Study of the acid‐base properties of a peat soil and its humin and humic acid fractions

For accurate interpretation of cation binding to natural organic matter, the proton binding behaviour of both solid and dissolved natural organic matter must first be established. In the present study, potentiometric titrations of samples of humin and humic acid extracted from a peat soil were performed at different ionic strengths. Humic acid (HA) samples in solution (dissolved humic acid, DHA) and in suspension (aggregated humic acid, AHA) were titrated. The corresponding charge curves were analysed with the NICA‐Donnan model and the results were compared with those previously obtained for the peat soil. Good reproduction of the DHA charge curves was obtained, and in the case of the AHA, the exact forms of the charge curves were not reproduced at pH < 6 because of the conformational changes and dissolution of the sample that took place throughout the titration. The peat and humin displayed similar proton binding behaviour, which was different to that of the humic acid. With the Donnan approach, the value of parameter b, that relates the Donnan volume to the ionic strength, was the same for peat and humin and less than that of the humic acid, for both the dissolved samples and those in suspension, indicating that the effect of ionic strength on the charge is greater in the peat and humin than in the HA. The ratio between the contents of phenolic groups and of carboxylic groups was greater in peat and humin than in humic acid. The model used revealed that the acid‐base behaviour of the peat is closer to that of the humin than to that of the humic acid.     

Analysis of the variable charge of two organic soils by means of the NICA-Donnan model

We have tested to see if the generic set of NICA‐Donnan model parameters, used to describe isolated humic substances, can also describe soil humic substances in situ. A potentiometric back‐titration technique was used to determine the variable surface charge of two organic peat soils at three different ionic strengths. The non‐ideal, competitive‐adsorption NICA‐Donnan model was used to simulate the surface charge, by assuming a bimodal distribution of H⁺ affinity on the soil solid phase. The model provided an excellent fit to the experimental data. The Donnan volume, V_D, varied slightly with ionic strength, although the variation was less than for humic substances in solution. The values obtained for the parameters that define the affinity distributions, the intrinsic proton binding constant (log K_i^int) and the heterogeneity of the site (m_i), were similar to those observed for isolated soil humic acids. The abundance of carboxylic groups in the whole soil represented 30% of the typical value for isolated soil humic acids. The composition of the organic matter of the whole soils, obtained by ¹³C CPMAS NMR, was comparable to the characteristic composition of soil humic acids.     

Partitioning of organic carbon, aluminium and cadmium between solid and solution in soils: application of a mineral–humic particle additivity model

The partitioning of chemical elements between the solid and solution phases in soil is fundamental in understanding processes such as leaching and bioavailability. Here I present a model in which the partitioning of Cd, Al and carbon in both mineral and organic soils can be simulated in the pH range 2–8. A two‐phase additivity approach simulates ion adsorption by the soils using a hydrous ferric oxide and humic type surface. A model for the partitioning of soil humic matter has also been developed in which the NICA–Donnan model calculates humic surface charge. Other key processes represented include mineral solubilization and solution speciation. Methods for deriving model input parameters either from analytical data or by parameter optimization were used. Acid ammonium‐oxalate‐extractable Fe was used to estimate the amount of hydrous ferric oxide, and reactive humic substances were estimated by a scaled down version of the International Humic Substances Society method for the extraction of humic and fulvic acid. For initial calculation the 0.1 m HCl‐extractable Al was used to estimate reactive Al. Optimization of reactive Al improved the fit of both the total dissolved Al data and the adsorbed Cd. The model for the solid–solution partitioning of humic substances could simulate reasonably well the release of carbon in the pH range 4–8 for both the organic and mineral soils.     

Effects of dissolved organic matter on the mobility of copper in a contaminated sandy soil

Changes in land use can result in increased soil organic matter content, and decreases in Ca and pH which will affect the mobility of Cu in soil. We studied how the mobility and coagulation of dissolved organic matter and pH affected the mobility of Cu in contaminated sandy soil by batch and column experiments in the laboratory. The soil, with pH ranging from 3.8 to 5.7, had been polluted with Cu in the range 0.13–1.9 mmol kg^?1 more than a decade ago. Calcium and Cu bound by dissolved organic matter (purified humic acid) was determined in the pH range 4–8; Cu²⁺ concentration ranged from 10^?4 to 10^?12M and Ca²⁺ concentration from 10^?3 to 10^?6M. Binding of Cu by dissolved organic matter as affected by Ca and pH could be predicted well with the non-ideal competitive adsorption (NICA) model. Coagulation of dissolved organic matter was affected by the amount of trivalent (Al³⁺) and divalent (Ca²⁺ and Cu²⁺) cations in solution. There was little effect of pH on coagulation between pH 4 and 6. The concentration of the divalent cations, Ca²⁺ and Cu²⁺, at which coagulation of dissolved organic matter appeared could be explained by differences in the binding of Ca and Cu by dissolved organic matter. Binding of Cu by dissolved organic matter as well as by solid organic matter, both affected by Ca and pH, could be described well with the NICA model. We investigated the coagulation and mobility of dissolved organic matter in column experiments and found that they enhanced Cu mobility. Three processes, Cu desorption by soil, dissolved organic matter coagulation and Cu complexation by dissolved organic matter, act simultaneously in the soil columns. All three with counteracting effects on Cu mobility are influenced by Ca and pH and could be adequately represented by the multicomponent NICA model.     

A model of solid-solution interactions in acid organic soils, based on the complexation properties of humic substances

CHAOS (Complexation by Humic Acids in Organic Soils) is a quantitative chemical model of organic soils that incorporates complexation by the functional groups of humic substances and non-specific ion-exchange reactions. The two types of interaction are linked by the net humic charge, Z, which depends on the extents of proton and metal complexation, and which in turn determines ionic concentrations in the diffuse part of the electrical double layer, by a Donnan equilibrium. CHAOS was found to account satisfactorily for the results of acid-base titration experiments (pH range 3–5) with soil samples, giving reasonable simultaneous predictions of solution pH and concentration of A1³⁺. Predictive calculations with CHAOS suggest that organic soils acidified by acid rain would respond on a time-scale of years-to-decades to reductions in rain acidity. An associated effect might be an increase in the concentration of dissolved organic matter in the soil solution.     

Proton interactions with soil organic matter: the importance of aggregation and the weak acids of humin

Samples of three organic‐rich soils (ombrotrophic peat, podzol H‐horizon, humic ranker) were extensively washed with dilute nitric acid, dialysed against deionised water, and then subjected to acid‐base titrations over the pH range 3–10, in 0.3–300 mm NaNO₃, and with soil concentrations in the range 2–150 g l^?1. The results for the three soils were quantitatively similar. Comparison of the titration data with previously published results for humic acids isolated from the same soils showed the soil organic matter to have a greater ionic strength dependency of proton binding and to possess relatively greater buffering capacity at high pH, attributable to weak acid groups (c. 2–5 mmol g^–1) in the humin fraction of the soils. To describe the soil titration data quantitatively, we modified Humic Ion‐Binding Model VI‐FD, which utilizes a fixed Donnan volume to describe counterion accumulation, by increasing the content of weak acid groups. When artefacts in pH measurement caused by the suspension effect were taken into account, the resulting Model VI‐FD2 provided good or fair simulations of all the titration data. The results suggest that soil structure, specifically aggregation, plays a significant role in cation binding by organic soils in situ. The lack of dependence of the titration results on soil suspension concentration suggests that the findings can be applied to soils in situ.     

Partitioning of polycyclic aromatic hydrocarbons (PAH) to water-soluble soil organic matter

The mobility of polycyclic aromatic hydrocarbons (PAH) in soils can be influenced by the presence of dissolved organic matter. Partition coefficients of selected polycyclic aromatic hydrocarbons, ranging from 3-ring to 6-ring compounds, to water-soluble soil organic matter (WSSOM) were determined. Partition coefficients were determined for WSSOM obtained from two soils under agricultural use and forest and for commercially available humic acid (Aldrich), taking advantage of a reversed phase (C₁₈) separation method. The WSSOM was characterised with regard to charge and hydrophilic/hydrophobic properties with a dissolved organic matter (DOM) fractionation method. No sorption to WSSOM was found for the tri- and tetracyclic PAH, whereas the penta- and hexacyclic PAH showed a significant binding to both types of WSSOM and to Aldrich humic acid. The affinity of penta- and hexacyclic PAH to WSSOM was considerably lower compared to the affinity to Aldrich humic acid. This is suggested to be due to the lower amount of hydrophobic fractions, c. 30%, in the natural WSSOM as compared to Aldrich humic acid. Effective partition coefficients (Koc_eff) for the sorption of PAH to bulk soil calculated from K_DOC and DOM in the naturally occurring concentration range were only 60–70% of the K_oc values in pure water. The impact of DOM on pollutant transport is further influenced by non-equilibrium behaviour of PAH in soils and by sorption of DOM to the solid-soil matrix. Several scenarios are described in which the effect of DOM on pollutant transport may become important.     

Effect of cultivation on chemical characteristics and respiratory activity of crusting soil from Mazowe (Zimbabwe)

Abstract

Clearing and cultivation in crusting soils from Mazowe (Zimbabwe) has lead to severe changes in most physico‐chemical characteristics related to the concentration and distribution patterns of plant nutrients and to the total amount of soil organic matter. Nevertheless, the concentration of the different humus fractions showed lower intensity changes, as did the mineralization rates of the organic matter. The most significant effects of cultivation on the soil chemical characteristics coincided with those considered to favor clay dispersion and crusting phenomena, including generalized desaturation of the exchange complex and losses of divalent ions with a potential bridging effect between soil particles. Concerning the soil organic matter, the humic acid tended to concentrate in the cultivated soils as a probable consequence of selective biodegradation of the other humic fractions. The composition and activity of soil humus suggest low‐performance organo‐mineral interactions: in these soils the active turnover of the plant wastes is not regulated by intense physico‐chemical interactions with the soil mineral fractions, or by physical encapsulation of organic particles. In consequence, the mineralization rates were relatively constant in the soils studied and unrelated to soil organic matter concentration. The results suggests that there is a possibility to revert the early degradation stages of these soils through a rational management of suitable amounts of crop wastes.     

Dissolved organic matter in lysimetric water of mountain forest soils in the southern Sikhote Alin

The fractional composition of dissolved organic matter and the chemical nature of humic and fulvic acids were studied in lysimetric waters from forest soils of different altitudinal zones in the Sikhote Alin Range. The elemental composition, infrared absorption spectra, concentrations of acid functional groups, and pK spectra of humic and fulvic acids were determined. Fulvic acids predominated in the upper soil horizons, and fraction of nonspecific dissolved organic substances predominated in the lower mineral horizons. The portion of humic acids in the humus horizons markedly decreased from the low-mountain soils to the high-mountain soils; the nitrogen content of humic and fulvic acids decreased in the same direction. Three classes of carboxyl and phenolic groups were determined in pK-spectra of humic and fulvic acids. The soils of high-mountain zones had stronger acidic properties of humic and fulvic acids in comparison with the soils of low-mountain zones. The determined characteristics of the composition of dissolved organic matter and the trends of their changes contribute to our knowledge of pedogenetic processes in the altitudinal sequence of forest landscapes of the Sikhote Alin Range.     

Transformation of organic matter from maize residues into labile and humic fractions of three European soils as revealed by 13C distribution and CPMAS-NMR spectra

The dynamics of incorporation of fresh organic residues into the various fractions of soil organic matter have yet to be clarified in terms of chemical structures and mechanisms involved. We studied by ¹³C‐dilution analysis and CPMAS‐¹³C‐NMR spectroscopy the distribution of organic carbon from mixed or mulched maize residues into specific defined fractions such as carbohydrates and humic fractions isolated by selective extractants in a year‐long incubation of three European soils. The contents of carbohydrates in soil particle size fractions and relative δ¹³C values showed no retention of carbohydrates from maize but rather decomposition of those from native organic matter in the soil. By contrast, CPMAS‐¹³C‐NMR spectra of humic (HA) and fulvic acids (FA) extracted by alkaline solution generally indicated the transfer of maize C (mostly carbohydrates and peptides) into humic materials, whereas spectra of organic matter extracted with an acetone solution (HE) indicated solubilization of an aliphatic‐rich, hydrophobic fraction that seemed not to contain any C from maize. The abundance of ¹³C showed that all humic fractions behaved as a sink for C from maize residues but the FA fraction was related to the turnover of fresh organic matter more than the HA. Removal of hydrophobic components from incubated soils by acetone solution allowed a subsequent extraction of HA and, especially, FA still containing much C from maize. The combination of isotopic measurements and NMR spectra indicated that while hydrophilic compounds from maize were retained in HA and FA, hydrophobic components in the HE fraction had chemical features similar to those of humin. Our results show that the organic compounds released in soils by mineralization of fresh plant residues are stored mainly in the hydrophilic fraction of humic substances which are, in turn, stabilized against microbial degradation by the most hydrophobic humic matter. Our findings suggest that native soil humic substances contribute to the accumulation of new organic matter in soils.     

Orthophosphate and organic phosphate in the soil solution of four sandy soils in relation to pH‐evidence for humic‐FE‐(AL‐) phosphate complexes

Abstract

Soil from the Ap‐horizon of four acid sandy soils differing mainly in Corg content was adjusted to pH values between 3 and 7.5 with NaOH and HCl respectively and incubated for two weeks. Afterwards, displaced soil solution was obtained and analyzed.

The concentrations of Fe, Al, and P showed a broad minimum in the pH range from 4 to 6. The concentration of these elements strongly increased with the increase of pH to 7.5. Acidification below pH values of 4 led to a slight increase.

Separation of dissolved organic carbon by ultrafiltration before the photometric orthophosphate determination decreased measured concentrations in comparison to direct determination in two of the four soils. This decrease was more pronounced for soil solutions with higher concentrations of organic carbon. The effect of acid hydrolysis of organic phosphorus during orthophosphate determination can be explained by existence of humic‐Fe‐(Al phosphate complexes in the soil solution. These complexes can account for more than 50% of the total organic P in solution.     

A comparison of extraction procedures for water‐extractable organic matter in soils

The characteristics of dissolved organic matter (DOM) in soils are often determined through laboratory experiments. Many different protocols can be used to extract organic matter from soil. In this study, we used five air‐dried soils to compare three extraction methods for water‐extractable organic matter (WEOM) as follows: (i) pressurised hot‐water‐extractable organic carbon (PH‐WEOC), a percolation at high pressure and temperature; (ii) water‐extractable organic carbon (WEOC), a 1‐hour end‐over shaking; and (iii) leaching‐extractable organic carbon (LEOC), a leaching of soil columns at ambient conditions. We quantified the extraction yield of organic carbon; the quality of WEOM was characterized by UV absorbance, potential biodegradability (48‐day incubation) and parallel factor analysis (PARAFAC) modelling of fluorescence excitation emission matrices (FEEMs). Biodegradation of dissolved organic carbon (DOC) was described by two pools of organic C. The proportions of labile and stable DOC pools differed only slightly between the WEOC and LEOC methods, while PH‐WEOC contains more stable DOC. The mineralization rate constants of both labile and stable DOC pools were similar for the three methods. The FEEMs were decomposed into three components: two humic‐like fluorophores and a tryptophan‐like fluorophore. The effect of extraction method was poorly discriminant and the most similar procedures were PH‐WEOC and LEOC while WEOC extracts were depleted in humic‐like fluorophores. This study demonstrates that WEOM quality is primarily determined by soil characteristics and that the extraction method has a smaller, but still significant, impact on WEOM quality. Furthermore, we observed considerable interaction between extraction procedure and soil type, showing that method‐induced differences in WEOM quality vary with soil characteristics.     

Modelling pH buffering and aluminium solubility in European forest soils

The pH buffering and aluminium solubility characteristics of acid soil are important in determining the soil's response to changes in precipitation acidity. The chemistry of soil organic matter (humic substances) plays a key role in both processes, yet is complex and still poorly understood. Nevertheless, models of humic substance chemistry have been developed, one of which is WHAM–S, which contains a model (Model V) of proton and metal binding at discrete sites on humic substances and considers electrostatic effects on the binding strength. Here we have tested the ability of WHAM–S to model solution pH and Al using batch titration studies on organic and mineral soil horizons from forested sites in Norway, Germany and Spain, with ambient pH values from 3.73 to 5.73. We optimized the model predictions by adjusting the amounts of soil aluminium and humic substances within defined limits, taking the contents of copper chloride‐extractable Al and the base‐extractable organic matter as starting values. The model simulated both pH and dissolved Al well with optimized amounts of aluminium and humic substances within the defined limits (root mean squared error for pH from 0.01 to 0.22, for p[Al]_aq (total dissolved Al) from 0.03 to 0.49, five data points). Control of dissolved Al by dissolved organic matter was important particularly at above‐ambient pH. In two mineral horizons we improved the fits by assuming that Al could precipitate as Al(OH)₃. The optimized model also gave reasonable predictions of pH and dissolved Al in supernatants obtained by repeated leaching of the soil horizons. The results show that humic substances dominate the control of pH and dissolved Al in most of the horizons studied. Control by Al(OH)₃ occurs but is the exception.     

Cation binding by acid-washed peat, interpreted with Humic Ion-Binding Model VI-FD

A sample of ombrotrophic peat from Moor House in northern England was extensively extracted with dilute nitric acid (pH 1) to free it of bound cations. Suspensions of the acid‐washed peat (5–30 g l^?1), prepared with different concentrations of background electrolyte (NaCl and KCl), were used to conduct batch acid–base titrations. A strong dependence of proton release on ionic strength (I) was observed, the apparent acid dissociation constant (pK_app) being found to decrease by approximately 1.0 for each tenfold increase in I. This behaviour could not be explained satisfactorily with Humic Ion‐Binding Model VI, a discrete‐site/electrostatic model of cation binding by humic substances, parameterized with data from laboratory studies on isolated samples. More success was obtained by abandoning the impermeable‐sphere electrostatic submodel used in Model VI, and instead assuming the peat to consist of aggregates with fixed internal volume, and with counterion accumulation described by the Donnan model, as proposed by Marinsky and colleagues. The fixed‐volume Donnan model (Model VI‐FD) could also approximately explain other reported results from acid–base titrations of peat, including the effects on the titrations of complexing cations (Al, Ca, Cu). Copper titrations of the Moor House sample were performed using an ion‐selective electrode, with peat suspensions in the acid pH range, at two ionic strengths, and in the presence of Al and Ca. The measured concentrations of Cu²⁺ were in the range 10^?13?10^?5 m . Model VI‐FD provided reasonable fits of the experimental data, after optimization of the intrinsic binding constant for Cu, the optimized value being close to the default value derived previously from data referring to isolated humic substances. The optimized constants for Al and Ca, derived from their competition effects, were also close to their default values. Additional experiments were performed in which the centrifugation‐depletion method was used to measure the binding of a cocktail of metals (Al, Ni, Cu, Zn, Cd, Eu, Pb) at a single pH. The model correctly predicted strong binding of Al, Cu, Eu and Pb, and weaker binding of Ni, Zn and Cd. For the strongly binding metals, the dissolved forms were calculated to be mainly due to complexes with dissolved humic matter, whereas the free ions (Ni²⁺, Zn²⁺, Cd²⁺) dominated for the weakly binding metals. Acid‐washed soil appears to provide a valuable intermediate between isolated humic substances and untreated soil for the investigation of cation binding by natural organic matter in the natural environment.     

Tea Plantation–Induced Activation of Soil Heavy Metals

Abstract

The accumulation of heavy metals in tea leaves is of concern because of its impact on tea quality. This study characterized long‐term changes of soil properties and heavy‐metal fractions in tea gardens and their effect on the uptake of metals from soils by the plants. Soil and tea leaf samples were collected from five plantations with a history of 2–70 years in Jinghua, Zhejiang Province, southeast China. The six chemical fractions (water‐soluble, exchangeable, carbonate‐bound, organic‐matterbound, oxide‐bound, and residual forms) of cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), nickel (Ni), manganese (Mn), lead (Pb), and zinc (Zn) in the soils were characterized. Dissolved organic‐matter accumulation in the soils and effects of low‐molecular‐weight organic acids on solubility of soil heavy metals were also tested. Long‐term tea plantation use resulted in accumulation of dissolved organic matter, decrease of soil pH, and elevation of water‐soluble and exchangeable metal fractions, thereby increasing metal contents in leaves. The influence was more significant when soil pH was less than 4.4. The results indicated that both acidification and accumulation of dissolved organic matter induced by tea plantations were also important causes of increased accumulation of the metals in the tea leaves. This was particularly true for the soils polluted with low concentration of heavy metals, because availability of the metals in these soils was mainly controlled by pH and dissolved organic matter.     

Influence of land use on the characteristics of humic substances in some tropical soils of Nigeria

In highly weathered tropical conditions, soil organic matter is important for soil quality and productivity. We evaluated the effects of deforestation and subsequent arable cropping on the qualitative and quantitative transformation of the humic pool of the soil at three locations in Nigeria. Cultivation reduced the humic pool in the order: acetone‐soluble hydrophobic fraction (HE) > humic acid (HA) > humin (HU) > fulvic acid (FA), but not to the same degree at all three sites. The C and N contents, as well as the C/N ratios of humic extracts, were large and not substantially influenced by land use. The δ¹³C values of the humic extracts were invariably more negative in forested soils thereby showing a dilution of δ¹³C signature with cultivation from C3 to C4 plants. The δ¹³C values of apolar HE fractions were generally more negative, indicating a reduced sensitivity compared with other humic fractions to turnover of crop residues. The contents of hydrophobic constituents (alkyl and aromatic C), as revealed by cross‐polarization magic angle spinning (CPMAS) ¹³C‐NMR spectroscopy, in HA, FA and HU were generally < 50%, with the exception of larger hydrophobicity in HU in the forested soil at Nsukka and HA in that at Umudike. The HE fraction contained significantly more apolar constituents, and consequently had a larger intrinsic hydrophobicity than the other humic fractions. The larger reduction of apolar humic constituents than of the less hydrophobic humic fractions, when these soils were deforested for cultivation, indicates that at those sites the stability of accumulated organic matter is to be ascribed mainly to the selective preservation of hydrophobic compounds.     

Validation of Transfer Functions Predicting Cd and Pb Free Metal Ion Activity in Soil Solution as a Function of Soil Characteristics and Reactive Metal Content

According to recent insight, the toxicity of metals in soils is better related to the free metal ion (FMI) activity in the soil solution than to the total metal concentration in soil. However, the determination of FMI activities in soil solution is a difficult and time-consuming task. An alternative is to use empirical equations (so called transfer functions (TFs)) that relate FMI activity in solution to the reactive metal concentration in the solid phase and to soil properties (pH and organic matter content). Here we test the applicability of two sets of TF for Cd and Pb using independent data from a wide range of soil types and regions that are not represented in the datasets used to derive the TFs. From these soils, soil solution was extracted using four different methods. For all these extracts, FMI activities were calculated from total concentrations in solution using the speciation program WHAM VI. In some of the soils, Cd and Pb FMI activities were also measured using a Donnan membrane technique. Most of these FMI activities deviated from the TF predictions by less than one order of magnitude and were within the 95% confidence interval of the TFs, irrespective of the method used to extract soil solution. Predictability was higher for Pb than for Cd and differed also between the two TF sets.     

Influence of pH on copper, lead and cadmium binding by an ombrotrophic peat

The effect of pH on the adsorption of copper (Cu), lead (Pb) and cadmium (Cd) by a peat soil was studied, and the results compared with those corresponding to cation binding by a dissolved peat humic acid (HA), and interpreted with a NICA–Donnan model. A potentiometric titration technique was used to determine the adsorption isotherms for H⁺, at different ionic strengths, and for Cu²⁺, Pb²⁺ and Cd²⁺ at different pH values, in a peat soil. The effect of the ionic strength on proton binding was similar for the soil (solid) organic matter and for dissolved HA. The adsorption isotherms for cation–peat and the binding curves cation–dissolved HA are almost parallel, although more cation was adsorbed per kg of C in the dissolved HA. The effect of pH on cation binding is similar for dissolved organic matter and for the organic soil. At low metal concentration the amount of adsorbed metal followed the order Cu²⁺ > Pb²⁺ > Cd²⁺. The cation-binding parameters obtained with the NICA–Donnan model allow excellent simulation of the effect of pH on the adsorption of Cu, Pb and Cd ions in the studied peat soil. The binding constants for the peat suspension were greater than the corresponding generic parameters for dissolved HA. Speciation calculations showed that for Cu and Pb, the most abundant fraction was the metal adsorbed on peat, whereas for Cd the most abundant fraction was dissolved metal.     

Sorption of cadmium by complexes of kaolinite with humic acid

Abstract

Levels of cadmium (Cd) in New Zealand pastoral soils have increased due to Cd impurities in applied fertilisers. As there is little information on the interaction of Cd with soil mineral‐organic matter complexes, the sorption of Cd by complexes of kaolinite with humic acid has been investigated. Sorption was measured at pH and ionic strength values typically found for solutions of pastoral soils in New Zealand. Sorption increased with the content of humic acid in the complex, and as the pH of the medium was raised from 4.2 to 6.3. Sorption was also influenced by the ionic strength of the ambient solution, notably by the nature of the cation in the added electrolyte. The experimental data were interpreted in terms of the effect of solution pH and ionic composition on the charge characteristics of kaolinite and humic acid. These factors, in turn, influence clay particle association as well as the clay‐humic and metal‐humic interaction.     

珠江三角洲地区土壤与表层沉积物有机质的性质结构研究

通过分析海洋、河流、池塘和稻田四种热带 /亚热带土壤与表层沉积物及用化学方法分离的有机质 ,证明了土壤与沉积物有机质是高度不均匀的 ,除了包括腐殖酸和演化程度较深的干酪根外 ,强调了演化程度更深的碳黑的存在 ,并对不同有机质的来源、性质和结构进行了表征。腐殖酸和干酪根来源于生物体的演化 ,在结构上后者比前者致密 ;碳黑来源于化石燃料和生物体的不完全燃烧 ,具有更致密的结构 ,对有机质的非均质性影响很大。因此可认为 ,系统地研究土壤与表层沉积物有机质的非均质性及组分特征对了解地球表层的生物地球化学过程和疏水性毒害有机污染物在环境中的迁移具有重要的意义。