Application of an ecosystem model to evaluate the importance of different processes and food web structure for transfer of 13 elements in a shallow lake.

In environmental risk assessments of nuclear waste, there is need to estimate the potential risks of a large number of radionuclides over a long time period during which the environment is likely to change. Usually concentration ratios (CRs) are used to calculate the activity concentrations in organisms. However, CRs are not available for all radionuclides and they are not easily scalable to the varying environment. Here, an ecosystem transport model of elements, which estimates concentrations in organisms using carbon flows and food transfer instead of CR is presented. It is a stochastic compartment model developed for Lake Eckarfjärden at Forsmark in Sweden. The model was based on available data on carbon circulation, physical and biological processes from the site and identifies 11 functional groups of organisms. The ecosystem model was used to estimate the environmental transfer of 13 elements (Al, Ca, Cd, Cl, Cs, I, Ni, Nb, Pb, Se, Sr, Th, U) to various aquatic organisms, using element-specific distribution coefficients for suspended particles (Kd PM) and upper sediment (Kd sed), and subsequent transfer in the foodweb. The modelled CRs for different organism groups were compared with measured CRs from the lake and literature data, and showed good agreement for many elements and organisms, particularly for lower trophic levels. The model is, therefore, proposed as an alternative to measured CR, though it is suggested to further explore active uptake, assimilation and elimination processes to get better correspondence for some of the elements. The benthic organisms (i.e. bacteria, microphytobenthos and macroalgae) were identified as more important than pelagic organisms for transfer of elements to top predators. The element transfer model revealed that most of the radionuclides were channelled through the microbial loop, despite the fact that macroalgae dominated the carbon fluxes in this lake. Thus, element-specific adsorption of elements to the surface of aquatic species, that may be food sources for organisms at higher trophic levels, needs to be considered in combination with generic processes described by carbon fluxes.

Evaluation of factors influencing accumulation of stable Sr and Cs in lake and coastal fish.

As a result of nuclear accidents and weapons tests, the radionuclides Cs-137 and Sr-90 are common contaminants in aquatic ecosystems. Concentration ratios (CR) based on concentrations of stable Cs and Sr in biota and media are used for the estimation of transfer of their radioisotopes for radiation dose calculations in environmental and human safety assessments. Available element-specific CRs vary by over an order of magnitude for similar organisms, thus affecting the dose estimates proportionally. The variation could be reduced if they were based on a better understanding of the influence of the underlying data and how that affects accumulation and potential biomagnification of stable Cs and Sr in aquatic organisms. For fish, relationships have been identified between water concentrations of K and CR of Cs-137, and between water concentrations of Ca and CR of Sr-90. This has not been confirmed for stable Cs and Sr in European waters. In this study, we analysed an existing dataset for stable Cs and Sr, as well as K and Ca, in four Swedish lakes and three Baltic Sea coastal areas, in order to understand the behaviour of these elements and their radioisotopes in these ecosystems. We found significant seasonal variations in the water concentrations of Cs, Sr, K and Ca, and in electrical conductivity (EC), especially in the lakes. CR values based on measurements taken at single or few time points may, therefore, be inaccurate or introduce unnecessarily large variation into risk assessments. Instead, we recommend incorporating information about the underlying variation in water concentrations into the CR calculations, for example by using the variation of the mean. The inverse relationships between fish CR(Cs)-[K]water and fish CR(Sr)-[Ca]water, confirmed that stable Cs and Sr follow the same trends as their radioisotopes. Thus, they can be used as proxies when radioisotope data are lacking. EC was also strongly correlated with K and Ca concentrations in the water and could potentially be used as a quick and cost-effective method to estimate water chemistry to obtain less variable CR. We also recommend some simple improvements to data collection that would greatly enhance our ability to understand Cs and Sr uptake by fish.

Radionuclide transfer in marine coastal ecosystems, a modelling study using metabolic processes and site data.

This study implements new site-specific data and improved process-based transport model for 26 elements (Ac, Ag, Am, Ca, Cl, Cm, Cs, Ho, I, Nb, Ni, Np, Pa, Pb, Pd, Po, Pu, Ra, Se, Sm, Sn, Sr, Tc, Th, U, Zr), and validates model predictions with site measurements and literature data. The model was applied in the safety assessment of a planned nuclear waste repository in Forsmark, Öregrundsgrepen (Baltic Sea). Radionuclide transport models are central in radiological risk assessments to predict radionuclide concentrations in biota and doses to humans. Usually concentration ratios (CRs), the ratio of the measured radionuclide concentration in an organism to the concentration in water, drive such models. However, CRs vary with space and time and CR estimates for many organisms are lacking. In the model used in this study, radionuclides were assumed to follow the circulation of organic matter in the ecosystem and regulated by radionuclide-specific mechanisms and metabolic rates of the organisms. Most input parameters were represented by log-normally distributed probability density functions (PDFs) to account for parameter uncertainty. Generally, modelled CRs for grazers, benthos, zooplankton and fish for the 26 elements were in good agreement with site-specific measurements. The uncertainty was reduced when the model was parameterized with site data, and modelled CRs were most similar to measured values for particle reactive elements and for primary consumers. This study clearly demonstrated that it is necessary to validate models with more than just a few elements (e.g. Cs, Sr) in order to make them robust. The use of PDFs as input parameters, rather than averages or best estimates, enabled the estimation of the probable range of modelled CR values for the organism groups, an improvement over models that only estimate means. Using a mechanistic model that is constrained by ecological processes enables (i) the evaluation of the relative importance of food and water uptake pathways and processes such as assimilation and excretion, (ii) the possibility to extrapolate within element groups (a common requirement in many risk assessments when initial model parameters are scarce) and (iii) predictions of radionuclide uptake in the ecosystem after changes in ecosystem structure or environmental conditions. These features are important for the longterm (>1000 year) risk assessments that need to be considered for a deep nuclear waste repository.

[Synthesis and luminescent spectral characteristics of porphyrin complexes with platinum group metals].

The synthesis of natural and synthetic porphyrin complexes with Pt, Pd, Rh, and Ru is reported. Their electronic absorption spectra, phosphorescence spectra, and lifetimes at room temperature both in the presence and in the absence of oxygen were studied. It has been shown that the variation of the nature of the central metal atom and of the substituents in pyrrole and phenyl rings allows the obtaining of metalloporphyrins with various phosphorescence excitation and phosphorescing emission spectra at room temperature. The English version of the paper: Russian Journal of Bioorganic Chemistry, 2008, vol. 34, no. 2; see also http://www.maik.ru.

[Formylation of porphyrin platinum complexes].

The formylation reaction of platinum complexes of beta-unsubstituted porphyrins was studied. The interaction of deuteroporphyrin IX derivatives with the Vilsmeyer reagent led to the selective formylation of their macrocycles in the beta position. The resulting formyl derivatives of the porphyrins are of interest for fluorescent immunoassay.

[Activity of cytochromes P-450p and P-450h in liver microsomes and blood corticosteroid levels in experimental animals under the action of physical factors]. / Aktivnost' tsitokhromov P-450p i P-450h mikrosom pecheni i uroven' kortikosteroidov v krovi éksperimental'nykh zhivotnykh v usloviiakh vozdeistviia fizicheskimi faktorami.

In experiments on male Wistar rats it has been found that physical factors applied in medicine (laser radiation of low intensity with wave length 0.89 microns, microwaves of centimeter range of 2450 MHz, and ultrasound of low intensity 880 KHz) changed catalytic activity of liver microsomal and rostenedione 16 alpha- and 6 beta-hydroxylating cytochromes P-450h and P-450p and blood corticosteroids level. Activities of these two steroid-metabolizing cytochromes decreased under ultrasonic skin application on liver region and increased under microwave and laser action. Contents of physiologically inactive form of corticosterone were not changed by the physical factors action while level of active hormone was increased under ultrasonic and microwave action. These findings suggest association of the activity of liver steroid-metabolizing cytochromes P-450 and level of physiologically active form of corticosterone in blood under physical factors skin application on liver region.