Origin of a barite-sulfide ore deposit in the Mykonos intrusion,cyclades: Trace element,isotopic, fluid inclusion and raman spectroscopy evidence

The polymetallic Mykonos vein system in the Cyclades, Greece, consists of 15 tension-gashes filled with barite, quartz, pyrite, sphalerite, chalcopyrite and galena in ca. 13.5 Ma, I-type, Mykonos monzogranite. Zones of silica and chlorite–muscovite alteration are associated with the veins and overprint pervasive silicification, phyllic and argillic alteration that affected large parts of the monzogranite. The mineralization cements breccias and consists of an early barite–silica–pyrite–sphalerite–chalcopyrite assemblage followed by later argentiferous galena. A combination of fluid inclusion and stable isotope data suggests that the barite and associated mineralization were deposited from fluids containing 2 to 17 wt.% NaCl equivalent, at temperatures of ~ 225° to 370 °C, under a hydrostatic pressure of ≤ 100 bars. The mineralizing fluids boiled and were saturated in H₂S and SO₂.Calculated δ¹⁸O_H2O and δD_H2O, initial ⁸⁷Sr/⁸⁶Sr isotope compositions and the trace and REEs elements contents are consistent with a model in which the mineralizing fluids were derived during alteration of the Mykonos intrusion and subsequently mixed with Miocene seawater. Heterogeneities in the calculated δ³⁴S_SO4^− 2 and δ³⁴S_H2S compositions of the ore fluids indicate two distinct sources for sulfur, namely of magmatic and seawater origin, and precipitation due to reduction of the SO₄^− 2 during fluid mixing. The physicochemical conditions of the fluids were pH = 5.0 to 6.2, logf_S2 = − 13.8 to − 12.5, logf_O2 = − 31.9 to − 30.9, logf_H2S(g) = − 1.9 to − 1.7, logf_Te2 = − 7.9 and logα(SO₄^− 2_(aq)/H₂S_(aq)) = + 2.6 to + 5.5. We propose that retrograde mesothermal hydrothermal alteration of the Mykonos monzogranite released barium and silica from the alkali feldspars. Barite was precipitated due to mixing of SO₄^− 2-rich Miocene seawater with the ascending Ba-rich magmatic fluid venting upwards in the pluton.     

Shear wave attenuation characteristics over the Central India Tectonic Zone and its surroundings

The study area lies between latitude 18–26°N and longitude 73–83°E, and mainly covers the Central India Tectonic Zone (CITZ). The frequency-dependent shear wave quality factor (Q_s) has been estimated over the CITZ and its surroundings using Double Spectral Ratio (DSR) method. We have considered 25 local earthquakes with magnitude (M_L) varies from 3.0 to 4.7 recorded at 11 stations running under national seismic network. The Fast Fourier Transformed (FFT) spectra were computed from the recorded waveform having time-window from onset of S-phase to 1.0 s and for a frequency-band of 0.1–10 Hz. Three different shear wave velocities (i.e., 3.87, 3.39 and 3.96 km/s) were obtained over the study area based on a pair of earthquakes recorded at a pair of stations. The low Q_s values of 51–96 at 1 Hz (i.e., Q_s = 51f^0.49; Q_s = 90f^0.488 and Q_s = 96f^0.53) were found in the area covering the Son–Narmada–Tapti (SONATA) lineament, CITZ, eastern part of the Satpura fold belt, Vindhyan and Gondwana basins, Godavari and Mahanadi grabens, and southern part of Gangetic plain. Intermediate Q_s values of the order of 204–277 (i.e., Q_s = 204f^0.56 and Q_s = 277f^0.55) were noted in the cartonic areas, namely, Bundelkhand, Dharwar-Bhandara and Bastar. While the higher Q_s values of 391–628 at 1 Hz (i.e., Q_s = 391f^0.49, Q_s = 409f^0.48, Q_s = 417f^0.48, Q_s = 500f^0.66, Q_s = 585f^0.65 and Q_s = 628f^0.69) were found in the eastern part of the SONATA, CITZ, and the northeastern part of the Satpura fold belt. The low Q_s values might be attributing to the more heterogeneous SONATA rift system. Low Q_s values further may presumably be associated with lower-level of seismicity and apparently account for higher tectonic stress accumulation over long duration. The long-term accumulated stress is generally released through occasional triggering of moderate magnitude earthquakes in the SONATA zone. Surrounding the SONATA region, the higher Q_s values possibly accounts for a more homogeneous subsurface structure along the SONATA zone.     

The Sarcheshmeh porphyry copper deposit,Kerman, Iran: A mineralogical analysis of the igneous rocks and alteration zones including halogen element systematics related to Cu mineralization processes

The giant Sarcheshmeh porphyry Copper deposit is located 65 km southwest of Kerman City, southeastern Iran. Numerous Miocene porphyry stocks and dykes intruded thick sequences of Upper Cretaceous sedimentary and Eocene volcanic rocks. Hypogene and supergene porphyry Cu mineralization occurs within the granodioritic porphyry and host rock sequence, which was extensively altered to a dominantly potassic, phyllic, and argillic assemblage with interstitial to distal propylitic types.Biotite-bearing assemblages occur as both primary phenocrysts and secondary replacements showing variable size, colour, and shape. Fluorine contents (0.22 to 1.33 wt.%) and X_Mg (0.54 to 0.71) in biotites from the potassic and phyllic zones are higher than those of non-mineralized granitoids (F = 0.09 to 0.56 wt.%, X_Mg = 0.43 to 0.54), whereas their Cl contents (Cl = 0.05 to 0.24 wt.%) are lower than those of the non-mineralized granitoids (Cl = .0.11 to 0.45). The biotites from the phyllic zone have higher log (fH₂O/fHF) and log (fH₂O/fHCl) values than those of the potassic zone, as well as the granitoid and andesitic dykes. The log (fHF/fHCl) values determined for the granitoid, potassic and phyllic zones are similar, though more negative than those of the andesitic dykes. The log (fHF/fHCl) values have a similar range for biotite from the granitoid, and potassic and phyllic zones. The halogen fugacity ratios established for fluids associated with the Sarcheshmeh deposit from their F and Cl contents in biotite show that the granitoid, potassic zone and phyllic zone are increasingly affected by meteoric waters. The fluids that circulated in the phyllic zone are predominantly of meteoric origin, possibly overprinting original phyllic zone halogen contents.The Cl intercept values of biotite in the granitoid, and phyllic and potassic are similar to other ore-forming systems and tend to be more Cl-rich than Cl-intercept values of biotites in common igneous rocks. Calculated F/Cl intercept values for biotite in the granitoid and potassic zone are also consistent with many other porphyry copper forming systems.     

Global calibration of a novel,branched GDGT-based soil pH proxy

Recently, 6-methyl branched glycerol dialkyl glycerol tetraethers (brGDGTs) were separated from 5-methyl brGDGTs, which are used in brGDGT-based proxies. Here we analyzed brGDGTs in 27 soil samples along the 400 mm isoline of mean annual precipitation in China by using tandem 2D liquid chromatography. The fractional abundance of 6-methyl brGDGTs showed a positive correlation with soil pH, while that of 5-methyl brGDGTs decreased with increasing soil pH. The abundance ratio of 6-/5-methyl brGDGTs, namely the isomerization of branched tetraethers (IBT), was calculated. The correlation of IBT with pH (pH = 6.33 − 1.28 × IBT; R² 0.89; root mean squared error, RMSE, 0.24) was much stronger than that of the traditionally used cyclization index of branched tetraethers (CBT) with pH (R² 0.52; RMSE 0.49) and comparable with that of CBT′ with pH (R² 0.88; RMSE 0.25). Compiling all available data from 319 soil samples resulted in a global calibration: pH = 6.53 − 1.55 × IBT (R² 0.72; RMSE 0.65), which has a better correlation than the CBT_5ME-pH proxy (R² 0.63; RMSE 0.78), but a weaker correlation than the CBT′-pH proxy (R² 0.85; RMSE 0.52). Our result suggests that the IBT is a promising indicator for soil pH, particularly in cases when some compounds in the CBT′ index cannot be determined.     

Mineral chemistry of hydrothermal biotite from the Kahang porphyry copper deposit (NE Isfahan), Central Province of Iran

The Kahang porphyry Cu deposit, located northeast of Isfahan city in central of Iran, is associated with a composite Miocene stock and ranges in composition from diorite through granodiorite to quartz-monzonite. Field observations and petrographic studies show that the emplacement of the Kahang stock occurred in several pulses, each associated with its related hydrothermal activity. Early hydrothermal alteration started with a potassic style in the central part of the system and produced a secondary biotite–K-feldspar–magnetite assemblage accompanied by chalcopyrite and pyrite mineralization. Propylitic alteration that took place at the same time as the potassic alteration occurred in the peripheral portions of the stock. Subsequent phyllic alteration overprinted earlier potassic and propylitic alterations. Biotite grains from the potassic and phyllic zones show distinct chemical compositions. The FeO, TiO₂, MnO, K₂O, and Na₂O concentrations in biotite from the phyllic alteration zone are lower than those from the potassic alteration zone. The F and Cl contents of biotite from the potassic alteration zone display relatively high positive correlation with the X_Mg. The fluorine intercept values [IV(F)] from the potassic and phyllic alteration zones are strongly correlated with the fluorine/chlorine intercept values [IV(F/Cl)]. Biotite geothermometry for the potassic and phyllic alteration zones, based on the biotite geothermometer of Beane (1974), yields a temperature range of 422° to 437 °C (mean = 430 °C) and 329° to 336 °C (mean = 333 °C), respectively. The position of data in log (X_F/X_OH) ratio vs. X_Mg and X_Fe diagram suggests that biotite formed under dissimilar composition and temperature conditions in the potassic and phyllic alteration zones. Calculated log fugacity ratios of (fH₂O/fHF), (fH₂O/fHCl), and (fHF/fHCl) show that hydrothermal fluids associated with the potassic alteration were distinctively different from those fluids associated with the phyllic alteration zone at Kahang porphyry Cu deposit. The results of this research indicate that the chemistry of biotite is related to the chemical composition of the magma and the prevailing physical conditions during crystallization.     

Hydrothermal alteration and ore-forming fluids associated with gold-tellurium mineralization in the Dongping gold deposit,China

The Dongping gold deposit hosted in syenites is one of the largest hydrothermal gold deposits in China and composed of ore veins in the upper parts and altered zones in the lower parts of the ore bodies. Pervasive potassic alteration and silicification overprint the wall rocks of the ore deposit. The alteration minerals include orthoclase, microcline, perthite, quartz, sericite, epidote, calcite, hematite and pyrite, with the quartz, pyrite and hematite assemblages closely associated with gold mineralization. The phases of hydrothermal alteration include: (i) potassic alteration, (ii) potassic alteration - silicification, (iii) silicification - epidotization - hematitization, (iv) silicification - sericitization - pyritization and (v) carbonation. Mass-balance calculations in potassic altered and silicified rocks reveal the gain of K₂O, Na₂O, SiO₂, HFSEs and transition elements (TEs) and the loss of REEs. Most major elements were affected by intense mineral reactions, and the REE patterns of the ore are consistent with those of the syenites. Gold, silver and tellurium show positive correlation and close association with silicification. Fluid inclusion homogenization temperatures in quartz veins range from 154 °C to 382 °C (peak at 275 °C–325 °C), with salinities of 4–9 wt.% NaCl equiv. At temperatures of 325 °C the fluid is estimated to have pH = 3.70–5.86, log fO₂ = − 32.4 to − 28.1, with Au and Te transported as Au (HS)₂⁻ and Te₂^2 − complexes. The ore forming fluids evolved from high pH and fO₂ at moderate temperatures into moderate-low pH, low fO₂ and low temperature conditions. The fineness of the precipitated native gold and the contents of the oxide minerals (e.g., magnetite and hematite) decreased, followed by precipitation of Au- and Ag-bearing tellurides. The hydrothermal system was derived from an alkaline magma and the deposit is defined as an alkaline rock-hosted hydrothermal gold deposit.     

Nature of ore-forming fluid and formation conditions of BIF-hosted gold mineralization in the Archean Amalia Greenstone Belt,South Africa: Constraints from fluid inclusion and stable isotope studies

Orogenic gold mineralization in the Amalia greenstone belt is hosted by oxide facies banded iron-formation (BIF). Hydrothermal alteration of the BIF layers is characterized by chloritization, carbonatization, hematization and pyritization, and quartz-carbonate veins that cut across the layers. The alteration mineral assemblages consist of ankerite-ferroan dolomite minerals, siderite, chlorite, hematite, pyrite and subordinate amounts of arsenopyrite and chalcopyrite. Information on the physico-chemical properties of the ore-forming fluids and ambient conditions that promoted gold mineralization at Amalia were deduced from sulfur, oxygen and carbon isotopic ratios, and fluid inclusions from quartz-carbonate samples associated with the gold mineralization.Microthermometric and laser Raman analyses indicated that the ore-forming fluid was composed of low salinity H₂O-CO₂ composition (~3 wt% NaCl equiv.). The combination of microthermometric data and arsenopyrite-pyrite geothermometry suggest that quartz-carbonate vein formation, gold mineralization and associated alteration of the proximal BIF wall rock occurred at temperature-pressure conditions of 300 ± 30 °C and ∼2 kbar. Thermodynamic calculations at 300 °C suggest an increase in fO₂ (10⁻³²–10⁻³⁰ bars) and corresponding decrease in total sulfur concentration (0.002–0.001 m) that overlapped the pyrite-hematite-magnetite boundary during gold mineralization. Although hematite in the alteration assemblage indicate oxidizing conditions at the deposit site, the calculated low fO₂ values are consistent with previously determined high Fe/Fe + Mg ratios (>0.7) in associated chlorite, absence of sulfates and restricted positive δ³⁴S values in associated pyrite. Based on the fluid composition, metal association and physico-chemical conditions reported in the current study, it is confirmed that gold in the Amalia fluid was transported as reduced bisulfide complexes (e.g., Au(HS)₂⁻). At Amalia, gold deposition was most likely a combined effect of increase in fO₂ corresponding to the magnetite-hematite buffer, and reduction in total sulfur contents due to sulfide precipitation during progressive fluid-rock interaction.The epigenetic features coupled with the isotopic compositions of the ore-forming fluid (δ³⁴S_ΣS = +1.8 to +2.3‰, δ¹⁸O_H2O = +6.6 to +7.9‰, and δ¹³C_ΣC = −6.0 to −7.7‰ at 300–330 °C) are consistent with an externally deep-sourced fluid of igneous signature or/and prograde metamorphism of mantle-derived rocks.     

Complex formation of Cm(III) with formate studied by time-resolved laser fluorescence spectroscopy

Pore waters of natural clays, which are investigated as potential host rock formations for high-level nuclear waste, are known to contain large amounts of low-molecular weight organic compounds. These small organic ligands might impact the aqueous geochemistry of the stored radionuclides and, thus, their migration behavior. In the present work, the complexation of Cm(III) with formate in aqueous NaCl solution is investigated by time-resolved laser fluorescence spectroscopy (TRLFS) as a function of the ionic strength (0.5–3.0 mol/kg), the ligand concentration (0–0.2 mol/kg) and the temperature (20–90 °C). The Cm(III) speciation is determined by deconvolution of the emission spectra. The obtained distribution of Cm(III) species is used to calculate the conditional stability constants (log K′(T)) at a given temperature and ionic strength which are extrapolated to zero ionic strength by using the specific ion interaction theory (SIT). Thus, the thermodynamic log K⁰_n(T) values for the formation of [Cm(Form)_n]⁽³⁻ⁿ⁾⁺ (n = 1, 2) and the ion interaction coefficients (ε(i,k)) for [Cm(Form)_n]⁽³⁻ⁿ⁾⁺ (n = 1, 2) with Cl⁻ are obtained. The log K⁰₁(T) (2.11 (20 °C)–2.49 (90 °C)) and log K⁰₂(T) values (1.17 (30 °C–2.01 (90 °C)) increase continuously with increasing temperature. The log K⁰_n(T) values are used to derive the standard reaction enthalpies and entropies (Δ_rH⁰_m, Δ_rS⁰_m) of the respective complexation reactions according to the Van’t Hoff equation. In all cases, positive Δ_rH⁰_m and Δ_rS⁰_m values are obtained. Thus, both complexation steps are endothermic and entropy-driven.     

Metasomatic silicate chemistry at the Bayan Obo Fe–REE–Nb deposit,Inner Mongolia,China: Contrasting chemistry and evolution of fenitising and mineralising fluids

Fenite aureoles around carbonatite dykes, and alteration associated with Fe–REE–Nb ore bodies at Bayan Obo, Inner Mongolia, China, show alkali silicate assemblages containing aegirine–augite, (magnesio-)riebeckite, (magnesio-)arfvedsonite, and phlogopite, accompanied by varying amounts of apatite, albite and quartz. In both fenites and orebodies simple thermodynamic constraints indicate mineral parageneses are consistent with rock buffered cooling accompanied by the infiltration of a range of externally buffered hydrothermal fluids. Statistical analysis of amphibole chemistry indicates that even in apparently texturally well constrained paragenetic stages wide variations in chemistry occur in both the ore bodies and fenites. Much of this variation is attributable to the Mg and F content of amphibole, and is therefore interpreted as a result of variation in externally controlled variables (P, T, initial fluid composition) rather than internally controlled variables such as protolith composition. Similarities in chemistry exist between fenite and some ore body amphiboles. Thermodynamic analysis of the composition of biotite and apatite allows constraints to be placed on the F-content of hydrothermal fluids, and indicates relatively consistent compositions in fenites and orebodies (log a_HF/a_H2O = − 3.8 to − 3.6 at 300 °C and 1 kbar). Amphibole and biotite associated with niobate mineralization are both enriched in fluorine relative to the rest of the paragenesis, and biotite compositions indicate significantly higher HF activities in the hydrothermal fluid (log a_HF/a_H2O = − 2.6 at 300 °C and 1 kbar). The data presented here reinforce previous interpretations of the complex, multistage nature of mineralisation at Bayan Obo, but are still consistent with a direct involvement of carbonatite derived fluids during ore genesis.     

Kinetic studies of the homogeneous abiotic reactions of several chlorinated aliphatic compounds in aqueous solution

The base mediated and neutral abiotic reactions of 4 chlorinated aliphatic compounds have been studied as a function of temperature and pH. Arrhenius parameters obtained for base mediated reactions were as follows: 1,1,2-trichloroethane, log₁₀A=14.36±0.55, E_a=95.6±3.6 kJ/mol; 1,1,1,2-tetrachloroethane, log₁₀A=14.56±0.33, E_a=101.4±2.1 kJ/mol; 1,2,3-trichloropropane, log₁₀A=13.31±0.53, E_a=95.9±3.5 kJ/mol. For the neutral reaction of 2,3-dichloro-1-propene the Arrhenius parameters were log₁₀A=10.2±1.3, E_a=98±9 kJ/mol. For 1,1,2-trichloroethane the product of the base mediated reaction was identified as 1,1-dichloroethene, in contrast to previous studies. 2,3-dichloro-1-propene was found as an intermediate in the base mediated reaction of 1,2,3-trichloropropane, with 2-chloro-2-propen-1-ol as the major final product. Results from the present study are compared to those found in previous work.     

Distribution of glycerol dialkyl glycerol tetraether lipids along an altitudinal transect on Mt. Xiangpi,NE Qinghai-Tibetan Plateau,China

The distribution of glycerol dialkyl glycerol tetraethers (GDGTs) can reflect continental environmental changes. Recently, the distribution of branched GDGTs (bGDGTs) has been proposed as a novel tool for paleoelevation reconstructions. Here we report the variation in TEX₈₆ (tetraether index of 86 carbon atoms) of isoprenoidal GDGTs (iGDGTs) and MBT (methylation of branched tetraether index) of bGDGTs along an altitudinal transect on Mt. Xiangpi, NE Qinghai-Tibetan Plateau. Both TEX₈₆ and MBT values of surface soils showed significant linear decreases with altitude (TEX₈₆: R² = 0.65; n = 50; MBT: R² = 0.69; n = 24). We suggest that the apparent relationships between the two indices and altitude may be related to temperature. Our preliminary investigation suggests that the TEX₈₆ index can potentially be applied as a paleoelevation indicator in addition to the MBT index on the Qinghai-Tibetan Plateau.     

Geochemical and isotopic approach to maturity/source/mixing estimations for natural gas and associated condensates in the Thrace Basin,NW Turkey

The Tertiary Thrace Basin located in NW Turkey comprises 9 km of clastic-sedimentary column ranging in age from Early Eocene to Recent in age. Fifteen natural gas and 10 associated condensate samples collected from the 11 different gas fields along the NW–SE extending zone of the northern portion of the basin were evaluated on the basis of their chemical and individual C isotopic compositions. For the purpose of the study, the genesis of CH₄, thermogenic C₂₊ gases, and associated condensates were evaluated separately.Methane appears to have 3 origins: Group-1 CH₄ is bacteriogenic (Calculated δ¹³C_C1–C = −61.48‰; Silivri Field) and found in Oligocene reservoirs and mixed with the thermogenic Group-2 CH₄. They probably formed in the Upper Oligocene coal and shales deposited in a marshy-swamp environment of fluvio-deltaic settings. Group-2 (δ¹³C_C1–C = −35.80‰; Hamitabat Field) and Group-3 (δ¹³C_1–C = −49.10‰; Değirmenköy Field) methanes are thermogenic and share the same origin with the Group-2 and Group-3 C₂₊ gases. The Group-2 C₂₊ gases include 63% of the gas fields. They are produced from both Eocene (overwhelmingly) and Oligocene reservoirs. These gases were almost certainly generated from isotopically heavy terrestrial kerogen (δ¹³C = −21‰) present in the Eocene deltaic Hamitabat shales. The Group-3 C₂₊ gases, produced from one field, were generated from isotopically light marine kerogen (δ¹³C = −29‰). Lower Oligoce ne Mezardere shales deposited in pro-deltaic settings are believed to be the source of these gases.The bulk and individual n-alkane isotopic relationships between the rock extracts, gases, condensates and oils from the basin differentiated two Groups of condensates, which can be genetically linked to the Group-2 and -3 thermogenic C₂₊ gases. However, it is crucial to note that condensates do not necessarily correlate to their associated gases.Maturity assessments on the Group-1 and -2 thermogenic gases based on their estimated initial kerogen isotope values (δ¹³C = −21‰; −29‰) and on the biomarkers present in the associated condensates reveal that all the hydrocarbons including gases, condensates and oils are the products of primary cracking at the early mature st age (R_eq = 0.55–0.81%). It is demonstrated that the open-system source conditions required for such an early-mature hydrocarbon expulsion exist and are supported by fault systems of the basin.     

Mineralogy and genetic features of the Cu-As-Ni-Sb-Pb mineralization from the Mlakva polymetallic deposit (Serbia) — New occurrence of (Ni-Sb)-bearing Cu-arsenides

(Ni-Sb)-bearing Cu-arsenides are rare minerals within the Mlakva and Kram mining sectors (Boranja ore field) one of the less-known Serbian Cu deposits. (Ni-Sb)-bearing Cu-arsenides were collected from the Mlakva skarn-replacement Cu(Ag,Bi)-FeS polymetallic deposit. The identified phases include β-domeykite, Ni-bearing koutekite and (Ni-Sb)-bearing α-domeykite. (Ni-Sb)-bearing Cu-arsenides are associated with nickeline, arsenical breithauptite, chalcocite, native Ag, native Pb and litharge. Pyrrhotite, pyrite, chalcopyrite, cubanite, bismuthinite, molybdenite, sphalerite, galena, Pb(Cu)-Bi sulfosalts and native Bi, as well as minor magnetite, scheelite and powellite are associated with the sulfide paragenesis. The electron microprobe analyses of the (Ni-Sb)-bearing Cu-arsenides yielded the following average formulae: (Cu_2.73,Ni_0.17,Fe_0.03,Ag_0.01)_∑ 2.94(As_0.98,Sb_0.05,S_0.02)_∑ 1.06–β-domeykite (simplified formula (Cu_2.7,Ni_0.2)_∑ 2.9As_1.1); (Cu_3.40,Ni_1.40,Fe_0.11)_∑ 4.91(As_1.94,Sb_0.13,S_0.02)_∑ 2.08–Ni-bearing koutekite (simplified formula (Cu_3.4Ni_1.5)_∑ 4.9As_2.1); and Cu_1.97(Ni_0.98,Fe_0.03)_∑ 1.01(As_0.81,Sb_0.22)_∑ 1.03–(Ni–Sb)-bearing α-domeykite (simplified formula Cu₂NiAs). The Rietveld refinement yielded the following unit-cell parameters for β-domeykite and Ni–bearing koutekite: a = 7.1331(4); c = 7.3042(5) Å; V = 321.86(2) ų, and a = 5.922(4); b = 11.447(9); c = 5.480(4) Å; V = 371.48(5) ų, respectively. Ore geology, paragenetic assemblages and genesis of the Mlakva deposit are discussed in detail and the Cu-As-Ni-Sb-Pb mineralization has been compared with similar well-known global deposits.     

Controls on biochemical oxygen demand in the upper Klamath River,Oregon

A series of 30-day biochemical oxygen demand (BOD) experiments were conducted on water column samples from a reach of the upper Klamath River that experiences hypoxia and anoxia in summer. Samples were incubated with added nitrification inhibitor to measure carbonaceous BOD (CBOD), untreated to measure total BOD, which included demand from nitrogenous BOD (NBOD), and coarse-filtered to examine the effect of removing large particulate matter. All BOD data were fit well with a two-group model, so named because it considered contributions from both labile and refractory pools of carbon: BOD_t = a₁(1 ? e^? a₀t) + a₂t. Site-average labile first-order decay rates a₀ ranged from 0.15 to 0.22/day for CBOD and 0.11 to 0.29/day for BOD. Site-average values of refractory zero-order decay rates a₂ ranged from 0.13 to 0.25 mg/L/day for CBOD and 0.01 to 0.45 mg/L/day for BOD; the zero-order CBOD decay rate increased from early- to mid-summer. Values of ultimate CBOD for the labile component a₁ ranged from 5.5 to 28.8 mg/L for CBOD, and 7.6 to 30.8 mg/L for BOD. Two upstream sites had higher CBOD compared to those downstream. Maximum measured total BOD₅ and BOD₃₀ during the study were 26.5 and 55.4 mg/L; minimums were 4.2 and 13.6 mg/L. For most samples, the oxygen demand from the three components considered here were: labile CBOD > NBOD > refractory CBOD, though the relative importance of refractory CBOD to oxygen demand increased over time. Coarse-filtering reduced CBOD for samples with high particulate carbon and high biovolumes of Aphanizomenon flos-aquae. There was a strong positive correlation between BOD, CBOD, and the labile component of CBOD to particulate C and N, with weaker positive correlation to field pH, field dissolved oxygen, and total N. The refractory component of CBOD was not correlated to particulate matter, instead showing weak but statistically significant correlation to dissolved organic carbon, UV absorbance at 254 nm, and total N. Particulate organic matter, especially the alga A.flos-aquae, is an important component of oxygen demand in this reach of the Klamath River, though refractory dissolved organic matter would continue to exert an oxygen demand over longer time periods and as water travels downstream.     

A LREE-depleted component in the Afar plume: Further evidence from Quaternary Djibouti basalts

Major, trace element and isotopic (Sr, Nd, Pb) data and unspiked K–Ar ages are presented for Quaternary (0.90–0.95 Ma old) basalts from the Hayyabley volcano, Djibouti. These basalts are LREE-depleted (La_n/Sm_n = 0.76–0.83), with ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.70369 to 0.70376, and rather homogeneous ¹⁴³Nd/¹⁴⁴Nd (ε_Nd = + 5.9–+ 7.3) and Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.47–18.55, ²⁰⁷Pb/²⁰⁴Pb = 15.52–15.57, ²⁰⁸Pb/²⁰⁴Pb = 38.62–38.77). They are very different from the underlying enriched Tadjoura Gulf basalts, and from the N-MORB erupted from the nascent oceanic ridges of the Red Sea and Gulf of Aden. Their compositions closely resemble those of (1) depleted Quaternary Manda Hararo basalts from the Afar depression in Ethiopia and (2) one Oligocene basalt from the Ethiopian Plateau trap series. Their trace element and Sr, Nd, Pb isotope systematics suggest the involvement of a discrete but minor LREE-depleted component, which is probably an intrinsic part of the Afar plume.     

Hydrosulfide/sulfide complexes of zinc to 250 °C and the thermodynamic properties of sphalerite

The solubility of synthetic ZnS_(cr) was measured at 25–250 °C and P = 150 bars as a function of pH in aqueous sulfide solutions (~ 0.015–0.15 m of total reduced sulfur). The solubility determinations were performed using a Ti flow-through hydrothermal reactor. The solubility of ZnS_(cr) was found to increase slowly with temperature over the whole pH range from 2 to ~ 10. The values of the Zn–S–HS complex stability constant, β, were determined for Zn(HS)₂⁰_(aq), Zn(HS)₃^?, Zn(HS)₄^2?, and ZnS(HS)^?. Based on the experimental values the Ryzhenko–Bryzgalin electrostatic model parameters for these stability constants were calculated, and the ZnS_(cr) solubility and the speciation of Zn in sulfide-containing hydrothermal solutions were evaluated. The most pronounced solubility increase, about 3 log units at m(S_total) = 0.1 for the temperatures from 25 to 250 °C, was found in acidic solutions (pH ~ 3 to 4) in the Zn(HS)₂⁰_(aq) predominance field. In weakly alkaline solutions, where Zn(HS)₃^? and Zn(HS)₄^2? are the dominant Zn–S–HS complexes, the ZnS_(cr) solubility increases by 1 log unit at the same conditions. It was found that ZnS(HS)^? and especially Zn(HS)₄^2? become less important in high temperature solutions. At 25 °C and m(S_total) = 0.1, these species dominate Zn speciation at pH > 7. At 100 °C and m(S_total) = 0.1, the maximum fraction of Zn(HS)₄^2? is only 20% of the total Zn concentration (i.e. at pH_t ~ 7.5), whereas at 350 °C and 3 <pH_t <10, the fraction of Zn(HS)₄^2? and ZnS(HS)^? is less than 0.05% and 2.5% respectively, of the total Zn concentration and Zn(HS)₂⁰ and Zn(HS)₃^? predominate. The measured equilibrium formation constants were combined with the literature data on the stability of Zn–Cl complexes in order to evaluate the concentration and speciation of Zn in chloride solutions. It was found that at acidic pH, and in more saline fluids having total chloride > 0.05 m, Zn–Cl complexes are responsible for hydrothermal Zn transport with no significant contribution of Zn–S–HS complexes. The hydrosulfide/sulfide complexes will play a more important role in lower salinity (< 0.05 m chloride) hydrothermal solutions which are characteristic of many epithermal ore depositing environments. The value of Δ_fG° (β-ZnS_(cr)) = ? 198.6 ± 0.2 kJ/mol at 25 °C was determined via solubility measurements of natural low-iron Santander (Spain) sphalerite.     

Metamorphic evolution of the Maud Belt: P–T–t path for high-grade gneisses in Gjelsvikfjella,Dronning Maud Land,East Antarctica

A metamorphic petrological study, in conjunction with recent precise geochronometric data, revealed a complex P–T–t path for high-grade gneisses in a hitherto poorly understood sector of the Mesoproterozoic Maud Belt in East Antarctica. The Maud Belt is an extensive high-grade, polydeformed, metamorphic belt, which records two significant tectono-thermal episodes, once towards the end of the Mesoproterozoic and again towards the late Neoproterozoic/Cambrian. In contrast to previous models, most of the metamorphic mineral assemblages are related to a Pan-African tectono-thermal overprint, with only very few relics of late Mesoproterozoic granulite-facies mineral assemblages (M₁) left in strain-protected domains. Petrological and mineral chemical evidence indicates a clockwise P–T–t path for the Pan-African orogeny. Peak metamorphic (M_2b) conditions recorded by most rocks in the area (T = 709–785 °C and P = 7.0–9.5 kbar) during the Pan-African orogeny were attained subsequent to decompression from probably eclogite-facies metamorphic conditions (M_2a).The new data acquired in this study, together with recent geochronological and geochemical data, permit the development of a geodynamic model for the Maud Belt that involves volcanic arc formation during the late Mesoproterozoic followed by extension at 1100 Ma and subsequent high-grade tectono-thermal reworking once during continent–continent collision at the end of the Mesoproterozoic (M₁; 1090–1030 Ma) and again during the Pan-African orogeny (M_2a, M_2b) between 565 and 530 Ma. Post-peak metamorphic K-metasomatism under amphibolite-facies conditions (M_2c) followed and is ascribed to post-orogenic bimodal magmatism between 500 and 480 Ma.     

Geological and isotopic constraints on the origin of the Anle carbonate-hosted Zn–Pb deposit in northwestern Yunnan Province,SW China

The Anle Zn–Pb deposit, hosted by Upper Cambrian dolostone, is located in the southern Songpan–Ganzi Block in southwest China. In this deposit, ore bodies occur as stratiform lenses and consist of galena, sphalerite and pyrite as ore minerals, and quartz, dolomite and calcite as gangue minerals. The mineralization shows mainly vein, banded and brecciated structures. Four ore bodies have been found in the Anle deposit, with a combined 2.0 million tonnes (Mt) of sulfide ores at average grades of 1.64 wt.% Pb, 6.64 wt.% Zn and 45 g/t Ag. Brown, brownish-yellow and yellow sphalerite samples have δ⁶⁶Zn values ranging from + 0.08 to + 0.10‰ (average + 0.09‰, n = 3), + 0.12 to + 0.38‰ (average + 0.24‰, n = 8) and + 0.40 to + 0.50‰ (average + 0.46‰, n = 3), respectively. We interpret the progressively heavier Zn isotopes from brown to yellow sphalerite as being led by kinetic Raleigh fractional crystallization. Calcite samples have δ¹³C_PDB and δ¹⁸O_SMOW values ranging from − 4.8 to − 0.2‰ (average − 1.7‰, n = 7) and + 17.9 to + 21.4‰ (average + 19.6‰, n = 7), respectively. Whole-rock δ¹³C_PDB and δ¹⁸O_SMOW values of the Cambrian ore-hosting dolostone range from + 0.1 to + 1.1‰ (average + 0.6‰, n = 3) and + 23.2 to + 24.1‰ (average + 23.6‰, n = 3), respectively. This suggests that carbon in the ore-forming fluids was provided by the host dolostone through carbonate dissolution. δ³⁴S_CDT values of sulfide samples range between − 1.3‰ and + 17.8‰ with an average value of + 6.3‰ (n = 25), lower than evaporites (such as barite + 19.8‰) in the overlaying Lower Ordovician sedimentary strata. The data suggest that sulfur in the hydrothermal fluids were derived from evaporites by thermo-chemical sulfate reduction (TSR). ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios for sulfide minerals range from 17.63 to 17.86, 15.58 to 15.69 and 37.62 to 37.95, respectively. The data are similar to those of the age-corrected Cambrian ore-hosting dolostone (²⁰⁶Pb/²⁰⁴Pb = 17.70–17.98, ²⁰⁷Pb/²⁰⁴Pb = 15.58–15.65 and ²⁰⁸Pb/²⁰⁴Pb = 37.67–38.06), but lower than those of age-corrected Ordovician sandstone and slate (²⁰⁶Pb/²⁰⁴Pb = 18.54–19.58, ²⁰⁷Pb/²⁰⁴Pb = 15.73–15.81 and ²⁰⁸Pb/²⁰⁴Pb = 38.44–39.60). This indicates that ore Pb was most likely to be derived from the Cambrian ore-hosting dolostone. Therefore, our new geological and isotopic evidence suggests that the Anle Zn–Pb deposit is best classified to be an epigenetic carbonate-hosted Mississippi Valley-type (MVT) deposit.     

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.     

Mineralogical and microfabric characteristics of magnetite in the Wuyang Precambrian BIFs,southern North China Craton: Implications for genesis and depositional processes of the associated BIFs

Precambrian Banded Iron Formations (BIFs) are widely distributed in the North China Craton (NCC). Among them, the Wuyang BIFs located in the southern margin of NCC occur in the Late Archaean Tieshanmiao Formation and can be subdivided in two different sub-types: (i) quartz–magnetite BIFs (QMB), consisting of magnetite, fine-microcrystalline quartz and minor calcite and (ii) pyroxene–magnetite BIFs (PMB), composed of pyroxene, fine-microcrystalline quartz and subordinate feldspars. Both sub-types display apparent discrepancies in terms of petrography and mineral composition.As shown in Electron BackScattered Diffraction (EBSD) images and micrographs, magnetite grains from the QMB range in size from tens up to hundreds of μm, whereas magnetite crystals from the PMB can be up to a few tens of μm across. The X-ray diffraction (XRD) structural data indicate that magnetite from both BIF sub-types is equiaxed (cubic) and was generated by sedimentary metamorphic processes. The cell parameters of magnetite in the QMB are a = b = c = 8.396 Å and Z = 8, which deviate slightly from these of magnetite in the PMB: a = b = c = 8.394 Å and Z = 8. The analytical results of Raman spectroscopy analysis revealed micro-structural signatures of both magnetite (Raman shifts near 552 cm⁻¹ and 673 cm⁻¹) and hematite (Raman shifts near 227 cm⁻¹, 295 cm⁻¹ and 413 cm⁻¹). In magnetite from both QMB and PMB, the crystallinity degree is similar for magnetite micro-structures but varies significantly for hematite micro-structures. Oxygen fugacity (fO₂) conditions fluctuated during the recrystallization of magnetite in the QMB, whereas no evident variation of fO₂ occurred during the formation of magnetite in the PMB. Analytical results of laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) show that the Si, Al and Mg abundances are higher in magnetite from the QMB, whereas the Ti and Mn contents are more elevated in magnetite from the PMB. Magnetite composition also denotes that both BIF sub-types are sedimentary-metamorphic origin, whereas the deposition of PMB was also affected by volcanic activities. Overall data indicate that the differences in the depositional environment of each BIF sub-type are due to the involvement of volcanic eruption processes in the genesis of the PMB. Thus, this paper indicated that the QMB was deposited by chemical deposition at the long-term interval of volcanic eruptions, and the PMB were the product of chemical deposition affected by the volcanic eruption.