Carbon and oxygen isotope zoning around Carlin-type gold deposits: a reconnaissance survey at Twin Creeks, Nevada

This study was undertaken to determine whether wallrocks around the Twin Creeks Carlin-type gold deposits exhibit oxygen isotope haloes similar to those found around other types of hydrothermal deposits. Mineralization at Twin Creeks is hosted by Ordovician Sequence shales containing some carbonate minerals and by Pennsylvanian–Permian Etchart Formation limestone. Analysis of orthophosphate-soluble carbonate from these rocks shows that oxygen isotope haloes are detectable in Ordovician Sequence shales but not in Etchart Formation limestone. The soluble fraction of Ordovician Sequence shales at Twin Creeks has δ¹⁸O values of 12 to 24‰ and δ¹³C values of 0 to −10‰. Most samples fall along a poorly defined trend that extends from δ¹⁸O of about 24‰ and δ¹³C values of about 0, which are typical of unaltered limestones, toward lower values for both isotope systems, which are typical of rocks that have undergone alteration by hydrothermal fluids. Plots of these values along two sections through the ore body show that δ¹⁸O values of wallrocks are lowest in the ore zone and increase outward, forming a halo several hundred meters in size. In the same plots, δ¹³C values of the wallrocks do not show systematic spatial variations. The soluble fraction of Etchart Formation limestones at Twin Creeks have δ¹⁸O values of 25 to 5‰ and δ¹³C values of 4 to −10‰, but do not show any systematic spatial variation relative to mineralization at the scale of our samples. Failure of the Etchart Formation samples to show detectable haloes is probably related to deposition of post-ore carbonate minerals or lower ore fluid : rock ratios. Material balance calculations used to model the isotopic composition of average Ordovician Sequence shales indicate that changes in temperature and water : rock ratio were probably not sufficient to account for the wide range of isotope compositions observed in these rocks. The most likely additional factor contributing to this range of values was a change in the composition of the altering fluid, probably by mixing of the ore fluid with surrounding meteoric water. These results suggest that Carlin-type gold deposits are surrounded by haloes of low δ¹⁸O values, but that detection of these haloes could be complicated by local compositional variations and post-ore modification of the wallrocks.     

Stable isotope variations in the Quaternary epithermal calcite-fluorite deposit at Monte delle Fate near Cerveteri (Latium,central Italy)

Carbon, oxygen and hydrogen isotope variations have been measured in samples from the epithermal fluorite vein deposit at Monte delle Fate, Latium. The ranges in ¹³C and ¹⁸O of calcite are –1.3 to 3.4 and 9.5 to 17.3, respectively. D values of water extracted from fluid inclusions are –49 to –39 for calcite and –41 to –34 for fluorite. Fluid inclusion filling temperatures (225°–240°C) and salinites (3.75) are nearly the same for both fluorite and sparry calcite. An elongated form of calcite, of minor abundance, precipitated at lower temperatures. The data indicate that (1) the CO₂ involved in the mineralization was provided by the local marine limestones, (2) the waters were meteoric in origin and underwent an ¹⁸O shift of 10 permil by exchange with marine country rocks, and (3) all geochemical features can be explained by the action of two hydrothermal fluids. Hot brines recently discovered in the Cesano geothermal area, 30 km to the east, have temperatures and some chemical characteristics similar to the hydrothermal fluids at Monte delle Fate.     

Origin of coarse-crystalline calcite cement in Early Ordovician carbonate rocks, Ordos basin, northern China: Insights from oxygen and carbon isotopes and fluid inclusion microthermometry

The calcite cement in the Lower Ordovician Majiagou Formation in the Ordos basin in northern China can be subdivided into three groups based on preliminary results of oxygen and carbon isotopes and fluid inclusion microthermometry. Group 1 has low oxygen isotopes (− 14‰ to − 18‰), low T_h values (92–103 °C), and low salinities (1.7–4.9 wt.% NaCl equivalent) and is interpreted to have precipitated during early burial from porewater influenced by meteoric water. Group 2 has much higher oxygen isotope values (− 5‰ to − 8‰), which, coupled with the higher T_h values (136–151 °C), suggest that the calcite was precipitated from fluids that were significantly enriched in ¹⁸O, possibly resulting from fluid–rock reaction during burial. Group 3 occurring along fractures is characterized by high salinities (21–28 wt.% NaCl equivalent) and is interpreted to have been precipitated from locally preserved residual evaporitic brines. The occurrence of primary hydrocarbon inclusions and its low carbon isotopes (− 11‰ to − 15‰) suggest that precipitation of group 3 calcite took place in the presence of hydrocarbons.     

Stable isotope analysis of the Cenomanian–Turonian (Late Cretaceous) oceanic anoxic event in the Crimea

Carbon and oxygen isotope data from Cenomanian–Turonian sediments from the southwest of the Crimea are presented. The sediments consist of limestones, marls and organic-rich claystones, the latter with total organic carbon values up to 2.6 wt. %, representing Oceanic Anoxic Event 2. A shift to more negative δ¹⁸O values through the uppermost Cenomanian into the lowermost Turonian may be the result of warming; however, petrographic analysis shows that the samples have undergone a degree of diagenetic alteration. The carbon isotope data reveal a positive excursion from 2.7‰ to a peak of 4.3‰ at the Cenomanian/Turonian boundary; values then decrease in the early Turonian. This excursion is comparable to those of other Cenomanian–Turonian sections, such as those seen in the Anglo-Paris Basin, and is thought to be due to global changes in the oceanic carbon reservoir. On this curve are a number of negative δ¹³C excursions, just below the Cenomanian/Turonian boundary. It is suggested that these negative excursions are associated with the uptake of light carbon derived from the oxidation and deterioration of organic material during localised exposure of the sediments to oxic or meteoric diagenetic conditions, possibly during sea-level fluctuations.     

鄂尔多斯盆地下古生界石灰岩岩相及碳、氧稳定同位素特征

鄂尔多斯盆地下古生界石灰岩的岩相及碳、氧稳定同位素组成变化大,具有多种成因类型。通过薄片鉴定、岩石及矿物微区碳、氧稳定同位素测试以及包裹体测温资料研究,发现正常海水成因的泥晶灰岩及颗粒灰岩具有较高的δ18O、δ13C;受淡水淋滤、溶蚀的颗粒灰岩、角砾泥晶灰岩、豹斑含云灰岩或灰云岩的δ13C随淡水淋滤及溶蚀程度升高而明显降低,但其δ18O变化较小;去膏化成因的巨晶次生灰岩在阴极发光下具环带结构,并具有较低的δ18O、δ13C,去云化成因的中-细晶次生灰岩多呈麦粒或蚕蛹结构,其δ18O、δ13C相对较高;早期及表生淡水方解石胶结物的δ18O、δ13C均为低值,Mn离子含量低,阴极发光暗淡;晚期热液方解石胶结物具异常低的δ18O、δ13C,包裹体均一温度介于100~150℃,富含Mn离子,阴极发光明亮。研究结果表明,岩相特征、碳、氧稳定同位素组成以及包裹体测温数据是确定石灰岩沉积、成岩环境以及成因类型的重要指标。     

Changes in carbon and oxygen isotope composition during limestone diagenesis

The calcite fossils of the Derbyhaven Beds, Isle of Man, have δ¹³C values (+ 1·8 PDB) similar to modern, shallow-water marine skeletons, but the δ¹⁸O values (?6·1 PDB) are much lighter than modern skeletons. The light oxygen values indicate either re-equilibration with isotopically light water before cementation started, or Carboniferous sea water with δ¹⁸O of ?6‰. Aragonite dissolution was followed by precipitation of zoned calcite cement. In this cement, up to six intracrystalline zones, recognized in stained thin sections, show isotopic variation. Carbon varies from + 3-8 to + 1-2‰. and oxygen from ? 2-6 to ? 12-4‰. with decreasing age of the cement. This trend is attributed to increasing temperature and to isotopic evolution of the pore waters during burial. The zoned calcite is sequentially followed by dolomite and kaolinite cements which continue the trend towards light isotopic values. This trend is continued with younger, fault-controlled dolomite, and is terminated by vein-filling calcite and dolomite. The younger calcite, interpreted as a near-surface precipitate from meteoric waters, is unrelated to the older sequence of carbonates and has distinctly different carbon isotope ratios: δ¹³C ? 6-8‰.     

Carbon, oxygen, and strontium isotope geochemistry of carbonate rocks of the upper Miocene Kudankulam Formation, southern India: Implications for paleoenvironment and diagenesis

The carbon, oxygen, and strontium isotope compositions of carbonate rocks from the upper Miocene Kudankulam Formation, southern India, were measured to understand palaeoenvironment and carbonate diagenesis of this formation. Both carbon and oxygen isotope ratios of various carbonate phases including whole rocks, ooids, molluscan mold-fill and sparry pore-fill calcite cements are depleted in ¹⁸O and ¹³C compared to those of contemporaneous seawater, indicating that the Kudankulam carbonates underwent extensive meteoric diagenesis. Based on δ¹³C and δ¹⁸O values for sparry calcite cements (pore-fill and molluscan mold-fill) formed in the meteoric diagenetic realm (δ¹³C from −7.8‰ to −6.0‰ and −9.0‰ to −7.0‰; δ¹⁸O from −9.2‰ to −6.5‰ and −9.4‰ to −2.6‰, respectively), it is interpreted that the diagenetic system was open and was proximal to the vadose water recharge zone. The negative δ¹⁸O values of various carbonate components (about −9.4‰ to −4.1‰ for whole rocks; about −8.4‰ to −2.6‰ for ooids) suggest that during the late Miocene the paleoclimate of the study area was humid, unlike today, probably due to the intense Indian monsoon system. The carbon isotope compositions (−7.9‰ to −3.6‰ for whole rocks; −4.9‰ to −1.5‰ for ooids) are consistent with the interpretation that the paleo-ecosystem comprised a significant proportion of C₄ type plants, supporting a scenario of expansion of C₄ plants during the late Miocene in the Indian subcontinent as far south as the southern tip of India. The ⁸⁷Sr/⁸⁶Sr ratios of the Kudankulam carbonates (0.70920 to 0.72130) are much greater than those of the contemporaneous or modern seawater (between 0.7089 and 0.7091) and show a general decrease up-sequence. Such high Sr isotope ratios indicate significant radiogenic ⁸⁷Sr influx to the system from the Archean rocks exposed in the drainage area, implying that the deep-seated Archean rocks were already exposed in southern India by the late Miocene.     

Carbonatite tuffs in the Laetolil Beds of Tanzania and the Kaiserstuhl in Germany

Carbonatite lava and tephra are now well known. The only modern eruptive carbonatites, from Oldoinyo Lengai, Tanzania, are of alkali carbonatite, whereas all of the pre-modern examples are of calcite or dolomite. Chemical and stable isotope analyses were made of separate phases of Pliocene carbonatite tuffs of the Laetolil Beds in Tanzania and of Miocene carbonatite tuffs of the Kaiserstuhl in Germany in order to understand the reasons for this major difference.The Laetolil Beds contain numerous carbonatite and melilitite-carbonatite tuffs. It is proposed that the carbonatite ash was originally of alkali carbonate composition and that the alkali component was dissolved, leaving a residuum of calcium carbonate. The least recrystallized melilitite-carbonatite tuff contains early-deposited calcite cement and calcite pseudomorphs after nyerereite (?) that have contents of strontium and barium and ¹⁸O and ¹³C values suggestive of incomplete chemical and isotopic exchange during alteration and replacement of alkali carbonatite ash.Carbonatite tuffs of the Kaiserstuhl contain globules composed of calcite phenocrysts and microphenocrysts in a groundmass of calcite with a small amount of clay, apatite, and magnetite. The SrO contents of phenocrysts, microphenocrysts, and groundmass calcite average 0.90, 1.42, and 0.59 percent, respectively. The average ¹⁸O and ¹³C values of globules (+14.3 and –9.0, respectively) fall between those of coarse-grained intrusive Kaiserstuhl carbonatite (avg. +6.6, –5.8) and those of low-temperature calcite cement in the carbonatite tuffs (+21.8, –14.9). The phenocrysts and microphenocrysts are primary magmatic calcite, but several features indicate that the groundmass has been recrystallized and altered in contact with meteoric water, resulting in weathering of silicate to clay, leaching of strontium, and isotopic exchange. The weight of evidence favors an original high content of alkali carbonatite in the groundmass, with recrystallization following leaching of the alkalies.     

Carbon isotopic study on graphite and carbonate in the Kamioka mining district,Gifu Prefecture,central Japan,in relation to the role of graphite in the pyrometasomatic ore deposition

Pyrometasomatic lead-zinc ore deposits of the Kamioka mine occur in the Hida metamorphic complex of central Japan. The pyrometasomatic ore deposition was followed by small scale hydrothermal ore deposition. Flaky graphite characteristically occurs in skarn, ores and in the surrounding crystalline limestone. ¹³C values of graphite in the skarn and the ores are close to those of graphites in the crystalline limestone. Graphite in the skarn and ores is considered to be remains of graphite in the crystalline limestone which was replaced by the skarn and the ores. At the pyrometasomatic stage, the oxygen fugacity of fluid would control the carbon isotopic composition of calcite precipitated. On the assumption that graphite played a role of oxygen buffer, the oxygen fugacity of the fluid was estimated to be from 10^–31,4 to 10^–301 bars at 350 °C and total pressure of 1,000 bars. The predominant carbon species in the fluid would be carbon dioxide. The ¹³C value of total carbon in fluid was estimated to be –3.6±1.7 (PDB) for the Tochibora and Maruyama deposits of the Kamioka mine, and the oxygen fugacity in the fluid was probably constant during the pyrometasomatic stage. It is likely that an important source of carbon was the carbon remained after the decarbonation of crystalline limestone. Oxygen isotopic studies on calcite of pyrometasomatic and hydrothermal stages revealed that meteoric water was an important source for most of the oxygen in fluid of both stages.     

Quantification of mixing processes in ore-forming hydrothermal systems by combination of stable isotope and fluid inclusion analyses

In the Schwarzwald area, southwest Germany, more than 400 hydrothermal veins hosting different gangue and ore mineral assemblages cross-cut the crystalline basement rocks. Many of the post-Variscan fluorite-barite-quartz veins are considered to have precipitated through mixing of a deep saline brine with meteoric, low salinity waters. This hypothesis was tested using carbon, sulfur, and oxygen isotope data of sulfides, sulfates and calcite, coupled with fluid inclusion studies. Primary hydrothermal calcites from the deposits show a positive correlation of their δ¹³C (V-PDB) and δ¹⁸O (V-SMOW) values, which range from −12 to −3‰ and from 12 to 18.5‰, respectively. Carbon and oxygen isotope compositions of paragenetically young, remobilized calcite types are shifted towards higher values and range from −12 to −1‰ and from 20 to 25‰, respectively. We developed an improved calculation procedure for modeling the covariation of carbon and oxygen isotopes in calcite resulting from mixing of two fluids with different isotopic compositions and total carbon concentrations. In our model, the carbon speciation in the two model fluid end-members and the fluid mixtures are calculated using a speciation and reaction path code. The carbon and oxygen isotope covariation of primary Schwarzwald calcites can effectively be modeled by a mixing trend of a deep saline brine and a meteoric, low salinity water. Sulfur isotope data of barites from 44 hydrothermal fluorite-barite-quartz veins vary from 9 to 18‰ (CDT), sulfide ore minerals show δ³⁴S values between −14.4 and 2.9‰. Calculated sulfide-sulfate equilibrium temperatures are in the range between 300 and 350 °C. These temperatures differ significantly from the formation temperatures of 150 to 200 °C of most of the deposits as estimated from fluid inclusions, and are interpreted as preserved paleotemperatures of the deep aquifer. This assumption has been carefully checked against possible contamination of an equilibrated sulfide-sulfate system from the deep aquifer with sulfate from surface-derived sources, considering also the kinetics of the sulfide-sulfate isotope exchange. A combination of the S isotopic results with microthermometric fluid inclusion data and constraints on the temperature of the meteoric water was used to calculate mixing ratios of the two fluid end-members. The results indicate that mass fractions of the deep saline brine in the mixed fluid were between 0.5 and 0.75. Considering all geologic, geochemical and isotopic information, we propose that the majority of the post-Variscan hydrothermal veins in the Schwarzwald area were precipitated by district-scale mixing of a homogeneous deep saline brine with meteoric waters.     

Carbonates and sources of fluids in ores and metasomatites of the Ermakovka fluorite-bertrandite-phenacite deposit (western Transbaikalia)

We present results of isotope-geochemical study of the Ermakovka F-Be deposit, including data on the oxygen and carbon isotope compositions in dolomite and calcite marbles and in carbonates accompanying skarns, of early and late stages of ore formation and of post-ore parageneses. To elucidate the sources of fluids participated in the ore formation, we calculated the oxygen isotope composition in water and the hydrogen isotope composition in hydroxyl-containing minerals. Phlogopite in marbleized dolomites, vesuvianite and amphibole in skarns, eudidimite and bertrandite in ore parageneses, and bavenite formed during post-ore processes are analyzed. Most of the ore-stage minerals are depleted in heavy oxygen. Their 5¹⁸O values are lower than 5-6%c (SMOW). Oxygen in carbonate minerals of the initial stage (dolomite and bastnaesite) is heavier (1.3-4.9%c) than that in calcite (+ 2 to -3.7%c). The 5¹⁸O values of water in equilibrium both with carbonate and with silicate minerals (-4 to -14%c) suggest the contribution of meteoric water to the mineral formation. A magmatic fluid (5¹⁸O from + 6 to + 9%c) participated in the skarn formation at the initial stage, and a meteoric fluid, at the final stage (5¹⁸O from -1 to -9%c). A meteoric source is confirmed by the depleted hydrogen isotope composition in minerals (5D from -119 to -192%c).     

Isotope signatures associated with early meteoric diagenesis

The environments in which carbonate diagenesis proceeds have been documented in previous studies of Holocene and late Pleistocene sediments and limestones on Barbados, West Indies. Variations in the carbon and oxygen isotopic composition of limestones, produced during early freshwater diagenesis, have been observed in this study to occur in specific patterns. Six potentially useful patterns emerge when one views stable isotope data within a stratigraphic framework: (1) the subaerial exposure surface is characterized by strongly ¹²C-enriched limestones. δ¹³C compositions of underlying limestones grow progressively heavier with increasing depth; (2) the subaerial exposure surface may also be marked by slight ¹⁸O-enrichment; (3) an abrupt shift in δ¹⁸O values may differentiate sediments above the exposure surface from those below; (4) sediments altered in the marine-meteoric mixing zone may be characterized by positive covariance between their δ¹⁸O and δ¹³C compositions; (5) the vadose-phreatic boundary may be marked by a sharp increase in δ¹³C values in the seaward portions of a fresh groundwater system; and (6) samples contemporaneously altered in a single fresh groundwater system within an areally restricted region should display a narrow range of δ¹⁸O and a wide range of δ¹³C compositions. Analysis of samples from five Palaeozoic and Mesozoic formations, which contained petrographic evidence of early freshwater diagenesis, showed that isotope patterns similar to those observed in Barbados limestones have been preserved in rocks as old as Mississippian. These isotope patterns could prove to be useful for identifying diagenetically induced porosity trends in carbonate rocks. They might be used to identify limestones diagenetically altered in meteoric environments, to identify mixing zone cements and dolomites, and to trace the regional and vertical distributions of early meteoric groundwater systems in ancient carbonate formations.     

Syntectonic hydrothermal calcite in a faulted carbonate platform margin (Albian of Jorrios, northern Spain)

ABSTRACT A calcite mass more than 1·5 km long and 20 m wide crops outs along the faulted margin of the Albian carbonate platform of Jorrios in northern Spain. The mass contains abundant dissolution cavities up to 7 m long and 1 m high, filled with cross‐stratified quartz sandstone and alternating sandstone–calcite laminae. Similar cavities are also present in a 50‐m‐wide zone of platform limestones adjacent to the calcite mass that are filled with limestone breccias and sandstone. The calcite mass has mean δ¹⁸O values of 19·6‰ (SMOW), whereas platform limestones have mean δ¹⁸O values of 24·4‰ (SMOW). Synsedimentary faulting of the carbonate margin and circulation of heated fault‐related waters resulted in replacement of a band of limestone by calcite. Soon after this replacement, dissolution by undersaturated fluids affected both the calcite mass and the adjacent limestones. Percolating marine quartz sand filled all dissolution cavities, sometimes alternating with precipitating calcite. The resulting cavities and fills, which recall products of meteoric diagenesis, are attributed to a hydrothermal origin based on their geometry, occurrence along the profile and synsedimentary tectonic relationships. The early faulting and diagenesis are related to local extensional tectonism in a large‐scale strike‐slip setting. Movements occurred during the early dispar/appenninica zone of the Late Albian.     

Diagenetic model of carbonate rocks of Guri Member of Mishan Formation (Lower to Middle Miocene) SE Zagros basin,Iran

In order to understand the post-depositional history of carbonate rocks of Guri Member (Lower to Middle Miocene), three stratigraphic sections were selected in north Bandar-Abbas in southeast of Iran. Sampling was carried out, analyzed for selective parameters such as oxygen and carbon isotopic compositions (δ¹⁸O and δ¹³C) and interpreted in the present study. We recognized several diagenetic processes including micritization, cementation, neomorphism, compaction, dissolution, silicification, dolomitization, fracturing and vein filling. Some of the diagenetic processes occurred at different conditions, so in order to achieve precise interpretation, samples from different carbonate components such as, micrite, fracture cement, solution pore cement, intergranular cement, and some biotic allochems were analyzed. In this study micrite samples were subdivided into two groups including micro-spary and micrite. They were recognized under Cathodoluminescence microscope. In addition, micrite samples were classified into five groups based on their depositional environments: supratidal, lagoon, coral bar, open sea, and open basin. There were minor changes in stable isotope ratios based on the sedimentary environments, stratigraphy successions, and micro-spary or micrite properties. In this study, similar calcite cements in petrography studies were differentiated by stable isotope data. Those calcite cements have formed in different diagenetic environments such as meteoric and burial cements. Paragenetic sequence of carbonate rocks were interpreted by integration of petrographic and isotopic studies. We have reconstructed diagenetic models of Guri Member into four stages including marine, meteoric, burial, and uplifting.     

Stable isotope and fluid inclusion studies of carbonate deposits from the Tolfa Mountains mining district (Latium,central Italy)

Carbon and oxygen isotope analyses were made of representative samples of calcite and quartz from the carbonate deposits in the Tolfa Mountains mining district. Measurements were also made of hydrogen isotope compositions, filling temperatures and salinities of fluid inclusions in these minerals. There are three stages of mineralization at Tolfa. In stage I, characterized by calc-silicate hornfels, the carbonates have relatively high ¹⁸O values of 14.5 to 21.6 suggesting a rather low water/rock ratio. ¹³C values of –0.3 to 2.1 indicate that appreciable decarbonation or introduction of deep-seated carbon did not occur. Stage II is marked by phanerocrystalline carbonates; ¹⁸O values of 13.1 to 20.0 and ¹³C values of 0.7 to 5.0 identify them as hydrothermal veins rather than marbles. D values of –56 to –50 for inclusion fluids suggest a possible magmatic component to the hydrothermal fluid. Filling temperatures of coarse-grained samples of Calcite II are 309° to 362° C with a salinity range of 5.3 to 7.1 weight percent NaCl. Calculated ¹⁸O values of 11–12 for these fluids are again indicative of low water/rock ratios. The sparry calcites of stage III have ¹⁸O and ¹³C values of 8.1 to 12.9 and –1.7 to 3.2, respectively. D values of inclusion fluids are –40 to –33, clearly heavier than in earlier stages and similar to values of modern local ground waters. A salinity measurement of <0.1 weight percent NaCl in a sample of Calcite III is compatible with a relatively unaltered ground water origin for this fluid. Precipitation of the sparry calcite took place at much lower temperatures, around 160° C. For quartz, ¹⁸O values of 9.3 to 12.4 and D values for inclusions of –53 to –28 are consistent with its late occurrence and paragenetic link with associated carbonates.     

Geochemistry of meteoric calcite cements in some Pleistocene limestones

In this study, the stable isotope and trace element geochemistries of meteoric cements in Pleistocene limestones from Enewetak Atoll (western Pacific Ocean), Cat Island (Bahamas), and Yucatan were characterized to help interpret similar cements in ancient rocks. Meteoric calcite cements have a narrow range of δ¹⁸O values and a broad range of δ¹³C values in each geographical province. These Pleistocene cements were precipitated from water with stable oxygen isotopic compositions similar to modern rainwater in each location. Enewetak calcite cements have a mean δ¹⁸O composition of ?6.5%₀ (PDB) and δ¹³C values ranging from ?9.6 to +0.4%0 (PDB). Sparry calcite cements from Cat Island have a mean δ¹⁸O composition of ?4.1%₀ and δ¹³C values ranging from ?6.3 to + 1.1%₀. Sparry cements from Yucatan have a mean δ¹⁸O composition of ?5.7%₀ and δ¹³C values of ?8.0 to ?2.7%₀. The mean δ¹⁸O values of these Pleistocene meteoric calcite cements vary by 2.4%₀ due to climatic variations not related directly to latitude. The δ¹³C compositions of meteoric cements are distinctly lower than those of the depositional sediments. Variations in δ¹³C are not simply a function of distance below an exposure surface. Meteoric phreatic cements often have δ¹³C compositions of less than —4.0%₀, which suggests that soil-derived CO₂ and organic material were washed into the water table penecontemporaneous with precipitation of phreatic cements. Concentrations of strontium and magnesium are quite variable within and between the three geographical provinces. Mean strontium concentrations for sparry calcite cements are, for Enewetak Atoll, 620 ppm (σ= 510 ppm); for Cat Island, 1200 ppm (σ= 980 ppm); and for Yucatan, 700 ppm (σ= 390 ppm). Equant cements, intraskeletal cements, and Bahamian cements have higher mean strontium concentrations than other cements. Equant and intraskeletal cements probably precipitated in more closed or stagnant aqueous environments. Bahamian depositional sediments had higher strontium concentrations which probably caused high strontium concentrations in their cements. Magnesium concentrations in Pleistocene meteoric cements are similar in samples from Enewetak Atoll (mean =1.00 mol% MgCO₃; σ= 0.60 mol% MgCO₃) and Cat Island (mean = 0.84 mol% MgCO₃; σ= 0.52mol% MgCO₃) but Yucatan samples have higher magnesium concentrations (mean = 2.20 mol% MgCO₃: σ= 0.84mol% MgCO₃). Higher magnesium concentrations in some Yucatan cements probably reflect precipitation in environments where sea water mixed with fresh water.     

Diagenetic alteration of early marine cements of Upper Silurian stromatactis

Stromatactis is a spar network whose elements in cross section have flat to undulose lower surfaces and digitate upper surfaces. The network is composed principally of isopachous crusts of centripetal cement and commonly occurs embedded in finely crystalline limestone. It is the cement filling of interconnected cavities. Stromatactis of Upper Silurian red stromatactis limestone from Gaspé Peninsula, Québec Appalachians, exhibits two types of cements: (1) an isopachous cement that lined the walls of the conduits and is interpreted as early marine; and (2) a later blocky cement that occupies the centres of cavities. The first cement is composed exclusively of non-ferroan calcite, whereas the second cement is mixed non-ferroan and ferroan calcite. The early isopachous cement is white on polished slabs and has a turbid aspect under transmitted light. In a few samples, the relative homogeneity of this early cement is broken by the presence of distinctive grey clear calcite. Under cathodoluminscence, the grey clear calcite is non-luminescent and exhibits well defined bladed crystal shapes, whereas the white turbid cement has a dull orange luminescence and indistinct crystal shapes. The relationships between the two cements indicate that the dull luminescent cement is a secondary form of the non-luminescent cement, and it is concluded that the dull cement is the product of alteration of the non-luminescent cement by burial or meteoric fluids. The later blocky cement has the same dull luminescence as the white turbid cement and is thought to have been precipitated from the same fluids as those responsible for the alteration of the early marine cements. Oxygen isotopic values of the dull cement of the early isopachous crusts (mean δ¹⁸O= -6.8%_o are intermediate between those of the non-luminescent early marine cement (mean δ¹⁸O= -5.3%_o) and the dull luminescent blocky cement (mean δ¹⁸O= -11.8%_o), while carbon isotopic values do not differ significantly (δ¹³C=+2.9, +2.4 and +2.6%_o, respectively). The alteration also has affected the distribution of some trace elements, particularly Mg. Both unaltered and altered cements contain less than 1% microdolomite inclusions, but the Mg content of the background calcite of unaltered cement is three times that of altered cement (14171 vs. 5502 ppm). Precursor early marine cement is thought to have been low-Mg calcite. The mean δ¹⁸O value (− 5.3%_o) of unaltered early marine cement is higher than values for the oxygen isotopic signature of Silurian oceans provided by brachiopod shells.     

Diagenetic development of a Precambrian limestone as interpreted from a modern analogue

A strong correlation in the geometry and mineralogy of two cement generations of a Quaternary with a Precambrian calcarenite enables us to reconstruct the diagenetic history of the Precambrian limestone. Both calcarenites contain two cement generations (A and B) of which A consists of dolomite, B of calcite. The following diagenetic stages can be recognized: after deposition of the allochems in a shallow marine environment, cementation in the intertidal zone with magnesian calcite (cement A) led to the formation of beachrock (Stage 1). By lowering of the sea level, the beach rock was shifted into the supratidal zone, but still remained under the predominant influence of the sea water (breakers, spray). During longer periods of aridity, the magnesian calcite of cement A and of the allochems was transformed into dolomite by brines derived from sea water with very high Mg/Ca ratio (> 15), whereas aragonite and calcite remained unaffected. After further lowering of the sea, an increasing influence of meteoric water caused the wet transformation of aragonitic allochems to sparry calcite and to the precipitation of sparry calcitic cement B.     

Stable isotopic compositions of Recent freshwater cyanobacterial carbonates from the British Isles: local and regional environmental controls

Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ¹⁸O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ¹⁸O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO₂ and aqueous HCO^?₃. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ¹⁸O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate.     

Radiaxial fibrous calcites as low-magnesian calcite cement precipitated in a marine-meteoric mixing zone

Abstract Radiaxial fibrous calcite (RFC) has previously been interpreted as a marine or replacive cement. Study of the Dongjeom Formation (Early Ordovician), Korea, shows that RFC can form in marine‐meteoric mixing zones as a low‐magnesian calcite (LMC) cement. RFC in the shallow‐marine Dongjeom Formation occurs in arenaceous limestones at the top of a transgressive facies overlying a regressive facies. It shows well‐developed growth zonation, and lighter oxygen isotope values and more radiogenic strontium isotope ratios than those of Early Ordovician marine calcite. Such petrographic and chemical evidence indicates that the RFC was precipitated as a primary LMC cement in a marine and meteoric mixing zone. Owing to the unique environment of formation, the Dongjeom RFC is characterized by growth zonal fabric comprising alternating subzones, which may indicate precipitation from varying fluids. In addition, this study documents the importance of substrate for development of RFC. Early ‘nucleation’ for RFC occurred mainly on microcrystalline skeletal grains and internal sediments, whereas on homogeneously altered substrates, thin‐coated banding structure developed, ultimately forming coarse crystalline spar. This suggests that microcrystalline substrates are preferred sites for nucleation of RFC.