Determining Biogenic Silica in Marine Samples by Tracking Silicate and Aluminium Concentrations in Alkaline Leaching Solutions

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.     

Dissolved Al in sediments and waters of the East China Sea: Implications for authigenic mineral formation

Numerous previous studies indicate that several different authigenic aluminosilicates form in the oceans. In this study we show, using dissolved Al distributions in sediments and waters from the nearshore regions of the East China Sea, that the process of aluminosilicate formation probably begins rapidly upon contact of detrital clays with seawater. Statistical analyses of dissolved Al-Si-H⁺ relations in surface sediments indicate that the minerals forming in East China Sea sediments low in dissolved Fe are dioctahedral chlorites with an average composition EX_0.91Mg_0.77Al_5.0Si_2.7O₁₀(OH)₈ (where EX = exchangeable + 1 cation). This composition is also consistent with dissolved Al and Si measurements as a function of salinity in turbid overlying waters. Results suggest a dissolution—reprecipitation mechanism for clay mineral reconstitution. This mechanism can help to explain why different authigenic clays are found in different areas of the oceans. In the East China Sea the total amount of authigenic clays present must constitute a very minor fraction of the bottom sediments. Thus, the formation of these minerals has a relatively small impact upon dissolved Si distributions. Clay mineral reconstitution in nearshore regions may provide a mechanism for buffering sediments and overlying waters with respect to pH, as the composition of minerals formed should be a direct function of the H⁺ activity in the surrounding environment.     

Germanium/silica ratios in diagenetic chert nodules from the Ediacaran Doushantuo Formation,South China

Germanium/silica (Ge/Si) ratios of dolostone- and mudstone-hosted chert nodules from the Ediacaran (635–542 Ma) Doushantuo Formation in the Yangtze Gorges area, South China, are reported. These chert nodules typically have a calcite rim, a pyrite rim, and a silica core, the latter sometimes containing disseminated pyrite. The silica core was precipitated by early diagenetic replacement of carbonate and silty/muddy sediments. Two types of chert nodules are identified based on their mineralogy and geochemistry. Type-1 chert nodules are poor in disseminated pyrite in the silica core. They also have low Al, and show a strong positive correlation between Al contents and Ge/Si with a near-zero or negative intercept. In contrast, Type-2 chert nodules contain abundant disseminated pyrite in the silica core and show a weakly positive correlation between Ge/Si ratios and Al contents (with a large positive intercept on the Ge/Si axis). The Ge/Si of Doushantuo nodules are greater than those of Cretaceous deep-sea cherts, suggesting that the Ge/Si ratio of Ediacaran seawater/porewater was greater than the Cretaceous due to the more effective discrimination against Ge by inorganic opal precipitation relative to biogenic opal precipitation. The positive correlation between Ge/Si and Al can be interpreted using a mixing model with a pure chert (characterized by a low Ge/Si ratio) and an Al-rich endmember (characterized by a high Ge/Si ratio). The latter is most likely represented by a clay component, but the model-based estimate of the Ge/Si ratio inferred for the Al-rich (clay) endmember is much higher than that of Phanerozoic clay minerals. These high Ge/Si ratios for the clay endmember may be related to the generally high Ge/Si ratio of Ediacaran seawater, but could also be related to clay–organic matter interactions. Organic matter absorbed to clays could provide an additional source of Ge because certain organic molecules are known to have a high affinity for Ge due to their strong metal ion-chelating properties. The high Ge/Si ratio of the Al-rich endmember in Type-1 chert nodules suggests that Ge in porewaters from which these cherts precipitated may have been dominated by Ge–organic complexes. The low Ge/Si ratio inferred for the Al-rich endmember in Type-2 chert nodules is therefore taken to indicate that Ge was released from organic matter, perhaps due to anaerobic degradation of organic matter (accompanied by the formation of pyrite), and was redistributed between clay–organic endmembers and pure chert, resulting in a non-zero intercept in the Ge/Si vs. Al₂O₃ plots. These observations suggest that a strong terrestrial influence in a restricted sedimentary basin or a high content of dissolved organic carbon in Ediacaran seawater and porewater may have contributed to the dominance of Ge–organic complexes in the Doushantuo basin in the Yangtze Gorges area.     

Sorption of silica by clay minerals

Clay minerals were reacted with silica-spiked solutions of unbuffered distilled water; water buffered at pH 5.5, 8 and 10; alkali chloride solutions; natural and artificial sea water to assess the influence of pH, silica and cation activities. The data are plotted as silica produced by dissolution or sorption of silica by clay surface as a function of initial silica concentration at a given pH and solution composition. This allows the determination of the dissolved silica value at which the clay mineral surface neither dissolves nor sorbs silica. The values of the various activities in different solutions are used to infer the phase equilibria between solution, clay mineral and the surface phase produced either by dissolution or sorption. Most intensively investigated were sorption reactions of kaolinite in sea water and other ionic solutions to form silica-rich, cation-rich surface phases in cationic solutions and silica-rich phases in cation-free solutions.Inferred equilibrium constants imply that silicate reconstitution is doubtful as a mechanism for partial control of silica and cation composition of sea water but is reasonable in silica-rich interstitial waters.     

Tracing mechanisms controlling the release of dissolved silicon in forest soil solutions using Si isotopes and Ge/Si ratios

The terrestrial biogenic Si (BSi) pool in the soil-plant system is ubiquitous and substantial, likely impacting the land-ocean transfer of dissolved Si (DSi). Here, we consider the mechanisms controlling DSi in forest soil in a temperate granitic ecosystem that would differ from previous works mostly focused on tropical environments. This study aims at tracing the source of DSi in forest floor leachates and in soil solutions under various tree species at homogeneous soil and climate conditions, using stable Si isotopes and Ge/Si ratios. Relative to granitic bedrock, clays minerals were enriched in ²⁸Si and had high Ge/Si ratios, while BSi from phytoliths was also enriched in ²⁸Si, but had a low Ge/Si ratio. Such a contrast is useful to infer the relative contribution of silicate weathering and BSi dissolution in the shallow soil on the release of DSi in forest floor leachate solutions. The δ³⁰Si values in forest floor leachates (−1.38‰ to −2.05‰) are the lightest ever found in natural waters, and Ge/Si ratios are higher in forest floor leachates relative to soil solution. These results suggest dissolution of ²⁸Si and Ge-enriched secondary clay minerals incorporated by bioturbation in organic-rich horizons in combination with an isotopic fractionation releasing preferentially light Si isotopes during this dissolution process. Ge/Si ratios in soil solutions are governed by incongruent weathering of primary minerals and neoformation of secondary clays minerals. Tree species influence Si-isotopic compositions and Ge/Si ratios in forest floor leachates through differing incorporation of minerals in organic horizons by bioturbation and, to a lesser extent, through differing Si recycling.     

铝硅酸盐矿物成岩演化对形成过渡带气的影响

生油成气的过程不只是简单的有机物之间的转化，而是无机和有机两个系统综合运动的产物，它们之间相互联系相互制约。成岩作用伊始，两系统独立演化，均受成岩环境的制约。一旦环境适合于有机物裂化分解，两系统就共同发挥作用，通过质子的转移而相互作用。由于生物热催化过渡带气埋藏浅、热演化程度不高等特点，铝硅酸盐矿物成岩作用主要表现为:砂质岩以机械压实作用、胶结作用、溶解作用、矿化交代、自生矿物充填作用为主，泥质岩最显著的变化就是矿物的成岩演化，即蒙脱石→伊／蒙混层→伊利石，及蒙脱石→绿／蒙→绿泥石的成岩演化，其实质是有机与无机相互作用，即赋存在粘土中有机质的有机酸使砂质岩发生溶解，和碎屑岩溶解孔隙水中的Ａｌ３＋替代蒙脱石晶层间的Ｓｉ４＋，形成质子酸，对有机质形成过渡带气起着催化作用。     

The association of organic molecules with clay minerals in aqueous solutions

The uptake of dissolved organic molecules by kaolinite and montomorillonite clay minerals was measured in distilled water and saltwater solutions. Glucose and valine exhibited low affinities for both clay minerals over a wide range of concentrations in distilled water and seawater solutions. Stearic acid was efficiently removed by both clay minerals from all solutions over the concentration range 10–1000 ppb. These experiments suggest that some dissolved organic molecules may be preferentially removed by clay minerals in natural waters. It is unlikely, however, that the partitioning of simple organic molecules between natural waters and suspended clay minerals could produce the high concentrations of organic matter that occur in most fine-grained sediments.     

Illite mineral synthesis at surface temperatures

The synthesis of illite mixed-layer minerals at surface conditions is possible through precipitation of Al hydroxides from Si-, Mg- and K-containing solutions. It has been shown that amorphous hydroxides of Al, Fe, etc. are capable of coprecipitating silica even from very dilute solutions. By aging of these X-ray amorphous hydroxide—silica precipitates under certain conditions, clay minerals can be synthesized at low temperatures. The presence of Mg particularly favors the formation of three-layer clay minerals. Mg-rich Al hydroxide—silica precipitates permit formation of tri- and di-octahedral smectite, illite and chlorite. The formation of three-layer clay minerals is only possible when the precipitates contain at least 6% MgO. The precipitates stay amorphous if the Mg content is lower. The adsorption of Mg and K on the hydroxide—silica precipitate controls the illite or montmorillonite portion in the mixture of the three-layer silicates. There is a competition for K and Mg adsorption on the hydroxide—silica precipitates. Higher K concentration inhibits the three-layer mineral formation through the lowering of the Mg content in the precipitates. Illite mineral formation is favored under certain K/Mg ratios. Higher NaCl contents do not favor the three-layer mineral formation.The enrichment of Mg and K in the precipitates is not as large as the enrichment of Si in the hydroxides. This means that the illite mineral formation is only possible from solutions with a high-salt content like seawater.     

Extent of diagenetic transformations in severely altered biogenic silica deposits from Tunisia: new insights from mineralogy and geochemistry

Sedimentary biogenic silica from Redeyef in Gafsa basin (southern Tunisia) was analysed for its ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra and complemented by X-ray diffraction and SEM observations. The ²⁹Si MAS NMR spectrum is characterized by the abundance of hydroxylated silicon, displayed in resonance intensities and reflects a clear tendency towards dissolution of diatomaceous amorphous silica and the occurrence of the hydrated silica, which is the main component that ensures the diagenetic transition via the mechanism of dissolution–precipitation to other more crystalline silica phases, after the lost of its hydroxyls groups (water) by heating (burial). ²⁷Al MAS NMR reveals two coordinations of Al; the octahedrally coordinated Al suggests the presence of clay relics trapped during crystal growth or a microcrystalline zeolite (clinoptilolite detected by SEM observations), while the tetrahedrally coordinated Al suggests the presence of minor quantities of minerals with tetrahedral Al, such as an Al-rich fluid and/or minerals such as feldspars.     

Silicification of Riphean Carbonate Sediments (Yurubcha-Tokhomo Zone,Siberian Craton)

Types and lateral and vertical distribution of silicification in Riphean (largely dolomitic) rocks of the Yurubcha-Tokhomo zone of the Siberian Craton are discussed. It is shown that quartz and pyroclastic material in sediments were subjected to intense dissolution in a highly alkaline Riphean basin with the release of silica. Rapid and abrupt decrease in alkalinity during hiatus and desiccation periods resulted in the precipitation of dissolved silica and silicification of near-surface sediments. Lateral distribution of silicification was controlled by the redistribution of silica during the pre-Vendian hiatus, when surface waters were filtered through a carbonate massif with the simultaneous karst formation and silica dissolution. In the water discharge area, secondary silica was precipitated owing to changes in pH values and other physicochemical conditions.     

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.     

Diagenesis of siliceous oozes—I. Chemical controls on the rate of opal-A to opal-CT transformation—an experimental study

Evidence from deep-sea sediments supports the following diagenetic maturation sequence: opal-A (siliceous ooze) → opal-CT (porcelanite) → chalcedony or cryptocrystalline quartz (chert). A solution-redeposition mechanism is involved in the opal-A to opal-CT transformation. Exceptions to the overall maturation sequence are numerous, suggesting that temperature and time are not the only important factors controlling these mineralogical transformations. The rates of the above transformations are strongly affected by the composition of the solution and of the host sediments ; in Mesozoic clayey sediments, opal-CT predominates, while in carbonate sediments quartz is most common.Experiments at 25 and 150°C over a period of one day to six months show that the transformation rate of opal-A to opal-CT is much higher in carbonate than in clay-rich sediments, and that opal-CT lepisphere formation is aided by the precipitation of nuclei with magnesium hydroxide as an important component. The role of carbonate is explained as follows : in carbonate-rich sediments, the dissolution of carbonate provides the necessary alkalinity, and sea water provides the magnesium for the magnesium hydroxide in the nuclei. In contrast, in clay-rich sediments the clay minerals compete with opal-CT formation for the available alkalinity from sea water. As a result, the clays are enriched in Mg, and the rate of opal-CT formation is strongly reduced. This mechanism also bears on the common observation of carbonate replacement by silica.     

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.     

Biodegradation of clay minerals: laboratory experiments and results from Wadden Sea tidal flat sediments

Laboratory experiments indicate that clay particles of the <2-üm fraction can be considerably degraded by the bivalve Mytilus edulis: dickite, kaolinite, smectite, chlorite and illite particles are partially dissolved and rounded by the digestive processes. Structural changes and a decrease in crystallinity of kaolinites, dickites and illites are striking. Investigations of clay minerals from tidal flat sediments highly populated by marine invertebrates, from marine suspensions and samples from profiles across Mytilis edulis beds on the North Sea coast of Germany show, however, that these materials have a uniform mineral composition. This uniformity of clay mineralogy can be explained by the hydrodynamic conditions in the nearshore area, where tidal currents and waves cause a periodic resuspension and transport of sediments introduced into the Wadden Sea from different sources (glacial, fluviatile). Processes of bioturbation also redistribute the sedimentary material. These mixing processes effectively erase any evidence of local enrichment of the biogenically degraded clays. However, the disordered clays should react more sensitively (i.e. have higher adsorption capacities for organic substances, hydroxides and metals) in sediments than untreated materials, so that biodegradation is of basic importance for clay diagenesis. During these processes, Pb, V, Ni and Fe are dissolved from the digested particles.     

Very early diagenesis in a calcareous,organic-rich mudrock from Jordan

The diagenesis in the organic-rich Cretaceous to Eocene Al Hisa Phosphorite Formation (AHP), Muwaqqar Chalk Marl Formation (MCM) and Umm Rijam Chert-Limestone Formation (URC) formations of Jordan can be linked directly to the fluctuating sedimentary environment of this shelf depositional system in the Middle to Late Eocene, and its influence on the composition of the deposited sediment and the early burial diagenetic environment. Most cementation was early, mostly within the first 10 m of burial, perhaps entirely within the first 100 m of burial. We propose that the siliceous cements are derived from biogenic silica, probably of diatoms, deposited in a shelf of enhanced productivity. Volumetrically, the most important processes were the redistribution of biogenic opal-A (diatoms) and calcite to form pervasive, layered and nodular cements. The formation of the silica and carbonate cements is closely linked through the effects their dissolution and precipitation have on pore fluid chemistry and pH. The chert beds have a biogenic silica origin, formed through replacement of diatoms and radiolaria by opal-CT, and subsequently by quartz. Calcite cement has carbonate derived from microbial diagenesis of organic matter and calcium derived from seawater. The Mg for early dolomite may have been generated by replacement of opal-CT by quartz, ore dissolution of unstable high Mg calcite bioclasts. The silica and carbonate diagenetic processes are both linked to microbial diagenesis of organic matter, and are intimately linked in both time and space, with pH possibly influencing whether a silica or a carbonate mineral precipitates. The paucity of metal cations capable of precipitating as sulphides is crucial to the creation of acidic pore water favourable to silica precipitation, either as opal-CT, chalcedony or quartz. The lack of clay minerals as a sink for the Mg required for opal-CT polymerisation is the principal factor responsible for the remarkably early silica cementation. All the diagenetic processes, with the probable exception of the opal-CT to quartz transition are early, almost certainly within the first 10 m of burial, possibly much less. A paragenetic sequence is presented here based on these two cores that should be tested against a wider core distribution to see whether this diagenetic history can be generalised throughout the basin. Warm bottom water temperatures probably led to silica diagenesis at much shallower burial depths than occurs in many other sedimentary basins. Silicified layers, in turn, commonly host fractures, suggesting that mechanical properties of the strata began to differentiate at a very early stage in the burial cycle. This has wide implications for processes linking diagenesis to deformation.     

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.     

Mineralogy and chemistry of bentonite (?) deposits at Minjingu, Lake Manyara, North Tanzania

Olive green clays likely to be bentonitic in composition have been mineralogically and chemically studied. They occur in association with other lacustrine sediments at Lake Manyara. Radiocarbon dates from four diatom horizons indicate ages ranging from 12 Ka to 135 Ka suggesting a Mid-Holocene age. Middle Pleistocene age have been assigned to the ridged oncolites of Lake Manyara. The olive green coloured clays in the Manyara basin are known to occur in association with other lake beds including phosphorite deposits, stromatolites, bioturbated silty clays, partly silicified marls, conglomerates and olive green coloured opal beds. The results presented herein are from the olive green coloured clays. The olive green clays (bentonite?) are a result of devitrification or alteration of volcanic ashes and/or pyroclasts. The green clays occur in different forms as they are separated from each other by other lacustrine sediments. The alteration might have taken place in slightly different environments in terms of salinity and alkalinity. One of the top layer is friable and shows conchoidal fractures when dry. The other beds below in the lacustrine sequence are cemented with calcite and some dolomite as well as zeolites. The lowermost layer in the sequence is friable and shows cracks filled with coarse crystalline calcite. Mineralogically the bentonite is composed of the clay minerals illite, illite-smectite mixed layer clays, and chlorite. Other authigenic minerals include various zeolites (analcime, clinoptilolite, erionite and some traces of mordenite), opal, and fluorapatite. The clays have magnesium contents varying from 3.01% to 7.43%. The calcium contents vary widely due to presence or absence of one of the two minerals calcite or apatite. Trace elements like Ba, Ce, Sr, Zr are equally attributed to the presence of calcite and apatite. The formation of the illite-smectite mixed layer clays in an alternating manner with other lake sediments depicts different episodes of volcanic eruptions in the area. The mineralogical composition of smectites, zeolites, and opal in the green clays suggests a deposition of pyroclasts and volcanic ashes in a closed lake system with fluctuating levels. Due to evaporation alkalinity and salinity levels were fluctuating. The clays might have been bentonite which have undergone illitisation, a phenomena noted in other neighbouring rift basins.     

Dissolution Characteristic Study on Dustfall in Citric

In this paper, the dissolution characteristics of Xining dustfall in citric acid solution was studied to evaluate the physical chemical change in acid conditions. pH along with conductivity was tested with time. FTIR, SEM and ICP analysis were applied to analyze the residuum and filtrate after 2 days’ dissolution experiment. It was shown in the pH/conductivity variation, solution’s pH rise sharply in the front 4 hours, then decrease slowly. After 4 hours, both the pH and conductivity become stable. Based on combined analysis of XRD and FTIR spectrum of dustfall before and after dissolution, that calcite and dolomite in dustfall are dissolved completely in the 0.05M citric acid solution in two days. Besides, amount of metal cations were extracted from the dustfall during the dissolution, including Ca2+,K+,Mg2+,Fe3+,Al3+,Si. In general, after the dissolution of dustall in citric acid, some minerals are dissolved and amount of metal elements are extracted. Carbonate minerals almost dissolved completely, also the structure of silicate minerals changed as the extraction of elements.     

Dissolution kinetics of soil clays in sulfuric acid solutions: Ionic strength and temperature effects

Significant amounts of sulfuric acid (H₂SO₄) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline–acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline–acidic conditions (pH 1–4; ionic strengths = 0.01 and 0.25 M; 25 °C) and over a range of temperatures (25–45 °C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2–4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; R_Si, R_Al, R_Fe) increased with decreasing solution pH and increasing temperature. For example, the highest log R_Si value was obtained at pH 1 and 45 °C (−9.07 mol g⁻¹ s⁻¹), while the lowest log R_Si value was obtained at pH 4 and 25 °C (−11.20 mol g⁻¹ s⁻¹). A comparison of these results with pure mineral dissolution rates from the literature suggests that the BB clay dissolved at a much faster rate compared to the pure mineral samples. Apparent activation energies calculated for the clay sample varied over the range 76.6 kJ mol⁻¹ (pH 1) to 37.7 kJ mol⁻¹ (pH 4) which compare very well with the activation energy values for acidic dissolution of monomineralic samples e.g. montmorillonite from previous studies. The acid neutralisation capacity (ANC) of the clay sample was calculated from the release of all structural cations except Si (i.e. Al, Fe, K, Mg). According to these calculations an ANC of 1.11 kg H₂SO₄/tonne clay/day was provided by clay dissolution at pH 1 (I = 0.25 M, 25 °C) compared to an ANC of 0.21 kg H₂SO₄/tonne clay/day at pH 4 (I = 0.25 M, 25 °C). The highest ANC of 6.91 kg H₂SO₄/tonne clay/day was provided by clay dissolution at pH 1 and at 45 °C (I = 0.25 M), which is more than three times higher than the ANC provided under the similar solution conditions at 25 °C. In wetlands with little solid phase buffering available apart from clay minerals, it is imperative to consider the potential ANC provided by the dissolution of abundantly occurring phyllosilicate minerals in devising rehabilitation schemes.