Study of Trace and Heavy Metals in Rural and Urban Aerosols of Uludağ and Bursa (Turkey)

The concentrations of heavy, trace elements and major ions measuredin the Uluda and Bursa aerosols were investigated to assess size distributions, spatial and temporal variability, sources and source regions affecting the composition of aerosols in Uluda and Bursa. A total of 81 samples were collected in two sites, one in Bursa city and another in the Uluda Mountain during two sampling campaigns. Daily samples were collected using a high volume sampler on Whatman 41 cellulose filters in Uluda, while three days interval samples were collected in Bursa using an automatic dichotomous sampler on PTFE Teflon filters. Samples were analysed for 15 trace and heavy metals (Al, Fe, Ba, Na, Mg, K, Mn, Ca, Cu), (V, Pb, Cd, Cr, Ni, Zn), and 4 major ions (SO₄ ^2-, NO₃ ^-, Cl^-), (NH₄ ⁺) using ICP-AES, GFAAS, HPLC and UV/VIS Spectrophotometer,respectively. In general, concentrations of the metals measured inUluda aerosols were lower than those in Bursa. The concentrations of crustal elements were higher in summer than winter, while anthropogenic elements had higher concentrations in winter than summer. Most of the mass of crustal elements was concentrated in the coarse mode while the mass of the heavy metals was concentrated in the fine mode. Factor analysis revealed four factors with sources including crustal, industrial and combustion. Back trajectory calculations were used to determine long range contributions. These calculations showed that contributions were mostly from European countries, former Soviet Union countries, Black Sea and North Africa.     

Modelling of Air Quality with CAMx: A Case Study in Switzerland

The three-dimensional Eulerian model CAMx (Comprehensive Air QualityModel with Extensions) was applied for the first time to simulate bothgaseous and particulate photochemical air pollution in Switzerland during July 28–30, 1993. The meteorological input data were prepared using the Systems Applications International Mesoscale Model (SAIMM). The CAMx model results were compared with the measurements carried out at ground level andfrom airborne measuring platforms within the frame of the Swiss POLLUMET research programme. In general, the CAMx performance for gaseous species wasfound to be better than that of the previously used Urban Airshed Model (UAM)and the Variable Grid Urban Airshed Model (UAM-V). The most significant improvement for the gaseous species is in the prediction of HNO₃ concentrations, due to the inclusion of aerosol chemistry. Aerosol species such as NO₃ ^-, NH₄ ⁺, SO₄ ^2-, and secondary organic aerosols were calculated in one particle size range (0.04–2.5 m) and compared with a few measurements available. Although July 29 was reasonably well simulated, overestimated wind speeds by SAIMM for July 30 caused a too fast transport of pollutants. Similarly to measurements, significant spatial correlation of the secondarily formed aerosols with ozone and formaldehyde is found in the afternoon.     

A Relaxed Eddy Accumulation System for the Automated Measurement of Atmospheric Ammonia Fluxes

A continuous relaxed eddy accumulation system ispresented for the automated measurement of surface/atmosphere exchange fluxes of atmospheric ammonia (NH₃) at a single height. The new system features sampling by parallel plate denuder inlets, online chemical analysis using the conductivity cell of a commercially available NH₃ analyzer and online flux calculation. The effective detection limit of the system for air concentrations is 0.2 g m^-3 and it is estimated to resolve fluxes > ± 20 ng m^-2 s^-1, depending on the NH₃ concentration and turbulence. The performance of the system was tested in two measurement campaigns above agricultural grassland, in which it was compared with a 3-point continuous gradient system. During the first campaign, after urea application of 47 kg N ha^-1 in autumn, the REA system derived fluxes which were on average twice as large as the gradient fluxes, while concentrations agreed closely (on average within 4%). Possible reasons include differences in the footprint and an over-correction of the gradient flux in stable conditions. Due to wet and cold conditions, only 0.3% of the fertilizer N was volatilized as NH₃ during the first week. Results from the deployment of an improved system are presented for a summer day, 6 days after fertilization with calcium ammonium nitrate. The agreement of both concentrations (on average within 13%) and fluxes (26%) was very encouraging and similar to the agreement found between two state-of-the-art gradient systems with online analysis.     

A New Diffusion Denuder System for Long-Term,Regional Monitoring of Atmospheric Ammonia and Ammonium

Estimating regional patterns in concentrations of atmosphericammonia (NH₃) gas and ammonium (NH₄ ⁺) in aerosolis essential to assess dry deposition, as well as to test theperformance of long-range transport models. Until now, methods for monitoring NH₃ and NH₄ ⁺ (collectively NH_x) have focused on either passive sampling, which does not sample aerosol NH₄ ⁺, or active sampling techniquessuitable for sampling over several minutes to 24 hr. The classicalactive sampling approach is the diffusion denuder, which typically involves either a complex annular denuder or a long(0.5 m) and fragile glass tube. A new denuder implementationis reported here that has been designed for long-term samplingof NH₃ and NH₄ ⁺. By sampling at just 0.35 L min^-1, the method is suitable for monthly measurementsand uses 0.1 m long glass denuders, which may be sent safelyby the normal postal service to monitoring sites. Two denudersare applied in series to test for adequate NH₃ captureefficiency in each sample, while a subsequent acidified paperfilter collects NH₄ ⁺. The method has been implementedat over 50 sites across the U.K. as part of a new national monitoring network. The detection limit is <0.01 μg m^-3 and the sampling is sufficiently accurate to show theseasonal patterns at different sites. This low-cost method willbe useful to address future trends in NH₃ and NH₄ ⁺, especially in relation to compliance with international agreements to reduce NH₃ emissions.     

Correlating the Spatial Distribution of Atmospheric Ammonia with δ15N Values at an Ammonia Release Site

A field ammonia (NH₃) release experiment and open top chambers containing moorland monoliths continuously fumigated with NH₃ or sprayed with NH₄Cl were used to assess the potential for using ¹⁵N values in determining the area of influence around a point NH₃ emission source. ¹⁵N values are being increasingly used as environmental tracers and we tested the hypothesis that the ¹⁵N signal from an NH₃ emission source is observable in nearby vegetation. Using modified monitoring devices, atmospheric NH₃ concentrations were found to decrease with distance from source, with ¹⁵N values also reflecting this trend, producing a signal shift with changing concentration. Open top chamber studies of ¹⁵N values of Calluna vulgaris (L.) Hull indicated a correlation with deposition treatments in current year shoots. Analysis of Calluna shoots from the NH₃ release showed a similar trend of ¹⁵N enrichment. Significant linear correlations between ¹⁵N and percent N in plant material were found, both in the controlled conditions of the open top chambers and at the NH₃ release site, illustrating the possible use of this technique in N deposition biomonitoring.     

Satellite and Ground Based Monitoring of Aerosol Plumes

Plumes of atmospheric aerosol have been studied using a rangeof satellite and ground-based techniques. The Sea-viewing WideField-of-view Sensor (SeaWiFS) has been used to observe plumesof sulphate aerosol and Saharan dust around the coast of theUnited Kingdom. Aerosol Optical Thickness (AOT) was retrievedfrom SeaWiFS for two events; a plume of Saharan dusttransported over the United Kingdom from Western Africa and aperiod of elevated sulphate experienced over the Easternregion of the UK. Patterns of AOT are discussed and related tothe synoptic and mesoscale weather conditions. Furtherobservation of the sulphate aerosol event was undertaken usingthe Advanced Very High Resolution Radiometer instrument(AVHRR). Atmospheric back trajectories and weather conditionswere studied in order to identify the meteorologicalconditions which led to this event. Co-located ground-basedmeasurements of PM₁₀ and PM_2.5 were obtained for 4sites within the UK and PM_2.5/10 ratios were calculatedin order to identify any unusually high or low ratios(indicating the dominant size fraction within the plume)during either of these events. Calculated percentiles ofPM_2.5/10 ratios during the 2 events examined show thatthese events were notable within the record, but were in noway unique or unusual in the context of a 3 yr monitoringrecord. Visibility measurements for both episodes have beenexamined and show that visibility degradation occurred duringboth the sulphate aerosol and Saharan dust episodes.     

Characterization of Dust Storms to Hong Kong in April 1998

In April 1998, two intense dust storms were generated in CentralAsia and transported eastward across East Asia (15 and 19 April). This article presents the chemical characterization ofHong Kong (HK) aerosols during the dust storms. During the 15 Aprildust storm, hourly respiratory suspended particles (RSP)(particle diameter smaller than 10 m) concentrationsmonitored at 7 sites in Hong Kong reached the peak valuessynchronously between 9 and 11 a.m. on 17 April, in which thehighest concentration was 267 g m^-3. Analysis ofthe RSP samples showed that concentrations of crustalelements (Ba, Ca, Cd, Cr, Fe, Mg, K⁺) and anthropogenicspecies (As, Ni, Pb, Zn, NH₄ ⁺, NO₃ ^-,SO₄ ^2- and total carbon) were substantiallyenhanced. Enhancement of these species was more than afactor of 2 to 14 relative to the non dust period. The totalcarbon content was high, at 59 g m^-3 (notincluding carbonate), and the enrichment factors of Asand Pb on 17 April were 122 and 117, respectively. Thisimplied that anthropogenic materials together with mineraldust were transported to HK from Mainland China. Based onmaterial balance calculations, mineral dust contributed41% to the observed RSP mass on 17 April, which was 2 times thatof the nondust sample (22%). From the 5-day backwardtrajectory analysis, this storm was transported directlyfrom Northwest China to HK. However, there was nocorresponding observation for the 19 April dust stormaerosol. Consequently, 15 April storm had stronger impact onHK's atmosphere than 19 April storm. Compared to the HK AirQuality Objective, 15 April dust storm did not cause seriousair pollution in HK.     

Quantifying dry NH3 deposition to an ombrotrophic bog from an automated NH3 field release system

Providing an accurate estimate of the dry component of N deposition to low N background, semi-natural habitats, such as bogs and upland moors dominated by Calluna vulgaris is difficult, but essential to relate nitrogen deposition to effects in these communities. To quantify the effects of NH₃ inputs to moorland vegetation growing on a bog at a field scale, a field release NH₃ fumigation system was established at Whim Moss (Scottish Borders) in 2002. Gaseous NH₃ from a line source was released along of a 60 m transect, when meteorological conditions (wind speed >2.5 m s^–1 and wind direction in the sector 180–215°) were met, thereby providing a profile of decreasing NH₃ concentration with distance from the source. In a complementary study, using a NH₃ flux chamber system, the relationships between NH₃ concentrations and cuticular resistances were quantified for a range of NH₃ concentrations and micrometeorological conditions for moorland vegetation. Cuticular resistances increased with NH₃ concentration from 11 s m^–1 at 3.0 g m^–3 to 30 s m^–1 at 30 g m^–3. The NH₃ concentration data and the concentration-dependent canopy resistance are used to calculate NH₃ deposition taking into account leaf surface wetness. The implications of using an NH₃ concentration-dependent cuticular resistance and the importance for refining critical loads are discussed.     

The influence of atmospheric n deposition on nitrous oxide and nitric oxide fluxes and soil ammonium and nitrate concentrations

The deposition of atmospheric N to soils provides sources of available N to the nitrifying and denitrifying microbial community and subsequently influences the rate of NO and N₂O emissions from soil. We have investigated the influence of three different sources of enhanced N deposition on NO and N₂O emissions 1) elevated NH₃ deposition to woodlands downwind of poultry and pig farms, 2) increased wet cloud and occult N deposition to upland forest and moorland and 3) enhanced N deposition to trees as NO^? ₃ and NH⁺ ₄ aerosol. Flux measurements of NO and N₂O were made using static chambers in the field or intact and repacked soil cores in the laboratory and determination of N₂O by gas chromatography and of NO by chemiluminescence analysis. Rates of N deposition to our study sites were derived from modelled estimates of N deposition, NH₃ concentrations measured by passive diffusion and inference from measurements of the ²¹⁰Pb inventory of soils under tree canopies compared with open grassland. NO and N₂O emissions and KCl-extractable soil NH⁺ ₄ and NO^? ₃ concentrations all increased with increasing N deposition rate. The extent of increase did not appear to be influenced by the chemical form of the N deposited. Systems dominated by dry-deposited NH₃ downwind of intensive livestock farms or wet-deposited NH⁺ ₄and NO^? ₃ in the upland regions of Britain resulted in approximately the same linear response. Emissions of NO and N₂O from these soils increased with both N deposition and KCl extractable NH⁺ ₄, but the relationship between NH⁺ ₄ and N deposition (ln NH⁺ ₄ = 0.62 ln N_deposition+0.21, r ² = 0.33, n = 43) was more robust than the relationship between N deposition and soil NO and N₂O fluxes.     

High Immobilization of NH4+ in Danish Heath Soil Related to Succession,Soil and Nutrients: Implications for Critical Loads of N

During recent decades heathlands havechanged into grasslands in regions with high atmosphericnitrogen deposition. In regions with intermediatedeposition level (e.g., Denmark) changes have been lesspronounced which may be due to delay or decrease inresponse of the ecosystem. The mor layer (O horizon) mayplay an important role for this delay due to high sinkstrength for N. In this study, the capacity for netNH₄ ⁺ immobilization and mineralization wasstudied during short- and long-term incubations (2–36 days)of mor samples from Danish dry inland heaths. High short-term capacity for net NH₄ ⁺ immobilization wasfound to be a general characteristic of Danish heath morlayers both under heather (Calluna vulgaris) andcrowberry (Empetrum nigrum ssp nigrum), the latterdominating late stages in heathland succession. The netNH₄ ⁺ immobilization was higher under youngcompared to old or dead vegetation, and higher on lessnutrient poor soils than on extremely nutrient poor soils.The addition of N, P and C stimulated CO₂ productionand net NH₄ ⁺ immobilization, but not net Nmineralization. The immobilization of ¹⁵NH₄ ⁺caused release of dissolved organic N, increased N anddecreased C/N ratio in the microbial biomass, and indicatedgrowth of microorganisms with other metabolic abilitiesthan the indigenous population. No evidence was obtained ofstabilization of immobilized ¹⁵NH₄ ⁺ intosoil organic matter during the experiment. On background ofthe results and current knowledge it was concluded that therecognition of the high capacity for net NH₄ ⁺immobilization in mor layers does not allow for a raiseof critical loads for N for northern dry inland heaths.     

The Control of SO2 Dry Deposition on to Natural Surfaces by NH3 and its Effects on Regional Deposition

Two years of continuous measurements of SO₂deposition fluxes to moorland vegetation are reported. The mean flux of 2.8 ng SO₂ m^-2 s^-1 is regulated predominantly by surface resistance (r _c) which, even for wet surfaces, was seldom smaller than 100 s m^-1. The control of surface resistance is shown to be regulated by the ratio of NH₃SO₂ concentrations with an excess of NH₃ generating the small surface resistances for SO₂. A dynamic surface chemistry model is used to simulate the effects of NH₃ on SO₂ deposition flux and is able to capture responses to short-term changes in ambient concentrations of SO₂, NH₃ and meteorological conditions. The coupling between surface resistance and NH₃/SO₂ concentration ratios shows that the deposition velocity for SO₂ is regulated by the regional pollution climate. Recent long-term SO₂ flux measurements in a transect over Europe demonstrate the close link between NH₃/SO₂ concentrations and rc (SO₂). The deposition velocity for SO₂ is predicted to have increased with time since the 1970s and imply a 40% increase in v _d at a site at which the annual mean ambient SO₂ concentrations declined from 47 to 3 g m^-3 between 1973 and 1998.     

Dynamics of Ammonia Exchange in Response to Cutting and Fertilising in an Intensively-Managed Grassland

Continuous micrometorological measurements of ammonia (NH₃)exchange were made for a period of 19 months (May 1998–November 1999) over intensively managed grassland in southern Scotland. This study focused on the influence of management activities, such as cutting and fertilising, on vegetation-atmosphere exchange of NH₃. Measurements were conducted within the European project GRAMINAE (GRassland AMmonia INteractions Across Europe) within which the Scottish site forms one of 6 sites in an E–W transect across Europe. NH₃ emissions were enhanced (up to 300 ng m^-2 s^-1) after cutting followed by larger emissions after fertilising (up to 1400 ng m^-2 s^-1). Annual budget calculations show the intensive grassland acted as a net source (1.8 kg N ha^-1 yr¹) although fluxes were bi-directional with deposition dominating in the winter and emission in the summer. Initial modelling of the NH₃ exchange using a `canopy compensation point' model has been conducted for key periods. The dynamics of the fluxes during these key periods, such as before and after cutting and fertilising, may be reproduced by introducing different values of the apoplastic ratio, = [NH₄ ⁺]/[H⁺].     

Sulphate and Nitrate in Precipitation and Soil Water in Pine Forests in Latvia

The SO₄–S and NO₃–N concentrations and pH in bulk precipitation, throughfall, stemflow and soil water for the 1994–2004 period were studied in pine forests in Latvia (Rucava and Taurene Integrated Monitoring stations). The SO₄–S and NO₃–N concentrations decreased over the study period, simultaneously with a decrease of acidity in precipitation. The changes were more evident in the western part of Latvia, probably due to declining long-range air pollution from West Europe. The trend of decreasing sulphate concentrations and increasing pH in precipitation were not followed by respective changes in soil water. In the upper soil horizon sulphate ion concentrations and acidity increased in soil water. Over the observation period, nitrate concentrations also showed an increasing trend in soil water at Rucava and Taurene, but these changes were not statistically significant.     

The spatial distribution of ammonia emitted from seabirds and its contribution to atmospheric nitrogen deposition in the UK

Simple bioenergetics models were used to derive annual nitrogen excretion rates of each seabird species occurring at colonies in the UK. These were combined with population distribution data and an estimated fraction of nitrogen volatilized to estimate the spatial distribution of NH₃ emissions from seabird colonies at a 1 km resolution. The effect of these emissions on atmospheric NH₃ concentrations and nitrogen deposition in the UK was assessed using the FRAME atmospheric chemistry and transport model. The total emission of NH₃ from the UK seabird colonies is estimated at 2.7 kt yr^–1. Emissions from seabirds are largely concentrated in remote parts of Britain, where agricultural and other anthropogenic emissions are minimal. Although seabirds account for less than 1% of total UK NH₃ emissions (370 kt yr^–1), their occurrence in remote areas and frequently large colony sizes results in seabirds providing a major fraction of the atmospheric nitrogen deposition for many remote ecosystems.     

Chemical augmentation for the remediation of a hydrocarbon‐contaminated site

Field trials with inorganic fertilizer (nitrogen, phosphorus, and potassium) nutrients were simulated in the greenhouse to remediate hydrocarbon‐polluted soils from a spill site in the Niger Delta, Nigeria. Samples of the polluted soils taken from two depths were displayed in a randomized complete block (RCB) design and treated with 10–100 g of (NH₄)₂SO₄, KH₂PO₄, and KCl. The agronomic addition of the chemical nutrients was found to enhance the concentrations of nitrate‐nitrogen, phosphate‐phosphorus, and potassium in the soils. Pretreated nitrate‐nitrogen content ranged from 432 to 590 mg/kg in the polluted samples (with a control at 522 mg/kg), while posttreatment concentrations were 3,285 ± 154 mg/kg and 3,254 ± 159 mg/kg for surface and subsurface soils, respectively. © 2007 Wiley Periodicals, Inc.     

Use of Natural 35S to Trace Sulphate Cycling in Small Lakes,Flattops Wilderness Area,Colorado, U.S.A.

Measurements of the cosmogenically-produced ³⁵S, a radioisotope of sulphur (t_1/2 = 87 days), are reported for the Ned Wilson Lake watershed in Colorado. The watershed contains two small lakes and a flowing spring presumed to be representative of local ground water. The watershed is located in the Flattops Wilderness Area and the waters in the system have low alkalinity, making them sensitive to increases in acid and sulphate deposition. Time series of ³⁵S measurements were made during the summers of 1995 and 1996 (July–September) at all three sites. The system is dominated by melting snow and an initial concentration of 16–20 mBq L^-1 was estimated for snowmelt based on a series of snow samples collected in the Rocky Mountains. The two lakes had large initial ³⁵S concentrations in July, indicating that a large fraction of the lake water and sulphate was introduced by meltwater from that year's snowpack. In 1995 and 1996, ³⁵S concentrations decreased more rapidly than could be accounted for by decay, indicating that other processes were affecting ³⁵S concentrations. The most likely explanation is that exchange with sediments or the biota was removing ³⁵S from the lake and replacing it with older sulphate devoid of ³⁵S. In September of 1995 and 1996, ³⁵S concentrations increased, suggesting that atmospheric deposition is important in the sulphate flux of these lakes in late summer. Sulphur-35 concentrations in the spring water were highly variable but never higher than 3.6 mBq L^-1 and averaged 2 mBq L^-1. Using a simple mixing model, it was estimated that 75% of the spring water was derived from precipitation of previous years.     

The Relative Influences of Primary and Secondary Particulates to Urban Air Quality in the United Kingdom

This study uses a combination of data from U.K. monitoringstations and from modelling undertaken with the U.K.Meteorological Office's NAME Model to investigate therelative influences of primary and secondary particulateson total PM₁₀ levels at sites in the United Kingdom. Co-located PM₁₀ and sulphate aerosol measurementsindicate that sulphate has a disproportionately largeinfluence on the variation of PM₁₀ levels incomparison to its contribution to their total mass.Comparisons of measured PM₁₀ at urban centre, roadsideand rural sites suggest that local primary sources havevery little influence on daily mean levels. NAME has beenused to model both primary particles and sulphate aerosolfrom sources across the whole of Europe. The discrepanciesbetween modelled and observed PM₁₀ suggest that coarseparticles, such as windblown dust and resuspended roaddust,may comprise a very large, if not dominant, proportion ofobserved PM₁₀ levels. The apparently minor role ofprimary particles (especially locally-sourced ones) raisesa number of issues regarding the suitability of current U.K.and European legislation to addressing the particle problem.     

Experimental Assessment of Atmospheric Ammonia Dispersion and Short Range Dry Deposition in a Maize Canopy

In order to study the effect of thevegetation structure on atmospheric ammonia(NH₃) dispersion and deposition, anexperiment was set up near Paris, in July 1997.Between 12 and 162 m downwind of a 200 m line-source releasing 600 to 1200 g NH₃hr^-1placed at the top of a maize canopy, NH₃concentration was measured, within and above thecanopy, with a set of 30 active, acid-coateddenuders over periods of 2 to 3 hr. Eight datasets were collected over a one-month period.NH₃ concentration decreased sharply withdistance to the source, from up to800 g NH₃ m^-3 at 12 m, to lessthan 10 g NH₃ m^-3 at 162 m andshowed strong vertical gradients. Within thecanopy, the concentration scaled using thefriction velocity, the canopy height, and thesource strength, exhibited a universal power lawrelationship as a function of the normaliseddownwind distance from the source. A mass balancemethod and a resistance model approach were usedas independent estimates of the cumulateddeposition at 162 m downwind from the source,which range between 1 and 29% of the emittedNH₃. Both methods agreed approximately inmagnitude. A sensitivity analysis showed that thecuticular uptake and the compensation point aremajor parameters that needs to be bettercharacterised under high NH₃ concentrationif one wants to improve NH₃ short-rangedeposition modelling.     

Nitrous Oxide in Agricultural Drainage Waters Following Field Fertilisation

Dissolved nitrous oxide (N₂O), nitrate (NO₃ ^-), and ammonium (NH₄ ⁺) concentrations in an agricultural field drain were intensively measured over the period of field nitrogen (N) fertilisation and for several weeks thereafter. Supersaturations of dissolved N₂O were observed in field drain waters throughout the study. On entry to an open drainage ditch, concentrations of dissolved N₂O rapidly decreased and a total N₂O-N emission via this pathway of 13.2 g over the period of study (45 days) was calculated. This compared with a predicted emission of the order of 300 g, based on measured losses of NO₃ ^- and NH₄ ⁺ in the field drainage water, and the default IPCC emission factor of 0.01 kg N₂O-N per kg Nentering rivers and estuaries. In contrast to widespread evidence of a clear relationship between the amount of N applied to agricultural land and subsequent direct N₂O emission from the soil surface, the relationship between the amount of N₂O in soil drainage waters and the amount of N applied was poor. We conclude that the complexity, both spatially and temporally, of the processes ultimately responsible for the amount of N₂O in agricultural drainage waters make a straightforward relationship between N₂O concentration and N application rate unlikely in all but the simplest of systems.