Distinguishing between seafloor alteration and fluid flow during subduction using stable isotope geochemistry: examples from Tethyan ophiolites in the Western Alps

Large amounts of fluid, bound up in the hydrated upper layers of the ocean crust, are consumed at convergent margins and released in subduction zones through devolatilization. The liberated fluids may play an integral role in subduction zone processes, including the generation of arc-magmas. However, exhumed subduction zone rocks often record little evidence of large-scale fluid flow, especially at deeper levels within the subduction zone. Basaltic pillows from the high-pressure Corsican and Zermatt-Saas ophiolites show a range of δ¹⁸O values that overall reflect seafloor alteration prior to subduction. However, comparison between the δ¹⁸O values of the cores and rims of the pillows suggests that the δ¹⁸O values of the pillow rims at least have been modified during subduction and high-pressure metamorphism. Pillows that have not undergone high-pressure metamorphism generally have rims with higher δ¹⁸O values than their cores, whereas the converse is the case in pillows that have undergone high-pressure metamorphism. This reversal in the core to rim oxygen isotope relationship between unmetamorphosed and metamorphosed pillows is strong evidence for fluid–rock interaction occurring during subduction and high-pressure metamorphism. However, the preservation of different δ¹⁸O values in the cores and rims of individual pillows and within and between different pillows suggests that fluid flow within the subduction zone was strongly channelled. Resetting of the δ¹⁸O values in the pillow rims was probably due to fluid-hosted diffusion that occurred over relatively short time-scales (<1 Myr).     

Oxygen isotope exchange and closure temperatures in cooling rocks

Retrograde exchange of oxygen isotopes between minerals in igneous and metamorphic rocks by means of diffusion is explored using a finite difference computer model, which predicts both the zonation profile of δ¹⁸O within grains, and the bulk δ¹⁸O value of each mineral in the rock. Apparent oxygen isotope equilibrium temperatures that would be observed in these rocks are calculated from the δ¹⁸O values of each mineral pair within the rock. In systems which cool linearly from a sufficiently high temperature or at a low enough cooling rate, such that the final oxygen isotope values are not dependent upon the initial oxygen isotope values ('slow cooling'), the apparent oxygen isotope temperature derived for a rock composed of a single mineral pair can be shown to be simply related to the Dodson closure temperatures ( T _c) for the two phases and the mode of the rock. Adding a third phase into a system which undergoes 'slow' cooling will cause the apparent temperature derived for the two minerals already present to differ from the simple relationship for a two-phase system. In some systems oxygen isotope reversals can be developed. If cooling is not 'slow', then the mineral δ¹⁸O values resulting from cooling will be partly dependent upon the initial temperature of the system concerned. The model successfully simulates the mineral δ¹⁸O values that are often observed in granitic rocks. Application of the model will help in assessing the validity of oxygen isotope thermometry in different geological settings, and allows quantitative prediction of the oxygen isotope fractionations that are developed in cooling closed systems.     

Oxygen Isotopic Characteristics of Granitic Intrusions Related to Haobugao Zn-Pb-Cu-Sn Skarn Deposit, East Inner Mongolia, China

Abstract. Granitic rocks related to the formation of Haobugao Zn-Pb-Cu-Sn skarn deposit, Inner Mongolia, China, show unusual low whole-rock δ¹⁸O values down to -8.8 % (V-SMOW), whereas separated quartz crystals from those rocks give positive δ¹⁸O values of+4.1 to +9.9 %. Chemical analyses and microscopic observation of those granitic rocks confirm that they suffered hydrothermal alteration. Some skarn specimens and quartz from the Haobugao deposit also show negative δ¹⁸O values. The isotopic evidence indicates that intensive meteoric water circulation occurred at the time of granitic intrusion, and caused the pervasive hydrothermal alteration of granitic rocks and the precipitation of skarn deposit in this area.     

Geochemical Characteristics of the Akiyoshi Limestones, Japan and Their Bearing on Exploration for Blind Skarn Deposits

Abstract. Carboniferous-Permian limestones of the Akiyoshi Plateau, in the Inner Zone of southwestern Japan, are composed of essentially pure calcium carbonate containing only small amounts of other elements, and they are accompanied by marble and copper skarn deposits near the contact with late Cretaceous granitoids. The δ¹⁸O values of the Akiyoshi limestones range widely from 7.6 to 28.3% and are mostly lower than those of other areas of the same age (23–29%), whereas the differences among the δ¹³C values are small. The δ¹⁸O values are negatively correlated with Mn and Fe contents. Samples with high δ¹⁸O (>25%) and δ¹³C (>2%) values do not contain Fe, Zn, or Pb, but those with low δ¹⁸O values tend to be rich in these elements, indicating that these elements were introduced by interaction with H₂O dominant fluids, possibly of magmatic origin. Potential scores for evaluating the degree of interaction with hydro thermal fluids were calculated for δ¹⁸O, δ¹³C, Fe, Mn, Zn, Pb, and Sr. Higher scores implying much hydrothermal interaction were evident in the Mt. Hananoyama area, where there are many skarn deposits, and along faults oriented mainly NNW-SSE. Therefore, these are promising areas for exploring for blind deposits. It is likely that the hydrothermal fluid traveled through the limestones along fractures at the time of the granitic intrusions. However, the potential scores here are much smaller than those in the Pb-Zn mineralized area of the Kamioka mine, so more detailed petrological and mineralogical investigations are necessary.     

Dolomites in the Tazekka Pb–Zn district, eastern Morocco: polyphase origin from hydrothermal fluids

Many different types of water and processes have been proposed for the formation of dolomites. The three phases of hydrothermal dolomites in the Middle Atlas Causse were investigated to elucidate their formation processes. The first two of these are associated with sphalerite and galena in stratiform and open space-filling deposits. These formed early in the history of the deposition of the Pb–Zn mineralization and commonly reveal a paragenetic overlap. A later phase, post-dating Pb–Zn mineralization, is reflected in saddle dolomite.
All three phases show a decrease in δ¹⁸O and δ¹³C values passing from sterile (unmineralized) to mineralized rocks, and isotopic signatures are independent of the carrier facies. However, early-formed dolomites can be separated into two distinct groups on the basis of δ¹⁸O values. Type 1 dolomites host stratiform ore deposits, whereas type 2 dolomites host an open space-filling ore-body. Later saddle dolomites are more depleted in ¹⁸O than either of these.
The early hydrothermal and saddle dolomites precipitated from similar fluids during three distinct events, but formed by two mechanisms: replacement (hydrothermal dolomite) and cement precipitation (saddle dolomite). They show different isotopic signatures and apparently formed at different temperatures. Field data, petrographic and stable isotope results suggest a continuum of replacement, during the Carixian for the early hydrothermal dolomite 1, and during the Toarcian for early hydrothermal dolomite 2, followed by a cement precipitation phase for saddle dolomite.     

Hydrothermal Alteration, Fluid Inclusion and Stable Isotope Studies of the North Roby Zone, Lac des Iles PGE Mine, Ontario, Canada

The Archean mafic–ultramafic complex of Lac des Iles, Ontario, Canada, hosts economic platinum group elements (PGE)-Au-Cu-Ni mineralization in the Roby Zone. All lithologies in the North Roby Zone have been affected by hydrothermal alteration. The alteration products include talc (the most dominant mineral), anthophyllite, serpentine, actinolite, tremolite, chlorite, hornblende, zoisite, clinozoisite, epidote and sericite. In the altered rocks, light rare earth elements (La, Ce, Nd, Sm), Pb, Rb, Ba, Cs, S and possibly Y have been added by hydrothermal solution whereas Eu and heavy rare earth elements (Yb, Gd, Dy, Er) remained immobile. There are five types of fluid inclusions in the pegmatitic plagioclase with homogenization temperature and salinity ranging from 240°C to 445°C and 15.37 to 48.52 wt% equivalent NaCl, respectively. The δ¹⁸O and δD of talc range form 6.2‰ to 6.9‰ and −28‰ to −48‰, respectively. δ¹⁸O and δD water in equilibrium with talc during the hydrothermal alteration suggest a modified source for the hydrothermal solution. Microthermometry and stable isotope studies suggest that high temperature–high salinity fluid was diluted by, and mixed with, low temperature–low salinity meteoric solution. This mechanism precipitated the hydrothermal assemblage and redistributed trace elements during and after pegmatite formation in the North Ruby Zone.     

Stable isotope study of carbonate sediments from the Coorong Area, South Australia

ABSTRACT
The mineralogy and isotope geochemistry of carbonate minerals in the Coorong area are determined by the water chemistry of different depositional environments ranging from seawater to evaporitically modified continental water. The different isotopic compositions of coexisting calcite and dolomite suggest that each of the above two minerals was formed from water of composition and origin unique to that specific mineral. In addition, the dolomite was not formed by simple solid state cation exchange.
The occurrence of two types of dolomite was shown by isotope analysis and SEM observations. The dolomite, which is isotopically light (δ¹³C = -1 to -2% 0 ; δ¹⁸O=+3 to +5%₀) and of fine grain size (˜ 0·5 μm) probably precipitated under the influence of evaporitically modified continental water. Coarser grained dolomite (up to 4 μm) is isotopically heavier (δ¹³C=+3 to +4%₀; δ¹⁸O=+5 to + 6%₀) contains Mg in excess of Ca and was formed in or close to equilibrium with atmospheric CO² probably by the dolomitization of aragonite.     

Stable isotopic evidence for fluid infiltration during contact metamorphism in a multiply-metamorphosed terrane: the Reynolds Range, Arunta Block, central Australia

The Lander Rock Beds form the local basement of the Reynolds Range in the Arunta Inlier of central Australia. These dominantly quartzose and pelitic lithologies underwent low-grade ( c.   400  °C) regional metamorphism prior to contact metamorphism ( c.   2.5  kbar) around S-type megacrystic granitoids at 1820–1800  Ma. The Lander Rock Beds are overlain by metasediments of the Reynolds Range Group, which were subsequently intruded by granitoids at c. 1780  Ma. Regional metamorphism at 1590–1580  Ma produced grades varying from greenschist (400  °C at 4–5  kbar) to granulite (750–800  °C at 4–5  kbar) from north-west to south-east along the length of the Reynolds Range. Oxygen isotope ratios of the Lander Rock Beds were reset from 13.4±0.8 to as low as 6.7 adjacent to the contacts of the larger plutons, and to 10.3±1.1 around the smaller plutons. Biotite in all the major rock types found in the aureoles has δD values between −52 and −69, probably reflecting resetting by a cooling igneous+metamorphic fluid near the plutons. Sapphirine-bearing and other Mg- and Al-rich rock types have low δ¹⁸O values (4.0±0.7). The precursors to these rocks were probably low-temperature ( c. 200  °C) diagenetic–hydrothermal deposits of Mg-rich chlorite, analogous to those in Proterozoic stratiform precious metal and uranium deposits that form by the infiltration of basin brines or seawater. As in the overlying Reynolds Range Group, regional metamorphism involved little fluid–rock interaction and isotopic resetting.     

Petrochemical constraints for dual origin of garnet peridotites from the Dabie-Sulu UHP terrane, eastern-central China

Garnet peridotites occur as lenses, blocks or layers within granulite–amphibolite facies gneiss in the Dabie-Sulu ultra-high-pressure (UHP) terrane and contain coesite-bearing eclogite. Two distinct types of garnet peridotite were identified based on mode of occurrence and petrochemical characteristics. Type A mantle-derived peridotites originated from either: (1) the mantle wedge above a subduction zone, (2) the footwall mantle of the subducted slab, or (3) were ancient mantle fragments emplaced at crustal depths prior to UHP metamorphism, whereas type B crustal peridotite and pyroxenite are a portion of mafic–ultramafic complexes that were intruded into the continental crust as magmas prior to subduction. Most type A peridotites were derived from a depleted mantle and exhibit petrochemical characteristics of mantle rocks; however, Sr and Nd isotope compositions of some peridotites have been modified by crustal contamination during subduction and/or exhumation. Type B peridotite and pyroxenite show cumulate structure, and some have experienced crustal metasomatism and contamination documented by high ⁸⁷Sr/⁸⁶Sr ratios (0.707–0.708), low ε_Nd( t ) values (−6 to −9) and low δ¹⁸O values of minerals (+2.92 to +4.52). Garnet peridotites of both types experienced multi-stage recrystallization; some of them record prograde histories. High- P–T  estimates (760–970 °C and 4.0–6.5±0.2 GPa) of peak metamorphism indicate that both mantle-derived and crustal ultramafic rocks were subducted to profound depths >100 km (the deepest may be ≥180–200 km) and experienced UHP metamorphism in a subduction zone with an extremely low geothermal gradient of <5 °C km⁻¹.     

Stable isotopic signature of a palaeoaquifer, Mississippian Alamogordo Member limestones, Sacramento Mountains, New Mexico, USA

Nine stratigraphic sections, each ≈5 m thick, were sampled from the Alamogordo Member limestones of the Lake Valley Formation, Sacramento Mountains, New Mexico, USA. Four stratigraphic sections consist entirely of lime mudstone and wackestone, whereas the other five sections have a prominent layer of crinoidal packstone about 1 m thick at their base. Stable isotopic analyses reveal that the lime muds in the sections with basal packstone layers show a downward decrease in δ¹⁸O and constant δ¹³C values, whereas those in the sections solely composed of lime mudstone and wackestone have, in general, relatively uniform δ¹⁸O and δ¹³C values. The diagenesis of the Alamogordo Member limestones was previously believed to have been governed by the downward percolation of meteoric water from a regional pre-Pennsylvanian exposure surface ≈100 m above this unit. However, the uniform δ¹³C and downward decrease in δ¹⁸O values in the lime muds in the sections with basal packstones indicate that the meteoric water ascended within the Alamogordo Member, rather than descended from the overlying exposure surface. This indicates that the basal packstones were probably a conduit for meteoric water. This is further supported indirectly by the relatively uniform δ¹⁸O and δ¹³C values of the lime mud in the sections without basal packstones. The implications are that the oxygen isotopic gradients may be used to identify palaeoaquifers, flow directions within these aquifers and that meteoric diagenesis below an exposure surface could be governed by flow through a palaeoaquifer.     

Structurally controlled fluid flow associated with breccia vein formation

A breccia vein sampled from a shear zone in greenschist facies metapelites at Mount Isa, Queensland, Australia, shows a systematic variation in vein geometry that is related to the geometry of folding and faulting within the sample. Calcite vein-fill is coarse grained and equigranular, suggesting precipitation in a fluid-filled space. Partially folded veins suggest that veining occurred during folding and faulting. The breccia vein contains a central zone in which dilation has occurred simultaneously in all directions in the plane of section, implying that this was a zone of high fluid pressure and nearly isostatic differential stress during folding and faulting. From these observations, it can be inferred that the breccia vein was a zone of high permeability and a likely fluid channel during deformation. This hypothesis was tested by stable isotope analysis of veins and host rocks. The calcite veins have δ¹³C values of -11.1 ± 0.1% and δ¹⁸O values of 6-10%_o, whereas the host metapelite has δ¹³C values of -10.62 and -10.11% and δ¹⁸O values of 14-15%_o. These values are consistent with an igneous-derived, H₂O-dominated fluid that exchanged little oxygen with the host rocks, but derived much of its carbon from the wall rock. The isotopic disequilibrium between the veins and the wall rock confirms that the fluid was externally derived, and that the breccia vein acted as a channel for large-volume fluid flow within the shear zone.     

A widespread positive δ13Ccarb anomaly at around 2.33–2.06 Ga on the Fennoscandian Shield: a paradox?

Carbon isotope measurements carried out on 201 carbonate samples from the early Proterozoic of the Kola Peninsula, N. Karelia and Norway yield δ¹³C (PDB) spanning - 20.5% to + 11%. A general δ¹³C secular trend shows that prior to 2.33 Ga values are typically 'normal' marine, averaging around - 3%0. Between 2.33 and 2.06 Ga, in Jatulian time, there follows a rapid excursion to positive δ¹³C of around + 6%. Post-Jatulian time is characterized by δ¹³C of sedimentary carbonates fluctuating between - 5% and +3%; also it is remarkable for the first pronounced development of diagenetic carbonates, which have δ¹³C between - 14 % and - 6% . The c. 6% positive δ¹³C shift with a duration of about 270 Myr coincides with a maximum in the diversity and abundance of stromatolites, and with widespread development of 'red beds', but does not coincide with the maximum of buried C_org mass. The Fennoscandian Shield represents the largest isotoically anomalous carbonate province yet reported, and the positive δ¹³C excursion together with a series of major global palaeoenviromental changes seems to be more intense than the Precambrian/Cambrian transition events. However, it is still not clear what kind of mechanism this phenomenon could be attributed to. An increase of the 'Ronov ratio', and/or 'Broecker ratio' and other possible models are discussed as the target for future investigations.     

Geochemical Process of Gas Hydrate Formation in the Nankai Trough Based on Chloride and Isotopic Anomalies in Interstitial Water

Abstract: Interstitial water expelled from gas hydrate-bearing and -free sediments in the Nankai Trough are analyzed in terms of Cl-, SO₄²-, δ¹⁸O and δD. The baselines for the Cl- concentration and δ¹⁸O value are close to seawater values (530 mM and 0%), indicating that the interstitial water is of seawater origin. The δD values decrease with depth, implying isotopic exchange of hydrogen between upwelling biogenic methane depleted in D and interstitial water. The Cl- concentrations in gas hydrate-bearing sediments are anomalously low, while the δ¹⁸O and δD values are both high, suggesting that the water forming these gas hydrates was poor in Cl- and enriched in ¹⁸O and D during gas hydrate formation. Calculation of the gas hydrate saturations using Cl "and δ¹⁸O anomalies gives results of up to 80 % in sand, and shows that the δ¹⁸O baseline is not consistent with the Cl" baseline. The δ¹⁸O baseline increases by +1% in gas hydrate-free clay and silt. This is considered to be caused by clustering of water molecules after gas hydrate dissociation in response to the upward migration of the base of gas hydrate stability, as indicated by the presence of a double bottom-simulating reflector at this site. The water clusters enriched in ¹⁸O are responsible for the increase in the δ¹⁸O baseline with normal Cl". The abrupt shallowing of the base of gas hydrate stability may induce the dissociation of gas hydrates and the accumulation of gases in the new stability zone, representing a geological process that increases gas hydrate saturation.     

Foraminiferal changes and geochemical profiles across the Cenomanian/Turonian boundary in central and south-east Poland

Two sections of the Upper Cenomanian and Lower Turonian in central and south-east Poland were investigated for foraminifers, CaCO₃content, carbon content insoluble in HCl (C_org) and in the carbonates (C_carb), carbon and oxygen isotopic composition of bulk-rock carbonates and elemental abundances. The Cenomanian/Turonian boundary interval is characterized by the appearance of more marly facies, a δ¹³C and δ¹⁸O stable isotope anomaly, a considerable increase in C_org content and decrease in C_carb content and substantial changes in the foraminiferal assemblages. A major carbon stable isotope excursion with a shift of +2 (PDB) occurs in the lowermost Whiteinella archaeocretacea Zone. The late Cenomanian δ¹³C anomaly is associated with heavy δ¹⁸O values. The peak value of δ¹³C corresponds to the minima in P/B ratio and in diversity of foraminiferal assemblages. A late Cenomanian anoxic event is thought to be responsible for changes in foraminiferal assemblages. However, elemental abundance analyses do not show changes in the concentrations of trace elements. This may be explained by the long distance between studied area and a source of enrichment which was probably located in the western hemisphere.     

江西德兴铜厂铜矿水－岩体系氢氧同位素演化

江西铜厂铜矿床露天采场岩石76个全岩氧同位素组成表明,该超大型铜矿的形成与具有5个水-岩交换成矿体系汇集在一起有关。水-岩体系计算表明,成矿流体储库形成是大气降水与千枚岩和花岗闪长斑岩在300℃以及W/R比值为0.5左右条件下形成,而后上升进入矿化沉积体系时温度降低,W/R比值超过10.0,计算的最少水量达1.9×10¹⁰t以上。     

Sulfur Isotopic Study of the Toyoha Deposit, Hokkaido, Japan Comparison between the Earlier-Stage and the Later-Stage Veins

Abstract: The sulfur isotopic ratios (δ³⁴S) of ore minerals from the Toyoha deposit, Hokkaido, one of the largest Pb–Zn–Ag polymetallic vein-type deposits in Japan, were studied. More than 90% of the δ³⁴S values of the studied sulfide minerals collected from the Toyoha deposit range from +5 to +9%, with an average of approximately +7% irrespective of the mineral species, veins, elevations, depth, mineralization stages and mineral assemblages. Relatively uniform δ³⁴S values obtained in this study suggest that the reduced aqueous sulfur species predominated over the oxidized sulfur in the ore solution throughout the mineralization stages. Thus, the source of sulfur for the ore sulfides is postulated to be magmatic.
The temperature obtained from the fluid inclusion study and the temperature of the sulfur isotopic geothermometer are not consistent. This suggests that each mineral precipitated under disequilibrated conditions with respect to the sulfur isotope.
The change in redox conditions presumably encountered between the mineralization stages did not account for the isotopic fluctuations since the isotopic exchanges between the oxidized and reduced aqueous sulfurs are much slower than the rate of oxidation of the ore solution.     

Refinements in BaSO4 to CO2 Preparation and δ18 O Calibration of the Sulfate Reference Materials NBS-127, IAEA SO-5 and IAEA SO-6

Refinements have been made to achieve over 99% yield in the conversion of CO to CO₂ in order to improve the reproducibility and accuracy of δ¹⁸ O measurements in sulfates. BaSO₄ (10-15 mg) was mixed with an identical amount of spectrographic-grade graphite and loaded into a Pt boat. The mixture was gradually heated to 1100 °C to reduce sulfate to CO and CO₂; the former gas was simultaneously converted to CO₂ by a glow discharge between Pt electrodes immersed in a magnetic field (produced by a pair of external neodymium magnets). A small memory effect was noticed during the analysis (less than 0.3‰ per 10‰ difference in δ¹⁸ O between two subsequently analysed samples). The memory effect, however, was suppressed by repetitive preparation of the same specimen. CO₂ produced in this way from sulfate reference samples was analysed on a dual inlet and triple collector mass spectrometer along with CO₂ equilibrated with VSMOW, GISP and SLAP water reference samples. To avoid large departures of measured isotope ratios from ¹⁸O/¹⁶O of the working calibrator we used CO₂ gas prepared from ocean water sulfate for this purpose. The calibrated δ¹⁸ O values (in ‰) obtained in this way for NBS-127, IAEA SO-5 and IAEA SO-6 reference materials were 8.73 ± 0.05, 12.20 ± 0.07 and -10.43 ± 0.12, respectively.     

Hydrogen, Oxygen and Sulfur Isotope Studies of Seafloor Hydrothermal System at the Desmos Caldera, Manus Back-arc Basin, Papua New Guinea: An Analogue of Terrestrial Acid Hot Crater-lake

Abstract. The Onsen site is an active submarine hydrothermal system hosted by the Desmos caldera in the Eastern Manus Basin, Papua New Guinea. The hydrothermal fluid is very acidic (pH=1.5) and abundant native sulfur is deposited around the vent. The δ³⁴S values of native sulfur range from -6.5 to -9.3 %o. δ³⁴S values of H₂S and SO₄ in the hydrothermal fluid are -4.3 to -9.9 %o and +18.6 to +20.0 %o, respectively. These δ³⁴S values are significantly lower than those of the other hydrothermal systems so far reported. These low δ³⁴S values and the acidic nature of the vent fluids suggest that volcanic SO₂ gas plays an important role on the sulfur isotope systematic of the Onsen hydrothermal system. Relationship among the δ³⁴S values of S-bearing species can be successively explained by the model based on the disproportionation reaction starting from the volcanic SO₂ gas. The predicted δ³⁴S values of SO₂ agree with the measured whole rock δ³⁴S values. δD and δ¹⁸O values of clay minerals separated from the altered rock samples also suggest the contribution of the magmatic fluid to the hydrothermal system. Present stable isotopic study strongly suggests that the Onsen hydrothermal site in the Desmos caldera is a magmatic submarine hydrothermal system.     

The isotopic composition of oxygen and carbon in the subfossil mollusc shells of the Baltic Sea as an indicator of palaeosalinity

The carbon (δ¹³ C) and oxygen (δ¹⁸O) isotopic composistion in mollusc shells in mainly determined by the isotopic composition of water and dissolved bicarbonate. The δ¹⁸O values of water show a good correlation with the salinity of the Baltic. This correlation served as a basis for reconstructing palaeosalinity and for stratifying the marine sediments according to the δ¹⁸O values of the carbonate skeletons of subfossil shells. The δ¹³C values in shells are mainly determined by the isotopic composition of land-originating bicarbonate, especially in the carbonate skeleton of Lymnaea balthica , which inhabits the immediate coastal zone. According to the δ¹⁸O data, salinity in the investigated area (the coastal area of W and NW Estonia) was highest (about 9–11%) during the Littorina stage. The Limnae a stage had, in general, a salinity similar to the contemporary one, but during some phases possibly exceeding it by 2–3%.     

Active skarn formation beneath Lascar Volcano, northern Chile: a petrographic and geochemical study of xenoliths in eruption products

Calcsilicate xenoliths occur in large numbers in some lavas and pyroclastic flows of Lascar Volcano. Their whole-rock major element and REE compositions indicate that the protolith was the Upper Cretaceous Yacoraite Formation, which crops out extensively in NW Argentina. The whole-rock major element compositions of the xenoliths fall into specific groups suggesting a strong geochemical zonation in the skarn zone. Three geochemical zones have been identified; (1) an outer metamorphic zone rich in wollastonite; (2) a middle zone rich in pyroxene and garnet; (3) an inner zone rich in pyroxene and magnetite. The two innermost zones have developed from the wollastonite zone by infiltration of metasomatic fluids rich in Fe, Mn, Mg, Ti and Al. Whole-rock REE patterns have not changed significantly during prograde metamorphism and metasomatism, indicating REE immobility in the altering fluids. Retrograde alteration by acid-sulphate fluids produced anhydrite skarns and secondary calcite and wilkeite veins in the wollastonite zone. The carbon and oxygen isotopic compositions of this calcite indicate that it formed by Rayleigh crystallization from a low-temperature (<200 °C) fluid containing dissolved H₂CO₃. The calculated δ¹⁸O of the water in this fluid suggests a magmatic origin whereas the calculated δ¹³C of the dissolved carbonate is consistent with derivation from rocks of the Yacoraite Formation at 350 °C. It is suggested that the magmatic acid-sulphate fluid was responsible for leaching carbonate from the surrounding carbonate rocks and redepositing it in the skarn zone. REEs were mobilized during the retrograde acid-sulphate and acid-carbonate alteration. A negative Ce anomaly associated with this carbonate and sulphate indicates high oxygen fugacities in the mineralizing fluids.