Real time ozone layer monitoring using ion mobility spectrometry

Abstract

The present invention provides a capability of Ion Mobility Spectrometry/Atmospheric Pressure Ionization Mass Spectrometry (IMS/MS) in the negative ion mode for Ozone detection and methods for ozone layer depletion monitoring in laboratory environment. Ammonium hydroxide vapors, as a dopant chemical, introduced to the inlet system of the IMS/MS interfaced with the reaction sphere enables ozone ionized to be O.sub.3.sup.. The data obtainable from proposed methods show how ozone is depleted and which compound affect the most for O.sub.3 destruction among the O.sub.3 depletion substances of Chloro Fluoro Carbons (CFCs), Hydro Fluoro Carbons (HFCs), Hydro Chloro Fluoro Carbons (HCFCs), Hydro Chloro Bromo Carbons (HCBCs), and Hydro Chloro lodo Carbons (HClCs). Based on the results obtainable, more likely the IMS alone system without coupling with the mass spectrometer (IMS/MS) will rather be selected to develop as a spatial real time ozone layer depletion monitor. Real time monitoring device of ozone concentration in ambient atmospheric conditions can also be developed with this technique.

Claims

1. A method for real time ozone layer depletion in stratospheric conditions monitoring comprising: introducing nitrogen carrier gas, ozone and a dopant, ammonium hydroxide vapors, into inlet system for a reaction sphere and reacting to produce pure ozone gas in nitrogen gas stream in reaction sphere; passing said ozone gas into an ion mobility spectrometer coupled to a quadrupole mass spectrometer (IMS/MS) wherein ozone molecule undergoes electron capture reaction with electrons formed by Ni-63 ionization source in reaction region to produce O.sub.3.sup. which drift through in drift tube and detected by an ion collector plate in said IMS and by electron multiplier in the MS and wherein said IMS/MS operating in negative mode; said (O.sub.3.sup.) ions leftover after depletion by ozone destroying substances being passed into said IMS/MS the resulting (O.sub.3.sup.) spectra thereby simulating ozone layer depletion in stratosphere.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1Ion Chemistry of the lower atmosphere the mesosphere, the stratosphere and the Troposphere.

(2) FIG. 2Schematic Diagram of Ion Mobility/Mass Spectrometer (IMS/MS) System Interfaced with Ion-Molecule Reaction Sphere.

(3) FIG. 3Schematic Diagram of Negative Ion Mode Mobility spectral data obtainable with IMS/MS using nitrogen, oxygen and ozone carrier gas for the analysis of halide compounds.

(4) FIG. 4Product ions spectra of halide compounds from negative ion mode of atmospheric pressure ionization mass spectrometry (APIMS) using oxygen and ozone gas doped into nitrogen carrier gas.

(5) negative ion attachment. This is typically accomplished with the reactant ions of (H.sub.2O).sub.nO.sub.2.sup., CO.sub.4.sup., CO.sub.3.sup., OH.sup., and (H.sub.2O).sub.nCl.sup.. For instance, Cl.sup. is added to the site of bivalent atom such as sulfur like mustard gas.

DETAILED DESCRIPTION OF THE INVENTION

(6) Experimental Set up.

(7) Our approach is to set up an IMS instrument with which we can perform a simulation work on O.sub.3 depletion phenomena in stratosphere at the laboratory conditions. Based on the report of Relativistic Electron Precipitation (REP), the electrons with the energy range of 1-30 MeV in the stratosphere [21-24,30], should produce electrons with energy lower level after interaction with air particles. Thus the environment of stratosphere appears to be similar to the environment of reaction region of the IMS (Ni-source) having electron energy 60 keV-0.5 eV. In order to identify the ions (m/z) produced accurately, ion mass analysis by mass spectrometer is required. A high resolution quadrupole or time of flight mass spectrometry is needed.

(8) FIG. 2 shows a modified schematic diagram of Ion Mobility Spectrometry/a quadrupole mass spectrometer (IMS/MS)[18, 19] interfaced with a reaction sphere. A reaction sphere can be made by face to face down welding of two St.St steel bowls. Special design has been made to have thermocouple, krypton UV lamp from Solar Light or Cathdeon Ltd. UK, which can scan wave length 175-380 nm range on the top area. Carrier gases such as N.sub.2, air, O.sub.2, or O.sub.3 can be introduced to the reaction sphere by closing valves V.sub.2 and V.sub.4. Samples of O.sub.3 depletion substances can then be introduced to the injection port S.sub.1 to perform analysis. The types of collectable data includes: 1) IMS Spectra by only IMS; 2) Total APIMS mass spectra collectable with the two IMS shutter grids open; 3) reconstructed total IMS spectrum by checking of the drift time of individual ions of total mass spectrum. Thus the IMS peak with accurate m/z can be identified. The correlation between IMS and APIMS data can be established for the compounds with interest. Temperature and pressure control, if necessary, can be established in the laboratory conditions.

(9) Using a quadrupole or time of flight mass spectrometer interfaced with IMS/MS system is necessary. The 56 compounds of ozone depletion substances, CFCs or HCFCs [www.epa.gov/ozone/ods.html] [41] can be analyzed with this IMS/MS system. Once the correlation of the IMS and APIMS data is fully interpreted, the library of data file for the algorithm program should be established for the compound identification. These results will verify the IMS alone data file is good enough for monitoring of ozone layer depletion. The reaction sphere can be made for instance by welding two Stainless steel bowls facing down against each other and volume turned out to be 3690 ml. A dopant flask A contained with ppm level of ammonium is installed at the entrance of carrier gas line. A neutralization reactions are expected to occur between ammonium hydroxide and acid radicals to precipitate out the radicals of NO.sub.3.sup., CO.sub.x.sup., SO.sub.x.sup.. So the reactions of (NH.sub.4)OH+HNO.sub.3--->(NH).sub.4NO.sub.3+H.sub.2O. will take place. Similarly (NH.sub.4).sub.2CO.sub.4 and (NH.sub.4).sub.2SO.sub.4 can also take place in the ammonium hydroxide trap before the inlet system.

(10) As a result, the acid radicals which have higher EA value than O.sub.3 can be eliminated from the reaction system to pave the way for ozone to be ionized. Now we expect to see a prominent O.sub.3.sup. IMS peak. Therefore the simulation work of the (e)ion-molecule reaction studies of O.sub.3 and related molecules such as CFCs, BrFCs, IFCs, HCFCs, HFCs, and NO.sub.x can be performed with the negative ion mode of IMS or IMS/MS system. Unlike positive ion mode, the response of negative ion mode of IMS is obtainable from only the compounds having polar groups appears to have inherently higher selectivity and lesser interference than the positive ion mode.

(11) FIG. 3 shows a schematic diagram of three modes of ozone depletion monitoring using negative ion mode IMS is shown. The data detected and identified with halide compounds by this system can be collected in three modes.

(12) Mode I: trace a shows standing thermal electron current when N.sub.2 is used as carrier gas. In Trace b and c, O.sub.2 reactant ion and O.sub.3 reactant ion to be formed by injecting 10 ppm level of bone dry air and ozone gas respectively. Reduced mobility K.sub.o=2.52 cm.sup.2V.sup.1s.sup.1 reported was for the (H.sub.2O).sub.nO.sub.2.sup. [53], and 2.55 cm.sup.2V.sup.1s.sup.1 [54] within workable error range. The reduced mobility K.sub.o of O.sub.3 was reported to be 2.69 cm.sup.2 V.sup.1s.sup.1 [55]. Under these conditions, individual halide contained Cl, Br, and I is will be introduced to collect the spectra. Depicted in Traces d, e, and f are the reduced ion mobilities for Cl. Br, I with K.sub.o=2.92, 2.61, and 2.51 cm.sup.2 V.sup.1 s.sup.1 respectively [46, 54].

(13) Mode II: one can simply collect invert spectra of these halides by tuning at the drift time O.sub.3 reactant ion. In this operation, the standing current of O.sub.3.sup. will be decreased down by charge transfer to the halides to become Cl.sup., Br.sup., I.sup. as seen in Traces of a, b, and c in Mode II. These type of operation needs two shutter grids in the drift tube to synchronize open and closing time delay between the two gates.

(14) Mode III: the obtainable spectrum by injecting the mixture of these three different compounds are shown in FIG. 3. The standing reactant ion current will produce spectra responded to these three different compounds as depicted in Mode III. As a result, the individual compound type caused ozone destruction can be identified. The X.sup. denotes Cl.sup., Br.sup., I.sup. and F.sup.. Fluorine ion however is not observed in IMS condition with probable reasons either high CF bond energy or too short life time of F.sup. as discussed above. The capability to provide these three sets of data with ozone depletion substances demonstrate that the negative ion mode of IMS can be developed as a real time monitoring device.

(15) Since the APIMS (=APCIMS) data obtainable from the IMS/MS system shown in FIG. 2, the three Modes of operation illustrated in FIG. 3 also possible with the APIMS system. In FIG. 4, product ions of halide compounds observable by the similar types of modes of operation using negative ion mode of APIMS are shown. In a similar manner as in FIG. 3, data can be produced by mass spectrometer with accurate m/z information of the ions produced shown in FIG. 4.

(16) Using micro syringe if 10-100 ppm level of oxygen (O.sub.2) is injected to the reaction sphere through sample injection port S.sub.1, one can collect the reactant ion of (H.sub.2O).sub.nO.sub.2.sup. with m/z 32 and m/z 50 in weak intensity as shown in Trace b of FIG. 4. Under these conditions, since the EA of O.sub.3, 2.103 eV and that of O.sub.2, 0.450 eV, with injection of 10-100 ppm of O.sub.3 the charge will be taken over by O.sub.3 to form the reactant ion of ozone (H.sub.2O).sub.nO.sub.3.sup. with m/z 48, as depicted in Trace c of FIG. 4. Since NO.sub.x gases have EA higher than that of O.sub.3, NO.sub.x will take over the charge. However NO.sub.2 (EA=2.270 eV) or NO.sub.3 (EA=3.973 eV) will be removed in the system by the dopant NH.sub.4OH (an acid scavenger), as discussed above. That means in Ni-63 reactor of IMS only air and ozone gas will remain. Under these conditions, the halide compounds (Freon gases) injected in 10-100 ppm level will take over the charge from O.sub.3.sup. to form X.sup.(XCl.sup., Br.sup., or I.sup.) with m/z 35, 37, for Cl.sup., m/z 79, 81 for Br.sup., and m/z 127 for I.sup. respectively as shown in Trace d, e, and f of FIG. 4.

(17) Based on the data collected throughout the phase I work, additional studies and investigation on the further miniaturization of hardware will be performed. Final design of the ozone monitoring IMS will be made. This Capability to provide the three sets of data with ozone depletion compounds demonstrate that the negative ion mode of the IMS can be developed as a real time ozone monitoring devise at the site of anywhere. This device can be loaded for monitoring O.sub.3 in a Balloon, Aircraft, Shuttle, and low orbital Satellite Flight.

Results and Discussion

(18) The Ion Mobility Spectrometry/Mass Spectrometry system is one of the most powerful gas phase analytical systems for the studies of ion-molecule reactions occurring under atmospheric pressure. In the negative ion mode in particular the environment of the IMS (Ni-63) interfaced with the reaction sphere is similar to that of stratosphere as shown in the FIGS. 2-4. As a result, simulation work of ion-molecule reaction studies between O.sub.3 and depleting substances such as CFCs, NO.sub.x, CO.sub.x, SO.sub.x, and HCFCs can be performed. Due to tough government regulation on radioactive material handling, IMS with Atmospheric Pressure Corona Discharge Ionization (IMS-APIMS) has been preferred to develop further in trace analysis by researchers in this area. Proton chemistry is dominating in the positive ion mode of both IMS (Ni-63) and IMS-APIMS, while negative ion mode reactant ions of these two IMS systems are different as summarized in Table 2.

(19) TABLE-US-00003 TABLE 2 Comparison of Major Reactant Ion Species of IMS (Ni-63) & IMS (APIMS) Ion Source Pos. RT. Ion Neg. RT. Ion Remarks: Carrier Gas IMS (Ni-63) Ni-63 (H.sub.2O).sub.n NH.sup.4 Thermal Electrons N.sub.2 Carrier & Drift Gas (H.sub.2O).sub.n NO.sup.+ (H.sub.2O).sub.n O.sub.2.sup. Dry Air Carrier & Drift Gas [54] (H.sub.2O).sub.n H.sup.+ (H.sub.2O).sub.n O.sub.3.sup., O.sub.3 ppm (2-8 ppm) in N.sub.2 *Carr. & Drift Gas Flow. IMS (APCDI) APCDI (H.sub.2O).sub.n H.sup.+ O.sub.2.sup., NO.sub.2.sup., CO.sub.3.sup., NO.sub.3.sup. Dry Air Carr. & Drift (H.sub.2O).sub.n NO.sup.+ Gas [55]. (H.sub.2O).sub.n NH.sub.4.sup.+ N.sub.2O.sub.2.sup., (N.sub.2)O.sub.3.sup., NO.sub.3.sup. Dry Pure O.sub.2 Carr. Drift Gas [56, 57]. IMS (Ni-63), IMS (APCDI) (H.sub.2O).sub.n NH.sub.4.sup.+ (H.sub.2O).sub.n O.sub.2.sup., (H.sub.2O).sub.n O.sub.3.sup. NH.sub.4OH Dopant (H.sub.2O)n H.sup.+ NH.sub.4.sup.+ Chemistry O.sub.3 2-10 ppm doped N.sub.2 Carrier & Drift gas. Note: *O.sub.3 generation with high purity O.sub.2 (0.05 ppm of N.sub.2 and 200 ppb of CO.sub.2) gas. It is predicted to have (H.sub.2O)n(N.sub.2)mO.sub.3.sup. as reactant ion in this proposal. Results obtained Sabo et al. [56, 60] support this view. The acid radicals such as NO.sub.3.sup., CO.sub.3.sup. and HSO.sub.4.sup. will be precipitated as ammonium salts (Basic Chemistry) [60]. O.sub.3 generator available from the Air-Zone Inc. is claimed not to contain any NO.sub.x gas as an impurity in the O.sub.3 quality [61, 62].

(20) In Table 2, major reactant ionic species of both positive and negative modes from two different type of IMS-Ni-63 and IMS-APCDI are compared. Ion of H.sub.2O).sub.nH.sup.+, regardless the kind of carrier gas i.e. N.sub.2, Air, or O.sub.2, used, is formed as major reactant ion from both IMS-Ni 63 and IMS-APCI. However in the negative ion mode, thermal electron current and (H.sub.2O).sub.nO.sub.2.sup. are reactant ionic species for N.sub.2 and O.sub.2 carrier gas respectively. On the other hand, due to the formation of NO.sub.x.sup., CO.sub.3.sup. and O.sub.3 gases from corona discharge in the APCDI source, O.sub.2.sup., NO.sub.2.sup., CO.sub.3.sup., (or N.sub.2O.sub.2.sup.), (N.sub.2)O.sub.3.sup., and NO.sub.3.sup. are the reactant ionic species observed [53, 56, 58].

(21) Using the reaction rate constant reported (58), k=6.010.sup.10 cm.sup.3/s, from the charge transfer reaction of O.sub.2.sup.+O.sub.3.fwdarw.O.sub.3.sup.+O.sub.2, reaction time, 9.3 ms was calculated by Ewing et al. [52] for the concentration of [NO.sub.2][O.sub.3]=1.810.sup.11 cm.sup.3 (0.01 ppm as initial concentration) assumed. With the IMS drift time base 20 ms set for the experiment was most reactant ion peaks were observed to be in between 10-15 ms range. This means reaction time range observed for reactant ions were to be within 1-5 ms. As a result, conclusion was made the reaction time of O.sub.3.sup., 9.3 ms, is too long to be observed in IMS under the conditions they employed. This conclusion seems to be reasonable and understandable. Their initial O.sub.3 concentration was assumed to be 0.01 ppm for the above discussion. However the reaction times calculated with 0.02 ppm and 0.1 ppm of the O.sub.3 concentration turned out to be 4.8 ms and 0.93 ms respectively. Which means O.sub.3.sup. very probably should have been observed with the higher concentration of O.sub.3.

(22) While even though the EA of O.sub.3, 2.103 eV is much higher than that of O.sub.2, 0.452 eV. NO.sub.2 formed in the APCDI with EA 2,270 eV effectively blocks the formation of O.sub.3.sup.. One more reason is that the faster reaction rate of O.sub.3.sup.+NO.sub.2--->NO.sub.2.sup.+O3, k=7.010.sup.10 cm.sup.3/s, than that of O.sub.2.sup.+O.sub.3=O.sub.3.sup.+O.sub.2, k=6.010.sup.10 cm.sup.3/s with zero air carrier gas in IMS is responsible for blocking forming of O.sub.3.sup.. With purer oxygen (N.sub.2=1 ppm), not zero air, carrier gas NO.sub.2 ion is drastically reduced down to - level of Trace b and only O.sub.2.sup. ion peak was prominent in intensity in FIG. 3 reported by Ewing et al [55]. This is a very good evidence if purer O.sub.2 is used the effect of NO.sub.2 to block O.sub.3 formation is minimal. Under these conditions O.sub.3.sup. ion would be formed by charge transfer from O.sub.2.sup. when ppm or higher level of O.sub.3 is introduced to the ionization source. Under these circumstances, the ammonium hydroxide dopant vapor effectively clean up the NO.sub.3 gas to provide an opportunity for ozone to be ionized as O.sub.3.sup..

(23) The ion species with m/z 60 and Ko=2.52 cm.sup.2 V.sup.s.sup.1 was interpreted as CO.sub.3.sup. in their IMS/MS work by Ewing et al. [54] while Sabo et al. [56,59] reported as (N.sub.2)O.sub.2.sup.. The mobility of this ion overlaps the mobility of O.sub.2.sup. ion peak which is normally prominent negative reactant ion in IMS when zero air is used. Suppose the (N.sub.2)O.sub.2.sup. is simply a cluster ion formed via the reaction of O.sub.2.sup.+N.sub.2<--->(N.sub.2)O.sub.2.sup. the resultant EA value is predicted to higher than 0452 eV. However The 100 ppt of CO.sub.2 in the O.sub.2 gas used by Sabo et al. and reported EA value 3.351 eV of N.sub.2O.sub.2.sup.[56], which is rather high, supports the interpretation made by Sabo et al. On the other hand based on data of the intensities of the ions vs discharge time reported by Ewing et al. [55] the ion with m/z 60 is favored to be CO.sub.3.sup. although the concentration of CO.sub.2 was 0.1 ppm in the Zero Air Carrier gas used. With ammonium hydroxide dopant, the ion with K.sub.0=2.52 and e/m 60 should be identified correctly.

(24) The ion peaks of CO.sub.3.sup., O.sub.2.sup., NO.sub.2.sup., and NO.sub.3.sup. appear to have their ion mobility (k.sub.0)=2.65, 2.61, 2.83. and 2.56 cm.sup.2 v.sup.1 s.sup.1 respectively [55]. While Sabo et al. [56,57] reported the mobility values of the corresponding similar ion such as (N.sub.2)O.sub.2.sup. (identical m/z with CO.sub.3.sup.), O.sub.3.sup., O.sub.2.sup., and NO.sub.3.sup. to be K.sub.0=2.54, 2.49, 2.44, and 2.14 cm.sup.2 v.sup.1 s.sup.1 respectively. Again ammonium hydroxide dopant will make a lot simpler reactant ion with a clear K.sub.0 value and will tell what is the real ionic species responsible for the ion with m/z 60. An application of the technique of FAIMS or DMS [14-16] may give a better resolution of the reactant ions mentioned above. Our future work planned includes the test with FAIMS when the system is available for handling of atmospheric sample analysis [63].

(25) Recently U.S. EPA is considering to bring tolerable ozone level down to 65 ppb level from 75 ppb presently [64]. This policy change is based on the advocates of the public health and environmental activists: ground ozone (bad ozone) is well known to cause coughing, wheezing, asthma attack, and other health threat such as cardiovascular harm, low weight birth, and loss of short term memory as well. On the other hand industries groups strongly oppose the tougher regulation policy. The national manufacturing association (NMA) says the compliance tag of the O3 limit down to 65 ppb level of the U.S. will cause to loose as much as $2.2 trillion annually because of international trade competition power. Under these circumstances, accurate & real time ozone monitoring is vitally important. The real time ozone monitoring proposed in this patent should help policy makers in evaluating the new O3 limit using more accurate ozone concentration in any site.

(26) Functioning at atmospheric pressure conditions, Ion Mobility Spectrometry (IMS) is Capable to detect and identify gas phase chemicals such as warfare agents, explosives, illidit drugs, and ambient air constituents. The negative ion mode in particular, when Ni-63 foil or corona discharge ionization source is used as ionization source, the environment of ionization region appears to be similar to that of the stratosphere. Simulation work on e-molecule reaction and charge transfer reactions occurring in stratosphere therefore can be performed in laboratory conditions. The response mechanism is not only as same as that of gas chromatographic ECD-GC detector but also pave the way to identify chemical identity by providing intrinsic ion mobility value (K.sub.o=cm.sup.2.Math.v.sup.1.Math.s.sup.1) difference of the product ions. As a result, scientifically clear pictures of the interactions between ChloroFluoro Carbons (CFCs), Hydro Fluoro Carbons (HFCs), Hydro Chloro Fluoro Carbons (HCFCs), Hydro Chloro Bromo Carbons (HCBrCs), Hydro Chloro Iodo Carbons and Ozone (O.sub.3) can be obtained.

(27) As ground based measurement instruments, spectrometers of Gordon Doowbson's Dowbsonometer and Mark III spectrometer have been in use since 1924. Through 1970s, the study of ozone concentration in atmosphere instruments have evolved from ground based spectrometers to balloons, aircraft, rockets, shuttles, and satellites. It measures the total ozone by measuring the relative intensity of the dangerous UVB (wavelength 305 nm) radiation to UVA (325 nm) radiation absorbed by ozone layer using Umker method to deduce vertical O.sub.3 distribution. However drawbacks are that it is strongly affected by aerosols and pollutants in the atmosphere because they absorb the UV light at the same wave length region. Recently LIDAR telescope is used to collect UV light that is scattered by two laser beams, one of which is absorbed by ozone (308 nm) and the other is not (351 nm). By comparing the intensity light scattered from each laser, a profile of ozone concentration vs. altitude is measured from 10 to 50 km. The said drawback still exist in this method. These absorption or emission spectroscopy methods are indirect procedure to measure.

(28) The O.sub.3.sup. formed by capturing electrons via direct e-molecule reaction in the said ozone analyzer of IMS drift through the drift tube to provide its characteristic drift time.

(29) Apparent interference compounds such as CO.sub.x, NO.sub.x, and SO.sub.x should be completely eliminated by the dopant chemical ammonium hydroxide solution installed at the sample inlet line.

(30) Thus the said ozone analyzer IMS not only detect ozone concentration level but also identify the compounds by which the ozone was destroyed in any situs.

(31) Unlike mass spectrometer, the miniaturized IMS instrument is simple to fabricate and able to operate in rugged mobile condition so that real time monitoring of the ozone concentration level is possible not only vertically but also horizontally as well.

REFERENCES

(32) 1. J. C. Farman, B. G. Gardiner, S. D. Shanklin, Nature, 315, P. 207-210, 1985. 2. J. Molina and F. S. Roulan, Nature, Vol. 249, No. 3460, June P. 810-812, 1974. 3. Scientific American, September 21, No. 1, 2009, Ozone Layer Depletion Leveling of? 4. AnneR. Douglass, Paul A. Newman, and Susan Solomon, Physics Today 67 (7), 42 (2014). 5. Johannes C. Laube, Mike J. Newland, Christopher Hogan, Carl A. M. Brenninkmeijer, Paul J. Fraser, Patricia Martinerie, David E. Oram, Thomas Rockman, Jacob Schwander, Emannuel Witrant, & William T. Sturges, Nature Geoscience, 7, 266-269 (2014) doi: 10.1038/ngeo 2109. 6. S. E. Strahan, A. R. Douglass, P. A. Newman, and S. D. Steenrod, J. of Geophysical Res. Atmosphere, Vol 120, Issue 70, 16 Apr. 2015. 7. A. R. Ravishankara, Andrew A. Turnipseed, Nids R. Jensen, Stephen Barone, Michael Mill, Carleton J. Howard, and Susan Solomon, Science Vol. 263, P. 71-75, 1994. 8. J. E. Loblock, R. J. Maggs, and R. J. Wade, Nature, Vol. 241, P. 194-196, 1973. 9. Stuart P. Cram and Stephen R. Chesler, J. of Chrom. Sci., Vol II, P. 391-400, 1973. 10. G. E. Spangler and Charles I. Collins, Anal. Chem., Vol. 47, No. 3. 1975, P. 393-402, 1975. 11. F. W. Karasek, Oswald Tatone, and David M. Kane, Anal. Chem., Vol. 46, No. 7, P. 1210-1214, 1973. 12. E. P. Grimsrud and D. A. Miller, Anal. Chem., 51, 851, 1979. 13. E. P. Grimsrud and S. H. Kim, Anal. Chem., 51, 537, 1979. 14. Roger Guevremont, J. of Chromgr., Vol. 1058 (1-2), November 26 P. 3-19, 2004. 15. Abu B. Kanu, Dwivedi Prabha; Tam, Maggi; Matz, Laura; Hill, Herb H. jr., J. of Mass Spec., Vol. 43, P. 1-22, 2008. 16. Ashley Wilks, Hart, Machew Hart, Andrew Koehl, Somerville, John Somerviile, Billy Boyle, and David Rutz-Alonso, Int. J. of Ion Mobil. Spec., Vol. 15, 2012, P. 199-222, 2012. 17. F. W. Karasek, S. H. Kim, Plasma chromatography Sensing Tubes, Final Report, University of Waterloo Research Institute Ontario Canada, Contract #8SUTT-00227, 1980. 18. Glenn E Spangler, D. N. Campbell, K. N. Vora and Carrico, J. P. Carrico, ISA, Transactions, Vol. 23, No. 1, P. 17-27, 1984. 19. Brochure for Phemto-Chem System, PCP Inc., 2155 Indian Rd., West Palm Beach, Fla. 33409. 20. McConnell, John C. McConnel and Jian Jun Jin, Atmosphere Ocean, 46, (1), P. 69-92, 2008. 21. Mansergh Richard Thorne, Science Vol. 195, No. 4275, January, P. 287-289, 1977. 22. A. M. Galper, V. M. Gratcher, V. V. Dmitranco, V. G. Kirillove-Ugryumove, A. V. Orlow, Ulin, S. E. Ulin, and E. M. Shermanon, Int. Union of Pure & Appl. Phys. Burg. Acad. Nana. LCCN, 78-307721, Vol. 12, P. 346, 1997. 23. S. Solomon, and G. Brasseur, Aeronomy of Middle Atmosphere Dovedrecht/Boston/Lancaster/Reidal D. Publishing Co., 1984. 24. N. A. Bui Van, I. M. Martin, A. Turtelli jr. (Brazil), M. I. Fradkin, V. V. Sibikin, Yu. I. Stohzkov, and A. Svirzhevskaya (USSR), I. L. NUOVO CIMENTO Vol. 12C, No. 5 September/October 1989. 25. W. R. Cook, A. C. Cummingo, J. R. Cummingo, T. L. Gerrard, B. Kecman, R. A. Mewardt, R. S. Selesnik, E. C. Stone, D. N. Baker, T. T. Rosenvinge, J. B. Blake, and L. B. Callis, IEEE Transaction on Geoscience and Remote Sensing, Vol. 31, No. 1, May 1993. 26. R. Hossaini, N. P. Chiperfield, S. A. Montzka, A. Rap, S. Dohmas & W. Feng, Nature, Geoscience 8, 186-190 (2015), doi: 10.1038/nge02363. 27. CNE. ACS. 28, Mar. 30, 2015 reportd by Steven K. Gibb. 28. P. Cicman, A. Pele, W. Sailer, S. Matejeik, P. Scheier and Mark, T. D. Mark, Chem. Phys., 371, P. 231-237, 2003. 29. D. D. M. Ho, K. T. Tsang, A. Y. Wong, and R. J. Siverson, UCRL-JC-105225, DE91 002951, Lawrence Livermore National Laboratory, University of California Livermore, Calif. 94550; Science Application International Corporation, Mclean Va. 22103; Department of Physics, University of California, Los Angeles, Calif. 90024. 30. Arther C. Alkin, Planetary Space Science Vol. 40, Issue 2-3, February-March, P. 413-431, 1992. 31. Michael T. Bowers, Edited (1979) Gas Phase Ion Chemistry, Vol. 2, 53-86 1979. 32. Q. B. Lu, and L. Sanche, J. of Chem. Phys., Vol. 120, 2434, 2004. 33. D. Smith, P. Spnel, Mass Spectrometry Review, 14 (1995) 255-278, 1995. 34. R. S. Narcisi, A. D. Bailey, L. Della Lucca, C. Sherman, D. M. Thomas, J. Atm. Terr. Phys. 1971, 33, 1147-1159. 35. R. Arnold, J. Kissel, D. Krankowsky, H. Wielder, J. Zahringer, J. Atm. Terr. Phys. 1971, 33, 1169-1175. 36. F. Arnold, G. henschen, Nature, 1978, 257, 521, 37. E. Arus, D. Nevejans, P. Frederick, J. Ingels, J. Atm. Terr. Phys. 1982, 44, 681-694. 38. G. M. B. Dobson Applied Optics, Vol. 7, No. 3, March, P. 387-405, 1968. 39. Brewer Spectrometer Technical Papers Courtecy Sci-Tech. Instruments Intl. September 18, Section 1-9, 1996. 40. S. A. Seebrook, J. A. Whiteway, L. H. Gary, R. Staebler, A. Herber, Atmos. Chem. Phys. Discuss., Vol. 13, 1435-1453, 2013. 41. Ozone in Our Atmosphere 2010 Update NOAA Earth Sci.; Noaanews.noaa.gov/Stories201; www.albany.edu/faculty/rgk/atm101/ozmeas.htm). 42. PDF Ozone Measurement Earth System Laboratory, www.esl.noaa.gov/escl/assessments/ozone/1994/Chapter 1. Lead Author: N. R. P. Harris, Coauthors: G. Ancellet, L. Bishop, D. J. Hopmann, J. B. Kerr, R. D. McPeters, M. Prendez, W. Randel, J. Staehelin, B. H. Subbaraya, A. Voltz-Thomas, J. M. Zawodny, & C. S. Zerefos. 43. Trends in Ozone Profile Measurements Earth System Laboratory, www.esl.noaa.gov/escl/assessments/ozone/2006 Chapter 5, N92-15456, by Panal Members Chair, H. Johnston, A. Akin, R. Nagatani, R. Barnes, W. Planet, S. Chandra, E. Remsberg, D. Cunnold, D. Rusch, J. Deluisi, C. Trepte, J. Gille, R. Viga, R. Hudson, P. Wang, M. P. McCormick, C. Wellemeyer, L. Mcmaster, J. Zowodny, & A. J. Miller. 44. F. W. Karasek, Anal. Chem., 46, 710 A, 1974. 45. S. H. Kim, Fundamental Aspects of Plasma Chromatography and its Application to Analytical Chemistry, Ph. D. Thesis, university of Waterloo, Ontario, Canada N2L 3G1 1977. 46. T. W. Carr, Plasma Chromatography, Plenum Press, new York, 1984. 47. G. A Eiceman and Zeev Karpas, Ion Mobility Spectrometry, CRC Press Inc., 1994. 48. G. A. Eiceman and Zeev Karpas, Ion Mobility Spectrometry, CRC Press Inc., 2005. 49. G. A. Eiceman, Zeev Karpas, Ion Mobility Spectrometry, CRC Press Inc., (Taylor & Francis Group, Boca Raton, Fla.) 2014. 50. J. B. Fenn, M. Mann; C. K. Meng, and C. M. Whiteheuse, Electrospray Ionization for Mass Spectrometry of large biomolecule, Science, 246 (4926); 64-71, Bibcode. Sci., 248-64F. 1989. 51. X. Tang, J. E. Bruce, and H. H. Hill jr., Rapid Commun. Mass Spectrometry, 21 (7) 1115-1122, John Wiley & Son Ltd. 2007. 52. G. A. Eiceman, Anal. Chem., October 1, 435A, Product Reviews Ion Mobility Spectrometry Rediscovered, 2003. 53. F. W. Karasek, and G. E. Spangler, Electron Capture Process and Ion Mobility Spectra in Plasma Chromatography, Edited by Zlatkis, A.; Poole, C. F., Elsvier, 1983, Chapter 15. 54. Francis W. Karasek, Oswald Tatone and David M Kane, Anal. Chem., Vol. 45, No. 7, June 1973. 55. Robert G. Ewing, and Melanie. J. Walton, Int. J. Ion Mobil. Spec., 12: 65-72, 2009. 56. Martin Sab, Jan Palenik, Marek Kucera, Haian Han, Hongmel Wang, Yahnan Chu and Stefan Matejcik, International Journal of Mass Spectrometry, 293 (2010) 23-17. 57. Martin Sab and Stefan Matejcik, Anal. Chem., 83, 1985-1989, 2011. 58. Michael T. Bowers, Edited Gas Phase Ion Chemistry, Vol. 1, Academic Press New York, 1979. 59. Martin Sabo, Jan Matusk, and Stefan Matejcik, Talanta, Vol. 85, 1, 13, July 400-405, 2011. 60. S. H. Kim, Internal Memorandom of Allied Bendix EPID, Identity of Controversial Negative Reactant Ion Peak at drift time 10.52 ms., Feb. 7, 1986. 61. G. Sipos, D. Horvas and A. Dombi, Ozone Science & Engineering, Vol. 18, P. 159-71, 1996. 62. D. W. Arnold and D. M. Newmark, J. Chem. Phys., 102, 7035, 1995. 63. Personal Communication, between Kim, Howard (Global Merit Dev., Inc.) and Boyle, Billy (Owlstone Air Monitoring Nanotech. Inc.) Nov. 28, 2012. 64. ACS Industry Vox Nov. 26, 2014. 65. Joseph E Roehl, Applied Spectroscopy Review, Vol. 26, (issue 1 &2), 1-57, 1991.