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.     

Local coordination of Zn in hydroxy-interlayered minerals and implications for Zn retention in soils

The objective of this study was to determine the local coordination of Zn in hydroxy-interlayered smectite (HIS) as a function of Zn loading and synthesis conditions and to assess the importance of hydroxy-interlayered minerals (HIM) for Zn retention in contaminated soils. Published and newly collected extended X-ray absorption fine structure (EXAFS) spectra of HIS reacted with Zn at molar Zn/hydroxy-Al ratios from 0.013 to 0.087 (corresponding to final Zn contents of 1615-8600 mg/kg Zn) were evaluated by shell fitting. In Zn-HIS, Zn was octahedrally coordinated to oxygen at 2.06-2.08 Å and surrounded by Al atoms at 3.03-3.06 Å in the second-shell. With increasing molar Zn/hydroxy-Al ratio, the coordination number of second-shell Al decreased from 6.6 to 2.1. These results were interpreted as a progressive shift from Zn incorporation in the vacancies of gibbsitic Al-polymers to Zn adsorption to incomplete Al-polymers and finally uptake by cation exchange in the polymer-free interlayer space of HIS with increasing Zn loadings. In a second part, we determined the speciation of Zn in eight contaminated soils (251-1039 mg/kg Zn) with acidic to neutral pH (pH 4.1-6.9) using EXAFS spectroscopy. All soils contained hydroxy-Al interlayered vermiculite (HIV). The analysis of EXAFS spectra by linear combination fitting (LCF) showed that a substantial fraction of total Zn (29-84%) was contained in HIM with high Zn loading. The remaining Zn was adsorbed to organic and inorganic soil components and incorporated into phyllosilicates. In sequential extractions of Zn-HIS spiked into quartz powder and the Zn contaminated soils, Zn was mainly released in the two most resistant fractions, in qualitative agreement with the findings from LCF. Our results suggest that formation of Zn-HIM may strongly retain Zn in pristine and moderately contaminated acidic to neutral soils. Due to their limited sorption capacity, however, HIM do not allow for the accumulation of high levels of Zn in response to continued Zn input into soils.     

Textural Characterization Using Gy’s Heterogeneity Functions

A solid can be regarded as a set of contiguous elementary units. The distribution within the solid of any properties, measurable within each elementary unit, can be characterized using two parameters. These parameters are built using the constitution and distribution heterogeneities of Gy. The former account for the granularity of the elementary units, whereas the latter assess the spatial distribution of the property. A texture which definition involves several properties can be described using a diagram where both parameters work as variables. Potential applications encompass (i) the textural classification of soils, ore, breccia, and concrete and (ii) the monitoring of textural transformation during process like dolomitization, metamorphism, weathering, deformation, or annealing.     

From paleostresses to paleoburial in fold-thrust belts: Preliminary results from calcite twin analysis in the Outer Albanides

This paper presents a new approach to constrain paleoburial and subsequent uplift by folding in fold-thrust belts, combining differential stress estimates from mechanically-induced calcite twins with the assumption that stress in the upper crust is in frictional equilibrium. Calcite twin data were collected from pre-folding veins in late Cretaceous limestones from the Ionian zone in Albania in order to (1) determine Paleogene-Neogene stresses associated with the development of the major vein sets in the frontal anticlines of the Outer Albanides and (2) estimate paleoburial of the Cretaceous reservoir rocks during pre-folding flexural subsidence of the foreland. The first vein set (set I) trends N140 (± 20) and the second set (set II) is oriented N060 (± 20). Calcite twinning analysis from set I veins reveals a pre-folding N030° extension likely related to foreland flexure; a later pre-folding, NE-directed compression (LPS) is identified either from one or from both vein sets in the samples from the Saranda anticline; this NE compression is instead recorded by twinning in set II veins from the Kremenara anticline during late stage fold tightening. This NE compression well agrees with independent microtectonic data, regional transport direction and contemporary stress. The differential stress values related to this NE compression are combined with the hypothesis of crustal frictional stress equilibrium to derive first-order estimates of paleoburial of the Cretaceous limestones just before they were uplifted by folding. The ~ 4 km paleoburial of these limestones estimated in the Saranda anticline is consistent with independent paleoburial estimates from stratigraphy, maturity rank of organic matter, paleotemperature/paleogeothermal gradients from fluid inclusions and predictions of kinematic modelling of the Albanian foreland. Our results therefore place reliable constraints on the amount and rate of vertical uplift of these Cretaceous limestones and yield a promising methodology for better constraining paleoburial and therefore erosion and uplift in fold-thrust belts.     

Modeling of a semi-real injection test in sand

This article presents a model of flow and transport with filtration in porous media which is used to analyze large-scale grouting tests. A program based on the finite element method is developed to solve the model equations; a particular attention is paid to inherent issues of transport problems. The analysis of these tests aims at providing insights on the propagation patterns associated to the injection of cement-based grouts in sand. To apprehend particular features that characterize field injections, the experiments are performed by using a tube-a-manchette and a patented grout. Finally, the role of filtration during the tests is discussed.     

Climate response to the physiological impact of carbon dioxide on plants in the Met Office Unified Model HadCM3

The concentration of carbon dioxide in the atmosphere acts to control the stomatal conductance of plants. There is observational and modelling evidence that an increase in the atmospheric concentration of CO₂ would suppress the evapotranspiration (ET) rate over land. This process is known as CO₂ physiological forcing and has been shown to induce changes in surface temperature and continental runoff. We analyse two transient climate simulations for the twenty-first century to isolate the climate response to the CO₂ physiological forcing. The land surface warming associated with the decreased ET rate is accompanied by an increase in the atmospheric lapse rate, an increase in specific humidity, but a decrease in relative humidity and stratiform cloud over land. We find that the water vapour feedback more than compensates for the decrease in latent heat flux over land as far as the budget of atmospheric water vapour is concerned. There is evidence that surface snow, water vapour and cloudiness respond to the CO₂ physiological forcing and all contribute to further warm the climate system. The climate response to the CO₂ physiological forcing has a quite different signature to that from the CO₂ radiative forcing, especially in terms of the changes in the temperature vertical profile and surface energy budget over land.     

Provenance record of late Maastrichtian–late Palaeocene Andean Mountain building in the Amazonian retroarc foreland basin (Madre de Dios basin,Peru)

Biostratigraphic, sedimentological and provenance analyses suggest that a proto‐Andean Cordillera already existed in southern Peru by late Maastrichtian–late Palaeocene times. A 270‐m‐thick stratigraphic section shows changes in depositional environments from shallow marine (early Maastrichtian) to non‐marine (late Maastrichtian) then back to estuarine (late Palaeocene) conditions. An erosional surface separates lower Maastrichtian from upper Maastrichtian deposits. Above this surface, the late Maastrichtian unit exhibits moderately developed palaeosols and syn‐sedimentary normal faults. The sedimentary evolution is accompanied by a decrease in sedimentation rate and by changes in provenance. Shallow marine lower Maastrichtian deposits have a cratonic provenance as shown by their low εNd(0) values (?15 to ?16) and the presence of Precambrian inherited zircon grains. The upper Maastrichtian deposits have a mixed Andean and cratonic origin with εNd(0) values of ~12.6 and yield the first Cretaceous and Permo‐Triassic zircon grains. Estuarine to shallow marine upper Palaeocene deposits have an Andean dominant source as attested by higher εNd(0) values (?6 to ?10) and by the presence of Palaeozoic and Late Cretaceous zircon grains. The changes in depositional environments and sedimentation rates, as well as the shift in detrital provenance, are consistent with a late Maastrichtian–late Palaeocene period of Andean mountain building. In agreement with recently published studies, our data suggest that an Andean retroarc foreland basin was active by late Maastrichtian–late Palaeocene times.     

Quantification of sediment source contributions in two paired catchments of the Brazilian Pampa using conventional and alternative fingerprinting approaches

The knowledge of the contribution of sediment sources to river networks is a prerequisite to understand the impact of land use change on sediment yield. We calculated the relative contributions of sediment sources in two paired catchments, one with commercial eucalyptus plantations (0.83 km²) and the other with grassland used for livestock farming (1.10 km²), located in the Brazilian Pampa biome, using different combinations of conventional [geochemical (G), radionuclide (R) and stable isotopes and organic matter properties (S)] and alternative tracer properties [spectrocolorimetric visible-based-colour parameters (V)]. Potential sediment sources evaluated were stream channel, natural grassland and oat pasture fields in the grassland catchment, and stream channel, unpaved roads and eucalyptus plantation in the eucalyptus catchment. The results show that the best combination of tracers to discriminate the potential sources was using GSRV tracers in the grassland catchment, and using GSRV, GSV and GS tracers in the eucalyptus catchment. In all these cases, samples were 100% correctly classified in their respective groups. Considering the best tracers results (GSRV) in both catchments, the sediment source contributions estimated in the catchment with eucalyptus plantations was 63, 30 and 7% for stream channel, eucalyptus stands and unpaved roads, respectively. In the grassland catchment, the source contributions to sediment were 84, 14 and 2% for natural grassland, stream channel and oats pasture fields, respectively. The combination of these source apportionment results with the annual sediment loads monitored during a 3-year period demonstrates that commercial eucalyptus plantations supplied approximately 10 times less sediment (0.1 ton ha⁻¹ year⁻¹) than the traditional land uses in this region, that is, 1.0 ton ha⁻¹ year⁻¹ from grassland and 0.3 ton ha⁻¹ year⁻¹ from oats pasture fields. These results demonstrate the potential of combining conventional and alternative approaches to trace sediment sources originating from different land uses in this region. Furthermore, they show that well-managed forest plantations may be less sensitive to erosion than grassland used for intensive livestock farming, which should be taken into account to promote the sustainable use of land in this region of South America.     

Skill assessment of three earth system models with common marine biogeochemistry

We have assessed the ability of a common ocean biogeochemical model, PISCES, to match relevant modern data fields across a range of ocean circulation fields from three distinct Earth system models: IPSL-CM4-LOOP, IPSL-CM5A-LR and CNRM-CM5.1. The first of these Earth system models has contributed to the IPCC 4th assessment report, while the latter two are contributing to the ongoing IPCC 5th assessment report. These models differ with respect to their atmospheric component, ocean subgrid-scale physics and resolution. The simulated vertical distribution of biogeochemical tracers suffer from biases in ocean circulation and a poor representation of the sinking fluxes of matter. Nevertheless, differences between upper and deep ocean model skills significantly point to changes in the underlying model representations of ocean circulation. IPSL-CM5A-LR and CNRM-CM5.1 poorly represent deep-ocean circulation compared to IPSL-CM4-LOOP degrading the vertical distribution of biogeochemical tracers. However, their representations of surface wind, wind stress, mixed-layer depth and geostrophic circulations (e.g., Antarctic Circumpolar Current) have been improved compared to IPSL-CM4-LOOP. These improvements result in a better representation of large-scale structure of biogeochemical fields in the upper ocean. In particular, a deepening of 20–40 m of the summer mixed-layer depth allows to capture the 0–0.5 μgChl L^?1 concentrations class of surface chlorophyll in the Southern Ocean. Further improvements in the representation of the ocean mixed-layer and deep-ocean ventilation are needed for the next generations of models development to better simulate marine biogeochemistry. In order to better constrain ocean dynamics, we suggest that biogeochemical or passive tracer modules should be used routinely for both model development and model intercomparisons.