Ar-40/-Ar-39 geochronology at the Instituto de Geociencias, USP: instrumentation, analytical procedures, and calibration

Laser heating Ar-40/Ar-39 geochronology provides high analytical precision and accuracy, mum-scale spatial resolution. and statistically significant data sets for the study of geological and planetary processes, A newly commissioned Ar-40/Ar-39 laboratory at CPGeo/USP, Sao Paulo, Brazil, equips the Brazilian scientific community with a new powerful tool applicable to the study of geological and cosmochemical processes. Detailed information about laboratory layout, environmental conditions, and instrumentation provides the necessary parameters for the evaluation of the CPGeo/USp Ar-40/Ar-39 suitability to a diverse range of applications. Details about analytical procedures, including mineral separation, irradiation at the IPEN/CNEN reactor at USP, and mass spectrometric analysis enable potential researchers to design the necessary sampling and sample preparation program suitable to the objectives of their study. Finally, the results of calibration tests using Ca and K salts and glasses, international mineral standards, and in-house mineral standards show that the accuracy and precision obtained at the Ar-40/Ar-39 laboratory at CPGeo/USP are comparable to results obtained in the most respected laboratories internationally. The extensive calibration and standardization procedures under-taken ensure that the results of analytical studies carried out in our laboratories will gain immediate international credibility, enabling Brazilian students and scientists to conduct forefront research in earth and planetary sciences.

Quaternary continental weathering geochronology by laser-heating Ar-40/Ar-39 analysis of supergene cryptomelane

Incremental laser-heating analyses of supergene cryptomelane clusters extracted from three distinct weathering profiles from the Mary Valley region, southeast Queensland, Australia, yield reproducible and well-defined plateau ages ranging from 346 +/- 15 to 291 +/- 14 ka (2 a). Precipitation of supergene cryptomelane in this period implies that relative humid climate prevailed in southeast Queensland from 340 to 290 ha, a result consistent with oxygen isotope analyses of marine sediments from Ocean Drilling Program Site 820 and with regional pollen and spore records. These results, the first report on the precise Ar-40/Ar-39 dating of Quaternary supergene cryptomelane, indicate that Ar-40/Ar-39 analysis of pedogenic minerals provides a reliable geochronometer for the study of Quaternary surficial processes useful in the study of soil formation rates, continental paleoclimates, and archaeological sites devoid of datable volcanic minerals.

Cenozoic continental weathering and its implications for the palaeoclimate: evidence from Ar-40/Ar-39 geochronology of supergene K-Mn oxides in Mt Tabor, central Queensland, Australia

One hundred and twenty-five mineral grains from 45 visually pure K-bearing Mn oxide (hollandite group) samples collected from weathering profiles in the Mt Tabor region of central Queensland, Australia, were analysed by the Ar-40/Ar-39 laser probe technique. These K-Mn oxides precipitated mainly through a process of cavity filling (direct precipitation from weathering solution), with botryoidal texture formed by micrometric mineral bands. Well-defined and reproducible plateau ages have been obtained for most samples, ranging from 27.2 +/- 0.8 to 6.8 +/- 0.5 Ma (2 sigma). Statistical analysis of the geochronological results by mixture modelling suggests an episodic mineral precipitation history, with two major peaks at 20.2 +/- 0.22 Ma and 16.5 +/- 0.17 Ma. The geochronological results, when combined with information on paragenetic relationships and mineralogical textures obtained from petrographic, scanning electron microscopy, and electron microprobe investigations, indicate that warm and humid palaeoclimatic conditions favourable to intense chemical weathering prevailed in central Queensland from late Oligocene to middle Miocene, particularly in the early Miocene. These results, in conjunction with previous and ongoing investigations in NW and eastern Queensland, suggest that most of Queensland was dominated by humid climates during the Miocene. (C) 2002 Elsevier Science BN. All rights reserved.

Behavior of argon gas release from manganese oxide minerals as revealed by Ar-40/Ar-39 laser incremental heating analysis

Manganese oxides in association with paleo-weathering may provide significant insights into the multiple factors affecting the formation and evolution of weathering profiles, such as temperature, precipitation, and biodiversity. Laser probe step-heating analysis of supergene hollandite and cryptomelane samples collected from central Queensland, Australia, yield well-defined plateaus and consistent isochron ages, confirming the feasibility, dating very-fined supergene manganese oxides by Ar-40/(39) Ar technique. Two distinct structural sites hosting Ar isotopes can be identified in light of their degassing behaviors obtained by incremental heating analyses. The first site, releasing its gas fraction at the laser power 0.2-0.4 W, yields primarily Ar-40(atm), Ar-38(atm), and Ar-36(atm), (atmospheric Ar isotopes). The second sites yield predominantly Ar-40* (radiogenic Ar-40), Ar-39(K), and Ar-38(K) (nucleogenic components), at similar to0.5-1.0 W. There is no significant Ar gas released at the laser power higher than 1.0 W, indicating the breakdown of the tunnel sites hosting the radiogenic and nucleogenic components. The excellent match between the degassing behaviors of Ar-40*, Ar-39(K), and Ar-38(K) suggests that these isotopes occupy the same crystallographic sites and that Ar-39(K) loss from the tunnel site by recoil during neutron irradiation and/or bake-out procedure preceding isotopic analysis does not occur. Present investigation supports that neither the overwhelming atmospheric Ar-40 nor the very-fined nature of the supergene manganese oxides poses problems in extracting meaningful weathering geo-chronological information by analyzing supergene manganese oxides minerals.

K-Ar and 40Ar/39Ar ages of dikes emplaced in the onshore basement of the Santos Basin, Resende area, SE Brazil: implications for the South Atlantic opening and tertiary reactivation

New K-Ar and Ar-40/Ar-39 data of tholeiitic and alkaline dike swarms from the onshore basement of the Santos Basin (SE Brazil) reveal Mesozoic and Tertiary magmatic pulses. The tholeiitic rocks (basalt, dolerite, and microgabbro) display high TiO2 contents (average 3.65 wt%) and comprise two magmatic groups. The NW-oriented samples of Group A have (La/Yb)N ratios between 15 and 32.3 and range in age from 192.9 +/- 2.2 to 160.9 +/- 1.9 Ma. The NNW-NNE Group B samples, with (La/Yb)(N) ratios between 7 and 16, range from 148.3 +/- 3 to 133.9 +/- 0.5 Ma. The alkaline rocks (syenite, trachyte, phonolite, alkaline basalts, and lamprophyre) display intermediate-K contents and comprise dikes, plugs, and stocks. Ages of approximately 82 Ma were obtained for the lamprophyre dikes, 70 Ma for the syenite plutons, and 64-59 Ma for felsic dikes. Because Jurassic-Early Cretaceous basic dikes have not been reported in SE Brazil, we might speculate that, during the emplacement of Group A dikes, extensional stresses were active in the region before the opening of the south Atlantic Ocean and coeval with the Karoo magmatism described in South Africa. Group B dikes yield ages compatible with those obtained for Serra Geral and Ponta Grossa magmatism in the Parana Basin and are directly related to the breakup of western Gondwana. Alkaline magmatism is associated with several tectonic episodes that postdate the opening of the Atlantic Ocean and related to the upwelling of the Trindade plume and the generation of Tertiary basins southeast of Brazil. In the studied region, alkaline magmatism can be subdivided in two episodes: the first one represented by lamprophyre dykes of approximately 82 Ma and the second comprised of felsic alkaline stocks of approximately 70 Ma and associated dikes ranging from 64 to 59 Ma. (c) 2005 Elsevier Ltd. All rights reserved.

Geochronology of weathering and landscape evolution, Dugald River valley, NW Queensland, Australia

40Ar/39Ar laser incremental heating analyses of individual grains of supergene jarosite, alunite, and cryptomelane from weathering profiles in the Dugald River area, Queensland, Australia, show a strong positive correlation between a sample’s age and its elevation. We analyzed 125 grains extracted from 35 hand specimens collected from weathering profiles at 11 sites located at 3 distinct elevations. The highest elevation profile hosts the oldest supergene minerals, whereas progressively younger samples occur at lower positions in the landscape. The highest elevation sampling sites (three sites), located on top of an elongated mesa (255 to 275 m elevation), yield ages in the 16 to 12 Ma range. Samples from an intermediate elevation site (225 to 230 m elevation) yield ages in the 6 to 4 Ma range. Samples collected at the lowest elevation sites (200 to 220 m elevation) yield ages in the 2.2 to 0.8 Ma interval. Grains of supergene alunite, jarosite, and cryptomelane analyzed from individual single hand specimens yield reproducible results, confirming the suitability of these minerals to 40Ar/39Ar geochronology. Multiple samples collected from the same site also yield reproducible results, indicating that the ages measured are true precipitation ages for the samples analyzed. Different sites, up to 3 km apart, sampled from weathering profiles at the same elevation again yield reproducible results. The consistency of results confirms that 40Ar/39Ar geochronology of supergene jarosite, alunite, and cryptomelane yields ages of formation of weathering profiles, providing a reliable numerical basis for differentiating and correlating these profiles. The age versus elevation relationship obtained suggest that the stepped landscapes in the Dugald River area record a progressive downward migration of a relatively flat weathering front. The steps in the landscape result from differential erosion of previously weathered bedrock displaying different susceptibility to weathering and contrasting resistance to erosion. Combined, the age versus elevation relationships measured yield a weathering rate of 3.8 m. Myr−1 (for the past 15 Ma) if a descending subhorizontal weathering front is assumed. The results also permit the calculation of the erosion rate of the more easily weathered and eroded lithologies, assuming an initially flat landscape as proposed in models of episodic landscape development. The average erosion rate for the past 15 Ma is 3.3 m. Myr−1, consistent with erosion rates obtained by cosmogenic isotope studies in the region.

40Ar/39Ar constraints on a temporal link between gold mineralization, magmatism, and continental margin transtension in the Jiaodong Gold Province, eastern China

The Jiaodong gold province is the largest gold repository in China. Both mineralization and granitoid hosts are spatially related to the crustal-scale Tan-Lu strike-slip fault system, which developed along the Mesozoic continental margin in eastern China. A series of Ar-40/Ar-39 laser incremental heating analyses of hydrothermal sericite/muscovite from three major gold deposits (Jiaojia, Xincheng, and Wangershan) and igneous biotite from the granodiorite hosts were performed to establish a possible temporal link between gold mineralization, magmatism, and movement along the Tan-Lu fault zone. Magmatic biotite crystals yield well-defined and concordant plateau ages between 124.5+/-0.4 Ma and 124.0+/-0.4 Ma (2sigma), whereas sericite and muscovite samples (a total of 30 single separates) give reproducible plateau ages ranging from 121.0+/-0.4 Ma to 119.2+/-0.2 Ma (2sigma). An integration of our Ar-40/Ar-39 results with age data from other major gold deposits in Jiaodong demonstrates that widespread gold mineralization occurred contemporaneously during a 2-3-m.yr. period. Most gold deposits show intimate spatial associations with abundant mafic to intermediate dikes. The mafic dikes have K-Ar ages of 123.5-119.6 Ma, in excellent agreement with those of the gold deposits. These newly obtained Ar-40/Ar-39 ages, in combination with other independent geological and geochronological data on granodioritic intrusions (130-126 Ma), volcanic rocks (1243.6-114.7 Ma), and deformed rocks within strike-slip faults (132-120 Ma) in Jiaodong or adjacent areas, also support the idea that gold mineralization postdated the granodioritic magmatism but was contemporaneous with mafic magmatism and volcanism, all controlled by the transtensional motion along the Tan-Lu fault in the Early Cretaceous.

Geochronological evidence for pervasive miocene weathering, Minas Gerais, Brazil

Ar-40/Ar-39 laser incremental-heating analyses of 22 individual grains of supergene cryptomelane from three weathering profiles, up to 400 km apart, in the Rio Doce valley and Barbacena regions at Minas Gerais, Brazil, show that the formation of weathering profiles in these regions is contemporaneous, suggesting a strong weathering event in the Middle to Late Miocene (10-8 Ma). The preservation of these Miocene samples at or near the present surface suggests that either erosion rates have been very low in the region since the Miocene or that a much thicker weathering mantle was present in the region originally. Assuming a constant thickness of weathering profiles in the region throughout the Tertiary, we may calculate weathering front propagation rates of 4-8 m Myr(-1) during the past 10 Ma. Copyright (C) 2004 John Wiley Sons, Ltd.

Weathering geochronology by (U-Th)/He dating of goethite

Nine samples of supergene goethite (FeOOH) from Brazil and Australia were selected to rest the suitability of this mineral for (U-Th)/He dating. Measured He ages ranged from 61 to 8 Ma and were reproducible to better than a few percent despite very large Variations in [U] and [Th]. In all Samples with internal stratigraphy or independent age constraints, the He ages corroborated the expected relationship's. These data demonstrate that internally consistent He ages can be obtained on goethite. but do not prove quantitative 4 He retention. To assess possible diffusive He loss, stepped-heating experiments were performed on two goethite samples that were subjected to proton irradiation to produce a homogeneous distribution of spallogenic He-3. The He-3 release pattern indicates the presence of at least two diffusion domains, one with high helium retentivity and the other with very low retentivity at Earth surface conditions. The low retentivity domain, which accounts for similar to 5% of He-3, contains no natural He-4 and may represent poorly crystalline or intergranular material which has lost all radiogenic He-4 by diffusion in nature. Diffusive loss of He-3 from the high retentivity domain is independent of the macroscopic dimensions of the analyzed polycrystalline aggregate, so probably represents diffusion from individual micrometer-size goethite crystals. The He-2/He-3 evolution during the incremental heating experiments shows that the high retentivity domain has retained 90%-95% of its radiogenic helium. This degree of retentivity is in excellent agreement with that independently predicted from the helium diffusion coefficients extrapolated to Earth surface temperature and held for the appropriate duration. Considering both the high and low retentivity domains, these data indicate that one of the samples retained 90% of its radiogenic He-4 over 47.5 Ma and the other retained 86% over 12.3 Ma. Thus while diffusive-loss corrections to supergene goethite He ages are required. these initial results indicate that the corrections are not extremely large and can be rigorously quantified using the proton-irradiation He-4/He-3 method. Copyright (C) 2005 Elsevier Ltd.

40Ar/39Ar geochronological constraints on the evolution of lateritic iron deposits in the Quadrilatero Ferrifero, Minas Gerais, Brazil

Weathering profiles overlying the Sapecado, Pico and Andaime iron ore deposits, Quadrilátero Ferrífero (QF), Minas Gerais, Brazil, reach depths of 150–400 m and host world-class supergene iron orebodies. In addition to hosting supergene ore bodies of global economic significance, weathered banded iron-formations at the Quadrilátero Ferrífero and elsewhere (e.g., Carajás, Hamersley) are postulated to underlie some of the most ancient continuously exposed weathering profiles on earth. Laser incremental-heating 40Ar/39Ar results for 69 grains of hollandite-group manganese oxides extracted from 23 samples collected at depths ranging from 5 to 150 m at the Sapecado, Pico and Andaime deposits reveal ages ranging from ca. 62 to 14 Ma. Older Mn-oxides occur near the surface, while younger Mn-oxides occur at depth. However, many samples collected at the weathering–bedrock interface yield ages in the 51–41 Ma range, suggesting that the weathering profiles in the Quadrilátero Ferrífero had already reached their present depth in the Paleogene. The antiquity of the weathering profiles in the Quadrilátero Ferrífero is comparable to the antiquity of dated weathering profiles on banded iron-formations in the Carajás Region (Brazil) and the Hamersley Province, Western Australia. The age versus depth distributions obtained in this study, but not available for other regions containing similar supergene iron deposits, suggest that little further advance of the weathering front has occurred in the Quadrilátero Ferrífero lateritic profiles during the Neogene. The results suggest that weathering in some of these ancient landscapes is not controlled by the steady-state advance of weathering fronts through time, but may reflect climatic and geomorphological conditions prevailing in a remote past. The geochronological results also confirm that the ancient landsurfaces in the Quadrilátero Ferrífero probably remained immune to erosion for tens of millions of years. Deep weathering, mostly in the Paleogene, combined with low erosion rates, account for the abundance and widespread distribution of supergene iron, manganese, and aluminum orebodies in this region.

Geochronology of the Pengjiakuang and Rushan gold deposits, Eastern Jiaodong Gold Province, Northeastern China: Implications for regional mineralization and geodynamic setting

The Jiaodong gold province, the largest gold-producing district in China, is located in the jiaodong peninsula at the eastern margin of the North China craton and bounded by the continental scale Tan-Lu fault, 40 kin to the west. Previous geochronological studies suggest that pervasive gold deposition took place in the western part of the province between 122 and 119 Ma. Here we report high-quality Ar-40/Ar-39 ages of the Pengjiakuang and Rushan deposits from the eastern part of the jiaodong gold province, placing additional chronological constraints on the timing of regional mineralization. Seven sericite grains extracted from auriferous alteration assemblages at the Pengiiakuang deposit yielded well-defined plateau ages between 120.9 +/- 0.4 and 119.1 +/- 0.2 Ma (2 sigma). Three separates of igneous biotite from a sample of the Queshan gneissic granite, adjacent to the Pengjiakuang deposit, gave reproducible plateau ages of 124.6 +/- 0.6 to 123.9 +/- 0.4 Ma (2 sigma). Six sericite separates front two samples in the Rushan deposit yielded Ar-40/Ar-39 plateau ages at 109.3 +/- 0.3 to 107.7 +/- 0.5 Ma (2 sigma), whereas biotite from the Kunyushan monzogranite that hosts the Rushan deposit had plateau ages ranging from 129.0 +/- 0.6 to 126.9 +/- 0.6 Ma (3 separates front one sample). The apparent age gap between hydrothermal sericite and magmtic biotite from both deposits, together with the similar argon closure temperatures for these mica minerals, suggest that gold mineralization had no direct relationship to the granitoid magmatism. Instead, gold deposition coincided with the emplacement of mafic to intermediate dikes widespread in the jiaodong gold province, which have been dated at ca. 122 to 119 Ma and, less commonly, at 110 to 102 Ma. The new Ar-40/Ar-39 ages from the eastern jiaodong peninsula, when combined with published data from the western part suggest that gold mineralization was broadly contemporaneous throughout the district. The Early Cretaceous gold mineralization also is widely developed in four other major gold districts along the Tan-Lu fault. The temporal and spatial correlation of these gold deposits with mafic to intermediate dikes commonly found in most mineralized areas, the presence of well-documented metamorphic core complexes and half-graben basins along the Tan-Lu fault, and voluminous basalts therein, suggest that the Early Cretaceous was an important period of lithospheric extension, possibly caused by the late Mesozoic lithospheric thinning beneath the eastern block of the North China craton. Lithospheric thinning and extension could have resulted in abnormally high heat and fluid fluxes necessary for large-scaled gold mineralization.

The Quaternary pyroclastic succession of southeast Tenerife, Canary Islands: Explosive eruptions, related caldera subsidence, and sector collapse

A much-revised Quaternary stratigraphy is presented for ignimbrites and pumice fall deposits of the Bandas del Sur, in southern Tenerife. New Ar-41/Ar-39 data obtained for the Arico, Granadilla, Fasnia, Poris, La Caleta and Abrigo formations are presented, allowing correlation with previously dated offshore marine ashfall layers and volcaniclastic sediments. We also provide a minimum age of 287 +/- 7 ka for a major sector collapse event at the Gaimar valley. The Bandas del Sur succession includes more than seven widespread ignimbrite sheets that have similar characteristics, including widespread basal Plinian layers, predominantly phonolite composition, ignimbrites with similar extensive geographic distributions, thin condensed veneers with abundant diffuse bedding and complex lateral and vertical grading patterns, lateral gradations into localized massive facies within palaeo-wadis, and widespread lithic breccia layers that probably record caldera-forming eruptions. Each ignimbrite sheet records substantial bypassing of pyroclastic material into the ocean. The succession indicates that Las Canadas volcano underwent a series of major explosive eruptions, each starting with a Plinian phase followed by emplacement of ignimbrites and thin ash layers, some of coignimbrite origin. Several of the ignimbrite sheets are compositionally zoned and contain subordinate mafic pumices and banded pumices indicative of magma mingling immediately prior to eruption. Because passage of each pyroclastic density current was characterized by phases of non-deposition and erosion, the entire course of each eruption is incompletely recorded at any one location, accounting for some previously perceived differences between the units. Because each current passed into the ocean, estimating eruption volumes is virtually impossible. Nevertheless, the consistent widespread distributions and the presence of lithic breccias within most of the ignimbrite sheets suggest that at least seven caldera collapse eruptions are recorded in the Bandas del Sur succession and probably formed a complex, nested collapse structure. Detailed field relationships show that extensive ignimbrite sheets (e.g. the Arico, Poris and La Caleta formations) relate to previously unrecognized caldera collapse events. We envisage that the evolution of the nested Las Cahadas caldera is more complex than previously thought and involved a protracted history of successive ignimbrite-related caldera collapse events, and large sector collapse events, interspersed with edifice-building phases.

Petrology and geochemistry of early cretaceous bimodal continental flood volcanism of the NW Etendeka, Namibia. Part 1: Introduction, mafic lavas and re-evaluation of mantle source components

The bimodal NW Etendeka province is located at the continental end of the Tristan plume trace in coastal Namibia. It comprises a high-Ti (Khumib type) and three low-Ti basalt (Tafelberg, Kuidas and Esmeralda types) suites, with, at stratigraphically higher level, interstratified high-Ti latites (three units) and quartz latites (five units), and one low-Ti quartz latite. Khumib basalts are enriched in high field strength elements and light rare earth elements relative to low-Ti types and exhibit trace element affinities with Tristan da Cunha lavas. The unradiogenic Pb-206/Pb-204 ratios of Khumib basalts are distinctive, most plotting to the left of the 132 Ma Geochron, together with elevated Pb-207/Pb-204 ratios, and Sr-Nd isotopic compositions plotting in the lower Nd-143/Nd-144 part of mantle array (EM1-like). The low-Ti basalts have less coherent trace element patterns and variable, radiogenic initial Sr (similar to0.707-0.717) and Pb isotope compositions, implying crustal contamination. Four samples, however, have less radiogenic Pb and Sr that we suggest approximate their uncontaminated source. All basalt types, but particularly the low-Ti types, contain samples with trace element characteristics (e.g. Nb/Nb-*) suggesting metasediment input, considered source-related. Radiogenic isotope compositions of these samples require long-term isolation of the source in the mantle and depletions (relative to unmodified sediment) in certain elements (e.g. Cs, Pb, U), which are possibly subduction-related. A geodynamic model is proposed in which the emerging Tristan plume entrained subducted material in the Transition Zone region, and further entrained asthenosphere during plume head expansion. Mixing calculations suggest that the main features of the Etendeka basalt types can be explained without sub-continental lithospheric mantle input. Crustal contamination is evident in most low-Ti basalts, but is distinct from the incorporation of a metasedimentary source component at mantle depths.

40Ar/39Ar geochronology constraints on late miocene weathering rates in Minas Gerais, Brazil

Ar-40/Ar-39 incremental heating ages for twenty one grains of cryptomelane, collected at 0, 42, 45, and 60 in depths in the Cachoeira Mine weathering profile, Minas Gerais, permit calculating long-term (10 Ma time scale) weathering rate (saprolitization rate) in SE Brazil. Pure well-crystallized cryptomelane grains with high K contents (3-5 wt.%) yield reliable geochronological results. The Ar-40/Ar-39 plateau ages obtained decrease from the top to the bottom of the profile (12.7 +/- 0.1 to 7.6 +/- 0.1 Ma at surface; 7.6 +/- 0.2 to 6.1 +/- 0.2 Ma at 42 m; and 7.1 +/- 0.2 to 5.9 +/- 0.1 Ma at 45 in; 6.6 +/- 0.1 to 5.2 +/- 0.1 Ma at 60 in), yielding a weathering front propagation rate of 8.9 +/- 1.1 m/m.y. From the geochronological results and the mineral transformations implicit by the current mineralogy in the weathering profiles, it is possible to calculate the saprolitization rate for the Cachoeira Mine lithologies and for adjacent weathering profiles developed on granodiorites and scbists. The measured weathering front propagation rate yields a saprolitization rate of 24.9 +/- 3.1 t/km(2)/yr. This average long-term (> 10 Ma) saprolitization rate is consistent with mass balance calculations results for present saprolitization rates in weathering watersheds. These results are also consistent with longterm saprolitization rates estimated by combining cosmogenic isotope denudation rates with mass balance calculations. (c) 2005 Elsevier B.V All rights reserved.