Geochemical and radioactivity characterization of rocks from the Rio Preto (Go) Project

The Rio Preto Project, developed by the extinct Brazilian nuclear state company, Nuclebrás, during the late 70s and early 80s, consisted of basic geological mapping and radiometric characterization by aerogeophysical gamma-ray spectrometry, without channel discrimination, of a surface area of 650 km2 located to the west of the Chapada dos Veadeiros National Park on the northeastern of Goiás State, Brazil, including the confluence area of Claro and Preto Rivers. Additionally, the natural radioelements U, Th and 40K were determined by gamma-ray spectrometry in 300 rock samples from cores of the Rio Preto Project area. The tests were conducted at LABIDRO-Isotopes and Hydrochemistry Laboratory of the Departament of Petrology and Metallogeny (DPM) of the Institute of Geosciences and Exact Sciences, UNESP, in Rio Claro, SP, Brazil. This paper reports the results of petrographic characterization and chemical analyses of major oxides (SiO2, TiO2, Al2O3, Fe2O3, MgO, MnO, K2O, Na2O, CaO and P2O5) for all samples used to determine the natural radioelements present in the region. The organic matter content results obtained by colorimetry are also reported for selected cores of different lithotypes in order to investigate the possible relationship between graphite and the radioelements uranium and thorium. Finally, uranium content and 234U/238U activity ratio data for selected samples of schists and gneisses of the Lower Member of the Ticunzal Formation suggest the influence of weathering processes in the area. © 2012 Sociedade Brasileira de Geofísica.

Sedimentary processes on the NW Iberian Continental Shelf since the Little Ice Age

The OMEX core CD110 W90, retrieved from the Douro Mud Patch (DMP) off the River Douro in the north of Portugal, records the period since the beginning of Little Ice Age (LIA). The core chronology is based upon the data attributes for Pb-210, Cs-137 and a C-14 dating from a level near the core base. Geochemical, granulometric, microfaunal (benthic foraminifera) and compositional data suggest the occurrence of precipitation changes which may have been, at least partially, influenced by the North Atlantic Oscillation (NAO), that contributes to the regulation of the ocean-atmosphere dynamics in the North Atlantic. Southwesterly Atlantic storm track is associated with the negative phases of the NAO, when the Azores High is anomalously weak, higher oceanographic hydrodynamism, downwelling events and increased rainfall generally occurs. Prevalence of these characteristics during the LIA left a record that corresponds to phases of major floods. During these phases the DMP received a higher contribution of relatively coarse-grained terrigenous sediments, enriched in quartz particles, which diluted the contribution of other minerals, as indicated by reduced concentrations of several lithogenic chemical elements such as: Al, As, Ba, Ce, Co, Cu, Fe, K, La, Li, Mg, Mn, Mo, Na, Ni, P, Rb, Sc, Sn, Th, V and Y. The presence of biogenic carbonate particles also underwent dilution, as revealed by the smaller abundance of foraminifera and correlative lower concentrations of Ca and Sr. During this period, the DMP also received an increased contribution of organic matter, indicated by higher values of lignin remains and a benthic foraminifera high productivity index, or BFHP, which gave rise to early diagenetic changes with pyrite formation. Since the beginning of the 20th century this contribution diminished, probably due to several drier periods and the impact of human activities in the river basins, e.g. construction of dams, or, on the littoral areas, construction of hard-engineering structures and sand extraction activities. During the first half of the 20th century mainly positive phases of the NAO prevailed, caused by the above normal strengthening of the subtropical high pressure centre of the Azores and the deepening of the low pressure centre in Iceland. These phases may have contributed to the reduction in the supply of both terrigenous sediments and organic matter from shallow water to the DMP. During the positive phases of the NAO, sedimentation became finer. The development of mining and industrial activities during the 20th century is marked, in this core, by higher concentrations of Pb. Furthermore, the erosion of heaps resulting from wolfram exploitation leaves its signature as a peak of W concentrations recorded in the sediments of the DMP deposited between the 1960s and the 1990s. Wolfram exploitation was an important activity in the middle part of the 20th century, particularly during the period of the Second World War. (C) 2012 Elsevier Ltd. All rights reserved.

Quantification of deformation processes in the Torlesse accretionary wedge, New Zealand

Zusammenfassung:In dieser Studie werden Deformationsprozesse im mesozoischen Torlesse Akkretionskeil (Neuseeland) quantifiziert, um Aufschluß über die Dynamik in Akkretionskeilen zu erhalten. Absolute und relative Verformungsmessungen zeigen sowohl im lokalen als auch regionalen Maßstab eine stark heterogene Deformation des Torlesse Keils. Die regionale Deformation wurde mit Hilfe einer Tensordurchschnittsberechnung, unter Benutzung einzelner lokaler Verformungsdaten, als uniaxiale Verkürzung entlang einer subvertikalen, maximalen Verkürzungsachse charakterisiert. Absolute Verformungsmessungen an niedriggradigen Metasandsteinen belegen darüber hinaus durchschnittliche Volumenverluste von ca. 20% SiO2. Volumenveränderungen in tieferkrustalen Aufschlüssen wurden mittels einer geochemischen Massenbilanzanalyse abgeschätzt. Chemische Zusammensetzungen höhergradiger Zonen weichen je nach Grad der Volumenverformung von der Protolitzusammensetzung ab und zeigen somit Verluste von 15% SiO2 an. Da Speicherorte für das gelöste Material nicht bekannt sind, muss angenommen werden, dass das Material aus dem Keil abtransportiert wurde. Die Verformungsergebnisse geben weiterhin Aufschluß über den Grad der Kopplung zwischen Akkretionskeil und subduzierter Platte. Die ermittelten Scherwerte in den Gesteinen liegen deutlich unter den zu erwartenden Scherwerten, die mittels eines einfachen Modells berechnet wurden, das sowohl verschiedene Konvergenzgeschwindigkeiten als auch Exhumierungsraten berücksichtigt. Dies belegt, dass der Torlesse Keil stark von der subduzierten pazifischen Platte entkoppelt war und die Deformation hauptsächlich durch den Fluß der Sedimente in und aus dem Keil bestimmt wurde.

Isotope geochemical and geochronologic studies of basement units in the Central Western Carpathians (Slovakia)

In dieser Arbeit werden geochronologische und isotopen-geochemische Daten zur Entwicklung der Zentralen Westlichen Karpathen präsentiert. Die Karpathen bilden die östliche Fortsetzung der Alpen und können in drei Alpine Grundgebirgsdecken unterteilt werden, von denen zwei, die Veporische und die Gemerische, bearbeitet wurden. In der Veporischen Einheit wurden polymetamorphe Grundgebirgseinheiten untersucht, um deren genaue Altersstellung zu definieren und sie isotopengeochemisch zu klassifizieren. Dagegen wurde in der der Gemerischen Einheit, welche die Veporische Einheit überlagert, ein spezialisierter S-Typ Granit im Detail untersucht, um die petrogenetischen Prozesse, die zur magmatischen Entwicklung dieses Granits geführt haben, zu identifizieren. U-Pb Datierungen an Zirkonen der Veporischen Grundgebirgseinheiten zeigen für die gesamte Veporische Einheit ordovizische Entsehungsalter an (440-470 Ma). Diese Datierungen revidieren publizierte kambrische Entstehungsalter dieses Grundgebirges. Die Isotopensignatur (epsilon Nd und 87Sr/86Sr) der ordovizischen Grundgebirgseinheiten, bestehend aus stark überprägten Amphiboliten und Gneissen, ist von der Signatur der sich im Norden anschliessenden Tatrischen Einheit gut unterscheidbar. Die Bleiisotopenzusammensetzung dieser Gesteine ist stark krustal geprägt und überschneidet sich mit der der Tatrischen Einheit. Zusammen mit den T-DM Altern sind diese Einheiten vergleichbar mit prävariskischen Einheiten der Alpen. Somit kann das ordovizische Grundgebirge zu den peri-Gondwana Terranen gezählt werden, die an einem aktiven Kontinentalrand im Norden von Gondwana gebildet wurden. In den Gesteinen der Veporischen Einheit wurde im Weiteren eine starke metamorphe überprägung und intensiver felsischer Magmatismus karbonischen Alters erkannt (320-350 Ma). Dieses Ereignis ist zeitgleich mit dem Magmatismus, welcher hauptsächlich in der sich im Norden anschliessenden Tatrischen Einheit beobachtet wird. Dieser gehört der variskischen Orogenese an. Intensive alpine Deformation und Metamorphose konnte in der südlichen Veporischen Einheit anhand der Einzelzirkondatierungen und der Isotopendaten der ordovizischen Einheiten nachgewiesen werden. Am Dlha Dolina Granit in der Gemerischen Einheit können starke Fraktionierungs- und Auto-Metasomatose-Effekte beobachtet werden. Durch die magmatische Fraktionierung wird eine Anreicherung der SEE erzeugt, wogegen die Metasomatose die SEE stark verarmt. Es kommt sogar zur Ausbildung eines Tetraden Effektes im SEE Muster, welche den starken Einfluss von Fluiden während der spät-magmatischen Phase belegt. Gesamtgesteins Pb-Pb Daten beschränken das minimale Intrusionsalter dieses Granites auf 240 Ma. Dieses Alter ist in guter übereinstimmung mit den Sr-Isotopendaten der magmatisch dominierten Gesteine, wohingegen die stark metasomatisch geprägten Gesteine ein zu radiogenes 87Sr/86Sri aufweisen. Während dieser Arbeit wurde intensiv mit der Blei-Isotopenzusammensetzung von Gesamtgesteinsproben gearbeitet. Um die Auswertung dieser Daten optimieren zu können wurde ein Computerscript für das GPL Programm Octave erstellt. Die Hauptaufgabe dieses Scripts besteht darin, Regressionen für geochronologische Anwendungen gemäss York (1969) zu berechnen. Ausserdem können mu und kappa-Werte für diese Regressionen berechnet und eine Hauptkomponentenanalyse, welche hilfreich für den Vergleich von zwei Datensätzen ist, durchgeführt werden. Am Ende der vorliegenden Arbeit wird die analytische Methode für einen Mikrowellen beschleunigten Säureaufschluss von granitoidem Material zur Bestimmung der Sr- und Nd-Isotopenzusammensetzung und der Elementkonzentrationen vorgestellt. Diese kombinierte Methode nutzt ein TIMS für die Sr und Nd Isotopenmessungen und eine Einzelkollektor-ICPMS zur Bestimmung der SEE, Rb und Sr Konzentrationen, welche mithilfe von relativen Sensitivitätsfaktoren gegenüber einem internen Standard quantifiziert werden. Diese Methode wird durch Messungen von internationalen Referenzmaterialien bewertet. Die Ergebnisse zeigen eine Reproduzierbarkeit von <10% für die Elementkonzentrationen und von <5% für Elementverhältnisse.

The influence of petrogenetic processes on the composition of Ocean Island Basalts

Ocean Island Basalts (OIB) provide important information on the chemical and physical characteristics of their mantle sources. However, the geochemical composition of a generated magma is significantly affected by partial melting and/or subsequent fractional crystallization processes. In addition, the isotopic composition of an ascending magma may be modified during transport through the oceanic crust. The influence of these different processes on the chemical and isotopic composition of OIB from two different localities, Hawaii and Tubuai in the Pacific Ocean, are investigated here. In a first chapter, the Os-isotope variations in suites of lavas from Kohala Volcano, Hawaii, are examined to constrain the role of melt/crust interactions on the evolution of these lavas. As 187Os/188Os sensitivity to any radiogenic contaminant strongly depend on the Os content in the melt, Os and other PGE variations are investigated first. This study reveals that Os and other PGE behavior change during the Hawaiian magma differentiation. While PGE concentrations are relatively constant in lavas with relatively primitive compositions, all PGE contents strongly decrease in the melt as it evolved through ~ 8% MgO. This likely reflects the sulfur saturation of the Hawaiian magma and the onset of sulfide fractionation at around 8% MgO. Kohala tholeiites with more than 8% MgO and rich in Os have homogeneous 187Os/188Os values likely to represent the mantle signature of Kohala lavas. However, Os isotopic ratios become more radiogenic with decreasing MgO and Os contents in the lavas, which reflects assimilation of local crust material during fractional crystallization processes. Less than 8% upper oceanic crust assimilation could have produced the most radiogenic Os-isotope ratios recorded in the shield lavas. However, these small amounts of upper crust assimilation have only negligible effects on Sr and Nd isotopic ratios and therefore, are not responsible for the Sr and Nd isotopic heterogeneities observed in Kohala lavas. In a second chapter, fractional crystallization and partial melting processes are constrained using major and trace element variations in the same suites of lavas from Kohala Volcano, Hawaii. This inverse modeling approach allows the estimation of most of the trace element composition of the Hawaiian mantle source. The calculated initial trace element pattern shows slight depletion of the concentrations from LREE to the most incompatible elements, which indicates that the incompatible element enrichments described by the Hawaiian melt patterns are entirely produced by partial melting processes. The “Kea trend” signature of lavas from Kohala Volcano is also confirmed, with Kohala lavas having lower Sr/Nd and La/Th ratios than lavas from Mauna Loa Volcano. Finally, the magmatic evolution of Tubuai Island is investigated in a last chapter using the trace element and Sr, Nd, Hf isotopic variations in mafic lava suites. The Sr, Nd and Hf isotopic data are homogeneous and typical for the HIMU-type OIB and confirms the cogenetic nature of the different mafic lavas from Tubuai Island. The trace element patterns show progressive enrichment of incompatible trace elements with increasing alkali content in the lavas, which reflect progressive decrease in the degree of partial melting towards the later volcanic events. In addition, this enrichment of incompatible trace elements is associated with relative depletion of Rb, Ba, K, Nb, Ta and Ti in the lavas, which require the presence of small amount of residual phlogopite and of a Ti-bearing phase (ilmenite or rutile) during formation of the younger analcitic and nephelinitic magmas.

Partial melting within the lower crust – Constraints from bulk rock geochemical data and trace element mineral analyses of granulites and migmatites from Central Finland

This PhD thesis concerns geochemical constraints on recycling and partial melting of Archean continental crust. A natural example of such processes was found in the Iisalmi area of Central Finland. The rocks from this area are Middle to Late Archean in age and experienced metamorphism and partial melting between 2.7-2.63 Ga. The work is based on extensive field work. It is furthermore founded on bulk rock geochemical data as well as in-situ analyses of minerals. All geochemical data were obtained at the Institute of Geosciences, University of Mainz using X-ray fluorescence, solution ICP-MS and laser ablation-ICP-MS for bulk rock geochemical analyses. Mineral analyses were accomplished by electron microprobe and laser ablation ICP-MS. Fluid inclusions were studied by microscope on a heating-freezing-stage at the Geoscience Center, University Göttingen. Part I focuses on the development of a new analytical method for bulk rock trace element determination by laser ablation-ICP-MS using homogeneous glasses fused from rock powder on an Iridium strip heater. This method is applicable for mafic rock samples whose melts have low viscosities and homogenize quickly at temperatures of ~1200°C. Highly viscous melts of felsic samples prevent melting and homogenization at comparable temperatures. Fusion of felsic samples can be enabled by addition of MgO to the rock powder and adjustment of melting temperature and melting duration to the rock composition. Advantages of the fusion method are low detection limits compared to XRF analyses and avoidance of wet-chemical processing and use of strong acids as in solution ICP-MS as well as smaller sample volumes compared to the other methods. Part II of the thesis uses bulk rock geochemical data and results from fluid inclusion studies for discrimination of melting processes observed in different rock types. Fluid inclusion studies demonstrate a major change in fluid composition from CO2-dominated fluids in granulites to aqueous fluids in TTG gneisses and amphibolites. Partial melts were generated in the dry, CO2-rich environment by dehydration melting reactions of amphibole which in addition to tonalitic melts produced the anhydrous mineral assemblages of granulites (grt + cpx + pl ± amph or opx + cpx + pl + amph). Trace element modeling showed that mafic granulites are residues of 10-30 % melt extraction from amphibolitic precursor rocks. The maximum degree of melting in intermediate granulites was ~10 % as inferred from modal abundances of amphibole, clinopyroxene and orthopyroxene. Carbonic inclusions are absent in upper-amphibolite facies migmatites whereas aqueous inclusion with up to 20 wt% NaCl are abundant. This suggests that melting within TTG gneisses and amphibolites took place in the presence of an aqueous fluid phase that enabled melting at the wet solidus at temperatures of 700-750°C. The strong disruption of pre-metamorphic structures in some outcrops suggests that the maximum amount of melt in TTG gneisses was ~25 vol%. The presence of leucosomes in all rock types is taken as the principle evidence for melt formation. However, mineralogical appearance as well as major and trace element composition of many leucosomes imply that leucosomes seldom represent frozen in-situ melts. They are better considered as remnants of the melt channel network, e.g. ways on which melts escaped from the system. Part III of the thesis describes how analyses of minerals from a specific rock type (granulite) can be used to determine partition coefficients between different minerals and between minerals and melt suitable for lower crustal conditions. The trace element analyses by laser ablation-ICP-MS show coherent distribution among the principal mineral phases independent of rock composition. REE contents in amphibole are about 3 times higher than REE contents in clinopyroxene from the same sample. This consistency has to be taken into consideration in models of lower crustal melting where amphibole is replaced by clinopyroxene in the course of melting. A lack of equilibrium is observed between matrix clinopyroxene / amphibole and garnet porphyroblasts which suggests a late stage growth of garnet and slow diffusion and equilibration of the REE during metamorphism. The data provide a first set of distribution coefficients of the transition metals (Sc, V, Cr, Ni) in the lower crust. In addition, analyses of ilmenite and apatite demonstrate the strong influence of accessory phases on trace element distribution. Apatite contains high amounts of REE and Sr while ilmenite incorporates about 20-30 times higher amounts of Nb and Ta than amphibole. Furthermore, trace element mineral analyses provide evidence for magmatic processes such as melt depletion, melt segregation, accumulation and fractionation as well as metasomatism having operated in this high-grade anatectic area.

Continuous geochemical monitoring by mass-spectometer in the Campi Flegrei geothermal area. An application at Pisciarelli-Solfatara (diffuse and fumarolic gases) and at the mud gases during drilling of the CFDDP pilot hole

During this work has been developed an innovative methodology for continuous and in situ gas monitoring (24/24 h) of fumarolic and soil diffusive emissions applied to the geothermal and volcanic area of Pisciarelli near Agnano inside the Campi Flegrei caldera (CFc). In literature there are only scattered and in discrete data of the geochemical gas composition of fumarole at Campi Flegrei; it is only since the early ’80 that exist a systematic record of fumaroles with discrete sampling at Solfatara (Bocca Grande and Bocca Nuova fumaroles) and since 1999, even at the degassing areas of Pisciarelli. This type of sampling has resulted in a time series of geochemical analysis with discontinuous periods of time set (in average 2-3 measurements per month) completely inadequate for the purposes of Civil Defence in such high volcanic risk and densely populated areas. For this purpose, and to remedy this lack of data, during this study was introduced a new methodology of continuous and in situ sampling able to continuously detect data related and from its soil diffusive degassing. Due to its high sampling density (about one measurement per minute therefore producing 1440 data daily) and numerous species detected (CO2, Ar, 36Ar, CH4, He, H2S, N2, O2) allowing a good statistic record and the reconstruction of the gas composition evolution of the investigated area. This methodology is based on continuous sampling of fumaroles gases and soil degassing using an extraction line, which after undergoing a series of condensation processes of the water vapour content - better described hereinafter - is analyzed through using a quadrupole mass spectrometer

Granulite facies metamorphism and partial melting processes in the Ivrea Zone, Northern Italy

The Ivrea Zone in northern Italy has been the focus of numerous petrological, geochemical and structural studies. It is commonly inferred to represent an almost complete section through the mid to lower continental crust, in which metamorphism and partial melting of the abundant metapelites was the result of magmatic underplating by a large volume of mantle-derived magma. This study concerns amphibolite and granulite facies metamorphism in the Ivrea Zone with focus on metapelites and metapsammites/metagreywackes from Val Strona di Omegna and metapelites from Val Sesia and Val Strona di Postua, with the aim to better constrain their metamorphic evolution as well as their pressure and temperature conditions via phase equilibria modelling.rnrnIn Val Strona di Omegna, the metapelites show a structural and mineralogical change from mica-schists with the common assemblage bi-mu-sill-pl-q-ilm ± liq at the lowest grades, through metatexitic migmatites (g-sill-bi-ksp-pl-q-ilm-liq) at intermediate grades, to complex diatexitic migmatites (g-sill-ru-bi-ksp-pl-q-ilm-liq) at the highest grades. Within this section several mappable isograds occur, including the first appearance of K-feldspar in the metapelites, the first appearance of orthopyroxene in the metabasites and the disappearance of prograde biotite from the metapelites. The inferred onset of partial melting in the metapelites occurs around Massiola. The prograde suprasolidus evolution of the metapelites is consistent with melting via the breakdown of first muscovite then biotite. Maximum modelled melt fractions of 30–40 % are predicted at the highest grade. The regional metamorphic field gradient in Val Strona di Omegna is constrained to range from conditions of 3.5–6.5 kbar at T = 650–730 °C to P &gt; 9 kbar at T &gt; 900 °C. The peak P–T estimates, particularly for granulite facies conditions, are significantly higher (around 100 °C) than those of most previous studies. In Val Sesia and Val Strona di Postua to the south the exposure is more restricted. P–T estimates for the metapelites are 750–850 °C and 5–6.5 kbar in Val Sesia and approximately 800–900 °C and 5.5–7 kbar in Val Strona di Postua. These results show similar temperatures but lower pressure than metapelites in Val Strona di Omegna. Metapelites in Val Sesia in contact with the Mafic Complex exhibit a metatexitic structure, while in Val Strona di Postua diatexitic structures occur. Further, metapelites at the contact with the Mafic Complex contain cordierite (± spinel) that overprint the regional metamorphic assemblages and are interpreted to have formed during contact metamorphism related to intrusion of the Mafic Complex. The lower pressures in the high-grade rocks in Val Sesia and Val Strona di Postua are consistent with some decompression from the regional metamorphic peak prior to the intrusion of the Mafic Complex, suggesting the rocks followed a clockwise P–T path. In contrast, the metapelites in Val Strona di Omegna, especially in the granulite facies, do not contain any cordierite or any evidence for a contact metamorphic overprint. The extrapolated granulite facies mineral isograds are cut by the rocks of the Mafic Complex to the south. Therefore, the Mafic Complex cannot have caused the regional metamorphism and it is unlikely that the Mafic Complex occurs in Val Strona di Omegna.

Geochemical and isotopic characterization of the Bodélé Depression dust source and implications for transatlantic dust transport to the Amazon Basin

The Bodélé Depression (Chad) in the central Sahara/Sahel region of Northern Africa is the most important source of mineral dust to the atmosphere globally. The Bodélé Depression is purportedly the largest source of Saharan dust reaching the Amazon Basin by transatlantic transport. Here, we have undertaken a comprehensive study of surface sediments from the Bodélé Depression and dust deposits (Chad, Niger) in order to characterize geochemically and isotopically (Sr, Nd and Pb isotopes) this dust source, and evaluate its importance in present and past African dust records. We similarly analyzed sedimentary deposits from the Amazonian lowlands in order to assess postulated accumulation of African mineral dust in the Amazon Basin, as well as its possible impact in fertilizing the Amazon rainforest. Our results identify distinct sources of different ages and provenance in the Bodélé Depression versus the Amazon Basin, effectively ruling out an origin for the Amazonian deposits, such as the Belterra Clay Layer, by long-term deposition of Bodélé Depression material. Similarly, no evidence for contributions from other potential source areas is provided by existing isotope data (Sr, Nd) on Saharan dusts. Instead, the composition of these Amazonian deposits is entirely consistent with derivation from in-situ weathering and erosion of the Precambrian Amazonian craton, with little, if any, Andean contribution. In the Amazon Basin, the mass accumulation rate of eolian dust is only around one-third of the vertical erosion rate in shield areas, suggesting that Saharan dust is “consumed” by tropical weathering, contributing nutrients and stimulating plant growth, but never accumulates as such in the Amazon Basin. The chemical and isotope compositions found in the Bodélé Depression are varied at the local scale, and have contrasting signatures in the “silica-rich” dry lake-bed sediments and in the “calcium-rich” mixed diatomites and surrounding sand material. This unexpected finding implies that the Bodélé Depression material is not “pre-mixed” at the source to provide a homogeneous source of dust. Rather, different isotope signatures can be emitted depending on subtle vagaries of dust-producing events. Our characterization of the Bodélé Depression components indicate that the Bodélé “calcium-rich” component, identified here, is most likely released via eolian processes of sand grain saltation and abrasion and may be significant in the overall global budget of dusts carried out by the Harmattan low-level jet during the winter.

Lithium isotope constraints on crust–mantle interactions and surface processes on Mars

Lithium abundances and isotope compositions are reported for a suite of martian meteorites that span the range of petrological and geochemical types recognized to date for Mars. Samples include twenty-one bulk-rock enriched, intermediate and depleted shergottites, six nakhlites, two chassignites, the orthopyroxenite Allan Hills (ALH) 84001 and the polymict breccia Northwest Africa (NWA) 7034. Shergottites unaffected by terrestrial weathering exhibit a range in δ7Li from 2.1 to 6.2‰, similar to that reported for pristine terrestrial peridotites and unaltered mid-ocean ridge and ocean island basalts. Two chassignites have δ7Li values (4.0‰) intermediate to the shergottite range, and combined, these meteorites provide the most robust current constraints on δ7Li of the martian mantle. The polymict breccia NWA 7034 has the lowest δ7Li (−0.2‰) of all terrestrially unaltered martian meteorites measured to date and may represent an isotopically light surface end-member. The new data for NWA 7034 imply that martian crustal surface materials had both a lighter Li isotope composition and elevated Li abundance compared with their associated mantle. These findings are supported by Li data for olivine-phyric shergotitte NWA 1068, a black glass phase isolated from the Tissint meteorite fall, and some nakhlites, which all show evidence for assimilation of a low-δ7Li crustal component. The range in δ7Li for nakhlites (1.8 to 5.2‰), and co-variations with chlorine abundance, suggests crustal contamination by Cl-rich brines. The differences in Li isotope composition and abundance between the martian mantle and estimated crust are not as large as the fractionations observed for terrestrial continental crust and mantle, suggesting a difference in the styles of alteration and weathering between water-dominated processes on Earth versus possibly Cl–S-rich brines on Mars. Using high-MgO shergottites (>15 wt.% MgO) it is possible to estimate the δ7Li of Bulk Silicate Mars (BSM) to be 4.2 ± 0.9‰ (2σ). This value is at the higher end of estimates for the Bulk Silicate Earth (BSE; 3.5 ± 1.0‰, 2σ), but overlaps within uncertainty.

Sedimentological processes and environmental variability at Lake Ohrid (Macedonia, Albania) between 637 ka and the present

Lake Ohrid (Macedonia, Albania) is thought to be more than 1.2 million years old and host more than 300 endemic species. As a target of the International Continental scientific Drilling Program (ICDP), a successful deep drilling campaign was carried out within the scope of the Scientific Collaboration on Past Speciation Conditions in Lake Ohrid (SCOPSCO) project in 2013. Here, we present lithological, sedimentological, and (bio-)geochemical data from the upper 247.8 m composite depth of the overall 569 m long DEEP site sediment succession from the central part of the lake. According to an age model, which is based on 11 tephra layers (first-order tie points) and on tuning of bio-geochemical proxy data to orbital parameters (second-order tie points), the analyzed sediment sequence covers the last 637 kyr. The DEEP site sediment succession consists of hemipelagic sediments, which are interspersed by several tephra layers and infrequent, thin (< 5 cm) mass wasting deposits. The hemipelagic sediments can be classified into three different lithotypes. Lithotype 1 and 2 deposits comprise calcareous and slightly calcareous silty clay and are predominantly attributed to interglacial periods with high primary productivity in the lake during summer and reduced mixing during winter. The data suggest that high ion and nutrient concentrations in the lake water promoted calcite precipitation and diatom growth in the epilimnion during MIS15, 13, and 5. Following a strong primary productivity, highest interglacial temperatures can be reported for marine isotope stages (MIS) 11 and 5, whereas MIS15, 13, 9, and 7 were comparably cooler. Lithotype 3 deposits consist of clastic, silty clayey material and predominantly represent glacial periods with low primary productivity during summer and longer and intensified mixing during winter. The data imply that the most severe glacial conditions at Lake Ohrid persisted during MIS16, 12, 10, and 6, whereas somewhat warmer temperatures can be inferred for MIS14, 8, 4, and 2. Interglacial-like conditions occurred during parts of MIS14 and 8.

Geochemical and physical sediment properties of sediment cores from the Portuguese shelf

Marine sediments from the Portuguese shelf are influenced by environmental changes in the surrounding continental and marine environment. These are largely controlled by the North Atlantic Oscillation, but additional impacts may arise from episodic tsunamis. In order to investigate these influences, a high resolution multi-proxy study has been carried out on a 5.4 m long gravity core and five box cores from the Tagus prodelta on the western Portuguese margin, incorporating geochemical (Corg/Ntotal ratios, d13Corg, d15N, d18O, Corg and CaCO3 content) and physical sediment properties (magnetic susceptibility, grain-size). Subsurface data of the five box cores indicate no major effect of early postdepositional alteration. Surface data show a higher fraction of terrigenous organic material close to the river mouth and in the southern prodelta. Gravity core GeoB 8903 covers the last 3.2 kyrs with a temporal resolution of at least 0.1 cm/yr. Very high sedimentation rates between 69 and 140 cm core depth indicate a possible disturbance of the record by the AD1755 tsunami, although no evidence for a disturbance is observed in the data. Sea surface temperature and salinity on the prodelta, the local budget of marine NO3- as well as the provenance of organic matter remained virtually constant during the past 3.2 kyrs. A positive correlation between magnetic susceptibility (MS) and North Atlantic Oscillation (NAO) is evident for the past 250 years, coinciding with a negative correlation between mean grain-size and NAO. This is assigned to a constant riverine supply of fine material with high MS, which is diluted by the riverine input of a coarser, low-MS component during NAO negative, high-precipitation phases. End-member modelling of the lithic grain-size spectrum supports this, revealing a third, coarse lithic component. The high abundance of this coarse end-member prior to 2 kyr BP is interpreted as the result of stronger bottom currents, concentrating the coarse sediment fraction by winnowing. As continental climate was more arid prior to 2 kyr BP (Subboreal), the coarse end-member may also consist of dust from local sources. A decrease in grain-size and CaCO3 content after 2 kyr BP is interpreted as a result of decreasing wind strength. The onset of a fining trend and a further decrease in CaCO3 around AD900 occurs simultaneous to climatic variations, reconstructed from eastern North Atlantic records. A strong increase in MS between AD1400 and AD1500 indicates higher lithic terrigenous input, caused by deforestation in the hinterland.

(Table 2) Geochemical composition of suspended matter samples from the northern Dvina River

The results of the analysis of samples of the Northern Dvina River's suspended particulate matter obtained by the sedimentation method from large water volumes in the periods of the spring high water and summer low water are presented. By the method of sequential leaching using different reagents, four fractions have been separated: the F1 is the sorbed complex and carbonates, the F2 is the amorphous hydroxides of Fe and Mn, the F3 is the form connected with the organic matter, and the F4 is the residual or silicate-detrital (inert) form. The data have shown that all ten elements determined were grouped with respect to the ratio of the distinguished forms: F4 is the predominant form for Al and Fe (73-88% of all the forms; however, the summer sample contains only 38% of this form of iron, and F2 is the predominant form for this period with 46.6%). As to Mn, the F1, F2, and F4 are nearly equally distributed in the spring high water samples, and only the F3 form is less important (5.4%). In the summer sample, the manganese sorbed complex is predominant (53.5%); for Cu, Ni, Cr, and Co, the inert F4 form is predominant (60-70%) in the sample of the spring suspended matter. The summer low water suspended matter has a lower F4 contribution (25-45%); for Zn, Pb, and Cd, the equal distribution of the forms in the spring samples is typical, while the summer suspended matter differs by the F2 form's predominance (53-61% for Zn and Pb). The main conclusion from the acquired data is that the geochemical mobility of all the studied elements, except for cadmium, in the summer low water suspended matter is higher than in the spring suspended matter. The more intensive biogeochemical processes in August, the high level of organic matter, and the higher contribution of phytoplankton lead to the intensification of the metals' geochemical activity in the Northern Dvina suspended matter in the end of the summer compared to the spring high water period when the physical processes are predominant over the biogeochemical ones due to the high speeds of the freshened waters flow.

Geochemical history at DSDP Leg 56 Holes

A geological model of subduction postulated by Karig, Ingle, et al. (1975) and Karig and Sharman (1975) proposes that the sedimentary prism at the foot of the landward wall is being actively built as sediment is scraped off the subducting oceanic and plastered onto the base of the wedge, forming an accretionary wedge containing overthrust sedimentary layers or intense sedimentary folding. Because overlying layers must continually be uplifted and compressed to accommodate new matter at the base, the accreting wedge will provide a geochemical record of this process at or near the Japan Trench. Several recent papers have discussed the metalliferous sediments on the active oceanic ridges. The geochemistry of such sediments is now reasonably well known: generally these deposits are considered products of volcanic processes (Boström and Peterson, 1969; Böstrom et al., 1969; Horowitz, 1970, 1974; Cronan et al., 1972; Cronan and Garrett, 1973). The geochemistry of subduction zone sediments, however, is less well known, and the need for studies of these sediments is particularly urgent if such sediments provide a record of the effects of subduction of oceanic plates under continental crust. Because the Japan Trench contains welldeveloped subduction zone deposits, Leg 56 sampling was of utmost importance to the discovery of how they originate.

Geochemical and biogeochemical parameters of bottom sediments from the area of the Spitsbergen (Svalbard) Archipelago

Quantitative characteristics for rates of diagenetic processes in the upper (0-30 cm) layer of sedimentary deposits in the area of the Spitsbergen (Svalbard) Archipelago (78°-80°N) were obtained by lithologo-geochemical, radioisotope (35S, 14C), and stable isotope (d34S, d13C) studies. It was proved that rates of diagenetic processes in polar deposits at 123-395 m depth affected by the East Spitsbergen ''warm'' current are mostly determined by bioproductivity and are commensurate with rates of processes in shelf deposits of temperate latitudes. High contents of migratory methane (up to 263 ml/dm**3) and isotopically-light organic carbon (Corg, d13C = -30 per mil PDB) were found in the 1 m layer of shelf deposits (at 123 m sea depth) with low bacterial in situ production of methane. It was shown that methane is not utilized in the deposits by the methanotrophic bacterial community and it may be supplied to the water mass and, probably, to the atmosphere.