Centennial-scale oscillations in oxygen and carbon isotopes of endogenic calcite from a 15,500 varve year record of the Piànico interglacial

The palaeolake record from Piànico (Southern Alps) comprises a sequence of 15,500 continuous calcite varves formed during peak interglacial conditions around 400 ka ago. The varved nature of these deposits allows precise sub-sampling of five varve year intervals for stable isotope analyses. All samples consist of calcite precipitated in the epilimnion of the lake, with contents of detrital carbonate below 4%. Four significant negative δ¹⁸O oscillations occurred during the upper half of the interglacial. The most prominent of these oscillations has an amplitude of −1.1‰ and lasted 780 varve years. The three other oscillations are shorter (125–195 varve years) and of lower amplitude (0.4–0.9‰). An additional major drop in δ¹⁸O occurs 315 varve years before the end of continuous calcite precipitation in the lake. This shift marks the end of long interglacial conditions and the beginning of harsher climate conditions and glacier advances in the Southern Alps. In contrast, the four δ¹⁸O oscillations within the period of continuous formation of calcite varves reflect natural intra–interglacial climate dynamics.     

Microfacies of detrital event layers deposited in Quaternary varved lake sediments of the Piànico-Sèllere Basin (northern Italy)

A Quaternary interglacial lake sediment record from the Piànico-Sèllere Basin (northern Italy) consists of biochemical calcite varves with intercalated detrital layers. At the end of the Piànico Interglacial, continuous varve formation was replaced by predominantly detrital sedimentation. However, 427 varve-years before this shift, an abrupt increase in the frequency and thickness of detrital layers occurred. Microfacies analyses reveal a total of 152 detrital layers, ranging from 0·2 to 20·15 mm in thickness, deposited during the last 896 years of the Piànico Interglacial. Three microfacies types are distinguished: (i) graded layers, (ii) non-graded silt layers, and (iii) matrix-supported layers. The position of detrital layers within an individual varve provides additional information on the season in which they have been deposited. Microfacies analyses in combination with varve counting further enabled precise varve-to-varve correlation of the detrital layers for two sediment sections cropping out ca 130 m apart. The detailed intra-basin correlation allows the source regions of detrital layers to be inferred. Moreover, micro-erosion at sub-millimetre scale has been established. Of the described facies types, only the accumulation of summer and spring graded and non-graded silt layers abruptly increased before the end of interglacial varve formation whereas non-graded winter silt and matrix-supported layers are randomly distributed over the entire study period. Heavy rainfalls are assumed to have triggered spring and summer graded layers, so that the occurrence of these layers is thought to be a proxy for extreme precipitation events in the past.     

Environmental responses to Lateglacial climatic fluctuations recorded in the sediments of pre‐Alpine Lake Mondsee (northeastern Alps)

Investigation of the sedimentary record of pre‐Alpine Lake Mondsee (Upper Austria) focused on the environmental reaction to rapid Lateglacial climatic changes. Results of this study reveal complex proxy responses that are variable in time and influenced by the long‐term evolution of the lake and its catchment. A new field sampling approach facilitated continuous and precisely controlled parallel sampling at decadal to sub‐annual resolution for µ‐XRF element scanning, carbon geochemistry, stable isotope measurements on ostracods, pollen analyses and large‐scale thin sections for microfacies analysis. The Holocene chronology is established through microscopic varve counting and supported by accelerator mass spectrometry ¹⁴C dating of terrestrial plant macrofossils, whereas the Lateglacial age model is based on δ¹⁸O wiggle matching with the Greenland NGRIP record, using the GICC05 chronology. Microfacies analysis enables the detection of subtle sedimentological changes, proving that depositional processes even in rather large lake systems are highly sensitive to climate forcing. Comparing periods of major warming at the onset of the Lateglacial and Holocene and of major cooling at the onset of the Younger Dryas reveals differences in proxy responses, reflecting threshold effects and ecosystem inertia. Temperature increase, vegetation recovery, decrease of detrital flux and intensification of biochemical calcite precipitation at the onset of the Holocene took place with only decadal leads and lags over a ca. 100 a period, whereas the spread of woodlands and the reduction of detrital flux lagged the warming at the onset of the Lateglacial Interstadial by ca. 500–750 a. Cooling at the onset of the Younger Dryas is reflected by the simultaneous reaction of δ¹⁸O and vegetation, but sedimentological changes (reduction of endogenic calcite content, increase in detrital flux) were delayed by about 150–300 a. Three short‐term Lateglacial cold intervals, corresponding to Greenland isotope substages GI‐1d, GI‐1c2 and GI‐1b, also show complex proxy responses that vary in time. Copyright © 2011 John Wiley & Sons, Ltd.     

Saddle-Dolomite-Bearing Fracture Fillings and Records of Hot Brine Activity in the Jialingjiang Formation, Libixia Section, Hechuan Area of Chongqing City

Most vein minerals deposited in fractures of the Jialingjiang Formation from Libixia section,Hechan area include a large amount of saddle dolomite and accompanying celestite,calcite and fluorite.This study analyzed the nature,source,evolution of the fluids by plane-light petrography,fluid-inclusion methods,cathodoluminescence images,and stable isotopic compositions.The homogenization temperatures of two-phase aqueous fluid inclusions in dolomite range between100 and 270℃.Combined with theδ~(18)O data,it is suggested that the fluid responsible for the precipitation of fracture fillings haveδ~(18)O values between 10‰and 18‰(relative to SMOW).The saddle dolomite and the accompanying minerals were the result of activity of dense brines at elevated temperatures.Moreover,analysis shows that the fluid was derived from a mixture of marine-derived brine and deeper circulating flow.This fluid was enriched in Sr during diagenesis and formed celestite in fracture and for regional mineralization.Dissolution of saddle dolomite was attributed to the cooling of Mg/Ca-decreased fluids,which may relate to a leaching of gypsum to celestite in surrounding carbonates.     

Semi-automatic determination of the carbon and oxygen stable isotope compositions of calcite and dolomite in natural mixtures

A semi-automatic, on-line method was developed to determine the δ¹³C and δ¹⁸O values of coexisting calcite and dolomite. An isotopic mass balance is used to calculate the compositions of dolomite after having measured that of calcite and of the “bulk” sample. The limit of validity of this method is established by performing isotopic measurements of artificial mixtures made of precisely weighted and isotopically-characterised dolomite and calcite. The accuracy and repeatability of the calculation of dolomite δ¹³C and δ¹⁸O are statistically determined with a Monte-Carlo procedure of error propagation. Stable isotope ratios are determined by using an automated MultiPrep™ system on-line with an isotope-ratio mass-spectrometer (IRMS). The reaction time and the temperature of reaction were optimised by comparing the results with the isotopic composition of known mixtures. The best results were obtained by phosphoric acid digestion after 20 min at 40 °C for calcite and 45 min at 90 °C for dolomite. This procedure allows an accurate determination of the isotopic ratios from small samples (300 μg). Application of this protocol to natural mixtures of calcite and dolomite requires the accurate determination of the relative abundance of calcite and dolomite by combining Mélières manocalcimetry (MMC) and X-ray diffractometry (XRD).     

Pleistocene speleothems of Mallorca: implications for palaeoclimate and carbonate diagenesis in mixing zones

The Pleistocene speleothems of Sa Bassa Blanca cave, Mallorca, are excellent indicators of palaeoclimate variations, and are samples that allow evaluation of the products and processes of mixing‐zone diagenesis in an open‐water cave system. Integrated stratigraphic, petrographic and geochemical data from a horizontal core of speleothem identified two main origins for speleothem precipitates: meteoric‐marine mixing zone and meteoric‐vadose zone. Mixing‐zone precipitates formed at and just below the water–air interface of cave pools during interglacial times, when the cave was flooded as a result of highstand sea‐level. Mixing‐zone precipitates include bladed and dendritic high‐Mg calcite, microporous‐bladed calcite with variable Mg content, and acicular aragonite; their presence suggests that calcium‐carbonate cementation is significant in the studied mixing‐zone system. Fluid inclusion salinities, δ¹³C and δ¹⁸O compositions of the mixing‐zone precipitates suggest that mixing ratio was not the primary control on whether precipitation or dissolution occurred, rather, the proximity to the water table and degassing of CO₂ at the interface, were the major controls on precipitation. Thus, simple two‐end‐member mixing models may apply only in mixing zones well below the water table. Meteoric‐vadose speleothems include calcite and high‐Mg calcite with columnar and bladed morphologies. Vadose speleothems precipitated during glacial stages when sea level was lower than present. Progressive increase in δ¹³C and δ¹⁸O of the vadose speleothems resulted from cooling temperatures and more positive seawater δ¹⁸O associated with glacial buildup. Such covariation could be considered as a valid alternative to models predicting invariant δ¹⁸O and highly variable δ¹³C in meteoric calcite. Glacio‐eustatic oscillations of sea‐level are recorded as alternating vadose and mixing‐zone speleothems. Short‐term climatic variations are recorded as alternating aragonite and calcite speleothems precipitated in the mixing zone. Fluid‐inclusion and stable‐isotope data suggest that aragonite, as opposed to calcite, precipitated during times of reduced meteoric recharge.     

Disseminated ‘jigsaw piece’ dolomite in Upper Jurassic shelf sandstones,Central North Sea: an example of cement growth during bioturbation?

Unusual textural and chemical characteristics of disseminated dolomite in Upper Jurassic shelf sediments of the North Sea have provided the basis for a proposed new interpretation of early diagenetic dolomite authigenesis in highly bioturbated marine sandstones. The dolomite is present throughout the Franklin Sandstone Formation of the Franklin and Elgin Fields as discrete, non‐ferroan, generally unzoned, subhedral to highly anhedral ‘jigsaw piece’ crystals. These are of a similar size to the detrital silicate grains and typically account for ≈5% of the rock volume. The dolomite crystals are never seen to form polycrystalline aggregates or concretions, or ever to envelop the adjacent silicate grains. They are uniformly dispersed throughout the sandstones, irrespective of detrital grain size or clay content. Dolomite authigenesis predated all the other significant diagenetic events visible in thin section. The dolomite is overgrown by late diagenetic ankerite, and bulk samples display stable isotope compositions that lie on a mixing trend between these components. Extrapolation of this trend suggests that the dolomite has near‐marine δ¹⁸O values and low, positive δ¹³C values. The unusual textural and chemical characteristics of this dolomite can all be reconciled if it formed in the near‐surface zone of active bioturbation. Sea water provided a plentiful reservoir of Mg and a pore fluid of regionally consistent δ¹⁸O. Labile bioclastic debris (e.g. aragonite, Mg‐calcite) supplied isotopically positive carbon to the pore fluids during shallow‐burial dissolution. Such dissolution took place in response to the ambient ‘calcite sea’ conditions, but may have been catalysed by organic matter oxidation reactions. Bioturbation not only ensured that the dissolving carbonate was dispersed throughout the sandstones, but also prohibited coalescence of the dolomite crystals and consequent cementation of the grain framework. Continued exchange of Mg²⁺ and Ca²⁺ with the sea‐water reservoir maintained a sufficient Mg/Ca ratio for dolomite (rather than calcite) to form. Irregular crystal shapes resulted from dissolution, of both the dolomite and the enclosed fine calcitic shell debris, before ankerite precipitation during deep‐burial diagenesis.     

Dolomitization,gypsum calcitization and silicification in carbonate–evaporite shallow lacustrine deposits

This paper describes and interprets the mineral and facies assemblages that occur in carbonate–evaporite shallow lacustrine deposits, considering the importance of the processes pathway (i.e. dolomitization, gypsum calcitization and silicification). The Palaeogene deposits of the Deza Formation (Almazán Basin, central‐northern Spain) are selected as a case study to determine the variety of physicochemical processes taking place in carbonate–evaporite shallow lakes and their resulting diagenetic features. Dolostones are the predominant lithology and are composed mainly of dolomite with variable amounts of secondary calcite (5 to 50%), which mainly mimic lenticular gypsum (pseudomorphs). Five morphological types of dolomite crystal were identified as follows: dolomite tubes, dolomite cylinders, rhombohedral dolomite, spheroidal and quasi‐rhombohedral dolomite, and cocoon‐shaped dolomite. The dolomite cylinders and tubes are interpreted as the dolomitized cells of a widespread microbial community. The sequence of diagenetic processes started with growth of microlenticular interstitial gypsum in a calcareous mud deposited on the playa margin mudflats, and that sometimes included microbial sediments. Immediately following growth of gypsum, dolomite replaced the original calcite (or possibly aragonite) muds, the microbial community and the gypsum. Partial or total replacement of gypsum by dolomite was related mainly to the biomineralization of endolithic microbial communities on gypsum crystals. Later calcitization took place under vadose, subaerial exposure conditions. The development of calcrete in distal alluvial settings favoured the release of silica and subsequent silicification on the playa margin mudflats. Stable isotope compositions of calcite range from ?9·02 to ?5·83‰ δ¹³C_PDB and ?7·10 to 1·22‰ δ¹⁸O_PDB; for the dolomite, these values vary from ?8·93 to ?3·96‰ δ¹³C_PDB and ?5·53 to 2·4‰ δ¹⁸O_PDB. Quartz from the cherts has δ¹⁸O_SMOW values ranging from 27·1 to 31·1‰. Wide variation and relatively high δ¹⁸O_SMOW values for dolomite indicate evaporitic and closed hydrological conditions; increased influx of meteoric waters reigned during the formation of secondary calcite spar.     

Stable isotopic and elemental characteristics of recent tufa from a karstic Krka River (south‐east Slovenia): useful environmental proxies?

Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO₂ degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ¹³C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO₂ degassing and tufa precipitation rate downstream. The Δ¹³C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous ¹²CO₂ degassing downstream leaving the carbon pool enriched in ¹³C. In the case of oxygen, the isotope fractionation (Δ¹⁸O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ¹⁸O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ¹⁸O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.     

Differential North Atlantic control of winter hydroclimate in late Holocene varved sediments of Lake Kortejärvi,eastern Finland

Sediment microfacies, geochemical μ‐XRF and X‐ray density analyses were conducted on varved sediments from Lake Kortejärvi (eastern Finland) covering the last 2700 years. The varves comprise couplets of detrital and organic sub‐layers throughout the complete time‐span. Based on their microfacies and stratigraphical position within a varve as well as comparisons with local discharge and meteorological data, thicker detrital layers are interpreted to reflect intensified snow‐melt floods following more humid winters. Detailed comparisons with monthly to annually resolved North Atlantic Oscillation (NAO) indices back to AD 1049 (901 a BP) suggest that multidecadal increases in snow‐melt layer thickness tend to be connected with a more positive phase of the NAO and, consequently, warmer winters. In contrast, distinct centennial intervals of thicker snow‐melt layers from −40 to 170, 280 to 460 and 1900 to 2300 a BP as well as around 2600 a BP do not consistently correspond to a particular NAO phase, but coincide with extended sea‐ice margins and a colder North Atlantic climate, causing intensified and southward shifted westerly cyclones. Our results point to a differential modification of North Atlantic winter hydroclimate working on varying time scales.     

Columnar calcites as testimony of diagenetic overprinting at the boundary between Upper Tournaisian dolomites and limestones (Belgium): multiple origins for apparently similar features

In topographic flat areas, sedimentary settings may vary from one outcrop to another. In these settings, calcite precipitates may yield macroscopically similar columnar features, although they are products of different sedimentary or diagenetic processes. Three columnar calcite crystal fabrics, i.e. rosettes, palisade crusts and macro-columnar crystal fans, have been differentiated near and at the contact between Upper Tournaisian dolomites and limestones along the southern margin of the Brabant-Wales Palaeohigh. Their petrographic characteristics, and geochemical and fluid inclusion data provide information on the (dia)genetic processes involved. Rosettes composed of non-luminescent columnar calcite crystal fans (1–5 cm in diameter) developed on top of one another, forming discrete horizons in repetitive sedimentary cycles. The cycles consist of three horizons: (I) a basal horizon with fragments from the underlying horizon, (II) a micrite/microspar horizon with incipient glaebules, (III) an upper horizon consisting of calcite rosettes, with desiccation features. The petrographical features and δ¹⁸O signatures of −10·0 to −5·5‰ and δ¹³C values of −5·5 to −3·2‰ support either evaporative growth, an evaporative pedogenic origin, or overprinting of marine precipitates. Palisade crusts, composed of a few to 10 mm long non-luminescent calcite crystals, coat palaeokarst cavities. Successive palisade growth-stages occur which are separated by thin laminae of micrite or detrital quartz, displaying a geopetal arrangement. Palisade crusts are interpreted as intra-Mississippian speleothems. This interpretation is supported by their petrographic characteristics and isotopic signature (δ¹⁸O = −8·7 to −6·5‰ and δ¹³C = −4·8 to −2·5‰). Macro-columnar crystals, 1–50 cm long, developed mainly perpendicular to cavity walls and dolomite clasts. Crystal growth stages in the macro-columnar crystals are missing. δ¹⁸O values vary between −16·4 and −6·8‰ and δ¹³C values between −5·2 and −0·9‰. These features possibly support a late diagenetic high temperature precipitation in relation to hydrothermal karstification.     

Multi‐proxy evidence for early to mid‐Holocene environmental and climatic changes in northeastern Poland

Lauterbach, S., Brauer, A., Andersen, N., Danielopol, D. L., Dulski, P., Hüls, M., Milecka, K., Namiotko, T., Plessen, B., von Grafenstein, U. & DecLakes participants 2010: Multi‐proxy evidence for early to mid‐Holocene environmental and climatic changes in northeastern Poland. Boreas, 10.1111/j.1502‐3885.2010.00159.x. ISSN 0300‐9483. We investigated the sedimentary record of Lake Hańcza (northeastern Poland) using a multi‐proxy approach, focusing on early to mid‐Holocene climatic and environmental changes. AMS ¹⁴C dating of terrestrial macrofossils and sedimentation rate estimates from occasional varve thickness measurements were used to establish a chronology. The onset of the Holocene at c. 11 600 cal. a BP is marked by the decline of Lateglacial shrub vegetation and a shift from clastic‐detrital deposition to an autochthonous sedimentation dominated by biochemical calcite precipitation. Between 10 000 and 9000 cal. a BP, a further environmental and climatic improvement is indicated by the spread of deciduous forests, an increase in lake organic matter and a 1.7‰ rise in the oxygen isotope ratios of both endogenic calcite and ostracod valves. Rising δ¹⁸O values were probably caused by a combination of hydrological and climatic factors. The persistence of relatively cold and dry climate conditions in northeastern Poland during the first one and a half millennia of the Holocene could be related to a regional eastern European atmospheric circulation pattern. Prevailing anticyclonic circulation linked to a high‐pressure cell above the retreating Scandinavian Ice Sheet might have blocked the influence of warm and moist Westerlies and attenuated the early Holocene climatic amelioration in the Lake Hańcza region until the final decay of the ice sheet.     

Dolomite formation in the dynamic deep biosphere: results from the Peru Margin

Early diagenetic dolomite beds were sampled during the Ocean Drilling Programme (ODP) Leg 201 at four reoccupied ODP Leg 112 sites on the Peru continental margin (Sites 1227/684, 1228/680, 1229/681 and 1230/685) and analysed for petrography, mineralogy, δ¹³C, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values. The results are compared with the chemistry, and δ¹³C and ⁸⁷Sr/⁸⁶Sr values of the associated porewater. Petrographic relationships indicate that dolomite forms as a primary precipitate in porous diatom ooze and siliciclastic sediment and is not replacing the small amounts of precursor carbonate. Dolomite precipitation often pre‐dates the formation of framboidal pyrite. Most dolomite layers show ⁸⁷Sr/⁸⁶Sr‐ratios similar to the composition of Quaternary seawater and do not indicate a contribution from the hypersaline brine, which is present at a greater burial depth. Also, the δ¹³C values of the dolomite are not in equilibrium with the δ¹³C values of the dissolved inorganic carbon in the associated modern porewater. Both petrography and ⁸⁷Sr/⁸⁶Sr ratios suggest a shallow depth of dolomite formation in the uppermost sediment (<30 m below the seafloor). A significant depletion in the dissolved Mg and Ca in the porewater constrains the present site of dolomite precipitation, which co‐occurs with a sharp increase in alkalinity and microbial cell concentration at the sulphate–methane interface. It has been hypothesized that microbial ‘hot‐spots’, such as the sulphate–methane interface, may act as focused sites of dolomite precipitation. Varying δ¹³C values from −15‰ to +15‰ for the dolomite are consistent with precipitation at a dynamic sulphate–methane interface, where δ¹³C of the dissolved inorganic carbon would likewise be variable. A dynamic deep biosphere with upward and downward migration of the sulphate–methane interface can be simulated using a simple numerical diffusion model for sulphate concentration in a sedimentary sequence with variable input of organic matter. Thus, the study of dolomite layers in ancient organic carbon‐rich sedimentary sequences can provide a useful window into the palaeo‐dynamics of the deep biosphere.     

衡阳盆地始新世含鱼地层的成因分析

衡阳市郊五马归槽始新世鱼化石保存在黑色湖相纹层中。根据纹层序列的对比,发现该地的鱼化石均为同一层位;根据鱼化石在纹层序列中的具体位置及鱼化石的保存状况,笔者推测鱼群的死亡并非由于季节更替,而是由气候干旱引起的湖水盐度升高所控制;黑白纹层的变化是由大气降雨所致。     

Post-Chicxulub depositional and diagenetic history of the northwestern Yucatan Peninsula,Mexico

The Chicxulub Sedimentary Basin of the northwestern Yucatan Peninsula, Mexico, which was formed because of the largest identified Phanerozoic bolide impact on Earth, became a site of deposition of dominantly marine carbonate sediments during most of the Cenozoic Era. This is a study of the filling and diagenetic history of this basin and surrounding areas. The study makes use of lithologic, biostratigraphic, petrographic, and geochemical data obtained on core samples from boreholes drilled throughout the northwestern Yucatan Peninsula.The core sample data indicate that: 1) The Chicxulub Sedimentary Basin concentrated the deposition of pelagic and outer-platform sediments during the Paleocene and Eocene, and, in places, during the Early Oligocene, as well, and filled during the Middle Miocene, 2) deeper-water limestone also is present within the Paleocene and Lower Eocene of the proposed Santa Elena Depression, which is located immediately south of the Basin, 3) shallow-water deposits are relatively more abundant outside the Basin and Depression than inside, 4) the autigenic and allogenic silicates from the Paleogene formations are the most abundant inside the Depression, 5) sediment deposition and diagenesis within the Basin also were controlled by impact crater topography, 6) the abundance of the possible features of subaerial exposure increases upward and outward from the center of the Basin, and 7) the formation of replacive low-magnesium calcite and dolomite, dedolomitization, dissolution, and precipitation of vug-filling calcite and dolomite cement have been more common outside the Basin than inside.δ¹⁸O in whole-rock (excluding vug-filling) calcite from core samples ranges from − 7.14‰ to + 0.85‰ PDB. δ¹³C varies from − 6.92‰ to + 3.30‰ PDB. Both stable isotopes correlate inversely with the abundance of subaerial exposure features indicating that freshwater diagenesis has been extensive especially outside and at the edge of the Chicxulub Sedimentary Basin.δ¹⁸O and δ¹³C in whole-rock (excluding vug-filling) dolomite ranges from − 5.54‰ to + 0.87‰ PDB and − 4.63‰ to + 3.38‰ PDB, respectively. Most dolomite samples have negative δ¹⁸O and positive δ¹³C suggesting that replacive dolomitization involved the presence of a fluid dominated by freshwater and/or an anomalously high geothermal gradient.Most dolomite XRD-determined mole percent CaCO₃ varies between 51 and 56. Replacive dolomite is larger, more euhedral, and less stoichiometric inside the Chicxulub Sedimentary Basin than outside.     

Oxygen and Carbon Isotope Study of Calcite and Dolomite in the Disseminated Au-Ag Telluride Bulawan Deposit, Negros Island, Philippines

Abstract: The disseminated Au‐Ag telluride Bulawan deposit, Negros island, Philippines, is hosted by dacite porphyry breccia pipes which formed in a Middle Miocene dacite porphyry stock. Electrum and Au‐Ag tellurides occur mostly as grains intergrown with or filling voids between sphalerite, pyrite, chalcopyrite, galena and tennantite. Calcite, quartz and rare dolomite are the principal gangue minerals. Four types of alteration were recognized in the deposit, namely; propylitic, K‐feldspar‐sericitic, sericitic and carbonate alteration. Carbonate alteration is correlatable to the gold deposition stage and occurs mostly along fault zones. The δ¹⁸O and δ¹³C compositions of calcite and dolomite in propylite zone and ore‐stage dacite porphyry breccia were determined. The δ¹⁸O values of calcite in propylitized andesite range from +12.2 to +14.7%, and their δ¹³C values range from ‐6.1 to ‐1.0%. The δ¹⁸O values of calcite and dolomite in sericite‐ and carbonate‐altered, mineralized dacite porphyry breccia and dacite porphyry rocks range from +15.1 to +23.1%, and the δ¹³C values of calcite and dolomite range from ‐3.9 to +0.9%. The δ¹⁸O and δ¹³C values of the hydrothermal fluids were estimated from inferred temperatures of formation on the basis of fluid inclusion microthermometry. The δ¹⁸O values of hydrothermal fluid for the propylitic alteration were calculated to be +8.5 ‐ +9.5%, assuming 375°C. On the other hand, the δ¹⁸O values of ore solutions for base metal and Au mineralization were computed to be +13.6 ‐ +14.6%, assuming 270°C. The hydrothermal fluids that formed the Bulawan deposit are dilute and ¹⁸O‐enriched fluids which reacted with ¹⁸O‐ and ¹³C‐rich wallrocks such as limestone.     

Silicification of sulphate evaporites and their carbonate replacements in Eocene marine sediments, Tunisia: two diagenetic trends

Samples of chert nodules, diagenetic carbonates and evaporites (gypsum/anhydrite) collected from the gypsiferous limestones of the Kef Eddour Member (Ypressian‐Priabonian) near Metlaoui and Sehib (Tunisia) show selective silicification with great variety in the silicified by‐products. Based on δ¹³C values, which support an organic origin for the carbon, carbonates replaced evaporites microbially through bacterial sulphate reduction. Observations and results suggest two scenarios for chert formation that are related to the rate and timing of diagenetic carbonate replacement of the evaporites (anhydrite/gypsum). In the absence of early diagenetic carbonate phases, silica with δ¹⁸O values from +25 to +28·6‰ [standard mean ocean water (SMOW)] replaced the outer parts of anhydrite nodules at pH < 9. In contrast, pore‐fluid pH values > 9 in the innermost parts of the anhydrite nodules prevented silica precipitation. The record of this chemical barrier is preserved in the microquartz rims and geode features that formed in the inner parts of the nodules after dissolution of the anhydrite nucleus. The microbial diagenetic replacement of evaporites (bacterial sulphate reduction) by carbonates (calcite, aragonite and dolomite) favoured silica replacement of carbonates rather than evaporites. Silica, with δ¹⁸O signature of +21 to +26‰ (SMOW), replaced carbonates on a volume‐for‐volume basis, yielding a more siliceous groundmass, and accounting for 90–95% of the nodules. The relatively higher δ¹⁸O values of quartz replacing anhydrite can be explained by a diagenetic fluid in equilibrium with mixed (meteoric/marine) to marine water. The lower δ¹⁸O values of the quartz that replaced the diagenetic carbonates are ascribed to flushing by meteoric water in a later diagenetic stage. The silica supply for chert formation could be derived from the reworked bio‐siliceous deposits (diatomites) to the west of the basin [vestiges of an opal‐CT precursor undetectable by X‐ray diffraction (XRD) were revealed by δ²⁹Si magic‐angle‐spinning nuclear magnetic resonance investigations], diagenesis of the extraformational and overlying clay‐rich beds (the host limestones are clay‐poor as shown by XRD measurements), and minor volcanogenic and hydrothermal contributions during early diagenetic stages.     

Formation of lacustrine dolomite in the late Miocene marginal lakes of the East Mediterranean (Northern Israel)

The study focuses on the formation of lacustrine dolomite in late Miocene lakes, located at the East Mediterranean margins (Northern Israel). These lakes deposited the sediments of the Bira (Tortonian) and Gesher (Messinian) formations that comprise sequences of dolostone and limestone. Dolostones are bedded, consist of small‐sized (<7 μm), Ca‐rich (52 to 56 mol %) crystals with relatively low ordering degrees, and present evidence for replacement of CaCO₃ components. Limestones are comprised of a wackestone to mudstone matrix, freshwater macrofossils and intraclasts (mainly in the Bira Formation). Sodium concentrations and isotope compositions differ between limestones and dolostones: Na = ~100 to 150 ppm; ~1000 to 2000 ppm; δ¹⁸O = ?3·8 to ?1·6‰; ?2·0 to +4·3‰; δ¹³C = ?9·0 to ?3·4‰; ?7·8 to 0‰ (VPDB), respectively. These results indicate a climate‐related sedimentation during the Tortonian and early Messinian. Wet conditions and positive freshwater inflow into the carbonate lake led to calcite precipitation due to intense phytoplankton blooms (limestone formation). Dry conditions and enhanced evaporation led to precipitation of evaporitic CaCO₃ in a terminal lake, which caused an increased Mg/Ca ratio in the residual waters and penecontemporaneous dolomitization (dolostone formation). The alternating lithofacies pattern reveals eleven short‐term wet–dry climate‐cycles during the Tortonian and early Messinian. A shift in the environmental conditions under which dolomite formed is indicated by a temporal decrease in δ¹⁸O of dolostones and Na content of dolomite crystals. These variations point to decreasing evaporation degrees and/or an increased mixing with meteoric waters towards the late Messinian. A temporal decrease in δ¹³C of dolostones and limestones and appearance of microbial structures in close association with dolomite suggest that microbial activity had an important role in allowing dolomite formation during the Messinian. Microbial mediation was apparently the main process that enabled local growth of dolomite under wet conditions during the latest Messinian.     

Dolomitization of the Capitan Formation forereef facies (Permian, west Texas and New Mexico): seepage reflux revisited

Abstract Interpretation of seepage reflux dolomitization is commonly restricted to intervals containing evaporites even though several workers have modelled reflux of mesosaline brines. This study looked at the partially dolomitized forereef facies of the Capitan Formation to test the extent of reflux dolomitization and evaluate the possible role of the near‐backreef mesosaline carbonate lagoon as an alternative source of dolomitizing fluids. The Capitan Formation forereef facies ranges from 10% to 90% dolomite. Most of the dolomite is fabric preserving and formed during early burial after marine cementation, before and/or during evaporite cementation and before stylolitization. Within the forereef facies, dolomite follows depositional units, with debris‐flow and grain‐flow deposits the most dolomitized and turbidity‐current deposits the least. The amount of dolomite increases with stratigraphic age and decreases downslope. Within the reef facies, dolomite is restricted to haloes around fractures and primary cavities except where the reef facies lacks marine cements and, in contrast, is completely dolomitized. This dolomite distribution supports dolomitization by sinking fluids. Oxygen isotopic values for fabric‐preserving dolomite (δ¹⁸O = 0·9 ± 1·0‰, N = 101) support dolomitization by sea water to isotopically enriched sea water. These values are closer to the near‐backreef dolomite (δ¹⁸O = 2·1 ± 0·7‰, N = 48) than the hypersaline backreef dolomite (δ¹⁸O = 3·6 ± 0·9‰, N = 11). Therefore, the fabric‐preserving dolomite is consistent with dolomitization during seepage reflux of mainly mesosaline brines derived from the near‐backreef carbonate lagoon. The occurrence of mesosaline brine reflux in the Capitan Formation has important implications for dolomitization in forereef facies and elsewhere. First, any area with a restricted carbonate lagoon may be dolomitized by refluxing brines even if there are no evaporite facies present. Secondly, such brines may travel significant distances vertically provided permeable pathways (such as fractures) are present. Therefore, the absence of immediately overlying evaporite or restricted facies is not sufficient cause to eliminate reflux dolomitization from consideration.     

Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.