ABSTRACT
The transport phenomena of laser-produced aerosols prior to analysis by inductively coupled plasma mass spectrometry (ICPMS) were examined. Aerosol particles were visualized over the cross section of a transport tube attached to the outlet of a conventional ablation cell by light scattering using a pulsed laser source. Experiments were carried out under laminar or turbulent in-cell flow conditions applying throughputs of up to 2.0 L/min and reveal the nature of aerosol transportation to strongly depend on both flow rate and carrier gas chosen. For instance, laser ablation (LA) using laminar in-cell flow and helium as aerosol carrier resulted in stationary but inhomogeneous dispersion patterns. In addition, aerosols appear to be separated into two coexisting phases consisting of (i) dispersed particles that accumulate at the boundary layer of several vortex channel flows randomly arranged along the tube axis and (ii) larger fragments moving inside. The occurrence of these fragments was found to affect the accuracy of Si-, Zn-, and Cd-specific ICPMS analyses of aerosols released by LA of silicate glass (SRM NIST610). Accuracy drifts of more than 10% were observed for helium flow rates of >1 L/min, most probably, due to preferential evaporation and diffusion losses of volatile constituents inside the ICP. The utilization of turbulent in-cell flow made the vortex channels collapse and resulted in an almost complete aerosol homogenization. In contrast, LA using argon as aerosol carrier generally yielded a higher degree of dispersion, which was nearly independent of the flow conditions applied. To illustrate the differences among laminar and turbulent in-cell flow, furthermore, the velocity field inside the ablation cell was simulated by computational fluid dynamics.
ABSTRACT
The applicability of two-step laser mass spectrometry (L2MS) to the analysis of water contaminants and environmental water samples is demonstrated. First, the ionization characteristics of a selection of naphthyl and carbamate pesticides and of phenol were determined. The ion signal of all compounds increased with ionization laser pulse energy, within the investigated range (20-200 microJ). Ion yields relative to an internal standard, benz[alanthracene, reached 30% for naphthyl pesticides ionized at 225 nm and 2-8% at 266 nm. At 266 nm, similar relative ion yields were found for phenol. Carbamate pesticides showed lower relative ion yields at all wavelengths, by a factor of approximately 10-100, but higher relative ion yields, on the order of 1%, were obtained when using short (ps) laser pulses for ionization. These data allow one to estimate the detection limits of these analytes in a variety of matrixes once they are known for one of the compounds. Second, the quantitative analysis of carbaryl, phenol, and polycyclic aromatic hydrocarbons in rainwater is demonstrated. The aqueous samples were frozen to permit direct L2MS analysis of organic pollutants without tedious sample preparation. Detection limits were in the low-microgram per liter concentration range and recoveries of phenol from spiked rainwater samples were above 90%. The specific advantages are exemplified with the investigation of dynamic washout processes of atmospheric organic pollutants with a resolution of 0.01 mm of precipitation.
