The distribution of total and electrochemically available copper in the northwestern atlantic ocean

Copper in a series of samples from the northwestern Atlantic has been determined by anodic stripping voltammetry (ASV) and atomic absorption spectrometry after preconcentration by cobalt—APDC coprecipitation. Samples from a transect across the continental shelf directly off the New York Bight showed a linear relationship between total copper and salinity (31–34‰) and less than 5% of the total copper was detectable by ASV. A slope water station showed less than 9% of the total copper to be ASV detectable in the upper 780m, below which the ASV detectable copper increased to 70% at 3000 m. The Sargasso Sea profiles showed less than 7% ASV detectable copper in the upper 150 m; the fraction of the total copper detected by ASV increased to about 80% of the total copper at greater depths. The reduced availability of copper to the ASV measurement in coastal waters and open ocean surface waters appears to be related to recent contact with waters where biological productivity occurs.     

Fluids in granulites of the Southern Marginal Zone of the Limpopo Belt, South Africa

The Southern Marginal Zone of the Limpopo Belt in South Africa is characterised by a granulite and retrograde hydrated granulite terrane. The Southern Marginal Zone is, therefore, perfectly suitable to study fluids during and after granulite facies metamorphism by means of fluid inclusions and equilibrium calculations. Isolated and clustered high-salinity aqueous and CO₂(-CH₄) fluid inclusions within quartz inclusions in garnet in metapelites demonstrate that these immiscible low H₂O activity fluids were present under peak metamorphic conditions (800-850 °C, 7.5-8.5 kbar). The absence of widespread high-temperature metasomatic alteration indicates that the brine fluid was probably only locally present in small quantities. Thermocalc calculations demonstrate that the peak metamorphic mineral assemblage in mafic granulites was in equilibrium with a fluid with a low H₂O activity (0.2-0.3). The absence of water in CO₂-rich fluid inclusions is due to either observation difficulties or selective water leakage. The density of CO₂ inclusions in trails suggests a retrograde P-T path dominated by decompression at T<600 °C. Re-evaluation of previously published data demonstrates that retrograde hydration of the granulites at 600 °C occurred in the presence of H₂O and CO₂-rich fluids under P-T conditions of 5-6 kbar and ~600 °C. The different compositions of the hydrating fluid suggest more than one fluid source.     

Diamond precipitation from ascending reduced fluids in the Kaapvaal lithosphere: Thermodynamic constraints

Previous research has shown that the Kaapvaal lithospheric mantle is generally reduced and characterised by a decreasing redox state with increasing depth. As a consequence, C-O-H fluids in the Kaapvaal lithospheric mantle are dominated by H₂O, CH₄, and C₂H₆. Thermodynamic calculations demonstrate that diamond precipitation from such a fluid during ascend is possible as it is exposed to a more oxidised environment and both CH₄ and C₂H₆ are oxidised. However, the calculations also demonstrate that the diamond precipitation potential from such a fluid decreases when: (1) the mantle is either more reduced or oxidised compared to the Kaapvaal mantle, or (2) the change in temperature with pressure is smaller compared to that of the Kaapvaal mantle. Therefore, the presence of reduced mantle fluid species and a generally decreasing oxygen fugacity with increasing depth do not necessarily warrant diamond precipitation from a rising reduced fluid.     

http://www.sciencedirect.com/science/article/pii/S1674987114000218

Fluid infiltration into retrograde granulites of the Southern Marginal Zone(Limpopo high grade terrain)is exemplified by hydration reactions.shear zone hosted metasomatism,and lode gold mineralisation.Hydration reactions include the breakdown of cordierite and orthopyroxene to gedrite kyanite,and anthophyllite,respectively.Metamorphic petrology,fluid inclusions,and field data indicate that a low H_2O-activity carbon-saturated CO_2-rich and a saline aqueous fluid infiltrated the Southern Marginal Zone during exhumation.The formation of anthophyllite after orthopyroxene eslablished a regional retrograde anthophyllite-in isograd and occurred at P-T conditions of- 6 kbar and 610 C,which fixes the minimum mole fraction of II.0 in the CO_2-rich fluid phase at- 0.1.The maximum H_2O mole fraction is hxed by the lower temperature limit(~800℃) for partial melting at ~0.3.C-O-H fluid calculations show that the CO_2-rich fluid had an oxygen fugacity that was 0.6 log10 units higher than that of the fayalite-magnetitequartz buffer and that the CO_2/(CO_2+CH_4) mole ratio of this fluid was 1.The presence of dominantly relatively low density CO_2-rich fluid inclusions in the hydrated granulites indicates that the fluid pressure was less than the lithostatic pressure.This can be explained by strike slip faulting and/or an increase of the rock permeability caused by hydration reactions.     

The Paleoproterozoic carbonate-hosted Pering Zn–Pb deposit, South Africa. II: fluid inclusion, fluid chemistry and stable isotope constraints

The Pering deposit is the prime example of Zn–Pb mineralisation hosted by stromatolitic dolostones of the Neoarchean to Paleoproterozoic Transvaal Supergroup. The hydrothermal deposit centers on subvertical breccia pipes that crosscut stromatolitic dolostones of the Reivilo Formation, the lowermost portion of the Campbellrand Subgroup. Four distinct stages of hydrothermal mineralisation are recognised. Early pyritic rock matrix brecciation is followed by collomorphous sphalerite mineralisation with replacive character, which, in turn, is succeeded by coarse grained open-space-infill of sphalerite, galena, sparry dolomite, and quartz. Together, the latter two stages account for ore-grade Zn–Pb mineralisation. The fourth and final paragenetic stage is characterised by open-space-infill by coarse sparry calcite. The present study documents the results of a detailed geochemical study of the Pering deposit, including fluid inclusion microthermometry, fluid chemistry and stable isotope geochemistry of sulphides (δ³⁴S) and carbonate gangue (δ¹³C and δ¹⁸O). Microthermometric fluid inclusion studies carried out on a series of coarsely grained crystalline quartz and sphalerite samples of the latter, open-space-infill stage of the main mineralisation event reveal the presence of three major fluid types: (1) a halite–saturated aqueous fluid H₂O–NaCl–CaCl₂ (>33 wt% NaCl equivalent) brine, (2) low-salinity meteoric fluid (<7 wt% NaCl) and (3) a carbonic CH₄–CO₂–HS⁻ fluid that may be derived from organic material present within the host dolostone. Mixing of these fluids have given rise to variable mixtures (H₂O–CaCl₂–NaCl ±(CH₄–CO₂–HS⁻), 2 to 25 wt% NaCl+CaCl₂). Heterogeneous trapping of the aqueous and carbonic fluids occurred under conditions of immiscibility. Fluid temperature and pressure conditions during mineralisation are determined to be 200–210°C and 1.1–1.4 kbar, corresponding to a depth of mineralisation of 4.1–5.2 km. Chemical analyses of the brine inclusions show them to be dominated by Na and Cl with lesser amounts of Ca, K and SO₄. Fluid ratios of Cl/Br indicate that they originated as halite saturated seawater brines that mixed with lower salinity fluids. Analyses of individual brine inclusions document high concentrations of Zn and Pb (∼1,500 and ∼200 ppm respectively) and identify the brine as responsible for the introduction of base metals. Stable isotope data were acquired for host rock and hydrothermal carbonates (dolomite, calcite) and sulphides (pyrite, sphalerite, galena and chalcopyrite). The ore-forming sulphides show a trend to ³⁴S enrichment from pyrite nodules in the pyritic rock matrix breccia (δ³⁴S = −9.9 to +3.7‰) to paragenetically late chalcopyrite of the main mineralisation event (δ³⁴S = +30.0‰). The observed trend is attributed to Rayleigh fractionation during the complete reduction of sulphate in a restricted reservoir by thermochemical sulphate reduction, and incremental precipitation of the generated sulphide. The initial sulphate reservoir is expected to have had an isotopic signature around 0‰, and may well represent magmatic sulphur, oxidised and leached by the metal-bearing brine. The δ¹⁸O values of successive generations of dolomite, from host dolostone to paragenetically late saddle dolomite follow a consistent trend that yields convincing evidence for extensive water rock interaction at variable fluid–rock ratios. Values of δ¹³C remain virtually unchanged and similar to the host dolostone, thus suggesting insignificant influx of CO₂ during the early and main stages of mineralisation. On the other hand, δ¹³C and δ¹⁸O of post-ore calcite define two distinct clusters that may be attributed to changes in the relative abundance in CH₄ and CO₂ during waning stages of hydrothermal fluid flow.     

Vein graphite deposits: geological settings,origin, and economic significance

Graphite deposits result from the metamorphism of sedimentary rocks rich in carbonaceous matter or from precipitation from carbon-bearing fluids (or melts). The latter process forms vein deposits which are structurally controlled and usually occur in granulites or igneous rocks. The origin of carbon, the mechanisms of transport, and the factors controlling graphite deposition are discussed in relation to their geological settings. Carbon in granulite-hosted graphite veins derives from sublithospheric sources or from decarbonation reactions of carbonate-bearing lithologies, and it is transported mainly in CO₂-rich fluids from which it can precipitate. Graphite precipitation can occur by cooling, water removal by retrograde hydration reactions, or reduction when the CO₂-rich fluid passes through relatively low-fO₂ rocks. In igneous settings, carbon is derived from assimilation of crustal materials rich in organic matter, which causes immiscibility and the formation of carbon-rich fluids or melts. Carbon in these igneous-hosted deposits is transported as CO₂ and/or CH₄ and eventually precipitates as graphite by cooling and/or by hydration reactions affecting the host rock. Independently of the geological setting, vein graphite is characterized by its high purity and crystallinity, which are required for applications in advanced technologies. In addition, recent discovery of highly crystalline graphite precipitation from carbon-bearing fluids at moderate temperatures in vein deposits might provide an alternative method for the manufacture of synthetic graphite suitable for these new applications.     

Thermodynamic modelling of C–O–H fluids

H₂O, CO₂, CH₄, CO, H₂ and O₂ are the most important species in crustal fluids. The composition of these C–O–H fluids can be calculated if the pressure, temperature, carbon activity, and either the oxygen fugacity or the atomic H/O ratio of the fluid is known. The calculation methods are discussed and calculation results are illustrated with isobaric T–X_i, P–T, and isobaric–isothermal ternary C–O–H diagrams. Fluid inclusion compositions, in particular, the X_CO2/(X_CO2+X_CH4) ratio, can be used for C–O–H model calculations. However, care should be taken about possible post-entrapment changes, which may have modified the chemical composition of the fluid inclusion.     

Thermodynamic modelling of a cooling C–O–H fluid–graphite system: implications for hydrothermal graphite precipitation

Carbon-saturated crustal fluids in the C–O–H system comprise H₂O, CO₂ and CH₄ as the most important fluid species. Graphite precipitation from a cooling C–O–H is discussed for two different systems, namely for a fluid–rock system in which no transfer of atomic oxygen and hydrogen between the fluid and the rock is possible (closed fluid system), and for an open fluid system. Thermodynamic model calculations show that the graphite-forming reactions and the graphite precipitation potential are different for these two systems. Furthermore, the calculations demonstrate that for both systems, the following factors play a role in determining the graphite precipitation potential, i.e. (1) the redox state of the fluid, (2) the initial pressure and temperature conditions and (3) whether cooling is combined with decompression. Open and closed fluid system graphite precipitation can be distinguished from each other using fluid inclusion and stable carbon isotope studies. The results of this study provide insight in the formation of hydrothermal graphite deposits.     

The graphite deposit at Borrowdale (UK): A catastrophic mineralizing event associated with Ordovician magmatism

The volcanic-hosted graphite deposit at Borrowdale in Cumbria, UK, was formed through precipitation from C-O-H fluids. The δ¹³C data indicate that carbon was incorporated into the mineralizing fluids by assimilation of carbonaceous metapelites of the Skiddaw Group by andesite magmas of the Borrowdale Volcanic Group. The graphite mineralization occurred as the fluids migrated upwards through normal conjugate fractures forming the main subvertical pipe-like bodies. The mineralizing fluids evolved from CO₂-CH₄-H₂O mixtures (XCO₂ = 0.6-0.8) to CH₄-H₂O mixtures. Coevally with graphite deposition, the andesite and dioritic wall rocks adjacent to the veins were intensely hydrothermally altered to a propylitic assemblage. The initial graphite precipitation was probably triggered by the earliest hydration reactions in the volcanic host rocks. During the main mineralization stage, graphite precipitated along the pipe-like bodies due to CO₂ → C + O₂. This agrees with the isotopic data which indicate that the first graphite morphologies crystallizing from the fluid (cryptocrystalline aggregates) are isotopically lighter than those crystallizing later (flakes). Late chlorite-graphite veins were formed from CH₄-enriched fluids following the reaction CH₄ + O₂ → C + 2H₂O, producing the successive precipitation of isotopically lighter graphite morphologies. Thus, as mineralization proceeded, water-generating reactions were involved in graphite precipitation, further favouring the propylitic alteration. The structural features of the pipe-like mineralized bodies as well as the isotopic homogeneity of graphite suggest that the mineralization occurred in a very short period of time.