ALBERT

Description: Particle size distributions in the range of 1.34–615.3 nm were recorded from 25 November 2013 to 25 January 2014 in urban Shanghai, using a combination of one nano Condensation Nucleus Counter system (nCNC), one nano-Scanning Mobility Particle Sizer (SMPS), and one long-SMPS. Measurements of sulfur dioxide by an SO2 analyzer with pulsed UV fluorescence technique allowed calculation of sulfuric acid proxy. In addition, concentrations of ammonia were recorded with a Differential Optical Absorption Spectroscopy (DOAS). During this 62-day campaign, 13 NPF events were identified with strong burst of sub-3 nm particles and subsequent fast growth of newly formed particles. The observed nucleation rate (J1.34), formation rate of 3 nm particles (J3), and condensation sink (CS) were 112.4–271.0 cm−3 s−1, 2.3–19.2 cm−3 s−1, and 0.030–0.10 s−1, respectively. Subsequent cluster/nanoparticle growth showed a clear size dependence, with average values of GR1.35~1.39 (from the bin of 1.34–1.37 nm to the bin of 1.37–1.41 nm), GR1.39~1.46 (from 1.37–1.41 to 1.41–1.52 nm), GR1.46~1.70 (from 1.41–1.52 to 1.52–1.89 nm), GR1.70~2.39 (from 1.52–1.89 to 1.89–3.0 nm), GR2.39~7 (from 1.89–3.0 to 7 nm), and GR7~20 (from 7 to 20 nm) being 1.6 ± 1.0, 1.4 ± 2.2, 7.2 ± 7.1, 9.0 ± 11.4, 10.9 ± 9.8, and 11.4 ± 9.7 nm h−1, respectively. Correlation between nucleation rate (J1.34) and sulfuric acid proxy indicates that nucleation rate J1.34 was proportional to a 0.64 power of sulfuric acid proxy. Correlation between nucleation rate (J1.34) and gas-phase ammonia suggests that ammonia was associated with NPF events. The calculated sulfuric acid proxy was sufficient to explain the subsequent growth of 1.34–3 nm particles, but insufficient for particles exceeding this size range. Qualitatively, NPF events in urban Shanghai likely occur on days with low levels of PM2.5.

Description: Nitric acid (HNO3) is one of the key products that are operationally retrieved by the European Space Agency (ESA) from the emission spectra measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard ENVISAT. The product version 4.61/4.62 for the observation period between July 2002 and March 2004 is validated by comparisons with a number of independent observations from ground-based stations, aircraft/balloon campaigns, and satellites. Individual HNO3 profiles of the ESA MIPAS level-2 product show good agreement with those of MIPAS-B and MIPAS-STR (the balloon and aircraft version of MIPAS, respectively), and the balloon-borne infrared spectrometers MkIV and SPIRALE, mostly matching the reference data within the combined instrument error bars. In most cases differences between the correlative measurement pairs are less than 1 ppbv (5–10%) throughout the entire altitude range up to about 38 km (~6 hPa), and below 0.5 ppbv (15–20% or more) above 30 km (~17 hPa). However, differences up to 4 ppbv compared to MkIV have been found at high latitudes in December 2002 in the presence of polar stratospheric clouds. The degree of consistency is further largely affected by the temporal and spatial coincidence, and differences of 2 ppbv may be observed between 22 and 26 km (~50 and 30 hPa) at high latitudes near the vortex boundary, due to large horizontal inhomogeneity of HNO3. Similar features are also observed in the mean differences of the MIPAS ESA HNO3 VMRs with respect to the ground-based FTIR measurements at five stations, aircraft-based SAFIRE-A and ASUR, and the balloon campaign IBEX. The mean relative differences between the MIPAS and FTIR HNO3 partial columns are within ±2%, comparable to the MIPAS systematic error of ~2%. %This should be the systematic error without spectroscopy since the ground-based data were retrieved using the same version of the HITRAN database. For the vertical profiles, the biases between the MIPAS and FTIR data are generally below 10% in the altitudes of 10 to 30 km. The MIPAS and SAFIRE chem{HNO_3} data generally match within their total error bars for the mid and high latitude flights, despite the larger atmospheric inhomogeneities that characterize the measurement scenario at higher latitudes. The MIPAS and ASUR comparison reveals generally good agreements better than 10–13% at 20–34 km. The MIPAS and IBEX measurements agree reasonably well (mean relative differences within ±15%) between 17 and 32 km. Statistical comparisons of the MIPAS profiles correlated with those of Odin/SMR, ILAS-II, and ACE-FTS generally show good consistency. The mean differences averaged over individual latitude bands or all bands are within the combined instrument errors, and generally within 1, 0.5, and 0.3 ppbv between 10 and 40 km (~260 and 4.5 hPa) for Odin/SMR, ILAS-II, and ACE-FTS, respectively. The standard deviations of the differences are between 1 to 2 ppbv. The standard deviations for the satellite comparisons and for almost all other comparisons are generally larger than the estimated measurement uncertainty. This is associated with the temporal and spatial coincidence error and the horizontal smoothing error which are not taken into account in our error budget. Both errors become large when the spatial variability of the target molecule is high.

Description: This paper characterizes vertical ozone profiles retrieved with the IMK-IAA (Institute for Meteorology and Climate Research, Karlsruhe – Instituto de Astrofisica de Andalucia) science-oriented processor from spectra measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the environmental satellite Envisat. Bias determination and precision validation is performed on the basis of correlative measurements by ground-based lidars, Fourier transform infrared spectrometers, and microwave radiometers as well as balloon-borne ozonesondes, the balloon-borne version of MIPAS, and two satellite instruments (Halogen Occultation Experiment and Polar Ozone and Aerosol Measurement III). Percentage mean differences between MIPAS and the comparison instruments for stratospheric ozone are within ±10%. The precision in this altitude region is estimated at values between 5 and 10% which gives an accuracy of 15 to 20%. Below 18 km, the spread of the percentage mean differences is larger and the precision increases to values of more than 20% depending on altitude and latitude. The main reason for the degraded precision at low altitudes is attributed to undetected thin clouds which affect MIPAS retrievals, and to the influence of uncertainties in the water vapor concentration.

Description: Nitric acid (HNO3) is one of the key products that are operationally retrieved by the European Space Agency (ESA) from the emission spectra measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard ENVISAT. The product version 4.61/4.62 for the observation period between July 2002 and March 2004 is validated by comparisons with a number of independent observations from ground-based stations, aircraft/balloon campaigns, and satellites. Individual HNO3 profiles of the ESA MIPAS level-2 product show good agreement with those of MIPAS-B and MIPAS-STR (the balloon and aircraft version of MIPAS, respectively), and the balloon-borne infrared spectrometers MkIV and SPIRALE, mostly matching the reference data within the combined instrument error bars. In most cases differences between the correlative measurement pairs are less than 1 ppbv (5–10%) throughout the entire altitude range up to about 38 km (~6 hPa), and below 0.5 ppbv (15–20% or more) above 30 km (~17 hPa). However, differences up to 4 ppbv compared to MkIV have been found at high latitudes in December 2002 in the presence of polar stratospheric clouds. The degree of consistency is further largely affected by the temporal and spatial coincidence, and differences of 2 ppbv may be observed between 22 and 26 km (~50 and 30 hPa) at high latitudes near the vortex boundary, due to large horizontal inhomogeneity of HNO3. Similar features are also observed in the mean differences of the MIPAS ESA HNO3 VMRs with respect to the ground-based FTIR measurements at five stations, aircraft-based SAFIRE-A and ASUR, and the balloon campaign IBEX. The mean relative differences between the MIPAS and FTIR HNO3 partial columns are within ±2%, comparable to the MIPAS systematic error of ~2%. For the vertical profiles, the biases between the MIPAS and FTIR data are generally below 10% in the altitudes of 10 to 30 km. The MIPAS and SAFIRE HNO3 data generally match within their total error bars for the mid and high latitude flights, despite the larger atmospheric inhomogeneities that characterize the measurement scenario at higher latitudes. The MIPAS and ASUR comparison reveals generally good agreements better than 10–13% at 20–34 km. The MIPAS and IBEX measurements agree reasonably well (mean relative differences within ±15%) between 17 and 32 km. Statistical comparisons of the MIPAS profiles correlated with those of Odin/SMR, ILAS-II, and ACE-FTS generally show good consistency. The mean differences averaged over individual latitude bands or all bands are within the combined instrument errors, and generally within 1, 0.5, and 0.3 ppbv between 10 and 40 km (~260 and 4.5 hPa) for Odin/SMR, ILAS-II, and ACE-FTS, respectively. The standard deviations of the differences are between 1 to 2 ppbv. The standard deviations for the satellite comparisons and for almost all other comparisons are generally larger than the estimated measurement uncertainty. This is associated with the temporal and spatial coincidence error and the horizontal smoothing error which are not taken into account in our error budget. Both errors become large when the spatial variability of the target molecule is high.

Description: This paper characterizes vertical ozone profiles retrieved with the IMK-IAA (Institute for Meteorology and Climate Research, Karlsruhe – Instituto de Astrofisica de Andalucia) science-oriented processor from high spectral resolution data (until March 2004) measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) aboard the environmental satellite Envisat. Bias determination and precision validation is performed on the basis of correlative measurements by ground-based lidars, Fourier transform infrared spectrometers, and microwave radiometers as well as balloon-borne ozonesondes, the balloon-borne version of MIPAS, and two satellite instruments (Halogen Occultation Experiment and Polar Ozone and Aerosol Measurement III). Percentage mean differences between MIPAS and the comparison instruments for stratospheric ozone are generally within ±10%. The precision in this altitude region is estimated at values between 5 and 10% which gives an accuracy of 15 to 20%. Below 18 km, the spread of the percentage mean differences is larger and the precision degrades to values of more than 20% depending on altitude and latitude. The main reason for the degraded precision at low altitudes is attributed to undetected thin clouds which affect MIPAS retrievals, and to the influence of uncertainties in the water vapor concentration.

Description: The existing solvents trichloroethylene (TCE) and perchloroethylene (PCE) and proposed solvent n-propyl bromide (nPB) have atmospheric lifetimes from days to a few months, but contain chlorine or bromine that could affect stratospheric ozone. Several previous studies estimated the Ozone Depletion Potentials (ODPs) for various assumptions of nPB emissions location, but these studies used simplified modeling treatments. The primary purpose of this study is to reevaluate the ODP for n-propyl bromide (nPB) using a current-generation chemistry-transport model of the troposphere and stratosphere. For the first time, ODPs for TCE and PCE are also evaluated in a three-dimensional, global atmospheric chemistry-transport model. Emissions representing industrial use of each compound are incorporated on land surfaces from 30° N to 60° N. The atmospheric chemical lifetime obtained for nPB is 24.7 days, similar to past literature, but the ODP is 0.0049, lower than in our past study of nPB. The derived atmospheric lifetime for TCE is 13.0 days and for PCE is 111 days. The corresponding ODPs are 0.00037 and 0.0050, respectively.

Description: The spatial and temporal distribution patterns of mercury (Hg) in precipitation were investigated in the core urban areas of Chongqing, China. During the period from July 2010 to June 2011, total mercury (THg) and methyl mercury (MeHg) concentrations in precipitation were analysed from three sampling sites. Our results suggested that the volume-weight mean THg and MeHg concentrations in precipitation were 30.67 ng l−1 and 0.31 ng l−1, respectively. The proportion of MeHg in THg ranged from 0.1% to 7.6% with a mean value of 1.3%. THg and MeHg concentrations showed seasonal variations, while the highest THg value was measured in winter. Contrarily, the highest MeHg concentration was observed in autumn. Additionally, a geographically gradual decline of THg concentration in precipitation was observed from the downtown to the suburb, then to the controlled site in the city. 5 mm rainfall might be a threshold for the full wash-out capability. Rainfall above 5 mm may have a diluting effect for the concentrations of THg. Moreover, the current research implies that the coal combustion and motor vehicles could be the dominant sources for Hg in the precipitation.

Description: An automated identification and integration method has been developed to investigate in-use vehicle emissions under real-world conditions. This technique was applied to high time resolution air pollutant measurements of in-use vehicle emissions performed under real-world conditions at a near-road monitoring station in Toronto, Canada during four seasons, through month-long campaigns in 2013–2014. Based on carbon dioxide measurements, over 100 000 vehicle-related plumes were automatically identified and fuel-based emission factors for nitrogen oxides; carbon monoxide; particle number, black carbon; benzene, toluene, ethylbenzene, and xylenes (BTEX); and methanol were determined for each plume. Thus the automated identification enabled the measurement of an unprecedented number of plumes and pollutants over an extended duration. Emission factors for volatile organic compounds were also measured roadside for the first time using a proton transfer reaction time-of-flight mass spectrometer; this instrument provided the time resolution required for the plume capture technique. Mean emission factors were characteristic of the light-duty gasoline dominated vehicle fleet present at the measurement site, with mean black carbon and particle number emission factors of 35 mg kg−1 and 7.7 × 1014 kg−1, respectively. The use of the plume-by-plume analysis enabled isolation of vehicle emissions, and the elucidation of co-emitted pollutants from similar vehicle types, variability of emissions across the fleet, and the relative contribution from heavy emitters. It was found that a small proportion of the fleet (〈 25%) contributed significantly to total fleet emissions; 95, 93, 76, and 75% for black carbon, carbon monoxide, BTEX, and particle number, respectively. Emission factors of a single pollutant may help classify a vehicle as a high emitter. However, regulatory strategies to more efficiently target multi-pollutants mixtures may be better developed by considering the co-emitted pollutants as well.

Description: The prospective future adoption of molecular hydrogen (H2) to power the road transportation sector could greatly improve tropospheric air quality but also raises the question of whether the adoption would have adverse effects on the stratospheric ozone. The possibility of undesirable impacts must be fully evaluated to guide future policy decisions. Here we evaluate the possible impact of a future (2050) H2-based road transportation sector on stratospheric composition and chemistry, especially on the stratospheric ozone, with the MOZART (Model for OZone And Related chemical Tracers) model. Since future growth is highly uncertain, we evaluate the impact of two world evolution scenarios, one based on an IPCC (Intergovernmental Panel on Climate Change) high-emitting scenario (A1FI) and the other on an IPCC low-emitting scenario (B1), as well as two technological options: H2 fuel cells and H2 internal combustion engines. We assume a H2 leakage rate of 2.5% and a complete market penetration of H2 vehicles in 2050. The model simulations show that a H2-based road transportation sector would reduce stratospheric ozone concentrations as a result of perturbed catalytic ozone destruction cycles. The magnitude of the impact depends on which growth scenario evolves and which H2 technology option is applied. For the evolution growth scenario, stratospheric ozone decreases more in the H2 fuel cell scenarios than in the H2 internal combustion engine scenarios because of the NOx emissions in the latter case. If the same technological option is applied, the impact is larger in the A1FI emission scenario. The largest impact, a 0.54% decrease in annual average global mean stratospheric column ozone, is found with a H2 fuel cell type road transportation sector in the A1FI scenario; whereas the smallest impact, a 0.04% increase in stratospheric ozone, is found with applications of H2 internal combustion engine vehicles in the B1 scenario. The impacts of the other two scenarios fall between the above two boundary scenarios. However, the magnitude of these changes is much smaller than the increases in 2050 stratospheric ozone projected, as stratospheric ozone is expected to recover due to the limits in ozone depleting substance emissions imposed in the Montreal Protocol.

Description: The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard the ENVISAT satellite provides profiles of temperature and various trace-gases from limb-viewing mid-infrared emission measurements. The stratospheric nitric acid (HNO3) from September 2002 to March 2004 was retrieved from the MIPAS observations using the science-oriented data processor developed at the Institut für Meteorologie und Klimaforschung (IMK), which is complemented by the component of non-local thermodynamic equilibrium (non-LTE) treatment from the Instituto de Astrofísica de Andalucía (IAA). The IMK-IAA research product, different from the ESA operational product, is validated in this paper by comparison with a number of reference data sets. Individual HNO3 profiles of the IMK-IAA MIPAS show good agreement with those of the balloon-borne version of MIPAS (MIPAS-B) and the infrared spectrometer MkIV, with small differences of less than 0.5 ppbv throughout the entire altitude range up to about 38 km, and below 0.2 ppbv above 30 km. However, the degree of consistency is largely affected by their temporal and spatial coincidence, and differences of 1 to 2 ppbv may be observed between 22 and 26 km at high latitudes near the vortex boundary, due to large horizontal inhomogeneity of HNO3. Statistical comparisons of MIPAS IMK-IAA HNO3 VMRs with respect to those of satellite measurements of Odin/SMR, ILAS-II, ACE-FTS, as well as the MIPAS ESA product show good consistency. The mean differences are generally ±0.5 ppbv and standard deviations of the differences are of 0.5 to 1.5 ppbv. The maximum differences are 2.0 ppbv around 20 to 25 km. This gives confidence in the general reliability of MIPAS HNO3 VMR data and the other three satellite data sets.