The Drybones Bay and Mud Lake kimberlites are Ordovician kimberlites located in the Slave Geological Province. The Drybones Bay pipe formed by multiple discrete eruptions, producing several texturally distinct phases of kimberlite, including hypabyssal kimberlite (HK) autoliths, tuffisitic kimberlite (TK), pyroclastic kimberlite (PK) and resedimented volcaniclastic kimberlite (RVK). The recognition of TK suggests this pipe represents a Class 1 kimberlite. The nearby Mud Lake kimberlite is a dolomite-rich HK dyke characterized by macrocrystic and segregation textures. Although the kimberlites are proximal, U-Pb zircon dates indicate they were not emplaced contemporaneously, and geochemical discrepancies that cannot be explained by known magma evolution processes indicate that these rocks formed from distinct parental magmas. Mineralogical and geochemical data is used to evaluate crystallization conditions and diamond potential. New geochemical modeling of compatible trace elements reveals convincing evidence of magma evolution by olivine fractionation, adding substantially to the published research on kimberlite geochemistry. / October 2016

As intrusões Indaiá I e II (também referidas como Perdizes 3-A e 3-B) são corpos intrusivos hipoabissais ultrabásicos de pequeno porte, associados ao magmatismo cretácico da Província Alcalina Alto Paranaíba, oeste do Estado de Minas Gerais. Esta dissertação de mestrado objetivou compreender a gênese e processos de evolução relacionados a intrusão Indaiá II, cuja classificação ambígua entre kimberlito e kamafugito dividiu autores em trabalhos anteriores.. Também buscou-se discutir a possível vinculação genética com a intrusão vizinha, Indaiá I. Para tanto, foram realizadas novas análises petrográficas, geoquímicas e isotópicas de rocha total, e química mineral. A intrusão principal (Indaiá I) é classificada como um kimberlito do Grupo I. Já a intrusão satélite (Indaiá II) distingue-se quimicamente e petrograficamente, possuindo uma composição ultrapotássica, similar à kamafugítica, e apresenta menor concentração de macrocristais de olivina, diopsídio como o principal constituinte da matriz ( e não a monticellita como Indaiá I) e possui uma presença abundante de microenclaves félsicos. Estes enclaves apresentam estrutura estirada, e são constituídos principalmente por kalsilita/ nefelina, vidro devitrificado, diopsídio e flogopita. A presença de texturas sugestivas de desequilíbrio físico-químico como embayment e sieve em grãos de olivina e clinopiroxênio em Indaiá II são indicativas de processos de sistema aberto. A abundância de diopsídio na matriz e a substituição de olivina por clinopiroxênio nas bordas de macrocristais e microcristais apontam para um aumento da atividade de sílica no decorrer do processo de cristalização. A alta proporção de xenólitos crustais na rocha, totalmente transformados ou com evidências de fusão parcial, e a presença de apatitas aciculares nas suas cercanias, indicam a operação de um processo de contaminação crustal. Novos dados de química mineral e litogeoquímica de elementos maiores e traços corroboram esse processo. Os trends composicionais de minerais como espinélio e flogopita são bastante similares a ocorrências de kimberlitos contaminados registrados na literatura. Além disso, amostras de Indaiá II apresentam elevado C.I. (Contamination Index, 2,12-2,25), maior percentual de SiO2, K2O e maior razão Rb/Sr que a intrusão principal. Modelos de contaminação crustal foram efetuados a partir da mistura do fundido de Indaiá I e do fundido das rochas granitoides encaixantes. Os fundidos de Indaiá I e II foram obtidos pela extração do volume dos núcleos de macrocristais de olivina, considerados xenocristais em ambas as ocorrências, das análises de rocha total. A quantidade de olivina foi obtida através de análises modais, e a composição considerada foi obtida através de uma média das análises pontuais de microssonda eletrônica e LA-ICP-MS. O fundido da encaixante foi estimado utilizando-se as análises de rocha-total das encaixantes crustais da área e calculando-se um fundido parcial desta rocha a 750ºC e pressões entre 1-5Kbar com o software RhyoliteMelts (para elementos maiores). A composição de elementos-traço do fundido foi modelada por balanço de massa, a partir de coeficientes de partição compilados da literatura e a proporção de minerais no resíduo sólido obtida dos modelos por elementos maiores. Curvas de mistura entre elementos maiores e traços também parecem confirmar o processo. Novos dados isotópicos de 87Sr/86Sr e 143Nd/144Nd foram obtidos para estas intrusões, como também para a encaixante local. Curvas de mixing isotópico foram feitas para tentar estabelecer a quantidade de contribuição crustal nos magmas de Indaiá II. Nestes modelos, as amostras de Indaiá II ajustam-se concordantemente às curvas de mistura entre os polos de Indaiá I e da encaixante. Concluimos que: 1) a intrusão Indaiá II representaria uma intrusão kimberlítica altamente contaminada, 2) a contaminação provavelmente ocorreu pela assimilação de fundidos anatéticos oriundos das principais rochas encaixantes crustais da área, 3) que Indaiá I e Indaiá II poderiam ter um mesmo magma progenitor, mas com diferentes graus de contaminação crustal. / The intrusions Indaiá I and II (also referred as Perdizes 3-A and 3-B) are hypoabissal ultrabasic bodies of small size associated with the Cretaceous magmatism of the Alto Paranaiba Alkaline Province, west of the Minas Gerais state. This master\'s dissertation aimed a better understanding of the genesis and the evolution processes related to the Indaiá II intrusion, whose ambiguous classification between kimberlite and kamafugite divided the authors of former works. Also, it is discussed the possible genetic linkage of Indaiá II with the neighbor intrusion, Indaiá I. For this purpose, new petrographic, whole rock geochemical, isotopic and mineral chemistry analyses were made. The main intrusion (Indaiá I) was classified as a group-I kimberlite. The satellite intrusion, Indaiá II, is petrographically and chemically distinct of the main one, having a ultrapotassic composition, similar to those of kamafugites, and presenting lower volumes of olivine macrocrysts, diopside as the main matrix phase (instead of monticellite as found in Indaiá I), and an abundant presence of felsic microenclaves. These enclaves present elongated structure and they mainly have kalsilite, devitrified glass, diopside and phlogopite. The presence of textures indicative of physical-chemical disequilibrium, such as embayment and sieve in olivine and clinopyroxene grains from Indaiá II are indicative of an open system process. The high amounts of diopside in the matrix and the substitution of the rims of olivine macro- and microcrysts by clinopyroxene point to an increase in the silica activity during the crystallization. The high proportion of crustal xenoliths in the rocks, most of these totally transformed or with evidences with partial melt, and the presence of acicular apatite in their border regions, indicate the action of crustal contamination processes. New mineral chemistry and whole rock geochemical (major and trace elements) data corroborate this process. The spinel and phlogopite compositional trends are very similar with those from contaminated kimberlitic occurrences registered in the literature. Moreover, samples from Indaiá II have high Contamination Index (C.I., 2.12-2.25), greater amounts of SiO2, K2O and higher Rb/Sr ratios than those from the main intrusion. Crustal contamination models were developed considering a mixing between the melt of Indaiá I and the partial melt of the granitoid host rocks of the area. The composition of melts from Indaiá I and II were calculated by the extraction of the amount of the cores of olivine macrocrysts, considered xenocrysts in both occurrences, from the whole-rock compositions. The amount of olivines was taken from modal concentrations and the considered composition was obtained by the average of electron microprobe and laser ablation inductively coupled plasma mass spectrometry (LA ICP-MS) analyses. The major element composition of the partial melt of the host rock was estimated using the algorithm RhyoliteMelts. For these models, we considered the whole-rock compositions of the main host rocks of the area and used 750ºC and 1-5Kbar. The trace element composition of the host rock partial melts was modeled by mass balance calculations, using partition coefficients from the literature and the proportion of minerals in the solid residue obtained for the major element models. After the calculation of these liquid compositions, mixing curve models using major and trace element compositions were made and they are concordant with the crustal contamination processes. New 87Sr/86Sr and 143Nd/144Nd isotopic data were obtained for Indaiá I and II intrusions, as well as for the local host rock. Isotopic mixing curves were also made trying to constrain the amount of crustal contribution in Indaiá II magmas. In these models, Indaiá II samples fit concordantly with the mixing curves having Indaiá I and the host rock ratios as the main poles. We conclude that 1) Indaiá II is representative of a highly contaminated kimberlitic intrusion, 2) the contamination possibly occurred by the assimilation of the anatetic melts from the main crustal host rocks of this area and 3) that Indaiá I and Indaiá II could have the same parent melt, but with different degrees of crustal contamination.

A presente dissertação se ocupou da investigação petrográfica e química mineral de rochas ultramáficas, potássica-ultrapotássicas, insaturadas em sílica, de afinidade kimberlítica, das intrusões Indaiá I e Indaiá II, oeste do Estado de Minas Gerais. Estas rochas afloram na Província Ígnea do Alto Paranaíba (PIAP, Cretáceo Superior), dentro de uma área alongada segundo N30W, perfazendo aproximadamente 250 km de extensão e 70 km de largura. As suítes do PIAP encontram-se à margem oeste do Cráton do São Francisco, alojadas em litologias pertencentes próprio Cráton e à Faixa Brasília. Os dados petrográficos, dentro das suas limitações, principalmente no que tange à sobreposição de características entre as rochas dos clãs kimberlitos, lamproítos, kamafugitos, orangeitos e lamprófiros, denotam na intrusão Indaiá I a presença de texturas porfiríticas, compostas de mega e fenocristais anédricos a subédricos de olivina, opacos e mais raramente de enstatita, fixados em matriz afanítica formada de cristais anédricos de olivina (crisolitaforsterita), minerais opacos, monticellita tabular, cristais amarronzados subédricos de perovskita, clinopiroxênio (diopsídio) esverdeado e carbonatos. Já na intrusão II se observa a presença de fenocristais anédricos a subédricos de olivina, fixados em matriz afanítica contendo alguns microfenocristais, prismáticos a subédricos, de clinopiroxênio diopsídico esverdeado, cristais anédricos de minerais opacos associados a espinélio avermelhado, cristais subédricos a anédricos de perovskita, grãos arredondados de olivina e também raro vidro intersticial, embora já devidrificado. A composição mineral observada nas rochas da intrusão Indaiá I é representada essencialmente por cristais de crisolita - forsterita (Mg/Mg+Fe2+ de 83 a 95), enstatita (En85,3Fs12,7Wo1,54), ilmenita magnesiana, Cr-espinélio representados por espinélio e membros da série chromite-magnetite-ulvöspinélio, monticellita (92% do membro final CaMgSiO4 ) e perovskita (93% do membro final CaTiO3). Na intrusão Indaiá II, a assembléia mineral presente é bastante similar à observada na intrusão I, contudo com um piroxênio diopsídico mais enriquecido em cálcio (En39,7Fs10,2Wo48,0) e ausência de minerais espinélio e monticellita. Com base na conjunção das características petrográficas e químicas dos minerais descritas no presente trabalho, propõe-se para as rochas das duas intrusões uma afinidade kimberlítica, pertencente ao clã dos kimberlitos do Grupo I. Apesar das ilmenitas magnesianas possuirem composições indicativas de que o líquido gerador das rochas favorece a preservação de diamantes, posto a inexistência de macrocristais de cromita com alta porcentagem de Cr2O3 e granadas G10 e/ou eclogitícas com altos teores de Na2O, a propensão à mineralização é frustada, isto porque, aparentemente, estas intrusões não amostraram xenólitos e macrocristais situados dentro da região do campo de estabilidade dos diamantes. As rochas de Indaiá I e Indaiá II apresentam uma assembléia mineral com possibilidades de existência de diamantes. As ilmenitas magnesianas presentes nessas rochas possuem uma composição indicativa de um ambiente gerador favorável à preservação de diamantes. Entretanto, a inexistência de macrocristais de cromita com alta porcentagem de Cr2O3 e de granadas do tipo G10 e/ou eclogitícas com altos teores de Na2O frusta essa propensão à mineralização. Isto porque, estas intrusões aparentemente não amostraram xenólitos e macrocristais de alta pressão situados dentro da região do campo de estabilidade dos diamantes no manto. / An integrated petrographic and mineral chemistry study has been carried out on ultramafic, potassic to ultrapotassic and silica-undersaturated rocks of kimberlitic affinity of the Indaiá I and Indaiá II intrusions, Western Minas Gerais State, Brazil. These rocks outcrop at the Alto Paranaíba Igneous Province (PIAP), within a N30W-trending, elongated area, which is 250-km long and 70-km wide. The PIAP suites are located on the western border of the São Francisco Craton and are emplaced in a basement composed of rocks from the Craton itself and late Proterozoic Brasília fold belt. Within the limitations imposed by the overlapping mineralogical characteristics of the kimberlite, lamproite, kamafugite, orangeite and lamprophyre clans, petrographic data show differences in the Indaiá I and II mineralogical compositions. Indaiá I consists of olivine, opaque mineral and orthopyroxene megacrysts and phenocrysts set in an aphanitic groundmass of olivine, opaque minerals, tabular monticellite, subeuhedral brown perovskite, green diopside and carbonates, whereas Indaiá II comprises anhedral to subeuhedral olivine phenocrysts set in an aphanitic matrix of prismatic to subeuhedral greenish diopside microphenocrysts, anhedral opaque minerals and related brownish spinel, perovskite, rounded olivine and occasional interstitial (devitrified) glass. The Indaiá I mineral chemistry comprises chrysolite to forsterite [83 < Mg/(Mg+Fe2+) < 95], enstatite (En85.3Fs12.7Wo1.54), magnesian ilmenite, Cr-bearing spinels from spinel to chromite-magnetite-ulvöspinel members, monticellite (92 mol% CaMgSiO4 end-member), and perovskite (93 mol% CaTiO3 end-member). Indaiá II is similar to Indaiá I, except for the slightly Ca-enriched diopsidic clinopyroxene (En39.7Fs10.2Wo48.0), and the lack of spinels and monticellite. On the basis of petrographic characteristics and mineral chemistry, it is proposed that the rocks from both Indaiá I and II belong to the Group I kimberlites. Both the intrusions are similar to many Group I kimberlites of the world and comprise some minerals that indicate the possible presence of diamonds, such as the magnesian ilmenite, whose composition reflects generation conditions to preserve diamonds. However, the generalized lack of chromite macrocrysts with high Cr2O3 contents and G10 and/or eclogitic garnets with high Na2O contents attests for the lack of diamonds, once these intrusions have not sampled highpressure xenoliths and macrocrysts within the diamond stability field in the mantle.

A presente dissertação se ocupou da investigação petrográfica e química mineral de rochas ultramáficas, potássica-ultrapotássicas, insaturadas em sílica, de afinidade kimberlítica, das intrusões Indaiá I e Indaiá II, oeste do Estado de Minas Gerais. Estas rochas afloram na Província Ígnea do Alto Paranaíba (PIAP, Cretáceo Superior), dentro de uma área alongada segundo N30W, perfazendo aproximadamente 250 km de extensão e 70 km de largura. As suítes do PIAP encontram-se à margem oeste do Cráton do São Francisco, alojadas em litologias pertencentes próprio Cráton e à Faixa Brasília. Os dados petrográficos, dentro das suas limitações, principalmente no que tange à sobreposição de características entre as rochas dos clãs kimberlitos, lamproítos, kamafugitos, orangeitos e lamprófiros, denotam na intrusão Indaiá I a presença de texturas porfiríticas, compostas de mega e fenocristais anédricos a subédricos de olivina, opacos e mais raramente de enstatita, fixados em matriz afanítica formada de cristais anédricos de olivina (crisolitaforsterita), minerais opacos, monticellita tabular, cristais amarronzados subédricos de perovskita, clinopiroxênio (diopsídio) esverdeado e carbonatos. Já na intrusão II se observa a presença de fenocristais anédricos a subédricos de olivina, fixados em matriz afanítica contendo alguns microfenocristais, prismáticos a subédricos, de clinopiroxênio diopsídico esverdeado, cristais anédricos de minerais opacos associados a espinélio avermelhado, cristais subédricos a anédricos de perovskita, grãos arredondados de olivina e também raro vidro intersticial, embora já devidrificado. A composição mineral observada nas rochas da intrusão Indaiá I é representada essencialmente por cristais de crisolita - forsterita (Mg/Mg+Fe2+ de 83 a 95), enstatita (En85,3Fs12,7Wo1,54), ilmenita magnesiana, Cr-espinélio representados por espinélio e membros da série chromite-magnetite-ulvöspinélio, monticellita (92% do membro final CaMgSiO4 ) e perovskita (93% do membro final CaTiO3). Na intrusão Indaiá II, a assembléia mineral presente é bastante similar à observada na intrusão I, contudo com um piroxênio diopsídico mais enriquecido em cálcio (En39,7Fs10,2Wo48,0) e ausência de minerais espinélio e monticellita. Com base na conjunção das características petrográficas e químicas dos minerais descritas no presente trabalho, propõe-se para as rochas das duas intrusões uma afinidade kimberlítica, pertencente ao clã dos kimberlitos do Grupo I. Apesar das ilmenitas magnesianas possuirem composições indicativas de que o líquido gerador das rochas favorece a preservação de diamantes, posto a inexistência de macrocristais de cromita com alta porcentagem de Cr2O3 e granadas G10 e/ou eclogitícas com altos teores de Na2O, a propensão à mineralização é frustada, isto porque, aparentemente, estas intrusões não amostraram xenólitos e macrocristais situados dentro da região do campo de estabilidade dos diamantes. As rochas de Indaiá I e Indaiá II apresentam uma assembléia mineral com possibilidades de existência de diamantes. As ilmenitas magnesianas presentes nessas rochas possuem uma composição indicativa de um ambiente gerador favorável à preservação de diamantes. Entretanto, a inexistência de macrocristais de cromita com alta porcentagem de Cr2O3 e de granadas do tipo G10 e/ou eclogitícas com altos teores de Na2O frusta essa propensão à mineralização. Isto porque, estas intrusões aparentemente não amostraram xenólitos e macrocristais de alta pressão situados dentro da região do campo de estabilidade dos diamantes no manto. / An integrated petrographic and mineral chemistry study has been carried out on ultramafic, potassic to ultrapotassic and silica-undersaturated rocks of kimberlitic affinity of the Indaiá I and Indaiá II intrusions, Western Minas Gerais State, Brazil. These rocks outcrop at the Alto Paranaíba Igneous Province (PIAP), within a N30W-trending, elongated area, which is 250-km long and 70-km wide. The PIAP suites are located on the western border of the São Francisco Craton and are emplaced in a basement composed of rocks from the Craton itself and late Proterozoic Brasília fold belt. Within the limitations imposed by the overlapping mineralogical characteristics of the kimberlite, lamproite, kamafugite, orangeite and lamprophyre clans, petrographic data show differences in the Indaiá I and II mineralogical compositions. Indaiá I consists of olivine, opaque mineral and orthopyroxene megacrysts and phenocrysts set in an aphanitic groundmass of olivine, opaque minerals, tabular monticellite, subeuhedral brown perovskite, green diopside and carbonates, whereas Indaiá II comprises anhedral to subeuhedral olivine phenocrysts set in an aphanitic matrix of prismatic to subeuhedral greenish diopside microphenocrysts, anhedral opaque minerals and related brownish spinel, perovskite, rounded olivine and occasional interstitial (devitrified) glass. The Indaiá I mineral chemistry comprises chrysolite to forsterite [83 < Mg/(Mg+Fe2+) < 95], enstatite (En85.3Fs12.7Wo1.54), magnesian ilmenite, Cr-bearing spinels from spinel to chromite-magnetite-ulvöspinel members, monticellite (92 mol% CaMgSiO4 end-member), and perovskite (93 mol% CaTiO3 end-member). Indaiá II is similar to Indaiá I, except for the slightly Ca-enriched diopsidic clinopyroxene (En39.7Fs10.2Wo48.0), and the lack of spinels and monticellite. On the basis of petrographic characteristics and mineral chemistry, it is proposed that the rocks from both Indaiá I and II belong to the Group I kimberlites. Both the intrusions are similar to many Group I kimberlites of the world and comprise some minerals that indicate the possible presence of diamonds, such as the magnesian ilmenite, whose composition reflects generation conditions to preserve diamonds. However, the generalized lack of chromite macrocrysts with high Cr2O3 contents and G10 and/or eclogitic garnets with high Na2O contents attests for the lack of diamonds, once these intrusions have not sampled highpressure xenoliths and macrocrysts within the diamond stability field in the mantle.

No description available.

Recent discoveries of kimberlites in North America have revealed that different processes are involved in the generation of kimberlite magma. A multi-disciplinary approach combining mineralogical, petrological, geochemical, and geochronological methods is used to classify the kimberlites, investigate possible sources of magma and evaluate current tectonic models proposed for the generation of kimberlite magma. The two main study areas are 1) the diamond-poor Churchill kimberlite field (Nunavut); and 2) the highly diamondiferous Lac de Gras kimberlite field (NWT). The Attawapiskat kimberlite field, the Kirkland Lake kimberlite field and the Timiskaming kimberlite field (Ontario) are also included in this study. The 55-56 Ma Diavik kimberlite cluster (NWT) have been classified as resedimented volcaniclastic > olivine-bearing volcaniclastic > mud-bearing volcaniclastic > macrocrystic oxide-bearing hypabyssal kimberlite > calcite oxide hypabyssal kimberlite > tuffisitic kimberlite breccia. Geochemical features of Diavik kimberlites include: 1) LREE enrichment, 2) large intra-field range in REE content, and 3) highly diamondiferous kimberlites at Diavik with primitive geochemical signatures. The Churchill kimberlites are classified as sparsely macrocrystic, oxide-rich calcite evolved hypabyssal kimberlite and macrocrystic oxide-rich monticellite phlogopite hypabyssal kimberlite. Electron microprobe analyses of olivine, phlogopite, spinel and perovskite support this petrographical classification. Twenty-seven precise U-Pb perovskite and Rb-Sr phlogopite emplacement ages indicate that magmatism spans ~45 million years (225-170 Ma). The crystallization ages and the Sr and Nd isotopic compositions of groundmass perovskite from a well-established, SE-trending Triassic-Jurassic corridor of kimberlite magmatism in Eastern North America (ENA) were determined to investigate the origin of this magmatism. The Sr isotopic results indicate that the Churchill (0.7032-0.7036) and Attawapiskat kimberlites (0.7049-0.7042) have unique isotopic compositions, while Kirkland Lake/Timiskaming perovskite have a larger range of 87Sr/86Sr ratios. This implies the derivation of kimberlite magma from two distinct sources in the mantle, a depleted MORB mantle source and a kimberlite magma with a Bulk Silicate Earth signature. The pattern of increasing 87Sr/86Srinitial with younging of kimberlite magmatism along the ~2000 km corridor of continuous Triassic/Jurassic magmatism could be explained from either a single or multiple hotspot track(s), responsible for the addition of heat required to generate small volume mantle melting of a kimberlite source.

Kimberlitos são rochas vulcânicas que, frequentemente, contêm diamante, grafite e/ou carbonato, sendo a presença destes componentes diretamente influenciada pela variabilidade da fugacidade de oxigênio (fO2) do magma durante a sua ascenção. Segundo Chakhmouradian and Mitchell (2000), CaTiO3-perovskitas podem ser usadas para revelar as condições de alguns dos múltiplos estágios de cristalização da história magmática destas rochas. No intuito de estabelecer a fugacidade de oxigênio de magmas kimberlíticos naturais, CaTiO3-perovskitas foram cristalizadas experimentalmente em equilíbrio com um líquido kimberlítico sintético em altas temperaturas e diferentes condições de pressão e de fugacidade de oxigênio. Os experimentos mostraram que a perovskita incorporou maiores quantidades de Fe3+ com o aumento da fO2. A equação do oxigênio barômetro desenvolvida neste estudo pode ser aplicada em rochas kimberlíticas de diferentes condições de fO2, que contêm CaTiO3-perovskita e olivina. Na presente pesquisa, nós aplicamos este oxigênio barômetro em amostras do kimberlito Rosário do Sul, que é um kimberlito transicional localizado no limite sudoeste da Bacia do Paraná. Os dados de minerais deste kimberlito sugerem que sua fonte é um produto da reação de um líquido silicático-carbonatítico com o manto. Idades U-Pb de ~ 128Ma em CaTiO3-perovskitas (Conceição et al., in prep.) revelam que o kimberlito Rosário do Sul provavelmente entrou em erupção logo após o vulcanismo da Província Paraná-Etendeka. Temperaturas de cristalização, pressões e fO2 dos kimberlitos Rosário do Sul e Alfeu-I, outro importante kimberlito situado no sul do Brasil, foram calculadas. As condições de suas fontes foram estimadas usando diferentes métodos a partir das composições de olivinas, espinélios, CaTiO3-perovskitas, granadas, ortopiroxênios e clinopiroxênios. As temperaturas, pressões e condições de fO2 dos kimberlitos Rosário do Sul e Alfeu-I sugerem que eles foram transportados para a superfície em condições nas quais fluidos ricos em CO2 podem reagir com o manto silicático e produzir carbonatos. A composição mineral e as condições de formação do kimberlito Rosário do Sul indicam que a sua fonte pode ter sido metassomatizada por fluidos provenientes da reciclagem de uma placa oceânica subductada durante a quebra do Gondwana e abertura do Atlântico Sul, logo depois do vulcanismo da Província Paraná-Etendeka. As condições de formação dos kimberlitos Rosário do Sul e Alfeu-I são usadas também para estimar o potencial destes kimberlitos em preservar diamantes. / Kimberlites are volcanic rocks which often contain diamonds, graphite and/or carbonate, and the stability of these minerals is directly influenced by the variability of oxygen fugacity (fO2) of the magma during its ascent. Second Chakhmouradian and Mitchell (2000), CaTiO3-perovskites may be used to unravel the conditions of some of the multiple stages of crystallization in the magmatic history of these rocks. In order to establish oxygen fugacities of natural kimberlititic magmas, we experimentally equilibrated CaTiO3-perovskites with synthetic kimberlitic melts at high temperatures, different oxygen fugacities and different pressures. The experiments show that perovskite incorporates increasing amounts of Fe3+ with increasing fO2. The oxygen barometer equation developed in this study can be applied in kimberlite rocks that contain CaTiO3-perovskite and olivine from different fO2 conditions. In the present research, we applied this oxygen barometer in the Rosário do Sul kimberlite samples, which is a transitional kimberlite located in the southwestern edge of the Paraná Basin. The mineral data of this kimberlite suggest that its source is a product of the reaction of a silicate-carbonate liquid in the mantle. U-Pb ages of ~ 128 Ma on CaTiO3-perovskites (Conceição et al., in prep.) reveal that the Rosário do Sul kimberlite probably erupted just after the volcanism of Paraná-Etendeka Province. We calculated crystallization temperatures, pressures and oxygen fugacities (fO2) of Rosário do Sul and Alfeu-I kimberlites, another important kimberlite situated in the South of Brazil. Their source conditions are estimated using different methods from olivines, spinels, CaTiO3-perovskites, garnets, orthopyroxenes and clinopyroxenes compositions. The calculated temperature, pressure and fO2 values of Rosário do Sul and Alfeu-I kimberlites suggest that they were transported to the surface under fO2 conditions in which CO2-rich fluids may react with mantle silicates to produce carbonates. The mineral composition and fO2 conditions of Rosário do Sul kimberlite indicate that its source may have been metasomatized by fluids generated from the recycling of a subducted oceanic plate during the Gondwana breakup and the South Atlantic opening, just after the Paraná-Etendeka Province volcanism. The source conditions of Rosário do Sul and Alfeu-I kimberlites are also used to estimate the potential of these kimberlites to preserve diamonds.

abstract: Oxygen fugacity (ƒO2) is a thermodynamic variable used to represent the redox state of a material or a system. It is equivalent to the partial pressure of oxygen in a particular environment corrected for the non-ideal behavior of the gas. ƒO2 is often used to indicate the potential for iron to occur in a more oxidized or reduced state at a particular temperature and pressure in a natural system. Secondary ion mass spectrometry (SIMS) is a powerful analytical instrument that can be used to analyze elemental and isotopic compositional information about microscopic features within solid materials. SIMS analyses of the secondary ion energy distribution of semi-pure metals demonstrate that the energy spectrum of individual mass lines can provide information about alterations in its surface environment. The application of high-resolution (see Appendix C) energy spectrum calibrations to natural ilmenite led to the investigation of zirconium (90Zr+) and niobium (93Nb+) as potential indicators of sample ƒO2. Energy spectrum measurements were performed on an array of ilmenite crystals from the earth’s upper mantle retrieved from kimberlites and from a reduced meteorite. In all studied materials, variability in the peak shape and width of the energy spectra has been correlated with inferred sample ƒO2. The best descriptor of this relationship is the full-width at half-maximum (FWHM; see Appendix C) of the energy spectra for each sample. It has been estimated that a 1eV change in the FWHM of 93Nb+ energy spectra is roughly equivalent to 1 log unit ƒO2. Simple estimates of precision suggest the FWHM values can be trusted to  1eV and sample ƒO2 can be predicted to ±1 log unit, assuming the temperature of formation is known. The work of this thesis also explores the applicability of this technique beyond analysis of semi-pure metals and ilmenite crystals from kimberlites. This technique was applied to titanium oxides experimentally formed at known ƒO2 as well as an ilmenite crystal that showed compositional variations across the grain (i.e., core to rim chemical variations). Analyses of titanium oxides formed at known ƒO2 agree with the estimation that 1 eV change in the FWHM of 93Nb+ is equivalent to ~1 log unit ƒO2 (in all cases but one); this is also true for analyses of a natural ilmenite crystal with compositional variations across the grain. / Dissertation/Thesis / Masters Thesis Geological Sciences 2019

In the James Bay Lowlands of northern Ontario, kimberlite pipes are concealed by peat, thick layers of till, and Tyrell sea sediments. Studies have shown that buried ore bodies produce geochemical signatures in surface media. This thesis explores the geochemistry of near-surface groundwater above concealed kimberlite pipes using factor analysis to determine whether (1) a factor analysis can reveal an underlying structure (factors) in a multivariate groundwater geochemical dataset, and whether (2) those factors are related to the presence of concealed kimberlite. Factor analysis was performed on two datasets of nearsurface groundwater, collected at 0.2 m and 1.1 m below ground surface in peat. Results revealed that (1) there is a significant difference in the behaviour of elements in groundwater near the surface compared to those in deeper groundwater, which is sheltered from the effects of the atmosphere; (2) for both datasets, the first factor is dominated by elements known to be enriched in kimberlite, notably rare earth elements (REE), U, Th, Ti – the composition of factor one is consistent with their derivation from kimberlite in a limestone background where such elements are in very low concentration; (3) high-valence and lowvalence kimberlite indicator elements (KIE) are found separated into distinct factors suggesting that once released from the kimberlite after weathering, KIE are subjected to various geochemical processes to be differentiated as they migrate upward to the surface; and (4) Fe and Mn load on a factor distinct from other metals, suggesting that in this environment Fe-Mn-O-OH is not a significant controller of metal mobility in groundwater. Overall, this research has further highlighted the multivariate nature of geochemical processes in groundwater. Compared with previous work in geochemical exploration where often only univariate or bivariate statistics or single element profiles over concealed ore bodies were used, this thesis has shown that factor analysis, as a multivariate data analysis technique, is a robust exploration tool, able to shed light on relevant geochemical processes hidden within geochemical datasets. This thesis shows that high-valence KIE, notably U,V, Th, Ti and the REE, as a group, are better indicators of the presence of kimberlites than other well-known KIE. Single element concentration profiles such as Ni or Cr (known KIE) show similar anomalies over a concealed kimberlite as a factor score profile for factor one (U, V, Th, Ti, REE, Ni) would; however, it is the peculiar assemblage of elements in factor one that makes it unique to kimberlites, a feature that can be used in future exploration work for concealed kimberlites in similar surficial environments, such as the Siberian wetlands. The results suggest that future geochemical exploration work involving groundwater should focus on the more stable groundwater located below the zone of oxidation, sheltered from the effects of the atmosphere.

In the James Bay Lowlands of northern Ontario, kimberlite pipes are concealed by peat, thick layers of till, and Tyrell sea sediments. Studies have shown that buried ore bodies produce geochemical signatures in surface media. This thesis explores the geochemistry of near-surface groundwater above concealed kimberlite pipes using factor analysis to determine whether (1) a factor analysis can reveal an underlying structure (factors) in a multivariate groundwater geochemical dataset, and whether (2) those factors are related to the presence of concealed kimberlite. Factor analysis was performed on two datasets of nearsurface groundwater, collected at 0.2 m and 1.1 m below ground surface in peat. Results revealed that (1) there is a significant difference in the behaviour of elements in groundwater near the surface compared to those in deeper groundwater, which is sheltered from the effects of the atmosphere; (2) for both datasets, the first factor is dominated by elements known to be enriched in kimberlite, notably rare earth elements (REE), U, Th, Ti – the composition of factor one is consistent with their derivation from kimberlite in a limestone background where such elements are in very low concentration; (3) high-valence and lowvalence kimberlite indicator elements (KIE) are found separated into distinct factors suggesting that once released from the kimberlite after weathering, KIE are subjected to various geochemical processes to be differentiated as they migrate upward to the surface; and (4) Fe and Mn load on a factor distinct from other metals, suggesting that in this environment Fe-Mn-O-OH is not a significant controller of metal mobility in groundwater. Overall, this research has further highlighted the multivariate nature of geochemical processes in groundwater. Compared with previous work in geochemical exploration where often only univariate or bivariate statistics or single element profiles over concealed ore bodies were used, this thesis has shown that factor analysis, as a multivariate data analysis technique, is a robust exploration tool, able to shed light on relevant geochemical processes hidden within geochemical datasets. This thesis shows that high-valence KIE, notably U,V, Th, Ti and the REE, as a group, are better indicators of the presence of kimberlites than other well-known KIE. Single element concentration profiles such as Ni or Cr (known KIE) show similar anomalies over a concealed kimberlite as a factor score profile for factor one (U, V, Th, Ti, REE, Ni) would; however, it is the peculiar assemblage of elements in factor one that makes it unique to kimberlites, a feature that can be used in future exploration work for concealed kimberlites in similar surficial environments, such as the Siberian wetlands. The results suggest that future geochemical exploration work involving groundwater should focus on the more stable groundwater located below the zone of oxidation, sheltered from the effects of the atmosphere.