We combined stable isotope tracers of blood plasma, blood cells and egg contents with faecal analysis during pre-breeding and egg laying phases in two dipper species Cinclus cinclus and Cinclus mexicanus to determine the occurrence of dietary shifts during egg production and to assess consequences for egg contaminant loads. In both species, changes in δ13C (C. cinclus) or δ15N (C. mexicanus) in female plasma relative to red blood cells indicated a dietary shift during laying that was not observed in males. Eurasian dippers increased prey consumption as breeding approached, shifting from primarily trichopteran insect larvae to ephemeropterans and plecopterans. In American dippers, egg-laying females switched to feeding at a higher trophic level by consuming more fish. Eggs derived from higher trophic level diets contained more mercury (American dipper), polychlorinated biphenyls and some organochlorines, especially DDT metabolites. The results demonstrate how dietary changes during egg laying accompany the demands for egg production with consequences for contaminant deposition in avian eggs. Changes in laying diet influences contaminant deposition in bird eggs.

The use of purge and trap gas chromatography–mass spectrometry (GC-MS) technique for the determination of methylmercury in biological and sediment samples was described. The GC-MS detection system was combined with the dithizone extraction method for biological samples and the distillation method for sediment samples to alleviate matrix interference problems. The method was validated by analysis of CRMs such as SRM 966 (human blood), BCR 463 (tuna fish), IAEA 407 (fish), ERM CC580 (estuarine sediment), and IAEA 405 (sediment). The performance of the purge and trap GC-MS method was also tested on field samples of freshwater fish and sediment. The results were compared with those of the GC-ECD and the GC-CVAFS, which were used widely for methylmercury analysis. Additionally, total mercury and methylmercury levels in freshwater fish and sediments from various reservoirs and streams in Korea were measured to understand mercury contamination status in Korean peninsula. Methylmercury concentrations in freshwater fish were found to correlate with body weight, diet habit, and food availability. In sediment, total mercury concentrations correlated with methylmercury concentrations and organic matter such as %C and %S. However, no significant relationships between methylmercury and sediment organic matter have been found.

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.