长期施肥对黑土团聚体中腐殖物质组成的影响

腐殖物质(HS)是土壤有机质的主体,在土壤固碳方面具有重要作用[1],近些年来,在土壤有机质化学研究中越来越受到重视。团聚体是土壤有机质(SOM)分解转化和HS形成的最主要“场所”,土壤中的一切生物化学活动均在这一骨架内进行(包括土壤腐殖化作用)。在正常的或特定的条件下,不仅微生物主导的腐殖化作用需要合适的“场所”,而且所形成的HS也只有在合适的“场所”或者说与土壤矿质部分相结合才能长时间保存[2-3]。这种“场所”或者说有机无机结合状况,是制约整个土壤固碳反应的关键。但至今为止关于这种“场所”(团聚体)的固碳机制尚不清楚,特别是很少注重HS化学方面。团聚体和HS二者关系密切,不可分割。可以假     

腐殖物质特异性及其产生机制

腐殖物质(HS)是天然有机质的主体,其组成、结构十分复杂。之所以称其为一类物质,就是基于他们具有不同于其形成前体的化学组成与结构特征的共性,或称"特异性",即在腐殖化过程中形成新的化学组合,甚至是"特异的"结合方式。但经历近200年的探索,人们对这种"特异性"的认识仍然不清楚,并缺少实验上的证据。加之近几年,一些研究结果被不适当的推演,HS的"特异性"更加受到质疑。HS到底有无"特异性"?"特异性"是什么?这涉及HS生物化学的根基,必须进行深入研究和回答。本文对已有的一些研究报道,包括HS的特异性、生物分子单体与HS结构特征的比较、基于生物多样性(进化)的天然生物材料与HS形成、HS形成机理及胡敏酸(HA)、富里酸(FA)形成顺序、矿物黏粒催化与HS形成、异核单量子相干谱(HSQC)和总相关谱(TOCSY)、傅里叶变换离子回旋共振质谱(FT-ICR-MS)和C1s软X射线近边吸收精细结构(NEXAFS)同步辐射技术应用等进行综合评述,并提出HS化学进一步研究的方向。     

土壤团聚体中有机质研究进展

团聚体和有机质是保持土壤结构和肥力的基础,二者相互作用,不可分割,前者是后者存在的场所,后者是前者存在的胶结物质。在现有资料中,分别以团聚体和有机质为主要研究对象的报道较多,而团聚体中有机质性质的研究较少。本文从土壤有机质物理分组与化学分组相结合的角度,介绍国内外有关土壤团聚体中有机质的数量和特性及其对农业措施的响应方面的研究进展,内容包括团聚体分组、数量和稳定性,团聚体中的有机质的数量、未分组有机质的性质和腐殖物质组分的性质,颗粒分组中的有机质数量和性质,团聚体-密度联合分组中的有机质的数量和性质,不同土地利用方式和长期耕作施肥对团聚体中的有机质的影响等。以期推动不同粒级团聚体和不同HS组分相互作用及其对土壤固碳和肥力贡献研究工作的开展,为探索土壤有机质物理保护与化学保护之间的关系,揭示土壤固碳和培肥机理提供依据。     

氮磷富集对森林土壤碳截存的影响研究进展

大气氮磷沉降增加森林土壤养分的可利用性,改变底物的化学质量、土壤微生物组成和功能,进而影响土壤有机质的储量与稳定性。然而,现有研究主要集中在氮素富集对自然森林生态系统碳截存的影响,有关磷富集以及氮磷交互对人工林土壤有机碳(SOC)截存的影响及其微生物学机制尚不清楚。本文综述了氮磷富集对森林土壤碳转化和净交换通量、土壤有机质(SOM)的激发效应、SOM组成与稳定性以及介导碳转化功能微生物群落的影响,并指出各个研究环节的不足,包括:(1)森林土壤碳通量及其组分对氮磷富集的非线性响应方程及临界阈值尚未确定;(2)氮磷富集对森林SOM激发效应的影响程度与潜在机制知之甚少;(3)SOM的物理-化学协同稳定机制研究不够深入;(4)土壤活性微生物群落组成、SOM化学结构与SOC累积之间的耦联关系尚不清晰。据此,指出未来研究重点与研究思路:基于多水平氮磷添加控制试验和~(13)C标记培养实验,利用原位监测、土壤化学(~(13)C-NMR和Py-GC/MS)、宏基因组测序的分子生物学方法,重点研究氮磷添加及其交互作用对人工林土壤碳排放与流失通量、微生物激发效应、SOM组成与化学稳定性以及功能微生物群落组成的影响,确定土壤碳输出通量对氮磷添加的非线性响应方程与氮沉降临界负荷,阐明分解微生物群落组成与土壤碳转化及稳定性的耦联关系,揭示氮磷交互影响人工林土壤碳积累与损耗的微生物学机制。研究结果有助于控制森林尤其是人工林土壤碳损失,有效降低陆地"氮促碳汇"评估的不确定性,并可为森林生态系统应对全球变化提供科学依据。     

东北黑土有机质组分与结构的研究进展

在全球气候变化背景下研究土壤有机质的转化过程对于评价陆地生态系统碳截获潜力具有重要意义,而土壤有机质的循环特征及其稳定性与土壤有机质的组成和结构密切相关.东北黑土区是我国重要的商品粮基地,近年来,黑土有机质含量呈显著下降趋势,造成黑土肥力和质量的严重退化.本文通过文献资料的整理,总结了不同农田管理措施下黑土土壤有机质的消长动态、组分变化以及结构特征的研究现状,并探讨了研究中存在的问题.开垦和耕作导致土壤有机质总量、活性组分以及腐殖物质含量的显著降低,而平衡施用化肥和有机肥是维持和提升土壤有机质数量和质量的有效途径,长期有机无机配施使土壤有机质结构趋于简单化,有利于土壤肥力的保持.黑土有机质组分化学结构变化的驱动机制是值得人们长期探索的问题.     

土壤有机质稳定性特征与影响因子研究综述

本文阐述了土壤有机质(SOM)稳定性的影响因素及其稳定性特征,包括有机物质化学稳定性、物理稳定性和生物化学稳定性,探讨了通过分子特征,即元素组成、功能团、分子构像;有机物、无机物质或其它有机物质之间的分子间相互作用;有机质与微生物和酶之间的作用;以及水热条件对SOM稳定性的影响。     

人工腐殖化及产品在农业增产中的应用

腐殖质（humic substance,HS）作为农业生产中土壤养分组成的重要指标,在维护土壤地力、碳储存、植物营养及生态环境稳定性等方面具有重大战略意义。然而,由于HS的天然提取源不足,导致HS市场供给需求逐年攀升。鉴于木质素与HS的结构相似,能否采用人工腐殖化方法,精准调控大分子木质素的氧化分解或其小分子衍生物的自由基耦合,生成可媲美甚至超越商业HS作用和功效的类HS产品？该创造性思路对实现我国农业连续增产增收具有极大的经济价值和应用前景。本文简述了天然HS的结构特征和多功能属性,探讨了人工腐殖化的最新理念、方式和机理,对比了人工腐殖化产物与天然HS的差异性,并总结了人工腐殖化产品在农业实践中的潜在应用和价值,旨在为研究者攻克木质素及其衍生物人工腐殖化的科技瓶颈提供理论支撑和技术指导。     

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.     

三种黑土中有机碳、氮、磷的形态分布与肥力的关系

土壤腐殖质是土壤的重要组分。土壤的许多属性都直接或间接地与腐殖质的性质有关。我们曾指出^[2]黑土的腐殖物质及其组分与土壤的物理、化学及生物化学有显著的相关性,这表明它们对氮、磷等营养物质的转化、供应及贮存起着重要的作用。     

土壤有机质的生物学稳定性及其转化模型

土壤有机质是土壤中最重要的一种物质，本文首先对土壤有机质各组分的生物学稳定性，以及非腐殖物质在转化为腐殖质的过程中进入腐殖质各组分的比例进行概述；然后分四种类型总结了土壤有机质的转化模型，提出各类模型的优缺点及建模的发展趋势。     

Soil organic matter beyond molecular structure Part II: Amorphous nature and physical aging

Glassy, rubbery, and crystalline phases are representatives of supramolecular structures which strongly differ in order, density, and other characteristics. In this contribution, the amorphous nature of soil organic matter (SOM) is reviewed with respect to the glassy/rubbery model, glass transition mechanisms, interactions of SOM with water, and physical aging. Glass‐transition behavior and physical aging are inherent properties of amorphous solids, and numerous spectroscopic investigations give insights into different domain mobilities of humic substances (HS). The correlation between sorption nonlinearity and glassiness of polymers and HS supports a relation between sorption and amorphicity in Aldrich humic acid. Further evidence is still required for the transfer to soil HS and SOM. Sorption and differential scanning calorimetry (DSC) data suggest a correlation between aromaticity and glassiness in HS, and the available data do currently not allow to decide unambiguously between specific sorption and hole filling as explanation. This needs to be verified in future research. Although parts of the investigations have up to now only been conducted with humic substances, the collectivity of available data give strong support for the glassy/rubbery conception of SOM. They clearly indicate that amorphous characteristics cannot be excluded in SOM. This is further supported by the observation of different types of glass‐transition behavior in samples of whole humous soil. In addition to classical glass transitions in water‐free soil samples, water surprisingly acts in an antagonistic way as short‐term plasticizer and long‐term antiplasticizer in a second, nonclassical transition type. Latter is closely connected with physico‐chemical interactions with water and suggests water bridges between structural elements of SOM (HBCL‐model). The gradual increase of T_g* in SOM indicates physico‐chemical aging processes, which are not restricted to polymers. They may be responsible for contaminant aging, changes in surface properties and increased soil compaction in agricultural soils.     

Qualitative and quantitative soil organic matter estimation for sustainable soil management

Purpose

The aims of this paper were to review tools and methods for qualitative and quantitative evaluation of soil organic matter (SOM) coming from diverse egzogenic sources for effective soil management, and to introduce a new approach to predict dynamics of SOM transformations, especially humification, as a key process in the formation of humic substances (HSs).

Materials and methods

A review of existing literature is presented on tools and methods for qualitative and quantitative assessment of organic matter in soil originating from various sources for reasonable soil management, attempting to provide a better understanding of the advances in organic matter transformations and new research directions for modeling. Diverse tools and methods for qualitative and quantitative evaluation of organic matter in soil coming from diverse sources have been adopted so far to express transformation processes.

Results and discussion

For the qualitative analysis of SOM and humic acids (HAs), the analytical techniques are applied, e.g., HPSEC, NMR, and ESI-FTICRMS. The quantitative analysis is done through the following parameters: humification index (HI), humification degree (HD), and humification rate (HR). These analyses indicated that because of lack of reliable data from sufficiently long-term experiments, mathematical modeling may be applied as a numerical tool for quantitative estimation and prediction of humification of SOM. The effective soil management should include soil properties as well as different functions: food production, nutrient and water cycling, storage, filtrating, buffering, biological habitat, gene pool, source of raw materials, climate regulations, heritage, platform for man-made structure. The soil utility value should be evaluated through the SOM qualitative and quantitative analysis of organic carbon and total nitrogen. Knowledge about dynamics of SOM transformations is essential, particularly in the context of stability and efficiency of different sources of organic matter applied into soil. A qualitative understanding of SOM dynamics transformations along with modeling for quantitative assessment of HS formation should be used to develop sustainable soil management. The modeling may be considered as a tool for predicting SOM humification dynamics and consequently the formation of HSs from the diverse sources. The existing archival data from a long-term experiment may be used to build and calibrate the reliable mathematical model of SOM humification.

Conclusions

Managing of SOM remains a sound basis for maintaining soil in a good condition for optimizing productivity. The development of land management strategies to optimize both the increase of soil organic carbon levels and the recycling of nutrients from SOM needs to be a priority. This should include policy makers and other users as well.

     

Soil organic matter beyond molecular structure Part I: Macromolecular and supramolecular characteristics

This contribution reviews and discusses structural aspects of soil organic matter (SOM) and humic substances (HS) with special respect to the macromolecular and the supramolecular view. It can be concluded that (1) dissolved humic acids behave as supramolecular associations of relatively small molecules with an enormous flexibility of reaction of environmental conditions, (2) multivalent cations may increase the apparent molecular weight by the formation of coordinative crosslinks in dissolved and undissolved natural organic matter (NOM), (3) sorption nonlinearity in solid humic acids and SOM may be due to polymer properties of NOM, (4) sorbates affect sorbent characteristics of SOM, and (5) hysteresis and conditioning effects in SOM can up to now best be explained with the polymer analogy. A distinct polydispersivity of SOM over a wide range of molecular masses is to be assumed. The supramolecular and the macromolecular models were derived from humic acids with different composition and on the basis of different sample states. Although the supramolecular model has not explicitely been shown for unfractionated DOM, the combination of all discussed studies suggests supramolecular as well as macromolecular characteristics of NOM. Neither macromolecules nor small molecules can be fully excluded in solid and dissolved SOM. Microregions with different properties provide different types of sorption sites. SOM is suggested to be regarded as amorphous material. This point of view is not restricted to high molecular masses and may supplement our understanding of SOM by the model of physical aging.     

Humus Status of Arable Podzoluvisols and the Role of Annual Litterfall in its Formation

In this work comparative research of the quantitative characteristics of the humus status (HS) of Estonian arable Podzoluvisols (PD) and some very closely related soils were carried out. This study was conducted to determine soil humus cover (HC) and subsoil humus content (percentage and pool) and to analyse the role of plant residues in their formation. The specific objective was to discuss the ecological factors and mechanisms which influence the flux of soil organic matter (SOM) through soils and to evaluate its contemporary status. For this purpose different databases (DB) were used: (1) DB of large-scale soil mapping (1958-78), (2) DB PEDON of pedoecological researches (1967-85), (3) DB of HS research transects (1986-91) and (4) data from two long-term field trials (1985-92). In the conditions of regular agricultural practice the mean SOM percentage in the HC of arable PD is within the range of 1.8-2.1 %, which is 0.1-0.3 units (%) the below optimal level and is in a critical state. Impoverishment is caused mainly by deep plowing. The dependence of humus retaining capacity (presumed to be a good criterion for evaluating the current HS of soils) on the mode and intensity of tillage, soil water regime, carbonate content and textural class was discussed. Mean annual inflow of organic matter into HC (4-5 Mg ha-yr^?1) forms an average 5.5-6.7 % from its pool in soil. Application of manures increases this percentage to 12-13. It may be concluded that the HC might be shallower, but must be richer in humus. The annual balance of SOM reflects better than annual balance of humus, the influence of fresh SOM on the soil current year productivity.     

Molecular modeling of soil organic matter: Squaring the circle?

The structure of soil organic matter (SOM) and humic substances (HS) has been discussed from different viewpoints including molecular conformation, molecular aggregation, macromolecularity, supramolecular characteristics, domain mobility, and many others. Until now, the individual models appear partly contradictory, although each viewpoint provides important information on the structural and functional properties of SOM. This is most probably due to the huge heterogeneity of SOM. Therefore, the question: “How can molecular modeling help to further understand structure and functioning of soil organic matter?” needs to be addressed with care. This contribution reviews and discusses the potential of important molecular modeling approaches currently applied in soil organic matter science.Computer models are useful in giving a visualization of the general structure and of the possible effects on soil chemistry and soil physics. Computational chemistry in this context aims to estimate a lowest energy conformation for a molecule or an assembly of molecules specified by the programmer. On the basis of the calculated conformation, physicochemical characteristics like surface area, polarity and other can be estimated and information on the stability of molecular assemblies can be derived. The significance of the obtained conformation and physicochemical information strongly depends on the initial hypothesis of the molecular structure of each involved molecule. Recent computer models have been developed on the base of computer assisted structure elucidation (CASE). In this procedure, all possible isomers or a statistically representative set of isomers consistent with the experimental input data are processed.Further interesting fields of computational chemistry in soil research follow a different conception, where specific processes of interest are elucidated with the help of computational models which simplify the humic molecules with respect to the individual modeling problem. This way helps to understand the relevance of principal processes expected to occur in soil. In this context, complexes of Al with organic acids, clay mineral sorption sites, interactions of pesticides with organic functional groups or organic soil constituents as well as cross-linking of molecule segments by water molecules were modeled in targeted process-orientated models. The act of simplification is the crucial process in these kinds of models, and if the models are based on good conceptions, they allow to learn about potential SOM functioning. The transfer to more complex situations, however, needs special care and the predictive character of these models needs to be judged with care. Still, any computer model is only as good as its initial hypothesis.     

Soil Organic Matter/Carbon Dynamics in Contrasting Tillage and Land Management Systems: A Case for Smallholder Farmers with Degraded and Marginal Soils

This study reveals that soil organic matter (SOM) is 58% soil organic carbon (SOC) and the processes that govern SOM dynamics include those that promote SOM synthesis from organic inputs and those that decrease SOM through decomposition. Land use is a key determinant of SOC dynamics and spatial differences in SOM. Agricultural soils can accommodate extra carbon (C) between 140 and 170 Pg C. Globally sub soils store more than half of total SOC. The SOM can increase under no-tillage management even with low crop residue input. Soil tillage induces loss of carbon in macroaggregates (>250 μm) and a gain of carbon in microaggregates (<250 μm). The stage of plant development rather than plant species determines carbon dynamics from plants to soil, and the rate depends on the plant development. However, sorption of dissolved organic matter to mineral soil influences the stabilization of dissolved organic matter.     

Soil Humic and Fulvic Acids from Different Land-Use Systems Evaluated By E4/E6 Ratios

Changes in land-use systems such as the introduction of trees on agricultural land can give rise to changes in the physicochemical properties of the soils, also affecting the quantity and quality of organic matter incorporated into the system. The present study assesses humic substances (HS) in the soil such as humic acid (HA) and fulvic acid (FA) by looking at the relationship between the optic densities determined at 465 and 665 nm (E4/E6 ratio). Topsoil samples (0–20 cm) from pine woodlands 60 years of age were compared with agricultural soils of similar age in the central-south region of the Province of Buenos Aires, Argentina. The pH of the topsoil from beneath the pine trees was highly acidic (5.0 vs. 6.2) and a significant increase in the level of organic carbon (OC) was registered. The carbon to nitrogen (C/N) ratio was also higher (by one order of magnitude) beneath the pine trees, although the humification conditions of the soil organic matter (SOM) were good in the soils of both studied land-use systems. The E4/E6 ratio was higher in the HA and FA 2º (second extraction) beneath the pines, indicating a smaller molecular size of the HS bound to the clay minerals. This fact can be attributed to the higher concentration of hydrogen ions beneath the pines and consequently the loss of polyvalent cations, mainly calcium. The most labile organic molecules (FA 1º – first extraction) were of a larger size in soils beneath the pines, most likely owing to a specific characteristic of the Pinus genus, although the fraction in question constitutes a minority fraction among the HS. Clear differences were established between the E4/E6 ratios in HA and FA, making this a highly useful method for determining molecular changes in HS as a result of changes in land use.     

有机质对土壤光谱特性的影响研究

为了探明土壤有机质的光谱特征及其影响作用,从而为有机质土壤铁氧化物的定量反演提供理论依据。利用去有机质前后土壤的光谱数据,研究了有机质对土壤反射率、土壤线参数、土壤铁氧化物定量反演的影响。研究结果表明,去除有机质后,能明显提高土壤反射率,变化最明显的为可见光橙黄光波段,即570～630 nm。相关性分析也显示橙黄光波段反射率的相对变化量或差值与有机质去除量之间的相关系数要比其他波段高,相关系数最大值在600 nm。因此,建议采用570～630 nm的光谱数据进行有机质的反演;土壤线斜率在去有机质后明显降低,截距显著增大,二者变化量与有机质去除量呈极显著相关关系,可用土壤线参数预测有机质含量。有机质对铁氧化物的反演具有明显影响,特别是有机质大于20 g kg-1的土壤,在进行反演时应考虑有机质对反演精度的影响,需采取有效地技术手段消减其影响作用,才能达到较好的效果。     

Kinetics of the release of dissolved organic matter (DOM) from air‐dried and pre‐moistened soil material

In this study, the kinetics of soil organic matter (SOM) dissolution from soil samples in different states of moisture was investigated, using a continuous extraction method. The investigation distinguished three processes of SOM dissolution. They include an initial, fast process (probably hydrophilic dissolved organic matter) and two slow, rate limited processes, which probably correspond to hydrophobic dissolved organic matter (DOM). The second process indicates a slow, continuous release of DOM, whereas the third process is determined by a power law. The rate of the third process strongly depends on temperature and state of moisture. It is diffusion limited, with the diffusion control probably being located in the solid soil organic matter. This was explained by a gel structure, which slowly forms in the hydrating SOM and allows diffusion of mobile particles of SOM. The results show the importance of considering the moisture state of SOM for the kinetics of DOM dissolution.