Rare earth elements determined in Antarctic ice by inductively coupled plasma--time of flight, quadrupole and sector field-mass spectrometry: An inter-comparison study.

Inductively coupled plasma mass spectrometry (ICP-MS) is a suitable tool for multi-element analysis at low concentration levels. Rare earth element (REE) determinations in standard reference materials and small volumes of molten ice core samples from Antarctica have been performed with an ICP-time of flight-MS (ICP-TOF-MS) system. Recovery rates for REE in e.g. SPS-SW1 amounted to approximately 103%, and the relative standard deviations were 3.4% for replicate analysis at REE concentrations in the lower ngL(-1) range. Analyses of REE concentrations in Antarctic ice core samples showed that the ICP-TOF-MS technique meets the demands of restricted sample mass. The data obtained are in good agreement with ICP-Quadrupole-MS (ICP-Q-MS) and ICP-Sector Field-MS (ICP-SF-MS) results. The ICP-TOF-MS system determines accurately and precisely REE concentrations exceeding 5ngL(-1) while between 0.5 and 5ngL(-1) accuracy and precision are element dependent.

Is the umbo matrix of bivalve shells (Laternula elliptica) a climate archive?

Heavy metal accumulation into bivalve soft tissues has received increasing interest in recent years with respect to biomonitoring of environmental change including pollution. To a lesser extent, accretion of elements from the environment into bivalve hard structures (shells) has been investigated, although the importance of the shells as environmental archives has been acknowledged. Here we report element distribution within consecutive growth bands in the shells of the Antarctic soft shell clam Laternula elliptica, which is currently exposed to vast environmental change in Antarctic Peninsula coastal environments that undergo rapid climate warming. We performed a high spatial resolution analysis for Al, Fe, Mn, Cu, Pb and U in the shell umbo, by means of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Element ratios within the umbo did not resemble either the ratios in the surrounding seawater, the sedimenting material in Potter Cove, or even the Earth's crust basal composition. Mn and Cu were preferentially incorporated into the umbo. A strong decrease of element accretion with time could be related to lifetime respiration mass (R) of the animals. This indicates element accretion into the umbo and shell matrix to be largely a function of animal ecophysiology and life history, and these effects need to be considered in the context of potential usefulness of L. elliptica shells as environmental archives.

Application of LA-ICP-MS in polar ice core studies.

The direct determination of element signatures in polar ice core samples from Greenland by laser ablation with subsequent inductively coupled plasma mass spectrometry analysis has been investigated. A cryogenic sample chamber enables the element determination in ice directly from the solid (frozen) state. A procedure was developed to analyse up to 38 elements (traces: Mg, Al, Fe, Zn, Cd, Pb and rare earth elements; minor constituents: Na) in ice samples from Greenland with a previously unachievable spatial resolution of 4 mm along the core axis. This resolution is helpful to detect seasonal variations of element concentration in thin annual layers of deep ice. We report operating conditions and analytical performance of the experimental set up, the improvement of signal stability by (17)OH internal standardisation and application of a desolvation unit. Calibration of the system was performed with frozen multielement standard solutions along a special preparation procedure. Detection limits for the tracers Na, Mg (sea salt), Al (mineral dust) and Zn (anthropogenic source) are 0.1-1 microg kg(-1). Best detection limits in the range of 0.001-0.01 microg kg(-1 )were reached for Co, Pb and all rare earth elements. To validate the method, frozen standard reference materials were measured. The recovery is about +/-10%. Greenland ice core samples from different ages were analysed with the new technique. The results obtained by laser ablation were compared with values from solution analysis, available published data and the particle content. Most elements have shown good correlation with the particle content in the Greenland samples; however, differences could be seen between the values obtained by laser ablation and solution bulk analysis after a tri-acid digestion. The influence of particles is discussed. The high spatially resolved 2D mapping of element concentrations shows strong inhomogeneities along the core axis most probably due to seasonal variations of element deposition.

Laser ablation inductively coupled plasma mass spectrometry: a new tool for trace element analysis in ice cores.

A new method for the detection of trace elements in polar ice cores using laser ablation with subsequent inductively coupled plasma mass spectrometry analysis is described. To enable direct analysis of frozen ice samples a special laser ablation chamber was constructed. Direct analysis reduces the risk of contamination. The defined removal of material from the ice surface by means of a laser beam leads to higher spatial resolution (300-1000 microm) in comparison to investigations with molten ice samples. This is helpful for the detection of element signatures in annual layers of ice cores. The method was applied to the successful determination of traces for the elements Mg, Al, Fe, Zn, Cd, Pb, some rare-earth elements (REE) and minor constituents such as Ca and Na in ice cores. These selected elements serve as tracer elements for certain sources and their element signatures detected in polar ice cores can give hints to climate changes in the past. We report results from measurements of frozen ice samples, the achievable signal intensities, standard deviations and calibration graphs as well as the first signal progression of 205Pb in an 8,000-year-old ice core sample from Greenland. In addition, the first picture of a crater on an ice surface burnt by an IR laser made by cryogenic scanning electron microscopy is presented.