Fe-Zn mixing energetics of the Iss phase in the system Cu-Fe-Zn-S

A thermodynamic analysis of the intermediate solid solution (Iss) of near-cubanite composition has been attempted by considering an Fe–Zn exchange equilibrium between Iss and sphalerite. The interchange free-energy parameter of Fe–Zn mixing in Iss (W^Iss) and the free energy of the exchange equilibrium (G_1,T ) have been deduced at 500, 600, 700 and 723° C using the compositional data of sphalerite and Iss from phase equilibrium experiments and by the standard method of linear regression analysis. For sphalerite, two independent activity-composition models have been chosen. The extracted values of G_1,T and W^Iss, using both models, are compared. Although the values match, the errors in the extracted parameters are relatively larger when Hutcheon's model is used. Both G_1,T and W^Iss show linear variations with temperature, as given by the following relations: G^1,T = –35.41 + 0.033 T in kcal (SE=0.229)W^ISS= 48.451 – 0.041 T in kcal (SE=0.565) Activity-composition relations and different mixing parameters have been calculated for the Iss phase. A large positive deviation from ideality is observed in Iss on the join CuFe₂S₃–CuZn₂S₃. No geothermometric application has been attempted in this study, even though Iss of cubanite composition (isocubanite) in association with sphalerite, pyrite and pyrrhotite is reported from seafloor hydrothermal deposits. This is due to the fact that: (a) the temperatures of formation of these deposits are significantly lower than 500° C, the lower limit of appropriate experimental data base; (b) microprobe data of the coexisting isocubanite and sphalerite in the relevant natural assemblages are not available.Symbols a _J ⁱ activity of component i in phase J - G_{1, T} standard free energy change of reaction (cal) - G^IM free energy of ideal mixing (cal) - G^EM free energy of excess mixing (cal) - G _M ^ex free energy of mixing (cal) - G _i excess free energy of mixing at infinite dilution (cal) - _i ^J activity coefficient of component i in phase J - _i ^{J, 0} standard chemical potential of component i in phase J (cal) - ; _i ^J chemical potential of component i in phase J (cal) - R universal gas constant (1.98717 cal/K·mol) - T temperature in degree (K) - W^J interchange free energy of phase J in (cal) - X _J ⁱ mole fraction of component i in phase J     

Rare Earth Element Enrichment in Late Archean Manganese Deposits from the Iron Ore Group,East India

The major, trace and rare earth element (REE) composition of Late Archean manganese, ferromanganese and iron ores from the Iron Ore Group (IOG) in Orissa, east India, was examined. Manganese deposits, occurring above the iron formations of the IOG, display massive, rhythmically laminated or botryoidal textures. The ores are composed primarily of iron and manganese, and are low in other major and trace elements such as SiO₂, Al₂O₃, P₂O₅ and Zr. The total REE concentration is as high as 975 ppm in manganese ores, whereas concentrations as high as 345 ppm and 211 ppm are found in ferromanganese and iron ores, respectively. Heavy REE (HREE) enrichments, negative Ce anomalies and positive Eu anomalies were observed in post‐Archean average shale (PAAS)‐normalized REE patterns of the IOG manganese and ferromanganese ores. The stratiform or stratabound shapes of ore bodies within the shale horizon, and REE geochemistry, suggest that the manganese and ferromanganese ores of the IOG were formed by iron and/or manganese precipitation from a submarine, hydrothermal solution under oxic conditions that occurred as a result of mixing with oxic seawater. While HREE concentrations in the Late Archean manganese and ferromanganese ores in the IOG are slightly less than those of the Phanerozoic ferromanganese ores in Japan, HREE resources in the IOG manganese deposits appear to be two orders of magnitude higher because of the large size of the deposits. Although a reliable, economic concentration technique for HREE from manganese and ferromanganese ores has not yet been developed, those ores could be an important future source of HREE.     

Species diversity variations in Neogene deep-sea benthic foraminifera at ODP Hole 730A,western Arabian Sea

Deep-sea benthic foraminifera are an important and widely used marine proxy to understand paleoceanographic and paleoclimatic changes on regional and global scales, owing to their sensitivity to oceanic and climatic turnovers. Some species of benthic foraminifera are sensitive to changes in water mass properties whereas others are sensitive to organic fluxes and deep-sea oxygenation. Benthic faunal diversity has been found closely linked to food web, bottom water oxygen levels, and substrate and water mass stability. The present study is aimed at analyzing species diversity trends in benthic foraminifera and their linkages with Indian monsoon variability during the Neogene. Species diversity of benthic foraminifera is examined in terms of number of species (S), information function (H), equitability (E) and Sanders’ rarefied values, which were combined with relative abundances of high and low productivity benthic foraminifera at Ocean Drilling Program Hole 730A, Oman margin, western Arabian Sea. The Oman margin offers the best opportunity to understand monsoon-driven changes in benthic diversity since summer monsoon winds have greater impact on the study area. The species diversity was higher during the early Miocene Climatic Optimum (～17.2–16.4 Ma) followed by a decrease during 16.4–13 Ma coinciding with a major increase in Antarctic ice volume and increased formation of Antarctic Bottom Water. All the diversity parameters show an increase during 13–11.6 Ma, a gradual decrease during 11.6–9 Ma and then an increase with a maximum at 7 Ma. Thereafter the values show little change until 1.2 Ma when all the parameters abruptly decrease. The benthic foraminiferal populations and diversity at Hole 730A were mainly driven by the Indian monsoon, and polar waters might have played a minor or no role since early Neogene period as the Arabian Sea is an enclosed basin.     

Comparative geochemical,magnetic susceptibility,and fluid inclusion studies on the Paleoproterozoic Malanjkhand and Dongargarh granitoids,Central India and implications to metallogeny

The Malanjkhand granodiorite (MG) hosting economic copper mineralization and the hitherto barren Dongargarh granitoids (DG) have subtle differences in their petrographic and bulk geochemical features. The two plutons are contiguous and occur in the northern part of the Bhandara Craton in Central India with intervening volcanosedimentary sequence of the Dongargarh Supergroup amidst older gneisses. The Dongargarh granitoids studied in two smaller units have higher bulk magnetic susceptibility than the Cu-bearing MG; the majority of samples studied from the latter being ilmenite-series rocks. DG crystallized at higher pressures compared to MG. Plagioclase composition ranges from albite to high bytownite in MG, whereas its compositional range is restricted to high andesine in DG. However, both intrusions give identical temperature ranges estimated by binary feldspar thermometry. Biotite in MG shows higher Fe/Mg ratios, as well as a greater range of compositional variation, than that in DG. MG has a moderately fractionated rare earth element distribution pattern without any significant Eu anomaly, showing depletion in mid-range rare earth elements (REE) and no depletion in heavy REE. DG is characterized by a prominent negative Eu anomaly. Geochemical features indicate subtle differences in the nature of source rocks and/or melting processes responsible for the generation of the two granitoids. MG displays more consistent bulk chemical features and is possibly a result of crystallization from a homogeneous granodioritic melt. DG displays a greater diversity and possibly incorporated a significant felsic crustal component that contributed to the parent melt. A fluid inclusion study of quartz grains from the granitoids and barren quartz veins occurring in MG indicates identical low-temperature nature of the fluid in both cases. They differ from the fluid in the mineralized zone in MG in the absence of a high-temperature component and CO₂ in the fluid. Late-stage fluids in DG and associated barren quartz veins compare well with those from MG. The hydrothermal activity following the granite emplacement seems to have operated under identical temperature conditions, and the aqueous fluid at the two occurrences seems to have been broadly similar. In both cases, internal evolution of the exsolved fluid to low temperatures and moderate salinity are visualized. Based on the existing information, the lack of ore potential in DG may be attributed to the metal and volatile (water + halogens) deficient nature of the parental granitic melt.     

Reconstruction of Physicochemical Environment of Hydrothermal Mineralization at Malanjkhand Copper Deposit,Central India: Constraints from Sulfur Isotope Ratios in Pyrite,Molybdenite and Chalcopyrite

δ³⁴S values of pyrite, molybdenite and chalcopyrite were determined from the Malanjkhand copper deposit. These minerals constitute the primary sulfide phases that were deposited after the initial magnetite deposition in the main orebody and host granitoid. Pyrite exhibits a depleted range of values (?2.63 to ?0.56‰), chalcopyrite, a very narrow range of values around zero (?0.039 to 0.201‰) and molybdenite furnishes a range of enriched values (0.68 to 1.98‰). On back calculation of the δ³⁴S values of H₂S in the fluid from which the minerals were likely to have precipitated, using standard expressions for equilibrium fractionation at the temperature range obtained from fluid inclusion and mineral fluid equilibria, it is observed that H₂S in the fluid at pyrite deposition was depleted and gradually became enriched towards molybdenite and chalcopyrite deposition. This trend is best explained as being due to inorganic reduction of SO₄^2? in the fluid and is very much in agreement with the paragenetic sequence indicating increasing activity of H₂S in the fluid. The very restricted range in the δ³⁴S values of sulfide minerals in the fluid does indicate a single, possibly magmatic, source of sulfur that also agrees well with the earlier deduced model of genesis of the deposit as an ancient geothermal system associated with granitic magmatism.     

Fluid evolution in the Kolar Gold Field: evidence from fluid inclusion studies

Gold mineralization in the Kolar schist belt of the Dharwar craton occurs dominantly in the form of a sulfide-poor Au-quartz lode (the Champion lode exposed in the Mysore and other mines) and sulfide-rich auriferous lodes (from the Nundydroog mine). Fluid inclusion microthermometric experiments were conducted on primary inclusions in quartz intimately associated with Au-mineralization. Homogenization studies on aqueous-biphase (L + V), aqueous polyphase (L + V+ halite) and aqueous-carbonic (L_CO2± V_CO2 + L_aq) inclusions from the Champion lode furnish a temperature range of 120 to 420 °C. Freezing of aqueous biphase inclusions and dissolution of halite in the aqueous polyphase inclusions provide salinity of 5 to 50 wt.% NaCl equivalent. Fluid inclusion thermobarometry from the total homogenization of aqueous-carbonic inclusions and from intersecting isochores of coeval pure-carbonic (L_CO2± V_CO2) and pure-aqueous inclusions constrain the P-T path of evolution of the fluid in the Champion lode. Gold precipitation was likely to have been brought about in response to a sharp fall in pressure with attendant unmixing of liquid-CO₂ from the parent H₂O-CO₂ fluid of possible metamorphic origin. This would imply transportation of gold by some pressure-sensitive complex such as the Au-carbonyl. Fluid characteristics are different in the sulfide-rich auriferous lodes, as indicated by the virtual absence of the CO₂-bearing and the halite-bearing inclusions. The fluid evolution path, as evident from the crude positive colinearity of temperature and salinity, is due to mixing of a low (≤200 °C) temperature-low saline (≤7 wt.% NaCl equivalent) fluid with a high temperature (≥400 °C)-high saline (≥50 wt.% NaCl equivalent) fluid. The lack of CO₂ and association of Au with sulfides indicate a different mode of gold transport, as chloride or bisulfide complexing, deposition of which was possibly brought about by fluid mixing. Received: 17 April 1997 / Accepted: 30 June 1998     

Numerical hindcast of extreme waves

The cyclone wave parameters are predicted using Young’s parametric hurricane wave prediction model. The input cyclone tracks for this work are obtained from Fleet Naval Meteorology and Oceanography Center, USA. Extreme value analysis is carried out to obtain the wave heights and periods for 1 in 5, 10, 50 and 100 years return periods, respectively. The deep-water hindcast wave corresponding to 100 years from probable directions are allowed to propagate to Visakhapatnam coastal waters using nearshore spectral wind-wave mode. The offshore wave height for one in 100-year return period is 11.9 m, and the corresponding nearshore wave height at 10-m water depth varies between 4.6 and 5.6 m depending on the directional spreading. Weibull distribution is chosen to fit the 24 cyclonic data sets over a total period of 30 years (September 1972 to November 2002). This paper demonstrates usefulness of Young’s wave model for deep-water extreme wave hindcasting. Further, the results of the present study would be highly useful for assessing the design wave height for Visakhapatnam coast.     

Contrasting fluid inclusion characteristics of staniferous and non-staniferous pegmatites of Southeast Bastar, Central India

Tin and rare metal-bearing granitic pegmatites in the Bastar–Malkangiri pegmatite belt of Central India are hosted by metabasic and metasedimentary country rocks. Fluid inclusion studies were conducted in spatially associated two-mica granite and the staniferous and non-staniferous pegmatites to characterize the physicochemical environment of mineralization, to distinguish different pegmatites in terms of their fluid characteristics and to envisage a possible genetic link between the pegmatites and spatially associated granite. Three different types of primary inclusions were identified. The type-I, aqueous bi-phase (L+V) inclusions are the most abundant and ubiquitous. Type-II polyphase (L+V+S) inclusions are rare. Type-III, monophase (L) and metastable aqueous inclusions, though less abundant than type-I inclusions, are ubiquitous. The fluid evolution trends indicate that mixing of two different fluids of contrasting salinities, one of high salinity (20–30 wt% NaCl equivalent) and another of low salinity (0–10 wt% NaCl equivalent), was responsible for precipitation of the bulk of the cassiterite. This mixing is the single most important characteristic that distinguishes the staniferous pegmatites from their non-staniferous counterparts. The non-staniferous pegmatites, on the other hand, are typified by the presence either of a high saline or a low saline fluid that evolved through simple cooling. The minimum pressure–temperature of entrapment, estimated from the intersections of the halide liquidus with the corresponding inclusion isochores of type-II inclusions, range between 2.1–2.2 kb and 300–325 °C. The similar P–T range of fluid entrapment of the staniferous and non-staniferous pegmatites indicates that they were possibly emplaced within a similar physical environment. Type-I inclusions from granite recorded only the high salinity fluid, the salinity of which compares well with that of the highly saline fluid component of type-I inclusions in the pegmatites. This is a possible indication of a genetic link between the pegmatites and spatially associated granite.     

Optimum tracking of ship routes in 3g-WAM simulated rough weather using IRS-P4 (MSMR) analysed wind fields

Rough weather ship routing is studied using model hindcast wave climate. With the launch of IRS-P4 (OCEANSAT-I), it became possible to carry out routine wave forecasting over the Indian Ocean. The MSMR channel of the satellite gives scalar wind, which is analysed at National center for Medium Range Weather Forecasting (NCMRWF), India for converting to vector winds. The same is used as input to third generation wave model for the rough weather month of July 2000. Simulations are carried out using Cycle-4 of third generation spectral wave model WAM for regional grid system. This simulated wave climate formed the basis for computing effective ship velocity in the irregular seaway. This study gives a quantitative estimation of change in ship velocity in the open Indian Ocean for a Liberty type ship. The optimal route is charted using Dijkstra’s algorithm for minimal time path between Calcutta and Sumatra. The optimum track information has broad scope for obtaining a safer route, least time route by avoiding delay in schedule with minimum fuel consumption.