Boron isotopic variations in tourmaline from metacarbonates and associated calc-silicate rocks from the Bohemian Massif: Constraints on boron recycling in the Variscan orogen

Various metacarbonate and associated calc-silicate rocks form minor but genetically significant components of the lithological units in the Bohemian Massif of the Variscan orogen in Central Europe.These rocks vary in terms of their lithostratigraphy,chemical composition and mineral assemblage(dolomite/calcite ratio,silicate abundance).Tourmaline is present in five paragenetic settings within the metacarbonate and calc-silicate units.TypeⅠcomprises individual,euhedral,prismatic grains and grain aggregates in a carbonate-dominant(calcite±dolomite)matrix poor in silicates.TypeⅡis characterized by euhedral to subhedral grains and coarse-to fine-grained aggregates in silicate-rich layers/nests within metacarbonate bodies whereas typeⅢoccurs as prismatic grains and aggregates at the contact zones between carbonate and associated silicate host rocks.TypeⅣis in veins crosscutting metacarbonate bodies,and typeⅣtourmaline occurs at the exocontacts of elbaite-subtype granitic pegmatite.Tourmaline from the different settings shows distinctive compositional features.Typical for typeⅠare Mg-rich compositions,with fluor-uvite>dravite>>magnesio-lucchesiite.Tourmalines from typeⅡsilicate-rich layers/nests are highly variable,corresponding to oxy-schorl,magnesio-foitite,Al-rich dravite and fluor-uvite.Typical for typeⅢtourmalines are Ca,Ti-bearing oxy-dravite compositions.The typeⅣveins feature dravite and fluor-uvite tourmaline compositions whereas typeⅤtourmaline is Li,F-rich dravite.Tourmaline is the only Bbearing phase in paragenetic typesⅠ-Ⅳ,where it is characterised by two principal ranges of B-isotope composition(δ^11B=-13‰to-9‰and-18‰to-14‰).These ranges correspond to regionally different units of the Moldanubian Zone.Thus,the Svratka Unit(Moldanubian Zone s.l.)contains only isotopically lighter tourmaline(δ^11B=-18‰to-14‰),whereas metacarbonates in the Poli?ka unit(Teplá-Barrandian Zone)and Olesnice unit(Moravicum of the Moravo-Silesian Zone)has exclusively isotopically heavier tourmaline(δ^11B=-9‰to-13‰).Tourmalines from metacarbonates in the Variegated Unit cover both ranges of isotope composition.The isotopically light end of the B isotope range may indicate the presence of continental evaporites within individual investigated areas.On the other hand,variations in the range of~8δ-units is consistent with the reported shift in B isotopic composition of metasedimentary rocks of the Bohemian Massif due to the prograde metamorphism from very-low grade to eclogite facies.In contrast to the metacarbonate-hosted settings,tourmaline of paragenetic type V from the exocontact of granitic pegmatites displays a significantly heavier range ofδ^11B(as low as-7.7‰to-0.6‰),which is attributed to partitioning of 10 B to cogenetic axinite and/or different B-signature of the source pegmatite containing tourmaline with heavyδ^11B signature.     

Tourmaline growth in pelitic schist and quartzite: A textural,chemical and B-isotopic study from the Gangpur Schist Belt,eastern India

Tourmaline is the principal repository of boron in crustal rocks and therefore useful for tracing B-cycling during prograde dehydration and retrogression of supracrustal rocks. Here, we use the major-trace element, and B isotope composition of tourmaline from schists, quartzites, and tourmaline-quartz veins of the Gangpur Schist Belt in eastern India to constrain the source of boron and the physicochemical evolution of B-rich fluids during prograde dehydration metamorphism. Tourmaline growth and re-equilibration in rocks of the Gangpur Schist Belt was a multi-stage process involving several fluid sources. The δ¹¹B varies between ?6‰ and ?18‰, indicating a dominantly continental source for boron. Tourmaline in schists, quartzites, and tourmaline-quartz veins grew over a wide range of P-T conditions and record multiple episodes of metamorphic dehydration between ca. 1.6 Ga and ca. 0.95Ga. The tourmaline in tourmaline-quartz veins and quartzites has lighter B-isotope composition, typical of continental detritus, while those in the schists and quartzites record pelite-dehydration signature with values decreasing gradually from ca. ?12‰ in the cores to ca. ?17‰ in the rims. Heavier isotopic compositions (δ¹¹B of ca. ?6‰) measured in some grains in the pelites and quartzites indicate boron contribution from meta?carbonate sources. The mixing of a heavier B-rich metacarbonate-derived fluid with pelite-derived metamorphic fluids could explain the lower B-isotope values in such tourmaline. The study also attempts to constrain the controls on the intake of trace elements in tourmaline. The results suggest that the partitioning of Mn, Y, V, Co and Ti in tourmaline is affected by the growth of porphyroblast phases such as garnet, staurolite, and biotite, while Li, Sr, Zn and Sn reflect the signature of the metamorphic fluid.     

Proto-Adamastor ocean crust (920 Ma) described in Brasiliano Orogen from coetaneous zircon and tourmaline

Proto-Adamastor ocean bathed Rodinia and successor continental fragments from 1.0–0.9 Ga up to 0.75 Ga, and evolved into world Adamastor Ocean at 0.75–0.60 Ga. Mesoproterozoic oceanic crust is poorly preserved on continents, only indirect evidence registered in Brasiliano Orogen. We report first evidence of ophiolite originated in proto-Adamastor. We use multi-technique U-Pb-Hf zircon and δ¹¹B tourmaline isotopic and elemental compositions. The host tourmalinite is enclosed in metaserpentinite, both belonging to the Bossoroca ophiolite. Zircon is 920 Ma-old, ?_{Hf(920 Ma)} = +12, Hf_TDM = 1.0 Ga and has ‘oceanic’ composition (e.g., U/Yb < 0.1). Tourmaline is dravite with δ¹¹B = +1.8‰ (Tur 1), 0‰ (Tur 2), ?8.5‰ (Tur 3). These characteristics are a novel contribution to Rodinia and associated world ocean, because a fragment of proto-Adamastor oceanic crust and mantle evolved at the beginning of the Brasiliano Orogen.     

Characteristic Features of REE and Pb–Zn–Ag Mineralizations in the Na Son Deposit,Northeastern Vietnam

The Na Son deposit is a small‐scale Pb–ZnPb–Zn–Ag deposit in northeast Vietnam and consists of biotite–chlorite schist, reddish altered rocks, quartz veins and syenite. The biotite–chlorite schist is intruded by syenite. Reddish altered rocks occur as an alteration halo between the biotite–allanite‐bearing quartz veins and the biotite–chlorite schist. Allanite occurs in the biotite–allanite‐bearing quartz veins and in the proximal reddish altered rocks. Rare earth element (REE) fluorocarbonate minerals occur along fractures or at rim of allanite crystals. The later horizontal aggregates of sulfide veins and veinlets cut the earlier reddish altered rocks. The earlier Pb–Zn veins consist of a large amount of galena and lesser amounts of sphalerite, pyrite and molybdenite. The later Cu veins cutting the Pb–Zn veins include chalcopyrite and lesser amounts of tetrahedrite and pyrite. The occurrences of two‐phase H₂O–CO₂ fluid inclusions in quartz from biotite–allanite‐bearing quartz veins and REE‐bearing fluorocarbonate minerals in allanite suggest the presence of CO₂ and F in the hydrothermal fluid. The oxygen isotopic ratios of the reddish altered rocks, biotite–chlorite schist, and syenite range from +13.9 to +14.9 ‰, +11.5 to +13.3 ‰, and +10.1 to +11.6 ‰, respectively. Assuming an isotopic equilibrium between quartz (+14.6 to +15.8 ‰) and biotite (+8.6 ‰) in the biotite–allanite‐bearing quartz vein, formation temperature was estimated to be 400°C. At 400°C, δ¹⁸O values of the hydrothermal fluid in equilibrium with quartz and biotite range from +10.5 to +11.7 ‰. These δ¹⁸O values are consistent with fluid that is derived from metamorphism. Assuming an isotopic equilibrium between galena (+1.5 to +1.7 ‰) and chalcopyrite (+3.4 ‰), the formation temperature was estimated to be approximately 300°C. The formation temperature of the Na Son deposit decreased with the progress of mineralization. Based on the geological data, occurrence of REE‐bearing minerals and oxygen isotopic ratios, the REE mineralization is thought to result from interaction between biotite–chlorite schist and REE‐, CO₂‐ and F‐bearing metamorphic fluid at 400°C under a rock‐dominant condition.     

In situ LA–MC–ICP–MS boron isotope and zircon U–Pb age determinations of Paleoproterozoic borate deposits in Liaoning Province,northeastern China

A large number of Paleoproterozoic borate deposits are hosted by the lower units of a volcanic-sedimentary sequence in Liaoning Province, northeastern China, and are a major source of boron in China. The ore-bearing wall rocks in the deposits are serpentinized ultrabasic rocks and carbonates, with layered leptynites, leptites, amphibolites, and migmatites adjacent to the ore. Both the borate ores and country rocks contain tourmaline, although the country rocks have much lower abundances of the mineral. Based on in situ boron isotope measurements using laser ablation–multi-collector–inductively coupled plasma–mass spectrometry (LA–MC–ICP–MS), boron isotope data show that: (1) δ¹¹B values of borate ores range from + 6.8‰ to + 13.9‰ (mean + 10.8‰); (2) tourmalines from the borate ores have δ¹¹B values from + 9.5‰ to + 12.7‰; and (3) the wall rocks within the borate ores yield slightly lower δ¹¹B values ranging from + 5.7‰ to + 7.6‰, and those outside the deposits from − 9.9‰ to − 5.9‰. Positive δ¹¹B values in borates as well as in tourmalines inside the mining area indicate that boron in these Paleoproterozoic borate deposits was derived from marine evaporites. δ³⁴S_V-CDT (where V-CDT is Vienna Canyon Diablo Troilite) values of borate ores, serpentinized marbles, and anhydrites range from + 16.1‰ to + 24.7‰, whereas δ¹³C_V-PDB (where V-PDB is Vienna Pee Dee Belemnite) values of marbles range from + 3.2‰ to + 5.9‰. These isotopic characteristics are interpreted to reflect formation in a marine evaporative environment. LA–MC–ICP–MS zircon weighted²⁰⁷Pb/²⁰⁶Pb ages of leptite and serpentinized olivine basalt from the hanging wall of the borate deposits are 2139 ± 13 Ma and 2130 ± 19 Ma, respectively. Therefore, the (~ 2.2 Ga) borate deposits may have originated from marine evaporative boron-bearing sediments, which were interbedded within bimodal volcanic rocks during the early stages of development of the Liaoji rift.     

Stable isotope compositions of tourmalines from granites and related hydrothermal rocks of the Karagwe-Ankolean belt,northwest Tanzania

Tourmaline is a ubiquitous mineral in the Mid-Proterozoic, peraluminous, syn- to post-tectonic granites and aplites and the related hydrothermal rocks of the Karagwe-Ankolean belt in northwest Tanzania. Electron microprobe analysis indicates that tourmalines from all of the intrusive and hydrothermal lithologies: (1) belong to the schorl-dravite solid-solution series; and (2) plot within the field occupied by tourmaline from Li-poor granitoids on the Fe-Al-Mg classification diagram. Oxygen isotope compositions range from +12.2 to +11.6‰ (SMOW) for magmatic tourmalines and from +10.8 to +9.8‰ for those of hydrothermal origin. Hydrogen isotope compositions vary from −79 to − 65‰ (SMOW) for magmatic tourmalines and from −99 to −84‰ for hydrothermal tourmalines. Water contents measured by manometry are constant at 3.0–3.2 wt.%. Within the broad grouping there arc systematic variations in both chemical [particularly Fe_tot/(Fe_tot + Mg ratio)] and isotopic composition that relate to evolving magmatic and hydrothermal conditions. Igneous differentiation [increasing Fe_tot/(Fe_tot + Mg) in magmatic tourmaline] has produced trends with higher δ¹⁸O in quartz, lower δ¹⁸O in tourmaline, and larger Δ_QTZ.−TOUR.-values, that reflect a combination of a reduction of crystallization temperature and an increase of Fe_tot/ (Fe_tot + Mg) in the residual melt. Subsequent cooling and interaction of an exsolved, B-rich magmatic fluid with the pelitic country rocks, resulted in the deposition of hydrothermal tourmaline with increasing Fe_tot/(Fe_tot + Mg) ratios, and progressively lower δ¹⁸O and δD -values.     

Oxygen isotope study of metamorphic and granitic rocks of the Yanai district in the Ryoke belt,Japan

¹⁸O/¹⁶O ratios have been obtained for 134 whole-rocks and minerals from metamorphic and granitic rocks of the Yanai district in the Ryoke belt, Southwest Japan. The ¹⁸O/¹⁶O ratios of pelitic rocks of the marginal metamorphic zone decrease progressively with increasing metamorphic grade. In the gneiss-granite complex (zone of migmatite [1]), the most characteristic feature of the rocks is that oxygen isotopic homogenization proceeds on both local and regional scales in parallel with “granitization” or chemical homogenization. Granitic rocks of various origin are fairly uniform in isotopic composition with δ ¹⁸O of quartz of 12 to 14‰ (SMOW) and δ ¹⁸O of biotite of 7 to 9‰ and are about 3 to 4‰ enriched in ¹⁸O compared to other Cretaceous granites of non-metamorphic terranes in Japan. The high ¹⁸O/¹⁶O ratios of granitic rocks of this district were discussed in relation to the ¹⁸O-depletion in metasediments. Oxygen isotopic fractionations among coexisting minerals from various rock-types of the gneiss-granite complex indicate that these minerals were formed under near isotopic equilibrium at a temperature of about 600 to 700° C. Some abnormal fractionations of quartz-biotite pairs also were obtained for rocks which had undergone a progressive ¹⁸O-depletion or ¹⁸O-enrichment. This is due to high resistivity of quartz and contrastive susceptibility of biotite to isotopic exchange during metamorphism and “granitization”.     

Geology,Pb Isotope Geochemistry and Ore Genesis of the Liziyuan Gold Deposit,West Qinling Orogen,Central China

The Liziyuan gold deposit, situated on the south side of the Shangdan suture zone, West Qinling Orogen, occurs in metamorphic volcanic rocks(greenschist facies) of the early Paleozoic Liziyuan Group and in Indosinian Tianzishan monzogranite. Orebodies in the Liziyuan gold field are controlled by the ductile-brittle shear zone, and by thrusting nappe faults related to the Indosinian orogeny. In detail, this paper analyzed the geological characteristics of the Liziyuan gold field, and the Pb isotopes of the Lziyuan host rocks, granitoids(Tianzishan monzogranite and Jiancaowan syenite porphyry), sulfides, and auriferous quartz veins by multiple-collector inductively coupled plasma mass spectrometry(MC-ICPMS). In addition, previous data on the sulfur, hydrogen, and oxygen isotopes were employed to discuss the possible sources of the ore-forming fluids and materials, and to further understand the tectonic setting of the Liziyuan gold deposit. The sulfides and their host rocks(Lziyuan Group), Tianzishan monzogranite and Jiancaowan syenite porphyry, and auriferous quartz veins have similar Pb isotopic compositions.Zartman's plumbotectonic model diagram shows that most of the data for the deposit fall near the orogenic Pb evolutionary curve or within the area between the orogenic and mantle Pb evolutionary curves. In the△β-△γ diagram, which genetically classifies the lead isotopes, most of the data fall within the range of the subduction-zone lead mixed with upper crust and mantle. This indicates that a complex source of the ore lead formed in the orogenic environment. The δ~(34)S values of the sulfides range from 3.90 to 8.50‰(average6.80‰), with a pronounced mode at 5.00‰-8.00‰. These values are consistent with that of orogenic gold deposits worldwide, indicating that the sulfur sourced mainly from reduced metamorphic fluids. The isotopic hydrogen and oxygen compositions support a predominantly metamorphic origin of the oreforming fluids, with possible mixing of minor magmatic fluids, but the late stage was dominated by meteoric water. The characteristics of the Liziyuan gold deposit formed in the Indosinian orogenic environment of the Qinling Orogen are consistent with those of orogenic gold deposits found worldwide.     

Fluid infiltration effects on stable isotope systematics of the Susurluk skarn deposit,NW Turkey

A calcic skarn deposit occurs along the contact zone between Oligo-Miocene Çatalda? Granitoid and Mesozoic limestones in Susurluk, northwestern Turkey. The skarn zone with little or no retrograde stage is represented by fluid inclusions with high homogenization temperatures (up to >600 °C) and a wide range of salinity (12 to >70 wt.% NaCl). Pluton-derived fluids facilitated occurrence of continuous prograde reactions in the country rocks (particularly in the proximal zone) and oxygen isotopic depletion in calc-silicate and calcite minerals. δ¹⁸O of anhydrous minerals within proximal and distal zones indicate that skarn-forming fluids had a magmatic origin. The δ¹⁸O values are 5.93–9.08‰ (mean 6.8‰) for garnet, 4.08–9.94‰ (mean 6.4‰) for pyroxene, 4.89–7.92‰ (mean 6.4‰) for wollastonite and 6.65–8.28‰ (mean 7.5‰) for vesuvianite. Temperatures estimated by isotopic compositions of mineral pairs are significantly lower than those measured from the fluid inclusions, indicating that isotopic equilibrium is not preserved between the skarn minerals. δ¹⁸O and δ¹³C values are systematically depleted from marbles to skarn carbonates. Calc-silicate forming reactions and permeability increase triggered by volatilization and consequent strong infiltration of H₂O-rich siliceous fluids into the system promoted fluid–rock interaction causing isotopic resetting and isotopic depletion of silicates (e.g. pyroxene and wollastonite) and skarn calcites.     

Sources and fluid regime of quartz-carbonate veins at the Sukhoi Log gold deposit,Baikal-Patom Highland

Complex (δ¹⁸O, δ¹³C, ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, and REE composition) data were obtained on quartz-carbonate veins in metasedimentary rocks to elucidate the material sources and to evaluate fluid regime during low-sulfide gold-quartz ore mineralization at the Sukhoi Log deposit. In order to use an oxygen isotopic thermometry for quartz veins, we calibrated empirical dependence of fractionation factors between vein quartz and altered wall rocks. The temperature range of quartz equilibration with wall rocks was evaluated at 380–190°C. Independent temperatures obtained using this thermometer indicate that the vein ankerite can be both earlier and later than vein quartz. The isotopic systematics (δ¹³C and δ¹⁸O) of ankerite in the quartz-carbonate veins, carbonates in the ore-hosting shales of the Khomolkho and Imnyakh formations both within and outside mineralized zones at the deposit indicate that the ore-hosting rocks and veins in the mineralized zone contain incoming carbonate, which was most probably borrowed from the carbonate rocks of the Imnyakh Formation. REE composition of vein ankerite shows that these elements were transported by fluid as carbonate complexes. The behavior of the Eu/Eu* and (La/Yb)_n ratios and Mn of the vein ankerite suggest that during carbonate crystallization the system was closed with respect to fluid. Sr-Nd isotope systematics indicates that the isotopic parameters of the vein ankerite were formed with the participation of metasedimentary host rocks of both the Imnyakh and Khomolkho formations, which are contrastingly different in Nd isotopic composition. A fluid/rock ratio during metasomatic processes in the wall rocks was calculated for two scenarios of their thermal history: with a continuously operating heat source beneath the Sukhoi Log structure and with a linear cooling of the structure. The effective integral W/R ratios calculated lie within the range of 0.046–0.226 and suggest that the veins were produced with the metamorphic fluid. Low W/R ratios are inconsistent with the mechanism of vein quartz crystallization due to fluid oversaturation with respect to SiO₂ at decreasing temperature. We believe that the main mechanism responsible for the origin of these veins was variations of fluid oversaturation due to pressure variations (pressure solution mechanism). This hypothesis is consistent with the reported isotopic-geochemical characteristics of the wall rocks at the Sukhoi Log deposit.     

18O/16O ratios of anorthosites and related rocks from the Rogaland Complex (SW Norway)

The South Rogaland Complex (South Western Norway) consists of several anorthositic intrusions emplaced in granulite facies metamorphic rocks. The anorthosites and related norites and jotunites have δ ¹⁸O values of 5.2 to 7‰ suggesting a mantle origin for these rocks, in agreement with the strontium isotopic evidence. The acidic rocks, mostly charnockitic, associated with the anorthosites have similar δ ¹⁸O values and thus a comagmatic relation between these two rock types is inferred. Small departures from mantle values are explained in terms of crustal contamination by surrounding gneisses that have δ ¹⁸O values between 4.3 and 10‰ Locally, this corresponds to important anatexis as has been suggested for the Farsund charnockite on the basis of strontium isotope and REE geochemistry. The isotopic temperatures calculated from the isotopic fractionations are in the range 500°–700° C, lower than the orthomagmatic temperatures and probably due to subsolidus isotopic exchange during the slow cooling of these plutonic rocks, either during a late magmatic deuteric stage or during a slow, postorogenic ascent under wet conditions.     

Characterization of the hydrogen isotopic composition of individual n-alkanes in terrestrial source rocks

In order to characterize the H isotopic compositions of individual lipid compounds from different terrestrial depositional environments, the δD values of C-bound H in individual n-alkanes from typical terrestrial source rocks of the Liaohe Basin and the Turpan Basin, China, were measured using gas chromatography–thermal conversion–isotope ratio mass spectrometry (GC–TC–IRMS). The analytical results indicate that the δD values of individual n-alkanes in the extracts of terrestrial source rocks have a large variation, ranging from −140‰ to −250‰, and are obviously lighter than the δD of marine-sourced n-alkanes. Moreover, a trend of depletion in ²H(D) was observed for individual n-alkanes from different terrestrial depositional environments, from saline lacustrine to freshwater paralic lacustrine, and to swamp. For example, the δD values of n-alkanes from a stratified saline lacustrine environment vary from −140‰ to −200‰, δD for n-alkanes from swamp facies range from −200‰ to −250‰, while those from freshwater paralic lacustrine–lacustrine environments fall between the δD values of the end members. The shift toward lighter δD from saltwater to freshwater environments indicates that the source water δD is the major controlling factor for the H isotopic composition of individual compounds. In addition, H exchange between formation water and sedimentary organic matter may possibly be important in regard to the δD of individual n-alkanes. Therefore, other lines of geochemical evidence must be considered when depositional paleoenvironments of source rocks are reconstructed based on the H isotopic composition of individual n-alkanes.     

The utilization of boron and strontium isotopes for the assessment of boron contamination of the Cecina River alluvial aquifer (central-western Tuscany,Italy)

The groundwater B concentration in the alluvial aquifer of the upper Cecina River basin in Tuscany, Italy, often exceeds the limit of 1 mg L⁻¹ set by the European Union for drinking water. On the basis of hydrogeological and geochemical observations, the main source of the B contamination of groundwater has been attributed to past releases into streams of exhausted, B-rich geothermal waters and/or mud derived from boric acid manufacturing in Larderello. The releases were discontinued 25–30 years ago.This study confirms that the B dissolved in groundwater is anthropogenic. In fact, the δ¹¹B values of groundwater B match the range −12.2‰ to −13.3‰ of the Turkish B mineral (colemanite) processed in boric acid manufacturing, in the course of which no significant isotopic effects have been observed. This isotopic tracing of the Cecina alluvial aquifer occurs just below the confluence of the Possera Creek, which carries the B releases from Larderello. Strontium isotope ratios support this conclusion.At about 18 km from the Possera Creek confluence, the groundwater δ¹¹B drops to much more negative values (−22‰ to −27‰), which are believed to be produced by adsorption–desorption interactions between dissolved B and the aquifer matrix. The δ¹¹B of B fixed in well bottom sediments shows a similar variation. At present, desorption is prevailing over adsorption because the releases of B-rich water have ceased. A theoretical model is suggested to explain the isotopic trends observed.Thus, B isotopes appear to be a powerful tool for identifying the origin of B contamination in natural waters, although isotopic effects associated with adsorption–desorption processes may complicate the picture, to some extent.     

The Cipoeiro gold deposit,Gurupi Belt,Brazil: Geology,chlorite geochemistry,and stable isotope study

The Cipoeiro gold deposit, located in the Gurupi Belt, northern Brazil, is hosted by tonalites of 2148 Ma. The deposit is controlled by splays related to the major strike-slip Tentugal shear zone, and at the deposit scale, the mineralization is confined to ductile–brittle shear zones. Mineralization style comprises thick quartz veins and narrow and discontinuous quartz-carbonate veinlets associated with disseminations in altered host rocks. The postmetamorphic hydrothermal paragenesis is composed of quartz, calcite, chlorite, white mica (phengite), pyrite, and minor albite. Electron microprobe analysis of chlorites reveals a relatively uniform chemical composition at depths of more than 100 m. The chlorites are characterized by (Fe + Mg) ratios between 0.37 and 0.47 and Al^IV ranging between 2.22 and 2.59 a.p.f.u. and are classified as Fe-chlinochlore. Temperatures calculated by applying the Al^IV contents of chlorites yield a relatively narrow interval of 305 ± 15°C. Stable isotope (O, H, C, S) compositions have been determined in silicate, carbonate, and sulfide minerals. The δ¹⁸O and δD values of the mineralizing fluid range from +2.4 to +5.7 and from −43‰ to −20‰, respectively, and are interpreted as having a metamorphic origin. The δ¹³C values of fluid CO₂ are in the range −10.7‰ to −3.9‰, whereas the fluid δ³⁴S is around 0‰. Carbon and sulfur compositions are not diagnostic of their sources, compatible as they are with mantle, magmatic, or average crustal reservoirs. The hydrothermal paragenesis, chlorite–pyrite coexistence, temperature of ore formation, and sulfur isotope evidence indicate relatively reduced fO₂ conditions for the mineralizing fluid. Geologic, chemical, and isotopic characteristics of the Cipoeiro deposit are compatible with the class of orogenic gold deposits.     

Boron,sulphur and copper isotope systematics in the orogenic gold deposits of the Archaean Hattu schist belt,eastern Finland

The Hattu schist belt is located in the western part of the Archaean Karelian domain of the Fennoscandian Shield. The orogenic gold deposits with Au–Bi–Te geochemical signatures are hosted by NE–SW, N–S and NW–SE oriented shear zones that deform 2.76–2.73 Ga volcanic and sedimentary sequences, as well as 2.75–2.72 Ga tonalite–granodiorite intrusions and diverse felsic porphyry dykes. Mo–W mineralization is also present in some tonalite intrusions, both separate from, and associated with Au mineralization. Somewhat younger, unmineralized leucogranite intrusions (2.70 Ga) also intrude the belt. Lower amphibolite facies peak metamorphism at 3–5 kbar pressures and at 500–600 °C temperatures affected the belt at around 2.70 Ga and post-date hydrothermal alteration and ore formation. In this study, we investigated the potential influence of magmatic-hydrothermal processes on the formation of orogenic gold deposits on the basis of multiple stable isotope (B, S, Cu) studies of tourmaline and sulphide minerals by application of in situ SIMS and LA ICP MS analytical techniques.Crystal chemistry of tourmaline from a Mo–W mineralization hosted by a tonalite intrusion in the Hattu schist belt is characterized by Fe^3 +–Al^3 +-substitution indicating relatively oxidizing conditions of hydrothermal processes. The range of δ¹¹B data for this kind of tourmaline is from − 17.2‰ to − 12.2‰. The hydrothermal tourmaline from felsic porphyry dyke swith gold mineralization has similar crystal chemistry (e.g. dravite–povondraite compositional trend with Fe^3 +–Al^3 + substitution) and δ¹¹B values between − 19.0‰ and − 9.6‰. The uvite–foitite compositional trend and δ¹¹B ‰ values between − 24.1% and − 13.6% characterize metasomatic–hydrothermal tourmaline from the metasediment-hosted gold deposits. Composition of hydrothermal vein-filling and disseminated tourmaline from the gold-bearing shear zones in metavolcanic rocks is transitional between the felsic intrusion and metasedimentary rock hosted hydrothermal tourmaline but the range of average boron isotope data is essentially identical with that of the metasediment-hosted tourmaline. Rock-forming (magmatic) tourmaline from leucogranite has δ¹¹B values between − 14.5‰ and − 10.8‰ and the major element composition is similar to that of the metasediment-hosted tourmaline.The range of δ³⁴S_VCDT values measured in pyrite, chalcopyrite and pyrrhotite is from − 9.1 to + 8.5‰, which falls within the typical range of sulphur isotope data for Archaean orogenic gold deposits. In the Hattu schist belt, positive δ³⁴S_VCDT values characterize metasediment-hosted gold ores with sulphide parageneses dominated by pyrrhotite and arsenopyrite. The δ³⁴S_VCDT values are both positive and negative in ore mineral parageneses within felsic intrusive rocks in which variable amounts of pyrrhotite are associated with pyrite. Purely negative values were only recorded from the pyrite-dominated gold mineralization within metavolcanic units. Therefore the shift of δ³⁴S_VCDT values to the negative values reflects precipitation of sulphide minerals from relatively oxidizing fluids. The range of measured δ⁶⁵Cu_NBS978 values from chalcopyrite is from − 1.11 to 1.19‰. Positive values are common for mineralization in felsic intrusive rocks and negative values are more typical for deposits confined to metasedimentary rocks. Positive and negative δ⁶⁵Cu_NBS978 values occur in the ores hosted by metavolcanic rocks. There is no correlation between sulphur and copper isotope data obtained in the same chalcopyrite grains.Evaluation of sulphur and boron isotope data together and comparisons with other Archaean orogenic gold provinces supports the hypothesis that the metasedimentary rocks were the major sources of sulphur and boron in the orogenic gold deposits in the Hattu schist belt. Variations in major element and boron isotope compositions in tourmaline, as well as in the δ³⁴S_VCDT values in sulphide minerals are attributed to localized involvement of magmatic fluids in the hydrothermal processes. The results of copper isotope studies indicate that local sources of copper in orogenic gold deposits may potentially be recognized if the original, distinct signatures of the sources have not been homogenized by widespread interaction of fluids with a large variety of rocks and provided that local chemical variations have been too small to trigger changes in the oxidation state of copper during hydrothermal processes.     

Depositional age and tectonic environment of the Gouap banded iron formations from the Nyong group,SW Cameroon:Insights from isotopic,geochemical and geochronological studies of drillcore samples

The discovery of the Gouap banded iron formations(BIFs)-hosted iron mineralization in the northwestern of the Nyong Group(Ntem Complex)in southwestern Cameroon provides unique insights into the geology of this region.In this contribution,we firstly report detailed study of geochemistry,isotopic and geochronology of well preserved samples of the Gouap BIFs collected from diamond drillcores.The Gouap BIFs consist mainly of amphibole BIFs and amphibole-pyrite BIFs characterized by dominant Fe₂O₃+SiO₂contents and variable contents of CaO,MgO and SO₃,consistent with the presence of amphibole,chlorite,epidote and pyrite,formed during amphibolite facies metamorphism and overprinted hydrothermal event.The amphibole–pyrite BIFs are typically enriched in trace and rare earth elements(REE)compared to the amphibole BIFs,suggesting the influence of detrital materials as well as secondary hydrothermal alteration.The Post Archean Australian Shale(PAAS)-normalized REE–Y profiles of the Gouap BIFs display positive La,Eu anomalies,weak negative Ce anomalies,indicating a mixture of low-temperature hydrothermal fluids and relatively oxic conditions probably under relative shallow seawater.We present here the first isotopic data of BIFs within the Ntem Complex.Theδ³⁰Si_NBS28values of the quartz from the Gouap BIFs vary from-1.5‰to-0.3‰and from-0.8‰to-0.9‰for the amphibole BIFs and amphibole–pyrite BIFs,respectively.The quartz hasδ¹⁸OV-SMOW values of 6.8‰–9.5‰(amphibole BIFs)and 9.2‰–10.6‰(amphibole–pyrite BIFs).The magnetite from the Gouap BIFs showsδ¹⁸O values ranging from-3.5‰to-1.8‰and from-3‰to-1.7‰for the amphibole BIFs and amphibole–pyrite BIFs,respectively.Moreover,the pyrite grains in the amphibole–pyrite BIFs displayδ34S values of 1.1‰–1.8‰.All isotopic data of the Gouap BIFs confirm that they might have precipitated from low-temperature hydrothermal fluids with detrital input distant from the volcanic activity.According to their geochemical and isotopic characteristics,we propose that the Gouap BIFs belong to the Superior type.In situ U–Pb zircon dating of BIFs was conducted to assess the BIF depositional age based on strong evidence of zircon in thin section.The Gouap BIFs were probably deposited at 2422±50 Ma in a region where sediments extended from continental shelf to deep-water environments along craton margins like the Caue Formation of the Minas Supergroup,Brazil.The studied BIFs have experienced regional hydrothermal activity and metamorphism at 2089±8.3 Ma during the Eburnean–Transamazonian orogeny.These findings suggest a physical continuity between the protocratonic masses of both Sao Francisco and Congo continents in the Rhyacian Period.     

Geochemical and boron,oxygen and hydrogen isotopic constraints on the origin of salinity in groundwaters from the crystalline basement of the Alpine Foreland

The B isotopic composition, in combination with O and H isotopes and hydrochemical tracers, is utilized to constrain the evolution of basement-hosted groundwaters via water–rock interactions and fluid infiltration from external (sedimentary) reservoirs. Two distinct groundwater types have been identified in the Central European crystalline basement (N Switzerland–SW Germany): (1) fresh groundwaters characterized by low values of δ¹¹B (−3.5 to −0.6‰), δ¹⁸O (−12.0 to −10.0‰), and δD (−86.8 to −71.9‰), and (2) brackish groundwaters with distinctly heavier B, O, and H isotopic compositions (δ¹¹B=+6.4 to +17.6‰, δ¹⁸O=−9.4 to −5.6‰, δD=−67.6 to −60.8‰). Fresh groundwaters show a systematic decrease in δ¹¹B, related to an increase in B concentrations (and degree of total mineralization), along the pathway of groundwater migration which can only be interpreted in terms of leaching of crystalline host rocks. A δ¹¹B value of −3.3‰ is inferred for the crustal B source (mainly Hercynian granites) involved in the leaching process, in agreement with the known δ¹¹B range of granitic rocks. The evolution of brackish groundwaters, derived from crystalline basement reservoirs with little water circulation, is more complex. As indicated by B–O–H stable isotope and hydrochemical (e.g. B/Cl, Na/Cl, and Br/Cl) constraints, brackish groundwaters from the study area are influenced by admixture of sediment-derived fluids which infiltrated from Late Paleozoic (Permo-Carboniferous) and Early Mesozoic (Lower Triassic) sedimentary strata. The data presented show that B isotopes are sensitive to mixing processes of fluids derived from different crustal reservoirs and, hence, may be utilized as a tracer for constraining the internal (autochthonous) vs external (allochthonous) origin of salinity in basement-hosted groundwaters.     

Distinct zircon U–Pb and O–Hf–Nd–Sr isotopic behaviour during fluid flow in UHP metamorphic rocks: evidence from metamorphic veins and their host eclogite in the Sulu Orogen,China

Fluid plays a key role in metamorphism and magmatism in subduction zones. Veins in high‐pressure (HP) to ultrahigh‐pressure (UHP) rocks are the products of fluid‐rock interaction, and can thus provide important constraints on fluid processes in subduction zones. This contribution is an integrated study of zircon U–Pb and O–Hf, as well as whole‐rock Nd–Sr isotopic compositions for a quartz vein, a complex vein, and their host eclogite in the Sulu UHP terrane to decipher the timing and source of fluid flow under HP‐UHP metamorphic conditions. The inherited magmatic zircon cores from the host eclogite constrain the protolith age at c. 750 Ma. Their variable ε_Hf(t) values from ?1.11 to 2.54 and low δ¹⁸O values of 0.32–3.40‰ reflect a protolith that formed in a rift setting due to the breakup of the supercontinent Rodinia. The hydrothermal zircon from the quartz and the complex veins shows euhedral shapes, relatively flat HREE pattern, slight or no negative Eu anomaly, low ¹⁷⁶Lu/¹⁷⁷Hf ratios, and low formation temperatures of 660–690 °C, indicating they precipitated from fluids under HP eclogite facies conditions. This zircon yielded similar U–Pb ages of 217 ± 2 and 213 ± 3 Ma within analytical uncertainty, recording the timing of fluid flow during the exhumation of the UHP rock. It is inferred that the fluids might be of internal origin based on the homogeneity of δ¹⁸O values of the hydrothermal zircon from the quartz (?2.41 ± 0.13‰) and complex veins (?2.35 ± 0.12‰), and the metamorphic grown zircon of the host eclogite (?2.23 ± 0.16‰). The similar ε_Nd(t) values of the whole rocks also support such a point. Zircon O and whole‐rock Nd isotopic compositions are therefore useful to identify the source of fluid, for they are major and trace components in minerals involved in metamorphic reactions during HP‐UHP conditions. On the other hand, the hydrothermal zircon from the veins and the metamorphic zircon from the host eclogite exhibit variable ε_Hf(t) values. Model calculation suggests that the Hf was derived from the breakdown of major rock‐forming minerals and recycling of the inherited magmatic zircon. The variable whole‐rock initial ⁸⁷Sr/⁸⁶Sr ratios might be caused by subsequent retrograde metamorphism after the formation of the veins.     

Laser ablation multicollector ICPMS determination of δ11B in geological samples

A method for the in situ single spot δ¹¹B characterisation of geological materials with laser ablation multicollector ICP mass spectrometry (LA-MC-ICPMS) has been developed. The mass spectrometer was equipped with both Faradays and multiple ion counters. Four samples with different B contents (12–31,400 ppm) and isotopic compositions (δ¹¹B are between −8.71 and +13.6‰) were analysed. Samples include the B4 tourmaline and 3 MPI-DING glasses (StHs6/80-G, GOR132-G and GOR128-G).All sources of B isotopic fractionation during the analysis (mass bias, laser-induced isotopic fractionation and detector efficiency drift) have been evaluated and quantified. Instrumental mass bias is the major source of fractionation, altering the original isotopic ratio up to 13%. Fractionation related to laser sampling and transport to the ICP was found to be very low (less than 0.0015% s⁻¹). Fractionation effects due to drift in ion counter efficiencies were found to be significant. Nevertheless, the “standard-sample-standard” bracketing approach could be used to correct for the above fractionation effects using NIST SRM 610 as external standard.With spot sizes of 60–80 μm in diameter, geologically meaningful results can be achieved on samples containing at least 10 ppm B, i.e., results with precisions that can discriminate between the different reservoirs on Earth. Data obtained with Faraday detectors on NIST SRM 610 and B4 tourmaline show high precision (down to 0.04‰, 1σ) and accuracy. Boron isotope ratios measured in the glass samples using multiple ion counting show significantly higher standard deviations (up to 2.5‰, 1σ), but they are very close to the values that can be expected from counting statistics. No significant variations with spot size or B contents were observed. Most of the values are within 1σ level of the reference values.The developed method was applied to a series of ashes from Mt. Etna erupted in 1995 having B contents between 14 and 20 ppm. The B isotope compositions of the ashes are between −4.8 and −10.7‰, with a weighted average value of −8.0 ± 1.9‰ (1σ).     

Channelized fluids in subducted continental crust: constraints from δD–δ18O of quartz and fluid inclusions in quartz veins from the Chinese Continental Scientific Drilling Project

Fluid inclusions hosted by quartz veins in high-pressure to ultrahigh-pressure (HP-UHP) metamorphic rocks from the Chinese Continental Scientific Drilling (CCSD) Project main drillhole have low, varied hydrogen isotopic compositions (δD?=??97‰ to??69‰). Quartz δ¹⁸O values range from??2.5‰ to 9.6‰; fluid inclusions hosted in quartz have correspondingly low δ¹⁸O values of??11.66‰ to 0.93‰ (T _h?=?171.2～318.8°C). The low δD and δ¹⁸O isotopic data indicate that protoliths of some CCSD HP-UHP metamorphic rocks reacted with meteoric water at high latitude near the surface before being subducted to great depth. In addition, the δ¹⁸O of the quartz veins and fluid inclusions vary greatly with the drillhole depth. Lower δ¹⁸O values occur at depths of ～900–1000 m and ～2700 m, whereas higher values characterize rocks at depths of about 1770 m and 4000 m, correlating roughly with those of wall-rock minerals. Given that the peak metamorphic temperature of the Dabie-Sulu UHP metamorphic rocks was about 800°C or higher, much higher than the closure temperature of oxygen isotopes in quartz under wet conditions, such synchronous variations can be explained by re-equilibration. In contrast, δD values of fluid inclusions show a different relationship with depth. This is probably because oxygen is a major element of both fluids and silicates and is much more abundant in the quartz veins and silicate minerals than is hydrogen. The oxygen isotope composition of fluid inclusions is evidently more susceptible to late-stage re-equilibration with silicate minerals than is the hydrogen isotope composition. Therefore, different δD and δ¹⁸O patterns imply that dramatic fluid migration occurred, whereas the co-variation of oxygen isotopes in fluid inclusions, quartz veins, and wall-rock minerals can be better interpreted by re-equilibration during exhumation.

Quartz veins in the Dabie-Sulu UHP metamorphic terrane are the product of high-Si fluids. Given that channelized fluid migration is much faster than pervasive flow, and that the veins formed through precipitation of quartz from high-Si fluids, the abundant veins indicate significant fluid mobilization and migration within this subducted continental slab. Many mineral reactions can produce high-Si fluids. For UHP metamorphic rocks, major dehydration during subduction occurred when pressure–temperature conditions exceeded the stability of lawsonite. In contrast, for low-temperature eclogites and other HP metamorphic rocks with peak metamorphic P–T conditions within the stability field of lawsonite, dehydration and associated high-Si fluid release may have occurred as hydrous minerals were destabilized at lower pressure during exhumation. Because subduction is a continuous process whereas only a minor fraction of the subducted slabs returns to the surface, dehydration during underflow is more prevalent than exhumation even in subducted continental crust, which is considerably drier than altered oceanic crust.