GB2203241A - Introduction of effluent into mass spectrometers and other gas-phase or particle detectors - Google Patents

Description

2203241 - 1 C114/E j

Title: Introduction of Effluent into Mass Spectrometers and other GasPhase or Particle Detectors

Background of the Invention

Successful liquid sample introduction into gas-phase or particle detectors is dependent upon the interface between the liquid stream and the detector. The co-existence of continuous liquid sample introduction and normal operating requirements of the gas-phase detectors present compatability problems. Difficulties are sometimes encountered in acCommodating the mass flow from the liquid stream into the detector. In addition, dearadation of thermally labile sample conniponents may occur during the evaporation processes prior to gas-phase detection. In the case=of gas-phase detectors such as mass spectrometers, where detection occurs at a reduced pressures, vacuum locks and pumping requirements may be considerations. General requirements for interfaces between liquid streams and gas-phase detectors are:

(1) The sample must be evaporated prior to detection; (2) Minimal thermal degradation should occur during the sample evaporation process; (3) The sample transport efficiency should be sufficiently high so that adequate sensitivity is observed; (4) The normal operating conditions of the detector 2 - should be maintained during sample introduction7 and (5) The sample's composition should be maintained while being transported to and through the interface (e.g. minimal chromatographic band broadening).

Success in interfacing liquid streams to gas-phase detectors depends on how well the foregoing requIrement-s The principal application of the present device to gasphase detection of liquid streams is the introduction of "he ettluent from a Iliquid chrom_atograph -n.o a mmass spectrometer. The interfacing between liquid chromatography (LC) and mass spectrometry (MS) is hereinafter. referred to as LC-MS. Although the present invention telat-es to the general field of liquid sample introduction into gas-phase or particle detectors, most prior work in this area has concentrated on LCMS because it has presented formidable obstacles to interface design. This background discussion therefore focuses on LC-MS.

Complex gas-phase detectors, mass spectrometers, detect gas-phase ions formed by a variety of mechanisms; electron impact (hereinafter EI) ionization, and chemical ionization (hereinafter CI) are the most commonly practiced approaches. With EI ionization, the sample gas at 10- 3 to 10- 6 tort. (133 mPa to 133 micro Pa) is bombarded with electrons of sufficient energy (generally 70 eV) to excite electronic energy levels of sample molecules beyond the ionization potential so that an electron is removed from the sample molecule, making it a positive ion. Upon sample ion formation in the EI mode, excess energy imparted to the sample molecule from. tline W1 i A bombarding electron causes bond cieavage or fLagmentation.

It is a characteristic and reproducible nature of E1 fragmentation, indicative of molecular, structure, that provides this technique with broad utility for the analysis of samples with an unknown composition. in contrast, the CI mode operates at higher pressures relative to EI (typically at one torr), whereby the ionization occurs due to collision of sample molecules with reagent gas ions. The analytical utility of CI is generally found in the presence of molecular weight information. With-CI, the limited and irreproducible fragmentation of sample mo.lecules is essentiali-y of no value. it should be stressed that the determines the qualitative information obtained with the mass spectrometer. Alternative ionization -t-e-Lln'Lques are atmospheric pressure ionization (hereinafter A.PI) at 760 101 kPa) 4 zorr k and field ionization at 10 tort (!.'i mPa). It is preferable to use a variety of ionization techniques, including EI and CI: tn obtain the inaximuTP - information for a given sample T11-MS techniques that place a restriction upon ionization conditions also are limited in the sample information obtained for. a given analysis.

Mass spectra of many compounds, usually those ionized under EI conditions, have been complied in massive computerized data-base libraries for subsequent comparison with acquired spectra (fragment ions) from samples of unknown composition. it would be therefore a significant advantage for LC-MS devices to make use of such spectral libraries because computer comparisons can be made in a matter of seconds. Hence, for the wide use there is a need for LC-MS devices that utilize EI ionization modes. Unfortunately only few prior art devices are reported to have the capability of producing EI spectra of thermally labile and/oi involatile compounds.

Effluent from either a liquid chromatogiaph or a liquid process stream must be accommodated by the mass sDectrometer interfacing techniques. The pressure requirements for ionization, as discussed., are dependent upon the mode of ionization, and limited by the mass flow into the ionization reqion of the mass spectrometer and the pumping capacity of the mass spectrometer. The evaporation of liquid flowing at 1-2 ml/min may produce as much as 1 litre/min of gaseous sample at STP, which amounts to 10 8 1/min of gas at 10- 5 torr. (1.3 mPa; i.e. EI conditions), far exceeding the pumping capabilities of conventional mass spectrometers. Ionization techniques which occur. at pressures of one millitorr (133 mPa) or. higher, such as C!, require less pumping but usually result in significant ion-molecule reaction chemistry which yields little structural fragmentation information. Due to the requirement of low pressure for EI ionization, direct introduction of a continous stream of liquid from a liquid chromatograph is difficult to attain without extremely large capacity pumping systems such as cryogenic pumping.

The evaporation or desorption process, whereby the sample is transformed into gas, may also result in thermal degradation (pyrolysis), reactions, or rearrangements of the original sample molecules. These sample losses are most prevalent with sample components that are thermally labile and/or involatile, commonly separated by liquid chromatography. Mass analysis of these thermally labile and/or involatile molecules is usually limited by the inability to produce intact gas-phase ions of these - species. Theiefore, it is important in development of interfaces between the LC and MS to vaporize the sample with minimal degradation or loss -of analyte.

There have been a variety of approaches to inteifacing the LC with the MS and this work has been extensively reviewed (1 to 4) -(these and subsequent bracketed numerals in this section referring to the Sources below). The common objective of all interfacing techniques is efficiency in the production of gas-phase sample ions.

Direct Liquid Introduction (DLI) is one of the simplest aiDnroaches to interfacing LC with MS. With DLI, the effluent from a liquid chromatograph flows through a tiny cit-cular aperture or tube with a diameter in the order of 3 to 10 micro m (microns). A high velocity cylindrical et is directed into the ionization c'ha--.iibet-. Therc have been a wide variety of designs using this approach and they all have the same basic configuration (reviewed in 5 and 6). The jet may proceed through a heated desolvation region before entering the ionization region to aid in solvent evaporation. This technique typically had been limited to micro- bore LC flow rates, less than 100 microlitres per minute. To accommodate direct introduction of liquid into ion source, cryogenic pumping has been used to trap the excess sample onto a cold surface of the outside of the ion source. In cases where normal LC flow rates are used, 1-2m1/min, the effluent has been split, leaving only a fraction of the sample to be sampled into the mass spectrometer. Another limitation of the DLI technique is that the spectra produced yield only CI data. Little or no structural information is thus obtained, in contrast to El. in addition, more costly differential pumping is required to maintain the mass

1 6 - zalyzei pressures sufficiently low. In piactice DLI has Xcen plagued by repeated clogging of the micron sized,..ifices, causing the approach to be cumbersome, with,oificant downtime. The alignment and the instability. g.micron sized liquid jets also make DLI experimentally:Oicult in that data acquired may be noisy and -t,g-eproducible. However, the advantage of this technique:;,;.the lack of thermal degradation when analyzing tbermally labile compounds. Further discussion of this.N-p,chnique may be found in U.S. Patents 3,997,298 of Zh_cember 14, 1976 and 4,403,147 of September 6, 1983.

-MS approach whereby the phanical Transport (MT) is an LC.Ptluent from the LC is deposited on a moving surface, ggph as a wire or belt. Heat may be applied to the sample 1g remove solvent and the desolvated sample is,.Wchanically transported on the wire or belt through a gries of vacuum locks into the low pressure ion source of t.,e mass spectrometer. Both EI and CI mass spectra have -b. ten obtained with this technique. A limitation of this -tg-.chnique is the requirement that the sample be evaporated desorbed from the moving surface prior to ionization. e.,e,rmal degradation may occur during the thermal oration process. Operation of mechanical transport devices is frequently cumbersome due to design complexity jamming of moving parts. The chromatographic profile sample may be degraded by the non-uniform application sample upon the moving surface. This approach is,gplained in greater depth in U.S. Patent 4,055,987 of 0ovemh-er 1, 1977.

T"ormospray (TSY) is a more widely used approach to LC-MS.,r,pp effluent from the LC flows through a thermal vaporizer 4,t-o a heated vaporizer chamber in the ion source region _i f.

A - 7 j of the MS. The thermal vaporizer transforms the sample into an ion-vapor plasma in a vaporizer chamber. A small fraction of the ionvapor is sampled into the ion optics region of the mass spectrometer through a small aperture. The efficiency of sampling analyte throught the sampling aperture is quite low. The majority of the ion-vapor is evacuated through a roughing line connected to the vaporizer chamber. As with DLI, costly differential pumping between the ion optics region and the mass analyzer region is required to maintain an adequate vacuum. The vaporization process produces gas-phase reagent ions when buffered solutions, such as aqueous ammonium acetate, are pumped through the thernial vaporizer.. This ionization process, known as thermospray ionization, produces CIlike spectra. Under normal operation conditions, thermal degradation has been observed with the use of the thermal vaporizer; however, a large number of thermally labile compounds have been analyzed with this technique with minimal degradation. TSY has several limitations, most notably is the lack of structural information such as that obtained under EI ionization conditions. The response of various compounds depends upon the chemical nature of the substance being analysed. Consequently, it is sometimes difficult to predict response for poorly characterized samples. Thermospray process are described in further detail in Canadian Patent 1, 162,331 of February 14, 1984,and U.S. Application Serial No. 527,751, filed August 30, 1985, and continuations thereof.

Monodispersed Aerosol Generation Interface for Combining liquid chromatography with mass spectrometry (MAGIC) is an approach to LC-MS whereby effluent is pumped through a tiny orifice or tube, forming a stable liquid jet. The 1 liquid jet breaks up into uniformly sized ot monodispeised droplets. The droplets are dispersed in a nearatmospheric pressure desolvation chamber with a dispersion gas that serves to prevent coagulation of the droplets as well as conduct thermal energy to the droplets a resulting in rapid desolvation. This approach requires a large diameter desolvation chamber at near atmospheric pressure to allow efficient desolvation. The effect of lowerinq desolvation chamber pressure on the rate of solvent evaporation has theroretically been treated by Fuchs and Sutugen (16). The rate of evaporation of a liquid droplet is significantly reduced with decreases in pressure. In the absence of dispersion gas, the droplets receive insufficient thermal energy which prevents their complete desolvation. Dispersion gas flows of greater than 1 litre/min have been used in-order to maintain sufficiently high pressure in the desolvation chamber. Subsequent to desolvation, solvent-depleted solute particles are accelerated through a nozzle into a vacuum chamber to form a high velocity aerosol beam. The lighter solvent vapor and dispersion gas, compared to the more massive solute particles, expand outward from the axis of the aerosol beam, leaving a collimated particle beam devoid of gaseous components. The gaseous components of the aerosol beam are removed in a two-stage pressure reduction process, accomplished by directing the particle beam through two successive skimmers that separate two successively lower pressure vacuum chambers. The solute particle beam proceeds through the skimmers into the ion source region where enriched solute is thermally desorbed from surfaces in the ion source region and ionized by conventional Cl or EI ionization process.

The MAGIC approach to LC-MS has the advantage of ionizing i solute under EI conditions. Howevei-, the requirement of near atmospheric pressure desolvatio n significantly reduces the solute transport efficiency into the low pressure ion source of the mass spectrometer. The addition of high flow rates of gas dispersion creates turbulence at the nozzles, and significant loss in transport efficiency is observed due to impact on the surfaces of the skimmers and. nozzles as well as walls of the desolvation chamber. The requisite high gas lead also tends to increase the solid angle expansion of the particle beam and to favour. the use of a less efficient two-stage separator device. Because of these conditions, transport efficiency of solute into the ion source is generally in the order, of 5%. With MAGIC, the mobile phase composition does not affect the response for various analytes as does the thermospray technique which in some cases required mobile phase additives for sensitive response. Also, no differential pumping is required with this technique when EI ionization is the only mode employed. Additional details on this technique are presented in U.S. Patent Application Serail No. 623,711 filed June 23, 1986 by Willoughby and Browner, and in a continuation thereof.

MAGIC can be considered a particle beam introduction technique. For this discussion, particle beam introduction is considered as a technique of accelerating an aerosol through a nozzle into successive vacuum chambers while skimming the aerosol particles on axis, forming a particle beam, and pumping away gaseous components of the aerosol beam off-axis. The result of this process is the efficient separation of aerosol particles from gaseous material, with the particles being transported more efficiently into lower pressure regions because of the higher momentum of the particle when compared to the gas molecules. Prior particle beam introduction techniques for mass spectrometry have applied to two areas: (1) Real-time aerosol monitoring (7-9); and (2) Liquid sample introductive where an aerosol generation step precedes the particle beam introduction (10-14). The MAGIC technique is an example of the latter. The present inventLion also includes a particle beam solute enrichment step when applied to sample introduction into the mass spectrometer.

Peformance of particle beam introduction techniques is dependent upon the properties of the aerosol. The solid angle dispersion of the particle beam is dependent upon the size of the solute particles, the pressure from the aerosol source, And the geometry of the nozzle. Israel and Friedlander (15) experimentally showed the relationships of these parameters on particle beam dispersion. Their results show: (1) Particle beam angular dispersion increases with aerosol source pressure; (2) Particle beam angular dispersion decreases with increase in particle size; and (3) Particle beam expansion is more uniform with changes in particle size when capillary versus converging nozzles are used. Therefore, the nature of the aerosol generation process in terms of gas flow and pressure, and particle size and distribution ultimately determines the efficiency of the particle beam introduction technique.

A variety of aerosol generators have been used with the particle beam approach to liquid sample introduction into the mass spectrometer. These include the Berglund-Liu,

J monodisperse aerosol generator (8, 10-14), the WilloughbyBtowner monodisperse aerosol generator (14), and DeVilbiss and ultrasonic nebulizer (10-13). A major limitation of prior particle beam techniques was the difficulty in desolvation of the aerosol droplets subsequent to aerosol generation. Prior techniques required a desolvation chamber or increased gas load to remove solvent from the droplets. 'the generation of droplets greater than about 10 microns in diameter with prior aerosol generation techniques leads to greater likelihood of particle losses in the desolvation chambers and nozzles due to impaction or settling process. The aerosol generation process of the present invention is designed to permit precise control over aerosol properties, including the droplet size, direction, and rate of evaporation. With enhanced control over the aerosol generation and desolvation processes, the efficiency of the particle transport to various detectors is increased.

The solid angle dispersion of particle beams has been shown to increases with increase in aerosol source pressure (15). Thus, the prior particle beam techniques that require high gas loads for aerosol generation or desolvation tend to have more divergent particle beams. This requires that only part of the particle beam crosssection can be sampled through axial skimmers because in subsequent chambers exceed the upper pressure limitation of the detector. Thus, the entire cross-section of a less divergent particle beam could in theory be collected with the same skimmer diameter while maintaining the same detector pressure. The result of a less divergent particle beam is more efficient sample transport to the detector. Consequently, an objective of the present device is to decrease the gas load from the aerosol - 12 generation process to enhance sample transport efficiency.

The use of particle beam techniques for sample introduction into the mass spectrometer has demonstrated the ability to produce spectra under electron impact ionization conditions (7-14). A major objective of the present device is to enhance the ability to volatilize the particles once the particle beam enters the ion source region of the mass spectrometer. The objective is to form intact gas-phase molecular species of substances originating in the particle. The prior particle beam sammie introduction devices have experienced difficulty in forming intact molecular ions because of thermal fragmentation of molecules during evaporation from heated surfaces (8). Particle volatilization process depends upon the equilibrium surface vapor pressure of molecules originating in thee particles, the temperature and material of the particle beam collection surface, and the presence of other components in the particle matrix. Control of these factors is essential to the performance of the present device.

Other applications of liquid sample introduction into gasphase or particle detectors have been reported for light scattering (17), flame ionization (18), atomic absorption or emission spectrophotometry (19). The enhanced control of aerosol generation, desolvation and solute- enrichment with the present device is applicable to a variety of detectors.

Sources mentioned in the above background history are:

P.J. Arpino, J. Chormatogr. 323, 3 (1985).

z 1 - 13 2. D.E. Games, Adv. Chomatogr. 21, 1 (1983).

3. C.G. Edmonds, J. A. McCloskey, V. A. Edmonds, Biomed Mass Spectrom. 10, 237 (1983).

4. R. C. Willoughby, R. F. Biownei, Trace Analysis. Vol 2, p.69, ed. J. F. Lawrence, Academic Press (1982).

5. W. M. A. Niessen, Chromatographia, 21, 5 (1986).

6. W. M. A. Niessen, Chromatographia, 21, 5 (1986).

7. J. J. Stoffels, "A Direct Air-Sampling Inlet for Surface Ionizationn Mass Spectrometry of Airborne Particles," presented at the 24th Annual Meeting of ASMS, San Diego, Cal. 1976.

8. M. P. Sinha, C. E. Griffin, D. D. Norris, and S. K. Friedlander, "Analysis of Aerosol Particles by Mass Spectrometry", presented at the 28th Annual Meeting of ASMS, New York, NY 1980.

9. J. Allen and R. K. Gould, Rev. Sci. Instum. 52 (6), June 1981.

10. F. T. Greene, "Particulate Impact Mass Spectrometry", presented at the 23rd Annual Meeting of ASMS, Houstnn Texas, 1975. F. T. Greene, "Mass Spectrometry of Nonvolatile Materials and Solutions y the Particulate Impact Technique," presented at the 24th Annual meeting of the ASMS, San Diego, Cal. 1976. F. T. Greene, "Fur-ther Development of Particulate Impact Mass Spectrometry," presented at the 29th Annual Meeting of the ASMS, New York, NY 1980. F. T. Greene, "The Current Status of Particulate Impact Mass Spectrometry," presented at the 29th Annual Meeting of the ASMS, Minneapolis, Minn. 1981.

14. R. C. Willoughby, "Studies with an Aerosol Generation Interface for Liquid Chromatography with Mass Spectrometry," PhD Thesis, Georgia Institute of Technology, 1983.

12.

13.

v 14 - G. W. Israel and S. K.

Interf. Sci. 24, 330 (1967 16. N. A. Fuchs and A. G Aerosols". Ann Arboi Fiiedlander. J. Colioid Sutugen. "Highly Dispeised Science, Ann Arbot (1970). 17. J. W. Jorgenson, S. L. Smith, and M. Novotny, J. Chromatogr., 142, 233 (1977). 18. E. Haakti and T. Nikkari, Acta Chem. Scand. 17, 2565 (1963). 19. R. F. Browner and A. W. Boorn, Anal. Chem. 56/71, 7871A (1984).

The above sources are incorporated by reference herein. Summary of the Invention

The disclosed invention, defined in the appended claims, is a method and apparatus for introducing into analytical devices liquid effluent from process streams, flow injection streams, or liquid chromatographs into gas-phase or particle detectors. It is applicable to liquid sample introductio n into a variety of analyical devices including mass spectrometers, flame ionization detectors, light scattering detectors, and other apparatuses suitable for determining the nature of analytes in the gaseous or particulate states.

Basic processes occurring in the present device are aerosol generation and desolvation, solute enrichment, and detection of solute by a suitable gas-phase or particle detector.

Aerosol generation with the present invention is obtained by concentric flow of liquid (inner flow) and gas streams (outer flow). The gas is heated by direct contact with a is heat souice, geneially a heated tube that sheathes the gas. The tube is heated by controlled resistive heating of the tube or direct contact of the tube with a cartridge heater. By precisely controlling the flow of jas through the outer tube, the flow of liquid through the inner tube, the dimensions of both tubes, and the power imput fox. the heat source, the aerosol properties are precisely deter-mined. Heat is conducted across the gaseous medium and therefore the thermal conductivity of the gas is preferred to be high (e.g. hydrogen, helium).

The amount of heat supplied across the gaseous medium to the liquid determines the degree of desolvation or evaporation of solvent that occurs during the aerosol generation process. The gas supply serves two functions in aerosol generation. First, it conducts the 'neat necessary for desolvation. Second, it confines or sheathes the aerosol particles, preventing the particles from wide dispersion and impacting chambei walls with expansion. The present device requires no desolvation chamber because solvent evaporation takes place entirely inside the inner tube of the aerosol generator.

The controlled aerosol generation and desolvation with the present device effectively separates the solvent from the solute due to the solute being generally less volatile than the solvent. The solvent will be in the gasphase and the solute will remain in the particulate state.

Once separate in phaSE the two methods. The separates the solvent or momentum separator, particles are carried solute enrichment occurs by one first method of solute enrichment from the solute in a particle beam where the higher momentum solute more efficiently into pioaressiveiy - 16 lower piessure regions separated by skimmer. apertutes. The present device utilizes either, single or dual-stage particle beam pressure reduction. The particle beam configuration in the present device transports most of solute to the low pressure detection region while removing more than ninety-nine per cent of the solvent. The second method of solute enrichment separates solvent from the solute because of mobility of particles compared to gases. The gaseous solvent components of the aerosol havinq higher. mobility interact appreciably with cold surfaces and are trapped on the surfaces, cryotrapping. The solutes, in the particular state, are carried in the gas flow by the poorly condensable carrier gas such as helium or. hydrogen, leaving the solvent vapors behind. A combination of crotrapping and particle beam solute enrichment is a third alternative.

Detection of enriched solute with the present device is accomplished by a variety of means. One embodime,-,."- of the present invention uses particle beam enrichment to direct solute particles into the ion source of the mass spectrometer. The particle beam is intersected by sources which may include primary ion beams, laser beams, discharge plasmas, electron beams, electric fields, or, magnetic fields. Under these operating conditions, energy for solute evaporation and ionization is supplied directly to the solute particles during flight. Another, embodiment utilizes a target surface to collect the solute particles. The target surface is generally composed of an inert material at a controlled temperature and serves to conduct heat to the particles for, obtaining rapid solute vaporization. once the solute is vaporized, normal gasphase processes provide ionization such as electron impact or chemical ionization. A target surface with collected z paLticles may be bombarded with ions, neutral, or electron beams to create gas-phase ions from the target surface. Alternatively, the solute is collected on a cold target surface for a period of time before heating the target, thus concentrating sample to lower, the detection limits. Measurement of power supplied to the target can also be used to determine heat of vaporization.

The use of othel. gas-phase detectors such as the flame ionization detector (FID) require cryopumping for solute enrichment and hydrogen as the nebulization gas. This embodiment operates with atmospheric pressure or low pressure flames.

The particle beam embodiment is also used with laser scattering or, continuum light scattering measurements and functions as a universal liquid chromatography detector.

Brief Description of the Drawings

The invention will now be described, by way of example only, with reference to preferred embodiments shown in the accompanying drawings, in which:

Figure 1 is a schematic diagram in cross-section of a thermal concentric aerosol generating apparatus with resistive heating of the conductive aerosol generation gas; Figure 2 is a schematic diagram in cross-section of a thermal concentric aerosol generating apparatus similar to Figure 1, but with cartridge heating of the conductive aerosol generation gas; Figure 3 is a schematic diagram in cioss-section of a thermal concentric aerosol generating apparatus and single-stage particle beam solute enrichment to interface with a conventional mass spectrometer ion source chamber flange; Figure 4 is a schematic diagram in cross-section of a thermal concentric aerosol generating apparatus similar to Figure 3, but with dual-stage particle beam solution enrichment to interface with aconventional mass spectrometer ion source chamber flange; Figure 5 is a schematic diagram in cross-scettion of a thermal concentric aerosol generating apparatus similar to Figure 4 but with an alternative embodiment of dual-stage particle beam solute enrichment to interface to a coventional mass spectrometer ion source (:namher- gate valve; and Figure 6 is a diagramatic view of a thermal concentric aerosol generating apparatus and solvent cryotrapping solute enrichment to interface to a flame ionization detector.

Detailed Description of Embodiments

The present device has three component parts: an aerosol generator 14, a solute enricher, and a solute collector or detector.

The first of these component parts, aerosol generator 14, is described in detail with reference to Figures 1 and 2. Flowing into aerosol generator 14 is liquid from supply 30, and gas from supply 31. Gas flows through a capillary 1 - 19 tube 11, and liquid through a tube 10. Critical to the operation of aerosol generator 14 is the coaxial supply of heat across the flowing gas medium, between tubes 10 and 11, to flowing liquid in tube 10. The dimensions of the tubes and the flow rates of gas, liquid, and heat determine the properties of the generated aerosol.

The liquid supply 30 for the present aerosol generator is the effluent from liquid process streams, liquid chromatographs, or flow injection streams, the effluent containing dissolved analytes of interest in addition to other less volatile constituents, either present naturally or added purposefully. Fused silica capillary tube 10 functions as a nozzle to confine the flow of the liquid effluent. Tube 10 restricts the flow of liquid resulting in increased linear velocity of as increased surface contact per the liquid stream as well unit volume of liquid with the heated walls"of the fused silica capillary. The inner diameter of the fused silica capillary tube 10 has dimensions that are determined by the liquid flow rate requirements for a given application. The minimum inner diameter of tube 10 is determined by the upper pumping pressure limit of liquid supply 30. Liquid flow rate, length, and inner diameter of tube 10 have effect on the liquid supply pressure. Typical dimensions of the fused. silica capillary for liquid flows in the range from 0.1 to 2.0 ml/min is 50 micrometers inner diameter and 250 micrometers outer diameter. inner diameter dimensions for tube 10 have been successfully tested at 10, 25, 50, 75, and-150 micrometers. The length of the fused silica capillary tubing is that sufficient to permit heat transfer.. to the liquid stream. A typical length is 20cm. The maximum length of fused silica capillary tube 10 is determined by the pressure limit of the liquid pumping A system.

Gas supply 31 for. the aet,osol gener'ator 14 comprises a regulated gas sout,ce, compressed or.. self-generated, of a thermally conductive gas or mixtur,e of gases. The gas passes through a tubular conduit 15 which is perpendicular to the tube 11 and to which it is joined by a tee union 16. The coaxial metal capillary tube 11 sheathes the fused silica tube 10 and confines the flow of neublizergas supplied from a regulated gas supply 31 and controlled by a precision valve 35 (seen in Figui,e 3). The inner diameter of the metal capillary tube 11 and the gas flow rate from supply 31 detetmine the linear vei-ocity of the gas through the metal capillary tube 11 and, consequently, the linear velocity of the resulting concentric sheath of gas 33 in the aer.osol generation process. The concentr'ic gas flow serves two functions in the present device: first, to sheath the aerosol exiting from the fused silica capillary tube 10; and second, to serve as a conductive medium for heat transpott from the heated outer metal capillat,y tube 11 to the inner fused silica capillary tube 10.

The heat supply for the present aerosol generator is composed of electrical resistance of the metal capillary tube 11 which causes it to heat. Figur,e 1 illustr'ates means for supplying heat to increase the tempex,ature of capillary tube 11 by passing current thtough same; the tube being the resistively heated part of the heating circuit. The length, composition, and wall thickness of outer tube 11 determine the power requirements of a heating power supply 20, controlled by a heater controller. 23. The heating circuit is controlled by maintaining either, constant resistance in the circuit or a constant - 21 temperature by means of a thermocouple feedback 24. The heated outer tube 11 is preferably composed of a pure metal such as nickel or platinum, because temperature is porportional to resistance for such pure metals as well as many other pure metals. This relationship permits control of the heat supply or temperature by direct resistance feedback measurement, without the requirement of thermocouple feedback control. This present device may also use thermocouple feedback for heat supply control and resistively heated alloys rather than pure metals. The resistive heating- circuit is electrically isolated from ground by appropriate mean's such as insulators located at 12 and 13. The inner diameter of the heated metal capillary tube 11 is slightly larger than the outer diameter of the inner. fused silica capillary tube 10. A typical range for the inner diameter of tube 11 is 300 to 400 micrometers. Within this range the gas velocity is sufficiently high to entrain a liquid jet or aerosol emerging from the fused silica capillary 10 at a position as shown by arrow 32. In addition, the interstitial spacing is small enough to allow efficient heat transport across the gas to the fuses silica tube 10. There is a portion of capillary tube 11 that is not part of the resistively heated circuit and is connected to the heated portion of tube 11 by the electrically insulated union or insulator 12. The region surrounding the outer metal capillary tube 11 conducts heat at a slower rate compared to the rate of heat transport to the inner fused silica tube 10. Consequently, the outer tube is thermally insulated with an air space, a thermal insulating substance, or a vacuum, to ensure heat transport to the flowing liquid stream.

Figure 2 illustrates an alternative means of heat supply .1 to the metal capillary tube 11 by cartridge heating. Cartridge heaters 26 are inserted into a metal block in thermal contact with the metal capillary tube 11. With cartridge heaters, the means of control for the beater power supply 20 is through thermocouple feedback 24 to controller 23.

The heated portion of the aerosol generator is contained in a protective housing 28 that serves to support the aerosol generator. as well as protect the operator from potential burns or electrical shock. The aerosol generator is attached to aerosol expansion chambers via connection 29 which may be a gasket or 0-ring seai or both.

The aerosol generation with the present device is obtained by combining the coaxial flow of liquid, gas, and heat in a precisely controlled manner. The aerosol is generated at position 32 and confined along the axis in the direction of flow by sheath gas 33. The coaxial heat transport to the flowing liquid is controlled by electrical feedback circuitry and by the flow of gas between the outer heated metal tube 11 and the inner fused silica capillary tube 10, the gas being the conductive medium across the interstitial space. The thermal conductivity of the gas is a critical parameter in the transport of heat to the inner fused silica tube 10. it is preferred to have the gas supply constitute a high conductivity gas such as hydrogen or helium, but not excluding other less conductive gases or gas mixtures.

The preferred operation conditions for the present aerosol generator depend upon the required aerosol properties for a given application. The range of aerosol properties varies from a pneumaticly nebulized solvent-iich aerosol with relatively large diameter droplets to a thermally nebulized solvent-depleted aerosol with relatively small diameter droplets. The combined pneumatic and thermal nebulization processes yield aerosols that have controlled variation in droplet size, degree of desolvation of droplets, and direction of flow of the generated aerosol generator, as described, functioning to produce solventdepleted solute particles, The aerosol generated with the present device requires a solute enrichment step in the embodiments where solute detection is degraded by the presence of proportionately large quantities of solvent. The present- device is most generally applicable to effluents where the solutes are less volatile than the associated solvent or soluents. The volatility difference between the solvent and solute results in solute being predominately located in the particulate portion of the aerosol and the solvent predominately located in the vapor portion of the aerosol.

Figures 3 to 5 illustrate embodiments of the present invention with aerosol generation, particle beam solute enrichment, and mass spectrometric detection respectively. Figure 6 illustrates an embodiment of the present device with aerosol generation, solvent cryotrapping for solute enrichment, and flame ionization detection. The application of the present device for aerosol generation, solute enrichment, and detection with other modes of detection are not illustrated, but the modifications necessary to attain same will occur to those knowledgeable in the field of liquid sample introduction into gas-phase or particulate'detectors from the embodiments disclosed

24 - herein.

Figure 3 depicts an embodiment of the present invention with single stage particle beam solute enrichment. The device is attached to an ion source chamber 60 of a mass spectrometer via a flange vacuum joint 62. The aerosol generator described previously is attached to an aerosol expansion chamber 40 by a sealed joint 29. The gas supply 31 is shown controlled by the precision valve 35. Expansion chamber 40 provides sufficient space for the high velocity aerosol generated at 32 to be slowed down in a viscous flow region and to proceed in the direction indicated by the dashed line-and arrows. The pressure in the expansion chamber may vary from near atmospheric pressure to 1 torr (133 Pa) depending upon the mass flow rate from the aerosol generator. The solute particles and solvent vapor are accelerated through a nozzle 42, forming a high velocity aerosol beam along a longitudinal axis between nozzle 42 and a skimmer 43. The beam forms due to the pressure drop between expansion chamber 40 and a vacuum chamber 41. Vacuum chamber 41 is evacuated by a pump 44, generally a large pumping capacity mechanical pump such as a 400 1/min rotary pump. In the region between the axially aligned nozzle 42 and the skimmer 43 the solvent vapor and conductive gases from the aerosol expand significantly more rapidly than the solute particles. As a consequence of differential expansion of gases and particles, the particles are highly enriched at the axis the expanding aerosol beam. The enriched solute particles are sampled into the ion source chamber of the mass spectrometer through skimmer 43. An enriched solute particle beam is formed from the skimmer 43 to an ionization region 61 for a mass spectrometer, shown by a dashed line at the centre of the chamber 60. The distance - between the point where the aerosol beam is formed at nozzle 42 and the ionization region should be kept to a minimum, generally 5 to 10 cm.

Figure 4 illustrates an embodiment of the present invention with twostage solute particle beam enrichment. As described with respect to Figure 3, the device is attached to the ion source chamber 60 of a mass spectrometervia flange joint 62. The aerosol generator is attached to the aerosol expansion chamber 40 at sealed joint 29. The aerosol axially expands from the aerosol generator at 32 and proceeds down the axis of the expansion chamber in the direction indicated by the dashed line and arrows. The aerosol is accelerated through nozzle 42 forming a high velocity aerosol beam between nozzle 42 and skimmer 43. The aerosol beam is formed due to the pressure drop between the expansion chamber 40 and the first vacuum chamber 41. A second vacuum chamber 46 provides a higher degree of solute enrichment by pumping away additional solvent vapor in the region between skimmer 43 and a further skimmer 49. The first vacuum chamber 41 is evacuated by pump 44 and the second vacuum chamber 46 is evacuated by a pump 45. Pumps 44 and 45 have sufficient pumping capability to remove most of the solvent vapor introduced by the aerosol generator. Nozzle 42 and skimmers 43 and 49 are, similar to before, axially aligned to permit sampling of enriched solute particles into progressively lower pressure regions. The distance between the nozzle 42, where the aerosol beam is formed, and the ionization region 61 is minimized to ensure solute particle transport efficiency. This distance is generally 1 to 10 cm.

Figure 5 illustrates an embodiment of the present invention with two-stage solute particle beam enrichment in an alternative embodiment to that shown in Figure 4. The device is removable from the ion source chamber 60 of the mass spectrometer through a standard gate valve 64. An insertion probe portion 65-of this device is inserted into the gate valve 64 (automatically opening same) so as to be axially aligned with the ionization region of the mass spectrometer. The aerosol generator is attached to aerosol expansion chamber 40 at sealed joint 29. The aerosol axially expands from the aerosol generator at 32 and proceeds down the axis of the expansion chamber in the direction indicated by the dashed line and arrows. The aerosol is accelerated through nozzle 42 forming a high velocity aerosol beam between nozzle 42 and skimmer 43. The aerosol beam is formed due to the pressure drop between the expansion chamber 40 and the first vacuum chamber 41. A second vacuum chamber 46 provides a higher degree of solute enrichment by pumping away additional solvent vapor in the region between skimmer 43 and skimmer 49. The first vacuum chamber 41 is again evacuated by pump 44 and the second vacuum chamber by pump 45. Pumps 44 and 45 have sufficient pumping capability to remove most of the solvent vapor and conductive gas introduced by the aerosol generator. Nozzle 42 and skimmers 43 and 49 are, as previously, axially aligned to permit sampling of enriched solute particles into progressively lower pressure regions. The distance between the nozzle 42, where the aerosol beam is formed, and the ionization region 61 is minimized to ensure solute particle transport efficiency; however, with this embodiment, the additional length of the insertion probe 65 is required. This distance is generally in a range of 20 to 40 cm.

Figure 5 also discloses optional attachments 67 which may be introduced into ion chamber 60 proximate to and around ionization region 61 for special purposes. For example, attachment 67 may be a laser whereby a laser beam is focused on to the surface of target region 61, thus subjecting the beam to photoionization and laser desorption analysis. Also attachment 67 may constitute an electron source for chemical ionization or a high voltage source to ionize particles and molecules by discharge or, -field ionization.

Yet further, attachment 67 may comprise a cryotrap for collecting solvent vapor on cold surfaces while allowing solute particles to pass through the cold trap for subsequent detection. Another form of attachment 67 is apparatus for providing an optical region across the axis of the particle beam for making light scattering measurements on the beam. Attachment 67 may further comprise a support for a moving target, a belt 68 shown in dashes lines, which collects solute particles as a function of time, and wherein apparatus incorporated in attachment 67, or separate apparatus, subsequently locates and analyzes the chromatographic profile so received by surface measurement techniques such as SIMS, infra-red, Xray, ultraviolet, or visible spectrophotometry scanning or the like such as reflectance or transmittance measurement techniques. Further, belt 68 may collect highly purified solute crystals for subsequent structure analysis. Belt 68 or its equivalent, such as a disc or moving strip, may be heated for a continuing on-line thermal analysis. In such event, attachment 67 also comprises means for heating the target, controlling such heat, and precisely measuring the thermal energy consumed by evaporation or desorption of solute from the target.

An attachment 67 can constitute apparatus for generating a high energy discharge of sufficient energy to charge surfaces of particles in the beam and thereby enhance ion desorption or particle fission by coulombic repulsion. Attachment 67 may be built-in or, preferably, readily attachable and removable, and a plurality of attachments 67 may be disposed in chamber 60 operably proximate the target and region 61 and so that they may be employed alone or in combinations, as desired.

The enriched particle beams produced with the embodiments shown in Figures 3 to 5 contain the solute particles into gas-phase ions in a similar manner as with each of these devices, the solute particles are collected on a target surface 50. The target surface is a resistively heated surface that supplies thermal energy to minute solute particles to vaporize the solute molecules. The target is inserted through gate valve 63 so that solute vporization occurs in the ionization region 61 of the mass spectrometer. The temperatue of target surface 50 is controlled by a controller 52 with a thermocouple feedback 53 and a power supply 51. The collected solute particles are heated at low temperatures for thermally sensitive compounds and at high temperatures for involatile species and atomization." The operating temperature range for the target surface 50 ranges generally from 100 to 3000'C. Ionization of the gas-phase solute molecules occurs by conventional ionization processes such as electron impact or chemical ionization.

The ionization processes occurring in the device described with respect to Figures 3 to 5 ar.e not limited to gasphase ionization. The solute particle beams are also collected on target surface 50 and ionized with 29 - conventional surface ionization techniques such as fast atom bombardment, secondary ion mass spectrometry, field desorption, thermal ionization, plasma desportion, and laser desorption as described with reference to Figure 5. These techniques require the introduction of an alternative energy soure to the target surface. In addition to surface ionization processes, the present device also permits the introduction of energy to the solute particle beam directly without collection of- the particles on a surface prior to ionization. With this embodiment, target surface 50 need not be present. The solute particle beam intercepts, in flight, a primary ion beam, -- primary atom beam, a laser beam. or a high field region.

Figure 6 illustrates an embodiment of the present invention with solvent cryotrapping to provide solute particle enrichment. The aerosol generator is attached to the aerosol expansion chamber 40 at sealed joint 29. The conductive gas used for aerosol generation with this embodiment is hydrogen gas. The aerosol axially expands from th aerosol generated at 32 and proceeds down the axis of the expansion chamber in the direction indicated by the dashed line and arrows. The walls of the expansion chamber 40 are cryogenically cooled to trap the solvent vaopr as shown by a cryotrap 80. The solute particles and hydrogen gas are passed through the expansion chamber more efficiently than the solvent vapor. The enriched solute particles and hydrogen gas are introduced into a burner chamber 71 through an inlet 70. Here, the particles are burned in a hydrogen flame 75 and the ions produced in the flame are collected for detection on electrode grid 73. Air or oxygen is introduced into the burner chamber 71 through an inlet 72.

The foregoing description of specific embodiments is for clearness of understanding by those skilled in the art and unnecessary limitations should not be understood therefrom. The cited prior art patents, literature and patent applications may assist in the understanding of the invention by those skilled in the art as well as those who may desire or need to acquire such an understanding.

9 1 -

Claims (57)

1. Claims

   C114/E 1. A thermal concentric aerosol generating device for obtaining solvent- depleted solute particles of micron and sub-micron size in a well defined direction from a liquid sample, the sample containing volatile solvent and less volatile solute, the device comprising: a. an inner fused silica capillary tube to transport liquid into a high velocity liquid jet, b. an outer metal capillary tube coaxial to the inner tube to transport a thermally conductive gas, c. heating means for controllaby heating said outer tube, d. a,union to connect liquid and gas supplies to sai4 coaxial tubes, e. means for supplying liquid to the inner tube, and f. means for supplying a thermally conductive gas (eg helium or hydrogen) to the outer tube to enhance transport of thermal energy from the outer tube to the inner tube and to the liquid therein, whereby the solvent is vaporized during the aerosol generation process, leaving highly enriched solute particles entrained in a high velocity stream of conductive gas.
2. 2. A device as defined in Claim 1, wherein said heating means comprises an electrical circuit with said outer metal capillary tube being the heating element of said circuit, said outer metal tube being composed of high purity metal having a comparatively high linear relationship between its temperature and resistance.
3. 3. A device as defined in Claim 1, wherein said heating means comprises an electrical circuit which includes as a heating element a cartridge beater in thermal contact with the outer metal capillary tube.
4. 4. A device as defined in any one preceding claim, which further includes an expansion chamber concentric to the flow from said inner tube which provides adequate space for the high velocity gases and particles to have their velocity reduced therein without significant loss of sample due to particle impaction or settling.
5. 5. A device as defined in Claim 4, which further includes a supply means for heating said expansion chamber, a control means for controlling the said supply means for controlling said supply means, and a sensing means for monitoring the temperature of said expansion chamber.
6. 6. A device as defined in claim 5, which further includes a nozzle restriction at the downstream side of said expansion chamber and coaxial to the flow of the aerosol generator, whereby the flow of said aerosol thereform is accelerated through said nozzle forming a high velocity particle beam.
7. 7. A device as defined in Claim 6, which further includes a low pressure chamber downstream from said nozzle, whereby the aerosol flow enamating from said nozzle is allowed to expand outwardly from the axis of said nozzle, and vacuum pumping means to maintain a sufficiently low pressure in said chamber.
8. 8. A device as def ined in Claim 7, which further includes a skimmer located in said chamber axially aligned with said nozzle, whereby the solute particles are - 3 3 - preferentially sampled compared to the solvent and conductive gas vapors by said skimmer.
9. 9. A devices as defined in Claim 8, which further includes an ion source region of a mass spectrometer axially aligned with said solute particle beam emanating from said skimmer.
10. 10. A device as defined in Claim 8 or Claim 9, which further includes a low pressure chamber downstream from saod skimmer, said secondlow pressure chamber being pumped by pumping means to maintain sufficiently low pressure in said chamber.
11. 11. A device as defined in Claim 10, which further includes a second skimmer located in said second low pressure chamber axially aligned with said skimmer, whereby the solute particles are preferentially sampled over the solvent and conductive gas vapors by said skimmer.
12. 12. A device as defined in Claim 11, which further includes an ion source region of a mass spectrometer axially aligned with a solute partice beam emanating from said skimmer.
13. 13. A device as defined in any one of Claims 9 to 12 comprising means for being affixed directly to the housing of a mass spectrometer.
14. 14. A device as defined in any one of Claims 9 to 12, in combination with a mass spectrometer interface including an insertion probe which is readily attachable and removable from the ion source region of said mass -5 4.

    spectrometer through a vacuum interlock.
15. 15. A device as defined in any one of Claims 9 to 14, which further includes a heated target axially aligned with the solute particle beam so that said target causes rapid evaporation or flash desorption of the collected solute particles.
16. 16. A device as defined in Claim 15, which further includes control means for controlling the desorption and/or evaporation or solute from the sad heated target so that: a. the collected solute particles are desorbed or evaporated as intact molecular species prior to ionization by electron impact or chemical ionization processes, or b. the collected solute particles are thermally ionized from the surface as intact molecular ions, or C. the collected solute particles are pyrolyzed on the surface of the target to form gas-phase thermal fragments prior to ionization by conventional methods such as electron impact or chemical ionization, and so that the target temperature is adjustable for controlled removal of solute from the said target.
17. 17. A device as defined in Claims 13 or 14, which further includes means for directing a primary ion beam onto the surface of the said target so that the collected solute molecules are sputtered from the surface of said target to form gas-phase solute ions.
18. 18. A device as defined in Claim 15, which further includes means for focussing a laser onto the surface of the said target so that laser desorption or photoionization processes occurs.

    -31
19. 19. A device as defined in any one of Claims 9, 15, which further includes a negative high volatge discharge as a source of electrons for chemical ionization processes and a positive high voltage discharge as a mdans to ionize particles and molecules by filed ionization.
20. 20. A device as defined in any one of Claims 1 to 7, which further includes means to collect solvent vapor on cold surfaces while allowing solute particles to pass through said cold trap for subsequent detection.
21. 21. A device as def ined in any one of Claims 1 to 7, which further. includes an optical region across the axis of said particle beam so that light scattering measurements can be made on said particle beam.
22. 22. A device as def ined in any one of Claims 1 to 7, which further includes a flat target axially aligned with the particle beam so that the particles impact on the surface in a narrow band.
23. 23. A device as defined in Claim 22, which further includes a moving target that rastors across the axis of said particle beam and collects solute particles as a function of time so that a target containing a chromatographic profile can subsequently be treated and analyzed with surface measurement techniques such as SIMS, scanning infra-red, ultraviolet, oz. visible spectrophotometry.
24. 24. A device as defined in Claim 23, which further includes a target for collection of highly purified solute crystals for subsequent crystal structure analysis.

    -- S Q -
25. 25. A device as defined in Claim 23, which furthet includes a heated target for collection of sample for online thermal analysis, comprising: a. means for supplying heat to said target, b. means for controlling the supply of heat to said target, and C. means for measuring the supply of heat to the target, whereby the thermal energy consumed by the evaporation or desorption of solute from the target is precisely measured.
26. 26. A method for, generating and transporting highly dispersed aerosols from solutions containing low volatility solutes for sample introduction into detection devices, concentration of solute or the purification of solute, comprising:. a. introducing a concentric flow of liquid and gas streams so that the gas flows outside the liquid flow, b. conducting heat to the inner liquid stream via the thermally conductive gas blanketing said liquid stream, C. nebulizing said liquid stream by, i. accelerating said liquid stream through a narrow tube to increase its linear velocity, ii. introducing into said liquid stream thermal energy across the conductive gas, and iii. introducing into said liquid stream mechanical energy from said conductive gas flow, so that properties of the generated aerosol cad be chnaged by controlling the amount of each source of energy imparted to the liquid stream, and d. controlling the supply of energy directed toward the aerosol generation process by, i. controlling the supply of heat to said - 3: - i i - conductive gas medium, controlling the flow of conductive gas onto the outer flow region, and iii. controlling the flow rate of liquid into the nozzle of the aerosol generator.
27. 27. A method as def ined in Claim 26, which further includes a separation step of removing the solvent vapor.'from the aerosol by cryogenic trapping of the vapor and passing dry solute particles for subsequent detection.
28. 28. A method as defined in Claim 26, which further includes a separation step of removing the solvent vapor from the aerosol by accelerating the aerosol through a nozzle so that a high velocity solute particle beam is formed axially aligned with the nozzle and by non-axial pumping of said solvent vapor.
29. 29. A method as defined in Claim 28, which further includes a pressure reduction step of directing said axial particle beam through at least two skimmers separating differentially pumped chambers.
30. 30. A method as defined in Claima 28, which further includes a step of collecting the solvent-depleted solute particles on a target surface for subseqtknet analysis, the analysis including a selected one or mor of the following: a. vaporization and ionization for mass spectrometric analysis, or b. x-ray diffraction analysis or other crystal or solid particle studying techniques, or C. optical analysis such as intra-red reflectance or transmittance or other optical techniques using any 1 -3g- appropriate wavelength, filter, or monochrometer.
31. 31. A method as defined in any one of Claims 26 to 30 which further includes flame ionization detecting of the particle stream, the conductive aerosol generation gas being hydrogen as required for flame ionization detection.
32. 32. A method as defined in any one of Claims 29 to 31 comrpising the step of vaporizing the enriched solute particles by directing the particle beam through a high energy electrical discharge of sufficient energy to charge the surface of the particles and thereby enhance ion desorption or particle fission by coulombic repulsion.
33. 33. A method as defined in any one of Claims 29 to 31 comprising the steps of vaporizing the enriched solute particles by directing the particle beam to a heated surface with sufficient surface area to collect said beam and with a sufficient supply of thermal energy to evaporate the solute.
34. 34. A method as defined in any one of Claims 29 to 31 comrpising the steps of vaporizing the enriched solute particles by directing the particle beam onto a heated surface with sufficient surface area to collect the said beam and an alternative source of energy to cause evaporation, the source of energy comprising a selected one or more of the following: a. a laser so that the solute molecules are desorbed from the collector surface using the process known as laser desorption, or b. an ion beam so that solute molecules are desorbed from the collector surface using the process known as ion sputtering, or C. a high voltgae field so that solute molecules are desorbed from the collector surface.
35. 35. A thermal aerosol generating device for obtaining solvent-depleted solute particles of micron or submicron size in a well defined direction from a liquid sample, the sample containing volatile solvent and less volatile solute, the device comprising: a. a capillary tube to transport liquid into a high velocity liquid jet, b. a means for supplying liquid at adequate flow and presure to the said capillary tube, C. a means for supplying heat to said capillary tube, d. a means for controlling the supply of heat to said capillary tube, e. an expansion chamber for storing high velocity particles, f. a nozzle restriction into a vacuum chamber to form a high velocity aerosol beam, g. at east one stage for pumping solvent vapor away from the axis of the solute particle beam, and h. at least one skimmer separating the pumping stages to axially sample the enriched solute particles, whereby enriched solute is collected or detected.
36. 36. A device as defined in Claim 35, wherein said means for supplying heat comprises an electrical circuit with an outer capillary tube being provided as the heating element of the circuit, said outer capillary tube being composed of high purity metal having a relatively high linear relationship between temperatures and resistance.
37. 37. A thermal aerosol generating device as defined in Claim 35 wherein, said means for supplying heat compLises an electrical circuit wherein the heating element is a cartridge heater in thermal contact with said outer metal capillary tube to heat same uniformally.
38. 38. A device as defined in any one of Claims 35 to 37, which further. includes a supply means for heating said expansion chamber, control means for controlling said supply means, and sensing means for monitoring the temperature of the expansion chamber.
39. 39. A device as defined in Claim 35, in combination with a mass spectrometer interface affixed directly to the housing of the mass spectrometer, whereby the efficiency of the transport of solute particle beam is enhanced by minimising the particle beam length.
40. 40. A device as defined in Claim 35, in combination with a mass spectrometer interface comprising readily attachable and removable insertion probe for the ion source region of mass spectrometer through a vacuum interlock.
41. 41. A device as defined in Claim 39 or 40, which further includes a heated target axially aligned with the solute particle beam so that the said target causes rapid evaporation or flash desorption of the collected solute particles.
42. 42. A device as defined in Claim 41, which further includes a control means for controlling the desorption and/or evaporation of solute from said heated target so that: a. the collected solute particles are desorbed of evaporated as intact molecular species prior to ionization by electron impact or chemical ionization process, or 1 - 4 1,- b. the collected solute particles are thermally ionized from the surface as intact molecular ions, as the collected solute particles are pyrolyzed on the surface of the target to form gas-phase thermal fragments prior to ionization, whereby the target temperature can be adjusted for controlled removal of solute from said target.
43. 43. A device as defined in Claims 41 or 42, which further includes means for directing a primary ion beam onto the surface of the said target so that the collected solute molecules are sputtered from the surface of the target to form gas-phase solute ions.
44. 44. A device as defind in Claims 41 or 42, which further includes means for focussing a high power laser into the surface of said target so that laser desorption or photoionization processes may occur.
45. 45. A device as defined in any of Claims 35 to 40, which further includes a high voltage discharge as an ionization source.
46. 46. A thermal aerosol generating device for obtaining solvent-depleted solute particles of micron or submicron size and well defined direction from a liquid sample, the sample containing volatile solvent and less volatile solute, the device comprising: a. a capillary tube to transport liquid into a high velocity liquid jet. b. means for supplying liquid at adequate flow and pressure to the said capillary tube, C. means for supplying heat to said capillary tube. d. means for controlling the supply of heat to said - Lt- 2_..0 capillary tube. e. an expansion chamber for showing high velocity particles. f. means for. collecting solvent vapor on cold surfaces while passing solute particles through the cold trap for subsequent detection selectively with one or, more ionization detectors including flame absorption, emission, or fluorescence spectrophotometers or plasma atomic em.Lssion spectrophotometers.
47. 47. A device as defined in any one of Claims 35 to 40, which further includes an optical region across the axis of the particle beam so that light scattering measurements can be made on the particle beam.
48. 48. A device as defined in any one of Claims 35 to 40, which further includes a flat target axially aligned with the particle beam so that the particle beam impacts on the surface in a narrow band.
49. 49. A device as defined in Claim 40, which further includes a moving target that rastors across the axis of the particle beam and collects solute particles as a function of time so that the target containing a chromatographic profile can subsequently be treated and analyzed with surface measurement techniques such as SIMS, scanning infra-red, ultraviolet, or visible spectrophotometry.
50. 50. A device as defined in Claim 48 which further includes a heated target for collection of sample for on-line thermal analysis, the target comprising; - a. means for supplying heat to said target, b. means for controlling the supply of heat to said a i -tt 11 target, and c. means for measuring the supply of heat to the target, so that the thermal energy consumed by the evaporation or desorption of solute from the target is precisely measured and related to concentration.
51. 51. A method for, thermally generating highly dispersed aerosols, which includes a separation step removing the solvent vapor from the aerosol by cryogenic trapping of the vapor and passing dry solute particles for subsequent detection.
52. 52. A method for thermally generating a highly dispersed aerosol, which includes a separation step of removing solvent vapor from the aerosol by accelerating the aerosol through a nozzle so that a high velocity solute particle beam is formed that is ax,,ally aligned with the nozzle, and removing solvent.vapor by non-axial pumping.
53. 53. A method as defined in Claim 52, which further.

    includes a pressure reduction step of dispersing said j axial particle beam through at least two skimmers which separate differentially pumped chambers.
54. 54. A method as defined in Claim 52 or Claim 53, which further includes a step of collecting the solvent-depleted solute particles from said aerosol on a target surface for subsequent analysis, the analysis selectively including: a. vaporization and ionization for mass spectrometric analysis, or b. x-ray diffraction analysis or other crystal or solid particle studying techniques. or C. optical analysis such as infra-i-ed reflectance or transmittance or other optical techniques using -41t - appropriate wavelenghts, filters, ot monochrometers.
55. 55. A method as defined in Claim 51, which further includes an ionization detection of the particle stream.
56. 56. A method for vaporizing the enriched solute particles by directing the particle beam in Claim 53 onto a heated surface with sufficient surface area to collect said beam and a sufficient supply of thermal energy to evaporate the solute.
57. 57. A method for, vaporizing the enriched solute particles by directing the particle beam in Claim 53 onto a heated surface with sufficient surface area to collect said beam and an alternative source of energy to cause evaporation, the alternative source of energy selectively comprising: a. a laser so that the solute moelcules are desorbed from the collector surface using the process known as laser desorption, or, b- by a beam so that solute molecules are desorbed from the collector surface using the process known as ion sputtering, or C. a high voltage field so that solute molecules are desorbed from the collector surface.

    Published 1988 at The Patent Office, Stale House, 66,71 High Holborn, London WC1R 4TP. Further copies may be obtained from The Patent office, Sales Branch, St Mary Cray, Orpington, Kent BR5 3RD. Printed by Multiplex techniques ltd, St Mary Cray, Kent. Con. 1187.