abstract: Banded iron formations (BIFs) are among the earliest possible indicators for oxidation of the Archean biosphere. However, the origin of BIFs remains debated. Proposed formation mechanisms include oxidation of Fe(II) by O2 (Cloud, 1973), photoferrotrophy (Konhauser et al., 2002), and abiotic UV photooxidation (Braterman et al., 1983; Konhauser et al., 2007). Resolving this debate could help determine whether BIFs are really indicators of O2, biological activity, or neither. To examine the viability of abiotic UV photooxidation of Fe, laboratory experiments were conducted in which Fe-bearing solutions were irradiated with different regions of the ultraviolet (UV) spectrum and Fe oxidation and precipitation were measured. The goal was to revisit previous experiments that obtained conflicting results, and extend these experiments by using a realistic bicarbonate buffered solution and a xenon (Xe) lamp to better match the solar spectrum and light intensity. In experiments reexamining previous work, Fe photooxidation and precipitation was observed. Using a series of wavelength cut-off filters, the reaction was determined not to be caused by light > 345 nm. Experiments using a bicarbonate buffered solution, simulating natural waters, and using unbuffered solutions, as in prior work showed the same wavelength sensitivity. In an experiment with a Xe lamp and realistic concentrations of Archean [Fe(II)], Fe precipitation was observed in hours, demonstrating the ability for photooxidation to occur significantly in a simulated natural setting. These results lead to modeled Fe photooxidation rates of 25 mg Fe cm-2 yr-1—near the low end of published BIF deposition rates, which range from 9 mg Fe cm-2 yr-1 to as high as 254 mg Fe cm-2 yr-1 (Konhauser et al., 2002; Trendall and Blockley, 1970). Because the rates are on the edge and the model has unquantified, favorable assumptions, these results suggest that photooxidation could contribute to, but might not be completely responsible for, large rapidly deposited BIFs such those in the Hamersley Basin. Further work is needed to improve the model and test photooxidation with other solution components. Though possibly unable to fully explain BIFs, UV light has significant oxidizing power, so the importance of photooxidation in the Archean as an environmental process and its impact on paleoredox proxies need to be determined. / Dissertation/Thesis / Masters Thesis Biochemistry 2017

Memoria para optar al título de Geólogo / En la región de Pilbara, Australia, hay una gran cantidad de depósitos de hierro. En la zona destaca un depósito coluvial, cuyo material está siendo estudiado para ser utilizado en obras civiles. El objetivo de este estudio es caracterizar mineralógica y geotécnicamente el material. Para caracterizar el material se hizo una clasificación granulométrica, se describió geológicamente el material y se analizó los datos de un triaxial gigante realizados por IDIEM que aún no han sido publicados. A modo de entender los procesos internos de lo que ocurre en el triaxial, se hizo dos ensayos especiales: un corte directo entre dos rocas y un corte directo entre roca y suelo. La caracterización del material granular grueso se basó en descripciones macroscópicas de partículas, descripciones microscópicas de cortes transparentes y pulidos y determinación de propiedades físicas (densidad, absorción y porosidad). La resistencia de las partículas se estimó mediante ensayos de carga puntual y martillo de Schmidt. Adicionalmente, el material grueso se sometió a un ensayo de desgaste (slake). La mineralogía del material fino se caracterizó a través de un análisis de difracción de rayos x y espectrometría por infrarrojo (FTIR). Las principales conclusiones de este estudio son: el material se clasificó como gravas bien graduadas, GW, el ángulo de fricción del material es 30,15°, el ángulo de fricción entre roca-roca varía entre 11,2° y 15,4°, y el ángulo de fricción entre roca-suelo varía entre 15,2° y 19,3° dependiendo de la humedad. La mineralogía del material granular grueso está compuesta en mayor parte por hematita, magnetita y cuarzo. La resistencia a la compresión simple de las partículas es 101,24 Mpa. La mineralogía del material fino está compuesta por magnetita, hematita, cuarzo, goethita, muscovita, caolín y rutilo. El material grueso resultó resistente al desgaste.

Original estimates of phosphorus (P) concentrations in the Precambrian oceans before 1.9 Ga gave a budget of ~10-25% of modern day levels. This budget was challenged by accounting for high silica (Si) concentrations that were believed to have outcompeted P for binding sites on precipitating iron oxide-hydroxide particles during the chemical oxidation and burial of iron (Fe). Such iron oxide-hydroxide particles are considered as proxies of ancient iron-rich sedimentary rocks, such as banded iron formations, which are often used to infer the dissolved chemistry of trace elements in the ancient oceans. This study raises the question of wether arsenic (As) had an effect of the binding of P to precipitating iron minerals, during the co-precipitation of Iron oxide- hydroxide in elevated Fe and Si concentrations characteristic of the early oceans. This hypothesis is based on the chemical similarities seen between P and As. Results show a more pH dependent competition between P and AsIII, whereby P outcompetes AsIII at a pH <7. The effect decreases as the pH rises until pH ~8 at which the effect cancels out and AsIII becomes somewhat predominant over P. AsV on the other hand, an analogue to P, is outcompeted by P throughout pH 5-10. Distribution coefficients (Kd) of P on iron oxide-hydroxide particles were not affected by the concentration of Si in solution. Average Kd and standard error between concentrations of Si, across the sample pH of 5-10 revealed an average Kd of 0.072 (±0.01) μM-1. This is strikingly similar to another experimental Kd at 0.075 (±0.003) μM-1, when the effects of Si are excluded. The average Kd in this study is also consistent with the average Kd of 0.06 μM-1 from a range of As-rich hydrothermal systems reported in a previous study, supporting the original idea of Precambrian P levels being low. The average Kd between concentrations of Fe revealed a Kd of 0.12 (±0.03) μM-1 although this was not statistically significant from the average Kd between groups of Si. In addition to low levels of P, the Precambrian oceans likely also contained high levels of As, due to the high hydrothermal activity. This scavenging of P from oceanic waters would have become increasingly important as surface oceans became more oxygenated and the presence of AsV would have been greater. Because the availability of Si does not show any great effect on the uptake of P by precipitating iron oxide-hydroxides, Si concentration is likely not a proxy for oceanic P concentrations. It is proposed that low dissolved P levels are consistent with early oceans that w!ere a lot more hydrothermally influenced than the oceans of today. / Prekambriska fosfor (P) nivåer var ursprungligen estimerade till ca 10-25% utav koncentrationen funnen i dagens havsvatten. Denna budget blev motsagd i och med att kisel (Si) sades kunna ersätta bundet fosfor på järn oxid-hydroxid partiklar som precipiterade genom kemisk oxidation och sedimentering av järn (Fe). Dessa järn oxid-hydroxid partiklar anses användbara som proxy för formationen av uråldriga järn-rika sedimentära bergarter såsom banded iron formation (BIF), vilka används idag för att bestämma mängden spårämnen i de uråldriga haven. Denna studie ställer frågan huruvida arsenik (As) påverkar mängden P som binder till precipiterande järn mineral under procession av co-precipitering av järn oxid-hydroxid i lösning med förhöjda koncentrationer av Fe och Si, karakteristiska för the uråldriga haven. Denna hypotes är baserad på de kemiska likheter som finns mellan P och As. Resultaten påvisar en pH beroende konkurrens mellan P och AsIII där P utkonkurrerar AsIII vid låg pH. Effekten av denna konkurrans minskar med ökande pH tills effekten blir omvänd omkring pH 8 och P blir istället till viss del utkonkurrerad av AsIII. AsV å andra sedan, en verklig kemisk analog till P, är kontinuerligt utkonkurrerad av P genom alla utförda pH, pH 5-10. Distribueringskoefficienter (Kd) för P på järn oxid-hydroxid partiklar visade ingen påverkan av mängden Si tillgängligt. Medelvärdet av Kd och standard error mellan data av alls pH, grupperat av Si, gav ett värde av 0.072 (±0.01) μM-1. Detta är påfallande nära ett experimentellt framtaget Kd värde av 0.075 (±0.03) μM-1 då effekten av Si är borttagen. Medelvärdet i denna studie är också sammanfallande med det Kd medelvärde man finner idag från olika hydrotemala system av 0.063 (±0.01) μM-1. Detta ger support till den originala idén att de prekambriska haven troligen hade låga halter P tillgängligt. Medelvärdet av Kd mellan koncentrationer av Fe gav ett värde av 0.12 (±0.03) μM-1, dock var detta värde ej statistiskt significant från det Kd utifrån koncentrationer av Si. Förutom de låga nivåer av P i de Prekambriska haven så var det troligen även höga halter av As på grund av utbredd hydrotermal aktivitet. Detta uppfångande av P i de tidiga haven var troligen en alltmer viktigare process då ytvatten blev syrerikare och den oxiderade formen av As, det vill säga AsV hade varit mer vanligt förekommande. Framför allt då den konkurrerande effekten av Si kan bortses när P såväl som As inte påverkas av dess närvaro till den grad man hade trott. Detta gör även att mängden Si troligen inte är en tillförlitlig proxy för att estimera P nivåer i de uråldriga haven. Därmed föreslås det att de prekambriska haven var k!arakteriserade av låga P nivåer, jämfört med idag.

Algoma-type banded iron formation is common in Neoarchean greenstone belts, and many of its distinctive features such as the banding of iron-rich and silica-rich material and deposition in volcanic terranes have been ascribed to their deposition related to volcanic-hydrothermal activity and cyclic variability in depositional pathways. The work presented in this thesis tests these assumptions and presents a model for the deposition and post-depositional processes now represented by the petrography and geochemistry of a 2.73 Ga type-locality of Algoma-type BIF in Temagami, ON. Adsorption of components onto the surface of Fe-oxyhydroxides forming in the anoxic Neoarchean water column is the most likely process capable of transferring silica, as well as trace quantities of transition metals, rare earth elements, Ge, P, U and other components to the sediment. The petrogenesis of the Temagami BIF lithologies suggests ongoing recrystallization processes and volume loss reactions leading to the formation of magnetite layers, while jasper is identified as the most pristine lithology best representative of the initially deposited Fe-oxyhydroxide-silica gel. Recrystallization and volume loss reactions are controlled by the ongoing dewatering during compaction and diagenesis, without the influence of external hydrothermal or metamorphic fluids. When corrected for the volume loss and small amounts of clastic contamination, little residual variability can be observed in the composition of jasper and magnetite layers, indicative of an originally homogenous primary precipitate instead of sorted and layered material deposited on the seafloor. This model is in stark contrast to previous interpretations of seasonal variability in biologic activity, cyclical seasonal or hydrothermal events responsible for primary layering in BIF. Instead, very little direct input of hydrothermal components is recorded in the chemistry of the Temagami BIF, and elements abundant in high-temperature hydrothermal fluids such as sulfur are instead sourced from atmospheric sources and deposited by bacterial pathways. Lack of primary chemical variability and non-hydrothermally sourced components captured in BIF argue against a genetic link to local hydrothermal venting, but rather an open ocean depositional setting. As such, the Temagami BIF does not represent a marker horizon related to local or regional hydrothermal venting and potential formation of associated massive sulfide deposits but reflects processes and the chemistry of the open Neoarchean ocean.

<p> The East South C (E.S.C.) ore zone at the Dickenson Mine, Red Lake, is a major auriferous banded sulphide orebody which cross-cuts sulphide facies banded iron formation (S.F.B.I.F.) near its eastern termination. Pyrite was obtained from sulphide-rich portions of the ore zone as well as from sulphide-poor E.S.C. mineralization not spatially associated with S.F.B.I.F., S.F.BI.F., shear zone hosted mineralization such as the 1492 and F ore zones, and from quartz-carbonate vein mineralization in the South C ore zone. Forty-three pyrite separates from the zones were analyzed by Atomic Absorption Spectrophotometry for Co and Ni, in order to determine the origin of the E.S.C. ore zone. The average Ni and Co content of these pyrites are as follows: S.F.B.I.F.,7.9 and 13.6 ppm respectively; remobilized S.F.B.I.F. 10.3 and 13.6; carbonatized S.F.B.I.F. 10.9 and 22.6; South C 14.9 and 50.6; 1492 zone 34.1 and 28.4; F-zone 11.2-27.6; sulphide-poor E.S.C. 26.2 and 48.4 and sulphide-rich E.S.C., 17.91 and 16.63.</p> <p> High and variable Co values were found to be associated with carbonate-rich samples, irrespective of the type of mineralization and low and similar Co values were found in all carbonate-poor samples irrespective of their origin. Therefore, the Co content of pyrite cannot be used as a discriminant of genetically dissimilar pyrite. The Ni content in pyrite from S.F.B.I.F. is low and constant, while in shear zone and vein mineralization it is higher and more variable. The E.S.C. ore zone has similar values to that found in the epigenetic mineralization, however, a few sulphide-rich samples are similar to those found in S.F.B.I.F., suggesting a bimodal source of sulphide for the E.S.C.. It is proposed that the hydrothermal system which produced the E.S.C., 1492, F and South C ore zones, locally incorporated sulphides from the S.F.B.I.F. to produce the sulphide-rich mineralization found at the eastern extremity of the E.S.C. ore zone.</p> / Thesis / Bachelor of Science (BSc)

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2016-09-20T12:04:31Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Usma Cuervo 2016_Dissertação Mestrado Geociências UFPE.pdf: 11366215 bytes, checksum: ea3d3e75aa36f118697420651fd55f20 (MD5) / Made available in DSpace on 2016-09-20T12:04:31Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Usma Cuervo 2016_Dissertação Mestrado Geociências UFPE.pdf: 11366215 bytes, checksum: ea3d3e75aa36f118697420651fd55f20 (MD5) Previous issue date: 2016-02-22 / FACEPE / Ao nordeste de São Jose de Belmonte, Pernambuco, o Complexo Riacho Gravatá Meso- a Neoproterozoico e o Grupo Cachoeirinha Neoproterozoico afloram. Ambas unidades de origem sedimentar e com intercalações de carbonato (mármore), formações de ferro bandado (BIF) e metavulcânicas são limitadas pela Zona de Cisalhamento Serra do Caboblo com direção NE. Outra importante caraterística da região é a abundante ocorrência de plutons graníticos criogenianosediacaranos que intruem o Grupo Cachoeirinha. O Complexo Riacho Gravatá com maior contribuição de material vulcânico, registra um evento extensional de formação de bacias relacionado com uma zona próxima de magmatismo de arco. O Grupo Cachoeirinha corresponde a uma sequência metaturbidítica, é dividido em Formação Santana dos Garrotes (unidade basal) e Formação Serra Olho d’Água (unidade superior) depositado numa bacia de retro arco. Quimioestratigrafia elemental e isotópica de seções selecionadas foi realizada objetivando estabelecer condições deposicionais de formação de carbonatos e formações ferríferas e estimar sua cronologia. Petrologia de plutons graníticos teve a intenção de elucidar ambiente tectônico e condições de cristalização destes corpos. A seção Barro do Complexo Riacho Gravatá é composto principalmente de mármores dolomíticos. A composição isotópica destes carbonatos com δ13C de -2,8 a -0,7‰ e δ18O de -15.0 a -15.8‰ podem ser correlatos com seções de final do Esteniano a inicio do Toniano. Os padrões de ETRY permitem inferir um ambiente deposicional marinho sob condições anóxicas e contribuição de fluidos hidrotermais. Da Formação Santana dos Garrotes, mármores calcíticos das localidades de Pedreira e Oiti mostram δ13C médios de +4,9‰ e +4,1‰, respectivamente, além de anomalias negativa de Ce e positiva de Y, sugerindo uma idade de deposição Criogeniano médio a tardio num ambiente levemente oxigenado. Os padrões de ETRY normalizados em relação ao PAAS para o BIF da Localidade Oiti são a favor de uma precipitação hidrogenética com influência hidrotermal. Química em rocha total e mineralde plutons granodioriticos com epidoto magmático ao norte do povoado Carmo permitem identifica-los como cálcio-alcalino principalmente, e cálcio-alcalinos de alto K, de origem mista. Estes granodioritos provavelmente forma intruidos durante a fase final de um regime de subdução, cristalizando sob pressões de 6,6 – 9,3 kbar e temperaturas entre 720 e 765°C, a uma profundidade ao redor de 22 Km. / To the northeast of the São Jose de Belmonte, Pernambuco, the Meso- to Neoproterozoic Riacho Gravatá Complex and the Neoproterozoic Cachoeirinha Group outcrops. Both units of sedimentary origin and with carbonate (marble), banded iron formation (BIF) and metavolcanic intercalations are limited by the Serra do Caboclo Shear Zone with a NE direction. Another important characteristic of the area is the abundant occurrence of Cryogenian-Ediacaran granitic plutons that intrude the Cachoeirinha Group. The Riacho Gravatá Complex with great contribution of volcanic material, record an extensional event of basin formation related to a nearby zone of arc magmatism. The Cachoeirinha Group corresponds to a metaturbiditic sequence, it is divided into the Santana dos Garrotes Formation (basal unit) and the Serra Olho d’Água Formation (upper unit) deposited in a back-arc basin. Elemental and isotope chemostratigraphy of selected sections was carried out aiming at precising the depositional conditions of carbonate and iron-bearing sediment formation and estimating their chronology. Petrology of granitic plutons had the intention of elucidate tectonic environment and crystallizing conditions of these bodies. The Barro section of Riacho Gravatá Complex is composed mainly of dolomitic marbles. The isotopic composition of these carbonates with δ13C varying from -2.8 to -0.7‰ and δ18O from -15.0 to -15.8‰ can be correlated with late Stenian – early Tonian sections. The REE+Y patterns led to infer a marine depositional environment under slightly anoxic conditions and hydrothermal fluids contribution. From Santana dos Garrotes Formation, calcitic marbles at the Pedreira and Oiti localities display average δ13C, respectively, of +4.9‰ and +4.1‰, besides negative Ce anomaly and positive Y anomaly, suggesting a middle to late Cryogenian depositional age in a slightly oxygenated environment. The PAAS normalized REE + Y patterns for BIFs at the Oiti locality favor a hydrogenetic precipitation with hydrothermal influence. Bulk and mineral phase chemistry analyses of magmatic epidote-bearing granodioritic plutons to the north of the Carmo village allow identify them as calc-alkalic and high K calc-alkalic, of mixed origin. These granodiorites were likely intruded during final stages of a subduction regime, crystallizing under pressures of 6.6–9.3 kbar and temperatures in the 720–765°C range, at depths around 22 Km.

The Pilbara region of Western Australia hosts the Hamersley Province, an area of abundant iron ore resources located in the lower Hamersley Groups, Brockman and Marra Mamba Iron Formations. This study consists of a geotechnical and a geochemical and mineralogical investigation into the Banded Iron Formation (BIF) and shale deposits of the lower Hamersley Group that reside in the pit walls of RTIO mines in Western Australia. Areas throughout Tom Price, Paraburdoo, Marandoo and West Angelas iron ore mines are geotechnically investigated for rock mass conditions through the use of the Slope Mass Rating (SMR) classification system and through point load and slake durability testing. Selected samples from these areas were then geochemically and mineralogically tested by X-ray Fluorescence (XRF), X-ray Diffraction (XRD) and microscopic analysis, to determine the geochemical and mineralogical changes of BIF and shale as they alter and weather through hypogene and supergene alteration and Recent weathering. It was found that the most efficient method for determining the alteration and/or weathering of lower Hamersley Group BIF and shale deposits was by the use of a chemical alteration index, calculated from enriched and depleted major elements in the BIF and shale as they alter and weather. It has been suggested here that this Pilbara Iron alteration index can be calculated efficiently and effectively from geochemical testing in intervals down boreholes throughout future or developing open pit mines to assist in estimating slope stability conditions. It is also suggested that many boreholes should be analysed in section or in 3D space to create cross sections or block models showing the varying extent of alteration and weathering throughout the area being studied. From the geotechnical investigation, it was found that the weakest region, in terms of pit slope stability, were the highly and extremely altered and/or weathered regions with Pilbara Iron alteration indices of between 61 and 80, and 81 and 100, respectively. If these zones are identified, slope stability analysis can be focused on these geotechnically vulnerable areas. Slope stability analysis should be completed by using a suitable technique, such as by the use of SMR, which, along with other risk identification measures, will identify potentially unstable areas and suggest the required course of action. Further hazard and risk analysis should be undertaken in potentially unstable areas and remedial measures undertaken as appropriate. Thereby, the Pilbara Iron alteration index can be used in the Hamersley Province as a predictive tool for pit slope stability.

The external silicon cycle during the Precambrian (4.5-0.5 Ga) is not well understood despite its key significance to apprehend ancient dynamics at the surface of the Earth. In the absence of silicifying organisms, external silicon cycle dramatically differs from nowadays. Our current understanding of Precambrian oceans is limited to the assumption that silicon concentrations were close to saturation of amorphous silica. This thesis aims to bring new insights to different processes that controlled the geochemical silicon cycle during the Archaean (3.8-2.5 Ga). Bulk rock Ge/Si ratio and Si isotopes (δ30Si) offer ideal tracers to unravel different processes that control the Si cycle given their sensitivity to fractionation under near-surface conditions. <p>First, this study focuses on Si inputs and outputs to ocean over a limited time period (~2.95 Ga Pongola Supergroup, South Africa) through the study of a palaeosol sequence and a contemporaneous banded iron formation. The palaeosol study offers precious clues in the comprehension of Archaean weathering processes and Si transfer from continent to ocean. Desilication and iron leaching were shown to be the major Archaean weathering processes. The occurrence of weathering residues issued of these processes as major component in fine-grained detrital sedimentary mass (shales) attests that identified weathering processes are widely developed and suggest an important dissolved Si flux from continent to the ocean. In parallel, banded iron formations (BIFs), typically characterised by alternation of iron-rich and silica-rich layers, represent an extraordinary record of the ocean-derived silica precipitation throughout the Precambrian. A detailed study of a 2.95 Ga BIF with excellent stratigraphic constraints identifies a seawater reservoir mixed with significant freshwater and very limited amount of high temperature hydrothermal fluids as the parental water mass from which BIFs precipitated. In addition, the export of silicon promoted by the silicon adsorption onto Fe-oxyhydroxides is evidenced. Then, both Si- and Fe-rich layers of BIFs have a common source water mass and a common siliceous ferric oxyhydroxides precursor. Thus, both palaeosols and BIFs highlight the significance of continental inputs to ocean, generally under- estimated or neglected, as well as the close link between Fe and Si cycles. <p>In a second time, this study explores secular changes in the Si cycle along the Precambrian. During this timespan, the world ocean underwent a progressive decrease in hydrothermal inputs and a long-term cooling. Effects of declining temperature over the oceanic Si cycle are highlighted by increasing δ30Si signatures of both chemically precipitated chert and BIF through time within the 3.8-2.5 Ga time interval. Interestingly, Si isotope compositions of BIF are shown to be kept systematically lighter of about 1.5‰ than contemporaneous cherts suggesting that both depositions occurred through different mechanisms. Along with the progressive increase of δ30Si signature, a decrease in Ge/Si ratios is attributed to a decrease in hydrothermal inputs along with the development of large and widespread desilication during continental weathering.<p><p><p>Le cycle externe du silicium au précambrien (4.5-0.5 Ga) reste mal compris malgré sa position clé dans la compréhension des processus opérant à la surface de la Terre primitive. En l’absence d’organismes sécrétant un squelette externe en silice, le cycle précambrien du silicium était vraisemblablement très différent de celui que nous connaissons à l’heure actuelle. Notre conception de l’océan archéen est limitée à l’hypothèse d’une concentration en silicium proche de la saturation en silice amorphe. Cette thèse vise à une meilleure compréhension des processus qui contrôlaient le cycle géochimique externe du silicium à l’archéen (3.8-2.5 Ga). Dans cette optique, le rapport germanium/silicium (Ge/Si) et les isotopes stables du silicium (δ30Si) représentent des traceurs idéaux pour démêler les différents processus contrôlant le cycle du Si. <p>Dans un premier temps, cette étude se focalise sur les apports et les exports de silicium à l’océan sur une période de temps restreinte (~2.95 Ga Pongola Supergroup, Afrique du Sud) via l’étude d’un paléosol et d’un dépôt sédimentaire de précipitation chimique quasi-contemporain. L’étude du paléosol apporte de précieux indices quant aux processus d’altération archéens et aux transferts de silicium des continents vers l’océan. Ainsi, la désilicification et le lessivage du fer apparaissent comme des processus majeurs de l’altération archéenne. La présence de résidus issus de ces processus d’altération en tant que composants majeurs de dépôts détritiques (shales) atteste de la globalité de ces processus et suggère des flux significatifs en silicium dissout des continents vers l’océan. En parallèle, les « banded iron formations » (BIFs), caractérisés par une alternance de niveaux riches en fer et en silice, représentent un enregistrement extraordinaire et caractéristique du précambrien de précipitation de silice à partir de l’océan. Une étude détaillée d’un dépôt de BIFs permet d’identifier une contribution importante des eaux douces dans la masse d’eau à partir de laquelle ces roches sont précipitées. Par ailleurs, un mécanisme d’export de silicium via absorption sur des oxyhydroxydes de fer est mis en évidence. Ainsi, les niveaux riches en fer et riche en silice constituant les BIFs auraient une même origine, un réservoir d’eau de mer mélangée avec des eaux douces et une contribution minime de fluides hydrothermaux de haute température, et un même précurseur commun. Dès lors, tant les paléosols que les BIFs mettent en évidence l’importance des apports continentaux à l’océan, souvent négligés ou sous estimés, ainsi que le lien étroit entre les cycles du fer et du silicium.<p>Dans un second temps, cette étude explore l’évolution du cycle du silicium au cours du précambrien. Durant cette période, l’océan voit les apports hydrothermaux ainsi que sa température diminuer. Dans l’intervalle de temps 3.8-2.5 Ga, les effets de tels changements sur le cycle du silicium sont marqués par un alourdissement progressif des signatures isotopiques des cherts et des BIFs. Le fort parallélisme entre l’évolution temporelle des compositions isotopiques des deux précipités met en évidence leur origine commune, l’océan. Cependant, les compositions isotopiques des BIFs sont systématiquement plus légères d’environ 1.5‰ que les signatures enregistrées pas les cherts. Cette différence est interprétée comme le reflet de mécanismes de dépôts différents. L’alourdissement progressif des compositions isotopiques concomitant à une diminution des rapports Ge/Si reflètent une diminution des apports hydrothermaux ainsi que la mise en place d’une désilicification de plus en plus importante et/ou généralisée lors de l’altération des continents.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Les conditions oxydantes de la surface terrestre actuelle sont dues à la teneur élevée en dioxygène de l’atmosphère. Au début de l’histoire de la Terre il y a 4.54 milliards d'années (Ga), l’oxygène n’était pas stable dans l’atmosphère. Il a fallu deux épisodes d’augmentation brutale de ce gaz atmosphérique pour qu’il atteigne son niveau actuel : l’un vers 2.4 Ga, nommé le Grand Evènement Oxydant (GOE) qui fait l’objet de ce projet, l’autre 2 milliards d’années plus tard, nommé l’Evènement Oxydant Néo-protérozoïque (NOE). Le GOE est vraisemblablement le résultat de l’émersion généralisée de larges continents dont l’érosion libère le phosphate dans l’océan, un nutriment nécessaire à la production biologique, qui a donc permis l’explosion de la photosynthèse oxygénée. Ces deux hausses d’oxygène atmosphérique coïncident avec deux évolutions majeures dans l’histoire de la vie : (i) peu après le GOE, les eucaryotes sont apparus, alors que (ii) le NOE correspond à l’apparition des métazoaires et à l’explosion cambrienne. L’étude de ces phénomènes atmosphériques primitifs peut avoir d’importantes répercussions sur notre compréhension de l’origine et de l’évolution de la vie, qu’on estime principalement marine à cet âge. Les seules archives de ces temps primitifs sur Terre sont les roches sédimentaires. Pour savoir comment l’oxygénation de l’atmosphère a pu être reliée à cette vie marine, il faut tout d’abord comprendre comment l’océan a interagi avec l’atmosphère lors de cet évènement d’oxygénation. Cette question est au coeur de ce projet : comment le GOE a-t-il affecté les cycles biogéochimiques océaniques dont la vie est dépendante ? Nous nous sommes intéressés aux formations ferrifères litées ou BIFs (Banded Iron Formations). La chimie de ces roches marines fait écho à celle de l’océan contemporain à leur formation. Déterminer quantitativement la composition de l’océan à partir de celles des sédiments, même chimiques, est un défi quasiment impossible à relever y compris dans l’océan moderne. C’est pourquoi nous avons proposé de déterminer le temps de résidence d’éléments sensibles aux conditions redox de la surface, le soufre, le fer et le cuivre dans l’océan pré-GOE. Nous avons obtenu, par des séries temporelles, le spectre des fluctuations isotopiques de ces éléments enregistrées dans des carottes de formations ferrifères litées. La limite inférieure du spectre donne le temps de résidence de ces éléments dans l’eau de mer et fournit donc une indication solide sur la teneur de ces éléments dans l’océan à cette période. Nous avons analysé des échantillons protérozoïques proches de la limite Archéen-Protérozoïque du Transvaal (Afrique du Sud) et d’Hamersley (Australie). Des échantillons eoarchéens de Nuvvuagittuq (Canada) ont été récoltés mais n'ont pas pu être analysés faute de temps. / The present-day oxidizing conditions at Earth's surface are due to the high oxygen content of the atmosphere. However, oxygen was not always stable in the terrestrial atmosphere. Two distinct periods during which oxygen increased in a step-like manner were required to reach the current atmospheric oxygen level. The first, at about 2.4 Ga, is known as the Great Oxidation Event (GOE) and is at the core of this Ph.D. thesis. The other, occurring almost two billion years later, is called the Neo-Proterozoic Oxidation Event (NOE). The GOE likely is the result of the beginning widespread emergence of large continental expanses whose subsequent erosion gradually released phosphate into the ocean. Phosphate, a nutrient essential to organic production, in turn allowed the explosion of oxygenated photosynthesis. The GOE and NOE coincide with two major changes in the history of life. Shortly after the GOE, eukaryotes appeared, while the NOE corresponds to the appearance of metazoans and the Cambrian explosion. A better grasp of the GOE hence may have important implications for the understanding of the origin and evolution of life, which is thought to have been mainly marine at this stage in Earth history. The only records of the oxygen level during these ancient times are found in terrestrial sedimentary rocks. To understand how oxygenation of the atmosphere relates to marine life, we must first understand how the ocean was connected to the atmosphere during the GOE and how the GOE affected life-dependent ocean biogeochemical cycles. To this end we focused on banded iron formations (BIF). The chemistry of these sedimentary marine rocks directly reflects the chemistry of the contemporary ocean. Deriving quantitatively the composition of the ocean from a hydrogenous sediment is a challenge almost impossible to meet, even for the modern ocean. This is why we instead determined the residence time of redox-sensitive elements (in this case sulfur, iron, and copper) in the pre-GOE ocean. We specifically targeted the periods of isotopic fluctuations in these elements as recorded in BIF cores. The lower limit of the spectrum provides the residence time of these elements in seawater, hence giving a robust indication of their contents in the pre-GOE ocean. We sampled early Proterozoic BIF near the Archean-Proterozoic boundary in Transvaal (South Africa) and Hamersley (Australia), as well as Archean BIF from Nuvvuagittuq (Canada), though the latter were not analyzed during this thesis due to shortage of time.

Ädelfors is situated ca 17 km east of Vetlanda, Jönköping County, in the N-S striking Trans-scandinavian igneous belt and is a part of the NE-SW striking 1.83-1.82 Ga Oskarshamn-Jönköping belt emplaced during a continental subduction towards the Svecofennian continental margin. The continental arc hosts the 1.83 Ga metasedimentary Vetlanda supergroup composed of foliated metagreywacke, metasandstone and metaconglomerate. The sequence is intercalated by mafic and felsic volcanites and hosts the Cu-Au-Fe-mines at Ädelfors. Ädelfors mining field consists of ca 330 mineralized quartz veins hosting both copper, gold and iron. The iron mines Nilsson’s iron mine (NFE) and Fe-mine (FE), the copper mine Kamelen (KM) and the gold mines Brånad’s mine (BR), Adolf Fredrik’s mine (AF), Old Kron mine (GKR), Old Kolhag’s mine (GKO), Thörn mine (TH), New Galon mine (NG), Stenborg’s mine (ST), Tysk mine (TG), Hällaskallen (HS) and Fridhem (FR) have been investigated to deduce a possible genetic relation between the veins and their origin. Sulfur isotope ratios have also been conducted on pyrite from KM, AF and FE. The veins can stucturally be divided into several groups. AF, GKR, ST, NG, TH and possibly NFE are striking 10-70° with a dip of 55-70°. BR, GKO and KM are striking 110-140° with a dip of 80-90° whereas TG and HS strike 90-110° dipping 85°. Fridhem, being distal to the other mines, strikes 70° and dips 80°. A chlorite-quartz-biotite-sericite-rich metapelite hosts the veins in all localities except; FR where a layered, beresitizised felsic volcanite rich in plagioclase, sericite, biotite and quartz hosts disseminated pyrite; and NFE, HS and NG which are hosted by a mafic tuffite. Quartz veins are mainly milky and equigranular, exceptions are FE with black pyrite-bearing quartz veins, cutting through the banded magnetite-metapelite and KM with its dynamically recrystallized quartz. Chlorite-, zeolite-, carbonate-, hematite-, amphibole-, kalifeldspar-, sericite-, biotite- and epidote alteration has been observed among the localities. The ore minerals are dominated by: fractured sub- to euhedral pyrite in cataclastic aggregates or selvage bands, interstitial chalcopyrite in pyrite, marcasite, pyrrhotite, gold and sporadic chalcopyrite diseased sphalerite and arsenopyrite. Previously not reported tetradymite, staurolite, galena and Ce-monazite have also been observed. Bismuthinite and tetradymite as inclusions in pyrite were observed in AF, GKR, FR and TG. Gold was observed in AF, BR, GKR and TG as inclusions in pyrite or quartz with a Au/Ag median of 78.41. HS distinguishes itself with Au/Ag ratios of 4.66-5.25. The trace element ratios in pyrite reveal two major types of pyrite. 1) found in FE and KM (pyrite type 1) with Co/Ni ratio of 10.94, Bi/Au of 1.79, Bi/S of 0.037, Au/Ag of 11.13, S/Se of 235.96 and As/S of 0.006. 2) found in NG, GKO, ST, TH, AF, NFE, HS, GKR, BR, FR, TG and as stringers in KM4 py1 pyrite type 2) with an average Co/Ni ratio of 5.26, Bi/Au of 1.95, Bi/S of 0.031, Au/Ag of 4.19, S/Se of 0 and As/S of 0. δ34S values strengthens this grouping as KM and FE has 1,3-2,6 ‰ and AF 3,6-3,8 ‰. The following geological interpretation has been concluded: The banded iron formation in FE is the earliest mineralization and was later fractured, emplacing quartz veins with pyrite of type 1. During this event, the Cu-vein in KM was also formed. A second generation of fractures, emplaced after the Småland granitoids formed, were filled with quartz and pyrite of type 2 at mesozonal depth. This is the main stage of gold mineralization and includes NG, GKO, ST, TH, AF, NFE, GKR, BR, FR and TG. During this event, pyrite of type 2 was added to KM, causing recrystallizing of the quartz. HS is possibly emplaced last or altered as it is more enriched in silver. Morphology, mineralogy, alterations, mineral chemistry and sulfur isotope signatures indicates an orogenic origin of the gold-rich quartz veins at Ädelfors as well as the copper-rich vein in KM. / Ädelfors ligger ca 17 km öster om Vetlanda, Jönköpings län, i det N-S strykande Transskandinaviska granit och porfyrbältet och är en del av det NÖ-SV strykande 1,83-1,82 Ga Oskarshamn-Jönköpingsbältet (OJB) bildad i en kontinental subduktionszon i kanten av den Svecofenniska kontinentalplattan. I denna kontinentalbåge ligger Vetlanda supergruppen som är en metasedimentär del av OJB bestående av starkt folierad 1,83 Ga metagråvacka, metasandsten och metakonglomerat med inlagringar av mafiska och felsiska vulkaniter. Ädelfors gruvfält består utav ca. 330 kvartsgångar förande mestadels guld men också koppar. Järnmineraliseringar i form av bandad järnmalm finns också i området. Geologin, mineralogin och pyritens kemiska sammansättning från järngruvorna Nilssons järngruva (NFE) och Fe-gruvan (FE), koppargruvan Kamelen (KM) och guldgruvorna Brånadsgruvan (BR), Adolf Fredriks gruva (AF), Gamla Krongruvan (GKR), Gamla Kolhagsgruvan (GKO), Thörngruvan (TH), Nya Galongruvan (NG), Stenborgs gruva (ST), Tyskgruvan (TG), Hällaskallen (HS) och Fridhem (FR) har undersökts för att finna eventuella genetiska likheter. Svavelisotopförhållande har fastställts för pyrit från AF, FE och KM. Strukturellt kan gångarna delas in i ett antal grupper. AF, GKR, ST, NG, TH och möjligtvis NFE stryker 10-70° och stupar 55-70°. BR, GKO och KM stryker 110-140° och stupar 80-90° medan TG och HS stryker 90-110° och stupar 85°. Fridhem stryker 70° och stupar 80°. En klorit-kvarts-sericit-biotitrik metapelit utgör värdbergarten i alla gruvor förutom; FR där den utgörs av en beresitiserad felsisk vulkanit rik på plagioklas, sericit, biotit och kvarts med disseminerad pyrit; och NFE, HS, NG vilka har en mafisk tuffitisk moderbergart. Kvartsgångarna är mjölkvita med undantag för FE:s svarta, pyritförande kvarts vilket uppträder som sprickfyllnad i den bandade järnmalmen och är senare bildad. Kvartsen i KM är starkt dynamiskt omkristalliserad. Svag till måttlig foliation är vanlig i sidoberget med undantag av stark foliation i TG och NFE, vilka är lokaliserade i förkastningssprickor med stark kloritförskiffring av värdbergarten. Klorit-, zeolit-, karbonat-, hematit-, amfibol-, kalifältspat-, sericit-, biotit- och epidotomvandling förekommer i majoriteten av lokalerna. Malmmineralen är dominerande sprött deformerad subhedral till euhedral pyrit som kataklastiska aggregat eller band, interstitiell kopparkis i pyrit, markasit, magnetkis, guld och sporadiskt kopparkissjuk zinkblände och arsenikkis. I det här arbetet har även tetradymit, staurolit, blyglans och Ce-monazit observerats. Bismutinit och tetradymit i form av inneslutningar i pyrit observerades i AF, GKR, FR och TG. Guld observerades i AF, BR, GKR och TG som inneslutningar i pyrit eller fritt i kvarts med Au/Ag medianvärde på 78,41, avvikande är HS med värden mellan 4,66-5,25.    Förhållanden mellan spårelement i pyrit indikerar två typer av pyrit. Typ 1 funnen i FE och KM har följande värden: Co/Ni = 10,94, Bi/Au = 1,79, Bi/S = 0,037, Au/Ag = 11,13, S/Se = 235,96 och As/S = 0,006. Typ 2 funnen i NG, GKO, ST, TH, AF, NFE, HS, GKR, BR, FR, TG och som sliror i KM4 py1 har följande värden Co/Ni = 5,26, Bi/Au = 1,95, Bi/S = 0,031, Au/Ag = 4,19, S/Se = 0 and As/S = 0. δ34S värden styrker denna uppdelning där KM och FE har värdena 1,3-2,6 ‰ och AF 3,6-3,8 ‰. Den geologiska utvecklingen av fältet har tolkats som följande: FE-gruvans bandade järnmalm är den tidigaste mineraliseringen vilket följs utav uppsprickning och läkning av kvarts med pyrit typ 1 som också bildar kopparmineraliseringen KM. Senare sprickzoner efter Smålandsgraniternas intrusion läks av kvarts med pyrit typ 2 på mesozonalt djup vilket bildar NG, GKO, ST, TH, AF, NFE, GKR, BR, FR, TG och omkristalliserar och introducerar nya pyritsliror i kvartsen i KM. HS bildas möjligtvis sist eller har blivit omvandlad eftersom den är anrikad på silver. Morfologi, omvandlingar och svavelisotop-signaturer tyder på ett orogent ursprung för Ädelfors guldrika kvartsådror samt den kopparrika kvartsådern i KM.