1402

Anal. Chem. 1902, 5 4 , 1402-1410

(1 7) IUPAC, "Recommedations for Publishing Manuscripts on Ion Selective Electrodes" Ion-Sel. Nectrode Rev. 1979, 7 . 139. (18) Gimblett, F. G. R. "Inorganic Polymer Chemistry"; Butterworth: London, 1963. (19) Gran, G. Analyst (London) 1952, 77,661. (20) Vogel, A. I. "Quantitative Inorganic Analysis", 3rd ed.; Woolwich Polytechnic: London, 1961;p 903.

(9) Moody, G. J.; Rigdon, L. P.; Meisenheimer, R. G.; Frazer, J. W. Analyst (London) 1981, 106, 547. (11) Srivastava, S. K.; Jain, A. K.; Agarwal, Sushma; Slngh, R. P. Talanta 1978,25, 157. (12) Jain, A. K.; Srivastava, s. K.; Agarwal, Sushma; Singh, R. P. J . Appl. Chem. Blotechnol. 1977,27, 680. (13) Malik, W. U.; Srivastava, S. K.; Bhandari, V. M.; Satish, Kumar J. Colloid Interface Scl. 1974, 47, I. (14) Malik, W. U.; Srivastava, S. K.; Razdan, P. N.; Satish, Kumar J . Electroanal. Chem. 1978, 72,111. (15) Ruedel, H. J., Ber. Kernforschungsanlage Juellch 1982,32,83. (16) Rodin, S.S.; Levrukhina, A. K. Radlokhlm/ya 1962, 4, 623.

(IO) Marshall, G. B.; Midgley, D. Analyst (London) 1979, 104, 55.

RECEIVED review August 11,1981. Accepted March 4, 1982. for Amla Bansal is grateful to C.S.I.R. for financing this research project.

Effects of Organic Solvents in Inductively Coupled Plasma Atomic Emission Spectrometry

Andrew W. Boorn' and Rlchard F. Browner+
School of Chemistry, Georgia Institute of Technology, Atlanta, Georgia 30332

The tolerance of a low power (1.75 kW) argon lnductlvely coupled plasma (Ai ICP) to 30 common organic solvents Is discussed In terms of their limiting aspiration rates. Good correlation was found between llmltlng aspiration rates and evaporation factors, E , for a number of solvents. Thls Indicates that solvent vapor loading is the major factor lnfluenclng plasma stablllty with organlc solvent Introduction. Signal magnitudes were compared for both aqueous and organic solutlons of several elements, and while enhancements were found for the Cu atom line in many solvents, Cr and Fe Ion lines were suppressed In volatlle solvents. Thls behavior was attributed to changes In plasma excitation characteristics, caused by solvent vapor lnteractlon wlth the plasma. Removal of solvent vapor from the aerosol stream by condensation produced signal enhancements of a magnitude consistent with transport efflclency predlctlons. The effects of rf power and aspiration rate on the tolerance to the solvent, the signal enhancement, and the detection limits are considered. Spectral Interferences due to the organlc solvents are discussed and found not to be very serious.

Inductively coupled plasma atomic emission spectrometry (ICPAES) has found wide acceptance as a rapid, versatile technique for the determination of trace, minor, and sometimes major elements in a wide range of sample matrices (1-4). The great majority of sample types are presented to the ICP as aqueous, frequently acidic, solutions and the fundamental properties of the plasma have therefore been well characterized for these solvents. However, there are certain circumstances in which the introduction of an organic solvent to the ICP may be preferred. The first is when solvent extraction is used in sample preparation to remove the analyte from a complex matrix. Matrix components might otherwise cause spectral interferences, nebulizer blockage due to the high solids content of the solution, or analyte emission enhancement. Solvent extraction may also be used to produce a preconcentration of the analyte. On occasion direct analysis of organic matrices Present address: SpectraMetrics, Inc., 204 Andover Street, Andover, MA 01810.

is desired, and finally the ICP may be used as an element selective detector for normal-phase high-performance liquid chromatography (HPLC). Solvent extraction of metal chelates for atomic absorption spectrometry (AAS) has been widely reported ( 5 ) . This approach has also been used to remove trace elements from complex geological samples (6) and from foodstuffs ( 7 ) and to achieve a necessary preconcentration prior to their determination by ICPAES. The determination of wear metals in used lubricating oil is the most frequently reported circumstance in which a sample, directly diluted with an organic solvent, is introduced into the ICP (8-16). The solvents employed in these reports were 4-methylpentan-2-one (MIBK) (5,10,12,13,16),xylenes (9, 11, 13-15), chlorobenzene (13),and toluene (8). Trace elements in a variety of other petroleum products have been determined by ICP spectrometry, specifically, fuel (14,15,17, 18),crude (17) and unused lubricating oils (19), bitumin and oils from synthetic tar sands (20), and gasoline diesel fuel and transmission fluids (9). Polymers and biological fluids have also been directly analyzed for trace elements, after dissolution in a variety of organic solvents (17, 19). Several reports of HPLC-ICP coupling have appeared in the literature (12-25) including a review (25), but these have mostly considered aqueous mobile phases for ion exchange or gel permeation chromatography. The use of organic solvents in the mobile phase to perform normal-phase separations has been reported in only two instances (26,27). Recently, the use of toluene and pyridine as mobile phases for size exclusion chromatography employing ICP detection has been described (28,29). Clearly this marriage of two such powerful analytical techniques has great potential, and in this respect, the information contained in this study regarding the interactions of a variety of organic solvents with the ICP may be particularly useful. A detailed investigation of the nebulization of organic solvents in atomic spectrometry has been reported previously (30). In that paper, the relative rates of solvent evaporation from aerosol droplets, were shown to be critical in determining the transport efficiencies of organic solvents more volatile than water. On comparison of the transport efficiency of an organic solvent of low volatility, such as nitrobenzene, to water, the difference in surface tension was considered to be the dom-

0003-2700/82/0354-1402$01.25/00 1982 American Chemlcal Society

ANALYTICAL CHEMISTRY, VOL. 54, NO. 8, JULY 1982

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Table I. ICP Instrumentation system I supplier ICP torch nebulizers nebulizer gas sample introduction assembled in-house system I1 Perkin-Elmer Corp (Norwalk, CT) Model ICP/5000 27.12 MHz, 2.5 kW PlasmaTherm (Kresson, NJ) ICP 2500 comprising HFP 2500D RF generator; AMN 2500-E automatic matching network; APCS-3 automatic power control PlasmaTherm Model T1.0 concentric: T. E. Meinhard and Associates (Santa Anna, CA) Model TR-30-A3 cross flow: PlasmaTherm, Model TN-5500 mass flow controller: Matheson Gas Supply Co. (East Rutherford, NJ) Model 8240 peristaltic pump, Buchler Instruments (Fort Lee, NJ) Model 2-6200 with 0.78 mm i.d. Tygon tubing (Nort,on Co., Akron, OH) formulation R-3603 for aqueous solutions; formulation F-4040A was suitable for many organic solvents. For highly polar solvents a syringe pump, Sage Instruments (Orion Research, Inc., Cambridge, MA) Model 341 and Intramedic polyethylene tubing (Clay Adama, Parsippany, NJ) was used 0.5-m Ebert, Jarrell-Ash (Waltham, MA) 1 80 1 0.408-m Czerny-Turner holographic grating, 2880 grooves/mm ruled diffraction grating blazed grooves/mm blazed at 210 nm used for 175at 300 nm. Manual wavelength selection 460 nm region. A ruled grating, 1440 grooves/ mm blazed at 580 nm used for 460-900 nm. Wavelength selection by microprocessor control of the grating drive microcomputer, P.-E. data Station 10, controlled. manually from picoammeter, Keithley Data output on CRT display and line printer (Cleveland, OH) Model 4145 and SargentP.-E. Model PR-80 Welch (Skokie, IL) Model SRG chart recorder Table 11. Limiting Aspiration Rates for Selected Organic Solvents limiting aspiraevaporation factor tion rate, ( E ) ,w 3 / s mL/min 0.1 47.2 2.5 45.6 3.0 22.5 >5.0 9.30 > 5.0 5.27 298 165 8.90 179 164 58.4
18.5 <0.1 <0.1

spectrometer

data acquisition

inant effect. The evaporation rate was also found to correlate with the tolerance of the low power argon ICP to organic solvents. A quantitative evaluation of the effects of a variety of common organic solvents on the analytical signal obtained from a low power, argon ICP is presented here. The effects of rf power, nebulizer parameters (gas fliow, sample aspiration rate, etc.), and nature of the solvent on the detection limits and spectral interferences are also discussed.

solvent methanol ethanol propanol butanol pentanol pentane hexane heptane isooctane decane cyclohexane benzene toluene xylene nitrobenzene chlorobenzene acetone 4-methylplentan-2-one (MIBK) diethyl ether tetrahydrofuran acetonitrile pyridine dimethylformamide methylene chloride chloroform carbon tetrachloride carbon disulfide dimethyl sulfoxide ethyl acetate propyl acetate water

EXPERIMENTAL SECTION Instrumental Section. Details of the two ICP instruments used are given in Table I. The organic solvent tolerance studies were performed mostly on system I, which vvas assembled in-house, as were the spectral interference studies. Signal enhancements, the effects of increased rf power, condensation of organic vapor in the sample introduction system, and most detection limits were determined on system 11, the Perkin-Elmer ICP/5000, which was used without modification. Reagents. Analytical Reagent grade metal salts (Fisher Scientific, Co.) and high purity, double dleionized water (Continental water conditioning system) were used for aqueous solutions. Analytical Reagent grade organic solvents (Fisher Scientific Co.) and Organo-metallic standards (metal cyclohexanebutyrates, Eastman Kodak, standards for AAS) were used for the organic solvent solutions. The standards were dried, either over fresh Pz05for 2-48 h or at 110 C for 2 h, as specified by the manufacturer. A 500 pg/mL stock solution was prepared by dissolving the appropriate amount of dry standard in 5 mL of a 1:l:lmixture with gentle of 2-ethylhexanoic acidl:2-ethylhexylamine:xylenes, heating. After being cooled, the solution was made to 100 mL with the required solvent. Working standards were prepared fresh each day. RESULIS AND DISCCrSSION ICP O p e r a t i n g Conditions for O r g a n i c Solvents. Thirty organic solvents were investigated for their compatibility with the ICP and are listed in Taible 11. A semiquantitative estimate of plasma stability was established in terms of the limiting aspiration rate. Solvents were fed to the nebulizer by peristaltic or syringe pump, and the limiting aspiration rate was established such that stable plasma operation, with no appreciable carbon deiposition on the inner torch surfaces, was possible for a period of 1h. These aspiration rates convey, in a semiquantitative manner only, the relative ease of plasma operation with different organic solvents. Values are given in Table 11.

0.2 0.5 2.0 <0.1 <0.1

1.0

4.0
>5.0

4.09 23.8 264 77.3

771

3.0
0.1

3.0
<0.1 <0.1 0.2 1.0
0.5

557 321 164 399 157 13.1

> 5.0

2.0 3.0 0.5 2.0 1.5 2.5

plasma Ar; 2.0 L/min auxiliary Ar;PlasmaTherm cross flow nebulizer operated at 1.00 L/min Ar. The ICP operating conditions which were employed for the aspiration rate study were 1.75 kW forward rf power, 12 L/min plasma gas, 2.0 L/min auxiliary gas (except for the lower alcohols where no auxiliary flow was used), and 1.00 L/min nebulizer gas flow to a PlasmaTherm cross flow nebulizer. Limiting aspiration rates for a Meinhard concentric nebulizer

ICP operating conditions:

1.75-kW rf power; 1 2 L/min

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ANALYTICAL CHEMISTRY, VOL. 54, NO. 8, JULY 1982

operated under identical conditions were not significantly different. It is important to realize that the natural aspiration rates for the organic solvents studied, at 1-00L/min nebulizer gas flow, were in the range 0.8-3.5 mL/min. The decision as to whether a particular organic solvent with a low limiting aspiration rate may be employed in a given analysis depends on the intensity of the emission lines for the elements to be determined and their concentration in the sample. Solvents with low limiting aspiration rates can be introduced to the ICP with a microsample introduction device, such as those previously reported (19,31). Flow injection analysis, where 10-100 pL of the sample in a low limiting aspiration rate solvent is injected into a flowing stream of a solvent with a high limiting aspiration rate, is a possible means of circumventing this problem. In general, it was found that an increase in forward rf power produced a corresponding increase in the ICP tolerance to organic solvents. However, in certain cases, such as benzene, ether, and acetone, for example, an increase in rf power to the generator limit of 2.75 kW, still allowed an increase in aspiration rate to only 50.5 mL/min. It appears that the tolerance of the ICP to organic solvents may be interpreted in terms of solvent evaporation from the aerosol droplets. The evaporation factor, E , given in Table I1 and defined below, shows a reasonable correlation with limiting aspiration rates. In general, the ICP has decreasing tolerance to solvents as their evaporation rates increase. Evaporation curves for organic solvent aerosols in nonturbulent flows have been calculated (32)and the derivation of the equations for the evaporation rate reported (32),so the equation is merely stated here. The diameter of an aerosol droplet, d (pm), at time, t (s), after formation is given by

d = (do3- E t ) 1 / 3
where do is the initial diameter (pm) and E is given by

(1)
(2)

= ~~D,UP,I@(~RT'-~

where D,is the diffusion coefficient for solvent vapor, M the molecular weight of the solvent, R the gas constant, T the absolute temperature, P, the saturated vapor pressure, u the surface tension, and d the density. This equation involves many simplifying assumptions, such as isothermal, laminar flow conditions, which cannot be present in the spray chambers used in ICP spectrometry. However, the trends indicated by the magnitude of E should be valid for diffusion limited evaporation processes. Two classes of solvents investigated did not show a correlation between evaporation rate and plasma stability, these being chlorinated hydrocarbons and alcohols. Methylene chloride, chloroform, and carbon tetrachloride have high evaporation factors, as would be expected, yet gave high limiting aspiration rates (Table 11). The unexpectedly high limiting aspiration rates for the chlorinated hydrocarbons may be due in part to efficient penetration of the central plasma channel resulting from the high solvent densities. Conversely, methanol and ethanol have only moderate evaporation rates, yet readily quenched the plasma. With these two alcohols very little green C2emission was observed around the outside of the plasma, indicating reasonable penetration. The instability with alcohols resulted from a gradual quenching of the luminous plasma core from beneath the coil, which finally reached into the core region and the plasma extinguished. Owing to this effect, no auxiliary gas was used when aspirating alcohols. The greater carbon content and lower volatility of the higher alcohols allowed their introduction to the plasma without difficulty, with the green edge to the plasma clearly visible again. Similar results to these have been reported (33) for ethanol-water mixtures, where the plasma resistance, as

indicated by the reflected power, increased with the ethanol concentration. The quenching of the plasma is accompanied by an increase in reflected power. When this can no longer be brought below about 200 W by the automatic and manual adjustment of the variable capacitors in the matching network, the plasma either extinguishes or, more seriously, reverts to a localized discharge at the torch wall, rapidly melting the torch. Increasing the nebulizer gas flow increases the velocity of the sample aerosol entering the ICP and this can be used to increase the tolerance of the plasma to the solvent. However, the resulting decrease in analytical signal due to the decreased residence time of the analyte in the plasma, and the shift in optimum viewing zone higher in the tail flame, can result in a considerable loss in precision. Furthermore, a substantial increase in nebulizer gas flow can give rise to significant interferences in samples with complex matrices. Both factors suggest that increasing gas flow is not an optimum approach to overcoming plasma instability problems. As would be expected, much greater tolerance to organic/aqueous solvent mixtures was observed than for pure solvents. This is of particular importance in HPLC/ICP interfacing, where mixed solvents are frequently employed in reversed-phase separations and gradient elution. For example, a 75% methanol 25% water mixture was aspirated at 3.0 mL/min routinely under the ICP conditions stated previously, whereas Table I1 indicates only 0.1 mL/min pure methanol could be introduced. The use of increased rf power and reduction of the vapor loading were both investigated in terms of signal enhancement compared to aqueous solutions, as discussed below. It should be noted, that in high power (6 kW), nitrogencooled plasmas the introduction of organic solvents appears to be relatively straightforward (34),largely as a result of the high power level efficiently decomposing the solvent vapor. Recent studies with the use of Ar plasma gas containing up to 5% O2have also shown improved tolerance of low powered Ar ICPs to some organic solvents (20). Signal Enhancements. In flame AAS, an enhancement of the analytical signal is generally observed when an organic solvent is used in place of an aqueous solvent. This enhancement has been attributed to changes in sample aspiration rate and median droplet diameter and discussed in terms of the surface tension and mass-flow terms, respectively, of the Nukiyama and Tanasawa equation (6, 35, 36)

This empirical equation expresses Sauter median (volume to surface area ratio) diameter (pm), in terms of V, the velocity difference between gas and liquid flows to the nebulizer (m/s), u, the surface tension of the liquid (dyn/cm), p , the liquid density (g/cm3),9, the liquid viscosity (poise), and Q1 and Qg, the volume flow rates of liquid and gas respectively (cm/s). In atomic spectrometry, the mass median diameter, d,, is a major parameter of relevance in relating transport efficiency and analytical signals to aerosol properties. Mass and Sauter median diameters are numerically equivalent for aerosols composed of unit density, spherical particles, such as dilute aqueous solutions. With organic solvent aerosols, the deviation from unit solvent density will affect this equivalence, but this will not give rise to significant variations in the trends discussed in this study. Values for d, and d , will, in any case, still remain close. The relative importance of the two terms in the Nukiyama and Tanasawa equation depends critically on the nebulizer gas flow and, if independently controlled, the aspiration rate. For a particular solvent, the first term of the equlation remains

ANALYTICAL CHEMISTRY, VOL. 54, NO. 8 , JULY 1982

1405

constant and fairly small, while the second term is comparable to the first at low aspiration rates ( 5 0 5 mL/min) and increases rapidly to 10-501 times the first term at high aspiration rates (13.5 mL/min). Primary droplet diameters were calculated as a function of aspiration rate, for i l PlasmaTherm cross flow nebulizer. A gas velocity of approKimately 236 m/s was assumed for 1.0 L/min flow through the 0.30 mm i.d. capillary. A similar calculation was also made for the Meinhard concentric nebulizer. However, gas velocities achieved1 with the Meinhard concentric nebulizer arc somewhat greater (approximately 320 m/s at 1.00 L/min), due to the smaller gas orifice (an annular spacing of 0.030 mm is typical). The first term in the Nukiyama and Tanasawa equation is thus smaller for the Meinhard nebulizer, but at common aspiration rates of 2-3 mL/min the second term predominaties and the primary droplet diameters calculated, and shown in Figure 1, are similar to those for the cross flow nebulizer. A curve for water is included for reference. A detailed discussion of the significance of the primary drop size distribution in ICP and AAS nebulizer/spray chamber systems wl be described elsewhere il (37). Greenfield et al. (34)l reported enhancement effects in the high-power (6 kW) N2-cooledAr ICP whlen organic acid- and methanol-water mixtures (up to 60% organic) were used as solvents. Using an AAS concentric nebulizer they obtained the following empirical equation

$
4

w*cot-wrl

r-

??Ym.p'.?l o orlrlrlr

;O O r l N r l O

I =I

-?-( (ap)0.5

7+

2
1,245) (4)

~ M M O N M

r-mr-marl

??r'."m.?

0 0 0 0 0 0

This relates the observed atom and ion lline signals, I , to the physical properties of the solvent, as defined above. I , is the emission intensity for an aqueous solutiion of the same concentration. In studies with the low-power Ar ICP, detection limits have been reported for several elements determined in selected organic solvents, and these were found to be comparable to detection limits obtained in aqueous solution (7-20). However, the question of signal enhancement in the low-power Ar ICP has not previously been addressed. In this study, six solvents were selected and three analytes determined in each solvent. The observed signal enhancement, i.e., the ratio of net emission intensity in the solvent to the net emission intensity for water, under conditions of 1. free aspiration rate, are given in Table 1 1 The measured aspiration rate, the primary median droplet diameter calculated from the Nukiyama and Tanasawa equation, and the enhancement factor calculated from tlhe Greenfield et al. equation are also given. The Greenfield et al. equation is based on the effect of changing aspiration rate and hence, via the Nukiyama and Tanasawa equation, the effect of changing the primary droplet diameter on the transport efficiency. However, as the calculated primary droplet sizes show, the effect of the variations in aspiration rate leads to larger droplets for some solvents, compared to water, and, therefore, a reduction in transport efficiency would be expected. A reduction in transport efficiency with all other operating parameters held constant, particularly nebulizer gas floa,would be expected to cause a reduction in emission signal rather than the enhancements predicted lby Greenfield et al. While the data in Table I11 clearly indicate a reduction in emission signals for certain cases, the magnitude of the signal reduction is greater than would be predicted on the basis of the shift in droplet diameter alone. Further, the difference in behavior of different elements and the vari,ations of enhancement with viewing height requires a more detailed explanation. The high evaporation rates and good plasma penetration observed for chloroform and carbon tetrachloride would be expected to produce enhancements. The particularly low

a m m o

oooorlrl

E *comooco ooalwmco E ooorlam

000000

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ANALYTICAL CHEMISTRY, VOL. 54, NO. 8, JULY 1982

300

to the chlorinated solvents (Table 111),but to a reduced extent

commensurate with the decrease in volatility. Xylenes, which evaporate slightly faster than water, would be expected to show a large reduction in transport efficiency owing to the larger droplet size. The evaporation effect appears to dominate the transport efficiency as indicated by the large enhancements a t 25 mm viewing height. The enhancements of 1.0-1.5 observed for butanol and nitrobenzene are related to the smaller primary droplet size; these solvents evaporate less than water but their higher viscosities result in smaller aspiration rates, which dominate their transport efficiencies via the reduced droplet diameters. The temperature lowering of the plasma was investigated in a comparative manner by measuring the copper atom to ion line ratio, Cu 1324.74 nm/Cu I1 224.70 nm. Water and three organic solvents of widely differing evaporation characteristics, butanol, xylenes, and carbon tetrachloride, were V tested. The results are shown in Table I for four observation heights in the plasma. The atom line intensity increased with d solvents at the expense of the ion line, indicating a decrease in excitation temperature due to the presence of the organic vapor. As would be expected on the basis of evaporation considerations, the greatest increases in atom to ion line ratio were observed with the more volatile solvents. In an attempt to confirm that it is indeed the solvent vapor loading which causes signal depressions in the plasma, the nebulizer/spray chamber unit was mounted beneath the plasma box and a 12-in. water condenser inserted between the spray chamber and torch. The condenser was fitted with a conical flask with a side arm to allow aerosol droplets to pass to the torch while collecting condensed solvent. This simple system did not condense all of the vapor, but a visible reduction in the green Cz emission around the outside of the plasma occurred. The signal enhancements measured with this system are given in Table V and the increase in enhancement for the volatile solvents, compared with those in Table 111, is considerable. Some temperature decrease was still observed for the very volatile solvent chloroform. The trend of increasing enhancement higher in the plasma was again observed for the ion lines. The reduction in signal observed for nitrobenzene was most likely a result of the increased time for gravitational settling in this system, causing a reduction of transport efficiency. During preparation of this paper the use of a water-cooled spray chamber in ICP spectrometry, with toluene and pyridine as solvents, was reported (28,29). Improvement in plasma stability and tolerance to the solvents was achieved, allowing higher solvent aspiration rates and improved detection limits. It is important to note that the enhancements measured at 25 mm observation height were greater than those predicted by the Greenfield et al. equation, indicating that evaporation increases the transport efficiency in spite of any aspiration rate effect on the primary droplet size. To further investigate the contributions of evaporation and aspiration rate to transport efficiency and signal enhancement, the enhancements were measured a t a fixed aspiration rate

f
U
W IW 1

200

100

1.0

2.0

30 .

4.0

ASPIRATION RATE (rnL/rnin)

Figure 1. Calculated primary median droplet diameters (d,)for organic solvents. Concentric glass nebulizer (Meinhard)operated at 1.00 L/min gas flow: 1 = butanol; 2 = nitrobenzene;3 = ethanol; 4 = xylenes; 5 = benzene; 6 = 4-methylpentan-2-one; 7 = ethyl acetate; 8 = carbon tetrachloride, 9 = chloroform.

Table IV. Cu Atom to Ion Line Ratios for Organic Solventsa observn height, mm
10 15 25 35
a

water 3.09 5.56 36.8 57.1

butanol 15.3 17.5 38.9 88.2

xylenes 31.0 30.4 47.4 93.5

carbon tetrachloride 51.3 65.1 75.7 14.4

ICP conditions are as in Table 111.

emission signals obtained with these solvents for the iron and chromium ion lines and the enhancements close to unity for the copper atom line indicate a change in excitation conditions, possibly through temperature lowering in the plasma. This is attributed to the large vapor loading, produced by these highly volatile solvents, absorbing rf power in both the central channel and through entrainment into the energy addition region. Greater signal enhancements were observed higher in the plasma, indicating that as solvent vapor is decomposed the excitation and ionization temperatures increase once more. The chromium ion line, which has the greatest excitation energy of those studied, was depressed to a greater extent than the iron ion line, supporting this conclusion. The solvent 4-methylpentan-2-one (MIBK), which has a moderate evaporation rate (Table 11), showed a similar trend

Table V. Signal Enhancements for Organic Solvents with Vapor Condensation, Natural Aspiration lCatea
aspiration
Ck I1 205.55 nm

solvent chloroform carbon tetrachloride 4-methylpentan-2-one xylenes nitrobenzene

a

rate, mL/min 1 0 m m 2.20 1.70 2.60 2.50 1.25 0.12 0.81 2.60 3.10
0.41

I J I W measured Fe I1 259.94 nm 1 5 m m 2 5 m m 1 0 m m 1 5 m m 25mm

Cu 1324.75 nm

1 0 m m 1 5 m m 25mm 1.75 2.24 3.01 3.17 0.89 2.23 2.84 3.24 3.16 0.99 2.94 3.14 3.36 3.18 1.07

0.24 0.91 3.10 3.31 0.29

1.90 2.19 3.73 3.67 1.07

0.24 0.69 2.29 3.04 0.44

0.43 0.99 2.76 2.96 0.46

1.86 2.15 3.18 3.11 0.97

ICP conditions are as in Table 111.

ANALYTICAL CHEMISTRY, VOL. 54, NO. 8, JULY 1982

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Table VI. Signal Enhancements for Organic Solvents at Fixed Aspiration Rate (1.40 mL/min)a primary median droplet Cr I1 205.55 nm diameter, pm 10mm 15mm 25mm 48.4 58.4 57.0 59.6 112 78.8 78.9 0.009 0.019 0.049 0.175 0.315 0.513
0.011 &/Iw measured

solvent chloroform carbon tetrachloride 4-methylpentan-2.one xylenes butanol nitrobenzene water

a

Fe I1 259.94 nm 10mm 15mm 25mm 0.073 0.135 0.133 0.350 0.498 0.688 0.128 0.183 0.429 0.709 0.640 0.987 0.640 1.13 1.98 2.04 1.97 1.39

Cu 1324.75 nm 10mm 15mm 25mm 0.532 1.29 1.81 2.22 2.21 1.57
1.18

0.053 0.22 0.545 0.533 0.895

0.330 0.884
1.01 1.81

1.94 0.836

1.15 2.66 2.51 1.77 1.52

1.59 1.79 2.29 2.21 2.09 1.18

-

ICP conditions are as in Table 111.

Table VII. Signal Enhancement at 2.45 kW RF Power'

IJIW measured
C I1 205.55 nm r

solvent carbon tetrachloride 4-methylpentan.2-one xylenes

a

10mm 0.06 0.37 0.70

15mm 0.31 0.84

1.11

25mm 0.91 2.07 1.84

Fe I1 259.94 nm 10mm 15mm 25mm 0.16 0.46 0.76 0.38 0.94 1.17 1.28 2.28 1.95

Cu 1324.75 nm 10mm 1.20 2.50 2.50 15mm 1.66 2.71 2.33 25mm 2.08 3.06 2.42

Aspiration rate 1.4 mL/min. decreased by 20% at 25 mm. This behavior is typical of that reported for atom and ion lines at increased rf power levels (38);in general, as the power increases, the ion population increases a t the expense of the atom population. The signal enhancements, and hence transport efficiencies, for organic solvents in the low power argon ICP are clearly dominated by evaporation effects for those solvents more volatile than water. The enhancements for nonvolatile solvents such as butanol and nitrobenzene are determined by the surface tension and aspiration rate differences (when this is not controlled) from water, as reflected by differences in the primary droplet diameter. Solvent Spectra. The molecular band systems observed for the solvents listed in Table I were CN (violet) 2 C2 (Swan) >> CS > OH > NO(y) > CH > NH 2 CC1, arranged in order of decreasing intensity. The wavelengths of the major band heads are given in Table VI11 and have been reported previously by several workers (39-41). Atomic hydrogen (Balmer Series) and carbon lines were also present, the latter being fairly intense for all solvents as expected. In general, the region 190-300 nm was free of molecular bands except for CS from sulfur-containing solvents. Only the NO y-band system and broadened atomic carbon lines at 193.09, 193.36, and 247.86 nm presented the possibility of direct or wing spectral overlap with the majority of solvents. Direct spectral overlap requires the use of correction factors to the measured intensity or, in severe cases, the choice of an alternative analyte line. Wing overlap generally causes a sloping background which may be corrected for by off-peak background measurements at carefully selected wavelengths on one or both sides of the analyte line. Atomic carbon lines and the NO y-band system are present when aqueous solvents are used, and although their intensities are naturally much greater with organic solvents, they cause little spectral interference. This is extremely fortuitous because many of the most intense analytical lines in the ICP are found in the spectral region below 300 nm. Little problem due to spectral interferences is therefore incurred by the use of organic solvents. In the region of the spectrum above 300 nm, the situation is more complex and, depending on the analyte concentration

of 1.4 mL/min, controlled by either a peristaltic or syringe pump. This aspiration rate represented a considerable reduction from the natural aspiration rates a t 1.00 L/min nebulizer gas flow for chloroform, carbon tetrachloride, 4methylpentan-2-one, and xylenes (cf. Table 111). These data are shown in Table VI. The reduced aspiration rates result in a reduction in the vapor loading in the plasma and smaller primary droplet diameters, effects which are clearly reflected l in the increased enhancements at d viewing heights compared to the data in Table 111. For butanol, a flow of 1.4 mL/min represented an increase in aspiration rate over the natural rate, causing a decrease in transport efficiency arid smaller enhancements. The anomalous increase in enhancement for butanol higher in the plasma may have resulted from a small reduction in excitation temperature lower in the plasma. This theory is supported by the atom line enhancements with butanol which were greater a t low observation heights, a t the expense of the ion lines. The aspiration rate was increased slightly for nitrobenzene and the expected small decrease in enhancement apparently resulted. However, the actual net emission signals for nitrobenzene did not change appreciably with the change in aspiration rate, so that the difference in enhancements was actually due to the change in transport efficiency compared to water. This was noit the case for the other solvents, since their changes in aspiration rates followecl those for water very closely. As has been stated previously, an increase in rf power produced a corresponding increase in plasma tolerance to organic solvents. For investigation of the effect on the signal enhancements the data shown in Table VI1 were collected at 2.45 kW forward rf power and a fixed aspiration rate of 1.4 mL/min. As expected, the increased power counteracted to some extent the temperature lowering due to the solvent vapor, and consequently larger enhancements were observed. Appreciable increases in the net emission intensities from the organic solutions were obtained, since in the aqueous solutions net ion line intensities increased by factors of 1.2, 2.5, and 1.7, a t 10, 15, and 25 mm observation heights, respectively. The atom line intensity remained unchanged at 10 and 15 mm and

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ANALYTICAL CHEMISTRY, VOL. 54, NO. 8, JULY 1982

Table VIII. Organic Species Emission Spectra in the I C P wavelength, nm

436.52 437.14 438.25 467.86 468.48 469.76 471.52 473.71 512.93 516.52 547.03 550.19 554.07 558.55 563.55 431.25 431.50 358.38 358.59 359.04 385.09 385.47 386.19 387.14 388.34 41 5.34 416.78 418.10 419.70 421.60 253.87 255.58 257.27 257.56 258.96 260.59 262.16 266.26 267.70 269.32 270.89 272.67 306.72 308.9 336.01 337.0 215.49 226.94 237.02 247.87 259.57 272.22 277.76 278.83 193.09 199.36 247.86

species
c 2

analyte lines suffering from potential spectral interferences

Cs 11, 452.67; Cs I, 455.53 Ba 11, 455.40 Li I, 460.29

Ba 11, 493.41; Li I, 497.17

HEIGHT ABOVE COIL (mm)

CH CN

Flgure 2. Spatial emission profiles of 358.38-nm CN band in the Ar ICP: (- -) pyridine, (.-) xylenes, (- - -) carbon tetrachloride, (-) dimethyl sulfoxide. ICP operating conditions are as in Table 11.

T 11, 350.92 b Dy I, 353.17, 353.60

Tb 11, 356.33; Zr 11, 357.25 Sc 11, 357.25; Sm 11, 359.26 Eu 11, 381.97; Tm 11, 384.80 Tb 11, 384.87; U 11, 385.96 Tb 11, 387.42; Ho 11, 389.10 Nd 11, 41 5.61 ; Ga, 417.21 Pr 11, 417.94; Ce 11, 418.66 Rb I, 420.19; Eu 11, 420.51 Sr 11, 421.55; Rb I, 421.56 P I , 253.57; Hg I, 253.65 Li I, 256.23; Zr 11, 257.14 Mn 11, 257.61 Mn 11, 259.37; Sb I, 259.81 Fe 11, 259.94; Mn 11, 260.57 Pb I, 261.42; Lu 11, 261.54 Ru 11, 266.16 Au I, 267.60; Cu 11, 267.72 Ru 11, 267.881; Ta 11, 268.52 Ru 11, 269.21; Nb 11, 269.71 Ru 11, 269.21; Nb 11, 269.71 very weak A1 I, 309.271, 309.284; V 11, 309.311,
310.230

cs

OH NH NO

very weak
Zrl I, 213.856; Cd 11, 214.438 Cd 11, 226.50 Cd 11, 228.802

Mn 11, 257.610; Mn 11, 259.373; Mn 11, 260.569 very weak

cc1
CI

As I, 193.70
Se I, 199.51

and sample aspiration rate, serious spectral interferences may be encountered. In this respect the flexibility of the sequential spectrometers employed in this study was very advantageous. Scanning of the spectral region around each analyte wavelength of interest was possible, enabling selection of appropriate background correction wavelengths. Reference to tables of molecular spectra (42) will give the positions of the major band heads, but in trace element determinations the broad molecular bands, comprised of the vibrational and rotational structure, can cause appreciable interference even several nanometers from the band head. Some of the potentially more serious spectral interferences

due to organic solvents are listed in Table VIII. Only analyte lines which are among the five most sensitive for that element, as determined by Winge et al. (43) are listed. The analyte lines listed in Table VI11 could potentially suffer spectral interference problems. Not all of these have been investigated in the present study, and the information is provided here only as an indication of a need for careful background scans in the region of the band heads listed, before final line selection. While the CS bands may be a source of spectral interference, they are only present when a sulfur-containing solvent is used. The interferences due to Cz and CN bands will be present to varying degrees with all organic solvents, but most of their potential interferences are with the less commonly determined elements, such as the lanthanides (Table VIII). This may present a problem in the use of the ICP for their determination, since these elements are frequently separated by chelation and solvent extraction (44). The OH band intensity is greatly reduced in organic solvents compared to water and is still fairly weak in alcohols. It presents little interference with the 309.37-nm A1 and 309.31-nm V lines except for trace level determinations. In general, it is fair to conclude that solvent spectral interferences will not normally be a limiting consideration for trace element determinations in organic solvents by ICP spectrometry, spectral interferences due to other elements in the sample being potentially more serious. Tables have recently been published for evaluating the possibility and extent of these spectral interferences in the ICP (45, 46). To ascertain if any other molecular species were present in the ICP, we recorded spectra at a variety of viewing heights, including measurements between the turns of the load coil and 3 and 5 mm below it. No additional spectral features were observed, indicating that the ICP effectively decomposed organic molecules to diatomic fragments very soon after they leave the sample introduction tube. This was also indicated by the intense green, C2 band emission visible below the plasma. Figures 2-4 show the variation of the three most intense organic spectral features, that is, the atomic carbon line at 193.09 nm and the 516.52 nm C2 and 358.38 nm CN emission bands, with viewing height. Atomic carbon and C2intensities decreased with increasing height in the plasma as expected. The CN emission intensity passed through a maximum for non-nitrogen-containing solvents. The maximum resulted from increasing entrainment of nitrogen from the air into the plasma above the end of the torch. This entrainment was reduced by using an extended outer tube on the plasma torch and by the purge chimney employed on the Perkin-Elmer instrument. Nitrogen-containing solvents, such as pyridine,

ANALYTICAL CHEMISTRY, VOL. 54, NO. 8, JULY 1982

1409

'+
5

1'5 20 HEIGHT ABOVE COIL lmmj

, 25 d 30

1 0 15 20 HEIGHT ABOVE COIL immJ

25

Figure 3. Spatial emission profiles o 193.09-,nmatomic carbon line. f Solvents and operating Conditions are as in Figure 1.

Flgure 4. Spatial emission profiles of 516.52-nm C2 band. Solvents and operating conditions are as in Figure 1.

Table IX. ICP Detection Limits-Organic Solvents; Meinhard Concentric Nebulizera detection limit, ng/mL Cr I1 FeII CUI 204.55 259.94 324.75 nm nm nm 2500 1000 180 56 26 29 29 28 15 4.8

solvent chloroform carbon tetrachloride 4-methylpentan-2-one xylenes butanol nitrobenzene water

4.4 2.5 1.4 1.8 0.73 6.0 1.8 5.8 2.8 3.7 3.6 ICP conditions as i n Table 111; 1 5 mm viewing height.

gave a CN emission maximum lower in the plasma, around 10 mm, with a second maximum around 25 mm due to the air entrainment. Detection Limits. Detection limits, CL, were calculated on the basis of the concentration requiredl to give a signal three times the standard deviation of the background, according to the equation given by Winge et al. (43)

O.Ol(3)C CL N I n/ I b

(5)

where I, is the net line intensity, I b the background intensity, and C the concentration used to obtain I,, in this case 50 kg/mL. The assumption in this equatilon that the standard

deviation, or noise, on the background is 170(0.01) or less of the background intensity was found to hold for all solvents and analyte wavelengths investigated. Detection limits obtained under the conditions given in Table I11 are shown in Table IX. The detection limits are in approximately the same ratios as the signal enhancements compared to water, which would be expected if no significant background shifts occurred in the organic solvents. While no background shifts due to the organic solvents listed in Table X were observed at the Cr and Fe wavelengths, a small decrease in background at the Cu line occurred, due to the reduction in OH band emission compared to water. The previously discussed signal enhancements were still largely a result of the increase in net signals, with the background reductions a minor contribution. Table X lists detection limits in four organic solvents and water, for 12 lines determined on the manual ICP with the PlasmaTherm cross flow nebulizer. The solvents are arranged in order of increasing evaporation rate from left to right; in many cases the detection limits reflect the reduction of ion line intensity owing to the lower plasma temperature. The Zn, Cu, and Na atom lines, as expected, gave equivalent or better detection limits than in water. The lower detection limits for V are due in part to the decrease in OH band intensity. Variations in aspiration rate make comparisons more difficult, but some ion lines clearly do not fit the trend expected from evaporation considerations, for instance, the low detection limit observed for Mn. As discussed previously the reduction in intensity for ion lines becomes less as the excitation energy of the line decreases.

Table X. ICP Detection Limits for Organic Solvents; PlasmaTherm Cross Flow Nebulizera detection limit, ng/mL water
Cr 11, 205.55 nm Zn I, 213.86 nm Cd 11, 214.44 nm Pb 11, 220.35 nm Ni 11, 221.615nm Fe 11, 238.ilO nm Co IT, 238.139 nm Mn 11, 257.61 nm Mg 11, 279.85 nm V 11, 309.311 nm Cu I, 3 24.7 5 nm Na I, 589.080 nm

xylenes 50 15 13 221 179

14

ethanol 39 19 43 293 132

27

4-methylpentan-2-one
40 12 19 206 256
13

carbon tetrachloride 78 22 69 550 866

37

23 16 13 175
38
12

10

3.0 0.40 23 2.0 146 0.75

15 3.5 0.80 29 3.0 61 1.20

14 3.4 0.20 59 2.7 73 1.20

16 3.2 3.7 15 2.6 96 1.20

34
21 .

8.0
11 .

3.2 98 0.70

aspiration rate, mL/min ICP conditions are as in Table 1 1 1.

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ANALYTICAL CHEMISTRY, VOL. 54, NO. 8, JULY 1982

(8) zurNedden, P. Presented at X X I Colloquium Spectroscopicum Internatlonalet8th International Conference on Atomic Spectroscopy. Cambridge, U.K., 1979; abstract 442. (9) Floyd, R. C. Presented at 31st Pittsburgh Conference, Atlantic City, NJ, 1980; abstract 51. (10) Fassel. V. A.: Peterson, C. A.; Abercrombie. F. N.: Kniseley, R. N. Anal. Chem. 1978, 48, 516. (11) Merryfield, R. N.; Loyd, R. C. Anal. Chem. 1979, 57, 1965. (12) Varnes, A. W.; Andrews, T. E. Jarrell-Ash Plasma Newsl. 1978, 7 . 12. (13) Ward, A. F.; Marclello, L. Jarrell-Ash Plasma News/. 1978, 1 . 10. (14) Smith, J. C. Jarrell-Ash Plasma Newsl. 1979, 2 , 4. (15) Carr, C. D.: Borst, J. E. Presented at 29th Pittsourgh Conference, Cleveland, OH, 1978; abstract 388. Eisentraut, K. J. Anal. Chem. 1979, 57. 1927. (16) Saba, C. S.: (17) Ward. A. F. Presenred at 27th Plttsburgh Conference, Clevelend, OH, 1976; abstract 493. (18) Boorn, A. W.: Browner, R. F. Presented at 30th Pittsburgh Conference, Cleveland, OH, 1979: abstract 349. (19) Greenfleld, S.;Smith, P. B. Anal. Chim. Acta 1972, 59,341. (20) Horlick, G.; Lau, M. I n Abstracts of Papers, Chemical Institute of Canada, 63rd Chemical Conference, Ottawa, Canada, 1980. (21) Hanal, T.; Hubert. J.; Lussler, G.; Bellarance. M.; Lefeavre. M. I n Abstracts of Papers, 4th International Symposium on Column Liauid . . Chromatography, Boston, MA, 1979. (22) Fraley, D. M.; Yates, D.; Manahan, S. E. Anal. Chem. 1979, 51, 2225. (23) Morita, M.; Uehiro, T.; Fuwa, K. Anal. Chem. 1980, 52, 349. (24) Whaley, B. S.:Snabie, K. R.; Browner, R. F. Anal. Chem. 1982, 54, 162. (25) Krull, I. S.; Jordan, S.Am. Lab. (Fairfield, Conn.) 1980, 72, 21. (26) Gast, C. H.; Kraak, J. C.; PoDDe, H.; Maessen, F. J. M. J. J. Chroma.. togr. 1979, 185, 549. (27) Snable, K. R. M.S. Thesis, Georga Institute of Technology, Atlanta, GA. 1980 ._. (28) Hausler, D. W.; Taylor, L. T. Anal. Chem. 1981, 5 3 , 1223. (29) Hausler, D. W.; Taylor, L. T. Anal. Chem. 1981, 53, 1227. Browner, R. F. Specfrochim, Acta, Part (30) Boorn, A. W.; Cresser, M. S.; B 1980, 35, 823. (31) Knlseley, R. N.: Fassel, V. A.; Butler, C. C. Clln. Chem. (Winston-Sa/em, N . C . ) 1973, 79, 807. (32) Cresser, M. S.; Browner, R. F. Spectrochim. Acta, Part B , 1980, 35, 73. (33) Ito, T.; Kawaguchi, H.; Mizuike, A. Bunseki Kagaku 1979, 28, 648. (34) Greenfield, S.: McGeachin, H. McD.; Smith, P. B. Anal. Chlm. Acta 1976, 84, 67. (35) Nukiyama, S.; Tanasawa, Y. Trans, SOC. Mech. Eng., Tokyo 1938-40, 4, 5 , and 6 (Translated by Hope, E., "Experiments on the Atomization of Liquids in an Air Stream"; Defense Research Board, Dept. of National Defense: Ottawa, Canada, 1950). (36) Stupar, J.; Dawson, J. B. Appl. Opt. 1988, 7, 1351. (37) Browner, R. F.; Boorn, A. W.; Smith, D. D. Anal. Chem. 1982, 54, 1411. (38) Barnes, R. M. CRC Crlt. Rev. Anal. Chem. 1978, 7, 203. (39) Windsor, D. L.; Denton, M. 6. Appl. Spectrosc. 1978, 32, 366. (40) Greenfield, S.; McGeachin, H. McD.; Smith, P. B. ICP I n f . Newsl. 1976, 2 , 167. (41) Truitt, D.; Robinson, J. W. Anal. Chim. Acta 1970, 57,61. (42) Pearse, R. W. B.; Gaydon, A. G. "The Identification of Molecular Spectra"; Chapman and Hall: London, 1976. (43) Winge, R. K.; Peterson, V. J.; Fassel, V. A. Appl. Spectrosc. 1979, 33, 206. (44) Zolotov, Yu. A. "Extraction of Chelate Compounds"; Ann Arbor-Humphrey: Ann Arbor, MI, 1970. (45) Parsons, M. L.; Forster, A,; Anderson, D. "An Atlas of Spectral Interferences in ICP Spectroscopy"; Plenum: New York, 1980. '(46) Boumans, P. W. J. M. "Line Coincidence Tables for Inductively Coupled Plasma Emission Spectrometry"; Pergamon: New York, 1981; 2 volumes.

As the data in Table I11 show, increased signal enhancements were observed above 15 mm observation height; this might suggest that improved detection limits would also be obtained. However, the variation in intensity of the spectral background and the increasing source flicker noise, which becomes appreciably greater than 1% of the background intensity, were found to counteract the gain in net signal. This resulted in detection limits in chloroform of 4200 and 290 ng/mL for Cr and Fe, respectively, a t 35 mm height, which are significantly poorer values than those given in Table IX.

CONCLUSIONS
Organic solvents have been widely used in ICP spectrometry with varying degrees of success. Conflicting reports on the ability of the ICP to tolerate organic solvents can be seen to reflect disparities in operating conditions between various groups of workers. The sensitivity of the Ar ICP to rf power level, nebulizer configuration and gas flow varies widely depending on the nature of the solvent used. Performance will also vary with measurement height and analyte line selection. The present study has indicated that when problems are experienced with organic solvent introduction to the ICP, the primary cause may be related to greater solvent volatility compared to water. Organic solvents less volatile than water require no change from the normal plasma operating conditions. Solvents with volatility comparable to, or slightly greater than, that of water require an increase in forward rf power (to 1.72-2.0 kW), together with additional plasma gas to protect the torch. With these changes in operating conditions, the solvents can be aspirated normally (approximately 1.0 L/min nebulizing gas flow, 1-3 mL/min aspiration rate). Both atom and ion lines can be usefully measured at 15 mm above the load coil. For highly volatile solvents, a cooled spray chamber or vapor condenser must be used to remove excess solvent vapor from the aerosol stream. In this case, atom lines are enhanced appreciably, while ion lines are enhanced slightly, provided vapor condensation is efficient and a viewing height 20-30 mm above the load coil is used.

ACKNOWLEDGMENT
The assistance of David D. Smith in preparing organometallic standard solutions is gratefully acknowledged.

LITERATURE CITED
(1) Fassel, V. A. Anal. Chem. 1979, 57,1290 A. (2) Barnes, R. M., Ed. "Applications of Inductively Coupled Plasmas to Emission Spectroscopy"; Franklin Institute Press: Philadelphia, PA, 1978. (3) Boumans, P. W. J. M. ICP I n f . News/. 1979, 5, 181. (4) Barnes, R. M. Anal. Chem. 1978, 50, 100R. (5) Cresser, M. S. "Solvent Extraction In Flame Spectroscopic Analysls"; Butterworths: London, 1978. (6) Motooka, J. M.; Mosler, E. L.; Sutley, S.J.; Vlets, J. G. Appl. Spectrosc. 1979, 33, 456. (7) Warren, J. ICP I n f . Newsl. 1977, 2 , 282.

RECEIVED review September 30, 1981. Resubmitted and for Accepted March 1, 1982. This work was supported by the National Science Foundation under Grant No. CHE80-19947.