Particulate content of savanna fire emissions

As part of the FOS-DECAFE experiment at Lamto (Ivory Coast) in January 1991, various aerosol samples were collected at ground level near prescribed fires or under local background conditions, to characterize the emissions of particulate matter from the burning of savanna vegetation. This paper deals with total aerosol (TPM) and carbon measurements. Detailed trace element and polycyclic hydrocarbon data are discussed in other papers presented in this issue.Near the fire plumes, the aerosols from biomass burning are primarily of a carbonaceous nature (C%70% of the aerosol mass) and consist predominantly of submicron particles (more than 90% in mass.) They are characterized by their organic nature (black to total carbon ratio Cb/Ct in the range 3–20%) and their high potassium content (K/Cb0.6). These aerosols undergo aging during their first minutes in the atmosphere causing slight alterations in their size distribution and chemical composition. However, they remain enriched in potassium (K/Cb=0.21) and pyrene, a polycyclic aromatic hydrocarbon, such that both of these species may be used as tracers of savanna burning aerosols. We show that during this period of the year, the background atmosphere experiences severe pollution from both terrigenous sources and regional biomass burning (44% of the aerosol). Daynight variations of the background carbon concentrations suggest that fire ignition and spreading occur primarily during the day. Simultaneous TPM and CO₂ real-time measurements point to a temporal and spatial heterogeneity of the burning so that the ratio of the above background concentrations (TPM/CO₂) varies from 2 to 400 g/kg C. Smoldering processes are intense sources of particles but particulate emissions may also be important during the rapidly spreading heading fires in connection with the generation of heavy brown smoke. We propose emission factor values (EF) for aerosols from the savanna biomass burning aerosols: EF (TPM)=11.4±4.6 and 69±25 g/kg C_{dry plant} and EF(Ct)=7.4±3.4 and 56±16 g C/kg C_{dry plant} for flaming and smoldering processes respectively. In these estimates, the range of uncertainty is mostly due to the intra-fire variability. These values are significantly lower than those reported in the literature for the combustion of other types of vegetation. But due to the large amounts of vegetation biomass being burnt in African savannas, the annual flux of particulate carbon into the atmosphere is estimated to be of the order of 8 Tg C, which rivals particulate carbon emissions from anthropogenic activities in temperate regions.     

Early miocene post-collisional calc-alkaline magmatism along the easternmost segment of the periadriatic fault system (Slovenia and Croatia)

Summary Early Miocene calc-alkaline igneous rocks from the easternmost segment of the Periadriatic fault system can be subdivided into two series of different alkalinity: (1) Volcanics which occur in the vicinity of the Velenje-Rogatec Line range from high-alumina basalt via low-K and medium-K andesites to medium-K dacites. (2) In the Pohorje Mountains mafic rocks are lacking. A high-K tonalitic pluton crystallized at pressures of about 0.7 GPa as indicated by Al-in-hornblende barometry and accessory magmatic epidote. Rapid exhumation of the tonalite during dextral transtension along the Periadriatic fault system is indicated by tonalitic pebbles in Helvetian (?) clastic sediments. High-K andesitic to dacitic volcanics are interlayered with, and dikes cut, the clastic sediments.Compositional variations shown by the volcanics from the Velenje-Rogatec Line are consistent with fractionation of the observed phenocryst assemblages (olivine, plagioclase, clinopyroxene, orthopyroxene, titanomagnetite). Substantial fractionation of plagioclase is indicated by decreasing Sr/Nd and Sr/Y values and increasing negative Eu anomalies with increasing SiO₂. All samples have chondrite-normalized HREE > 9.6 and low (Tb/Yb)_n ratios (1.29–1.08). With increasing SiO₂, the abundances of HREE and Y (18 to 39 ppm) increase and those of Sc (32.5 to 20.9 ppm) decrease slightly. These features, together with low Hf/Lu and Zr/Y values (10.1–5.7 and 5.7–3.6, respectively), rule out garnet as a major fractionating phase. Since (La/Yb)_n values (3.24–6.59) do not increase with SiO₂ and chondrite-normalized REE patterns do not show concave-upward shapes, fractionation of amphibole was probably insignificant. Although Rb/Cs values ( 18) are generally low, a significant contribution by continental crustal materials to the magmas by an AFC process is suggested by negative correlations of Nb/U(7.16 to 3.14) and Nb/Th(2.14 to 0.87) values with SiO₂, as well as by low Hf/Ta(7.8–3.4), and in part also by K/Rb (340-71) and Zr/Rb (5.0–1.7) values.Rocks from the Pohorje Mountains have high abundances of U. Values of Nb/U and Nb/Th are low (3.55 to 1.85 and 1.27 to 0.64, respectively) and are negatively correlated with SiO₂. These features, in combination with high values of Ba/Nb (56 to 93), Ba/La (23–30), and Rb/Cs (19–56), as well as with previously published ¹⁸O values ( 9) for the tonalite indicate a substantial contribution of the continental crust to these magmas. High Sr abundances (455 to 984 ppm) and moderate negative Eu anomalies suggest that fractionation of plagioclase was of minor importance. Although the rocks have relatively low Sc (9.3 to 3.8 ppm) and Y (21 to 14 ppm) contents, low (Tb/Yb)_n values (1.67–1.14) indicate that garnet was not a major fractionating phase. Instead, fractionation of amphibole is a viable mechanism to explain the combination of high (La/Yb)_n (21.8–13.1) and low (Tb/Yb)_n.

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Untermiozäner, kalkalkaliner Post-Kollisions-Magmatismus entlang des östlichsten Segmentes des periadriatischen Störungssystems (Slowenien und Kroatien)

Zusammenfassung Untermiozäne Kalkalkali-Magmatite aus dem östlichen Bereich des Periadriatischen Lineaments gliedern sich in zwei Serien unterschiedlicher Alkalinität: (1) Entlang der Velenje-Rogatec-Linie treten High-Al-Basalte, Low-K- und Medium-K-Andesite und Medium-K-Dazite auf. (2) Im Pohorje-Gebirge, wo basische Magmatite fehlen, kristallisierte ein High-K-Tonalit bei Drücken von ca. 0.7 GPa (Al-in-Hornblende-Barometer, magmatischer Epidot). Gerölle dieses Tonalits in einer untermiozänen (Helvet?) klastischeu Abfolge belegen eine schnelle Heraushebung des Tonalits durch dextrale Transtension im östlichsten Bereich des periadriatischen Lineaments. Eingeschaltet in die klastischen Sedimente sind andesitische bis dazitische Pyroklastika und Laven sowie diskordante dazitische Gänge, die alle der High-K-Serie angehören.Die chemische Variation innerhalb der Vulkanitserie von der Velenje-Rogatec-Linie läßt sich durch Fraktionierung der Einsprenglingsminerale Olivin, Plagioklas, Klinopyroxen, Orthopyroxen und Titanomagnetit erklären. Abnehmende Sr/Nd- und Sr/Y-Werte und zunehmende negative Eu-Anomalien mit steigendem SiO₂ weisen auf eine bedeutende Plagioklas-Fraktionierung hin. Alle Vulkanite besitzen hohe Gehalte an schweren Seltenen Erden (chondritnormiert > 9.6) und geringe (Tb/Yb)_n-Werte (1.29–1.08). Mit zunehmendem SiO₂ nehmen die Gehalte an Yb(2.02 bis 4.30 ppm) und Y(18 bis 39 ppm) zu, während die Sc-Gehalte (32.5 bis 20.9 ppm) nur geringfügig abnehmen. Diese Charakteristika, zusammen mit geringen Hf/Lu- und Zr/Y-Werten (10.1–5.87 bzw. 5.7–3.6), schließen Granat als wesentliche, fraktionierende Phase aus. Da die (La/Yb)_n-Verhältnisse (3.24–6.59) nicht mit SiO₂ korrelieren und die chondritnormierten SeltenenErden-Muster keine nach oben konkaven Formen aufweisen, spielte die Fraktionierung von Amphibol keine wesentliche Rolle. Trotz geringer Rb/Cs-Werte ( 18) wird eine beträchtliche krustale Kontamination der Magmen angenommen. Für einen AFC-Prozeß sprechen negative Korrelationen von Nb/U(7.16–3.14) und Nb/Th(2.14–0.87) mit SiO₂ (bei steigenden Nb-, U- und Th-Gehalten), geringe Hf/Ta-Werte (7.8–4.3) und teilweise auch geringe K/Rb- (340-71) und Zr/Rb-Verhältnisse (5.0–1.7).Die Magmatite des Pohorje-Gebirges weisen hohe U-Gehalte sowie geringe Nb/U-und Nb/Th-Verhältnisse auf (3.55–1.85 bzw. 1.27–0.64), die eine schwache negative Korrelation mit SiO₂ zeigen. Zusammen mit hohen Ba/Nb-(56–93), Ba/La-(23-30) und Rb/Cs-Verhältnissen (19–56) sowie bereits publizierten ⁸O-Werten ( 9) weisen diese Eigenschaften auf einen beträchtlichen Anteil assimilierten Krustenmaterials in den Magmen hin. Hohe Sr-Gehalte (455–984 ppm) und relativ geringe negative Eu-Anomalien machen es unwahrscheinlich, daß während des AFC-Prozesses in der Unterkruste wesentliche Mengen an Plagioklas fraktioniert wurden. Obwohl die Gehalte an Sc (9.3–3.8 ppm) und Y (21–14 ppm) relativ gering sind, scheidet Granat aufgrund der geringen (Tb/Yb)_n- Verhältnisse (1.67–1.14) als dominierende Fraktionierungsphase aus. Die Kombination von hohen (La/Yb)_n- Verhältnissen (21.8–13.1) und geringen (Tb/Yb)_n-Verhältnissen deutet eher auf Amphibol als wichtige, fraktionierende Phase hin.

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Geochemical and structural evolution of micas in the Rožná and Dobrá Voda pegmatites,Czech Republic

Summary The chemistry, structural parameters, polytypism, optical properties and Rb-Sr isotopes were examined in 11 to 60 samples of biotite, muscovite and lepidolite from the pegmatites at Roná (the type locality of lepidolite; 323 ± 4Ma) and Dobrá Voda (306 ± 9Ma) in western Moravia. At both localities, early endocontact biotite is followed inwards by muscovite and lepidolite, which is concentrated in and around the core. At Roná, a 1M lepidolite follows after 2M₁ muscovite but all later generations of lepidolite are 2M₂, close to Tri₅₀ Ply₅₀ and in part associated with muscovite 2M₁. At Dobrá Voda, all lepidolite types are 1M and free of muscovite, and the late varieties approximate Tri₃₀ Ply₇₀. At both localities, a trend of increasing HF is indicated during the progress of mica crystallization, culminating in precipitation of topaz. Polytypism of lepidolite is not correlatable with any compositional or growth feature, or their combination. Throughout the mica crystallization, Rb/Cs decreases but K/Rb becomes reversed after an initial decrease. Boron is partitioned preferentially into muscovite (up to 1.10 wt.% B₂O₃) but Be, Zn, Mn and Sc are enhanced in lepidolite. A slight increase in Fe, Ba and Cl in the last generation of lepidolite might be possibly due to mixing of residual pegmatite fluids with metamorphic pore solutions.

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Geochemische und strukturelle Entwicklung der Glimmer in den Pegmatiten von Roná und Dobrá Voda, Tschechische Republik

Zusammenfassung In 11 bis 60 Proben von Biotit, Muskovit und Lepidolith aus den Pegmatiten von Roná (Typlokalität des Lepidoliths; 323 ± 9 Ma) in Westmähren wurden Chemie, Struktur-parameter, Polytypie, optische Eigenschaften und Rb-Sr-Isotopie untersucht. An beiden Lokalitäten wird früher Biotit an Endokontakten nach Innen von Muskovit und Lepidolith gefolgt, letzterer ist in und um den Kern konzentriert. In Roná folgt 1M-Lepidolith auf 2M₁-Muskovit, aber alle späteren Lepidolithgenerationen sind 2M₂, nahe Tri₅₀Ply₅₀ und zum Teil mit 2M₁-Muskovit vergesellschaftet. In Dobrá Voda sind alle Lepidolithe vom Typ 1M und frei von Muskovit, die späten Varietäten kommen Tri₅₀Ply₅₀ nahe. An beiden Lokalitäten ist während des Fortschreitens der Glimmerkristallisation eine Tendenz von steigendem HF angezeigt, die in der Ausfällung von Topas ihren Höhepunkt findet. Die Polytypie des Lepidoliths kann nicht mit irgendeiner Eigenheit der Zusammensetzung oder des Wachstums korreliert worden, auch nicht mit einer Kombination von diesen. Während der ganzen Glimmerkristallisation nimmt Rb/Cs ab, aber die Tendenz von K/Rb ändert sich nach anfänglichem Abfall. Das Bor verteilt sich bevorzugt auf den Muskovit (bis zu 1.10 Gew. -% B₂O₃), aber die Be-, Zn-, Mn- und Sc-Gehalte sind im Lepidolith erhöht. Ein leichter Ansteig von Fe, Ba und Cl in der letzten Lepidolithgeneration könnte vielleicht durch eine Mischung von pegmatitischen Restlösungen mit metamorphen Porenlösungen verursacht sein.

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Probabilistic seismic hazard zonation of Syria

Earthquake hazard maps for Syria are presented in this paper. The Peak Ground Acceleration (PGA) and the Modified Mercalli Intensity (MMI) on bedrock, both with 90% probability of not being exceeded during a life time of 50, 100 and 200 years, respectively are developed. The probabilistic PGA and MMI values are evaluated assuming linear sources (faults) as potential sources of future earthquakes. A new attenuation relationship for this region is developed. Ten distinctive faults of potential earthquakes are identified in and around Syria. The pertinent parameters of each fault, such as theb-parameter in the Gutenberg-Richter formula, the annual rate ₄ and the upper bound magnitudem ₁ are determined from two sets of seismic data: the historical earthquakes and the instrumentally recorded earthquake data (AD 1900–1992). The seismic hazard maps developed are intended for preliminary analysis of new designs and seismic check of existing civil engineering structures.     

Metamorphism, Fluid Flow and Partial Melting in Pelitic Rocks from the Onawa Contact Aureole, Central Maine, USA

Field, petrologic and geochemical data were used to characterizefluid infiltration and partial melting during metamorphism ofpelitic rocks in the contact aureole of the Onawa pluton, centralMaine, USA. Mineral assemblages delineate five metamorphic zoneswithin the contact aureole: chlorite zone, andalusite–cordierite(a–c) zone, alkali feldspar zone, sillimanite zone andleucocratic-vein (l–v) zone. The sequence of observedmineral assemblages and mineral–fluid reactions calculatedby mass balance is similar to those observed in other contactaureoles. Pressure of contact metamorphism is 3 kbar, on thebasis of optimum geothermobarometry calculations. Metamorphictemperatures vary from 500C in the andalusite–cordieritezone to 65OC in the leucocratic-vein zone. Data from fieldobservations, mineral textures, observed reaction stoichiometry,geothermometry and major-element geochemistry suggest that theleucocratic veins of the l-v zone represent crystallized, partialmelts. Two overall calculated mineral reactions are responsiblefor vein formation: which can be modeled as combinations of two NKFMTASH meltingreactions: Progress of (M1) and (M2) was measured in eight samples, andreaction (M1) is the dominant melt-forming reaction in all samples.Partial melting (and vein formation) was therefore driven byinfiltration of the l-v zone by H²O-rich fluids. Calculatedtime-integrated fluid fluxes for l-v zone samples range from09 10⁴ to 31 10⁴ mol/cm², and flow was in the directionof increasing temperature. KEY WORDS: pelites; contact metamorphism; fluid infiltration; partial melting; Onawa Pluton; Maine; USA ^*Corresponding author. Telephone:(516) 632–8192. Fax (516)632–8240 e-mail: gsymmes{at}ccmail.sunysb.edu     

A study of bernalite,Fe(OH)3, using Mössbauer spectroscopy,optical spectroscopy and transmission electron microscopy

To study the crystal chemistry of bernalite, Fe(OH)₃, and the nature of the octahedral Fe³⁺ environment, Mössbauer spectra were recorded from 80 to 350 K, optical spectra were recorded at room temperature and a sample was studied using transmission electron microscopy. The Mössbauer spectrum of bernalite consists of a single six-line magnetic spectrum at 80 K. A broadened six-line magnetic spectrum with significantly less intensity is observed at higher temperatures, and is attributed to a small fraction of bernalite occurring as small particles. The variation of hyperfine magnetic field data for bulk bernalite with temperature is well described by the Weiss molecular field model with parameters of H ₀ = 55.7±0.3 T and T _N = 427±5K. The centre shift data were fitted to the Debye model with parameters ₀=0.482±0.005 mm/s (relative to -Fe) and _M=492±30 K. The quadrupole shift is near zero at 300 K, and does not vary significantly with temperature. Absorption spectra in the visible and near infrared range show three crystal field bands of Fe³⁺ at 11 300, 16000 and 23 200 cm^-1, giving a crystal field splitting of 14 570 cm^-1 and Racah parameters of B=629 cm^-1 and C=3381 cm^-1. Infrared reflection spectra show two distinct OH-stretching frequencies, which could correspond to two structurally different types of OH groups. A band was also observed at 2250 cm^-1, suggesting the presence of molecular CO₂ in the large cation site. Analytical transmission electron microscopy indicates that Si occurs within the bernalite structure as well as along domain boundaries. Electron diffraction and imaging show that bernalite is polysynthetically twinned along {100} planes with twin domains ranging from 3 to 20 nm in thickness. Results are discussed with respect to the nature of the octahedral Fe³⁺ site, and compared with values for other iron oxides and hydroxides.     

Oxygen and carbon isotopic study on the genesis of the Steirischer Erzberg siderite deposit (Austria)

The carbon and oxygen isotopic composition of Fe-carbonate ore and its calcitic to dolomitic Devonian host rocks at the Steirischer Erzberg siderite deposit (Greywacke zone, Upper Austroalpine Unit) were determined in order to constrain the source and nature of the Fe-rich mineralizing fluid. The ¹⁸O-values obtained for various Fe-carbonate generations and the carbonate host lie within a similar range between + 14.6 and + 21.6 (V-SMOW). No good correlation exists between the relative ages of the carbonate phases and their O isotopic composition. The variation in ¹⁸O-values is due to metamorphic recrystallization with locally variable fluid/rock ratios. The average ¹³C-value of the carbonate host is +0.5 ± 1.2 (PDB) which corresponds well to worldwide Phanerozoic marine carbonate values. The first Fecarbonate generation has slightly lower ¹³C-values, on average -1.4 ± 0.8 (PDB). Recrystallization of both the carbonate host minerals and the ankerite/siderite led to significantly lower ¹³C-values of -4.2 ± 0.6 and-4.7 ± 0.7, respectively. Within the basal breccia of the post-Hercynian transgression series matrix calcite/ dolomite shows an average ¹³C-value of -2.9 ± 0.7, and matrix siderite/ankerite an average value of-4.1 ± 0.4. These data, together with Sr isotope data published previously, strongly support a late-diagenetic or epigenetic first Fe-mineralization from convecting formation waters. They ascended along extension faults and were driven by an increased heat flow caused by crustal thinning during a Devonian rifting phase that initiated the separation of the Noric terrane from Africa. A potential source of the Fe could have been the underlying Ordovician acid volcanics. Regional metamorphism related to collision tectonics in the Late Carboniferous (Hercynian) and later during the Alpine orogeny, caused intensive recrystallization and partial mobilization of the various carbonate phases.     

Radiometric constraints on hydrothermal circulation in cooling granite plutons

Improved precision of radiometric dating of ore deposits can provide information about the thermal history of hydrothermal circulation in cooling plutons. In Jales a Hercynian porphyritic two-mica granite and pre-Ordovician mica schists are cut and intensely altered by the Campo gold-quartz vein. The unaltered granite must be younger than 320 ± 6 Ma, and gives mica Rb-Sr ages of 308.5 ± 2.4 (1) Ma (muscovite) and 294.5 ± 1.1 Ma (biotite). Alteration muscovites from the granite give a weighted mean Rb-Sr age of 308.1 ± 1.5 Ma, and a mean ³⁹Ar-⁴⁰Ar age of 300.7 ± 2.8 Ma. Alteration muscovites from the mica schists give similar ³⁹Ar-⁴⁰Ar ages, averaging 303.0 ± 2.8 Ma. The results suggest that circulation of the Campo mineralising fluids took place no more than 2–4 Ma after the granite cooled through the muscovite Rb-Sr closure temperature, about 500 °C, and that subsequent cooling to biotite closure at about 300 °C took place at less than 14°C/Ma. The mean cooling rate following emplacement was 15 to 25 °C/Ma. The most detailed comparable published data, for the Cornubian ore field, imply much faster cooling rates.     

Powder- and single crystal Mössbauer spectroscopy on synthetic fayalite

Mössbauer measurements on synthetic iron orthosilicate Fe₂SiO₄ (fayalite) were carried out in the antiferromagnetic spin state below T _N 65 K. The Mössbauer parameters isomer shift , inner magnetic field H(0), angle between H(0) and the z-component of the electric field gradient (efg), quadrupole splitting QS and asymmetry parameter were determined as a function of temperature. These parameters could be attributed to the two crystallographic sites M1 and M2.The smaller isomer shift on M1 with respect to M2 displays the more covalent character of the Fe-O bond on M1, which is supported by previous neutron diffraction experiments. H(0) shows a Brillouin-type behaviour with different fields on the two crystallographic sites (stronger on M1) and a small discontinuity at T = 23 K which corresponds with previous magnetic measurements. The quadrupole splitting is equal on both sites within error bars, in agreement with previous theoretical results and in contradiction to previous Mössbauer refinements published elsewhere.     

Mineralogical and geochemical compositions of modern bivalve shells from the Mediterranean coast of Egypt

The stable isotopic composition (¹³C and ¹⁸O) and elemental (Sr and Mg) of marine molluscs are presented for Carditacea and Solenacea shells collected off the Mediterranean coast of Egypt. Based on shell microstructures and mineralogy, the bivalve shells are preserved in their original mineralogy and chemistry.The Sr and Mg concentrations of the bivalve shells have mean values of 1960 ppm and 226 ppm respectively. The stable isotopic composition generally show high values of ¹⁸O and ¹³C. The ¹⁸O values range from +0.1 to –1.8 PDB and most shells are highly enriched in¹³C; averaging +2.5 PDB. These elemental and isotopic signatures are analogous to modern marine bivalves from other localities.The oxygen and carbon isotopes, together with the calculated temperatures, suggest that the aragonitic bivalve shells were precipitated in isotopic equilibrium from warm marine waters.