Dating minerals by ID-TIMS geochronology at times of in situ analysis: selected case studies from the CPGeo-IGc-USP laboratory

Since 1964, the Center for Geochronological Research - CPGeo, one of the interdepartmental centers of the Instituto de Geociências (IG) of São Paulo University, has developed studies related to several geological processes associated with different rock types. Thermal Ionization Mass Spectrometry Isotopic Dilution (ID-TIMS) has been the technique widely used in the CPGeo U-Pb Laboratory. It provides reliable and accurate results in age determination of superposed events. However, the open-system behavior such as Pb-loss, the inheritance problem and metamictization processes allow and impel us to a much richer understanding of the power and limitations of U-Pb geochronology and thermochronology. In this article, we present the current methodology used at the CPGeo-IGc-USP U-Pb laboratory, the improvements on ID-TIMS method, and report high-precision U-Pb data from zircon, monazite, epidote, titanite, baddeleyite and rutile from different rock types of several domains of the Brazilian south-southeast area, Argentina and Uruguay.O Centro de Pesquisas Geocronológicas (CPGeo), um dos centros interdepartamentais do Instituto de Geociências (IG) da Universidade de São Paulo (USP), desde 1964 desenvolve estudos relacionados a diversos processos geológicos que se associam a diferentes tipos de rochas. A técnica amplamente utilizada no Laboratório U-Pb é a diluição isotópica por espectrometria de massa termo ionizada (ID-TIMS). Esta sistemática proporciona resultados bastante confiáveis e precisos na determinação das idades de eventos geológicos superpostos. Entretanto, o comportamento de sistema aberto como perda de Pb, problemas de herança isotópica e processos de metamictização, nos permite o entendimento do poder e limitação da geocronologia e termocronologia U-Pb. Neste artigo apresentamos a metodologia atualmente utilizada no Laboratório U-Pb do CPGeo-IGc-USP, as melhorias atingidas na técnica ID-TIMS e alguns dados obtidos em zircão, epídoto, titanita, baddeleyita e rutilo de diferentes tipos de rochas de alguns domínios da região sul-sudeste brasileira e da Argentina e Uruguai.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Análises in situ de U e Pb em zircão por SHRIMP II por controle remoto e de Hf por LA-ICP-MS: um exemplo de datação e da evolução genética de zircão através da razão 176Hf/177Hf em amostra da pedreira Ita no Complexo Atuba, SE Brasil

Operar o espectrômetro de massa SHRIMP à distância, remotamente via Internet, é sem dúvida uma técnica alternativa de grande interesse para a datação de cristais de zircão. Embora não represente avanço no método geocronológico U-Pb em zircão, a técnica de operação remota traz, além de facilidade, grande economia nesse tipo de análise. Foi executada pela primeira vez em análises espectrométicas envolvendo dois laboratoratórios internacionais (São Paulo, Brasil - Beijing, China) possibilitando a obtenção de resultados em tempo real. O procedimento foi aplicado em três amostras de rochas gnáissico-migmatíticas da pedreira Ita (próxima à cidade de Curitiba - Paraná - Brasil) pertencentes ao Complexo Atuba. Tais rochas, quando analisadas através do método U-Pb (TIMS) demonstraram uma evolução complexa, com idades bastante imprecisas. A presença de importantes heranças arqueanas e paleoproterozoicas, neste complexo, foram confirmadas nas zonas internas de cristais de zircão obtidas em leucossomas neoproterozoicos. Análises adicionais realizadas em rochas dioríticas indicaram ser intrusivas, e não encaixantes, e apresentaram idades relacionadas às colisões continentais (0.6 Ga) envolvidas durante a assembléia de Gondwana, no Neoproterozoico. A determinação das razões de isótopos de Hf em cristais de zircão, por meio de LA-ICP-MS, representa uma nova opção para checar a importância relativa da contribuição de material do manto (&#949;Hf >; 0) e crosta (&#949;Hf ; 0) and crustal contributions (&#949;Hf < 0) during the growth of the zircon crystals. While the archean component in the complex was derived from the mantle (&#949;Hf +1.5 to +8.7) the paleoproterozoic component had a crustal contribution (&#949;Hf-9.1 to -10.1)

Novas técnicas aplicadas ao método U-Pb no CPGeo - IGc/USP: avanços na digestão química, espectrometria de massa (TIMS) e exemplos de aplicação integrada com SHRIMP

O presente trabalho tem como principal objetivo apresentar novas técnicas relativas ao método geocronológico U-Pb, principalmente em zircão, utilizadas no CPGeo-IGc/USP. Trata-se de um método que vem sendo constantemente aprimorado desde sua implantação na década de 90. Técnicas de separação ou concentração de zircão, digestão química parcial e total envolvendo lixiviamento e dissolução completa, concentrações de U e Pb em microcolunas de troca aniônica, utilização de spike 205Pb, bem como equações de cálculo de idade são comentadas. À guisa de exemplo, são discutidas aplicações de dados isotópicos U-Pb, obtidos em zircão com heranças isotópicas (presença de núcleo e borda), envolvendo técnicas de lixiviamento e forno de microondas convencional. Estudos relativos à gênese de zircão com base em isótopos de 176Hf/177Hf inicial complementam este trabalho. Por último, encontram-se totalmente desenvolvidas nos anexos, as formulações matemáticas utilizadas no programa PBDAT.The present work describes new techniques of U-Pb ID-TIMS developed at the CPGeo-IGc/USP. Techniques of partial and total chemical digestions, U and Pb concentration using anion exchange in a micro column, and the utilization of a 205Pb spike are discussed. Main geochronological equations used are also discussed. Examples of the application of U-Pb data, obtained by leaching technique using a microwave oven in zircon with isotopic inheritances in the core and border, are presented. The genesis of zircon based on the initial 176Hf/177Hf ratio is discussed. Finally complete listings of the mathematical formulations used in the PBDAT software are given in the appendix

A Comprehensive Patient-Derived Xenograft Collection Representing the Heterogeneity of Melanoma

Therapy of advanced melanoma is changing dramatically. Following mutational and biological subclassification of this heterogeneous cancer, several targeted and immune therapies were approved and increased survival significantly. To facilitate further advancements through pre-clinical in vivo modeling, we have established 459 patient-derived xenografts (PDX) and live tissue samples from 384 patients representing the full spectrum of clinical, therapeutic, mutational, and biological heterogeneity of melanoma. PDX have been characterized using targeted sequencing and protein arrays and are clinically annotated. This exhaustive live tissue resource includes PDX from 57 samples resistant to targeted therapy, 61 samples from responders and non-responders to immune checkpoint blockade, and 31 samples from brain metastasis. Uveal, mucosal, and acral subtypes are represented as well. We show examples of pre-clinical trials that highlight how the PDX collection can be used to develop and optimize precision therapies, biomarkers of response, and the targeting of rare genetic subgroups

New Techniques Applied to the U-Pb Method at the Centre for Geochronological Research of the University of São Paulo: Chemical Digestions, TIMS Mass Spectrometry and Examples of Integrated Application of SHRIMP

The present work describes new techniques of U-Pb ID-TIMS developed at the CPGeo-IGc/USP. Techniques of partial and total chemical digestions, U and Pb concentration using anion exchange in a micro column, and the utilization of a 205Pb spike are discussed. Main geochronological equations used are also discussed. Examples of the application of U-Pb data, obtained by leaching technique using a microwave oven in zircon with isotopic inheritances in the core and border, are presented. The genesis of zircon based on the initial 176Hf/177Hf ratio is discussed. Finally complete listings of the mathematicalformulations used in the PBDAT software are given in the appendix

In situ Sr isotope analyses by LA-MC-ICP-MS of igneous apatite and plagioclase from magmatic rocks at the CPGeo-USP

ABSTRACT: This contribution describes the successful implementation of in situ Sr isotope analyses by LA-MC-ICP-MS at the CPGeo-USP. The choice for an analytical configuration using measurements of half-masses allows the accurate assessment of lanthanide interferences, permitting the determination of Sr isotopes in important REE-rich accessory phases, such as apatite. Likewise, the on-peak-zero method effectively corrects the background contribution (both from Kr and residual Sr contributions from previous ablations) to the signals of the unknown samples. The analytical campaigns resulted in an accuracy, in respect to reference TIMS values, better than 57 ppm (~ ±0.000057 2&#963; SD) for a modern coral and the Batjberg clinopyroxene which impart significant quality to our data. Similarly, the majority of the stable Sr isotope ratios are close to the accepted values, which also confirms the effectiveness of the method. The achieved accuracy allows the identification and investigation of spatially-controlled isotopic heterogeneities on the micrometric scale in several Sr-rich minerals (apatite, carbonates, plagioclase, and clinopyroxene) with important implications to the understanding of relevant geochemical processes, particularly AFC, source geochemical heterogeneities and magma-mixing

In situ Sr isotope analyses by LA-MC-ICP-MS of igneous apatite and plagioclase from magmatic rocks at the CPGeo-USP

ABSTRACT: This contribution describes the successful implementation of in situ Sr isotope analyses by LA-MC-ICP-MS at the CPGeo-USP. The choice for an analytical configuration using measurements of half-masses allows the accurate assessment of lanthanide interferences, permitting the determination of Sr isotopes in important REE-rich accessory phases, such as apatite. Likewise, the on-peak-zero method effectively corrects the background contribution (both from Kr and residual Sr contributions from previous ablations) to the signals of the unknown samples. The analytical campaigns resulted in an accuracy, in respect to reference TIMS values, better than 57 ppm (~ ±0.000057 2σ SD) for a modern coral and the Batjberg clinopyroxene which impart significant quality to our data. Similarly, the majority of the stable Sr isotope ratios are close to the accepted values, which also confirms the effectiveness of the method. The achieved accuracy allows the identification and investigation of spatially-controlled isotopic heterogeneities on the micrometric scale in several Sr-rich minerals (apatite, carbonates, plagioclase, and clinopyroxene) with important implications to the understanding of relevant geochemical processes, particularly AFC, source geochemical heterogeneities and magma-mixing

A Comprehensive Patient-Derived Xenograft Collection Representing the Heterogeneity of Melanoma

Summary: Therapy of advanced melanoma is changing dramatically. Following mutational and biological subclassification of this heterogeneous cancer, several targeted and immune therapies were approved and increased survival significantly. To facilitate further advancements through pre-clinical in vivo modeling, we have established 459 patient-derived xenografts (PDX) and live tissue samples from 384 patients representing the full spectrum of clinical, therapeutic, mutational, and biological heterogeneity of melanoma. PDX have been characterized using targeted sequencing and protein arrays and are clinically annotated. This exhaustive live tissue resource includes PDX from 57 samples resistant to targeted therapy, 61 samples from responders and non-responders to immune checkpoint blockade, and 31 samples from brain metastasis. Uveal, mucosal, and acral subtypes are represented as well. We show examples of pre-clinical trials that highlight how the PDX collection can be used to develop and optimize precision therapies, biomarkers of response, and the targeting of rare genetic subgroups. : Krepler et al. have established a collection of melanoma patient-derived xenografts (PDX). Melanoma is a very heterogeneous cancer, and this large collection includes even rare subtypes and genetic aberrations in sufficient numbers. Multiple PDX from therapy-resistant patients are characterized and tested in pre-clinical trials for second line therapies. Keywords: melanoma, patient-derived xenografts, targeted therapy, immune checkpoint blockade, melanoma brain metastasis, in vivo models, BRAF inhibitor resistance, ERK inhibitor, MDM2 inhibitor, PI3K beta inhibito