Paleomagnetism of the Middle–Late Jurassic to Cretaceous red beds from the Peninsular Thailand: Implications for collision tectonics

Jurassic to Cretaceous red sandstones were sampled at 33 sites from the Khlong Min and Lam Thap formations of the Trang Syncline (7.6°N, 99.6°E), the Peninsular Thailand. Rock magnetic experiments generally revealed hematite as a carrier of natural remanent magnetization. Stepwise thermal demagnetization isolates remanent components with unblocking temperatures of 620–690 °C. An easterly deflected declination (D = 31.1°, I = 12.2°, α₉₅ = 13.9°, N = 9, in stratigraphic coordinates) is observed as pre-folding remanent magnetization from North Trang Syncline, whereas westerly deflected declination (D = 342.8°, I = 22.3°, α₉₅ = 12.7°, N = 13 in geographic coordinates) appears in the post-folding remanent magnetization from West Trang Syncline. These observations suggest an occurrence of two opposite tectonic rotations in the Trang area, which as a part of Thai–Malay Peninsula received clockwise rotation after Jurassic together with Shan-Thai and Indochina blocks. Between the Late Cretaceous and Middle Miocene, this area as a part of southern Sundaland Block experienced up to 24.5° ± 11.5° counter-clockwise rotation with respect to South China Block. This post-Cretaceous tectonic rotation in Trang area is considered as a part of large scale counter-clockwise rotation experienced by the southern Sundaland Block (including the Peninsular Malaysia, Borneo and south Sulawesi areas) as a result of Australian Plate collision with southeast Asia. Within the framework of Sundaland Block, the northern boundary of counter-clockwise rotated zone lies between the Trang area and the Khorat Basin.     

High-pressure and ultrahigh-temperature metamorphism at Komateri,northern Madurai Block,southern India

We report for the first time the evidence for prograde high-pressure (HP) metamorphism preceding a peak ultrahigh-temperature (UHT) event in the northernmost part of the Madurai Block in southern India. Mg–Al-rich Grt–Ged rocks from Komateri in Karur district contain poikiloblastic garnet with numerous multi-phase inclusions. Although most of the inclusion assemblages are composed of gedrite, quartz, and secondary biotite, rare staurolite + sapphirine and spinel + quartz are also present. The X_Mg (=Mg/[Fe+Mg]) of staurolite (0.45–0.49) is almost consistent with that reported previously from Namakkal district in the Palghat–Cauvery Shear Zone system (X_Mg = 0.51–0.52), north of the Madurai Block. The HP event was followed by peak UHT metamorphism at T = 880–1040 °C and P = 9.8–12.5 kbar as indicated by thermobarometric computations in the Grt–Ged rock and associated mafic granulite. Symplectic intergrowth of spinel (X_Mg = 0.50–0.59, ZnO < 1.7 wt.%) and quartz, a diagnostic indicator of UHT metamorphism, probably formed by decompression at UHT conditions. The rocks subsequently underwent retrograde metamorphism at T = 720–760 °C and P = 4.2–5.1 kbar. The P–T conditions and clockwise exhumation trajectory of the Komateri rocks, comparable to similar features recorded from the Palghat–Cauvery Shear Zone system, suggest that the Madurai Block and the Palghat–Cauvery Shear Zone system underwent similar HP and UHT metamorphic history probably related to the continent–continent collision during the final stage of amalgamation of Gondwana supercontinent.     

Paleomagnetic data and K–Ar ages from Mesozoic units of the Santa Marta massif: A preliminary interpretation for block rotation and translations

We report 6 K–Ar ages and paleomagnetic data from 28 sites collected in Jurassic, Lower Cretaceous and Paleocene rocks of the Santa Marta massif, to test previous hypothesis of rotations and translations of this massif, whose rock assemblage differs from other basement-cored ranges adjacent to the Guyana margin. Three magnetic components were identified in this study. A first component has a direction parallel to the present magnetic field and was uncovered in all units (D = 352, I = 25.6, k = 57.35, a95 = 5.3, N = 12). A second component was isolated in Cretaceous limestone and Jurassic volcaniclastic rocks (D = 8.8, I = 8.3, k = 24.71, a95 = 13.7, N = 6), and it was interpreted as of Early Cretaceous age. In Jurassic sites with this component, Early Cretaceous K–Ar ages obtained from this and previous studies are interpreted as reset ages. The third component was uncovered in eight sites of Jurassic volcaniclastic rocks, and its direction indicates negative shallow to moderate inclinations and northeastward declinations. K–Ar ages in these sites are of Early (196.5 ± 4.9 Ma) to early Late Jurassic age (156.6 ± 8.9 Ma). Due to local structural complexity and too few Cretaceous outcrops to perform a reliable unconformity test, we only used two sites with (1) K–Ar ages, (2) less structural complexity, and (3) reliable structural data for Jurassic and Cretaceous rocks. The mean direction of the Jurassic component is (D = 20.4, I = −18.2, k = 46.9, a95 = 5.1, n = 18 specimens from two sites). These paleomagnetic data support previous models of northward along-margin translations of Grenvillian-cored massifs. Additionally, clockwise vertical-axis rotation of this massif, with respect to the stable craton, is also documented; the sense of rotation is similar to that proposed for the Perija Range and other ranges of the southern Caribbean margin. More data is needed to confirm the magnitudes of rotations and translations.     

Regimes of subduction and lithospheric dynamics in the Precambrian: 3D thermomechanical modelling

Comparing the early Earth to the present day, geological–geochemical evidence points towards higher mantle potential temperature and a different type of tectonics. In order to investigate possible changes in Precambrian tectonic styles, we conduct 3D high-resolution petrological–thermomechanical numerical modelling experiments for oceanic plate subduction under an active continental margin at a wide range of mantle potential temperature T_P (∆ T_P = 0 − 250 K, compared to present day conditions). At present day mantle temperatures (∆ T_P = 0 K), results of numerical experiments correspond to modern-style subduction, whereas at higher temperature conditions important systematic changes in the styles of both lithospheric deformation and mantle convection occur. For ∆ T_P = 50 − 100 K a regime of dripping subduction emerges which is still very similar to present day subduction but is characterised by frequent dripping from the slab tip and a loss of coherence of the slab, which suggests a close relationship between dripping subduction and episodic subduction. At further increasing ∆ T_P = 150 − 200 K dripping subduction is observed together with unstable dripping lithosphere, which corresponds to a transitional regime. For ∆ T_P = 250 K, presumably equivalent to early Archean, the dominating tectonic style is characterised by small-scale mantle convection, unstable dripping lithosphere, thick basaltic crust and small plates. Even though the initial setup is still defined by present day subduction, this final regime shows many characteristics of plume-lid tectonics. Transition between the two end-members, plume-lid tectonics and plate tectonics, happens gradually and at intermediate temperatures elements of both tectonic regimes are present. We conclude, therefore, that most likely no abrupt geodynamic regime transition point can be specified in the Earth's history and its global geodynamic regime gradually evolved over time from plume-lid tectonics into modern style plate tectonics.     

Geochemical and oxygen isotope signatures of mantle corundum megacrysts from the Mbuji-Mayi kimberlite,Democratic Republic of Congo,and the Changle alkali basalt,China

Oxygen isotope signatures of ruby and sapphire megacrysts, combined with trace-element analysis, from the Mbuji-Mayi kimberlite, Democratic Republic of Congo, and the Changle alkali basalt, China, provide clues to specify their origin in the deep Earth. At Mbuji-Mayi, pink sapphires have δ¹⁸O values in the range 4.3 to 5.4‰ (N = 10) with a mean of 4.9 ± 0.4‰, and rubies from 5.5 to 5.6‰ (N = 3). The Ga/Mg ratio of pink sapphires is between 1.9 and 3.9, and in rubies, between 0.6 and 2.6. The blue or yellow sapphires from Changle have δ¹⁸O values from 4.6 to 5.2 ‰, with a mean of 4.9 ± 0.2‰ (N = 9). The Ga/Mg ratio is between 5.7 and 11.3. The homogenous isotopic composition of ruby suggests a derivation from upper mantle xenoliths (garnet lherzolite, pyroxenite) or metagabbros and/or lower crustal garnet clinopyroxenite eclogite-type xenoliths included in kimberlites. Data from the pink sapphires from Mbuji-Mayi suggest a mantle origin, but different probable protoliths: either subducted oceanic protolith transformed into eclogite with δ¹⁸O values buffered to the mantle value, or clinopyroxenite protoliths in peridotite. The Changle sapphires have a mantle O-isotope signature. They probably formed in syenitic magmas produced by low degree partial melting of a spinel lherzolite source. The kimberlite and the alkali basalt acted as gem conveyors from the upper mantle up to the surface.     

Melting phase relations of the Udachnaya-East Group-I kimberlite at 3.0–6.5 GPa: Experimental evidence for alkali-carbonatite composition of primary kimberlite melts and implications for mantle plumes

Experiments on the origin of the Udachnaya-East kimberlite (UEK) have been performed using a Kawai-type multianvil apparatus at 3–6.5 GPa and 900–1500 °C. The studied composition represents exceptionally fresh Group-I kimberlite containing (wt.%): SiO₂ = 25.9, TiO₂ = 1.8, Al₂O₃ = 2.8, FeO = 9.0, MgO = 30.1, CaO = 12.7, Na₂O = 3.4, K₂O = 1.3, P₂O₅ = 1.0, Cl = 0.9, CO₂ = 9.9, and H₂O = 0.5. The super-solidus assemblage consists of melt, olivine (Ol), Ca-rich (26.0–30.2 wt.% CaO) garnet (Gt), Al-spinel (Sp), perovskite (Pv), a CaCO₃ phase (calcite or aragonite), and apatite. The low pressure assemblage (3–4 GPa) also includes clinopyroxene. The apparent solidus was established between 900 and 1000 °C at 6.5 GPa. At 6.5 GPa and 900 °C Na–Ca carbonate with molar ratio of (Na + K)/Ca ≈ 0.44 was observed. The UEK did not achieve complete melting even at 1500 °C and 6.5 GPa, due to excess xenogenic Ol in the starting material. In the studied P–T range, the melt has a Ca-carbonatite composition (Ca# = molar Ca/(Ca + Mg) ratio = 0.62–0.84) with high alkali and Cl contents (7.3–11.4 wt.% Na₂O, 2.8–6.7 wt.% K₂O, 1.6–3.4 wt.% Cl). The K, Na and Cl contents and Ca# decrease with temperature. It is argued that the primary kimberlite melt at depths > 200 km was an essentially carbonatitic (< 5 wt.% SiO₂), but evolved toward a carbonate–silicate composition (up to 15–20 wt.% SiO₂) during ascent. The absence of orthopyroxene among the run products indicates that xenogenic orthopyroxene was preferentially dissolved into the kimberlite melt. The obtained subliquidus phase assemblage (Ol + Sp + Pv + Ca-rich Gt) at P–T conditions of the UEK source region, i.e. where melt was in the last equilibrium with source rock before magma ascent, differs from the Opx-bearing peridotitic mineral assemblage of the UEK source region. This difference can be ascribed to the loss of substantial amounts of CO₂ from the kimberlite magma at shallow depths, as indicated by both petrological and experimental data. Our study implies that alkali-carbonatite melt would be a liquid phase within mantle plumes generated at the core–mantle boundary or shallower levels of the mantle, enhancing the ascent velocity of the plumes. We conclude that the long-term activity of a rising hot mantle plume and associated carbonatite melt (i.e. kimberlite melt) causes thermo-mechanical erosion of the subcontinental lithosphere mantle (SCLM) roots and creates hot and deformed metasomatic regions in the lower parts of the SCLM, which corresponds to depths constrained by P–T estimates of sheared Gt-peridotite xenoliths. The sheared Gt-peridotites undoubtedly represent samples of these regions.     

Correlations between metals in tree-rings of Prosopis julifora as indicators of sources of heavy metal contamination

Heavy-metals (Cu, Pb and Zn) in tree-ring sequences of Prosopis juliflora, a tree species native to arid environments, were analyzed by ICP-MS. The tree-ring sequences were obtained from three specimens growing in an urban area previously reported as contaminated by the activity of a Cu smelter facility. The metal found in highest concentration in the wood was Zn, with concentrations up to 120 mg/kg and an enrichment factor up to 26; followed by Cu (up to 9.6 mg/kg, enrichment factor up to 8.6) and Pb (up to 1.4 mg/kg, enrichment factor up to 3). By assessing the correlation between different metal concentration trends, it was possible to infer two main pollution sources: vehicle traffic and Cu smelter emissions. Vehicle traffic is indicated by a correlation between Pb and Zn over time within individual trees, whereas contamination from the Cu-smelting facility is indicated by a correlation of Cu over time between trees. In tree A there was a significant within-tree correlation between Pb and Zn concentration trends (r = 0.856, P < 0.001), whereas Cu showed no correlation with the other metals. For tree B, there were no within-tree correlations between these metals, but when comparing the concentration–time trends between trees A and B, there was a significant correlation for Cu (r = 0.768, P < 0.01). The tree-ring sequence from tree C showed significant within-tree correlation for Cu:Zn (r = 0.430, P < 0.01) and for Pb:Zn (r = 0.753, P < 0.001). The highest enrichment values were found in tree A, located along the path of the growing-season dominant wind direction from the smelter facility, and not in the tree growing closer to the smelter (tree C), suggesting that the smelter’s emissions are dispersed to longer distances through the tall chimneys, attenuating the impact to the area directly closest to the smelter facility. It is concluded that Prosopis juliflora appears as a good bioindicator based on its metal accumulation capacity and lack of metal mobility among tree rings, thus providing information on the chronology and sources of heavy-metal pollution in urban and industrial areas.     

Dielectric loss in ore-forming chromium spinel at temperatures from 20 to 800 °C

Physical, physicochemical, and mineralogical-petrographic methods have been applied to samples of ophiolite-hosted chromite ore from different deposits and occurrences in the Urals. Temperature dependences of dielectric loss obtained for nine chromite ore samples consisting of 95–98% Cr spinel show prominent peaks indicating a relaxation origin of the loss. The analyzed samples have the loss peaks at different temperatures depending mainly on H = (FeO/Fe₂O₃)^? : (FeO/Fe₂O₃)^??, where (FeO/Fe₂O₃)^? and (FeO/Fe₂O₃)^?? are, respectively, the ferrous/ferric oxide ratios in the samples before and after heating to 800 °C, and H is thus the heating-induced relative change in the FeO/Fe₂O₃ ratio. These peak temperatures vary from 550 °C (sample 1, high-Cr chromium spinel with more than 52% Cr₂O₃) to 750 °C (sample 2, aluminous and magnesian spinel with less than 30% Cr₂O₃), and H ranges correspondingly from 1.61 to 5.49. The temperature of the loss peaks is related with H as H = 34.30 ? 11.52N + 1.20N², with an error of σ = 0.19 (N = T · 10^?2, T is temperature in °C).     

Metamorphism of volcanogenic massive sulphide deposits in the Urals. Ore geology

The Urals VMS province comprises a broad spectrum of variably metamorphosed deposits, from unmetamorphosed to those without any primary ore textures, which are the results of high-grade metamorphic processes. Contact metamorphism near large granite and granodiorite plutons caused the most significant changes of ores, with coarse-grained to pegmatoidal ores with magnetite closest to its contact with the intrusion, followed by pyrrhotite-enriched copper ores, and more distal zinc (± Pb ± Ag) mineralisation. Koktau, Tarnyer and Vesenneye deposits are metamorphosed to the hornblende-hornfels and pyroxene-hornfels facies (t = 400–800 °C, P = 1–6 kbar). Metamorphism of Tash-Yar, Dzhusinskoe and Krasnogvardeiskoe deposits corresponds to the greenschist and albite-epidote-hornfels facies (t = 250–450 °C, P = 1–4 kbar).The regional metamorphism of VMS ores varies from prehnite-pumpellyite facies (t = 150–300 °C, P = 0.5–4 kbar) in the South Urals to the epidote-amphibolite and amphibolite facies (t = 400–600 °C (up to 700 °C), P = 1–6 kbar) in the Karabash area in the Middle Urals. In the Magnitogorsk zone, the metamorphism of host rocks and VMS bodies increases to the north, reaching its peak near the Ufa promontory of the East European platform. With increased metamorphism, the morphology of orebodies evolves from gently dipping thick lenses (Alexandrinskoe and Uzelga fields), to subvertical and folded (Uchaly and Novo-Uchaly deposits) and pseudomonoclinal steeply-dipping vein-like bodies (Karabash district).The massive sulphide transformation in PTX-gradient fields led to partial redistribution of ore material. An enrichment in Cu, Zn, Ag and Au, ± Pb occur in the uppermost parts of large steeply-dipping massive sulphide lenses in wide tectonic zones (e.g., Gai deposit) or as gold-sulphide disseminated bodies near large metamorphosed VMS lenses, distal to a granite pluton (Tarnyer deposit). Partial melting probably occurred in some highly metamorphosed deposits (Tarnyer, Koktau and Mauk). Redeposition of base metals sulphides (chalcopyrite, tennantite, sphalerite, ± bornite, galena), as well as the presence of “visible” gold and tellurides, took place during retrograde metamorphism, which produced a transfer of ore matter towards the low stress areas, such as the outer parts of shear zones, the uppermost parts of steeply-dipping ore lenses, pressure shadows, hinge zones of small folds, and small extension fractures (i.e., Alpine-type veins) in deformed ore body or its immediate surroundings.     

Magma mixing origin for the Aolunhua porphyry related to Mo–Cu mineralization,eastern Central Asian Orogenic Belt

Many Cu–Mo–Au deposits are considered to be related to adakitic porphyries formed in non-arc settings, e.g., in collisional orogenic zones and intra-plate environments, but their genesis is still under discussion. The Aolunhua porphyry complex and its related Mo–Cu deposit from the eastern Central Asian Orogenic Belt (CAOB) provide important insights into this issue. The porphyries are characterized by high Sr (496–705 ppm) and Sr/Y and La/Yb ratios similar to those of typical adakitic rocks, and low I_Sr ratios (0.7049–0.7052) and positive ε_Nd(t) (+ 0.5 to + 1.4) and ε_Hf(t) (+ 3.5 to + 9.8) values. These features, along with the occurrence of mafic microgranular enclaves (MMEs), compositional and textural disequilibrium of plagioclase phenocrysts and relatively high Mg# values (45–52), indicate that they were derived from mixing of felsic magma from partial melting of a juvenile arc-type lower crust and mafic magma from a lithospheric mantle previously metasomatized by subduction zone fluids/melts. High Sr/Y and La/Yb ratios are indicative of contribution from enriched mantle-derived materials (with high LILEs; e.g., Sr, La), which were strengthened by subsequent fractionation of ferromagnesian phases such as pyroxene and hornblende. MMEs hosted by the ore-bearing porphyry have zircon U–Pb ages of ca. 132 Ma, similar to those of the host rocks. The enclaves have elevated Mg^# (56–63), LILEs (e.g., Sr = 660–891 ppm), LREE (La_N = 68–150, (La/Sm)_N = 3.0–4.0, (La/Yb)_N = 12.0–19.6) and ratios of radiogenic isotopes of Nd- and Hf (ε_Nd = + 0.7 to + 1.6; ε_Hf = + 3.3 to + 10.9), suggesting that their parental magmas were derived from the metasomatized mantle source. The Mo–Cu mineralization was probably related to the high water content, high oxygen and sulfur fugacity of hybrid magma. Formation of the adakitic porphyries and related Mo–Cu deposits of the eastern CAOB could be related to the Early Cretaceous lithospheric extension, caused by the subduction of the Paleo-Pacific plate and its induced reactivation of juvenile arc-type lower crust.     

Geodynamic regimes of thermochemical mantle plumes

Laboratory and numerical experiments simulating the heat transfer and flow structure of thermochemical mantle plumes provide insights into the mechanisms of plume eruption onto the surface depending on the relative thermal power of plumes Ka = N/N₁, where N and N₁ are the heat transferred from the plume base to the plume conduit and the heat transferred from the plume conduit to the surrounding mantle, respectively, under steady thermal conduction. There are three main types of plumes according to the Ka criterion: (i) plumes with low thermal power (Ka < 1.15), which fail to reach the surface, (ii) plumes with intermediate thermal power (1.15 < Ka < 1.9), which occur beneath cratons and transport melts from depths below 150 km, where diamond is stable (diamondiferous plumes), and (iii) plumes with a mushroom-shaped head (1.9 < Ka < 10), which are responsible for large intrusive bodies, including batholiths. The volume of erupted melt and the depth from which the melt is transported to the surface are estimated for plumes of types (ii) and (iii). The relationship between the plume head area (along with the plume head diameter) and the relative thermal power is obtained. The relationship between the thickness of the block above the plume head and the relative thermal power is derived. On the basis of the results obtained, the geodynamic-regime diagram of thermochemical mantle plumes, including the plumes with Ka > 10, has been constructed.     

Combined paleomagnetic and geochronological study on Cretaceous strata of the Qiangtang terrane,central Tibet

A combined paleomagnetic and geochronological investigation has been performed on Cretaceous rocks in southern Qiangtang terrane (32.5°N, 84.3°E), near Gerze, central Tibetan Plateau. A total of 14 sites of volcanic rocks and 22 sites of red beds have been sampled. Our new U–Pb geochronologic study of zircons dates the volcanic rocks at 103.8 ± 0.46 Ma (Early Cretaceous) while the red beds belong to the Late Cretaceous. Rock magnetic experiments suggest that magnetite and hematite are the main magnetic carriers. After removing a low temperature component of viscous magnetic remanence, stable characteristic remanent magnetization (ChRM) was isolated successfully from all the sites by stepwise thermal demagnetization. The tilt-corrected mean direction from the 14 lava sites is D = 348.0°, I = 47.3°, k = 51.0, α₉₅ = 5.6°, corresponding to a paleopole at 79.3°N, 339.8°E, A₉₅ = 5.7° and yielding a paleolatitude of 29.3° ± 5.7°N for the study area. The ChRM directions isolated from the volcanic rocks pass a fold test at 95% confidence, suggesting a primary origin. The volcanic data appear to have effectively averaged out secular variation as indicated by both geological evidence and results from analyzing the virtual geomagnetic pole (VGP) scatter. The mean inclination from the Late Cretaceous red beds, however, is 13.1° shallower than that of the ~ 100 Ma volcanic rocks. After performing an elongation/inclination analysis on 174 samples of the red beds, a mean inclination of 47.9° with 95% confidence limits between 41.9° and 54.3° is obtained, which is consistent with the mean inclination of the volcanic rocks. The site-mean direction of the Late Cretaceous red beds after tilt-correction and inclination shallowing correction is D = 312.6°, I = 47.7°, k = 109.7, α₉₅ = 3.0°, N = 22 sites, corresponding to a paleopole at 49.2°N, 1.9°E, A₉₅ = 3.2° (yielding a paleolatitude of 28.7° ± 3.2°N for the study area). The ChRM of the red beds also passes a fold test at 99% confidence, indicating a primary origin. Comparing the paleolatitude of the Qiangtang terrane with the stable Asia, there is no significant difference between our sampling location in the southern Qiangtang terrane and the stable Asia during ~ 100 Ma and Late Cretaceous. Our results together with the high quality data previously published suggest that an ~ 550 km N–S convergence between the Qiangtang and Lhasa terranes happened after ~ 100 Ma. Comparison of the mean directions with expected directions from the stable Asia indicates that the Gerze area had experienced a significant counterclockwise rotation after ~ 100 Ma, which is most likely caused by the India–Asia collision.     

Geochronological and geochemical constraints on the petrogenesis of the early Paleoproterozoic potassic granite in the Lushan area,southern margin of the North China Craton

We conducted a geochronological and geochemical study on the Paleoproterozoic potassic granites in the Lushan area, southern margin of the North China Craton (NCC) to understand the tectonic regime of the NCC at 2.2–2.1 Ga. This rock suite formed at 2194 ± 29 Ma. The rocks are rich in SiO₂ (76.10–77.73 wt.%), and K₂O (5.94–6.90 wt.%) with high K₂O + Na₂O contents from 7.56 wt.% to 8.48 wt.%, but poor in CaO (0.10–0.28 wt.%), P₂O₅ (0.02–0.05 wt.%) and MgO (0.01–0.30 wt.%, Mg# = 1.08–27.3), indicating they experienced fractional crystallization. Major element compositions suggest the potassic granites share an affinity with high K calc-alkaline granite. Even though the Lushan potassic granitic rocks have high A/CNK ratios (1.11–1.25), which can reach peraluminous feature, the very low P₂O₅ contents and negative correlation of P₂O₅ and SiO₂ ruling out they are S-type granites. Different from peralkaline A-type granites, the Lushan potassic granites have variable Zr concentrations (160–344 ppm, 226 ppm on average) and 10,000 Ga/Al ratios (1.76–3.00), together with high zircon saturation temperatures (T_Zr = 826–885 °C), indicating they are fractionated aluminous A-type granites. Enriched LREE ((La/Yb)_N = 9.72–81.8), negative Eu anomalies, and low Sr/Y with no correlations in Sr/Y and Sr/Zr versus CaO suggest the possible presence of Ca-rich plagioclase and absence of garnet in the residual. Magmatic zircon grains have variable ε_Hf(t) values (−2.4 to +7.3) with zircon two-stage Hf model ages (T_DM^C) varying from 2848 Ma to 2306 Ma (mostly around ca. 2.5 Ga), and are plotted in the evolution line of crustal felsic rock. We propose that the rocks mainly formed by partial melting of ca. 2.50 Ga tonalitic–granodioritic crust as a result of upwelling mantle-derived magmas which provided thermal flux and source materials in an intra-continent rifting. The ca. 2.2 Ga magmatism suggests that intra-continental rifting occurred at 2.35–1.97 Ga at least in the southern margin of the NCC after its final cratonization in the late Neoarchean.     

Diagenetic state and source characterization of marine sediments from the inner continental shelf of the Gulf of Cádiz (SW Spain), constrained by terrigenous biomarkers

Surface sediments from the Gulf of Cádiz (GoC) were analyzed by alkaline CuO oxidation, in order to estimate the contribution of terrigenous organic matter (TOM) to the inner continental shelf of the southwest Iberian Peninsula. The parallel analysis of sediment samples from the two most important rivers draining to this coastal area (i.e. Guadiana River and Tinto–Odiel fluvial system) provided fundamental information regarding local terrestrial sources. Relatively constant intensive lignin parameters (S:V = 1.0 ± 0.1 and C:V = 0.22 ± 0.04) and high values of the lignin phenol vegetation index (LPVI = 155 ± 43) indicated that non-woody angiosperm tissues constitute the dominant component of vascular plant material reaching the shelf sediments. The NW to SE decreasing isotopic (¹³C) and molecular (Λ₈) signatures found among the sediments, coinciding with the Guadiana delivery plume, suggest that this river is the main terrestrial source in the inner GoC shelf. Slightly elevated values of degradation indicative ratios ([Ad:Al]_V = 0.41 ± 0.10; [Ad:Al])_S = 0.34 ± 0.07; [3,5-Bd:V] = 0.14 ± 0.05; P:[V + S] = 0.24 ± 0.09) suggested the alteration state of the shelf sediments. The two fold higher ratios of the river sediments (Guadiana: [Ad:Al]_V = 0.82 ± 0.08; [Ad:Al]_S = 0.84 ± 0.03; Tinto–Odiel: [Ad:Al]_V = 0.86 ± 0.12; [Ad:Al]_S = 0.83 ± 0.013) and the increasing degradation trend observed outward in the shelf, lead us to consider preferential sorption processes, instead of in situ diagenesis, to affect the degradation signature of the shelf sediments. Preferentially solubilized degraded OM is more likely to be sorbed and stabilized prior to transport to the marine system, showing an apparently more advanced degradation state. The use of the 3,5-Bd:V ratio in conjunction with (Ad:Al)_V revealed a composition continuum of the sedimentary OM ranging from fresh plant materials to highly altered soil humic constituents. Elemental and molecular analyses show a land to sea gradient by a NW to SE decrease of the terrestrial influence, accounting for larger terrestrial inputs (TOM: 71–98%) in those sediments near the Guadiana mouth, and predominantly autochthonous composition (TOM: 42–50%) in those located offshore. This work utilizes lignin derived biomarkers to determine the contribution of terrigenous OM delivered to this poorly described coastal area from regional rivers. Within a context of increasing international efforts to better understand the global C cycling, this study illustrates the relevance of using the alkaline CuO oxidation approach to evaluate C budgets and continental influence in river dominated ocean margins.     

Geochronological and geochemical study of mafic dykes from the northwest Chinese Altai: Implications for petrogenesis and tectonic evolution

Fifteen zircons separated from a mafic dyke in the Chinese Altai give a concordant age population with a weighted mean ²⁰⁶Pb/²³⁸U age of 375.5 ± 4.8 Ma, suggesting a Devonian emplacement. On the basis of their mineralogical compositions and textures, the coeval dykes can be divided into gabbroic and doleritic types. They are both sub-alkaline, tholeiitic, characterized by similarly low SiO₂ contents (45.2–52.7 wt.%) and total alkaline (K₂O + Na₂O = 0.99–4.93 wt.%). Rare earth element patterns of the gabbroic dykes are similar to N-MORB (La/Yb_N = 0.86–1.1), together with their high ε_Nd(t) values (+ 7.6 to + 8.1), indicating that their precursor magma was mainly derived from a N-MORB-type depleted asthenospheric mantle. While the REE patterns of the doleritic dykes resemble that of E-MORB (La/Yb_N = 1.12–2.28), enriched in LILEs and strongly depleted in HFSEs, with relative low ε_Nd(t) values (+ 3.4 to + 5.4) and high initial ⁸⁷Sr/⁸⁶Sr ratios (0.7057–0.7060). The zircon Hf isotopic analysis of the doleritic dykes give ε_Hf(t) values from + 10.7 to + 13.8. These signatures suggest that a depleted mantle wedge metasomatized by slab-derived fluids and/or melts was possibly involved in the generation of the doleritic magma. The refractory peridotite may have been melted with variable degrees caused by upwelling of the hot asthenosphere. The petrogenesis of the mafic dykes suggest a high heat flux as a result of upwelling of the hot asthenosphere and the contrast geochemical signatures can be interpreted by a ridge subduction, which could be an important tectonic control in the accretionary process of the Chinese Altai.     

The impact of severe biodegradation on the molecular and stable (C,H, N,S) isotopic compositions of oils in the Alberta Basin,Canada

Although the effects of biodegradation on the composition and physical properties of crude oil have been well studied, effects of in-reservoir petroleum biodegradation on molecular and isotopic compositions of crude oils are not yet clearly understood. The Alberta Basin, in western Canada, is one of the world’s largest petroleum accumulations and constitutes an ideal example of a natural suite of sequentially biodegraded oils. The basin hosts moderately to severely biodegraded petroleum, regionally distributed and in single, more or less continuous, oil columns. In this study, a series of oil samples from the Alberta heavy oil and oil sands provinces, with varying degrees of biodegradation, were analyzed to assess the impact of progressive biodegradation on the molecular and C, H, N, and S isotopic compositions of oils. The results of the molecular characterization of the hydrocarbon fraction of the studied oils show that the oils have suffered biodegradation levels from 2 to 10⁺ (toward the Alberta–Saskatchewan border) on the Peters and Moldowan scale of biodegradation (abbreviated PM 2 to PM 10) and from tens to hundreds on the Manco scale. Within single reservoirs, increasing biodegradation was observed from top to bottom of the oil columns at all sites studied. The whole oil stable isotopic compositions of the samples varied in the ranges δ¹³C = −31.2‰ to −29.0‰, δ²H = −147‰ to −133‰, δ¹⁵N = 0.3–4.7‰ and δ³⁴S = 0.4–6.4‰. The maximum differences between δ values of samples (Δ) within single oil columns were Δ¹³C = 1.4‰, Δ²H = 7‰, Δ¹⁵N = 1.7‰ and Δ³⁴S = 1.0‰. Regional variations in the isotopic compositions of oil samples from different wells (averaged values from top to bottom) were 1.2‰ for δ¹³C, 12‰ for δ²H, 4.1‰ for δ¹⁵N and 5.5‰ for δ³⁴S and hence generally significantly larger variations were seen than variations observed within single oil columns, especially for N and S. It appears that even severe levels of biodegradation do not cause observable systematic variations in carbon, nitrogen or sulfur isotope composition of whole oils. This indicates that sulfur and nitrogen isotopic compositions may be used in very degraded oils as indicators for oil charge from different source rock facies.     

Synthesis and characterization of polycrystalline KAlSi3O8 hollandite [liebermannite]: Sound velocities vs. pressure to 13 GPa at room temperature

A polycrystalline specimen of liebermannite [KAlSi₃O₈ hollandite] was synthesized at 14.5 GPa and 1473 K using glass starting material in a uniaxial split-sphere apparatus. The recovered specimen is pure tetragonal hollandite [SG: I4/m] with bulk density of within 98% of the measured X-ray value. The specimen was also characterized by Raman spectroscopy and nuclear magnetic resonance spectroscopy. Sound velocities in this specimen were measured by ultrasonic interferometry to 13 GPa at room T in a uniaxial split-cylinder apparatus using Al₂O₃ as a pressure marker. Finite strain analysis of the ultrasonic data yielded K_S0 = 145(1) GPa, K₀′ = 4.9(2), G₀ = 92.3(3) GPa, G₀′ = 1.6(1) for the bulk and shear moduli and their pressure derivatives, corresponding to V_P0 = 8.4(1) km/s, V_S0 = 4.9(1) km/s for the sound wave velocities at room temperature. These elasticity data are compared to literature values obtained from static compression experiments and theoretical density functional calculations.     

Geochronology and geochemistry of Mesozoic mafic–ultramafic complexes in the southern Liaoning and southern Jilin provinces,NE China: Constraints on the spatial extent of destruction of the North China Craton

LA–ICP–MS zircon U–Pb ages, geochemical and Sr–Nd–Pb isotope data are presented for mafic–ultramafic complexes from the southern Liaoning–southern Jilin area with the aim of determining the nature of the Mesozoic lithospheric mantle and to further constrain the spatial extent of destruction of the North China Craton (NCC). The complexes consist of olivine-websterite, gabbro, dolerite, and gabbro-diorite. Zircons from the complexes show typical zoning absorption, are euhedral–subhedral in shape, and yield high Th/U ratios (1.23–2.87), indicating a magmatic origin. Zircon U–Pb age data indicate that they formed in the Early Cretaceous (129–137 Ma). Geochemically, they have SiO₂ = 44.3–49.8%, MgO = 6.8–26.5%, Cr = 102–3578 ppm, and Ni = 31–1308 ppm, and are characterized by enrichment in large ion lithophile elements (LILEs) and light rare earth elements (LREEs), and depletion in high field strength elements (HFSEs) and heavy rare earth elements (HREEs), as well as a wide range of Sr–Nd–Pb isotopic compositions [(⁸⁷Sr/⁸⁶Sr)i = 0.70557–0.71119; ε_Nd (t) = ?5.4 to ?20.1; (²⁰⁶Pb/²⁰⁴Pb)i = 15.13–17.85; Δ7/4 = ?11.49 to 16.00; Δ8/4 = 102.64–203.48]. Compared with the southern Liaoning mafic–ultramafic rocks, the southern Jilin mafic–ultramafic rocks have high TiO₂ and Al₂O₃ contents, high ε_Nd (t) values, low (La/Yb)_N values, low initial ⁸⁷Sr/⁸⁶Sr ratios, and low radiogenic Pb isotopic compositions. These findings indicate that the primary magmas of the southern Jilin complexes were derived from lithospheric mantle that was previously metasomatized by a melt derived from the delaminated ancient lower crust, whereas the primary magmas of the southern Liaoning complexes originated from partial melting of a lithospheric mantle source that was previously modified by melt derived from the broken-off Yangtze slab. Therefore, the lateral extent of the NCC destruction should include the southern Liaoning–southern Jilin area.     

Fluid types and their genetic meaning for the BIF-hosted iron ores,Krivoy Rog,Ukraine

This paper contributes to the understanding of the genesis of epigenetic, hypogene BIF-hosted iron deposits situated in the eastern part of Ukrainian Shield. It presents new data from the Krivoy Rog iron mining district (Skelevatske–Magnetitove deposit, Frunze underground mine and Balka Severnaya Krasnaya outcrop) and focuses on the investigation of ore genesis through application of fluid inclusion petrography, microthermometry, Raman spectroscopy and baro-acoustic decrepitation of fluid inclusions. The study investigates inclusions preserved in quartz and magnetite associated with the low-grade iron ores (31–37% Fe) and iron-rich quartzites (38–45% Fe) of the Saksaganskaya Suite, as well as magnetite from the locally named high-grade iron ores (52–56% Fe). These high-grade ores resulted from alteration of iron quartzites in the Saksaganskiy thrust footwall (Saksaganskiy tectonic block) and were a precursor to supergene martite, high-grade ores (60–70% Fe). Based on the new data two stages of iron ore formation (metamorphic and metasomatic) are proposed.The metamorphic stage, resulting in formation of quartz veins within the low-grade iron ore and iron-rich quartzites, involved fluids of four different compositions: CO₂-rich, H₂O, H₂O–CO₂(± N₂–CH₄)–NaCl(± NaHCO₃) and H₂O–CO₂(± N₂–CH₄)–NaCl. The salinities of these fluids were relatively low (up to 7 mass% NaCl equiv.) as these fluids were derived from dehydration and decarbonation of the BIF rocks, however the origin of the nahcolite (NaHCO₃) remains unresolved. The minimum P–T conditions for the formation of these veins, inferred from microthermometry are T_min = 219–246 °C and P_min = 130–158 MPa. The baro-acoustic decrepitation analyses of magnetite bands indicated that the low-grade iron ore from the Skelevatske–Magnetitove deposit was metamorphosed at T = ~ 530 °C.The metasomatic stage post-dated and partially overlapped the metamorphic stage and led to the upgrade of iron quartzites to the high-grade iron ores. The genesis of these ores, which are located in the Saksaganskiy tectonic block (Saksaganskiy ore field), and the factors controlling iron ore-forming processes are highly controversial. According to the study of quartz-hosted fluid inclusions from the thrust zone the metasomatic stage involved at least three different episodes of the fluid flow, simultaneous with thrusting and deformation. During the 1^st episode three types of fluids were introduced: CO₂–CH₄–N₂(± C), CO₂(± N₂–CH₄) and low salinity H₂O–N₂–CH₄–NaCl (6.38–7.1 mass% NaCl equiv.). The 2^nd episode included expulsion of the aqueous fluids H₂O–N₂–CH₄–NaCl(± CO₂, ± C) of moderate salinities (15.22–16.76 mass% NaCl equiv.), whereas the 3^rd event involved high salinity fluids H₂O–NaCl(± C) (20–35 mass% NaCl equiv.). The fluids most probably interacted with country rocks (e.g. schists) supplying them with CH₄ and N₂. The high salinity fluids were most likely either magmatic–hydrothermal fluids derived from the Saksaganskiy igneous body or heated basinal brines, and they may have caused pervasive leaching of Fe from metavolcanic and/or the BIF rocks. The baro-acoustic decrepitation analyses of magnetite comprising the high-grade iron ore showed formation T = ~ 430–500 °C. The fluid inclusion data suggest that the upgrade to high-grade Fe ores might be a result of the Krivoy Rog BIF alteration by multiple flows of structurally controlled, metamorphic and magmatic–hydrothermal fluids or heated basinal brines.     

Paleomagnetic and 40Ar/39Ar geochronological results from the Linzizong Group,Linzhou Basin,Lhasa Terrane,Tibet: Implications to Paleogene paleolatitude and onset of the India–Asia collision

The Linzizong Group (64–44 Ma) of the Lhasa Terrane in Tibet is critically positioned for establishing the paleoposition of the southern leading edge of the Asian continent during Paleogene times and constraining onset of the India–Asia collision. Here we report paleomagnetic results from a collection comprising 384 drill-core samples from 34 sites embracing all three formations of this group. Comprehensive demagnetization and field tests isolate characteristic remanent magnetizations (ChRM) summarized by overall tilt-corrected formation-mean directions of D = 183.6°, I = −12.4° (α₉₅ = 8.1°) for the Dianzhong (64–60 Ma), D = 1.0°, I = 18.1° (α₉₅ = 8.1°) for the Nianbo (60–50 Ma), and D = 12.4°, I = 23.2° (α₉₅ = 7.3°) for the Pana (50–44 Ma). Fold tests are positive in each formation suggesting a pre-folding origin and we interpret the magnetizations as quasi-primary and acquired at, or slightly later than, formation of the Linzizong Group. Revised Paleogene paleopoles with Ar–Ar age constraints for the Lhasa Terrane indicate that onset of the India–Asia collision occurred no later than ∼60.5 ± 1.5 Ma at a low paleolatitude of ∼10°N. Analysis of 60 site-mean observations from a range of studies of the Pana Formation in the higher part of the succession highlight a large dispersion of ChRM directions; a number of possible causes are suggested but further study of this formation over a wider area is required to resolve this issue.