Light δ18O Values Research Articles

Bimodality in zircon oxygen isotopes and implications for crustal melting on the early Earth

Zircons from the oldest dated felsic crust, the Acasta Gneiss Complex, Canada, provide key information that may help understand the generation of crust on our nascent planet. When screened to eliminate grains with secondary alteration by measuring relative hydration (Δ16O1H/16O), primary ≥ 3.99 Ga zircon cores show δ18O of 5.88 ± 0.15 ‰, at the extreme upper (heavy) range for mantle values. Another early (≥3.96 Ga) zircon component indicates distinctly different, primary light δ18O values (δ18O ≤ 4.5 ‰). This bimodality in ancient zircon oxygen isotopes implies partial melting of both deep (lower crustal) and shallower (near surface) source rocks, responsible for felsic crust production on the early Earth. A similar bimodality in zircon δ18O is recognised in data from other ancient cratons, albeit at different times. Although alternative (uniformitarian) interpretations may also satisfy the data, the tempo of this bimodality matches models of planetary high-energy impact flux, consistent with a fundamental role for bolide impacts in the formation of crustal nuclei on the early Earth.

Karst hydrological changes during the Late-Holocene in Southwestern China

The frequent alternation between droughts and floods in the karst regions of Southwestern China has a serious impact on the ecological environment and socio-economic development. Although some high-resolution records for this region have been published, there is a lack of multi-proxy geological records that could be used to reconstruct the relationships between the changes in the Asian summer monsoon (ASM) and the regional hydrology and ecological environment since the Late Holocene. In this study, the history of the ASM from 3109 to 694 yr BP with a mean temporal resolution of 2.5 yr is reconstructed based on 47 high-precision 230Th dating results (mean 2-sigma error of ±14 yr), 959 pairs of δ18O/δ13C data, and multiple trace element analyses of a stalagmite from Shijiangjun (SJJ) Cave in the karst area of Southwestern China. The positive δ18O and δ13C excursions accurately recorded eight interdecadal-centennial weak summer monsoon events at ∼779, 1013–911, 1282–1172, 1736–1638, 1961–1864, 2472–2375, 2931–2818, and 3050–3014 yr BP. The cross-wavelet spectrum analysis of the δ18O and δ13C of stalagmite SJJ7 indicates that they have similar periods. The 7 yr period of the δ18O record was determined to have the maximum contribution rate (36.8%) to the periods using ensemble empirical mode decomposition (EEMD) analysis. In the Late Holocene, the weak ASM events were dominated by the southward shift of the Intertropical Convergence Zone (ITCZ) and the frequent El Niño events on an interdecadal-centennial timescale. The southward migration of the ITCZ lead to frequent El Niño events, and the resultant Hadley Circulation and Walker Circulation were weakened, leading to a weak ASM and changes in the hydrological conditions in the monsoon region. The δ13C values of the stalagmite changed relatively slowly compared with the δ18O values, which may indicate that the degradation and restoration of the regional ecological environment caused by abrupt changes in the climate is a relatively slow process. When the summer monsoon decreased, the stalagmite’s Mg/Ca and Sr/Ca ratios were relatively high due to CO2 degassing, and the prior calcite precipitation (PCP)/prior aragonite precipitation (PAP) increased in the karst zone. However, the Mg/Ca ratio increased and the Sr/Ca ratio rapidly decreased during the calcite deposition due to differences in the crystal structures and partition coefficients of aragonite and calcite. The dark layers in stalagmite SJJ7 correspond to transition from heavy to light δ18O values, reflecting the transition in the ASM. The pulsed increases in the elements (Mn, Fe, Al, and Si) in the dark layers reflect the stronger mechanical transport caused by more rainfall. The multi-proxy analysis of this stalagmite may reflect the interactions between the changes in the ASM and the atmosphere-hydrosphere-pedosphere-biosphere-lithosphere in the karst critical zone during the Late Holocene.

Molecular and chemical response signatures illustrate species differences of developing neural progenitor cells from human, mouse and rat

The Ediacaran Schisto-Calcaire Group is a ∼1300 m-thick succession belonging to the West Congo Supergroup in Central Africa. In the Comba Basin, it consists of three carbonate-dominated units defined as formations (SCI to SCIII) that are unconformably overlain by clastic deposits (Mpioka Group) interpreted as a molassic formation associated with the Panafrican Orogen. The underlying Upper Tillite and Cap Carbonate (SCIa) units, considered as markers of the Snowball Earth event were studied in three sections. We investigated the carbonates of the Schisto-Calcaire Group by defining new microfacies (MF1-MF7) and we performed C and O isotopic analyses in order to constraint the depositional and diagenetic events directly after the Marinoan interval. Stratigraphic variations of the stable isotopes are important in the series with lighter δ18O values (>1.5‰) than those of the Neoproterozoic ocean in the SCIc unit. According to regional stratigraphy a temperature effect can be dismissed and a freshwater surface layer is the origin of such negative δ18O values in this unit. The negative δ13C anomaly (−3.5‰ on average) of the Cap Carbonate is similarly to the δ18O values (−6.4‰ on average) in the range of the marine domain during postglacial sea level rise. The sample suite as a whole (SCII and SCIII formations) displays heavier δ18O and δ13C than those of the lower part (SCI unit) of the Schisto-Calcaire Group. The comparison with the Lower Congo (Democratic Republic of Congo) and Nyanga (Gabon) basins shows that the meteoric flushing in SCIc unit of the Schisto-Calcaire Group was regional and not local, and could be derived from a climatic evolution. Although an overall overprint is present, our isotopic relationships argue against overall diagenetic resetting of primary compositions and suggest that with careful examination combined with detailed petrographic analysis general depositional and diagenetic controls can be discerned in oxygen and carbon isotopic data in the Schisto-Calcaire Group.

Causes and consequences of Arctic freshwater routing into the Nordic Seas during late Marine Isotope Stage 5

ABSTRACTSediment core PS1904 reveals continuous records of planktic and benthic foraminiferal stable isotopes (δ18O/δ13C) from the north‐eastern Greenland continental margin. The data show good comparability with other records from the Nordic Seas, allowing the stratigraphic range of PS1904 to be dated to Marine Isotope Stage (MIS) 6. Focusing on MIS 5 reveals light δ18O values during MIS 5a compared to the last interglacial peak (MIS 5e) which indicates that surface and bottom water layers were strongly affected by freshwater during the former event. We present two possible scenarios explaining the origin and routing of the freshwater: (i) drainage of a Eurasian proglacial lake coupled with the collapse of the Kara Sea Ice Sheet at the MIS 5b/a boundary, and (ii) destabilization and melting of the nearby Greenland Ice Sheet. Although both scenarios could have acted simultaneously, sediment records from the Eurasian sector of the Arctic Ocean hint at the proglacial lake system in north‐western Siberia as the largest freshwater source. Regardless of the actual source, the freshwater lowered the surface ocean salinity causing water column stratification and sea ice expansion. Increased sea‐ice abundance led to a higher albedo and probably contributed to the cooling and global ice sheet growth that occurred subsequently during MIS 4.

Palaeohydrogeology using geochemical, isotopic and mineralogical analyses: Salinity and redox evolution in a deep groundwater system through Quaternary glacial cycles

Mineralogical, geochemical and isotopic analyses of secondary calcites are interpreted as part of an investigation of deep groundwaters in fractured metavolcanic rock overlain by sedimentary rock. Drillcore rock samples and groundwater samples from deep boreholes (maximum depth 1950 m) were analysed. This produces information about the evolution of salinity and redox in relation to past groundwater movements including the impacts of climatic change through the Quaternary period.Salinities of present-day groundwaters vary from dilute to brine concentrations and are related to three distinct groundwater flow regimes. Crystal morphology, stable isotopic analyses and isotopic dating, cathodoluminescence and microanalyses of Fe, Mn and REEs in the latest generation of secondary calcite, plus other analyses, have provided insights into variations of salinity over time and of redox in past groundwaters. Interpretation suggests that groundwater in the depth range of the transition from dilute to brackish/saline concentrations has been gradually diluted over time by meteoric water ingress. 230Th/234U whole-crystal ages indicate that at least part of the late-stage calcite mineralisation in the present groundwater flow system is of Quaternary age, although the mineralisation may have been initiated much earlier by meteoric invasion in the Miocene, following regional uplift. The calcites exhibit a wide range in oxygen isotope composition (δ18OPDB −2 to −22‰), although no extremely light or heavy δ13C values indicative of microbial methane oxidation or deep methanogenesis were observed. The very light δ18O values suggest that glacial or other cold-climate waters flowed to more than 700 m depth in the centre of the study area and formed a greater proportion of groundwater at that depth than at present.Fe and Ce are interpreted as semi-quantitative proxies for past redox conditions over the period when secondary calcite was deposited. Variability of Fe and Mn contents of secondary calcites in deeper rock, presently containing saline groundwater, is evidence of reducing conditions being maintained in the long term, though the strength of negative redox has probably fluctuated due to other redox-active chemistry. Depth-wise changes of groundwater redox in the past are also indicated by Ce concentrations versus other REEs in secondary calcites. Shallow calcites show a negative Ce anomaly in some growth zones due to oxidation to CeIV whilst deeper calcites do not exhibit this Ce behaviour, indicating that reducing conditions prevailed. Distribution of Fe-Mn oxyhydroxides and pyrite confirm, at a broader scale over depth and time, the findings about redox variations that secondary calcites indicate.Mineralogical and geochemical studies add further information to the understanding of past geochemical conditions in deep groundwaters in this area. Interpretations provide semi-quantitative constraints on the evolution and likely variations and directions of movement of groundwater salinity and redox over the Quaternary timescale.

Stable isotope and fluid inclusion study of sediment-hosted stratiform copper deposits from the Neuquén Basin, Argentina

The Los Chihuidos and El Porvenir deposits of the Neuquen Basin are examples of sediment-hosted stratiform Cu deposits generated by interaction of hydrocarbons and formation water with host red beds and metal-charged basinal brines. During early diagenesis of red beds precipitated hematite, kaolinite at 60 °C from meteoric water followed by calcite 1 (δ13C − 8 to − 3.3‰) and barite (δ34S + 4.1‰) with increasing temperature (75–85 °C) from an evolved surface fluid (δ18Ofluids + 0.9 to + 2.7‰). During the Tertiary Andean orogeny, hydrocarbons and formation water migrated and reacted with the red beds resulting in bleaching of the sandstone. Smectite (fluid δ18O − 2.2‰ and δD − 73.7‰), chlorite-smectite mixed-layer minerals (fluid δ18O − 6.9‰ and δD − 84‰), pyrite (δ34S + 10.2‰), and calcite 2 (δ13C − 12.9 to − 6.8‰) formed as by-product of the redox reactions. Calcite 2 formed from low-salinity fluids (0.4 to 5.9 wt% NaCl equiv.) at slightly higher temperatures (125–145 °C) at El Porvenir and at Los Chihuidos deposit (80–105 °C). During subsequent uplift, metal-charged basinal brines flowed into the bleached sandstone and precipitated chalcopyrite-bornite (δ34S + 12.3‰) followed by chalcocite-spionkopite (δ34S − 64 to + 4.1‰). Calcites 3a (δ13C − 19 to − 10.1‰) and 3b (δ13C − 31.4 to − 9.5‰) that accompanied Fe-Cu and Cu sulfides, respectively, formed from saline fluids (up to 21.3 wt% NaCl equiv.) at temperatures of 159–70 °C. The δ18O values (+ 5.6 to + 11.4‰) of fluids in equilibrium with calcite 3a are similar to oilfield and basinal brines. Fluids in equilibrium with calcite 3 in Los Chihuidos and calcite 3b in El Porvenir show much lighter δ18O values (− 7.3 to − 4.6‰ and − 0.6 to + 2.3‰, respectively), which suggests the involvement of methane as the main reductant and possibly meteoric water interaction.

Sea ice, ice‐rafting, and ocean climate across Denmark Strait during rapid deglaciation (∼16–12 cal ka BP) of the Iceland and East Greenland shelves

ABSTRACTA suite of cores from the North‐West Iceland and East Greenland shelves sampled fossiliferous or unfossiliferous basal glacial diamictons. Radiocarbon dates above the diamictons are similar on both shelves, but the value of the ocean reservoir correction, ΔR, is unknown. Deglaciation occurred either ∼16 or 14 cal ka BP depending on the choice of ΔR. The ice sheets were behind the present coastline by 12.2 cal ka BP. We examine seven cores that record the glacial/deglacial transition and present new data on the sea‐ice biomarkers IP25 and C25:2 from four of the cores plus data on ice‐rafted debris counts, grain‐size spectra, δ18O on the near‐surface planktonic foraminifera Neogloboquadrina pachyderma (s), foraminifera assemblages, and quartz percentage. IP25 concentrations are markedly higher for the East Greenland sites, while they are frequently below the limit of quantification off Iceland, observations that parallel the wt% quartz in the sediments. The δ18O N. pachyderma (s) data show a strong gradient across Denmark Strait with lighter δ18O values towards the East Greenland shelf indicative of a large freshwater flux. The presence of the chilled Atlantic Water benthic foraminifera, Cassidulina neoteretis indicates that rapid ice sheet retreat was associated with ocean forcing, combined with other factors.

Paleoenvironments, δ13C and δ18O signatures in the Neoproterozoic carbonates of the Comba Basin, Republic of Congo: Implications for regional correlations and Marinoan event

The Ediacaran Schisto-Calcaire Group is a ∼1300 m-thick succession belonging to the West Congo Supergroup in Central Africa. In the Comba Basin, it consists of three carbonate-dominated units defined as formations (SCI to SCIII) that are unconformably overlain by clastic deposits (Mpioka Group) interpreted as a molassic formation associated with the Panafrican Orogen. The underlying Upper Tillite and Cap Carbonate (SCIa) units, considered as markers of the Snowball Earth event were studied in three sections. We investigated the carbonates of the Schisto-Calcaire Group by defining new microfacies (MF1-MF7) and we performed C and O isotopic analyses in order to constraint the depositional and diagenetic events directly after the Marinoan interval. Stratigraphic variations of the stable isotopes are important in the series with lighter δ18O values (>1.5‰) than those of the Neoproterozoic ocean in the SCIc unit. According to regional stratigraphy a temperature effect can be dismissed and a freshwater surface layer is the origin of such negative δ18O values in this unit. The negative δ13C anomaly (−3.5‰ on average) of the Cap Carbonate is similarly to the δ18O values (−6.4‰ on average) in the range of the marine domain during postglacial sea level rise. The sample suite as a whole (SCII and SCIII formations) displays heavier δ18O and δ13C than those of the lower part (SCI unit) of the Schisto-Calcaire Group. The comparison with the Lower Congo (Democratic Republic of Congo) and Nyanga (Gabon) basins shows that the meteoric flushing in SCIc unit of the Schisto-Calcaire Group was regional and not local, and could be derived from a climatic evolution. Although an overall overprint is present, our isotopic relationships argue against overall diagenetic resetting of primary compositions and suggest that with careful examination combined with detailed petrographic analysis general depositional and diagenetic controls can be discerned in oxygen and carbon isotopic data in the Schisto-Calcaire Group.

High-frequency surface water changes in the Tagus prodelta off Lisbon, eastern North Atlantic, during the last two millennia

Abstract A high-resolution sedimentary sequence recovered from the Tagus prodelta has been studied with the objective to reconstruct multi-decadal to centennial-scale climate variability on the western Iberian Margin and to discuss the observations in a wider oceanographic and climatic context. Between ca. 100 BC and AD 400 the foraminiferal fauna and high abundance of Globorotalia inflata indicate advection of subtropical waters via the Azores Current and the winter-time warm Portugal Coastal Current. Between ca. AD 400 and 1350, encompassing the Medieval Climate Anomaly (MCA), enhanced upwelling is indicated by the planktonic foraminiferal fauna, in particular by the high abundance of upwelling indicator species Globigerina bulloides. Relatively light δ18O values and high sea surface temperature (SST) (reconstructed from foraminiferal assemblages) point to upwelling of subtropical Eastern North Atlantic Central Water. Between ca. AD 1350 and 1750, i.e. most of the Little Ice Age, relatively heavy δ18O values and low reconstructed SST, as well as high abundances of Neogloboquadrina incompta, indicate the advection of cold subpolar waters to the area and a southward deflection of the subpolar front in the North Atlantic, as well as changes in the mode of the North Atlantic Oscillation. In addition, the assemblage composition together with the other proxy data reveals less upwelling and stronger river input than during the MCA. Stronger Azores Current influence on the Iberian Margin and strong anthropogenic effect on the climate after AD 1750 is indicated by the foraminiferal fauna. The foraminiferal assemblage shows a significant change in surface water conditions at ca. AD 1900, including enhanced river runoff, a rapid increase in temperature and increased influence of the Azores Current. The Tagus record displays a high degree of similarity to other North Atlantic records, indicating that the site is influenced by atmospheric–oceanic processes operating throughout the North Atlantic, as well as by local changes.

LATE MIOCENE SEASONAL TO SUBDECADAL CLIMATE VARIABILITY IN THE INDO-WEST PACIFIC (EAST KALIMANTAN, INDONESIA) PRESERVED IN GIANT CLAMS

ABSTRACT Two late Miocene Tridacna (giant clam) shells from East Kalimantan (Indonesia) were investigated in order to evaluate their potential as subannually resolved paleoenvironmental archives. Via a combination of X-ray diffraction (XRD), laser ablation–inductively coupled plasma–mass spectrometry (LA-ICPMS) trace element analysis, scanning electron microscopy (SEM) and cathodoluminescence (CL) imaging, pristine versus diagenetically altered domains within the shells were identified. LA-ICPMS transects targeting altered aragonite and calcite zones reveal distinct compositional differences in elemental ratios (B/Ca, Mg/Ca, Sr/Ca/ Ba/Ca, Mn/Ca, Al/Ca, La/Ca, Ce/Ca) relative to primary shell aragonite. Pristine shell domains are characterized by an intact banding pattern of alternating dark and light growth bands, with which spatially resolved LA-ICPMS element/Ca and micromilled δ18O records were aligned. Light δ18O values correspond to dark growth bands, indicating growth during warm seasons. The Mg/Ca a...

Evolution of subpolar North Atlantic surface circulation since the early Holocene inferred from planktic foraminifera faunal and stable isotope records

Past changes in the surface flow regime of two main eastern North Atlantic warm water pathways toward the Nordic seas were reconstructed based on faunal analyses in combination with carbon and oxygen stable isotope measurements in planktic foraminifera. The investigated sites, in the surroundings of the Faroe Islands, are located in the transitional area where surface waters of subpolar and subtropical origin mix before entering the Arctic Mediterranean. In these areas, large-amplitude millennial variability in the characteristics of the upper-water column appears modulated by changes in the intensity of the Subpolar Gyre circulation. From 7.8 to 6 ka BP, faunal records indicate a deep mixed-layer which, in conjunction with lighter δ18O values, suggest that the inflowing Atlantic waters were dominated by a relatively cooler and fresher water mass, reflecting a strengthening of the Subpolar Gyre under conditions of enhanced positive NAO-like forcing and reduced meltwater input. A shift in the hydrographic conditions occurred during the Mid-Holocene (centered at 5 ka BP). At this time, increasing upper water column stratification and the incipient differentiation of the stable isotopic signal of the Iceland–Faroe and Faroe–Shetland surface water masses, suggest increasing influx of warmer, more saline surface waters from the Subtropical Gyre, as Subpolar Gyre circulation weakened. The mid-Holocene decline in Subpolar Gyre strength is presumably related to a shift toward a low state of the NAO-like forcing associated with decreased solar irradiance. Later in the Holocene, from 4 ka BP to present, the increased frequency and reduced amplitude of the surface hydrographic changes reflect corresponding fluctuations in Subpolar Gyre circulation. These high frequency oscillations in Subpolar Gyre strength suggest increased surface circulation sensitivity to moderate freshwater fluxes to the Labrador–Irminger Sea basin, highlighting the importance of the salinity balance in modulating Subpolar Gyre dynamics, particularly under conditions of low NAO atmospheric forcing.

Palaeoceanography of the Miocene (Tortonian) deposits of the Pre-Apulian zone, western Greece, as recorded by foraminifer and stable isotope records

An integrated faunal and geochemical dataset has been generated by the study of a late Miocene (early Tortonian) sedimentary section outcropping at Manassi, Levkas Island (eastern Mediterranean). Quantitative analysis of benthic foraminifers from the 25-m-thick section indicates changes of bottom palaeoecological conditions in this part of the eastern Mediterranean, during the analyzed time interval. Benthic foraminifer assemblages are typical of a bathyal environment and testify to relatively oxygenated conditions with low to moderate food supply alternating with periods with an increase in organic matter content. The long-term palaeoceanographic analyses indicate an anti-estuarine circulation model based on the benthic foraminifer and stable isotope results, which evolved in a strong estuarine circulation. The positive relationship existing between the plankton δ18O and δ13C, in most of the record, agrees well with the hypothesis of a variable contribution of runoff. In three stratigraphic levels, samples record heavy bottom water δ18O and δ13C values and light surface δ18O values, representing a wet, warm, estuarine climate with a stratified water column. In two stratigraphic levels, samples have depleted δ13C and δ18O values for both surface and bottom waters. These two samples represent wet, warm climates with some ocean mixing and stratification. The stable isotope signal of foraminifer tests from the Manassi section was influenced by the global temperature changes, but the local factors also played an important role. The palaeoenvironments derived from stable isotope analysis in this study are interpreted as responses to the local tectonic instability together with monsoon intensities that enhanced continental runoff, characteristic for the time interval studied in the study area. Due to the limited data available from this study, no correlations with the precessional, obliquity, or eccentricity cycles can be made.

Late Miocene sedimentary environments in south-western Amazonia (Solimões Formation; Brazil).

In Miocene times a vast wetland existed in Western Amazonia. Whereas the general development of this amazing ecosystem is well established, many questions remain open on sedimentary environments, stratigraphical correlations as well as its palaeogeographical configuration. Several outcrops located in a barely studied region around Eirunepé (SW Amazonas state, Brazil) were investigated to obtain basic sedimentological data. The observed deposits belong to the upper part of the Solimões Formation and are biostratigraphically dated to the Late Miocene. Vertically as well as laterally highly variable fine-grained clastic successions were recorded. Based on the lithofacies assemblages, these sediments represent fluvial deposits, possibly of an anastomosing river system. Sand bodies formed within active channels and dominant overbank fines are described (levees, crevasse splays/channels/deltas, abandoned channels, backswamps, floodplain paleosols). Lacustrine environments are restricted to local floodplain ponds/lakes. The mollusc and ostracod content as well as very light δ18O and δ13C values, measured on ostracod valves, refer to exclusively freshwater conditions. Based on palaeontological and geological results the existence of a long-lived lake (“Lake Pebas”) or any influx of marine waters can be excluded for that region during the Late Miocene.

Historic magmatism on the Reykjanes Peninsula, Iceland: a snap-shot of melt generation at a ridge segment

We present new compositional data on a suite of historic lava flows from the Reykjanes Peninsula, Iceland. They were erupted over a short time period between c. 940 and c. 1340 ad and provide a snap-shot view of melt generation and evolution processes beneath this onshore, 65 km long, ridge segment. The lavas are tholeiitic basalts (MgO 6.5–9.2 wt%) and sparsely (≪5%) olivine and/or plagioclase phyric (±trace clinopyroxene). Individual eruptive events show remarkable compositional homogeneity. Despite a limited variation in Sr–Nd isotope compositions, high-precision double-spike Pb isotope data show tight coherent arrays that, together with correlations with incompatible trace element ratios, indicate control by binary mixing processes. Poor correlations with elemental abundances require that this mixing took place prior to extensive fractional crystallisation. Olivines in the historic lavas have light δ18O values (+4.2 to +4.3‰), which is likely to be a feature of the enriched mantle source to Reykjanes Peninsula lavas. High precision Pb isotope analyses of other post-glacial Reykjanes Peninsula lavas show significant variability in 207Pb/204Pb and 208Pb/204Pb at lower 206Pb/204Pb values than in the historic lavas. This variation demonstrates that at least three compositionally distinct components within the mantle are required to explain the Pb isotope variations within the Reykjanes Peninsula as a whole.

Geochemical, and stable and radiogenic isotope records in Devonian and Early Carboniferous carbonates from Valle de Tena, central Pyrenees (Spain): evidence for their diagenetic environments

Mineralogical, textural and geochemical investigations were made to determine the post-depositional evolution of Devonian and Early Carboniferous carbonates from Valle de Tena. The carbonate association is made up of low-Mg calcite, which occurs as micrite, spar cements, neomorphic patches and spar filling veinlets. Non-stoichiometric dolomite and ankerite occur as cements (dolomite also as replacements) in the Middle Devonian, post-dating calcite types. All these phases pre-date tectonic stylolites, indicating compaction after stabilization of the carbonate minerals. Strontium concentrations indicate that Early Devonian and Early Carboniferous micrites initially precipitated as aragonite; Middle and Late Devonian micrites precipitated as high-Mg calcites. Both precursors were diagenetically stabilized to low-Mg calcites through interaction with meteoric waters in phreatic environments. Trace elements in dolomite and ankerite indicate precipitation from Sr-enriched meteoric water. All studied carbonates, except Middle Devonian limestones, precipitated in reducing environments, which favoured incorporation of Fe and Mn. Late calcite generations precipitated from more saline waters than micrites. Light δ18O values in micrites suggest alteration mainly in meteoric-phreatic environments. The dolomites and ankerites precipitated from more 18O-depleted fluids than the calcites, suggesting a greater contribution from meteoric waters. Variations in δ13C of micrites represent primary secular trends, according to published δ13C variations. The δ13C oscillations within each succession probably relate to sea-level oscillations. Strontium isotopes also point to a meteoric origin of diagenetic fluids. Model calculations suggest that O and Sr isotopes equilibrated between calcites and fluid at relatively low water/rock ratios, whereas C isotopic signatures are inherited from limestones.

A Late Pleistocene marine clay succession at Kriegers Flak, westernmost Baltic, southern Scandinavia

In the Baltic Sea south of Skane county in southern Sweden, an over- consolidated marine clay succession on the northeastern slope of Kriegers Flak was observed in shallow seismic data as a unit overlain by younger Weichselian sediments. Two cores were taken from the clay succession. The Foraminifera present were predominantly of two species, Elphidium excavatum and Elphidium albiumbilicatum, reflecting deposition under arctic– boreal conditions. Stable oxygen isotope analyses were performed on foraminiferal tests, and the results show extremely light δ18O values ranging between −11‰ and −12‰. The cause of these extreme values is uncertain but may result from the high influence of meltwater. Brackish conditions are also indicated by the tolerance for low salinity shown by the Foraminifera. Radiocarbon dating shows an infinite age >40000 yr BP. The pollen flora seems mainly to have been redeposited, which makes interpretation difficult. The sea may have entered the Baltic basin during periods with high eustatic levels, an isostatic downloading of the crust, or a combination of both. It is suggested that the deposition of the overconsolidated marine clay succession occurred in the Late Saalian, Early Eemian or Early Weichselian. © 1998 John Wiley & Sons, Ltd.

The nature and origin of sideritic ironstone bands in the Tertiary Lowmead and Duaringa Basins, Queensland

Sideritic ironstones in Tertiary lacustrine oil shale from the Lowmead and Duaringa Basins in Queensland, contain two distinctive types of siderite in the ironstone bands: sphaerosiderite in the mudstone and coal, and finely crystalline siderite in the lamosite. The petrological evidence indicates that the siderite in the ironstone bands formed eogenetically by growing displacively within the soft sediment. Chemically the siderite is very pure though the sphaerosiderite sometimes shows compositional zoning. Stable oxygen and carbon isotope analyses of the siderite show a wide range of values from ‐12.8‰ to ‐2.4 %0 δ18O (PDB) and ‐5.5‰ to +12.9‰ δ13C (PDB) for the Lowmead Basin; and ‐9.6‰ to ‐1.2‰ δ18O (PDB) and ‐18.6‰ to +16.4‰ δ13C (PDB) for the Duaringa Basin. The oxygen isotope data indicate that the siderite formed in freshwater environments but not in isotopic equilibrium with the formation waters. Kinetic factors offer the most plausible explanation for the anomalously light δ18O values of many of t...

Early life history and habitat of Nautilus pompilius inferred from oxygen isotope examinations

Ontogenetic change of habitat depths of Nautilus pompilius in the Philippines (Tanon Strait) and Fiji is considered by comparing 18O/16O ratios in septa and cameral fluid of live-caught specimens and ambient sea-water. δ 18O values of cameral liquid become heavier with decreasing volume within a chamber, which may be due to isotopic fractionation during discharge across the siphuncular wall. All of the seven Philippine and Fiji specimens analyzed show a distinct change in δ18O from light values in the first seven septa to heavier values in the succeeding septa. Two different isotopic temperature scales are obtained for the Fiji and Philippine populations, suggesting a differential vital effect of metabolism between them. Sightly light δ18O values in Septa 1 to 7 and hatching at relatively high temperatures in aquaria both suggest that N. pompilius hatch at the shallowest depths within their inhabitable vertical range. Depths of postembryonic animals in the Philippines and Fiji waters estimated from the isotopic temperature-depth diagrams range from 120 to 160 m and from 440 to 520 m, respectively, both of which correlate well with capture records. More than several tens of small-scale δ18O cycles are detected in the sequence of nacreous layers within the single septum of a submature Philippine specimen. This can be interpreted as reflecting daily vertical migration.

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

ABSTRACTNodular 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 + 28.80/00 (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.

The diagenesis of the late Dinantian Derbyshire‐East Midland carbonate shelf, central England

ABSTRACTCarbonate cements in late Dinantian (Asbian and Brigantian) limestones of the Derbyshire carbonate platform record a diagenetic history starting with early vadose meteoric cementation and finishing with burial and localized mineral and oil emplacement. The sequence is documented using cement petrography, cathodoluminescence, trace element geochemistry and C and O isotopes.The earliest cements (Pre‐Zone 1) are locally developed non‐luminescent brown sparry calcite below intrastratal palaeokarsts and calcretes. They contain negligible Fe, Mn and Sr but up to 1000 ppm Mg. Their isotopic compositions centre around δ18O =−8.5‰, δ13C=−5.0‰. Calcretes contain less 13C. Subsequent cements are widespread as inclusion‐free, low‐Mg, low‐Fe crinoid overgrowths and are described as having a‘dead‐bright‐dull’cathodoluminescence. The‘dead’cements (Zone 1) are mostly non‐luminescent but contain dissolution hiatuses overlain by finely detailed bright subzones that correlate over several kilometres. Across‘dead'/bright subzones there is a clear trend in Mg (500–900 ppm), Mn (100–450 ppm) and Fe (80‐230 ppm). Zone 1 cements have isotopic compositions centred around δ18O =−8.0‰ and δ13C=−2.5‰. Zone 2 cement is bright, thin and complexly subzoned. It is geochemically similar to bright subzones of Zone 1 cements. Dull Zone 3 cement pre‐dates pressure dissolution and fills 70% or more of the pore space. It generally contains little Mn, Fe and Sr but can have more than 1000 ppm Mg, increasing stratigraphically upwards. The δ18O compositions range from −5.5 to −15‰ and the δ13C range is −1 to + 3.20/00. Zone 4 fills veins and stylolite seams in addition to pores. It is synchronous with Pb, Ba, F ore mineralization and oil migration. Zone 4 is ferroan with around 500 ppm Fe, up to 2500 ppm Mg and up to 1500 ppm Mn. Isotopic compositions range widely; δ15O =−2.7 to −9‰ and δ13C=−3.8 to+2.50‰.Unaltered marine brachiopods suggest a Dinantian seawater composition around δ15O = 0‰ (SMOW), but vital isotopic effects probably mask the original δ13C (PDB) value. Pre‐Zone 1 calcites are meteoric vadose cements with light soil‐derived δ13C and light meteoric δ18O. An unusually fractionated‘pluvial’δ15O(SMOW) value of around — 6‰ is indicated for local Dinantian meteoric water. Calcrete δ18O values are heavier through evaporation. Zone 1 textures and geochemistry indicate a meteoric phreatic environment. Fe and Mn trends in the bright subzones indicate stagnation, and precipitation occurred in increments from widespread cyclically developed shallow meteoric water bodies. Meteoric alteration of the rock body was pervasive by the end of Zone 1 with a general resetting of isotopic values. Zone 3 is volumetrically important and external sources of water and carbonate are required. Emplacement was during the Namurian‐early Westphalian by meteoric water sourced at a karst landscape on the uplifted eastern edge of the Derbyshire‐East Midland shelf. The light δ18O values mainly reflect burial temperatures and an unusually high local heat flow, but an input of highly fractionated hinterland‐derived meteoric water at the unconformity is also likely. Relatively heavy δ13C values reflect the less‐altered state of the source carbonate and aquifer.Zone 4 is partly vein fed and spans burial down to 2000 m and the onset of tectonism. Light organic‐matter‐derived δ13C and heavy δ18O values suggest basin‐derived formation water. Combined with textural evidence of geopressures, this relates to local high‐temperature ore mineralization and oil migration. Low water‐to‐rock ratios with host‐rock buffering probably affected the final isotopic compositions of Zone 4, masking extremes both of temperature and organic‐matter‐derived CO2.