Bodo Hattendorf

Quantitative multi-element analysis of minerals, fluid and melt inclusions by laser-ablation inductively-coupled-plasma mass-spectrometry

Laser-ablation ICPMS has become widely accessible as a powerful and efficient multi-element microanalytical technique. One of its key strengths is the ability to analyse a wide concentration range from major (tens of wt.%) to trace (ng/g) levels in minerals and their microscopic inclusions. An ArF excimer laser system (λ = 193 nm) with imaging optics for controlled UV ablation and simultaneous petrographic viewing was designed specifically for representative sampling and quantitative multi-element analysis of microscopic fluid, melt and mineral inclusions beneath the sample surface. After a review of the requirements and recent technical developments, results are presented which together document the reliability and reproducibility of quantitative microanalysis of complex samples such as zoned crystals or fluid and melt inclusions in various host minerals. Analytical errors due to elemental fractionation are reduced to the typical precision achieved by quadrupole LA-ICPMS in multi-element mode (2–5% RSD). This progress is largely due to the small size of aerosol particles generated by the optimized UV optical system. Depth profiling yields representative and accurate concentration results at a resolution of ∼0.1 μm perpendicular to the ablation surface. Ablation is largely matrix-insensitive for different elements, such that silicate and borate glasses, silicates and oxide minerals, or direct liquid ablation can be used interchangeably for external standardization of any homogeneous or heterogeneous material. The absolute ablation rate is material dependent, however, so that quantitative LA-ICPMS analysis requires an internal standard (i.e., an independent constraint such as the absolute concentration of one element). Our approach to quantifying fluid and melt inclusion compositions is described in detail. Experiments with synthetic fluid inclusions show that accurate results are obtained by combining the LA-ICPMS analysis of element concentration ratios with a microthermometric measurement of the NaCl equivalent concentration and an empirical description of the effect of major cations on the final melting temperatures of ice, hydrohalite or halite. Expected calibration errors for NaCl-H2O-dominated fluids are smaller than the typical analytical scatter within an assemblage of simultaneously trapped fluid inclusions. Analytical precision is limited by representative ablation of all phases in heterogeneous inclusions and the integration of transient ICPMS signals, to typically ±10 to 20% RSD. Element concentrations in devitrified and even coarsely crystallized silicate melt inclusions can be reconstituted from LA-ICPMS signals. Deconvolution of inclusion and host signals with internal standardization automatically corrects for sidewall crystallization after melt entrapment at high temperature. A test using melt inclusions in a midocean ridge basalt, a summary of published geochemical studies and a new application to REE analysis of coexisting fluids and mineral phases in carbonatite-related veins illustrate the versatility and some of the strengths and limitations of LA-ICPMS, in comparison with other microanalytical techniques.

Highly multiplexed imaging of tumor tissues with subcellular resolution by mass cytometry

Mass cytometry enables high-dimensional, single-cell analysis of cell type and state. In mass cytometry, rare earth metals are used as reporters on antibodies. Analysis of metal abundances using the mass cytometer allows determination of marker expression in individual cells. Mass cytometry has previously been applied only to cell suspensions. To gain spatial information, we have coupled immunohistochemical and immunocytochemical methods with high-resolution laser ablation to CyTOF mass cytometry. This approach enables the simultaneous imaging of 32 proteins and protein modifications at subcellular resolution; with the availability of additional isotopes, measurement of over 100 markers will be possible. We applied imaging mass cytometry to human breast cancer samples, allowing delineation of cell subpopulations and cell-cell interactions and highlighting tumor heterogeneity. Imaging mass cytometry complements existing imaging approaches. It will enable basic studies of tissue heterogeneity and function and support the transition of medicine toward individualized molecularly targeted diagnosis and therapies.

Persistence of engineered nanoparticles in a municipal solid-waste incineration plant

More than 100 million tonnes of municipal solid waste are incinerated worldwide every year. However, little is known about the fate of nanomaterials during incineration, even though the presence of engineered nanoparticles in waste is expected to grow. Here, we show that cerium oxide nanoparticles introduced into a full-scale waste incineration plant bind loosely to solid residues from the combustion process and can be efficiently removed from flue gas using current filter technology. The nanoparticles were introduced either directly onto the waste before incineration or into the gas stream exiting the furnace of an incinerator that processes 200,000 tonnes of waste per year. Nanoparticles that attached to the surface of the solid residues did not become a fixed part of the residues and did not demonstrate any physical or chemical changes. Our observations show that although it is possible to incinerate waste without releasing nanoparticles into the atmosphere, the residues to which they bind eventually end up in landfills or recovered raw materials, confirming that there is a clear environmental need to develop degradable nanoparticles.

Characteristics and capabilities of an ICP-MS with a dynamic reaction cell for dry aerosols and laser ablation

The characteristics of a dynamic reaction cell (DRC), used to reduce interferences from molecular or elemental ions in an inductively coupled plasma quadrupole mass spectrometer (ICP-MS), were investigated for dry sample introduction. The dependence of the signals from molecular ions formed in the ICP or in the interface region was monitored with the variation of the concentration of reaction or buffer gas used. The differences between wet aerosols, generated with a standard cyclonic spray chamber and concentric nebulizer, to dry aerosols, generated by a desolvating nebulizer or laser ablation, were determined. The comparison of prominent background signals to ion signals from selected analyte ions was used to determine parameters that lead to optimum signal/background ratios and analytical performance for laser ablation analysis. Ammonia and hydrogen were used as reactive gases in these experiments. Additionally, He, Ne and Xe were used as a buffer gas to enhance thermalization in the DRC. The reaction rate with ammonia was found to be distinctly higher than with hydrogen. On the other hand, side reactions with analyte ions, leading to additional interferences and analyte loss through the formation of clusters, were severe with ammonia. Hydrogen, having a smaller reactivity, reduces cluster formation and retains analyte sensitivity even at a high gas concentration. It is therefore better suited for methods that allow only short measurement times, like laser ablation (LA) or electrothermal vaporization (ETV). The capabilities of the DRC for LA are demonstrated through the determination of Ca in a quartz sample and Nb in a chromium matrix, which suffer from either Ar-ions or Ar-based interferences. Reduction of the background intensities and use of the most abundant isotope led to a reduction of the limit of detection for Ca in quartz by two orders of magnitude and an improvement of accuracy for the determination of Nb in a chromium-matrix.

A prototype of a new inductively coupled plasma time-of-flight mass spectrometer providing temporally resolved, multi-element detection of short signals generated by single particles and droplets

A prototype inductively coupled plasma time-of-flight mass spectrometer (ICPTOFMS) for time resolved measurements of transient signals in the microsecond regime is described in this work. Analytical figures of merit for the prototype are given for both liquid nebulization and single droplet introduction and are compared to a conventional quadrupole-based ICPMS using the same ICP source and vacuum interface. Quasi-simultaneous detection at a time resolution of 33 μs of the prototype ICPTOFMS allows multi-isotope monitoring of short signals (200–500 μs duration) generated from individual droplets and particles. The capabilities of the instrument for the analysis of single nanoparticles are studied using microdroplets consisting of a multi-element standard solution and containing 114 nm Au particles. The detection efficiencies for Ag and Au, calculated from the response of individual droplets and particles, are similar to those of the quadrupole-based instrument and amount to 1.3 × 10−6 ions per atom and 3.1 × 10−6 ions per atom, respectively. The sizes of the smallest detectable Ag, Au and U metallic nanoparticles are estimated to be 46 nm, 32 nm and 22 nm, respectively. Furthermore, time shifts of the signals of different elements within single droplets were observed. These new results demonstrate the advantage of the temporal resolution of the instrument for studying processes taking place in the plasma on the μs-time scale.

GFAJ-1 Is an Arsenate-Resistant, Phosphate-Dependent Organism

Resisting Arsenic The discovery of a bacterium living in the extreme conditions of Mono Lake, California, created a major controversy because it was claimed to be able to grow solely on arsenic and could substitute arsenate for phosphate in its key macromolecules, including DNA. Working with the same Halomonas spp. bacterium, known as GFAJ-1, and ultrapure reagents, Erb et al. (p. 467) found that the bacterium needed a low level of phosphate (1.6 µM) to grow at all. Rather than significant specific arsenic incorporation, when the organism was grown in 40 mM arsenic, its nucleic acids acquired a trace of arsenic. Similarly, Reaves et al. (p. 470) found that GFAJ-1 could not grow in the absence of phosphate and, moreover, that its growth was not stimulated by the addition of arsenate, although a trace amount of arsenic was also detected in DNA. Thus, GFAJ-1 shows no particular facility to substitute arsenic for phosphate, when phosphate is limiting, but it can tolerate high concentrations of the poison while efficiently scavenging phosphate. Claims of arsenic substitution for phosphorus in the biomolecules of a Mono Lake bacterium are not independently reproduced. The bacterial isolate GFAJ-1 has been proposed to substitute arsenic for phosphorus to sustain growth. We have shown that GFAJ-1 is able to grow at low phosphate concentrations (1.7 μM), even in the presence of high concentrations of arsenate (40 mM), but lacks the ability to grow in phosphorus-depleted (<0.3 μM), arsenate-containing medium. High-resolution mass spectrometry analyses revealed that phosphorylated central metabolites and phosphorylated nucleic acids predominated. A few arsenylated compounds, including C6 sugar arsenates, were detected in extracts of GFAJ-1, when GFAJ-1 was incubated with arsenate, but further experiments showed they formed abiotically. Inductively coupled plasma mass spectrometry confirmed the presence of phosphorus in nucleic acid extracts, while arsenic could not be detected and was below 1 per mil relative to phosphorus. Taken together, we conclude that GFAJ-1 is an arsenate-resistant, but still a phosphate-dependent, bacterium.

Zirconium isotope evidence for incomplete admixing of r-process components in the solar nebula

Abstract Isotopic anomalies in Mo and Zr have recently been reported for bulk chondrites and iron meteorites and have been interpreted in terms of a primordial nucleosynthetic heterogeneity in the solar nebula. We report precise Zr isotopic measurements of carbonaceous, ordinary and enstatite chondrites, eucrites, mesosiderites and lunar rocks. All bulk rock samples yield isotopic compositions that are identical to the terrestrial standard within the analytical uncertainty. No anomalies in 92Zr are found in any samples including high Nb/Zr eucrites and high and low Nb/Zr calcium–aluminum-rich inclusions (CAIs). These data are consistent with the most recent estimates of

Differential passage of fluids and different-sized particles in fistulated oxen (Bos primigenius f. taurus), muskoxen (Ovibos moschatus), reindeer (Rangifer tarandus) and moose (Alces alces): Rumen particle size discrimination is independent from contents stratification

Ruminant species differ in the degree that their rumen contents are stratified but are similar insofar that only very fine particles are passed from the forestomach to the lower digestive tract. We investigated the passage kinetics of fluid and particle markers (2, 10 and 20 mm) in fistulated cattle (Bos primigenius f. taurus), muskoxen (Ovibos moschatus), reindeer (Rangifer tarandus) and moose (Alces alces) on different diets. The distribution of dry matter in the rumen and the viscosity of rumen fluids suggested that the rumen contents were more stratified in muskoxen than moose. Correspondingly, as in previous studies, the species differed in the ratio of mean retention times of small particles to fluids in the reticulorumen, which was highest in cattle (2.03) and muskoxen (1.97-1.98), intermediate in reindeer (1.70) and lowest in moose (0.98-1.29). However, the ratio of large to small particle retention did not differ between the species, indicating similarity in the efficiency of the particle sorting mechanism. Passage kinetics of the two largest particle classes did not differ, indicating that particle retention is not a continuous function of particle size but rather threshold-dependent. Overall, the results suggest that fluid flow through the forestomach differs between ruminant species. A lower relative fluid passage, such as in moose, might limit species to a browse-based dietary niche, whereas a higher relative fluid passage broadens the dietary niche options and facilitates the inclusion of, or specialization on, grass. The function of fluid flow in the ruminant forestomach should be further investigated.

Strategies for method development for an inductively coupled plasma mass spectrometer with bandpass reaction cell. Approaches with different reaction gases for the determination of selenium

Abstract An inductively coupled plasma mass spectrometer with dynamic reaction cell (DRC) was used to investigate different approaches for chemical resolution of Ar 2 + ions and to improve the determination of Se. Hydrogen, methane, oxygen and nitrous oxide were used as reaction gases. The method development for each approach consists of the acquisition of spectra for blank and spiked samples at different operating parameters, including reaction gas flow and transmission settings, of the DRC. Isotope ratio studies and the analytes signal to background ratio (SBR), were used as criteria to determine the operating conditions of the DRC where spectral interferences from the ion source or from polyatomic ions formed inside the DRC are minimized. Methane was found to provide the highest reaction efficiency for determination of Se. Nitrous oxide and oxygen also very efficiently suppress the Ar 2 + interference but reaction or scattering losses of Se + and SeO + are significant. Hydrogen is the least efficient gas for Ar 2 + reduction but little scattering or reactive loss lead to a good SBR. The determination of Se as SeO + was investigated with oxygen and nitrous oxide as reaction gases. The efficiency when using the oxygenation reaction was found to be similar to the efficiency for the charge transfer reactions but the slow oxygenation of the potentially interfering Mo + renders this approach less useful for analytical purposes. Using a natural water sample it could be shown that very good agreement is obtained using methane or hydrogen for analysis of 80 Se + at the μg/l level. Limits of detection are lowest (2 ng/l) when methane is used to suppress the Ar 2 + ion and when 80 Se + is used for analysis.

Effects of operating conditions and matrix on mass bias in MC-ICPMS

Isotope ratio measurements by multicollector inductively coupled plasma mass spectrometry are affected by mass bias, the mass-dependent sensitivity of the isotopes. This study evaluates the variation of mass bias on different instrumental parameters such as the carrier gas flow rate, the sampling depth in the plasma as well as the ion optic settings. Differences and similarities are shown between the isotope ratio variation profiles for liquid sample introduction by solution nebulization only and for membrane desolvation. They are assigned to the different behaviour of their resulting aerosols in the plasma. A promising approach towards stabilization of mass bias by measuring at elevated carrier gas flow rates is shown. Operation at 60% sensitivity reduced the bias on 146Nd/144Nd introduced by a matrix of 10 µg/g Ho up to six times compared to the highest sensitivity conditions.