Spatial and temporal distribution of groundwater recharge in northern Nigeria

Moisture samples obtained from unsaturated-zone profiles in sands from northern Nigeria were used to obtain recharge estimates using the chloride (Cl) mass-balance method and to produce records of past recharge and climatic events. Recharge rates range from 14–49 mm/year, on the basis of unsaturated-zone Cl values and rainfall chemistry measured over eight years at three local stations. The unsaturated-zone results also provide a record of the changing recharge and climatic events of the past 80 years; this record compares quite well with modelling results using precipitation data from Maiduguri, especially for the late 20th-century period of drought. The best fit for the model is made, however, by using a lower mean rainfall Cl (0.65 mg/l) than that obtained from the mean of the field results (1.77 mg/l Cl). This result implies that the measured rainfall Cl probably overestimates the depositional flux of Cl, although the lower value is comparable to the minimum of the measured rainfall Cl values (0.6 mg/l Cl). Recharge estimates made using these lower Cl values range from 16–30 mm/year. The spatial variability was then determined using results from 360 regional shallow wells over 18,000 km². Using the revised rainfall estimate, the Cl balance indicates a value of 43 mm for the regional recharge, suggesting that either additional preferential flow is taking place over and above that from the vadose one, or that the regional recharge represents inputs from earlier wetter periods. These recharge estimates compare favourably with those from hydraulic modelling in the same area and suggest that the recharge rates are much higher than values previously published for this area. High nitrate (NO₃) concentrations (NO₃-N>Cl) preserved under aerobic conditions in the vadose zone reflect secondary enrichment from N-fixing vegetation, as occurs elsewhere in the Sahel. Electronic Publication     

Oxygen isotopic composition of coexisting minerals of sillimanite-hypersthene rocks from the Por’ya bay area: Evidence of fluid involvement in granulite-facies metamorphism

Hypersthene-garnet-sillimanite-quartz enclaves were studied in orthopyroxene-plagioclase and orthopyroxene-clinopyroxene crystalline schists and gneisses from shear zones exposed in Palenyi Island in the Early Proterozoic Belomorian Mobile Belt. Qualitative analysis of mineral assemblages indicates that these rocks were metamorphosed to the granulite facies (approximately 900°C and 10–11 kbar). Oxygen isotopic composition was determined in rock-forming minerals composing zones of the enclaves of various mineralogical and chemical composition. The closure temperatures of the isotopic systems obtained by methods of oxygen isotopic thermometry are close to the values obtained with mineralogical geothermometers (Grt-Opx and Grt-Bt) and correspond to the high-temperature granulite facies (860–900°C). Identified systematic variations in the δ¹⁸O values were determined in the same minerals from zones of different mineral composition. Inasmuch as these zones are practically in contact with one another, these variations in δ¹⁸O cannot be explained by the primary isotopic heterogeneity of the protolith. The model calculations of the extent and trend of the δ¹⁸O variations in minerals suggest that the only mechanism able to generate the zoning was fluid-rock interaction at various integral fluid/rock ratios in discrete zones. This demonstrates that a focused fluid flux could occur in lower crustal shear zones. The preservation of high-temperature isotopic equilibria of minerals testifies that the episode of fluid activity at the peak of metamorphism was very brief.     

Investigation of groundwater mineralization in the Hammamet–Nabeul unconfined aquifer,north-eastern Tunisia: geochemical and isotopic approach

Detailed hydrogeochemical and isotopic data of groundwaters from the Hammamet–Nabeul unconfined aquifer are used to provide a better understanding of the natural and anthropogenic processes that control the groundwater mineralization as well as the sources of different groundwater bodies. It has been demonstrated that groundwaters, which show Na–Cl and Ca–SO₄–Cl water facies, are mainly influenced by the dissolution of evaporates, the dedolomitization and the cation-exchange process; and supplementary by anthropogenic process in relation with return flow of irrigation waters. The isotopic signatures permit to classify the studied groundwaters into two different groups. Non-evaporated groundwaters that are characterized by depleted δ ¹⁸O and δ ²H contents highlighting the importance of modern recharge at higher altitude. Evaporated groundwaters with enriched contents reflecting the significance infiltration of return flow irrigation waters. Tritium data in the studied groundwaters lend support to the existence of pre-1950 and post-1960 recharge. Carbon-14 activities in shallow wells that provide evidence to the large contamination by organic ¹⁴C corroborate the recent origin of the groundwaters in the study area.     

Isotopic composition of dissolved boron and its geochemical behavior in a freshwater-seawater mixture at the estuary of the Changjiang （Yangtze） River

The isotopic composition of dissolved boron, in combination with the elemental concentrations of B, Cl and salinities in freshwater-seawater mixed samples taken from the estuary of the Changjiang River, the largest one in China, was investigated in detail in this study. Brackish water and seawater samples from the estuary of the Changjiang River were collected during low water season in November, 1998. Boron isotopic compositions were determined by the Cs2BO^＋2-graphite technique with a analytical uncertainty of 0.2‰ for NIST SRM 951 and an average analytical uncertainty of 0.8‰ for the samples. The isotopic compositions of boron, expressed in δ^11B, and boron concentrations in the Changjiang River at Nanjing and seawater from the open marine East Sea, China, are characterized by δ^11B values of -5.4‰ and 40.0‰, as well as 0.0272 and 4.43 mg B/L, respectively. Well-defined correlations between δ^11B values, B concentrations and Cl concentrations are interpreted in terms of binary mixing between fiver input water and East Sea seawater by a process of straightforward dilution. The offsets of δ^11B values are not related to the contents of clastic sediment and to the addition of boron. These relationships favor a conservative behavior of boron at the estuarine of the Changjiang River.     

Salinization properties of a shallow groundwater in a coastal reclaimed area,Yeonggwang, Korea

The need for more agricultural or residential land has encouraged reclamation at the coastal areas of Korea since 1200 ad (approximately). The groundwaters of these reclaimed areas could be expected to reveal hydrogeochemical properties different from those of areas directly affected by seawater intrusion. The purpose of this study, therefore, was to examine the salinization of shallow groundwater in a coastal reclaimed area and to identify the effect of land reclamation on groundwater quality. Major cations and anions, iodide, total organic carbon, δD, δ ¹⁸O and δ ¹³C were measured to assist the hydrogeochemical analysis. Chloride, δD and δ ¹⁸O data clearly show that the Na–Cl type water results from mixing of groundwater with seawater. In particular, the δD and δ ¹⁸O of Ca+Mg–Cl+NO₃ type groundwaters are close to the meteoric water line, but Na–Cl type waters enriched in chloride are ¹⁸O-enriched with respect to the meteoric water line. Meanwhile, carbon isotopic data and I/Cl ratios strongly suggest that there are various sources of salinity. The δ ¹³C values of Na–Cl type groundwaters are generally similar to those of Ca+Mg–Cl+NO₃ type waters, which are depleted in ¹³C with respect to seawater. I/Cl ratios of Na–Cl type groundwater are 10–100 times higher than that of seawater. Because the reclamation has incorporated a large amount of organic matter, it provides optimum conditions for the occurrence of redox processes in the groundwater system. Therefore, the salinization of groundwater in the study area seems to be controlled not only by saltwater intrusion but also by other effects, such as those caused by residual salts and organic matter in the reclaimed sediments.     

Phase equilibrium and stable isotope constraints on the formation of metasomatic garnet-vesuvianite veins (SW Adamello,N Italy)

 Metasomatic garnet-vesuvianite veins occur within the contact metamorphic marble sequence of the Lower Triassic Prezzo formation in a narrow, 1–5 m wide zone along an intrusive marble-granodiorite contact at the southwestern border of the Tertiary Adamello batholith. The metasomatic mineral assemblage is comprised of garnet, vesuvianite, clinopyroxene, wollastonite, and pyrrhotite, which were precipitated from the vein-forming fluid in a preexisting calcite matrix at conditions of about 2800 bars and 630° C. The veins are enriched in silicon, aluminum, iron, magnesium, titanium and depleted in calcium with respect to the unaltered contact metamorphic marble. Graphite, which is present in the unaltered Prezzo Marble is absent in the veins. Irregularly shaped mineralogically distinct zones with different degrees of silicification can be distinguished within the veins. The isotopic compositions of calcite (cc) in the unaltered marble are about δ¹⁸O (SMOW; Standard mean Ocean Water)=21.0‰ and δ¹³C(PDB; Peedee belemnite)=0.0‰. They are reset to significantly lower values within the veins, where δ¹⁸O_cc is 15.0 to 16.0‰ and δ¹³C_cc is −4.5 to −3.5‰. The isotopic front coincides with an abrupt change in the microscopic texture of matrix carbonate which occurs at the sharp boundary between graphite-bearing and graphite-free material. Within the veins the oxygen isotope fractionation between calcite and garnet (gar) varies systematically with distance from highly silicified zones. The variations in Δ¹⁸O_cc-gar are as large as 2‰, on a millimeter scale, indicating garnet-calcite isotopic disequilibrium. Vein formation was due to the infiltration of a water rich fluid of magmatic provenance into the carbonate country rock along fractures. Removal of graphite from the wall rock by dissolution through the metasomatic fluid induced recrystallization of matrix calcite. Permeability was enhanced during calcite recrystallization facilitating material transport into the wall rock and metasomatic alteration. Vein garnet was precipitated in isotopic equilibrium with the metasomatic fluid. The isotopic composition of preexisting calcite was initially out of equilibrium with the vein-forming fluid and it was shifted towards equilibrium by surface-reaction controlled calcite-fluid isotopic exchange during calcite recrystallization. Due to the short lifetime of the metasomatic system, calcite-fluid isotopic equilibrium was generally not attained. Within the veins, oxygen and carbon transport was fast relative to mineral-fluid exchange of their isotopes and the geometry of the isotopic pattern is largely controlled by the kinetics of mineral-fluid exchange. Received: 16 June 1994/Accepted: 20 May 1995     

Petrology, isotope geochemistry and chemical budgets of oceanic gabbros-seawater interactions in the Equatorial Atlantic

 Petrological and chemical variations, as well as oxygen and strontium isotopic data are presented for metagabbros from the Romanche and Vema fracture zones. These rocks were affected by several types and degrees of alterations ranging from slight hydrothermal alteration to complete amphibolitization. Five major kinds of alteration processes ranging from late-magmatic deuteric alteration (stage I) to low temperature (<150 °C) alteration (stage V) were identified. Water-rock interactions between 300 and 650 °C are the most dominant interactions resulting in the most prevailing secondary mineralogical assemblages which characterize the amphibolite and/or greenschist facies (amphibole ± plagioclase ± epidote ± titanite ± chlorite ± prehnite). Hydrothermal alteration of these gabbroic rocks results in isotopic exchanges between rocks and seawater-derived fluids. These exchanges lead to decrease of gabbroic δ¹⁸O toward values as low as +3.9‰, and larger Sr isotopic variations than other oceanic gabbroic rocks (⁸⁷Sr/⁸⁶Sr ratios shift to 0.7029–0.7051). Calculation of a chemical budget indicates that metagabbros are hydrated and enriched in Fe and probably in Mg and Cl, while Si, Ca and Ti are released to the hydrothermal fluids. In addition to metamorphic recrystallization and geochemical transformation, hydrothermal alteration of oceanic gabbros contributes to the control of the global ocean geochemistry. Received: 8 March 1999 / Accepted: 12 July 1999     

Fluid migration through thrust faults in the Helvetic nappes (Western Swiss Alps)

The δ¹⁸O, δ¹³C and ⁸⁷Sr/⁸⁶Sr values of calcite and organic matter were measured for carbonate mylonites from numerous thrusts in the Helvetic Alps. Carbonate mylonites in most of the thrusts retain essentially unaltered protolith δ¹⁸O and δ¹³C values, consistent with there having been little to no advection of isotopically distinct fluid through these faults. Only carbonate mylonites from the basal thrusts of the largest nappes have δ¹⁸O and/or δ¹³C values that differ from those of their protoliths. The zone of isotopic alteration/exchange is confined to c. 10 to 20 meters of these fault contacts. We propose the fluids that migrated through these faults contained variable amounts of organically derived carbon and radiogenic strontium, and were probably derived from dewatering of the sedimentary rocks and prograde metamorphic reactions in the nappes' root zones. Apart from the basal thrusts of the largest nappes that behaved as narrow, laterally extensive conduits for fluids, there is little isotopic evidence that large quantities of fluids passed through most of the carbonate-hosted thrusts in the Helvetic Alps. Received: 25 August 1998 / Accepted: 26 February 1999     

Quantifying regional groundwater flow between Continental Intercalaire and Djeffara aquifers in southern Tunisia using isotope methods

Large-scale interaction between the Continental Intercalaire and the Djeffara aquifer systems in the southeast of Tunisia has been investigated with the aid of chemical and isotopic tracers. Two distinct groundwater types have been identified: (1) the Continental Intercalaire groundwater characterized by elevated temperatures (50–61.4°C), low δ¹⁸O (−8.4 to−7.87) and δ²H (−67.2 to−59) values and negligible radiocarbon content, both testifying its great age dating from the late Pleistocene period, and (2) the Djeffara groundwater with distinctly heavier isotopic composition (δ¹⁸O = −8.31 to −5.80, δ²H = −65.9 to −31.9). The Djeffara groundwaters reveal a distinct changes of physico-chemical and isotopic parameters near El Hamma Faults in the northwestern part of the Djeffara basin. These changes could possibly be explained by a vertical leakage from the Continental Intercalaire aquifer through El Hamma Faults. The mixing proportions inferred from stable isotope mass balance prove that the contribution of the Continental Intercalaire to the recharge of Djeffara aquifer is very significant and may reach 100% in the El Hamma region and in the northern part of Gabes. Isotope tracers strongly suggest that recent recharge to the Djeffara aquifer system is very limited. Its current yield, particularly in its central and northern parts can be maintained only thanks to large-scale underground inflow from the Continental Intercalaire aquifer system, which carries late Pleistocene palaeowater. Consequently, current exploitation of groundwater resources of the Djeffara aquifer has non-sustainable character.     

Prograde and retrograde fluid-rock interaction in calc-silicates northwest of the Idaho batholith: stable isotopic evidence

Carbon and oxygen isotopic analyses of silicate and carbonate minerals indicate that isotopic compositions in metasediments of the Wallace Formation (Belt Supergroup) exposed northwest of the Idaho batholith have been affected by both prograde and retrograde fluid-rock interaction. Silicates retain isotopic fractionations that reflect equilibration at peak metamorphic temperatures. In contrast, calcite oxygen isotopic compositions range from δ¹⁸O(Calcite)=+2.3 to +18.6‰ SMOW (standard mean oceanic water) and indicate that some calcites have exchanged with low-δ¹⁸O meteorichydrothermal fluids. Values of Δ¹⁸O (Quartz-Calcite) as large as +15.5 clearly indicate that the isotopic depletion of these calcites postdates the peak of regional metamorphism. Carbon isotopic compositions of ¹⁸O-depleted calcites are not significantly shifted relative to δ¹³C values in undepleted calcites, suggesting that the retrograde fluid was carbon-poor. Petrographically, retrograde fluid-rock interaction is associated with the occurrence of fine-grained, highly-luminescent calcite overgrowths on less-luminescent, metamorphic calcites, slight to moderate argillic alteration, and pseudomorphing of scapolite porphyroblasts by fine-grained albite. Retrograde isotopic depletions may be related to shallow meteoric-hydrothermal fluid flow developed around the Idaho batholith after intrusion and rapid uplift of the terrane. Peak metamorphic isotopic compositions in the Wallace Formation reflect mineralogically heterogeneous protolith compositions and isotopic fractionation due to devolatilization and/or infiltration. Variability in oxygen isotopic compositions on the order of 4–6‰ within the same rock type can be attributed to the combined effects of inherited isotopic compositions and isotopic shifts resulting from prograde devolatilization. Isotopic and compositional heterogeneity on the scale of mm to m precludes generalization of isotopic gradients on a regional scale. The isotopic data presented here, and metamorphic fluid compositions determined in previous studies, are best reconciled with heterogeneous bulk compositions, dominantly channelized prograde and retrograde fluid flow, and locally low fluid-rock ratios.     

Nature of ore-forming fluids of the Dal’negorsk deposit: Isotopic and geochemical parameters of the altered host rocks

Oxygen isotopic composition was studied in the altered host rocks of the Dal’negorsk borosilicate deposit in order to establish a boron source and the origin of ore-forming fluids responsible for deposition of economic borosilicate ore. The relationships between oxygen isotopic composition and geochemistry of the altered igneous rocks occupying various structural and temporal positions in the ore zone were studied, including premineral high-potassium minor intrusions located in the zones of datolite mineralization; alkali basalt, gabbro, and breccia from the sedimentary framework of the deposit; and postmineral basaltic andesite, basalt, and dolerite dikes. It was suggested that interaction of aqueous fluid with host rocks brought about not only variation in oxygen isotopic composition but also shifts in geochemistry of these rocks, especially as concerns the chemical elements contained in ore-forming fluid. The disturbance of oxygen isotopic system is typical of all studied rocks: δ¹⁸O values sharply decrease indicating interaction with aqueous fluid at elevated temperatures. The lowest δ¹⁸O (from −2.9 to +0.1‰) is characteristic of the premineral high-potassium and ultrapotassium minor intrusions from skarn-datolite zone. Igneous rocks from the sedimentary framework of the deposit have δ¹⁸O of +2 to −0.9‰ The δ¹⁸O of postmineral basaltic andesite, basalt, and dolerite dikes varies from 0 to +7‰ with increasing distance from the ore zone. The oxygen isotopic composition of aqueous fluid evidences its exogenic origin. The geochemical and isotopic characteristics of ore-forming fluid show that it could have been deep-seated subsurface water similar to the contemporary water of the Alpine fold zone, which contain up to 700–1000 mg/l B and is distinguished by high K, Li, Rb, Cs contents and high K/Na ratio. Similar geochemistry is characteristic of the fluid inclusions in quartz from ore zones. It cannot be ruled out that continental evaporites were a source of boron as well. The relationships between δ¹⁸O, K-Ar age, and geochemical parameters of premineral and postmineral altered intrusive bodies allow us to suggest that the subsurface B-bearing water discharged through narrow channels controlled by premineral basaltic bodies. The discharge was probably initiated by emplacement of basalt and dolerite dikes.     

Oxygen isotope mapping of the Archean Sturgeon Lake caldera complex and VMS-related hydrothermal system, Northwestern Ontario, Canada

The hydrothermal and magmatic evolution of the Sturgeon Lake caldera complex is graphically documented by a regional-scale (525 km²) analysis of oxygen isotopes. Spatial variations in whole-rock oxygen isotope compositions provide a thermal map of the cumulative effects of multiple stages of hydrothermal metasomatism before, during, and after volcanogenic massive sulfide (VMS) mineralization. There is a progressive, upward increase in δ¹⁸O from less than 2‰ to greater than 15‰ through a 5-km-thick section above the Biedelman Bay subvolcanic intrusive complex. This isotopic trend makes it clear that at least the earlier phases of this intrusive complex were coeval with the overlying VMS-hosting cauldron succession and provided thermal energy to drive a convective hydrothermal circulation system. The sharp contrast in δ¹⁸O values between late stage phases of the Biedelman Bay intrusion and immediate hanging wall strata indicates that the main phase of VMS-related hydrothermal activity took place before late-stage resurgence in the cauldron-related magmatic activity. Mineralogical and isotopic evidence indicates the presence of both syn- and postmineralization hydrothermal activity defined by the presence of widespread semiconformable and more restricted discordant alteration zones that affect the pre- and syncauldron strata. The semiconformable alteration zones formed during early stages of hydrothermal circulation and are defined by widespread silicification and carbonatization in association with relatively high δ¹⁸O values. The discordant alteration assemblages, containing Al-silicate minerals with chloritoid and/or Fe-rich carbonate or chlorite, centered on synvolcanic faults represent restricted zones of both seawater inflow and hydrothermal fluid upflow. A rapid increase in δ¹⁸O values (∼7–9‰) over a short distance (<200 m) suggests marked cooling of hydrothermal fluid from ∼350°C to less than 130°C either just before or during discharge onto the seafloor. Late emplacement of diorite sills and a dacite dome disrupted the isotopic imprint of cauldron-stage hydrothermal activity. The abrupt lowering of δ¹⁸O values at the transition from explosive to passive volcanism (andesite flows and dacite domes) indicates postcauldron emergence. Subsequently, thrust faulting disrupted the older synvolcanic hydrothermal isotopic patterns.     

An Experimental Apparatus for Laboratory and Field-Based Perfusion of Sediment Porewater with Dissolved Tracers

The water–sediment interface is a dynamic zone where the benthic and pelagic environments are linked through exchange and recycling of organic matter and nutrients. However, it is often difficult to measure rate processes in this zone. To that end, we designed an experimental apparatus for continuous and homogeneous perfusion of sediment porewater with dissolved conservative (SF₆, Rhodamine WT dye) and isotopic (H¹³CO₃⁻ and ¹⁵NH₄⁺) tracers to study nitrogen and carbon cycling by the sediment microbial community of shallow illuminated sediments. The perfusionator consists of a 60-cm ID × 60-cm high cylinder that includes a reservoir for porewater at the base of the sediment column. Porewater amended with conservative and stable isotopic tracers was pumped through a mixing reservoir and upward through the overlying sediments. We tested the perfusionator in a laboratory setting, as part of an outdoor mesocosm array, and buried in coastal sediments. Conservative and isotopic tracers demonstrated that the porewater tracers were distributed homogeneously through the sediment column in all settings. The perfusionator was designed to introduce dissolved stable isotope tracers but is capable of delivering any dissolved ionic, organic, or gaseous constituent. We see a potentially wide application of this technique in the aquatic and marine sciences in laboratory and field settings.     

Stable carbon isotopic composition of soil organic matter in the karst areas of Southwest China

This study dealt with the distribution characteristics of soil organic carbon （SOC） and the variation of stable carbon isotopic composition （δ^13C values） with depth in six soil profiles, including two soil types and three vegetation forms in the karst areas of Southwest China. The δ^13C values of plant-dominant species, leaf litter and soils were measured using the sealed-tube high-temperature combustion method. Soil organic carbon contents of the limestone soil profiles are all above 11.4 g/kg, with the highest value of 71.1 g/kg in the surface soil. However, the contents vary between 2.9 g/kg and 46.0 g/kg in three yellow soil profiles. The difference between the maximum and minimum δ^13C values of soil organic matter （SOM） changes from 2.2‰ to 2.9‰ for the three yellow soil profiles. But it changes from 0.8‰ to 1.6‰ for the limestone soil profiles. The contrast research indicated that there existed significant difference in vertical pattems of organic carbon and δ^13C values of SOM between yellow soil and limestone soil. This difference may reflect site-specific factors, such as soil type, vegetation form, soil pH value, and clay content, etc., which control the contents of different organic components comprising SOM and soil carbon turnover rates in the profiles. The vertical variation patterns of stable carbon isotope in SOM have a distinct regional character in the karst areas.     

H and O isotopic compositions of layered silicates in metasomatites from the Gai Zn-Cu massive sulfide deposit, southern urals

Substantial differences in isotopic compositions of micas and pyrophyllites from metasomatites related to various stages of the process that formed the giant Gai massive sulfide deposit have been established. The illite from the earliest and predominant chlorite-illite-quartz metasomatite is characterized by the least δD values of −(50–85)‰ and δ¹⁸O=7–11‰. The pyrophyllite-quartz metasomatite as well as illite and pyrophyllite schists developed locally in the southern part of the deposit that likely correspond to the site of discharge of late geothermal paleosystem, contain pyrophyllite and illite with much higher values of δD=−(25–45)‰ and δ¹⁸O=4–9‰. Local zones of illite-paragonite schist complete the mineral formation and are characterized by the transitional δD values of −(30–55)‰ and elevated δ¹⁸O of 10–11‰. The most plausible model of isotopic evolution in the hydrothermal system, with an initial temperature of mica formation at 250°C, assumes the mixing of transformed sea water with a magmatic (metamorphic) water at the initial stage when the background metasomatites and massive sulfide orebodies of the northern lode have been formed. Subsequently, after the burial of the northern lode beneath basaltic andesite flows, the repeated sea water invasions took place in the southern discharge site of the system. As a result, the pyrophyllite-quartz metasomatite was formed; the pyrophyllite and illite schists originated in tectonic compression zones. The interaction of this water with silicate rocks was completed by a formation of illite-paragonite schist. In general, the substantial contribution of sea water to the formation of metasomatic halo of the deposit casts no doubt.     

Groundwater recharge and flow in the Lower Cretaceous Nubian Sandstone aquifer in the Sinai Peninsula, using isotopic techniques and hydrochemistry

The present work was conducted in the Sinai Peninsula (1) to identify the recharge and flow characteristics and to evaluate the continuity of the Lower Cretaceous Nubian Sandstone aquifer; and (2) to provide information for the aquifer's rational appraisal. Isotopic and hydrochemical compositions combined with the geological and hydrogeological settings were used for this purpose. A considerable depletion in isotopic content (oxygen-18 and deuterium) and low d-excess values exist in the studied groundwater, reflecting the contribution of old meteoric water that recharged the aquifer in pluvial times. Modern recharge also occurs from precipitation that falls on the aquifer outcrops. The wide scatter of the data points around the two meteoric lines, the global meteoric water line (GMWL) and Mediterranean meteoric water line (MMWL), in the δ¹⁸O–δD diagram indicates considerable variation in recharge conditions (amount, altitude, temperature, air masses, distances from catchment, overland flow, etc.). The isotopic composition in the El-Bruk area is minimum (¹⁸O=–9.53‰), very close to the average value of the Western Desert Nubian Sandstone (¹⁸O=–10‰), where the local structural and lithologic conditions retard groundwater flow and the main bulk of water becomes noncyclic. The continuity of the aquifer in northern and central Sinai is evidenced by the isotopic similarity between samples taken from above and below the central Sinai Ragabet El-Naam fault, the distribution of potentiometric head, and hydrogeological cross sections. The combination of isotopic composition in terms of ¹⁸O and chemical composition in terms of TDS and salt contents is the basis for separating the studied groundwater into groups that reflect the recharge sources and isotopic and chemical modifications during flow. Electronic Publication     

Salt Waters of the Northern Apennine Foredeep Basin (Italy): Origin and Evolution

The salt waters from the Emilia-Romagna sector of the Northern Apennine Foredeep have been investigated using major and trace element and stable isotope (δ²H, δ¹⁸O, δ³⁷Cl, δ⁸¹Br and ⁸⁷Sr/⁸⁶Sr ratio). Ca, Mg, Na, K, Sr, Li, B, I, Br and SO₄ vs. Cl diagrams suggest the subaerial evaporation of seawater beyond gypsum and before halite precipitation as primary process to explain the brine’s salinity, whereas saline to brackish waters were formed by mixing of evaporated seawater and water of meteoric origin. A diagenetic end-member may be a third component for mud volcanoes and some brackish waters. Salinization by dissolution of (Triassic) evaporites has been detected only in samples from the Tuscan side of the Apennines and/or interacting with the Tuscan Nappe. In comparison with the seawater evaporation path, Ca–Sr enrichment and Na–K–Mg depletion of the foredeep waters reveal the presence of secondary processes such as dolomitization–chloritization, zeolitization–albitization and illitization. Sulfate concentration, formerly buffered by gypsum-anhydrite deposition, is heavily lowered by bacterial and locally by thermochemical reduction during burial diagenesis. From an isotopic point of view, data of the water molecule confirm mixing between seawater and meteoric end-members. Local ¹⁸O-shift up to +11‰ at Salsomaggiore is related to water–rock interaction at high temperature (≈150°C) as confirmed by chemical (Mg, Li, Ca distribution) and isotopic (SO₄–H₂O) geothermometers. ³⁷Cl/³⁵Cl and ⁸¹Br/⁷⁹Br ratios corroborate the marine origin of the brines and evidence the diffusion of halogens from the deepest and most saline aquifers toward the surface. The ⁸⁷Sr/⁸⁶Sr ratio suggests a Miocene origin of Sr and rule out the hypothesis of a Triassic provenance of the dissolved components for the analyzed waters issuing from the Emilia-Romagna sector of the foredeep. Waters issuing from the Tuscan side of the Apennines and from the Marche sector of the foredeep show higher ⁸⁷Sr/⁸⁶Sr ratios because of the interaction with siliciclastic rocks.     

Oxygen isotope mapping in the Panorama VMS district, Pilbara Craton, Western Australia: applications to estimating temperatures of alteration and to exploration

Whole rock oxygen isotope data are presented for the Panorama district, in the Archean Pilbara Craton of Western Australia, where near-perfect exposure reveals a cross section through a complete volcanogenic massive sulfide (VMS) hydrothermal alteration system. The δ¹⁸O values decrease with depth in the volcanic pile, across semi-conformable alteration zones, to values below 6‰ immediately above a large (180 km²) subvolcanic intrusion. Altered rocks in the upper parts of the subvolcanic intrusion have lower δ¹⁸O values (6–8‰) than least altered granite (8‰), apart from sericite–quartz altered zones, which are slightly higher (8–10‰). Corridors of low δ¹⁸O values crosscut this regional zonation, and are coincident with transgressive feldspar-destructive alteration zones, which underlie VMS mineralization. The whole rock oxygen isotope distribution patterns are interpreted to represent alteration temperature, where high δ¹⁸O values correspond to low temperature alteration and low δ¹⁸O values correspond to high temperature alteration. Alteration temperatures, which were calculated using modal alteration mineral abundances and an assumed fluid δ¹⁸O, are consistent with this interpretation. Increasing temperatures with depth in the volcanic pile and high temperatures in transgressive corridors leading up to VMS deposits, are consistent with a convective hydrothermal model, in which heat from the subvolcanic intrusion drove seawater through the volcanic pile. Granite-hosted sericite–quartz alteration zones are ¹⁸O-enriched, and are tentatively interpreted to have formed from a mixed magmatic-evolved seawater fluid. Received: 12 April 1999 / Accepted: 6 April 2000     

Hydrochemistry,origin and evolution of sedimentary subsurface fluids: III. Early diagenetic mineralization reactions in high sedimentation—rate basins

The early diagenetic evolution of pore-water chemistry is closely linked to mineralization reactions which consume significant portions of the metabolites released by bacterial organic matter decomposition. These reactions are most intense in high-sedimentation rate basins and include the precipitation of iron-sulfides and various carbonates leading to concretion growth. Early diagenetic pyrite is typically framboidal attesting to its recrystallization from precursor mackinawite, greigite or amorphous FeS which are the favored phases at high supersaturation levels during the initial sulfate reduction stages. The sulfur isotopic composition of early diagnetic pyrite can be used to differentiate diffusion-controlled, open-system conditions with isotopically light sulfide (δ ³⁴S = − 35 to − 20‰) from closed system conditions, under which Raleigh distillation produces increasingly heaver sulfide (δ ³⁴ S = − 35 to + 18‰). Alabandite (Mn-sulfide) is a rare authigenic sulfide in Mn-rich environments such as certain restricted, semi-stagnant basins (Baltic Sea). pH-buffering by hydrogen sulfide and hydrogen ion uptake by the reduction of manganese and iron oxides and hydroxides in the nitrate and sulfate reduction zones raise the pH sufficiently to cause supersaturation of the porewaters with respect to Ca-, Mg-, Fe- and Mn-carbonates and complex solid solutions of them. Fe-carbonates cannot form in the sulfate reduction zone in the presence of dissolved sulfide which competes for the dissolved iron. Likewise, dolomite formation appears to be inhibited or slowed down in the presence of substantial dissolved sulfate. The appearance of siderite and ankerite therefore signals carbonate precipitation below the sulfate reduction zone. Supporting evidence for the early diagenetic origin of many carbonate concertions is provided by their high carbonate contents (70 to 90% reflecting the porosity existing at the time of precipitation, called “minus-cement porosity”), isotopic composition, clay fabrics, and preservation of original bedding features including the shapes of fossils and fecal pellets. In these environments increasing carbon isotope ratios (δ ¹³ C = − 20 to + 15‰) indicate concretion growth below the sulfate reduction zone, i.e., in the methane generation zones. Continuing concretion growth at greater burial depth explains pore water profiles with constantly low Ca and downward decreasing Mg concentrations. Dissolved ammonia and phosphate profiles reguire adsorption and ion-exchange reactions as additional removal machanisms (besides apatite precipitation) in order to explain their downward decrease after they have reached maximum concentrations below the alkalinity maximum. Classification of early diagnetic environments into oxic and anoxic and further subdivision of the latter into sulfidic and non-sulfidic (with suboxic or post-oxic and methanic as further subcategories of the non-sulfidic environment) according to Berner (1981) is preferred over the previous classification in terms of pH/Eh fields. The temperature range of the early diagenetic stage extends from O to about 75°C, at which temperature thermocatalytic organic matter decomposition replaces the earlier bacterially mediated reactions and causes a whole set of new diagenetic reactions (such as feldspar dissolution, smectite to illite transformation) to start.