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.     

硅同位素动力学分馏的实验研究及地质应用

由于硅在自然界中没有化学阶态变化，主要呈硅氧四面体形式存在，因此硅同位素的热力学分馏很小，由此产生的硅同位素变化不大。溶液中ＳｉＯ２沉淀过程的同位素动力学分馏是引起自然界硅同位素明显变化的主要原因。本文实验测定了溶液中ＳｉＯ２沉淀过程的硅同位素动力学分馏系数α，并结合所测定的硅同位素动力学分馏系数对现代海底黑烟囱、太古代条带状磁铁石英岩、风化成因粘土矿物的δ＾３０Ｓｉ值明显偏低；浅海碳酸盐台地中硅     

草地退化对植物硅分布和植硅体碳汇的影响:以北方农牧交错带草地为例

草地生态系统中,硅(Si)不仅在植物生长过程中扮演着重要的角色,而且通过形成植硅体碳(Phytolith-Occluded Carbon,简称PhytOC)的方式参与陆地生态系统碳循环。近几十年来,由于人为干扰等因素导致的草地退化引起了广泛的关注。本研究中,我们选取了我国北方农牧交错带中30个不同退化程度的样地,分析了8种常见植物(共71个样品)地上部分Si含量和分布特征,并估算了植硅体碳产生通量。结果发现,随着草地退化的加剧,糙隐子草(Cleistogenes squarrosa)地上部分Si含量呈下降趋势,而羊草(Leymus chinensis)表现为先上升后下降的倒"V"型。不同退化程度样地植物地上部分Si平均含量分别为12.25±1.02 g/kg(轻度)、10.56±1.15 g/kg(中度)和8.06±0.93 g/kg(重度),而植硅体碳产生通量显著下降,分别为0.320±0.038 kg/(ha·a)、0.190±0.021 kg/(ha·a)和0.068±0.006 kg/(ha·a)(P<0.05)。研究表明,草地退化对不同种类植物的Si含量和产生通量的影响不同,这可能是由于植物的功能类型不同造成的。草地退化可以导致种群结构的变化和地上净初级生产力(ANPP)的降低,从而影响草地植物地上部分Si的分布和植硅体的固碳能力。当退化严重时,初步估算北方农牧交错带内草地植物地上部分植硅体固碳速率将下降5倍以上。     

植硅体化学组成研究进展

现代植物植硅体化学组成研究有利于揭示植硅体的化学组成与细胞形态、植物种类及植物生长环境之间的关系,认识植硅体形成机制、植物分类及生态意义。植硅体化学组成测试方法多种多样,主要涉及植硅体化学元素组成及Si、O和C元素同位素组成测定,研究表明植硅体主要含二氧化硅和水,封闭有少量的有机成分及多种矿质元素。在植硅体封闭有机成分存在形式,部分元素的形成、迁移等循环机理,稳定碳同位素组成、分布及其生态指示意义以及^14C测年研究等方面取得一定认识。植物种类、组织部位、细胞微环境以及植物生长的环境因子能够影响植硅体的化学组成。植硅体化学组成研究对植硅体形成机制及碳、硅等元素循环具有重要意义,植硅体部分化学元素、植硅体稳定同位素组成及^14C测年具有较好的古环境及考古研究潜力。现代植物植硅体化学组成及其与环境因子的关系,以及植硅体电子探针微区研究有待于进一步深入开展。     

扬子地台硅岩的稳定同位素地球化学特点

本文利用硅岩中Si、O、C和Rb-Sr多种同位素的组成特点及分布趋势作为重要的地球化学标志，来判别扬子地台晚震旦世以来硅岩的成因、物质来源和形成环境。     

大厂锡矿床硅,氧同位素地球化学

本文对大厂锡矿床不同类型石英和岩石进行系统的硅、氧同位素研究表明，各类矿化体中石英的硅同位素组成几乎相同，而且它们又与直接容矿硅质岩的δ30Si值十分接近，但完全不同于矿区侵入岩的有关值。这说明层状矿体中的石英与直接窑矿硅质岩有相同的硅质来源，后期各类脉状矿化过程中的硅质来自容矿硅质岩，而不是花岗岩。层状矿体中荣带状岩石和含冰长石混合样的δ30Si值为-0．3‰±0．2‰，这组负值可能是由冰长石引起的。但冰长石中的硅是由海底热水活动系统还是火山灰尘提供尚待研究。对比发现，本矿区硅质岩δ30Si值与部分深海（洋壳区）、半深海（陆壳区）放射虫硅质岩有关资料相似，但其δ18O值低于全球各类硅质岩，它们可能是在海底热水活动与生物化学作用共同参与下形成的。     

多接收电感耦合等离子体质谱法测定岩石和土壤等国家标准物质的硅同位素组成

随着分析方法的进步和分析精度的提高，硅(Si)同位素被越来越多地应用于地球化学、宇宙化学和环境化学研究中，可以用于示踪壳幔物质循环、俯冲流体的来源，以及制约月球和地外天体的起源与演化等。为确保不同类型样品中硅同位素测量的准确性和不同实验室间数据可以进行对比，需标定一系列标准物质的硅同位素组成。前人工作中已经标定一系列来自美国地质调查局(USGS)的标准物质的硅同位素，为硅同位素的研究奠定了坚实的基础。但由于这些标准物质已经售罄，今后继续开展硅同位素研究面临无标样可用的境况。为了能持续性地用高精度硅同位素数据对相关领域研究提供支持，急需对新的标准物质进行高精度的硅同位素的测量。本文采用氢氧化钠碱熔法消解样品，经化学纯化后，利用多接收电感耦合等离子体质谱法精确测量了30个国家标准物质的硅同位素组成，δ³⁰Si值测试精度优于0.08‰。这些标准物质包括11个火成岩、2个变质岩、2个沉积岩、6个河流和海洋沉积物以及9个土壤，SiO₂含量范围为32.69%～90.36%,覆盖了大部分自然样品的变化范围。在这些标准物质中，河流沉积物GBW07310具有最...     

直接熔融热电离质谱法测定硼硅玻璃中硼同位素比值

硼硅玻璃是目前压水堆应用最多的可燃毒物材料,产品中硼同位素组成的准确测定对燃耗预估及产品质量判定具有重要意义。文章基于直接熔融热电离质谱法,首先探讨了硅元素对硼酸中硼同位素测量结果的影响,结果表明:Si/B质量比小于9时,硅对NIST 951a硼酸标准物质测量结果无显著干扰,采用直接熔融热电离质谱法测定核电用硼硅玻璃中硼同位素比值具有可行性;随后,详细分析了Na/B摩尔比、甘露醇和石墨加入量3个参数对测试结果的影响,得到的最佳参数为Na/B摩尔比9、加入甘露醇及3μL石墨发射剂;最后,采用优化测试参数,对实际硼硅玻璃样品进行了测试,并以NIST 951a硼酸标准物质为外标对测量结果进行分馏校正,结果发现分馏校正后样品的不确定度来源主要是标准物质。研究成果可满足硼硅玻璃的燃耗预估及产品质量的快速判定需要。     

高精度硅同位素分析方法研究进展

基于碱熔法的改进和多接收电感耦合等离子质谱仪（MC-ICP-MS）的发展,近年来高精度Si同位素组成（δ30Si）分析方法取得了长足进步,分析精度（2SD）自气体质谱仪（GS-MS）时代的±0.15‰~±0.30‰ 提高到优于±0.10‰,足以辨析高温过程中Si同位素发生的微小分馏,并且避免了实验流程中使用含氟等危险化学品。二次离子质谱（SIMS）和飞秒激光剥蚀（fs LA）的发展使得原位Si同位素组成分析精度近期也优化到±0.10‰~±0.22‰。文章对近年来Si同位素分析方法的发展沿革进行综述,探讨建立溶液法MC-ICP-MS的高精度Si同位素分析方法的进展与局限,并比对了国内外各个实验室已发表国际国内Si同位素标准物质测定值,最后总结了硅酸盐地球（BSE）、地壳和陨石等主要地质储库的δ30Si组成范围。     

新疆望峰金矿区成矿流体的Si同位素示踪研究及其成矿意义

新疆望峰金矿区金的成矿作用与硅化作用密切相关,文章通过对矿区典型矿体的赋矿围岩、蚀变岩石及矿石进行Si同位素组成研究,探讨了成矿流体中硅质来源、演化过程及其成矿意义。结果表明:1望峰金矿体围岩具有较均一的Si同位素组成,δ30Si=-0.2‰(n=3),显示了花岗质原岩Si同位素组成特征,动力变质作用对原岩硅同位素组成无明显影响;2蚀变岩石Si同位素组成均一性较高,δ30Si=-0.1‰(n=3),显示了花岗质原岩Si与成矿期热液Si的混合特征;3矿石Si同位素组成变化范围较大,不同类型矿石的Si同位素组成差异较明显:硅化蚀变糜棱岩型δ30Si=-0.5‰~-0.2‰(n=9),集中于-0.3‰~-0.2‰,平均-0.3‰;硅化蚀变岩型δ30Si=-0.3‰~-0.1‰(n=9),平均-0.2‰;热液石英脉型δ30Si=-0.3‰~0.1‰(n=6),平均-0.1‰。望峰金矿区金成矿流体中的硅质,主要来源于花岗质赋矿围岩。矿石中Si同位素组成变化较大,是富硅成矿流体演化过程中发生Si同位素动力学分馏的结果,矿体下部及矿区深部应有一定的找矿前景。     

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.     

Silicon isotope fractionation between rice plants and nutrient solution and its significance to the study of the silicon cycle

The silicon isotope fractionation between rice plant and nutrient solution was studied experimentally. Rice plants were grown to maturity with the hydroponic culture in a naturally lit glasshouse. The nutrient solution was sampled for 14 times during the whole rice growth period. The rice plants were collected at various growth stages and different parts of the plants were sampled separately. The silica contents of the samples were determined by the gravimetric method and the silicon isotope compositions were measured using the SiF₄ method.In the growth process, the silicon content in the nutrient solution decreased gradually from 16 mM at starting stage to 0.1-0.2 mM at harvest and the amount of silica in single rice plant increased gradually from 0.00013 g at start to 4.329 g at harvest. Within rice plant the SiO₂ fraction in roots reduced continuously from 0.23 at the seedling stage, through 0.12 at the tiller stage, 0.05 at the jointing stage, 0.023 at the heading stage, to 0.009 at the maturity stage. Accordingly, the fraction of SiO₂ in aerial parts increased from 0.77, through 0.88, 0.95, 0.977, to 0.991 for the same stages. The silicon content in roots decreased from the jointing stage, through the heading stage, to the maturity stage, parallel to the decrease of silicon content in the nutrient solution. At the maturity stage, the silicon content increased from roots, through stem and leaves, to husks, but decreased drastically from husks to grains. These observations show that transpiration and evaporation may play an important role in silica transportation and precipitation within rice plants.It was observed that the δ³⁰Si of the nutrient solution increased gradually from −0.1‰ at start to 1.5‰ at harvest, and the δ³⁰Si of silicon absorbed by bulk rice plant increased gradually from −1.72‰ at start to −0.08‰ at harvest, reflecting the effect of the kinetic silicon isotope fractionation during silicon absorption by rice plants from nutrient solutions. The calculated silicon isotope fractionation factor between the silicon instantaneously absorbed by rice roots and the silicon in nutrient solution vary from 0.9983 at start to 0.9995 at harvest, similar to those reported for bamboo, banana and diatoms in direction and extent. In the maturity stage, the δ³⁰Si value of rice organs decreased from −1.33‰ in roots to −1.98‰ in stem, and then increased through −0.16‰ in leaves and 1.24‰ in husks, to 2.21‰ in grains. This trend is similar to those observed in the field grown rice and bamboo.These quantitative data provide us a solid base for understanding the mechanisms of silicon absorption, transportation and precipitation in rice plants and the role of rice growth in the continental Si cycle.     

Mechanisms controlling silicon isotope distribution in the Eastern Equatorial Pacific

The distribution of silicon isotopes along a meridional transect at 140°W longitude in the Eastern Equatorial Pacific was used to test the hypothesis that δ³⁰Si of silicic acid in surface waters should correlate with net silica production rates (gross silica production minus silica dissolution) rather than rates of gross silica production due to the opposing Si isotope fractionations associated with silica production and silica dissolution. Variations in δ³⁰Si appeared significantly correlated with net silica production rates in equatorial surface waters and not with gross production rates. Around the Equator, values of δ³⁰Si as low as deep water values occurred in the upper mesopelagic in a zone of net silica dissolution and high detrital biogenic silica content, where the release of low δ³⁰Si silicic acid from opal dissolution would be expected to decrease δ³⁰Si. The δ³⁰Si of the deep water at 140°W appears constant for depths >2000 m and is similar to the deep water at 110°W. This study brings to light the importance of considering Si fractionation during diatom silica dissolution, the biological fractionation during silica production and physical factors such as currents and mixing with adjacent water masses when interpreting silicon isotope distributions.     

Experimental identification of Ca isotopic fractionations in higher plants

Hydroponic experiments have been performed in order to identify the co-occurring geochemical and biological processes affecting the Ca isotopic compositions within plants. To test the influence of the Ca concentration and pH of the nutritive solution on the Ca isotopic composition of the different plant organs, four experimental conditions were chosen combining two different Ca concentrations (5 and 60 ppm) and two pHs (4 and 6). The study was performed on rapid growing bean plants in order to have a complete growth cycle. Several organs (root, stem, leaf, reproductive) were sampled at two different growth stages (10 days and 6 weeks of culture) and prepared for Ca isotopic measurements.The results allow to identify three Ca isotopic fractionation levels. The first one takes place when Ca enters the lateral roots, during Ca adsorption on cation-exchange binding sites in the apoplasm. The second one takes place when Ca is bound to the polygalacturonic acids (pectins) of the middle lamella of the xylem cell wall. Finally, the last fractionation occurs in the reproductive organs, also caused by cation-exchange processes with pectins. However, the cell wall structures of these organs and/or number of available exchange sites seem to be different to those of the xylem wall. These three physico-chemical fractionation mechanisms allow to enrich the organs in the light ⁴⁰Ca isotope. The amplitude of the Ca isotopic fractionation within plant organs is highly dependent on the composition of the nutritive solution: low pH (4) and Ca concentrations (5 ppm) have no effect on the biomass increase of the plants but induce smaller fractionation amplitudes compared to those obtained from other experimental conditions. Thus, Ca isotopic signatures of bean plants are controlled by the external nutritive medium. This study highlights the potential of Ca isotopes to be applied in plant physiology (to identify Ca uptake, circulation and storage mechanisms within plants) and in biogeochemistry (to identify Ca recycling, Ca content and pH evolutions in soil solutions through time).     

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.     

Silicon isotope fractionation between plant parts in banana: In situ vs. in vitro

We recently showed that silicon isotopic fractionation in banana (Musa acuminata Colla, cv Grande Naine) was related to phytolith production, and therefore to silica content in plant. The present study focuses on isotopic fractionation between the different plant parts. Silicon isotopic compositions were measured using a Nu plasma multicollector plasma source mass spectrometer (MC–ICP–MS) operating in dry plasma mode. The results are expressed as δ²⁹Si relatively to the NBS28 standard, with an average precision and accuracy of ± 0.08‰ (± 2σ). On mature banana (Musa acuminata Colla, cv Grande Naine) from Cameroon, δ²⁹Si ranged from + 0.13‰ in the petiole to + 0.49‰ in the lamina, yielding to a 0.36‰ change towards heavier isotopic composition in the upper parts of the plant. This strongly accords with results obtained on in vitro banana plantlets cultivated in hydroponics, where the δ²⁹Si increase from pseudostems to lamina is 0.26‰. These preliminary results on in situ banana show a trend of intra-plant fractionation comparable with that of in vitro hydroponics banana plantlets and with previous data obtained on bamboo.     

Experimental study of silicon isotope dynamic fractionation and its application in geology

Silicon shows no variation in its chemical valence in nature and exists mainly in the form of silicon-oxygen tetrahedra, so very small silicon isotope thermodynamic fractionation occurs and the resultant silicon isotope variation is limited. Dynamic fractionation of Si isotopes during precipitation of SiO₂ from a solution is a main factor leading to substantial variations in silicon isotopes in nature. In this experimental study, we determined the dynamic fractionation factorα for silicon isotopes during precipitation of SiO₂ from the solution. And in combination of α, a theoretical explanation is presented of the considerably low δ³⁰Si values of black smokers on modern seafloor, Archean banded magnetite-quartzite and clay minerals of weathering origin, and of clearly high δ³⁰Si values of siliceous rocks in shallow-sea carbonate platforms. This paper won the Paper of Excellence in the Second National Young Scientist Symposium on Geochemistry of Minerals and Rocks.     

Copper isotope fractionation by desert shrubs

Copper has two naturally occurring stable isotopes of masses 63 and 65 which can undergo mass dependent fractionation during various biotic and abiotic chemical reactions. These interactions and their resulting Cu isotope fractionations can be used to determine the mechanisms involved in the cycling of Cu in natural systems. In this study, Cu isotope changes were investigated at the organismal level in the metal-accumulating desert plant, Prosopis pubescens. Initial results suggest that the lighter Cu isotope was preferentially incorporated into the leaves of the plant, which may suggest that Cu was actively transported via intracellular proteins. The roots and stems show a smaller degree of Cu isotope fractionation and the direction and magnitude of the fractionations was dependent upon the levels of Cu exposure. Based on this and previous work with bacteria and yeast, a trend is emerging that suggests the lighter Cu isotope is preferentially incorporated into biological components, while the heavier Cu isotope tends to become enriched in aqueous solutions. In bacteria, plants and animals, intracellular Cu concentrations are strictly regulated via dozens of enzymes that can bind, transport, and store Cu. Many of these enzymes reduce Cu(II) to Cu(I). These initial results seem to fit into a broader picture of Cu isotope cycling in natural systems where oxidation/reduction reactions are fundamental in controlling the distributions of Cu isotopes.     

Effect of Zn deficiency and excessive bicarbonate on the allocation and exudation of organic acids in two Moraceae plants

The effect of zinc (Zn) deficiency and excessive bicarbonate on the allocation and exudation of organic acids in plant organs (root, stem, and leaf) and root exudates of two Moraceae plants (Broussonetia papyrifera and Morus alba) were investigated. Two Moraceae plants were hydroponically grown and cultured in nutrient solution in four different treatments with 0.02 mM Zn or no Zn, combined with no or 10 mM bicarbonate. The variations of organic acids in different plant organs were similar to those of root exudates in the four treatments except B. papyrifera, which was in a treatment that was a combination of 0.02 mM Zn and no bicarbonate. The response characteristics in the production, translocation, and allocation of organic acids in the plant organs and root exudates varied with species and treatments. Organic acids in plant organs and root exudates increased under Zn-deficient conditions, excessive bicarbonate, or both. An increase of organic acids in the leaves resulted in an increase of root-exuded organic acids. B. papyrifera translocated more oxalate and citrate from the roots to the rhizosphere than M. alba under the dual influence of 10 mM bicarbonate and Zn deficiency. Organic acids of leaves may be derived from dark respiration and photorespiration. By comparison, organic acids in stems, roots, and root exudates may be derived from dark respiration and organic acid translocation from the leaves. These results provide evidence for the selective adaptation of plants to environments with low Zn levels or high bicarbonate levels such as a karst ecosystem.     

Silicon isotope and trace element constraints on the origin of ∼3.5 Ga cherts: Implications for Early Archaean marine environments

Silicon (Si) isotope variability in Precambrian chert deposits is significant, but proposed explanations for the observed heterogeneity are incomplete in terms of silica provenance and fractionation mechanisms involved. To address these issues we investigated Si isotope systematics, in conjunction with geochemical and mineralogical data, in three well-characterised and approximately contemporaneous, ∼3.5 Ga chert units from the Pilbara greenstone terrane (Western Australia).We show that Si isotope variation in these cherts is large (−2.4‰ to +1.3‰) and was induced by near-surface processes that were controlled by ambient conditions. Cherts that formed by chemical precipitation of silica show the largest spread in δ³⁰Si (−2.4‰ to +0.6‰) and are characterised by positive Eu, La and Y anomalies and overall depletions in lithophile trace elements. Silicon isotope systematics in these orthochemical deposits are explained by (1) mixing between hydrothermal fluids and seawater, and/or (2) fractionation of hydrothermal fluids by subsurface losses of silica due to conductive cooling. Rayleigh-type fractionation of hydrothermal fluids was largely controlled by temperature differences between these fluids and seawater. Lamina-scale Si isotope heterogeneity within individual chemical chert samples up to 2.2‰ is considered to reflect the dynamic nature of hydrothermal activity. Silicified volcanogenic sediments lack diagnostic REE+Y anomalies, are enriched in lithophile elements, and exhibit a much more restricted range of positive δ³⁰Si (+0.1‰ to +1.1‰), which points to seawater as the dominant source of silica.The proposed model for Si isotope variability in the Early Archaean implies that chemical cherts with the most negative δ³⁰Si formed from pristine hydrothermal fluids, whereas silicified or chemical sediments with positive δ³⁰Si are closest to pure seawater deposits. Taking the most positive value found in this study (+1.3‰), and assuming that the Si isotope composition of seawater is governed by input of fractionated hydrothermal fluids, we infer that the temperature of ∼3.5 Ga seawater was below ∼55 °C.