A new view on gold speciation in sulfur-bearing hydrothermal fluids from in situ X-ray absorption spectroscopy and quantum-chemical modeling

Despite the common belief that Au^I complexes with hydrogen sulfide ligands (H₂S/HS⁻) are the major carriers of gold in natural hydrothermal fluids, their identity, structure and stability are still subjects of debate. Here we present the first in situ measurement, using X-ray absorption fine structure (XAFS) spectroscopy, of the stability and structure of aqueous Au^I–S complexes at temperatures and pressures (T–P) typical of natural sulfur-rich ore-forming fluids. The solubility of native gold and the local atomic structure around the dissolved metal in S–NaOH–Na₂SO₄–H₂SO₄ aqueous solutions were characterized at temperatures 200–450 °C and pressures 300–600 bar using an X-ray cell that allows simultaneous measurement of the absolute concentration of the absorbing atom (Au) and its local atomic environment in the fluid phase. Structural and solubility data obtained from XAFS spectra, combined with quantum-chemical calculations of species geometries, show that gold bis(hydrogensulfide) Au(HS)₂⁻ is the dominant Au species in neutral-to-basic solutions (5.5  pH  8.5; H₂O–S–NaOH) over a wide range of sulfur concentrations (0.2 < ΣS < 3.6 mol/kg), in agreement with previous solubility studies. Our results provide the first direct determination of this species structure, in which two sulfur atoms are in a linear geometry around Au^I at an average distance of 2.29 ± 0.01 Å. At acidic conditions (1.5  pH  5.0; H₂O–S–Na₂SO₄–H₂SO₄), the Au atomic environment determined by XAFS is similar to that in neutral solutions. These findings, together with measured high Au solubilities, are inconsistent with the predominance of the gold hydrogensulfide Au(HS)⁰ complex suggested by recent solubility studies. Our spectroscopic data and quantum-chemical calculations imply the formation of species composed of linear S–Au–S moieties, like the neutral [H₂S–Au–SH] complex. This species may account for the elevated Au solubilities in acidic fluids and vapors with H₂S concentrations higher than 0.1–0.2 mol/kg. However, because of the complex sulfur speciation in acidic solutions that involves sulfite, thiosulfate and polysulfide species, the formation of Au^I complexes with these ligands (e.g., AuHS(SO₂)⁰, Au(HS₂O₃)₂⁻, Au(HS_n)₂⁻) cannot be ruled out. The existence of such species may significantly enhance Au transport by high T–P acidic ore-forming fluids and vapors, responsible for the formation of a major part of the gold resources on Earth.     

A semi-empirical velocity-porosity-clay model for petrophysical interpretation of P- and S-velocities

We design a velocity–porosity model for sand-shale environments with the emphasis on its application to petrophysical interpretation of compressional and shear velocities. In order to achieve this objective, we extend the velocity–porosity model proposed by Krief et al., to account for the effect of clay content in sandstones, using the published laboratory experiments on rocks and well log data in a wide range of porosities and clay contents. The model of Krief et al. works well for clean compacted rocks. It assumes that compressional and shear velocities in a porous fluid-saturated rock obey Gassmann formulae with the Biot compliance coefficient. In order to use this model for clay-rich rocks, we assume that the bulk and shear moduli of the grain material, and the dependence of the compliance on porosity, are functions of the clay content. Statistical analysis of published laboratory data shows that the moduli of the matrix grain material are best defined by low Hashin–Shtrikman bounds. The parameters of the model include the bulk and shear moduli of the sand and clay mineral components as well as coefficients which define the dependence of the bulk and shear compliance on porosity and clay content. The constants of the model are determined by a multivariate non-linear regression fit for P- and S-velocities as functions of porosity and clay content using the data acquired in the area of interest. In order to demonstrate the potential application of the proposed model to petrophysical interpretation, we design an inversion procedure, which allows us to estimate porosity, saturation and/or clay content from compressional and shear velocities. Testing of the model on laboratory data and a set of well logs from Carnarvon Basin, Australia, shows good agreement between predictions and measurements. This simple velocity-porosity-clay semi-empirical model could be used for more reliable petrophysical interpretation of compressional and shear velocities obtained from well logs or surface seismic data.     

Geophysical flows with anisotropic turbulence and dispersive waves: flows with a β-effect

Geostrophic turbulence is a key paradigm in the current understanding of the large-scale planetary circulations. It implies that a flow is turbulent, rotating, stably stratified, and in near-geostrophic balance. When a small-scale forcing is present, geostrophic turbulence features an inverse energy cascade. When the meridional variation of the Coriolis parameter (or a β-effect) is included, the horizontal flow symmetry breaks down giving rise to the emergence of jet flows. The presence of a large-scale drag ensures that the flow attains a steady state. Dependent on the governing parameters, four steady-state flow regimes are possible, two of which are considered in this study. In one of these regimes, a flow is dominated by the drag while in the other one, the recently discovered regime of zonostrophic turbulence, a flow becomes strongly anisotropic and features slowly evolving systems of alternating zonal jets. Zonostrophic turbulence is distinguished by anisotropic inverse energy cascade and emergence of a new class of nonlinear waves known as zonons. In addition, meridional scalar diffusion is strongly modified in this regime. This paper provides an overview of various regimes of turbulence with a β-effect, elaborates main characteristics of friction-dominated and zonostrophic turbulence, elucidates the physical nature of the zonons, discusses the meridional diffusion processes in different regimes, and relates these results to oceanic observations.     

Hydroclimatic change disparity of Peruvian Pacific drainage catchments

Peruvian Pacific drainage catchments only benefit from 2% of the total national available freshwater while they concentrate almost 50% of the population of the country. This situation is likely to lead a severe water scarcity and also constitutes an obstacle to economic development. Catchment runoff fluctuations in response to climate variability and/or human activities can be reflected in extreme events, representing a serious concern (like floods, erosion, droughts) in the study area. To document this crucial issue for Peru, we present here an insightful analysis of the water quantity resource variability of this region, exploring the links between this variability and climate and/or anthropogenic pressure. We first present a detailed analysis of the hydroclimatologic variability at annual timescale and at basin scale over the 1970–2008 period. In addition to corroborating the influence of extreme El Niño events over precipitation and runoff in northern catchments, a mean warming of 0.2 °C per decade over all catchments was found. Also, higher values of temperature and potential and actual evapotranspiration were found over northern latitudes. We chose to apply the Budyko-Zhang framework that characterizes the water cycle as a function of climate only, allowing the identification of catchments with significant climatic and anthropogenic influence on water balance. The Budyko-Zhang methodology revealed that 11 out of 26 initial catchments are characterized by low water balance disparity related to minor climatic and anthropogenic influence. These 11 catchments were suitable for identifying catchments with contrasting change in their hydroclimatic behavior using the Budyko trajectories. Our analysis further reveals that six hydrological catchment responses can be characterized by high sensitivity to climate variability and land use changes.     

Non-isothermal scavenging of highly soluble gaseous pollutants by rain in the atmosphere with non-uniform vertical concentration and temperature distributions

We suggest a non-isothermal one-dimensional model of precipitation scavenging of highly soluble gaseous pollutants in inhomogeneous atmosphere. When gradients of soluble trace gases’ concentrations and temperature in the atmosphere are small, scavenging of gaseous pollutants is governed by two linear wave equations that describe propagation of a scavenging and temperature waves in one direction. If wash-down front velocity is much larger than the velocity of the temperature front, scavenging is determined by propagating scavenging front in the atmosphere with inhomogeneous temperature distribution. We solved the derived equation by the method of characteristics and determined scavenging coefficient and the rates of precipitation scavenging for wet removal of sulfur dioxide using measured initial distributions of trace gases and temperature in the atmosphere. It is shown that in the case of exponential initial distribution of soluble trace gases and linear temperature distribution in the atmosphere, scavenging coefficient in the region between the ground and the position of a scavenging front is proportional to rainfall rate, solubility parameter in the under-cloud region, adjacent to a bottom of a cloud and to the growth constant in the formula for the initial profile of a soluble trace gas in the atmosphere. The derived formula yields the same value of scavenging coefficient for sulfur dioxide scavenging by rain as field estimates presented by McMahon and Denison (Atmos Environ 13:571–585, 1979). It is demonstrated that in the case when the altitude variation of temperature in the atmosphere is determined by the environmental lapse rate, scavenging coefficient increases with height in the region between the scavenging front and the ground. In the case when altitude temperature variation in the atmosphere is determined by temperature inversion, scavenging coefficient decreases with height in a region between the scavenging front and the ground. Theoretical predictions of the value of the scavenging coefficient for sulfur dioxide washout by rain and of the dependence of the magnitude of the scavenging coefficient on rain intensity are in good agreements with the atmospheric measurements of Martin (Atmos Environ 18:1955–1961, 1984).     

An Investigation of the Reliability of HF Acid Mixtures in the Bomb Digestion of Silicate Rocks for the Determination of Trace Elements by ICP‐MS

The influence of the mixtures HF‐HNO₃ and HF‐NH₄F‐HNO₃ in bomb digestion for trace element determination from different rock types was studied using ICP‐MS. It is shown that the HF concentration, not the ratio of reagents in the decomposing mixture, controls the digestion process of a rock. Data for Zr in the granite G‐2 as a function of HF concentration gave the same results as reaction mixtures of various compositions. A complete digestion in 50‐mg sample bombs was achieved by 1.0 ml of HF alone, or with a mixture of other acids at a HF concentration of at least 35% m/m at 196 °C over 18 h. The results of the analysis of basalts BCR‐1, BIR‐1, mica schist SDC‐1, shale SBC‐1, granites G‐2, SG‐1A, garnet‐biotite plagiogneiss GBPg‐1, rhyolite RGM‐1, granodiorite GSP‐1, trachyandesite MTA‐1 and rhyolite MRh‐1 are given and compared against available data. The reproducibility of the element determinations by ICP‐MS and XRF as an independent non‐destructive analysis for a quality check in the range of concentrations typical for routine rock samples is given.     

Oxygen isotope biogeochemistry of pore water sulfate in the deep biosphere: Dominance of isotope exchange reactions with ambient water during microbial sulfate reduction (ODP Site 1130)

Microbially mediated sulfate reduction affects the isotopic composition of dissolved and solid sulfur species in marine sediments. Experiments and field data show that the composition is also modified in the presence of sulfate-reducing microorganisms. This has been attributed either to a kinetic isotope effect during the reduction of sulfate to sulfite, cell-internal exchange reactions between enzymatically-activated sulfate (APS), and/or sulfite with cytoplasmic water. The isotopic fingerprint of these processes may be further modified by the cell-external reoxidation of sulfide to elemental sulfur, and the subsequent disproportionation to sulfide and sulfate or by the oxidation of sulfite to sulfate. Here we report values from interstitial water samples of ODP Leg 182 (Site 1130) and provide the mathematical framework to describe the oxygen isotope fractionation of sulfate during microbial sulfate reduction. We show that a purely kinetic model is unable to explain our data, and that the data are well explained by a model using oxygen isotope exchange reactions. We propose that the oxygen isotope exchange occurs between APS and cytoplasmic water, and/or between sulfite and adenosine monophosphate (AMP) during APS formation. Model calculations show that cell external reoxidation of reduced sulfur species would require up to 3000 mol/m³ of an oxidant at ODP Site 1130, which is incompatible with the sediment geochemical data. In addition, we show that the volumetric fluxes required to explain the observed data are on average 14 times higher than the volumetric sulfate reduction rates (SRR) obtained from inverse modeling of the porewater data. The ratio between the gross sulfate flux into the microbes and the net sulfate flux through the microbes is depth invariant, and independent of sulfide concentrations. This suggests that both fluxes are controlled by cell density and that cell-specific sulfate reduction rates remain constant with depth.     

Ecosystem dynamics of the Pacific-influenced Northern Bering and Chukchi Seas in the Amerasian Arctic

The shallow continental shelves and slope of the Amerasian Arctic are strongly influenced by nutrient-rich Pacific waters advected over the shelves from the northern Bering Sea into the Arctic Ocean. These high-latitude shelf systems are highly productive both as the ice melts and during the open-water period. The duration and extent of seasonal sea ice, seawater temperature and water mass structure are critical controls on water column production, organic carbon cycling and pelagic–benthic coupling. Short food chains and shallow depths are characteristic of high productivity areas in this region, so changes in lower trophic levels can impact higher trophic organisms rapidly, including pelagic- and benthic-feeding marine mammals and seabirds. Subsistence harvesting of many of these animals is locally important for human consumption. The vulnerability of the ecosystem to environmental change is thought to be high, particularly as sea ice extent declines and seawater warms. In this review, we focus on ecosystem dynamics in the northern Bering and Chukchi Seas, with a more limited discussion of the adjoining Pacific-influenced eastern section of the East Siberian Sea and the western section of the Beaufort Sea. Both primary and secondary production are enhanced in specific regions that we discuss here, with the northern Bering and Chukchi Seas sustaining some of the highest water column production and benthic faunal soft-bottom biomass in the world ocean. In addition, these organic carbon-rich Pacific waters are periodically advected into low productivity regions of the nearshore northern Bering, Chukchi and Beaufort Seas off Alaska and sometimes into the East Siberian Sea, all of which have lower productivity on an annual basis. Thus, these near shore areas are intimately tied to nutrients and advected particulate organic carbon from the Pacific influenced Bering Shelf-Anadyr water. Given the short food chains and dependence of many apex predators on sea ice, recent reductions in sea ice in the Pacific-influenced sector of the Arctic have the potential to cause an ecosystem reorganization that may alter this benthic-oriented system to one more dominated by pelagic processes.     

The relationship between intraseasonal tropical variability and ENSO and its modulation at seasonal to decadal timescales

The intraseasonal tropical variability (ITV) patterns in the tropical troposphere are documented using double space-time Fourier analysis. Madden and Julian oscillations (MJO) as well as equatorial coupled waves (Kelvin and Rossby) are investigated based on the NCEP/NCAR Reanalysis data for the 1977–2006 period and the outputs of an intermediate ocean-atmosphere coupled model named LODCA-OTCM. A strong seasonal dependence of the ITV/ENSO relationship is evidenced. The leading relationship for equatorial Rossby waves (with the correlation of the same order than for the MJO) is documented; namely, it is shown that intensification of Rossby waves in the central Pacific during boreal summer precedes by half a year the peak of El Niño. The fact that MJO activity in spring-summer is associated to the strength of subsequent El Niño is confirmed. It is shown that LODCA-QTCM is capable of simulating the convectively coupled equatorial waves in outgoing long wave radiation and zonal wind at 850 hPa fields with skill comparable to other Coupled General Circulation Models. The ITV/ENSO relationship is modulated at low frequency. In particular the periods of low ENSO amplitude are associated with weaker MJO activity and a cancellation of MJO at the ENSO development phase. In opposition, during the decaying phase, MJO signal is strong. The periods of strong ENSO activity are associated with a marked coupling between MJO, Kelvin and equatorially Rossby waves and ENSO; the precursor signal of MJO (Rossby waves) in the western (central) Pacific is obvious. The results provide material for the observed change in ENSO characteristics in recent years and question whether the characteristics of the ITV/ENSO relationship may be sensitive to the observed warming in the central tropical Pacific.     

The 11-year solar cycle, the Sun's rotation, and the middle stratosphere in winter. Part II: Response of planetary waves

The effect of the 11-year solar cycle on the response of planetary wavenumbers 1 and 2 at 10 and 30 hPa in winter to solar activity oscillations on the time scale of the Sun's rotation (27.2 day) is discussed in terms of statistical spectral analysis. The three oscillations studied are the 27.2 d (period of the Sun's rotation), 25.3 d (periodicity caused by modulation of the 27.2 d stratospheric response by annual atmospheric variation), and 54.4 d (doubled period of the solar rotation). A significant effect of the 11-year solar cycle is found for the 54.4 d periodicity in planetary wavenumber 1, and for the 27.2 and 25.3 d periodicities in planetary wavenumber 2. The effect of the 11-year solar cycle is expressed in the evident differences between the amplitudes of responses of planetary waves at maximum and minimum of the solar cycle: the amplitudes are much larger at high than at low solar activity. The 11-year modulation of planetary wave activity is most pronounced at mid-latitudes, mainly at 40–60°N, where the observed variability of planetary waves is large. The results obtained are in good agreement with results of the recent modeling study by Shindell et al. (Science 284 (1999) 305).