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1.
The cubic equation recently derived for the increase in concentration of a solute with time, as the solid dissolves in batch according to the shrinking sphere model at high under-saturation, is extended to dissolutions of mixtures of differently sized particles. This problem needs to be solved if batch dissolutions are to play their part in the proposed amelioration of global warming and associated climate change by accelerated ‘re-burial’ of excess CO2 in ocean sediment. The upgraded model was tested using sodium chloride dissolved in 50% aqueous propanone, whence the model fitted two separate runs with 500 and 212 μm, and 212 and 38 μm, diameter crystals, respectively. The key to simulating dissolution in this way lies in the dissolutions being independent of each other. It is further shown that although this condition was implicit in the recent derivation of the cubic equation, it was not recognised at the time. The work should be applicable to any batch dissolution of mixed particles at high under-saturation, and hence, may find use in many industrial and laboratory dissolutions. Simulations show how agglomerated mixtures can yield a straight line on the plot of ln(1 − C/C T) versus time, as was reported to occur recently with sodium chloride taken ‘straight from the bottle’. It is shown that this probably explains why exponential dissolutions may have seemed appropriate to the dissolution of biogenic silica in earlier literature. This study suggests that a new round of biogenic silica dissolutions, but with sieved samples, would be worthwhile, with the likelihood that shrinking sphere behaviour might well be found to characterise the kinetics. The opportunity is taken to investigate a number of aspects of the shrinking sphere model not generally discussed before, e.g. the graph for the change in surface area with time. The limitations of using cubic salt crystals with the shrinking sphere model are discussed.  相似文献   

2.
The dissolution of sieved sucrose crystals has been studied spectrophotometrically by observing the increase in dissolved sucrose concentration with time. Equations recently derived from the shrinking sphere model for the batch dissolution of a solid in under-saturated conditions tested successfully on both single crystal-size and mixtures of two sizes of sucrose crystals. Single-sized crystals provided a straight line for the plot of the fraction of un-dissolved solid to the power one-third, versus time ( vs. t). The dissolution of mixtures of two crystal sizes fitted the non-linear equation tested earlier on sodium chloride in water-propanone mixtures. Together, these two sets of tests on ionic and covalent substances verify that many simple dissolutions will be easily modelled using this physical model based on shrinkage, where the chemical composition of the solids is very much of secondary importance. Consequently, there is an increased chance that the equations will describe the dissolution of biogenic silica in seawater, the problem which originally inspired this study. More than this, though, the equations are discovered to be mathematically generic; very many geometries other than the sphere satisfy the same equations, and the “shrinking object dissolution model” is thereby defined. The approach should also apply even to non-aqueous dissolutions. A prototype plot of shrinking object rate constant (obtained from numerical fitting of the model to sucrose) versus particle size is presented, and it is shown how analogous treatments for other substances will be central to collection and use of much dissolution data in the future. The study is placed in context with much earlier solid phase decomposition studies, concluding that the key characteristic of the simplest of all dissolutions is that the interface between solid and liquid should advance at a uniform linear rate. It is shown how this approach leads to equations of the same mathematical forms already discussed above.  相似文献   

3.
Recent work has emphasized that the empirical rate equation for batch dissolution of a solid consists of a forward term involving the surface area minus a back reaction term involving surface area and concentration of dissolved solid. Integrated forms exist for use at extremes of high under-saturation and of very heavy solid loadings which lead to saturation. A middle condition allows for significant decrease in solid supply and simultaneous arrival at saturation. This study tests the three approaches simultaneously to the batch dissolution of gypsum, thereby demonstrating a consistent applicability of the afore-mentioned rate equation. Previously, some mineral dissolutions have displayed so-called nonlinear kinetics and hence have not appeared to conform to this rate equation. This paper provides a template for future investigation of those situations; dissolution experiments are not easy to perform, and instances of the so-called nonlinear kinetics may represent experimental artefact. The relationship between this empirical approach and that of Transition State Theory used in mineral dissolution is discussed, and a new, linear proof for the applicability of the ‘middle ground’ equations is demonstrated. Stirring experiments highlight the difference between the conditions in fluidized bed and laminar flow reactors. Gypsum dissolution is found to be transport limited at all but very vigorous laboratory stirring conditions, although the relationship between the rate of shrinkage of gypsum particles and stirring seems to be relatively simple. A stirring factor is applied to the rate equation overall to allow for differences in reactor design, and it is suggested that this should also be applicable to laminar flow reactors. The link between batch and chemo-stat dissolutions is stressed, together with a need to contour dissolution data on a new graph of particle size versus stirring rate.  相似文献   

4.
Recent success in fitting the shrinking object model for dissolution kinetics to biogenic silica, silica gel, simple salts, sucrose and gypsum prompted this study of the effects of common ions upon gypsum dissolution kinetics. Middle-ground dissolutions were mainly studied, in which shrinkage of the surface area, S, is significant, and the system approaches, but does not reach, saturation, c sat. Dissolution was monitored by conductimetry. At a constant ionic strength of 0.060 M, the net rate for gypsum dissolution is given by \textNet \textRate = k\textb ·S ·(c\textsat - c ) {\text{Net}}\,{\text{Rate}} = k_{\text{b}} \cdot S \cdot (c_{\text{sat}} - c ) , where k b is a rate constant, and c can be expressed alternatively in terms of either [Ca2+], [SO4 2−] and [ε±], that part of the electrolyte concentration contributed by gypsum dissolution, or as the equivalent total concentrations of these species, for example, [SO4 2−]T. The presence of either calcium or sulphate as a common ion slows dissolution, and the effect of this upon c sat, k b and k f, the forward rate constant, is discussed. Contrary to previous experience, it is emphasised that each fitting of the shrinking object model demands its own value of the Solubility of gypsum, c sat, which can be derived from the Solubility Product. This experience with gypsum is aligned with previous work on calcite, to develop a unified approach to the batch dissolution of salts. It highlights serious deficiencies in the way earlier common-ion experiments were conceived and enacted, and in particular with the rate equation of Sj?berg (Geochim Cosmochim Acta 40:441–447, 1976) for calcite above a pH of 7. Common-ion experiments are shown to be crucially important for probing the back reaction to dissolutions and might be applied to the far bigger problem of silicate-mineral dissolution, where ‘non-linear kinetics’ are often observed.  相似文献   

5.
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 (Casympt; 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 Casympt 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 Casympt 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.  相似文献   

6.
The full potential of batch dissolution experiments in geochemical and industrial applications has been hampered by the lack of an equation to describe the increase in dissolved solid concentration with time. This study provides new experimental results on the dissolution of salts and new equations, which describe dissolution according to the shrinking sphere model. Sieved salts were found to dissolve according to the shrinking sphere model while the dissolution of the parent material, raw (agglomerated) salt, fitted an exponential dissolution curve. The implications of this to the development of a systematic approach to batch dissolution, irrespective of the solid, is explored. Mathematical equations are derived for the dissolution of solids in under-saturated systems, which are much simpler than ones available, so far. In turn these provide easier comprehension of the workings of the shrinking sphere model. Finally, existing results for biogenic silica dissolution are reviewed in the light of the above-mentioned experimental and modelling advances. An earlier claim that shrinking sphere dissolution had been observed is refuted.  相似文献   

7.
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   

8.
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   

9.
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   

10.
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   

11.
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.  相似文献   

12.
利用粉煤灰制备多孔氧化硅的实验   总被引：3，自引：2，他引：1  
利用相分离原理,以粉煤灰经硅铝分离后所得的硅酸凝胶为原料,选用聚乙烯醇为造孔剂,硝酸为催化剂,成功地制备了多孔氧化硅。实验结果表明:制备的多孔氧化硅的孔道发育良好,含有三级孔道。扫描电镜分析显示:大孔孔径为1～2 μm,比表面积为12.03 m2/g,这与实际应用的硅藻土助滤剂制品大致相当。对实验制品在啤酒液中的稳定性实验结果显示:多孔氧化硅制品在浸泡于啤酒过程中几乎没有Ca2+、Fe3+离子溶出,浸泡后的啤酒液的pH值基本不变。上述结果表明:实验制备的多孔氧化硅制品作为硅藻土助滤剂的替代品具有良好的实际应用前景。  相似文献   

13.
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   

14.
Reactivity of biogenic silica: Surface versus bulk charge density   总被引：2，自引：0，他引：2  
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.  相似文献   

15.
通过对位于东海内陆架泥质区中部的MZ02孔进行粒度和生物硅分析,AMS14C测年,获得了粒度和生物硅随时间变化的高分辨率曲线.结果表明,近2 ka以来研究区沉积环境稳定,以沿岸流控制的浅海沉积为主;沉积物中生物硅含量<1.5%,属于低含量海区,主要受低硅质骨骼供给量、高溶解作用以及陆源物质冲淡作用的影响.生物硅含量及其...  相似文献   

16.
Observation under the electron microscope of diatom frustules from Bolivian Altiplano saline lakes shows that many of these are coated with particles occurring as tiny sheets. The frustules can be found to be almost completely replaced by these sheets. Isolated sheet aggregates seem to have resulted from completely transformed frustules. Section observations of altered frustules bear out that the sheets have grown from biogenic silica through replacement. Selected area diffraction, dark field observation, microdiffraction, and elemental microanalysis show that the particles on the diatom frustules consist of a poorly crystallized MG-smectite.The unambiguous localisation of this authigenesis allows us to reconstruct its hydrochemical and sedimentological environment. Observation of the most recent lake sediments has pointed out that at least two main conditions are required for this authigenesis at 5°C: saturation with respect to amorphous silica, and a pH above 8.2. Variations in the Mg concentration have no significant effect.  相似文献   

17.
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.  相似文献   

18.
Diatom ooze and diatomaceous mudstone overlie terrigenous mudstone beds at Leg 19 Deep Sea Drilling Project sites. The diatomaceous units are 300-725 m thick but most commonly are about 600 m. Diagenesis of diatom frustules follows a predictable series of physical and chemical changes that are related primarily to temperature (depth of burial and local geothermal gradient). During the first 300-400 m of burial frustules are fragmented and undergo mild dissolution. By 600 m dissolution of opal-A (biogenic silica) is widespread. Silica reprecipitates abundantly as inorganic opal-A between 600 and 700 m sub-bottom depth. Inorganic opal-A is rapidly transformed by crystal growth to opal-CT. The result is formation of silica cemented mudstone and porcelanite beds. A regional acoustic reflector (called the bottom-simulating reflector, or BSR) occurs near 600 m depth in the sections. This acoustic event marks the upper surface where silicification (cementation) is active. In Bering Sea deposits, opal-A is transformed to opal-CT at temperatures between 35° and 50°C. This temperature range corresponds to a sub-bottom depth of about 600 m and is the area where silicification is most active. Thus, the BSR represents an isothermal surface; the temperature it records is that required to transform opal-A to opal-CT. Deposition of at least 500 m of diatomaceous sediment was required before the temperature at the base of the diatomaceous section was appropriate (35°-50°C) for silica diagenesis to occur. Accordingly, silica diagenesis did not begin until Pleistocene time. Once silicification began, in response to sediment accumulation during the Quaternary, the diagenetic front (the BSR) moved upsection in pace with the upward migrating thermal boundary. X-ray diffractograms and SEM photographs show three silica phases, biogenic opal-A, inorganic opal-A’, and opal-CT. These have crystallite sizes of 11-16 A, 20-27 A, and 40-81 A, respectively, normal to 101. The d(101) reflection of opal-CT decreases with depth of burial at DSDP Site 192. This occurs by solid-state ordering and requires at least 700 m of burial. Most clinoptilolite in Leg 19 cores forms from the diagenesis of siliceous debris rather than from the alteration of volcanic debris as is commonly reported.  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.
Summary The kinetics of phytoplankton frustule dissolution has generally been studied as the appearance of silicic acid in a batch reactor. Unfortunately, this approach, though often illuminating, has not so far been successful because of the difficulty of parameterising the full reaction curve. This current study shows how the initial rate approach to chemical kinetics offers a way around this bottleneck, thereby allowing much chemical kinetics information about frustule dissolution to be collected. The technique is shown to be flexible and suited to short reaction times which facilitate detailed quantitative kinetics investigation, indeed, as would be expected in a solution phase, kinetics study. The technique is exemplified by a dissolution study of uncleaned frustules of Cyclotella crypticaat 40 °C and above. The frustules were found to yield the same dissolution rate after 5 weeks dark storage, at 4 °C. Meanwhile, log dissolution rate was found to vary linearly with pH, with gradient 0.38 ± 0.01 (r 2=0.990). Linearity was upheld even at pHs as high as 14. Finally, a robust Arrhenius plot was established between 40 and 90 °C yielding an activation energy for dissolution of 84 ± 3 kJ mol −1. Follow through with the Eyring equation yielded an activation enthalpy, ΔH ‡, and an activation entropy, ΔS ‡, of 81 and 85 J mol −1 K −1, respectively. The discussion brings salient aspects of existing knowledge about diatom frustule dissolution kinetics into the wider context of silicate mineral dissolution.  相似文献   

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