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.     

Uptake and loss of technetium-95m in the crab Pachygrapsus marmoratus

The uptake and loss kinetics of ^95mTc in seawater have been investigated in the crab Pachygrapsus marmoratus. Both the uptake and loss kinetics can be represented as the sum of two exponential functions, one short-term ($\text{tb}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 16}\text{d}$) and one long-term ($\text{tb}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 63}\text{d}$), $\text{tb}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ being the biological half-time. The predicted steady state concentration factor was estimated to be about 18.No significant linear correlation between Tc uptake rate and animal weight was found during the accumulation phase. At the end of this phase, 77% of the Tc was found to be distributed in the digestive system and particularly in the hepatopancreas (56%); this organ also appeared to lose the radionuclide most quickly. During the loss phase, 90% of the incorporated radioactivity was eliminated in about three months. Therefore P. marmoratus does not appear to be a good bioindicator of Tc in the marine environment nor an important pathway for Tc contamination along marine food chains.     

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.     

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.     

Natural and anthropogenic radionuclides in airborne particulate samples collected in Barcelona (Spain)

Results for naturally occurring ⁷Be, ²¹⁰Pb, ⁴⁰K, ²¹⁴Bi, ²¹⁴Pb, ²¹²Pb, ²²⁸Ac and ²⁰⁸Tl and anthropogenic ¹³⁷Cs in airborne particulate matter in the Barcelona area during the period from January 2001 to December 2005 are presented and discussed. The ²¹²Pb and ²⁰⁸Tl, ²¹⁴Bi and ²¹⁴Pb, ⁷Be and ²¹⁰Pb radionuclide levels showed a significant correlation with each other, with correlation coefficients of 0.99, 0.78 and 0.69, respectively, suggesting similar origin/behaviour of these radionuclides in the air. Caessium-137 and Potassium-40 were transported to the air as resuspended particle from the soil. The ⁷Be and ²¹⁰Pb concentrations showed similar seasonal variations, with a tendency for maximum concentrations during the summer months. An inverse relationship was observed between the ⁷Be, ²¹⁰Pb, ⁴⁰K and ¹³⁷Cs concentrations and weekly rainfall, indicating washout of atmospheric aerosols carrying these radionuclides.     

Temporal variation of 212Pb concentration in outdoor air of Milan and a comparison with 214Bi

Continuous measurement of hourly concentrations of 212Pb attached to aerosol particles was carried out during the whole year 2000 in the outdoor air of Milan (Italy). An improved experimental method based on on-line alpha spectroscopy during atmospheric particulate matter sampling allowed the contemporary determination of 212Pb and 214Bi through the deconvolution of the alpha energy spectral distribution analysis. The 212Pb hourly concentrations were about 100 times lower than 214Bi but showed a similar characteristic diurnal time trend. However, the influence of meteorological parameters such as rain and wind was more evident in 212Pb than in 214Bi concentrations. The 212Pb average annual concentration was 0.090 +/- 0.060 Bq/m3 with daily mean concentration varying from 0.013 to 0.333 Bq/m3.     

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.     

Po-210 and Pb-210 as atmospheric tracers and global atmospheric Pb-210 fallout: a review

Over the past ∼5 decades, the distribution of ²²²Rn and its progenies (mainly ²¹⁰Pb, ²¹⁰Bi and ²¹⁰Po) have provided a wealth of information as tracers to quantify several atmospheric processes that include: i) source tracking and transport time scales of air masses; ii) the stability and vertical movement of air masses iii) removal rate constants and residence times of aerosols; iv) chemical behavior of analog species; and v) washout ratios and deposition velocities of aerosols. Most of these applications require that the sources and sink terms of these nuclides are well characterized.Utility of ²¹⁰Pb, ²¹⁰Bi and ²¹⁰Po as atmospheric tracers requires that data on the ²²²Rn emanation rates is well documented. Due to low concentrations of ²²⁶Ra in surface waters, the ²²²Rn emanation rates from the continent is about two orders of magnitude higher than that of the ocean. This has led to distinctly higher ²¹⁰Pb concentrations in continental air masses compared to oceanic air masses. The highly varying concentrations of ²¹⁰Pb in air as well the depositional fluxes have yielded insight on the sources and transit times of aerosols. In an ideal enclosed air mass (closed system with respect to these nuclides), the residence times of aerosols obtained from the activity ratios of ²¹⁰Pb/²²²Rn, ²¹⁰Bi/²¹⁰Pb, and ²¹⁰Po/²¹⁰Pb are expected to agree with each other, but a large number of studies have indicated discordance between the residence times obtained from these three pairs. Recent results from the distribution of these nuclides in size-fractionated aerosols appear to yield consistent residence time in smaller-size aerosols, possibly suggesting that larger size aerosols are derived from resuspended dust. The residence times calculated from the ²¹⁰Pb/²²²Rn, ²¹⁰Bi/²¹⁰Pb, and ²¹⁰Po/²¹⁰Pb activity ratios published from 1970’s are compared to those data obtained in size-fractionated aerosols in this decade and possible reasons for the discordance is discussed with some key recommendations for future studies.The existing global atmospheric inventory data of ²¹⁰Pb is re-evaluated and a ‘global curve’ for the depositional fluxes of ²¹⁰Pb is established. A current global budget for atmospheric ²¹⁰Po and ²¹⁰Pb is also established. The relative importance of dry fallout of ²¹⁰Po and ²¹⁰Pb at different latitudes is evaluated. The global values for the deposition velocities of aerosols using ²¹⁰Po and ²¹⁰Pb are synthesized.     

Relationship between variations of Be, Pb and Pb concentrations and sub-regional atmospheric transport: Simultaneous observation at distant locations

In order to investigate the applicability of ²¹²Pb as a tracer for atmospheric transport in the sub-regional scale (few hundred kilometers in horizontal direction and up to ∼1 km by height), we measured the air concentrations of the short-lived radionuclide ²¹²Pb along with the long-lived ⁷Be and ²¹⁰Pb near the ground surface. For this purpose, simultaneous observations were continued for several days at three locations: a reference point representative for standard land surface atmosphere conditions, a second location at an altitude 650 m near the reference point, and on a solitary island ∼180 km from the reference point. Measurements of radioactivity in aerosol particle samples collected at intervals of 2-3 h with a high-volume air sampler were performed by extremely low background gamma-ray spectrometry with the use of Ge detectors located at the Ogoya Underground Laboratory. Concentration of ⁷Be or ²¹⁰Pb and their variation patterns was found to be similar among the three points during the whole observation period except for moment of the passage of a cold front. The results indicate that distributions of concentrations of the long-lived nuclides were uniform in this range. On the other hand, concentration levels and the variation patterns of the short-lived ²¹²Pb differed greatly from one location to another, reflecting differences in geographical location and altitude of the observation points. Additionally, there were certain indications that observed concentration of ²¹²Pb contained two components: an autogenous component from sources nearby and a heterogenous one from faraway sources carried by atmospheric horizontal transport. Results of this study provide experimental proof that ²¹²Pb can be used as a tracer of sub-regional atmospheric transport.     

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.     

The sources and fate of 210Po in the urban air: A review

The origin of ²¹⁰Po activity and its fluctuations in the air are discussed in this paper. In the case of atmospheric aerosol samples, a comparison of the ²¹⁰Po/²¹⁰Pb and ²¹⁰Bi/²¹⁰Pb activity ratios makes it possible not only to determine aerosol residence times but also to appraise the contribution of the unsupported ²¹⁰Po coming from other sources than ²²²Rn decay, such as human industrial activities, especially coal combustion. A simple mathematical method makes it possible to observe the seasonal fluctuations of the anthropogenic excess of ²¹⁰Po in the urban air. The average doses of ²¹⁰Po intake with food (including drinking water) and inhalation of urban aerosols are usually lower than those from ²¹⁰Po intake by cigarette smokers and negligible in comparison to total natural radiation exposure.     

Pre-concentration of naturally occurring radionuclides and the determination of (212)Pb from fresh waters

A novel technique has been developed for determining the ²¹²Pb activity of fresh waters. This is of interest to environmental monitoring programmes that utilise gross α-activity methods to screen for anthropogenic radionuclides. The contribution from ²¹²Pb varies, and is difficult to experimentally measure due to its relatively short half-life (t_½ = 10.6 h) and low environmental activity (<0.1 Bq l⁻¹). The use of a three-stage technique that encompasses a unique form of pre-concentration, separation and analysis by liquid scintillation counting allows a lower detection limit of 0.006 Bq l⁻¹ with a chemical yield of 92.5 ± 5.6%. The measurement can be obtained within 7 h of sample collection, and is calculated using the radioactive decay of ²¹²Bi. Other naturally occurring radionuclides may also be extracted using the pre-concentration stage of the technique, with efficiencies above 90% at a range of pH values.     

Seasonal variation of 210Pb activity concentration in outdoor air of Milan (Italy)

Weekly measurements of 210Pb activity concentration on aerosol particles were performed at ground level in outdoor air in Milan (Italy) during the years 2000-2001. The experimental method was based on the delayed alpha spectrometry of in-grown 210Po activity detected on airborne particles collected on a filter support. On the same filter the 214Pb activity concentration was also measured during the sampling. 210Pb weekly concentration values showed a great variability and the average monthly values exhibited a seasonal pattern characterised by maxima in winter and minima in spring-summer. The same seasonal trend was also observed in 214Pb concentration values. 210Pb average yearly values were 0.70 and 0.82 mBq/m3 in 2000 and 2001, respectively, in good agreement with literature data registered at continental sites of similar latitude and longitude. The activity ratio 210Pb/214Pb was used to evaluate the residence time of fine aerosols in the urban air of Milan, which was 1-2 days.     

Observations and modelling of thoron and its progeny in the soil-atmosphere-plant system

Samples of pasture vegetation, mainly Trifolium pratensis, were collected at the Botanic Garden of the University of Bologna during the period 1998-2000 and measured by gamma-spectrometry for determining thoron progeny. Concentrations of ²¹²Pb were between 1.5 and 20 Bq m⁻², with individual peaks up to 70 Bq m⁻². Soil samples were collected at the same location and physically characterised. Their chemical composition (particularly Th and U) was determined by X-ray fluorescence spectroscopy. Lead-212 on plants mainly originates from dry and wet deposition of this isotope generated in the lower atmosphere by the decay of its short-lived precursor ²²⁰Rn, which is produced in the upper soil layers as a member of the natural thorium decay chain and exhales into the atmosphere. Concentrations of ²²⁰Rn in the atmosphere depend on (1) the amount of Th present in soil, (2) the radon fraction which escapes from the soil minerals into the soil pore space, (3) its transport into the atmosphere, and (4) its redistribution within the atmosphere. The mobility of radon in soil pore space can vary by orders of magnitude depending on the soil water content, thus being the main factor for varying concentrations of ²²⁰Rn and ²¹²Pb in the atmosphere. We present a simple model to predict concentrations of thoron in air and its progeny deposited from the atmosphere, which takes into account varying soil moisture contents calculated by the OPUS code. Results of this model show close agreement with our observations.     

Krypton-85 in the atmosphere 1950–1977: a data review

For over 20 years the radioactive noble gas ⁸⁵Kr, the product of nuclear industry, has been released to the environment mainly from nuclear fuel reprocessing plants. Owing to its relatively long half-life $\text{T(}\text{1}\text{2}\text{= 10.76}\text{y}\text{)}$ and the absence of other appreciable sinks, a cumulative buildup of ⁸⁵Kr in the atmosphere is observed. The mean ⁸⁵Kr surface air activity in the northern hemisphere has increased from about 20 dpm/mmol Kr in 1950 to about 750 dpm/mmol Kr in 1977. In recent years, a substantial slow-down of the ⁸⁵Kr emission rate to the atmosphere has been observed. The published data indicate rather good mixing of ⁸⁵Kr in the northern hemisphere, but a gradient is observed in the southern hemisphere due to the fact that all nuclear fuel reprocessing plants are situated in the northern hemisphere and due to poor mixing of the atmosphere in the meridional direction.This paper summarizes nearly all of the data on ⁸⁵Kr activity in the atmosphere published up to the middle of 1978. The spatio-temporal distribution of ⁸⁵Kr atmospheric activity is discussed. Some forecasts of future ⁸⁵Kr concentration in the atmosphere and its possible ecological consequences are also presented.     

Recent atmospheric lead deposition recorded in an ombrotrophic peat bog of Great Hinggan Mountains, Northeast China, from Pb and Cs dating

Radioactive markers are useful in dating lead deposition patterns from industrialization in peat archive. Peat cores were collected in an ombrotrophic peat bog in the Great Hinggan Mountains in Northeast China in September 2008 and dated using ²¹⁰Pb and ¹³⁷Cs radiometric techniques. The mosses in both cores were examined systematically for dry bulk density, water and ash content. Lead also was measured using atomic emission spectroscopy with inductively coupled plasma (ICP-AES). Both patterned peat profiles were preserved well without evident anthropogenic disturbance. Unsupported ²¹⁰Pb and ¹³⁷Cs decreased with the depth in both of the two sample cores. The ²¹⁰Pb chronologies were established using the constant rate of supply model (CRS) and are in good agreement with the ¹³⁷Cs time marker. Recent atmospheric ²¹⁰Pb flux in Great Hinggan Mountains peat bog was estimated to be 337 Bq m⁻² y⁻¹, which is consistent with published data for the region. Lead deposition rate in this region was also derived from these two peat cores and ranged from 24.6 to 55.8 mg m⁻² y⁻¹ with a range of Pb concentration of 14-262 μg g⁻¹. The Pb deposition patterns were consistent with increasing industrialization over the last 135-170 y, with a peak of production and coal burning in the last 50 y in Northeast China. This work presents a first estimation of atmospheric Pb deposition rate in peatlands in China and suggests an increasing trend of environmental pollution due to anthropogenic contaminants in the atmosphere. More attention should be paid to current local pollution problems, and society should take actions to seek a balance between economic development and environmental protection.