A modeling study of SOx-NOx-Hydrocarbon plumes and their transport to the background troposphere

A model which emulates the behavior of urban-industrial plumes has been developed and used to analyze the chemical reaction processes occurring as a polluted air mass is transported from an urban area. A 73-step reaction mechanism describing hydrocarbon/NO_xSO_x chemistry was used, with photolytic rate constants depending on the latitude, time of day and time of year. The model includes the physical processes of plume dilution, entrainment and dry deposition, and is simulated under a diurnally varying mixing layer or neutral atmospheric stability conditions.Simulation results are compared with reported field measurements for plumes from St. Louis, Milwaukee, and a power plant plume entrained in the Milwaukee urban plume. The agreement with field concentrations and SO₂ transformation rate data is good, the latter ranging from 1 to 12 % h⁻¹. The study was extended to hypothetical plumes for parametric analysis. In every case considered, the classic O₃ peak occurred at about 3:30 p.m., essentially independent of initial concentrations and plume departure time. The analysis also indicated that substantial SO₂ oxidation via homogeneous gas phase chemistry can occur at night-time, the prerequisite being a high HG/NO_x ratio.     

Dynamic-chemical coupling of the upper troposphere and lower stratosphere region

The importance of the interaction between chemistry and dynamics in the upper troposphere and lower stratosphere for chemical species like ozone is investigated using two chemistry-climate models and a Lagrangian trajectory model. Air parcels from the upper troposphere, i.e. regions of lightning and aircraft emissions, are able to be transported into the lowermost stratosphere (LMS). Trajectory calculations suggest that the main transport pathway runs via the inter tropical convergence zone, across the tropical tropopause and then to higher latitudes, i.e. into the LMS. NOx from aircraft emissions at mid-latitudes are unlikely to perturb the LMS since they are washed-out while still in the troposphere. In contrast, NOx from tropical lightning has the chance to accumulate in the LMS. Because of the longer residence times of NOx in the LMS, compared to the upper troposphere, this excess NOx from lightning has the potential to form ozone in the LMS, which then is transported back to the troposphere at mid-latitudes. In the models, around 10% of the ozone concentration and 50% of the NOx concentration in the northern hemisphere LMS is produced by lightning NOx At least 5% of the ozone concentration and 35% the NOx concentration at 150 hPa at mid-latitudes originates from tropical lightning in the climate-chemistry simulations.     

Modeling of ozone reactions on aircraft-related soot in the upper troposphere and lower stratosphere

Several studies in modeling atmospheric processes have suggested that heterogeneous chemistry on soot emitted from high altitude aircraft could affect stratospheric ozone depletion. However, these modeling studies were limited because they did not adequately consider the decrease in reaction probability with time as the surface of the soot becomes “poisoned” by its interactions with various gases. Here we extend UIUC's two-dimensional chemical-transport model to investigate possible effects of heterogeneous reactions of ozone on aircraft-generated carbon particles, including a treatment of soot poisoning in the model. We generally follow literature recommendations for ozone uptake probabilities and determine the available active sites on soot given partial pressures of the reactants, temperature, and time since soot emission in order to investigate ozone decrease. The regeneration of soot active sites is also taken into account in this study. We find that, even if active sites on soot surfaces are regenerated, upper troposphere and lower stratosphere ozone losses on aircraft emitted soot occurring through heterogeneous reactions are insignificant once poisoning effects are considered.     

Vertical distributions of non-methane hydrocarbons and halocarbons in the lower troposphere over northeast China

Vertical distributions of air pollutants are crucial for understanding the key processes of atmospheric transport and for evaluating chemical transport models. In this paper, we present measurements of non-methane hydrocarbons (NMHCs) and halocarbons obtained from an intensive aircraft study over northeast (NE) China in summer 2007. Most compounds exhibited a typical negative profile of decreasing mixing ratios with increasing altitude, although the gradients differed with different species. Three regional plumes with enhanced VOC mixing ratios were discerned and characterized. An aged plume transported from the northern part of the densely populated North China Plain (NCP; i.e. Beijing–Tianjin area) showed relatively higher levels of HCFC-22, 1,2-dichloroethane (1,2-DCE) and toluene. In comparison, the plume originating from Korea had higher abundances of CFC-12, tetrachloroethene (C₂Cl₄) and methyl chloride (CH₃Cl), while regional air masses from NE China contained more abundant light alkanes. By comparing these results with the earlier PEM-West B (1994) and TRACE-P (2001) aircraft measurements, continuing declining trends were derived for methyl chloroform (CH₃CCl₃), tetrachloromethane (CCl₄) and C₂Cl₄ over the greater China–northwestern Pacific region, indicating the accomplishment of China in reducing these compounds under the Montreal protocol. However, the study also provided evidence for the continuing emissions of several halocarbons in China in 2007, such as CFCs (mainly from materials in stock) and HCFCs.     

On springtime high ozone events in the lower troposphere from Southeast Asian biomass burning

Ozone peaks with mixing ratios as high as 138 ppbv were observed in the lower troposphere (2.5–4.5 km) over Hong Kong in spring. Simultaneously observed high humidity suggests that this enhanced ozone was not the result of transport from the upper troposphere. Back trajectory analysis suggests that these enhancements resulted from lateral transport. Air masses arriving at the altitude of the ozone peaks appear to have passed over continental Southeast Asia where the bulk of biomass burning occurs at this time of the year (February–April). We hypothesize that biomass burning in this region provided the necessary precursors for the observed ozone enhancement. As far as we know this is the first observation of highly enhanced ozone layers associated with biomass burning in continental Southeast Asia.     

The role of halogen species in the troposphere

While the role of reactive halogen species (e.g. Cl, Br) in the destruction of the stratospheric ozone layer is well known, their role in the troposphere was investigated only since their destructive effect on boundary layer ozone after polar sunrise became obvious. During these 'Polar Tropospheric Ozone Hole' events O(3) is completely destroyed in the lowest approximately 1000 m of the atmosphere on areas of several million square kilometres. Up to now it was assumed that these events were confined to the polar regions during springtime. However, during the last few years significant amounts of BrO and Cl-atoms were also found outside the Arctic and Antarctic boundary layer. Recently even higher BrO mixing ratios (up to 176 ppt) were detected by optical absorption spectroscopy (DOAS) in the Dead Sea basin during summer. In addition, evidence is accumulating that BrO (at levels around 1-2 ppt) is also occurring in the free troposphere at all latitudes.In contrast to the stratosphere, where halogens are released from species, which are very long lived in the troposphere, likely sources of boundary layer Br and Cl are autocatalytic oxidation of sea salt halides (the 'Bromine Explosion'), while precursors of free tropospheric BrO and coastal IO probably are short-lived organo-halogen species. At the levels suggested by the available measurements reactive halogen species have a profound effect on tropospheric chemistry: In the polar boundary layer during 'halogen events' ozone is usually completely lost within hours or days. In the free troposphere the effective O(3)-losses due to halogens could be comparable to the known photochemical O(3) destruction. Further interesting consequences include the increase of OH levels and (at low NO(X)) the decrease of the HO(2)/OH ratio in the free troposphere.     

The oxidation of isoprene in the troposphere: Mechanism and model calculations

A chemical mechanism describing the oxidation of isoprene by OH and O³ in the troposphere has been developed and incorporated into a one-dimensional steady-state photochemical model. Calculations have been performed for continental conditions at two latitudes, 15°N and 45°N. At 45°N latitude, the effects of anthropogenic hydrocarbon emissions on the vertical profiles of NO_x (NO + NO₂) and HNO₃ overshadow the effects of isoprene emissions; at 15°N, the reduced anthropogenic emissions and the increased isoprene emissions produce increases of 26 and 4% in the column contents of NO_x and HNO₃, respectively. The integrated columns of CO at 45°N and 15°N latitude increased by 10 and 31 %, respectively, when isoprene chemistry was included, but these increases are much smaller than those that would have been obtained if all the carbon in isoprene had been photochemically transformed into CO. It appears that the fate of a significant quantity of isoprene is in the formation of longer carbon-chain (R > CH₃) oxygenated organic species. The longer carbon-chain alkylhydroperoxides and alkylperoxyacids appear to be important free radical sinks in the tropics given the lower NO_x concentrations generally found in the tropics.     

Impacts of boundary layer mixing on pollutant vertical profiles in the lower troposphere: Implications to satellite remote sensing

Mixing in the planetary boundary layer (PBL) affects vertical distributions of air tracers in the lower troposphere. An accurate representation of PBL mixing is critical for chemical-transport models (CTMs) for applications sensitive to simulations of the vertical profiles of tracers. The full mixing assumption in the widely used global CTM GEOS-Chem has recently been supplemented with a non-local PBL scheme. This study analyzes the impact of the non-local scheme on model representation of PBL mixing, consequences for simulations of vertical profiles of air tracers and surface air pollution, and implications for model applications to the interpretation of data retrieved from satellite remote sensing. The non-local scheme significantly improves simulations of the vertical distributions for NO₂ and O₃, as evaluated using aircraft measurements in summer 2004. It also reduces model biases over the U.S. by more than 10 ppb for surface ozone concentrations at night and by 2–5 ppb for peak ozone in the afternoon, as evaluated using ground observations. The application to inverse modeling of anthropogenic NO_x emissions for East China using satellite retrievals of NO₂ from OMI and GOME-2 suggests that the full mixing assumption results in 3–14% differences in top–down emission budgets as compared to the non-local scheme. The top–down estimate combining the non-local scheme and the Lin et al. inverse modeling approach suggests a magnitude of 6.6 TgN yr^?1 for emissions of NO_x over East China in July 2008 and 8.0 TgN yr^?1 for January 2009, with the magnitude and seasonality in good agreement with bottom–up estimates.     

Chemical components of aerosol particles in the lower troposphere above central europe measured under pure-air conditions

Aerosol particles have been separated by filter at an alpine observatory at 1780m a.s.l. continuously since the fall of 1969, for the purpose of subsequent chemical processing of the samples, to determine by chemical analysis concentrations of the following substances Na⁺, K⁺, Ca²⁺, CaO, Fe₂O₃, SiO₂, A1₂O₃, Pb²⁺, Cl⁻, SO²⁻₄, NO₃⁻, and NH₄⁺.Recently, an interim statistical analysis was made of the data obtained, to study aerosol concentration and the matrix of chemical aerosol composition, as controlled by atmospheric, physical and meteorological parameters. The following were taken into consideration: Precipitation intensity; relative humidity; air temperature; number and size distribution of Aitken nuclei; concentration of Radium B in air; vertical exchange coefficient between valley level and summit of the station; air mass type; and season. This synoptical approach and evaluation technique will permit systematic analysis of the functional relationships between aerosol components, on the one hand, and the controlling meteorological conditions and processes, on the other.The geographical location of the observatory permits measurements to be made under genuine pure-air conditions, especially above inversions and the mixing layer. Consideration of vertical exchange intensity, Ra-B concentration and number of Aitken nuclei offer the possibility of measuring aerosol concentration and aerosol matrix in unadulterated air masses, that is air masses having had practically no ground contact above the European continent. Hence, globally representative aerosol components are established.     

Large-scale aircraft observations of ultra-fine and fine particle concentrations in the remote Siberian troposphere: New particle formation studies

Ultra-fine particle number concentrations were measured over Siberia during two large-scale airborne measurement campaigns in April and September 2006. During both campaigns, an aircraft flew between Novosibirsk and Yakutsk, collecting every 200 km vertical profiles up to 7 km. This dataset was completed by 5 years of monthly profiles above Novosibirsk. Particle number concentration was measured in the size ranges 3–70 and 70–200 nm, along with other tracers. Free troposphere (FT) particle concentrations (N_3–200) varied between 60 and 460 cm^?3, inferior to boundary layer concentrations (100–7000 cm^?3). In April, high concentrations of ～500 cm^?3 were observed in a polluted air mass recently uplifted at 5–6 km altitude over eastern Siberia, with no sign of significant new particle formation. In September, particle concentrations decreased with altitude, but with a steeper gradient in N_70–200 compared to N_3–70, the latter accounting for 90% of the total particle concentration in the free troposphere at 6–7 km altitude. Because ultra-fine particles presumably have short lifetimes, these observed particles could have been formed in situ in the clean Siberian atmosphere. Two cases of possible nucleation with high concentration and N_3–70/N_70–200 ratios are reported for the September campaign, in the upper troposphere and in cloud outflow in the mid-troposphere. In the seasonal analysis, a FT N_3–70 maximum is found in July–August between 6 and 7 km altitude, with N_3–70 accounting for ～90% of N_3–200 supporting the hypothesis of in situ formation in the FT. A secondary FT maximum of N_3–70 was identified later in autumn. In the boundary layer, seasonally maximum N_3–70 concentrations were found over Novosibirsk in May and September, but not in summer, possibly due to scavenging by precipitations and a large condensational sink from biomass burning aerosols. Our dataset has a limited size resolution and no speciation capability; more investigation is thus required to understand the conditions leading to in situ nucleation processes in the Siberian air shed.     

Photochemical oxidation of halocarbons in the troposphere

Measurements of the reactivity of hydroxyl radicals with some simple halocarbons are reported, together with some new measurements of the air concentration of halocarbons in the N-and S hemisphere. The OH reactivities are used to derive life-times of the halocarbons with respect to photooxidation in the troposphere. It is found that the chlorohydrocarbons containing H atoms are moderately reactive with lifetimes of 1 y or less but the fully halogenated compounds carbon tetrachloride and Freons 11 and 12 are essentially inert towards photo-oxidation.The air concentration and reactivity data are combined to provide an estimate of the magnitude of the tropospheric sink for the halocarbons due to oxidation by OH radicals. For some of the more reactive halocarbons this sink exceeds the estimated anthropogenic emissions and an additional, possibly natural, source is indicated.     

Temperature modeling in activated sludge systems: a case study.

A model of temperature dynamics was developed as part of a general model of activated-sludge reactors. Transport of heat was described by the one-dimensional, advection-dispersion equation, with a source term based on a theoretical heat balance over the reactor. The model was compared to several reference models, including a tanks-in-series model and the dispersion model with heat components neglecting biochemical-energy inputs and other activated-sludge, heat-balance terms. All the models were tested under steady-state and dynamic conditions at a full-scale facility, the Rock Creek wastewater treatment plant in Hillsboro, Oregon, using meteorological data from a station located 16 km from the plant. The dispersion model and tanks-in-series model matched in situ temperature data with absolute-mean errors less than 0.1 degrees C. Neglecting biochemical-heat-energy inputs in the activated-sludge reactor underestimated temperatures by up to 0.5 degrees C. The biochemical-heat-energy inputs accounted for 30 to 40% of the total heat flux throughout the year.     

Sulfur dioxide measurements in the lower,middle and upper troposphere: Deployment of an aircraft-based chemical ionization mass spectrometer with permanent in-flight calibration

Measurements of atmospheric SO₂ have been made at altitudes between ground level and 12 km in the lower, middle and upper troposphere. The measurements were carried out within the framework of the ITOP (Intercontinental Transport of Ozone and Precursors) campaign in summer 2004 above Europe and the Eastern Atlantic. They were made using a novel very sensitive and fast-response aircraft-based ion trap CIMS instrument (ITCIMS; CIMS=chemical ionization mass spectrometry), which was continuously calibrated using isotopically labelled SO₂. During a total of eight flights of the research aircraft FALCON (DLR) air masses of different origin and different degree of pollution, indicated by measured elevated atmospheric SO₂ mole fractions, were intercepted. Often elevated concentrations of SO₂, which stemmed from North America were observed over Europe and the eastern Atlantic.     

Chemistry of HOx radicals in the upper troposphere

Aircraft observations from three recent missions (STRAT, SUCCESS, SONEX) are synthesized into a theoretical analysis of the factors controlling the concentrations of HO_x radicals (HO_x=OH+peroxy) and the larger reservoir family HO_y (HO_y=HO_x+2H₂O₂+2CH₃OOH+HNO₂+HNO₄) in the upper troposphere. Photochemical model calculations capture 66% of the variance of observed HO_x concentrations. Two master variables are found to determine the variance of the 24 h average HO_x concentrations: the primary HO_x production rate, P(HO_x), and the concentration of nitrogen oxide radicals (NO_x=NO+NO₂). We use these two variables as a coordinate system to diagnose the photochemistry of the upper troposphere and map the different chemical regimes. Primary HO_x production is dominated by the O(¹D)+H₂O reaction when [H₂O]>100 ppmv, and by photolysis of acetone (and possibly other convected HO_x precursors) under drier conditions. For the principally northern midlatitude conditions sampled by the aircraft missions, the HO_x yield from acetone photolysis ranges from 2 to 3. Methane oxidation amplifies the primary HO_x source by a factor of 1.1–1.9. Chemical cycling within the HO_x family has a chain length of 2.5–7, while cycling between the HO_x family and its HO_y reservoirs has a chain length of 1.6–2.2. The number of ozone molecules produced per HO_y molecule consumed ranges from 4 to 12, such that ozone production rates vary between 0.3 and 5 ppbv d⁻¹ in the upper troposphere. Three chemical regimes (NO_x-limited, transition, NO_x-saturated) are identified to describe the dependence of HO_x concentrations and ozone production rates on the two master variables P(HO_x) and [NO_x]. Simplified analytical expressions are derived to express these dependences as power laws for each regime. By applying an eigenlifetime analysis to the HO_x–NO_x–O₃ chemical system, we find that the decay of a perturbation to HO_y in the upper troposphere (as from deep convection) is represented by four dominant modes with the longest time scale being factors of 2–3 times longer than the steady-state lifetime of HO_y.     

Photodissociation of acetone in the troposphere: an algorithm for the quantum yield

Results of recent measurements of quantum yields for the photodissociation of acetone in air are evaluated to derive formulae for the dependence on wavelength and pressure. These are used to calculate acetone photodissociation coefficients in the troposphere. The results are compared to another algorithm suggested previously.     

Ozone formation in California's San Joaquin Valley: a critical assessment of modeling and data needs

Data from the 1990 San Joaquin Valley Air Quality Study/Atmospheric Utility Signatures, Predictions, and Experiments (SJVAQS/AUSPEX) field program in California's San Joaquin Valley (SJV) suggest that both urban and rural areas would have difficulty meeting an 8-hr average O3 standard of 80 ppb. A conceptual model of O3 formation and accumulation in the SJV is formulated based on the chemical, meteorological, and tracer data from SJVAQS/AUSPEX. Two major phenomena appear to lead to high O3 concentrations in the SJV: (1) transport of O3 and precursors from upwind areas (primarily the San Francisco Bay Area, but also the Sacramento Valley) into the SJV, affecting the northern part of the valley, and (2) emissions of precursors, mixing, transport (including long-range transport), and atmospheric reactions within the SJV responsible for regional and urban-scale (e.g., down-wind of Fresno and Bakersfield) distributions of O3. Using this conceptual model, we then conduct a critical evaluation of the meteorological model and air quality model. Areas of model improvements and data needed to understand and properly simulate O3 formation in the SJV are highlighted.     

Adsorption study for the removal of a basic dye: experimental and modeling

An effective adsorbent is developed from saw dust and its various adsorption characteristics are studied for removing a basic dye (crystal violet) from its aqueous solution. Equilibrium data are fitted to various adsorption isotherms. It is seen that about 341 mg of crystal violet can be removed using 1g of the adsorbent at 298 K. Kinetic study is also carried out to observe the effects of various process parameters viz. particle size of the adsorbent, initial concentration of the dye, temperature and adsorbent amount. A generalized two-resistance mass transfer model, which includes a film mass transfer coefficient (k(f)) and an internal effective diffusivity (Dp), is used to interpret the adsorption kinetic data. The model parameters (k(f) and Dp) are estimated by fitting the experimental data to the model. The evaluated parameters are used to predict the concentration profiles at various other operating conditions. The average deviation of the predicted values lies within 10% in all the cases. Sensitivity analysis is performed to observe the sensitivity of the model to the variations in the model parameters.     

In situ measurements of HNO3, NOy,NO, and O3 in the lower stratosphere and upper troposphere

In situ measurements of nitric acid (HNO₃), reactive nitrogen (NO_y), nitric oxide (NO), and ozone (O₃) made in the upper troposphere (UT) and lower stratosphere (LS) between 29° and 33°N latitudes during September 1999 are used to examine NO_y partitioning and correlations between the measured species in these regions. The fast-response (1 s) HNO₃ measurements are acquired with a new autonomous CIMS instrument. In the LS, HNO₃ accounts for the majority of NO_y, and the sum of HNO₃ and NO_x accounts for approximately 90% of NO_y. In the UT, the sum of HNO₃ and NO_x varies between 40% and 100% of NO_y. Both HNO₃ and NO_y are strongly positively correlated with O₃, with larger correlation slopes in the UT than in the LS. In the UT at low values of the quantity (NO_y–NO_x–HNO₃), it is uncorrelated with O₃, while at higher values, a positive correlation with O₃ is found. Of these two air mass types, those with higher (NO_y–NO_x–HNO₃) mixing ratios are likely associated with the presence of peroxyacetyl nitrate (PAN) that is produced by NO_x-hydrocarbon chemistry.     

Recent decline of methyl bromide in the troposphere

Atmospheric methyl bromide (CH₃Br) measured at a remote ground station in the Arctic (mid-1996 to early 2002) and in the free troposphere at mid-latitude (early 1999 to early 2002) showed a steady annual average decrease of 4–6%. The trend was consistent with a simulation of the response to the phase-out schedule of anthropogenic emissions under the Montreal Protocol and its amendments, suggesting that a decrease in CH₃Br abundance in the Northern Hemisphere of as much as 40% from the level of the early 1990s would be possible by the completion date of the program.     

Source apportionment of DDTs in maricultured fish: a modeling study in South China

Fish is one of the most important nutrition sources for humanity. Contaminant exposure risk in fish farming will eventually deliver to the crowd through diet. China is the largest fish producing as well as exporting country, where mariculture plays an important role in fish production, especially in South China. Previous investigations indicated that a variety of compartments in farming areas of South China Sea were polluted by persistent organic pollutants, including DDT (dichlorodiphenyltrichloroethane) and its derivatives, some of which is designated as DDTs. In the present study, Hailing Bay and Daya Bay of Guangdong Province, China, were selected as the study sites and DDTs as the target compounds. A fish enrichment model was developed to assess the relative contributions of various pathways to the mass loadings of DDTs in the fish. Average concentrations (and concentration ranges) of DDTs in various environmental compartments of Hailing Bay and Daya Bay were included in modeling and analysis. Modeling results indicated that fish food and seawater contributed approximately the same proportions for the DDTs in maricultured fish. Antifouling paint was supposed to be the primary source of water DDTs in mariculture zone of Hailing Bay and Daya Bay, which contributed 69 % of the total DDTs to the mariculture water. We suggest that in order to protect people from consuming highly contaminated maricuture zone fish, the most effective and feasible methods are using environment-friendly antifouling paint and applying less polluted fish food in the fish reproduction process.