The quality of the quantitative information in single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS) depends directly on the number concentration of the nanoparticles in the sample analyzed, which is proportional to the flux of nanoparticles through the plasma. Particle number concentrations must be selected in accordance with the data acquisition frequency, to control the precision from counting statistics and the bias, which is produced by the occurrence of multiple-particle events recorded as single-particle events. With quadrupole mass spectrometers, the frequency of data acquisition is directly controlled by the dwell time. The effect of dwell times from milli- to microseconds (10 ms, 5 ms, 100 μs, and 50 μs) on the quality of the quantitative data has been studied. Working with dwell times in the millisecond range, precision figures about 5 % were achieved, whereas using microsecond dwell times, the suitable fluxes of nanoparticles are higher and precision was reduced down to 1 %; this was independent of the dwell time selected. Moreover, due to the lower occurrence of multiple-nanoparticle events, linear ranges are wider when dwell times equal to or shorter than 100 μs are used. A calculation tool is provided to determine the optimal concentration for any instrument or experimental conditions selected. On the other hand, the use of dwell times in the microsecond range reduces significantly the contribution of the background and/or the presence of dissolved species, in comparison with the use of millisecond dwell times. Although the use of dwell times equal to or shorter than 100 μs offers improved performance working in single-particle mode, the use of conventional dwell times (3-10 ms) should not be discarded, once their limitations are known.
The behaviour of arsenic and antimony in the Ría de Arousa (Galicia, north west of Spain) and the influence of the Prestige accident in the estuary is evaluated. As and Sb were simultaneously determined by HG-ICPOES in seawater samples after a preconcentration with La in a knotted reactor. The highest As concentration is in the inner and middle parts of the ría where the current is weaker and next to the main ports of the area. The largest Sb concentrations were found in the bay of the ría. Linear variation of concentration vs. salinity for As and As/Sb ratios indicated that there was no pollution in the waters of Arousa. The Prestige oil spillage had no serious influence and the values of arsenic (most of them <1.5 microg L(-1)) are similar to the average oceanic concentration, whereas concentrations for antimony (most of them <0.15 microg L(-1)) are less than the oceanic ones.
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