Hydrogen and oxygen isotope evidence for fluid–rock interactions in the stages of pre- and post-UHP metamorphism in the Dabie Mountains

Hydrogen and oxygen isotope studies were carried out on high and ultrahigh pressure metamorphic rocks in the eastern Dabie Mountains, China. The δ¹⁸O values of eclogites cover a wide range of −4.2 to +8.8‰, but the δD values of micas from the eclogites fall within a narrow range of −87 to −71‰. Both equilibrium and disequilibrium oxygen isotope fractionations were observed between quartz and the other minerals, with reversed fractionations between omphacite and garnet in some eclogite samples. The δ¹⁸O values of −4 to −1‰ for some of the eclogites represent the oxygen isotope compositions of their protoliths which underwent meteoric water–rock interaction before the high to ultrahigh pressure metamorphism. Heterogeneous δ¹⁸O values for the eclogite protoliths implies not only the varying degrees of the water–rock interaction before the metamorphism at different localities, but also the channelized flow of fluids during progressive metamorphism due to rapid plate subduction. Retrograde metamorphism caused oxygen and hydrogen isotope disequilibria between some of the minerals, but the fluid for retrograde reactions was internally buffered in the stable isotope compositions and could be derived from structural hydroxyls dissolved in nominally anhydrous minerals.     

C, O, S and Sr isotope studies on the genesis of Fe-carbonate and barite mineralizations in the Attepe iron district (Adana, Southern Turkey)

The Attepe district consists of Precambrian, Lower–Middle Cambrian, Upper Cambrian–Lower Ordovician and Mesozoic formations. It contains several iron deposits and occurrences. Three types of iron-mineralizations can be distinguished in the area; (i) Sedimentary Fe-sulfide in Precambrian bituminous metapelitic rocks, and Fe-oxides in Precambrian metasandstones (SISO), (ii) vein-type Fe-carbonate and oxides composed of mainly siderite, ankerite and hematite including barite in Lower–Middle Cambrian metacarbonates of the Çaltepe Formation (HICO), (iii) karstic Fe-oxides and hydroxides essentially in the Lower–Middle Cambrian metacarbonates and the unweathered Fe-carbonates (KIO). The latter type is more widespread and located at the upper parts of the most important mineable iron deposits like Attepe deposit.

Oxygen-, carbon-, sulfur- and strontium-isotope studies have been performed on siderites and barites in the vein-type ores, and on calcites in the recrystallized Çaltepe Limestones to investigate the sources and formation mechanism of primary ore-forming constituents. The δ¹³C values of siderites and calcites in limestones of the Çaltepe Formation range from −10.10‰ to −8.20‰, and from −0.8‰ to 2.30‰. Both carbonate minerals show δ¹⁸O values between 17.50–18.30‰ and 16.20–23.00‰, respectively. The δ¹³C and δ¹⁸O isotopic variations do not indicate any direct or linear relations between siderites and limestones. However, it is possible that the carbon and oxygen isotopic compositions of carbonate minerals could be changed to some extent, when limestones were subjected to hydrothermal processes or thermal alterations during metamorphism.

The isotopic values of barites display 32.40–38.30‰ for δ³⁴S and 12.20–14.70‰ for δ¹⁸O. The strontium isotope ratios (0.717169–0.718601) of barites and the sulfur isotope compositions of barites and pyrites suggest that there are no direct linkages of ore-forming compounds neither with a magmatic source nor with sedimentary pyrite formations in the Precambrian bituminous shales of the Attepe formation.

According to the field observations and the stable isotope data, siderites and ankerites should be formed by interaction between iron-rich hydrothermal fluids and Çaltepe limestones, whereas isotope ratios of barites indicate that they were formed by mixing of sulfur-rich meteoric waters and deeply circulated hydrothermal solutions.     

Fluid evolution in the W–Cu–Zn–Pb San Cristobal vein, Peru: fluid inclusion and stable isotope evidence

The Zn–Pb±Ag±Cu San Cristobal district is located 100 km east of Lima in the western cordillera of Peru. It is centred around the Chumpe intrusion and is composed of vein and carbonate replacement ore types. The main San Cristobal vein presents a paragenesis that can be divided into three stages: (a) an early wolframite–quartz–pyrite stage, (b) a quartz–base metal stage, and (c) a late quartz–carbonate–barite stage.

Fluid inclusions in quartz from the tungsten stage are biphase (LV) at room temperature and homogenise to the liquid phase between 146 and 257 °C. Their salinities range between 2.1 and 5.1 wt.% NaCl equiv. Rare inclusions contain an additional crystal of halite and have salinities of 46–54 wt.% NaCl equiv. Data of the first two stages show a decrease in homogenisation temperatures concomitant with a salinity decline. Fluid inclusions in quartz from the late stage homogenise at higher temperatures, between 252 and 323 °C, with salinities ranging between 4.6 and 6.7 wt.% NaCl equiv.

Hydrogen and oxygen isotope data indicate a two-stage evolution. Isotopic compositions of the fluid associated with the first two stages define a trend with constant δ¹⁸O values and decreasing δD values (δ¹⁸O=3.2‰ to 5.0‰ V-SMOW and δD=−60‰ to −112‰ V-SMOW), which is interpreted as mixing of a dominantly magmatic component with minor meteoric water that had equilibrated with the host rocks. This interpretation is supported by sulphur and lead isotopic data from previous studies. By contrast, the quartz–carbonate–barite stage bears isotopic characteristics defining a trend with a coupled decrease of δ¹⁸O and δD (δ¹⁸O=−8.1‰ to 2.5‰ V-SMOW and δD=−57‰ to −91‰ V-SMOW) and is explained by addition of meteoric water to the system and subsequent mixing with a less important magmatic component.

Different fluid origins are confirmed by laser ablation ICP-MS analyses of the triphase (LVH) and biphase (LV) primary inclusions. The concentrations of the major ore elements, i.e., W, Cu, Zn and Pb, decrease throughout the paragenesis; W, and to a lesser extent Cu, show significant variations, associated with a steep decrease in their concentration. The decreasing concentrations can be explained by mineral deposition and dilution by the meteoric fluid; differences in the rate of decrease indicate selective precipitation of W. Fluid inclusions of the quartz–carbonate stages show an abrupt increase in Ba and Sr concentrations. This is interpreted to reflect a higher volume of host rock silicate alteration, probably due to the increasing size of the fluid flow cell and is explained by the input of a third fluid of unknown origin. LA-ICP-MS analyses show that the fluids were already depleted in W and Cu before reaching the emplacement of carbonate replacement ore type, whereas Zn and Pb were still present in considerable amounts. This is again due to selective precipitation and is consistent with the interpretation that the economically interesting metals were dominantly introduced by magmatic fluids.     

Post-collisional granitoids from the Dabie orogen in China: Zircon U–Pb age, element and O isotope evidence for recycling of subducted continental crust

While recycling of subducted oceanic crust is widely proposed to be associated with oceanic island, island arc, and subduction-related adakite magmatism, it is less clear whether recycling of subducted continental crust takes place in continental collision belts. A combined study of zircon U–Pb dating, major and minor element geochemistry, and O isotopes in Early Cretaceous post-collisional granitoids from the Dabie orogen in China demonstrates that they may have been generated by partial melting of subducted continental crust. The post-collisional granitoids from the Dabie orogen comprise hornblende-bearing intermediate rocks and hornblende-free granitic rocks. These granitoids are characterized by fractionated REE patterns with low HREE contents and negative HFSE anomalies (Nb, Ta and Ti). Although zircon U–Pb dating gives consistent ages of 120 to 130 Ma for magma crystallization, occurrence of inherited cores is identified by CL imaging and SHRIMP U–Pb dating; some zircon grains yield ages of 739 to 749 Ma and 214 to 249 Ma, in agreement with Neoproterozoic protolith ages of UHP metaigneous rocks and a Triassic tectono-metamorphic event in the Dabie–Sulu orogenic belt, respectively. The granitoids have relatively homogeneous zircon δ¹⁸O values from 4.14‰ to 6.11‰ with an average of 5.10‰ ± 0.42‰ (n = 28) similar to normal mantle zircon. Systematically low zircon δ¹⁸O values for most of the coeval mafic–ultramafic rocks and intruded country rocks preclude an AFC process of mafic magma or mixing between mafic and felsic magma as potential mechanisms for the petrogenesis of the granitoids. Along with zircon U–Pb ages and element results, it is inferred that the granitic rocks were probably derived from partial melting of intermediate lower crust and the intermediate rocks were generated by amphibole-dehydration melting of mafic rocks in the thickened lower crust, coupled with fractional crystallization during magma emplacement. The post-collisional granitoids in the Dabie orogen are interpreted to originate from recycling of the subducted Yangtze continental crust that was thickened by the Triassic continent–continent collision. Partial melting of orogenic lithospheric keel is suggested to have generated the bimodal igneous rocks with the similar crustal heritage. Crustal thinning by post-collisional detachment postdated the onset of bimodal magmatism that was initiated by a thermal pulse related to mantle superwelling in Early Cretaceous.     

Oxygen and carbon isotope composition of cold-water Berriedale Limestone (Lower Permian), Tasmania, Australia

The Berriedale Limestone formed at about 80°S paleolatitude and contains many glacial dropstones. It formed during a period of major Gondwana deglaciation.

The Berriedale Limestone contains mostly bryozoans, brachiopods and bivalves, with some intraclasts and rare pellets. The faunal diversity is low and the fauna are similar to the modern cold-water foramol faunal assemblage. Micrite, microspar and spar occur as equant to well developed rhombs of calcite. The coarse spar cements are bored and are ruptured by dropstones, indicating submarine origin of low-Mg calcite at water-temperatures of around 3°C. The mixing zone cementation was preceded by erosion of early formed crystals. The eroded crystals occur as inclusions in mixing zone cements.

The fauna are characterized by heavy δ¹³C and light δ¹⁸O. The whole-rock field of δ¹⁸O-δ¹³C falls at the edge of “Normal Marine Limestone” and deviates to lighter δ¹⁸O values (down to −16.7‰ PDB). Lightest δ¹⁸O values ( −22‰ PDB) of fresh-water sparry calcite cement are similar to those in the Early Permian continental tillites, suggesting that the Permian sea was diluted by isotopically light melt waters. Micrite δ¹⁸O values (−9.2 to −12.6‰ PDB) are within the range of whole-rock values. The δ¹⁸O values of calcite in shales are lighter than limestone values.

The δ¹⁸O values of the fauna give an unrealistic range of sea-water temperatures because the fauna have equilibrated with variable amounts of melt waters. However, calculated original δ¹⁸O values of the fauna indicate temperatures < 4°C. The heaviest δ¹⁸O of fauna gives cold temperatures of 9°C (with δ_w −2.8‰) and −3°C (with δ_w −6‰). The lightest values of sparry calcite cements (−22‰ PDB) indicate that the limestone reacted with cold melt waters.

The δ¹⁸O of Permian sea is estimated to be about +1.2‰ and was diluted by melt waters as light as −27‰ SMOW.     

Interrelations between coeval mafic and A-type silicic magmas from composite dykes in a bimodal suite of southern Israel, northernmost Arabian–Nubian Shield: Geochemical and isotope constraints

Late Neoproterozoic bimodal dyke suites are abundant in the Arabian–Nubian Shield. In southern Israel this suite includes dominant alkaline quartz porphyry dykes, rare mafic dykes, and numerous composite dykes with felsic interiors and mafic margins. The quartz porphyry chemically corresponds to A-type granite. Composite dykes with either abrupt or gradational contacts between the felsic and mafic rocks bear field, petrographic and chemical evidence for coexistence and mixing of basaltic and rhyolitic magmas. Mixing and formation of hybrid intermediate magmas commenced at depth and continued during emplacement of the dykes. Oxygen isotope ratios of alkali feldspar in quartz porphyry (13 to 15‰) and of plagioclase in trachydolerite (10–11‰) are much higher than their initial magmatic ratios predicted by equilibrium with unaltered quartz (8 to 9‰) and clinopyroxene (5.8‰). The elevation of δ¹⁸O in alkali feldspar and plagioclase, and extensive turbidization and sericitization call for post-magmatic low-temperature (≤ 100 °C) water–rock interaction. Hydrous alteration of alkali feldspar, the major carrier of Rb and Sr in the quartz–porphyry, also accounts for the highly variable and unusually high I(Sr) of 0.71253 to 0.73648.

The initial ¹⁴³Nd/¹⁴⁴Nd ratios, expressed by ε_Nd(T) values, are probably unaltered and show small variation in mafic and felsic rocks within a narrow range from + 1.4 to + 3.3. The Nd isotope signature suggests either a common mantle source for the mafic and silicic magmas or a juvenile crustal source for the felsic rocks (metamorphic rocks from the Elat area). However, oxygen isotope ratios of zircon in quartz porphyry [δ¹⁸O(Zrn) = 6.5 to 7.2‰] reveal significant crustal contribution to the rhyolite magma, suggesting that mafic and A-type silicic magmas are not co-genetic, although coeval. Comparison of ¹⁸O/¹⁶O ratios in zircon allows to distinguish two groups of A-type granites in the region: those with mantle-derived source, δ¹⁸O(Zrn) ranging from 5.5 to 5.8‰ (Timna and Katharina granitoids) and those with major contribution of the modified juvenile crustal component, δ¹⁸O(Zrn) varying from 6.5 to 7.2‰ (Elat quartz porphyry dykes and the Yehoshafat alkaline granite). This suggests that A-type silicic magmas in the northern ANS originated by alternative processes almost coevally.     

Inclusions in diamonds from the K14 and K10 kimberlites, Buffalo Hills, Alberta, Canada: diamond growth in a plume?

Analyses of mineral inclusions, carbon isotopes, nitrogen contents and nitrogen aggregation states in 29 diamonds from two Buffalo Hills kimberlites in northern Alberta, Canada were conducted. From 25 inclusion bearing diamonds, the following paragenetic abundances were found: peridotitic (48%), eclogitic (32%), eclogitic/websteritic (8%), websteritic (4%), ultradeep? (4%) and unknown (4%). Diamonds containing mineral inclusions of ferropericlase, and mixed eclogitic-asthenospheric-websteritic and eclogitic-websteritic mineral associations suggests the possibility of diamond growth over a range of depths and in a variety of mantle environments (lithosphere, asthenosphere and possibly lower mantle).

Eclogitic diamonds have a broad range of C-isotopic composition (δ¹³C=−21‰ to −5‰). Peridotitic, websteritic and ultradeep diamonds have typical mantle C-isotope values (δ¹³C=−4.9‰ av.), except for two ¹³C-depleted peridotitic (δ¹³C=−11.8‰, −14.6‰) and one ¹³C-depleted websteritic diamond (δ¹³C=−11.9‰). Infrared spectra from 29 diamonds identified two diamond groups: 75% are nitrogen-free (Type II) or have fully aggregated nitrogen defects (Type IaB) with platelet degradation and low to moderate nitrogen contents (av. 330 ppm-N); 25% have lower nitrogen aggregation states and higher nitrogen contents (30% IaB; <1600 ppm-N).

The combined evidence suggests two generations of diamond growth. Type II and Type IaB diamonds with ultradeep, peridotitic, eclogitic and websteritic inclusions crystallised from eclogitic and peridotitic rocks while moving in a dynamic environment from the asthenosphere and possibly the lower mantle to the base of the lithosphere. Mechanisms for diamond movement through the mantle could be by mantle convection, or an ascending plume. The interaction of partial melts with eclogitic and peridotitic lithologies may have produced the intermediate websteritic inclusion compositions, and can explain diamonds of mixed parageneses, and the overlap in C-isotope values between parageneses. Strong deformation and extremely high nitrogen aggregation states in some diamonds may indicate high mantle storage temperatures and strain in the diamond growth environment. A second diamond group, with Type IaA–IaB nitrogen aggregation and peridotitic inclusions, crystallised at the base of the cratonic lithosphere. All diamonds were subsequently sampled by kimberlites and transported to the Earth's surface.     

Petrogenesis of the Maowu pyroxenite–eclogite body from the UHP metamorphic terrane of Dabieshan: chemical and isotopic constraints

The Maowu eclogite–pyroxenite body is a small (250×50 m) layered intrusion that occurs in the ultra-high-pressure (UHP) metamorphic terrane of Dabieshan, China. Like the adjacent Bixiling complex, the Maowu intrusion was initially emplaced at a crustal level, then subducted along with the country gneisses to mantle depths and underwent UHP metamorphism during the collision of the North and South China Blocks in the Triassic. This paper presents the results of a geochemical and isotopic investigation on the metamorphosed Maowu body. The Maowu intrusion has undergone open system chemical and isotopic behavior three times. Early crustal contamination during magmatic differentiation is manifested by high initial ⁸⁷Sr/⁸⁶Sr ratios (0.707–0.708) and inhomogeneous negative _Nd(T) values of −3 to −10 at 500 Ma (probable protolith age). Post-magmatic and pre-UHP metamorphic metasomatism is indicated by sinusoidal REE patterns of garnet orthopyroxenites, lack of whole-rock (WR) Sm–Nd isochronal relationship, low δ¹⁸O values and an extreme enrichment of Th and REE in a clinopyroxenite. Finally, K and Rb depletion during UHP metamorphism is deduced from the high initial ⁸⁷Sr/⁸⁶Sr ratios unsupported by in situ Rb/Sr ratios. Laser ICP-MS spot analyses on mineral grains show that (1) Grt and Cpx attained chemical equilibrium during UHP metamorphism, (2) Cpx/Grt partition coefficients for REE correlate with Ca, and (3) LREE abundances in whole rocks are not balanced by that of the principal phases (Grt and Cpx), implying that the presence of LREE-rich accessory phases, such as monazite and apatite, is required to account for the REE budget.

Sm–Nd isotope analyses of minerals yielded three internal isochrons with ages of 221±5 Ma and (T)=−5.4 for an eclogite, 231±16 Ma and (T)=−6.2 for a garnet websterite, and 236±19 Ma and (T)=−6.9 for a garnet clinopyroxenite. The Cpx/Grt chemical equilibrium and the consistent mineral isochron ages indicate that the metasomatic processes mentioned above must have occurred prior to the UHP metamorphism. These Sm–Nd ages agree with published zircon and monazite U–Pb ages and constrain the time of UHP metamorphism to 220–236 Ma. The Maowu and Bixiling layered intrusions are similar in their in situ tectonic relationship with their country gneisses, but the two bodies are distinguished by their magma-chamber processes. The Bixiling magmas were contaminated by the lower crust, whereas the Maowu magmas were contaminated by the upper crustal rocks during their emplacement and differentiation. The two complexes represent two distinct suites of magmatic rocks, which have resided in the continental crust for about 300–400 Ma before their ultimate subduction to mantle depths, UHP metamorphism and return to the crustal level.     

Crystalline inclusions and C isotope ratios in diamonds from the Snap Lake/King Lake kimberlite dyke system: evidence of ultradeep and enriched lithospheric mantle

U-type paragenesis inclusions predominate (94.7%) among the crystalline inclusion suite of 115 diamonds (−4+2 mm) obtained from the recently discovered Snap Lake/King Lake (SKL) kimberlite dyke system, Southern Slave, Canada. The most common inclusions are olivine (90) and enstatite (22). Sulfide, Cr-pyrope, chromite and Cr-diopside inclusion are less abundant (15, 10, 5 and 1, respectively). Results of the inclusion composition study demonstrate the following. (a) The relatively enriched character of the mantle parent rocks of the U-type diamonds. The average Mg# of olivine inclusions is 92.1, and of enstatite inclusions average 93.3. CaO content in Cr-pyrope inclusions is relatively high (3.73–5.75 wt.%). (b) Four of ten U-type Cr-rich pyrope inclusions contain a majoritic component up to 16.8 mol.% which requires pressures of 110 kbar. Carbon isotopes compositions for 34 diamonds with U-type inclusions have a δ¹³C range from −3.2‰ to −9‰ with a strong peak around −3.5‰. This is much heavier than the ratios of U-type diamonds from Siberia and South Africa (4.5‰). Diamonds with olivine inclusions can be divided into two groups based on their δ¹³C values as well as the Mg# and Ni/Fe ratio in the olivines. Most show a narrow range of δ¹³C values from −3.2‰ to −4.8‰ (average −3.72‰) and have olivine inclusions with Mg# less than 92.3 and relatively high Fe/Ni ratios. A second group is characterized by a much wider variation of C isotope composition (δ¹³C varies from −3.8‰ to −9.0‰, average −5.97‰), and the olivine inclusions having a higher Mg# (up to 93.6) and relatively low Fe/Ni ratios. This difference in the C isotope composition may have several explanations: (a) peculiarities of asthenosphere degassing coupled with an abnormal thickness of lithosphere; (b) the abnormal thickness and enriched character of lithospheric mantle; (c) involvement of subducted C of crustal origin in the processes of the diamond formation. The presence of subcalcic Cr-rich majorite (up to 17 mol.%) pyropes of low-Ca harzburgite paragenesis among the crystalline inclusion suite of SKL diamonds is strong evidence for the existence of diamondiferous depleted peridotite in lithospheric mantle at depth near 300 km beneath Southern Slave area and is postulated to be one of the main reasons for the much heavier C isotope composition of SKL U-type diamonds in comparison with those from Siberian and South African kimberlites.     

Stable isotope geochemistry of marbles from the coesite UHP terrains of Dabieshan and Sulu, China

Marbles from Dabieshan and Sulu, China, suffered ultra high pressure (UHP) metamorphism in the coesite–eclogite facies at approximately 700°C and 30 kbars during Triassic continental collision and subduction. The marbles range in isotopic composition from +7 to +25 δ¹⁸O_VSMOW and from 0 to +6 δ¹³C_VPDB. High δ¹³C values are representative of unmodified protoliths and are similar to those of ¹³C-enriched Sinian carbonate rocks from the Yangtze craton. High oxygen isotope ratios reflect pristine protoliths but the low values may have been caused by infiltration of low ¹⁸O meteoric water during diagenesis and dolomitization, by fracture-controlled infiltration of water during subduction, by metamorphic mineral reactions, or by a combination of these processes. No evidence of regional isotopic transport during UHP metamorphism has been found. Sampling on scales of 1 to 100 m shows marbles to be inhomogeneous in both carbon and oxygen isotopes. Only samples separated by less than 10 cm have equilibrated oxygen and carbon isotope compositions. Limited isotopic equilibration between adjacent rocks is consistent with the preservation of unaltered UHP minerals and indicates that the metamorphic fluid–rock system was rock-dominated during and following peak metamorphism. A freely flowing, pervasive fluid phase was not present during UHP metamorphism. There is no evidence of isotopic exchange between marble and the upper mantle into which it was subducted. Correlation of geochemical similarities of UHP marbles with Sinian limestones implies that the subducted edge of the Yangtze craton extends at least as far north as the coesite–eclogite facies rocks of Dabieshan. Deposition of protolith carbonates may have taken place in a cold climate either preceding or following but not coincident with Neoproterozoic glaciation.     

Cenozoic “radiobarite” occurrences in the Ohře (Eger) Rift, Bohemian Massif: Mineralogical and geochemical revision

Barite occurrences related to the Cenozoic (Late Alpine) low-temperature hydrothermal activity are present in the continental Ohře (Eger) Rift area. A specific, Ra-bearing type of barite has been known under the name “radiobarite” from this area since 1904. Revision of 12 localities revealed the presence of alleged radiobarite only in the Teplice (Lahošť–Jeníkov) and Karlovy Vary areas. Barite from other localities is radium-poor. Barite crystals showing concentric oscillation colour zoning totally prevail. Isomorphous substitution of Sr (X×10⁻¹ to X×wt%), Ca (X×10⁻² wt%) and Fe (X×10⁻¹ wt%) for Ba was proved. Average SrO contents of 0.4 wt% are markedly exceeded in some samples from Lahošť–Jeníkov (max. 3.2 wt%) and Karlovy Vary (max. 4.9 wt%). Besides inclusions of stoichiometric iron disulphide, the same samples also contain iron disulphides with unusual high contents of Co (max. 12.2 wt%) and Ni (max. to 8.4 wt%). Specific activity of ²³⁸U in the studied barites is very low while that of ²²⁶Ra reaches 8 Bq/g in several samples. Therefore, ²²⁶Ra is not in equilibrium with its parent uranium. These “radiobarites” or their parts must be therefore relatively young, not older than 10–15 ka. Very low uranium contents (<0.4 ppm) were also confirmed by neutron activation analyses of barite samples.

Unit-cell dimensions refined from X-ray powder diffraction data do not show any systematic variation with the measured chemical composition. Their values agree with the data given in the literature. Reflection half-widths, however, seem to correlate with chemistry. Peaks are wider in samples from Lahošť–Jeníkov and Karlovy Vary.

Sulphur and oxygen stable isotope compositions of the Cenozoic barite mineralization of Teplice area are very uniform (δ³⁴S values between 3.9‰ and 7.1‰ CDT, and δ¹⁸O values between 6.1‰ and 7.7‰ SMOW), while the barites of Děc˘ín area show more variable sulphur sources. Sulphate derived from sediments of the Tertiary Most Basin seems to dominate for the Teplice area, while Cretaceous sediments are a more probable sulphur source in the Děc˘ín area. Calculation of oxygen isotope composition of hydrothermal fluids based on fluid inclusion homogenization temperatures and barite δ¹⁸O data shows δ¹⁸O_fluid values in the range of meteoric waters or δ¹⁸O – shifted deep circulating meteoric or basinal waters.     

Stable isotope studies and processes of carbonate formation in Hungarian alkali basalts and lamprophyres: evolution of magmatic fluids and magma-sediment interactions

Processes of carbonate formation have been related to C and O isotopic compositions in the Mesozoic alkali basalt (Mecsek Mts.) and lamprophyre (Transdanubian Range) suites of Hungary. In the studied magrnatic rocks, carbonates are present as ocelli, amygdales, xenoliths, veins and groundmass carbonate. C and O isotope studies of these types of carbonate have yielded information on the origin of the carbonates and indicated the following processes of formation that determined the δ¹³C and δ¹⁸O values of the carbonates:(1)Crystallization of magmatic carbonate. Textural characteristics and δ¹³C values suggest formation of magmatic carbonate in alkali basalt and lamprophyre dikes, whereas the δ¹⁸O compositions of these carbonates indicate low temperature oxygen isotope exchange with magmatic fluids.(2) Assimilation of sedimentary carbonate by silicate magmas. Even completely recrystallized amygdales and ocelli of basalts and lamprophyres have preserved their sedimentary δ¹³C values. In contrast, variations in the extent of mobilization and isotope exchange with magmatic fluids are reflected in differences in the ranges of the δ¹⁸O values of amygdales, ocelli and veins, and can be attributed to different amounts of fluids involved in the magmatic events.(3) Low temperature alteration of magmatic rocks caused only ¹⁸O-enrichment in the carbonate amygdales of basalts and the groundmass carbonates of lamprophyres, indicating that no externally-derived CO₂ was present in the alteration fluids.(4) Degassing of magma and magmatic fluid. Correlations between δ¹³C and δ¹⁸O data, magma crystallization depths and amygdale sizes in the alkali basalts suggest that CO₂ degassing has been responsible for the negative δ¹³C and positive δ¹⁸O shifts observed. A similar trend was found in the lamprophyres, but the extent of the δ¹⁸O shift indicates that in these rocks H₂O degassing also played an important role.     

Oxygen, carbon, and strontium isotope geochemistry of diamond-bearing carbonate rocks from Kumdy-Kol, Kokchetav Massif, Kazakhstan

Diamond-bearing carbonate rocks from Kumdy-Kol, Kokchetav massif, Kazakhstan, were strongly altered by fluids flowing through fractures and infiltrating along grain boundaries during exhumation. Alteration includes retrogradation of high-grade silicate assemblages by hydrous minerals, replacement of diamond by graphite and of dolomite by calcite. Diamond-bearing carbonate rocks are among the most intensely altered isotopically with δ¹⁸O_VSMOW values as low as +9‰, δ¹³C_VPDB=−9‰, and ⁸⁷Sr/⁸⁶Sr as high as 0.8050. Evidence of isotopic equilibration between coexisting dolomite and high-Mg calcite during ultrahigh-pressure metamorphism (UHPM) is preserved only rarely in samples isolated from infiltrating fluids by distance from fractures. Isotopic heterogeneity and isotopic disequilibrium are widespread on a hand-specimen scale. Because of this lack of homogeneity, bulk analyses cannot provide definitive measurements of ¹³C/¹²C fractionation between coexisting diamond and carbonate. Our study adequately documents alteration on a scale commensurate with observed vein structures. But, testing the hypothesis of metamorphic origin of microdiamonds has not fully succeeded because our analytical spatial resolution, limited to 0.5 mm, is not small enough to measure individual dolomite inclusions or individual diamond crystals.     

Constraining diamond metasomatic growth using C- and N-stable isotopes: examples from Namibia

The present paper provides C- and N-stable isotope characteristics, N-contents and N-aggregation states for alluvial diamonds of known paragenesis from placers along the Namibian coast. The sample set includes diamonds with typical peridotitic and eclogitic inclusions and the recently reported “undetermined” suite of Leost et al. [Contrib. Mineral. Petrol. 145 (2003) 15] which resulted from infiltration of high temperature, carbonate-rich melts. δ¹³C-values range from −20.3‰ to −0.5‰ (n=48) for peridotitic diamonds and from −38.5‰ to −1.6‰ (n=45) for eclogitic diamonds. Diamonds belonging to the “undetermined” suite span a narrower range in δ¹³C from −8.5‰ to −2.7‰ (n=13). When compared with previous studies, diamonds from Namibia are characterised by unusually low proportions of N-free (i.e. Type II) peridotitic and eclogitic diamonds (3% and 2%, respectively) and an unprecedented high proportion of N-rich diamonds (15% and 73%, respectively, have N-contents >600 ppm). δ¹⁵N-values for diamonds of the peridotitic, eclogitic and “undetermined” suites range from −10‰ to +13‰ without correlations with either N-content or δ¹³C. The similarity in N-isotopic composition and the N-rich character of diamonds belonging to the eclogitic, peridotitic and “undetermined” suites is striking and suggests a close genetic relationship. We propose that a large part of the diamonds mined in Namibia formed during metasomatic events of similar style that introduced carbon and nitrogen into a range of different host lithologies.     

New insights into the occurrence of C-depleted carbon in the mantle from two closely associated kimberlites: Letlhakane and Orapa, Botswana

Carbon isotope measurements on diamonds from the Letlhakane kimberlite, and the analyses of their inclusions, permit the examination of km-scale mantle-composition variations by comparing the results with those for the nearby Orapa kimberlite. Diamonds from Letlhakane have a wide range in carbon isotopic composition (−3‰ to −21‰); however, the relative abundance of diamonds depleted in ¹³C is significantly lower than in the Orapa kimberlite. Most of the ¹³C-depleted diamonds belong to the eclogictic or websteritic paragenesis. The relative abundance of inclusions in diamonds and their composition indicate that there are significant differences in petrology in the mantle below the two locations. At Letlhakane, peridotitic compositions are more prevalent than at Orapa and the protolith of P-Type inclusions in diamonds may have experienced a higher degree of partial melting at Letlhakane compared to Orapa. P/T estimates for both W- and E-Type diamonds indicate that a region of ¹³C-depletion may exist beneath the two kimberlites. The relationships between carbon isotopic composition of the host diamond and the Al₂O₃/Cr₂O₃ ratios of their websteritic and eclogitic garnet inclusions indicate that the low δ¹³C regions may represent a primary mantle feature, unrelated to a crustal component.     

Neo-Proterozoic rift-related syenites (Northern Damara Belt, Namibia): Geochemical and Nd–Sr–Pb–O isotope constraints for mantle sources and petrogenesis

Major element, trace element and Nd–Sr–Pb–O isotope data for a suite of Neo-Proterozic, pre-orogenic, rift-related syenites from the Northern Damara orogen (Namibia) constrain their sources and petrogenesis. New U–Pb ages obtained on euhdreal titanite of inferred magmatic origin constrain the age of intrusion of the Lofdal and Oas syenites to ca. 750 Ma compatible with previous high-precision zircon analyses from the Oas complex. Major rock types from Lofdal and Oas are mildly sodic nepheline-normative and quartz-normative syenites and were primarily generated by fractional crystallization from a mantle-derived alkaline magma. Primitive samples from Lofdal and Oas show depletion of Rb, K and Th relative to Ba and Nb together with variable negative anomalies of P and Ti on a primitive mantle-normalized diagram. Evolved samples from Oas develop significant negative Ba, Sr, P and Ti anomalies and positive U and Th anomalies mainly as a function of crystal fractionation processes. The lack of a pronounced negative Nb anomaly in samples from Lofdal suggests that involvement of a crustal component is negligible. For the nepheline-normative samples from Lofdal, the unradiogenic Sr and radiogenic Nd isotope composition and low δ¹⁸O values suggest derivation of these samples from a moderately depleted lithospheric upper mantle with crustal-like U/Pb ratios (⁸⁷Sr/⁸⁶Sr: 0.7031–0.7035, ε Nd: ca. + 1, δ¹⁸O: 7‰, ²⁰⁶Pb/²⁰⁴Pb: ca.18.00, ²⁰⁷Pb/²⁰⁴Pb: 15.58–15.60). Primitive samples of the Oas quartz-normative syenites have identical isotope characteristics (⁸⁷Sr/⁸⁶Sr: 0.7034, ε Nd: ca. + 1, δ¹⁸O: 6.5‰, ²⁰⁶Pb/²⁰⁴Pb: ca.18.00, ²⁰⁷Pb/²⁰⁴Pb: 15.59) whereas more differentiated samples have higher ⁸⁷Sr/⁸⁶Sr ratios (0.709–0.714), slightly higher δ¹⁸O values (7.0–7.1‰), less radiogenic ε Nd values (− 1.1 to − 1.4) and more radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios up to 18.27. These features together with model calculations using Sr–Nd–Pb isotopes suggest modification of a primary syenite magma by combined AFC processes involving ancient continental crust. In this case, high Nb abundances of the parental syenite liquid prevent the development of significant negative Nb anomalies that may be expected due to interaction with continental crust.     

Petrogenesis of A-type granites and origin of vertical zoning in the Katharina pluton, Gebel Mussa (Mt. Moses) area, Sinai, Egypt

The central pluton within the Neoproterozoic Katharina Ring Complex (area of Gebel Mussa, traditionally believed to be the biblical Mt. Sinai) shows a vertical compositional zoning: syenogranite makes up the bulk of the pluton and grades upwards to alkali-feldspar granites. The latters form two horizontal subzones, an albite–alkali feldspar (Ab–Afs) granite and an uppermost perthite granite. These two varieties are chemically indistinguishable. Syenogranite, as compared with alkali-feldspar granites, is richer in Ca, Sr, K, Ba and contains less SiO₂, Rb, Y, Nb and U; Eu/Eu* values are 0.22–0.33 for syenogranite and 0.08–0.02 for alkali-feldspar granites. The δ¹⁸O (Qtz) is rather homogeneous throughout the pluton, 8.03–8.55‰. The δ¹⁸O (Afs) values in the syenogranite are appreciably lower relative to those in the alkali–feldspar granites: 7.59–8.75‰ vs. 8.31–9.12‰. A Rb–Sr isochron (n = 9) yields an age of 593 ± 16 Ma for the Katharina Ring Complex (granite pluton and ring dikes).

The alkali–feldspar granites were generated mainly by fractional crystallization of syenogranite magma. The model for residual melt extraction and accumulation is based on the estimated extent of crystallization ( 50 wt.%), which approximates the rigid percolation threshold for silicic melts. The fluid-rich residual melt could be separated efficiently by its upward flow through the rigid clusters of crystal phase. Crystallization of the evolved melt started with formation of hypersolvus granite immediately under the roof. Fluid influx from the inner part of the pluton to its apical zone persisted and caused increase of P_H2O in the magma below the perthite granite zone. Owing to the presence of F and Ca in the melt, P_H2O of only slightly more than 1 kbar allows crystallization of subsolvus Ab–Afs granite. Abundance of turbid alkali feldspars and their ¹⁸O/¹⁶O enrichment suggest that crystallization of alkali-feldspar granites was followed by subsolvus fluid–rock interaction; the δ¹⁸O (Fsp) values point to magmatic origin of fluids.

The stable and radiogenic isotope data [δ¹⁸O (Zrn) = 5.82 ± 0.06‰, I_Sr = 0.7022 ± 0.0064, ε_Nd (T) values are + 3.6 and + 3.9] indicate that the granite magma was generated from a ‘juvenile’ source, which is typical of the rocks making up most of the Arabian–Nubian shield.     

Petrogenesis of tourmaline rocks associated with Fe-carbonate–graphite metapelite, metabasite and strata-bound polymetallic sulphide mineralisation, Peloritani Mountains, Sicily, Southern Italy

Tourmalinite and tourmaline-rich rocks associated with Fe-carbonate–graphite phyllite, strata-bound polymetallic sulphide deposits, metabasite and marble were studied, for information on the mechanism of tourmaline formation in the pre-Hercynian low-grade metamorphic sequence of the Mandanici Unit in the Peloritani Mountains of Sicily, southern Italy. The major and trace element compositions of the tourmaline rocks suggest the existence of a sedimentary protolith with pre-metamorphic black shale and bedded chert. Boron was interpreted to be accumulated in a restricted sedimentary basin, between platform carbonate formations, with abundant organic matter and Fe–Al–Ti-rich laterite–bauxite soil-derived clastic supply, under a continental volcano-tectonic extensional regime accompanied by a local convective hydrothermal system along faults. Petrographic, crystal–chemical and δ¹¹B isotopic data are compatible with a model of marine sediment dewatering at temperatures below 200 °C, which caused the removal of boron from clay. Metamorphism led to the development of tourmaline in an Al–Ti-rich environment, in equilibrium with other minerals such as ilmenite, albite and muscovite. The upper temperature of metamorphism (almost 375 °C), estimated on the basis of δ¹¹B, fits geothermometric results from Δ¹³C_{carbonate–graphite} on associated rocks. The estimated value of δ¹¹B in the tourmalinite protolith, − 7.5‰ , is also compatible with continental-derived Al-rich sediments.     

Isotopic (O, Sr, Nd) and trace element geochemistry of the Laouni layered intrusions (Pan-African belt, Hoggar, Algeria): evidence for post-collisional continental tholeiitic magmas variably contaminated by continental crust

The three layered intrusions studied in the Laouni area have been emplaced within syn-kinematic Pan-African granites and older metamorphic rocks. They have crystallized at the end of the regional high-temperature metamorphism, but are free from metamorphic recrystallization, revealing a post-collisional character. The cumulate piles can be interpreted in terms of two magmatic liquid lines of descent: one is tholeiitic and marked by plagioclase–olivine–clinopyroxene cumulates (troctolites or olivine bearing gabbros), while the other is calc-alkaline and produced orthopyroxene–plagioclase rich cumulates (norites). One intrusion (WL (West Laouni)-troctolitic massif), shows a Lower Banded Zone where olivine-chromite orthocumulates are interlayered with orthopyroxene-rich and olivine–plagioclase–clinopyroxene cumulates, whereas the Upper Massive Zone consists mainly of troctolitic and gabbroic cumulates. The other two massifs are more homogeneous: the WL-noritic massif has a calc-alkaline differentiation trend whereas the EL (East Laouni)–troctolitic massif has a tholeiitic one. Separated pyroxene and plagioclase display similar incompatible trace element patterns, regardless of the cumulate type. Calculated liquids in equilibrium with the two pyroxenes for both noritic and troctolitic cumulates are characterized by negative Nb, Ta, Zr and Hf anomalies and light REE enrichment inherited from the parental magmas. Troctolitic cumulates have mantle-derived δ¹⁸O (+5 to +6‰), initial ⁸⁷Sr/⁸⁶Sr (Sr_i=0.7030 to 0.7054), _Nd (+5 to −1) values whereas noritic cumulates are variably enriched in δ¹⁸O (+7 to +9‰), show negative _Nd (−7 to −12) and slightly higher Sr_i (0.7040–0.7065). Based on field, isotopic ratios are interpreted as resulting from a depleted mantle source (Sr_i=0.7030; _Nd=+5.1; δ¹⁸O=+5.1‰) having experience short term incompatible element enrichment and variable crustal contamination. The mantle magma was slightly contaminated by an Archaean lower crust in troctolitic cumulates, more strongly and with an additional contamination by an Eburnian upper crust in noritic cumulates. Lower crust input is recorded mainly by Sr and Nd isotopes and upper crust input by O isotopes. This is probably due to the different water/rock ratios of these two crust types. Assimilation of low amounts (<10%) of quartz-bearing felsic rocks, coming from both lower and upper crust, can explain the rise of SiO₂ activity, the enrichment in ¹⁸O and ⁸⁷Sr and the lowering of _Nd in the noritic cumulates compared to troctolitic ones. The geodynamic model proposed to account for the Laouni tholeiitic magmatism involves a late Pan-African asthenospheric rise due to a rapid lithospheric thinning associated with functioning of shear zones, which allowed tholeiitic magmas to reach high crustal levels while experiencing decreasing degrees of crustal contamination with time.     

The isotopic composition of zircon and garnet: A record of the metamorphic history of Naxos, Greece

Growth of zircon with respect to that of garnet has been studied using a combination of petrography, U–Pb dating and oxygen isotope analysis. The aim is to document the mechanism and pressure–temperature conditions of zircon growth during metamorphism in order to better constrain the Tertiary metamorphic history of Naxos, Greece. Two metamorphisms are recognised: (1) an Eocene Franciscan metamorphism (M1) and (2) a widespread Miocene Barrovian metamorphism (M2) that increases from greenschist facies up to partial melting. An amphibolite sample contains zircon crystals characterised by a magmatic core and two metamorphic rims, denoted as A and B, dated at 200–270, 42–69, and 14–19 Ma, respectively. The first metamorphic rim A (δ¹⁸O = 7 ± 1‰) preserves the δ¹⁸O value of the magmatic core (6.2 ± 0.8‰), whereas rim B is characterised by higher δ¹⁸O values (7.8 ± 1.8‰). These observations indicate the formation of A rims by solid-state recrystallisation in a closed system with regard to oxygen and those of B in an open system. Compositional zoning in garnet is interpreted as the result of decompressional heating. Zircon B rims and garnet rims display similar δ¹⁸O values which indicates a contemporaneous growth of garnet and zircon rims during the Miocene Barrovian event (M2). Calcic gneiss and metapelite samples contain zircon crystals with single metamorphic overgrowths aged 41–57 Ma. δ¹⁸O values measured in zircon overgrowths (11.8 ± 1.4‰) from the calcic gneiss are similar to those measured in garnet rims (11.4 ± 1.1‰) from the same rock. This suggests that garnet rims and zircon overgrowths grew during the high pressure–low temperature event in equilibrium with prograde fluids. In the metapelite sample, δ¹⁸O values are similar in garnet cores (14.8 ± 0.2‰) and in zircon metamorphic overgrowths (14.2 ± 0.5‰). As zircon overgrowths have been dated at ca. 50 Ma by U–Pb, garnet cores and zircon overgrowths are interpreted to have grown during the high pressure event.

As demonstrated here for the island of Naxos, correlating the crystallisation of zircon with that of metamorphic index minerals such as garnet using stable isotope composition and U–Pb determination is a powerful tool for deciphering the mechanism of zircon growth and pin-pointing zircon crystallisation within the metamorphic history of a terrain. This approach is potentially hampered by an inability to verify the degree of textural equilibrium of zircon with other mineral phases, and the possible preservation (in metamorphic rims) of isotopic signatures from pre-existing zircon when they form by recrystallisation. Nevertheless, this study illustrates the application of this approach in providing key constraints on the timing and mechanism of growth of minerals important to understanding metamorphic petrogenesis.