High temperature calorimetry of sulfide systems

The standard enthalpies of formation of FeS (troilite), FeS₂ (pyrite), Co_0.9342S, Co₃S₄ (linnaeite), Co₉S₈ (cobalt pentlandite), CoS₂ (cattierite), CuS (covellite), and Cu₂S (chalcocite) have been determined by high temperature direct reaction calorimetry at temperatures between 700 K and 1021 K. The following results are reported: $$\Delta {\rm H}_{f,FeS}^{tr} = - 102.59 \pm 0.20kJ mol^{ - 1} ,$$ $$\Delta {\rm H}_{f,FeS}^{py} = - 171.64 \pm 0.93kJ mol^{ - 1} ,$$ $$\Delta {\rm H}_{f,Co_{0.934} S} = - 99.42 \pm 1.52kJ mol^{ - 1} ,$$ $$\Delta {\rm H}_{f,Co_9 S_8 }^{ptl} = - 885.66 \pm 16.83kJ mol^{ - 1} ,$$ $$\Delta {\rm H}_{f,Co_3 S_4 }^{In} = - 347.47 \pm 7.27kJ mol^{ - 1} ,$$ $$\Delta {\rm H}_{f,CoS_2 }^{ct} = - 150.94 \pm 4.85kJ mol^{ - 1} ,$$ $$\Delta {\rm H}_{f,Cu_2 S}^{cc} = - 80.21 \pm 1.51kJ mol^{ - 1} ,$$ and $$\Delta {\rm H}_{f,CuS}^{cv} = - 53.14 \pm 2.28kJ mol^{ - 1} ,$$ The enthalpy of formation of CuFeS₂ (chalcopyrite) from (CuS+FeS) and from (Cu+FeS₂) was determined by solution calorimetry in a liquid Ni_0.60S_0.40 melt at 1100 K. The results of these measurements were combined with the standard enthalpies of formation of CuS, FeS, and FeS₂, to calculate the standard enthalpy of formation of CuFeS₂. We found \(\Delta {\rm H}_{f,CuFeS_2 }^{ccp} = - 194.93 \pm 4.84kJ mol^{ - 1}\) . Our results are compared with earlier data given in the literature; generally the agreement is good and our values agree with previous estimates within the uncertainties present in both.     

Dependence on pressure of conduction by hopping of small polarons in minerals of the Earth's lower mantle

Electrical conductivity of the lower mantle-like assemblage (Mg,Fe)SiO₃ perovskite-(Mg,Fe)O magnesiowüstite is usually analyzed using the quasi-chemical Arrhenian approach of diffusion. The conductivity of this assemblage has often been attributed to hopping of small polarons, because of the low value of the activation energy and the small negative activation volume. However, the solid-state physics approach can provide more arguments, for or against conduction by polarons. We have tried to bridge the gap between the two approaches and identify the physical quantities entering the phenomenological activation parameters. In particular, we have investigated the pressure dependence of the activation energy, and the physical meaning of the activation volume. Hopping is controlled by the binding energy of the polaron and by the value of the exchange integral, which increases with pressure causing the observed decrease of the activation energy. From the physical theory and the results of experiments at pressures up to 40 GPa and temperatures up to 400 ^∘C, we have estimated the values of parameters characteristic of polarons: radius, mobility, time between jumps and adiabaticity. These values are compatible with conduction by small adiabatic polarons. The consequences for extrapolations to lower mantle conditions of the presence of a temperature dependent preexponential term in the expression for conductivity have been examined. It was found that the extrapolations are not significantly different from those using the Arrhenius equation. Received: 5 November 1998 / Revised, accepted: 4 May 1999     

Hydrogeochemistry of two river main floodplain lakes,Hessia, FR Germany

Two lakes, Lake Gänseweiher (LGW) and Lake Fechenheimer Weiher (LFW) occupy groundwater filled abandoned gravel pits which serve as fishing grounds and are part of recreational areas, respectively.Both lakes are cut into a near-surface groundwater aquifer, which is located in the pleistocene River Main gravel terrace t₆. They are sealed at the base by miocene clays and above by overlying flood deposits of the River Main. The latter provide protection from pollutants derived from wet and dry deposition of atmospheric contaminants.Groundwater chemistry determines the pool of dissolved constituents in lake water. The temporal and spatial distribution patterns of chemical compounds in lake water are brought about by endo-biogenic processes, of which the indicators are nitrate-nitrogen and dissolved silica. The latter illustrates an instantaneous response to pulses of diatom blooms.Both lakes are eutrophic (polytrophic) according to the classification guidelines presented in literature.     

The role of stratification in the deoxygenation of Mobile Bay and adjacent shelf bottom waters

Oxygen depletion in the shallow bottom waters of Mobile Bay, Alabama, and in adjacent nearshore and continental shelf waters, is shown to be directly related to the intensity of water column stratification. Low winds speeds are coincidental with the onset of water column stratification and the occurrence of hypoxic events. Hourly, daily, and seasonal changes in the relationship between percent oxygen saturation or oxygen concentration in the bottom waters and surface-bottom density differences indicate that the oxidized materials are recently formed, and not relic or overwintering carbon sources. The influence of density structure (water column stratification) in other oxygen-depleted coastal water masses is compared to Mobile Bay.     

Behaviour of radiogenic Pb in zircon during ultrahigh-temperature metamorphism: an ion imaging and ion tomography case study from the Kerala Khondalite Belt,southern India

Zircon crystals from a locally charnockitized Paleoproterozoic high-K metagranite from the Kerala Khondalite Belt (KKB) of southern India have been investigated by high-spatial resolution secondary ion mass spectrometry analysis of U–Th–Pb and rare earth elements (REE), together with scanning ion imaging and scanning ion tomography (depth-profiled ion imaging). The spot analyses constrain the magmatic crystallization age of the metagranite to ca. 1,850 Ma, with ultrahigh-temperature (UHT) metamorphism occurring at ca. 570 Ma and superimposed charnockite formation at ca. 520–510 Ma, while the ion imaging reveals a patchy distribution of radiogenic Pb throughout the zircon cores. Middle- to heavy-REE depletion in ca. 570 Ma zircon rims suggests that these grew in equilibrium with garnet and therefore date the UHT metamorphism in the KKB. The maximum apparent ²⁰⁷Pb/²⁰⁶Pb age obtained from the unsupported radiogenic Pb concentrations is also consistent with formation of the Pb patches during this event. The superimposed charnockitization event appears to have caused additional Pb-loss in the cores and recrystallization of the rims. The results of depth-profiling of the scanning ion tomography image stack show that the Pb-rich domains range in size from <5 nm to several 10 nm (diameter if assumed to be spherical). The occurrence of such patchy Pb has previously been documented only from UHT metamorphic zircon, where it likely results from annealing of radiation-damaged zircon. The formation of a discrete, heterogeneously distributed and subsequently immobile Pb phase effectively arrests the normal Pb-loss process seen at lower grades of metamorphism.     

Correction: Hydraulic tomography analysis of municipal-well operation data with geology-based groundwater models

Hydrogeology Journal - A Correction to this paper has been published: https://doi.org/10.1007/s10040-021-02351-x     

Lake-Level Fluctuations and Small-Scale Vegetation Patterns During the Late Glacial in The Netherlands

Late glacial changes in the vegetation were studied in and around a former lake on the southeastern side of a coversand ridge near Milheeze (southern Netherlands). Analyses of microfossils and macroremains and AMS ¹⁴C dating were performed on four sediment cores along a transect from sand ridge to the lake centre. Small-scale vegetation patterns and lake-level fluctuations were reconstructed in detail based on the information provided by the transect. For the first time in The Netherlands, cores along a transect within one lake were used to reconstruct the amplitude of late glacial lake-level fluctuations. Near Milheeze, a small and shallow lake was formed during the Bølling. The large increase in the water level during the Bølling and early Allerød, and the transition to more eutrophic conditions at the start of the Allerød, were probably related to the disappearance of permafrost. During the Allerød, open birch and pine woodlands developed in the area. In the lake, organic deposits accumulated, and the lake size and depth fluctuated. At the start of the Younger Dryas, higher lake water levels were recorded and woodlands became more open as a result of both a drop in the temperature and an increase in the effective precipitation. During the late Younger Dryas the lake water level dropped as the climate became drier and temperatures slightly increased. Accumulation of organic deposits in the lake ceased at the end of the Younger Dryas, which was caused by a drop in the water level in combination with the hydroseral succession process within the lake itself. The climatic signal reflected in the late glacial flora and lake-level fluctuations agree well with other published data from The Netherlands.