稻草腐解过程中形成胡敏酸的组成和结构研究

通过稻草腐解实验,采用化学分析方法,研究了稻草腐解过程中土壤胡敏酸的化学特征的动态变化,旨在丰富农作物秸秆还田过程中的胡敏酸化学组成、性质与结构变化的特征。在试验培养条件下,施用稻草后土壤的有机碳含量提高了31.71%,腐殖质含量增加了51.93%,都在90d时达到最大值。施用稻草45d时的PQ值(HA在HS中所占的比例)明显降低,在90d和135d时的PQ值与45d时变化不大。施用稻草后土壤胡敏酸的色调系数(ΔlogK)逐渐减少,相对色度(RF)值迅速增大,胡敏酸的氧化程度和芳构化程度增强。胡敏酸的元素组成以碳为主,含量在52%左右,其次为氧。H/C的比值逐渐降低,O/C的比值不断增大。羧基和酚羟基为主要的酸性基团。羧基含量先降低,后随着腐解的进行,其含量不断升高;酚羟基的含量变化与羧基的含量变化趋势相反;羰基含量逐渐增加。施用稻草会引起紫色水稻土胡敏酸化学组成和结构的变化。     

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用对土壤胡敏酸性质的影响机制提供理论依据。     

紫色水稻土胡敏酸的形成——稻草腐解试验

土壤腐植酸类物质的形成是土壤固碳的重要过程,但对腐植酸类物质形成过程的了解仍不甚清楚,为了丰富土壤腐植酸类物质形成理论,采用富立叶变换红外光谱和固态交叉极化-魔角旋转^13C-核磁共振光谱技术分析了紫色水稻土稻草腐解过程中胡敏酸的波谱学特征。结果表明,稻草腐解的前期,胡敏酸的红外光谱所有吸收峰（3364、2933、1653、1599、1508、1461、1421、1331、1225、1126、1033cm^-1）强度皆有明显减弱,核磁共振光谱的烷基、多羟基和芳基的共振峰明显减弱且甲氧基的共振峰显著增强,即表明提取的胡敏酸为类胡敏酸的木质素;随着腐解的进行,胡敏酸的红外光谱的吸收峰强度皆显著增强,核磁共振光谱的烷基、芳基和羰基的共振峰增强,即表明此时的胡敏酸已是以木质素残体为核心并结合烷基、酰胺以及糖类物质反应形成的高分子聚合体;稻草腐解的后期,胡敏酸的红外光谱的2933cm^-1处的吸收峰强度减弱,1651、1599、1508、1461、1422和1224cm^-1处的吸收峰小幅增强,核磁共振光谱的烷基共振峰减弱,甲氧基共振峰增强,表明此时的胡敏酸发生脱烷基（主要是甲基）过程。因此,红外光谱吸收峰强度与核磁共振光谱共振峰强度的规律性变化反映了稻草腐解过程紫色水稻土胡敏酸的形成过程具有阶段性,紫色水稻±胡敏酸的形成过程符合木质素学说。     

有机肥腐解过程的红外光谱研究

对玉米秸秆、树叶、鸡粪及牛粪4种有机肥腐解过程中形成的水溶性有机物(WOM)进行了化学分析并做了红外光谱研究。结果表明,不同的有机肥的WOM总量及各组分的含量有很大的差异,树叶和玉米秸秆腐解形成的WOM中,水溶性胡敏酸(WHA)所占的比例较大;而牛粪和鸡粪腐解形成的WOM中,水溶性小分子有机物(WLOM)所占的比例较大。随着有机肥的腐解,所形成的WLOM中,脂肪族化合物、酰胺类化合物逐渐减少,有机酸的比例不断增大。WHA中的甲基、亚甲基和次甲基的含量升高,脂族性增强,酰胺结构成分逐渐减少。树叶腐解形成的碱提胡敏酸(AHA)的脂肪链结构和碳水化合物成分含量较低。牛粪腐解形成的AHA的脂肪链结构成分和碳水化合物成分含量较高。鸡粪腐解形成的AHA缺乏脂肪链结构成分,碳水化合物成分含量较高。而玉米秸秆腐解形成的AHA在不同的腐解时期有一定差异。     

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。     

不同施氮量下潮土中小麦秸秆腐解特性及其养分释放和结构变化特征

  【目的】  秸秆腐解与元素转化涉及复杂的生物化学过程，提高土壤氮素水平是加速秸秆腐解和养分释放的关键措施。研究不同施氮水平下潮土中小麦秸秆腐解特性、养分释放特征及其结构组分变化规律，深入了解秸秆腐解过程与机制，为完善作物秸秆还田技术、实现秸秆资源的高效利用及农田可持续发展提供科学依据和技术支撑。  【方法】  本试验点位于河南省原阳县，土壤类型为潮土，种植制度为小麦–玉米轮作，以小麦秸秆为研究对象，设置0 (SN0)、180 (SN1) 和240 (SN2) kg/hm2 3个氮肥用量，进行187天的秸秆包填埋试验，利用超高分辨场发射扫描电镜 (SEM)、固态核磁共振 (13C-NMR) 等方法研究小麦秸秆腐解过程中的养分释放和结构组分动态变化规律。  【结果】  1) 小麦秸秆腐解呈现前期快后期慢的特征，前两周为快速腐解期，该阶段秸秆平均腐解率为46%，整个玉米季 (100天) 秸秆平均腐解率为71%；高氮营养环境对前两周的秸秆腐解率无显著影响；从第二周开始，施用氮肥处理加速了秸秆腐解，SN1和SN2处理秸秆腐解率平均高于SN0处理6个百分点，但SN1和SN2处理间无显著差异；秸秆碳释放率与秸秆腐解率变化趋势基本一致。2) 腐解187天后，秸秆氮磷钾养分最终释放率大小顺序为钾 (96%～97%) > 氮 (52%～86%) > 磷 (29%～45%)，其中钾在前两周基本完全释放，而氮、磷释放率在后期有负增长现象。3) 纤维素、半纤维素腐解率与秸秆腐解规律基本一致，均表现出前期快后期慢的特点，而木质素则在中后期腐解较快；纤维素、半纤维素和木质素最终腐解率分别为78%～87%、86%～91%和66%～73%（187天后）。4) 扫描电镜结果显示，小麦秸秆结构逐渐遭到破坏，表面变得粗糙，断层增多，空洞增大，纤维束变得松散，形成近似网状结构；高氮处理下小麦秸秆表观结构受破坏程度大于不施氮处理。5) 核磁共振结果显示，不同有机碳官能团信号强度分布表现为:烷氧碳 (47.02%～60.13%) > 烷基碳 (11.41%～17.38%) > 双烷氧碳 (10.79%～13.31%) > 甲氧基碳/烷氮碳 (7.53%～12.02%) > 芳基碳 (2.70%～7.18%) > 羧基碳 (1.07%～2.60%) > 酚基碳 (0.75%～2.02%)；腐解过程中烷基碳、甲氧基碳/烷氮碳、酚基碳和羧基碳相对含量显著增加，而烷氧碳相对含量显著降低。6) 相关分析表明，秸秆残余物所有有机碳官能团均与腐解率、碳释放率有显著或极显著相关性；有机碳官能团中只有烷氧碳、甲氧基碳/烷氮碳与氮释放率有显著相关性；烷氧碳、双烷氧碳与纤维素、半纤维素和木质素腐解率均呈极显著负相关，羧基碳和甲氧基碳/烷氮碳均与木质素腐解率呈现极高的正相关性。  【结论】  施用氮肥能够促进小麦秸秆腐解和碳释放，其效果在秸秆还田两周后才能显现出来；在腐解过程中，秸秆残余物中代表易分解碳水化合物的烷氧碳相对含量随腐解时间延长而不断降低，且占比均高于其它碳官能团，对指示秸秆腐解进程具有重要意义；固态核磁共振技术更有利于监测秸秆腐解过程中不同有机碳官能团结构变化，从而更深刻地认识秸秆腐解机制。     

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。     

土壤中无机纳米粒子对玉米秸秆有机质分解的影响

该文从纳米尺度分析土壤颗粒对作物残体有机质分解的影响。将黑土B层提取出的纳米粒子溶液施入正在腐解的秸秆中，在不同的培养时期提取腐解产物，并用重铬酸钾—硫酸容量法测定有机质各分解组分含量和傅里叶红外光谱仪分析主要分解组分 功能团。含量分析结果表明：无机纳米粒子对水溶性有机化合物的生成在腐解前期和后期有显著抑制作用；腐解前期促进碱溶性有机化合物和碱溶性富里酸的生成，在后期没有显著影响；整个腐解过程均促进秸秆腐解生成小分子化合物，并降低水溶性胡敏酸含量。红外光谱分析结果表明：无机纳米粒子在腐解前期和中期抑制碳水化合物生成，腐解中期促进碳酸盐物质生成；整个腐解周期均能显著提高脂肪链结构、甲基、亚甲基生成。该研究证明土壤无机纳米微粒对有机质分解转化有显著影响。     

土壤有机培肥后胡敏酸结构特征变化规律的探讨--Ⅰ.胡敏酸的化学性质和热性质

通过在棕壤、草甸土和水稻土上进行的田间和模拟试验表明,土壤有机培肥一般使胡敏酸(HA)的数均分子量、缩合度(C/H)、羧基含量和反应热下降。除草甸土外,土壤有机培肥还能使胡敏酸的氧化度(O/C)和高温与低温放热之比降低。说明胡敏酸变得简单化和年轻化。此外,施用猪粪可以增加胡敏酸的含氮量和降低酚羟基含量,玉米秸秆则相反。     

Effect of aromatic compounds,humic acids and lignins on growth of the earthworm eisenia foetida

Thirty eight low molecular weight aromatic compounds, two humic acids, and five lignins were tested for their effects on the growth and survival of the earthworm Eisenia foetida with activated sludge as food source. Benzenoid molecules with two methoxyl or methyl groups were generally more toxic than analogous molecules substituted with one or two hydroxyl groups instead. Placing a carboxyl group or groups on a molecule of relatively high toxicity tended to reduce its toxicity or to result in a totally innocuous substance. Tannins and molecules which could be easily polymerized to form tannin-like substances were generally non-inhibitory to growth, as were humic acids and lignins.     

Comparison of humic acids derived from city refuse with more developed humic acids

Abstract

The humic acids (HA) from composted and uncomposted city refuse (CR) were characterized by degradative (oxidation with persulphate and permanganate) and non-degradative techniques (FT-IR and ¹³C-NMR) in order to analyze the effect of the composting process on these HA. They were also compared with commercial HA extracted from leonardite. The carboxyl and carbonyl group content of the HA from CR increased slightly during composting. Since the HA from the composted CR showed a lower N and H content, the FT-IR spectra showed a lower intensity in the bands corresponding to peptides and carbohydrates. Differences were revealed when the HA from both CR were compared with those from leonardite which showed a much lower N and H content and a less aliphatic character. The percentage of degraded products by persulphate was higher for the HA from uncomposted CR. For the HA from both CR the major components among the oxidation products were dicarboxylic acids and normal fatty acids. In the leonardite HA, the major components consisted of benzene polycarboxylic acids. ¹³C-NMR revealed an attenuation of the aliphatic character of the HA from CR with composting.     

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.     

Characteristics of Humic Substances in Paddy Soils

In the present paper,the composition of humus and the charateristics of humic acid from seven paddy soils were compared with those of upland (and/or natural) soils.Results show that:(1) in each group of the soil samples for comparison the HA/FA ratio of the humus of a paddy soil,in most cases,was appreciable higher than that of adjacent upland(and/or natural) soil derived from the same parent material;(2) the humic acid extracted from the paddy soils was characterized by a higher C/O ratio,a higher content of methoxyl groups,and a lower content of carboxyl groups than those from the corresponding upland (and/or natural) flooded soils,implying that the humic acid formed under rice cultivation is in a lower degree of humification than that formed under upland(and/or natural) conditions;and (3) the humic acid of paddy soils,however,was not always characterized by a lower aromaticity than that of the corresponding upland(and/or natural) soils.     

Chemical studies on soil humic acids

The levels of alcoholic and phenolic hydroxyl, methoxyl, carboxyl, and carbonyl groups of 33 to 38 humic acids obtained from various types of soils were determined to analyze the relationships between the amounts of these functional groups and the degree of humification or the types of soils. The amounts of various oxygen-containing functional groups examined were all proven to be significantly different among the various types of humic acids by analyses of variance. During humification. generally, the carboxyl and carbonyl groups increased while alcoholic and phenolic hydroxyl and methoxyl groups decreased. Linear and logarithmic regression analyses of carboxyl group contents on RF values (optical density of the alkaline solution of humic acids at 600 nm) gave very significant positive correlations. The carboxyl group contents of Rp type humic acids and humic acids from calcareous soils were largely distributed in the upper side of the regression curve. The carbonyl group contents showed a very significant linear positive correlation with carboxyl group contents. and both of them showed high linear positive correlation with RF values. Phenolic hydroxyl group contents decreased with humification in Rp(l). B. and A type humic acids. Alcoholic hydroxyl group contents showed a significant negative linear association with _RF values. Methoxyl group contents decreased rapidly with increasing humification in low humified humic acids, and their negative correlation with _RF values were proven to be very significant by logarithmic regression analysis. The complicated relationship between oxygen content and RF value which was reported previously (7) has been accounted for by the results obtained in the experiments conducted here.     

石灰性母质对土壤腐殖质组成和性质的影响

本文研究了采自泰安、南京、昆明3地在相近植被类型下的石灰性土壤和非石灰性土壤的腐殖质组成和胡敏酸的结构特征。结果表明,和同一地区的非石灰性土壤相比,石灰性土壤不但胡敏酸/富里酸比值恒较高,活性胡敏酸的相对含量显著较低,且其胡敏酸的芳化度和羧基含量较高,全氮及酰胺态氮的含量较低。看来,土壤呈微碱性反应不仅有利于有机物质腐解过程的进行,而且有利于游离基的形成,从而有利于酚类物质相互之间以及酚类物质与含氮化合物之间的缩聚反应和腐殖酸的脱胺作用的进行。     

Interactions of three s-triazines with humic acids of different structure

The adsorption of three s-triazines (atrazine, terbutylazine, and simazine) on three different humic acids (HAs), before and after acidic hydrolysis, was studied at four diverse pH values from 3 to 4.5. The Freundlich sorption affinity (K(f)) and intensity (1/n) of s-triazines were related to the chemical and structural composition of HA and used in a multivariate statistical analysis. At low pH, the sorption values for s-triazines were not directly justified by the content of carboxyl groups in original HA, while only an increase of phenolic carbons in hydrolyzed HA supported the increased s-triazine adsorption. The structural composition of both s-triazines and humic samples explained 86% of the significance in multivariate analyses, whereas the role of pH remained hidden in only 14% of the statistical significance. Adsorption of s-triazines was mainly related to carbon content, hydrophobicity, and aromaticity of HA, thereby implying a predominant binding role of weak dispersive forces. Steric properties explained the larger adsorption affinity of atrazine and terbutylazine with respect to simazine. The occurrence of charge-transfer interactions between atrazine and mainly hydrolyzed HA was further suggested by the increased number of free radicals detected in atrazine-HA complexes at different pH values. Charge-transfer interactions were postulated to occur when HA conformations became progressively controlled by aromatic components. This work indicates that humic matter rich in hydrophobic and aromatic constituents is more likely to adsorb s-triazines and reduce their environmental mobility.     

Dissolved organic matter in lysimetric water of mountain forest soils in the southern Sikhote Alin

The fractional composition of dissolved organic matter and the chemical nature of humic and fulvic acids were studied in lysimetric waters from forest soils of different altitudinal zones in the Sikhote Alin Range. The elemental composition, infrared absorption spectra, concentrations of acid functional groups, and pK spectra of humic and fulvic acids were determined. Fulvic acids predominated in the upper soil horizons, and fraction of nonspecific dissolved organic substances predominated in the lower mineral horizons. The portion of humic acids in the humus horizons markedly decreased from the low-mountain soils to the high-mountain soils; the nitrogen content of humic and fulvic acids decreased in the same direction. Three classes of carboxyl and phenolic groups were determined in pK-spectra of humic and fulvic acids. The soils of high-mountain zones had stronger acidic properties of humic and fulvic acids in comparison with the soils of low-mountain zones. The determined characteristics of the composition of dissolved organic matter and the trends of their changes contribute to our knowledge of pedogenetic processes in the altitudinal sequence of forest landscapes of the Sikhote Alin Range.     

Molecular characteristics of humic acids extracted from compost at increasing maturity stages

The molecular composition of humic acids (HA) extracted from compost at increasing maturity stages was determined by off-line TMAH-thermochemolysis-GC-MS, in combination with solid-state nuclear magnetic resonance (NMR) and infrared (IR) spectroscopies. While spectroscopy measurements followed the bulk changes, thermochemolysis provided a detailed molecular variation of HA composition. Both thermochemolysis and spectroscopy indicated that polysaccharides, alkyl, cyclic, and aromatic compounds were the predominant components of HA, the stable fraction of compost. NMR dipolar dephasing (DD) experiments confirmed that HA extracts contained lignin in lower amount than its oxidized degradation products. The progressive compost maturity was reflected in HA extracts by a decrease of carbohydrate content and a selective preservation of hydrophobic alkyl molecules, such as medium- and long-chain fatty acids, aliphatic alcohols, linear hydrocarbons, and plant polyester derivatives, like long-chain alkyl dicarboxylic acids, and ω-hydroxyacids. Spectroscopy results showed a concomitant entrapment in HA of biolabile compounds, such as peptidic moieties. The wide range of identified lipid components and plant biomarkers may represent useful tools to trace origin, quality, and transformation of amended compost in soil ecosystems.     

ACIDIC PROPERTIES OF PLANT LIGNINS AND HUMIC MATERIALS OF SOILS

The acidic properties of lignins from the native vegetation of a virgin Ella loamy sand and the humic acids, the 1, 4-dioxane extractable humic fraction and residual humic acids from the virgin and cultivated soils were investigated by determining solid-state cation exchange capacities for Cu and Ca and by non-aqueous potentiometric titration, using potassium methoxide in a benzene-methanol mixture as titrant. The lignins and soil dioxane extracts were titrated in pyridine; the humic acids in dimethylformamide. Platinized Pt and CH₃OH modified calomel electrodes formed the electrode combination. The CEC of the humic acids were much higher than the CEC of lignins with both cations but the Cu: Ca absorption ratios were less for humic acids than for lignins. Titration curves of lignins showed two potential breaks with total acidities of 960 to 1,190 me/100 g. Titration curves of the humic acids showed three to six potential breaks while curves of the soil dioxane extracts showed three and four. The total acidities of the two types of humic isolates were 1,100-1,200 me/100 g. The equivalent weights of most lignins and humic materials were very similar although the acid groups might be different with respect to types and acid strength. Lignins from other plant materials and humic isolates from other soils were also investigated by non-aqueous titration to determine the general applicability of the results obtained with isolates from the Ella soils.