植硅体圈闭碳地球化学研究进展

植硅体是一种地球化学稳定性非常高的植源性非晶质二氧化硅颗粒物,在其形成过程中会圈闭一定量的有机碳。目前,植硅体圈闭碳(简称植硅体碳)被认为是一种稳定的碳汇机制,对调节全球气候变化具有重要意义,同时,植硅体碳同位素的研究对于古环境、古气候重建等研究领域具有重要的价值,因此,植硅体圈闭碳的地球化学研究受到许多学者的关注。基于国内外学者对植硅体、植硅体圈闭碳及其相关领域的研究成果,综述了植硅体的形成过程、化学元素组成、地球化学稳定性、植硅体碳汇以及植硅体碳同位素在古环境研究中的应用5个方面的研究进展,同时总结了当前植硅体及其圈闭碳在地球化学过程研究中所面临的主要问题,对于未来继续开展植硅体地球化学研究工作具有重要意义。     

植硅体稳定同位素生物地球化学研究进展

植硅体形态鉴定与组合分析广泛应用于古环境重建和农作物起源分析等.鉴于植硅体的抗腐蚀、抗降解,易保存,锢囚的碳不易污染,且保存了植物的原始信息等特性,其有机地球化学研究日益被重视.植硅体稳定同位素分析表明植硅体是植物通过吸收单硅酸,以蒸腾作用为主要动力,在植物的不同部位发生同位素分馏淀积形成,其稳定同位素组成具有丰富的植物生理和环境信息.植物不同部位植硅体稳定同位素组成具有差异,其含量和硅、氧同位素值沿蒸腾流通常有增加的趋势.沉积物植硅体碳同位素分析不仅可以用于恢复草本的C3、C4植物生物量的比例,并且有可能重建古大气的碳同位素构成,是三者中最具有潜力的考古学、古环境研究的指标.植硅体有机化学组成分析,特别是类脂物分析,有利于认识植硅体碳同位素值相对于总有机碳偏负,C3、C4草本植硅体同位素差值范围缩小的原因.     

有机碳同位素示踪古环境变化研究

对有机碳同位素示踪环境变化的原理、研究对象、取得的进展和存在的问题等进行了详细研究，认识到C～H键比C-O键有利于富集^12C，从而导致生物或有机碳δ^13C为极低的负值，使有机碳与无机碳之间存在显著的碳同位素差异。光合作用类型的不同使植物分为C3，C4和CAM3种类群，并导致不同类群的植物具有不同的碳同位素组成，C3植物δ^13C=-20‰～-32‰，平均-28‰，而C4植物δ^13C=-9‰～-17‰，平均-14‰。气候环境的差异影响了光合作用的类型和强度，使不同环境的植物类群特征不同，不仅造成植物组合的碳同位素组成不同，而且导致不同食性的动物牙齿等化石的碳同位素组成的差异，甚至相应的无机碳同位素的变化，因此生物链及其衍生物的碳同位素研究也就成为反演某一地区或某一时期气候环境的有效手段。被作为研究对象的地质记录可分为有机和无机两类，有机类主要包括树轮等植物化石、牙齿等动物化石、煤等陆相沉积有机质、海相沉积有机质、土壤(前者的衍生物)，这些研究对象分别适合于目的不同的环境研究，并获得了较好的效果。进而发现有机碳同位素在研究重大生物灭绝事件、C4植物起源、地球早期生命起源、地外生命存在与否、矿产资源形成时的有机质作用等问题上将有重要作为。     

浙江余姚田螺山遗址土壤植硅体AMS~(14)C测年初步研究

植硅体(phytolith)是植物体细胞中非晶体二氧化硅脱水后的产物。非晶体二氧化硅的一个聚合基有活性,能够结合植物细胞中的有机碳。植物体死亡后,非晶体二氧化硅脱水,形成坚硬的硅质物,具有抗风化、抗腐蚀、耐酸的特点。植物原生的有机碳被封闭在植硅体内,与外界隔绝,被很好地保存了下来。利用植硅体进行~(14)C年代测定,可以得到植物体死亡的年龄。本研究采集浙江田螺山新石器时代遗址水稻田土壤样本,提取其中的植硅体,通过元素分析、红外光谱进行鉴定,并利用加速器质谱对植硅体样品进行~(14)C年代测定,以期得到水稻田的使用年代;对同层位炭化植物种子也利用加速器质谱进行了~(14)C年代测定。对比结果显示,植硅体年代数据与炭化植物种子的年代在3σ误差范围内一致,植硅体年代数据的中值比炭化植物种子的年代数据中值略有偏老。可以认为植硅体的年代基本上代表了水稻田被使用的年代,植硅体测年可以作为植物年代测定的有效手段。同时,本文尝试针对本研究植硅体年代数据偏老的部分原因做了一点讨论。     

沈北煤田煤中琥珀的植物来源和稳定同位素的古环境意义

琥珀是由古代植物代谢产生的树脂聚合物形成的化石。琥珀中的有机质保存环境稳定、封闭,能很好地记载其形成时期的古植物和古环境等信息。本次研究运用气象色谱质谱联用仪（GC-MS）和元素分析稳定同位素质谱仪（EA-IRMS）等测试方法,研究了沈北煤田煤中琥珀的有机地球化学组成、稳定同位素和化合物单体碳同位素特征。结果表明,琥珀中的饱和烃以二萜化合物为主（占73.45%）,芳香烃以松香烷型化合物为主（56.17%）;高含量的贝壳杉烷、雪松烷、扁枝烷和松香烷型化合物指示琥珀来源于松柏类植物,且以柏科植物为主。沈北琥珀的δ13C值为-22.8‰ ~ -21.2‰,与同时期其他地区琥珀的δ13C值相似;氢同位素变化范围较小（-297.2‰ ~ -276.0‰）,氧同位素值为17.4‰ ~ 31.6‰。琥珀的稳定同位素组成（碳、氢和氧）进一步证明琥珀来源于裸子植物。琥珀的δ13C值主要与其形成时的全球气温变化和大气组成有关。沈北琥珀的氢和氧同位素组成主要受植物种类（松柏类）以及植物生长的局部气温和降水条件有关。琥珀稳定碳同位素有望成为研究古气候和古大气组成的良好载体,琥珀的氢和氧同位素可以反映形成时期的古环境条件,但仍需进一步深入研究。     

植硅体碳与陆地生态系统碳循环：机遇和挑战

植硅体在形成过程中能够包裹植物有机碳,是已被证明的一种非常有潜力的大气CO₂封存方式,对于增加陆地生态系统碳汇和延缓温室气体效应带来的全球变暖具有重要意义,因此受到了学术界的广泛关注。简要回顾了植硅体碳的研究历史和现状,并着重从植硅体碳长期变化入手,探讨了植硅体碳与陆地生态系统碳汇存在的问题与挑战,以及近来有关植硅体碳存在被严重高估的论点。同时指出为了更加准确地估算植硅体碳汇,应充分考虑植硅体包裹碳能力的差异、植硅体碳来源、植硅体稳定性、土壤中植硅体碳含量衰减速率以及植硅体提取方法等在植硅体碳的长期变化中的作用,进一步提高植硅体碳在陆地碳汇研究中的地位与重要性。     

植硅体14C测年研究:过去、现在与未来

文章回顾了植硅体14C测年发展的历史,对当前其研究的现状进行了全面的总结和评述,对近年来其研究的争议进行了梳理。植硅体测年研究中存在的问题(如污染和老碳效应等)在其他材料测年过程同样存在,不能基于少量现代植物植硅体测年的异常数据而完全否定其意义。大量的测年数据显示,并不是所有的植硅体年代都偏老,相反地层中的植硅体年代与同层位其他材料的年代重合或接近。因此,在一些缺少其他有机质测年材料的地层,植硅体14C测年仍然是一种极具潜力的年代学方法,在构建一些重要环境和考古文化时间标尺上将会发挥更重要的作用。     

化学地层学及其研究进展

化学地层学是利用岩层中化学元素及其化合物的演变规律及含量分布特征进行地层的划分和对比,进而推断地层形成时的地球化学环境的一门地层学分支。根据所采用的化学信号,化学地层学可进一步划分为放射性同位素地层学、稳定同位素地层学、分子化学地层学、有机碳和碳酸盐碳化学地层学和元素化学地层学等。     

中国陆地生态系统植硅体碳汇研究进展

植硅体碳(Phytolith-Occluded Carbon,Phyt OC)是一种相对稳定的碳组分,在生物地球化学碳循环和减缓全球变暖中扮演着重要角色。在总结前人研究的基础上,论述了植硅体碳的形成机制和其碳汇能力的影响因素,综述了当前中国陆地生态系统植硅体碳汇的研究成果,探讨了中国陆地生态系统植硅体碳汇的调控机制,最后对未来中国陆地生态系统植硅体碳汇的研究方向进行了展望。气候、地表植被类型、土壤环境及植硅体自身化学组份等诸多因素都将直接或间接影响植硅体的碳汇能力。中国草地、农田、森林、湿地和灌丛生态系统植硅体碳产生速率分别为(0.6±0.1)×106,(4.9±1.7)×106,(1.9±0.4)×106,(0.6±0.5)×106和(1.3±0.3)×106t CO2/a。含硅材料施加、高硅植物栽培和传统的提高植物地上净初级生产力等措施均可显著提高中国陆地生态系统植硅体碳汇潜力。今后应进一步研究不同植物产生植硅体碳的机理,加强不同陆地生态系统中植物地下部分植硅体碳汇能力的研究,对不同陆地生态系统土壤植硅体碳汇量进行量化,并提出更加全面、经济、合理的管理措施以提高植硅体碳汇量。     

增温、施氮、CO2浓度升高对羊草(C3)、芦苇(C4)植硅体组合的影响

研究未来全球变暖和氮沉降下C3、C4植物植硅体的变化规律,对松嫩草原优势群落演替方向的预判、古植被及古气候的重建和全球环境变化的预测等工作具有重要意义.本文选取松嫩草原的优势物种羊草(Leymus chinensis,C3)和芦苇(Phragmites communis,C4),对其进行模拟增温、施氮、CO2浓度升高处理,研究叶片部位植硅体的组合规律及形态变化特征,试图寻找在改变某一单一环境要素条件下,C3、C4植物所含各类型植硅体百分含量及形态的变化规律,以探究C3、C4植物植硅体对不同环境因素响应的异同.结果显示:CO2浓度升高、增温对羊草植硅体发育具有促进作用,对芦苇植硅体发育起抑制作用;氮素过高对羊草和芦苇植硅体的发育都不利,但增温能减轻施氮对羊草植硅体的负面效应.棒型、板型、方型、块状、蜂窝状植硅体对模拟增温、施氮、CO2浓度升高反应敏感,可作为指示环境变化的新指标.     

植硅体在河流硅输送中的作用

高等植物产生的植硅体是古气候和古环境研究的重要手段,也是陆地硅循环中重要的硅的储库;植硅体通过河流的跨区域输送在全球硅的生物地球化学循环中起着重要作用,是区域硅循环研究的重要载体,然而这方面的关注却很少。河流输送的生物硅大致分为自源和异源两种类别。"自源"生物硅主要包括河流水体本身自生浮游植物(主要是淡水硅藻)产生的硅质颗粒;"异源"生物硅主要由流域土壤的侵蚀输出到河流的植硅体所构成。流域地表过程是使得部分土壤中的植硅体进入河流的主要途径,并成为河流生物硅输送中重要的形式,这对河流-河口水循环体系的硅生物地球化学循环过程产生了重要的影响,但人们对河流输送的植硅体在硅循环中的作用的研究还不够。文章着眼于陆海相互作用研究,以河流中水体携带的植硅体为中心,总结了河流植硅体输送在地表水体硅循环系统中贡献的研究进展,分析了长江与黄河植硅体入海通量与河口行为及对近海海洋环境的影响。最后,对未来河流输送的植硅体参与硅循环研究可能需要加强的科学问题提出了建议。     

长白山泥炭湿地主要植物植硅体形态特征研究

对长白山地区常见的泥炭地25个属31个种植物进行了植硅体形态鉴定统计,共发现植硅体类型15种,它们分别是硅化气孔、棒型、扇型、板型、硅质突起、尖型、导管型、帽型、齿型、哑铃型、鞍型、多边帽型、毛发型等。除禾本科和莎草科、菊科部分植物植硅体含量高外,木贼科、堇菜科、茜草科、蓼科等部分植物植硅体的含量也较高。禾本科植物的短细胞植硅体对植物分类有意义,但可能因采样环境和种类差异等原因,长白山泥炭湿地禾本科植物的植硅体在形态和数量上都与其他区域同类研究结果有所差异,如禾本科早熟禾亚科的菵草中新发现了含量丰富的枕木型植硅体,黍亚科的荩草和水稗中还发现少量帽型植硅体; 另外菊科兴安一枝黄花和齿苞风毛菊含有大量的特殊的尖形植硅体。硅化气孔宽度大小可指示环境湿度状况,对硅化气孔的数量和大小的深入研究将对古环境和古CO₂浓度的恢复有一定帮助。长白山泥炭湿地植物的植硅体与植物的分类关系密切,湿地植物植硅体中硅质突起、棒型、哑铃型和尖型植硅体特征组合代表湿冷组合,本研究中的5块泥炭湿地植硅体的组合特征受纬度变化影响不明显。     

植物微体化石分析揭示阿敦乔鲁遗址古人生存策略

新疆地区是史前游牧文化与农业文化交融的重要区域,而地处新疆西天山地区的阿敦乔鲁青铜时代遗址,是古代人类活动、文化发展与演化过程的重要时空节点。但是目前对该遗址古人生存策略,尤其是对于当时人们的饮食结构和遗址的季节性使用的认识,存在不同观点。本研究通过对阿敦乔鲁遗址中房址内堆积物、羊粪化石以及遗址周边现代羊粪、自然地层进行植硅体、孢粉分析,发现了农作物植硅体以黍(Panicum miliaceum)和麦类作物的稃片为主,遗址使用后期出现少量的粟(Setaria italica),揭示了该遗址农作物组成以黍、大/小麦(Hordeum spp./Triticum spp.)为主,兼有粟的混合结构。在秋季(9月份)采集的现代羊粪中,孢粉种类(24个科/属)和浓度(平均65533粒/g)显著高于羊粪化石的孢粉种类(9个科/属)和浓度(平均27189粒/g),且现代羊粪以蒿属(Artemisia)植物(7~10月开花结籽)花粉为主(平均54.95%),羊粪化石中蒿属植物花粉仅有19.20%。来自早熟禾亚科(Pooideae)种子稃片的植硅体,在现代羊粪中的含量(平均3.62%)显著低于在羊粪化石中的含量(平均13.84%),羊粪孢粉和植硅体分析结果,揭示了阿敦乔鲁遗址羊类放牧时间应该处于花期结束后,植物已结籽的秋-冬季节,为阿敦乔鲁遗址冬季牧场的性质提供了植物学证据。同时房址内火塘、活动面和储藏间的堆积中植硅体组合与羊粪化石植硅体组合接近,暗示了羊粪可能被大量收集储藏,作为主要的铺垫物和冬季燃料使用。研究结果对于深化青铜时代以来新疆西天山地区古人生存策略、食物结构等的认识具有重要的推动作用。     

Laser Ablation In Situ Silicon Stable Isotope Analysis of Phytoliths

Silicon is a beneficial element for many plants and is deposited in plant tissue as amorphous bio‐opal called phytoliths. The biochemical processes of silicon uptake and precipitation induce isotope fractionation: the mass‐dependent shift in the relative abundances of the stable isotopes of silicon. At the bulk scale, δ³⁰Si ratios span from ?2 to +6‰. To further constrain these variations in situ, at the scale of individual phytolith fragments, we used femtosecond laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (fsLA‐MC‐ICP‐MS). A variety of phytoliths from grasses, trees and ferns were prepared from plant tissue or extracted from soil. Good agreement between phytolith δ³⁰Si ratios obtained by bulk solution MC‐ICP‐MS analysis and in situ isotope ratios from fsLA‐MC‐ICP‐MS validates the method. Bulk solution analyses result in at least twofold better precision for δ³⁰Si (2s on reference materials ≤ 0.11‰) over that found for the means of in situ analyses (2s typically ≤ 0.24‰). We find that bushgrass, common reed and horsetail show large internal variations up to 2‰ in δ³⁰Si, reflecting the various pathways of silicon from soil to deposition. Femtosecond laser ablation provides a means to identify the underlying processes involved in the formation of phytoliths using silicon isotope ratios.     

Effect of fire on phytolith coloration

Dark‐colored phytoliths are often found preserved in paleosols and archaeological sediments. Some practitioners believe these darkened phytoliths provide evidence of fire histories, while others suggest alternative reasons for their occurrence. This study examines the effect of fire on phytolith appearance and discusses the extent to which color may be used as proxy evidence for fire. The results of this study demonstrate that under oxidative conditions of openair fire, the color of phytoliths can be altered, although dark‐colored phytoliths also occur naturally in some unburned plant species. Despite some overlap observed between burned and unburned color in phytoliths, clear differences are apparent in the way this color appears optically. In particular, transparent and opalescent qualities were found to occur in nature as opposed to a dull opaque appearance of charred phytoliths. Although fire‐induced color change is probably limited to a portion of the phytolith assemblage, phytolith color remains a tool that can be confidently used to indicate the presence of fire in various sedimentary contexts. © 2006 Wiley Periodicals, Inc.     

Opaline and Al–Si phytoliths from a tropical mire system of West Malaysia: abundance, habit, elemental composition, preservation and significance

Abundant and unique opaline and Al–Si phytoliths and opaline bioliths have been discovered in Holocene peat deposits of tropical Tasek Bera in Peninsular Malaysia. These are secreted mainly by plants (higher plants and algae) and incorporated in the sediment cycle during the rapid biomass turnover. Many wetland plants have entire skeletons secreted. The study shows that differing plant parts of same species as well as same parts of differing plant species incorporate different amounts of elements. Whilst deciduous trees of the swamp forest have phytoliths enriched in Al, most phytoliths of palms, sedges and grasses of the littoral swamp are composed of opaline silica. Incorporation of Al and many other elements into relatively stable phytoliths is the result of high evapotranspiration rate and ample plant-available elements and can serve to detoxify the soil solution. Because of the abundance of such opaline and Al–Si structures, spongillid and algal remains in acid peat-accumulating environments, tropical peatlands represent repositories of Si and Al, which together with variable amounts of other elements could provide the prime material for silicate neoformation during later diagenetic processes. Neoformation of minerals from bioliths would explain the scarcity of biogenic remains in Carboniferous and Tertiary coal deposits. Furthermore, incorporation of major elements in phytoliths may limit the rate of leaching of these elements in an environment where biomass turnover is rapid, thus reducing the loss of nutrients and other plant-essential elements. Most nutrients of tropical peats are recycled by plants within the top 150 cm and an upward migration of plant-essential elements, such as Mg, Ca, or P, but also of Si and Al, occurs during peat accumulation. Such elemental cycling strongly influences the geochemical composition of the peats during mire evolution. Utilizing Al for normalization of major and minor elements of tropical peats for paleoclimatic and paleodepositional analyses may thus result in incorrect interpretations.     

Identifying the δO signature of precipitation in grass cellulose and phytoliths: Refining the paleoclimate model

Cellulose and silica phytoliths were extracted from the leaves and stems of Calamovilfa longifolia, a C₄ grass, grown under varying climatic conditions across the North American prairies. The oxygen-isotope compositions of both cellulose and silica record a complex signal of the isotopic composition of the soil water that feeds the plants and the relative humidity conditions that influence transpiration rates, stomatal conductance, and ultimately the ¹⁸O-enrichment of leaf water. As the initial stages of cellulose formation occur in the leaves, cellulose in both the leaves and stems forms primarily from leaf water and does not differ greatly in its oxygen-isotope composition between these locations. In contrast, the δ¹⁸O values of leaf phytoliths are significantly enriched in ¹⁸O relative to stem phytoliths, reflecting the varying isotopic composition of the water in these tissues. The oxygen-isotope compositions of leaf cellulose may be used as a proxy for the isotopic composition of water involved in leaf phytolith formation, while the δ¹⁸O values of stem phytoliths can be used to determine the δ¹⁸O values of stem water involved in partial exchange reactions during the transport of carbohydrates through the plant. A comparison of the isotopic compositions of phytoliths with cellulose allows for the deduction of soil and leaf water δ¹⁸O values as well as temperature and relative humidity conditions during plant growth. This approach has application in paleoclimate studies that traditionally have required estimations of one or more of these variables because direct measurements were unavailable.     

Silicon isotope fractionation in bamboo and its significance to the biogeochemical cycle of silicon

A systematic investigation on silica contents and silicon isotope compositions of bamboos was undertaken. Seven bamboo plants and related soils were collected from seven locations in China. The roots, stem, branch and leaves for each plant were sampled and their silica contents and silicon isotope compositions were determined. The silica contents and silicon isotope compositions of bulk and water-soluble fraction of soils were also measured. The silica contents of studied bamboo organs vary from 0.30% to 9.95%. Within bamboo plant the silica contents show an increasing trend from stem, through branch, to leaves. In bamboo roots the silica is exclusively in the endodermis cells, but in stem, branch and leaves, the silica is accumulated mainly in epidermal cells. The silicon isotope compositions of bamboos exhibit significant variation, from −2.3‰ to 1.8‰, and large and systematic silicon isotope fractionation was observed within each bamboo. The δ³⁰Si values decrease from roots to stem, but then increase from stem, through branch, to leaves. The ranges of δ³⁰Si values within each bamboo vary from 1.0‰ to 3.3‰. Considering the total range of silicon isotope composition in terrestrial samples is only 7‰, the observed silicon isotope variation in single bamboo is significant and remarkable. This kind of silicon isotope variation might be caused by isotope fractionation in a Rayleigh process when SiO₂ precipitated in stem, branches and leaves gradually from plant fluid. In this process the Si isotope fractionation factor between dissolved Si and precipitated Si in bamboo (α_pre-sol) is estimated to be 0.9981. However, other factors should be considered to explain the decrease of δ³⁰Si value from roots to stem, including larger ratio of dissolved H₄SiO₄ to precipitated SiO₂ in roots than in stem. There is a positive correlation between the δ³⁰Si values of water-soluble fractions in soils and those of bulk bamboos, indicating that the dissolved silicon in pore water and phytoliths in soil is the direct sources of silicon taken up by bamboo roots. A biochemical silicon isotope fractionation exists in process of silicon uptake by bamboo roots. Its silicon isotope fractionation factor (α_bam-wa) is estimated to be 0.9988. Considering the distribution patterns of SiO₂ contents and δ³⁰Si values among different bamboo organs, evapotranspiration may be the driving force for an upward flow of a silicon-bearing fluid and silica precipitation. Passive silicon uptake and transportation may be important for bamboo, although the role of active uptake of silicic acid by roots may not be neglected. The samples with relatively high δ³⁰Si values all grew in soils showing high content of organic materials. In contrast, the samples with relatively low δ³⁰Si values all grew in soil showing low content of organic materials. The silicon isotope composition of bamboo may reflect the local soil type and growth conditions. Our study suggests that bamboos may play an important role in global silicon cycle.