Proton binding by humic and fulvic acids from pig slurry and amended soils

The knowledge of acid-base characteristics of humic acid (HA) and fulvic acid (FA) fractions of organic amendments and amended soils is of considerable importance for assessing their agronomic efficacy and environmental impact. In this work, the acid-base properties of HAs and FAs isolated from pig slurry, soils amended with either 90 or 150 m(3) ha(-1) yr(-1) of pig slurry for 3 yr, and the corresponding nonamended control soil were investigated by using a current potentiometric titration method. The nonideal competitive adsorption (NICA) model that describes proton binding by two classes of binding sites (carboxylic- and phenolic-type groups) was successfully fit to titration data. With respect to the control soil HA and FA, pig-slurry HA and FA were generally characterized by smaller carboxylic-type group contents, slightly smaller phenolic-type group contents, larger affinities for proton binding by the carboxylic-type groups, and much smaller, in the case of the HA fraction, or similar, in the case of the FA fraction, affinities for proton binding by the phenolic-type groups. Amendment with pig slurry determined a number of modifications in soil HAs and FAs, including decrease of acidic functional group contents, and slight increase of the proton affinity of the carboxylic-type groups. Further, a slight decrease of the affinities for proton binding by the phenolic-type groups of HAs was observed. These effects can have a large impact on the biological availability, mobilization, and transport of macro- and micronutrients, toxic metal ions, and xenobiotic organic cations in pig slurry-amended soils.     

Cadmium binding by fractions of dissolved organic matter and humic substances from municipal solid waste compost

The agricultural practice of amending soils with composted municipal solid waste (MSW) adds significant amounts of organic matter and trace metals, including Cd. Under these conditions, soluble organic complexes of Cd formed in the compost may be more significant than previously thought, due to Cd bioavailability and mobility in the soil environment. To study the relative importance of different types of organic ligands in MSW compost for the binding of Cd, six fractions of the dissolved organic matter (DOM) in addition to humic acid (HA) and fulvic acid (FA) were extracted and their complexation of Cd quantified at pH 7 using an ion-selective electrode (ISE). The highest complexing capacities (CC) for Cd were found for the most humified ligands: HA (2386 micromol Cd g(-1) C of ligand), predialyzed FA (2468 micromol Cd g(-1) C), and HoA, a fulvic-type, easily soluble fraction (1042 micromol Cd g(-1) C). The differences in CC for Cd of the various organic ligands were not directly related to total acid-titratable or carboxylic groups, indicating the importance of sterical issues and other functional groups. The strength of association between Cd and the organic ligands was characterized by calculating stability constants for binding at the strongest sites (pK(int)) and modeling the distribution of binding site strengths. The pK(int) values of the DOM fractions ranged between 6.93 (HiN: polysaccharides) and 8.11 (HiB: proteins and aminosugars), compared with 10.05 for HA and 7.98 for FA. Hence, the highly complex and only partially soluble organic molecules from compost such as HA and FA demonstrated the highest capacity to sequester Cd. However, strong Cd binding of organic ligands containing N-functional groups (HiB) in addition to a high CC of soluble, humified ligands like HoA indicated the relevance of these fractions for the organic complexation of Cd in solution.     

Interactions of organic compounds with wastewater dissolved organic matter: role of hydrophobic fractions

The role of structural fractions of dissolved organic matter (DOM) from wastewater in the sorption process of hydrophobic organic compounds is still not clear. In this study, DOM from two wastewater treatment plants (Lachish and Netanya, Israel) was fractionated to hydrophobic acid (HoA) and hydrophobic neutral (HoN) fractions. The fractions were characterized and their sorptive capabilities for s-triazine herbicides and polycyclic aromatic hydrocarbons (PAHs) were studied. For all sorbates, the binding to the HoN fractions was much higher than to HoA fractions. The HoA fractions were more polar than the HoN fractions, containing a higher level of carboxylic functionalities. However the higher binding coefficients of atrazine (2-chloro-4-ethylamine-6-isopropylamino-s-triazine) and ametryn [2-(ethylamino)-4-isopropylamino-6-methyl-thio-s-triazine] obtained for the HoN fractions suggest that their sorption is governed by hydrophobic-like interactions rather than H bonding. The values of binding coefficients of PAHs measured for the HoN fractions were within the range reported for humic acids and much higher than other fractions, suggesting that this fraction plays an important role in the overall sorption of these compounds by DOM. Higher sorption coefficients were measured for the Netanya DOM sample containing higher level of hydrophobic fractions (HoA + HoN) than the Lachish DOM, suggesting that the sorption of hydrophobic organic compounds by DOM is governed by the level of these structural substances. The evaluation of mobility of organic pollutants by wastewater irrigation requires not only assessment of the total carbon concentration but also, more importantly, the content of the hydrophobic fractions.     

Comparative analysis of partial structures of a peat humic and fulvic acid using one- and two-dimensional nuclear magnetic resonance spectroscopy

Nuclear magnetic resonance (NMR) resonance integrals obtained from one-dimensional NMR spectra provide semiquantitative contents of humic constituents with limited resolution in structural detail. When supplemented by connectivity information available from homo- and heteronuclear two-dimensional NMR spectra a more reliable assignment of humic substructures becomes available. This is demonstrated with a comparative one- and two-dimensional NMR analysis of a fulvic and a humic acid obtained from Eriophorum peat. An example of a detailed analysis of the proton chemical shift region normally attributed to carbohydrates shows substantial contributions from amino acids, amino and desoxy sugars, and highly oxidized aliphatic chains of intermediate length. The very good resolution of structural detail by a combined analysis of all NMR spectra shows that the effect of the fractionation procedure on the composition and chemical structure of humic materials is very significant. The comparison of the partial structures comprising humic acid (HA) and fulvic acid (FA) of the peat humic materials studied indicates that FA is diagenetically downstream of HA, favoring the biopolymer degradation (BD) model of humification.     

Enzymatic transformation and binding of labeled 2,4,6-trinitrotoluene to humic substances during an anaerobic/aerobic incubation

Organic pollutants are degraded in soil and simultaneously nonextractable residues are formed. However, proof is lacking that this fixation has a detoxifying effect. We investigated the transformation and binding of 2,4,6-trinitrotoluene (TNT) with catechol or soil humic acid as cosubstrates. Carbon-14-labeled TNT and its reaction products were quantified by radiocounting; extractable compounds were identified by high performance liquid chromatography (HPLC). Bound and extractable residues of 15N-labeled TNT and metabolites were studied by 15N nuclear magnetic resonance spectroscopy (15N NMR). Since TNT is not easily transformed under oxidizing conditions an anaerobic/aerobic treatment was used. Anaerobic microorganisms from cow manure were used to reduce TNT during the anaerobic phase and subsequently, a laccase from Trametes villosa was used in the aerobic phase to oxidatively couple the metabolites to humic matter. Seventy-four percent of TNT was immobilized with catechol as cosubstrate, but only 25% with humic acid. With catechol the main extractable component was TNT, while with humic acid it was mostly the metabolite 4-aminodinitrotoluene. For both co-substrates, the spectra of immobilized metabolites obtained by solid-state 15N-cross polarization magic angle spinning (CPMAS) NMR spectroscopy showed signals in the chemical shift region for protonated aromatic amino compounds. However, in the presence of catechol, an additional signal from nonextractable nitro groups was found, which could represent sequestered TNT. The partially reduced metabolites of TNT that formed nonextractable residues in humic acid are not likely to be remobilized easily and are thus regarded as detoxified.     

Structural and sorption characteristics of adsorbed humic acid on clay minerals

Clay-humic complexes are commonly distributed in natural environments. They play very important roles in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study examined the structural changes of humic acid (HA) after adsorption by clay minerals and determined phenanthrene sorption by clay-humic complexes. Solid- and liquid-state 13C nuclear magnetic resonance (NMR), for the first time, provided direct evidence for HA fractionation during adsorption on mineral surfaces, that is, aliphatic fractions were preferentially adsorbed by clay minerals while aromatic fractions were left in the solution. The ratio of UV absorbance of HA at 465 and 665 nm (E4 to E6 ratio), which is related to aromaticity, corroborated with the NMR results. For both montmorillonite and kaolinite, adsorbed HA fractions had higher sorption linearity (N) and affinity (K(oc)) than the source HA. The K(oc) of adsorbed HA for the clay-humic complexes could be up to several times higher than that of the source HA. This large increase may be contributed by the low polarity of the bound HA. Moreover, for each mineral, the N values of adsorbed HA increased with increasing HA loading. It is believed that HA may develop a more condensed structure on mineral surface at lower HA loading level due to the stronger interactions between HA and mineral surface as a result of close contacts.     

Direct link between fluoranthene biodegradation and the mobility and sequestration of its residues during aging

The aim of this study was to assess the influence of the polycyclic aromatic hydrocarbons (PAH)-degrading activity in the fate of fluoranthene in soils. Three soil samples with different degrading activities (an industrial soil, the same industrial soil after biostimulation, and an agricultural soil) were spiked with 14C-fluoranthene and incubated for 6 mo with monitoring of biodegradation and mineralization. To follow the distribution of the 14C-fluoranthene residues (i.e., 14C-fluoranthene and its degradation products) among the soil compartments, we performed successively leaching, centrifugation (to collect intra-aggregate pore water), solvent extraction, and combustion of the soil columns. In the industrial soil, no mineralization of 14C-fluoranthene was observed, and only 3% of the initial 14C-activity was non-extractable (with acetone:dichloromethane) after 165 d of incubation. The biostimulation (addition of unlabeled polycyclic aromatic hydrocarbons) increased the degrading activity in this soil (59% of 14C-fluoranthene was mineralized) and increased the residues sequestration (13% of 14C-activity was non-extractable). The microflora of the agricultural soil mineralized 14C-fluoranthene more slowly and to a lesser extent (25%) than the biostimulated soil, but a higher amount of 14C-activity was sequestered (41%). Thus, the rate and extent of 14C-fluoranthene mineralization seemed to be related to the 14C-activity sequestration by controlling the accumulation of degradation products in the soil. 14C-Fluoranthene biodegradation enhanced the concentration of 14C-polar compounds in the intra-aggregate pore water. Our results point out the close link between fluoranthene biodegradation and two key aging processes, diffusion and sequestration, in soils. Biodegradation controls the mobility and sequestration of residues by transforming fluoranthene into more polar molecules that can diffuse into the intra-aggregate pore water and then might become bound to the matrix or entrapped in the microporosity.     

Transport and retention of fullerene nanoparticles in natural soils

Commercial production and use of fullerene (C60) nanomaterials will inevitably lead to their release into the environment, where knowledge of C60 fate and transport is limited. In this study, a series of one-dimensional column experiments was conducted to assess the transport and retention of nanoscale fullerene aggregates (nC60) in water-saturated soils. Under the experimental conditions, complete retention of nC60 was observed in columns (2.5 cm inside diameter x 11 cm length) packed with Appling or Webster soil, which contain 0.75 and 3.33% organic carbon by weight, respectively. When the volume of aqueous nC60 suspension (approximately 4.5 mg L(-1)) applied to Appling soil was increased from 5 to 65 pore volumes, the travel distance increased from 3 to 8 cm, and the retention capacity approached a limiting value of 130 microg g(-1), although nC60 was not detected in the column effluent. The addition of 20 mg C L(-1) Suwannee River humic acid to the influent suspension increased the nC60 transport in Appling soil but did not resul in breakthrough. Attempts to simulate the experimental data using clean-bed filtration theory were not satisfactory, yielding retention profiles that failed to match observed data. Subsequent incorporation of a limiting retention capacity expression into the mathematical model resulted in accurate predictions of the measured nC60 retention profiles and transport behavior. The sizable retention capacities observed in this study suggest that transport of nC60 is limited in relatively fine-textured soils containing appreciable amounts of clay minerals and organic matter, with substantial accumulation of nC60 aggregates near the point of release.     

Relationship between compost stability and extractable organic carbon

Establishing a simple yet reliable compost stability test is essential for a better compost quality control and utilization efficiency. The objective of this study was to examine the relationship between extractable organic carbon (OC) and compost stability based on 18 compost samples from five composting facilities. The compost samples were extracted sequentially with water for 2 h [water(2h)] and 0.1 M NaOH for 2 and 24 h [NaOH(2h) and NaOH(24h), respectively]. The extractable OC was further separated into fulvic acid (FA) and humic acid (HA) fractions by adjusting the pH to <2. The mass specific absorbance (MSA) of OC in the six fractions was measured. Compost stability was estimated with a CO2 evolution method. The extractable OC concentration was influenced by the total volatile solids and decreased with curing time for compost with a high level of extractable OC. The OC levels in each fraction were significantly correlated (p < 0.05) to each other except for the water(2h)-extractable HA. In addition, all the FA and HA fractions except for water(2h)-extractable HA were highly (P < 0.01) and linearly correlated to CO2 evolution, but multiple regression showed that NaOH(24h)-extractable OC was insignificant for CO2 evolution. The relatively high slope of NaOH(2h)-extractable FA versus CO2 evolution suggests that this fraction may contribute the most to compost CO2 evolution. The water(2h)- and/or NaOH(2h)-extractable FA tests are recommended for measuring compost stability because of their high correlation with CO2 evolution. This estimation can be obtained through a simple photometric method covering a wide range of carbon concentrations up to 4,000 mg L(-1).     

Distribution behavior of pyrene to adsorbed humic acids on kaolin

The distribution behavior of pyrene on humic acid (HA)-kaolin complexes, prepared by adsorbing HA on kaolin, was investigated by batch experiments. The distribution coefficient (Kd) of pyrene on the HA-kaolin complex increased with the fraction (f(oc)) of organic carbon adsorbed to the surface of the kaolin. This can be attributed to hydrophobic interactions between pyrene and the adsorbed HAs. The effects of adsorbed HAs were quantitatively evaluated by calculating the distribution coefficient (K(oc)) and affinity constant (K(oc)ads) for pyrene to the adsorbed HAs. A fluorescence quenching method was employed to determine the affinity constant (K(oc)aq) of pyrene to HAs dissolved in an aqueous solution. When the K(oc) values were compared with the K(oc)aq values, the K(oc) values were found to be 4 to 11 times larger than the K(oc)aq values. On the other hand, the K(oc)ads values were 4 to 9 times larger than the K(oc)aq values. These indicate that the affinity for pyrene is enhanced by the adsorption of HAs to kaolin. In addition, the K(oc) values increased with increasing average molecular weights of the HAs. These results demonstrate that HAs, when they are adsorbed to clay minerals, play an important role in the deposition of polycyclic aromatic hydrocarbons (PAHs) in a soil environment.     

Sorption and desorption of naphthalene by soil organic matter: importance of aromatic and aliphatic components

Nonlinear isotherm behavior has been reported for the sorption of hydrophobic organic compounds (HOCs) in soil organic matter (SOM), but the exact mechanisms are unknown. Our objective was to provide insight into the sorption mechanism of HOCs in SOM by studying the sorption-desorption processes of naphthalene in a mineral soil, its humic fractions, and lignin. Additionally, humin and lignin were used for studying the effects of temperature and cosolvent on HOC sorption. All isotherms were nonlinear. The humin and lignin isotherms became more linear at elevated temperatures and with the addition of methanol indicating a condensed to expanded structural phase transition. Isotherm nonlinearity and hysteresis increased in the following order: soil humic acid (HA) < soil < soil humin. Of the samples, aliphatic-rich humin exhibited the largest degree of nonlinearity and had the highest sorption capacity for naphthalene. High nonlinearity and hysteresis in humin were most likely caused by its condensed structure. A novel aliphatic, amorphous condensed conformation is proposed. This conformation can account for both high sorption capacities and increased nonlinearity observed for aliphatic-rich samples and can explain many sorption disparities discussed in the literature. This study clearly illustrates the importance of both aliphatic and aromatic moieties for HOC sorption in SOM.     

Characterization and coagulation of a polyaluminum chloride (PAC) coagulant with high Al13 content

A polyaluminum chloride (PAC) coagulant was prepared from AlCl3 x 6H2O and Na2CO3. The Al13 species in PAC was separated and purified by the SO4(2-)/Ba2+ deposition-replacement method, and characterized by 27Al-NMR and XRD. From 27Al-NMR spectroscopy, it was found that PAC obtained after separation and purification contained more Al13 (PAC-Al13, for short) than original PAC before separation and purification. In XRD spectra, a strong Al13 signal appeared in the range of 2theta from 5 to 25 degrees. Jar tests were performed to test the coagulation efficiency of AlCl3, PAC and PAC-Al13 in treating synthetic or actual water samples. Compared with PAC and AlCl3, PAC-Al13 gives the best results for turbidity, humic acid and color removal, and achieves the highest charge-neutralizing ability. Under the study conditions, PAC-Al13 gave about 90% humic acid removal and almost 100% reactive blue dye removal when its dosages were 4.0 and 15 mg/L as Al, respectively. The Al13 species has a higher positive charge and is the most effective polymeric Al species in water and wastewater treatment.     

Degradation of 14C-atrazine bound residues in brown soil and rendzina fractions

The remobilization and the fate of 14C-ring labeled atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) bound residues was examined in relation with the turnover of natural soil organic matter. Soil fractions of a brown soil and a rendzina were incubated under controled laboratory conditions. The mineralization of natural organic matter and atrazine-bound residues was respectively estimated by the amounts of CO2 and 14CO2 evolved during the incubation. The remobilization and distribution of 14C residues among the soil organic fractions were achieved after physical-chemical extractions of the samples. Comparisons of samples in abiotic and biotic conditions allowed us to assess the influence of microbial activity on the fate of atrazine-bound residues. The mineralization curves showed that natural organic matter and atrazine-bound residues had similar decomposition patterns. After 100 d of incubation, 0.8 to 3.6% of total organic C was evolved as CO2, while only 0.1% of the initial radioactivity was mineralized as CO2, and 7 to 15% was becoming extractable with water and methanol. Few differences were observed in the distribution of residues within organic compounds for both fractions of the rendzina, except a decrease of the 14C radioactivity of the 50- to 5000-microm fraction and a slight increase of that of humin. For the 0- to 5000-microm brown soil fraction, increased radioactivity in humin at the expense of humic (HA) and fulvic (FA) acids was detected after incubation, while for the 0- to 50-microm fraction more radioactivity was recovered with FA.     

黄腐酸的萃取和性质研究

黄腐酸是腐植酸中最具活力的组成部分,蕴藏量丰富,萃取方法简便。研究了从红原1#泥炭中萃取黄腐酸和降解物。它的分子量较小,易溶于水,抗絮凝性能好,分子内含有较多的活性官能团,具有很高的化学活性和生物活性,用途广泛。     

东营市大气颗粒物中有机污染物的色谱－质谱分析

报道了应用气相色谱和气相色谱。质谱联用法对东营市大气颗粒物中正构烷烃和多环芳烃的分析结果，实际分析中共鉴定出正构烷烃２１种，多环芳烃６３种。定量测定结果表明，东营市冬季大气颗粒物中的总正构烷烃浓度和苯并（ａ）芘浓度均低于国内其他大城市。     

Sorption of aromatic compounds to clay mineral and model humic substance-clay complex: effects of solute structure and exchangeable cation

Clay minerals and humic substance (HS)-clay complexes are widely distributed in soil environments. Improved predictions on the uptake of organic pollutants by soil require a better understanding of fundamental mechanisms that control the relative contribution from organic and inorganic constituents. Five selected aromatic compounds varying in electronic structure, including nonpolar phenanthrene (PHEN), 1,2,4,5-tetrachlorobenzene (TeCB), polar 1,3-dinitrobenzene (DNB), 2,6-dichlorobenzonitrile (dichlobenil [DNL]), and 1-naphthalenyl methylcarbamate (carbaryl [CBL]), were sorbed separately from aqueous solution to Na(+)-, K(+)-, Cs(+)-, and Ca(2+)-saturated montmorillonites with and without the presence of dissolved HS at pH about 6. Upon normalizing for hydrophobic effects by solute aqueous solubility, the overall trend of sorptive affinity to HS-free K(+)-clay is DNB > DNL, CBL > PHEN, TeCB, indicating preferential adsorption of the polar solutes. With the presence of HS, sorption of PHEN, TeCB, and CBL increases by several times compared with the pure clay, attributed to HS-facilitated hydrophobic partition (PHEN and TeCB) or H-bonding (CBL). The enhanced sorption of PHEN by HS is cation dependent, where Cs(+) shows the strongest facilitative effect. Coadsorption of HS does not affect sorption of DNB and DNL to clays except that of DNB to Ca(2+)-clay because cation-dipole interactions between the polar group (NO(2) or CN) of solute and weakly hydrated exchangeable cations dominate the overall sorption.     

Validation of procedures to quantify nonextractable polycyclic aromatic hydrocarbon residues in soil

This study was conducted to optimize butanol solvent shake extraction, dichloromethane soxtec extraction, and methanolic saponification extraction for the selective extraction of aged polycyclic aromatic hydrocarbons from soil. Extraction kinetics for these methods was established to determine the optimal time necessary to achieve exhaustive compound extraction. This resulted in times of 12, 6, and 5 h, respectively, for butanol, dichloromethane, and saponification, to extract polycyclic aromatic hydrocarbons from previously spiked, then aged soil. Increasing the soil mass to butanol volume ratio reduced the proportion of polycyclic aromatic hydrocarbon extracted by butanol, highlighting the importance of determining and maintaining a constant soil to solvent ratio for comparative purposes. Drying soil samples before dichloromethane soxtec extraction reduced by 30 to 76% the amount of polycyclic aromatic hydrocarbons extracted. The effect of sample drying is discussed with relevance to enhancing the formation of nonextractable compounds in soil and compound losses previously assumed by volatilization. The optimized extraction procedures provided low variability with relative standard deviations < or = 5.2% for analysis of multiple replicates. The results obtained by the optimized procedures provided equivalent or improved reproducibility to those obtained by other methods reported in the literature.     

Sorption interactions between imazaquin and a humic acid extracted from a typical Brazilian oxisol

Soil sorption of most hydrophobic organic compounds (e.g., nonpolar pesticides) is directly related to soil organic matter (SOM) content. Humic substances are the major SOM components, containing carboxylic, phenolic, amine, quinone, and other functional groups, and specific structural configurations. In this paper, sorption interactions between imazaquin (2-[4,5-dydro-4-methyl-4-(1-methylethyl)-5-oxo-1H- imidazol-2-yl]-3-quinoline-carboxylic acid) herbicide (IM) and a humic acid (HA) extracted from a typical Brazilian Oxisol were studied with electron paramagnetic resonance (EPR) and Fourier-transform infrared (FTIR) spectroscopic techniques. A polarographic technique was used to quantify sorption. The IM amount sorbed on the HA was much higher than that on the whole soil within the pH range studied, emphasizing the prominent role played by SOM on IM sorption. Moreover, IM sorption increased as the soil-solution pH decreased. This enhancement in sorption was attributed to the hydrophobic affinity of the herbicide by the HA and to the electrostatic interaction between the protonated quinoline group of IM and the negative sites of the HA. Hydrophobic regions in the HA's interior at low pH (< 5.0) were recently demonstrated by an EPR detectable spin-label molecule. The FTIR and EPR spectroscopy and polarography data indicated weak interaction between IM and the soil and its HA, involving hydrogen bonding, proton transfer, and cation exchange (at low pH), and mainly hydrophobic interactions. However, no strong reaction mechanism, such as charge transfer, was involved. In addition, this research suggested that soil amendment with organic material might increase magnitude of IM sorption, consequently avoiding leaching and carryover problems usually found for mobile and persistent herbicides such as imazaquin.     

不同物质对垃圾渗滤液中腐殖酸的吸附研究

垃圾渗滤液是一种有毒有害的高浓度有机废水,其中含大量腐殖酸。腐殖酸具有离子交换能力、吸附能力和脱除杂质能力,因此在很多方面有实用价值。活性碳、土壤、堆肥对废水中的有机物有一定的吸附能力。本文采用正交设计的方法,研究了活性碳、土壤、堆肥在不同温度,液／固,腐殖酸初始浓度的条件下对垃圾渗滤液中腐殖酸的吸附效果。实验结果表明：四种实验因素对吸附剂的吸附能力的影响程度为：吸附剂类型〉腐殖酸的初始浓度〉吸附反应温度〉液固比。在温度为25℃,液固比为50／0．5（mL/g）,腐殖酸初始浓度为41．99（mg／L）,吸附剂类型为活性碳时,腐殖酸吸附量最大,为40．86mg。同时分析了响应指标随因素的变化趋势。     

The influence of lipids on the energetics of uptake of polycyclic aromatic hydrocarbons by natural organic matter

Although most of the organic carbon in soils and sediments may be composed of humic substances, their interaction with other compounds, especially their sorption interactions, may be significantly affected by the presence of small amounts of the other components of natural organic matter (NOM). In this investigation, the influence of the lipid fraction of NOM on the sorption thermodynamics of fluorene, phenanthrene, and pyrene to several geosorbent samples was examined before and after extraction of lipids. Batch experiments were performed at the same concentration for all polycyclic aromatic hydrocarbons (PAHs) (0.025 x their solubility in water) at different temperatures (10, 20, 30, and 40 degrees C), and the thermodynamic parameters were calculated. Removal of the lipids increases the sorption capacity of the samples as well as the exothermicity of the process. The free energy change was negative for all the samples and no significant differences were noticed on lipid removal. The entropy changes were small and positive for the whole geosorbent samples, but even smaller or more negative when the lipids were removed. This indicates that the interaction of PAHs with soils and sediments in the absence of extractable lipids is stronger and the mechanisms involved may be different, changing from a partitioning-like mechanism to specific adsorption. Because of the competition between lipids and PAHs for the same sorption sites, the lipids can be viewed as an "implicit sorbate."