不同施肥处理土壤胡敏酸及其级分与Fe2+络合特征Ⅱ.胡敏酸级分与Fe2+络合特征

采用酒精沉淀法对不同施肥处理胡敏酸进行分级 ,在研究胡敏酸级分组成变异以及各级分性质变化的基础上 ,研究了胡敏酸各级分与Fe2+的络合特征。结果表明 ,胡敏酸各级分随级分数的增大芳构化度逐渐降低 ,分子结构趋于简单。在所分离的 7个级分中 ,均以级分 3与Fe2+的络合能力最强。从级分 1到级分 3络合能力逐渐增强 ,级分 3到级分 7络合能力逐渐降低。胡敏酸A型级分的络合能力一般大于P型。但若A型级分芳构化度过高 ,也存在A型级分小于P型现象。Rp型级分的络合能力明显比A型、P型级分小。不同施肥处理胡敏酸原样与Fe2+络合能力差异与其级分组成变异以及各级分的络合能力有密切关系     

有机物料腐解过程胡敏酸与Fe~(2+)的络合特征

采用玉米秸、绿豆秸、猪粪、羊粪4种有机物料进行腐解试验,研究了腐解过程形成的胡敏酸在不同条件下(pH、离子强度)与Fe2+的络合特征,结果表明,在相同条件下,粪肥腐解形成的胡敏酸与Fe2+的络合能力相对比秸秆的强。腐解过程胡敏酸与Fe2+的络合能力呈动态变化,胡敏酸与Fe2+的络合稳定常数与其羧基、总酸度成极显著正相关。在碱性条件下(pH=8.0),各有机物料腐解形成的胡敏酸与Fe2+的络合能力下降。     

不同施肥处理土壤胡敏酸及其级分 与 Fe2+的络合特征 Ⅰ.胡敏酸原样与 Fe2+的络合特征

采用 17年不同施肥处理 (无肥、化肥、秸秆、厩肥 )土耕层土样 ,在对土壤胡敏酸性质研究的基础上 ,着重研究不同施肥处理土壤胡敏酸与Fe2+的络合特征 ,揭示络合作用与胡敏酸性质以及环境条件的关系。结果表明 ,不同施肥处理土壤胡敏酸与Fe2+的络合能力不同。和无肥处理相比 ,化肥处理胡敏酸的络合能力加强 ,logk值 (络合稳定常数 )增大 ,有机肥处理则使胡敏酸的络合能力下降 ,logk值减小。logk值大小与胡敏酸的羧基、酚羟基以及总酸度有关。pH值、温度、离子强度是影响络合稳定常数大小的环境因素 ,pH值由 4到 7,各处理胡敏酸的logk值增大 ,络合配位数也有增加趋势。温度升高 ,离子强度增大 ,logk值降低。胡敏酸与Fe2+络合反应是一个自发的放热反应 ,络合后整个体系的有序性增强 ,熵值减小。     

腐殖酸对汞的络合稳定特性及其环境学意义

对3种腐殖酸与Hg的络合稳定特性研究结果表明,腐殖酸与Hg的结合存在松结态与紧结态2种形态,其中富里酸主要以松结态为主,灰色胡敏酸与棕色胡敏酸则以紧结态占绝对优势。3种腐殖酸中富里酸对Hg的络合容量最高,但络合强度最低,其络合汞的环境活性将较高;灰色胡敏酸对Hg的络合容量最低,但络合稳定性最高,故所结合Hg的环境活性最弱。但受容量因素制约,灰色胡敏酸对Hg的络合稳定性将因Hg/灰色胡敏酸相对比例的升高而急剧下降。棕色胡敏酸对Hg络合特性介于富里酸与灰色胡敏酸之间。     

土壤胡敏酸与铜、锌离子的络合特征及生物有效性的研究

通过田间试验研究了胡敏酸(HA)与铜、锌离子的络合特性。结果表明,施肥后土壤HA向结构复杂方向转化,HA与Cu2+、Zn2+之间的络合稳定性提高。HA-Cu2+的logk值,有机肥大于化肥;HA-Zn2+的logk值,以化肥的作用更明显。土壤HA与Cu2+或Zn2+络合,倾向于形成混合或多核络合物。施有机肥可提高HA-Cu2+或HA-Zn2+的结合强度和增加结合数量,而施化肥处理则相反。培养试验结果表明,有机肥处理的HA,玉米吸收Cu2+、Zn2+量下降,单施化肥处理下降较小;其中Cu2+吸收量受影响程度较大,而Zn2+吸收量没有那么明显。     

腐殖酸对矿物结合汞活性的影响I. 腐殖酸对矿物结合汞挥发活性的影响

挥发试验结果表明,试验条件下,富里酸能极显著地促进Fe2O3-Hg,MnO2-Hg与高岭土结合汞的挥发,对膨润土结合汞和碳酸钙结合汞的挥发则表现抑制作用.棕色胡敏酸能促进各矿物结合汞的挥发.灰色胡敏酸影响最为微弱.腐殖酸对矿物结合态汞挥发性的影响与其对汞的络合容量与络合稳定性,矿物对汞的吸持特性,以及矿物与腐殖酸的作用特性密切相关.     

不同培肥方式黑土腐殖质形态特征研究

针对吉林省黑土区存在的土壤有机质下降、耕地质量退化等问题,利用公主岭国家黑土肥力与肥料效益监测基地连续20年的长期定位试验,采用核磁共振波谱分析法(NMR)、红外光谱分析法(IR)等现代分析方法,研究了不同培肥途径耕层土壤腐殖质的组成、形态结构及动态变化趋势。结果表明:不同培肥途径对耕层土壤腐殖质特征影响明显。施用玉米秸秆处理(S+NPK)和施用有机肥+轮作处理(M+NPK+R)均显著增加了土壤胡敏酸中脂肪族结构成分,单施有机肥处理(M+NPK)显著增加了土壤胡敏酸中羟基含量,S+NPK处理游离羧基含量显著增多。S+NPK、M+NPK及M+NPK+R处理,土壤富啡酸的甲基、亚甲基和次甲基结构成分显著增多,游离羧基含量也显著增多。单施化肥处理,浸提的富啡酸中无机碳酸盐和硅酸盐成分明显增多,化肥长期施用导致土壤中游离富啡酸数量显著减少,土壤的耗竭式利用,导致土壤中铁、铜结合态或络合态的富啡酸增加。不同培肥方式对黑土胡敏酸和富啡酸的元素组成影响有较大的差异,但均可引发胡敏酸C含量降低,N含量增加,富啡酸C、N、H含量增加,O含量降低,可通过不同的培肥方式对土壤腐殖质的元素组成进行调节。     

锰离子与胡敏酸络合反应特征研究

采用离子交换平衡法研究了在不同酸度、离子强度、温度条件下胡敏酸(HA)与Mn2+络合反应稳定性和热力学特征。结果表明,在相同离子强度、反应温度条件下,随着pH的升高,HA与Mn2+络合反应稳定常数增大;络合反应配位数在pH 3.0～5.0范围内随着pH的升高而增加,在5.0～7.0范围内随着pH的升高而降低;离子强度增加,HA与Mn2+络合反应表观稳定常数增加,离子强度从0.00升至0.10 mol L-1,HA与Mn2+络合反应配位数增加,但离子强度从0.10 mol L-1继续上升至0.15 mol L-1,配位数呈现下降的趋势;胡敏酸络合Mn2+标准自由能变ΔGmθ、焓变ΔHθm、熵变ΔSθm在298.2K、308.2K温度下均为负值,反应是自发进行的放热反应,较低的温度有利于反应的进行。     

两种培肥措施对黑钙土有机无机复合体腐殖质组成的影响

采用Kumada法研究了两种培肥措施对黑钙土及其复合体腐殖质组成的影响。结果表明,在根茬还田的基础上增施有机肥,可使全土及各级复合体的游离态和结合态腐殖质的胡敏酸、富里酸含量及△logK等不同程度地增大,PQ和RF值减小．腐殖化度降低,这种作用在粉粒复合体中表现最为明显。粘粒和粉粒复合体的游离态胡敏酸均为A或B型,细砂均为Rp型。随复合体粒径的增大,游离态胡敏酸类型的变化序列为A型(粘粒)→A型(粉粒)→Rp型(细砂);结合态胡敏酸大多为A型,少数为P或B型。黑钙土增施有机肥培肥后,腐殖质的腐殖化度会发生量变和型变。在黑钙土中,胡敏酸的型变,主要表现在全土和粉粒复合体的游离态腐殖质中。     

用凝胶层析法和示踪技术评估腐植酸分子量分级组成及其与Cd、Zn的络合特性

通过凝胶层析法对土壤腐植酸进行了分组提取,并对其各分子量分级组成及其与Cd、Zn的络合特性进行了研究.结果表明:土壤胡敏酸通过G-50可以分成3个较集中的组分,分子量分别为M=78180、M=48339及M=22863;通过G-100可以得到2个组分,分子量分别为M=63343和M=19870.富里酸通过G-50、G-100层析,则从总体上成为单一的宽带,分子量约为M=2300.腐植酸对Cd、Zn络合量的测定显示:胡敏酸对Cd、Zn的络合量呈2个明显的峰值,而富里酸只有1个峰值.两者对Cd、Zn络合量随洗脱体积的变化曲线与其吸光值随洗脱体积的变化曲线相一致.65Zn示踪技术研究65Zn与胡敏酸、富里酸络合的结论与常规方法一致.     

The involvement of iron and aluminum in the bonding of phosphorus to soil humic acid

Abstract

With a peat soil similar amounts of phosphorus (P) were coprecipitated with humic acid from alkali extracts over a limited range of strongly acidic pH, whereas with a mineral soil the amount was pH dependent. The difference between the two soils relates to the much greater total amounts of inorganic P and aluminum (Al) present in the extract of the mineral soil. In this acid mineral soil, Al rather than iron (Fe) may be involved in the formation of metal bridges in humic acid‐metal‐inorganic P complexes. Neither Al or Fe were implicated in binding of organic P to humic acid. The P species observed in humic acids was dependent on the pH at which they were precipitated from the alkali extracts. In the peat soil the inorganic P was an order of magnitude lower than the organic P.     

Effect of organic amendment on amount and chemical characteristics of humic acids in upland field soils

To assess the effect of continuous organic material (OM) application on soil humic acids, the amount and chemical characteristics of humic acids in various types of soils (n = 10) were compared between plots treated with farmyard manure (FYM) or rice straw compost (RSC) plus chemical fertilizer (CF) and plots treated with CF alone. The degree of humification (degree of darkening), molecular size distribution and ¹³C cross polarization/magic angle spinning nuclear magnetic resonance spectra of humic acids from CF‐treated soils showed wide variation among the soils. Humic acid content was generally larger in OM + CF soils than in corresponding CF soils, and the stable C isotopic ratio suggested partial replacement of indigenous humic acids with OM‐derived ones even where no apparent increase in humic acid content was observed. The rate of OM application and the indigenous humic acid content were related positively and negatively, respectively, to the apparent accumulation rate of humic acids among soils. The degree of humification of humic acids was generally smaller in OM + CF soils than in CF soils. Humic acids extracted from FYM and RSC exhibited chemical characteristics typical of humic acids having a smaller degree of humification, which suggested the contribution of OM‐derived humic acids to the differences between OM + CF and CF soil humic acids, such as larger average molecular sizes and smaller and larger proportions of aromatic C and O‐alkyl C, respectively, relative to total C in the OM + CF soil humic acids. Little change was observed in the chemical characteristics of humic acids when the degree of humification of indigenous humic acids was small. The effect of OM application on the chemical characteristics of humic acids was most conspicuous in soils containing humic acids having an intermediate degree of humification, possibly resulting from the combination of accelerated degradation of indigenous humic acids and the accumulation of OM‐derived humic acids.     

MOLECULAR SIZES AND FUNCTIONAL GROUPS OF HUMIC SUBSTANCES EXTRACTED BY 0.1M PYROPHOSPHATE FROM SOIL AGGREGATES OF DIFFERENT STABILITY1

Aggregates from non-cultivated soil and from cultivated soil enriched with mineral fertilizers or farmyard manure were separated into fractions of different diameter and stability. The humic substances extracted from each type of aggregate were subjected to gel-filtration on Sephadex. The more stable aggregates had a higher content of Na₄P₂O₇-extractable humus and free iron hydroxides, and a predominance of humic substances of apparent molecular weight >100 000, whereas the less stable aggregates were richer in compounds of low molecular weight. Structure stability was lower in the cultivated soil than in the non-cultivated, and in the soil with mineral fertilizers in comparison to that with farmyard manure. Humus of m.w. >100 000 had a COOH content twice as great and a phenolic OH content five times greater per unit of molecular weight than humus with m.w. <100 000. The former is the more suitable stabilizer of soil aggregates.     

三种有机肥水溶性分解产物对铜、镉吸附的影响

研究了稻草、紫云英和猪粪的水溶性分解产物对铜和镉的沉淀作用及其在红壤和潮土上的吸附影响。结果表明三种水溶性分解产物对铜镉的沉淀及吸附有双重效应：铬合效应和ｐＨ提高效应。在相同的ｐＨ值条件下,有机分解产物通过络合作用而不同程度地抑制了铜和镉的沉淀作用及其在两种土壤上的吸附。由于铜具有较强的形成络合物的能力,所以有机分解产物对铜的抑制效果对于镉的抑制效果。吸附等温线表明,在不调节ｐＨ时,三种有机分解产     

Effect of Organic Waste and Humic Acid on Some Growth Parameters and Nutrient Concentration of Pistachio Seedlings

Pistachio crops in Iran are grown in soil with low soil organic matter. Therefore, a field experiment was conducted at Izadyaran Company, Sirjan, Iran to study the effects of municipal solid waste compost (MSWC), cow manure, and methods of humic acid application (soil and foliar) on growth parameters and nutrients concentration of pistachio seedlings in a complete randomized design with six replications for two years (2011–2013). Results showed that cow manure decreased the leakage percent and maximum leaf number and leaf surface area were obtained in MSWC with foliar application of humic acid and cow manure without humic acid, respectively. The highest chlorophyll b and carotenoid were observed in the second year with cow manure treatment whereas foliar application of humic acid increased total chlorophyll. Calcium (Ca) and iron (Fe) decreased in the second year. At the first year Cow manure application increased phosphorus (P) and manganese (Mn) but in the second year increased magnesium (Mg) concentration. MSWC at the first year increased copper (Cu) and zinc (Zn) concentration. Cow manure and foliar application of humic acid increased the Nitrogen (N) concentration in the first year. These results may have implications for pistachio production in arid and semi-arid soils.     

化肥配施不同剂量有机肥对黑土团聚体中有机碳与腐殖酸分布的影响

【目的】 团聚体的形成为土壤有机碳的稳定提供了重要的物理保护,施用有机肥影响着土壤团聚体的形成,量化有机肥施用剂量与团聚体有机碳稳定性之间的关系对于阐明农田土壤有机碳的固碳机制具有重要意义。 【方法】 以黑龙江省海伦市国家野外科学观测研究站为平台,选择连续10年进行化肥配施不同剂量有机肥处理[0、7.5、15、22.5 t/(hm2·a)]的黑土为研究对象,将团聚体分组与腐殖酸提取相结合,分析了不同粒径团聚体中有机碳和腐殖酸的含量与光学特性。 【结果】 1)与单施化肥相比,化肥配施有机肥增加了大团聚体( > 0.25 mm)的分配比例与团聚体的平均重量直径,二者均随着有机肥剂量的增加而逐渐升高,回归拟合分析表明,团聚体的平均重量直径与有机肥剂量之间呈现显著的正相关关系(P=0.03)。2) 2~0.25 mm团聚体是黑土有机碳的主要贮存场所,约占有机碳总量的64.8%~68.8%,大团聚体中有机碳的含量与储量均随着有机肥剂量的增加而逐渐升高, < 0.053 mm团聚体中有机碳含量与储量则维持在较稳定的水平。3)各粒级团聚体中腐殖酸碳含量以0.25~0.053 mm团聚体最高,各粒级团聚体中腐殖酸碳占有机碳百分比之间的差异不显著。化肥配施有机肥提高了各粒级团聚体中腐殖酸碳的含量,使团聚体对有机碳的固持能力增加,且各粒级团聚体中腐殖酸碳的含量随着有机肥剂量的增加逐渐升高。4)化肥配施有机肥增加了各粒级团聚体中腐殖酸的E4/E6比值,表明其分子结构简单化,且以 > 2 mm和0.25~0.053 mm团聚体中腐殖酸E4/E6比值的增加最显著。 【结论】 在黑土中,长期连续进行化肥配施有机肥,促进了团聚体的形成,改善了耕层土壤结构,增加了团聚体中有机碳的积累与固持能力,并使各粒级团聚体中腐殖酸的结构“年轻化”,这种促进作用在高剂量有机肥施用下更为显著。实际生产中,在短期内可通过适当提高有机肥的施用量以提高黑土肥力及其固碳能力。     

溶液培养条件下腐殖酸对铁异化还原的影响

腐殖酸对土壤和水体环境中铁(Fe)的还原过程有重要影响。本文采用从山西大同风化煤、河南巩县褐煤、云南昆明滇池底泥中提取制备的腐殖酸,通过布置培育试验并接种土壤悬液,研究了不同来源的腐殖酸对无定形氧化铁异化还原的影响。结果表明:单独添加腐殖酸对氧化铁的还原几乎没有影响;而当同时添加腐殖酸与葡萄糖时,培养基质中氧化铁的还原过程显著加强;腐殖酸浓度越高对氧化铁还原的促进作用越明显。不同来源的腐殖酸因其复杂程度和结构不同,对氧化铁还原的促进作用有明显差异,其中山西大同风化煤提取的腐殖酸促进作用最大,云南昆明滇池底泥和河南巩县褐煤提取的腐殖酸之间则无显著差异。     

Elemental,functional group and infrared spectroscopic analysis of actinomycete melanins from brazilian soils

Eleven actinomycete melanins were characterized by elemental and functional group and infrared analysis. A soil humic acid from a Brazilian topsoil, a darkred latosol under savanna grassland, analysed previously, was used for comparative purposes. C, N, total acidity, COOH, and phenolic OH contents were within the ranges reported for soil humic acids and fungal melanins. Compared to the soil humic acid, the actinomycete melanins showed greater detail, indicative of higher aliphaticity. Most of these were, in varying degrees, similar to the type III IR spectra of humic acids, which are characteristically high in proteinaceous material, and with variable amounts of polysaccharides. The exceptions were two melanin spectra that showed more resemblance to the humic acid from the dark-red latosol, which belongs to the type I spectra of soil humic acids, a category that includes most soil humic acids. The probable participation of melanic actinomycetes in the formation of humic polymers in discussed.     

Iron oxidation in different types of groundwater of Western Siberia

Background, aim, and scope  The groundwaters of Western Siberia contain high concentrations of iron, manganese, silicon, ammonium, and, in several cases, hydrogen sulfide, carbonic acids, and dissolved organic substances. Generally, the groundwaters of Western Siberia can be divided into two major types: one type with a relatively low concentration of humic substances and high hardness (water of A type) and a second type with a relatively low hardness and high concentration of humic substances (water of B type). For drinking water production, the waters of A type are mostly treated in the classical way by aeration followed by sand bed filtration. The waters of B type often show problems when treated for iron removal. A part of iron practically does not form the flocs or particles suitable for filtration or sedimentation. The aim of this work was to determine the oxidizability of Fe(II), to characterize the iron colloids, and to investigate the complexation of the iron ions with humic substances and the coagulation of the iron colloids in the presence of dissolved organic matter. Materials and methods  Water samples of the A and B types were taken from bore holes in Western Siberia (A type: in Tomsk and Tomsk region, B type: in Beliy Yar and Kargasok). Depth of sampling was about 200 m below surface. The oxidation of the groundwater samples by air oxygen and ozone was done in a bubble reactor consisting of a glass cylinder with a gas-inlet tube. To produce ozone, a compact ozone generator developed by Tomsk Polytechnic University was used. For the characterization of the colloids in the water of B type, the particle size distribution and the zeta potential were measured. To investigate the formation of complexes between iron and humic substances in the water of B type, size exclusion chromatography was used. The coagulation behavior of iron in the presence of dissolved organic substances was investigated at different pH values. The agglomerates were detected by measuring the optical density using a UV-Vis spectrometer. Results  Ozone showed, as expected, a faster oxidation of Fe(II) than air oxygen. The rate constants for Fe(II) oxidation were not much different for the waters of A and B types when the same oxidation process was used. However, the removal of iron after oxidation and filtration was higher in the water of A type than in the water of B type. No evidence for the formation of soluble complexes between iron and humic substances were found. In the water of A type, the coagulation process started at pH = 4.5 and accelerated with increasing pH value. In the water of B type, the coagulation of colloids occurred only at pH = 11 and higher. Discussion  The oxidation experiments indicated no major effect of dissolved organic carbon concentration on the kinetics of Fe(II) oxidation. In contrast to this, the humic substances showed a significant influence on the aggregation behavior of the iron hydroxide colloids. Due to the sorption of humic substances on the iron hydroxide colloids, they were highly stable in the pH range between 4.5 and 10. The particle size measurements confirmed the presence of small colloids in the water of B type. In contrast to this, the iron hydroxide colloids aggregated rapidly at pH = 11. Conclusions  The results showed a great influence of humic substances on the iron removal from groundwaters of Western Siberia with high organic content. The sorption of humic substances on the iron colloids does not obviously allow their coagulation and formation of flocs suitable for filtration or sedimentation. Recommendations and perspectives  By treatment of groundwaters containing high amounts of humic substances, some problems with the removal of iron are likely to occur. To increase the effectiveness of iron removal, the surface coating and pH-dependent charge effects should be taken into account by the selection and optimization of water treatment processes. The iron colloids coated by humic substances should be separated from the water phase by membrane filtration or by flocculation followed by filtration through different solid materials.