Gold partitioning in melt-vapor-brine systems

We used laser-ablation inductively coupled plasma mass spectrometry to measure the solubility of gold in synthetic sulfur-free vapor and brine fluid inclusions in a vapor + brine + haplogranite + magnetite + gold metal assemblage. Experiments were conducted at 800°C, oxygen fugacity buffered at Ni-NiO (NNO), and pressures ranging from 110 to 145 MPa. The wt% NaCl eq. of vapor increases from 2.3 to 19 and that of brine decreases from 57 to 35 with increasing pressure. The composition of the vapors and brines are dominated by NaCl + KCl + FeCl₂ + H₂O. Gold concentrations in vapor and brine decrease from 36 to 5 and 50 to 28 μg/g, respectively, and the calculated vapor:brine partition coefficients for gold decrease from 0.72 to 0.17 as pressure decreases from 145 to 110 MPa. These data are consistent with the thermodynamic boundary condition that the concentration of gold in the vapor and brine must approach a common value as the critical pressure is approached along the 800°C isotherm in the NaCl-KCl-FeCl₂-HCl-H₂O system.We use the equilibrium constant for gold dissolution as AuOH⁰, extrapolated from lower temperature and overlapping pressure range, to calculate expected concentrations of AuOH⁰ in our experimental vapors. These calculations suggest that a significant quantity of gold in our experimental vapors is present as a non-hydroxide species. Possible chloridogold(I) species are hypothesized based on the positively correlated gold and chloride concentrations in our experimental vapors. The absolute concentration of gold in our synthetic vapor, brine, and melt and calculated mass partition coefficients for gold between these physicochemically distinct magmatic phases suggests that gold solubility in aqueous fluids is a function of aqueous phase salinity, specifically total chloride concentration, at magmatic conditions. However, though we highlight here the effect of salinity, the combination of our data with data sets from lower temperatures evinces a significant decrease in gold solubility as temperature drops from 800°C to 600°C. This decrease in solubility has implications for gold deposition from ascending magmatic fluids.     

Late Dinantian palaeokarst of England and Wales: implications for exposure surface development

Palaeokarst is an important feature of late Dinantian exposure surfaces. Soil-filled depressions are widely developed. These are comparable to modern day solution dolines and were probably interspersed by areas of relatively bare limestone pavement. The palaeokarst primarily exhibits a smooth, mamillated to potholed surface form, consistent with its formation beneath a soil cover. Areas between the depressions have been extensively stylolitised and would likely have originally been characterized by small-scale fretted and sculpted karren forms typical of subaerial karstification. Palaeokarst pits making up the depressions are thought to have been initiated through stem-flow drainage from trees. Rain water, intercepted by the crown of the tree, was concentrated at specific sites on the emergent surface and dissolution beneath the trunk produced cylindrical pits that propagated vertically downwards. Trees responsible for concentrating drainage may also have enhanced the acidic nature of the rain water through leaching of organic acids from foliar and woody tissues. Downward propagation of the pits was limited to the uppermost 1–2 m and enlargement primarily occurred through lateral amalgamation of adjacent pits. Once initiated, continued development of the depressions would have been self perpetuating; the preferential accumulation of volcanic ash and organic matter enhancing water retention and encouraging further vegetation growth. In contrast, intervening areas would have been characterized by slow vertical denudation only. Karstification likely took of the order of a few hundred years in the case of potholed palaeokarstic surfaces formed solely by stem-flow drainage, to a few tens of thousands of years where the palaeokarst is more mature.     

Micro- and nano-textural evidence of Ti(–Ca–Fe) mobility during fluid–rock interactions in carbonaceous lawsonite-bearing rocks from New Zealand

Understanding the mobility of chemical elements during fluid–rock interactions is critical to assess the geochemical evolution of a rock undergoing burial and metamorphism and, more generally, to constrain the geochemical budget of the subduction factory. In particular, determining the behavior and mobility of Ti in aqueous fluids constitutes a great challenge that is still under scrutiny. Here, we study plant fossils preserved in blueschist metasedimentary rocks from the Marybank Formation (New Zealand). Using scanning and transmission electron microscopies (SEM and TEM), we show that the carbonaceous material (CM) composing the fossils contains abundant nano-inclusions of Ti- and Fe-oxides. These nanocrystals are mainly anatase, rutile, and Fe–Ti oxides. The mineral composition observed within the fossils is significantly different from that detected in the surrounding rock matrix. We propose that Ti and Fe might have been mobilized by the alteration of a detrital Ti–Fe-rich protolith during an early diagenetic event under acidic and reducing conditions. Aqueous fluids rich in organic ligands released by the degradation of organic matter may have been involved. Moreover, using mass balance and petrological observations, we show that the contrasted mineralogy between the rock matrix and the fossil CM might be the consequence of the chemical isolation of fossil CM during the prograde path of the rock. Such an isolation results from the early formation of quartz and Fe-rich phyllosilicate layers enclosing the fossil as characterized by SEM and TEM investigations. Overall, this study shows that investigating minerals associated with CM down to the nanometer scale in metamorphic rocks can provide a precious record of early prograde geochemical conditions.     

Vulnerability of population and transportation infrastructure at the east bank of Delaware Bay due to coastal flooding in sea-level rise conditions

Catastrophic flooding associated with sea-level rise and change of hurricane patterns has put the northeastern coastal regions of the United States at a greater risk. In this paper, we predict coastal flooding at the east bank of Delaware Bay and analyze the resulting impact on residents and transportation infrastructure. The three-dimensional coastal ocean model FVCOM coupled with a two-dimensional shallow water model is used to simulate hydrodynamic flooding from coastal ocean water with fine-resolution meshes, and a topography-based hydrologic method is applied to estimate inland flooding due to precipitation. The entire flooded areas with a range of storm intensity (i.e., no storm, 10-, and 50-year storm) and sea-level rise (i.e., current, 10-, and 50-year sea level) are thus determined. The populations in the study region in 10 and 50 years are predicted using an economic-demographic model. With the aid of ArcGIS, detailed analysis of affected population and transportation systems including highway networks, railroads, and bridges is presented for all of the flood scenarios. It is concluded that sea-level rise will lead to a substantial increase in vulnerability of residents and transportation infrastructure to storm floods, and such a flood tends to affect more population in Cape May County but more transportation facilities in Cumberland County, New Jersey.     

The end of the Ediacara biota: Extinction,biotic replacement,or Cheshire Cat?

The Ediacaran–Cambrian transition signals a drastic change in both diversity and ecosystem construction. The Ediacara biota (consisting of various metazoan stem lineages in addition to extinct eukaryotic clades) disappears, and is replaced by more familiar Cambrian and Paleozoic metazoan groups. Although metazoans are present in the Ediacaran, their ecological contribution is dwarfed by Ediacaran-type clades of uncertain phylogenetic affinities, while Ediacaran-type morphologies are virtually non-existent in younger assemblages. Three alternative hypotheses have been advanced to explain this dramatic change at, or near, the Ediacaran–Cambrian boundary: 1) mass extinction of most Ediacaran forms; 2) biotic replacement, with early Cambrian organisms eliminating Ediacaran forms; and 3) a Cheshire Cat model, with Ediacaran forms gradually disappearing from the fossil record (but not necessarily going extinct) as a result of the elimination of unique preservational settings, primarily microbial matgrounds, that dominated the Ediacaran. To evaluate these proposed explanations for the biotic changes observed at the Ediacaran–Cambrian transition, environmental drivers leading to global mass extinction are compared to biological factors such as predation and ecosystem engineering. We explore temporal and biogeographic distributions of Ediacaran taxa combined with evaluations of functional guild ranges throughout the Ediacaran. The paucity of temporally-resolved localities with diverse Ediacaran assemblages, combined with difficulties associated with differences in taphonomic regimes before, during, and after the transition hinders this evaluation. Nonetheless, the demonstration of geographic and niche range changes offers a novel means of assessing the downfall of Ediacara-type taxa at the hands of emerging metazoans, which we hypothesize to be most likely due to the indirect ecological impact metazoans had upon the Ediacarans. Ultimately, the combination of studies on ecosystem construction, biostratigraphy, and biogeography showcases the magnitude of the transition at the Ediacaran–Cambrian boundary.     

Numerical modelling of the application of capillary barrier systems for prevention of rainfall-induced slope instability

Acta Geotechnica - The most common cause of slope instability is intense or sustained rainfall, which may induce reduction in soil suction, and thus, shear strength. Capillary barrier systems...     

In situ measurement of Re-Os isotopes in mantle sulfides by laser ablation multicollector-inductively coupled plasma mass spectrometry: analytical methods and preliminary results

A method has been developed for the in situ determination of Re-Os isotopes in single grains of sulfides in mantle-derived peridotites using a laser ablation microprobe attached to a multicollector-induced coupled plasma mass spectrometer (MC-ICPMS). High-precision Os isotope analysis by MC-ICPMS is demonstrated by the measurement of interlaboratory Os standards. Evaluation of mass bias correction procedures shows that the exponential law provides the best fit to the Os isotope data and that the ratio of the mass fractionation coefficients for Re and Os remains constant for the range of typical instrument operating conditions. This relationship enables the accurate and precise correction of the isobaric interference of ¹⁸⁷Re on ¹⁸⁷Os for ¹⁸⁷Re/¹⁸⁸Os values up to 1.6.Results are presented for single sulfide inclusions in olivine macrocryts from kimberlites in the Siberian and Slave Cratons, and sulfides enclosed in silicates and interstitial to silicates in peridotite xenoliths from the Slave Craton and Massif Central, France. Enclosed sulfides larger than 50 μm in diameter and with Os contents ≥40 ppm give ¹⁸⁷Os/¹⁸⁸Os ratios with a precision of 0.1% (2 SE), which is equivalent to N-TIMS whole-rock data. Interstitial sulfides typically have lower Os (10 to 30 ppm) and give analyses with lower precision (∼1 to 2%) but still provide valuable information on the movement of Os within the lithosphere. The sulfide inclusions in silicates preserve significantly less radiogenic Os isotopic compositions than interstitial sulfides and accordingly produce significantly older and more realistic Re-Os age information. Whole-rock Os isotope compositions reflect the proportions of different generations of enclosed and interstitial sulfides; this calls into question the significance of many published “depletion ages.”     

Generation of mid-ocean ridge basalts at pressures from 1 to 7 GPa

We propose a model for the generation of average MORBs based on phase relations in the CaO-MgO-Al₂O₃-SiO₂-CO₂ system at pressures from 3 to 7 GPa and in the CaO-MgO-Al₂O₃-SiO₂-Na₂O-FeO (CMASNF) system at pressures from ∼0.9 to 1.5 GPa. The MELT seismic tomography (Forsyth et al., 2000) across the East Pacific Rise shows the largest amount of melt centered at ∼30-km depth and lesser amounts at greater depths. An average mantle adiabat with a model-system potential temperature (T_p) of 1310°C is used that is consistent with this result. In the mantle, additional minor components would lower solidus temperatures ∼50°C, which would lower T_p of the adiabat for average MORBs to ∼1260°C. The model involves generation of carbonatitic melts and melts that are transitional between carbonatite and kimberlite at very small melt fractions (<0.2%) in the low-velocity zone at pressures of ∼2.6 to 7 GPa in the CMAS-CO₂ system, roughly the pressure range of the PREM low-velocity zone. These small-volume, low-viscosity melts are mixed with much larger volumes of basaltic melt generated at the plagioclase-spinel lherzolite transition in the pressure range of ∼0.9 to 1.5 GPa.In this model, solidus phase relations in the pressure range of the plagioclase-spinel lherzolite transition strongly, but not totally, control the major-element characteristics of MORBs. Although the plagioclase-spinel lherzolite transition suppresses isentropic decompression melting in the CMAS system, this effect does not occur in the topologically different and petrologically more realistic CMASNF system. On the basis of the absence of plagioclase from most abyssal peridotites, which are the presumed residues of MORB generation, we calculate melt productivity during polybaric fractional melting in the plagioclase-spinel lherzolite transition interval at exhaustion of plagioclase in the residue. In the CMASN system, these calculations indicate that the total melt productivity is ∼24%, which is adequate to produce the oceanic crust. The residual mineral proportions from this calculation closely match those of average abyssal peridotites.Melts generated in the plagioclase-spinel lherzolite transition are compositionally distinct from all MORB glasses, but do not have a significant fractional crystallization trend controlled by olivine alone. They reach the composition field of erupted MORBs mainly by crystallization of both plagioclase and olivine, with initial crystallization of either one of these phases rapidly joined by the other. This is consistent with phenocryst assemblages and experimental studies of the most primitive MORBs, which do not show an olivine-controlled fractionation trend. The model is most robust for the eastern Pacific, where an adiabat with a T_p of ∼1260°C is supported by the MELT seismic data and where the global inverse correlation of (FeO)₈ with (Na₂O)₈ is weak. Average MORBs worldwide also are well modeled. A heterogeneous mantle consisting of peridotite of varying degrees of major-element depletion combined with phase-equilibrium controls in the plagioclase-spinel lherzolite transition interval would produce the form of the global correlations at a constant T_p, which suggests a modest range of T_p along ridges. Phase-composition data for the CMASNF system are presently not adequate for quantitative calculation of (FeO)₈-(Na₂O)₈-(CaO/Al₂O₃)₈ systematics in terms of this model. The near absence of basalts in the central portion of the Gakkel Ridge suggests a lower bound for T_p along ridges of ∼1240°C, a potential temperature just low enough to miss the solidus for basalt production at ∼0.9 GPa. An upper bound for T_p is poorly constrained, but the complete absence of picritic glasses in Iceland and the global ridge system suggests an upper bound of ∼1400°C. In contrast to some previous models for MORB generation that emphasize large potential temperature variations in a relatively homogeneous peridotitic mantle, our model emphasizes modest potential temperature variations in a peridotitic mantle that shows varying degrees of heterogeneity. Calculations indicate that melt productivity changes from 0 to 24% for a change in T_p from 1240 to 1260°C, effectively producing a rapid increase to full crustal thickness or decrease to none as ridges appear and disappear.     

Origin of the Oceanic Lithosphere

In a global examination of mid-ocean ridge basalt (MORB) glasscompositions, we find that Na₈–Fe₈–depth variationsdo not support modeling of MORBs as aggregates of melt compositionsgenerated over a large range of temperature and pressure. However,the Na₈–Fe₈ variations are consistent with the compositionalsystematics of solidus melts in the plagioclase–spinellherzolite transition in the CaO–MgO–Al₂O₃–SiO₂–Na₂O–FeO(CMASNF) system. For natural compositions, the P–T rangefor melt extraction is estimated to be 1·2–1·5GPa and 1250–1280°C. This P–T range is a closematch with the maximum P–T conditions for explosive pressure-releasevaporization of carbonate-bearing melts. It is proposed thatfracturing of the lithosphere induces explosive formation andescape of CO₂ vapor. This provides the vehicle for extractionof MORBs at a relatively uniform T and P. The upper portionof the CO₂-bearing and slightly melted seismic low-velocityzone flows toward the ridge, rises at the ridge axis to lower-lithospheredepths, melts much more extensively during this rise, and releasesMORB melts to the surface driven by explosively escaping CO₂vapor. The residue and overlying crust produced by this meltingthen migrate away from the ridge axis as new oceanic lithosphere.The entire process of oceanic lithosphere creation involvesonly the upper 140 km. When lithospheric stresses shift fractureformation to other localities, escape of CO₂ ceases, the vehiclefor transporting melt to the surface disappears, and ridgesdie. Inverse correlations of Na₈ vs Fe₈ for MORB glasses areexplained by mantle heterogeneity, and positive variations superimposedon the inverse variations are consistent with progressive extractionof melts from short, ascending melting columns. The uniformlylow temperatures of MORB extraction are not consistent withthe existence of hot plumes on or close to ocean ridges. Inthis modeling, the southern Atlantic mantle from Bouvet to about26°N is relatively homogeneous, whereas the Atlantic mantlenorth of about 26°N shows significant long-range heterogeneity.The mantle between the Charlie Gibbs and Jan Mayen fracturezones is strongly enriched in FeO/MgO, perhaps by a trappedfragment of basaltic crust. Iceland is explained as the productof this enrichment, not a hot plume. The East Pacific Rise,Galapagos Ridge, Gorda Ridge, and Juan de Fuca Ridge samplemantle that is heterogeneous over short distances. The mantlebeneath the Red Sea is enriched in FeO/MgO relative to the mantlebeneath the northern Indian Ocean.