Jacqueline F. Hamilton

The Molecular Identification of Organic Compounds in the Atmosphere: State of the Art and Challenges

Atmosphere: State of the Art and Challenges Barbara Nozier̀e,*,† Markus Kalberer,*,‡ Magda Claeys,* James Allan, Barbara D’Anna,† Stefano Decesari, Emanuela Finessi, Marianne Glasius, Irena Grgic,́ Jacqueline F. Hamilton, Thorsten Hoffmann, Yoshiteru Iinuma, Mohammed Jaoui, Ariane Kahnt, Christopher J. Kampf, Ivan Kourtchev,‡ Willy Maenhaut, Nicholas Marsden, Sanna Saarikoski, Jürgen Schnelle-Kreis, Jason D. Surratt, Sönke Szidat, Rafal Szmigielski, and Armin Wisthaler †Ircelyon/CNRS and Universite ́ Lyon 1, 69626 Villeurbanne Cedex, France ‡University of Cambridge, Cambridge CB2 1EW, United Kingdom University of Antwerp, 2000 Antwerp, Belgium The University of Manchester & National Centre for Atmospheric Science, Manchester M13 9PL, United Kingdom Istituto ISAC C.N.R., I-40129 Bologna, Italy University of York, York YO10 5DD, United Kingdom University of Aarhus, 8000 Aarhus C, Denmark National Institute of Chemistry, 1000 Ljubljana, Slovenia Johannes Gutenberg-Universitaẗ, 55122 Mainz, Germany Leibniz-Institut für Troposphar̈enforschung, 04318 Leipzig, Germany Alion Science & Technology, McLean, Virginia 22102, United States Max Planck Institute for Chemistry, 55128 Mainz, Germany Ghent University, 9000 Gent, Belgium Finnish Meteorological Institute, FI-00101 Helsinki, Finland Helmholtz Zentrum München, D-85764 Neuherberg, Germany University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States University of Bern, 3012 Bern, Switzerland Institute of Physical Chemistry PAS, Warsaw 01-224, Poland University of Oslo, 0316 Oslo, Norway

Meteorology, air quality, and health in London: The ClearfLo project

AbstractAir quality and heat are strong health drivers, and their accurate assessment and forecast are important in densely populated urban areas. However, the sources and processes leading to high concentrations of main pollutants, such as ozone, nitrogen dioxide, and fine and coarse particulate matter, in complex urban areas are not fully understood, limiting our ability to forecast air quality accurately. This paper introduces the Clean Air for London (ClearfLo; www.clearflo.ac.uk) project’s interdisciplinary approach to investigate the processes leading to poor air quality and elevated temperatures.Within ClearfLo, a large multi-institutional project funded by the U.K. Natural Environment Research Council (NERC), integrated measurements of meteorology and gaseous, and particulate composition/loading within the atmosphere of London, United Kingdom, were undertaken to understand the processes underlying poor air quality. Long-term measurement infrastructure installed at multiple levels (street and eleva...

Aerosol and trace-gas measurements in the Darwin area during the wet season

[1] The composition of the planetary boundary layer in regions of deep tropical convection has a profound impact on the Tropical Tropopause Layer ( TTL). The Aerosol and Chemical Transport in tropIcal conVEction ( ACTIVE) aircraft campaign was conducted from November 2005 to February 2006 from Darwin, Australia, to characterize the influence of both monsoonal and localized land-based deep convection on the composition of the TTL. This paper summarizes the composition of the potential inflow to such convection in terms of aerosol particle size and composition, carbon monoxide, and ozone, as measured in the lowest 4 km of the atmosphere by the NERC Dornier-228 aircraft during 28 flights in different meteorological regimes over the course of ACTIVE. Six contrasting periods are identified in the boundary layer background as a result of the prevailing meteorology and sources of pollution. The campaign began with a relatively polluted and variable biomass burning season in November, followed by a transition to the monsoon season through December with much less burning. A clean maritime flow dominated the wet-active, and dry-inactive, monsoon period in January; it was followed by a monsoon break period in February, with a return to continental flow and a more premonsoon background state. Deep convective systems, capable of transporting boundary layer air to the TTL, were observed daily outside of the monsoon periods. The chemical composition of submicron aerosols in the premonsoon periods was dominated by a mix of fresh and aged organic material with significant black carbon, well-correlated with carbon monoxide indicating a common burning source, while marine aerosol during the monsoon changed markedly between the wet and dry phases. High concentrations of coarse-mode aerosols were also observed in the monsoon: the clean, marine air masses and high surface winds imply that sea salt may be the dominant aerosol type under these conditions. The climatology presented here will provide a valuable data set for model simulation of chemical and aerosol transport by deep convection in the Darwin region.

Determination of volatile nitrosamines in various meat products using comprehensive gas chromatography-nitrogen chemiluminescence detection.

An optimized method was developed for the extraction, pre-concentration and analysis of nitrosamines (NAs) in various meat products. Values of reproducibility, linearity, limit of detection (LOD) and limit of quantitation (LOQ) for six NA standards (N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosodi-n-propylamine, N-nitrosopyrrolidine, N-nitrosopiperidine, N-nitrosodi-n-butylamine) were determined. The LODs using this method were between 1.66-3.86 and LOQs between 6.96-16.71 μg L(-1). The screening of four different types of meat samples (sausage, salami, sucuk and doner kebab) showed that all samples contained levels of various NAs, identified with high confidence using comprehensive gas chromatography (GCxGC) and a fast responding element specific nitrogen chemiluminescence detector (NCD). The sum of the six NAs were highest in the doner kebab samples, being between 0.51-16.63 μg kg(-1) and were lowest in the sausage samples at 0.45-2.93 μg kg(-1). The described method is simple, rapid, selective and sensitive.

Microfabricated planar glass gas chromatography with photoionization detection

We report the development of a microfabricated gas chromatography system suitable for the separation of volatile organic compounds (VOCs) and compatible with use as a portable measurement device. Hydrofluoric acid etching of 95x95mm Schott B270 wafers has been used to give symmetrical hemi-spherical channels within a glass substrate. Two matching glass plates were subsequently cold bonded with the channels aligned; the flatness of the glass surfaces resulted in strong bonding through van der Waals forces. The device comprised gas fluidic interconnections, injection zone and 7.5 and 1.4m long, 320microm internal diameter capillaries. Optical microscopy confirmed the capillaries to have fully circular channel profiles. Direct column heating and cooling could be achieved using a combination of resistive heaters and Peltier devices. The low thermal conductivity of glass allowed for multiple uniform temperature zones to be achieved within a single glass chip. Temperature control over the range 10-200 degrees C was achieved with peak power demand of approximately 25W. The 7.5m capillary column was static coated with a 2microm film of non-polar dimethylpolysiloxane stationary phase. A standard FID and a modified lightweight 100mW photoionization detector (PID) were coupled to the column and performance tested with gas mixtures of monoaromatic and monoterpene species at the parts per million concentration level. The low power GC-PID device showed good performance for a small set of VOCs and sub ng detection sensitivity to monoaromatics.

Modelling the ambient distribution of organic compounds during the August 2003 ozone episode in the southern UK

A photochemical trajectory model containing speciated emissions of 124 non-methane volatile organic compounds (VOC), and a comprehensive description of the chemistry of VOC degradation, has been used to simulate the chemical evolution of boundary layer air masses arriving at a field campaign site in the southern UK during a widespread and prolonged photochemical pollution event in August 2003. The simulated concentrations and distributions of organic compounds at the arrival location are compared with observations of a series of hydrocarbons and carbonyl compounds, which were measured using GC-FID and multidimensional GC methods. The comparison of the simulated and observed distributions of 34 emitted hydrocarbons provides some support for the magnitude and applied emissions speciation of anthropogenic hydrocarbons, but is indicative of an under representation of the input of biogenic hydrocarbons, particularly at elevated temperatures. Simulations of the detailed distribution of ca. 1250 carbonyl compounds, formed primarily from the degradation of the 124 emitted VOC, focus on 61 aldehydes, ketones, dicarbonyls, hydroxycarbonyls and aromatic aldehydes which collectively account for ca. 90% of the simulated total molar concentration of carbonyls. The simulated distributions indicate that the photolysis of formaldehyde and alpha-dicarbonyls make major contributions to free radical production for the arrival conditions of five case study trajectories. The simulated concentrations of hydroxycarbonyls demonstrate preferential formation of the 1,4-substituted isomers (compared with 1,2- and 1,3-isomers of the same carbon number), which are formed during the initial oxidation sequence of longer chain alkanes.

New Sensitive and Quantitative Analysis Method for Organic Nitrogen Compounds in Urban Aerosol Samples

Atmospheric aerosols contain a highly complex mixture of organic and inorganic compounds; however, as a chemical class relatively little is known about organic nitrogen (ON) content, with few satisfactory methods for speciated analysis. In this paper we report a sensitive and quantitative method for the speciation of ON within ambient atmospheric aerosol. Aerosol samples, collected on quartz microfiber filters, were extracted in water followed by solid phase extraction, elution, and concentration before analysis by comprehensive gas chromatography with a nitrogen chemiluminescence detection system (GCxGC-NCD). The NCD detection method was optimized using liquid standards. The GCxGC-NCD method showed high selectivity, sensitivity, and equimolarity in its response to individual organic compounds. Limits of detection (LOD) and limits of quantitation (LOQ) for four ON standards (1-nitropentane, o-toluidine, nonanenitrile, and quinoline) were determined to be in the range 0.16-0.27 pgN and 0.71-1.19 pgN, respectively. Between 21 and 57 different ON compounds were found in urban aerosol, (including 10 nitriles, 9 alkyl nitro compounds, 4 nitro-phenols, 4 amides, 3 nitrosamines, and 2 nitro-PAHs) on different dates from a city center location. Pyrrole (8.26-39.21 ngN m(-3) air) and N-butyl-benzenesulfonamide (6.23-20.87 ngN m(-3) air) were the most abundant ON compounds observed in all samples analyzed. The average mass loading of the total identified ON was 532.51 ngON m(-3) air. The sensitivity, selectivity, and relative ease of quantitation of unknown ON components makes the technique a significant improvement over previous laboratory methods.

Protein sequences bound to mineral surfaces persist into deep time

Proteins persist longer in the fossil record than DNA, but the longevity, survival mechanisms and substrates remain contested. Here, we demonstrate the role of mineral binding in preserving the protein sequence in ostrich (Struthionidae) eggshell, including from the palaeontological sites of Laetoli (3.8 Ma) and Olduvai Gorge (1.3 Ma) in Tanzania. By tracking protein diagenesis back in time we find consistent patterns of preservation, demonstrating authenticity of the surviving sequences. Molecular dynamics simulations of struthiocalcin-1 and -2, the dominant proteins within the eggshell, reveal that distinct domains bind to the mineral surface. It is the domain with the strongest calculated binding energy to the calcite surface that is selectively preserved. Thermal age calculations demonstrate that the Laetoli and Olduvai peptides are 50 times older than any previously authenticated sequence (equivalent to ~16 Ma at a constant 10°C). DOI: http://dx.doi.org/10.7554/eLife.17092.001

The first UK measurements of nitryl chloride using a chemical ionization mass spectrometer in central London in the summer of 2012, and an investigation of the role of Cl atom oxidation

The first nitryl chloride (ClNO2) measurements in the UK were made during the summer 2012 ClearfLo campaign with a chemical ionization mass spectrometer, utilizing an I− ionization scheme. Concentrations of ClNO2 exceeded detectable limits (11 ppt) every night with a maximum concentration of 724 ppt. A diurnal profile of ClNO2 peaking between 4 and 5 A.M., decreasing directly after sunrise, was observed. Concentrations of ClNO2 above the detection limit are generally observed between 8 P.M. and 11 A.M. Different ratios of the production of ClNO2:N2O5 were observed throughout with both positive and negative correlations between the two species being reported. The photolysis of ClNO2 and a box model utilizing the Master Chemical Mechanism modified to include chlorine chemistry was used to calculate Cl atom concentrations. Simultaneous measurements of hydroxyl radicals (OH) using low pressure laser-induced fluorescence and ozone enabled the relative importance of the oxidation of three groups of measured VOCs (alkanes, alkenes, and alkynes) by OH radicals, Cl atoms, and O3 to be compared. For the day with the maximum calculated Cl atom concentration, Cl atoms in the early morning were the dominant oxidant for alkanes and, over the entire day, contributed 15%, 3%, and 26% toward the oxidation of alkanes, alkenes, and alkynes, respectively.

Determination of airborne carbonyls via pentafluorophenylhydrazine derivatisation by GC–MS and its comparison with HPLC method

The classical analytical method for gaseous carbonyl measurements based on solid sorbent coated with 2,4-dinitrophenylhydrazine (DNPH) and analysis by HPLC/UV suffers from limited resolution of carbonyls with similar molecular structures and high molecular weights. In this paper, we report the development of a sensitive and reliable analytical method for simultaneous determination of 21 airborne carbonyls within the C(1)-C(9) range. Carbonyls were collected on a sampling tube filled with 100mg Tenax TA (60-80 mesh) sorbent coated with 1 μmol pentafluorophenyl hydrazine (PFPH), followed by solvent desorption and analysis by gas chromatography (GC)/mass spectrometry (MS). Common carbonyl gases including formaldehyde, acetaldehyde, butyraldehyde, hexaldehyde and benzaldehyde at ppbv levels were collected with efficiency greater than 90% onto sampling tubes at a flow rate of 100 mL min(-1). The limits of detection (LODs, signal/noise=3) of the tested carbonyls were in the range of 0.08-0.20 ppbv for a sampled volume of 24.0 L. These limits are less than or comparable with those that can be obtained using the DNPH-HPLC method. The method has been field-tested both in ambient air of York and in diluted cigarette smoke. Comparing field tests with the classical DNPH-HPLC method, good agreement was displayed between the two methods for the same carbonyls, but with more carbonyl species detected by the PFPH-GC/MS method. The PFPH-GC/MS method provides better molecular separation for carbonyls with similar structures, is highly sensitivity and gives confirmation of identification by structures when detected using MS.