Geochemistry of a chert breccia

A complex history of diagenetic interactions between a siliceous sediment, seawater and fresh water is revealed by intraformational chert breccias. Chert breccias were formed in the Campanian Mishash Formation in Israel, by “practically contemporaneous” fracturing of lithified cherty layers followed by silicification and lithification of the matrix. Pairs of fragments and matrix were compared with respect to their chemical (Ca, Sr, Na, K, Mg, Li, B, SO₄, Ba) and isotopic (δ¹⁸O, δD, δ¹¹B) composition. δ¹¹B was analyzed by ion-probe and includes a profile across a fragment-matrix contact. The epicontinental cherts of the Mishash Fm. are enriched by a factor of 10 to 50 in all elements other than O and Si in comparison with Deep-Sea cherts. All results are compatible with the proposition that the lithification of the matrix occurred in contact with fresh-water, as opposed to seawater in which the fragments, as well as most of the Mishash sediments were formed. The strongest evidence for this difference is in the higher concentration of B in the fragments (27-70 ppm vs. 11-21ppm in the matrix) and higher δ¹⁸O (29 to 35‰ vs. 21 to 33‰). δD is a less efficient discriminator, though compatible with fresher water diagenesis of the matrix: −115‰ to −76‰ for hydrogen in the chert of the fragments, compared to −141 to −85‰ for the matrix. δ¹¹B in the matrix shows some of the lowest values recorded in sediments (δ¹¹B = −33‰), but varies strongly, suggesting that the source of boron in the matrix is a mixture of a freshwater and a marine component. Both seawater and the freshwater that has equilibrated with the cherts underwent varying degrees of evaporation. Ca, Sr and SO₄ are carried by apatite, trapped as detritus in the matrix. The concentration of lithium in the matrix is high (11-16 ppm), whereas in the adjacent fragments it is mostly only within 1-2 ppm. Li probably enters the matrix from the interstitial solution, during the opal → quartz transformation. The second, prolonged, transformation takes place in a (freshwater) flow-through, open system. This allows a much larger mass of Li to be scavenged by the transforming silica despite its low concentration in freshwater.     

Oxygen and hydrogen isotope ratios in freshwater chert as indicators of ancient climate and hydrologic regime

The oxygen and hydrogen isotopic composition of Eocene and Miocene freshwater cherts in the western United States records regional climatic variation in the Cenozoic. Here, we present isotopic measurements of 47 freshwater cherts of Eocene and Miocene age from the Great Basin of the western United States at two different sites and interpret them in light of regional climatic and tectonic history. The large range of δ¹⁸O of terrestrial cherts measured in this study, from 11.2‰ to 31.2‰ (SMOW: Standard Mean Ocean), is shown to be primarily the result of variations in δ¹⁸O of surface water. The following trends and patterns are recognized within this range of δ¹⁸O values. First, in Cenozoic rocks of northern Nevada, chert δ¹⁸O records the same shift observed in authigenic calcite between the Eocene and Miocene that has been attributed to regional surface uplift. The consistent covariation of proxies suggests that chert reliably records and retains a signal of ancient meteoric water isotopic composition, even though our analyses show that chert formed from warmer waters (40°C) than coexisting calcite (20°C). Second, there is a strong positive correlation between δ¹⁸O and δD in Eocene age chert from Elko, Nevada and Salina, Utah that suggests large changes in lake water isotopic composition due to evaporation. Evaporative effects on lake water isotopic composition, rather than surface temperature, exert the primary control on the isotopic composition of chert, accounting for 10‰ of the 16‰ range in δ¹⁸O measured in Eocene cherts. From authigenic mineral data, we calculate a range in isotopic composition of Eocene precipitation in the north-central Great Basin of −10 to −14‰ for δ¹⁸O and −70 to −100‰ for δD, which is in agreement with previous estimates for Eocene basins of the western United States. Due to its resistance to alteration and record of variations in both δ¹⁸O and δD of water, chert has the potential to corroborate and constrain the cause of variations in isotope stratigraphies.     

Isotopic fractionation of nitrogen and carbon in Paleoarchean cherts from Pilbara craton, Western Australia: Origin of N-depleted nitrogen

Nitrogen and carbon isotopic compositions, together with mineralogy and trace element geochemistry, were studied in a few kerogen-rich Paleoarchean cherts, a barite and a dolomitic stromatolite belonging to the eastern (Dixon Island Formation) and western (Dresser and Strelley Pool Chert Formations; North Pole Dome and Marble Bar) terranes of Pilbara Craton, Western Australia. The aim of the study was to search for ¹⁵N-depleted isotopic signatures, often found in kerogens of this period, and explain the origin of these anomalies. Trace elements suggest silica precipitation by hydrothermal fluids as the main process of chert formation with a contamination from volcanoclastic detritus. This is supported by the occurrence of hydrothermal-derived minerals in the studied samples indicating precipitation temperatures up to 350 °C. Only a dolomitic stromatolite from Strelley Pool shows a superchondritic Y/Ho ratio of 72 and a positive Eu/Eu^* anomaly of 1.8, characteristic of chemical precipitates from the Archean seawater. The bulk δ¹³C vs. δ¹⁵N values measured in the cherts show a roughly positive co-variation, except for one sample from the North Pole (PI-85-00). The progressive enrichment in ¹⁵N and ¹³C from a pristine source having δ¹³C ? −36‰ and δ¹⁵N ? −4‰ is correlated with a progressive depletion in N content and to variations in Ba/La and Co/As ratios. These trends have been interpreted as a progressive hydrothermal alteration of the cherts by metamorphic fluids. Isotopic exchange at 350 °C between NH₄⁺_(rock) and N_2(fluid) may explain the isotopic and elemental composition of N in the studied cherts. However, we need to assume isotopic exchange at 350 °C between carbonate C and graphite to explain the large ¹³C enrichment recorded. Only sample PI-85-00 shows a large N loss (90%) with a positive δ¹⁵N value (+11‰), while C (up to 120 ppm and δ¹³C −38‰) seems to be unaffected. This pattern has been interpreted as the result of devolatilization and alteration (oxidation) of graphite by low-temperature fluids. The ¹⁵N-¹³C-depleted pristine source has δ ¹⁵N values from −7‰ to −4‰ and ⁴⁰Ar/³⁶Ar ratios from 30,000 to 60,000, compatible with an inorganic mantle N source, although the elemental abundance ratios N/C and ⁴⁰Ar/C are not exactly the same with the mantle source. The component alternatively could be explained by elemental fractionation from metabolic activity of chemolithoautotrophs and methanogens at the proximity to the hydrothermal vents. However, ambiguities between mantle vs organic sources of N subsist and need further experimental work to be fully elucidated.     

Silicon isotope and trace element constraints on the origin of ∼3.5 Ga cherts: Implications for Early Archaean marine environments

Silicon (Si) isotope variability in Precambrian chert deposits is significant, but proposed explanations for the observed heterogeneity are incomplete in terms of silica provenance and fractionation mechanisms involved. To address these issues we investigated Si isotope systematics, in conjunction with geochemical and mineralogical data, in three well-characterised and approximately contemporaneous, ∼3.5 Ga chert units from the Pilbara greenstone terrane (Western Australia).We show that Si isotope variation in these cherts is large (−2.4‰ to +1.3‰) and was induced by near-surface processes that were controlled by ambient conditions. Cherts that formed by chemical precipitation of silica show the largest spread in δ³⁰Si (−2.4‰ to +0.6‰) and are characterised by positive Eu, La and Y anomalies and overall depletions in lithophile trace elements. Silicon isotope systematics in these orthochemical deposits are explained by (1) mixing between hydrothermal fluids and seawater, and/or (2) fractionation of hydrothermal fluids by subsurface losses of silica due to conductive cooling. Rayleigh-type fractionation of hydrothermal fluids was largely controlled by temperature differences between these fluids and seawater. Lamina-scale Si isotope heterogeneity within individual chemical chert samples up to 2.2‰ is considered to reflect the dynamic nature of hydrothermal activity. Silicified volcanogenic sediments lack diagnostic REE+Y anomalies, are enriched in lithophile elements, and exhibit a much more restricted range of positive δ³⁰Si (+0.1‰ to +1.1‰), which points to seawater as the dominant source of silica.The proposed model for Si isotope variability in the Early Archaean implies that chemical cherts with the most negative δ³⁰Si formed from pristine hydrothermal fluids, whereas silicified or chemical sediments with positive δ³⁰Si are closest to pure seawater deposits. Taking the most positive value found in this study (+1.3‰), and assuming that the Si isotope composition of seawater is governed by input of fractionated hydrothermal fluids, we infer that the temperature of ∼3.5 Ga seawater was below ∼55 °C.     

Deciphering formation processes of banded iron formations from the Transvaal and the Hamersley successions by combined Si and Fe isotope analysis using UV femtosecond laser ablation

To investigate the genesis of BIFs, we have determined the Fe and Si isotope composition of coexisting mineral phases in samples from the ∼2.5 billion year old Kuruman Iron Formation (Transvaal Supergroup, South Africa) and Dales Gorges Member of the Brockman Iron Formation (Hamersley Group, Australia) by UV femtosecond laser ablation coupled to a MC-ICP-MS. Chert yields a total range of δ³⁰Si between −1.3‰ and −0.8‰, but the Si isotope compositions are uniform in each core section examined. This uniformity suggests that Si precipitated from well-mixed seawater far removed from its sources such as hydrothermal vents or continental drainage. The Fe isotope composition of Fe-bearing mineral phases is much more heterogeneous compared to Si with δ⁵⁶Fe values of −2.2‰ to 0‰. This heterogeneity is likely due to variable degrees of partial Fe(II) oxidation in surface waters, precipitation of different mineral phases and post-depositional Fe redistribution. Magnetite exhibits negative δ⁵⁶Fe values, which can be attributed to a variety of diagenetic pathways: the light Fe isotope composition was inherited from the Fe(III) precursor, heavy Fe(II) was lost by abiotic reduction of the Fe(III) precursor or light Fe(II) was gained from external fluids. Micrometer-scale heterogeneities of δ⁵⁶Fe in Fe oxides are attributed to variable degrees of Fe(II) oxidation or to isotope exchange upon Fe(II) adsorption within the water column and to Fe redistribution during diagenesis. Diagenetic Fe(III) reduction caused by oxidation of organic matter and Fe redistribution is supported by the C isotope composition of a carbonate-rich sample containing primary siderite. These carbonates yield δ¹³C values of ∼−10‰, which hints at a mixed carbon source in the seawater of both organic and inorganic carbon. The ancient seawater composition is estimated to have a minimum range in δ⁵⁶Fe of −0.8‰ to 0‰, assuming that hematite and siderite have preserved their primary Fe isotope signature. The long-term near-zero Fe isotope composition of the Hamersley and Transvaal BIFs is in balance with the assumed composition of the Fe sources. The negative Fe isotope composition of the investigated BIF samples, however, indicates either a perturbation of the steady state, or they have to be balanced spatially by deposition of isotopically heavy Fe. In the case of Si, the negative Si isotope signature of these BIFs stands in marked contrast to the assumed source composition. The deviation from potential source composition requires a complementary sink of isotopically heavy Si in order to maintain steady state in the basin. Perturbing the steady state by extraordinary hydrothermal activity or continental weathering in contrast would have led to precipitation of light Si isotopes from seawater. Combining an explanation for both elements, a likely scenario is a steady state ocean basin with two sinks. When all published Fe isotope records including BIFs, microbial carbonates, shales and sedimentary pyrites, are considered, a complementary sink for heavy Fe isotopes must have existed in Precambrian ocean basins. This Fe sink could have been pelagic sediments, which however are not preserved. For Si, such a complementary sink for heavy Si isotopes might have been provided by other chert deposits within the basin.     

SIMS analyses of silicon and oxygen isotope ratios for quartz from Archean and Paleoproterozoic banded iron formations

Banded iron formations (BIFs) are chemical marine sediments dominantly composed of alternating iron-rich (oxide, carbonate, sulfide) and silicon-rich (chert, jasper) layers. Isotope ratios of iron, carbon, and sulfur in BIF iron-bearing minerals are biosignatures that reflect microbial cycling for these elements in BIFs. While much attention has focused on iron, banded iron formations are equally banded silica formations. Thus, silicon isotope ratios for quartz can provide insight on the sources and cycling of silicon in BIFs. BIFs are banded by definition, and microlaminae, or sub-mm banding, are characteristic of many BIFs. In situ microanalysis including secondary ion mass spectrometry is well-suited for analyzing such small features. In this study we used a CAMECA IMS-1280 ion microprobe to obtain highly accurate (±0.3‰) and spatially resolved (∼10 μm spot size) analyses of silicon and oxygen isotope ratios for quartz from several well known BIFs: Isua, southwest Greenland (∼3.8 Ga); Hamersley Group, Western Australia (∼2.5 Ga); Transvaal Group, South Africa (∼2.5 Ga); and Biwabik Iron Formation, Minnesota, USA (∼1.9 Ga). Values of δ¹⁸O range from +7.9‰ to +27.5‰ and include the highest reported δ¹⁸O values for BIF quartz. Values of δ³⁰Si have a range of ∼5‰ from −3.7‰ to +1.2‰ and extend to the lowest δ³⁰Si values for Precambrian cherts. Isua BIF samples are homogeneous in δ¹⁸O to ±0.3‰ at mm- to cm-scale, but are heterogeneous in δ³⁰Si up to 3‰, similar to the range in δ³⁰Si found in BIFs that have not experienced high temperature metamorphism (up to 300 °C). Values of δ³⁰Si for quartz are homogeneous to ±0.3‰ in individual sub-mm laminae, but vary by up to 3‰ between multiple laminae over mm-to-cm of vertical banding. The scale of exchange for Si in quartz in BIFs is thus limited to the size of microlaminae, or less than ∼1 mm. We interpret differences in δ³⁰Si between microlaminae as preserved from primary deposition. Silicon in BIF quartz is mostly of marine hydrothermal origin (δ³⁰Si < −0.5‰) but silicon from continental weathering (δ³⁰Si ∼ 1‰) was an important source as early as 3.8 Ga.     

Subsurface processes at the lucky strike hydrothermal field, Mid-Atlantic ridge: evidence from sulfur, selenium, and iron isotopes

At Lucky Strike near the Azores Triple Junction, the seafloor setting of the hydrothermal field in a caldera system with abundant low-permeability layers of cemented breccia, provides a unique opportunity to study the influence of subsurface geological conditions on the hydrothermal fluid evolution. Coupled analyses of S isotopes performed in conjunction with Se and Fe isotopes have been applied for the first time to the study of seafloor hydrothermal systems. These data provide a tool for resolving the different abiotic and potential biotic near-surface hydrothermal reactions. The δ³⁴S (between 1.5‰ and 4.6‰) and Se values (between 213 and 1640 ppm) of chalcopyrite suggest a high temperature end-member hydrothermal fluid with a dual source of sulfur: sulfur that was leached from basaltic rocks, and sulfur derived from the reduction of seawater sulfate. In contrast, pyrite and marcasite generally have lower δ³⁴S within the range of magmatic values (0 ± 1‰) and are characterized by low concentrations of Se (<50 ppm). For ⁸²Se/⁷⁶Se ratios, the δ⁸²Se values range from basaltic values of near −1.5‰ to −7‰. The large range and highly negative values of hydrothermal deposits observed cannot be explained by simple mixing between Se leached from igneous rock and Se derived from seawater. We interpret the Se isotope signature to be a result of leaching and mixing of a fractionated Se source located beneath hydrothermal chimneys in the hydrothermal fluid. At Lucky Strike we consider two sources for S and Se: (1) the “end-member” hydrothermal fluid with basaltic Se isotopic values (−1.5‰) and typical S isotope hydrothermal values of 1.5‰; (2) a fractionated source hosted in subsurface environment with negative δ³⁴S values, probably from bacterial reduction of seawater sulfate and negative δ⁸²Se values possibly derived from inorganic reduction of Se oxyanions. Fluid trapped in the subsurface environment is conductively cooled and has restricted mixing and provide favorable conditions for subsurface microbial activity which is potentially recorded by S isotopes. Fe isotope systematic reveals that Se-rich high temperature samples have δ⁵⁷Fe values close to basaltic values (∼0‰) whereas Se-depleted samples precipitated at medium to low temperature are systematically lighter (δ⁵⁷Fe values between −1 to −3‰). An important implication of our finding is that light Fe isotope composition down to −3.2‰ may be explained entirely by abiotic fractionation, in which a reservoir effect during sulfide precipitation was able to produce highly fractionated compositions.     

Conceptual model for early diagenetic chert and dolomite, Amuri Limestone Group, north-eastern South Island, New Zealand

The Late Cretaceous to Early Eocene, dominantly micritic, Amuri Limestone Group (ALG) was deposited in an approximately NW trending trough, in eastern Marlborough, New Zealand. The ALG comprises: the Mead Hill Formation; the Teredo, Lower and Middle Limestone formations; and the Upper and Lower Marl formations. Chert and dolomite are concentrated in the Mead Hill Formation, which contains five of six recognized diagenetic zones: Zone I at the base of the ALG consists almost entirely of chert; Zone II consists solely of chert and dolomite; Zone III comprises chert and limestone; Zone IV is composed of chert plus dolomite; Zone V is a chertified mudstone; and the minor amounts of chert found in the Middle Limestone Formation comprise Zone VI. With the exception of Zones IV and V, chert decreases stratigraphically upwards and away from the basin centre. All the dolomites are composed of <1 mm diameter rhombohedra in discontinuous beds and lenses. Generally Ca-rich, and non- to slightly ferroan, the dolomite contains approximately 500–900 ppm Mn and 200–400 ppm Sr. δ¹³C values average 1–2%_PDB with δ¹⁸O ratios of about -4%_PDB. Mass balance calculations indicate that the Mg²⁺ for dolomitization was derived from sea water. Sr, Fe and Mn concentrations are interpreted as indicating dolomite formation in the marine environment, with no influence from meteoric waters. The intimate association with pyrite implies dolomite formation in association with sulphate reduction, in the upper sediment column. δ¹⁸O data show that the bulk of the dolomite formed at temperatures below 50°C. All chert samples contain in excess of 90 wt% SiO₂, about 1 wt% Al₂O₃ and 1 wt% from losses on ignition. Generally all other major elements total less than 2 wt% oxide. δ¹⁸O values range from 26·8 to 29·0%_SMOW. Chert chemistry is consistent with the replacement of host carbonate and expulsion of carbonate-bound components from the site of chertification, and the effective dilution by SiO₂ of non-carbonate-bound insoluble residues. δ¹⁸O data indicate that chert formed in fluids of similar composition and temperature as the dolomite. The abundance of disseminated pyrite in cherts implies an association with sulphate reduction. Silica for chertification is thought to have initially come from dissolution of siliceous organisms. However, there is insufficient biogenic silica available to form the volumes of chert observed. It is suggested that the bulk of the silica came from SiO₂-rich pore waters generated by clay mineral reactions in the thick underlying mudstones. The ALG compacted down through these pore waters. Chert and dolomite nucleation are considered to have been penecontemporaneous. Dolomitization was initially probably the faster process, continuing as long as sulphate reduction prevailed and there was an adequate supply of Mg²⁺. The nucleation of chert, although initially slower (probably due to a relatively lower initial SiO₂ supply), continued after cessation of dolomitization to the extent of completely chertifying the dolomite intercrystalline matrix. The amount of chertification decreased progressively as SiO₂ supplies diminished, both stratigraphically upwards and away from the basin centre.     

Carbon isotopes and petrography of kerogens in ∼3.5-Ga hydrothermal silica dikes in the North Pole area, Western Australia

More than 600 specimens of ∼3.5 Ga-old hydrothermal silica dikes from the North Pole area, Pilbara craton, Western Australia, have been studied petrographically. The kerogens in 44 samples have been analyzed isotopically (C and N) and chemically (C, N, and H). The silica dikes are composed mainly of fine-grained silica (modal abundance: >97%) and are classified into two types by minor mineral assemblages: B(black)-type and G(gray)-type. The B-type silica dikes contain kerogen (0.37 to 6.72 mgC/g; average 2.44 mgC/g, n = 21) and disseminated sulfides, dominantly pyrite and Fe-poor sphalerite. In some cases, carbonate and apatite are also present. Their silica-dominated and sulfide-poor mineral assemblages suggest precipitation from low-temperature reducing hydrothermal fluid (likely 100-200°C). On the other hand, the G-type silica dikes are sulfide-free and concentrations of kerogen are relatively low (0.05 to 0.41 mgC/g; average 0.17 mgC/g, n = 13). They typically contain Fe-oxide (mainly hematite) which commonly replaces cubic pyrite and rhombic carbonate. Some G-types occur along secondary quartz veins. These textures indicate that the G-type silica dikes were formed by postdepositional metasomatism (oxidation) of the B-types, and that the B-types probably possess premetasomatic signatures. The δ¹³C values of kerogen in the B-types are −38.1 to −33.1‰ (average −35.9‰, n = 21), which are ∼4‰ lower than those of the G-types (−34.5 to −30.0‰; average −32.2‰, n = 19), and ∼6‰ lower than bedded chert (−31.2 to −29.4‰; average −30.5‰, n = 4). This indicates the preferential loss of ¹²C during the metasomatism (estimated fractionation factor: 0.9985). Considering the metasomatic effect on carbon isotopes with probably minor diagenetic and metamorphic overprints, we conclude that the original δ¹³C values of the kerogen in the silica dikes would have been heterogeneous (∼5‰) and at least some material had initial δ¹³C values of ≤ −38‰. The inferred ¹³C-depletions of organic carbon could have been produced by anaerobic chemoautotrophs such as methanogen, but not by aerobic photoautotrophs. This is consistent with the estimated physical and chemical condition of the hydrothermal fluid, which was probably habitable for anaerobic and thermophilic/hyperthermophilic chemoautotrophs. Alternatively, the organic matter may have been possibly produced by abiological reaction such as Fischer-Tropsch Type (FTT) synthesis under the hydrothermal condition. However, the estimated condition is inconsistent with the presence of the effective catalysts for the FTT reaction (i.e., Fe-Ni alloy, magnetite, and hematite). These lines of evidence suggest the possible existence of biosphere in the ∼3.5 Ga sub-seafloor hydrothermal system.     

The oxygen-isotope composition of chondrules and isolated forsterite and olivine grains from the Tagish Lake carbonaceous chondrite

The oxygen-isotope compositions (obtained by laser fluorination) of hand-picked separates of isolated forsterite, isolated olivine and chondrules from the Tagish Lake carbonaceous chondrite describe a line (δ¹⁷O = 0.95 * δ¹⁸O − 3.24; R² = 0.99) similar to the trend known for chondrules from other carbonaceous chondrites. The isolated forsterite grains (Fo_99.6-99.8; δ¹⁸O = −7.2‰ to −5.5‰; δ¹⁷O = −9.6‰ to −8.2‰) are more ¹⁶O-rich than the isolated olivine grains (Fo_39.6-86.8; δ¹⁸O = 3.1‰ to 5.1‰; δ¹⁷O = −0.3‰ to 2.2‰), and have chemical and isotopic characteristics typical of refractory forsterite. Chondrules contain olivine (Fo_97.2-99.8) with oxygen-isotope compositions (δ¹⁸O = −5.2‰ to 5.9‰; δ¹⁷O = −8.1‰ to 1.2‰) that overlap those of isolated forsterite and isolated olivine. An inverse relationship exists between the Δ¹⁷O values and Fo contents of Tagish Lake isolated forsterite and chondrules; the chondrules likely underwent greater exchange with ¹⁶O-poor nebular gases than the forsterite. The oxygen-isotope compositions of the isolated olivine grains describe a trend with a steeper slope (1.1 ± 0.1, R² = 0.94) than the carbonaceous chondrite anhydrous mineral line (CCAM_slope = 0.95). The isolated olivine may have crystallized from an evolving melt that exchanged with ¹⁶O-poor gases of somewhat different composition than those which affected the chondrules and isolated forsterite. The primordial components of the Tagish Lake meteorite formed under conditions similar to other carbonaceous chondrite meteorite groups, especially CMs. Its alteration history has its closest affinities to CI carbonaceous chondrites.     

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.     

Oxygen isotopic variability associated with multiple stages of serpentinization, Duke Island Complex, southeastern Alaska

Ultramafic rocks of the Duke Island Complex in southeastern Alaska crystallized in a supra-subduction zone setting, but the serpentinization of olivine-bearing rocks involved the incursion of late-stage meteoric waters. Three textural types of serpentine (primarily lizardite) have been identified which in part reflect progress in reactions during multiple stages of fluid infiltration. The overall mesh texture of serpentine has been subdivided into a massive-type, found in dunites and wehrlites, and a dendritic-type found in wehrlites and olivine clinopyroxenites. Serpentine veins represent a late-stage in the hydrothermal alteration process. Both FeO contents and δ¹⁸O values of the three textural types of serpentine are variable at the centimeter scale. Magnetite abundance in association with serpentine is also variable with up to 5 vol% of magnetite found in samples with dendritic serpentine. Continued reaction of FeO-bearing serpentine with fluid appears to control the formation of most magnetite. Oxygen isotope ratios of the three textural types of serpentine are distinct, with the massive variety characterized by δ¹⁸O values between −3‰ and 3‰, the dendritic variety showing values between 2‰ and 6‰ and the veins having the highest values between 4‰ and 10‰. Although the δ¹⁸O values may vary by as much as 5‰ on the centimeter scale, δD values tend to show relatively less variation with over 90% of the measured values between −100‰ and −120‰. The O and H isotopic values are consistent with the involvement of meteoric water that had undergone variable degrees of isotopic exchange with country rocks prior to reacting with olivine in the Duke Island Complex. Small-scale variability in both serpentine FeO content and δ¹⁸O values suggests that chemical and isotopic equilibria may have not been attained at larger than centimeter scales. Oxygen isotopic variability in serpentine produced during relatively low-temperature hydrothermal alteration is in large part a function of exchange mediated via fluid flow through microfractures.     

Volcanic degassing,hydrothermal circulation and the flourishing of early life on Earth: A review of the evidence from c. 3490-3240 Ma rocks of the Pilbara Supergroup,Pilbara Craton,Western Australia

New data gathered during mapping of c. 3490–3240 Ma rocks of the Pilbara Supergroup in the Pilbara Craton show that most bedded chert units originated as epiclastic and evaporative sedimentary rocks that were silicified by repeated pulses of hydrothermal fluids that circulated through the footwall basalts during hiatuses in volcanism. For most cherts, fossil hydrothermal fluid pathways are preserved as silica ± barite ± Fe-bearing veins that cut through the footwall and up to the level of individual bedded chert units, but not above, indicating the contemporaneity of hydrothermal silica veining and bedded chert deposition at the end of volcanic eruptive events. Silica ± barite ± Fe-bearing vein swarms are accompanied by extensive hydrothermal alteration of the footwall to the bedded chert units, and occurred under alternating high-sulphidation and low-sulphidation conditions. These veins provided pathways to the surface for elements leached from the footwall (e.g., Si, Ba, Fe) and volcanogenic emissions from underlying felsic magma chambers (e.g., CO₂, H₂S/HS⁻, SO₂).Stratigraphic evidence of shallowing upward and subsequent deepening associated with the deposition of Warrawoona Group cherts is interpreted to relate to the emplacement of subvolcanic laccoliths and subsequent eruption and/or degassing of these magmas. Heat from these intrusions drove episodes of hydrothermal circulation. Listric normal faulting during caldera collapse produced basins with restricted circulation of seawater. Eruption of volcanogenic emissions into these restricted basins formed brine pools with concentration of the volcanogenic components, thereby providing habitats suitable for early life forms.Fossil stromatolites from two distinct stratigraphic units in the North Pole Dome grew in shallow water conditions, but in two very different geological settings with different morphologies. Stratiform and domical stromatolites in the stratigraphically lower, c. 3490 Ma, Dresser Formation of the Warrawoona Group are intimately associated with barite and chert precipitates from hydrothermal vents, suggesting that component microbes may have been chemoautotrophic hyperthermophiles. Evidence of shallow water to periodically exposed conditions, active growth faulting and soft sediment deformation indicates that the volcanogenic emissions were erupted into a shallow water, tectonically active caldera and concentrated therein to produce an extreme habitat for early life.Widespread conical and pseudocolumnar stromatolites in the c. 3400 Ma, Strelley Pool Chert at the base of the unconformably overlying Kelly Group occur in shallow marine platform carbonates. Silicification was the result of later hydrothermal circulation driven by heat from the overlying, newly erupted Euro Basalt. The markedly different morphology and geological setting of these only slightly younger stromatolites, compared with the Dresser Formation, suggests a diversity of microbial life on early Earth.The biogenicity of putative microfossils from this and younger hydrothermal silica veins in the Warrawoona Group remains controversial and requires further detailed study.     

华南热水沉积硅质岩建造及其成矿效应

华南地区热水沉积建造发育。文中介绍该地区热水沉积建造 ,特别是震旦系顶部、泥盆系榴江组和二叠系当冲组 3个重要层位的硅质岩建造 ,分析它们的地质地球化学特征。研究表明 ,华南三层位沉积硅质岩的共同特征是TiO2 、Al2 O3 和K2 O含量一致偏低 ,大部分微量元素含量偏低 (与地壳克拉克值相比 ) ,但Ba、As、Sb富集 ,具有较为典型的热水沉积成因特点。多元统计分析显示 ,大部分微量元素在第一个主因子上均有显著因子载荷 ,与它们在基底的富集或亏损无关 ,代表了古地热系热水循环中的淋滤因子。华南三层位热水成因硅质岩具有相似的REE地球化学特征。REE总量低 ,稀土配分模式落在典型热水沉积物的上、下限之间 ,多数样品呈现δCe和δEu负异常。正常沉积的混入使部分硅质岩的REE配分模式复杂化。最后 ,讨论了与热水沉积建造相关的成矿效应 ,为金属矿床成因和评价提供约束条件     

40Ar39Ar studies of Precambrian cherts; an unsuccessful attempt to measure the time evolution of the atmospheric 40Ar/36Ar ratio

KAr isochron techniques can provide, in principle, an experimental reconstruction of the time evolution of the atmospheric ⁴⁰Ar/³⁶Ar ratio if minerals can be found which contain samples of argon from the ancient atmosphere and which have had a simple geologic history. Authigenic sedimentary minerals with low potassium content appear to be the best candidates. An experimental reconstruction of the evolution of the atmospheric ⁴⁰Ar/³⁶Ar ratio will serve as a test of various models for the chemical and thermal evolution of the Earth.⁴⁰Ar³⁹Ar studies of five chert samples from the Swaziland sequence and the Bulawayan and Gunflint Formations indicate that lower Precambrian cherts do not contain appreciable samples of the ancient atmospheric argon and have experienced complicated geologic histories. The chert sample from the Kromberg Formation contains excess ⁴⁰Ar. The other four samples yield age spectra which are complicated but which are interpretable in terms of geologically reasonable ages.The lack of evidence for argon loss in the chert data suggests that some cherts may prove to be datable sedimentary minerals.     

Archaeal lipids in Neogene dolomites (Monterey and Sisquoc Formations, California) - Planktic versus benthic archaeal sources

The distribution of archaeal lipids, including archaeol and glycerol dibiphytanyl glycerol tetraethers (GDGTs), in dolomite concretions and surrounding sediment from the Monterey Formation (Miocene) and the Sisquoc Formation (Miocene-Pliocene) were examined to distinguish planktic from benthic contributions. For this purpose, dolomites with positive δ¹³C values (+7‰ to +13‰) were chosen; such highly positive values point to pronounced methanogenesis of benthic archaea in the sedimentary column. At first glance, distributions and relative abundances of GDGTs in both dolomites and background sediment were similar, resembling patterns of marine planktic crenarchaea. A contribution of benthic euryarchaea to the GDGT pool became evident only from variations in the δ¹³C values of different biphytanes obtained after ether cleavage of GDGTs. Whereas bi- and tricyclic biphytanes had an isotopic signal typical of planktic archaea (δ¹³C −23.6‰ to −20.5‰ and −23.4‰ to −21.2‰, respectively) for both dolomite and background sediment, acyclic and monocyclic biphytanes showed lower values for dolomite samples (−25.1‰ to −22.6‰ and −27.6‰ to −24.7‰, respectively), indicating a contribution of lipids from benthic archaea. The isoprenoid diether archaeol (δ¹³C −23.9‰ to −22.9‰), assigned to euryarchaea, was only detected in dolomite samples, also reflecting additional input from sedimentary archaea, probably autotrophic methanogens. The occurrence of lipids derived from methanogenic archaea agrees with the strong ¹³C-enrichment of dolomites and with mineral formation taking place in the zone of archaeal methanogenesis. This implies that the lipid biomarker inventory of sedimentary strata needs to be interpreted carefully, as it is often not straightforward to discriminate between input from the water column and sedimentary microbial activity.     

信江盆地石炭纪硅质岩地球化学特征及沉积环境意义

在信江盆地中存在数层和石炭纪海相火山岩及其海底块状硫化物矿层相伴生,与石炭纪地层整合产出的层状硅质岩。由对硅质岩常量元素、微量元素、稀土元素、硅和氧同位素等地球化学特征研究表明,本区硅质岩具有一定的热水沉积硅质岩地球化学特征。在Al-Fe-Mn和Fe-Mn-(Ni+Co+Cu)三角图上,本区硅质岩属热水沉积硅质岩。由硅质岩MnO/TiO₂比值、δCe值和δ³⁰Si值分析表明,信江盆地石炭纪硅质岩的沉积环境主要为浅海。     

Extreme oxygen isotope signature of meteoric water in magmatic zircon from metagranite in the Sulu orogen, China: Implications for Neoproterozoic rift magmatism

Unusual ¹⁸O depletion, with δ¹⁸O values as negative as −10‰ to −4‰ relative to VSMOW, was reported in zircons from ultrahigh-pressure eclogite-facies metamorphic rocks in the Dabie-Sulu orogenic belt, China. But it is critical for the negative δ¹⁸O zircons to be distinguished between magmatic and metamorphic origins, because the ¹⁸O depletion can be acquired by high-T eclogite-facies metamorphism of meteoric-hydrothermally altered low δ¹⁸O rocks. While zircon O diffusion kinetics has placed a reasonable constraint on this, zircon trace element compositions can provide a straightforward distinction between the magmatic and metamorphic origins. This paper reports our finding of unusual ¹⁸O depletion in zircon from granitic gneiss in the northeastern end of the Sulu orogen. Zircon δ¹⁸O values vary from −7.8‰ to −3.1‰ along a profile of 50 m length at Zaobuzhen. They are close to extremely low δ¹⁸O values of −9.0‰ to −5.9‰ for metagranite at Qinglongshan and adjacent areas in the southwestern end of the Sulu orogen. CL imaging suggests that the low δ¹⁸O zircons at Zaobuzhen are primarily of magmatic origin, but underwent different degrees of metamorphic modification. Zircon U-Pb dating yields middle Neoproterozoic ages of 751 ± 27 to 779 ± 25 Ma for protolith crystallization and Triassic ages of 214 ± 10 to 241 ± 33 Ma for metamorphic resetting. However, no metamorphic modification occurs in zircon REE patterns that only indicate magmatic recrystallization and hydrothermal alteration, respectively. Thus, the negative δ¹⁸O zircons are interpreted as crystallizing from negative δ¹⁸O magmas due to melting of meteoric-hydrothermally altered negative δ¹⁸O rocks in an active rift setting at about 780 Ma. The variation in zircon δ¹⁸O values indicates considerable O isotope heterogeneity in its granitic protolith. Zircon Lu-Hf isotope analyses give positive ε_Hf(t) values of 1.6-4.1 and Hf model ages of 1.18-1.30 Ga. This suggests that the granitic protolith was derived from the mid-Neoproterozoic reworking of late Mesoproterozoic juvenile crust. The metagranites at Zaobuzhen and Qinglongshan, about 450 km apart, are two known occurrences of the unusually low δ¹⁸O zircons below −6‰ so far reported in the Sulu orogen. They are similar to each other in both protolith and metamorphic ages, so that they share the same nature of both Neoproterozoic protolith and Triassic metamorphism. Therefore, the locally negative δ¹⁸O zircons may register centers of low δ¹⁸O magmatism during the supercontinental rifting.     

Oxygen isotopic and chemical compositions of cosmic spherules collected from the Antarctic ice sheet: Implications for their precursor materials

Bulk chemical compositions and oxygen isotopic compositions were analyzed for 48 stony cosmic spherules (melted micrometeorites) collected from the Antarctic ice sheet using electron- and ion-microprobes. No clear correlation was found between their isotopic compositions and textures. The oxygen isotopic compositions showed an extremely wide range from −28‰ to +93‰ in δ¹⁸O and from −21‰ to +13‰ in Δ¹⁷O. In δ¹⁸O-δ¹⁷O space, most samples (38 out of 48) plot close to the terrestrial fractionation line, but 7 samples plot along the carbonaceous chondrite anhydrous mineral (CCAM) line. Three samples plot well above the terrestrial fractionation line. One of these has a Δ¹⁷O of +13‰, the largest value ever found in solar system materials. One possible precursor for this spherule could be ¹⁶O-poor planetary material that is still unknown as a meteorite. The majority of the remaining spherules are thought to be related to carbonaceous chondrites.     

Insights into C and H storage in the altered oceanic crust: Results from ODP/IODP Hole 1256D

Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with δD values from −64‰ to −25‰. All samples are enriched in water relative to fresh basalts. The δD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO₂, extracted by step-heating technique, ranges between 564 and 2823 ppm with δ¹³C values from −14.9‰ to −26.6‰. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with δ¹³C = −4.5‰ and (2) an organic compound with δ¹³C = −26.6‰. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO₂ yield after H₃PO₄ attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO₂ degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO₂ is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when “fresh” oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO₂, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ∼ −4.7‰, similar to the δ¹³C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 × 10¹² molC/yr.