SOME NEW EQUATIONS TO DESCRIBE PHOSPHATE SORPTION BY SOILS

Phosphate sorption was studied on surface and subsurface soils sampled from the old field experiments at Askov, Denmark. Two empirical three-parameter equations, an extended Freundlich and an extended Langmuir equation are proposed and compared with the Langmuir, the Freundlich, the ‘double’ Langmuir, the Gunary, and the Fitter-Sutton equations. In the proposed equations the affinity parameter of the Langmuir equation and the exponent of the Freundlich equation are replaced by the term Bc ^?D the value of which decreases with increasing phosphate concentration, c. On average the Freundlich equation thus modified yielded the closest fit to the sorption data. This was followed by the Fitter-Sutton, the modified Langmuir, the ‘double’ Langmuir, the Gunary, the Freundlich, and finally the Langmuir equation. Out of the three equations that yielded the closest fit to the sorption data the correlation between the parameters within the equations, furthermore, was least for the proposed extended Freundlich equation. Therefore, this equation may be generally suitable for describing phosphate sorption by soils.     

Response of the sorption behavior of Cu,Cd, and Zn to different soil management

This study investigated the effect of different farming practices over long time periods on the sorption‐desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long‐term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients K_F increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO₃)₂ < animal manure ≤ grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants K_F and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water‐soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.     

活化过硫酸钠氧化土壤对挥发性有机污染物吸附特性的影响

活化过硫酸钠(Sodium persulfate,SPS)氧化技术是一种新型的土壤修复技术。为了更科学地评价化学氧化处理后土壤的环境风险,本文通过亚铁离子活化过硫酸钠法对有机质(Organic matter,OM)含量存在显著差别的两种土壤进行氧化处理,比较了活化过硫酸钠氧化前后两种土壤样品对3种挥发性有机污染物的吸附特性。结果表明,亚铁活化的SPS能够氧化土壤中腐殖酸和胡敏素类的有机质。对OM含量较高的1号土,SPS氧化对有机质的去除率为71.9%。而对OM含量较低的2号土,SPS氧化对有机质的去除率为49.9%。1号土样对3种挥发性有机物的吸附以分配作用为主,氧化后的1号土样对3种物质的吸附机制不变,但吸附量有所增加;2号土样对3种挥发性有机污染物的吸附有一定的非线性,而氧化后的2号土样对3种物质的吸附线性特征增强。吸附数据用对数形式的Freundlich方程拟合得到分配系数lg Kf值,比较有机碳标化后的分配系数lg Kfoc,氧化后的土壤有机质对3种挥发性有机污染物的吸附特性有所提高。分析表明,SPS氧化了有机质中较多的极性组分(如羧基及羟基等),从而使处理后的土壤中有机质的非极性增强,强化了对非极性化合物的吸附。     

Sorption of phosphorus in field-moist and air-dried samples from four weakly developed cultivated soil profiles

Sorption of phosphorus (P) in complete soil profiles in northern Europe is not adequately documented. I measured the sorption in genetic horizons of four cultivated soils (Inceptisols, Spodosol) in Finland using both field‐moist and air‐dried soil samples, fitted modified Freundlich equations (Q = a × I^b ? q) to the data, and presented the results in quantity/intensity (Q/I) graphs. Least‐squares‐estimates for the parameters of the modified Freundlich equation (a, b, q) were found to be imprecise measures of sorption. Values derived from the fitted equations (the amount of P sorbed at the P concentration of 2 mg litre^?1 and P buffering capacity at the same concentration) were more precise. Both were correlated with concentrations of oxalate‐extractable iron and aluminium. In all soils, there was a distinct difference in sorption between the fertilized Ap horizons and the subsurface horizons, which retained P strongly. Most of the sorption capacity was located in the B horizons at depths between 0.3 and 0.7 m. The results demonstrate the effects of soil‐forming processes and human impact on the sorption of P in the soils. Drying the samples prior to the sorption experiments altered the shape of the Q/I graphs. It increased dissolution of P at small P concentrations, sorption at large P concentrations, and the estimates for P buffering capacity. The effects of drying soil samples on the results and the imprecision of the parameters estimated with the modified Freundlich equation should be taken into account when interpreting results of Q/I experiments.     

Behavior of phenol and aniline on selected sorbents and energy-related solid wastes

The sorption and desorption of phenol and aniline on selected soils and soil components and on some energy-related solid wastes were investigated. Isotherms were generally nonlinear and were described usually by the Freundlich equation. Most partition coefficients were low, and no significant correlation was shown with organic C content, pH, cation exchange capacity, or particle-size of the sorbent. It appears that sorption of small polar aromatic compounds, such as phenol and aniline, cannot be defined by a single sorbent characteristic, but is affected by both the organic and mineral components of the sorbents. Hysteresis was observed in most sorption-desorption experiments; a fraction of the sorbate was irreversibly held by the sorbent.     

Sorption of atrazine, 2,4‐D,nitrobenzene and pentachlorophenol by urban and industrial wastes

This study was carried out to investigate the sorption properties of man‐made soil developed from sewage sludge, municipal wastes, brick and mortar debris, harbour sludge, sand fills, fly ash, and wastes from coking plants and coal mines. The composition of organic matter in the samples was analysed, and the sorption isotherms of four reference chemicals (nitrobenzene, atrazine, 2,4‐D, pentachlorophenol) were determined. Fly ash, which contains up to 89% of its carbon as Black Carbon, showed a strong affinity to all four chemicals. For the other waste materials, a strong correlation between the logarithm of the Freundlich adsorption constant, K_f, and the logarithm of organic carbon, C_o, was established (r = 0.85–0.96). This holds for the non‐ionic nitrobenzene and also, within a certain pH range depending on the pK_a of the compound, for the three ionizable organic compounds (atrazine: pH > 4; 2,4‐D: pH > 5; PCP: pH > 6). At pH near the pK_a value the sorption is sensitive to pH. There were no statistically significant differences between the waste materials and the natural soils in the relations between logK_f and logC_o for either ionic or non‐ionic chemicals. This result suggests that the method devised for estimating the sorption of organic chemicals in natural soils based on their content of organic carbon is equally valuable for the waste materials, with the exception of fly ash which contains a large amount of Black Carbon.     

Cyanogenic Residues: Environmental Impacts,Complexation with Humic Substances,and Possible Application as Biofertilizer

Treated and untreated rice straw extensively exists in the soil. In order to elucidate its possible effect on the fate of organic pollutants, sorption of pyrene by rice straw and its main constituents (lignin, cellulose, and hemi-cellulose) were studied, as single solute and in the presence of other co-existing organic pollutants, phenanthrene (Phen), benzo[a]pyrene (BaP), phenol, and pentachlorophenol (PCP). Pyrene showed the greatest sorption on lignin with greater aromaticity and smaller polarity, and the sorption coefficient was almost two orders of magnitude greater than those on cellulose and hemi-cellulose. Bi-solute sorption results showed that Phen, BaP and PCP exhibited apparent competitive sorption with pyrene on the four sorbents; while the existence of phenol promoted the sorption of pyrene on rice straw and lignin but inhibited the sorption on cellulose and hemi-cellulose. For the two polycyclic aromatic hydrocarbon (PAH) co-solutes and PCP, hydrophobicity and molecular size played important roles in competition, suggesting the direct competition for hydrophobic sorption sites and pore blockage mechanisms. In contrast, the polar co-solute, phenol showed different effects on pyrene sorption onto the four sorbents, suggesting that multiple interactions between polar organic compounds and sorbents are involved in the sorption.     

土壤中黑碳对农药敌草隆的吸附-解吸迟滞行为研究

采用批处理振荡法和连续稀释法分别测定了敌草隆在人工添加黑碳土壤和自然形成的不同有机质和黑碳含量的土壤中的吸附一解吸行为。吸附结果表明，人工添加黑碳的土壤对敌草隆的吸附强度和吸附容量以及吸附等温线的非线性均随土壤黑碳添加浓度的增加而逐步增大；自然土壤的吸附容量和吸附强度随土壤总有机质含量增加而增加，但吸附等温线的非线性则与土壤中黑碳对有机质的相对含量有关，黑碳比例越高，等温线非线性越大。解吸实验结果表明，无论是人工添加黑碳的土壤还是自然土壤，对敌草隆的解吸迟滞作用均随土壤黑碳含量增高而愈明显。     

Dissolved organic matter sorption by mineral constituents of subsoil clay fractions

The retention of dissolved organic matter in soils is mainly attributed to interactions with the clay fraction. Yet, it is unclear to which extent certain clay‐sized soil constituents contribute to the sorption of dissolved organic matter. In order to identify the mineral constituents controlling the sorption of dissolved organic matter, we carried out experiments on bulk samples and differently pretreated clay‐size separates (untreated, organic matter oxidation with H₂O₂, and organic matter oxidation with H₂O₂ + extraction of Al and Fe oxides) from subsoil horizons of four Inceptisols and one Alfisol. The untreated clay separates of the subsoils sorbed 85 to 95% of the dissolved organic matter the whole soil sorbed. The sorption of the clay fraction increased when indigenous organic matter was oxidized by H₂O₂. Subsequent extraction of Al and Fe oxides/hydroxides caused a sharp decrease of the sorption of dissolved organic matter. This indicated that these oxides/hydroxides in the clay fraction were the main sorbents of dissolved organic matter of the investigated soils. Moreover, the coverage of these sorbents with organic matter reduced the amount of binding sites available for further sorption. The non‐expandable layer silicates, which dominated the investigated clay fractions, exhibited a weak sorption of dissolved organic matter. Whole soils and untreated clay fractions favored the sorption of ”︁hydrophobic” dissolved organic matter. The removal of oxides/hydroxides reduced the sorption of the lignin‐derived ”︁hydrophobic” dissolved organic matter onto the remaining layer silicates stronger than that of ”︁hydrophilic” dissolved organic matter.     

Specific sorption of trace amounts of cadmium by soils

Abstract

Sorption of trace quantities of Cd in four soils of different chemical and mineralogical properties, was studied. Initial Cd concentrations were between 15 to 150 μg. 1^?1. The sorption isotherms were linear and had a positive intercept in three of the soils, indicating a constant partition‐high affinity sorption isotherm (Giles et. al⁶). The data also followed the Freundlich sorption isotherm, and the Freundlich K parameter was taken as a measure of the relative affinity of the different soils for the Cd metal sorbed. Cadmium sorbed was extracted by IN‐NH₄C1 followed by 0.1N HC1, and the fraction remaining in the soils was considered specifically sorbed Cd. This fraction also followed a linear sorption isotherm, and was around 30% for the four soils studied. The sorption order for the amount of specifically sorbed Cd showed that the Boomer soil (kaolinite‐iron oxides) had the lowest affinity for specific sorption of this metal. This was taken as evidence that kaolinite and iron oxides have a lower capacity for retaining cadmium through specific sorption mechanism(s) than the materials present on the other soils (2:1 layer silicates and humic substances). The existence of specific mecha‐nism(s) responsible by the sorption of trace quantities of Cd in soil solutions has important implications on soil‐plant relationships, Cd mobility in soil profiles and control of Cd activity in soil solutions.     

Low-molecular weight organic acids improve plant availability of phosphorus in different textured calcareous soils

Understanding the role of organic acids on phosphorus (P) sorption capacity of soils is very important for its economic and friendly management. Combining P application with low-molecular weight organic acids could result in its higher plant availability for prolonged time. Therefore, citric and oxalic acid (at the rate of 1.0 mM kg^?1 soil) were evaluated for their effect on P sorption capacity and its plant availability in two different textured calcareous soils. Organic acids decreased P sorption capacity and organic carbon partition coefficient (K_oc) whereas increased Gibbs free energy (ΔG) of P. Organic-acid-treated soils required lesser quantity of P fertilizer to produce soil solution P concentration optimum for plant growth (external P requirement [EPR_0.2]), that is, 0.2 mg L^?1. Citric acid was efficient than oxalic acid in the above effects. P sorption parameters of Freundlich model were negatively correlated with lime potential and ΔG whereas had positive correlation (P < 0.05) with EPR_0.2 and K_oc. Incubation with oxalic acid increased available P in loamy sand and loam soil by 20% and 30%, respectively. Thus, organic acids could help reduce application rate of P fertilizer through lowering its adsorption in highly P-fixing soils without compromise on yield.     

Retention of dissolved organic matter by illitic soils and clay fractions: Influence of mineral phase properties

The dependency of the retention of dissolved organic carbon (DOC) on mineral phase properties in soils remains uncertain especially at neutral pH. To specifically elucidate the role of mineral surfaces and pedogenic oxides for DOC retention at pH 7, we sorbed DOC to bulk soil (illitic surface soils of a toposequence) and corresponding clay fraction (< 2 μm) samples after the removal of organic matter and after removal of organic matter and pedogenic oxides. The DOC retention was related to the content of dithionite‐extractable iron, specific surface area (SSA, BET‐N₂ method) and cation exchange capacity (pH 7). The reversibility of DOC sorption was determined by a desorption experiment. All samples sorbed 20–40 % of the DOC added. The DOC sorption of the clay fractions explained the total sorption of the bulk soils. None of the mineral phase properties investigated was able to solely explain the DOC retention. A sorption of 9 to 24 μg DOC m^–2 indicated that DOC interacted only with a fraction of the mineral surface, since loadings above 500 μg m^–2 would be expected for a carbon monolayer. Under the experimental conditions used, the surface of the silicate clay minerals seemed to be more important for the DOC sorption than the surface of the iron oxides. The desorption experiment removed 11 to 31 % of the DOC sorbed. Most of the DOC was strongly sorbed.     

Sorption of copper (II) and sulphate to different biochars before and after composting with farmyard manure

Biochar application has been suggested for reducing toxic levels of metals in contaminated soils and enhancing nutrient retention in agro‐ecosystems. We studied sorption of copper (Cu(II)) and sulphate‐sulphur (SO₄‐S) to charcoal, gasification coke and flash‐pyrolysis biochar in order to relate sorption to char properties. Furthermore, we investigated the effect of composting of charcoal and gasification coke on sorptive properties. Langmuir sorption affinity coefficients for Cu(II) for non‐composted biochars increased in the order flash‐pyrolysis char < charcoal < gasification coke. The sorption capacity for Cu(II) of the chars decreased in the order gasification coke (629 mg kg^?1) > flash‐pyrolysis char (196 mg kg^?1) > charcoal (56 mg kg^?1). Composting significantly increased the sorption affinity coefficient approximately by a factor of 5 for charcoal (up to 1.1 l mg^?1) and by a factor of 3–4 for gasification coke (up to 3.2 l mg^?1). Whereas Cu(II) sorption to gasification coke (composted or not) was largely irreversible, sorption to flash‐pyrolysis char and charcoal showed higher reversibility. Relationships between Cu(II) sorption and biochar properties such as cation exchange capacity, specific surface area or aromaticity suggest that sorption was largely determined by complexation with organic matter. Sorption of SO₄‐S was negligible by non‐composted and composted biochars. Composted gasification coke might be suited to reducing toxic Cu(II) concentrations in contaminated soils. Composted charcoal can potentially improve Cu(II) retention in a plant available form in acidic, sandy soils with small organic matter contents. Transient effects of biochars on soil pH can over‐ride the influence of sorption to biochars on concentrations of trace elements in soil solution and their availability to plants.     

Adsorption and Desorption of Copper in Pasture Soils

Abstract

Copper (Cu) is bound strongly to organic matter, oxides of iron (Fe) and manganese (Mn), and clay minerals in soils. To investigate the relative contribution of different soil components in the sorption of Cu, sorption was measured after the removal of various other soil components; organic matter and aluminum (Al) and Fe oxides are important in Cu adsorption. Both adsorption and desorption of Cu at various pH values were also measured by using diverse pasture soils. The differences in the sorption of Cu between the soils are attributed to the differences in the chemical characteristics of the soils. Copper sorption, as measured by the Freundlich equation sorption constants [potassium (K) and nitrogen (N)], was strongly correlated with soil properties, such as silt content, organic carbon, and soil pH. The relative importance of organic matter and oxides on Cu adsorption decreased and increased, respectively, with increasing solution Cu concentrations. In all soils, Cu sorption increased with increasing pH, but the solution Cu concentration decreased with increasing soil pH. The cumulative amounts of native and added soil Cu desorbed from two contrasting soils (Manawatu and Ngamoka) during desorption periods showed that the differences in the desorbability of Cu were a result of differences in the physico‐chemical properties of the soil matrix. This finding suggests that soil organic matter complexes of Cu added through fertilizer, resulted in decreased desorption. The proportions of added Cu desorbed during 10 desorption periods were low, ranging from 2.5% in the 24‐h to 6% in the 2‐h desorption periods. The desorption of Cu decreased with increasing soil pH. The irreversible retention of Cu might be the result of complex formation with Cu at high pH.     

Indicative properties of fly‐ash affected forest soils in Northeastern Germany

Many forest ecosystems in Germany are strongly influenced by emissions of pollutants like SO₂ and alkaline dusts. To quantify and evaluate the consequences of long‐term fly ash deposition on forest soils, a study was conducted in pine stands (Pinus sylvestris) in the Dübener Heide in Northeastern Germany. This forest area has been influenced mainly by emissions from coal‐fired power plants and the chemical industry of the industrial region Bitterfeld‐Wolfen‐Zschornewitz since the early 1900. The study sites are located along a fly ash deposition gradient of 8, 16, 14, 18, and 25 km away from the main emission source in Bitterfeld (sites 1, 2, 3, 4, and 5, respectively). Samples of the organic horizons (Oi, Oe, and Oa) and mineral topsoil (0—10 cm) were taken in fall 1998 and analyzed for their ferromagnetic susceptibility and total ash content. Scanning electron microscopy (SEM) and energy dispersive X‐ray microanalysis (EDX) were performed on selected samples to differentiate between the pedogenic and atmospheric origin of the mineral components in the organic horizons. As a result of the long‐term deposition, ferromagnetic fly ash components are mainly accumulated in the Oe and Oa horizons of the forest soils studied. Ferromagnetic susceptibility was significantly higher (p ≤ 0.05) in the Oe horizon of sites 1 and 2 compared to sites 3, 4, and 5. Unusually high total ash contents for organic horizons of > 74 % were determined in the Oa at all sites. SEM revealed 3 distinct features of persistent fly ash deposits from coal‐fired power plants within the organic horizons that can be defined as ”︁stable glasses” with magnetic properties, aluminum‐silicate‐minerals, and slag fragments. SEM and EDX indicated that a great portion of the mineral particles found in the organic horizons of forests soils influenced by fly ash are from atmospheric sources. For detection of atmospheric lignite‐derived deposition into forest soils, the Oe and Oa horizons have to be considered as specific diagnostic horizons because they show indicative properties for such soils.     

Role of Different Soil Fractions in Copper Sorption by Soils

Abstract

To evaluate contributions of organic matter, oxides, and clay fraction to copper (Cu) adsorption in six characterized soils, adsorption isotherms and distribution coefficients were obtained by a batch experimental method. Copper adsorption isotherms from untreated soil, organic matter removed from samples, and organic‐matter‐ and oxide‐removed samples were compared with curve patterns and correlated to Langmuir and Freundlich models. Copper sorption data on untreated soils described L or H‐curves, whereas in soils deprived of any component, their curves were S‐type. Distribution coefficients allowed knowing Cu adsorption capacity of untreated soil and of organic matter, oxides, and clay fraction. Soil organic matter is the main component that affects Cu adsorption as long as soil pH is near neutrality. At acid pH, oxides are the main component that affects Cu adsorption, although to a much smaller extent than organic matter near neutral conditions. Soil pH is the main soil factor that determines Cu adsorption.     

Properties and bioavailability of particulate and mineral‐associated organic matter in Arctic permafrost soils,Lower Kolyma Region,Russia

Permafrost degradation may cause strong feedbacks of arctic ecosystems to global warming, but this will depend on if, and to what extent, organic matter (OM) is protected against biodegradation by mechanisms other than freezing and anoxia. Here, we report on the amount, chemical composition and bioavailability of particulate (POM) and mineral‐associated OM (MOM) in permafrost soils of the East Siberian Arctic. The average total organic carbon (OC) stock across all soils was 24.0 ± 6.7 kg m^?2 within 100 cm soil depth. Density fractionation (density cut‐off 1.6 g cm^?3) revealed that 54 ± 16% of the total soil OC and 64 ± 18% of OC in subsoil horizons was bound to minerals. As well as sorption of OM to clay‐sized minerals (R² = 0.80; P < 0.01), co‐precipitation of OM with hydrolyzable metals may also transfer carbon into the mineral‐bound fraction. Carbon:nitrogen ratios, stable carbon and nitrogen isotopes, ¹³C‐NMR and X‐ray photoelectron spectroscopy showed that OM is transformed in permafrost soils, which is a prerequisite for the formation of mineral‐organic associations. Mineral‐associated OM in deeper soil was enriched in ¹³C and ¹⁵N, and had narrow C:N and large alkyl C:(O‐/N‐alkyl C) ratios, indicating an advanced stage of decomposition. Despite being up to several thousands of years old, when incubated under favourable conditions (60% water‐holding capacity, 15°C, adequate nutrients, 90 days), only 1.5–5% of the mineral‐associated OC was released as CO₂. In the topsoils, POM had the largest mineralization but was even less bioavailable than the MOM in subsoil horizons. Our results suggest that the formation of mineral‐organic associations acts as an important additional factor in the stabilization of OM in permafrost soils. Although the majority of MOM was not prone to decomposition under favourable conditions, mineral‐organic associations host a readily accessible carbon fraction, which may actively participate in ecosystem carbon exchange.     

Sorption of primisulfuron on soil, and inorganic and organic soil colloids

Inorganic and organic soil colloids are responsible for the sorption of many pesticides. We studied the sorption of the herbicide primisulfuron [methyl 2 N‐[[[[[4,6‐bis(difluoromethoxy)‐2‐pyrimidinyl]amino]carbonyl]amino]sulfonyl]benzoate] on Fe³⁺‐, Al³⁺‐, Ca²⁺‐ and Na⁺‐exchanged montmorillonite, soil organic matter (H⁺‐ and Ca²⁺‐saturated), amorphous iron oxide, and three soils in aqueous media. The sorption on soils was negatively correlated with pH. Ca²⁺‐ and Na⁺‐exchanged montmorillonites are ineffective in the sorption of primisulfuron. The sorption on Fe³⁺‐ and Al³⁺‐exchanged montmorillonite is rapid and follows the Freundlich equation. Fourier transform infrared (FT‐IR) and X‐ray powder diffraction studies of the Fe³⁺‐ and Al³⁺‐montmorillonite samples after the interaction with primisulfuron in chloroform solution suggest that primisulfuron is adsorbed and degraded in the interlayer. Humic acid is more effective in the sorption than is Ca humate, suggesting that the pH of the suspension (3.5 for humic acid and 6.0 for Ca humate) has a strong influence on the sorption of primisulfuron. Experiments on amorphous iron oxide indicate similar pH dependence. Infrared spectra indicate that the protonation of the pyrimidine nitrogen moiety of herbicide and subsequent hydrogen bonding with the surface hydroxyls of Fe oxide is the mechanism acting in the primisulfuron sorption.     

Isotopic fractionation of dissolved organic carbon in shallow forest soils as affected by sorption

Isotopic fractionation of dissolved organic carbon percolating through the soil is often interpreted as due to microbial transformation. We investigated the potential effects of sorption on the δ¹³C of dissolved organic C in field and laboratory experiments. We sampled the organic C in soil water at two forested sites and measured sorption with intact mineral soil and individual minerals (dolomite, ferrihydrite, goethite, and quartz). The dissolved organic C was separated into hydrophilic and hydrophobic fractions using a resin approach. The δ¹³C values of bulk soils, alkaline‐extractable organic C, and dissolved organic C and its fractions were measured. Hydrophilic and hydrophobic fractions in forest floor seepage water were characterized by ¹³C‐NMR spectroscopy. At both sites, δ¹³C of dissolved organic C increased with increasing depth, suggesting that decomposition contributes to the loss of the dissolved organic C. However, there was an enrichment of hydrophilic organic C in the soil solution as the water moved down the soil. The δ¹³C values of hydrophilic fractions were less negative than those of hydrophobic fractions. The smaller δ¹³C in the hydrophobic fraction was due to the large contribution of compounds derived from lignin that are depleted in ¹³C. As the isotope composition of both fractions of dissolved organic C did not change throughout the profile, changes in δ¹³C of total organic C reflected changes in the relative proportions of its hydrophilic and hydrophobic fractions. The sorption experiments with minerals and soil cores gave similar results. When dissolved organic C came into contact with mineral material, the δ¹³C of that remaining in solution increased due to preferential sorption of the ¹³C‐depleted hydrophobic fractions. Moreover, the soils released hydrophilic organic C with large δ¹³C values, increasing the δ¹³C of organic C in effluents from soil compared with that in the inflow. Thus, selective sorption of organic C fractions changes δ¹³C in a way that mimics metabolic transformation and decomposition.