浙江温州山地丘陵区土壤碳储量研究

基于温州市山地丘陵区开展的多目标地球化学调查获得的深、表层土壤有机碳和全碳数据,采用直线模型法计算了研究区表层(0~0.2 m)、中层(0~1.0 m)和深层(0~2 m)土壤无机碳的单位储量及密度;采用指数模型法计算了研究区表层(0~0.2 m)、中层(0~1.0 m)和深层(0~2 m)土壤有机碳的单位储量及密度。利用这些数据分别编制了表层、中层、深层无机碳和有机碳的碳密度图,分析了无机碳、有机碳的分布范围和特点以及它们在不同土壤类型中的分布特征。结果表明研究区单位土壤无机碳平均储量为2881.333t,平均密度为0.720 kg/m^2,单位土壤有机碳平均储量为43128.667t,平均密度为10.782 kg/m^2;有机碳和无机碳在表层、中层和深层土壤中含量分布趋势一致;在不同土壤类型中含量分布趋势也一致,均为滨海岩土中最高,粗骨土中最低。     

河北泃河流域第四纪沉积相对土壤有机碳库的影响

成土母质是影响土壤有机碳储量的重要因素之一。以河北省三河市泃河流域为研究对象,根据全新统沉积环境特征,将研究区成土母质划分为冲洪积相沉积母质、冲积相沉积母质和湖沼积相淤积母质,探讨不同成土母质区土壤的有机碳密度变化及其影响机制。单因素方差分析显示,不同成土母质中土壤有机碳密度存在显著差异,呈冲积相<冲洪积相<湖沼积相变化趋势。对比不同成土母质的土壤质地、养分特征及理化性质,表明土壤通过影响植被的生长发育、土壤动植物、微生物活性、有机碳固存机制等,对土壤有机碳储量发挥直接或间接作用。研究区由冲积相→冲洪积相→湖沼积相,沉积环境发生显著变化,土壤粘粒组分增多,促进与土壤有机碳有关的有机-无机复合体的形成,降低微生物对土壤有机碳的分解;土壤含水率和养分含量增加,利于植被生长,提升土壤微生物活性,其代谢产物及死亡残体作为土壤有机碳的碳源,提高了土壤有机碳储量。该研究成果为流域土壤有机碳的保护利用提供技术支撑。     

菲和萘的非线性吸附过程研究

分配模型认为疏水性有机物在土壤上的吸附过程是一种分配的过程[1,2],平衡分配系数与土壤有机碳的含量存在线性相关关系.Weber和Huang[3,4]提出土壤吸附有机污染物的三端员模式.认为无机矿物表面和无定形有机质对有机污染物的吸附以相分配为主,而凝聚态有机质对有机污染物吸附则表现为非线性的.Pignatello和Xing[5,6]指出双模式吸附模型可将土壤有机质分为溶解相和孔隙填充相两个部分;认为有机污染物在溶解相上的吸附是一个分配过程,而在孔隙填充相中的吸附则服从兰格缪尔吸附等温模型,表现为非线性.可以肯定土壤有机质是引起疏水性有机物非线性吸附过程的主要组分.因此,本研究利用现代分析方法表征土壤有机质的化学组成和结构;定量研究多环芳技烃化合物菲和萘在吸附剂上的等温吸附过程;探讨疏水性有机污染物的非线性等温吸附与吸附剂中有机质化学组成和结构之间的关系.     

三氯乙烯在模拟有机质-矿质复合体中的吸附行为研究

土壤中有机质与无机矿物长期共存,其存在形式发生着变化。本文利用批实验的方法对三氯乙烯的吸附行为进行模拟研究,结果表明,土壤中有机质与无机矿物是以有机质-矿质复合体形式存在的,有机质与无机矿物的相互作用影响复合体的吸附性能,与有机质、无机矿物单体相比,复合体Kd、Koc明显发生变化;并提出了有机质-矿质复合体模型。     

内蒙古鄂伦春旗东部主要农耕区土壤有机碳含量及主要影响因素分析

利用鄂伦春自治旗东部主要耕地区1：25万土地质量地球化学调查数据,查明了研究区内表层和深层土壤有机碳储量和有机碳密度分布特征,分析了研究区内土壤有机碳储量、有机碳密度与土壤类型、土地利用方式之间的关系,探讨了土壤类型和土地利用方式对土壤有机碳的作用机理.结果表明研究区内土壤有机碳含量分布不均,土壤类型和土地利用方式是土壤有机碳储量和有机碳密度的主要影响因素.     

模拟有机质—矿质复合体对三氯乙烯的吸附

为了研究土壤中有机质-矿质复合体结合形式对有机污染物吸附的影响, 利用批实验的方法, 对比研究有机质-矿质复合体与无机矿物和腐殖酸简单的混合物对三氯乙烯的吸附.结果表明, 与腐殖酸相比, 高岭石和石英砂吸附三氯乙烯量很小.模拟有机质-矿质复合体吸附三氯乙烯是线性吸附, K_oc值随腐殖酸含量的增加而减小, 并且比纯腐殖酸样品的K_oc值小.有机质与矿质的相互作用影响了有机质的吸附性能.对有机质在复合体中的形态变化进行了分析, 提出了有机质-矿质复合体模型, 并对实验结果进行了合理的解释.      

土壤碳赋存形态及分析方法研究进展

研究土壤碳的赋存形态不仅利于了解碳的迁移转化规律,而且可以为土壤固碳提供科学依据。目前对各形态碳(尤其是有机碳中的慢性及惰性组分)缺乏系统的分析研究。基于此,本文综述了土壤中碳的主要赋存形态,各形态碳的组成、分布及作用,土壤碳的分析、分离方法。土壤无机碳储量约占全球总碳库的38%,赋存形态以碳酸盐为主。土壤有机碳主要分为活性碳库(周转期0.1～4.5年)、慢性碳库(周转期5～50年)和惰性碳库(周转期50～3000年)。其中可溶性有机碳、易氧化有机碳和微生物量碳属于活性有机碳库这一范畴,可以较为灵敏地反映土壤理化性质的微小变化;轻组有机碳和颗粒有机碳属于慢性有机碳库,可作为土壤有机质周转变化的重要指标;重组有机碳和矿物结合态有机碳属于惰性有机碳库,是土壤有机碳固持的重要机制之一。目前土壤中碳酸盐测定方法主要为气量法和滴定法;有机碳分析方法包括容量法、比色法和重量法。本文提出,今后应加强对无机碳及有机碳中的惰性组分研究,同时对土壤有机碳各组分概念及测定方法进行统一,并开展不同地域、不同土壤类型、不同浓度的土壤碳形态标准物质研制工作。     

泥炭沼泽源酚酸对铁有机复合体的溶解作用及其环境意义

泥炭沼泽是具有全球意义的湿地类型,研究泥炭沼泽源酚酸对铁有机复合体的溶解作用有助于深入了解铁碳耦合地球化学循环过程.以中国东北金川泥炭沼泽为研究对象,提取了泥炭腐殖质,并实验合成了铁有机复合体及一系列的铁氧化物.选择原儿茶酸、咖啡酸和没食子酸等代表性泥炭沼泽源酚酸对铁有机复合体以及铁氧化物等系统开展了不同条件下的溶解试验.结果表明酚酸对无定型的水铁矿和新合成的铁有机复合溶解能力相对较弱,而对结晶态的赤铁矿、针铁矿和老化后的铁有机复合体的溶解能力较强.pH值、酚酸浓度和铁氧化物自身的结构和组成都对铁矿物的溶解作用产生影响.反映了铁有机复合体在酚酸溶液体系中比无机铁氧化物更稳定,这与泥炭沼泽中有机结合态铁比例较高、而普通矿质土壤中结晶态铁氧化物占比更大的事实相吻合.证明了铁有机复合体是泥炭沼泽中影响铁碳循环耦合的关键载体.泥炭沼泽中铁碳作用十分复杂,既能以铁有机络合物形式向海洋等水生生态系统输出大量的溶解性铁,也能通过铁有机复合体的形成促进泥炭沼泽有机碳的保存,进而影响全球铁碳循环耦合,具有重要的生态环境意义.      

上扬子地区下寒武统页岩有机质孔隙类型及发育特征

为揭示古老层系过成熟页岩有机质孔隙的发育特征,以上扬子地区下寒武统页岩为例,采用岩石薄片、有机岩石学、有机地球化学、氩离子抛光-扫描电镜等多种技术方法,重点从有机质组成及有机质的赋存方式的角度,开展了有机质孔隙类型的识别,分析了各类孔隙的发育特征及形成机制。研究结果表明:下寒武统页岩主要发育3种有机质孔隙类型:固体沥青内有机质孔隙、有机质-无机矿物复合体内有机质孔隙及莓状黄铁矿集合体内有机质孔隙;页岩固体沥青内有机质孔隙普遍较发育,但孔径小(30 nm),页岩中天然气大量散失是导致有机质孔隙坍塌萎缩变小的主要原因;有机黏土复合体和莓状黄铁矿集合体形成的稳定抗压结构,有利于有机质孔隙及页岩气的保存。     

香溪河流域土壤有机碳储量影响因素的空间相关性分析

采用第二次土壤普查资料估算了香溪河流域不同类型土壤的有机碳密度和碳库,并通过野外土样采集和室内测试获取土壤有机碳含量数据,选取信息熵模型定量研究香溪河流域不同土壤类型、地形地貌类型、成土母质类型、植被覆盖度、土壤厚度、坡度和土地利用方式与土壤有机碳密度之间的关系。研究结果表明,香溪河流域土壤有机碳总储量为75.18Tg,香溪河流域SOC密度主要集中在6.00~16.00kg/m2范围内,SOC密度呈现流域北部高、干流高,其他区域SOC密度高低相间的分布特征,这种分布特征与主要土壤类型和地形地貌类型的地理分布关系密切。香溪河流域各种土壤类型对各级有机碳密度的信息熵值差异明显,土壤类型对有机碳密度的影响作用与香溪河流域土壤有机碳密度与碳库计算结果一致,高山区,林地、农田和灌丛利于高密度有机碳的存储;植被覆盖度越高,越利于有机碳的存储;土壤厚度与有机碳密度的相关性高,而坡度与有机碳密度的相关性不明显;信息熵法实现了对各影响因子定量计算分析,结果较合理和可靠。      

Molecular simulation of humic substance-Ca-montmorillonite complexes

An understanding of the processes that lead to long-term stabilization of organic matter in soils is essential to the effective implementation of strategies designed to mitigate CO₂ loss from the soil carbon reservoir in temperate climatic zones. Decomposition studies indicate that montmorillonite, a smectite that often forms with interlayers rich in Ca²⁺, greatly retards the microbial mineralization of soil organic matter. We performed a series of atomistic simulations designed to identify favorable molecular-scale organo-mineral interactions within nanoscale, hydrated complexes consisting of a humic substance and Ca-montmorillonite. Both protonated and Ca-saturated forms of the model humic molecule, representing acidic and circumneutral solution conditions, respectively, were studied within the hydrated interlayer region of a rigid-atom model of Ca-montmorillonite. The protonated humic substance formed direct hydrophobic and hydrogen bonding (H-bonding) interactions with the clay mineral. A few polar organic groups adsorbed via water bridging interactions. The Ca-saturated humic substance adsorbed via numerous cation bridges, less numerous water bridges, and indirect H-bonding interactions mediated by water molecules. Application of molecular modeling techniques to this complex organo-mineral system thus allowed identification of interactions favorable to carbon sequestration under both acidic and circumneutral conditions.     

Experimental Research on the Photodegradation of the Organic Compounds of Natural Waters

The photodegradation of organo-mineral complexes in natural conditions was studied using samples of soil and swamp waters to study the effect of sunlight on the composition and properties of organic matter and metal forms dissolved in natural waters. The total contents of certain aliphatic and aromatic carboxylic acids increased in the samples after irradiation. Photodegradation of organic matter of the natural waters with the high Fe content is accompanied by the formation of colloidal particles (Fe hydroxides). The number of negatively-charged complexes of Ni, Cu, Zn, and Cd increased under insolation in swamp waters and decreased in soil waters.     

红壤中矿物表面对腐殖质吸附萘的影响

矿物表面可改变土壤腐殖质对疏水性有机污染物的结合能力。采用红壤和高岭石分别与胡敏酸结合制备得到的两种复合体对萘的吸附等温线非线性显著,其n=0.76或0.74,并且有机碳归一化吸附分配系数的实验值Koacds是采用Kow计算得出的理论值Koc的5倍以上,表明红壤、高岭石均对腐殖质吸附萘有强化作用,且红壤较之高岭石对腐殖质吸附萘的影响稍强些。主要原因是,红壤中除了高岭石外,还有与腐殖质结合力很强的铁氧化物,而且很可能是吸附态腐殖质组成结构形态发生了有利于对萘吸附的改变。     

A Review of Study on Fe-C Interaction and Their Adsorption Properties to Soil Heavy Metal

Nowadays, the Fe-C coprecipitate mechanism is recognized by more and more scholars and becomes the hot topic in the environmental science. On the basis of discussing the interaction between iron oxide and organic matter, and the adsorption research progress of Fe-C complexes on heavy metals, the immobilization potential of Fe-C complexes on heavy metals in polluted soil were illustrated. The surface properties and physical characterizations of iron oxide are changed regularly with the interaction of organic matter, which lead to the higher adsorption capacity of Fe-C complexes in contrast to single iron oxide. Besides, the influences of pH values, organic matter types and surface properties of iron oxides on the adsorption capacity of Fe-C complexes on heavy metals were discussed. The excellent adsorption performance of Fe-C complexes in certain conditions will provide important theoretical basis for contaminated soil remediation.     

土结构性本构模型研究现状综述

土本构模型的建立是一个重要而又复杂的问题,到目前为止,国内外学者们已提出数以百计的土本构模型,诸多文献也对这些模型进行了评述和归纳。然而这些土本构模型多是在扰动土或砂土的基础上发展和建立起来的,它们难以描述由于土结构性引起的各种非线性行为,其计算结果与实际情况相差甚远。天然土体一般都具有一定的结构性,所以有必要建立考虑土结构性影响的土本构模型。针对这个现实,目前有些学者已基于各种理论和方法,提出了一些可以考虑土结构性影响的土本构模型,并得了较好的应用。但在目前的文献中还很少有对土的结构性本构模型研究进行归纳,基于此,本文简要介绍了一下目前土的结构性本构模型研究现状,并提出了这些本构模型在应用中所存在的问题。     

Metal Speciation in Water of the Flooded Mine “Arsenic” (Karelia,Russia): Equilibrium-Kinetic Modeling with a Focus on the Influence of Humic Substances

Equilibrium-kinetic modeling allows investigating metal behavior in the water–rock-organic matter system with time to evaluate anthropogenic effects on the environment. In the article, the interactions of stagnant mine drainage water of the flooded mine “Arsenic” with ore and gangue minerals were simulated using different organic matter incorporation approaches. If the model is closed to humic substances (no additional organic matter input), most fulvic acids are bound in the Fe fulvate complex. While under the removal of Fe fulvate from the model, the Cu fulvate becomes prevalent, the contribution of the fulvate complexes with Zn, Mg, and Ca also increases. This scenario simulates the organo-mineral complexes behavior well and allows identifying the sequence of metal binding to organic ligands as follows Fe?>?Cu?>?Zn?>?Mg?>?Ca. The second scenario imitates the constant input of organic matter to the model (open system regarding humic substances). The dissolved metal concentrations in the model solution are extremely high in comparison to the mine drainage water. This scenario demonstrates that excessive input of organic matter leads to the accumulation of the metals in a dissolved form and blocks the secondary mineral formation despite the faster dissolution of the primary minerals under a more acidic pH than in the first scenario. However, despite the differences between the model solution and the mine drainage water, this scenario is useful to address specific issues associated with changes in natural and anthropogenic conditions. Both scenarios show the importance of organic matter incorporation to the equilibrium-kinetic models.

     

论土体结构各层次的功能及其相互关系

土体广泛分布于地球的表层,是一个十分复杂的自然体。本文在论述了土体7个结构层次功能的基础上,从系统科学的角度阐述了各层次之间的辩证关系,包括低层次是高层次结构的基础;高层次对低层次结构的影响;层次间的协同作用;层次间交错、重叠与演变等。在与土体相关的研究工作和工程实践中,将土体作为一个系统进行合理的层次划分和分析,有助于复杂问题的简化,从而全面正确地掌握土体的工程性质及其形成机理。     

从土壤腐殖质分组到分子有机质组学认识土壤有机质本质

梳理了与土壤生态系统功能相联系的,特别是对固碳减排的土壤有机质本质认识的研究进展及路径,探讨了经典腐殖质学说存在的问题,概述了新近的有机质保护稳定学说及腐殖质组学学说,并追溯了生物标志物有机质分子研究,最后从土壤学的基本理念和理论出发讨论和重新认识土壤有机质的本质及其价值。从形成条件、分离条件和分子鉴定等多方面分析,土壤腐殖质形成和稳定学说越来越显示出局限性;而面向气候变化的碳固定研究可以深入探析土壤有机质的复杂存在状态。越来越认识到土壤有机质是投入土壤的有机物质经不同程度生物利用或降解的产物残留,只是被土壤不同程度地区隔和封闭,本质上仍是分子量变化极大的生命源有机物的集合。因此,可通过生物标志物分子作为靶标在土壤中提取和识别,该技术的发展将孕育萌生土壤有机质分子组学。后者可以用于判读土壤有机质的结构支撑、反应活性和促生功能等方面的本质差别,这些差别可能是由有机分子组成结构及存在状态所决定而不是由有机分子稳定性决定的。从这个概念出发,类似于土壤微生物分子生态,土壤有机质的丰度、组成、结构与功能间的联系可能是土壤有机质本质的核心问题。对这种关系的量化和参数化表征可用以探索土壤有机质永续固定,且可以保持生命活性的土壤有机质的管理策略及技术,并配合土壤的团聚体理论诠释土壤的本质和生态系统功能服务,这将是未来土壤学服务人类可持续发展的理论立足点。     

Exploring the Nature of Soil Organic Matter from Humic Substances Isolation to SOMics of Molecular Assemblage

In this review, the evolution of Soil Organic Matter (SOM) research was traced back to outline the main achievement of understanding SOM in relation to its ecological functioning, particularly of carbon sequestration against climate change. The short-coming of soil humus theory, knowledge of SOM protection and stabilization, framework of newly emerged Humeomics as well as the increasingly active study of molecular organics in soils were analyzed and discussed, highlighting the importance of re-visiting SOM in term of structure-property-functions for the main mission of modern soil science. There were limitations of soil forming conditions, fraction separation procedure and single molecule identification for understanding the huge complex humus of larger sized synthesized molecules. Thanks to the ever-active studies of soil (organic) carbon sequestration and stabilization focusing on the association status of SOM with soil components, SOM has been increasingly recognized as an assemblage of metabolites from life activities on or in soil, with different allocation or protected in mineral/organic complex phases, which could be traced by biomarker molecules. Using such biomarker molecules as a target (like primer in molecular microbiology), all the molecules of SOM could be digested and isolated for qualitative or quantitative identification with GC/MS high resolution technologies. Such development has emerged a new paradigm of molecular SOM study, finally as SOMics as a modern soil science frontier. The functioning of SOM for stabilizing soil structure, enhancing reactivity and promoting biological resistance could be correlated to the paradigm of abundance, composition, structure and functions rather than the content and recalcitrance of SOM. This may deserve urgent studies to quantify and parameterize the defined paradigm based on the molecular composition of SOM. Again, such theory and technology development could provide a tool to manage SOM in term of carbon sequestration but revalorizing bioactivity in ecosystems, especially in agroecosystems. We believe such studies could rather depict the nature of SOM and of soil in relation to its ecological services and functioning, which will be the focus of soil science in serving the sustainable development of human society.     

Vertical patterns of stable carbon isotope in soils and particle-size fractions of karst areas, Southwest China

Taking limestone soil and yellow soil, the two major soil types in karst areas as examples, analyzing stable carbon isotope composition (δ¹³C value) of soil organic matter (SOM) in bulk soils and particle-size fractions of four soil profiles under three vegetable forms, the following results are reached: in the limestone soil profile, soil organic carbon contents are all above 1.0%, the highest value is 7.1% in the surface soil; however, they are between 0.3% and 4.6% in the three yellow soil profiles. From the surface to the bottom of the soil profiles, the variation of δ¹³C value of soil organic carbon for limestone soil profile is only between −24.1‰ and −23.0‰, however, it’s between −24.8‰ and −21.1‰ for yellow soil profiles. The variation range of δ¹³C value of soil organic carbon associated with particle-size separates is slight for limestone soil but is considerable for yellow soil. The contrast research indicates that the changes between the contents and the δ¹³C value of soil organic carbon with depth are complex. The vertical patterns of stable carbon isotope in soil organic matter have a distinct regional characteristic in karst areas.