Long-Term Observations of Isotope Ratio Accuracy and Reproducibility Using Quadrupole ICP-MS

High precision isotope ratio and trace element determination can be achieved with modern quadrupole ICP-MS provided that short and long-term instrument performance is accurately monitored. Here we present results for the isotope ratios ⁶Li/⁷Li, ¹⁴⁷Sm/¹⁴⁹Sm, ¹⁶⁰Dy/¹⁶¹Dy, ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁶Pb/²⁰⁴Pb and ²³⁵U/²³⁸U with which we determined long-term isotope ratio stability of relevance to both trace element and isotope determination. With respect to trace element determination, we first present long-term observations regarding oxide formation rates of Ba and Nd on light REE and heavy REE, as well as Zr on Ag. These showed good correlations and could be used to correct effectively the interference. The efficacy of this correction was demonstrated with analyses of the rock reference material BHVO-2 at both low and high oxide formation rates. Next, we studied the long-term reproducibility of a Dy isotope ratio that was measured to correct for the isobaric interference on Gd. It was found that, regardless of tuning condition, the ratio reproduced very well (0.58% RSD, 1s) and that the estimate of the Gd concentration did not suffer from the large correction (> 10%) caused by the Dy isobar. Long-term reproducibilities of Li, Sm and U isotope ratios, required for accurate mass bias correction when isotopically enriched internal standards of these elements are employed, were measured in the rock reference materials AGV-2 and JA-3 over a time period of up to 3 years. As expected, the Li isotope ratio showed the largest variability (RSD = 7%), but the other two ratios had relative external reproducibilities of only 1.01% (1s, U) and 0.67% (Sm). The mass bias-induced scatter in measurements for Sm and U was so small that the internal standard correction was effective, even for samples with high concentrations of these elements. With regard to Pb-isotope ratio determination, we also present long-term reproducibility for NIST SRM 982, run as an unknown and two accuracy tests for Pb separated from granitoids and from meteorites. It is demonstrated that the obtained ratios, including those involving ²⁰⁴Pb, are accurate relative to MC-ICP-MS determinations and of comparable precision to conventional TIMS analysis. The excellent agreement between all data sets shows the potential of modern quadrupole ICP-MS instrumentation for Pb-isotope determination, particularly for samples with very low Pb content.     

The Puerto Lápice eucrite

Abstract— Puerto Lápice is a new eucrite fall (Castilla‐La Mancha, Spain, 10 May 2007). In this paper, we report its detailed petrography, magnetic characterization, mineral and bulk chemistry, oxygen and noble gas isotope systematics, and radionuclide data. Study of four thin sections from two different specimens reveal that the meteorite is brecciated in nature, and it contains basaltic and granulitic clasts, as well as recrystallized impact melt and breccia fragments. Shock veins are ubiquitous and show evidence of at least three different shock events. Bulk chemical analyses suggest that Puerto Lápice belongs to the main group of basaltic eucrites, although it has a significantly higher Cr content. Oxygen isotopes also confirm that the meteorite is a normal member of the HED suite. Noble gas abundances show typical patterns, with dominant cosmogenic and radiogenic contributions, and indicate an average exposure age of 19 ± 2 Ma, and a Pu‐fission Xe age well within typical eucrite values. Cosmogenic radionuclides suggest a preatmospheric size of about 20–30 cm in diameter.     

Search for extinct aluminum‐26 and titanium‐44 in nanodiamonds from the Allende CV3 and Murchison CM2 meteorites

Abstract– We report Mg‐Al and Ca‐Ti isotopic data for meteoritic nanodiamonds separated from the Allende CV3 and Murchison CM2 meteorites. The goal of this study was to search for excesses in ²⁶Mg and ⁴⁴Ca, which can be attributed to the in situ decay of radioactive and now extinct ²⁶Al and ⁴⁴Ti, respectively. Previous work on presolar SiC and graphite had shown that ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti ratios in presolar grains can be used to discriminate between different types of stellar sources. Aluminum and Ti concentrations are low in the meteoritic nanodiamonds of this study. Murchison nanodiamonds have higher Al and Ti concentrations than the Allende nanodiamonds. This can be attributed to contamination and the presence of presolar SiC in the Murchison nanodiamond samples. ²⁶Mg/²⁴Mg and ⁴⁴Ca/⁴⁰Ca ratios are close to normal in Allende nanodiamonds with upper limits on the initial ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti ratios of approximately 1 × 10^?3. These ratios are factors of 10–1000 and, respectively, 1–1000 lower than those of presolar SiC and graphite grains from supernovae. The ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti data for nanodiamonds are compatible with an asymptotic giant branch star or solar system origin, but not with a supernova origin of a major fraction of meteoritic nanodiamonds. The latter possibility cannot be excluded, though, as the diamond separates may contain significant amounts of contaminating Al and Ti, which would lower the inferred ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti ratios considerably.     

Über die kurzfristige Veränderung des Rassencharakters einerDaphnia-longispina-Population

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Quantifying preferential flow in soils: A review of different techniques

Preferential flow (PF) in soil has both environmental and human health implications since it favours contaminant transport to groundwater without interaction with the chemically and biologically reactive upper layer of soil. PF is, however, difficult to measure and quantify. This paper reviews laboratory and field techniques, such as breakthrough curves, dye tracing, and scanning techniques, for evaluating PF in soil at different scales. Advanced technologies, such as scanning techniques, have increased our capability to quantify transport processes within the soil with minimal soil disturbance. Important issues with respect to quantifying PF concern large-scale studies, frozen soil conditions, tracing techniques for particles and gases, a lack of simple mathematical tools for interpreting field data, and the lack of a systematic approach for comparing PF data resulting from different measurement techniques. Also, more research is required to quantify the relative importance of the various PF processes that occur in soil rather than the integrated result of all PF processes in soils.     

A novel ozone sensor for direct eddy flux measurements

A small, lightweight (1.5 kg) and fast-response ozone sensor for direct eddy flux measurements has been built. The basis for detection is the chemiluminescence of an organic dye adsorbed on dry silica gel in the reaction with ozone. The chemiluminescence is monitored with a cheap and small blue-sensitive photomultiplier. At a flow rate of 100 l min^-1 the ozone sensor has a 90% response time of significantly better than 0.1 s with a detection limit lower than 50 ppt at S/N=3. There are no interferences from other atmospheric trace gases like NO_x, H₂O₂ and PAN. Water vapour and SO₂ enhance the chemiluminescence efficiency of the ozone sensor. Since their response times are 22 seconds and 30 minutes, respectively, no correlation between rapid ozone fluctuations and those of these two trace gases is noticed by the ozone sensor when operating at a frequency of 10 Hz.The ozone sensor was tested for several weeks in continuous measurements of ozone fluxes and deposition velocities over different croplands using the eddy correlation technique. Good agreement was found between ozone dry deposition velocities derived from profile measurements and by eddy correlation.     

Subgrid-Scale Dynamics of Water Vapour, Heat, and Momentum over a Lake

We examine the dynamics of turbulence subgrid (or sub-filter) scales over a lake surface and the implications for large-eddy simulations (LES) of the atmospheric boundary layer. The analysis is based on measurements obtained during the Lake-Atmosphere Turbulent EXchange (LATEX) field campaign (August–October, 2006) over Lake Geneva, Switzerland. Wind velocity, temperature and humidity profiles were measured at 20 Hz using a vertical array of four sonic anemometers and open-path gas analyzers. The results indicate that the observed subgrid-scale statistics are very similar to those observed over land surfaces, suggesting that the effect of the lake waves on surface-layer turbulence during LATEX is small. The measurements allowed, for the first time, the study of subgrid-scale turbulent transport of water vapour, which is found to be well correlated with the transport of heat, suggesting that the subgrid-scale modelling of the two scalars may be coupled to save computational resources during LES.     

Placing geography in the New Zealand Curriculum

The design of a school‐based geography curriculum presents opportunities and challenges for teachers in New Zealand secondary schools. This article discussed the considerations that teachers need to make when developing a school‐based curriculum that is suited to the needs and interests of the students in their school and community. An example of a programme that has been developed to meet the needs and interests of students in a particular secondary school in Christchurch, New Zealand, was outlined.     

Clay mineralogical,geochemical and isotopic tracing of the evolution of the Woodleigh impact structure,Southern Carnarvon Basin,Western Australia

Chaotically structured diamictite from the inner ring syncline surrounding the central uplift of the Woodleigh impact structure contains shocked metamorphic and impact melt-rock fragments, largely derived from Ordovician and Devonian target sandstones. Coarse illite fractions (<2 m) from the sandstones containing no K-feldspar yield K–Ar ages of around 400 Ma, whereas the K–Ar ages of authigenic clays of >0.2 m fractions from the diamictite without smectite and K-feldspar cluster around 360 Ma, consistent with Rb–Sr data. Crystallisation of newly formed illite in the impact melt rock clasts and recrystallisation of earlier formed illite in the sandstone clasts preserved in the diamictite, are attributed to impact-induced hydrothermal processes in the Late Devonian. The illitic clays from the diamictite and from the sandstones have very similar trace element compositions, with significantly enriched incompatible lithophile elements, which increase in concentrations correlatively with those of the compatible ferromagnesian elements. The unusual trace element associations in the clays may be due to the involvement of hot gravity-driven basinal fluids that interacted with rocks of the Precambrian craton to the east of the study area, or with such material transported and reworked in the studied sedimentary succession.