CIMS

The measurement of gas phase peroxide species, H2O2 and CH3OOH, contribute to our scientific understanding of the photochemistry of trace gases and particles prior to and after their transport and processing through deep convective clouds. The PCIMS instrument used to make these measurements in the DC3/SEAC4RS mission is new and this will be its first use in an airborne science campaign.

The PCIMS instrument is a slightly modified CIMS instrument manufactured by THS Instruments LLC. Mechanically it consists of a differentially pumped quadrupole mass spectrometer. The instrument operates in negative ion mode and currently I^- and O2^- reagent ions are used to measure hydrogen peroxide and methylhydroperoxide, respectively, by the formation of cluster ions at masses 80 and 161. The reagent ions are produced by flowing a N2/CH3I/O2 mixture past a ²¹⁰Po foil.

On the G-V, the PCIMS inlet system starts with a PFA Teflon lined heated G-V HIMIL inlet. From the HIMIL the inlet line is comprised of PFA Teflon and is also heated (Hot-Tube, Clayborn Lab). Analytical blanks are performed by diverting the ambient sample flow through a trap filled with Carulite 200 catalyst. Gas phase calibrations are performed through standard additions to ambient air. H2O2 is added from a urea hydrogen peroxide solid decomposition source or by the evaporation of a nano-fluidic flow of a dilute aqueous solution. CH3OOH is added by the evaporation of a nano-fluidic flow of a dilute aqueous solution. The ambient, calibration and reagent gases are vented overboard through the G-V common exhaust.

An inlet collects ambient air from the free air stream and adds reagents, including O2 or N2 dilutents, and NO and SO2 reagent gases. This method, called "oxygen dilution modulation" leads to nearly 100% measurement of HO2 and RO2 in the O2 dilution/low reagent concentration mode, whereas RO2 is measured with less than 10% efficiency in the N2 dilution/higher reagent concentration mode. This is because the chemistry converts peroxy radicals to H2SO4 efficiently in the O2 mode, but RO2 radicals are converted to RONO in the N2 mode. The H2SO4 thus produced is ionized by reaction with NO3- ions. The reagent and product ions are detected by mass spectrometry using quadrupole mass filtering and counting by a channel electron multiplier operating in the negative ion mode.

The CIMS instrument consists of a low pressure ion molecule reactor (IMR) coupled to a quadrupole mass filter by an actively pumped collisional dissociation chamber (CDC) and an octopole ion guide. The vacuum system is a 100 mm outer diameter stainless steel chamber evacuated with two small turbo pumps (70 l s^-1). The mass filter is a set of 9.5 mm diameter quadrupole rods housed in the main vacuum chamber. The CDC is a short 80 mm diameter chamber that houses an octopole ion guide and is evacuated with a hybrid molecular drag pump. The IMR is evacuated with a scroll pump (300 l min^-1) that also serves as the backing pump for the mass spectrometer.

Click here for the Collaborative Ground and Airborne Observations description page.

Titration of OH in H2SO4 and measurement of H2SO4 and MSA via proton exchange with NO3-. DMSO and DMSO2 are reacted with NH4+ ions. In all cases concentrations are determined by product/reactant ion ratios. Ion ratios are measured with quadrupole mass spectrometers.

OH measurements used to understand fast photooxidation chemistry; H2SO4 used to investigate particle nucleation; H2SO4 and MSA used to understand particle growth; DMSO and DMSO2 to investigate DMS oxidation process and its relation to particle production and growth.

The PAN-CIGAR chemical ionization mass spectrometer which measures up to 7 PAN species simultaneously and semi-continuously with a time resolution of ~2 seconds. The method is based on the detection of the acylperoxy radicals formed from thermal decomposition of the PAN species at the inlet by reacting them with iodide ions, which are formed by passing methyl iodide diluted in nitrogen through an α–particle source. The reaction of the peroxy acyl radicals with I- forms IO and the acyl ion, which is detected using a quadrupole mass spectrometer (Extrel) at a mass to charge ratio of 59 in the case of PAN. The method is very specific for PAN type compounds and the limit of detection is ~1 pptv/s or better for most PAN species. The instrument employs a realtime continuous calibration using isotopically labeled PAN produced in-situ by a photolytic calibration source.

The NOAA chemical ionization mass spectrometer (CIMS) instrument was developed for high-precision measurements of gaseous nitric acid (HNO3) specifically under high- and variable-humidity conditions in the boundary layer. The instrument’s background signals (i.e., signals detected when HNO3-free air is measured), which depend on the humidity and HNO3 concentration of the sample air, are the most important factor affecting the limit of detection (LOD). A new system to provide HNO3-free air without changing both the humidity and the pressure of the sampled air was developed to measure the background level accurately. The detection limit was about 23 parts per trillion by volume (pptv) for 50-s averages. Field tests, including an intercomparison with the diffusion scrubber technique, were carried out at a surface site in Tokyo, Japan, in October 2003 and June 2004. A comparison between the measured concentrations of HNO3 and particulate nitrate indicated that the interference from particulate nitrate was not detectable (i.e., less than about 1%). The intercomparison indicated that the two independent measurements of HNO3 agreed to within the combined uncertainties of these measurements.

The single mass analyzer CIMS (S-CIMS) was developed for use on NASA’s ER-2 aircraft. Its first measurements were made in 2000 (SOLVE, see photo). Subsequently, it has flown on the NASA DC-8 aircraft for INTEX-NA, DICE, TC4, ARCTAS, ATom, KORUS, FIREX, as well as on the NCAR C-130 during MILAGRO/INTEX-B. HNO3 is measured by selective ion chemical ionization via the fluoride transfer reaction: CF3O^- + HNO3 → HF • NO3^- + CF2O In addition to its fast reaction rate with HNO3, CF3O^- can be used to measure additional acids and nitrates as well as SO2 [Amelynck et al., 2000; Crounse et al., 2006; Huey et al., 1996]. We have further identified CF3O^- chemistry as useful for the measurement of less acidic species via clustering reactions [Crounse et al., 2006; Paulot et al., 2009a; Paulot et al., 2009b; St. Clair et al., 2010]: CF3O^- + HX → CF3O^- • HX where, e.g., HX = HCN, H2O2, CH3OOH, CH3C(O)OOH (PAA) The mass analyzer of the S-CIMS instrument was first upgraded from a quadrupole to a unit-mass resolution time-of-flight (ToF) analyzer. In 2023, the mass filter was again upgraded to an 1m flight path (~5000 deltaM/M).  The ToF admits the sample ion beam to the ion extractor, where a pulse of high voltage orthogonally deflects and accelerates the ions into the reflectron, which in turn redirects the ions toward the multichannel plate detector. Ions in the ToF follow a V-shaped from the extractor to detector, separating by mass as the smaller ions are accelerated to greater velocities by the high voltage pulse. The detector collects the ions as a function of time following each extractor pulse. The rapid-scan collection of the ToF guarantees a high temporal resolution (1 Hz or faster) and simultaneous data products from the S-CIMS instrument for all mass channels [Drewnick et al., 2005]. We have flown a tandem CIMS (TCIMS) instrument in addition to the SCIMS since INTEX-B (2006). The T-CIMS provides parent-daughter mass analysis, enabling measurement of compounds precluded from quantification by the S-CIMS due to mass interferences (e.g. MHP) or the presence of isobaric compounds (e.g. isoprene oxidation products) [Paulot et al., 2009b; St. Clair et al., 2010]. Calibrations of both CIMS instruments are performed in flight using isotopically-labeled reagents evolved from a gas cylinders or from a thermally-stabilized permeation tube oven [Washenfelder et al., 2003]. By using an isotopically labeled standard, the product ion signals are distinct from the natural analyte and calibration can be performed at any time without adversely affecting the ambient measurement.