Study on Water-Soluble Organic Reducing Substances: II. Organic Reducing Substances Produced from Anaerobic Decomposition of Milk Vetch (Astragalus sinicus L.)

The characteristics of electric charge and molecular weight distribution,oxidation-reduction regimes,e.g.Eh and amounts of organic reducing substances produced by milk vetch during anaerobic decomposition process,were studied by using electrochemical methods.Interaction between soils and organic reducing substances was also observed.The results indicate that the organic reducing substances were mainly the organic compounds with negative and amphoteric charges,which were distributed in two groups at anodic peak potentials of 0.25 and 0.69 volt in differential pulse voltammograms,respectively.Their apparent molecular weights are all less than 700 daltons,in which those active in oxidation-reducion reaction were distributed in the fraction with apparent molecular weight less than 200 daltons.The organic reduction substances can be oxidized by manganese oxides in their interaction with soils.     

Study on Water-Soluble Organic Reducing Substances. I. Determination of Organic Reducing Substances by Differential Pulse Voltammetry

A new method was proposed for study of organic reducing substances in soils.According to the theoretical relationship between the voltammetric behaviors and reduction-oxidation reaction of reducing substances,the working conditions of differential pulse voltammetry (d.p.v.)for determining the organic reducing substances produced during the processes of the anaerobic decomposition of plant materials were established with a glass carbon electrode as working electrode,1M Ag-AgCl electrode with large area as reference electrode,0.2M NH4Ac as supporting from -0.5 to 1.2 voltage(vs.M Ag-AgCl).The peak current proportional to the concentration of reducing substances,and the characteristic peak potential of each organic reducing substance were regarded as the quantitative and qualitative base,respectively.These results obtained under the conditions mentioned above directly reflect both the reducing intensity and capacity of the organic reducing system in soils.     

土壤水溶性有机物质的吸附、氧化和复合反应

A greater part of water-soluble organic substances,accounting for 60-70% of the total,could be adsorbed by soils,which included strongly and weekly reducing substances,positively and negatively charged substances and substances containing amido.There existed a tendency of decrease in adsorption of the negatively charged organic substances by the soil from South China to North China,with expression as Coulombian adsorption.A simulatneous reduction of iron and manganese appeared with clear voltammertric behaviours upon oxidation of water-soluble organic substances,Complexation of organic ligands with ferrous iron and manganous manganee was proved by differential pulse voltammetric method,with disappearance of oxidation peaks of ferrous iron and manganous manganese at 0.00 V and 0.35 V and occurrence of Fe^2 -complex and Mn^2 -complex at 0l75 V and 1.2V respectively,whose peak potentials shifted backward.     

配位体交换在减慢由酸雨造成的可变电荷土壤酸化速度中的意义

For the purpose of evaluating the role of ligand exchange of sulfate ions in retarding the rate of acidification of variable charge soils,the changes in pH after the addition of different amounts of HNO3 or H2SO4 to representative soils of China were measured .A difference between pH changes caused by the two kinds of acids was observed only for variable charge soils and kaolinite,but not for constant charge soils and bentonite,The larger the proportion of H2SO4 in the HNO3-H2SO4 mixture,the lower the calculated H^ ion activities remained in the suspension.The difference in H^ ion activities between H2SO4 systems and HNO3 systems was larger for soils with a low base-saturation(BS) percentage than those with a high BS percentage.The removal of free iron oxides from the soil led to a decrease in the difference,while the coating of Fe2O3 on a bentonite resulted in a remarkable appearance of the difference.The effect of ligand exchange on the acidity status of the soil varied with the soil type.Surface soils with a high organic matter content showed a less pronounced effect of ligand exchange than subsoils did.It was estimated that when acid rain chiefly containing H2SO4 was deposited on variable charge soils the acidification rate might be slower by 20%-40% than that when the acid rain chiefly contained HNO3 for soils with a high organic matter content,and that the rate might be half of that caused by HNO3 for soils with a low organic matter content,especially for latosols.     

Adsorption of Phosphate on Variable Charge Soils

The study about the adsorption of phosphate on four variable charge soils and some minerals revealed that two stage adsorption appeared in the adsorption isotherms of phosphate on 4 soils and there was a maximum adsorption on Al-oxide-typed surfaces between pH 3.5 to pH 5.5 as suspension pH changed from 2 to 9, but the adsorption amount of phosphate decreased continually as pH rose on Fe-oxide typed surfaces. The adsorption amount of phosphate and the maximum phosphate adsorption pH decreased in the order of yellow-red soil > lateritic red soil > red soil > paddy soil, which was coincided with the content order of amorphous Al oxide. The removement of organic matter and Fe oxide made the maximum phosphate adsorption pH rise from 4.0 to 5.0 and 4.5, respectively. The desorption curves with pH of four soils showed that phosphate desorbed least at pH 5. Generally the desorption was contrary to the adsorption with pH changing.     

外生菌根真菌Laccaria bicolor S238N增强花旗松生长及其对磷钾吸收的能力

Two variable charge soils were submerged after the addition of 30g/kg of organic matter to examine the differences in behavior between iron and manganese with respect to reduction and the distribution of different froms of the reduced elements.The reduction of manganese proceeded almost synchronously with the fall in redox potential,while the reduction of iron showed a remarkable lag behind the Eh change.Once formed,the distribution of water-soluble,exchangeable and precipitatied forms of ferrous iron was controlled by pH,CEC of the soil and total concentration of the element.For manganous ions,the proportions of water-soluble and exchangeable forms in total Mn^2 were larger than those for ferrous ions.The reduction of the two elements led to a mobilization of them,and such effect persisted even after drying of the soil,i.e.,the content of amorphous Fe became higher than that of the original soil.     

氧化土和老成土中自然产生的有机酸对磷的活化

Citric and malic acids at concentrations of 0.1,1.0,10,and 100 mmol/L were added to three Ultisols and one Oxisol,The amount of P in solution increased with increasing organic acid concentrations,while the amount of Fe-and Al-bound P decreased.This result suggested that naturally occurring products of organicmatter decomposition could increase the P availability to plants in soils where there is a relatively large pool of Fe-and Al-bound P.The interactions between citric and malic acids at the above concentrations,and p added at rates of 10,20,40,and 80mg/kg were determined.At zero levels of organic acids,all added P became either labile or bound ,and greater proportions remained soluble as the concentration of orgaic acids increased,which suggested that organic acids reduced fixation of dissolved P in Fe-and AL-rich soils .Agricultural practices which increase organic matter input on P-deficient acid soild could decrease P deficiency,This would be important in many tropical and subtropical regions where these soils are common,and where the costs of fertilizers and lime are relatively high.     

磷的吸附对老成土和淋溶土中Cu、Zn离子吸附-解吸及其有效性的影响

Surface charge,secondary adsorption-desorption and form distribution of Cu^2 and Zn^2 in Ultisols and Alfisols having adsorbed phosphate were studied by potentiometric titration,adsorption equilibrium and sequential extraction method,respectively,The soil surface negative charges increased whereas the amount sequential extraction method,respectively.The soil surface ngative charges increased whereas the amount of positive charges decreased with increase of P adsorbed,The soil secondary adsorption capacity for Cu^2 and Zn^2 was positively significantly correlated with the amount of P adsorbed by the soils,which could be described by the Langmuir equation.The amounts of Cu^2 and Zn^2 desorption from soils were decreased after P adsorption by the soils and the relationship between them was linear,After the soils adsorbed P,form distribution of Cu^2 and Zn^2 in soils changed remarkably.     

长江中游水稻土潜育作用的特点

The gleyization of representative paddy soils in the middle reaches of the Yangtze River was characterized, taking oxidation-reduction potential(Eh), the amount of active reducing substances and the forms of iron and manganese as the parameters. The Eh value was linearly related with the logarithm of the amount of active reducing substances, which was contributed by ferrous iron by 83% on an average. The degree of gleyization of different horizons was graded as ungleyed, slightly gleyed, mildly gleyed and gleyed. The Eh of the four grades was > 500, 300-500, 100-300 and < 100 mV, respectively, and the corresponding amount of active reducing substances was < 1, 1-7, 7-30 and > 30 mmol_c kg^-1, respectively. The amount of ferrous iron of the four grades was < 0.5, 0.5-5, 5-25 and > 25 mmol kg^-1, respectively. The extent of gleyization of a soil was classified as upper-gleyed, middle-gleyed and lower-gleyed, depending on whether the depth of the gley horizon was less than 30 cm, 30-60 cm or more than 60 cm.     

中性盐和pH对红壤、砖红壤胶体交换性酸的影响

In the present work, the exchangeable acidity of a red soil colloid and a latosol colloid at different pH during reacting with four neutral salts was measured. The results show that the exchangeable acidity increased with increasing amounts of the neutral salts added, and the relation between them was almost linear. When the amount of the neutral salt added was lower than a certain value, the slope of the line was high, and the slope turned low when the amount exceeded that value, so there was a turning point in each line. The addition amounts of the neutral salts for the turning points were affected by the cation species of the neutral salts, but pH had less effect on them. After the turning points occurred, the exchangeable acidity of the red soil colloid still gradually increased with the addition amounts of the neutral salts, but that of the latosol colloid did not increase any more. The exchangeable acidity in NaClO₄, KClO₄ and NaCl solutions increased at first, and then decreased with increasing pH, that is to say, peak values appeared. The peak positions of the exchangeable acidity in relation to pH changed with neutral salt solutions and were affected by the surface characteristics of the soil colloids, but not affected by the amounts of the neutral salts added. The exchangeable acidity in the Ba(NO₃)₂ solution increased continuously with increasing pH. The exchangeable acidity of the red soil colloid was obviously larger than that of the latosol colloid.     

澳大利亚东部地区一些酸性硫酸盐土壤磷的特征

Forty-five acid sulfate topsoil samples (depth < 0.5 m) from 15 soil cores were collected from 11 locations along the New South Wales coast, Australia. There was an overall trend for the concentration of the HC1-extractable P to increase along with increasing amounts of organic C and the HCl-extractable trivalent metals in the topsoils of some less-disturbed acid sulfate soils (pH < 4.5). This suggests that inorganic P in these soils probably accumulated via biological cycling and was retained by complexation with trivalent metals or their oxides and hydroxides. While there was no clear correlation between pH and the water-extractable P, the concentration of the water-extractable P tended to increase with increasing amounts of the HCl-extractable P. This disagrees with some established models which suggest that the concentration of solution P in acid soils is independent of total P and decreases with increasing acidity. The high concentration of sulfate present in acid sulfate soils appeared to affect the chemical behavior of Pin these soil systems. Comparison was made between a less disturbed wetland acid sulfate soil and a more intensively disturbed sugarcane acid sulfate soil. The results show that reclamation of wetland acid sulfate soils for sugarcane production caused a significant decrease in the HCl-extractable P in the topsoil layer as a result of the reduced bio-cycling of phosphorus following sugarcane farming. Simulation experiment shows that addition of hydrated lime had no effects on the immobilization of retained P in an acid sulfate soil sample within a pH range 3.54.6. When the pH was raised to above 4.6, soluble P in the soil extracts had a tendency to increase with increasing pH until the 15th extraction (pH 5.13). This, in combination with the poor pH-soluble P relationship observed from the less-disturbed acid sulfate soils, suggests that soluble P was not clearly pH-dependent in acid sulfate soils with pH < 4.5.     

与有机物质的分解相关的还原作用对红壤磁性质的影响

Five soils derived from different parent materials were sampled from red soil region of southern China and studied by magnetic methodology to understand to what extent iron reduction would affect soil magnetic properties and how iron reduction would affect the magnetic minerals in soils.Reduction associated with organic matter decomposition strongly affected soil magnetic parameters at low pH.The losses of original soil magnetic signals in terms of magnetic susceptibility(χ),‘Soft’ isothermal remanent magnetization (‘Soft’ IRM),anhysteretic remanent magnetization(ARM) and saturation isothermal remanent magnetization(SIRM) at pH 4-6 during the two-month saturation treatment,were 66%-94%,54%-90%,64%-95% and 33%-83%,respectively.These changes were interpreted as a consequence of substantial dissolution of maghaemite and haematite in the soils.At pH 10,however,there was no significant magnetic change observed.Moreover,stable single domain soil maghaemite grains were also sensitive to reduction,which suggested that both pedogenic and detrital maghaemite were not stable in acid and reducing environments.Goethite,instead,was the most stable iron form under reducing conditions.     

四川省紫色土天然和添加的镍不同形态的分布及转化

The distribution and transformation of added and native Ni in purple soils were investigated with both sequential extraction procedure and isotopic tracer technique.The distribution of added and native Ni was greatly dependent on soil properties.Low soil pH was favorable for soluble plus exchangeable(EX) Fraction,while Fe/Mn oxides and clay for Fe/Mn oxide bound(OX) and residual(RES) fractions.The added Ni,however,has not yet reached the distribution equilibrium up to the 150th day after incubation.This was reflected in the fact that the proportion of EX fraction from added Ni was 150%-600% as much as that of native Ni,while that of RES fraction was only about 80%,Once entering soil,the applied soluble Ni was rapidly transformed into other fractions,but the organic complexe (OM) fraction of added Ni was relatively stable during incubation.The carbonate bound(CAB)fraction showed a progressive increase and attained a peak value after 0-14d of incubation and thereafter decreased gradually.The occurrence time of this peak advanced as initial soil pH increased.but the peak would disappear when initial soil pH was higher than 7.5(or containing free CaCO3).The transformation processes of the EX,OX and RES fractions could be described by Elovich and two-constant rate equations,and the rate were positively correlated with soil pH,CEC and clay.These finding could explain why there are differences in ecological and environmental effects of Ni in different soils and at various intervals.     

半干旱土添加有机改良剂后有机质的化学结构变化

A 9-month incubation experiment using composted and non-composted amendments derived from vine pruning waste and sewage sludge was carried out to study the effects of the nature and stability of organic amendments on the structural composition of organic matter (OM) in a semi-arid soil.The changes of soil OM,both in the whole soil and in the extractable carbon with pyrophosphate,were evaluated by pyrolysis-gas chromatography and chemical analyses.By the end of the experiment,the soils amended with pruning waste exhibited less organic carbon loss than those receiving sewage sludge.The non-composted residues increased the aliphatic-pyrolytic products of the OM,both in the whole soil and also in the pyrophosphate extract,with the products derived from peptides and proteins being significantly higher.After 9 months,in the soils amended with pruning waste the relative abundance of phenolic-pyrolytic products derived from phenolic compounds,lignin and proteins in the whole soil tended to increase more than those in the soils amended with sewage sludge.However,the extractable OM with pyrophosphate in the soils amended with composted residues tended to have higher contents of these phenolic-pyrolytic products than that in non-composted ones.Thus,despite the stability of pruning waste,the composting of this material promoted the incorporation of phenolic compounds to the soil OM.The pyrolytic indices (furfural/pyrrole and aliphatic/aromatic ratios) showed the diminution of aliphatic compounds and the increase of aromatic compounds,indicating the stabilization of the OM in the amended soils after 9 months.In conclusion,the changes of soil OM depend on the nature and stability of the organic amendments,with composted vine pruning waste favouring humification.     

Effect of Zn Adsorption on Charge of Variable Charge Soils

The variation in appa rent carge of two typical variable charge soils resulting from Zn adsorption were studied by KCl saturation and NH4NO3 replacement methods.Results showed that zinc were adsorbed specifically to those sites with negative charge.As in different pH ranges,the percantages of specific and electrostatic adsorptions of zine and the mechanisms of specific adsorption were different,the effects of Zn adsorption on apparent charge were varied and could be characterized as:when 1 mmol Zn^2 was adsorbed,a change about 1 mmol in the apparent charge was observed in the low pH range(1),1.4 to 1.5mmol in the moderate pH range(II) and 0.55 to 0.6mmol in the high pH range (III).These experimental data,in terms of soil charge,proved once more author‘s conclusion in the preceding paper(Sun,1993) that in accordance with the behaviors of Zn adsorption by the variable charge soils in relation to pH,three pH ranges with different adsorption mechanisms were delineated;that is,in Range I,specific adsorption was the predominant mechanism,in Ranges II and III,specific and electrostatic adsorptions co-existed,but their specific adsorption mechanisms were not identical.     

Titratable Acidity and Alkalinity of Red Soil Surfaces

The surfaces of red soils have an apparent amphotenc character, carrying titratable acidity and titratable alkalinity simultaneously. The titratable acidity arises from deprotonation of hydroxyl groups of hydrous oxide-type surfaces and dissociation of weak-acid functional groups of soil organic matter, while the titratable alkalinity is derived from release of hydroxyl groups of hydrous oxide-type surfaces. The titratable acidity and titratable alkalinity mainly depended on the composition and content of iron and aluminum oxides in the soils. The results showed that the titratable acidity and titratable alkalinity were in significantly positive correlation not only with the content of amorphous aluminum oxide(Alo) and iron oxide(Feo) extracted with acid ammonium oxalate solution, free iron ox-ide(Fed) extracted with sodium dithionite-citrate-bicarbonate (DCB) and clays, but also with the zero point of charge (ZPC) of the samples. Organic matter made an important contribution to the titratable acidity.     

Adsorption of emerging sodium p-perfluorous nonenoxybenzene sulfonate (OBS) onto soils: Kinetics, isotherms and mechanisms

The widespread use of sodium p-perfluorous nonenoxybenzene sulfonate(OBS), a typical alternative to perfluorooctane sulfonate, has resulted in potential threats to the environment, but the adsorption behavior of OBS in soils has not yet been reported. In this study, the adsorption behaviors of OBS on five soils with different physicochemical properties were investigated. The rate of OBS adsorption was fast, and most of the OBS uptake was completed within 12 h. The good model fit of OBS adsorption to the pseudo-second-order and Elovich models indicated the occurrence of chemical adsorption. The adsorption isotherms of OBS on the soils were better described by the Freundlich model than by the Langmuir model, suggesting that the OBS adsorption sites on the soils were heterogeneous. This is possibly associated with various adsorption mechanisms including hydrophobic, π-π, hydrogen bonding, and electrostatic interactions,further confirmed by the good model fit to the D-R isotherm. Adsorption of OBS occurred on the soils, and the adsorption process was spontaneous and endothermic. In addition, the soils were more suitable for OBS adsorption at lower pH values due to the stronger electrostatic adsorption. The OBS adsorption on the soils decreased with the increase of soil depth from 0 to 30 cm. Moreover, the presence of organic matter and ammonia nitrogen in the soils was favorable for OBS adsorption, and these parameters decreased with increasing soil depth, making OBS adsorption less prominent in the deeper soil. This study indicates that OBS is easily enriched in surface soils, and that soil organic matter and ammonia nitrogen significantly affect OBS migration in soil.     

有机物料对淹水土壤中施入的镉形态的影响

The effect of three organic materials(rice straw,Chinese milk vetch and pig manure)on the fractionation of cadmium added into two soils(a red soil and a fluvo-aquic soil) was studied using submerged incubation experiment.The organic materials increased soil soild organic carbon(SOC),pH value,the concentration of active Si in all the treatments and active Fe and Mn in some treatments.Accumulated SOC caused directly the increase of Cd bound to solid organic matter and consequently the decrease of exchangeable Cd.Higher active Si and pH,as well as lower Eh,were also responsible for the reduction of exchangeable Cd.Cd bound to mn oxide was positively correlated with pH values and rose significantly after one-month incubation,but decreased after three-month incubation.Cd bound to amporphous Fe oxide increased with the incubation time,but was not affected significantly by adding organic materials.     

碱稳定污泥污水对土壤可提取有机碳和铜的影响

An incubation experiment was conducted to evaluate the potential for water contamination with sludge-derived organic substances and copper following land application of alkaline-stabilised sewage sludge. Two contrasting sludge-amended soils were studied. Both soils were previously treated with urban and ruralalkaline biosolids separately at sludge application rates of 0, 30 and 120 t ha^-1 fresh product. The air-driedsoil/sludge mixtures were wetted with distilled water, maintained at 40 % of water-holding capacity and equilibrated for three weeks at 4 ℃ before extraction. Subsamples were extracted with either distilled wateror 0.5 mol L^-1 K₂SO₄ solution. The concentrations of organic C in the aqueous and chemical extracts were determined directly with a total organic carbon (TOC) analyser. The concentrations of Cu in the twoextracts were also determined by atomic absorption spectrophotometry The relationship between the two extractable organic C fractions was examined, together with that between extractable organic C concentration and extractable Cu concentration. Application of alkaline biosolids increased the concentrations of soil mobile organic substances and Cu. The results are discussed in terms of a possible increase in the potential for leaching of sludge-derived organics and Cu in the sludge-amended soils.     

七种钾释放动力学方程的比较和动力学参数的应用

Batch equilibrium experiments were conducted to investigate cadmium （Cd） sorption by two permanent-charge soils, a yellow-cinnamon soil and a yellow-brown soil, and two variable-charge soils, a red soil and a latosol, with addition of selected organic acids （acetate, tartrate, and citrate）. Results showed that with an increase in acetate concentrations from 0 to 3.0 mmol L^-1, Cd sorption percentage by the yellow-cinnamon soil, the yellow-brown soil, and the latosol decreased. The sorption percentage of Cd by the yellow-clnnamon soil and generally the yellow-brown soil （permanent-charge soils） decreased with an increase in tartrate concentration, but increased at low tartrate concentrations for the red soil and the latosol. Curves of percentage of Cd sorption for citrate were similar to those for tartrate. For the variable-charge soils with tartrate and citrate, there were obvious peaks in Cd sorption percentage. These peaks, where organic acids had maximum influence, changed with soil type, and were at a higher organic acid concentration for the variable-charge soils than for the permanent charge soils. Addition of cadmium after tartrate adsorption resulted in higher sorption increase for the varlable-charge soils than permanent-charge soils. When tartrate and Cd solution were added together, sorption of Cd decreased with tartrate concentration for the yellow-brown soil, but increased at low tartrate concentrations and then decreased with tartrate concentration for the red soil and the latosol.