Determination of 99Tc, 63Ni and 121m+126Sn in the marine environment

Four artificially produced radionuclides (${}^{99}\text{Tc, t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 2·15 × 10}{}^5\text{y;}{}^{63}\text{Ni, t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 93 y}$ and ${}^{\mathrm{121m+126}}\text{Sn, t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 55·5 y}$) have been analyzed in sediments and organisms from the marine environment. The samples were obtained from the vicinities of nuclear energy facilities, at sites of nuclear weapon tests and at sites remote from both of these locales. The activities of these nuclides per unit dry weight are remarkably similar at the first two of the above areas but are usually detectable only with difficulty, if at all, in the third area. Techniques for sample treatment and measurement are given.     

Experimental studies on the bioaccumulation of plutonium from sea water and a deep-sea sediment by clams and polychaetes

The bioavailability of ²³⁷Pu in the (III + IV) and (V + VI) oxidation states from sea water and a NE Atlantic deep-sea sediment has been studied for clams (Venerupis decussata) and polychaete worms (Hermione hystrix). After 22 days' exposure in sea water transfer factors (TF) had not reached equilibrium, and were 74 ± 5 and 61 ± 1 for clams and 370 ± 10 and 275 ± 11 for polychaetes, for Pu (III + IV) and Pu (V + VI) respectively. Depuration rates after sea water exposure followed a single exponential form ($\text{T}{}_{\mathrm{<mtext>b</mtext><mtext>1</mtext><mtext>2</mtext>}}\text{= 50}\text{days}$) for clams, and for polychaetes at least a two component from with $\text{T}{}_{\mathrm{<mtext>b</mtext><mtext>1</mtext><mtext>2</mtext>}}\text{= 1·3}\text{days}$ and 54 days. TF values for ²³⁷Pu bioaccumulation from sediments were very low, 6 × 10^?3 and 5 × 10^?2 for clams and polychaetes, respectively, after 20 days' exposure.Plotonium appears to be about 50% more bioavailable to the same species than americium as measured by laboratory experiments using a similar deep-sea sediment. Depuration experiments with clams after 40 days' exposure to labelled sediment indicated loss followed a single exponential form with a $\text{T}{}_{\mathrm{<mtext>b</mtext><mtext>1</mtext><mtext>2</mtext>}}\text{= 24}\text{days}$. Significant differences in the behaviour of Pu introduced into the uptake and loss experiments in different oxidation states were not observed in general.     

Nonidentifiability of competing risks

Frequently one is interested in examining the survival experience of a set of individuals exposed to k risks. If W is the time of failure for the individual and J is the indicator variable for cause of death, then the competing risk framework assumes that W = min X_i and J = j if X_j is the minimum, where the X_i's are the survival lifetimes when only risk R_i is operating on the population. To examine the underlying structure of the survival experience one has to know the joint distribution of the $\text{X}{}_{\mathrm{i}}\text{(F}{}_{\mathrm{<mtext>x</mtext>}}\text{)}$. It is shown here that if only W and J are observed, the joint distribution of the $\text{X}{}_{\mathrm{i}}\text{(F}{}_{\mathrm{<mtext>x</mtext>}}\text{)}$ is nonidentifiable.     

Air-to-vegetation transfer rates of natural submicron aerosols

Submicron aerosol deposition to outdoor vegetation was evaluated by measuring vegetation and air concentrations of ²¹²Pb, ²¹⁴Pb, and ⁷Be attached to atmospheric aerosols. A biomass-normalized deposition velocity (V_D), with units of m³ kg^?1 s^?1, was used to compare species and isotopes with respect to air-to-vegetation transfer rates. For ²¹²Pb ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 10·64 h}$), higher night-time air concebtrations dominate deposition, while for ²¹⁴Pb ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 26·8}\text{min}$), deposition measurements over shorter time periods relative to changing atmospheric conditions were possible. Calculated V_D values were usually higher for ²¹⁴Pb, possibly reflecting wind-enhanced deposition during the afternoon period of sampling. Evergreen species, including pines, were not appreciably different from deciduous species. Most striking was the narrow range of results (factor of 6 for 34 ²¹²Pb measurements of 20 species). Beryllium-7 ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 53·3 d}$) was used to evaluate time-integrated deposition by sampling vegetation in California near the end of dry summers. Similar deposition rates were found for this isotope. The results of the study indicated that naturally radioactive atmospheric aerosols can be used to understand the dynamics of submicron aerosol deposition to ecosystems.     

Threshold and dose response estimation using the “filter model”

The “filter model” has been developed to explain the biologic effects of radiation and chemicals. We have examined nearly 300 sets of dose response data, of which 50 are presented here. Responses (induced by radiation and chemicals) which have been examined include in vitro survival studies on animal and plant tissues, induction of cellular aberrations and time to tumor or death. Similar data from in vivo studies has also been examined. All of the data appear to fit the model R = a lnD + b(lnD)² + c, where R is the response, a and b are parameters fitted by regression to a particular set of data, and c is the response at zero (or lowest) dose. By writing this model in exponential form, it can be seen that the response R results from multistage filtering (by net amounts a and b) of the initial dose, D. The threshold is obtained from this model as the point, $\text{D}\text{?}{}_{\mathrm{T}}$, at which the second derivative becomes zero. This is given by $\text{D}\text{?}{}_{\mathrm{T}}\text{=}\text{exp}\text{(1 ?}\text{a}\text{2b}\text{)}$ when a and b are oppositelt signed.     

Comparing computing formulas for estimating concentration ratios

The purpose of this paper is to provide guidance on the choice of computing formulas (estimators) for estimating average concentration ratios and other ratio-type measures of radionuclides and other environmental contaminant transfers between ecosystem components. Mathematical expressions for the expected value of three commonly used estimators (arithmetic mean of ratios, geometric mean of ratios, and the ratio of means) are obtained when the multivariate lognormal distribution is assumed. These expressions are used to explain why these estimators will not in general give the same estimate of the average concentration ratio. They illustrate that the magnitude of the discrepancies depends on the magnitude of measurement biases, and on the variance and correlations associated with spatial heterogeneity and measurement errors. This paper also reports on a computer simulation study that compares the accuracy of eight computing formulas for estimating a ratio relationship that is constant over time and/or space. Statistical models appropriate for both controlled spiking experiments and observational field studies for either normal or lognormal distributions are considered. Our results indicate that for either type of study the geometric mean is generally preferred if the lognormal distribution applies. However, the geometric mean has the disadvantage that its expected value depends on n, the number of measurements taken. Ricker's estimator, $\text{R}\text{?}{}_{\mathrm{rt}}$, appears to perform worse than the other estimators studied when the observations are lognormal. All eight estimators appear to be equally accurate for the controlled spiking study when data are normally distributed. For observational field studies when data are normally distributed the ratio of means or slight modifications thereof are preferred to other estimators investigated. Before one chooses a computing formula for estimating a concentration ratio, thought should be given to what target value needs to be estimated to satisfy study objectives, and to whether the normal or lognormal distribution is a more realistic model. The geometric mean performs well for lognormal distributions, but comparison of geometric means or of a geometric mean with environmental limits can be misleading if n is small. The arithmetic mean of ratios is a conservative choice in that it will always give a larger estimate than will the geometric mean. It may also be severely biased when data are lognormal and the variances of measurement errors are large. The ratio of the means is a reasonable choice if the distribution is normal. The median of the observed ratios, $\text{R}\text{?}{}_{\mathrm{<mtext>md</mtext>}}$, is useful estimate since it is easily obtained and has an easily understood interpretation as the point above which and below which 50% of the observed ratios lie. Also, it is appropriate no matter what the distribution of the observed ratios may be. Confidence limits on the median are also easily obtained. Finally, while this paper emphasizes applications in radionuclide research, our results should be applicable to a wide range of environmental contaminants since many contaminants have approximately lognormal distributions.     

Statistical assessment of subsampling procedures

As shown by the examples in this paper, the concentrations in subsamples are not necessarily independently and normally distributed despite vigorous grinding and mixing of the original sample. Studies of the statistical properties of subsample concentrations should test for deviations from independence and normality and, if deviations are found, should model the observed distribution. The tests include an analysis of variance to check for less variation among nearby subsamples than among widely spaced subsamples, as well as the computation of the probability plot correlation coefficient to check for nonnormality. These tests are illustrated with ${}^{239}\text{Pu}\text{+}{}^{240}\text{Pu}$ measurements on subsamples prepared for use as standard reference materials. These materials are used in quality assurance for environmental radioactivity measurements. The material consisting of Human Liver (SRM 4352) exhibits dependence, which may be due to inadequate mixing or to later handling that caused segregation. The material consisting of Human Lung (SRM 4351) and the material consisting of soil from Rocky Flats (SRM 4353) exhibit nonnormality due to the particulate nature of some plutonium-bearing fractions of the material. The lung measurements are modeled with the gamma distribution. The soil measurements are modeled with a combination of the normal distribution and a distribution that models the occurrence of outliers. The use of these models to describe the subsamples involves assessment of the contribution of the measurement error.     

A review of the biological and geochemical behavior of technetium in the Marine environment

Present understanding of the behavior of Tc in the marine environment is summarized. The prevalent valence state of Tc in oxygenated seawater is +7, arguing that pertechnetate ion, TcO₄⁻, represents the most likely form of this radioelement in seawater. Laboratory experiments using radiolabeled pertechnetate ion have shown that binding of this anion to different classes of marine sediments is slight. Concentration factors for the majority of marine organisms studied to date are small; notable exceptions are seen in certain species of brown algae, polychaetes and macrocrustaceans. Uptake and loss kinetics are generally rapid with the majority of the Tc being associated with shell, exoskeleton and gut. There are, as yet, no data supporting the contention that stable element analogs such as iodate can be used to predict the long-term behavior of ⁹⁹Tc (as pertechnetate) in the marine environment.     

Variability of the sorption of Cs, Zn, Sr, Co, Cd, Ce, Ru, Tc and I at trace concentrations by a forest soil along a transect

The variability of the sorption properties (characterized by the distribution coefficient K_d) of a forest soil for Cs, Zn, Sr, Co, Cd, Ce, Ru, Tc, and I were determined along a transect of 150 m in regular intervals of 3 m. Radioactive tracers were used to ensure trace concentrations of these elements. For comparison, for each soil sample the loss on ignition, as a measure of the soil organic matter content, and the pH were also determined. On average, the K_d values increase in the sequence Tc < I < Ru ≈ Co ≈ Zn ≈ Sr < Cd < Ce < Cs; the spatial variability in the sequence I < Zn ≈ Sr ≈ Co ≈ Cd ≈ Ru ≈ Tc < Cs, and I ≈ Ce < Tc. Correlation analysis revealed that, when moving along the transect, the K_d values for some elements changed in a similar, and for others in a dissimilar pattern. In a few cases a correlation between the pH or the loss on ignition and the K_d values was also present. The spatial structure of the data was examined by semivariograms. For the elements Co, Cd, Zn, and Sr, the K_d values showed an almost periodic behaviour along the transect, which is probably due to periodic changes of some soil properties in a forest with regularly spaced trees.     

Bioavailability of sediment-associated and low-molecular-mass species of radionuclides/trace metals to the mussel Mytilus edulis

Sediments can act as a sink for contaminants in effluents from industrial and nuclear installations or when released from dumped waste. However, contaminated sediments may also act as a potential source of radionuclides and trace metals to the water phase due to remobilisation of metals as dissolved species and resuspension of particles. The marine mussel Mytilus edulis is a filter-feeding organism that via the gills is subjected to contaminants in dissolved form and from contaminants associated to suspended particles via the digestive system. In this paper the bioavailability of sediment-associated and seawater diluted Cs, Co, Cd and Zn radioactive tracers to the filtering bivalve M. edulis has been examined. The mussels were exposed to tracers diluted in ultrafiltered (<10 kDa) seawater (Low Molecular Mass form) or to tracers associated with sediment particles from the Stepovogo Fjord at Novaya Zemlya in short-term uptake experiments, followed by 1-month depuration experiments in flow-through tanks. A toxicokinetic model was fitted to the uptake and depuration data, and the obtained parameters were used to simulate the significance of the two uptake pathways at different suspended sediment loads and sediment-seawater distribution coefficients. The results of the model simulations, assuming steady state conditions, suggest that resuspended particles from contaminated sediments can be a highly significant pathway for mussels in the order ¹⁰⁹Cd ≌ ⁶⁵Zn < ¹³⁴Cs < ⁶⁰Co. The significance increases with higher suspended sediment load and with higher K_d. Furthermore, the experimental depuration data suggest that Cs is retained longer and Co, Cd and Zn shorter by the mussels when associated with ingested sediments, than if the metals are taken up from the low molecular mass (LMM) phase.     

Environmental fate and distribution of technetium-99 in a deciduous forest ecosystem

The aims of the present research are to describe the uptake of ⁹⁹Tc by trees intercepting contaminated groundwater from a radioactive waste storage site, to identify the major ⁹⁹Tc pools within the woodland ecosystem and to assess the relative mobility of ⁹⁹Tc in the existing element cycle. Technetium in the groundwater freely passed through a dialysis membrane with a molecular weight exclusion limit of approximately 3500 amu and ⁹⁹Tc in the groundwater chromatographed on Biogel P-2 in a manner similar to pertechnetate anion (TcO₄⁻). Reducing conditions and organic associations at the study site were probably responsible for the relatively large amount (83–92%) of the ⁹⁹Tc that was nonextractable from soil by 0·01 m CaCl₂. More than one-third of the ⁹⁹Tc was released from the soil by oxidizing reagents, indicating the presence of chemically reduced forms. The highest average ⁹⁹Tc concentrations in vegetation were found in herbaceous plants (18 530 pCi g⁻¹ dry wt). Although ⁹⁹Tc was progressively accumulated over the growing season in tree leaves, average concentrations in tree wood and twigs were equal to or greater than concentrations in leaves. Tree wood was the major above-ground pool for ⁹⁹Tc because of the high concentrations in wood as well as the large amount of wood relative to other biomass at the site. Technetium was not easily leached from the trees by rainfall and was not readily extractable from forest floor leaf litter by water. The relative importance of return pathways for ⁹⁹Tc to the forest floor was leaf fall>stemflow >throughfall, indicating that ⁹⁹Tc was conserved by the trees. Snails and millipedes from the leaf litter layer concentrated technetium 20- and 16-fold, respectively, above levels found in the soil. Pertechnetate was rendered less bioavailable after ingestion by a leaf litter macroinvertebrate (Porcellio sp.) common to the study site.