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Results of the first air ion spectrometer calibration and intercomparison workshop

The Air Ion Spectrometer (AIS) measures mobility and size distributions of atmospheric ions. The Neutral cluster and Air Ion Spectrometer (NAIS) can additionally measure neutral particles. The number of the (N)AIS instruments in the world is only 11. Nevertheless, they are already widely used in atmospheric ion studies, particularly related to the initial steps of new particle formation. There is no standard method applicable for calibrating the ion spectrometers in the sub-3 nm ion range. However, recent development of high resolution DMAs has enabled the size separation of small ions with good mobility resolution. For the first time, the ion spectrometers were intercompared and calibrated in a workshop, held in January–February 2008 in Helsinki, Finland. The overall goal was to experimentally determine the (N)AIS transfer functions. Monomobile mobility standards, 241-Am charger ions and silver particles were generated and used as calibration aerosols. High resolution DMAs were used to size-separate the smaller (1–10 nm) ions, while at bigger diameters (4–40 nm) the size was selected with a HAUKE-type DMA. Negative ion mobilities were detected by (N)AISs with slightly better accuracy than positive, nonetheless, both were somewhat overestimated. A linear fit of slope of one to the whole dataset of mobilities suggested that (N)AISs measured the negative mobilities 1.36±0.16 times larger compared with the reference instruments. Similarly, positive mobilities were measured 1.39±0.15 times larger compared with the reference instruments. The completely monomobile mobility standards were measured with the best accuracy. The (N)AIS concentrations were compared with an aerosol electrometer (AE) and a condensation particle counter (CPC). At sizes below 1.5 nm (positive) and 3 nm (negative) the ion spectrometers detected higher concentrations while at bigger sizes they showed similar concentrations as the reference instruments. The total particle concentrations measured by the NAISs were within ±50% of the reference CPC concentration at 4–40 nm sizes. The lowest cut-off size of the NAIS in neutral particle measurements was determined to be between 1.5 and 3 nm, depending on the measurement conditions and the polarity.
Airborne measurement of OH reactivity during INTEX-B

The measurement of OH reactivity, the inverse of the OH lifetime, provides a powerful tool to investigate atmospheric photochemistry. A new airborne OH reactivity instrument was designed and deployed for the first time on the NASA DC-8 aircraft during the second phase of Intercontinental Chemical Transport Experiment-B (INTEX-B) campaign, which was focused on the Asian pollution outflow over Pacific Ocean and was based in Hawaii and Alaska. The OH reactivity was measured by adding OH, generated by photolyzing water vapor with 185 nm UV light in a moveable wand, to the flow of ambient air in a flow tube and measuring the OH signal with laser induced fluorescence. As the wand was pulled back away from the OH detector, the OH signal decay was recorded; the slope of −Δln(signal)/Δ time was the OH reactivity. The overall absolute uncertainty at the 2σ confidence levels is about 1 s−1 at low altitudes (for decay about 6 s−1), and 0.7 s−1 at high altitudes (for decay about 2 s−1). From the median vertical profile obtained in the second phase of INTEX-B, the measured OH reactivity (4.0±1.0 s−1) is higher than the OH reactivity calculated from assuming that OH was in steady state (3.3&plusmn0.8 s−1), and even higher than the OH reactivity that was calculated from the total measurements of all OH reactants (1.6±0.4 s−1). Model calculations show that the missing OH reactivity is consistent with the over-predicted OH and under-predicted HCHO in the boundary layer and lower troposphere. The over-predicted OH and under-predicted HCHO suggest that the missing OH sinks are most likely related to some highly reactive VOCs that have HCHO as an oxidation product.
Spatial distribution of Δ14CO2 across Eurasia: measurements from the TROICA-8 expedition

Because fossil fuel derived CO2 is the only source of atmospheric CO2 that is devoid of 14C, atmospheric measurements of Δ14CO2 can be used to constrain fossil fuel emission estimates at local and regional scales. However, at the continental scale, uncertainties in atmospheric transport and other sources of variability in Δ14CO2 may influence the fossil fuel detection capability. We present a set of Δ14CO2 observations from the train-based TROICA-8 expedition across Eurasia in March–April 2004. Local perturbations in Δ14CO2 are caused by easily identifiable sources from nuclear reactors and localized pollution events. The remaining data show an increase in Δ14CO2 from Western Russia (40° E) to Eastern Siberia (120° E), consistent with depletion in 14CO2 caused by fossil fuel CO2 emissions in heavily populated Europe, and gradual dispersion of the fossil fuel plume across Northern Asia. Other trace gas species which may be correlated with fossil fuel CO2 emissions, including carbon monoxide, sulphur hexafluoride, and perchloroethylene, were also measured and the results compared with the Δ14CO2 measurements. The sulphur hexafluoride longitudinal gradient is not significant relative to the measurement uncertainty. Carbon monoxide and perchloroethylene show large-scale trends of enriched values in Western Russia and decreasing values in Eastern Siberia, consistent with fossil fuel emissions, but exhibit significant spatial variability, especially near their primary sources in Western Russia. The clean air Δ14CO2 observations are compared with simulated spatial gradients from the TM5 atmospheric transport model. We show that the change in Δ14CO2 across the TROICA transect is due almost entirely to emissions of fossil fuel CO2, but that the magnitude of this Δ14CO2 gradient is relatively insensitive to modest uncertainties in the fossil fuel flux. In contrast, the Δ14CO2 gradient is more sensitive to the modeled representation of vertical mixing, suggesting that Δ14CO2 may be a useful tracer for training mixing in atmospheric transport models.
Laboratory measurements of the optical properties of sea salt aerosol

The extinction spectra of laboratory generated sea salt aerosols have been measured from 1 μm to 20 μm using a Bruker 66v/S FTIR spectrometer. Concomitant measurements include temperature, pressure, relative humidity and the aerosol size distribution. The refractive indices of the sea salt aerosol have been determined using a simple harmonic oscillator band model (Thomas et al., 2004) for aerosol with relative humidities at eight different values between 0.4% to 86%. The resulting refractive index spectra show significant discrepancies when compared to existing sea salt refractive indices calculated using volume mixing rules (Shettle and Fenn, 1979). Specifically, an additional band is found in the refractive indices of dry sea salt aerosol and the new data shows increased values of refractive index at almost all wavelengths. This implies that the volume mixing rules, currently used to calculate the refractive indices of wet sea salt aerosols, are inadequate. Furthermore, the existing data for the real and imaginary parts of the refractive indices of dry sea salt aerosol are found not to display the Kramers-Kronig relationship. This implies that the original data used for the volume mixing calculations is also inaccurate.
Measurements of aerosol absorption and scattering in the Mexico City Metropolitan Area during the MILAGRO field campaign: a comparison of results from the T0 and T1 sites

In March 2006, a multiagency field campaign was undertaken in Mexico City called the Megacities Initiative: Local and Global Research Observations (MILAGRO). Two of the five field components of the MILAGRO study focused a major part of their efforts on atmospheric particulate emissions from the Mexico City basin and their effects on radiative balance as a function of time, location and processing conditions. As part of these two MILAGRO components, measurements of aerosol optical properties were obtained at a site located in the northern part of Mexico City (T0) and also at a site located 29 km northwest (T1) to estimate the regional effects of aerosol emissions from the basin. Measurements of aerosol absorption and scattering for fine mode aerosols were obtained at both sites. Aerosol absorption at 550 nm was similar at both sites, ranging from 7–107 Mm−1 at T0 and from 3–147 Mm−1 at T1. Aerosol scattering measured at 550 nm at T0 ranged from 16–344 Mm−1 while the aerosol scattering values at T1 were much lower than at T0 ranging from 2–136 Mm−1. Aerosol single scattering albedos (SSAs) were calculated at 550 nm for the fine mode aerosols at both sites using these data. The SSAs at T0 ranged from 0.47–0.92 while SSAs at T1 ranged from 0.35–0.86. The presence of these highly absorbing fine aerosols in the lower atmosphere of the Mexico City area will result in a positive climate forcing and a local warming of the boundary layer in the region. Broadband UVB intensity was found to be higher at site T0, with an average of 64 μW/cm2 at solar noon, than at site T1, which had an average of 54 μW/cm2 at solar noon. Comparisons of clear-sky modeled UVB intensities with the simultaneous UVB measurements obtained at sites T0 and T1 for cloudless days indicate a larger diffuse radiation field at site T0 than at site T1. The determination of aerosol Ångstrom scattering coefficients at T0 suggests that this is due to the predominance of aerosols in the size range of 0.3 micron, which leads to scattering of UVB radiation peaked in the forward direction and to an enhanced UVB radiation observed at ground level. This enhancement of the UVB diffuse radiation field would explain the enhanced photochemistry observed in the Mexico City area despite the reduction in UVB anticipated from light absorbing species.
In situ measurements of speciated atmospheric mercury and the identification of source regions in the Mexico City Metropolitan Area

In order to expand the currently limited understanding of atmospheric mercury source-receptor relationships in the Mexico City Metropolitan Area, real time measurements of atmospheric mercury were made at a downtown urban site, and a rural site on the outskirts of Mexico City, during March 2006. Numerous short-lived increases in particulate mercury (PHg) and reactive gaseous mercury (RGM) concentrations were observed at the urban site during the 17 day study, and less frequent increases in gaseous elemental mercury (GEM) concentrations were measured at both the urban and rural sites. The episodic increases observed were attributed to plume impacts from industrial point source emissions in and around Mexico City. Average concentrations and standard deviations measured during the study were as follows: i) urban site; PHg=187±300 pg m−3, RGM=62±64 pg m−3, GEM=7.2±4.8 ng m−3, and; ii) rural site; GEM=5.0±2.8 ng m−3. Several source regions of atmospheric mercury to the urban and rural sites were determined using Concentration Field Analysis, in which atmospheric mercury measurements were combined with back trajectory data to determine source regions. Only some source regions correlated to mercury emission sources listed in the Federal Pollutant Release and Transfer Register, leaving the rest unaccounted for. Contributions of anthropogenic mercury point sources in and around Mexico City to concentration averages measured at the urban site during the study were estimated to be: 93±3% of reactive mercury (PHg and RGM), and; 81±0.4% of GEM. Point source contributions to GEM measured at the rural site were 72±1%. GEM and reactive mercury (PHg+RGM) were not found to correlate with biomass burning at either of the measurement sites.
A QBO-signal in mesospheric water vapor measurements at ALOMAR (69.29° N, 16.03° E) and in model calculations by LIMA over a solar cycle

Microwave water vapor measurements between 40 and 80 km over a solar cycle (1996–2006) were carried out in high latitudes at ALOMAR (69.29° N, 16.03° E), Norway. Three larger interuptions in the winters of 1996/97 and 2005/06, and from spring 2001 to spring 2002, a few smaller interruptions of monitoring occurred during this period. The observed year-to-year variability is not directly related to the solar activity. The analysis of the observations by the Fast Fourier Transform (FFT) method revealed peaks close to two years, particularly in the upper monitoring domain. Model calculations by means of the real date model LIMA, Leibniz-Institute Middle Atmosphere model, reflect essential patterns of the water vapor variation. The FFT-analysis of the calculated water vapor mixing ratios also showed peaks of around two years. The real period of the QBO during the monitoring period ranged quite close to two years within the time interval considered, with the exception of the years 2001/02 when the period was essentially longer. Although the QBO is a phenomenon occurring in the zonal wind of the tropical stratosphere, we suppose an influence of the QBO on the water vapor distribution of the mesosphere of high latitudes controlled by transport processes. A possible link could be given by the planetary wave activity triggered by the QBO.
Emissions of volatile organic compounds inferred from airborne flux measurements over a megacity

Toluene and benzene are used for assessing the ability to measure disjunct eddy covariance (DEC) fluxes of Volatile Organic Compounds (VOC) using Proton Transfer Reaction Mass Spectrometry (PTR-MS) on aircraft. Statistically significant correlation between vertical wind speed and mixing ratios suggests that airborne VOC eddy covariance (EC) flux measurements using PTR-MS are feasible. City-median midday toluene and benzene fluxes are calculated to be on the order of 14.1±4.0 mg/m2/h and 4.7±2.3 mg/m2/h, respectively. For comparison the adjusted CAM2004 emission inventory estimates toluene fluxes of 10 mg/m2/h along the footprint of the flight-track. Wavelet analysis of instantaneous toluene and benzene measurements during city overpasses is tested as a tool to assess surface emission heterogeneity. High toluene to benzene flux ratios above an industrial district (e.g. 10–15 g/g) including the International airport (e.g. 3–5 g/g) and a mean flux (concentration) ratio of 3.2±0.5 g/g (3.9±0.3 g/g) across Mexico City indicate that evaporative fuel and industrial emissions play an important role for the prevalence of aromatic compounds. Based on a tracer model, which was constrained by BTEX (BTEX– Benzene/Toluene/Ethylbenzene/m, p, o-Xylenes) compound concentration ratios, the fuel marker methyl-tertiary-butyl-ether (MTBE) and the biomass burning marker acetonitrile (CH3CN), we show that a combination of industrial, evaporative fuel, and exhaust emissions account for >87% of all BTEX sources. Our observations suggest that biomass burning emissions play a minor role for the abundance of BTEX compounds in the MCMA (2–13%).
An extreme CO pollution event over Indonesia measured by the MOPITT instrument

In the fall of 2006, the Measurements Of Pollution In The Troposphere (MOPITT) instrument on the Terra satellite observed an extremely high Carbon monoxide (CO) concentration over Indonesia. This extreme event was caused by huge fire activity during the 2006 El Nino event. From our comparison with other high CO pollution events over Indonesia during similar and moderate El Nino events, we conclude that the 2006 fire activity, which caused large-scale pollution in this region, was probably amplified by an increase in frequency and/or intensity of lightning activity in a feedback mechanism. We also observed that after the fire episodes in El Nino years, the "lightning rate" was less than during the fire episode but displayed an increasing trend across the three events observed that might have been be caused by interactions with fire smoke plumes.
Properties of aerosols and their wet deposition in the arctic spring during ASTAR2004 at Ny-Alesund, Svalbard

During the period of scientific campaign "Arctic Study of Tropospheric Aerosols, Clouds and Radiation 2004" (ASTAR2004), precipitation samples were collected in late spring at Ny-Alesund, Svalbard and their ionic components were analyzed in parallel with the measurement of properties of atmospheric aerosol particles at the same place. Backward trajectory analyses indicated that the air mass above the observatory initially dominated by air masses from the Arctic Ocean, then those from western Siberia and later those from Greenland and the Arctic Ocean. In the measurement period, six precipitation samples were obtained and five of them were analyzed their ionic components by ionchromatography. The concentrations of nss-sulphate in precipitations were between 1.8 and 24.6 ppm from which the scavenging ratio and scavenging coefficients were calculated using the data such as the concentrations of nss-sulphate in aerosol particles, amounts of precipitations, and the heights of precipitations obtained from radar echo data. The scavenging ratio ranged from 1.0×106 to 17×106 which are comparable values reported in other areas. A detailed comparison between precipitation events and the number concentration of aerosol particles obtained from optical particle counters suggests that the type of precipitations, i.e. rain or snow, significantly affects the number concentrations of aerosol particles.