长期施有机肥和化肥对潮土胡敏酸结构特征的影响

以河南封丘长期肥料试验为平台,选择有机肥(OM)、化肥NPK(NPK)和不施肥(CK)3种处理,研究了不同施肥措施对潮土胡敏酸(HA)结构特征的影响。HA样品经提取纯化后,采用一系列固态~(13)C核磁共振(NMR)技术并结合元素分析和稳定碳同位素(δ~(13)C)技术对其结构进行定量表征。其中NMR技术包括高速多重倾斜幅度交叉极化/魔角自旋(multiCP/MAS)、偶极相移、化学位移各向异性过滤和质子碳编辑技术。结果表明:长期施有机肥和NPK肥增加了HA的饱和程度、氧化程度和极性,但缩合程度降低;HA的δ~(13)C值降低,表明有新的有机碳进入HA中。潮土HA以脂肪族化合物为主,烷基比例最高,占全碳的24.1%~26.3%;δ64~44处同时存在含氮烷基和甲氧基,且含氮烷基比例更高;另外异头碳和烷氧基中的非质子碳比例均很低。HA的芳香族成分中,δ142~113芳香碳以质子碳为主,且有少量质子芳香碳存在于δ113~93。结果还表明施肥均降低了HA的羧基和δ142~113芳香碳比例,增加了烷氧基和甲氧基比例;施有机肥还增加了酚碳和含氮烷基比例,降低了烷基比例。本研究表明长期施用有机肥和NPK肥使潮土HA结构向着疏水性程度和分解程度降低的方向发展;OM和NPK处理均使糖类物质增加,OM处理还使木质素和多肽增加,脂类物质降低。不同施肥模式下HA的形成机制不同。     

论胡敏酸和胡敏酸盐与二、三氧化物相互作用产物的本性和性质

取生荒地表层黑土,用酒精-笨浸提脂蜡质,和0.1NH_2SO_4脱钙后,用0.1NNaOH 提取出胡敏酸,再重复净化而进行电滲析,所得胡敏酸的 pH 3.41,灰分含量为1.79%。以此胡敏酸与 FeCl_3、Fe_2(S04)3和 Al_2(SO_4)3溶     

胡敏酸的酒精分级沉淀法分级

本文利用酒精分级沉淀法，将胡敏酸分成１２个级分，并对各级分的结构进行了表征。结果表明，随着溶液中乙醇浓度的增大，各级分胡敏酸的腐殖化程度大体上逐渐由强变弱，分子量逐渐变小，全氮，水解性总氮和氨基酸氮的含量逐渐增大，而氨基糖氮和铵态氮逐渐减少 ，同时还讨论了本法与凝胶分级法所获得的结果不同的可能原因。     

秸秆深还对土壤腐殖质组成和胡敏酸结构特征的影响

以辽宁省阜新县试验基地培肥3年的草甸褐土为研究对象,设CK(不施秸秆)和CS(秸秆深还施用量为24 000 kg hm-2)2个处理,每个处理随机选取3个采样点,采集深度为0～20 cm和20～40 cm。采用腐殖质组成修改法提取水溶性物质(WSS)、胡敏酸(HA)、富里酸(FA)和胡敏素(Hu),研究秸秆深还对土壤腐殖质各组分含量的影响,并提取土壤胡敏酸(HA)固体样品进行结构表征。研究表明:秸秆深还更有助于表层土壤及其各腐殖质组分WSS、HA、FA和Hu有机碳含量的积累,分别较CK增加了33.11%、26.39%、11.09%、9.197%和18.55%,亚表层土壤WSS有机碳含量变化不显著,但HA和Hu的含碳量降低;表层和亚表层土壤PQ值的变化不显著;表层和亚表层土壤HA,缩合度变大,分子结构变复杂,芳香结构增加,热稳定性相对提高,亚表层土壤HA脂族结构稳定性增强。     

秸秆深还及配施化肥对土壤腐殖质组成和胡敏酸结构的影响

中国每年农作物秸秆总量巨大,大部分农民选择焚烧,焚烧秸秆会减少表层土壤有机质,损害土壤墒情,引起环境污染,进而危害人类健康。将玉米秸秆施入土壤亚表层(20~40 cm之间),即"秸秆深还"(Corn stover deep incorporation,CSDI),可以有效解决秸秆利用问题,以及由于焚烧秸秆造成的诸多问题,继而达到固碳、蓄水、培肥、稳产的目的。以吉林农业大学试验站玉米连作耕地0~20 cm和20~40 cm土层土壤为研究对象,设CK(未施用秸秆)、CS(秸秆深还)、NPK(单施化肥)、CS+NPK(秸秆深还配施化肥)4种处理,主要研究秸秆深还及配施化肥对土壤腐殖质组成和胡敏酸(HA)结构的影响。腐殖质组成采用腐殖质组成修改法测定,胡敏酸样品采用IHSS方法提取纯化,其结构经元素组成、红外光谱进行研究。结果表明:秸秆深还及秸秆配施化肥对不同土层土壤有机碳(SOC)含量以及腐殖质各组分含碳量均有显著积累作用,PQ值(胡敏酸在腐殖酸中所占的比例)无显著变化。秸秆深还及秸秆配施化肥均能使HA分子的芳香结构比例增加,但CS处理还能同时增加脂族链烃的比例;而CS+NPK处理则使HA的缩合度提高,氧化度下降。说明CS和CS+NPK使HA变稳定的机制有所不同,除了分子结构芳香性提高的作用以外,前者还体现在疏水性的提高上;而后者则体现在分子结构变复杂上。     

几种胡敏酸和富里酸分子结构模型的三维可视化与特性研究

针对已提出的几种胡敏酸和富里酸的二维分子结构模型,应用HyperChem软件转换为三维结构并进行几何优化,计算了这些三维模型的能量以及定量构效关系(QSAR)参数。结果表明:几种模型在三维结构和特性上都各不相同,这为从空间角度更直观地认识腐殖物质的分子结构提供了可能性。     

蜉金龟堆肥和自然堆肥类胡敏酸的表征及特性研究

分别用焦磷酸钠和氢氧化钠浸提新鲜牛粪、蜉金龟堆肥(APCM)和自然堆肥(腐熟牛粪)产物中的类胡敏酸,采用元素组成、红外光谱及差热分析研究了其结构特征。元素分析结果表明,蜉金龟堆肥焦磷酸钠浸提物——类胡敏酸(NaHLA)的芳香性低于新鲜牛粪和自然堆肥,而碳水化合物及氮元素含量增加。蜉金龟堆肥氢氧化钠浸提物——类胡敏酸(PAHLA)的碳水化合物和氮元素含量也高于新鲜牛粪和自然堆肥,而自然堆肥PAHLA的芳香性略低于新鲜牛粪和蜉金龟堆肥。红外光谱分析结果表明,与自然堆肥NaHLA相比,蜉金龟堆肥NaHLA中羧酸脂类化合物、酮类化合物、脂肪族化合物及碳水化合物有所增加。与新鲜牛粪PAHLA相比,蜉金龟堆肥和自然堆肥PAHLA的碳水化合物、脂肪族化合物、酚类化合物及纤维素酯类减少,同时蜉金龟堆肥PAHLA的酰胺化合物在蜉金龟消化过程中被其吸收。差热分析结果表明,自然堆肥NaHLA的热稳定性高于新鲜牛粪和蜉金龟堆肥,而蜉金龟堆肥NaHLA的脂族化合物、外围官能团和分子内部芳香结构含量较高,分子结构较复杂。蜉金龟堆肥PAHLA存在两个放热峰,而新鲜牛粪和自然堆肥的中温放热峰消失。综上,蜉金龟堆肥和自然堆肥采用两种提取液浸提出类胡敏酸的结构特征存在差异性。     

施用有机肥料对土壤胡敏酸结构特征的影响──胡敏酸的光学性质

本工作通过田间试验和模拟试验研究了施用有机物料对棕壤、草甸土和水稻土中胡敏酸光学性质的影响。结果表明，施用有机物料后使土壤胡敏酸的吸光值和相对色度下降，色调系数升高，甚至发生类型改变。还使胡敏酸紫外２８５ｎｍ和红外２９２０ｃｍ＾－１吸收增强，１７２０ｃｍ＾－１和萤光强度减弱，激发光谱最大强度波长紫移。说明胡敏酸的分子结构变得脂族化，简单化和年轻化。两种有机物料相比，玉米秸杆对胡敏酸的木质素特征作用     

土壤胡敏酸的温和水解及分组研究 Ⅱ.胡敏酸水解产物中的醇类化合物

采用温和水解及薄层层析等分组方法 ,并应用气—质联机技术对土壤胡敏酸 (HA)水解产物中的醇类化合物进行了初步研究。结果表明 :HA水解产物中醇类含量顺序是饱和醇 >甾醇 >非饱和线性醇。饱和醇中主要是C12～ 3 0 中的偶数碳和C15,非饱和线性醇主要是C2 0 -1π、C2 0 -2π和C19-4π。C3 和C4植物条件下形成的HA有一定的差异 ,C3 -HA含有较多的非饱和醇 ,而C4-HA含有更多的饱和醇特别是C12 和C2 6。     

蒙脱石对不同施肥处理土壤胡敏酸及其级分的吸附特征Ⅰ.蒙脱石对胡敏酸的吸附特征

以17年不同施肥处理土壤胡敏酸为材料,研究了不同性质胡敏酸与钙饱和蒙脱石的 吸附特征。结果表明,钙饱和蒙脱石对土不同施肥处理胡敏酸的吸附曲线可用单表面Langmuir方程、双表面Langmuir方程以及Freundlich方程来描述。由单表面Langmuir方程计算的有机肥处理（厩肥、秸秆）胡敏酸的吸附量和吸附强度大于无肥、化肥处理。温度升高各处理胡敏酸吸附量增加,但吸附强度下降。双表面Langmuir揭示,蒙脱石对胡敏酸的吸附呈现高低两种能位的吸附。高能点位的吸附以化学吸附为主,是吸热反应,低能点位的吸附以物理吸附为主,是放热反应。有机肥处理和无肥、化肥处理相比,高能点位吸附相对减弱,低能点位吸附相对增强。     

土壤胡敏酸与富里酸热力学稳定性及其驱动因素初步研究

从过程考虑,腐殖质的形成和转化主要是微生物主导的生物化学过程,但就其始态和终态的能量水平变化而言,是热力学稳定性问题。在土壤中,影响腐殖质的形成转化的因素很多,如黏粒含量和类型,植被和微生物状况,土壤湿度、温度和空气组成,土壤溶液的化学组成、浓度、酸度和氧化还原状况等。但从热力学角度,为了计算反应平衡常数(logKR)和吉普斯生成自由能(ΔGfθ),如果将温度设为25℃,我们可以将土壤条件诸多因素简化为水活度([H2O])、氧分压(PO2)和二氧化碳分压(PCO2)这3个参数。之所以简化为这3个参数,因为任何有机成分均是由含有这3种元素的物质形成的,最终又均可以分解为含有这3种元素的H2O和CO2。本文按照上述新思路,以黑土为例探讨了胡敏酸(HA)、富里酸(FA)形成转化的驱动因素和热力学稳定性的研究方法,用元素组成-土壤条件参数法计算HA、FA的logKR和ΔGfθ及热力学稳定性范围。同时通过土壤添加有机物料的模拟培养实验研究了氧气和二氧化碳等单因素对HA和FA数量积累的影响。结果表明,黑土HA和FA的元素组成分子式分别为nC21H21O9N和nC24H33O17N。FA在缺氧、多水和高浓度二氧化碳条件下较稳定;HA则相反。培养实验中,高二氧化碳和低氧气浓度处理使FA与HA的相对比例增加。这一研究方法和结果将有助于解释和推测土壤腐殖质组成的空间变异规律,指导土壤肥力、土壤固碳的调控实践。     

Compositional and functional features of humic acids from organic amendments and amended soils in Minnesota, USA

The use of organic amendments requires an adequate control of the chemical quality of their humic acid (HA)-like fractions and of the effects that these materials may have on the status, quality, chemistry and functions of native soil HAs. In this work, the compositional, functional and structural properties of the HA-like fractions isolated from a liquid swine manure (LSM), a municipal sewage sludge (SS), and two municipal solid waste composts (MSWCs) were evaluated in comparison to those of HAs isolated from three unamended soils and from the corresponding soils amended with LSW, SS, and MSWC at various rates in three field plot experiments conducted in Minnesota, USA. With respect to the unamended soil HAs, the HA-like fractions of the three amendments featured a greater aliphatic character, a marked presence of proteinaceous, S-containing and polysaccharides-like structures, an extended molecular heterogeneity, small organic free radical contents and a small degree of humification. The MSWC-HAs featured a larger degree of humification than LSM-HA and SS-HA. The three amendments affected in different ways and by various extents the compositional, structural and functional properties of soil HAs depending upon the nature, origin and application rate of the amendment. In general, the data obtained suggested that proteinaceous, S-containing and aliphatic structures contained in HA-like fractions of organic amendments were partially incorporated into native soil HAs.     

腐殖酸对钾在褐土中迁移和转化的影响

采用室内土柱实验研究了腐殖酸与钾共施时腐殖酸对钾在褐土施肥点附件微域中迁移和形态转化的影响。研究结果表明,与单施KCl处理相比,共施腐殖酸没有明显改变肥料钾在褐土中的迁移距离,在培养7天时增加了肥际微域中的水溶性钾含量,而在培养28天时则降低了其含量;共施腐殖酸明显增加了交换性钾含量以及在土壤中的迁移量,但减少了非交换性钾的含量和迁移量。说明共施腐殖酸减少了土壤晶格对钾离子的固定,提高了外源钾在褐土中的有效性。     

Chemical characteristics of glomalin-related soil protein (GRSP) extracted from soils of varying organic matter content

Glomalin is described in the literature as a N-linked glycoprotein and the putative gene product of arbuscular mycorrhizal fungi (AMF). Since the link between glomalin and various protein fractions in soil is not yet clearly defined, glomalin-related soil protein (GRSP) more appropriately describes glomalin's existence in natural organic matter (NOM). The objective of this study was to examine the chemical characteristics of GRSP present in several mineral and organic soils of varying organic carbon content. GRSP was isolated using high temperature sodium citrate extraction followed by either trichloroacetic acid (TCA) or hydrochloric acid (HCl) precipitation. GRSP was characterized by quantitative solid-state ¹³C DPMAS NMR, infrared (IR) spectroscopy, elemental analysis, and the Bradford assay for protein content. GRSP accounted for 25% and 52% of total C in the mineral soils and organic soil, respectively. Molar C/N and H/C ratios reveal that GRSP has less nitrogen than bovine serum albumin (BSA), and that GRSP extracted from the Pahokee peat soil possessed a more unsaturated, and thus aromatic character relative to the mineral soil GRSP, respectively. GRSP's high aromatic (42-49%) and carboxyl (24-30%) carbon contents and low aliphatic (4-11%) and carbohydrate-type carbon contents (4-16%) suggests that GRSP does not resemble a typical glycoprotein. In fact, the NMR spectra of GRSP closely resemble that of humic acid. GRSP extracted from mineral and organic soils possessed the same NMR fingerprint regardless of the precipitation method used (i.e., either TCA or HCl). It is likely that the current GRSP extraction methods, because of their similarity to the method used to extract humic acid, are coextracting both materials.     

秸秆深还对土壤团聚体中胡敏酸结构特征的影响

秸秆深还(Deep application of straw,DAS)是指将玉米秸秆施入土壤亚表层(20~40cm),可以解决秸秆焚烧的问题,同时提高土壤肥力、蓄水能力和作物产量。本文采集了吉林农业大学试验站玉米连作耕地试验田中的秸秆深还土壤和未秸秆深还土壤,采用湿筛法将其分为2 mm、2~0.25 mm、0.25~0.053 mm和0.053 mm 4个粒级,定性分析提取胡敏酸(HA),通过元素组成、红外光谱和差热分析研究了秸秆深还对黑土各粒级团聚体中HA结构特征的影响。结果表明:黑土团聚体中的优势粒级为2~0.25 mm粒级,优势粒级的团聚体含量和有机碳含量均是表层较亚表层低,DAS有利于优势粒级团聚体的形成,促使优势粒级团聚体中有机碳增多;与亚表层相比,表层各粒级团聚体HA的缩合度、氧化度和热稳定性普遍较低,脂族碳/羧基碳和脂族碳/芳香碳较高;DAS促使土壤表层和亚表层各粒级团聚体中HA的缩合度、氧化度和热稳定性下降,其中表层HA的缩合度降低更明显;而亚表层氧化度和热稳定性的降低幅度较大。表层中HA的分子结构较亚表层的简单、年轻,秸秆深还促使土壤中有机碳含量增加,HA的结构简单化、年轻化。     

不同气候带水稻土有机碳δ13C及胡敏酸结构特征变化

选取位于吉林龙井、河南封丘、浙江慈溪和江西进贤的4种水稻土剖面,分析比较了不同气候带水稻土剖面和各粒级复合体的有机碳及其δ13C值的分布特征,探讨了不同水稻土胡敏酸结构和功能基团构成的差异,旨在为深入研究水稻土有机碳动态变化和运转机理提供参考依据。结果表明:不同气候带水稻土剖面中,有机碳δ13C值均随着土层深度的增加逐渐升高;样点位置愈往北,水稻土表层有机碳δ13C值愈高。各样点水稻土表层有机碳主要集中在<10μm复合体部分,其有机碳分配系数均大于50%。水稻土不同粒级复合体δ13C值随着粒级的减小不断升高,高δ13C的老碳在细粒中富集;水稻土表层<10μm复合体中有机碳的降解程度为:封丘>慈溪>进贤>龙井。各样点水稻土胡敏酸结构大致相似,封丘和龙井的水稻土胡敏酸含有较多CO基团,氧化程度较高,另外,其胡敏酸的芳化度和聚合程度也高于慈溪和进贤的水稻土。     

农田生态条件对灰漠土养分及胡敏酸特性的影响

通过比较荒地和玉米地土壤养分、胡敏酸热解特性和红外光谱特征,研究了灰漠土农田生态条件对土壤养分和有机质特性的影响。结果表明,种植玉米增加土壤有机质、全N、全P、全K、缓效钾和碱解氮的含量,但使速效磷和速效钾含量下降,土壤pH略有下降。荒地土壤胡敏酸的脂肪族侧链较多,胡敏酸较年轻,而玉米地土壤胡敏酸侧链较少,胡敏酸相对较老。荒地土壤胡敏酸的脂族性强于玉米地。农田生态条件使土壤胡敏酸老化。     

淹水还原条件下红壤中葡萄糖及腐殖酸对铁锰形态的影响

通过设置不同的葡萄糖/腐殖酸配比模拟还原性土壤体系,考察长期(约74 d)淹水培养过程中铁锰元素在土壤溶液/矿物相中的分布形态演变。结果表明:在淹水培养初期,葡萄糖的添加可以促进铁锰离子的还原溶出,同时土壤中可交换态和酸可提取态铁、以及可交换态锰的含量也会随之增加;而腐殖酸的添加则会促进土壤中可氧化态铁/锰含量的升高。随着培养时间的增加,铁锰离子浓度及各个土壤提取形态的铁锰含量大多呈现降低趋势,铁锰元素逐渐转化成提取性更低的矿物形态。因此,淹水环境中铁锰还原溶出-分布形态演变受到土壤中有机物质种类和含量的显著影响,呈现出不同的金属移动性和生物有效性。     

Land use effects on carbon quality and soil biological properties in Eutric Cambisol

Abstract

The choice of prospective type of farming requires knowledge about the specific relationships that exist between farm management practices and base environmental conditions. Nowadays the protection of soil organic carbon is one of the main tasks, because organic carbon in addition to soil fertility can act in elimination of soil contamination and carbon sequestration. Field experiments were focused on the effect of intensive farming without organic inputs versus grassland on organic carbon content. Organic carbon content (C_ox) and humic substance fractions (C-humic acids and fulvic acid fractions), hot water extractable carbon and selected microbial characteristics in Eutric Cambisol were monitored during the period 1999–2010. A priming effect of soil cultivation was detected immediately after tillage. Arable soil with ‘intensive’ crop sequences (exclusively cash crops, cereals, oil plants) and with an optimal level of chemical inputs (mineral fertilizers, pesticides), but without organic farmyard manure had lower content of all carbon forms compared with grassland. ¹³C NMR spectroscopy and thermal analysis (TGA) were applied to characterize humic acid (HA) structure and stability. More carbon, less oxygen and more aromatic compounds were detected in grassland HA. Slight differences were found in HA thermo-oxidative stability and degradability, which was probably caused by changes in elemental composition and structure. Even the land use had no significant effect on basic microbiological characteristics (basal respiration, microbial biomass and qCO₂); the physiology of the microbial community of grassland was altered by a higher ability to utilize L- and D-glutamic acid. The L/D ratio of glutamic acid mineralization indicated no occurrence of stress in soil for both types of farming. It has been demonstrated that although losses of carbon as a result of land-use conversions are generally more rapid, gains of carbon in grassland followed by changes in management practices can also occur.