Stable isotopic information for hydrological investigation in Hailuogou watershed on the eastern slope of Mount Gongga, China

Hydrological systems have been seriously affected by changes of glaciations and snow covers in Mount Gongga, Sichuan, China, but the relevance of ice-snow melt for alpine river basin hydrology is so far not well known. To better understand hydrological features of the Hailuogou River, changes of δ¹⁸O and δ²H were investigated by analyzing 117 water samples collected from May 2008 to November 2009. Our results show that the stream water contains a relatively intermediate magnitude of isotopic variations, with δ¹⁸O ranging from ?18.09 to ?13.08 ‰ and δ²H from ?126.5 to ?88.8 ‰. The average values are both higher than those of ice-snow meltwater, but lower than those of meteoric water. These data also show a gradually increasing trend from upstream to downstream, and these changes might document the fingerprint of ice-snow melt in the headwater region and indicate the increasing recharge of heavy isotope-enriched waters with flow distance. The similarity in slopes of δ²H and δ¹⁸O relationship for meteoric waters and stream waters suggests that the isotopic signature of precipitation is well preserved in stream flow, and during the rainfall and stream flow the evaporation is only minor. Based on δ¹⁸O model, the results suggested that the fraction of ice-snow meltwater input over the total stream flow ranged from 84.50 to 86.52 % in the headwater region, but the fraction of ice-snow meltwater input from upper basin downward was significantly decreased. The study demonstrates that ice-snow meltwater is a substantially important water source in alpine regions on the edge of Tibetan Plateau.     

Assessment of paleo-recharge under the Fennoscandian Ice Sheet and its impact on regional groundwater flow in the northern Baltic Artesian Basin using a numerical model

The study investigates the mechanism of glacial meltwater recharge under the Fennosciandian Ice Sheet during the last glacial maximum (LGM) and its impact on regional groundwater flow in the northern Baltic Artesian Basin (BAB) in Estonia and Latvia. The current hypothesis is that a flow reversal occurred in the BAB due to subglacial recharge during the LGM. This hypothesis is supported by an extensive dataset of geochemical and isotopic measurements in the groundwater of northern Estonia, exhibiting significant depletion in δ¹⁸O with respect to modern precipitation. To verify the consistency of this hypothesis and better understand groundwater flow dynamics during the LGM period, a numerical model is developed for this area. Two cross-sectional models have been created across the northern BAB, in which groundwater flow and the transport of δ¹⁸O have been simulated from the beginning of the LGM to present-day. Several simulations were performed with different subglacial boundary conditions, to investigate the uncertainty related to subglacial recharge of meltwater during the LGM and the subsequent flow reversal in the northern BAB. Several simulations provide a satisfying fit between computed and observed values of δ¹⁸O, which means that the hypothesis of subglacial recharge of meltwater is consistent with δ¹⁸O distribution. The numerical model suggests that preservation of meltwater in northern Estonia is controlled by confining layers and the proximity to the outcrop area of aquifers, located in the Gulf of Finland. The results also suggest that glacial meltwater has been preserved under the Baltic Sea in the Gulf of Riga.     

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.     

Investigation on the hydrodynamics of Ganga Alluvial Plain using environmental isotopes: a case study of the Gomati River Basin, northern India

An investigation using environmental isotopes (δ¹⁸O and δD) was conducted to gain insight into the hydrological processes of the Ganga Alluvial Plain, northern India. River-water, shallow-groundwater and lake-water samples from the Gomati River Basin were analyzed. During the winter season, the δ¹⁸O and δD compositions of the Gomati River water ranged from ?1.67 to ?7.62 ‰ and ?25.08 to ?61.50 ‰, respectively. Deuterium excess values in the river water (+0.3 to ?13 ‰) and the lake water (?20 ‰) indicate the significance of evaporation processes. Monthly variation of δ¹⁸O and δD values of the Gomati River water and the shallow groundwater follows a similar trend, with isotope-depleted peaks for δ¹⁸O and δD synchronized during the monsoon season. The isotopically depleted peak values of the river water (δ¹⁸O?=??8.30 ‰ and δD?=??57.10 ‰) can be used as a proxy record for the isotopic signature of the monsoon precipitation in the Ganga Alluvial Plain.     

The recharge of glacial meltwater and its influence on the geochemical evolution of groundwater in the Ordovician-Cambrian aquifer system,northern part of the Baltic Artesian Basin

The geochemical evolution of groundwater in the Ordovician-Cambrian aquifer system in the northern part of the Baltic Artesian Basin (BAB) illustrates how continental glaciations have influenced groundwater systems in proglacial areas. The aquifer system contains water that has originated from various end-members: recent meteoric water, glacial meltwater and relict Na-Cl brine. The saline formation water that occupied the aquifer system prior to the glacial meltwater intrusion has been diluted by meltwaters of advancing-retreating ice sheets. The diversity in the origin of groundwater in the aquifer system is illustrated by a wide variety in δ¹⁸O values that range from −11‰ to −22.5‰. These values are mostly depleted with respect to values found in modern precipitation in the area. The chemical and isotopic composition of groundwater has been influenced by mixing between waters originating from different end-members. In addition, the freshening of a previously saline water aquifer due to glacial meltwater intrusion has initiated various types of water-rock interaction (e.g. ion exchange, carbonate mineral dissolution).     

Snowmelt runoff and groundwater discharge in Himalayan rivers: a case study of the Satluj River,NW India

The Himalayas are one of the largest cryospheric systems outside the Polar Regions, and include more than 12,000 glaciers spread over an area of about 33,000 km². The Himalayan glaciers and snow packs retreating at an accelerating rate, thereby creating an alarming situation for the huge population that resides in northwestern India and southeastern Pakistan, as they depend on surface water resources in the region and rivers emanating from the Himalayas. This work attempts to quantify the contribution of different sources such as glacial/ice/snow melt and groundwater discharge to the Satluj River using the stable isotopes based hydrograph separation method at Ropar (foot hill) and Yusufpur in plain of Punjab, India. A mass balance model of three-component mixing has been engaged using the values of δ¹⁸O and electrical conductivity of the river water, and its discharge fraction, to estimate the time-varying relative proportion of each component from July 2013 to January 2014. The proportion of glacier melt was found to peak up to ~?64% at Ropar and ~?15% at Yusufpur during the wet summer months. The fraction of groundwater discharge was found to vary between 10–20% at Ropar and 25–35% at Yusufpur (Punjab plain) over time. The observed trend of d-excess (deuterium excess) values of river water also suggests that the glaciers and snow packs at higher altitudes contain a significant fraction of snow derived from vapor originating in the Mediterranean region, driven by the mid-latitude westerlies known as western disturbances.     

Development of glacial and interglacial conditions in the Nordic seas between 1.5 and 0.35 Ma

Sedimentological and geochemical proxy records of a deep-sea sediment core from the southern central Nordic seas were used to reconstruct the development of glacial and interglacial conditions during the Early and Middle Pleistocene, i.e., late Matuyama to middle Brunhes Chron (1.5–0.35 Ma). An enhancement of both glacial and interglacial characteristics is observed during early Brunhes oxygen isotope stages (OIS) 16 and 15, respectively. Any intensification of the climatic conditions prior to this, as was previously described for the eastern part of the Nordic seas, is not recognized at our study site. It is further shown that the glacial–interglacial environmental contrasts increased from the early to the middle Bruhnes Chron. Of all glacial periods investigated OIS 12 is characterized by the most severe conditions, showing both maximum input of iceberg-rafted debris (IRD) as well as planktic foraminiferal δ¹⁸O values comparable to those of the Last Glacial Maximum. Among the interglaciations, OIS 11 is by far the longest interval and the first to show fully developed interglacial conditions, i.e., Holocene-like δ¹⁸O values and a minimum of IRD deposition. Hence, our comparison supports bottom water δ¹⁸O studies that have indicated the existence of a gradual intensification of glacial–interglacial climate contrasts during the Middle Pleistocene.     

Surface studies of water isotopes in Antarctica for quantitative interpretation of deep ice core data

Polar ice cores are unique climate archives. Indeed, most of them have a continuous stratigraphy and present high temporal resolution of many climate variables in a single archive. While water isotopic records (δD or δ¹⁸O) in ice cores are often taken as references for past atmospheric temperature variations, their relationship to temperature is associated with a large uncertainty. Several reasons are invoked to explain the limitation of such an approach; in particular, post-deposition effects are important in East Antarctica because of the low accumulation rates. The strong influence of post-deposition processes highlights the need for surface polar research programs in addition to deep drilling programs. We present here new results on water isotopes from several recent surface programs, mostly over East Antarctica. Together with previously published data, the new data presented in this study have several implications for the climatic reconstructions based on ice core isotopic data: (1) The spatial relationship between surface mean temperature and mean snow isotopic composition over the first meters in depth can be explained quite straightforwardly using simple isotopic models tuned to d-excess vs. δ¹⁸O evolution in transects on the East Antarctic sector. The observed spatial slopes are significantly higher (～ 0.7–0.8‰·°C^?1 for δ¹⁸O vs. temperature) than seasonal slopes inferred from precipitation data at Vostok and Dome C (0.35 to 0.46‰·°C^?1). We explain these differences by changes in condensation versus surface temperature between summer and winter in the central East Antarctic plateau, where the inversion layer vanishes in summer. (2) Post-deposition effects linked to exchanges between the snow surface and the atmospheric water vapor lead to an evolution of δ¹⁸O in the surface snow, even in the absence of any precipitation event. This evolution preserves the positive correlation between the δ¹⁸O of snow and surface temperature, but is associated with a much slower δ¹⁸O-vs-temperature slope than the slope observed in the seasonal precipitation. (3) Post-deposition effects clearly limit the archiving of high-resolution (seasonal) climatic variability in the polar snow, but we suggest that sites with an accumulation rate of the order of 40 kg.m^?2.yr^?1 may record a seasonal cycle at shallow depths.     

Zircon U-Pb and oxygen isotope evidence for a large-scale O depletion event in igneous rocks during the Neoproterozoic

Oxygen isotope analysis and U-Pb dating were carried out on zircons from granite, granitic gneiss and eclogite in the Dabie-Sulu orogenic belt of east-central China. The results show a wide variation in zircon δ¹⁸O values from −10.9 to 8.5‰. Most of the values are lower than normal mantle zircon and almost half have prominently negative values. The low δ¹⁸O zircons have protolith ages of 700 to 800 Ma and metamorphic ages of 205 to 250 Ma, respectively. Fluid availability within the metaigneous rocks dictates the extent of metamorphic recrystallization and overgrowth. The igneous zircons have preserved their magmatic zoning and middle Neoproterozoic U-Pb age during the Triassic metamorphism, indicating low fluid availability. Widespread low δ¹⁸O values are identified in the magmatic zircons of middle Neoproterozoic age, within an outcrop area of over 20,000 km² along the northern edge of the South China Block. The low δ¹⁸O zircons record the presence of large volumes of low δ¹⁸O igneous rocks that were derived from remelting of meteoric-hydrothermally altered rocks at some time between 700 and 800 Ma.The U-Pb ages for metaigneous protoliths and granites are correlated not only with the timing of rifting accompanying the breakup of Rodinia, but also with contemporary glacial deposits in the South China Block at paleolatitudes of 30 to 40°N. Melting of glacial ice and snow is suggested, instead of the direct involvement of meteoric water, to produce the low δ¹⁸O fluid with oxygen isotopic signatures like the cold-climate meteoric water. The rifting created conditions favorable to anatexis of meteoric-hydrothermally altered rocks. Glaciated regions supplied copious water for the water-rock interaction during magma emplacement along rifting zones. Both rifting and glaciation favored the generation of the low δ¹⁸O magmas in the region. The low δ¹⁸O zircons are thus interpreted to have crystallized from the low δ¹⁸O magmas of middle Neoproterozoic age, and onset of the generation of low δ¹⁸O magmas in the northern margin of the South China Block is estimated to occur at about 758 ± 15 Ma. The large-scale remelting of hydrothermally altered crust not only results from repetitive emplacement of mafic magmas along the rifting zones with protracted episodes of water-rock interaction, but also involves rift systems that rapidly introduce large volumes of fluid through confined pathways and traps in a short space of time in response to tectonic triggers. Occurrence of the large-scale ¹⁸O depletion during the middle Neoproterozoic may be a manifestation of the cold paleoclimate related to the snowball Earth event.     

The reef builder gastropod Dendropomapetreaum - A proxy of short and long term climatic events in the Eastern Mediterranean

High-resolution δ¹⁸O and δ¹³C records obtained from seven cores were drilled from ledges of the reef builder gastropod Dendropomapetreaum and used to reconstruct variations in the Levantine basin sea surface temperature, hydrology and productivity during the past 500 years. The δ¹⁸O of the aragonite shell of living D. petreaum indicate that skeletal deposition occurs under isotopic equilibrium and faithfully record the temperature and surface water δ¹⁸O during summer and autumn. The mean down core δ¹⁸O record clearly captures global and local climatic events, such as the Little Ice Age (LIA) and the recent warming of surface waters in the Eastern Mediterranean. Comparison to the Western Mediterranean vermetid δ¹⁸O record reveals changes in the freshwater/evaporation budgets of the two basins during cold and warm periods. The Eastern basin had lower surface temperatures and excess evaporation during the LIA and experienced a relatively larger warming and/or a decrease in freshwater/evaporation during the past 70 years. The D. petraeum δ¹³C is strongly related to δ¹³C of dissolved inorganic carbon and to the primary productivity of the surface water. The mean down core δ¹³C record exhibits enrichment during the LIA maximum and a strong depletion trend during the last century. The LIA δ¹³C enrichment is attributed to an increase in primary production and high nutrient levels which resulted from increased vertical mixing and upwelling. The last century δ¹³C depletion is mostly related to the increased anthropogenic emissions of ¹³C depleted carbon dioxide and to a certain decrease in primary production. The data indicate that D. petraeum isotopic signatures are unique proxies for last 500 years high-resolution reconstruction of paleo-oceanographic environments in the Mediterranean and potentially in the sub-tropical Atlantic regions.     

A hydrogeochemical survey of Kilimanjaro (Tanzania): implications for water sources and ages

Kilimanjaro, Tanzania, the highest mountain in Africa, has undergone extensive hydrologic changes over the past century in an area where water resources are critical. A hydrochemical and isotopic synoptic sampling program in January 2006 is used to characterize hydrogeology, hydrology, and water quality of the area. Samples were collected from the summit and southern side of Kilimanjaro and the Moshi region (Tanzania). Sample sources included four glaciers, seven groundwater wells, 12 rivers, 10 springs, precipitation, and a lake. Analyses included major ion chemistry, stable isotopes of water (¹⁸O and D); in addition, seven samples were analyzed for tritium. The samples generally have good water quality with the exception of three samples with elevated fluoride concentrations (>3 mg/L) and elevated nitrate concentrations (>2.5 mg/L NO₃ as N). There is a strong elevation control on stable isotopes, with an apparent elevation effect of – 0.1 ‰ δ¹⁸O per 100 m rise in elevation (R ² = 0.79). The results, including the tritium values, show that the hydrogeologic system is comprised of both local and regional flow systems, and that regional rivers are receiving significant inflow from shallow groundwater, and at very high elevations the hydrologic system is derived from groundwater, precipitation, and glacial melt water.     

Deciphering late Quaternary land snail shell δO and δC from Franchthi Cave (Argolid,Greece)

This paper investigates the stable isotopic composition from late Pleistocene–Holocene (~ 13 to ~ 10.5 cal ka BP) shells of the land snail Helix figulina, from Franchthi Cave (Greece). It explores the palaeoclimatic and palaeoenvironmental implications of the isotope palaeoecology of archaeological shells at the time of human occupation of the cave. Modern shells from around the cave were also analysed and their isotopic signatures compared with those of the archaeological shells. The carbon isotope composition of modern shells depicts the consumption of C₃ vegetation. Shell oxygen isotopic values are consistent with other Mediterranean snail shells from coastal areas. Combining empirical linear regression and an evaporative model, the δ¹⁸Os suggest that modern snails in the study area are active during periods of higher relative humidity and lower rainfall δ¹⁸O, probably at night. Late glacial and early Holocene δ¹⁸Os show lower values compared to modern ones. Early Holocene δ¹⁸Os values likely track enhanced moisture and isotopic changes in the precipitation source. By contrast, lower late glacial δ¹⁸O could reflect lower temperatures and δ¹⁸Op, compared to the present day. Shell carbon isotope values indicate the presence of C₃ vegetation as main source of carbon to late glacial and early Holocene snails.     

Oxygen and carbon isotope composition of Gordon Group carbonates (Ordovician), Florentine Valley,Tasmania, Australia

The Gordon Group carbonates consist of biota of the Chlorozoan assemblage, diverse non‐skeletal grains and abundant micrite and dolomite, similar to those of modern warm water carbonates. Cathodoluminescence studies indicate marine, meteoric and some burial cements. Dolomites replacing burrows, mudcracks and micrite formed during early diagenesis.

δ¹⁸O values (‐5 to ‐7%ō PDB) of the non‐luminescent fauna and marine cement are lighter than those of modern counterparts but are similar to those existing within low latitudes during the Ordovician because of the light δ¹⁸O values of Ordovician seawater (‐3 to ‐5%o SMOW). The δ¹⁸O difference (2%o) between marine and meteoric calcite indicates that Ordovician meteoric water was similar to that in modern subtropics. Values of δ¹³C relative to δ¹⁸O indicate that during the Early Ordovician there were higher atmospheric CO₂ levels than at present but during the Middle and Late Ordovician they became comparable with the present because of a change from ‘Greenhouse’ to glacial conditions. δ¹⁸O values of Late Ordovician seawater were heavier than in the Middle Ordovician mainly because of glaciation.

Dolomitization took place in marine to mixed‐marine waters while the original calcium carbonate was undergoing marine to meteoric diagenesis.     

Preliminary research on hydrogen and oxygen stable isotope characteristics of different water bodies in the Qilian Mountains,northwestern Tibetan Plateau

Hydrogen and oxygen stable isotope in water bodies is a widely used tracer in hydrological process studies. In order to provide a basis for stable isotopic characteristics in different water bodies at the high mountainous area of northwestern Tibetan Plateau, samples for river water, groundwater, soil water, and plant water were collected from 10 sites in the Qilian Mountains during July and August 2015, and then analyzed for δ¹⁸O and δD, respectively. Results indicated that the stable isotope values of soil water were mostly plotted below the global meteoric water line (GMWL), which suggested that evaporation made heavy isotope in soil water enriched. The stable isotope values of soil water were quite different in the top soil layer, but tended to be uniform in the deep soil layer. Furthermore, the stable isotope difference of plant water is related to climatic conditions, water isotopes utilized by plant, plant species, growing season, and so on. Additionally, the variation of δ¹⁸O values for river water and groundwater relatively coincided with each other, and this showed the recharge sources of above two water bodies may be consistent. The stable isotope values of river water and groundwater were mainly plotted on the upper left of GMWL, and the lower level of isotopic fractionation due to weak evaporation may accountable for this.     

Isotopic abundances of water of crystallization of gypsum from the Miocene evaporite formation,Carpathian Foredeep,Poland

For sulfates of Miocene evaporites in the Carpathian Foredeep, the waters of crystallization of gypsum (w.c.g.) have $\text{δD = ?38 to ?113\%.}$ and $\text{δ}{}^{18}\text{O = 0 to ?11\%.}$ (SMOW). The $\text{δ}{}^{34}\text{S}$ and $\text{δ}{}^{18}\text{O}$ values of the sulfates are uniform and consistent with a marine origin. It is proposed that the original w.c.g. was equilibrated with marine water. Subsequently, it re-equilibrated towards very isotopically light water (δD ～ ?100%., δ¹⁸O ～ ?14%) during a glacial or postglacial period and is now trending towards current waters circulating through the deposits (δD ～ ?50%., δ¹⁸ ～ ?7%). The extent of reequilibration increased with decreasing crystal size.     

Evaluation of nitrate source in surface water of southwestern China based on stable isotopes

Stable isotope tracing and analysis play an important role in interpretation of hydrological and ecological processes at the watershed scale and can provide information regarding the flow path, water source, nutrient loss and biogeochemical cycles of a system. In this study, environmental isotopes (δ¹⁸O-H₂O, δD, δ¹⁵N-NO₃ ^?, δ¹⁸O-NO₃ ^?) and chemical compositions of surface water in Guizhou Province, China, were measured to evaluate the primary sources of nitrate and characterize the processes affecting nitrate as well as its correlation with vegetation cover in karstic areas. The δ¹⁵N and δ¹⁸O-NO₃ ^? levels ranged from +1.3 to +9.8 ‰ and +4.7 to +16.9 ‰, respectively, which indicated that nitrate in water from the investigated area primarily originated from nitrification of soil organic matter during the sampling period. There was also a wide range of isotopes in the water and high contents of nitrate in karstic areas with poor vegetation cover, indicating that water and nutrient loss were serious problems hindering plant growth in the study areas. For example, there was a positive relationship between isotopic composition and nitrate content in the natural forest and negative relationship in Libo County nearby, which suggested that the nitrate fate was affected by land use and human disturbance.     

Stable isotopic compositions of waters in the karst environments of China: Climatic implications

A total of 117 water samples, including cave water, ground water, spring water and river water, collected from the monsoonal area of China have been analyzed for their H- and O-isotope composition. Overall, a δ¹⁸O–δD correlation is observed of δD = −4.45 + 6.6δ¹⁸O (R² = 0.90) and a significant evaporation effect observed for the southern sites. Average δ¹⁸O and δD site values generally correspond to those of precipitation in nearby cities, with correlations of δD = 2.18 + 7.23δ¹⁸O (R² = 0.95) for the sample sites and δD = 11.05 + 7.95δ¹⁸O (R² = 0.95) for the cities. The effects of rainfall amount and temperature on precipitation δ¹⁸O were calculated using a simplified theoretical model derived from the Rayleigh distillation equation, which demonstrated that the sign of δ¹⁸O_pvs. T correlation is dependent on precipitation intensity. The mean δ¹⁸O value of cave waters exhibit decreasing trends with increasing latitude and reveal a spatial pattern of positive correlation with annual mean temperature and precipitation, mainly reflecting isotopic fractionations in the moisture source traveling from the ocean side to the inland continent. This spatial pattern implies that the δ¹⁸O values recorded in the proxy climate records derived from speleothems might be influenced by shifts in monsoon boundary during the past, especially between glacial and interglacial intervals.     

Influence of Changing Atmospheric Circulation on Precipitation δO–Temperature Relations in Canada during the Holocene

Postglacial precipitation δ¹⁸O history has been reconstructed for two regions of Canada. Long-term shifts in the oxygen-isotope composition of annual precipitation (δ¹⁸O_p) in southern Ontario appear to have occurred with a consistent isotope–temperature relation throughout the past 11,500¹⁴C yr. The modern isotope–temperature relation in central Canada near present boreal treeline evidently became established between 5000 and 4000 years ago, although the relation during the last glacial maximum and deglaciation may also have been similar to present. In the early Holocene, however, unusually high δ¹⁸O_papparently persisted, in spite of low temperature locally, probably associated with high zonal index. A rudimentary sensitivity analysis suggests that a small reduction in distillation of moisture in Pacific air masses traversing the western Cordillera, perhaps accompanied by a higher summer:winter precipitation ratio, could have been responsible for the observed effect. Equivalent isotope–temperature “anomalies” apparently occurred elsewhere in western North America in response to changing early-Holocene atmospheric circulation patterns, suggesting that a time-slice map of δ¹⁸O_pfor North America during this period might provide a useful target for testing and validation of atmospheric general circulation model simulations using isotopic water tracers.     

The use of oxygen isotope variation in shells of estuarine mollusks as a quantitative record of seasonal and annual Colorado river discharge

We describe a new method for the calculation of river flow that uses the oxygen isotope composition of bivalve mollusk shells that grew in the river-water/seawater mixing zone of the Colorado River estuary. Sclerochronological techniques are used to identify tidally-induced, fortnight-scale bundles of daily growth increments within shell cross-sections. These fortnightly markers are used to establish a chronology for samples taken for δ¹⁸O analysis. A composite seasonal δ¹⁸O profile derived from five shells that grew in the absence of river-water flow is used as a baseline against which profiles of river-influenced shells are compared. Because this comparison is between matched fortnights within a year, the temperature of shell growth is likely to be very similar. The difference in δ¹⁸O between the river-influenced shell and the “no-flow” composite shell therefore represents the change in the δ¹⁸O of the water due to the presence of river water in the mixing zone. The river water end-member is also determined within a fortnightly context so that the change in the δ¹⁸O of mixing-zone water can be used to calculate the relative proportions of seawater and fresh-water. The fresh-water end-member is calculated from the δ¹⁸O of bivalves alive prior to the emplacement of dams and water diversions on the Colorado River. The marine end-member is based on direct measurements of the δ¹⁸O of northern Gulf of California water during times of no Colorado River flow. The system has been calibrated to absolute flow amounts using recent releases of known volume and rate.     

Climatic dependence of stable carbon and oxygen isotope signals recorded in speleothems: From soil water to speleothem calcite

Understanding the relationship between stable isotope signals recorded in speleothems (δ¹³C and δ¹⁸O) and the isotopic composition of the carbonate species in the soil water is of great importance for their interpretation in terms of past climate variability. Here the evolution of the carbon isotope composition of soil water on its way down to the cave during dissolution of limestone is studied for both closed and open-closed conditions with respect to CO₂.The water entering the cave flows as a thin film towards the drip site. CO₂ degasses from this film within approx. 10 s by molecular diffusion. Subsequently, chemical and isotopic equilibrium is established on a time scale of several 10-100 s. The δ¹³C value of the drip water is mainly determined by the isotopic composition of soil CO₂. The evolution of the δ¹⁸O value of the carbonate species is determined by the long exchange time T_ex, between oxygen in carbonate and water of several 10,000 s. Even if the oxygen of the CO₂ in soil water is in isotopic equilibrium with that of the water, dissolution of limestone delivers oxygen with a different isotopic composition changing the δ¹⁸O value of the carbonate species. Consequently, the δ¹⁸O value of the rainwater will only be reflected in the drip water if it has stayed in the rock for a sufficiently long time.After the water has entered the cave, the carbon and oxygen isotope composition of the drip water may be altered by CO₂-exchange with the cave air. Exchange times, , of about 3000 s are derived. Thus, only drip water, which drips in less than 3000 s onto the stalagmite surface, is suitable to imprint climatic signals into speleothem calcite deposited from it.Precipitation of calcite proceeds with time constants, τ_p, of several 100 s. Different rate constants and equilibrium concentrations for the heavy and light isotopes, respectively, result in isotope fractionation during calcite precipitation. Since T_ex ? τ_p, exchange with the oxygen in the water can be neglected, and the isotopic evolution of carbon and oxygen proceed analogously. For drip intervals T_d < 0.1τ_p the isotopic compositions of both carbon and oxygen in the solution evolve linearly in time. The calcite precipitated at the apex of the stalagmite reflects the isotopic signal of the drip water.For long drip intervals, when calcite is deposited from a stagnant water film, long drip intervals may have a significant effect on the isotopic composition of the DIC. In this case, the isotopic composition of the calcite deposited at the apex must be determined by averaging over the drip interval. Such processes must be considered when speleothems are used as proxies of past climate variability.