Effect of low-molecular-weight organic acids on Cl- adsorption by variable charge soils

Low-molecular-weight (LMW) organic acids exist widely in soils and have been implicated in many soil processes.The objective of the present paper was to evaluate effect of two LMW organic acids, citric acid and oxalic acid, on Cl^- adsorption by three variable charge soils, a latosol, a lateritic red soil and a red soil, using a batch method. The results showed that the presence of citric acid and oxalic acid led to a decrease in Cl- adsorption with larger decreases for citric acid. Among the different soils Cl- adsorption in the lateritic red soil and the red soil was more affected by both the LMW organic acids than that in the latosol.     

小麦分泌的有机酸影响钙质土中锌的释放

Rhizosphere drives plant uptake of sparingly soluble soil zinc(Zn).An investigation with three experiments was conducted to study organic acid exudation by two contrasting wheat genotypes(Sehar-06 and Vatan),Zn fractions in 10 different calcareous soils from Punjab,Pakistan,and release of different soil Zn fractions by organic acids.The two genotypes differed significantly in biomass production and Zn accumulation under deficient and optimum Zn levels in nutrient solution.At a deficient Zn level,Sehar-06 released more maleic acid in the rhizosphere than Vatan.Ten soils used in the present study had very different physicochemical properties;their total Zn and Zn distribution among different fractions varied significantly.Zinc release behaviour was determined by extracting the soils with 0.005 mol L-1 citric acid or maleic acid.The parabolic diffusion model best described Zn release as a function of time.Parabolic diffusion model fitting indicated more maleic acid-driven than citric acid-driven soil Zn mobility from different fractions.Cumulative Zn release in six consecutive extractions during 24 h ranged from 1.85 to 13.58 mg kg-1 using maleic acid and from 0.37 to 11.84 mg kg-1 using citric acid.In the selected calcareous soils,the results of stepwise linear regression indicated significant release of Fe-Mn oxide-bounded soil Zn by maleic acid and its availability to the Zn-effcient genotype.Hence,release of maleic acid by plants roots played an important role in phytoavailability of Zn from calcareous soils.     

Release of Soil Nonexchangeable K by Organic Acids

The amounts of soil nonexchangeable K extracted with 0.01mL/L oxalic acid and citric acid solutions and that with boiling 1mL/L HNO3 for ten minutes were remarkably significantly correlated with each other,and the amount extracted with the oxalic acid solution was higher than that with the citric acid solution.The soil nonexchangeable K release was comprised of two first-order kinetic processes.The faster one was ascribed to the interlayer K in outer sphere,while the slower one to that in inner sphere.The rate constants of the soil nonexchageable K were significantly correlated with the amounts of nonexchangeable K ex tracted with boiling 1mL/L HNO3 for ten minutes.Study on the fitness of different kinetic equations indicated that the first-order,parabolic diffusion and zero-order equations could all describe the release of soil nonexchangeable K well,but Elovich equation was not suitable to describe it.     

中国福建省土壤的主要粘土矿物

The clay minerals of more than 200 soil samples collected from various sites of Fujian Province were studied by the X-ray diffraction method and transmission electron microscopy to study their distribution and evolution.Montmorillonite was found in coastal solonchak,paddy soils derived from marine deposit,lacustrine deposit and river deposit,and some lateritic red soil,red soil and yellow soil with a low weathering degree.Chlorite existed mainly in coastal solonchak and paddy soil developed from marine deposit.1.4nm intergradient mineral appeared frequently in yellow soil,red soil and lateritic red soil.The content of 1.4nm intergradient mineral increased with the decrease of weathering degree from lateritic red soil to red soil to yellow soil.Hydrous micas were more in coastal solonchak,paddy soils derived from marine deposit,lacustrine deposit and river deposit.and puple soil from purple shale than in other soils.Kaolinte was the most important clay mineral in the soils iun this province.The higher the soil weathering degree,the more the kaolinite existed.From yellow soil to red soil to lateritic red soil,kaolinite increased gradually,Kaolinite was the predominant clay mineral accompanied by few other minerals in typical lateritic red soil. Tubular halloysite was a widespread clay mineral in soils of Fujian Province with varying quantities.The soil derived from the paent rocks rich in feldspar contained more tubular halloysite.Spheroidal halloysite was found in a red soil and a paddy soil developed from olivine basalt gibbsite in the soils in this district was largely“primary gibbsite” which formed in the early weathering stage.Gibbsite decreased with the increase of weathering degree from yellow soil to red soil to lateritic red soil.Goethite also decreased in the same sequence while hematite increased.     

有机酸和质子对淹水水稻土非交换性铵释放的影响

In a model experiment, which imitated the rhizosphere of rice, the effect of organic acids (oxalic acid, citric acid) and protons on the release of non-exchangeable NH4^ and the resin adsorption of N was studied in a paddy soil, typical for Zhejiang Province, China. Oxalic and citric acids under low pH conditions, in combination with proton secretion, favored the mobilization of NH4^ ions and increased resin adsorption of N. The release of non-exchangeable NH4^ was associated with less formation of iron oxides. These could coat clay minerals and thus hinder the diffusion of NH4^ ions out of the interlayer. Protons enhanced the release of NH4^ , and then they could enter the wedge zones of the clay minerals and displace non-exchangeable NH4^ ions.     

土壤中氮磷钾肥转化中的交互作用: Ⅰ.土壤pH的动态变化

Dynamic changes of soil pH as influenced by ammonium sulfate (AS), monocalcium phosphate (MCP),potassium chloride (KCl) and their interaction in soils were evaluated in incubation experiments. Applyingthese fertilizers significantly reduced soil pH values in all cases and followed sequences of AS ＞ MCP ＞KCl, MCP ＞ KCl ＞ AS and KCl ＞ AS ＞ MCP for the paddy, calcareous and red soils, respectively. TheAS-induced reduction of pH in the three soils followed the sequence of red soil ＞ paddy soil ＞ calcareous soil,while in MCP and KCl systems the reduction of pH followed the sequences of calcareous soil ＞ paddy soil ＞red soil and red soil ＞ calcareous soil ＞ paddy soil, respectively. The interactions of the NPK fertilizers on pHwere significant. MCP plus KCl or MCP plus AS reduced pH values more than the fertilizers applied solelyin the paddy soil, but AS partly counteracted the effect of MCP on pH in the 1 d sample of the calcareoussoil. The effect of MCP on pH was trivial when MCP was applied in combination with KCl or AS in the redsoil. When applied in combination with AS, KCl did not affect soil pH initially, but suppressed the reductionof pH at the later incubation stage, which was related to inhibition of nitrification by KCl in the soils.     

可变电荷土壤对酸雨敏感度的影响因子

The sensitivity of a large number of variable charge soils to acid rain was evaluated through examining pH-H₂SO₄ input curves. Two derivative parameters, the consumption of hydrogen ions by the soil and the acidtolerant limit as defined as the quantity of sulfuric acid required to bring the soil to pH 3.5 in a 0.001mol L^-1 Ca(NO₃)₂ solution, were used. The sensitivity of variable charge soils was higher than that of constant charge soils, due to the predominance of kaolinite in clay mineralogical composition. Among these soils the sensitivity was generally of the order lateritic red soil > red soil > latosol. For a given type of soil within the same region the sensitivity was affected by parent material, due to differences in clay minerals and texture. The sensitivity of surface soil may be lower or higher than that of subsoil, depending on whether organic matter or texture plays the dominant role in determining the buffering capacity. Paddy soils consumed more acid within lower range of acid input when compared with upland soils, due to the presence of more exchangeable bases, but consumed less acid within higher acid input range, caused by the decrease in clay content.     

我国某些土壤中硫素的氧化

The status and activities of boron in soils were studied by the approach of electro-ultrafiltration(EUF).The samples of soils,including brown-red soil and calcareous alluvial soil,were collected from Hubei Province of China.The soil samples were incubated in saturated water and then their nutrients were ultrafiltrated with EUF equipment.Filtration and extraction were conducted in accordance with routine process,but fractions in anode and cathode were all collected.Analyses of B,K^ ,Mg^2 ,Ca^2 ,Cl^- and pH in fractions supposed that boron existed not only in a simple form of borate but also in ion -pair with cations partly in acidic soil,and borate was the primary form existing in the calcareous soil.In studying desorption kinetics with EUF,the boron content of Fractions 2-6 was accumulated.and the accumlative quantities were fit to time factors in three kinetic equations:the zero-order,first-order,and parabolic diffusion equations,Fit degree of the parabolic diffusion equation was the best,followed by the zero-order equation,and the first-order equation was the worst。     

Interaction of NPK fertilizers during their transformation in soils: Ⅲ. Transformations of monocalcium phosphate

Interactions of N, P and K fertilizers in soil-plant systems are widely recognized. This study focused on the transformations of monocalcium phosphate (Ca(H2PO4)2) (MCP) with co-application of ammonium and potassium fertilizers in three different soils. The results showed that after 1 d incubation a large portion of the MCP applied in the paddy,calcareous and red soils became the water-insoluble form and the recoveries of P applied as Olsen P varied greatly in these three soils. Application of ammonium sulfate ((NH4)2SO4) (AS) or potassium chloride (KC1) reduced WSP significantly in the soils with AS more effective than KC1 in the calcareous soil, while the reverse occurred in the red soil. Meanwhile, in the paddy soil, co-application of the two fertilizers reduced WSP more than when the fertilizers were applied individually. The co-application of AS with MCP in the paddy and calcareous soils significantly reduced Olsen P, but the opposite occurred in the red soil. The experiment on the effect of different accompanying anions showed that the ammonium fertilizers (PNC1 and PNS) reduced WSP more effectively than the corresponding potassium fertilizers (PKC1 and PKS) in the calcareous soil due to the difference of the cations, whereas in the red soil, the chlorides reduced WSP more effectively than the sulfates. Overall, co-application of ammonium or potassium fertilizers with MCP significantly decreased availability of P from MCP during its transformation in soils, especially when MCP was applied in combination with ammonium in the calcareous soil.     

Natural Nitrogen-15 Abundance of Ammonium Nitrogen and Fixed Ammonium in Soils

The present article deals with the natural nitrogen-15 abundance of ammonium nitrogen and fixed ammonium in different soils.Variations in the natural ^15N abundance of ammonium nitrogen mineralized in soils under anaerobic incubation condition were related to soil pH.The δ ^15N of mineralizable N in acid soils was lower but that in neutral and calcareous soils was higher compared with the δ ^15N of total N in the soils.A variation tendence was also found in the δ ^15N of amino-acid N in the hydrolysates of soils.The natural ^15N abundance of fixed ammonium was higher than that of total N in most surface soils and other soil horizons,indicating that the increase of δ ^15N in the soil borizons beneath subsurface horizon of some forest soils and acid paddy soils was related to the higher δ ^15N value of fixed ammonium in the soil.     

Oxalic Acid Effect on Potassium Release from Typical Rice Soils of Kashmir

Batch experiments were employed to examine the influence of oxalic acid on release kinetics of potassium (K) from soils along with adsorption and desorption of soil K⁺. The soils used were three rice soils from high-, mid-, and low-altitude zones. The results showed that soil K extracted using 0.2 mol L^–1 oxalic acid was similar to that of 1 mol L^–1 boiling nitric acid (HNO₃). The relation between K release (y) and concentrations of oxalic acid (c) could be best described as y = a + b log c, whereas the best-fit kinetic equation of K release was y = a + b √t. The K release for soils was in the order Bonbagh > Ganasthan > Kreeri. An oxalic acid solution with low pH was able to release more K. Oxalic acid decreased soil K⁺ adsorption and increased desorption, the effect of which tended to be greater at lower pH.     

The dissolution of micas by fulvic acid

Three micas commonly occurring in soils, that is, biotite, phlogopite and muscovite, were shaken with 0.2% (W/V) aqueous fulvic acid (FA) solution for 710 h at room temperature. Proportions of major constituent elements extracted (Fe, Al, Mg, K and Si from biotite, Al, Mg, K and Si from phlogopite and Al, K and Si from muscovite) were determined.Depending on the type of mineral and its Fe content, substantial amounts of Fe, Al, Mg, K and Si were brought into aqueous solution by the FA under mild conditions. The ease with which the micas were attacked by the FA decreased in the following order: biotite > phlogopite > muscovite. IR and ESR analyses indicated the formation of metal—FA complexes as a major reaction mechanism by which the minerals were dissolved. Our data show that aqueous FA solution can dissolve from micas relatively large amounts of metals and Si, which may then become more available to plant roots and microbes, active in soil genesis processes, as well as participants in the synthesis of new minerals.     

含钾矿物中钾的释放及其与溶液环境中离子种类的关系

通过室内试验研究探讨5种含K矿物中K在不同溶液中的释放规律(释放量和释放速率).结果表明,不同含K矿物中K释放速率和释放量的顺序均表现为:黑云母>蛭石>金云母≥白云母>钾长石,不同K矿物释K速率在酸溶液中差异最大,其次在钙和钠盐溶液中,在水中的速率差异最小,这主要是受其矿物本身结构的影响.不同离子对含K矿物中非交换态K释放的促进作用差异显著:H~+>>Ca~(3+)>Na~+>H_2O>NH_4~+.随矿物K有效性增加,H~+和Ca~(2+)对矿物K释放的促进作用越大,而且H~+较Ca~(2+)对黑云母、金云母和长石中的K有更突出的促释作用.此外,Ca~(2+)较Na~+显著促进了黑云母和蛭石中K的释放,但对其他矿物中K释放的影响两者无显著差异.NH~+_4则显著抑制了各种矿物中K的释放,对黑云母和蛭石的抑制作用更强于对金云母和白云母的作用.     

Alkalinity exacerbates phosphorus deficiency in subtropical red soils: Insights from phosphate-solubilizing fungi

Red soils in subtropical regions are often low in available phosphorus (P), a vital plant nutrient. Phosphate-solubilizing microorganisms (PSMs) can release P from phosphate reservoir, making it accessible to plants. However, the complex interactions between PSMs and minerals in red soils are not yet fully understood. In this study, we investigated the effects of Aspergillus niger, a typical phosphate-solubilizing fungus (PSF), on phosphate dissolution in two representative red soils – an acidic soil and an alkaline soil. In the acidic red soil, the fungal abundance reached 3.01 × 10 ⁷ cfu g⁻¹ after a 28-day incubation period, with respiration of ~2000 mg C kg⁻¹. The secretion of oxalic acid promoted P release from inorganic phosphate (from ~1 to 187 mg kg⁻¹). Additionally, the contents of amorphous Fe/Al oxides decreased, which otherwise could have contributed to P sorption in the soil. In contrast, P availability declined in the alkaline red soil after the addition of A. niger, regardless of the P source (inorganic or organic phosphate). Meanwhile, the fungal respiration decreased to ~780 mg C kg⁻¹. Therefore, alkaline red soils with abundant carbonates are susceptible to P deficiency due to both the diminished function of PSMs and strong soil buffering. These findings have important implications for sustainable agriculture on alkaline red soils, as they suggest that the use of PSMs to improve P availability may be limited.     

富钾植物籽粒苋(Amaranthus spp.)对土壤矿物钾的吸收利用研究

运用土培、石英砂培、有机酸释钾实验及矿物X衍射分析研究了不同基因型籽粒苋(Amaranthusspp.)对土壤矿物钾的吸收利用及其机制。结果表明,籽粒苋能有效地利用土壤和云母(黑云母和金云母)中的钾;籽粒苋品种R104、CX4对钾的吸收量高于一般型品种(CX77);籽粒苋根系能引起云母矿物向蛭石转化;籽粒苋根系分泌物中的草酸比一般有机酸具有更高的释放矿物中钾素的能力。     

四苯硼钠溶液中含钾矿物非交换态钾的释放特性研究

含钾矿物的全钾含量、非交换态钾总量以及非交换态钾的释放速率因矿物种类而异,且3种参数之间没有必然的相关性。供试5种含钾矿物非交换态钾总量由高到低的顺序是:金云母 5.19% 黑云母3.08% 蛭石2.01% 白云母1.18% 钾长石0.24%,占各矿物全钾的比例分别为:58.4% 、99.7% 、62.5% 、14.2% 和4.98% ,平均达48%。选择较弱提取力的四苯硼钠溶液进行非交换态钾的释放特性研究,5种矿物非交换态钾3d释放累积量顺序为:黑云母 蛭石 金云母 白云母 钾长石;非交换态钾平均释放速率也表现为同样的顺序。上述5种矿物在弱提取力的四苯硼钠溶液中释放3 d,非交换态钾的平均释放速率分别为5.99、2.34、0.52、0.22和0.17 mg/(kgmin),差异明显。如何根据非交换态钾的释放量和释放速率来综合评价矿物钾的生物有效性是未来研究中需要明确的问题。     

Effect of Oxalic and Citric Acids on Zinc Release Kinetic in Two Calcareous Soils

Rate of zinc (Zn) release from solid to solution phase by organic acids can influence Zn availability in calcareous soils. The objective of the present study was to investigate the effect of different concentrations (1.1, 2.2, and 3.3 mM) of oxalic acid and citric acid on the kinetic release of Zn from two calcareous soils from Eastern Iran. The two organic acids showed significant difference in Zn release from studied soils. Cumulative Zn release during 72 h ranged from 5.85 to 10.4 mg kg^?1 in soil 1 and ranged from 8.7 to 16.9 mg kg^?1 in soil 2 using different concentrations of oxalic acid. The amount of cumulative Zn release after 72 h in soil 1 ranged from 13.65 to 28.77 mg kg^?1 and from 17.63 to 23.13 mg kg^?1 when different concentrations of citric acid was used. In general, Citric acid released 38% more Zn from soils than oxalic acid. The release of Zn from soils increased with citric acid concentration but decreased with increasing of oxalic acid concentrations in the solution. The simplified Elovich equation best described Zn release as a function of time (r² = 0.93 and SE = 0.78). From the present study, Zn release from soils can be limited by the higher concentration of oxalic acid, while citric acid is suitable for enhancing soil lability of Zn.     

Comparison of silicate minerals as sources of potassium for plant nutrition in sandy soil

Given the cost of conventional fertilizers and increasing demand as a result of increasing population growth, new sources of potassium (K) for plant nutrition need to be considered. Readily soluble nutrients are rapidly lost from well‐drained soils, and so it is appropriate to consider silicate minerals that release K slowly during weathering. In this paper, we compare the availability to plants grown in sandy soils of K from microcline (feldspar), biotite (mica) and nepheline syenite (nepheline + microcline) using leek (Allium ampeloprasum var. porrum L.) as a model plant. Pot experiments were carried out under controlled environmental conditions using natural and artificial soil. The performance of the minerals was compared with treatment with KCl and a negative control (no K added). Plant shoot diameter was measured weekly to assess growth rates. After 10 weeks, plant dry mass and soil and plant contents of soluble K were measured to determine offtake; mineralogical changes in biotite‐treated soils were assessed. Results for artificial and natural soil differed, reflecting differences in their mineralogy. With no added K, plant growth ceased after 2 weeks. Growth rates were greatest for KCl, followed by biotite; linear growth continued for 5 weeks in the natural soil and for the entire 10 weeks in the artificial soil. Growth rates with nepheline syenite (natural soil) and microcline (both soils) did not differ significantly from the negative control, but for nepheline syenite, leek shoot K content was significantly greater, demonstrating availability of K from this source. X‐ray diffraction analysis showed that biotite reacted to form vermiculite.     

Potassium fixation of some calcareous soils after short term extraction with different solutions

This investigation was done to determine the release of potassium (K) from five calcareous soils of southern Iran using 0.025 M CaCl₂, HCl and citric acid during six successive extractions and to study the K fixation capacity of the soils after K release experiment. Mineralogical study indicated that Vertisols and Mollisols were dominated with smectites; while other soils had illite, chlorite, palygorskite and smectite. Results indicated that citric acid extracted more K than CaCl₂ and HCl (137 vs. 111 and 113 mg kg^?1, respectively). The analysis of calcium (Ca), magnesium (Mg) and K concentrations in the solutions suggests that the exchange of K with soluble Ca and Mg (originated from dissolution of carbonates by acidic solutions) is the main mechanism of K release, but citrate is able to dissolve K-bearing minerals and release K in slightly calcareous soils. Soils with more illite released more K. Potassium fixation capacity of soils increased after extractions of soils with different extractants from 324 to 471 mg kg^?1, with no significant difference. It is suggested to apply more K fertilizers in K-depleted calcareous soils and use of different solutions for extracting K from soil minerals may be a temporary and short term solution.     

Adsorption of Cadmium and Zinc onto Micaceous Minerals: Effect of Siderophore Desferrioxamine B

The mobility, bioavailability, and environmental fate of heavy metals in soil are controlled by their adsorption onto soil minerals and solid organic matter. The adsorption is strongly affected by the presence of various low-molecular-weight organic acids. In this study, effect of hydroxamate siderophore desferrioxamine B (DFOB) on cadmium (Cd) and zinc (Zn) adsorption onto two micaceous clay minerals, muscovite and phlogopite, was evaluated in batch experiments. Results showed that the presence of DFOB diminished the adsorption of Cd and Zn onto both minerals, particularly under neutral to alkaline pH conditions. For instance, at pH 8.2, the presence of DFOB caused a decrease in the adsorption of Zn onto phlogopite by nearly 50%. The equilibrium adsorption of Cd and Zn was satisfactorily described using Freundlich isotherm. The adsorption isotherms showed that the affinity of Cd and Zn onto the minerals decreased in the presence of DFOB. For example, at pH 8.0, the presence of siderophore caused a decrease in the Freundlich adsorption isotherm coefficient K_F for Zn adsorption onto muscovite and phlogopite from 4.60 to 0.07 L g^-1 and from 3.56 to 0.36 L g^-1, respectively. These findings confirm the potential influence of siderophore on the fate of Cd and Zn in arid soils containing substantial contributions of micaceous silicate minerals.