Reactivity of biogenic silica: Surface versus bulk charge density

Acid-base titrations were carried out at three different ionic strengths (0.01, 0.1 and 0.7 M NaCl) on a range of marine and continental biosiliceous materials. The large variability in electrical charging behavior of the various materials is consistent with the existence of two pools of ionizable groups, one on the outer surface of and the other within the silica particles. The relative amounts of internal and external silanols were estimated by fitting a two-site complexation model to excess proton versus pH curves obtained at the different ionic strengths. For fresh diatom frustules and phytoliths, as well as recently deposited biosiliceous sediments, the abundance of internal silanols was of the same order of magnitude as, or exceeded, that of silanols on the external surface. Older biosiliceous materials exhibited lower proportions of internal groups, while a decrease in the relative amount of internal silanols was also observed for diatom frustules artificially aged in seawater. The existence of internal ionizable functional groups explains measured charge densities of biogenic silicas that largely exceed the theoretical site density of silica surfaces. Variations in the relative abundance of internal versus surface silanols further explain the non-uniform dependence of electrical charging on ionic strength, the lack of correlation between total charge density and dissolution kinetics, and the variable 950 cm⁻¹ peak intensity in the infrared spectra of biogenic silicas. Dissolution rates correlate positively with the external charge, rather than the total charge build-up, as expected if dissolution only involves the removal of silicate units from the external surfaces of the particles. The progressive reduction with time of the internal to external silanol concentration ratio represents one of the mechanisms altering the material properties that affect the recycling and preservation of biogenic silica in earth surface environments.     

Surface chemistry and reactivity of plant phytoliths in aqueous solutions

In order to better understand the reactivity of plant phytoliths in soil solutions, we determined the solubility, surface properties (electrophoretic mobilities and surface charge) and dissolution kinetics of phytoliths extracted from fresh biomass of representative plant species (larch tree and elm, horsetail, fern, and four grasses) containing significant amount of biogenic silica. The solubility product of larch, horsetail, elm and fern phytoliths is close to that of amorphous silica and soil bamboo phytoliths. Electrophoretic measurements yield isoelectric point pH_IEP = 0.9, 1.1, 2.0 and 2.2 for four grasses, elm, larch and horsetail phytoliths respectively, which is very close to that of quartz or amorphous silica. Surface acid–base titrations allowed generation of a 2-pK surface complexation model (SCM) for larch, elm and horsetail phytoliths. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 1 ≤ pH ≤ 8, were found to be very similar among the species, and close to those of soil bamboo phytoliths. Mechanistic treatment of all plant phytoliths dissolution rates provided three-parameters equation sufficient to describe phytoliths reactivity in aqueous solutions:$R(\text{mol}/{\text{cm}}^2/\text{s})=6?{10}^{?16}?a_{\text{H+}}+5.0?{10}^{?18}+3.5?{10}^{?13}?a_{\text{OH}?}^{0.33}$Alternatively, the dissolution rate dependence on pH can be modeled within the concept of surface coordination theory assuming the rate proportional to concentration of > SiOH₂⁺, > SiOH⁰ and > SiO^? species. In the range of Al concentration from 20 to 5000 ppm in the phytoliths, we have not observed any correlation between their Al content and solubility, surface acid–base properties and dissolution kinetics.It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ～ 3. Mass-normalized dissolution rates are similar among all four types of plant species studied and these rates are an order of magnitude higher than those of typical soil clay minerals. The minimal half life time of larch and horsetail phytoliths in the interstitial soil solution ranges from 10–12 years at pH = 2–3 to < 1 year at pH above 6, comparable with mean residence time of phytoliths in soil from natural observations.     

Fractionation of silicon isotopes during biogenic silica dissolution

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 ε_DSi–BSi of −0.55‰, corresponding to a fractionation factor α_30/28 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.     

Inter-laboratory comparison of oxygen isotope compositions from biogenic silica

Several techniques have been introduced in the last decades for the dehydration and release of O₂ from biogenic silica (opal-A) for oxygen-isotope analysis. However, only one silica standard is universally available: a quartz standard (NBS28) distributed by the IAEA, Vienna. Hence, there is a need for biogenic silica working standards. This paper compares the existing methods of oxygen-isotope analyses of opal-A and aims to characterize additional possible working standards to calibrate the δ¹⁸O values of biogenic silica. For this purpose, an inter-laboratory comparison was organized. Six potential working standard materials were analysed repeatedly against NBS28 by eight participating laboratories using their specific analytical methods. The materials cover a wide range of δ¹⁸O values (+23 to +43‰) and include diatoms (marine, lacustrine), phytoliths and synthetically-produced hydrous silica. To characterize the proposed standards, chemical analyses and imaging by scanning electron microscopy (SEM) were also performed. Despite procedural differences at each laboratory, all methods are in reasonable agreement with a standard deviation (SD) for δ¹⁸O values between 0.3‰ and 0.9‰ (1σ). Based on the results, we propose four additional biogenic silica working standards (PS1772-8: 42.8‰; BFC: 29.0‰; MSG60: 37.0‰; G95-25-CL leaves: 36.6‰) for δ¹⁸O analyses, available on request through the relevant laboratories.     

Production and pelagic dissolution of biogenic silica in the Southern Ocean

Vertical distributions of particulate silica, and of production and dissolution rates of biogenic silica, were determined on two N-S transects across the Pacific sector of the Antarctic Circumpolar Current during the austral spring of 1978. Particulate silica profiles showed elevated levels in surface water and near the bottom, with low (35–110 nmol Si · 1^?1) and vertically uniform values through the intervening water column. Both the particulate silica content of the upper 200 m and the production rate of biogenic silica in the photic zone increased from north to south, reaching their highest values near the edge of the receding pack ice. A significant, but variable, fraction (18–58%) of the biogenic silica produced in the surface layer was redissolving in the upper 90–98 m. Net production of biogenic silica in the surface layer (production minus dissolution) was proceeding at a mean rate of ca. 2 mmol Si · m^?2 · day^?1. This is ca. 4 times greater than the most recent estimate of the mean accumulation rate of siliceous sediments beneath the ACC. We estimate, based on mass balance, that the mean dissolution rate of biogenic silica in subsurface water column in the Southern Ocean is 1.2–2.9 mmol Si · m^?2 · day^?1.     

Dissolution kinetics of biogenic silica from the water column to the sediments

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.     

Climatic influences on the oxygen isotopic composition of biogenic silica in prairie grass

Samples of Calamovilfa longifolia were collected from across the North American prairies to investigate the relationship between the oxygen-isotope composition of biogenic silica (phytoliths) deposited in this grass and relative humidity, temperature, and the oxygen-18 enrichment of soil water relative to local precipitation. The δ¹⁸O values of silica in nontranspiring tissues were controlled by soil-water composition and temperature, whereas the oxygen-18 content of silica formed in leaf and inflorescence tissues was enriched further by transpiration. Accurate calculation of growing temperature was possible only when the oxygen-isotope compositions of both stem silica and soil water were known. However, the oxygen-isotope values of stem phytoliths can be used to calculate the variation in the isotopic composition of soil water across a North American temperature gradient.As plant organic matter decays and phytoliths are transferred to the soil, the temperature and soil-water signals carried by the oxygen-isotope composition of silica from nontranspiring tissues can be masked by the oxygen-18 enrichment of phytoliths from transpiring tissues. However, the overall oxygen-isotope composition of a soil-phytolith assemblage can be related to temperature using an empirical relationship based on temperature and the difference between soil-phytolith and estimated soil-water oxygen-isotope compositions.     

Dissolution of silica from montmorillonite: effect of solution chemistry

The rate of silica removal from two montmorillonites (Chambers and Polkville) has been measured as a function of time, temperature, solution composition, and exchange ion on the clay. Silica removal rate increased with temperature from 200 to 350°C, decreased with time, and could be approximated initially by a parabolic rate law. Solution composition influenced silica removal rate by determining the exchange population of the clay; silica removal is most rapid when K-exchange ions are present. Thus increasing the concentration of K⁺ accelerated silica removal, whereas increasing the concentration of Na⁺, Ca²⁺, and Mg²⁺ inhibited silica removal. Activation energies for silica removal range from 5 to 10 kcal/mol. The largest values are associated with the largest concentrations of inhibitor ions in solution. Activation energies of this magnitude suggest that the rate-limiting step for silica removal is transport through a hydrated, expanded interlayer space. Application of experimental results to diagenesis in moderately to deeply buried sediments suggests that K⁺ uptake by montmorillonite may precede and accelerate illite formation.     

Benthic fluxes and the cycling of biogenic silica and carbon in two southern California borderland basins

Benthic fluxes in two southern California borderland basins have been estimated by modeling water column property gradients, by modeling pore water gradients and by measuring changes in concentration in a benthic chamber. Results have been used to compare the different methods, to establish budgets for biogenic silica and carbon and to estimate rate constants for models of CaCO₃ dissolution. In San Pedro Basin, a low oxygen, high sedimentation rate area, fluxes of radon-222 (86 ± 8 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.9 ± 0.3 mmol m⁻² d⁻¹) and nitrate (−0.8 ± 0.1 mmol m⁻² d⁻¹) measured in a benthic chamber agree within the measurement uncertainty with fluxes estimated from modeling profiles of nutrients and radon obtained in the water column. The diffusive fluxes of radon, SiO₂ and TCO₂ determined from modeling the sediment and pore water also agree with the other approaches. Approximately 33 ± 13% of the organic carbon and 37 ± 47% of the CaCO₃ arriving at the sea floor are recycled. In San Nicolas Basin, which has larger oxygen concentrations and lower sedimentation rates than San Pedro, the fluxes of radon (490 ± 16 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.7 ± 0.2 mmol m⁻² d⁻¹), oxygen (−0.7 ± 0.1 mmol m⁻² d⁻¹) and nitrate (-0.4 ± 0.1 mmol m⁻² d⁻¹) determined from chamber measurements agree with the water column estimates given the uncertainty of the measurements and model estimates. Diffusion from the sediments matches the lander-measured SiO₂ and PO₄³⁻ (0.017 ± 0.002 mmol m⁻² d⁻¹) fluxes, but is not sufficient to supply the radon or TCO₂ fluxes observed with the lander. In San Nicolas Basin 38 ± 9% of the organic carbon and 43 ± 22% of the CaCO₃ are recycled. Approximately 90% of the biogenic silica arriving at the sea floor in each basin is recycled. The rates of CaCO₃ dissolution determined from chamber flux measurements and material balances for protons and electrons are compared to those predicted by previously published models of CaCO₃ dissolution and this comparison indicates that in situ rates are comparable to those observed in laboratory studies of bulk sediments, but orders of magnitude less than those observed in experiments done with suspended sediments.     

Deep-sea biogenic silica: new structural and analytical data from infrared analysis - geological implications

The main parameters of infrared spectra have been investigated for marine siliceous skeletons and for silica polymorphs. From infrared (IR)data, the mean values for the Si-O bond length (1.62 Å) and for the Si-O-Si angle (about 142°6) are inferred for biogenic silica. A model is proposed for the molecular structure of biogenic, amorphous silica, which consists of a discontinuous, three-dimensional framework of short chains of [SiO₄] tetrahedra, bounded with apical hydroxyls. According to the relationship between the structure of the silica polymorphs and their infrared spectra, it is shown that a quantitative analysis of biogenic silica seems to be possible in quartz-rich sediments. Some geological implications of these data are emphasized, including the processes of siliceous skeleton sedimentation and diagenetic evolution.     

Surface chemistry,etch pits and mineral-water reactions

The role of surface chemistry and defects in the formation of etch pits in minerals is analyzed. Elastic properties, surface free energies, and dislocation characteristics are incorporated into a theory which predicts the outcome of dislocation-controlled dissolution for a variety of free energies of reaction with aqueous solutions. The influence of the core regions of dislocations on the etch pit formation is also developed. The predictions of the analytic theory are compared with the situations to be expected in natural solutions. Finally, the powerful Monte Carlo method is introduced as a means to study mineral dissolution. The method enables a close scrutiny of the simplified analytic theory and significantly extends it.     

Effects of river damming on biogenic silica turnover: implications for biogeochemical carbon and nutrient cycles

Rivers link terrestrial ecosystems and marine ecosystems, and they transport large amounts of substances into oceans each year, including several forms of silicon (Si), carbon (C), and other nutrients. However, river damming affects the water flow and biogeochemical cycles of Si, C, and other nutrients through biogeochemical interacting processes. In this review, we first summarize the current understanding of the effects of river damming on the processes of biogeochemical Si cycle, especially the source, composition, and recycling process of biogenic silica (BSi). Then, we introduce dam impacts on the cycles of C and some other nutrients. Dissolved silicon in rivers is mainly released from phytolith dissolution and silicate weathering. BSi in suspended matter or sediments in most rivers mainly consists of phytoliths and mainly originates from soil erosion. However, diatom growth and deposition in many reservoirs formed by river interception may significantly increase the contribution of diatom Si to total BSi, and thus significantly influence the biogeochemical Si, C, and nutrient cycles. Yet the turnover of phytoliths and diatoms in different rivers formed by river damming is still poorly quantified. Thus, they should be further investigated to enhance our understanding about the effects of river damming on global biogeochemical Si, C and nutrient cycles.     

近33ka以来辽河口沉积环境演变与生物硅记录

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。     

Distribution and sources of carbon,nitrogen, phosphorus and biogenic silica in the sediments of Chilika lagoon

The present study investigated the spatial and vertical distribution of organic carbon (OC), total nitrogen (TN), total phosphorus (TP) and biogenic silica (BSi) in the sedimentary environments of Asia’s largest brackish water lagoon. Surface and core sediments were collected from various locations of the Chilika lagoon and were analysed for grain-size distribution and major elements in order to understand their distribution and sources. Sand is the dominant fraction followed by silt + clay. Primary production within the lagoon, terrestrial input from river discharge and anthropogenic activities in the vicinity of the lagoon control the distribution of OC, TN, TP and BSi in the surface as well as in the core sediments. Low C/N ratios in the surface sediments (3.49–3.41) and cores (4–11.86) suggest that phytoplankton and macroalgae may be major contributors of organic matter (OM) in the lagoon. BSi is mainly associated with the mud fraction. Core C5 from Balugaon region shows the highest concentration of OC ranging from 0.58–2.34%, especially in the upper 30 cm, due to direct discharge of large amounts of untreated sewage into the lagoon. The study highlights that Chilika is a dynamic ecosystem with a large contribution of OM by autochthonous sources with some input from anthropogenic sources as well.     

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.     

A new protocol for oxygen isotope analysis of authigenic and biogenic fine silica grains using laser-extraction technique

We report here a 30 W CO₂ laser heating protocol for analyzing oxygen isotope composition (δ¹⁸O in ‰ vs. V-SMOW) of quartz and amorphous silica grains lower than 50 and 2 μm with a good external precision (1σ < 0.15‰). This technique is used to investigate δ¹⁸O composition of macro-, micro- and crypto-crystalline quartz cements of quartzite levels occurring in a sand sequence from the South of France (Apt Series), after a physical separation of the quartz cements. δ¹⁸O data obtained from this technique are compared with δ¹⁸O data obtained from in situ ion microprobe analyses. This study also presents promising results on δ¹⁸O analysis of phytoliths obtained with the laser heating protocol (1σ < 0.1‰).     

Surface chemistry of disordered mackinawite (FeS)

Disordered mackinawite, FeS, is the first formed iron sulfide in ambient sulfidic environments and has a highly reactive surface. In this study, the solubility and surface chemistry of FeS is described. Its solubility in the neutral pH range can be described by K_s^app = {Fe²⁺} · {H₂S(aq)} · {H⁺}⁻² = 10^+4.87±0.27. Acid-base titrations show that the point of zero charge (PZC) of disordered mackinawite lies at pH ∼7.5. The hydrated disordered mackinawite surface can be best described by strongly acidic mono-coordinated and weakly acidic tricoordinated sulfurs. The mono-coordinated sulfur site determines the acid-base properties at pH < PZC and has a concentration of 1.2 × 10⁻³ mol/g FeS. At higher pH, the tricoordinated sulfur, which has a concentration of 1.2 × 10⁻³ mol/g FeS, determines surface charge changes. Total site density is 4 sites nm⁻². The acid-base titration data are used to develop a surface complexation model for the surface chemistry of FeS.     

Estimation of authigenic alteration of biogenic and reactive silica in Pearl River estuarine sediments using wet-chemical digestion methods

The extent of authigenic alteration of biogenic and reactive silica in Pearl River estuarine sediments has been estimated using wet-chemical digestion methods. Results show relatively constant distributions of biogenic and reactive Si horizontally and vertically. Based on three core measurements, the biogenic and total reactive Si average 77.91 and 264.77 μmol Si g⁻¹, respectively. Their extents of authigenic alteration are correspondingly estimated as ~55.6 and ~70.6%. The average biogenic Si accumulation rate is calculated as 1.91 × 10⁹ mol Si year⁻¹, which translates into storage of ~7.15% of the annual riverine dissolved silica input. By contrast, the total reactive Si accumulation rate is as high as 6.49 × 10⁹ mol Si year⁻¹, improving annual riverine silicic acid storage to ~24.19%. Detailed investigation is required for a good understanding of early diagenetic process of biogenic and reactive silica in this subtropical area.     

High-temperature carbon reduction of silica: A novel approach for oxygen isotope analysis of biogenic opal

A new technique has been developed for the determination of the oxygen isotope composition from biogenic silica. The iHTR method (inductive high temperature carbon reduction) is based on the reduction of silica by carbon with temperatures of up to 1830°C (maximum T 2200°C) to produce carbon monoxide for isotope analysis. Basically, samples of silica are mixed with graphite and filled into a sample holder made of a glassy carbon rod. The rod is introduced into a glassy carbon cylinder liner closed at the top which itself is enclosed by a double-walled glass vessel. The glassy carbon rod is inductively heated under vacuum to the temperature needed for quantitative conversion of the particular silica material to CO. The most critical process of dehydration (in the case of opal) and reduction to CO is routinely achieved in the iHTR device. Weakly bound oxygen and oxygen-containing contaminants, like hydroxyl groups, as well as remaining minor organic constituents are volatilized stepwise under high vacuum at temperatures of 850°C and 1050°C without isotopic exchange before the reduction of the silica. After completion of dehydration, the temperature is raised to the value needed for silica reduction. For both biogenic silica and quartz a temperature of 1550°C was found to be adequate. The technical design with a standard preparation routine and various test experiments is presented proving the reliability and capability of the new iHTR method, especially with respect to fresh diatom materials and diatom opal. The amount of sample material necessary at present is ∼1.5 mg of silica and the reproducibility achieved for natural samples is better than ±0.15‰. Replicate analysis of the quartz standard NBS28 resulted in a δ¹⁸O value of 9.62‰ ± 0.11‰ (n = 17).