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.     

Proximity to ice fields and lake depth as modulators of paleoclimate records: a regional study from southwest Yukon,Canada

Pronounced climate warming during the past century has been well documented in high-latitude regions. Nonetheless, considerable heterogeneity exists in northern climate trends. We examined the roles of cryospheric landscape and lake depth in modulating the rate and magnitude of local climate responses through a paleolimnological study of lakes from southwest Yukon, Canada. By sampling lakes at varying distances from the Wrangell-St. Elias ice fields, we hypothesized that, for lakes of similar maximum depth, sites closest to the ice fields would be relatively complacent in terms of their chironomid and diatom assemblage changes over the past ~200 years. This hypothesis is based on the moderating effect of the glaciers on local climate, which would be most pronounced in the lakes nearest to the ice fields. However, given the known ecological differences between deep and shallow lakes, we further predicted that, for a given distance from the ice fields, a sediment record from a shallower lake would show the greatest change in stratigraphic subfossil assemblages. Because of the complicated shape of the ice fields, we applied the longitude for each site (which decreases from west to east) to approximate the proximity of our study lakes to the ice fields. Consistent with our predictions, we observed a space-transgressive pattern in the chironomid assemblage turnover that was associated with their proximity to the ice fields (r = ?0.75, P = 0.034, n = 8) across lakes of similar depth (mean maximum depth ± 1, SE = 18.1 ± 2.6 m). Considering a broader network of lakes that represented a greater range in maximum depth (4.9–29 m), we found that differences in subfossil chironomid assemblages between the modern and ca. AD 1800 sediment layers were strongly related to lake depth (r = ?0.77, P < 0.001, n = 15), but failed to detect a significant relationship with latitude or longitude (i.e. our proxy for proximity to the ice fields). Similarly, our comparative high-resolution analyses of two lakes with distinct lake morphometries, but similar proximities to the ice fields, demonstrated the predicted contrasting pattern: we observed pronounced post-1880 changes in the biotic assemblages in the shallow lake and a muted and delayed response (i.e. ~1970s) in the deeper lake. Our findings confirm that cryospheric landscape features can strongly modulate regional climate. Furthermore, our work shows that investigators need to be conscious of how climate change affects the structure and functioning of lakes of different typologies, which influences the way in which paleoclimate signals are recorded and interpreted.     

Contrasting perspectives on barriers to adaptation in Australian climate change policy

Barriers to adaptation have emerged as key concerns in climate change theory and practice, however there remains little consensus about which barriers are the most significant to different groups and how competing concerns may be addressed. We investigate the significance of different barriers to adaptation for governments, the private sector, and civil society in Australia through a systematic analysis of submissions to the Australian Productivity Commission’s inquiry into barriers to adaptation. Our results show that respondents prioritise barriers differently according to their respective sectors, and that there are competing concerns about which barriers should be addressed first. Nevertheless, some barriers are more persistent in the submissions than others, with governance and policy seen by most groups as being the major impediments to adaptation. We explain the implications of our analysis for adaptation politics and policy.     

Petrological imaging of an active pluton beneath Cerro Uturuncu,Bolivia

Uturuncu is a dormant volcano in the Altiplano of SW Bolivia. A present day ~70 km diameter interferometric synthetic aperture radar (InSAR) anomaly roughly centred on Uturuncu’s edifice is believed to be a result of magma intrusion into an active crustal pluton. Past activity at the volcano, spanning 0.89 to 0.27 Ma, is exclusively effusive and almost all lavas and domes are dacitic with phenocrysts of plagioclase, orthopyroxene, biotite, ilmenite and Ti-magnetite plus or minus quartz, and microlites of plagioclase and orthopyroxene set in rhyolitic groundmass glass. Plagioclase-hosted melt inclusions (MI) are rhyolitic with major element compositions that are similar to groundmass glasses. H₂O concentrations plotted versus incompatible elements for individual samples describe a trend typical of near-isobaric, volatile-saturated crystallisation. At 870 °C, the average magma temperature calculated from Fe–Ti oxides, the average H₂O of 3.2 ± 0.7 wt% and CO₂ typically <160 ppm equate to MI trapping pressures of 50–120 MPa, approximately 2–4.5 km below surface. Such shallow storage precludes the role of dacite magma emplacement into pre-eruptive storage regions as being the cause of the observed InSAR anomaly. Storage pressures, whole-rock (WR) chemistry and phase assemblage are remarkably consistent across the eruptive history of the volcano, although magmatic temperatures calculated from Fe–Ti oxide geothermometry, zircon saturation thermometry using MI and orthopyroxene-melt thermometry range from 760 to 925 °C at NNO ± 1 log. This large temperature range is similar to that of saturation temperatures of observed phases in experimental data on Uturuncu dacites. The variation in calculated temperatures is attributed to piecemeal construction of the active pluton by successive inputs of new magma into a growing volume of plutonic mush. Fluctuating temperatures within the mush can account for sieve-textured cores and complex zoning in plagioclase phenocrysts, resorption of quartz and biotite phenocrysts and apatite microlites. That Fe–Ti oxide temperatures vary by ~50–100 °C in a single thin section indicates that magmas were not homogenised effectively prior to eruption. Phenocryst contents do not correlate with calculated magmatic temperatures, consistent with crystal entrainment from the mush during magma ascent and eruption. Microlites grew during ascent from the magma storage region. Variability in the proportion of microlites is attributed to differing ascent and effusion rates with faster rates in general for lavas >0.5 Ma compared to those <0.5 Ma. High microlite contents of domes indicate that effusion rates were probably slowest in dome-forming eruptions. Linear trends in WR major and trace element chemistries, highly variable, bimodal mineral compositions, and the presence of mafic enclaves in lavas demonstrate that intrusion of more mafic magmas into the evolving, shallow plutonic mush also occurred further amplifying local temperature fluctuations. Crystallisation and resorption of accessory phases, particularly ilmenite and apatite, can be detected in MI and groundmass glass trace element covariation trends, which are oblique to WRs. Marked variability of Ba, Sr and La in MI can be attributed to temperature-controlled, localised crystallisation of plagioclase, orthopyroxene and biotite within the evolving mush.     

Radar observations of asteroid 1998 ML14

Abstract— Goldstone and Arecibo delay‐Doppler radar imaging of asteroid 1998 ML 14 shortly after its discovery reveals a 1 km diameter spheroid with prominent topography on one side and subdued topography on the other. The object's radar and optical properties are typical for S‐class near‐Earth asteroids. The gravitational slopes of a shape model derived from the images and assumed to have a uniform density are shallow, exceeding 30° over only 4% of the surface. If 1998 ML14's density distribution is uniform, then its orbital environment is similar to a planetary body with a spheroidal gravitational field and is relatively stable. Integration of a radar‐refined orbit reveals that the 1998 apparition was the asteroid's closest approach to Earth since at least 1100 and until 2283, when it approaches to within 2.4 lunar distances. Outside of that time interval, orbit uncertainties based on the present set of observations preclude reliable prediction.     

4U 1957+11: a persistent low-mass X-ray binary and black hole candidate in the high state?

We report on several pointed Rossi X-ray Timing Explorer observations of the enigmatic low-mass X-ray binary (LMXB) 4U 1957+11 at different X-ray luminosities. The luminosity of the source varied by more than a factor of 4 on time-scales of months to years. The spectrum of the source tends to become harder when its luminosity increases. Only very weak  (1–2  per cent rms amplitude,  0.001–10 Hz  ,  2–60 keV)  rapid X-ray variability was observed during the observations. A comparison of the spectral and temporal behaviour of 4U 1957+11 with other X-ray binary systems, in particular LMC X-3, indicates that 4U 1957+11 is likely to be a persistent LMXB harbouring a black hole and it is persistently in the black hole high state. If confirmed, it would be the only such system known.     

An evaluation of the use of halogen and water abundances in efforts to distinguish mineralized and barren intrusive rocks

Analysis of the chlorine, fluorine and water content of approximately 200 samples from a total of fourteen mineralized and ten barren intrusive rocks from the Caribbean and Central America indicates that abundances of these constituents fail to distinguish mineralized rocks from barren rocks. Variations in background abundances arise from the increase in halogen content of potassium-rich rocks and from the depletion of halogens in altered and porphyritic rocks. A particularly well developed potassium-fluorine covariance is observed in tin-bearing granites, but such a covariance cannot be used to distinguish intrusive rocks associated with porphyry copper mineralization.     

Palaeoecology of a late Allerød peat bed at Godøy,western Norway

A peat bed found under solifluction deposits on Godøya island, western Norway, accumulated during a few decades around 11 000 yr BP, at the end of the Allerød period of the Late Weichselian. Palaeoecological investigations showed a local vegetation succession on wet sand culminating in a mire community dominated by Carex nigra. Periodic flooding brought in sand and silt, which decreased as drainage was impeded sufficiently for standing water to develop. The surrounding terrestrial vegetation was dominated by Salix scrub, with some open heath and alpine habitats nearby. Apart from two aquatic species, the 29 insect taxa recorded are characteristic of alpine heaths, plant litter (under Salix scrub) and stream-sides. Their remains, together with the terrestrial plant macrofossils, were washed into the mire from nearby. Because the fossils are locally derived, the environmental reconstructions are of the actual conditions at Godøy at ca. 11 000 yr BP. Palaeotemperature estimates from beetles and plants are in agreement. The coleopteran estimates (Mutual Climatic Range Method) suggest mean July temperatures of 10–13°C, slightly cooler than today (13.5°), and January temperatures between +1 and ?10°C, similar to or much colder than today. Summer temperature estimates from individual plant taxa indicate that temperatures during the Allerød period were similar to today's, but estimates from the reconstructed vegetation and timber-line positions give estimates up to 3.5° cooler. Temperatures fell 2.5–7.5°C at the Younger Dryas. This abrupt and severe cooling initiated the solifluction processes on Godøya that buried the peat. The Godøy peat bed and its contained fossils provide a rare glimpse of Allerød biota and environments at the local (site) scale.     

Stacking for the frequencies and Qs of 0S0 and 1S0

Summary. Using nine IDA records for the Indonesian earthquake of 1977 August 19, we have formed an optimal linear combination of the records and have measured the frequency and Q of ₀ S ₀ and ₁ S ₀. The frequency was measured using the moment ratio method. The attenuation was measured by the minimum width method and by the time-lapse method. The frequency and attenuation were measured simultaneously by varying them to obtain a best fit to the data. A 2000-hr stack, the sum of nine individual records, for ₀ S ₀ gave a frequency of 0.814664 mHz±4 ppm. The values for the Q of ₀ S ₀ for the three different methods of measurement were 5600,5833 and 5700, respectively. The error in the estimates of Q ^-1 is about 5 per cent for the minimum power method. For ₁ S ₀ a 300-hr stack yielded a frequency of 1.63151 mHz±30 ppm. The values of Q for this mode were 1960, 1800 and 1850, respectively, with an error in Q ^-1 of about 12 per cent for the minimum power method.