Evaluation of bulk carbonate δ13C data from Triassic hemipelagites and the initial composition of carbonate mud

Bulk carbonate samples of hemipelagic limestone–marl alternations from the Middle and Upper Triassic of Italy are analysed for their isotopic compositions. Middle Triassic samples are representative of the Livinallongo Formation of the Dolomites, while Upper Triassic hemipelagites were sampled in the Pignola 2 section, within the Calcari con Selce Formation of the Southern Apennines in Southern Italy. Triassic hemipelagites occur either as nodular limestones with chert nodules or as plane‐bedded limestone–marl alternations which are locally silicified. In the Middle Triassic Livinallongo Formation, diagenetic alteration primarily affected the stable isotopic composition of sediment surrounding carbonate nodules, whereas the latter show almost pristine compositions. Diagenesis lowered the carbon and oxygen isotope values of bulk carbonate and introduced a strong correlation between δ¹³C and δ¹⁸O values. In the Middle Triassic successions of the Dolomites, bulk carbonate of nodular limestone facies is most commonly unaltered, whereas carbonate of the plane‐bedded facies is uniformly affected by diagenetic alteration. In contrast to carbonate nodules, plane‐bedded facies often show compaction features. Although both types of pelagic carbonate rocks show very similar petrographic characteristics, scanning electron microscopy studies reveal that nodular limestone consists of micrite (< 5 μm in diameter), whereas samples of the plane‐bedded facies are composed of calcite crystals ca 10 μm in size showing pitted, polished surfaces. These observations suggest that nodular and plane‐bedded facies underwent different diagenetic pathways determined by the prevailing mineralogy of the precursor sediment, i.e. probably high‐Mg calcite in the nodular facies and aragonite in the case of the plane‐bedded facies. Similar to Middle Triassic nodular facies, Upper Triassic nodular limestones of the Lagonegro Basin are also characterized by uncorrelated δ¹³C and δ¹⁸O values and exhibit small, less than 5 μm size, crystals. The alternation of calcitic and aragonitic precursors in the Middle Triassic of the Dolomites is thought to mirror rapid changes in the type of carbonate production of adjacent platforms. Bioturbation and dissolution of metastable carbonate grains played a key role during early lithification of nodular limestone beds, whereby early stabilization recorded the carbon isotopic composition of sea water. The bulk carbonate δ¹³C values of Middle and Upper Triassic hemipelagites from Italy agree with those of Tethyan low‐Mg calcite shells of articulate brachiopods, confirming that Triassic hemipelagites retained the primary carbon isotopic composition of the bottom sea water. A trend of increasing δ¹³C from the Late Anisian to the Early Carnian, partly seen in the data set presented here, is also recognized in successions from tropical palaeolatitudes elsewhere. The carbon isotopic composition of Middle and Upper Triassic nodular hemipelagic limestones can thus be used for chemostratigraphic correlation and palaeoenvironmental studies.     

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.     

Fluid mixing in carbonate aquifers near Rapolano (central Italy): chemical and isotopic constraints

Chemical (major and trace elements) and isotopic compositions (δD and δ¹⁸O in waters and δ¹³C in CO₂ and ³He/⁴He in gases) of natural thermal (11) and cold (39) fluids (spring waters and gases) discharging from a tectonic window of Mesozoic limestones in central Italy, have proved to be the result of mixing processes inside the limestone formations. The limestones provide a preferential route for subsurface fluid migration and they gather both descending cold, Ca-HCO₃, B-depleted groundwaters and rising convective Ca-SO₄(HCO₃), CO₂-saturated, B-rich thermal waters. Atmospherically-derived descending gas components (N₂, Ne, He), dissolved in rainfall that infiltrates the limestone system mix with N₂, Ne, He-depleted hot rising waters. Boron in the liquid phase and N₂ and Ne in the gas phase are the most useful elements to trace the mixing process. The deeper gas samples recognised in the area are associated with the hotter waters emerging in the area. In spite of being depleted in Ne and He and light hydrocarbons they have the higher measured ³He/⁴He ratios, suggesting a contribution of mantle ³He to the gas phase. This contrasts with deep circulation in the crust which would lead to increased concentration of ⁴He in the deeper gases. Paradoxically, there is more relative concentration of ⁴He in the more air-contaminated gas samples than in the deeper gas samples. A similar paradox exists when the δ¹³C of CO₂ in the deeper gas samples is considered. The shallower air-contaminated gas samples, although they should be affected by the addition of soil-¹³C depleted organic C, have δ¹³C in CO₂ more positive than the deeper gas samples recognized. Since any deep hydrothermal source of CO₂ should generate CO₂ with more positive values of δ¹³C than those measured at surface, a multiple (single) calcite precipitation process from hydrothermal solutions, with C isotopic fractionation along the rising path inside the Mesozoic limestone formations, is proposed.     

Carbon and Oxygen Isotope Compositions of Some Upper Cretaceous–Paleocene Sequences in Argentina and Chile

The Cretaceous-Paleocene (K-T) transition has been recorded in sedimentary carbonate rocks in northwestern Argentina and southern Chile. In the Yacoraite Basin, Argentina, this transition has been preserved in a 2 m thick marly layer, at the base of the Tunal Formation, which overlies lacustrine/marine carbonates of the Yacoraite Formation (Cabra Corral dam). The K-T transition is also preserved at Maimara, where Tertiary sandstones overlie a 50 m thick limestone bed of the Yacoraite Formation. In the Magellan Basin, Chile, glauconitic sandstones with calcitic cement and limestone concretions of the Maastrichtian Punta Rocallosa Formation are overlain by sandstones, claystones, and limestones of the Chorillo Chico Formation. The K-T transition is preserved in the lower portion of the Chorillo Chico Formation.

Carbonates of the Yacoraite Formation display bulk-rock δ¹³C values from +1 to +2‰ PDB, with a negative incursion (?4‰ PDB) at the K-T transition. δ¹³C values in the Tunal Formation marls vary from ?3 to ?1‰ PDB. At Rocallosa Point, δ¹³C values in limestone strata, calcite cement, and limestone concretions vary from ?4 to ?33 ‰ PDB, and the lowest value in the Chorillo Chico Formation apparently marks the K-T transition. The δ¹⁸O fluctuations in the Yacoraite and Magellan carbonate rocks suggest a temperature drop at the K-T transition, followed by a temperature rise.

High ⁸⁷Sr/⁸⁶Sr ratios (0.7140-0.7156) characterize the studied profiles of the Yacoraite Formation, documenting an important ⁸⁷Sr-enriched source of Sr to the water from which these carbonates precipitated. At the Magellan basin, ⁸⁷Sr/⁸⁶Sr ratios are closer to the expected values for the global Late Cretaceous-Paleocene ocean.     

Carbon isotope stratigraphy: a tool for basin to carbonate platform correlation

The Early Cretaceous carbonate carbon isotope stratigraphy established in pelagic limestones is marked by several pronounced excursions towards positive δ¹³C values. We investigated a biostratigraphically and palaeomagnetically calibrated Aptian section to see whether C isotope stratigraphy could be recognized in shallow-water carbonates. The chosen carbonate platform sections are located in southern Italy and have been dated by biostratigraphy. Bulk samples, chosen from the Barremian-Albian part of the sequence, were analysed for their O and C isotope compositions. The C isotope curve established shows two major positive excursions which can be correlated with the synchronous and globally recognized Aptian C isotope events. The data provide evidence that C isotope stratigraphy can be used as a powerful correlation tool between pelagic and shallow-water limestone sequences.     

Carbon and Oxygen Isotopic Signatures in Albian-Danian Limestones of Cauvery Basin, Southeastern India

The Albian-Danian limestones of Cauvery Basin show a wide range of d¹³C and d¹⁸O values (–13.2 to +1.1% and –9.0 to –2.5%, respectively). The cement samples show negative carbon and oxygen isotope values (–18.9 to –3.9% and –9.0 to –4.3%, respectively). The petrographic study reveals the presence of algae, molluscs, bryozoans, foraminifers and ostracods as major framework constituents. The limestones have microspar and equant sparry calcite cements. The pore spaces and vugs are filled with sparry calcite cement. The bivariate plot of d¹³C and d¹⁸O suggests that most of the samples fall in the freshwater limestone and meteoric field, while few samples fall in the marine limestone and soil calcite fields. The presence of sparry calcite cement, together with negative carbon and oxygen isotope values, indicates that these limestones have undergone meteoric diagenesis.     

Contrast in the isotopic composition of oxygen and carbon between the Mud Tank Carbonatite and the marbles in the granulite terrane of the Strangways Range,central Australia

Three samples from the Mud Tank Carbonatite have very similar isotopic ratios, averaging δ¹³C=‐4.3 and δ¹⁸O=+7.5(SMOW). These isotope values are distinct from those of nearby highly metamorphosed Carpentarian marbles, which have marine limestone values of δ¹³C=‐1.3±0.5, and δ¹⁸O=+17.6+0.7 with n=11. Minor variations in the values for the normal marbles show no correlation with stratigraphy or geographic location; however, somewhat lighter oxygen is found in some other marbles known to be affected by low‐temperature fluids within the Woolanga Lineament. Isotopes of C and O, if discretely used in conjunction with other geochemical features, not only may discriminate between deep‐seated carbona‐tites and marbles, but may also help to identify zones of carbonate metasomatism and define the isotopic characters of the fluids.     

Carbon isotopic composition of diamonds from the Archangelsk diamond province

The first data are reported on the carbon isotopic composition of diamond crystals from the Grib pipe kimberlite deposit of the Archangelsk diamond province (ADP). The δ¹³C value of the crystals ranges from ?2.79 to ?9.61‰. The isotopic composition of carbon was determined in three zoned crystals (δ¹³C of ?5.8 ?6.96 ‰, ?5.64/ ?5.85 ‰, and ?5.94/ ?5.69 ‰), two “diamond in diamond” samples (diamond inclusion with δ¹³C of ?4.05 and ?6.34 ‰ in host diamond crystals with δ¹³C of ?8.05 and ?7.54 ‰, respectively), and two samples of coated diamonds (cores with δ¹³C of ?6.98 and ?6.78‰ and coats with δ¹³C of ?7.51 and ?8.01 ‰, respectively). δ¹³C values were obtained for individual diamond crystals from bort-type aggregates (δ¹³C of ?4.24/ ?4.05 ‰, ?6.58/ ?7.48 ‰, and ?5.48/ ?6.08 ‰). Correlations were examined between the carbon isotopic composition of diamonds and their crystal morphology; the color; the concentration of nitrogen, hydrogen, and platelet defects; and mineral inclusions content. It was supposed that the observed δ¹³C variations in the crystals are most likely related to the fractionation of carbon isotopes rather than to the heterogeneity of carbon sources involved in diamond formation. The isotopic characteristics of diamonds from the Grib pipe were compared with those of previously investigated diamonds from the Lomonosov deposit. It was found that diamonds from these relatively closely spaced kimberlite fields are different; this also indicates the existence of spatially localized peculiarities of isotope fractionation in processes accompanying diamond formation.     

Evidence for high temperature and 18O‐enriched fluids in the Arab‐D of the Ghawar Field,Saudi Arabia

Using the clumped isotope method, the temperature of dolomite and calcite formation and the oxygen isotopic composition (δ¹⁸O_w) of the diagenetic fluids have been determined in a core taken from the Arab‐D of the Ghawar field, the largest oil reservoir in the world. These analyses show that while the dolomites and limestones throughout the major zones of the reservoir recrystallized at temperatures between ca 80°C and 100°C, the carbonates near the top of the reservoir formed at significantly lower temperatures (20 to 30°C). Although the δ¹⁸O values of the diagenetic fluids show large variations ranging from ca <0‰ to ca +8‰, the variations exhibit consistent downhole changes, with the highest values being associated with the portion of the reservoir with the highest permeability and porosity. Within the limestones, dolomites and dolomites associated with the zone of high permeability, there are statistically significant different trends between the δ¹⁸O_w values and recrystallization temperature. These relationships have different intercepts suggesting that fluids with varying δ¹⁸O_w values were involved in the formation of dolomite and limestone compared to the formation of dolomite associated with the zone of high permeability. These new data obtained using the clumped isotope technique show how dolomitization and recrystallization by deep‐seated brines with elevated δ¹⁸O_w values influence the δ¹⁸O values of carbonates, possibly leading to erroneous interpretations unless temperatures can be adequately constrained.     

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.     

Lithofacies associations and stable isotopes of palustrine and calcrete carbonates: examples from an Indian Maastrichtian regolith

Detailed information on semi‐arid, palustrine carbonate–calcrete lithofacies associations in a sheetwash‐dominated regolith setting is sparse. This is addressed by studying the Lower Limestone of the Lameta Beds, a well‐exposed Maastrichtian regolith in central India. The general vertical lithofacies assemblage for this unit comprises: (a) basal calcareous siltstones and marls with charophytes, ostracods and gastropods; (b) buff micritic limestones associated in their upper parts with calcretized fissure‐fill sandstones; (c) sheetwash as fissure‐fill diamictites and thin pebbly sheets, locally developed over a few metres; and (d) sandy, nodular, brecciated and pisolitic calcretes at the top. The sequence is ‘regressive’, with upsection filling of topographic lows by increased sheetwash. Lateral lithofacies change is marked, but there are no permanent open‐water lake deposits. In topographic lows close to the water table, marshy palustrine or groundwater calcretes formed, whereas on better drained highs, brecciation and calcretization occurred. Prolonged exposure is implied, suggesting that shrinkage was the main cause of brecciation. Evidence for rhizobrecciation and other biological calcrete fabrics is sparse, contrasting with the emphasis on root‐related brecciation in many studies of palustrine lithofacies. Stable isotope (δ¹⁸O and δ¹³C) values are consistent with the palustrine limestones being fed from meteoric‐derived groundwater with a strong input of soil‐zone carbon. There is overlap of both δ¹⁸O and δ¹³C values from the various palustrine and calcrete fabrics co‐occurring at outcrop. This suggests that, in groundwater‐supported wetlands, conversion from palustrine carbonate to calcrete need not show isotopic expression, as the groundwater source and input of soil‐zone carbon are essentially unchanged. Cretaceous–Tertiary δ¹⁸O and δ¹³C values from palustrine lithofacies and associated calcretes appear to be strongly influenced by the inherited values from lakes and wetlands. Hydrologically closed lakes and marine‐influenced water bodies tend to result in low negative palustrine δ¹⁸O and δ¹³C values. During brecciation and calcretization, the degree of isotopic inheritance depends on whether or not alteration occurs in waters that are different from those of the original water body or wetland. Marked biological activity (e.g. rhizobrecciation or root mat development) during calcretization may lower δ¹³C values where C₃ plants are abundant but, in shrinkage‐dominated systems, δ¹³C values will be largely inherited from the palustrine limestones.     

New data on Sr-and C-isotopic chemostratigraphy of the Upper Riphean type section (Southern Urals)

New data on Sr-and C-isotopic systematics of carbonate rocks from the Upper Riphean stratotype (Karatau Group of the southern Urals) are obtained for several southwestern sections of the Bashkirian meganticlinorium, which have not been studied before. The results obtained supplement the Sr-and C-isotopic information for the group upper horizons thus detailing chemostratigraphic characterization of the entire succession. Limestone and dolostone samples used to analyze the Sr isotope composition satisfy strict geochemical criteria of the isotopic system retentivity and have been subjected to preliminary treatment in ammonium acetate to remove secondary carbonate phases. Data on 255 samples of carbonate rocks (171 studied for the first time) show that δ¹³C value varies in the Karatau Group succession from ?2.8 to +5.9 ‰ V-PDB with several in-phase excursions from the general trend in all the sections studied in the area 90 × 130 km. The δ¹³C variation trend demarcates several levels in the carbonate succession of the Karatau Group suitable for objectives of regional stratigraphy and for C-isotope chemostratigraphic subdivision of the Upper Riphean. The results of Sr isotopic analysis of 121 samples (51 unstudied before) from the Karatau Group imply that rocks in its lower part (the Katav Formation and basal horizon of the Inzer Formation) experienced considerable secondary alterations, while limestones and dolostones of the overlying interval of the group are frequently unaltered. In the “best” samples satisfying geochemical criteria of the isotopic system retentivity, the ⁸⁷Sr/⁸⁶Sr initial ratio increases from 0.70521–0.70532 in the lower Inzer deposits to 0.70611 in the upper Min’yar carbonates, decreasing to <0.70600 near the top of the latter. Above the regional hiatus separating the Min’yar and Uk formation, this ratio grows from 0.70533 to 0.70605–0.70609 in the limestone succession of the last formation.     

Unique Origin of Skarn at the Ohori Base Metal Deposit,Yamagata Prefecture,NE Japan: C,O and S Isotopic Study

The Ohori ore deposit is one of the Cu–Pb–Zn deposits in the Green Tuff region, NE Japan, and consists of skarn‐type (Kaninomata) and vein‐type (Nakanomata) orebodies. The former has a unique origin because its original calcareous rocks were made by hydrothermal precipitation during Miocene submarine volcanism. Carbon and oxygen isotope ratios of skarn calcite and sulfur isotope ratios of sulfides were measured in and around the deposit. Carbon and oxygen isotope ratios of the skarn calcite are δ¹³C = ?15.51 to ?5.1‰, δ¹⁸O = +3.6 to +22.5‰. δ¹³C values are slightly lower than those of the Cretaceous skarn deposits in Japan. These isotope ratios of the Kaninomata skarn show that the original calcareous rocks resemble the present submarine hydrothermal carbonates at the CLAM Site, Okinawa Trough, than Cenozoic limestones, even though some isotopic shifts had occurred during later skarnization. δ³⁴S ratios of the sulfide minerals from the Kaninomata and Nakanomata orebodies are mostly in a narrow range of +4.0 to +7.0‰ and they resemble each other, suggesting the same sulfur origin for the both deposits. The magnetite‐series Tertiary Kaninomatasawa granite is distributed just beneath the skarn layer and has δ³⁴S ratios of +7.5 to 8.1‰. The heavy sulfur isotope ratio of the skarn sulfides may have been affected by the Kaninomatasawa granite.     

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.     

Isotopic signature of burial diagenesis and primary lithological contrasts in periplatform carbonates (Miocene, Great Bahama Bank)

The stable isotope geochemistry of Miocene sediments from the leeward margin of the Great Bahama Bank was examined to investigate burial diagenetic processes in periplatform carbonates. Data indicate that, in addition to differences in bulk proportions of neritic and pelagic carbonate along the slope, rhythmic variation in primary carbonate content has controlled patterns of burial diagenesis and associated geochemical signatures throughout much of the succession examined. The present study focuses on Ocean Drilling Program Sites 1006 and 1007, the most distal of five sites drilled from marginal to deep basin environments during Leg 166. These Miocene sections are characterized by their cyclic appearance, manifest as decimetre‐ to metre‐scale alternations between light‐coloured ooze/chalk/limestone and dark‐coloured marl/marlstone. The section at Site 1006 contains a high proportion of pelagic carbonate and is unlithified to a subbottom depth of ～675 m. Fluctuations in δ¹⁸O and δ¹³C values at this site are independent of lithological variation and reflect primary conditions. At Site 1007, located at the toe‐of‐slope and composed of a mixture of bank‐derived and pelagic carbonate, limestones are densely cemented, show little evidence of compaction and have δ¹⁸O values up to 2‰ higher than coeval sediments at Site 1006. Marlstones at Site 1007 are poorly cemented, exhibit an increase in compaction‐related features with depth and have lower and more variable δ¹⁸O values that are similar to those of coeval sediments at Site 1006. Isotopic and petrographic characteristics of limestone interbeds result from cement precipitation from cold sea water during the first ～100 m of burial. Higher proportions of insoluble materials and pelagic carbonate seem to have inhibited diagenetic alteration in adjacent marlstones; in spite of significant compaction and pressure solution during burial, original isotopic compositions appear to be best preserved in these intervals at Site 1007. The documented contrasts in petrographic and isotopic patterns illustrate the role of primary sediment composition in controlling lithification processes in periplatform carbonates and stress the importance of considering such factors when interpreting geochemical data from ancient shelf and slope limestones.     

广西香田弗拉斯-法门阶界线事件标志——碳、氧稳定同位素异常特征

本文对广西香田晚泥盆世弗拉斯-法门阶界线剖面进行了系统的碳、氧稳定同位素研究。发现随着弗拉斯-法门期之交的生物大量死亡和绝灭,在弗拉斯-法门阶界线层中,碳、氧稳定同位素组成出现了明显的异常。这和白垩—第三系界线灾变事件中出现的异常颇为相似。碳同位素异常达-6.6‰左右,氧同位素出现正异常达2‰。此外,在界线层中出现铱异常为230×10^-12g/g。这些表明,上述同位素地球化学异常是地球历史中生物绝灭灾变事件的重要标志。     

Milankovitch cyclicity in Purbeck peritidal limestones of the Prebetic (Berriasian, southern Spain)

Peritidal carbonate rocks (Purbeck facies) of the uppermost Portlandian to Berriasian in the type section of the Sierra del Pozo Formation in the Prebetic Zone, southern Spain, are divisible into 141 shallowing upward cycles averaging 2 m in thickness. The subtidal facies in these cycles consist of micritic or marly limestones with dasycladacean algae and lituolids; the intertidal facies are micritic limestones containing birdseyes and miliolids; the supratidal facies comprise laminated algal limestones, the tops of which display desiccation cracks and rhizocretions, or more locally palaeosols, calcretes, or palaeokarst surfaces. A statistical study, using power spectra of the Fast Fourier Transform, demonstrates that the periodicity of these cycles is in the Milankovitch frequency band. Most sedimentary cycles correspond to the obliquity cycles; eccentricity and precession cycles have also been recognized. Using a Fischer plot, third-order tectono-eustatic cycles are recognized, which can be correlated with the eustatic curve of the Exxon chart. The shallowing upward sequences are characterized by a distinctive pattern of geochemical parameters. Carbon and oxygen isotopic (δ¹³C and δ¹⁸O) variations, calcium and magnesium carbonate contents and the abundance of organic matter and trace elements (Mn and Sr) all have predictable patterns of distribution within the sequences. The Sr content of the subtidal facies is relatively high whereas the δ¹³C and δ¹⁸O ratios are quite low; in the intertidal facies the Sr and Mn levels fall concomitantly with a rise in δ¹³C and δ¹⁸O. The highest δ¹³C and δ¹⁸O values occur in the lower part of the supratidal facies, whereas in the upper part of δ values and Sr contents drop sharply. Cyclic variations in evaporation and in meteoric water influence, determined from oxygen isotopic composition, reveal that the cyclicity of the beds containing the most limestones (supratidal) and those with the most marls (subtidal) is related to climatic changes. The coldest periods are those represented by supratidal deposits, when the sea level was at its lowest. During the warmest periods, when the overall sea level was higher, subtidal deposits accumulated in the region. A genetic model is proposed, according to which the asymmetrical sedimentary cycles occur in response to glacio-eustatic changes with a periodicity similar to that of Plio-Pleistocene sea-level variations, but with a much lower range due to the smaller extent of polar ice caps during the Early Cretaceous. The glacio-eustatic changes involved a rapid sea-level rise and a slow sea-level fall.     

Isotopic signatures of otoliths and the stock structure of canary rockfish along the Washington and Oregon coast

Canary rockfish are one of the commercially important rockfish species along the US Pacific coast. Yet little is known about their life history and stock structure. In this study 120 canary rockfish otoliths were collected from waters off the Washington and Oregon coast and subjected to stable O and C isotope (δ¹⁸O and δ¹³C) analyses. One powder sample was taken from the nucleus of each otolith, and the other from the 5th annual ring. Data from otolith nuclei can provide information on the natal sources and spawning stock separations, while data from age-1 to age-5 may indicate changes in fish habitat. Overall the δ¹⁸O values in otoliths of canary rockfish ranged from −0.2‰ to +1.7‰, whereas δ¹³C values of the same samples ranged from −5.4‰ to −1.4‰. The isotopic data and correlation of δ¹⁸O versus δ¹³C did not show clear separation between Washington and Oregon samples, similar to those for a previous study on yelloweye rockfish from the same region. These results suggest that canary rockfish may belong to a single spawning stock or population along the Washington and Oregon coast.     

The nature of O18/O16 and C13/C12 secular trends in sedimentary carbonate rocks

Measurements on 170 carbonate rocks show decreasing δO¹⁸ of similar magnitude for both limestones and dolomites over a time span of ~ 2800 m.y. The Proterozoic dolomites are on average heavier by ~5%. in δO¹⁸ than their coeval limestones. The data may indicate displacement in δC¹³ of about 3%. at approximately 570 m.y. ago, with Precambrian carbonates being heavier in δC¹³ at a given δO¹⁸ level than their Phanerozoic counterparts. The compilation of the previously published data is consistent with the above described features.     

Microfacies analysis and paleoenvironmental significance of palustrine carbonates in the Thakkhola-Mustang Graben (Nepal Himalaya)

The Thakkhola-Mustang Graben represents the extensional tectonic phase of the Tibetan Plateau uplift and whole Himalayan orogeny. It is situated at the northern side of the Dhaulagiri and Annapurna Ranges and south of the Yarlang Tsangpo Suture Zone. Stratigraphically, the oldest sedimentary units are the Tetang and Thakkhola Formations (Miocene), while the Sammargaon, Marpha and Kaligandaki Formations lying disconformably above these formations represent Plio-Pleistocene units. In this study, different lacustrine carbonates and calcretes were investigated within different lithological units and depositional environments to interpret the palaeoenvironmental and palaeoclimatological evolution of the area.Geological mapping, construction of columnar sections and carbonate sampling were carried out in the field, and stable oxygen and carbon isotope analyses and thin section analyses were done in the laboratory. Lacustrine facies contained abundant pelletal, charophytic algae, oncolitic algal micritic palustrine limestones with ostracods, and micritic mudstones with root traces. Stable carbon and oxygen isotope analysis from the carbonates show a range of δ¹³C values from −0.6‰ to 11.1‰ (V-PDB) and δ¹⁸O values from −13.5‰ to −25‰ (V-PDB).Discontinuous growth of oncolites and spherical pellets (25–40 μm in diameter) in micritic limestone, algal mats and charophyte algae indicate the presence of both shallow and deep water carbonates. Ostracods in dark micritic carbonates indicate quiet and calm water conditions. Microfabrics of the carbonates suggest that they were deposited in a flat and shallow lacustrine environment. The δ¹⁸O values of the investigated limestones of the Thakkhola-Mustang Graben suggest that it attained the current elevation level prior to the east-west extension of the Himalaya.