Goldilocks at the dawn of complex life: mountains might have damaged Ediacaran-Cambrian ecosystems and prompted an early Cambrian greenhouse world.

We combine U-Pb in-situ carbonate dating, elemental and isotope constraints to calibrate the synergy of integrated mountain-basin evolution in western Gondwana. We show that deposition of the Bambuí Group coincides with closure of the Goiás-Pharusian (630-600 Ma) and Adamastor (585-530 Ma) oceans. Metazoans thrived for a brief moment of balanced redox and nutrient conditions. This was followed, however, by closure of the Clymene ocean (540-500 Ma), eventually landlocking the basin. This hindered seawater renewal and led to uncontrolled nutrient input, shallowing of the redoxcline and anoxic incursions, fueling positive productivity feedbacks and preventing the development of typical Ediacaran-Cambrian ecosystems. Thus, mountains provide the conditions, such as oxygen and nutrients, but may also preclude life development if basins become too restricted, characterizing a Goldilocks or optimal level effect. During the late Neoproterozoic-Cambrian fan-like transition from Rodinia to Gondwana, the newborn marginal basins of Laurentia, Baltica and Siberia remained open to the global sea, while intracontinental basins of Gondwana became progressively landlocked. The extent to which basin restriction might have affected the global carbon cycle and climate, e.g. through the input of gases such as methane that could eventually have collaborated to an early Cambrian greenhouse world, needs to be further considered.

Trace metal dynamics in an industrialized Brazilian river: A combined application of Zn isotopes, geochemical partitioning, and multivariate statistics.

The Paraiba do Sul (PSR) and Guandu Rivers (GR) water diversion system (120 km long) is located in the main industrial pole of Brazil and supplies drinking water for 9.4 million people in the metropolitan region of Rio de Janeiro. This study aims to discern the trace metals dynamics in this complex aquatic system. We used a combined approach of geochemical tools such as geochemical partitioning, Zn isotopes signatures, and multivariate statistics. Zinc and Pb concentrations in Suspended Particulate Matter (SPM) and sediments were considerably higher in some sites. The sediment partition of As, Cr, and Cu revealed the residual fraction (F4) as the main fraction for these elements, indicating low mobility. Zinc and Pb were mostly associated with the exchangeable/carbonate (F1) and the reducible (F2) fractions, respectively, implying a higher susceptibility of these elements to being released from sediments. Zinc isotopic compositions of sediments and SPM fell in a binary mixing source process between lithogenic (δ66/64ZnJMC ≈ + 0.30‰) and anthropogenic (δ66/64ZnJMC ≈ + 0.15‰) end members. The lighter δ66/64ZnJMC values accompanied by high Zn concentrations in exchangeable/carbonate fraction (ZnF1) enable the tracking of Zn anthropogenic sources in the studied rivers. Overall, the results indicated that Hg, Pb, and Zn had a dominant anthropogenic origin linked to the industrial activities, while As, Cr, and Cu were mainly associated with lithogenic sources. This work demonstrates how integrating geochemical tools is valuable for assessing geochemical processes and mixing source effects in anthropized river watersheds.

Microbially induced chromium isotope fractionation and trace elements behavior in lower Cambrian microbialites from the Jaíba Member, Bambuí Basin, Brazil.

In east-central Brazil, the Ediacaran-Cambrian Bambuí Basin has the potential to provide a record of unique geochemical responses of Earth's ocean and atmosphere evolution during this key time interval. From this perspective, we studied an interval of the upper Bambuí Basin using sedimentologic, stratigraphic, and chemostratigraphic tools. The lower Cambrian Jaíba Member of the uppermost Serra da Saudade Formation is an interval of up to 60 m-thick of carbonate rocks disposed into two shallowing upward trends. Inner to outer ramp and high-energy shoal deposits are described, in which laminated microbialites are the prevailing sedimentary facies. REE + Y data suggest contamination by iron (oxy)hydroxides that are dissociated from the riverine detritic flux. Sedimentary iron enrichment may be related to the settling of iron nanoparticles in coastal environments, diagenetic iron mobilization, or both. MREE enrichment is caused by microbial degradation of organic matter in the iron reduction zone during the anoxic early-diagenetic stage. Chromium isotopes yielded negatively fractionated values (δ53 Cr = -0.69 to -0.27‰), probably resulting from biotic and abiotic reduction of dissolved Cr(VI) to light and less toxic Cr(III) within pores of microbial mats. The δ53 Cr data of the Jaíba microbialite are thus a product of metabolic reactions in microbial mats and do not reflect seawater signal. The isotopic offset from seawater is feasible from molecular diffusion of Cr into pore water and reduction reactions occurring deep inside the mat, although the exact mechanism and consequences are not yet fully understood due to the poor preservation of metabolic reactions in the geological record. Our study suggests that Cr isotopes can be used to reconstruct Cr and other metals cycling within ancient microbial mats, and that caution should be taken when using past microbialites to infer seawater Cr records and redox state of the atmosphere and ocean.

Behavior of metallurgical zinc contamination in coastal environments: A survey of Zn from electroplating wastes and partitioning in sediments.

The contamination of coastal environments by metallurgical wastes involves multiple biogeochemical processes; accordingly, understanding metal behavior and risk evaluation of contaminated areas, such as Sepetiba Bay (Rio de Janeiro, Brazil), remains challenging. This study coupled Zn isotopic analyses with sequential extractions (BCR) to investigate the mechanisms of Zn transfer between legacy electroplating waste and the main environments in Sepetiba Bay. This metallurgical waste showed a light bulk isotopic signature (δ66/64ZnbulkJMC = +0.30 ±â€¯0.01‰, 2 s, n = 3) that was not distinct from the lithogenic geochemical baseline, but was different from signature of mangrove sediment considered as anthropogenic end member (δ66/64ZnJMC = +0.86 ±â€¯0.15‰) in a previous isotopic study in this area. Zn isotopic compositions of sediment samples (ranging from +0.20 to +0.98‰) throughout the bay fit a mixing model involving multiple sources, consistent with previous studies. In the metallurgic zone, the exchangeable/carbonate fraction (ZnF1) exhibited high Zn concentrations (ZnF1 = 9840 µg g-1) and a heavy isotopic composition (δ66/64ZnF1JMC = +1.10 ±â€¯0.01‰). This finding showed that, in some cases, the bulk isotopic signature of waste is not the most relevant criterion for evaluating trace metal dispersion in the environment. Indeed, based on the BCR, it was observed that part of the anthropogenic metallurgical Zn was redistributed from the exchangeable/carbonate fraction in the waste to the surrounding mangrove sediment. Then, this contaminated sediment with heavy δ66/64Zn values was exported to other coastal environments. In Sepetiba Bay, contaminated sediments revealed a large concentration of ZnF1 fraction (up to 400 µg g-1) with a heavy Zn isotopic signature. This signature also matched the Zn isotopic signature of oysters in Sepetiba Bay reported by other studies; hence, measurement of the isotopic exchangeable/carbonate fraction has important implications for tracing the transfer of anthropogenic Zn to biota.

Arc accretion and crustal reworking from late Archean to Neoproterozoic in Northeast Brazil.

New systematic Nd isotope and U-Pb geochronology data were applied to Precambrian rocks of northeastern Brazil to produce a crustal-age distribution map for a small basement inlier (1,500 km2). The results support episodic crustal growth with five short periods of crustal formation at ca. 2.9 Ga, 2.65 Ga, 2.25 Ga, 2.0 Ga, and 0.6 Ga. Based on the frequency histogram of U-Pb zircon ages and Nd isotopic data, we suggest that about 60% of the continental crust was formed during the Archean between 2.9 Ga and 2.65 Ga. The remaining 40% of crust was generated during the Rhyacian to Neoproterozoic (~2.0-0.6 Ga). This overall continental growth is manifested by accretionary processes that involved successive accretions surrounding an older core, becoming younger toward the margin. Strikingly, this repetitive history of terrane accretion show a change from lithospheric peeling dominated accretionary setting during the late Archean to a more, modern-day akin style of arc-accretion during the Proterozoic. Similar tectonic processes are observed only in large continental areas (>1,000,000 km2) as in the North American continent basement and in the Amazonian Craton.

Fractionation of rare earth and other trace elements in crabs, Ucides cordatus, from a subtropical mangrove affected by fertilizer industry.

Fractionation of rare earth elements (REE) and other trace metal concentrations (Th, U, Cd, Cr, Cu, Ni, Pb, and Zn) between mangrove sediments and claw muscles and shells of male crabs (Ucides cordatus) from a subtropical estuary highly impacted by fertilizer industry activities was investigated. This is the first record of REE distribution in these organisms, and the results showed higher accumulations of these metals, U and Th in shells, probably related to the replacement of Ca during molting. Contents of Cd, Cr and Ni were similar in both tissues, but Cu, Zn and Pb were mostly accumulated in the claw muscle with concentrations above those considered safe for human consumption according to the Brazilian legislation. REE fractionation was different in the analyzed tissues being softer in the shells. The results provided evidences that the water absorbed during molting controls the chemistry of REE in shells. In contrast, the chemistry of REE in the claw muscle, in which was observed preferential absorption of light REE, is controlled by diet. REE fractionation obtained for the claw muscles was closely correlated to the observed in the contaminated substrate and in materials related to the production of phosphate fertilizers (contamination source), which supports their transference to this Ucides cordatus tissue without fractionation by the ingestion of sediments. Our results showed the potential use of crab tissues for monitoring REE and trace element sources in mangrove areas, with claw muscle exhibiting the contaminant source fingerprint.

A critical examination of the possible application of zinc stable isotope ratios in bivalve mollusks and suspended particulate matter to trace zinc pollution in a tropical estuary.

The application of zinc (Zn) isotopes in bivalve tissues to identify zinc sources in estuaries was critically assessed. We determined the zinc isotope composition of mollusks (Crassostrea brasiliana and Perna perna) and suspended particulate matter (SPM) in a tropical estuary (Sepetiba Bay, Brazil) historically impacted by metallurgical activities. The zinc isotope systematics of the SPM was in line with mixing of zinc derived from fluvial material and from metallurgical activities. In contrast, source mixing alone cannot account for the isotope ratios observed in the bivalves, which are significantly lighter in the contaminated metallurgical zone (δ66ZnJMC = +0.49 ± 0.06‰, 2σ, n = 3) compared to sampling locations outside (δ66ZnJMC = +0.83 ± 0.10‰, 2σ, n = 22). This observation suggests that additional factors such as speciation, bioavailability and bioaccumulation pathways (via solution or particulate matter) influence the zinc isotope composition of bivalves.

Combined U-Pb and Lu-Hf isotope analyses by laser ablation MC-ICP-MS: methodology and applications

The Lutetium-Hafnium isotopic system represents one of the most innovative and powerful tools for geochronology and isotopic studies. Combined U-Pb and Lu-Hf in situ analyses on zircon by LA-MC-ICP-MS permit to characterize isotopically the host magma from which it crystallized furnishing significant information for sediment provenance and crustal evolution studies. In this paper e describe the Lu-Hf systematic by LA-MC-ICP-MS developed in the laboratory of Geochronology of the University of Brasilia and report the results obtained by repeated analyses of 176Hf/177Hf isotopic ratio of three zircon standards: GJ-1 = 0.282022 ± 11 (n=56), Temora 2 = 0.282693 ± 14 (n=25) and UQZ = 0.282127 ± 33 (n=11). The 176Hf/177Hf ratio (0.282352 ± 22, n=14) of gem quality zircon used as in-house standard have been also characterized. As a geological application, we analyzed two complex zircons selected from a migmatitic rocks from the Borborema Province, NE Brazil. On the basis of U-Pb and Lu-Hf data, two main crystallization events have been identified in both studied zircons. An older event at ca. 2.05 Ga recognized in the inherited cores represents a well-characterized paleoproterozoic magmatic event that affected the whole Borborema Province. A second crystallization event at ~ 575 Ma, recognized at the rims, represents a Neoproterozoic (Brazilian) high grade metamorphic-magmatic event.

O sistema isotópico Lutécio-Hafnio representa uma das ferramentas mais recentes e poderosas para estudos isotópicos e geocronológicos. Análises combinadas in situ de U-Pb e Lu-Hf sobre zircão pelo LA-MC-ICP-MS permitem caracterizar iso-topicamente o magma onde ele cristalizou, fornecendo valiosas informações para estudos de proveniência de sedimento e de evolução crustal. Nesse trabalho descrevemos a sistemática de Lu-Hf pelo LA-MC-ICP-MS implantada no laboratório de Geocronologia da Universidade de Brasília e reportamos os resultados obtidos de repetidas análises de três padrões de zircão: GJ-1 = 0.282022 ± 11 (2SD, n=56), Temora 2 = 0.282693 ± 14 (2SD, n=25) and UQ-Z = 0.282127 ± 33 (2SD, n=11). Foi também caracterizada arazão isotópica 176Hf/177Hf(0.282352 ± 22, 2SD, n=14) de um zircão usado como padrão interno do laboratório. Como aplicação geológica, analisamos dois zircões complexos selecionados a partir de uma amostra de migmatito da Província de Borborema, NE do Brasil. Sobre a base dos dados U-Pb e Lu-Hf foram identificados em ambos os zircões dois eventos de cristalização. Um evento mais antigo de 2.05 Ga nos núcleos herdados, representa um evento magmático Paleoproterozoico bem conhecido na Província Borborema. Um segundo evento de ~ 575 Ma, reconhecido nas bordas, representa um evento magmático-metamórfico Neoproterozóico (Brasiliano).

High spatial resolution analysis of Pb and U isotopes for geochronology by laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS)

Age determinations using the 235U and 238U radioactive decay series to the daughter isotopes 207Pb and 206Pb, respectively, using the mineral zircon (ZrSiO4), are widely used to decipher geological processes. A new method developed in the last couple of years, the laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS), overcomes previous laborious sample preparation, and yields isotopic ratios and age data with a high spatial resolution of ten of microns. The present study describes the analytical set-up and data reduction process as presently applied at the Laboratory for Geochronology of the University of Brasília. It explores the precision and accuracy of the method by cross-analysing three international zircon standards. We arrive at a precision of 1.9 to 3.7 percent (2σ SD) and an accuracy of 0.6 to 3.8 percent (2σ SD) for and U isotopic ratios of the standards. We also apply the method to two natural zircon samples, which have previously been dated by other analytical methods. A comparison of the results show a good conformity of the age data,being whitin the error limits. The data demonstrate the great analytical potential of the method for rapid, precise and accurate U-Pb isotopic analyses on the micron scale.

A determinação de idades através do decaimento dos isótopos radioativos 235U e 238U para os isótopos radiogênicos 207Pb e 206Pb, respectivamente, utilizando o mineral zircão (ZrSiO4), é amplamente aplicada para decifrar processos geológicos. Um novo método tem sido desenvolvido nos últimos anos, a ablação a laser multi-coletor espectrometria de massas com plasma indutivamente acoplado (LA-MC-ICP-MS), superando o laborioso trabalho anteriormente necessário em outros métodos, na preparação de amostras, e permite obtenção de razões isotópicas com alta resolução espacial de micrômetros. O presente estudo descreve os procedimentos analíticos e os métodos usados na redução de dados que estão sendo aplicados no Laboratório de Geocronologia da Universidade de Brasília. Explora-se a precisão e exatidão do método através da análise de três padrões internacionais de zircão. Observa-se uma precisão entre 1,9 a 3,7 por cento (2σ desvio padrão) e uma exatidão de 0,6 a 3,8 por cento (2σ desvio padrão) para as razões isotópicas de Pb e U dos padrões. Também foram obtidas idades pelo método LA-ICP-MS de duas amostras de zircões naturais, que já foram datadas anteriormente por outros métodos analíticos. A comparação dos resultados mostra uma boa conformidade das idades obtidas, dentro dos limites de erro.Os dados demonstram o grande potencial do método analítico para análises isotópicas rápidas, precisas e exatas de U-Pb, numa escala de micrômetros.