Jacek
Giersz
*,
Magdalena
Bartosiak
and
Krzysztof
Jankowski
Warsaw University of Technology, Faculty of Chemistry, Noakowskiego Street 3, Warszawa, PL-00664, Poland. E-mail: jgiersz@ch.pw.edu.pl
First published on 10th July 2017
Both argon inductively coupled plasma (ICP) and argon microwave induced plasma (MIP) coupled to photochemical vapor generation (PCVG) and pneumatic nebulization (PN) inside a programmable temperature cyclonic spray chamber (PTSC) have been widely characterized via optical emission spectrometry. Plasma diagnostics revealed an interesting relationship between fundamental plasma parameters and PTSC temperature in the examined range of 0–60 °C which was different for the two plasmas examined. For ICP, all measured parameters including rotational temperature (Trot), excitation temperature (Texc), ionization temperature (Tion) and electron number density (ne) consequently increased (3–22%) with increasing PTSC temperature. In turn, for MIP only Trot and Texc for Fe showed a similar trend while the other examined parameters slightly decreased (about 15% for ne and Texc for Ar with increasing PTSC temperature). As a result, ICP robustness increased with increasing PTSC temperature while MIP robustness decreased. Three factors influencing changes of plasma parameters were selected and considered including water transport efficiency, carbon-related matrix effect and analyte volatility. The observed trends are consistent with analytical data obtained previously and are supported by additional investigation of the sample transport efficiency of the sampling system. Thus, partial sample evaporation at elevated PTSC temperature is finally confirmed, although saturation of the nebulizer gas with water vapor is not achieved when it exits the PTSC. Enhancements of analyte emission intensity related to PTSC heating are due to the improved plasma robustness rather than higher sample transport efficiency.
It was found that water vapor loading has a high impact on analyte signals in both ICP-OES and MIP-OES. Zhu and Browner11 reported the influence of water vapor loading as a function of Scott-type spray chamber temperature on ICP-OES spectral characteristics. In addition, they observed variations of Ti(II) excitation temperature (Texc) and electron number density (ne) and found that these parameters were practically independent of sample loading for the chamber wall temperature varying between 0 and 40 °C. Giersz and Jankowski studied the relationship between the temperature of the sample introduced to the plasma and plasma OES characteristics for Ar MIP, He MIP and Ar ICP.9 They reported that the intensity ratio for the line pair Mg(II) 280.270/Mg(I) 285.213 for Ar-ICP increases from 12 to 13 with increasing PTSC temperature. Long and Browner12 investigated the effect of water loading on the plasma properties including the background level, ne and ionization temperature (Tion) for Ar ICP. They observed a slight increase of both Tion and ne with increasing water vapor loading in the range of 5–27 mg L−1, and a significant drop of Tion from 7960 K to 7020 K for water vapor plus aerosol loadings exceeding 27 mg L−1. In turn, Pohl and Broekaert13 observed that Texc values measured for Ar, Au, Bi and Fe atomic species in Ar ICP increased after replacing pneumatic nebulization by a simultaneous hydride generation and pneumatic nebulization system providing combined aerosol and vapor loading. Moreover, sample introduction in the vapor form alone led to further increase of Texc for Ar, Au and Bi. Similar trends were observed for Ar MIP.14
In a number of papers, carbon-related matrix effect on plasma properties has been studied15,16 including the effect of low-molecular-weight organic acids.17–20 Also, the ethanol concentration influence on plasma characteristics for Ar-MIP-OES coupled with CVG and a gas–liquid separator has been described by Włodarczyk and Żyrnicki.21 They found that with ethanol concentration in the sample from 10 to 90% Trot increased from 2970 to 3820 K while Texc of Ar, H and Sb lowered in the ranges 5670–4800, 6190–3950 and 10500–7390 K, respectively. Simultaneously, the decrease of ne value from 2.5 × 1015 to 0.57 × 1015 cm−3 was observed.
The PTSC influence on multiple plasma characteristics in both Ar-MIP and ICP-OES in the examined range of 0–60 °C during PCVG has not been studied yet. Recently, only the OH rotational temperature for both Ar-ICP and Ar-MIP coupled with PN-PTSC has been measured.9 The aim of this study was careful investigation of the PCVG-PN-PTSC sampling system and examination of its influence on ICP and MIP characteristics in order to determine the optimal PTSC temperature for both PCVG-PN-PTSC-ICP-OES and PCVG-PN-PTSC-MIP-OES techniques.
ICP | |
---|---|
Plasma power supply | 1250 W |
Plasma gas flow rate | 14 L min−1 |
Auxiliary gas flow rate | 1 L min−1 |
Carrier gas flow rate | 450 mL min−1 |
MIP | |
---|---|
Plasma power supply | 240 W |
Plasma/carrier gas flow rate | 450 mL min−1 |
Quartz tube inner diameter | 4 mm |
The optimization of both sources was very brief as the aim of the study was to investigate commonly used plasma sources operating close to standard conditions. For both sources it was performed in order to obtain robust, stable plasmas, not affected by frequent changes of conditions and increased solvent load at elevated PTSC temperature. Mainly plasma supply power (for ICP and MIP) and sample flow (for MIP only) rate were the optimized parameters. The sampling setup (previously described in ref. 10), consisted of a lab-made photochemical reactor, a concentric nebulizer AR40-07 (Glass Expansion, Australia) working at 2 mL min−1 sample flow rate and a standard cyclonic spray chamber V2 equipped with an Isomist Module (Glass Expansion, Australia) for controlling and monitoring spray chamber temperature between −10 °C and +60 °C with an accuracy of ±0.1 °C. The PCVG reactor consisted of a 3 mm i.d. wide and 68 cm long quartz tube (4.6 cm3 volume) coiled around a low-pressure 11 W, UV-C mercury lamp (Philips). For investigation of the solvent transport efficiency, a filter housing with a glass filter (47 mm diameter, Pall-Gelman, Mexico) and a lab-made water adsorber filled with molecular sieves type 13X were used (Fig. 1). A Minipuls 3 peristaltic pump (Gilson, Switzerland) was used for delivering the sample to the experimental setup.
![]() | ||
Fig. 1 Schematic diagram of the experimental setup for solvent transport efficiency measurements and spectroscopic diagnostics. |
For plasma diagnostics measurements, the emission from both examined plasmas was axially viewed and directed via an optical fiber P600-2-SR with a collimating quartz lens to four miniature optic CCD spectrometers: AvaSpec-2048 XL, AvaSpec-3648-UF, AvaSpec-3648-UE (Avantes Netherlands), and USB4000 (Ocean Optics USA) covering spectral ranges of 190–355, 270–330, 330–430 and 430–630 nm, respectively, and a spectral resolution of 0.08, 0.015, 0.03 and 0.06 nm, respectively.
Diagnostic parameters characterize fundamental plasma features including vaporization efficiency of sample aerosol droplets, the energy of excited atoms or plasma gas temperature. The electron number density was calculated from the Stark broadening of the Hβ line at 486.16 nm based on the full width of half maximum (FWHM). Useful equations are given below:
ne = C(ne,Te)d1.5 | (1) |
![]() | (2a) |
gT = (gD2 + gI2)0.5 | (2b) |
![]() | (2c) |
![]() | (3) |
Object | Wavelength/nm | Energy or hcF/eV | gA or FCF |
---|---|---|---|
T exc(Ar) | 425.118 | 14.473 | 0.0396 |
425.936 | 14.748 | 0.45 | |
426.629 | 14.539 | 0.18 | |
427.217 | 14.535 | 0.27 | |
430.010 | 14.516 | 0.21 | |
T exc(Fe) | 367.992 | 3.371 | 0.1242 |
370.557 | 3.399 | 0.2296 | |
371.994 | 3.334 | 1.793 | |
372.256 | 3.419 | 0.2525 | |
373.487 | 4.180 | 8.536 | |
373.713 | 3.371 | 1.26 | |
374.949 | 4.223 | 6.129 | |
375.824 | 4.259 | 4.277 | |
376.379 | 4.286 | 2.615 | |
T exc(Ni) | 301.09 | 4.541 | 15 |
337.97 | 4.092 | 6.1 | |
341.34 | 3.658 | 5.7 | |
344.53 | 3.708 | 3.8 | |
352.45 | 3.545 | 4.6 | |
T rot(OH) | 307.8 | 4.029 | 10.0 |
308.0 | 4.038 | 17.0 | |
308.3 | 4.067 | 33.7 | |
308.5 | 4.088 | 42.2 | |
308.7 | 4.113 | 50.6 | |
311.0 | 4.399 | 100.6 | |
311.5 | 4.456 | 108.8 | |
312.0 | 4.516 | 125.2 | |
313.7 | 4.716 | 149.6 | |
T vib(N2) | 353.67 | 0.37 | 0.2033 |
357.69 | 0.13 | 0.3291 | |
371.05 | 0.61 | 0.1605 | |
375.56 | 0.37 | 0.1990 | |
380.49 | 0.13 | 0.1462 | |
T ion(Mg) | 279.55 | 4.434 | 10.40 |
285.21 | 4.346 | 14.73 |
The other plasma temperatures including Texc, Trot, and Tvib can be determined by the Boltzmann-plot method. Correlation equations for each temperature type are given below, respectively:
![]() | (4) |
![]() | (5) |
![]() | (6) |
E k, hcF′(J′), and Eν signify energies of a particular level change (energy of transition), SJ′J′′ is the Honl–London factor, q is the Frank–Condon factor (transition probability), S(λ) is the detector sensitivity, ν is the vibrational quantum number, and J is the rotational quantum number. Rotational temperature has been measured using the OH (A2Σ → X2Π) transition. The vibrational temperature of N2 has been measured using the second positive system (C3Πu → B3Πg) of nitrogen molecule. Tvib measurements were carried out for MIP only, since no N2 emission was observed for ICP. Also, for ICP measurements, the intensities of some lines from the OH band were not sufficiently high to be used for reliable temperature calculation by the Boltzmann plot method. For better comparison between the two examined plasmas, in both cases, a simplified method of OH rotational temperature determination was used, as described by Izarra.24 Additionally, Trot determination by the Boltzmann plot method was applied for the MIP spectrum for comparison. In the method proposed by Izarra, intensities of the main OH band heads R1, R2 and Q2 are used at 306.573 nm, 306.776 nm and 308.986 nm, respectively, and the method is applicable even at low optical resolution of the experimental setup. Trot can be easily calculated from R1/Q2 or R2/Q2 intensity ratio. However, instrumental broadening Δ of the optical system used should be known. This parameter is defined as the full width of an atomic line at 1/e of its height. For the spectrometer used (AvaSpec-2048 XL), Δ was measured using the mercury line at 296.728 nm taken from a low pressure mercury lamp and it was estimated to be 0.28 nm. According to Izarra,24 the accuracy of Trot determination for ICP by this method is lower than that for MIP since for Trot above 4000 K the slopes of both function plots R1/Q2 = f(Trot) and R2/Q2 = f(Trot) decrease resulting in an increase of error in the temperature determination. For the other temperatures determined, the uncertainty was calculated based on the error estimated for the slope of the respective Boltzmann plot.25 All spectroscopic data are listed in Table 2. All diagnostic parameters were calculated as average values of three independent measurements.
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Fig. 3 Water vapor and aerosol loading variation versus PTSC temperature: (A) shows data obtained for water, and (B) for 10% formic acid solution. |
While water aerosol transport efficiency seems to be slightly dependent on PTSC temperature, water vapor transport efficiency increases by 4-fold when heating PTSC from 0 to 60 °C (see Fig. 3A). The results obtained show a similar trend to those reported by Zhu and Browner11 where the effect of the Scott-type chamber operating in the 0–35 °C temperature range on water loading was investigated. However, in our study the increase is less pronounced than that determined in ref. 11 where 4-fold increase of vapor loading was obtained even faster between 0 and 30 °C. This indicates that heat transfer between the PTSC wall and carrier gas is less effective than that in the Scott-type chamber. Moreover, one can conclude that Ar is not saturated with water vapor when leaving the PTSC.11
The results obtained for formic acid solution differ in some aspects. While vapor transport efficiency is very similar for the two solutions (about 3%), both total solvent transport and aerosol transport efficiencies for formic acid solution are visibly higher compared to pure water nebulization. The boiling points of water and formic acids are comparable (for HCOOH 100–101 °C) so vaporization effects for these liquids are expected to be similar. However, Tormen et al.17 reported about 25% increase of signals by PN-ICP-MS for a number of elements when about 10%v/v of formic acid was present in the sample. They suspected that the addition of an organic acid caused decrease of surface tension of the sample solution, thus favoring the formation of a finer and more stable aerosol. Owing to these effects, sample aerosol was both generated and transferred to the plasma with better efficiency. This explains our observation that sample aerosol transport rate is 2 times higher when formic acid is present in the sample. Moreover, the ratio of aerosol transport efficiency is practically independent of the PTSC temperature in the whole temperature range examined. Consequently, the total sample loading is also significantly higher for formic acid solution compared to water.
It is well known that UV irradiation causes decomposition of formic acid into gaseous products.30 In order to evaluate the formic acid degradation rate under UV irradiation in our experimental setup, the HCOOH concentration has been determined in the collected drain by acid–base titration. No difference was observed for HCOOH concentration in solution before and after UV irradiation. It means that a very small amount of formic acid was decomposed during the photochemical process. Also, the temperature of PTSC did not affect HCOOH concentration in the collected drain for the whole temperature range.
Plasma parameter, unit | n e, 10−15 cm−3 | T exc(Ar), K | T exc(Fe), K | T exc(Ni), K | T rot (OH), K | T ion (Mg), K | T vib (N2), K |
---|---|---|---|---|---|---|---|
a T PTSC – PTSC temperature. | |||||||
MIP (TPTSC = 0 °C) | 2.3 ± 0.23 | 4550 ± 300 | 6100 ± 250 | 6600 ± 350 | 3150 ± 200 | 6950 ± 700 | 3600 ± 100 |
MIP (TPTSC = 50 °C) | 1.9 ± 0.19 | 3850 ± 250 | 6650 ± 250 | 5900 ± 350 | 3700 ± 200 | 7000 ± 700 | 4600 ± 150 |
ICP (TPTSC = 0 °C) | 1.7 ± 0.17 | 6300 ± 400 | 5700 ± 200 | 3900 ± 250 | 4300 ± 350 | 8400 ± 850 | — |
ICP (TPTSC = 60 °C) | 2.0 ± 0.20 | 6650 ± 400 | 6050 ± 250 | 4000 ± 250 | 5250 ± 400 | 8600 ± 850 | — |
As expected, Ar ICP is characterized by generally much higher temperatures than Ar MIP (see Table 3). This is a result of applying much higher plasma power. For ICP, the difference between Texc for Ar and that for Fe is about 600 K, while for MIP it is 1500 K, which indicates strong departure from thermal equilibrium for the examined Ar MIP. However, when operating at low PTSC temperature, both plasma sources are characterized by a typical sequence of temperatures of non-LTE plasma: Tion > Texc > Tvib > Trot. The temperature values are comparable to those available in the literature.12,17–20,31 Comparing pneumatic nebulization and hydride generation with simultaneous introduction of the sample aerosol into ICP, Pohl and Broekaert13 found that Texc for Ar, Au, Bi and Fe atoms varied in the range 6700–7000, 6400–6600, 2900–3000, and 6800–7400 K, respectively, being higher in the case of combined vapor plus aerosol sample loading.
In turn, when operating at an elevated PTSC temperature, for MIP Texc(Ar) is very close to Trot(OH) and it is lower than Tvib(N2) indicating that argon low-energy states are not in Saha equilibrium.32 By contrast, Texc(Ni) is only slightly lower than Tion(Mg). This can be explained by the formation of volatile nickel carbonyl by using the PCVG technique. Under the applied conditions, the efficiency of Ni(CO)4 generation was found to be about 20–30%,33,34 and Ni(CO)4 easily decomposes in plasma to Ni0 and CO since its thermolysis begins at 180 °C.
This conclusion is further confirmed by additional experiments on the determination of Texc(Ni) for both ICP and MIP combined with pneumatic nebulization. For MIP, when Ni standard solutions were introduced by PN, Texc(Ni) reached 4450 K and 5600 K for water-based solution and that containing 10%v/v of formic acid, respectively. It seems that the decomposition of formic acid in Ar MIP, forming CO and H2 leads to Texc increase of about 800 K. However, additional UV radiation of the HCOOH-containing solution under PCVG conditions and formation of volatile Ni(CO)4 caused further elevation of Texc(Ni) to 6600 K. A similar effect has been observed in the ICP-based system where Texc(Ni) value reached 3600 K for both water-based and formic acid containing solution vs. 3900–4000 K after PCVG. This effect in MIP is even stronger21 probably due to the lower ionization degree of Ni in this plasma.
For ICP, increasing the PTSC temperature led to increase of all calculated plasma temperatures and ne which actually means that despite increased water loading ICP becomes more robust and dense. Long and Browner reported similar observations after increasing water vapor loading to ICP operating under robust conditions.12 According to Tang and Trassy31 water dissociation products (OH, H, O, H+, O+, OH+) improve the energy transfer efficiency and emission rate of plasma species. As it was further confirmed in our previous studies by determining numerous analytes, the higher the PTSC temperature, the stronger the emission intensity of the analytes and the lower their LOD values.8,9 These results clearly state that ICP robustness rises with increasing PTSC temperature leading to increased signal intensity. Actually, the value of the Mg 280.270 nm to Mg 285.213 nm line intensity ratio increased from 7.7 at 0 °C to 8.5 at 60 °C of the PTSC temperature. Moreover, the ne value increased by 20% due to increased water vapor loading, which is significantly higher compared with the change observed by Grotti et al. in their study while increasing water aerosol loading.35
MIP response on increasing PTSC temperature seems to be more significant than ICP. Both Texc(Fe) and Trot(OH) increase, however Texc(Ar), Texc(Ni), and ne definitely decrease. Again, Grotti et al.35 observed similar ne decrease with increasing water amount delivered to ICP under non-robust conditions (800 W). Since some measured temperatures become lower and others higher, stronger deviation from thermal equilibrium is expected for the MIP. The decrease of Texc(Ar) with simultaneous increase of Texc(Fe), Tvib(N2) and Trot(OH) may suggest that under plasma conditions related to elevated PTSC temperature some energy is transferred from Ar atoms to other heavy particles present in the plasma. In particular, this is confirmed by 28% increase of Tvib(N2) with increasing the PTSC temperature between 0 °C and 50 °C. It is known that nitrogen vibration states can trap energy and play the role of an energy reservoir in the plasma, which is important for specific excitation pathways.36 Also, plasma stability may be affected since plasma sustenance depends on Ar energy. In turn, the observed extensive Trot(OH) increase is disadvantageous from the point of view of the source durability. Too high gas temperature may cause torch material etching since the distance between the MIP discharge and torch inner wall is relatively low. However, the most important effect here is the decrease of ne indicating that plasma is being suppressed under the examined conditions. It is known that low-power MIP plasma can accept only a limited amount of water, even in the vapor form. Reducing the sample flow rate would likely allow for MIP measurement at PTSC temperature exceeding 50 °C. It has been noted that increase of water transport efficiency with increasing PTSC temperature caused an even depressive effect on analyte signal intensity and LOD values (an opposite effect compared to ICP).8,9 The highest emission intensity for all analytes for MIP was reached at a PTSC temperature of 0 °C. All these facts suggest that, despite the increase in some parameters, the MIP robustness worsens with increasing PTSC temperature.
The PTSC temperature setting presents a more distinct influence on MIP than ICP plasma parameters. The MIP was less resistant to both excessive water loading and influence of water vapor. For the plasma loaded with increasing amount of water aerosol and vapor, the ne value was found to gradually decrease. The excitation temperatures for Ar, Fe and Ni were observed to be dramatically dependent on experimental conditions. Also, the vibrational temperature for nitrogen molecules is also much higher in the presence of water vapor. In contrast to the ICP, increase of PTSC temperature worsens plasma robustness and plasma stability for Ar-MIP.
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