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.     

Particulate pollution monitoring in the Elefsis Gulf: The role of mineral magnetic studies

Measurements of ‘quadrature’ susceptibility (X_q) at low and high frequency on seabottom sediments of the Gulf of Elefsis supplement the results derived from the study of magnetic susceptibility (X) and saturation isothermal remanent magnetization (SIRM) (Scoullos et al., 1979) and make possible the distinction between the background soil erosional fraction and that of anthropogenic combustion origin. New devices speed up the on-site appraisal of the impact of discharges on marine sediment quality.     

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.     

Natural geobatteries associated with sulphide ore deposits, II. Field studies at the viburnum trend, southeast Missouri, U.S.A.

Any conductive sulphide ore body can generate electrical ore potentials and this can be regarded as a geobattery, with an upper positive cathode and a lower negative anode. Two mechanisms which can occur simultaneously and which appear to explain these potentials are the oxygen concentration cell (OCC) and the sulphide galvanic cell (SGC). When there is a difference of O₂ concentration between the cathode and anode, the OCC operates by contributing oxygen to the anode, and ceases when the difference is diminished. However, gradients of pH, temperature or pressure can keep the cell operating. In the SGC the sulphides dissolve at the anode (producing metal ions, sulphur and electrons), while at the cathode, either sulphides dissolve producing metal and sulphur ions, or reaction is as in the OCC. The ore potential measured in the field is the sum of the oxygen concentration cell and at times locally dominant sulphide galvanic cells.     

The thermal boundary-layer interpretation of D″ and its role as a plume source

The “anomalous” layer in the lowermost mantle, identified as D″ in the notation of K.E. Bullen, appears in the PREM Earth model as a 150 km-thick zone in which the gradient of incompressibility with pressure, $\text{d}\text{K}\text{d}\text{P}$, is almost 1.6, instead of 3.2 as in the overlying mantle. Since PREM shows no accompanying change in density or density gradient, we identify D″ as a thermal boundary layer and not as a chemically distinct zone. The anomaly in $\text{d}\text{K}\text{d}\text{P}$ is related to the temperature gradient by the temperature dependence of K_s, for which we present a thermodynamic identity in terms of accessible quantities. This gives the numerical result (?K_s/?T)_P=?1.6×10⁷ Pa K^?1 for D″ material. The corresponding temperature increment over the D″ range is 840 K. Such a layer cannot be a static feature, but must be maintained by a downward motion of the lower mantle toward the core-mantle boundary with a strong horizontal flow near the base of D″. Assuming a core heat flux of 1.6 × 10¹² W, the downward speed is 0.07 mm y^?1 and the temperature profile in D″, scaled to match PREM data, is approximately exponential with a scale height of 73 km. The inferred thermal conductivity is 1.2 W m^?1 K^?1. Using these values we develop a new analytical model of D″ which is dynamically and thermally consistent. In this model, the lower-mantle material is heated and softened as it moves down into D″ where the strong temperature dependence of viscosity concentrates the horizontal flow in a layer ～ 12 km thick and similarly ensures its removal via narrow plumes.     

Adsorption and Desorption of Phosphate on Calcite and Aragonite in Seawater

The adsorption and desorption of phosphate on calcite and aragonite were investigated as a function of temperature (5–45 °C)and salinity (0–40) in seawater pre-equilibrated with CaCO₃. An increase in temperature increased the equilibrium adsorption; whereas an increase in salinity decreased the adsorption. Adsorption measurements made in NaCl were lower than the results in seawater. The higher values in seawater were due to the presence of Mg²⁺ and Ca²⁺ ions. The increase was 5 times greater for Ca²⁺ than Mg²⁺. The effects ofCa²⁺ and Mg²⁺ are diminished with the addition of SO₄ ^2- apparently due to the formation of MgSO₄ and CaSO₄ complexes in solution and/or SO₄ ^2- adsorption on the surface of CaCO₃. The adsorbed Ca²⁺ and Mg²⁺ on CaCO₃ (at carbonate sites) may act as bridges to PO₄ ^3- ions. The bridging effect of Ca²⁺is greater than Mg²⁺ apparently due to the stronger interactions of Ca²⁺ with PO₄ ^3-.The apparent effect of salinity on the adsorption of PO₄ was largely due to changes in the concentration of HCO₃ ^- in the solutions. An increase in the concentration of HCO₃ ^- caused the adsorption of phosphate to decrease, especially at low salinities. The adsorption at the same level of HCO₃ ^- (2 mM) was nearly independent of salinity. All of the adsorption measurements were modeled empirically using a Langmuir-type adsorption isotherm[ [PO₄]_ad = K_mC_m[PO₄]_T/(1 +K_m [PO₄]_T) , ]where [PO₄]_ad and [PO₄]_T are the adsorbed and total dissolved phosphate concentrations, respectively. The values of C_m (the maximum monolayer adsorption capacity, (mol/g) and K_m (the adsorption equilibrium constant, g/(mol) over the entire temperature (t, °C) and salinity (S) range were fitted to[ C_m = 17.067 + 0.1707t - 0.4693S + 0.0082S² ( = 0.7) ][ ln K_m = - 2.412 + 0.0165t - 0.0004St - 0.0008S² ( = 0.1) ]These empirical equations reproduce all of our measurements of[PO₄]_ad up to 14 mol/g and within ±0.7 mol/g.The kinetic data showed that the phosphate uptake on carbonate minerals appears to be a multi-step process. Both the adsorption and desorption were quite fast in the first stage (less than 30 min) followed by a much slower process (lasting more than 1 week). Our results indicate that within 24 hours aragonite has a higher sorption capacity than calcite. The differences between calcite and aragonite become smaller with time. Consequently, the mineral composition of the sediments may affect the short-term phosphate adsorption and desorption on calcium carbonate. Up to 80 % of the adsorbed phosphate is released from calcium carbonate over one day. The amount of PO₄ left on the CaCO₃ is close to the equilibrium adsorption. The release of PO₄ from calcite is faster than from aragonite. Measurements with Florida Bay sediments produced results between those for calcite and aragonite. Our results indicate that the calcium carbonate can be both a sink and source of phosphate in natural waters.