A vacuum ultraviolet ion source (VUV-IS) for iodide–chemical ionization mass spectrometry: a substitute for radioactive ion sources
Abstract. A new ion source (IS) utilizing vacuum ultraviolet (VUV) light is developed and characterized for use with iodide–chemical ionization massspectrometers (I−-CIMS). The VUV-IS utilizes a compact krypton lamp that emits light at two wavelengths corresponding to energies of∼10.030 and 10.641 eV. The VUV light photoionizes either methyl iodide (ionization potential, IP = 9.54 ± 0.02 eV)or benzene (IP = 9.24378 ± 0.00007 eV) to form cations and photoelectrons. The electrons react with methyl iodide to formI−, which serves as the reagent ion for the CIMS. The VUV-IS is characterized by measuring the sensitivity of a quadrupole CIMS (Q-CIMS) toformic acid, molecular chlorine, and nitryl chloride under a variety of flow and pressure conditions. The sensitivity of the Q-CIMS, with theVUV-IS, reached up to ∼700 Hz pptv−1, with detection limits of less than 1 pptv for a 1 min integration period. Thereliability of the Q-CIMS with a VUV-IS is demonstrated with data from a month-long ground-based field campaign. The VUV-IS is further tested byoperation on a high-resolution time-of-flight CIMS (TOF-CIMS). Sensitivities greater than 25 Hz pptv−1 were obtained for formic acid andmolecular chlorine, which were similar to that obtained with a radioactive source. In addition, the mass spectra from sampling ambient air wascleaner with the VUV-IS on the TOF-CIMS compared to measurements using a radioactive source. These results demonstrate that the VUV lamp is a viablesubstitute for radioactive more »
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Award ID(s):
Publication Date:
NSF-PAR ID:
10170363
Journal Name:
Atmospheric Measurement Techniques
Volume:
13
Issue:
7
Page Range or eLocation-ID:
3683 to 3696
ISSN:
1867-8548
2. Abstract. Chemical ionization massspectrometry (CIMS) instruments routinely detect hundreds of oxidized organic compoundsin the atmosphere. A major limitation of these instruments is the uncertaintyin their sensitivity to many of the detected ions. We describe thedevelopment of a new high-resolution time-of-flight chemical ionization massspectrometer that operates in one of two ionization modes: using eitherammonium ion ligand-switching reactions such as for ${\mathrm{NH}}_{\mathrm{4}}^{+}$ CIMS orproton transfer reactions such as for proton-transfer-reaction massspectrometer (PTR-MS). Switching between the modes can be done within 2&thinsp;min.The ${\mathrm{NH}}_{\mathrm{4}}^{+}$ CIMS mode of the new instrument has sensitivities of upto 67&thinsp;000&thinsp;dcps&thinsp;ppbv−1 (duty-cycle-corrected ion counts per second perpart per billion by volume) and detection limits between 1 and 60&thinsp;pptv at2σ for a 1&thinsp;s integration time for numerous oxygenated volatileorganic compounds. We present a mass spectrometric voltage scanning procedurebased on collision-induced dissociation that allows us to determine thestability of ammonium-organic ions detected by the ${\mathrm{NH}}_{\mathrm{4}}^{+}$more » CIMS instrument.Using this procedure, we can effectively constrain the sensitivity of theammonia chemical ionization mass spectrometer to a wide range of detectedoxidized volatile organic compounds for which no calibration standards exist.We demonstrate the application of this procedure by quantifying thecomposition of secondary organic aerosols in a series of laboratoryexperiments.