Biogenic nitric oxide emissions from soils: impact on NOx and ozone over West Africa during AMMA (African Monsoon Multidisciplinary Analysis) - observational study

Chemical and meteorological parameters measured on board the Facility for Airborne Atmospheric Measurements (FAAM) BAe 146 Atmospheric Research Aircraft during the African Monsoon Multidisciplinary Analysis (AMMA) campaign are presented to show the impact of NOx emissions from recently wetted soils in West Africa. NO emissions from soils have been previously observed in many geographical areas with different types of soil/vegetation cover during small scale studies and have been inferred at large scales from satellite measurements of NOx. This study is the first dedicated to showing the emissions of NOx at an intermediate scale between local surface sites and continental satellite measurements. The measurements reveal pronounced mesoscale variations in NOx concentrations closely linked to spatial patterns of antecedent rainfall. Fluxes required to maintain the NOx concentrations observed by the BAe-146 in a number of cases studies and for a range of assumed OH concentrations (1×106 to 1×107 molecules cm−3) are calculated to be in the range 8.4 to 36.1 ng N m−2 s−1. These values are comparable to the range of fluxes from 0.5 to 28 ng N m−2 s−1 reported from small scale field studies in a variety of non-nutrient rich tropical and sub-tropical locations reported in the review of Davidson and Kingerlee (1997). The fluxes calculated in the present study have been scaled up to cover the area of the Sahel bounded by 10 to 20 N and 10 E to 20 W giving an estimated emission of 0.03 to 0.30 Tg N from this area for July and August 2006. The observed chemical data also suggest that the NOx emitted from soils is taking part in ozone formation as ozone concentrations exhibit similar fine scale structure to the NOx, with enhancements over the wet soils. Such variability can not be explained on the basis of transport from other areas. Delon et al. (2008) is a companion paper to this one which models the impact of soil NOx emissions on the NOx and ozone concentration over West Africa during AMMA. It employs an artificial neural network to define the emissions of NOx from soils, integrated into a coupled chemistry-dynamics model. The results are compared to the observed data presented in this paper. Here we compare fluxes deduced from the observed data with the model-derived values from Delon et al. (2008).

Biogenic nitric oxide emissions from soils: impact on NOx and ozone over West Africa during AMMA (African Monsoon Multidisciplinary Analysis) - Modelling study

Nitrogen oxide biogenic emissions from soils are driven by soil and environmental parameters. The relationship between these parameters and NO fluxes is highly non linear. A new algorithm, based on a neural network calculation, is used to reproduce the NO biogenic emissions linked to precipitations in the Sahel on the 6 August 2006 during the AMMA campaign. This algorithm has been coupled in the surface scheme of a coupled chemistry dynamics model (MesoNH Chemistry) to estimate the impact of the NO emissions on NOx and O3 formation in the lower troposphere for this particular episode. Four different simulations on the same domain and at the same period are compared: one with anthropogenic emissions only, one with soil NO emissions from a static inventory, at low time and space resolution, one with NO emissions from neural network, and one with NO from neural network plus lightning NOx. The influence of NOx from lightning is limited to the upper troposphere. The NO emission from soils calculated with neural network responds to changes in soil moisture giving enhanced emissions over the wetted soil, as observed by aircraft measurements after the passing of a convective system. The subsequent enhancement of NOx and ozone is limited to the lowest layers of the atmosphere in modelling, whereas measurements show higher concentrations above 1000 m. The neural network algorithm, applied in the Sahel region for one particular day of the wet season, allows an immediate response of fluxes to environmental parameters, unlike static emission inventories. Stewart et al (2008) is a companion paper to this one which looks at NOx and ozone concentrations in the boundary layer as measured on a research aircraft, examines how they vary with respect to the soil moisture, as indicated by surface temperature anomalies, and deduces NOx fluxes. In this current paper the model-derived results are compared to the observations and calculated fluxes presented by Stewart et al (2008).

HOx observations over West Africa during AMMA: impact of isoprene and NOx

Aircraft OH and HO2 measurements made over West Africa during the AMMA field campaign in summer 2006 have been investigated using a box model constrained to observations of long-lived species and physical parameters. "Good" agreement was found for HO2 (modelled to observed gradient of 1.23 ± 0.11). However, the model significantly overpredicts OH concentrations. The reasons for this are not clear, but may reflect instrumental instabilities affecting the OH measurements. Within the model, HOx concentrations in West Africa are controlled by relatively simple photochemistry, with production dominated by ozone photolysis and reaction of O(1D) with water vapour, and loss processes dominated by HO2 + HO2 and HO2 + RO2. Isoprene chemistry was found to influence forested regions. In contrast to several recent field studies in very low NOx and high isoprene environments, we do not observe any dependence of model success for HO2 on isoprene and attribute this to efficient recycling of HOx through RO2 + NO reactions under the moderate NOx concentrations (5–300 ppt NO in the boundary layer, median 76 ppt) encountered during AMMA. This suggests that some of the problems with understanding the impact of isoprene on atmospheric composition may be limited to the extreme low range of NOx concentrations.

NOx and O3 above a tropical rainforest: an analysis with a global and box model

A cross-platform field campaign, OP3, was conducted in the state of Sabah in Malaysian Borneo between April and July of 2008. Among the suite of observations recorded, the campaign included measurements of NOx and O3 – crucial outputs of any model chemistry mechanism. We describe the measurements of these species made from both the ground site and aircraft. We then use the output from two resolutions of the chemistry transport model p-TOMCAT to illustrate the ability of a global model chemical mechanism to capture the chemistry at the rainforest site. The basic model performance is good for NOx and poor for ozone. A box model containing the same chemical mechanism is used to explore the results of the global model in more depth and make comparisons between the two. Without some parameterization of the nighttime boundary layer – free troposphere mixing (i.e. the use of a dilution parameter), the box model does not reproduce the observations, pointing to the importance of adequately representing physical processes for comparisons with surface measurements. We conclude with a discussion of box model budget calculations of chemical reaction fluxes, deposition and mixing, and compare these results to output from p-TOMCAT. These show the same chemical mechanism behaves similarly in both models, but that emissions and advection play particularly strong roles in influencing the comparison to surface measurements.

Design and development of a low NOx Coanda ejector burner

Small gaseous combustion systems are being targeted by strict pollution legislation which will provide challenges to reduce the NOx being emitted. A novel type of gas burner has been successfully designed and developed which incorporates a Coanda ejector to promote recirculation of flue gas from the burner exit. This provides a combustion system which gives very low emissions of NOx and CO, whilst maintaining a high degree of flame stability over a range of air/fuel ratios and fuel flow rates. Recirculation of flue gas was obtained by manipulating the aerodynamics of the system, without the aid of external duct work or moving parts. The design of the burner allowed very low pollutant emissions near stoichiometric conditions, resulting in high temperatures of the exit gas. Potential applications of this type of burner are in small and intermediate furnaces where low NOx emissions are required. Moreover, very high-temperature applications, such as glass furnaces could benefit in both cost and pollutant emissions from such a burner.

Latitudinal variation of the effect of aviation NOx emissions on atmospheric ozone and methane and related climate metrics

We evaluate the response to regional and latitudinal changes in aircraft NOx emissions using several climate metrics (radiative forcing (RF), Global Warming Potential (GWP), Global Temperature change Potential (GTP)). Global chemistry transport model integrations were performed with sustained perturbations in regional aircraft and aircraft-like NOx emissions. The RF due to the resulting ozone and methane changes is then calculated. We investigate the impact of emission changes for specific geographical regions (approximating to USA, Europe, India and China) and cruise altitude emission changes in discrete latitude bands covering both hemispheres. We find that lower latitude emission changes (per Tg N) cause ozone and methane RFs that are about a factor of 6 larger than those from higher latitude emission changes. The net RF is positive for all experiments. The meridional extent of the RF is larger for low latitude emissions. GWPs for all emission changes are positive, with tropical emissions having the largest values; the sign of the GTP depends on the choice of time horizon.

Reactive Halogens in the Marine Boundary Layer (RHaMBLe): the tropical North Atlantic experiments

The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe) programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period. This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental). Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv. Consistency with these air mass classifications is observed in the time series of soluble gas and aerosol composition measurements, with additional identification of periods of slightly elevated dust concentrations consistent with the trajectories passing over the African continent. The CVAO is shown to be broadly representative of the wider North Atlantic marine boundary layer; measurements of NO, O3 and black carbon from the ship are consistent with a clean Northern Hemisphere marine background. Aerosol composition measurements do not indicate elevated organic material associated with clean marine air. Closer to the African coast, black carbon and NO levels start to increase, indicating greater anthropogenic influence. Lower ozone in this region is possibly associated with the increased levels of measured halocarbons, associated with the nutrient rich waters of the Mauritanian upwelling. Bromide and chloride deficits in coarse mode aerosol at both the CVAO and on D319 and the continuous abundance of inorganic gaseous halogen species at CVAO indicate significant reactive cycling of halogens. Aircraft measurements of O3 and CO show that surface measurements are representative of the entire boundary layer in the vicinity both in diurnal variability and absolute levels. Above the inversion layer similar diurnal behaviour in O3 and CO is observed at lower mixing ratios in the air that had originated from south of Cape Verde, possibly from within the ITCZ. ECMWF calculations on two days indicate very different boundary layer depths and aircraft flights over the ship replicate this, giving confidence in the calculated boundary layer depth.

Peroxy radicals and ozone photochemistry in air masses undergoing long-range transport

Concentrations of peroxy radicals (HO2+ΣiRiO2) in addition to other trace gases were measured onboard the UK Meteorological Office/Natural Environment Research Council British Aerospace 146-300 atmospheric research aircraft during the Intercontinental Transport of Ozone and Precursors (ITOP) campaign based at Horta Airport, Faial, Azores (38.58° N, 28.72° W) in July/August 2004. The overall peroxy radical altitude profile displays an increase with altitude that is likely to have been impacted by the effects of long-range transport. The peroxy radical altitude profile for air classified as of marine origin shows no discernable altitude profile. A range of air-masses were intercepted with varying source signatures, including those with aged American and Asian signatures, air-masses of biomass burning origin, and those that originated from the east coast of the United States. Enhanced peroxy radical concentrations have been observed within this range of air-masses indicating that long-range transported air-masses traversing the Atlantic show significant photochemical activity. The net ozone production at clear sky limit is in general negative, and as such the summer mid-Atlantic troposphere is at limit net ozone destructive. However, there is clear evidence of positive ozone production even at clear sky limit within air masses undergoing long-range transport, and during ITOP especially between 5 and 5.5 km, which in the main corresponds to a flight that extensively sampled air with a biomass burning signature. Ozone production was NOx limited throughout ITOP, as evidenced by a good correlation (r2=0.72) between P(O3) and NO. Strong positive net ozone production has also been seen in varying source signature air-masses undergoing long-range transport, including but not limited to low-level export events, and export from the east coast of the United States.

Tracer correlations in the northern high latitude lowermost stratosphere: Influence of cross‐tropopause mass exchange

We present an analysis of trace gas correlations in the lowermost stratosphere. In‐situ aircraft measurements of CO, N2O, NOy and O3, obtained during the STREAM 1997 winter campaign, have been used to investigate the role of cross‐tropopause mass exchange on tracer‐tracer relations. At altitudes several kilometers above the local tropopause, undisturbed stratospheric air was found with NOy/NOy * ratios close to unity, NOy/O3 about 0.003–0.006 and CO mixing ratios as low as 20 ppbv (NOy * is a proxy for total reactive nitrogen derived from NOy–N2O relations measured in the stratosphere). Mixing of tropospheric air into the lowermost stratosphere has been identified by enhanced ratios of NOy/NOy * and NOy/O3, and from scatter plots of CO versus O3. The enhanced NOy/O3 ratio in the lowermost stratospheric mixing zone points to a reduced efficiency of O3 formation from aircraft NOx emissions.

Studies on particulate matter (PM10) and its precursors over urban environment of Reading, UK

The extent to which airborne particles penetrate into the human respiratory system is determined mainly by their size, with possible health effects. The research over the scientific evidence of the role of airborne particles in adverse health effects has been intensified in recent years. In the present study, seasonal variations of PM10 and its relation with anthropogenic activities have been studied by using the data from UK National Air Quality Archive over Reading, UK. The diurnal variation of PM10 shows a morning peak during 7:00-10:00 LT and an evening peak during 19:00-22:00 LT. 3 The variation between 12:00 and 17:00 LT remains more or less steady for PM10 with the minimum value of similar to 16 mu g m(-3). PM10 and black smoke (BS) concentrations during weekdays were found to be high compared to weekends. A reduction in the concentration of PM10 has been found during the Christmas holidays compared to normal days during December. Seasonal variations of PM10 showed high values during spring compared to other seasons. A linear relationship has been found between PM10 and NO, during March, July, November and December suggesting that most of the PM10 is due to local traffic exhaust emissions. PM10 and SO2 concentrations showed positive correlation with the correlation coefficient of R-2 = 0.65 over the study area. Seasonal variations of SO2 and NOx showed high concentrations during winter and low concentrations during spring. Fraction of BS in PM10 has been found to be 50% during 2004 over the study area. (C) 2005 Elsevier Ltd. All rights reserved.

Quasi-biennial oscillation and tracer distributions in a coupled chemistry-climate model

[ 1] We have used a fully coupled chemistry-climate model (CCM), which generates its own wind and temperature quasi-biennial oscillation (QBO), to study the effect of coupling on the QBO and to examine the QBO signals in stratospheric trace gases, particularly ozone. Radiative coupling of the interactive chemistry to the underlying general circulation model tends to prolong the QBO period and to increase the QBO amplitude in the equatorial zonal wind in the lower and middle stratosphere. The model ozone QBO agrees well with Stratospheric Aerosol and Gas Experiment II and Total Ozone Mapping Spectrometer satellite observations in terms of vertical and latitudinal structure. The model captures the ozone QBO phase change near 28 km over the equator and the column phase change near +/- 15 degrees latitude. Diagnosis of the model chemical terms shows that variations in NOx are the main chemical driver of the O-3 QBO around 35 km, i.e., above the O-3 phase change.

Cross-hemispheric transport of Central African biomass burning pollutants: Implications for downwind ozone production

Pollutant plumes with enhanced concentrations of trace gases and aerosols were observed over the southern coast of West Africa during August 2006 as part of the AMMA wet season field campaign. Plumes were observed both in the mid and upper troposphere. In this study we examined the origin of these pollutant plumes, and their potential to photochemically produce ozone (O3) downwind over the Atlantic Ocean. Their possible contribution to the Atlantic O3 maximum is also discussed. Runs using the BOLAM mesoscale model including biomass burning carbon monoxide (CO) tracers were used to confirm an origin from central African biomass burning fires. The plumes measured in the mid troposphere (MT) had significantly higher pollutant concentrations over West Africa compared to the upper tropospheric (UT) plume. The mesoscale model reproduces these differences and the two different pathways for the plumes at different altitudes: transport to the north-east of the fire region, moist convective uplift and transport to West Africa for the upper tropospheric plume versus north-west transport over the Gulf of Guinea for the mid-tropospheric plume. Lower concentrations in the upper troposphere are mainly due to enhanced mixing during upward transport. Model simulations suggest that MT and UT plumes are 16 and 14 days old respectively when measured over West Africa. The ratio of tracer concentrations at 600 hPa and 250 hPa was estimated for 14–15 August in the region of the observed plumes and compares well with the same ratio derived from observed carbon dioxide (CO2) enhancements in both plumes. It is estimated that, for the period 1–15 August, the ratio of Biomass Burning (BB) tracer concentration transported in the UT to the ones transported in the MT is 0.6 over West Africa and the equatorial South Atlantic. Runs using a photochemical trajectory model, CiTTyCAT, initialized with the observations, were used to estimate in-situ net photochemical O3 production rates in these plumes during transport downwind of West Africa. The mid-troposphere plume spreads over altitude between 1.5 and 6 km over the Atlantic Ocean. Even though the plume was old, it was still very photochemically active (mean net O3 production rates over 10 days of 2.6 ppbv/day and up to 7 ppbv/day during the first days) above 3 km especially during the first few days of transport westward. It is also shown that the impact of high aerosol loads in the MT plume on photolysis rates serves to delay the peak in modelled O3 concentrations. These results suggest that a significant fraction of enhanced O3 in mid-troposphere over the Atlantic comes from BB sources during the summer monsoon period. According to simulated occurrence of such transport, BB may be the main source for O3 enhancement in the equatorial south Atlantic MT, at least in August 2006. The upper tropospheric plume was also still photochemically active, although mean net O3 production rates were slower (1.3 ppbv/day). The results suggest that, whilst the transport of BB pollutants to the UT is variable (as shown by the mesoscale model simulations), pollution from biomass burning can make an important contribution to additional photochemical production of O3 in addition to other important sources such as nitrogen oxides (NOx) from lightning.

Overview: oxidant and particle photochemical processes above a south-east Asian tropical rain forest (the OP3 project); introduction, rationale, location, characteristics and tools

In April–July 2008, intensive measurements were made of atmospheric composition and chemistry in Sabah, Malaysia, as part of the "Oxidant and particle photochemical processes above a South-East Asian tropical rainforest" (OP3) project. Fluxes and concentrations of trace gases and particles were made from and above the rainforest canopy at the Bukit Atur Global Atmosphere Watch station and at the nearby Sabahmas oil palm plantation, using both ground-based and airborne measurements. Here, the measurement and modelling strategies used, the characteristics of the sites and an overview of data obtained are described. Composition measurements show that the rainforest site was not significantly impacted by anthropogenic pollution, and this is confirmed by satellite retrievals of NO2 and HCHO. The dominant modulators of atmospheric chemistry at the rainforest site were therefore emissions of BVOCs and soil emissions of reactive nitrogen oxides. At the observed BVOC:NOx volume mixing ratio (~100 pptv/pptv), current chemical models suggest that daytime maximum OH concentrations should be ca. 105 radicals cm−3, but observed OH concentrations were an order of magnitude greater than this. We confirm, therefore, previous measurements that suggest that an unexplained source of OH must exist above tropical rainforest and we continue to interrogate the data to find explanations for this.

Forest fire plumes over the North Atlantic: p-TOMCAT model simulations with aircraft and satellite measurements from the ITOP/ICARTT campaign

Intercontinental Transport of Ozone and Precursors (ITOP) (part of International Consortium for Atmospheric Research on Transport and Transformation (ICARTT)) was an intense research effort to measure long-range transport of pollution across the North Atlantic and its impact on O3 production. During the aircraft campaign plumes were encountered containing large concentrations of CO plus other tracers and aerosols from forest fires in Alaska and Canada. A chemical transport model, p-TOMCAT, and new biomass burning emissions inventories are used to study the emissions long-range transport and their impact on the troposphere O3 budget. The fire plume structure is modeled well over long distances until it encounters convection over Europe. The CO values within the simulated plumes closely match aircraft measurements near North America and over the Atlantic and have good agreement with MOPITT CO data. O3 and NOx values were initially too great in the model plumes. However, by including additional vertical mixing of O3 above the fires, and using a lower NO2/CO emission ratio (0.008) for boreal fires, O3 concentrations are reduced closer to aircraft measurements, with NO2 closer to SCIAMACHY data. Too little PAN is produced within the simulated plumes, and our VOC scheme's simplicity may be another reason for O3 and NOx model-data discrepancies. In the p-TOMCAT simulations the fire emissions lead to increased tropospheric O3 over North America, the north Atlantic and western Europe from photochemical production and transport. The increased O3 over the Northern Hemisphere in the simulations reaches a peak in July 2004 in the range 2.0 to 6.2 Tg over a baseline of about 150 Tg.