典型黑土区不同生态系统下土壤团聚体中胡敏酸的结构特征

为了揭示生态系统类型对土壤团聚体中腐殖质分子结构的影响,本研究以黑土区24 a长期定位试验处理下的自然草地(GL)、耕地(CL)和裸地(BL)土壤为研究对象,采用湿筛法将土壤团聚体分为2 mm、2～0.25 mm、0.25～0.053 mm和0.053 mm 4个粒级,运用元素分析、红外光谱和差热分析技术,对团聚体中胡敏酸(HA)的结构性质进行了研究。结果表明,生态系统类型对团聚体中HA的分子结构产生了影响。耕地各级团聚体中HA的O+S含量以及(O+S)/C比值(摩尔比)普遍高于草地相应粒级团聚体,反映了耕地土壤团聚体中HA的氧化程度高于草地;差热分析中,耕地和裸地土壤团聚体中HA的中温放热量低于草地相应粒级团聚体,且二者的热量高/中比值均高于草地,说明耕地和裸地土壤团聚体中HA的芳香性/脂族性高于草地;草地和耕地土壤团聚体中HA在2 920和2 850 cm-1处代表脂族聚亚甲基和末端甲基中C-H伸缩振动的吸收峰明显强于裸地,脂族碳/羧基碳(2 920/1 720)以及脂族碳/芳香碳(2 920/1 620)比值高于后者。与自然草地相比,耕地和裸地生态系统会增强土壤团聚体中HA的缩合度、氧化度和芳香性,提高其分子结构的稳定性。     

施用猪粪对棕壤富里酸结构特征的影响

在棕壤上进行的田间试验田取样,从化学性质(元素组成)、光学性质(色调系数、相对色度、紫外光谱、红外光谱)和波谱学性质(13C核磁共振波谱)三个方面研究了施用猪粪对棕壤富里酸结构特征的影响。结果表明,施用猪粪后,棕壤富里酸的C/H比值增加,O/C比值下降;色调系数下降,相对色度增加;红外光谱中,2932cm-1和1639cm-1吸收峰强度增加;13C核磁共振波谱中,羰基C含量下降,芳香C和烷基C含量增加。这些结果说明,施用猪粪使棕壤富里酸的氧化程度下降,缩合程度和脂族链烃含量增加,其结构变得复杂化和脂族化。     

秸秆深还不同年限对黑土腐殖质组成和胡敏酸结构特征的影响

秸秆深还(Corn stover deep incorporation,CSDI)指将作物秸秆深埋于土壤亚表层20~40 cm深处,用以解决秸秆焚烧和土壤肥力退化的可持续利用模式。本文以吉林农业大学玉米连作耕地试验田未施用秸秆和秸秆深还不同年限的土壤为研究对象,设置CK、CSDI(2014)、CSDI(2013)和CSDI(2012)共4种处理,分别代表未施入秸秆、2014年秸秆深还(深还第1年)、2013年秸秆深还(深还第2年)、2012年秸秆深还(深还第3年),研究秸秆深还不同年限对黑土腐殖质组成和胡敏酸结构特征的影响。通过腐殖质组成修改法提取富里酸(Fulvic acid,FA)、胡敏酸(Humic acid,HA)和胡敏素(Humin,HM),国际腐殖质协会(International Humic Substances Society,IHSS)推荐的方法提取HA样品,通过元素组成、红外光谱和差热分析测定HA结构。结果表明:与CK相比,秸秆深还1年后显著提高了土壤和腐殖质各组分有机碳含量,亚表层累积效果更明显,其土壤有机碳(SOC)、HA、FA和HM有机碳含量分别增加了23.7%、30.5%、27.3%和46.1%,但PQ值(HA在可提取腐殖物质的比例)没有显著变化;HA氧化度和缩合度降低明显,表层和亚表层(O+S)/C比值分别降低14.31%和14.68%,H/C比值分别增加27.74%和28.86%,脂族链烃和芳香碳含量增加,热稳定性降低,HA结构趋于简单化。随着年限增加,深还3年后SOC、FA和HM有机碳含量呈下降趋势,HA有机碳含量呈上升趋势,PQ值变化显著,HA缩合度、氧化度呈上升趋势,脂族性减弱,芳香性增强,HA结构趋于复杂化。说明随着年限增加,秸秆不断矿化分解,秸秆深还对土壤腐殖质组成和结构特征的影响效果减弱。     

土壤溶解性有机质分子特征对不同来源有机肥分解的响应

从有机肥料中提取的溶解性有机质（DOM）可为不同的商业有机肥料的潜在应用提供新的见解。选用四种不同来源有机肥（生物质炭肥,WSB;羊粪有机肥,SM;海藻有机肥,SW;虾肽有机肥,SP）与昌化矿区周边土壤为研究材料,进行为期三个月的培养试验,采用多元光谱分析研究土壤DOM分子特征对有机肥分解的响应。与对照组相比,在培养过程中添加四种有机肥均增加土壤DOM的含量,WSB处理增加量最低,SW处理增加最高。激发发射矩阵结合平行因子分析 (EEM-PARAFAC) 表明培养过程中添加WSB提高了土壤DOM中类胡敏酸组分,减少了类富里酸组分;添加SM、SW和SP在0~45 d内降低了土壤DOM中微生物转化的类胡敏酸组分的比例而提高类富里酸组分,在45~90 d内增加难降解的类胡敏酸组分的比例。二维红外相关分析 ( 2D-FTIR-COS) 表明CK和SP处理中土壤DOM的芳香性或羧酸碳优先对分解时间发生响应;而添加WSB、SW和SM处理组中土壤DOM的烯烃或多糖类碳优先对分解时间发生响应;添加WSB和SP处理土壤提取液中也出现了Si-O-Al等土壤纳米矿物类官能团响应信号。碳近边X射线吸收精细结构 (C 1s NEXAFS) 分析结果表明：培养结束后,与未添加有机肥处理相比,WSB处理提高土壤DOM中含氧脂肪族碳组分比例,而减少芳香与酚类碳比例;SW处理主要增加了芳香碳、羰基碳的比例,而减少了脂族碳和氧烷基碳含量;SM、SP处理增加了酚类碳、芳香碳以及脂族碳比例,减少了羧基碳、氧烷基碳和羰基碳比例。本研究结果可增强对不同来源有机肥分解影响土壤DOM分子特征的了解,对于评估土壤中施用商品有机肥料的生态环境效应至关重要。     

施用有机肥料对胡敏酸结构特征的影响─—胡敏酸的1H-核磁共振波谱

通过在棕壤，草甸土和水稻土上进行田间试验和模拟试验表明，施用有机肥料一般使胡敏酸的脂族Ｈ的相对含量增加，聚亚甲基链长，变短，芳香Ｈ相对含量和由之计算的芳香度下降，从而导致ＨＡ中脂族Ａｌｉ－Ｈ与Ａｒ－Ｈ的比值增加，即发生了脂族化。     

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。     

牛粪配施生物质炭的土壤碳净变化率和腐殖物质组成研究

牛粪是农业生产中常用的有机肥,牛粪配施生物质炭是否会提高有机物料在土壤中的碳净变化率是高效利用有机物料重要问题。通过1年田间试验施用常量(M1)和倍量(M2)牛粪、常量(CBM1)和倍量(CBM2)牛粪配施生物质炭对比了短期腐殖物质碳净变化率差异和结构特征。结果表明,与单施牛粪(M1和M2)相比,牛粪配施生物质炭(CBM2)土壤胡敏酸、富里酸和胡敏素的含量增至1.36g·kg~(–1)、2.50g·kg~(–1)和5.03g·kg~(–1);土壤胡敏酸和富里酸碳净变化率分别提高1.18%和3.67%。与施用牛粪相比,牛粪配施生物质炭胡敏酸、富里酸和胡敏素脂族碳和多糖相对含量增加;CBM2处理胡敏酸和胡敏素芳香碳相对含量增加,CBM1处理富里酸芳香碳相对含量增加。表明牛粪配施生物质炭在土壤固碳效果上优于单施牛粪,可形成更多的腐殖物质,提高胡敏酸和富里酸的碳净变化率;同时也有利于腐殖物质脂族碳和多糖相对含量的增加,而生物质炭用量不变的情况下,配施更多的牛粪可增加胡敏酸和胡敏素芳香碳相对含量。施用牛粪或牛粪配施低量生物质炭可使Hu和FA的缩合度增加,氧化度降低,而HA则相反。     

有机物料施用下原生盐碱土胡敏酸结构特征

为研究不同有机物料对原生盐碱土胡敏酸官能团组成的影响,以吉林省大安市原生盐碱地为研究对象,设置空白处理(CK)、颗粒状秸秆处理(KL)、正常玉米秸秆处理(JG)、牧草处理(MC)和羊粪处理(YF),通过红外光谱与主成分分析(Principal component analysis,PCA)相结合,研究不同有机物料施用下土壤胡敏酸红外光谱特征。结果表明,有机物料各处理与CK处理相比增加了土壤胡敏酸中脂肪碳和芳香碳的相对含量,减少了羧基碳的含量。除KL处理外,其他处理均增加了土壤胡敏酸中氨基化合物的相对含量。同时有机物料的施用增加了土壤胡敏酸的脂族碳/羧基碳和脂族碳/芳香碳比值,表征有机物料的施用使得土壤胡敏酸结构缩合度和氧化度下降,脂族性增强,芳香性降低,胡敏酸结构趋于脂族化、简单化、年轻化。对比两种秸秆处理,发现KL处理更有利于土壤新形成结构年轻化、简单化、脂族性强的胡敏酸分子。根据PCA结果,有机物料的施用是土壤中脂族性碳、芳香族碳以及氨基化合物的主要来源之一,为探讨胡敏酸官能团的来源提供依据。通过红外光谱结合PCA,发现了土壤胡敏酸官能团组成对有机物料的不同响应,为研究有机物料的施...     

玉米秸秆腐解过程中形成胡敏酸的组成和结构研究

采用化学方法和谱学方法对玉米秸秆腐解生成胡敏酸（CCSR HA）的组成和结构进行了研究.结果表明,CCSR HA的碳组成可分成三个部分：脂肪族碳、芳香族碳和羧基碳,它们的含量分别为59.62%、26.94%和13.44%.CCSR HA主要的官能团包括羟基、烷基、羧基、酰胺基、苯环、烷氧基及碳水化合物结构,木质素残体是其骨架,碳水化合物结构或类糖结构及烷基片段是其主要组成单元.其类型属于Rp型胡敏酸.未腐解的玉米秸秆本身就含有类胡敏酸物质（OCSR HA）,OCSR HA和CCSR HA的官能团组成上有一定差异,后者结构中,甲基、亚甲基、次甲基、醚键官能团和酚羟基的含量降低,而酰胺成分、游离的羧基、甲氧基、碳水化合物组分相对含量升高,脂族性升高,芳香性降低,芳香度由初始的42.19降至腐解后的29.97,并且与无机物质的结合能力增强.就元素组成的变化看,CCSR HA中C和H元素的含量趋于降低,而N和O元素的含量趋于升高.CCSR HA同土壤胡敏酸相比,糖类结构含量较高,并且以片段的形式与水解木质素残体相连.羧基含量较低,但以不同的连接方式存在着.     

水稻种植对吉林省西部苏打盐碱土改良培肥效果

通过田间调查取样和室内分析,研究了水稻种植(5~30年)对吉林省西部苏打盐碱土的改良和培肥效果。结果表明:与种稻前的荒地土壤相比,种稻后土壤的pH、全盐量、交换性钠、碱化度、CO32-、HCO3-、Cl-、Ca2+、Na+和<0.053 mm粉黏粒含量显著降低,而SO42-、总有机碳、水溶性有机碳、胡敏酸碳、富里酸碳、碱解氮和2~0.25 mm大团聚体含量显著增加;同时,有机碳组成中的烷基碳和烷氧碳含量增加,而芳香碳和羰基碳含量降低,脂族碳/芳香碳比值增加,而烷基碳/烷氧碳和疏水碳/亲水碳比值降低;随种稻年限的延长,以上变化规律通常表现的更为明显。上述结果表明,种稻不仅能够降低土壤碱性和盐分含量,而且有助于提高土壤有机碳的含量和品质,以及改善土壤结构性,因此是改良和培肥苏打盐碱土的有效方式。     

中国黑土上腐殖酸和腐殖物质的提取及其描述

Twenty-three progressive extractions were performed to study individual humic acids (HAs) and humin fractions from a typical black soil (Mollisol) in Heilongjiang Province, China using elemental analysis and spectroscopic techniques. After 23 HA extractions the residue was separated into high and low organic carbon humin fractions. HA yield was the highest for the first extraction and then gradually decreased with further extractions. Organic carbon (OC) of the humin fractions accounted for 58% of total OC even after 23 successive HA extractions. In addition, the atomic C/H ratio decreased during the course of extraction while C/O increased; the E4/E6 ratio from the UV analysis decreased with further extraction while E~/E3 increased; the band assigned to aliphatic carbon (2 930 cm-1) in the diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) spectra gradually increased with progressive extraction; the calculated ratio of the sum of aromatic carbon peak heights to that of aliphatic carbon peak heights from DRIFTS spectra declined with extractions; and nuclear magnetic resonance (NMR) data suggested that HA aliphatic carbons increased with extractions while aromatic carbons decreased. Thus, hydrophobicity and aliphaticity of HAs increased with extractions while polarity and aromaticity decreased. These data showed substantial chemical, structural, and molecular differences among the 23 HAs and two humin fractions. Therefore, these results may help explain why soil and sediment humin fractions have high sorption capacity for organic contaminants.     

固态13C和15N核磁共振法研究15N标记土壤的腐殖质组分

Five humic fractions were obtained from a uniformly ^15N-labelled soil by extraction with 0.1 mol L^-1 Na4P2O7,0.1mol L^-1 NaOH ,and HF/HCl-0.1 mol L^-1 NaOH,consecutively,and analyzed by ^13C and ^15N CPMAS NMR (cross polarization and magic angle spinning nuclear magnetic resonace).Compared with those of native soils humic fractions studied as a whole contained more alkyls ,methoxyls and O-alkyls,being 27%-36%,17%-21%and 36%-40%,respectively,but fewer aromatics and carboxyls(bein 14%-20% and 13%-90%,respectively),Among those humic fractions ,the humic acid(HA)and fulvic acid(FA) extracted by 0.1 mol L^-1 Na4P2O7 contained slightly more carboxyls than corresponding humic fractions extracted by 0.1 mol L^-1 NaOH ,and the HA extacted by 0.1 mol L^-1 NaOH after treatment with HF/HCl contained the least aromatics and carboxyls.The distribution of nitrogen functional groups of soil humic fractions studied was quite similar to each other and also quite similar to that of humic fraction from native soils.More than 75% of total N in each fraction was in amide from,with 9%-13% present as aromatic and /or aliphatic amines and the remainder as heerocyclic N.     

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。     

Soil Organic Matter Quality and Zinc and Lead Sorption as Affected by a Sewage Sludge Or a Sewage Sludge Compost Application

Sewage sludge (SS) or sewage sludge compost (SSC) were applied to soil under controlled conditions, at rates of 0 or 200 Mg ha^?1, to investigate changes in dissolved organic matter (DOM), humic acids (HA), and Pb and Zn sorption in the soil. Infrared spectroscopy, visible spectrophotometry, and sorption isotherms (mono-metal and competitive sorption systems) methods were used to assess the changer. The E₄/E₆ ratio (λ at 465 / λ at 665 nm) and the infrared spectra of DOM and HA showed aromatic behaviour in compost-soil (SSC-S); in contrast sewage sludge-soil (SS-S) showed an aliphatic behaviour. Application of either SS or SSC increased the Pb and Zn sorption capacity of soil. The Pb and Zn sorption increased in soil and soil mixtures with a competitive metal system. The metal affinity sequence for soil, SS-S, and SSC-S was compared with the predicted affinity sequences obtained from metal properties. Poor correspondence was observed between the metal affinity sequence and the metal affinity sequence predicted by ionic potential, indicating that metals bonding to soils were not predominantly electrostatic. An affinity sequence based on Pearson's theory agreed with the metal affinity sequences for soils. A statistical analysis showed that the bands assigned to esters (1080 cm^?1) of DOM, phenolic OH (1420 cm^?1), amide I (1650 cm^?1), carboxyl and carbonyl C=O stretches of different nature, C=O stretch of aromatic esters, aliphatic cetone, aldehyde (1720 cm^?1), ethers and esters (1230 cm^?1), aliphatic alcohols (1125 cm^?1), and lignin (1380 cm^?1) of HA were correlated with Zn constants of Langmuir adsorption isotherm (P < 0.05).     

The carbon distribution among the functional groups of humic acids isolated by sequential alkaline extraction from gray forest soil

Preparations of humic acids (HAs) were isolated from a gray forest soil by sequential alkaline extraction. From a sample of 500 g, HA preparations of 2.24, 0.23, and 0.20 g were obtained from the first, second, and third alkaline extracts, respectively. The structure of the preparations was determined by ¹³C NMR spectroscopy. At each next extraction step, the portion of aliphatic fragments in the HA preparations increased and the content of aromatic structures decreased. The conclusion was drawn that a single extraction is sufficient for obtaining a representative HA sample.     

FTIR‐spectroscopic characterization of humic acids and humin fractions obtained by advanced NaOH,Na4P2O7, and Na2CO3 extraction procedures

Aim of our study was the development of the methodological basis for the characterization of humic fractions of a long‐term field experiment. Humic acids (HAs) were extracted from three layers of a nontilled soil using three different extractants (1 M NaOH, 0.1 M Na₄P₂O₇, 1 M Na₂CO₃), and the humin fraction was enriched. NaOH as extractant for FTIR analysis of humic substances yields higher resolved IR spectra, especially in the important regions of stretching vibrations including aromatic and aliphatic groups and in the fingerprint area including amides, aliphats, and aromats than the other extractants. The NaOH extraction has lower extraction yields as compared to Na₄P₂O₇ and Na₂CO₃ and represents a different part of the soil organic matter (SOM). This is reflected by lower C : N ratios and higher E₄ : E₆ and fulvic acid–to–humic acid ratios as compared to the other extractants. The FTIR band areas of HA fraction obtained by NaOH showed an increase of the aromatic and carbonyl groups and a decrease of amide groups with increasing soil depth. Aliphatic groups showed contradicting results: The bands of the stretching vibrations increased, and the band of the bending vibrations decreased. We assume that band interactions in the bending vibrations were responsible for that phenomenon under the assumption of an increase of aliphatic groups with increasing soil depth. The IR bands of the enriched humin fraction showed a decreasing trend in case of both aliphatic bands deriving from stretching vibrations and an increase of aromatic characteristics with depth. Our study led to the conclusion that HA fractions obtained by 1 M NaOH represent a small and dynamic fraction indicated by the measured yields in combination with values of N_t, C : N, E₄ : E₆ ratios, and ratios of fulvic acids (FA) to HA. The humin fraction has a high contribution to the total organic C and represents a more stabilized fraction of SOM which still shows changes in its aromatic and aliphatic characteristics with soil depth.     

长施马粪对暗棕壤团聚体腐殖质数量和质量的影响

运用元素和红外光谱分析研究了暗棕壤长期施用马粪(每3年施肥1次)、施低量化肥和马粪配施高量化肥对水稳性大团聚体(2 mm和2~0.25 mm)、微团聚体(0.25~0.053 mm)和粉/黏粒粒级(0.053 mm)中腐殖物质-胡敏酸(HA)的分布及其结构特征的影响,探讨施肥对农田土壤肥力的贡献及其团聚体的固碳机制。施用马粪和马粪配施高量化肥分别提高(49.06%)和降低(31.04%)了2~0.25 mm大团聚体比例,3种施肥措施均提高了土壤有机碳(SOC)数量,但对土壤HA数量影响不显著。不同施肥措施对不同粒级团聚体中HA的分子结构特征影响不同,3种施肥措施均降低了2~0.25 mm大团聚体HA的缩合度,芳香性增加;微团聚体HA缩合度降低,脂族性增强;施用马粪提高了粉/黏粒HA的缩合度和脂族性,马粪配施高量化肥提高了粉/黏粒HA的缩合度和芳香性,施用低量化肥,粉/黏粒HA缩合度下降,芳香性提高。因此,长施马粪提高了土壤SOC数量,促进2~0.25 mm大团聚体的形成,大团聚体中HA的稳定性提高,利于土壤固碳,而0.25~0.053 mm微团聚体和0.053 mm粉/黏粒HA的活性增强,利于土壤肥力供给,这些团聚体是评估长施马粪对腐殖质质量产生影响的重要粒级。     

Chemical and spectroscopic characteristics of humic acid from a clay loam soil in Ontario after 52 years of consistent fertilization and crop rotation

Long-term fertilization and crop rotation can influence both organic C sequestration as well as the C composition of soils and the more resistant organic C compounds contained in humic acid(HA). This study examined the effects of fertilization and cropping type(monoculture corn(MC) and Kentucky bluegrass sod(KBS) and corn-oat-alfalfa-alfalfa rotation(RC)) on the HA composition of soil from a 52-year field study in southern Ontario, Canada. Humic acid samples were extracted from soil, and elemental analysis, infrared spectroscopy, solid state 13C nuclear magnetic resonance spectra, and electron paramagnetic resonance methods were used to determine the influence of the cropping type on the characteristics of HA. Both fertilization and cropping type affected the chemical characteristics of HA. Fertilization led to a 5.9% increase in C, a 7.6% decrease in O, and lower O/C and(N + O)/C ratios in HA as compared to the corresponding non-fertilized treatments. Rotation resulted in a lower proportion of C(48.1%) and a greater(N + O)/C ratio(0.7) relative to monoculture cropping. Infrared spectroscopy analysis showed that HA contained more C-O groups in fertilized soil than in non-fertilized soil under MC and KBS. Fertilization increased the O-alkyl-C, phenolic-C, and free radical contents of HA relative to non-fertilization treatments. Rotation decreased the aliphatic and carboxyl groups and increased the O-alkyl, carbohydrate, aryl, and phenolic groups and free radicals, relative to MC and KBS. Both long-term crop rotation and fertilization dramatically modified the soil HA composition. Significant relationships were observed between the molecular composition of HA and soil organic C. Hence, humic acid characterization could be used as an indicator of the long-term sustainability of crop management practices.     

The significance of solid‐state 13C NMR spectroscopy of whole soil in the characterization of humic matter

Abstract

Differences in characteristics of humic matter were investigated by solid‐state CP/MAS ¹³C NMR spectroscopy of whole (nontreated) materials and their extracted humic fractions. Samples used in the analysis were lignite, a commercial humate AG, and the Bh horizons of a Mascotte and a Lawnwood soil. Humic fractions were extracted by the 0.1 M NaOH or Na₄P₂O₇ (pH 9.8) method. The humic (HA) and fulvic acid (FA) obtained were weighed and analysed for total acidity, carboxyl and phenolic‐OH group contents. Whole lignite, humate AG and soil samples, and the HA and FA fractions were analyzed by solid state CP MAS ¹³C NMR and infrared spectroscopy. Carbon, H, and N contents were determined by chemical analysis. NMR spectra of the combined HA+FA extracts resembled the spectra of the whole materials. No additional signals were detected, indicating that alien compounds were not produced during the extraction. The best spectra were obtained with HA samples produced by the NaOH method. These spectra closely resembled those of the untreated materials. Spectral and chemical differences noticed between the HA (or FA) fractions were attributed more to differences in origin than to the extraction procedure. Aliphatic, aromatic and carboxyl groups were the major components of HA from lignite and humate AG. In contrast, HA from the two Haplaquods were characterized by four major components: the aliphatic, polysaccharide, aromatic, and carboxyl groups. Regardless of origin, all the HA fractions contained similar functional groups, as indicated by their close similarities in infrared spectra.     

有机物料对白土土壤胡敏酸结构特征的影响

【目的】研究有机物料施入对白土土壤的腐殖质含量组成和胡敏酸(HA)结构特征的影响,为明确不同腐殖质组分对土壤肥力的影响提供理论依据。【方法】供试土壤为江苏省溧阳市南渡镇"白土改良大田示范试验核心区"的南方中低产水稻土(白土)。试验设秸秆还田(ST)、施有机肥(OM)和对照(CK,不施有机物)3个处理,培肥3年。同时采集试验田周围相邻的江苏省耕地质量监测点(2007~2013年)的每年施化肥(LAF)和长期不施肥(NF)的两种处理土壤进行比对研究。分别测定土壤的基本理化性质及其腐殖质含量的组成,并提取土壤胡敏酸(HA)固体样品利用红外光谱和元素分析来进行结构表征。【结果】秸秆还田和施有机肥处理的有机碳、全氮含量明显高于对照;与对照相比,施有机物料土壤HA的E4/E6比值增加,且秸秆还田施有机肥对照。红外光谱显示,试验区域和耕地监测点的不同处理土壤HA均在1650 cm-1处(酰胺I带)和1550 cm-1处(1500~1580 cm-1酰胺II带伸缩振动)有特征吸收。施有机肥和秸秆还田处理土壤HA的2920/1720、2920/1650比值显著大于对照。在元素组成上,OM、ST处理的土壤腐殖质(HA)中C、H、N的含量比均高于CK,相对长期施化肥(LAF)和不施肥(NF)的土壤有明显提高,而氧元素的含量呈降低的趋势;OM和ST处理土壤HA的[H]/[C]和[O]/[C]原子数比均低于CK;与LAF和NF处理相比,试验区域各处理土壤腐殖质的[H]/[C]和[O]/[C]原子数比均有明显降低。【结论】有机物料施入土壤后可增加土壤有机碳含量,改善土壤理化性质,提高作物产量和品质,且施入土壤的有机物料可转化为新的腐殖质,降低土壤的腐殖化程度。土壤腐殖质(HA)的红外光谱分析说明,白土土壤HA具有明显的酰胺类化合物特征。有机物料施入后使得土壤脂族性增强,羧基量减少,芳香度降低;秸秆还田和施有机肥处理与对照相比,土壤HA的[H]/[C]和[O]/[C]比均有下降的趋势,且HA的氮素含量明显增加,这显示有机物料施入后白土土壤腐殖质发生"脱水"过程,同时也反映了白土土壤腐殖质形成的特征。