Airborne measurements within the urban mixing layer (360 m) over Greater London are used to quantify CO2 emissions at the meso-scale. Daytime CO2 fluxes, calculated by the Integrative Mass Boundary Layer (IMBL) method, ranged from 46 to 104 μmol CO2m−2s−1 for four days in October 2011. The day-to-day variability of IMBL fluxes is at the same order of magnitude as for surface eddy-covariance fluxes observed in central London. Compared to fluxes derived from emissions inventory, the IMBL method gives both lower (by −37%) and higher (by 19%) estimates. The sources of uncertainty of applying the IMBL method in urban areas are discussed and guidance for future studies is given.

This study investigates the dispersion and transport of reactive pollutants in a deep urban street canyon with an aspect ratio of 2 under neutral meteorological conditions using large-eddy simulation. The spatial variation of pollutants is significant due to the existence of two unsteady vortices. The deviation of species abundance from chemical equilibrium for the upper vortex is greater than that for the lower vortex. The interplay of dynamics and chemistry is investigated using two metrics: the photostationary state defect, and the inferred ozone production rate. The latter is found to be negative at all locations within the canyon, pointing to a systematic negative offset to ozone production rates inferred by analogous approaches in environments with incomplete mixing of emissions. This study demonstrates an approach to quantify parameters for a simplified two-box model, which could support traffic management and urban planning strategies and personal exposure assessment.

Long-term trends in observed carbon monoxide (CO) concentrations were analyzed in seven major South Korean cities from 1989 to 2013. Temporal trends were evident on seasonal and annual timescales, as were spatial gradients between the cities. As CO levels in the most polluted cities decreased significantly until the early 2000s, the data were arbitrarily divided into two time periods (I: 1989–2000 and II: 2001–2013) for analysis. The mean CO concentration of period II was about 50% lower than that of period I. Long-term trends of annual mean CO concentrations, examined using the Mann–Kendall (MK) method, confirm a consistent reduction in CO levels from 1989 to 2000 (period I). The abrupt reduction in CO levels was attributed to a combination of technological improvements and government administrative/regulatory initiatives (e.g., emission mitigation strategies and a gradual shift in the fuel/energy consumption mix away from coal and oil to natural gas and nuclear power).

This study investigated the mass dependent (MDF) and independent fractionation (MIF) of stable mercury isotopes in fish during the uptake and elimination of inorganic species. Mercury accumulation during the exposure led to re-equilibration of organ isotopic compositions with the external sources, and elimination terminated the equilibrating with isotope ratios moving back to the original values. Generally, the isotopic behaviors corresponded to the changes of Hg accumulation in the muscle and liver, causing by the internal transportation, organ redistribution, and mixing of different sources. A small degree of MDF caused by biotransformation of Hg in the liver was documented during the elimination, whereas MIF was not observed. The absence of MIF during geochemical and metabolic processes suggested that mercury isotopes can be used as source tracers. Additionally, fish liver is a more responsive organ than muscle to track Hg source when it is mainly composed of inorganic species.

The four–dimensional data assimilation (FDDA) technique in the Weather Research and Forecasting (WRF) meteorological model has recently undergone an important update from the original version. Previous evaluation results have demonstrated that the updated FDDA approach in WRF provides more accurate wind fields aloft than the original approach, particularly during the nocturnal period when low level jets are a common feature in the Eastern United States. Due to the importance of WRF/FDDA meteorological fields in retrospective air quality applications, a modeling study with the Community Multiscale Air Quality (CMAQ) model was undertaken to ascertain if the improved wind flow fields translate into better performance for ozone. To undertake this objective, separate CMAQ model simulations were performed with meteorological inputs generated by WRF using the original and the updated FDDA approaches for a three month summer period. The evaluation effort focused on observed and modeled surface ozone from a mid–morning hour (10 local daylight time (LDT)). Comparisons of modeled results against concentrations aloft from an instrumented tall tower and from available morning vertical profile measurements were also examined. Surface concentrations near 10 LDT are desirable for evaluating the transport process since they are often representative of ozone that has been transported aloft overnight and has undergone downward entrainment in response to convective mixing the following morning. Statistical results from surface observed and modeled concentration pairs indicated modeled ozone from the CMAQ simulation using the updated FDDA meteorology displayed smaller biases and lower absolute errors at 88% and 80% of monitoring sites, respectively, in the Eastern United States. The CMAQ results with the updated FDDA generally exhibited smaller biases and lower absolute errors at monitoring sites across the northern states than in the southeastern states. The results provide evidence that the more accurate wind flows generated with the updated WRF/FDDA approach improved CMAQ model performance based on the statistical results from 10 LDT ozone concentrations.

Application of chemical dispersants or mechanical dispersion on surface oil is a trade-off between surface effects (impact of floating oil) and sub-surface effects (impact of suspended oil). Making an informed decision regarding such response, requires insight in the induced change in fate and transport of the oil.We aim to identify how natural, chemical and mechanical dispersion could be quantified in oil spill models. For each step in the dispersion process, we review available experimental data in order to identify overall trends and propose an algorithm or calculation method. Additionally, the conditions for successful mechanical and chemical dispersion are defined.Two commonly identified key parameters in surface oil dispersion are: oil properties (viscosity and presence of dispersants) and mixing energy (often wind speed). Strikingly, these parameters play a different role in several of the dispersion sub-processes. This may explain difficulties in simply relating overall dispersion effectiveness to the individual parameters.

The atmospheric dispersion of the NOX plume that will be emitted from a new power–plant, at present under installation, was simulated at micro–scale with Micro–Swift–Spray (MSS) Model. The plant will be constructed in a residential urban area in the town of Modena (Po Valley, Northern Italy), where low wind speeds and thermal inversions are quite frequent. Simulation results point out a different behavior of urban canopy in influencing the 3D dispersion patterns among urban obstacles, according to atmospheric mixing conditions: in case of moderate wind events, urban canyon phenomena may occur with a consequent increasing of NOX concentration gradients among buildings, while with low winds the near–field influence of the buildings emphasizes pollutant accumulation. The MSS simulated NOX concentrations result always much lower than the regulatory limits for air quality. The comparison of simulation results with measured concentration data for NOX shows the importance of micro–scale dispersion modeling to perform an accurate and reliable assessment of meteorological condition effects on pollutant distribution, and the ability of MSS in providing reliable simulations of atmospheric dispersion.

A summer campaign in Central Italy was carried out to study the impact of fire emissions on the mixing ratios of surface trace gases. Observations with a selective and sensitive instrument that uses the laser induced fluorescence technique for direct measurements of nitrogen dioxide (NO2), show a significant increase of NO2 mixing ratios, in the evening, when a fire plume reached the observations site. The increase of NO2 mixing ratios is well correlated (R=0.83) with that of particulate matter (PM), which is one of the primary product of forest and grassland fires. The tight correlation between NO2 and PM is used to improve the performance of a statistical regression model to simulate the observed O3, and to highlight the effect of fire emissions on the O3 mixing ratios. The statistical regression model of O3 improves in terms of performance (bias reduction of 77% and agreement enhancement of 10% for slope and correlation coefficient) when PM2.5 is included as additional input and proxy of the fire emissions among the usual input parameters (meteorological data and NO2 mixing ratios). A case study, comparing observed and modeled O3 in different days (with and without fire plume), suggests an impact of fire emissions on the O3 mixing ratios of about 10%.

Weathered oil can mix with sediment to form heavier-than-water sand and oil agglomerates (SOAs) that can cause beach re-oiling for years after a spill. Few studies have focused on the physical dynamics of SOAs. In this study, artificial SOAs (aSOAs) were created and deployed in the nearshore, and shear stress-based mobility formulations were assessed to predict SOA response. Prediction sensitivity to uncertainty in hydrodynamic conditions and shear stress parameterizations were explored. Critical stress estimates accounting for large particle exposure in a mixed bed gave the best predictions of mobility under shoaling and breaking waves. In the surf zone, the 10-cm aSOA was immobile and began to bury in the seafloor while smaller size classes dispersed alongshore. aSOAs up to 5cm in diameter were frequently mobilized in the swash zone. The uncertainty in predicting aSOA dynamics reflects a broader uncertainty in applying mobility and transport formulations to cm-sized particles.

In order to compare the effects of weathering on two types of mixed oil, simulated weathering experiments were performed. The first sample was a mixture of two fresh oils and the second sample was a mixture of one fresh oil and another oil sample that had undergone a serious weathering process. Comparative studies evaluated decay rates and changes in diagnostic ratios of some fingerprinting biomarkers. Results showed that the mixing process affected the weathering rate of some compounds in the oils and also that certain diagnostic ratios are more suitable for estimating mixing proportions. A Pr/n-C17 versus Ph/n-C18 plot can be used to identify the end-numbers of mixed oils and the (C13+C14)/(C25+C26) ratio is a useful diagnostic ratio to detect the degree of weathering. Finally, hopane, sterane, and alkylated PAH fingerprints were found to give useful insights about the sources of the mixed oils.