U-Pb zircon in situ dating with LA-MC-ICP-MS using a mixed detector configuration

The LA-MC-ICP-MS method applied to U-Pb in situ dating is still rapidly evolving due to improvements in both lasers and ICP-MS. To test the validity and reproducibility of the method, 5 different zircon samples, including the standard Temora-2, ranging in age between 2.2 Ga and 246 Ma, were dated using both LA-MC-ICP-MS and SHRIMP. The selected zircons were dated by SHRIMP and, after gentle polishing, the laser spot was driven to the same site or on the same zircon phase with a 213 nm laser microprobe coupled to a multi-collector mixed system. The data were collected with a routine spot size of 25 μm and, in some cases, of 15 and 40 μm. A careful cross-calibration using a diluted U-Th-Pb solution to calculate the Faraday reading to counting rate conversion factors and the highly suitable GJ-1 standard zircon for external calibrations were of paramount importance for obtaining reliable results. All age results were concordant within the experimental errors. The assigned age errors using the LA-MC-ICP-MS technique were, in most cases, higher than those obtained by SHRIMP, but if we are not faced with a high resolution stratigraphy, the laser technique has certain advantages.

Geochronological constraints on the age of a Permo-Triassic impact event: U-Pb and Ar-40/Ar-39 results for the 40 km Araguainha structure of central Brazil

Impact cratering has been a fundamental geological process in Earth history with major ramifications for the biosphere. The complexity of shocked and melted rocks within impact structures presents difficulties for accurate and precise radiogenic isotope age determination, hampering the assessment of the effects of an individual event in the geological record. We demonstrate the utility of a multi-chronometer approach in our study of samples from the 40 km diameter Araguainha impact structure of central Brazil. Samples of uplifted basement granite display abundant evidence of shock deformation, but U/Pb ages of shocked zircons and the Ar-40/Ar-39 ages of feldspar from the granite largely preserve the igneous crystallization and cooling history. Mixed results are obtained from in situ Ar-40/Ar-39 spot analyses of shocked igneous biotites in the granite, with deformation along kink-bands resulting in highly localized, partial resetting in these grains. Likewise, spot analyses of perlitic glass from pseudotachylitic breccia samples reflect a combination of argon inheritance from wall rock material, the age of the glass itself, and post-impact devitrification. The timing of crater formation is better assessed using samples of impact-generated melt rock where isotopic resetting is associated with textural evidence of melting and in situ crystallization. Granular aggregates of neocrystallized zircon form a cluster of ten U-Pb ages that yield a "Concordia" age of 247.8 +/- 3.8 Ma. The possibility of Pb loss from this population suggests that this is a minimum age for the impact event. The best evidence for the age of the impact comes from the U-Th-Pb dating of neocrystallized monazite and Ar-40/Ar-39 step heating of three separate populations of post-impact, inclusion-rich quartz grains that are derived from the infill of miarolitic cavities. The Pb-206/U-238 age of 254.5 +/- 3.2 Ma (2 sigma error) and Pb-208/Th-232 age of 255.2 +/- 4.8 Ma (2 sigma error) of monazite, together with the inverse, 18 point isochron age of 254 +/- 10 Ma (MSWD = 0.52) for the inclusion-rich quartz grains yield a weighted mean age of 254.7 +/- 2.5 Ma (0.99%, 2 sigma error) for the impact event. The age of the Araguainha crater overlaps with the timing of the Permo-Triassic boundary, within error, but the calculated energy released by the Araguainha impact is insufficient to be a direct cause of the global mass extinction. However, the regional effects of the Araguainha impact event in the Parana-Karoo Basin may have been substantial. (C) 2012 Elsevier Ltd. All rights reserved.

Paper-based diffusive gradients in thin films technique coupled to energy dispersive X-ray fluorescence spectrometry for the determination of labile Mn, Co, Ni, Cu, Zn and Pb in river water

The diffusive gradients in thin films (DGT) technique has shown enormous potential for labile metal monitoring in fresh water due to the preconcentration, time-integrated, matrix interference removal and speciation analytical features. In this work, the coupling of energy dispersive X-ray fluorescence (EDXRF) with paper-based DGT devices was evaluated for the direct determination of Mn, Co. Ni, Cu, Zn and Pb in fresh water. The DGT samplers were assembled with cellulose (Whatman 3 MM chromatography paper) as the diffusion layer and a cellulose phosphate ion exchange membrane (Whatman P 81 paper) as the binding agent. The diffusion coefficients of the analytes on 3 MM chromatography paper were calculated by deploying the DGT samplers in synthetic solutions containing 500 mu g L-1 of Mn. Co, Ni, Cu, Zn and Pb (4 L at pH 5.5 and ionic strength at 0.05 mol L-1). After retrieval, the DGT units were disassembled and the P81 papers were dried and analysed by EDXRF directly. The 3 MM chromatographic paper diffusion coefficients of the analytes ranged from 1.67 to 1.87 x 10(-6) cm(2) s(-1). The metal retention and phosphate group homogeneities on the P81 membrane was studied by a spot analysis with a diameter of 1 mm. The proposed approach (DGT-EDXRF coupling) was applied to determine the analytes at five sampling sites (48 h in situ deployment) on the Piracicaba river basin, and the results (labile fraction) were compared with 0.45 mu m dissolved fractions determined by synchrotron radiation-excited total reflection X-ray fluorescence (SR-TXRF). The limits of detection of DGT-EDXRF coupling for the analytes (from 7.5 to 26 mu g L-1) were similar to those obtained by the sensitive SR-TXRF technique (3.8 to 9.1 mu g L-1). (C) 2012 Elsevier B.V. All rights reserved.

In situ effect of chewing gum containing CPP–ACP on the mineral precipitation of eroded bovine enamel

Objectives: Stimulation of salivary flow is considered a preventive strategy for dental erosion. Alternatively, products containing calcium phosphate, such as a complex of casein phosphopeptide–amorphous calcium phosphate (CPP–ACP), have also been tested against dental erosion. Therefore, this in situ study analyzed the effect of chewing gum containing CPP–ACP on the mineral precipitation of initial bovine enamel erosion lesions. Methods: Twelve healthy adult subjects wore palatal appliances with two eroded bovine enamel samples. The erosion lesions were produced by immersion in 0.1% citric acid (pH 2.5) for 7 min. During three experimental crossover in situ phases (1 day each), the subjects chewed a type of gum, 3 times for 30 min, in each phase: with CPP–ACP (trident total), without CPP–ACP (trident), and no chewing gum (control). The Knoop surface microhardness was measured at baseline, after erosion in vitro and the mineral precipitation in situ. The differences in the degree of mineral precipitation were analyzed using repeated measures (RM-) ANOVA and post hoc Tukey’s test ( p < 0.05). Results: Significant differences were found among the remineralizing treatments ( p < 0.0001). Chewing gum (19% of microhardness recovery) improved the mineral precipitation compared to control (10%) and the addition of CPP–ACP into the gum promoted the best mineral precipitation effect (30%). Conclusions: Under this protocol, CPP–ACP chewing gum improved the mineral precipitation of eroded enamel. Clinical significance: Since the prevalence of dental erosion is steadily increasing, CPP–ACP chewing gum might be an important strategy to reduce th eprogression of initial erosion lesions.