Verifying emission factors and national POPs emission inventories for the UK using measurements and modelling at two rural locations

Different approaches are used to verify the adequacy of emission factors (EFs) and their use in emission inventories of persistent organic pollutants (POPs). The applicability of EFs was tested using atmospheric dispersion modelling to predict atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and resulting toxic equivalents (SigmaTEQ) and particulate matter <10 microm (PM(10)) in two rural locations in northern England (UK). The modelling was based on general assumptions of fuel composition, consumption and heating needs to simulate emissions of POPs from the domestic burning of coal and wood where ambient measurements were made in the winter of 1998. The model was used to derive the local contribution to ambient air concentrations, which were estimated independently based on comparative air measurements. The results support the hypothesis that in both villages, the majority of PAHs and the lower chlorinated PCDFs were locally released. The situation for PCBs and polychlorinated naphthalenes (PCNs) was different. While the EFs show the release of both compound groups from the domestic burning of coal and wood, the ambient levels of these "legacy POPs" in the villages were still clearly dominated by other sources. Rural areas relying mainly on fossil fuels can exceed the proposed UK ambient air quality standard for benzo[a]pyrene during winter. The measured EFs were then used to estimate the importance of the domestic burning of coal and wood to national emission inventories for these compound classes. Extrapolations to the UK suggest that the domestic burning of pure wood and coal were minor emitters for chlorinated POPs but contributed strongly to PAH and PM(10) levels in 2000. Finally, the UK's national POPs emission inventories based on source inventories and EF, as used here, were compared to estimates derived using the increase in atmospheric concentration of selected POPs.     

A study of ground-level ozone pollution, ozone precursors and subtropical meteorological conditions in central Taiwan

Hourly concentrations of ozone (O(3)), 55 volatile organic compounds (VOCs, ozone precursors) and nitrogen oxides (NOx) were measured at an upwind urban site, a downwind suburban site, and a rural site in central Taiwan, from January 2003 to December 2006. VOC and NOx mean concentrations showed a gradient from high to low across the urban (56 ppb and 34 ppb), suburban (38 ppb and 27 ppb) and rural sites (25 ppb and 21 ppb) but a reverse gradient in ozone across these sites (24, 27, and 29 ppb, respectively). Although there was about twice the difference in VOC concentrations between the urban and rural sites, nearly 65% ozone formation potential was contributed to by the same 9 VOCs. Seasonal patterns showed peak ozone levels in autumn and minima in summer at the urban site, but minima in winter at the downwind suburban and rural sites. Ozone precursor levels, on the other hand, were lowest in summer and highest in winter. The diurnal pattern showed that ozone levels peaked one hour later at the rural site than at the urban site. The ethylbenzene to m,p-xylene ratio, an indicator of the age of the air mass, increased from 0.4 at the urban site to 0.6 at the suburban site and 0.8 at the rural site during daily peak ozone times. This finding suggests the transport of ozone and precursors from upwind to downwind producing elevated ozone levels in the suburban and rural areas. Ozone episodes occurred mostly in days with a mean midday UV index of 6.5 (1 UV index=100 J m(-2)) and wind speed at 1.3 m s(-1) at all three sites.     

典型化工园区大气中挥发性有机物污染调查

对常州市某典型化工园区大气中挥发性有机物(VOCs)污染状况进行了调查。结果表明,该化工园区大气中检出挥发性有机物共有58种,组分有芳香烃、饱和烷烃、卤代烃、烯烃、醛酯类化合物及其他类;苯、甲苯、乙苯、二甲苯为主要挥发性有机污染物,质量浓度为1.0~194μg/m~3;均未超出参考标准的限值。背景点位和园区点位大气中主要ρ总(VOCs)在秋冬季最高,敏感点大气VOCs随季节变化也较为明显;园区T1和T2ρ总(VOCs)年均值高于敏感点位,背景点位年均值最低;园区点位除了汽车尾气排放之外,溶剂的挥发和生产工艺中污染物的排放也增加了大气中苯系物的浓度,同时也对敏感点位和对照点位的大气质量产生了一定的影响。     

Analysis of acidic components, heavy metals and PAHS of particulate in the Changwon–Masan area of Korea

This study is an analysis of the concentrations and components of heavy metals in PM_2.5 and the total suspended particulate (TSP) collected at a mechanical industrial complex (IC) site in Changwon and at a residential site in Masan, Korea. Particulate was collected during two sampling periods, from the late summer to the early fall and from the middle to late fall, at the IC site and one sampling period, from the middle fall to the early winter, at the residential site. PM_2.5 and TSP samples were taken by an annular denuder system and a hi-volume air sampler, respectively. The authors also identified the concentrations and components of heavy metals extracted from the PM_2.5 and TSP filters, the acidic components extracted from the PM_2.5 filters, and the polycyclic aromatic hydrocarbons (PAHs) extracted from polyurethane foam (PUF) plug. The average concentrations of the PM_2.5 collected at the IC and residential sites were very similar. Major sources of PM_2.5 at the study sites, however, were air emissions from vehicles and industry as well as emissions from residential heating and soil origins, respectively. The higher concentrations of the TSP at the IC site, as compared to those at the residential site, were due to either increased suspended dust from vehicle emissions or re-suspended road dust because of increased vehicle speeds near the IC site. Heavy metal concentrations in the TSPs were higher than those in the PM_2.5. The heavy metal concentrations in the PM_2.5 and TSP at the IC site with heavy traffic were substantially greater than those at the residential site. The concentrations of TSP and heavy metals and PAHs in PM during the period of the middle to late fall was much higher than those during the period of the late summer to early fall at the IC site. This is because of the difference in meteorological characteristics and energy uses between two periods. The residential site also showed higher concentrations of acidic anions while the IC site showed higher concentrations of acidic cation. Secondary aerosols or particulates, such as ammonium nitrate or ammonium nitrite, might have been important constituents of the PM_2.5 at the residential site. The PAHs in the TSP collected at the IC site was greatly affected by traffic and industry emissions consisting mostly of high molecular weight PAHs with two to four rings. PAHs in the TSP at the site, however, were affected by residential heating and air emissions from small chemical plants having higher concentrations of low molecular weight PAHs with five to six rings.     

Seasonal variation of polycyclic aromatic hydrocarbons in soil and air of Dalian areas, China: an assessment of soil-air exchange

The seasonal variations of concentrations of PAHs in the soil and the air were measured in urban and rural region of Dalian, China in 2007. In soil, mean concentrations of all PAHs in summer were larger than those in winter, whereas the concentrations of heavier weight PAHs in winter were larger than those in summer. Winter/summer concentration ratios for individual PAHs (R(W/S)) increased with the increase of molecular weight of PAHs in soil, indicating that PAHs with high molecular weight were more easily deposited to soil in winter than summer. In air, mean concentrations of all PAHs in winter were larger than those in summer. In comparison with the R(W/S) in soil, all the values of R(W/S) in air were larger than one indicating that the entire individual PAH concentrations in winter were larger than those in summer. The average concentration composition for each PAH compound in soil and air samples was determined and the seasonal change of PAH profile was very small. It was suggested that PAHs in soils and air had the same or similar sources both in winter and summer. The approach to the soil-air equilibrium was assessed by calculating fugacity quotients between soil and air using the soil and air concentrations. The calculated soil-air fugacity quotients indicated that soil acted as a secondary source to the atmosphere for all lighter weight PAHs (two-three rings) and it will continue to be a sink for heavier weight PAHs (five-six rings) in the Dalian environment, both in winter and summer. Medium weight PAHs (four-five rings) were close to the soil-air equilibrium and the tendency shifted between soil and air when season or function region changed. The fugacity quotients of PAHs in summer (mean temperature 298 K) were larger than those in winter (mean temperature 273 K), indicating a higher tendency in summer than winter for PAHs to move from soil to air. The variation of ambient conditions such as temperature, rainfall, etc. can influence the movement of PAHs between soil and air. Most of the fugacity quotients of PAHs for the urban sites were larger than that for the rural site both in winter and summer. This phenomenon may be related with that the temperatures in urban sites were higher than those in the rural site because of the urban heat island effect.     

Polycyclic aromatic hydrocarbons (PAHs) in the air of Chinese cities

Polycyclic aromatic hydrocarbons (PAHs) were determined in the air of 37 cities and 3 rural locations across China during the winter, spring, summer and autumn of 2005, using polyurethane foam (PUF) disks as passive air samplers (PAS). Winter and autumn concentrations in cities exceeded spring and summer values. Concentrations were amongst the highest in the world; seasonally averaged autumn/winter values in some cities in the north and north-west of China exceeded proposed European Union air quality standards. Several factors, acting in combination, influenced air concentrations. A significant negative correlation was found between average annual city concentrations and the annual average temperature, while winter time PAH concentrations correlated with estimated coal consumption. The highest total PAH concentrations and loadings of high molecular weight compounds generally occurred in major cities located on higher land (500-2000 m), where relatively cold winters and higher coal consumption occurs. Lower values occurred in cities located in the south and east China and along the coastal regions. Molecular markers indicated incomplete combustion of fossil fuels dominated the urban air and gave evidence for photo-decomposition of selected compounds.     

Ambient air concentrations of PCDDs,PCDFs, coplanar PCBs,and PAHs at the Mississippi Sandhill Crane National Wildlife Refuge,Jackson County,Mississippi

Our objective was to determine the levels of selected airborne contaminants in ambient air at the Mississippi Sandhill Crane National Wildlife Refuge, Mississippi, that might be affecting the health of endangered cranes living there. Two high-volume air samplers were operated at separate locations on the Refuge during May–September 1991. The sampling media were micro-quartz filters in combination with polyurethane foam plugs. Composite bimonthly samples from each station were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), coplanar polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). Overall, residue concentrations were low. The toxic PCDD isomer 2,3,7,8-tetra-CDD was not detected, nor was penta-CDD. There was no difference (P>0.05) in residue concentrations between stations or over time and meteorological parameters were not correlated with residue concentrations. Because contaminant levels and patterns may differ seasonally, we recommend that air samples collected during winter months also be analyzed for these same chemical groups.     

Persistent organic pollutants in European background air: derivation of temporal and latitudinal trends

Data are presented for polynuclear aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated diphenyls ethers (PBDEs) and selected organochlorine compounds (OCs) in passive air samplers (PAS) along a rural/remote latitudinal transect from southern UK to northern Norway during 2002-2004. This study is part of an ongoing campaign, using semi-permeable membrane devices (SPMDs) as PAS over two year intervals since 1994. Data for PCBs, selected OCs and PBDEs are compared with that from previous campaigns. Absolute sequestered amounts of selected PCB congeners have decreased in a first order fashion between 1994-2004, with an average atmospheric clearance rate of 4.1 +/- 0.6 years and continue to fractionate with latitude. HCB has also declined between 1998-2004, with a clearance rate of 6 +/- 2.4 years. Data on DDT and its breakdown products indicate little fresh release in Europe. Comparison of PBDEs in 2000-02 and 2002-04 indicates site differences, generally with increases at UK sites and decreases in Norway. BDE-28, 47 and 49 decreased with increasing latitude (p < 0.04), while the other congeners did not show any significant latitudinal dependence. Transect data are presented for PAHs the first time. Three- and 4-ringed compounds dominated the mixture present in the SPMD. The PAH composition of the SPMDs at site 3 was compared to the average composition taken by active sampling at the same site. SPMD performance for sampling PAHs leaves many uncertainties, but they can be successfully used to semiquantitatively detect PAHs in the atmosphere. Fluorene and phenanthrene increased with latitude (p > 0.05), while 1-methylphenanthere, fluoranthene, benzo[b]fluoranthene and indeno[123-cd]pyrene decreased. Results are discussed in terms of sources, long-range atmospheric transport, global fractionation and clearance processes.     

Assessment of sorbent impregnated PUF disks (SIPs) for long-term sampling of legacy POPs

Two field studies were conducted for one year using sorbent-impregnated polyurethane foam (SIP) disks for PCB and PBDE air sampling. SIP disks were introduced by Shoeib et al. (2008) as an alternative passive air sampling medium to the polyurethane foam (PUF) disk and have the advantage of a higher holding capacity for organic chemicals. The first study on SIP disks confirmed their application for measuring volatile perfluorinated compounds (PFCs) and their ability to maintain time-integrated (linear) air sampling. In this study, the suitability of the SIP disks for long-term sampling of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexachlorobenzene (HCB) was assessed. SIP disks were deployed at a rural site in the UK and harvested after periods ranging from 35-350 days. Atmospheric POP concentrations were monitored with a high-volume air sampler during the deployment period. Linear uptake was observed for all monitored PCBs and PBDEs over the full exposure time. Air-sampler equilibrium was observed for HCB after 6 months. In a second field study, SIP disks were deployed for one year at 10 sites on a latitudinal transect in the UK and Norway, at which air sampling has been undertaken previously with different passive air sampling media since 1994. The estimated concentrations and spatial distributions derived from the SIP disks were largely in agreement with previously reported data.     

Local and regional air pollution in Ireland during an intensive aerosol measurement campaign

An intensive two month measurement campaign has been performed during a two year study of major component composition of urban PM10 and PM2.5 in Ireland (J. Yin, A. G. Allen, R. M. Harrison, S. G. Jennings, E. Wright, M. Fitzpatrick, T. Healy, E. Barry, D. Ceburnis and D. McCusker, Atmos. Res., 2005, 78(3-4), 149-165). Measurements included size-segregated mass, soluble ions, elemental carbon (EC) distributions, fine and coarse fraction organic carbon (OC) and major gases along with standard meteorological measurements. The study revealed that urban emissions in Ireland had mainly a local character and therefore were confined within a limited area of 20-30 km radius, without significantly affecting regional air quality. Gaseous measurements have shown that urban emissions in Ireland had clear, but fairly limited influence on the regional air quality due to favorable mixing conditions at higher wind speeds, in particular from the western sector. Size-segregated mass and chemical measurements revealed a clear demarcation size between accumulation and coarse modes at about 0.8 microm which was constant at all sites. Carbonaceous compounds at the urban site accounted for up to 90% of the particle mass in a size range of 0.066-0.61 microm. Nss SO4(2-) concentrations in PM2.5 were only slightly higher at the urban site compared to the rural or coastal sites, while NO3- and NH4+ concentrations were similar at the urban and coastal sites, but were a factor of 2 to 3 higher than at the rural site. OC was highly variable between the sites and revealed clear seasonal differences. Natural or biogenic OC component accounted for <10% in winter and up to 30% in summer of the PM2.5 OC at urban sites. A contribution of biogenic OC component to PM2.5 OC mass at rural site was dominant.     

Air quality at a snowmobile staging area and snow chemistry on and off trail in a Rocky Mountain subalpine forest, Snowy Range, Wyoming

A study was begun in the winter of 2000–2001 and continued through the winter of 2001–2002 to examine air quality at the Green Rock snowmobile staging area at 2,985 m elevation in the Snowy Range of Wyoming. The study was designed to evaluate the effects of winter recreation snowmobile activity on air quality at this high elevation site by measuring levels of nitrogen oxides (NO _x , NO), carbon monoxide (CO), ozone (O₃) and particulate matter (PM₁₀ mass). Snowmobile numbers were higher weekends than weekdays, but numbers were difficult to quantify with an infrared sensor. Nitrogen oxides and carbon monoxide were significantly higher weekends than weekdays. Ozone and particulate matter were not significantly different during the weekend compared to weekdays. Air quality data during the summer was also compared to the winter data. Carbon monoxide levels at the site were significantly higher during the winter than during the summer. Nitrogen oxides and particulates were significantly higher during the summer compared to winter. Nevertheless, air pollutants were well dispersed and diluted by strong winds common at the site, and it appears that snowmobile emissions did not have a significant impact on air quality at this high elevation ecosystem. Pollutant concentrations were generally low both winter and summer. In a separate study, water chemistry and snow density were measured from snow samples collected on and adjacent to a snowmobile trail. Snow on the trail was significantly denser and significantly more acidic with significantly higher concentrations of sodium, ammonium, calcium, magnesium, fluoride, and sulfate than in snow off the trail. Snowmobile activity had no effect on nitrate levels in snow.     

An analysis of spatial and temporal properties of daily sulfate, nitrate and chloride concentrations at UK urban and rural sites

Daily measurements of sulfate, nitrate and chloride in PM(10) have been made at three geographically separated UK sites over a three year period. Chloride shows a clear seasonal pattern with highest concentrations in winter, whilst sulfate and nitrate both show highest concentrations in the spring, apparently related to weather patterns. Spatial variability of both sulfate and nitrate is low in comparison to temporal variations, with high correlations of both species between all three sites, London (North Kensington), Harwell and Belfast, despite a geographic separation of 510 km. Both SO/SO(2) and NO/NO(x) ratios are considerably higher in summer than winter, reflecting a greater oxidising capacity of the atmosphere. SO(4)(2-)/NO(3)(-) ratios are higher in summer than winter, suggesting that aqueous phase oxidation of SO(2), expected to be most important in the winter months is not appreciably influencing production of sulfate aerosol, although greater dissociation of ammonium nitrate in summer may also play a role. Regression of concentrations at London, North Kensington with those from the proximate rural site of Harwell is interpreted as showing a similar effect of regional transport at the two sites and a small influence of local formation in the urban atmosphere or primary emissions, averaging 0.46 microg m(-3) of nitrate and 0.22 microg m(-3) of sulfate.     

Air pollution associated with airports

Air quality in the vicinity of airports is examined with particular reference to a detailed study of Gatwick Airport (UK). Ambient air concentrations of carbon monoxide, hydrocarbons (total and non-methane), oxides of nitrogen, smoke and airborne particulate lead have been measured at seven locations around the airport. The results obtained have been compared with ambient air quality guidelines, where available, and with results from other monitoring sites in the UK. It is concluded that the airport cannot be considered to be a significantly more important contributor to average pollutant ground-level concentrations than other sources in the area.     

Trends in motor-vehicle related air pollutants in central London

Results of intermittent monitoring of six aromatic hydrocarbons (benzene, toluene, ethyl-benzene, m-xylene, p-xylene and o-xylene), carbon monoxide and oxides of nitrogen over a thirteen year period at a site in central London (Exhibition Road) are presented. Four monitoring regimes were undertaken; namely, 1979, 1982/83, 1986/87 and 1991/92. The summertime daytime mean ambient concentrations of the measured parameters at this site are presented. The reported concentrations show a reduction from 1979 to 1992 by approximately a factor of two, despite national increases in motor fuel consumption and the volume of traffic. Relevant European Community legislation covering emissions from motor-vehicles are outlined and comparisons are made with emissions from motor vehicles predicted from the UK national inventory. The importance of the frequency of measurements was also noted.     

An analysis of total gaseous mercury (TGM) concentrations across the UK from a rural sampling network

Total gaseous mercury was collected at ten sites, which comprise part of the UK rural heavy metals monitoring network, between 2005 and 2008. Using the gold amalgam technique to capture total gaseous mercury, samples were analysed using a Tekran 2537A mercury vapour analyser. The data showed no upward or downward trend in atmospheric mercury concentrations over the period, with 4 year average concentrations between 1.3 and 1.9 ng m(-3), which are in line with other studies' observed northern hemispheric background concentrations of between 1.5 and 1.7 ng m(-3). Using data from nine of the sites, we were able to show seasonality within the data and through kriging we were able to interpolate the TGM concentrations over the UK, revealing a south-east to north-west declining concentration gradient. Using continuous speciated mercury measurements from one of the network sites, we show through wind sector analysis and air-mass back trajectories that this spatial trend is likely to be due to air masses moving over the UK from continental Europe on easterly winds. The levels of TGM recorded in the south-east of the UK also more closely match observed background TGM levels on the continent, which could indicate that the TGM concentrations from the north of the UK are a better reflection of the true North Atlantic atmospheric mercury background level.     

Nine-year trend of air pollution by CO in Athens,Greece

Air quality data obtained by the Athens air pollution monitoring system from the nine-year period started in 1986 were analysed to determine time variations and the effect of various meteorological parameters on air quality by CO. From the ten monitoring stations measuring CO, the station located in a street with high traffic was selected since this site had the longest time record and presented the highest values of CO during the period examined. The time variations show that higher concentrations of CO were measured during the winter months, on working days and between 09.00 and 23.00 hours. The long-term trend shows a definite decline of CO concentrations after 1990 resulting from the substitution of gasoline-powered vehicles with vehicles equipped with three-way catalysts. Finally, it was found that during days with calm or S-SW blowing light winds the CO concentrations presented their higher values.     

A comparison of European and North American atmospheric deposition networks: polycyclic aromatic hydrocarbons and lindane

A comparison between the sampling and analytical methods used by Canadian (IADN) and German (OSPAR) regional monitoring networks for persistent organic pollutants was conducted from September 2002 to October 2003 at a rural site in Ontario, Canada. Polycyclic aromatic hydrocarbons (PAHs) and the currently-used pesticide lindane were measured in precipitation and ambient air samples. Overall the two networks sampling and analytical methods agreed well in their results of deposition (wet and dry particulate). Lindane concentrations between the two networks agreed well in the air samples while too few precipitation samples could be compared to conclude on agreement. The lindane seasonal profile with a peak in spring-early summer was consistent with previous results pointing to the continued use of this pesticide in 2002-2003 in Canada. Annual lindane wet depositions were comparable between the two network methodologies. PAHs concentrations in precipitation and in gas phase agreed well while there was a discrepancy for particulate PAHs in air. This study confirmed that the use of data from the two regional POPs monitoring networks for hemispherical modelling studies is warranted.     

Air quality assessment of benzo(a)pyrene from asphalt plant operation

A study has been carried out to assess the contribution of Polycyclic Aromatic Hydrocarbons (PAHs) from asphalt plant operation, utilising Benzo(a)pyrene (BaP) as a marker for PAHs, to the background air concentration around asphalt plants in the UK. The purpose behind this assessment was to determine whether the use of published BaP emission factors based on the US Environmental Protection Agency (EPA) methodology is appropriate in the context of the UK, especially as the EPA methodology does not give BaP emission factors for all activities. The study also aimed to improve the overall understanding of BaP emissions from asphalt plants in the UK, and determine whether site location and operation is likely to influence the contribution of PAHs to ambient air quality. In order to establish whether the use of US EPA emissions factors is appropriate, the study has compared the BaP emissions measured and calculated emissions rates from two UK sites with those estimated using US EPA emission factors. A dispersion modelling exercise was carried out to show the BaP contribution to ambient air around each site. This study showed that, as the US EPA methodology does not provide factors for all emission sources on asphalt plants, their use may give rise to over- or under-estimations, particularly where sources of BaP are temperature dependent. However, the contribution of both the estimated and measured BaP concentrations to environmental concentration were low, averaging about 0.05 ng m(-3) at the boundary of the sites, which is well below the UK BaP assessment threshold of 0.25 ng m(-3). Therefore, BaP concentrations, and hence PAH concentrations, from similar asphalt plant operations are unlikely to contribute negatively to ambient air quality.     

Volatile hydrocarbon emissions from vehicles and vertical ventilations in the Hsuehshan traffic tunnel, Taiwan

The concentrations of 56 volatile organic hydrocarbons (VOCs) were measured simultaneously in the southbound bore, the northbound bore and the exhaust air shafts of the Hsuehshan tunnel near Yilan, Taiwan during 2007 and 2008. A total of 60 integrated air samples were collected using stainless steel canisters and analyzed using GC/FID and GC/MS. The highest temperature and lowest relative humidity were observed at the exit of the tunnel owing to the accumulation in the tunnel of waste heat that was exhausted from vehicles. The five most abundant species in all samples were ethylene, acetylene, isopentane, propylene, and toluene. The exit/entrance ratios of total non-methane hydrocarbon (NMHC) concentration were 7.8 and 4.8 for the southbound and northbound bores, respectively. Furthermore, the most abundant species of emission rate (ER) is toluene (21.93-42.89 mg s(-1)), followed by isopentane, ethylene, propylene and 1-butene, with ER ranging from 2.50 to 9.31 mg s(-1) for the three shafts. The ozone formation potential (OFP)/total NMHC ratios in three exhaust air shafts show that the reactivities of these emissions are similar to those of vehicle emissions.