Pu/Cs ratios in the water column of the North Pacific: a proxy of biogeochemical processes

Anthropogenic radionuclides in seawater have been used as transient tracers of processes in the marine environment. Especially, plutonium in seawater is considered to be a valuable tracer of biogeochemical processes due to its particle-reactive properties. However, its behavior in the ocean is also affected by physical processes such as advection, mixing and diffusion. Here we introduce Pu/¹³⁷Cs ratio as a proxy of biogeochemical processes and discuss its trends in the water column of the North Pacific Ocean. We observed that the ^239,240Pu/¹³⁷Cs ratio in seawater exponentially increased with increasing depth (depth range: 100–1000 m). This finding suggests that the profiles of the ^239,240Pu/¹³⁷Cs ratios in shallower waters directly reflect biogeochemical processes in the water column. A half-regeneration depth deduced from the curve fitting the observed data, showed latitudinal and longitudinal distributions, also related to biogeochemical processes in the water column.     

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.     

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.     

Sources of anthropogenic radionuclides in the environment: a review

Studies of radionuclides in the environment have entered a new era with the renaissance of nuclear energy and associated fuel reprocessing, geological disposal of high-level nuclear wastes, and concerns about national security with respect to nuclear non-proliferation. This work presents an overview on sources of anthropogenic radionuclides in the environment, as well as a brief discussion of salient geochemical behavior of important radionuclides. We first discuss the following major anthropogenic sources and current developments that have lead, or could potentially contribute, to the radionuclide contamination of the environment: (1) nuclear weapons program; (2) nuclear weapons testing; (3) nuclear power plants; (4) uranium mining and milling; (5) commercial fuel reprocessing; (6) geological repository of high-level nuclear wastes that include radionuclides might be released in the future, and (7) nuclear accidents. Then, we briefly summarize the inventory of radionuclides ⁹⁹Tc and ¹²⁹I, as well as geochemical behavior for radionuclides ⁹⁹Tc, ¹²⁹I, and ²³⁷Np, because of their complex geochemical behavior, long half-lives, and presumably high mobility in the environment; biogeochemical cycling and environment risk assessment must take into account speciation of these redox-sensitive radionuclides.     

Movement of pertechnetate through soils: Hydrodynamic dispersion

Measurement of the hydrodynamic dispersion of pertechnetate (⁹⁹TcO^?₄) migrating towards the water-table complements other investigations of the partition of pertechnetate between soil solution and soil colloids. This study was performed on soil columns equilibrated with distilled water and through which a solution of ⁹⁹TcO₄NH₄ or ³⁶ClNa was percolated at constant rate. A theoretical elution curve was adjusted to the experimental points obtained from a sand column. An estimate could thus be made of the parameters characterizing the migration of pertechnetate. The model used here considered the presence of a ‘dead water’ zone in the column into which the solute penetrates by molecular diffusion only at a given rate. The elution curves obtained experimentally and theoretically have been compared with those for a non-reactive anion, ³⁶Cl^?. A simulationof the change of pertechnetate concentration in the eluate has been made for increasing values of the retention factor. The calculated curves confirm the very low mobility of this anion in soil.     

Vertical distributions of (99)Tc and the (99)Tc/(137)Cs activity ratio in the coastal water off Aomori, Japan

Using a sector-field ICP-MS the vertical distributions of the ⁹⁹Tc concentration and ⁹⁹Tc/¹³⁷Cs activity ratio were measured in the coastal waters off Aomori Prefecture, Japan, where a spent-nuclear-fuel reprocessing plant has begun test operation. The ⁹⁹Tc concentrations in surface water ranged from 1.8 to 2.4 mBq/m³, no greater than the estimated background level. Relatively high ⁹⁹Tc/¹³⁷Cs activity ratios (10-12 × 10⁻⁴) would be caused by the inflow of the high-⁹⁹Tc/¹³⁷Cs water mass from the Japan Sea. There is no observable contamination from the reprocessing plant in the investigated area. The ⁹⁹Tc concentration and the ⁹⁹Tc/¹³⁷Cs activity ratio in water column showed gradual decreases with depth. Our results implied that ⁹⁹Tc behaves in a more conservative manner than ¹³⁷Cs in marine environments.     

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.     

Dose assessment for marine biota and humans from discharge of (131)I to the marine environment and uptake by algae in Sydney, Australia

Iodine-131 reaches the marine environment through its excretion to the sewer by nuclear medicine patients followed by discharge through coastal and deepwater outfalls. ¹³¹I has been detected in macroalgae, which bio-accumulate iodine, growing near the coastal outfall of Cronulla sewage treatment plant (STP) since 1995. During this study, ¹³¹I levels in liquid effluent and sludge from three Sydney STPs as well as in macroalgae (Ulva sp. and Ecklonia radiata) growing near their shoreline outfalls were measured. Concentration factors of 176 for Ulva sp. and 526 for E. radiata were derived. Radiation dose rates to marine biota from ¹³¹I discharged to coastal waters calculated using the ERICA dose assessment tool were below the ERICA screening level of 10 μGy/hr. Radiation dose rates to humans from immersion in seawater or consumption of Ulva sp. containing ¹³¹I were three and two orders of magnitude below the IAEA screening level of 10 μSv/year, respectively.     

Plutonium isotopes concentration in seawater and bottom sediment off the Pacific coast of Aomori sea area during 1991-2005

A radioactivity survey was launched in 1991 to determine the background levels of ^239+240Pu in the marine environment off a commercial spent nuclear fuel reprocessing plant before full operation of the facility. Particular attention was focused on the ²⁴⁰Pu/²³⁹Pu atom ratio in seawater and bottom sediment to identify the origins of Pu isotopes. The concentration of ^239+240Pu was almost uniform in surface water, decreasing slowly over time. Conversely, the ^239+240Pu concentration varied markedly in the bottom water and was dependent upon the sampling point, with higher concentrations of ^239+240Pu observed in the bottom water sample at sampling points having greater depth. The ²⁴⁰Pu/²³⁹Pu atom ratio in the seawater and sediment samples was higher than that of global fallout Pu, and comparable with the data in the other sea area around Japan which has likely been affected by close-in fallout Pu originating from the Pacific Proving Grounds. The ²⁴⁰Pu/²³⁹Pu atom ratio in bottom sediment samples decreased with sea depth. The land-originated Pu is not considered as the reason of the increasing ^239+240Pu concentration and also decreasing the ²⁴⁰Pu/²³⁹Pu atom ratio with sea depth, and further study is required to clarify it.     

The concentration of Cs in the surface of the Greek marine environment

The radiological status of the Greek marine environment, prior to the Chernobyl accident, was characterized mainly by the fallout from nuclear weapon tests. However, the release of radioactivity into the environment from the accident in the Chernobyl Nuclear Power Plant and its deposition in the Greek marine environment resulted in an increase of the ¹³⁷Cs activity concentration by approximately one order of magnitude. In addition, the direct transport of radiocaesium into the North Aegean Sea has been further influenced by the late impact of the Chernobyl accident on the Greek marine environment, related to the transfer of ¹³⁷Cs, mainly through the Dnieper but also the Danube rivers, to the Black Sea and further to the North Aegean Sea through the Straits of Dardanelles. The aim of this work is to provide a present day picture of the geographic variation of the concentration of ¹³⁷Cs in the surface layer of the Greek marine environment and hence, to evaluate the annual committed effective dose delivered to humans through the ingestion pathway from marine sources.     

Solid partitioning and solid-liquid distribution of Po and Pb in marine anoxic sediments: roads of Cherbourg at the northwestern France

A sequential extraction protocol has been used to determine the solid-phase partition of ²¹⁰Po and ²¹⁰Pb in anoxic marine sediment from the roads of Cherbourg (France) in the central English Channel. Measurements were also obtained in pore waters, in which ²¹⁰Po activities range between 1 and 20 mBq L⁻¹ and ²¹⁰Pb activities between 2.4 and 3.8 mBq L⁻¹, with highest activities in the topmost layer. These activities are higher than in seawater, suggesting that sediment act as a source of both ²¹⁰Po and ²¹⁰Pb for overlying water. The ²¹⁰Po profile in the pore waters is apparently correlated with those obtained for Fe, Mn and SO₄²⁻, suggesting an influence of early diagenetic processes on the ²¹⁰Po solid-liquid distribution. In the sediment, ²¹⁰Po is predominantly bound to organic matter or chromium reducible sulphides, and residuals (clay minerals and refractory oxides). Our results indicate that ²¹⁰Po is not significantly bound to AVS, i.e. acid volatile sulphides: bioturbation could play a role by the early redistribution of ²¹⁰Po bound to acid volatile sulphides in the sediment. ²¹⁰Po, ²¹⁰Pb and Pb exhibit differences in terms of distribution, probably due to a different mode of penetration in the sediment. This work provides information on solid and liquid distribution of ²¹⁰Po and ²¹⁰Pb in marine sediment. These data are very scarce in the litterature.     

137Cs in marine samples from the Brazilian southeastern coastal region

The present work presents the results of ¹³⁷Cs concentration in seawater, fish and sediments samples collect in 11 sampling points, crossing the Brazilian Southeastern coastal region, from Vitória (ES) to Santos (SP), on a routine basis from 1997 to 2002. This monitoring program was carried out by the Instituto de Radioproteção e Dosimetria (IRD/CNEN/MCT), in cooperation with the Instituto de Estudos do Mar Almirante Paulo Moreira (IEAPM/Brazilian Navy), aiming at determining artificial radionuclides in marine samples. Additionally to the ¹³⁷Cs results, ⁹⁰Sr concentrations in fish samples from 1998 to 2002 are also reported.The ¹³⁷Cs in seawater follows a lognormal distribution, with a geometric mean of 1.8 Bq m^-3 and a geometric standard deviation of 1.4 (n=54), decay corrected to June/2002. For ¹³⁷Cs levels in fish samples a geometric mean of 0.19 Bq kg⁻¹ and a geometric standard deviation of 2.9 (n=39), decay corrected to June/2002, with a range of 0.03 to 1.7 Bq kg⁻¹, were obtained. Based on the ¹³⁷Cs mean concentration in fish as well as in seawater, a transfer factor of 1 × 10² was calculated, which is quite in agreement with the recommended value found in the Safety Report Serie 19.     

210Po in the marine environment with emphasis on its behaviour within the biosphere

The distribution and behaviour of the natural-series alpha-emitter polonium-210 in the marine environment has been under study for many years primarily due to its enhanced bioaccumulation, its strong affinity for binding with certain internal tissues, and its importance as a contributor to the natural radiation dose received by marine biota as well as humans consuming seafoods. Results from studies spanning nearly 5 decades show that ²¹⁰Po concentrations in organisms vary widely among the different phylogenic groups as well as between the different tissues of a given species. Such variation results in ²¹⁰Po concentration factors ranging from approximately 10³ to over 10⁶ depending upon the organism or tissue considered. ²¹⁰Po/²¹⁰Pb ratios in marine species are generally greater than unity and tend to increase up the food chain indicating that ²¹⁰Po is preferentially taken up by organisms compared to its progenitor ²¹⁰Pb. The effective transfer of ²¹⁰Po up the food chain is primarily due to the high degree of assimilation of the radionuclide from ingested food and its subsequent strong retention in the organisms. In some cases this mechanism may lead to an apparent biomagnification of ²¹⁰Po at the higher trophic level. Various pelagic species release ²¹⁰Po and ²¹⁰Pb packaged in organic biodetrital particles that sink and remove these radionuclides from the upper water column, a biogeochemical process which, coupled with scavenging rates of this radionuclide pair, is being examined as a possible proxy for estimating downward organic carbon fluxes in the sea. Data related to preferential bioaccumulation in various organisms, their tissues, resultant radiation doses to these species, and the processes by which ²¹⁰Po is transferred and recycled through the food web are discussed. In addition, the main gaps in our present knowledge and proposed areas for future studies on the biogeochemical behaviour of ²¹⁰Po and its use as a tracer of oceanographic processes are highlighted in this review.     

Colonized beads as inoculum for marine biodegradability assessment: Application to Linear Alkylbenzene Sulfonate

An innovative biodegradation test system was developed in order to fill the current gap for cost effective and environmentally relevant tools to assess marine biodegradability. Glass beads were colonized by a biofilm in an open flow-through system of seawater with continuous pre-exposure to Linear Alkylbenzene Sulfonate (LAS) (20 μg/L). Thereafter, such colonized beads were added as inoculum in different test systems. [¹⁴C]-LAS (5–100 μg/L) was added and primary and ultimate biodegradation were assessed. The bacterial density collected on the beads (10⁹ bact./mL beads) was ca. 3 orders of magnitude higher than the typical seawater content. The LAS mineralization lag phase duration decreased from 55 to < 1 days and the mineralization extent increased from 53 to 90% as the colonized beads volume increased from 10 to 275 mL. This is the first demonstration of marine bacteria's ability to mineralize LAS. On the opposite, less than 13% LAS was mineralized in seawater only. The colonized beads possibly enhanced the probability to encounter the full degraders' consortium in a low volume of seawater (100 mL).     

99Tc in the sub-arctic food chain Lichen-Reindeer-man

The deposition, migration and annual variations of ⁹⁹Tc fallout in carpets of lichen collected during the period 1956–1981 have been investigated. The transfer of ⁹⁹Tc to reindeer and man has also been studied. Technetium showed a shorter mean residence time than ¹³⁷Cs in the lichen carpet. The activity ratio ⁹⁹Tc/¹³⁷Cs was generally lower than the theoretical fission ratio of 1·43 × 10⁻⁴. The maximum concentration of ⁹⁹Tc in lichens occurred in 1967 (ca. 60 mBq kg⁻¹) but in 1975 higher values were found than would have been predicted from fallout. The average depth integrated concentration of ⁹⁹Tc at 62·3°N, 12·4° E in 1972 was 540 ± 100 mBq m⁻². The studies of reindeer tissues show that technetium has a short mean residence time in the muscle tissues (ca. 5 days) and is not accumulated like ¹³⁷Cs. The committed dose equivalent from ⁹⁹Tc to the local Lapp population engaged in reindeer breeding is negligible.     

Modelling the reworking effects of bioturbation on the incorporation of radionuclides into the sediment column: implications for the fate of particle-reactive radionuclides in Irish Sea sediments

A microcosm laboratory experiment was conducted to determine the impact of biological reworking by the ragworm Nereis diversicolor on the redistribution of particle-bound radionuclides deposited at the sediment-water interface. Over the course of the 40-day experiment, as much as 35% of a ¹³⁷Cs-labelled particulate tracer deposited on the sediment surface was redistributed to depths of up to 11 cm by the polychaete. Three different reworking models were employed to model the profiles and quantify the biodiffusion and biotransport coefficients: a gallery-diffuser model, a continuous sub-surface egestion model and a biodiffusion model. Although the biodiffusion coefficients obtained for each model were quite similar, the continuous sub-surface egestion model provided the best fit to the data. The average biodiffusion coefficient, at 1.8 ± 0.9 cm² y⁻¹, is in good agreement with the values quoted by other workers on the bioturbation effects of this polychaete species. The corresponding value for the biotransport coefficient was found to be 0.9 ± 0.4 cm y⁻¹. The effects of non-local mixing were incorporated in a model to describe the temporal evolution of measured ⁹⁹Tc and ⁶⁰Co radionuclide sediment profiles in the eastern Irish Sea, influenced by radioactive waste discharged from the Sellafield reprocessing plant. Reworking conditions in the sediment column were simulated by considering an upper mixed layer, an exponentially decreasing diffusion coefficient, and appropriate biotransport coefficients to account for non-local mixing. The diffusion coefficients calculated from the ⁹⁹Tc and ⁶⁰Co cores were in the range 2-14 cm² y⁻¹, which are consistent with the values found by other workers in the same marine area, while the biotransport coefficients were similar to those obtained for a variety of macrobenthic organisms in controlled laboratories and field studies.     

Assessing field-scale migration of radionuclides at the Nevada Test Site: “mobile” species

Many long-lived radionuclides are present in groundwater at the Nevada Test Site (NTS) as a result of 828 underground nuclear weapons tests conducted between 1951 and 1992. In conjunction with a comprehensive geochemical review of radionuclides (³H, ¹⁴C, ³⁶Cl, ⁹⁹Tc and ¹²⁹I) that are presumably mobile in the subsurface, we synthesized a body of radionuclide activity data measured from groundwater samples collected at 18 monitoring wells, to qualitatively assess their migration at the NTS over distances of hundreds of meters and over timescales of decades. Tritium and ³⁶Cl showed little evidence of retardation, while the transport of ¹⁴C may have been retarded by its isotopic exchange with carbonate minerals in the aquifer. Observed local reducing conditions (either natural or test-induced) will impact the mobility of certain redox-sensitive radionuclides (especially ⁹⁹Tc) that were otherwise soluble and readily transported under oxidizing conditions. Conversely, strongly oxidizing conditions may impact the mobility of ¹²⁹I which is mobile under reducing conditions. The effect of iodine speciation on its transport deserves further attention. Indication of delayed transport of some “mobile” radionuclides (especially ⁹⁹Tc) in the groundwater at the NTS suggested the importance of redox conditions of the natural system in controlling the fate and transport of radionuclides, which has implications in the enhanced performance of the potential Yucca Mountain repository, located adjacent to the NTS, to store high-level nuclear wastes as well as management of radionuclide contamination in legacy nuclear operations facilities.     

The effects of plant traits and phylogeny on soil-to-plant transfer of Tc

Assessments of the behaviour of ⁹⁹Tc in terrestrial environments necessitate predicting soil-to-plant transfer. An experiment with 116 plant taxa showed that ⁹⁹Tc transfer to plants was positively related to plant dry weight but negatively related to % dry matter and age at exposure. Activities of ⁹⁹Tc analysed by hierarchical ANOVA coded with an angiosperm phylogeny revealed significant effects, with 55% of the variance between species explained at the Ordinal level and above. Monocots had significantly lower transfer of ⁹⁹Tc than Eudicots, within which Caryophyllales > Solanales > Malvales > Brassicales > Asterales > Fabales. There was a significant phylogenetic signal in soil-to-plant transfer of ⁹⁹Tc. This phylogenetic signal is used to suggest that, for example, a nominal Tc Transfer Factor of 5 could be adjusted to 2.3 for Monocots and 5.3 for Eudicots.     

陆域产业结构演进对海洋环境的动态影响研究——以长江流域与东海沿岸地区为例

以往研究已经证明海洋经济发展中产生的污染对海洋环境质量的变化没有显著性影响,海洋污染物的主要来源是陆地,海洋环境与陆域经济之间存在着较为密切的关系,但关于陆域产业结构演进对海洋环境影响的研究非常少见,加深该研究对推动海洋环境改善具有重要的意义。利用VAR模型和Tapio脱钩模型,研究2001～2017年间长江流域和东海沿岸地区的产业结构高度化和产业结构合理化对东海海域的海洋环境的动态冲击,借助它们的脱钩状态证实该影响。研究结果显示:(1)陆域产业结构高度化有利于海洋环境改善,其原因包括产业间优势地位的更替和产业内部的技术创新;陆域产业结构合理化的发展存在波动性,导致它对海洋环境的影响不够显著;一部分海洋污染物可以通过海水自身的净化能力而消解,残存污染给海洋环境带来了不利影响。(2)在2002～2017年,东海的海洋环境与长江流域和东海沿岸地区的产业结构高度化、合理化分别表现为"大幅变化-稳步变化-脱钩持续"、"剧烈变化-起伏波动-脱钩持续"的脱钩变化规律,该脱钩分析结果证实了陆域产业结构演进对海洋环境的影响。