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.     

Trihalomethane reactivity of water- and sodium hydroxide-extractable organic carbon fractions from peat soils

Certain organic carbon moieties in drinking source waters of the Sacramento-San Joaquin Delta can react with chlorine during disinfection to form potentially carcinogenic and mutagenic trihalomethanes. The properties of reactive organic carbon in Delta waters, particularly those of soil origin, have been poorly understood. This study attempts to characterize trihalomethane reactivity of soil organic carbon from three representative Delta peat soils. Soil organic carbon was extracted from all three soils with either deionized H2O or 0.1 M NaOH and sequentially separated into humic acids, fulvic acids, and nonhumic substances for quantitation of trihalomethane formation potential. Water-extractable organic carbon represented only 0.4 to 0.7% of total soil organic carbon, whereas NaOH extracted 38 to 51% of total soil organic carbon. The sizes and specific trihalomethane formation potential (STHMFP) of individual organic carbon fractions differed with extractants. Fulvic acids were the largest fraction in H2O-extractable organic carbon, whereas humic acids were the largest fraction in NaOH-extractable organic carbon. Among the fractions derived from H2O-extractable carbon, fulvic acids had the greatest specific ultraviolet absorbance and STHMFP and had the majority of reactive organic carbon. Among the fractions from NaOH-extractable organic carbon, humic acids and fulvic acids had similar STHMFP and, thus, were equally reactive. Humic acids were associated with the majority of trihalomethane reactivity of NaOH-extractable organic carbon. The nonhumic substances were less reactive than either humic acids or fulvic acids regardless of extractants. Specific ultraviolet absorbance was not a good predictor of trihalomethane reactivity of organic carbon fractions separated from the soils.     

Removal of natural organic matter by cationic hydrogel with magnetic properties

Magnetic cationic hydrogel (MCH) was synthesized, and its removal efficiency and mechanisms in regard to natural organic matter (NOM, represented by humic acid and fulvic acid) from the aqueous environment were studied. The effects of time, adsorbent dosage, initial pH, ionic strength, background ions, and NOM types were also investigated. MCH was characterized and found to have a strong magnetic character, yielding an extra advantage for recycling and reuse. Batch studies showed that the removal of Aldrich humic acid (AHA) by MCH was effective. The main mechanism for the removal of NOM is believed to be due to electrostatic interaction. NOM with larger molecular weight tended to be preferentially removed. Solutions with low pH, high ionic strength, and background electrolytes containing calcium, sulfate and bicarbonate were unfavorable for AHA removal. The adsorption-desorption of MCH was evaluated in three cycles, and demonstrated high regeneration rates.     

Effects of mineral surfaces on pyrene partitioning to well-characterized humic substances

Mineral surfaces can alter the ability of humic substances (HS) to bind hydrophobic organic contaminants. In this study, complete adsorption (i.e., to avoid HS adsorptive fractionation effects) of a small subset of well-characterized terrestrial and aquatic HS on kaolinite and hematite significantly changed their subsequent organic carbon-normalized partition coefficients K(ads)(oc) for pyrene relative to their original respective dissolved organic carbon-normalized partition coefficients K(dis)(oc). Parallel experiments with ultrafiltration (UF) fractions obtained from purified Aldrich humic acid (PAHA) (Aldrich Chemical, Milwaukee, WI) gave similar results. The heterogeneity among the PAHA UF fractions was examined via their mineral surface adsorption characteristics and their subsequent ability to bind pyrene. As expected, variations in maximum adsorption densities (q(max)), Langmuir adsorption constants (K(q)), and pyrene K(ads)(oc) values were observed among the PAHA UF fractions. However, general trends of q(max), K(q), and pyrene log K(ads)(oc) values for the PAHA UF fractions versus the logarithm of their weight-average molecular weights (MW(w)) did not typically match the corresponding trends obtained with the four aquatic and terrestrial HS. In general, an ideal mixture competitive adsorption model gave reasonable predictions for PAHA sorption to kaolinite and hematite based on their corresponding UF isotherm parameters. Ideal mixture predictions of pyrene partitioning to adsorbed PAHA from the corresponding UF fraction results were better for kaolinite versus hematite, indicating that the underlying mineral surface can alter the effects of HS heterogeneity on hydrophobic organic contaminant sorption.     

Treatment of 2,4-dichlorophenol polluted soil with free and immobilized laccase

Enzyme treatment is currently considered for remediation of terrestrial systems polluted with organic compounds. In this study, two soils from Pennsylvania with 2.8 or 7.4% organic matter contents (Soils 1 and 2, respectively) were amended with 14C-labeled 2,4-dichlorophenol (2,4-DCP) and incubated with a laccase from Trametes villosa (free or immobilized on montmorillonite). 2,4-DCP was either transformed to methanol-soluble polymeric products (11-32%) or covalently bound to soil organic matter (53-85%); unaltered 2,4-DCP could be recovered from soil by methanol extraction (0-38%) at the completion of a 14-d incubation period. In Soil 1, both free and immobilized laccase removed 100% of 2,4-DCP without regard for moisture conditions. In Soil 2, immobilized laccase removed more 2,4-DCP (about 95%, regardless of moisture conditions) than free enzyme (55, 75, and 90% at 30, 55, and 100% of maximum water-holding capacity, respectively). Binding of 2,4-DCP in the humin fraction was nearly the same for free and immobilized laccase. More 2,4-DCP, however, was bound to humic and fulvic acids in the presence of immobilized laccase than in the presence of free laccase. In general, immobilized laccase performed better than free laccase. However, for practical applications, the higher activity of immobilized laccase is offset by a 23% loss in enzyme activity during immobilization, which approximates the 30% increase in free laccase needed to achieve the same level of remediation. Furthermore, immobilized laccase is more costly than free T. villosa laccase.     

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.     

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."     

Refined tunable methodology for characterization of contaminant-particle relationships in surface water

To understand contaminant transport in aquatic systems, it is essential to define the physical characteristics of the primary particulate carriers. The distribution of organic pollutants with particle-size class and particle morphology in a freshwater embayment (Hamilton Harbor, western Lake Ontario) was studied using a sequence of novel sample preparation and characterization techniques. Water samples (24 L) were fractionated according to particle-size distribution using differential cascade sedimentation and centrifugation methods. These size fractions were subsequently subjected to a physicochemical characterization using scanning transmission electron microscopy and energy-dispersive spectroscopy to identify flocs and individual colloidal particles in the size range of 1 nm to 1 mm in diameter. Analytical chemical analyses were performed to identify organic contaminants in extracts prepared from particle-size classes, including polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). The contaminant distribution trends were very similar for all compound classes studied; contaminants were primarily associated with fractions containing particles less than 2 mum in diameter. Morphological characterization of these fractions showed the majority of the particulates to be humic fractals. The results of this study show that contaminants in aquatic systems can be preferentially associated with specific types of particle carriers, the characteristics of which can be clearly defined in terms of size and morphology.     

Source identification and characterization of the accumulating non-biodegradable organics in Korean reservoirs

An increase in the chemical oxygen demand (COD) has been noticed in most Korean reservoirs. Therefore, this research systematically investigated the causes of organic accumulation. Samples of soil affecting the quality of water of reservoirs were collected at various sources and analyzed for their organic characteristics. The COD to biochemical oxygen demand (BOD) ratio was used as the key parameter in the evaluation of non-biodegradable (NBD) organic accumulation in the reservoirs. Soil samples containing plant roots were agitated, with the supernatant showing COD/BOD ratios of less than 2.8, while those of the composted tree leaves were greater than 5.0, suggesting that humic substances produced in forest areas are a major cause of NBD organic accumulation in reservoirs. In addition, the organic fractionation of the leachate from leaching tests showed that of the various types of hydrophobic natural organic matter (NOM), the larger molecular weight humic acid makes a greater contribution than fulvic acid to the increase in the NBD COD in Korean reservoirs.     

Investigation of the inorganic and organic phosphorus forms in animal manure

The most viable way to beneficially use animal manure on most farms is land application. Over the past few decades, repeated manure application has shown adverse effects on environmental quality due to phosphorus (P) runoff with rainwater, leading to eutrophication of aquatic ecosystems. Improved understanding of manure P chemistry may reduce this risk. In this research, 42 manure samples from seven animal species (beef and dairy cattle, swine, chicken, turkey, dairy goat, horse, and sheep) were sequentially fractionated with water, NaHCO?, NaOH, and HCl. Inorganic (P(i)), organic (P(o)), enzymatic hydrolyzable (P(e); monoester-, DNA-, and phytate-like P), and nonhydrolyzable P were measured in each fraction. Total dry ash P (P(t)) was measured in all manures. Total fractionated P (P(ft)) and total P(i) (P(it)) showed a strong linear relationship with P(t). However, the ratios between P(ft)/P(t) and P(it)/P(t) varied from 59 to 117% and from 28 to 96%, respectively. Water and NaHCO? extracted most of the P(i) in manure from ruminant+horse, whereas in nonruminant species a large fraction of manure P was extracted in the HCl fraction. Manure P(e) summed over all fractions (P(et)) accounted for 41 to 69% of total P(0) and 4 to 29% of P(t). The hydrolyzable pool in the majority of the manures was dominated by phytate- and DNA-like P in water, monoester- and DNA-like P in NaHCO?, and monoester- and phytate-like P in NaOH and HCl fractions. In conclusion, if one assumes that the P(et) and P(it) from the fractionation can become bioavailable, then from 34 to 100% of P(t) in animal manure would be bioavailable. This suggests the need for frequent monitoring of manure P for better manure management practices.     

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.     

Molecular-level investigation of monoaromatic compound sorption to suspended soil particles by deuterium nuclear magnetic resonance

Molecular-level sorption behavior of monoaromatic compounds in suspensions of water-dispersable clay components was studied by measuring 2H nuclear magnetic resonance (NMR) spin-spin relaxation times (T2). In general, decreased T2 values indicate stronger solute-sorbent interactions and increased sorption of the solute. A decreasing trend for T2 values in the order benzene > fluorobenzene > toluene (-C6D5 moiety) was observed, which was probably caused by the hydrophobic effect. The T2 values for benzene and the -C6D5 moiety of toluene increased with increasing pH, whereas the trend with pH was much weaker and less consistent for fluorobenzene and the methyl group of toluene. Conversely, no clear relationship was found between T2 values and pH for dichloromethane. These contrasting results cannot be explained by the pH-dependent self-assembly and hydrophobicity of humics. Instead, directed specific forces, including hydrogen bonding, cation-pi interactions, and aromatic-aromatic interactions, are proposed between the benzene ring of monoaromatic solutes and soil organic matter (SOM). Substituents of benzene affect these interactions by varying the pi electron density. When the soil fraction was treated with NaOH to remove humic and fulvic acids, T2 values for the different monoaromatic solutes were surprisingly lower compared with those for the untreated soil fraction. This result is probably caused by the increased ratio of solutes adsorbed to "hard" or "glassy" SOM components, which leads to less mobile sorbed solute molecules, after removing NaOH-extractable humics that contain more "soft" or "rubbery" SOM components.     

Thermal analysis of whole soils and sediment

Thermal analysis techniques were utilized to investigate the thermal properties of two soils and a lignite coal obtained from the International Humic Substances Society (IHSS), and sediment obtained from The Netherlands. Differential scanning calorimetry (DSC) revealed glass transition behavior of each sample at temperatures ranging from 52 degrees C for Pahokee peat (euic, hyperthermic Lithic Medisaprists), 55 degrees C for a Netherlands (B8) sediment, 64 degrees C for Elliott loam (fine, illitic, mesic Aquic Arguidolls), to 70 degrees C for Gascoyne leonardite. Temperature-modulated differential scanning calorimetry (TMDSC) revealed glass transition behavior at similar temperatures, and quantified constant-pressure specific heat capacity (Cp) at 0 degrees C from 0.6 J g(-1) degrees C(-1) for Elliott loam and 0.8 J g(-1) degrees C(-1) for the leonardite, to 1.0 J g(-1) degrees C(-1) for the peat and the sediment. Glass transition behavior showed no distinct correlation to elemental composition, although Gascoyne Leonardite and Pahokee peat each demonstrated glass transition behavior similar to that reported for humic acids derived from these materials. Thermomechanical analysis (TMA) revealed a large thermal expansion followed by a matrix collapse for each sample between 20 and 30 degrees C, suggesting the occurrence of transition behavior of unknown origin. Thermal transitions occurring at higher temperatures more representative of glass transition behavior were revealed for the sediment and the peat.     

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).     

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。     

Sorption kinetics of toluene in humin under two different levels of relative humidity

To identify any resistant fraction for desorption of toluene from humin and to quantify the sorption-desorption rates, the time courses of toluene sorption to compressed humin disks and to a thin humin film were investigated. The apparent diffusivity of toluene with humin disks ranges from 10(-8) to 10(-9) cm2/s and increases with temperature, based on the weight change of humin disks mounted on a microbalance and on the results simulated by use of a diffusion model. No detectable level of residual toluene was found after desorption, as revealed either by the gravimetric analysis or by the Fourier transform infrared (FTIR) spectrum obtained at either low or high humidity. The time scale for intrinsic vapor sorption without mass transfer hindrance is less than a few minutes with the thin film. All the results indicate that the sorption of toluene to humin is reversible and mainly diffusion controlled. This finding helps to better understand the sorption kinetics associated with humin and soil organic matter.     

Combined effect of natural organic matter and surfactants on the apparent solubility of polycyclic aromatic hydrocarbons

Both natural organic matter (NOM) and surfactants are known to enhance the apparent aqueous solubility of hydrophobic organic contaminants (HOCs) in aqueous systems. In this study, the combined effect of NOM and surfactants on enhancing the solubility of HOCs was investigated, since both may occur and affect the fate and transport of HOCs in natural aqueous environments. Experimental results indicated that the apparent solubility of naphthalene, phenanthrene, and pyrene in NOM and anionic surfactant solution was lower than their solubility in NOM solution alone. However, the apparent solubility of an HOC in NOM and nonionic surfactant solution is almost the same as the sum of the HOC's solubility in NOM solution plus its solubility in nonionic surfactant solution. The observation that apparent aqueous solubility of HOCs in NOM and anionic surfactant solution is decreased is probably due to the fact that the cations that are released when the anionic surfactant dissociates may form ion pairs with acidic or phenolic groups associated with the NOM. This serves to increase the size of hydration of these groups, thereby decreasing the effective size of the nonpolar moieties associated with the NOM, and thus decreasing hydrophobic partitioning of the HOCs into the NOM. The results presented here will help us to understand the effect of NOM and surfactants on the fate and transport of HOCs in aquatic systems.     

Bioavailability of organic phosphorus in a submerged aquatic vegetation-dominated treatment wetland

Enzymatic hydrolysis and mineralization of organic phosphorus (P) were determined in surface water samples collected from inflow and outflow of a submerged aquatic vegetation (SAV)-dominated treatment wetland of the Florida Everglades. Water samples were fractionated into three size fractions (> 0.4 micron, < 0.4 to > 0.05 micron, and < 0.05 micron) with a sequential flow filtration technique. The fractionated water samples were incubated to hydrolyze with alkaline phosphatase (APase) and phosphodiesterase (PDEase), and to mineralize at different redox and pH. Unlike APase, which hydrolyzed < or = 10% of organic P, PDEase hydrolyzed > or = 71% of organic P in unfiltered water from both inflow and outflow waters, suggesting the domination of bioavailable diester P in the water. Phosphodiesterase completely hydrolyzed organic P in the < 0.4- to > 0.05-micron and < 0.05-micron fractions, as compared with < or = 35% in the > 0.4-micron fraction. However, the P mineralization in inflow and outflow waters at different redox and pH showed that P associated with particulate > 0.4 micron had been mineralized the most. Phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy showed that surficial sediments from the inflow region contained a high proportion of polynucleotides, nucleoside monophosphates, and previously unreported glycerophosphoethanolamine and phosphoenolpyruvates. However, at the outflow, the relative proportion of polynucleotides and nucleoside monophosphates was reduced substantially. This suggests that the SAV wetland may sequester P via accretion of organic matter.     

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.