Comparison of the impact of ships to size-segregated particle concentrations in two harbour cities of northern Adriatic Sea.

Detailed information on in-harbour shipping contribution to size segregated particles in coastal cities are scarce, especially in the busy Mediterranean basin. This poses issues for human exposure and air quality in urban harbour agglomerates, where only criteria pollutants (i.e. PM10 and/or PM2.5) are usually monitored. In this work, particle number and mass size distributions, in a large size range (0.01-31 µm), were obtained in two coastal cities of northern Adriatic Sea: Venice (Italy) and Rijeka (Croatia). Three size ranges were investigated: nanoparticles (diameter D < 0.25 µm); fine particles (0.25 1 µm). Absolute concentrations were larger in Venice for all size ranges showing, using analysis of daily trends, a large influence of local meteorology and boundary-layer dynamics. Contribution of road transport was larger (in relative terms) in Rijeka compared to Venice. The highest contributions of shipping were in Venice, mainly because of the larger ship traffic. Maximum impact was on nanoparticles 7.4% (Venice) and 1.8% (Rijeka), the minimum was on fine range 1.9% (Venice) and <0.2% (Rijeka) and intermediate values were found in the coarse fraction 1.8% (Venice) and 0.5% (Rijeka). Contribution of shipping to mass concentration was not distinguishable from uncertainty in Rijeka (<0.2% for PM1, PM2.5, and PM10) and was about 2% in Venice. Relative contributions as function of particles size show remarkable similitudes: a maximum for nanoparticles, a quick decrease and a successive secondary maximum (2-3 times lower than the first) in the fine range. For larger diameters, the relative contributions reach a minimum at 1-1.5 µm and there is a successive increase in the coarse range. Size distributions showed a not negligible contribution of harbour emissions to nanoparticle and fine particle number concentrations, compared to PM2.5 or PM10, indicating them as a better metric to monitor shipping impacts compared to mass concentrations (PM2.5 or PM10).

Airborne Ns (NO2 and NH3) in the Rijeka Bay area (Croatia), 1980-1995.

The determination of ambient levels of nitrogen dioxide (NO2) and ammonia (NH3) in the Rijeka Bay area started in 1980, as a part of the air quality monitoring programme. The results of 15 years of surveying (1980/81-1994/95) on ambient levels of these pollutants at two sampling sites are given in this work. Site 1 is located in the city, opposite the old petroleum refinery facilities, while Site 2 is located in the settlement 25 km from the city, opposite the eastern industrial zone. Annual means of NO2 varied between 34 and 60 g/m3 at Site 1 and between 14 and 26 g/m3 at Site 2, but do not follow the 40% reduction in industrial emissions of this pollutant, probably due to the dominant impact of other minor sources, like traffic. Yearly averages of NH3 were in the range of 13 to 26 g/m 3 at Site 1 and 7 to 16 g/m3 at Site 2, and are practically constant during the period studied.

Airborne metal concentrations in shipyard environment.

Protection against corrosion in the shipyard is a source of airborne particles. From October 1996 to September 1997 samples of suspended particles (1 site) and dustfall (6 sites) were collected in the vicinity of a repairs shipyard situated in the martinscica Cove, east of the city of Rijeka, Croatia. Collected samples were analysed for lead, cadmium, iron, copper, and zinc content. Though annual mean concentrations of suspended particles, lead, and cadmium kept below the guideline values, the metal contents were generally higher than values measured in the city centre. The correlation between the quantity of abrasives used at the shipyard and monthly mean concentrations of all parameters except cadmium suggests that the shipyard was the main source of those pollutants. The annual mean, as well as maximum monthly amount of dustfall at the site next to the shipyard zone exceeded the national limit values, indicating considerable pollution of this area with coarse particles. The annual mean quantity of lead in dustfall exceeded the guideline values at the same site. The content of metals occasionally observed in dustfall at particular sites surrounding the shipyard depended on the location of corrosion protection activities and meterological conditions within the Martinscica Cove.

Kinetics of heterogeneous ozone reactions.

Earlier results on ozone destruction on solid surfaces gave apparent first order kinetics. Estimating the reaction kinetics from our data on ozone destruction on various powders (silica-gel, alumina, wood ash, coal ash, Saharan sand, calcite), we found that only calcite and wood ash exhibited such a behaviour. Removal of ozone by other powders used showed two straight lines in ln c-t plot with two different half-lives, t'(1/2) < t''(1/2). Comparing the kinetic constants for ozone removal on silica-gel and that of ozone reactions with polynuclear aromatic hydrocarbons (PAHs) adsorbed in submonolayer coverage on the same powder, the first reaction seems to be more likely in the case of pyrene and particularly fluoranthene. Enhanced ozone destruction on airborne aerosols could be an additional reason for fluoranthene stability in the real atmosphere.

Emissions and ambient levels of sulphur dioxide in the Rijeka Bay area.

During the eighties the city of Rijeka was one of the most polluted cities in Croatia with sulphur dioxide due to high emission of this pollutant from industrial plants. In mid-eighties, annual means of SO2 exceeded 100 micrograms/m3 in the city centre, in the Bakar Bay area varied between 70-80 micrograms/m3, while in the suburban residential area they were up to 40 micrograms/m3. In 1995 annual means were below the guideline value of 50 micrograms/m3 in the whole Rijeka Bay area. Emission inventory based on 1989 data estimated total SO2 emission to approximately 36,000 t a year, 95% of which from industrial sources. The update from 1995 data gave a new estimate of approximately 11,000 t a year, which is a 70.5% reduction of SO2 emission. However, the contribution of emissions from industrial sources remained practically unchanged (95%). The emission reduction resulted in the decrease of ambient levels of SO2. The paper presents trends in SO2 annual mean concentrations in the period 1986-1995 for two urban sites, two sites situated in the industrial area east of the city, and a suburban residential site.

Chemical composition of rainwater collected at two sampling sites in the city of Rijeka.

This study compares the chemical composition of rainwater samples collected at two sampling sites, the first situated in the Rijeka city centre and the second in a suburban site 120 m above the sea level. The rainwater samples were analysed for precipitation weighted average concentrations of hydrogen, sulphate, nitrate, chloride, ammonium, sodium, potassium, calcium, and magnesium. The results suggest that the local washout of the atmosphere enhanced the rainwater acidity in the city centre which also received significant marine contributions of sulphate, calcium, magnesium, and potassium content. Rainwater in the suburban site was affected by soil dust and/or fertilizers used in the nearby gardens, resulting in partial neutralization with rising of pH value. While the content of S-SO4 was practically equal at both sites, the quantities of N-NO3 and N-NH4 nearly doubled at the suburban site.

Zinc levels in human milk and umbilical cord blood.

Zinc levels were determined in human milk and umbilical cord blood samples collected in the Rijeka Clinical Hospital during the period from September 1995 to January 1996. The average concentrations of zinc were 4.98 +/- 2.53 mg/l in breast milk (range: 1.69-11.60 mg/l) and 1.18 +/- 0.21 mg/l in umbilical cord blood (range: 0.87-1.91 mg/l). Results of group comparisons regarding mothers' age, parity, residence and smoking habits indicate that parity affected Zn levels in both, breast milk and umbilical cord blood, with higher content found in primiparae. Younger mothers (aged < or = 25 years) also had higher levels of Zn in breast milk compared to those whose age was > 25 years. Residence and smoking habits did not seem to have any impact on Zn concentrations in biological tissues studied. A weak association between umbilical cord blood Zn levels and anthropometric measurements of newborns, like birthweight and head circumference, is also observed.

[Man, the environment and ozone]. / Covjek, okolis i ozon.

Ozone is a naturally occurring gas, formed in the trimolecular reaction of oxygen atoms with molecular oxygen. Its strong absorption in the UV region provides protection from excessive irradiation of the Earth's surface. Occupational exposure to ozone involves electric arc welding, mercury vapour lamps, office photocopy machines, X-ray generators and other high voltage electrical equipment, water purification and bleaching. Ozone is the most abundant oxidant in the photochemical smog. The lung cell injury induced by ozone involves a complex biochemical mechanism which is due to free radical generation. Moderate exposure produces upper respiratory tract symptoms and eye irritation, severe acute exposure results in pulmonary oedema. Measurements of atmospheric ozone concentrations in Croatia began at the end of the 19th century; continuous monitoring has been carried out since 1975.

[Toxicology of polycyclic aromatic hydrocarbons and the mutagenicity of the air]. / Toksikologija policiklickih aromatskih ugljikovodika i mutagenost atmosfere.

Toxicological properties of polynuclear aromatic hydrocarbons (PAH) and their derivatives concerning their carcinogenicity, embryotoxicity and phototoxicity are reviewed. The importance of the Ames test and biologically directed chemical analysis for identification of these mutagenic compounds is emphasized. Possible chemical reactions acting as sources of mutagenic PAH derivatives in the atmosphere are given.