Compact FTICR Mass Spectrometry for Real Time Monitoring of Volatile Organic Compounds

International audienceIn this paper, we present a compact Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS) designed for real time analysis of volatile organic compounds (VOCs) in air or in water. The spectrometer is based on a structured permanent magnet made with NdFeB segments. Chemical ionization is implemented inside the ICR cell. The most widely used reaction is the proton transfer reaction using H 3 O + precursor ions, but other ionic precursors can be used to extend the range of species that can be detected. Complex mixtures are studied by switching automatically from one precursor to another. The accuracy obtained on the mass to charge ratio (∆m/z 5 × 10 −3), allows a precise identification of the VOCs present and the limit of detection is 200 ppb without accumulation. The time resolution is a few seconds, mainly limited by the time necessary to come back to background pressure after the gas pulses. The real time measurement will be illustrated by the monitoring of VOCs produced during the thermal degradation of a polymer and by an example where three different precursor ions are used alternatively to monitor a gas sample

An experimental study of the reactivity of CN- and C3N- anions with cyanoacetylene (HC3N)

International audienceThe reactions of the CN- and C3N- anions with cyanoacetylene HC3N, of special interest for the chemistry of Titan’s upper atmosphere, have been investigated by means of FTICR mass-spectrometry. Primary ions, CN- and C3N-, have been produced by dissociative electron attachment (DEA) from BrCN and BrC3N, and prepared in a clean way before reaction. Total rate constants have been measured for both reactions at 300 K and are found to be: (3.9 ± 0.5) 10-9 and (1.0 ± 0.2) 10-10 cm3.s-1 for the reaction of HC3N with CN- and C3N-, respectively. For the CN- + HC3N reaction, proton transfer is found to be the only reactive channel within our detection limits. Proton transfer is also dominant for the C3N- + HC3N reaction but the resulting ionic product being identical to the primary ion C3N-, this process is transparent for the kinetics of the C3N- + HC3N reaction and the kinetic rate retrieved corresponds to a slow and competitive detachment pathway. Yet the nature and energetics of the neutral product(s) formed through this process remain unknown. Additional experiments using isotopic products have allowed to retrieve specific rate constants associated to the proton transfer channel in the C315N- + HC3N and C3N- + HC315N reactions and the measured rates are found to be significantly lower than for the CN- + HC3N system. This decrease and the evolution of reactivity when going from CN- to C3N- and the opening of a new detachment pathway is finally discusse

Direct and real-time analysis in a plasma reactor using a compact FTICR/MS: degradation of acetone in nitrogen and by-products formation

Methods for reduction of Volatile Organic Compounds (VOCs) content in air depend on the 10 application considered. For low concentration and low flux, non-thermal plasma methods are often considered as efficient. However, the complex chemistry involved is still not well understood as there is a lack of datasets of byproducts formation. So as to overcome this issue, rapid analytical methods are needed. We present the coupling of a rapid chemical ionization mass spectrometer (CIMS) for the real-time analysis of the VOCs formed during a degradation experiment. The high resolution instrument used 15 allows for chemical ionization and direct quantification of non-targeted compounds. We present degradation experiments of acetone in a photo-triggered nitrogen plasma discharge. Two regimes were highlighted: efficient conversion at low concentrations (100ppm). Those two regimes were clearly delimited as the sum of two exponential curves occuring at respectively low and high concentrations. Many by-products were detected, in 20 particular HCN presented a significantly high yield. Nitrile compounds (acetonitrile, propionitrile,...) are formed as well. To a lower extent, ketene, acetaldehyde and formaldehyde are observed. The association of the high resolution mass spectrometer to the plasma reactor will allow further insights into the plasma chemistry and comparison to modelisation

Modeling substrate interactions during aerobic biodegradation of mixtures of vinyl chloride and ethene

Ethene (ETH) is often associated with vinyl chloride (VC) in contaminated groundwater, as it is formed along with vinyl chloride during reductive dechlorination of higher chloroethenes (e.g., perchloroethylene and trichloroethylene). In the present study the interaction between VC and ETH during their aerobic biodegradation by enrichment cultures was investigated. The cultures were able to use both compounds as growth substrates. In mixture experiments, the degradation rate of one substrate was affected by the presence of the other. A biokinetic model based on competitive inhibition described well the observed substrate interactions over a range of initial VC (0-144 mu mol L-1) and ETH (0-37.5 mu mol L-1) concentrations, using parameters estimated from single-substrate experiments. Notably, half-velocity coefficients could be used as competitive inhibition coefficients. This finding shows the importance of obtaining accurate measurements of half-velocity coefficients in order model competitive inhibition processes. Simulation results showed that when the initial ETH concentration was raised from 0 to 30 mu mol L-1, the apparent half-velocity coefficient for VC (K-VC(APP)) increased by nearly three times, from 12.9 to 35.4 mu mol L-1. This finding has strong environmental implications because a low half-velocity coefficient for VC is regarded as the major prerequisite for achieving efficient and complete VC degradation. Moreover, the effect of ETH on the efficiency of VC removal is strongly dependent on the K-VC/K-ETH ratio, consequently determination of K-ETH for VC-degrading microbes is important when biodegradation (or bioaugmentation) is considered for clean up of VC-contaminated sites. Additional model simulations, using the ratio of K-VC to K-ETH for previously characterized VC- and ETH-utilizing microorganisms (values ranged from 0.06 to 1.2) showed that their ability to degrade VC in the presence of ETH may differ significantly

Protonated 1,4-difluorobenzene C6H5F2+: A promising precursor for proton-transfer chemical ionization

International audienc

Evidence of Reactivity in the Membrane for the Unstable Monochloramine during MIMS Analysis

Membrane Inlet Mass Spectrometry (MIMS) was used to analyze monochloramine solutions (NH2Cl) and ammonia solutions in a compact FTICR. Chemical ionization enables identification and quantification of the products present in the permeate. The responses of protonated monochloramine and ammonium increase linearly with the solution concentration. The enrichments were respectively 1.2 and 5.5. Pervaporation is dependent on pH and only the basic form of ammonia NH3 pervaporates through the membrane. Unexpectedly, the small ammonia molecule permeated very slowly. It could be due to interactions with water molecules inside the membrane that create clusters. Moreover, NH2Cl solutions, in addition to the NH3Cl+ signal, presented a strong NH4+ signal at m/z 18.034. Ammonia presence in the low-pressure zone before ionization is probable as NH4+ was detected with all the precursors used, particularly CF3+ and trimethylbenzene that presents a proton affinity higher than monochloramine. Ammonia may be formed inside the membrane due to the fact that NH2Cl is unstable and may react with the water present in the membrane. Those results highlight the need for caution when dealing with chloramines in MIMS and more generally with unstable molecules

Real time analysis of toluene degradation in a dielectric barrier discharge plasma

International audienc

Gas Analysis by Electron Ionization Combined with Chemical Ionization in a Compact FTICR Mass Spectrometer

International audienc