A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.     

Quantitative reconstruction of Holocene precipitation changes in southern Patagonia

Holocene variations in annual precipitation (P_ann) were reconstructed from pollen data from southern Argentinian Patagonia using a transfer function developed based on a weighted-averaging partial least squares (WA-PLS) regression. The pollen–climate calibration model consisted of 112 surface soil samples and 59 pollen types from the main vegetation units, and modern precipitation values obtained from a global climate database. The performance (r² = 0.517; RMSEP = 126 mm) of the model was comparable or slightly lower than in other comparable pollen–climate models. Fossil pollen data were obtained from a sediment core from Cerro Frias site (50°24'S, 72°42'W) located at the forest-steppe ecotone. Reconstructed P_ann values of about 200 mm suggest dry conditions during the Pleistocene–Holocene transition (12,500–10,500 cal yr BP). P_ann values were about 300–350 mm from 10,500 to 8000 cal yr BP and increased to 400–500 mm between 8000 and 1000 cal yr BP. An abrupt decrease in P_ann at about 1000 cal yr BP was associated with a Nothofagus decline. The reconstructed P_ann suggests a weakening and southward shift of the westerlies during the early Holocene and intensification, with no major latitudinal shifts, during the mid-Holocene at high latitudes in southern Patagonia.     

The activation energy values estimated by the Arrhenius equation as a controlling factor of platinum-group mineral formation

In ophiolite complexes and Ural/Alaskan-type intrusions the platinum-group element minerals (PGM) occur as laurite (RuS₂), erlichmanite (OsS₂), irarsite (IrAsS) and alloys (Os-Ir-Ru and Pt-Fe). They are commonly found as small inclusions (normally less than 10 μm, occasionally up to 100 μm) in chromite. The origin of coarse-grained PGM, in the form of 0.5-10 mm nuggets, in placer deposits related with mafic/ultramafic complexes remains still unclear. Literature data on grain size (r) of platinum-group minerals (PGM) and their formation temperature (range of temperatures between 700 and 1100 °C), revealed an Arrhenius temperature dependence. Correlation of the rate of crystal formation that depends on temperature (T) with the size (r) of the grain results in a linear relationship between ln(r) and 1/T. From the slope of the line n × ln(r) = −const. + E_act/RT the activation energy for the formation of IPGM (Ir-platinum-group minerals) was estimated, for the first time in the present study, to be approximately 450 ± 45 kJ mol⁻¹. Applying the Arrhenius equation, the corresponding formation temperature for extremely large IPGM grains (up to 1.3 mm) in chromite ores related to ophiolites was found to be approximately 740 °C. It seems to be consistent with a lower formation temperature than with the typical formation temperature of small PGM grains associated with ophiolitic chromitites. This suggests that coarse-grained PGM in mafic/ultramafic complexes, along the permeable shear zones, may have been re-crystallized during plastic deformation at relatively lower temperatures (700-800 °C), under appropriate pressure, temperature, redox conditions and an increased H₂O content. Thus, applying the plot of ln(r) versus 1/T on large Os-Ir-Ru-minerals (sulfides or alloys), characterized by an r value falling into the linear part of the graph and having evidence supporting their formation at relatively high temperatures, then the corresponding formation temperature of those IPGM can be found.     

Search for nucleosynthetic and radiogenic tellurium isotope anomalies in carbonaceous chondrites

Tellurium isotope data acquired by multiple-collector inductively coupled plasma-mass spectrometry (MC-ICPMS) are presented for sequential acid leachates of the carbonaceous chondrites Orgueil, Murchison, and Allende. Tellurium isotopes are produced by a broad range of nucleosynthetic pathways and they are therefore of particular interest given the isotopic anomalies previously identified for other elements in these meteorites. In addition, the data provide new constraints on the initial solar system abundance of the r-process nuclide ¹²⁶Sn, which decays to ¹²⁶Te with a half-life of 234,500 years. The ¹²⁶Te/¹²⁸Te ratios of all leachates were found to be identical, within uncertainty, despite variations in ¹²⁴Sn/¹²⁸Te of between about 0.002 and 1.4. The data define a ¹²⁶Sn/¹²⁴Sn ratio of <7.7 × 10⁻⁵ at the time of last isotopic closure, consistent with the value of <18 × 10⁻⁵ previously reported for bulk carbonaceous chondrites. How close this is to the initial ¹²⁶Sn/¹²⁴Sn ratio of the solar system depends on when the investigated samples last experienced redistribution of Sn and Te. No clear evidence is found for nucleosynthetic anomalies in the abundances of p-, s-, and r-process nuclides. The largest effect detected in this study is a small excess of the r-process nuclide ¹³⁰Te in a nitric acid leachate of Murchison. This fraction displays an anomalous ε¹³⁰Te of +3.5 ± 2.5. Although barely resolvable given the analytical uncertainties, this is consistent with the presence of a small excess r-process component or an s-process deficit. The general absence of anomalies contrasts with previous results obtained for K, Cr, Zr, Mo, and Ba isotopes in similar leachates, which display nucleosynthetic anomalies of up to 3.8%. The reason for this discrepancy is unclear but it may reflect volatility and more efficient mixing of Te in the solar nebula.     

Multiple magnetization events in the Red River carbonates, Williston Basin, Canada: Evidence for fluid-flow?

Samples collected from the Upper Ordovician Red River carbonates in a well at the centre of the Williston Basin revealed two paleomagnetic components with different inclinations, 60.3 ± 3.9° (k = 70.7, N = 12) and 20.4 ± 3.3° (k = 141.2, N = 8), but similar declination values in individual specimens. Inclination-only analysis indicates two possible scenarios for the age of these two magnetizations: in scenario (a) the timing of magnetization happened sometime between Late Ordovician to Devonian; and in scenario (b) there are two different remagnetizations, one that overlaps Pennsylvanian to Permian time while the other can have either a Late Jurassic or a Tertiary age. Whereas dolomitization and some isotopic data tend to support scenario (a), previous paleomagnetic data from the Williston Basin and from younger units in the same well, the tectonic evolution of the basin, and the hydrocarbon maturation pattern in the Red River carbonates all favour chemical remagnetization(s) driven by orogenic fluids during the Alleghenian and Laramide orogenies.     

The bimodal rift-related Juscelândia volcanosedimentary sequence in central Brazil: Mesoproterozoic extension and Neoproterozoic metamorphism

The Barro Alto Complex and Juscelândia volcanosedimentary sequence are exposed in the central part of the Neoproterozoic Brasília belt of central Brazil. The former is a large (approximately 150 km long), boomerang-shaped, mafic-ultramafic, layered complex formed by two different intrusions metamorphosed under granulite facies. These rocks are tectonically overlain by rocks of the Juscelândia volcanosedimentary sequence, represented mainly by biotite-gneiss and amphibolite, or amphibolite facies metamorphic equivalents of rhyolite and basalt, respectively. New SIMS U–Pb zircon data and Sm–Nd isochron data presented herein help clarify the igneous and metamorphic evolution of the Juscelândia volcanosedimentary sequence, as well as its relationship with the Barro Alto Complex. Zircon grains from two biotite gneisses were analyzed by SIMS (SHRIMP) and indicate Mesoproterozoic dates, approximately 1.28 Ga, interpreted as the time of bimodal volcanism in a tectonic setting transitional between a continental rift and an ocean basin. Metamorphism is constrained by Sm–Nd garnet-whole-rock isochrons for garnet amphibolite and pelitic schists of the Juscelândia sequence, as well as for clinopyroxene-garnet amphibolite and garnet granulite of the Barro Alto Complex, which give ages between 0.74 and 0.76 Ga, in agreement with SIMS dates for metamorphic zircon rims. These new data are significant, because they establish that a single metamorphic event affected both the Barro Alto Complex and the Juscelândia sequence. Based on these new data, we present a modified tectonic model for the Brasília belt.     

Sulfur Determination in Geological Samples Based on Coupled Analytical Techniques: Electric Furnace-IC and TGA-EGA

A study has been undertaken to determine sulfur in geological samples by coupled analytical techniques. Two measurement methods have been developed: one using an electric furnace coupled to an ion chromatograph (electric furnace-IC) and another using infrared (IR) and quadrupole mass spectrometry (QMS) for evolved gas analysis (EGA) coupled with a thermogravimetric analyser (TGA). In the electric furnace-IC method, measurement was performed without any sample pre-treatment. The measurement conditions were optimised by varying sample quantity, type of catalyst (WO₃, Cu, W and V₂O₅) and sample/catalyst ratio, and the detection limit was 10 μg g⁻¹. Sulfur ores decompose at different temperatures. However, TGA-EGA allowed identification of the different forms of sulfur in the sample, even when they were found in very low concentrations, because the sulfur was continuously analysed. The developed chromatographic method allowed simultaneous analysis of several sample components, such as S, Cl and F, with a low detection limit. The method was much faster and more specific than the methods described in the literature. The results of the sulfur determination had low scatter, possibly because the samples underwent little handling during analysis: the operator only weighed and placed the sample in the furnace, the rest of the measurement process was fully automated. The results obtained by both the developed methods have been validated by using reference materials and comparison with combustion-IR spectroscopy, a standard method for determining total sulfur in a sample.     

Soil erosion prediction using the Revised Universal Soil Loss Equation (RUSLE) in a GIS framework,Chania, Northwestern Crete,Greece

Soil erosion is a growing problem in southern Greece and particularly in the island of Crete, the biggest Greek island with great agricultural activity. Soil erosion not only decreases agricultural productivity, but also reduces the water availability. In the current study, an effort to predict potential annual soil loss has been conducted. For the prediction, the Revised Universal Soil Loss Equation (RUSLE) has been adopted in a Geographical Information System framework. The RUSLE factors were calculated (in the form of raster layers) for the nine major watersheds which cover the northern part of the Chania Prefecture. The R-factor was calculated from monthly and annual precipitation data. The K-factor was estimated using soil maps available from the Soil Geographical Data Base of Europe at a scale of 1:1,000,000. The LS-factor was calculated from a 30-m digital elevation model. The C-factor was calculated using Remote Sensing techniques. The P-factor in absence of data was set to 1. The results show that an extended part of the area is undergoing severe erosion. The mean annual soil loss is predicted up to ∼200 (t/ha year⁻¹) for some watersheds showing extended erosion and demanding the attention of local administrators.     

Geochemistry of Neogene quartz andesites from the Oaş and Gutâi Mountains,Eastern Carpathians (Romania): a complex magma genesis

The Neogene quartz andesites from the Oa? and Gutâi Mountains (Romania) are mid-K calc-alkaline rocks and contain plagioclase-orthopyroxene-clinopyroxene-amphibole-magnetite phenocrysts as well as quartz crystals. They are associated with a volcanic sequence ranging from basalts and basaltic andesites to dacites and rhyolites, but form a separate magma group, mostly in respect to the trace elements. Based on the geochemical data combined with inferences from complex zoning patterns in plagioclase and pyroxene, the evolution of quartz andesites is interpreted in terms of fractional crystallization, AFC and magma mixing. A parental magma deriving from a MORB- or OIB-type source modified by fluids and melts originating from sediments is envisaged.