Petrological and isotopic implications of some contrasting Late Precambrian carbonates, NE Spitsbergen

The dominantly shallow-marine Vendian succession of NE Spitsbergen contains distinctive types of carbonate rock. Limestones deposited before Vendian glaciation resemble those described from other Upper Proterozoic successions, being high in Sr and inferred to have been originally aragonitic, including the distinctive 5–10 Jim equant polygonal calcite of cemented shrinkage cracks. In contrast, manganoan stromatolitic limestones within marginal-marine glacial-outwash deposits, and consisting of micrite, microspar and fascicular-optic calcite are interpreted as originally calcitic. The restriction of primary marine calcite to cold seawater is comparable with Recent and Permian carbonates, although the Precambrian example formed in a sea diluted with meltwater. There is good textural preservation of relatively ¹⁸O-rich oolitic dolostones which were cemented in a supratidal environment by artesian fluids. Nevertheless, early diagenetic replacement is inferred, immediately prior to a glacial episode. Post-glacial dolostones are either replacive marine, or evaporative lacustrine, but share rather more negative δ¹⁸O values, closer to the mean of Late Precambrian dolostones. The heaviest oxygen isotope values constrain seawater δ¹⁸O to no more negative than — 2 to — 4_SMOW. The main reason for the pronounced oxygen isotopic depletion of most Late Precambrian carbonates is their initial metastable mineralogy. The possibility of determining palaeolatitudes of the enigmatic widespread Late Proterozoic glaciations by isotopic analysis of freshwater periglacial calcareous precipitates is raised. Significant carbon isotope variations reflect changes in depositional water chemistry: some of these could be global in extent.     

B, Sr, O and H Isotopic Compositions of Formation Waters from the Bachu Bulge in the Tarim Basin

In order to elucidate the origin and migration of basinal brines in the Bachu Bulge, Tarim Basin, we have carried out analyses on chemical composition, and boron, hydrogen and oxygen isotopes of formation waters together with the XRD of clay minerals from the Paleozoic strata. The waters show Ca, B, Li and Sr enrichment and SO4 depletion in the Carboniferous and Ordovician and K enrichment in part of the Ordovician relative to seawater. The relationship between δD and δ^18O shows that all the data of the waters decline towards the Global Meteoric Water Line with the intersection of them close to the present-day local meteoric water, suggesting that modern meteoric water has mixed with evaporated seawater. The ^87Sr/^86Sr ratios range from 0.7090 to 0.7011, significantly higher than those of the contemporary seawater. The δ^11B values range from ＋19.7 to ＋32.3‰, showing a decrease with the depth and B concentrations. The results suggest that isotopically distinct B and Sr were derived from external sources. However, since the percentages of illite are shown to increase with depth among clay minerals in the study area, i.e., illite is due to precipitation rather than leaching during deeper burial, it is unlikely for illite to have contributed a significant amount of B to the waters. Thus, B with low δ^11B values is interpreted to have been added mainly from thermal degradation of kerogen or the basalts in the Cambrian and Lower Ordovician.     

Sr, C, and O isotope geochemistry of Ordovician brachiopods: a major isotopic event around the Middle-Late Ordovician transition

Here we present Sr, C, and O isotope curves for Ordovician marine calcite based on analyses of 206 calcitic brachiopods from 10 localities worldwide. These are the first Ordovician-wide isotope curves that can be placed within the newly emerging global biostratigraphic framework. A total of 182 brachiopods were selected for C and O isotope analysis, and 122 were selected for Sr isotope analysis. Seawater ⁸⁷Sr/⁸⁶Sr decreased from 0.7090 to 0.7078 during the Ordovician, with a major, quite rapid fall around the Middle-Late Ordovician transition, most probably caused by a combination of low continental erosion rates and increased submarine hydrothermal exchange rates. Mean δ¹⁸O values increase from −10‰ to −3‰ through the Ordovician with an additional short-lived increase of 2 to 3‰ during the latest Ordovician due to glaciation. Although diagenetic alteration may have lowered δ¹⁸O in some samples, particularly those from the Lower Ordovician, maximum δ¹⁸O values, which are less likely to be altered, increase by more than 3‰ through the Ordovician in both our data and literature data. We consider that this long-term rise in calcite δ¹⁸O records the effect of decreasing tropical seawater temperatures across the Middle-Late Ordovician transition superimposed on seawater δ¹⁸O that was steadily increasing from ≤−3‰ standard mean ocean water (SMOW). By contrast, δ¹³C variation seems to have been relatively modest during most of the Ordovician with the exception of the globally documented, but short-lived, latest Ordovician δ¹³C excursion up to +7‰. Nevertheless, an underlying trend in mean δ¹³C can be discerned, changing from moderately negative values in the Early Ordovician to moderately positive values by the latest Ordovician. These new isotopic data confirm a major reorganization of ocean chemistry and the surface environment around 465 to 455 Ma. The juxtaposition of the greatest recorded swings in Phanerozoic seawater ⁸⁷Sr/⁸⁶Sr and δ¹⁸O at the same time as one of the largest marine transgressions in Phanerozoic Earth history suggests a causal link between tectonic and climatic change, and emphasizes an endogenic control on the O isotope budget during the Early Paleozoic. Better isotopic and biostratigraphic constraints are still required if we are to understand the true significance of these changes. We recommend that future work on Ordovician isotope stratigraphy focus on this outstanding Middle-Late Ordovician event.     

Discussion: Stratigraphy and structural summary of the Cooma metamorphic complex

Field and petrographic studies on granitic, hematitic and chloritic breccias in the central portion of the Mount Painter Inlier, South Australia, indicate that: (i) breccias and brecciated basement extend to depths exceeding 400 m and have gradational contacts; (ii) clasts are mainly autochthonous and contain fine‐scale hematite, chlorite or quartz veinlets and fractures; (iii) K‐metasomatism preceded hematitisation and chloritisation; (iv) hematitic breccia intrudes a pegmatite dyke correlated with the Ordovician Arkaroola Pegmatite; and (v) U, F and REE‐containing minerals are present in the Proterozoic basement rocks, and concentrated in the breccias.

With a single exception, δ³⁴S values for pyrite from the breccias and brecciated granites fall in the narrow range —2.9% to +3.5%, implying formation from magmatic emanations or reducing fluids that leached sulphide minerals of magmatic derivation. δ³⁴S values for three barite samples are all close to +16%o, and firm conclusions cannot be drawn from these data. Calcites from the same rock‐types as the pyrite have δ¹³C values of — 22.3%o to —4.2%o and δ¹⁸O values of —4.0%o to +23.1%., with an inverse δ¹³C/δ¹⁸O relationship. The more ¹³C‐depleted calcites probably incorporated CO₂ from organic C, and their δ¹⁸O values are compatible with precipitation from magmatic or metamorphic fluids; mixing of such fluids with meteoric waters is implied by the calcites with variably lower δ¹⁸O values.

The above features indicate that the major processes leading to brecciation and associated metasomatism were hydraulic fracturing and hydrothermal activity resulting from ascent of granitic magmas to shallow crustal levels during late stages (late Ordovician‐?Silurian) of the Delamerian Orogeny. Tectonic and sedimentary processes appear to have played relatively minor roles in breccia formation.     

Behavior of carbonate-associated sulfate during meteoric diagenesis and implications for the sulfur isotope paleoproxy

Although carbonate-associated sulfate (CAS) is used widely as a proxy for the sulfur isotope composition of ancient seawater, little is known about the effects of diagenesis on retention of primary δ³⁴S signals. Our case study of the Key Largo Limestone, Pleistocene, Florida, is the first systematic assessment of the impact of meteoric diagenesis on CAS properties. Geochemical and petrographic data show that meteoric diagenesis has affected the exposed coralline facies to varying degrees, yielding differences now expressed as sharp reaction fronts between primary and secondary carbonate minerals within individual coral heads. Specifically, analyses across high-resolution transects in the Key Largo Limestone show that concentrations of strontium and sodium decrease across the recrystallization front from original aragonite to meteoric low-magnesium calcite by factors of roughly 5 and 10, respectively. Predictably, δ¹⁸O values decrease across these same fronts. The δ¹³C relationships are more complex, with the most depleted values observed in the latest-formed calcite. Such trends likely reflect carbon isotope buffering capacity that decreased as reaction progressed, as well as protracted development of soil profiles and the associated terrestrial biomass and thus depleted δ¹³C during sea-level lowstand. Conversely, δ³⁴S values of CAS vary within a narrow ‘buffered’ range from 20.6 to 22.6‰ (compared to 20.8-22.0‰ of coeval Pleistocene seawater) across the same mineralogical transition, despite sulfate concentrations that drop in the diagenetic calcite by an average factor of 12. Collectively, these data point to robust preservation of primary δ³⁴S for carbonates that have experienced intense meteoric diagenesis, which is encouraging news for those using the isotopic composition of CAS as a paleoceanographic proxy. At the same time, the vulnerability of CAS concentrations to diagenetic resetting is clear.     

Diagenesis of Ordovician carbonates from the north-east Michigan Basin, Manitoulin Island area, Ontario: evidence from petrography, stable isotopes and fluid inclusions

Middle to Late Ordovician subtidal carbonates in the Manitoulin Island area of Ontario are predominantly limestone in composition, but non-ferroan and ferroan dolomite is a common cement as well as a selective or locally pervasive replacement phase. Integration of field, petrographic, geochemical (δ¹³C, δ¹⁸O) and fluid inclusion data indicates that lithification of these carbonates occurred during burial diagenesis, with much of the alteration controlled by regional fracturing and hydrothermal influences. Aqueous (type 1) fluid inclusions in early calcite (pre-dolomite) and dolomite are saline (> 29 wt% NaCl eq.) solutions with Ca and/or Mg in excess of Na and display homogenization temperatures with modes of 95 and 101°C, respectively. These temperatures can be explained by significantly more burial than can be accounted for either by the available stratigraphic information or by an unusually high palaeogeothermal gradient, which also is not well supported. The fluid inclusion temperatures are interpreted to have resulted from hydrothermal fluids which circulated during the burial diagenesis of these strata. Type 1 inclusions in late (post-dolomite) calcite are less saline (<19 wt% NaCl eq.) and have a bimodal distribution of homogenization temperatures with a relatively well defined low temperature peak similar to those in early calcite and dolomite and a broad higher temperature grouping with a mode at 183°C. A small proportion of methane and light hydrocarbon-bearing fluid inclusions (type 2) are present in all stages of carbonate. Dolomitizing fluids were derived from burial compaction of argillaceous sediments in the more central parts of the Michigan Basin and the updip migration of these brines along fractures to the basin margin where the carbonates of the Manitoulin Island area were dolomitized. Alternatively, migration of dolomitizing brines downward from the overlying pervasively dolomitized Silurian sequence into fractures in the Ordovician carbonates may have occurred. Integration of the aqueous fluid inclusion data into the diagenetic history of these carbonates remains equivocal because most of the inclusions are secondary or indeterminate in origin. Nevertheless, high salinities resulting from interaction with evaporitic strata and hydrothermal effects are clearly implicated although the origin of the latter remains unclear. The alteration styles of the Ordovician carbonates in the Manitoulin area are similar to those of Ordovician hydrocarbon reservoirs described from other parts of the Michigan Basin. They indicate that fracture-related diagenesis occurred on a basin-wide scale and that hydrothermal effects were important.     

Stable carbon‐isotope record of shallow‐marine evaporative epicratonic basin carbonates,Ordovician Williston Basin,North America

Secular variations in stable carbon‐isotope values of marine carbonates are used widely to correlate successions that lack high‐resolution index fossils. Various environmental processes, however, commonly may affect and alter the primary marine carbon‐isotope signal in shallow epicratonic basins. This study focuses on the marine carbon‐isotope record from the carbonate–evaporite succession of the upper Katian (Upper Ordovician) Red River Formation of the shallow epicratonic Williston Basin, USA. It documents the carbon‐isotope signal between the two major Ordovician positive shifts in δ¹³C, the early Katian Guttenberg and the Hirnantian excursions. Eight δ¹³C stages are identified based on positive excursions, shifts from positive to negative values and relatively uniform δ¹³C_carb values. A correlation between carbon‐isotope trends and the relative sea‐level changes based on gross facies stacking patterns shows no clear relation. Based on the available biostratigraphy and δ¹³C trends, the studied Williston Basin curves are tied to the isotope curves from the North American Midcontinent, Québec (Anticosti Island) and Estonia, which confirm the Late Katian age (Aphelognathus divergens Conodont Zone) of the upper Red River Formation. The differences in the δ¹³C overall trend and absolute values, coupled with the petrographic and cathodoluminescence evidence, suggest that the carbon‐isotope record has been affected by the syndepositional environmental processes in the shallow and periodically isolated Williston Basin, and stabilized by later burial diagenesis under reducing conditions and the presence of isotopically more negative fluids.     

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

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

Sedimentology and isotopic composition of Upper Palaeocene to Eocene non-marine stromatolites, eastern Ebro Basin, NE Spain

Stromatolites are abundant in Upper Palaeocene to Eocene fluvial deposits from the Eastern Ebro Basin, whereas they are scarce in the lacustrine facies. The fluvial stromatolites display a variety of growth forms: oncoids, domes, laminated crusts and locally irregular bioherms. These morphologies are related to the hydrological behaviour of the fluvial systems. Elongate domes, dome heads and ovoid to subspherical oncoids accreted in flowing water. Laminated crusts and small-sized cylindrical to lenticular oncoids formed during low-discharge and ponding phases. In the lacustrine environments only small-sized ovoid oncoids occur. The main characteristics of the Ebro Basin non-marine stromatolites are: (1) laminations and concentric banding exhibited by all morphologies; (2) the occurrence of well-preserved cyanobacterial filaments in several laminae, suggesting that these microbiotas are the major contributors in growth; (3) the asymmetrical growth of cortices in domes and oncoids with polar thickening on the upper side suggesting in situ growth under low energy conditions. δ¹³C values of carbonate stromatolites range from - 11.3%o (Late Palaeocene) to — 4.4%o (Middle-Late Eocene). During the Late Palaeocene, under tectonically quiescent conditions, the δ¹³C values mainly reflect the influence of soil-derived CO₂. During the Eocene, the progressive uplift of the surrounding catchment areas led to an increase of exposures of Mesozoic rocks. Consequently, the δ¹³C values of the Eocene stromatolites reflect the influence of the CO₂ derived from the dissolution of Mesozoic marine carbonates. There is a 2.5%o shift in δ¹⁸O values of stromatolites from the Late Palaeocene to Middle-Late Eocene which is consistent with the variation in δ¹⁸O of precipitation due to changes in altitude of the catchment area during this time. The isotopic values of all Middle-Upper Eocene laminated crust samples show distinct covariant trends, suggesting that these stromatolites were formed either in ponding zones of fluvial channels or in disconnected pools developed during low-discharge episodes.     

Stable isotope,petrological, and fluid inclusion studies of minor mineral deposits from the McArthur Basin: Implications for the genesis of some sediment‐hosted base metal mineralization from the Northern Territory

The geology, stable isotopes and fluid inclusions from mineralized and unmineralized Middle Proterozoic sequences of the McArthur Basin, Northern Territory, have been studied at Eastern Creek, Bulman Mines, Beetle Springs, and other localities in the McArthur Basin where disseminated sulphides in unmineralized black shales were available from drill core. At Eastern Creek, galena and minor chalcopyrite (δ³⁴S+3.6 to +11.2%o) occur in an evaporitic sedimentary sequence. Barite (δ³⁴S+18.4 to +24.7%o) also occurs, and saline brines are trapped along healed fractures in the barite. Pressure‐corrected trapping temperatures in the barite (95–138°C), and in vein dolomite (158–168°C) agree with temperature estimates from the degree of maturation of the sedimentary organic matter. The δ¹⁸O and δ¹³C_Co2 values of the mineralizing fluid were calculated to be +3.5 to +4.5%o and ‐2.7%o, respectively. Sedimentary dolomite has restricted δ¹³C and δ¹⁸O ranges, within the reported ranges for non‐mineralized Middle Proterozoic dolomite. An ore formation model developed for Eastern Creek, in which a basinal fluid at about 200°C carrying base metals and sulphide was released from underlying sediments during local fault movement, may be applicable to a number of other deposits. The mineralization deposited from these fluids occurs only below the pre‐Roper Group unconformity, implying that it may be older than the basal Roper Group. The δ³⁴S values of iron sulphides in fine grained black dolostones (not associated with mineral deposits) from the McArthur Basin were assessed in the light of the values found for sulphides in modern organic‐rich sedimentary environments. The data so obtained suggest that the considerable concentration of iron sulphide in the mineral deposits formed, at least in part, from heated basinal waters and that disseminated iron sulphides remote from mineralization also formed from a similar source.     

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.     

Calcium-isotope fractionation in selected modern and ancient marine carbonates

The calcium-isotope composition (δ^44/42Ca) was analyzed in modern, Cretaceous and Carboniferous marine skeletal carbonates as well as in bioclasts, non-skeletal components, and diagenetic cements of Cretaceous and Carboniferous limestones. In order to gain insight in Ca²⁺_aq-CaCO₃-isotope fractionation mechanisms in marine carbonates, splits of samples were analyzed for Sr, Mg, Fe, and Mn concentrations and for their oxygen and carbon isotopic composition. Biological carbonates generally have lower δ^44/42Ca values than inorganic marine cements, and there appears to be no fractionation between seawater and marine inorganic calcite. A kinetic isotope effect related to precipitation rate is considered to control the overall discrimination against ⁴⁴Ca in biological carbonates when compared to inorganic precipitates. This is supported by a well-defined correlation of the δ^44/42Ca values with Sr concentrations in Cretaceous limestones that contain biological carbonates at various stages of marine diagenetic alteration. No significant temperature dependence of Ca-isotope fractionation was found in shells of Cretaceous rudist bivalves that have recorded large seasonal temperature variations as derived from δ¹⁸O values and Mg concentrations. The reconstruction of secular variations in the δ^44/42Ca value of seawater from well preserved skeletal calcite is compromised by a broad range of variation found in both modern and Cretaceous biological carbonates, independent of chemical composition or mineralogy. Despite these variations that may be due to still unidentified biological fractionation mechanisms, the δ^44/42Ca values of Cretaceous skeletal calcite suggest that the δ^44/42Ca value of Cretaceous seawater was 0.3-0.4‰ lower than that of the modern ocean.     

Mineralogical and isotopic record of biotic and abiotic diagenesis of the Callovian-Oxfordian clayey formation of Bure (France)

The Callovian-Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ³⁴S (−38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (−38‰ to −22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ³⁴S values (−14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ³⁴S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The ⁸⁷Sr/⁸⁶Sr ratio of celestite (0.706872-0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ¹⁸O consistent with a marine environment. Its δ¹³C is however lower than those of marine carbonates, suggesting a contribution of ¹³C-depleted carbon from degradation of organic matter. δ¹⁸O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite crosscutting a vein filled with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ¹⁸O values (∼+19‰), suggesting that they precipitated from meteoric fluids, isotopically close to present-day pore waters of the formation. Finally, the study illustrates the transition from very active, biotic diagenesis to abiotic diagenesis. This transition appears to be driven by compaction of the sediment, which inhibited movement of bacterial cells by reduction of porosity and pore sizes, rather than a lack of inorganic carbon or sulphates.     

Origin of quartz geodes from Laño and Tubilla del Agua sections (middle–upper Campanian,Basque‐Cantabrian Basin,northern Spain): isotopic differences during diagenetic processes

Quartz geodes and nodular chert have been found within middle–upper Campanian carbonate sediments from the Laño and Tubilla del Agua sections of the Basque‐Cantabrian Basin, northern Spain. The morphology of geodes together with the presence of anhydrite laths included in megaquartz crystals and spherulitic fibrous quartz (quartzine‐lutecite), suggest an origin from previous anhydrite nodules. The anhydrite nodules at Laño were produced by the percolation of marine brines, during a period corresponding to a sedimentary gap, with δ³⁴S and δ¹⁸O mean values of 18.8‰ and 13.6‰ respectively, consistent with Upper Cretaceous seawater sulphate values. Higher δ³⁴S and δ¹⁸O mean values of 21.2‰ and 21.8‰ recorded in the Tubilla del Agua section are interpreted as being due to a partial bacterial sulphate reduction process in a more restricted marine environment. The idea that sulphates may have originated from the leaching of previously deposited Keuper sulphate evaporites with subsequent precipitation as anhydrite, is rejected because the δ³⁴S, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr values of anhydrite laths observed at both the Tubilla del Agua and Laño sections suggest an origin from younger marine brines. Later calcite replacement and precipitation of geode‐filling calcite is recorded in both sections, with δ¹³C and δ¹⁸O values indicating the participation of meteoric waters. Synsedimentary activity of the Peñacerrada diapir, which lies close to the Laño section, played a significant role in the local shallowing of the basin and the formation of quartz geodes. In contrast, eustatic shallowing of the inner marine series of the Tubilla del Agua section led to the generation of morphologically similar quartz geodes. Copyright © 2002 John Wiley & Sons, Ltd.     

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.     

Terrestrial and freshwater carbonates in Hoxnian interglacial deposits, UK: micromorphology, stable isotopic composition and palaeoenvironmental significance

MIS 11 is often considered to be the best climatic analogue for the Holocene. Many studies have suggested, however, that it is a period of extreme climate warmth comparable in temperatures to the Middle and Late Pliocene. In Britain deposits of the Hoxnian interglacial are correlated to MIS 11 and multi-proxy techniques can be used to reconstruct the climate of this interglacial. Soil, groundwater and freshwater carbonates are common in Hoxnian deposits and the stable isotopic composition of these precipitates can be used to increase our understanding of MIS 11 environments in Britain. Carbonates from Marks Tey, Clacton, Swanscombe, Elveden and West Stow are studied, the stratigraphic context of which indicates that their formation is broadly synchronous (in the mid-Hoxnian, pollen zones Ho II to Ho III). The carbon isotopic composition of groundwater and pedogenic carbonates is typically depleted with respect to δ¹³C (ca −9 to −8‰ VPDB) reflecting uptake of plant respired CO₂ during water migration/recharge. The carbon isotopic composition of lacustrine carbonate is more enriched with respect to δ¹³C (ca 0-1‰VPDB) reflecting the equilibration of lake waters with atmospheric CO₂. The δ¹⁸O of groundwater and pedogenic carbonates is slightly more enriched than modern soil carbonates but not as enriched as soil carbonates formed under interglacials that were warmer than the Holocene (i.e. the Cromerian). The stable isotopic composition of Hoxnian carbonates does not, therefore, indicate that this interglacial was characterised by uniquely warm climates in the context of other Middle Pleistocene interglacials and the Holocene. This is contrary to many marine and littoral records from around the world but consistent with environmental records from Britain and Europe.     

Variations of the Ca/Ca ratio in seawater during the past 24 million years: evidence from δCa and δO values of Miocene phosphates

The Ca isotope variation of 11 Miocene and Pleistocene, authigenic, marine phosphates is rather small compared to the corresponding variation in δ¹⁸O values. The δ⁴⁴Ca values are not correlated with the δ¹⁸O values and, therefore, they are not temperature controlled. It is likely that the δ⁴⁴Ca values of the phosphorites reflect the variation in the δ⁴⁴Ca values of paleo-seawater but, in contrast to Sr, not the isotopic composition of seawater itself. Furthermore, Ca and Sr isotopic compositions are decoupled with decreasing stratigraphic age of the phosphate peloids with Sr isotopic compositions changing to more radiogenic values while Ca isotopic compositions remain rather stable. All samples have δ⁴⁴Ca values below present-day seawater values, suggesting that phosphate formation discriminates against heavy Ca isotopes.Phosphorites and carbonaceous sediments have a similar Ca isotopic variation during the Miocene. A systematic and more or less constant shift between marine carbonates and phosphates is observed: the phosphate samples are slightly less enriched in ⁴⁰Ca compared to carbonates. This shift has been related to a mineral-dependent kinetic mass fractionation during precipitation from seawater. The rather stable δ⁴⁴Ca value for the 19 to 9 Ma old phosphorites points to a constant δ⁴⁴Ca fractionation of about 1.1 between seawater and phosphorites during the past and suggests steady-state conditions for the Mid-Miocene seawater (sedimentation flux equals erosion flux).     

An alternative model for positive shifts in shallow-marine carbonate δ13C and δ18O

Abstract Positive shifts in global seawater δ¹³C_DIC are related to changes in the ratio of organic relative to inorganic carbon burial in oceanic basins, whereas factors such as climatic cooling and the accumulation of polar ice are known to cause positive shifts in δ¹⁸O. Here, an alternative model is proposed for the formation of local positive isotope shifts in shallow-marine settings. The model involves geochemically altered platform-top water masses and the effects of early meteoric diagenesis on carbonate isotopic composition. Both mechanisms are active on modern (sub)tropical carbonate platforms and result in low carbonate δ¹³C and δ¹⁸O relative to typical oceanic values. During high-amplitude transgressive events, the impact of isotopically light meteoric fluids on the carbonate geochemistry is much reduced, and ¹³C-depleted platform-top water mixes with open oceanic water masses having higher isotope values. Both factors are recorded as a transient increase in carbonate ¹³C and ¹⁸O relative to low background values. These processes must be taken into consideration when interpreting the geochemical record of ancient epeiric seas.     

Calcite cementation during bacterial manganese, iron and sulphate reduction in Jurassic shallow marine carbonates

Faunally restricted argillaceous wackestones from the Middle Jurassic of eastern England contain evidence of early diagenetic skeletal aragonite dissolution and stabilization of the carbonate matrix, closely followed by precipitation of zoned calcite cements, and precipitation of pyrite. Distinctive cathodoluminescence and trace element trends through the authigenic calcites, their negative δ¹³C compositions and the location of pyrite in the paragenetic sequence indicate that calcite precipitation took place during sequential bacterial Mn, Fe and sulphate reduction. Calcite δ¹⁸O values are compatible with cementation from essentially marine pore fluids, although compositions vary owing to minor contamination with ¹⁸O-depleted ‘late’cements. Mg and Sr concentrations in the calcites are lower than those in recent marine calcite cements. This may be a result of kinetic factors associated with the shallow burial cementation microenvironments. Bicarbonate for sustained precipitation of the authigenic calcites was derived largely from aragonite remobilization, augmented by that produced through anaerobic organic matter oxidation in the metal and sulphate reduction environments. Aragonite dissolution is thought to have been induced by acidity generated during aerobic bacterial oxidation of organic matter. Distinction of post-oxic metal reduction and anoxic sulphate reduction diagenetic environments in modern carbonate sediments is uncommon outside pelagic settings, and early bacterially mediated diagenesis in modern platform carbonates is associated with extensive carbonate dissolution. High detrital Fe contents of the Jurassic sediments, and their restricted depositional environment, were probably the critical factors promoting early cementation. These precipitates constitute a unique example of calcite authigenesis in shallow water limestones during bacterial Mn and Fe reduction.     

Diagenesis of a mixed siliciclastic/evaporitic sequence of the Middle Muschelkalk (Middle Triassic), the Catalan Coastal Range, NE Spain

The Middle Muschelkalk (Middle Triassic) of the Catalan Coastal Range (north-east Spain) comprises sandstone, mudstone, anhydrite and minor carbonate layers. Interbedded sandstones and mudstones which are dominant in the north-eastern parts of the basin are terminal alluvial fan deposits. South-westward in the basin, the rocks become dominated by interbedded evaporites and mudstones deposited in sabkha/mudflat environments. The diagenetic and pore water evolution patterns of the Middle Muschelkalk suggest a strong facies control. During eodiagenesis, formation of microdolomite, anhydrite, baryte, magnesite, K-feldspar and mixed-layer chlorite/smectite was favoured within and adjacent to the sabkha/mudflat facies, whereas calcite, haematite, mixed-layer illite/smectite and quartz formed mainly in the alluvial facies. Low δ¹⁸O_SMOW values for microdolomite (+23.7 to +28.4%) and K-feldspar overgrowths (+17.3 to +17.7%) suggest either low-temperature, isotopic disequilibrium or precipitation from low-¹⁸O porewaters. Low-¹⁸O waters might have developed, at least in part, during low-temperature alteration of volcanic rock fragments. During mesodiagenesis, precipitation of quartz overgrowths and coarse dolomite occurred in the alluvial sandstones, whereas recrystallization of microdolomite was dominant in the sabkha/mudflat facies. The isotopic compositions of these mesogenetic phases reflect increasing temperature during burial. Upon uplift and erosion, telogenetic calcite and trace haematite precipitated in fractures and replaced dolomite. The isotopic composition of the calcite (δ¹⁸O_SMOW=+21.5 to +25.6%o; δ¹³C= 7.7 to - 5.6%o) and presence of haematite indicate infiltration of meteoric waters.