Impact of biogenic VOC emissions on a tropical cyclone-related ozone episode in the Pearl River Delta region,China

For quantitative estimate of biogenic volatile organic compound emissions (BVOCs) in South China and their impact on the regional atmospheric chemistry, a 3-day tropical cyclone-related ozone episode was modeled using chemical transport model CMAQ, which was driven by the mesoscale meteorological model MM5. Hourly biogenic emission inventories were constructed using the Sparse Matrix Operator Kernel Emissions (SMOKE) model. The simulation results show good agreement with observation data in air temperature, ozone and NO_x levels. The estimated biogenic emissions of isoprene, terpene, and other reactive VOCs (ORVOCs) during this tropical cyclone-related episode are 8500, 3400, and 11 300 ton day⁻¹, respectively. The ratio of isoprene to the total BVOCs was 36.4%. Two test runs were carried out with one incorporated biogenic emissions and the other without. The simulations show that Guangdong province, particularly the Pearl River Delta (PRD) region, was the area most reactive to biogenic emissions in South China. More ozone was produced in all layers under 1500 m when biogenic emissions were included in comparison to that without BVOCs. The net formation of ozone from 9:00 to 15:00 h was the highest near the surface and could reach 38 ppb, which include 4 ppb attributed to biogenic impact. The enhanced ozone due to biogenic emissions first appeared in the PRD region and slowly spread to a greater area in South China. Process analysis indicated that the surface ozone budget was dominated by the vertical transport and dry deposition. The horizontal transport and gas-phase chemical production were relatively small in the surface layer. Presumably, ozone was produced in upper layers within the atmospheric boundary layer and convected down to surface where it is destroyed. When BVOCs was included, apart from the enhancement of gas-phase chemical production of ozone, both the surface deposition and vertical transport were also augmented.     

PCDD/F and dioxin-like PCB in Hong Kong air in relation to their regional transport in the Pearl River Delta region

PCDD/F and dioxin-like PCB were measured in 142 air samples of Hong Kong. The annual average PCDD/F and dioxin-like PCB concentrations obtained for Hong Kong air at Tap Mun (PCDD/F: 1724+/-1984; dioxin-like PCB: 1572+/-1170 fg m(-3)), Yuen Long (PCDD/F: 2927+/-2695; dioxin-like PCB: 4331+/-1962 fg m(-3)) and Tsuen Wan (PCDD/F: 1875+/-1502; dioxin-like PCB: 2972+/-1510 fg m(-3)) from January 2004 to March 2005 were comparable to other urban centers around the world and were within the Japanese and USA ambient air quality guidelines. A clear seasonal pattern was observed for PCDD/F, generally with a 50-60 times higher air concentration in winter when background northerly wind was weaker and land-sea breeze prevailed, resulting in regional transport; and a lower concentration in summer, due to the inflow of clean oceanic southeasterly wind from the South China Sea. A higher WHO-TEQ value of dioxin-like PCB (mainly attributed to the relatively higher WHO-TEQ value of PCB 126) in Yuen Long during winter, compared with other months, could also be related to the regional transport by the winter monsoon wind and the low mixing height in winter. Spatially, air concentrations of PCDD/F and dioxin-like PCB demonstrated a west-to-east gradient (with Yuen Long>Tsuen Wan>Tap Mun). It is suggested that PCDD/F and dioxin-like PCB were transported into the western airshed of Hong Kong from the Pearl River Delta by land-sea breeze circulation and confined to the northwestern part, due to the blocking effect of the northwestern airshed in Hong Kong.     

Dynamic evaluation of a regional air quality model: Assessing the emissions-induced weekly ozone cycle

Air quality models are used to predict changes in pollutant concentrations resulting from envisioned emission control policies. Recognizing the need to assess the credibility of air quality models in a policy-relevant context, we perform a dynamic evaluation of the Community Multiscale Air Quality (CMAQ) modeling system for the “weekend ozone effect” to determine if observed changes in ozone due to weekday-to-weekend (WDWE) reductions in precursor emissions can be accurately simulated. The weekend ozone effect offers a unique opportunity for dynamic evaluation, as it is a widely documented phenomenon that has persisted since the 1970s. In many urban areas of the Unites States, higher ozone has been observed on weekends than weekdays, despite dramatically reduced emissions of ozone precursors (nitrogen oxides [NO_x] and volatile organic compounds [VOCs]) on weekends. More recent measurements, however, suggest shifts in the spatial extent or reductions in WDWE ozone differences. Using 18 years (1988–2005) of observed and modeled ozone and temperature data across the northeastern United States, we re-examine the long-term trends in the weekend effect and confounding factors that may be complicating the interpretation of this trend and explore whether CMAQ can replicate the temporal features of the observed weekend effect. The amplitudes of the weekly ozone cycle have decreased during the 18-year period in our study domain, but the year-to-year variability in weekend minus weekday (WEWD) ozone amplitudes is quite large. Inter-annual variability in meteorology appears to influence WEWD differences in ozone, as well as WEWD differences in VOC and NO_x emissions. Because of the large inter-annual variability, modeling strategies using a single episode lasting a few days or a few episodes in a given year may not capture the WEWD signal that exists over longer time periods. The CMAQ model showed skill in predicting the absolute values of ozone concentrations during the daytime. However, early morning NO_x concentrations were underestimated and ozone levels were overestimated. Also, the modeled response of ozone to WEWD differences in emissions was somewhat less than that observed. This study reveals that model performance may be improved by (1) properly estimating mobile source NO_x emissions and their temporal distributions, especially for diesel vehicles; (2) reducing the grid cell size in the lowest layer of CMAQ; and, (3) using time-dependent and more realistic boundary conditions for the CMAQ simulations.     

Process analysis of a regional air pollution episode over Pearl River Delta Region,China, using the MM5-CMAQ model

This study focuses on the influences of a warm high-pressure meteorological system on aerosol pollutants, employing the simulations by the Models-3/CMAQ system and the observations collected during October 10–12, 2004, over the Pearl River Delta (PRD) region. The results show that the spatial distributions of air pollutants are generally circular near Guangzhou and Foshan, which are cities with high emissions rates. The primary pollutant is particulate matter (PM) over the PRD. MM5 shows reasonable performance for major meteorological variables (i.e., temperature, relative humidity, wind direction) with normalized mean biases (NMB) of 4.5–38.8% and for their time series. CMAQ can capture one peak of all air pollutant concentrations on October 11, but misses other peaks. The CMAQ model systematically underpredicts the mass concentrations of all air pollutants. Compared with chemical observations, SO₂ and O₃ are predicted well with a correlation coefficient of 0.70 and 0.65. PM_2.5 and NO are significantly underpredicted with an NMB of 43% and 90%, respectively. The process analysis results show that the emission, dry deposition, horizontal transport, and vertical transport are four main processes affecting air pollutants. The contributions of each physical process are different for the various pollutants. The most important process for PM₁₀ is dry deposition, and for NO_x it is transport. The contributions of horizontal and vertical transport processes vary during the period, but these two processes mostly contribute to the removal of air pollutants at Guangzhou city, whose emissions are high. For this high-pressure case, the contributions of the various processes show high correlations in cities with the similar geographical attributes. According to the statistical results, cities in the PRD region are divided into four groups with different features. The contributions from local and nonlocal emission sources are discussed in different groups.

Implications: The characteristics of aerosol pollution episodes are intensively studied in this work using the high-resolution modeling system MM5/SMOKE/CMAQ, with special efforts on examining the contributions of different physical and chemical processes to air concentrations for each city over the PRD region by a process analysis method, so as to provide a scientific basis for understanding the formation mechanism of regional aerosol pollution under the high-pressure system over PRD.     

Environmental lead pollution threatens the children living in the Pearl River Delta region, China

Introduction and purpose

The objective of this study is to determine children??s blood lead levels and identify sources of lead exposure. Childhood lead exposure constitutes a major pediatric health problem today in China. A blood lead screening survey program for children in the age group of 2?C12?years residing in Pearl River Delta region, south of China, was carried out from Dec 2007 to Jan 2008.

Methods

Blood lead levels and lead isotope ratios of a total of 761 participants were assessed by inductively coupled plasma mass spectroscopy. Measurements of urban environmental samples for source identification of children lead exposure were also performed.

Results and conclusions

The geometric mean value of the children??s blood lead levels was 57.05???g/L, and 9.6% of them were higher than 100???g/L. The blood lead levels were still much higher than those in developed countries. Based on the data of environmental lead source inventories, lead isotopic tracing revealed that there is about 6.7% past used gasoline Pb embedded in Shenzhen residential dust and about 15.6% in Guangzhou dust, respectively.     

Formation of submicron sulfate and organic aerosols in the outflow from the urban region of the Pearl River Delta in China

Size-resolved chemical compositions of non-refractory submicron aerosols were measured using a quadrupole Aerodyne aerosol mass spectrometer at a rural site near Guangzhou in the Pearl River Delta (PRD) of China in the summer of 2006. Two cases characterized as the outflows from the PRD urban region with plumes of high SO₂ concentration were investigated. The evolution of sulfate size distributions was observed on a timescale of several hours. Namely mass concentrations of sulfate in the condensation mode (with vacuum aerodynamic diameters (D_va) < 300 nm) increased at a rate of about 0.17–0.37 ppbv h^?1 during the daytime. This finding was consistent with the sulfuric acid production rates of about 0.17–0.3 ppbv h^?1, as calculated from the observed gas-phase concentrations of OH (～3.3 × 10⁶–1.7 × 10⁷ cm^?3) and SO₂ (～3–21.2 ppbv). This implies that the growth of sulfate in the condensation mode was mainly due to gas-phase oxidation of SO₂. The observed rapid increase was caused mainly by the concurrent high concentrations of OH and SO₂ in the air mass. The evolution of the mass size distributions of m/z 44, a tracer for oxygenated organic aerosol (OOA), was very similar to that of sulfate. The mass loadings of m/z 44 were strongly correlated with those of sulfate (r² = 0.99) in the condensation mode, indicating that OOA might also be formed by the gas-phase oxidation of volatile organic compound (VOC) precursors. It is likely that sulfate and OOA were internally mixed throughout the whole size range in the air mass.     

Combined effect of boundary layer recirculation factor and stable energy on local air quality in the Pearl River Delta over southern China

Atmospheric boundary layer (ABL) has a significant impact on the spatial and temporal distribution of air pollutants. In order to gain a better understanding of how ABL affects the variation of air pollutants, atmospheric boundary layer observations were performed at Sanshui in the Pearl River Delta (PRD) region over southern China during the winter of 2013. Two types of typical ABL status that could lead to air pollution were analyzed comparatively: weak vertical diffusion ability type (WVDAT) and weak horizontal transportation ability type (WHTAT). Results show that (1) WVDAT was featured by moderate wind speed, consistent wind direction, and thick inversion layer at 600~1000 m above ground level (AGL), and air pollutants were restricted in the low altitudes due to the stable atmospheric structure; (2) WHTAT was characterized by calm wind, varied wind direction, and shallow intense ground inversion layer, and air pollutants accumulated in locally because of strong recirculation in the low ABL; (3) recirculation factor (RF) and stable energy (SE) were proved to be good indicators for horizontal transportation ability and vertical diffusion ability of the atmosphere, respectively. Combined utilization of RF and SE can be very helpful in the evaluation of air pollution potential of the ABL.

Implications: Air quality data from ground and meteorological data collected from radio sounding in Sanshui in the Pearl River Delta showed that local air quality was poor when wind reversal was pronounced or temperature stratification state was stable. The combination of horizontal and vertical transportation ability of the local atmosphere should be taken into consideration when evaluating local environmental bearing capacity for air pollution.     

Phased and polarized development of ecological quality in the rapidly-urbanized Pearl River Delta,China

Environmental Science and Pollution Research - Urbanization is one of the most significant human activities in the Anthropocene, with profound impacts on environmental quality. The lack of an...     

Nitric oxide emission from a typical vegetable field in the Pearl River Delta, China

Croplands contribute to atmospheric nitric oxide (NO), but very limited data are available about NO fluxes from intensively managed croplands in China. In this study, NO fluxes were measured in a typical vegetable field planted with flowering Chinese cabbage (Brassica campestris L. ssp. Chinensis var. utilis Tsen et Lee), which is the most widely cultivated vegetable in Guangdong province, south China. NO emission drastically increased after nitrogen fertilizer application, and other practices involving loosening the soil also enhanced NO emission. Mean NO emission flux was 47.5 ng N m⁻² s^–1 over a complete growth cycle. Annual NO emission from the vegetable field was about 10.1 kg N ha⁻¹ yr⁻¹. Fertilizer-induced NO emission factor was estimated to be 2.4%. Total NO emission from vegetable fields in Guangdong province was roughly estimated to be 11.7 Gg N yr⁻¹ based on the vegetable field area and annual NO emission rate, and to be 13.3 Gg N yr⁻¹ based on fertilizer-induced NO emission factor and background NO emission. This means that NO emission from vegetable fields was approximately 6% of NO_x from commercial energy consumption in Guangdong province.     

On the relationship between ozone and its precursors in the Pearl River Delta: application of an observation-based model (OBM)

Background, aim, and scope  

Photochemical smog, characterized by high concentrations of O₃ and fine particles, is of great concern in the urban areas, in particular megacities and city clusters like the Pearl River Delta.     

A highly resolved temporal and spatial air pollutant emission inventory for the Pearl River Delta region, China and its uncertainty assessment

A highly resolved temporal and spatial Pearl River Delta (PRD) regional emission inventory for the year 2006 was developed with the use of best available domestic emission factors and activity data. The inventory covers major emission sources in the region and a bottom–up approach was adopted to compile the inventory for those sources where possible. The results show that the estimates for SO₂, NO_x, CO, PM₁₀, PM_2.5 and VOC emissions in the PRD region for the year 2006 are 711.4 kt, 891.9 kt, 3840.6 kt, 418.4 kt, 204.6 kt, and 1180.1 kt, respectively. About 91.4% of SO₂ emissions were from power plant and industrial sources, and 87.2% of NO_x emissions were from power plant and mobile sources. The industrial, mobile and power plant sources are major contributors to PM₁₀ and PM_2.5 emissions, accounting for 97.7% of the total PM₁₀ and 97.2% of PM_2.5 emissions, respectively. Mobile, biogenic and VOC product-related sources are responsible for 90.5% of the total VOC emissions. The emissions are spatially allocated onto grid cells with a resolution of 3 km × 3 km, showing that anthropogenic air pollutant emissions are mainly distributed over PRD central-southern city cluster areas. The preliminary temporal profiles were established for the power plant, industrial and on-road mobile sources. There is relatively low uncertainty in SO₂ emission estimates with a range of −16% to +21% from power plant sources, medium to high uncertainty for the NO_x emissions, and high uncertainties in the VOC, PM_2.5, PM₁₀ and CO emissions.     

Pragmatic estimation of a spatio-temporal air quality model with irregular monitoring data

Statistical analyses of health effects of air pollution have increasingly used GIS-based covariates for prediction of ambient air quality in “land use” regression models. More recently these spatial regression models have accounted for spatial correlation structure in combining monitoring data with land use covariates. We present a flexible spatio-temporal modeling framework and pragmatic, multi-step estimation procedure that accommodates essentially arbitrary patterns of missing data with respect to an ideally complete space by time matrix of observations on a network of monitoring sites. The methodology incorporates a model for smooth temporal trends with coefficients varying in space according to Partial Least Squares regressions on a large set of geographic covariates and nonstationary modeling of spatio-temporal residuals from these regressions. This work was developed to provide spatial point predictions of PM_2.5 concentrations for the Multi-Ethnic Study of Atherosclerosis and Air Pollution (MESA Air) using irregular monitoring data derived from the AQS regulatory monitoring network and supplemental short-time scale monitoring campaigns conducted to better predict intra-urban variation in air quality. We demonstrate the interpretation and accuracy of this methodology in modeling data from 2000 through 2006 in six U.S. metropolitan areas and establish a basis for likelihood-based estimation.     

Seasonal variation of polycyclic aromatic hydrocarbons (PAHs) in Pearl River Delta region,China

A level IV fugacity model was applied to simulate the seasonal variation of polycyclic aromatic hydrocarbons (PAHs) in various bulk media in Pearl River Delta (PRD), China. The predictions were validated against monthly observed concentrations of gaseous and particulate phase PAHs in air and annual mean concentrations of all other bulk media. The uncertainty of the predictions was evaluated using Monte Carlo simulation. The influential parameters were identified using sensitivity analysis on both media concentrations and seasonal variations. The predicted concentrations and the patterns of seasonal variation generally agreed with the field observations. Concentrations of gaseous phase PAHs in air increased in the summer and decreased in the winter while concentrations of particulate phase PAHs in summer were lower than those in the winter. The relative variations of PAHs in the other bulk media were not as profound as those in air and the variation patterns were chemical compound dependent. Temperature and precipitation were the most important parameters leading to the seasonalities of PAH concentrations. Other key parameters included dry precipitation rate, advective water flow from upstream, and solid fractions in air and water.     

Temporal,spatial characteristics and uncertainty of biogenic VOC emissions in the Pearl River Delta region,China

Using the Global Biosphere Emissions and Interactions System model (GloBEIS), 3 × 3 km gridded and hourly biogenic volatile organic compound (BVOC) emissions in the Pearl River Delta (PRD) were estimated for the year 2006. The study used newly available land cover database, observed meteorological data, and recent measurements of emission rates for tree species in China. The results show that the total BVOC emission in the PRD region in 2006 was 296 kt (2.2 × 10¹¹ gC), of which isoprene contributes about 25% (73 kt, 6.4 × 10¹⁰ gC), monoterpenes about 34% (102 kt, 8.9 × 10¹⁰ gC), and other VOCs (OVOC) about 41% (121 kt, 6.8 × 10¹⁰ gC). BVOC emissions in the PRD region exhibit a marked seasonal pattern with the peak emission in July and the lowest emission in January, and are mainly distributed over the outlying areas of the PRD region, where the economy and land use are less developed. The uncertainties in BVOC emission estimates were quantified using Monte Carlo simulation; the results indicate high uncertainties in isoprene emission estimates, with a relative error of ?82 to +177%, ranging from 12.4 to 186.4 kt; ?41 to +58% uncertainty for monoterpenes emissions, ranging from 67.7 to 181.9 kt; and ?26 to +30% uncertainty in OVOC emissions, ranging from 88.8 to 156.2 kt on the 95% confidence intervals. The key uncertainty sources include emission factors and the model empirical coefficients α, C_T1, C_L, and E_opt for estimating isoprene emission, and emission factors and foliar density for estimating monoterpenes and OVOC emissions. This implies that determining these empirical coefficient values properly and conducting more field measurements of emission rates of tree species are key approaches for reducing uncertainties in BVOC emission estimates. Improving future BVOC emission inventory work in the PRD region requires giving priority to research on shrub land, coniferous forests, and irrigated cropland and pasture.     

On the forest fires and the analysis of air quality data and total atmospheric ozone

In Canada about 1.3 million hectares (M ha) of forests are destroyed by wildfires each year, and about 63 % of all these fires are man-caused. During the 1980 and 1981 fire seasons, however, about 10 M ha were damaged; estimated annual emissions from forest fires were ~ 224 million tonnes (M t) of CO₂; and over 22 M t of CO, total suspended particulates (TSP), hydrocarbons (HC), nitrogen oxides (NO_x), etc.One of the major problems resulting from these forest fires was the severe reduction of visibility over large areas. Daily values of TSP recorded at Fort McMurray, Alberta were in the range of 163–257 μg m⁻³, while TSP observed at Edmonton, about 850km downstream from large fires, were in the range of 134–220 μg m⁻³. Nevertheless, surface ozone (O₃) and total O₃ in vertical air columns had evidently decreased in the area affected by smoke plumes. It is plausible that the O₃ depletion might have occurred in the lower troposphere from the overwhelming existence of forest fire smoke in the region.     

Sources of ambient volatile organic compounds and their contributions to photochemical ozone formation at a site in the Pearl River Delta, southern China

The Positive Matrix Factorization (PMF) receptor model and the Observation Based Model (OBM) were combined to analyze volatile organic compound (VOC) data collected at a suburban site (WQS) in the PRD region. The purposes are to estimate the VOC source apportionment and investigate the contributions of these sources and species of these sources to the O₃ formation in PRD. Ten VOC sources were identified. We further applied the PMF-extracted concentrations of these 10 sources into the OBM and found "solvent usage 1", "diesel vehicular emissions" and "biomass/biofuel burning" contributed most to the O₃ formation at WQS. Among these three sources, higher Relative Incremental Reactivity (RIR)-weighted values of ethene, toluene and m/p-xylene indicated that they were mainly responsible for local O₃ formation in the region. Sensitivity analysis revealed that the sources of "diesel vehicular emissions", "biomass/biofuel burning" and "solvent usage 1" had low uncertainties whereas "gasoline evaporation" showed the highest uncertainty.     

An ozone budget for the UK: using measurements from the national ozone monitoring network; measured and modelled meteorological data,and a 'big-leaf' resistance analogy model of dry deposition

Data from the UK national air-quality monitoring network are used to calculate an annual mass budget for ozone (O3) production and loss in the UK boundary layer during 1996. Monthly losses by dry deposition are quantified from 1 km x 1 km scale maps of O(3) concentration and O(3) deposition velocities based on a big-leaf resistance analogy. The quantity of O(3) deposition varies from approximately 50 Gg-O(3) month(-1) in the winter to over 200 Gg-O(3) month(-1) in the summer when vegetation is actively absorbing O(3). The net O(3) production or loss in the UK boundary layer is found by selecting days when the UK is receiving "clean" Atlantic air from the SW to NW. In these conditions, the difference in O(3) concentration observed at Mace Head and a rural site on the east coast of the UK indicates the net O(3) production or loss within the UK boundary layer. A simple box model is then used to convert the concentration difference into a mass. The final budget shows that for most of the year the UK is a net sink for O(3) (-25 to -800 Gg-O(3) month(-1)) with production only exceeding losses in the photochemically active summer months (+45 Gg-O(3) month(-1)).