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中国西南喀斯特地区典型土壤/泥炭剖面胡敏酸分子特征及演化研究
马连刚
导师肖保华
2014
学位授予单位中国科学院研究生院
学位授予地点北京
学位名称博士
学位专业环境科学
关键词喀斯特地区 泥炭 典型土壤 胡敏酸 超滤组分
摘要近几十年来,由于不当的人类活动,喀斯特地区区域石漠化和土壤污染形势严峻。土壤腐殖质对土壤结构稳定性和污染物的迁移、转化及生物有效性有显著影响。对于大多数土壤/沉积物来说,胡敏酸是腐殖质的主要组成部分。在喀斯特地区开展胡敏酸研究,能为该地区区域石漠化的防治和重点污染物的风险评估提供基础数据。 本工作选取喀斯特地区典型土壤(黄壤和石灰土)和泥炭剖面,对赋存于土壤/泥炭剖面的胡敏酸进行连续提取、纯化和超滤分组,同时利用元素分析、电位滴定、紫外-可见光光谱、傅里叶变换红外光谱及核磁共振技术进行分析表征。 总结起来,本研究获得了如下结论和一些新认识: 在泥炭剖面上,随着深度增加,胡敏酸含量逐渐增加,胡敏酸的碳含量没有变化,胡敏酸的氮、氢和脂肪组分含量逐渐降低,胡敏酸的氧、碳水化合物组分、芳香组分、羧基、酮基含量及总酸度逐渐升高。因此推测,在泥炭中,胡敏酸的降解受泥炭孔隙中氧含量影响,随泥炭埋藏深度增加,胡敏酸降解程度降低。 在黄壤剖面上,随深度增加,胡敏酸含量急剧降低,胡敏酸的碳、脂肪组分、芳香组分、羧基、酚羟基含量及总酸度逐渐降低,胡敏酸的氮、氢和碳水化合物组分逐渐升高,胡敏酸的氧含量变化不明显。因此推测,在黄壤中,胡敏酸的降解不受土壤溶液中氧含量的限制,处于不同土壤层位的胡敏酸,其物质来源及降解程度不同。 与泥炭胡敏酸和黄壤胡敏酸相比,石灰土胡敏酸的C/N原子比最低,H/C和O/C原子比最高。从胡敏酸结构本身和石灰土中微生物活性来看,在石灰土剖面上,胡敏酸的含量和性质会产生较大变化,但事实却是,随土壤深度增加,胡敏酸的含量有所降低,但幅度不大,胡敏酸的羧基、酚羟基、酮基含量和总酸度有所增加,但幅度也不大,胡敏酸的氮、氢变化不大。因此推断,在石灰土中,可能存在碳酸钙沉淀对胡敏酸的包裹或钙离子与胡敏酸络合形成胡敏酸钙两种机制,阻碍了微生物对胡敏酸的摄取。 利用超滤系统,泥炭胡敏酸和表层黄壤胡敏酸都被分为八个组分,其分子量分布具有一定的偏向性。随着分子量降低,胡敏酸的碳、氮、氢、脂肪组分、甲氧基和碳水化合物组分含量逐渐降低,胡敏酸的氧、芳香组分、羧基、酮基含量和总酸度逐渐升高。说明,分子越小,胡敏酸酸性官能团含量越高,分子极性越高,较容易被微生物摄取,分子中容易降解的组分(含氮组分及碳水化合物组分)被微生物同化后含量降低,难降解的芳香组分及其酸性取代基团含量升高。超滤组分的氧含量与其总酸度的显著正相关性指出,对于泥炭胡敏酸和黄壤胡敏酸,氧原子主要分布在芳香结构的酸性取代基团中。 表层石灰土胡敏酸仅被分为5个组分,其分子量分布也具有同样的偏向性。随着分子量降低,胡敏酸的碳、芳香组分、羧基、酚羟基、酮基含量及总酸度逐渐升高,胡敏酸的氮、氢、氧和碳水化合物组分含量逐渐降低。石灰土胡敏酸超滤组分的氧含量与其总酸度呈显著负相关而与其碳水化合物碳含量呈显著正相关指出,对于石灰土胡敏酸,氧原子主要分布在碳水化合物组分的醇羟基中,当小分子胡敏酸被降解时,分子中含氮组分及碳水化合物组分含量降低,使得胡敏酸的氮和氢含量降低,氧含量也随着碳水化合物组分的降解而降低,碳含量则相应升高。
其他摘要For decades, the soil deterioration and pollution became urgent issues resulted from the increasing artificial activities in Karst area in southwestern of China. Humic substances (HS) are the major part of organic matters in soil and peat, which could improve the soil structure and influence the transportation, transformation and bioavailability of pollutants in ecosystem. For most of soils and peat, humic acids (HA) are the major part of HS. The study of HA in typical soils and peat could support the reconstruction of the damaged ecosystem and the risk assessment of typical pollutants of Karst area. This work was focus on HA from peat and major soils (yellow earth and limestone soil) in Karst area. First, sample the peat and soils by layer. Second, extract and purify the HA from the peat and soil samples. Third, use tangential ultrafiltration system to separate the HAs from peat and soils into different fractions with different nominal molecular weight. Last, characterize these HA and their size fractions by using the Elemental analysis, Potentiometric titration, UV-visible spectroscopy, Fourier transform infrared spectroscopy and Cross polarization-magic angle spinning 13C-nuclear magnetic resonance. In summary, the main conclusion and new insight about HA from peat, yellow earth and limestone soil and their size fractions are as follows: With increasing depth of peat, the amount of HA increase, as well the oxygen, aromatic components, carbohydrates, carboxyl, ketonic groups and total acidity of HA, while the nitrogen, hydrogen and aliphatic constituents of HA continue to decrease. It is expected by the analysis results, the degradation of HA is influenced by the oxygen content in the pore of peat. In yellow earth profile, with soil depth increase, the amount of HA decrease, as well the carbon, aliphatic constituents, aromatic components, carboxyl, phenolic hydroxyl, ketonic groups and total acidity of HA, while the nitrogen, hydrogen and carbohydrate components of HA increase. The results imply that, in soil, the activities of microorganism are not limited by oxygen concentration in the soil solution and that, in different soil horizon, the precursors and the degradation extent of HA are different. Comparing with the HA from peats and yellow earth, the HA from limestone soils are lower in the atomic ratio of C/N and higher in the atomic ratios of H/C and O/C. In limestone soil, the microbial activity could also be higher. From these two points, in limestone soil, the microbial degradation of HA could be fierce and results in the change in amount and properties of HA in the soil profile dramatically. However, in limestone soil, with soil depth increase, the amount of HA decrease slightly, and the carboxyl, phenolic hydroxyl, ketonic groups and total acidity of HA increase slightly, while the change in the nitrogen and hydrogen of HA is not significant. We propose that, in the limestone soil, the HA are preserved by the CaCO3 package or complexing with the calcium ions from uptake by microorganism. Using tangential ultrafiltration system, the three HAs from peats and the HA extracted from the upper horizon in yellow earth were separated into 8 fractions with different nominal molecular weight. The mass distribution of the size fractions indicates that HA from peats and yellow earth have preferential range of MW values. With the molecular weight decrease, the carbon, nitrogen and hydrogen of HA decrease, as well the aliphatic constituents, methoxyl and carbohydrates in HA, while the oxygen, aromatic constituents, carboxyl, ketonic groups and total acidity of HA increase. We propose that the smaller size fractions, which are higher in oxygen functional groups such as ketonic and carboxyl groups, are more polar and soluble, more easily uptaken by microorganisms. Therefore, the more degradable components (nitrogen-containing constituents and carbohydrate constituents) in smaller size fractions are assimilated by microorg
学科领域环境地球化学
语种中文
文献类型学位论文
条目标识符http://ir.gyig.ac.cn/handle/352002/5886
专题研究生_研究生_学位论文
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马连刚. 中国西南喀斯特地区典型土壤/泥炭剖面胡敏酸分子特征及演化研究[D]. 北京. 中国科学院研究生院,2014.
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