Studies on bedded cherts

Radiolarian cherts from two localities in North-western Italy have been studied by optical and scanning electron microscopy, X-ray diffraction and X-ray fluorescence analysis. The quality of preservation of the radiolarians decreased from dark red to pale cherts. The effect of diagenetic processes (solution, reprecipitation and recrystallization) was least in red cherts where contained hematitic and clay material inhibited the movement of pore solutions, and greatest in the pale cherts resulting in the destruction of the original skeletal material. It is suggested that these radiolarian cherts were produced from an accumulation of siliceous radiolarian skeletons subsequently altered diagenetically with consequent loss of skeletal structure.     

The implication of the oxygen isotope records in coexisting cherts and phosphates

δ¹⁸O values have been determined for 53 coexisting chert-phosphate pairs from the Phanerozoic and Precambrian. In addition, δ¹⁸O values were also determined for 18 biogenic phosphates from the Phanerozoic.The oxygen isotope data for the chert-phosphate pairs permit the calculation of the temperatures of formation of the chert-phosphate pairs as well as the δ¹⁸O of the waters in which they equilibrated. In turn the calculated δ¹⁸O of the waters permit the calculation of temperatures from the isotopic data of the biogenic phosphates. The temperatures for the Tertiary and Mesozoic samples are compatible with the literature values determined from oxygen isotope data for well-preserved calcareous marine skeletal remains. The temperatures calculated from the chert-phosphate pairs of the Paleozoic are usually higher and vary in cycles of about a 150 million year period. The early Precambrian temperatures are as high as 80°C and decrease with time. The use of chert-phosphate pairs for temperature determinations are sufficiently promising to warrant further investigations of this type on well preserved chert-phosphate or carbonate-phosphate pairs.     

K-feldspar rich shales from Jurassic bedded cherts in southeastern Slovenia

The study area in southeastern Slovenia is part of the transitional zone between the internal and the external Dinarides. Within Jurassic bedded cherts there are up to 2 cm thick shale intercalations, consisting of laminated, soft, fine-grained, green to brown material whose origin has been in question. In the majority of Tethyan cherts, the interbedded material is reported to be volcanogenic and/or terrigenous, although a detailed mineralogical analysis of the material is lacking. An XRD analysis confirmed the presence of quartz, illite, chlorite and K-feldspar, which is the prevailing component in some samples. Major and trace element data exclude both a volcanogenic and an hydrothermal origin. Several discrimination diagrams indicate the upper crustal terrigenous nature of shales and a biogenic silica source. The source material was probably from a Variscan crust, which at the time of deposition had already been weathered to kaolinite, and some sporadic muscovite. The MnO/Al₂O₃ ratio suggests a slow sedimentation rate of cherts and a faster one for shales, which probably settled from distal turbidity currents. The negative Ce anomaly indicates prolonged contact with ocean water. Sediments were deposited on a Tethyan passive margin, originally as silica-rich carbonate beds intercalated with mud. During late diagenesis, the mixing of marine and meteoric waters caused the further silicification of limestone and simultaneous potassium enrichment of shale which led to their alteration into illite or chlorite and, in sediments already rich in K-minerals, into K-feldspar.     

Inorganic bedded cherts from the Magadi area,Kenya

The High Magadi beds can be divided into a lower and an upper sequence, separated by a bed rich in Tilapia nilotica remains. The lower sequence contains one or more magadiite horizons. Through digging of trenches it has been possible to establish that the cherts of the Chert Series are stratigraphically equivalent to the magadiite horizons. The transition magadiite-chert has been observed in many places and may occur over a distance of less than 50 cm. It is accomplished by removal of sodium by percolating waters. The resulting bedded chert may preserve the fine lamination present in magadiite. The conversion is accompanied by many textural and structural features such as large desiccation polygons, buckling, reticulation, extrusion, casts of mud-cracks and calcite.The precipitation of magadiite is postulated to have taken place in annual increments in a stratified lake at the brine-epilimnion interface. The maximum duration is estimated at 4,000–6,000 years. Solubility measurements indicate that most Magadi waters at the present time are supersaturated with respect to magadiite and kenyaite, though no precipitation has been observed. The presence of chert chips in intraformational gravels indicates that the conversion to chert was already initiated during the magadiite precipitation interval.The inorganic mechanism for the formation of bedded chert observed at Magadi is suggested to apply also to the Dales Gorge Member of the Precambrian Brockman Iron Formation of W. Australia. Evidence for magadiite as chert precursor is found in the depositional rates, the presence of riebeckite and in textures such as macules and cross-pods. The proposed model is extended to include Precambrian banded iron formations in general and the restriction of these formations to the early history of the earth is explained by the likely compositions of waters from closed basins.     

Carbon and oxygen isotope ratios in diagenetic carbonates from marine sediments

The isotopic composition of some sixty samples of penecontemporaneous diagenetic carbonates from marine horizons shows that they are strikingly different from normal marine limestones. The variation of C¹³ ratio is 5·6 per cent, the lightest carbonate measuring -54%. A mechanism for the formation of such light carbon dioxide is postulated, involving the enzymic decarboxylation of organic compounds at low temperatures. A study of the oxygen isotopic composition of coexisting calcite and rhodochrosite indicates that, whereas the latter has retained its isotopic composition from the time of precipitation, the calcite has undergone equilibration during diagenesis. Isotopic measurements on such diagenetic carbonates would confuse palaeoenvironmental studies but may throw light on the processes of diagenesis.     

Stable isotope geochemistry of deep sea cherts

Seventy four samples of DSDP recovered cherts of Jurassic to Miocene age from varying locations, and 27 samples of on-land exposed cherts were analyzed for the isotopic composition of their oxygen and hydrogen. These studies were accompanied by mineralogical analyses and some isotopic analyses of the coexisting carbonates. δ¹⁸O of chert ranges between 27 and 39%. relative to SMOW, δ¹⁸O of porcellanite—between 30 and 42%.. The consistent enrichment of opal-CT in porcellanites in ¹⁸O with respect to coexisting microcrystalline quartz in chert is probably a reflection of a different temperature (depth) of diagenesis of the two phases.δ¹⁸O of deep sea cherts generally decrease with increasing age, indicating an overall cpoling of the ocean bottom during the last 150 m.y. A comparison of this trend with that recorded by benthonic foraminifera (Douglas and Savin, 1975) indicates the possibility of δ¹⁸O in deep sea cherts not being frozen in until several tens of millions of years after deposition. Cherts of any Age show a spread of δ¹⁸O values, increasing diagenesis being reflected in a lowering of δ¹⁸O. Drusy quartz has the lowest δ¹⁸O values.On-land exposed cherts are consistently depleted in ¹⁸O in comparison to their deep sea time equivalent cherts.Water extracted from deep sea cherts ranges between 0.5 and 1.4 wt %. δD of this water ranges between ?78 and ?95%. and is not a function of δ¹⁸O of the cherts (or the temperature of their formation).     

Variations in carbon and oxygen isotope ratios as a possible guide to ore

Contour maps showing variations in carbon and oxygen isotope ratios may be useful as a guide to ore. Previous literature suggests that the isotopic composition of carbon is related to the environment in which it is deposited. Sedimentary syngenetic ore deposits are also related to the depositional environment in which they occur and should therefore be related to the isotopic composition of the carbon deposited along with the ore. Although metamorphism may obscure palaeontological and stratigraphic indicators of environment, the isotopic composition of organic carbon appears to be unaffected by it. Previous literature suggests that variations in oxygen isotopes can be used also as a guide to certain epigenetic ore deposits.

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Zusammenfassung Isotopenverteilungskarten sind nützliche Hilfsmittel bei der Erzprospektion. In der Literature wird auf die Abhängigkeit der Isotopen-Zusammensetzung vom Ablagerungsmilieu aufmerksam gemacht. Sedimentäre syngenetische Erzlagerstätten sind ohne Zweifel vom Ablagerungsmilieu abhängig. Es liegt deshalb nahe, die Isotopen-Zusammensetzung des darin enthaltenen Kohlenstoffs mit derjenigen der erzbildenden chemischen Elemente zu vergleichen. Obwohl metamorphe Prozesse paläontologische und stratigraphische Prozesse verwischen können, scheint die Isotopen-Zusammensetzung davon unbeeinflußt zu bleiben. Als Hilfsmittel können weiterhin die in der Literatur beschriebenen Isotopenverhältnisse des Sauerstoffs herangezogen werden.

     

Hydrogen and oxygen isotope fractionation during crystallization of mirabilite and ice

The equilibrium fractionation factors between mirabilite (Na₂SO₄·10H₂O) and saturated sodium sulphate solution at 25°C and 0°C and between ice and 2·5 molal sodium chloride solution at ?10°C have been measured. For mirabilite, the deuterium factors are 1·017 and 1·019, and the oxygen-18 factors are 1·0014 and 1·0020 at 25°C and 0°C, respectively. For ice, the factors are 1·024 for deuterium and 1·0022 for oxygen-18 at ?10°C. These fractionation factors are used to estimate the fractionation factors between ice and mirabilite and concentrated sea water at ?10°C. It is concluded that the average binding strengths of hydrogen in ice and mirabilite are very similar.     

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100–350° for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100°. Exchange rates were 3–5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure.Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O¹⁸ exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O¹⁸ exchange.At 350° kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O¹⁸ exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor.     

Hydrogen isotope ratios of recent lacustrine sedimentary n-alkanes record modern climate variability

Hydrogen isotope ratios were measured on n-alkanes (n-C₁₂ to n-C₃₁) extracted from recent lake surface sediments along a N-S European transect to test if modern climate variability is recorded in these biomarkers. δD values of the n-alkanes are compared to δD values of meteoric water from the IAEA-GNIP database spanning a range from −119‰ in northern Sweden to −41‰ in southern Italy, to lake water δD values, and to mean annual temperatures, varying between −2.0°C in the north and 13.7°C in the south.δD values of the short-chained n-alkanes n-C₁₂ to n-C₂₀, excluding algal derived n-C₁₇ and n-C₁₉, are higher in the north and lower in the south. The isotopic fractionation ε for hydrogen between meteoric water and the short-chained n-alkanes is increasing from N to S by more than 100‰ and is significantly correlated to mean annual temperature for n-C₁₆ and n-C₁₈. This suggests that these n-alkanes may originate from a different source in the northern lakes, possibly due to petroleum contamination, or are synthesized using a different biochemical pathway.The n-C₁₇ and n-C₁₉ alkanes of algal origin, the n-C₂₁ and n-C₂₃ alkanes originating from water plants, and the long-chain n-alkanes n-C₂₅, n-C₂₇, n-C₂₉, and n-C₃₁ of terrestrial origin, clearly correlate with δD values of meteoric water, lake water, and mean annual temperature, indicating that they excellently record the δD value of meteoric water. The mean hydrogen isotope fractionation ε_C17/w of −157‰ (SD = 13) between n-C₁₇ and meteoric water is fairly constant over the wide range of different climates and lake environments, suggesting only minor influence of environmental factors on this biochemical fractionation. This suggests that δD values of n-C₁₇ are suitable to reconstruct the isotopic composition of source water. The mean fractionation between the long-chain n-alkanes and water is −128‰ (SD = 12). The mean difference of 31‰ between both ε values is likely due to evaporative enrichment of deuterium in the leaf water. If this is the only influence on the enrichment, the difference between the δD values of terrestrial and aquatic compounds might be suitable to reconstruct terrestrial evapotranspiration of the lake environment.     

Zonal distribution of oxygen isotope ratios in the Hiroshima granite complex,Southwest Japan

¹⁸O/¹⁶O ratios have been obtained for 99 minerals from rocks of the Hiroshima granite complex and adjacent Ryoke granites. Zonal distribution of oxygen isotopes is observed on a regional scale almost parallel to the extension of the Ryoke plutono-metamorphic belt, granites in or around the metamorphic belt being 2–3%₀ richer in ¹⁸O than those farther away from the belt. Isotopic fractionations among coexisting minerals indicate that isotopic zonation existed at a magmatic stage. The zonal enrichment of ¹⁸O in the granite magma in the Ryoke belt and its periphery is a result of isotopic interaction between country rocks and the magma through fluid media. Genetic relationship between granites of the Ryoke and Chugoku belts are discussed with regard to the geological situation of the former belt.     

Hydrogen isotope ratios of leaf wax n-alkanes in grasses are insensitive to transpiration

We analyzed hydrogen isotope ratios of high-molecular weight n-alkanes (δD_l) and oxygen isotope ratios of α-cellulose (δ¹⁸O_C) for C₃ and C₄ grasses grown in the field and in controlled-environment growth chambers. The relatively firm understanding of ¹⁸O-enrichment in leaf water and α-cellulose was used to elucidate fractionation patterns of δD_l signatures. In the different relative humidity environments of the growth chambers, we observed clear and predictable effects of leaf-water enrichment on δ¹⁸O_C values. Using a Craig-Gordon model, we demonstrate that leaf water in the growth chamber grasses should have experienced significant D-enriched due to transpiration. Nonetheless, we found no effect of transpirational D-enrichment on the δD_l values. In field samples, we saw clear evidence of enrichment (correlating with relative humidity of the field sites) in both δ¹⁸O_C and δD_l. These seemingly contrasting results could be explained if leaf waxes are synthesized in an environment that is isotopically similar to water entering plant roots due to either temporal or spatial isolation from evaporatively enriched leaf waters. For grasses in the controlled environment, there was no enrichment of source water, whereas enrichment of grass source water via evaporation from soils and/or stems was likely for grass samples grown in the field.Based on these results, evaporation from soils and/or stems appears to affect δD_l, but transpiration from leaves does not. Further evidence for this conclusion is found in modeling expected net evapotranspirational enrichment. A Craig-Gordon model applied to each of the field sites yields leaf water oxygen isotope ratios that can be used to accurately predict the observed δ¹⁸O_C values. In contrast, the calculated leaf water hydrogen isotope ratios are more enriched than what is required to predict observed δD_l values. These calculations lend support to the conclusion that while δ¹⁸O_C reflects both soil evaporation and transpiration, δD_l appears to only record evaporation from soils and/or stems. Therefore, the δD of n-alkanes can likely be used to reconstruct the δD of water entering a leaf, supporting the soil-enrichment model of Smith and Freeman (2006). In both the field and controlled studies, we found significant photosynthetic pathway effects on n-alkane δD suggesting that biochemical pathways or plant phylogeny have a greater effect on leaf wax δD than leaf-water enrichment in grasses.     

4.4 billion years of crustal maturation: oxygen isotope ratios of magmatic zircon

Analysis of δ¹⁸O in igneous zircons of known age traces the evolution of intracrustal recycling and crust-mantle interaction through time. This record is especially sensitive because oxygen isotope ratios of igneous rocks are strongly affected by incorporation of supracrustal materials into melts, which commonly have δ¹⁸O values higher than in primitive mantle magmas. This study summarizes data for δ¹⁸O in zircons that have been analyzed from 1,200 dated rocks ranging over 96% of the age of Earth. Uniformly primitive to mildly evolved magmatic δ¹⁸O values are found from the first half of Earth history, but much more varied values are seen for younger magmas. The similarity of values throughout the Archean, and comparison to the composition of the “modern” mantle indicate that δ¹⁸O of primitive mantle melts have remained constant (±0.2‰) for the past 4.4 billion years. The range and variability of δ¹⁸O in all Archean zircon samples is subdued (δ¹⁸O(Zrc)=5–7.5‰) ranging from values in high temperature equilibrium with the mantle (5.3± 0.3‰) to slightly higher, more evolved compositions (6.5–7.5‰) including samples from: the Jack Hills (4.4–3.3 Ga), the Beartooth Mountains (4.0–2.9 Ga), Barberton (3.5–2.7 Ga), the Superior and Slave Provinces (3.0 to 2.7 Ga), and the Lewisian (2.7 Ga). No zircons from the Archean have been analyzed with magmatic δ¹⁸O above 7.5‰. The mildly evolved, higher Archean values (6.5–7.5‰) are interpreted to result from exchange of protoliths with surface waters at low temperature followed by melting or contamination to create mildly elevated magmas that host the zircons. During the Proterozoic, the range of δ¹⁸O(Zrc) and the highest values gradually increased in a secular change that documents maturation of the crust. After ∼1.5 Ga, high δ¹⁸O zircons (8 to >10‰) became common in many Proterozoic and Phanerozoic terranes reflecting δ¹⁸O(whole rock) values from 9 to over 12‰. The appearance of high δ¹⁸O magmas on Earth reflects nonuniformitarian changes in the composition of sediments, and rate and style of recycling of surface-derived material into magmas within the crust. Electronic Supplementary Material Supplementary material is available for this article at     

Microscale oxygen isotope variations in 1.9 Ga Gunflint cherts: Assessments of diagenesis effects and implications for oceanic paleotemperature reconstructions

Variations in the oxygen isotope composition (δ¹⁸O) of five cherts from the 1.9 Ga Gunflint iron formation (Canada) were studied at the micrometer scale by ion microprobe to try to better understand the processes that control δ¹⁸O values in cherts and to improve seawater paleotemperature reconstructions. Gunflint cherts show clearly different δ¹⁸O values for different types of silica with for instance a difference of ≈15‰ between detrital quartz and microquartz. Microquartz in the five samples is characterized by large intra sample variations in δ¹⁸O values, (δ¹⁸O of quartz varies from 4.6‰ to 6.6‰ at the 20 μm scale and from ≈12‰ to 14‰ at 2 μm scale). Isotopic profiles in microquartz adjacent to hydrothermal quartz veins demonstrate that microquartz more than ≈200 μm away from the veins has preserved its original δ¹⁸O value.At the micrometer spatial resolution of the ion probe, data reveal that microquartz has preserved a considerable δ¹⁸O heterogeneity that must be regarded as a signature inherited from its diagenetic history. Modelling of the δ¹⁸O variations produced during the diagenetic transformation of sedimentary amorphous silica precursors into microquartz allows us to calculate seawater temperature (T_sw at which the amorphous silica precipitated) and diagenesis temperature (T_diagenesis at which microquartz formed) that reproduce the δ¹⁸O distributions (mean, range and shape) measured at micrometer scale in microquartz. The two critical parameters in this modelling are the δ¹⁸O value and the mass fraction of the diagenetic fluid. Under these assumptions, the most likely ranges for T_sw and T_diagenesis are from 37 to 52 °C and from 130 to 170 °C, respectively.     

Calcium isotope ratios in animal and human bone

Calcium isotopes in tissues are thought to be influenced by an individual’s diet, reflecting parameters such as trophic level and dairy consumption, but this has not been carefully assessed. We report the calcium isotope ratios (δ^44/42Ca) of modern and archaeological animal and human bone (n = 216). Modern sheep raised at the same location show 0.14 ± 0.08‰ higher δ^44/42Ca in females than in males, which we attribute to lactation by the ewes. In the archaeological bone samples the calcium isotope ratios of the herbivorous fauna vary by location. At a single site, the archaeological fauna do not show a trophic level effect. Humans have lower δ^44/42Ca than the mean site fauna by 0.22 ± 0.22‰, and the humans have a greater δ^44/42Ca range than the animals. No effect of sex or age on the calcium isotope ratios was found, and intra-individual skeletal δ^44/42Ca variability is negligible. We rule out dairy consumption as the main cause of the lower human δ^44/42Ca, based on results from sites pre-dating animal domestication and dairy availability, and suggest instead that individual physiology and calcium intake may be important in determining bone calcium isotope ratios.     

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.     

Oxygen isotope ratios in magnetite core-and-mantle structures

In a polymetamorphic, felsic, biotite-bearing gneiss, biotite has reacted to form magnetite and microcline. The resulting structure is a magnetite core surrounded by a mantle of feldspar and quartz normally not exceeding 20mm in diameter. Measurements of oxygen isotope ratios disclose disequilibrium between mantle microcline and mantle quartz and also between mantle and matrix minerals of the same species. A clustering of temperature estimates from the oxygen isotope distribution between magnetite and quartz and between magnetite and microcline in the interval 550 to 600°C suggests an approach to oxygen isotope equilibrium. No signs of a re-equilibriation of the reacting biotite can be found.