Student Number : 0006342N - PhD thesis - School of Chemistry - Faculty of Science / An improved slurry method for determination of PGMs, gold and base metals (Ni, Cu, Fe and Co) using ICP-OES analytical instrument has been developed. This method has been successfully applied to quantitate metals in mineral concentrates and biological samples (grass, lichens, leaves and tree trunks) and validated using analytical figure of merit that include limits of detection, limits of quantition, accuracy and precision. Sample grinding using Fritsch GmbH Pulverissette Planetary Mono Mill was optimized to get > 60% and >80% of the particles to < 5.0 μm and < 10 μm respectively. The optimum grinding conditions for a sample mass of 0.4 g was determined as 130 rpm grinding speed and 30 minutes grinding time. An additional 15 minutes mixing with reagent was employed to ensure better slurry homogeneity for improved precisions. Five slurry dispersants; tetrasodium pyrophosphate, Triton X-100, dodecylbenzene sulfonic acid sodium salt, potassium cyanide and potassium thiocyanate, were evaluated at varied concentrations and 0.1% v/v Triton X-100 established as the best dispersant for slurry preparation. The ICP-OES sample delivery system was modified by introducing an extension elbow between the torch and the spray chamber that not only effectively reduced the sample residence time in the plasma for efficient atomization of the particles but also acted as a gravitational sieve eliminating larger particles and droplets. Prepared slurries were continuously agitated using an ultrasonic bath prior to and during aspiration into ICP-OES to prevent sedimentation and ensure constant stability of the slurry. Optimum operating conditions for ICP-OES established as 1600 W and 1450 W plasma power for PGMs and base metals respectively, using a nebulizer flow rate of 0.8 mL min-1, coolant gas flow rate of 13.0 mL min-1, auxiliary gas flow rate of 1.0 L min-1 with a sample uptake rate of 0.2 mL min-1. Limits of detection for the developed technique were determined in μg g-1 as 0.075, 0.039, 0.115, 0.071, 0.035 and 0.118 for Au, Ir, Pd, Pt, Rh and Ru respectively and 0.15, 0.391, 0.345 and 0.217 for Ni, Cu, Fe and Co respectively. Limits of quantitation in μg g-1 were obtained as 0.250, 0.130, 0.383, 0.237, 0.117 and 0.393 for Ir, Pd, Pt, Rh and Ru respectively and 0.5, 1.31, 1.15 and 0.723 for Ni, Cu, Fe and Co respectively. Good accuracy was recorded for all the base metals as well as for the platinum group metals and gold except iridium that was susceptible to copper interference. Two measurements of precision, reproducibility and repeatability were assessed. Reproducibility was obtained in percentages as 12, 7.93, 5.54, 10 and 12 for Au, Pd, Pt, Rh and Ru respectively and 9.9, 10, 9.8 and 10 for Ni, Cu, Fe and Co respectively. Repeatability was obtained in percentages as 11, 7.03, 4.94, 8.08 and 9.85 for Au, Pd, Pt, Rh and Ru respectively and 9.4, 9.6, 9.7 and 10 for Ni, Cu, Fe and Co respectively. Good percentage recoveries were obtained of 104.3%, 98.3%, 98%, 90.5% and 92.8% for Au, Pd, Pt, Rh and Ru respectively. Percentage recoveries of 109%, 111%, 89.9% and 100% for Ni, Cu, Fe and Co respectively were obtained. The simplicity and low cost of sample preparation used in this method enables it to be easily adopted in any ICP-OES laboratory. A single analyst may achieve more sample through-puts than before per day (including re-grinding and analysis), resulting in a highly economical and rapid technique for determination of metals.

A Província Aurífera de Alta Floresta insere-se na porção sul do Cráton Amazônico e constitui uma região alongada na direção WNW-ESSE onde se situam depósitos auríferos associados ao magmatismo plutonovulcânico Paleoproterozoico. A área pesquisada abrange o garimpo de ouro do Papagaio, situado em Paranaíta, Mato Grosso. Durante o mapeamento geológico, foram identificados corpos de rochas plutônicas a subvulcânicas de composições granodiorítica e granítica, além de rochas vulcânicas e piroclásticas dacíticas e riolíticas. Estes litotipos são pertencentes à série calcioalcalina de médio a alto potássio, meta- a peraluminosas correspondentes a granitos do tipo I de arco vulcânico em margem continental ativa. As idades U-Pb mostraram que o magmatismo na região ocorreu aproximadamente entre 1.80 - 1.78 Ga. com zircões herdados de até 2,1 Ga, mostrando evidências da existência de uma crosta mais profunda e antiga durante a subducção. Os dados de \'épsilon\'Nd(t) mostraram a existência de contribuição crustal e mantélica na fonte de idade TDM entre 2.15-2.02 Ga. Estes dados revelaram que o vulcanismo na área é pertencente a Suíte Colíder, correspondente de um magmatismo que ficou ativo por aproximadamente 16 Ma e que evoluiu de composição dacítica a riolítica. A lavra garimpeira ocorre sobre uma mineralização aurífera com cobre, zinco e baixos teores de chumbo, preferencialmente confinada em veios que cortam os halos de alteração potássica, sericítica e propilítica. Os veios existentes na região evoluem de forma sistematica em seis tipos: (I) Veio de quartzo estéril associado ao halo da alteração potássica; (II) Veio de quartzo com minerais de minério, por vezes, associado ao halo sericítico; (III) Veio sulfetado com halo de alteração sericítica bem desenvolvido nas salbandas; (IV) e (V) Veios de quartzo e carbonato tardios; (VI) sistema de veios de quartzo mais novo e sem relação com a evolução do depósito. Os três primeiros tipos são semelhantes ao sistema A-B-D descrito em depósitos do tipo pórfiro, enquanto que os mais novos apresentam características de um ambiente mais raso e epitermal. O ouro ocorre principalmente na zona central dos veios do tipo II, em paragênese com a calcopirita + esfalerita + pirita ± galena ± magnetita. O quartzo dos veios sofreu diferentes intensidades de recristalização decorrente de subsequentes pulsos hidrotermais e as imagens de catodoluminescência mostraram que as inclusões fluidas aquocarbônicas representam fluidos primários com importante participação no transporte de conteúdo metalífero. Os resultados de isótopos estáveis de D, O e S em quartzo, sericita e pirita hidrotemais mostram que os fluidos são magmáticos com contribuições de fluidos meteóricos. Neste contexto, o Garimpo do Papagaio se desenvolveu sobre um arco magmático continental, a partir da intrusão de corpos graníticos hidratados e oxidados que marcam o evento magmático final da Suíte Colíder. Representa um depósito do tipo pórfiro que foi sobreposto por características epitermais intermediate-sulfidation, como resultado da telescopagem hidrotermal consequente do rebaixamento da câmara magmática. / The Alta Floresta Gold Province is situated on the southern portion of Amazonian Craton and forms an elongate region with WNW-ESSE direction where auriferous deposits are associated with Paleoproterozoic plutonovolcanic magmatism. The area of research covers the Papagaio artisanal gold mining, located in Paranaíta, Mato Grosso. During geological mapping, plutonic to subvolcanic rocks bodies of granodioritic and granitic compositions were identified, as well as dacitic and rhyolitic volcanic and pyroclastic rocks. These lithotypes belong to the calc-alkaline series of medium to high potassium, meta- to peraluminous corresponding to type I granites of volcanic arc in an active continental margin. U-Pb ages showed that magmatism in the region has crystallized in the range of 1.80-1.78 Ga with inherited zircons up to 2.1 Ga, showing evidence of a deeper and older crust during subduction. \'épsilon\'Nd (t) data showed the contribution of crustal and mantle material in the source with TDM age between 2.15- 2.02 Ga. These data revealed that volcanism in the area belongs to the Colíder Suite, corresponding to a magmatism that was active for approximately 16 Ma and evolved from dacitic to a rhyolitic composition. The mining prospect occurs on gold mineralization with copper, zinc and low levels of lead, preferably confined in veins that cut potassic, seritic and propylitic alteration halos. The existing veins in the region evolve systematically into six types: (I) Barren quartz vein associated with potassic alteration halo; (II) Quartz vein with ore minerals, sometimes associated with sericitic halo; (III) Sulphide vein with a well developed sericitic alteration halo in the salbands; (IV) and (V) Late quartz and carbonate veins; (VI) system of quartz veins newer and unrelated to deposit evolution. The first three types are similar to A-B-D system described in porphyry deposits, while the newer ones have characteristics of a shallower and epithermal environment. Gold occurs mainly in the central zone of the type II veins, in paragenesis with chalcopyrite + sphalerite + pyrite ± galena ± magnetite. The quartz of the veins underwent different intensities of recrystallization due to subsequent hydrothermal pulses and cathodoluminescence images showed that aquocarbonic fluid inclusions represent primary fluids with important participation in metalliferous content transportation. The results of D, O and S stable isotope in hydrothermal quartz, sericite and pyrite show that fluids are magmatic with meteoric contributions. In this context, the Papagaio artisanal mining developed on a continental magmatic arc, from the intrusion of hydrated and oxidized granite bodies that mark the final magmatic event of the Colíder Suite. It represents a porphyry deposit that was superimposed by epithermal intermediate-sulfidation characteristics as a result of hydrothermal telescoping, resulting from the lowering of the magma chamber.

A Província Aurífera de Alta Floresta insere-se na porção sul do Cráton Amazônico e constitui uma região alongada na direção WNW-ESSE onde se situam depósitos auríferos associados ao magmatismo plutonovulcânico Paleoproterozoico. A área pesquisada abrange o garimpo de ouro do Papagaio, situado em Paranaíta, Mato Grosso. Durante o mapeamento geológico, foram identificados corpos de rochas plutônicas a subvulcânicas de composições granodiorítica e granítica, além de rochas vulcânicas e piroclásticas dacíticas e riolíticas. Estes litotipos são pertencentes à série calcioalcalina de médio a alto potássio, meta- a peraluminosas correspondentes a granitos do tipo I de arco vulcânico em margem continental ativa. As idades U-Pb mostraram que o magmatismo na região ocorreu aproximadamente entre 1.80 - 1.78 Ga. com zircões herdados de até 2,1 Ga, mostrando evidências da existência de uma crosta mais profunda e antiga durante a subducção. Os dados de \'épsilon\'Nd(t) mostraram a existência de contribuição crustal e mantélica na fonte de idade TDM entre 2.15-2.02 Ga. Estes dados revelaram que o vulcanismo na área é pertencente a Suíte Colíder, correspondente de um magmatismo que ficou ativo por aproximadamente 16 Ma e que evoluiu de composição dacítica a riolítica. A lavra garimpeira ocorre sobre uma mineralização aurífera com cobre, zinco e baixos teores de chumbo, preferencialmente confinada em veios que cortam os halos de alteração potássica, sericítica e propilítica. Os veios existentes na região evoluem de forma sistematica em seis tipos: (I) Veio de quartzo estéril associado ao halo da alteração potássica; (II) Veio de quartzo com minerais de minério, por vezes, associado ao halo sericítico; (III) Veio sulfetado com halo de alteração sericítica bem desenvolvido nas salbandas; (IV) e (V) Veios de quartzo e carbonato tardios; (VI) sistema de veios de quartzo mais novo e sem relação com a evolução do depósito. Os três primeiros tipos são semelhantes ao sistema A-B-D descrito em depósitos do tipo pórfiro, enquanto que os mais novos apresentam características de um ambiente mais raso e epitermal. O ouro ocorre principalmente na zona central dos veios do tipo II, em paragênese com a calcopirita + esfalerita + pirita ± galena ± magnetita. O quartzo dos veios sofreu diferentes intensidades de recristalização decorrente de subsequentes pulsos hidrotermais e as imagens de catodoluminescência mostraram que as inclusões fluidas aquocarbônicas representam fluidos primários com importante participação no transporte de conteúdo metalífero. Os resultados de isótopos estáveis de D, O e S em quartzo, sericita e pirita hidrotemais mostram que os fluidos são magmáticos com contribuições de fluidos meteóricos. Neste contexto, o Garimpo do Papagaio se desenvolveu sobre um arco magmático continental, a partir da intrusão de corpos graníticos hidratados e oxidados que marcam o evento magmático final da Suíte Colíder. Representa um depósito do tipo pórfiro que foi sobreposto por características epitermais intermediate-sulfidation, como resultado da telescopagem hidrotermal consequente do rebaixamento da câmara magmática. / The Alta Floresta Gold Province is situated on the southern portion of Amazonian Craton and forms an elongate region with WNW-ESSE direction where auriferous deposits are associated with Paleoproterozoic plutonovolcanic magmatism. The area of research covers the Papagaio artisanal gold mining, located in Paranaíta, Mato Grosso. During geological mapping, plutonic to subvolcanic rocks bodies of granodioritic and granitic compositions were identified, as well as dacitic and rhyolitic volcanic and pyroclastic rocks. These lithotypes belong to the calc-alkaline series of medium to high potassium, meta- to peraluminous corresponding to type I granites of volcanic arc in an active continental margin. U-Pb ages showed that magmatism in the region has crystallized in the range of 1.80-1.78 Ga with inherited zircons up to 2.1 Ga, showing evidence of a deeper and older crust during subduction. \'épsilon\'Nd (t) data showed the contribution of crustal and mantle material in the source with TDM age between 2.15- 2.02 Ga. These data revealed that volcanism in the area belongs to the Colíder Suite, corresponding to a magmatism that was active for approximately 16 Ma and evolved from dacitic to a rhyolitic composition. The mining prospect occurs on gold mineralization with copper, zinc and low levels of lead, preferably confined in veins that cut potassic, seritic and propylitic alteration halos. The existing veins in the region evolve systematically into six types: (I) Barren quartz vein associated with potassic alteration halo; (II) Quartz vein with ore minerals, sometimes associated with sericitic halo; (III) Sulphide vein with a well developed sericitic alteration halo in the salbands; (IV) and (V) Late quartz and carbonate veins; (VI) system of quartz veins newer and unrelated to deposit evolution. The first three types are similar to A-B-D system described in porphyry deposits, while the newer ones have characteristics of a shallower and epithermal environment. Gold occurs mainly in the central zone of the type II veins, in paragenesis with chalcopyrite + sphalerite + pyrite ± galena ± magnetite. The quartz of the veins underwent different intensities of recrystallization due to subsequent hydrothermal pulses and cathodoluminescence images showed that aquocarbonic fluid inclusions represent primary fluids with important participation in metalliferous content transportation. The results of D, O and S stable isotope in hydrothermal quartz, sericite and pyrite show that fluids are magmatic with meteoric contributions. In this context, the Papagaio artisanal mining developed on a continental magmatic arc, from the intrusion of hydrated and oxidized granite bodies that mark the final magmatic event of the Colíder Suite. It represents a porphyry deposit that was superimposed by epithermal intermediate-sulfidation characteristics as a result of hydrothermal telescoping, resulting from the lowering of the magma chamber.