Leah S. Riter

Single-sided membrane introduction mass spectrometry for on-line determination of semi-volatile organic compounds in air.

Construction, optimization, and testing of a novel single-sided configuration for a semi-permeable [poly(dimethylsiloxane); PDMS] membrane introduction system for mass spectrometry is described. On-line detection of semi-volatile organic compounds of environmental interest is shown, including lindane (a pesticide), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) (an explosive), butylated hydroxytoluene (BHT) (an antioxidant), 1,2-dichlorobenzene, dimethylmethyl phosphonate (DMMP) (a chemical warfare agent simulant) and naphthalene. The technique has limits of detection in the sub-ppb range. with rise times of 4 to 7 s and fall times of 12 to 36 s and a response that is linear over 4 orders of magnitude (from 0.1 ppb to 1000 ppb for DMMP). The cycle time, from crude air sampling to acquisition of results, is approximately 1 min. No sample preparation is necessary.

Solid phase micro-extraction in a miniature ion trap mass spectrometer

Fiber introduction mass spectrometry (FIMS), a variation of solid-phase microextraction (SPME) and membrane introduction mass spectrometry (MIMS), is employed with a miniature mass spectrometer. The inlet system, constructed of commercially available vacuum parts, allows the direct introduction of the SPME needle vacuum chamber into the mass spectrometer. Thermal desorption of the analyte from the poly(dimethylsiloxane) (PDMS) coated fiber was achieved with a built in nichrome heater, followed by electron ionization of the analytes internal to the cylindrical ion trap (CIT). The system has been tested with several volatile organic compounds (VOC) in air and to analyze the headspace over aqueous solutions, with limits of detection in the low ppb range. The signal rise (10-90%) and fall (90-10%) times for the system ranged from 0.1 to 1 s (rise) and 1.2 to 6 s (fall) using heated desorption. In addition, this method has been applied to quantitation of toluene in benzene, toluene, xylene (BTX) mixtures in water and gasoline. This simple and rapid analysis method, coupled to a portable mass spectrometer, has been shown to provide a robust, simple, rapid, reproducible, accurate and sensitive (low ppb range) fieldable approach to the effective in situ analysis of VOC in various matrices.

Ion/molecule reactions performed in a miniature cylindrical ion trap mass spectrometer

A recently constructed miniature mass spectrometer, based on a cylindrical ion trap (CIT) mass analyzer, is used to perform ion/molecule reactions in order to improve selectivity for in situ analysis of explosives and chemical warfare agent simulants. Six different reactions are explored, including several of the Eberlin reaction type (M. N. Eberlin and R. G. Cooks, Org. Mass Spectrom., 1993, 28, 679-687) as well as novel gas-phase Meerwein reactions. The reactions include (1) Eberlin transacetalization of the benzoyl, 2,2-dimethyloximinium, and 2,2-dimethylthiooximinium cations with 2,2-dimethyl-1,3-dioxolane to form 2-phenyl-1,3-dioxolanylium cations, 2,2-dimethylamine-1,3-dioxolanylium cations and the 2,2-dimethylamin-1,3-oxathiolanylium cations, respectively; (2) Eberlin reaction of the phosphonium ion CH3P(O)OCH3+, formed from the chemical warfare agent simulant dimethyl methylphosphonate (DMMP), with 1,4-dioxane to yield the 1,3,2-dioxaphospholanium ion, a new characteristic reaction for phosphate ester detection; (3) the novel Meerwein reaction of the ion CH3P(O)OCH3+ with propylene sulfide forming 1,3,2-oxathionylphospholanium ion; (4) the Meerwein reaction of the benzoyl cation with propylene oxide and propylene sulfide to form 4-methyl-2-phenyl-1,3-dioxolane and its thio analog, respectively; (5) ketalization of the benzoyl cation with ethylene glycol to form the 2-phenyl-1,3-dioxolanylium cation; (6) addition/NO2 elimination involving benzonitrile radical cation in reaction with nitrobenzene to form an arylated nitrile, a diagnostic reaction for explosives detection and (7) simple methanol addition to the C7H7+ ion, formed by NO2 loss from the molecular ion of p-nitrotoluene to form an intact adduct. Evidence is provided that these reactions occur to give the products described and their potential analytical utility is discussed.

Denitration of nitroaromatic compounds by arylnitrile radical cations.

Substituted nitrobenzenes react with substituted benzonitrile radical cations in an ion trap mass spectrometer by a novel ion/molecule reaction involving NO2 elimination. Formation of an arylated nitrile, Ar1+N≡CAr2 (where Ar1, Ar2 = aryl), is indicated by collision induced dissociation and comparison with the behavior of the authentic ion. Ab initio calculations (MP2/6-31G*//HF/6-31G*) show the reaction of the unsubstituted compounds (Ar1, Ar2 = phenyl) to be exothermic by 48 kcal/mol, consistent with the experimental observation that the reaction rate decreases as the collision energy is increased. Electron withdrawing and donating substituents on either the ionic or the neutral reagent have little effect on the relative amount of product observed, pointing to a radical mechanism. Related denitration reactions were found to occur, between nitrobenzene and its radical cation and between phenylisonitrile and ionized nitrobenzene. These reactions are suggested to yield Ar1+N(=O)OAr2 and Ar2+ N≡CAr1, respectively. The denitration reaction was applied to trinitrotoluene (TNT) as a possible diagnostic reaction for the presence of nitroaromatic explosives.

Trace analysis of organics in air by corona discharge atmospheric pressure ionization using an electrospray ionization interface

A corona discharge ion source operating at atmospheric pressure in the point-to-plane configuration was constructed by reconfiguring the ion source of a commercial electrospray ionization (ESI) quadrupole mass spectrometer. This new source allows direct air analysis without modification to the mass spectrometer. Detection and quantitation of semi-volatile compounds in air is demonstrated. The analytical performance of the system was established using the chemical warfare agent simulants methyl salicylate and dimethyl methylphosphonate. Limits of detection are 60 pptr in the negative-ion mode and 800 pptr in the positive-ion mode for methyl salicylate and 800 pptr in the negative-ion mode and 3.6 ppb in the positive-ion mode for dimethyl methylphosphonate. A linear response was observed from 60 pptr to 8 ppb for methyl salicylate in air in the negative-ionization mode. Cluster ion formation versus production of analyte ions was investigated and it was found that dry air or an elevated capillary interface temperature (130°C) was needed to avoid extensive clustering, mostly of water. Reagent gases are not needed as proton sources, as is usually the case for atmospheric pressure chemical ionization, and this, together with the simplicity, sensitivity and speed of the technique, makes it promising for miniaturization and future field studies.

Gas-phase reactions for selective detection of the explosives TNT and RDX.

Highly selective gas-phase reactions with ethyl vinyl ether (EVE) of major electron (EI) and chemical ionization (CI) fragment ions of the explosives TNT and RDX have been uncovered. The fragment ion of m/z 210 from TNT undergoes [4(+)+ 2] cycloaddition with EVE to form an oxo-iminium ion of m/z 282, which dissociates by acetaldehyde loss after a [1,5-H] shift to form a quinolynium ion of m/z 238. The fragment ion of m/z 149 from RDX reacts with EVE by a formal vinylation reaction, that is, the elusive cyclic adduct loses ethanol to yield a nitro-iminium ion of m/z 175, which reacts further with EVE to form a second cyclic product ion of m/z 247. Calculations and MS/MS experiments support the proposed structures. These highly characteristic reactions of diagnostic EI and CI fragment ions improve selectivity for TNT and RDX detection.