Transport and transformation of sulfur compounds over East Asia during the TRACE-P and ACE-Asia campaigns

On the basis of the recently estimated emission inventory for East Asia with a resolution of 1×1°, the transport and chemical transformation of sulfur compounds over East Asia during the period of 22 February through 4 May 2001 was investigated by using the Models-3 Community Multi-scale Air Quality (CMAQ) modeling system with meteorological fields calculated by the regional atmospheric modeling system (RAMS). For evaluating the model performance simulated concentrations of sulfur dioxide (SO₂) and aerosol sulfate (SO₄²⁻) were compared with the observations on the ground level at four remote sites in Japan and on board aircraft and vessel during the transport and chemical evolution over the Pacific and Asian Pacific regional aerosol characterization experiment field campaigns, and it was found that the model reproduces many of the important features in the observations, including horizontal and vertical gradients. The SO₂ and SO₄²⁻ concentrations show pronounced variations in time and space, with SO₂ and SO₄²⁻ behaving differently due to the interplay of chemical conversion, removal and transport processes. Analysis of model results shows that emission was the dominant term in regulating the SO₂ spatial distribution, while conversion of SO₂ to SO₄²⁻ in the gas phase and the aqueous phase and wet removal were the primary factors that controlled SO₄²⁻ amounts. The gas phase and the aqueous phase have the same importance in oxidizing SO₂, and about 42% sulfur compounds (25% in SO₂) emitted in the model domain was transported out, while about 57% (35% by wet removal processes) was deposited in the domain during the study period.     

Modeling of Sulfur Dioxide Emissions and Acidic Precipitation at Mesoscale Distances

A steady state mesoscale model developed to predict primary SO₂ concentrations from a single point source is presented. The model was validated with data from the Midwest Interstate Sulfur Transport and Transformation (MISTT) project, with root mean square errors of 9.69 μg m^?3 and 0.42 μg m^?3 for SO₂ and SO₄ respectively. Wet deposition (washout and rainout), eddy dispersivity, dry deposition of SO₂ and mean wind speed were found to be the most important factors controlling sulfur dioxide and sulfate concentrations. Estimation of precipitation acidity was then carried out using scavenging theory. The greatest potential acidification occurred approximately 200 km from the source along plume centerllne, which indicates a rather local effect as opposed to a long distance effect. The cross-plume influence was up to 60 km in width at a distance of 400 km from the source.     

Application of the nested grid STEM to an early summer acid rain in South Korea

The nested grid Sulfur Transport Eulerian Model (STEM) was developed and used to simulate the acid rain in Korea that occurred on 10 June 1996. The present nested grid system consists of three-grid systems. The coarsest grid system includes China, Korean Peninsula and Japan with the horizontal grid size of 80 km and the finest grid system includes only Korea with the horizontal grid size of 8.9 km. The calculated gas-phase SO₂ and O₃ concentrations agree relatively well with the field measurements. In addition, the model successfully reproduces the measured sulfate and nitrate concentrations in the rain water and futhermore identified the high concentration regions of liquid-phase sulfate and nitrate. In the present simulation conditions, most of the gas-phase of SO₂ and HNO₃ were washed out. A close relationship between wet deposition fluxes and precipitation rates were found for sulfate and nitrate. Finally, the model results also showed that a fine grid size is required to accurately calculate gas-phase concentrations as well as acid deposition fluxes.     

Effects of the density of meteorological observations on the diagnostic wind fields and the performance of photochemical modeling in the greater Seoul area

The high ozone episode in the greater Seoul area (GSA) for the period of 27 July–1 August 1997 was modeled by the California Institute of Technology (CIT) three-dimensional photochemical model. During the period, ozone concentrations around 140 ppb were observed for 2 days. Two sets of diagnostic wind fields were constructed by using observations from the weather stations operated by the Korea Meteorological Administration. One set of wind fields utilized only observations from the surface weather stations (SWS) and the other set also utilized observations from the automatic weather stations (AWS) that were more densely distributed than the SWS. The results showed that utilizing observations from the AWS could represent fine variations in the wind field such as those caused by topography. A better wind field gave a more reasonable spatial distribution of ozone concentrations. The model performance of ozone prediction was also improved to some extent, but only marginally acceptable owing to large day-to-day variations. Overshoots of primary pollutants particularly for NO₂ were observed as pollutants were accumulated where low wind speeds were maintained. More precise information on diurnal and daily variations in emissions was warranted in order to better model the photochemical phenomena over the GSA.     

The NOAA Twin Otter and its role in BRACE: A comparison of aircraft and surface trace gas measurements

A DeHavilland DHC-6 Twin Otter, operated by the National Oceanic and Atmospheric Administration, was deployed in Tampa, FL to measure aerosols and primary and secondary trace gases in support of the Bay Regional Atmospheric Chemistry Experiment (BRACE). The Twin Otter repeatedly overflew the surface chemistry monitoring super site near Sydney, FL to assess the comparability of surface and airborne datasets and the spatial representativeness of the surface measurements. Prior to comparing the chemical datasets, we evaluated the comparability of the standards used to calibrate surface and airborne detectors, as well as the uniformity of wind fields aloft and at the surface. Under easterly flow, when the dearth of significant upwind emission sources promoted chemical homogeneity at Sydney, trace gas concentrations at the surface and aloft were generally well correlated; R² ranged from 0.4396 for H₂O₂ to 0.9738 for O₃, and was typically better than 0.70 for NO, NO₂, NO_Y, HNO₃, HCHO, and SO₂. Mean ratios of aircraft-to-surface concentrations during 10 overflights of Sydney were as follows: 1.002±0.265 (NO), 0.948±0.183 (NO₂), 1.010±0.214 (NO_Y), 0.941±0.263 (HCHO), and 0.952±0.046 (O₃). Poorer agreement and larger variability in measured ratios were noted for SO₂ (1.764±0.559), HNO₃ (1.291±0.391), and H₂O₂ (1.200±0.657). Under easterly flow, surface measurements at Sydney were representative of conditions over horizontal scales as large as 50 km and agreed well with airborne values throughout the depth of the turbulently mixed boundary layer at mid-day. Westerly flow advected the Tampa urban plume over the site; under these conditions, as well as during transitional periods associated with the development of the land–sea breeze, surface conditions were representative of smaller spatial scales. Finally, we estimate possible errors in future measurement-model comparisons likely to arise from fine scale (or subgrid;<2 km) variability of trace gas concentrations. Large subgrid variations in concentration fields were observed downwind of large emission point sources, and persisted across multiple model grid cells (distances>4 km) in coherent plumes. Variability at the edges of the well-mixed urban plume, and at the interface of the land–sea breeze circulation, was significantly smaller. This suggests that even a failure of modeled wind fields to resolve the sea breeze return can induce moderate, but not overwhelming, errors in simulated concentration fields and dependent chemical processes.     

WRF-Chem simulation of East Asian air quality: Sensitivity to temporal and vertical emissions distributions

This study develops fine temporal (seasonal, day-of-week, diurnal) and vertical allocations of anthropogenic emissions for the TRACE-P inventory and evaluates their impacts on the East Asian air quality prediction using WRF-Chem simulations in July 2001 at 30-km grid spacing against available surface measurements from EANET and NEMCC. For NO₂ and SO₂, the diurnal and vertical redistributions of emissions play essential roles, while the day-of-week variation is less important. When all incorporated, WRF-Chem best simulates observations of surface NO₂ and SO₂ concentrations, while using the default emissions produces the worst result. The sensitivity is especially large over major cities and industrial areas, where surface NO₂ and SO₂ concentrations are reduced by respectively 3–7 and 6–12 ppbv when using the scaled emissions. The incorporation of all the three redistributions of emissions simulates surface O₃ concentrations higher by 4–8 ppbv at night and 2–4 ppbv in daytime over broad areas of northern, eastern and central China. To this sensitivity, the diurnal redistribution contributes more than the other two.     

旋转填料床/柠檬酸盐法吸收-解吸SO2

提出采用旋转填料床结合柠檬酸盐法脱除烟气中SO2的方法,考察了旋转填料床转子转速、液气比、初始柠檬酸根浓度和初始pH值等因素对脱硫效率的影响。结果表明,采用超重力法超重机转子转速为1 000 r/min、液气比为7L/m3、初始柠檬酸根浓度为1.5 mol/L、吸收液的初始pH值为5.0,脱硫效率稳定在99%左右。研究了水蒸气汽提法解吸SO2时初始柠檬酸根浓度、初始pH值、SO2浓度、富液流量和水蒸气流量对解吸效率的影响,得出了影响SO2解吸率的基本规律,并进行了分析。通过实验证明该方法在技术上是可行的,具有良好的应用前景。     

Assessment of pollutant fluxes across the frontiers of the Federal Republic of Germany on the basis of aircraft measurements

Forty operational measurements by aircraft are described, which were performed during 1985–1987. The purpose was to obtain an overall picture of transboundary transports of SO₂, NO_x sulfate, nitrate and O₃ between the F.R.G. and its neighbours. Transboundary fluxes were calculated by means of measurement results with respect to the concentrations of the considered pollutants, depth of the planetary boundary layer, wind speed and wind direction. The largest SO₂ fluxes have been observed across the eastern border of the F.R.G., during periods characterized by easterly winds (300–2500 ton SO₂ h⁻¹ across a 500–600 km border section). The major fraction of this SO₂ appeared to have originated from the easterly neighbours of the F.R.G. and to a lesser extent also from countries further eastward. During easterly winds it has been observed that SO₂, which originated from countries east of the F.R.G., contributed considerably to SO₂ fluxes across the western border to countries west of the F.R.G. The results of the measurement flights as presented have provided valuable indications about transboundary transports of pollutants despite considerable uncertainties in the fluxes due to inaccuracies in the concentration profiles, wind data and depth of the planetary boundary layer.     

A model of wet deposition to complex terrain

A two dimensional model of the seeder-feeder mechanism of orographic rainfall enhancement has been developed. The model has been extended to include the deposition of aerosol material incorporated into the orographic feeder cloud by nucleation scavenging. Parameterizations of any changes in the concentration of SO₄²⁻ in the cloud due to chemical reactions have also been included. The model is used to predict the rainfall enhancement and SO₄²⁻ deposition over terrain consisting of two parallel ridges oriented perpendicular to the wind. A wide range of spatial scales has been used of up to 150 km. It is found that the patterns of rainfall enhancement and deposition are strongly dependent on the spatial scales, the atmospheric structure and the cloud chemistry.     

Using pollution roses to assess sulfur dioxide impacts in a township downwind of a petrochemical complex

This study used pollution roses to assess sulfur dioxide (SO₂) pollution in a township downwind of a large petrochemical complex based on data collected from a single air quality monitoring station. The pollution roses summarized hourly SO₂ concentrations at the Taishi air quality monitoring station, located approximately 7.8–13.0 km south of the No. 6 Naphtha Cracking Complex in Taiwan, according to 36 sectors of wind direction during the preoperational period (1995–1999) and two postoperational periods (2000–2004 and 2005–2009). The 99th percentile of hourly SO₂ concentrations 350? downwind from the complex increased from 28.9 ppb in the preoperational period to 86.2–324.2 ppb in the two postoperational periods. Downwind SO₂ concentrations were particularly high during 2005–2009 at wind speeds of 6–8 m/sec. Hourly SO₂ levels exceeded the U.S. Environmental Protection Agency (EPA) health-based standard of 75 ppb only in the postoperational periods, with 65 exceedances from 0–10? and 330–350? downwind directions during 2001–2009. This study concluded that pollution roses based on a single monitoring station can be used to investigate source contributions to air pollution surrounding industrial complexes, and that it is useful to combine such directional methods with analyses of how pollution varies between different wind speeds, times of day, and periods of industrial development.

Implications: The pollution roses summarize SO₂ concentrations by wind direction and to investigate source contribution to air quality. Percentile statistics can catch pollution episodes occurring in a very short time at specific wind directions and speeds. The downwind areas have already exceeded regulated 1-hr SO₂ standard since the operation of the complex.     

Evaluation of low wind modeling approaches for two tall-stack databases

The performance of the AERMOD air dispersion model under low wind speed conditions, especially for applications with only one level of meteorological data and no direct turbulence measurements or vertical temperature gradient observations, is the focus of this study. The analysis documented in this paper addresses evaluations for low wind conditions involving tall stack releases for which multiple years of concurrent emissions, meteorological data, and monitoring data are available. AERMOD was tested on two field-study databases involving several SO₂ monitors and hourly emissions data that had sub-hourly meteorological data (e.g., 10-min averages) available using several technical options: default mode, with various low wind speed beta options, and using the available sub-hourly meteorological data. These field study databases included (1) Mercer County, a North Dakota database featuring five SO₂ monitors within 10 km of the Dakota Gasification Company’s plant and the Antelope Valley Station power plant in an area of both flat and elevated terrain, and (2) a flat-terrain setting database with four SO₂ monitors within 6 km of the Gibson Generating Station in southwest Indiana. Both sites featured regionally representative 10-m meteorological databases, with no significant terrain obstacles between the meteorological site and the emission sources. The low wind beta options show improvement in model performance helping to reduce some of the overprediction biases currently present in AERMOD when run with regulatory default options. The overall findings with the low wind speed testing on these tall stack field-study databases indicate that AERMOD low wind speed options have a minor effect for flat terrain locations, but can have a significant effect for elevated terrain locations. The performance of AERMOD using low wind speed options leads to improved consistency of meteorological conditions associated with the highest observed and predicted concentration events. The available sub-hourly modeling results using the Sub-Hourly AERMOD Run Procedure (SHARP) are relatively unbiased and show that this alternative approach should be seriously considered to address situations dominated by low-wind meander conditions.

Implications: AERMOD was evaluated with two tall stack databases (in North Dakota and Indiana) in areas of both flat and elevated terrain. AERMOD cases included the regulatory default mode, low wind speed beta options, and use of the Sub-Hourly AERMOD Run Procedure (SHARP). The low wind beta options show improvement in model performance (especially in higher terrain areas), helping to reduce some of the overprediction biases currently present in regulatory default AERMOD. The SHARP results are relatively unbiased and show that this approach should be seriously considered to address situations dominated by low-wind meander conditions.     

A study of surface ozone and the relation to complex wind flow in Hong Kong

Ozone measurements made from 5 sites in Hong Kong have been analyzed, including those from one upwind, one downwind, and three urban locales. The data are analyzed in terms of the seasonal and diurnal trends. A subset of data in autumn is further analyzed to study the relationship between the ozone spatial pattern and wind flow as well as other meteorological parameters. The results show that averaged ozone levels at most sites exhibit maxima in autumn, which appears to be a unique feature for eastern Asia. On average the daily maximum 1-h concentrations are found to be higher in the western (normally downwind) site than those on the eastern side and in urban areas. Examination of surface wind patterns and other meteorological parameters suggest that elevated ozone concentrations on the western side occur during the days with intense solar radiation, light winds, and in the presence of a unique wind circulation. The wind reversal in the western parts under the “convergence” flow is believed to be an important cause of the high-ozone events observed there. Such wind flow may re-circulate/transport nearby urban plumes (in this case the Hong Kong–Shenzhen urban complex). Examination of chemical data from the western site has shown that averaged afternoon SO₂ to NO_x ratios on days with wind reversal are larger than those of typical urban Hong Kong and that a significant SO₂ enhancement was clearly indicated on several occasions. The SO₂ enhancement may be interpreted as being the evidence to suggest the contribution of regional sources and/or Hong Kong’s power plants (both containing high SO₂). A case study has shown that when moderately strong northwesterly wind prevails, elevated ozone and SO₂ can be transported to western Hong Kong from the inner Pearl Delta region. This study has also indicated that under the impact of ENE winds the eastern side of Hong Kong is not frequently affected by the re-circulating ozone plumes present in the western side.     

Opacity Reduction Using Dry Hydrated Lime Injection

Abstract

This investigation studied the effects of injecting dry hydrated lime into flue gas to reduce sulfur trioxide, (SO₃) concentrations and consequently stack opacity at the University of Missouri-Columbia power plant. The opacity was due to sulf uric acid mist forming at the stack from high SO₃ concentrations. As a result of light scattering by the mist, a visible plume leaves the stack. Therefore, reducing high concentrations of SO₃ reduces the sulfuric acid mist and consequently the opacity. To reduce SO₃ concentrations, dry hydrated lime is periodically injected into the flue gas upstream of a baghouse and downstream of an induced draft fan. The hydrated lime is transported downstream by the flue gas and deposited on the filter bags in the baghouse forming a filter cake. The reaction between the SO₃ and the hydrated lime takes place on the filter bags. The hydrated lime injection system has resulted in at least 95% reduction in the SO₃ concentration and has reduced the opacity to acceptable limits. Low capital equipment requirements, low operating cost, and increased bag life make the system very attractive to industries with similar problems.     

Anthropogenic sulphate aerosol from India: estimates of burden and direct radiative forcing

A one-box chemical-meteorological model had been formulated to make preliminary estimates of sulphate aerosol formation and direct radiative forcing over India. Anthropogenic SO₂ emissions from India, from industrial fuel use and biomass burning, were estimated at 2.0 Tg S yr^-1 for 1990 in the range of previous estimates of 1.54 and 2.55 Tg S yr ^-1 for 1987. Meteorological parameters for 1990 from 18 Indian Meteorological Department stations were used to estimate spatial average sulphate burdens through formation from SO₂ reactions in gas and aqueous phase and removal by dry and wet deposition. The hydrogen peroxide reaction was found dominating for undepleted oxidant-rich conditions. Monthly mean sulphate burdens ranged from 2–10 mg m^-2 with a seasonal variation of winter–spring highs and summer lows in agreement with previous GCM studies. The sulphate burdens are dominated by sulphate removal rates by wet deposition, which are high in the monsoon period from June–November. Monthly mean direct radiative forcing from sulphate aerosols is high (−3.5 and −2.3 W m^-2) in December and January, is moderate (−1.3 to −1.5 W m^-2) during February to April and November and low (−0.4 to −0.6 W m^-2) during May to October also in general agreement with previous GCM estimates. This model, in reasonable agreement with detailed GCM results, gives us a simple tool to make preliminary estimates of sulphate burdens and direct radiative forcing.     

Sulfur dioxide dispersion and source contribution to receptors of downtown Patras, Greece

Background The development of the city of Patras, including harbour relocation, in conjunction with the protection of the regional ecosystems, requires air quality assessment and management. For this reason, a model applicable in the Patras area is necessary and valuable. The goal of this study was to validate a model suitable for predicting the dispersion of sulfur dioxide (SO₂), based on particular activity, topography and weather conditions. Methods We used the US-EPA ISCLT3 integral dispersion model to predict SO₂ concentrations for Patras, Greece. We assumed that the major contribution to Patras air pollution came from central heating, harbour and traffic. We calculated traffic emissions using COPERTIII. Results and Discussion Assigning suitable values of the mixing height, the model predicted the local and spatial distribution of the mean monthly SO₂ concentrations in downtown Patras, as well computed the contribution of the SO₂ emissions originating from each particular source at each receptor location on a seasonal and annual basis. The comparison between predictions and measurements shows that the model performance for estimating the SO₂ concentrations and period pattern is satisfactory. Conclusion The mixing height was the critical parameter for calibrating the model. Model validation promises satisfactory predictions for SO₂ pollution levels on monthly basis. Recommendations and Outlook The model could be used in predicting SO₂ concentrations and source contribution for several downtown Patras receptors using pertinent meteorological and emission information. It could be also extended to predict the dispersion of other primary air pollutants. The calibrated model predictions could be used to fill gaps in monitoring data, saving money and time, and help in assess and manage air quality as Patras develops.     

A numerical model for the simulation of SO2 concentrations in the Kyongin region,Korea

A method for solving the non-reactive tracer continuity equation using a time splitting technique and a Galerkin technique with chapeau functions as finite elements for the horizontal advection has been developed and employed to simulate SO₂ concentrations in the Kyongin region in Korea for a synoptic case of high pollution potential days in autumn with the relatively strong southwesterly geostrophic wind at the 850 hPa pressure level. The paired comparisons between hourly observed and the simulated SO₂ concentrations are made to test the model performance. The result indicates that the present model simulates quite well horizontal distribution patterns of SO₂ concentration. However, the simulated concentrations depend largely on the emission rate, suggesting the importance of accurate source identification for the accurate simulation of the concentration field.     

Description and evaluation of a model of deposition velocities for routine estimates of dry deposition over North America. Part II: review of past measurements and model results

Numerical sensitivity tests and four months of complete model runs have been conducted for the Routine Deposition Model (RDM). The influence of individual model inputs on dry deposition velocity as a function of land-use category (LUC) and pollutant (SO₂, O₃, SO²⁻₄ and HNO₃) were examined over a realistic range of values for solar radiation, stability and wind speed. Spatial and temporal variations in RDM deposition velocity (V_d) during June – September 1996 time period generated using meteorological input from a mesoscale model run at 35 km resolution over north-eastern North America were also examined. Comparison of RDM V_d values to a variety of measurements of dry deposition velocities of SO₂, O₃, SO²⁻₄ and NHO₃ that have been reported in the literature demonstrated that RDM produces realistic results. Over northeastern NA RDM monthly averaged dry deposition velocities for SO₂ vary from 0.2 to 3.0 cm s⁻¹ with the highest deposition velocities over water surfaces. For O₃, the monthly averaged dry deposition velocities are from 0.05 to 1.0 cm s⁻¹ with the lowest values over water surfaces and the highest over forested areas. For HNO₃, the monthly averaged dry deposition velocities have the range of 0.5 to 6 cm s⁻¹, with the highest values for forested areas. For SO²⁻₄, they range from 0.05–1.5 cm s⁻¹, with the lowest values over water and the highest over forest. The monthly averaged dry deposition velocities for SO₂ and O₃ are higher in the growing season compared to the fall, but this behaviour is not apparent for HNO₃ and sulphate. In the daytime, the hourly averaged dry deposition velocities for SO₂, O₃, SO²⁻₄ and HNO₃ are higher than that in the nighttime over most of the vegetated area. The diurnal variation is most evident for surfaces with large values for leaf area index (LAI), such as forests. Based on the results presented in this paper, it is concluded that RDM V_d values can be combined with measured air concentrations over hourly, daily or weekly periods to determine dry deposition amounts and with wet deposition measurements to provide seasonal estimates of total deposition and estimates of the relative importance of dry deposition.     

A full year evaluation of the CALIOPE-EU air quality modeling system over Europe for 2004

The CALIOPE-EU high-resolution air quality modeling system, namely WRF-ARW/HERMES-EMEP/CMAQ/BSC-DREAM8b, is developed and applied to Europe (12 km × 12 km, 1 h). The model performances are tested in terms of air quality levels and dynamics reproducibility on a yearly basis. The present work describes a quantitative evaluation of gas phase species (O₃, NO₂ and SO₂) and particulate matter (PM2.5 and PM10) against ground-based measurements from the EMEP (European Monitoring and Evaluation Programme) network for the year 2004. The evaluation is based on statistics. Simulated O₃ achieves satisfactory performances for both daily mean and daily maximum concentrations, especially in summer, with annual mean correlations of 0.66 and 0.69, respectively. Mean normalized errors are comprised within the recommendations proposed by the United States Environmental Protection Agency (US-EPA). The general trends and daily variations of primary pollutants (NO₂ and SO₂) are satisfactory. Daily mean concentrations of NO₂ correlate well with observations (annual correlation r = 0.67) but tend to be underestimated. For SO₂, mean concentrations are well simulated (mean bias = 0.5 μg m^?3) with relatively high annual mean correlation (r = 0.60), although peaks are generally overestimated. The dynamics of PM2.5 and PM10 is well reproduced (0.49 < r < 0.62), but mean concentrations remain systematically underestimated. Deficiencies in particulate matter source characterization are discussed. Also, the spatially distributed statistics and the general patterns for each pollutant over Europe are examined. The model performances are compared with other European studies. While O₃ statistics generally remain lower than those obtained by the other considered studies, statistics for NO₂, SO₂, PM2.5 and PM10 present higher scores than most models.