Sulphur source and genesis of polymetallic sulphide occurrences of the Ofoten district in the Central–North Norwegian Caledonides: evidence from sulphur isotopic studies

Fourteen stratiform, stratabound and vein-type sulphide occurrences in the Upper Allochthon of the Central–North Norwegian Caledonides have been studied for their sulphur, oxygen and hydrogen isotope composition. Depositional ages of host rocks to the stratabound and stratiform sulphide occurrences range from 590 to 640?Ma. The sulphides and their host rocks have been affected by polyphase deformation and metamorphism with a peak temperature of 650?°C dated to 432?Ma. A total of 104 sulphide and 2 barite samples were analysed for δ³⁴S, 16 whole-rock and quartz samples for δ¹⁸O and 12 samples of muscovite for δD. The overall δ³⁴S values range from ?14 to +31‰ with the majority of sampled sulphides lying within a range of +4 to +15‰. In most cases δ³⁴S within each hand specimen behaves in accordance with the equilibrium fractionation sequence, δ³⁴S_gn<δ³⁴S_cp<δ³⁴S_sph<δ³⁴S_py. A systematic increase in δ³⁴S from the vein sulphides (?8‰) through schist/amphibolite-hosted (+6‰) and schist-hosted (+7 to +12‰) to dolomite-hosted (+12 to +31‰) occurrences is documented. The δ³⁴S averages of the stratiform schist-hosted sulphides are 17 to 22‰ lower than in the penecontemporaneous seawater sulphate. The Bjørkåsen (+4 to +6‰) occurrence is a volcanogenic massive sulphide (VMS) transitional to sedimentary massive sulphide (SMS), exhalative, massive, pyritic deposit of Cu–Zn–Pb sulphides formed by fluids which obtained H₂S via high-temperature reduction of seawater sulphate by oxidation of Fe²⁺ during the convective circulation of seawater through underlying rock sequences. The Raudvatn, volcanic-hosted, disseminated Cu sulphides (+6 to +8‰) obtained sulphur via a similar process. The Balsnes, stratiform, ‘black schist’-hosted, pyrite–pyrrhotite occurrence (?6 to ?14‰) is represented by typical diagenetic sulphides precipitated via bacteriogenic reduction of coeval (ca. 600?Ma) seawater sulphate (+25 to +35‰) in a system open to sulphate supply. The δ³⁴S values of the Djupvik–Skårnesdalen (+7 to +12‰), Hammerfjell (+5 to 11‰), Kaldådalen (+10 to +12‰) and Njallavarre (+7 to +8‰) stratiform, schist-hosted, massive and disseminated Zn–Pb (±Cu) sulphide occurrences, as well as the stratabound, quartzite-hosted, Au-bearing arsenopyrite occurrence at Langvatnet (+7 to +11‰), suggest that thermochemically reduced connate seawater sulphate was a principal sulphur source. The Sinklien and Tårstad, stratabound, dolomite- and dolomite collapse breccia-hosted, Zn (±Cu–Pb) sulphides are marked by the highest enrichment in ³⁴S (+20 to +31‰). The occurrences ?are?assigned to the Mississippi-Valley-type deposits.?High δ³⁴S values require reduction/replacement of contemporaneous (ca. 590?Ma) evaporitic sulphate (+23 to +34‰) with C_org-rich fluids in a closed system. The Melkedalen (+12 to +15‰), stratabound, fault-controlled, Cu–Zn sulphide deposit is hosted by the ca. 595?Ma dolomitised Melkedalen marble. The deposit is composed of several generations of ore minerals which formed by replacement of host dolomite. Polyphase hydrothermal fluids were introduced during several reactivation episodes of the fault zone. The positive δ³⁴S values with a very limited fractionation (<3‰) are indicative of the sulphide-sulphur generated through abiological, thermochemical reduction of seawater sulphate by organic material. The vein-type Cu (±Au–W) occurrences at Baugefjell, Bugtedalen and Baugevatn (?8 to ?4‰) are of hydrothermal origin and obtained their sulphur from igneous sources with a possible incorporation of sedimentary/diagenetic sulphides. In a broad sense, all the stratiform/stratabound, sediment-hosted, sulphide occurrences studied formed by epigenetic fluids within two probable scenarios which may be applicable separately or interactively: (1) expulsion of hot metal-bearing connate waters from deeper parts of sedimentary basins prior to nappe translation (late diagenetic/catagenetic/epigenetic fluids) or (2) tectonically driven expulsion in the course of nappe translation (early metamorphic fluids). A combination of (1) and (2) is favoured for the stratabound, fault-controlled, Melkedalen and Langvatnet occurrences, whereas the rest are considered to have formed within option (1). The sulphides and their host rocks were transported from unknown distances and thrust on to the Fennoscandian Shield during the course of the Caledonian orogeny. The displaced/allochthonous nature of the Ofoten Cu–Pb–Zn ‘metallogenetic province’ would explain the enigmatically high concentration of small-scale Cu–Pb–Zn deposits that occur only in this particular area of the Norwegian Caledonides.     

The Hakkari nonsulfide Zn–Pb deposit in the context of other nonsulfide Zn–Pb deposits in the Tethyan Metallogenic Belt of Turkey

The Hakkari nonsulfide zinc deposit is situated close to the southeastern border of Turkey. Here both sulfide and nonsulfide Zn ≫ Pb ores are hosted in carbonate rocks of the Jurassic Cudi Group with features typical of carbonate-hosted supergene nonsulfide zinc mineralization. The regional strike extent of the mineralized district is at least 60 km. The age of the supergene deposit has not been determined, but it is probable that the main weathering happened during Upper Tertiary, possibly between Upper Miocene and Lower Pliocene. The Hakkari mineralization can be compared to other carbonate-hosted Zn–Pb deposits in Turkey, and an interpretation made of its geological setting. The zinc mineral association at Hakkari typically comprises smithsonite and hemimorphite, which apparently replace both sulfide minerals and carbonate host rock. Two generations of smithsonite are present: the first is relatively massive, the second occurs as concretions in cavities as a final filling of remnant porosity. Some zinc is also hosted within Fe–Mn-(hydr)oxides. Lead is present in cerussite, but also as partially oxidized galena. Lead can also occur in Mn-(hydr)oxides (max 30% PbO). The features of the supergene mineralization suggest that the Hakkari deposit belongs both to the “direct replacement” and the “wall-rock replacement” types of nonsulfide ores. Mineralization varies in style from tabular bodies of variable thickness (< 0.5 to 13 m) to cross-cutting breccia zones and disseminated ore minerals in pore spaces and fracture planes. At Hakkari a As–Sb–Tl(≫ Hg) geochemical association has been detected, which may point to primary sulfide mineralization, quite different from typical MVT.     

U–Pb dating of silicic lavas,sills and syneruptive resedimented volcaniclastic deposits of the Lower Devonian Crudine Group,Hill End Trough,New South Wales

The Hill End Trough of central‐western New South Wales was an elongate deep marine basin that existed in the Lachlan Fold Belt from the early Late Silurian to late Early Devonian. It is represented by a regionally extensive, unfossiliferous sequence of interbedded turbidites and hemipelagites of substantially silicic volcanic derivation, which passes laterally into contemporaneous shallow‐water sedimentary rocks. The Turondale and Merrions Formations of the Lower Devonian Crudine Group are two prominent volcanogenic formations in the predominantly sedimentary trough sequence. They contain a range of primary and resedimented volcanic facies suitable for U–Pb dating. These include widespread subaqueous silicic lavas and/or lava cryptodomes, and thick sequences of crystal‐rich volcaniclastic sandstone emplaced by a succession of mass‐flows that were generated by interaction between contemporaneous subaerial pyroclastic flows and the sea. Ion microprobe dating of the two volcanogenic formations by means of the commonly used SL 13 zircon standard yields ages ranging between 411.3 ± 5.1 and 404.8 ± 4.8 Ma. Normalising the data against a different zircon standard (QGNG) yields preferred slightly older mean ages that range between 413.4 ± 6.6 and 407.1 ± 6.9 Ma. These ages broadly approximate the Early Devonian age that has been historically associated with the Crudine Group. However, the biostratigraphically inferred late Lochkovian ‐ early Emsian (mid‐Early Devonian) age for the Merrions Formation is inconsistent with the current Australian Phanerozoic Timescale, which assigns an age of 410 Ma to the Silurian‐Devonian boundary, and ages of 404.5 Ma and 395.5 Ma to the base and top of the Pragian, respectively. There is, however, good agreement if the new ages are compared with the most recently published revision of the Devonian time‐scale. This suggests that the Early Devonian stage boundaries of the Australian Phanerozoic Timescale need to be revised downward. The new ages for the Merrions Formation could also provide a time point on this time‐scale for the Pragian to early Emsian, for which no data are presently available.     

S,Pb, and Sr isotope geochemistry and genesis of Pb–Zn mineralization in the Huangshaping polymetallic ore deposit of southern Hunan Province,China

The Huangshaping Pb–Zn–W–Mo polymetallic deposit, located in southern Hunan Province, China, is one of the largest deposits in the region and is unique for its metals combination of Pb–Zn–W–Mo and the occurrence of significant reserves of all these metals. The deposit contains disseminated scheelite and molybdenite within a skarn zone located between Jurassic granitoids and Carboniferous sedimentary carbonate, and sulfide ores located within distal carbonate-hosted stratiform orebodies. The metals and fluids that formed the W–Mo mineralization were derived from granitoids, as indicated by their close spatial and temporal relationships. However, the source of the Pb–Zn mineralization in this deposit remains controversial.Here, we present new sulfur, lead, and strontium isotope data of sulfide minerals (pyrrhotite, sphalerite, galena, and pyrite) from the Pb–Zn mineralization within the deposit, and these data are compared with those of granitoids and sedimentary carbonate in the Huangshaping deposit, thereby providing insights into the genesis of the Pb–Zn mineralization. These data indicate that the sulfide ores from deep levels in the Huangshaping deposit have lower and more consistent δ³⁴S values (− 96 m level: + 4.4‰ to + 6.6‰, n = 13) than sulfides within the shallow part of the deposit (20 m level: + 8.3‰ to + 16.3‰, n = 19). The δ³⁴S values of deep sulfides are compositionally similar to those of magmatic sulfur within southern Hunan Province, whereas the shallower sulfides most likely contain reduced sulfur derived from evaporite sediments. The sulfide ores in the Huangshaping deposit have initial ⁸⁷Sr/⁸⁶Sr ratios (0.707662–0.709846) that lie between the values of granitoids (0.709654–0.718271) and sedimentary carbonate (0.707484–0.708034) in the Huangshaping deposit, but the ratios decreased with time, indicating that the ore-forming fluids were a combination of magmatic and formation-derived fluids, with the influence of the latter increasing over time. The lead isotopic compositions of sulfide ores do not correlate with sulfide type and define a linear trend in a ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb diagram that is distinct from the composition of the disseminated pyrite within sedimentary carbonates and granitoids in the Huangshaping deposit, but is similar to the lead isotopic composition of sulfides within coeval skarn Pb–Zn deposits in southern Hunan Province. In addition, the sulfide ores have old signatures with relative high ²⁰⁷Pb/²⁰⁶Pb ratios, suggesting that the underlying Paleoproterozoic basement within southern Hunan Province may be the source of metals within the Huangshaping deposit.The isotope geochemistry of sulfide ores in the Huangshaping deposit shows a remarkable mixed source of sulfur and ore-forming fluids, and the metals were derived from the basement. These features are not found in representative skarn-type Pb–Zn mineralization located elsewhere. The ore-forming elements (S, Pb, and Zn) from the granitoids made an insignificant contribution to sulfide precipitation in this deposit. However, the emplacement of granitoids did provide large amounts of heat and fluids to the hydrothermal system in this area and extracted metals from the basement rocks, indicating that the Jurassic magmatism associated with the Huangshaping deposit was crucial to the Pb–Zn mineralization.     

The nature and genesis of marginal Cu–PGE–Au sulphide mineralisation in Paleogene Macrodykes of the Kangerlussuaq region, East Greenland

The Kangerlussuaq region of East Greenland hosts a variety of early Tertiary extrusive and intrusive igneous rocks related to continental break up and the passage of the ancestral Iceland plume. These intrusive bodies include a number of gabbroic macrodykes, two of which—the Miki Fjord Macrodyke, and the newly discovered Togeda Macrodyke—contain Cu–PGE–Au sulphide mineralisation along their margins. Sulphides occur as disseminated interstitial blebs and rounded globules of chalcopyrite and pyrrhotite with some Fe–Ti oxides and platinum-group minerals, comprising largely Pd bismuthides and tellurides. The globules are interpreted to have formed from fractionation of trapped droplets of an immiscible Cu- and Pd-rich sulphide melt and show geopetal indicators. Sulphur isotopes imply a local crustal source of S in these from pyritic sediments of the Kangerlussuaq Basin. Thus, generation of these sulphide occurrences was controlled by local country rock type. Low Ni/Cu and Pt/Pd ratios, also present in the Platinova reefs in the Skaergaard Intrusion, indicate that early fractionation of olivine may have depleted the magma of Ni and suggest the likely presence of a large magma chamber at depth. Xenoliths of Ni-rich olivine cumulates in the Miki Fjord Macrodyke may have been sourced from such a body. The location of thus far unidentified conduit or feeder zones to the macrodykes beneath the present day surface may represent potential targets for more massive sulphide orebodies.     

Paleomagnetic constraints on Zn–Pb ore genesis of the Pillara Mine, Lennard Shelf, Western Australia

The Pillara Zn–Pb deposit is the largest of several known Mississippi Valley-type (MVT) deposits in the Lennard Shelf of the Canning Basin. Paleomagnetic and rock magnetic measurements are reported for 294 specimens from 23 sites in mineralization and its carbonate host rocks from the deposit as well as on 15 artificial specimens of zinc and lead concentrate and of tailings. Pyrrhotite carries the characteristic remanent magnetization (ChRM) in nearly all specimens. The ChRM postdates most faulting as shown by breccia tests and most minor regional tilting as shown by the degraded fit on tilt correction. The mean ChRM direction for all sites is D=20.6°, I=–27.5° (N=23, ₉₅=5.3°, k=34.1), yielding an age of 358±5 Ma (2) that is similar to the comparable age of 354±8 Ma (2) for the Kapok MVT deposit. Host rock diagenesis with attendant secondary remagnetization yields an age of 361±5 Ma (1) and the MVT mineralization with a primary chemical remanent magnetization gives an age of 356±3 Ma (1), co-eval with a published Rb–Sr sphalerite age of 357±3 Ma. Interpretation of this temporal data suggests that the MVT deposits of the southeastern Lennard Shelf originated during extension, probably in response to rift-related topography-driven fluid flow.Editorial handling: C. Brauhart     

Geology,isotope geochemistry and ore genesis of the Shanshulin carbonate-hosted Pb–Zn deposit,southwest China

The Shanshulin Pb–Zn deposit occurs in Upper Carboniferous Huanglong Formation dolomitic limestone and dolostone, and is located in the western Yangtze Block, about 270 km west of Guiyang city in southwest China. Ore bodies occur along high angle thrust faults affiliated to the Weishui regional fault zone and within the northwestern part of the Guanyinshan anticline. Sulfide ores are composed of sphalerite, pyrite, and galena that are accompanied by calcite and subordinate dolomite. Twenty-two ore bodies have been found in the Shanshulin deposit area, with a combined 2.7 million tonnes of sulfide ores grading 0.54 to 8.94 wt.% Pb and 1.09 to 26.64 wt.% Zn. Calcite samples have δ¹³C_PDB and δ¹⁸O_SMOW values ranging from − 3.1 to + 2.5‰ and + 18.8 to + 26.5‰, respectively. These values are higher than mantle and sedimentary organic matter, but are similar to marine carbonate rocks in a δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, suggesting that carbon in the hydrothermal fluid was most likely derived from the carbonate country rocks. The δ³⁴S_CDT values of sphalerite and galena samples range from + 18.9 to + 20.3‰ and + 15.6 to + 17.1‰, respectively. These values suggest that evaporites are the most probable source of sulfur. The δ³⁴S_CDT values of symbiotic sphalerite–galena mineral pairs indicate that deposition of sulfides took place under chemical equilibrium conditions. Calculated temperatures of S isotope thermodynamic equilibrium fractionation based on sphalerite–galena mineral pairs range from 135 to 292 °C, consistent with previous fluid inclusion studies. Temperatures above 100 °C preclude derivation of sulfur through bacterial sulfate reduction (BSR) and suggest that reduced sulfur in the hydrothermal fluid was most likely supplied through thermo-chemical sulfate reduction (TSR). Twelve sphalerite samples have δ⁶⁶Zn values ranging from 0.00 to + 0.55‰ (mean + 0.25‰) relative to the JMC 3-0749L zinc isotope standard. Stages I to III sphalerite samples have δ⁶⁶Zn values ranging from 0.00 to + 0.07‰, + 0.12 to + 0.23‰, and + 0.29 to + 0.55‰, respectively, showing the relatively heavier Zn isotopic compositions in later versus earlier sphalerite. The variations of Zn isotope values are likely due to kinetic Raleigh fractional crystallization. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of the sulfide samples fall in the range of 18.362 to 18.573, 15.505 to 15.769 and 38.302 to 39.223, respectively. The Pb isotopic ratios of the studied deposit plot in the field that covers the upper crust, orogenic belt and mantle Pb evolution curves and overlaps with the age-corrected Proterozoic folded basement rocks, Devonian to Lower Permian sedimentary rocks and Middle Permian Emeishan flood basalts in a ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb diagram. This observation points to the derivation of Pb metal from mixed sources. Sphalerite samples have ⁸⁷Sr/⁸⁶Sr_200 Ma ratios ranging from 0.7107 to 0.7115 similar to the age-corrected Devonian to Lower Permian sedimentary rocks (0.7073 to 0.7111), higher than the age-corrected Middle Permian basalts (0.7039 to 0.7078), and lower than the age-corrected Proterozoic folded basement (0.7243 to 0.7288). Therefore, the Sr isotope data support a mixed source. Studies on the geology and isotope geochemistry suggest that the Shanshulin deposit is a carbonate-hosted, thrust fault-controlled, strata-bound, epigenetic, high grade deposit formed by fluids and metals of mixed origin.     

Palynostratigraphy of the Chapada Group and its significance in the Devonian stratigraphy of the Paraná Basin,south Brazil

The Alto Garças Sub-basin in the northern part of the Paraná Basin evolved differently from the Apucarana Sub-basin in the south. The marine environment was shallower in the Alto Garças Sub-basin, which contains proportionately more silty and arenaceous rocks. The formations and members defined in the Apucarana Sub-basin are therefore difficult to apply in the Alto Garças Sub-basin, where the Chapada Group (units 1–4) is more applicable. An integrated miospore and chitinozoan biozonation of the Chapada Group facilitates direct correlation between the Chapada Group’s units and the classical formations of the Paraná Basin as defined in the Apucarana Sub-basin. The Furnas Formation and Chapada unit 1 constitute the same lithostratigraphic unit. Beds with rhyniophytes in the uppermost part of the Furnas Formation contain palynomorphs representative of the Si phylozone within the MN spore Zone (late Lochkovian), and the rhyniophyte beds occupy the same stratigraphic interval within Chapada unit 1 (the Lochkovian of the Paraná Basin lacks chitinozoans). The lower part of Chapada unit 2 contains spores of the PoW Su spore Zone and chitinozoans of the Ramochitina magnifica and Ancyrochitina pachycerata zones, together indicating a late Pragian–early Emsian age-span. The upper part of Chapada unit 2 corresponds to the GS (AP) and Per (AD pre-Lem) spore Zones, and chitinozoans of the Ancyrochitina parisi, the informal Ancyrochitina varispinosa and Alpenachitina eisenacki chitinozoan zones, thus suggestive of a late Emsian – earliest Givetian age-span. Unit 3 is a proximal and lateral facies equivalent of the upper part of unit 2. The lower part of unit 4 includes spores typical of the early Givetian Lli (AD Lem) spore Zone and chitinozoans of the Ramochitina stiphrospinata chitinozoan Zone; the uppermost (early late Frasnian) part contains spores of the lower BMu (IV) spore Zone and chitinozoans of the Lagenochitina avelinoi chitinozoan Zone. The sandstones of unit 3 were inundated during the earliest Givetian, and the resultant flooding surface marks the base of unit 4 basin-wide. Clearly, the two sub-basins were distinct depositional centers during the Devonian.     

The mixing of multi-source fluids in the Wusihe Zn–Pb ore deposit in Sichuan Province,Southwestern China

The Sichuan–Yunnan–Guizhou (SYG) metallogenic province of southwest China is one of the most important Zn–Pb ore zones in China, with ~ 200 Mt Zn–Pb ores at mean grades of 10 wt.% Zn and 5 wt.% Pb. The source and mechanism of the regional Zn–Pb mineralization remain controversial despite many investigations that have been conducted. The Wusihe Zn–Pb deposit is a representative large-scale Zn–Pb deposit in the northern SYG, which mainly occurs in the Dengying Formation and yields Zn–Pb resources of ~ 3.7 Mt. In this paper, Zn and S isotopes, and Fe and Cd contents of sphalerite from the Wusihe deposit were investigated in an attempt to constrain the controls on Zn and S isotopic variations, the potential sources of ore-forming components, and the possible mineralization mechanisms. Both the δ⁶⁶Zn and δ³⁴S values in sphalerite from the Wusihe deposit increase systematically from the bottom to the top of the strata-bound orebodies. Such spatial evolution in δ⁶⁶Zn and δ³⁴S values of sphalerite can be attributed to isotopic Rayleigh fractionation during sphalerite precipitation with temperature variations. The strong correlations between the Zn–S isotopic compositions and Fe–Cd concentrations in sphalerite suggest that their variations were dominated by a similar mechanism. However, the Rayleigh fractionation mechanism cannot explain the spatial variations of Fe and Cd concentrations of sphalerite in this deposit. It is noted that the bottom and top sphalerites from the strata-bound orebodies document contrasting Zn and S isotopic compositions which correspond to the Zn and S isotopic characteristics of basement rocks and host rocks, respectively. Therefore, the mixing of two-source fluids with distinct Zn–S isotopic signatures was responsible for the spatial variations of Zn–S isotopic compositions of sphalerite from the Wusihe deposit. The fluids from basement rocks are characterized by relatively lighter Zn (~ 0.2 ‰) and S (~ 5 ‰) isotopic compositions while the fluids from host rocks are marked by relatively heavier Zn (~ 0.6 ‰) and S (~ 15 ‰) isotopic compositions.

     

Pb–Pb Age of Carbonate Rocks of the Kamo Group,Baikit Anteclise of the Siberian Platform

Doklady Earth Sciences - The first direct Pb–Pb dating of carbonate rocks of the Kamo Group has been carried out. The Pb–Pb age of carbonates of the lower units (the Madra, Jurubchen,...     

Age and correlations of the Siluro‐Devonian strata in the Yass Basin,New South Wales

An early Ludlovian (early eβ1) to early Gedinnian (early eγ) age is assigned to the Cliftonwood Limestone—Elmside Formation strata of the Yass Basin, New South Wales. Several Australian sequences are correlated with the Yass Basin succession.     

Insights into ore genesis of the Jinding Zn–Pb deposit,Yunnan Province,China: Evidence from Zn and in-situ S isotopes

The Jinding Zn–Pb deposit located in the Mesozoic-Cenozoic Lanping Basin of southwest China has ore reserves of ∼ 220 Mt with an average grade of 6.1% Zn and 1.3% Pb. The mineralization is hosted by sandstone in the Early Cretaceous Jingxing Formation and limestone breccia in the Paleocene Yunlong Formation. Mineralization in both types of host rocks is characterized by a paragenetic sequence beginning with marcasite–sphalerite (Stage 1) followed by pyrite–marcasite–sphalerite–galena (Stage 2), and then galena–sphalerite–pyrite–sulfate–carbonate (Stage 3). Pyrite from these stages have different δ³³S compositions with pyrite from Stage 1 averaging − 9.6‰, Stage 2 averaging − 8.9‰, and Stage 3 averaging + 0.3‰. Sphalerite hosted by the sandstone has similar δ⁶⁶Zn values ranging from 0.10 to 0.30‰ in all stages of the mineralization, but sphalerite samples from the limestone breccia-hosted ore show variable δ⁶⁶Zn values between − 0.03 and 0.20‰. Our data on sphalerite precipitated during the earlier stages of mineralization has a constant δ⁶⁶Zn value and cogenetic pyrite displays a very light sulfur isotope signature, which we believe to reflect a sulfur source that formed during bacterial sulfate reduction (BSR). The Stage 3 sphalerite and pyrite precipitated from a late influx of metal-rich basinal brine, which had a relatively constant variable δ⁶⁶Zn isotopic composition due to open system isotope fractionation, and a near zero δ³³S composition due to the influence of abiotic thermochemical sulfate reduction from observed sulfates in the host rock.     

Researches on Plants from the Lower Devonian Xujiachong Formation in the Qujing District, Eastern Yunnan

Fossil plants Hedeia sinica Hao et Gensel 1998, Huia gracilis Wang et Hao 2001 and Guangnania cuneata Wang et Hao are described from the Lower Devonian Xujiachong Formation, the Qujing district, eastern Yunnan, China. They contribute to our knowledge of the flora in this district. Based on the occurrence of common plants (Hedeia, Huia, Guangnania and Zosterophyllum australianum) and their horizons, it is proved for the first time that the mid-lower assemblage of the Xujiachong flora is comparable with the Early Devonian ((late) Pragian) Posongchong flora of southeastern Yunnan and the upper Baragwanathia flora of Australia. In view of this fact and the stratigraphic sequence, the mid-lower part of the Xujiachong Formation is considered to be of (late) Pragian age. Through comprehensive analyses of plant, bivalve and fish assemblages and the lithology, the upper part of the Xujiachong Formation is dated to be of early Emsian age. The Xujiachong flora belonged to the northeastern Gondwana palaeophytogeogr     

Geochemistry of deep formation waters in the Canning Basin,Western Australia,and their relationship to Zn‐Pb mineralization

The Canning Basin contains several Mississippi Valley‐type Zn‐Pb sulphide prospects and deposits in Devonian carbonate reef complexes on the northern edge of the Fitzroy Trough, and in Ordovician and Silurian marine sequences on the northern margin of the Willara Sub‐basin. This study uses the ionic composition and 5D, δ¹⁸O, δ³⁴S, ⁸⁷Sr/⁸⁶Sr isotopic data on present‐day deep formation waters to determine their origin and possible relationship to the Zn‐Pb mineralizing palaeofluids.

The present‐day Canning Basin formation waters have salinity ranging from typically less than 5000 mg/L up to 250 000 mg/L locally. The brines are mixtures of highly saline water, formed by seawater which evaporated beyond halite saturation (bittern water), with meteoric water ranging in salinity from low (<5000 mg/L) to hypersaline water (up to about 50 000 mg/L) formed by re‐solution of halite and calcium sulphate minerals. The original marine chemical composition of the bittern‐dominated brines was changed to that of a Na‐Ca‐Cl water by addition of Ca and removal of Mg and SO₄, initially by bacterial sulphate reduction and later by dolomitization of carbonate. Other reactions with terrigenous components of the sediment have provided additional Ca and Sr, including a small proportion of ⁸⁷Sr‐rich material. The δ³⁴S values of the bittern‐containing waters are within the range over which marine sulphate has fluctuated from the Ordovician to the Holocene, although one of the hypersaline waters has a value of +6.8%, indicating SO₄ of non‐marine origin. The pH of the bittern‐containing waters is low (about 5) and they contain significant concentrations of dissolved Fe (up to 120 mg/L).

The Canning Basin bitterns appear similar in origin and chemical composition to highly saline marine brines in the Mississippi Salt Dome Basin, USA, which are known to be either metal or sulphide‐rich depending on the organic content of the host rock. In the Canning Basin, mixing of the bittern water with the various types of meteoric water has resulted in decreases in salinity, Na, Ca, Mg, K, Sr, Li and Fe, and increases in HCO₃, SO₄ and pH.

Mixing of the bitterns with other types of metalliferous fluids and/or with sulphate‐containing hypersaline meteoric waters formed from the same marine evaporite sequence should produce ore‐precipitating fluids which are relatively hot and saline, and the resulting ore deposit should be of high grade and contain abundant sulphate minerals. In the southern Canning Basin, this type of mixing and the corresponding style of ore deposit is evident in the evaporite‐associated areas of Zn‐Pb mineralization near the Admiral Bay Fault. If the bitterns mix with low salinity HCO₃‐waters in near‐surface environments, then the ore‐precipitating fluids should have relatively low salinities and carbonate minerals would precipitate during later stages of mixing. In the Lennard Shelf, the present‐day formation waters, the style of the Zn‐Pb deposits, and range of salinity and temperature of the ore‐forming palaeofluids are consistent with this type of mixing.     

Significance of Middle Devonian granitoid‐bearing conglomerates in the Mt Morgan region,central Queensland

The presence of granitoid clasts in Devonian sequences of the Mt Morgan area has been considered indicative of a Late Devonian age, with the clasts derived from the Middle Devonian (377 Ma) Mt Morgan Trondhjemite. However, a sequence of limestone and volcanolithic arenites and breccias containing Middle Devonian corals and conodonts, overlies a granitoid‐bearing conglomerate in Station Creek. This sequence, previously mapped as Dee Volcanics, is now assigned to the Raspberry Creek Formation of the Capella Creek Group. Petrographic and geochemical similarities between the granitoid clasts and phases of the Mt Morgan Trondhjemite indicate formation in similar tectonic environments by similar magmatic processes. These clasts were derived from either an earlier phase of Mt Morgan Trondhjemite magmatism, or from a discrete earlier magmatic episode of similar type and inferred tectonic setting to the Mt Morgan intrusion.     

Mid‐Devonian movements in the Northeastern Lachlan Fold Belt

Calculations of the angular discordance between the Upper Devonian Lambie/Catombal Groups and underlying Lower Devonian formations at 130 separate locations in six areas in the northeastern Lachlan Fold Belt show that the unconformity is of a low angle except for one locality, near Limekilnes (100°). Fewer than 3% of the calculated angular discordances exceed 30°, and 73%” are less than 20°. Attempts to discover a mid‐Devonian fold direction from the restored orientation of the Lower Devonian beds, after the Upper Devonian beds have been rotated to horizontal, have been unsuccessful. Scatter of the restored bedding poles, either primary, or introduced by deformation or imprecision inherent in the measurement technique, camouflages any consistent mid‐Devonian fold axis.

Although there was demonstrable uplift, tilting, and erosion in the mid‐Devonian, limb dips on any mid‐Devonian folds do not exceed 30°. From consideration of our data, and the interpretation of angular unconformities, we conclude that there is insufficient evidence in the northeastern Lachlan Fold Belt to support an orogenic scheme in which the intense meridional deformation is synchronous with the major mid‐Devonian facies change, and part of a terminal orogeny. Only when the structures above, below and across unconformities have been mapped in some detail, will it be possible to define the nature and extent of any diastrophism that accompanied the formation of the unconformities.     

The Middle Devonian Bimodal Association of Volcanic Rocks in the Northern Area of East Junggar, Xinjiang

The Middle Devonian volcanic rocks in the northern area of East Junggar, located between the Ertix andUlungur rivers of northern Xinjiang, may be divided into basic and acid ones. It is evident that a compositionalgap exists between the two groups so that the volcanic rocks are not in line with a calc-alkaline series becausethe intermediate rocks are absent in the area. The fact shows that the volcanic rocks are a typical bimodal asso-ciation. The formation of the bimodal association of volcanic rocks in the area was closely related to continen-tal rifting or continental extension in the Middle Devonian. In such a tectonic setting, magmas were first pro-duced by partial melting of the mantle. Where crustal thinning was greater, the magmas ascended and eruptedon the surface directly so that the basic volcanic rocks formed, but olivine and/or partial pyroxenefractionation occurred in the magmas during their ascent through the thinning crust. On the other hand, wherecrustal thinning was less, ascending mantle-derived magmas reached the lower crust and accumulated there, re-sulting in partial melting of the lower crust and thus giving rise to the contaminated magma which was consoli-dated as acid volcanic rocks on the surface.