Indications for changing deposition patterns in central Europe

The German Federal Environmental Agency (Umweltbundesamt) currently runs a network of 17 air pollution monitoring stations in rural areas within the Federal Republic of Germany. Since 1982, daily bulk precipitation samples have been collected and analysed at five of these stations. As no changes in sampling and chemical analysis techniques have been introduced in this time period, an interpretation with respect to trends is possible. An increase in pH is most obvious at Deuselbach in the western part of Germany. It is related to a decrease in sulphate ions. Reduced SO2 emissions in the western part of Europe have resulted in decreasing ambient air concentrations mainly in the western part of Germany, whereas changes in concentrations close to the eastern border of West Germany were not as pronounced. Part of the decrease, however, was a consequence of three mild winters in sequence at the end of the period, with little easterly air flow. Estimated dry deposition fluxes of sulphur at 3 rural stations in West Germany were lower in 1988/1989 compared to 1980-1987 by 44-69%. Wet deposition showed between 8% increase and 25% decrease. The resulting reduction in total sulphur deposition ranged from 17-54%. Deposition via interception of fog droplets was not measured.     

The atmospheric chemistry of sulphur and nitrogen in power station plumes

Emissions of sulphur and nitrogen compounds from power stations represent a significant fraction of the total emissions of these elements to the atmosphere. Understanding their subsequent chemical reactions in the atmosphere is of fundamental importance as without it, a quantitative assessment of their contribution to local and regional scale air pollution is not possible. Here the atmospheric chemistry of sulphur dioxide and the oxides of nitrogen, and their resultant likely behaviour in the plumes of power stations are reviewed.     

Changes in the atmospheric deposition of acidifying compounds in the UK between 1986 and 2001

Emissions of a precursor of acidity in precipitation, sulphur dioxide (SO2), declined in the UK and the EU (15) by 71% and 72%, respectively, between 1986 and 2001, while nitrous oxide emissions declined by about 40%. Acidity in UK precipitation and the deposition of sulphate in precipitation halved during this period, but reductions were larger in the English Midlands than at the west coast and in high rainfall areas (>2000 mm). There is evidence that the smaller reductions in sulphur deposition in the west and south are due in part to shipping sources of SO2. Reductions in sulphur dry deposition (74%) are larger than in wet deposition (45%), due to changes in the canopy resistance to dry deposition. For reduced nitrogen, there has been a small (10%) reduction in emissions and deposition, while for oxidized nitrogen, a substantial reduction in emissions (40%) occurred but wet deposition of nitrate changed by less than 10%.     

Levels and trends of brominated flame retardants in the Arctic

Polybrominated diphenyl ethers (PBDEs) containing two to seven bromines are ubiquitous in Arctic biotic and abiotic samples (from zooplankton to polar bears (Ursus maritimus) and humans; air, soil, sediments). The fully brominated decabromodiphenyl ether (BDE-209), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA) and polybrominated biphenyls (PBBs) are also present in biotic and abiotic samples. Spatial trends of PBDEs and HBCD in top predators are similar to those seen for polychlorinated biphenyls (PCBs) and indicate western Europe and eastern North America as source regions. Concentrations of tetra- to heptaBDEs have increased significantly in North American and Greenlandic Arctic biota and in Greenland freshwater sediments paralleling trends seen further south. For BDE-209, increasing concentrations in Greenlandic peregrine falcons (Falco peregrinus) and in dated lake sediment cores in the Canadian Arctic have been seen during the 1990s. BDE-47, -99, -100 and -153 are observed to biomagnify in Arctic food webs. summation operatorPBDE concentrations in Arctic samples are lower than in similar sample types from more southerly regions and are one or more orders of magnitude lower than summation operatorPCB concentrations except for some levels for air. Air and harbor sediment results for PBDEs indicate that there are local sources near highly populated areas within the Arctic. Findings of PBBs on moss and TBBPA on an air filter, and that both are found in biota at high trophic levels indicates that these compounds may also reach the Arctic by long-range atmospheric transport. Based on the evidence of their presence in the Arctic and indications that most if not all are undergoing long-range transport, these brominated flame retardants (BFRs) have characteristics that qualify them as POPs according to the Stockholm Convention.     

Seasonal and long-term trends in atmospheric PAH concentrations: evidence and implications

Atmospheric monitoring data for selected polynuclear aromatic hydrocarbons (PAHs) were compiled from remote, rural and urban locations in the UK, Sweden, Finland and Arctic Canada. The objective was to examine the seasonal and temporal trends, to shed light on the factors which exert a dominant influence over ambient PAH levels. Urban centres in the UK have concentrations 1-2 orders of magnitude higher than in rural Europe and up to 3 orders of magnitude higher than Arctic Canada. Interpretation of the data suggests that proximity to primary sources 'drives' PAH air concentrations. Seasonality, with winter (W) > summer (S), was apparent for most compounds at most sites; high molecular weight compounds (e.g. benzo[a]pyrene) showed this most clearly and consistently. Some low molecular weight compounds (e.g. phenanthrene) sometimes displayed S>W seasonality at some rural locations. Strong W>S seasonality is linked to seasonally-dependent sources which are greater in winter. This implicates inefficient combustion processes, notably the diffusive domestic burning of wood and coal. However, sometimes seasonality can also be strongly influenced by broad changes in meteorology and air mass origin (e.g. in the Canadian Arctic). The datasets examined here suggest a downward trend for many PAHs at some sites, but this is not apparent for all sites and compounds. The inherent noise in ambient air monitoring data makes it difficult to derive unambiguous evidence of underlying declines, to confirm the effectiveness of international source reduction measures.     

Changes of emissions and atmospheric deposition of mercury,lead, and cadmium

This paper reviews the information on trends of past emissions of mercury, lead, and cadmium in Europe, as well as examines current levels and future scenarios of these emissions. The impact of various factors on emission changes is discussed including the implementation of various strategies of emission controls in Europe. Future emissions are forecasted on the basis of various scenarios of economy growth in Europe, implementation of European and global legislation (e.g. the Kyoto agreement), population changes, etc.Changes of emissions of mercury, lead, and cadmium are then related to the changes of concentrations of these contaminants in air and precipitation samples at selected stations in Europe. It can be concluded that the reduction trends of anthropogenic emissions of cadmium and lead in Europe are similar to the reduction trends of air concentrations of these metals during the last 2 decades. Somewhat different relationship has been noted for changes in emissions and precipitation. In general for Europe, 60% reduction of Cd emissions was met by about 45% reductions of Cd concentrations in precipitation at the studied stations during the last 2 decades.There is a potential for further reduction of these emissions until the year 2010 up to about 37% for Cd, 51% for Pb, and 49% for Hg as estimated within various emission scenarios presented in the paper.     

The significance of PCBs in the atmosphere of the southern hemisphere

Air monitoring stations were set up at 2 sites in the southern hemisphere--Moody Brook, Falkland Island (51 degrees 25' S, 57 degrees 56' W) and Halley, Research Station, Antarctica (75 degrees 35' S, 26 degrees 30' W). PCBs were monitored at the stations throughout 1999. Highest concentrations were observed when temperatures were greater. In general, concentrations were greater at Moody Brook than at Halley, although the difference in concentrations between sites was less for more chlorinated congeners. Air concentrations at both sites were compared with samples collected nearby over-water. Over water air concentrations were found to be greater than over land air concentrations. Concentrations were also compared with literature data for air concentrations at a remote site in the Canadian Arctic. Atmospheric concentrations of tri-chlorinated biphenyls were found to be approximately double those reported for Ellesmere Island in the Canadian Arctic, whilst concentrations in samples from Antarctica were very similar to those found in the high Arctic. Most other PCBs were a factor of 2-4 greater in the Canadian Arctic.     

Major ions and scavenging of sulphate in the norwegian arctic

Precipitation samples at eight sites in the Norwegian Arctic and Northern Norway have been collected and analyzed for the period June 1982–June 1984. The results are compared with data for airborne SO²⁻₄ and SO₂ measured at ground level, and information on concentrations at higher levels from aircraft measurements and model calculations.The scavenging coefficients are generally low under Arctic winter conditions, and high during summer. This can be explained by the different vertical distributions of scavenged material in summer and winter, and differences in precipitation-forming processes. In addition, local climatic conditions with high relative humidity and high concentrations of sea-spray particles result in locally enhanced scavenging efficiencies at the island stations Bjørnøya and Jan Mayen. High NH⁺₄ concentrations in precipitation occur near bird colonies during the breeding period.The wet deposition in the Arctic is small, i.e. an order of magnitude lower than in Southern Norway.     

Air concentrations of currently used herbicides and legacy compounds in the Canadian prairies,subarctic, and arctic

Passive air samplers were installed in the summers of 2005 and 2007 for 90 days at four locations in the agricultural region of the Canadian Prairies and at five locations in the Canadian Subarctic and Arctic. The presence and masses of ten currently used herbicides and three legacy compounds in the polyurethane foam disks were quantified. Herbicides 2,4-D, bromoxynil and MCPA were detected at all locations in the Canadian Prairies and in both years because these herbicides are widely applied to control broadleaf weeds in cereal crops that are an integral part of Prairie agricultural production systems. MCPA was also detected at one location in the Arctic in 2007. The detection of the other seven herbicides in the 2 years combined ranged from no detections (atrazine only) to five detections for the relatively volatile herbicides trifluralin and triallate. Triallate was the only other herbicide detected in the Arctic (2005). Legacy compounds were either not detected (alachlor) or at levels near their detection level (γ-HCH and α-HCH). γ-HCH and α-HCH were more frequently detected in 2005 than in 2007 indicating that their concentrations in Canadian air have decreased over time. γ-HCH, widely used as an insecticide in Prairie oilseed production until 2002, was detected at larger concentrations in the Canadian Prairies than in the Subarctic and Arctic. α-HCH, a manufacturing by-product in technical HCH prior to 1971 in Canada, was not detected in the Canadian Prairies but was at detectable levels in the Subarctic and Arctic as the Arctic Ocean is reported to be a major source of α-HCH to the atmosphere. We conclude that some of the most widely used herbicides in Canadian agriculture today are commonly present in the air in regions where they are applied and that a portion of these herbicides may be traveling as parent molecules to the Canadian Arctic. To the authors’ knowledge, this is the first evidence of the presence of MCPA and triallate in Arctic air samples, perhaps because previous research has seldomly monitored for currently used herbicides in this region.     

Crown condition of Norway spruce in relation to sulphur and nitrogen deposition and soil properties in southeast Norway

Atmospheric deposition of sulphur and nitrogen compounds may lead to enhanced leaching of base cations, accumulation of nitrogen in organic matter, lowered pH and increased concentration of toxic aluminium in soil, which in turn may affect the vitality of forest trees. A general monitoring of forest condition has been initiated in many European countries, partly in order to reveal stresses caused by acidification. However, forest condition is also affected by many other factors. This paper examines a seven-year series of crown-condition data from Local County Monitoring Plots in Norway spruce stands in Norway. Average, time trend and lability variables were calculated for crown density and crown colour for each plot. Wet deposition of sulphate, ammonium and nitrate for each plot were estimated using data from the national air and precipitation monitoring programmes. Soil data are based on soil sampling within the plots. The analysis gave no evident support for the hypothesized negative effect on crown condition from sulphur and nitrogen deposition and related alterations in soil.     

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.     

Chemical fluxes in time through forest ecosystems in the UK - Soil response to pollution recovery

Long term trend analysis of bulk precipitation, throughfall and soil solution elemental fluxes from 12 years monitoring at 10 ICP Level II forest sites in the UK reveal coherent national chemical trends indicating recovery from sulphur deposition and acidification. Soil solution pH increased and sulphate and aluminium decreased at most sites. Trends in nitrogen were variable and dependant on its form. Dissolved organic nitrogen increased in bulk precipitation, throughfall and soil solution at most sites. Nitrate in soil solution declined at sites receiving high nitrogen deposition. Increase in soil dissolved organic carbon was detected - a response to pollution recovery, changes in soil temperature and/or increased microbial activity. An increase of sodium and chloride was evident - a possible result of more frequent storm events at exposed sites. The intensive and integrated nature of monitoring enables the relationships between climate/pollutant exposure and chemical/biological response in forestry to be explored.     

Local Arctic air pollution: Sources and impacts

Local emissions of Arctic air pollutants and their impacts on climate, ecosystems and health are poorly understood. Future increases due to Arctic warming or economic drivers may put additional pressures on the fragile Arctic environment already affected by mid-latitude air pollution. Aircraft data were collected, for the first time, downwind of shipping and petroleum extraction facilities in the European Arctic. Data analysis reveals discrepancies compared to commonly used emission inventories, highlighting missing emissions (e.g. drilling rigs) and the intermittent nature of certain emissions (e.g. flaring, shipping). Present-day shipping/petroleum extraction emissions already appear to be impacting pollutant (ozone, aerosols) levels along the Norwegian coast and are estimated to cool and warm the Arctic climate, respectively. Future increases in shipping may lead to short-term (long-term) warming (cooling) due to reduced sulphur (CO₂) emissions, and be detrimental to regional air quality (ozone). Further quantification of local Arctic emission impacts is needed.     

Trends of nitrogen in air and precipitation: model results and observations at EMEP sites in Europe, 1980--2003

We analyze trends of some nitrogen compounds using long-term measurements and results from the EMEP (co-operative programme for monitoring and evaluation of the long-range transmissions of air pollutants in Europe) chemical transport model at EMEP sites. We find statistically significant declines at the majority of sites for NH(x) (sum of ammonia and ammonium) in air and for nitrate and ammonium in precipitation, but only at a few sites for xNO3 (sum of nitrate and nitric acid) in air. Model calculations and measurements give similar results. We demonstrate that the lack of trends for xNO3 in air at least partly can be attributed to a shift in the equilibrium between nitric acid and ammonium nitrate towards particulate phase, caused by reductions in the sulfur dioxide emissions.     

Surface water acidification in the South Pennines II. Temporal trends

Data for eight reservoirs in the South Pennines covering the period 1980-98, and for 1988-98 at the River Etherow Acid Waters Monitoring Network site, have been analysed for temporal trends using the Seasonal Kendall test. Rising trends in pH were identified at seven of the eight reservoirs, generally accompanied by declining aluminium levels. Nitrate concentrations have, however, increased sharply at the two reservoirs for which adequate data were available. Data for a wider range of determinands at the Etherow suggest that pH increases in the region can be attributed to declining sulphate concentrations, as a result of reductions in sulphur deposition. Nitrate concentrations have again increased at this site. Results are significant in a national context in that pH recovery, although widely believed to have taken place in the UK since the 1970s, has rarely been shown to have occurred. For the South Pennine region, which has been severely acidified by historically high acid deposition levels, there have clearly been improvements over the last 18 years, although many surface waters remain acidic. Observed trends for nitrate suggest that some of the pH recovery resulting from reduced sulphur deposition may have been offset by nitrogen saturation in the region, due in part to continued high levels of nitrogen deposition.     

Air pollution characteristics associated with mesoscale atmospheric patterns in northwest continental Europe

An impact related daily air quality index (DAQx), calculated for 15 air quality monitoring stations (traffic, background, and industry) in Belgium, France, Germany and Luxembourg, was compared to mesoscale atmospheric patterns between 2001 and 2007. Meteorological conditions were described by the Hess and Brezowsky synoptic weather classification system and gridded data of the EU FP6 ENSEMBLES project of total precipitation and mean surface temperature. DAQx values indicate sufficient to poor air quality in the urban area of Brussels and at urban traffic stations, as well as satisfactory air quality at the background stations. The air quality index refers to more than 90% to the presence of high PM₁₀, O₃ and NO₂ concentrations. SO₂ and CO play only a minor role. The investigation of weather regimes indicates that zonal and mixed cyclonic circulation regimes are associated with better air quality than meridional and anticyclonic weather regimes. In general, weather regimes with high daily precipitation lead to better air quality than dryer air masses because of lower contribution of PM₁₀ to the air quality index. A trend analysis of weather regimes from 1978 to 2007 shows significant (α = 0.05) positive trends for weather classes associated with lower PM₁₀ concentrations. The results of a case study at a German station examining the relationship between PM₁₀ concentrations and local meteorological quantities (wind speed and precipitation) confirm the results of the regional analysis.     

Wet and dry deposition of sulfur and nitrogen compounds in Ontario

Measurements have been made of sulfur and nitrogen compounds in precipitation since 1980 and in air since 1981 in Ontario. This paper presents results of the atmospheric deposition measurement program to the end of 1985. As is to be expected from the distribution of emission sources, annual concentrations of SO₄²⁻ andNO₃⁻ in precipitation, and of SO₂,SO₄²⁻ andNO₃⁻ in air are higher in southern Ontario than in northern Ontario. The corresponding distribution pattern for deposition is similar to that of concentration. A wet SO₄²⁻ deposition rate of 20 kg ha¹⁻ y¹⁻, a value considered critical for the acidification of sensitive water bodies, is exceeded in all of central and southern Ontario. On a province-wide basis, sulfur wet deposition is about four times higher than sulfur dry deposition. For nitrogen, wet and dry deposition are more comparable, though the former is still higher. The S- and N-species display different seasonal trends in concentration and deposition reflecting a dependence on meteorological factors, and on the associated chemical transformation rates. On the other hand, year to year variations are small.     

Trends in atmospheric ammonium concentrations in relation to atmospheric sulfate and local agriculture

Ammonium (NH(4)(+)) concentrations in air and precipitation at the Institute of Ecosystem Studies (IES) in southeastern New York, USA declined over an 11-year period from 1988 to 1999, but increased from 1999 to 2001. These trends in particulate NH(4)(+) correlated well with trends in particulate SO(4)(2-) over the 1988-2001 period. The NH(4)(+) trends were not as well correlated with local cattle and milk production, which declined continuously throughout the period. This suggests that regional transport of SO(4)(2-) may have a greater impact on concentrations of NH(4)(+) and subsequent deposition than local agricultural emissions of NH(3). Ammonium concentrations in precipitation correlated significantly with precipitation SO(4)(2-) concentrations for the 1984-2001 period although NH(4)(+) in precipitation increased after 1999 and SO(4)(2-) in precipitation continued to decline after 1999. The correlation between NH(4)(+) and SO(4)(2-) was stronger for particulates than for precipitation. Particulate NH(4)(+) concentrations were also correlated with particulate SO(4)(2-) concentrations at 31 of 35 eastern U.S. CASTNet sites that had at least 10 years of data. Air concentrations of NH(4)(+) and SO(4)(2-) were more strongly correlated at the sites that were located within an agricultural landscape than in forested sites. At most of the sites there was either no trend or a decrease in NH(4)(+) dry deposition during the 1988-2001 period. The sites that showed an increasing trend in NH(4)(+) dry deposition were generally located in the southeastern U.S. The results of this study suggest that, in the northeastern U.S., air concentrations of NH(4)(+) and subsequent deposition may be more closely linked to SO(4)(2-) and thus SO(2) emissions than with NH(3) emissions. These results also suggest that reductions in S emissions have reduced NH(4)(+) transport to and NH(4)(+)-N deposition in the Northeast.     

Phenolic compounds content in Pinus halepensis Mill. needles: a bioindicator of air pollution

Foliar phenol concentrations (total and simple phenols) were determined in Aleppo pine (Pinus halepensis Mill.) needles collected in June 2000, from 6 sites affected by various forms of atmospheric pollutants (NO, NO(2), NO(x), O(3) and SO(2)) monitored during two months. Results show an increase in total phenol content with exposure to sulphur dioxide and a reduction with exposure to nitrogen oxide pollution. p-Coumaric acid, syringic acid and 4-hydroxybenzoic acid concentrations increase with exposure to nitrogen oxide pollution, whereas gallic acid and vanillin decrease in the presence respectively of sulphur dioxide and ozone. This in situ work confirms the major interest of using total and simple phenolic compounds of P. halepensis as biological indicators of air quality.