O/O and D/H in goethite from a North American Oxisol of the Early Eocene climatic optimum

An Early Eocene Oxisol in the Ione Formation of California formed in a coastal continental weathering environment at a paleolatitude of ∼38°N. The dominant minerals in the Oxisol are goethite, quartz, and kaolinite. Material balance calculations were applied to new measurements of chemical composition, D/H, and ¹⁸O/¹⁶O ratios of Oxisol samples to determine the δD (−150 ± 3‰) and δ¹⁸O (−2.4 ± 0.3‰) values of the goethite (α-FeOOH). These data, in combination with the global meteoric water line (MWL), yielded an isotopic temperature of 21(±4) °C. The nominal value of 21 °C contrasts with the modern mean annual temperature (MAT) of 16 °C in that area. The warmer temperature is consistent with formation of the goethite during the Early Eocene climatic optimum. The isotopic composition of the goethite and a temperature of 21 °C imply ancient water with a δD value of −61(±4)‰ and a δ¹⁸O value of −8.9(±0.5)‰. This Early Eocene δ¹⁸O (or δD) value is more negative than values in the range of isotopic scatter observed for modern global precipitation at sites with a MAT of 21 °C.At times of warm global climates, the location of a near-surface atmospheric isotherm would generally shift relative to its location under modern climatic conditions. A simple Rayleigh-type condensation model indicates that, if one “follows the isotherm”, the associated scatter in δD and δ¹⁸O of precipitation in very warm global climates should shift (for a given isotherm) to more negative values that may be detectable in proxy records. The isotopic results from the goethite of the Early Eocene Oxisol appear to add to evidence in support of this idea.     

Early diagenetic processes during Mn-carbonate formation: evidence from the isotopic composition of authigenic Ca-rhodochrosites of the Baltic Sea

The formation of authigenic Ca-rich rhodochrosite (ACR) in sapropelic sediments of the Gotland Basin, Baltic Sea, is governed by deepwater renewal processes whereby saline water from the North Atlantic flushes the brackish anoxic Baltic Deeps. The carbon and oxygen isotopic compositions of these Mn-carbonates suggest that ACR formation takes place just below the sediment surface and that dissolved compounds from the deepwater column, such as water and bicarbonate molecules, were incorporated in ACR during authigenesis. Porewaters near the sediment surface display δ¹⁸O values of −5.4‰ (VSMOW) and are generally depleted in ¹⁸O, compared to the oxygen isotopic composition of water in equilibrium with Mn-carbonate solid solutions (ACR δ¹⁸O values are −4.6‰). This suggests that early burial diagenetic processes significantly modify the initial isotopic composition of water during Mn-carbonate formation. The reduction of sulfate having δ¹⁸O values of +8.4‰ accounts for a permanent enrichment of porewater ¹⁸O and observed δ¹⁸O values at depth equal to −4.6‰. However, this process does not explain the observed disequilibrium in the oxygen isotopic composition between water and ACR close to the sediment surface where Mn-carbonate formation takes place. Based on isotopic mass balance calculations, we suggest that MnO₂ with δ¹⁸O values of +8.9‰ released oxygen enriched in ¹⁸O into the anoxic porewaters close below the sediment surface. This process should occur after oxygenation events during deepwater renewal when MnO₂ accumulates at the surface of anoxic sediments. Manganese carbonates formed in these waters display δ¹⁸O values of ∼1.0‰ heavier than values expected solely from the initial deepwater composition. This quantitatively explains the discrepancy between paleosalinities calculated from ACR δ¹⁸O based on Mn-carbonate/water isotopic equilibrium fractionation and direct observations for the same period. Our results emphasize the important role of microbial MnO₂ reduction during rhodochrosite authigenesis and suggest that Mn(II) activity, rather than alkalinity, is the limiting component for sedimentary Mn-carbonate formation.     

Environmental memory and a possible seasonal bias in the stable isotope composition of (U-Th)/He-dated goethite from the Canadian Arctic

Goethite (Ax-2) from Axel Heiberg Island (∼80°N) on the margin of the Arctic Ocean is the dominant mineral in a sample of “petrified” Eocene wood, but U, Th, and He measurements suggest that the goethite (α-FeOOH) crystallized in the latest Miocene/Pliocene (ca. 5.5 to 2.8 Ma). Measured δD and δ¹⁸O values of Ax-2 are −221 (±6)‰ and −9.6 (±0.5)‰, respectively. The inferred δD and δ¹⁸O values of the ancient water were about −139‰ and −18.6‰, respectively, with a calculated temperature of crystallization of 3 (±5)°C, which compares with the modern summer (J-J-A) temperature of 3 °C and contrasts with a modern MAT of −19 °C. Published results from various biological proxies on nearby Ellesmere Island indicate a Pliocene (∼4 Ma) MAT of either −6 or −0.4 °C and corresponding seasonal amplitudes of about 18 or 13 °C. A conductive heat flow model suggests that a temperature of 3 °C could represent goethite crystallization at depths of ∼100-200 cm (for MAT = −6 °C) or ∼250-450 cm (for MAT = −0.4 °C) over seasonally restricted intervals of time.The δ¹⁸O value of the Ax-2 water (−18.6‰) is more positive than the modern J-J-A precipitation (−22‰). In combination, the paleotemperatures and δ¹⁸O values of ancient waters (from Ax-2 and published results from three Eocene or Pliocene proxy sites on Axel Heiberg and Ellesmere Islands) are consistent with a warm season bias in those isotopic proxies. The results are also consistent with higher proportions of J-J-A precipitation in the annual total. If so, this emphasizes the importance of seasonality at high latitudes even in times of warmer global climates, and suggests that the Arctic hydrologic cycle, as expressed in the seasonal distribution and isotopic composition of precipitation (perhaps modified by a warmer Arctic Ocean), differed from modern.The δ¹³C value of the Fe(CO₃)OH component in the Ax-2 goethite is +6.6‰, which is much more positive than expected if crystallizing goethite incorporated CO₂ derived primarily from oxidation of relict Eocene wood with δ¹³C values of about −24‰. This apparent paradox may be resolved if the goethite is a product of oxidation of ¹³C-rich siderite, which had previously replaced wood in an Eocene methanogenic burial environment. Thus, the goethite retains a carbon isotope “memory” of a diagenetic Eocene event, but a δD and δ¹⁸O record of the latest Miocene/Pliocene Arctic climate.     

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.     

Hydrogen and oxygen isotope ratios in nodular and bedded cherts

Hydrogen and oxygen isotopic compositions of cherts (δD for hydroxyl hydrogen in the chert, δ¹⁸O for the total oxygen) have been determined for a suite of samples from the central and western United States. When plotted on a δD-δ¹⁸O diagram, Phanerozoic cherts define domains parallel to the meteoric water line which are different for different periods of geologic time. The elongation parallel to the meteoric water line suggests that meteoric waters were involved in the formation of many cherts.The existence of different chert δ-values for different geologic times indicates that once the granular microcrystalline quartz of cherts crystallizes its isotopic composition is preserved with time. An explanation for the change with time of the isotopic composition of cherts involving large changes with time in the isotopic composition of ocean water is unlikely since δ¹⁸O of the ocean would have had to decrease by about 3‰between Carboniferous and Triassic time and then increase about 5%.` from Triassic to Cretaceous time. Such isotopic changes cannot be accounted for by extensive glaciation, sedimentation of hydrous minerals, or input of water from the mantle into the oceans.The variation with time of the chert δ-values can be satisfactorily explained in terms of past climatic temperature fluctuations if the chert-water isotope fractionation with temperature is approximated by 1000 lnα = 3.09 × 10⁶T^?2 – 3.29. Crystallization temperatures so inferred suggest that the average climatic temperatures for the central and western U.S. decreased from about 34 to 20°C through the Paleozoic, increased to 35–40°C in the Triassic, and then decreased through the Mesozoic to Tertiary values of about 17°C. A few data for the Precambrian suggest the possibility that Earth surface temperatures may have reached about 52°C at 1.3 b.y. and about 70°C at 3 b.y.     

Sea-rain-lake relation in the Last Glacial East Mediterranean revealed by δO-δC in Lake Lisan aragonites

We investigated the Sea-Rain-Lake relation during the Last Glacial-Holocene in the East Mediterranean region by comparing the δ¹⁸O and δ¹³C records of authigenic aragonite deposited in Lake Lisan, the Dead Sea, Mediterranean foraminifera, and speleothems. The Lisan Formation data display long- and short-term variations of δ¹⁸O, representing steady-state conditions of the lake (e.g., 5.6‰ ± 0.5‰ and 4.5‰ ± 1‰ in the Upper and Lower Members of the Lisan Formation, respectively), and short-term excursions reflecting large floods and droughts. The long-term (steady-state) δ¹⁸O values of the Lisan aragonites show similarity to the corresponding time-equivalent records of the Eastern Mediterranean foraminifera and Judea Mountain speleothems: The Last Glacial deposits are in all of them 2‰-3‰ heavier than the Holocene ones. We interpret this similarity as reflecting the significance of the source effect on the long-term behavior of isotopic reservoirs: Speleothem δ¹⁸O is strongly influenced by the marine reservoir that contributes its vapor to rain formation; the lake δ¹⁸O is dominated by the composition of the inflowing water. Short-term variations in the isotopic composition of rainfall are dominated by the amount effect and the temperature and those of the Lake’s upper water mass by the lake’s water balance.δ¹³C values are more variable than δ¹⁸O in the same Lisan sequences (e.g., δ¹³C in the Lower Member is 1.0‰ ± 1.7‰, whereas δ¹⁸O is 4.6‰ ± 0.7‰) and are 1‰ to 1.5‰ higher in the Upper Member than in the Lower and Middle Members of the Lisan Formation. These variations reflect significant increase in primary productivity of the lake and algal bloom activity. It appears that the hypersaline-saline lakes were not as “dead” as the Dead Sea is and that algal activity had an important impact upon the geochemistry of Lake Lisan.The δ¹⁸O data combined with independent geochemical and limnologic information (e.g., level fluctuations) indicate that Lisan time was characterized by high precipitation-high lake stands-high atmospheric humidity, whereas the Holocene Dead Sea shows the opposite behavior. This paleoclimatic reconstruction is consistent with independent evidence for significantly wetter conditions in the East Mediterranean region during the Last Glacial period.     

Stable isotope composition of Hellenic bottled waters

Bottled waters are an increasingly significant product in the human diet. In this work, we present a dataset of stable isotope ratios for bottled waters sampled in Greece. A total of 25 domestic brands of bottled still waters, collected on the Greek market in 2009, were analysed for δ¹⁸O and δ²H. The measured stable isotope ratios range from − 9.9‰ to − 6.9‰ for δ¹⁸O and from − 67.50‰ to − 46.5‰ for δ²H. Comparison of bottled water isotope ratios with natural spring water isotope ratios demonstrates that on average the isotopic composition of bottled water tends to be similar to the composition of naturally available local water sources, showing that bottled water isotope ratios preserve information about the water sources from which they were derived and suggesting that in many cases bottled water should not be considered as an isotopically distinct component of the human diet. This investigation also helped to determine the natural origin of bottled water, and to indicate differences between the natural and production processes. The production process may influence the isotopic composition of waters. No such modification was observed for sampled waters in this study. The isotopic methods applied can be used for the authentication of bottled waters and for use in the regulatory monitoring of water products.     

Isotopic evidence for the incorporation of methane-derived carbon into foraminifera from modern methane seeps, Hydrate Ridge, Northeast Pacific

The presence of modern methane seeps at Hydrate Ridge, offshore Oregon, provide an opportunity to study the influence of methane seeps on the ecology and geochemistry of living foraminifera. A series of cores were collected from the southern summit of Hydrate Ridge in 2002. Samples were preserved and stained to determine the δ¹³C composition of three species of live (stained) and dead benthic foraminifera: Uvigerina peregrina, Cibicidoides mckannai, and Globobulimina auriculata. Specimens were examined under light and Scanning Electron Microscopy (SEM) and exhibit no evidence of diagenesis or authigenic carbonate precipitation. Individual living foraminifera from seep sites recorded δ¹³C values from −0.4‰ to −21.2‰, indicating the isotopic influence of high methane concentrations. Average δ¹³C values (calculated from single specimens) range from −1.28 to −5.64‰ at seep sites, and −0.81 to −0.85‰ at a control (off seep) site.Two distinct seep environments, distinguished by the presence of microbial mats or clam fields, were studied to determine environmental influences on δ¹³C values. Individual foraminifera from microbial mat sites exhibited more depleted δ¹³C values than those from clam field sites. We interpret these differences as an effect of food source and/or symbiotic microbes on foraminiferal carbon isotopic values, acting to magnify the negative δ¹³C values recorded via the DIC pool. No statistical difference was found between δ¹³C values of live vs. dead specimens. This suggests that authigenic carbonate precipitation did not play a dominant role in the observed isotopic compositions. However, a few dead specimens with extremely negative δ¹³C composition (<-12‰) do indicate potential evidence for an authigenic influence on the recorded δ¹³C composition.     

Effects of aridity and vegetation on plant-wax δD in modern lake sediments

We analyzed the deuterium composition of individual plant-waxes in lake sediments from 28 watersheds that span a range of precipitation D/H, vegetation types and climates. The apparent isotopic fractionation (ε_a) between plant-wax n-alkanes and precipitation differs with watershed ecosystem type and structure, and decreases with increasing regional aridity as measured by enrichment of ²H and ¹⁸O associated with evaporation of lake waters. The most negative ε_a values represent signatures least affected by aridity; these values were −125 ± 5‰ for tropical evergreen and dry forests, −130‰ for a temperate broadleaf forest, −120 ± 9‰ for the high-altitude tropical páramo (herbs, shrubs and grasses), and −98 ± 6‰ for North American montane gymnosperm forests. Minimum ε_a values reflect ecosystem-dependent differences in leaf water enrichment and soil evaporation. Slopes of lipid/lake water isotopic enrichments differ slightly with ecosystem structure (i.e. open shrublands versus forests) and overall are quite small (slopes = 0-2), indicating low sensitivity of lipid δD variations to aridity compared with coexisting lake waters. This finding provides an approach for reconstructing ancient precipitation signatures based on plant-wax δD measurements and independent proxies for lake water changes with regional aridity. To illustrate this approach, we employ paired plant-wax δD and carbonate-δ¹⁸O measurements on lake sediments to estimate the isotopic composition of Miocene precipitation on the Tibetan plateau.     

Oxygen and carbon isotopic systematics of aragonite speleothems and water in Furong Cave, Chongqing, China

To understand oxygen and carbon stable isotopic characteristics of aragonite stalagmites and evaluate their applicability to paleoclimate, the isotopic compositions of active and fossil aragonite speleothems and water samples from an in situ multi-year (October 2005-July 2010) monitoring program in Furong Cave located in Chongqing of China have been examined. The observations during October 2005-June 2007 show that the meteoric water is well mixed in the overlying 300-500-m bedrock aquifer, reflected by relatively constant δ¹⁸O, ±0.11-0.14‰ (1σ), of drip waters in the cave, which represents the annual status of rainfall water. Active cave aragonite speleothems are at oxygen isotopic equilibrium with drip water and their δ¹⁸O values capture the surface-water oxygen isotopic signal. Aragonite-to-calcite transformation since the last glaciation is not noticeable in Furong stalagmites. Our multi-year field experiment approves that aragonite stalagmite δ¹⁸O records in this cave are suitable for paleoclimate reconstruction. With high U, 0.5-7.2 ppm, and low Th, 20-1270 ppt, the Furong aragonite stalagmites provide very precise chronology (as good as ±20s yrs (2σ)) of the climatic variations since the last deglaciation. The synchroneity of Chinese stalagmite δ¹⁸O records at the transition into the Bølling-Allerød (t-BA) and the Younger Dryas from Furong, Hulu and Dongge Caves supports the fidelity of the reconstructed East Asian monsoon evolution. However, the Furong record shows that the cold Older Dryas (OD) occurred at 14.0 thousand years ago, agreeing with Greenland ice core δ¹⁸O records but ∼200 yrs younger than that in the Hulu record. The OD age discrepancy between Chinese caves can be attributable to different regionally climatic/environmental conditions or chronological uncertainty of stalagmite proxy records, which is limited by changes in growth rate and subsampling intervals in absolute dating. Seasonal dissolved inorganic carbon δ¹³C variations of 2-3‰ in the drip water and 5-7‰ in the pool and spring waters are likely attributed to variable degrees of CO₂ degassing in winter and summer. The variable δ¹³C values of active deposits from −11‰ to 0‰ could be caused by kinetically mediated CO₂ degassing processes. The complicated nature of pre-deposition kinetic isotopic fractionation processes for carbon isotopes in speleothems at Furong Cave require further study before they can be interpreted in a paleoclimatic or paleoenvironmental context.     

Antiphase hydrogen and oxygen isotope periodicity in chert nodules

Oxygen and hydrogen isotope analyses were made of Jurassic-age chert nodules from the Holy Cross Mountains, SE Poland, along radial transects at high spatial resolution. There is a radial “sigmoidal” periodicity for both isotope ratios, but the two are out of phase, with high δD values corresponding to low δ¹⁸O values. Periodicity for a 100- to 120-mm diameter nodule is approximately 16 mm, increasing slightly toward the rim, with amplitudes approaching 20 and 3.0‰ for hydrogen and oxygen, respectively. The combined hydrogen-oxygen isotope data for one nodule fall on a published curve for chert forming in equilibrium with seawater (Knauth and Epstein, 1976); the range of delta values corresponds to temperature variations of ∼10°C. Data for a second chert fall on a subparallel δD-δ¹⁸O line with δD values that are almost 50‰ lower. The δD-δ¹⁸O patterns for the nodules cannot be explained by periodic mixing of meteoric and ocean water because the hydrogen and oxygen isotope data are out of phase. Two possible explanations for the antiphase periodicity are (a) cyclical temperature variations, perhaps related to an unstable convection system (e.g., Bolton et al., 1999), and (b) self-organizing catalytic precipitation (e.g., Wang and Merino, 1990). The systematic isotopic variations are difficult to explain by diagenesis and strongly suggest that primary isotopic compositions are preserved. The isotopic data provide important information on the thermal history of the sedimentary basin, if temperature variations are the cause of the isotopic periodicity.     

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.     

Isotopic compositions of oxygen, iron, chromium, and nickel in cosmic spherules: Toward a better comprehension of atmospheric entry heating effects

Large, correlated, mass-dependent enrichments in the heavier isotopes of O, Cr, Fe, and Ni are observed in type-I (metal/metal oxide) cosmic spherules collected from the deep sea. Limited intraparticle variability of oxygen isotope abundances, typically <5‰ in δ¹⁸O, indicates good mixing of the melts and supports the application of the Rayleigh equation for the calculation of fractional evaporative losses during atmospheric entry. Fractional losses for oxygen evaporation from wüstite, assuming a starting isotopic composition equal to that of air (δ¹⁸O = 23.5‰; δ¹⁷O = 11.8‰), are in the range 55%-77%, and are systematically smaller than evaporative losses calculated for Fe (69%-85%), Cr (81%-95%), and especially Ni (45%-99%). However, as δ¹⁸O values increase, fractional losses for oxygen approach those of Fe, Cr, and Ni indicating a shift in the evaporating species from metallic to oxidized forms as the spherules are progressively oxidized during entry heating. The observed unequal fractional losses of O and Fe can be reconciled by allowing for a kinetic isotope mass-dependent fractionation of atmospheric oxygen during the oxidation process and/or that some metallic Fe may have undergone Rayleigh evaporation before oxidation began.In situ measurements of oxygen isotopic abundances were also performed in 14 type-S (silicate) cosmic spherules, 13 from the Antarctic ice and one from the deep sea. Additional bulk Fe and Cr isotopic abundances were determined for two type-S deep-sea spherules. The isotopic fractionation of Cr isotopes suggest appreciable evaporative loss of Cr, perhaps as a sulfide. The oxygen isotopic compositions for the type-S spherules range from δ¹⁸O = −2‰ to + 27‰. The intraspherule isotopic variations are typically small, ∼5% relative, except for the less-heated porphyritic spherules which have preserved large isotopic heterogeneities in at least one case. A plot of δ¹⁷O vs. δ¹⁸O values for these spherules defines a broad parallelogram bounded at higher values of δ¹⁷O by the terrestrial fractionation line, and at lower values of δ¹⁷O by a line parallel to it and anchored near the isotopic composition of δ¹⁸O = −2.5‰ and δ¹⁷O = −5‰. Lack of independent evidence for substantial evaporative losses suggests that much of this variation reflects the starting isotopic composition of the precursor materials, which likely resembled CO, CM, or CI chondrites. However, the enrichments in heavy isotopes indicate that some mixing with atmospheric oxygen was probably involved during atmospheric entry for some of the spherules. Isotopic fractionation due to evaporation of incoming grain is not required to explain most of the oxygen isotopic data for type-S spherules. However spherules with barred olivine textures that are thought to have experienced a more intense heating than the porphyritic ones might have undergone some distillation. Two cosmic spherules, one classified as a radial pyroxene type and the other showing a glassy texture, show unfractionated oxygen isotopic abundances. They are probably chondrule fragments that survived atmospheric entry unmelted.Possible reasons type-I spherules show larger degrees of isotopic fractionation than type-S spherules include: a) the short duration of the heating pulse associated with the high volatile content of the type-S spherule precursors compared to type-I spherules; b) higher evaporation temperatures for at least a refractory portion of the silicates compared to that of iron metal or oxide; c) lower duration of heating of type-S spherules compared to type-I spherules as a consequence of their lower densities.     

Paleogene paleoclimate reconstruction using oxygen isotopes from land and freshwater organisms: the use of multiple paleoproxies

Understanding past climate change is critical to the interpretation of earth history. Even though relative temperature change has been readily assessed in the marine record, it has been more difficult in the terrestrial record due to restricted taxonomic distribution and isotopic fractionation. This problem could be overcome by the use of multiple paleoproxies. Therefore, the δ¹⁸O isotopic composition of five paleoproxies (rodent tooth enamel, δ¹⁸O_Phosphate = +17.7 ± 2.0‰ n = 74 (VSMOW); fish scale ganoine δ¹⁸O_Phosphate = +19.7 ± 0.7‰ n = 20 (VSMOW); gastropod shell δ¹⁸O_Calcite = −1.7 ± 1.3‰ n = 50 (VPDB); charophyte gyrogonite δ¹⁸O_Calcite = −2.4 ± 0.5‰ n = 20 (VPDB); fish otolith δ¹⁸O_Aragonite = δ¹⁸O = −3.6 ± 0.6‰ n = 20 (VPDB)) from the Late Eocene (Priabonian) Osborne Member (Headon Hill Formation, Solent Group, Hampshire Basin, UK) were determined. Because diagenetic alteration was shown to be minimal the phosphate oxygen component of rodent tooth enamel (as opposed to enamel carbonate oxygen) was used to calculate an initial δ¹⁸O_{Local water} value of 0.0 ± 3.4‰. However, a skewed distribution, most likely as a result of the ingestion of evaporating water, necessitated the calculation of a corrected δ¹⁸O_{Local water} value of −1.3 ± 1.7‰ (n = 62). This δ¹⁸O_{Local water} value corresponds to an approximate mean annual temperature of 18 ± 1°C. Four other mean paleotemperatures can also be calculated by combining the δ¹⁸O_{Local water} value with four independent freshwater paleoproxies. The calculated paleotemperature using the fish scale thermometry equations most likely represents the mean temperature (21 ± 2°C) of the entire length of the growing season. This should be concordant with the paleotemperature calculated using the Lymnaea shell thermometry equation (23 ± 2°C). The lack of concordance is interpreted to be the result of diagenetic alteration of the originally aragonitic Lymnaea shell to calcite. The mean paleotemperature calculated using the charophyte gyrogonite thermometry equation (21 ± 2°C), on the other hand, most likely represents the mean temperature of a single month toward the end of the growing season. The fish otolith mean paleotemperature (28 ± 2°C) most likely represents the mean temperature of the warmest months of the growing season. An approximate mean annual temperature of 18 ± 1°C, in addition to a mean growing season paleotemperature of 21 ± 2°C (using fish scale only) with a warmest month temperature of 28 ± 2°C, and high associated standard deviations suggest that a subtropical to warm temperate seasonal climate existed during the deposition of the Late Eocene Osborne Member.     

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.     

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.     

Paleoclimatic implications of the spatial patterns of modern and LGM European land-snail shell δO

The oxygen isotopic composition of land-snail shells may provide insight into the source region and trajectory of precipitation. Last glacial maximum (LGM) gastropod shells were sampled from loess from Belgium to Serbia and modern land-snail shells both record δ¹⁸O values between 0‰ and − 5‰. There are significant differences in mean fossil shell δ¹⁸O between sites but not among genera at a single location. Therefore, we group δ¹⁸O values from different genera together to map the spatial distribution of δ¹⁸O in shell carbonate. Shell δ¹⁸O values reflect the spatial variation in the isotopic composition of precipitation and incorporate the snails' preferential sampling of precipitation during the warm season. Modern shell δ¹⁸O decreases in Europe along a N-S gradient from the North Sea inland toward the Alps. Modern observed data of isotopes in precipitation (GNIP) demonstrate a similar trend for low-altitude sites. LGM shell δ¹⁸O data show a different gradient with δ¹⁸O declining toward the ENE, implying a mid-Atlantic source due to increased sea ice and a possible southern displacement of the westerly jet stream. Balkan LGM samples show the influence of a Mediterranean source, with δ¹⁸O values decreasing northward.     

Changing moisture sources over the last 330,000 years in Northern Oman from fluid-inclusion evidence in speleothems

Speleothems from Hoti Cave in northern Oman provide a record of continental pluvial periods over the last 330,000 yr. Periods of rapid speleothem deposition occurred from 6000 to 10,500, 78,000 to 82,000, 120,000 to 135,000, 180,000 to 200,000, and 300,000 to 330,000 yr ago, with little or no growth during the intervening periods. During each of these five pluvial periods, δD values of water extracted from speleothem fluid inclusions (δD_FI) are between −60 and −20‰ (VSMOW) and δ¹⁸O values of speleothem calcite (δ¹⁸O_C) are between −12 and −4‰ to (VPDB). These values are much more negative than modern rainfall (for δD) or modern stalagmites (for δ¹⁸O). Previous work on the isotopic composition of rainfall in Oman has shown that northern and southern moisture sources are isotopically distinct. Combined measurements of the δD values of fluid-inclusion water with calculated δ¹⁸O values from peak interglacial speleothems indicate that groundwater was predominantly recharged by the southern (Indian Ocean) moisture source, when the monsoon rainfall belt moved northward and reached Northern Oman during each of these periods.     

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.     

Carbonaceous cherts of the Barberton Greenstone Belt, South Africa: Isotopic, chemical and structural characteristics of individual microstructures

Carbonaceous matter occurring in chert deposits of the 3.4-3.2 Ga old Barberton Greenstone Belt (BGB), South Africa, has experienced low grade regional metamorphism and variable degrees of local hydrothermal alteration. Here a detailed study is presented of in situ analysis of carbonaceous particles by LRS (laser Raman spectroscopy) and SIMS (secondary ion mass spectrometry), reporting degree of structural disorder, carbon isotope ratio and nitrogen-to-carbon ratio. This combination of in situ analytical tools is used to interpret the δ¹³C values of only the best preserved carbonaceous remains, enabling the rejection of non-indigenous (unmetamorphosed) material as well as the exclusion of strongly hydrothermally altered carbonaceous particles. Raman spectroscopy confirmed that all carbonaceous cherts studied here have experienced a regional sub- to lower-greenschist facies metamorphic event. Although this identifies these organics as indigenous to the cherts, it is inferred from petrographic observations that hydrothermal alteration has caused small scale migration and re-deposition of organics. This suggest that morphological interpretation of these carbonaceous particles, and in general of putative microfossils or microlaminae in hydrothermally altered early Archean cherts, should be made with caution. A chert in the Hooggenoeg Formation, which is older than and has been hydrothermally altered by a volcanic event 3445 Ma ago, contains strongly altered carbonaceous particles with a uniform N/C-ratio of 0.001 and a range of δ¹³C that is shifted from its original value. Cherts of the Kromberg Formation post-date this volcanic event, and contain carbonaceous particles with a N/C-ratio between 0.002 and 0.006. Both the Buck Reef Chert and the Footbridge Chert of the Kromberg Formation have retained fairly well-preserved δ¹³C values, with ranges from −34‰ to −24‰ and −40‰ to −32 ‰, respectively. Abiologic reactions associated with hydrothermal serpentinization of ultramafic crust (such as Fischer-Tropsch synthesis) were an unlikely source for carbonaceous material in these cherts. The carbonaceous matter in these cherts has all the characteristics of metamorphosed biologic material.