The seasonal cycles and photochemistry of C2–C5 alkanes at Mace Head

Continuous in-situ measurements of NMHCs at Mace Head, Ireland during two full annual cycles from January 2005 to January 2007 were used to investigate NMHC emission sources and transport including dilution and photochemical oxidation. The Mace Head research station is ideally located to sample a wide range of air masses including polluted European transport, clean North Atlantic and Arctic air masses and the ultra-clean, Southern Atlantic air masses. The variety in air mass sampling is used to investigate interaction of emissions, transport, dilution and photochemistry. Variability of long-lived hydrocarbon ratios is used to assess and estimate typical transport times from emission source to the Mace Head receptor. Seasonality in the ratios of isomeric alkane pairs (for butane and pentanes) are used to assess the effects of atmospheric transport and photochemical ageing. Finally, the natural logarithms of NMHC ratios are used to assess photochemical oxidation.     

Comprehensive analysis of the carbon impacts of vehicle intelligent speed control

In recent years sophisticated technologies have been developed to control vehicle speed based on the type of road the vehicle is driven on using Global Positioning Systems and in-car technology that can alter the speed of the vehicle. While reducing the speed of road vehicles is primarily of interest from a safety perspective, vehicle speed is also an important determinant of vehicle emissions and thus these technologies can be expected to have impacts on a range of exhaust emissions. This work analyses the results from a very large, comprehensive field trial that used 20 instrumented vehicles with and without speed control driven almost 500,000 km measuring vehicle speed at 10 Hz. We develop individual vehicle modal emissions models for CO₂ for 30 Euro III and Euro IV cars at a 1-Hz time resolution. Generalized Additive Models were used to describe how emissions from individual vehicles vary depending on their driving conditions, taking account of variable interactions and time-lag effects. We quantify the impact that vehicle speed control has on-vehicle emissions of CO₂ by road type, fuel type and driver behaviour. Savings in CO₂ of ≈6% were found on average for motorway-type roads when mandatory speed control was used compared with base case conditions. For most other types of road, speed control has very little effect on emissions of CO₂ and in some cases can result in increased emissions for low-speed limit urban roads. We also find that there is on average a 20% difference in CO₂ emission between the lowest and highest emitting driver, which highlights the importance of driver behaviour in general as a means of reducing emissions of CO₂.     

Assimilation of conventional and satellite wind observations in a mesoscale atmospheric model for studying atmospheric dispersion

A mesoscale atmospheric model PSU/NCAR MM5 is used to provide operational weather forecasts for a nuclear emergency response decision support system on the southeast coast of India. In this study the performance of the MM5 model with assimilation of conventional surface and upper-air observations along with satellite derived 2-d surface wind data from QuickSCAT sources is examined. Two numerical experiments with MM5 are conducted: one with static initialization using NCEP FNL data and second with dynamic initialization by assimilation of observations using four dimensional data assimilation (FDDA) analysis nudging for a pre-forecast period of 12 h. Dispersion simulations are conducted for a hypothetical source at Kalpakkam location with the HYSPLIT Lagrangian particle model using simulated wind field from the above experiments. The present paper brings out the differences in the atmospheric model predictions and the differences in dispersion model results from control and assimilation runs. An improvement is noted in the atmospheric fields from the assimilation experiment which has led to significant alteration in the trajectory positions, plume orientation and its distribution pattern. Sensitivity tests using different PBL and surface parameterizations indicated the simple first order closure schemes (Blackadar, MRF) coupled with the simple soil model have given better results for various atmospheric fields. The study illustrates the impact of the assimilation of the scatterometer wind and automated weather stations (AWS) observations on the meteorological model predictions and the dispersion results.     

Chemical speciation,transport and contribution of biomass burning smoke to ambient aerosol in Guangzhou,a mega city of China

Intensive measurements of aerosol (PM₁₀) and associated water-soluble ionic and carbonaceous species were conducted in Guangzhou, a mega city of China, during summer 2006. Elevated levels of most chemical species were observed especially at nighttime during two episodes, characterized by dramatic build-up of the biomass burning tracers levoglucosan and non-sea-salt potassium, when the prevailing wind direction had changed due to two approaching tropical cyclones. High-resolution air mass back trajectories based on the MM5 model revealed that air masses with high concentrations of levoglucosan (43–473 ng m^?3) and non-sea-salt potassium (0.83–3.2 μg m^?3) had passed over rural regions of the Pearl River Delta and Guangdong Province, where agricultural activities and field burning of crop residues are common practices. The relative contributions of biomass burning smoke to organic carbon in PM₁₀ were estimated from levoglucosan data to be on average 7.0 and 14% at daytime and nighttime, respectively, with maxima of 9.7 and 32% during the episodic transport events, indicating that biomass and biofuel burning activities in the rural parts of the Pearl River Delta and neighboring regions could have a significant impact on ambient urban aerosol levels.     

Simulating chemistry–aerosol–cloud–radiation–climate feedbacks over the continental U.S. using the online-coupled Weather Research Forecasting Model with chemistry (WRF/Chem)

The chemistry–aerosol–cloud–radiation–climate feedbacks are simulated using WRF/Chem over the continental U.S. in January and July 2001. Aerosols can reduce incoming solar radiation by up to ?9% in January and ?16% in July and 2-m temperatures by up to 0.16 °C in January and 0.37 °C in July over most of the continental U.S. The NO₂ photolysis rates decrease in July by up to ?8% over the central and eastern U.S. where aerosol concentrations are high but increase by up to 7% over the western U.S. in July and up to 13% over the entire domain in January. Planetary boundary layer (PBL) height reduces by up to ?23% in January and ?24% in July. Temperatures and wind speeds in July in big cities such as Atlanta and New York City reduce at/near surface but increase at higher altitudes. The changes in PBL height, temperatures, and wind speed indicate a more stable atmospheric stability of the PBL and further exacerbate air pollution over areas where air pollution is already severe. Aerosols can increase cloud optical depths in big cities in July, and can lead to 500–5000 cm^?3 cloud condensation nuclei (CCN) at a supersaturation of 1% over most land areas and 10–500 cm^?3 CCN over ocean in both months with higher values over most areas in July than in January, particularly in the eastern U.S. The total column cloud droplet number concentrations are up to 4.9 × 10⁶ cm^?2 in January and up to 11.8 × 10⁶ cm^?2 in July, with higher values over regions with high CCN concentrations and sufficient cloud coverage. Aerosols can reduce daily precipitation by up to 1.1 mm day^?1 in January and 19.4 mm day^?1 in July thus the wet removal rates over most of the land areas due to the formation of small CCNs, but they can increase precipitation over regions with the formation of large/giant CCN. These results indicate potential importance of the aerosol feedbacks and an urgent need for their accurate representations in current atmospheric models to reduce uncertainties associated with climate change predictions.     

Analysis of 3-year observations of CFC-11, CFC-12 and CFC-113 from a semi-rural site in China

In-situ measurements of atmospheric chlorofluorocarbons (CFCs) can be used to the assess their global and regional emissions and to check for compliance with phase-out schedules under Montreal protocol and its amendments. The atmospheric mixing ratios of CFC-11 (CCl₃F), CFC-12 (CCl₂F₂) and CFC-113 (CCl₂F–CClF₂) have been measured by an automated in-situ GC-ECDs system at the regional Chinese Global Atmosphere Watch (GAW) station Shangdianzi (SDZ), from November 2006 to October 2009. The time series for these three principal CFCs showed large episodic events and background conditions occurred for approximately 30% (CFC-11), 52% (CFC-12) and 56% (CFC-113) of the measurements. The mean background mixing ratios for CFC-11, CFC-12 and CFC-113 were 244.8 ppt (parts per trillion, 10^?12, molar) 539.6 ppt and 76.8 ppt, respectively, for 2006–2009. The enhanced CFC mixing ratios compared to AGAGE sites such as Trinidad Head (THD), US and Mace Head (MHD), Ireland suggest regional influences even during background conditions at SDZ, which is much closer to highly-populated areas. Between 2006 and 2009 background CFCs exhibited downward trends at rates of ?2.0 ppt yr^?1 for CFC-11, ?2.5 ppt yr^?1 for CFC-12 and ?0.7 ppt yr^?1 for CFC-113. De-trended 3-year average background seasonal cycles displayed small fluctuations with peak-to-trough amplitudes of 1.0 ± 0.02 ppt (0.4%) for background CFC-11, 1.3 ± 2.1 ppt (0.3%) for CFC-12 and 0.2 ± 0.4 ppt (0.3%) for CFC-113. On the other hand, during pollution periods these CFCs showed much larger seasonal cycles of 11.2 ± 10.7 ppt (5%) for CFC-11, 7.5 ± 6.5 ppt (2%) for CFC-12 and 1.0 ± 1.2 ppt (1.2%) for CFC-113, with apparent winter minima and early summer maxima. This enhancement was attributed to prevailing wind directions from urban regions in summer and to enhanced anthropogenic sources during the warm season. In general, horizontal winds from northeast showed negative contribution to atmospheric CFCs loading, whereas South Western advection (urban sector: Beijing) had positive contributions.     

Characterisation of PM10 emissions from woodstove combustion of common woods grown in Portugal

A series of source tests was performed to evaluate the chemical composition of particle emissions from the woodstove combustion of four prevalent Portuguese species of woods: Pinus pinaster (maritime pine), Eucalyptus globulus (eucalyptus), Quercus suber (cork oak) and Acacia longifolia (golden wattle). Analyses included water-soluble ions, metals, radionuclides, organic and elemental carbon (OC and EC), humic-like substances (HULIS), cellulose and approximately l80 organic compounds. Particle (PM₁₀) emission factors from eucalyptus and oak were higher than those from pine and acacia. The carbonaceous matter represented 44–63% of the particulate mass emitted during the combustion process, regardless of species burned. The major organic components of smoke particles, for all the wood species studied, with the exception of the golden wattle (0.07–1.9% w/w), were anhydrosugars (0.2–17% w/w). Conflicting with what was expected, only small amounts of cellulose were found in wood smoke. As for HULIS, average particle mass concentrations ranged from 1.5% to 3.0%. The golden wattle wood smoke presented much higher concentrations of ions and metal species than the emissions from the other wood types. The results of the analysis of radionuclides revealed that the ²²⁶Ra was the naturally occurring radionuclide more enriched in PM₁₀. The chromatographically resolved organics included n-alkanes, n-alkenes, PAH, oxygenated PAH, n-alkanals, ketones, n-alkanols, terpenoids, triterpenoids, phenolic compounds, phytosterols, alcohols, n-alkanoic acids, n-di-acids, unsaturated acids and alkyl ester acids.     

Chemical mass balance source apportionment for combined PM2.5 measurements from U.S. non-urban and urban long-term networks

The Minnesota Particulate Matter 2.5 (PM_2.5) Source Apportionment Study was undertaken to explore the utility of PM_2.5 mass, element, ion, and carbon measurements from long-term speciation networks for pollution source attribution. Ambient monitoring data at eight sites across the state were retrieved from the archives of the Interagency Monitoring of Protected Visual Environments (IMPROVE) and the Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]) and analyzed by an Effective Variance – Chemical Mass Balance (EV-CMB) receptor model with region-specific geological source profiles developed in this study. PM_2.5 was apportioned into contributions of fugitive soil dust, calcium-rich dust, taconite (low grade iron ore) dust, road salt, motor vehicle exhaust, biomass burning, coal-fired utility, and secondary aerosol. Secondary sulfate and nitrate contributed strongly (49–71% of PM_2.5) across all sites and was dominant (≥60%) at IMPROVE sites. Vehicle exhausts accounted for 20–70% of the primary PM_2.5 contribution, largely exceeding the proportion in the primary PM_2.5 emission inventory. The diesel exhaust contribution was separable from the gasoline engine exhaust contribution at the STN sites. Higher detection limits for several marker elements in the STN resulted in non-detectable coal-fired boiler contributions which were detected in the IMPROVE data. Despite the different measured variables, analytical methods, and detection limits, EV-CMB results from a nearby IMPROVE-STN non-urban/urban sites showed similar contributions from regional sources – including fugitive dust and secondary aerosol. Seasonal variations of source contributions were examined and extreme PM_2.5 episodes were explained by both local and regional pollution events.     

Influence of roads and inhabited areas on metal concentrations in terrestrial mosses

The guidelines regarding sampling terrestrial mosses for biomonitoring the atmospheric contamination in a region specifically recommend that sampling close to focal points of contamination (i.e. roads, populated areas, etc.) should be avoided for satisfactory characterization of general patterns of contamination. However, these recommendations cannot always be followed in many parts of the world with dense, highly dispersed populations. The aim of the present study was to determine how the distances between sampling sites (SS) and contamination foci such as roads, isolated houses and urban nuclei affect regular, large-scale sampling networks. Metal concentrations obtained in biennial sampling surveys carried out between 2000 and 2006 in Galicia (NW Spain) were used, and the relative proportions of the concentrations corresponding to small-scale and large-scale processes were calculated. The possible relationship between the mean concentrations corresponding to small-scale processes in the different sampling surveys and the distances from SS to roads, buildings and urban nuclei was established by a GIS. Outliers in the data were identified at many of the SS and frequency statistics revealed the absence of any relationship between the distance to these foci and the concentrations of metals in the moss. The method also revealed many instances of the influence of one or more small-scale contamination foci such as airports and railways (often not considered in the sampling recommendations) on SS. Relocation of such SS would improve the representativeness of the sampling grid.     

Inferring coastal processes from regional-scale mapping of Radon and salinity: examples from the Great Barrier Reef, Australia

The radon isotope ²²²Rn and salinity in coastal surface water were mapped on regional scales, to improve the understanding of coastal processes and their spatial variability. Radon was measured with a surface-towed, continuously recording multi-detector setup on a moving vessel. Numerous processes and locations of land-ocean interaction along the Central Great Barrier Reef coastline were identified and interpreted based on the data collected. These included riverine fluxes, terrestrially-derived fresh submarine groundwater discharge (SGD) and the tidal pumping of seawater through mangrove forests. Based on variations in the relationship of the tracers radon and salinity, some aspects of regional freshwater inputs to the coastal zone and to estuaries could be assessed. Concurrent mapping of radon and salinity allowed an efficient qualitative assessment of land-ocean interaction on various spatial and temporal scales, indicating that such surveys on coastal scales can be a useful tool to obtain an overview of SGD locations and processes.