Conjunctive K–Ca and Rb–Sr dating of glauconies

The glaucony series (of which glauconitic mica is the K-rich end member) is one of the few widely occurring minerals in the sedimentary record. So their isotopic ages determined mainly by the K–Ar method represent a major database for the geologic time scale. Many K–Ar ages were, however, found to be too young and often also discordant with available corresponding Rb–Sr ages. This discrepancy may reflect the disparate responses of the chemically contrasting daughter elements, Ar and Sr to postdepositional processes, and renders either age equivocal. A potentially promising approach to evaluate the intrinsic potential of glauconies and other K-rich minerals for direct and reliable dating of sediments is the conjunctive use of the chemically very similar K–Ca and Rb–Sr systems. The relationship between K–Ca and Rb–Sr ages may show a coherence or regularity indicative of a geologically meaningful age like in the case of the well known chemically identical dual U–Pb decay systems. As a crucial first step, this report presents the first successful precise K–Ca dating in conjunction with Rb–Sr dating of an Ordovician glauconite using the same sample aliquot, chemical procedure and mass spectrometer.     

The process of glauconitization: chemical and isotopic evidence

Sequential leaching experiments were made on Recent glauconies and clay fractions of the associated mud from off-shore Africa near the estuary of the Congo River. Analyses of major/rare earth elements (REE) and Nd isotopic compositions on the resulting leachate and residue pairs allow identification of at least three important and isotopically distinct components which contributed to the glauconitization process: (1) a detrital component with relatively high ⁸⁷Sr/⁸⁶Sr and relatively low ¹⁴³Nd/¹⁴⁴Nd isotopic ratios; (2) a phosphate phase rich in REE and Sr with sea water Sr and Nd isotopic characteristics; (3) a component rich in organic matter and Ca with a sea water Sr isotopic signature, a relatively low Nd isotopic composition and elevated Sm/Nd ratios. This latter component probably represents the suspended organic and carbonate-rich river load. The detrital and the river components were mixed up in the muddy off-shore sediment, ingested by worms, and integrated into faecal pellets. The resulting material has Sr and Nd isotopic signatures intermediate between those of the detrital and river components, and represents the precursor of the glaucony minerals. During the subsequent dissolution-crystallization process, the glauconitic pellets remain isotopically closed to any external supply, but expulsion of Sr and Nd with increasing degree of maturation is observed without any effect on the Sr and Nd isotopic compositions. At a higher maturation stage (K₂O>4.5%), the Sr and Nd isotopic compositions tend to decrease and increase, respectively, approximating the isotopic composition values of the phosphate-rich phase. Because the Sr and Nd concentrations decrease, the evolution of the glauconies toward lower Sr and higher Nd isotopic compositions can only be explained by expulsion of Sr and Nd of the detrital component with high Sr and low Nd isotopic signatures. Dissolution of the chemically unstable, wormdigested clay material from mud may be responsible for the liberation of these elements. Consequently, the phosphate-rich phase with sea water Sr and Nd isotopic signatures becomes increasingly important for the isotopic characteristics of the maturing glauconite grains, and sea water isotopic signatures can be reached during the stage of mature glauconite (K₂O>6.5%), without chemical exchange with the depositional environment.     

Genesis of Pb–Zn Mineralization Beneath the Xiangshan Uranium Orefield,South China: Constraints from H–O–S–Pb Isotopes and Rb–Sr Dating

The volcanic‐hosted Xiangshan uranium orefield is the largest uranium deposit in South China. Recent exploration has discovered extensive Pb–Zn mineralization beneath the uranium orebodies. Detailed geological investigation reveals that the major metallic minerals include pyrite, sphalerite, galena, and chalcopyrite, whilst the major non‐metallic minerals include quartz, sericite, and calcite. New δ¹⁸O_fluid and δD_fluid data indicate that the ore‐forming fluids were mainly derived from magmatic, and the sulfide δ³⁴S values (2.2–6.9‰) suggest a dominantly magmatic sulfur source. The Pb isotope compositions are homogeneous (²⁰⁶Pb/²⁰⁴Pb = 18.120–18.233, ²⁰⁷Pb/²⁰⁴Pb = 15.575–15.698, and ²⁰⁸Pb/²⁰⁴Pb = 37.047–38.446). The ⁸⁷Sr/⁸⁶Sr ratios of sulfide minerals range from 0.7197 to 0.7204, which is much higher than volcanic rocks and fall into the range of metamorphic basement. Lead and strontium isotopic compositions indicate that the metallogenic materials probably were derived from metamorphic basement. Pyrite Rb–Sr dating of the ores yielded 131.3 ± 4.0 Ma, indicating that the Pb–Zn mineralization occurred in the Early Cretaceous.     

Dolomitization by penesaline sea water in Early Jurassic peritidal platform carbonates, Gibraltar, western Mediterranean

Peritidal carbonates of the Lower Jurassic (Liassic) Gibraltar Limestone Formation, which form the main mass of the Rock of Gibraltar, are replaced by fine and medium crystalline dolomites. Replacement occurs as massive bedded or laminated dolomites in the lower 100 m of an ≈460‐m‐thick platform succession. The fine crystalline dolomite has δ¹⁸Ο values either similar to, or slightly higher than, those expected from Early Jurassic marine dolomite, and δ¹³C values together with ⁸⁷Sr/⁸⁶Sr ratios that overlap with sea‐water values for that time, indicating that the dolomitizing fluid was Early Jurassic sea water. Absence of massive evaporitic minerals and/or evaporite solution‐collapse breccias in these carbonate rocks indicates that the salinity of sea water during dolomitization was below that of gypsum precipitation. The occurrence of peritidal facies, a restricted microbiota and rare gypsum pseudomorphs are also consistent with penesaline conditions (salinity 72–199‰). The medium crystalline dolomite has some δ¹⁸Ο and δ¹³C values and ⁸⁷Sr/⁸⁶Sr ratios similar to those of Early Jurassic marine dolomites, which indicates that ambient sea water was again a likely dolomitizing fluid. However, the spread of δ¹⁸Ο, δ¹³C and ⁸⁷Sr/⁸⁶Sr values indicates that dolomitization occurred at slightly increased temperatures as a result of shallow (≈500 m) burial or that dolomitization was multistage. These data support the hypothesis that penesaline sea water can produce massive dolomitization in thick peritidal carbonates in the absence of evaporite precipitation. Taking earlier models into consideration, it appears that replacement dolomites can be produced by sea water or modified sea water with a wide range of salinities (normal, penesaline to hypersaline), provided that there is a driving mechanism for fluid migration. The Gibraltar dolomites confirm other reports of significant Early Jurassic dolomitization in the western Tethys carbonate platforms.     

Depositional controls on glaucony texture and composition, Upper Jurassic, West Siberian Basin

This study examines textural inhomogeneity and variable chemical composition of Upper Jurassic glaucony in relation to small‐scale synsedimentary and postsedimentary authigenic processes controlled by the palaeonvironmental and palaeogeographical context. Four glaucony types with complex textural and compositional features have been recognized in cores of the Georgiev Formation of the West Siberian Basin. Samples exclusively made of light green type 1 glaucony (K₂O < 6·5%: the less mature type, richer in glauconite–smectite mixed layer) formed under dysoxic conditions in the deepest distal marine environments of the northern sectors of the West Siberian Basin. Dark green type 2 glaucony is the most mature (richest in glauconitic mica: K₂O up to 8·5%), is sometimes associated with type 1 glaucony, and is typical of high bottom areas with a low sedimentation rate within the central sectors of the basin. Type 3 glaucony is formed by brown grains, poorer in K and Fe but richer in Al and Si than type 2 glaucony, and is only present in strongly condensed successions of the central‐eastern sectors of the West Siberian Basin. Type 4 glaucony is much richer in Fe than any other type, shows fresh yellowish green cores slightly less mature than type 2 glaucony, and brown rims and cracks with composition similar to that of type 3 grains; it was formed in western sectors of the West Siberian Basin, close to Urals. Weathering under a subtropical to temperate climate, and erosion of badly drained peneplaned lowland areas around the basin, provided Al‐rich terrigenous clays as substratum for glauconitization, which explains Al and Si enrichment in Siberian glaucony. Maturation from glauconite–smectite to glauconitic mica is monitored by a change from light to dark green colour related to decrease in Al, Si, Mg, Ca and Na, and to increase in K and Fe. Brown rims of type 4 glaucony, and brown type 3 grains formed after leaching of Fe and K from mature glauconite, with formation of clays and Fe oxyhydroxides as reaction products, as a result of free oxygen exposure related to a hydrodynamic regime and temporary sea‐level fall. Glauconitization stopped and diagenetic pyrite formed due to basin deepening and burial under black shales during the latest Jurassic–earliest Cretaceous transgression. This study demonstrates that, due to the complex nature of glaucony, the authigenesis of glauconitic minerals in the rock record cannot be correctly understood if the palaeoenvironmental context and the palaeogeographical context of glaucony‐bearing sediments are not considered.     

De glauconiarum origine

The glauconitic facies is widespread on present-day continental shelves from 50° S to 65° N and at water depths between 50 and 500 m, and is in particularly great abundance on the upper slope and outer shelf between 200 and 300 m. It is also common in many ancient rocks of post-late Precambrian age. It occurs as sand- to pebble-sized, essentially green particles (granular facies) but also as a surface coating on particles and hardgrounds and as a diffuse impregnation (film and diffuse facies). We suggest the replacement of the term ‘glauconite’, which has been interchangeably used to designate a morphological form and a specific mineral, by glaucony (facies) and glauconitic smectite and glauconitic mica as end members of the glauconitic mineral family. The widely accepted model of Burst and Hower for glauconitization requires a degraded, micaceous (2: 1 layer lattice structure) parent clay mineral. However, detailed analysis of numerous samples of Recent glaucony reveals that such a parent substrate is exceptional. The model therefore requires modification. Generally the parent material is carbonate particles, argillaceous (kaolinitic) faecal pellets, infillings of foraminiferal tests, various mineral grains and rock fragments, that pass gradually into the commonly occurring green grains. We show that the process of glauconitization is achieved by de novo authigenic growth of automorphous crystallites in the pores of the substrate, accompanied by progressive alteration and replacement of the substrate. It is this two-fold evolution that causes the ‘verdissement’of granular substrates, macrofossils and hardgrounds. The authigenic mineral is an iron-rich and potassium-poor glauconitic smectite. While new smectites are growing into the remaining pore space the earlier smectites are modified by incorporation of potassium, producing decreasingly expandable minerals with a non-expandable glauconitic mica as the end member. This mineralogical diversity of the glauconitic mineral family explains the highly variable physical and chemical properties of glaucony. Four categories, nascent, little-evolved, evolved and highly-evolved glaucony are distinguished. Glauconitization appears to be controlled by a delicate balance between degree of physical confinement of a particle and the amount of ionic exchange between the micro-environment and ambient open marine sea water. The optimum conditions for glauconitization are those of semi-confinement. As a result the interior of a grain is more glauconitized than its less confined periphery. Similarly, for identical substrate types, large grains (500μm) provide more favourable substrates for glauconitization than lesser confined small grains. On a larger scale the formation of glaucony is governed by the availability of iron and potassium and the balance between detrital influx and winnowing. Low accumulation rates expose grains to the open marine environment for sufficiently long times (10⁵-10⁶ years for highly-evolved glaucony).     

Isotopic measurements in the Cape York Peninsula area,North Qeensland

K‐Ar and Rb‐Sr isotopic measurements have been made on the north‐south belt of igneous and metamorphic rocks from the Peninsula Ridge and Yambo Inlier of Cape York Peninsula. Four periods of Palaeozoic igneous activity appear to have been denned. These are (⁸⁷’Rb^λ = 1.39 X 10^–11y–1) about 415 m.y., about 400 m.y., 385–390 m.y., and 255–280 m.y., with the youngest dates to the north and northeast. The largest volume of magma, the Kintore Adamellite was emplaced during the 285–390 m.y. period. Initial ⁸⁷Sr/⁸⁶Sr ratios range from 0.715 (a granodiorite) through 0.72–0.74 (muscovite adamellite) to 0.76 (leuco‐adamellite), which suggests a high component of old crustal material in the latter types.

The host metamorphics grade from greenschist facies in the west to almandine‐amphibolite facies in the centre and south. Limited direct data suggest that the greenschists are older than 1400 m.y. This is supported by intrusive dolerite dating greater than 1800 m.y. Rocks possibly 2000 m.y. old are thus adjacent to the Australian northeast coast and place drastic limitations on the possibility of continual continental growth to the east.

Rb/Sr measurements on minerals of the almandine amphibolite rocks record the major Kintore event. Total rock measurements have high uncertainties but give only slightly older figures. Initial ⁸⁷Sr/⁸⁶Sr ratios of these apparent total rock isochrons are high, 0.735–0.745. Gross isotopic redistribution must have occurred during the Palaeozoic metamorphism.

The Rb/Sr isotopic and geochemical relationships suggest that some of the granitic rocks have been derived from the equivalent of the present greenschist facies suite, and that the almandine amphibolite facies was, in part, remetamorphosed during the Palaeozoic and is possibly partly residual after metamorphic segregation.

The region has been examined from the plate tectonic point of view and shows that many of the requirements of a cordilleran‐type mountain belt of Dewey & Bird (1970) existed during the mid‐upper Palaeozoic. The Palmerville Fault and the Hodgkinson Basin are key units in this interpretation.

Dolerite, possibly 2000 m.y. old, could be contemporaneous with voluminous dolerites of similar age from the Kimberley region (Australia) and of Venezuela and Guyana. They may be a useful continental breakup indicator, as are the Gondwana dolerites.     

Strontium and hydrogen isotope geochemistry of fresh and metabasalt dredged from the Mid-Atlantic Ridge

Fresh basalt and metabasalt dredged from the Mid-Atlantic Ridge were studied for Na, K, Rb, Sr, and H₂O(+) contents, and strontium and hydrogen isotope ratios. Na, K, Rb, and Sr contents of these samples are within the range of those of oceanic tholeiite. H₂O(+) content, strontium, and hydrogen isotope ratios vary widely. The variation in water content of metabasalt is apparently related to the chlorite content. The metamorphic temperature was about 550 °C based on the estimated δD value of chlorite. There is positive linear relationship between water content and strontium isotope ratio. Based on this relationship, the variation of strontium isotope ratio of the metabasalt was interpreted as follows: complete exchange occurred between strontium in the chlorite portion of the metabasalt and strontium in sea water (⁸⁷Sr/⁸⁶Sr ratio=0.7090), while the original strontium (⁸⁷Sr/⁸⁶Sr∼0.7023) was retained in the non-altered portion of the basalts.     

Formation of modern dolomite in hypersaline pans of the Western Cape,South Africa

Authigenic calcite and dolomite and biogenic aragonite occur in Holocene pan sediments in a Mediterranean‐type climate on the western coastal plain of South Africa. Sediment was analysed from a Late Pleistocene coastal pan at Yzerfontein and four Holocene inland pans ranging from brackish to hypersaline. The pans are between 0·08 and 0·14 km² in size. The δ¹⁸O_PDB values of carbonate minerals in the pan sediments range from ?2·41 to 5·56‰ and indicate precipitation from evaporative waters. Covariance of total organic content and percentage carbonate minerals, and the δ¹³C_PDB values of pan carbonate minerals (?8·85 to ?1·54‰) suggest that organic matter degradation is a significant source of carbonate ions. The precipitation of the carbonate minerals, especially dolomite, appears to be mediated by sulphate‐reducing bacteria in the black sulphidic mud zone found in the brine‐type hypersaline pans. The knobbly, sub‐spherical texture of the carbonate minerals suggests that the precipitation of the carbonate minerals, particularly dolomite, is related to microbial processes. The ⁸⁷Sr/⁸⁶Sr ratios of pan carbonate minerals (0·7108 to 0·7116) are slightly higher than modern sea water and indicate a predominantly sea water (marine aerosol) source for calcium (Ca²⁺) ions with relatively minor amounts of Ca²⁺ derived from the chemical weathering of bedrock.     

Mineralization age and sources of ore‐forming material of the Nanmushu Zn‐Pb deposit in the Micangshan Tectonic Belt at the northern margin of the Yangtze Craton,China: Constraints from Rb‐Sr dating and Sr‐Pb isotopes

The Nanmushu Zn‐Pb deposit, hosted by the Neoproterozoic Dengying Formation dolostone, is located in the eastern part of the Micangshan tectonic belt at the northern margin of the Yangtze Craton, China. This study involves a systematic field investigation, detailed mineralogical study, and Rb‐Sr and Pb isotopic analyses of the deposit. The results of Rb‐Sr isotopic dating of coexisting sphalerite and galena yield an isochron age of 486.7 ± 3.1 Ma, indicating the deposit was formed during the Late Cambrian to Early Ordovician. This mineralization age is interpreted to be related to the timing of destruction of the paleo‐oil reservoir in the Micangshan tectonic belt. All initial ⁸⁷Sr/⁸⁶Sr ratios of sphalerite and galena (0.70955–0.71212) fall into the range of the Mesoproterozoic Huodiya Group basement rocks (0.70877–0.71997) and Dengying Formation sandstone (0.70927–0.71282), which are significantly higher than those of Cambrian Guojiaba Formation limestone (0.70750–0.70980), Cambrian Guojiaba Formation carbonaceous slate (0.70766–0.71012), and Neoproterozoic Dengying Formation dolostone (0.70835–0.70876). Such Sr isotope signatures suggest that the ore strontium was mainly derived from a mixed source, and both of the Huodiya Group basement rocks and Dengying Formation sandstone were involved in ore formation. Both sphalerite and galena are characterized by an upper‐crustal source of lead (²⁰⁶Pb/²⁰⁴Pb = 17.849–18.022, ²⁰⁷Pb/²⁰⁴Pb = 15.604–15.809, and ²⁰⁸Pb/²⁰⁴Pb = 37.735–38.402), and their Pb isotopes are higher than, but partly overlap with, those of the Huodiya Group basement rocks, but differ from those of the Guojiaba and Dengying Formations. This suggests that the lead also originated from a mixed source, and the Huodiya Group basement rocks played a significant role. The Sr and Pb isotopic results suggest that the Huodiya Group basement rocks were one of the most important sources of metallogenic material. The geological and geochemical characteristics show that the Nanmushu Zn‐Pb deposit is similar to typical Mississippi Valley type, and the fluid mixing may be a reasonable metallogenic mechanism for Nanmushu Zn‐Pb deposit.     

The glauconite–Fe‐illite–Fe‐smectite problem: a critical review

Iron silicate minerals are a significant component of sedimentary systems but their modes of formation remain controversial. Our analysis of published data identifies end‐member compositions and mixtures and allows us to recognize controls of formation of different mineral species. The compositional fields of glaucony, Fe‐illite, Fe–Al smectites are determined in the M⁺/4Si vs. Fe/Sum of octahedral cations (M⁺ = interlayer charge). Solid solutions could exist between these phases. The Fe–Al and Fe‐rich clay minerals form two distinct solid solutions. The earliest phases to be formed are Fe–Al smectites or berthierine depending on the sedimentation rate. Reductive microsystems appear in the vicinity of organic debris in unconsolidated sediments. The Fe is incorporated first in pyrite and then in silicates after oxidation. Potassium ions diffuse from the sea‐water–sediment interface. If not interrupted, the diffusion process is active until reaction completion is reached, i.e. formation of Fe‐illite or glauconite or a mineral assemblage (berthierine–nontronite) according to the available Al ion amounts in the microsystem. Mixed‐layer minerals are formed when the diffusion process is interrupted because of sedimentation, compaction or cementation. Despite the common belief of their value as palaeoenvironment indicators, these minerals can form in a variety of environments and over a period of millions of years during sediment burial.     

Rubidium,strontium and the isotopic composition of strontium in ultramafic nodule minerals and host basalts

The concentrations of rubidium and strontium and the isotopic composition of strontium have been determined in minerals separated from ultramaflc nodules occurring in late Tertiary and Quaternary basalts of wide geographic distribution. Clinopyroxene, orthopyroxene and olivine from each of three Iherzolite nodules show a relatively wide range of ⁸⁷Sr/⁸⁶Sr disequilibrium and none of the minerals is in isotopic equilibrium with its host basalt. In two cases there is a correlation between ⁸⁷Sr/⁸⁶Sr and ⁸⁷Rb/⁸⁶Sr ratios of the nodule minerals, indicating apparent isochron relationships which may represent relict mantle events. Clinopyroxene and olivine from each of two wehrlite nodules are not in isotopic equilibrium, although the magnitude of the disequilibrium is smaller than that observed in the Iherzolite nodules. None of these ultramafic nodules can be a crystal cumulate from its host basalt, and it is doubtful that any type of genetic relationship exists. The strontium isotopic disequilibrium between nodule minerals seems to be a primary feature inherited from past mantle histories.     

Carbon and Strontium Isotopes of Late Palaeozoic Marine Carbonates in the Upper Yangtze Platform,Southwest China

238 marine carbonate samples were collected from seven sedimentary sections ofthe entire late Palaeozoic (Permian, Carboniferous and Devonian) in the Upper Yangtze Plat-form, southwest China. Based on the absence of cathodoluminescence and very low Mn (gener-ally<50 ppm) contents of the samples, it is thought that they contain information on the orig-inal sea water geochemistry. The results of isotopic analyses of these samples are presented interms of δ~(13)C and ~(87)Sr/~(86)Sr ratios versus geological time. The strontium data, consistent withother similar data based on samples from North America, Europe, Africa and other areas inAsia, support the notion of a global consistency in strontium isotope composition of marinecarbonates. The strontium data exhibit three intervals of relatively low ~(87)Sr/~(86)Sr ratios in thelate Middle Devonian to early Late Devonian, Early Carboniferous and Early Permian, corre-sponding to global eustatic high sea level stands. The lowest ~(87)Sr/~(86)Sr ratio recorded in theLate Permian was probably caused by substantial basalt eruptions in the Upper Yangtze Plat-form at the time. Three corresponding periods of relatively high δ~(13)C values at roughly the samethe intervals were caused by a relatively high rate of accumulation of organic carbon duringsea level rises at these times. The deposition of coal was probably responsible for the increaseof sea water δ~(13)C at other times. The δ~(13)C values drop dramatically near theDevonian/Carboniferous, Carboniferous/Permian and Permian/Triassic boundaries, con-sistent with other similar data, which further support the notion that geological time boundariesare associated with mass extinction and subsequent rejuvenation.     

Isotope hydrology of the Chalk River Laboratories site,Ontario, Canada

This paper presents results of hydrochemical and isotopic analyses of groundwater (fracture water) and porewater, and physical property and water content measurements of bedrock core at the Chalk River Laboratories (CRL) site in Ontario. Density and water contents were determined and water-loss porosity values were calculated for core samples. Average and standard deviations of density and water-loss porosity of 50 core samples from four boreholes are 2.73 ± 12 g/cc and 1.32 ± 1.24 percent. Respective median values are 2.68 and 0.83 indicating a positive skewness in the distributions. Groundwater samples from four deep boreholes were analyzed for strontium (⁸⁷Sr/⁸⁶Sr) and uranium (²³⁴U/²³⁸U) isotope ratios. Oxygen and hydrogen isotope analyses and selected solute concentrations determined by CRL are included for comparison. Groundwater from borehole CRG-1 in a zone between approximately +60 and −240 m elevation is relatively depleted in δ¹⁸O and δ²H perhaps reflecting a slug of water recharged during colder climatic conditions. Porewater was extracted from core samples by centrifugation and analyzed for major dissolved ions and for strontium and uranium isotopes. On average, the extracted water contains 15 times larger concentration of solutes than the groundwater. ²³⁴U/²³⁸U and correlation of ⁸⁷Sr/⁸⁶Sr with Rb/Sr values indicate that the porewater may be substantially older than the groundwater. Results of this study show that the Precambrian gneisses at Chalk River are similar in physical properties and hydrochemical aspects to crystalline rocks being considered for the construction of nuclear waste repositories in other regions.     

The effects of diagenesis on the redistribution of strontium isotopes in shales

The rubidium-strontium method has often been used in attempts to date shales, but has yielded mixed results. In order to explore the effects of diagenesis on this system, samples of a Miocene shale section collected from an oil well drilled in coastal Louisiana were separated into fractions and analyzed for Sr⁸⁷/Sr⁸⁶, Rb and Sr. The diagenetic changes involve the destruction of detrital mica and feldspar and the formation of an illite-rich clay from smectite. Strontium from interstitial waters, calcium carbonate and adsorbed on the clay minerals is released and then sequestered by the newly forming phases, together with the strontium mobilized from the silicate minerals. Attending these changes there is a trend towards the homogenization of the shale with respect to its strontium isotopes, but diagenesis and homogenization are not complete in the deepest part (5523 m) of the section studied. Therefore, the interpretation of rubidium-strontium shale dates remains uncertain, but the dates in many cases most probably represent the time equal to or younger than the time of the major construction of new phases and the attendant homogenization of the strontium isotopes.     

Rb–Sr dating of sulfides and S–Pb isotopic study of the Bayanbaolege Ag polymetallic deposit,Inner Mongolia,NE China

The large-scale Bayanbaolege Ag polymetallic deposit is situated in the Tuquan–Linxi Fe-Sn-Cu-Pb-Zn-Ag metallogenic sub-belt in eastern slopes of the southern Great Xing’an Range, NE China. The sulfide-quartz vein-type orebodies in the deposit are hosted primarily in the Early Cretaceous granodiorite porphyry and Late Permian strata. Three primary paragenetic stages of veining have been identified: (I) arsenopyrite- pyrite-quartz stage, (II) pyrite-sphalerite-quartz stage, and (III) galena-silver minerals (pyrargyrite, argentite, and pearceite)-calcite stage. The Rb–Sr dating of sulfides yielded an isochron age of 129.9 ± 2.9 Ma (MSWD = 2.1) for the sphalerite, which constrains the mineralization age to the Early Cretaceous. Rb and Sr concentrations in the sulfides ranged from 0.0940 to 1.0294 ppm and 0.0950–3.3818 ppm, respectively. The initial ⁸⁷Sr/⁸⁶Sr value of the sphalerite was 0.70852 ± 0.00018, indicating that the mineralized materials were derived from the mixed crust-mantle source area. S isotope analysis showed that the δ³⁴S values of the sulfide samples varied in a narrow range, from −1.5‰ to +1.3‰ (mean −0.65‰), indicating a magmatic S source. Pb isotopic ratios of the sulfides (²⁰⁶Pb/²⁰⁴Pb = 18.306–18.416, ²⁰⁷Pb/²⁰⁴Pb = 15.524–15.605, ²⁰⁸Pb/²⁰⁴Pb = 38.095–38.479) and the granodiorite porphyry (²⁰⁶Pb/²⁰⁴Pb = 18.341–18.933, ²⁰⁷Pb/²⁰⁴Pb = 15.539–15.600, ²⁰⁸Pb/²⁰⁴Pb = 38.134–38.944) reflect that the ore-forming materials originated from contemporaneous magma with Early Cretaceous granodiorite porphyry. This study of the Bayanbaolege deposit and other hydrothermal deposits in the area provides compelling evidence that the widespread Mesozoic magmatism and mineralization in the southern Great Xing’an Range occurred in an intracontinental extensional tectonic setting, which was associated with the westward subduction of the paleo-Pacific plate.     

Application of the trace element and isotope geochemistry of strontium to studies of carbonate diagenesis

Carbonate rocks and natural waters exhibit a wide range in the concentration and isotopic composition of strontium. This wide range and the quantifiable covariation of these parameters can provide diagnostic tools for understanding processes of fluid-rock interaction. Careful consideration of the uncertainties associated with trace element partitioning, sample heterogeneity and fluid-rock interaction mechanisms is required to advance the application of the trace element and isotope geochemistry of strontium to studies of diagenesis, goundwater evolution, ancient seawater chemistry and isotope stratigraphy. A principal uncertainty involved in the application of Sr concentration variations to carbonate systems is the large range of experimental and empirical results for trace element partitioning of Sr between mineral and solution. This variation may be a function of precipitation rate, mineral stoichiometry, crystal growth mechanism, fluid composition and temperature. Calcite and dolomite in ancient limestones commonly have significantly lower Sr concentrations (20–70 p.p.m.) than would be expected from published trace element distribution coefficient values and Sr/Ca ratios of most modern sedimentary pore waters. This discrepancy probably reflects the uncertainties associated with determining distribution coefficient values. As techniques improve for the analytical measurement and theoretical modelling of Sr concentration and isotopic variations, the petrological analysis of carbonate samples becomes increasingly important. The presence of even small percentages of non-carbonate phases with high Rb concentrations and high ⁸⁷ Sr⁸⁶ Sr values, such as clay minerals, can have significant effects on the measured ⁸⁷ Sr/⁸⁶ Sr values of carbonate rocks, due to the decay of ⁸⁷Rb to ⁸⁷ Sr. For example, a Permian marine limestone with 50 p.p.m. Sr and 1 p.p.m. Rb will have a present-day ⁸⁷ Sr/⁸⁶ Sr value that is >2 × 10^?4 higher than its original value. This difference is an order of magnitude greater than the analytical uncertainty, and illustrates the importance of assessing the need for and accuracy of such corrections. A quantitative evaluation of the effects of water-rock interaction on Sr concentrations and isotope compositions in carbonates strengthens the application of these geochemical tracers. Geochemical modelling that combines the use of trace elements and isotopes can be used to distinguish between different mechanisms of water-rock interaction, including diffusive and advective transport of diagenetic constituents in meteoric pore fluids during the recrystallization of carbonate minerals. Quantitative modelling may also be used to construct diagnostic fluid-rock interaction trends that are independent of distribution coefficient values, and to distinguish between mixing of mineral end-members and fluid-rock interaction.     

Correlation between strontium and oxygen isotopic compositions of rocks from the Adamello massif (Northern Italy)

Rock samples from the lithologic units forming the Adamello massif were analyzed for Rb and Sr concentrations and for⁸⁷Sr/⁸⁶Sr and¹⁸O/¹⁶O ratios. The most important features are as follows:

1. the strontium and oxygen isotopes show a systematic variation from south to northwest across the massif, the older units in the south being lower both in⁸⁷Sr and¹⁸O;
2. a good positive correlation was found between strontium and oxygen isotopic compositions.

Two genetic models are advanced for explaining the results: (1) the mixing of two magmas with different¹⁸O and⁸⁷Sr contents; (2) magma formation at different depths in a crust layered with respect to both oxygen and strontium isotope composition.     

Roles of sorting and chemical weathering in the geochemistry and magnetic susceptibility of Xiashu loess, East China

Uncertainties in paleoenvironmental interpretations for traditional chemical analysis of bulk samples result from different grain-size sub-populations of sediments containing variable distributions of elements and minerals. Therefore, it is important to understand the elemental and mineral distribution in different grain sizes in determining the quantitative relationship between chemical weathering and climatic change. We sieved a series of Xiashu loess samples into three sub-populations of different grain sizes (<2, 2–45 and >45 μm, respectively), and then analyzed each population for rubidium (Rb), strontium (Sr), rare earth elements and magnetic susceptibility. In comparison with elemental concentrations of bulk samples, clay mineralogy and illitic crystallinity, our results show that distinct elemental distributions and magnetic susceptibilities for different grain-size sub-populations are controlled by sorting and/or chemical weathering, although we also suggest that the Xiashu loess may have the same provenance as the Central Chinese Loess. Maximum concentrations of Rb and fine-grained magnetic minerals in the less than 2 μm sub-population, coupled with our finding of maximum Sr in the larger than 45 μm fraction, indicate that Sr was lost during chemical weathering. Grain-size sub-population analysis is, therefore, an effective method for extracting paleoenvironmental information, because individual sub-populations show minimal variations in initial Rb/Sr ratios compared to bulk analysis of all sizes together. Furthermore, a negative correlation between Rb/Sr ratios and Sr concentrations for the <2 μm fraction (R² = 0.97) may indicate that clay is a sensitive indicator of intensity of chemical weathering and is an ideal sub-population for determining Rb/Sr ratios, but not for magnetic susceptibility.     

广西钦州石炭-二叠纪深海硅质岩的锶同位素组成及其地质意义

报道了广西钦州海槽早石炭世-早二叠世深水硅质岩的锶同位素测定结果和经年代校正后的87Sr/86Sr初始值,建立了锶同位素演化曲线;通过与同时代上扬子地区台地相碳酸盐岩87Sr/86Sr比值和演化曲线的对比,研究了二者的异同和造成差异的原因。深水硅质岩和同期台地相碳酸盐岩的锶同位素演化曲线在总体特征上具有一定的相似性,反映海平面变化对其影响的一致性。玄武岩喷发等局部事件和硅质岩中无法回避的陆源碎屑的影响是造成87Sr/86Sr比值和演化曲线差异的主要原因。硅质岩锶同位素演化曲线显示,海平面上升发生于早石炭世,在晚石炭世早期达到最大值,晚石炭世晚期,海平面有所下降,在其后的早二叠世,海平面再次上升。