Increase In δ18O Research Articles

Isoscapes of δ18O and δ2H reveal climatic forcings on Alaska and Yukon precipitation

AbstractSpatially extensive Arctic stable isotope data are sparse, inhibiting the climatic understanding required to interpret paleoclimate proxy records. To fill this need, we constrained the climatic and physiographic controls on δ18O and δD values of stream waters across Alaska and the Yukon to derive interpolated isoscape maps. δ18O is strongly correlated to winter temperature parameters and similarity of the surface water line (δ2H = 8.0 × δ18O + 6.4) to the Global Meteoric Water Line suggests stream waters are a proxy for meteoric precipitation. We observe extreme orographic δ18O decreases and a trans‐Alaskan continental gradient of −8.3‰ 1000 km−1. Continental gradients are high in coastal zones and low in the interior. Localized δ18O increases indicate inland air mass penetration via topographic lows. Using observed δ18O/temperature gradients, we show that δ18O decreases in a ∼24 ka permafrost ice wedge relative to the late Holocene indicate mean annual and coldest quarter temperature reductions of 8.9 ± 1.7°C and 17.2 ± 3.2°C, respectively.

The Eocene-Oligocene climate transition in the Central Paratethys

We studied two boreholes (Cserépváralja-1 and Kiscell-1) with continuous sedimentary records across the Eocene-Oligocene climate transition from the Central Paratethyan area. Assemblages of benthic foraminifera display a shift in dominance by epifaunal taxa in the late Eocene to shallow and deep infaunal taxa in the early Oligocene. Using the benthic foraminiferal oxygen index (BFOI), a decreasing trend of bottom-water oxygen levels is established across the Eocene-Oligocene transition (EOT), leading to the development of dysoxic conditions later in the early Oligocene.Trends in δ18O and δ13C values measured on tests of selected benthic and planktic foraminifera roughly parallel those of the global record of stepped EOT δ18O increase and deviate only later in the early Oligocene, related to the isolation of the Paratethys. The overall similarity of the isotope curves and the presence of a planktic-benthic ecological offset suggest that the original isotope trends are preserved, despite the systematically more negative δ18O values. Of different scenarios, a quasi-uniform diagenetic overprint by fluids with low δ18O values, during burial or uplift, appears best supported. We conclude that the globally established isotopic expression of Antarctic ice sheet growth across the EOT may be recognizable in the Paratethys. Deviations from the global trends after the EOT were caused by regional paleoceanographic changes induced by the progressing Alpine orogeny and sea-level change, which led to a restricted connection with the open ocean, freshwater influx from increased precipitation, and gradual development of bottom-water oxygen depletion.

Last glacial-interglacial productivity and associated changes in the eastern Arabian Sea

We reconstruct paleo-productivity and bottom water oxygenation changes during the past 32ka, from the southeastern Arabian Sea, using absolute abundance of planktic foraminifera, relative abundance of Globigerina bulloides, angular asymmetrical benthic foraminifera (AABF), measurements of total organic carbon (Corg), %CaCO3, and Globigerinoides ruber δ18O and δ13C. The faunal and geochemical proxies suggest that productivity in the southeastern Arabian Sea was high during MIS 3. A distinct decrease in productivity is inferred during the last glacial maximum (19–23ka) (LGM). Bottom water was well oxygenated during MIS3, only to become oxygen-depleted during the LGM. Productivity decreased abruptly during Heinrich Stadial 1 (HS-1), but the response to Heinrich Stadial 2 (HS-2) was different. Low productivity during the early deglaciation is also synchronous with an increase in ice-volume corrected δ18O (δ18Osw-ivc), a salinity proxy, between 18.9 (18.3–18.9) ka BP and 15.9 (15.0–16.3) ka BP, and a concomitant decrease in δ13C between 18.2 (17.5–18.7) ka BP and 16.4 (15.3–16.7) ka BP. These patterns suggest that the global δ13C minimum event during the last deglaciation was associated with the weak monsoon interval during HS-1 and a drop in productivity in tropical regions. A progressive increase in productivity is observed throughout the Holocene, with a distinct jump at 5.4 (3.8–6.3) ka BP. We infer that although productivity was higher in the eastern Arabian Sea during most of the last glacial interval, the overall resultant carbon sequestration was confined only to a restricted zone and not large enough to substantially alter atmospheric CO2.

Oxygen isotope perspective on crustal evolution on early Earth: A record of Precambrian shales with emphasis on Paleoproterozoic glaciations and Great Oxygenation Event

We present stable isotope and chemical data for 206 Precambrian bulk shale and tillite samples that were collected mostly from drillholes on all continents and span the age range from 0.5 to 3.5 Ga with a dense coverage for 2.5–2.2 Ga time interval when Earth experienced four Snowball Earth glaciations and the irreversible rise in atmospheric O2. We observe significant, downward shift of several ‰ and a smaller range of δ18O values (7 to 9‰) in shales that are associated with the Paleoproterozoic and, potentially, Neoproterozoic glaciations. The Paleoproterozoic samples consist of more than 50% mica minerals and have equal or higher chemical index of alteration than overlying and underlying formations and thus underwent equal or greater degrees of chemical weathering. Their pervasively low δ18O and δD (down to −85‰) values provide strong evidence of alteration and diagenesis in contact with ultra-low δ18O glacial meltwaters in lacustrine, deltaic or periglacial lake (sikussak-type) environments associated with the Paleoproterozoic glaciations. The δDsilicate values for the rest of Precambrian shales range from −75 to −50‰ and are comparable to those for Phanerozoic and Archean shales. Likewise, these samples have similar ranges in δ13Corg values (−23 to −33‰ PDB) and Corg content (0.0 to 10 wt%) to Phanerozoic shales. Precambrian shales have a large range of δ18O values comparable to that of the Phanerozoic shales in each age group and formation, suggesting similar variability in the provenance and intensity of chemical weathering, except for the earliest 3.3–3.5 Ga Archean shales, which have consistently lower δ18O values. Moreover, Paleoproterozoic shales that bracket in age the Great Oxidation Event (GOE) overlap in δ18O values. Absence of a step-wise increase in δ18O and δD values suggests that despite the first-order change in the composition of the atmosphere, weathering cycle was not dramatically affected by the GOE at ∼2.4–2.3 Ga. Shales do not show comparable δ18O rise in the early Phanerozoic as is observed in the coeval δ18O trends for cherts and carbonates. There is however a sharp increase in the average δ18O value from the Early Archean to the Late Archean followed by a progressively decelerating increase into the Phanerozoic. This decelerating increase with time likely reflects declining contribution of mantle-extracted, normal-δ18O crust and lends support to crustal maturation and increasing 18O sequestration into the crust and recycling of high-δ18O (and 87Sr/86Sr) sedimentary rocks. This secular increase in the δ18O composition of the continental crust could have also had a mild effect on seawater δ18O composition.

Simultaneous assessment, through sap flow and stable isotopes, of water use efficiency (WUE) in thinned pines shows improvement in growth, tree-climate sensitivity and WUE, but not in WUEi

In water-limited regions, adaptive management of forest and water relationships has been put forward, to implement hydrology-oriented silviculture to reduce stand evapotranspiration and, at the tree level, to improve growth and water use efficiency (WUE). The main goal of this study was to evaluate the effect of thinning in the short and medium term on tree growth, climate (drought) sensitivity, WUE performed using growth and sap flow measurements and WUEi performed using δ13C and δ18O isotopes, in a typical semiarid forest. This approach also evaluated the reliability of isotopes as indicators of the effects of adaptive forest management. A stagnated Aleppo pine plantation was experimentally thinned at high intensity (H98) in 1998 and at High (H), Medium (M) and Low (L) intensities in 2008, along with a control (C). Substantial limitation of tree growth was observed in C. Thinning not only increased growth, but also changed the tree growth–precipitation relationships, with C trees depending more on precipitation than thinned trees did. WUEi after thinning was significantly affected only in the medium term, with C trees being more efficient (94.4 μmolCO2/molH2O) than H98 trees (88.7), especially in dry spells (100.7). WUEi was found to increase when precipitation decreased, regardless of the treatment. However, WUE increased sharply from C (1.26g biomass/L H2O) to H (3.20g/L), showing a clear difference with WUEi observed in the same years. Thinning caused an increase in δ18O in the short term, but no relationship was found between δ18O and tree water use. It can be concluded that forest management improved WUE in spite of higher tree transpiration, but WUEi remained unchanged, probably due to an underestimate of photosynthetic capacity. The dual isotope (δ13C and δ18O) conceptual model was not consistent with our experimental data. Thus, the question of whether stable isotopes can be used as a tool for addressing the ecophysiological impacts of thinning remains open.

Continuous monitoring of stream δ18O and δ2H and stormflow hydrograph separation using laser spectrometry in an agricultural catchment

AbstractA portable Wavelength Scanned‐Cavity Ring‐Down Spectrometer (Picarro L2120) fitted with a diffusion sampler (DS‐CRDS) was used for the first time to continuously measure δ18O and δ2H of stream water. The experiment took place during a storm event in a wet tropical agricultural catchment in north‐eastern Australia. At a temporal resolution of one minute, the DS‐CRDS measured 2160 δ18O and δ2H values continuously over a period of 36 h with a precision of ±0.08 and 0.5‰ for δ18O and δ2H, respectively. Four main advantages in using high temporal resolution stream δ18O and δ2H data during a storm event are highlighted from this study. First, they enabled us to separate components of the hydrograph, which was not possible using high temporal resolution electrical conductivity data that represented changes in solute transfers during the storm event rather than physical hydrological processes. The results from the hydrograph separation confirm fast groundwater contribution to the stream, with the first 5 h of increases in stream discharge comprising over 70% pre‐event water. Second, the high temporal resolution stream δ18O and δ2H data allowed us to detect a short‐lived reversal in stream isotopic values (δ18O increase by 0.4‰ over 9 min), which was observed immediately after the heavy rainfall period. Third, δ18O values were used to calculate a time lag of 20 min between the physical and chemical stream responses during the storm event. Finally, the hydrograph separation highlights the role of event waters in the runoff transfers of herbicides and nutrients from this heavily cultivated catchment to the Great Barrier Reef. Copyright © 2015 John Wiley & Sons, Ltd.

A mechanistic analysis of early Eocene latitudinal gradients of isotopes in precipitation

AbstractWe use a one‐dimensional reactive transport model of isotopes in precipitation (δ18O) to investigate the physical mechanisms controlling global meridional isotope profiles under early Eocene hothouse conditions. Simulations of early Eocene precipitation isotopes display reduced meridional gradients relative to the modern climate with the largest increases in δ18O occurring at high latitudes, matching proxy data. These reduced gradients are controlled primarily by polar amplification that increases high‐latitude length scales of specific humidity and match our compilation of proxy‐based reconstructions. Comparing Eocene general circulation model simulations run with pCO2 of 2240 and 4480 ppm, we find that meridional isotopic profiles are insensitive to the associated 5°C change in global temperatures due to the relative lack of polar amplification. Finally, we hypothesize that observed negative δD anomalies in precipitation during peak warming of early Eocene hyperthermal events are the result of a theorized reduction in the strength of midlatitude transient eddies.

Importance of groundwater in propagating downward integration of the 6–5 Ma Colorado River system: Geochemistry of springs, travertines, and lacustrine carbonates of the Grand Canyon region over the past 12 Ma

We applied multiple geochemical tracers (87Sr/86Sr, [Sr], δ13C, and δ18O) to waters and carbonates of the lower Colorado River system to evaluate its paleohydrology over the past 12 Ma. Modern springs in Grand Canyon reflect mixing of deeply derived (endogenic) fluids with meteoric (epigenic) recharge. Travertine (<1 Ma) and speleothems (2–4 Ma) yield 87Sr/86Sr and δ13C and δ18O values that overlap with associated water values, providing justification for use of carbonates as a proxy for the waters from which they were deposited. The Hualapai Limestone (12–6 Ma) and Bouse Formation (5.6–4.8 Ma) record paleohydrology immediately prior to and during integration of the Colorado River. The Hualapai Limestone was deposited from 12 Ma (new ash age) to 6 Ma; carbonates thicken eastward to ∼210 m toward the Grand Wash fault, suggesting that deposition was synchronous with fault slip. A fanning-dip geometry is suggested by correlation of ashes between subbasins using tephrochronology. New detrital-zircon ages are consistent with the “Muddy Creek constraint,” which posits that Grand Wash Trough was internally drained prior to 6 Ma, with limited or no Colorado Plateau detritus, and that Grand Wash basin was sedimentologically distinct from Gregg and Temple basins until after 6 Ma. New isotopic data from Hualapai Limestone of Grand Wash basin show values and ranges of 87Sr/86Sr, δ13C, and δ18O that are similar to Grand Canyon springs and travertines, suggesting a long-lived spring-fed lake/marsh system sourced from western Colorado Plateau groundwater. Progressive up-section decrease in 87Sr/86Sr and δ13C and increase in δ18O in the uppermost 50 m of the Hualapai Limestone indicate an increase in meteoric water relative to endogenic inputs, which we interpret to record progressively increased input of high-elevation Colorado Plateau groundwater from ca. 8 to 6 Ma. Grand Wash, Hualapai, Gregg, and Temple basins, although potentially connected by groundwater, were hydrochemically distinct basins before ca. 6 Ma. The 87Sr/86Sr, δ13C, and δ18O chemostratigraphic trends are compatible with a model for downward integration of Hualapai basins by groundwater sapping and lake spillover.

Vertical decoupling of nitrate assimilation and nitrification in the Sargasso Sea

The fraction of phytoplankton growth that leads to the rain of organic carbon out of the sunlit surface ocean (“export production”) is central to the ocean׳s sequestration of atmospheric carbon dioxide. Nitrate assimilation has long been taken as a measure of export production; however, this has recently been questioned by suggestions that much of the nitrate in the sunlit layer (the “euphotic zone”) originates from biological nitrogen (N) already in surface waters. This view has been supported by recent observations of euphotic zone nitrate elevated in δ18O relative to its δ15N, taken as indicative of nitrification (the oxidation of recycled ammonium to nitrite and then nitrate). To evaluate the potential importance of nitrification in the Sargasso Sea euphotic zone, we measured the δ15N and δ18O of seawater nitrate for samples with ≥0.2µM nitrate collected on 18 cruises in the Sargasso Sea, and here we present the first large data set to correct for the low but often measurable concentrations of nitrite. Regardless of season, nitrate (i.e., nitrate-only rather than nitrate+nitrite as is commonly reported) δ15N and δ18O increase in unison from below the base of the euphotic zone toward the surface. This pattern derives from nitrate assimilation by phytoplankton, implying that nitrification is much slower than the upward transport of nitrate into the lower Sargasso Sea euphotic zone. In the twilight zone below the euphotic zone, we observe a rise in nitrate δ18O (relative to deeper waters) that is not accompanied by a rise in δ15N, suggesting nitrification co-occurring with nitrate assimilation. Nitrification, therefore, does not appear to occur in euphotic zone waters overlapping with nitrate assimilation only in the ~150m-thick twilight zone layer below it. In net, the data argue for a simpler N cycle for the Sargasso Sea euphotic zone than has recently been suggested, with the rate of euphotic zone nitrate assimilation approximating that of organic carbon export to the deep ocean.

Use of isotopic compositions of nitrate in TSP to identify sources and chemistry in South China Sea

NO3− concentration, nitrogen and oxygen isotopic compositions (δ15N and δ18O) of NO3− were measured in total suspended particulates (TSP) at Yongxing Island in the South China Sea (SCS) between Feb. 2013 and Jan. 2014, as well as on two cruises in the northern South China Sea (NSCS). Measurements aimed to identify NO3− sources, and possible chemical formation processes of NO3−. The δ15N and δ18O of NO3− in TSP at Yongxing Island ranged from −2.5 to +4.9‰, and +48.1 to +99.0‰, with annual weighted averages of +1.5‰ and +83.2‰, respectively. Both δ15N and δ18O had higher values in cool months, indicating that NOx sources and oxidants were different between seasons. In cool months, NOx was mainly from anthropogenic sources, particularly from coal combustion in South China, resulting in high nitrogen deposition that was oxidized by O3 to NO3−. In warm months, natural emissions were an important source of NOx. TSP samples in the NSCS had higher NO3− concentrations, higher δ15N and lower δ18O values than samples from Yongxing Island over the same period. This suggests that atmospheric processes caused a decrease in NO3− concentrations and δ15N but increase in δ18O from coast to remote marine. Assuming to oxygen atoms were derived from O3 during transport in cool months, the mean ratio of NO3− formed by NOx to total NO3− was calculated to be 47.9%. This suggests the mean loss ratio of NOx was 89% while the loss ratio of NO3− was 87% during transport between Chinese coastal areas and Yongxing Island in Nov., 2013.

Origin of particulate organic matter in a river with remarkable water pollution in Shikoku Island, Japan

This study on the origin of particulate organic matter (POM) in a river under efficient water use for irrigation in a basin was carried out on the Shin River in Kagawa Prefecture, Japan. The organic pollution in the basin where water resources are scarce was studied. The level of POM in the Shin River was significantly influenced by the natural and artificial hydrological environment in the river basin. The degree of organic pollution in the Shin River was high, and most of the organic matter was algae. The δ18O of water of the middle and lower reaches of the Shin River was high, and water subjected to evaporation for a lengthy time period in the basin flows into the river. The concentration of organic matter in the Shin increases along with the increase in δ18O. Algae also increases in the stay waters in the basin of the middle–lower reaches and flows into the Shin. It was thought that the irrigation ponds in the basin were the main sources of water and organic matter for the river. This tendency was notable during the nonirrigation season in that the volume of water in the basin decreased. On the other hand, the proportion of algae in organic matter in the river decreased when there was considerable precipitation.

Assessment of the sources and transformations of nitrogen in a plain river network region using a stable isotope approach

The great spatial and temporal variability in hydrological conditions and nitrogen (N) processing introduces large uncertainties to the identification of N sources and quantifying N cycles in plain river network regions. By combining isotopic data with chemical and hydrologic measurements, we determined the relative importance of N sources and biogeochemical N processes in the Taige River in the East Plain Region of China. The river was polluted more seriously by anthropogenic inputs in winter than in summer. Manure and urban sewage effluent were the main nitrate (NO3−) sources, with the nitrification of N-containing organic materials serving as another important source of NO3−. In the downstream, with minor variations in hydrological conditions, nitrification played a more important role than assimilation for the decreasing ammonium (NH4+-N) concentrations. The N isotopic enrichment factors (ε) during NH4+ utilization ranged from −13.88‰ in March to −29.00‰ in July. The ratio of the increase in δ18O and δ15N of river NO3− in the downstream was 1.04 in January and 0.92 in March. This ratio indicated that NO3− assimilation by phytoplankton was responsible for the increasing δ15N and δ18O values of NO3− in winter. The relationships between δ15N of particulate organic nitrogen and isotopic compositions of dissolved inorganic nitrogen indicated that the phytoplankton in the Taige River probably utilized NH4+ preferentially and mainly in summer, while in winter, NO3− assimilation by phytoplankton was dominant.

The impact of neogene grassland expansion and aridification on the isotopic composition of continental precipitation

AbstractThe late Cenozoic was a time of global cooling, increased aridity, and expansion of grasslands. In the last two decades numerous records of oxygen isotopes have been collected to assess plant ecological changes, understand terrestrial paleoclimate, and to determine the surface history of mountain belts. The δ18O values of these records, in general, increase from the mid‐Miocene to the Recent. We suggest that these records record an increase in aridity and expansion of grasslands in midlatitude continental regions. We use a nondimensional isotopic vapor transport model coupled with a soil water isotope model to evaluate the role of vapor recycling and transpiration by different plant functional types. This analysis shows that increased vapor recycling associated with grassland expansion along with biomechanistic changes in transpiration by grasses themselves conspires to lower the horizontal gradient in the δ18O of atmospheric vapor as an air mass moves into continental interiors. The resulting signal at a given inland site is an increase in δ18O of precipitation with the expansion of grasslands and increasing aridity, matching the general observed trend in terrestrial Cenozoic δ18O records. There are limits to the isotopic effect that are induced by vapor recycling, which we refer to here as a “hydrostat.” In the modern climate, this hydrostatic limit occurs at approximately the boundary between forest and grassland ecosystems.

Constraining Holocene hydrological changes in the Carpathian–Balkan region using speleothem δ&amp;lt;sup&amp;gt;18&amp;lt;/sup&amp;gt;O and pollen-based temperature reconstructions

Abstract. Here we present a speleothem isotope record (POM2) from Ascunsă Cave (Romania) that provides new data on past climate changes in the Carpathian–Balkan region from 8.2 ka until the present. This paper describes an approach to constrain the effect of temperature changes on calcite δ18O values in stalagmite POM2 over the course of the middle Holocene (6–4 ka), and across the 8.2 and 3.2 ka rapid climate change events. Independent pollen temperature reconstructions are used to this purpose. The approach combines the temperature-dependent isotope fractionation of rain water during condensation and fractionation resulting from calcite precipitation at the given cave temperature. The only prior assumptions are that pollen-derived average annual temperature reflects average cave temperature, and that pollen-derived coldest and warmest month temperatures reflect the range of condensation temperatures of rain above the cave site. This approach constrains a range of values between which speleothem δ18O changes should be found if controlled only by surface temperature variations at the cave site. Deviations of the change in δ18Ocspel values from the calculated temperature-constrained range of change are interpreted towards large-scale variability of climate–hydrology. Following this approach, we show that an additional ∼0.6‰ enrichment of δ18Oc in the POM2 stalagmite was caused by changing hydrological patterns in SW Romania across the middle Holocene, most likely comprising local evaporation from the soil and an increase in Mediterranean moisture δ18O. Further, by extending the calculations to other speleothem records from around the entire Mediterranean basin, it appears that all eastern Mediterranean speleothems recorded a similar isotopic enrichment due to changing hydrology, whereas all changes recorded in speleothems from the western Mediterranean are fully explained by temperature variation alone. This highlights a different hydrological evolution between the two sides of the Mediterranean. Our results also demonstrate that during the 8.2 ka event, POM2 stable isotope data essentially fit the temperature-constrained isotopic variability. In the case of the 3.2 ka event, an additional climate-related hydrological factor is more evident. This implies a different rainfall pattern in the Southern Carpathian region during this event at the end of the Bronze Age.

Variations of oxygen-18 in West Siberian precipitation during the last 50 years

Abstract. Global warming is associated with large increases in surface air temperature in Siberia. Here, we apply the isotope-enabled atmospheric general circulation model ECHAM5-wiso to explore the potential of water isotope measurements at a recently opened monitoring station in Kourovka (57.04° N, 59.55° E) in order to successfully trace climate change in western Siberia. Our model is constrained to atmospheric reanalysis fields for the period 1957–2013 to facilitate the comparison with observations of δD in total column water vapour from the GOSAT satellite, and with precipitation δ18O measurements from 15 Russian stations of the Global Network of Isotopes in Precipitation. The model captures the observed Russian climate within reasonable error margins, and displays the observed isotopic gradients associated with increasing continentality and decreasing meridional temperatures. The model also reproduces the observed seasonal cycle of δ18O, which parallels the seasonal cycle of temperature and ranges from −25 ‰ in winter to −5 ‰ in summer. Investigating West Siberian climate and precipitation δ18O variability during the last 50 years, we find long-term increasing trends in temperature and δ18O, while precipitation trends are uncertain. During the last 50 years, winter temperatures have increased by 1.7 °C. The simulated long-term increase of precipitation δ18O is at the detection limit (&lt;1 ‰ per 50 years) but significant. West Siberian climate is characterized by strong interannual variability, which in winter is strongly related to the North Atlantic Oscillation. In winter, regional temperature is the predominant factor controlling δ18O variations on interannual to decadal timescales with a slope of about 0.5 ‰ °C−1. In summer, the interannual variability of δ18O can be attributed to short-term, regional-scale processes such as evaporation and convective precipitation. This finding suggests that precipitation δ18O has the potential to reveal hydrometeorological regime shifts in western Siberia which are otherwise difficult to identify. Focusing on Kourovka, the simulated evolution of temperature, δ18O and, to a smaller extent, precipitation during the last 50 years is synchronous with model results averaged over all of western Siberia, suggesting that this site will be representative to monitor future isotopic changes in the entire region.

Southward shift of the Intertropical Convergence Zone due to Northern Hemisphere cooling at the Oligocene-Miocene boundary

The Mi-1 glaciation (ca. 23 Ma), which marks the Oligocene-Miocene boundary, was an aberrant cooling event that led to a build-up of the Antarctic ice sheet, which reached the near-modern volume (or greater) from its ephemeral or partial existence. An increase of ∼1‰ in the δ18O of benthic foraminifera during this interval has been attributed to the development of Antarctic ice sheets and deep-water cooling. Without definitive evidence, Northern Hemisphere (NH) glaciation has not been a material consideration for the δ18O increase. Here we investigate the interhemispheric temperature contrast during Mi-1, with the movement of the Intertropical Convergence Zone (ITCZ) at a site (10°31′N) in the East Pacific (Integrated Ocean Drilling Program Site U1333), to understand NH cooling and the possibility of NH glaciation. The measured 143Nd/144Nd, 87Sr/86Sr, and clay mineral compositions of eolian dust fractions indicate unequivocally the deposition of Asian dust during Mi-1, and of Central American and South American dust before and after Mi-1. This is attributed to the southward displacement of the ITCZ over Site U1333 during Mi-1. The ITCZ shifts toward the warmer hemisphere. Thus our results suggest that the cooling during Mi-1 was more significant in the NH than in the Southern Hemisphere, which underwent a sudden expansion of continental ice sheets. Our data call for a forcing mechanism to drive significant NH cooling during this episode. Based on the available data, we propose that the widespread growth of NH ice sheets and/or changes in the production of North Atlantic–origin deep water could be possible causes of the NH cooling at that time.

Multiple Dolomitization Episodes In Deep-Water Limestones of the Triassic Lagonegro Basin (Southern Italy): From Early Reflux To Tectonically Driven Fluid Flow

Abstract Massive dolomitization does not commonly occur in deep-water carbonates. However, this regional study on outcrops and subsurface samples of Triassic Lagonegro basinal carbonates from the southern Apennines fold and thrust belt (Italy) shows that the evolution of the Lagonegro basin was punctuated by two events of massive dolomitization. These processes resulted in two distinct dolomite types, displaying different petrographic and geochemical features. A medium-crystalline and fabric-preservative dolomite in the northern area (Molise, Campagna, and San Fele–Mount Pierno) contrasts with a medium- to coarse-crystalline and fabric-destructive dolomite in the southern area (from Pignola to the high Val d'Agri). Geochemical data (increase in δ18O with respect to typical Late Triassic seawater values, high Sr and low Mn and Fe content, Sr isotopes consistent with Late Triassic seawater) indicate that the dolomite in the northern area is the result of an early replacement caused by a marine and possibly oxidizing fluid during shallow burial. Dolomitizing fluids likely were expelled through reflux from the Norian Apenninic carbonate platform towards the proximal Lagonegro basin. This reflux was promoted by the Norian peculiar paleoceanographic and climatic conditions in the Tethyan region, and affected only the proximal basinal facies. Dolomites in the southern area display a decrease in δ18O compared to Late Triassic seawater values and show lower Sr, higher Mn and Fe contents, and higher Sr isotope ratios compared to the early dolomites of the northern area. Fluid-inclusion microthermometry reveals homogenization temperatures between 70 and 120°C and salinities of 1.9 to 6.4 wt % NaCl eq. for saddle dolomites. These geochemical signatures indicate that the southern area was affected by late diagenetic burial dolomitization, interpreted to be the result of large scale tectonically driven fluid flow during the second compressional phase characterizing the southern Apennines fold and thrust belt emplacement. The dolomite distribution across the Lagonegro basin (northern and southern) is possibly controlled by the paleogeographic distribution of the facies (proximal vs. distal) as well as by their proximity to thrust faults. The Lagonegro case study demonstrates that basinal successions may undergo multiple dolomitization episodes in a manner similar to carbonate platform successions, from early shallow to deep-burial diagenesis. One of the relevant implications is that in areas of restricted oceanographic circulation, during periods of aridity, reflux dolomitization may extend beyond the platform margin, into deep-water carbonates, having the potential to alter their reservoir quality.

The isotopic composition of water vapour and precipitation in Ivittuut, southern Greenland

Abstract. Since September 2011, a wavelength-scanned cavity ring-down spectroscopy analyser has been remotely operated in Ivittuut, southern Greenland, providing the first record of surface water vapour isotopic composition based on continuous measurements in South Greenland and the first record including the winter season in Greenland. The comparison of vapour data with measurements of precipitation isotopic composition suggest an equilibrium between surface vapour and precipitation. δ18O and deuterium excess are generally anti-correlated and show important seasonal variations, with respective amplitudes of ~10 and ~20‰, as well as large synoptic variations. The data depict small summer diurnal variations. At the seasonal scale, δ18O has a minimum in November–December and a maximum in June–July, while deuterium excess has a minimum in May–June and a maximum in November. The approach of low-pressure systems towards South Greenland leads to δ18O increase (typically +5‰) and deuterium excess decrease (typically −15‰). Seasonal and synoptic variations coincide with shifts in the moisture sources, estimated using a quantitative moisture source diagnostic based on a Lagrangian back-trajectory model. The atmospheric general circulation model LMDZiso correctly captures the seasonal and synoptic variability of δ18O, but does not capture the observed magnitude of deuterium excess variability. Covariations of water vapour isotopic composition with local and moisture source meteorological parameters have been evaluated. δ18O is strongly correlated with the logarithm of local surface humidity, consistent with Rayleigh distillation processes, and with local surface air temperature, associated with a slope of ~0.4‰ °C−1. Deuterium excess correlates with local surface relative humidity as well as surface relative humidity from the dominant moisture source area located in the North Atlantic, south of Greenland and Iceland.

Palaeoclimate inferred from δ18O and palaeobotanical indicators in freshwater tufa of Lake Äntu Sinijärv, Estonia

We investigated a 3.75-m-long lacustrine sediment record from Lake Äntu Sinijärv, northern Estonia, which has a modeled basal age >12,800 cal yr BP. Our multi-proxy approach focused on the stable oxygen isotope composition (δ18O) of freshwater tufa. Our new palaeoclimate information for the Eastern Baltic region, based on high-resolution δ18O data (219 samples), is supported by pollen and plant macrofossil data. Radiocarbon dates were used to develop a core chronology and estimate sedimentation rates. Freshwater tufa precipitation started ca. 10,700 cal yr BP, ca. 2,000 years later than suggested by previous studies on the same lake. Younger Dryas cooling is documented clearly in Lake Äntu Sinijärv sediments by abrupt appearance of diagnostic pollen (Betula nana, Dryas octopetala), highest mineral matter content in sediments (up to 90 %) and low values of δ18O (less than −12 ‰). Globally recognized 9.3- and 8.2-ka cold events are weakly defined by negative shifts in δ18O values, to −11.3 and −11.7 ‰, respectively, and low concentrations of herb pollen and charcoal particles. The Holocene thermal maximum (HTM) is palaeobotanically well documented by the first appearance and establishment of nemoral thermophilous taxa and presence of water lilies requiring warm conditions. Isotope values show an increasing trend during the HTM, from −11.5 to −10.5 ‰. Relatively stable environmental conditions, represented by only a small-scale increase in δ18O (up to 1 ‰) and high pollen concentrations between 5,000 and 3,000 cal yr BP, were followed by a decrease in δ18O, reaching the most negative value (−12.7 ‰) recorded in the freshwater tufa ca. 900 cal yr BP.

Community N and O isotope fractionation by sulfide-dependent denitrification and anammox in a stratified lacustrine water column

We investigated the community nitrogen (N) and oxygen (O) isotope effects of fixed N loss in the northern basin of Lake Lugano, where sulfide-dependent denitrification and anammox are the main drivers of suboxic N2 production. A decrease in nitrate (NO3−) concentration toward the redox transition zone (RTZ) at mid-water depth was paralleled by an increase in δ15N and δ18O from approximately 5‰ to >20‰ and from 0‰ to >10‰, respectively. Ammonium (NH4+) concentrations were highest in the near-bottom water and decreased toward the RTZ concomitant with an increase in δ15N–NH4+ from ∼7‰ to >15‰. A diffusion-reaction model yielded N and O isotope enrichment factors that are significantly smaller than isotope effects reported previously for microbial NO3− reduction and NH4+ oxidation (15εNO3≈10‰, 18εNO3≈7‰, and 15εNH4≈10−12‰). For the Lake Lugano north basin, we constrain the apparent under-expression of the N isotope effects to: (1) environmental conditions (e.g., substrate limitation, low cell specific N transformation rates), or (2) low process-specific (chemolithotrophic denitrification and anammox) isotope fractionation. Our results have confirmed the robust nature of the co-linearity between N and O isotope enrichment during microbial denitrification beyond its organotrophic mode. However, the ratio of 18O to 15N enrichment (18εNO3:15εNO3) associated with NO3− reduction in the RTZ was ∼0.89, which is lower than observed in marine environments and in most culture experiments. We propose that chemolithotrophic NO3− reduction in the Lake Lugano north basin was partly catalyzed by the periplasmic dissimilatory nitrate reductase (Nap) (rather than the membrane-bound dissimilatory Nar), which is known to express comparably low 18εNO3:15εNO3 ratios in the ambient NO3− pool. However, NO2− re-oxidation, e.g., during anammox or microaerobic nitrification, could have contributed to the lowered 18O to 15N enrichment ratios. Although we do not yet understand the exact controls on the observed N (and O) isotope fractionation in the Lake Lugano north basin, our study implies that caution is advised when assuming canonical (i.e., high) N isotope effects for NO3− reduction and NH4+ oxidation in natural environments. In Lake Lugano, the community N (and O) isotope effects by sulfide-dependent denitrification and anammox in a natural ecosystem appear to be significantly lower than for organotrophic denitrification and aerobic ammonium oxidation.