichlorophenol (2,4-DCP) on 19 soil/sediment samples and the sorption of 13 organic solutes on one sediment were investigated. All sorption isotherms are nonlinear and can be described satisfactorily by a simple dual-mode model (DMM): q(e)=KpCe+Q0 . bCe/(1+bCe), where Kp (mlg(-1)) is the partition coefficient; Ce (microgml(-1)) is the equilibrium concentration; Q0 (microgg(-1)) is the maximum adsorption capacity; Q0 . b (mlg(-1)) is the Langmuir-type isotherm slope in the low concentration (Henry's law) range and b (mlmicrog(-1)) is a constant related to the affinity of the surface for the solute. Based on these nonlinear sorption isotherms and similar other nonlinear isotherms, it is observed that, for both polar 2,4-DCP and nonpolar phenanthrene, Kp, Q0 and Q0 . b are linearly correlated with soil/sediment organic carbon content (f(oc) in the range of 0.118-53.7%). The results indicate that the nonlinear sorption of organic solutes results primarily from interactions with soil/sediment organic matter. The K*oc K*oc=Kp/f(oc)), Qoc (Qoc=Q0/f(oc)), Loc (Loc=Q0 . b/f(oc)) and b for a given organic solute with different soils/sediments are largely invariant. Furthermore, logK*oc, logb and logLoc for various organic solutes are correlated significantly with the solute logKow or logSw (logKow in the range of 0.9 to 5.13 and logSw in the range of -6.176 to -0.070). A fundamental empirical equation was then established to calculate approximately the nonlinear sorption from soil/sediment f(oc) and solute Sw for a given solute equilibrium concentration.     

Sorption of 1-naphthol to soil and geologic samples with varying diagenetic properties

Remediation of contaminated land requires a firm understanding of the processes that occur between xenobiotics and soil colloids. It is currently accepted that the extent of xenobiotic uptake is proportional to the carbon quantity and character of the soil or geologic sample. Previous studies have developed empirical equations to predict the extent of sorption based on the aromatic carbon content. We examined these relationships with an independent set of soil and geologic samples and 1-naphthol. The 1-naphthol sorption coefficients varied significantly (P < 0.01) among sorbents and are consistent with the diagenetic properties of the organic matter in these samples. The cross-polarization magic angle spinning (CPMAS) 13C nuclear magnetic resonance (NMR) and elemental data did not concur with the sorption data for most of the soil samples. We suggest that this contradiction may be due to a third variable, the physical organization of the organic matter. Chemical methods measure the whole sample, whereas short-term sorption occurs on the surface; therefore, only some organic matter domains in the soil are available for interaction with 1-naphthol. Hence, chemical data alone may be insufficient for predicting the sorption behavior of xenobiotics in soil and geologic samples.     

Temporal change in the distribution patterns of hexachlorobenzene and dichlorodiphenyltrichloroethane among various soil organic matter fractions

Residence time-dependent distribution patterns of hexachlorobenzene (HCB) and dichlorodiphenyltrichloroethane (DDT) among different soil organic matter fractions of three Chinese soils were investigated. Soil organic matter (SOM) was fractionated into fulvic acid (FA), humic acid (HA), bound-humic acid (BHA), lipid, and insoluble residue (IR) fractions using methyl isobutyl ketone (MIBK) method. Results revealed that as the residence time prolonged, the amounts of HCB and DDT in the FA, HA and BHA fractions decreased, while those in the lipid and IR fractions increased. One- and two-compartment first order, and one- and two-parameter pore-diffusion kinetic models were used to describe the mobility of HCB and DDT from the FA, HA and BHA fractions. The results suggest that excellent agreements were achieved between the experimental data and fits to the two-compartment first order kinetic model (R2>0.97). The transfer rates of HCB and DDT followed the order FA>HA>BHA.     

The equilibria of bisolute sorption on soil

The goal of this study was to investigate the effects of both concentration levels and loading sequence or contamination history of each pollutant on the equilibrium sorption of mixed organic pollutants on soils. We measured binary sorption equilibria for a soil using ten concentration levels for both phenanthrene and naphthalene. Both solutes were either simultaneously loaded or sequentially loaded (i.e., the second sorbate was loaded after the sorption of the first sorbate had attained equilibrium) on soil. The results showed different competitive sorption equilibria between phenanthrene and naphthalene. In the presence of phenanthrene and regardless of loading sequence, naphthalene exhibited consistently lower sorption capacities and the ideal adsorbed solution theory (IAST) slightly underestimates the naphthalene sorption equilibria. Conversely, the sorption equilibria of phenanthrene in the presence of naphthalene depended upon the loading sequence of the two sorbates on the soil. Little competition from naphthalene on the sorption equilibria of phenanthrene was observed when phenanthrene was loaded either simultaneously with or sequentially after naphthalene, but appreciable competition from naphthalene was observed when the soil had been pre-contaminated with phenanthrene. IAST slightly underestimates the phenanthrene sorption equilibria observed in the latter system, but it cannot estimate the phenanthrene sorption equilibria in the former two systems. We proposed that adsorption on internal surfaces of ink-bottle shaped pores within relatively flexible sorbent matrix may have caused the competitive sorption phenomena observed in this study. The study suggests that contamination history may have strong influence on the equilibrium sorption of organic pollutant mixtures.