scholarly journals Direct detection of gas-phase mercuric chloride by ion drift - Chemical ionization mass spectrometry

2020 ◽  
Vol 238 ◽  
pp. 117687 ◽  
Author(s):  
Alexei F. Khalizov ◽  
Francisco J. Guzman ◽  
Matthew Cooper ◽  
Na Mao ◽  
John Antley ◽  
...  
2010 ◽  
Vol 10 (12) ◽  
pp. 30539-30568
Author(s):  
T. Kurtén ◽  
T. Petäjä ◽  
J. Smith ◽  
I. K. Ortega ◽  
M. Sipilä ◽  
...  

Abstract. The state-of-the art method for measuring atmospheric gas-phase sulfuric acid is chemical ionization mass spectrometry (CIMS) based on nitrate reagent ions. Using computed proton affinities and reaction thermodynamics for the relevant charging reactions, we show that in the presence of strong bases such as amines, which tend to cluster with the sulfuric acid molecules, a significant fraction of the total gas-phase sulfuric acid may not be measured by a CIMS instrument. If this is the case, this effect has to be taken into account in the interpretation of atmospheric sulfuric acid measurement data, as well as in intercomparison of different CIMS instruments, which likely have different susceptibilities to amine-sulfuric acid clustering.


2016 ◽  
Vol 9 (8) ◽  
pp. 3851-3861 ◽  
Author(s):  
Javier Sanchez ◽  
David J. Tanner ◽  
Dexian Chen ◽  
L. Gregory Huey ◽  
Nga L. Ng

Abstract. Hydroperoxy radicals (HO2) play an important part in tropospheric photochemistry, yet photochemical models do not capture ambient HO2 mixing ratios consistently. This is likely due to a combination of uncharacterized chemical pathways and measurement limitations. The indirect nature of current HO2 measurements introduces challenges in accurately measuring HO2; therefore a direct technique would help constrain HOx chemistry in the atmosphere. In this work we evaluate the feasibility of using chemical ionization mass spectrometry (CIMS) and propose a direct HO2 detection scheme using bromide as a reagent ion. Ambient observations were made with a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) in Atlanta over the month of June 2015 to demonstrate the capability of this direct measurement technique. Observations displayed expected diurnal profiles, reaching daytime median values of ∼ 5 ppt between 2 and 3 p.m. local time. The HO2 diurnal profile was found to be influenced by morning-time vehicular NOx emissions and shows a slow decrease into the evening, likely from non-photolytic production, among other factors. Measurement sensitivities of approximately 5.1 ± 1.0 cps ppt−1 for a bromide ion (79Br−) count rate of 106 cps were observed. The relatively low instrument background allowed for a 3σ lower detection limit of 0.7 ppt for a 1 min integration time. Mass spectra of ambient measurements showed the 79BrHO2− peak was the major component of the signal at nominal mass-to-charge 112, suggesting high selectivity for HO2 at this mass-to-charge. More importantly, this demonstrates that these measurements can be achieved using instruments with only unit mass resolution capability.


2003 ◽  
Vol 3 (2) ◽  
pp. 417-436 ◽  
Author(s):  
M. Hanke ◽  
B. Umann ◽  
J. Uecker ◽  
F. Arnold ◽  
H. Bunz

Abstract. The EU-project MINATROC (MINeral dust And TROpospheric Chemistry) aims at enabling an estimation of the influence of mineral dust, a major, but to date largely ignored component of tropospheric aerosol, on tropospheric oxidant cycles. Within the scope of this project continuous atmospheric measurements of gas-phase HNO3 and SO2 were conducted in June and July 2000 at the CNR WMO station, situated on Monte Cimone (MTC) (44°11' N --10°42' E, 2165 m asl), Italy. African air transporting dust is occasionally advected over the Mediterranean Sea to the site, thus mineral aerosol emitted from Africa will encounter polluted air masses and provide ideal conditions to study their interactions. HNO3 and SO2 were measured with an improved CIMS (chemical ionization mass spectrometry) system for ground-based measurements that was developed and built at MPI-K Heidelberg. Since HNO3  is a very sticky compound special care was paid for the air-sampling and background-measurement system. Complete data sets could be obtained before, during and after major dust intrusions. For the first time these measurements might provide a strong observational indication of efficient uptake of gas-phase HNO3 by atmospheric mineral-dust aerosol particles.


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