TW200937487A - Chemical ionization reaction or proton transfer reaction mass spectrometry with a quadrupole or time-of-flight mass spectrometer - Google Patents

Abstract

A system and methods are described for generating reagent ions and product ions for use in a mass spectrometry system. Applications for the system and method are also disclosed for detecting volatile organic compounds in trace concentrations. A microwave or high-frequency RF energy source ionizes particles of a reagent vapor to form reagent ions. The reagent ions enter a chamber, such as a drift chamber, to interact with a fluid sample. An electric field directs the reagent ions and facilitates an interaction with the fluid sample to form product ions. The reagent ions and product ions then exit the chamber under the influence of an electric field for detection by a mass spectrometer module. The system includes various control modules for setting values of system parameters and analysis modules for detection of mass and peak intensity values for ion species during spectrometry and faults within the system.

Description

200937487 IX. INSTRUCTIONS OF THE INVENTION: FIELD OF THE INVENTION The present invention relates generally to mass spectrometry and, in particular, to mass spectrometry for the formation of reagent ions using microwave or high frequency radio frequency plasmas and their applications. Related Applications This application was filed on October 10, 2007 and titled "Chemical j"

Ionization Reaction or Proton Transfer Reaction Mass ❹ Spectrometry with a Quadrupole Mass Spectrometer " U.S. Patent Application Serial No. 11/869,978, the entire disclosure of which is hereby incorporated by reference herein . U.S. Patent Application Serial No. 11/869,980, entitled "Chemical Ionization Reaction or Proton Transfer Reaction Mass Spectrometry with a Time-of-Flight Mass Spectrometer", filed on October 10, 2007, which is hereby incorporated by reference. The manner of reference is incorporated herein in its entirety. ❿ [Prior Art] Mass spectrometry generally refers to the direct measurement of the mass value of a particle or the implicit measurement of the mass value of a particle by measuring other physical quantities using spectral data. Mass spectrometry often involves determining the mass to charge ratio of ionized molecules or components. When the charge of the ionized particles is known, the mass value of the particles can be determined from the spectrum of the mass values. The system used to perform mass spectrometry is called a mass spectrometer. Mass spectrometer systems typically include an ion source, a mass filter or a separator and a detector. For example, 133727.doc 200937487 A sample of a knife or group of knives can be ionized by electron impact in an ion source to generate ions. Ions having different mass values are separated into a mass 77 cloth or spectrum by a mass analyzer, for example, by applying an electric or magnetic field to the ions. (d) II collects ions and can observe and/or record the amount of f. The relative abundance of the mass values in the spectrum is used to compare the composition of the sample with the mass or identity of the molecules or components of the sample. There are many different types of mass spectrometers, including those known as ion-molecular reaction mass spectrometers. In this class, there are several techniques, including proton transfer reaction mass spectrometry (ptr_ms) and selective ion flow mass spectrometry (8) FT. These types usually involve the generation of ions

method. By way of example, a proton transfer reaction mass spectrometer includes an ion source that produces reagent ions (typically hydronium ions (H3〇+)) to transfer charge to the sample components, for example, by proton transfer. In the selected ion flow tube mass spectrometer, the carrier gas is transported along the flow tube through the ions. In the ring by I〇nie()n a

In a proton transfer reaction mass spectrometer sold by the company of Innsbruck, Austda, a hollow cathode tube is used as an ion source to apply helium to the water vapor stream. The plasma is discharged to generate reagent ions. Some mass spectrometry systems are classified according to the type of mass analyzer used. For example, some mass spectrometry systems are based on, in tandem, &quot;, where another analytical technique is used in combination with a mass spectrometry device. An example is gas chromatography mass spectrometry (GC-MS) where a gas chromatography column is used to separate the components of the sample prior to analysis by mass spectrometry. The canister is measured by $* to determine the amount of volatile organic compounds (V0C) in the sample. The measurement of voc has become important because even the presence of traces 133727.doc 200937487 V〇c can be an important diagnostic indicator in many different applications and may affect human health. For example, when the frequency of v〇c rises above a certain level, it may cause harmful health effects in humans, such as respiratory symptoms. In addition, the type and amount of voc in a particular sample may indicate the presence of explosives, hazardous chemical agents, combustion products, disease agents, rot or contamination, arson 'sonics or overdose. In addition, monitoring the presence and amount of the beast is suitable for industrial processing, such as biochemical or pharmaceutical manufacturing processes. For existing mass 4 assay systems, a number of disadvantages are inherent in the general sense and when applied to the test ❹. For example, f-spectral measurement systems using gas chromatography are not suitable for continuous, immediate monitoring of fluid samples due to the relatively slow analysis of the samples. In addition, the above mass spectrometry systems often require sample collection from the field prior to analysis (rather than in situ analysis) of the sample in a laboratory-based environment. The mass spectrometry system described above is relatively insensitive to the lower concentration components in the sample, for example because the ion source does not produce an amount of ions sufficient to produce a identifiable mass spectrum of the lower concentration component. The mass spectrum of the lower concentration components in such systems is often not distinguishable from noise caused by dynamic range limitations or by noise interference from peak interference from higher concentration components or noise generated by electronic or mechanical equipment. . A mass spectrometry system with a suitable level of sensitivity may aid in the detection of the presence of VOCs, but may be susceptible to interference with the presence of other compounds that are present and therefore indefinitely identify compounds or substances. SUMMARY OF THE INVENTION There is a need for a robust mass spectrometry system that provides continuous, immediate, and in situ analysis. In addition, there is a need for a system that can reliably determine the presence and identification of 133727.doc 200937487 v〇c (including trace voc) in a particular sample. The system and method embodied by the present invention is characterized by the use of microwave energy or an intermediate frequency RF to generate a reagent ion such as hydronium ion ions for mass spectrometry interaction with a fluid sample. It has been found that the use of microwave energy produces a number of reagent ions such as hydronium ions that are more abundant than other reported ionization methods (e.g., using a source), while also avoiding electrode erosion and instability associated with dc discharge sources. A greater amount of reagent ions allows for (4) more sensitive sensitivity, which facilitates the quantitative measurement and/or identification of even trace amounts of individual v〇Cs. High frequency RF energy also exhibits advantages in mass spectrometry that are similar to those achieved when using microwave energy to generate reagent ions. Furthermore, the present invention relates to systems and methods for instantaneous measurement of 〇(:) at relatively high pressures (e.g., in excess of about 1 mbar (about 10,000 Pascals). In some embodiments, the invention is The system and method can be used to &lt;detect a VOC having a concentration on the order of mega-volume fraction (pptv). In some implementations, the module analyzes and classifies a particular detected VOC based on the obtained mass spectrum. System components in embodiments of the invention are suitable for portable mass spectrometry and/or in situ applications. The concepts described herein can be used to determine by chemical ionization mass spectrometry (CIRMS) or proton transfer reaction mass spectrometry. In a mass spectrometry system of the method (PTR-MS) technology. In some embodiments, the invention includes an analysis or control module for processing acquired, detected or collected data during system operation. Some systems include multivariate analysis modules to aid in the measurement and identification of VOCs based on mass spectrometry. Multivariate analysis modules can also be used to monitor errors in mass spectrometry systems or to detect systems. The control module or feedback loop can be used in a mass spectrometry system to control the generation of reagent ions and sample ions and their yield, for example, by controlling various process parameters of the system. Various electric fields, pressure values, ion and vapor flow rates, and ion energies. The present invention is also directed to couplings, connections, or interfaces between various system components for influencing the movement of reagent ion sample components and product ions across a mass spectrometry system. The sensitivity of the chemical ionization mass spectrometer and the proton transfer reaction mass spectrometer described above can be varied based on various system parameters. The sensitivity can be varied based on the reagent ion concentration of the drift zone A (eg, hydronium ion concentration). The ratio of the electric field to the neutral particle concentration E/N (expressed in Townsend (Td)) affects the sensitivity of the spectrometer. The E/N ratio is a function of the pressure (eg gas density) and electric field strength in the drift region. The ε/ν&amp; rate affects the time required for the ion to traverse the drift region. Sensitivity can be attached to the mass spectrum after exiting the drift region. The effect of the intensity of the ion beam (composed of reagent ions and product ions) on the transfer optics (eg electrode/lens aperture geometry), electric field and pressure state in the transfer region that affect beam focusing and beam transport properties ( The sensitivity can be varied based on the ratio between the partial pressure of the bulk sample gas and the neutral reagent material in the drift zone. The proton transfer rate constant (k) of the monitored gas sample material is the sensitivity. The length of the drift region is sensitive because the longer drift region requires more time for the material to traverse the drift region, and therefore the reagent ions have more chance of reacting with the sample material. Sensitivity may also be affected by various mass spectrometer-related sensitivity factors ( For example, the effects of ion transmission/quality discrimination, picker/preamplifier gain, and signal noise ratio. 133727.doc 200937487 In one aspect, the invention relates to a system. The system includes a microwave or high frequency RF energy source for ionizing particles of reagent vapors with microwave or R F energy to form one or more reagent ions. The system also includes a chamber including an inlet end that allows a sample to enter the chamber to interact with one or more reagent ions from the microwave or helium frequency RF energy source to form one or more product ions. The chamber has an electromagnetic field generated therein. The system also includes a quadrupole mass spectrometer module positioned relative to one of the chambers to exit the orifice for collecting one or more product ions and one or more reagent ions to aid in product ions and reagents Determination of the peak intensity and/or mass of each of the ions. In some embodiments, the microwave energy source includes a microwave plasma generator. High frequency RF energy sources can include capacitive coupling!^^ Plasma generators. In some embodiments, the reagent ions include hydronium ions, oxygen ions, or nitrous oxide ions. The sample may include one or more volatile organic compounds (v〇c). Some embodiments of the system are characterized by a set of electrodes disposed relative to the chamber to generate an electromagnetic field in the chamber. The electromagnetic field facilitates interaction between the reagent ions and the sample and directs product ions and reagent ions to pass through. Exit the orifice through the chamber. The electrode set can be disposed radially about one of the axes of the chamber, and the electromagnetic field substantially directs product ions and reagent ions axially. In some embodiments, a control module is in communication with the electrode set. The control module is operative to determine a value of an electromagnetic field (or electromagnetic field gradient) inside the chamber based on operating parameters of the system. The system can include a mass flow controller, capillary or leak valve for determining the amount of sample entering the chamber. The system can include a mass filter disposed between the microwave or high frequency RF energy source and the chamber to selectively allow reagent ions to enter the chamber. Examples of suitable mass filters include quadrupole mass filters. In some implementations, the system includes a multivariate analysis module </ RTI> coupled to the system operative to analyze data from the quadrupole mass spectrometer module. The microwave energy source can include a microwave generator, a resonator portion, a tube portion disposed within the resonator portion and in communication with the chamber, and one or more flow resistors that pass through the (equal) choke to reduce The amount of microwave energy in the reagent vapor supply, chamber, or both. In some implementations, the system includes a control module in communication with the system operable to vary input parameters of the system based in part on operating parameters of the system. These parameters include the composition of the sample, the pressure of the chamber, the rate at which product ions or reagent ions pass through the chamber, the flow rate of sample or reagent ions into the chamber, the energy of the product or reagent ions, reagent ions, product ions, or The chemical composition of the sample, or any combination thereof. In some implementations, the control module is operative to vary input parameters of a set of electrodes that generate an electromagnetic field within the chamber based in part on operational parameters. In some implementations, the system includes a control module in communication with the system to detect or identify errors in operational parameters of the system. The control module can also change the value of the operational parameter based in part on the detection or discrimination of the error. The system can include a control module in communication with the system for monitoring the system. The control module sets or adjusts the value of the operating parameter of the system in response to the monitoring, and the control module is based on a multivariate statistical analysis algorithm. In some implementations, the control module includes a multivariate statistical analysis module. 133727.doc -13- 200937487 The multivariate system δ1&quot; analysis module can be used for process monitoring and/or for the integration of mass spectrometry systems with $4UL @ 曰 -, ° multivariate statistical analysis module for detection and / Or identify the error. In some embodiments, the multivariate data analysis module is used to interpret mass spectrometry data (e.g., data in a mass spectrum) and to identify components from the composition of the mass. The township variable statistical analysis module can be used with a quadrupole mass spectrometer or a time-of-flight mass spectrometer. In some implementations, the control module or the multivariate statistical analysis module is used to detect and/or identify errors in the system and to interpret and/or analyze the data, for example, to identify from the mass spectrometer. The component of the composition peak.

The system can also include an extraction electrode disposed relative to the chamber. The extraction electrode defines a orifice through which reagent ions or product ions are passed to the quadrupole mass spectrometer module. The extraction electrode can also be operated to specify the energy value of the reagent ion or product ion for collection by the quadrupole mass spectrometer module. Some embodiments of the system are characterized by a lens assembly disposed relative to the chamber for concentrating reagent ions and product ions on an extraction orifice that facilitates reagent ions and product ions Transfer to the mass spectrometer module. In another aspect, the present invention is directed to a method for generating one or more reagent ions for a proton transfer reaction mass spectrometer or a chemical ionization reaction mass spectrometer. The method involves supplying a reagent Qin gas and providing microwave energy to the reagent vapor to produce one or more reagent ions. The method may also involve directing one or more reagent ions to a region to interact with components of the sample to form a product. ion. Reagent ions can be generated by microwave plasma. The reagent vapor may comprise water vapor, oxygen or oxidized nitrogen, and the reagent ions may be hydronium ions, oxygen ions or oxidized gas ions. In some embodiments, the microwave energy is provided by electromagnetic waves or radiation having a frequency greater than about MHz. In another aspect, the invention is directed to a method for generating one or more reagent ions for a proton transfer reaction mass spectrometer or a chemical ionization reaction mass spectrometer. The method involves supplying reagent vapors and supplying high frequency RF energy to the reagent vapors to produce reagent ions.

In some embodiments, the RF energy is provided by electromagnetic waves having a frequency between about 4 kHz and about 800 MHz. Reagent ions can be generated by capacitively coupling RF plasma. In another aspect, the present invention/1 IfW /ΓΓ kiss&quot;/2: the spleen reagent vapor is supplied to a plasma zone and the microwave or high frequency RF energy is supplied to the plasma zone. The reagent vapor forms one or more reagent ions. The method involves interacting the reagent ions with a gas sample to produce one or more product ions. The method also involves directing product and reagent ions to a collector region of a quadrupole mass spectrometer module, and determining the peak intensity and/or mass of the product ions and reagent ions by the mass spectrometer module. Another aspect of the invention pertains to a mass spectrometry system. The mass spectrometry system includes means for generating one or more reagent ions from a reagent vapor supply source by providing a reagent microwave or high frequency RF energy. The system also includes means for interacting the sample with the reagent ions to form one or more product ions. The system includes a means for directing product ions and reagent ions to a collector region, the member including an electromagnetic field. The system also includes means for connecting to the peak intensity and/or mass of each of the reagent ions 133727.doc •15-200937487 and the reagent ions. In one aspect, the invention relates to a system. The system includes a microwave or high frequency RF energy source for ionizing reagent vapors with microwave or RF energy to form one or more reagent ions. The system also includes a chamber including an inlet end, the inlet end allowing the sample The chamber is entered to interact with reagent ions from the microwave or RF energy source to form one or more product ions. The system also includes a mass spectrometer module that exits the orifice relative to one of the chambers. The mass spectrometer module includes a flight zone, product ions

Or reagent ions travel through the flight zone and the flight zone defines a path length. The mass spectrometer module also includes a collector region to receive product ions or reagent ions from the flight region. The mass value of the product ion or reagent ion is determined based on the amount of time that each of the product ion and the test smear traverses the length of the path. In some embodiments, the mooncake also includes an ion beam regulator that is positioned relative to the exit orifice of the chamber to pulse the product ions and test substreams into the flight zone. The mass spectrometer module also includes an optical system disposed in the flight zone for increasing the path length value of the product ions and reagent ions. The ion beam modulator can utilize a pseudo-random sequence provided from a controller to regulate the flow of product ions and reagent ions. In some implementations, an analysis module performs the most approximate (four) processing calculations on the data received from the mass spectrometer module (4) to determine the peak intensity and/or mass of the product (iv). The sub- &lt; art in the collection of the enchanting I I 3 knife analysis group can be deconvoluted from the data received by the mass spectrometer module to determine the value of the product ion or test or quality. The collector region #intensity and/or operation in pulse counting mode 133727.doc -16 - 200937487 a stacked microchannel plate finder or a bipolar detector ^ In some embodiments, the optical system includes a Reflector. The system can be characterized as: a lens that concentrates reagents and product ions on the ion beam adjuster, and the ion beam adjuster includes an ion beam interceptor, an ion beam gate, an ion beam adjuster, a Bradbury-Nielsen gate Extreme or any combination of these. In some embodiments, the system is also characterized by an optical system disposed relative to the chamber and mass spectrometer modules. The optical system includes at least one quadrupole & lens for directing reagent ions and product ion currents toward an ion beam regulator. In some embodiments, the mass spectrometer module defines a generally linear axis that passes through the flight zone. The generally linear axis may be substantially parallel to a second cypress (e.g., Uthoff track) passing through the flight zone. In some embodiments, the system includes a mass transitioner disposed relative to the microwave energy source and the chamber for selectively allowing a subset of reagent ions to enter the chamber. The filter can be a quadrupole mass filter. The system can be characterized by an analysis module for receiving data from the mass spectrometer module to interpret data in the mass spectrum. The data includes the peak intensity of the product ions and reagent ions and/or the value of the mass. The analysis module can be used to detect and/or identify errors in the mass spectrometry system. The analysis module can be based on multivariate statistical analysis. In some embodiments, the system features a multivariate statistical analysis module for identifying components of the sample based on mass spectrometry generated by the mass spectrometer module. The system can include a control module in communication with the system operable to detect or identify errors in the system based on operating parameters of the system. The control module can change the value of the operational parameter based in part on the detection or discrimination of the error. The system can include a system in communication with the system for operating parameters based on the system 133727.doc • 17· 200937487

A control module that changes the input parameter values of the system. In some embodiments, the system includes a set of electrodes disposed relative to the chamber for generating an electromagnetic field that facilitates interaction between the reagent ions and the sample and for directing product ions and reagent ions through the chamber Exit the orifice. Such a system may be characterized by a control module in communication with the electrode set for determining an electromagnetic field value within the chamber based on operating parameters of the system. The operating parameters of the system may include the composition of the sample, the pressure of the chamber, the velocity of the product ions or reagent ions passing through the chamber, the flow rate of the sample or reagent ions entering the chamber, the energy of the product or reagent ions, product ions, reagents The chemical composition of the ion or sample, or any combination of these parameters. The control module is also operative to vary the input parameters of the electrode set based in part on operational parameters. In another aspect, the invention is directed to a system. The system includes a microwave or high frequency RF energy source for ionizing particles of reagent vapors with microwave or RF energy to form one or more reagent ions. The system includes a chamber containing an end that allows a sample to enter the chamber to interact with reagent ions from the microwave or RF energy source to form - or a plurality of product ions. The system also includes a time-of-flight mass spectrometer module disposed relative to one of the chamber exiting the orifices for generating time based on the amount of time that each of the product ions and reagent ions traverse the mass spectrometer A spectrum of mass values including product ions and reagent ions. In some embodiments, the time-of-flight mass spectrometer module includes a flight product and helium ions traveling through the flight zone. The flight zone defines a path length. The time-of-flight mass spectrometer module also includes an ion beam adjuster for regulating the flow of reagent or product ions into the flight zone and a placement 133727.doc • 18· 200937487 in the flight zone for increasing product ions and reagents The optical system of the path length through which the ions travel. The mass spectrometer module also includes a collector for receiving product ions and reagent ions from the flight zone. In another aspect, the invention is directed to a method for processing signals in a time-of-flight mass spectrometer. The signals are based on one or more reagent ions generated by supplying microwave or energy to the reagent vapor and also based on one or more product ions produced by interacting the reagent ions with the fluid sample in an electromagnetic field. The method involves establishing a first ion stream comprising reagent ions and product ions, and varying the first ion current to produce a second ion current according to a specified flow pattern. The method also involves receiving the second ion stream at a - (IV) and determining a mass spectrum based on data conveyed by the detector based on a most approximate haptic statistical algorithm. The mass spectrum includes "data for the mass and/or peak intensity of the tester and product ions. In some embodiments, the second stream is a pulse stream. The pulse stream can be based on a specified flow pattern generated from the quasi-random binary sequence. In another aspect, the invention relates to a method of supplying reagent vapor to a plasma zone and providing microwave or high frequency RF energy to the reagent vapor in the plasma zone to form one or more Reagent ions. The method also involves interacting the reagent ions with a gas sample to produce one or more products. The method involves directing product ions and reagent ions along an orbit in a flight zone of a time-of-flight mass spectrometer module. It also relates to determining the peak intensity and/or mass of the product ions and reagent ions by the mass spectrometer module. One aspect of the invention relates to a method for measuring one or more reagent ions 133727.doc -19- 200937487 And a system of the mass of the product ions. The reagent ions are generated by supplying microwave or RF energy to the reagent vapor. The product ions are made by one or more The reagent ions are generated by interacting with the fluid sample in an electromagnetic field. The system includes a set of quadrupole lenses disposed relative to one of the drift tube assemblies and exiting the orifice for receiving reagent ions and product ions. Ion stream. The lens group receives product ions and "agent ions" through the exit orifice and produces a second ion stream that is directed to an ion beam regulator. The system also includes the ion beam modifier operative to selectively allow the second ion stream to be delivered to the flight zone of the time-of-flight mass spectrometer. In another aspect, the invention is directed to a system comprising a member for ionizing particles of reagent vapors with microwave or high frequency RF energy to form one or more reagent ions. The system also includes a means for interacting the sample with the reagent ions to form one or more product ions, including an electromagnetic field. The system also includes means for determining the peak intensity and/or mass of each of the product ions and reagent ions based on the amount of time that the product ions and reagent ions traverse a specified distance. In another aspect, the invention is directed to a system for measuring the quality of one or more reagent ions and one or more product ions. Reagent ions are generated by supplying microwave or RF energy to the reagent vapor. The product ions are generated by interacting the reagent ions with the fluid sample in an electromagnetic field. The system includes a means for establishing a first ion stream comprising reagent ions and product ions. The system also includes a means for adjusting the first ion current to produce a second ion current in accordance with a specified interruption pattern. The system also includes a means for generating a mass spectrum from the data conveyed by the free detecting component. The data pair 133727.doc -20- 200937487 should be in the second ion stream. In another aspect, the invention is directed to a system for measuring the quality of one or more reagent ions and/or product ions. Reagent ions are produced by supplying microwave or RF energy to the reagent vapor. The product ions are produced by interacting the reagent ions with the fluid sample in an electromagnetic field. The system includes an optical member for receiving a first ion stream comprising reagent ions and product ions. The optical member also produces a second ion stream directed to an adjustment member. The system also includes the adjustment member for selectively controlling the second ion stream toward a mass spectrometer. In another aspect, the invention relates to a method. This method involves introducing a sample gas. The method also involves supplying reagent vapor to a plasma zone and providing microwave or high frequency RF energy to the reagent vapor in the plasma zone to form one or more reagent ions. The method also involves interacting one or more reagent ions with the sample gas to produce one or more product ions and directing the product ions and reagent ions to a quadrupole or time-of-flight mass spectrometer module. The method involves determining the peak intensity or mass of the product ions and reagent ions by the mass spectrometer module. In another aspect, the invention is directed to a system. The system includes a microwave or high frequency RF energy source for ionizing particles of reagent vapors with microwave or RF energy to form one or more reagent ions. The system includes a supply source that facilitates analysis of a sample gas comprising at least one trace of one or more volatile organic compounds. The system also includes a chamber having an inlet end that allows the sample gas to enter the chamber to interact with reagent ions from the microwave or high frequency RF energy source to form one or more of 133727.doc -21 - 200937487 child. The chamber has an electromagnetic field generated in the chamber. The system = - a quadrupole or time-of-flight mass spectrometer module disposed relative to one of the chambers exiting the orifice for collecting product ions and reagent ions to aid in peak intensity or mass of product ions and reagent ions Determination of the value. In another aspect, the invention relates to a mass spectrometry system comprising a member for introducing a sample gas comprising at least a trace concentration of - or a plurality of volatile organic compounds. The system includes a reagent vapor for use

The supply source is a component that produces - or a plurality of reagent ions by providing microwave or high frequency (four) quantities to the reagent vapor supply source. The system includes a means for interacting the sample gas with the reagent ions to form - or a plurality of product ions. The system also includes - for directing product ions and reagent ions to a mass spectrometer module for determining at least one of peak intensity or mass of product ions and reagent ions or for identifying volatility in the sample gas A component of an organic compound. Additional features are related to the above. For example, the sample gas includes at least one or more volatile organic compounds at a trace concentration. The trace concentration can be between about megahertz and about one billionth of a gram by volume. The trace amount can be between about one part per billion and one part per million by volume. The method may also involve joining the gas sample inlet end to the enclosed space. The method may also involve positioning the gas sample inlet end in a non-closed space. The gas sample inlet can be connected to the container. In some embodiments, the gas sample inlet end is coupled to a venting member of a car or aircraft. The gas sample inlet end can be coupled to the headspace above the food or beverage product to, for example, determine the level of the food or beverage product. 133727.doc -22- 200937487 In some embodiments, the method involves positioning a gas sample inlet end proximate to a human oral cavity to introduce exhalation into the port. The method may involve positioning the gas sample inlet end adjacent to a solid sample material that emits a gas or vapor. In some embodiments, the gas sample inlet end is coupled to a supply of gas. A quadrupole or time-of-flight mass spectrometer module can be used to determine at least one of the peak strength or mass of a volatile organic compound in a gas sample, or the characteristics of a volatile organic compound. Volatile organic compounds (including trace concentrations of volatile organic compounds) that can be measured, detected, and/or identified include dioxin-based compounds, furan-based compounds, naphthalene, and benzene. , stupid, ethylbenzene, xylene, non-combustible organic compounds, primary organic aerosols, isobaric compounds, chemical warfare agents, battlefield gases, combustion improvers, by body fluids or via fungal substances (eg mycotoxins) The VOC substance emitted by the action of xin)), or any combination of these. In some embodiments, the volatile organic compounds include artificial or biologically derived volatile organic compounds. In some embodiments, the sample gas comprises an inorganic gas or a vaporous material (e.g., hydrogen sulfide). The details of one or more examples are set forth in the accompanying drawings and are set forth in the embodiments below. Other features, aspects, and advantages of the present invention will become apparent from the Detailed Description. [Embodiment] FIG. 1 is a plan view showing a component of a system 1 to which the present invention is embodied. System 100 includes a reagent vapor supply source 〇4 and a plasma generator 1〇8. The microwave/RF plasma generator 108 can generate plasma using microwave energy (microwave plasma) or high frequency scale 1 133727.doc • 23- 200937487 energy (RF plasma). The rf energy can be supplied by a capacitive surface combined with a high frequency rF energy source (not shown). The reagent vapor (not shown) from the reagent vapor supply source 〇4 interacts with the plasma in the plasma zone 112 to form a desired or specific reagent ion 'which can be one or more of a plurality of different substances, as such Depending on the particular application of system 100. In some embodiments, the plasma zone i丨2 and the microwave/RF plasma generator 1〇8 form part of the same component (not shown) to allow reagent vapor and plasma to interact within the assembly. In some embodiments, the plasma zone 112 is disposed inside a glass tube. The plasma zone 112 is in fluid communication with an electrically isolating orifice plate electrode 120 mounted within the flange 116. An insulator (not shown) is disposed between the flange 116 and the orifice plate electrode 120 to provide electrical isolation therebetween. A potential is applied to the f-flow plate electrode 120 to increase the potential of the plasma, thereby directing one or more reagent ions through the aperture 122 defined by the flange 116 and the orifice plate electrode 12 and into the drifting outer cavity. The chemical ionization/drift region 136 inside the chamber 124. The chemical ionization/drift region 136 is maintained at a lower potential than the orifice plate electrode 120. The sample supply source 128 is in fluid communication with the chemical ionization/drift zone 136 to provide a sample fluid (e.g., sample gas) to the system. The sample gas flows into an inlet port (not shown) to pass through the surface of the outer chamber 124 (not shown) and into the chemical ionization/drift region 136. The inlet end is positioned downstream of the orifice plate electrode 12A at the center of the flange 116, which allows reagent ions to be mixed with the sample gas within the chemical ionization/drift zone 136. There are other configurations for introducing reagent ions and sample gases into the chemical ionization/drift region 136 and are within the scope of the present invention. For example, the π-end can be directly coupled to the flange 116 to create a "shower head" effect when the sample 133727.doc 24-200937487 gas flows through a fluid path (not shown) that is radially positioned around the aperture 122. The drift assembly 126 includes a chemical ionization/drift region 136 and a pumping drift external chamber 124. The pumping drift external chamber 24 effectively accommodates the chemical ionization/drift zone 136. The chemical ionization/drift region 136 can be defined by a series of % electrodes and an insulating plate (with an intermediate 0 ring seal (not shown)) each having a channel disposed through its center. Chemical ionization/drift region 136 is discussed in more detail with reference to Figures 5 and 6. The chemical ionization/drift region 136 facilitates interactions between the sample and the reagent ions (e.g., chemical reactions). The interaction between the sample and the reagent ions forms one or more product ions. Typically, the reagent ions greatly exceed the composition of the sample gas and the reagent ions in the product ion stream can be monitored after product ion generation. The chemical ionization/drift region 136 typically includes an electromagnetic field (not shown) to facilitate interaction between the sample and the reagent ions as the sample and reagent ions are mixed within the chemical ionization/drift region 136. The electromagnetic field in the chemical ionization/drift region 136 also directs reagent ions and product ions toward the exit orifice 丨38. Ions passing through the chemical ionization/drift zone 136 and passing through the exit orifice 138 are concentrated on the exit orifice 144 defined by the flange 140. Exiting the orifice 144 allows ions to exit the drifting outer chamber 124. The ions are concentrated by the lens assembly 142 on the exit orifice 144. In some implementations, the lens assembly 142 includes a focusing aperture. Some embodiments use a three-element single lens for the lens assembly 142. Lens assembly 142 directs ions toward mass spectrometer module 148, for example, according to specified flow parameters such as ion flux, velocity, or momentum. Lens assembly 142 can be used to optimize passage through exit section 133727.doc • 25- 200937487 The number of ions in the aperture 144. In some implementations, the system 1 does not include a lens assembly. ❹

The mass spectrometer module 148, for example, measures the mass and quantity of reagent ions and product ions by collecting ions. The mass spectrometer module 148 generates and/or analyzes the resulting mass spectrum indicative of the characteristics of the reagents and product ions passing through the exit orifice 144. The mass spectrum associated with the product ions can be used to determine the presence, amount, volume, concentration, or characteristics of the components of the sample provided by the sample supply source 128. The reagent ion measurement is used to calibrate and/or error the system. The mass spectrometer module 148 can be a quadrupole mass spectrometer or a time-of-flight mass spectrometer. The system 1 also includes a control module 152. Control module 152 receives data regarding operating conditions or parameters of system 100. Based on the data, control module 152 can determine or set input values for system components or input operational parameters. For example, the control module 152 can receive from the reagent vapor supply source ι 4, the plasma generator 108, the plasma region 112, the orifice plate electrode 12, the chemical ionization/drift region 136, the lens assembly 142, The data of the orifice electrode 144 or the mass spectrometer module 148 is exited. The control module 152 can set the input values for each of the components in response to the collected data, for example, when the system is activated or in response to data received regarding the operational parameters. The control module 152 automatically updates the value of the input A of the operational parameter in response to the data received in some embodiments with respect to the operational parameters. For example, if the material parameters of the pressure or electromagnetic field of the chemical ionization/drift region 136(4) deviate from the specified or desired values of the parameters, the control module M2 can adjust the pressure in the set chemical ionization/drift region 136. Sample supply source 128 or an electrode that generates an electromagnetic field (not shown) until the parameters meet the input values or correct values of their parameters 133727.doc •26- 200937487. Other operational parameters include the velocity or energy of the reagent or product ions in the system, the flow rate of the fluid sample into the chemical ionization/drift region 丨36, and the flow rate of reagent ions into the chemical ionization/drift region 136. The composition of the sample, the relative concentration of the sample and reagent ions, or the relative concentrations of reagent ions and product ions. In some implementations, the control module 152 monitors a plurality of operational parameters of the system 1〇〇. In some implementations, control module 152 uses a plasma metering method to receive and/or update parameters of system 100. The plasma metering method can monitor, for example, the light emission spectrum from the plasma zone 112. Based on the light emission spectroscopy, the control module 152 determines the value of the operating parameters (eg, &quot;plasma parameters") within the plasma zone ,2, such as the intensity of a particular emission wavelength, and if the parameter deviates from the index or desired value, then The control module 15 2 can adjust the plasma parameters until the parameters meet the optimal values of the parameters. If the control module 152 fails to achieve the optimal conditions or parameters, the error conditions can be detected and/or recorded. In an embodiment, a mass filter (not shown) can be positioned between the microwave/RF plasma region 112 and the chemical ionization/drift region 136. The mass filter can be used to selectively allow reagent ions to enter the chemistry. In the ionization/drift zone 136. In some embodiments, the mass filter is a quadrupole mass filter. The system 100 includes one or more coupled to one or more pumps (not shown) for establishing the system 100. Port of pressure value (not shown). For example, the pressure values inside the microwave/RF plasma zone 112, the chemical ionization/drift zone 136, the pumping drift external chamber 124, and the mass spectrometer module 148 are By one or more fruits 133727.doc -27- 200937487 Figure 2 is a cross-sectional view of a reagent vapor supply assembly 200 of a mass spectrometry system (e.g., system 图 of Figure j). Component 2〇〇 is configured to be energy ( For example, the plasma generator 108 of Figure 1 provides a consistent or stable flux or flow of vapor. The vapor provided by the assembly 200 includes one or more reagent molecules that can be ionized by microwave or RF plasma, and is sometimes referred to as The reagent vapor comprises a reservoir 2 〇 2 for containing a fluid supply source. The reservoir 2 〇 2 may be constructed of stainless steel or other suitable metal. In some embodiments, the reservoir 202 contains water or pure Water to produce water vapor. As shown, 'Reservoir 2〇2 includes 5 ports. Port 2〇4 can be connected to a tube for introducing fluid into the reservoir (for example, to complete water or fluid supply) Or channel. Port 206 can be coupled to a tube or channel for delivering or delivering reagent vapors to the mass spectrometry system. Port 2〇8 can be coupled to a tube or channel for obtaining a measurement of fluid within reservoir 202 For example, port 208 Coupled with a capacitor pressure gauge for determining headspace pressure inside the reservoir 208. In some implementations, port 208 is not used. Port 216 can be coupled to a fluid used to measure reservoir 2〇2 A number of tubes or channels (e.g., connected to a water level indicator). Port 218 can be connected to a tube or channel for draining or evacuating a reservoir 2〇2 with fluid. Ports 208 and 216 are each Selected, and in some embodiments, 'not included in system 200 or used for mass spectrometry operations. In some implementations, each of ports 204, 206, 208, 216, and 218 can be connected to have 0.25. The diameter of the tube (about 635 cm). Other sized tubes or channels may be connected to the ports, and the tubes or channels do not have to be the same size. 133727.doc -28- 200937487 In some embodiments, the reservoir 202 is heated to a particular elevated temperature using a heater jacket 214 of the package reservoir 202. In some implementations, the control module 152 of FIG. 1 is coupled to the thermocouple 212. The temperature of the reservoir 202. (and the fluid therein) can be an operational parameter maintained, adjusted, and adjusted by the control module 152 in response to operation of the mass spectrometry system. This control allows the user to maintain the vapor pressure in the headspace 213 above the liquid surface 210 at a specified or desired value. Assembly 200 also includes a tube 222 that is fluidly coupled to mass flow controller 224. The mass flow controller 224 can determine the amount of reagent vapor flowing through the tube 226 and into the electrical zone 230. In the plasma zone 230, reagent ion generation occurs by applying microwave or RF energy to the reagent vapor. In some implementations, mass flow controller 224 can be a heated mass flow controller with separate electronic components that are remotely located from assembly 2 (not shown). Other types of flow controllers can be used in conjunction with the mass flow controller 224 or the alternate mass flow controller 2 24 . As shown, the assembly 2 〇 includes a gauge or monitor 228 for indicating the pressure value inside the plasma zone 230. The gauge can be a capacitive pressure gauge. In some embodiments, the control module 152 of Figure 1 is coupled to the gauge or monitor 228 and the pressure within the plasma zone 230 is an operational parameter maintained, adjusted, and adjusted by the control module 152. In some embodiments, the gauge or monitor 228 is not included in the assembly 200. In some embodiments, tube 222 and tube 226 are made of stainless steel and have an outer diameter of about 0.25 Å (about 0.635 cm). Tube 229 electrically isolates the body of assembly 200 from plasma zone 23 。. In some embodiments, tube 133727.doc • 29-200937487 229 is made of polytetrafluoroethylene (&quot;pTFE&quot;) and defines an outer diameter of about 〇 (about 0.635 cm). The pressure inside the plasma reaction zone 23 可 may be about 1-5 Torr (about 1 〇〇 7 7 Pascals) during the mass spectrometry operation. The pressure inside the component 2 (8) is maintained by a pump (not shown) located outside the module 2〇〇. For example, a pump coupled to the drift external chamber 124 (and in conjunction with the chemical ionization/drift region 136) can be used to establish pressure within the assembly 200 via fluid communication with the assembly 2 . The chemical ionization region 136 of Figure 5 can be fluidly coupled to the component 2 via vias 122 and plasma zone/tube u2. In some embodiments, port 220 is used to mix reagent vapors with another gas to improve reagent ion generation during application of microwave or RF energy. For example, the mixed gas can be an argon, nitrogen or argon/nitrogen mixture. In some embodiments, a gas or gas mixture (eg, NO or 〇2) to be used for reagent ion generation is introduced via port 22, and reservoir 202 and tube 222 are utilized by a valve (not shown). The flow between them is isolated. 3 is a flow chart 3 of a method for generating reagent ions. In step 305, a reagent vapor is supplied. For example, reagent vapor can be supplied according to system 200 shown in Figure 2 to supply a relatively consistent or stable flow of reagent vapor. The reagent vapor can be pure water vapor or water vapor mixed with a plasma mixed gas such as argon or nitrogen or a mixture thereof. In some embodiments, the reagent vapor comprises a reagent material such as nitrous oxide (N〇) or diatomic oxygen (〇2). In step 310, energy is supplied to the reagent vapor. In some embodiments, the energy is microwave radiation that is used to form an ionized microwave plasma. In some embodiments, the energy is a high frequency RF power source, which is used to form RF power. 133727.doc.30·200937487 A 'for example' is a type of rf electricity generated by a capacitive shank combined with RF energy. Refers to energy (eg, radiant energy) produced by electromagnetic waves having frequency values greater than about 800 MHz and less than about 300 GHz. High frequency RF energy generally refers to frequency values having greater than about 4 kHz and less than about 800 MHz. Energy generated by electromagnetic waves (eg, radiant energy) ^ In other words, RF energy can be provided at frequency values specified by the frequency bands of industrial, scientific, and medical radio centers. The energy applied in step 3 10 excites the molecules in the reagent vapor flux to

Reagent ions are generated. The molecules in the reagent vapor stream are ionized by the plasma. For example, when water vapor is used as the reagent vapor, hydronium ions are generated via a multi-step reaction: Reaction 1 Reaction 2 e_+H20-H20++2e_H20++H20-&gt;Η30++〇η Reaction/step and from The free electrons (6) of the ionized plasma interact with water molecules (KG) to form positively charged, ionized water molecules and second free electrons. In the reaction 2, the positively charged water molecules interact with the neutral water molecules to form water alpha hydrogen ions (Η3〇+) and a meridine. Hydronium ions can be reagent ions that subsequently interact with components of the fluid sample. It is desirable to have an intra-frequency RF plasma, as it provides an efficient means of generating a sufficient source of ions and electrons that are required for the production of reagent ionic species (e.g., hydrated ammonia ions). The high-frequency RF plasma is in contact with the rabbit, and the slurry is in direct contact with the 'very ^, with or without the internal splash and high coffee source associated with the electrode and the electric two cathode / glow discharge plasma source. The "less electrode" property means that it can reduce the effects of instability and drift with 133727.doc 200937487 electrode rot (4). In addition, microwave and high frequency RF plasma sources provide relatively high levels of reagent ions. In some embodiments, the method of FIG. 3 includes an additional step involving measuring the force of the microwave or high frequency RF plasma (not shown) the value of the plasma pressure can be a control parameter of the mass spectrometry system (eg, The plasma pressure can also be used to determine the appropriate supply of reagent vapor (e.g., reagent vapor from assembly 200).

Fig. 4 is a flow chart showing a mass spectrometry method for embodying the present invention. Step 405 involves supplying reagent vapors, and the steps are all directed to providing microwave or RF energy to the reagent vapor to produce reagent ions, for example, as discussed above with respect to Figure 3. Subsequently, by the combination of the fluid flow % produced by the pressure drop between the money reaction zone and the chemical ionization/drift zone, and the electromagnetic field gradient influence from the ion extraction orifice or electrode inside the chemical ionization/drift zone, The reagent ions are directed to the chemical ionization/drift zone. In step 415, a fluid sample (e.g., a gas containing one or more volatile organic compound molecules) interacts with reagent ions. Mixing the fluid sample with the reagent ions results in an interaction between the fluid sample and the reagent ions. For example, a fluid sample can be supplied to a reagent ion stream via an inlet line that passes through the drifting external chamber and into the chemical ionization/drift zone "pressure drop between the sample supply source and the chemical ionization/drift zone The fluid stream carrying the fluid sample can be assisted into the chemical ionization/drift zone. The chemical ionization/drift region includes an electromagnetic field that facilitates the movement of reagent ions within the region and facilitates collisions between reagent ions and components of the fluid sample. The collision between the reagent ions and the components of the fluid sample results in a chemical reaction that ionizes the particles of the sample 133727.doc -32- 200937487. Examples of sample materials and chemical reactions involving hydronium ions and component molecules having a proton affinity greater than the proton affinity of water are as follows: H30++R-&gt;RH++H20 Reaction 3 involves hydronium ions and substances The chemical reaction of π is a low energy and/or soft ionization interaction. For example, when compared to a high energy ionization process such as electron impact ionization, the integrity of the sample molecules does not change significantly and the molecular fragmentation of the sample is reduced or minimized. In addition, the substance in the sample with a proton affinity of less than the proton affinity of water was not ionized by collision with hydrated hydrogen atoms and was therefore not detected during mass spectrometry. Examples of such materials include common components of air, including diatomic nitrogen, diatomic oxygen, argon, carbon dioxide, and methane. In general, the components of air produce high intensity spectral peaks in a mass spectrum based on a ratio of the composition of the air in the sample to a significant proportion of the components present in the sample in trace amounts. High-intensity spectral peaks may blur nearby low-intensity peaks or may increase the difficulty of distinguishing between low-intensity peaks and high-intensity peaks. Therefore, the selective nature of this chemical ionization technology enhances the ability to distinguish spectral peaks attributed to low intensity/trace materials in the sample. In step 420, reagent ions and product ions are drawn from the chemical ionization/drift region via a lens or exit/throttle assembly and directed to the collector region of the mass spectrometer. In some embodiments, the reagent ions and product ions are extracted from the chemical ionization/drift region using an electromagnetic field established in the chemical ionization/drift region. Reagents and product ions can be passed through the lens assembly through the ion extraction orifice from the orifice at the end of the chemical ionization/drift zone to 133727.doc -33- 200937487 and enter the mass spectrometer module. The lens assembly may be characterized or may be characterized by a three-element single lens. Here, the ', , , , , and ion extraction orifices are placed inside a flange. In the second embodiment, the mirror assembly and the material extract the orifice, and the reading produces f plus the permeate ions passing through the orifice. Generally... in the phase = guiding reagents and production looking for the city, operating the mass in the relative vacuum, the instrument group to ensure that the molecular flow conditions can be "" effective operation.," instrument and its components

The instrument module can include a quadrupole f spectrometer or a time-of-flight mass spectrometer. For the HE type, the reagent and product ions are directed to the area of the mass spectrometer. The ions collide with the collector region, and the current is amplified in the mass spectrometer (for example, using a combination of an electron multiplier and a preamplifier 2). Based on input from the collector, the mass spectrometer accumulates data on reagents and product ions and produces a signal spectrum indicative of the mass value (or mass to charge ratio) and amount of collected ions. Step 425 involves, for example, determining the mass and amount of reagent ions and product ions based on the mass spectrum produced. (d) A good analytical peak of the towel can be used to determine the exact mass or mass-to-charge ratio of the reagent and product ions. The particular position of the peaks can also aid in the identification of the components of the fluid sample by comparing the mass values determined from the spectra or signal peaks to molecules or ions of known mass. In some implementations, the '-analysis module can be used to reveal the signal spectrum and/or to determine the presence and location of peaks in the spectrum. Fig. 5 is a cross-sectional view showing a quadrupole mass spectrometry system 5 of the present invention. System 500 includes a reagent ion source 504 coupled to a chemical ionization/drift zone 5〇8. The reagent ion source 5〇4 in system 500 is based on microwave energy, 133727.doc 34-200937487 which includes a magnetron 512 having a short antenna 514 disposed through aperture 516 of cavity 520. In some implementations, reagent ion source energy source 504 can be based on a high frequency energy source, such as an RF energy source. Reagent ion source 504 also includes a tube 524 that passes through cavity 520 through aperture 528. Tube 524 also passes through two microwaves 532 disposed on outer surface 536 of cavity 520. The microwave choke 532 lowers the amount of microwave energy that escapes the cavity 520 or tube 524 and reduces the microwave energy that extends to other components of the system 500. Tube 524 can be made of vermiculite or a vermiculite material such as quartz. In some implementations, tube 524 can be made of sapphire ©. End 540 of tube 524 can be coupled to a corresponding end (not shown) of a reagent vapor supply (not shown) for providing reagent vapor to reagent ion source 504. For example, end 532 can be coupled to tube 229 of reagent vapor supply system 200 shown in FIG. In some embodiments, tube 524 has an outer diameter of about 6 millimeters. The resonant cavity 520 defines the length / along the y-axis. The length / corresponds to or is approximately equal to one full wavelength λ of the lowest level resonant mode of the cavity 520. Tube 524 is positioned at a distance of about 5% from the top 544 of cavity 520 along the y-axis. More specifically, tube 524 is positioned at the opposite node of resonant cavity 520 to maximize the resonant energy transferred from resonant cavity 520 to tube 524. In some implementations, magnetron 512 is a 900 watt magnetron with short antenna 514 that provides microwave power to resonant cavity 520. The power is distributed in the cavity 520 by electromagnetic wave radiation having a frequency value in the microwave spectrum and transferred to the tube 524. Plasma is generated inside the tube 524 due to the resonance energy inside the cavity 520 that interacts with the reagent vapor inside the tube 524. The reagent vapor enters the tube via a tip 540 coupled to the reagent vapor supply source 133727.doc • 35- 200937487 524 due to the pressure drop between the tube 524 and the chemical ionization/drift chamber 5〇8, the reagent vapor supply source (eg) along The helium shaft provides or directs a reagent vapor stream into tube 524. The continued flow of reagent vapor ensures that the microwave plasma is maintained inside tube 524 to produce one or more reagent ions, for example as discussed above. In some embodiments, the resonant cavity 520 is constructed of a silver plated aluminum extrudate having a closed end (e.g., a top 544 and a bottom 548 of the cavity 520). In some embodiments, the microwave choke 532 is cylindrical in shape having a centerline (not shown) that is parallel, coaxial, or collinear with the x-axis. The microwave reactor 532 can be made of stainless steel or aluminum. In some implementations, the channel 533 is placed within one or both of the microwaves 532. The length of the channel 533 can be approximately % of the y-axis. The second end 552 of the tube 524 terminates at a face 557 (see Figure 6) that is clamped inside the flange 560 and connected to the orifice plate 556 of the chemical ionization/drift zone 508. Reagent ions pass through orifice plate 556 from tube 524 and into chemical ionization/drift region 508. The chemical ionization/drift region 508 is defined in part by a ring electrode 564 disposed in a spatial relationship along the axis of the drifting outer chamber 562 along the re-axis. A potential is applied to each of the electrodes 564 to generate an electromagnetic field. In some embodiments, the electromagnetic field has a linear field gradient guided along the x-axis. The value of the positive potential applied to each electrode decreases in the positive direction of the X-axis to produce an axially-directed linear field gradient. Nonlinear field gradients can also be used. The electrodes 564 are electrically isolated from one another by an annular insulating component 568 disposed therebetween. The electric field facilitates interaction between reagent ions from reagent ion source 504 (e.g., tube 524) and samples introduced at chemical ionization/drift chamber port 566. 133727.doc -36- 200937487 The drift external chamber 562 also includes a fruit pumping port 576 that is lightly coupled to the pumping system 58. The drift external chamber 562 also includes an electrical feedthrough port (not shown) and has a sample introduction line (not shown) for fluid communication with the total dust gauge 572 and a second gauge (not shown). Port 571 of the fitting (not shown). In one embodiment, the chest pumping system 58 includes a thirsty wheel molecule and a diaphragm pre-pump (not shown). Pumping system 580 establishes the desired pressure within the drift outer chamber and chemical ionization/drift region 508. The pressure inside the drift chamber 508 can be monitored by the total pressure gauge 572, and the pressure in the drift external chamber 562 can be monitored by the first gauge (data not provided by the gauges can be supplied as input to the input) The control group (not shown), for example, is used for system diagnostic processing. The chemical ionization/drift zone 508 and the drift external chamber 562 include a flange 584 that is opposite the mass spectrometer 592 via the double-sided flange 586. The flange 5-1 is shown in the system 500. The mass spectrometer 592 shown in the system 500 is four-inclusive and includes a fluid flow = & the pumping system 596 establishes the pressure inside the mass spectrometer 592 (eg ) to measure the mass of reagent ions and product ions, and to reduce the negative effects of this measurement of ion mass produced by interaction with environmental components in the mass spectrometer. Self-chemical ionization / drift The ions passed to the mass spectrometer 592 in region 508 are directed to mass spectrometer probe 594 by ion extraction electrode 582. In some implementation green samples, an ion optical assembly (not shown) can be used in conjunction with ion extraction electrode m = Pass to mass spectrometer 592 The number of reagent ions and product ions is exemplified by § '彳 using a $ coke or three-element single lens. Spectrometer probe 133727.doc -37· 200937487 ::What is an electric offset quadrupole mass analyzer or mass filter. Quadrupole Mass: The thief consists of four (for example) flat metal 'stems that are positioned as square vertices and positioned parallel to the X-axis. The opposite pair of poles are electrically coupled to produce two electrical coupling couples j. With a positive DC voltage component A second amount of RF energy or voltage that can be applied to the rod of the first dipole and that has a negative DC (quad) component can be applied to the rod of the second dipole. The ions in the stable orbit through the mass filter are The rods are transferred in a direction generally parallel to the 捍 (9), for example, parallel to the central axis of the square. The RFw or DC energy applied to spectrometer probe 594 produces a mass selective vibrating field. The mass selective field produces ion orbitals having a specified geometry, such as a vibrating geometry having a direction that is often along the X axis. The trajectory is commanded so that the mass-to-charge ratio within the specified range reaches the (four) device, and the ions outside the reduced range do not follow = the channel reaches the detection IS 598. Unselected ions collide with the rod and are not collected by the debt detector 598. In some embodiments, the mass selective field varies depending on the value of the energy (e.g., potential, DC energy, or RF energy) applied to the quadrupole. The bandwidth of the quality value can be selected using a particular field strength or flux. Additionally, spectrometer probe 594 can scan the mass range by varying the f-quantity selective field. In some embodiments, the spectrometer probe 594 includes a three-pole linear, coaxial series called a triple filter quadrupole mass analyzer. In such embodiments, the first and third elements of the triple passer are relatively short (eg, approximately W or 2.54 cm) &quot;single RF&quot; filtered $, carried by the second or main filter To (4) the pressure element. These &quot;separate rf&quot; pre and post filters act as ion lenses and concentrate ions on the mass filter assembly 133727.doc -38- 200937487 focus on the mass filter assembly. The purpose of using the pre- and post-filters in this manner is to improve the transport of ions through the filter assembly by increasing the amount of ions transported, especially with higher mass (eg, over about 80 atomic mass units). Plasma transfer. The front and rear filters also improve the mass resolution and abundance sensitivity of the filter. Successfully worn • The ions of the double filter assembly are collected by detector 598. In some implementations, the detector 598 is an electron multiplier detector. The electron multiplier detector amplifies the electricity generated by the ion collision with the entrance or front of the detector (not shown). signal. Figure 6 is an enlarged view of the chemical ionization/drift region 5〇8 shown in Figure 5. The chemical ionization/drift zone 508 includes a chemical ionization/drift chamber 62A that can be worn on the ion extraction electrode 612 that defines the extraction orifice 616. As the reagent ions move from the plasma zone 608 to the chemical ionization/drift zone 5〇8, the reagent ions pass through the extraction orifice 616. The ion extraction electrode 612 can be fluidly coupled to an energy source (not shown). The ions pass through the extraction orifice 616 under the influence of an electromagnetic field generated by the zeta potential applied to the extraction electrode 612. The extraction electrode 612 is coupled to the flange 6〇4 by one or more screws (not shown) having a ceramic insert or an insert made of another insulating material. The screws and inserts pass through an insulating (e.g., ceramic or PEEK) collar 014 to further electrically isolate the extraction electrode 612 from the flange 604. In some embodiments, the value of the potential applied across the extraction electrode 612 affects the chemical ionization of the reagent ions along their centerline a (substantially parallel to the X-axis) to the chemical ionization/drift region 5〇8/ The average energy in the drift chamber 620. Additionally, the size and/or geometry of the extraction orifice 616 determines the amount of reagent ions flowing into the chemical ionization/drift 133727.doc • 39-200937487 shift chamber 620. Ions pass through the extraction orifice 616 in the extraction electrode 612 and enter the chemical ionization/drift chamber 620 generally along the centerline A (e.g., in the axial direction of the X-axis or parallel to the X-axis). An electromagnetic field is generated in the drift region 620 by the potential applied to each of the one or more plate electrodes 624 and the drift end plate electrodes 625 (also referred to as electrode stacks). The electrodes may be made of metal or other conductive material. In some implementations, plate electrode 624 and drift end plate electrode 625 each have an annular shape with central orifices 630 and 633 aligned with centerline A. The center orifice 630 of each plate electrode may have a diameter of approximately 10 mm. The center orifice 633 of the drift end plate electrode may have a diameter of approximately 2 mm. Other diameters and geometries (e.g., non-circular) are within the scope of the present invention. The plate electrode 624 and the drift end plate electrode 625 are physically and electrically isolated by one or more insulating collars 628. In some embodiments, the insulating collar 628 has an annular shape with a central orifice 631 aligned with the centerline A. The central orifice 631 in the insulating collar 628 can have a diameter of approximately 20 mm. Other diameters and geometries are within the scope of the present invention. Suitable materials for the insulating collar 628 include polymeric materials such as those made from PEEK:TM sold by Victrex pic of Lancashire, England, or static consumption plastics such as those from Quadrant Engineering Plastic Products of Reading, Pennsylvania. SEMITRON® for sale. Ring 0 (not shown) is located inside the annular groove on either side of the insulating collar 628. The ankle ring facilitates a hermetic seal at the interface between the insulating collar and the plate electrode 624 or the drift end plate electrode 625. In some embodiments, the 0 ring can be obtained from VITON® fluoroelastomer sold by Du Pont Performance Elastomers of Wilmington, Delaware 133727.doc -40-200937487. The extraction electrode 612, the plate electrode 624, and the drift end plate electrode 625 cooperate to generate an electromagnetic field inside the chemical ionization/drift chamber 620. In some implementations, the electromagnetic field has a linear field gradient along the X axis. The electromagnetic field gradient can also be non-linear, for example, based on the difference between the potential applied to each of the extraction electrode 丨2, the plate electrode 624, and the drift end plate electrode 625. The electromagnetic field directs the reagent ions and aids in the interaction between the reagent ions and the components of the sample fluid. © In some embodiments, along the centerline A, a decreasing potential is applied to each of the plate electrode 624 and the drift end plate electrode 62 5 in an increasing direction along the X axis to facilitate reagent ions and The product ions flow within the chemical ionization/drift chamber 620. The sample gas system is, for example, as discussed in Figure 1, via a port in one of the drifting external chambers (e.g., port 57A of Figure 5) and then via port 632 in the side of insulating collar 628, from the sample supply source (not shown) is supplied to the chemical ionization/drift chamber 62A. A similar port in the side of the other insulating collar 0 628 can circulate with the gauge 572 fluid on port 571 of Figure 5 to aid in the measurement of the pressure inside the chemical ionization/drift chamber 62. In some embodiments, the sample supply source is comprised of a mass flow controller that controls the flow of the fluid sample entering the chemical ionization/drift chamber 020. The sample gas is released along the centerline A in an increasing direction along the X-axis and interacts with the reagent ions. The plate electrode 624 and the drift end plate electrode 625 are fixed to an extraction electrode 612 that supports the plate electrode 624 and the drift end plate electrode 625 inside the chemical ionization/penetration chamber 620. In some implementations, a control module (not shown) is coupled to each of the ion extraction 133727.doc 200937487 pole 612, the plate electrode 624, and the drift end plate electrode 625 to provide a potential to the electrodes 612, 624. And each of 625. The control module also monitors other parameters within the chemical ionization/drift chamber 620, such as field gradients, pressure, or detected ionic strength. The control module resets or adjusts the value of the potential applied to each of ion extraction electrode 612, plate electrode 624, and drift end plate electrode 625 when the value of the particular monitored parameter deviates from the predetermined threshold. In some implementations, the control module automatically changes the potential of each of the ion extraction electrode 612, the plate electrode 624, and the drift end plate electrode 625 via a feedback loop in response to a change in the parameters of the chemical ionization/drift chamber 620. . For example, the control module can establish an electric field gradient and pressure as an initial condition or mode that determines the optimal e/n (e.g., charge density) setting for a given sample monitoring demand. In some implementations, the control module can monitor the parameters of the chemical ionization/drift chamber 620 and maintain an optimal e/n level via an immediate adjustment of the electric field gradient and/or pressure. In some embodiments, the control module can be based on user-induced adjustments at the e/n level - for example, chemical ionization when different e/n levels are used to distinguish between two isostatic compounds / Drift chamber 620 changes in field gradient and/or pressure level. In some embodiments, the electric field gradient established by ion extraction electrode 612, plate electrode 624, and drift end plate electrode 625 is linear along the x-axis (or centerline A). In some implementations, the electric field gradient is non-linear. Another parameter that can be monitored by the control module and associated with the electric field, pressure, and e/n levels within the chemical ionization/drift chamber 620 is the ratio of product ions to reagent ions. The drift outer chamber 562 incorporates a fixed flange 636 that is secured to the corresponding flange 640 of the mass spectrometer 644 by a bilateral flange 648 disposed therebetween in the middle of the 133727.doc • 42·200937487. Ion extraction electrode 652 defining extraction orifice 656 is affixed to flange 648, for example, using one or more insulating screws 660. An insulating collar 658 (e.g., made of ceramic) electrically isolates the ion extraction electrode 652 from the bilateral flange 648. The metal plate 659 shields the insulating collar 658 and reduces the accumulation of surface charges, which may interfere with the ion optics in the region 657 between the chemical ionization/drift chamber 620 and the mass spectrometer 644. A potential is applied to ion extraction electrode 652 to generate an electromagnetic field that directs reagent ions and product ions from chemical ionization/© drift chamber 620 to mass spectrometer 644. Mass spectrometer 644 includes a spectrometer probe 664 having one or more apertures 668 to facilitate vacuum pumping and/or evacuation of mass spectrometer 644 and spectrometer probe 664. Spectrometer probe 664 is generally aligned with centerline A, and ions can enter spectrometer probe 664 via focus electrode 676 along centerline A. Spectrometer probe 664 is coupled to an analysis module that generates and/or exhibits a mass spectrum based on reagents and product ions collected by a detector (not shown) coupled to spectrometer probe 664. In some embodiments, additional ion optics (not shown) are used in region 657 between chemical ionization/drift chamber 620v and mass spectrometer 644, for example, to optimize mass spectrometer 644 The amount of reagent and product ions. Ion optics can be in the form of a focal hole or a three-element single lens. Figure 7 is a plan view of a time-of-flight mass spectrometer system 700 embodying the present invention. System 700 includes an ion source 704 for supplying ions to system 700. Ion source 704 can supply product ions and reagent ions from chemical ionization/drift chamber 620 of, for example, chemical ionization/drift region 508. Ions are transferred from ion source 704 to time-of-flight mass spectrometer 708 via ion current. From 133727.doc -43- 200937487, an ion extraction orifice (not shown) in an ion extraction electrode (not shown) that is electrically isolated from time-of-flight mass spectrometer 708 can be introduced into time-of-flight mass spectrometer 708. The potential can be applied to the ion extraction electrofine to generate an electromagnetic field for use in ionizing the time-of-flight mass spectrometer 708.

The time-of-flight mass spectrometer 708 is in fluid communication with a pumping system 7U that establishes pressure within the flight chambers 7〇8. The ions (4) apply an ion optic assembly 716&lt;&gt; to the ion lens assembly 720 comprising one or more potentials to the ion lens 720 to provide an electromagnetic field that directs the ion beam and defines the geometry of the ion beam. For example, ion lens 720 can constrain the possible orbits of the ion current and thereby concentrate the ion current or increase the ion flux through a smaller volume. Ion lens 720 also reduces the variability in the velocity spectrum or distribution of ions. In some embodiments, ion lens 720 is an electrostatic lens, such as a quadrupole lens that applies a plurality of DC potentials. Ion lens 72G produces a focus field that interacts with the ion stream to minimize spatial variability in the direction of ion flow (e.g., along track 728). Optical component 716 can optimize the characteristics of the ion beam or ion current to, for example, increase the ion flux, momentum or velocity of the ion current. The improvement of the beam characteristics allows for improved resolution of the mass spectrum and improved yield measurements of the peaks in the mass spectrum. The peaks in the mass spectrum indicate the (four) or number of specific ions with a particular f magnitude. Improved resolution of mass spectra and spectral peaks allows for improved peak-to-spectral or signal-to-signal differences. The ions exit the optical assembly 716 in a concentrated flow directed toward the ion beam regulator 724. The ion beam adjuster 724 can be a shutoff assembly that interrupts or regulates the flow of ions through the flight zone 732 along the track 728. In some implementations, the ion beam adjuster 724 is coupled to a drive system (not shown) (e.g., a digital electronic control module that controls the parameters of the ion 133727.doc • 44· 200937487 beam adjuster 724). Parameters can be controlled based on the specified interrupt or flow pattern. The parameters include positive and negative voltages applied to alternating lines in the ion beam regulator that produce ion scattering when a voltage is applied and produce uninterrupted flow of ions along the lane 72 8 when no potential is applied. (or pulse). The magnitude of the positive and negative voltages applied in some embodiments can be adjusted for optimum performance. In some implementations, the drive system controls the parameters of the ion beam regulator 724 according to a specified pattern, e.g., repeatedly opening and closing the ion beam regulator gate for a particular period of time. The drive system can also control the parameters of the ion beam adjuster 724 based on a random or unspecified pattern. In some implementations, the drive system is based on a quasi-random binary sequence that produces a pulsed flow of ions along the track 728. In some embodiments, ion beam modifier 724 is an ion beam that can be rapidly switched to produce a pulsed ion current, e.g., according to a specified flow pattern. An example of a suitable ion gate is referred to as a Bradbury_Nielsen gate ion along track 728 that moves in the decreasing direction of the X axis and moves toward the second optical system 736. Optical system 736 can be a reflective member (also referred to herein as 736) that affects and/or changes the direction of track 728 by reflecting ions, wherein the path of track 728a is symmetrical with the path of track 728, and its axis of symmetry passes through the reflection The center of piece 736. In some implementations, the reflector 736 includes a set of electrostatic lenses (not shown) to reflect and/or redirect the flow of ions along the reflective track 728a. In some embodiments, the reflector 736 is comprised of two portions of a resistive glass tube that are bonded together. A gate (not shown) is located on the front side 730 of the reflector 736 and a second gate 738 is located between the two bonded tube portions. Solid 133727.doc •45- 200937487 A constant potential can be applied to the front side 730 of the reflector 736, the gate between the two portions of the tube, and the gate at the back side 734. This type of configuration allows an electric field gradient to be established inside the tube for ion reflection. Upon exiting the optical system 736, the ions follow the reflective track 72 8 a to reach the detector 740 » The optical system 736 can be used to increase the path length/increase beyond the length of the ions traveling in the flight zone 732, for example, to increase the mass spectrum obtained. The resolution of the signal peak. The path length/can have known or measured values, for example, the sum of the lengths of each of the track 728 and the reflective track 728a. Ion traverse path length / amount of time required can be used to determine the mass or mass to charge ratio of reagent or product ions. For example, the length of the traversing path/the amount of time required indicates the velocity or kinetic energy of the ions in the flight chamber 708 under the influence of the electromagnetic field generated by the optical system 716 after acceleration. The length of the ion traversing path/time spent can be used with L'rentz f〇rce law and Newton's second law to determine mass or mass-to-charge ratio. Optical system 736 can also be used to correct for kinetic changes in reagent ions and product ions. Ions with relatively higher kinetic energy travel farther in the optical system (along the decreasing 乂 axis) than ions with relatively lower kinetic energy. This phenomenon is sometimes referred to as penetration or penetration of the reflector. Positioning the detector 7 4 at or near the focus of the track 728 or the reflective track 728a reduces the effect of the energy distribution on the mass spectrum. Ions of different pulses from ion beam modifier 724 that move through flight zone 732 can be mixed in flight zone 732, which causes a signal in the mass spectrum produced by the detector or by the detector 74(). The convolution 4 detector 74 is typically located at or near the Moon &amp; volume focus so that ions of the same quality but different energies exiting the optical system are collected by the detector at approximately the same time 133727.doc • 46· 200937487 episodes. In some implementations, detector 740 is a stacked microchannel plate type detector. The detector 740 operates in a pulse counting mode. The pulse count mode allows individual ions to be collected as they pass through the flight zone 732 as they reach the detector. In some implementations, the detector 74 is used in conjunction with a signal discriminator, an amplifier, and/or a time digital converter (TDC). • When the ion beam adjuster 724 uses a quasi-random binary sequence type pulse, the signal obtained from the ions collected by the (four) detector 74G can be deconvoluted using techniques from the (4) processing technique, such as statistical signals. Statistical Signal Processing Techniques amp &amp; statistical analysis of convolved signals or spectra to provide information about signals or spectra. One example of a suitable signal processing technique for deconvolving the resulting signal is the most approximate signal processing. Most likely signal processing typically performs statistical calculations based on measured events. For example, for a set of measurements/indicators of 丨 to # and variables and events, the fitting function can be determined based on the measured data & The fitting function will consist of m parameters α, ., 丨 from 1 to speak. The fitting function can be written in the form of a curry (6)~, α2 ..) for each event. For each event, the 〆X:·) fitting function can be transformed into a normalized probability density function (7); with ~,,.,, ‘). The probability density function 计 can be calculated under the observed value of ^. The approximate function illusion, ..., ~) is the product of the individual probability densities, so that 屯~.,~) = ten and the most approximate values of the various parameters can be minimized by minimizing the approximate function of the parameters Ζ ( In some embodiments, the time-of-flight mass spectrometer 7 is operated using a pseudo-random binary sequence pulse of the ion beam adjuster 724 to produce a convolved signal or spectrum. (4) The most approximate use The signal processing convolves the convolved signal or spectral solution 133727.doc •47· 200937487. When this mode is used, the ion beam regulator 724 allows the ion to pass through approximately 50% of the total available time, which allows the total available ion Approximately 50% passes through the flight zone 732. This &quot;high duty cycle&quot; operation of the time-of-flight mass spectrometer provides performance benefits in terms of increased signal to noise ratio, improved sensitivity, and wide dynamic range. In an embodiment, the time-of-flight mass spectrometer 700 operates in a single pulse mode in which all of the ions from a single pulse of the ion beam adjuster 724 are collected by the detector 74 before the subsequent pulse triggering of the ion beam adjuster. In addition to the benefits of operation provided by the high-load cycle of the time-of-flight mass spectrometer 700, most likely signal processing provides additional performance improvements over other signal deconvolution methods. Most likely signal processing such as Bosson noise (Poisson noise) signal noise instead of Gaussian noise (which (6) noise). Most likely signal processing can also refer to the actual instrument response function, such as the actual ion beam regulator pulse shape ' instead of the idealized instrument response function. Such performance improvement will help increase the signal resolution and further increase the signal noise ratio and dynamic range. In some implementations, the most approximate signal processing is performed by a data analysis module (not shown). The module can also be used to identify substances in the mass spectrum, for example, based on lookup tables or single variable or multivariate probability methods. In some implementations, the data analysis module can be based on multivariate statistical analysis. Examples include, for example, partial least square discriminant analysis using Hotelling-type analysis or DModX type analysis PLS-DA) or primary component analysis. In some implementations, the data analysis module is used to interpret the sample data to determine if the sample is associated with a particular group 133727.doc -48 - 200937487. In some implementations The data analysis module monitors the diagnostic output of the system to determine if an error has occurred in a system such as the system of Figure 1. There are many applications of the mass spectrometry systems and techniques described herein. Detection of trace amounts or concentrations of volatile organic compounds. The sensitivity and ability to detect and identify trace amounts of volatile organic compounds in real time provides a variety of applications for the systems and methods herein. Specific applications include sampling of gases (e.g., ambient air, gases from a confined space, gases from a gas supply, from a solid sample, or from a container or from a top of a food or beverage product). Subsequently, the taken gas is introduced into the gas sample inlet end and interacts with the reagent ions to form product ions. The specific application and detection of volatile organic compounds is related to how and where the gas sample inlet is located. In some embodiments, the gas sample population end includes specific application features to adapt the gas sample inlet end to the needs of the application. For example, in medical diagnostic applications, the gas sample inlet end can be coupled to a mask covering the nose and mouth of a person. The gas sample inlet or mask may also incorporate a bacterial filter. In applications involving sampling from an environment containing particles, the particle filter can be incorporated into, for example, a sample line or a gas sample inlet end. In applications where the sample vapor contains condensable material, the heater can be incorporated into a system (e.g., a sample line) to heat the sample line to a particular temperature. Examples of sample gas collectors include vessels, canisters or vacuum based products containing gas for delivery into the inlet end of the gas sample inlet. The gas collector collects gas in the environment where the gas is found internally and stores the gas for later analysis. In this case, the collector is relatively gas impermeable. In some embodiments, the gas collector includes an outlet end that feeds into the gas sample inlet end and into the drift chamber for immediate detection and/or monitoring. Various applications of the mass spectrometry systems and methods described hereinafter are within the scope and spirit of the invention. One type of application of the mass spectrometry technique involves measuring trace concentrations of volatile organic compounds in air including ambient air. "Environmental air can be self-enclosed or non-enclosed (eg, by approaching the gas sample inlet end) Sampling for ambient air positioning). VOCs in urban areas can be monitored to detect vehicle emissions or contaminants in cities and towns and/or industrial sites. These volatile organic compounds are sometimes referred to as artificial vocs. For example, industrial sites may include chemical plants, waste incineration plants, steel and/or cement production facilities. Industrial facilities can distribute materials such as dioxin substitute (and dioxin-based compounds), furan (and furan-based compounds), gas phenol, naphthalene, stupid 'toluene, ethylbenzene, xylene (collectively BTEX) substances. 〇c. In addition, VOCs or urban hazardous air pollutants are responded to by a regulatory agency (such as the Environmental Protection Agency in the US or other national environmental agencies (MfE)), such as V〇C starting or non-methane organic compounds. Start with a specific program to identify. In some embodiments, positioning the gas sample inlet end adjacent to the waste incineration plant or stack is suitable for immediate monitoring and adjustment (e.g., immediate feedback) to reduce emissions. This instant monitoring is also suitable for confirming the specified efficiency of the scrubber and optimizing the combustion process. 133727.doc • 50· 200937487 In some embodiments, the gas sample population end is positioned in an enclosed space to monitor the v〇c content in the air in the enclosed space. Examples of enclosed spaces include interiors of buildings, interiors of vehicles and interiors of aircraft inspections. Gas can be sampled from the location of the work area (for example, a semiconductor manufacturing facility or a clean room in a caster yard) to ensure that environmental regulations (such as occupational safety and heahh regUlatl〇nS) are met. ) compliance. The gas sample inlet can also be used for immediate monitoring, detecting air conditioning and filtration systems in buildings for ambient air control, 'for research, diseased buildings' syndromes, (iv) including buildings inside steam leak buildings Degradation of materials and testing of consumable products inside the building (eg, fumes from coatings and materials). The mass spectrometry described herein can be used to monitor and detect, for example, the stomachs of forests and/or factories that are not in urban, rural, or remote locations. Typically, this type of VOC is referred to as a "biological source". In some embodiments, a gas sample is taken from the headspace of a container containing a soil sample (eg, for testing from a contaminated site or its surroundings) The vocabulary in soil samples. Mass spectrometry can be used to monitor, detect, and analyze gas generated by landfills, livestock areas (including concentrated animal feeding operations), and/or water systems. In non-enclosed spaces, The gas sample inlet end can be positioned downstream of the vehicle or aircraft engine vent to monitor and/or quantify the vocal content of the stimuli or other gases of interest (including hydrogen sulfide (Hj)). It can also be applied to study atmospheric chemistry and/or atmospheric composition by positioning the gas sample inlet end to obtain atmospheric gases. The gases are analyzed to evaluate the photooxidation process and/or lead to organic aerosols. 133727.doc 51 200937487 Other mechanisms of formation, including the second-level technology of specializing in fossils, can also be applied to the food and beverage industry. For example, go to the top space above the eight/drink products. The gas can be analyzed using mass spectrometry. The headspace can be in an enclosed space (for example, inside a sealed container) or in a non-enclosed space. Examples of food and beverage applications include monitoring, sanctioning, and grouping of various foods: taste and/or aroma Such foods as coffee, olive oil, dairy products, meat products (including poultry and pork), fish products, herbs and spices, beer, wine and their money materials can be determined based on the voc component that contributes to the taste And/or identifying the taste of the gas. Chemical ionization and/or proton transfer reaction mass spectrometry can be used to monitor food spoilage and/or decay, for example, by analyzing VOCs produced by bacterial activity in food. Mass spectrometry can be used to determine the freshness of foods (such as bread), and to provide quality assurance and quality control, as well as to help determine product stability and shelf life. Mass spectrometry technology can be used to include mixing, blending, baking and cooking. The process of food manufacturing is monitored and used to determine if a particular batch of food is unsuitable for distribution or consumption. In the beverage industry, mass spectrometry can be used to detect contamination from food packaging in foods (eg, solvent residues or contaminants from plastic food packaging). The mass spectrometry techniques in this paper test water-soluble and fat-soluble antioxidants and / or applicability when used in other food additives in various foods. Chemical ionization and / or proton transfer reaction mass spectrometer is also in medicine and 133727.doc • 52- 200937487

The health=domain has applications as an instrument for diagnosis or prognosis. The gas sample population can be brought close to human oral positioning to provide human beer to the mass spectrometry system. V〇c in the breath can indicate the presence of a specific U disease or physical condition in the body. There are several examples of applications involving v〇c; For example, breathing can be analyzed to detect various types of cancer, such as lung cancer, by detecting: brothel k or benzene organisms. For reasons such as tuberculosis, diabetes, fungal instimulation as in (4) patients, schizophrenia and/or other conditions of bipolar disorder, breathing may also be analyzed based on the vocal substance in the patient's breath and its amount. ~ Mass spectrometry as described herein can also be used to monitor kidney or other renal function. g In the presence of a bacterial infection, the human breath of a patient with cystic fibrosis may include a specific VOC&apos; and may diagnose the infection. In some embodiments, human breathing includes a particular vocium indicative of an organ transplant rejection. Human respiration can also include trace levels of potency enhancing drugs that can be detected by the spectroscopy. VOC respiratory analysis and detection can also be used for diet and training programs for athletes and patients. Using the mass spectrometer described in this document, VOC analysis of human respiration can be used to assess and monitor metabolic function and to diagnose thyroid problems. Chemical ionization and/or proton transfer mass spectrometry have applications in the fields of safety, biosafety, forensic science and criminal investigation. For example, the systems and methods described herein can be used to monitor and detect explosive materials, chemical warfare agents (CWA) and/or battlefield gases, combustion improvers (in arson investigations), and locations where corpses are buried. In addition, the inlet end of the gas sample can be positioned to collect human breath for screening for exposure to CWA or battlefield gases. Quality 133727.doc -53- 200937487 Spectral assays can be used to detect and analyze specific vocatures that characterize different body fluids (eg, evidence collected at a crime scene). The concepts described herein may also be applicable to screening and detecting abuse of anesthetics and/or drugs via a breath analysis or by coupling a gas sample inlet end to a container suspected of containing a drug. More generally, the gas sample inlet end can be coupled to a shipping container or package to detect voc, which is characteristic of the material or substance (e.g., anthrax or spore) that poses a biosafety threat. The technique can also be used to monitor agricultural pest and pathogen contamination as indicated by the presence of V〇C in crops. For example, the gas sample inlet end can be positioned near the sputum to detect the presence of mycotoxins (mycotoxins) in the grain. Chemical ionization reactions and/or proton transfer reaction mass spectrometry can also be used to measure fungi or insects in post-harvest crops (e.g., prior to distribution to food and beverage production companies). Chemical ionization and/or proton transfer reaction mass spectrometry applications are also found in the cosmetics, cosmetics and consumer pharmaceutical industries, such as analyzing and testing products during the product development phase. Mass spectrometry can also be used during the manufacturing process to detect any defects or defective products prior to dispensing. Examples of applications from the cosmetics, cosmetics, and consumer pharmaceutical industries include the research and development of fragrances based on the identification of VOC components that contribute to particular fragrances (e.g., perfumes, antiperspirants, and deodorants). The concepts described herein are also applicable to the development and testing of cosmetics and consumer products (for example, monitoring VOC levels and detecting VOC levels during testing or in a laboratory setting). These products include mouthwash, toothpaste, soap, antiseptic soft 133727.doc •54· 200937487 creams and creams, deodorants and antiperspirants. Oral hygiene products can also be analyzed and monitored using respiratory analysis. Like the food and beverage industry, chemical ionization and/or proton transfer mass spectrometry can be used for general quality control and/or quality assurance programs for cosmetics, cosmetics and consumer pharmaceutical products, including evaluation of product stability and/or storage. period. There are additional applications for chemical ionization and/or proton transfer reaction mass spectrometry. For example, the concepts can be used for process monitoring and control in the biopharmaceutical industry, for example, to monitor and identify VOCs produced during the fermentation process. Some regulatory authorities (for example, International ASTM) have announced targets aimed at improving the quality, safety and efficiency of biopharmaceutical manufacturing. Positioning the gas sample inlet end to collect samples for online analysis during the manufacturing process can facilitate the achievement of their management objectives. In some embodiments, mass spectrometry can be used for biological research purposes to detect trace concentrations of VOC associated with plant leaf wound and defense mechanisms. In some embodiments, the gas sample inlet end is positioned to collect a sample from a gas supply source such as a hydrocarbon plume. The VOC content of the gas supply is determined according to the method described above. Hydrocarbon plumes can be used to deduct oil and/or gas deposits, and the mass spectrometry techniques herein can be used for petroleum exploration. Chemical ionization and/or proton transfer reactions Mass spectrometry can also be used to analyze and optimize the catalytic performance of the automotive industry. In such applications, the gas sample inlet end is positioned to collect the pre-catalyst and post-catalyst gas species, for example, for comparison purposes. Other applications will be apparent to those skilled in the art and are within the scope and spirit of the invention. I33727.doc -55- 200937487

In the second embodiment, the spectrometer incorporating the principles of the present invention is used as an assembly of an electronic nose system. In some embodiments, the electronic nose system also includes an analysis module for analyzing signals output by the instruments. The electronic nose system can be used to analyze vapors and gases, including those vapors and gases in the top m above solid or liquid materials, which include a plurality of components. The analysis module analyzes the signals output by the spectrometer and is capable of identifying specific components in the sample. In addition, the analysis module performs an overall fingerprint analysis of the material present, which is compared to the fingerprint of other substances in the previously stored information. In some implementations, the analysis module includes a computer processor that performs, for example, a multivariate analysis algorithm that is particularly well suited for processing many sample parameters (eg, many VOC component peaks that are characteristic of certain odors and tastes). , pattern identification algorithms or neural network algorithms to characterize and compare samples. In the case of I, multivariate analysis techniques are useful for observing and analyzing more than one statistical variable, and can reduce data from complex fingerprint spectra to enable simple comparisons. Using this method, similar tastes and odors can be grouped and identified and highlighted as outliers. The electronic nose system has been used for analysis consisting of many components, for example, a plurality of different v〇c substances. The overall fingerprint of the VOC issued by the food and beverage. For example, f, the odor is composed of molecules each having a specific size and shape. Each of these molecules has a corresponding size and shape in the human nose (4). The spectrometer can be used to (4) acquire fingerprints of many different molecules within the odor sample. Additional applications for electronic nose systems include the detection of specific odors for disease for medical diagnosis and detection of contamination. 133727.doc -56- 200937487 Dyes and gas leaks are used for environmental protection. In some embodiments, the electronic nose system includes additional sensors (eg, 'one or more gas sensors, including metal oxide semi-conductive germanium (MOS), conductive polymer (CP), quartz crystal microbalance, and field effect electricity A crystal (MOSFET) inductor whose output is analyzed by an analysis module. Although the present invention has been particularly shown and described with reference to the specific embodiments of the present invention, it will be understood by those skilled in the art, without departing from the spirit and scope of the invention as defined by the appended claims Among them, the shape δ and details are changed. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a plan view showing the components of a system embodying the present invention. 2 is a cross-sectional view of a reagent vapor supply source assembly of a mass spectrometry system. Figure 3 is a flow diagram of a method for generating reagent ions. Fig. 4 is a flow chart showing a mass spectrometry method for embodying the present invention. Figure 5 is a cross-sectional view of a quadrupole mass spectrometry system embodying the present invention. Figure 6 is an enlarged view of the drift chamber assembly shown in Figure 5. Figure 7 is a plan view of a time-of-flight mass spectrometer module embodying the present invention. [Main component symbol description] 100 104 108 112 133727.doc System reagent vapor supply source microwave / RF plasma generator plasma zone -57- 200937487 116 , 140 flange 120 orifice plate electrode 122 hole 124 drift external chamber / pumping drift external chamber 126 drift component. 128 sample supply source 136 chemical ionization / drift zone 138, 144 exit throttle ❹ 142 lens component 148 mass spectrometer module 152 control module 200 reagent vapor supply source component 202 Collector 204, 206' 208, 216 &gt; 218 '220 Port 210 Liquid Surface Ο w 212 Thermocouple 213 Headspace 214 Heater Jacket 222 Tube 224 Mass Flow Controller 226, 229 Tube 228 Gauge or Monitor 230 Pulp/plasma reaction zone 133727.doc -58- 200937487 500 Quadrupole mass spectrometry system 504 Reagent ion source 508 Chemical ionization/drift zone 512 Magnetron 514 Short antenna. 516 Sub L 520 Resonant cavity 524 Tube 528 Hole 532 Microwave choke 533 channel 536 outer surface 540 end 544 top 548 bottom 552 second end - 556 orifice plate 557 560 flange 562 outer chamber 564 drift ring electrode 566 chemical ionization / drift chamber an annular insulating member 571 port 568 port 133727.doc -59- 200937487

572 Total Pressure Gauge 576 Pumping Port 580, 596 Chest Pumping System 582 Ion Extraction Electrode 584, 588, 604 Flange 586 Bilateral Flange 592, 644 Mass Spectrometer 594, 664 Spectrometer Probe 598 Detector 608 Plasma Zone 612, 652 ion extraction electrodes 614, 628, 658 insulation collar 616 ' 656 extraction orifice 620 chemical ionization / drift chamber 624 plate electrode 625 drift end plate electrode 630, 633 central orifice 631 central orifice 632 port 636 fixing flange 640 flange 648 bilateral flange 657 area 659 metal plate -60- 133727.doc 200937487

660 668 676 700 704 708 712 716 720 724 728 728a 730 732 734 736 738 740 Insulated screw hole focusing electrode time-of-flight mass spectrometer system ion source time-of-flight mass spectrometer / flight chamber system pumping system ion optics component ion lens ion beam regulator Orbital reflection track frontal flight area back second optical system / reflector second gate detector 133727.doc -61 -

Claims (1)

200937487 X. Patent application scope: 1. A method comprising: introducing a sample gas; supplying reagent vapor to a plasma region; supplying microwave or high frequency RF energy to the reagent in the plasma region to vaporize One or more reagent ions; interacting the one or more reagent ions with the sample gas to produce one or more product ions; and directing the one or more product ions and the one or more reagent ions to a quadrupole or time-of-flight mass spectrometer a module; and determining, by the mass spectrometer module, a value of at least one of peak intensities or masses of the one or more product ions and each of the one or more reagent ions 〇2. The method of 1, wherein the sample gas comprises at least one or more volatile organic compounds in a trace concentration. 3. The method of claim 1, wherein the introducing comprises joining a gas sample inlet end to a closed space, such as the method of "Calling Item 1", wherein the introducing comprises placing a gas sample inlet end in a In a non-enclosed space. The method of item 1, wherein the introducing comprises joining the inlet end of a gas sample to a container. 6. If requested by the method of C§ 1 «V +, _L - 7·, wherein the introduction comprises joining a gas sample inlet end downstream of a gas or aircraft. The method of claim 1: The method of soil wherein the introduction comprises joining a gas sample inlet 133727.doc 200937487 end to a headspace above a food or beverage product. 8. The method of claim i, wherein the introducing comprises placing a body sample inlet end proximate to a human mouth to collect exhalation. 9. The method of claim </RTI> wherein the introduction comprises placing the inlet end of the gas sample adjacent to a solid sample material that emits gas or vapor. 10. The method of claim 2, wherein the introducing comprises coupling the gas sample inlet end to a gas supply source coupling. 11. A system comprising: a microwave or high frequency RF energy source for ionizing particles of reagent vapors with microwave or RF energy to form one or more reagent ions; facilitating inclusion of at least one or more traces of volatility a supply of analysis of a sample gas of an organic compound; a chamber including an inlet end that allows the sample gas to enter the chamber to interact with the one or more reagent ions from the microwave or high frequency RF energy source, thereby Forming one or more product ions, the chamber having an electromagnetic field generated therein; and a quadrupole or time-of-flight mass spectrometer module disposed relative to the exit orifice of the chamber for collecting the one or more product ions And the one or more reagent ions to facilitate determination of the value of at least one of peak intensities or masses of the one or more product ions and each of the one or more reagent ions. 12. The system of claim 11, wherein the quadrupole or time-of-flight mass spectrometer module facilitates determination of at least one of peak intensities or masses of the one or more volatile organic compounds in the gas sample. 133727.doc -2- 200937487 13·If the ash &lt; 崎11的系统', the quadrupole or time-of-flight mass spectrometer module contributes to the determination of the characteristics of the one or more volatile organic compounds in the steroid sample . I4. The system of claim 11, wherein the one or more volatile organic compounds include a compound mainly composed of dioxin, a compound mainly composed of furan, Cai, benzene, benzene, ethylbenzene, and Toluene, non-cave organic compounds, secondary organic aerosols, isobaric compounds, chemical warfare agents, trench gases, combustion improvers, volatile organic compounds in the presence of body fluids and fungi f and mycotoxin , or any combination thereof. K. The system of claim U wherein the or more volatile organic compounds include artificial or biologically derived volatile organic compounds. 16. A mass spectrometry system comprising: means for introducing a sample gas comprising at least a trace concentration of one or more volatile organic compounds; = from a reagent vapor supply source, by supplying the reagent vapor to microwave or a component of RF energy to generate one or more reagent ions; a member for interacting the sample gas with the one or more reagent ions to form one or more product ions; for the one or more product ions and The one or more reagents are directed to the mass spectrometer for determining the peak intensity or mass of the _ or more product ions and the enthalpy of each of the reagent ions to a value of 2 or 17, or for counting the one or more volatile organic compounds A system comprising: #件° 133727.doc 200937487 a microwave or high frequency RF energy source for ionizing reagent particles of a microwave or RF energy to form one or more reagent ions; including a chamber at the inlet end, the inlet The end allows the sample to enter the chamber to interact with the one or more reagent ions from the microwave or high frequency RF energy source to form one or more a product ion, the chamber having an electromagnetic field generated therein; and a quadrupole mass spectrometer module disposed opposite the chamber to the exit orifice, collecting 13⁄4 or more product ions and the one or more reagents from the ® A determination of the value of the peak intensity or mass of the respective product ions and each of the reagent ions or ions. For example, &quot;System of Monthly Item 1&apos; wherein the microwave energy source comprises a microwave electropolymer generator. The system of claim 1 wherein the high frequency RF energy source comprises a capacitively coupled RF plasma generator. &quot;The system of claim 1, wherein the one or more reagent ions comprise hydrated gas ions, oxygen ions or gasified nitrous ions. A system of month length 17, wherein the sample comprises one or more volatile organic compounds. The system of claim 1, further comprising a set of electrodes disposed relative to the chamber for generating the electromagnetic field to facilitate interaction between the one or more J ions and the sample, and Directing the object ion; or the reagent ion passing through the chamber exiting the orifice 0, such as the system of the kiss 22, wherein the electrode group surrounds the axis of the chamber 133727.doc 200937487 Radially disposed 'and the electromagnetic field substantially axially directs the one or more product ions and the one or more reagent ions. 24_ The system of claim 22, further comprising a control module in communication with the electrode set operable to determine a value of the electromagnetic field within the chamber based on operational parameters of the system. 25. The system of claim 17 which additionally comprises a mass flow controller, capillary or leak valve for determining the amount of the sample entering the chamber. 26. The system of claim 17, further comprising a mass filter disposed between the microwave or high frequency source and the chamber to selectively allow reagent ions to enter the chamber. 27', as in the system of claim 26, wherein the mass filter is a quadrupole mass filter. A system such as -month = item 17, further comprising a multivariate analysis module in communication with the system and operable to analyze data from the quadrupole mass spectrometer module. 29. The system of claim 17, a microwave generator; a resonator portion; the female device is disposed in the resonator; and wherein the microwave energy source comprises: a portion of the tube portion that is internal and in communication with the chamber, further comprising a 30. Control of the system of claim 17 in communication with the system 133727.doc 200937487 The module 'is operable to vary the input parameters of the system based in part on the operating parameters of the system. 3). The system of claim 3, wherein the operating parameter of the system comprises at least one of the following parameters: the composition of the sample, the pressure of the chamber, the more than 2 product ions or the - or a plurality of reagent ions passing through the chamber, the flow rate of the sample or the reagent ions entering the chamber, the energy of the 2# product ion or the reagent ion or reagent ions, the reagent j, and the product ion Chemical composition or any combination thereof. In the system of 2 items 30, which makes the control module operable to partially base the cavity? The f number is used to change the input parameters of a set of electrodes, and the set of electrodes is at . This electromagnetic field is generated internally. The system of group = item 17' additionally includes a control module that communicates with (d) to determine or determine the error of the operating parameters of the system. In the gods section, the control module is operable to change the value of the operating parameter by partial detection or discrimination by a portion of the ground. Group, &quot; it = 17m which additionally contains a control module or adjustment in communication with the system = a multivariate statistical analysis algorithm that monitors the system and is operable to set or adjust operational parameters of the system in response to the monitoring. γ The control group is based on 36. According to the system of claim 17, the lightning is taken directly; ', the dice 3 is arranged relative to the chamber, which defines the orifice, and the reagent_flow hole is transmitted to the four. The dose ion or product ion indicates the $#1° meter module via the section, and the extraction electrode is operable to know the energy value of the reagents from the mass spectrometer module to be received by the quadrupole 133727.doc 200937487 The system of claim 17, further comprising a member disposed relative to the chamber for concentrating the reagent ions and product ions on the extraction h-holes, the orifice facilitating reagent ions and products The transfer of ions to the spectrometer module. ^ 38 - A method for producing one or more reagent ions for a proton transfer reaction mass spectrometer or a chemical ion reaction mass spectrometer, the method comprising: supplying a reagent vapor; Microwave energy is supplied to the reagent vapor to produce one or more reagent ions. 39. The method of claim 38, further comprising directing the one or more reagent ions to a region to interact with a component of the sample to form a product ion. 40. The method of claim 38, wherein the one or more reagent ions are generated by microwave plasma. 41. The method of claim 38, wherein the reagent vapor comprises water vapor, oxygen or nitrous oxide&apos; and the one or more reagent ions comprise hydronium ions, oxygen ions or nitrous oxide ions. 42. The method of claim 38, wherein the microwave energy is provided by electromagnetic waves having a frequency greater than about 800 MHz. 43. A method for producing one or more reagent ions for a proton transfer reaction mass spectrometer or a chemical ion reaction mass spectrometer, the method comprising: supplying a reagent vapor; and providing high frequency RF energy to the reagent vapor to produce One or more reagent ions. 133727.doc. The method of claim 43, wherein the rF energy is provided by electromagnetic waves having a frequency between about 400 kHz and about 800 MHz. 45. The method of claim 43, wherein the one or more reagent ions are generated by capacitively coupling RF plasma. 46. A method comprising: supplying a reagent vapor to a plasma zone; providing microwave or high frequency RF energy to the reagent vapor in the plasma zone to form one or more reagent ions; Interacting the one or more reagent ions with a gas sample to produce one or more product ions; directing the one or more product ions and the one or more reagent ions to a collector region of the quadrupole mass spectrometer module, and by using the A mass spectrometer module measures values of peak intensities or masses of each of the one or more product ions and the one or more reagent ions. 47. A mass spectrometry system comprising: a component for supplying a microwave or a plurality of reagent ions of the reagent vapor; a reagent ion interacting to form a source for supplying a reagent or a high frequency RF energy to generate a a member for causing a sample to be associated with the one or more product ions; a member comprising an electromagnetic field, the one or more test elements 5 ||^: or a plurality of product ions and communicating with the collector region for The domain 'and the reagent ion or ions are one or more of the product ion members. 133727.doc 200937487 48. A system comprising: a microwave or high frequency RF for ionizing reagent particles of microwave or RF energy to form one or more reagent ions Energy; a chamber including an inlet end that allows a sample to enter the chamber to interact with the one or more reagent ions from the microwave or RF energy source to form one or more product ions; and relative to the chamber One of the mass spectrometer modules exiting the orifice, the mass spectrometer module comprising: a flight zone, the one or more product ions and the one or more reagent ions traveling through the flight zone, the flight zone defining a path length; And a collector region for receiving the one or more product ions and the one or more reagent ions from the flight zone, wherein the value of the quality is based on each of the one or more product ions and the one or more reagent ions The amount of time elapsed across the length of the path is measured. 49. The system of claim 48, wherein the mass spectrometer module further comprises: the exit orifice relative to the chamber disposed to pulse the one or more differential ions and the one or more reagent ion streams An ion beam modulator to the flight zone; and an optical system disposed in the flight zone for adding the value of the path length of the one or more product ions and the one or more reagent ions. 50. The system of claim 49 wherein the ion beam modulator utilizes a pseudo-random binary sequence provided from a controller to adjust the flow of the one or more product ions and the one or more reagent ions. 133727.doc 200937487 5 1. The system of claim 5, wherein an analysis module performs a most approximate signal processing algorithm on data received from the mass spectrometer module to determine the one or more product ions and the one Or the value of the peak intensity or mass of each of the plurality of reagent ions. [beta] 52. The system of Kiss 49, wherein an analysis module deconvolutes data received from the mass spectrometer module to determine the one or The value of the peak intensity or mass of each of the plurality of product ions and the one or more reagent ions. 53. The system of claim 49, wherein the collector region comprises a stacked microchannel plate detector or a bipolar detector operating in a pulse counting mode. 54. The system of claim 49, wherein the optical system comprises a reflective member. 55' The system of claim 49, further comprising a lens for concentrating the reagents and product ions on the ion beam modifier, wherein the ion beam modulator comprises an ion beam interceptor, an ion beam gate, An ion beam adjuster or any combination thereof, wherein the system of claim 48 further comprises an optical system disposed relative to the chamber and the mass spectrometer module, the optical system comprising at least one for the one or A plurality of product ions and a flow of the one or more reagent ions are directed toward a quadrupole lens guided by an ion beam regulator. 57. The system of claim 48, wherein the mass spectrometer module defines a substantially linear axis passing through the flight zone. The system of claim 57, wherein the substantially linear vehicle is substantially parallel to a second axis passing through the flight zone. 59. The system of item 48, further comprising a mass filter disposed in the chamber relative to the microwave energy source and the chamber for selectively allowing a subset of the one or more reagent ions to enter 133727.doc 200937487. 6. The system of claim 59, wherein the mass filter comprises a quadrupole mass filter. For example, the system of the long term 48 further includes an analysis module for receiving data from the mass spectrometer of the mass spectrometer, the mass spectrum including the one or more product ions and the one or more kinds of contact ions. The peak of each of the towels. Or the value of the quality. The system 62', such as the system of claim 48, additionally includes a multivariate statistical analysis module for identifying components of the sample based on a mass spectrum generated by the mass spectrometer module, the system of claim 48, additionally comprising Connected to the system and operable to (4) or identify a control module of the system based on operational parameters of the system. False 64. The system of claim 63, wherein the control module is operative to vary the value of the operational parameter based in part on the detecting or authenticating of the error. A system of earthly item 48, further comprising a system in communication with the system and operable to change a control parameter of the input parameter of the system based on operational parameters of the system, the system further comprising a a set of electrodes disposed relative to the chamber for generating an interaction between the one or more reagent ions and the sample, and for directing the one or more products away; and the one or more reagent ions The electric field exiting the orifice through the chamber. Field 67&apos; is the system of claim 66, which additionally includes a control 133727.doc 200937487^ group&apos; that is in communication with the electrode set operable to determine the value of the electromagnetic field within the chamber based on operational parameters of the system. 68. The system of claim 67, wherein the operational parameter of the system comprises at least one of the following: a composition of the sample, a pressure of the chamber, the one or more product ions, or the reagent ions or ions pass through The velocity of the chamber, the flow rate of the sample or the reagent ions into the chamber, the energy of the product ion or the reagent ions or reagent ions, or the chemical composition of the reagent ion or product ion or Any combination of them. Φ 69. The system of claim 67, wherein the control module is operative to change an input parameter of the electrode set based in part on the operational parameter. 7 0. A system comprising: a microwave or high frequency RF energy source for ionizing reagent vapors with microwave or RF energy to form one or more reagent ions; including a chamber at the inlet end, the inlet end allowing the sample Entering the chamber to interact with the one or more reagent ions from the microwave or RF energy source to form one or more product ions; and a time-of-flight mass spectrometer module disposed relative to the exit orifice of the chamber The method for generating a package based on the amount of time that the one or more product ions and the one or more reagent ions traverse the mass spectrometer includes the one or more product ions and the one or more reagents A spectrum of values of the mass of each of the ions. The system of claim 70, wherein the time-of-flight mass spectrometer module comprises: a flight zone, the one or more product ions and the one or more reagent ions traveling via the flight zone, the flight zone defining a path length; 133727 .doc • 12-200937487 an ion beam regulator for regulating the flow of the one or more product ions and the one or more reagent ions into the flight zone; disposed in the flight zone to increase the one or more product ions And a light source of the path length value of the one or more horn ions; and a collector region for receiving the one or more product ions and the one or more reagent ions from the flight zone. 72. A method for processing signals in a time-of-flight mass spectrometer based on - or a plurality of reagent ions generated by supplying microwave or RF energy to a reagent vapor and based on Generating a plurality of reagent ions with a fluid sample in an electromagnetic field to produce one or more product ions, the method comprising: establishing a first ion stream comprising the one or more reagent ions and the one or more product ions; The flow pattern changes the first ion current to produce a second ion current; the second ion stream is received at the debt detector; and the mass spectrum is determined by the data conveyed by the detector according to a most approximate haptic statistical algorithm Data indicative of the mass or peak intensity of the one or more reagent ions and the one or more product ions are included. 73. The method of claim 72, wherein the second ion stream is a pulsed stream. 74' The method of claim 73, wherein the pulse flow is based on the specified flow pattern generated from the quasi-random binary sequence. 75. A method comprising: 133727.doc • 13· 200937487 supplying reagent vapor to a plasma zone; supplying microwave or high frequency RF energy to the reagent vapor in the plasma zone to form one or more reagent ions Passing the one or more reagent ions with a gas sample to produce one or more product ions; directing the one or more product ions and the one or more reagent ions along a flight zone of the time-of-flight mass spectrometer module And determining, by the mass spectrometer module, values of peak intensities or masses of the one or more product ions and each of the one or more reagent ions. 76. A system for measuring the mass of one or more reagent ions and one or more product ions by means of microwave or rf energy. The reagent is produced by steaming, and the one or more product ions are generated by interacting the one or more reagent ions with a fluid sample in an electromagnetic field. The system comprises: a set of ions exiting relative to the drift tube assembly a quadrupole of the orifice arrangement ϋ mirror for receiving a first ion stream comprising the one or more reagent ions and the one or more product ions passing through the exit orifice, and for generating a directed a second ion stream of the ion beam modulator; and the ion beam modulator operative to selectively allow the second ion stream to pass to a flight zone of the time-of-flight mass spectrometer. 7 7. A system comprising: means for ionizing particles of a reagent vapor at a microwave or high frequency lamp to form one or more reagent ions; including an electromagnetic field for aligning the same with the one or more reagent ions 133727.doc •14· 200937487 A component that interacts to form one or more product ions and: a time taken to traverse a fixed distance based on the one or more product ions and the one or more reagents The amount of the component to determine the peak intensity or mass of each of the one or more product ions and the _ or reagent ions. 78. A meter or a plurality of reagent ions for measuring - or a plurality of reagent ions and - or a plurality of product ions - are generated by supplying microwave or rF energy to the reagent vapor and the product ion Produced by interfering with the -(iv) sample in an -electromagnetic field, the system comprising: for establishing a first ion current comprising the one or more reagent ions and the one or more product ions a member for adjusting the first ion current to generate a second ion current according to a specified interruption pattern; and means for generating a mass spectrum from the data conveyed by the detector member, the data corresponding to the second ion current . ❹ 79. A system for measuring the mass of one or more reagent ions and one or more product ions. The one or more reagent ions are generated by supplying microwave or RF energy to the reagent vapor, and One or more product ions are generated by interacting the one or more reagent ions with a fluid sample in an electromagnetic field. The system includes: for receiving the one or more reagent ions and the one or more product ions a first ion stream and an optical member for generating a second ion current directed to an adjustment member; and 133727.doc • 15· 200937487 the adjustment member for selectively controlling the second ion toward the mass spectrometer flow. 133727.doc 16-