Studies on Real Time Ozone Layer Depletion Monitoring using the Negative Ion Mode of Ion Mobility Spectrometry / Atmospheric Pressure Ionization Mass Spectrometry (NEG. MODE IMS/APIMS) in Upper and Lower Atmosphere

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) In order to simulate the conditions of stratosphere, a St. St. reaction sphere is provisionally installed between O.sub.3 exit line from ozone generator or ambient sample inlet and said analyzer. A UV lamp to scan through the wave length range 200-400 nm was designed to install in the culminant part of the sphere together with a thermometer and pressure gauze set on it. As a result, a simulation work on reaction phenomena occurring in the stratosphere can be observed in laboratory conditions.

2) In order to remove the interference acidic radicals such as NO.sub.x and CO.sub.x, a dopant chemical, ppm level of ammonium hydroxide solution source flask was designed to install at the O.sub.3 out let of ozone generator (so called ammonium chemistry established). The said radicals will then be eliminated from the phase and ozone molecules without interference to react with the thermal electrons in the said analyzer reaction region and drift through drift region to reach the ion collector plate as O.sub.3.sup..

3) Operating IMS only, collecting the drift time of the O.sub.3.sup. thus formed provide characteristic ion mobility value (K.sub.0=2.550.02 cm.sup.2v.sup.1s). Tuning at the O.sub.3.sup. peak keep on scanning gives a horizontal line; encountering with chlorine contained ozone depleting chemical, the O.sub.3.sup. level decrease down to form the characteristic peaks at mobility value K.sub.0=2.920.02 cm.sup.2v.sup.1s.sup.1 for Cl.sup. K.sub.0=2.61.sup.0.02 cm.sup.2v.sup.1s.sup.1 for Br.sup., and K.sub.0=2.51.sup.0.02 cm.sup.2v.sup.1s.sup.1 for I.sup. respectively to detect and identify that the type of compound involved in the ozone destruction.

4) Collecting total ion m/z mass spectra, with opening of the two shutter gates of the IMS, can be performed to get the product ions from the reaction of ozone and the ozone depletion chemicals. This spectrum is nothing but atmospheric pressure ion mass spectra (APIMS).

5) Collecting drift time of IMS mode for every individual ion of total mass spectra, we can reconstruct ion mobility spectra which should be identical with the IMS spectra collectable in 2. & 3 with only tiny bit delayed drift time.

6) Correlation data obtained from IMS and APIMS spectra will be stored in library should pave the way complete identification of the ionic species detected in the ozone depletion reaction.

7) Based on these results, with the aid of algorithm, the IMS alone only is a capable instrument to detect and identify the ozone depletion substances especially in the rugged mobile operation. As a result IMS in the negative ion mode can be developed as a device of real time ozone layer depletion monitor. It can be loaded in Ozone Sonde balloon, Airplane, Shuttle, and lower level satellite for measurement ozone concentration in site.

8) Said IMS in the negative ion mode with ammonium dopant at the sample inlet can also be developed as a real time O.sub.3 monitor in ambient environment.

Description

BRIEF DESCRIPTION OF FIGURES

[0054] In FIG. 1, two body ion-molecule reactions and electron attachment reactions are indicated by thin arrows, three ion-molecule reactions are indicated by thick arrows where M represents a third body (N.sub.2 or O.sub.2). The neutralization process of electron-positive ion (dissociative) recombination and ion-ion recombination are indicated by dashed lines. As shown, Important thing is that CO.sub.2, NO, NO.sub.2 gases is hindering O.sub.3.sup. in keeping its negative charge on it. i.e. O.sub.3.sup.+CO.sub.2.fwdarw.CO.sub.3.sup.+O.sub.2. Similarly NO and NO.sub.2 end up to NO.sub.3.sup.. If there is SO.sub.2 would be ended up to HSO.sub.3.sup. and HSO.sub.4.sup. acid radicals. This is the reason why we need ammonium hydroxide (NH.sub.4OH) chemistry. Discussion of FIGS. 2-4 were made Experimental results expected as discussed above.

[0055] FIG. 2 shows schematic diagram of ion mobility spectrometer/mass spectrometry (IMS/MS) system interfaced with newly designed e- ion-molecule reaction sphere.

[0056] In FIG. 3, Schematic diagram of negative ion mode ion mobility spectrometry using N.sub.2, O.sub.2, O.sub.3 gas as carrier and drift gases for the detection of halide compounds. The obtainable product ions halide compounds from negative ion mode of atmospheric pressure ionization mass spectrometry (APIMS) using O.sub.2 or O.sub.3 gas doped into N.sub.2 carrier gas stream.

BRIEF SUMMARY OF INVENTION

[0057] 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.1s.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 lodo Carbons and Ozone (O.sub.3) can be obtained.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

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[0128] Appendix: Due to page limitation, applicant invites reviewers to read the References of [18] and [65] in regard to available the IMS hard ware development which can be used for the work proposed here with some modification.