Atmospheric lead and bromine in Germany: post-abatement levels,variabilities and trends

INTENTION, GOAL, SCOPE, BACKGROUND: Abatement measures since the 1970s have depleted lead and bromine levels in the atmosphere over large parts of Europe. Our knowledge of the atmospheric cycling of these elements while a several decade-long period of intensive mobilization reaches its end is incomplete. OBJECTIVE: We have characterized the trends in the atmospheric levels of Pb and Br and present-day temporal and spatial variabilities. METHODS: This was achieved by short-term (weeks) and long-term (years) measurements of particulate Pb and Br at various sites in Germany. Samples of atmospheric particulate matter were collected on filter membranes and analyzed by x-ray fluorescence. RESULTS AND DISCUSSION: Average Pb levels at rural and urban inland sites did not exceed concentrations in background aerosols, sampled at a Baltic Sea coastal site, by more than a factor of 3. Due to sea salt, bromide inland particulate Br levels are below those at a coastal site. There, non-sea salt Br, however, is significant as well. Urban Pb and Br levels are not necessarily higher than rural levels. The concentration levels have decreased in such a way that the previously common source, local vehicular traffic emissions, is no longer predominant. Regional rather than local sources have been increasingly determining the concentrations since the 1990s. This is more pronounced for Br than for Pb. We found indications for coal burning and long-range transport as significant Pb sources. For particulate Pb species, a range of ages (elapsed time since Pb emission) has been found. This range shows two maxima corresponding to characteristic times of 72 and 24 h. CONCLUSIONS: The (mean) atmospheric residence time of particulate Pb is longer than the residence time of Br, in particular in the wintertime. The chemical species contributing to atmospheric Pb should be addressed in future studies. RECOMMENDATION AND OUTLOOK: Clearly, despite effective abatement measures, atmospheric Pb will continue to be dominated by anthropogenic mobilization. The influence from long-range transport can be expected to decrease with the effectiveness of abatement programmes in neighbouring countries of the region.     

Changes in elemental composition and mass of atmospheric aerosol pollution between 1996 and 2002 in a Central European city

Median atmospheric concentrations of Pb, Br, S, As, Se, and particulate matter (PM) decreased, and median concentrations of Sb, Cu, Zn, Fe, Ca, Cr and Ba increased in urban aerosol in downtown Budapest between 1996 and 2002. The changes in Pb and Br concentrations were unambiguously attributed to the phasing out of leaded gasoline. The increments were mainly related to and explained by non-exhaust vehicular emissions. The mechanical wear of asbestos-free brake linings of road vehicles contributed to the concentration of Cu and Sb on average by 69% and 66%, respectively in the PM10 size fraction. Tire rubber abrasion was a major source for atmospheric Zn; on average, non-crustal sources accounted for 67% of Zn in the PM10 size fraction. Contribution of the tire wear component to the PM10 mass was estimated to be 6% at most, while its contribution to organic aerosol was of the order of 15%.     

The use of Br/Pb ratios in atmospheric particles to discriminate between vehicular and industrial lead aerosol sources in the vicinity of a lead works—II. Ellesmere port,Cheshire

Lead and bromide in atmospheric particles were measured at two sites in the vicinity of a tetraalkyllead manufacturing plant. The Br results were used to estimate the relative proportions of vehicular and non-vehicular (presumably industrially-derived) particulate lead present in the atmosphere. The non-vehicular component was very variable over the 2-month study period, overall contributing about a quarter of the observed Pb. The relative proportions were found to be in good agreement with estimates of ground-level concentrations of Pb originating from the lead works stack derived from a Gaussian plume dispersion model.     

Trace elements in vegetables grown in an industrial area in relation to soil and air particulate matter

The relationships between the trace element content of vegetables, agricultural soil and airborne particulate matter were investigated in the greater industrial area of Thessaloniki, northern Greece. Most elements were found at concentrations normally observed in vegetables grown in uncontaminated areas, however, elevated concentrations of Pb, Zn, Cr and Mn were found particularly in leafy vegetables. The trace element content of agricultural soil was low, despite the airborne particulate matter that was highly enriched with Zn, Cd, Pb and Mn. Multivariate statistical analysis indicated that the compositional patterns of the vegetables, the soil and the atmospheric particulates were largely different. The dominant pathway for most trace elements to vegetable roots was from the soil, while trace elements in vegetable leaves appeared to originate mostly from the atmosphere. High accumulation due to atmospheric deposition was found for Pb, Cr and Cd, especially in leafy vegetables. Root vegetables were found to accumulate soil Cd more efficiently than the other trace elements.     

Atmospheric trace element concentrations in total suspended particles near Paris,France

To evaluate today’s trace element atmospheric concentrations in large urban areas, an atmospheric survey was carried out for 18 months, from March 2002 to September 2003, in Saclay, nearby Paris. The total suspended particulate matter (TSP) was collected continuously on quartz fibre filters. The TSP contents were determined for 36 elements (including Ag, Bi, Mo and Sb) using two analytical methods: Instrumental Neutron Activation Analysis (INAA) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The measured concentrations were in agreement within the uncertainties with the certified values for the polycarbonate reference material filter SRM-2783 (National Institute for Standard Technology NIST, USA). The measured concentrations were significantly lower than the recommended atmospheric concentrations. In 2003, the Pb atmospheric level at Saclay was 15 ng/m³, compared to the 500 ng/m³ guideline level and to the 200 ng/m³ observed value in 1994. The typical urban background TSP values of 1–2, 0.2–1, 4–6, 10–30 and 3–5 ng/m³ for As, Co, Cr, Cu and Sb, respectively, were inferred from this study and were compared with the literature data. The typical urban background TSP concentrations could not be realised for Cd, Pb and Zn, since these air concentrations are highly influenced by local features. The Zn concentrations and Zn/Pb ratio observed in Saclay represented a characteristic fingerprint of the exceptionally large extent of zinc-made roofs in Paris and its suburbs. The traffic-related origin of Ba, Cr, Cu, Pb and Sb was demonstrated, while the atmospheric source(s) of Ag was not identified.     

Receptor modelling using Positive Matrix Factorisation,back trajectories and Radon-222

PM_2.5 aerosols were sampled and atmospheric ²²²Rn (radon) was measured, at Hong Kong, China, over 3 years 2001–2003. The aerosol samples were analysed using accelerator-based Ion Beam Analysis (IBA) techniques to provide quantitative information on 21 of their major and minor elemental contributions. The radon concentration on aerosol sampling days was then used to classify the degree of land contact (high or low) experienced by air masses en route to the receptor site. It was found that elements known to originate from anthropogenic sources (e.g. Zn, K, Br, Pb and Black Carbon) were positively correlated with observed radon concentration. An eight-factor Positive Matrix Factorisation (PMF) analysis was performed on the data set, which resulted in elemental profiles (“fingerprints”) for eight potential sources and we identified source factors that were correlated with radon. The Potential Source Contribution Function technique was then used to identify the geographic regions most likely to have significantly contributed to the aerosol samples collected at the receptor site.     

Distribution and seasonal variability of trace elements in atmospheric particulate in the Venice Lagoon

Size distribution and selected element concentrations of atmospheric particulate matter (PM) were investigated in the Venice Lagoon, at three sites characterised by different anthropogenic influence. The PM₁₀ samples were collected in six size fractions (10-7.2, 7.2-3.0, 3.0-1.5, 1.5-0.95; 0.95-0.49 and <0.49 μm) with high volume cascade impactors, and the concentration of 17 elements (Al, As, Ca, Cd, Co, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb, Sr, V, Zn) was determined by inductively coupled plasma quadrupole mass spectroscopy. More than 1 year of sampling activities allowed the examination of seasonal variability in size distribution of atmospheric particulates and element contents for each site.At all the stations, particles with an aerodynamic diameter <3 μm were predominant, thus accounting for more than 78% of the total aerosol mass concentration. The highest PM₁₀ concentrations for almost all elements were found at the site which is more influenced by industrial and urban emissions. Similarity in size distribution of elements at all sites allowed the identification of three main behavioural types: (a) elements found mainly within coarse particles (Ca, Mg, Na, Sr); (b) elements found mainly within fine particles (As, Cd, Ni, Pb, V) and (c) elements with several modes spread throughout the entire size range (Co, Cu, Fe, K, Zn, Mn).Factor Analysis was performed on aerosol data separately identified as fine and coarse types in order to examine the relationships between the inorganic elements and to identify their origin. Multivariate statistical analysis and assessment of similarity in the size distribution led to similar conclusions on the sources.     

Elemental analysis of airborne particulates in Chile

Aerosol samples collected in three characteristic Chilean cities-including urban and remote zones-have been analyzed by the PIXE spectroscopic technique. Elemental composition, total suspended particulate matter (TSP), particle size distribution, and the peculiar geographic and meteorological parameters have been included in this study. Santiago--the polluted capital of Chile--registered high TSP indexes and important amounts of hazardous elements in air such as S, V, Cr, Zn, Br and Pb. The atmosphere of Antofagasta city showed marine and mineral activity influence. Results from Chillán city are similar to those from rural environments. Protons and deuterons-provided by the isochronous cyclotron of the University of Chile-were used to excite X-ray radiation from the sample. Signals were processed by an energy dispersive detection system, including a cryogenic Si(Li) detector, electronic for pulse amplification and an analog to digital converter. The absolute elemental concentration of the particulate matter in air was obtained through a fundamental parameter equation. Samples consist of particulate material collected directly on Nuclepore filters or deposited over Kapton foils. Typical elements analyzed were Mg, Al, Si, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, As, Br and Pb.     

Characteristic study of particulates and metallic elements at an urban sampling site in Taichung, central Taiwan

Atmospheric total suspended particulate concentrations and metallic element concentrations were measured at three locations, characteristic of urban, suburban and rural sites. The sampling period was from July 2000 to August 2000. The results indicated that the urban sampling site had the highest total suspended particulate concentrations (average 108.61μ1m3), followed by the suburban site (average 60.11μ1m3) and the rural site (average 53.31μ1m3). The average PM_2.5 concentrations (24.11μ1m3) were higher than the PM_2.5-10 concentrations (12.81μ1m3) at the urban site. The average distributed ratios for PM_2.5/PM_2.5-10 were about 1.29, 1.53, 0.12, 1.12 and 2.31 for Pb, Zn, Fe, Ni and Cr, respectively. The average total suspended particulate mass ratios for daytime and nighttime were about 1.72. As for the elements Cu, Pb, Zn, Fe, Ni and Cr, these ratios were about 0.63, 0.97, 0.54, 1.66, 0.53 and 1.12, respectively. The total suspended particulate daytime concentrations of Pb and Zn were positively correlated (R = 0.925) at the urban sampling site. The elements Ni and Cr were positively correlated both during the daytime (R = 0.648) and the nighttime (R = 0.511), revealing that they came from the same emission source during daytime and nighttime, at the urban sampling site.     

Separate dissolved and particulate trace metal budgets for an estuarine system: an aid for management decisions

The sources and sinks of dissolved and particulate Pb, Cu and Zn were determined for the main basin of Puget Sound to understand the effect man has had on metal concentrations in both the water column and in the sediments. Municipal, industrial and atmospheric sources contributed about 66% of the total Pb added to the main basin of Puget Sound during the early 1980s. Advective inputs were the major sources of total Cu and Zn (approximately 40%) while riverine and erosional sources contributed about 30%. The discharge of the particle-bound trace metals from rivers minimized the influence of particulate anthropogenic sources, which constituted 50%, 23% and 18% of the total particulate Pb, Cu and Zn inputs, respectively. While advective transport was the major source of dissolved Cu and Zn (approximately 60% of all dissolved inputs), industrial, municipal and atmospheric inputs contributed about 85%, 30% and 38% of the dissolved Pb, Cu and Zn inputs, respectively. The sources of dissolved and particulate Cu and Zn were comparable with the sinks within the errors of the analyses indicating their quasi-conservative nature. Advection removed about 60% of the total Cu and Zn added to the main basin while 40% was deposited in the sediments of Puget Sound. Because of this quasi-conservative nature of Cu and Zn, anthropogenic inputs of Cu and Zn were dispersed from the system more than they were contained within main basin sediments. About 75% of the dissolved Pb discharged into the main basin of Puget Sound was lost from the dissolved phase and was balanced by a similar gain in the particulate phase. Because of this extensive scavenging and the effective retention of particles within the main basin, about 70% of the total Pb added to the main basin was retained within its sediments. These separate mass balances have utility in management decisions because they show the relative contributions from different sources and demonstrate whether the influences of dissolved and particulate inputs are reflected solely in the water column or the sediments, respectively.     

Characterization of atmospheric trace elements on PM2.5 particulate matter over the New York–New Jersey harbor estuary

The purpose of this work is to characterize trace elements associated with atmospheric particulate matter of 2.5 μm and smaller in size (PM_2.5) over the New York–New Jersey (NY–NJ) Harbor Bight. Using low-volume PM_2.5 samplers, aerosol particulate samples were simultaneously collected for the first time at three locations in the region, Sandy Hook in the coast, New Brunswick and Liberty Science Center (Jersey City) in nearby urban areas, during January 1998–January 1999. Sample analysis for trace elements was accomplished by inductively coupled plasma mass spectrometry. Many elements in ambient air exhibit strong spatial gradients from urban centers to the coast, and the concentrations of most elements at Liberty Science Center are significantly higher than at the other two locations. Seasonal patterns are not apparent for most elements at all locations, suggesting continuous contributions from their sources. The elements Pb, Cd, Zn, Cu, Ni, V, Sb, are enriched by factors of 200 to 20,000 relative to their natural abundance in crustal soil. Major sources that contribute to the atmospheric loading of these elements include fossil fuel combustion, oil combustion, metal processing industry, and waste incineration. Atmospheric dry deposition of these trace elements associated with PM_2.5 to the coastal waters of the NY–NJ estuary may account for a significant portion of the total dry deposition fluxes for these elements.     

Atmospheric pollution in an urban environment by tree bark biomonitoring--part I: trace element analysis

Tree bark has been shown to be a useful biomonitor of past air quality because it accumulates atmospheric particulate matter (PM) in its outermost structure. Trace element concentrations of tree bark of more than 73 trees allow to elucidate the impact of past atmospheric pollution on the urban environment of the cities of Strasbourg and Kehl in the Rhine Valley. Compared to the upper continental crust (UCC) tree barks are strongly enriched in Mn, Ni, Cu, Zn, Cd and Pb. To assess the degree of pollution of the different sites in the cities, a geoaccumulation index I_geo was applied. Global pollution by V, Ni, Cr, Sb, Sn and Pb was observed in barks sampled close to traffic axes. Cr, Mo, Cd pollution principally occurred in the industrial area. A total geoaccumulation index I_GEO-tot was defined; it is based on the total of the investigated elements and allows to evaluate the global pollution of the studied environment by assembling the I_geo indices on a pollution map.     

The study of fine and coarse particles, and metallic elements for the daytime and night-time in a suburban area of central Taiwan, Taichung

Daily average concentrations of fine and coarse particulates, and TSP samples have been measured simultaneously at daytime and night-time periods by using Universal and PS-1 sampler in a suburban area of central Taiwan from June to August 1998. The samples were analyzed by atomic absorption spectrometry to determine the fine and coarse particulate concentrations of metallic elements (Ca, Fe, Mn, Pb, Cu, Zn and Cr). The concentration of PM2.5 and TSP showed a decreased trend for the daytime period. The fine particle concentrations were about two times as that of coarse particulate concentrations. The averaged fine particulate concentrations at daytime are higher than at night-time. Ca and Fe were mostly in the coarse particulate mode. The correlation coefficients were 0.63 and 0.69 for elements Ca and Fe in the coarse particle mode for day and night periods. Pb showed a similar distribution ratio with Mn for the fine to coarse particle ratios at both day and night period. Pb and Mn are highly correlated for the day (R = 0.78) and night period (R = 0.61) at particle size <2.5 microm. Cu and Zn were mainly in fine particles at both day and night period. Fe and Ca consist of the major parts of all the elements. Elemental Mn is the lowest among the rest of the heavy metals.     

Determination of atmospheric nitrogen input to Lake Greenwood,South Carolina--I. PM measurements

The Reedy River branch of Lake Greenwood, SC, has repeatedly experienced summertime algal blooms, upsetting the natural system. This lake's shallow depth makes It susceptible to atmospheric influence. A series of experiments were carried out in order to investigate the effect of atmospheric nitrogen deposition into the lake. Nitrogen was examined because of the insignificant phosphorus dry atmospheric flux and the unique nutrient demands of the dominant algae (Pithophora oedogonia) contributing to the blooms. In this paper, results are presented, of the experimental measurement of coarse and fine atmospheric concentrations of atmospheric particulate nitrogen adjacent to and in the watershed of the Reedy River (downtown Greenville) and Lake Greenwood. Experiments were carried out during four 24-hr periods in January 2001 and again during four 24-hr periods in March 2001. Results are presented here for atmospheric particulate nitrogen as well as other constituents of the airborne aerosol. Mass concentrations of PM2.5 averaged 14.0 and 21 microg/m3 for Lake Greenwood and downtown Greenville, respectively. Mass concentrations of total suspended particulates (TSP) averaged 22.6 and 38.5 microg/m3 for Lake Greenwood and downtown Greenville, respectively. This ambient aerosol concentration was apportioned to its chemical constituents, and the greatest contributors to PM2.5 mass were organics (45 and 42% for downtown Greenville and the lake, respectively) and sulfate (14.1 and 19.7% for downtown Greenville and the lake, respectively). The information gathered here, despite its episodic nature, is important not only in determining atmospheric nitrogen but also in documenting the composition of aerosol in South Carolina, which so far has not been studied. In a companion paper, results for gaseous pollutants as well as thermodynamic modeling of the aerosol and nitrogen flux determinations are presented.     

Elemental characterization of PM10, PM2.5 and PM1 in the town of Genoa (Italy)

The particulate matter (PM) concentration and composition, the PM10, PM2.5, PM1 fractions, were studied in the urban area of Genoa, a coastal town in the northwest of Italy. Two instruments, the continuous monitor TEOM and the sequential sampler PARTISOL, were operated almost continuously on the same site from July 2001 to September 2004. Samples collected by PARTISOL were weighted to obtain PM concentration and then analysed by PIXE (particle induced X-ray emission) and by ED-XRF (energy dispersion X-ray fluorescence), obtaining concentrations for elements from Na to Pb. Some of the filters used in the TEOM microbalance were analysed by ED-XRF to calculate Pb concentration values averaged over 7-30 d periods.     

Distribution of trace metals in moss biomonitors and assessment of contamination sources in Portugal

A biomonitoring survey using the moss species [Hypnum cupressiforme Hedw. and Scelopodium touretii (Brid.) L. Kock] was performed in the whole territory of Portugal, in order to evaluate the atmospheric deposition of the following elements: Cd. Cr, Cu, Fe, Mn, Ni, Pb and Zn. The concentrations of the same elements were also obtained in two types of soil samples, collected under the moss and in nearby plots without any plant coverage, and relationships between moss and soil concentrations was investigated using the multivariate statistical method of Co-inertia Analysis. Also, relationships between concentrations in moss and several anthropogenic, geologic, pedologic and environmental parameters were screened using the same method of Co-inertia Analysis. Higher concentrations of Cu, Pb and Zn were found in areas of higher population density, with higher gasoline consumption, while higher values of Fe and Cr occur in the driest region, with lower plant coverage, indicating strong contamination by resuspended soil particles. Results also show good agreement between moss and soil contents, even for elements with high contribution of anthropogenic sources. The spatial pattern in Portugal of element contents in mosses were also detected and discussed in relation to local contamination sources.     

Heavy metals and Pb isotopic composition of aerosols in urban and suburban areas of Hong Kong and Guangzhou,South China—Evidence of the long-range transport of air contaminants

Rapid urbanization and industrialization in South China has placed great strain on the environment and on human health. In the present study, the total suspended particulate matter (TSP) in the urban and suburban areas of Hong Kong and Guangzhou, the two largest urban centres in South China, was sampled from December 2003 to January 2005. The samples were analysed for the concentrations of major elements (Al, Fe, Mg and Mn) and trace metals (Cd, Cr, Cu, Pb, V and Zn), and for Pb isotopic composition. Elevated concentrations of metals, especially Cd, Pb, V and Zn, were observed in the urban and suburban areas of Guangzhou, showing significant atmospheric trace element pollution. Distinct seasonal patterns were observed in the heavy metal concentrations of aerosols in Hong Kong, with higher metal concentrations during the winter monsoon period, and lower concentrations during summertime. The seasonal variations in the metal concentrations of the aerosols in Guangzhou were less distinct, suggesting the dominance of local sources of pollution around the city. The Pb isotopic composition in the aerosols of Hong Kong had higher ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb ratios in winter, showing the influence of Pb from the northern inland areas of China and the Pearl River Delta (PRD) region, and lower ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb ratios in summer, indicating the influence of Pb from the South Asian region and from marine sources. The back trajectory analysis showed that the enrichment of heavy metals in Hong Kong and Guangzhou was closely associated with the air mass from the north and northeast that originated from northern China, reflecting the long-range transport of heavy metal contaminants from the northern inland areas of China to the South China coast.     

Trends in airborne particulates in Stuttgart, Germany: 1972-2005

Since 1972, at the University of Hohenheim in Stuttgart, Germany, airborne particulate matter (PM12 and then PM10) was continuously collected on filters and analyzed for environmentally relevant elements by X-ray fluorescence analysis. The resulting long-term time series are suitable for the investigation of trends and of seasonal variation. For the period 1972-2005, monthly and annual concentration mean values of 13 elements (Br, Ca, Cr, Cu, Fe, K, Mn, Ni, Pb, S, Ti, V, and Zn) in the air are presented. Trend curves were fitted and the mean yearly variation of the concentration for these elements was calculated and represented graphically. All trend curves show a diminution of the air pollution during this period, but to different extents. Mean trends in percent per year were calculated for each element both for the entire investigation period and for three data subsets of 10-11 years. Possible explanations are discussed in detail.     

The history of methyl chloroform emissions: 1951–2000

A complete record of annual methyl chloroform production has been compiled by combining early estimates in the technical literature (1951–1976) with audited production data supplied by chemical manufacturers (1970–1996) and with production and consumption estimates provided by the countries party to the Montreal Protocol (1989 to the present). From this, a new and comprehensive estimate of annual emissions has been developed. However, when the atmospheric concentrations calculated from these annual emissions are compared with measured concentrations, there are significant discrepancies, particularly during recent years, that merit further examination.     

Reconstructing temporal trends in heavy metal deposition: assessing the value of herbarium moss samples

The use of the herbarium moss archive for investigating past atmospheric deposition of Ni, Cu, Zn, As, Cd and Pb was evaluated. Moss samples from five UK regions collected over 150 years were analysed for 26 elements using ICP-MS. Principal components analysis identified soil as a significant source of Ni and As and atmospheric deposition as the main source of Pb and Cu. Sources of Zn and Cd concentrations were identified to be at least partly atmospheric, but require further investigation. Temporal and spatial trends in metal concentrations in herbarium mosses showed that the highest Pb and Cu levels are found in Northern England in the late 19th century. Metal concentrations in herbarium moss samples were consistently higher than those in mosses collected from the field in 2000. Herbarium moss samples are concluded to be a useful resource to contribute to reconstructing trends in Pb and Cu deposition, but not, without further analysis, for Cd, Zn, As and Ni.