Diagenesis of late Cenozoic diatomaceous deposits and formation of the bottom simulating reflector in the southern Bering Sea*

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.     

苏皖坡缕石粘土中蛋白石特征及其成因意义

TEM和XRD研究表明，在苏皖坡缕石粘土矿床的蛋白石坡缕石层中存在0pal-A和0pal-CT两种结构的蛋白石。蛋白石坡缕石层主要含坡缕石、opal-A、opal-CT，以及少量白云石和其它矿物，由富opal-A层和富opal-CT层互层组成，交互层的厚度在几个厘米左右。蛋白石坡缕石层中的矿物基本是自生矿物，从蒸发湖水中化学沉淀形成。矿物组成特征研究表明，蛋白石坡缕石层的矿物组分(Si、Mg、Al)来源于盆地周围玄武岩淋滤的浅层地下水。根据Opal-A和Opal-CT溶解度图解和城缕石、白云石形成物理化学条件图解，当湖水具有高浓度溶解SiO2和Mg^2 时，有利于opal-A和坡缕石形成，当湖水具有低浓度溶解SiO2时，有利于opal-CT结晶。因此，沉淀SiO2的结构状态取决于地下水补给的湖水溶解SiO2浓度。富opal-A和富opal-CT交互层的形成是古气候、古水文周期性变化的指示。富opal-CT层指示高地下水补给流入量，低蒸发量，湖水低盐度和溶解组分，代表湿润气候时期；而富opal-A层代表低地下水补给流入量，高蒸发量，高溶解组分浓度，代表干旱气候时期。     

Diagenesis of the Sedimentary Rocks Enclosing Coaly Layers in Gavatha Area,Lesvos Island,Based on Silica Polymorph‘s Transformations

A Tertiary non-marine stratigraphic sequence composed of carbonates(limestone),siliceous carbonates,coaly layers overlain by pyroclastic rocks and lavas,outcrops in the Gavatha area of northwestern Lesvos Island.Pure earbonates eonsist almost completely of calcite,the siliceous carbonate sediments of quartz,opal-CT and calcite,the shales of quartz,opal CT, K-feldspar,smecite-illite and ealcite,and the coaly layers of organic matter,quartz,opal-CT,feldspars and pyrite,Geochemical data indicate that smectite-illite,feldspars and associated elements(La,Zr,Y,Ba,Ce)are the products of alteration of volcanic rocks in a subtropical area A combination of sources in suggested for the formation of silica polymorphs:(a) biogenic or non-biogenic silica(opal-A) that was originally present in the form of diatiom frustules of in the form of inorganically prccipitated silica;(b)transformation o opall-A to opal-CT and quartz opal-C from alteration of volcanic glass of intercalated tuffites and overlying volcanics;and(c)opal-CT deposited primarily from hydrothermal solutions.     

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

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

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.     

Mineralogical and textural changes accompanying ageing of silica sinter

Twenty nine samples of silica sinter, ranging in age from modern to Miocene, record temporal changes in both mineralogy and texture. When first deposited, sinters consist largely of noncrystalline spheres (<1–8 μm diameter) of opal-A exhibiting varying degrees of close-packing. Particle densities range from 1.5 to 2.1 g cm⁻³, total water 4–10 wt%, and porosities 35–60%. Changes over ∼10,000 years following deposition are slight although the spheres may be invested by an additional film of secondary silica. For the next 10,000 to ∼50,000 years, the silica incrementally crystallises to become poorly crystalline opal-CT and/or opal-C; spherical particles of thin-bladed crystals (lepispheres) replace opal-A particles and coalesce in microbotryoidal aggregates (∼10–30 μm diameter). Amygdaloidal fibrous clusters occur with lepispheres. As silica lattice ordering becomes enhanced, total water content drops to <7 wt%, particle density increases to ∼2.3 g cm⁻³, and porosity reduces to <30%. The change from opal-A to opal-C takes place over a briefer periods (∼50 years) in silica sinters that contain other materials (e.g. calcite, sulfur, alunite, plant remains). Sinters older than ∼50,000 years have recrystallised to microcrystalline quartz. With the onset of quartz crystallisation at ∼20,000 years, total water is <0.2 wt%, particle density approximates quartz (2.65 g cm⁻³), and porosity is <4%. The progressive changes in silica species and texture yield ageing profiles for sinters that may serve as guides to the paleohydrology of geothermal systems and/or epithermal ore deposits in areas where surface thermal activity has declined or ceased. Received: 18 November 1998 / Accepted: 6 July 1999     

Diagenetic trends in the siliceous facies of the Monterey Shale in the Santa Maria region, California

X-ray diffraction and oxygen isotopic analyses of outcrop and subsurface samples of siliceous rocks were used to reconstruct thermal and diagenetic histories of the Miocene Monterey Shale near Santa Maria, California. Within many stratigraphic sections soft, porous diatomaceous rocks change gradationally to underlying hard and brittle chert, porcellanite, and siliceous shale; the accompanying silica mineral zones are, in descending stratigraphic order: (1) biogenic silica (opal-A), (2) cristobalitic silica (opal-CT), and (3) microcrystalline quartz. Boundaries between silica mineral zones and stratigraphic horizons are often discordant. Within the opal-CT zone, the d(101)-spacing of opal-CT decreases in a smooth non-linear fashion from about 4 10 Å to 4-04 Å. In the Santa Maria Valley and Bradley oil field areas the thicknesses of the opal-CT zones are greater and the present thermal gradients less than in the adjacent Orcutt oil field. Thin opal-CT zones at shallow maximum burial depths apparently correlate with higher thermal gradients. Using present thermal gradients and reconstructed maximum burial depths from well data in the Santa Maria region, the ranges in temperatures for the top and base of the opal-CT zone are 38–54 °C and 55–110 °C, respectively. The temperature difference between these two boundaries ranges from 17 to 60 °C. In comparison, temperature ranges for these two boundaries computed from oxygen isotopic compositions of opal-CT and quartz, extrapolated experimental quartz-water fractionations, and assuming δO¹⁸= 0%_o for the isotopic composition of the equilibrating fluid are 18–56 °C and 31–80 °C for the top and base of the opal-CT zone, respectively. The temperature difference between these boundaries is 11–36 °C using this method. Thermal gradients and sedimentation rates strongly influence rates of silica transformations. Reconstructed thermal and diagenetic histories of siliceous rocks of the Monterey Shale at four well sites in the Santa Maria region demonstrate that most silica conversions probably occurred during the last 3–4 Myr in response to accelerated rates of sedimentation (and therefore burial heating) during the Pliocene.     

Origin and evolution of the Steamboat Springs siliceous sinter deposit, Nevada, U.S.A.

Siliceous hot spring deposits from Steamboat Springs, Nevada, U.S.A., record a complex interplay of multiple, changing, primary environmental conditions, fluid overprinting and diagenesis. Consequently these deposits reflect dynamic geologic and geothermal processes. Two surface sinters were examined—the high terrace, and the distal apron-slope, as well as 13.11 m (43 ft) of core material from drill hole SNLG 87-29. The high terrace sinter consists of vitreous and massive-mottled silica horizons, while the distal deposit and core comprise dominantly porous, indurated fragmental sinters. Collectively, the three sinter deposits archive a complete sequence of silica phase diagenetic minerals from opal-A to quartz. X-ray powder diffraction analyses and infrared spectroscopy of the sinters indicate that the distal apron-slope consists of opal-A and opal-A/CT mineralogy; the core yielded opal-A/CT and opal-CT with minor opal-A; and the high terrace constitutes opal-C, moganite, and quartz. Mineralogical maturation of the deposit produced alternating nano–micro–nano-sized silica particle changes. Based on filament diameters of microbial fossils preserved within the sinter, discharging thermal outflows fluctuated between low-temperatures (< 35 °C, coarse filaments) and mid-temperatures ( 35–60 °C, fine filaments). Despite transformation to quartz, primary coarse and fine filaments were preserved in the high terrace sinter. AMS ¹⁴C dating of pollen from three horizons within core SNLG 87-29, from depths of 8.13 to 8.21 m (26′8″ to 26′11″), 10.13 to 10.21 m (33′3″ to 33′6″), and 14.81 to 14.88 m (48′7″ to 48′10″), yielded dates of 8684 ± 64 years, 11,493 ± 70 years and 6283 ±60 years, respectively. In the upper section of the core, the stratigraphically out-of-sequence age likely reflects physical mixing of younger sinter with quartzose sinter fragments derived from the high terrace. Within single horizons, mineralogical and morphological components of the sinter matrix were spatially patchy. Overall, the deposit was modified by sub-surface flow of alkali-chloride thermal fluids depositing a second generation of silica, and periodically, by acidic steam condensate formed during periods when the water table was low. Local faulting produced considerable fracturing of the sinter. Hence, the Steamboat Springs sinter experienced a complex history of primary and secondary hydrothermal, geologic and diagenetic events, and their inter-relationships and effects are locked within the physical, chemical and biological signatures of the deposit.     

The nature and origin of pigments in black opal from Lightning Ridge,New South Wales,Australia

Abstract

Black opal (opal-AG) owes its dark coloration to a fine-grained pigment commonly inferred to be mainly carbon, yet chemical compositions for black opals suggest there may be additional components. Here we search for such components in pigment concentrates prepared by dissolving black opal nodules (nobbies) from Lightning Ridge (NSW) in hydrofluoric acid, using electron microscopy (scanning electron microscopy, transmission electron microscopy), X-ray diffraction and laser-ablation ICP-MS. The results demonstrate the presence of sulfides—predominantly pyrite and chalcopyrite, with minor galena and Ti-oxide phases, as additional components of the pigment. ATR-FTIR analysis indicates the presence of C=O and C–H groups, consistent with an organic origin. Transmission electron microscopy images of pigment show variously deformed, originally spherical ～100?nm particles rich in sulfide and carbon, which are interpreted as thin coatings of pigment on now dissolved opaline silica spheres. Laser-ablation ICP-MS analysis identifies remnant silica in pigment concentrates, which may be interpreted as opaline silica surviving HF treatment protected as inclusions in sulfides. When examined within the context of petrographic observations from more than 1000 opal nodules (nobbies) at Lightning Ridge, these new results suggest that pigment carbon and sulfides in the nodules formed microbially under initially anoxic groundwater conditions, within pre-existing cavities concurrently being filled with silica sol ultimately derived from chemical weathering of feldspar-rich volcaniclastic sediment. Intensely black pigment layers observed at the floor of many nodules indicate settling of dark, high-density (sulfide–Ti-oxide-rich) pigment within cavities, with the implication that sulfate-reducing bacterial (SRB) activity commences early during the silica sol-gel ripening process. Microbial activity may persist until after the cavity has completely filled with the silica sol, as illustrated by abundant black opals with uniformly distributed pigment. Pigment formed at this stage may no longer be able to settle out within the ripening and increasingly viscous silica gel, thus forming pigmentation throughout the opal cavity. The existence of ‘amber’, pigment-poor opal with intensely black basal pigment layers is interpreted as signalling a lack of sulfate to sustain further SRB activity, or a change to more oxidising conditions, possibly related to interaction with surface waters within a downward-penetrating weathering front. A change in redox conditions would shut off activity of SRB and thus sulfide pigment production and allow development of aerobic microbial activity as described by others.     

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.     

Miocene silcretes in argillaceous playa deposits, Madrid Basin, Spain: petrological and geochemical features

Four regressive sequences are present in the opaline rocks and related deposits of the Miocene Intermediate Unit of the Madrid Basin. The sequences consist of silty mudstones and argillaceous opals, separated by transitional facies. The silty mudstone consists mainly of dioctahedral smectites, whereas the argillaceous opal is principally opal-CT and variable amounts of sepiolite. In the transitional facies, lamina of dioctahedral smectite co-exist with neoformed opal-CT and sepiolite. Petrological and geochemical features (major, trace and REE elements) indicate that the opaline levels and the transitional facies are related and are a consequence of silcrete formation in an argillaceous playa deposit. The isocon method was used to calculate changes in element concentration associated with silcrete formation. The geochemical data suggest silicification in an arid environment. The silcrete profile occurs four times, possibly as a result of highstand–lowstand fluctuations of the lake level caused by climatic changes. Structures and cements in the silcretes indicate that, although silicification may have commenced at the top of a groundwater table, it continued in the unsaturated zone above the water table.     

Silica diagenesis of Neogene diatomaceous and volcaniclastic sediments in northern Japan*

Marine diatomaceous siliceous sediments in Neogene sections of northern Japan contrast with the Monterey Shale of California in containing many intercalations of acidic volcaniclastic sediments. Diagenesis of these sediments from deep boreholes and surface sections was investigated. Three diagenetic zones—biogenic opal, opal-CT and quartz zones—are recognized in siliceous sediments, corresponding roughly to amorphous silica, low cristobalite and quartz zones in acidic vitric volcaniclastic sediments. Opal-CT consists almost exclusively of silica and water, while low cristobalite contains appreciable amounts of A1, Ca, Na and K. In subsurface sections, values of d(101) spacing of opal-CT decrease progressively with increasing burial depth. The progressive ordering is not associated with additional silica cementation. In surface sections, the behaviour of d(101) spacing is complicated owing to the modification of the progressive ordering developed during burial diagenesis by later silica cementation during uplift. The cementing opal-CT is probably precipitated from percolating groundwater which dissolves siliceous skeletons in porous diatomaceous mudstones overlying the opal-CT porcellanite. Opaline cherts that form during burial diagenesis are designated as early opaline chert, while those which form during uplift are later opaline chert. The later opaline chert contains two groups of opal-CT; one is progressively ordered opal-CT and the other is additionally cemented opal-CT with higher d(101) spacing than that in the host porcellanite. In diatomaceous siliceous sediments, early opaline chert is scarce. Most, if not all, opaline cherts in surface sections are of later origin.     

Factors governing subaqueous siliceous sinter precipitation in hot springs: examples from Yellowstone National Park, USA

Abstract Siliceous sinter precipitation within hot spring systems has been attributed to a variety of mechanisms: evaporative concentration, cooling, changes in pH and cation effects. Repetitive in situ (T, pH, alkalinity, etc.) and laboratory (major, minor and trace elemental, stable isotopic) analyses of the waters plus observations of silica precipitation on natural (e.g. twigs, pine cones) as well as artificial substrates (glass slides and copper plates) in the waters substantiate that subaqueous precipitation is occurring throughout the vent to distal end of flow in both Cistern Spring (Norris Geyser Basin) and Deerbone Spring (Lower Geyser Basin), Yellowstone National Park, Wyoming, USA. Quartz and sodium–potassium geothermometers indicate that Cistern Spring is fed by a subsurface reservoir that is between 232 and 272 °C. Calculated reservoir temperatures are significantly lower at Deerbone Spring (182–197 °C). Based on a suite of measured and theoretical saturation indices, downflow changes in the system resulting from evaporative concentration (e.g. Cl increases 10%), changes in pH (e.g. 5·6–7·1) and cation effects (Al and Fe) are of negligible importance in the subaqueous precipitation of hot spring opal‐A. Similarly, at the macroenvironmental scale, potential biotic effects on opal‐A precipitation appear to be minimal. Modelling of the two active siliceous sinter precipitating systems indicates that cooling (e.g. 80–17 °C) is the predominant process governing subaqueous mineral precipitation.     

云南腾冲地热区主要蚀变矿物含量与蚀变母岩的关系

腾冲地热区出露有众多热泉泉群,地热活动频繁,岩石发生强烈蚀变,形成的主要蚀变矿物包括高岭石、绢云母、蒙脱石、I/M间层矿物、石英和蛋白石。主要蚀变矿物的种类和含量受蚀变母岩性质的控制,花岗质砂砾岩和花岗岩形成高岭石,玄武岩形成伊利石和蒙托石,安山岩中发育硅化作用。泥化作用增强的趋势是安山岩→花岗岩→玄武岩→花岗质砂砾岩。由于花岗质砂砾岩在热区内广泛分布,通过蚀变作用形成了有经济价值的高岭土矿床。     

Nodular chert from the Arbuckle Group, Slick Hills, SW Oklahoma: a combined field, petrographic and isotopic study

Nodular chert from the middle and upper Arbuckle Group (Early Ordovician) in the Slick Hills, SW Oklahoma, was formed by selective replacement of grainstones, burrow fillings, algal structures, and evaporite nodules. Chert nodules are dominantly microquartz with minor fibrous quartz (both quartzine and chalcedony), megaquartz, and microflamboyant quartz. Lepisphere textures of an opal-CT precursor are preserved in many (especially in finely-crystalline) chert nodules. The δ¹⁸O values of microquartz chert range from +23.4 to + 28.8^0/00 (SMOW), significantly lower than those of Cenozoic and Mesozoic microquartz chert formed both in the deep sea and from near-surface sea water. The δ¹⁸O values of chert decrease with increasing quartz crystal size. Silicification in the Arbuckle Group occurred during early diagenesis, with the timing constrained by the relative temporal relationships among silicification, burial compaction, and early dolomite stabilization. Silica for initial chert nucleation may have been derived from both dissolution of sponge spicules and silica-enriched sea water. Chert nucleation appears to have been controlled by the porosity, permeability, and organic matter content of precursor sediments. This conclusion is based on the fact that chert selectively replaced both porous grainstones and burrows and algal structures enriched in organic matter. Growth of chert probably occurred by a maturation process from opal-A(?), to opal-CT, to quartz, as indicated by the presence of opal-CT precursor textures in many chert nodules. Although field and petrographic evidence argues for an early marine origin for chert in the Arbuckle Group, the light δ¹⁸O values are inconsistent with this origin. Meteoric resetting of the δ¹⁸O values of the chert during exposure of the carbonate platform best explains the light δ¹⁸O values because: (i) the δ¹⁸O values of chert nodules decrease with decreasing δ¹⁸O values of host limestones, and (ii) chert nodules from early dolomite, which underwent more extensive meteoric modification than associated limestones, have lighter δ¹⁸O values than chert nodules from limestones. Increasing recrystallization of chert nodules by meteoric water resulted in progressive ¹⁸O depletion and (quartz) crystal enlargement.     

NMR,XRD and IR study on microcrystalline opals

Microcrystalline opal-CT and opal-C were investigated by ²⁹Si MAS NMR and ²⁹Si {¹H} cross polarisation MAS NMR spectroscopy, X-ray small angle scattering, X-ray powder diffraction and infrared absorption spectroscopy. The results are compared with those for non-crystalline precious opal (opal-AG), non-crystalline hyalite (opal-AN), moderately disordered cristobalite and with well ordered low-cristobalite and low-tridymite. Opal-C is confirmed to be strongly stacking disordered low-cristobalite with about 20 to 30% probability for tridymitic stacking. More extensively stacking disordered opal-CT does not contain detectable domains of low-cristobalite or low-tridymite. The stacking sequence is close to 50% cristobalite and 50% tridymitic. The local order decreases with increasing stacking disorder, so that the structural state of microcrystalline opals lies between cristobalite, tridymite and non-crystalline opals.     

The hot spring and geyser sinters of El Tatio, Northern Chile

The siliceous sinter deposits of El Tatio geothermal field in northern Chile have been examined petrographically and mineralogically. These sinters consist of amorphous silica (opal-A) deposited around hot springs and geysers from nearly neutral, silica-saturated, sodium chloride waters. Water cooling and evaporation to dryness are the main processes that control the opal-A deposition in both subaqueous and subaerial settings, in close spatial relation to microbial communities. All fingerprints of organisms observed in the studied sinter samples represent microbes and suggest that the microbial community is moderately diverse (cyanobacteria, green bacteria, and diatoms). The most important ecological parameter is the temperature gradient, which is closely related to the observed depositional settings: 1) Geyser setting: water temperature = 70–86 °C (boiling point at El Tatio: 4200 m a.s.l.); coarse laminated sinter macrostructure with rapid local variations; biota comprises non-photosynthetic hyperthermophilic bacteria. 2) Splash areas around geysers: water temperature = 60–75 °C; laminated spicule and column macrostructure, locally forming cupolas (< 30 cm); predominant Synechococcus-like cyanobacteria. 3) Hot spring setting: water temperature = 40–60 °C; laminated spicules and columns and subspherical oncoids characterize the sinter macrostructure; filamentous cyanobacteria Phormidium and diatoms (e.g., Synedra sp.) are the most characteristic microbes. 4) Discharge environments: water temperature = 20–40 °C; sinter composed of laminated spicules and oncoids of varied shape; cyanobacterial mats of Phormidium and Calothrix and diatoms (e.g., Synedra sp.) are abundant. El Tatio is a natural laboratory of great interest because the sedimentary macrostructures and microtextures reflect the geological and biological processes involved in the primary deposition and early diagenesis of siliceous sinters.     

Diagenesis of silica-rich mound-bedded chalk,the Coniacian Arnager Limestone,Denmark

The Coniacian Arnager Limestone Formation is exposed on the Danish island of Bornholm in the Baltic Sea. It is composed of mound-bedded siliceous chalk, and X-ray diffraction and scanning electron microscopy indicate a content of 30–70% insoluble minerals, including authigenic opal-CT, quartz, clinoptilolite, feldspars, calcite, dolomite, and barite. Opal-CT and clinoptilolite are the most common and constitute 16–53% and 2–9%, respectively. The content of insoluble minerals varies laterally both within the mounds and in planar beds, and the opal-CT content varies by up to 10% vertically. The mounds consist of two microfacies, spiculitic wackestone and bioturbated spiculitic wackestone, containing 10–22% and 7–12% moulds after spicules, respectively.Subsequent to deposition and shallow burial, dissolution of siliceous sponge spicules increased the silica activity of the pore water and initiated precipitation of opal-CT. The opal-CT formed at temperatures around 17 °C, the precipitation lowered the silica activity and the Si/Al ratio of the pore water, resulting in precipitation of clinoptilolite, feldspar and smectite. Calcite formed synchronously with the latest clinoptilolite. Minor amounts of quartz precipitated in pore water with low silica activity during maximum burial, probably to depths of 200–250 m. The dissolution of sponge spicules and decomposition of the sponge tissue also resulted in the release of Ba²⁺, Sr²⁺, Mg²⁺, Ca²⁺ and CO₃^2?, facilitating precipitation of barite and dolomite. Precipitation of especially opal-CT reduced the porosity to an average of 40% and cemented the limestone. The study highlights the diagenetic pathways of bio-siliceous chalk and the effects on preservation of porosity and permeability.     

Iron–bentonite interactions in the Kawasaki bentonite deposit,Zao area,Japan

Greenish veins occurring in brecciated bentonite were found in the Kawasaki bentonite deposit of the Zao region in Miyagi Prefecture, Japan. Their occurrence possibly indicates the interaction of bentonite with Fe-rich hydrothermal solutions. In order to prove the hypothesis and understand the long-term mineralogical and petrographic evolution of bentonite during such interactions, the greenish veins and the surrounding altered bentonite were analyzed using X-ray fluorescence (XRF), scanning electron microscopy (SEM), X-ray diffraction (XRD), electron probe micro-analysis (EPMA), scanning transmission electron microscopy with energy dispersed spectroscopy (STEM-EDS) and micro X-ray absorption near-edge structure (XANES). The greenish veins resulting from hydrothermal solution are composed of mixed-layer minerals consisting of smectite and glauconite (glaucony), pyrite and opal. The occurrences indicate that glaucony and pyrite formed almost simultaneously from hydrothermal solution prior to opal precipitation. The mineral assemblages of the greenish veins and their surroundings indicate that the hydrothermal activity had most likely taken place at a temperature of less than 100 °C and that the pH and Eh conditions of the reacted solution were neutral to alkaline pH and reducing. The unaltered bentonite is composed mainly of Al smectite and opal. These minerals coexist as a mixture within the resolution level of the microprobe analyses. On the other hand, the bentonite in contact with the greenish veins consists of discrete opal grains and dioctahedral Al smectite containing Fe and was altered mineralogically and petrographically by the hydrothermal activity. Both the clay minerals and the opal were formed by dissolution and subsequent precipitation from the interaction of the original bentonite with the hydrothermal solution.     

Formation of Fe-Mn-Si oxide and nontronite deposits in hydrothermal fields on the Valu Fa Ridge, Lau Basin

Hydrothermal Fe-Mn-Si oxides and nontronite are pervasive in the Hine Hina, Vai Lili and Mariner hydrothermal fields along the central Valu Fa Ridge, Lau Basin. Morphometric and mineralogical analyses reveal that the iron-rich filaments are the most important constituents of these Fe-Mn-Si oxide deposits. Both the morphologies and chemical composition of the filaments indicate that neutrophilic Fe-oxidizing bacteria have played a key role in the formation of these deposits. A key process of the formation of these deposits is the creation of a complicated filamentous network in which a series of metabolic activities and passive sorption and nucleation processes occur. The precipitation of dissolved Si in unsaturated and saturated states leads to a “two-generation” growth model in the hydrothermal vents. The precipitation of amorphous opal occurs in a relatively narrow temperature range (41.1-42.9 °C) based on oxygen isotope analyses, indicating a fast precipitation rate of opal-A when conductive cooling of the hydrothermal fluid occurrs. Patchy nontronite in the Mariner fields is a product of the direct precipitation from hydrothermal fluids at a temperature of ∼87.9 °C, whereas the scattered nontronite at the Hine Hina field is the product of the replacement of hydrothermal Fe-Si oxides at a temperature of ∼46.2 °C.