Major,minor element chemistry and oxygen and hydrogen isotopic compositions of Marun oil‐field brines,SW Iran: Source history and economic potential

Cation and anion concentrations and oxygen and hydrogen isotopic ratios of brines in the Asmari Formation (Oligocene–early Miocene) from the Marun oil field of southwest Iran were measured to identify the origin of these brines (e.g. salt dissolution vs. seawater evaporation) as well as the involvement of water–rock reaction processes in their evolution. Marun brines are characterized by having higher concentrations of calcium (11 000–20 000 mg/L), chlorine (120 000–160 000 mg/L) and bromide (600–1000 mg/L) compared to modern seawater. Samples are also enriched in ¹⁸O relative to seawater, fall to the right of the Global Meteoric Water Line and local rain water, and plot close to the halite brine trajectory on the δD versus δ¹⁸O diagram. Geochemical characteristics of Marun brines are inconsistent with a meteoric origin, but instead correspond to residual evaporated seawater modified by water–rock interaction, most significantly dolomitization. In addition, anhydrite precipitation or sulphate reduction appears to be important in chemical modification of the Marun brines, as indicated by lower sulphate contents relative to evaporated seawater. Extensive dolomitization, the presence of anhydrite nodules and high salinity fluid inclusions in the upper parts of the Asmari Formation fit a model whereby the Marun brines likely originated from the seepage reflux of concentrated seawater during the deposition of the overlying Gachsaran Formation evaporites in the Miocene. Copyright © 2010 John Wiley & Sons, Ltd.     

Formation of bed‐scale spatial patterns in dolomite abundance during early dolomitization: Part I. Mechanisms and feedbacks revealed by reaction–transport modelling

Dolomites of varied ages exhibit metre‐scale nested patterns of lateral periodic variation in permeability and porosity and, by inference, dolomite abundance as most examples are 100% dolomite. Two‐dimensional reaction–transport modelling simulations of bed‐scale dolomitization were used to assess whether those patterns in dolomite abundance could form during near‐surface replacement dolomitization. Simulations used a 2 m high and 18 m long model domain, a low‐Mg calcite grainstone precursor and an evaporated Mississippian seawater brine (430 parts per thousand salinity) as the dolomitizing fluid. The domain was initially populated with random variations in porosity and/or grain size. Results reveal that spatial patterns in dolomite abundance emerge when there is as little as 1% dolomite formed, with similarities between the modelled patterns and outcrop‐documented patterns. The nested patterns include a near‐random component that constitutes ≤40% of the total variance, short‐range correlation ranging from 1·5 to 3·3 m and a longer‐range periodic trend with a wavelength up to 6·5 m. The emergence of pattern in dolomite abundance is the result of an autogenic self‐organizing phenomenon. It is triggered by variation in initial calcite reactive surface area that occurs due to the random heterogeneities in initial porosity and/or grain sizes. The pattern develops due to a combination of kinetic disequilibrium reactions (dolomite precipitation and calcite dissolution) and positive feedbacks between dolomite growth, calcite dissolution and fluid flow. Flow is around loci of higher dolomite, lower porosity and higher reactive surface areas, but through loci of lower dolomite, higher porosity and lower reactive surface areas. The resulting less porous/more dolomite and more porous/less dolomite structures at the metre‐scale arise from those localized interactions. This self‐organizing mechanism for pattern formation constitutes a new model for geochemical self‐organization during dolomitization and is the only self‐organization model that is proven applicable to the formation of metre‐scale patterns during early, near‐surface dolomitization.     

Origin of coarse-crystalline calcite cement in Early Ordovician carbonate rocks, Ordos basin, northern China: Insights from oxygen and carbon isotopes and fluid inclusion microthermometry

The calcite cement in the Lower Ordovician Majiagou Formation in the Ordos basin in northern China can be subdivided into three groups based on preliminary results of oxygen and carbon isotopes and fluid inclusion microthermometry. Group 1 has low oxygen isotopes (− 14‰ to − 18‰), low T_h values (92–103 °C), and low salinities (1.7–4.9 wt.% NaCl equivalent) and is interpreted to have precipitated during early burial from porewater influenced by meteoric water. Group 2 has much higher oxygen isotope values (− 5‰ to − 8‰), which, coupled with the higher T_h values (136–151 °C), suggest that the calcite was precipitated from fluids that were significantly enriched in ¹⁸O, possibly resulting from fluid–rock reaction during burial. Group 3 occurring along fractures is characterized by high salinities (21–28 wt.% NaCl equivalent) and is interpreted to have been precipitated from locally preserved residual evaporitic brines. The occurrence of primary hydrocarbon inclusions and its low carbon isotopes (− 11‰ to − 15‰) suggest that precipitation of group 3 calcite took place in the presence of hydrocarbons.     

Combining trace-element compositions, U–Pb geochronology and Hf isotopes in zircons to unravel complex calcalkaline magma chambers in the Upper Cretaceous Srednogorie zone (Bulgaria)

Precise U–Pb geochronology and Hf isotope tracing of zircon is combined with whole-rock geochemical and Sr and Nd isotope data in order to unravel processes affecting mafic to felsic calcalkaline magmas prior to and during their crystallization in crustal magma chambers along the southern border of Central Srednogorie tectonic zone in Bulgaria (SE Europe). ID-TIMS U–Pb dating of single zircons from felsic and mixed/mingled dioritic to gabbroic horizons of single plutons define crystallization ages of around 86.5–86.0, 85.0–84.5 and 82 Ma. Concordia age uncertainties are generally less than 0.3 Ma (0.35%–2σ), and as good as 0.08 Ma (0.1%), when the weighted mean ²⁰⁶Pb/²³⁸U value is used. Such precision allows the distinction of magma replenishment processes if separated by more than 0.6–1.0 Ma and when they are marked by newly saturated zircons. We interpret zircon dates from a single sample that do not overlap to reflect new zircon growth during magma recharge in a long-lived crustal chamber. Mingling/mixing of the basaltic magma with colder granitoid mush at mid- to upper-crustal levels is proposed to explain zircon saturation and fast crystallization of U- and REE-rich zircons in the hybrid gabbro.Major and trace-element distribution and Sr and Nd whole-rock isotope chemistry define island arc affinities for the studied plutons. Slab derived fluids and a sediment component are constrained as enrichment sources for the mantle wedge-derived magma, though Hf isotopes in zircon suggest crustal assimilation was also important. Inherited zircons, and their corresponding ε-Hf, from the hybrid gabbroic rocks trace the lower crust as possible source for enrichment of the mantle magma. These inherited zircons are about 440 Ma old with ε-Hf of − 7 at 82 Ma, whereas newly saturated concordant Upper Cretaceous zircons reveal mantle ε-Hf values of + 7.2 to + 10.1. The upper and middle crusts contribute in the generation of the granitoid rocks. Their zircon inheritance is Lower Palaeozoic or significantly older and crustal dominated with 82–85 Ma corrected ε-Hf values of − 28. The Cretaceous concordant zircons in the granitoids are mantle dominated with a ε-Hf values spreading from + 3.9 to + 7.     

Genesis of the Xuebaoding W–Sn–Be Crystal Deposits in Southwest China: Evidence from Fluid Inclusions,Stable Isotopes and Ore Elements

The Xuebaoding crystal deposit, located in northern Longmenshan, Sichuan Province, China, is well known for producing coarse‐grained crystals of scheelite, beryl, cassiterite, fluorite and other minerals. The orebody occurs between the Pankou and Pukouling granites, and a typical ore vein is divided into three parts: muscovite and beryl within granite (Part I); beryl, cassiterite and muscovite in the host transition from granite to marble (Part II); and the main mineralization part, an assemblage of beryl, cassiterite, scheelite, fluorite, apatite and needle‐like tourmaline within marble (Part III). No evidence of crosscutting or overlapping of these ore veins by others suggests that the orebody was formed by single fluid activity. The contents of Be, W, Sn, Li, Cs, Rb, B, and F in the Pankou and Pukouling granites are similar to those of the granites that host Nanling W–Sn deposits. The calculated isotopic compositions of beryl, scheelite and cassiterite (δD, ?69.3‰ to ?107.2‰ and δ¹⁸O_H2O, 8.2‰ to 15.0‰) indicate that the ore‐forming fluids were mainly composed of magmatic water with minor meteoric water and CO₂ derived from decarbonation of marble. Primary fluid inclusions are CO₂? CH₄+ H₂O ± CO₂ (vapor), with or without clathrates and halites. We estimate the fluid trapping condition at T = 220 to 360°C and P > 0.9 kbar. Fluid inclusions are rich in H₂O, F^‐ and Cl^‐. Evidence for fluid‐phase immiscibility during mineralization includes variable L/V ratios in the inclusions and inclusions containing different phase proportions. Fluid immiscibility may have been induced by the pressure released by extension joints, thereby facilitating the mineralization found in Part III. Based on the geochemical data, geological occurrence, and fluid inclusion studies, we hypothesize that the coarse‐grained crystals were formed by: (i) the high content of ore elements and volatile elements such as F in ore‐forming fluids; (ii) occurrence of fluid immiscibility and Ca‐bearing minerals after wall rock transition from granite to marble making the ore elements deposit completely; (iii) pure host marble as host rock without impure elements such as Fe; and (iv) sufficient space in ore veins to allow growth.     

Formation of the Dongmozhazhua Pb–Zn Deposit in the Thrust‐Fold Setting of the Tibetan Plateau,China: Evidence from Fluid Inclusion and Stable Isotope Data

The Dongmozhazhua deposit, the largest Pb–Zn deposit in south Qinghai, China, is stratabound, carbonate‐hosted and associated with epigenetic dolomitization and silicification of Lower–Middle Permian—Upper Triassic limestones in the hanging walls of a Cenozoic thrust fault system. The mineralization is localized in a Cenozoic thrust‐folded belt along the northeastern edge of the Tibetan plateau, which was formed due to the India–Asia plate collision during the early Tertiary. The deposit comprises 16 orebodies with variable thicknesses (1.5–26.3 m) and lengths (160–1820 m). The ores occur as dissemination, vein, and breccia cement. The main sulfide assemblage is sphalerite + galena + pyrite + marcasite ± chalcopyrite ± tetrahedrite, and gangue minerals consist mainly of calcite, dolomite, barite, and quartz. Samples of pre‐ to post‐ore stages calcite yielded δ¹³C and δ¹⁸O values that are, respectively, similar to and lower than those yielded by the host limestones, suggesting that the calcite formed from fluids derived from carbonate dissolution. Fluid inclusions in calcite and sphalerite in the polymetallic sulfidization stage mostly comprise liquid and gas phases at room temperature, with moderate homogenization temperatures (100–140°C) and high salinities (21–28 wt% NaCl eq.). Micro‐thermometric fluid inclusion data point to polysaline brines as ore‐forming fluids. The δD and δ¹⁸O values of ore fluids, cation compositions of fluid inclusions, and geological information suggest two main possible fluid sources, namely basinal brines and evaporated seawater. The fluid inclusion data and regional geology suggest that basinal brines derived from Tertiary basins located southeast of the Dongmozhazhua deposit migrated along deep detachment zones of the regional thrust system, leached substantial base metals from country rocks, and finally ascended along thrust faults at Dongmozhazhua. There, the base‐metal‐rich basinal brines mixed with bacterially‐reduced H₂S‐bearing fluids derived from evaporated seawater preserved in the Permo–Triassic carbonate strata. The mixing of the two fluids resulted in Pb–Zn mineralization. The Dongmozhazhua Pb–Zn deposit has many characteristics that are similar to MVT Pb–Zn deposits worldwide.     

Petrogenesis of the Yangchang Mo‐bearing granite in the Xilamulun metallogenic belt,NE China: geochemistry,zircon U–Pb ages and Sr–Nd–Pb isotopes

The Yangchang granite‐hosted Mo deposit is typical of the Xilamulun metallogenic belt, which is one of the important Mo–Pb–Zn–Ag producers in China. A combination of major and trace element, Sr, Nd and Pb isotope, and zircon U–Pb age data are reported for the Yangchang batholith to constrain its petrogenesis and Mo mineralization. Zircon LA‐ICPMS U–Pb dating yields mean ages of 138 ± 2 and 132 ± 2 Ma for monzogranite and granite porphyry, respectively. The monzogranites and granite porphyries are calc‐alkaline with K₂O/Na₂O ratios of 0.75–0.92 and 1.75–4.42, respectively. They are all enriched in large‐ion lithophile elements (LILEs) and depleted in high‐field‐strength elements (HFSEs) with negative Nb and Ta anomalies in primitive‐mantle‐normalized trace element diagrams. The monzogranites have relatively high Sr (380–499 ppm) and Y (14–18 ppm) concentrations, and the granite porphyries have lower Sr (31–71 ppm) and Y (5–11 ppm) concentrations than those of monzogranites. The monzogranites and granite porphyries have relatively low initial Sr isotope ratios of 0.704573–0.705627 and 0.704281, respectively, and similar ²⁰⁶Pb/²⁰⁴Pb ratios of 18.75–18.98 and 18.48–18.71, respectively. In contrast, the ε_Nd(t) value (−3.7) of granite porphyry is lower than those of monzogranites (−1.5 to −2.7) with Nd model ages of about 1.0 Ga. These geochemical features suggest that the monzogranite and granite porphyries were derived from juvenile crustal rocks related to subduction of the Paleo‐Pacific plate under east China. Copyright © 2013 John Wiley & Sons, Ltd.