Experimental determination of the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions to 400°C

The solubility of silver sulphide (acanthite/argentite) has been measured in aqueous sulphide solutions between 25 and 400°C at saturated water vapour pressure and 500 bar to determine the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions. The experiments were carried out in a flow-through autoclave, connected to a high-performance liquid chromatographic pump, titanium sampling loop, and a back-pressure regulator on line. Samples for silver determination were collected via the titanium sampling loop at experimental temperatures and pressures. The solubilities, measured as total dissolved silver, were in the range 1.0 × 10⁻⁷ to 1.30 × 10⁻⁴ mol kg⁻¹ (0.01 to 14.0 ppm), in solutions of total reduced sulphur between 0.007 and 0.176 mol kg⁻¹ and pH_T,p of 3.7 to 12.7. A nonlinear least squares treatment of the data demonstrates that the solubility of silver sulphide in aqueous sulphide solutions of acidic to alkaline pH is accurately described by the reactions0.5Ag₂S(s) + 0.5H₂S(aq) = AgHS(aq) K_s,1110.5Ag₂S(s) + 0.5H₂S(aq) + HS⁻ = Ag(HS)2− K_s,122Ag₂S(s) + 2HS⁻ = Ag₂S(HS)22− K_s,232where AgHS(aq) is the dominant species in acidic solutions, Ag(HS)2− under neutral pH conditions and Ag₂S(HS)22− in alkaline solutions. With increasing temperature the stability field of Ag(HS)2− increases and shifts to more alkaline pH in accordance with the change in the first ionisation constant of H₂S(aq). Consequently, Ag₂S(HS)22− is not an important species above 200°C. The solubility constant for the first reaction is independent of temperature to 300°C, with values in the range logK_s,111 = −5.79 (±0.07) to −5.59 (±0.09), and decreases to −5.92 (±0.16) at 400°C. The solubility constant for the second reaction increases almost linearly with inverse temperature from logK_s,122 = −3.97 (±0.04) at 25°C to −1.89 (±0.03) at 400°C. The solubility constant for the third reaction increases with temperature from logK_s,232 = −4.78 (±0.04) at 25°C to −4.57 (±0.18) at 200°C. All solubility constants were found to be independent of pressure within experimental uncertainties. The interaction between Ag⁺ and HS⁻ at 25°C and 1 bar to form AgHS(aq) has appreciable covalent character, as reflected in the exothermic enthalpy and small entropy of formation. With increasing temperature, the stepwise formation reactions become progressively more endothermic and are accompanied by large positive entropies, indicating greater electrostatic interaction. The aqueous speciation of silver is very sensitive to fluid composition and temperature. Below 100°C silver(I) sulphide complexes predominate in reduced sulphide solutions, whereas Ag⁺ and AgClOH⁻ are the dominant species in oxidised waters. In high-temperature hydrothermal solutions of seawater salinity, chloride complexes of silver(I) are most important, whereas in dilute hydrothermal fluids of meteoric origin typically found in active geothermal systems, sulphide complexes predominate. Adiabatic boiling of dilute and saline geothermal waters leads to precipitation of silver sulphide and removal of silver from solution. Conductive cooling has insignificant effects on silver mobility in dilute fluids, whereas it leads to quantitative loss of silver for geothermal fluids of seawater salinity.     

Late Pliocene to late Pleistocene environments preserved at the Palisades Site, central Yukon River, Alaska

The Palisades Site is an extensive silt-loam bluff complex on the central Yukon River preserving a nearly continuous record of the last 2 myr. Volcanic ash deposits present include the Old Crow (OCt; 140,000 yr), Sheep Creek (SCt; 190,000 yr), PA (2.02 myr), EC (ca. 2 myr), and Mining Camp (ca. 2 myr) tephras. Two new tephras, PAL and PAU, are geochemically similar to the PA and EC tephras and appear to be comagmatic. The PA tephra occurs in ice-wedge casts and solifluction deposits, marking the oldest occurrence of permafrost in central Alaska. Three buried forest horizons are present in association with dated tephras. The uppermost forest bed occurs immediately above the OCt; the middle forest horizon occurs below the SCt. The lowest forest bed occurs between the EC and the PA tephras, and correlates with the Dawson Cut Forest Bed. Plant taxa in all three peats are common elements of moist taiga forest found in lowlands of central Alaska today. Large mammal fossils are all from common late Pleistocene taxa. Those recovered in situ came from a single horizon radiocarbon dated to ca. 27,000 ¹⁴C yr B.P. The incongruous small mammal assemblage in that horizon reflects a diverse landscape with both wet and mesic environments.     

A coupled model study on ENSO, MJO and Indian summer monsoon rainfall relationships

Summary In this paper, we have tried to understand the ENSO, MJO and Indian summer monsoon rainfall relationships from observation as well as from coupled model results. It was the general feeling that El-Niño years are the deficient in Indian monsoon rainfall and converse being the case for the La-Niña years. Recent papers by several authors noted the failure of this relationship. We find that the model output does confirm a breakdown of this relationship. In this study we have seen that a statistically defined modified Indian summer monsoon rainfall (MISMR) index, a linearly regressed ISMR index and dynamical Webster index (WBSI), shows an inverse relationship with ENSO index during the entire period of integration (1987 to 1999). It is also seen from this study that the amplification of the MJO signals were large and the ENSO signals were less pronounced during the years of above normal ISMR. The MJO signal amplitudes were small and ENSO signals were strong during the years of deficient ISMR. It has been noted that here is a time lag between the MJO and ENSO signal in terms of their modulation aspect. If time lag is added with the ENSO signal then both signals maintain the amplitude modulation theory. A hypothesis is being proposed here to define a relationship between MJO and ENSO signals for the entire period between 1987 and 1999.Received September 18, 2002; revised November 22, 2002; accepted December 20, 2002 Published online: May 8, 2003     

Evolution of the equatorial and dipole modes of the sea-surface temperature in the Tropical Atlantic at decadal scale

Summary ?One hundred and thirty six years (1856–1991) of monthly sea-surface temperature (SST) data in the Tropical Atlantic Ocean are used to investigate the propagating signals of the SST at a decadal (DD) time scale. The first and the third evolving modes show a relationship between the equatorial and the inter-hemispheric patterns, one evolving into the other mode and vice-versa. These modes describe two different evolutions of the SST at DD time-scale. The first EEOF features a 12-year period oscillatory regime with a strong 2-year duration inter-hemispheric pattern evolving into a weak 1-year duration equatorial pattern and vice-versa. This mode exhibits also a northward displacement of the anomalies in the band 15° S–15° N. The third EEOF also shows an oscillatory regime, but with a period of 10 years and with a relatively strong 2-year duration equatorial pattern evolving into a weak 1-year duration inter-hemispheric pattern and vice-versa. For this mode, the SST anomalies show a southward displacement in the band 15° S–15° N. These results have not yet been documented in previous works and explain some of the previous findings on the DD variability in the Tropical Atlantic. Received December 31, 2001; revised April 9, 2002; accepted September 4, 2002 Published online: March 20, 2003     

Turbulence Statistics Inside and Over Forest: Influence on Footprint Prediction

Observations of wind statistics within and above a Scots pine forest are comparedwith those predicted from an analytical second-order closure model. The roughnesssublayer (RSL) effects, and the influence of stability on similarity functions, arestudied using observations. The commonly accepted forms of similarity functionsdescribe the influence of diabatic effects above the RSL well. According to earlierstudies they are expected also to apply within the RSL. As an exception, the averagewind speed normalised with friction velocity was found to be invariant with stabilityclose to the canopy top under unstable conditions. Lagrangian stochastic trajectorysimulations were used to evaluate the influence of canopy turbulence profiles onfootprint prediction. The main uncertainty was found to arise from parameterisationof the random forcing term in the Lagrangian velocity equation. The influence ofdiabatic conditions was studied, and it was found that thermal stability affectssignificantly the footprint function above the forest canopy, but significantuncertainty exists because of uncertainties in the formulation of stability functions.     

Description and evaluation of the bergen climate model: ARPEGE coupled with MICOM

A new coupled atmosphere–ocean–sea ice model has been developed, named the Bergen Climate Model (BCM). It consists of the atmospheric model ARPEGE/IFS, together with a global version of the ocean model MICOM including a dynamic–thermodynamic sea ice model. The coupling between the two models uses the OASIS software package. The new model concept is described, and results from a 300-year control integration is evaluated against observational data. In BCM, both the atmosphere and the ocean components use grids which can be irregular and have non-matching coastlines. Much effort has been put into the development of optimal interpolation schemes between the models, in particular the non-trivial problem of flux conservation in the coastal areas. A flux adjustment technique has been applied to the heat and fresh-water fluxes. There is, however, a weak drift in global mean sea-surface temperature (SST) and sea-surface salinity (SSS) of respectively 0.1 °C and 0.02 psu per century. The model gives a realistic simulation of the radiation balance at the top-of-the-atmosphere, and the net surface fluxes of longwave, shortwave, and turbulent heat fluxes are within observed values. Both global and total zonal means of cloud cover and precipitation are fairly close to observations, and errors are mainly related to the strength and positioning of the Hadley cell. The mean sea-level pressure (SLP) is well simulated, and both the mean state and the interannual standard deviation show realistic features. The SST field is several degrees too cold in the equatorial upwelling area in the Pacific, and about 1 °C too warm along the eastern margins of the oceans, and in the polar regions. The deviation from Levitus salinity is typically 0.1 psu – 0.4 psu, with a tendency for positive anomalies in the Northern Hemisphere, and negative in the Southern Hemisphere. The sea-ice distribution is realistic, but with too thin ice in the Arctic Ocean and too small ice coverage in the Southern Ocean. These model deficiencies have a strong influence on the surface air temperatures in these regions. Horizontal oceanic mass transports are in the lower range of those observed. The strength of the meridional overturning in the Atlantic is 18 Sv. An analysis of the large-scale variability in the model climate reveals realistic El Niño – Southern Oscillation (ENSO) and North Atlantic–Arctic Oscillation (NAO/AO) characteristics in the SLP and surface temperatures, including spatial patterns, frequencies, and strength. While the NAO/AO spectrum is white in SLP and red in temperature, the ENSO spectrum shows an energy maximum near 3 years.     

Cloud type and cloud cover effects on the surface radiative balance at several Polar sites

Summary ?The present work concerns measurements performed at five Polar sites in order to study the influence of cloud type and cloud cover on the surface radiative balance. Cloud cover index was retrieved with the Kasten and Czeplak formula (1980), and comparison with observed values showed the possibility of applying this formula in Polar regions. The Duchon and O’Malley (1999) methodology was adopted to estimate the cloud types present during the measurement period for each site. The results show that during the Antarctic summer clouds have a warming effect on the surface, while during a melting event recorded in the Arctic site clouds have a net cooling effect on the surface. This result allows us to conclude that, during a melting period a different cloud type formation, and a lower surface albedo, modify the effects of clouds on the surface radiation balance. Received April 5, 2002; revised August 1, 2002; accepted August 17, 2002     

A profile of General Carlos Ibáñez e Ibáñez de Ibero: first president of the International Geodetic Association

 The exploits of the multifaceted scientist (engineer-geodesist-metrologist) General Carlos Ibá?ez e Ibá?ez de Ibero (1825–1891), Marqués de Mulhacén, are recounted. A bibliography of his relevant work is included. Received 27 September 1996; Accepted 2 October 1996     

Internet teaching foundation for the Remote Sensing Core Curriculum program

The Remote Sensing Core Curriculum (RSCC) was initiated in 1993 to meet the demands for a college-level set of resources to enhance the quality of education across national and international campuses. The American Society of Photogrammetry and Remote Sensing adopted the RSCC in 1996 to sustain support of this educational initiative for its membership and collegiate community. A series of volumes, containing lectures, exercises, and data, is being created by expert contributors to address the different technical fields of remote sensing. The RSCC program is designed to operate on the Internet taking full advantage of the World Wide Web (WWW) technology for distance learning. The issues of curriculum development related to the educational setting, with demands on faculty, students, and facilities, is considered to understand the new paradigms for WW-influenced computer-aided learning. The WWW is shown to be especially appropriate for facilitating remote sensing education with requirements for addressing image data sets and multimedia learning tools. The RSCC is located at http://www.umbc.edu/rscc     

On the Spatial Distribution and Seasonal Variation of Lower-Troposphere Ozone over Europe

Surface ozone data from 25 Europeanlow-altitude sites and mountain sites located between79°N and 28°N were studied. The analysiscovered the time period March 1989–February 1993.Average summer and winter O₃ concentrations inthe boundary layer over the continent gave rise togradients that were strongest in the north-west tosouth-east direction and west-east direction, respectively. WintertimeO₃ ranged from 19 to 27 ppbover the continent, compared to about 32 ppb at thewestern border, while for summer the continentalO₃ values ranged between 39 and 56 ppb and theoceanic mixing ratios were around 37 ppb. In the lowerfree troposphere average wintertime O₃ mixingratios were around 38 ppb, with only an 8 ppbdifference between 28°N and 79°N. For summerthe average O₃ levels decreased from about 55 ppbover Central Europe to 32 ppb at 79°N. Inaddition, O₃ and O_x(= O₃ + NO₂)in polluted and clean air were compared. Theamplitudes of the seasonal ozone variations increasedin the north-west to south-east direction, while thetime of the annual maximum was shifted from spring (atthe northerly sites) to late summer (at sites inAustria and Hungary), which reflected the contributionof photochemical ozone production in the lower partsof the troposphere.