Novel ionization reagent for the measurement of gas-phase ammonia and amines using a stand-alone atmospheric pressure gas chromatography (APGC) source.

RationaleContaminants present in ambient air or in sampling lines can interfere with the target analysis through overlapping peaks or causing a high background. This study presents a positive outcome from the unexpected presence of N-methyl-2-pyrrolidone, released from a PALL HEPA filter, in the analysis of atmospherically relevant gas-phase amines using chemical ionization mass spectrometry.MethodsGas-phase measurements were performed using a triple quadrupole mass spectrometer equipped with a modified atmospheric pressure gas chromatography (APGC) source which allows sampling of the headspace above pure amine standards. Gas-phase N-methyl-2-pyrrolidone (NMP) emitted from a PALL HEPA filter located in the inlet stream served as the ionizing agent.ResultsThis study demonstrates that some alkylamines efficiently form a [NMP + amine+H]+ cluster with NMP upon chemical ionization at atmospheric pressure. The extent of cluster formation depends largely on the proton affinity of the amine compared with that of NMP. Aromatic amines (aniline, pyridine) and diamines (putrescine) were shown not to form cluster ions with NMP.ConclusionsThe use of NMP as an ionizing agent with stand-alone APGC provided high sensitivity for ammonia and the smaller amines. The main advantages, in addition to sensitivity, are direct sampling into the APGC source and avoiding uptake on sampling lines which can be a significant problem with ammonia and amines

EMSL Science Theme Advisory Panel Workshop - Atmospheric Aerosol Chemistry, Climate Change, and Air Quality

This report contains the workshop scope and recommendations from the workshop attendees in identifying scientific gaps in new particle formation, growth and properties of particles and reactions in and on particles as well as the laboratory-focused capabilities, field-deployable capabilities and modeling/theory tools along with linking of models to fundamental data

Kinetics, mechanisms and ionic liquids in the uptake of n-butylamine onto low molecular weight dicarboxylic acids

Atmospheric particles adversely affect visibility, health, and climate, yet the kinetics and mechanisms of particle formation and growth are poorly understood. Multiphase reactions between amines and dicarboxylic acids (diacids) have been suggested to contribute. In this study, the reactions of n-butylamine (BA) with solid C3-C8 diacids were studied at 296 ± 1 K using a Knudsen cell interfaced to a quadrupole mass spectrometer. Uptake coefficients for amines on the diacids with known geometric surface areas were measured at initial amine concentrations from (3-50) × 1011 cm-3. Uptake coefficients ranged from 0.7 ± 0.1 (2σ) for malonic acid (C3) to <10-6 for suberic acid (C8), show an odd-even carbon number effect, and decrease with increasing chain length within each series. Butylaminium salts formed from evaporation of aqueous solutions of BA with C3, C5 and C7 diacids (as well as C8) were viscous liquids, suggesting that ionic liquids (ILs) form on the surface during the reactions of gas phase amine with the odd carbon diacids. Predictions from the kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB) were quantitatively consistent with uptake occurring via dissolution of the underlying diacid into the IL layer and reaction with amine taken up from the gas phase. The butylaminium salts formed from the C4 and C6 diacids were solids, and their uptake coefficients were smaller. These experiments and kinetic modeling demonstrate the unexpected formation of ILs in a gas-solid reaction, and suggest that ILs should be considered under some circumstances in atmospheric processes

Introductory lecture: atmospheric chemistry in the Anthropocene.

The term "Anthropocene" was coined by Professor Paul Crutzen in 2000 to describe an unprecedented era in which anthropogenic activities are impacting planet Earth on a global scale. Greatly increased emissions into the atmosphere, reflecting the advent of the Industrial Revolution, have caused significant changes in both the lower and upper atmosphere. Atmospheric reactions of the anthropogenic emissions and of those with biogenic compounds have significant impacts on human health, visibility, climate and weather. Two activities that have had particularly large impacts on the troposphere are fossil fuel combustion and agriculture, both associated with a burgeoning population. Emissions are also changing due to alterations in land use. This paper describes some of the tropospheric chemistry associated with the Anthropocene, with emphasis on areas having large uncertainties. These include heterogeneous chemistry such as those of oxides of nitrogen and the neonicotinoid pesticides, reactions at liquid interfaces, organic oxidations and particle formation, the role of sulfur compounds in the Anthropocene and biogenic-anthropogenic interactions. A clear and quantitative understanding of the connections between emissions, reactions, deposition and atmospheric composition is central to developing appropriate cost-effective strategies for minimizing the impacts of anthropogenic activities. The evolving nature of emissions in the Anthropocene places atmospheric chemistry at the fulcrum of determining human health and welfare in the future