Evaluation of trace element availability from secondary metallurgical slag generated in steelmaking by sequential chemical extraction

During carbon steel manufacture, slag residues are generated to remove material impurities from liquid metal and thus control the quality of carbon steel. As the utilization of secondary metallurgical slags is not as efficient as those of primary slags, a comprehensive characterization of steel ladle slag was performed. Pseudo-total concentrations of a wide range of elements were determined during a 6-week sampling period with relevant physical and chemical properties, sequential extraction of trace elements, and parallel mineralogical characterization of extraction residues from a representative combined sample. According to the results, only Cr and V occurred in elevated concentrations with respective 6-week mean values of 198 and 310 mg kg^?1 (d.w.). The residual standard deviation of the weekly pseudo-total concentration values of the aforementioned elements (24 and 31 %, respectively) indicated that significant variation in the concentration of trace elements can occur due to fluctuation in process conditions and/or slag characteristics. The sequential extraction procedure suggested potential phytoavailability of V (123 mg kg^?1, d.w., amounting to 41 % of the respective pseudo-total concentration) through, e.g., changes in prevailing redox conditions. Although the analytical approach was validated by the analysis of a certified reference material and the calculation of extraction recoveries, the mineralogical characterization of parallel extraction residues indicated non-selectivity of the procedure coupled with potential redistribution phenomena during extraction with hydrogen peroxide and ammonium acetate.     

Water in garnet of garnetite (metarodingite) and eclogite from the Erzgebirge and the Lepontine Alps

Little is known about water in nominally anhydrous minerals of orogenic garnet peridotite and enclosed metabasic rocks. This study is focused on peridotite-hosted eclogite and garnetite (metarodingite) from the Erzgebirge (EG), Germany, and the Lepontine Alps (LA), Switzerland. Newly discovered, peridotite-hosted eclogite in the Erzgebirge occurs in the same ultra-high pressure (UHP) unit as gneiss-hosted coesite eclogite, from which it is petrologically indistinguishable. Garnet is present in all mafic and ultramafic high pressure (HP) rocks providing for an ideal proxy to compare the H₂O content of the different rock types. Garnet composition is very similar in EG and LA samples and depends on the rock type. Garnet from garnetite, compared to eclogite, contains more CaO (garnetite: 10.5–16.5 wt%; eclogite: 5–11 wt%) and is also characterized by an anomalous REE distribution. In contrast, the infrared (IR) spectra of garnet from both rock types reveal the same OH absorption bands that are also identical to those of previously studied peridotitic garnet from the same locations. Two groups of IR bands, SW I (3,650 ± 10 cm⁻¹) and SW II (3,570–3,630 cm⁻¹) are ascribed to structural hydroxyl (colloquially ‘water’). A third, broad band is present in about half of the analysed garnet domains and related to molecular water (MW) in submicroscopic fluid inclusions. The primary content of structural H₂O, preserved in garnet domains without fluid inclusions (and MW bands), varies systematically—depending on both the location and the rock type. Garnet from EG rocks contains more water compared to LA samples, and garnet from garnetite (EG: 121–241 wt.ppm H₂O; LA: 23–46 wt.ppm) hosts more water than eclogitic garnet (EG: 84 wt.ppm; LA: 4–11 wt.ppm). Higher contents of structural water (SW) are observed in domains with molecular water, in which the SW II band (being not restricted to HP conditions) is simultaneously enhanced. This implies that fluid influx during decompression not only led to fluid inclusions but also favoured the uptake of secondary SW. The results signify that garnet from all EG and LA samples was originally H₂O-undersaturated. Combining the data from eclogite, garnetite and previously studied peridotite, H₂O and CaO are positively correlated, pointing to the same degree of H₂O-undersaturation at peak metamorphism in all rock types. This ubiquitous water-deficiency cannot be reconciled with the derivation of any of these rocks from the lowermost part of the mantle wedge that was in contact with the subducting plate. This agrees with the previously inferred abyssal origin for part of the rocks from the LA (Cima di Gagnone). A similar origin has to be invoked for the Erzgebirge UHP unit. We suggest that all mafic and ultramafic rocks of this unit not only shared the same metamorphic evolution but also a common protolith origin, most probably on the ocean floor. This inference is supported by the presence of peridotite-hosted garnetite, representing metamorphosed rodingite.     

Die lokale Beeinflussung eines stehenden Gewässers durch eine punktförmige Abwasserbelastung; ein direkter Nachweis der wachstumsbegrenzenden Wirkung des Phosphors im Vierwaldstättersee

Zusammenfassung Die Beeinflussung des Vierwaldst?ttersees (Horwer Bucht) durch den mit dem Abwasser von 10 000 Einwohnern belasteten Steinibach liess sich im Oberfl?chenwasser auf eine Distanz von mehr als 2 km verfolgen (Abb. 1a, 1b, 1c). Es zeigte sich, dass eine erh?hte Phosphorzufuhr eine verst?rkte biogene Nitratzehrung erm?glicht. Die Abh?ngigkeit der Pigmentkonzentration y von der Gesamtphosphorkonzentrationx liess sich durch die folgende Mitscherlich-Gleichung beschreiben: log(30-y)=log 30–0,012 (x−6) Damit wurde im Vierwaldst?ttersee erstmals unter v?llig natürlichen Bedingungen die Beeinflussung der Prim?rproduktion durch eine erh?hte Phosphorkonzentration nachgewiesen (Abb. 2). Die Erfolgsaussichten von Abwassersanierungsmassnahmen an Seen verschiedener Trophiegrade werden diskutiert.

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Summary The influence of the ‘Steinibach” tributary, into which the wastewater of 10,000 inhabitants is discharged, on the Lake of Lucerne (Horwer Bucht) is detectable in the surface water over a distance of more than 2 km (Picture 1a, 1b, 1c). It was revealed that the increased phosphorus supply enables more intensive biological nitrate consumption. The dependence of the pigment concentration,y, on the total phosphorus concentration,x can be expressed by the following Mitscherlich equation: log (30−y)=log 30–0.012 (x−6). This was the first time that the influence of an increased phosphorus concentration on primary production was proved in the Lake of Lucerne under completely natural conditions (Picture 2). The possibilities of implementing successful water pollution control measures in lakes with various trophic levels are discussed.

     

Unusual exsolution phenomena in omphacite and partial replacement of phengite by phlogopite + kyanite in an eclogite from the Erzgebirge

In the Erzgebirge Crystalline Complex, eclogites occur in three different high pressure (HP) units (1, 2 and 3) recording contrasting pressure (P)–temperature (T) conditions. Eclogites from HP-unit 1 experienced peak metamorphic conditions in the coesite stability field at about 33 kbar/850 °C. Commonly, these eclogites from HP-unit 1 are all very similar, with an eclogitic peak assemblage of omphacite–garnet–coesite–K-feldspar, rarely accompanied by kyanite, and omphacites systematically deviating from a stoichiometric composition. In contrast, an eclogite recently found near Blumenau, is mineralogically and geochemically different from the typical eclogites of HP-unit 1. This unusual eclogite reveals the eclogitic equilibrium assemblage omphacite–garnet–coesite–phengite–phlogopite–kyanite, and yields metamorphic peak conditions of 870 °C and >29 kbar. There is clear textural evidence of the formation of phlogopite and kyanite under partial consumption of phengite and garnet. Moreover, the omphacite is stoichiometric and contains abundant exsolution lamellae, the thickest of which were identified as quartz by the electron microprobe. The finer lamellae were studied by transmission electron microscopy (TEM). Oligoclase was identified as an exsolution phase. Other lamellae proved to consist of K-white mica, also interpreted as exsolution. Prior to exsolution, the omphacite composition must have been cation-deficient, as that of the other, common HP-unit 1 eclogites. These non-stoichiometric compositions are ascribed to partial substitution by the Ca-Eskola pyroxene component, which calculates to an average of 8 mol% for omphacite in HP-unit 1 eclogites. According to experiments, this substitution becomes significant at P > 30 kbar. Exsolution of K-white mica may indicate hydroxyl defects in the original omphacite, also favoured by high pressure. Oligoclase and K-white mica exsolution from Ca-Eskola-rich clinopyroxene has not previously been reported. The omphacite has a disordered C2/c structure; and in just one case very small (a few tens of nanometres) antiphase domains, resulting from the C2/c to P2/n transformation, are present. These features may indicate a brief thermal history and rapid tectonic processes. Received: 4 January 1999 / Accepted: 20 April 2000     

Experimental investigation of the metamorphism of siliceous dolomites

For the reaction: 1 diopside+3 dolomite ?2 forsterite+4 calcite+2 CO₂ (14) the following P _total?T-brackets have been determined experimentally in the presence of a gasphase consisting of 90 mole%CO₂ and 10 mole%H₂O∶1 kb, 544°±20° C; 3kb, 638°±15° C; 5kb, 708°±10° C; 10kb, 861°±10° C. The determination was carried out with well defined synthetic minerals in the starting mixture. The MgCO₃-contents of the magnesian calcites formed by the reaction in equilibrium with dolomite agree very well with the calcite-dolomite miscibility gap, which can be recalculated from the activities and the activity coefficients of MgCO₃ as given by Gordon and Greenwood (1970). The equilibrium constant K _14b was calculated with respect to the reference pressure P ₀=1 bar using the experimentally determined \(P_{total} TX_{CO_2 }\) brackets, the activities of MgCO₃ and CaCO₃ (Gordon and Greenwood 1970; Skippen 1974) and the fugacities of CO₂ Holloway (1977) considering the correction of Flowers (1979). Results are plotted as function of the absolute reciprocal temperature in Fig. 1. For the temperature range of 530° to 750° C the following linear expression can be given for the natural logarithm of K_14b: (g) $$[ln K_{14b} ]_T^P = - \frac{{18064.43}}{{T\left( {^\circ K} \right)}} + 38.58 + \frac{{0.308(P - 1 bar)}}{{T\left( {^\circ K} \right)}}$$ where P is the total pressure in bars and T the temperature in degrees Kelvin. Combining Equation (g) with the activities of MgCO₃ and CaCO₃ gives the equilibrium fugacity \(f_{CO_2 }\) : (i) $$[ln f_{CO_2 } ]_T^P = - \frac{{11635.44}}{{T\left( {^\circ K} \right)}} + 21.09 + \frac{{0.154(P - 1 bar)}}{{T\left( {^\circ K} \right)}}$$ Equation (i) and the fugacities of CO₂ permit to calculate the equilibrium data in terms of \(P_{CO_2 }\) and T (see Fig. 3) or P _total, T and \(X_{CO_2 }\) (see Fig. 5). Combining the \(P_{total} TX_{CO_2 }\) equilibrium data of the above reaction with those of the previously investigated reaction (Metz 1976): 1 tremolite+11 dolomite ?8 forsterite+13 calcite+9 CO₂+1 H₂O yields the stability conditions of the four-mineral assemblage: diopside+calcian dolomite+forsterite +magnesian calcite and the stability conditions of the five-mineral assemblage: tremolite+calcian dolomite+forsterite +magnesian calcite+diopside both shown in Fig. 6. Since these assemblages are by no means rare in metamorphic siliceous dolomites (Trommsdorff 1972; Suzuki 1977; Puhan 1979) the data of Fig. 6 can be used to determine the pressure of metamorphism and to estimate the composition of the CO₂-H₂O fluid provided the temperature of the metamorphic event was determined using the calcite-dolomite geothermometer.     

Early Triassic potassic volcanism in the Afyon Zone of the Anatolides/Turkey: implications for the rifting of the Neo-Tethys

Afyon Zone, which was derived from the Anatolide–Tauride platform during closure of the Neo-Tethys, is made up of pre-Mesozoic basement and unconformably overlying Triassic–Early Tertiary cover series. The Afyon Zone contains widespread metavolcanic rocks, which are dominated by rhyolite, dacite, and trachyandesite. They form a distinct volcanic succession, which is separated from the underlying Silurian–Lower Carboniferous metacarbonates and meta-siliciclastics by a regional unconformity. Trachyandesitic metavolcanics are made up of massive lava flows, pyroclastics and epiclastics, less frequently, domes and dikes, which were developed on a deeply eroded subaerial landmass. U/Pb and Pb/Pb zircon geochronology yielded Lower Triassic (~250 Ma) ages, which are interpreted as extrusion age of trachyandesitic volcanics. Based on the stratigraphic, geochronological, and geochemical data, we suggest that these Lower Triassic magmatic rocks represent an extensional tectonic setting on the northern active margin of the Gondwana, which led to the development of the northern branch of the Neo-Tethys.     

Luminescence dating of ice‐marginal deposits in northern Germany: evidence for repeated glaciations during the Middle Pleistocene (MIS 12 to MIS 6)

The exact number, extent and chronology of the Middle Pleistocene Elsterian and Saalian glaciations in northern Central Europe are still controversial. This study presents new luminescence data from Middle Pleistocene ice‐marginal deposits in northern Germany, giving evidence for repeated glaciations during the Middle Pleistocene (MIS 12 to MIS 6). The study area is located in the Leine valley south of the North German Lowlands. The data set includes digital elevation models, high‐resolution shear wave seismic profiles, outcrop and borehole data integrated into a 3D subsurface model to reconstruct the bedrock relief surface. For numerical age determination, we performed luminescence dating on 12 ice‐marginal and two fluvial samples. Luminescence ages of ice‐marginal deposits point to at least two ice advances during MIS 12 and MIS 10 with ages ranging from 461±34 to 421±25 ka and from 376±27 to 337±21 ka. The bedrock relief model and different generations of striations indicate that the older ice advance came from the north and the younger one from the northeast. During rapid ice‐margin retreat, subglacial overdeepenings were filled with glaciolacustrine deposits, partly rich in re‐worked Tertiary lignite and amber. During MIS 8 and MIS 6, the study area may have been affected by two ice advances. Luminescence ages of glaciolacustrine delta deposits point to a deposition during MIS 8 or early MIS 6, and late MIS 6 (250±20 to 161±10 ka). The maximum extent of both the Elsterian (MIS 12 and MIS 10) and Saalian glaciations (MIS 8? and MIS 6) approximately reached the same position in the Leine valley and was probably controlled by the formation of deep proglacial lakes in front of the ice sheets, preventing a further southward advance.