Physicochemical simulation of the ion exchange between humus acids and cations of different valencies

An approximate calculation was made for the ion exchange of black humic acids and the related fulvic acids with the cations H⁺, K⁺, Na⁺, Ca²⁺, Mg²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Fe³⁺, and Al³⁺. The calculation was based on the method of physicochemical simulation, the concepts of the chemical potentials of the elements, the experimental study of the equilibriums, and the determination of the activity coefficients of the monoionic forms of humus acids. Because of the presence of different functional groups, humus acids are considered as two-phase systems with specific activity coefficients for the monoionic forms of these acids in each phase. Examples of experimental studies and practical calculations of ion-exchange equilibriums in wide ranges of humus and solution cationic compositions were compared. Although the proposed approaches require perfecting, they can be used for solving practical problems and controlling equilibriums at the experimental stage.     

Influence of environmental factors upon the leaching of cations from undisturbed microcosms of beech and spruce litters

The leaching of nutrient cations (Na⁺, K⁺, Mg²⁺ and Ca²⁺) from undisturbed beech and spruce litters was followed in relation to the following environmental factors: nature of the organic layers, temperature, rainfall, quality of rain and stage of humus development. Among them, temperature, quality of rain and type of humus were predominant in modifying leaching rates of the nutrients. But, when the time of sampling was considered, the effects of physical, chemical and biological transformations of the humus on the leaching of cations had to be accounted for. The complexity of the interactions occurring during leaching is also exemplified.     

Systems of solutions,minerals, and humic substances in soils

The equilibrium composition of solutions, minerals, and humic substances of the humus-clay plasma from the humus horizon of a leached chernozem was calculated using the method of computerized physicochemical simulation based on Gibbs’ principle of minimum free energy in the equilibrium state of the system. It was shown that the plasma from the humus horizons of chernozems and soddy-deeply podzolic soil mainly consists of oxides, hydroxides, humic substances, kaolinite, and 2: 1 illite-smectite minerals. The stoichiometry of the humic substances corresponds to calcium-saturated humus acids with appreciable contents of iron and aluminum. The crystallochemical composition of the 2: 1 layered minerals classifies them among ferruginated mixed-layered illite-montmorillonites. Simulation at an increased concentration of carbon dioxide indicated the degradation of the humus-clay plasma in a leached chernozem under extensive soil use, which can be restored by application of potassium at rates 1-to ?1.5-fold its removal.     

Soil organic matter alteration under biochar amendment: study in the incubation experiment on the Podzol soils of the Leningrad region (Russia)

Purpose

Biochar is one of the most widely used ameliorants for soil amendment, which is known as factor which rises crop yields and levels of soil biological activity. Nowadays, it is under investigated how biochar application affects the dynamics of the humic components and whole soil organic matter (SOM) and the processes of its alteration. This investigation is aimed to evaluate the influence of biochar on the content, composition, and transformation of humic acids (HAs) as the main component of the SOM.

Materials and methods

The incubation experiment was carried out on three Podzol Antric soils, with varying amounts of initial total organic carbon. The incubation time was 90 days, using biochar gravimetric doses of 0.1 and 1.0%. The biochar was produced by fast pyrolysis of birch and aspen wood at 550 °С. Humus composition was analyzed for the organic matter fractions extracted with 0.1 M NaOH (containing HAs 1 + fulvic acids (FAs) 1) and 0.1 M Na₄P₂O₇ (containing HAs 1 + FAs 1 + HAs 2 + FAs 2). Isolated HAs were characterized for their elemental composition (C, N, H, and S) and molecular composition with the use of solid-state 13C nuclear magnetic resonance (13C-NMR) techniques.

Results and discussion

We found that 0.1% of biochar amendment does not influence SOM mineralization, but 1.0% of biochar increases the mineralization by 15–18%. This process is accompanied by changes in the composition and properties of the HS. The increased proportion of HA aromatic fragments in biochar indicates an increasing of their stability. However, in soils with high humus content and a significant amount of insoluble matter, the processes of mineralization and the growth of HAs are taking place simultaneously. The replenishment of HAs could be the outcome of both the intensification of the transformation processes (mineralization and humification) of the more sustainable insoluble matter compounds and the humification of the biochar itself.

Conclusions

The influence of biochar on humification in Podzol Antric soils was revealed on the basis of incubation experiment. Both negative and positive changes under biochar in HS system were demonstrated. The active decrease of humus total contents and also the labile HS ought to qualify as negative changes. The increase of HA chemical maturity that leads to the stability of humus in whole as well as the intensive new HA formation thought to qualify as positive changes.

     

Effect of the particle-size distribution on the adsorption of copper, lead, and zinc by Chernozemic soils of Rostov oblast

The parameters of adsorption of Cu²⁺, Pb²⁺, and Zn²⁺ cations by soils and their particle-size fractions were studied. The adsorption of metals by soils and the strength of their fixation on the surface of soil particles under both mono- and polyelement contamination decreased with the decreasing proportion of fine fractions in the soil. The adsorption capacity of the Lower Don chernozems for Cu²⁺, Pb²⁺, and Zn²⁺ depending on the particle-size distribution decreased in the following sequence: clay loamy ordinary chernozem ∼ clay loamy southern chernozem > loamy southern chernozem > loamy sandy southern chernozem. According to the parameters of the adsorption by the different particle-size fractions (C _max and k), the heavy metal cations form a sequence analogous to that obtained for the entire soils: Cu²⁺ ≥ Pb²⁺ > Zn²⁺. The parameters of the heavy metal adsorption by similar particle-size fractions separated from different soils decreased in the following order: clay loamy chernozem > loamy chernozem > loamy sandy chernozem. The analysis of the changes in the parameters of the Cu²⁺, Pb²⁺, and Zn²⁺ adsorption by soils and their particlesize fractions showed that the extensive adsorption characteristic, namely, the maximum adsorption (C _max), was a less sensitive parameter characterizing the soil than the intensive characteristic of the process—the adsorption equilibrium constant (k).     

Structure of humic acids in zonal soils from <Superscript>13</Superscript>C NMR data

The structure of humic acids (HAs) in zonal soil types—soddy-podzolic soils (two samples), gray forest soil (one sample), and chernozems (two samples)—was quantitatively studied by ¹³C NMR spectros-copy. In the series considered, the content of unsubstituted carbon in the aromatic fragments of HAs increased, and the fraction of unsubstituted aliphatic structures decreased. HAs of soddy-podzolic soils were found to be enriched with carbohydrate fragments compared to HAs of chernozems and gray forest soil. The carbon skeleton of HAs from typical rich chernozem contained significantly more aliphatic and carbohydrate fragments compared to typical chernozem, which probably reflected the lower degree of HA transformation in rich chernozem.     

Uptake of cations by annual ryegrass as related to cations adsorbed onto root exchange sites

Abstract

Previously published results on exchange capacities for Ca²⁺, Mg²⁺, Mn²⁺, and K⁺ in the Donnan free space of roots of two ryegrass cultivars (Lolium multiflorum Lam. cv. Marshall and Wilo) grown at two Al levels in the nutrient solution (0 and 74 μM) were correlated with the average net uptakes of the same cations. For Al‐treated plants regressed separately, significant correlations r=0.906 and r=0.963 were found for Mn²⁺ and Ca²⁺/Mg²⁺, respectively. No significant correlations were observed for these cations in control plants. In contrast, when data of control and Al‐treated plants were combined, significant linear correlations r=0.805, r=0.924, and r=0.968 were found for Ca²⁺, K⁺, and K⁺/(Ca²⁺+Mg²⁺)^1/2, respectively. The influence of cations adsorbed onto the root exchange sites and the effect of Al on the cation uptake processes were discussed.     

Deposition and Leaching of Sulphate and Base Cations in a Mixed Boreal Forest in Eastern Finland

Monthly fluxes of sulphate (SO₄ ^2-) and base cations(Ca²⁺, Mg²⁺, K⁺) were studied from 1993 to 1996 as precipitation passed through forest vegetation and surfacesoil layers in an area receiving low and declining levels of atmospheric sulphate pollution. The canopy was dominated by mature Norway spruce (Picea abies Karsten) and the soilwas a podzol developed on glacial till material. The mean annual bulk deposition of SO₄ ^2- collected in the open was 136 mol_c ha^-1 and that of Ca²⁺, Mg²⁺ and K⁺ was 44, 11 and 25 mol_c ha^-1, respectively. The annual total throughfall deposition of SO₄ ^2- was 318 mol_c ha^-1 and that of Ca²⁺, Mg²⁺ and K⁺ was 151, 64 and 181 mol_cha^-1, respectively. Sulphate was the dominant anion accompanying the base cations leached from the canopy. More than half (58%) of the annual total throughfall deposition ofSO₄ ^2- was retained by the O-horizon and only 15% leached from below the B-horizon. The annual leaching of Ca²⁺, Mg²⁺ and K⁺ from below the B-horizon was14, 25 and 9% of the annual total throughfall deposition, respectively. The transport of base cations through the soil was predominantely countered by SO₄ ^2- anions.     

Cultivation-Induced Effects on the Organic Matter in Degraded Southern African Soils

We studied quantitative and qualitative changes in soil organic matter (SOM) due to different land uses (reference woodland versus cultivated) on six soils from Tanzania (Mkindo and Mafiga), Zimbabwe (Domboshawa and Chickwaka), and South Africa (Hertzog and Guquka). Structural characteristics of the humic acids (HAs) were measured by Curie-point pyrolysis–gas chromatography/mass spectrometry (P_y–GC/MS) and solid-state ¹³C nuclear magnetic resonance (CPMAS ¹³C NMR) spectroscopy. Significant changes in concentration and composition of SOM were observed between land uses. Losses of organic carbon after cultivation ranged from 35% to 50%. Virgin soils showed large proportions of colloidal humus fractions: humic acids (HAs) and fulvic acids (FAs) but negligible amounts of not-yet decomposed organic residues. The change in land use produced a contrasting effect on the composition of the HAs: a noteworthy “alkyl enhancement” in Mkindo soil and “alkyl depletion” in Chikwaka and to a lesser extent in Domwoshawa. The remaining soils displayed only minor alterations.     

电解质对酸性土壤铝的溶解及铝形态在土壤溶液中的分布的影响

KCl, CaCl₂, NH₄Cl, NaCl, K₂SO₄ and KF solutions were used for studying the effects of cations and anions on the dissolution of aluminum and the distribution of aluminum forms respectively. Power of exchanging and releasing aluminum of four kinds of cations was in the decreasing order Ca²⁺ >K⁺ >NH₄⁺ >Na⁺. The dissolution of aluminum increased with the cation concentration. The adsorption affinity of various soils for aluminum was different. The aluminum in the soil with a stronger adsorption affinity was difficult to be exchanged and released by cations. The Al-F complexes were main species of inorganic aluminum at a low concentration of cations, while Al³⁺ became major species of inorganic aluminum at a high concentration of cations. The results on the effect of anions indicated that the concentrations of total aluminum, three kinds of inorganic aluminum (Al³⁺, Al-F and Al-OH complexes) and organic aluminum complexes (Al-OM) when SO₄^2- was added into soil suspension were lower than those when Cl^- was added. The dissolution of aluminum from soils and the distribution of aluminum forms in solution were affected by the adsorption of F^- on the soil. For soils with strong affinity for F^-, the concentrations of the three inorganic aluminum species in soil solution after addition of F^- were lower than those after addition of Cl^-; but for soils with weak affinity for F^-, the concentrations of Al³⁺ and Al-OM were lower and the concentrations of Al-F complexes and total inorganic aluminum after addition of F^- were higher than those after addition of Cl^-. The increase of F^- concentration in soil solution accelerated the dissolution of aluminum from soils.     

Competitivity,selectivity, and heavy metals-induced alkaline cation displacement in soils

Abstract

The simultaneous incorporation of heavy metals into the soil is still a matter of great concern. Interaction (competitive sorption) between these metals and the soil solid phase may result in a deterioration of soil quality which relies basically on amounts of alkaline cations saturating soils sorptive complex. Results of this study indicate that Pb, Cu, C d, and Zn have induced solution pH decreases which were more intensive at highest metal loading rates. Partition parameters (Kd)-based sequences showed that Pb and Cu were more competitive than Cd and Zn and the overall selectivity sequence followed: Pb > Cu > Cd > Zn. Metal loadings and their competitive sorption have led to a strengthened displacement of alkaline cations (i.e. Ca²⁺, Mg²⁺, K⁺, Na⁺), especially of Ca²⁺ as a factor “stabilizing” soil sorptive complex. Such metals impact jointly with soils acidification are of great environmental concern since tremendous amounts of alkaline cations (especially Ca²⁺) may be potentially leached out, irrespective of the degree of soil contamination, as evidenced in the current study. High and positive ΔG values implied that the studied soils were characterized by generally low concentrations of exchangeable potassium which required high energy to get displaced (desorbed). Further studies on heavy metal uncontaminated or contaminated areas should be undertaken to provide with data which should be used for predictions on changes related to soil buffering capacity as impacted by heavy metal inputs.     

Evaluating the fraction of electrically associated cations on surfaces of soil particles by extrapolation of strong-field Wien effect measurements in dilute suspensions

Purpose

For agricultural production and environment protection, it is cations loosely bound to the soil particles that have a great significance in short-term processes of adsorption–desorption, exchange, and transport. It is beneficial to be able to evaluate the fractions of these cations in order to correctly predict potential pollution of soils by heavy metals and availability of plant nutrients.

Materials and methods

The homionic suspensions of yellow-brown soil (YB) and black soil I (BI) saturated with Na⁺ and Ca²⁺ and three subsamples of black soil II (BII) saturated with Ca²⁺ and Cd²⁺ were prepared to determine the electrical conductivity (EC) of the suspensions. On the basis of electrical conductivity vs. field strength (EC-E) curve, the fraction of electrically associated cations on surfaces of soil particles was evaluated by extrapolation of strong-field Wien effect measurements in dilute suspensions.

Results and discussion

The maximum dissociation degree (α _max) of Na⁺ adsorbed on surfaces of yellow-brown soil and black soil I was about 0.21, which is approximately twice as much as those of Ca²⁺ (0.07–0.10) adsorbed on surfaces of two soils. The soil type was not the main factor in evaluating α _max, and the valence of the cations was. For divalent cations, α _max of Ca²⁺ and Cd²⁺ adsorbed on soil particles with different contents of organic matter descended in the order: top black soil II?>?bottom black soil II?>?OM-free bottom black soil II.

Conclusions

The relatively small fractions of electrically adsorbed cations—about 0.2 for Na⁺ and 0.1 for Ca²⁺ on yellow-brown and black soils particles indicated that even for the more loosely adsorbed Na⁺ ions, most of the cations in the double layers of soil particles were adsorbed strongly by other, more specific mechanisms and cannot be stripped off into the solution, which would increase its electrical conductivity in a strong applied field.

     

VARIABILITY OF ORGANIC MATTER AND EXCHANGEABLE CATIONS WITHIN THE A2 HORIZON OF AN IRON PODZOL

Analysis of variance has been carried out between soil samples separated by distances of 0.5 m, 10 m and 0.5–8 km. The samples were taken from the A₂ horizon of the Countesswells series iron podzol, thus maintaining the same pedological feature, profile class and parent material. The organic matter has been examined by the pyrolysis characteristics, total carbon and nitrogen, and the cations by exchangeable Ca²⁺, Mg²⁺, Na⁺, K⁺ and H⁺, whilst pH and total phosphorus have also been determined. The analysis of variance with respect to distance between the samples shows that all the properties examined exhibit considerable variation over short distances, many showing the major proportion of their total variance at a distance of 0.5 m. This markedly limits the interpretation of data from single samples. Those properties reflecting base status and humus type show, in addition, a variation of similar size over distances of the order of a kilometre.     

Effects of Weak Acids on Canopy Leaching and Uptake Processes in a Coniferous-Deciduous Mixed Evergreen Forest in Central-South China

The effects of Weak acids (WA) on the canopy leaching and uptake processes are evaluated by comparing the leached base cations or the absorbed protons while including and excluding WA, e.g. the WA-included method and the WA-excluded method. The seasonal WA throughfall flux is even larger than twice the bulk precipitation flux except summer, which not only partly agrees with the conclusion that the total deposition of WA equals twice the bulk or dry deposition flux in European Intensive Monitoring plots (level II), but also indicates the significant canopy leaching of WA in Shaoshan forest. The seasonal canopy leaching of base cations in association with WA accounts for 6–30% of the total base cations in throughfall, with an annual mean of 23%, which is slightly higher than the 15% at the Speulder forest in The Netherlands. The canopy exchange capacity of H⁺ to NH₄ ⁺ is closed to 6.0 while neglecting the WA exchange, which probably supports the assumption that the exchange capacity of H⁺ is six times that of NH₄ ⁺. Simultaneously, we suggest that the WA is competitive to a certain extent with protons to leach base cations of plant tissues during the canopy exchange processes.     

Solute Release from Weathering of Spent Mushroom Substrate under Controlled Conditions

Weathering of piled material in the field is a popular method to treat spent mushroom substrate (SMS) before reuse. During the weathering process, rainfall and snowmelt pass through SMS piles and a large amount of solutes is released in the leachate. To investigate solute release patterns, the field weathering process was simulated under controlled conditions in the laboratory. Fresh SMS was packed in an acrylic column (20 cm i.d.) to 150 cm height and leached intermittently with a cumulative total of 230 cm of deionized water over 180 days. Leachate was collected and analyzed for dissolved organic carbon (DOC), dissolved organic nitrogen (DON), electrical conductivity (EC), and inorganic salts. Solute release patterns were described using first order models, and total released solutes were calculated. The SMS leachate had DOC, DON and EC values ranging from 450 to 15,500 mg L^?1, 50 to 1,700 mg L^?1, and 3 to 50 dS m^?1, respectively. The major inorganic cations were K⁺, Na⁺, Ca²⁺, Mg²⁺ and NH₄⁺, and anions were Cl^? and SO₄^2?. Release of DOC, DON, and bivalent cations Ca²⁺ and Mg²⁺ were described by a first order Exponential Rise to Maximum model, while releases of monovalent ions Cl^?, K⁺, Na⁺ and NH₄⁺ were described as a first order Sigmoidal Logistic process, and SO₄^2? release was best modeled by a Sigmoidal Chapman equation. Following six months and 230 cm applied water, 3.1 kg of DOC, 0.58 kg of dissolved N, and 8.6 kg of inorganic salts were leached per cubic meter of bulk SMS (220 kg oven dry mass). Weathering of SMS involves a significant removal of nutrients from the composted material, which can contribute to pollution of soil and groundwater.     

Predicting cation exchange equilibria in soil containing three heterovalent cations

Theoretical cation exchange equilibria relationships in a soil for a ternary system containing Na⁺, Ca²⁺ and Mg²⁺ are presented. The solid phase activity coefficients of cations for the three binary systems (i. e., Na⁺ – Ca²⁺, Na⁺ – Mg²⁺ and Ca²⁺ – Mg²⁺) were used to calculate the Wilson parameters. Adsorbed phase activity coefficients of Na⁺, Ca²⁺ and Mg²⁺ corresponding to their equivalent fractions on the adsorbed phase of A horizon of a Camborthid for the ternary system (i. e., Na⁺ – Ca²⁺ – Mg²⁺) were evaluated, using these Wilson parameters. Using the values of activity coefficients of adsorbed Na⁺, Ca²⁺ and Mg²⁺ in a ternary soil system and of thermodynamic equilibrium constants for the binary systems, the multiple linear regression relationships between the equivalent fractions of Na⁺, Ca²⁺ and Mg²⁺ on the adsorbed phase and their mole fractions in the equilibrium solution were obtained. The amounts of adsorbed phase cations so predicted showed a fair agreement with those observed experimentally in a ternary system.     

Paramagnetic Properties of Humic Substances in Taiga and Tundra Soils of the European Northeast of Russia

The study of paramagnetic activity of humic substances in taiga and tundra soils of the Komi Republic and the assessment of the influence of soil hydromorphism on concentrations of free radicals in the structure of humic acids (HAs) and fulvic acids (FAs) have been performed. The concentration of free radicals in HA specimens was up to 11 times higher than that in FA specimens due to a higher content of aromatic and other condensed structures in HA molecules. This fact attests to the high capacity of HAs to polymerization and complexation reactions with participation of radicals. The average value of g-factor is higher for FA specimens than for HA specimens, which attests to a greater electron density shift of unpaired electron to oxygen atom in the structure of FAs because of its spin-orbital interaction with oxygen-containing functional groups, the concentrations of which are significantly higher in FAs than in HAs. An increase in the concentration of free radicals in the molecular structure of HAs is observed in taiga soils with an increase in the degree of their hydromorphism (from automorphic to semihydromorphic soils), which is related to the biohydrothermal conditions of humus formation in bog-podzolic soils with retarded biochemical processes and low degree of plant litter humification. As a result, HAs with the high content of free radicals in their structure are formed. An opposite situation is observed for HAs in tundra soils with a decrease in the content of unpaired electrons under conditions of the increased hydromorphism. The difference in the character of changes in the paramagnetic activity of HAs in taiga and tundra soils with different degrees of hydromorphism may be related to different natures of plant residues participating in humification processes. A tendency for a decrease in the paramagnetic activity in both HAs and FAs from the south to the north is observed, which may be related to a general decrease in the content of poly-conjugated systems in the structure of humic substances in tundra soils.     

Chemical Composition of Precipitation, Throughfall and Soil Solutions at Two Forested Sites in Guangzhou, South China

Rain water at two forested sites in Guangzhou (south China) show high concentrations of SO₄ ^2?, NO₃ ^? and Ca²⁺ and display a remarkable seasonal variation, with acid rain being more important during the spring and summer than during the autumn and winter. The amount of acid rain represents about 95% of total precipitation. The sources of pollutants from which acid rain developed includes both locally derived and long-middle distance transferred atmosphere pollutants. The seasonal variation in precipitation chemistry was largely related to the increasing neutralizing capacity of base cations in rainwater in winter. Soil acidification is highlighted by high H⁺ and Al³⁺ concentrations in soil solutions. The variation in elemental concentration in soil solution was related to nitrification (H⁺, NH₄ ⁺ and NO₃ ^?) and cation exchange reaction (H⁺, Al³⁺) in soil. The negative effect of soil acidification is partly dampened by substantial deposition of base cations (Ca²⁺, Mg²⁺ and K⁺) in this area.     

Acidity of podzolic soils subjected to sulphur pollution near a Cu-Ni smelter at the Kola Peninsula

The acidity of the podzolic soils in coniferous forests on the northern tree line (Kola Peninsula) subjected to severe sulphur pollution is considered. The pH values of precipitation were positively correlated with the distance from the pollution point source. There was also a correlation between base saturation of the organic horizon and distance. The long-term SO₂-emissions have resulted in the higher leachability of base cations and dissolution of fulvic acids in the humus horizon. In polluted areas the flux of H⁺ from the organic layer could be stronger owing to higher proportion of hydrolysable humus compounds. Inputs of H⁺ from the atmosphere and humus horizon have resulted in the higher concentrations of the exchangeable aluminium in the illuvial horizon.     

新疆典型草原土壤腐殖酸组分的变化规律

以新疆典型草原黑钙土、栗钙土和棕漠土为对象,研究了3种土壤不同土层腐殖质矿物复合体组分及其垂直分布规律。结果表明:13种典型草原土壤腐殖质总碳量的顺序为黑钙土(35、46g/kg)、栗钙土(31.30g/kg)和棕漠土(0.68g/kg);23种草原土壤都是以胡敏素(HM)含量最高,黑钙土、栗钙土和棕漠土的含量分别为68.17%、65.47%和42.81%;3按照腐殖酸类型分析,黑钙土和栗钙土是以胡敏酸(HA)为主的富啡酸(FA)-胡敏酸(HA)型,CH/CF＞1;而棕漠土则相反,是胡敏酸-富啡酸型,CH/CF＜1;4黑钙土、栗钙土和棕漠土腐殖质组分中游离R₂O₃结合的胡敏酸分别为6.85%、5.65%和1.65%,而富啡酸分别为0.53%、0.84%和4.91%;5在3种草原土壤中,游离腐殖酸从0~20cm到40~60cm的垂直变化规律分别为:黑钙土中游离胡敏酸和富啡酸分别从5.74和2.33g/kg降到2.70和0.89g/kg;栗钙土中游离胡敏酸和富啡酸分别从1.88和1.03g/kg降到0.59和0.75g/kg;棕漠土中游离胡敏酸和富啡酸分别由2.10和2.90g/kg降到1.92和0.67g/kg。