Relative levels of natural and anthropogenic lead in recent Antarctic snow

Concentrations of lead have been measured by ultraclean isotope dilution mass spectrometry in large blocks of surface snow collected along a 433-km coast-interior axis in East Antarctica and near the geographic south pole. Slight contamination existed on the outside of the blocks, but concentration profiles from their exteriors to their interiors indicate that lead concentrations in the innermost parts of the blocks do represent the original concentrations in present-day Antarctic snow. Geographical variations of lead concentrations appear to be mainly due to local emissions from Dumont d'Urville and Amundsen Scott stations. The globally significant lead concentration in present-day Antarctic snow is found to be about 2 pg Pb/g. The corresponding value in Antarctic air is estimated to be about 7 pg Pb/m^3 STP, which is approximately fivefold larger than total natural lead contributed by soil dusts, volcanoes and sea salts. A tentative temporal curve of globally significant lead concentrations in Antarctic ice and snow for the last 13,000 years is given. It shows concentrations of about 0.4 pg Pb/g throughout most of the Holocene, with recent fivefold increases to about 2 pg Pb/g today. The general picture is then that four-fifths of total lead in the Antarctic troposphere today is anthropogenic

Detection of Trace Amounts of Toxic Metals in Environmental Samples by Laser-excited Atomic Fluorescence Spectrometry

Results for the direct determination of trace amounts of Pb and Cd in Antarctic and Greenland ancient ice and recent snow by laser-excited atomic fluorescence spectrometry (LEAFS) are presented. The whole procedure starting from field sampling, mechanical decontamination of the samples in an ultra-clean laboratory and final analysis of the decontaminated samples is described. The measured concentrations varied in the ranges 0.1–3 pg ml^(–1) for Cd and 0.3–30 pg ml^(–1) for Pb. The results for direct analysis by LEAFS agree favourable with those obtained by isotope dilution mass spectrometry and electrothermal atomic absorption spectrometry, which require time-consuming pre-treatment and pre-concentration stages

Anthropogenic lead isotopes in Antarctica

We report the first measurements of Pb isotopes in Antarctic snow, which show that even recent snow containing 2.3 pg/g is highly polluted with anthropogenic Pb. This follows from a comparison of isotope abundances of Pb in surface snow and terrestrial dust extracted from ancient Antarctic ice (Dome C, depth 308 m, approximate age 7,500 a BP), the latter being distinctly more radiogenic. This result is independent of geochemical arguments based on measurements of Al, Na and SO_4. South America is suggested as a likely source of this anthropogenic Pb. The presence of significantly less radiogenic Pb in the snow adjacent to two Antarctic base stations indicates that there is contamination from station emissions, although emission from Australia is an alternative explanation for a site 33 km from Dumont d'Urville

Iron in Ice Cores from Law Dome, East Antarctica: Implications for Past Deposition of Aerosol Iron

Total-dissolvable iron has been measured in sections of three ice cores from Law Dome, East Antarctica, and the results used to calculate atmospheric iron deposition over this region during the late Holocene and to provide a preliminary est. of aerosol iron deposition during the Last Glacial Maximum (LGM). Ice-core sections dating from 56-2730 BP (late Holocene) and ∼18 000 BP (LGM) were decontaminated using trace-metal clean techniques, and total-dissolvable iron was determined in the acidified meltwaters by flow-injection analysis. Our results suggest that the atmospheric iron flux onto the Law Dome region has varied significantly over time-scales ranging from seasonal to glacial-interglacial. The iron concentrations in ice-core sections from the past century suggest (1) a 2-4-fold variation in the atmospheric iron flux over a single annual cycle, with the highest flux occurring during the spring and summer, and (2) a nearly 7-fold variation in the annual maximum atmospheric iron flux over a 14 yr period. The average estimated atmospheric iron flux calculated from our late-Holocene samples is 0.056-0.14 mg m-2 a-1, which agrees well with Holocene flux estimates derived from aluminum measurements in inland Antarctic ice cores and a recent order-of-magnitude estimate of present-day atmospheric iron deposition over the Southern Ocean. The iron concentration of an ice-core section dating from the LGM was more than 50 times higher than in the late-Holocene ice samples. Using a snow-accumulation rate est. of 130 kg m-2 a-1 for this period, we calculate 0.87 mg m-2 a-1 as a preliminary estimate of atmospheric iron deposition during the LGM, which is 6-16 times greater than our average Late-Holocene iron flux. Our data are consistent with the suggestion that there was a significantly greater flux of atmospheric iron onto the Southern Ocean during the LGM than during the Holocene

Magnetic field and pressure effects on charge density wave, superconducting, and magnetic states in Lu5_5Ir4_4Si10_{10} and Er5_5Ir4_4Si10_{10}

We have studied the charge-density-wave (CDW) state for the superconducting Lu$_5$Ir$_4$Si$_{10}$ and the antiferromagnetic Er$_5$Ir$_4$Si$_{10}$ as variables of temperature, magnetic field, and hydrostatic pressure. For Lu$_5$Ir$_4$Si$_{10}$, the application of pressure strongly suppresses the CDW phase but weakly enhances the superconducting phase. For Er$_5$Ir$_4$Si$_{10}$, the incommensurate CDW state is pressure independent and the commensurate CDW state strongly depends on the pressure, whereas the antiferromagnetic ordering is slightly depressed by applying pressure. In addition, Er$_5$Ir$_4$Si$_{10}$ shows negative magnetoresistance at low temperatures, compared with the positive magnetoresistance of Lu$_5$Ir$_4$Si$_{10}$.Comment: 12 pages, including 6 figure

Lead Isotopes and Selected Metals in Ice from Law Dome, Antarctica

The isotopic composition. of Pb and the concentrations of Pb, Ba and Bi were measured in selected ice-core samples from Law Dome, East Antarctica, to a depth of 1196 m. The range of concentrations found in decontaminated ice was 0.03-1.5 pg g-1 for Pb, 0.9-6.1 pg g-1 for Ba and 0.4-17 fg g-1 for Bi, excluding the deepest sample which contained ∼1 ppm of rock dust. The abundances of all four stable lead isotopes were measured and gave 206Pb/207Pb ratios ≤ ∼1.23. A value of 208Pb/207Pb = 2.78 was measured in the deepest sample and is consistent with reported Pb isotope ratios of Antarctic granulites. Although the element concentrations in some samples were lower than have been reported elsewhere, geochemical and isotopic evidence indicated that a number of samples were contaminated with Pb not present in the original ice. However, it appears that the technical skills now available are approaching the level where careful sample selection, decontamination and analysis can yield accurate results for the concentration and isotopic composition of Pb in Earth\u27s purest naturally occurring ice

Spin-Atomic Vibration Interaction and Spin-Flip Hamiltonian of a Single Atomic Spin in a Crystal Field

We derive the spin-atomic vibration interaction $V_{\rm SA}$ and the spin-flip Hamiltonian $V_{\rm SF}$ of a single atomic spin in a crystal field. We here apply the perturbation theory to a model with the spin-orbit interaction and the kinetic and potential energies of electrons. The model also takes into account the difference in vibration displacement between an effective nucleus and electrons, \Delta {{\boldmath r}}. Examining the coefficients of $V_{\rm SA}$ and $V_{\rm SF}$, we first show that $V_{\rm SA}$ appears for \Delta {{\boldmath r}}$\ne$0, while $V_{\rm SF}$ is present independently of \Delta {{\boldmath r}}. As an application, we next obtain $V_{\rm SA}$ and $V_{\rm SF}$ of an Fe ion in a crystal field of tetragonal symmetry. It is found that the magnitudes of the coefficients of $V_{\rm SA}$ can be larger than those of the conventional spin-phonon interaction depending on vibration frequency. In addition, transition probabilities per unit time due to $V_{\rm SA}$ and $V_{\rm SF}$ are investigated for the Fe ion with an anisotropy energy of $-|D|S_Z^2$, where $D$ is an anisotropy constant and $S_Z$ is the $Z$ component of a spin operator.Comment: 55 pages, 17 figures, to be published in J. Phys. Soc. Jpn. 79 (2010) No. 11, typos correcte