Seasonal changes in the isotopic composition of planktonic foraminifera collected in Panama Basin sediment traps

Isotopic analyses have been made on five species of planktonic foraminifera collected in two deployments of PARFLUX Mark II time-series sediment traps in the Panama Basin. The automated sampling system on the traps provided 4 one-month samples from 29 July to 16 November 1979 and 6 two-month samples from December 1979 to November 1980.The δ¹⁸O values of Globigerinoides ruber and Globigerinoides sacculifer in this region are primarily affected by a low-salinity surface layer that forms during the early winter. These species each show a 1‰ total range in δ¹⁸O. The δ¹⁸O values of the colder-water species Globorotalia menardii, Neogloboquadrina dutertrei, and Globorotalia theyeri show smaller seasonal changes in δ¹⁸O. The δ¹³C values of G. ruber and G. sacculifer exhibit small seasonal changes (0.35 and 0.4‰ respectively) despite large seasonal changes in surface water productivity. The colder-water species exhibit only slightly larger changes in δ¹³C (up to 0.55‰) throughout the year. All colder-water species exhibit minimum or near minimum δ¹³C values during February and March, which is the period of maximum upwelling and primary productivity. Seasonal variations in the flux of foraminifera in the water column at this location will have only a small effect on the isotopic composition of the sediment assemblage; extreme values of δ¹⁸O and δ¹³C do not occur during the periods which are associated with the high flux of foraminiferal tests.     

Isotopic composition (δ18O and δD) of precipitation and groundwater in a semi‐arid,mountainous area (Guadiana Menor basin,Southeast Spain)

We characterize the precipitation and groundwater in a mountainous (peaks slightly above 3000 m a.s.l.), semi‐arid river basin in SE Spain in terms of the isotopes ¹⁸O and ²H. This basin, with an extension of about 7000 km², is an ideal site for such a study because fronts from the Atlantic and the Mediterranean converge here. Much of the land is farmed and irrigated both by groundwater and runoff water collected in reservoirs. A total of approximately 100 water samples from precipitation and 300 from groundwater have been analysed. To sample precipitation we set up a network of 39 stations at different altitudes (800–1700 m a.s.l.), with which we were able to collect the rain and snowfall from 29 separate events between July 2005 and April 2007 and take monthly samples during the periods of maximum recharge of the aquifers. To characterize the groundwater we set up a control network of 43 points (23 springs and 20 wells) to sample every 3 months the main aquifers and both the thermal and non‐thermal groundwater. We also sampled two shallow‐water sites (a reservoir and a river). The isotope composition of the precipitation forms a local meteoric water line (LMWL) characterized by the equation δD = 7·72δ¹⁸O + 9·90, with mean values for δ¹⁸O and δD of − 10·28‰ and − 69·33‰, respectively, and 12·9‰ for the d‐excess value. To correlate the isotope composition of the rainfall water with groundwater we calculated the weighted local meteoric water line (WLMWL), characterized by the equation δD = 7·40δ¹⁸O + 7·24, which takes into account the quantity of water precipitated during each event. These values of (dδD/dδ¹⁸O)< 8 and d‐excess (δD–8δ¹⁸O)< 10 in each curve bear witness to the ‘amount effect’, an effect which is more manifest between May and September, when the ground temperature is higher. Other effects noted in the basin were those of altitude and the continental influence. The isotopic compositions of the groundwater are represented by the equation δD = 4·79δ¹⁸O − 18·64. The groundwater is richer in heavy isotopes than the rainfall, with mean values of − 8·48‰ for δ¹⁸O and − 59·27‰ for δD. The isotope enrichment processes detected include a higher rate of evaporation from detrital aquifers than from carbonate ones, the effects of recharging aquifers from irrigation return flow and/or from reservoirs' leakage and enrichment in δ¹⁸O from thermal water. Copyright © 2010 John Wiley & Sons, Ltd.     

Groundwater recharge sources in semiarid irrigated mountain fronts

High-elevation mountains often constitute for basins important groundwater recharge sources through mountain-front recharge processes. These processes include streamflow losses and subsurface inflow from the mountain block. However, another key recharge process is from irrigation practices, where mountain streamflow is distributed across the irrigated piedmont. In this study, coupled groundwater fluctuation measurements and environmental tracers (¹⁸O, ²H, and major ions) were used to identify and compare the natural mountain-front recharge to the anthropogenically induced irrigation recharge. Within the High Atlas mountain front of the Ourika Basin, Central Morocco, the groundwater fluctuation mapping from the dry to wet season showed that recharge beneath the irrigated area was higher than the recharge along the streambed. Irrigation practices in the region divert more than 65% of the stream water, thereby reducing the potential for in-stream groundwater recharge. In addition, the irrigation areas close to the mountain front had greater water table increases (up to 3.5 m) compared with the downstream irrigation areas (<1 m increase). Upstream crops have priority to irrigation with stream water over downstream areas. The latter are only irrigated via stream water during large flood events and are otherwise supplemented by groundwater resources. These changes in water resources used for irrigation practices between upstream and downstream areas are reflected in the spatiotemporal evolution of the stable isotopes of groundwater. In the upstream irrigation area, the groundwater stable isotope values (δ¹⁸O: −8.4‰ to −7.4‰) reflect recharge by the diverted stream water. In the downstream irrigation area, the groundwater isotope values are lower (δ¹⁸O: −8.1‰ to −8.4‰) due to recharge via the flood water. In the nonirrigation area, the groundwater has the highest stable isotope values (δ¹⁸O: −6.8‰ to −4.8‰). This might be due to recharge via subsurface inflow from the mountain block to the mountain front and/or recharge via local low altitude rainfall. These findings highlight that irrigation practices can result in the dominant mountain-front recharge process for groundwater.     

The δ13C–δ18O variations in marble in the Hida Belt,Japan

Marble has a great potential to understand a history of various geological events occurring during tectonic processes. In order to decode metamorphic–metasomatic records on C–O isotope compositions of marble at mid-crustal conditions, we conducted a C–O–Sr isotope study on upper amphibolite-facies marbles and a carbonate–silicate rock from the Hida Belt, which was once a part of the crustal basement of the East Asian continental margin. Carbon and oxygen isotope analyses of calcite from marbles (Kamioka area) and a carbonate–silicate rock (Wadagawa area) show a large variation of δ¹³C [VPDB] and δ¹⁸O [VSMOW] values (from −4.4 to +4.2 ‰ and +1.6 to +20.8 ‰, respectively). The low δ¹³C values of calcites from the carbonate–silicate rock (from −4.4 to −2.9 ‰) can be explained by decarbonation (CO₂ releasing) reactions; carbon–oxygen isotope modeling suggests that a decrease of δ¹³C strongly depends on the amount of silicate reacting with carbonates. The occurrence of metamorphic clinopyroxene in marbles indicates that all samples have been affected by decarbonation reactions. All δ¹⁸O values of calcites are remarkably lower than the marine-carbonate values. The large δ¹⁸O variation can be explained by the isotope exchange via interactions between marble, external fluids, and/or silicates. Remarkably low δ¹⁸O values of marbles that are lower than mantle value (~+5 ‰) suggest the interaction with meteoric water at a later stage. Sr isotope ratios (⁸⁷Sr/⁸⁶Sr = 0.707255–0.708220) might be close to their protolith values. One zircon associated with wollastonite in a marble thin-section yields a U–Pb age of 222 ± 3 Ma, which represents the timing of the recrystallization of marble, triggered by H₂O-rich fluid infiltration at a relatively high-temperature condition. Our isotope study implies that the upper amphibolite-facies condition, like the Hida Belt, might be appropriate to cause decarbonation reactions which can modify original isotope compositions of marble if carbonates react with silicates.     

Diagenetic fluid evolution and water-rock interaction model of carbonate cements in sandstone: An example from the reservoir sandstone of the Fourth Member of the Xujiahe Formation of the Xiaoquan-Fenggu area,Sichuan Province,China

Carbonate cement is the most abundant cement type in the Fourth Member of the Xujiahe Formation in the Xiaoquan-Fenggu area of the West Sichuan Depression. Here we use a systematic analysis of carbonate cement petrology, mineralogy, carbon and oxygen isotope ratios and enclosure homogenization temperatures to study the precipitation mechanism, pore fluid evolution, and distribution of different types of carbonate cement in reservoir sand in the study area. Crystalline calcite has relatively heavy carbon and oxygen isotope ratios(δ13C = 2.14‰, δ18O = -5.77‰), and was precipitated early. It was precipitated directly from supersaturated alkaline fluid under normal temperature and pressure conditions. At the time of precipitation, the fluid oxygen isotope ratio was very light, mainly showing the characteristics of a mixed meteoric water-seawater fluid(δ18O = -3‰), which shows that the fluid during precipitation was influenced by both meteoric water and seawater. The calcite cement that fills in the secondary pores has relatively lighter carbon and oxygen isotope ratios(δ13C = -2.36‰, δ18O = -15.68‰). This cement was precipitated late, mainly during the Middle and Late Jurassic. An important material source for this carbonate cement was the feldspar corrosion process that involved organic matter. The Ca2+, Fe3+ and Mg2+ ions released by the clay mineral transformation process were also important source materials. Because of water-rock interactions during the burial process, the oxygen isotope ratio of the fluid significantly increased during precipitation, by about 3‰. The dolomite cements in calcarenaceous sandstone that was precipitated during the Middle Jurassic have heavier carbon and oxygen isotope ratios, which are similar to those of carbonate debris in the sandstone(δ13C = 1.93‰, δ18O = -6.11‰), demonstrating that the two are from the same source that had a heavier oxygen isotope ratio(δ18O of about 2.2‰). The differences in fluid oxygen isotope ratios during cement precipitation reflect the influences of different water-rock interaction systems or different water-rock interaction strengths. This is the main reason why the sandstone containing many rigid particles(lithic quartz sandstone) has a relatively negative carbon isotope ratio and why the precipitation fluid in calcarenaceous sandstone has a relatively heavier oxygen isotope ratio.     

Investigating the distribution and sources of organic matter in surface sediment of Coombabah Lake (Australia) using elemental,isotopic and fatty acid biomarkers

Extensive physical and biological measurements were made of the surface sediments within the shallow, semi-urbanised Coombabah Lake in southern Moreton Bay, Australia. Sediment bulk parameters (C/N ratios, δ¹³C and δ¹⁵N) and fatty acid biomarkers were used to determine distributions and sources of organic matter in the intertidal sediments. The determination of organic matter sources within coastal and estuarine settings is important in understanding the roles of organic matter as energy and nutrient sources. Spatial variability of biomarker values within the sediments were interpreted by thematic maps employing the Krigging algorithm. Grain size analysis indicated the lake was dominated by mud (<63 μm) in the southern (landward) and sand (>63 μm) in the northern (seaward) lake regions, respectively. Surface sediment organic C and N values ranged from 0.12% to 1.76% and 0.01% to 0.12% dry weight, respectively, and C/N ratios averaged 16.3±3.19%. Sedimentary δ¹³C values ranged from −26.1‰ to −20.9‰, with an average value of −23.9±1.0‰. Sedimentary δ¹⁵N values ranged from +1.7‰ to +4.8‰, with an average value of +2.8±0.8‰. Bulk sediment parameters suggested that sedimentary organic matter is provided predominantly by allochthonous sources in the form of fringing mangroves. Thirty-nine individual fatty acids were identified using gas chromatography–mass spectrometry. The mean contributions of long chain fatty acids (LCFAs), polyunsaturated fatty acids (PUFAs), saturated fatty acids (SAFAs) and bacterial fatty acids (BAFAs) were, respectively, 13.9±11.4%, 7.6±4.1%, 53.6±8.6% and 18.2±4.6% of the identified fatty acid methyl esters (FAMEs), with BAFAs occurring in all sampled sediments. Fatty acid compositions varied throughout lake sediments, which indicated spatial differences in autochthonous and allochthonous organic matter sources, including terrestrial and planktonic (i.e. zooplankton, diatoms and other algal species) sources. The contribution of organic matter from shoreline mangroves was confirmed by the presence of LCFAs and 18:2ω6 and 18:3ω3, which are markers for mangroves in this ecosystem. BAFAs were identified in increased proportions in sediments adjacent to urban developments and dominated by mud. Grain size was identified as a dominant factor in the fatty acid compositions and contributing values to FAME pool. Spatial patterns of C/N ratios, δ¹³C and δ¹⁵N values, and fatty acid biomarker contributions illustrated that there is a greater contribution of autochthonous and labile organic matter to the sedimentary organic matter pool in the northern (marine entrance) sediments compared to the more allochthonous sourced organic matter of the southern region of the lake. This study details the distribution and sources of organic matter within Coombabah Lake and illustrates the usefulness of a multiple biomarker approach in discriminating organic matter sources within estuarine environments.     

Organic carbon isotope gradient and ocean stratification across the late Ediacaran-Early Cambrian Yangtze Platform

Organic carbon isotope(δ13Corg) data from two well-preserved sections across a shallow-to-deep water transect of the late Ediacaran-Early Cambrian Yangtze Platform in South China show significant temporal and spatial variations. In the shallow-water Jiulongwan-Jijiapo section, δ13Corg values of the late Ediacaran Dengying Formation range from -29‰ to -24‰. In the deep-water Longbizui section, δ13Corg values from time-equivalent strata of the Dengying Formation are mostly between –35‰ and -32‰. These new data, in combination with δ13Corg data reported from other sections in South China, reveal a 6‰–8‰ shallow-to-deep water δ13Corg gradient. High δ13Corg values(-30‰) occur mostly in shallow-water carbonate rocks, whereas low δ13Corg values(-32‰) dominate the deep-water black shale and chert. The large temporal and spatial δ13Corg variations imply limited buffering effect from a large dissolved organic carbon(DOC) reservoir that was inferred to have existed in Ediacaran-Early Cambrian oceans. Instead, δ13Corg variations between platform and basin sections are more likely caused by differential microbial biomass contribution to total organic matter. High δ13Corg values(-30‰) documented from shallow-water carbonates are within the range of typical Phanerozoic δ13Corg data and may record the isotope signature of organic matter from primary(photosynthetic) production. In contrast, low δ13Corg values(-32‰) from deep-water sections may have resulted from higher chemoautotrophic or methanotrophic biomass contribution to bulk organic matter in anoxic environments. The δ13Corg data provide indirect evidence for ocean stratification and episodic chemocline fluctuations in the Ediacaran-Early Cambrian Yangtze Platform.     

Typhoon rainfall impact on drip water δ18O in Xianyun cave,Southeast China

Precisely dated high-resolution speleothems may record past typhoon events, however, the state of the art cave monitoring is a prerequisite to identify suitable stalagmites for the reconstruction of such events. With this motivation, we examined the isotopic composition (δ¹⁸O and d-excess values) of rainfall, outside river, cave drip water, and an underground river in the Xianyun cave system, located in southeastern China. Monthly to bi-monthly monitoring of environmental and isotopic conditions was conducted for 1 year, from December 2018 to December 2019, including a typhoon event (August 24, 2019 to August 26, 2019), called Bailu. The δ¹⁸O of rainfall samples over the cave and outside river water ranged from −9.7‰ to −1.9‰ and −8.2‰ to −6.3‰, respectively, while the δ¹⁸O of Typhoon Bailu rainfall and instantaneous outside river water ranged from −19.6‰ to −6.3‰ and −10.4‰ to −7.7‰, respectively. Typhoon Bailu-induced rainfall showed distinctly negative δ¹⁸O values as compared to those of the monthly and bi-monthly rainfall, exhibiting a three-stage inverted U-shaped variation characteristic. Four drip water monitoring sites inside the cave revealed low variations during the studied period with average values of −7.8‰, −8.0‰, −8.0‰, and −8.1‰. However, during the typhoon, the drip water δ¹⁸O values exhibited similar characteristic as outside rainfall but with just 0.2‰ negative deviation owing to precipitation amount and drip water source reservoir. The integration of rainfall amount with drip water source reservoir determines the degree to which a typhoon isotopic signature gets diluted during epikarst infiltration. This study provides the first instrumental evidence of typhoon signal in karst system in southeastern China. Our results imply that the δ¹⁸O of drip water in Xianyun cave can instantaneously respond to typhoon rainfall. However, the 0.2‰ shift in drip water δ¹⁸O is difficult to be recorded by speleothems. We suggest multi-year monitoring to ascertain fully if the stalagmites could be used as paleotyphoon proxy.     

A long‐term study of stable isotopes as tracers of processes governing water flow and quality in a lowland river basin: the upper Thames,UK

A long‐term study of O, H and C stable isotopes has been undertaken on river waters across the 7000‐km² upper Thames lowland river basin in the southern UK. During the period, flow conditions ranged from drought to flood. A 10‐year monthly record (2003–2012) of the main River Thames showed a maximum variation of 3‰ (δ¹⁸O) and 20‰ (δ²H), although interannual average values varied little around a mean of –6.5‰ (δ¹⁸O) and –44‰ (δ²H). A δ²H/δ¹⁸O slope of 5.3 suggested a degree of evaporative enrichment, consistent with derivation from local rainfall with a weighted mean of –7.2‰ (δ¹⁸O) and –48‰ (δ²H) for the period. A tendency towards isotopic depletion of the river with increasing flow rate was noted, but at very high flows (>100 m³/s), a reversion to the mean was interpreted as the displacement of bank storage by rising groundwater levels (corroborated by measurements of specific electrical conductivity). A shorter quarterly study (October 2011–April 2013) of isotope variations in 15 tributaries with varying geology revealed different responses to evaporation, with a well‐correlated inverse relationship between Δ¹⁸O and baseflow index for most of the rivers. A comparison with aquifer waters in the basin showed that even at low flow, rivers rarely consist solely of isotopically unmodified groundwater. Long‐term monitoring (2003–2007) of carbon stable isotopes in dissolved inorganic carbon (DIC) in the Thames revealed a complex interplay between respiration, photosynthesis and evasion, but with a mean interannual δ¹³C‐DIC value of –14.8 ± 0.5‰, exchange with atmospheric carbon could be ruled out. Quarterly monitoring of the tributaries (October 2011–April 2013) indicated that in addition to the aforementioned factors, river flow variations and catchment characteristics were likely to affect δ¹³C‐DIC. Comparison with basin groundwaters of different alkalinity and δ¹³C‐DIC values showed that the origin of river baseflow is usually obscured. The findings show that long‐term monitoring of environmental tracers can help to improve the understanding of how lowland river catchments function. Copyright © NERC 2015. Hydrological Processes © 2015 John Wiley & Sons, Ltd.     

Modern stable isotopic (δ18O, δ2H, δ13C) variation in terrestrial,fluvial, estuarine and marine waters from north‐central Sarawak,Malaysian Borneo

Stable isotope data on humid tropical hydrology are scarce and, at present, no such data exist for Borneo. Delta¹⁸O, δ²H and δ¹³C were analysed on 22 water samples from different parts of the Sungai (river) Niah basin (rain, cave drip, rainforest pool, tributary stream, river, estuary, sea) in north‐central Sarawak, Malaysian Borneo. This was done to improve understanding of the modern stable isotope systematics of the Sungai Niah basin, essential for the palaeoenvironmental interpretation of the Late Quaternary stable isotope proxies preserved in the Great Cave of Niah. The Niah hydrology data are put into a regional context using the meteoric water line for Southeast Asia, as derived from International Atomic Energy Agency/World Meteorological Organization isotopes in precipitation network data. Although the Niah hydrological data‐set is relatively small, spatial isotopic variability was found for the different subenvironments of the Sungai Niah basin. A progressive enrichment occurs towards the South China Sea (δ¹⁸O ?4·6‰; δ²H ?29·3‰; δ¹³C ?4·8‰) from the tributary stream (δ¹⁸O ?8·4‰; δ²H ?54·7‰; δ¹³C ?14·5‰) to up‐river (δ¹⁸O c. ?8‰; δ²H c. ?51‰; δ¹³C c. ?12‰) and down‐river values (δ¹⁸O c. ?7·5‰; δ²H c. ?45‰; δ¹³C c. ?11‰). This is thought to reflect differential evaporation and mixing of different components of the water cycle and a combination of depleted biogenic δ¹³C (plant respiration and decay) with enriched δ¹³C values (due to photosynthesis, atmospheric exchange, mixing with limestone and marine waters) downstream. Cave drip waters are relatively enriched in δ¹³C as compared to the surface waters. This may indicate rapid degassing of the cave drips as they enter the cave atmosphere. Copyright © 2005 John Wiley & Sons, Ltd.     

Using stable isotopes of surface water and groundwater to quantify moisture sources across the Yellow River source region

Characterization of stable isotope compositions (δ²H and δ¹⁸O) of surface water and groundwater in a catchment is critical for refining moisture sources and establishing modern isotope–elevation relationships for paleoelevation reconstructions. There is no consensus on the moisture sources of precipitation in the Yellow River source region during summer season. This study presents δ²H and δ¹⁸O data from 111 water samples collected from tributaries, mainstream, lakes, and groundwater across the Yellow River source region during summertime. Measured δ¹⁸O values of the tributaries range from ?13.5‰ to ?5.8‰ with an average of ?11.0‰. Measured δ¹⁸O values of the groundwater samples range from ?12.7‰ to ?10.5‰ with an average of ?11.9‰. The δ¹⁸O data of tributary waters display a northward increase of 1.66‰ per degree latitude. The δ¹⁸O data and d‐excess values imply that moisture sources of the Yellow River source region during summertime are mainly from the mixing of the Indian Summer Monsoon and the Westerlies, local water recycling, and subcloud evaporation. Analysis of tributary δ¹⁸O data from the Yellow River source region and streamwater and precipitation δ¹⁸O data from its surrounding areas leads to a best‐fit second‐order polynomial relationship between δ¹⁸O and elevation over a 4,600 m elevation range. A δ¹⁸O elevation gradient of ?1.6‰/km is also established using these data, and the gradient is in consistence with the δ¹⁸O elevation gradient of north and eastern plateau. Such relationships can be used for paleoelevation reconstructions in the Yellow River source region.     

Improved high-resolution global and regionalized isoscapes of δ18O, δ2H and d-excess in precipitation

Patterns of δ¹⁸O and δ²H in Earth's precipitation provide essential scientific data for use in hydrological, climatological, ecological and forensic research. Insufficient global spatial data coverage promulgated the use of gridded datasets employing geostatistical techniques (isoscapes) for spatiotemporally coherent isotope predictions. Cluster-based isoscape regionalization combines the advantages of local or regional prediction calibrations into a global framework. Here we present a revision of a Regionalized Cluster-Based Water Isotope Prediction model (RCWIP2) incorporating new isotope data having extensive spatial coverage and a wider array of predictor variables combined with high-resolution gridded climatic data. We introduced coupling of δ¹⁸O and δ²H (e.g., d-excess constrained) in the model predictions to prevent runaway isoscapes when each isotope is modelled separately and cross-checked observed versus modelled d-excess values. We improved model error quantification by adopting full uncertainty propagation in all calculations. RCWIP2 improved the RMSE over previous isoscape models by ca. 0.3 ‰ for δ¹⁸O and 2.5 ‰ for δ²H with an uncertainty <1.0 ‰ for δ¹⁸O and < 8 ‰ for δ²H for most regions of the world. The determination of the relative importance of each predictor variable in each ecoclimatic zone is a new approach to identify previously unrecognized climatic drivers on mean annual precipitation δ¹⁸O and δ²H. The improved RCWIP2 isoscape grids and maps (season, monthly, annual, regional) are available for download at https://isotopehydrologynetwork.iaea.org .     

Carbon isotopic compositions of organic matter across continental Cretaceous–Tertiary (K–T) boundary sections: Implications for paleoenvironment after the K–T impact event

To assess the environmental perturbation induced by the impact event that marks the Cretaceous–Tertiary (K–T) boundary, concentrations and isotopic compositions of bulk organic carbon were determined in sedimentary rocks that span the terrestrial K–T boundary at Dogie Creek, Montana, and Brownie Butte, Wyoming in the Western Interior of the United States. The boundary clays at both sites are not bounded by coals. Although coals consist mainly of organic matter derived from plant tissue, siliceous sedimentary rocks, such as shale and clay, may contain organic matter derived from microbiota as well as plants. Coals record δ¹³C values of plant-derived organic matter, reflecting the δ¹³C value of atmospheric CO₂, whereas siliceous sedimentary rocks record the δ¹³C values of organic matter derived from plants and microbiota. The microbiota δ¹³C value reflects not only the δ¹³C value of atmospheric CO₂, but also biological productivity. Therefore, the siliceous rocks from these sites yields information that differs from that obtained previously from coal beds.Across the freshwater K–T boundary at Brownie Butte, the δ¹³C values decrease by 2.6‰ (from − 26.15‰ below the boundary clay to − 28.78‰ above the boundary clay), similar to the trend in carbonate at marine K–T sites. This means that the organic δ¹³C values reflect the variation of δ¹³C of atmospheric CO₂, which is in equilibrium with carbon isotopes at the ocean surface. Although a decrease in δ¹³C values is observed across the K–T boundary at Dogie Creek (from − 25.32‰ below the boundary clay to − 26.11‰ above the boundary clay), the degree of δ¹³C-decrease at Dogie Creek is smaller than that at Brownie Butte and that for marine carbonate.About 2‰ decrease in δ¹³C of atmospheric CO₂ was expected from the δ¹³C variation of marine carbonate at the K–T boundary. This δ¹³C-decrease of atmospheric CO₂ should affect the δ¹³C values of organic matter derived from plant tissue. As such a decrease in δ¹³C value was not observed at Dogie Creek, a process that compensates the δ¹³C-decrease of atmospheric CO₂ should be involved. For example, the enhanced contribution of ¹³C-enriched organic matter derived from algae in a high-productivity environment could be responsible. The δ¹³C values of algal organic matter become higher than, and thus distinguishable from, those of plant organic matter in situations with high productivity, where dissolved HCO₃⁻ becomes an important carbon source, as well as dissolved CO₂. As the δ¹³C-decrease of atmospheric CO₂ reflected a reduction of marine productivity, the compensation of the δ¹³C decrease by the enhanced activity of the terrestrial microbiota means that the microbiota at freshwater environment recovered more rapidly than those in the marine environment.A distinct positive δ¹³C excursion of 2‰ in the K–T boundary clays is superimposed on the overall decreasing trend at Dogie Creek; this coincides with an increase in the content of organic carbon. We conclude that the K–T boundary clays include ¹³C-enriched organic matter derived from highly productive algae. Such a high biological productivity was induced by phenomena resulting from the K–T impact, such as nitrogen fertilization and/or eutrophication induced by enhanced sulfide formation. The high productivity recorded in the K–T boundary clays means that the freshwater environments (in contrast to marine environments) recovered rapidly enough to almost immediately (within 10 yr) respond to the impact-related environmental perturbations.     

Oxygen and carbon isotope evidence for seawater-hydrothermal alteration of the Macquarie Island ophiolite

Rocks of the Miocene Macquarie Island ophiolite, south of New Zealand, have oxygen and carbon isotopic compositions comparable to those of seafloor rocks. Basalt glass and weathered basalts have δ¹⁸O values at 5.8–6.0‰ and 7.9–9.5‰, respectively, similar to drilled seafloor rocks including samples from the Leg 29 DSDP holes near Macquarie Island. Compared to the basalt glass, the greenschist to amphibolite facies metaintrusives are depleted in¹⁸O (δ¹⁸O=3.2–5.9‰) similar to dredged seafloor samples, whereas the metabasalts are enriched (δ¹⁸O=7.1–9.7‰). Although the gabbros are only slightly altered in thin-section they have exchanged oxygen with a hydrothermal fluid to a depth of at least 4.5 km. There is an approximate balance between¹⁸O depletion and enrichment in the exposed ophiolite section. The carbon isotopic composition of calcite in the weathered basalts (δ¹³C=1.0–2.0‰) is similar to those of drilled basalts, but the metamorphosed rocks have low δ¹³C values (?14.6 to 0.9‰).These data are compatible with two seawater circulation regimes. In the upper regime, basalts were weathered by cold seawater in a circulation system with high water/rock ratios (?1.0). Based on calcite compositions weathering temperatures were less than 20°C and the carbon was derived from a predominantly inorganic marine source. As previously suggested for the Samail ophiolite, it is postulated that the lower hydrothermal regime consisted of two coupled parts. At the deeper levels, seawater circulating at low water/rock ratios (0.2–0.3) and high temperatures (300–600°C) gave rise to¹⁸O-depleted gabbro and sheeted dikes via open system exchange reactions. During reaction the seawater underwent a shift in oxygen isotopic composition (δ¹⁸O=1.0–5.0‰) and subsequently caused¹⁸O enrichment of the overlying metabasalts. In the shallower part of the hydrothermal regime the metabasalts were altered at relatively high water/rock ratios (1.0–10.0) and temperatures in the range 200–300°C. The relatively low water/rock ratios in the hydrothermal regime are supported by the low δ¹³C values of calcite, interpreted as evidence of juvenile carbon in contrast to the inorganic marine carbon found in the weathered basalts.     

Coupled silicon–oxygen isotope fractionation traces Archaean silicification

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

Evolution of the oceanic calcium cycle during the late Mesozoic: Evidence from δ44/40Ca of marine skeletal carbonates

The Ca isotope compositions of 37 late Mesozoic skeletal carbonates, belemnites and brachiopods, from the Tethyan realm were analyzed by thermal (TIMS) and plasma (MC-ICP-MS) ionization mass spectrometry. A poor correlation between δ^44/40Ca and δ¹⁸O values of belemnites suggests only a weak temperature dependency for the Ca isotope composition of belemnites, likely less than 0.02‰/°C. The δ^44/40Ca record of belemnites was therefore used to reconstruct the Ca isotope composition of paleo-seawater (δ^44/40Ca_SW), based on an experimentally determined fractionation factor between seawater Ca and belemnite calcite (α_CC–SW) of ∼ 0.9986. The inferred δ^44/40Ca_SW record, with an average stratigraphic resolution of 1 Ma, shows systematic temporal variation of ∼ 0.5‰ with the Middle/Late Jurassic (∼ 154 Ma) minimum of ∼ 1.4‰ and a subsequent general increase to the Early Cretaceous (∼ 124 Ma) maximum of ∼ 1.9‰. The global nature of the δ^44/40Ca_SW record is supported by identical Ca isotope compositions of coeval (Kimmeridgian) belemnites collected from two distinct paleogeographic regions, the southern (New Zealand) and northern (Germany) margin of the Tethys Ocean. The observed late Mesozoic δ^44/40Ca_SW record was simulated using a simple Ca isotope mass balance model, and the results indicate that the variation in δ^44/40Ca_SW record can be explained by changes in oceanic input fluxes of Ca that were independent of the carbonate ion fluxes, such as the hydrothermal Ca flux or the release of Ca to the oceans via dolomitization of marine carbonates.     

Isotope hydrology of the Allt a' Mharcaidh catchment,Cairngorms, Scotland: implications for hydrological pathways and residence times

The hydrology of oxygen‐18 (¹⁸O) isotopes was monitored between 1995 and 1998 in the Allt a' Mharcaidh catchment in the Cairngorm Mountains, Scotland. Precipitation (mean δ¹⁸O=−7·69‰) exhibited strong seasonal variation in δ¹⁸O values over the study period, ranging from −2·47‰ in the summer to −20·93‰ in the winter months. As expected, such variation was substantially damped in stream waters, which had a mean and range of δ¹⁸O of −9·56‰ and −8·45 to −10·44‰, respectively. Despite this, oxygen‐18 proved a useful tracer and streamwater δ¹⁸O variations could be explained in terms of a two‐component mixing model, involving a seasonally variable δ¹⁸O signature in storm runoff, mixing with groundwater characterized by relatively stable δ¹⁸O levels. Variations in soil water δ¹⁸O implied the routing of depleted spring snowmelt and enriched summer rainfall into streamwaters, probably by near‐surface hydrological pathways in peaty soils. The relatively stable isotope composition of baseflows is consistent with effective mixing processes in shallow aquifers at the catchment scale. Examination of the seasonal variation in δ¹⁸O levels in various catchment waters provided a first approximation of mean residence times in the major hydrological stores. Preliminary estimates are 0·2–0·8 years for near‐surface soil water that contributes to storm runoff and 2 and >5 years for shallow and deeper groundwater, respectively. These ¹⁸O data sets provide further evidence that the influence of groundwater on the hydrology and hydrochemistry of upland catchments has been underestimated. Copyright © 2000 John Wiley & Sons, Ltd.     

Spatial and temporal variability of stable isotopes (δ18O and δ2H) in surface waters of arid,mountainous Central Asia

Characterization of spatial and temporal variability of stable isotopes (δ¹⁸O and δ²H) of surface waters is essential to interpret hydrological processes and establish modern isotope–elevation gradients across mountainous terrains. Here, we present stable isotope data for river waters across Kyrgyzstan. River water isotopes exhibit substantial spatial heterogeneity among different watersheds in Kyrgyzstan. Higher river water isotope values were found mainly in the Issyk‐Kul Lake watershed, whereas waters in the Son‐Kul Lake watershed display lower values. Results show a close δ¹⁸O–δ²H relation between river water and the local meteoric water line, implying that river water experiences little evaporative enrichment. River water from the high‐elevation regions (e.g., Naryn and Son‐Kul Lake watershed) had the most negative isotope values, implying that river water is dominated by snowmelt. Higher deuterium excess (average d = 13.9‰) in river water probably represents the isotopic signature of combined contributions from direct precipitation and glacier melt in stream discharge across Kyrgyzstan. A significant relationship between river water δ¹⁸O and elevation was observed with a vertical lapse rate of 0.13‰/100 m. These findings provide crucial information about hydrological processes across Kyrgyzstan and contribute to a better understanding of the paleoclimate/elevation reconstruction of this region.     

Evaluation of the carbon isotopic effects of NDIR and CRDS analyzers on atmospheric CO2 measurements

Non-dispersive infrared(NDIR) and cavity ring-down spectroscopy(CRDS) CO_2 analyzers use 12CO_2 isotopologue absorption lines and are insensitive to all or part of other CO_2-related isotopologues. This may produce biases in CO_2 mole fraction measurements of a sample if its carbon isotopic composition deviates from that of the standard gases being used. To evaluate and compare the effects of carbon isotopic composition on NDIR and CRDS CO_2 analyzers, we prepared three test sample air cylinders with varying carbon isotopic abundances and calibrated them against five standard cylinders with ambient carbon isotopic composition using CRDS and NDIR systems. We found that the CO_2 mole fractions of the sample cylinders measured by G1301(CRDS) were in good agreement with those measured by Lo Flo(NDIR). The CO_2 values measured by both instruments were higher than that of a CO_2 isotope measured by G2201i(CRDS) analyzer for a test cylinder with depleted carbon isotopic composition δ~(13)C =-36.828‰, whereas no obvious difference was found for other two test cylinders with δ~(13)C=-8.630‰ and δ~(13)C=-15.380‰, respectively. According to the theoretical and experimental results, we concluded that the total CO_2 mole fractions of samples with depleted isotopic compositions can be corrected on the basis of their 12CO_2 values calibrated by standard gases using Lo Flo and G1301 if the δ~(13)C and δ18O values are known.