ALBERT

Description: During the MILAGRO campaign centered in the Mexico City area, Pacific Northwest National Laboratory (PNNL) and Argonne National Laboratory (ANL) operated atmospheric profiling systems at Veracruz and at two locations on the Central Mexican Plateau in the region around Mexico City. These systems included radiosondes, wind profilers, a sodar, and an aerosol backscatter lidar. An additional wind profiler was operated by the University of Alabama in Huntsville (UAH) at the Mexican Petroleum Institue (IMP) near the center of Mexico City. Because of the opportunity afforded by collocation of profilers, radiosondes, and a lidar, and because of the importance of boundary layer depth for aerosol properties, we have carried out a comparison of mixing layer depth as determined independently from these three types of measurement systems during the campaign. We have then used results of this comparison and additional measurements to develop a detailed description of the daily structure and evolution of the boundary layer on the Central Mexican Plateau during MILAGRO. Our analysis indicates that the profilers were more consistently successful in establishing the mixing layer depth during the daytime. The boundary layer growth was similar at the three locations, although the mixing layer tended to be slightly deeper in the afternoon in central Mexico City. The sodar showed that convection began about an hour after sunrise. Maximum daily mixing layer depths always reached 2000 m a.g.l. and frequently extended to 4000 m. The rate and variability of mixing layer growth was essentially the same as that observed during the IMADA-AVER campaign in the same season in 1997. This growth did not seem to be related to whether deep convection was reported on a given day. Wind speeds within the boundary layer exhibited a daily low-altitude maximum in the late afternoon with lighter winds aloft, consistent with previous reports of diurnal regional circulations. Norte events, which produced high winds at Veracruz, did not appreciably modulate the winds on the plateau. Finally, despite the typically dry conditions at the surface, radiosonde profiles showed that relative humidity often exceeded 50% in the early morning and in the upper part of the boundary layer. This suggests that aerosol particles would have experienced hygroscopic growth within the boundary layer on many days.

Description: The main purpose of the NASA Goddard Space Flight Center TROPospheric OZone DIfferential Absorption Lidar (GSFC TROPOZ DIAL) is to measure the vertical distribution of tropospheric ozone for science investigations. Because of the important health and climate impacts of tropospheric ozone, it is imperative to quantify background photochemical ozone concentrations and ozone layers aloft, especially during air quality episodes. For these reasons, this paper addresses the necessary procedures to validate the TROPOZ retrieval algorithm and confirm that it is properly representing ozone concentrations. This paper is focused on ensuring the TROPOZ algorithm is properly quantifying ozone concentrations, and a following paper will focus on a systematic uncertainty analysis. This methodology begins by simulating synthetic lidar returns from actual TROPOZ lidar return signals in combination with a known ozone profile. From these synthetic signals, it is possible to explicitly determine retrieval algorithm biases from the known profile. This was then systematically performed to identify any areas that need refinement for a new operational version of the TROPOZ retrieval algorithm. One immediate outcome of this exercise was that a bin registration error in the correction for detector saturation within the original retrieval was discovered and was subsequently corrected for. Another noticeable outcome was that the vertical smoothing in the retrieval algorithm was upgraded from a constant vertical resolution to a variable vertical resolution to yield a statistical uncertainty of

Description: The MILAGRO field campaign was a multi-agency international collaborative project to evaluate the regional impacts of the Mexico City air pollution plume as a means of understanding urban impacts on the global climate. Mexico City lies on an elevated plateau with mountains on three sides and has complex mountain and surface-driven wind flows. This paper asks what the wind transport was in the basin during the field campaign and how representative it was of the climatology. Surface meteorology and air quality data, radiosoundings and radar wind profiler data were collected at sites in the basin and its vicinity. Cluster analysis is used to identify the dominant wind patterns both during the campaign and within the past 10 years of operational data from the warm dry season. Our analysis shows that March 2006 was representative of typical flow patterns experienced in the basin. Six episode types were identified for the basin scale circulation providing a way of interpreting atmospheric chemistry and particulate data collected during the campaign. Decoupling between surface winds and those aloft had a strong influence in leading to convection and poor air quality episodes. Hourly characterisation of wind circulation during the MILAGRO, MCMA-2003 and IMADA field campaigns will enable the comparisons of similar air pollution episodes and the evaluation of the impact of wind transport on measurements of the atmospheric chemistry taking place in the basin.

Description: Tropospheric ozone profiles have been retrieved from the new ground-based National Aeronautics and Space Administration (NASA) Goddard Space Flight Center TROPospheric OZone DIfferential Absorption Lidar (GSFC TROPOZ DIAL) in Greenbelt, MD (38.99° N, 76.84° W, 57 m a.s.l.), from 400 m to 12 km a.g.l. Current atmospheric satellite instruments cannot peer through the optically thick stratospheric ozone layer to remotely sense boundary layer tropospheric ozone. In order to monitor this lower ozone more effectively, the Tropospheric Ozone Lidar Network (TOLNet) has been developed, which currently consists of five stations across the US. The GSFC TROPOZ DIAL is based on the DIAL technique, which currently detects two wavelengths, 289 and 299 nm, with multiple receivers. The transmitted wavelengths are generated by focusing the output of a quadrupled Nd:YAG laser beam (266 nm) into a pair of Raman cells, filled with high-pressure hydrogen and deuterium, using helium as buffer gas. With the knowledge of the ozone absorption coefficient at these two wavelengths, the range-resolved number density can be derived. An interesting atmospheric case study involving the stratospheric–tropospheric exchange (STE) of ozone is shown, to emphasize the regional importance of this instrument as well as to assess the validation and calibration of data. There was a low amount of aerosol aloft, and an iterative aerosol correction has been performed on the retrieved data, which resulted in less than a 3 ppb correction to the final ozone concentration. The retrieval yields an uncertainty of 16–19% from 0 to 1.5 km, 10–18% from 1.5 to 3 km, and 11–25% from 3 to 12 km according to the relevant aerosol concentration aloft. There are currently surface ozone measurements hourly and ozonesonde launches occasionally, but this system will be the first to make routine tropospheric ozone profile measurements in the Baltimore–Washington, D.C. area.

Description: Tropospheric ozone profiles have been retrieved from the new ground based National Aeronautics and Space Administration (NASA) Goddard Space Flight Center TROPospheric OZone DIfferential Absorption Lidar (GSFC TROPOZ DIAL) in Greenbelt, MD (38.99° N, 76.84° W, 57 m a.s.l.) from 400 m to 12 km a.g.l. Current atmospheric satellite instruments cannot peer through the optically thick stratospheric ozone layer to remotely sense boundary layer tropospheric ozone. In order to monitor this lower ozone more effectively, the Tropospheric Ozone Lidar Network (TOLNet) has been developed, which currently consists of five stations across the US. The GSFC TROPOZ DIAL is based on the Differential Absorption Lidar (DIAL) technique, which currently detects two wavelengths, 289 and 299 nm. Ozone is absorbed more strongly at 289 nm than at 299 nm. The DIAL technique exploits this difference between the returned backscatter signals to obtain the ozone number density as a function of altitude. The transmitted wavelengths are generated by focusing the output of a quadrupled Nd:YAG laser beam (266 nm) into a pair of Raman cells, filled with high pressure hydrogen and deuterium. Stimulated Raman Scattering (SRS) within the focus generates a significant fraction of the pump energy at the first Stokes shift. With the knowledge of the ozone absorption coefficient at these two wavelengths, the range resolved number density can be derived. An interesting atmospheric case study involving the Stratospheric–Tropospheric Exchange (STE) of ozone is shown to emphasize the regional importance of this instrument as well as assessing the validation and calibration of data. The retrieval yields an uncertainty of 16–19% from 0–1.5 km, 10–18% from 1.5–3 km, and 11–25% from 3 km to 12 km. There are currently surface ozone measurements hourly and ozonesonde launches occasionally, but this system will be the first to make routine tropospheric ozone profile measurements in the Baltimore–Washington DC area.

Description: The Super Dual Auroral Radar Network (SuperDARN) network of HF coherent backscatter radars form a unique global diagnostic of large-scale ionospheric and magnetospheric dynamics in the Northern and Southern Hemispheres. Currently the ground projections of the HF radar returns are routinely determined by a simple rangefinding algorithm, which takes no account of the prevailing, or indeed the average, HF propagation conditions. This is in spite of the fact that both direct E- and F-region backscatter and 1½-hop E- and F-region backscatter are commonly used in geophysical interpretation of the data. In a companion paper, Chisham et al. (2008) have suggested a new virtual height model for SuperDARN, based on average measured propagation paths. Over shorter propagation paths the existing rangefinding algorithm is adequate, but mapping errors become significant for longer paths where the roundness of the Earth becomes important, and a correct assumption of virtual height becomes more difficult. The SuperDARN radar at Hankasalmi has a propagation path to high power HF ionospheric modification facilities at both Tromsø on a ½-hop path and SPEAR on a 1½-hop path. The SuperDARN radar at Þykkvibǽr has propagation paths to both facilities over 1½-hop paths. These paths provide an opportunity to quantitatively test the available SuperDARN virtual height models. It is also possible to use HF radar backscatter which has been artificially induced by the ionospheric heaters as an accurate calibration point for the Hankasalmi elevation angle of arrival data, providing a range correction algorithm for the SuperDARN radars which directly uses elevation angle. These developments enable the accurate mappings of the SuperDARN electric field measurements which are required for the growing number of multi-instrument studies of the Earth's ionosphere and magnetosphere.

Description: This paper presents a quantitative comparison of the four most commonly used receptor models, namely absolute principal component scores (APCS), pragmatic mass closure (PMC), chemical mass balance (CMB) and positive matrix factorization (PMF). The models were used to predict the contributions of a wide variety of sources to PM2.5 mass in Halifax, Nova Scotia during the experiment to quantify the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS). However, particular emphasis was placed on the capacity of the models to predict the boreal wildfire smoke contributions during the BORTAS experiment. The performance of the four receptor models was assessed on their ability to predict the observed PM2.5 with an R2 close to 1, an intercept close to zero, a low bias and low RSME. Using PMF, a new woodsmoke enrichment factor of 52 was estimated for use in the PMC receptor model. The results indicate that the APCS and PMC receptor models were not able to accurately resolve total PM2.5 mass concentrations below 2 μg m−3. CMB was better able to resolve these low PM2.5 concentrations, but it could not be run on 9 of the 45 days of PM2.5 samples. PMF was found to be the most robust of the four models since it was able to resolve PM2.5 mass below 2 μg m−3, predict PM2.5 mass on all 45 days and utilise an unambiguous woodsmoke chemical tracer. The median woodsmoke relative contributions to PM2.5 estimated using PMC, APCS, CMB and PMF were found to be 0.08, 0.09, 3.59 and 0.14 μg m−3 respectively. The contribution predicted by the CMB model seemed to be clearly too high based on other observations. The use of levoglucosan as a tracer for woodsmoke was found to be vital for identifying this source.

Description: Ambient air monitoring as part of the US Environmental Protection Agency's (US EPA's) Clean Air Status and Trends Network (CASTNet) currently uses filter packs to measure weekly integrated concentrations. The US EPA is interested in supplementing CASTNet with semi-continuous monitoring systems at select sites to characterize atmospheric chemistry and deposition of nitrogen and sulfur compounds at higher time resolution than the filter pack. The Monitor for AeRosols and GAses in ambient air (MARGA) measures water-soluble gases and aerosols at an hourly temporal resolution. The performance of the MARGA was assessed under the US EPA Environmental Technology Verification (ETV) program. The assessment was conducted in Research Triangle Park, North Carolina, from 8 September to 8 October 2010 and focused on gaseous SO2, HNO3, and NH3 and aerosol SO42-, NO3-, and NH4+. Precision of the MARGA was evaluated by calculating the median absolute relative percent difference (MARPD) between paired hourly results from duplicate MARGA units (MUs), with a performance goal of ≤ 25%. The accuracy of the MARGA was evaluated by calculating the MARPD for each MU relative to the average of the duplicate denuder/filter pack concentrations, with a performance goal of ≤ 40%. Accuracy was also evaluated by using linear regression, where MU concentrations were plotted against the average of the duplicate denuder/filter pack concentrations. From this, a linear least squares line of best fit was applied. The goal was for the slope of the line of best fit to be between 0.8 and 1.2. The MARGA performed well in comparison to the denuder/filter pack for SO2, SO42−, and NH4+, with all three compounds passing the accuracy and precision goals by a significant margin. The performance of the MARGA in measuring NO3- could not be evaluated due to the different sampling efficiency of coarse NO3- by the MUs and the filter pack. Estimates of "fine" NO3- were calculated for the MUs and the filter pack. Using this and results from a previous study, it is concluded that if the MUs and the filter pack were sampling the same particle size, the MUs would have good agreement in terms of precision and accuracy. The MARGA performed moderately well in measuring HNO3 and NH3, though neither met the linear regression slope goals. However, recommendations for improving the measurement of HNO3 and NH3 are discussed. It is concluded that SO42-, SO2, NO3-, HNO3, NH4+, and NH3 concentrations can be measured with acceptable accuracy and precision when the MARGA is operated in conjunction with the recommendations outlined in the manuscript.

Description: Peroxy radical (HO2+ΣRO2) measurements, using the PEroxy Radical Chemical Amplification (PERCA) technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX) at Mace Head in summer 2002, are presented and put into the context of marine, boundary-layer chemistry. A suite of other chemical parameters (NO, NO2, NO3, CO, CH4, O3, VOCs, peroxides), photolysis frequencies and meteorological measurements, are used to present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon. Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to the model increases the level of model/measurement agreement, apparently by respeciation of HOx. A good correlation exists between j(HCHO).[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere as a HOx source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NO2] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The HO2/(HO2+ΣRO2) ratios are dependent on [NOx] ranging between 0.2 and 0.6, with the ratio increasing linearly with NOx. Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO3-alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv h-1. The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O3))/dln(NO)=1.0). The results imply that the N(O3) (the in-situ net photochemical rate of ozone production/destruction) will be strongly sensitive in the marine boundary layer to small changes in [NO] which has ramifications for changing NOx loadings in the European continental boundary layer.

Description: We infer CO2 surface fluxes using satellite observations of mid-tropospheric CO2 from the Tropospheric Emission Spectrometer (TES) and measurements of CO2 from surface flasks in a time-independent inversion analysis based on the GEOS-Chem model. Using TES CO2 observations over oceans, spanning 40° S–40° N, we find that the horizontal and vertical coverage of the TES and flask data are complementary. This complementarity is demonstrated by combining the datasets in a joint inversion, which provides better constraints than from either dataset alone, when a posteriori CO2 distributions are evaluated against independent ship and aircraft CO2 data. In particular, the joint inversion offers improved constraints in the tropics where surface measurements are sparse, such as the tropical forests of South America. Aggregating the annual surface-to-atmosphere fluxes from the joint inversion for the year 2006 yields −1.13±0.21 Pg C for the global ocean, −2.77±0.20 Pg C for the global land biosphere and −3.90±0.29 Pg C for the total global natural flux (defined as the sum of all biospheric, oceanic, and biomass burning contributions but excluding CO2 emissions from fossil fuel combustion). These global ocean and global land fluxes are shown to be near the median of the broad range of values from other inversion results for 2006. To achieve these results, a bias in TES CO2 in the Southern Hemisphere was assessed and corrected using aircraft flask data, and we demonstrate that our results have low sensitivity to variations in the bias correction approach. Overall, this analysis suggests that future carbon data assimilation systems can benefit by integrating in situ and satellite observations of CO2 and that the vertical information provided by satellite observations of mid-tropospheric CO2 combined with measurements of surface CO2, provides an important additional constraint for flux inversions.