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.

Long term investigation of 137Cs in chicken meat and eggs from northwest Croatia.

This paper presents the results of long-term investigations of 137Cs activity concentrations in chicken meat and eggs from northwest Croatia for the period 1987-2018. The research has been done as a part of monitoring program of radioactive contamination in Croatia. The highest activity concentrations in both of these foodstuffs were measured in 1987 and have been decreasing exponentially ever since. The Fukushima-Daiichi accident in 2011 did not cause any increase of 137Cs activity concentrations. The ecological half-life for 137Cs was estimated to be 8.0 and 8.4 years for chicken meat and eggs respectively. The correlation between 137Cs in fallout and chicken meat as well as between 137Cs in fallout and eggs is very good, the respective correlation coefficients being 0.79 and 0.72, indicating that fallout was the main source of 137Cs contamination in both foodstuffs. The estimated effective doses received by adult members of the Croatian population due to the intake of radiocaesium by chicken meat and egg consumption for the overall observed period are very small, 2.0 and 0.6 µSv respectively. Therefore, chicken meat and chicken egg consumption was not a critical pathway for the transfer of radiocaesium to humans.

Assessing the radiological load on the environment in the middle Danube river basin on the basis of a study of the Kopacki Rit Nature Park, Croatia.

A study of the environmental radioactivity in the Kopacki Rit Nature Park, Croatia, is presented. This wildlife reserve is part of the Middle Danube River Basin, and it is exposed to various pollutants due to a number of human activities in the surroundings, where there is a nuclear power plant and also urban centres and areas of intense agricultural production. Results for the activity concentrations of soil and surface water samples do not indicate any elevated radioactivity level, which is confirmed by on-site measurements of ambient dose rate equivalent. An assessment of the radiological load on the local biota, carried out using the ERICA tool, implies an overall low radiological risk even if conservative values of the risk quotient are used. Therefore, human activities do not have a significant effect on the radiological load on the Kopacki Rit area. A similar conclusion might be made with regard to numerous similar environments in the Middle Danube River Basin.

Radiocaesium in mosses from the Kopacki rit Nature Park in Croatia: searching for undeclared releases from nuclear facilities in war-torn Ukraine.

The invasion of Ukraine and military operations around Ukrainian nuclear power plants and other nuclear facilities have prompted us to search for radiocaesium in mosses from the Kopacki Rit Nature Park in Croatia, since mosses are known bioindicators of airborne radioactive pollution, and Kopacki Rit is a known low radiocaesium background area. Sampling was finished in August 2023, and our analysis found no elevated radiocaesium levels. Kopacki Rit therefore remains a suitable place for future detection of anthropogenic radioactive pollutants.

Assessment of the radionuclide remediation potential of novel miscanthus hybrids.

There are few studies related to the radionuclide remediation options, which comply to the demands of the environmentally non-destructive physical remediation methods. So far, most of the research was conducted on the phytoremediation capacity of different energy crops, as well as the established miscanthus hybrids which involved metal and heavy metal contaminants. Hence, the objective of this research was the radioecological characterization of the examined agroecosystem, including the initial source of the radionuclides (soil) as well as different miscanthus hybrids grown on the same soil. The results have shown that the radioactive content of soil was similar to the global averages. All measurements of the activity concentration of 137Cs in miscanthus samples were below the detection limits. There is also an indication that 210Pb is leaching into the lower layers (or is being taken up by miscanthus plant from the upper layers). Moreover, transfer factors (TFs) for radionuclides, as a more precise parameter for evaluating the phytoremediation potential, were calculated; the TFs were found to be very low for 226Ra (≤0.07), TFs for 40K (≤0.39) and for 232Th (≤0.21) were in the lower limits, whereas the TFs for 238U were found to be the highest (≤0.92). For 210Pb, the TFs were not calculated, since the expectation was that a significant part of the measured quantity came from the air, and not through the soil. Having in mind the sustainability and the circularity aspect of the radionuclide phytoremediation system, the appropriate management method should be applied for the disposal and utilization of the biomass contaminated with radionuclides. This research has shown that the radiological content in miscanthus is high enough and the ash content is low enough that miscanthus ash could be considered as a NORM (Naturally Occurring Radioactive Material), and it can be further used for the construction industry (i.e. concrete, tiles), in mixtures with other materials with certain limitations, similar to the utilization of ash from other sources such as coal or wood.

Elemental and Radiological Characterisation of Arbutus unedo L. Leaves and Tea: Impact of Preparation Method on Nutritional Risk/Benefit.

The aim of this study was to characterise the elemental and radiological composition of strawberry tree (Arbutus unedo L.) leaves and tea preparations and compare it with commercial Uvin H herbal mixture, widely used in treatment of urinary tract infections. The concentration of 17 elements and the activity concentration of selected radionuclides were measured in strawberry tree leaves/Uvin H herbal mixture, as well as in herbal tea prepared by infusion or decoction of leaves for 5 or 10 min. In both leaves and tea preparations, Ca, K, Mg, and Na were the most abundant elements, while the lowest levels were measured for As, Co, Mo, and Se. Only 137Cs and 40K were detected in analysed leaves/herbal mixture, while the activity of radionuclides in tea preparations was below the detection limit. The maximum possible health benefits can be obtained by a 10-min decoction of leaves, which resulted in the highest total phenolic content and antioxidant activity and levels of K, Ca, Mg, Na, Fe, Mn, and Se in comparison to the other preparation methods evaluated in this study. The calculated intake of potentially toxic elements and radionuclides does not represent a health risk to consumers.

Development of a solid phase microextraction method for the determination of nicotine in dried mushrooms.

Official control of EU market foodstuffs repeatedly reports high nicotine levels in dried wild mushrooms without any clear scientific consensus about their origin. The advised constant monitoring calls for improvements to existing methods. For this purpose, our aim was to develop a headspace solid phase microextraction (HS-SPME) method coupled to gas chromatography with mass spectrometric detection (GC-MS) that would eliminate the need for extensive sample pre-treatment. The type of fiber coating, amount of sample, extraction temperature and time, desorption time and salt addition were investigated and optimized as parameters affecting the SPME procedure. The optimized conditions were used to validate a quantitative method for nicotine analysis by matrix-matched calibration and isotopically labelled internal standard correction. The method provided good linearity (r2 = 0.9994) over the tested concentration range (0.025-1 mg kg-1), low detection limit (0.005 mg kg-1) and low quantification limit (0.017 mg kg-1) for nicotine, being below the EU foodstuff regulations. For both of the tested concentration levels (0.050 and 0.200 mg kg-1), precision expressed as relative standard deviation was below 10% (4.5% and 8.5%, respectively), while accuracy was 98.2% and 100.3%. The optimized method was then used to determine nicotine levels in 18 samples of dried Boletus mushrooms from southeastern European countries entering the EU market. We demonstrated our HS-SPME procedure to be fast, simple, sensitive, solvent-free, cost-effective and thus suitable for controlling consumer safety regarding nicotine level in dried mushrooms.

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.

Radiological impact of an active quarry in the Papuk Nature Park, Croatia.

Papuk Nature Park, unlike most similar parks and preserves in the world, contains active quarries. Quarries dig stone from the ground, creating dust and exposing deeper, potentially more radioactive layers. Since the forest trails in the Park lead right up to the quarries, we believed it was important to determine the radiological impact of the quarries on the Park environment. We measured ambient dose rate equivalent H*(10) and sampled moss at 26 Park locations along two of four quarries, along the road between them, and near Lake Orahovac, a very popular tourist destination close to the quarries. Moss is a standard bioindicator of exposure to heavy metals, including radionuclides. Using-gamma ray spectrometry we determined the activity concentration of 137Cs and of representative naturally occurring radionuclides - 238U, 226Ra, 210Pb, 232Th, and 40K - in sampled moss. H*(10) at selected locations was similar to the background H*(10) measured continuously all over Croatia. The ranges of measured activity concentrations of 137Cs and naturally occurring radionuclides in moss did not differ significantly from other parts of Croatia and nearby countries.

Mosses in the Kopacki Rit Nature Park, Croatia, as bioindicators of a potential radioactive contamination of the middle Danube River basin.

We studied activity concentrations of radionuclides in the Kopacki Rit Nature Park using mosses as bioindicators. This area of intact nature is at the tripoint of Croatia, Hungary, and Serbia, being located basically at the centre of the middle Danube River basin. Therefore, it can be easily affected by airborne pollution from various locations in the Middle Europe and beyond. The goal of our research was to assess whether the Park could serve as a location where any new radioactive contamination could be sensitively detected, which implied a necessity for low activity concentrations at the present time. Our gamma-ray spectrometry revealed the presence of only one anthropogenic gamma emitter, that is, 137Cs. Its activity concentration in the mosses ranged from 0.7 to 13.1 Bq kg-1, being low indeed. Another radionuclide in our focus was 210Pb. Generally, its elevated concentrations may signify ecologically undesirable human activities that involve naturally occurring radioactive matter. The activity concentration of 210Pb in the mosses was in the range from 183 to 690 Bq kg-1. This did not depart from the results of other similar studies and was again low enough for a detection of possible excess amounts of this radionuclide in the future.

Application of a new in situ calibration technique for gamma spectrometry and comparison of in situ and laboratory measurements.

In situ gamma ray spectrometry was developed to quickly measure large areas of land following nuclear accidents. However, a proper calibration of detectors for in situ measurements is a long and complicated process. One tool designed to make this calibration quick is the InSiCal software. We compared 5,000 s in situ measurements with two different HPGe detectors calibrated using the InSiCal software and laboratory measurements of samples collected at the same locations. Our findings suggest that in situ gamma spectrometry using InSiCal software can provide reasonably accurate data, but some improvements are needed.

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.

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.

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.

Natural radioactivity of 226Ra and 228Ra in thermal and mineral waters in Croatia.

Thermal waters are known as valuable natural resources of a country. They contain certain degree of natural radioactivity attributable to the elements of the uranium and thorium natural decay series. Among these elements, the most radiotoxic and the most important is radium that exists in several isotopic forms (226Ra and 228Ra). The focus of attention was the content of radium in samples of thermal and mineral spring water from several spas in Croatia. These waters are mainly used for medical, bathing and recreational purposes, and some of them are used for drinking. Measured activity concentrations of 226Ra ranged from 87 to 6200 mBq l(-1) which, in some springs, exceed the maximal permissible level of 1 Bq l(-1) for drinking water. Measured activity concentrations of 228Ra ranged from 23 to 3480 mBq l(-1). The study showed that radium content for the investigated thermal and mineral waters is below the levels at which negative consequences would arise due to ingestion.

Long-term investigations of post-Chernobyl radiocaesium in fallout and air in North Croatia.

The long-term behaviour of (137)Cs activity concentrations in air and fallout has been studied in the city of Zagreb for the post-Chernobyl period (1986-2006) as a part of an extended monitoring program of radioactive contamination of human environment in Croatia. Annual mean (137)Cs activity concentrations in air and annual total deposition fluxes (wet plus dry) decreased from 2.8 x 10(-4) Bq m(-3) in September 1986 to 3.0 x 10(-6) Bq m(-3) in last quarter of 2006 and from 6,410 Bq m(-2) year(-1) in 1986 to 2 Bq m(-2) year(-1) in 2006 respectively. By fitting the measured (137)Cs activity concentrations to the theoretical curve the ecological half-lives of (137)Cs in air and fallout were estimated with respective values of 0.46 and 0.54 years for immediate post-Chernobyl period, increasing to 5.52 and 3.97 years afterwards. Using the data on (137)Cs activity concentrations in air and fallout total caesium deposition velocity of (3.34 +/- 3.13) x 10(-2) ms(-1) was estimated with median value being 2.13 x 10(-2) ms(-1). Such relatively high (137)Cs deposition velocities compared with pre-Chernobyl ones, are characteristic for the post-Chernobyl period and, according to Stokes' settling law, indicate that the diameters of aerosol particles associated with (137)Cs originated from the Chernobyl accident are pretty large, i.e. >1 microm. (134)Cs/(137)Cs activity ratio in fallout and in air has been found to be similar to the theoretically predicted values, initial value being about 0.5 and decreasing according to differential radioactive decay. The similar ratio has been observed in most of the other environmental samples.

The role of physics in radioecology and radiotoxicology.

This article gives an overview of physical concepts important for radioecology and radiotoxicology to help bridge a gap between non-physicists in these scientific disciplines and the intricate language of physics. Relying on description and only as much mathematics as necessary, we discuss concepts ranging from fundamental natural forces to applications of physical modelling in phenomenological studies. We first explain why some atomic nuclei are unstable and therefore transmute. Then we address interactions of ionising radiation with matter, which is the foundation of both radioecology and radiotoxicology. We continue with relevant naturally occurring and anthropogenic radionuclides and their properties, abundance in the environment, and toxicity for the humans and biota. Every radioecological or radiotoxicological assessment should take into account combined effects of the biological and physical half-lives of a radionuclide. We also outline the basic principles of physical modelling commonly used to study health effects of exposure to ionising radiation, as it is applicable to every source of radiation but what changes are statistical weighting factors, which depend on the type of radiation and exposed tissue. Typical exposure doses for stochastic and deterministic health effects are discussed, as well as controversies related to the linear no-threshold hypothesis at very low doses.

226Ra and 228Ra in Croatian rivers.

The presence of natural radionuclides in Croatian rivers emphasizes the need for its continuous monitoring. Therefore results of 226Ra and 228Ra determination in Croatian river waters are presented in this paper. 226Ra and 228Ra were chosen as a possible source of human exposure due to their high radio-toxicity. Fifty liters of river water samples were collected from the Danube, Drava, Sava, Krka and Neretva rivers twice a year from 2002 to 2006. It is showed that activity concentrations of 226Ra ranged from 6.54 mBq/L to 59.44 mBq/L and 228Ra activity concentrations ranged from 2.57 mBq/L to 20.76 mBq/L. The highest values of both 226Ra and 228Ra were measured in the river Drava, and the lowest values in the river Sava. Statistically significant differences were not observed between radium concentrations from two watersheds (the Black Sea and the Adriatic Sea watershed), nor between 226Ra/228Ra ratio in rivers individually. The number of collected samples is insufficient to make more statistically significant conclusions. However the data obtained in this study could be the baseline for evaluating possible future changes.