Long-term assessment of the wet precipitation chemistry in Austria (1984-1999)

The aim of the present study was to determine the long-time trends in concentrations and depositions of major ions in wet precipitation samples collected at 11 sampling sites from the Austrian precipitation chemistry network in the period 1984-1999. The analytical results were treated by the use of least square linear regression method. It is shown that a serious decrease of sulfate (between 30% and 60% for the period) and hydrogen ion (between 60% and 102% for the period) concentrations and depositions is achieved at almost all sampling sites and in most of these cases the linear trend proves to be statistically significant. Nitrogen containing ions and base cations do not reveal a distinct trend of changing and in the majority of the sites the linear models are not adequate. In principle, an overall slight concentration and deposition decrease for these major ions is observed (up to 30% for the period of observation) but some substantial exceptions are also found (site Haunsberg or site Lobau). The changes in chloride concentration and deposition, too, do not indicate significant linear trend and, in general, are decreasing for the period of monitoring. In order to give some explanation of the exceptional behaviour of some of the major ions in several sites, an additional comparison with Austrian emission data (sulfur dioxide, nitrogen oxides, ammonium) and with data from five EMEP sites from neighbouring countries is performed. A significant West-East trend of acidity increase is found as well as a good correlation with the emission trends. Therefore, both transboundary and specific local factors could be substantial factors in the wet precipitation chemistry in the region.     

Source apportionment of fine particles at urban background and rural sites in the UK atmosphere

Airborne fine particulate matter (PM_2.5) has been collected at two sites in the West Midlands conurbation, UK, representing urban background and rural locations. Chemical analyses have been carried out for major anions, trace metals, total OC and EC, and for individual organic marker species including n-alkanes, hopanes, PAHs, organic acids and sterols. Source apportionment has been conducted using both a pragmatic mass closure model and the US EPA chemical mass balance (CMB) model. The pragmatic mass closure model is well able to account for the measured PM_2.5 mass in terms of chemical/source components, and the chemical mass balance model has been used to apportion the carbonaceous component of the aerosol. The dominant components of PM_2.5 at both sites are secondary inorganic (sulphate and nitrate) and carbonaceous particles. The CMB model shows the latter to arise mainly from road traffic sources, with smaller contributions from vegetative detritus, wood smoke, natural gas, coal, and dust/soil. The CMB model also identifies an important component of the organic aerosol not associated with these primary sources, which correlates very strongly with secondary organic aerosol estimated from the OC/EC ratio. The split between different automotive source types does not relate well to UK emission inventories, and may indicate that CMB source profiles from North American studies and different carbon analysis protocols may lead to erroneous conclusions.     

Methyl tert-butyl ether (MTBE) in urban and rural precipitation in Germany

The use of the oxygenate methyl tert-butyl ether (MTBE) in gasoline has led to detectable concentrations in urban and rural air up to 160 ppbV. Results from MTBE measurement in precipitation have not been reported so far. In the present study, 120 samples of precipitation collected at 17 sampling locations all over Germany have been analyzed for their MTBE content. Analysis is performed by a combination of headspace-solid-phase microextraction (HS-SPME) and gas chromatography/mass spectrometry (GC-MS). A 75 μm poly(dimethylsiloxane)/Carboxene fiber and a cryostat is used for SPME. The detection limit is 10 ng/l. In precipitation samples, MTBE was detected in wintertimes only with a maximum concentration of 85 ng/l. Measurement at Frankfurt/M City from 6 September 2000 to 12 March 2001 provided for 49% of the data concentrations in the range of 30–85 ng/l (n=17). Sampling in winter 2000/2001 at several German cities and rural locations showed that MTBE is more often detectable in urban (86%, n=78) than in rural (18%, n=42) precipitation. By comparing the results with corresponding temperatures and amounts of precipitation it can be concluded that the detection of MTBE in urban precipitation is observed at ambient temperatures lower than about 10–15°C. Moreover, the first precipitation after a dry period accumulates more MTBE than precipitation during or at the end of a wet period (wash-out effect). Highest concentrations occurred in snow samples. Corresponding mean air equilibrium concentrations of 0.04 ppbV (urban samples) and 0.01 ppbV (rural samples) are calculated. This is about one magnitude lower than year round and summertime measurements in the US and in Switzerland. Urban runoff (n=12) and corresponding precipitation sampling indicate that urban runoff might be composed of about 20% MTBE that is already transported by air and precipitation, whereas about 80% may be attributed to direct uptake of vehicle emissions and leakage near the road during precipitation.     

Spatial variability of different fractions of particulate matter within an urban environment and between urban and rural sites

The spatial variability of different fractions of particulate matter (PM) was investigated in the city of Basel, Switzerland, based on measurements performed throughout 1997 with a mobile monitoring station at six sites and permanently recorded measurements from a fixed site. Additionally, PM10 measurements from the following year, which were concurrently recorded at two urban and two rural sites, were compared. Generally, the spatial variability of PM4, PM10, and total suspended particulates (TSP) within this Swiss urban environment (area = 36 km2) was rather limited. With the exception of one site in a street canyon next to a traffic light, traffic density had only a weak tendency to increase the levels of PM. Mean PM10 concentration at six sites with different traffic densities was in the range of less than +/- 10% of the mean urban PM10 level. However, comparing the mean PM levels on workdays to that on weekends indicated that the impact of human activities, including traffic, on ambient PM levels may be considerable. Differences in the daily PM10 concentrations between urban and more elevated rural sites were strongly influenced by the stability of the atmosphere. In summer, when no persistent surface inversions exist, differences between urban and rural sites were rather small. It can therefore be concluded that spatial variability of annual mean PM concentration between urban and rural sites in the Basel area may more likely be caused by varying altitude than by distance to the city center.     

Measurements of nitrogen dioxide concentrations at rural sites in the United Kingdom using diffusion tubes

Nitrogen dioxide concentrations have been measured at rural sites in the United Kingdom and have revealed a marked spatial variation. The annual mean NO2 concentration varies from approximately 1 microg Nm-3 in Northern Ireland to approximately 7 microg Nm-3 in East Anglia. Though the temporal resolution of the diffusion tube method is limited by exposure periods of 2-4 weeks, it was possible to detect a marked seasonal variation in NO2 concentration at all sites, with higher values in the winter than in the summer. This is in contrast to the small seasonal variation previously observed at sites in London. Sulphur dioxide concentrations were measured daily using a bubbler method and, if expressed in terms of mass of sulphur and nitrogen, the SO2 and NO2 annual mean concentrations were similar. This is in contrast to an S/N ratio of greater than 3 in total UK emissions of SO2 and NOx. It seems likely that this difference is due to a combination of the different spatial distributions and heights of emissions of SO2 and NOx, the influence of local sources of NOx, and the smaller S/N ratio in Continental European emissions.     

Relating meteorological variables and trends in motor vehicle emissions to monthly urban carbon monoxide concentrations

A model which quantifies the relationship between the monthly time series for CO emissions, the monthly time series in ambient CO concentration, and meteorologically driven dispersion was developed. Fifteen cities representing a wide range of geographical and climatic conditions were selected. An eight-year time series (1984–1991 inclusive) of monthly averaged data were examined in each city. A new method of handling missing ambient concentration values which is designed to calculate city-wide average concentrations that follow the trend seen at individual monitor sites is presented. This method is general and can be used in other applications involving missing data. The model uses emissions estimates along with two meteorological variables (wind speed and mixing height) to estimate monthly averages of ambient air pollution concentrations. The model is shown to have a wide range of applicability; it works equally well for a wide range of cities that have very different temporal CO distributions. The model is suited for assessing long-term trends in ambient air pollutants and can also be used for estimating seasonal variations in concentration, estimation of trends in emissions, and for filling in gaps in the ambient concentration record.     

Carbonaceous aerosol in urban and rural European atmospheres: estimation of secondary organic carbon concentrations

Aerosol samples from urban, rural and coastal areas in Europe were analysed for carbonaceous content by a thermaloptical transmission method. The fraction of particulate organic carbon with a secondary origin in gas/particle conversion of volatile organic compounds was estimated from the minimum ratio between particulate organic and black carbon, which occurred during periods of reduced photochemical activity. Values calculated by this method ranged from a minimum of 17%, in Birmingham, UK, during winter, to a maximum of 78% at a rural coastal area, in Portugal, with air masses transported directly from the ocean. A clear seasonal dependence was observed at both rural and urban environments, with minimum secondary organic carbon production during winter.     

Seasonal variation in atmospheric aerosol concentration and composition at urban and rural sites in northern England

Seasonal variations in atmospheric aerosol concentration and composition have been determined at two nearby sites, one urban and one rural, near Leeds, W. Yorkshire. Aerosols, sampled on a daily basis and collected in the size ranges < 2.5 μm and 2.5−15 μm, were analysed for total mass, SO²⁻₄, NO⁻₃, Cl⁻ and NH⁺₄. Dark smoke and SO₂ were also measured at both sites. Results are given covering the period October 1982–September 1983. The average concentration of particles was higher at the urban site. The urban-rural difference in coarse particle concentration, which was about a factor of 2, was more significant than the difference in the fine particle concentration, which was only 1.3. Smoke and SO₂ concentrations showed strong wintertime maxima and summertime minima. Fine NO⁻₃ and Cl⁻ concentrations also had pronounced wintertime maxima and summertime minima attributed to the variation in volatility of their ammonium salts. Total mass, SO²⁻₄ and NH⁺₄ did not show any clear seasonal variations. Anti-cyclonic conditions in summer resulted in elevated mass concentrations of secondary pollutants, e.g. SO²⁻₄. The fine fraction contained ca 50% water-soluble inorganic ions at Leeds and slightly more at the rural site. These proportions showed little seasonal variation.     

Dissolved sulphur dioxide and sulphate in urban and rural precipitation (Norfolk,U.K.)

Sulphur dioxide washout and total sulphate scavenging by precipitation at a rural and urban site have been measured in Norfolk (easternmost part of U.K.) over a period of one year. The basic sampling period was one day although, on occasions, more intensive sampling was undertaken. Estimates have been made of the role of sulphur dioxide washout in the total sulphur removal process. Because the “same” rainfall was collected in the urban and rural locations, attempts have been made to compare city and rural sulphur dioxide washout and sulphate scavenging rates in relation to precipitation amount, intensity, atmospheric sulphur dioxide, rainfall pH and weather-type. There is a greater difference between urban and rural sulphur dioxide washout levels than between the respective precipitation sulphate levels. The field measurements of sulphur dioxide solubilities agree reasonably well with some previous theoretical work.     

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.     

Stable sulphur and nitrogen isotopes of the moss Haplocladium microphyllum at urban,rural and forested sites

Elemental (S and N) and isotopic (δ³⁴S and δ¹⁵N) contents in the moss Haplocladium microphyllum at urban, rural and forested sites in acid rain area of South China have been analyzed for comparisons to show whether they are different and can be effectively used to identify S and N sources of atmospheric deposition. Average moss S content at rural sites (0.29 ± 0.06%) was found to be in between those at urban (0.35 ± 0.05%) and forested (0.25 ± 0.04%) sites, which are significantly different. Average N contents of urban (2.60 ± 0.56%) and rural mosses (2.84 ± 0.77%) are not significantly different, while both are significantly different to that of forested mosses at most areas, indicating that the atmosphere over rural sites has been polluted by N as seriously as that over urban sites. Nitrogen supply, relative to S supply, was in excess of the requirement for protein synthesis, especially at rural and forested sites. Moss stable isotope signatures have been proven to be effective tools for deciphering atmospheric S and N sources at these sites. Through moss δ³⁴S signatures, we found that atmospheric S at urban and forested sites was mainly from local coal combustion and domestic biomass burning, respectively, whereas northerly air masses contributed more S to forested sites. The relatively negative moss δ¹⁵N values (?7.5 ± 3.0, ?3.4 ± 2.1 and ?0.8 ± 2.1‰) demonstrated that the main form in the N deposition was NH_x in these sites. More negative δ¹⁵N signatures in urban mosses (?7.5 ± 3.0‰) indicated the contribution of NH₃ released from untreated city sewage and wastes, while relatively less negative δ¹⁵N for rural and forested mosses (3.4 ± 2.1 and ?0.8 ± 2.1‰) was largely derived from agricultural NH₃.     

Effects of sampling,preparation and defecation on metal concentrations in selected invertebrates at urban sites

In order to obtain basic information for designing standardized test preparation methods, the heavy metals Zn, Cu, Cd and Pb were measured in gastropods (Xerolenta obvia), oligochaetes (Lumbricus terrestris), isopods (Armadillidium vulgare, Trachelipus rathkei) and carabids (Harpalus rubripes, Calathus fuscipes) using different sampling methods and different modes of sample treatment. In some of the experiments, higher Zn, Cd and Pb, and lower Cu-contents were observed in isopods and carabids trapped with formalin-pitfalls compared to manually collected specimens (which were allowed to defecate). Defecation had marked effects on the levels of all four metals investigated in oligochaetes, and on Cd and Pb in gastropods and isopods. Cellulose was fed as an accelerator of gut passage and showed a significant effect on the Pb concentration in the soft body of gastropods. Deionate-washed isopods (A. vulgare) showed higher Cd concentrations than ultrasonic-cleaned individuals. No marked differences were observed between heat-dried and freeze-dried isopods. Carabids showed strong sex-specific differences in metal concentrations. Based on these and previous results, invertebrates should be: collected in vivo, allowed to defecate, be freeze-fixed and (at least in arthropods) ultrasonic-cleaned, determined to species level and in certain groups (carabids) also to sex, and then be sized or sorted by size (age) before further preparation and analysis. If any of these treatments is impractical, comparable sampling and preparation methods are recommended as a minimum requirement in order to avoid bias in the results and/or interpretation.     

Spatio-temporal trends and influencing factors of PM2.5 concentrations in urban agglomerations in China between 2000 and 2016

An urban agglomeration (UA), similar to a megalopolis or a metropolitan area, is a region where cities and people are concentrated, and where air pollution has adversely impacted on sustainable and high quality development. Studies on the spatio-temporal trends and the factors which influence PM_2.5 concentrations may be used as a reference to support air pollution control policy for major UAs throughout the world. Nineteen UAs in China covering the years 2000–2016 were chosen as the research object, the PM_2.5 concentrations being used to reflect air pollution and being estimated from analysis of remote sensing images. The Exploratory Spatial Data Analysis method was used to study the spatio-temporal trends for PM_2.5 concentrations, and the Geodetector method was used to examine the factors influencing the PM_2.5 concentrations. The results revealed that (i) the temporal trend for the average values of the PM_2.5 concentrations in the UAs followed an inverted U-shaped curve and the inflection points of the curve occurred in 2007. (ii) The PM_2.5 concentrations in the UAs exhibited significant global spatial autocorrelation with the high–high type and the low–low type being the main categories. (iii) The rate of land urbanization and the structure of energy consumption were the main factors which influenced the PM_2.5 concentrations in the UAs.

     

Nitrogen oxides and ozone in Portugal: trends and ozone estimation in an urban and a rural site

Environmental Science and Pollution Research - This study provides an analysis of the spatial distribution and trends of NO, NO2 and O3 concentrations in Portugal between 1995 and 2010....     

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.     

Trace element concentrations in summer aerosols at rural sites in New York state and their possible sources

Eighty five samples of air particulates collected during the summers of 1975–1977 at three rural and one urban sites in New York State were analyzed for up to 13 elements by instrumental neutron activation analysis. Sixteen samples showed high episodic concentrations of several trace elements and sulfate. SO₄²⁻, Cr, Zn, As, Se, Br and Sb were distinctly enriched in these aerosols, relative to their crustal abundances. Sc was used as the reference for the crustal component. Episodic and non-episodic events were statistically indistinguishable if only the means and ranges of elemental concentrations and the enrichment factors were considered. However, correlation matrix and factor analysis showed that while non-episodic cases had inexplicably complex factor loading structures, the structure for episodic cases was simple. Episodic events therefore appear to be better indicators of the sources of non-urban aerosols. Five factors were sufficient to account for 87 % of the total variance in the episodic system. When the dependence of the factors on the set of elements was correlated with the elemental emission patterns of probable sources five sources of the trace elements in these aerosols were identified: distant coal-fired power plants (for SO₄²⁻, As. Se), refuse incinerators (for Zn, Sb), iron and steel works (for Cr and possibly Fe, Mn). crustal material (for K, Sc, Mn, Fe) and automotive emissions (for Br).     

Estimates of average major ion concentrations in bulk precipitation at two high-altitude sites near the continental divide in southwestern colorado

The composition of bulk precipitation from two high-altitude sites, established in 1971 near the Continental Divide in southwestern Colorado, has been monitored by season during the past decade. Calcium ions are the predominant cationic species; sulfate is the major anionic consitituent. Bulk precipitation major ion concentrations exhibit log-normal distributions. Representative mean and standard deviation values for the major inorganic ionic species present in bulk precipitation have been calculated for three years of consecutive seasons. Standard deviations for all species, except nitrate, are similar. For two years of data grouped into quarters, deviations from mean values fall well within the plus or minus two standard deviation limit. There does not seem to be a systematic deviation from the mean concentration values, with respect to either ionic component or season.