Positive δ18O Values Research Articles

Stable isotopes of atmospheric water vapour and precipitation in the northeast Qinghai‐Tibetan Plateau

AbstractStable water isotopes (δ18O and δ2H) are an important source signature for understanding the hydrological cycle and altered climate regimes. However, the mechanisms underlying atmospheric water vapour isotopes in the northeast Qinghai‐Tibetan Plateau of central Asia remain poorly understood. This study initially investigated water vapour isotopic composition and its controls during the premonsoon and monsoon seasons. Isotopic compositions of water vapour and precipitation exhibited high variability across seasons, with the most negative average δ18O values of precipitation and the most positive δ18O values of water vapour found during the premonsoon periods. Temperature effect was significant during the premonsoon period but not the monsoon period. Both a higher slope and intercept of the local meteoric water line were found during the monsoon period as compared with in the premonsoon period, suggesting that raindrops have been experienced a greater kinetic fractionation process such as reevaporation below the cloud during the premonsoon periods. The δ2H and δ18O signatures in atmospheric water vapour tended to be depleted with the occurrence of precipitation events especially during the monsoon period and probably as a result of rainout processes. The monthly average contribution of evaporation from the lake to local precipitation was 35.2%. High d‐excess values of water vapour were influenced by the high proportion of local moisture mixing, as indicated by the gradually increasing relative humidity along westerly and Asian monsoon trajectories. The daily observation (observed ε) showed deviations from the equilibrium fractionation factors (calculated ε), implying that raindrops experienced substantial evaporative enrichment during their descent. The average fraction of raindrops reevaporation was estimated to be 16.4± 12.9%. These findings provide useful insights for understanding the interaction between water vapour and precipitation, moisture sources, and help in reconstructing the paleoclimate in the alpine regions.

Oceanographic and sedimentological influences on carbonate geochemistry and mineralogy in hypersaline coastal lagoons, Rio de Janeiro state, Brazil

AbstractThe Região dos Lagos situated along the coast east of Rio de Janeiro, Brazil, is dominated by a semiarid microclimate attributed to the occurrence of oceanographic upwelling at nearby Cabo Frio. The upwelling is strongly associated with the dominance of NE winds during austral spring/summer and the directional change of the shoreline orientation. Some coastal hypersaline lagoons from this region have been studied intensively over the last 25 yr because they represent relatively rare sites of modern primary dolomite precipitation. Comparison of environmental signals in three lagoons indicates that during the last ~ 3.0 kyr, changes in oceanographic parameters may have influenced biogeochemical processes associated with the production of carbonate‐bearing sediments. The timing of a decrease in sea level may have influenced a period of more intense upwelling, which coincides with precipitation of stoichiometric dolomite at ~ 2.3 kyr BP in the lagoons located along the coast directly west of Cabo Frio. The dolomite found in the lower sections of cores from Lagoa Vermelha and Brejo do Espinho contains more positive δ18O values, indicating greater evaporation with a period of increased semiarid conditions corresponding to greater terrestrial input. The lower δ13C values indicate re‐equilibration with the input of new carbonate ions derived from the decomposition of organic matter during dolomite formation. In contrast, the sediment core from Lagoa Salgada, located northeast of Cabo Frio, contains no dolomite, and very positive δ13C values recorded in carbonate sediments are attributed to microbially mediated methanogenesis, whereas δ18O values remain relatively constant throughout the core at around zero.

Petrological and geochemical constraints on the origin of dolomites: a case study from the early Cambrian Qingxudong Formation, Sichuan Basin, South China

Several types of dolomite had occurred pervasively in the lower Cambrian Qingxudong Formation in the Sichuan Basin. However, the origin of these dolomites remains particularly controversial until now. Here, we describe the petrographic and geochemical characteristics of dolomites from the lower Cambrian Qingxudong Formation in the southeastern Sichuan Basin, which can potentially provide useful information to constrain the origin and evolution of dolomitization fluid. Three fabric types and five dolomite generations were identified in this study: fabric-retentive dolomites (dolomicrite, Dol-1, and dolomitic microbialite, Dol-2), fabric-destructive dolomites (sucrosic dolomite, Dol-3) and pore-filling dolomites (medium- to coarse-crystalline dolomite, Dol-4, and saddle dolomite, Dol-5). The δ13C and δ18O values, 87Sr/86Sr ratios and rare earth element (REE) pattern of Dol-1, Dol-2 (except the δ13C values) and Dol-3 are approximately consistent with original seawater values, suggesting that the dolomitization fluids were mediated by seawater. The calculated dolomitization temperature (25.66 °C) and Z values (125.2) of Dol-1 with evaporite minerals indicate that the dolomitization fluid was high-salinity concentrated seawater derived from evaporation. The calculated dolomitization temperature (24.20 °C) and Z value (121.8) of Dol-2, and no traces of evaporite minerals in Dol-2 imply that the dolomitization fluid was slightly hypersaline seawater. The more negative δ13C and abundant microbial features of Dol-2 indicate that microbial mats were involved in dolomite formation. The dolomitization temperature (30.55 °C) and Z value (125) of Dol-3 also indicate that the dolomitization fluid was high-salinity concentrated seawater. However, Dol-3 is commonly distributed in reef and shoal facies (high porosity and permeability) throughout the Qingxudong Formation. Moreover, the abundant organic matters in the dolomitization fluid likely overcame the kinetic and thermodynamic barriers in the process of dolomitization. The geochemical data (except the δ18O values) of Dol-4 are approximately consistent with fabric-retentive dolomites, suggesting that the Dol-4 had been inherited from precursor carbonates. The negative δ18O values of Dol-4 revealed a further burial environment. High LREE/HREE ratios, positive europium anomalies and negative δ18O values of Dol-5 suggest that these dolomites were affected by hydrothermal fluids under deep burial conditions. Thus, Dol-1, Dol-2 and Dol-3 are likely attributed to sabkha, organogenic (microbial) and seepage-reflux dolomitization models during early-stage diagenesis, respectively. Dol-4 and Dol-5 are commonly attributed to burial and hydrothermal dolomitization models during deep burial diagenesis. This study provides new insights into the origin of dolomites and is especially useful for the further understanding of dolomite reservoir formation in the Qingxudong Formation.

Unusual Uranium‐rich Fluid Flow During Exhumation of Deeply Subducted Continental Crust

AbstractIn‐situ SIMS analyses of O and U‐Pb isotopes were carried out for zircons from a quartz vein hosted by ultrahigh‐pressure metagranite (UHP) in the Dabie orogen. The results are integrated to decipher the property of unusual U‐rich aqueous fluids and their effects on both metamorphic and magmatic zircons during exhumation of the UHP metagranite. In CL images, most zircon grains show distinct core‐rim structures. Relict cores are bright and exhibit oscillatory or patchy zonation, giving Neoproterozoic upper‐intercept ages of 795 ± 26 Ma. Newly grown rims are dark and exhibit no zoning, yielding Triassic concordant ages of 215 ± 5 Ma. The cores give Th contents of 59 to 463 ppm and U contents of 98 to 558 ppm, with Th/U ratios of 0.263 to 1.423. The rims yield reduced Th contents of 11 to 124 ppm but significantly elevated U contents of 1051 to 3531 ppm, with Th/U ratios of 0.010 to 0.035. Comparison with the cores of magmatic origin, the unusual enrichment in U but depletion in Th in the rims of metamorphic origin are interpreted as zircon growth from Cl‐rich oxidized vein‐forming aqueous fluids that were produced by dehydration reactions of the wallrock during continental exhumation. The cores have variably positive δ18O values with concordant or discordant Neoproterozoic U‐Pb ages, suggesting their solid‐state modification of both O and U‐Pb isotopes through interaction with the fluids. The rims yield negative δ18O values, indicating their growth from the negative δ18O fluids. Taken together, the proposed Cl‐rich oxidized negative‐δ18O vein‐forming aqueous fluids have such an ability to not only cause variable metamorphic recrystallization in the relict magmatic zircons but also produce dramatic fractionation of U over Th in the metamorphic zircons during quartz veining, and potentially impact on the overlain metasomatite in the mantle wedge.

Quantitative organic-walled dinoflagellate cyst stratigraphy across the Eocene-Oligocene Transition in the Gulf of Mexico: A record of climate- and sea level change during the onset of Antarctic glaciation

The Eocene – Oligocene Transition (EOT, 34–33.5 Ma) marks a major transition in Cenozoic climate evolution through the relatively rapid establishment of a continental-scale ice sheet on Antarctica. The EOT is characterized by two 200 kyr spaced shifts (termed EOT-1 and Oi-1) in the oxygen isotopic composition (δ18O) of benthic foraminifera, representing both changes in continental ice-volume and temperature. Estimates of the timing and magnitude of these changes during this critical phase in Earth’s climatic evolution are controversial. Here we present marine palynological assemblage data, in particular of organic-walled dinoflagellate cysts (dinocysts), across a classic upper Eocene to lower Oligocene neritic succession cored in Alabama, USA; the Saint Stephens Quarry (SSQ) borehole. These palynological data combined with lithological information allow the identification of three sequence boundaries across the EOT. Critically, we identify a sequence boundary at the level corresponding to the EOT-1. Integrated sea level and paleotemperature records show that EOT-1 primarily represents cooling with some minor and transient continental ice sheet expansion. Furthermore, we identify a significant hiatus, likely caused by major sea level fall at the base of Magnetochron C13n that corresponds to the Oi-1 shift. This clarifies the δ18O records from SSQ that essentially lack the expected pronounced shift to positive δ18O values so characteristic for Oi-1. Furthermore, we document originations and extinctions of potentially temperature-sensitive dinocysts associated with the EOT-1. In contrast, the Oi-1 does not stand out as period of substantial dinoflagellate turnover. The combined results illustrate that major cooling, limited and transient ice growth and major biotic change were occurring before the full-size expansion of the Antarctic cryosphere. © 2018 The Authors.

Nd-O-Hf isotopic decoupling in S-type granites: Implications for ridge subduction

The generation of S-type granites in the continental crust generally requires partial melting of metasedimentary rocks at relatively high temperatures, and is typically associated with syn- or post-collisional tectonics. These melts are generally expected to inherit the geochemical characteristics of their metasedimentary protoliths, and their Nd, Hf, and O isotopic compositions have been widely used to trace the origin of the magmas. Here we show that these isotopic systems are decoupled in S-type granites from the Chinese Altai, displaying a wide range of zircon ɛHf(t) values (−0.7 to +6.2), and a limited range of whole rock ɛNd(t) values (−6.1 to −2.2) and zircon δ18O values (+8.49‰ to +12.91‰). Zircon xenocrysts are common in these plutons, and show markedly negative ɛHf(t) values (from −30.7 to −18) and highly positive δ18O values (from +9.61‰ to +13.03‰). In addition, these granites exhibit high Lu/Hf (0.15 to 1.38) ratios, and substantial depletions in Zr and Hf. We develop a new model to explain the observed relationship between residual zircon content and Nd–Hf–O isotope decoupling. We propose that these S-type granites formed from partial melting of metasedimentary crustal rocks, associated with a ridge subduction-related heat source. Limited crustal heating, due to mantle upwelling through the slab window on a small scale, may have resulted in significant disequilibrium melting of the metasedimentary crust. Our findings provide new insights into melting processes in the deep continental crust.

Stable isotope ratios of typhoon rains in Fuzhou, Southeast China, during 2013–2017

Stable isotope ratios (δ2H and δ18O) in precipitation not only show a certain response to climate change at different time scales, but also have strong linkages to extreme weather events such as tropical cyclones (hurricanes/typhoons). Typhoon activity in the coastal region of Southeast China is quite intense, bringing huge amounts of moisture; thus, contributing to extreme rainfall in this region. The existing isotope data in Southeast China is available on a monthly or daily temporal resolution, which is inadequate to study 1–2-day-long typhoon rainfall events at a particular location. In this study, hourly rainfall δ2H and δ18O data are collected for eight typhoon events from 2013 to 2017 in Fuzhou, Southeast China. The total correlation between δ2H and δ18O is obtained as δ2H = 7.41 δ18O + 0.81 (R2 = 0.96, N = 220). All the eight typhoon events reveal a similar variability pattern in δ18O values which can be divided into three stages. More positive δ18O values occur in the first and third stages, while the second stage is dominated by most negative δ18O values, exhibiting an inverted U-shaped pattern. The positive δ18O values during the first and third stages are governed by re-evaporation. The precipitation during the second stage has distinctly lower δ18O values than the weighted average δ18O of summer precipitation in Fuzhou. Some of these values are slightly lower than those of the water vapor over the Pacific Ocean’s surface. No significant relationship is observed between precipitation δ18O and temperature as well as the amount of precipitation during the second stage. We hypothesize that the significant 18O-depletion is mainly caused by the ‘rain shield effect’, which refers to combination of large-scale convection, high condensation efficiency, and recycling of isotopically depleted vapor in rain shield areas leading to very negative δ18O values during typhoon system. These findings suggest the use of stable isotope ratios as important tracers of typhoon water.

Silica-rich septarian concretions in biogenic silica-poor sediments: A marker of hydrothermal activity at fossil hyper-extended rifted margins (Err nappe, Switzerland)

Silica-rich septarian concretions occur within Pliensbachian-Oxfordian syn-rift to early post-rift sediments of the fossil distal Adriatic rifted margin today exposed in the Err nappe (Central Alps). The concretions, ranging in size from few centimeters to about 2 m, consist of partially to completely siliceous spheroidal bodies developed within fine-grained sedimentary rock (mud to fine sand) with no or very scarce content in biogenic silica such as radiolarian tests. These concretions are characterized by a network of septarian cracks filled with chalcedony, quartz and locally, saddle dolomite. Some concretions are in their original position, whereas others are fragmentary and preserved in coarse-grained turbiditic beds, implying that concretionary growth had occurred prior to significant burial. Fluid inclusion temperatures (~150 °C), the positive δ18O values for original fluids (up to +7‰ SMOW), and the high 87Sr/86Sr values of dolomite point to a deep circulation of seawater into fault damage zones developed in granitic basement rocks. In their ascent, these hot, silica-rich fluids crossed compact sediments giving rise to quartz-dolomite veins. Lastly, when reaching the uncompacted soft sediments close to the seafloor, silica (quartz and chalcedony) locally precipitated in sediment pores and/or fissures leading to the formation of the siliceous septarian concretions. The anomalous quartz-rich mineralogy of the concretion body and of the authigenic crack-filling minerals, the occurrence in clastic sediments from deep-water distal rifted margins as well as high formation temperatures represent a new discovery enlarging the spectrum of septarian concretion types and the environment where they may grow. They provide a possible record of the subbottom products of hydrothermal venting typifying hyper-extended rifted margins where extensional detachment faults exhume crustal rocks to the seafloor and lead to an intense fluid-rock interaction and silica enrichment in the fluids.

Isotopic composition of daily precipitation along the southern foothills of the Himalayas: impact of marine and continental sources of atmospheric moisture

Abstract. The flow of the Himalayan rivers, a key source of fresh water for more than a billion people primarily depends upon the strength, behaviour and duration of the Indian summer monsoon (ISM) and the western disturbances (WD), two contrasting circulation regimes of the regional atmosphere. An analysis of the 2H and 18O isotope composition of daily precipitation collected along the southern foothills of the Himalayas, combined with extensive backward trajectory modelling, was used to gain deeper insight into the mechanisms controlling the isotopic composition of precipitation and the origin of atmospheric moisture and precipitation during ISM and WD periods. Daily precipitation samples were collected during the period from September 2008 to December 2011 at six stations, extending from Srinagar in the west (Kashmir state) to Dibrugarh in the east (Assam state). In total, 548 daily precipitation samples were collected and analysed for their stable isotope composition. It is suggested that the gradual reduction in the 2H and 18O content of precipitation in the study region, progressing from δ18O values close to zero down to ca. −10 ‰ in the course of ISM evolution, stems from regional, large-scale recycling of moisture-driven monsoonal circulation. Superimposed on this general trend are short-term fluctuations of the isotopic composition of rainfall, which might have stem from local effects such as enhanced convective activity and the associated higher degree of rainout of moist air masses (local amount effect), the partial evaporation of raindrops, or the impact of isotopically heavy moisture generated in evapotranspiration processes taking place in the vicinity of rainfall sampling sites. Seasonal footprint maps constructed for three stations representing the western, central and eastern portions of the Himalayan region indicate that the influence of monsoonal circulation reaches the western edges of the Himalayan region. While the characteristic imprint of monsoonal air masses (increase of monthly rainfall amount) can be completely absent in the western Himalayas, the onset of the ISM period in this region is still clearly visible in the isotopic composition of daily precipitation. A characteristic feature of daily precipitation collected during the WD period is the gradual increase of 2H and 18O content, reaching positive δ2H and δ18O values towards the end of the period. This trend can be explained by the growing importance of moisture of continental origin as a source of daily precipitation. High deuterium-excess (d-excess) values of daily rainfall recorded at the monitoring stations (38 cases in total, range from 20.6 to 44.0 ‰) are attributed to moisture of continental origin released into the atmosphere during the evaporation of surface water bodies and/or soil water evaporation.

Petrography, fluid-inclusion, isotope, and trace-element constraints on the origin of quartz cementation and feldspar dissolution and the associated fluid evolution in arkosic sandstones

Feldspar dissolution, quartz cementation, and clay cementation are significant diagenetic processes in deep-water fan feldspar-rich sandstones in the Shengtuo area, Dongying sag (East China). The timing and origin of these water–rock interactions as well as the paleofluids in which relevant chemical reactions occurred were deduced using data from microscopy, fluid-inclusion microthermometry, oxygen-isotope microanalysis, and trace-element microanalysis. Three distinct, separate episodes of quartz overgrowths (referred to as Q1, Q2, and Q3) were distinguished by cathodoluminescence microscopy. The Q1 quartz, identified in all porous sandstones from 2500 to 3600 m (8200 to 11,800 ft), was formed at approximately 100°C–115°C (212°F–239°F) before oil filled the reservoirs. The Q2 quartz was mainly precipitated at 115°C–130°C (239°F–275°F), accompanying or slightly postdating the main phase of oil filling, and was identified in samples from 2800 to 3600 m (9200 to 11,800 ft). The Q3 quartz was only identified in sandstones buried deeper than 3500 m (11,400 ft) and was likely precipitated in the Quaternary when temperature exceeded 130°C–135°C (266°F–275°F). Secondary ion mass spectrometry oxygen-isotope microanalyses yielded δ18OVSMOW (Vienna standard mean ocean water) values ranging from 21.42‰ to 24.35‰ for Q1 quartz, from 22.03‰ to 24.99‰ for Q2 quartz, and from 21.72‰ to 22.91‰ for Q3 quartz. A mass-balance calculation and quantitative petrography data of the amount of leached feldspars and associated secondary minerals suggest that the internal feldspar dissolution is likely the primary source for the authigenic clays and quartz cements in these sandstones. Positive δ18O(water) values (+0.5‰ to +4.5‰ VSMOW) of quartz-forming waters indicate that quartz cementation and feldspar dissolution occurred in a geochemical system with a limited volume of diagenetically modified connate water. The variations of δ18O(cements) and trace-element compositions from Q1 quartz to Q2 quartz in individual overgrowth suggest that hydrocarbon filling changed the chemistry of the pore fluid significantly; further, δ18O(water) values of the pore water increased by approximately 2‰ VSMOW after oil filling. Meteoric freshwater did not contribute to quartz cementation and simultaneous feldspar dissolution. The detected CO2 and hydrocarbons in fluid inclusions in the quartz cements, the existence of CO2 in hydrocarbon-rich natural gas, and the pyrobitumen in the feldspar-hosted pores suggest that acids derived from organic matter (kerogen in source rocks and hydrocarbons in reservoirs) probably have promoted the extensive subsurface leaching reactions of feldspars in these sandstones. The ongoing development of Q2 and Q3 quartz suggests that quartz precipitation did not cease after oil filling. Further, diagenetic reactions likely have proceeded from water–rock interactions to hydrocarbon–water–rock interactions.

Mesolithic human occupation and seasonality: sclerochronology, δ18O isotope geochemistry, and diagenesis verification by Raman and LA-ICP-MS analysis of Argyrosomus regius (meagre) sagittae otoliths from layer 1 of Cabeço da Amoreira Mesolithic shell midden (Muge, Portugal)

We present preliminary sclerochronological analysis on 15 Argyrosomus regius (meagre) otoliths collected from two different human occupation levels from the Cabeco da Amoreira shell midden (Muge valley, Portugal). The otoliths were sectioned and observed under a reflected light stereomicroscope to examine seasonal growth rings. Carbonates collected from individual growth rings subsampled with a micromill sampling device were analyzed for their stable oxygen isotope content with the objective of determining the predominant season of capture and therefore season of site use, environmental conditions, and sites of resource procurement (local versus regional). The otoliths’ stable isotope records show clear seasonality and a season of capture estimate that seems consistent with a “good season” (warmer season, i.e., from spring to late summer/beginning of autumn in this area) site use in the last occupation layer (the great majority of otoliths are from layer 1), except for four samples giving heaver oxygen isotope (δ18O) values that suggest colder conditions and only one with markedly positive δ18O values. Potential effect of diagenesis on the otolith records was also assessed through coupled laser ablation–inductively coupled plasma mass spectrometry (LA-ICP-MS) and by micro-X-Ray diffraction (μ-XRD). Results revealed the presence of only aragonite and no traces of calcite, providing no evidence of diagenesis that could significantly alter isotope results and lead to erroneous interpretations. The implications of these results are discussed and compared with data from other archeological sites, as well as data from micromorphology regarding continuity or interruption of site use and other faunal remains.

Revised interpretations of stable C and O patterns in carbonate rocks resulting from meteoric diagenesis

A positive correlation between the δ13C and δ18O values of carbonate rocks is a screening tool widely used to identify the overprint of meteoric diagenesis on the original isotopic composition of a sample. In particular, it has been suggested that systematic change from negative to positive δ13C and δ18O values with increasing depth in the core is an indicator of alteration within the zone of mixing between meteoric and marine waters. In this paper, we propose that such covariance is not generated within the traditionally defined mixing zone, and that positive correlations between δ13C and δ18O values in marine carbonates are not necessarily indicators of meteoric alteration. This new interpretation is based on data collected from the shallow sub-surface of the Bahamas, a region unequivocally influenced by meteoric waters to depths of at least 200m below the current sediment-water interface. The classic interpretation of the diagenetic environments, based on changes in the δ13C and δ18O values, would suggest the maximum penetration of freshwater occurs between 65 and 100m below seafloor. Below these depths, a strong positive covariation between the δ13C and δ18O values exists, and would traditionally be defined as the mixing zone. However, based upon known changes in sea level, the penetration of the freshwater lens extends significantly below this limit. We contend that the zone showing covariance of δ13C and δ18O values is actually altered within the freshwater lens, and not the mixing zone as previously proposed. The co-varying trend in δ13C and δ18O values is the result of diagenetic processes occurring at the interface between vadose and phreatic zones. Significantly greater rates of recrystallization and neomorphism are driven by the increased rates of oxidation of organic matter at this transition with progressively less alteration occurring with increasing depth. As sea level oscillates, the position of this interface moves through the deposit, causing cumulative alteration throughout the section. Hence, we propose that the covariation between δ13C and δ18O values is a consequence of varying degrees of alteration, rather than the result of diagenesis occurring within the zone where marine and freshwater fluids mix. Furthermore, within the pervasively altered vadose zone, there is little correlation between δ13C and δ18O values, and therefore covariation between δ13C and δ18O values is not an unequivocal indicator of meteoric diagenesis.

Impacts of dominated landscape types on hydrogen and oxygen isotope effects of spring water in the Hani Rice Terraces

Analysis of hydrogen and oxygen stable isotopes is an effective method to track the water cycle in watershed. Impact of landscape pattern on the isotope effects of spring water is a new interdisciplinary topic between landscape ecology and isotope hydrology. Taking the Quanfuzhuang River basin located in the core area of UNESCO World Cultural Heritage of Honghe Hani Rice Terrace as the object, collecting the monthly samples of 78 points of spring water and 39 precipitation at altitude of 1500 m (terraces), 1700 m (terraces) and 1900 m (forest) from March 2015 to March 2016, we analyzed the hydrogen and oxygen stable isotopes of water samples under the different landscape types. The results indicated that the dominated landscape types were forests and rice terraces, being 66.6% and 22.1% of the whole landscape area respectively, and they had a spatial vertical pattern of forest located at the mountain top and rice terraces at the down-slope. The correlation analysis showed that the spring water not only came from the precipitation, but also from other water sources which had a more positive δ18O and δD values, the spring water in up-slope forests mainly came from precipitation, while that in down-slope rice terraces came from precipitation, ri-ver water, rice terrace water and under ground water. Therefore, the mixing effects of spring water δ18O and δD were more significant in rice terraces. The overall altitude effect of the hydrogen and oxygen stable isotopes in spring water was obvious. The linear decreasing rates of δ18O and δD values were -0.125‰·(100 m)-1and -0.688‰·(100 m)-1, respectively. The deuterium surplus value increased with the altitude because of the impacts of landscape pattern and the local cycle of water isotopes. In summary, the dominant landscape types had a significant impact on the hydrogen and oxygen isotopes of spring water, which could be used as response indicator to reveal the impacts of landscape pattern on hydrological process.

A Nd- and O-isotope study of the REE-rich peralkaline Strange Lake granite: implications for Mesoproterozoic A-type magmatism in the Core Zone (NE-Canada)

It is well established that A-type granites enriched in high field strength elements, such as Zr, Nb and the REE, form in anorogenic tectonic settings. The sources of these elements and the processes controlling their unusual enrichment, however, are still debated. They are addressed here using neodymium and oxygen isotope analyses of samples from the 1.24 Ga Strange Lake pluton in the Paleoproterozoic Core Zone of Quebec-Labrador, an A-type granitic body characterized by hyper-enrichment in the REE, Zr, and Nb. Age-corrected eNd values for bulk rock samples and sodic amphiboles (mainly arfvedsonite) from the pluton range from −0.6 to −5.7, and −0.3 to −5.3, respectively. The eNd values for the Napeu Kainiut quartz monzonite, which hosts the pluton, range from −4.8 to −8.1. The 147Sm/144Nd ratios of the suite and the host quartz monzonite range from 0.0967 to 0.1659, large variations that can be explained by in situ fractionation of early LREE-minerals (Strange Lake), and late hydrothermal HREE remobilization. Oxygen isotope analyses of quartz of both Strange Lake and the host yielded δ18O values between +8.2 and +9.1, which are considerably higher than the mantle value of 5.7 ± 0.2‰. Bulk rock oxygen isotope analyses of biotite-gneisses in the vicinity of the Strange Lake pluton yielded δ18O values of 6.3, 8.6 and 9.6‰. The negative eNd values and positive δ18O values of the Strange Lake and Napeu Kainiut samples indicate that both magmas experienced considerable crustal contamination. The extent of this contamination was estimated, assuming that the contaminants were sedimentary-derived rocks from the underlying Archean Mistinibi (para-) gneiss complex, which is characterized by low eNd and high δ18O values. Mixing of 5–15% of a gneiss, having an eNd value of −15 and a δ18O value of +11, with a moderately enriched mantle source (eNd = +0.9, δ18O = +6.3) would produce values similar to those obtained for the Strange Lake granites. Based on analogies between the Nain Plutonic Suite and the Gardar alkaline igneous province (SW-Greenland), we conclude that the Strange Lake pluton and associated REE-mineralized anorogenic bodies formed from a combination of subduction-induced fertilization of the sublithospheric mantle, crustal extension and in situ magma evolution.

Authigenic minerals from the Paola Ridge (southern Tyrrhenian Sea): Evidences of episodic methane seepage

Paola Ridge, along the NW Calabrian margin (southern Tyrrhenian Sea), is one of the few reported deep sea sites of precipitation of authigenic carbonates in the Tyrrhenian Sea. Here, the changing composition of the seeping fluids and the dynamic nature of the seepage induced the precipitation of pyrite, siderite and other carbonate phases. The occurrence of this array of authigenic precipitates is thought to be related to fluctuation of the sulfate-methane transition zone (SMTZ).Concretions of authigenic minerals formed in the near sub-bottom sediments of the Paola Ridge were investigated for their geochemical and isotopic composition. These concretions were collected in an area characterized by the presence of two alleged mud volcanoes and three mud diapirs. The mud diapirs are dotted by pockmarks and dissected by normal faults, and are known for having been a site of fluid seepage for at least the past 40 kyrs. Present-day venting activity occurs alongside the two alleged mud volcanoes and is dominated by CO2-rich discharging fluids. This discover led us to question the hypothesis of the mud volcanoes and investigate the origin of the fluids in each different domed structure of the study area.In this study, we used stable isotopes (carbon and oxygen) of carbonates coupled with rare earth element (REE) composition of different carbonate and non-carbonate phases for tracing fluid composition and early diagenesis of authigenic precipitates. The analyses on authigenic precipitates were coupled with chemical investigation of venting gas and sea-water.Authigenic calcite/aragonite concretions, from surficial sediments on diapiric structures, have depleted 13C isotopic composition and slightly positive δ18O values. By contrast, siderite concretions, generally found within the first 6 m of sediments on the alleged mud volcanoes, yielded positive δ13C and δ18O values. The siderite REE pattern shows consistent LREE (light REE) fractionation, MREE (medium REE) enrichment and positive Gd and La anomalies. As shown by the REE distribution, the 13C-depleted composition and their association with chemosymbiotic fauna, calcite/aragonite precipitated at time of moderate to high methane flux close to the seafloor, under the influence of bottom seawater. Authigenic siderite, on the other hand, formed in the subseafloor, during periods of lower gas discharges under prolonged anoxic conditions within sediments in equilibrium with 13C-rich dissolved inorganic carbon (DIC) and 18O-rich water, likely related to methanogenesis and intermittent venting of deep-sourced CO2.

Dolomite geochemistry of the Cambrian Longwangmiao Formation, eastern Sichuan Basin: Implication for dolomitization and reservoir prediction

Based on petrology and mineralogy, the geochemical characteristics of dolomite in the Cambrian Longwangmiao Formation in the eastern Sichuan Basin, were carried out. Results showed that dolomites mainly occurred in the middle and upper parts of Longwangmiao Formation, with most commonly as a crystalline dolomite and less commonly as a gain dolomite; the percentage content of dolostone in dolomite ranged from 48.6% to 75%, ratios of Mg/Ca were generally small, and positive and negative relationships between content of MgO and content of CaO were identified, respectively; the dolostones were generally characterized by high contents of Fe and Na while low contents of Sr and Mn, and only a part of dolostones had high content of Mn; compared with composition of contemporaneous seawater, most of dolostones were characterized by positive δ13C values and negative δ18O values. Based on the analyses of regional geological setting and geochemical characteristics, the dolomite in Longwangmiao Formation was mainly from the seepage-refluxion dolomitization, while evaporative-concentration dolomitization and burial dolomitization were not developed. In general, the dolomitization of Longwangmiao Formation was not complete. Furthermore, through the dolomitization model of Longwangmiao Formation, the distribution of sedimentary facies as well as the controlling effect of dolomitization on reservoir, the favorable reservoir was predicted, and was mainly developed around Qiyueshan fault zone.

Mineralogical and chemical distribution of the Es3L oil shale in the Jiyang Depression, Bohai Bay Basin (E China): Implications for paleoenvironmental reconstruction and organic matter accumulation

The Es3L (lower sub-member of the third member of the Eocene Shahejie Formation) shale in the Jiyang Depression is a set of relatively thick and widely deposited lacustrine sediments with elevated organic carbon, and is considered to be one of the most important source rocks in East China. We can determine the mineralogy, organic and inorganic geochemistry of the Es3L shale and calculate paleoclimate indexes by using multiple geochemical proxies based on organic chemistry (total organic carbon [TOC] and Rock-Eval pyrolysis), major and trace elements, X-Ray diffraction, and carbon and oxygen isotope data from key wells alongside ECS (Elemental Capture Spectroscopy) well log data. These indicators can be used to analyze the evolution of the paleoenvironment and provide a mechanism of organic matter (OM) accumulation. The Es3L oil shale has high TOC abundance (most samples >3.0%) and is dominated by Type I kerogens. Additionally, the organic-rich shale is rich in CaO and enrichment in some trace metals is present, such as Sr, Ba and U. The positive δ13C and negative δ18O values, high Sr/Ba, B/Ga and Ca/Ca + Fe ratios and low C/S ratios indicate that the Es3L shales were mainly deposited in a semi-closed freshwater-brackish water lacustrine environment. The consistently low Ti/Al and Si/Al ratios reflect a restricted but rather homogeneous nature for the detrital supply. Many redox indicators, including the Th/U, V/(V + Ni), and δU ratios, pyrite morphology and TOC-TS-Fe diagrams suggest deposition under dysoxic to suboxic conditions. Subsequently, the brackish saline bottom water evolved into an anoxic water body under a relatively arid environment, during which organic-lean marls were deposited in the early stage. Later, an enhanced warm-humid climate provided an abundant mineral nutrient supply and promoted the accumulation of algal material. OM input from algal blooms reached a maximum during the deposition of the organic-rich calcareous shale with seasonal laminations. High P/Ti ratios and a strongly positive relationship between the P and TOC contents indicate that OM accumulation in the oil shale was mainly controlled by the high primary productivity of surface waters with help from a less stratified water column. Factors such as the physical protection of clay minerals and the dilution of detrital influx show less influence on OM enrichment.

Sedimentary response of lake El Tobar, Spain, to climate: lake level changes after the Maunder Minimum

ABSTRACTLake level reconstructions from a littoral core in lake El Tobar, Spain, are presented for the last 350 years. These are based on plant macrofossils and stable isotopes from lacustrine carbonates. Our data suggest five episodes of advance and regression of the shoreline coupled with changes in water retention in the lake. A low lake level and high water renewal episode at ca. AD 1650–1715 is indicated by oxidized facies with abundant remains from terrestrial/marsh plant macrofossils and low δ18O and δ13C values. A fluctuating lake level episode at ca. AD 1715–1772 during changing climatic conditions in the Little Ice Age (LIA) caused periods of erosion and sediment deposition that intermittently blocked the lake outlet, resulting in more positive δ18O and δ13C values. The lake became progressively more closed with increased level in the wet years at the end of the LIA (ca. AD 1772–1850). During the Dalton Minimum, δ13C values reached a minimum, indicating low productivity, but increased after this with development of submerged Chara. From ca. AD 1850 to 1960 lake levels were high but are marked by changes in marsh communities, mainly the shift from Juncus to Typha (ca. AD 1850–1960) predominance, which indicates low and high levels, respectively.

Low palaeoelevation of the northern Lhasa terrane during late Eocene: Fossil foraminifera and stable isotope evidence from the Gerze Basin.

The Lhasa terrane is a key region for understanding the paleoelevation of the southern Tibetan Plateau after India-Asia collision. The Gerze Basin, located in the northern part of the Lhasa terrane, is a shortening-related basin. We discovered Lagena laevis (Bandy) fossils in upper Eocene strata of the Gerze Basin. This type of foraminifera is associated with lagoon and estuarine environments, indicating that the northern part of the Lhasa terrane was near sea level during the late Eocene. We speculate that these foraminifera were transported inland by storm surges to low elevation freshwater lakes during times of marine transgressions. This inference is consistent with the relatively positive δ18O values in carbonate from the same deposits that indicate low palaeoelevations close to sea level. Considering the palaeoelevation results from the nearby Oligocene basins at a similar latitude and the volcanic history of the Lhasa terrane, we infer that large-magnitude surface uplift of the northern Lhasa terrane occurred between late Eocene and late Oligocene time.

Oxygen isotope records of Holocene climate variability in the Pacific Northwest

Oxygen isotope (δ18O) measurements of authigenic carbonate from Cleland Lake (southeastern British Columbia), Paradise Lake (central British Columbia), and Lime Lake (eastern Washington) provide a ∼9000 year Holocene record of precipitation-evaporation balance variations in the Pacific Northwest. Both Cleland Lake and Paradise Lake are small, surficially closed-basin systems with no active inflows or outflows. Lime Lake is surficially open with a seasonally active overflow. Water isotope values from Cleland and Paradise plot along the local evaporation line, indicating that precipitation-evaporation balance is a strong influence on lake hydrology. In contrast, Lime Lake water isotope values plot on the local meteoric water line, signifying minimal influence by evaporation. To infer past hydrologic balance variations at a high temporal resolution, we sampled the Cleland, Paradise, and Lime Lake sediment cores at 1–60 mm intervals (∼3–33 years per sample on average) and measured the isotopic composition of fine-grained (<63 μm) authigenic CaCO3 in each sample. Negative δ18O values, which indicate wetter conditions in closed-basin lakes, occur in Cleland Lake sediment from 7600 to 2200 years before present (yr BP), and are followed by more positive δ18O values, which suggest drier conditions, after 2200 yr BP. Highly negative δ18O values in the Cleland Lake record centered on ∼2400 yr BP suggest that lake levels were high (and that the lake may have been overflowing) at this time as a result of a substantially wetter climate. Similarly, Paradise Lake sediment δ18O values are relatively low from 7600 to 4000 yr BP and increase from ∼4000 to 3000 yr BP and from ∼2000 yr BP to present, indicating that climate became drier from the middle through the late Holocene. The δ18O record from Lime Lake, which principally reflects changes in the isotopic composition of precipitation, exhibits less variability than the closed-basin lake records and follows a generally increasing trend from the mid-Holocene to present. These results are consistent with several proximal reconstructions of changes in lake-level, precipitation amount, and precipitation isotopic composition and may also reflect the establishment of modern El Niño Southern Oscillation (ENSO) variability in the late Holocene, as inferred from proxy evidence of synoptic ocean-atmosphere changes in the Pacific basin. Results from mid-Holocene (6000 yr BP) climate model simulations conducted as part of the Paleoclimate Modeling Intercomparison Project Phase 3 (PMIP3) indicate that in much of western North America, the cold season (October–March) was wetter and the warm season (April–September) was considerably drier relative to the late Holocene, leading to an overall drier climate in western North America with enhanced hydroclimatic seasonality. This is consistent with inferences from the Cleland and Paradise δ18O records, which lake modeling experiments indicate are strongly influenced by cold season precipitation-evaporation balance. This also explains apparent inconsistencies between the lake δ18O records and other proxies of hydroclimatic change from the greater Pacific Northwest region that are less sensitive to cold season climate and thus indicate relatively drier conditions during the mid-Holocene. The abrupt negative excursion at ∼2400 yr BP in the Cleland Lake δ18O data, as well as the marked shift to more positive values after this time, demonstrate that gradual changes in ocean-atmosphere dynamics can produce abrupt, non-linear hydroclimate responses in the interior regions of western North America.