The objective of this thesis is to calibrate two oxygen barometers for kimberlite magmas in the system CaO-MgO-Al2O3-SiO2-TiO2-FeO based on the Fe and V content of monticellite, CaMgSiO4, that may be utilized in cases where oxides in olivine phenocrysts and perovskite are absent from a kimberlite pipe. I first calibrate a new oxygen barometer for kimberlite magmas based on the Fe content of monticellite in equilibrium with kimberlite liquids in experiments at 100kPa from 1230 to 1350C and at fO2 from NNO-4.1 to NNO+5.3 (where NNO is the nickel-nickel oxide buffer). The XFeMtc/XFeliq (where XFeMtc/XFeliq is the ratio of mole fraction of total Fe in monticellite and Fe in liquid) decreases with increasing fO2, consistent with only Fe2+ entering the monticellite structure. Although the XFe in monticellite varies with temperature and bulk composition, these dependencies are small (0.03) compared to that with fO2. The experimental data were fitted by weigted least square regression to the following relationship: DNNO= (log (0.858(0.021)*XFeliq/XFeMtc-1)-0.139(0.022))/0.193(0.004) (uncertainties at 2 sigma). I apply this oxygen barometer to natural kimberlite assuming the bulk rock FeO is that of their liquid FeO. Monticellite compositions of five kimberlites from both literature and my own investigations revealed a range in fO2 from NNO-3.5 to NNO+1.7. I finally use my well-defined monticellite-liquid Kd Fe2+-Mg to derive a range of Mg/(Mg+Fe2+) (Mg number) for kimberlite melts of 0.40-0.90. This range in composition is broader than previous estimates of 'primary' kimberlites, reflecting the diverse mantle sources and processes that occur during generation and ascent of kimberlites. Second, I calibrate a new oxygen barometer for kimberlite magmas based on the V content of monticellite in equilibrium with kimberlite liquids doped with 0.5 wt% V2O5 at 100kPa at 1280 and 1350C and at fO2 from NNO-4.1 to NNO_0.5. The DV Mtc/liq (DV Mtc/liq = V (ppm) in monticellite/V (ppm) in liquid) decreases with increasing fO2. The partitioning data can be fitted to a model consistent with V5+ as the dominant species in the melt phase above NNO whereas V4+ dominates below those conditions in kimberlitic magmas. The total DV Mtc/liq, which embodies both DV3+ Mtc/liq and DV4+ Mtc/liq, shows a very slight temperature and bulk composition dependence. The experimental data can be fitted by weighted least square regression to the following relationship: DNNO= (log(0.354(1.785)*Vliq/VMtc-1)-1.172(2.302))/0.111(0.071) (uncertainties at 2 sigma and V in ppm). In order to apply this oxygen barometer rigorously, the V concentrations of the kimberlite melt coexisting with monticellite need to be constrained. In contrast to the Fe-in-monticellite oxygen barometer for which the concentration of Fe in monticellite was close to that of the whole rock composition, the concentration of V in the bulk rock composition reflects mostly the large accumulation of olivine xenocrysts which contain low V concentrations. For that reason, the V-in-monticellite oxygen barometer cannot be applied to natural kimberlites until we find a way to overcome this problem. The vanadium concentrations of kimberlite melts are likely higher than the V concentrations of the whole rock compositions leading to underestimated fO2 values. / Graduate

Foram estudados as propriedades de absorção ótica, de termoluminescência e de ressonância paramagnética eletrônica do mineral natural de silicato de nome MONTICELITA do grupo Olivina, para caracterização desse mineral, cuja formula química é CaMgSiO4. A absorção ótica mostrou que há três bandas de absorção em 450 nm, 660 nm e 1050 nm. As duas primeiras bandas, a primeira no azul e a segunda no amarelo-vermelho são responsáveis pela cor verde da Monticelita. Essas duas bandas são consequência do elemento cromo contido no mineral absorver fótons do feixe universal no visível de frequências centradas em 450 nm e 660 nm. A banda em 1050 nm é devido ao Fe2+. As curvas de emissão de uma amostra de Monticelita irradiada com raios gama de doses entre 10 e 1000 Gy apresenta três picos em 150 °C , 270 °C e 370 °C . Pelo método da deconvolução e de várias taxas de aquecimento foram obtidos energia E1=1,35 eV e fator de frequência s1=4,98x1011 s-1 para o pico 270 °C e E2=1,70 eV e s2=1,88x1011 s-1 para pico 370 °C . A irradiação com raios gama de doses entre 5 kGy e 50 kGy produziram pico TL de 380 °C com intensidade TL em função da dose linear e crescente. Este resultado e importante para dosimetria da radiação de altas doses. O espectro EPR de uma amostra natural, mostrou um resultado não esperado e interessante. Além dos sinais típicos de interação hiperfina do Mn2+, um sinal avantajado de g =6,34 indica que o ferro formou moléculas de hematita, Fe2O3. Esse sinal desaparece com aquecimento acima de 800 °C de recozimento, dando origem dipolos magnéticos de Fe3+, que dá origem a um sinal típico em g =2. Esta descrição mostra bem a caracterização do mineral Monticelita. / The properties of optical absorption, thermoluminescence and electron paramagnetic resonance of natural silicate mineral named MONTICELLITE belonging to Olivine group have been investigate in order to characterize this mineral of chemical formula CaMgSiO4. The optical absorption spectrum has shown that there are three bands in visible and near infrared. They occur at 450, 660 and 1050 nm. The two first absorption bands, first one around blue and second one around yellow-red are responsible for green colour of mineral. It was shown that these two absorption bands are due to absorption by chromium contained in the material of 450 nm photon and 660 nm photon from incident beam in the spectrophotometer causing excitation from fundamental to two excited states. 1050 nm band is due to Fe2+. Glow curves of Monticellite sample irradiated with γ-rays have shown TL peaks at 150, 270 e 370 °C. Using deconvolution method and various heating rates method following activation energy and frequency factor values for 270 °C peak, E1=1.35 eV and s1=4,98x1011 s-1 and for 370 °C peak E2=1.70 eV and s2=1,88x1011 s-1. Irradiation with y-rays with dose varying from 5 to 50 kGy a linear TL vs dose curve was obtained. This result shows that Monticellite Mineral can be used for high dose radiation dosimetry. The EPR spectrum of the natural sample presented an unexpected and interesting result. Besides a typical six lines due to hyperfine interaction in Mn2+ ion, a large signal with g =6,34 indicate an aggregate of hematite (Fe2O3). This signal changes into Fe3+ signal with g =2, under annealing at high temperatures of 800 to 1100 °C. Altogether these results characterize sufficiently enough the mineral Monticellite.

Foram estudados as propriedades de absorção ótica, de termoluminescência e de ressonância paramagnética eletrônica do mineral natural de silicato de nome MONTICELITA do grupo Olivina, para caracterização desse mineral, cuja formula química é CaMgSiO4. A absorção ótica mostrou que há três bandas de absorção em 450 nm, 660 nm e 1050 nm. As duas primeiras bandas, a primeira no azul e a segunda no amarelo-vermelho são responsáveis pela cor verde da Monticelita. Essas duas bandas são consequência do elemento cromo contido no mineral absorver fótons do feixe universal no visível de frequências centradas em 450 nm e 660 nm. A banda em 1050 nm é devido ao Fe2+. As curvas de emissão de uma amostra de Monticelita irradiada com raios gama de doses entre 10 e 1000 Gy apresenta três picos em 150 °C , 270 °C e 370 °C . Pelo método da deconvolução e de várias taxas de aquecimento foram obtidos energia E1=1,35 eV e fator de frequência s1=4,98x1011 s-1 para o pico 270 °C e E2=1,70 eV e s2=1,88x1011 s-1 para pico 370 °C . A irradiação com raios gama de doses entre 5 kGy e 50 kGy produziram pico TL de 380 °C com intensidade TL em função da dose linear e crescente. Este resultado e importante para dosimetria da radiação de altas doses. O espectro EPR de uma amostra natural, mostrou um resultado não esperado e interessante. Além dos sinais típicos de interação hiperfina do Mn2+, um sinal avantajado de g =6,34 indica que o ferro formou moléculas de hematita, Fe2O3. Esse sinal desaparece com aquecimento acima de 800 °C de recozimento, dando origem dipolos magnéticos de Fe3+, que dá origem a um sinal típico em g =2. Esta descrição mostra bem a caracterização do mineral Monticelita. / The properties of optical absorption, thermoluminescence and electron paramagnetic resonance of natural silicate mineral named MONTICELLITE belonging to Olivine group have been investigate in order to characterize this mineral of chemical formula CaMgSiO4. The optical absorption spectrum has shown that there are three bands in visible and near infrared. They occur at 450, 660 and 1050 nm. The two first absorption bands, first one around blue and second one around yellow-red are responsible for green colour of mineral. It was shown that these two absorption bands are due to absorption by chromium contained in the material of 450 nm photon and 660 nm photon from incident beam in the spectrophotometer causing excitation from fundamental to two excited states. 1050 nm band is due to Fe2+. Glow curves of Monticellite sample irradiated with γ-rays have shown TL peaks at 150, 270 e 370 °C. Using deconvolution method and various heating rates method following activation energy and frequency factor values for 270 °C peak, E1=1.35 eV and s1=4,98x1011 s-1 and for 370 °C peak E2=1.70 eV and s2=1,88x1011 s-1. Irradiation with y-rays with dose varying from 5 to 50 kGy a linear TL vs dose curve was obtained. This result shows that Monticellite Mineral can be used for high dose radiation dosimetry. The EPR spectrum of the natural sample presented an unexpected and interesting result. Besides a typical six lines due to hyperfine interaction in Mn2+ ion, a large signal with g =6,34 indicate an aggregate of hematite (Fe2O3). This signal changes into Fe3+ signal with g =2, under annealing at high temperatures of 800 to 1100 °C. Altogether these results characterize sufficiently enough the mineral Monticellite.