Showing papers in "Journal of Atmospheric Chemistry in 2004"

A laser induced fluorescence instrument for detecting tropospheric OH and HO2: Characteristics and calibration

Abstract: Measurement capability for the detection of atmospheric OH and HO2 has been developed at the Pennsylvania State Universityover the last decade. The instrument is used in two forms: an aircraft configuration, Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS), and the configuration used on towers, Ground-based Tropospheric Hydrogen Oxides Sensor (GTHOS). The instrument uses ultraviolet laser induced fluorescence (LIF) to detect OH in air that is pulled by a vacuum pump through a small inlet into a low-pressure detection chamber; HO2 is detected by reacting it with NO to form OH, which is detected by LIF in a second detection chamber. In the calibration, equal amounts of OH and HO2 ranging from 0.15 pptv to 100 pptv are produced via photolysis of water vapor by the 185 nm emission from a low-pressure Hg lamp. Estimated absolute uncertainty at the 2σ confidence level is ± 32% for bothOH and HO2. The dependence of the instrument detection sensitivity hasbeen quantified for changes in ambient water vapor, pressure, laser power, and the flow velocity of ambient air past the inlet. During the last 7 years, the instrument has been deployed in multi-investigator intensive field studies 5 times on the NASA DC-8 aircraft and 8 times on ground-based towers. The descriptions in this manuscript detail our cumulative wisdom of the instrumental response and calibration techniques developed over this time.

Determination of Secondary Organic Aerosol Products from the Photooxidation of Toluene and their Implications in Ambient PM2.5

Abstract: A laboratory study was carried out to investigate the secondary organic aerosol products from photooxidation of the aromatic hydrocarbon toluene. The laboratory experiments consisted of irradiating toluene/propylene/NOx/air mixtures in a smog chamber operated inthe dynamic mode and collecting submicron secondary organic aerosol samples through a sampling train that consisted of an XAD denuder and a ZefluorTM filter. Oxidation products in the filter extracts were treated using O-(2,3,4,5,6,-pentafluorobenzyl)-hydroxylamine (PFBHA) to derivatize carbonyl groups followed by treatment with N,O-Bis(trimethylsilyl)-acetamide (BSTFA) to derivatize OH groups. The derivatized products were detected with a positive chemical ionization (CI) gas chromatography ion trap mass spectroscopy (GC-ITMS) system. The results of the GC-ITMS analyses were consistent with the previous studies that demonstrated the formation of multi-functional oxygenates. Denuder results showed that many of these same compounds were present in the gas, as well as, the particle phase. Moreover, evidence was found for a series of multifunctional acids produced as higher order oxidation products of the toluene/NOx system. Products having nearly the same mass spectrumwere also found in the ambient environment using identical analytical techniques. These products having multiple acid and alcoholic-OH moieties have substantially lower volatility than previously reported SOA products of the toluene photooxidation and might serve as an indicator for aromatic oxidation in the ambient atmosphere.

Precipitation Chemistry in Semi-Arid Areas of Southern Africa: A Case Study of a Rural and an Industrial Site

Abstract: Experimental data on the precipitation chemistry in the semi-arid savanna of South Africa is presented in this paper. A total of 901 rainwater samples were collected with automatic wet-only samplers at a rural site, Louis Trichardt, and at an industrial site, Amersfoort, from July 1986 to June 1999. The chemical composition of precipitation was analysed for seven inorganic and two organic ions, using ion chromatography. The most abundant ion was SO4 2 − and a large proportion of theprecipitation is acidic, with 98% of samples at Amersfoort and 94% at LouisTrichardt having a pH below 5.6 (average pH of 4.4 and 4.9, respectively). This acidity results from a mixture of mineral and organic acids, with mineral acids being the primary contributors to the precipitation acidity in Amersfoort, while at Louis Trichardt, organic and mineral acids contribute equal amounts of acidity. It was found that the composition of rainwater is controlled by five sources: marine, terrigenous, nitrogenous, biomass burning and anthropogenic sources. The relative contributions of these sources at the two sites were calculated. Anthropogenic sources dominate at Amersfoort and biomass burning at Louis Trichardt. Most ions exhibit a seasonal pattern at Louis Trichardt, with the highest concentrations occurring during the austral spring as a result of agricultural activities and biomass combustion, while at Amersfoort it is less pronounced due to the dominance of relatively constant industrial emissions. The results are compared to observations from other African regions.

Heavy Metal Concentrations in European Mosses: 2000/2001 Survey

Abstract: The heavy metals in mosses survey was originally established in 1980 as a joint Danish- Swedish initiative under the leadership of ˚ Ake Ruhling, Sweden and has, since then, been repeated at five-yearly intervals with an increasing number of countries and individuals participating. Twenty- eight European countries, almost 7000 sites and about 100 individuals have been involved in the most recent survey in 2000/2001. The survey provides data on concentrations of 10 heavy metals (arsenic, cadmium, chromium, copper, iron, lead, mercury, nickel, vanadium, zinc) in naturally growing mosses throughout Europe. The technique of moss analysis provides a surrogate measure of the spatial patterns of heavy metal deposition from the atmosphere to terrestrial systems, and is easier and cheaper than conventional precipitation analysis. The aims of the survey are to determine patterns of variation in the heavy metal concentration of mosses across Europe, identify the main polluted areas, produce regional maps and further develop the understanding of long-range transboundary pollution. As in previous surveys, there was an east/west decrease in heavy metal concentrations in mosses, related in particular to industrial emissions. Former industrial sites and historic mines accounted for the location of some high concentrations in areas without contemporary industries. Long-range transboundary transport appears to account for elevated concentrations of heavy metals in areas without emission sources, such as lead in southern Scandinavia (presumably from emission sources elsewhere in Europe). Ke yw ords: atmospheric deposition, heavy metals, long-range transboundary air pollution, mosses, trace elements

Mapping Lichen Diversity as a First Step for Air Quality Assessment

Abstract: The evaluation of air quality is an important topic. It is well known that lichens have a set of characteristics that make them well suited for biomonitoring purposes. Sampling lichen diversity is not as expensive as chemical analysis, allowing a dense sampling grid and reducing the costs. Lichen diversity can be used to identify more disturbed areas, resulting from pollution, land use or ecological variables. In recent years, in order to enable extended use of lichens and to reduce ambiguities, i.e., variations due to unwanted environmental variables, efforts have been made to develop a feasible protocol for lichen sampling for biomonitoring purposes. This work aims at providing the information needed a priori for an air quality assessment study, in the form of a map showing areas where lichen diversity and abundance is lower. This study was done by sampling foliose and fruticulose lichen diversity and frequency, in a region in southwest Portugal (Sines) with large industrial facilities. A long-term study has been underway in the same area since the 1970s using lichens as bioindicators to evaluate air quality. In this work, we used a standard protocol to determine a lichen diversity value (LDV), to be used as an indicator of environmental quality. In order to reduce uncertainty concerning the type of disturbance affecting lichens, sampling sites were restricted using well-defined criteria. Whenever possible, sampling site variables were quantified. This method allowed us to reduce the many sources of variability affecting lichen diversity.

A generalized structure-activity relationship for the decomposition of (substituted) alkoxy radicals

Abstract: A novel and readily applicable Structure-Activity Relationship (SAR) for predicting the barrier height Eb to decomposition by β C-C scission of (substituted) alkoxy radicals is presented. Alkoxy radicals are pivotal intermediates in the atmospheric oxidation of (biogenic) volatile organic compounds, and their fate is therefore of crucial importance to the understanding of atmospheric VOC degradation mechanisms. The SAR is based on available theoretical energy barriers and validated against barriers derived from experimental data. The SAR is expressed solely in terms of the number(s) Ni of alkyl-, hydroxy- and/or oxo-substituents on the α- and β-carbons of the breaking bond: Eb(kcal/mol) =17.5 − 2.1 × Nα(alk) − 3.1 ×Nβ(alk) − 8.0 × Nα,β(OH) − 8.0 × Nβ(O=) − 12 × Nα(O=). For barriers below 7 kcal/mol, an additional, second-order term accounts for the curvature. The SAR reproduces the available experimental and theoretical data within 0.5 to 1 kcal/mol. The SAR generally allows conclusive predictions as to the fate of alkoxy radicals; several examples concerning oxy radicals from prominent atmospheric VOC are presented. Specific limitations of the SAR are also discussed. Using the predicted barrier height Eb, the high-pressure rate coefficient for alkoxy decomposition k diss ∞ (298 K) can be obtained from k diss ∞ (298 K) = L ×1.8 × 1013 exp(−Eb/RT) s−1, with L the reaction path degeneracy.

An Algorithm for the Determination of All Significant Pathways in Chemical Reaction Systems

Abstract: When the output of a complex chemical model is analysed, a typical topic isthe determination of pathways, i.e., reaction sequences, that produce ordestroy a chemical species of interest.A representative example is the investigation of catalytic ozone destruction cycles in the stratosphere.An algorithm for the automatic determination of pathways in any given reactionsystem is presented. Under the assumption that reaction rates are known, it finds all significant pathways, i.e., all pathways with a rate above a prescribed threshold.The algorithm forms pathways step by step, starting from single reactions.The chemical species in the system are consecutively considered as `branching points'.For every branching-point species, each pathway producing it is connected witheach pathway consuming it.Rates proportional to `branching probabilities' are calculated.Pathways with a rate that is smaller than a prescribed threshold arediscarded.If a newly formed pathway contains sub-pathways, e.g., null cycles, it is split into these simpler pathways.In order to demonstrate the performance of the algorithm, it has been applied to the determination of catalytic ozone destruction cycles and methaneoxidation pathways in the stratosphere.

Synchronous Scan and Excitation-Emission Matrix Fluorescence Spectroscopy of Water-Soluble Organic Compounds in Atmospheric Aerosols

Abstract: Three-dimensional excitation–emission matrix (EEM) fluorescence spectra of water-soluble organic compounds (WSOC) from aerosol samples were measured and compared with those reported in the literature for natural dissolved organic matter. The EEM profiles of the WSOC presented three characteristic excitation/emission (λExc/λEm) peaks: 240/405 nm, 310/405 nm and 280/340 nm. The fluorescence intensities at λExc/λEm≈240/405 nm and λExc/λEm≈310/405 nm are located at wavelengths shorter than those reported for aquatic humic substances, indicating a smaller content of both aromatic structures and condensed unsaturated bond systems in the WSOC fraction. The EEM profiles of fractions obtained by the isolation procedure of the WSOC by the XAD resins showed that a fractionation has occurred and the XAD-8 eluate is highly representative of the total WSOC of collected aerosol. Synchronous scan spectra were more detailed than conventional fluorescence emission spectra, appearing more suitable for studying multicomponent samples such as the WSOC from atmospheric aerosols.

AGAGE Observations of Methyl Bromide and Methyl Chloride at Mace Head, Ireland, and Cape Grim, Tasmania, 1998–2001

Abstract: In situ AGAGE GC-MS measurements of methyl bromide (CH3Br) and methyl chloride (CH3Cl) at Mace Head, Ireland and Cape Grim, Tasmania (1998–2001) reveal a complex pattern of sources. At Mace Head both gases have well-defined seasonal cycles with similar average annual decreases of 3.0% yr−1 (CH3Br) and 2.6% yr−1 (CH3Cl), and mean northern hemisphere baseline mole fractions of 10.37 ± 0.05 ppt and 535.7 ± 2.2 ppt, respectively. We have used a Lagrangian dispersion model and local meteorological data to segregate the Mace Head observations into different source regions, and interpret the results in terms of the known sources and sinks of these two key halocarbons. At Cape Grim CH3Br and CH3Cl also show annual decreases in their baseline mixing ratios of 2.5% yr−1 and 1.5% yr−1, respectively. Mean baseline mole fractions were 7.94 ± 0.03 ppt (CH3Br) and 541.3 ± 1.1 ppt (CH3Cl). Although CH3Cl has astrong seasonal cycle there is no well-defined seasonal cycle in the Cape Grim CH3Br record. The fact that both gases are steadily decreasing in the atmosphere at both locations implies that a change has occurred which is affecting a common, major source of both gases (possibly biomass burning) and/or their major sink process (destruction by hydroxyl radical).

Characterization of Water-Soluble Macromolecular Substances in Cloud Water

Abstract: In this contribution we present to our knowledge the first investigations of macromolecular, often called humic-like substances (HULIS) in cloud water samples and compare them with water-soluble extracts from atmospheric PM2.5, soils and waters to study its possible origin. Chemical analysis was done using high performance liquid chromatography (HPLC) coupled with UV and diode array detector, and HPLC coupled with ESI-MS (electrospray ionization mass spectrometer). The data have been treated by principle component analysis (PCA) and cluster analysis to state similarities and/or differences between different types of samples. Our results show that the content of organic and inorganic species is distinctly different in smaller and larger droplets suggesting varying origin. We conclude that smaller droplets are formed more from organic containing condensation nuclei (CCN) and larger droplets more from inorganic containing CCN organic compounds. Putting all experimental findings together we state that HULIS in cloud water—and consequently in particulate CCN precursors—are produced in an atmospheric polymerization process from low molecular weighted organics of different origin. Evidence is found that anthropogenic sources contribute to this pathway. Cloud drops may act as reactor in this HULIS formation process but more likely are gas-phase or gas-to-particle interactions.

Heavy Metal Accumulation in the Lichen Evernia prunastri Transplanted at Urban, Rural and Industrial Sites in Central Italy

Abstract: The lichen Evernia prunastri has been employed for biomonitoring the atmospheric deposition of heavy metals at urban, rural and industrial sites in Central Italy. Lichen samples have been collected in a control site 1500 m a. s. l. (Parco Nazionale d’Abruzzo, Central Italy) and subsequently transplanted at urban site (Cassino city center), at rural location 7 km away from Cassino (S. Elia Fiumerapido) and at industrial location (Piedimonte S. Germano) surrounding an automobile factory. Once defined the surface of impact relevant to this work, the lichen samples were transplanted at the four cardinal points of each site. Studies of bioaccumulation of Pb, Cd, Cr, Cu and Zn in lichen samples were performed five times at regular intervals between November 2000–December 2001. Microwave digestion of the samples and graphite furnace atomic absorption spectrometry were employed for the heavy metal determinations. Suitable certified reference materials (CRM) were used for validation of the analytical methodology. Results showed the ability of Evernia prunastri to accumulate the heavy metals under study. As expected, the area chosen as control site showed significantly (Friedman test, cluster analysis) lower impact in comparison to the other sites and the rural site showed smaller impact than the urban and the industrial sites.

Seasonal and Diurnal Variation of Surface Ozone and a Preliminary Analysis of Exceedance of its Critical Levels at a Semi-arid Site in India

Abstract: The mixing ratios of surface O3 were measured at St. John's College, Agra, an urban and traffic influenced area for the period of 2000–2002. The monthly averaged O3 mixing ratios ranged between 8 to 40 ppb with an annual average of 21 ppb. Strong diurnal and seasonal variations in O3 mixing ratios were observed throughout the year except for monsoon season. The mixing ratios of O3 follow the surface temperature cycle and solar radiation (r = 0.72 and r = 0.65 with temperature and solar radiation, respectively). Concentrations were higher with winds associated with NE and NW direction indicating the impact of pollution sources on surface O3 concentration. Exceedance of ozone critical level was calculated using the AOT 40 index and found to be 840 ppb.h and 2430 ppb.h for summer and winter seasons, respectively. The present O3 exposures are lower than the critical level of O3 and suggest that the present level of O3 does not have any impact on reduction in crop yields.

Vegetable Crops for Biomonitoring Lead and Cadmium Deposition

Abstract: Leafy vegetables are of particular interest for the active biomonitoring of the heavy metal deposition in the environment. The leaves accumulate the deposited airborne trace elements, however, they are also influenced by soilborne metals. The level of root uptake and accumulation depends on the element concerned and specific plant characteristics that influence the sensitivity of the biomonitoring system to a large extend. Standardization of the soil substrate and a precise estimation of the root uptake are very important in order to improve the sensitivity of biomonitoring. Spinach (Spinacea oleracea), lettuce (Lactuca sativa), endive (Cichorium endivia) and lamb’s lettuce (Valerianella locusta), grown in containers filled with a common peat soil and supplied with a semi-automatic watering system, were successfully used as bioaccumulators for the Cd and Pb deposition in gardens of an industrial and a residential area. Comparisons were made between the Cd and Pb contents in the crops and the deposition flux measured with NILU particulate fallout collectors in order to determine the accumulation efficiency of each crop. The correlations found were very useful to estimate the tolerable dust deposition levels with reference to the EU Guideline for maximum levels of contaminants in leafy vegetables. Exposure of the crops in open-top chambers, which were supplied with filtered air, (provided with a roof), proved that the Pb dust deposition significantly increases the “normal” concentration in the vegetables from the reference area, whereas the cadmium deposition was too low to be measured biologically. Comparisons of exposure of the crops to ambient air with or without chamber enclosure, and in open-top chambers with filtered air allowed to determine the “normal” metal concentrations and to estimate the “biological detection limits”.

Atmospheric Dioxin and Furan Deposition in Relation to Land-Use and Other Pollutants: A Survey with Lichens

Abstract: Polychlorodibenzeno-dioxins and polychlorodibenzeno-furans (PCDD/Fs) are considered among the most toxic compounds on earth. The aim of the present study was to evaluate atmospheric PCDD/F deposition and identify the areas with greater deposition of these compounds in an important industrialized and urbanized region of Portugal, using lichens as biomonitors. For this purpose, samples of the lichen Xanthoria parietina were collected at 60 sampling sites, covering urban, industrial, forestry and agriculture areas, and analyzed for PCDD/Fs, sulfur, nitrogen, zinc, iron, chromium, lead, cobalt, nickel, copper, calcium, manganese, magnesium and potassium. The concentrations of PCDD/Fs in lichens were compared with the other elements and related to land-use and population density. The results obtained through the geostatistical interpolations and after principal component analysis have shown that PCDD/F deposition estimated by lichens is greater near industrial and highly populated urban areas. We found that lichens are suitable biomonitors of PCDD/F atmospheric deposition and can contribute to a better knowledge of air quality in a region, enabling identification of critical pollutant deposition areas.

Arsenic Speciation in Lichens and in Coarse and Fine Airborne Particulate Matter by HPLC–UV–HG–AFS

Abstract: A three-step sequential extraction procedure with Milli-Q, CaCl2 and H3PO4 was applied for extraction of arsenic species in lichen transplants and airborne particulate matter (fine and coarse fractions) The samples used in this work were collected in 1994–1995 near coal-fired power plants Both transplant lichens and airborne particulate matter were submitted to the same environment simultaneously Arsenic species identification and quantification was performed by HPLC–UV–HG–AFS Inorganic forms of arsenic (arsenite and arsenate) were present in significant amounts in most of the samples Only in lichens also organic forms of arsenic (monomethyl arsonic acid and dimethyl arsinic acid) were identified which may indicate biotransformation of inorganic arsenic

Interference Testing for Atmospheric HOx Measurements by Laser-induced Fluorescence

Abstract: Accurate OH and HO2 (collectively called HOx) measurements by laser-induced fluorescence (LIF) may be contaminated by spurious signals from interfering atmospheric chemicals or from the instrument itself. Interference tests must be conducted to ensure that observed OH signal originates solely from ambient OH and is not due to instrument artifacts. Several tests were performed on the Penn State LIF HOx instrument, both in the laboratory and in the field. Theseincluded measurements of the instrument's zero signal by using either zero air or perfluoropropylene to remove OH, examination of spectral interferences from naphthalene, sulfur dioxide, and formaldehyde, and tests of interferences by addition of suspected interfering atmospheric chemicals, including ozone, hydrogen peroxide, nitrous acid, formaldehyde, nitric acid, acetone, and organic peroxy radicals (RO2). All tests lacked evidence ofsignificant interferences for measurements in the atmosphere, including highly polluted urban environments.

Validation and application of plants as biomonitors of trace element atmospheric pollution a co-ordinated effort in 14 countries

Abstract: The International Atomic Energy Agency (IAEA) organized a co-ordinated research project (CRP) on “Validation and application of plants as biomonitors of trace element atmospheric pollution analysed by nuclear and related techniques” involving 14 participating countries. The CRP’s objective was to identify appropriate bioindicators for local and/or regional application and validate them for general air pollution monitoring. Activities included quantification studies, research into spatial and time resolution for particular organisms, and physiological studies. A number of suitable bioindicators were identified in different parts of the globe and tested during the CRP. Sampling strategies were reviewed and the recommended approach adopted by the group. Appropriate sample preparation procedures were assessed and harmonised to the degree allowed by different geographic and climatic conditions in the participating countries. Two interlaboratory comparison exercises were carried out on lichen and moss materials. Results confirmed definite improvement in analytical performance of the participating laboratories, but also revealed possible inconsistencies due to different sample processing procedures. Several monitoring surveys were carried out and consequently pollution maps drawn for extended areas or countries. Overall results confirmed applicability of lower plants for assessing the degree of atmospheric pollution and provided several countries with effective monitoring tools not used before.

Assessment of Lichen Vitality During a Transplantation Experiment to a Polluted Site

Abstract: The present work evaluates the stress effects in two epiphytic lichen species with different thallus morphology, the foliose Parmelia caperata and the fruticose Evernia prunastri, as resulting from transplanting from an unpolluted to an air-polluted area Lichen samples were collected in Portugal in a clean area, during the spring 2003, and transplanted (1) to the same zone nearby and (2) to a polluted area as affected by an industrial complex Transplant samples were taken periodically during four months in both places At the same time lichen samples from the clean-air site native (in-situ) populations were also collected For each sample were measured the chlorophyll content, the chlorophyll degradation and the cell membrane damage, the latter represented by leacheate conductivity During the experiment the meteorological conditions were registered The results indicate the absence of stress effects of transplanting as such, and suggest that leachate conductivity may be the more sensitive indicator of general lichen vitality

Atmospheric Deposition of Trace Elements in Romania Studied by the Moss Biomonitoring Technique

Abstract: The first systematic study in Romania of atmospheric pollution from heavy metals and other toxic elements based on moss analysis was undertaken as a Romanian-Russian-Norwegian collaboration, primarily in order to assess the general state of heavy metal pollution in Romania. An additional goal was to contribute to the European heavy metals in mosses survey, conducted under the auspices UNECE ICP Vegetation 1 which reports to the Working Group of Effects of the Long-range Transboundary Air Pollution Convention. Samples of the moss species Hypnum cupressiforme, Hylo- comium splendens and Brachytechium salebrosum and B. rutabulum were collected during the period 1995-2001. A total of 40 elements were determined using NAA and AAS. The total concentrations of arsenic, cadmium, copper, nickel, vanadium and zinc are presented in the form of contour maps. Generally, the observed concentrations in Romania are markedly higher than those observed in most other countries of Europe using the moss technique. Ke yw ords: atomic absorption spectrometry, heavy metal pollution, moss biomonitoring technique, neutron activation analysis, trace elements.

Spatial and temporal variations of trace element contents in Xanthoria Parietina Thalli collected in a highly industrialized area in Northern France as an element for a future epidemiological study

Abstract: This work was made in Dunkirk, which is located on the French coast, in the north, near Belgium and Great Britain. The study concerned the industrial and urban surroundings of Dunkirk and Dunkirk itself. Objectives of our study is (1) to monitor spatial patterns and temporal trends (1995–2003) of trace element (As, Cd, Hg, Ni, Pb, V, Zn) deposition and (2) to make a first evaluation of exposed population to highest metals concentrations. This work is the first step of future epidemiological investigation. In 1995, the high lead concentrations were due to industrial emissions and to traffic. Zinc and arsenic concentrations were also high and widespread in the entire studied zone, but higher near industrial area. Mercury concentrations were limited in the western part and clearly revealed the impact of waste incinerator. We did not find any significant difference between trace element contents in lichens between 1995 and 2003 except for mercury, which decreased. In 2003, the contamination by lead was more focused in the biggest metallurgical plant, which is now the predominant source for this element. The traffic impact decreased, but there was still lead remaining. For the other elements the highest concentrations were observed near the industrial zone. Highest contaminations concern 25–33% of the population, who live near industrial zone in districts where annual average incomes are the lowest. Those results confirm the needs for a further epidemiological study, which could take place in priority where population is the most exposed.

Could Ornamental Plants Serve as Passive Biomonitors in Urban Areas

Abstract: A search for cheap and efficient method to monitor atmospheric particulates in city centres has raised new interest to measure foliar element concentrations after the role of particulate pollution for respiratory illnesses was discovered. Leaf samples of Golden dewdrop (Duranta repens L.) collected in Palermo (South of Italy) between 1998 and 2000 were analysed to study the possible use of this shrub as a passive biomonitor for atmospheric pollution in urban areas. Concentrations of Ba, Cd, Cu, Fe, Mg, Mn, Pb and Zn were determined from leaf samples collected from six sampling sites representing either (a) areas of high traffic density or (b) areas not directly affected by the city traffic (e.g. gardens). Most of the elements showed a significant temporal variation but no consistent trends could be seen, i.e. the highest (or lowest) values were not detected consistently at some particular time of the year. Furthermore temporal changes were of same magnitude in polluted versus less polluted areas; no statistically significant interaction between pollution level and collection period was detected. Pollution level (traffic density) was the primary factor to explain spatial variation only in the case of foliar Mg concentrations. On the other hand, variation in foliar concentrations between sampling sites (irrespective of the pollution level) was large. Our results suggest that particulate deposition needs to be quite high before spatial segregation can be done on the basis of foliar element concentrations.

Pollen Viability for Air Pollution Bio-Monitoring

Abstract: Biological characterization of Corylus avellana L. and Pinus nigra L. pollen samples was carried out to determine the actual value of pollen as a bio-indicator of the effects of atmospheric pollution, using samples from plants naturally developed in sites controlled for air pollution. In Trentino (North Italy), we selected six stations at three different levels of air pollution, which are constantly monitored with automatic gauges by the Environmental Protection Agency of Trento. First results showed that pollen viability of both species, germinability and pollen tube length of P. nigra, were higher in areas with no road traffic compared to heavy traffic ones. Pollen viability of P. nigra was positively correlated to ozone (O3) concentrations and altitude but negatively to sulphur dioxide (SO2), particulate matter with a diameter less than 10 μ m (PM10), nitrogen oxides (NOx) and nitrogen dioxide (NO2) concentrations.

Bioaccumulation of Cobalt in Parmelia sulcata

Abstract: Six locations across mainland Portugal were selected for exposing Parmelia sulcata, for a one-year period (8 months for one site), with simultaneous measurement of total (dry + wet) deposition (one-month periods). The exposed lichens and the total (dry + wet) deposition were analysed for cobalt contents by INAA (instrumental neutron activation analysis) and ICP-MS (inductively coupled plasma mass spectroscopy), respectively. The designated “wet” deposition was evaluated through the collected water volume; the designated “dry” deposition was assessed after the (dried) residual mass of the “wet” deposition. An excellent agreement between Co contents in exposed lichens and the cumulative (1) Co contents in the “dry” deposition, (2) “dry” deposition, and (3) “wet” deposition has been found for the locations with alternate drought and precipitation months, high “dry” deposition, and high Co contents in the latter. Continuous rainfall was found to hinder the Co accumulation in the lichen due to its release from the lichen and/or lower Co contents in the “dry” deposition. At three locations, P. sulcata Co contents, after subtraction of the background (before exposure), equalled or exceeded the Co contents in the cumulative “dry” deposition at the end of the exposure time. The optimal exposure period for this species likely depends on the exposure conditions.

Biological and Temporal Variations of Trace Element Concentrations in the Moss Species Scleropodium purum (Hedw.) Limpr.

Abstract: Over a period of one year, the moss Scleropodium purum was sampled every two weeks in a French rural area to determine the levels of Li, Na, Al, Si, P, Ca, V, Mn, Fe, Zn, Ba, Hg, and Pb. The element distribution in the moss shoot was studied throughout the year. An apical bioconcentration was discovered for Na, P, Ca, Mn, and Zn, whereas higher levels were found in the basal fraction for Li, Al, Si, V, Fe, Ba, Hg, and Pb. A significant variation of element concentrations was observed during the sampling period. In the apical part Li, Al, Si, V, Fe, Ba, and Hg show maximum levels in the summer and minimum in the autumn. The same pattern was found with Ca and Mn in the whole plant, whereas Na showed opposite fluctuations.

Monitoring of Short-Term Heavy Metal Deposition by Accumulation in Epiphytic Lichens (Hypogymnia Physodes (L.) Nyl.)

Abstract: Many lichens are very sensitive to air pollution due to their symbiotic nature. However, they are generally less sensitive to toxic effects of trace elements; therefore they can be used as accumulator organisms for estimating concentrations of these elements in the environment. Heavy metal accumulation in lichens is a commonly used bioindication method for assessing heavy metal ambient levels. An active biomonitoring method was used for the determination of short-term accumulation of zinc, lead, arsenic and cadmium by epiphytic lichens transplanted at different localities in Slovenia polluted by heavy metals. The atomic absorption spectrophotometry method was used for the determination of heavy metal content in lichen thalli. The content of heavy metals in lichens collected in the background area with clean air (Rogla, Pohorje Mountains) was used as the reference value. Lichens were transplanted from Rogla using the branch transplantation technique for a period of 6 months in the surroundings of Slovenian thermal power plants (Velenje, Sostanj, Zavodnje, Veliki Vrh, Vnajnarje, and Dobovec) and close to the lead and zinc ore smelter at Žerjav. The monthly accumulation of heavy metals was comparable within years at selected locations. Heavy metal pollution was the highest at Žerjav despite of remediation of lead and zinc ore smelter. The monthly accumulation of all four heavy metals was statistically significantly higher in lichens exposed at Žerjav than at other localities.

Uranium Isotopes, Metals and Other Elements in Lichens and Tree Barks Collected in Bosnia–Herzegovina

Abstract: The United Nations Environment Programme (UNEP) performed field surveys at 15 sites in Bosnia–Herzegovina where depleted uranium (DU) ammunition was used by the North Atlantic Treaty Organization (NATO) during the Balkans conflict (1994–1995). During the field missions, the Italian Environmental Protection Agency (APAT) evaluated airborne contamination due to DU dusts or aerosol particles, generated at the time of the conflict by the impact of DU ammunition on hard “targets,” using lichens and tree barks as biomonitors. Each sample was analyzed by alpha-spectrometry for DU determination. The 234U/238U activity concentration ratios were used to distinguish natural from anthropogenic uranium. This paper reports the data obtained by the UNEP investigation, including (non-radioactive) metal and other element concentrations in lichen and tree bark samples measured by instrumental neutron activation analysis (INAA). The results indicated: (i) lichens and tree barks are sensitive bio-accumulators of past airborne contamination by depleted uranium dusts; (ii) 8 years after the conflict, environmental DU contamination is still present at some of the target sites; and (iii) the highest concentrations of most non-radioactive elements were found at sites used for ammunition destruction.

Particle Size Distribution and Gas-Particle Partition of Polycyclic Aromatic Hydrocarbons in Helsinki Urban Area

Abstract: Ambient concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured in Helsinki (Finland). Particle mass size distributions were obtained with a cascade impactor (12 stages) with glass fibre filters as substrates. Simultaneously with the impactor measurements, particulate and gaseous PAHs were collected on a quartz filter and XAD-2 adsorbent, respectively, for evaluation of gas-partition coefficients. Samples were analysed for PAHs by on-line coupled supercritical fluid extraction - liquid chromatography - gas chromatography - mass spectrometry. The impactor results showed that most of the PAHs in Helsinki urban area were concentrated in fine particles (<2.5 µm diameter) with unimode peak at about 1 µm. The results were comparable with the number distri- bution measured with a differential mobility particle sizer. Total amounts of PAHs (gas + particle) varied from 15 (acenaphthylene) to 1990 (fluorene) pg/m 3 . The PAHs lighter than 202 amu (pyrene and fluoranthene) were exclusively in gas phase, whereas those heavier than 202 amu were mostly as- sociated with particles. A plot of the partition coefficients (logKp) versus the temperature dependent sub-cooled vapour pressures (logp 0 ) showed a gradient of -0.66, which deviated from equilibrium

Zinc, lead and cadmium content in meadow plants and mosses along the M3 motorway (Hungary)

Abstract: The heavy metal content was investigated in meadow plants located in a cultivated area and situated along the M3 motorway (Hungary). In addition to the meadow plants used as passive bioindicators, active bioindicators were also exposed to examine the accumulation rate of air pollutants. Tortula ruralis (Hedw.) Geartn. ssp. ruralis was applied to monitor the status of the environment. Meadow plant samples were collected at distances of 5, 10, 25, 50 and 100 m from the motorway and moss samples were exposed at the same distances. The zinc, lead and cadmium content of meadow plants and moss samples were analysed by ICP spectrophotometry. It was found that the zinc, lead and cadmium contents of the meadow plants decreased as the distance increased from the motorway. There was a significant difference even between values measured at the distances of 5 m and 10 m. The heavy metal contents in the moss samples exceeded those of the meadow plants. The heavy metal content in moss samples decreased with distance from the motorway. On comparing the data with Hungarian standards, it was found that measured values did not exceed the maximum allowed concentration levels.

Field and laboratory exposures of two moss species to low level metal pollution

Abstract: Moss transplants of the species Rhytidiadelphus squarrosus and Pleurozium schreberi were used as active biomonitoring organisms as a part of a monitoring study to assess the impact of metals associated with ambient particles on mosses at roadsides. The moss samples were exposed at a semi-urban and roadside site for 3 months for subsequent analysis of metal concentration (Cu, Pb and Zn). This field experiment was carried out to investigate the accumulation of the metals over a period of 0, 4, 8 and 12 weeks at the two sites. The metal concentration in the moss samples generally increased with the length of exposure and was higher at the roadside site. The two species, however, showed slightly different accumulation patterns. In addition to the metal analysis chlorophyll concentrations were analysed as a measure of stress response in the moss samples of the above mentioned field exposures. The chlorophyll concentrations of exposed mosses showed no or only weak correlations to the concentration of the three metals measured in the moss, which suggests that other conditions have a greater influence on the chlorophyll concentration. The effect of a single metal on the moss was studied in laboratory experiments exposing R. squarrosus to the metals copper, lead and zinc at concentrations based on the above field data. At the concentrations used there was a significant reduction in the chlorophyll a concentration after exposure to copper.

The APE-THESEO tropical campaign: An overview

Abstract: The APE-THESEO campaign was held from 15 February to 15 March 1999 from the Seychelles in the western Indian Ocean. APE-THESEO stands for ‘Airborne Platform for Earth observation — (contribution to) the Third European Stratospheric Experiment on Ozone’. The campaign aimed to study processes controlling the low water content of the stratosphere, including the mechanisms of cloud formation in the tropical tropopause region, and transport processes, studied using measurements of long-lived trace gases and ozone. Two aircraft were used: the high-altitude research aircraft, M-55 Geophysica, which can fly up to 21 km, and the Falcon of the Deutsches Zentrum fur Luft- und Raumfahrt, a tropospheric aircraft. Seven flights were performed, including the first simultaneous in situ and remote sensing of sub-visible cirrus clouds, the first interception of sub-visible cirrus using in-flight guidance from a path-finding aircraft, and guided descent of a high-altitude research aircraft into the anvil cloud at the top of a tropical cyclone. In this paper we describe the payload used, the objectives for each flight, and the meteorological conditions encountered. First results show that a new type of cloud, which we have dubbed ultra-thin tropical tropopause cloud (UTTC), has been observed frequently, and observed to cover areas of 105 km2. The frequent coincidence of the tropopause and hygropause implies that the western Indian Ocean played an important role in the dehydration of the lower tropical stratosphere during the season of the mission. UTTCs, sub-visible cirrus, and visible cirrus, have all been implicated in the observed dehydration. Tracer measurements indicate little mixing of stratospheric air into the upper tropical troposphere.