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.     

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.     

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.     

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.     

Two types of gneisses associated with eclogite at Shuanghe in the Dabie terrane: carbon isotope, zircon U–Pb dating and oxygen isotope

There are two types of gneisses, biotite paragneiss and granitic orthogneiss, to be closely associated with UHP eclogite at Shuanghe in the Dabie terrane. Both concentration and isotope composition of bulk carbon in apatite and host gneisses were determined by the EA-MS online technique. Structural carbonate within the apatite was detected by the XRD and FTIR techniques. Significant ¹³C-depletion was observed in the apatite with δ¹³C values of −28.6‰ to −22.3‰ and the carbon concentrations of 0.70–4.98 wt.% CO₂ despite a large variation in δ¹⁸O from −4.3‰ to +10.6‰ for these gneisses. There is significant heterogeneity in both δ¹³C and δ¹⁸O within the gneisses on the scale of several tens meters, pointing to the presence of secondary processes after the UHP metamorphism. Considerable amounts of carbonate carbon occur in some of the gneisses that were also depleted in ¹³C primarily, but subjected to overprint of ¹³C-rich CO₂-bearing fluid after the UHP metamorphism. The ¹³C-depleted carbon in the gneisses is interpreted to be inherited from their precursors that suffered meteoric–hydrothermal alteration before plate subduction. Both low δ¹³C values and structural carbonate in the apatite suggest the presence of ¹³C-poor CO₂ in the UHP metamorphic fluid. The ¹³C-poor CO₂ is undoubtedly derived from oxidation of organic matter in the subsurface fluid during the prograde UHP metamorphism.

Zircons from two samples of the granitic orthogneiss exhibit low δ¹⁸O values of −4.1‰ to −1.1‰, demonstrating that its protolith was significantly depleted in ¹⁸O prior to magma crystallization. U–Pb discordia datings for the ¹⁸O-depleted zircons yield Neoproterozoic ages of 724–768 Ma for the protolith of the granitic orthogneiss, consistent with protolith ages of most eclogites and orthogneisses from the other regions in the Dabie–Sulu orogen. Therefore, the meteoric–hydrothermal alteration is directly dated to occur at mid-Neoproterozoic, and may be correlated with the Rodinia supercontinental breakup and the snowball Earth event. It is thus deduced that the igneous protolith of the granitic orthogneiss and some eclogites would intrude into the older sequences composing the sedimentary protoliths of the biotite paragneiss and some eclogites along the northern margin of the Yangtze plate at mid-Neoproterozoic, and drove local meteoric–hydrothermal circulation systems in which both ¹³C- and ¹⁸O-depleted fluid interacted with the protoliths of these UHP rocks now exposed in the Dabie terrane.     

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.     

Oxygen isotopic composition of minerals in the Kenna ureilite

The δ¹⁸O and δ¹⁷O values of olivine from Kenna are 7.6 and 3.0%, respectively, relative to SMOW. These values are typical of ureilites which form a unique group on a δ¹⁷O -δ¹⁸O graph. The ureilites are related to, but not directly derived from, the anhydrous phases of C2 and C3 meteorites. The ¹⁸O/¹⁶O fractionation between pyroxene and olivine is 0.60, indicating a temperature of last equilibration of 1000 ± 100°C.     

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.     

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.     

Geochemistry of microgranular enclaves and host granite from Telões (Vila Pouca de Aguiar), Northern Portugal

At Telões, a subaluminous medium- to coarse-grained porphyritic biotite granite, crops out along the Vila Real NNE–SSW fault. It is a post-tectonic granite of 299±3 Ma old given by U–Pb isotopic data on zircon. It contains metaluminous to subaluminous tonalitic, granodioritic and monzogranitic enclaves. All granitoids have Fe²⁺-biotite and some enclaves contain magnesiohornblende and subsolidus actinolite. Monzogranitic enclaves show obvious similarities to the host granite. Linear array between enclaves and host granite is observed in Rb–Sr typical isochron diagram and gives the age of 286±11 Ma and (⁸⁷Sr/⁸⁶Sr)₀=0.7063±0.0011. Microgranular enclaves have δ¹⁸O values similar to those of the hosting granite. Microgranular enclaves are hybrid rocks probably formed by mixing between a tonalitic enclave magma and a host granite magma as supported by the modelling of major and trace elements. The similar isotopic signatures suggest a subsequent partial equilibration of the enclaves and granite magmas.     

Geochemistry of mafic and ultramafic xenoliths from Fidra (Southern Uplands, Scotland): implications for lithospheric processes in Permo-Carboniferous times

Several types of xenoliths occur in a Permian basanite sill in Fidra, eastern central Scotland. One group consists of spinel lherzolites, which have geochemical and isotopic characteristics similar to those of lithospheric upper mantle from elsewhere in western Europe, with both LREE-depleted and LREE-enriched compositions. A separate group comprises pyroxenites and wehrlites, some of which contain plagioclase; these have compositions and textures that indicate that they are cumulates from mafic magmas. In terms of Sr and Nd isotope compositions, the pyroxenites closely resemble the host basanite and most likely formed by high-pressure fractionation of Permo-Carboniferous alkaline magmas at lower crustal depths. They also have mantle-like δ¹⁸O values. A third group is composed of granulite xenoliths that vary between plagioclase-rich and clinopyroxene-rich compositions, some of which probably form a continuum with the pyroxenites and wehrlites. They are all LREE-enriched and most have positive Eu anomalies; thus, they are also mostly cumulates from mafic magmas. Many of the granulites also have Sr and Nd radiogenic isotope ratios similar to those of the host basanite, indicating that they have formed from a similar magma. However, several of the granulites show more enriched isotopic compositions, including higher δ¹⁸O values, trending towards an older crustal component. Thus, the pyroxenites and granulites are largely cogenetic and are mainly the product of a mafic underplating event that occurred during the widespread magmatism in central Scotland during Permo-Carboniferous times.     

37 ka以来日本海沉积物有机质碳和氮稳定同位素变化及其古海洋学意义

海洋沉积物有机质碳氮稳定同位素(δ¹³C、δ¹⁵N)广泛用于有机质来源示踪、古生产力和古海洋环境重建。日本海沉积物δ¹³C和δ¹⁵N值一个显著特征是在末次冰盛期(LGM)同步负偏,但是对这一现象产生的原因以及他们的演化过程的认识仍然存在明显不足。在本研究中,我们详细调查了37 ka以来日本海中部LV53-23-1岩心沉积物δ¹³C和δ¹⁵N演化历史。结果显示,沉积物δ¹³C和δ¹⁵N分别介于-26.3‰至-22.5‰和1.6‰至6.1‰,低值出现在LGM(26.5~17 ka)暗色层状泥发育时期,指示较强的陆源输入贡献。在Heinrich冰阶1时期(17~14.5 ka),δ¹³C和δ¹⁵N快速正偏,表明日本海海洋环境发生了明显的转换,对应于对马海峡淹没及对马暖流入侵。14.5 ka之后,沉积物δ¹⁵N值恢复到5‰,与开阔大洋海水硝酸盐的δ¹⁵N值近似。我们采用二端员混合模型粗略地估算了有机质来源的相对贡献。LGM时期陆源有机质贡献介于65%至80%,14.5 ka以后海源有机质贡献介于60%至80%。除了增加的陆源有机质贡献以外,LGM时期沉积物δ¹⁵N亏损还涉及如下过程:(1)较高的含Fe沙尘供给提高日本海表层海洋生物固氮效率;(2)缺氧环境盛行减弱成岩作用对沉积物δ¹⁵N影响。37 ka以来,日本海沉积物δ¹³C和δ¹⁵N变化与有机质来源、营养盐的供给、表层生产力和沉积物氧化还原条件相关,实际受海平面和全球气候制约。     

Geochemistry and mineralogy of bentonites from Ishirini (Libya)

Smectites from the Ishirini bentonite deposit (Libya) were analysed for their oxygen and hydrogen isotopic ratios. Based on published isotopic fractionation data, the results indicate a predominantly meteoric origin of the fluids responsible for the transformation of pyroclastic rocks to bentonite at temperatures ranging from 30 to 90 °C. The thermal effect of the subsequent emplacement of volcanic intrusions was further evaluated by a detailed study of δ¹⁸O isotopic composition of smectites and fluid inclusions in quartz separated from silicified rings produced by the thermal action of a basalt dike. Five different groups of fluids were distinguished based on salinity and homogenization temperatures.

The contact zone of bentonite affected by high concentrated saline solution exhibit mineralogical changes. High salinity and high temperature also remarkably influence the technical parameters of bentonites and reduce, for example, the cation exchange capacity (CEC) or microporosity.     

Geochemistry of granitoids and their minerals from Rebordelo–Agrochão area, northern Portugal

Deformed Hercynian peraluminous granitoids ranging from tonalite to granite crop out in the Rebordelo–Agrochão area, northern Portugal and some of them contain tonalitic and granodioritic enclaves. Variation diagrams of major and trace elements of the rocks, biotites and sphenes show fractionation trends. The most- and the least-deformed samples of granite and their biotites also define fractionation trends. There is decrease in all rare earth element (REE) contents and increase in the Eu anomaly in REE patterns from the most- to the least-deformed samples of granite. All the granitoids define a whole-rock Rb–Sr errorchron. A whole-rock Rb–Sr isochron for the least-deformed samples of granite yields an age of 357±9 Ma and an initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7087±0.0007. Geochemical modelling suggests that the tonalitic magma evolved by AFC (fractional crystallization of magnesiohornblende, plagioclase, quartz, biotite and ilmenite, and assimilation of metasediments) to originate tonalitic and granodioritic enclaves, granodiorite and granite. δ¹⁸O values support this mechanism. The tonalite is hybrid and derived by interaction of a mantle-derived magma and crustal materials.     

A high precision U–Pb age of metamorphic rutile in coesite-bearing eclogite from the Dabie Mountains in central China: a new constraint on the cooling history

This paper first reports a high precision U–Pb age of 218±1.2 Ma for rutile in coesite-bearing eclogite from Jinheqiao in the Dabie Mounteins, east–central China. This work shows that the U–Pb mineral (rutile+omphacite) isochron age of 218±2.5 Ma and conventional rutile U–Pb concordia age of 218±1.2 Ma obtained by common Pb correction based on the Pb isotopic composition of omphacite in the same eclogite sample are consistent, proving that the omphacite with low U/Pb ratio (μ=2.8) can be used for common Pb correction in U–Pb dating of rutile. Oxygen isotope analysis of rutile aliquots gave the consistent δ¹⁸O values of −6.1±0.1%, demonstrating oxygen isotope homogenization in the rutile of different grains as inclusion in garnet and grain in matrix. Oxygen isotope thermometry yields temperatures of 695±35 and 460±15 °C for quartz–garnet and quartz–rutile pairs, respectively. These oxygen isotopic observations suggest that the diffusion of oxygen in rutile as inclusion in garnet is not controlled by garnet. According to field-based thermochronological studies of rutile, an estimate of the T_c of about 460 °C for U–Pb system in rutile under rapid cooling conditions (20 °C/Ma) was advised. Based on this U–Pb age as well as the reported chronological data with their corresponding metamorphic and/or closure temperature, an improved T–t path has been constructed. The T–t path confirms that the UHPM rocks in South Dabie experienced a rapid cooling following the peak metamorphism before 220 Ma and a long isothermal stage from 213 to 180 Ma around 425 °C.     

环境同位素硫在大同南寒武-奥陶系地下水资源研究中的应用

对山西大同口泉沟南寒武-奥陶系碳酸盐岩地下水(岩溶水)资源的开发研究中,利用不同价态硫富集34S的不同以及硫同位素分馏,主要是硫酸盐和硫化物中δ34S(SO₄2-)、δ34S(HS-)的变化,分析了岩溶水的来源,区分出表征循环交替和补给条件的三种地下水类型和环境,识别出口泉南水文地质区内各个地下水子系统及其相互关系。对岩溶水开发中泉域划分问题,使用硫同位素之间的关系,并结合硫酸盐中氧同位素δ18O(SO₄2-)以及14C关系,表明本区与相邻的两泉域相互独立。岩溶水中δ34S(SO₄2-)、δ34S(HS-)和δ18O(SO₄2-)有很大变幅,神头泉Z1岩溶水有罕见的异常值。     

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.     

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.     

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.     

Boron isotopic composition of subduction-zone metamorphic rocks

Many arc lavas contain material derived from subducted oceanic crust and sediments, but it remains unresolved whether this distinctive geochemical signature is transferred from the subducting slab by aqueous fluids, silicate melts, or both. Boron isotopic measurements have the potential to distinguish between slab transfer mechanisms because ¹¹B fractionates preferentially into aqueous fluids whereas little fractionation may occur during partial melting. Previous studies have shown that δ¹¹B values of island arc lavas (−6 to +7) overlap the range of δ¹¹B values for altered oceanic crust (−5 to +25) and pelagic sediments and turbidites (−7 to +11). Secondary ion mass spectrometry (SIMS) analyses of minerals in subduction-zone metamorphic rocks yield δ¹¹B=−11 to −3 suggesting that slab dehydration reactions significantly lower the δ¹¹B values of subducted oceanic crust and sediments. In order to explain the higher δ¹¹B values reported for arc lavas as compared to subduction-zone metamorphic rocks, the B-bearing component derived from the metamorphosed slab must be enriched in ¹¹B relative to the slab, favoring an aqueous fluid as the slab transfer mechanism.