土壤胡敏素分组及特性的研究
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摘要
土壤腐殖质是土壤中所特有的一类特殊的高分子化合物，对土壤肥力、结构和性质具有重要的调节功能，因此对腐殖质的研究在农业生产和环境保护等方面都具有重要的意义。以往的研究都集中在可溶性的腐殖质组分(胡敏酸、富里酸)上，对于不溶性的腐殖质组分(胡敏素)则研究较少。
本文将Pallo有机质分组法进行简化，将土壤胡敏素分为三个组分。并用此法对我国东北不同土壤类型的有机质组成，主要是胡敏素的不同组分的数量及结构特性以及不同比例的玉米秸秆与土壤培养后胡敏素的动态变化进行研究。从而探讨胡敏素各组分的形成、转化机制，为胡敏素在土壤肥力上的作用提供理论依据，也为土壤有机质化学和腐殖质化学研究提供新的资料。主要研究结果如下：
(1)在黑土、草甸土、风沙土中，腐殖酸HE的含量较高，占全碳的30～50％。胡敏素各组分中，以不溶性的胡敏素(HMr)为主，占全碳的30～60％；其次是铁结合胡敏素(HMi)，占全碳的3-6％；含量最少的是粘粒结合的胡敏素(HMc)，占全碳量的1-5％。对HMi、HMc的E4／E6、△LogK值研究得出HMi的分子结构较简单，而HMc分子结构相对较复杂。新形成的HMi、HMc的分子结构比自然土壤简单。对有机质各组分的红外光谱研究得出：HMi、HMc中的脂族结构都高于胡敏酸(HA)各组分及焦磷酸钠提取的富里酸(FAP)。在不同类型土壤中，以培养土新形成的有机质各组分的脂族性最强；风沙土HMi、HMc的脂族性强于黑土，草甸土最弱。
(2)不同比例的玉米秸秆与黑土底土培养后，随着培养时间的延长，土壤有机碳总量、游离富里酸(FFA)的相对数量都呈现下降的趋势；可提取的腐殖物质(HE)的相对数量随着时间先增加后下降。胡敏素各组分中HMi、HMc相对数量随着时间逐渐上升；HMr随着时间的变化则有先升高后下降的趋势。
(3)随着玉米秸秆的不断腐解，土／秸比1：1、2：1的处理PQ值先下降后增加，说明在培养初期，FA形成速度大于HA；土／秸(灭)比2：1处理的PQ值先增加后下降，HA形成速度大于FA。
(4)在玉米秸秆腐解初期，HA、FA要比HMi、HMc的形成速度快，但随着培养时间的延长，向着有利于HMi、HMc形成和积累的方向发展。与HA相比，土／秸为1：1处理，有利于HMi、HMc的积累。与FA相比，土／秸比为3：1处理，不利于HMi、HMc的形成与积累。
吉林农业大学硕士学位论文
土壤胡敏素分组及特性的研究
(5)在玉米秸秆腐解期间，A处理在O一30天时HMi形成较多;30天后，HMc
积累增多。在培养结束时，土/桔比为3:1的HMi/HM。值高于土/秸比2:1，土/
秸比1:一的HMi/HMc值最低，推测经过长时间培养后，HMi/HMc比值与土/秸比
成正相关，土/桔比越大越有利于HMi的形成。
(6)在玉米桔秆培养过程中，胡敏素各组分中HMi、HMc形成速度较快，而不
利于HMr的形成与积累。说明玉米桔秆腐解过程中，随着时间的延长，向着可提
取胡敏素组分方向转化。
(7)在玉米桔秆不断腐解过程中HMi、HMc的△LogK随着培养时间的延长不断
降低，RF值逐渐升高，说明HMi、HMc的分子结构逐渐向复杂化的方向发展，氧
化程度和芳构化程度逐渐增加。
Soil humus is a special high molecule compound in soil. It has important function in soil fertility, structure and character. So, it is important to the study of humus in agriculture produce and environmental protection. Previously, we mainly studied solvable humus fraction(humic acid,fulvic acid), however, the study of unsolvable humus faction(humin) was litter.
This paper makes the method of Pallo simply, and humin was divided into three fractions. The paper studied the fractional composition of organic matter by the method, mainly the mounts and some chemical characteristic of humin fraction from three different soil types, namely black soil, meadow soil and wind-blown soil in the northeast of china, and the dynamic changes of humin fraction during incubation experiments. The objects are to provide scientific basis for clarifying the formation and transformation mechanism of humin , and give new data for fertility of soil and organic chemistry and humic substances chemistry .The major results are as follows:
In the fraction of organic matter from three different soils , the amounts of extractable humus was higher, accounting for 30%~50% of total carbon. The result of humin fraction indicated that the amount of isolatable humin (HMr) was the highest , accounting for 30%~60% of total carbon .The amount of humin linked to iron (HMi) was more than the humin linked to clay (HMc) .The amount of HMi accounted for 3%~6% of total carbon. The amount of HMc accounted for 1%~5% of total carbon.
The study of HMi and HMc's E4/E6 and ALogK indicated that the molecular structure of HMi was simpler, but the molecular structure of HMc was more complex .The molecular structure of the new formed HMi and HMc were the simplest. The study of IR showed :The aliphatic of HMi and HMc was stronger than humic acids extracted with pyrophosphate of sodium, humic acids extracted with soda and fulvic acids extracted with pyrophosphate of sodium. In different type soils , The aliphatic of new formed organic matter compose is the strongest among these soil. The aliphatic of HMi and HMc in Wind-blown soil was stronger than in black soil. Meadow soil was weak.
During corn stalk decomposition , the amounts of organic matter carbon and the relative amounts of free fulvic acid(FFA) gradually decreased with prolonged incubation time ; The
relative amounts of extractable humus (HE)increased before 90 day and then decreased .The relative amounts of HMi and HMc increased gradually , the amounts of HMr first increased , then decreased.
At early stage of incubation, PQ gradually decreased, then increased in the treatment of soil/corn stalk 1:1 and soil/corn stalk 2:1, it indicated that the formed velocity of FA was more faster than HA in initial stage, then the formed velocity of HA gradually increased .While in the treatment of soil/corn stalk(sterilization) 2:1, the formed velocity of HA was faster than FA at initial stage .
During corn stalk decomposition, the formed velocity of HA and FA were more faster than HMi and HMc , while with prolonged incubation time , each treatment was benefit to formation and accumulation of HMi and HMc . Compared with HA, it was benefit to the accumulation of HMi and HMc in soil/corn stalk 1:1 's treatment. Compared with FA, it was not benefit to the accumulation of HMi and HMc in soil/corn stalk 3:l's treatment.
In early stage(0~30d) of corn stalk decomposition , the amount of HMi accumulation was higher than in the soil/corn stalk 1:1 's treatment. After 30d, the accumulation of HMc increased. At the end of incubation, the value of HMi/HMc in the soil/corn stalk 3:l's treatment was higher, then is the soil/corn stalk 2:1 's treatment , the value of HMi/HMc in the soil/corn stalk 1:1 's treatment was lower. So we speculated that HMi/HMc and soil/corn stalk is positive after a long time cultivation, the value of soil/corn stalk was higher , more benefit to formation of huniin fraction, the formation velocity of HMi and HMc was faster than HMr. So during corn stalk decomposition , it was benefit to the transformation
本文将Pallo有机质分组法进行简化，将土壤胡敏素分为三个组分。并用此法对我国东北不同土壤类型的有机质组成，主要是胡敏素的不同组分的数量及结构特性以及不同比例的玉米秸秆与土壤培养后胡敏素的动态变化进行研究。从而探讨胡敏素各组分的形成、转化机制，为胡敏素在土壤肥力上的作用提供理论依据，也为土壤有机质化学和腐殖质化学研究提供新的资料。主要研究结果如下：
(1)在黑土、草甸土、风沙土中，腐殖酸HE的含量较高，占全碳的30～50％。胡敏素各组分中，以不溶性的胡敏素(HMr)为主，占全碳的30～60％；其次是铁结合胡敏素(HMi)，占全碳的3-6％；含量最少的是粘粒结合的胡敏素(HMc)，占全碳量的1-5％。对HMi、HMc的E4／E6、△LogK值研究得出HMi的分子结构较简单，而HMc分子结构相对较复杂。新形成的HMi、HMc的分子结构比自然土壤简单。对有机质各组分的红外光谱研究得出：HMi、HMc中的脂族结构都高于胡敏酸(HA)各组分及焦磷酸钠提取的富里酸(FAP)。在不同类型土壤中，以培养土新形成的有机质各组分的脂族性最强；风沙土HMi、HMc的脂族性强于黑土，草甸土最弱。
(2)不同比例的玉米秸秆与黑土底土培养后，随着培养时间的延长，土壤有机碳总量、游离富里酸(FFA)的相对数量都呈现下降的趋势；可提取的腐殖物质(HE)的相对数量随着时间先增加后下降。胡敏素各组分中HMi、HMc相对数量随着时间逐渐上升；HMr随着时间的变化则有先升高后下降的趋势。
(3)随着玉米秸秆的不断腐解，土／秸比1：1、2：1的处理PQ值先下降后增加，说明在培养初期，FA形成速度大于HA；土／秸(灭)比2：1处理的PQ值先增加后下降，HA形成速度大于FA。
(4)在玉米秸秆腐解初期，HA、FA要比HMi、HMc的形成速度快，但随着培养时间的延长，向着有利于HMi、HMc形成和积累的方向发展。与HA相比，土／秸为1：1处理，有利于HMi、HMc的积累。与FA相比，土／秸比为3：1处理，不利于HMi、HMc的形成与积累。
吉林农业大学硕士学位论文
土壤胡敏素分组及特性的研究
(5)在玉米秸秆腐解期间，A处理在O一30天时HMi形成较多;30天后，HMc
积累增多。在培养结束时，土/桔比为3:1的HMi/HM。值高于土/秸比2:1，土/
秸比1:一的HMi/HMc值最低，推测经过长时间培养后，HMi/HMc比值与土/秸比
成正相关，土/桔比越大越有利于HMi的形成。
(6)在玉米桔秆培养过程中，胡敏素各组分中HMi、HMc形成速度较快，而不
利于HMr的形成与积累。说明玉米桔秆腐解过程中，随着时间的延长，向着可提
取胡敏素组分方向转化。
(7)在玉米桔秆不断腐解过程中HMi、HMc的△LogK随着培养时间的延长不断
降低，RF值逐渐升高，说明HMi、HMc的分子结构逐渐向复杂化的方向发展，氧
化程度和芳构化程度逐渐增加。
Soil humus is a special high molecule compound in soil. It has important function in soil fertility, structure and character. So, it is important to the study of humus in agriculture produce and environmental protection. Previously, we mainly studied solvable humus fraction(humic acid,fulvic acid), however, the study of unsolvable humus faction(humin) was litter.
This paper makes the method of Pallo simply, and humin was divided into three fractions. The paper studied the fractional composition of organic matter by the method, mainly the mounts and some chemical characteristic of humin fraction from three different soil types, namely black soil, meadow soil and wind-blown soil in the northeast of china, and the dynamic changes of humin fraction during incubation experiments. The objects are to provide scientific basis for clarifying the formation and transformation mechanism of humin , and give new data for fertility of soil and organic chemistry and humic substances chemistry .The major results are as follows:
In the fraction of organic matter from three different soils , the amounts of extractable humus was higher, accounting for 30%~50% of total carbon. The result of humin fraction indicated that the amount of isolatable humin (HMr) was the highest , accounting for 30%~60% of total carbon .The amount of humin linked to iron (HMi) was more than the humin linked to clay (HMc) .The amount of HMi accounted for 3%~6% of total carbon. The amount of HMc accounted for 1%~5% of total carbon.
The study of HMi and HMc's E4/E6 and ALogK indicated that the molecular structure of HMi was simpler, but the molecular structure of HMc was more complex .The molecular structure of the new formed HMi and HMc were the simplest. The study of IR showed :The aliphatic of HMi and HMc was stronger than humic acids extracted with pyrophosphate of sodium, humic acids extracted with soda and fulvic acids extracted with pyrophosphate of sodium. In different type soils , The aliphatic of new formed organic matter compose is the strongest among these soil. The aliphatic of HMi and HMc in Wind-blown soil was stronger than in black soil. Meadow soil was weak.
During corn stalk decomposition , the amounts of organic matter carbon and the relative amounts of free fulvic acid(FFA) gradually decreased with prolonged incubation time ; The
relative amounts of extractable humus (HE)increased before 90 day and then decreased .The relative amounts of HMi and HMc increased gradually , the amounts of HMr first increased , then decreased.
At early stage of incubation, PQ gradually decreased, then increased in the treatment of soil/corn stalk 1:1 and soil/corn stalk 2:1, it indicated that the formed velocity of FA was more faster than HA in initial stage, then the formed velocity of HA gradually increased .While in the treatment of soil/corn stalk(sterilization) 2:1, the formed velocity of HA was faster than FA at initial stage .
During corn stalk decomposition, the formed velocity of HA and FA were more faster than HMi and HMc , while with prolonged incubation time , each treatment was benefit to formation and accumulation of HMi and HMc . Compared with HA, it was benefit to the accumulation of HMi and HMc in soil/corn stalk 1:1 's treatment. Compared with FA, it was not benefit to the accumulation of HMi and HMc in soil/corn stalk 3:l's treatment.
In early stage(0~30d) of corn stalk decomposition , the amount of HMi accumulation was higher than in the soil/corn stalk 1:1 's treatment. After 30d, the accumulation of HMc increased. At the end of incubation, the value of HMi/HMc in the soil/corn stalk 3:l's treatment was higher, then is the soil/corn stalk 2:1 's treatment , the value of HMi/HMc in the soil/corn stalk 1:1 's treatment was lower. So we speculated that HMi/HMc and soil/corn stalk is positive after a long time cultivation, the value of soil/corn stalk was higher , more benefit to formation of huniin fraction, the formation velocity of HMi and HMc was faster than HMr. So during corn stalk decomposition , it was benefit to the transformation
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