Reconstructing seawater δO from paired coral δO and Sr/Ca ratios: Methods, error analysis and problems, with examples from Tahiti (French Polynesia) and Timor (Indonesia)

We compare several statistical routines that may be used to calculate δ¹⁸O_sw and SSS from paired coral Sr/Ca and δ¹⁸O measurements. Typically, the δ¹⁸O_coral-SST relationship is estimated by linear regression of coral δ¹⁸O vs. SST. If this method is applied, evidence should be given that at a particular site SST and SSS do not co-vary. In the tropical oceans, SST and δ¹⁸O_sw (SSS) often co-vary, and this will bias the estimate of the regression slope of δ¹⁸O_coral-SST. Using a stochastic model, we show that covariance leads to a bias in the coefficients of the univariate regression equations. As the slope of the δ¹⁸O_coral-SST relationship has known, we propose to insert this value for γ₁ in the regression models. This requires that the constants of the regression equations are removed. To omit the constants, we propose to center the regression equations (i.e., to remove the mean values from the variables). The statistical error propagation is calculated to assess our ability to resolve past variations in δ¹⁸O_sw (SSS). At Tahiti, we find that the combined analytical uncertainties of coral δ¹⁸O and Sr/Ca equal the amplitude of the seasonal cycle of δ¹⁸O_sw (SSS). Therefore, we cannot resolve the seasonal cycle of SSS at Tahiti. At Timor, the error of reconstructed δ¹⁸O_sw (SSS) is lower than the magnitude of seasonal variations of δ¹⁸O_sw (SSS), and the seasonal cycle of δ¹⁸O_sw (SSS) can be resolved.     

The major ion, δCa, δCa, and δMg geochemistry of granite weathering at pH = 1 and T = 25 °C: power-law processes and the relative reactivity of minerals

We dissolved Boulder Creek Granodiorite in a plug flow reactor for 5794 h at pH = 1 and T = 25 °C. The primary purpose of the experiment was to identify controls on dissolved δ^44/40Ca, δ^44/42Ca, and δ^26/24Mg values during granite weathering. Herein, we also examine the origin of Ca and Mg isotopic variability among minerals composing the Boulder Creek Granodiorite, and we constrain fundamental characteristics of granite weathering important for quantifying the elemental and isotopic geochemistry of the reactor output. Nine Ca-bearing minerals display an 8.80‰ range of δ^44/40Ca values and a 0.51‰ range of δ^44/42Ca values. Three Mg-bearing minerals display a 1.53‰ range of δ^26/24Mg values. These ranges expressed at the mineralogical scale are higher than the ranges thus far reported for bulk igneous rocks. Most of the δ^44/40Ca variability reflects ⁴⁰Ca enrichment in K-feldspar, and to a lesser extent, biotite, due to the radioactive decay of ⁴⁰K over the 1.7 Ga age of the rock, whereas the entire range of δ^44/42Ca values reflects mass-dependent isotope fractionation during igneous differentiation and crystallization. The range of δ^26/24Mg values may represent either fractionation during the chloritization of biotite or interaction of the Boulder Creek Granodiorite with Mg-rich metamorphic fluids having low δ^26/24Mg values.The elemental and isotopic composition of the reactor output varied substantially during the experiment. We synthesize the mineralogical and fluid data using coupled mass-conservation equations solved at non-steady-state. Model calculations reveal an intricate balance between increasing specific surface area and decreasing mineral concentrations. While surface area normalized dissolution rate constants were time-invariant, specific surface area increased as a power-law function of time through positive feedbacks between mechanical disaggregation, chemical dissolution, and mineral depletion. Variations in dissolved δ^44/40Ca, δ^44/42Ca, and δ^26/24Mg values reflect conservative mixing rather than fractionation. Apatite and calcite initially control δ^44/40Ca and δ^44/42Ca values, followed by biotite, titanite, epidote, hornblende, and plagioclase. The release of radiogenic ⁴⁰Ca clearly defines the period where biotite dissolution dominates. The brucite layer of chlorite initially controls δ^26/24Mg values, followed by biotite, the TOT layer of chlorite, and hornblende. Through direct isotopic tracking, these results demonstrate that trace minerals, such as apatite and calcite in the case of Ca and brucite in the case of Mg, dominate elemental release during the incipient stages of granite weathering. The results further show that biotite dissolution dominates the middle stages of granite weathering and that plagioclase dissolution only becomes important during relatively late stages. The Ca and Mg isotope variations associated with these stages are distinct and potentially resolvable in soil mineral weathering studies.     

The Origin of Paleokarst in the Huanglong Formation of the Eastern Sichuan Basin: Evidence from δ13C, δ18O and 87Sr/86Sr

Karst rocks from the Huanglong Formation exposed at the margin of the Eastern Sichuan Basin can be divided into four types:slightly corroded, moderately corroded porous, intensely corroded brecciated and intensely corroded and replaced secondary calcic karstic rocks. The carbon, oxygen and strontium isotope compositions of the various karst rocks are analyzed systematically and compared to rocks without karst corrosion. The results indicate that(1) the Huanglong Formation in the eastern Sichuan Basin was a restricted bay supplied and controlled by freshwater in which mudmicrite and mud-dolomicrite exhibit low δ13C and δ18O values and high 87Sr/86 Sr ratios;(2) all types of karstic rocks in the paleokarst reservoirs of the Huanglong Formation in the research area are affected by atmospheric freshwater with the δ13C and δ18O values and 87Sr/86 Sr ratios in the original formation approaching those of atmospheric freshwater, which reflects ancient hydrological conditions, fluid properties, isotopic source and the fractionation effect;(3) the intensely corroded and replaced secondary limestone is affected by a variety of diagenetic fluids, often reflected by δ13C and δ18O values, while the 87Sr/86 Sr ratios exhibit the strong degree of the corrosion;(4) after comparing the 87Sr/86 Sr ratios of each type of karst rock, the diagenetic fluids are determined to be mainly atmospheric freshwater, and depending on the strength of corrosion, and the low 87Sr/86 Sr ratio fluids in the layer will participate in the karst process. The carbon, oxygen, and strontium isotopes of different karstic reservoirs can provide meaningful geochemical information for forecasting and evaluating the development and distribution rules of the Huanglong Formation at the margin of the eastern Sichuan Basin in time and space.     

Speleothem calcite farmed in situ: Modern calibration of δO and δC paleoclimate proxies in a continuously-monitored natural cave system

Understanding the relationships between speleothem stable isotopes (δ¹³C δ¹⁸O) and in situ cave forcing mechanisms is important to interpreting ancient stalagmite paleoclimate records. Cave studies have demonstrated that the δ¹⁸O of inorganically precipitated (low temperature) speleothem calcite is systematically heavier than the δ¹⁸O of laboratory-grown calcite for a given temperature. To understand this apparent offset, rainwater, cave drip water, groundwater, and modern naturally precipitated calcite (farmed in situ) were grown at multiple locations inside Hollow Ridge Cave in Marianna, Florida. High resolution micrometeorological, air chemistry time series and ventilation regimes were also monitored continuously at two locations inside the cave, supplemented with periodic bi-monthly air gas grab sample transects throughout the cave.Cave air chemistry and isotope monitoring reveal density-driven airflow pathways through Hollow Ridge Cave at velocities of up to 1.2 m s⁻¹ in winter and 0.4 m s⁻¹ in summer. Hollow Ridge Cave displays a strong ventilation gradient in the front of the cave near the entrances, resulting in cave air that is a mixture of soil gas and atmospheric CO₂. A clear relationship is found between calcite δ¹³C and cave air ventilation rates estimated by proxies pCO₂ and ²²²Rn. Calcite δ¹³C decreased linearly with distance from the front entrance to the interior of the cave during all seasons, with a maximum entrance-to-interior gradient of Δδ¹³C_CaCO3 = −7‰. A whole-cave “Hendy test” at multiple contemporaneous farming sites reveals that ventilation induces a +1.9 ± 0.96‰ δ¹³C offset between calcite precipitated in a ventilation flow path and calcite precipitated on the edge or out of flow paths. This interpretation of the “Hendy test” has implications for interpreting δ¹³C records in ancient speleothems. Calcite δ¹³C_CaCO3 may be a proxy not only for atmospheric CO₂ or overlying vegetation shifts but also for changes in cave ventilation due to dissolution fissures and ceiling collapse creating and plugging ventilation windows.Farmed calcite δ¹⁸O was found to exhibit a +0.82 ± 0.24‰ offset from values predicted by both theoretical calculations and laboratory-grown inorganic calcite. Unlike δ¹³C_CaCO3, oxygen isotopes showed no ventilation effects, i.e. Δδ¹⁸O_CaCO3 appears to be a function of growth temperature only although we cannot rule out a small effect of (unmeasured) gradients in relative humidity (evaporation) accompanying ventilation. Our results support the findings of other cave investigators that water-calcite fractionation factors observed in speleothem calcite are higher that those measured in laboratory experiments. Cave and laboratory calcite precipitates may differ mainly in the complex effects of kinetic isotope fractionation. Combining our data with other recent speleothem studies, we find a new empirical relationship for cave-specific water-calcite oxygen isotope fractionation across a range of temperatures and cave environments:

1000lnα=16.1(10³T^-1)-24.6     

δB, Sr, Mg and B in a modern Porites coral: the relationship between calcification site pH and skeletal chemistry

Sr/Ca, B/Ca, Mg/Ca and δ¹¹B were determined at high spatial resolution across ∼1 year of a modern Hawaiian Porites lobata coral by secondary ion mass spectrometry (SIMS). We observe significant variations in B/Ca, Mg/Ca, Sr/Ca and δ¹¹B over short skeletal distances (nominally equivalent to periods of <20 days). This heterogeneity probably reflects variations in the composition of the extracellular calcifying fluid (ECF) from which the skeleton precipitates. Calcification site pH (total scale) was estimated from skeletal δ¹¹B and ranged from 8.3 to 8.8 (± ∼0.1) with a mean of ∼8.6. Sr/Ca and B/Ca heterogeneity is not simply correlated with calcification site pH, as might be expected if Ca-ATPase activity increases the pH and decreases the Sr/Ca and B(OH)₄⁻/CO₃²⁻ ratios of the ECF. We produced a simple model of the ECF composition and the skeleton deposited from it, over a range of calcium transport and carbonate scenarios, which can account for these observed geochemical variations. The relationship between the pH and Sr/Ca of the ECF is dependent on the concentration of DIC at the calcification site. At higher DIC concentrations the ECF has a high capacity to buffer the [H⁺] changes induced by Ca-ATPase pumping. Conversely, at low DIC concentrations, this buffering capacity is reduced and ECF pH changes more rapidly in response to Ca-ATPase pumping. The absence of a simple correlation between ECF pH and skeletal Sr/Ca implies that calcification occurred under a range of DIC concentrations, reflecting variations in the respiration and photosynthesis of the coral and symbiotic zooxanthellate in the overlying coral tissues. Our observations have important implications for the use of coral skeletons as indicators of palaeo-ocean pH.     

Climatology of the Eastern Arabian Sea during the last glacial cycle reconstructed from paired measurement of foraminiferal δO and Mg/Ca

Paired measurements of Mg/Ca and δ¹⁸O of Globigerenoides sacculifer from an Eastern Arabian Sea (EAS) sediment core indicate that sea-surface temperature (SST) varied within 2°C and sea-surface salinity within 2 psu during the last 100 ka. SST was coldest (∼ 27°C) during Marine Isotope Stage (MIS) 4 and 2. Sea-surface salinity was highest (∼ 37.5 psu) during most of the last glacial period (∼ 60–18 ka), concurrent with increased δ¹⁸O_G.sacculifer and C/N ratios of organic matter and indicative of sustained intense winter monsoons. SST time series are influenced by both Greenland and Antarctic climates. However, the sea-surface salinity time series and the deglacial warming in the SST record (beginning at ∼ 18 ka) compare well with the LR04 benthic δ¹⁸O-stack and Antarctic temperatures. This suggests a teleconnection between the climate in the Southern Hemisphere and the EAS. Therefore, the last 100-ka variability in EAS climatology appears to have evolved in response to a combination of global climatic forcings and regional monsoons. The most intense summer monsoons within the Holocene occurred at ∼ 8 ka and are marked by SST cooling of ∼ 1°C, sea-surface salinity decrease of 0.5 psu, and δ¹⁸O_G.sacculifer decrease of 0.2‰.     

The record of temperature, wind velocity and air humidity in the δD and δO of water inclusions in synthetic and Messinian halites

Deuterium and oxygen isotope fractionations between liquid and vapor water were experimentally-determined during evaporation of a NaCl solution (35 g L⁻¹) as a function of water temperature and wind velocity. In the case of a null wind velocity, slopes of δD-δ¹⁸O trajectories of residual waters hyperbolically decrease with increasing water temperatures in the range 23-47 °C. For wind velocities ranging from 0.8 to 2.2 m s⁻¹, slopes of the δD-δ¹⁸O trajectories linearly increase with increasing wind velocity at a given water temperature. These experimental results can be modeled by using Rayleigh distillation equations taking into account wind-related kinetics effects. Deuterium and oxygen isotope compositions of water inclusions trapped by the precipitated halite crystals were determined by micro-equilibration techniques.These isotopic compositions accurately reflect those of the surrounding residual waters during halite growth. Isotopic compositions of water inclusions in twenty natural halites from the Messinian Realmonte mine in Sicily suggest precipitation temperatures of that match the homogenization temperatures obtained by microthermometry (median = 34 ± 5 °C). The similarity between the measured and experimental slopes of the δD-δ¹⁸O evaporation trajectories suggests that the effect of wind was negligible during the genesis of these halite deposits. Hydrogen and oxygen isotope compositions of water inclusions from Realmonte halite also define a linear trend whose extrapolation until intersection with the Mediterranean Meteoric Water Line allows the characterization of the water source with δD and δ¹⁸O values of −70 ± 10‰ and −11.5 ± 1.5‰, respectively. These results reveal that the huge amounts of salts deposited in Sicily result from the evaporation of seawater mixed with a dominant fraction (?50%) of meteoric waters most likely deriving from alpine fluvial discharge.     

Sr/Ca,Mg/Ca:珊瑚岛鸟粪沉积的物源指示计*

文章尝试用Sr/Ca,Mg/Ca比值作物源指示计,区分了珊瑚岛屿受到海鸟粪影响的湖泊沉积物中鸟粪、珊瑚砂、植物这几种主要的环境介质对沉积物的相对贡献,据此恢复1800年来西沙群岛东岛海鸟数量变化和植被演化的历史。结果表明,东岛海鸟数量的变化历史可划分为潜伏期、增长期、稳定期和衰退期4个阶段,历史时期东岛海鸟生态系统的建立和发展与岛屿植被的演变有着密切的联系。研究获得的方法和初步结论为进一步开展西沙岛屿海鸟数量变化、植被演化的广泛对比并探讨与气候变化、人类活动的相互联系提供了基础。     

Origin and migration of brines from Paleozoic strata in Central Tarim,China: constraints from 87Sr/86Sr, δD, δ18O and water chemistry

Chemistry of major and minor elements, ⁸⁷Sr/⁸⁶Sr, δD, and δ¹⁸O of oilfield waters, and ⁸⁷Sr/⁸⁶Sr of whole rock were measured from Paleozoic strata in the Central Tarim basin, NW China. The aim is to elucidate the origin and migration of formation water and its relation to petroleum migration. High salinity oilfield waters in Carboniferous, Silurian and Ordovician reservoirs have maintained the same Na/Cl ratio as seawater, indicative of subaerially evaporated seawater. Two possible sources of evaporitic water are Carboniferous (C_II) and Cambrian, both of which contain evaporitic sediments. Geographic and stratigraphic trends in water chemistry suggest that most of the high salinity water is from the Cambrian. Strontium, H and O isotopes as well as ion chemistry indicate at least 3 end member waters in the basin. High-salinity Cambrian evaporitic water was expelled upward into Ordovician, Silurian and Carboniferous reservoirs along faults and fractures during compaction and burial. Meteoric water has likely invaded the section throughout its history as uplift created subaerial unconformities. Meteoric water certainly infiltrated Silurian and older strata during development of the C_III unconformity and again in recent times. Modern meteoric water enters Carboniferous strata from the west and flows eastward, mixing with the high salinity Cambrian water and to a lesser degree with paleometeoric water. The third end member is highly radiogenic, shale-derived water which has migrated eastward from the Awati Depression to the west. Enrichment of Ca and Sr and depletion of K, Mg, and SO₄ relative to the seawater evaporation trajectory suggest waters were affected by albitization of feldspars, dolomitization, illitization of smectite, and SO₄ reduction. The mixing of meteoric water occurred subsequently to seawater evaporation, main water-rock interactions, and brine migration. The direction of brine migration is consistent with that of petroleum migration, suggesting water and petroleum have followed the same migration pathways.     

Can sedimentary leaf waxes record D/H ratios of continental precipitation? Field, model, and experimental assessments

D/H ratios of leaf waxes (δD_wax) derived from terrestrial plants and preserved in lake sediments can provide important information on past continental hydrology. Ideally, δD_wax can be used to reconstruct precipitation D/H ratios (δD_P) which is a well-established paleoclimate proxy. However, many other factors, such as vegetation and relative humidity (RH), also affect δD_wax variation. How the combination of these factors affects sedimentary δD_wax is unclear. Here, we use a transect of 32 lake surface sediments across large gradients of precipitation, relative humidity, and vegetation composition in the southwestern United States to study the natural factors affecting sedimentary δD_wax. δD values of C₂₈n-alkanoic acids show significant correlation with δD_P values (R² = 0.76) with an apparent isotopic enrichment of ∼99 ± 8‰, indicating that sedimentary δD_wax values track overall δD_P variation along the entire transect. Leaf waxes produced by plants grown under controlled conditions (RH = 80%, 60%, 40%) show a small increase in D/H ratios as RH decreases, consistent with prediction from the Craig-Gordon model. However, the isotopic effect of RH on δD_wax along the natural transect is partially countered by the opposing influence of vegetation changes. The correlation between δD_wax and δD_P values is significantly higher (R² = 0.84) in the drier portions of the transect than in the wetter regions (R² = 0.64). This study suggests that D/H ratios of sedimentary leaf waxes can be used as a proxy for precipitation δD variations, with particularly high fidelity in dry regions, although more studies in other regions will be important to further test this proxy.     

Intra-shell boron isotope ratios in the symbiont-bearing benthic foraminiferan Amphistegina lobifera: Implications for δB vital effects and paleo-pH reconstructions

The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ¹¹B has some limitations such as the knowledge of the fractionation factor (α_4-3) between boric acid and the borate ion and the amplitude of “vital effects” on this proxy that are not well constrained. Using secondary ion mass spectrometry (SIMS) we have examined the internal variability of the boron isotope ratio in the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24 ± 0.1 °C) in seawater with pH ranging between 7.90 and 8.45. Intra-shell boron isotopes showed large variability with an upper limit value of ≈30‰. Our results suggest that the fractionation factor α_4-3 of 0.97352 (Klochko et al., 2006) is in better agreement with our experiments and with direct pH measurements in seawater vacuoles associated with the biomineralization process in these foraminifera. Despite the large variability of the skeletal pH values in each cultured specimen, it is possible to link the lowest calculated pH values to the experimental culture pH values while the upper pH limit is slightly below 9. This variability can be interpreted as follows: foraminifera variably increase the pH at the biomineralization site to about 9. This increase above ambient seawater pH leads to a range in δ¹¹B (Δ¹¹B) for each seawater pH. This Δ¹¹B is linearly correlated with the culture seawater pH with a slope of −13.1 per pH unit, and is independent of the fractionation factor α_4-3, or the δ¹¹B_sw through time. It may also be independent of the pK_B (the dissociation constant of boric acid) value. Therefore, Δ¹¹B in foraminifera can potentially reconstruct paleo-pH of seawater.     

Seasonal changes of fulvic acid,Ca and Mg concentrations of water samples collected above and in the Béke Cave of the Aggtelek karst system (Hungary)

Magnesium and Ca concentration ratios, fulvic acid content, total dissolved inorganic carbon (DIC) and pH were determined in seepage water and drip water samples collected during one seasonal cycle between June 2000 and May 2001 above and in the Béke Cave of Aggtelek (Hungary). Seepage water samples were collected at 0.5 and 7 m below ground level from an observation point situated above the cave. Drip water was collected 40 m underground from a group of stalactites. The fulvic acid concentrations were determined by fluorescence spectrometry after pre-concentration on a XAD-8 chromatographic column. Calcium and Mg concentrations were measured by inductively coupled plasma atomic-emission spectrometry. DIC was determined with a CO₂ – selective electrode. DIC values increased and the fulvic acid concentrations and Mg and Ca concentration ratios, generally, decreased with depth. The highest flux of fulvic acid was observed in spring. The fulvic acid flux increased by a factor of 2.6–3.6 and 1.4 for groundwater and drip water, respectively, compared with those registered in the winter samples. The variations in the Ca, Mg and fulvic acid concentrations of the seepage and drip water samples relate to the variable drip rate. The results revealed that there is a strong correlation between the daily average surface temperature, daily amount of precipitation and drip water rate registered in the cave.     

Paired Measurements of Foraminiferal δ~ (18) O and Mg/Ca Ratios of Indian Monsoons Reconstructed from Holocene to Last Glacial Record

The effect of seasonally reversing monsoons in the northern Indian Ocean is to impart significant changes in surface salinity(SS).Here,we report SS changes during the last 32 kyr in the Lakshadweep Sea(southeastern Arabian Sea)estimated from paired measurements of δ~(18)O and sea surface temperature(SST)using Globigerinoides sacculifer,an upper mixed layer dwelling foraminifera.The heaviest δ~(18)O_(G.sacculifer)(-0.07±0.08‰)is recorded between 23 and 15 ka,which could be defined as the last glacial maxi...     

Constraining the marine strontium budget with natural strontium isotope fractionations (Sr/Sr∗, δSr) of carbonates, hydrothermal solutions and river waters

We present strontium (Sr) isotope ratios that, unlike traditional ⁸⁷Sr/⁸⁶Sr data, are not normalized to a fixed ⁸⁸Sr/⁸⁶Sr ratio of 8.375209 (defined as δ^88/86Sr = 0 relative to NIST SRM 987). Instead, we correct for isotope fractionation during mass spectrometry with a ⁸⁷Sr-⁸⁴Sr double spike. This technique yields two independent ratios for ⁸⁷Sr/⁸⁶Sr and ⁸⁸Sr/⁸⁶Sr that are reported as (⁸⁷Sr/⁸⁶Sr∗) and (δ^88/86Sr), respectively. The difference between the traditional radiogenic (⁸⁷Sr/⁸⁶Sr normalized to ⁸⁸Sr/⁸⁶Sr = 8.375209) and the new ⁸⁷Sr/⁸⁶Sr∗ values reflect natural mass-dependent isotope fractionation. In order to constrain glacial/interglacial changes in the marine Sr budget we compare the isotope composition of modern seawater ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_Seawater) and modern marine biogenic carbonates ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_Carbonates) with the corresponding values of river waters ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_River) and hydrothermal solutions ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_HydEnd) in a triple isotope plot. The measured (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_River values of selected rivers that together account for ∼18% of the global Sr discharge yield a Sr flux-weighted mean of (0.7114(8), 0.315(8)‰). The average (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_HydEnd values for hydrothermal solutions from the Atlantic Ocean are (0.7045(5), 0.27(3)‰). In contrast, the (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_Carbonates values representing the marine Sr output are (0.70926(2), 0.21(2)‰). We estimate the modern Sr isotope composition of the sources at (0.7106(8), 0.310(8)‰). The difference between the estimated (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_input and (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_output values reflects isotope disequilibrium with respect to Sr inputs and outputs. In contrast to the modern ocean, isotope equilibrium between inputs and outputs during the last glacial maximum (10-30 ka before present) can be explained by invoking three times higher Sr inputs from a uniquely “glacial” source: weathering of shelf carbonates exposed at low sea levels. Our data are also consistent with the “weathering peak” hypothesis that invokes enhanced Sr inputs resulting from weathering of post-glacial exposure of abundant fine-grained material.     

Formation of helictite in the cave Dragon Belly (Sardinia,Italy)—Microstructure and incorporation of Mg,Sr, and Ba

In the Dragon Belly cave helictites, a special type of irregular speleothem, are found, which grew on stalactites in all vertical and horizontal directions without any affinity to gravity. Microstructural and mineralogical analyses of this stalactite–helictite system indicate that its evolution is initiated by clogging of the central stalactite channel at its tip, probably when the cave was flooded by muddy water. Clogging caused the formation of secondary channels (≈0.2 mm in diameter) for water passage through the outer surface of the stalactite, where helictites start to grow. The secondary channel passes into the central channel of the helictite.The helictites consist of stacked idiomorphic calcite crystals with uniform orientation. Growth of calcite is essentially controlled by water transfer through the central channel and via canalicules (narrow channels of ≈0.05 mm in diameter) following the crystal boundaries of the calcite mesocrystal induced by capillary hydrostatic forces. At straight parts of the helictites calcite crystals are almost uniform in size, but at bended parts crystals are significantly smaller inside (≤0.1 mm in length) than outside of the bend (≤0.5 mm). It is proposed that the difference in calcite volume (larger crystals) vs. the inside of the bend leads to a helix form, which explains the origin of the term helictite.The Sr and Ba concentrations measured by laser ablation along helictites can be explained by cation incorporation during calcite precipitation close to equilibrium. Dilution effects caused by seasonality control the elemental distribution in the helictite, which result in a positive correlation between Sr and Ba. Variability of Mg is unrelated with Sr and Ba, and is probably due to the incongruent dissolution of Mg–calcite from the host rock.     

Geochemistry,isotopic composition (δO, δH,Sr/Sr,Nd/Nd) in the groundwater of French Guiana as indicators of their origin,interrelations

The current use of untreated river water for drinking purposes by the population of French Guiana has important impacts on public health. Consequently, groundwater is of major importance as a possible alternative drinking water supply to reduce these impacts. Since French Guiana belongs to the Guyana Shield, sustainable water management can be expected to depend increasingly on water from fissured aquifers in hard rocks. Groundwater samples were collected from shallow drill holes in the densely populated coastal area, and deeper wells in the basement (around Cayenne and along the Maroni and Oyapock rivers). This study reports on major and trace elements for which Na⁺ and Ca²⁺ excess with regard to Cl reflect the role of water-rock interaction, as well as Sr and Nd isotopes that reflect the role of the different lithologies. δ¹⁸O and δD in waters give constraints on the water cycle (recharge and evaporation processes).     

Isotopic evidence (Sr/Sr, δLi) for alteration of the oceanic crust at deep-rooted mud volcanoes in the Gulf of Cadiz, NE Atlantic Ocean

The chemical and isotopic composition of pore fluids is presented for five deep-rooted mud volcanoes aligned on a transect across the Gulf of Cadiz continental margin at water depths between 350 and 3860 m. Generally decreasing interstitial Li concentrations and ⁸⁷Sr/⁸⁶Sr ratios with increasing distance from shore are attributed to systematically changing fluid sources across the continental margin. Although highest Li concentrations at the near-shore mud volcanoes coincide with high salinities derived from dissolution of halite and late-stage evaporites, clayey, terrigenous sediments are identified as the ultimate Li source to all pore fluids investigated. Light δ⁷Li values, partly close to those of hydrothermal vent fluids (δ⁷Li: +11.9‰), indicate that Li has been mobilized during high-temperature fluid/sediment or fluid/rock interactions in the deep sub-surface. Intense leaching of terrigenous clay has led to radiogenic ⁸⁷Sr/⁸⁶Sr ratios (∼0.7106) in pore fluids of the near-shore mud volcanoes. In contrast, non-radiogenic ⁸⁷Sr/⁸⁶Sr ratios (∼0.7075) at the distal locations are attributed to admixing of a basement-derived fluid component, carrying an isotopic signature from interaction with the basaltic crust. This inference is substantiated by temperature constraints from Li isotope equilibrium calculations suggesting exchange processes at particularly high temperatures (>200 °C) for the least radiogenic pore fluids of the most distal location.Advective pore fluids in the off-shore reaches of the Gulf of Cadiz are influenced by successive exchange processes with both oceanic crust and terrigenous, fine-grained sediments, resulting in a chemical and isotopic signature similar to that of fluids in near-shore ridge flank hydrothermal systems. This suggests that deep-rooted mud volcanoes in the Gulf of Cadiz represent a fluid pathway intermediate between mid-ocean ridge hydrothermal vent and shallow, marginal cold seep. Due to the thicker sediment coverage and slower fluid advection rates, the overall geochemical signature is shifted towards the sediment-diagenetic signal compared to ridge flank hydrothermal environments.