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Optimization and Calibration of Laser AblationInductively Coupled Plasma Atomic Emission Spectrometry by Measuring Vertical Spatial Intensity Profiles

XIANGLEI MAO AND RICHARD E. RUSSO *


L awrence Berkeley National L aboratory, Berkeley, CA 94720, USA

Vertical spatial emission intensity proles for ICP-AES were measured to optimize and calibrate laser ablation sampling. Laser ablation sampling and laser ablation plus liquid nebulization sampling were studied. The position of maximum ICP emission intensity above the rf load coil changes with gas ow rate for both cases, with the maximum position shifting to higher regions in the plasma at higher ow rates. The maximum emission intensity occurs at a ow rate of approximately 0.20.3 l min1 and at approximately 510 mm above the load coil, which are signicantly different to the values normally employed for liquid nebulization. In addition, by measuring the spatial emission proles for laser ablation and nebulization sampling, solutions can be used as standards to calibrate the composition of the laser ablated mass. Calibrated Zn5Cu ratios were measured using UV nanosecond and picosecond laser pulses. Stoichiometric laser ablation sampling of a brass alloy was achieved only by using UV picosecond laser pulses at high power density. Keywords: L aser ablation sampling; inductively coupled plasma atomic emission spectrometry; vertical spatial prole; optimization; calibration The intensity of an analyte line in ICP-AES is a complex function of several parameters, including analyte concentration, carrier gas ow rate, rf power, and the observation height in the plasma. For nebulized aqueous solutions and electrothermal vaporization, optimum conditions for ICP-AES have been well investigated.114 Commonly used conditions are a nebulizer gas ow rate of 0.61 l min1, an rf power of 1.11.3 kW, and an observation height of 1418 mm above the load coil. Vertical analyte emission intensity in the ICP is dependent on the rf power and gas ow rates.1521 Solid sample introduction using laser ablation provides numerous benets for chemical analysis including direct characterization of any solid sample and no sample preparation, eliminating dissolution, additional solvent waste, and personnel exposure to samples and solvents. Laser ablation requires a smaller amount of sample (<micrograms) than that required for solution nebulization (milligrams). Because there is no water in the ICP, analyte line intensity may be stronger and molecular background emission weaker. The elimination of solvent is also benecial to ICP-MS because of the lower interference of oxide and hydrogen molecular species.22 Analyte excitation behavior during direct solid sample introduction will be different to that with nebulized aqueous solutions. Previous studies have addressed transfer tube and ablation chamber designs.2328 However, to the best of our knowledge, no study has addressed optimization of the ICP for laser ablation sampling. Such a study is possible only when measuring the entire ICP vertical spatial emission intensity prole. The use of repetitively pulsed laser ablation sampling also provides the necessary precision to carry out

these studies.29,30 In this paper, the vertical spatial emission intensity proles of ICP-AES were measured for laser ablation and liquid nebulization sampling. The inuence of carrier gas ow rate and rf power on laser ablation sampling with the ICP is discussed in the rst part of this paper. A concern of laser ablation sampling is preferential ablation of volatile elements from multicomponent samples. Preferential ablation depends on the sample properties, laser uence, laser power density, and laser pulse width.3037 To determine the extent of preferential ablation for various laser conditions, it is necessary to know the exact composition of the laser ablated mass. However, because of preferential ablation, solid standards may not provide accurate calibration of the ICP. Solution standards have been proposed for calibration in ICPMS23 and ICP-AES.38 For aqueous solution nebulization, the analyte dries from liquid droplets to form very small particles in the plasma. For laser ablation, larger dry particles (#15 mm) are directly introduced into the ICP. The atomization and excitation processes are expected to be different in these two cases. Because the composition of the ICP and excitation mechanism will be different for aqueous solution nebulization and laser ablation sampling, it is prudent to characterize the ICP response for these two cases before using solutions as standards. For ICP-AES, the spectral emission intensity spatial proles are governed by ICP electron temperature, electron number density, total amount of analyte, kinetics of vaporization and atomization of larger analyte particles, number of incompletely evaporated droplets, and excitation mechanism.1521,39 In a previous study, we demonstrated that the emission spatial prole remained constant for a diverse range of laser power densities and sample targets.40 However, the vertical spatial proles are not constant for laser ablation and solution nebulization. If solutions are used to calibrate laser ablation sampling, one has to keep all ICP operating conditions constant for both cases; the total gas ow, rf power and amount of water must be constant in order to maintain similar excitation characteristics and temperature spatial proles. Even so, it is still possible that the proles will be different because of a different vaporization mechanism for nebulized solution versus laser ablated particles. Solution standards can be used to calibrate laser ablationICP-AES only if the emission intensity spatial proles are the same using both laser ablation and liquid nebulization. Spatial proles for laser ablation and solution nebulization were measured for different ICP conditions. A parameter range was established that provided similar emission spatial proles so that liquid standards could be used to calibrate the ICP. A calibration graph of Zn5Cu mole ratio versus ICP Zn5Cu intensity ratio was obtained. The Zn5Cu mole ratio as a function of laser power density was measured using a 177

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nanosecond excimer laser (30 ns, 248 nm) and a picosecond Nd5YAG laser (35 ps, 266 nm). The inuence of these laser conditions on accuracy is discussed in the second part of this paper. EXPERIMENTAL A diagram of the experimental system is shown in Fig. 1. Two different lasers were used for ablation: a KrF excimer laser with l=248 nm and a Nd5YAG laser with l=266 nm. The pulse durations of the excimer and Nd5YAG lasers are 30 ns and 35 ps, respectively. Each laser was pulsed at a repetition rate of 10 Hz. The area of the beam was reduced by using a 6 mm diameter aperture, then focused into the ablation sample chamber using a plano-convex UV-grade quartz lens ( f=200 mm). The laser beam spot size at the sample surface was varied by changing the lens-to-sample distance. The energy of the excimer laser is 25 mJ after the aperture for most of the experiments. The laser power density at the sample surface is 0.07200 GW cm2. For the Nd5YAG laser, the energy is approximately 2.5 mJ at the sample surface. The power density is 12000 GW cm2. The laser ablation chamber was mounted on a xyz micrometre translation stage so that the sampling spot could be changed after each measurement.29 The samples consisted of small discs (20 mm diameter and 1 mm thickness) of brass. The composition of brass is approximately 36% Zn and 64% Cu measured by energy dispersive X-ray spectrometry. A brass solution was prepared by dissolving a portion of this brass sample in nitric acid. Standard solutions of Zn and Cu were prepared by dissolving 99.999% Cu and 99.9% Zn metal, respectively, in dilute HNO . 3 The ICP (RFPP; ICP20P) system included a 2.2 kW rf generator, impedance matching network, and mass ow controllers (Matheson; 8274). The ow rate of Ar plasma gas was 14 l min1 and that of the auxiliary gas was 1.0 l min1. To study the inuence of gas ow rate on ICP intensity proles during laser ablation sampling, the carrier gas transports the ablated mass directly into the ICP, without a spray chamber. For calibration studies, the exit port of the ablation chamber was connected to a steel T-connector (Swagelok), so that the carrier gas could be mixed with gas from a spray chamber. The ow rate of gas into the spray chamber was xed at 0.4 l min1, the lowest level at which stability could be maintained for this nebulizer. The ow rate of carrier gas into the laser ablation chamber was varied from 0.2 to 1.0 l min1. The mixed gas was introduced into the central channel of the ICP torch. When using laser ablation to transport the sample into the ICP, water was introduced into the spray chamber to maintain constant ICP conditions.

The measurement system consists of a monochromator (Spex industries; 270M) with a 1200 grooves mm1 holographic grating and an entrance slit-width of 12.5 mm, and a Peltier-cooled, charged-coupled device (CCD) detector with 512512 pixels (EG&G Princeton Applied Research; OMA VISION). The spectral emission from the ICP was imaged using a quartz lens (5 cm focal length) onto the monochromator. This spectrometer simultaneously measures a 30 nm wavelength range. The size of the CCD is 11 cm. The data from the CCD were digitized and transferred to a microcomputer. For all data reported in this paper, emission intensities are integrated for 6 s during repetitive ablation. In a previous paper, the spatial emission prole was not inuenced by the integration time of the CCD detector.40 The brass sample was pre-ablated for 120 s before ICP intensity measurements to achieve enhanced precision. For calibration studies of laser ablation with solution nebulization, the experimental procedure is to set the ICP power, set the gas ow rate through the laser ablation chamber, and introduce water into the ICP from the spray chamber. Without laser ablation, an ICP background emission spectrum prole is recorded. The laser is then repetitively pulsed on the sample and the spectral emission intensity prole is measured. The brass solution is then introduced into the spray chamber without laser ablation. The gas ow rate in the laser ablation chamber was kept constant. With this procedure, the Cu and Zn emission intensity spatial proles were obtained with laser ablation and solution nebulization, respectively, using the same ICP conditions. The procedure is repeated at different gas ow rates into the laser ablation chamber. The Hilbert space distance was used to characterize the differences between laser ablation sampling and solution nebulization emission spatial proles. First, the spatial proles were normalized to their maximum value. Then, f (x) and g(x) were obtained with maximum values equal to 1 for laser ablation and solution nebulization, respectively. For functions f (x) and g(x), the Hilbert space distance (L2 distance) was dened as [f (x)g(x)]2 dx (1) a where x is the vertical distance and a and b are the boundaries for the low and high observation region in the ICP. The Hilbert distance between spatial functions of laser ablation and solution nebulization describes the error when solutions are used as standards for calibration and the spatial proles do not overlap. D= RESULTS AND DISCUSSION Optimization of Laser AblationICP-AES The main parameters that inuence spectral emission intensity in the ICP are carrier gas ow rate, rf power, and observation height above the load coil (HALC). To optimize these conditions for laser ablation sampling and laser ablation sampling with solution nebulization, the ICP spatial emission intensity proles were measured for different gas ow rates and rf powers. Both sample introduction congurations were used for this study. Fig. 2 shows the Cu 224.7 nm ( brass sample) spatial emission intensity proles for different carrier gas ow rates with an rf power of 1500 W using the conguration in which the carrier gas ows through the laser ablation chamber and transports the ablated sample directly into the ICP torch. The ow rates were 0.1, 0.15, 0.2, 0.3, 0.5 and 1.0 l min1. Fig. 3 shows the Cu 224.7 nm spatial emission intensity proles for different carrier gas ow rates through the laser ablation chamber with a 0.4 l min1 Ar ow rate through the nebulizer while aspirating water. The ow rates through the laser ablation chamber were 0.2, 0.3, 0.4, 0.6, 0.8 and 1.0 l min1.

SP

Fig. 1 Diagram of experimental system for laser ablationICP-AES.

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Fig. 2 Vertical spatial emission intensity proles of Cu in the ICP at different gas ow rates (l min1). Carrier gas through laser ablation chamber and directly into the ICP. Rf power, 1500 W.

Fig. 3 Vertical spatial emission intensity proles of Cu in the ICP at different gas ow rates (l min1). Carrier gas through laser ablation chamber with a 0.4 l min1 gas ow through spray chamber with water nebulization. Rf power, 1500 W.

The intensities shown in Figs. 2 and 3 were backgroundcorrected. The laser power density used in these experiments was 0.9 GW cm2 and the brass samples were pre-ablated for each measurement. Therefore, the ablated mass was approximately constant for each of these proles. The Cu intensity was measured at ve separate spots on the brass sample for the 0.3 l min1 ow rate to determine the error associated with these measurements, primarily due to the laser ablation sampling. The error at this ow rate is approximately 3% RSD for the Cu measurements and is consistent with previous studies using repetitive pulsing and pre-ablation.29 As expected, the position of maximum ICP emission intensity changes with gas ow rate for both congurations, with the maximum shifting to higher regions in the plasma at higher ow rates. The Zn emission intensity spatial proles behaved similarly to those of Cu and are therefore not shown. The Cu peak intensity initially increases with gas ow rate, reaches a maximum, and then decreases in the laser ablation conguration (Fig. 2). The maximum occurs at a ow rate of approximately 0.20.3 l min1. For laser ablation plus water, the Cu intensity decreases with increasing gas ow rate above 0.2 l min1 in the laser ablation chamber (with a constant 0.4 l min1 gas ow through the nebulizer) (Fig. 3). Increasing the ICP power increases the ICP intensity, but the maximum analyte intensity always occurs at 0.20.3 l min1 for both cases. This ow rate is considerably lower than that generally accepted for optimum performance using liquid nebulization alone. For the laser ablation case (cf. Figs. 2 and 4), the emission intensity is

improved by a factor of about 3 with a lower ow rate. For the laser ablation plus water case (Figs. 3 and 5), the intensity is improved by almost a factor of 10. These studies also show that the best HALC for maximum emission is lower than that generally used for conventional liquid nebulization sampling. It is interesting that the maximum intensity is similar for both cases, considering that the ICP excitation conditions are different with and without water. For ICP=1500 W, a maximum intensity of #7.8105 occurs with a ow rate of 0.2 l min1 in the laser ablation chamber plus 0.4 l min1 through the nebulizer (0.6 l min1 total), compared with #8.5105 with a ow rate of 0.3 l min1 in the laser ablation chamber. The emission intensity depends on two primary factors: the amount of sample and the excitation conditions of the ICP. For this xed laser power density study, the amount of ablated sample was approximately constant for this homogeneous sample; the RSD is approximately 3%. When the carrier gas ow rate increases, transport efficiency improves and the amount of mass delivered to the ICP increases.41 However, increasing the ow rate decreases the excitation temperature of the ICP.17 There are more Ar atoms per unit time in the ICP for higher gas ow rates. With increasing Ar gas ow rate, the maximum emission intensity in the ICP decreases and the peak position shifts upward.1517,1921 There is a trade off in transport efficiency versus temperature that governs the intensity and spatial properties of these emission data. A complete analysis would require measurement of the ICP temperature behavior versus ow rate. Monitoring peak intensity is important for studying changes related to ow rate. However, peak intensity alone does not dene analytical sensitivity. The ratio of analyte spectral intensity to continuum emission background is important for optimization of sensitivity.11 To determine the optimum height for AES observation, it is necessary to know the spatial proles of both line intensity and background. The ICP background emission decreased with increasing ow rates for both laser ablation and laser ablation plus water. Figs. 4 and 5 show the spatial proles for the Cu intensity ratio to background for laser ablation and laser ablation plus water, respectively. Comparing Fig. 4 with Fig. 2, the maximum position (HALC) for the ratio is approximately 5 mm higher than that of absolute intensity. The absolute intensity at 0.2 l min1 is approximately three times stronger than that at 1.0 l min1; the ratio is almost the same. The maximum ratio occurs at a ow rate of 0.5 l min1, whereas maximum intensity occurs at 0.2 l min1. For laser ablation plus water, the absolute intensity at 0.2 l min1 is approximately ten times stronger than that

Fig. 4 Ratio of Cu line intensity to ICP background as a function of height above load coil at different gas ow rates ( l min1). Carrier gas through laser ablation chamber and directly into the ICP. Rf power, 1500 W.

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Fig. 5 Ratio of Cu line intensity to ICP background as a function of height above load coil at different gas ow rates ( l min1). Carrier gas through laser ablation chamber with a 0.4 l min1 gas ow through spray chamber with water nebulization. Rf power, 1500 W.

at 1.0 l min1; the line-to-background ratio is approximately four times better. The maximum ratio and absolute intensity occur at the same ow rate (0.2 l min1 through the laser ablation chamber and 0.4 l min1 through the spray chamber). Analyte and background intensity are increased at lower ow rates, and optimum sensitivity is a balance between the two. If absolute intensity is used for optimization, a carrier gas ow rate of 0.20.3 l min1 is best for both laser ablation and laser ablation plus water sampling. The observation height should be 15 mm and 38 mm above the load coil for laser ablation and laser ablation plus water, respectively. As regards both net intensity and line-to-background ratio, the best ow rate is 0.20.3 l min1 and the best observation height is 15 mm for laser ablation sampling. For laser ablation plus water, 0.2 l min1 provides the best performance with our nebulizer at 0.4 l min1. The best observation height is 511 mm above the load coil. All of these observations were based on Cu and Zn emission lines located between 200 and 230 nm. Other element lines are expected to have different proles. However, the research indicates that lower gas ow rates and lower observation heights provide enhanced sensitivity for laser ablation sampling. Calibration of Laser Ablation Sampling with Solution Standards To calibrate laser ablation sampling, the composition of the sample introduced into the ICP has to be known. The ICP line intensity can be expressed as:42 hc A g i i g(x) eE /[k T(x)] (2) i B 4p l Q i where A is the Einstein transition probability for spontaneous i emission, E the energy of the transition, g the statistical weight i i of level E , T the excitation temperature, l the wavelength, g i i the emitting atom density, h Plancks constant, k Boltzmans B constant, c the speed of light and Q the internal partition function. In order to calibrate laser ablation using solution standards, the temperature proles have to be the same for both laser ablation sampling and solution nebulization. Therefore, for laser ablation the same amount of water and acid must be nebulized into the ICP. However, even with the same amount of Ar gas and water, it is still possible that excitation conditions and vertical spatial emission proles may not be similar because of different particle sizes and different vaporization behavior. For liquid nebulization, aqueous droplets undergo evaporation, atomization, ionization, excitation and recombination processes. These processes are a function I(x)= 180

of vertical height (temperature) in the ICP. For laser ablation, the analyte already exists in the solid particle or atomic form; melt ejection or sublimation occurs from the solid and there is no aqueous evaporation. Measurement of emission spatial proles provides a good way to determine the conditions under which standard solutions can be used for calibration. From eqn. (2), the intensity prole I(x) is a function of the temperature prole T (x), and the number density of atoms or ions g(x). If T (x) or g(x) in laser ablation and solution sampling is different, I(x) will be different. Therefore, the ICP conditions must be established to ensure that I(x) is the same for both laser ablation and solution nebulization. The carrier gas ow rate and rf power can be optimized to minimize the difference between laser ablation and solution nebulization. For this study, the spatial proles for laser ablation plus water versus brass (Cu+Zn) solutions were compared. Fig. 6(a) and (b) shows the normalized Cu emission intensity spatial proles for laser ablation plus water at 1.0 and 0.2 l min1 gas ow rates, respectively. The nebulizer ow rate was 0.4 l min1 in both cases. The total ow was always the ow through the ablation chamber plus the nebulizer; 1.4 l min1 in Fig. 6(a) and 0.6 l min1 in Fig. 6(b). When the ablation chamber ow rate is 1.0 l min1, the spatial proles are different [Fig. 6(a)], even though the total water loading into the ICP is the same. The different particle behavior in the ICP is apparent under these conditions. The spatial proles using a 0.2 l min1 ow rate in the ablation chamber are almost identical for both laser ablation plus water versus nebulized standard solutions [Fig. 6(b)]. Under these ow conditions, the difference in particle behavior is minimized. The Hilbert space distance was used to quantify the difference between two emission intensity proles; the smaller the value, the more identical the proles. The difference between laser

A B

Fig. 6 Normalized Cu emission intensity in the ICP as a function of height above load coil with gas ow rates of (a) 1.0 and (b) 0.2 l m1, in the laser ablation chamber and 0.4 l min1 through the spray chamber. Solid line is laser ablation sampling plus water. The broken line is for a brass solution through the nebulizer without laser ablation.

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ablation and solution nebulization of standards was calculated for different gas ow rates and rf powers. The offset in Cu and Zn spatial proles with carrier gas ow rate was measured at three different ICP powers [Fig. 7(a) and (b)]. The difference (error) for Cu ranges from approximately 0.05 at 0.2 l min1 to 0.4 at 1 l min1. For Zn, the difference is small (#0.02) until the gas ow rate reaches 0.8 l min1, and is not very sensitive to ICP power at low ow rates. Zn intensity proles were not as sensitive as those for Cu when the gas ow rate changed. A possible explanation is that Zn is easier to atomize because of its lower melting- and boiling-point than Cu. Zn may be completely atomized for both laser ablation and solution nebulization sampling for gas ow rates less than 0.8 l min1. A lower gas ow rate and increased temperature may be required to atomize Cu efficiently. In general, the offset in spatial proles will depend on the particular species, the excitation state and ICP characteristics. Better overlap was measured for both species at the lower ow rate. If two intensity proles are the same, the Hilbert space distance is equal to zero. Because of instrumental errors and uctuations in laser ablation and solution nebulization, the Hilbert space distance cannot be zero in these experiments. To determine the instrumental and laser ablation errors, three laser ablation and solution ICP proles were obtained at a gas ow rate of 0.6 l min1 and an rf power of 1500 W. The error between laser ablation spatial emission proles themselves is from 0.04 to 0.09. The error between repetitive solution nebulization spatial emission proles is about 0.02. The larger values for laser ablation demonstrate the noise from this sampling technology. This error represents a jitter in the overall ICP behavior to the particle size distribution introduced during laser ablation. At a gas ow rate of 0.2 l min1, the difference between laser ablation and solution nebulization is approximately 0.05. Therefore, for these conditions the spatial proles are essentially identical for laser ablation and solution nebulization, since the Hilbert space distance is approximately equal to that of laser ablation sampling alone. From the earlier

discussion on optimization, emission line intensity was maximum at a gas ow rate of 0.2 l min1. A gas ow rate of 0.2 l min1 also provided the optimum overlap in spatial proles for accurate calibration. From Fig. 7(a) and (b), it can be seen that laser ablation and solution nebulization provided identical spatial emission intensity proles using a ow rate of 0.2 l min1. Therefore, these conditions were used to calibrate the Zn5Cu ratio using standard solutions. An analytical working curve was generated and used to determine the accurate ratio for the brass sample (0.56 mole ratio). The calibrated Zn5Cu mole ratio as a function of laser power density is shown in Fig. 8 for ablation with the 30 ns UV excimer laser. Zn is severely preferentially ablated at lower laser power density, below 0.3 GW cm2. When the laser power density is higher than 0.3 GW cm2, the ratio is close to accurate. The insert in Fig. 8 shows that even at high power density, the composition of the ablated mass is different to the composition of the solid sample. Similar data have been measured previously, but not against a calibrated ICP.43 At lower power density the laser ablation process is mainly thermal; Zn is easier to vaporize than Cu. As the power density is increased, the amount of Cu increases faster than that of Zn, because of a higher surface temperature.32,33,43 The stoichiometric ratio is approached as the power density reaches #0.3 GW cm2, the roll-off region for mass ablation efficiency previously observed.32,33 There are several competing mechanisms inuencing mass removal. When the laser power density reaches 0.3 GW cm2, plasma shielding may be important.32,33,43 The plasma is dense and hot enough to absorb a portion of the laser energy. The hot, high pressure plasma will interact with the solid sample causing sputtering. There is a trade off between direct laser heating and plasma heating that will provide the most accurate analysis. A higher laser power density provides better accuracy, although accurate analysis is not achieved for the brass sample using the UV nanosecondpulsed laser. The error is approximately 10% at 0.3 GW cm2. Fig. 9 shows the calibrated Zn5Cu ratio as a function of laser power density using the picosecond-pulsed laser with l= 266 nm. The behavior is different to that using the nanosecondpulsed laser; the ratio increases with increasing power density and becomes stoichiometric after approximately 10 GW cm2. The region of accurate analysis, after #10 GW cm2 is also the region after which roll-off occurs for the picosecond-pulsed laser material interaction.32,33 These data demonstrate that the mechanisms for nanosecond- and picosecond-pulsed laser

Fig. 7 Hilbert space distance between laser ablation and solution ICP spatial intensity proles versus gas ow rate in laser ablation chamber. (a) Cu and (b) Zn.

Fig. 8 Zn5Cu mole ratio from laser ablated mass as a function of laser power density. Solid line is the calibrated ratio from a brass solution. Excimer laser with l=248 nm and pulse duration=30 ns. Insert shows an expanded scale for the higher power density.

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Fig. 9 Zn5Cu mole ratio from laser ablated mass as a function of laser power density. Solid line is the calibrated ratio from a brass solution. Nd5YAG laser with l=266 nm and pulse duration=35 ps.

ablation are different. For brass analysis, the picosecond-pulsed laser with l=266 nm provides a wide power density region in which the ablated material has the same composition as the solid. In previous work, we demonstrated that the picosecondpulsed laser also provides better sensitivity than the nanosecond-pulsed laser.32

CONCLUSION By measuring vertical spatial emission intensity proles, ICPAES operating conditions can be established for optimum response during laser ablation sampling. Compared with the ICP operating conditions for nebulized aqueous solutions, laser ablation sampling provides its best sensitivity at lower carrier gas ow rates and lower observation heights in the plasma. The inuence of rf power on emission intensity was not as sensitive as gas ow rate for the elements investigated. By measuring vertical spatial emission intensity proles, laser ablation sampling with the ICP can be calibrated by using standard solutions. The gas ow rate should be less than 0.3 l min1 when a standard nebulizer system is used with a 0.4 l min1 Ar ow. With calibrated ICP, preferential vaporization is shown to exist throughout a wide power density range using a UV-pulsed laser. The Zn5Cu ratio from ablation of brass samples with a UV nanosecond-pulsed laser decreased with increasing laser power density, and stabilized for power densities higher than 0.3 GW cm2. However, the composition of the ablated mass was always Zn-rich. Using UV picosecondlaser pulses, the Zn5Cu ratio increased with increasing laser power density and stabilized at an accurate level; the composition of the laser ablated mass was the same as that of the solid sample when the laser power density was higher than 10 GW cm2. The picosecond-pulsed laser provided better ablation efficiency and better accuracy for chemical analysis than the nanosecond-pulsed laser. Standard solutions represent a potential methodology for calibrating the ICP for laser ablation sampling. However, it would be desirable not to use solutions. Additional work is necessary to understand laser ablation better so that solids can be used as standards without matrix effects. It may be possible that operating conditions can be established for the ICP and UV picosecond-laser pulses to provide stoichiometric analysis, in which case solid standards can be trusted for calibration. This research was supported by the US Department of Energy, Office of Basic Energy Sciences, Chemical Sciences Division, Processes and Techniques Branch, under Contract No. DE-AC0376SF00098. 182

Paper 6/06059E Received September 3, 1996 Accepted October 8, 1996

Journal of Analytical Atomic Spectrometry, February 1997, Vol. 12