Evaluation of the effect of long-range transport of air pollutants on coastal atmospheric monitoring sites in and around Taiwan

Long-range transport of pollution outflow from Asian mainland has been noticed and expected to play a significant role in Pacific background. Since 1993 the Taiwanese Environmental Protection Administration (TEPA) is conducting ground-based observations of various particulate and gaseous pollutants at 74 monitoring stations in Taiwan. One of these stations, Heng-Chun at the south coast of Taiwan can be considered as a background station with only negligible amounts of local pollution, and another one, Wan-Li at the north coast, predominantly receives air that has not passed over Taiwan, so that background air can be analysed by means of sectorisation. In this work, the sectorised 13-year time series of measurements of CO, SO₂, O₃, NO_x and PM₁₀, from the Wan-Li station are presen and compared to data from the Heng-Chun station and another TEPA background station off the coast of mainland China, Ma-Zu. The CO and O₃ measurements are also compared to data from the Yonaguni station, a Pacific island site, part of the Global Atmospheric Watch (GAW) network.The similarity of the sectorised data from the Wan-Li station with the data of the other station indicates that atmospheric measurements from the Wan-Li site can be used to make inferences about trends in western Pacific background air pollution and the effect of long-range transport of pollutants. The measurement time series from 1993 to 2006 do not indicate a significant trend in the monthly mean O₃ concentrations in accordance with other research about ozone in tropical latitudes. An increasing trend in CO concentrations of 2.8% per annum is observed between 1999 and 2006 for long-range transport to northern Taiwan, and a doubling of the SO₂ and NO_x concentrations observed at the Wan-Li and Heng-Chun sites within the period 2001–2006. SO₂ concentrations are found to quadruple at Ma-Zu within the same period. The data suggest that pollution from the Asian mainland enhances significantly the background air pollution over the Pacific.     

Comparison of measured and modeled surface ozone concentrations at two different sites in Europe during the solar eclipse on August 11, 1999

The effects of the solar eclipse on 11 August 1999 on surface ozone at two sites, Thessaloniki, Greece (urban site) and Hohenpeissenberg, Germany (elevated rural site) are investigated in this study and compared with model results. The eclipse offered a unique opportunity to test our understanding of tropospheric ozone chemistry and to investigate with a simple photochemical box model the response of surface ozone to changes of solar radiation during a photolytical perturbation such as the solar eclipse. The surface ozone measurements following the eclipse display a decrease of around 10–15 ppbv at the urban station of Eptapyrgio at Thessaloniki while at Hohenpeissenberg, the actual ozone data do not show any clear effect of eclipse on surface ozone. For Thessaloniki, the model results suggest that solely photochemistry can account for a significant amount of the observed surface ozone decrease during the eclipse but transport effects mask part of the photochemical effect of eclipse on surface ozone. For Hohenpeissenberg, the box model predicted an ozone decrease, due to the eclipse, of about 2 ppbv in relative agreement with the magnitude of the observed ozone decrease from the 2 h moving average while at the same time it inhibits the foreseen diurnal ozone increase. However, this modeled ozone decrease during the eclipse is small compared to the diurnal ozone variability due to transport effects, and hence, transport really masks such relative small changes. The different magnitude of the surface ozone decrease between the two sites indicates mainly the role of the NO_x levels. Measured and modeled NO and NO₂ concentrations at Hohenpeissenberg during the eclipse are also compared and indicate that the partitioning of NO and NO₂ in NO_x is influenced clearly from the eclipse. This is not observed at Thessaloniki due to local NO_x sources.     

Origin and variability of upper tropospheric nitrogen oxides and ozone at northern mid-latitudes

Year-long measurements of NO_x and ozone performed during the NOXAR project are compared to results from the ECHAM4.L39(DLR)/CHEM (E39/C) and GISS coupled chemistry–climate models. The measurements were taken on flights between Europe and the eastern United States and between Europe and the Far East in the latitude range 40–65°N. Our comparison concentrates on the upper troposphere and reveals strong longitudinal variations in seasonal mean NO_x of more than 200 pptv, which both models are able to reproduce qualitatively. Vertical profiles show maximum NO_x values 2–3 km below the tropopause (“E-shape”) with a strong seasonal cycle. E39/C simulates a maximum located at the tropopause and with a reasonable seasonal cycle. The GISS model reproduces the seasonal cycle but not the profile's shape due to its coarser vertical resolution. A comparison of NO_x frequency distributions reveals that both models are capable of reproducing the observed variability, except that E39/C shows no very high NO_x mixing ratios.Both models show that lightning and surface NO_x emissions contribute the most to the seasonal cycle of NO_x at tropopause altitudes. The impact of lightning in the upper troposphere does not vary strongly with altitude, whereas the impact of surface emissions decreases with altitude. Among all sources, lightning contributes the most to the variability of NO_x in the upper troposphere in northern mid-latitudes during summer.     

Impact of clouds and aerosols on ozone production in Southeast Texas

A radiative transfer model and photochemical box model are used to examine the effects of clouds and aerosols on actinic flux and photolysis rates, and the impacts of changes in photolysis rates on ozone production and destruction rates in a polluted urban environment like Houston, Texas. During the TexAQS-II Radical and Aerosol Measurement Project the combined cloud and aerosol effects reduced j(NO₂) photolysis frequencies by nominally 17%, while aerosols reduced j(NO₂) by 3% on six clear sky days. Reductions in actinic flux due to attenuation by clouds and aerosols correspond to reduced net ozone formation rates with a nearly one-to-one relationship. The overall reduction in the net ozone production rate due to reductions in photolysis rates by clouds and aerosols was approximately 8 ppbv h^?1.     

Harbour of Ravenna: The contribution of harbour traffic to air quality

Ravenna is one of the main Italian ports and has assumed a leadership position in Italy for some products and markets. The commercial harbour and the adjacent industrial area are very important for the economic system of Ravenna but, at the same time, they are highly critical areas.In particular, on average 8000 ships per year pass through the harbour of Ravenna, influencing air quality in harbour environment.The paper originates from a study about the contribution of different sources of air pollution in Ravenna and its aim is to evaluate the maritime traffic contribution to the air quality in the port area and to determine the suitability of an urban air quality model to support the air quality management in Ravenna. NO_x and PM are selected as modelled pollutants.The study is made up of two parts. The first deals with the evaluation of annual emission of PM₁₀ and NO_x coming from ships through a standard European methodology while in the second we simulated the diffusion of these pollutants in the whole area. In order to evaluate the capability of the model to treat maritime traffic emissions, we compared hour-by-hour simulated concentrations with data collected by a fixed monitoring station located near the Candiano Canal.NO_x concentrations obtained by short- and long-term simulations show a good match with the values measured by the fixed monitoring station, located in the centre of harbour area, and these results are also supported by FA2 performance index.Instead the omission of the secondary particulate and the contribution of other sources of particulate matter in the port area are probably the most important causes of the PM₁₀ underestimation.The worse results obtained according to the performance indexes indicate the need to consider the formation and transport of secondary particulate matter in order to obtain more reliable predictions.     

Long-range transport of gaseous and particulate oxidized nitrogen compounds

Measurements of NO₂, PAN, HNO₃ and particulate NO₃⁻ as 24-h mean concentration values have been carried out at a clean air station. The station is situated on the Swedish west coast 40 km south of Gothenburg. Measurements from November 1981 to October 1982 are presented. NO₂ was measured with the Saltzman method after removal of ozone and PAN with a gas Chromatographic method. HNO₃ was sampled in a denuder and particulate NO₃⁻ was sampled on an impregnated filter behind the denuder. The denuder and filter were then analysed by ion chromatography. Episodes of high concentrations occurred several times during the year. On these occasions the air was transported over a long range from the continent. 72-h back trajectories are available for this station at 6-h intervals during the whole period of measurements. Monthly mean concentrations of these four species, together with data on SO₂ and particulate sulphate are presented. Analysis of the data as a function of the direction of the back trajectory and correlations between nitrogen and sulphate compounds are also given.     

In situ measurements of NO,NO2, NOy,and O3 in Dinghushan (112°E, 23°N), China during autumn 2008

Measurements of O₃, NO, NO₂, and NO_y mixing ratios were carried out at a station-Dinghushan in Guangdong province of China from Oct. 18th, 2008 to Nov. 7th, 2008. This research shows that under conditions of a strong subtropical high (temperature high, relative humidity low), on Oct. 29th, 2008 the Dinghushan station observed severe photochemical pollution. The Maximum hour average concentration of O₃ reached 128 ppbv, and the serious photochemical pollution is caused by superposition of local photochemical reaction and regional transport. The observation that NO_x ozone production efficiency (OPE) values for high O₃ pollution on Oct. 29–30th, 2008 were 10.5 and 15, which were more than the values of the city source region and lower than that of the surrounding clean areas. It means the sensitivity of O₃ generated was transitioning from VOCs limited condition to NOx-limited regime. By applying a Smog Production Model, the results show that the extent of reaction values less than 0.6 were occurred on 17 days during campaign, and 13 days for the extents of reactions more than 0.6. However, there were no data with values over 0.8, which indicates that the observation station represent a VOCs sensitive system during campaign. Analysis of the extents of reactions and wind data show that the pollution is mostly subject to a southeasterly airflow influence.     

The Chemical and Meteorological Conditions Associated with High and Low Ozone Concentrations in Southeastern Michigan and Nearby Areas of Ontario

This analysis represents the first characterization of the photochemistry and transport of ozone in the Detroit metropolitan area and provides a basis for comparing data for Detroit to that for other cities. The characterization is based on a comprehensive set of meteorological and chemical measurements obtained at a site in the urban core of Detroit during the summer of 1981, together with measurements of O₃, nitrogen oxides (NO _X ), and nonmethane organic compounds (NMOC) from rural, suburban, and urban areas in southeastern Michigan and adjacent areas of Ontario.

For the quartile (23 days) with highest ozone maxima (97-180 ppb), the maxima occurred 10-70 km north-northeast of the city on days that were warm and hazy with light southsouthwest winds. On such days there was a marked accumulation of ozone precursors (NMOC and NO_X) in the early morning, as well as a rapid chemical removal of NO _X (NO _X half-life of ～5 h) from morning to midday. The timing of the daily ozone increase across the study region suggests that local photochemical generation in a moving plume was responsible for more than half of the ozone measured downwind. However, there was also evidence that ozone transported into Detroit as part of the regional background was a significant part of the O₃ maxima on high ozone days. The average contributions of photochemistry and transport for the 23 days with the highest ozone maxima were estimated to be 57 ppb and 47 ppb, respectively.     

Retrospective assessment of air quality management practices in Taiwan

In 1995, Taiwan's Environmental Protection Administration (EPA/TW) instituted a policy of levying emission taxes on polluters in order to combat the rampant national issue of pollution. Since that time, pollution control strategies, tightening exhaust emission standards for industry, improvements in fuel quality, and new stricter vehicle emission standards, etc., have been implemented. This study evaluates the effectiveness of these measures and examines the improvement of Taiwan's air quality. In this paper, we conduct a detailed analysis of change in the concentrations of pollutants (SO₂, NO_x and particulate matter [PM]) between two three-year periods (from 1996 to1998 and from 2000 to 2002). The pollution levels were generally lower in the latter period. Concentrations at 14 EPA/TW stations in central Taiwan were simulated and source apportionment analyses in three of Central Taiwan's largest cities were conducted using a trajectory transfer-coefficient air quality model. Correlation coefficients (r) between simulations and observations for the monthly means of the concentrations of SO₂, NO_x, PM_2.5 and PM₁₀ during the study periods at the 14 stations are 0.56, 0.63, 0.70 and 0.31, respectively. The sulfur control policy greatly reduced SO₂ concentration island-wide, a stringent emission standard put into place for gasoline vehicles reduced NO_x concentration along highways, and an emissions tax placed on construction sites, as well as a regular program for road-dust sweeping, reduced primary particulate matter. Among all of the pollution abatement policies implemented, the most effective method for reducing PM_2.5 concentrations in the three largest cities involved the reduction of fine ammonium sulfate aerosols from point sources (56–63% of net PM_2.5 reduction). The next largest reduction was attributed to a diminishment in primary PM_2.5 emanating from point sources (27–56% of net PM_2.5 reduction). Secondary particulate matter, especially sulfate, was reduced from distances up to 150 km leeward of major pollution point sources such as Taichung Power Plant.     

Photo-oxidant chemistry in the polluted boundary layer under changing UV-B radiation

UV-B radiation is a driving factor for the chemistry of the polluted boundary layer. It is involved in the formation of radicals and consequently influences the formation and concentration of photo-oxidants. The 3-D mesoscale photochemical Metphomod model was employed to study the effect of changes in UV-B radiation on the concentration of photo-oxidants in the boundary layer over the Swiss Plateau. The model chemistry is based on the RACM mechanism and a two-stream approximation of radiative transfer. A summer (July) and a late winter (February) episode were simulated. All simulations were replicated with relatively large changes in the prescribed total ozone. The results for an increase in UV-B radiation show increases in PAN, HNO₃, and ozone at noon in NO_x-rich areas and a decrease in NO_x. In NO_x-poor areas in summer the effect on ozone is weak and has a negative sign, the main effect being an increase in H₂O₂. The spatial variability of NO_x concentrations in the Swiss Plateau in the summer case is such that the effect of increased UV-B radiation on ozone is spatially variable. The effect on the ozone production rate in summer is strongest positive at the surface in the NO_x-rich regions in the morning and strongest negative at some altitude above ground in NO_x-poor regions in the early afternoon. In the winter episode, NO_x-rich conditions are found almost everywhere on the Swiss Plateau, the effect of increased UV-B radiation on the ozone production rate is positive all day long and is largest at 300 m above ground at noon. In this case, in contrast to the summer case, the increase in ozone is carried over to the next day. The model results for ozone are in good agreement with results from a case study and a time series analysis of surface ozone measurements. We estimate the effect of day-to-day changes in total ozone on surface ozone peaks to range from 4 to 6 ppb at most.     

Modelling NOx from lightning and its impact on global chemical fields

We have used a three-dimensional off-line chemical transport model (CTM) to assess the impact of lightning emissions in the free troposphere both on NO_x itself and on other chemical species such as O₃ and OH. We have investigated these effects using two lightning emission scenarios. In the first, lightning emissions are coupled in space and time to the convective cloud top height calculated every 6 h by the CTM's moist convection scheme. In the second, lightning emissions are calculated as a constant, monthly mean field. The model's performance against observed profiles of NO_x and O₃ in the Atlantic and Pacific ocean improves significantly when lightning emissions are included. With the inclusion of these emissions, the CTM produces a significant increase in the NO_x concentrations in the upper troposphere, where the NO_x lifetime is long, and a smaller increase in the lower free troposphere, where the surface NO_x sources dominate. These changes cause a significant increase in the O₃ production in the upper troposphere and hence higher calculated O₃ there. The model indicates that lightning emissions cause local increases of over 50 parts per 10¹² by volume (pptv) in NO_x, 200 pptv in HNO₃ and 20 parts per 10⁹ by volume (ppbv) (>40%) in O₃. In addition, a smaller increase of O₃ in the lower troposphere occurs due to an increase in the downward transport of O₃. The O₃ change is accompanied by an increase in OH which is more pronounced in the upper troposphere with a corresponding reduction in CO. The method of emission employed in the model does not appear to have a significant effect globally. In the upper troposphere (above about 300 hPa) NO_x concentrations are generally lower with monthly mean emissions, because of the de-coupling of emissions from the model's convection scheme, which vents NO_x aloft more efficiently in the coupled scheme. Below the local convective outflow altitude, NO_x concentrations are larger when using the monthly mean emissions than when coupled to the convection scheme, because the more dilute emissions, and nighttime emissions, lead to a slower NO_x destruction rate. Only minor changes are predicted in the monthly average fields of O₃ if we emit lightning as a monthly constant field. However, the method of emission becomes important when we make a direct comparison of model results with time varying data. These differences should be taken into account when a direct comparison of O₃ with measurements collected at particular times and locations is attempted.     

Correlations among atmospheric elements,airborne particulate matter,benzene extracts,benzo(a)pyrene,NO, NO2 and so2 concentrations in Japan

Concentration levels of elements, airborne particulate matter, benzene extracts, benzo(a)pyrene B(a)P, NO, NO₂ and SO₂ in five residential areas were seasonally determined from May 1979 to January 1980. These air pollutants exhibited higher concentration in autumn and winter than in spring and summer. These were correlations among Pb, Cu, Ni, V and Se, among Si, Fe, Al and Ti and among NO, NO₂, B(a)P, benzene extracts and airborne particulate matter. NO, NO₂, B(a)P, benzene extracts and airborne particulate matter were correlated with Pb, Cu, Ni, V and Se, but not appreciably with Si, Fe, Al and Ti. On the basis of correlations between various air pollutants, the emitting source of the air pollutants and the health hazard by combined air pollution were discussed.     

Air pollutant concentrations near three Texas roadways, part II: Chemical characterization and transformation of pollutants

Spatial gradients of vehicular emitted air pollutants were measured in the vicinity of three roadways in the Austin, Texas area: (1) State Highway 71 (SH-71), a heavily traveled arterial highway dominated by passenger vehicles; (2) Interstate 35 (I-35), a limited access highway north of Austin in Georgetown; and (3) Farm to Market Road 973 (FM-973), a heavily traveled surface roadway with significant truck traffic. A mobile monitoring platform was used to characterize the gradients of CO and NO_x concentrations with increased distance from each roadway, while concentrations of carbonyls in the gas-phase and fine particulate matter mass and composition were measured at stationary sites upwind and at one (I-35 and FM-973) or two (SH-71) downwind sites. Regardless of roadway type or wind direction, concentrations of carbon monoxide (CO), nitric oxide (NO), and oxides of nitrogen (NO_x) returned to background levels within a few hundred meters of the roadway. Under perpendicular wind conditions, CO, NO and NO_x concentrations decreased exponentially with increasing distance perpendicular to the roadways. The decay rate for NO was more than a factor of two greater than for CO, and it comprised a larger fraction of NO_x closer to the roadways than further downwind suggesting the potential significance of near roadway chemical processing as well as atmospheric dilution. Concentrations of most carbonyl species decreased with distance downwind of SH-71. However, concentrations of acetaldehyde and acrolein increased farther downwind of SH-71, suggesting chemical generation from the oxidation of primary vehicular emissions. The behavior of particle-bound organic species was complex and further investigation of the size-segregated chemical composition of particulate matter (PM) at increasing downwind distances from roadways is warranted. Fine particulate matter (PM_2.5) mass concentrations, polycyclic aromatic hydrocarbons (PAHs), hopanes, and elemental carbon (EC) concentrations generally exhibited concentrations that decreased with distance downwind of SH-71. Concentrations of organic carbon (OC) increased from upwind concentrations immediately downwind of SH-71 and continued to increase further downwind from the roadway. This behavior may have primarily resulted from condensation of semi-volatile organic species emitted from vehicle sources with transport downwind of the roadway.     

Summertime photochemical ozone formation in Santiago,Chile

The city of Santiago, Chile experiences frequent high pollution episodes and as a consequence very high ozone concentrations, which are associated with health problems including increasing daily mortality and hospital admissions for respiratory illnesses. The development of ozone abatement strategies requires the determination of the potential of each pollutant to produce ozone, taking into account known mechanisms and chemical kinetics in addition to ambient atmospheric conditions. In this study, the photochemical formation of ozone during a summer campaign carried out from March 8–20, 2005 has been investigated using an urban photochemical box model based on the Master Chemical Mechanism (MCMv3.1). The MCM box model has been constrained with 10 min averages of simultaneous measurements of HONO, HCHO, CO, NO, j(O¹D), j(NO₂), 31 volatile organic compounds (VOCs) and meteorological parameters. The O₃–NO_x–VOC sensitivities have been determined by simulating ozone formation at different VOC and NO_x concentrations. Ozone sensitivity analyses showed that photochemical ozone formation is VOC-limited under average summertime conditions in Santiago. The results of the model simulations have been compared with a set of potential empirical indicator relationships including H₂O₂/HNO₃, HCHO/NO_y and O₃/NO_z. The ozone forming potential of each measured VOC has been determined using the MCM box model. The impacts of the above study on possible summertime ozone control strategies in Santiago are discussed.     

A semi-empirical model for urban PM10 concentrations,and its evaluation against data from an urban measurement network

We have developed a model for evaluating the mass-based concentrations of urban particulate matter. The basic model assumption is that local vehicular traffic is responsible for a substantial fraction of the street-level concentrations of both PM₁₀ and NO_x, either due to primary emissions or resuspension from street surfaces. The modelling system utilises the data from an air quality monitoring network in the Helsinki Metropolitan Area. We have determined linear relationships between the measured urban PM₁₀ data against those of NO_x in various urban surroundings, based on continuously measured hourly concentration values. The data was obtained from two stations in central Helsinki and one suburban station in the Helsinki Metropolitan Area during a period of 3 yr, from 1996 to 1998. The model also includes a treatment of the regional background concentrations, and resuspended particulate matter. The model performance was evaluated against the measured PM₁₀ data from the above-mentioned three stations and from two other stations, using data that was measured in 1999. We used two alternative model versions, one based on separate correlation parameters (PM₁₀ vs. NO_x) for each station, and another based on parameters averaged over the stations considered. We analysed the agreement between the measured and predicted hourly concentration time series, utilising the values of the fractional bias (FB) and the so-called index of agreement (IA). As expected, the model predicts relatively well the yearly mean concentrations of PM₁₀: the FB values range from −0.05 to +0.09. Model performance is also relatively good when predicting the yearly mean values that are classified separately for each hour of the day: the corresponding IA values range from 0.85 to 0.96. However, model performance is substantially worse in predicting the hourly time series of the year: the IA values using the station-specific parameters range from 0.46 to 0.65. The model was applied in evaluating the yearly average spatial concentration distribution of PM₁₀ in central Helsinki, based on the corresponding modelled NO_x concentrations. With re-evaluation of a few parameters that can be determined empirically, the model could be evaluated, and most probably applied, in other urban areas as well.     

China’s air pollution reduction efforts may result in an increase in surface ozone levels in highly polluted areas

China, as a fast growing fossil-fuel-based economy, experiences increasing levels of air pollution. To tackle air pollution, China has taken the first steps by setting emission–reduction targets for nitrogen oxides (NO_x) and sulphur dioxide (SO₂) in the 11th and 12th Five Year Plans. This paper uses two models—the Energy–Environment–Economy Model at the Global level (E3MG) and the global Chemistry Transport Model pTOMCAT—to test the effects of these policies. If the policy targets are met, then the maximum values of 32 % and 45 % reductions below ‘business as usual’ in the monthly mean NO_x and SO₂ concentrations, respectively, will be achieved in 2015. However, a decrease in NO_x concentrations in some highly polluted areas of East, North-East and South-East China can lead to up to a 10% increase in the monthly mean concentrations in surface ozone in 2015. Our study demonstrates an urgent need for the more detailed analysis of the impacts and designs of air pollution reduction guidelines for China.     

Greenhouse effect of NOX

Through various processes the nitrogen oxides (NO_X) interact with trace gases in the troposphere and stratosphere which do absorb in the spectral range relevant to the greenhouse effect (infrared wavelengths). The net effect is an enhancement of the greenhouse effect. The catalytic role of NO_X in the production of tropospheric ozone provides the most prominent contribution. The global waming potential is estimated as GWP (NO_X = 30 – 33 and 7 – 10 for the respective time horizons of 20 and 100 years, and is thereby comparable to that of methane. NO_X emissions in rural areas of anthropogenically influenced regions, or those in the vicinity of the txopopause caused by air traffic, cause the greenhouse effectivity to be substantially more intense. We estimate an additional 5–23 % for Germany’s contribution to the anthropogenic greenhouse effect as a result of the indirect greenhouse effects stemming from NO_X. Furthermore, a small and still inaccurately defined amount of the deposited NO_X which has primarily been converted into nitrates is again released from the soil into the atmosphere in the form of the long-lived greenhouse gas nitrous oxide (N₂O). Thus, anthropogenically induced NO_X emissions contribute to enhanced greenhouse effect and to stratospheric ozone depletion in the time scale of more than a century.     

Quantitative assessment of Chicago air pollution through analysis of covariance

A covariance analysis of source-receptor relationships is reported based on a 6-month air-pollution monitoring study in Chicago. Regular simultaneous measurements were made of total and respirable particulate matter (dp, particle diameter, < 2 μm); sulfate, nitrate and 18 elemental compositions for both size ranges; electrical aerosol analyzer size distributions; condensation nuclei counts; light scatter; CO, SO₂, NO, NO₂ and O₃; temperature, u.v. radiation, rainfall, humidity and wind speed and direction.The ratio between light scatter and respirable particle concentration was 2.72 m²g⁻¹ which agrees well with ratios measured at a variety of other locations. Analysis of covariance by wind direction found enrichment, with respect to TSP, for Fe, V, As and NO⁻₃. The patterns were consistent with existing point source locations and strengths. The effect of street salting was also evident as Na was enriched with respect to the winter season for dp > 2 μm. On days of low humidity (< 8 mm Hg) SO²⁻₄ concentrations were linearly associated with SO₂ levels (r² = 0.72). This relationship probably reflects primary source contributions, defined as sulfate directly emitted or formed relatively soon after discharge. At higher humidities the SO₂–SO²⁻₄ relationship was not linear; and secondary contributions, as reflected in ozone concentrations from preceding days, appeared to be important. The average primary source contribution to SO²⁻₄ concentration was estimated at 5.5 μg m⁻³ which represented about 60 % of the average level. An analysis of nitrate—NO₂ concentrations suggested a linear relationship (r² = 0.58).Analysis of covariance was found to better discriminate between source categories responsible for differences in particulate matter components than the more commonly used analysis of variance and linear regression techniques.     

Time study of trace elements and major ions during two cloud events at the Mt. Brocken

Cloud water investigations have been performed at the highest elevation of Central Germany in 1997. Results of extensive trace element measurements are presented. Besides conductivity, pH, liquid water content and major ions the data set includes 49 minor and trace elements. Estimation of crustal enrichment factors (EFs) provides an indication of the anthropogenic contributions to the cloud water concentrations. The variation of cloud composition with time has been illustrated for two selected events with different air mass origins. The chemical composition of the cloud condensation nuclei on which the droplets grow mainly determines the cloud water chemistry. For a cloud event in June 1997 the concentrations of the crustally derived elements Si, Al, Fe, Ti, Ce, La and Nd follow each other closely. The fact that SO₄²⁻, NO₃⁻ and NH₄⁺ are only moderately correlated with the particular pollutants with high enrichment factors such as Cd, Sb, Pb, Zn, Cu, As, Bi, Sn, Mo, Ni, Tl and V indicates that their source regions are more widespread. During an event in October 1997 the time trends for most minor and trace elements follow rather closely those for the major ions NH₄⁺, SO₄²⁻ and NO₃⁻. Back trajectories show that the transport from continental and marine European sources was the likely cause of the sample concentrations. EFs of trace elements in cloud water samples during the June and October event show a strong correlation with those obtained for urban particulate matter. Although both events are influenced by air masses of different origin, there is a good agreement between the EF signatures.