Variability of atmospheric pesticide concentrations between urban and rural areas during intensive pesticide application

Intensive pesticide use leads to the contamination of water, soil and atmosphere. Atmospheric transport is responsible for pesticide dispersal over long distances. In this study, we evaluate the local dispersal of pesticides from agricultural to urban areas. For this purpose, three high-volume samplers, each equipped with a glass fiber filter and XAD-2 resin for the sampling of particulate and gas phase have been placed in a south-west transect (predominant wind direction) characteristic of rural and urban areas. The urban site (Strasbourg centre) is situated in the middle of two rural sites. Samples were taken simultaneously at three sites during pesticide treatments in autumn and spring 2002–2003. Sampling took place for 24 h at a flow rate of 10–15 m³ h⁻¹. The pesticides studied were those commonly used in the Alsace region for all crops (maize, cereal, vines …). Many of the pesticides analysed in atmospheric samples were not detected or observed very episodically at very low concentrations. For metolachlor, alachlor, trifluralin, atrazine and diflufenican, higher concentrations were observed, essentially during the application of these compounds. Moreover, some “spraying peaks” were observed for alachlor in the south rural site (near crops) at a level of 31 ng m⁻³ on 16–17 May 2003. These results show site and time dependence of atmospheric contamination by pesticides. A limited dispersal was also observed especially in the urban area during the application periods of pesticides.     

Pesticides analysed in rainwater in Alsace region (Eastern France): Comparison between urban and rural sites

Current-used pesticides commonly applied in Alsace region (Eastern France) on diverse crops (maize, vineyard, vegetables, etc.) were analysed, together with Lindane, in rainwater between January 2002 and June 2003 simultaneously on two sites situated in a typical rural (Erstein, France) and urban area (Strasbourg, France).Rainwater samples were collected on a weekly basis by using two automatic wet only collectors associated with an open collector for the measurement of rainwater height.Pesticides were analysed by GC-MSMS and extracted from rainwater by SPME. Two runs were performed. The first one was performed by using a PDMS (100 μm) fibre for pesticides where direct injection into GC is possible (alachlor, atrazine, azinphos-ethyl, azinphos-methyl, captan, chlorfenvinphos, dichlorvos, diflufenican, α- and β-endosulfan, iprodione, lindane, metolachlor, mevinphos, parathion-methyl, phosalone, phosmet, tebuconazole, triadimefon and trifluralin). The second run was performed by using PDMS/DVB fibre and this run concerns pesticides where a preliminary derivatisation step with pentafluorobenzylbromide (PFBBr) is required for very low volatiles (bromoxynil,2,4-MCPA, MCPP and 2,4-D) or thermo labiles (chlorotoluron, diuron and isoproturon) pesticides.Results showed that the more concentrated pesticides detected were those used as herbicides in large quantities in Alsace region for maize crops (alachlor, metolachlor and atrazine). Maximum concentrations for these herbicides have been measured during intensive applications periods on maize crops following by rapid decrease immediately after use.For Alachlor, most important peaks have been observed between 21 and 28 April 2003 (3327 ng L⁻¹ at Erstein and 5590 ng L⁻¹ at Strasbourg). This is also the case for Metolachlor where most important peak was observed during the same week.Concentrations of pesticides measured out of application periods were very low for many pesticides and some others where never detected during this period. This is the case for diflufenican which was detected only during application. Two important peaks of concentrations were observed; a first one (101 ng L⁻¹) in Erstein in November 2002 (4–11 November) and a second one (762 ng L⁻¹) also in Erstein (28 April–15 May).The same behaviour can be seen for chlorfenvinphos and phosalone which have been detected, respectively, 2 and 4 times in Erstein and Strasbourg at high concentrations (28 April 2003–15 May 2003, 187 ng L⁻¹ of phosalone and 157 ng L⁻¹ of chlorfenvinphos in Erstein).MCPP, 2,4 MCPA and 2,4-D have been detected at high concentrations in rainwater but for the other pesticides very episodically and mainly during their use in agriculture. Maximal concentrations of MCPP and 2,4 MCPA have been measured in Erstein between 28 April and 15 May (904 and 746 ng L⁻¹, respectively).Comparison between rural and urban sites showed that concentrations in rural areas are generally higher except for pesticides commonly applied in urban areas like Diuron.No seasonal phenomenon was observed for Diuron. This herbicide has been detected in practically all of the rainwater samples in Strasbourg (40/41) with a maximum of 1025 ng L⁻¹ (16–23 September 2002) in 38 samples on 41 in Erstein with a maximum of 317 ng L⁻¹ (15–23 October 2002). The total concentration of Diuron measured between 4 March 2002 and 20 July 2003 is of 4721 ng L⁻¹ in Strasbourg and 5025 ng L⁻¹ in Erstein. This result shows that wet deposition of Diuron in urban and rural sites was equivalent and can be explained by the “urban use” of this molecule together with its potential persistence.     

Influence of usage and chemical–physical properties on the atmospheric transport and deposition of pesticides to agricultural regions of Manitoba,Canada

This study quantified the masses of 14 pesticides deposited as wet (precipitation) versus dry (gaseous and particle) atmospheric deposition at a research farm in southwestern Manitoba, Canada. The concentration in air of these pesticides was also measured. Total bulk deposition amounts (wet + dry) ranged from 0.009 to 2.3 μg m^?2 for the 12 pesticides detected, and for the six pesticides with both wet and dry deposition detections, dry deposition contributed 12–51% of the total deposition over the crop growing season. Although not applied at the site, eight herbicides registered for use in Canada, as well as lindane (γ-HCH), were all frequently detected (92–100%) in the 12 air samples analyzed during the crop growing season, with by-product isomer α-HCH (75%), clopyralid (50%) and atrazine (8%) detected to a lesser extent. The chemical’s physicochemical properties and the relative mean mass of each agricultural pesticide applied in the province of Manitoba and in a 13 km radius were significant parameters in explaining the trends in the concentrations of pesticides detected in our samples. The important contribution of dry deposition to total pesticide deposition warrants greater attention in arid and semi-arid areas such as the Prairie Region of Canada, also because under a changing climate this region is estimated to experience more severe droughts while the more favorable conditions predicted for pest infestations could lead to increased pesticide applications in agricultural and urban areas.     

A mobile pollutant measurement laboratory—measuring gas phase and aerosol ambient concentrations with high spatial and temporal resolution

A mobile pollutant measurement laboratory was designed and built at the Paul Scherrer Institute (Switzerland) for the measurement of on-road ambient concentrations of a large set of trace gases and aerosol parameters with high time resolution (<15 s for most instruments), along with geographical and meteorological information. This approach allowed for pollutant level measurements both near traffic (e.g. in urban areas or on freeways/main roads) and at rural locations far away from traffic, within short periods of time and at different times of day and year. Such measurements were performed on a regular base during the project year of gas phase and aerosol measurements (YOGAM). This paper presents data measured in the Zürich (Switzerland) area on a late autumn day (6 November) in 2001. The local urban particle background easily reached 50 000 cm⁻³, with additional peak particle number concentrations of up to 400 000 cm⁻³. The regional background of the total particle number concentration was not found to significantly correlate with the distance to traffic and anthropogenic emissions of carbon monoxide and nitrogen oxides. On the other hand, this correlation was significant for the number concentration of particles in the size range 50–150 nm, indicating that the particle number concentration in this size range is a better traffic indicator than the total number concentration. Particle number size distribution measurements showed that daytime urban ambient air is dominated by high number concentrations of ultrafine particles (nanoparticles) with diameters <50 nm, which are immediately formed by traffic exhaust and thus belong to the primary emissions. However, significant variation of the nanoparticle mode was also observed in number size distributions measured in rural areas both at daytime and nighttime, suggesting that nanoparticles are not exclusively formed by primary traffic emissions. While urban daytime total number concentrations were increased by a factor of 10 compared to the nighttime background, corresponding factors for total surface area and total volume concentrations were 2 and 1.5, respectively.     

Determination of priority pesticides in water samples combining SPE and SPME coupled to GC–MS. A case study: Suquía River basin (Argentina)

This study reports a combined method using solid phase extraction (SPE), followed by solid phase microextraction (SPME) to concentrate different pesticides, including chlorinated, organophosphorus, triazines, pyretroids and chloroacetamides, present at trace levels in water samples. Identification and quantification was carried out by gas chromatography coupled to Mass Spectrometry (GC–MS). The optimized methodology showed LOQs at ng L^?1 levels (ranging 0.2–3.5 ng L^?1) in addition to acceptable precision and robustness (recoveries ranged 63–104%, RSD from 4% to 23%), presenting a novel method to reach trace levels, similar to that obtainable using EC detector, with structural confirmation by MS during the analysis of a wide range of environmental pollutants.This method was applied to the study of temporal and spatial distribution of pesticides in the Suquía River basin (Córdoba-Argentina). As expected, highest levels of agrochemicals were observed in areas with intensive agricultural practices, being atrazine (max. = 433.9 ng L^?1), alpha-cypermetrine (max. = 121.7 ng L^?1) and endosulfan sulfate (max. = 106.7 ng L^?1) predominant. In urban areas, the prevalent pesticide was alpha-cypermethrine. These results draw attention to the need of pesticide monitoring programs in rivers, considering both urban and rural sections.     

Atmospheric deposition of organochlorine contaminants to Galveston Bay,Texas

Atmospheric monitoring of PCBs and chlorinated pesticides (e.g., HCHs, chlordanes, and DDTs) in Galveston Bay was conducted at Seabrook, Texas. Air and wet deposition samples were collected from 2 February 1995 and continued through 6 August 1996. Vapor total PCB (tPCB) concentrations in air ranged from 0.21 to 4.78 ng m⁻³ with a dominance of tri-chlorinated PCBs. Dissolved tPCBs in rain ranged from 0.08 to 3.34 ng l⁻¹, with tetra-chlorinated PCBs predominating. The predominant isomers found in air and rain were α- and γ-HCH, α- and γ-chlordanes, 4,4′-DDT, and dieldrin. The concentrations of PCBs and pesticides in the air and rain revealed no clear seasonal trend. Elevated levels of PCBs in the air occurred when temperatures were high and wind came from urban and industrialized areas (S, SW, NW, and W of the site). Concentrations of HCHs were elevated in April, May, and October, perhaps due to local and/or regional applications of γ-HCH (lindane). Other pesticides showed no notable temporal variation. When winds originated from the Gulf of Mexico (southeasterly), lower concentrations of organochlorines were detected in the air. The direct deposition rate (wet+dry) of PCBs to Galveston Bay (6.40 μg m⁻² yr⁻¹) was significantly higher than that of pesticides by a factor of 5–10. The net flux from gas exchange estimated for PCBs was from Galveston Bay water to the atmosphere (78 μg m⁻² yr⁻¹). Gas exchange of PCBs from bay water to the atmosphere was the dominant flux.     

Production and removal of aerosol in a polluted fog layer: model evaluation and fog effect on PM

A radiation fog physics, gas- and aqueous-phase chemistry model is evaluated against measurements in three sites in the San Joaquin Valley of California (SJV) during the winter of 1995. The measurements include for the first time vertically resolved fog chemical composition measurements. Overall the model is successful in reproducing the fog dynamics as well as the temporal and spatial variability of the fog composition (pH, sulfate, nitrate, and ammonium concentrations) in the area. Sulfate production in the fog layer is relatively slow (1–4 μg m⁻³ per fog episode) compared to the episodes in the early 1980s because of the low SO₂ concentrations in the area and the lack of oxidants inside the fog layer. Sulfate production inside the fog layer is limited by the availability of oxidants in the urban areas of the valley and by SO₂ in the more remote areas. Nitrate is produced in the rural areas of the valley by the heterogeneous reaction of N₂O₅ on fog droplets, but this reaction is of secondary importance for the more polluted urban areas. The gas-phase production of HNO₃ during the daytime is sufficient to balance the nitrate removed during the nighttime fog episodes. Entrainment of air from the layer above the fog provides another source of reactants for the fog layer. Wet removal is one of most important processes inside the fog layer in SJV. We estimate based on the three episodes investigated during IMS95 that a typical fog episode removes 500–2000 μg m⁻² of sulfate, 2500–6500 μg m⁻² of nitrate, and 2000–3500 μg m⁻² of ammonium. For the winter SJV valley the net fog effect corresponds to reductions in ground ambient concentrations of 0.05–0.2 μg m⁻³ for sulfate, 3–6 μg m⁻³ for total nitrate, and 1–3 μg m⁻³ for total ammonium.     

Air concentrations and wet deposition of major inorganic ions at five non-urban sites in China, 2001–2003

Air and precipitation measurements at five sites were undertaken from 2001 to 2003 in four different provinces in China, as part of the acid rain monitoring program IMPACTS. The sites were located in Tie Shan Ping (TSP) in Chongqing, Cai Jia Tang (CJT) in Hunan, Lei Gong Shan (LGS) and Liu Chong Guan (LCG) in Guizhou and Li Xi He (LXH) in Guangdong. The site characteristics are quite varied with TSP and LCG located relatively near big cites while the three others are situated in more regionally representative areas. The distances to urban centres are reflected in the air pollution concentrations, with annual average concentrations of SO₂ ranging from 0.5 to above 40 μg S m⁻³. The main components in the airborne particles are (NH₄)₂SO₄ and CaSO₄. Reduced nitrogen has a considerably higher concentration level than oxidised nitrogen, reflecting the high ammonia emissions from agriculture. The gas/particle ratio for the nitrogen compounds is about 1:1 at all the three intensive measurement sites, while for sulphur it varies from 2.5 to 0.5 depending on the distance to the emission sources. As in air, the predominant ions in precipitation are sulphate, calcium and ammonium. The volume weighted annual concentration of sulphate ranges from about 70 μeq l⁻¹ at the most rural site (LGS) to about 200 μeq l⁻¹ at TSP and LCG. The calcium concentration ranges from 25 to 250 μeq l⁻¹, while the total nitrogen concentration is between 30 and 150 μeq l⁻¹; ammonium is generally twice as high as nitrate. China's acid rain research has traditionally been focused on urban sites, but these measurements show a significant influence of long range transported air pollutants to rural areas in China. The concentration levels are significantly higher than seen in most other parts of the world.     

Organic Matter of the Troposphere—II.: Natural Background of biogenic lipid matter in aerosols over the rural western United States

Higher plant waxes are the predominant natural components in the lipid fractions (> C₁₅) of aerosols sampled over rural and oceanic regions. Hydrocarbon, fatty acid, ketone and fatty alcohol fractions of the lipids were characterized in terms of their contents of homologous compound series and specific biogenic molecular markers. Particulate samples from the rural western United States have been analyzed and compared with samples from urban Los Angeles and remote areas over the Atlantic Ocean. The samples from rural sites contained predominantly vascular plant wax and lesser amounts of higher plant sterols and resin residues. Urban samples and, to varying degrees, some rural samples contained primarily higher weight residues of petroleum products. The loadings of hydrocarbons derived from higher plant waxes ranged approximately from 10 to 160 ng m⁻³ of air (for fatty acids, 10–100 ng m⁻³ and for fatty alcohols, 10–200 ng m⁻³). Higher molecular weight lipids (i.e. plant epicuticular wax, terpenes, etc.) from flora comprise a significant component of the organic carbon in rural aerosols. Primary biogenic residues are major components of aerosols in all areas and they are important components in the global cycling of organic carbon.     

Urban and rural ultrafine (PM0.1) particles in the Helsinki area

In June 1996–June 1997 Berner low-pressure impactors were used at an urban and at a rural site in the Helsinki area for sampling ultrafine particles (UFP, PM_0.1). Ten sample pairs, each pair measured simultaneously, were collected in the size range of 0.03–15 μm of particle aerodynamic diameter. More than 40 chemical components were measured. Surprisingly, the average UFP mass concentration was higher at the rural site (520 ng/m³) than at the urban site (490 ng/m³). The average chemical composition of UFP was similar at the two sites. The most abundant of the measured components were sulphate (32 and 40 ng/m³ for the urban and rural sites, respectively), ammonium (22 and 25 ng/m³), nitrate (4 and 11 ng/m³) and the Ca²⁺ ion (5 and 7 ng/m³). The most important metals at both sites were Ca, Na, Fe, K and Zn with concentrations between 0.7 and 5 ng/m³. Of the heavy metals, Ni, V, Cu, and Pb were important with average ultrafine concentrations between about 0.1 and 0.2 ng/m³. Also the organic anions oxalate (urban 2.1 ng/m³ and rural 1.9 ng/m³) and methanesulphonate (1.3 and 1.7 ng/m³) contributed similarly at both sites. The measured species accounted for only about 15–20% of the total ultrafine mass. The fraction that was not measured includes mainly carbonaceous material and water. It was estimated that the amount of water was about 10% (50 ng/m³) and that of carbonaceous material about 70% (350 ng/m³) at both sites. Aitken modes were observed for most components with the average mass mean mode diameters being between about 0.06 and 0.12 μm. The average concentrations in the Aitken mode differed clearly from those in the UFP for several components.The average contribution of ultrafine mass to the fine particle mass (PM_2.5) was about 7% at the urban site and 8.5% at the rural site. At both sites the contribution of ultrafine to fine was especially high for Se, Ag, B, and Ni (10–20%) and at the rural site also for Co (20%), Ca²⁺ (16%) and Mo (11%). Enrichment in the ultrafine particles suggests that local sources may exist for these elements.Aitken modes turned out to be useful indicators of local sources for several components. The Aitken modes of Ba, Ca, Mg and Sr were similar in several samples, suggesting a common local combustion source for these elements, possibly traffic exhaust. Co, Fe, Mo and Ni formed another group of elements often having similar Aitken modes, the likely source being combustion of heavy fuel oil.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta

Twenty-four hour PM_2.5 samples from a rural site, an urban site, and a suburban site (next to a major highway) in the metropolitan Atlanta area in December 2003 and June 2004 were analyzed for 19 polycyclic aromatic hydrocarbons (PAH). Extraction of the air samples was conducted using an accelerated solvent extraction method followed by isotope dilution gas chromatography/mass spectrometry determination. Distinct seasonal variations were observed in total PAH concentration (i.e. significantly higher concentrations in December than in June). Mean concentrations for total particulate PAHs in December were 3.16, 4.13, and 3.40 ng m^?3 for the urban, suburban and rural sites, respectively, compared with 0.60, 0.74, and 0.24 ng m^?3 in June. Overall, the suburban site, which is impacted by a nearby major highway, had higher PAH concentration than did the urban site. Total PAH concentrations were found to be well correlated with PM_2.5, organic carbon (OC), and elemental carbon (EC) in both months (r² = 0.36–0.78, p < 0.05), although the slopes from the two months were different. PAHs represented on average 0.006% of total PM_2.5 mass and 0.017% of OC in June, compared with 0.033% of total PM_2.5 and 0.14% of OC in December. Total PAH concentrations were also correlated with potassium ion (r² = 0.39, p = 0.014) in December, but not in June, suggesting that in winter biomass burning can potentially be an important source for particulate PAH. Retene was found at a higher median air concentration at the rural site than at the urban and suburban sites—unlike the rest of the PAHs, which were found at lower levels at the rural site. Retene also had a larger seasonal difference and had the weakest correlation with the rest of the PAHs measured, suggesting that retene, in particular, might be associated with biomass burning.     

Elevated atmospheric CO2 concentration and temperature across an urban–rural transect

The heat island effect and the high use of fossil fuels in large city centers are well documented, but by how much fossil fuel consumption is elevating atmospheric CO₂ concentrations and whether elevations in both atmospheric CO₂ and air temperature from rural to urban areas are consistently different from year to year are less well known. Our aim was to record atmospheric CO₂ concentrations, air temperature and other environmental variables in an urban area and compare it to suburban and rural sites to see if urban sites are experiencing climates expected globally in the future with climate change. A transect was established from Baltimore city center (Urban site), to the outer suburbs of Baltimore (suburban site) and out to an organic farm (rural site). At each site a weather station was set-up to monitor environmental variables for 5 years. Atmospheric CO₂ was consistently and significantly increased on average by 66 ppm from the rural to the urban site over the 5 years of the study. Air temperature was also consistently and significantly higher at the urban site (14.8 °C) compared to the suburban (13.6 °C) and rural (12.7 °C) sites. Relative humidity was not different between sites whereas the vapor pressure deficit (VPD) was significantly higher at the urban site compared to the suburban and rural sites. An increase in nitrogen deposition at the rural site of 0.6% and 1.0% compared to the suburban and urban sites was small enough not to affect soil nitrogen content. Dense urban areas with large populations and high vehicular traffic have significantly different microclimates compared to outlying suburban and rural areas. The increases in atmospheric CO₂ and air temperature are similar to changes predicted in the short term with global climate change, therefore providing an environment suitable for studying future effects of climate change on terrestrial ecosystems.     

Preliminary study of the determination of ambient carbonyls in Xalapa City,Veracruz, Mexico

A preliminary study of ambient carbonyls was performed in Xalapa City to measure carbonyls in the atmosphere of this City, because it has an explosive increase in population and traffic density, but few industries. The city is located at the eastern flanks of the Sierra Madre Oriental, between 1350 and 1550 m above sea level. Acetone was the most abundant carbonyl in June, followed by formaldehyde and acetaldehyde, whereas acetaldehyde was the most abundant one in November. Higher concentrations were observed in autumn than in spring, probably due to stagnation conditions in autumn and heavy rains from late spring to early autumn. The very high concentrations of acetaldehyde found in November could have been caused by an accidental leak or spill from a truck, since no stationary sources were identified and acetaldehyde concentrations steeply rose and constantly decreased after few days. Moreover, a highly transited highway traverses Xalapa. The most important ozone and carbon monoxide concentrations were below the Mexican Air Quality Standards; 216 μg m⁻³ (0.11 ppm) for 1 h average and 12.6 mg m⁻³ (11 ppm) for 8 h moving average, respectively. The low concentrations of the main carbonyls, compared with the values reported for other urban areas, and of carbon monoxide, seem to indicate that air quality is still satisfactory in Xalapa City.     

Airborne cadmium in the major monitoring locations in Korea between 1991 and 2004

Air quality monitoring data for cadmium (Cd) collected in 13 cities in Korea over a 14-year period (1991–2004) have been analyzed. In the course of this study, variation of Cd was examined over time and with location to learn about its sources, transport, and removal processes and to help improve air quality control. The results of this study indicate that the spatial distribution of Cd is clearly distinguishable between different cities and that such a pattern is sensitively reflected by such a factor as the level of industrialization. Comparison of the Cd data sets between different cities indicated that its concentration levels observed in highly industrialized cities approached or exceeded 10 ng m⁻³, while those of urban background cities were found to lie in a narrow range of 1–3 ng m⁻³. As such, Cd values determined from the polluted areas were notably higher than the relatively clean ones, at least by several times. The Cd data collected from all study sites were also evaluated with respect to temporal behavior. Inspection of seasonal patterns generally showed the occurrences of the highest Cd value during spring (and winter) and the lowest one during summer. When the long-term pattern of Cd was assessed across all study years, the results differed greatly between different cities in relation to their pollution status. Although Cd concentrations tended to decrease rather abruptly in highly industrialized cities, its patterns for most cities were too variable to project a definitive trend. The results of this analysis thus suggest that Cd concentration levels in most urban areas of Korea are fairly comparable with those commonly seen in the urban background areas of western countries. Considering that most urban areas are affected by various pollution sources and that Cd concentrations have been reduced significantly through the years, more deliberate efforts are needed to further control Cd concentrations in the atmosphere.     

An empirical model for predicting urban roadside nitrogen dioxide concentrations in the UK

An annual mean concentration of 40 μg m⁻³ has been proposed as a limit value within the European Union Air Quality Directives and as a provisional objective within the UK National Air Quality Strategy for 2010 and 2005, respectively. Emissions reduction measures resulting from current national and international policies are likely to deliver significant reductions in emissions of oxides of nitrogen from road traffic in the near future. It is likely that there will still be exceedances of this target value in 2005 and in 2009 if national measures are considered in isolation, particularly at the roadside. It is envisaged that this `policy gap’ will be addressed by implementing local air quality management to reduce concentrations in locations that are at risk of exceeding the objective. Maps of estimated annual mean NO₂ concentrations in both urban background and roadside locations are a valuable resource for the development of UK air quality policy and for the identification of locations at which local air quality management measures may be required. Maps of annual mean NO₂ concentrations at both background and roadside locations for 1998 have been calculated using modelling methods, which make use of four mathematically straightforward, empirically derived linear relationships. Maps of projected concentrations in 2005 and 2009 have also been calculated using an illustrative emissions scenario. For this emissions scenario, annual mean urban background NO₂ concentrations in 2005 are likely to be below 40 μg m⁻³, in all areas except for inner London, where current national and international policies are expected to lead to concentrations in the range 40–41 μg m⁻³. Reductions in NO_x emissions between 2005 and 2009 are expected to reduce background concentrations to the extent that our modelling results indicate that 40 μg m⁻³ is unlikely to be exceeded in background locations by 2009. Roadside NO₂ concentrations in urban areas in 2005 and 2009 are expected to be significantly higher than in background locations. 21% of urban major road links are expected to have roadside NO₂ greater than or equal to 40 μg m⁻³ in 2005 for our illustrative emissions scenario. The continuing downward trend in traffic emissions is likely to further reduce the number of links exceeding this value by 2009, with about 6% of urban major road links predicted to have concentrations higher than 40 μg m⁻³. The majority of these links are in the London area. The remaining links are generally confined to the most heavily trafficked roads in other big cities.     

Saharan dust contributions to PM10 and TSP levels in Southern and Eastern Spain

The analysis of PM10 and TSP levels recorded in rural areas from Southern and Eastern Spain (1996–1999) shows that most of the PM10 and TSP peak events are simultaneously recorded at monitoring stations up to 1000 km apart. The study of the atmospheric dynamics by back-trajectory analysis and simulations with the SKIRON Forecast System show that these high PM10 and TSP events occur when high-dust Saharan air masses are transported over the Iberian Peninsula. In the January–June period, this dust transport is mainly caused by cyclonic activity over the West or South of Portugal, whereas in the summer period this is induced by anticyclonic activity over the East or Southeast Iberian Peninsula. Most of the Saharan intrusions which exert a major influence on the particulate levels occur from May to September (63%) and in January and October. In rural areas in Northeast Spain, where the PM10 annual mean is around 18 μg PM10 m⁻³, the Saharan dust accounts for 4–7 annual daily exceedances of the forthcoming PM10-EU limit value (50 μg PM10 m⁻³ daily mean). Higher PM10 background levels are recorded in Southern Spain (30 μg PM10 m⁻³ as annual mean for rural areas) and very similar values are recorded in industrial and urban areas. In rural areas in Southern Spain, the Saharan dust events accounts for 10–23 annual daily exceedances of the PM10 limit value, a high number when compared with the forthcoming EU standard, which states that the limit value cannot be exceeded more than 7 days per year. The proportion of Sahara-induced exceedances with respect to the total annual exceedances is discussed for rural, urban and industrial sites in Southern Spain.     

The composition and sources of PM2.5 organic aerosol in two urban areas of Chile

Fine particle (PM_2.5) samples were collected, using a charcoal diffusion denuder, in two urban areas of Chile, Santiago and Temuco, during the winter and spring season of 1998. Molecular markers of the organic aerosol were determined using GC/MS. Diagnostic ratios and molecular tracers were used to investigate the origin of carbonaceous aerosols. As main sources, road and non-road engine emissions in Santiago, and wood burning in Temuco were identified. Cluster analysis was used to compare the chemical characteristics of carbonaceous aerosols between the two urban environments. Distinct differences between Santiago and Temuco samples were observed. High concentrations of isoprenoid (30–69 ng m⁻³) and unresolved complex mixture (UCM) of hydrocarbons (839–1369 ng m⁻³) were found in Santiago. High concentrations of polynuclear aromatic hydrocarbons (751±304 ng m⁻³) and their oxygenated derivatives (4±2 ng m⁻³), and of n-alk-1-enes (16±13 ng m⁻³) were observed in Temuco.     

Bioaccumulation of polybrominated diphenyl ethers in harbor seals from the northwest Atlantic

Polybrominated diphenyl ethers (PBDEs) were analyzed in blubber of harbor seals (Phoca vitulina concolor) collected between 1991 and 2005 along the northwest Atlantic. ∑PBDE concentrations (mono- to hexa-BDEs) detected in blubber samples (n = 42) ranged from 80 to 25 720 ng g⁻¹ lw, (overall mean 2403 ± 5406 ng g⁻¹ lw). By age, mean ∑PBDE concentrations were: 3645 ± 7388, 2945 ± 5995, 1385 ± 1265, and 326 ± 193 ng g⁻¹ lw in pups, yearlings, adult males, and adult females, respectively. Unlike the trend for PCBs, no decreasing gradient from urban to rural/remote areas was observed for PBDEs in these samples, likely reflecting inputs from local sources. No significant temporal trend was observed for PBDEs in harbor seals between 1991 and 2005, although congener profiles shifted over time. Tetra-BDE-47 was the dominant congener, followed by BDEs-99, -100, -153, -154, and -155 in varying order, suggesting exposure to the penta-BDE product. In adult males, the hexa-BDEs contributed more to the total (22%) than BDEs-99 and -100 (14%), and concentrations of BDE-155 were elevated compared with -154. Higher BDEs were detected in a subset of seals (n = 12) including hepta-BDE-183, the marker for the octa-BDE mixture, and octa-BDE-197, along with several unidentified hepta- and octa- congeners. BDE-209 was detected in seal blubber at concentrations ranging from 1.1 to 8 ng g⁻¹ lw, indicating that deca-BDE is bioavailable in this marine food web. This is the first study to document the accumulation of BDE-209 at measurable levels in wild harbor seals. While the PBDE patterns in blubber indicate exposure to all three BDE commercial mixtures, the data also suggest that BDE-209 debromination by seal prey fish may contribute to the loading of lower brominated congeners (hexa- to octa-BDEs) in these seals.     

Aromatic hydrocarbons at urban,sub-urban,rural (8°52′N; 67°19′W) and remote sites in Venezuela

Using the novel on-line proton transfer reaction mass spectrometry (PTR-MS) technique, atmospheric concentrations of benzene, toluene, xylenes, and C₉-benzenes were measured in Caracas (urban), Altos de Pipe (sub-urban), Calabozo (rural) and Parupa (remote), during various campaigns in 1999 and 2000.Average daytime mixing ratios measured in Caracas are 1.1, 3.2, 3.7, and 2.7 nmol/mol for benzene, toluene, xylenes, and C₉-benzenes. At the sub-urban site, located only few km from Caracas, relatively low levels (∼20% of the levels measured in Caracas) of these aromatic hydrocarbons were observed.At the rural site during the dry season, higher concentrations of benzene (0.15 nmol/mol) were recorded, whereas those of toluene (0.08 nmol/mol) were lower during that time. The aromatic hydrocarbon ratios in the wet season (benzene: 0.08 nmol/mol; toluene: 0.09 nmol/mol) are consistent with an aged urban plume, whereas biomass burning emissions dominate during the dry season. From rural and urban [benzene]/[toluene] ratios a mean HO concentration of 2.6×10⁶ molecules/cm³ was estimated during the wet season. This value must be considered an overestimate because it does not account for background concentrations which are likely for benzene and toluene.At the remote “La Gran Sabana” region (Parupa) very low mixing ratios (0.031 and 0.015 nmol/mol for benzene and toluene) are showing the pristine region to be unaffected by local sources. From the [benzene]/[toluene] ratio we deduced, that “urban” air arriving from the coastline (350 km) is likely mixed with air containing some background of benzene and toluene.Urban emissions (automobiles) should be the major source of aromatic compounds, however, during the dry season biomass burning seems to make an important contribution.     

Air pollutants in rural homes in Guizhou,China – Concentrations,speciation, and size distribution

Several types of fuels, including coal, fuel wood, and biogas, are commonly used for cooking and heating in Chinese rural households, resulting in indoor air pollution and causing severe health impacts. In this paper, we report a study monitoring multiple pollutants including PM₁₀, PM_2.5, CO, CO₂, and volatile organic compounds (VOCs) from fuel combustion at households in Guizhou province of China. The results showed that most pollutants exhibited large variability for different type of fuels except for CO₂. Among these fuels, wood combustion caused the most serious indoor air pollution, with the highest concentrations of particulate matters (218～417 μg m^?3 for PM₁₀ and 201～304 μg m^?3 for PM_2.5), and higher concentrations of CO (10.8 ± 0.8 mg m^?3) and TVOC (about 466.7 ± 337.9 μg m^?3). Coal combustion also resulted in higher concentrations of particulate matters (220～250 μg m^?3 for PM₁₀ and 170～200 μg m^?3 for PM_2.5), but different levels for CO (respectively 14.5 ± 3.7 mg m^?3 for combustion in brick stove and 5.5 ± 0.7 mg m^?3 for combustion in metal stove) and TVOC (170 mg m^?3 for combustion in brick stove and 700 mg m^?3 for combustion in metal stove). Biogas was the cleanest fuel, which brought about the similar levels of various pollutants with the indoor case of non-combustion, and worth being promoted in more areas. Analysis of the chemical profiles of PM_2.5 indicated that OC and EC were dominant components for all fuels, with the proportions of 30～48%. A high fraction of SO₄^2? (31～34%) was detected for coal combustion. The cumulative percentages of these chemical species were within the range of 0.7～1.3, which was acceptable for the assessment of mass balance.