90Sr and stable element levels in bones of brown bears: long-term trends in bear populations from Croatia and Poland.

The aim of this study was to investigate the temporal trends and geographical differences in 90Sr and stable element (Ba, Ca, Mn, Sr, Pb, Zn) levels in the bones of Croatian and Polish brown bear (Ursus arctos) populations. Experimental data suggest that in the decades after nuclear weapon tests and the Chernobyl accident, 90Sr bone activity concentrations decreased from 352 to 11 Bq kg-1 in the Croatian bear population (period 1982-2015) and from 831 to 27 Bq kg-1 in Polish bears (period 1962-2020). Calculated effective and ecological half-lives were 9 and 13 years for Croatian bears, and 15 and 31 years for Polish bears, respectively. Different temporal trends were noted in levels of Ba, Mn, Pb and Zn between the two countries with majority of bones having lower Pb, Sr and Zn in Croatian than in Polish bears. Estimated values for the soil-to-bear transfer of 90Sr were the same order of magnitude in the studied populations. Contrary to this, the estimated transfer of stable Sr was an order of magnitude lower for the Croatian bear population compared to Polish bears. The observed differences in soil-to-bear transfer between stable Sr and 90Sr found for Croatian bears might suggest the need for careful consideration on the use of stable Sr data as an analogue for 90Sr. To our knowledge, this is the first study that analysed 90Sr activity in tissue of brown bears. As such, it provides insight into the fate and behaviour of one of the most relevant anthropogenic radionuclides at the top of the food chain.

Does exposure to weathered coal ash with an enhanced content of uranium-series radionuclides affect flora? Changes in the physiological indicators of five referent plant species.

Coal ash deposited in open landfills is a potential source of environmental pollutants due to the contained toxic element content. The weathered coal ash used in this study additionally contains enhanced activity concentrations of 238U series radionuclides. This study aimed to determine the physiological effects of enhanced ionizing radiation and toxic elements on five plant species (smilo grass, sticky fleabane, blackberry, mastic and pine tree) inhabiting the coal ash disposal site. Among the potentially toxic measured elements, contents of Sb, As and especially V significantly exceeded their respective levels at the control site, as well as the content of 238U and its progenies. Significant changes in photosynthetic pigments were recorded following chronic exposure to the plants growing on the coal ash site. Different responses were also observed in the plant species regarding the activity of catalase and glutathione-S-transferase (GST). The level of lipid peroxidation markedly increased in plants from the disposal site, except in blackberry, wherein GST activity was the strongest, indicating an important role of that enzyme in the adaptation to coal ash pollutants. The results of this study suggest that the modulation of the studied biochemical parameters in plants growing on coal ash is primarily species-dependent.

Spatio-temporal monitoring of mercury and other stable metal(loid)s and radionuclides in a Croatian terrestrial ecosystem around a natural gas treatment plant.

The natural gas industry bears a certain contamination risk to human and biota due to, among others, mercury, arsenic, and naturally occurring radioactive material content in gas. We tracked multiple stabile metal(loid)s and radionuclides within the natural gas treatment plant Molve, Croatia, ecosystem during the last decade through a comprehensive monitoring of soil, earthworms, moss, livestock (blood, milk, hair, urine, and feces from cows), and wildlife animals (brain, muscle, liver, and kidney of European hare and pheasant). The level of mercury and other stable metal(loid)s has shown temporal variation, but without an obvious trend. The found spatial differences in soil and earthworms were based on the differing soil characteristics of the sampled locations and exceeded the maximal allowable concentration of arsenic and zinc for agricultural soil. The status of essential copper, selenium, and zinc in cows, hares, and pheasants inclined towards deficiency. The measured stable metal(loid) levels in soil and animal samples were generally in the same range of values reported in earlier decades from the same area or non-polluted areas across Europe. The consumption of local cow and game products (e.g., milk, meat) can be considered safe for human health, although game offal is advised to be avoided as a food item due to the low risk of lead and cadmium's adverse effects. Although the activity concentrations of some radionuclides in moss were higher than reported for pristine areas, transfer from soil to moss was assessed as average (except for lead-210). Radiological risk to human and biota around the gas treatment plant Molve was estimated as negligible.

Phosphogypsum and its potential use in Croatia: challenges and opportunities.

Phosphogypsum (PG) is a waste by-product (residue) originating from the production of phosphoric acid and phosphate fertilisers. PG contains chemical and radioactive impurities, which is why it is mostly stockpiled in controlled areas. Worldwide, only about 15 % of PG is recycled or reused. Today, policies and business strategies prioritise sustainable development through circular economy, which certainly includes PG. This provides new opportunities for Croatia to manage its PG and make an effort to use it as an additive in different industries, such as agriculture and construction. Due to its chemical and radiological properties, PG can potentially cause problems for the environment and human health. Hence, before using PG, detailed knowledge of potential hazards is necessary to protect people and the environment. The aim of this review is to summarise available data on Croatian PG, compare them with other countries, and to identify knowledge gaps and the lack of data on potential hazardous substances in PG in order to assess the opportunities of using PG in Croatia.

Radioactivity of soil in Croatia I: naturally occurring decay chains.

The assessment of environmental radioactivity much relies on radionuclide content in soil. This stems from the significant contribution of soil to both external and internal exposure to ionising radiation via direct emission of gamma radiation and soil-to-plant radionuclide transfer, respectively. This motivated us to carry out a systematic research on the radioactivity of soil in Croatia to obtain relevant data that can be used as a basis for understanding the related effects of geomorphological, biogeographical, and climatological properties of the environment. We collected samples of the surface layer of uncultivated soil (0-10 cm) at 138 sites from all over the country and measured them for radionuclide activity concentrations by means of high-resolution gamma-ray spectrometry. This resulted in radioactivity maps containing data on activity concentrations of representative radionuclides in the environment. In this paper, which is the first in our two-part presentation, we focus on the naturally occurring 232Th and 238U decay chains and their correlations with the diversity of Croatian regions. For both of the chains, activity concentrations were the highest in the Dinaric region, the lowest in the Pannonian region, and intermediate in the Adriatic region. Relatively high concentrations of 226Ra in the soil of the Dinaric region implied a possibility of an enhanced emanation of its progeny 222Rn into the air. Activity concentrations of 210Pb were additionally elevated in areas with dense vegetation, most probably due to an atmospheric deposition of airborne 210Pb onto the surface of plants and their eventual decomposition on the ground.

Radioactivity of soil in Croatia II: 137Cs, 40K, and absorbed dose rate.

We took samples of uncultivated soil from the surface layer (0-10 cm) at 138 sites from all over Croatia and measured their radionuclide activity concentrations with high-resolution gamma-ray spectrometry. This second part of our report brings the results on 40K and 137Cs to complement those on the 232Th and 238U decay chains addressed in the first part. Together they give the most complete picture of radioactivity of Croatian soil so far. Activity concentrations of 40K were the highest in the Pannonian region, and there was an opposite trend for 137Cs. We found that the concentrations of 137Cs tended to increase with altitude, annual precipitation, and vegetation density. The concentration ratio of 137Cs and K in soil, which indicates the potential for 137Cs entering food chains via uptake by plants, was the lowest in agriculturally important areas in the east of the Pannonian region. In addition, we used the obtained results on activity concentrations to calculate the related absorbed dose rate as a measure of external exposure to ionising radiation from soil. The sum of the absorbed dose rates for naturally occurring radionuclides and 137Cs showed that external exposure was generally the highest in the Dinaric region and Istrian Peninsula.

Distribution and transfer of naturally occurring radionuclides and 137Cs in the freshwater system of the Plitvice Lakes, Croatia, and related dose assessment to wildlife by ERICA Tool.

The aim of this study was to investigate the natural radioactivity of Plitvice Lakes, under the assumption that due to its status as a National Park, the area can be considered an example of a natural freshwater system. Also, considering the transfer parameter data as the largest source of uncertainty in radiological risk assessments, the impact of site-specific data on dose rate assessment, as opposed to currently available data, was investigated. The study included gamma and alpha spectrometric measurements of 238U, 226Ra, 210Pb, 228Ra, and 40K in water, sediment, and fish samples, as well as 137Cs due to the coinciding of the study with the Fukushima accident. The content of naturally occurring radionuclides significantly varied in sediments of different Lakes, probably as a reflection of the different underlying geology of the area. Also, the 210Pb distribution in sediments indicated an up to 312 Bq kg-1 of the allochthonous contribution of this radionuclide at the beginning of the Lake's watercourse, which probably entered into the lake system by the major inlet river with its steady decrease along downstream lakes. Low 40K activity concentrations (27.5 ± 20.1 mBq L-1) in the Lake's waters might be one of the causes of increased 137Cs activity concentrations in fish samples (1.5 ± 0.4 Bq kg-1), which was found to be an order of magnitude higher than average values for different fish species from other Croatian freshwater systems (0.2 ± 0.1 Bq kg-1). A temporary increase of 137Cs activity concentrations was measured in water samples collected immediately after the Fukushima accident. Calculated site-specific sediment/water distribution coefficients and fish/water concentration ratios for radium and caesium were on average lower than generic ones found in the literature. Background dose rate assessments performed by the ERICA Tool indicated a profound impact of different input data on assessment results with water activity concentrations resulting in significantly higher dose rates (0.1-67 µGy h-1) in comparison to sediment activity concentrations (0.03-9 µGy h-1). An incremental dose rate due to 137Cs was found to be in the range of < 0.001-0.023 µGy h-1 which, in comparison to background dose rates, can be considered negligible.

Baseline radioecological data for the soil and selected bioindicator organisms in the temperate forest of Plitvice Lakes National Park, Croatia.

The aim of this study was to provide baseline radioecological data for the temperate forest ecosystem in Plitvice Lakes National Park. Emphasis was placed on the determination of naturally occurring radionuclides since there is an acknowledged lack of data for these radionuclides in non-accident conditions in wildlife, even for bioindicator organisms. Activity concentrations of 238U, 226Ra, 210Pb, 232Th, 40K, 134Cs, and 137Cs were measured by gamma spectrometry in soil and bioindicators: earthworms, conifer needles, mosses, and lichens. From the measured activity concentrations, concentration ratios were calculated to quantify the transfer of these radionuclides from soil to bioindicators. Our results show that soil activity concentrations are biased toward results from other studies conducted within the Dinaric mountain region. However, in moss and lichen samples, we measured higher activity concentrations of 226Ra and lower activity concentrations of 40K and 137Cs in comparison to similar studies. Also, we estimated lower concentration ratios for all radionuclides from soil to these organisms, except for 210Pb, in comparison to generic values. The transfer of 238U was generally low for all of the bioindicator organisms. For conifer needles, a correlation was found between activity concentrations of 226Ra and 137Cs in soil and related concentration ratios. Correlation was also found between the activity concentration of 40K in soil and transfer of 40K and 137Cs to mosses and lichens. A comparison with literature data highlighted the lack of 226Ra related concentration ratios for conifer trees and especially for earthworms. Therefore, the results of this study could supplement the sparse data currently available on radionuclide background data in similar ecosystems and related soil-to-wildlife transfer of radionuclides. Dose rate assessments, performed by the ERICA Tool, estimated that 96% of the overall exposure of wildlife in the Park area is due to the background dose rates, while 0.06 µGy h-1 on average can be attributed as an incremental dose rate from 134Cs and 137Cs.

Environmental radiological risk assessment of a coal ash and slag disposal site with the use of the ERICA Tool.

The aim of this study was to assess the environmental radiological risk of coal ash and slag to terrestrial wildlife. The research site used in this study was a disposal site of coal ash and slag with enhaced content of uranium decay chain radionuclides. With the use of the ERICA Tool, total dose rates to wildlife and risk of resultant radiobiological effects were estimated. As input data for the assessment, experimental activity concentrations of 238U, 226Ra and 210Pb in coal ash and slag and best estimates of activity concentrations for related daughter radionuclides and 235U decay chain were used. Where possible, the experimental data for activity concentrations of 238U, 226Ra and 210Pb in plants and related concentration ratios were used. Results were compared to background dose rates, also estimated by the Tool. The Tool's assessment data indicated internal exposure as the prevalent exposure pathway with 226Ra and 210Po as the main dose contributors. Also, the contribution of 235U decay chain to the total dose rate was not negligible since for some organisms it represented up to 11% of the total dose rate. The risk of an occurrence of radiobiological effects in plants on the coal ash and slag disposal site can be considered negligible since the estimated total dose rates were below the screening dose of 10 µGyh-1 and near the dose rates estimated for plants in the control area. However, the estimated dose rates for reference animals and Lichen & Bryophytes were above the screening dose rate for most organisms and on average 13 times higher than the estimated background dose rates. At the given dose rates, an occurrence of different radiobiological effects could not be excluded for animals in close contact with coal ash and slag such as earthworms and small burrowing mammals. A separate assessment performed on an example of reference plants showed that the use of activity concentrations in organisms as input data can result in an order of magnitude smaller estimates of dose rates in comparison to activity concentration in coal and ash as input data. Our study highlighted the need for experimental data in radiological risk assessments to mitigate the conservatism of the ERICA Tool and its tendency to overestimate dose rates.

Plant uptake of 238U, 235U, 232Th, 226Ra, 210Pb and 40K from a coal ash and slag disposal site and control soil under field conditions: A preliminary study.

The aim of this study was to investigate the uptake of 238U, 235U, 232Th, 226Ra, 210Pb and 40K by plants that grow on a coal ash and slag disposal site known for its higher content of naturally occurring radionuclides. Plant species that were sampled are common for the Mediterranean flora and can be divided as follows: grasses & herbs, shrubs and trees. To compare the activity concentrations and the resultant concentration ratios of the disposal site with those in natural conditions, we used control data specific for the research area, obtained for plants growing on untreated natural soil. Radionuclide activity concentrations were determined by high resolution gamma-ray spectrometry. Media parameters (pH, electrical conductivity and organic matter content) were also analysed. We confirmed significantly higher activity concentrations of 238U, 235U, 226Ra and 210Pb in ash and slag compared to control soil. However, a significant increase in the radionuclide activity concentration in the disposal site's vegetation was observed only for 226Ra. On the contrary, a significantly smaller activity concentration of 40K in ash and slag had no impact on its activity concentration in plant samples. The calculated plant uptake of 238U, 235U, 226Ra and 210Pb is significantly smaller in comparison with the uptake at the control site, while it is vice versa for 40K. No significant difference was observed between the disposal site and the control site's plant uptake of 232Th. These results can be the foundation for further radioecological assessment of this disposal site but also, globally, they can contribute to a better understanding of nature and long-term management of such disposal sites.

Measuring and modelling the radiological impact of a phosphogypsum deposition site on the surrounding environment.

Phosphogypsum (PG) is a waste product (residue) from the production of phosphoric acid characterized by technologically enhanced natural radioactivity. Croatia's largest PG deposition site is situated at the edge of Lonjsko Polje Nature Park, a sensitive ecosystem possibly endangered by PG particles. This field study investigates two aspects relevant for the general radiological impact of PG: risk assessment for the environment and risk assessment for occupationally exposed workers and local inhabitants. Activity concentrations of natural radionuclides ((238)U, (235)U, (232)Th, (226)Ra, (210)Pb, and (40)K) were measured in the PG (at the deposition site), soil, and grass samples (in the vicinity of the site). The ERICA Assessment Tool was used to estimate the radiological impact of PG particles on non-human biota of the Lonjsko Polje Nature Park. The average annual effective dose for occupationally exposed workers was 0.4 mSv which was within the worldwide range.