Coastal and oceanic SST variability along the western Iberian Peninsula

The inter-annual variability of the sea surface temperature (SST) was analyzed along the western Iberian Peninsula in the region ranging from 9.5 °W to 21.5 °W and from 37.5 °N to 42.5 °N with a spatial resolution of 1°×1° from 1900 to 2008. Both coastal and oceanic SST showed an overall increase with warming and cooling cycles similar to those observed in the North Atlantic region and in previous regional studies. In addition, the evolution of coastal and ocean water has been observed to be different. In general, ocean water is more affected by the different warming–cooling cycles than coastal water. In spite of coast and ocean are highly influenced by global changes affecting the whole North Atlantic region, near shore SST has been observed to be correlated with local wind regime, which is itself a manifestation of the Eastern Atlantic (EA) teleconnection pattern.     

Decoupled warming and monsoon precipitation in East Asia over the last deglaciation

Our understanding of the continental climate development in East Asia is mainly based on loess–paleosol sequences and summer monsoon precipitation reconstructions based on oxygen isotopes (δ¹⁸O) of stalagmites from several Chinese caves. Based on these records, it is thought that East Asian Summer Monsoon (EASM) precipitation generally follows Northern Hemisphere (NH) summer insolation. However, not much is known about the magnitude and timing of deglacial warming on the East Asian continent. In this study we reconstruct continental air temperatures for central China covering the last 34,000 yr, based on the distribution of fossil branched tetraether membrane lipids of soil bacteria in a loess–paleosol sequence from the Mangshan loess plateau. The results indicate that air temperature varied in phase with NH summer insolation, and that the onset of deglacial warming at ~ 19 kyr BP is parallel in timing with other continental records from e.g. Antarctica, southern Africa and South-America. The air temperature increased from ~ 15 °C at the onset of the warming to a maximum of ~ 27 °C in the early Holocene (~ 12 kyr BP), in agreement with the temperature increase inferred from e.g. pollen and phytolith data, and permafrost limits in central China.Comparison of the tetraether membrane lipid-derived temperature record with loess–paleosol proxy records and stalagmite δ¹⁸O records shows that the strengthening of EASM precipitation lagged that of deglacial warming by ca. 3 kyr. Moreover, intense soil formation in the loess deposits, caused by substantial increases in summer monsoon precipitation, only started around 12 kyr BP (ca. 7 kyr lag). Our results thus show that the intensification of EASM precipitation unambiguously lagged deglacial warming and NH summer insolation, and may contribute to a better understanding of the mechanisms controlling ice age terminations.     

Early onset and origin of 100-kyr cycles in Pleistocene tropical SST records

The large 100-kyr cycles evident in most late-Pleistocene (0–0.6 Ma) paleoclimatic records still lack a satisfactory explanation. Previous studies of the nature of the transition from the early Pleistocene (1.2–1.8 Ma) 41-kyr-dominated climate regime to the 100-kyr world have been based almost exclusively on benthic foraminiferal oxygen isotopic (δ¹⁸O) data. It is generally accepted that the late Pleistocene 100-kyr cycles represent a newly evolved sensitivity to eccentricity/precession, superimposed on an earlier, and largely constant, response to obliquity and precession forcing. However, orbitally-resolved Pleistocene sea surface temperature (SST) records from a variety of oceanic regions paint a rather different picture of the global climate transition across the mid-Pleistocene transition (MPT, 0.6–1.2 Ma). Reanalysis of these SST records shows that: (1) an early onset of strong 100-kyr-like cycles in two low-frequency bands (～ 120–145 kyr and ～ 60–80 kyr), derived from the bundling of two/three obliquity cycles into grand cycles (obliquity subharmonics), occurred in tropical SST records during the early Pleistocene, (2) these two early Pleistocene periods converge into the late-Pleistocene 100-kyr period in tropical SST records, (3) the dominance of 100-kyr SST power in the late Pleistocene coincides with a dramatic decline in the 41-kyr SST power, and (4) the correlation of timing of glacial terminations with eccentricity/precession variation could well extend back into the early Pleistocene. We demonstrate that most of these features also occur in δ¹⁸O records, but in a much more subtle manner. These features could be explained in two plausible ways: a shift in climate sensitivity from obliquity to eccentricity/precession (a modified version of the conventional view) or an increasingly nonlinear response to orbital obliquity across the MPT. However, our examination of the development of ～100-kyr cycles favors an obliquity bundling mechanism to form late Pleistocene 100-kyr cycles. We therefore suggest that the late Pleistocene 100-kyr climatic cycles are likely a nonlinear response to orbital obliquity, although the timing of late Pleistocene 100-kyr climatic cycles and their early forms appears to be paced by eccentricity/precession.     

Spring and summer blooms of phytoplankton (SeaWiFS/MODIS) along a ferry line in the Bay of Biscay and western English Channel

The seasonal cycle of chlorophyll concentration in the Bay of Biscay and western English Channel has been examined using satellite data (chlorophyll, sea surface temperature (SST), photosynthetically available radiation (PAR) and wind) along the line of the ferry Pride of Bilbao (Bilbao to Portsmouth). The spring phytoplankton bloom develops regularly in the oceanic region of the Bay of Biscay from mid March to the beginning of May with peak chlorophyll concentrations ranging 2–4 mg m^?3. Low wind turbulence is a major factor allowing the development of productivity pulses in the Bay of Biscay during spring. Exceptional blooms of phytoplankton take place in summer (July–August) in the western English Channel with chlorophyll concentrations as high as 40 mg m^?3. Some environmental factors (SST, wind, pressure and tide) are examined. Autumn blooms of phytoplankton (1–2 mg m^?3) are also detected in the northern Bay of Biscay, shelf-break and Celtic Sea in October. A 11 years pluri-annual synthesis of SeaWiFS satellite measurements is presented.     

Decadal scale variability of sea surface temperature in the Mediterranean Sea in relation to atmospheric variability

Twenty-four years of AVHRR-derived sea surface temperature (SST) data (1985–2008) and 35 years of NOCS (V.2) in situ-based SST data (1973–2008) were used to investigate the decadal scale variability of this parameter in the Mediterranean Sea in relation to local air–sea interaction and large-scale atmospheric variability. Satellite and in situ-derived data indicate a strong eastward increasing sea surface warming trend from the early 1990s onwards. The satellite-derived mean annual warming rate is about 0.037°C year^–1 for the whole basin, about 0.026°C year^–1 for the western sub-basin and about 0.042°C year^–1 for the eastern sub-basin over 1985–2008. NOCS-derived data indicate similar variability but with lower warming trends for both sub-basins over the same period. The long-term Mediterranean SST spatiotemporal variability is mainly associated with horizontal heat advection variations and an increasing warming of the Atlantic inflow. Analysis of SST and net heat flux inter-annual variations indicates a negative correlation, with the long-term SST increase, driving a net air–sea heat flux decrease in the Mediterranean Sea through a large increase in the latent heat loss. Empirical orthogonal function (EOF) analysis of the monthly average anomaly satellite-derived time series showed that the first EOF mode is associated with a long-term warming trend throughout the whole Mediterranean surface and it is highly correlated with both the Eastern Atlantic (EA) pattern and the Atlantic Multidecadal Oscillation (AMO) index. On the other hand, SST basin-average yearly anomaly and NAO variations show low and not statistically significant correlations of opposite sign for the eastern (negative correlation) and western (positive correlation) sub-basins. However, there seems to be a link between NAO and SST decadal-scale variations that is particularly evidenced in the second EOF mode of SST anomalies. NOCS SST time series show a significant SST rise in the western basin from 1973 to the late 1980s following a large warming of the inflowing surface Atlantic waters and a long-term increase of the NAO index, whereas SST slowly increased in the eastern basin. In the early 1990s, there is an abrupt change from a very high positive to a low NAO phase which coincides with a large change in the SST spatiotemporal variability pattern. This pronounced variability shift is followed by an acceleration of the warming rate in the Mediterranean Sea and a change in the direction (from westward to eastward) of its spatial increasing tendency.     

Galactic cosmic rays—clouds effect and bifurcation model of the Earth global climate. Part 2. Comparison of theory with experiment

The solution of energy-balance model of the Earth global climate and the EPICA Dome C and Vostok experimental data of the Earth surface palaeotemperature evolution over past 420 and 740 kyr are compared.In the framework of proposed bifurcation model (i) the possible sharp warmings of the Dansgaard-Oeschger type during the last glacial period due to stochastic resonance is theoretically argued; (ii) the concept of climatic sensitivity of water in the atmosphere, whose temperature instability has the form of so-called hysteresis loop, is proposed, and based on this concept the time series of global ice volume over the past 1000 kyr, which is in good agreement with the time series of δ¹⁸O concentration in the sea sediments, is obtained; (iii) the so-called “CO₂ doubling” problem is discussed.     

Present warming within the context of cooling–warming cycles observed since 1854 in the Bay of Biscay

The warming trend observed during the last decades in the Bay of Biscay is put within the context of sea surface temperature (SST) changes observed in the area since 1854. Macroscopically, two consecutive warming–cooling cycles were detected during this period of time: cooling from 1867 to 1910; warming from 1910 to 1945; cooling from 1945 to 1974; and warming from 1974 to nowadays. Warming rates of 0.17 and 0.22 °C per decade were measured during the warming sub-periods and cooling rates of ?0.14 and ?0.10 °C per decade were measured during the cooling sub-periods. The present warming period is on the same order of magnitude although slightly more intense than the one observed from 1910 to 1945, which is consistent with previous analysis carried for the North Atlantic. Finally, the thermal amplitude defined as the difference between the maximum and minimum annual values has increased since 1974 at a rate of 0.06 °C per decade due to the different increasing rates of the maximum (0.26 °C per decade) and minimum (0.20 °C per decade) SSTs.     

Late Cenomanian to Middle Turonian high-resolution carbon isotope stratigraphy: New data from the Münsterland Cretaceous Basin,Germany

New high resolution carbon isotope stratigraphies from two basinal pelagic carbonate successions in northern Germany (Halle and Oerlinghausen, Münsterland Cretaceous Basin) resolve late Cenomanian to early Mid-Turonian carbon cycle variations at timescales of less than 100 kyr. Beside the major carbon isotope excursion of the late Cenomanian oceanic anoxic event (OAE 2), 11 small-scale distinct features are precisely resolved in the δ¹³C carbonate curve and related to boreal macrofossil zonations. The small-scale carbon isotope events correspond to secular δ¹³C carbonate variations identified previously in the English Chalk. The boreal high-resolution δ¹³C carbonate curve shows a detailed coincidence with two Tethyan δ¹³C curves from Italy, what demonstrates the interregional significance of the δ¹³C dates and allows their correlation within error limits of ± 40 kyr. Furthermore, the new δ¹³C curve enables the calibration of boreal and tethyan macro- and microfossil zonations. Accordingly, the Tethyan calcareous nannoplankton boundary NC13/NC14 corresponds to the boreal FO of C. woollgari, the index taxon for the Lower-Middle Turonian boundary. The cyclic appearance and the temporal spacing of the small-scale carbon isotope events suggest that orbital forcing exerted control on surface water productivity and organic matter preservation at the sea floor.     

Coupled silicon–oxygen isotope fractionation traces Archaean silicification

Silica alteration zones and cherts are a conspicuous feature of Archaean greenstone belts worldwide and provide evidence of extensive mobilisation of silica in the marine environment of the early Earth. In order to understand the process(es) of silicification we measured the silicon and oxygen isotope composition of sections of variably silicified basalts and overlying bedded cherts from the Theespruit, Hooggenoeg and Kromberg Formations of the Barberton Greenstone Belt, South Africa.The δ³⁰Si and δ¹⁸O values of bulk rock increase with increasing amount of silicification from unsilicified basalts (?0.64‰ < δ³⁰Si < ?0.01‰ and + 8.6‰ < δ¹⁸O < + 11.9‰) to silicified basalts (δ³⁰Si and δ¹⁸O values as high as + 0.81‰ and + 15.6‰, respectively). Cherts generally have positive isotope ratios (+ 0.21‰ < δ³⁰Si < + 1.05‰ and + 10.9 < δ¹⁸O < + 17.1), except two cherts, which have negative δ³⁰Si values, but high δ¹⁸O (up to + 19.5‰).The pronounced positive correlations between δ³⁰Si, δ¹⁸O and SiO₂ imply that the isotope variation is driven by the silicification process which coevally introduced both ¹⁸O and ³⁰Si into the basalts. The oxygen isotope variation in the basalts from about 8.6‰ to 15.6‰ is likely to represent temperature-dependent isotope fractionation during alteration. Our proposed model for the observed silicon isotope variation relies on a temperature-controlled basalt dissolution vs. silica deposition process.     

Century-long record of Mo isotopic composition in sediments of a seasonally anoxic estuary (Chesapeake Bay)

A double-spike method was used to obtain Mo isotope data for sediments and waters of the seasonally anoxic Chesapeake Bay, and its primary tributary, the Susquehanna River. The dissolved Mo distribution in the estuary is non-conservative, reflecting minor Mo loss to the sediments, although removal of Mo to the sediments does not have a large influence on the isotopic composition of the water column. The δ⁹⁸Mo of dissolved Mo in most of the estuary is dominated by seawater. Six samples with salinity > 15 have an average δ⁹⁸Mo = + 2.17‰ (± 0.12), which agrees well with a δ⁹⁸Mo value for the CASS-4 seawater standard of + 2.23‰. A single sample of Susquehanna River water has a δ⁹⁸Mo of + 1.02‰, consistent with recent findings of positive δ⁹⁸Mo in rivers worldwide. Susquehanna river sediments, in contrast, have δ⁹⁸Mo ～ ? 0.1‰. The difference between the river water and sediment values implies that isotopic fractionation occurs within the river basin. The δ⁹⁸Mo values for estuarine sediments are offset from values in the overlying water. Most samples deposited before 1925 have δ⁹⁸Mo less than 0‰, similar to the Susquehanna sediments. Subsequently, there is an increase in the variability of δ⁹⁸Mo, with values ranging up to + 0.8‰. The transition to increased variability coincides with the onset of authigenic Mo deposition, which was previously attributed to escalating summertime anoxia. Authigenic Mo concentrations correlate poorly with δ⁹⁸Mo in core samples, suggesting that independent mechanisms influence the two parameters. Authigenic Mo concentrations may be controlled by shifting pore water H₂S levels, while δ⁹⁸Mo may be primarily affected by annual variations in Mn refluxing.     

Persistent organic pollutants and stable isotopes in pinnipeds from King George Island,Antarctica

In the present work, fat, skin, liver and muscle samples from Leptonychotes weddellii (Weddell seal, n = 2 individuals), Lobodon carcinophagus (crabeater seal, n = 2), Arctocephalus gazella (Antarctic fur seal, n = 3) and Mirounga leonina (southern elephant seal, n = 1) were collected from King George Island, Antarctica, and analysed for POPs (PCBs, organochlorine pesticides and PBDEs) and stable isotopes (δ¹³C and δ¹⁵N in all tissues but fat). PBDEs could be found in only one sample (L. weddellii fat). Generally, PCBs (from 74 to 523 ng g⁻¹ lw), DDTs (from 14 to 168 ng g⁻¹ lw) and chlordanes (from 9 to 78 ng g⁻¹ lw) were the prevailing compounds. Results showed a clear stratification in accordance with ecological data. Nonetheless, stable isotope analyses provide a deeper insight into fluctuations due to migrations and nutritional stress. Correlation between δ¹⁵N and pollutants suggests, to some degree, a considerable ability to metabolize and/or excrete the majority of them.     

Isotopic fractionation of zinc in tektites

Tektites are terrestrial natural glasses produced during a hypervelocity impact of an extraterrestrial projectile onto the Earth's surface. The similarity between the chemical and isotopic compositions of tektites and terrestrial upper continental crust implies that the tektites formed by fusion of such target rock. Tektites are among the driest rocks on Earth. Although volatilization at high temperature may have caused this extreme dryness, the exact mechanism of the water loss and the behavior of other volatile species during tektite formation are still debated. Volatilization can fractionate isotopes, therefore, comparing the isotope composition of volatile elements in tektites with that of their source rocks may help to understand the physical conditions during tektite formation.For this study, we have measured the Zn isotopic composition of 20 tektites from four different strewn fields. Almost all samples are enriched in heavy isotopes of Zn compared to the upper continental crust. On average, the different groups of tektites are isotopically distinct (listed from the isotopically lightest to the heaviest): Muong-Nong type indochinites (δ^66/64Zn = 0.61 ± 0.30‰); North American bediasites (δ^66/64Zn = 1.61 ± 0.49‰); Ivory Coast tektites (δ^66/64Zn = 1.66 ± 0.18‰); the Australasian tektites (others than the Muong Nong-type indochinites) (δ^66/64Zn = 1.84 ± 0.42‰); and Central European moldavites (δ^66/64Zn = 2.04 ± 0.19‰). These results are contrasted with a narrow range of δ^66/64Zn = 0–0.7‰ for a diverse spectrum of upper continental crust materials.The elemental abundance of Zn is negatively correlated with δ^66/64Zn, which may reflect that isotopic fractionation occurred by evaporation during the heating event upon tektite formation. Simple Rayleigh distillation predicts isotopic fractionations much larger than what is actually observed, therefore, such a model cannot account for the observed Zn isotope fractionation in tektites. We have developed a more realistic model of evaporation of Zn from a molten sphere: during its hypervelocity trajectory, the molten surface of the tektite will be entrained by viscous coupling with air that will then induce a velocity field inside the molten sphere. This velocity field induces significant radial chemical mixing within the tektite that accelerates the evaporation process. Our model, albeit parameter dependent, shows that both the isotopic composition and the chemical abundances measured in tektites can be produced by evaporation in a diffusion-limited regime.     

Magnesium isotopes constraints on the origin of Mg-rich olivines from the Allende chondrite: Nebular versus planetary?

High precision Mg isotope measurements by multi-collector ion microprobe show that refractory olivines from the Allende chondrite, either olivines isolated in the matrix (2 samples studied) or olivines in type I chondrules (6 samples studied), have variable δ²⁶Mg* enrichments and deficits (calculated in permil as the ²⁶Mg deviation from the instrumental mass fractionation line) relative to the Earth. Most average δ²⁶Mg* (noted δ²⁶Mg*_av) values (between 10 and 20 analyses per chondrule) are negative but the total range is from ?0.029 (± 0.010) ‰ (2 sigma errors) to + 0.011 (± 0.011) ‰ with an exception of one olivine at + 0.043 (± 0.023) ‰. These variations in δ²⁶Mg*_av reflect the formation of the olivines from reservoirs enriched in various amounts of ²⁶Mg by the decay of short-lived ²⁶Al (T_1/2 = 0.73 Ma). Similarly, 30 analyses of olivines from the Eagle Station pallasite show a δ²⁶Mg*_av value of ?0.033 ± 0.008‰, as negative as some olivines from Allende chondrules and the Solar system initial δ²⁶Mg* value of ?0.038 ± 0.004‰ (defined at the time of formation of type B Ca–Al-rich inclusions – CAIs – when ²⁶Al/²⁷Al = 5.23 × 10^?5, Jacobsen et al., 2008).Because olivines are Al-poor and because their Mg isotopic compositions are not reset during the chondrule forming events, their δ²⁶Mg*_av can be used to calculate model crystallization ages relative to various theoretical Mg isotope growth curves. The two end-member scenarios considered are (i) a “nebular” growth in which the Al/Mg ratio remains chondritic and (ii) a “planetary” growth in which a significant increase of the Al/Mg ratio can be due to, for instance, olivine magmatic fractionation. The low δ²⁶Mg*_av value of olivines from the Eagle Station pallasite demonstrate that metal-silicate differentiation occurred as early as ~ 0. 15_- 0. 23^+ 0. 29 Ma after CAIs in either of the growth scenarios. Similarly the variable δ²⁶Mg*_av values of refractory olivines can be understood if they were formed in planetesimals which started to differentiate as early as the Eagle Station parent body. Accretion of these planetesimals must have been coeval to the formation of CAIs and their disruption could explain why their fragments (Mg-rich olivines) were distributed in the chondrule forming regions of the disk.     

The Himalayan foreland basin crust and upper mantle

Modeling of multimode surface wave group velocity dispersion data sampling the eastern and the western Ganga basins, reveals a three layer crust with an average V_s of 3.7 km s^?1, draped by ～2.5 km foreland sediments. The Moho is at a depth of 43 ± 2 km and 41 ± 2 km beneath the eastern and the western Ganga basins respectively. Crustal V_p/V_s shows a felsic upper and middle crust beneath the eastern Ganga basin (1.70) compared to a more mafic western Ganga basin crust (1.77). Due to higher radiogenic heat production in felsic than mafic rocks, a lateral thermal heterogeneity will be present in the foreland basin crust. This heterogeneity had been previously observed in the north Indian Shield immediately south of the foreland basin and must also continue northward below the Himalaya. The high heat producing felsic crust, underthrust below the Himalayas could be an important cause for melting of midcrustal rocks and emplacement of leucogranites. This is a plausible explanation for abundance of leucogranites in the east-central Himalaya compared to the west. The uppermost mantle V_s is also significantly lower beneath the eastern Ganga basin (4.30 km s^?1) compared to the west (4.44 km s^?1).     

The Late Eocene 187Os / 188Os excursion: Chemostratigraphy,cosmic dust flux and the Early Oligocene glaciation

High resolution records (ca. 100 kyr) of Os isotope composition (¹⁸⁷Os / ¹⁸⁸Os) in bulk sediments from two tropical Pacific sites (ODP Sites 1218 and 1219) capture the complete Late Eocene ¹⁸⁷Os / ¹⁸⁸Os excursion and confirm that the Late Eocene ¹⁸⁷Os / ¹⁸⁸Os minimum, earlier reported by Ravizza and Peucker-Ehrenbrink [Earth Planet. Sci. Lett. 210 (2003) 151–165], is a global feature. Using the astronomically tuned age models available for these sites, it is suggested that the Late Eocene ¹⁸⁷Os / ¹⁸⁸Os minimum can be placed at 34.5 ± 0.1 Ma in the marine records. In addition, two other distinct features of the ¹⁸⁷Os / ¹⁸⁸Os excursion that are correlatable among sections are proposed as chemostratigraphic markers which can serve as age control points with a precision of ca. ± 0.1 Myr. We propose a speculative hypothesis that higher cosmic dust flux in the Late Eocene may have contributed to global cooling and Early Oligocene glaciation (Oi-1) by supplying bio-essential trace elements to the oceans and thereby resulting in higher ocean productivity, enhanced burial of organic carbon and draw down of atmospheric CO₂. To determine if the hypothesis that enhanced cosmic dust flux in the Late Eocene was a cause for the ¹⁸⁷Os / ¹⁸⁸Os excursion can be tested by using the paired bulk sediment and leachate Os isotope composition; ¹⁸⁷Os / ¹⁸⁸Os were also measured in sediment leachates. Results of analyses of leachates are inconsistent between the south Atlantic and the Pacific sites, and therefore do not yield a robust test of this hypothesis. Comparison of ¹⁸⁷Os / ¹⁸⁸Os records with high resolution benthic foraminiferal δ¹⁸O records across the Eocene–Oligocene transition suggests that ¹⁸⁷Os flux to the oceans decreased during cooling and ice growth leading to the Oi-1 glaciation, whereas subsequent decay of ice-sheets and deglacial weathering drove seawater ¹⁸⁷Os / ¹⁸⁸Os to higher values. Although the precise timing and magnitude of these changes in weathering fluxes and their effects on the marine ¹⁸⁷Os / ¹⁸⁸Os records are obscured by recovery from the Late Eocene ¹⁸⁷Os / ¹⁸⁸Os excursion, evidence of the global influence of glaciation on supply of Os to the ocean is robust as it has now been documented in both Pacific and Atlantic records.     

Stratification and mixing of a post-glacial Neoproterozoic ocean: Evidence from carbon and sulfur isotopes in a cap dolostone from northwest China

To improve our knowledge about the geochemical and environmental aftermath of Neoproterozoic global glaciations, we analyzed stable isotopes (δ¹³C, δ¹⁸O, δ³⁴S) and elemental concentrations (Ca, Mg, S, Sr, Fe, and Mn) of the ～ 10-m-thick Zhamoketi cap dolostone atop the Tereeken diamictite in the Quruqtagh area, eastern Chinese Tianshan. Available chemostratigraphic data suggest that the Tereeken diamictite is probably equivalent to the Marinoan glaciation. Our new data indicate that organic and carbonate carbon isotopes of the Zhamoketi cap dolostone show little stratigraphic variations, averaging ? 28.2‰ and ? 4.6‰, respectively. In contrast, sulfur isotopes show significant stratigraphic variations. Carbonate associated sulfate (CAS) abundance decreases rapidly in the basal cap dolostone and δ³⁴S_CAS composition varies between + 9‰ and + 15‰ in the lower 2.5 m. In the overlying interval, CAS abundance remains low while δ³⁴S_CAS rises ～ 5‰ and varies more widely between + 10‰ and + 21‰. The range of δ³⁴S_py of the cap dolostone overlaps with that of δ³⁴S_CAS, but direct comparison shows that δ³⁴S_py is typically greater than δ³⁴S_CAS measured from the same samples. Hypotheses to explain the observations must account for both the remarkable sulfur isotope enrichment of pyrites and the inverse fractionation. We propose that CAS and pyrite were derived from two isotopically distinct reservoirs in a chemically stratified basin or a basin with a sulfate minimum zone. In this model, CAS was derived from shallow, oxic surface waters with moderate sulfate concentration and depleted in ³⁴S due to the post-glacial influx of sulfur from continental weathering. In contrast, pyrite was derived from anoxic bottom waters (or a sulfate minimum zone) with low sulfate concentration and ³⁴S enrichment due to long-term syn-glacial sulfate reduction. The rapid shift in CAS abundance and sulfur isotope composition within the cap dolostone is interpreted to reflect the mixing of the two reservoirs after initial deglaciation. Comparison with other post-Marinoan cap carbonates shows significant spatial heterogeneity in δ³⁴S_CAS, which together with strong temporal variation in δ³⁴S_CAS, points to generally low sulfate concentrations in post-Marinoan oceans.     

Transient ocean warming and shifts in carbon reservoirs during the early Danian

A long-standing question in Paleogene climate concerns the frequency and mechanism of transient greenhouse gas-driven climate shifts (hyperthermals). The discovery of the greenhouse gas-driven Paleocene–Eocene Thermal Maximum (PETM; ～ 55 Ma) has spawned a search for analogous events in other parts of the Paleogene record. On the basis of high-resolution bulk sediment and foraminiferal stable isotope analyses performed on three lower Danian sections of the Atlantic Ocean, we report the discovery of a possible greenhouse gas-driven climatic event in the earliest Paleogene. This event – that we term the Dan-C2 event – is characterized by a conspicuous double negative excursion in δ¹³C and δ¹⁸O, associated with a double spike in increased clay content and decreased carbonate content. This suggests a double period of transient greenhouse gas-driven warming and dissolution of carbonates on the seafloor analogous to the PETM in the early Paleocene at ～ 65.2 Ma. However, the shape of the two negative carbon isotope excursions that make up the Dan-C2 event is different from the PETM carbon isotope profile. In the Dan-C2 event, these excursions are fairly symmetrical and each persisted for about ～ 40 ky and are separated by a short plateau that brings the combined duration to ～ 100 ky, suggesting a possible orbital control on the event. Because of the absence of a long recovery phase, we interpret the Dan-C2 event to have been associated with a redistribution of carbon that was already in the biosphere. The Dan-C2 event and other early Paleogene hyperthermals such as the short-lived early Eocene ELMO event may reflect amplification of a regular cycle in the size and productivity of the marine biosphere and the balance between burial of organic and carbonate carbon.     

Permo-Pennsylvanian palaeotemperatures from Fe-Oxide and phyllosilicate δ18O values

The oxygen isotope composition of fossil roots that have been permineralized by hematite are presented from eight different stratigraphic levels spanning the Upper Pennsylvanian and Lower Permian strata of north-central Texas. Hematite δ¹⁸O values range from − 0.4% to 3.7%. The most negative δ¹⁸O values occur in the upper Pennsylvanian strata, and there is a progressive trend toward more positive δ¹⁸O values upward through the lower Permian strata. This stratigraphic pattern is similar in magnitude and style to δ¹⁸O values reported for penecontemporaneous authigenic palaeosol phyllosilicates and calcites, suggesting that all three minerals record similar paragenetic histories that are probably attributed to temporal palaeoenvironmental changes across the Late Pennsylvanian and Early Permian landscapes.Palaeotemperature estimates based on paired δ¹⁸O values between penecontemporaneous hematite and phyllosilicate samples suggest these minerals co-precipitated at relatively low temperatures that are consistent with a supergene origin in a low-latitude soil-forming environment. Hematite–phyllosilicate δ¹⁸O pairs indicate (1) relatively low soil temperatures (∼ 24 ± 3 °C) during deposition of the upper Pennsylvanian strata followed by (2) a considerable rise in soil temperatures (∼ 35–37 ± 3 °C) during deposition of the lowermost Permian strata. Significantly, δD and δ¹⁸O values of contemporaneous phyllosilicates provide single mineral palaeotemperature estimates that are analytically indistinguishable from temperature estimates based on hematite–phyllosilicate oxygen isotope pairs. The results between the two temperature-proxy methods suggest that the inferred large temperature change across the Upper Pennsylvanian–Lower Permian boundary might be taken seriously. If real, such a significant climate change would have undoubtedly had far-reaching ecological effects within this region of Pangaea. Notably, there are important lithological and palaeobotanical changes, such as disappearance of coal and coal swamp floras, across the Upper Pennsylvanian–Early Permian boundary of north-central Texas that may be consistent with major climatic change toward warmer conditions.     

Oxygen isotope constraints on the origin and differentiation of the Moon

We report new high-precision laser fluorination three-isotope oxygen data for lunar materials. Terrestrial silicates with a range of δ¹⁸O values (− 0.5 to 22.9‰) were analyzed to independently determine the slope of the terrestrial fractionation line (TFL; λ = 0.5259 ± 0.0008; 95% confidence level). This new TFL determination allows direct comparison of lunar oxygen isotope systematics with those of Earth. Values of Δ¹⁷O for Apollo 12, 15, and 17 basalts and Luna 24 soil samples average 0.01‰ and are indistinguishable from the TFL. The δ¹⁸O values of high- and low-Ti lunar basalts are distinct. Average whole-rock δ¹⁸O values for low-Ti lunar basalts from the Apollo 12 (5.72 ± 0.06‰) and Apollo 15 landing sites (5.65 ± 0.12‰) are identical within error and are markedly higher than Apollo 17 high-Ti basalts (5.46 ± 0.11‰). Evolved low-Ti LaPaz mare-basalt meteorite δ¹⁸O values (5.67 ± 0.05‰) are in close agreement with more primitive low-Ti Apollo 12 and 15 mare basalts. Modeling of lunar mare-basalt source composition indicates that the high- and low-Ti mare-basalt mantle reservoirs were in oxygen isotope equilibrium and that variations in δ¹⁸O do not result from fractional crystallization. Instead, these differences are consistent with mineralogically heterogeneous mantle sources for mare basalts, and with lunar magma ocean differentiation models that result in a thick feldspathic crust, an olivine–pyroxene-rich mantle, and late-stage ilmenite-rich zones that were convectively mixed into deeper portions of the lunar mantle. Higher average δ¹⁸O (WR) values of low-Ti basalts compared to terrestrial mid ocean ridge basalts (Δ=0.18‰) suggest a possible oxygen isotopic difference between the terrestrial and lunar mantles. However, calculations of the δ¹⁸O of lunar mantle olivine in this study are only 0.05‰ higher than terrestrial mantle olivine. These observations may have important implications for understanding the formation of the Earth–Moon system.     

Spatial–temporal changes in Andean plateau climate and elevation from stable isotopes of mammal teeth

Paleoelevation constraints from fossil leaf physiognomy and stable isotopes of sedimentary carbonate suggest that significant surface uplift of the northern Andean plateau, on the order of 2.5 ± 1 km, occurred between ～ 10.3 and 6.4 Ma. Independent spatial and temporal constraints on paleoelevation and paleoclimate of both the northern and southern plateau are important for understanding the distribution of rapid surface uplift and its relation to climate evolution across the plateau. This study focuses on teeth from modern and extinct mammal taxa (including notoungulates, pyrotheres, and litopterns) spanning ～ 29 Ma to present, collected from the Altiplano and Eastern Cordillera of Bolivia (16.2°S to 21.4°S), and lowland Brazil. Tooth enamel of large, water-dependent mammals preserves a record of surface water isotopes and the type of plants that animals ingested while their teeth were mineralizing. Previous studies have shown that the δ¹⁸O of modern precipitation and surface waters decrease systematically with increasing elevations across the central Andes. Our results from high elevation sites between 3600 and 4100 m show substantially more positive δ¹⁸O values for late Oligocene tooth samples compared to < 10 Ma tooth δ¹⁸O values. Late Oligocene teeth collected from low elevation sites in southeast Brazil show δ¹⁸O values similar (within 2‰) to contemporaneous teeth collected at high elevation in the Eastern Cordillera. This affirms that the Andean plateau was at a very low elevation during the late Oligocene. Late Oligocene teeth from the northern Eastern Cordillera also yield consistent δ¹³C values of about ? 9‰, indicating that the environment was semi-arid at that time. Latitudinal gradients in δ¹⁸O values of late Miocene to Pliocene fossil teeth are similar to modern values for large mammals, suggesting that by ～ 8 Ma in the northern Altiplano and by ～ 3.6 Ma in the southern Altiplano, both regions had reached high elevation and established a latitudinal rainfall gradient similar to modern.