The key aims of this project were: (i) investigation of atmospheric nitrogen deposition, focused on discrimination between bulk, wet and dry deposition, and between particulate matter and gas phase, (ii) accurate quantification of the contributions of dissolved organic and inorganic nitrogen to each type of deposition, and (iii) exploration of the origin and potential sources of atmospheric water soluble organic nitrogen (WSON). This project was particularly focused on the WSON fraction because, despite it being a potentially important source of bioavailable reactive nitrogen, a number of questions regarding its deposition mechanism (wet vs. dry), composition and origin (natural, anthropogenic or mixed) remain unanswered. There are two major difficulties in WSON determination: (i) the diversity of organic nitrogen compounds compared with the inorganic forms, and (ii) the lack of a direct determination method: the derivation of organic nitrogen concentrations in an aqueous sample involves the determination of the dissolved inorganic nitrogen (DIN) species concentration, comprising nitrate and ammonium, the determination of the total dissolved nitrogen (TDN) concentration, and the subtraction of the DIN concentrations from the TDN concentration. TDN determination requires a preparatory digestion step: high-temperature catalytic oxidation was the method used in this study. Ion chromatography (IC) was the method of choice for nitrate determination, whilst ammonium determination was by IC for rain samples, and by flow injection analysis for air samples collected into aqueous media. This thesis is structured in 3 main parts: the first part examines weekly rain data over a period of 22 months from June 2005 to March 2007 collected in 2 types of rain collector (bulk deposition and “dry+wet” deposition) located in a semi-rural area 15 km southwest of Edinburgh, UK (N55°51′44″, W3°12′19″). Bulk deposition collectors were the standard rain gauges used in the UK national network for monitoring precipitation composition. “Dry+wet” deposition collectors were flushing rain gauges equipped with a rain detector, a spray nozzle, a 2-way valve and two independent bottles to collect funnel washings (dry deposition) and true wet deposition. A key objective in this part of the work was the accurate quantification of inorganic and organic water-soluble nitrogen species contribution to each type of deposition. On average, for the 27 weekly samples with 3 valid replicates for the 2 types of collectors, DON represented 23% of the TDN in bulk deposition. Dry deposition of particles and gas on the funnel surface, rather than rain, contributed over half of all N-containing species (inorganic and organic). Some discrepancies were found between bulk and flushing rain gauges, for deposition of both TDN and DON, suggesting biological conversion and loss of inorganic N in the flushing samplers. The second stage of this project was the investigation of in situ atmospheric concentrations of WSN species, both organic and inorganic. Simultaneous daily measurements of ammonium, nitrate and WSON were made between July and November 2008 at the same semi-rural site in south-east Scotland. Discrimination between material from the gas and particle phases was achieved by means of Cofer scrubbers and PTFE membrane filters, respectively. Average concentrations of NH3 (determined as NH4+), NO2/HNO3 (determined as NO3-) and WSON in the gas phase were 82 ± 54 nmol N m-3, 2.6 ± 2.5 nmol N m-3 and 18 ± 12 nmol N m-3 respectively, and in the particle phase were 20 ± 24 nmol N m-3, 10 ± 9 nmol N m-3 and 8 ± 7 nmol N m-3 respectively (± represent standard deviation across all valid daily samples, not error of triplicate samples). Except for oxidised inorganic N, average concentrations in the gas phase were larger than in the particle phase. No evidence of solely agricultural or solely combustion sources of WSON was found, as no correlation in either phase between WSON and either NH4+ or NO3- could be established. The final stage of this project was to gain a broader picture of nitrogen deposition across Europe. Rain samples were analysed for TDN and DIN from a network of 21 different sampling locations, from the south of Portugal to the north of Finland. The average DON contribution across the 21 sampling sites was ~ 19% and, according to the data gathered in this study, DON species appeared largely unrelated specifically to agricultural or to combustion nitrogen sources, although the results varied widely from site to site. Overall, this work has shown that ON and its deposition comprises a significant component of total atmospheric reactive nitrogen.

In this work, wet deposition samples were collected at Middle East Technical University campus, Ankara, between December 2000 and May 2002. Snow samples were collected from 50 grids in January, 2001 in Ankara to investigate dry deposition of PAHs. The collected samples were preconcentrated by Solid Phase Extraction and ultrasonic extraction tecniques. Extraction methodologies were improved prior to analysis of samples. Extracted samples were analyzed by Gas Chromotography-Mass Spectrometry for 14 Polycyclic Aromatic Hydrocarbons. Selected Ion Monitoring mode was used throughout the analysis. Phenanthrene, fluoranthene, pyrene and benzo (b+k) fluoranthene were found to be dominant PAHs in wet deposition samples. Seasonal variation of PAHs were observed having higher concentrations in winter period. Meterological parameters were also examined together with PAH concentrations. Contribution of PAHs coming from North East and South West direction were found to be dominant. Wet deposition fluxes were calculated and compared with other urban sites. Wet deposition fluxes are lower than industrial sites and comparable with urban sites in Europe. PAH ratios and factor analysis results demostrated combustion and traffic emissions are major sources of pollutants in the city. Dry deposition of PAHs were invesigated using snow as a natural collecting surface. Dry deposition fluxes calculated using snow surface are compareble with other similar sites. Dry deposition pollution maps of PAHs were drawn by MapInfo software and it was observed that the major pollution regions are the localities where low income families live and low quality coal used for heating purpose. Ratio calculations showed that the central parts of the city is mostly affected from traffic emissions while coal emissions are dominating at the other parts of the city. Factor analysis applied to data set and 6 factors distinquished as coal, soil, traffic, oil combustion, mixed combustion and road dust.

An extensive investigation with parallel field andlaboratory exposures has been conducted to elucidateatmospheric corrosion and metal runoff processes on copper andzinc used for roofing applications. Detailed studies have beenperformed to disclose the effect of various parameters on therunoff rate including: surface inclination and orientation,natural patination (age), patina composition, rain duration andvolume, rain pH, and length of dry periods inbetween rainevents. Annual and average corrosion rates and runoff rateshave been determined consecutively during urban field exposuresin Stockholm on naturally patinated copper and zinc of varyingage and patina composition. The corrosion rate was found todecrease with time, amounting to 6.7 g Cu/(m2.y) and 5.0 gZn/(m2.y) after 48 weeks of exposure, whereas the runoff ratewas relatively constant with time on a yearly basis, being 1.3g/(m2.y) and 3.1 g/(m2.y) for copper and zinc, respectively.The annual runoff rate was found to be significantly lower thanthe corresponding corrosion rate for both copper and zinc.Somewhat higher runoff rates of copper were determined fromnaturally green-patinated copper (&gt;40 years old, 2.0g/(m2.y)) compared to brown-patinated copper (1 year old). Themain reasons are specific environmental conditions combinedwith characteristics of the patina layer, which increase themagnitude of dissolved species flushed from the surface duringthe first flush volume of a rain event. No intrinsic effect ofpanel age on the runoff rate was seen for naturally patinatedzinc. However, differences in prevailing environmentalconditions during the initial exposure period and, hence,differences in formation rate and surface coverage of thecorrosion patina, resulted in variations in runoff rate. Thisinitial difference remained also during prolonged exposureperiods and was referred to as a memory effect. Model roof investigations and laboratory studies showedsurface orientation and inclination to have a detrimentaleffect on the runoff rate with high runoff rates from surfacesof low inclination from horizon and surfaces exposed towardsthe wind direction. Based on fieldexposures and literature data, a correlationwas established between the runoff rate and the prevailingSO2-concentration. The runoff rate increases with increasingSO2 level for exposure sites of similar annual precipitationquantities (500-1000 mm/y). A rain device, using artificialrain, was shown to successfully simulate outdoor rain events ofvarying intensity and pH and result in realistic runoff ratesof both copper and zinc. The device was used to monitor changesin metal concentration and quantity of runoff water duringindividual rain events. High metal concentrations are found inthe initial rain volume flushing the surface (first flush),which decreased to rather constant metal concentrations duringthe subsequent rain volume (steady-state). The magnitude offirst flush depends primarily on environmental conditions priorto a rain event and the characteristics of the corrosionpatina. The metal concentration in runoff water increases withrain acidity, decreases with rain intensity and increases withlength of the dry period preceding a rain event. A comparison between instantaneous corrosion rates,monitored by electrochemical impedance spectroscopy using a2-electrode set-up, and runoff rates during a continuous rainevent was performed for naturally patinated copper panels.Corrosion rates were found to be approximately 10 (brownishpatina) and 25 times (greenish patina) lower than correspondinginstantaneous runoff rates. A schematic description of the first flush and steady-stateregion of the runoff process was established. The magnitude ofthe concentration during first flush is primarily affected byprevailing environmental conditions prior to a rain event,while rain pH and intensity primarily affect the concentrationduring steady-state. <b>Key words:</b>atmospheric corrosion, corrosion rate, runoffrate, copper, zinc, field study, laboratory study, roof, firstflush, rain quantity, rain intensity, rain pH, dry and wetdeposition, corrosion and runoff process.

<p>An extensive investigation with parallel field andlaboratory exposures has been conducted to elucidateatmospheric corrosion and metal runoff processes on copper andzinc used for roofing applications. Detailed studies have beenperformed to disclose the effect of various parameters on therunoff rate including: surface inclination and orientation,natural patination (age), patina composition, rain duration andvolume, rain pH, and length of dry periods inbetween rainevents. Annual and average corrosion rates and runoff rateshave been determined consecutively during urban field exposuresin Stockholm on naturally patinated copper and zinc of varyingage and patina composition. The corrosion rate was found todecrease with time, amounting to 6.7 g Cu/(m2.y) and 5.0 gZn/(m2.y) after 48 weeks of exposure, whereas the runoff ratewas relatively constant with time on a yearly basis, being 1.3g/(m2.y) and 3.1 g/(m2.y) for copper and zinc, respectively.The annual runoff rate was found to be significantly lower thanthe corresponding corrosion rate for both copper and zinc.Somewhat higher runoff rates of copper were determined fromnaturally green-patinated copper (>40 years old, 2.0g/(m2.y)) compared to brown-patinated copper (1 year old). Themain reasons are specific environmental conditions combinedwith characteristics of the patina layer, which increase themagnitude of dissolved species flushed from the surface duringthe first flush volume of a rain event. No intrinsic effect ofpanel age on the runoff rate was seen for naturally patinatedzinc. However, differences in prevailing environmentalconditions during the initial exposure period and, hence,differences in formation rate and surface coverage of thecorrosion patina, resulted in variations in runoff rate. Thisinitial difference remained also during prolonged exposureperiods and was referred to as a memory effect.</p><p>Model roof investigations and laboratory studies showedsurface orientation and inclination to have a detrimentaleffect on the runoff rate with high runoff rates from surfacesof low inclination from horizon and surfaces exposed towardsthe wind direction.</p><p>Based on fieldexposures and literature data, a correlationwas established between the runoff rate and the prevailingSO2-concentration. The runoff rate increases with increasingSO2 level for exposure sites of similar annual precipitationquantities (500-1000 mm/y). A rain device, using artificialrain, was shown to successfully simulate outdoor rain events ofvarying intensity and pH and result in realistic runoff ratesof both copper and zinc. The device was used to monitor changesin metal concentration and quantity of runoff water duringindividual rain events. High metal concentrations are found inthe initial rain volume flushing the surface (first flush),which decreased to rather constant metal concentrations duringthe subsequent rain volume (steady-state). The magnitude offirst flush depends primarily on environmental conditions priorto a rain event and the characteristics of the corrosionpatina. The metal concentration in runoff water increases withrain acidity, decreases with rain intensity and increases withlength of the dry period preceding a rain event.</p><p>A comparison between instantaneous corrosion rates,monitored by electrochemical impedance spectroscopy using a2-electrode set-up, and runoff rates during a continuous rainevent was performed for naturally patinated copper panels.Corrosion rates were found to be approximately 10 (brownishpatina) and 25 times (greenish patina) lower than correspondinginstantaneous runoff rates.</p><p>A schematic description of the first flush and steady-stateregion of the runoff process was established. The magnitude ofthe concentration during first flush is primarily affected byprevailing environmental conditions prior to a rain event,while rain pH and intensity primarily affect the concentrationduring steady-state.</p><p><b>Key words:</b>atmospheric corrosion, corrosion rate, runoffrate, copper, zinc, field study, laboratory study, roof, firstflush, rain quantity, rain intensity, rain pH, dry and wetdeposition, corrosion and runoff process.</p>