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1.
Stirred flow-through experiments were conducted for the first time with planktonic biogenic silica (BSi). We investigated the dissolution kinetics of uncleaned and chemically cleaned BSi collected in ocean surface water, sediment traps, and sediments from the Norwegian Sea, the Southern Ocean, and the Arabian Sea. The solubility at 2°C is rather constant (1000 to 1200 μM). The dissolution rates are, however, highly variable, declining with water depth, and phytoplankton reactivity is two to three orders of magnitude higher than pure siliceous oozes. The reactivity decrease correlates well with an increase in the integrated peak intensity ratios of Si-O-Si/Si-OH measured by Fourier transform infrared (FTIR) spectroscopy. The removal of organic or inorganic coatings enhance the reactivity by at least an order of magnitude. Atomic Al/Si ratios of 0.03 to 0.08 in sedimentary diatom frustules decrease significantly to 0.02 as a result of removal of inorganic coatings and detritals present. Near equilibrium, the dissolution rates exhibit a linear dependence on the degree of undersaturation. At higher degrees of undersaturation—that is, at low concentrations of dissolved silica—the dissolution rates of uncleaned samples define a nonlinear trend.The nonlinear kinetics imply that the dissolution of natural BSi is strongly accelerated in silica-depleted surface waters. The FTIR results suggest that internal condensation reactions reduce the amount of surface reaction sites and are partly responsible for the reactivity decrease with depth. The high content of Al in sedimentary BSi is likely caused by precipitation of dissolved silica with Al dissolved from minerals in sediment. Nonbiogenic silica as coatings or detritals are partly responsible for the solubility and reactivity decrease of BSi in sediments. One order of magnitude different rate constants measured in Norwegian Sea and Southern Ocean sediment trap material support the so-called opal paradox—that is, high BSi accumulation rates in sediments in spite of low BSi production rates in surface waters of the Southern Ocean.  相似文献   

2.
生物硅的测定及其生物地球化学意义   总被引:19,自引:1,他引:19  
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。  相似文献   

3.
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.  相似文献   

4.
The long-term stability of biogenic uraninite with respect to oxidative dissolution is pivotal to the success of in situ bioreduction strategies for the subsurface remediation of uranium legacies. Batch and flow-through dissolution experiments were conducted along with spectroscopic analyses to compare biogenic uraninite nanoparticles obtained from Shewanella oneidensis MR-1 and chemogenic UO2.00 with respect to their equilibrium solubility, dissolution mechanisms, and dissolution kinetics in water of varied oxygen and carbonate concentrations. Both materials exhibited a similar intrinsic solubility of ∼10−8 M under reducing conditions. The two materials had comparable dissolution rates under anoxic as well as oxidizing conditions, consistent with structural bulk homology of biogenic and stoichiometric uraninite. Carbonate reversibly promoted uraninite dissolution under both moderately oxidizing and reducing conditions, and the biogenic material yielded higher surface area-normalized dissolution rates than the chemogenic. This difference is in accordance with the higher proportion of U(V) detected on the biogenic uraninite surface by means of X-ray photoelectron spectroscopy. Reasonable sources of a stable U(V)-bearing intermediate phase are discussed. The observed increase of the dissolution rates can be explained by carbonate complexation of U(V) facilitating the detachment of U(V) from the uraninite surface. The fraction of surface-associated U(VI) increased with dissolved oxygen concentration. Simultaneously, X-ray absorption spectra showed conversion of the bulk from UO2.0 to UO2+x. In equilibrium with air, combined spectroscopic results support the formation of a near-surface layer of approximate composition UO2.25 (U4O9) coated by an outer layer of U(VI). This result is in accordance with flow-through dissolution experiments that indicate control of the dissolution rate of surface-oxidized uraninite by the solubility of metaschoepite under the tested conditions. Although U(V) has been observed in electrochemical studies on the dissolution of spent nuclear fuel, this is the first investigation that demonstrates the formation of a stable U(V) intermediate phase on the surface of submicron-sized uraninite particles suspended in aqueous solutions.  相似文献   

5.
沉积物岩心记录着沉积环境的演变过程,其中生物硅(BSi)记录能反映硅质生物的生产力时间和空间变化,2012年5月在下辽河平原西南缘得到了ZK2钻孔柱状样,通过对其沉积物原位密度、生物硅、碳埋藏、粒度、AMS~(14)C和OSL测年、有孔虫鉴定、孢粉鉴定,将ZK2孔的沉积环境主要划分为上三角洲平原相沉积、海洋主导的沉积、湖相沉积、河道沉积4个沉积单元,其相应的生物硅(BSiO_2)浓度分布依次为(2.85±0.23)%、(1.55±0.10)%、(1.96±0.10)%、(0.92±0.05)%,并且生物硅的波动与颗粒有机碳浓度的波动同步。特别是在17~25 cal ka BP冰期形成的湖沼沉积出现较大的颗粒无机碳(PIC)浓度的波动,推测与当时干冷气候条件下CaCO_3过饱和从湖水中沉淀析出有关。钻孔沉积物生物硅浓度记录对格陵兰冰芯~(18)O同位素值的响应存在大约300 a的滞后现象。  相似文献   

6.
Analyses for silica in the interstitial water of five cores from the southeast Pacific are presented. Silica is enriched in these interstitial waters resulting in a vertical flux of silica of between 10 and 50 μmol cm?2 yr?1 from the sediment into the overlaying seawater. This flux is generated by the dissolution of biogenic silica, the dissolution of which is increased in areas of bottom water turbulence. The Si, Al and calculated opal (Leinen, 1977) contents of the bulk sediment of these cores are also presented. Small scale variations over depth intervals of tens of centimetres are present as a result of chaning conditions of sedimentation.  相似文献   

7.
The occurrence and significance of biogenic opal in the regolith   总被引:1,自引:0,他引:1  
Jonathan   《Earth》2003,60(3-4):175-194
Biogenic opal produced by vascular plants, diatoms, and siliceous sponges have been found in soils and terrestrial sediments of all continents except Antarctica since the middle of the 19th century. The opal particles range in size from fine silt to fine sand. Almost all soils contain detectable opal up to levels of 2–3%, and a significant number contain values in excess of 5%. Even higher values have been found from soils and sediments of all continents in a wide range of soil types. The most important factor is poor soil drainage and seasonal to permanent water logging. This encourages the proliferation of silica producing organisms. Such conditions have been found in the soils and aquatic sediments of the monsoonal tropics, tropical rain forests, temperate forests, tropical savanna, tropical islands, semi-arid grasslands and savanna, and temperate woodland and grassland. The presence of a volcanic substrate also appears favourable in some cases, but is not necessary. Biogenic opal preferentially collects in the A horizon of soils and, to a lesser extent, in the B horizon. This preferential distribution facilitates identification of palaeosols in stacked soil sequences. Biogenic opal is also a component of windblown dust, even in arid environments. Biogenic opal is significant to regolith processes in a number of ways. Firstly, as in the case in marine environments, it is likely to be important in silica cycling and storage because of its greater lability compared to quartz. Secondly, dissolution and reprecipitation of opal A as opal CT or micro-quartz may play a role in cementation and silicification of regolith to form silica hardpans and silcrete. Thirdly, the organisms that form biogenic opal can have considerable palaeoenvironmental significance and be valuable in reconstructing regolith evolution. Finally, some forms of biogenic silica, in particular sponge spicules, can present a health hazard. Their high abundance in some soils and sediments needs to be considered when assessing the health implications of airborne dust.  相似文献   

8.
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.  相似文献   

9.
The chemistry and mineralogy of much of the Late Eocene Blanche Point Formation of South Australia show that biogenic and volcanogenic products were the only significant contributor to the sedimentary record. Intermittent volcanic activity followed by dissolution of the resultant silicic ash and small scale migration of silicon with reprecipitation as the oxide, provides the simplest and most likely explanation for the repetitive nature of the silicification. Seemingly, this was controlled by local silica concentrations which in turn were apparently controlled by the biota. Changes in circulation patterns and/or water depth may have initiated the environmental variations recorded in the formation.  相似文献   

10.
An annual budget for dissolved silica (DSi) and biogenic silica (BSi) was constructed for the Scheldt estuary and for the entire riverine and estuarine Scheldt tidal system (Belgium/The Netherlands) using previously published silica concentrations and fluxes for the period 2003–2005. The annual estuarine DSi mass-balance was established, based on seasonal fluxes estimated using measured DSi concentrations and (fully transient) model simulations of conservative transport. The annual BSi mass-balance was deduced from measured BSi contents in the suspended particulate matter and annual mud fluxes taken from the literature. The Scheldt estuary acted as a net sink not only for the BSi carried by the tidal river as well as that produced by diatoms in the estuary, but also for large amounts of BSi imported from the coastal zone. This results in the retention of dissolved and biogenic silica higher than that of DSi alone, which is in contrast with the classical consideration that rivers act as a source of BSi for the coastal zone. DSi and silica (DSi + BSi) retentions amounted to, respectively, 28 and 64 % in the estuary, and 33 and 66 % in the entire tidal system. This study highlights thus the predominant role of the estuary in the entire Scheldt tidal system when dealing with silica dynamics, as well as the importance of including BSi when investigating estuarine silica retention.  相似文献   

11.
Recently, the increase in dissolved concentration in the batch dissolution of various salts or sucrose has been successfully modelled with three equations, one a cubic in time. However, from three separate earlier investigations with ocean sediments and phytoplankton frustules, there is residual suspicion that biogenic silica does not follow this behaviour. This paper shows that the Shrinking Object Model applies to the dissolution of sieved silica gel particles, as well as to a sample of unsieved, freeze-dried frustules of Odentella sp. Silica gel, being readily available in quantities that can be sieved, is a useful surrogate for biogenic silica in allowing problems of experimental design to be overcome. The dissolutions covered three possible analytic integrations that arise from the model: an exponential for approach to saturation with excess solid silica; the approach to near saturation with either a slight excess or deficiency of silica; dissolution at high under-saturation. Good agreement was found between experimental results and mathematical modelling. The paper provides template calculations by which future raw results can be parameterized. Nevertheless, the reasons for non-linear kinetics reported in earlier work have not been identified, and so controversy over non-linear dissolution kinetics is enhanced. Stirring regime was found to be important with silica gel dissolution, and so biogenic silica dissolution is therefore likely to be ‘transport limited’ at low stirring rate. Accordingly, all archived and future data should be scrutinized for stirring effects before being applied to the oceanic environment. A rigorous test for determining whether a substance’s dissolution deviates from the model is recommended as a preliminary to any future dissolutions, whether in batch or with the chemo-stat. A fixed amount of frustule sample is added to a series of buffered mixtures containing increasing background silicic acid concentrations. Absence of any problem is marked by a linear plot between the increase in silicic concentration accruing over a fixed reaction period and that of the background silicic acid. A novel mathematical proof is provided to justify the test’s use. The reasons for the earlier deviations from expected behaviour of, for example, oceanic sediments, are discussed. Lastly, the paper provides a novel approach to the dissolution of a population of particles of mixed sizes which will probably find ready future application in oceanography.  相似文献   

12.
Sediment and water from the Meiliang Bay of Lake Taihu were analyzed to examine the historical relation between the accumulation of biogenic silica (BSi) and total phosphorus (TP). The results indicate that BSi accumulation in the northern part of Lake Taihu had been controlled by diatom production and phosphorus loading since the 1950s. BSi accumulation increased with the growing agricultural activity since the 1950s, up to a maximum level in the 1960s. After that, BSi accumulation decreased due to the diatom dissolution till the 1980s, and then the diatom biomass decreased with BSi accumulation increased. Lake Taihu came into an accelerated eutrophication periods since the 1990s, while BSi accumulation began to increase but the proportion of diatom decreased. Although the onset of silica depletion cannot be confirmed in the present work, it is clear that BSi accumulation was restrained by the input of TP.  相似文献   

13.
Water column and seabed samples were obtained from 92 stations on the Amazon continental shelf during October of 1979. Uptake of silica near and southeast of the river mouth began at a salinity of 8%. and accounted for 17% of the riverine silica flux to this region. Uptake northwest of the river mouth began at a salinity of 20%. and resulted in 33% removal of the riverine silica flux. Examination of filtered suspended solids revealed abundant diatoms in the surface waters, including Coscinodiscus. Skeletonema, Synedra. and Thalassiosira. The biological uptake of silica appears to be dependent on three factors: turbidity, turbulence, and nutrient availability. There was no evidence of abiological removal of silica in the Amazon estuary. 75 to 88% of the silica removed from surface waters by diatoms dissolves prior to accumulation in the seabed. Based on the mean biogenic silica content of shelf sediment (0.25%) and estimates of rates of sediment accumulation, the biogenic silica accumulation rate on the shelf is 2 × 1012 g/yr, which represents only 4% of the dissolved silica supplied by the Amazon River. Biological uptake of silica in estuarine surface waters may not accurately reflect permanent removal of biogenic silica to the seabed because of dissolution which occurs in bottom waters and near the sediment-water interface.  相似文献   

14.
Fractionation of silicon isotopes during biogenic silica dissolution   总被引:2,自引:0,他引:2  
Silicon isotopes have been investigated for their potential to reveal both past and present patterns of silicic acid utilization, primarily by diatoms, in surface waters of the ocean. Interpretation of this proxy has thus far relied on characteristic trends in the isotope composition of the dissolved and particulate silicon pools in the upper ocean, as driven by biological fractionation during the production of biogenic silica (bSiO2, or opal) by diatoms. However, other factors which may influence the silicon isotope composition of diatom opal, particularly post-formational aging and maturation processes, remain largely uninvestigated. Here, we report a consistent fractionation of silicon isotopes during the physicochemical dissolution of diatom bSiO2 suspended in seawater under closed conditions. This fractionation acts counter to that occurring during bSiO2 production and at about half its absolute magnitude, with dissolution discriminating against the release of the heavier isotopes of silicon at an enrichment factor εDSi–BSi of −0.55‰, corresponding to a fractionation factor α30/28 of 0.99945. The enrichment factor did not vary with source material, indicating the lack of a significant species effect, or with temperature from 3 to 20 °C. Thus, the dissolution of bSiO2 produces dissolved silicon with a δ30Si value that is 0.55‰ more negative than its parent bSiO2, an effect that must be accounted for when interpreting oceanic δ30Si distributions. The δ30Si values of both the dissolved and particulate silicon pools increased linearly as dissolution progressed, implying a measurable (±0.1‰) change in the relative δ30Si of opal samples whenever the difference in preservation efficiency between them is >20%. This effect could account for 10–30% of the difference in diatom δ30Si values observed between glacial and interglacial conditions. It is unlikely, however, that the inferred maximum possible change in δb30SiO2 of +0.55‰ would be manifested in situ, as a high mean percentage of dissolution would include complete loss of the more soluble members of the diatom assemblage.  相似文献   

15.
The sediments of the Bauer Deep, an open ocean basin situated on the northwest Nazca Plate in the southeast Pacific, constitute a regional metalliferous deposit dominated by authigenic smectite.Two 2-metre long cores from the Bauer Deep were examined to investigate the nature and origin of the smectite.Infra-red and Mossbauer spectroscopy and wet chemical analysis (LiBO2 fusion) of isolated smectite, indicate the mineral is a Mg-rich, Al-rich nontronite. Oxygen isotopic compositions for isolated smectite are uniform and translate to a non-hydrothermal temperature of formation of about 3°C. SEM observations show an abundance of well-preserved biogenic opal in surface and near surface sediment but postburial dissolution and transformation of this phase to smectite is evident at depth.Smectite formation is the result of interaction between iron oxyhydroxide, ponded in the Bauer Deep following a hydrothermal origin at the adjacent East Pacific Rise, and biogenic opal. A reaction mechanism is proposed.Regional factors control smectite formation. In particular, formation is inhibited in areas of CaCO3 accumulation (topographic elevations) but favoured in areas of oxyhydroxide and opal ponding (topographic depressions).  相似文献   

16.
Silicic acid (H4SiO4) flux from the sediment, H4SiO4 concentration and river flow were used to obtain an annual dissolved silicon budget for Chesapeake Bay. H4SiO4 concentrations vary seasonally in the estuary: for a 12-year period, mean H4SiO4 concentrations in the mesohaline region were high both in spring and in late summer to early fall, and were low in late spring—occasionally approaching levels potentially limiting to diatom growth. Most of the annual allochthonous H4SiO4 supply to the estuary derives from the three major rivers, but regenerative H4SiO4 flux from the sediment to the water column exceeds the total riverine input by a factor of at least five. Sediment H4SiO4 efflux exhibits seasonality and averages approximately 2–3 mol Si m?2 yr?1. The high rates of sediment dissolution and efflux appear to maintain high levels of H4SiO4 in the mesohaline region, and Si-limitation of diatom growth there seems unlikely. The relative rates of biogenic silica formation and dissolution do not vary synchronously: seasonal variations in diatom productivity, sedimentary release of H4SiO4 and river flow all contribute to the observed late winter and late summer seasonal maxima and late spring minimum in water column H4SiO4 concentrations. If the only source of Si to support sedimentary H4SiO4 efflux is biogenic particulate silica recently deposited from the water column and this silica in turn was produced by diatoms in a ratio of 8C:1 Si, the minimum annual primary production by diatoms is at least 260 g C m?2, approximately half of annual total plankton primary production. This estimate would be revised upwards according to the amount of particulate biogenic silica dissolving in the water column. Burial of biogenic silica amounts to from 2 to 84% of the sediment efflux of H4SiO4, depending on location in the bay. On an annual basis, burial represents from 60 to 100% of fluvial H4SiO4-Si inputs.  相似文献   

17.
This study introduces an alkaline leaching technique for the simultaneous analysis of biogenic silica and aluminium in sediments. Measuring aluminium facilitates the discrimination between silica from the biogenic (BSiO2) and the non-biogenic fraction, because it originates almost solely from the lithogenic phase. The method was tested using fine-grained silicagel, standard clay minerals, artificial sediments, and natural samples ranging from fresh diatoms to aged sediment from different depositional settings. To determine the BSiO2 content, four different models each describing the dissolution curves, but of increasing complexity, were applied and for each different type of sample the optimum model was selected on the basis of F-test statistics. For mixtures of silicagel and clay minerals, the contribution of Si from the dissolution of clay was negligible compared to Si originating from silicagel. For natural samples with high clay content, complex dissolution curves were observed and single-phase first order dissolution was the exception. This deviation from `ideal' behavior could only be recognized because of high-resolution sampling, especially in the first 20 minutes of the experiment. For most of the samples, the distinction between the biogenic silica fraction and the silica originating from dissolution of clays could be made on the basis of the Si/Al ratios and reactivity constants of the dissolving phases calculated with the models. Clay minerals typically dissolve slowly at a Si/Al ratio close to 1–2, depending on the type of clay mineral. In contrast, biogenic silica displays a wide range of reactivities and Si/Al ratios. Fresh biogenic silica from the water column usually has a high reactivity and a low Al content. Aged biogenic silica from the sediments has a lower reactivity, but Si/Al ratios as low as 5 were found. The method as described here therefore presents an accurate method to analyze biogenic silica in marine sediments with a relatively high clay mineral content.  相似文献   

18.
乌江流域水库沉积物中生物硅的测定方法及其环境意义   总被引:1,自引:0,他引:1  
采用碱提取法中的单点法与多点法相结合,测定了乌江流域水库沉积物中生物硅的含量,并对多点提取法进行了改良。采用多个离心管分装定量样品进行连续振荡,每小时提取1个样品进行测定。对多个时间点的提取结果,利用线性回归法分析得出最佳提取时间,优化最佳提取液,然后利用单点提取-硅钼蓝检测法测定沉积物中生物硅的含量。该方法既保证了单点法的快速,也减小了多点法的多次提取操作与提取时的体积误差。本文根据测定结果探讨了乌江流域水库沉积物中生物硅含量变化规律及其环境意义。  相似文献   

19.
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.  相似文献   

20.
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.  相似文献   

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