Late Holocene inter-annual temperature variability reconstructed from the δ18O of archaeological Ostrea angasi shells

Two multi-year oxygen isotope (δ¹⁸O) records were obtained from archaeological Ostrea angasi shells, confirming the potential of this species to provide valuable environmental records for the late Holocene period in southeastern Australia. High-resolution δ¹⁸O_shell samples from the O. angasi clearly display a seasonal variability, offering insight into past climate conditions in a region where such information is presently limited.

The oxygen isotope record in O. angasi reflects a combined temperature–salinity signal. Observations of δ¹⁸O_shell data from modern specimens are used as a point of reference to assist in decoupling these two influences, with the two archaeological samples compared with the δ¹⁸O_shell profile of four modern O. angasi. Assuming similar paleo- δ¹⁸O_water values at the collection sites, data from these archaeological shells present a record of temperatures during the period of their growth that are consistently lower than modern day, with mean annual temperatures ～2°C cooler.     

The effect of species on lacustrine δ18Odiatom and its implications for palaeoenvironmental reconstructions

The oxygen isotope composition of diatom silica (δ¹⁸O_diatom) is increasingly being used to reconstruct climate from marine and lacustrine sedimentary archives. Although diatoms are assumed to precipitate their frustule in isotopic equilibrium with their surrounding water, it is unclear whether internal processes of a given species affect the fractionation of oxygen between the water and the diatom. We present δ¹⁸O_diatom data from two diatom size fractions (3–38 and >38 µm) characterized by different species in a sediment core from Heart Lake, Alaska. Differences in δ¹⁸O_diatom between the two size fractions varies from 0 to 1.2‰, with a mean offset of 0.01‰ (n = 20). Fourier transform infrared spectroscopy confirms our samples consist of pure biogenic silica (SiO₂) and δ¹⁸O_diatom trends are not driven by contamination. The maximum offset is outside the range of error, but the mean is within analytical error of the technique (± 1.06‰), demonstrating no discernible species‐dependent fractionation in δ¹⁸O_diatom. We conclude that lacustrine δ¹⁸O_diatom measurements offer a reliable and valuable method for reconstructing δ¹⁸O_water. Considering the presence of small offsets in our two records, we advise interpreting shifts in δ¹⁸O_diatom only where the magnitude of change is greater than the combined analytical error.     

An approach to estimate Lower Jurassic seawater oxygen‐isotope composition using δ18O and Mg/Ca ratios of belemnite calcites (Early Pliensbachian,northern Spain)

Palaeotemperature estimates from the oxygen‐isotope compositions of belemnites have been hampered by not knowing ancient seawater isotope compositions well enough. We have tackled this problem using Mg/Ca as a proxy for temperature and here, we present a ~2 Ma record of paired Mg/Ca and δ¹⁸O measurements of Jurassic (Early Pliensbachian) belemnites from the Asturian basin as a palaeo‐proxy of seawater oxygen‐isotope composition. From the combined use of the two approaches, we suggest a δ¹⁸O_w composition of about ?0.1‰ for the Jamesoni–Ibex zones. This value may have been increased by about 0.6‰ during the Davoei Zone due to the effect of waters with a different δ¹⁸O_w composition. These findings illustrate the inaccuracy of using a globally homogeneous ice‐free value of δ¹⁸O_w = ?1‰ for δ¹⁸O_carb‐based palaeotemperature reconstructions. Our data suggest that previous palaeotemperatures calculated in the region from δ¹⁸O values of belemnites may have been underestimated as the seawater oxygen isotopic composition could have been higher.     

Oxygen and carbon stable isotopes of modern land snail shells as environmental indicators from a low-latitude oceanic island

Land snails provide a unique opportunity to study terrestrial paleoenvironments because their shells, which are generally highly abundant and well-preserved in the fossil record, contain a temporal record of environmental change in the form of isotope codes. To evaluate the utility of this approach for a low-latitude oceanic setting, 207 modern shells of 18 species of land snail were analyzed for their oxygen and carbon isotope composition along a north and south facing altitudinal gradient (10-2160 m a.s.l.) in Tenerife Island (∼28°N) of the Canary Archipelago.Shells collected at each locality showed a relatively large range in isotope composition which was greater along the south facing transect (drier and hotter), suggesting that the variance in shell isotope values may be related to water-stress. Although pooled isotope values did not generally show strong relationships with environmental variables (i.e., altitude, temperature and precipitation), mean isotope values were strongly associated with some climatic factors when grouped by site. The mean δ¹⁸O value of the shell (δ¹⁸O_shell) by site displayed a negative correlation with elevation, which is consistent with the positive relationship observed between temperature and the δ¹⁸O value of rain (δ¹⁸O_rain). Calculated δ¹⁸O values of the snail body water (δ¹⁸O_body) derived from observed temperatures and δ¹⁸O_shell values (using the equation of Grossman and Ku [Grossman E. L. and Ku T. L. (1986) Oxygen and carbon isotope fractionation in biogenic aragonite. Chem. Geol. (Isotope Geosci. Sec.)59, 59-74]) displayed a trend with respect to altitude that was similar to measured and hypothetical δ¹⁸O values for local rain water. The calculated δ¹⁸O_body values from the shell declined 0.17‰ (VSMOW) per 100 m, which is consistent with the “altitude effect” observed for tropical rains in Western Africa, and it correlated negatively with rainfall amount. Accordingly, lower δ¹⁸O_shell values indicate lower temperatures, lower δ¹⁸O_rain values and possibly, higher rainfall totals. A positive correlation between the mean δ¹³C values of shells (δ¹³C_shell) and plants by site suggests that shells potentially record information about the surrounding vegetation. The δ¹³C_shell values varied between −15.7 and −0.6‰ (VPDB), indicating that snails consumed C₃ and C₄/CAM plants, where more negative δ¹³C_shell values probably reflects the preferential consumption of C₃ plants which are favored under wetter conditions. Individuals with more positive δ¹³C_shell values consumed a larger percentage of C₄ plants (other potential factors such as carbonate ingestion or atmospheric CO₂ contribution were unlikely) that were more common at lower elevations of the hotter and drier south facing transect. The relatively wide range of shell isotope values within a single site requires the analysis of numerous shells for meaningful paleoclimatic studies. Although small differences were observed in isotope composition among snail species collected at a single sampling site, they were not significant, suggesting that isotope signatures extracted from multi-taxa snail data sets may be used to infer environmental conditions over a broad range of habitats.     

High‐resolution diatom δ18O records,from the last 150 years,reflecting changes in amount of winter precipitation in two sub‐Arctic high‐altitude lakes in the Swedish Scandes

Waters from high‐altitude alpine lakes are mainly recharged by meteoric water. Because of seasonal variations in precipitation and temperature and relatively short hydraulic residence times, most high‐altitude lakes have lake water isotopic compositions (δ¹⁸O_lake) that fluctuate due to seasonality in water balance processes. Input from snowmelt, in particular, has a significant role in determining lake water δ¹⁸O. Here we compare two high‐resolution δ¹⁸O_diatom records from lake sediments in the Swedish Scandes with instrumental data from the last century obtained from nearby meteorological stations. The time period AD 1900–1990 is characterised by an increase in winter precipitation and high winter/summer precipitation ratios and this is recorded in δ¹⁸O_diatom as decreasing trends. Lowest δ¹⁸O_diatom values and highest amount of winter precipitation are found around AD 1990 when the winter North Atlantic Oscillation index was above +2. We conclude that for the last 150 a the main factor affecting the δ¹⁸O_diatom signal in these sub‐Arctic high‐altitude lakes with short residence times has been changes in amount of winter precipitation and that δ¹⁸O_diatom derived from high‐altitude lakes in the Swedish Scandes can be used as a winter precipitation proxy. Copyright © 2010 John Wiley & Sons, Ltd.     

USGS46 Greenland Ice Core Water – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

Ice core from Greenland was melted, filtered, homogenised, loaded into glass ampoules, sealed, autoclaved to eliminate biological activity, and calibrated by dual‐inlet isotope‐ratio mass spectrometry. This isotopic reference material (RM), USGS46, is intended as one of two secondary isotopic reference waters for daily normalisation of stable hydrogen (δ²H) and stable oxygen (δ¹⁸O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The measured δ²H and δ¹⁸O values of this reference water were ?235.8 ± 0.7‰ and ?29.80 ± 0.03‰, respectively, relative to VSMOW on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5‰. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95‐percent probability of encompassing the true value. This reference water is available in cases containing 144 glass ampoules that are filled with either 4 ml or 5 ml of water per ampoule.     

Climate shifts vs. edaphic humidity and the difficulty of palaeoreconstructions – a malacological study on stable isotopes in Quaternary dune sequences of Fuerteventura

Dune palaeosurface sequences on the Eastern Canary Islands were investigated for stable isotope records in gastropod shells of the genus Theba. Due to the ecology of the taxon and the special oceanic insularity of the study site, we assume that δ¹⁸O_shell signals in our case mainly reflect shifts in δ¹⁸O signals of sea surface water. We found that a rapid decrease in δ¹⁸O_shell signals is associated with significant changes in gastropod associations. We suggest that these faunal changes were caused by strong (hot) winds at the end of glacial phases, that were described previously by Moreno et al. In addition, we assume that rapid declines in δ¹⁸O_shell signals due to marine transgressions were followed by geomorphologically stable phases, dominated by dust enrichment. Such palaeosurfaces correlate with maxima of gastropod biodiversity and with more negative δ¹³C_shell signals indicating a higher proportion of C3 plants. Based on our results, we also assume that these silty palaeosurfaces were associated with increased soil moisture conditions due to a higher water storage capacity of the finer substrate, independent of climatic moisture conditions.     

The δ18O of UST Quartz in Two Porphyry Deposits,China

The unidirectional solidification textures (UST) quartz is generally thought to form from fluids exsolved from shallow intrusions and/or magma chambers, but such an idea is still poorly constrained from the evidence of stable isotopes. In this study, we report for the first time the δ¹⁸O of quartz that shows UST from the Qulong Cu–Mo and the Yechangping Mo porphyry deposits in China. The analysis results show that the UST quartz samples from the Qulong deposit have δ¹⁸O values ranging from +6.2 ‰ to +7.6 ‰, which are similar to that of quartz phenocrysts (+6.7 ‰ to +7.8 ‰). In contrast, the UST quartz samples from the Yechangping porphyry Mo deposit yield a high δ¹⁸O value (+10.0 ‰). The δ¹⁸O_water value of Yechangping UST quartz (+8.5 ‰) is also higher than that of Qulong (+4.6 ‰ to +5.8 ‰). Hydrothermal biotite from potassic alteration and sericite from early phyllic alteration at Qulong have similar δ¹⁸O values to UST quartz, suggesting the involvement of magmatic fluids during this stage of deposit evolution.     

Techniques for assessing spatial heterogeneity of carbonate δ13C values: Implications for craton‐wide isotope gradients

The sedimentary record of carbonate carbon isotopes (δ¹³C_carb) provides one of the best methods for correlating marine strata and understanding the long‐term evolution of the global carbon cycle. This work focuses on the Late Ordovician Guttenberg isotopic carbon excursion, a ca 2·5‰ positive δ¹³C_carb excursion that is found in strata globally. Substantial variability in the apparent magnitude and stratigraphic morphology of the Guttenberg excursion at different localities has hampered high‐resolution correlations and led to divergent reconstructions of ocean chemistry and the biogeochemical carbon cycle. This work investigates the magnitude, spatial scale and sources of isotopic variability of the Guttenberg excursion in two sections from Missouri, USA. Centimetre‐scale isotope transects revealed variations in δ¹³C_carb and δ¹⁸O_carb greater than 2‰ across individual beds. Linear δ¹³C_carb to δ¹⁸O_carb mixing lines, together with petrographic and elemental abundance data, demonstrate that much of the isotopic scatter in single beds is due to mixing of isotopically distinct components. These patterns facilitated objective sample screening to determine the ‘least‐altered’ data. A δ¹⁸O_carb filter based on empirical δ¹⁸O_carb values of well‐preserved carbonate mudstones allowed further sample discrimination. The resulting ‘least‐altered’ δ¹³C_carb profile improves the understanding of regional as well as continental‐scale stratigraphic relations in this interval. Correlations with other Laurentian sections strongly suggest that: (i) small‐scale variability in Guttenberg excursion δ¹³C_carb values may result in part from local diagenetic overprinting; (ii) peak‐Guttenberg excursion δ¹³C_carb values of the Midcontinent are not distinct from their Taconic equivalents; and (iii) no primary continental‐scale spatial gradient in δ¹³C_carb (for example, arising from chemically distinct ‘aquafacies’) is required during Guttenberg excursion‐time. This study demonstrates the importance of detailed petrographic and geochemical screening of samples to be used for δ¹³C_carb chemostratigraphy and for enhancing understanding of epeiric ocean chemistry.     

Antarctic Ice‐Core Water (USGS49) – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from ice‐core water from the Amundsen–Scott South Pole Station. This isotopic reference material, designated as USGS49, was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity and measured by dual‐inlet isotope‐ratio mass spectrometry. The δ²H and δ¹⁸O values of USGS49 are ?394.7 ± 0.4 and ?50.55 ± 0.04 mUr (where mUr = 0.001 = ‰), respectively, relative to VSMOW, on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5 mUr. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95% probability of encompassing the true value. This isotopic reference material is intended as one of two isotopic reference waters for daily normalisation of stable hydrogen and oxygen isotopic analysis of water with an isotope‐ratio mass spectrometer or a laser absorption spectrometer. It is available by the case of 144 glass ampoules or as a set of sixteen glass ampoules containing 5 ml of water in each ampoule.     

Seasonal temperatures from δ18O in recent Spanish tufa stromatolites: Equilibrium redux!

This study focuses on recent debate over the value of stable isotope‐based environmental proxies recorded in riverine tufa stromatolites. A twelve‐year record (1999 to 2012) of river‐bed tufa stromatolites in the River Piedra (north‐east Spain) was recovered in this study, along with a partly overlapping fifteen‐year record (1994 to 2009) of accumulations in a drainage pipe: both deposits formed in water with near identical physico/chemical parameters. Measured water temperature data and near‐constant δ ¹⁸O_water composition allowed selection of an ‘equilibrium’ palaeotemperature equation that best replicated actual temperatures. This study, as in some previous studies, found that just two published formulas for water temperature calculation from equilibrium calcite δ ¹⁸O compositions were appropriate for the River Piedra, where tufa deposition rates are high, with means between 5·6 mm and 10·8 mm in six months. The δ ¹⁸O_calcite in both the river and the pipe deposits essentially records the full actual seasonal water temperature range. Only the coldest times (water temperature <10°C), when calcite precipitation mass decreased to minimum, are likely to be unrepresented, an effect most noticeable in the pipe where depositional masses are smaller and below sample resolution. While kinetic effects on δ ¹⁸O_calcite‐based calculated water temperature cannot be ruled out, the good fit between measured water temperature and δ ¹⁸O_calcite‐calculated water temperature indicates that temperature is the principal control. Textural and deposition rate variability between the river and pipe settings are caused by differences in flow velocity and illumination. In the river, calcification of growing cyanobacterial mat occurred throughout the year, producing composite dense and porous laminae, whereas in the pipe, discontinuous cyanobacterial growth in winter promoted more abiogenic calcification. High‐resolution δ ¹⁸O_calcite data from synchronous pipe and river laminae show that reversals in water temperature occur within laminae, not at lamina boundaries, a pattern consistent with progressive increase in calcite precipitation rate as cyanobacterial growth re‐established in spring.     

First detection of glacial meltwater signature in tree‐ring δ18O: Reconstructing past major glacier runoff events at Lago Verde (Miage Glacier,Italy)

With the aim of evaluating the influence of glacial meltwater signature on tree‐ring stable isotopes, we analysed δ¹⁸O and δ¹³C in the tree rings of Larix decidua Mill. specimens growing in the area of an ice‐contact lake (Lago Verde, at Miage Glacier, European Alps). Additionally, we analysed δ¹⁸O in the glacial meltwater of the lake and of the glacier stream and compared it with the δ¹⁸O of precipitation predicted by a spatial model. We found that tree‐ring cellulose of trees fed by glacial meltwaters (LVW site) is significantly more depleted in δ¹⁸O than at a control site LVM (?0.91‰) fed only by precipitation, thus reflecting the measured higher depletion of glacial meltwaters with respect to local precipitation. δ¹³C values did not show significant differences in mean values between the two sites but an anomalous correlation with summer temperature was found at the LVW site, probably due to the different responses of trees stomatal conductance. Over the 30‐year period of analysis, four years at LVW (1992, 1995, 2003 and 2009) were markedly depleted in δ¹⁸O. These years are those when the highest summer temperatures were recorded in the area (the ones during which glacier ablation usually increases and more depleted meltwaters fill the lake), with the exception of 1995 during which high water levels occurred following the year with the second highest summer temperature (1994). Overall, our analysis demonstrates that tree‐ring δ¹⁸O, driven by the glacial meltwater signature in the lake, can be used for detecting past major glacier runoff events. The proposed approach could also be used for quantifying past glacier runoff and for defining past distribution areas of glacial meltwaters in glacier forefields, thus contributing to past environmental reconstructions and to hazard assessment.     

Biogeochemical characterization of a Mediterranean shallow lake using stable isotopes: Laguna del Cristo (NW Iberian Peninsula)

The present multi-isotopic study (δ¹⁸O–δD_water, δ³⁴S–δ¹⁸O_{dissolved-sulphate}, δ¹³C_{dissolved-inorganic-carbon}, δ¹³C–δ¹⁸O_{shells-modern-gastropods}, δ¹³C_plants, and δ¹³C_{sedimentary-organic-matter}) is aimed at assessing the hydrogeochemical changes and biogeochemical dynamics in a Mediterranean shallow lake fed by a Quaternary–Tertiary aquifer, the “Laguna del Cristo” (NW Iberian Peninsula), a system sensitive to climate fluctuations, between 2010 and 2011. Lake water is of the bicarbonate type, and there are no major pollutants. δ¹⁸O-δD_water values plot on a local evaporation line (δD=5.29δ¹⁸O–12.29) indicating that evaporative enrichment had a significant impact on lake water isotopic features. Periods of high water levels are characterized by lower δ³⁴S–δ¹⁸O_{dissolved-sulphate} and δ¹³C_{dissolved-inorganic-carbon} values and suggest sulphate derived from weathering of sulphides in the catchment area, delivered to the lake by surface run-off or via groundwater, and in situ decay of organic matter. During lower water levels, sulphate reduction and enhanced primary productivity lead to higher δ³⁴S_{dissolved-sulphate} and δ¹³C_{dissolved-inorganic-carbon} values. Evaporation induced enrichment in ¹⁸O_sulphate, ¹³C_{dissolved-inorganic-carbon} and ¹³C–¹⁸O_{shells-Galba-Gyraulus}. δ¹³C_plant confirms the C3 photosynthetic pathway. Enrichment in ¹³C submerged aquatic plants indicates that HCO₃^? is the main carbon source, except for ¹³C-depleted Potamogeton. The TOC, δ¹³C_org values, and TC/TN ratios in sediments all confirm the autochthonous character of organic matter contribution. This study provides a baseline for isotopic research into shallow, flow-through lakes fed by siliciclastic aquifers, and stresses the importance of evaporation and refilling (direct precipitation and groundwater discharge) in controlling the solute chemistry and stable isotopic composition in temperate regions with contrasting seasonal climates. The results also provide a snapshot of modern lake isotope variability that can be applied to paleoenvironmental reconstructions.     

Holocene hydrological variability of Lake Ladoga,northwest Russia,as inferred from diatom oxygen isotopes

This article presents a new comprehensive assessment of the Holocene hydrological variability of Lake Ladoga, northwest Russia. The reconstruction is based on oxygen isotopes of lacustrine diatom silica (δ¹⁸O_diatom) preserved in sediment core Co 1309, and is complemented by a diatom assemblage analysis and a survey of modern isotope hydrology. The data indicate that Lake Ladoga has existed as a freshwater reservoir since at least 10.8 cal. ka BP. The δ¹⁸O_diatom values range from +29.8 to +35.0‰, and relatively higher δ¹⁸O_diatom values around +34.7‰ between c. 7.1 and 5.7 cal. ka BP are considered to reflect the Holocene Thermal Maximum. A continuous depletion in δ¹⁸O_diatom since c. 6.1 cal. ka BP accelerates after c. 4 cal. ka BP, indicating Middle to Late Holocene cooling that culminates during the interval 0.8–0.2 cal. ka BP, corresponding to the Little Ice Age. Lake‐level rises result in lower δ¹⁸O_diatom values, whereas lower lake levels cause higher δ¹⁸O_diatom values. The diatom isotope record gives an indication for a rather early opening of the Neva River outflow at c. 4.4–4.0 cal. ka BP. Generally, overall high δ¹⁸O_diatom values around +33.5‰ characterize a persistent evaporative lake system throughout the Holocene. As the Lake Ladoga δ¹⁸O_diatom record is roughly in line with the 60°N summer insolation, a linkage to broader‐scale climate change is likely.     

A reassessment of late glacial – Holocene diatom oxygen isotope record from Lake Baikal using a geochemical mass‐balance approach

We present a new palaeoenvironmental record of hydrological variability in Lake Baikal, based on re‐modelled δ¹⁸O_diatom values of diatom silica (δ¹⁸O_modelled), where the residual contaminants are identified and compensated for using electron optical imaging and whole‐sample geochemistry. δ¹⁸O_modelled interpretations are based on the balance between rivers with high δ¹⁸O values and rivers with low δ¹⁸O values. Isotopic variability is related to latitudinal differences in precipitation which feed these rivers. The δ¹⁸O_modelled record suggests that rather moist conditions prevailed in the Lake Baikal region during the latter stages of the Younger Dryas. Throughout the Holocene, episodes of low δ¹⁸O_modelled values are, in general, in good agreement with increases in percentage haematite‐stained grains in North Atlantic sediments (indicative of ice‐rafted debris events). Rivers with southerly catchments dominate fluvial input especially between c. 3.3 and 2 cal ka BP, concurrent with high precipitation in the Lake Baikal region. Copyright © 2011 John Wiley & Sons, Ltd.     

The influence of hydrology and climate on the isotope geochemistry of playa carbonates: a study from Pilot Valley, NV, USA

Carbonates often accompany lake and lake‐margin deposits in both modern and ancient geological settings. If these carbonates are formed in standing water, their stable isotope values reflect the aquatic chemistry at the time of precipitation and may provide a proxy for determining regional hydrologic conditions. Carbonate rhizoliths and water samples were collected from a playa lake in eastern Nevada. Pilot Valley (～43°N) is a closed‐basin, remnant playa from the Quaternary desiccation of palaeo‐Lake Bonneville. Water is added to the playa margin by free convection of dense brines to the east and forced convection of freshwater off the alluvial fan to the west. Both freshwater and saline springs dot the playa margin at the base of an alluvial fan. Water samples collected from seven springs show a range from ?16 to ?0·2‰ (Vienna Standard Mean Ocean Water), and are consistent with published values. The δ¹⁸O_calcite values from rhizolith samples range from ?18·3 to ?6·7‰ (Vienna Pee Dee Belemnite), and the average is ?12‰ V‐PDB (1 ? σ SD 2‰). With the exception of samples from Little Salt Spring, the range in the δ¹⁸O_calcite values collected from the rhizoliths confirms that they form in equilibrium with ambient water conditions on the playa. The initial geochemical conditions for the spring waters are dictated by local hydrology: freshwater springs emerge in the northern part of the basin to the east of a broad alluvial fan, and more saline springs emerge to the south where the influence of the alluvial fan diminishes. Rhizoliths are only found near the southern saline springs and their δ¹³C_calcite values, along with their morphology, indicate that they only form around saltgrass (Distichlis sp.). As the residence time of water on the playa increases, evaporation, temperature change and biological processes alter the aquatic chemistry and initiate calcite precipitation around the plant stems. The range in δ¹⁸O_calcite values from each location reflects environmental controls (e.g. evaporation and temperature change). These rhizoliths faithfully record ambient aquatic conditions during formation (e.g. geochemistry and water depth), but only record a partial annual signal that is constrained by saltgrass growth and the presence of standing water on the playa margin.     

Climatic and non-climatic effects on the δO and δC compositions of Lake Awassa, Ethiopia, during the last 6.5 ka

A comparison of a 6450 ¹⁴C yr δ¹⁸O and δ¹³C record of authigenic calcite from Lake Awassa, Ethiopia, with other proxy climate records in the area suggests that the lake records long-term regional climate changes. Co-varying and increasing δ¹⁸O and δ¹³C values from 4800 BP suggest an aridification of climate after the early Holocene insolation maximum. After 4000 BP, humid conditions return until after 2800 BP when δ¹⁸O increases again, reflecting more arid conditions recorded elsewhere in Ethiopia. In addition to these long-term changes, there are abrupt decreases in both δ¹⁸O_calcite and δ¹³C_calcite immediately after tephra layers. The likeliest explanation for these abrupt decreases in isotopes is the effect of tephra on the lake's catchment vegetation. δ¹⁸O, δ¹³C and lake-level measurements from Lake Awassa since the 1970s suggest that the lake is currently isotopically sensitive to short-term (annual–decadal) climate change. However, during this period, the catchment has undergone progressive deforestation that may have caused an increase in runoff. Caution is therefore required when reconstructing palaeoclimates as a contemporary lake may not always be a good analogue for lake hydrology in the past.     

Diagenetic overprinting of the sphaerosiderite palaeoclimate proxy: are records of pedogenic groundwater δ18O values preserved?

Meteoric sphaerosiderite lines (MSLs), defined by invariant δ¹⁸O and variable δ¹³C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre‐scale FeCO₃ nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well‐preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO₃) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca²⁺, Mg²⁺ and Mn²⁺ for Fe²⁺. Examples of diagenetically altered Cretaceous sphaerosiderite‐bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic δ¹⁸O and δ¹³C values are preserved. All three units contain poikilotopic calcite cements with significantly different δ¹⁸O and δ¹³C values from the co‐occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant δ¹⁸O vs. δ¹³C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric δ¹⁸O and δ¹³C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end‐member compositions. Modelled hyperbolic fluid mixing curves for the Success S2 Formation suggest precipitation from fluids that were < 25% sea water.     

Evidence for high temperature and 18O‐enriched fluids in the Arab‐D of the Ghawar Field,Saudi Arabia

Using the clumped isotope method, the temperature of dolomite and calcite formation and the oxygen isotopic composition (δ¹⁸O_w) of the diagenetic fluids have been determined in a core taken from the Arab‐D of the Ghawar field, the largest oil reservoir in the world. These analyses show that while the dolomites and limestones throughout the major zones of the reservoir recrystallized at temperatures between ca 80°C and 100°C, the carbonates near the top of the reservoir formed at significantly lower temperatures (20 to 30°C). Although the δ¹⁸O values of the diagenetic fluids show large variations ranging from ca <0‰ to ca +8‰, the variations exhibit consistent downhole changes, with the highest values being associated with the portion of the reservoir with the highest permeability and porosity. Within the limestones, dolomites and dolomites associated with the zone of high permeability, there are statistically significant different trends between the δ¹⁸O_w values and recrystallization temperature. These relationships have different intercepts suggesting that fluids with varying δ¹⁸O_w values were involved in the formation of dolomite and limestone compared to the formation of dolomite associated with the zone of high permeability. These new data obtained using the clumped isotope technique show how dolomitization and recrystallization by deep‐seated brines with elevated δ¹⁸O_w values influence the δ¹⁸O values of carbonates, possibly leading to erroneous interpretations unless temperatures can be adequately constrained.     

The δ60/58Ni Values of Twenty‐Six Selected Geological Reference Materials

The high‐precision δ^60/58Ni values of twenty‐six geological reference materials, including igneous rocks, sedimentary rocks, stream sediments, soils and plants are reported. The δ^60/58Ni values of all samples were determined by double‐spike MC‐ICP‐MS (Nu Plasma III). Isotope standard solution (NIST SRM 986) and geological reference materials (BHVO‐2, BCR‐2, JP‐1, PCC‐1, etc.) were used to evaluate the measurement bias and intermediate precision over a period of six months. Our results show that the intermediate precision of Ni isotope determination was 0.05‰ (2s, n = 69) for spiked NIST SRM 986 and typically 0.06‰ for actual samples, and the δ^60/58Ni _{NIST SRM 986} values were in excellent agreement with previous studies. Eighteen high‐precision Ni isotope ratios of geological reference materials are first reported here, and their δ^60/58Ni values varied from ?0.27‰ to 0.52‰, with a mean of 0.13 ± 0.34‰ (2s, n = 18). Additionally, SGR‐1b (0.56 ± 0.04‰, 2s), GSS‐1 (?0.27 ± 0.06‰, 2s), GSS‐7 (?0.11 ± 0.01‰, 2s), GSD‐10 (0.46 ± 0.06‰, 2s) and GSB‐12 (0.52 ± 0.06‰, 2s) could potentially serve as candidate reference materials for Ni isotope fractionation and comparison of Ni isotopic compositions among different laboratories.