Background, aim, and scope Zinc is an essential micronutrient element but its concentrations found in contaminated soils frequently exceed those required by the plant and soil organisms, and thus create danger to animal and human health. Phytoremediation is a technique, often employed in remediation of contaminated soils, which aims to remove heavy metals or other contaminants from soils or waters using plants. Arabidopsis (A.) halleri ssp. gemmifera is a plant recently found to be grown vigorously in heavy metal contaminated areas of Japan and it contained remarkably high amount of heavy metals in its shoots. However, the magnitude of Zn accumulation and tolerance in A. halleri ssp. gemmifera need to be investigated for its use as a phytoremediation plant. Materials and methods A. halleri ssp. gemmifera was grown for 3 weeks into half-strength nutrient solution with Zn (as ZnSO₄) levels ranging from 0.2 to 2,000 µM. The harvested plants were separated into shoots and roots, dried in the oven, and ground. The plant tissue was digested with nitric-perchloric acid, and the Zn concentration in the digested solution was measured by atomic absorption spectrophotometer. Results and discussion The results showed no reduction in shoot and root dry weight when plants were grown at 0.2 to 2,000 µM Zn in the solution. The highest Zn concentration measured in the shoots was 26,400 mg kg⁻¹ at 1,000 µM Zn, while in the roots, it was 71,000 mg kg⁻¹ at 2,000 µM Zn treatment. Similar to the Zn concentration in plant parts, maximum Zn accumulation of 62 mg plant⁻¹ in the shoots and 22 mg plant⁻¹ in the roots was obtained at 1,000 and 2,000 µM Zn in the solution. The percentage of Zn translocation in shoot varied from 69% to 90% of the total Zn, indicating that the shoot was the major sink of Zn accumulation in this plant. Conclusions The results of this study indicate that the growth of A. halleri ssp. gemmifera was not affected by the Zn level of up to 2,000 µM in the nutrient solution. The concentration of Zn found in shoot indicated that A. halleri ssp. gemmifera has an extraordinary ability to tolerate and accumulate Zn and hence a good candidate for the phytoremediation of Zn-polluted soil. Recommendations and outlook Based on the results presented in this study and earlier hydroponics, and field study, A. halleri ssp. gemmifera seems to be a potential heavy metals hyperaccumulator, and could be recommended to use for phytoremediation of Cd- and Zn-contaminated soils.

Background, aim and scope The paper presents concentrations of trace elements in blood of homebred animals (cows and sheep) from Southern Serbia (Bujanovac) and the contents of natural and anthropogenic radionuclides and some heavy metals in feed. The region of Southern Serbia was exposed to contamination by depleted uranium ammunition during NATO attacks in 1999 and therefore, is of great concern to environmental pollution and human and animal health. Materials and methods Conventional instrumental and epithermal neutron activation analyses are used to measure trace elements in cow and sheep blood samples collected randomly at six locations in the region of Bujanovac (village of Borovac) in the spring of 2005. Samples of feed (grass and crops: corn, wheat and oats), collected on the same locations (households), are analysed for the contents of radionuclides on an HPGe detector (Ortec, relative efficiency 23%) by standard gamma spectrometry. The content of Hg, Pb and Cd in feed is determined by standard atomic absorption spectrometry on the VarianSpectra220/ThermoSolar GFS97 spectrometer. Results Concentrations of 29 elements (Na, Al (P), Cl, K, Sc, Cr, Mn, Ni, Fe, Co, Zn, Se, As, Br, Sr, Rb, Sb, In, I, Ba, Cs, La, Nd, Eu, Sm, Tb, Hf, Ta and Th) are determined in blood of the examined animals. In feeds, natural ⁴⁰K is found in all of the samples, cosmogenic ⁷Be and fission product ¹³⁷Cs are detected only in the grass samples, while heavy metals Hg, Cd and Pb are found in the range of 0.01-0.02, 0.84-1.15 and 0.74-7.34 mg/kg, respectively. Calculated soil-to-blood transfer factors are in a wide range of 8·10⁻⁶ to 64, as a result of varying significance of the elements in animal metabolism and feeding habits. Discussion The results of trace elements' concentrations in animal blood are in good agreement with available data for K, Ni, Zn, Se and Rb. Higher Br concentrations in animal blood are most probably caused by large biomass burning events during blood sampling. Very low concentration of Fe in cows and sheep confirms the results of previous biochemical studies on animal anaemia in the region. High concentration of As correlates with geochemical peculiarities of the Balkans and is also likely influenced by the use of pesticides in the agricultural production. For some of the elements (La, Nd, Eu, Sm, Tb, Sb, Hf, Ta, Th, In, Ba, Sr, Sc and Cs), there are few or no literature data. Therefore, some of the presented data are significant not only for the country and the region, but on a wider scale. Activities of natural radionuclides in feeds are within the average values reported for the region, while the activities of ²¹⁰Pb and ²³⁵/²³⁸U are below the limit of detection. This is in accordance with previous investigations showing no widespread contamination by depleted uranium in the area. Contents of Hg and Pb in feeds are below the nationally permissible levels, unlike the content of Cd which exceeds it, probably caused by the use of phosphate fertilisers and fossil fuel combustion in the area. Conclusions In general, the concentrations of trace elements in blood of homebred cows and sheep are in good agreement with reference materials, available literature data and the results of previous studies in the area. The exceptions are Fe, As and Br. The contents of natural and anthropogenic radionuclides in feeds are within the expected levels, and there are no signs of contamination by depleted uranium or other fission products. Apart from Cd, there are no signs of pollution by heavy metals in feeds. The highly sensitive method of instrumental neutron activation analysis provides data on the concentration of some elements in animal blood not previously reported for the region and elsewhere. Recommendations and perspectives The presented study is a part of the long term ongoing project on the health risk assessment on animals and humans in the region. The collected data is intended to provide a base for the animal and human risk assessment as well as an estimate of the general pollution status of the environment in the region. Since some of the investigated elements are classified as important trace elements for livestock, the results could also be used to balance and improve the animal diet and thus, improve the growth and reproduction rate.

PURPOSE: Chlor-alkali plants are one of the most important point sources of mercury to aquatic environment. The problem of Hg contamination has been studied in a region, Rm Valcea (Romania), impacted by the wastewater discharge of a chlor-alkali plant. The purpose of the present study is to evaluate the current status of mercury pollution in the Babeni reservoir (Olt River) and the exposure of local population via fish consumption to mercury originating from the chlor-alkali plant. METHODS: Sediments were collected from Valcea, Govora and Babeni reservoirs. Grain size distribution, organic content and total mercury (THg) concentrations were analysed in sediments. Fish were purchased from local anglers, and the scalp hair was collected from volunteers. THg in sediment, fish and hair samples was determined using an atomic absorption spectrophotometer for Hg determination. Monomethylmercury (MMHg) was analysed in the muscle and liver tissues by species-specific isotope dilution and capillary gas chromatography hyphenated to inductively coupled plasma mass spectrometer. RESULTS: High mercury concentrations were found in the sediments and in fish from Babeni reservoir, with a median of 2.1 mg/kg (IQR = 3.2) in sediments and a mean value of 1.8 ± 0.8 mg/kg_ww in fish muscle. MMHg concentrations in fish were well above the WHO guidelines for fish consumption. Local population consuming fish from the Babeni reservoir had THg concentrations in hair significantly higher than those consuming fish from upstream reservoirs and/or from the shops and reached a median value of 2.5 mg/kg (IQR = 3.6). CONCLUSIONS: The remnant pollution in the fish of this reservoir, and probably many other lakes and reservoirs receiving Hg polluted wastewater, represents a considerable health risk for the local fish consumers.

Purpose The aim of this study was to compare the level of metal contamination in two bays in the middle part of the Eastern Adriatic coastal zone in Croatia using the gills of mussels Mytilus galloprovincialis as indicator tissue. Despite the existing sources of contamination, previous studies with caged mussels only indicated moderate metal contamination of the Kaštela Bay, contrary to the Trogir Bay in which marina and shipyard present a probable source of Cu- and Zn-contamination. Methods The measurements of metallothioneins (MTs) and metals that induce MT synthesis (Cu, Zn, and Cd) were performed in the heat-treated gill cytosol and total proteins (TPs) in the untreated gill cytosol. MTs were determined by differential pulse voltammetry, Cu and Zn by flame atomic absorption spectrometry (AAS), Cd by graphite furnace AAS, and TPs by Bradford spectrophotometric procedure. Results The results collected in four sampling campaigns (autumn periods from 2001 to 2004) indicated that MT levels in mussel gills (expressed on dry mass basis 2.3 ± 0.3 mg g⁻¹) were comparable with basal levels reported in the literature (2.5 ± 0.8 mg g⁻¹). Observed interindividual, temporal, and spatial MT variability could be associated with different confounding factors, such as the time of sampling, total protein concentration, and mussel size rather than cytosolic levels of Cu and Zn. Metal levels, expressed on wet mass basis, in the heat-treated gill cytosol ranged from 1.33 to 11.31 μg g⁻¹ for Zn, from 0.72 to 2.96 μg g⁻¹ for Cu, and from 0.036 to 0.100 μg g⁻¹ for Cd. The highest Zn level was measured at Vranjic (Kaštela Bay)—the site influenced by untreated domestic wastewater, while somewhat increased Zn and the highest Cu levels were found at marina and shipyard locations (Trogir Bay). The highest Cd level was measured at Inavinil (Kaštela Bay). Conclusions The observed association of gill MT levels with several biotic and abiotic factors limits its use as the biomarker of low-level metal exposure. Therefore, the use of the metal concentrations in the heat-treated gill cytosol of Mediterranean mussels should be considered for the assessment of the low-level metal contamination of coastal marine areas.

INTRODUCTION: In this work, we propose an innovative application of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as a methodological approach for the chemical characterisation of black crusts on stone monuments, associated with traditional micro-morphological (optical and scanning electron microscopy) and infrared spectroscopic techniques (FTIR). METHODS: This new approach was tested on black crusts developing on two marble substrates, one, the columns of the San Cosimato cloister in Rome, and the other, a sculpture representing an angel, located in Pessano con Bornago, a small industrial town near Milan. DISCUSSION: The main aim of this study was to develop and test the reliability of the LA-ICP-MS analytical method on black crusts and to explore the idea that trace element concentrations in black crusts can be applied to investigate their origin and the relations between concentrations of polluting elements in black crusts and environmental conditions. CONCLUSION: The results obtained by applying traditional techniques find considerable support in the innovative method used here, which could determine the concentrations of a large number of trace elements (including heavy metals) in the black crusts examined, and thus could also be used as a reliable indicator of environmental pollution.

Purpose As one component of the German ecological environment observation, the Environmental Specimen Bank program was initiated in the mid-1980s. Under the program, representative specimens of marine, fresh water, and terrestrial ecosystems are sampled regularly and archived under chemically stable conditions. An initial characterization of the samples provides data regarding the status quo of the respective ecosystems. The aim of the present publication is to give insight into these real-time monitoring data, which have been generated for the last 10 to 20 years. This is done exemplarily for the heavy metals cadmium (Cd), mercury (Hg), and lead (Pb) in marine specimens of the Baltic and the North Sea. Methods Bladder wrack (Fucus vesiculosus), blue mussel (Mytilus edulis), eelpout (Zoarces viviparus), and eggs of herring gulls (Larus argentatus) were sampled at one location in the Baltic Sea and at two sites in the North Sea (Schleswig-Holstein Wadden Sea and Lower Saxony Wadden Sea). Annual samples were pooled, homogenized, and analyzed for a set of elements. Cd and Pb were quantified after freeze-drying and microwave digestion using inductively coupled plasma-mass spectrometry. Total Hg in freeze-dried samples was determined by atomic absorption spectrometry using a direct mercury analyzer. Results Time series data covering up to two decades revealed comparable cadmium levels at all three locations. Concentrations in bladder wrack ranged between 0.10 and 0.37 µg/g on a wet weight basis (ww). Respective values for blue mussel and eelpout liver were 0.07-0.29 and 0.01-0.10 µg/g ww. Herring gull eggs were not included in cadmium analyses. Declining trends were observed in North Sea bladder wrack and mussels, eelpout from the Lower Saxony site, and mussels from the Baltic Sea. Upward trends were apparent in eelpout from the Schleswig-Holstein location. Mercury concentrations in Baltic Sea specimens ranged from 1.1-2.7 ng/g ww in bladder wrack to 2.6-5.1, 26-52, and 86-226 ng/g ww in blue mussel, eelpout muscle, and herring gull eggs, respectively. No temporal trends were observed. North Sea bladder wrack had accumulated 5.4-24 ng/g ww Hg. The respective Hg values for blue mussel and eelpout muscle were 19-64 and 73-187 ng/g ww. Highest Hg contents were detected in herring gull eggs (90-1,100 ng/g ww). Declining trends of Hg were observed in herring gull eggs at both North Sea locations and in blue mussels at the Lower Saxony site. Lead concentrations in Baltic Sea specimens were 48-222 ng/g ww in bladder wrack, 85-189 ng/g ww in blue mussel, 2.0-9.5 and 10-42 ng/g ww in eelpout muscle and liver, and 2.7-26 ng/g ww in herring gull eggs. In the North Sea, Pb concentrations were as follows: 68-397 ng/g ww in bladder wrack, 101-507 ng/g ww in blue mussels, 2.6-35 and 5.9-158 ng/g ww in eelpout muscle and liver, and 3.5-55 ng/g ww in herring gull eggs. Highest Pb-levels were found at the Lower Saxony site. Declining Pb-trends were observed in bladder wrack from the Baltic Sea; in bladder wrack and mussel at the Schleswig-Holstein location; and in bladder wrack, mussels, eelpout liver, and herring gull eggs at the Lower Saxony site. Conclusions During the 10 to 20 years of monitoring, reliable data were obtained which allow a good insight into metal contamination of marine biota. Assessment of the data according to OSPAR criteria (OSPAR 2005) revealed cadmium levels above the derived background concentrations in mussels of all three sites. Mercury levels above background concentrations were found at both North Sea locations, whereas only mussels at the Lower Saxony site had Pb concentrations above the reference value. Archived specimens are available for further analyses and questions which may arise in the future (speciation of elements, metallomics).