The effects of adding nitrogen to the central gas flow (Ar + He) of an Ar plasma in laser ablation inductively coupled plasma mass spectrometry are presented. The optimum central gas flow rate was found to be negatively correlated with the N 2 gas flow rate. The addition of 5-10 ml min À1 nitrogen to the central channel gas in LA-ICP-MS increases the sensitivity for most of the 65 investigated elements by a factor of 2-3. The degree of enhancement depends, to some extent, on the 1st ionization energy. Another important advantage of N 2 mixed gas plasma for LA-ICP-MS is that the oxide ratios (ThO + / Th + ) are significantly reduced (one order of magnitude). The hydride ratio (ArH + /Ar + ) is also reduced up to a factor of 3, whereas the doubly charged ion ratio (Ca 2+ /Ca + ) is increased. The background signals at masses 29, 31, 42, 51, 52 and 55 are significantly increased due to the nitrogen based polyatomic interferences. Compared to the spatial profiles of the ion distributions in the normal mode (without nitrogen), the addition of 5 ml min À1 nitrogen leads to significant wider axial profiles and more uniform distribution of ions with different physical and chemical properties. Our results also show that the makeup gas flow (central channel gas) rate has a significant effect on the ion distribution of elements with different physical and chemical properties. A very consistent increase of argon signal by the addition of nitrogen (5 ml min À1 ) corroborates better energy transfer effect of nitrogen in the plasma.

A novel "wave" signal-smoothing and mercury-removing device has been developed for laser ablation quadrupole and multiple collector ICPMS analysis. With the wave stabilizer that has been developed, the signal stability was improved by a factor of 6.6-10 and no oscillation of the signal intensity was observed at a repetition rate of 1 Hz. Another advantage of the wave stabilizer is that the signal decay time is similar to that without the signal-smoothing device (increased by only 1-2 s for a signal decay of approximately 4 orders of magnitude). Most of the normalized elemental signals (relative to those without the stabilizer) lie within the range of 0.95-1.0 with the wave stabilizer. Thus, the wave stabilizer device does not significantly affect the aerosol transport efficiency. These findings indicate that this device is well-suited for routine optimization of ICPMS, as well as low repetition rate laser ablation analysis, which provides smaller elemental fractionation and better spatial resolution. With the wave signal-smoothing and mercury-removing device, the mercury gas background is reduced by 1 order of magnitude. More importantly, the (202)Hg signal intensity produced in the sulfide standard MASS-1 by laser ablation is reduced from 256 to 0.7 mV by the use of the wave signal-smoothing and mercury-removing device. This result suggests that the mercury is almost completely removed from the sample aerosol particles produced by laser ablation with the operation of the wave mercury-removing device. The wave mercury-removing device that we have designed is very important for Pb isotope ratio and accessory mineral U-Pb dating analysis, where removal of the mercury from the background gas and sample aerosol particles is highly desired. The wave signal-smoothing and mercury-removing device was applied successfully to the determination of the (206)Pb/(204)Pb isotope ratio in samples with low Pb content and/or high Hg content.

Inductively coupled plasma mass spectrometry (ICPMS) has been successfully used for the detection of element-tagged biomolecules with the advantage of multielement capability. However, this technique cannot be used for microarray detection due to the necessity to dissolve the elemental tags before introducing them to the plasma source. Here, we report the detection of multiple proteins on each spot of the immuno-microarray by laser ablation ICPMS. alpha-Fetoprotein IgG (AFP), carcinoembryonic antigen (CEA), and human IgG, as model proteins, have been detected on the basis of sandwich-type immunoreactions on a microarray with Sm3+-labeled AFP antibody, Eu3+-labeled CEA antibody, and Au-labeled goat-anti-human IgG (GAH) as labeled antibodies. The detection limits were 0.20, 0.14, and 0.012 ng mL-1 (3sigma) with the RSD of 5.7%, 2.6%, and 2.3% at the concentration of 1.0 ng mL-1 for AFP, CEA, and human IgG, respectively. The present detection method permits detecting multiple analytes from each spot of microarray with a spatial resolution at micrometer range, which can alleviate the stress to fabricate high-density arrays. Furthermore, the substrate materials and immobilized proteins do not interfere with the detection. The present technique provides a new strategy for readout of microarray.