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.     

水溶性有机还原物质研究: Ⅲ. 稻草分解产物的电化学性质及其与可变电荷土壤的相互作用

Some electrochemical properties,such as pH,Eh,and voltammetric behavior.of the decomposition products of rice straw and the interactions of these products with soils were studied.The pH,Eh,and amounts of organic reducing substances changed markedly during the 6-day anaerobic decomposition.pH decreased sharply to pH 5 on the tenth day and then increased gradually to 7 on the 45rh day.The amounts of organic reducing substances increased almost synchronously with the fall of redox potential during the first 15 days.The differential pulse voltammetric(dpv) behavior changed not only in the peak current but also in the peak potential.The fractions with apparent molecular weights lower than 200 daltons appeared to be active in dpv behavior.The electric charge and positively charged,respectively.The group with a low apparent molecular weight and a negative charge was the main components responsible for the lower anodicpeak potentials.They were oxidized first during the interactions of the organic reducing substances with soils.     

施加有机物料对土壤有机质影响的研究

研究结果证明,有机物料的矿化速度在绵土中,牛粪>麦草>玉米秆>草术樨;在塿土中,牛粪>玉米秆>麦草。各类还田有机物的腐殖化系数,在绵土中玉米秆为0.25,麦草为0.25,草木樨为0.26,牛粪为0.21,在塿土中玉米秆为0.35,麦草为0.37,牛粪为0.31。施入物料后土壤有机质的累积与物料的矿化速度和施后时间呈负相关,与加入有机物量呈正相关。文中计算了本地区维持土壤耕层一定的有机质水平,每亩耕地每年需加入有机物料的数量。     

土壤中水溶性有机物质的数量、性质及其变化

水溶性有机物质的数量可因绿肥种类、土壤和时间而异。该物质是一类分子量低、带不同电荷(正、负电荷)和等电点的物质,并含有羧基和胺基。其中的某些性质随时间而变。该物质的数量与Eh的相关系数显著。其还原性因绿肥种类而异。工作中应用了凝胶层析、红外、可见光谱分析和等电聚焦技术。     

低分子量有机酸对土壤有效磷及重金属释放影响的研究进展

农药化肥的过量施用、重金属矿产开发冶炼、污水灌溉等导致土壤磷素养分降低和重金属污染,对生态环境、粮食安全和人类健康带来一定的风险隐患。土壤低分子量有机酸是一类重要的土壤有机活性物质,在土壤质地、养分循环和重金属毒害等方面起重要作用,但低分子量有机酸对土壤磷素和重金属释放影响的研究尚没有系统归纳。本文结合国内外研究进展,综述了土壤低分子量有机酸的来源、浓度、功能及其影响因素,举例说明了低分子量有机酸种类、浓度等对土壤磷及重金属释放的影响。系统总结了低分子量有机酸对土壤磷活化及重金属释放的机制。低分子量有机酸与其他物质协同提升土壤磷素有效性和降低重金属污染,这些结果为土壤磷素有效性的提升和重金属污染土壤修复提供科学依据和技术支撑。     

Sorption of Water-Soluble Organic Substances by Mineral Horizons of Podzol

Transformation of water-soluble organic substances entering mineral horizons of podzol from the forest litter was studied in a model column experiment. The concentration of organic matter in the solution after its interaction with the E horizon increased by 10–44% due to the release of native soluble organic matter. This was accompanied by changes in the quality of water-soluble organic matter: the portion of hydrophobic components increased, the coefficients of extinction at 254–280 nm decreased, and the portion of low-molecular-weight compounds slightly decreased with a corresponding increase in the portion of high-molecular-weight compounds. Upon the interaction of water-soluble organic substances with the E horizon, the pH values first decreased and then slightly increased, which could be due to sequential desorption of organic acids of different strengths. Dissolved organic substances from the E horizon were partly sorbed in the BF horizon at the rate of about 65 mg С/100 g, or 22% of C_org in the BF horizon. The sorption resulted in the removal of mainly hydrophobic medium- and high-molecular-weight (>7000 Da) organic substances from the solution. As judged from the coefficients of extinction in the UV area, the sorbed substances were characterized by a higher aromaticity in comparison with the substances remaining in the solution. The sorption of organic substances in the BF horizon was accompanied by the rise in the pH of the solution, which corresponded to binding of organic anions on the surface of iron hydroxides according to the mechanism of ligand exchange with OH ions.     

Macromolecule‐P associations and inositol phosphates in some chilean volcanic soils of temperate regions

Abstract

Total organic P, humic and fulvic acid‐P associations and inositol phosphates in nine volcanic soils of southern Chile were determined. The concentration of organic P (Po) ranged from 654 to 1942 ppm accounting for 49% to 64% of total soil P. Phosphorus associated to humic (HA‐P) and fulvic acids (FA‐P) accounted for 51–68% and 32–49% of Po, respectively. Inositol penta‐ and hexaphosphates represented 42% to 67% of Po suggesting that significant amounts are associated with both humic and fulvic acids. Po content was significantly correlated to organic C, total soil P and HA‐P. HA‐P and FA‐P fractions obtained from the most representative soil were examined by dyalisis and gel filtration. While approximately 96% of HA‐P presented a molecular weight higher than 100,000 daltons, 53% of FA‐P had a molecular weight under 12,000 daltons. It is suggested that these more labile organic P forms would be more easily mineralized, thus increasing the available P pool.     

Valorization of Organic Wastes to Reduce the Movement of Priority Substances Through a Semiarid Soil

In this work, we examined the effect of two different organic wastes, composted sheep manure and coir, on the sorption, persistence, and mobility of three pesticides (alachlor, chlorfenvinphos, and chlorpyrifos) included as priority substances in European Directive 2013/39/EU. With this aim, leaching studies were conducted using disturbed soil columns filled with a typical agricultural soil (hipercalcic calcisol) from a semiarid area (southeastern Spain) to determine their potential for groundwater pollution. The three compounds were found in leachates of unamended soil although in different proportions: 53% (alachlor), 9% (chlorfenvinphos), and 6% (chlorpiryfos). The addition of organic wastes significantly increased the sorption of the studied pesticides. As a consequence, the half-lives of the studied pesticides were higher in amended than in unamended soils. A marked reduction of the amount recovered in leachates was observed in the amended soils, except for chlorpiryfos, whose recoveries barely changed. According to their potential groundwater pollution calculated as the groundwater ubiquity score (GUS) index, alachlor and chlorfenvinphos show medium leachability while chlorpiryfos is unlikely to leach.     

Characterization of humic substances obtained from calcareous soils from Greece with various extractants. II. Physical characterization

Humic substances from the Ah horizons of five differently calcareous soils from Greece were successively extracted with organic solvents and/or 0.1 N NaOH and they were characterized by UV/VIS/IR spectroscopy and differential thermal analysis (DTA). Diethylether, acetone and dioxane extracts contained non-humic substances such as aliphatic and aromatic ethers, esters, alcoholes and long aliphatic chains, while low molecular weight humic substances were found in the ethanol extracts. All the extracts were found to contain phenolic and ?-acceptor compounds. Some differences in the physical characteristics of the humic substances were associated with the kinds of vegetation. The IR-spectra showed no essential differences between HA's and FA's extracted directly with NaOH or after previous soil extraction with organic solvents. HA's extracted directly by NaOH from soil samples under grass had a higher degree of condensation and thermal stability and generally higher carbon contents than those from soils under pine, cultivation and sedges.     

Molecular size distribution and enzymatic degradation of organic phosphorus in root exudates of spring barley

Seeds from two varieties of spring barley (Prisma and Camorgue) were grown axenically in water. After 14 days, the culture solutions contained organic P substances (about 4 g P per plant) derived from root exudation, representing about 3% of the total P found in the seed. Gel filtration, separated the organic P into two well defined peaks, one with a high molecular weight (>45000 daltons) and the other with a low molecular weight (<500 daltons). The bioavailability of the soluble organic P released was assessed enzymatically and chemically. At the optimum pH of 5.0, phytase and acid phosphatase hydrolysed about 80% and 65%, respectively of the organic P in the exudate after 24 h whereas at the optimum pH of 9.8, alkaline phosphatase hydrolysed up to 40% P after the same length of time. In a pH 5.0 buffer, up to 10% of the organic P was hydrolysed compared with up to 45% in a pH 9.8 buffer. The high molecular weight organic P fraction recovered from the G-75 Sephadex behaved similarly.     

Amino acid composition of soil peptides chromatographed by high performance liquid chromatography on C18 and C8 columns

Summary Low molecular weight fractions (LMW; <5000 daltons) of organic matter were isolated from three soils by a mild extraction procedure and gel-permeation chromatography. The peptides present in the LMW soil extracts were separated on a Whatman Partisphere C18 and a Beckman Ultrapore C8 column by reverse-phase high performance liquid chromatography (HPLC). The peptide fractions were collected, acid hydrolyzed, and analyzed for amino acid composition. The C8 bonded-phase column gave better separation of the LMW soil peptide material than the C18 column. The total quantities of amino acids released from LMW peptides by acid hydrolysis were greater than the quantities released by immobilized protease hydrolysis (Warman and Isnor 1990). Total soil N present in the form of LMW peptides in these three soils ranged from 4 to 15%. The total recovery of peptide amino acid-N showed little difference between the C18 and C8 columns for two of the soils tested.     

第二松花江干流底泥有机无机复合体组成及有机碳分布特征

以第二松花江干流为对象,研究其底泥有机无机复合体的组成及有机碳分布的差异,同时分析底泥有机无机复合体组成及其有机碳分布与岸边土壤之间的关系。结果表明:底泥与岸边土壤在有机无机复合体组成、有机碳分配和腐殖质组成方面表现出较好的一致性,说明岸边土壤对底泥的有机碳组成和分布有显著贡献。底泥的中央粒径呈现上游高、下游低的特点,抚松底泥中央粒径为200μm,吉林底泥中央粒径在70μm左右,榆树、松原底泥中央粒径在50μm左右;底泥的有机碳和腐殖酸含量也表现出上游高于下游的特点。底泥有机无机复合体组成以砂粒复合体为主,黏粒、粉粒复合体含量次之;并且随着复合体粒径的增加,有机碳含量减少。底泥HA/FA均大于1,从上游至下游表现为抚松>吉林>榆树>松原;底泥HA/FA均小于岸边土壤。     

不同开垦年限水稻土还原性物质含量及其分布

以辽宁省各地棕壤型、草甸土型水稻土为研究对象,探讨了不同开垦年限的棕壤型、草甸土型水稻土中还原性物质总量、活性还原性物质、络合态铁、水溶性亚铁、水溶性亚锰含量及其分布状况。结果表明,不同开垦年限供试水稻土随着开垦年限增加表层还原性物质总量、活性还原性物质、络合态铁、水溶性亚铁和水溶性亚锰含量明显增加,且均随土壤深度增加而减少,其积累主要集中在土壤上层。土壤络合态铁与还原性物质总量和活性还原性物质均呈极显著正相关,表层土壤有机质对铁、锰的络合减少了铁、锰元素向剖面下层的迁移数量。开垦10年以上,水稻土耕层中还原性物质就明显积累,直至60年,其积累量仍不断增加,因此生产上必须采取措施抑制水稻土中还原性物质的累积。     

Effect of Low Molecular Weight Organic Anions on the Adsorption of NO3− by Variable Charge Soils

Low molecular weight organic acids exist widely in soils and have been implicated in many soil processes. The results in the present paper showed that the presence of organic anions led to a decrease in the adsorption of NO₃⁻. The effect of citrate was much larger than that of oxalate and malate. Among different soils, the effect for Hyper-Rhodic Ferralsol and Rhodic Ferralsol was larger than that for Haplic Acrisol, which was related to the content of iron oxides in these soils. The effect of organic anions decreased with the increases in pH value and the amount of organic anions added. The organic anions depressed the adsorption of NO₃⁻ through two mechanisms, the competition of the organic anions for adsorption sites with NO₃⁻ and the change of soil surface charge caused by the specific adsorption of organic anions.     

生物炭添加对旱作农田土壤溶解性有机质及其

为揭示生物炭添加对旱作农田土壤溶解性有机质（DOM）及其动态的影响,通过定位试验,探讨了不同生物炭施用量小区土壤在2012—2017年间溶解性有机碳、溶解性无机碳和DOM的荧光光谱组分及其紫外光谱特征的变化特征。结果表明：添加生物炭总体上能够提高土壤DOC和DIC含量,且随着添加量的增加而递增。相同生物炭添加量处理中,DOC含量随施用时间增加显著降低,而DIC含量呈逐渐升高的趋势。DOM芳香化程度随施用时间延长而显著增大,施用3年后3%和5%添加量处理的芳香化程度较CK显著降低,而1%添加量处理与CK无显著差异。DOM分子量在不同施用年限之间呈增大趋势。随着生物炭添加量的增加,分子量在不同施用年限间的差异逐渐减小。土壤DOM主要由UVC类腐殖酸（C1）、UVA类腐殖酸（C2）、土壤富里酸（C3）和类色氨酸（C4）4种物质组成,其中以C1和C2为主。整体而言,除添加1%生物炭时C2随施用年限增加而降低之外,不同处理中C1及C2均随着施用年限的增加而逐渐增加,而C3和C4则显著降低。不同处理下DOM的来源以外源输入为主,微生物内源输入为辅,添加生物炭在一定程度上增强了DOM的生物可利用性。生物炭的长期施入会引起旱作农田土壤DOM组分变化,总体趋势是大分子量腐殖酸类物质在增加,而小分子量蛋白类物质在减少。     

Influence of Organic Manure on Organic Phosphorus Fraction in Soils

The transformation of organic P(Po) from organic manures in two types of soils (ultisol and entisol) and the influences of external addition of organic substance or inorganic P(Pi) on Po under the condition of the 60% maximum water capacity were investigated.The results obtained from Po fractionation experiments indicated that all the Po fractions except for the highly resistant Po fraction decreased during incubation.Application of pig feces and cow feces could largely increase each fraction of Po in the soils.Immediately after application of organic manure into the soils a large part of labile and moderately labile Po from organic manure was transferred into moderately resistant Po,which might be due to the fact that Ca-or Mg-inositol P was precipitated into Fe-inositol P.However,the availability of Po from organic manure in the soils would increase again after incubation because of the transformation of moderately labile and resistant Po fractions into labile Po fractions.Addition of cellulose or Pi into the soils showed a good effect on increasing all the Po fractions except for the highly resistant Po,and this effect was much more pronounced when cellulose was applied in combination with Pi.Therefore,in view of the effect of organic manure on improving P nutrition to plant,attention should be paid to both the Po and the organic substances from organic manure,It is suggested that application of Pi fertilizer combined with organic manure may be referred to as an effective means of protecting Pi from chemical fixation in soil.     

Transformation of Water-Soluble Organic Substances in Litters of Podzols in the Background and Technogenic Areas of the Kola Peninsula

Mineralization of water-soluble organic substances in forest litters of different compositions under conditions of their pollution with heavy metals from aerogenic emissions is considered. Water-soluble organic substances of the pine forest litters are shown to be less stable than that under the spruce forests irrespective of their pollution; the portion of mineralized at 20°C carbon for a month reached 40%. In the spruce litters, mineralizable amounts of carbon are related to their pollution: in the technogenic areas, compared to the background ones, carbon losses from the litters are twice greater. In the course of decomposition, in the spruce and pine litters, phenol compounds accumulate among the water-soluble organic compounds, and this process is more intense in the contaminated areas. After the decomposition of all the litters, irrespectively of their composition and the distance from the pollution sources, the water-soluble organic substances are characterized by higher indices of humification (HIX), more intense fluorescence, and greater coefficients of specific extinction (E₂₆₀). In the ultraviolet spectra, bands appear in the region of aromatic amines absorption. These changes indicate the transformation of water-soluble organic substances: the degrees of their condensation and aromaticity increase and nitrogen-containing aromatic compounds are formed.     

沈阳市郊日光温室土壤有机碳组成特征研究

对沈阳市郊东陵、于洪、苏家屯、新城子四区蔬菜栽培15年左右的日光温室土壤有机碳组成特征进行了研究,以相应温室外的露地栽培土壤为对照,结果表明:日光温室蔬菜栽培的有机肥用量远远高于温室外露地栽培。随着有机肥用量增加,温室土壤水溶性碳、腐殖酸碳的增加比例小于胡敏素碳的增加比例。各区温室土壤总有机碳、非腐殖质碳、腐殖质碳数量的平均值分别是温室外露地的1.76～3.06倍、3.41～5.23倍、1.57～2.99倍。温室土壤中非腐殖质所占比例较对照露地的大,其水浮物碳占总有机碳比例是对照露地的1.80～2.63倍,温室和露地土壤水溶性物质碳占总有机碳的百分比大多低于2%。温室土壤胡敏酸碳、富里酸碳、胡敏素碳数量均高于对照露地,但有1/3以上的温室土壤H/F低于对照露地土壤。由于不同农户的水、肥管理水平差异较大,不同温室土壤的总有机碳及各组分的碳变异性较大。     

低分子量有机酸对石灰性潮土无机磷形态转化的影响

无菌培养条件下,模拟缺磷胁迫时植物根系分泌的低分子量有机酸种类和数量,采用石灰性土壤无机磷分级方法,研究了低分子量有机酸对石灰性潮土无机磷形态转化的影响。结果表明:①在石灰性潮土中无机磷主要以有效性较低的磷酸钙盐(Ca10-P等)形式存在,而有效性较高的形式(Ca8-P等)含量较少,Ca2-P就更少。②有机酸通过结合土壤中可以使磷固定的Ca、Fe及Al,致使根际范围酸化,促进磷酸盐的形态转换,增加磷的有效性。这种促进能力因有机酸种类和性质的不同而异,其促进能力大小顺序为草酸>柠檬酸>酒石酸。     

集约经营下雷竹林土壤低分子量有机酸的初步研究

低分子量有机酸对养分循环与植物生长起着重要作用,雷竹具有发达的鞭根系统,因此了解其土壤中的有机酸状况显得尤为重要。本研究采集了雷竹主产区浙江省临安市太湖源镇不同种植年限的雷竹土样,通过高效液相色谱法对其中的低分子量有机酸进行初步的定性和定量分析。结果表明:雷竹林土壤中主要含有马来酸和丁二酸,并含有少量富马酸;随着雷竹种植年限的增加,土壤中有机酸总量有增加的趋势。