The effect of ionic interactions on the oxidation of metals in natural waters

The effect of ionic interactions of the major components of natural waters on the oxidation of Cu(I) and Fe(II) has been examined. The various ion pairs of these metals have been shown to have different rates of oxidation. For Fe(II), the chloride and sulfate ion pairs are not easily oxidized. The measured decrease in the rate constant at a fixed pH in chloride and sulfate solutions agrees very well with the values predicted. The effect of pH (6 to 8) on the oxidation of Fe(II) in water and seawater have been shown to follow the rate equation

$\text{-d in [Fe(II)]/dt = k}{}_1\text{β}{}_1\text{α}{}_{\mathrm{Fe}}\text{/[H}{}^{\mathrm{+}}\text{] + k}{}_2\text{β}{}_2\text{α}{}_{\mathrm{Fe}}\text{/[H}{}^{\mathrm{+}}\text{]}{}^2$

where k₁ and k₂ are the pseudo first order rate constants, β₁ and β₂ are the hydrolysis constants for Fe(OH)⁺ and Fe(OH)⁰. The value of α_FE is the fraction of free Fe²⁺. The value of k₁ (2.0 ±0.5 min^?1) in water and seawater are similar within experimental error. The value of k₂ (1.2 × 10⁵ min^?1) in seawater is 28% of its value in water in reasonable agreement with predictions using an ion pairing model.For the oxidation of Cu(I) a rate equation of the form

$\text{?d ln [Cu(I)]/dt = k}{}_0\text{α}{}_{\mathrm{Cu}}\text{+ k}{}_1\text{β}{}_1\text{α}{}_{\mathrm{Cu}}\text{[Cl]}$

was found where k₀ (14.1 sec^?1) and k₁ (3.9 sec^?1) are the pseudo first order rate constants for the oxidation of Cu⁺ and CuCl⁰, β₁ is the formation constant for CuCl⁰ and α_Cu is the fraction of free Cu⁺. Thus, unlike the results for Fe(II), Cu(I) chloride complexes have measurable rates of oxidation.     

Thermal histories of the core and mantle

Recognition that the cooling of the core is accomplished by conduction of heat into a thermal boundary layer (D″) at the base of the mantle, partly decouples calculations of the thermal histories of the core and mantle. Both are controlled by the temperature-dependent rheology of the mantle, but in different ways. Thermal parameters of the Earth are more tightly constrained than hitherto by demanding that they satisfy both core and mantle histories. We require evolution from an early state, in which the temperatures of the top of the core and the base of the mantle were both very close to the mantle solidus, to the present state in which a temperature increment, estimated to be ～ 800 K, has developed across D″. The thermal history is not very dependent upon the assumption of Newtonian or non-Newtonian mantle rheology. The thermal boundary layer at the base of the mantle (i.e., D″) developed within the first few hundred million years and the temperature increment across it is still increasing slowly. In our preferred model the present temperature at the top of the core is 3800 K and the mantle temperature, extrapolated to the core boundary without the thermal boundary layer, is 3000 K. The mantle solidus is 3860 K. These temperatures could be varied within quite wide limits without seriously affecting our conclusions. Core gravitational energy release is found to have been remarkably constant at ～ 3 × 10¹¹ W. nearly 20% of the core heat flux, for the past 3 × 10⁹ y, although the total terrestrial heat flux has decreased by a factor of 2 or 3 in that time. This gravitational energy can power the “chemical” dynamo in spite of a core heat flux that is less than that required by conduction down an adiabatic gradient in the outer core; part of the gravitational energy is used to redistribute the excess heat back into the core, leaving 1.8 × 10¹¹ W to drive the dynamo. At no time was the dynamo thermally driven and the present radioactive heating in the core is negligibly small. The dynamo can persist indefinitely into the future; available power 10¹⁰ y from now is estimated to be 0.3 × 10¹¹ W if linear mantle rheology is assumed or more if mantle rheology is non-linear. The assumption that the gravitational constant decreases with time imposes an implausible rate of decrease in dynamo energy. With conventional thermodynamics it also requires radiogenic heating of the mantle considerably in excess of the likely content of radioactive elements.     

Use of Pitzer's equations to determine the media effect on the formation of lead chloro complexes

The spectrophotometric measurements of chloro complexes of lead in aqueous HCl, NaCl, MgCl₂ and CaCl₂ solutions at 25°C have been analyzed using Pitzer's specific interaction equations. Parameters for activity coefficients of the complexes PbCl⁺, PbCl₂⁰ and PbCl₃^? have been determined for the various media. Values of $\text{K}{}_1\text{= 30.0 ± 0.6}$, $\text{K}{}_2\text{= 106.7 ± 2.1}$ and $\text{K}{}_3\text{= 73.0 ± 1.5}$ were obtained for the cumulative formation constants. [$\text{Pb}{}^{\mathrm{2+}}\text{+ nCl}{}^{\mathrm{?}}\text{→ PbCl}{}_{\mathrm{n}}{}^{\mathrm{2?n}}\text{)}$]. These values are in reasonable agreement with literature data. The Pitzer parameters for the PbCl ion pairs in various media were used to calculate the speciation of Pb²⁺ in an artificial seawater solution.     

Magmatism and metamorphism in the Ladakh Himalayas (the Indus-Tsangpo suture zone)

Ladakh (India) provides a complete geological section through the northwestern part of the Himalayas from Kashmir to Tibet. Within this section the magmatic, metamorphic and geotectonic evolution of the northern Himalayan orogeny has been studied using petrographic, geochemical and isotope analytical techniques.The beginning of the Himalayan cycle was marked by large basaltic extrusions (Panjal Trap) of Permian to Lower Triassic age at the “northern” margin of the Gondwana continent (Indian Shield). These continental type tholeiitic basalts were followed by a more alkaline volcanism within the Triassic to Jurassic Lamayuru unit of the Gondwana continental margin.Lower Jurassic to Cretaceous oceanic crust and sediments (ophiolitic mélange s.s.) accompany the Triassic to Cretaceous flysch deposits within the Indus-Tsangpo suture zone, the major structural divide between the Indian Shield (High Himalaya) and the Tibetan Platform. So far, no relic of Paleozoic oceanic crust has been found.Subduction of the Tethyan oceanic crust during Upper Jurassic and Cretaceous time produced an island arc represented by tholeiitic and calc-alkaline volcanic rock series (Dras volcanics) and related intrusives accompanied by volcaniclastic flysch deposits towards the Tibetan continental margin.Subsequent to the subduction of oceanic crust, large volumes of calc-alkaline plutons (Trans-Himalayan or Kangdese plutons) intruded the Tibetan continental margin over a distance of 2000 km and partly the Dras island arc in the Ladakh region.The collision of the Indian Shield and Tibetan Platform started during the middle to upper Eocene and caused large-scale, still active intracrustal thrusting as well as the piling up of the Himalayan nappes. The tectonically highest of these nappes is built up of oceanic crust and huge slices of peridotitic oceanic mantle (Spongtang klippe).In the High Himalayas the tectonic activity was accompanied and outlasted by a Barrovian-type metamorphism that affected Triassic sediments of the Kashmir-Nun-Kun synclinorium up to kyanite/staurolite grade and the deeper-seated units up to sillimanite grade. Cooling ages of micas are around 20 m.y. (muscovite) and 13 m.y. (biotite). Towards the Indus-Tsangpo suture zone metamorphism decreases with no obvious discontinuity through greenschist, prehnite-pumpellyite to zeolite grade. Remnants of possibly an Eo-Himalayan blueschist metamorphism have been found within thrust zones accompanying ophiolitic mélange in the suture zone.     

Statistical analysis of time-dependent earthquake occurrence and its impact on hazard in the low seismicity region Lower Rhine Embayment

The time-dependence of earthquake occurrence is mostly ignored in standard seismic hazard assessment even though earthquake clustering is well known. In this work, we attempt to quantify the impact of more realistic dynamics on the seismic hazard estimations. We include the time and space dependences between earthquakes into the hazard analysis via Monte Carlo simulations. Our target region is the Lower Rhine Embayment, a low seismicity area in Germany. Including aftershock sequences by using the epidemic type aftershock-sequence (ETAS) model, we find that on average the hypothesis of uncorrelated random earthquake activity underestimates the hazard by 5–10 per cent. Furthermore, we show that aftershock activity of past large earthquakes can locally increase the hazard even centuries later. We also analyse the impact of the so-called long-term behaviour, assuming a quasi-periodic occurrence of main events on a major fault in that region. We found that a significant impact on hazard is only expected for the special case of a very regular recurrence of the main shocks.     

Comment on “Is there a paleolimnological explanation for ‘walking on water’ in the Sea of Galilee?”

In a recent paper, Nof et al. (J Paleolimnol 35:417–439, 2006) suggest a physical mechanism which could account for the formation of ice on Lake Kinneret (Sea of Galilee) in northern Israel. Based on the sea surface temperature record of sediment cores from the Mediterranean Sea the authors argue that centennial-scale cold events had the potential to trigger local ‘springs ice’ formation on the lake in the past. Here, we demonstrate that a closer inspection of the paleoceanographic record in combination with correlation and regression analyses of meteorological data provides no evidence for such cold events in the lake region during the last 10,000 years. Thus, the formation of ‘springs ice’ on Lake Kinneret was unlikely at least since the beginning of the Neolithic.     

Developing a high-resolution climatology for the Central California coastal region

This work presents a procedure for developing a high-resolution, regional climatology estimate, named RClimo, off the coast of central California. This high-resolution climatology may provide an alternative way to initialize numerical nowcast/forecast exercises in coastal regions. The methodology includes two primary steps: (1) averaging available data on a high-resolution grid and (2) objective interpolating the resulting average profiles onto a regular grid. The first step involves the computation of averages over density layers in the vertical and allowing for data gaps in the horizontal if data are unavailable at a high resolution. The OA in the second step uses anisotropic correlation length scales derived from the data themselves and an averaging radius to preserve the scales and variability of the synoptic fields.