Biomass effects on stalagmite growth and isotope ratios: A 20th century analogue from Wiltshire, England

Increases in calcite deposition rates combined with decreases in δ¹³C and δ¹⁸O in three modern stalagmites from Brown's Folly Mine, Wiltshire, England, are correlative with a well-documented re-vegetation above the mine. Increased soil P_CO2 resulted in greater amounts of dissolved CaCO₃ in the drip waters, which consequently increased annual calcite deposition rates. The absence of deposition prior to 1916 (28 years after the mine was closed) indicates that vegetation had not yet sufficiently developed to allow higher P_CO2 values to form in the soil. Lower δ¹³C values through time may reflect the increased input of isotopically light biogenic carbon to the total dissolved inorganic carbon (DIC). δ¹⁸O decreased synchronously with δ¹³C, reflecting the increased importance of isotopically light winter recharge due to greater biomass-induced summer evapotranspiration. This is the first empirical demonstration that vegetation density can control stalagmite growth rates, δ¹³C, and δ¹⁸O, contributing critical insights into the interpretation of these climate proxies in ancient stalagmites.     

Epikarst hydrology and implications for stalagmite capture of climate changes at Grotta di Ernesto (NE Italy): results from long‐term monitoring

Grotta di Ernesto is a cave site well suited for palaeoclimate studies because it contains annually laminated stalagmites and was monitored from 1995 to the end of 2008 for microclimate, hydrology and hydrochemistry. Long‐term monitoring highlighted that cave drips show three different hydrological responses to rainfall and infiltration: (1) fast seasonal drips in the upper part of the cave, which are mostly fed by fractures, (2) slow seasonal drips, located at mid‐depth in the cave characterized by mixed feeding and (3) slow drips, mostly located in the deeper gallery, which are fed by seepage flow from bulk porosity with a minor fracture‐fed component. The slow drips display daily cycles during spring thaw. Monitoring also indicated that drip waters are only slightly modified by degassing within the soil zone and aquifer and by prior calcite precipitation. Hydrochemical studies show a clear seasonality in calcite saturation index, which results in most cave calcite precipitation occurring during late autumn and winter with similar amounts of precipitated calcite on most stalagmites, regardless of drip rate (discharge) differences. Drip rate, and drip rate variability, therefore, has a minor role in modulating the amount of annual calcite formation. In contrast, drip rate, when associated with moderate reduction in calcite saturation index, clearly influences stalagmite morphology. Increasing drip rate yields a passage from candle‐, to cone‐ to dome‐shaped stalagmites. Very high drip rates feed speleothems with flowstone morphology. In summary, monitoring provides information about the karst aquifer and how hydrology influences those physical and chemical characteristics of speleothems which are commonly used as climate proxies. Copyright © 2010 John Wiley & Sons, Ltd.     

Cave air ventilation and CO2 outgassing by radon-222 modeling: How fast do caves breathe?

In general, the rate and timing of calcite precipitation is in part affected by variations in cave air CO₂ concentrations. Knowledge of cave ventilation processes is required to quantify the effect variations in CO₂ concentrations have on speleothem deposition rates and thus paleoclimate records. In this study we use radon-222 (²²²Rn) as a proxy of ventilation to estimate CO₂ outgassing from the cave to the atmosphere, which can be used to infer relative speleothem deposition rates. Hollow Ridge Cave, a wild cave preserve in Marianna, Florida, is instrumented inside and out with multiple micro-meteorological sensor stations that record continuous physical and air chemistry time-series data. Our time series datasets indicate diurnal and seasonal variations in cave air ²²²Rn and CO₂ concentrations, punctuated by events that provide clues to ventilation and drip water degassing mechanisms. Average cave air ²²²Rn and CO₂ concentrations vary seasonally between winter (²²²Rn = 50 dpm L^? 1, where 1 dpm L^? 1 = 60 Bq m^? 3; CO₂ = 360 ppmv) and summer (²²²Rn = 1400 dpm L^? 1; CO₂ = 3900 ppmv). Large amplitude diurnal variations are observed during late summer and autumn (²²²Rn = 6 to 581 dpm L^? 1; CO₂ = 360 to 2500 ppmv).We employ a simple first-order ²²²Rn mass balance model to estimate cave air exchange rates with the outside atmosphere. Ventilation occurs via density driven flow and by winds across the entrances which create a ‘venturi’ effect. The most rapid ventilation occurs 25 m inside the cave near the entrance: 45 h^? 1 (1.33 min turnover time). Farther inside (175 m) exchange is slower and maximum ventilation rates are 3 h^? 1 (22 min turnover time). We estimate net CO₂ flux from the epikarst to the cave atmosphere using a CO₂ mass balance model tuned with the ²²²Rn model. Net CO₂ flux from the epikarst is highest in summer (72 mmol m^? 2 day^? 1) and lowest in late autumn and winter (12 mmol m^? 2 day^? 1). Modeled ventilation and net CO₂ fluxes are used to estimate net CO₂ outgassing from the cave to the atmosphere. Average net CO₂ outgassing is positive (net loss from the cave) and is highest in late summer and early autumn (about 4 mol h^? 1) and lowest in winter (about 0.5 mol h^? 1). Modeling of ventilation, net CO₂ flux from the epikarst, and CO₂ outgassing to the atmosphere from cave monitoring time-series can help better constrain paleoclimatic interpretations of speleothem geochemical records.     

Isotope geochemistry of minerals and fluids from Newberry volcano, Oregon

Isotopic compositions were determined for hydrothermal quartz, calcite, and siderite from core samples of the Newberry 2 drill hole, Oregon. The δ¹⁵O values for these minerals decrease with increasing temperatures. The values indicate that these hydrothermal minerals precipitated in isotopic equilibrium with water currently present in the reservoirs. The δ¹⁸O values of quartz and calcite from the andesite and basalt flows (700–932 m) have isotopic values which require that the equilibrated water δ¹⁸O values increase slightly (− 11.3 to −9.2‰) with increasing measured temperatures (150–265°C). The lithic tuffs and brecciated lava flows (300–700 m) contain widespread siderite. Calculated oxygen isotopic compositions of waters in equilibrium with siderite generally increase with increasing temperatures (76–100°C). The δ¹⁸O values of siderite probably result from precipitation in water produced by mixing various amounts of the deep hydrothermal water (− 10.5 ‰) with meteoric water (− 15.5 ‰) recharged within the caldera. The δ¹³C values of calcite and siderite decrease with increasing temperatures and show that these minerals precipitated in isotopic equilibrium with CO₂ of about −8 ‰.The δ¹⁸O values of weakly altered (<5% alteration of plagioclase) whole-rock samples decrease with increasing temperatures above 100°C, indicating that exchange between water and rock is kinetically controlled. The water/rock mass ratios decrease with decreasing temperatures. The δ¹⁸O values of rocks from the bottom of Newberry 2 show about 40% isotopic exchange with the reservoir water.The calculated δ¹⁸O and δD values of bottom hole water determined from the fluid produced during the 20 hour flow test are −10.2 and −109‰, respectively. The δD value of the hydrothermal water indicates recharge from outside the caldera.     

A discontinuous climatic record from 187 to 74 ka from a speleothem of the Clamouse Cave (south of France)

This study presents a continental paleoclimatic record in the south of France, based on δ¹⁸O, δ¹³C and the ²³⁴U/²³⁸U activity ratio, dated by the ²³⁰Th/²³⁴U disequilibrium method with thermal ionization mass spectrometry. A stalagmite (Cla4) from the Clamouse Cave offers a discontinuous stable isotopic record between 189 ka and 74 ka which covers marine isotope stages (MIS) 7, 6.4, 5.5, 5.3 and 5.1. The growth phases of the Cla4 stalagmite correspond to high sea level stages, except during MIS 6.4 (169-162 ka). All the growth phases of Cla4 correspond to humid periods, corresponding to the sapropel events observed in the eastern Mediterranean basin. Thus, the influence of a strong hydrological activity in the eastern Mediterranean basin during these periods prevailed as far west as the south of France. Because the karstic system studied strongly buffers the isotopic composition of water, isotopic variations of the calcite deposited in the cave represent mainly global and large-scale environmental variations when isotopic equilibrium conditions prevailed for calcite crystallization. Sub-stage 5.3, the end of 5.5 and MIS 7 were colder by about 4-6°C (calculated temperature) compared to present-day temperature while the growth phases of sub-stages 5.1 and the beginning of 5.5 reflect environmental conditions close to present ones. The δ¹⁸O and δ¹³C values of cave deposits of the sub-stage 6.4 are: (1) strongly marked by kinetic fractionation processes such as evaporation due to moisture deficit within the cave atmosphere during the first step of this growth phase and (2) related to higher humidity due to a second period of enhanced rainfall during the second step of growth. This study shows that even if calcite has not been deposited at isotopic equilibrium, its isotopic composition can give insights into the environmental conditions at the time of deposition.     

Tritium and stable isotopes of magmatic waters

To investigate the isotopic composition and age of water in volcanic gases and magmas, we analyzed samples from 11 active volcanoes ranging in composition from tholeiitic basalt to rhyolite: Mount St. Helens (USA), Kilauea (USA), Pacaya (Guatemala), Galeras (Colombia), Satsuma Iwo-Jima (Japan), Sierra Negra and Alcedo (Ecuador), Vulcano (Italy), Parícutin (Mexico), Kudryavy (Russia), and White Island (New Zealand). Tritium at relatively low levels (0.1–5 T.U.) is found in most emissions from high-temperature volcanic fumaroles sampled, even at discharge temperatures >700°C. Although magmatic fluids sampled from these emissions usually contain high CO₂, S_total, HCl, HF, B, Br, ³He R/R_A, and low contents of air components, stable isotope and tritium relations of nearly all such fluids show mixing of magmatic volatiles with relatively young meteoric water (model ages≤75 y). Linear δD/δ¹⁸O and ³H/δ¹⁸O mixing trends of these two end-members are invariably detected at arc volcanoes. Tritium is also detected in fumarole condensates at hot spot basalt volcanoes, but collecting samples approaching the composition of end-member magmatic fluid is exceedingly difficult. In situ production of ³H, mostly from spontaneous fission of ²³⁸U in magmas is calculated to be <0.001 T.U., except for the most evolved compositions (high U, Th, and Li and low H₂O contents). These values are below the detection limit of ³H by conventional analytical techniques (about 0.01 T.U. at best). We found no conclusive evidence that natural fusion in the Earth produces anomalous amounts of detectable ³H (>0.05 T.U.).     

δCa evolution in a carbonate aquifer and its bearing on the equilibrium isotope fractionation factor for calcite

To improve understanding of Ca isotope transport during water-rock interaction on the continents, we measured dissolved δ⁴⁴Ca values along a 236 km flow path in the Madison aquifer, South Dakota, where fluids have chemically evolved according to dolomite and anhydrite dissolution, calcite precipitation, and Ca-for-Na ion-exchange over a timescale spanning ~ 15 kyr. We used a reactive transport model employing rate data constrained from major ion mass-balances to evaluate the extent to which calcite precipitation and ion-exchange fractionate Ca isotopes. Elevated δ⁴⁴Ca values during the initial and final stages of water transport possibly result from calcite precipitation under supersaturated conditions and Ca-for-Na ion-exchange, respectively. However, for the bulk of the flow path, δ⁴⁴Ca values evolve by mixing between anhydrite and dolomite dissolution, with no fractionation during calcite precipitation under saturated conditions. We attribute the absence of Ca isotope fractionation to the long timescale of water-rock interaction and slow rate of calcite precipitation, which have enabled fluids to chemically and isotopically equilibrate with calcite. We therefore conclude that the equilibrium Ca isotope fractionation factor between calcite and water (Δ_cal–w) is very close to zero. To the extent that the Madison aquifer typifies other groundwater systems where calcite slowly precipitates from solutions at or near chemical equilibrium, this study suggests that groundwater contributions to δ⁴⁴Ca variability on the continents can be modeled according to simple mixing theory without invoking isotope discrimination.     

Relationship between13C and18O fractionation and changes in major element composition in a recent calcite-depositing spring — A model of chemical variations with inorganic CaCO3 precipitation

A theoretical model is derived in which isotopic fractionations can be calculated as a function of variations in dissolved carbonate species on CO₂ degassing and calcite precipitation. This model is tested by application to a calcite-depositing spring system near Westerhof, Germany. In agreement with the model,¹³C of the dissolved carbonate species changes systematically along the flow path. The difference in δ values between the upper and lower part of the stream is about 1‰. The¹³C content of the precipitated calcite is different from that expected from the theoretical partitioning. The isotopic composition of the solid CaCO₃ is similar to that of the dissolved carbonate, though in theory it should be isotopically heavier by about 2.4‰. The¹⁸O composition of dissolved carbonate and H₂O is constant along the stream. Calculated calcite-water temperatures differ by about +5°C from the observed temperatures demonstrating isotopic disequilibrium between the water and precipitated solid. This is attributed to kinetic effects during CaCO₃ deposition from a highly supersaturated solution, in which precipitation is faster than equilibration with respect to isotopes.Plant populations in the water have virtually no influence on CO₂ degassing, calcite saturation and isotopic fractionation. Measurements of P_CO2, S_C and¹³C within a diurnal cycle demonstrate that metabolic effects are below the detection limit in a system with a high supply-rate of dissolved carbonate species. The observed variations are due to differences in CO₂ degassing and calcite precipitation, caused by continuously changing hydrodynamic conditions and carbonate nucleation rates.     

Authigenic carbonates in sediments from the Gulf of Mexico

The carbon isotopic composition of diagenetic dolomite and calcite in some sediments of the Gulf of Mexico varies between “normal-marine” (δ¹³C ca. 0‰) and −14.6‰ which suggests that biogenic CO₂ contributed to the carbonate formation. The δ¹³O values of dolomite and coexisting calcite are very similar but variable down-core.Dolomite and calcite precipitated early from pore water where SO₄²⁻ was not reduced. However, during (and after?) SO₄²⁻ reduction dolomite and calcite still formed and there are at least two generations of carbonate minerals present.     

Two modes of climatic control in the Holocene stalagmite record from the Japan Sea side of the Japanese islands

The Holocene stalagmite FG01 collected at the Fukugaguchi Cave in Itoigawa, central Japan provides a unique high‐resolution record of the East Asian winter monsoon. Because of the climate conditions on the Japan Sea side of the Japanese islands, the volume of precipitation during the winter is strongly reflected in the stalagmite δ¹⁸O signal. Examination of the carbon isotopes and the Mg/Ca ratio of FG01 provided additional information on the Holocene climate in Itoigawa, which is characterized by two different modes separated at 6.4 ka. Dripwater composition and the correlation between the δ¹³C and Mg/Ca data of FG01 indicate the importance of prior calcite precipitation (PCP), a process that selectively eliminated ¹²C and calcium ions from infiltrating water from CO₂ degassing and calcite precipitation. In an earlier period (10.0–6.4 ka), an increase in soil pCO₂ associated with warming and wetting climate trends was a critical factor that enhanced PCP, and resulted in an increasing trend in the Mg/Ca and δ¹³C data and a negative correlation between the δ¹³C and δ¹⁸O profiles. A distinct peak in the δ¹³C age profile at 6.8 ka could be a response to an increase of approximately 10% in C4 plants in the recharge area. At 6.4 ka, the climate mode changed to another, and correlation between δ¹⁸O and δ¹³C became positive. In addition, a millennial‐scale variation in δ¹⁸O and pulsed changes in δ¹³C and Mg/Ca became distinct. Assuming that δ¹⁸O and PCP were controlled by moisture in the later period, the volume of precipitation was high during 6.0–5.2, 4.4–4.0, and 3.0–2.0 ka. In contrast, the driest interval in Itoigawa was during 0.2–0.4 ka, and broadly corresponds to the Little Ice Age.     

Carbon and oxygen isotope composition of shell carbonate of desert land snails

Variation in¹³C/¹²C and¹⁸O/¹⁶O ratios in the shell carbonate of several species of land snails was studied along a climatic gradient in semi-arid to arid areas in the southern Levant.¹³C was found to be enriched in snails from communities having plants with a C₄ photosynthetic pathway. Depleted δ¹³C values were found in areas with high mean annual rainfall, apparently due to higher input of metabolic CO₂ as a result of greater snail activity. Shell carbonate δ¹⁸O values show a weak relation to the δ¹⁸O values of rainwater. The shell δ¹⁸O values are enriched by 2–8‰ relative to isotopic equilibrium with environmental waters. Enrichment is suggested to result from metabolic effects on body water (with lower activity producing greater enrichment) but evaporation could also be a factor. Consistent differences in both¹³C and¹⁸O were found among species and may relate to the time when shell deposition occurs. As with most paleoenvironmental indicators, the application of shell isotopes is complicated by the multiplicity of controls of isotopic composition.     

Seasonal variations in pCO2 and its controlling factors in surface seawater of the northern East China Sea

Surface partial pressure of CO₂ (pCO₂), temperature, salinity, nutrients, and chlorophyll a were measured in the East China Sea (ECS; 31°30′–34°00′N to 124°00′–127°30′E) in August 2003 (summer), May 2004 (spring), October 2004 (early fall), and November 2005 (fall). The warm and saline Tsushima Warm Current was observed in the eastern part of the survey area during four cruises, and relatively low salinity waters due to outflow from the Changjiang (Yangtze River) were observed over the western part of the survey area. Surface pCO₂ ranged from 236 to 445 μatm in spring and summer, and from 326 to 517 μatm in fall. Large pCO₂ (values >400 μatm) occurred in the western part of the study area in spring and fall, and in the eastern part in summer. A positive linear correlation existed between surface pCO₂ and temperature in the eastern part of the study area, where the Tsushima Warm Current dominates; this correlation suggests that temperature is the major factor controlling surface pCO₂ distribution in that area. In the western part of the study area, however, the main controlling factor is different and seasonally complex. There is large transport in this region of Changjiang Diluted Water in summer, causing low salinity and low pCO₂ values. The relationship between surface pCO₂ and water stability suggests that the amount of mixing and/or upwelling of CO₂-rich water might be the important process controlling surface pCO₂ levels during spring and fall in this shallow region. Sea–air CO₂ flux, based on the application of a Wanninkhof [1992. Relationship between wind speed and gas exchange over the ocean. Journal of Geophysical Research 97, 7373–7382] formula for gas transfer velocity and a set of monthly averaged satellite wind data, were −5.04±1.59, −2.52±1.81, 1.71±2.87, and 0.39±0.18 mmol m⁻² d⁻¹ in spring, summer, early fall, and fall, respectively, in the northern ECS. The ocean in this study area is therefore a carbon sink in spring and summer, but a weak source or in equilibrium with the atmosphere in fall. If the winter flux value is assumed to have been the mean of autumnal and vernal values, then the northern ECS absorbs about 0.013 Pg C annually. That result suggests that the northern ECS is a net sink for atmospheric CO₂, a result consistent with previous studies.     

Sulfur isotopic effects in the disproportionation reaction of sulfur dioxide in hydrothermal fluids: implications for the δS variations of dissolved bisulfate and elemental sulfur from active crater lakes

Sulfur isotope effects during the SO₂ disproportionation reaction to form elemental sulfur (3SO₂+3H₂O→2HSO₄⁻+S+2H⁺) at 200–330°C and saturated water vapor pressures were experimentally determined. Initially, a large kinetic isotopic fractionation takes place between HSO₄⁻ and S, followed by a slow approach to equilibrium. The equilibrium fractionation factors, estimated from the longest run results, are expressed by 1000 ln α_HSO4⁻–S=6.21×10⁶/T²+3.62. The rates at which the initial kinetic fractionation factors approach the equilibrium ones were evaluated at the experimental conditions.δ³⁴S values of HSO₄⁻ and elemental sulfur were examined for active crater lakes including Noboribetsu and Niseko, (Hokkaido, Japan), Khloridnoe, Bannoe and Maly Semiachik (Kamchatka), Poás (Costa Rica), Ruapehu (New Zealand) and Kawah Ijen and Keli Mutu (Indonesia). Δ_HSO4⁻–S values are 28‰ for Keli Mutu, 26‰ for Kawah Ijen, 24‰ for Ruapehu, 23‰ for Poás, 22‰ for Maly Semiachik, 21‰ for Yugama, 13‰ for Bannoe, 9‰ for Niseko, 4‰ for Khloridonoe, and 0‰ for Noboribetsu, in the decreasing order. The SO₂ disproportionation reaction in the magmatic hydrothermal system below crater lakes where magmatic gases condense is responsible for high Δ_HSO4⁻–S values, whereas contribution of HSO₄⁻ produced through bacterial oxidation of reduced sulfur becomes progressively dominant for lakes with lower Δ_HSO4⁻–S values. Currently, Noboribetsu crater lake contains no HSO₄⁻ of magmatic origin. A 40-year period observation of δ³⁴S_HSO4⁻ and δ³⁴S_S values at Yugama indicated that the isotopic variations reflect changes in the supply rate of SO₂ to the magmatic hydrothermal system. This implies a possibility of volcano monitoring by continuous observation of δ³⁴S_HSO4⁻ values. The δ¹⁸O values of HSO₄⁻ and lake water from the studied lakes covary, indicating oxygen isotopic equilibration between them. The covariance gives strong evidence that lake water circulates through the sublimnic zone at temperatures of 140±30°C.     

An isotopic calibration study of precipitation,cave dripwater,and climate in west‐central Florida

A calibration study of oxygen and hydrogen isotopic composition from precipitation and cave dripwater was conducted in west‐central Florida at Legend Cave during 2007–2008. This study was performed to better understand how modern precipitation patterns can be discerned through examination of cave dripwater and speleothem calcite for paleoclimate reconstruction. The ‘amount effect’ was shown to be a dominant control on the oxygen isotopic composition of precipitation for the study area. A meteoric water line with a slope of 6·7 suggests evaporative effects occur either during precipitation or subsequent hydrological processes. However, δ¹⁸O values of cave dripwater averaged near the mean annual amount‐weighted average of precipitation, suggesting that the isotopic composition of dripwater tracks the long‐term average of rainfall. An observed weak seasonal influence occurred in the d‐excess values, with summer precipitation being more enriched due to increased evaporative effects. Comparison of precipitation δ¹⁸O values to synoptic weather data shows the dominant amount effect influence occurs due to strong convective storms producing highly ¹⁸O‐depleted rainfall at greater amounts during the year. Constant δ¹⁸O values of the dripwater indicate that paleoclimate reconstructions using speleothems from this area would record changes in annual to interannual shifts in precipitation amount above the cave. Copyright © 2011 John Wiley & Sons, Ltd.     

Stalagmite from the Austrian Alps reveals Dansgaard-Oeschger events during isotope stage 3:: Implications for the absolute chronology of Greenland ice cores

A mass-spectrometric uranium-series dated stalagmite from the Central Alps of Austria provides unprecedented new insights into high-altitude climate change during the peak of isotope stage 3. The stalagmite formed continuously between 57 and 46 kyr before present. A series of ‘Hendy tests’ demonstrates that the outer parts of the sample show a progressive increase of both stable C and O isotope values. No such covariant increase was detected within the axial zone. This in conjunction with other observations suggests that the continuous stable oxygen isotope profile obtained from the axial zone of the stalagmite largely reflects the unaltered isotopic composition of the cave drip water. The δ¹⁸O record shows events of high δ¹⁸O values that correlate remarkably with Interstadials 15 (a and b), 14 and 12 identified in the Greenland ice cores. Interstadial 15b started rapidly at 55.6 kyr and lasted ∼300 yr only, Interstadial 15a peaked 54.9 kyr ago and was even of shorter duration (∼100 yr), and Interstadial 14 commenced 54.2 kyr ago and lasted ∼3000 yr. This stalagmite thus represents one of the first terrestrial archives outside the high latitudes which record precisely dated Dansgaard-Oeschger (D/O) events during isotope stage 3. Provided that rapid D/O warmings occurred synchronously in Greenland and the European Alps, the new data provide an independent tool to improve the GRIP and GISP2 chronologies.     

Tracing effects of decalcification on solute sources in a shallow groundwater aquifer, NW Germany

δ⁸⁷Sr values and Ca/Sr ratios were employed to quantify solute inputs from atmospheric and lithogenic sources to a catchment in NW Germany. The aquifer consists primarily of unconsolidated Pleistocene eolian and fluviatile deposits predominated by >90% quartz sand. Accessory minerals include feldspar, glauconite, and mica, as well as disperse calcium carbonate in deeper levels. Decalcification of near-surface sediment induces groundwater pH values up to 4.4 that lead to enhanced silicate weathering. Consequently, low mineralized Ca–Na–Cl- and Ca–Cl-groundwater types are common in shallow depths, while in deeper located calcareous sediment Ca–HCO₃-type groundwater prevails. δ⁸⁷Sr values and Ca/Sr ratios of the dissolved pool range from 7.3 to −2.6 and 88 to 493, respectively. Positive δ⁸⁷Sr values and low Ca/Sr ratios indicate enhanced feldspar dissolution in shallow depths of less than 20 m below soil surface (BSS), while equilibrium with calcite governs negative δ⁸⁷Sr values and elevated Ca/Sr ratios in deep groundwater (>30 m BSS). Both positive and negative δ⁸⁷Sr values are evolved in intermediate depths (20–30 m BSS). For groundwater that is undersaturated with respect to calcite, atmospheric supplies range from 4% to 20%, while feldspar-weathering accounts for 8–26% and calcium carbonate for 62–90% of dissolved Sr²⁺. In contrast, more than 95% of Sr²⁺ is derived by calcium carbonate and less than 5% by feldspar dissolution in Ca–HCO₃-type groundwater. The surprisingly high content of carbonate-derived Sr²⁺ in groundwater of the decalcified portion of the aquifer may account for considerable contributions from Ca-containing fertilizers. Complementary tritium analyses show that equilibrium with calcite is restricted to old groundwater sources.     

Modern and Pleistocene boron isotope composition of the benthic foraminifer Cibicidoides wuellerstorfi

Here we present the first species-specific study of boron isotopes in the epibenthic foraminifer species Cibicidoides wuellerstorfi. Coretop samples from a water depth profile from 1000 to 4500 m on the northern flank of the Walvis Ridge are 4.4‰ lower than the values expected, based on calculations of the δ¹¹B_borate of ambient seawater. Similar values for this foraminifer species are presented from ODP site 668B at the Sierra Leone Rise, in the equatorial Atlantic. The consistency between data of the same species suggests the offsets are primary, rather than diagenetic. Glacial C. wuellerstorfi from ODP 668B and Walvis Ridge have boron isotope compositions only slightly different to interglacial samples, that is no larger than + 0.10 pH units, or + 23 µmol kg^− 1 in [CO₃²⁻] above the reconstructed glacial lysocline, and − 0.07 pH units, or − 14 µmol kg^− 1 in [CO₃²⁻] below. We use these results to suggest that glacial deep water pH in the Atlantic was similar to interglacial pH. The new data resolve the inconsistency between the previously reported high bottom water pH and the lack of significant carbonate preservation of the glacial deep ocean.     

Earthquake-induced variations in the composition of the water in the geothermal reservoir at Vulcano Island, Italy

During 1979–1989, variations were observed in the oxygen composition of the water contained in the geothermal reservoir at Vulcano Island, Italy.The reservoir water, that has a magmatic origin, showed an oxygen composition of +1.0±0.5‰ δ¹⁸O during periods without local tectonic earthquakes, and an oxygen composition of +3.4±0.5‰ δ¹⁸O after the highest-energy seismic activity that occurred recently near the island. A slight increase of the δ¹⁸O value in the reservoir water was also observed after a low-energy sequence of tectonic earthquakes that occurred at very shallow depth just beneath Vulcano Island. These ¹⁸O variations in the reservoir water are consistent with earthquake-induced increases in the contribution from high-temperature δ¹⁸O-rich magmatic condensate to the geothermal reservoir, and with subsequent decreases in the δ¹⁸O value due to ¹⁸O exchanges at the temporarily increased reservoir temperature during reactions between the highly reactive magmatic condensate and the local rocks.Only minor changes in the deuterium composition of the reservoir water occurred with time, as the δD value in the magmatic condensate released from the magma after major local earthquakes quickly approached the δD value of the water contained in the geothermal reservoir.Also the chloride concentration in the reservoir water appears to be linked to the contribution from the magmatic fluid. This chloride content seems not to have undergone major changes with time, as it may be buffered by temporary increases in the reservoir temperature up to values >300°C induced by major local earthquakes. This mechanism may possibly occur also in other magmatic–hydrothermal systems.     

Kinetic processes and stable isotopes in cave dripwaters as indicators of winter severity

We examine how the stable isotope composition of meteoric water is transmitted through soil and epikarst to dripwaters in a cave in western Romania. δ²H and δ¹⁸O in precipitation at this site are influenced by temperature and moisture sources (Atlantic and Mediterranean), with lower δ¹⁸O in winter and higher in summer. The stable isotope composition of cave dripwaters mimics this seasonal pattern of low and high δ¹⁸O, but the onset and end of freezing conditions in the winter season are marked by sharp transitions in the isotopic signature of cave dripwaters of approximately 1 ‰. We interpret these shifts as the result of kinetic isotopic fractionation during the transition phase from water to ice at the onset of freezing conditions and the input of meltwater to the cave at the beginning of the spring season. This process is captured in dripwaters and therefore speleothems from Ur?ilor Cave, which grew under such dripping points, may have the potential to record past changes in the severity of winters. Similar isotopic changes in dripwaters driven by freeze–thaw processes can affect other caves in areas with winter snow cover, and cave monitoring during such changes is essential in linking the isotopic variability in dripwaters and speleothems to surface climate.     

Sub-Milankovitch climatic cycles in Holocene stalagmites from Sauerland, Germany

Calcitic stalagmites from caves in the Sauerland, Germany, prove the existence of sub-Milankovitch cycles in precipitation during the last 6000 yr. The δ¹⁸O record dated with Th/U is interpreted as an indicator of paleohumidity. Spectral analysis of δ¹⁸O from 6000 a BP up to the recent top of a stalagmite from the Atta cave yields statistically significant peaks at 1450, 117, 64 and 57 a. Additionally we find a good correlation of the stalagmite’s δ¹⁸O and Δ¹⁴C from European tree rings. The 1450 a cycle in the stalagmite probably is analogous to the pervasive millennial scale climate cycle described by Bond et al. [Science 278 (1997) 1257-1266; 294 (2001) 2130-2136] derived from the amount of ice rafted debris in deep sediments from the North Atlantic. Our results suggest that the centennial to millennial shifts observed in the North Atlantic are accompanied by synchronous shifts of the climate in Northern and Central Europe, which most probably can be attributed to solar irradiation variations.