Search

South Korea routinely experiences poor air quality with ozone and small particles exceeding air quality standards. To build a better understanding of this problem, in 2016, the KORea-United States cooperative Air Quality (KORUS-AQ) study collected surface and airborne measurements of many chemical species, including the reactive gases hydroxyl (OH) and hydroperpoxyl (HO2). Several different results are reported here. First, OH and HO2 measured on the NASA DC-8 agree to within uncertainties with values calculated by two different box models, both in statistical comparisons and as a function of altitude from the surface to 8 km. These comparisons show substantial scatter, likely due to both variability in instrument performance and the difficulty in interpolating measurements made with frequencies different from those of the model time step. Second, OH and HO2 calculated by a model including HO2 uptake on aerosol particles in the chemical mechanism are inconsistent with observations. Third, in the planetary boundary layer over both ocean and land, measured and model-calculated OH reactivity are sometimes different, and this missing OH reactivity, which is as much as ∼4 s−1, increased from April to June and originated primarily from the Korean peninsula. Fourth, repeated missed approaches at the Seoul Air Base during several days show that the changes in the sum of ozone and nitrogen dioxide are consistent with ozone production rates calculated from HO2 either observed or modeled by the Langley Research Center model.

Obtaining the full spatial coverage of daily surface ozone fields is challenging because of the sparsity of the surface monitoring network and the difficulty in direct satellite retrievals of surface ozone. We propose an indirect satellite retrieval framework to utilize the information from satellite-measured column densities of tropospheric NO2 and CH2O, which are sensitive to the lower troposphere, to derive surface ozone fields. The method is applicable to upcoming geostationary satellites with high-quality NO2 and CH2O measurements. To prove the concept, we conduct a simulation experiment using a 3-D chemical transport model for July 2011 over the eastern US. The results show that a second order regression using both NO2 and CH2O column densities can be an effective predictor for daily maximum 8-h average ozone. Furthermore, this indirect retrieval approach is shown to be complementary to spatial interpolation of surface observations, especially in regions where the surface sites are sparse. Combining column observations of NO2 and CH2O with surface site measurements leads to an improved representation of surface ozone over simple kriging, increasing the R2 value from 0.53 to 0.64 at a surface site distance of 252 km. The improvements are even more significant with larger surface site distances. The simulation experiment suggests that the indirect satellite retrieval technique can potentially be a useful tool to derive the full spatial coverage of daily surface ozone fields if satellite observation uncertainty is moderate.

To investigate the variability of in situ profile shapes under a variety of meteorological and pollution conditions, results are presented of an agglomerative hierarchical cluster analysis of the in situ O3 and NO2 profiles for each of the four campaigns of the NASA DISCOVER-AQ mission. Understanding the observed profile variability for these trace gases is useful for understanding the accuracy of the assumed profile shapes used in satellite retrieval algorithms as well as for understanding the correlation between satellite column observations and surface concentrations. The four campaigns of the DISCOVER-AQ mission took place in Maryland during July 2011, the San Joaquin Valley of California during January–February 2013, the Houston, Texas, metropolitan region during September 2013, and the Denver-Front Range region of Colorado during July–August 2014. Several distinct profile clusters emerged for the California, Texas, and Colorado campaigns for O3, indicating significant variability of O3 profile shapes, while the Maryland campaign presented only one distinct O3 cluster. In contrast, very few distinct profile clusters emerged for NO2 during any campaign for this particular clustering technique, indicating the NO2 profile behavior was relatively uniform throughout each campaign. However, changes in NO2 profile shape were evident as the boundary layer evolved through the day, but they were apparently not significant enough to yield more clusters. The degree of vertical mixing (as indicated by temperature lapse rate) associated with each cluster exerted an important influence on the shapes of the median cluster profiles for O3, as well as impacted the correlations between the associated column and surface data for each cluster for O3. The correlation analyses suggest satellites may have the best chance to relate to surface O3 under the conditions encountered during the Maryland campaign Clusters 1 and 2, which include deep, convective boundary layers and few interruptions to this connection from complex meteorology, chemical environments, or orography. The regional CMAQ model captured the shape factors for O3, and moderately well captured the NO2 shape factors, for the conditions associated with the Maryland campaign, suggesting that a regional air quality model may adequately specify a priori profile shapes for remote sensing retrievals. CMAQ shape factor profiles were not as well represented for the other regions.

This investigation examines aerosol dynamics during major fine mode aerosol transboundary pollution events in South Korea primarily during the KORUS-AQ campaign from May 1 – June 10, 2016, particularly when cloud fraction was high and/or fog was present to quantify the change in aerosol characteristics due to near-cloud or fog interaction. We analyze the new AERONET Version 3 data that have significant changes to cloud screening algorithms, allowing many more fine-mode observations in the near vicinity of clouds or fog. Case studies for detailed investigation include May 25–26, 2016 when cloud fraction was high over much of the peninsula, associated with a weak frontal passage and advection of pollution from China. These cloud-influenced Chinese transport dates also had the highest aerosol optical depth (AOD), surface PM2.5 concentrations and fine mode particle sizes of the entire campaign. Another likewise cloud/high relative humidity (RH) case is June 9 and 10, 2016 when fog was present over the Yellow Sea that appears to have affected aerosol properties well downwind over the Korean peninsula. In comparison we also investigated aerosol properties on air stagnation days with very low cloud cover and relatively low RH (May 17 & 18, 2016), when local Korean emissions dominated. Aerosol volume size distributions show marked differences between the transport days (with high RH and cloud influences) and the local pollution stagnation days, with total column-integrated particle fine mode volume being an order of magnitude greater on the pollution transport dates. The PM2.5 over central Seoul were significantly greater than for coastal sites on the transboundary transport days yet not on stagnation days, suggesting additional particle formation from gaseous urban emissions in cloud/fog droplets and/or in the high RH humidified aerosol environment. Many days had KORUS-AQ research aircraft flights that provided observations of aerosol absorption, particle chemistry and vertical profiles of extinction. AERONET retrievals and aircraft in situ measurements both showed high single scattering albedo (weak absorption) on the cloudy or cloud influenced days, plus aircraft profile in situ measurements showed large AOD enhancements (versus dried aerosol) at ambient relative humidity (RH) on the pollution transport days, consistent with the significantly larger fine mode particle radii and weak absorption.

We quantify both the spatial and temporal variability of column integrated O3, NO2, CO, SO2, and HCHO over the Baltimore/Washington, DC area using output from the Weather Research and Forecasting model with on-line chemistry (WRF/Chem) for the entire month of July 2011, coinciding with the first deployment of the NASA Earth Venture program mission Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ). Using structure function analyses, we find that the model reproduces the spatial variability observed during the campaign reasonably well, especially for O3. The Tropospheric Emissions: Monitoring of Pollution (TEMPO) instrument will be the first NASA mission to make atmospheric composition observations from geostationary orbit and partially fulfills the goals of the Geostationary Coastal and Air Pollution Events (GEO-CAPE) mission. We relate the simulated variability to the precision requirements defined by the science traceability matrices of these space-borne missions. Results for O3 from 0 to 2 km altitude indicate that the TEMPO instrument would be able to observe O3 air quality events over the Mid-Atlantic area, even on days when the violations of the air quality standard are not widespread. The results further indicated that horizontal gradients in CO from 0 to 2 km would be observable over moderate distances (≥20 km). The spatial and temporal results for tropospheric column NO2 indicate that TEMPO would be able to observe not only the large urban plumes at times of peak production, but also the weaker gradients between rush hours. This suggests that the proposed spatial and temporal resolutions for these satellites as well as their prospective precision requirements are sufficient to answer the science questions they are tasked to address.

The first field campaign of DISCOVER-AQ (Deriving Information on Surface conditions from COlumn and VERtically resolved observations relevant to Air Quality) took place in July 2011 over Baltimore–Washington Corridor (BWC). A suite of airborne remote sensing and in-situ sensors was deployed along with ground networks for mapping vertical and horizontal distribution of aerosols. Previous researches were based on a single lidar station because of the lack of regional coverage. This study uses the unique airborne HSRL (High Spectral Resolution Lidar) data to baseline PM 2.5 (particulate matter of aerodynamic diameter less than 2.5 μm) estimates and applies to regional air quality with satellite AOD (Aerosol Optical Depth) retrievals over BWC (∼6500 km 2 ). The linear approximation takes into account aerosols aloft above AML (Aerosol Mixing Layer) by normalizing AOD with haze layer height (i.e., AOD/HLH). The estimated PM 2.5 mass concentrations by HSRL AOD/HLH are shown within 2 RMSE (Root Mean Square Error ∼9.6 μg/m 3 ) with correlation ∼0.88 with the observed over BWC. Similar statistics are shown when applying HLH data from a single location over the distance of 100 km. In other words, a single lidar is feasible to cover the range of 100 km with expected uncertainties. The employment of MPLNET–AERONET (MicroPulse Lidar NETwork – AErosol RObotic NETwork) measurements at NASA GSFC produces similar statistics of PM 2.5 estimates as those derived by HSRL. The synergy of active and passive remote sensing aerosol measurements provides the foundation for satellite application of air quality on a daily basis. For the optimal range of 10 km, the MODIS-estimated PM 2.5 values are found satisfactory at 27 (out of 36) sunphotometer locations with mean RMSE of 1.6–3.3 μg/m 3 relative to PM 2.5 estimated by sunphotometers. The remaining 6 of 8 marginal sites are found in the coastal zone, for which associated large RMSE values ∼4.5–7.8 μg/m 3 are most likely due to overestimated AOD because of water-contaminated pixels.

To investigate the ability of column (or partial column) information to represent surface air quality, results of linear regression analyses between surface mixing ratio data and column abundances for O3 and NO2 are presented for the July 2011 Maryland deployment of the DISCOVER-AQ mission. Data collected by the P-3B aircraft, ground-based Pandora spectrometers, Aura/OMI satellite instrument, and simulations for July 2011 from the CMAQ air quality model during this deployment provide a large and varied data set, allowing this problem to be approached from multiple perspectives. O3 columns typically exhibited a statistically significant and high degree of correlation with surface data (R(sup 2) > 0.64) in the P- 3B data set, a moderate degree of correlation (0.16 < R(sup 2) < 0.64) in the CMAQ data set, and a low degree of correlation (R(sup 2) < 0.16) in the Pandora and OMI data sets. NO2 columns typically exhibited a low to moderate degree of correlation with surface data in each data set. The results of linear regression analyses for O3 exhibited smaller errors relative to the observations than NO2 regressions. These results suggest that O3 partial column observations from future satellite instruments with sufficient sensitivity to the lower troposphere can be meaningful for surface air quality analysis.

During a classic heat wave with record high temperatures and poor air quality from July 18 to 23, 2011, an elevated reservoir of air pollutants was observed over and downwind of Baltimore, MD, with relatively clean conditions near the surface. Aircraft and ozonesonde measurements detected approximately 120 parts per billion by volume ozone at 800 meters altitude, but approximately 80 parts per billion by volume ozone near the surface. High concentrations of other pollutants were also observed around the ozone peak: approximately 300 parts per billion by volume CO at 1200 meters, approximately 2 parts per billion by volume NO2 at 800 meters, approximately 5 parts per billion by volume SO2 at 600 meters, and strong aerosol optical scattering (2 x 10 (sup 4) per meter) at 600 meters. These results suggest that the elevated reservoir is a mixture of automobile exhaust (high concentrations of O3, CO, and NO2) and power plant emissions (high SO2 and aerosols). Back trajectory calculations show a local stagnation event before the formation of this elevated reservoir. Forward trajectories suggest an influence on downwind air quality, supported by surface ozone observations on the next day over the downwind PA, NJ and NY area. Meteorological observations from aircraft and ozonesondes show a dramatic veering of wind direction from south to north within the lowest 5000 meters, implying that the development of the elevated reservoir was caused in part by the Chesapeake Bay breeze. Based on in situ observations, Community Air Quality Multi-scale Model (CMAQ) forecast simulations with 12 kilometers resolution overestimated surface ozone concentrations and failed to predict this elevated reservoir; however, CMAQ research simulations with 4 kilometers and 1.33 kilometers resolution more successfully reproduced this event. These results show that high resolution is essential for resolving coastal effects and predicting air quality for cities near major bodies of water such as Baltimore on the Chesapeake Bay and downwind areas in the Northeast.

We examine the results from a regional-scale chemical-transport model with 4-km resolution to determine the spatial variability of trace gases on this scale. Model-derived variability statistics are generated using 1st-order structure functions and then compared with in situ trace gas measurements from a series of aircraft campaigns. The variability of the observations and the model-derived concentrations are found to be in reasonable agreement for O 3 and CO, but the model underestimates the observed variability of NO 2 . Variability statistics are then calculated for model-derived tropospheric column integrals. These integrals are calculated for 0–10 km (representative of the entire tropospheric column), 0–2 km (representative of the planetary boundary layer, PBL) and 2–10 km (representative of the free troposphere, FT). For each of the species examined, the variability of the tropospheric column is generally controlled by the variability in the lowest 2 km. The degree of control for each trace gas, however, is different. Whereas NO 2 is completely dominated by PBL processes, CO variability in the FT contributes appreciably to the variability of the entire tropospheric column, suggesting that two independent pieces of information for CO would be most helpful for describing the variability of the entire tropospheric column. Likewise, the variability of an independent free tropospheric measurement of O 3 would provide additional insight into the observed variability of the entire column, but the amount of additional information provided by a separate FT measurement is not as beneficial to what was found for CO. We provide additional analyses to quantify relationships that can be used to better understand the model-derived structure functions and their dependence on grid size and time of day. Lastly we present a practical example of how this information may be used for guidance in the development of science requirements for future satellite instruments since measurements from these instruments must be able to resolve smaller scale gradients to be used successfully for air quality applications.

We analyze detailed atmospheric gas/aerosol composition data acquired during the 2008 NASA ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) airborne campaign performed at high northern latitudes in spring (ARCTAS-A) and summer (ARCTAS-B) and in California in summer (ARCTAS-CARB). Biomass burning influences were widespread throughout the ARCTAS campaign. MODIS data from 2000 to 2009 indicated that 2008 had the second largest fire counts over Siberia and a more normal Canadian boreal forest fire season. Near surface arctic air in spring contained strong anthropogenic signatures indicated by high sulfate. In both spring and summer most of the pollution plumes transported to the Arctic region were from Europe and Asia and were present in the mid to upper troposphere and contained a mix of forest fire and urban influences. The gas/aerosol composition of the high latitude troposphere was strongly perturbed at all altitudes in both spring and summer. The reactive nitrogen budget was balanced with PAN as the dominant component. Mean ozone concentrations in the high latitude troposphere were only minimally perturbed (

A radiative transfer model and photochemical box model are used to examine the effects of clouds and aerosols on actinic flux and photolysis rates, and the impacts of changes in photolysis rates on ozone production and destruction rates in a polluted urban environment like Houston, Texas. During the TexAQS-II Radical and Aerosol Measurement Project the combined cloud and aerosol effects reduced j (NO 2 ) photolysis frequencies by nominally 17%, while aerosols reduced j (NO 2 ) by 3% on six clear sky days. Reductions in actinic flux due to attenuation by clouds and aerosols correspond to reduced net ozone formation rates with a nearly one-to-one relationship. The overall reduction in the net ozone production rate due to reductions in photolysis rates by clouds and aerosols was approximately 8 ppbv h −1 .

A comparison of a model using five widely known mechanisms (RACM, CB05, LaRC, SAPRC-99, SAPRC-07, and MCMv3.1) has been conducted based on the TexAQS II Radical and Aerosol Measurement Project (TRAMP-2006) field data in 2006. The concentrations of hydroxyl (OH) and hydroperoxy (HO2) radicals were calculated by a zero-dimensional box model with each mechanism and then compared with the OH and HO2 measurements. The OH and HO2 calculated by the model with different mechanisms show similarities and differences with each other and with the measurements. First, measured OH and HO2 are generally greater than modeled for all mechanisms, with the median modeled-to-measured ratios ranging from about 0.8 (CB05) to about 0.6 (SAPRC-99). These differences indicate that either measurement errors, the effects of unmeasured species or chemistry errors in the model or the mechanisms, with some errors being independent of the mechanism used. Second, the modeled and measured ratios of HO2/OH agree when NO is about 1 ppbv, but the modeled ratio is too high when NO was less and too low when NO is more, as seen in previous studies. Third, mechanism–mechanism HOx differences are sensitive to the environmental conditions – in more polluted conditions, the mechanism–mechanism differences are less. This result suggests that, in polluted conditions, the mechanistic details are less important than in cleaner conditions, probably because of the dominance of reactive nitrogen chemistry under polluted conditions.

We investigated variations in the relative sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NOx) as inferred from the ratio of the tropospheric columns of formaldehyde to nitrogen dioxide (the "Ratio") from the Aura Ozone Monitoring Instrument (OMI). Our modeling study suggests that ozone formation decreases with reductions in VOCs at Ratios less than 1 and NOx at Ratios greater than 2; both NOx and VOC reductions may decrease ozone formation for Ratios between 1 and 2. Using this criteria. the OMI data indicate that ozone formation became: 1. more sensitive to NOx over most of the United States from 2005 to 2007 because of the substantial decrease in NOx emissions, primarily from stationary sources, and the concomitant decrease in the tropospheric column of NO2. and 2. more sensitive to NOx with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. In cities with relatively low isoprene emissions (e.g .. Chicago). the data clearly indicate that ozone formation became more sensitive to NOx from 2005 to 2007. In cities with relatively high isoprene emissions (e.g ., Atlanta), we found that the increase in the Ratio due to decreasing NOx emissions was not obvious as this signal was convolved with variations in the Ratio associated with the temperature dependence of isoprene emissions and, consequently, the formaldehyde concentration.

Measurements of OH, H2SO4, and MSA at South Pole (SP) Antarctica were recorded as a part of the 2003 Antarctic Chemistry Investigation (ANTCI 2003). The time period 22 November, 2003–2 January, 2004 provided a unique opportunity to observe atmospheric chemistry at SP under both natural conditions as well as those uniquely defined by a solar eclipse event. Results under natural solar conditions generally confirmed those reported previously in the year 2000. In both years the major chemical driver leading to large scale fluctuations in OH was shifts in the concentration levels of NO. Like in 2000, however, the 2003 observational data were systematically lower than model predictions. This can be interpreted as indicating that the model mechanism is still missing a significant HOx sink reaction(s); or, alternatively, that the OH calibration source may have problems. Still a final possibility could involve the integrity of the OH sampling scheme which involved a fixed building site. As expected, during the peak in the solar eclipse both NO and OH showed large decreases in their respective concentrations. Interestingly, the observational OH profile could only be approximated by the model mechanism upon adding an additional HOx radical source in the form of snow emissions of CH2O and/or H2O2. This would lead one to think that either CH2O and/or H2O2 snow emissions represent a significant HOx radical source under summertime conditions at SP. Observations of H2SO4 and MSA revealed both species to be present at very low concentrations (e.g., 5 × 105 and 1 × 105 molec cm−3, respectively), but similar to those reported in 2000. The first measurements of SO2 at SP demonstrated a close coupling with the oxidation product H2SO4. The observed low concentrations of MSA appear to be counter to the most recent thinking by glacio-chemists who have suggested that the plateau's lower atmosphere should have elevated levels of MSA. We speculate here that the absence of MSA may reflect efficient atmospheric removal mechanisms for this species involving either dynamical and/or chemical processes.

The Antarctic Tropospheric Chemistry Investigation (ANTCI) was carried out from late November to December 2003 with both extended ground-based and tethered balloon studies at Amundsen Scott Station, South Pole. ANTCI 2003 was the first of two Antarctic field studies with the primary goal of further exploring the active photochemistry of the South Pole region that was first identified in the previous Investigation of Sulfur Chemistry in the Antarctic Troposphere (ISCAT) program. Since ISCAT was fully ground-based, ANTCI 2003 goals included expanding chemical studies both vertically upward to investigate mixing and horizontally to better understand large-scale plateau NOx production and transport. Thus, in addition to ground-based experiments at South Pole, Twin Otter aircraft sampling took place out to hundreds of kilometers in several directions from the South Pole. These were designed to specifically address the issue of how representative past South Pole chemical measurements are of the surrounding high plateau region. The Twin Otter was also used to make transects along the coast both north and south of McMurdo Station. The present paper summarizes the overall setting and results of this investigation and highlights the many new findings that were obtained.

The first airborne measurements of nitric oxide (NO) on the Antarctic plateau have demonstrated that the previously reported elevated levels of this species extend well beyond the immediate vicinity of South Pole. Although the current database is still relatively weak and critical laboratory experiments are still needed, the findings here suggest that the chemical uniqueness of the plateau may be substantially greater than first reported. For example, South Pole ground-based findings have provided new evidence showing that the dominant process driving the release of nitrogen from the snowpack during the spring/summer season (post-depositional loss) is photochemical in nature with evaporative processes playing a lesser role. There is also new evidence suggesting that nitrogen, in the form of nitrate, may undergo multiple recycling within a given photochemical season. Speculation here is that this may be a unique property of the plateau and much related to its having persistent cold temperatures even during summer. These conditions promote the efficient adsorption of molecules like HNO3 (and very likely HO2NO2) onto snow-pack surface ice where we have hypothesized enhanced photochemical processing can occur, leading to the efficient release of NOx to the atmosphere. In addition, to these process-oriented tentative conclusions, the findings from the airborne studies, in conjunction with modeling exercises suggest a new paradigm for the plateau atmosphere. The near-surface atmosphere over this massive region can be viewed as serving as much more than a temporary reservoir or holding tank for imported chemical species. It defines an immense atmospheric chemical reactor which is capable of modifying the chemical characteristics of select atmospheric constituents. This reactor has most likely been in place over geological time, and may have led to the chemical modulation of some trace species now found in ice cores. Reactive nitrogen has played a critical role in both establishing and in maintaining this reactor.

An interpretative modeling analysis is conducted to simulate the diurnal variations in OH and HO 2 +RO 2 observed at Summit, Greenland in 2003. The main goal is to assess the HO x budget and to quantify the impact of snow emissions on ambient HO x as well as on CH 2 O and H 2 O 2 . This analysis is based on composite diurnal profiles of HO x precursors recorded during a 3-day period (July 7–9), which were generally compatible with values reported in earlier studies. The model simulations can reproduce the observed diurnal variation in HO 2 +RO 2 when they are constrained by observations of H 2 O 2 and CH 2 O. By contrast, model predictions of OH were about factor of 2 higher than the observed values. Modeling analysis of H 2 O 2 suggests that its distinct diurnal variation is likely controlled by snow emissions and loss by deposition and/or scavenging. Similarly, deposition and/or scavenging sinks are needed to reproduce the observed diel profile in CH 2 O. This study suggests that for the Summit 2003 period snow emissions contribute ∼25% of the total CH 2 O production, while photochemical oxidation of hydrocarbon appears to be the dominant source. A budget assessment of HO x radicals shows that primary production from O( 1 D)+H 2 O and photolysis of snow emitted precursors (i.e., H 2 O 2 and CH 2 O) are the largest primary HO x sources at Summit, contributing 41% and 40%, respectively. The snow contribution to the HO x budget is mostly in the form of emissions of H 2 O 2 . The dominant HO x sink involves the HO 2 +HO 2 reaction forming H 2 O 2 , followed by its deposition to snow. These results differ from those previously reported for the South Pole (SP), in that primary production of HO x was shown to be largely driven by both the photolysis of CH 2 O and H 2 O 2 emissions (46%) with smaller contributions coming from the oxidation of CH 4 and the O( 1 D)+H 2 O reaction (i.e., 27% each). In sharp contrast to the findings at Summit in 2003, due to the much higher levels of NO x , the SP HO x sinks are dominated by HO x –NO x reactions, leading to the formation and deposition of HNO 3 and HO 2 NO 2 . Thus, a comparison between SP and Summit studies suggests that snow emissions appear to play a prominent role in controlling primary HO x production in both environments. However, as regards to maintaining highly elevated levels of OH, the two environments differ substantially. At Summit the elevated rate for primary production of HO x is most important; whereas, at SP it is the rapid recycling of the more prevalent HO 2 radical, through reaction with NO, back to OH that is primarily responsible.

Several groups have now shown that snow covered polar areas can lead to the release of NO x to the atmosphere as a result of the UV photolysis of nitrate ions. Here we focus on a detailed examination of the NO observations recorded at South Pole (SP). Topics explored include: (1) why SP NO x levels greatly exceed those at other polar sites; (2) what processes are responsible for the observed large day to day NO concentration shifts at SP; and (3) possible explanations for the large variability in NO seen between SP studies in 1998 and 2000. As discussed in the main body of the text, the answer to all three questions lies in the uniqueness of the summertime SP environment. Among these characteristics is the presence of a large plateau region just to the east of SP. This region defines one of the world's largest air drainage fields, being nearly 1000 km across and having elevation of ∼ 3 km . In addition, summertime SP surface temperatures typically do not exceed - 25 ° C , leading to frequent cases where strong near surface temperature inversions occur. It experiences 24 h of continuous sunlight, giving rise to non-stop photochemical reactions both within the snowpack and in the atmosphere. The latter chemistry is unique at SP in that increasing levels of NO x lead to an enhanced lifetime for NO x , thereby producing non-linear increases in NO x . In addition, the rapid atmospheric oxidation of NO x , in conjunction with very rapid dry deposition of the products ( HNO 3 and HO 2 NO 2 ), results in a very efficient recycling of NO x back to the snowpack. Details concerning these unique SP characteristics and the extension of these findings to the greater plateau region are discussed. Finally, the relationship of NO x recycling and total nitrogen deposition to the plateau is explored.

Reported here are modeling results based on ISCAT (Investigation of Sulfur Chemistry of Antarctic Troposphere) 2000 observations recorded at the South Pole (SP) during the Austral Summer of 2000. The observations included a comprehensive set of photochemical parameters, e.g., NO, O3, and CO. It is worthy to note that not only were OH and HO2 observed, but also HOx precursor species CH2O, H2O2, and HONO were measured. Previous studies have suggested that HONO is the major source of OH/HOx in the Arctic; however, observed HONO levels at SP induced dramatic model overprediction of both HOx and NOx when used to constrain the model calculations. In contrast, model predictions constrained by observed values of CH2O and H2O2 are consistent with the observations of OH and HO2 (i.e., within 20%) for more than half of the data. Significant model overpredictions of OH, however, were seen at the NO levels lower than 50 pptv or higher than 150 pptv. An analysis of HOx budget at the median NO level suggests that snow emissions of H2O2 and CH2O are the single most important primary source of SP HOx, contributing 46% to the total source. Major sinks for HOx are found to be dry deposition of HO2NO2 and HNO3 as well as their reactions with OH. Although ISCAT 2000 led to a major progress in our understanding of SP HOx chemistry, critical aspects of this chemistry are still in need of further investigation.

The Investigation of Sulfur Chemistry in the Antarctic Troposphere (ISCAT) took place over the timer period of 15 November to 31 December in the year 2000. The study location was the Amundsen Scott Station in Antarctica. ISCAT 2000 defines the second phase of a program designed to explore tropospheric chemistry in Antarctica. As in 1998, the 2000 ISCAT study revealed a strong oxidizing environment at South Pole (SP). During the 2000 investigation, however, the suite of measurements was greatly expanded. These new measurements established the recycling of reactive nitrogen as a critical component of this unique environment. This paper first presents the historical background leading up to the ISCAT 2000 observations; then it focuses on providing a summary of the year 2000 results and contrasts these with those recorded during 1998. Important developments made during the 2000 study included the recording of SP data for several species being emitted from the snowpack. These included NO, H2O2 and CH2O. In this context, eddy-diffusion flux measurements provided the first quantitative estimates of the SP NO and NOx snow-to-atmosphere fluxes. This study also revealed that HNO3 and HO2NO2 were major sink species for HOx and NOx radicals. And, it identified the critical factors responsible for SP NO levels exceeding those at other polar sites by nearly an order of magnitude. Finally, it reports on the levels of gas phase sulfur species and provides evidence indicating that the absence of DMS at SP is most likely due to its greatly shorten chemical lifetime in the near vicinity of the plateau. It is proposed that this is due to the influence of NO on the distribution of OH in the lower free troposphere over a region that extends well beyond the plateau itself. Details related to each of the above findings plus others can be found in the 11 accompanying Special Issue papers.