Strontium isotopic composition of some brines from the Precambrian Shield of Canada

Twenty-four groundwater samples from seven operating mines at Sudbury, Yellow-knife and Thompson (Ontario, North West Territories and Manitoba, resp.), all from depths greater than 1 km and ranging in total dissolved solids (TDS) from 1900 to 250,000 mg l^?1, were measured for their ${}^{87}\text{Sr}{}^{86}\text{Ar}$ values. Each geographic location gives a limited range in values and each location is distinct from the others. This is interpreted as the result of extensive water-rock interaction on a local scale. For most of the time, these brines were isolated and only recently have been exposed to surface water as a result of the mining operations. The extent of the isolation is shown by the contrasting isotopic values of two “pockets” of water (0.711 vs. 0.716) located on opposite sides of the same fault system on the North Range at Sudbury. The exchange at all sites probably has continued until the present, as indicated by the close agreement between water and present-day${}^{87}\text{Sr}{}^{86}\text{Sr}$ whole-rock values. If so, it suggests that there is no single age for such brines, but it may be possible to date stages in the water's evolution by determining the age of secondary minerals that equilibrated with the water.     

Strontium isotopic composition of oil-field and gas-field waters,Japan

The⁸⁷Sr/⁸⁶Sr ratios of 10 formation waters in petroleum and natural gas reservoirs along the western coast of northeastern Honshu, Japan, ranged from 0.7052 to 0.7084, and are distinctly lower than the ratio in seawater. This forms a marked contrast to oil-field brines from the U.S.A. which have higher⁸⁷Sr/⁸⁶Sr ratios. Taking into consideration that petroleum and natural gas in Japan accumulate in volcanic rocks derived from intense submarine volcanism in the Middle Miocene, the⁸⁷Sr/⁸⁶Sr ratios of the water samples are explained in terms of the isotope exchange between waters containing seawater Sr and reservoir rocks with lower ratios.     

Evolution of isotopic composition and deuterium excess of brines in the Sichuan Basin, China

The isotopic composition and parameters for deuterium excess of brines, which were sampled in the Si-chuan Basin, show obvious regularities of distribution. The brine isotopic composition shows distinct two systems of marine and terrestrial deposits, with the Middle Triassic strata as the boundary. Brine hydrogen isotopic composition of marine deposits is lower while oxygen isotopic composition is higher than that of the SMOW, respectively, indicating that the brines were derived from seawater with different evaporating degrees at different times. From the Sinian strata, up to the Cambrian, Permian Maokou Formation and the Triassic Jialingjiang Formation, the δD values of brines tend to become relatively positive with the strata becoming younger. Brines of terrestrial deposits are considered to have been derived from precipitation and their isotopic composition is close to the globe meteoric water line (GMWL). Brines of transitional deposits between marine and terrestrial ones (the Upper Triassic Xujiahe Formation) have δD and δ18O values falling between the two end members of marine deposit brines and precipitation, indicating that the brines are a mixture of precipitation and vaporing seawater. Water samples from the brine-bearing strata of different ages show various deuterium excesses (d) with an evident decreasing trend as the age of strata gets older and older. Brine-bearing strata of the Triassic Leikoupo-Jialingjiang Formation, the Permian Maokou Formation, the Cambrian and Sinian strata are all carbonate rocks which have experienced intensive water/rock reaction and the deuterium excess essentially changes with time. All brine-bearing-strata surrounding the basin or faults, as well as those brine wells exploited for resources, have been obviously influenced by the precipitation supply. Therefore, the deuterium excesses of their brines have increased to different extents, depending on the amount of involvement of meteoric water. The variation and distribution of d values of the brines from different Triassic strata are related to the embedded depth of the strata. The deuterium excesses of brines become lower with increasing burial depth of the strata.     

Strontium isotopic composition of some recent basic volcanites of the Southern Tyrrhenian Sea and Sicily Channel

The ⁸⁷Sr/⁸⁶Sr ratios have been determined on the volcanic rocks of Ustica, Linosa and Pantelleria Islands. The petrology of these islands is typical of volcanic products belonging to the alkalic suite. The volcanites of Ustica and Linosa Islands are mainly represented by basic terms (alkalibasalts and hawaiites), with minor mugearitic and trachytic differentiates. In addition to alkali-basalts and hawaiites, also some alkaline and peralkaline rocks of Pantelleria have been isotopically analysed. The ⁸⁷Sr/⁸⁶Sr ratios are consistent with a subcrustal origin for all the volcanic products of these islands. Some differences in the ⁸⁷Sr/⁸⁶Sr ratios have been found and tentatively related to an inhomogeneous Rb/Sr distribution in the mantle source material. The genetic relationships of these rocks with some products of the recent Tyrrhenian volcanism are also briefly discussed.     

A strontium, oxygen and hydrogen isotopic composition of brines, Michigan and appalachian basins, Ontario and Michigan

⁸⁷Sr/⁸⁶Sr ratios of brine from samples from the Michigan and Appalachian Basins, in Ontario and Michigan, covering the stratigraphic interval from the Cambrian to Mississippian, vary from 0.708 to 0.711. With the exception of the salt units of the Salina Formation (Silurian), most values are greater than seawater for the time in question, indicating water-rock interaction. The sources of the radiogenic Sr has not been identified. All samples plot below the GMWL in δ¹⁸O−δ²H space, with the Cambrian and Ordovician samples closest to the line. Mixing of brines meteoric and glacial (Pleistocene) water is indicated in some cases. The more concentrated brines from each stratigraphic unit show a very narrow spread in values. All the Ordovician brines show a narrow range over a 200 km area for Sr, O and H isotopes, indicating extensive lateral migration of the fluids.Strontium in the brine has not equilibrated isotopically with its host rock. In some cases the late-stage minerals saddle dolomite, calcite and anhydrite have the same ⁸⁷Sr/⁸⁶Sr ratios as the brine, indicating that they precipitated from the brine in isotopic equilibrium.     

Strontium isotopic composition of the Madera Formation (Pennsylvanian) near Albuquerque,New Mexico

⁸⁷Sr/⁸⁶Sr ratios of fourteen unaltered limestone and six fossil samples show a range of 0.7066-0.7118 for the depositional water of the Middle to Upper Pennsylvanian Madera Formation. The variation of these ⁸⁷Sr/⁸⁶Sr ratios may be due to the restricted depositional basin and nature of the source of the Madera Formation.While fossil and limestone samples are equally good for determination of strontium isotopic composition of depositional waters, leaches of calcareous shales contain significant amount of ⁸⁷Sr leached from the noncarbonate fraction during acid treatment.     

Geochemistry and modification of oilfield brines in surface pits in Northern Kuwait

Oilfield brines (produced water) are produced as a waste product daily at the gathering centers (GCs) in Kuwait oilfields. The geochemical evolution of the water produced at the GC (fresh brine) to stagnant pit water (evaporate) has been investigated in the northern fields of Kuwait, and a model is presented showing time-dependent variations. Kuwait oilfield brines are globally similar to others in other large sedimentary basins (USA, Canada), but modifications have occurred due to seawater injection practices performed episodically during the oil extraction process. Brine water chemistry changes from generally average brine chemistry (based on cations and anions) to saturated mixture of seawater, oilfield brine, and anthropogenic chemical pollutants. The objective of this study was to harmonize the database of brine waters in terms of regional identity by comparison with oilfield brines elsewhere, identify water–rock interaction, and statistically treat daily recordings from the pits in order to identify injection peaks and troughs. Laboratory analysis of major and minor cations and anions from the Rawdatayn samples gave the following concentration ranges in parts per million (ppm): (Na⁺, 11,698–203,977), (Ca²⁺, 2,216–98,514), (Mg²⁺, 1,602–28,885), (K⁺, 1,528–16,573), (Sr²⁺, 70–502), (Ba²⁺, 0.01–18.04), (Fe²⁺, 0.01–8.93), (Li⁺, 0.09–6.48), (Si²⁺, 0.00–13.18), (B³⁺, 0.05–37.45), (SO ₄ ²⁺ , 330–3100). For the Sabriyah oilfield samples, the major and minor cations and anions concentration ranges in ppm are: (Na⁺, 9,807–274,947), (Ca²⁺, 2,555–77,992), (Mg²⁺, 1,415–28,183), (K⁺, 764–19,201), (Sr²⁺, 77.84–641), (Ba²⁺, 0.15–6.76), (Fe²⁺, 0.016–38.88), (Li⁺, 0.05–6.83), (Si²⁺, 0.0195–16.84), (B³⁺, 7.17–55.33), (SO ₄ ²⁺ , 44,812–135,264). The stable isotopic analysis of five samples indicates normal trends in oxygen and hydrogen isotopes that classify the waters as “connate” which follow an evaporation trend. Carbon isotopic signatures are normal for hydrocarbon fields and average out around GC15, δ¹⁸O‰?=?1.4, δD‰?=??10, δ¹³C‰?=??3.6; while for GC23, δ¹⁸O‰?=?2.3, δD‰?=??4, δ¹³C‰?=??2.5; for GC25, δ¹⁸O‰?=??2.0, δD‰?=??14, δ¹³C‰?=??4.6; for pit1, δ¹⁸O‰?=?2.3, δD‰?=??5, δ¹³C‰?=??18.3; and for pit 2, δ¹⁸O‰?=?2.5, δD‰?=??4, δ¹³C‰?=??17.8. Carbon isotope average values for all brine samples from the GCs is?=??56 which falls within normal hydrocarbon formation water category. Data spikes coincide with injection periods at the following times (A: May–Jun, 2006), (B: Sep–Oct, 2006), (C: Jan–Feb, 2007), (D: Mar, 2007), (E: May–Jun, 2007), (F: Feb, 2006), (G: Mar–Apr, 2006) and, subsequently the decay to “normal” brine occurs over a period of several weeks. The database was large enough to apply a principal component statistical analysis (PCA). PCA and geo-statistical techniques reveal several distinct population groups. The main chemical groups in the data are as follows: plateau, spike groups, and pit evaporation group. The spike periods correlate closely with seawater injection periods (Jan–Feb, Mar–Apr, May–Jun, and Sep–Oct). The pit chemistry reveals exceptionally high evaporation processes coinciding with summer peak temperature. PCA results show distinct groupings centered around the major elements reminiscent of other oilfields, but with the added evaporation trend strongly enhanced.     

Strontium isotope composition of runoff from a glaciated carbonate terrain

The relationship between subglacial chemical weathering processes and the Sr isotope composition of runoff from Robertson Glacier, Alberta, Canada, is investigated. This glacier rests on predominantly carbonate bedrock of Upper Devonian age, but silicate minerals are also present. The provenance of solute in meltwaters is found to vary systematically with solute concentration and, by inference, subglacial water residence time. In dilute waters, the principal process of solute acquisition is calcite dissolution fueled by protons derived from the dissolution of CO₂ and subsequent dissociation of carbonic acid. At higher solute concentrations, dolomite dissolution coupled to sulfide oxidation is more important. Sr concentration is found to increase with total solute concentration in two separate meltwater streams draining from the glacier, but ⁸⁷Sr/⁸⁶Sr only increases in the eastern melt stream. Carbonate and K-feldspar sources are shown to dominate the Sr content of the western stream, irrespective of concentration. They also dominate the Sr content of the eastern stream at low and intermediate concentrations, but at higher concentrations, muscovite (with high ⁸⁷Sr/⁸⁶Sr) is also an important Sr source. This reflects the outcrop of muscovite-bearing lithologies in the catchment of the eastern stream and an increase in the rate of weathering of K-silicates relative to that of carbonates as more concentrated solutions approach saturation with respect to carbonates. Nonstoichiometric release of ⁸⁷Sr/⁸⁶Sr and preferential release of Sr over K from freshly ground K-silicate surfaces may also occur. This may help to explain the radiogenic nature of runoff from distributed subglacial drainage systems, which are characterized by long water:rock contact times and water flow through environments in which crushing and grinding of bedrock are active processes.Although the exchangeable Sr in tills has higher ⁸⁷Sr/⁸⁶Sr than local carbonate bedrock, only the more concentrated meltwaters from the eastern stream display similarly high values. The most dilute waters, which probably transport the bulk of the dissolved Sr flux from the glacier, have ⁸⁷Sr/⁸⁶Sr characteristic of local carbonate bedrock. Thus, the results suggest that although enhanced weathering of silicate minerals containing radiogenic Sr (such as muscovite) does occur in glaciated carbonate terrains, it is unlikely to contribute to any enhanced flux of radiogenic Sr from glaciated continental surfaces to the oceans.     

南秦岭大巴山大型钡成矿带中锶同位素组成及其成因意义

为探讨南秦岭大巴山大型钡成矿带中毒重石矿床与重晶石矿床的差异性,文中对大型钡成矿带的锶同位素组成特点进行了研究。结果表明,寒武系地层钡矿床中23件钡解石、毒重石、重晶石样品的87Sr/86Sr比值集中在0.707 771~0.708 869,平均值为0.708 379,低于寒武纪海水87Sr/86Sr比值(0.709),反映了成矿流体中有幔源物质的混入,锶同位素组成可能是海水与海底热卤水混合的结果,该过程类似于造成重晶石在海底沉积物中富集的现代洋底热水活动。志留系地层钡矿床中12件钡解石、毒重石、重晶石样品87Sr/86Sr比值集中在0.708 242~0.708 809,平均值为0.708 447,高于志留纪海水87Sr/86Sr比值(0.707 93),可能是同时代海水与深部热水混合所致,并有较高放射性成因壳源锶的混染。锶同位素组成可能是海水与海底热卤水混合的结果。文中锶同位素的研究为南秦岭大巴山大型钡成矿带的海底热水沉积成因提供了新的证据。     

The behavior of lithium and its isotopes in oilfield brines: evidence from the Heletz-Kokhav field, Israel

Twenty-four brine samples from the Heletz-Kokhav oilfield, Israel, have been analyzed for chemical composition and Li isotope ratios. The chemical composition of the brines, together with geological evidence, suggests derivation from (Messinian) seawater by evaporation that proceeded well into the gypsum stability field but failed to reach the stage of halite crystallization. The present salinity of the samples (18-47 g Cl/L) was achieved by dilution of the original evaporitic brine by local fresh waters. Like brines from other sedimentary basins, the Li/Cl ratios in the Heletz-Kokhav samples show a prominent Li enrichment (five-fold to eight-fold) relative to modern seawater. The isotopic ratios of Li, expressed in the δ ⁶Li notation, vary from −26.3 to −17.9‰, all values being significantly higher than that of modern seawater (−32‰) irrespective of their corresponding Li concentration (1.0-2.3 mg/L). The isotopic composition of Li and the Li/Cl ratio in the oilfield brines were acquired in two stages: (a) The original evaporated seawater gained isotopically light Li during the diagenetic interaction between the interstitial Messinian brine and the basin sediments. A parent brine with an elevated Li/Cl ratio was formed. The brine was later diluted in the oilfields. (b) The δ ⁶Li values of the final brines were determined during epigenetic interaction with the Heletz-Kokhav aquifer rocks. At the same time, the Li/Cl ratio inherited from stage (a) remained largely unchanged. This work represents the first use of lithium isotopic composition to elucidate the origin and evolution of formation waters in sedimentary basins.     

A strontium isotopic study of Smackover brines and associated solids,southern Arkansas

The isotopic composition of Sr has been measured in brine samples from the Upper Jurassic Smackover Formation in southern Arkansas; ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios range from 0.7071 to 0.7101. With one exception, the 32 Smackover brines contain Sr which is significantly more radiogenic than the Sr in Late Jurassic sea water, indicating sizable Sr contributions from detrital sources. Isotopic analyses of core samples from rock units associated with the brines and regional stratigraphic relationships suggest that the radiogenic Sr was released from detrital minerals in Bossier shale to interstitial fluids expelled from the underlying Louann Salt in the North Louisiana salt basin. These fluids migrated through the Bossier Formation updip to the South Arkansas shelf, where they entered the upper Smackover carbonate grainstone. The radiogenic fluids mixed with Sr-rich interstitial marine waters that had the isotopic composition of Late Jurassic sea water; mixing in variable proportions resulted in the random distribution pattern of variable ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios that is observed in Smackover brines within the 5000 km² study area. Isotopic analyses of nonskeletal carbonate grains and coexisting coarse calcspar cement from the upper Smackover grainstone imply that the grains were diagenetically stabilized in the presence of interstitial marine waters, whereas the calcspar cement is a relatively late diagenetic phase precipitated after the arrival of radiogenic fluids.     

Strontium isotopic constraints on the origin of proterozoic anorthosites

The Proterozoic Giles Complex, central Australia contains an almost complete range of anorthosite types from minor or major layers in gabbronorite intrusions to large anorthosite-troctolite bodies to small orthopyroxene anorthosite massifs; each type has a distinctive Sr isotopic signature. Anorthosite-dominated masses have a regular relationship between ferromagnesian mineralogy, initial ⁸⁷Sr/⁸⁶Sr and anorthite contents in plagioclase: anorthosite-troctolite bodies have significant olivine, relatively low initial ⁸⁷Sr/⁸⁶Sr (0.7038–0.7043) and An_50–69; orthopyroxene-dominant anorthosites have relatively high ⁸⁷Sr/⁸⁶Sr (0.7045–0.7063) and An₄₅₋₆₀. The pattern is found worldwide. Detailed study of one intrusion demonstrates that contamination by wall-rock granulite produces the higher ⁸⁷Sr/⁸⁶Sr values, anti-correlation between ⁸⁷Sr/⁸⁶Sr and An, and determines olivine/orthopyroxene proportions. Olivine-bearing anorthosites form from a primary aluminous tholeiite magma with plagioclase dominating the liquidus; progressive contamination of this parent magma produces a gradation to orthopyroxene anorthosites.     

Strontium isotopic equilibration during metamorphism of tillites from the Ogcheon Belt,South Korea

The NE/SW trending Ogcheon Belt formed during the Mesozoic by deformation and metamorphism of a sedimentary sequence which includes tillite formations of late Precambrian or Lower Palaeozoic age. In this study Rb-Sr isotopic data are reported from cm-scale sampling of clasts and matrix in these tillites, which underwent metamorphism at grades ranging from the biotite zone to the kyanite zone. Sr-isotopic disequilibrium between clasts and matrix persists up to the highest grade but in four out of five rocks the matrix samples approximate to isochrons (MSWD's<12). The mechanism for this selective isotopic equilibration is considered to be related to the metamorphic reactions in the matrix, which were probably accompanied by a substantial fluid flow. The matrix isochrons for three of the rocks, together with separated white micas from associated schists, suggest that metamorphism took place in the Trias, approximately 200 Myr ago. Metamorphism was followed by slow cooling and biotite closure temperatures were not reached until 190-150 Myr. — These results suggest that where high fluid/rock ratios can be demonstrated on independent petrological grounds, the analysis of small-scale whole-rock samples may allow effective Rb/Sr dating of metamorphism.     

Comparison of the Sr isotopic signatures in brines of the Canadian and Fennoscandian shields

A synthesis of Sr isotope data from shallow and deep groundwaters, and brines from the Fennoscandian and Canadian Shields is presented. A salinity gradient is evident in the water with concentrations varying from approximately 1–75 g L⁻¹ below 1500 m depth in the Fennoscandian Shield and from 10 up to 300 g L⁻¹ below 650 m depth in the Canadian Shield. Strontium isotope ratios were measured to assess the origin of the salinity and evaluate the degree of water–rock interaction in the systems. In both shields, the Sr concentrations are enriched relative to Cl, defining a positive trend parallel to the seawater dilution line and indicative of Sr addition through weathering processes. The depth distribution for Sr concentration increases strongly with increasing depth in both shields although the variation in Sr-isotope composition does not mirror that of Sr concentrations. Strontium-isotope compositions are presented for surface waters, and groundwaters in several sites in the Fennoscandian and Canadian Shields. Numerous mixing lines can be drawn reflecting water–rock interaction. A series of calculated lines links the surface end-members (surface water and shallow groundwater) and the deep brines; these mixing lines define a range of ⁸⁷Sr/⁸⁶Sr ratios for the deep brines in different selected sites. All sites show a specific ⁸⁷Sr/⁸⁶Sr signature and the occurrence of large ⁸⁷Sr/⁸⁶Sr variations is site specific in both shields. In Canadian Shield brines, the Sr isotope ratios clearly highlight large water rock interaction that increases the ⁸⁷Sr/⁸⁶Sr ratio from water that could have been of marine origin. In contrast to the Canadian Shield, groundwater does not occur in closed pockets in the Fennoscandian, and the well-constrained ⁸⁷Sr/⁸⁶Sr signatures in deep brines should correspond to a large, well-mixed and homogeneous water reservoir, whose Sr isotope signature results from water–rock interaction.     

Iodine-129 chronological study of brines from an Ordovician paleokarst reservoir in the Lunnan oilfield,Tarim Basin

Previous studies have shown that brines in an Ordovician paleokarst reservoir of the Lunnan oilfield in the Tarim Basin, China, are the product of mixing of paleo-evaporated seawater in the east with paleometeoric waters in the west. In order to put time constraints on the brine and related hydrocarbons in this field, 10 brine samples were collected, for which the iodine concentrations and ¹²⁹I/I ratios were measured and discussed. The iodine concentration (3.70–31.2 mg/L) and the ¹²⁹I/I ratio (189–897 × 10⁻¹⁵) show that the iodine in the paleoseawater and meteoric water (MW) had different origins and ¹²⁹I characteristics. The paleoseawater has a high iodine content (∼31 mg/L), indicating that iodine was introduced into the reservoir along with thermally generated hydrocarbons, possibly in the Cretaceous, from the Caohu Sag in the eastern area. Based on consideration of all possible origins of iodine and ¹²⁹I in the brines, it is suggested that the meteoric water maintained its initial iodine content (0.01 mg/L) and ¹²⁹I/I ratio (1500 × 10⁻¹⁵), whereas the iodine-enriched paloseawater (IPSW) exhibited a secular ¹²⁹I equilibrium (N_sq = 39 atom/μL) as a result of fissiogenic ¹²⁹I input in the reservoir over a long period of time. The model of brine evolution developed on that basis confirmed that meteoric water entered the reservoir in the Miocene at about 10 Ma, and partially mixed with the iodine-enriched paleoseawater. The movement of meteoric water was facilitated by faults created during the Himalayan orogeny, then became more dense after dissolving Paleogene halite and infiltrated into the reservoir at high pressure. The iodine and ¹²⁹I concentration in the brine contains information about the path and history of the fluid in the reservoir. This may be useful in oil exploration, since the movement of water was, to some extent, related to hydrocarbon migration.