Paleowaters in Silurian-Devonian carbonate aquifers: Geochemical evolution of groundwater in the Great Lakes region since the Late Pleistocene

Changes in the climatic conditions during the Late Quaternary and Holocene greatly impacted the hydrology and geochemical evolution of groundwaters in the Great Lakes region. Increased hydraulic gradients from melting of kilometer-thick Pleistocene ice sheets reorganized regional-scale groundwater flow in Paleozoic aquifers in underlying intracratonic basins. Here, we present new elemental and isotopic analyses of 134 groundwaters from Silurian-Devonian carbonate and overlying glacial drift aquifers, along the margins of the Illinois and Michigan basins, to evaluate the paleohydrology, age distribution, and geochemical evolution of confined aquifer systems. This study significantly extends the spatial coverage of previously published groundwaters in carbonate and drift aquifers across the Midcontinent region, and extends into deeper portions of the Illinois and Michigan basins, focused on the freshwater-saline water mixing zones. In addition, the hydrogeochemical data from Silurian-Devonian aquifers were integrated with deeper basinal fluids, and brines in Upper Devonian black shales and underlying Cambrian-Ordovician aquifers to reveal a regionally extensive recharge system of Pleistocene-age waters in glaciated sedimentary basins. Elemental and isotope geochemistry of confined groundwaters in Silurian-Devonian carbonate and glacial drift aquifers show that they have been extensively altered by incongruent dissolution of carbonate minerals, dissolution of halite and anhydrite, cation exchange, microbial processes, and mixing with basinal brines. Carbon isotope values of dissolved inorganic carbon (DIC) range from −10 to −2‰, ⁸⁷Sr/⁸⁶Sr ratios range from 0.7080 to 0.7090, and δ³⁴S-SO₄ values range from +10 to 30‰. A few waters have elevated δ¹³C_DIC values (>15‰) from microbial methanogenesis in adjacent organic-rich Upper Devonian shales. Radiocarbon ages and δ¹⁸O and δD values of confined groundwaters indicate they originated as subglacial recharge beneath the Laurentide Ice Sheet (14-50 ka BP, −15 to −13‰ δ¹⁸O). These paleowaters are isolated from shallow flow systems in overlying glacial drift aquifers by lake-bed clays and/or shales. The presence of isotopically depleted waters in Paleozoic aquifers at relatively shallow depths illustrates the importance of continental glaciation on regional-scale groundwater flow. Modern groundwater flow in the Great Lakes region is primarily restricted to shallow unconfined glacial drift aquifers. Recharge waters in Silurian-Devonian and unconfined drift aquifers have δ¹⁸O values within the range of Holocene precipitation: −11 to −8‰ and −7 to −4.5‰ for northern Michigan and northern Indiana/Ohio, respectively. Carbon and Sr isotope systematics indicate shallow groundwaters evolved through congruent dissolution of carbonate minerals under open and closed system conditions (δ¹³C_DIC = −14.7 to−11.1‰ and ⁸⁷Sr/⁸⁶Sr = 0.7080-0.7103). The distinct elemental and isotope geochemistry of Pleistocene- versus Holocene-age waters further confirms that surficial flow systems are out of contact with the deeper basinal-scale flow systems. These results provide improved understanding of the effects of past climate change on groundwater flow and geochemical processes, which are important for determining the sustainability of present-day water resources and stability of saline fluids in sedimentary basins.     

Note on the isotopic geochemistry of fossil-lacustrine tufas in carbonate plateau—A study from Dungul region (SW Egypt)

Lithological, chemical, and stable isotope data are used to characterize lacustrine tufas dating back to pre-late Miocene and later unknown times, capping different surfaces of a Tertiary carbonate (Sinn el-Kedab) plateau in Dungul region in the currently hyperarid south-western Egypt. These deposits are composed mostly of calcium carbonate, some magnesium carbonate and clastic particles plus minor amounts of organic matter. They have a wide range of (Mg/Ca)_molar ratios, from 0.03 to 0.3. The bulk-tufa carbonate has characteristic isotope compositions: (δ¹³C_mean = −2.49 ± 0.99‰; δ¹⁸O_mean = −9.43 ± 1.40‰). The δ¹³C values are consistent with a small input from C4 vegetation or thinner soils in the recharge area of the tufa-depositing systems. The δ¹⁸O values are typical of fresh water carbonates. Covariation between δ¹³C and δ¹⁸O values probably is a reflection of climatic conditions such as aridity. The tufas studied are isotopically similar to the underlying diagenetic marine chalks, marls and limestones (δ¹³C_mean = −2.06 ± 0.84‰; δ¹⁸O_mean = −10.06 ± 1.39‰). The similarity has been attributed to common meteoric water signatures. This raises large uncertainties in using tufas (Mg/Ca)_molar, δ¹³C and δ¹⁸O records as proxies of paleoclimatic change and suggests that intrinsic compositional differences in material sources within the plateau may mask climatic changes in the records.     

Magnesium isotope systematics of the lithologically varied Moselle river basin, France

Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, ⁸⁷Sr/⁸⁶Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ²⁶Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ²⁶Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ²⁶Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ²⁶Mg vs. ⁸⁷Sr/⁸⁶Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ²⁶Mg and ⁸⁷Sr/⁸⁶Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.     

Geothermal waters from the Taupo Volcanic Zone,New Zealand: Li,B and Sr isotopes characterization

Chemical and isotopic data for 23 geothermal water samples collected in New Zealand within the Taupo Volcanic Zone (TVZ) are reported. Major and trace elements including Li, B and Sr and their isotopic compositions (δ⁷Li, δ¹¹B, ⁸⁷Sr/⁸⁶Sr) were determined in high temperature geothermal waters collected from deep boreholes in different geothermal fields (Ohaaki, Wairakei, Mokai, Kawerau and Rotokawa geothermal systems). Lithium concentrations are high (from 4.5 to 19.9 mg/L) and Li isotopic compositions (δ⁷Li) are homogeneous, ranging between −0.5‰ and +1.4‰. In particular, it is noteworthy that, except for the samples from the Kawerau geothermal field having slightly higher δ⁷Li values (+1.4%), the other geothermal waters have a near constant δ⁷Li signature around a mean value of 0‰ ± 0.6 (2σ, n = 21). Boron concentrations are also high and relatively homogeneous for the geothermal samples, falling between 17.5 and 82.1 mg/L. Boron isotopic compositions (δ¹¹B) are all negative, and display a range between −6.7‰ and −1.9‰. These B isotope compositions are in agreement with those of the Ngawha geothermal field in New Zealand. Lithium and B isotope signatures are in a good agreement with a fluid signature mainly derived from water/rock interaction involving magmatic rocks with no evidence of seawater input. On the other hand, Sr concentrations are lower and more heterogeneous and fall between 2 and 165 μg/L. The ⁸⁷Sr/⁸⁶Sr ratios range from 0.70549 to 0.70961. These Sr isotope compositions overlap those of the Rotorua geothermal field in New Zealand, confirming that some geothermal waters (with more radiogenic Sr) have interacted with bedrocks from the metasedimentary basement. Each of these isotope systems on their own reveals important information about particular aspects of either water source or water/rock interaction processes, but, considered together, provide a more integrated understanding of the geothermal systems from the TVZ in New Zealand.     

Mg isotope constraints on soil pore-fluid chemistry: Evidence from Santa Cruz, California

Mg isotope ratios (²⁶Mg/²⁴Mg) are reported in soil pore-fluids, rain and seawater, grass and smectite from a 90 kyr old soil, developed on an uplifted marine terrace from Santa Cruz, California. Rain water has an invariant ²⁶Mg/²⁴Mg ratio (expressed as δ²⁶Mg) at −0.79 ± 0.05‰, identical to seawater δ²⁶Mg. Detrital smectite (from the base of the soil profile, and therefore unweathered) has a δ²⁶Mg value of 0.11‰, potentially enriched in ²⁶Mg by up to 0.3‰ compared to the bulk silicate Earth Mg isotope composition (although within the range of all terrestrial silicates). The soil pore-waters show a continuous profile with depth for δ²⁶Mg, ranging from −0.99‰ near the surface to −0.43‰ at the base of the profile. Shallow pore-waters (<1 m) have δ²⁶Mg values that are similar to, or slightly lower than the rain waters. This implies that the degree of biological cycling of Mg in the pore-waters is relatively small and is quantified as <32%, calculated using the average Mg isotope enrichment factor between grass and rain (δ²⁶Mg_grass-δ²⁶Mg_rain) of 0.21‰. The deep pore-waters (1-15 m deep) have δ²⁶Mg values that are intermediate between the smectite and rain, ranging from −0.76‰ to −0.43‰, and show a similar trend with depth compared to Sr isotope ratios. The similarity between Sr and Mg isotope ratios confirms that the Mg in the pore-waters can be explained by a mixture between rain and smectite derived Mg, despite the fact that Mg and Sr concentrations may be buffered by the exchangeable reservoir. However, whilst Sr isotope ratios in the pore-waters span almost the complete range between mineral and rain inputs, Mg isotopes compositions are much closer to the rain inputs. If Mg and Sr isotope ratios are controlled uniquely by a mixture, the data can be used to estimate the mineral weathering inputs to the pore-waters, by correcting for the rain inputs. This isotopic correction is compared to the commonly used chloride correction for precipitation inputs. A consistent interpretation is only possible if Mg isotope ratios are fractionated either by the precipitation of a secondary Mg bearing phase, not detected by conventional methods, or selective leaching of ²⁴Mg from smectite. There is therefore dual control on the Mg isotopic composition of the pore-waters, mixing of two inputs with distinct isotopic compositions, modified by fractionation. The data provide (1) further evidence for Mg isotope fractionation at the surface of the Earth and (2) the first field evidence of Mg isotope fractionation during uptake by natural plants. The coherent behaviour of Mg isotope ratios in soil environments is encouraging for the development of Mg isotope ratios as a quantitative tracer of both weathering inputs of Mg to waters, and the physicochemical processes that cycle Mg, a major cation linked to the carbon cycle, during continental weathering.     

Oxygen isotopic studies of the interaction between xenoliths and mafic magma, Voisey’s Bay Intrusion, Labrador, Canada

Sulfide mineralization in the Voisey’s Bay Intrusion, Labrador, Canada, is closely associated with country rock xenoliths that have extensively reacted with basaltic magma. In order to better understand the processes that control the assimilation of country rocks by mafic magma, a detailed study of oxygen isotope systematics related to magma-country rock interaction in the Voisey’s Bay area was undertaken. Protracted interaction of the xenoliths with magma produced refractory mineral assemblages in the xenoliths (2-10 cm in diameter) composed of Ca-rich plagioclase, corundum, hercynite, and minor magnetite. Overgrowth rims of plagioclase and biotite that surround most xenoliths separate the restites from the enclosing igneous matrix. The δ¹⁸O values of minerals from regionally metamorphosed pelitic and quartzofeldspathic protoliths are: plagioclase (8.7-12.3‰), orthoclase (9.5-9.8‰), biotite (5.2-8.7‰), garnet (8.3-10.8‰), pyroxene (8.0-10.1‰), and quartz (9.6-14.0). The δ¹⁸O values of minerals from the hornfels in the contact aureole of the intrusion are consistent with modeling which indicates that as a result of essentially closed system contact metamorphism oxygen isotope values should differ only slightly from those of the protoliths. Hercynite, plagioclase, and corundum separates from the xenoliths have δ¹⁸O values that vary from 2.9‰ to 10.5‰, 5.6‰ to 10.9‰, and 2.0‰ to 6.8‰, respectively. Although a siliceous ¹⁸O-enriched melt has been lost from the xenoliths, corundum, and feldspar δ¹⁸O values are significantly lower than expected through melt loss alone. The relatively low δ¹⁸O values of minerals from the xenoliths may be a function of incomplete isotopic exchange with surrounding mafic magma which had a δ¹⁸O value of ∼5.5‰ to 6.0‰. The high-¹⁸O melt that was released from the xenoliths is partially recorded in the plagioclase overgrowth on the margin of the xenoliths (δ¹⁸O values from 6.2‰ to 10.7‰), and in hercynite that replaced corundum. However, mass balance calculations indicate that a portion of the partial melt must have been transferred to magma that was moving through the conduit system. δ¹⁸O and δD values of biotite surrounding the plagioclase overgrowth range from 5.0‰ to 6.2‰ and −58‰ to −80‰, respectively. These data suggest that the outermost rim associated with many xenoliths has closely approached isotopic equilibrium with uncontaminated mafic magma. The current gabbroic to troctolitic matrix of the xenoliths shows no evidence for contamination by the high-¹⁸O partial melt from the xenoliths. The feldspar and biotite overgrowths on the xenoliths that formed after the motion of the xenoliths relative to the magma had stopped prevented further isotopic exchange between the xenoliths and final magma. The minerals within the xenoliths are not in oxygen isotopic equilibrium with each other, due in part to rapid thermal equilibration, partial melting, and partial exchange with flow through magma.     

Deciphering interaction of regional aquifers in Southern Tunisia using hydrochemistry and isotopic tools

Groundwater is the most important source of water supply in southern Tunisia. Previous hydrogeologic and isotopic studies carried out in this region revealed the existence of two major aquifer systems: the “Complex Terminal” (CT) and the “Continental Intercalaire” (CI). Turonian carbonates constitute one of the major aquifer levels of the CT multilayered aquifer. It extends over most of southern Tunisia, and its hydrodynamic regime is largely influenced by tectonics, lithology and recharge conditions. Forty-eight groundwater samples from the CI and Turonian aquifers were collected between January and April 2004 for chemical and isotopic analyses. Hydrochemistry and isotopic tools were combined to get an insight into the processes controlling chemical composition of groundwater and wide-scale interaction of these two aquifer systems. Analysis of the dissolved constituents revealed that several processes control the observed chemical composition: (i) incongruent dissolution of carbonate minerals, (ii) dissolution of evaporitic minerals, and (iii) cation exchange. Dissolution alone cannot account for the observed high supersaturation states of groundwater with respect to calcite and dolomite. The observed supersaturation is most probably linked to geogenic CO₂ entering water-bearing horizons of the CT and CI aquifers via deep tectonic faults and discontinuities and subsequent degassing in the exploitation wells. Presence of geogenic CO₂ in the investigated region was confirmed by C isotope data of the DIC reservoir. The radiocarbon content of the Turonian samples varied between 9.5 and 43 pmc. For CI samples generally lower values were recorded, between 3.8 and 22.5 pmc. Stable isotope composition of Turonian groundwater samples varied from −8.3 to −5.3‰ for δ¹⁸O and from −60 to −25‰ for δ²H. The corresponding ranges of δ values for the Continental Intercalaire samples were from −8.9‰ to −6.9‰ for δ¹⁸O and from −68.2‰ to −45.7‰ for δ²H. Stable isotope composition of groundwater representing CT and CI aquifers provide strong evidence for regional interaction between both systems.     

Controls, variation, and a record of climate change in detailed stable isotope record in a single bryozoan skeleton

The long-lived (about 20 yr) bryozoan Adeonellopsis sp. from Doubtful Sound, New Zealand, precipitates aragonite in isotopic equilibrium with seawater, exerting no metabolic or kinetic effects. Oxygen isotope ratios (δ¹⁸O) in 61 subsamples (along three branches of a single unaltered colony) range from −0.09 to +0.68‰ PDB (mean = +0.36‰ PDB). Carbon isotope ratios (δ¹³C) range from +0.84 to +2.18‰ PDB (mean = +1.69‰ PDB). Typical of cool-water carbonates, δ¹⁸O-derived water temperatures range from 14.2 to 17.5 °C. Adeonellopsis has a minimum temperature growth threshold of 14 °C, recording only a partial record of environmental variation. By correlating seawater temperatures derived from δ¹⁸O with the Southern Oscillation Index, however, we were able to detect major events such as the 1983 El Niño. Interannual climatic variation can be recorded in skeletal carbonate isotopes. The range of within-colony isotopic variability found in this study (0.77‰ in δ¹⁸O and 1.34 in δ¹³C) means that among-colony variation must be treated cautiously. Temperate bryozoan isotopes have been tested in less than 2% of described extant species — this highly variable phylum is not yet fully understood.     

Iron isotopes in natural carbonate minerals determined by MC-ICP-MS with a Fe-Fe double spike

We have developed a method for iron isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) using a ⁵⁸Fe-⁵⁴Fe double spike. A 20 min analysis produces mass-bias-corrected iron isotope data with an external reproducibility of ±0.05 (2 SD) on δ⁵⁶Fe, which represents a decrease in analysis time compared to sample-standard bracketing techniques. The estimation of external reproducibility is based on replicate analysis of the ETH hematite in-house standard. The double spike method has two advantages. First, matrix effects during MC-ICP-MS analysis are decreased with tests showing that accurate iron isotope data can, in some cases, be obtained even when matrix levels exceed iron concentration (Na/Fe, Mg/Fe, and Ca/Fe up to 5, 2, and 0.1, respectively). Because chemical separation reduces matrix/Fe to levels more than three orders of magnitude lower than this, measured Fe isotope compositions are unlikely to be compromised by matrix effects. Second, it is possible to spike samples before chemical purification, which enables any isotopic fractionation effect because of incomplete recovery of iron from a sample to be accounted for. This may be important where obtaining quantitative iron yields from samples is difficult, such as the extraction of dissolved iron from water samples. Fe isotope data on a set of standard reference materials (igneous rocks, ferromanganese nodules, sedimentary rocks, and ores) are presented, which are in agreement with previously published data considering analytical uncertainties. Mantle-derived standard rock samples that are the source of iron for surficial, (bio)geochemical cycling yield a mean δ⁵⁶Fe of 0.041 ± 0.11‰ (n = 8; 2 SD) with reference to IRMM-14. Hydrothermal and metamorphic calcium carbonate rocks with a relatively low iron content (100-4000 ppm) have δ⁵⁶Fe = −1.25 to −0.07‰. Structural Fe(II) in hydrothermal calcites has δ⁵⁶Fe = −1.25 to −0.27‰. The light iron in this range of carbonate minerals may reflect the iron isotope composition of the hydrothermal fluids from which the carbonate precipitated, or the presence of Fe(III) and/or organic material in the hydrothermal fluids during calcite precipitation.     

Paleohydrogeological events recorded by stable isotopes,fluid inclusions and trace elements in fracture minerals in crystalline rock,Simpevarp area,SE Sweden

Fracture minerals calcite, pyrite, gypsum, barite and quartz, formed during several events have been analysed for δ¹³C, δ¹⁸O, δ³⁴S, ⁸⁷Sr/⁸⁶Sr, trace element chemistry and fluid inclusions in order to gain knowledge of the paleohydrogeological evolution of the Simpevarp area, south-eastern Sweden. This area is dominated by Proterozoic crystalline rocks and is currently being investigated by the Swedish Nuclear Fuel and Waste Management Co. (SKB) in order to find a suitable location for a deep-seated repository for spent nuclear fuel. Knowledge of the paleohydrogeological evolution is essential to understand the stability or evolution of the groundwater system over a time scale relevant to the performance assessment for a spent nuclear fuel repository. The ages of the minerals analysed range from the Proterozoic to possibly the Quaternary. The Proterozoic calcite and pyrite show inorganic and hydrothermal-magmatic stable isotope signatures and were probably formed during a long time period as indicated by the large span in temperatures (c. 200–360 °C) and salinities (0–24 wt.% eq. CaCl₂), obtained from fluid inclusion analyses. The Paleozoic minerals were formed from organically influenced brine-type fluids at temperatures of 80–145 °C. The isotopic results indicate that low temperature calcite and pyrite may have formed during different events ranging in time possibly from the end of the Paleozoic until the Quaternary. Formation conditions ranging from fresh to brackish and saline waters have been distinguished based on calcite crystal morphologies. The combination of δ¹⁸O and crystal morphologies show that the fresh–saline water interface has changed considerably over time, and water similar to the present meteoric water and brackish seawater at the site, have most probably earlier been residing in the bedrock. Organic influence and closed system in situ microbial activity causing disequilibrium are indicated by extremely low δ¹³C (down to −99.7‰), extreme variation in δ³⁴S (−42.5‰ to +60.8‰) and trace element compositions. The frequency of calcite low in δ¹³C and high in Mn, as well as pyrite with biogenically modified δ³⁴S decreases with depth. Strontium isotopes have been useful to separate the different generations and the Sr isotope ratios in the groundwaters have been determined mainly by in situ water–rock interaction processes. The difficulty of separating late Paleozoic calcite from possibly recent calcite, and the fact that these calcites are usually found in the same fracture systems indicate that water conducting structures have been intermittently conductive from the Paleozoic and onwards. The methodology used has been successful in separating the different generations and characterising their formation conditions.     

Pore water evolution in oilfield sandstones: constraints from oxygen isotope microanalyses of quartz cement

Oxygen isotope microanalyses of authigenic quartz, in combination with temperatures of quartz precipitation constrained by fluid inclusion microthermometry and burial history modelling, are employed to trace the origin and evolution of pore waters in three distinct reservoirs of the Brae Formation in the Miller and Kingfisher Fields (North Sea). Oxygen isotope ratios of quartz cements were measured in situ in nine sandstone thin sections with a Cameca ims-4f ion microprobe. In conjunction with quartz cement paragenesis in the reservoirs, constrained from textural and cathodoluminescence (CL) microscopy studies, pore water evolution was reconstructed from the time of deposition of the sandstones in the Upper Jurassic until the present.CL photomicrographs of quartz overgrowths in the Brae Formation sandstones show three cement zones (A, B and C) which can be related to different oxygen isotope compositions: (1) the earliest, and thinnest, zone A (homogeneous CL pattern with probable δ¹⁸O values between +23‰ and +26‰—direct measurements were not possible) precipitated in the sandstones at temperatures <60 °C; (2) the second zone B (complex CL pattern and directly measured δ¹⁸O values between +15‰ and +18‰) precipitated in the sandstones most likely between 70 and 90 °C; (3) the third zone C (homogeneous CL pattern and directly measured δ¹⁸O values between +16‰ and +22‰) precipitated in the sandstones most likely at temperatures >90 °C. Calculated oxygen isotope compositions of pore waters show that zone A quartz cements, and enclosing concretionary calcite, precipitated from a meteoric-type fluid (∼−7‰) during shallow burial (<1.5 km). Zone B quartz cements precipitated from fluids which evolved in composition from a meteoric-type fluid (δ¹⁸O −7‰) to a more ¹⁸O-enriched fluid (δ¹⁸O −4‰) as burial continued to ∼3.0 km. Data from zone C quartz cements are consistent with further fluid evolution from δ¹⁸O −4‰ to basinal-type fluids with δ¹⁸O similar to the present-day formation water oxygen isotope composition (+0.6‰ at 4.0 km burial). A similar pore water evolution can be derived for all three reservoirs studied, indicating that hydrogeologic evolution was similar across sandstones of the whole Brae Formation.The quartz cement zones observed in the Brae Formation sandstones, and the pore water history derived for the area studied, is analogous to published petrographic and pore water evolution data from the nearby Brent Group reservoirs and from reservoirs located in the Haltenbanken area on the Atlantic margin offshore Norway. Considering quartz cement is a major porosity-occluding phase in many reservoir sandstones, and because pore waters both dissolve quartz and carry the dissolved silica to cementation sites, the data presented are valuable for improving the understanding and prediction of reservoir quality development in sandstones globally.     

Isotopic constraints on ice age fluids in active geothermal systems: Reykjanes, Iceland

The Reykjanes geothermal system is located on the landward extension of the Mid-Atlantic Ridge in southwest Iceland, and provides an on-land proxy to high-temperature hydrothermal systems of oceanic spreading centers. Previous studies of elemental composition and salinity have shown that Reykjanes geothermal fluids are likely hydrothermally modified seawater. However, δD values of these fluids are as low as −23‰, which is indicative of a meteoric water component. Here we constrain the origin of Reykjanes hydrothermal solutions by analysis of hydrogen and oxygen isotope compositions of hydrothermal epidote from geothermal drillholes at depths between 1 and 3 km. δD_EPIDOTE values from wells RN-8, -9, -10 and -17 collectively range from −60 to −78‰, and δ¹⁸O_EPIDOTE in these wells are between −3.0 and 2.3‰. The δD values of epidote generally increase along a NE trend through the geothermal field, whereas δ¹⁸O values generally decrease, suggesting a southwest to northeast migration of the geothermal upflow zone with time that is consistent with present-day temperatures and observed hydrothermal mineral zones. For comparative analysis, the meteoric-water dominated Nesjavellir and Krafla geothermal systems, which have a δD_FLUID of ∼ −79‰ and −89‰, respectively, show δD_EPIDOTE values of −115‰ and −125‰. In contrast, δD_EPIDOTE from the mixed meteoric-seawater Svartsengi geothermal system is −68‰; comparable to δD_EPIDOTE from well RN-10 at Reykjanes.Stable isotope compositions of geothermal fluids in isotopic equilibrium with the epidotes at Reykjanes are computed using published temperature dependent hydrogen and oxygen isotope fractionation curves for epidote-water, measured isotope composition of the epidotes and temperatures approximated from the boiling point curve with depth. Calculated δD and δ¹⁸O of geothermal fluids are less than 0‰, suggesting that fluids of meteoric or glacial origin are a significant component of the geothermal solutions. Additionally, δD_FLUID values in equilibrium with geothermal epidote are lower than those of modern-day fluids, whereas calculated δ¹⁸O_FLUID values are within range of the observed fluid isotope composition. We propose that modern δD_EPIDOTE and δD_FLUID values are the result of diffusional exchange between hydrous alteration minerals that precipitated from glacially-derived fluids early in the evolution of the Reykjanes system and modern seawater-derived geothermal fluids. A simplified model of isotope exchange in the Reykjanes geothermal system, in which the average starting δD_ROCK value is −125‰ and the water to rock mass ratio is 0.25, predicts a δD_FLUID composition within 1‰ of average measured values. This model resolves the discrepancy between fluid salinity and isotope composition of Reykjanes geothermal fluids, explains the observed disequilibrium between modern fluids and hydrothermal epidote, and suggests that rock-fluid interaction is the dominant control over the evolution of fluid isotope composition in the hydrothermal system.     

Carbon, sulfur, and oxygen isotope evidence for a strong depth gradient and oceanic oxidation after the Ediacaran Hankalchough glaciation

In order to understand spatial variations of stable isotope geochemistry in the Quruqtagh basin (northwestern China) in the aftermath of an Ediacaran glaciation, we analyzed carbonate carbon isotopes (δ¹³C_carb), carbonate oxygen isotopes (δ¹⁸O_carb), carbonate associated sulfate sulfur (δ³⁴S_CAS) and oxygen isotopes (δ¹⁸O_CAS), and pyrite sulfur isotopes (δ³⁴S_py) of a cap dolostone atop the Ediacaran Hankalchough glacial diamictite at four sections. The four studied sections (YKG, MK, H and ZBS) represent an onshore-offshore transect in the Quruqtagh basin. Our data show a strong paleobathymetry-dependent isotopic gradient. From the onshore to offshore sections, δ¹³C_carb values decrease from −2‰ to −16‰ (VPDB), whereas δ¹⁸O_carb values increase from −4‰ to −1‰ (VPDB). Both δ³⁴S_CAS and δ³⁴S_py show stratigraphic variations in the two onshore sections (MK and YKG), but are more stable in the two offshore sections (H and ZBS). δ¹⁸O_CAS values of onshore samples are consistent with terrestrial oxidative weathering of pyrite. We propose that following the Hankalchough glaciation seawater in the Quruqtagh basin was characterized by a strong isotopic gradient. The isotopic data may be interpreted using a three-component mixing model that involves three reservoirs: deep-basin water, surface water, and terrestrial weathering input. In this model, the negative δ¹³C_carb values in the offshore sections are related to the upwelling of deep-basin water (where anaerobic oxidation of dissolved organic carbon resulted in ¹³C-depleted DIC), whereas sulfur isotope variations are strongly controlled by surface water sulfate and terrestrial weathering input derived from oxidative weathering of pyrite. The new data provide evidence for the oceanic oxidation following the Hankalchough glaciation.     

Sr, C, and O isotope geochemistry of Ordovician brachiopods: a major isotopic event around the Middle-Late Ordovician transition

Here we present Sr, C, and O isotope curves for Ordovician marine calcite based on analyses of 206 calcitic brachiopods from 10 localities worldwide. These are the first Ordovician-wide isotope curves that can be placed within the newly emerging global biostratigraphic framework. A total of 182 brachiopods were selected for C and O isotope analysis, and 122 were selected for Sr isotope analysis. Seawater ⁸⁷Sr/⁸⁶Sr decreased from 0.7090 to 0.7078 during the Ordovician, with a major, quite rapid fall around the Middle-Late Ordovician transition, most probably caused by a combination of low continental erosion rates and increased submarine hydrothermal exchange rates. Mean δ¹⁸O values increase from −10‰ to −3‰ through the Ordovician with an additional short-lived increase of 2 to 3‰ during the latest Ordovician due to glaciation. Although diagenetic alteration may have lowered δ¹⁸O in some samples, particularly those from the Lower Ordovician, maximum δ¹⁸O values, which are less likely to be altered, increase by more than 3‰ through the Ordovician in both our data and literature data. We consider that this long-term rise in calcite δ¹⁸O records the effect of decreasing tropical seawater temperatures across the Middle-Late Ordovician transition superimposed on seawater δ¹⁸O that was steadily increasing from ≤−3‰ standard mean ocean water (SMOW). By contrast, δ¹³C variation seems to have been relatively modest during most of the Ordovician with the exception of the globally documented, but short-lived, latest Ordovician δ¹³C excursion up to +7‰. Nevertheless, an underlying trend in mean δ¹³C can be discerned, changing from moderately negative values in the Early Ordovician to moderately positive values by the latest Ordovician. These new isotopic data confirm a major reorganization of ocean chemistry and the surface environment around 465 to 455 Ma. The juxtaposition of the greatest recorded swings in Phanerozoic seawater ⁸⁷Sr/⁸⁶Sr and δ¹⁸O at the same time as one of the largest marine transgressions in Phanerozoic Earth history suggests a causal link between tectonic and climatic change, and emphasizes an endogenic control on the O isotope budget during the Early Paleozoic. Better isotopic and biostratigraphic constraints are still required if we are to understand the true significance of these changes. We recommend that future work on Ordovician isotope stratigraphy focus on this outstanding Middle-Late Ordovician event.     

Stable silicon isotopes of groundwater, feldspars, and clay coatings in the Navajo Sandstone aquifer, Black Mesa, Arizona, USA

We present some of the first analyses of the stable isotopic composition of dissolved silicon (Si) in groundwater. The groundwater samples were from the Navajo Sandstone aquifer at Black Mesa, Arizona, USA, and the Si isotope composition of detrital feldspars and secondary clay coatings in the aquifer were also analyzed. Silicon isotope compositions were measured using high-resolution multi-collector inductively coupled mass spectrometry (HR-MC-ICP-MS) (Nu1700 & NuPlasma HR). The quartz dominated bulk rock and feldspar separates have similar δ³⁰Si of −0.09 ± 0.04‰ and −0.15 ± 0.04‰ (±95% SEM), respectively, and clay separates are isotopically lighter by up to 0.4‰ compared to the feldspars. From isotopic mass-balance considerations, co-existing aqueous fluids should have δ³⁰Si values heavier than the primary silicates. Positive δ³⁰Si values were only found in the shallow aquifer, where Si isotopes are most likely fractionated during the dissolution of feldspars and subsequent formation of clay minerals. However, δ³⁰Si decreases along the flow path from 0.56‰ to −1.42‰, representing the most negative dissolved Si isotope composition so far found for natural waters. We speculate that the enrichment in ²⁸Si is due to dissolution of partly secondary clay minerals and low-temperature silcretes in the Navajo Sandstone. The discovery of the large range and systematic shifts of δ³⁰Si values along a groundwater flow path illustrates the potential utility of stable Si isotopes for deciphering the Si cycling in sedimentary basins, tracing fluid flow, and evaluating global Si cycle.     

Multi-proxy approach (H/H, O/O, C/C and Sr/Sr) for the evolution of carbonate-rich groundwater in basalt dominated aquifer of Axum area, northern Ethiopia

Isotopic and chemical composition of groundwater from wells and springs, and surface water from the basalt-dominated Axum area (northern Ethiopia) provides evidence for the origin of water and dissolved species. Shallow (depth < 40 m) and deep groundwater are distinguished by both chemical and isotopic composition. Deep groundwater is significantly enriched in dissolved inorganic carbon up to 40 mmol l⁻¹ and in concentrations of Ca²⁺, Mg²⁺, Na⁺ and Si(OH)₄ compared to the shallow type.The δ²H and δ¹⁸O values of all solutions clearly indicate meteoric origin. Shifts from the local meteoric water line are attributed to evaporation of surface and spring water, and to strong water–rock interaction. The δ¹³C_DIC values of shallow groundwater between −12 and −7‰ (VPDB) display the uptake of CO₂ from local soil horizons, whereas δ¹³C_DIC of deep groundwater ranges from −5 to +1‰. Considering open system conditions with respect to gaseous CO₂, δ¹³C_DIC = +1‰ of the deep groundwater with highest PCO₂ = 10^−0.9 atm yields δ¹³C_CO2(gas) ≈ −5‰, which is close to the stable carbon isotopic composition of magmatic CO₂. Accordingly, stable carbon isotope ratios within the above range are referred to individual proportions of CO₂ from soil and magmatic origin. The uptake of magmatic CO₂ results in elevated cations and Si(OH)₄ concentrations. Weathering of local basalts is documented by ⁸⁷Sr/⁸⁶Sr ratios of the groundwater from 0.7038 to 0.7059. Highest values indicate Sr release from the basement rocks. Besides weathering of silicates, neoformation of solids has to be considered, which results in the formation of, e.g., kaolinite and montmorillonite. In several solutions supersaturation with respect to calcite is reached by outgassing of CO₂ from the solution leading to secondary calcite formation.     

Oxygen and hydrogen isotopes of rainfall and dripwater at DeSoto Caverns (Alabama, USA): Key to understanding past variability of moisture transport from the Gulf of Mexico

The Southeast and the US Gulf Coast in particular are notably lacking isotope data in the water cycle despite the fact that moisture transport from the Gulf of Mexico (GOM) has a considerable influence on both regional and continental rainfall patterns. This study reports time-series of oxygen and hydrogen isotopes acquired over a 3-year period (2005-2008) from GOM-derived rainfall, cave dripwater and shallow groundwaters, and offers valuable insights on the links between factors controlling regional rainfall and the ubiquitous karst hydrology.Amount-weighted mean monthly rainwater δ¹⁸O and δD values in Tuscaloosa, Alabama range from −1.5 to −8.3‰ and −1.2 to −49.5‰, respectively, and show mean seasonal amplitudes of ∼4‰ (δ¹⁸O) and ∼25‰ (δD). In comparison d-excess values display large seasonal amplitudes of 10-20‰ resulting from differences in the degree of evaporation from falling raindrops between summer and winter months, and correlate well with the coeval air temperature (r² = 0.59; p < 0.05). Deviations of the Gulf Coast Meteoric Water Line (GCMWL) slope and d-excess from the global meteoric water line (GMWL) are attributed to different rates of evaporation after condensation, and to humidity contrast between the cloud boundary layer and the surrounding atmosphere in the vapor source region, respectively. Rainfall amounts declined during the study interval from an excessive “wet” year, ascribed to six tropical storms incursions during an unusually active hurricane season in 2005, to an onset of a regional drought during 2007-2008 with monthly rainfall amounts substantially below normal values (30-year monthly means). An interannual trend of ¹⁸O and ²H enrichments is discerned from 2005 to 2008 (1.4‰ and 11.6‰, respectively) coeval with the decline in rainfall amounts.Dripwater samples from nearby DeSoto Caverns show weak δ¹⁸O and δD seasonal variations and record only 20% and 51% of the ¹⁸O and ²H enrichments, respectively, discerned in the rainwater 3-year time-trends. The seasonal and interannual amplitude attenuations in the dripwaters are attributed to a relatively thick overlying bedrock (∼30-40 m) and a relatively large, well-mixed, epikarst-storage reservoir. Residence time of water in the cave’s epikarst is estimated to be 1-3 months based on high-resolution flow-rate data.Our investigation suggests that global atmospheric circulation patterns (ENSO and Bermuda High) likely govern the interannual δ¹⁸O and δD isotope trends discerned in the water cycle compartments but much longer time-series are required to confirm our conjectures. The results of this study form a solid basis for future acquisition and interpretation of climate proxy records from regional speleothems.     

Oxygen isotope measurements of individual unmelted Antarctic micrometeorites

We present oxygen isotope measurements of 28 unmelted Antarctic micrometeorites measuring 150-250 μm (long axis) collected in the South Pole water well. The micrometeorites were all unmelted and classified as either fine-grained, scoriaceous, coarse-grained or composite (a mix of two other classes). Spot analyses were made of each micrometeorite type using an ion microprobe. The oxygen isotope values were measured relative to standard mean ocean water (SMOW) and range from δ¹⁸O = 3‰ to 60‰ and δ¹⁷O = −1‰ to 32‰, falling along the terrestrial fractionation line (TFL) within 2σ errors. Several analytical spots (comprising multiple phases) were made on each particle. Variability in the oxygen isotope ratios was observed among micrometeorite types, between micrometeorites of the same type and between analytical spots on a single micrometeorite indicating that micrometeorites are isotopically heterogeneous. In general, the lowest isotope values are associated with the coarse-grained micrometeorites whereas most of the fine-grained and scoriaceous micrometeorites have an average δ¹⁸O ? 22‰, suggesting that the matrix in micrometeorites is isotopically heavier than the anhydrous silicate phases. The oxygen isotope values for the coarse-grained micrometeorites, composed mainly of anhydrous phases, do not lie along the carbonaceous chondrite anhydrous mineral (CCAM) line, as observed for olivines, pyroxenes and some kinds of chondrules in carbonaceous chondrites, suggesting that coarse-grained MMs are not related to chondrules, as previously thought. Our measurements span the same range as values found for melted micrometeorites in other studies. Although four of the micrometeorites have oxygen isotope values lying along the TFL, close to the region where the bulk CI carbonaceous chondrites are found, 21 particles have very enriched ¹⁷O and ¹⁸O values that have not been reported in previous analyses of chondrite matrix material, suggesting that they could be a new type of Solar System object. The parent bodies of the micrometeorites with higher ¹⁸O values may be thermal metamorphosed carbonaceous asteroids that have not been found as meteorites either because they are friable asteroids that produce small particles rather than rocks upon collision with other bodies, or because the rocks they produce are too friable to survive atmospheric entry.     

Carbonate xenoliths in La Palma: Carbonatite or alteration product?

Carbonate xenoliths containing olivine and rimmed by kaersutitic amphibole were collected in basaltic rocks of the Basal Complex of La Palma. The mineralogical composition and microscopic appearance may suggest a relationship with carbonatites in general, thus a major element, trace element and stable isotope study was conducted to investigate the origin of the carbonate formation. Based on electron microprobe analyses, the carbonate is calcite with up to 6.3 wt% MgO and 7.2 wt% SiO₂. The elevated SiO₂ content may suggest a melt origin for the carbonate. However, the C and O isotope compositions of the carbonate xenoliths (δ¹³C and δ¹⁸O around −1‰ and 13‰, respectively) are similar to those of calcite veins and amygdales in basaltic rocks of the Basal Complexes of La Palma and Fuerteventura and are interpreted as produced by fluid degassing and metasomatism by CO₂-H₂O fluid derived from mobilization of sedimentary material. Trace element contents determined by laser-ablation ICP-MS analyses support the assumed origin, thus, the relationship with carbonatitic melts can be excluded. Based on trace element compositions, the amphibole surrounding the xenoliths is not related genetically to the carbonate. The elevated SiO₂ content of the calcite can be attributed to submicron relics of pyroxene, thus, the use of this feature as an evidence for melt origin is questionable.