Quantification of Hourly Variability in NOx Emissions for Baseload Coal-Fired Power Plants

Abstract

The objectives of this paper are to (1) quantify variability in hourly utility oxides of nitrogen (NO_x) emission factors, activity factors, and total emissions; (2) investigate the autocorrelation structure and evaluate cyclic effects at short and long scales of the time series of total hourly emissions; (3) compare emissions for the ozone (O₃) season versus the entire year to identify seasonal differences, if any; and (4) evaluate interannual variability. Continuous emissions monitoring data were analyzed for 1995 and 1998 for 32 units from nine baseload power plants in the Charlotte, NC, airshed. Unit emissions have a strong 24-hr cycle attributable primarily to the capacity factor. Typical ranges of the coefficient of variation for emissions at a given hour of the day were from 0.2 to 0.45. Little difference was found when comparing weekend emissions with the entire week or when comparing the O₃ season with the entire year. There were substantial differences in the mean and standard deviation of emissions when comparing 1995 and 1998 data, indicative of the effect of retrofits of control technology during the intervening time. The wide range of variability and its autocorrelation should be accounted for when developing probabilistic utility emission inventories for analysis of near-term future episodes.     

Methods for Quantifying Variability and Uncertainty in AP-42 Emission Factors: Case Studies for Natural Gas-Fueled Engines

Abstract

Quantitative methods for characterizing variability and uncertainty were applied to case studies of oxides of nitrogen and total organic carbon emission factors for lean-burn natural gas-fueled internal combustion engines. Parametric probability distributions were fit to represent inter-engine variability in specific emission factors. Bootstrap simulation was used to quantify uncertainty in the fitted cumulative distribution function and in the mean emission factor. Some methodological challenges were encountered in analyzing the data. For example, in one instance, five data points were available, with each data point representing a different market share. Therefore, an approach was developed in which parametric distributions were fitted to population-weighted data. The uncertainty in mean emission factors ranges from as little as ~±10% to as much as -90 to 21+180%. The wide range of uncertainty in some emission factors emphasizes the importance of recognizing and accounting for uncertainty in emissions estimates. The skewness in some uncertainty estimates illustrates the importance of using numerical simulation approaches that do not impose restrictive symmetry assumptions on the confidence interval for the mean. In this paper, the quantitative method, the analysis results, and key findings are presented.     

小型燃油锅炉NOx的排放特征与管理控制

以68台燃油锅炉（≤10～MW）NOx排放实测数据为基础,通过统计分析方法,研究了NOx的排放特征;通过对比分析,探讨了我国燃油锅炉NOx排放控制与管理现状,讨论了进一步加强我国燃油锅炉NOx排放管理控制的可能性与可行性,并提出了相应的管理控制建议。结果表明,NOx平均排放浓度为318．2mg／m^3,基于燃料消耗量的平均排放因子为4．4kg／t,基于燃料发热量的平均排放因子为102．8ng／J,基于燃料氮含量的平均排放因子为2．1mg／mg;建议采取分阶段控制的方式,逐步提高NOx排放限制,从而实现控源减排目标。     

Anthropogenic emissions of SO2 and NOx in Asia: Emission inventories

The anthropogenic emissions of SO₂ and NO_x for 25 Asian countries east of Afghanistan and Pakistan have been calculated for 1975, 1980, 1985, 1986 and 1987 based on fuel consumption, sulfur content in fuels and emission factors for used fuels in each emission category. The provincial- and regional-based calculations have also been made for China and India. The total SO₂ emissions in these parts of Asia have been calculated to be 18.3 and 29.1 Tg in 1975 and 1987, respectively. The calculated total NO_x emissions were 9.4 and 15.5 Tg in 1975 and 1987, respectively. The SO₂ and NO_x emissions in East Asia (China, Japan, South Korea, North Korea and Taiwan) were 23.4 and 10.7 Tg in 1975 and 1987, respectively.Keyword: Emission inventories, sulfur dioxide emissions, nitrogen oxide emissions, Asian emissions, anthropogenic emissions.     

Quantification of variability and uncertainty in lawn and garden equipment NOx and total hydrocarbon emission factors

Variability refers to real differences in emissions among multiple emission sources at any given time or over time for any individual emission source. Variability in emissions can be attributed to variation in fuel or feedstock composition, ambient temperature, design, maintenance, or operation. Uncertainty refers to lack of knowledge regarding the true value of emissions. Sources of uncertainty include small sample sizes, bias or imprecision in measurements, nonrepresentativeness, or lack of data. Quantitative methods for characterizing both variability and uncertainty are demonstrated and applied to case studies of emission factors for lawn and garden (L&G) equipment engines. Variability was quantified using empirical and parametric distributions. Bootstrap simulation was used to characterize confidence intervals for the fitted distributions. The 95% confidence intervals for the mean grams per brake horsepower/hour (g/hp-hr) emission factors for two-stroke engine total hydrocarbon (THC) and NOx emissions were from -30 to +41% and from -45 to +75%, respectively. The confidence intervals for four-stroke engines were from -33 to +46% for THCs and from -27 to +35% for NOx. These quantitative measures of uncertainty convey information regarding the quality of the emission factors and serve as a basis for calculation of uncertainty in emission inventories (EIs).     

实际工况下内河航行船舶NOx排放测试与分析

为获得NOx的排放特征,利用便携式排放测试系统（PEMS）对7艘京杭运河中航行的内河船舶进行了实际工况下的排放测试。测量结果表明：进、离港工况下NO和NO2的浓度波动明显,而在巡航工况下NO浓度保持稳定且处于较高的排放水平。巡航工况下NO的基于时间的平均排放因子分别是进港和离港工况排放因子的3.22倍和1.74倍。而NO2离港工况下的平均排放因子分别是巡航工况和进港工况下的平均排放因子1.18倍和1.96倍。受到航行距离的影响,进港工况下NO和NO2基于距离的平均排放因子高于其他2个工况下的排放因子。当发动机处于高转速时,NO的排放因子最高,而NO2则在中转速下的排放因子最高。     

Quantification of variability and uncertainty in air pollutant emission inventories: method and case study for utility NOx emissions

The quality of stationary source emission factors is typically described using data quality ratings, which provide no quantification of the precision of the emission factor for an average source, nor of the variability from one source to another within a category. Variability refers to actual differences caused by differences in feedstock composition, design, maintenance, and operation. Uncertainty refers to lack of knowledge regarding the true emissions. A general methodology for the quantification of variability and uncertainty in emission factors, activity factors, and emission inventories (EIs) is described, featuring the use of bootstrap simulation and related techniques. The methodology is demonstrated via a case study for a selected example of NOx emissions from coal-fired power plants. A prototype software tool was developed to implement the methodology. The range of interunit variability in selected activity and emission factors was shown to be as much as a factor of 4, and the range of uncertainty in mean emissions is shown to depend on the interunit variability and sample size. The uncertainty in the total inventory of -16 to +19% was attributed primarily to one technology group, suggesting priorities for collecting data and improving the inventory. The implications for decision-making are discussed.     

Factors Influencing the Variability of SO2 Concentrations in Istanbul

ABSTRACT

The correlation between sulfur dioxide (SO₂) concentrations measured at the European and Asian sides of Istanbul and meteorological parameters is investigated using principal component analysis (PCA) and multiple regression analysis techniques. Several meteorological parameters are selected to represent the atmospheric conditions during two winter periods: 1993–1994 and 1994–1995. Six principal components are found to explain the majority of the observed meteorological variability. Surface pressure, 850-mb temperature, and surface zonal (east-west) and meridional (north-south) winds show high loadings on separate factors identified by PCA. We seek dominant meteorological parameters that control the SO₂ levels at each monitoring station. Several multiple regression analysis models are fitted to the data from each monitoring station using six principal components and previous day SO₂ concentrations as independent variables.

Results suggest that the most important parameters, highly correlated with SO₂ concentrations in the Istanbul metropolitan area, are atmospheric pressure and surface zonal and meridional winds. These components have more influence on the determination of the air pollution levels at the Asian side than at the European side.     

Uncertainty Analysis of Ozone Formation and Response to Emission Controls Using Higher-Order Sensitivities

Abstract

Understanding ozone response to its precursor emissions is crucial for effective air quality management practices. This nonlinear response is usually simulated using chemical transport models, and the modeling results are affected by uncertainties in emissions inputs. In this study, a high ozone episode in the southeastern United States is simulated using the Community Multiscale Air Quality (CMAQ) model. Uncertainties in ozone formation and response to emissions controls due to uncertainties in emission rates are quantified using the Monte Carlo method. Instead of propagating emissions uncertainties through the original CMAQ, a reduced form of CMAQ is formulated using directly calculated first- and second-order sensitivities that capture the nonlinear ozone concentration-emission responses. This modification greatly reduces the associated computational cost. Quantified uncertainties in modeled ozone concentrations and responses to various emissions controls are much less than the uncertainties in emissions inputs. Average uncertainties in modeled ozone concentrations for the Atlanta area are less than 10% (as measured by the inferred coefficient of variance [ICOV]) even when emissions uncertainties are assumed to vary between a factor of 1.5 and 2. Uncertainties in the ozone responses generally decrease with increased emission controls. Average uncertainties (ICOV) in emission-normalized ozone responses range from 4 to 22%, with the smaller being associated with controlling of the relatively certain point nitrogen oxide (NO_x) emissions and the larger resulting from controlling of the less certain mobile NO_x emissions. These small uncertainties provide confidence in the model applications, such as in performance evaluation, attainment demonstration, and control strategy development.     

Emission Factors of Air Toxics from Semiconductor Manufacturing in Korea

Abstract

The development of local, accurate emission factors is very important for the estimation of reliable national emissions and air quality management. For that, this study is performed for pollutants released to the atmosphere with source-specific emission tests from the semiconductor manufacturing industry. The semiconductor manufacturing industry is one of the major sources of air toxics or hazardous air pollutants (HAPs); thus, understanding the emission characteristics of the emission source is a very important factor in the development of a control strategy. However, in Korea, there is a general lack of information available on air emissions from the semiconductor industry. The major emission sources of air toxics examined from the semiconductor manufacturing industry were wet chemical stations, coating applications, gaseous operations, photolithography, and miscellaneous devices in the wafer fabrication and semiconductor packaging processes. In this study, analyses of emission characteristics, and the estimations of emission data and factors for air toxics, such as acids, bases, heavy metals, and volatile organic compounds from the semiconductor manufacturing process have been performed. The concentration of hydrogen chloride from the packaging process was the highest among all of the processes. In addition, the emission factor of total volatile organic compounds (TVOCs) for the packaging process was higher than that of the wafer fabrication process. Emission factors estimated in this study were compared with those of Taiwan for evaluation, and they were found to be of similar level in the case of TVOCs and fluorine compounds.     

Atmospheric Sample Pumps —A Possible Source of Error in Total Hydrocarbon,Methane, and Carbon Monoxide Measurement

Errors in measurement due to the use of pressure pumps to feed atmospheric samples to combination total hydrocarbon, methane, and carbon monoxide detectors are pointed out. The type of errors involved are detected only by a comparison study of monitors. The use of vacuum pumps as a superior method of sample introduction is discussed.     

我国氮氧化物排放因子的修正和排放量计算:2000年

根据我国城市的发展状况 ,采用城市分类的方法 ,将我国 2 6 1个地级市按照人口数量分为 5个类别。每类城市选取一个典型城市进行实地调查 ,对我国燃烧锅炉和机动车的NOx 的排放因子进行了修正 ,提出了适合我国目前排放水平的各类城市的固定源和移动源的排放因子。并依据 2 0 0 0年中国大陆地区的电站锅炉、工业锅炉和民用炉具的燃料消耗量和机动车保有量 ,以地级市为基本单位 ,估算了 2 0 0 0年我国各地区的NOx 排放量 ,分析了分地区、分行业、分燃料类型的NOx 排放特征。 2 0 0 0年我国NOx 排放总量为 11.12Mt,其中固定源占 6 0 .8% ;移动源占 39.2 %。NOx 排放在地域、行业和燃料类型上分布均不平衡。NOx 的排放主要集中在华东和华北地区 ,其排放量占全国排放量的一半以上。燃煤为最重要的NOx 排放源 ,其排放量占燃料型NOx 排放量的 72 .3%左右。     

Observations and Model Simulations of Carbon Monoxide Emission Factors from a California Highway

ABSTRACT

A series of twelve intensively monitored 1-hr CO dispersion studies were conducted near Davis, CA, in winter 1996. The experimental equipment included twelve CO sampling ports at elevations up to 50 m, three sonic anemometers, a tethersonde station, aircraft measurements of wind and temperature profile aloft, and a variety of conventional meteorological equipment. The study was designed to explore the role of vehicular exhaust buoyancy during worst-case meteorological conditions, such as low winds oriented in near-parallel alignment with the road during a surface-based nocturnal inversion. From the study, field estimates of the CO emission factor (EF) from a California vehicle fleet were computed using two different methods. The analysis suggests that the CT-EMFAC/ EMFAC (EMission FACtor) models currently used to conduct federal conformity modeling significantly overpredict CO emissions for high-speed, free-flowing traffic on California highways.     

Ammonia Flux from Open-Lot Dairies: Development of Measurement Methodology and Emission Factors

Abstract

Ammonia emissions contribute to the formation of secondary particulate matter (PM) and violations of the National Ambient Air Quality Standard. Ammonia mass concentration measurements were made in February 1999 upwind and downwind of an open-lot dairy in California, using a combination of active bubbler and passive filter samplers. Ammonia fluxes were calculated from concentrations measured at 2, 4, and 10 m above ground at three locations on the downwind edge of the dairy, using micrometeorological techniques. A new method was developed to interpolate fluxes at six additional locations from ammonia concentrations measured at a single height, providing measurements at sufficient spatial resolution along the downwind border of the dairy to account for the heterogeneity of the source. PM measured up- and downwind of the dairy demonstrated insignificant ammonium particle formation in the immediate vicinity of the dairy and negligible contribution of dissociated ammonium nitrate to measured ammonia concentrations. Ammonium nitrate concentrations measured downwind of the dairy ranged from 26 to 0.26 μg m^?3 and from 2 to 43% of total PM_2.5 mass concentrations. Measured ammonia fluxes showed that liquid manure retention ponds represented relatively minor sources of ammonia in winter on the dairy studied. Ammonia emission factors derived from the measurements ranged from 19 to 143 g head^?1 day^?1, showing an increase with warmer, drier weather and a decrease with increased relative humidity and lower temperatures.     

Measurements of aromatic hydrocarbon ratios and NOx concentrations in the rural troposphere: Observation of air mass photochemical aging and NOx removal

Measurements of the aromatic hydrocarbons (benzene, toluene, ethylbenzene and ortho(o)-xylene) at Niwot Ridge, Colorado have shown distinct correlations between the ratios of the concentrations of these compounds and the degree of direct urban influence. The major atmospheric removal mechanism of aromatic hydrocarbons is reaction with the hydroxyl radical, OH. This allows the decrease in the ratios of aromatic hydrocarbon concentrations to be related to the transport time and average OH number density within an air mass, if assumptions are made concerning background sources of aromatic hydrocarbons. Measured ratios of aromatic compounds at this site, along with ratios reported for several cities in the western United States, and estimates of transport times from these cities were used to calculate temporally and spatially averaged OH number densities. Hydroxyl radical number density estimates using toluene-, ethylbenzene-, and o-xylene-to-benzene ratios, were 1.2 ± 0.6 × 10⁶, 1.0 ±0.8 × 10₆ and 0.48 ± 0.8 × 10⁶ molecules cm⁻³, respectively. Considering the uncertainties in the assumptions used in the above estimates, we obtain a diurnal-average upper limit of 2.4 × 10⁶ molecules cm⁻³. The correlations between measured ratios are found to yield slopes consistent with those predicted by experimental OH rate constants for benzene, toluene and ethylbenzene, and approximately a factor of two different in the case of benzene, toluene and o-xylene. The ratio of NO_x: benzene was found to yield no correlation with toluene: benzene ratio for periods of westerly flow, but was well correlated with toluene: benzene ratio during periods of direct urban impact on the site (upslope easterly winds). The correlation of these ratios in urban plume air masses was consistent with NO₂ + OH + M being the major daytime removal mechanism of NO_x in the summertime.     

奥里油燃烧过程中的NOx形成机理及控制技术

介绍了奥里油的特性及其在电厂中的应用情况，对奥里油燃烧过程中NOx的形成机理和影响因素作了初步分析，同时比较了燃烧粉煤、重油或奥里油时的NOx排放量，为我国开展相关研究提供了参考。     

中国钢铁行业NO_X减排情景预测

钢铁行业是NOX污染减排的重点领域。在预测钢铁行业未来发展趋势的基础上,基于情景分析法,设置3个NOX排放情景,估算出2020年不同情景下钢铁行业NOX排放量及不同控制措施的减排贡献。研究结果表明,未来钢铁行业产品产量的快速上涨加大了NOX减排压力。在不实施额外NOX控制措施的情况下,2020年钢铁行业NOX排放量约为108万t,相比2013年上涨9%。实施钢铁行业NOX排放控制措施可取得显著的减排效果,根据两种控制情景预计NOX的减排比例分别为5%和13%。淘汰落后产能和烧结烟气循环技术是NOX减排的最有效手段。     

Modelling the spatial distribution of SO2 and NOx emissions in Ireland

The spatial distributions of sulphur dioxide (SO2) and nitrogen oxides (NOx) emissions are essential inputs to models of atmospheric transport and deposition. Information of this type is required for international negotiations on emission reduction through the critical load approach. High-resolution emission maps for the Republic of Ireland have been created using emission totals and a geographical information system, supported by surrogate statistics and landcover information. Data have been subsequently allocated to the EMEP 50 x 50-km grid, used in long-range transport models for the investigation of transboundary air pollution. Approximately two-thirds of SO2 emissions in Ireland emanate from two grid-squares. Over 50% of total SO2 emissions originate from one grid-square in the west of Ireland, where the largest point sources of SO2 are located. Approximately 15% of the total SO2 emissions originate from the grid-square containing Dublin. SO2 emission densities for the remaining areas are very low, < 1 t km-2 year-1 for most grid-squares. NOx emissions show a very similar distribution pattern. However, NOx emissions are more evenly spread over the country, as about 40% of total NOx emissions originate from road transport.     

城郊气象因素与NOx、PM10的多重分形分析

针对城区和郊区气象因素与NOx、PM10浓度间的互相关性的特征,采用多重分形去趋势波动互相关分析法（MF-DCCA）,对气象因素与NOx、PM10浓度时间序列进行研究。首先验证了温度与NOx、PM10具有互相关性和多重分形特征,然后,逐次分析城区和郊区在夏冬两季温度、湿度、风速、气压与NOx、PM10的多重分形特征。结果表明,城区天气因素与PM10、NOx的多重分形特征要强于郊区,两地天气因素对PM10的影响程度要强于对NOx的程度,城区和郊区夏季的天气因素与PM10的多重分形特征均强于冬季。     

Interlaboratory and Intralaboratory Variability in the Analysis of Mercury in Coal

Abstract

With the passage of the 1990 Clean Air Act Amendments (CAAA), accurate determination of the concentration of mercury in coal has become an increasingly important issue. To address this issue, CONSOL R&D conducted a round robin analytical program to determine the interlaboratory and intralaboratory variability in the measurement of mercury in coal. CONSOL supplied homogeneous splits of Pittsburgh and Illinois #6 seam coals, and the NIST 1632b coal standard to eleven laboratories, twice each, over a one-year period. A twelfth laboratory analyzed the coals once. A European coal standard, certified for mercury, was analyzed at the completion of the round robin study to evaluate accuracy. The round robin participants included representatives from industry, government, and academia. The laboratories, which are experienced in mercury-in-coal analysis, used various state-of-the-art sample preparation and analysis procedures in the study. The round robin results indicate that a substantial level of variability exists in the mercury-in-coal determination. Earlier studies1 found similar results. The relative intralaboratory repeatability was 0.02 ppm and the relative interlaboratory reproducibility ranged from 0.04 to 0.05 ppm. The study showed that laboratory variability can be greatly skewed by outlier values. Fifty-six percent of the results for the European coal standard fell within a 95% confidence interval of the standard (0.138 ± 0.11 ppm). These results indicate that accuracy is not method-dependent.