In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry.
We propose detecting a fragment ion (Ph2As(+)) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH(+)) of DA, DC, DPAH, and BDPAO could produce Ph2As(+) through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph2As(+) signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH(+) signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph2As(+). Graphical Abstract ᅟ.
Central Research Laboratory, Hitachi, Ltd., Kokubunji, Tokyo, 185-8601, Japan. a.oku@nifty.com.
Akihiko
A
Okumura
Central Research Laboratory, Hitachi, Ltd., Kokubunji, Tokyo, 185-8601, Japan.
Yasuaki
Y
Takada
Hitachi High-Tech Solutions Corporation, Mito, Ibaraki, 319-0316, Japan.
Susumu
S
Watanabe
Hitachi High-Tech Solutions Corporation, Mito, Ibaraki, 319-0316, Japan.
Hiroaki
H
Hashimoto
Hitachi, Ltd., Defense Systems Company, Chiyoda, Tokyo, 101-8608, Japan.
Naoya
N
Ezawa
National Research Institute of Police Science, Kashiwa, Chiba, 277-0882, Japan. seto@nrips.go.jp.
Yasuo
Y
Seto
National Research Institute of Police Science, Kashiwa, Chiba, 277-0882, Japan.|Tokyo Metropolitan Police Department, Chiyoda, Tokyo, 100-8929, Japan.
Yasuo
Y
Takayama
National Research Institute of Police Science, Kashiwa, Chiba, 277-0882, Japan.|Tokyo Metropolitan Police Department, Chiyoda, Tokyo, 100-8929, Japan.
Ryoji
R
Sekioka
National Research Institute of Police Science, Kashiwa, Chiba, 277-0882, Japan.|Tokyo Metropolitan Police Department, Chiyoda, Tokyo, 100-8929, Japan.
Shintaro
S
Yamaguchi
National Research Institute of Police Science, Kashiwa, Chiba, 277-0882, Japan.|Tokyo Metropolitan Police Department, Chiyoda, Tokyo, 100-8929, Japan.
Shintaro
S
Kishi
National Research Institute of Police Science, Kashiwa, Chiba, 277-0882, Japan.|Tokyo Metropolitan Police Department, Chiyoda, Tokyo, 100-8929, Japan.
Takafumi
T
Satoh
National Research Institute of Police Science, Kashiwa, Chiba, 277-0882, Japan.|Tokyo Metropolitan Police Department, Chiyoda, Tokyo, 100-8929, Japan.
Tomohide
T
Kondo
National Research Institute of Police Science, Kashiwa, Chiba, 277-0882, Japan.|Tokyo Metropolitan Police Department, Chiyoda, Tokyo, 100-8929, Japan.
Hisayuki
H
Nagashima
National Research Institute of Police Science, Kashiwa, Chiba, 277-0882, Japan.
Tomoki
T
Nagoya
Air monitoring; Atmospheric pressure chemical ionization; Chemical warfare agent; Diphenylchloroarsine; Diphenylcyanoarsine; Hydrolysis; In-source fragmentation; Multiple-stage mass spectrometry; Protonation