NOx Emission Trends Research Articles

Multi-annual changes of NO<sub>x</sub> emissions in megacity regions: nonlinear trend analysis of satellite measurement based estimates

Abstract. Hazardous impact of air pollutant emissions from megacities on atmospheric composition on regional and global scales is currently an important issue in atmospheric research. However, the quantification of emissions and related effects is frequently a difficult task, especially in the case of developing countries, due to the lack of reliable data and information. This study examines possibilities to retrieve multi-annual NOx emissions changes in megacity regions from satellite measurements of nitrogen dioxide and to quantify them in terms of linear and nonlinear trends. By combining the retrievals of the GOME and SCIAMACHY satellite instrument data with simulations performed by the CHIMERE chemistry transport model, we obtain the time series of NOx emission estimates for the 12 largest urban agglomerations in Europe and the Middle East in the period from 1996 to 2008. We employ then a novel method allowing estimation of a nonlinear trend in a noisy time series of an observed variable. The method is based on the probabilistic approach and the use of artificial neural networks; it does not involve any quantitative a priori assumptions. As a result, statistically significant nonlinearities in the estimated NOx emission trends are detected in 5 megacities (Bagdad, Madrid, Milan, Moscow and Paris). Statistically significant upward linear trends are detected in Istanbul and Tehran, while downward linear trends are revealed in Berlin, London and the Ruhr agglomeration. The presence of nonlinearities in NOx emission changes in Milan, Paris and Madrid is confirmed by comparison of simulated NOx concentrations with independent air quality monitoring data. A good quantitative agreement between the linear trends in the simulated and measured near surface NOx concentrations is found in London.

Trans-Pacific transport of reactive nitrogen and ozone to Canada during spring

Abstract. We interpret observations from the Intercontinental Chemical Transport Experiment, Phase B (INTEX-B) in spring 2006 using a global chemical transport model (GEOS-Chem) to evaluate sensitivities of the free troposphere above the North Pacific Ocean and North America to Asian anthropogenic emissions. We develop a method to use satellite observations of tropospheric NO2 columns to provide timely estimates of trends in NOx emissions. NOx emissions increased by 33% for China and 29% for East Asia from 2003 to 2006. We examine measurements from three aircraft platforms from the INTEX-B campaign, including a Canadian Cessna taking vertical profiles of ozone near Whistler Peak. The contribution to the mean simulated ozone profiles over Whistler below 5.5 km is at least 7.2 ppbv for Asian anthropogenic emissions and at least 3.5 ppbv for global lightning NOx emissions. Tropospheric ozone columns from OMI exhibit a broad Asian outflow plume across the Pacific, which is reproduced by simulation. Mean modelled sensitivities of Pacific (30° N–60° N) tropospheric ozone columns are at least 4.6 DU for Asian anthropogenic emissions and at least 3.3 DU for lightning, as determined by simulations excluding either source. Enhancements of ozone over Canada from Asian anthropogenic emissions reflect a combination of trans-Pacific transport of ozone produced over Asia, and ozone produced in the eastern Pacific through decomposition of peroxyacetyl nitrates (PANs). A sensitivity study decoupling PANs globally from the model's chemical mechanism establishes that PANs increase ozone production by removing NOx from regions of low ozone production efficiency (OPE) and injecting it into regions with higher OPE, resulting in a global increase in ozone production by 2% in spring 2006. PANs contribute up to 4 ppbv to surface springtime ozone concentrations in western Canada. Ozone production due to PAN transport is greatest in the eastern Pacific; commonly occurring transport patterns advect this ozone northeastward into Canada. Transport events observed by the aircraft confirm that polluted airmasses were advected in this way.

Modeling Diesel Spray Flame Liftoff, Sooting Tendency, and NOx Emissions Using Detailed Chemistry With Phenomenological Soot Model

A detailed chemistry-based CFD model was developed to simulate the diesel spray combustion and emission process. A reaction mechanism of n-heptane is coupled with a reduced NOx mechanism to simulate diesel fuel oxidation and NOx formation. The soot emission process is simulated by a phenomenological soot model that uses a competing formation and oxidation rate formulation. The model is applied to predict the diesel spray lift-off length and its sooting tendency under high temperature and pressure conditions with good agreement with experiments of Sandia. Various nozzle diameters and chamber conditions were investigated. The model successfully predicts that the sooting tendency is reduced as the nozzle diameter is reduced and/or the initial chamber gas temperature is decreased, as observed by the experiments. The model is also applied to simulate diesel engine combustion under premixed charge compression ignition (PCCI) conditions. Trends of heat release rate, NOx, and soot emissions with respect to EGR levels and start-of-injection timings are also well predicted. Both experiments and models reveal that soot emissions peak when the start of injection (SOI) occurs close to TDC. The model indicates that low soot emission at early SOI is due to better oxidation while low soot emission at late SOI is due to less formation. Since NOx emissions decrease monotonically with injection retardation, a late injection scheme can be utilized for simultaneous soot and NOx reduction for the engine conditions investigated in this study.

Changes in the photochemical environment of the temperate North Pacific troposphere in response to increased Asian emissions

Measurements during the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) field study characterized the springtime, eastern Pacific ozone distribution at two ground sites, from the National Oceanic and Atmospheric Administration WP‐3D aircraft, and from a light aircraft operated by the University of Washington. D. Jaffe and colleagues compared the 2002 ozone distribution with measurements made in the region over the two previous decades and show that average ozone levels over the eastern midlatitude Pacific have systematically increased by ∼10 ppbv in the last two decades. Here we provide substantial evidence that a marked change in the photochemical environment in the springtime troposphere of the North Pacific is responsible for this increased O3. This change is evidenced in the eastern North Pacific ITCT 2K2 study region by (1) larger increases in the minimum observed ozone levels compared to more modest increases in the maximum levels, (2) increased peroxyacetyl nitrate (PAN) levels that parallel trends in NOx emissions, and (3) decreased efficiency of photochemical O3 destruction, i.e., less negative O3 photochemical tendency (or net rate of O3 photochemical production; P(O3)). This changed photochemical environment is hypothesized to be due to anthropogenic emissions from Asia, which are believed to have substantially increased over the two decades preceding the study. We propose that their influence has changed the springtime Pacific tropospheric photochemistry from predominately ozone destroying to more nearly ozone producing. However, chemical transport model calculations indicate the possible influence of a confounding factor; unusual transport of tropical air to the western North Pacific during one early field study may have played a role in this apparent change in the photochemistry.

00/03575 Modelling of combustion of low grade lignites in fluidized beds with heat extraction

Based on the flamelet concept, a numerical model has been developed for fast predictions of NOX and CO emissions from laminar flames. The model is applied to studying NO formation in the secondary nonpremixed flame zone of fuel-rich methane Bunsen flames. By solving the steady-state flamelet equations with the detailed GRI2.1 methane–air mechanism, a flamelet library is generated containing thermochemical information for a range of scalar dissipation rates at the ambient pressure condition. Modeling of NO formation is made by solving its conservation equation with chemical source term evaluated based on flamelet library using the extended Zeldovich mechanism and “NO reburning reactions.” The optically-thin radiation heat transfer model is used to explore the potential effect of heat loss on thermal NO formation. The numerical scheme solves the two-dimensional Navier–Stokes equations as well as three additional equations: the mixture fraction, the NO mass fraction, and the enthalpy deficit due to radiative heat loss. With an established flamelet library, typical computing times are about 5 hours per calculation on a DEC-3000 300LX workstation. The predicted mixing field, radial temperature profiles, and NO distributions compare favorably with recent experimental data obtained by Nguyen et al. [2]. The dependence of NOX emission on equivalence ratio is studied numerically and the predictions are found to agree reasonably well with the measurements by Muss [3]. The computed results show a decreasing trend of NOX emission with the equivalence ratio but an increasing trend in the CO emission index. By examining this trade-off between NOX and CO, an optimal equivalence ratio of 1.4 is found to yield the lowest combined emission.

Effects of oxygenated blending compounds on emissions from a turbocharged direct injection diesel engine

An experimental investigation was conducted to evaluate the effect of three different oxygenated compounds, diglyme, diethyl maleate and dibutyl maleate, on emissions from a Volkswagen 1.9 litre, turbocharged, direct injection diesel engine. Sampling was performed using a mini-dilution tunnel technique to obtain particulate matter and a Fourier transform infrared (FTIR) spectrometer for gaseous emissions. The particulate samples were analysed using thermal analysis and Soxhlet extraction to determine the fraction of volatile and soluble organic material respectively. All three oxygenated compounds were found to be effective at reducing particulate emissions, with the maleate compounds being more effective overall than the diglyme. Analysis of the relative contributions of changes in the soot and soluble organic fraction (SOF) to the reduction of particulate matter indicated that, for diethyl maleate and diglyme, reductions in soot were the dominant effect. No consistent trends in NOx emissions were observed, although the diethyl maleate, which was most effective at reducing the particulate matter, increased the NOx slightly at most of the test conditions. Differences in the combustion chemistry of the additives are discussed as a possible explanation of the greater effectiveness of the maleate compounds in reducing soot, as well as for the difference in the effectiveness of diethyl and dibutyl maleate.

Fuel Effect on Exhaust Emission of a Lean-Burn Spark-Ignition Engine.

Detailed composition of exhaust emission from various gaseous fuels and gasoline was obtained including unregulated species by using an FTIR analyser, and dependency of the composition mainly on equivalence ratio was compared paying emphasis on relation between NOx and unburned species. The results show that NO emission is increased when liquified petroleum gas and propane were used compared with the other gaseous fuels, and that NO2 concentration becomes comparable with NO when the charge mixture comes close to its lean limit. Trends of NOx and unburned hydrocarbon emissions are quantitatively similar for the gas fuels and gasoline, however, there are some differences on constituents in the unburned species.

A Semi-Analytical Finite Rate Two-Reactor Model for Gas Turbine Combustors

A gas turbine combustor is modeled using a two-reactor, finite-rate mixing and chemistry gas particle approach. The first reactor, used to simulate combustion in the primary zone, permits independent definition of the rates of macromixing and micromixing within the reactor, and the amount of premixing of fuel and air entering the reactor. Finite-rate macromixing is simulated by consideration of the fluid particle residence time distribution frequency function and the ages of the particles in the reactor. Finite-rate micromixing is simulated using a modified Coalescence-Dispersion (C-D) model. The second reactor model simulates combustion in the dilution zone of the combustor, and is modeled as a plug flow reactor with cross-flowing jets of dilution air and co-flowing streams of cooling film air. The primary zone reactor model predicts physically reasonable trends in mean temperature, and CO and NOx emissions as the macromixing and micromixing parameters are varied with respect to the perfectly stirred reactor limit. The model also has shown to predict the correct trends in modeling NOx and CO emissions from aircraft engine gas turbine combustors.

Verification of expected trends in urban traffic NOx emissions from long-term measurements of ambient NO2 concentrations in urban air

Data from long-term measurements of ambient NO2 concentrations at roof level in 15 Swedish cities have been used to verify expected trends in urban traffic NOx emission, resulting mainly from the growth in the number of threeway catalyst (TWC) cars in Sweden since the mid 1980s. The results show that, with few exceptions, all cities exhibit a highly significant downward trend in ambient NO2 concentration since the winter season 1986/1987, as regards both winter season averages and 98th percentiles of daily averages, with an average decrease in both cases of approximately 30% through the winter season 1993/1994. The same trend is also observed when meteorological variations between years are taken into account. Corrections for NO2 in background air yield an even stronger downward trend, or an average 40% decrease for the study period. Simultaneously, rough calculations indicate a 30% decrease in urban traffic NOx emissions during the study period. The conclusions are that, since emission calculations always involve a high degree of uncertainty, use of data from long-term measurements of NO2 concentrations in urban air can be very helpful in establishing real-world trends for urban traffic NOx emissions, as soon as NOx-levels are low enough for the NO + ozone reaction to become ‘NOx-limited’.

Bodennahes Ozon: Trends in Bayern

Long-term ground-based measurements of ozone in Bavaria (Germany) are evaluated in respect of their trend during the last 20 years. First a method is described to characterize the measuring-sites in relation to the levels of precursors: The derived division in three classes proved its worth interpreting the results. Following, the trend of ozone-concentration are calculated by linear regression analysis and are tested in respect of their significance. Generally the Bavarian results fit in the trends of a long-term increase of ozone-concentrations observed at several central European stations. In detail, there are differences between stations situated at elevated sites or at other sites without traffic (class I) and stations situated at sites with significant influence of nearby traffic (classes II and III). At stations of class I an increase of ozone until the mid 80’s is recorded. Afterwards this trend seems to be stopped. But at the stations of classes II and III an increase of ozone is occuring only since the mid 80’s. The observed trends are correlated with the trends of NOx-emissions.