生物硅的测定及其生物地球化学意义

生物硅（BSi）指用化学方法测定的沉积物中的无定形硅含量。生物硅的含量与水体中初级生产息息相关。硅藻、放射虫、海绵骨针和硅鞭毛虫产生的生物硅是地球化学和古海洋学研究的重要参数。重点讨论了目前生物硅测定方法中的化学提取法，评述了提取过程中存在的一些问题，并对BSi测定的生物地球化学意义进行了讨论。     

Interactions of biogenic opal,sediment and seawater in the Central Equatorial Pacific

The solution rate of biogenic opal in near-surface sediments in the Central Equatorial Pacific is three to eight orders of magnitude lower than similar acid-cleaned samples. Iron, magnesium and calcium aluminosilicates may be the minerals which are forming on the surface of the opal and reducing its solution rate. The scale height of the system studied suggests that diffusive and not advective processes are primarily responsible for the removal of dissolved silica in sediments. Solution budget calculations for this area suggest that 90–99 per cent of the biogenic opal produced in surface waters dissolves before reaching the sediment-water interface; an additional amount dissolves within the sediment and diffuses into bottom waters leaving 0.05–0.15 per cent of the original amount of opal produced by organisms in the sedimentary record. The relative solution potential of the upper 1000 m of the water column varies by more than an order of magnitude from the Antarctic to Equator and may have a pronounced effect on the accumulation rate of biogenic opal in underlying sediments.     

The importance of water column processes on the dissolution properties of biogenic silica in deep-sea sediments I. Solubility

Flow-through experiments have been performed to study the thermodynamics of biogenic silica (opal) dissolution in deep-sea sediments. They were applied for the first time on sediment from the Southern Ocean [Van Cappellen and Qiu 1997a] and [Van Cappellen and Qiu 1997b] We have extended the use of these experiments to other deep-sea settings, thereby covering a wide range of in situ silicic acid asymptotic concentrations (C_asympt; 200 to 900 μmol/L) and biogenic opal content (BSi; 0.5 to 80%). Performing these experiments under in situ bottom temperatures allows for the comparison between experimental apparent solubilities and C_asympt concentrations. Low values of BSi apparent solubilities have been measured in the deepest sections of the multicores collected in the northeast Atlantic (229 μmol/L) and in the equatorial Pacific (505 μmol/L). They are only 10 to 20% higher than the in situ C_asympt concentrations. This demonstrates a clear control of pore water silicic acid concentrations by the in situ apparent solubility of the BSi, i.e., the solubility of BSi within a complex sedimentary matrix that includes important quantities of silicate minerals.In regions where the percentage detrital/percentage biogenic ratio is low, the apparent solubility of the biogenic silica is close to that of in situ biogenic silica. In the opposite case, when the percentage detrital/percentage biogenic ratio is high, reprecipitation reactions induce strong interference on the dissolution properties of the opal, both in situ and in flow-through experiments. In such a sedimentary matrix, it is important to determine the appropriate opal solubility to be used in early diagenetic models, i.e., the solubility of the biogenic silica just before deposition on the seabed. This has been achieved by performing flow-through experiments on sediment trap material from the north Atlantic site. Comparison of apparent biogenic silica solubility measured by flow-through experiments and the silicic acid concentrations measured in the cups of the sediment traps suggested that the solubility of biogenic silica that reaches the sediment-water interface is not unique and varies spatially and temporally. In fact, it is the degree of coupling between surface waters and the sediment-water interface that will control the aging of biogenic silica in the water column and hence the dissolution properties of the biogenic silica deposited at the sediment-water interface. All these results call for a strong improvement of biogenic silica early diagenetic models that should include not only a reprecipitation term that takes into account interaction with silicate minerals but also the existence of several phases of biogenic silica and thus that should operate in a non-steady-state mode to account for seasonal variations in the quality of deposited biogenic silica.     

Geochemical processes controlling silica concentrations in groundwaters of the Salado River drainage basin, Argentina

Chemical analyses of dissolved silica in the shallow groundwater of the lower part of the Salado River drainage basin indicate that silica values averaged 60 ppm. The groundwaters are oversaturated in relation to quartz, Na-plagioclase, K-feldspar, and the weathering of quartz and aluminosilicates appear to have little control on silica concentrations in solution. Groundwater is undersaturated with respect to amorphous silica present in the loessic sediments, and these sediments are specially important in the control of the groundwater composition. The sources of amorphous silica are volcanic glass shards and biogenic silica derived from plant (silicophytoliths, diatom frustules) or animal remains (sponge spicules) also present in the Pampean loess. Silicophytoliths and diatoms have also been reported in A soil horizon samples. The dissolution of amorphous silica most likely controls the high dissolved silica concentrations in groundwater.     

Evolution of silica accumulation in the earth’s history and its relation to biota development

Two branches of silica rockevolution related to oceans and continental blocks have been outlined. The boundaries of changes in types of silica rocks, their formation, and development of the organic world were established: (i) the beginning of the Phanerozoic was related to transformation from microbial to biogenic silica deposition (or to a change in the influence of microbial activity on silica accumulation); (ii) cessation of the formation of cherts enriched in organic matter, which was synchronized with land colonization by organisms in the Devonian, and (iii) an explosive style of global silica accumulation related to the appearance and development of diatoms, which correlates with appearance of angiosperm plants in tropical forests.     

Biogenic soil crusts and soil depth: a long‐term case study from the Central Negev desert highland

Wind‐blown soil degradation is a major problem in arid regions. Biogenic soil crust consists of a dense growth of many small organisms covering bare desert soil surfaces in arid regions worldwide. These organisms perform essential services in the ecosystem, for example, soil surface stabilization and carbon and nitrogen fixation. A unique service provided by biogenic crusts is the incorporation of large quantities of deposited atmospheric particles, leading to a significantly enhanced rate of increase in soil depth in windy and arid environments. A long‐term study (over 42 months) was conducted to investigate the contribution of a biogenic crust to the accumulation of atmospheric particles in an arid zone. Undisturbed and treated biogenic crusts were studied for their capacity to incorporate deposited particles. Atmospheric particles were found to accumulate on marble dust collectors at a rate of 120 g m^?2 year^?1 and on sterilized crust at a rate of 208 g m^?2 year^?1, while the accumulation rate on live, intact crusts was 277 g m^?2 year^?1, suggesting a soil depth accretion rate on an undisturbed biogenic crust of 10 mm every 33 years. Maintenance of a healthy biogenic crust in dry land environments should, therefore, be a major consideration for improving soil quality and increasing soil depth in arid regions.     

干旱荒漠覆盖区隐伏金矿上方覆盖层三维地球化学分布模式

深穿透地球化学已被证明是干旱荒漠区寻找隐伏矿的有效方法,但其对元素在覆盖层中的分布模式的探知还较少。为此,在新疆金窝子金矿运用了空气动力反循环钻探技术,以揭示元素三维分布模式,并了解元素迁移轨迹和迁移机理。形成的元素三维分布图表明：(1）元素异常在矿体上方不同深度覆盖层中具有继承性;(2）在覆盖层垂向剖面上,Au趋向于在顶层和底层富集,中间层含量较低;(3）底部异常主要分布在覆盖层和基岩接触部位的低洼位置;(4）底部异常横向延伸,范围较窄,仅数十米宽,而地表异常分布范围广,可扩展至数千米。     

Early diagenesis of biogenic silica in the Amazon delta: alteration, authigenic clay formation, and storage

Deltaic environments are commonly assumed to be relatively minor sites of biogenic silica burial because of the small quantities of opaline silica detected by most operational analytical techniques. Rapid conversion of biogenic silica into authigenic silicates is also often discounted as a significant control on oceanic silica budgets. A variety of evidence for extensive early diagenetic alteration of biogenic silica in rapidly accumulating Amazon delta sediments indicates that both of these general assumptions are unjustified. Apparent lack of significant biogenic silica storage in deltaic environments, particularly in the tropics, may be largely an artifact of operational definitions that do not include early diagenetic products of biogenic silica. Biogenic silica particles buried in suboxic Amazon delta deposits can be unaltered, partially dissolved, covered with aluminosilicate or metal-rich coatings, or completely reconstituted into authigenic K-Fe-rich aluminosilicate minerals. Pore water (K, Mg, F, Si) and solid-phase distributions, direct observations of particles, laboratory experiments, and depositional context indicate that authigenic clays form rapidly (<1 yr) in the seasonally reworked surface layer (∼ 0.5-2 m) of the delta topset and are disseminated during sediment remobilization. Fe, Al-oxide rich debris derived from the tropical drainage basin is an abundant reactant, and thus the supply of biogenic silica is a major control on the amount of clay formed.The mild 1% Na₂CO₃ alkaline leach procedure commonly used to estimate biogenic silica was modified to include an initial mild leach step with 0.1N HCl to remove metal oxide coatings and to activate poorly crystalline authigenic phases for alkaline dissolution. Well-crystallized clays are not significantly affected by this modification nor is bulk Amazon River bed sediment. The two-step procedure indicates that ∼90% of the biogenic silica originally present in deposits is converted to clay or otherwise altered, raising the effective quantity of biogenic silica stored from ∼33 to ∼296 μmol Si g⁻¹ (∼1.8% SiO₂). Biogenic Si stored in the delta increases away from the river mouth, across shelf and along the dispersal system where primary production is highest. The K/Si ratio of labile authigenic material is ∼0.19 mol mol⁻¹, far higher than Amazon River suspended matter (∼0.07 mol mol⁻¹). Diagenetic models indicate formation rates in the mobile sediment layer of ∼2.8 μmol K g⁻¹ yr⁻¹ (∼16 μmol Si g⁻¹ yr⁻¹). Inclusion of authigenic alteration products of biogenic silica in estimates of reactive Si burial increases the deltaic storage of riverine Si to ∼22% of the Amazon River input. The rapid formation of aluminosilicates from biogenic SiO₂, seawater solutes, and remobilized Fe, Al-oxides represents a form of reverse weathering. Rapid reverse weathering reactions in tropical muds and deltaic deposits, the largest sediment depocenters on Earth, confirms the general importance of these processes in oceanic elemental cycles.     

湿碱消解-等离子体发射光谱法测定海洋沉积物中的生物硅

利用湿碱式化学提取技术和电感耦合等离子体发射光谱仪,优化样品碱式消解方法,确定仪器最佳工作条件,建立了测定海洋沉积物中不同含量级别生物硅的方法。结果表明,仪器检出限为0.724μmol/L,方法检出限为0.942μmol/L。用于测定硅酸盐-硅溶液成分分析国家一级标准物质(GBW08648和GBW 08649,标准值分别为50.0μmol/L和100.0μmol/L),测定值分别为(49.888±0.275)μmol/L、(99.578±0.651)μmol/L,相对标准偏差为0.443%、0.527%;对于不同生物硅含量级别海洋沉积物样品的平行、独立测量,其相对标准偏差8.9%。方法快速、简便、准确,可满足古海洋学不同时空尺度气候和环境分析的应用。     

The Ge/Si ratio as a tool to recognize biogenic silica in chert

Germanium and silicon, dissolved in seawater, are considered to be incorporated into biogenic opal with no or little fractionation, which permitted to use diatoms as reliable recorders of seawater Ge/Si. Does some fractionation occur during diagenesis, preventing the use of Ge/Si in ancient sediments? We examined the Ge/Si ratio of fossil sponges and flint nodules of the Cretaceous Chalk Formation of northern France. Though disputed, silica in this formation is considered to originate from sponges. No fractionation is observed between sponges and diagenetic flints, which allows us to observe whether Ge/Si bears a biogenic or detrital signature. We may thus confirm that sponges were the main silica supplier during the chalk deposition. The Ge/Si ratio may be used to identify a biogenic signature in cherts where the origin of silica is dubious.     

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。     

Elemental and mineralogical changes in soils due to bioturbation along an earthworm invasion chronosequence in Northern Minnesota

Minnesota forested soils have evolved without the presence of earthworms since the last glacial retreat. When exotic earthworms arrive, enhanced soil bioturbation often results in dramatic morphological and chemical changes in soils with negative implications for the forests’ sustainability. However, the impacts of earthworm invasion on geochemical processes in soils are not well understood. This study attempts to quantify the role of earthworm invasion in mineral chemical weathering and nutrient dynamics along an earthworm invasion chronosequence in a sugar maple forest in Northern Minnesota. Depth and rates of soil mixing can be tracked with atmospherically derived short lived radioisotopes ²¹⁰Pb and ¹³⁷Cs. Their radioactivities increase in the lower A horizon at the expense of the peak activities near the soil surface, which indicate that soil mixing rate and its depth reach have been enhanced by earthworms. Enhanced soil mixing by earthworms is consistent with the ways that the vertical profiles of elemental and mineralogical compositions were affected by earthworm invasion. Biologically cycled Ca and P have peak concentrations near the soil surface prior to earthworm invasion. However, these peak abundances significantly declined in the earthworm invaded soils presumably due to enhanced soil mixing. It is clear that enhanced soil mixing due to earthworms also profoundly altered the vertical distribution of most mineral species within A horizons. Though the mechanisms are not clear yet, earthworm invasion appears to have contributed to net losses of clay mineral species and opal from the A horizons. As much as earthworms vertically relocated minerals and elements, they also intensify the contacts between organic matter and cations as shown in the increased amount of Ca and Fe in organically complexed and in exchangeable pools. With future studies on soil mixing rates and elemental leaching, this study will quantitatively and mechanically address the role of earthworms in geochemical evolution of soils and forests’ nutrient dynamics.     

云南种子植物区系地理成分分布格局及其意义

以覆盖云南全境的31个地区植物区系研究报告为基础, 使用Arcview软件制作了14个种子植物属的地理成分多度分布图。 对这些种子植物属的多度分布格局进行分析,获得以下结果:①热带成分合计占所统计的地区植物区系属的29.6%~94.1%, 其最小值是在云南西北部, 最大值出现在云南南部; 温带成分合计占所统计的地区植物区系属的6%~70.4%, 其多度分布恰与热带成分相反。②在热带成分中, 全热带分布属占13.64%~46%, 居热带成分之首, 其最大值出现在云南怒江和元江的干热河谷; 热带亚洲分布属占3.33%~42.26%, 最大值出现在云南南部。③在温带成分中, 北温带分布属占所统计的地区植物区系的2%~30.39%, 居温带成分之首, 最大值出现在云南西北部山地, 其次是东亚分布属, 占2%~14.57%, 最大值出现在滇西北横断山区。④在与云南植被的关系上,热带亚洲分布属、旧世界热带分布属和热带亚洲至热带大洋洲分布属是云南热带森林的主要成分; 全热带分布属和热带亚洲至热带非洲分布属是干热河谷植被的主要成分,北温带分布属主要出现在冷湿山地森林植被中,而东亚分布属、东亚和北美洲间断分布属及旧世界温带分布属与温凉气候地区的森林植被联系相对密切。⑤生物地理上,云南种子植物属的多度分格局暗示了所谓的“田中线”在印度—马来西亚热带植物区系与东亚亚热带—温带植物区系的地理界限上有意义;热带亚洲至热带非洲分布属主要存在于云南的干热河谷,暗示了干热河谷植被具有一定非洲亲缘;云南西部的热带性很强,暗示了在印度板块同亚洲板块相撞、推挤北移及喜马拉雅隆升过程中, 云南西部至东南部的地块可能发生了顺时针转动。⑥在云南, 不论其纬度, 只要是海拔低的区域都是热带区域, 支持云南应是一个基带为热带的大的山原观点。     

Stepwise fluorination—a useful approach for the isotopic analysis of hydrous minerals

Analytical uncertainties in oxygen isotopic studies of hydrous silica have been investigated using a partial fluorination procedure in which fractional oxygen yields are achieved by reducing the amount of fluorine. Stepwise reaction of opaline silica results in a set of sequential oxygen fractions which show a wide range of δ¹⁸O values due to variable amounts of water, organic matter, and other impurities, δ-values for successive fractions in non-biogenic opal systematically increase as water is reacted away and then remain constant to within ±0.2%. as the remaining silica reacts, δ-values in biogenic silica increase similarly but then decrease when low ¹⁸O oxide(?) impurities begin to react.The troublesome water component in opal is readily removed by Stepwise fluorination. This technique allows more precise oxygen isotope analysis of non-biogenic opal-A, and may improve the analytical precision for biogenic silica and any silicate mineral containing a significant water component.     

Clay mineralogy of the pleistocene soil horizon in Barind Tract, Bangladesh

Pleistocene red soil horizons were exposed in different areas of the Barind Tract in north-west Bangladesh. X-ray diffractions of twenty seven samples from different depths of these soil horizons revealed that the soil horizons consisted of kaolinite, illite and chrysotile with significant amount of opal-CT. Samples from Maddhapara, Bogra, and Nachole contain kaolinite, illite, quartz and opal-CT, and the samples from Kantabari contain chrysotile instead of kaolinite. Clay mineral compositions of different soil horizons indicated two different types of clay assemblages, viz. (a) illitekaolinite and (b) illite-chrysotile. In the village of Kantabari, illite-chrysotile clay mineral assemblage indicate that soil horizons were formed under low temperatures with alkaline and reducing conditions. However, other soil horizons of illite-kaolinite clay mineral assemblage indicate that soils were possibly formed under humid, temperate and welldrained conditions. These two soil horizons were formed under different geochemical, geomorphological and climatic conditions from different parent materials. Scanning Electron Microscopy photographs showing the presence of glass shards and no opal-A were found using XRD, suggesting that the opal-A might not be a precursor to opal-CT in the red soil horizon of the study area. This opal-CT along with the general lack of fossils and presence of glass shards was indicative of a volcanogenic rather than biogenic origin for the Opal-CT in the study area, and X-ray fluorescence data reveals higher percentages of silica which is comparable to the Toba Ash of Toba Caldera, Indonesia of about 75,000 B.P.     

古环境研究中深海沉积物粒度测试的预处理方法

对深海沉积物样品进行粒度测试前,应根据研究目的,在预处理过程中有效去除碳酸盐和生物硅,同时完好保留陆源碎屑组分,才能使测试结果准确反映古气候和古环境变化。对采于南海的样品分别加入不同剂量浓度为10％的盐酸或浓度为25％的醋酸,以及不同剂量的NaOH或Na2CO3,同时利用有机元素分析仪、硅钼蓝比色法、环境扫描电子显微镜分析、观察不同方法的预处理效果,并结合粒度测试的结果认为,对于碳酸盐,盐酸和醋酸均可将其有效去除,但由于少量盐酸仍会对陆源矿物组分造成破坏,因此应使用酸性较弱的醋酸;对于生物硅,大剂量的Na2CO3仍难将其有效去除,而使用小剂量的NaOH即可去除干净,但需控制剂量以避免破坏矿物组分。针对南海沉积物中的各种生物组分含量,确定了醋酸和NaOH的使用剂量并建立了预处理流程。     

Chemical and mineralogical development of the Sidamo nickeliferous serpentinites (Ethiopia)

The Sidamo serpentinites have developed by metamorphism of alpine-type peridotites and have been metamorphosed to talc schists, tremolite-chlorite schists and actinolite schists. Magnesite replacement, and opal and chalcedony veining result from weathering, though some magnesia and silica may have formed during metamorphism. Nickel concentration was negligible during metamorphism, but occurred to a significant extent during soil formation to form nickeliferous lateritic soils. Unfortunately most of the Sidamo serpentinites are undergoing high erosion (steep sided hills) and/or slow weathering (arid climate), so that soil formation and nickel concentration is poor.     

A normative calculation technique for determining opal in deep-sea sediments

The opal content of deep-sea sediment can be estimated by subtracting non-biogenic silica, calculated from the aluminum and magnesium concentrations in the sediment, from the total silica content of the samples. Unlike most previously described methods, this calculation is capable of yielding reliable estimates of opal in pre-Pleistocene sediments because it is unaffected by structural changes that take place in opal as it ages.     

Influence of hydrodynamic regime on the mineral composition of deep-sea sediments

The composition of sand-silt and pelite fractions of deep-sea sediments deposited under different hydrodynamic conditions was studied. Assemblages of clastic, clayey, biogenic, and authigenic minerals formed under the influence of surface and bottom currents were traced. It is shown that biogenic opal, fine-dispersed celestobarite, and authigenic protosyngenetic ferromanganese micronodules, which are composed of only manganese phases, represent indicators of cyclonic gyres characterized by enhanced bioproductivity. Collophane (bone detritus), phillipsite, palagonite, and large celestobarite crystals prevail in mineral assemblages below the anticyclonic gyres, whereas ore micronodules are depleted in manganese. Surface and bottom currents control the distribution of clastic (terrigenous edaphogenic, terrestrial-volcanogenic) and clay minerals, as well as biogenic opal in the form of Ethmodiscus frustules in sediments. Edaphogenic mineral assemblages represent the reliable indicators of bottom currents.     

A Study of Pretreatment Methods for Terrigenous Grain-Size Analysis of Marine Sediments

The prerequisite for obtaining variations of terrigenous grain-size of marine sediments is how to effectively remove non-terrigenous matters and preserve terrigenous particles synchronously. Combined with observations under biological microscope and scanning electron microscope, a comparative study of biogenic debris removal effect and terrigenous grain-size analysis under different pretreatment condition was performed on core sediments, which were retrieved in the South China Sea during the MD190 cruise. Our new results showed that the main three biogenic particles, namely, organic matter, carbonate, and opal in marine sediments could be removed effectively by 30% H₂O₂ in a stirring water bath at 60 ℃ for 3 h, 0.5% HCl for 1 h, and 2 mol/L Na₂CO₃ in a stirring water bath at 85 ℃ for 5 h, in turn. Such pretreatments achieved the goals of biogenic debris removal efficiency and relatively well-preserved terrigenous particles. Prior to selecting an appropriate pretreatment method, this study suggested that the actual effects of biogenic detritus on grain-size results of diverse marine sediment samples should be taken into account. If the laboratory data are ensured to be closer to the natural grain-size distribution of terrigenous particles, the removals of all biogenic debris are not always needed, and the less pretreatment processes the better. For example, opal particles have little effect on terrigenous grain-size distribution when their percentage is lower than 2%. Thus, there is no use to remove them from marine sediments before laboratory grain-size analysis of terrigenous particles. Additionally, ultrasonic is not suggested through the whole process of terrigenous grain-size analysis because the strong energy of ultrasonic can lead to the fragmentation of some fragile terrigenous particles.