Mineralogical,geochemical and microfabric evidences of gypsum crusts: a case study from Budapest

High levels of SO₂ and particulate pollution enable the rapid development of gypsum-rich weathering crusts in Budapest. Two types of white crusts, thin and thick ones, and two forms of black crusts, laminar and framboidal ones, were studied in limestone buildings of the parliament and Citadella. The percentage of crust cover and damage categories were documented on selected walls. Petrographic, XRD, XRF and sulphur isotope analyses were performed under laboratory conditions to understand the mechanism of crust formation. White crusts found both on exposed and sheltered walls display a calcite-rich layer with gypsum, while black crusts are enriched with gypsum. The sulphur isotopic composition of white and black crusts overlaps, but the crusts are slightly enriched in heavy isotopes compared to rainwater. S content, Si/Al ratios and particulates in black crusts suggest that air pollution (SO₂, dust) contributes to black crust formation. The accumulation of sulphur and Zn enrichment of white crusts were also documented indicating that under high pollution levels, even these compound can accumulate on exposed facades.     

Benthic foraminifers in upper Quaternary sediments of the southern Bering Sea: Distribution and paleoceanographic interpretations

Composition and distribution of benthic foraminifers, being coupled with isotopic-geochemical data on Upper Pleistocene and Holocene sediments from the southern Bering Sea (Core GC-11; 53°31′ N, 178°51′E, water depth 3060 m), demonstrate variations in bottom water properties during the last 54 kyr. Their abundance increased to some extent during short periods corresponding to warm Dansgaard-Oeshger interstadials 14, 12, 8, and 2 of marine isotopic stages (MIS) 3 and 2. The first and second deglaciation phases separated by the Younger Dryas cooling episode are marked by significant abundance peaks of benthic foraminifers (an order magnitude higher than in the glacial period), although their share in community of benthic and planktonic foraminifers taken together decreases. Species typical of stable high-productivity areas gain the dominant position. A significant proportion of agglutinated species in the Holocene sediments is indicative of Ca ions deficiency that accelerates dissolution of carbonate tests up to their disappearance approximately 2.5–3 ka ago.     

The relationships between tropical Atlantic sea level variability and major climate indices

Relationships were examined between variability in tropical Atlantic sea level and major climate indices with the use of TOPEX/POSEIDON altimeter and island tide gauge data with the aim of learning more about the external influences on the variability of the tropical Atlantic ocean. Possible important connections were found between indices related to the El Niño–Southern Oscillation (ENSO) and the sea levels in all three tropical regions (north, equatorial, and south), although the existence of only one major ENSO event within the decade of available altimetry means that a more complete investigation of the ENSO-dependence of Atlantic sea level changes has to await for the compilation of longer data sets. An additional link was found with the Indian Ocean Dipole (IOD) in the equatorial region, this perhaps surprising observation is probably an artifact of the similarity between IOD and ENSO time series in the 1990s. No evidence was obtained for significant correlations between tropical Atlantic sea level and North Atlantic Oscillation or Antarctic Oscillation Index. The most intriguing relationship observed was between the Quasi-Biennial Oscillation and sea level in a band centered approximately on 10°S. A plausible explanation for the relationship is lacking, but possibilities for further research are suggested.     

Evaluation of the first GOCE static gravity field models using terrestrial gravity,vertical deflections and EGM2008 quasigeoid heights

Recently, four global geopotential models (GGMs) were computed and released based on the first 2 months of data collected by the Gravity field and steady-state Ocean Circulation Explorer (GOCE) dedicated satellite gravity field mission. Given that GOCE is a technologically complex mission and different processing strategies were applied to real space-collected GOCE data for the first time, evaluation of the new models is an important aspect. As a first assessment strategy, we use terrestrial gravity data over Switzerland and Australia and astrogeodetic vertical deflections over Europe and Australia as ground-truth data sets for GOCE model evaluation. We apply a spectral enhancement method (SEM) to the truncated GOCE GGMs to make their spectral content more comparable with the terrestrial data. The SEM utilises the high-degree bands of EGM2008 and residual terrain model data as a data source to widely bridge the spectral gap between the satellite and terrestrial data. Analysis of root mean square (RMS) errors is carried out as a function of (i) the GOCE GGM expansion degree and (ii) the four different GOCE GGMs. The RMS curves are also compared against those from EGM2008 and GRACE-based GGMs. As a second assessment strategy, we compare global grids of GOCE GGM and EGM2008 quasigeoid heights. In connection with EGM2008 error estimates, this allows location of regions where GOCE is likely to deliver improved knowledge on the Earth’s gravity field. Our ground truth data sets, together with the EGM2008 quasigeoid comparisons, signal clear improvements in the spectral band ~160–165 to ~180–185 in terms of spherical harmonic degrees for the GOCE-based GGMs, fairly independently of the individual GOCE model used. The results from both assessments together provide strong evidence that the first 2 months of GOCE observations improve the knowledge of the Earth’s static gravity field at spatial scales between ~125 and ~110 km, particularly over parts of Asia, Africa, South America and Antarctica, in comparison with the pre-GOCE-era.     

Trends in the solubility of iron,aluminium, manganese and phosphorus in aerosol collected over the Atlantic Ocean

The solubility of iron, aluminium, manganese and phosphorus has been determined in aerosol samples collected between 49°N and 52°S during three cruises conducted in the Atlantic Ocean as part of the European Union funded IRONAGES programme. Solubilities (defined at pH 4.7) determined for Fe and Al in samples of Saharan dust were significantly lower (medians 1.7% and 3.0%, respectively) than the solubilities of these metals in aerosols from other source regions (whole dataset medians 5.2% and 9.0%, respectively). Mn solubility also varied with aerosol source, but the median solubility of Mn in Saharan dust was very similar to the median for the dataset as a whole (55% and 56%, respectively). The observed solubility of aerosol P was ∼ 32%, with P solubility in Saharan aerosol perhaps as low as 10%. Laboratory studies have indicated that aerosol Fe solubility is enhanced by acid processing. No relationship could be found between Fe solubility and the concentrations of acid species (non-seasalt SO₄²⁻, NO₃⁻) nor the net acidity of the aerosol, so we are unable to confirm that this process is significant in the atmosphere. In terms of the supply of soluble Fe to oceanic ecosystems on a global scale, the observed higher solubility for Fe in non-Saharan aerosols is probably not significant because the Sahara is easily the dominant source of Fe to the Atlantic. On a smaller scale however, higher solubility for aerosol Fe may alter our understanding of Fe cycling in regions such as the remote Southern Ocean.     

Copper sulphide formation chemistry at low temperatures

Summary Covellite, blaubleibender covellite, djurleite and chalcocite have been synthesized by the reaction between Cu₂O with aqueous Na₂S solutions at low temperatures. Digenite was produced by heating the dried products of the aqueous experimentation at 105°C for 50 days, but not directly from aqueous solution. Anilite was formed through air oxidation of chalcocite at room temperature. The pH and Eh conditions of formation of these phases have been studied and it has been shown that the synthetic results broadly reflect the theoretical stability fields for these compounds, inasmuch as more reduced copper sulphides are formed under higher pH and lower Eh conditions. Studies of the changes in these parameters during the course of the experiments have been used to outline the mechanisms involved in the reactions. It has been demonstrated that the form of the copper sulphide produced around neutral pH values is almost independent of the oxidation state of the copper reactant, but highly sensitive to the presence and concentration of elemental sulphur. A detailed discussion of the formation chemistry of copper sulphides in low temperature aqueous solutions is presented.

---

Chemie der Kupfersulfidbildung bei niedrigen Temperaturen

Zusammenfassung Covellin, blaubleibender Covellin, Djurleit und Chalkosin wurden durch Reaktion zwischen Cu₂O und wäßrigen Na₂S-Lösungen bei niedrigen Temperaturen synthetisiert. Digenit entstand, wenn die getrockneten Produkte aus wäßrigen Lösungen 50 Tage bei 105°C getempert wurden, aber nicht direkt aus wäßriger Lösung. Anilit bildete sich aus Chalkosin bei Zimmertemperatur durch Oxidation an der Luft. Die pH- und Eh-Bedingungen für die Bildung dieser Phasen wurden untersucht und es wurde gezeigt, daß die Syntheseergebnisse im wesentlichen den theoretischen Stabilitätsfeldern dieser Verbindungen entsprechen, indem sich die stärker reduzierten Kupfersulfide unter höherem pH und kleinerem Eh bilden. Untersuchungen über die Änderung dieser Parameter im Verlauf der Experimente wurden zur Umreißung der Reaktionsmechanismen benützt. Es wurde gezeigt, daß die Art des Kupfersulfides, welches sich um neutrale pH-Werte bildet, fast nicht vom Oxidationszustand des reagierenden Kupfers, aber stark von der Anwesenheit und der Konzentration von elementarem Schwefel abhängt. Die Chemie der Bildung von Kupfersulfiden in wäßrigen Lösungen niedriger Temperatur wird ausführlich diskutiert.

---

---

With 2 Figures     

Structure of Cu-bearing orthopyroxene, Mg(Cu.56,Mg.44)Si2O6, and behavior of Cu2+ in the orthopyroxene structure

Cu-bearing pyroxene, Mg(Cu.₅₆,Mg.₄₄)Si₂O₆, has been synthesized by a flux method and crystal structure refinement has been performed by single crystal X-ray diffraction. It is found that the crystal structure is orthorhombic (space group Pbca) with unit cell dimensions of a=18.221(4), b=8.890(1), c=5.2260(7)Å and the cell volume of 846.5( )3ų. In the M2-site one of the M-O bonds(M-O3B) is extremely expanded from 2.444(2) in enstatite to 2.732(2), thus the coordination polyhedron around M2-site is regarded as square pyramidal rather than square planar or octahedral. It is also found that the M1-site in the pyroxene structure is occupied almost exclusively by Mg, while the M2-site is almost evenly occupied by Mg and Cu. The observed extreme site preference shown by Cu²⁺ is unusual among the divalent cations with similar ionic sizes.     

Rare earth element geochemistry of potassic lavas from the Birunga and Toro-Ankole regions of Uganda,Africa

Neutron activation determination of La, Ce, Sm, Eu, Tb, Yb, Lu, Ta, Hf, Sc, Co and Th in potassic lavas from the Birunga and Toro-Ankole regions show that the rocks are characterized by high rare earth element (REE) contents (161–754 ppm) and form two groups based upon differing La/Yb ratios. One group is made up of katungite, ugandite and mafurite with La/Yb =146–312, and the other of rocks of the leucitite and phonolitic tephrite series, La/Yb =30–56. The trace element content of the ugandite group is similar to that of kimberlites. The data do not indicate any trends of differentiation or simple relationships between the two groups of rocks, although katungite is unlikely to be parental to rocks of lower La/Yb ratios. It is unlikely that in terms of La/Yb ratios that partial melting of mica-garnet-lherzolite mantle can form katungite because of the very small amounts of partial melting required (0.2%), although the La/Yb ratios of 150–200 (ugandites, mafurites) and 30–60 (leucitites, phonolitic tephrites) can be accounted for by 0.3–1.5% and 1–9% melting respectively, if the REE are then concentrated without further La and Yb fractionation. Partial melting of mantle which has been metasomatized by alkaline earths and REE bearing fluids or mixing of carbonatite and nephelenite are also compatable with the observed geochemistry of the lavas. It is considered that gas transfer processes which selectively enrich the light REE may have obscured REE evidence pertaining to early partial melting and/or differentiation processes and therefore that REE geochemistry is of little use in determining the petrogenetic processes involved in the formation of potassic lavas.     

B-polarization induction in two thin half-sheets coupled to the mantle by a conducting crust—II. Solution by the mode-matching method, the fields above the conductors, and example results

The mode-matching method is used to obtain an exact analytical solution to the problem of B -polarization induction in two adjacent thin half-sheets, lying on a conducting layer that is terminated by a perfect conductor at finite depth. These components of the model represent, respectively, the Earth's conducting surface layers, crust, and mantle. In dimensionless variables, the model has three independent parameters, these being the two thin-sheet conductances and the layer thickness. The mode-matching solution obtained in this paper is shown to be identical lo that derived via the Wiener-Hopf method in a companion paper (Dawson 1996), and so provides additional verification of that solution. As was shown in the companion paper, the solution for the present model contains, as special limiting cases, those for three models considered earlier by various authors. The second part of the present paper addresses the solutions for the electric fields in the non-conducting half-space above the conductors, which represents the atmosphere. In the final part, sample numerical calculations are presented to illustrate the solution.