土壤中水溶性有机质的结构特征及其与富里酸、胡敏酸的比较

采用元素分析、1HNMR和FTIR研究了黄泥土中水溶性有机质组成及结构特征,并与富里酸、胡敏酸进行比较。结果表明:胡敏酸含有大量的芳香族不饱和物质,烷基链烃多,支链长;富里酸以含有大量的羧基为主要结构特征;水溶性有机质主要由碳水化合物组成,含有大量的羟基,芳香族不饱和物质少。     

水稻秸秆燃烧对土壤有机质组成的影响研究

研究生物质(水稻秸秆)燃烧行为对土壤有机质含量和组成的影响,探讨不同燃烧次数下土壤中胡敏酸(HA)、富里酸(FA)、水溶性有机质(DOM)的含量和结构特征的变化情况。结果表明:土壤有机碳的变化仅在土壤表层几厘米以内,随燃烧频次增加土壤有机碳含量减少量增加,而水溶性有机质及组分则呈现不断增加的趋势。不同来源土壤的腐殖物质对生物质燃烧作用的响应不同,3种供试土样中腐殖物质随不同次数同强度秸秆燃烧并未呈现较一致的变化趋势,但每一种土壤的HA和FA含量及HA/FA、E4/E6值均随燃烧频次的增加呈现规律性的升高或者降低,而且FA含量的变化是影响HA/FA值大小的主导因素。此外,通过红外光谱图可知,随燃烧频次增加,FA中芳香性成分和含脂肪族C—OH、C—O物质增加,而HA由于本身芳香缩和度高而无明显变化。     

短期增温及减少降雨对杉木人工林土壤DOM的数量及其光谱学特征的影响

本文选取我国中亚热带杉木人工林土壤进行短期增温以及减少50%降雨试验,利用光谱技术研究增温及减少降雨对土壤可溶性有机质(DOM)数量和结构的影响。试验设对照(CT)、增温(W,土壤温度增高5℃)、减少降雨(P,自然降雨量减少50%)、增温与减少降雨交互作用(WP)4种处理。结果表明:1)增温增加了土壤可溶性有机碳(DOC)数量,使DOM的芳香性指数和腐殖化指数减小,结构变得简单易于分解;0~10 cm土层的土壤DOM含有较多的烷烃,酯类物质较少;10~20 cm土层的DOM则含有较多的碳水化合物。2)减少降雨使土壤水分相对减少,土壤DOC的数量降低。0~10 cm土层土壤DOM的芳香性指数和腐殖化程度降低,DOM含有大量的烷烃;而10~20 cm土层土壤DOM的芳香性指数和腐殖化指数升高,碳水化合物少。减少降雨处理使土壤可溶性有机氮(DON)数量增加。3)增温和减少降雨的交互作用增加了DOC和DON的数量,降低了DOM的芳香化程度和腐殖化程度;使0~10 cm土层的DOM含有较多的碳水化合物,而10~20 cm土层的DOM碳水化合物较少。4)对于0~10 cm土壤,增温对土壤DOM的数量及结构的作用最强;随着土壤深度增加到10~20 cm,减少降雨的作用逐渐明显,其对DOM结构的影响也达到显著水平。温度及降水对DOM的数量及化学结构的变化具有重要意义,该研究结果可以为阐释全球气候变化背景下土壤DOM的动态周转及预测未来森林土壤碳氮的变化趋势提供科学依据。     

亚热带典型地貌下旱地和水田可溶性有机物化学组成特征

阐明亚热带典型地貌下旱地与水田土壤可溶性有机物(DOM)化学组成差异可为农田土壤DOM稳定性评价提供理论依据。研究采用XAD-8树脂分组和热裂解气质联用仪(Py-GCMS)技术,分析比较休闲期、耕作期亚热带喀斯特山区、丘陵区及平原湖区旱地和水田土壤DOM化学组成特征。结果表明:休闲期,亲、疏水性可溶性有机碳(DOC)含量以水田(10.2、33.4 mg/kg)显著高于旱地(4.15、12.8 mg/kg),耕作期无显著性差异。与休闲期相比,耕作期水田亲、疏水性DOC含量均显著降低,而旱地亲、疏水性组分DOC含量在两个时期间保持相对稳定。休闲期旱地和水田土壤DOM中有机酸相对比例分别为31.9%、35.6%,耕作期显著降至17.9%、20.0%(P0.05)。脂类相对比例趋势与有机酸相反,旱地和水田土壤DOM中脂类相对比例在休闲期分别为55.0%、49.5%,耕作期显著增至70.1%、62.9%(P0.05)。Adonis分析表明,亲、疏水性DOC含量在旱地和水田、休闲期和耕作期差异显著(P0.05);DOM化学组成在不同时期(休闲期和耕作期)及地貌(喀斯特山区和丘陵区、丘陵区和平原湖区)差异显著(P0.05)。Random Forest分析表明,有机酸和脂类参与微生物代谢过程,在休闲期和耕作期差异显著(P0.05);芳香化合物作为DOM稳定性组分,在不同地貌区差异较大(P0.05)。总体上,田间条件下水田DOC比旱地DOC对时期响应更敏感,且土壤DOM中微生物代谢相关组分(有机酸、脂类)和稳定性组分(芳香族化合物)在不同时期及地貌区的差异性不同,这对评价旱地和水田土壤DOM稳定性及土壤有机碳积累具有一定的参考意义。     

不同来源有机肥释放的溶解有机质粒径分布与光谱特征

  【目的】  研究不同来源有机肥释放的溶解有机质 (DOM) 的粒径分布与光谱特征,为有机肥在农业生产中的应用及DOM后续环境行为的研究提供理论指导。  【方法】  本研究选择海藻、羊粪、虾肽以及小麦秸秆生物炭4种有机肥,提取有机肥中的DOM (<0.7 μm)。利用超滤分级技术对提取的DOM进一步区分为 <1 kDa、1～100 kDa、100 kDa～0.2 μm和0.2～0.7 μm 4个粒级,使用总有机碳 (TOC) 分析仪测定各粒径DOM的含量并使用傅里叶变换红外光谱 (FTIR)、紫外?可见吸收光谱 (UV-Vis) 和三维荧光光谱 (3D-EEM) 进行光谱表征。  【结果】  从全量 (粒径<0.7 μm) 溶解有机碳(DOC)来看,小麦秸秆生物炭 (308 mg/kg)<虾肽 (1060 mg/kg)<海藻 (1266 mg/kg)<羊粪 (2989 mg/kg)。供试有机肥中不同粒径的DOC所占比例和含量差异明显,均以最小粒径 (<1 kDa) 所占比例最高,除海藻为47%外,其余有机肥处理皆达到50%及以上。4种不同来源有机肥DOM的紫外和荧光特征值表明,4种有机肥的荧光指数 (FI) 和自生源指数(BIX)随着DOM粒径的减小而增大,而SUVA₂₅₄、SUVA₂₆₀和腐殖化指数 (HIX)随着DOM粒径的减小而减小。虾肽DOM各粒径的类蛋白组分含量高且主要为内源DOM,自生来源有机质丰富,生物可利用性高;羊粪DOM各粒径受人类活动影响较大;而小麦秸秆生物炭的DOM大粒径(>100 kDa)组分的FI<1.4,表明其大粒径DOM主要为外源性的,自身生产和微生物活动贡献相对较低。此外,尽管海藻、羊粪和虾肽各粒径的DOM的HIX值随着粒径的减小而逐渐减小,除虾肽DOM的<1 kDa组分外,其腐殖化程度依旧较高 (HIX>10),而小麦秸秆生物炭小粒径DOM的HIX<4,表明小麦秸秆生物炭的小粒径DOM疏水组分含量高,腐殖化程度相对较低。荧光组分和红外光谱表明了4种不同来源有机肥DOM以类腐殖质物质为主,且含有大量氨基酸N—H键、O—H键和C—O键等官能团。  【结论】  依据有机肥释放的DOM的粒径分布和光谱特征,海藻、羊粪、虾肽有机肥中的DOM主要以小粒径为主,其腐殖化程度高,蛋白组分含量较低。小麦秸秆生物炭DOM的生物稳定性要高于其他有机肥,生物可利用性较低,因此,施加过量的生物炭不利于微生物对土壤DOM的降解利用;而虾肽来源有机肥的DOM类蛋白组分贡献最大,生物可利用性高,施用虾肽有机肥可能有利于微生物对土壤DOM的降解利用。     

生物炭添加对旱作农田土壤溶解性有机质及其动态影响的定位研究

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。     

海南北部滨海区不同土地利用模式下土壤DOM粒径分布与光谱特性

为研究海南热带滨海区不同土地利用模式对土壤溶解态有机质(DOM)含量组成及其分子粒径依赖性的影响,分别采集琼北滨海地区四种代表性土地利用模式下(水稻田、菜园、果园和橡胶园)土壤为研究材料,通过超滤技术对土壤水提液进行分级(所选滤膜孔径大小分别为0.7、0.45、0.2、0.1μm和100、10、1 kDa),并对样品中DOM的碳、氮含量和光谱特性(紫外-可见吸收光谱、三维荧光光谱、傅立叶变换红外光谱)进行表征。结果表明,四种地类土壤溶解态有机碳(DOC)含量(0.7μm)为水稻土(171.9 mg·kg~(-1))最高,胶园土(116.7 mg·kg~(-1))最低;而C/N值则为胶园土(22.26)最高,菜园土(11.39)最低。在不同粒径中,4种地类土壤DOC含量为1 kDa组分占比最高(45%以上),C/N值则在1 kDa粒径中最高(31.43),10～100 kDa中最低(4.80)。紫外-可见吸收光谱和红外光谱表明了水稻土和菜园土DOM的分子芳香性(SUVA_(254))、分子量大小(S_R)和疏水组分(SUVA_(260))比例显著高于胶园土和果园土,且含有较多的醇、酚、芳香类物质。三维荧光光谱特征表明四种土地利用模式土壤DOM的来源均为土壤微生物活动产生的"内源"。由此可见,不同的土地利用模式和粒径大小会影响土壤DOM的含量和组成结构,人类活动干扰是引起地类间DOM差异显著的重要因素。     

不同处理牛粪对植菜土壤腐殖质结构特征的影响

通过元素组成分析法、红外光谱分析法(IR)、核磁共振光谱分析法(13 C-NMR)等现代分析方法,研究施用新鲜牛粪、腐解牛粪和蛴螬牛粪2a后对植菜轮作土壤胡敏酸(HA)和富里酸(FA)的影响。结果表明,与单施化肥(CK)相比,不同牛粪处理对植菜土壤胡敏酸和富里酸的元素组成影响有较大的差异,各牛粪处理均引发植菜土壤胡敏酸C含量和C/H降低,O含量、O/C和(N+O)/C升高,富里酸C含量和C/N升高,N、O含量和O/C降低,降低了植菜土壤胡敏酸的缩合程度,升高了土壤胡敏酸的氧化程度和极性,降低了植菜土壤富里酸的氧化程度。不同牛粪处理使植菜土壤胡敏酸的脂肪族化合物减少,且均含有苯基碳、酚羟基C、芳香醚和(或)与O、N等取代基邻、对位的连H芳香C,使芳构化程度增加,富里酸的脂肪族化合物增加,芳香类、羧基类化合物减少,芳构化程度降低。不同牛粪处理的植菜土壤未改变土壤腐殖质的基本结构特征,只引起植菜土壤的结构单元和官能团数量上的差异。     

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。     

水稻秸杆腐解过程溶解性有机质红外光谱研究

采用傅里叶红外光谱(FTIR)分析方法研究了水稻秸杆不同腐解阶段产生溶解性有机质(dissolvedorganic matter,DOM)及其分组组分的结构特征.结果表明,水稻秸杆腐解过程中DOM组成成分的变化呈现出明显的阶段性.在第0～3天,秸杆本身含有的糖类、氨基酸等小分子物质因微生物繁殖迅速消失;第3～ 63天,主要是秸杆中的半纤维素、纤维素的分解阶段,DOM组成中多糖类、烷烃类物质呈现起伏性变化;第63天后,主要是腐殖化阶段,DOM分子结构复杂化.各分组组分的结构特征有明显差异,且各组分均随腐解延长而发生变化,即多糖类物质减少,芳香族物质增多,分子结构复杂化.     

Composition and spectroscopic characteristics of dissolved organic matter extracted from the sediment of Erhai Lake in China

Purpose

The content and composition of dissolved organic matter (DOM) in sediment directly affect nutrient cycling and material exchange in lake ecosystems. This study investigated the content and composition of DOM and its fractions in sediments, as well as the relationship between the different parameters and nitrogen (N) forms in DOM. The main aim of this study was to evaluate the compositional characteristics of DOM, hydrophobic bases (HOB), hydrophobic acids (HOA), hydrophobic neutral fractions (HON), and hydrophilic matter (HIM) in sediments from Erhai Lake, China.

Materials and methods

Seven surface sediment samples with different environmental characteristics were collected. The DOM in the sediment was fractionated into HOB, HOA, HON, and HIM using XAD-8 resin based on compound hydrophobicity. The contents of DOM and its fractions were measured using a TOC analyzer. The structural characteristics of DOM and its fractions were investigated using fluorescence spectroscopy and UV–Vis absorbance. Correlation analyses were carried out to better understand the relationships between the parameters of the spectral characteristics and the contents of the different N forms in DOM and its fractions.

Results and discussion

The content, spatial distribution and structure of DOM and its fractions in Erhai Lake sediment were affected by water depth and aquatic plants. The DOM content in sediment ranged from 0.2 to 0.5 g kg^?1. HON accounted for 41.3 to 85.7 % of DOM, whereas HIM constituted 15.0 to 58.7 % and was significantly negatively correlated with HON (R ² ?=?0.856, P?Conclusions (1) Hydrophobic fractions are the major components of DOM in the sediments from the seven sites in Erhai Lake. (2) DOM and its fractions mainly originated from microbial sources. (3) The A ₂₅₃/A ₂₀₃ ratio is useful for evaluating the contents of N forms. The structure of DOM and its fractions are important in affecting the contents of DON. Nitrate (NO₃-N) contributes to eutrophication, and thus cannot be ignored from studies of Erhai Lake sediment.     

Differences in the chemical composition of dissolved organic matter from waste material of different sources

The chemical composition of waste-material-derived dissolved organic matter (DOM) was characterized by chemolytic analyses and ¹H, ¹³C and ³¹P nuclear magnetic resonance (NMR) spectroscopy. Dissolved organic matter was extracted by water from an aerobic fermented urban waste compost, a sewage sludge and a pig slurry and then fractionated using the XAD-8 method. The amount of water-extractable dissolved organic carbon (DOC) ranged from 3% in the sewage sludge to 22% in the pig slurry. Dissolved organic matter isolated from pig slurry was equally distributed between hydrophilic and hydrophobic DOC, whereas in the sewage-sludge-derived material the hydrophobic fraction was predominant. Dissolved organic C from the urban waste compost was mainly within the hydrophilic fraction. Wet-chemical analysis and ¹H- and ¹³C-NMR spectra showed that both DOM fractions from the urban waste compost were low in neutral, acidic and amino sugars as well as in lignin-derived compounds. In turn, the materials were rich in low-molecular-weight aliphatic compounds. The chemical structure of both fractions is probably the result of the intensive transformation of urban waste compost during its fermentation. The hydrophilic fractions of DOM from sewage sludge and pig slurry contained considerable amounts of carbohydrates but were also rich in low-molecular-weight aliphatics. The respective hydrophobic fractions had the largest contents of CuO-extractable phenols which may in part derive from sources other than lignin. By contrast with the other materials, the hydrophobic fraction from the pig slurry seemed to contain polymeric rather than low-molecular-weight material. The ³¹P-NMR spectrum of the hydrophilic DOM fraction from urban waste compost did not show signals of inorganic or organic P compounds while the spectrum of the hydrophobic fraction revealed traces of monoester P, diester P, and orthophosphate. ³¹P-NMR spectroscopy suggested that both the hydrophobic and hydrophilic fractions from pig slurry did not contain organic P. The hydrophilic DOM fraction from sewage sludge contained orthophosphate, organic monoester P and a little pyrophosphate. The hydrophobic fraction contained mainly organic diester P and smaller amounts of teichoic acids and organic monoester P. Considering that water-soluble fractions of urban waste compost contained no easily plant-available P and a low content of labile organics, we conclude that this material contains less labile nutrients and is more refractory than the soluble constituents of pig slurry and sewage sludge.     

Changes in properties of soil-derived dissolved organic matter induced by biodegradation

Properties of dissolved organic matter (DOM) determine its biodegradation. In turn, biodegradation changes the properties of the remaining DOM, which may be decisive for the formation of stable organic carbon in soil. To gain information on both mechanisms and controlling factors of DOM biodegradation and the properties of biodegraded DOM, we investigated changes in the composition of 13 different DOM samples extracted from maize straw, forest floors, peats, and agricultural soils during a 90-day incubation using UV absorbance, fluorescence emission spectroscopy, FTIR-spectroscopy, ¹H-NMR spectroscopy, pyrolysis-field ionization mass spectroscopy (Py-FIMS), and ¹³C natural abundance before and after incubation. Changes in the DOM properties were related to the extent of biodegradation determined by the release of CO₂. Increasing UV absorption and humification indices deduced from fluorescence emission spectra, and increasing portions of aromatic H indicated relative enrichment of aromatic compounds during biodegradation. This enrichment significantly correlated with the amount of DOC mineralized suggesting that aromatic compounds were relatively stable and slowly mineralized. ¹³C depletion during the incubation of highly degradable DOM solutions indicated an enrichment of lignin-derived aromatic compounds. Py-FI mass spectra indicated increasing contents of phenols and lignin monomers at the expense of lignin dimers and alkylaromatics during incubation. This partial degradation of higher-molecular, lignin-derived DOM compounds was accompanied by relative increases in the proportions of lower-molecular degradation products and microbial metabolites. Carbohydrates, especially when abundant at high initial contents, seem to be the preferred substrate for microorganisms. However, four independent methods suggested also some microbial production of carbohydrates and peptides during DOM degradation. After incubation, the composition of highly degradable DOM samples became similar to relatively stable DOM samples with respect to aromaticity, carbohydrate content, and thermal stability. We conclude that DOM biodegradation seems to result in organic matter properties being a precondition for the formation of stable carbon. These structural changes induced by DOM biodegradation should also result in stronger DOM sorption to the soil matrix additionally affecting DOM stabilization.     

Chemical Nature and Composition of Compost During Mushroom Growth

Improvement of the process of mushroom composting is of importance in order to provide an optimal growing medium needed for the mushroom. Since composting produces a food source for the mushroom, the compositional changes of mushroom compost occurring during the growth cycle of the button mushroom, Agaricus bisporus, were studied. Samples were collected during spawning, casing and the following four flushes. Samples were analyzed for their elemental composition, carbohydrates, FTIR, ¹³C-NMR, pyrolysis-GC/MS and tetramethylammonium hydroxide (TMAH) thermochemolysis-GC/MS. The carbohydrate analysis revealed a decrease in the total amount of about 40% of the identified monosaccharides during mushroom growth. The ¹³C-NMR data also confirm that polysaccharides are the main fraction degraded (or utilized by the mushrooms) during the cropping period. These findings were also confirmed by changes in the absorbance of functional groups observed in the FTIR spectra. Pyrolysis data revealed chromatographic peaks related to polysaccharides-, proteins- and lignin-derived compounds. Both pyrolysis and TMAH thermochemolysis data show degradation of lignin structures during the growth period. Lignin alteration primarily involved a preferential degradation of syringyl units and oxidation of side chains of guaiacyl moieties. This study suggests that the polysaccharide fraction of the mushroom substrate is the main organic fraction utilized during the process. In addition, alterations of lignin structures have occurred although its relative content usually increases during mushroom cropping.     

CP-MAS-13C-NMR-Spektren organischer Lagen einer Tangelrendzina

CP-MAS-¹³C-NMR Spectra of a Lithic Cryofolist CP-MAS-¹³C-NMR spectra of the organic layers of a lithic cryofolist show typical changes during litter decomposition and humification. Peaks due to alkyl-C (mainly polymethylene) and carboxyl-C increase, those due to ether-C (carbohydrates), acetal-C and aromatic-C decrease. These results are in agreement with the results obtained from conventional extractive techniques. The aliphatic character is far more pronounced than the aromatic one.     

Nuclear Magnetic Resonance,Infra-Red and Pyrolysis: Application of Spectroscopic Methodologies to Maturity Determination of Composts

Compost maturity or stability reflects the degree of decomposition of the organic matter (OM). Since stability of natural OM is a relative term, defining it is not a trivial challenge. In addition, it requires a series of chemical, physico-chemical and spectroscopic determinations. Among the methods applied, ¹³C-NMR and FTIR (or DRIFT) and pyrolysis have been shown to be of significance and therefore this review will be dedicated to studies focusing on the application of these methods to composting research. In fact, solid-state ¹³C-NMR spectroscopy has become the most important tool for examining the chemical structure of natural OM (NOM) and the chemical changes associated with OM decomposition. Changes can be measured on the bulk OM either fresh or composted, on humic substances (HS) extracted from the compost or on dissolved organic matter (DOM). Recently, 2D ¹H NMR has been employed to study properties of HS extracted from MSW compost. In general, changes measured on decomposing OM are more distinct in the following order of tested materials: DOM > Bulk OM > HS > Core HS. In conclusion, compost HS which are “young” relative to soil HS were shown to differ from the latter mostly in their high levels of aliphatic and polysaccharide components, which tend to decompose during composting. ¹³C-NMR is the most effective instrument applied to date to structural studies of NOM.     

Dissolved organic matter sorption on sub soils and minerals studied by 13C-NMR and DRIFT spectroscopy

Sorption on the mineral matrix is an important process restricting the movement of dissolved organic matter (DOM) in soils. In this study, we aimed to identify the chemical structures responsible for the retention of DOM by sorption experiments with total DOM and acidic humic substances (AHS), containing humic and fulvic acids, on soil samples and minerals (goethite, ferrihydrite, and amorphous Al(OH)₃). The AHS remaining in solution after sorption were studied by ¹³C nuclear magnetic resonance (NMR) analysis, and total DOM and AHS for bed on the surfaces of minerals by diffuse reflectance Fourier-transform infrared (DRIFT) spectroscopy. The soil samples were taken from strongly sorbing Bw horizons of two Inceptisols rich in pedogenetic Fe (29 and 35 g kg ^?1) and containing little C (7 and 22 g kg^?1). The ¹³C-NMR spectra showed that sorption causes a preferential removal of aromatic and carboxyl C from the solution, whereas alkyl-C accumulates in the solution. No change was observed for O-alkyl C. The DRIFT spectra of sorbed total DOM and AHS showed a relative increase of the band intensity of carboxyl groups compared to DOM in the initial solution, confirming the importance of those groups for the sorption to mineral surfaces. The spectra also indicated reactions of carboxyl groups with metals at the mineral surfaces. The extent to which the carboxyl groups are bound depended on the surface coverage with DOM and the type of mineral.     

Analysis of the green fraction of humic acids

The green fraction of humic acids (HAs), Pg, was fractionated by gel chromatography on Sephadex G-50. Repeated chromatography of the crude Pg obtained by the first chromatography of HA yielded a sharp peak (G₁) and two broad bands (G₂) of purified Pg. The recovery of Pg in G₁ and G₂ as percentages of the total Pg content of the HA were 16.2 and 14.5%, respectively. Distinct peaks were detected at 615, 570, 450 and 280 nm in the UV-visible spectra of both G₁ and G₂ in alkali solutions. Estimates of weight-average molecular weight were 9.7 * 10³ for G₁ and 1.23 * 10⁴ for G₂. In the ¹H-NMR spectra the percentage of hydroxyl groups of 4,9-dihydroxy-perylene-3, 10-quinone (DHPQ) nuclei, which are known to be the chromophore of Pg, was 4.1 and 4.5% of the total H, respectively. Based on these values and the H/C ratios, DHPQ-C was estimated as 28% of total C. ¹³C-NMR spectra obtained using inverse-gated decoupling yielded 40–41% aromatic C, which suggested the presence of aromatic rings other than DHPQ. All of the IR, ¹³C- and ¹H-NMR spectra indicated that the two purified Pg samples largely differed from each other in their contents of alkyl and polysaccharide components.     

3C-NMR structural features of soil humic acids and their methylated,hydrolyzed and extracted derivatives

¹³C-NMR spectra of aqueous solutions of three humic acids (1 Typic Chromoxerert (HA-V), 1 Humic Haplorthod (HA-P), and 1 Inceptisol (HA-D)) are presented. The influence of chemical modifications (hydrolysis with 6N HCl, diazomethane methylation, and organic solvent extraction) of the humic substances and their spectra is studied. The spectra of the various humic substances show significant differences.Methylation of the compounds introduces changes in the aromatic and aliphatic (sp³) region of the spectra. Acid hydrolysis removes residual carbohydrates and amino acid signals from the spectra, whereas solvent extraction has the most pronounced influence upon the aliphatic high field region of the spectra, and shows also, that a significant amount of the paraffinic carbons is bound covalently to the aromatic nuclei of the compounds.     

Transformation of organic matter from maize residues into labile and humic fractions of three European soils as revealed by 13C distribution and CPMAS-NMR spectra

The dynamics of incorporation of fresh organic residues into the various fractions of soil organic matter have yet to be clarified in terms of chemical structures and mechanisms involved. We studied by ¹³C‐dilution analysis and CPMAS‐¹³C‐NMR spectroscopy the distribution of organic carbon from mixed or mulched maize residues into specific defined fractions such as carbohydrates and humic fractions isolated by selective extractants in a year‐long incubation of three European soils. The contents of carbohydrates in soil particle size fractions and relative δ¹³C values showed no retention of carbohydrates from maize but rather decomposition of those from native organic matter in the soil. By contrast, CPMAS‐¹³C‐NMR spectra of humic (HA) and fulvic acids (FA) extracted by alkaline solution generally indicated the transfer of maize C (mostly carbohydrates and peptides) into humic materials, whereas spectra of organic matter extracted with an acetone solution (HE) indicated solubilization of an aliphatic‐rich, hydrophobic fraction that seemed not to contain any C from maize. The abundance of ¹³C showed that all humic fractions behaved as a sink for C from maize residues but the FA fraction was related to the turnover of fresh organic matter more than the HA. Removal of hydrophobic components from incubated soils by acetone solution allowed a subsequent extraction of HA and, especially, FA still containing much C from maize. The combination of isotopic measurements and NMR spectra indicated that while hydrophilic compounds from maize were retained in HA and FA, hydrophobic components in the HE fraction had chemical features similar to those of humin. Our results show that the organic compounds released in soils by mineralization of fresh plant residues are stored mainly in the hydrophilic fraction of humic substances which are, in turn, stabilized against microbial degradation by the most hydrophobic humic matter. Our findings suggest that native soil humic substances contribute to the accumulation of new organic matter in soils.