Abstract
Abstract. Iodide chemical ionization mass spectrometry (CIMS) is a common analytical
tool used in both laboratory and field experiments to measure a large suite
of atmospherically relevant compounds. Here, we describe a systematic ion
molecule reactor (IMR) temperature dependence of iodide CIMS analyte
sensitivity for a wide range of analytes in laboratory experiments. Weakly
bound iodide clusters, such as HCl, HONO, HCOOH, HCN, phenol, 2-nitrophenol,
and acyl peroxynitrate (PAN) detected via the peroxy radical cluster, all
exhibit strong IMR temperature dependence of sensitivity ranging from −3.4 % ∘C−1
to 5.9 % ∘C−1 (from 37 to 47 ∘C). Strongly
bound iodide clusters, such as Br2, N2O5, ClNO2, and PAN
detected via the carboxylate anion, all exhibit little to no IMR temperature
dependence ranging from 0.2 % ∘C−1 to −0.9 % ∘C−1 (from 37 to 47 ∘C). The IMR temperature relationships of weakly bound clusters
provide an estimate of net reaction enthalpy, and comparison with database
values indicates that these clusters are in thermal equilibrium. Ground site
HCOOH data collected in the summer of 2021 in Pasadena (CA) are corrected
and show a reversal in the diel cycle, emphasizing the importance of this
correction (35±6 % during the day, -26±2 % at night).
Finally, we recommend two approaches to minimize this effect in the field,
namely heating or cooling the IMR; the latter technique has the added benefit of
improving absolute sensitivity.
Funder
California Air Resources Board
NOAA Center for Earth System Sciences and Remote Sensing Technologies
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