Macerals in sediments

The study of particulate organic matter (OM) in Arctic Ocean sediments from the Late Cretaceous to the Eocene (IODP Expedition 302) has revealed detailed information about the aquatic/marine OM fluxes, biological sources, preservation and export of terrestrial material. Here, we present detailed data from maceral analysis, vitrinite reflectance measurements and organic geochemistry. During the Campanian/Paleocene, fluxes of land-derived OM are indicated by reworked and oxidized macerals (vitrinite, inertinite) and terrigenous liptinite (cutinite, sporinite). In the Early Eocene, drastic environmental changes are indicated by peaks in aquatic OM (up to 40-45%, lamalginite, telalginite, liptodetrinite, dinoflagellate cysts) and amorphous OM (up to 50% bituminite). These events of increased aquatic OM flux, similar to conditions favoring black shale deposition, correlate with the global d13C events "Paleocene/Eocene Thermal Maximum" (PETM) and "Elmo-event". Freshwater discharge and proximity of the source area are documented by freshwater algae material (Pediastrum, Botryococcus) and immature land-plant material (corphuminite, textinite). We consider that erosion of coal-bearing sediments during transgression time lead to humic acids release as a source for bituminite deposited in the Early Eocene black shales.

(Appendix B) Benthic foraminifera in Indian Ocean surface sediments

Multivariate analysis was performed on percentages of 46 species of unstained deep-sea benthic foraminifera from 131 core-top to near-core-top samples (322-5013 m) from across the Indian Ocean. Faunal data are combined with GEOSECS geochemical data to investigate any relationship between benthic foraminifera (assemblages and species) and deep-sea properties. In general, benthic foraminifera show a good correlation to surface productivity, organic carbon flux to the sea floor, deep-sea oxygenation and, to a lesser extent, to bottom temperature, without correlation with the water depths. The foraminiferal census data combined with geochemical data has enabled the division of the Indian Ocean into two faunal provinces. Province A occupies the northwestern Indian Ocean (Arabian Sea region) where surface primary production has a major maximum during the summer monsoon season and a secondary maximum during winter monsoon season that leads to high organic flux to the seafloor, making the deep-sea one of the most oxygen-deficient regions in the world ocean, with a pronounced oxygen minimum zone (OMZ). This province is dominated by benthic foraminifera characteristic of low oxygen and high organic food flux including Uvigerina peregrina, Robulus nicobarensis, Bolivinita pseudopunctata, Bolivinita sp., Bulimina aculeata, Bulimina alazanensis, Ehrenbergina carinata and Cassidulina carinata. Province B covers southern, southeastern and eastern parts of the Indian Ocean and is dominated by Nuttallides umbonifera, Epistominella exigua, Globocassidulina subglobosa, Uvigerina proboscidea, Cibicides wuellerstorfi, Cassidulina laevigata, Pullenia bulloides, Pullenia osloensis, Pyrgo murrhina, Oridorsalis umbonatus, Gyroidinoides (= Gyroidina) soldanii and Gyroidinoides cf. gemma suggesting well-oxygenated, cold deep water with low (oligotrophic) and pulsed food supply.

Elemental composition of various manganese nodules

Manganese nodules have been observed over wide areas of both the Pacific and Atlantic Oceans, however, deposits in the Pacific Ocean are generally much richer in elements of economic interest such as nickel, copper and cobalt. In understanding the genesis and the geochemistry involved in their formation and growth, it is important to know the total chemical composition of these nodules and how they vary within a given deposit and between deposits in the oceans of the world. The concentrations of elements: nickel, copper, cobalt, iron, manganese, silicon, and calcium, in all of the manganese nodules which have been analyzed were recently summarized by Horn et al. (1972). These observations indicate certain correlations, both positive and negative, between Mn and the associated elements within the nodules. Their data suggest similarities in chemical composition for nodules from a given area; however, the analyses of Mn nodules, like that of the ocean water, itself, has large errors associated with some of the measurements. This is understandable, since many of these measurements were intended to provide an approximate indication of elemental content. Where one is interested in carefully preparing a description of Mn nodule chemical composition which can serve as a basis for formulating theories regarding their genesis and subsequent geochemical changes in the ocean environment, then very precise and accurate analyses are essential. The purpose of this study has been to measure the concentrations of 18 elements in Mn nodules with a high degree of accuracy and determine what correlations exist between element concentrations. The scope of this study was seriously limited and therefore was confined to one area of the Pacific Ocean at approximately 22 N latitude, 114 W longitude, at an ocean depth of approximately 11,000 feet.

Plutonium release from Fukushima Daiichi fosters the need for more detailed investigations

The contamination of Japan after the Fukushima accident has been investigated mainly for volatile fission products, but only sparsely for actinides such as plutonium. Only small releases of actinides were estimated in Fukushima. Plutonium is still omnipresent in the environment from previous atmospheric nuclear weapons tests. We investigated soil and plants sampled at different hot spots in Japan, searching for reactor-borne plutonium using its isotopic ratio Pu-240/Pu-239. By using accelerator mass spectrometry, we clearly demonstrated the release of Pu from the Fukushima Daiichi power plant: While most samples contained only the radionuclide signature of fallout plutonium, there is at least one vegetation sample whose isotope ratio (0.381 +/- 0.046) evidences that the Pu originates from a nuclear reactor (Pu239+240 activity concentration 0.49 Bq/kg). Plutonium content and isotope ratios differ considerably even for very close sampling locations, e.g. the soil and the plants growing on it. This strong localization indicates a particulate Pu release, which is of high radiological risk if incorporated.

Microbiologia do ciclo do nitrogênio em solos do cerrado

Dissertação (mestrado)—Universidade de Brasília, Instituto de Ciências Biológicas, Programa de Pós-Graduação em Biologia Microbiana, 2016.

An investigation into the suitability of time-of-flight mass spectrometry in forensic toxicology

Liquid chromatography coupled with mass spectrometry is one of the most powerful tools in the toxicologist’s arsenal to detect a wide variety of compounds from many different matrices. However, the huge number of potentially abused substances and new substances especially designed as intoxicants poses a problem in a forensic toxicology setting. Most methods are targeted and designed to cover a very specific drug or group of drugs while many other substances remain undetected. High resolution mass spectrometry, more specifically time-of-flight mass spectrometry, represents an extremely powerful tool in analysing a multitude of compounds not only simultaneously but also retroactively. The data obtained through the time-of-flight instrument contains all compounds made available from sample extraction and chromatography, which can be processed at a later time with an improved library to detect previously unrecognised compounds without having to analyse the respective sample again. The aim of this project was to determine the utility and limitations of time-of-flight mass spectrometry as a general and easily expandable screening method. The resolution of time-of-flight mass spectrometry allows for the separation of compounds with the same nominal mass but distinct exact masses without the need to separate them chromatographically. To simulate the wide variety of potentially encountered drugs in such a general screening method, seven drugs (morphine, cocaine, zolpidem, diazepam, amphetamine, MDEA and THC) were chosen to represent this variety in terms of mass, properties and functional groups. Consequently, several liquid-liquid and solid phase extractions were applied to urine samples to determine the most general suitable and unspecific extraction. Chromatography was optimised by investigating the parameters pH, concentration, organic solvent and gradient of the mobile phase to improve data obtained by the time-of-flight instrument. The resulting method was validated as a qualitative confirmation/identification method. Data processing was automated using the software TargetAnalysis, which provides excellent analyte recognition according to retention time, exact mass and isotope pattern. The recognition of isotope patterns allows excellent recognition of analytes even in interference rich mass spectra and proved to be a good positive indicator. Finally, the validated method was applied to samples received from the A& E Department of Glasgow Royal Infirmary in suspected drug abuse cases and samples received from the Scottish Prison Service, which we received from their own prevalence study targeting drugs of abuse in the prison population. The obtained data was processed with a library established in the course of this work.

GEOCHEMISTRY AND GEOCHRONOLOGY OF SURFICIAL ACRE BASIN SEDIMENTS (WESTERN AMAZONIA): KEY INFORMATION FOR CLIMATE RECONSTRUCTION.

Geochemical and geochronological analyses of samples of surficial Acre Basin sediments and fossils indicate an extensive fluvial-lacustrine system, occupying this region, desiccated slowly during the last glacial cycle (LGC). This research documents direct evidence for aridity in western Amazonia during the LGC and is important in establishing boundary conditions for LGC climate models as well as in correlating marine and continental (LGC) climate conditions.

Geochemistry and stable isotope composition of fresh alkaline porphyry copper tailings: Implications on sources and mobility of elements during transport and early stages of deposition

Prevention of acid mine drainage (AMD) in sulfide-containing tailings requires the identification of the geochemical processes and element pathways in the early stages of tailing deposition. However, analyses of recently deposited tailings in active tailings impoundments are scarce because mineralogical changes occur near the detection limits of many assays. This study shows that a detailed geochemical study which includes stable isotopes of water (delta H-2, delta O-18), dissolved sulfates (delta S-34, delta O-18) and hydrochernical parameter (pH, Eh, DOC, major and trace elements) from tailings samples taken at different depths in rainy and dry seasons allows the understanding of weathering (oxidation, dissolution, sorption, and desorption), water and element pathways, and mixing processes in active tailings impoundments. Fresh alkaline tailings (pH 9.2-10.2) from the Cu-Mo porphyry deposit in El Teniente, Chile had low carbonate (0.8-1.1 Wt-% CaCO3 equivalent) and sulfide concentrations (0.8-1.3 wt.%, mainly as pyrite). In the alkaline tailings water, Mo and Cu (up to 3.9 mg/L Mo and 0.016 mg/L Cu) were mobile as MoO42- and Cu (OH)(2)(0). During the flotation, tailings water reached equilibrium with gypsum (up to 738 mg/L Ca and 1765 mg/ L SO4). The delta S-34 VS. delta O-18 covariations of dissolved sulfate (2.3 to 4.5% delta S-34 and 4.1 to 6.0 % delta O-18) revealed the sulfate sources: the dissolution of primary sulfates (12.0 to 13.2%. delta S-34, 7.4 to 10.9%.delta O-18) and oxidation of primary sulfides (-6.7 to 1.7%. delta S-34). Sedimented tailings in the tailings impoundment can be divided into three layers with different water sources, element pathways, and geochemical processes. The deeper sediments (> 1 m depth) were infiltrated by catchment water, which partly replaced the original tailings water, especially during the winter season. This may have resulted in the change from alkaline to near-neutral pH and towards lower concentrations of most dissolved elements. The neutral pH and high DOC (up to 99.4 mg/L C) of the catchment water mobilized Cu (up to 0.25 mg/L) due to formation of organic Cu complexes; and Zn (up to 130 mg/L) due to dissolution of Zn oxides and desorption). At I m depth, tailings pore water obtained during the winter season was chemically and isotopically similar to fresh tailings water (pH 9.8-10.6, 26.7-35.5 mg/L Cl, 2.3-6.0 mg/L Mo). During the summer, a vadose zone evolved locally and temporarily up to 1.2 m depth. resulting in a higher concentration of dissolved solids in the pore water due to evaporation. During periodical new deposition of fresh tailings, the geochemistry of the surface layer was geochemically similar to fresh tailings. In periods without deposition, sulfide oxidation was suggested by decreasing pH (7.7-9.5), enrichment of MoO42- and SO42-, and changes in the isotopic composition of dissolved sulfates. Further enrichment for Na, K, Cl, SO4, Mg, Cu, and Mo (up to 23.8 mg/L Mo) resulted from capillary transport towards the surface followed by evaporation and the precipitation of highly soluble efflorescent salts (e.g., mirabilite, syngenite) at the tailing surface during summer. (C) 2008 Elsevier B.V. All rights reserved.

Discovery of an albite gneiss from the Ile de Groix (Armorican Massif, France): Geochemistry and LA-ICP-MS U-Pb geochronology of its Ordovician protolith

For the first time, an albite orthogneiss has been recognised and dated within the HP-LT blueschist facies metabasites and metapelites of the Ile de Groix. It is characterised by a peraluminous composition, high LILE, Th and U contents, MORB-like HREE abundances and moderate Nb and Y values. A U-Pb age of 480.8 +/- A 4.8 Ma was obtained by LA-ICP-MS dating of zircon and titanite. It is interpreted as the age of the magmatic emplacement during the Early Ordovician. Morphologically different zircon grains yield late Neoproterozoic ages of 546.6-647.4 Ma. Zircon and titanite U-Pb ages indicate that the felsic magmatism from the Ile de Groix is contemporaneous with the acid, pre-orogenic magmatism widely recognised in the internal zones of the Variscan belt, related to the Cambro-Ordovician continental rifting. The magmatic protolith probably inherited a specific chemical composition from a combination of orogenic, back-arc and anorogenic signatures because of partial melting of the Cadomian basement during magma emplacement. Besides, the late Devonian U-Pb age of 366 +/- A 33 Ma obtained for titanite from a blueschist facies metapelite corresponds to the age of the HP-LT peak metamorphism.

Geochemistry and 40Ar/39Ar geochronology of pseudotachylyte associated with UHP whiteschists from the Dora Maira massif, Italy

In situ UV-Iaser ablation Ar-40/(39) Ar geochronological and geochemical data, together with rock and mineral compositional data, have been determined from pseudotachylyte and surrounding mylonitic gneiss associated with the UHP whiteschists of the Dora Maira Massif, Italy. Several generations of fresh pseudotachylyte occur as irregular veins up to a few cur thick both parallel and at high angles to the foliation. Whole rock XRF data collected from representative lithologies of mylonitic gneiss are uniformly consistent with a mildly alkalic granitic protolith. Minimal compositional variation is observed between the pseudotachylyte and its surrounding mylonitic gneiss. The pseudotachylyte contains newly crystallized grains of biotite and K-feldspar in a matrix of glass with partially fused grains of quartz, zircon, apatite, and titanite. Electron microprobe analyses of the glass show significant compositional variation that is probably strongly influenced by micrometer-scale changes in mineralogy. UV-Iaser ablation ICP-MS traverses across the mylonitic gneiss-pseudotachylyte contact are consistent with cataclastic communition of REE carriers such as epidote, monazite, allanite, zircon, and apatite before melting as an efficient mechanism of REE homogenization in the pseudotachylyte. The 40Ar/39Ar data from one band of pseudotachylyte indicate formation at 20.1 +/- 0.5 Ma, when the mylonitic gneisses were already in a near surface position. The variable effects of top-to-the-west shear deformation within outcrops of the coesite-bearing unit are reflected in localized zones of protomylonite, cataclasite, ultracataclasite, and pseudotachylyte. Preservation of several generations of pseudotachylyte suggests that seismic events may have played a significant role in triggering late unroofing of the UHP rocks. It is speculated that deeper crustal seismic events potentially played a role in the unroofing of the UHP rocks at earlier stages in their exhumation history. (c) 2005 Elsevier B.V. All rights reserved.