Long-term phenol, cresols and BTEX monitoring in urban air

This paper reports the results of a long-term monitoring of benzene, toluene, ethylbenzene, xylenes (BTEX), phenol and cresols in the air of Padua during a wide period of the year 2007 using two radial passive samplers (Radiello system) equipped with BTEX- and phenol-specific cartridges. Two sites were monitored, one in the industrial area and one close to the town centre. Relevant pollution episodes have been observed during both the winter and summer periods. Benzene, together with toluene, ethylbenzene and xylenes showed their maximum concentrations during the winter season, but the secondary pollutant phenol was higher than benzene for a large period of the year when the meteorological conditions blocked the pollutants in the lower layers of the atmosphere and solar radiation increased the benzene photo-oxidation process.     

Long-term measurement of volatile organic compounds in ambient air by canister-based one-week sampling method

A canister-based 1 week sampling method using a mechanical flow controller and a 6 L fused-silica-lined canister was evaluated for the long-term measurement of 47 VOCs in ambient air at pptv (volume/volume) to ppbv levels by use of a three-stage preconcentation method followed by GC-MS analysis. The GC conditions were initially optimized for complete separations of several pptv-level VOCs (e.g. vinyl chloride, 1,3-butadiene, acrylonitrile, 1,2-dichloroethane and chloroform) in ambient air because the selected ions are easily interfered with by coexisting C4-, C5-hydrocarbons and analytes presented at ppbv levels. Thirty-four VOCs determined by the 1 week and 24 h sampling method in December 16-22 (2002) had concentrations of 6.0-15000 pptv per compound. Concentrations of 28 VOCs (including polar VOCs (e.g. methyl isobutyl ketone and butyl acetate)) obtained by the method were approximately equal to the mean values calculated from 24 h sampling (< +/- 10% deviation). Six VOCs that had low concentrations of 6.0-43 pptv showed more than +/- 10% deviation. Thirteen VOCs were not detected during the entire sampling period. The effect of relative humidity or ozone for the specific VOCs (e.g. MIBK, butyl acetate, vinyl chloride, 1,3-butadiene and styrene) was negligible.     

Radiocaesium Activity Concentrations in Milk in the Republic of Croatia and Dose Assessment

Results of systematic measurements of radiocaesium activities in milk after the Chernobyl nuclear accident are summarized. ¹³⁷Cs fallout activity affects milk activity, the coefficient of correlation being 0.89. The ¹³⁷Cs activities in milk in Croatia are log-normally distributed, reflecting the exponential decrease of activity. After the Chernobyl nuclear accident the ¹³⁴Cs:¹³⁷ Cs activity ratio in milk was 0.5, and did not differ from that for other environmental samples. The dose due to radiocaesium ingestion by milk consumption was estimated for the Croatian population, the annual collective equivalent dose being approximately 205 manSv in 1986 and 1.5 manSv in 1994.     

226Ra in Tap and Mineral Water and Related Health Risk in the Republic of Croatia

The presence of 226Ra in drinking water may sometimes make important contribution to natural background radiation exposures. The paper describes the study of 226Ra content in drinking water of Croatia: tap water from the public supply system of several major towns and bottled mineral water from two selected mineral water springs. 226Ra was determined by alpha-spectrometric measurement after radiochemical separation. The radiation doses originating from drinking tap water and bottled mineral water were estimated. The annual dose from consumption of bottled mineral water was compared to that received from ingestion of public system tap water. The study showed that 226Ra content for investigated categories of waters is below the levels at which any unacceptable dose due to ingestion would arise.     

Recent trends of plutonium fallout observed in Japan: plutonium as a proxy for desertification

Plutonium in monthly deposition samples collected in Tsukuba (the Meteorological Research Institute), Japan from 1990 to end of 2001 is reported, together with monthly plutonium deposition in Nagasaki and Yonaguni in 2000. The annual deposition of (239,240)Pu during the period from 1990 to 2001 shows no systematic interannual variation. However, monthly (239,240)Pu depositions show a typical seasonal variation with a maximum in spring season (March to April), which corresponds to seasonal cycle of soil dusts originating from the East Asian arid area. Plutonium isotopic ratios in the deposition samples suggest that significant amounts of the recent (239,240)Pu deposition observed in Japan are attributed to the resuspension of plutonium-bearing surface soil particles; resuspended plutonium originates from the East Asian arid areas. The recent increased tendency of (239,240)Pu content in residues in deposition samples may reflect desertification in the East Asian continent.     

Monitoring of nitrates in drinking water from agricultural and residential areas of Podravina and Prigorje (Croatia)

Nitrates are the most common chemical pollutant of groundwater in agricultural and suburban areas. Croatia must comply with the Nitrate Directive (91/676/EEC) whose aim is to reduce water pollution by nitrates originating from agriculture and to prevent further pollution. Podravina and Prigorje are the areas with a relatively high degree of agricultural activity. Therefore, the aim of this study was, by monitoring nitrates, to determine the distribution of nitrates in two different areas, Podravina and Prigorje (Croatia), to determine sources of contamination as well as annual and seasonal trends. The nitrate concentrations were measured in 30 wells (N?=?382 samples) in Prigorje and in 19 wells (N?=?174 samples) in Podravina from 2002 to 2007. In Podravina, the nitrate content was 24.9 mg/l and 6 % of the samples were above the maximum available value (MAV), and in Prigorje the content was 53.9 mg/l and 38 % of the samples above MAV. The wells were classified as correct, occasionally incorrect and incorrect. In the group of occasionally incorrect and incorrect wells, the point sources were within 10 m of the well. There is no statistically significant difference over the years or seasons within the year, but the interaction between locations and years was significant. Nitrate concentrations’ trend was not significant during the monitoring. These results are a prerequisite for the adjustment of Croatian standards to those of the EU and will contribute to the implementation of the Nitrate Directive and the Directives on Environmental Protection in Croatia and the EU.     

The effects of water diversion and climate change on hydrological alteration and temperature regime of karst rivers in central Croatia

Karst rivers in Croatia have been heavily dammed in the past. However, long-term impacts of dams, water diversion and climate change on karst rivers in Croatia have rarely been examined. This study analyzes long-term trends of hydrological and temperature conditions, prior to closure of new large dam, in five connected karst rivers of central Croatia: the sinking rivers Gornja Dobra and Zagorska Mre?nica that have underground connections with the Goja?ka Dobra, Tounj?ica and Mre?nica Rivers. It was established that hydrological conditions of these rivers have been greatly changed after the Gojak HPP, located at spring of Goja?ka Dobra, became operational in 1959. Water diversion from the reservoirs on Zagorska Mre?nica and Gornja Dobra to the Gojak HPP has increased mean annual discharge (52-106%), causing great subdaily fluctuations and overall modification of natural flow regime along the whole course of Goja?ka Dobra. By cutting the connection between Zagorska Mre?nica and Tounj?ica, water diversion has caused a reduction of mean annual discharges of the Tounj?ica (-60%) and Mre?nica (-29%) Rivers. Analyses of long-term trends in water temperature over the last 50 years have revealed significant positive trends in average annual temperature at three gauging stations on three rivers with increase of 0.17, 0.44 and 0.48°C per decade and climate change as the primary cause. The highest significant increasing trend was established at the lower course of Mre?nica where discharge was reduced by water diversion. Mitigation measures for the improvement of hydrological conditions of affected rivers and underground systems are proposed and discussed.     

Effect of dibenzopyrene measurement on assessing air quality in Beijing air and possible implications for human health

Size fractionated particulate matter (PM) was collected in summer and winter from Beijing, China for the characterization of an expanded list of PAHs and evaluation of air pollution metrics. Summertime ΣPAHs on PM was 14.6 ± 29(PM 1.5), 0.88 ± 0.49(PM 1.5-7.2) and 0.29 ± 0.076(PM 7.2) ng m(-3) air while wintertime concentrations were 493 ± 206(PM 1.5), 26.7 ± 14(PM 1.5-7.2) and 5.3 ± 2.5(PM 7.2) ng m(-3) air. Greater than 90% of the carcinogenic PAHs were concentrated on PM(1.5). Dibenzopyrene isomers made up a significant portion (～30%) of the total carcinogenic PAH load during the winter. To our knowledge, this is the first report of dibenzopyrenes in the Beijing atmosphere and among the few studies that report these highly potent PAHs in ambient particulate matter. Lifetime risk calculations indicated that 1 out of 10,000 to over 6 out of 100 Beijing residents may have an increased risk of lung cancer due to PAH concentration. Over half of the lifetime risk was attributed to Σdibenzopyrenes. The World Health Organization and Chinese daily PM(10) standard was exceeded on each day of the study, however, PAH limits were only exceeded during the winter. The outcomes of the air pollution metrics were highly dependent on the individual PAHs measured and seasonal variation.     

Mercury and other elements in lichens near the INA Naftaplin gas treatment plant, Molve, Croatia

This paper describes the use of epiphytic lichens as bioindicators for spatial monitoring of mercury and other elements in air near the natural gas treatment facilities at Molve, Croatia. It is well known that at this location the concentration of mercury in natural gas is very high and therefore it has to be removed from natural gas before further processing in order to prevent technological and environmental problems. In order to monitor the efficiency of an industrial facility for removal of mercury from natural gas, mercury measurements in air and lichens were performed during 9 months in 1997/1998. In situ lichens Parmelia sulcata, Xantoria parientina and Hypogymnia physodes and transplanted lichen species Hypogymnia physodes were used. A good correlation between mercury concentrations in air and lichens was found. The concentrations of barium and bromium were also significantly elevated in transplanted lichens, most probably related to technological process at the gas treatment plant and/or other geological factors. It was confirmed that lichens can successfully be used as bioindicators, provided a careful experiment is designed, particularly the amount of lichens transplanted, the duration of exposure and the initial levels and homogeneity of transplanted lichens.     

Bricks as historical record of heavy metals fallout: Study on copper accumulation in Agra soils since 1910

Peat, ice deposits and aquatic sediments, which have been used as a geochemical monitor of atmospheric heavy metal pollution until now, are open and dynamic systems and can be easily affected by climatic variations. In contrast, bricks, which are more compact, can act as a better geochemical monitor. Analysis of Cu, Cr, Ni, Pb and Zn in scores of soil and brick (baked/unbaked) samples, collected from a large area in and around a rapidly growing Indian city, Agra, reveals approximately similar concentrations in soils and bricks, thereby showing insignificant fractionation of these metals during brick making. Further, metals concentration in the core of bricks remains unaffected by any significant amount of acidic and alkaline rain. Thus, the feasibility of a novel role of bricks as a geochemical monitor of atmospheric heavy metal pollution has been tested. Utilizing this concept, an attempt has also been made to trace the history of atmospheric copper depositions in the soils of Agra during the last 100 years.     

Dose equivalent commitments from fallout radionuclides in the open waters of the Great Lakes. 1973–1981

The levels of ¹⁴⁴Ce, ¹³⁷Cs, ¹²⁵Sb, and ⁹⁰Sr in the open waters of the Great Lakes were measured over the period 1973–81. The levels were found to be very low. ¹⁴⁴Ce was detected only up to 1975 after which it dropped below the detection limit. The data indicate that the concentrations of the remaining three radionuclides have decreased with time. ⁹⁰Sr and ¹³⁷Cs provide essentially all of the radiological dose from drinking Great Lakes water. The dose equivalant commitments have been calculated from these measurements and found to be well within the Great Lakes Water Quality Agreement's water quality objective for radioactivity.     

Determination of isocyanic acid in air

A method is presented for the determination of isocyanic acid (ICA), HNCO, in air samples as a di-n-butylamine (DBA) derivative. The method is based on sampling in midget impinger flasks containing 10 ml of 0.01 mol l-1 DBA in toluene. Quantification was made using liquid chromatography (LC) and electrospray mass spectrometry (MS) monitoring positive ions. The instrumental detection limit for the LC-MS was 10 fmol of ICA-DBA. ICA was generated by thermal decomposition of urea. A standard solution containing the DBA derivatives of ICA was prepared by collecting the emitted ICA in an impinger flask containing DBA. ICA in the reference solution was characterised by LC and time-of-flight (TOF) MS and quantified by LC chemiluminescent nitrogen detection (LC-CLND). The instrumental detection limit for the LC-CLND was 1 ng of nitrogen. ICA was emitted during thermal degradation of PFU resins and polyurethane (PUR) lacquers, from car metal sheets. ICA was the most dominant isocyanate and in PUR coating up to 8% of the total weight was emitted as ICA and for PFU resins up to 14% was emitted as ICA. When air samples were collected in an iron foundry during casting in sand moulds with furan resins, concentrations of ICA in the range 50-700 micrograms m-3 were found in the working atmosphere.     

Periphyton and Sediment Bioassessment in North Florida Bay

Periphyton colonization and sediment bioassessment were used ina survey to compare the relative environmental condition ofsampling sites located in Florida Bay and four peripheral sloughareas during the summer of 1995. Periphyton biomass, pigmentcontent, tissue quality and community composition weredetermined. In addition, benthic community composition and thetoxicities of whole sediments and associated pore waters weredetermined for two species of rooted macrophytes, an epibenthicinvertebrate and bioluminescent bacteria. Several locational differences were observed for the response parameters.Periphyton biomass was significantly greater in the Taylor Riverand the least in Shell Creek (P < 0.05). Most sediments were notacutely toxic to mysid shrimp nor phytotoxic. However, sedimentsfrom the Taylor River were more phytostimulatory than others (P< 0.05). Contaminant bioresidues were similar at most sites,however, mercury, chromium and nickel concentrations weregreater for periphyton colonized in the Taylor River and TroutCreek areas. Structural characteristics of the periphytic algalcommunity usually were statistically similar but a consistenttrend of lower density and diversity was evident for ShellCreek. The benthic community was the least diverse and dense inthe Canal C-111. The results of this study provide an initialindication of differences in the role of several slough areas aspossible sources of bioavailable contaminants to Florida Baywhich warrants additional investigation.     

Pesticide concentrations in air and precipitation in the Netherlands

Atmospheric deposition may be an important source of persistent organic compounds (POP) and pesticides for the Dutch coastal and inland waters. Current estimates of the atmospheric input have been made using atmospheric dispersion models. The uncertainty is however large. A project was defined with the aim to assess the input on the basis of measurements. For a period of two years (1999-2001) a monitoring network was operated. At eighteen stations, located across the whole country, air and precipitation samples were taken on a weekly and monthly basis. In these samples the concentrations of pesticides, PCB's and PAH's were determined. Up to 50 different pesticides were observed in precipitation and air. The concentration of 17 of these in precipitation exceeded the maximum permissible level for surface water and 22 exceeded the standard for drinking water of 100 ng l(-1). The input from the atmosphere to Dutch inland waters appeared to be as large as the input of pesticides by other sources such as spray drift. Model calculations were also carried out to identify the sources of these compounds. The occurrence of atrazine could be related to emissions outside the Netherlands.     

Calibration of two passive air sampler configurations for monitoring concentrations of hexabromocyclododecanes in indoor air

While polyurethane foam (PUF) disk passive air samplers are employed increasingly to monitor persistent organic pollutants in indoor air, they essentially sample only the vapour phase. As a previous investigation of the vapour : particle phase partitioning of hexabromocyclododecanes HBCDs in (outdoor) air reported them to be present largely in the particulate phase, we monitored three offices using active air samplers. In each, approximately 65% of HBCDs were present in the vapour phase, suggesting PUF disk passive samplers are suitable for monitoring HBCDs in indoor air. Concentrations in the three offices (239-359 pg Sigma HBCD m(-3)) exceed substantially those reported in outdoor air from the United States (2.1-11 pg Sigma HBCD m(-3)), but are in line with outdoor air from Stockholm. The relative abundance of the three principal diastereomers in office air was closer to that found in technical HBCD formulations (i.e. predominantly gamma-HBCD) than in most US outdoor air samples. Time integrated air concentrations of alpha-, beta-, and gamma-HBCD were obtained for an office using a low volume sampler operated over a 50 d period alongside PUF disk samplers. This calibration exercise yielded the following passive air sampling rates for both a fully- and part-sheltered PUF disk sampler design: for alpha-, beta-, and gamma-HBCD, 0.87, 0.89, and 0.91 m3 d(-1) respectively (fully-sheltered) and 1.38, 1.54, and 1.55 m3 d(-1) respectively (part-sheltered). Deployment of the part-sheltered configuration yielded concentrations approximately 35% lower than those obtained using a high volume sampler, consistent with PUF disk samplers measuring primarily the vapour phase.     

Assessment of multiple anthropogenic contaminants and their potential genotoxicity in the aquatic environment of Plitvice Lakes National Park,Croatia

In this study, the influence of anthropogenic pollution on the aquatic environment of Plitvice Lakes National Park (PLNP) was investigated during 2011–2012 using a combination of chemical and cytogenetic analyses. Four groups of major contaminants [(volatile organic compounds: benzene, toluene, ethylbenzene, and xylenes (BTEX); persistent organochlorine pollutants: organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs); major and trace elements; anthropogenic radionuclides (⁹⁰Sr, ¹³⁴Cs, and ¹³⁷Cs)] were determined in three aquatic compartments (water, sediment, fish). Mass fractions of inorganic constituents in different compartments reflected the geological background of the area, indicating their origin from predominantly natural sources. Levels of volatile and persistent organic compounds in water and fish, respectively, were very low, at levels typical for remote pristine areas. Analysis of anthropogenic radionuclides in water and sediment revealed elevated activity concentrations of ¹³⁷Cs in water, and measurable ¹³⁴Cs in the upper sediment layers from April 2011, possibly as a consequence of the Fukushima nuclear accident in March 2011. The potential genotoxicity of river and lake water and lake sediment was assessed under laboratory conditions using the alkaline comet assay on human peripheral blood lymphocytes, and measured levels of primary DNA damage were within acceptable boundaries. The results showed that despite the protected status of the park, anthropogenic impact exists in both its terrestrial and aquatic components. Although contaminant levels were low, further monitoring is recommended to make sure that they will not rise and cause potentially hazardous anthropogenic impacts.     

Evaluation and improvement of air quality in school public elevator

Public elevators are an essential requirement in modern high-rise buildings. However, the confined, crowded interior of an elevator provides an ideal breeding ground for all manners of biological aerosols. Consequently, when using an elevator at a university in Taiwan as the research target, this study performs an experimental investigation into the effectiveness of hand-sprayed gaseous chlorine dioxide as a disinfection agent. The air quality before and after disinfection is evaluated by measuring the bioaerosol concentrations of bacteria and fungi, respectively. The average background levels of bacteria and fungi before disinfection are found to be 635.7?±?469.6 and 1296.8?±?966.6 colony-forming unit (CFU)/m³, respectively. Following disinfection, the bacteria and fungi concentrations reduced by an average of 35 and 25 %, respectively. The multivariate analysis of variance (MANOVA) results showed that the residual bacteria and fungi concentration levels were determined primarily by the number of individuals within the elevator and the elapsed time following disinfection. In general, the present results show that given a maximum of five individuals within the elevator, a disinfection schedule of once every 40 min is sufficient to reduce the bioaerosol concentrations of bacteria and fungi to the levels specified by the Taiwan Environmental Protection Agency (EPA).     

Characteristics and origin of the hydrogen sulphide spring water from the Split spa (Southern Croatia)

The objective of this paper is to study the hydrological characteristics and origin of the hydrogen sulphide spring water from the Split spa in Southern Croatia in 1987, 1988 and 2003. This paper presents the results of monitoring the content of chlorides and hydrogen sulphide as well as the temperature of the hydrogen sulphide spring water. Since the hydrogen sulphide content during the dry periods significantly differs from the hydrogen sulphide content during rainy periods, this paper also compares the results obtained for those two periods. Under the influence of great quantities of rainfall during cold periods (winter and the beginning of spring) the ratio between seawater and surface water changes and thus the reduction of chlorides and other minerals occurs. The lowered temperature also reduces hydrogen sulphide which can disappear completely. The concentration of 12‰ chlorides (76–94.4% days/year) and 12 mg/L hydrogen sulphide (66.7–88.9% days/year) has been taken as a limit value between water with a normal typical content and water in cold rainy periods. According to the monitoring results it can be concluded that hydrogen sulphide spring water consists of seawater and hydrogencarbonate surface water with a fairly constant content during dry periods while the hydrogencarbonate content increases during rainy periods.