Variations of the increasing trend of tropospheric NO2 over central east China during the past decade

A numerical analysis using a regional chemical transport model (CTM) is presented in comparison with Global Ozone Monitoring Experiment (GOME) and SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) satellite NO₂ measurements over East Asia from 1996 to 2005 from a climatological perspective. Modeling results agree well with satellite retrievals in geographical distribution patterns, with systematic underestimation of the absolute values. The sharp increase in NO₂ vertical column densities (VCDs) over central east China (CEC) after the year 2000 (14.1–20.5% yr⁻¹ for the satellite observations and 10.8% yr⁻¹ for model simulations) is analyzed quantitatively over different megacity clusters. The distinct emission increase patterns are responsible for the different increase trends observed over the Beijing megacity cluster (BJ), the Yangtze Delta (YD) and other CEC regions. The growth rate of satellite measured and CMAQ-modeled NO₂ VCDs for the YD is much higher than that in other regions, with no clear seasonal variation. Apart from BJ and YD, NO₂ emissions from other regions in CEC also expand considerably.     

Trend reversal from source region to remote tropospheric NO2 columns

Environmental Science and Pollution Research - Global tropospheric nitrogen dioxide (NO2) changes have different or even opposite impacts on the photochemical formation of ozone in different...     

Adjoint inverse modeling of NOx emissions over eastern China using satellite observations of NO2 vertical column densities

A four-dimensional variational data assimilation system for optimization of NO_x emissions (RC4-NO_x) was developed. A parameterized NO_x chemistry scheme was introduced into the RC4-NO_x system, and key parameters such as chemical production and loss terms of NO_x were calculated in advance using the Community Multiscale Air Quality (CMAQ) modeling system. RC4-NO_x was applied to optimize NO_x emissions over eastern China (EC) in July 1996, 1999, and 2002 using Global Ozone Monitoring Experiment (GOME) satellite observations of NO₂ vertical column densities (VCDs) and a priori emissions from the Regional Emission Inventory in Asia (REAS). After assimilation, RC4-NO_x generally reproduced the spatial distribution, regional averaged values, and time evolution of GOME NO₂ VCDs. Over EC, a priori emissions were reduced by 20% in 1996 and by 8% in 1999, whereas a posteriori emissions were almost the same as a priori emissions in 2002. A priori emissions in the Beijing region were reduced by optimization over the whole simulation period. A posteriori emissions over the Yangtze Delta were larger than a priori emissions in 2002, although they were smaller in both 1996 and 1999. As in other areas, a priori emissions over the North China Plain were reduced in 1996; but those over the eastern part of the plain were increased in 1999, and the area of increased emissions moved slightly westward in 2002. In each region, the growth rates of a posteriori emissions during both 1996–1999 and 1999–2002 became generally larger than those of a priori emissions, and the trends of a posteriori emissions became similar to those of GOME NO₂ VCDs. Our inverse modeling analysis indicates that the rate of increase of NO_x emissions over EC from 1996 to 2002 was much larger for a posteriori emissions (49%) than for a priori emissions (19%).     

乌鲁木齐市夏季大气对流层NO_2垂直柱浓度特征研究

为掌握乌鲁木齐市夏季大气对流层NO2垂直柱浓度(VCD)变化特征,2013年6—8月利用地基多轴差分吸收光谱仪,依据该市南高北低的地形和常年主风向(西北风/东南风),分别在商业区、生活区、工业区和农田区进行大气对流层NO2VCD的监测。结果表明:(1)乌鲁木齐市夏季大气对流层NO2VCD均值为5.70×1015 molec/cm2,早、晚的浓度较高;随南高北低地势,大气对流层NO2VCD呈现南部北部中部的趋势;从不同功能区看,商业区农田区工业区生活区;(2)比较不同天气条件下的大气对流层NO2VCD,晴天的浓度大于多云的浓度;且多云条件的日变化幅度小于晴天,但在不同天气条件下大气对流层NO2VCD在市区不同空间点各有差异;(3)功能区因素、地形地貌因素、主要污染物因素、气象因素和风场效应等的共同作用是乌鲁木齐市夏季大气对流层NO2VCD变化特征空间差异的原因。     

Anomalous low tropospheric column ozone over Eastern India during the severe drought event of monsoon 2002: a case study

Background, aim, and scope  

The present study is an attempt to examine some of the probable causes of the unusually low tropospheric column ozone observed over eastern India during the exceptional drought event in July 2002.     

UV Fourier transform measurements of tropospheric O3, NO2, SO2, benzene, and toluene.

Using the differential optical absorption spectroscopy (DOAS) technique and a Fourier transform spectrometer, NO2, SO2, O3, benzene. and toluene were measured during three measurement campaigns held in Brussels in 1995, 1996, and 1997. The O3 concentrations could be explained as the results of the local photochemistry and the dynamical properties of the mixing layer. NO2 concentrations were anti-correlated to the O3 concentrations, as expected. SO2 also showed a pronounced dependence on car traffic. Average benzene and toluene concentrations were, respectively 1.7 ppb and between 4.4 and 6.6 pbb, but high values of toluene up to 98.8 ppb were observed. SO2 concentrations and to a lesser extent, those of NO2 and 03, were dependent on the wind direction. Ozone in Brussels has been found to be influenced by the meteorological conditions prevailing in central Europe. Comparisons with other measurements have shown that 03 and SO2 data are in general in good agreement, but our NO2 concentrations seem to be generally higher.     

A new model of tropospheric hydroxyl radical concentrations

A chemistry model of the global troposphere is presented which focuses on the hydroxyl radical, OH. Global distributions of OH are calculated based on known chemical reaction pathways, experimentally measured values of precursor species O3, H2O, NOx (defined as NO+NO2), CO, CH4, and actinic flux (which includes the effects of cloud cover and O3 column absorption). Model grid resolution is 1 km in altitude by 10 degrees latitude, and zonally divided into land or ocean. Species are calculated as seasonal averages. Global annual mean OH in the troposphere (up to 14 km altitude) is calculated to be 9.2 x 10(5) molcm(-3) with averages of 9.8 x 10(5) in the northern hemisphere, and 8.5 x 10(5) in the southern hemisphere. Global CO and CH(4) oxidation rates by OH are calculated to be 1840 Tgyear(-1) and 580 Tgyear(-1), respectively. OH is found to be most sensitive to O3 and H2O concentrations, as well as to the photolysis rate of O3 to O1D. Sensitivity of CO and CH4 oxidation rates to cloud presence shows an inverse relationship to cloud amount and optical depth. Model results are shown to be consistent with results from two other published models.     

Evaluation of historical CMIP6 model simulations and future projections of temperature over the Pan-Third Pole region

Environmental Science and Pollution Research - The Pan-Third Pole (PTP) region, which encompasses the Eurasian highlands and their surroundings, has experienced unprecedented, accelerated warming...     

Trans-boundary air pollution over remote islands in Japan: observed data and estimates from a numerical model

Observations of air pollutants were conducted in remote Japanese islands (Oki Island and Okinawa Island) in early spring to clarify the extent of trans-boundary air pollution from the Asian continent. A three-dimensional Eulerian model calculation, which included parameters on emission, transport and transformation of sulfur oxides, nitrogen oxides and ammonia, was performed to compile sulfate isosurface concentrations over the observational sites. Concentrations of non-sea-salt sulfate (nss-SO₄²⁻) of greater than 10 μg m⁻³ were observed at Oki after the northeastward passage of low-pressure systems in the Sea of Japan. At these times, the weather showed a typical winter pattern and air pollutants over China were transported southeastward to Japan with the northwesterly wind. The model calculation reproduced the observed variations of nss-SO₄²⁻ concentration well, except for one case in which the model calculation could not reproduce the extremely low nss-SO₄²⁻ concentration observed on 8 March. In Hedo (Okinawa Island), we observed long-lasting (3 days) medium concentrations of nss-SO₄²⁻ (approximately 5 μg m⁻³). Although the model reproduced these observed medium concentrations well, in general the observed results were reproduced better for Oki than for Hedo. Under the synoptic weather conditions of early spring, high concentrations of nss-sulfate were sometimes transported to these remote Japanese islands from areas of continental Asia with a strong outflow of air pollutants.     

Climate simulations using the GCRC 2-D zonally averaged statistical dynamical climate model

The two-dimensional statistical dynamical climate model, recently developed at the Global Change Research Center (GCRC 2D climate model) is presented and discussed. The model solves the 2-D primitive equations in finite difference form (mass continuity, Newton's second law, and the first law of thermodynamics) for the prognostic variables zonal mean density, zonal mean zonal velocity, zonal mean meridional velocity, and zonal mean temperature on a grid that has 18 nodes in latitude and 9 vertical nodes (plus the surface). The equation of state, p = ρRT and an assumed hydrostatic atmosphere, δp = −ρgδz, are used to diagnostically calculate the zonal mean pressure and vertical velocity for each grid node, and the moisture balance equation is used to estimate the precipitation rate.

The performance of the model at simulating the two-dimensional temperature, zonal winds, and mass stream function is discussed here. The strengths and weaknesses of the model are highlighted and plans for future model experiments and improvements are given. The parameterization of the transient eddy fluxes of heat and momentum developed by Stone and Yao (1987 and 1990) are used with small modifications. These modifications are shown to improve the performance of the model at simulating the observed climate system as well as increase the model's computational stability.     

Sulfur deposition simulations over China, Japan, and Korea: a model intercomparison study for abating sulfur emission

In response to increasing trends in sulfur deposition in Northeast Asia, three countries in the region (China, Japan, and Korea) agreed to devise abatement strategies. The concepts of critical loads and source?Creceptor (S?CR) relationships provide guidance for formulating such strategies. Based on the Long-range Transboundary Air Pollutants in Northeast Asia (LTP) project, this study analyzes sulfur deposition data in order to optimize acidic loads over the three countries. The three groups involved in this study carried out a full year (2002) of sulfur deposition modeling over the geographic region spanning the three countries, using three air quality models: MM5-CMAQ, MM5-RAQM, and RAMS-CADM, employed by Chinese, Japanese, and Korean modeling groups, respectively. Each model employed its own meteorological numerical model and model parameters. Only the emission rates for SO₂ and NO_x obtained from the LTP project were the common parameter used in the three models. Three models revealed some bias from dry to wet deposition, particularly the latter because of the bias in annual precipitation. This finding points to the need for further sensitivity tests of the wet removal rates in association with underlying cloud?Cprecipitation physics and parameterizations. Despite this bias, the annual total (dry plus wet) sulfur deposition predicted by the models were surprisingly very similar. The ensemble average annual total deposition was 7,203.6?±?370 kt S with a minimal mean fractional error (MFE) of 8.95?±?5.24?% and a pattern correlation (PC) of 0.89?C0.93 between the models. This exercise revealed that despite rather poor error scores in comparison with observations, these consistent total deposition values across the three models, based on LTP group's input data assumptions, suggest a plausible S?CR relationship that can be applied to the next task of designing cost-effective emission abatement strategies.     

Generation and growth of aerosols over Pune,India

The measured physical size distributions of sub-micron particles during cold season at Pune, India are analyzed to explore the characteristics of nucleation and growth properties. Preliminary analysis of aerosol size distribution in time-series shows large increase in number concentration due to nucleation events between 0800 h and 1030 h at this location. The observable quantities such as condensable vapor concentration (C), its source rate (Q), growth rate (GR) and condensable sink (CS) are estimated from the time-series evolutions of aerosol size distributions. The concentration of vapor and its source rate were about 19.8 ± 2.15 × 10⁷ molecules cm^?3 and 1.28 ± 0.084 × 10⁷ cm^?3 s^?1 respectively. The average condensation sink and growth rate were 7.1 ± 0.4 × 10^?2 s^?1 and 16.95 ± 1.86 nm h^?1 respectively during the growth period. The values are high enough to trigger the nucleation bursts and enhance subsequent growth rates of nucleation mode particles at this location. The magnitudes are in the range of those observed at New Delhi, India and much higher than those of European cities. The ratio of apparent to real nucleation rate is found to be a measure of number concentration of freshly produced particles by photo-chemical nucleation. The predicted number concentrations corresponding to measured distributions of mid-point diameter increases with the size for both 1 nm nucleated clusters and 3 nm particles. The database of all the possible event days and the event characteristics forms the basis for future works into the causes and implications of atmospheric particle formation at this location.     

Influence of boundary conditions on CMAQ simulations over the Iberian Peninsula

The influence of chemical boundary conditions (BC) on the response of the Community Multiscale Air Quality (CMAQ) model over the Iberian Peninsula was investigated in this study. Three strategies to supply boundary conditions in the context of the Integrated Assessment Modelling System for the Iberian Peninsula (SIMCA) were tested. Alternative methods consist in providing BC from (1) fixed, time-independent, concentration profiles, (2) concentrations predicted in a CMAQ mother domain (48 km, 1 h resolution) and (3) concentration values from the GEOS-Chem chemical-transport global model (2 × 2.5°, 3 h resolution). High resolution (3 km) simulated concentrations of the main pollutants (NO₂, NO, SO₂, O₃, PM₁₀ and PM_2.5) were compared through a comprehensive statistical analysis including observational data from 165 monitoring stations all over the Iberian Peninsula. It was found that model sensitivity to BC for nitrogen and sulphur oxides was limited, being restricted to the vicinity of model boundaries. However, significant domain-wide differences were found when modelling ozone and PM depending on the BC provided to run the tests. Although model performance was affected by spatial and seasonal factors, the results indicate that model-derived, dynamic BC improved CMAQ predictions when compared to those based on static concentrations prescribed in the boundaries. Aggregated statistics suggest that the GEOS-Chem produced the best results for O₃ and PM_2.5 while NO₂ and PM₁₀ were slightly better predicted under the CMAQ nesting approach. Besides the statistical evaluation some other relevant issues in the context of Integrated Assessment Modelling (IAM) are discussed to gain a better insight into the suitability of the methods analyzed and limitations of downscaling methods. Despite being useful to get a better understanding of the role of BC in SIMCA, this study contributed to highlight model deficiencies and therefore to point out future research needs to improve IAM activities in the Iberian Peninsula.     

NO2 and SO2 dispersion modeling and relative roles of emission sources over Map Ta Phut industrial area, Thailand

Map Ta Phut industrial area (MA) is the largest industrial complex in Thailand. There has been concern about many air pollutants over this area. Air quality management for the area is known to be difficult, due to lack of understanding of how emissions from different sources or sectors (e.g., industrial, power plant, transportation, and residential) contribute to air quality degradation in the area. In this study, a dispersion study of NO2 and SO2 was conducted using the AERMOD model. The area-specific emission inventories of NOx and SO2 were prepared, including both stack and nonstack sources, and divided into 11 emission groups. Annual simulations were performed for the year 2006. Modeled concentrations were evaluated with observations. Underestimation of both pollutants was Jbund, and stack emission estimates were scaled to improve the modeled results before quantifying relative roles of individual emission groups to ambient concentration overfour selected impacted areas (two are residential and the others are highly industrialized). Two concentration measures (i.e., annual average area-wide concentration or AC, and area-wide robust highest concentration or AR) were used to aggregately represent mean and high-end concentrations Jbfor each individual area, respectively. For AC-NO2, on-road mobile emissions were found to be the largest contributor in the two residential areas (36-38% of total AC-NO2), while petrochemical-industry emissions play the most important role in the two industrialized areas (34-51%). For AR-NO2, biomass burning has the most influence in all impacted areas (>90%) exceptJor one residential area where on-road mobile is the largest (75%). For AC-SO2, the petrochemical industry contributes most in all impacted areas (38-56%). For AR-SO2, the results vary. Since the petrochemical industry was often identified as the major contributor despite not being the largest emitter, air quality workers should pay special attention to this emission group when managing air quality for the MA.     

NO2 and SO2dispersion modeling and relative roles of emission sources over Map Ta Phut industrial area,Thailand

Map Ta Phut industrial area (MA) is the largest industrial complex in Thailand. There has been concern about many air pollutants over this area. Air quality management for the area is known to be difficult, due to lack of understanding of how emissions from different sources or sectors (e.g., industrial, power plant, transportation, and residential) contribute to air quality degradation in the area. In this study, a dispersion study of NO₂ and SO₂ was conducted using the AERMOD model. The area-specific emission inventories of NO_x and SO₂ were prepared, including both stack and nonstack sources, and divided into 11 emission groups. Annual simulations were performed for the year 2006. Modeled concentrations were evaluated with observations. Underestimation of both pollutants was found, and stack emission estimates were scaled to improve the modeled results before quantifying relative roles of individual emission groups to ambient concentration over four selected impacted areas (two are residential and the others are highly industrialized). Two concentration measures (i.e., annual average area-wide concentration or AC, and area-wide robust highest concentration or AR) were used to aggregately represent mean and high-end concentrations for each individual area, respectively. For AC-NO₂, on-road mobile emissions were found to be the largest contributor in the two residential areas (36–38% of total AC-NO₂), while petrochemical-industry emissions play the most important role in the two industrialized areas (34–51%). For AR-NO₂, biomass burning has the most influence in all impacted areas (>90%) except for one residential area where on-road mobile is the largest (75%). For AC-SO₂, the petrochemical industry contributes most in all impacted areas (38–56%). For AR-SO₂, the results vary. Since the petrochemical industry was often identified as the major contributor despite not being the largest emitter, air quality workers should pay special attention to this emission group when managing air quality for the MA.

Implications: Effective air quality management in Map Ta Phut Industrial Area, Thailand requires better understanding of how emissions from various sources contribute to the degradation of ambient air quality. Based on the dispersion study here, petrochemical industry was generally identified as the major contributor to ambient NO₂ and SO₂. By accounting for all stack and non-stack sources, on-road mobile emissions were found to be important in some particular areas.     

Application of CALINE4 to roadside NO/NO2 transformations

The CALINE4 roadway dispersion model has been applied to concentrations of NO_x and NO₂ measured near Gandy Boulevard in Tampa, FL (USA) during May 2002. A NO_x emission factor of 0.86 gr mi⁻¹ was estimated by treating NO+NO₂ (NO_x) as a conserved species and minimizing the differences between measured and calculated NO_x concentrations. This emission factor was then used to calculate NO₂ concentrations using the NO/NO₂ transformation reactions built into CALINE4. A comparison of measured and calculated NO₂ concentrations indicates that for ambient O₃ concentrations less than 40 ppb the model under-predicts the chemical transformation of NO. The enhanced transformation of NO may be due to reactions of NO with oxidants such as peroxy radicals that are present either in the atmosphere or in vehicle exhaust.     

Chemical characteristics of atmospheric aerosols over southwest coast of India

Ambient aerosol samples, collected from Mangalore region in the southwest coast of India during the period of late winter (February and March) to early summer (April and May), have been analysed for water-soluble ionic species. Their abundance pattern is dominated by HCO₃⁻, SO₄²⁻, Na⁺, Cl⁻, with minor contribution from NO₃⁻, Ca²⁺, NH₄⁺, K⁺ and Mg²⁺ indicating the contribution from not only sea salt, but also from anthropogenic and dust sources; with pronounced seasonal variability. The suspended particulate matter concentration varied from 35 to 160 μg m⁻³, with consistently higher values during the late winter. Back trajectory analysis suggests the origin of the air masses shifting from Indo-Gangetic Plains (during late winter) to those from the Arabian Sea and the area around Persian Gulf during April–May. Air masses passing over Northern India (Indo-Gangetic Plains) impart characteristic contribution of ionic species from fossil fuel combustion, biomass burning and eolian dust as asserted by the factor analysis. A detailed study on characterisation of aerosols from south Asian region is rather sparse but essential for modelling the effect of tropospheric aerosols on climate.     

Night-time tropospheric chemistry of the unsaturated alcohols (Z)-pent-2-en-1-ol and pent-1-en-3-ol: Kinetic studies of reactions of NO3 and N2O5 with stress-induced plant emissions

The night-time tropospheric chemistry of two stress-induced volatile organic compounds (VOCs), (Z)-pent-2-en-1-ol and pent-1-en-3-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO₃) with these pentenols were measured using the discharge-flow technique. Because of the relatively low volatility of these compounds, we employed off-axis continuous-wave cavity-enhanced absorption spectroscopy for detection of NO₃ in order to be able to work in pseudo first-order conditions with the pentenols in large excess over NO₃. The rate coefficients were determined to be (1.53±0.23)×10⁻¹³ and (1.39±0.19)×10⁻¹⁴ cm³ molecule⁻¹ s⁻¹ for reactions of NO₃ with (Z)-pent-2-en-1-ol and pent-1-en-3-ol. An attempt to study the kinetics of these reactions with a relative-rate technique, using N₂O₅ as source of NO₃ resulted in significantly higher apparent rate coefficients. Performing relative-rate experiments in known excesses of NO₂ allowed us to determine the rate coefficients for the N₂O₅ reactions to be (5.0±2.8)×10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ for (Z)-pent-2-en-1-ol, and (9.1±5.8)×10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ for pent-1-en-3-ol. We show that these relatively slow reactions can indeed interfere with rate determinations in conventional relative-rate experiments.