New Insight into the Measurements of Particle-Bound Metals in the Urban and Remote Atmospheres of the Sarajevo Canton and Modeled Impacts of Particulate Air Pollution in Bosnia and Herzegovina.

The Sarajevo Canton Winter Field Campaign 2018 (SAFICA) was a project that took place in winter 2017-2018 with an aim to characterize the chemical composition of aerosol in the Sarajevo Canton, Bosnia and Herzegovina (BiH), which has one of the worst air qualities in Europe. This paper presents the first characterization of the metals in PM10 (particulate matter aerodynamic diameters ≤10 µm) from continuous filter samples collected during an extended two-months winter period at the urban background Sarajevo and remote Ivan Sedlo sites. We report the results of 18 metals detected by inductively coupled plasma mass spectrometry (ICP-MS) and electrothermal atomic absorption spectrometry (ETAAS). The average mass concentrations of metals were higher at the Sarajevo site than at Ivan Sedlo and ranged from 0.050 ng/m3 (Co) to 188 ng/m3 (Fe) and from 0.021 ng/m3 (Co) to 61.8 ng/m3 (Fe), respectively. The BenMAP-CE model was used for estimating the annual BiH health (50% decrease in PM2.5 would save 4760+ lives) and economic benefits (costs of $2.29B) of improving the air quality. Additionally, the integrated energy and health assessment with the ExternE model provided an initial estimate of the additional health cost of BiH's energy system.

Associating Air Pollution with Cytokinesis-Block Micronucleus Assay Parameters in Lymphocytes of the General Population in Zagreb (Croatia).

Air pollution is recognized as one of the most serious public health issues worldwide and was declared to be a leading environmental cause of cancer deaths. At the same time, the cytokinesis-block micronucleus (CBMN) assay serves as a cancer predictive method that is extensively used in human biomonitoring for populations exposed to environmental contamination. The objective of this cross-sectional study is two-fold: to evaluate genomic instability in a sample (N = 130) of healthy, general population residents from Zagreb (Croatia), chronically exposed to different levels of air pollution, and to relate them to air pollution levels in the period from 2011 to 2015. Measured frequencies of CBMN assay parameters were in agreement with the baseline data for the general population of Croatia. Air pollution exposure was based on four factors obtained from a factor analysis of all exposure data obtained for the examined period. Based on the statistical results, we did not observe a significant positive association between any of the CBMN assay parameters tested and measured air pollution parameters for designated time windows, except for benzo(a)pyrene (B[a]P) that showed significant negative association. Our results show that measured air pollution parameters are largely below the regulatory limits, except for B[a]P, and as such, they do not affect CBMN assay parameters' frequency. Nevertheless, as air pollution is identified as a major health threat, it is necessary to conduct prospective studies investigating the effect of air pollution on genome integrity and human health.

Determination of Platinum Group Elements in Particulate Matter by Inductively Coupled Plasma Mass Spectrometry.

This study examined a method for determination of rhodium (Rh), palladium (Pd) and platinum (Pt) in particulate matter using standard solutions, model samples and certified reference materials (NIST 1648a and ERM CZ120). The method was based on microwave digestion followed by inductively coupled plasma mass spectrometry (ICP-MS). The results showed that the stability of the standard solution mixture of Rh, Pd and Pt was better when chlorides were present in the solution. A membrane filter and one type of quartz filter were the most adequate for analyzing platinum group elements (PGE). Respective limits of detection for Rh, Pd and Pt were 0.028, 0.503 and 0.0265 pg/m3 with a membrane filter and 0.478, 4.530 and 0.070 pg/m3 for one type of quartz filters. The sample matrix had no significant effects on the determination of three PGEs.

The impact of multiple anthropogenic contaminants on the terrestrial environment of the Plitvice Lakes National Park, Croatia.

The anthropogenic impact on the terrestrial environment of the Plitvice Lakes National Park (PLNP) was investigated through the analysis of three groups of major contaminants (persistent organochlorine pollutants including 15 organochlorine pesticides (OCPs) and 17 polychlorinated biphenyls (PCBs), trace elements/heavy metals (6 major and 23 trace constituents), and anthropogenic radionuclides ((90)Sr, (134)Cs, and (137)Cs)) in three terrestrial compartments (soil, air, and bioindicators of air contamination) during 2011-2013. The correlation coefficients of element mass fractions with soil properties indicated that total Fe and Al minerals, soil organic matter (OM), and organic carbon (OC) content affected the mass fractions of most trace elements in the topsoils. The annual and spatial distributions of heavy metals in total deposited matter (TDM) indicated that the metals came from natural sources and long-range transfer of particulate matter. The PCB and OCP levels found in soil and conifer needles corresponded to global environmental pollution levels by persistent organic pollutants and represented the lower end of the mass fraction ranges reported in the relevant literature. Analyses of anthropogenic radionuclides in bioindicators (conifer needles, lichens, and mosses) showed low but measurable activity concentrations of (134)Cs (for the first time after the Chernobyl accident), which indicated origin from the March 2011 Fukushima Nuclear Power Plant accident. Our overall results indicated that human activity inside or near the PLNP had no significant impact either on contaminant spread by air or on their content in topsoils.

Air Pollution and Primary DNA Damage among Zagreb (Croatia) Residents: A Cross-Sectional Study.

More than eight million premature deaths annually can be attributed to air pollution, with 99% of the world's population residing in areas below recommended air quality standards. Hence, the present study aimed to examine the association between primary DNA damage and air pollution data among 123 participants enrolled between 2011 and 2015 in Zagreb, Croatia. While most measured air pollutants adhered to regulatory limits, benzo[a]pyrene concentrations bound to PM10 exceeded them. Factorial analysis narrowed down air pollution data to four exposure factors (particulate matter, two metal factors, and other pollutants). Despite the absence of significant positive associations between modeled air pollution exposure factors and comet assay descriptors (tail length, tail intensity, tail moment, and highly damaged nuclei), the critical health implications of air pollution warrant further investigations, particularly with biomarkers of exposure and different biomarkers of effect in populations facing air pollution exposure.

Sources, Ionic Composition and Acidic Properties of Bulk and Wet Atmospheric Deposition in the Eastern Middle Adriatic Region.

Atmospheric bulk and wet deposition samples were collected simultaneously at the background coastal site in the Eastern Middle Adriatic region in order to assess the impact of major ions (Cl-, NO3-, SO42-, Na+, K+, NH4+, Mg2+, Ca2+) on deposition acidity and distinguish the main sources. Higher ion levels were observed during the cold period, especially for Cl-, Na+, Mg2+ and K+. Dust intrusion caused significant increases in levels of Ca2+, Mg2+ and K+, while open-fire events increased the levels of K+. Deposition acidity showed seasonal differences as well as the influence of dust intrusion. Low ionic balance ratios indicated acidic deposition properties and the presence of organic anions. The highest neutralization ability was found for Ca2+, Na+ and NH4+. Several natural (marine, crustal) and anthropogenic sources were determined, as well as the formation of secondary aerosols. Wet deposition was characterized by higher contribution of sea salt fraction compared to bulk deposition and lower contribution of crustal fraction.

Variabilities of biochemical properties of the sea surface microlayer: Insights to the atmospheric deposition impacts.

Atmospheric deposition (AD) of nutrients and its impact on the sea surface requires consideration of interfacial processes within the sea surface microlayer (SML), the ocean-atmosphere boundary layer of major importance for many global biogeochemical and climate-related processes. This study comprised a comprehensive dataset, including dissolved NO3-, NH4+ and PO43- in ambient aerosol particles, wet deposition and sea surface samples collected from February to July 2019 at a central Adriatic coastal site. The aerosol mean concentration of dissolved nitrogen (DIN = NO3- + NH4+) and PO43- were 48.8 ± 82.8 µmol m-3 and 0.8 ± 0.6 µmol m-3, respectively, while their total fluxes (dry + wet) ranged from 24.2 to 212.3 µmol m-2 d-1 (mean 123.2 ± 53.2 µmol m-2 d-1) and from 1.2 to 2.1 µmol m-2 d-1 (mean 1.5 ± 0.3 µmol m-2 d-1), respectively. Intensive local episodes of open biomass burning (BB) significantly increased aerosol DIN concentrations as well as DIN deposition fluxes, particularly altering the molar DIN/PO43- ratio of atmospheric samples. The DIN temporal patterns showed high variability in the SML (range 0.2-24.6 µmol L-1, mean 5.0 ± 7.1 µmol L-1) in contrast to the underlying water samples (range 0.5-4.2 µmol L-1, mean 1.9 ± 1.2 µmol L-1), with significant increases during BB periods. Variability in abundance of heterotrophic bacteria and autotrophs in the SML along with concentrations of bulk dissolved and particulate organic carbon as well as dissolved and particulate lipids and carbohydrates, gel particles and surfactants followed DIN enhancements with a two-week delay. This study showed that AD can affect the short-term scale enrichments of organic matter in the SML, especially when accompanied by BB emissions typical of the overall Mediterranean coastal environment. This could have strong implications for global air-sea exchange processes, including those of climate relevant gases, mediated by the SML.

Arsenic in air and soil in the vicinity of the central gas station Molve, Croatia.

Spatial and temporal distribution of arsenic levels in soil during the 9 year monitoring period was investigated on four different soil types in the area of the gas borehole system Podravina in Croatia. Arsenic levels in the PM(10) particle fraction were measured periodically at the same locations for 3 years. Arsenic levels in soil significantly depended on soil types. Elevated levels were found on gleysol vertic, at two sampling sites, with values exceeding 30 mg/kg of arsenic in soil. Arsenic levels in air were low and they were not significantly different between sampling sites, suggesting that gas borehole activities have no influence on arsenic levels in the environment.

Atmospheric deposition of biologically relevant trace metals in the eastern Adriatic coastal area.

Aerosol (PM10), bulk deposition, sea surface microlayer (SML) and underlying water (ULW) samples were collected simultaneously during a field campaign at the middle Adriatic coastal site between February and July 2019, to assess the impact of atmospheric deposition (AD) of biologically relevant trace metals (TM) (Zn, Cu, Co, Ni, Cd and Pb) on the sea surface responses in an oligotrophic coastal region. Anthropogenic emissions from continental Europe, alongside local/regional domestic heating, likely affected the concentrations of Zn, Cd and Pb in aerosols during winter-early spring, while traffic emissions during the tourist season impacted Ni, Co and Cu aerosol concentrations. Additionally, open-fire biomass burning (BB) episodes caused considerable TM concentration increases, while Saharan dust intrusion in spring led to a 10-fold increase in Co concentrations in PM10 samples. These intensive episodes significantly affected the bulk deposition fluxes of TMs, showing that a small number of such extreme events, common to Mediterranean coastal areas, could be responsible for most of the AD. Enrichments and concentrations of total TMs in SML samples collected following BB events indicated that such events, along with high precipitation, influenced TM partitioning in surface water layers. We estimated that AD represents a significant source of TM to the shallow middle Adriatic coastal area, highlighting the need to further explore the atmosphere-sea surface links, to expand our understanding of the biogeochemistry of these important micronutrients and pollutants, including their impact on the aquatic community.

Pollution levels and deposition processes of airborne organic pollutants over the central Adriatic area: Temporal variabilities and source identification.

First data on polycyclic aromatic hydrocarbons (PAHs) and nitro-aromatic compounds (NACs) in aerosols as well as of PAHs, polychlorinated biphenyls (PCBs) and NACs in bulk and wet atmospheric deposition samples were simultaneously obtained during 6-month-long field campaign at the costal central Adriatic area. Special attention was given to open-fire biomass burning episodes as extreme events common for the overall Mediterranean coastal area in order to gain a better understanding of the atmospheric variabilities and potential sources of trace organic pollutants in coastal environments. Diesel and gasoline combustion related to land and maritime traffic as well as occasional open-fire episodes (forest fires) were found to be the dominant pollution sources of PAHs in PM10 particles. NACs were determined almost exclusively in samples affected by biomass burning episodes. Open-fire episodes had a strong contribution to the overall NACs atmospheric deposition fluxes. Several chlorinated congeners of PCBs were predominantly contributed in deposition samples.

Influence of waste dump remediation on the levels of mercury in the air.

Mercury concentrations in air were measured at three measuring sites in the vicinity of a waste dump Jakusevec in Zagreb, Croatia over a 4-year period, from the beginning to the end of remediation. Measurements at the beginning of the remediation show that the concentrations of mercury at all three measuring sites were relatively high. Annual mercury mass concentrations in 2001 were between 17 and 445 ng m(-3). Annual mercury averages in 2004 ranged from 8 to 10 ng m(-3). Mercury variations were analysed with regard to the meteorological conditions. The results of this investigation show that in regard to mercury, the remediation was successful.

Zinc levels in suspended particulate matter in Zagreb air.

Monitoring of zinc in total suspended particulate matter (TSPM) started in Zagreb, Croatia in 1972 at two measuring sites, located in the city centre and in the northern part of the city. Monitoring of zinc concentrations in PM10 started in the northern part of the city in 2003. The obtained data show a decreasing trend of zinc in TSPM. Over the past 3 years, the measurement of zinc in PM10 particles has been performed, and the obtained data, in comparison to zinc in TSPM, have shown that 82%-93% of zinc was in the small PM10 particles.

Cadmium and Mercury phytostabilization from soil using Miscanthus × giganteus.

The determination of the effects of cadmium and mercury on the growth, biomass productivity and phytoremediation potential of Miscanthus × giganteus (MxG) grown on contaminated soil was the main aim of this paper. The use of bioenergy plants as an innovative strategy in phytotechnology gives additional benefits, including mitigation and adaptation to climate change, and soil remediation without affecting soil fertility. An experiment was set up as a randomized complete block design with the treatments varied in concentrations of Cd (0, 10 and 100 mg kg-1 soil) and Hg (0, 2 and 20 mg kg-1 soil) added to the soil. Three vegetative years were studied. Yield values ranged from 6.3-15.5 tDM ha-1, cadmium concentration in plants varied from 45-6758 µg kg-1 and Hg varied from 8.7-108.9 µg kg-1. Values between treatments and years were significantly different. MxG can accumulate and remove very modest amount (up to 293.8 µg Cd and 4.7 µg Hg) per pot per year in aboveground biomass. Based on this data it can be concluded that MxG, as a valuable energy crop, is a potential candidate for the phytostabilization and biomass production on soils contaminated with Cd and Hg moderately.

Determination of benzene in urine by static headspace gas chromatography.

This paper describes the application of static headspace gas chromatography in determining benzene in urine. The method was analytically validated for sensitivity (DL = 42 ng/l), repeatability (RSD = 3% and 4%), and accuracy (71%), and was applied in measuring urine benzene in nonsmokers (N = 14) and smokers (N = 18). All urine samples had measurable benzene concentrations. The method proved sensitive enough to establish a significant statistical difference (P < 0.000614) in urine benzene concentrations between smokers (mean = 760; range = 181-1869 ng/l) and nonsmokers (mean = 214; range = 61-515 ng/l).

Sulphur cycling between terrestrial agroecosystem and atmosphere.

Central gas station of the natural gas borehole system Podravina is located near the village Molve. It delivers more than a quarter of total energy used in Croatia to its consumers. Over the years, adapting technology to increasingly demanding and rigorous standards in environmental protection has become paramount. Yet, despite all the industry has undertaken to address the risk of harmful substances entering the food chain, a multidisciplinary research team of independent scientists monitors the content of specific substances in all components of the ecosystem. This paper presents measurements of total sulphur contents in soil surface [(0 to 3) cm] and subsurface [(3 to 8) cm] layers (study period: autumn 2006 - spring 2010) and in plants (study period: spring 2000 - spring 2010), and the concentration of gaseous sulphur compounds in the air. Concentrations of hydrogen sulphide (H2S) and mercaptans (RSH) were measured from the summer of 2002 until the autumn of 2010, while concentrations of sulphur dioxide (SO2) were measured from the spring of 2008 until the autumn of 2010. The paper also shows total annual atmospheric sulphur (S-SO4) deposition at Bilogora measuring station (study period: 2001 - 2010). Average monthly concentrations of H2S in air varied between 0.2 µg m-3 and 2.0 µg m-3, RSH between 0.1 µg m-3 and 24.5 µg m-3, and SO2 between 0.4 µg m-3 and 2.8 µg m-3 depending on the location and the season of sampling. Mean values of total sulphur in soil and in Plantago lanceolata plant ranged between 610 mg kg-1 and 1,599 mg kg-1 and between 3,614 mg kg-1 and 4,342 mg kg-1, respectively, depending on the soil type, location, and sampling depth. Average values of total sulphur mass ratio for all examined single soil samples (n=80) were 1,080 mg kg-1 for both studied layers, and 4,108 mg kg-1 for all analysed plant samples (n=85). Average total annual atmospheric sulphur deposition at Bilogora measuring station was 6.3 kg of S-SO4 per hectare.

[Polycyclic aromatic hydrocarbons in air]. / Policiklicki aromatski ugljikovodici u zraku.

Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds consisting of two or more condense aromatic rings. They are products of incomplete combustion or pyrolysis of organic matter. Because some PAHs such as Benzo[a]pyrene (BaP) are proven carcinogens and mutagens, it is necessary to continuously monitor their concentrations in the air, water, and soil. PAHs with two or three aromatic rings are stable in the gas phase, while most PAHs with five or more aromatic rings bond to particles. Higher concentrations of PAHs are present in the atmosphere of urban areas, mostly in the winter, due to heating. In the summer, these concentrations drop because most PAHs are unstable at high temperatures and break down by oxidation and photooxidation. Measurements of PAHs in the air include sampling on the filter paper or solid adsorbent, extraction, and chromatographic analysis. This review presents the measurements of BaP in some locations in the world and compares them with the findings in Croatia.

Summer ozone concentrations in Zagreb area.

Ozone concentrations were measured at three sites in Zagreb (Croatia) in the summer of 2005. Two measuring sites were in urban areas, while the third site was in a rural area about 30 km to the south from the centre of Zagreb. Hourly ozone averages varied between 1 microg m(-3) and 209 microg m(-3). Average concentrations were the lowest in the rural area, even though elevated concentrations were recorded occasionally. However, the weather conditions during measurements were untypical for that time of the year; over the summer of 2005 there were many rainy and cloudy days. Ozone concentrations at all three sites were the highest on Saturdays and Sundays, and the lowest on Thursdays. All the results were analysed with regard to the meteorological conditions (wind velocity and direction, temperature, relative humidity).