Identifying sources of groundwater in the lower Colorado River valley, USA, with δ18O, δD, and 3H: implications for river water accounting

Isotope measurements (¹⁸O, D, ³H) indicate groundwater origin in the Lower Colorado River Valley (LCRV) and provide an alternative, or supplement, to the US Bureau of Reclamations proposed accounting surface method. The accounting surface method uses a hydraulic criterion to identify certain wells away from the flood plain that will eventually yield mainstream Colorado River water. New isotope data for 5 surface-water and 18 groundwater sites around Topock Marsh, Arizona, are compared with river-water data (1974–2002) from 11 sites between Utah and Mexico and with groundwater data from previous LCRV studies. Three groundwater sources are repeatedly identified in the LCRV: (1) local recharge derived from precipitation, usually winter rain, plots slightly below the global meteoric water line (GMWL) and has D values that are 20 greater than those of recent river water; (2) older (pre-1950) upper basin river-water plots on or near the GMWL, distinct from local rainfall and recent river water; and (3) recent (post-1950) Colorado River water, including Topock Marsh samples, plots below the GMWL along an evaporation trend. Large floods, as in 1983, complicate interpretation by routing less evaporated upper basin water into the LCRV; however, tritium content can indicate the age of a water. River-water tritium has declined steadily from its peak of 716 TU in 1967 to about 11 TU in 2002. Mixtures of all three groundwater sources are common.

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Resumen Mediciones isotópicas (¹⁸O, D, ³H) indican cual es el origen del agua subterránea en el Valle Bajo del Río Colorado (LCRV) y aportan una alternativa, o complemento, para el método superficie de conteo propuesto por el Buró de Reclamación de Estados Unidos. El método superficie de conteo utiliza un criterio hidráulico para identificar ciertos pozos alejados de la planicie de inundación que eventualmente producirán agua a partir de la corriente principal del Río Colorado. Los nuevos datos isotópicos para 18 sitios de agua subterránea y 5 sitios de agua superficial cerca de los Pantanos Topock, Arizona, se comparan con datos de agua de río (1974–2002) provenientes de 11 sitios localizados entre Utah y México, y con datos de aguas subterráneas de estudios previos realizados en el LCRV. Se identifican reiteradamente tres fuentes de aguas subterráneas en el LCRV: (1) recarga local derivada de precipitación, generalmente lluvia de invierno, cuya composición cae ligeramente por debajo de la línea de agua meteórica global (GMWL) y tiene valores D que son 20 mayores que los reportados para agua de río reciente; (2) el agua de río más vieja (pre-1950) de la cuenca alta cuya composición cae sobre o cerca de la GMWL, diferente de la lluvia local y del agua de río reciente; (3) agua reciente (post-1950) del Río Colorado, incluyendo muestras de los Pantanos Topock, con composición por debajo de la GMWL a lo largo de una tendencia a la evaporación. Inundaciones grandes, como en 1983, complican la interpretación al transmitir menos agua evaporada de la cuenca alta hacia el LCRV; sin embargo, el contenido de tritio puede indicar la edad del agua. El contenido de tritio en agua de río ha disminuido constantemente desde la concentración pico de 716 TU en 1967 a cerca de 11 TU en 2002. Es común que exista mezclas de las tres fuentes de agua subterránea.

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Résumé Les mesures isotopiques (d18O, dD, 3H) indiquent les origine de leaux souterraines dans la Vallée de la Rivière du Bas Colorado (LCRV) et sont une alternative, ou un supplément, à la méthode des bilans hydrologiques proposée par du «US Bureau of Reclamation». Cette méthode de bilan hydrologique utilise un critère hydraulique permettant didentifier certains puits hors de la plaine dinondation qui pomperaient une part non négligeable de leur eau dans la rivière Colorado. De nouvelles données isotopiques provenant de 5 sites deau de surface et 18 deaux souterraines autour de Topock Marsh en Arizona, sont comparées avec les données (1974–2000) de 11 sites localisés entre Utah et Mexico, ainsi que des données dautres études sur la LCRV. Ces sources deaux souterraines sont identifiées à plusieurs reprises dans la LCRV: (1) la recharge locale dérivant des précipitations, généralement les pluies hivernales, se retrouvent légèrement sous la ligne deau météoritique globale (GMWL) et possède des valeurs de dD 20% supérieures aux valeurs des eaux récentes de la rivière; (2) les eaux vieilles (pre-1950) du bassin supérieur de la rivière possèdent une valeurs très proches de la GMWL, distinctes des valeurs de la pluie locale et des eaux récentes de la rivière; et (3) les eaux récentes (post-1950) de la Rivière Colorado, incluant les échantillons de Topock Marsh, se positionnent à côté de la GMWL sur une droite dévaporation. Les grandes inondations, par exemple celle de 1983, compliquent linterprétation en reprenant dans la LCRV moins deaux marquées comme évaporées et provenant du bassin supérieur; par ailleurs le pic de tritium est descendu de 716 TU en 1967 à 11 TU en 2002. Les mélanges de ces trois sources sont assez fréquentes.

     

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.     

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.     

Isotopes (δD and δ18O) in precipitation, groundwater and surface water in the Ordos Plateau, China: implications with respect to groundwater recharge and circulation

The characteristics of δD and δ¹⁸O in precipitation, groundwater and surface water have been used to understand the groundwater flow system in the Ordos Plateau, north-central China. The slope of the local meteoric water line (LMWL) is smaller than that of the global meteoric water line (GMWL), which signifies secondary evaporation during rainfall. The distribution of stable isotopes of precipitation is influenced by temperature and the amount of precipitation. The lake water is enriched isotopically due to evaporation and its isotopic composition is closely related to the source of recharge and location in the groundwater flow systems. River water is enriched isotopically, indicating that it suffers evaporation. The deep groundwater (more than 150?m) is depleted in heavy isotopes relative to the shallow groundwater (less than 150?m), suggesting that deep groundwater may have been recharged during the late Pleistocene and early Holocene, when the climate was wetter and colder than at present. All groundwater samples plot around the LMWL, implying groundwater is of meteoric origin. Shallow groundwater has undergone evaporation and the average evaporation loss is 53%. There are two recharge mechanisms: preferential flow, and the mixture of evaporated soil moisture and subsequent rain.     

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).     

Major-ion chemistry, ��13C and 87Sr/86Sr as indicators of hydrochemical evolution and sources of salinity in groundwater in the Yuncheng Basin, China

Processes controlling hydrogeochemistry in the Yuncheng Basin, China, were characterised using major-ion chemistry, ⁸⁷Sr/⁸⁶Sr ratios and ??¹³C values. Evapotranspiration during recharge increased solute concentrations by factors of ??5?C50 in deep palaeowaters, while higher degrees of evapotranspiration have occurred in shallow, modern groundwater. Aquifer sediments (loess) contain approximately 15 weight% calcite; trends in groundwater HCO₃ concentrations and ??¹³C values (ranging from ?16.4 to ?8.2??) indicate that carbonate weathering is a significant source of DIC. Groundwater ⁸⁷Sr/⁸⁶Sr ratios (0.7110?C0.7162, median of 0.7116) are similar to those in both loess carbonate (0.7109?C0.7116) and local rainfall (0.7112), and are significantly lower than Sr in aquifer silicates (0.7184?C0.7251). Despite evidence for substantial carbonate dissolution, groundwater is generally Ca-poor (<?10% of total cations) and Na-rich, due to cation exchange. Saturation with respect to carbonate minerals occurs during or soon after recharge (all calcite and dolomite saturation indices are positive). Subsequent carbonate dissolution in the deep aquifer must occur as a second-stage process, in response to Ca loss (by ion exchange) and/or via incongruent dissolution of dolomite and impure calcite. The latter is consistent with positive correlations between ??¹³C values and Mg/Ca and Sr/Ca ratios (r ²?=?0.32 and 0.34).     

Paleo-climate of the Boise area, Idaho from the last glacial maximum to the present based on groundwater δH and δO compositions

A 30 ka paleo-climate record of the Boise area, Idaho, USA has been delineated using groundwater stable isotopic compositions. Groundwater ages are modern (cold batholith), 5-15 ka (thermal batholith) , 10-20 ka (frontal fault) , and 20-30 ka (Snake River plain thermal). The stable isotopic composition of groundwaters have been used as a surrogate for the stable isotopic composition of precipitation. Using δ²H and δ¹⁸O compositions, local groundwater lines (LGWL's) were defined for each system. Each LGWL has been evaluated with defined slopes of 6.94 and 8, respectively, and resulting deuterium excess values (d) were found for each groundwater system for each slope. Time dependent changes in moisture source humidity and temperature, and Boise area recharge temperatures, calculated from stable isotopic data and the deuterium excess factors, agree with previous paleo-climate studies. Results indicate that from the last glacial maximum to the present time the humidity over the ocean moisture source increased by 9%, sea surface temperature at the moisture source increased 6-7°C, and local Boise temperature increased by 4-5°C. A greater increase of temperature at the moisture source as compared to the Boise area may impart be due to a shift in the moisture source area.     

Using stable isotopes (δD, δ<Superscript>18</Superscript>O, δ<Superscript>34</Superscript>S and <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr) to identify sources of water in abandoned mines in the Fengfeng coal mining district,northern China

With depleted coal resources or deteriorating mining geological conditions, some coal mines have been abandoned in the Fengfeng mining district, China. Water that accumulates in an abandoned underground mine (goaf water) may be a hazard to neighboring mines and impact the groundwater environment. Groundwater samples at three abandoned mines (Yi, Er and Quantou mines) in the Fengfeng mining district and the underlying Ordovician limestone aquifer were collected to characterize their chemical and isotopic compositions and identify the sources of the mine water. The water was HCO₃·SO₄-Ca·Mg type in Er mine and the auxiliary shaft of Yi mine, and HCO₃·SO₄-Na type in the main shaft of Quantou mine. The isotopic compositions (δD and δ¹⁸O) of water in the three abandoned mines were close to that of Ordovician limestone groundwater. Faults in the abandoned mines were developmental, possibly facilitating inflows of groundwater from the underlying Ordovician limestone aquifers into the coal mines. Although the Sr²⁺ concentrations differed considerably, the ratios of Sr²⁺/Ca²⁺ and ⁸⁷Sr/⁸⁶Sr and the ³⁴S content of SO₄^2? were similar for all three mine waters and Ordovician limestone groundwater, indicating that a close hydraulic connection may exist. Geochemical and isotopic indicators suggest that (1) the mine waters may originate mainly from the Ordovician limestone groundwater inflows, and (2) the upward hydraulic gradient in the limestone aquifer may prevent its contamination by the overlying abandoned mine water. The results of this study could be useful for water resources management in this area and other similar mining areas.     

Fluid Composition, δD of Channel H2O,and δ18O of Lattice Oxygen in Beryls: Genetic Implications for Brazilian,Colombian, and Afghanistani Emerald Deposits

The fluid composition, δD of channel H₂O, and δ₁₈O of lattice oxygen have been determined in beryl and emerald from a variety of geological environments and used to constrain the origin of the parental fluids from which beryl has grown. Step-heating analyses performed by quadrupolar mass spectrometry were used to quantify the composition of the fluid phases in beryl from granitic pegmatites and greisens and emerald from Brazil, Colombia, and Afghanistan. An important conclusion is that beryl and emerald have a similar fluid composition, with concentrations of H₂O being greater than 90% of the total water in the mineral irrespective of the age of formation (2.0 Ga to 32 Ma) and tectonic settings. However, the Brazilian Santa Terezinha shear-zone emerald deposit contains abundant CO₂, up to 13 wt% of the total fluid. A second conclusion is that the channel H₂O content for some Brazilian emeralds is higher than the range defined for beryl in the literature, especially for those related to the shear-zone type (2.99 lt; H₂O < 3.16 wt%) and the pegmatite type from the Pombos, Pela Ema, and Pirenopolis deposits (2.78 < H₂O < 3.01 wt%). Colombian emeralds have very low H₂O contents (1.30 < H₂O < 1.96 wt%), among the lowest in the world.

Brazilian, Colombian, and Afghanistani emeralds have contrasting and restricted ranges of δ¹⁸O values. In Brazil, emeralds related to pegmatites have a systematic δ¹⁸O inter-deposit variability (+6.3 < δ¹⁸O < +12.4‰). The calculated δ¹⁸O of the fluid was buffered by the host ultrabasic rocks during fluid-rock interaction. Emerald and cogenetic phlogopite related to shear-zone-type deposits have a quite restricted δ¹⁸O range (+12.0 < δ¹⁸O 7lt; +12.4‰); the calculated is interpreted to represent the original isotopic composition of the hydrothermal fluid. Relative to Brazil, the δ¹⁸O of Colombian and Afghanistani emeralds shows strong enrichment in ¹⁸O (+13.4 < δ¹⁸O < +23.6‰), and the high calculated δ¹⁸O of the fluid suggests extensive reaction with 18O-rich sedimentary or metasedimentary rocks.

In Brazil, the δD composition of channels in emerald and the calculated δ¹⁸O^H₂O for phlogopite are compatible with both magmatic and metamorphic origins. A magmatic origin is supported for emeralds associated with the pegmatitic Socotó and Carnaiba deposits (mean δD = ?37.8 ± 8‰) and a metamorphic origin is suggested for the Santa Terezinha shear-zone type (mean δD = ?32.4 ± 3‰). A metamorphic origin is proposed for Colombian emeralds. Afghanistani emeralds have a δD composition of channels (mean δD = ?46.3 ± 1.3‰) that is compatible with both magmatic and metamorphic origins.     

Variations in composition and δ18O values within the Kaffo albite—Riebeckite granite of Liruei Complex,Younger Granites of Nigeria

The peralkaline Kaffo albite—riebeckite granite is an albitised, low-temperature intrusion in Liruei Complex, one of the oldest of the ring-complexes in the Younger Granite province of Nigeria. Analyses of borehole samples from different parts of the intrusion show it to be compositionally heterogeneous, especially in respect of Si, Al, Na, K and F distribution and this, in part, can be correlated with the variable degree of albitisation. Isotopically the granite is a normal plutonic type with δ¹⁸ O values of $\text{+ 8.1 ± 0.2‰}$, and albitisation does not seem to have been accompanied by exchange of isotopes between albitising fluid and the granite. Co-existing riebeckitic-arfvedsonite and aegirine pairs from borehole samples show extreme enrichment in Na and Fe; the amphibole also shows considerable substitution of Fe by Ti, Zn and Mn, and of OH by F. Isotopically the amphibole and pyroxene are different from others, having low, variable δ¹⁸ O values (+5.3–+6.4 and $\text{+4.4–+5.1‰}$, respectively), and the fractionation value Δ Px — Am is always large, negative and constant (—$\text{1.2 ± 0.2‰}$). The low δ¹⁸ O values are considered to be due to special features of the crystal chemistry of the alkali amphiboles and pyroxenes, and the spread of each set of values may be due to sub-solidus isotope exchange between the minerals and albitising fluid.     

Chemical and isotopic investigations (δ<Superscript>18</Superscript>O, δ<Superscript>2</Superscript>H, <Superscript>3</Superscript>H, <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr) to define groundwater processes occurring in a deep-seated landslide in flysch

Deep-seated landslides are complex systems. In many cases, multidisciplinary studies are necessary to unravel the key hydrological features that can influence their evolution in space and time. The deep-seated Berceto landslide, in the northern Apennines of Italy, has been investigated in order to define the origin and geochemical evolution of groundwater (GW), to identify the slope system hydrological boundary, and to highlight the GW flow paths, transit time and transfer modalities inside the landslide body. This research is based on a multidisciplinary approach that involves monitoring GW levels, obtaining analyses of water chemistry and stable and unstable isotopes (δ¹⁸O-δ²H, ³H, ⁸⁷Sr/⁸⁶Sr), performing soil leaching tests, geochemical modelling (PHREEQC), and principal component analysis (PCA). The results of δ¹⁸O-δ²H and ⁸⁷Sr/⁸⁶Sr analyses show that the source of GW recharge in the Berceto landslide is local rainwater, and external contributions from a local stream can be excluded. In the landslide body, two GW hydrotypes (Ca-HCO₃ and Na-HCO₃) are identified, and the results of PHREEQC and PCA confirm that the chemical features of the GW depend on water–rock interaction processes occurring inside the landslide. The ³H content suggests a recent origin for GW and appears to highlight mixing between shallow and deep GW aliquots. The ³H content and GW levels data confirm that shallow GW is mainly controlled by a mass transfer mechanism. The ³H analyses with GW levels also indicate that only deep GW is controlled by a pressure transfer mechanism, and this mechanism is likely the main influence on the landslide kinematics.     

Spatio-temporal variations of δ<Superscript>2</Superscript>H and δ<Superscript>18</Superscript>O in precipitation and shallow groundwater in the Hilly Loess Region of the Loess Plateau,China

Groundwater is of utmost significance to socio-economic development and ecological recovery for the Loess Plateau. However, studies regarding the mechanism governing groundwater recharge over this area appear to be inadequate. This study is to examine the spatio-temporal variations of δ²H and δ¹⁸O in precipitation and shallow groundwater. On the basis of this, the mechanisms governing shallow groundwater recharge were explored. Precipitation and groundwater were sampled monthly from May to October during the period 2004–2006 at 13 sites in the Chabagou Catchment (187 km²). In the Caopingxigou Experimental Watershed (0.1 km²), meteorological variables were observed and rainfall larger than 5 mm was sampled immediately after each rain event. Across the area, 90% of the precipitation occurred from May to September primarily in the form of heavy rains or rainstorms with great spatial variability. There were about 30 localized rains in each year. It was indicated that there existed notable seasonality and pronounced spatial variability in precipitation isotopic compositions. Contributing factors and indications of isotopic compositions, as well as their climatic indications such as monsoon intensities and mixing processes of water vapor, were investigated. The δ²H–δ¹⁸O relation of groundwater was found to be δ²H = 3.22 × δ¹⁸O − 38.1, deviating from the local meteoric water line δ²H = 7.57 × δ¹⁸O + 3.9. The range of δ values in groundwater is shrunken to be 15–21% of that in individual precipitations, and groundwater in the middle reaches shows a wider range of δ values. Isotopic results showed that groundwater originates from precipitation with hydrogen and oxygen isotopic compositions being −69 and −9.7‰, respectively, and most groundwater experiences serious evaporation and adequate mixing with old water during infiltration or percolation in the aerated zone. It was also founded that obvious fluctuations of isotopic compositions in groundwater mainly appear in the middle reaches especially at sites that are close to valleys, suggesting varying sources of groundwater from precipitation, precipitation runoff, isotopically enriched surface water and/or lateral recharge of adjacent groundwater.     

Environmental controls on the δ18O composition of freshwater calcite and aragonite in a temperate,lowland river system: significance for palaeoclimatic studies

The oxygen and carbon isotopic composition of surficial carbonates is a key technique for reconstructing past environments and climates. The understanding of modern isotopic systems is, however, a vital first step before applying these techniques to fossil examples. In this study the δ¹⁸O of aragonite shells from three different freshwater mollusc species and the δ¹⁸O of tufa stromatalites are analysed and compared to the modern temperature and isotopic regime of the river system in which they form (the river Gipping, Sproughton, southeast England). In all cases this range of carbonates appear to form in isotopic equilibrium with the δ¹⁸O of modern waters at water temperatures experienced during the summer months. It is, therefore, likely that in Quaternary interglacial deposits of the UK and western Europe the δ¹⁸O of fossil freshwater molluscs and tufa stromatolite carbonates will provide an indication of past summer temperature regimes and not mean annual temperatures, as has been previously suggested. The paper concludes by discussing the implications of this study for the isotopic analysis of interglacial deposits in Britain and western Europe.     

Early Cretaceous (late Berriasian to early Aptian) palaeoceanographic change along the northwestern Tethyan margin (Vocontian Trough,southeastern France): δ13C, δ18O and Sr-isotope belemnite and whole-rock records

Stable carbon, oxygen, and strontium isotope records were obtained from uppermost Hauterivian to lowermost Aptian belemnite rostra, which were collected in well-dated sections from the Vocontian Trough (southeastern France). This data set complements previously published belemnite-isotope records from the uppermost Berriasian-Hauterivian interval from the same basin. The belemnite carbon and oxygen isotope record is compared to the carbonate bulk-rock isotope record from the same sections, and from additional Italian sections. With regards to their long-term trends, both belemnite and whole-rock δ¹⁸O records are well correlated, except for the uppermost Hauterivian-lower Barremian interval, within which they deviate. This discrepancy is interpreted to be linked to the latest Hauterivian Faraoni oceanic anoxic event and its early Barremian aftermath. The Faraoni level is characterized by enhanced sea-water stratification, probably induced by the onset of a warmer and more humid climate along the northern Tethyan margin. The early Barremian was characterized by stronger vertical sea-water mixing reflected by a decrease in density contrast between sea-surface and deeper waters. The belemnite oxygen isotope record shows a more stable evolution with smaller fluctuations than its bulk-rock counterpart, which indicates that deeper water masses were not as much subjected to density fluctuations as sea-surface water. The comparison of belemnite and bulk-rock carbon isotope records allows observing the impact of regional influence exerted by platform carbonate ooze shedding on the carbon cycle. Discrepancies in the two records are observed during time of photozoan carbonate platform growth. The strontium isotopic record shows a gradual increase from the uppermost Berriasian to the uppermost lower Barremian followed by a rapid decrease until the uppermost Barremian and a renewed small increase within the lowermost Aptian. The major inflection point in the uppermost lower Barremian appears to predate the onset in the formation of the Ontong-Java volcanic plateau.     

Origin and evolution of oilfield brines from Tertiary strata in western Qaidam Basin: Constraints from <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr, δD, δ<Superscript>18</Superscript>O, δ<Superscript>34</Superscript>S and water chemistry

Chemistry of major and minor elements, ⁸⁷Sr/⁸⁶Sr, δD, δ¹⁸O and δ³⁴S of brines were measured from Tertiary strata and Quaternary salt lakes in the western Qaidam Basin. The water chemistry data show that all oilfield brines are CaCl₂ type. They were enriched in Ca²⁺, B³⁺, Li⁺, Sr²⁺, Br⁻, and were depleted in Mg²⁺, SO₄ ²⁻, which indicated that these brines had the characteristics of deeply circulated water. The relationship between δD and δ¹⁸O shows that all data of these brines decline towards the Global Meteoric Water Line (GWL) and Qaidam Meteoric Water Line (QWL), and that the intersection between oilfield brines and Meteoric Water Lines was close to the local spring and fresh water in the piedmont in the western Qaidam Basin. The results suggest that oilfield brines has initially originated from meteoric water, and then might be affected by water-rock metamorphose, because most oilfield brines distribute in the range of metamorphosing water. The ⁸⁷Sr/⁸⁶Sr values of most oilfield brines range from 0.71121 to 0.71194, and was less than that in salt lake water (>0.712), but close to that of halite in the study area. These imply that salt dissolution occurred in the process of migration. In addition, all oilfield brines have obviously much positive δ³⁴S values (ranging from 26.46‰ to 54.57‰) than that of salt lake brines, which was caused by bacterial sulfate reduction resulting in positive shift of δ³⁴S value and depleteed SO₄ ²⁻ in oilfield brines. Combined with water chemical data and δD, δ¹⁸O, ⁸⁷Sr/⁸⁶Sr, δ³⁴S values, we concluded that oilfield brines mainly originate from the deeply circulated meteoric waters, and then are affected by salt dissolution, water-rock metamorphose, sulfate reduction and dolomitization during the process of migration. These processes alter the chemical compositions of oilfield brines and accumulate rich elements (such as B, Li, Sr, Br, K and so on) for sustainable utilization of salt lake resources in the Qaidam Basin.     

Dynamic scheme of water circulation in karstic aquifers as constrained by Sr and Pb isotopes. Application to the Hérault watershed,Southern France

This paper focuses on the relationship between the karst aquifers and the Hérault River (southern France) as a function of hydrologic conditions. The combination of major and trace element, and Sr and Pb isotopes determined on dissolved load in karstic springs makes it possible to identify a dynamic scheme of the hydrology of the karstic area.In the headwaters part of this area, the Sourcettes Spring is fed by an interrupted stream that infiltrates at the basement-sedimentary cover contact. Internal geochemical processes are also pointed out: (1) water–rock interactions during underground circulation, and (2) water originating from different layers of the aquifer may show different chemistry depending on the hydrological conditions. The Vernède Spring, is fed by a second water supply during high flows (previously considered as unconnected). Finally, the Cent-Fonts Springs have been confirmed to be fed by the Buège interrupted stream.Pb isotopes on the dissolved and particulate loads of the river samples make it possible to discriminate the natural (local rocks) versus anthropogenic (mining district and road traffic) Pb sources. The Pb isotope investigations on karstic water make it possible to differentiate between neighboring springs presenting identical Sr isotope and element ratios, and to point out different underground circulation.

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Resumen Este artículo trata de la relación río-acuífero kárstico en la cuenca de Hérault (Francia), en función de las condiciones hidrológicas. La combinación de elementos principales, elementos traza, e isótopos de estroncio y plomo en muestras de manantiales kársticos permite construir un esquema dinámico de la zona.El manantial de Sourcettes, en la parte alta de la región, está alimentado por una corriente interrumpida que se infiltra a través la cubierta sedimentaria del lecho. También, se apunta a los procesos internos geoquímicos: (1) interacciones roca-acuífero, (2) aguas procedentes de capas diferentes del acuífero, dependiendo de las condiciones hidrológicas. El manantial de Vernède, en el sector oriental de la cuenca, se nutre de una segunda fuente de agua en períodos de aguas altas, que anteriormente se consideraba desconenctada. Finalmente, se ha confirmado que los manantiales de Cent-Fonts captan las aguas del curso interrumpido del Buège.Los isótopos de plomo, tanto en fase disuelta como en suspensión de muestras de río, permiten discriminar entre orígenes naturales (rocas naturales) y antrópicos (minería y tráfico) de este elemento. Las investigaciones en aguas kársticas llevan a diferenciar entre manantiales vecinos que tienen relaciones de isótopos de estroncio idénticas, así como a proponer circulaciones distintas en el acuífero por drenaje o por mineralización no diseminada del plomo.

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Résumé Cet article s'intéresse à la relation entre le karst et une rivière dans le bassin de l'Hérault (France), en fonction des conditions hydrologiques. La combinaison des éléments majeurs, des traces et des isotopes de Sr et Pb déterminés dans la charge dissoute de sources karstiques permet de construire un schéma dynamique de la région karstique.Dans la partie la plus haute de cette région, la source des Sourcettes est alimentée par un cours d'eau qui s'infiltre au contact de la série sédimentaire sur le socle. Des processus géochimiques sont également mis en évidence: (1) des interactions eau-roche au cours du trajet souterrain, (2) de l'eau provenant de différents niveaux de l'aquifère en fonction des conditions hydrologiques. Dans la partie orientale du bassin, la source Vernède reçoit une seconde alimentation lors des fortes crues, précédemment considérée comme n'étant pas connectée. Finalement, on confirme que la source des Cent-Fonts est alimentée par les pertes de la rivière de la Buèges.Les isotopes du Pb dans les charges dissoute et solide des échantillons de rivières ont conduit à faire la distinction entre les sources naturelle (roches locales) et anthropique (mines et trafic routier). Les études sur les isotopes du Pb dans les eaux karstiques permettent de différencier les sources voisines présentant des rapports d'éléments et de signatures isotopiques du Sr identiques, et à distinguer différentes circulations souterraines drainant ou non des minéralisations disséminées de Pb.

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Groundwaters of the Central Ethiopian Rift: diagnostic trends in trace elements, δ<Superscript>18</Superscript>O and major elements

The Ethiopian Rift (a major portion of the Great East African Rift) is characterized by a narrow elongated depression bounded by highlands from both sides. This topographic configuration leads to a monsoon redistribution which resulted in an arid rift floor and humid high rainfall highlands. The rifting and associated volcanism also caused a thinning of the crust and facilitates influx of CO₂ and other mantle gases as diffuse sources or along faults from deeper sources. Groundwaters in the rift floor are usually of high mineral content (high F, U, As and salinity) while those on the plateau are of low mineral content. Among many factors, groundwater availability and quality in the rift floor aquifers is the function of their connection to the aquifers in the high rainfall plateau and the residence time of groundwater prior to reaching the rift floor. This entails the need for addressing one basic hydrologic question in such a setting: at what depth and rate does recharge from the high rainfall highland reach the lowland rift aquifers? This study uses spatial variations in trace elements and relates them to ¹⁴C variations, thereby investigating the suitability of using trace elements as proxies for residence time estimation of groundwaters of relatively short (1,000–2,000 years) residence time. This work also investigates the behavior of trace element trends along the groundwater flow path in a rifted setting and compares them with such trends in sedimentary aquifers elsewhere. The comparison shows a clear difference in behavior of trace elements along the groundwater flow path when compared with such variations in big sedimentary basins with no prominent rifting and volcanism, suggesting the need of calibrating the relation between trace elements and any direct residence time indicators. An integrated use of major elements, trace elements, and environmental isotopes reveals that the main recharge of the aquifers originates from mountain blocks and that recharge takes place via fractures with no evidence of evaporation prior to recharge. Redox processes appear to play a limited role in trace element geochemistry of groundwaters in the region. Progressive trends in trace element composition along the groundwater flow path suggest continuous groundwater flow from the plateau.