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.     

'Cap carbonates' and Neoproterozoic glacigenic successions from the Kimberley region, north-west Australia

The term ‘cap carbonate’ is commonly used to describe carbonate units associated with glacigenic deposits in Neoproterozoic successions. Attempts to use carbonate units as stratigraphic markers have been counfounded by inconsistent identification of ‘cap carbonates’ and a somewhat broad use of the term. Systematic sedimentological and geochemical analysis of carbonate rocks (mostly dolomite) associated with glacigenic deposits from the Neoproterozoic succession of the Kimberley region, north‐western Australia, shows that it is possible to characterize such units by their specific mineralogical, sedimentological, petrographic, geochemical and stratigraphic features. Hence, it is possible to differentiate true ‘cap carbonates’ from other carbonate units that are associated with glacigenic deposits. In the Kimberley successions two broad carbonate types are identified that reflect two stratigraphically distinct depositional realms. Carbonate rocks from the Egan Formation and Boonall Dolomite (the youngest carbonate units in the succession) are characterized by sedimentary components and features that are consistent with deposition on shallow platforms or shelves, analogous to Phanerozoic warm‐water carbonate platform deposits. In contrast, dolomite from the Walsh, Landrigan and Moonlight Valley Tillites preserves a suite of sedimentary and geochemical characteristics that are distinctly different from Phanerozoic‐like carbonate rocks; they are thin (ca 6 m), laterally persistent units of thinly laminated dolomicrite/dolomicrospar recording δ¹³C fluctuations from −1‰ to −5‰. These latter features are consistent with a ‘Marinoan‐style cap‐carbonate’ rock described from other Neoproterozoic successions. The similarity and broad distribution of these rocks in Australia, when considered within the context of genetic models suggesting a global oceanographic–atmospheric event, support their use as a lithostratigraphic marker horizon for the start of the Ediacaran Period at ca 635 Ma.     

Characteristics and Dolomitization of Upper Cambrian to Lower Ordovician Dolomite from Outcrop in Keping Uplift, Western Tarim Basin, Northwest China

Late Cambrian to Early Ordovician sedimentary rocks in the western Tarim Basin, Northwest China, are composed of shallow-marine platform carbonates. The Keping Uplift is located in the northwest region of this basin. On the basis of petrographic and geochemical features, four matrix replacement dolomites and one type of cement dolomite are identified. Matrix replacement dolomites include (1) micritic dolomites (MD1); (2) fine–coarse euhedral floating dolomites (MD2); (3) fine–coarse euhedral dolomites (MD3); and (4) medium–very coarse anhedral mosaic dolomites (MD4). Dolomite cement occurs in minor amounts as coarse saddle dolomite cement (CD1) that mostly fills vugs and fractures in the matrix dolomites. These matrix dolomites have δ18O values of ?9.7‰ to ?3.0‰ VPDB (Vienna Pee Dee Belemnite); δ13C values of ?0.8‰ to 3.5‰ VPDB; 87Sr/86Sr ratios of 0.708516 to 0.709643; Sr concentrations of 50 to 257 ppm; Fe contents of 425 to 16878 ppm; and Mn contents of 28 to 144 ppm. Petrographic and geochemical data suggest that the matrix replacement dolomites were likely formed by normal and evaporative seawater in early stages prior to chemical compaction at shallow burial depths. Compared with matrix dolomites, dolomite cement yields lower δ18O values (?12.9‰ to ?9.1‰ VPDB); slightly lower δ13C values (?1.6‰–0.6‰ VPDB); higher 87Sr/86Sr ratios (0.709165–0.709764); and high homogenization temperature (Th) values (98°C–225°C) and salinities (6 wt%–24 wt% NaCl equivalent). Limited data from dolomite cement shows a low Sr concentration (58.6 ppm) and high Fe and Mn contents (1233 and 1250 ppm, respectively). These data imply that the dolomite cement precipitated from higher temperature hydrothermal salinity fluids. These fluids could be related to widespread igneous activities in the Tarim Basin occurring during Permian time when the host dolostones were deeply buried. Faults likely acted as important conduits that channeled dolomitizing fluids from the underlying strata into the basal carbonates, leading to intense dolomitization. Therefore, dolomitization, in the Keping Uplift area is likely related to evaporated seawater via seepage reflux in addition to burial processes and hydrothermal fluids.     

Microcrystalline dolomite in a middle Permian volcanic lake: Insights on primary dolomite formation in a non-evaporitic environment

Lacustrine dolomite nucleation commonly occurs in modern and Neogene evaporitic alkaline lakes. As a result, ancient lacustrine microcrystalline dolomite has been conventionally interpreted to be formed in evaporitic environments. This study, however, suggests a non-evaporitic origin of dolomite precipitated in a volcanic–hydrothermal lake, where hydrothermal and volcanic processes interacted. The dolomite occurs in lacustrine fine-grained sedimentary rocks in the middle Permian Lucaogou Formation in the Santanghu intracontinental rift basin, north-west China. Dolostones are composed mainly of nano-sized to micron-sized dolomite with a euhedral to subhedral shape and a low degree of cation ordering, and are interlaminated and intercalated with tuffaceous shale. Non-dolomite minerals, including quartz, alkaline feldspars, smectite and magnesite mix with the dolomite in various proportions. The ⁸⁷Sr/⁸⁶Sr ratios (0.704528 to 0.705372, average = 0.705004) and δ²⁶Mg values (−0.89 to −0.24‰, average = −0.55‰) of dolostones are similar to those of mantle rocks, indicating that the precipitates mainly originated from fluids that migrated upward from the mantle and were subject to water–rock reactions at a great depth. The δ¹⁸O values (−3.1 to −22.7‰, average = −14.0‰) of the dolostones indicate hydrothermal influence. The trace and rare earth element concentrations suggest a saline, anoxic and volcanic–hydrothermally-influenced subaqueous environment. In this subaqueous environment of Lucaogou lake, locally high temperatures and a supply of abundant Mg²⁺ from a deep source induced by volcanic–hydrothermal activity formed favourable chemical conditions for direct precipitation of primary dolomite. This study's findings deepen the understanding of the origin and processes of lacustrine primary dolomite formation and provide an alternative possibility for environmental interpretations of ancient dolostones.     

皖南新元古代两次冰期事件

新元古代的冰期事件一直是地质界研究的热点之一。包括中国在内 ,世界许多地区新元古代地层中普遍发育有一至两层冰碛岩 ,有的地区甚至可以见到三层冰碛岩 ,在冰碛岩之上往往有碳酸盐岩盖层 ( Cap Carbonate)。通过对皖南休宁新元古代冰碛岩的岩石地层学 ,以及碳、氧稳定同位素化学地层学的研究 ,证实了休宁新元古代地层存在两期冰川的记录 ,并通过与国内外同时代典型地层剖面的对比 ,认为休宁蓝田剖面的两层冰碛岩可能分别相当于 Sturtian冰期和 Marinoan冰期的沉积 ,其时代分别约为 710— 73 0 Ma,5 90— 60 0 Ma     

Application of carbon isotope chemostratigraphy to the Renison dolomites,Tasmania: A Neoproterozoic age

This study uses carbon isotope chemostratigraphy to propose an age for the Success Creek Group and Crimson Creek Formation in the absence of any direct radiometric dates, palaeomagnetic or reliable palaeontological data. The δ¹³C values were determined for the least‐altered dolomite samples. Suitable samples were selected on the basis of grainsize, cathodoluminescence petrography, most enriched δ¹⁸O values (> ‐2%o) low Mn/Sr ratios and low Fe and Mn concentrations. The average least‐altered, most ¹³C‐enriched dolomicrite samples in the youngest (No. 1) dolomite horizon are + 4.6%o. This is typical of Neoproterozoic (but not Cambrian) carbonates. The δ¹³C values of all dolomite samples in the succession are significantly positive (up to + 7.5%o) and the excursion characteristic of the Proterozoic/Cambrian boundary has not been observed. The lack of negative δ¹³C values in all dolomite samples studied also suggests an absence of correlatives of Sturtian and Varanger tillites in the dolomite successions. The δ¹³C values in all three dolomite horizons suggest a Neoproterozoic age between about 820 to 570 Ma (Cryogenian to Neoproterozoic III) on the current global compilation carbon isotope curves. This age for the Success Creek Group and Crimson Creek Formation, inferred from carbon isotope chemostratigraphy, can be substantiated by other evidence. The age of the Renison dolomites is constrained by K‐Ar dates of 708 ± 6 Ma from detrital muscovite in the underlying Oonah Formation and 588 ± 8 and 600 ± 8 Ma from doleritic rock in a lithostratigraphic equivalent of the Crimson Creek Formation from the Smithton Basin. Furthermore, acritarchs and the stromatolite Baicalia cf. B. burra also suggest a Neoproterozoic rather than Cambrian age.     

Chemostratigraphy and lithological characters of Neoproterozoic cap carbonates from the Kuruktag Mountain, Xinjiang, western China

The Neoproterozoic Era includes some of the most largest ice ages in the geological history. The exact number of glaciations is unknown, though there were at least two events of global glaciation. Neoproterozoic glacial deposits in the Kuruktag Mountain, Xinjiang, western China have proven that there had occurred three discrete Neoproterozoic glaciations. Diamictite units occurred in the Bayisi, Tereeken, and Hankalchough formations, carbonate units were recognized among the diamictites and immediately overlied the Bayisi, Tereeken and Hankalchough diamictites. Carbonates at the top of the Bayisi Formation are characterized by the dolo-sility stones with negative δ13C values ranging from -4.10‰ to -8.17‰ (PDB), comparable to the Sturtian cap carbonates that overlie the Sturtian glacial deposits from other Neoproterozoic sequences. Carbonates overlying the Tereeken Formation are characterized by the pinkish cap dolostones (ca. 10 m thick) with negative δ13C values ranging from -2.58‰ to -4.77‰ (PDB), comparable to the Marinoan cap carbonates. The cap is also characterized by tepee-like structures, barite precipitates and pseudomorphous aragonite crystal fan limestones. Carbonates at the top of the Hankalchough Formation are characterized by subaerial exposure crust (vadose pisolite structure, calcareous crust structure) dolostones with negative δ13C values ranging from -4.56‰ to -11.45‰ (PDB) and the calcareous crust dolostones, implying that the Hankalchough cap carbonates differ from either the Sturtian or Marinoan cap carbonates in sedimentary environment and carbon isotopic composition. In addition, it is suggested the Hankalchough glaciation belongs to a terrestrial glaciation and it is the third largest glaciation during the Neoproterozoic period on the Tarim platform.     

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.     

Tracking connection and restriction of West Gondwana São Francisco Basin through isotope chemostratigraphy

C and Sr isotope compositions of carbonate rocks from the intracontinental São Francisco basin can track ocean connections and restriction. The lower three formations of the Bambuí Group can be grouped into three chemostratigraphic intervals (CI), recording different evolution stages of the basin. Lowermost CI-1 comprises the basal cap carbonates of the Sete Lagoas Formation displaying an initial C negative excursion, followed by a coeval C and Sr positive excursions (δ¹³C values from − 5 to 0‰ and ⁸⁷Sr/⁸⁶Sr ratios from 0.7074 to 0.7082) in 10 m of stratigraphic record. It marks a change from a restricted shallow basin influenced by freshwater to a basin connected to external seawaters due to marine transgression. CI-2 comprises carbonates of the middle portion of the Sete Lagoas Formation with δ¹³C values around 0‰ and ⁸⁷Sr/⁸⁶Sr ratios around 0.7082 that matches those observed worldwide for the Late Ediacaran. It records the onset of a Gondwana sea pathway connecting several epicontinental basins, allowing migration of index-fossil Cloudina sp. Uppermost CI-3 starts after a major positive excursion in the δ¹³C values reaching + 16‰ and a steepened decrease of ⁸⁷Sr/⁸⁶Sr ratios to 0.7075 which are lower than those expected for the Ediacaran-Cambrian boundary. This interval comprises the upper Sete Lagoas, Serra de Santa Helena and Lagoa do Jacaré formations and records the end of the connection of the São Francisco basin to the Gondwana sea pathway setting a restricted epeiric sea. Restriction was probably caused by Late Ediacaran uplifting of orogenic belts surrounding the basin. Other West Gondwana Cloudina bearing units also display the same mismatch in the Sr isotope ratios, suggesting that the establishment of intracontinental basins inside large continental masses may challenge the use of isotope chemostratigraphy for interbasinal correlations.     

塔里木盆地柯坪地区上寒武统表生溶蚀型藻格架白云岩的地球化学特征及意义*

采用野外观察、室内薄片鉴定及多项地球化学分析技术方法,对塔里木盆地柯坪地区上寒武统表生溶蚀型藻格架白云岩的特征及成因进行了研究。宏观上,藻格架白云岩呈丘状、透镜状夹于潮坪相白云岩层间,由于差异性溶蚀,发育了大量表生溶蚀孔。微观上,藻格架由富藻的泥粉晶白云石组成,而架间孔由浅色的亮晶白云石充填。藻格架泥粉晶白云石呈他形—半自形,镶嵌结构,具有暗红色—橙红色的阴极发光,较高的Na、K含量,较低的Fe含量;δ¹³C为-0.572‰～0.124‰、平均值-0.116‰,δ¹⁸O为-5.391‰～-4.983‰、平均值-5.240‰,表明其形成于准同生阶段盐度较高的相对氧化环境中。架间充填的亮晶白云石胶结物,呈半自形—自形中细晶,具有昏暗的阴极发光或者不发光,较低的Na、K含量,较高的Fe含量,δ¹³C值为-0.662‰～-0.251‰、平均值为-0.460‰;δ¹⁸O值为-6.639‰～-5.939‰、平均值-6.267‰,表明其形成于相对还原的埋藏环境。稀土元素分析结果表明,二者均具有LREE轻微富集、HREE亏损、Eu负异常特征,与海相泥晶灰岩稀土元素配分模式相似,揭示了其白云化流体均来自于原始的海水。在溶蚀作用方面,亮晶白云石胶结物相对泥粉晶白云石藻格架更易于溶蚀。前者在大气水表生溶蚀过程中,主量元素Ca、Mg丢失显著,Mg/Ca值由0.955降至0.007,微量元素Na、K丢失相对明显,Na/Ca值由原来的3.8×10^-4降为1.9×10^-4,K/Ca值由1.1×10^-3降至检测限以下,而不改变稀土元素的配分模式。这些特征表明,表生溶蚀过程在元素特征上是一个去白云化的盐度降低过程,而这一过程中基本无稀土元素的带入带出。     

Nucleation and stabilization of Eocene dolomite in evaporative lacustrine deposits from central Tibetan plateau

In past decades, the formation of dolomite at low temperature has been widely studied in both natural systems and cultured experiments, yet the mechanism(s) involved in the nucleation and precipitation of dolomite remains unresolved. Late Eocene dolomitic deposits from core in the upper Niubao Formation (Lunpola Basin, central Tibetan Plateau, China) are selected as a case study to understand the dolomitization process(es) in the geological record. Dolomite formation in Lunpola Basin can be ascribed to a different mechanism forming the large quantities of replacive dolostones in the geological record; and provides a potential fossil analogue for primary dolomite precipitation at low temperature. This analogue consists of an alternation of laminated dolomitic beds, organic-rich and siliciclastic layers; formed in response to intense evaporation interpreted to take place in a continental shallow lake environment. Mineralogical, textural and stable isotopic evaluations suggest that the dolomite from those dense-clotted laminated beds is a primary precipitate. At the nanoscale, these dolomitic beds are composed of Ca–Mg carbonate globular nanocrystals (diameter 80 to 100 nm) embedded in an organic matrix and attached to clay flakes. Micro-infrared spectroscopy analyses have revealed the presence of aliphatic compounds in the organic matrix. Microscopic and elemental compositional studies suggest that clay surfaces may facilitate the nucleation of dolomite at low temperature in the same way as the organic matrix does. The dolomite laminae show values for δ¹⁸O_VPDB from −3.2 to −1.76‰ and for δ¹³C_VPDB from −2.62 to −3.78‰. Inferred δ¹⁸O_SMOW values of the lake water reveal typical evaporitic hydrological conditions. These findings provide a potential link to primary dolomite formation in ancient and modern sedimentary environments; and shed new light on the palaeoenvironmental conditions in central Tibet during the Eocene.     

Palaeoproterozoic magnesite: lithological and isotopic evidence for playa/sabkha environments

Magnesite forms a series of 1‐ to 15‐m‐thick beds within the ≈2·0 Ga (Palaeoproterozoic) Tulomozerskaya Formation, NW Fennoscandian Shield, Russia. Drillcore material together with natural exposures reveal that the 680‐m‐thick formation is composed of a stromatolite–dolomite–‘red bed’ sequence formed in a complex combination of shallow‐marine and non‐marine, evaporitic environments. Dolomite‐collapse breccia, stromatolitic and micritic dolostones and sparry allochemical dolostones are the principal rocks hosting the magnesite beds. All dolomite lithologies are marked by δ¹³C values from +7·1‰ to +11·6‰ (V‐PDB) and δ¹⁸O ranging from 17·4‰ to 26·3‰ (V‐SMOW). Magnesite occurs in different forms: finely laminated micritic; stromatolitic magnesite; and structureless micritic, crystalline and coarsely crystalline magnesite. All varieties exhibit anomalously high δ¹³C values ranging from +9·0‰ to +11·6‰ and δ¹⁸O values of 20·0–25·7‰. Laminated and structureless micritic magnesite forms as a secondary phase replacing dolomite during early diagenesis, and replaced dolomite before the major phase of burial. Crystalline and coarsely crystalline magnesite replacing micritic magnesite formed late in the diagenetic/metamorphic history. Magnesite apparently precipitated from sea water‐derived brine, diluted by meteoric fluids. Magnesitization was accomplished under evaporitic conditions (sabkha to playa lake environment) proposed to be similar to the Coorong or Lake Walyungup coastal playa magnesite. Magnesite and host dolostones formed in evaporative and partly restricted environments; consequently, extremely high δ¹³C values reflect a combined contribution from both global and local carbon reservoirs. A ¹³C‐rich global carbon reservoir (δ¹³C at around +5‰) is related to the perturbation of the carbon cycle at 2·0 Ga, whereas the local enhancement in ¹³C (up to +12‰) is associated with evaporative and restricted environments with high bioproductivity.     

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.     

Stable chlorine and carbon isotope measurements of selected chlorinated organic solvents

Stable Cl and C isotope ratio results for 3 selected chlorinated solvents, perchloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) provided by 4 different manufacturers are presented. The isotope ratio for all compounds range between −3.5 and +6.0‰ forδ³⁷Cl and from −37.2 to −23.3%. forδ¹³C. The greatest³⁷Cl difference between manufacturers is observed in the TCE samples which showδ³⁷CI values of −2.5%o for PPG, +2.43‰ for ICI and +4.4‰ for DOW. TCAs show a smaller range (−2.4 to +2.0‰), while the TCEs have slightly different³⁷Cl contents. The¹³C data show the most distinctδ¹³C values for PCEs (−23.3 for DOW, −24.1 for Vulcan, −33.8 for PPG and −37.2‰ for ICI) while both TCEs and TCAs show a smallerδ¹³C range, but still distinct differences. These preliminary data suggest that each manufacturer and solvent type may have distinctiveδ⁶³⁷Cl andδ¹³C values. These results show that by using a combination of³⁷Cl and¹³C, there is a potential to indicate a specific source of chlorinated solvents, as well as an ability to delineate contamination episodes caused by these compounds in groundwaters.     

2H/1H ratio of hopanes,tricyclic and tetracyclic terpanes in oils and source rocks from the Potiguar Basin,Brazil

We report the hydrogen isotope ratio ²H/¹H (expressed as δ²H values) of 8 selected hopanes, tricyclic and tetracyclic terpanes from oils and source rocks in the Potiguar Basin, and of associated formation water. Hopanes ranged in δ²H value from −79‰ to −142‰, whereas tri- and tetracyclic terpanes (TTTs) ranged from −137‰ to −225‰. Formation water δ²H values ranged from −23‰ to −32‰. The most significant pattern in the data is the systematic ²H enrichment of hopanes relative to TTTs, by an average of 45‰ in oils and 78‰ in source rock extracts. The hopanes appear close to hydrogen isotopic equilibrium with coeval formation water, whereas TTTs are significantly more ²H depleted. Given the similarities in structure between the two compound classes, it is unlikely that hopanes would be exchanged completely while the others would not. More likely, both classes have undergone a limited extent of exchange, but with the hopanes being biosynthesized with δ²H values closer to equilibrium. Our data suggest that at least some primary environmental and/or biotic information can be retained in the δ²H values of biomarkers in oils and extracts, and is not completely obscured by hydrogen exchange.     

Origin of CO2 and carbonate veins in mantle-derived xenoliths in the Pannonian Basin

The origin and evolution of CO₂ inclusions and calcite veins in peridotite xenoliths of the Pannonian Basin, Hungary, were investigated by means of petrographic investigation and stable isotope analyses. The fluid inclusions recovered in paragenetic olivine and clinopyroxene belong to distinct populations: type A (texturally early) inclusions with regular shapes (often with negative crystal forms) forming intragranular trails; type B (texturally late) inclusions defining randomly oriented trails that reach grain boundaries. Type B inclusions are often associated with silicate melt (type C) inclusions. Stable carbon isotope compositions in inclusion-hosted CO₂ were obtained by vacuum crushing followed by conventional dual inlet as well as continuous flow mass spectrometry in order to eliminate possible lab artifacts. Olivines, clino- and orthopyroxenes of the host peridotite have oxygen isotope compositions from 5.3 to 6.0‰ (relative to V-SMOW), without any relationship with xenolith texture. Some of the xenoliths contained calcite in various forms: veins and infillings in silicate globules in veins, secondary carbonate veins filling cracks and metasomatic veins with diffuse margins. The former two carbonate types have δ¹³C values around –13‰ (relative to V-PDB) and low Sr contents (< 0.5 wt.%), whereas the third type,veins with high-temperature metasomatic features have a δ¹³C value of –5.0‰ and high Sr contents up to 3.4 wt.%. In spite of the mantle-like δ¹³C value and the unusually high Sr content typical for mantle-derived carbonate, trace element compositions have proven a crustal origin. This observation supports the conclusions of earlier studies that the carbonate melt droplets found on peridotite xenoliths in the alkaline basalts represent mobilized sedimentary carbonate. The large δ¹³C range and the ¹²C-enrichment in the carbonates can be attributed to devolatilization of the migrating carbonate or infiltration of surficial fluids containing ¹²C-rich dissolved carbon.Carbon isotope compositions of inclusion-hosted CO₂ range from –17.8 to –4.8‰ (relative to V-PDB) with no relation to the amount of CO₂ released by vacuum crushing. Low-δ¹³C values measured by stepwise heating under vacuum suggest that the carbon component is pristine and not related to surficial contamination, and that primary mantle fluids with δ¹³C values around –5‰ were at least partly preserved in the xenoliths. Tectonic reworking and heating by the basaltic magma resulted in partial CO₂ release and local ¹³C-depletion.     

Characterization of the hydrogen isotopic composition of individual n-alkanes in terrestrial source rocks

In order to characterize the H isotopic compositions of individual lipid compounds from different terrestrial depositional environments, the δD values of C-bound H in individual n-alkanes from typical terrestrial source rocks of the Liaohe Basin and the Turpan Basin, China, were measured using gas chromatography–thermal conversion–isotope ratio mass spectrometry (GC–TC–IRMS). The analytical results indicate that the δD values of individual n-alkanes in the extracts of terrestrial source rocks have a large variation, ranging from −140‰ to −250‰, and are obviously lighter than the δD of marine-sourced n-alkanes. Moreover, a trend of depletion in ²H(D) was observed for individual n-alkanes from different terrestrial depositional environments, from saline lacustrine to freshwater paralic lacustrine, and to swamp. For example, the δD values of n-alkanes from a stratified saline lacustrine environment vary from −140‰ to −200‰, δD for n-alkanes from swamp facies range from −200‰ to −250‰, while those from freshwater paralic lacustrine–lacustrine environments fall between the δD values of the end members. The shift toward lighter δD from saltwater to freshwater environments indicates that the source water δD is the major controlling factor for the H isotopic composition of individual compounds. In addition, H exchange between formation water and sedimentary organic matter may possibly be important in regard to the δD of individual n-alkanes. Therefore, other lines of geochemical evidence must be considered when depositional paleoenvironments of source rocks are reconstructed based on the H isotopic composition of individual n-alkanes.     

Characterization of C‐isotope variability in the Delhi Supergroup,northwestern India and the Mesoproterozoic ocean

Marine carbonate rocks of the Delhi Supergroup of northwestern India show little deviation in whole‐rock δ ¹³Ccarb and δ ¹⁸Ocarb values, which generally are around 0 and –10‰ respectively. These narrow ranges and almost constant δ ¹³Ccarb values persist despite close sampling through long sections. The data suggest that the global rate of organic carbon burial was probably constant during deposition of the Delhi Supergroup. The nearly invariant C isotopic profile of the Delhi Supergroup is similar to C isotopic profiles of Mesoproterozoic carbonates older than 1.3 Ga, as reported from different parts of world. Carbonate units on the western margin of the Delhi Supergroup however, have on average moderately positive δ ¹³C values (from 2 to +4.96‰). These high δ ¹³C carbonates may represent the Mesoproterozoic–Neoproterozoic transition (from ～1.25 to ～0.85 Ga), a period characterized by high positive δ ¹³C values globally.     

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.     

Massive dolomitization of a late Miocene carbonate platform: a case of mixed evaporative brines with meteoric water,Nijar, Spain

Late Miocene platform carbonates from Nijar, Spain, have been extensively dolomitized. Limestones are present in the most landward parts of the platform, in stratigraphically lower units and topographically highest outcrops, suggesting that dolomitizing fluids were derived from the adjacent Nijar Basin. The dolomite crystals range from <10 to ≈100 μm existing as both replacements and cements. Na, Cl and SO₄ concentrations in the dolomites range from 200 to 1700 p.p.m., 250–650 p.p.m., and 600–7000 p.p.m., respectively, comparable with other Tertiary and modern brine dolomite values, and also overlapping values from mixing-zone dolomites. Sr concentrations range between 50 and 300 p.p.m., and the molar Sr/Ca ratios of dolomitizing fluids are estimated to range between 7× seawater brine to freshwater ratios. The δ¹⁸O and δ¹³C of the dolomites range from ?1·0 to +4·2‰ PDB, and ?4·0 to +2·0‰ PDB, respectively. ⁸⁷Sr/⁸⁶Sr values (0·70899–0·70928) of the dolomites range from late Miocene seawater to values greater than modern seawater. Mixtures of freshwater with seawater and evaporative brines probably precipitated the Nijar dolomites. Modelled covariations of molar Sr/Ca vs. δ¹⁸O and Na/Ca vs. δ¹⁸O from these mixtures are consistent with those of the proposed Nijar dolomitizing fluids. Complete or partial dolomite recrystallization is ruled out by well preserved CL zoning, nonstoichiometry and quantitative water–rock interaction modelling of covariations of Na vs. Sr and δ¹⁸O vs. δ¹³C. The possibility of multiple dolomitization events induced by evaporative brines, seawater and freshwater, respectively, is consistent with mineral-mineral mixing modelling. The basin-derived dolomitizing brines probably mixed with freshwater in the Nijar Basin or mixed with fresh groundwater in the platform, and were genetically related either to deposition of the Yesares gypsum or the Feos gypsum. Dolomitization occurred during either the middle Messinian or the early upper Messinian. Nijar dolomitization models may be applicable to dolomitization of other late Miocene platform carbonates of the western Mediterranean. Moreover, the Nijar models may offer an analogue for more ancient evaporite-absent platform carbonates fringing evaporite basins.