Possible effect of solar tides on radon signals

Large temporal variations of radon (²²²Rn) are often encountered in air in the geologic environment, at time scales from diurnal to annual. Interpretations as to the nature of these variations, unique to ²²²Rn, often invoke either above surface atmospheric variations, or the influence of subtle active geodynamic processes. So far the eventual geophysical drivers of the variation of ²²²Rn as well as its specific qualities enabling this temporal variation are not known. New insight on the temporal variation of ²²²Rn is gained by experimental simulation in confined air. Two short laboratory experiments, and one external experiment lasting over 3 years, were performed inside closed canisters and using natural and commercial ²²²Rn sources. Internal and external gamma and alpha detectors recorded variations of the radiation, up to around 20% of the equilibrium level. Radon signals of different time scale occurred with: a) periodic annual and semi-annual signals; b) non-periodic multi-day signals; c) periodic daily signals. Similar, related, inversely-related and dissimilar temporal patterns were manifested in the measured time series of the different sensors. Diurnal periodicity was dominated by the solar tide components S1, S2 and S3, exhibiting unlike relative amplitudes and different phases at the different sensors. A compound association occurs among the amplitudes and phases of the diurnal and seasonal periodicities of the daily ²²²Rn signal, linking the periodic phenomena to the rotation of earth around its axis and around the sun. ²²²Rn variation patterns in the frequency-time domain cannot be driven by the corresponding atmospheric variation patterns. These results, obtained under static and isolated conditions, are in disagreement with the expected radioactive equilibrium and its spatially uniform expression within and around the experimental volume. The external influence which drives the daily signals evolving from ²²²Rn inside the canister is non-atmospheric and seemed to be from a remote source and traversed a 5-cm thick lead shield. The similarities with observations on ²²²Rn signals from upper crustal levels imply that such an external influence, possibly as a component of solar irradiance, drives the ²²²Rn signals to a depth of at least 100 m. New combined prospects for the research are indicated in terms of the radioactive behavior of ²²²Rn in air and in terms of an above surface geophysical driver for this behavior.     

Isotope tracing of submarine groundwater discharge offshore Ubatuba, Brazil: results of the IAEA–UNESCO SGD project

Results of groundwater and seawater analyses for radioactive (³H, ²²²Rn, ²²³Ra, ²²⁴Ra, ²²⁶Ra, and ²²⁸Ra) and stable (D and ¹⁸O) isotopes are presented together with in situ spatial mapping and time series ²²²Rn measurements in seawater, direct seepage measurements using manual and automated seepage meters, pore water investigations using different tracers and piezometric techniques, and geoelectric surveys probing the coast. This study represents first time that such a new complex arsenal of radioactive and non-radioactive tracer techniques and geophysical methods have been used for simultaneous submarine groundwater discharge (SGD) investigations. Large fluctuations of SGD fluxes were observed at sites situated only a few meters apart (from 0 cm d⁻¹ to 360 cm d⁻¹; the unit represents cm³/cm²/day), as well as during a few hours (from 0 cm d⁻¹ to 110 cm d⁻¹), strongly depending on the tidal fluctuations. The average SGD flux estimated from continuous ²²²Rn measurements is 17 ± 10 cm d⁻¹. Integrated coastal SGD flux estimated for the Ubatuba coast using radium isotopes is about 7 × 10³ m³ d⁻¹ per km of the coast. The isotopic composition (δD and δ¹⁸O) of submarine waters was characterised by significant variability and heavy isotope enrichment, indicating that the contribution of groundwater in submarine waters varied from a small percentage to 20%. However, this contribution with increasing offshore distance became negligible. Automated seepage meters and time series measurements of ²²²Rn activity concentration showed a negative correlation between the SGD rates and tidal stage. This is likely caused by sea level changes as tidal effects induce variations of hydraulic gradients. The geoelectric probing and piezometric measurements contributed to better understanding of the spatial distribution of different water masses present along the coast. The radium isotope data showed scattered distributions with offshore distance, which imply that seawater in a complex coast with many small bays and islands was influenced by local currents and groundwater/seawater mixing. This has also been confirmed by a relatively short residence time of 1–2 weeks for water within 25 km offshore, as obtained by short-lived radium isotopes. The irregular distribution of SGD seen at Ubatuba is a characteristic of fractured rock aquifers, fed by coastal groundwater and recirculated seawater with small admixtures of groundwater, which is of potential environmental concern and has implications on the management of freshwater resources in the region.     

Environmental and climatic signals from stable isotopes in Anatolian tree rings, Turkey

Dendrochronological and oxygen–carbon isotopic analysis was conducted on tree rings collected at two different elevations from three different regions in western Anatolia, Turkey. Tree rings were sampled from Anatolian black pines (Pinus nigra Arn. subsp. pallasiana (Lamb.) Holmboe) of at least 200?years old through an N–S transect covering Bolu-Mengen (north), Kütahya–Simav, and Antalya–Alanya (south) forests. Cellulose was extracted from 5-year blocks of tree rings from lower to upper altitudes in each region. Dendrochronological site chronologies were built for each of the 6 sites, and response to climate was evaluated. The long-term δ¹³C chronologies comprising the period 1800–2008 strongly decline by an average of 2.5‰ from the mid-twentieth century, which corresponds with the commencement of industrialization in Turkey. Oxygen isotope (δ¹⁸O) time series show dominantly low undulations, although some high-frequency variations of up to 6‰ are also observed. As a result of latitude and continent effects, oxygen isotope values of tree rings show an average of 3‰ increase from south (Antalya) to the north (Bolu). Correlations between carbon isotope ratios yield high positive values indicating that industrial pollution exerts a major control on the δ¹³C systematics of the studied trees. Corrected δ¹³C ratios are mostly represented by strong positive responses to variations in temperature and precipitation, whereas δ¹⁸O and summer temperature/precipitation are negatively correlated. Tree-ring widths and δ¹⁸O display similar responses to the temperature and sensitivity to the climatic impact of historic volcanic eruptions, and changes in the solar irradiance record are also detected in other high-resolution paleoclimate archives for the region.     

Experimental studies of the transfer of neptunium from sea water to sediments and organisms (annelids and molluscs)

This paper deals with the physico-chemical behaviour of neptunium in sea water and with its capacity for transfer to coastal or deep-sea sediments and for uptake by two benthic species, Arenicola marina (L.) and Cerastoderma edule (L.). We used the ²³⁹Np isotope with mass concentrations in sea water of about 2·5 × 10⁻¹⁰−5·4×10⁻¹² g litre⁻¹, which are close to the concentrations observed in the environment for ²³⁷Np. The experimental results show that Np occurs in solution mainly as the neptunyl ion NpO₂⁺, but soluble anionic and neutral complexes and particulate forms were also detected. The distribution coefficients for the sediments varied from 350 to 6500. The carbonate phase plays a decisive role in neptunium transfer but other fixation processes are also possible. Concentration factors after 13 days were found to have values of 40 and 14 for the shells and soft parts of cockles, respectively, while polychaetes had a concentration factor of 2. Thus Np has a smaller probability of transfer to sediments and organisms than have plutonium and americium.     

Geochemical associations of plutonium and γ-emitting radionuclides in caithness soils and marine particulates

Geochemical associations of plutonium and artificial γ-emitting radionuclides have been investigated in soils and marine particulate material from the immediate vicinity of the Dounreay Nuclear Power Development Establishment (DNPDE) Caithness. The artificial radionuclides present in these materials arise from a variety of sources: world-wide nuclear weapons test fallout, direct deposition from atmospheric discharges at DNPD, and the return to land of activity previously discharged to sea (containing contributions from Dounreay and Sellafield). The levels, although sufficient to permit satisfactorily low counting errors, are of negligible radiological significance, the plutonium being more than 1000 times less than the NRPB Generalised Derived Limit (GDL) for well-mixed soil. Sequential leaching using selective extractants was performed to quantify the percentages of each nuclide in the following notional fractions: (a) readily available, (b) exchangeable and bound at specific adsorption sites, (c) chelated as insoluble organic complexes, (d) associated with sesquioxides, and (e) residual. Plutonium was found to be associated mainly with phases (c) and (d), while the γ-emitters present in the marine particulate material showed quite varied distributions. The degree of chemical fixation in the particulates follows the sequence ⁴⁰K¹³⁷Cs¹⁰⁶Ru¹²⁵Sb^239,240Pu¹⁴⁴Ce⁶⁰Co^154,155Eu.     

Spatio-temporal variations in the technetium-99 content of fucus serratus in the english channel during 1982–1984

Spatio-temporal variations in the technetium-99 content of Fucus serratus samples from the French coast of the English Channel were studied between 1982 and 1984 using various sampling strategies. The lack of constancy in measurements from within the seaweed zone of the same station is revealed by a variation of 18% in the mean contents of samples collected from different sampling levels, a variation which reaches 41% if the extreme values of all results are taken into account. Regional variations over the Channel as a whole show an asymmetric diminution of the ⁹⁹Tc content of the seaweed on the two sides of the liquid effluent discharge outlet from the reprocessing plant at La Hague and this confirms a predominant drift of Channel waters towards the North Sea. Variations with time at three stations during 1983 and 1984 have revealed that there is a time-lag between fluctuations observed in the discharges and those in F. serratus. In addition, a periodic component observed at the Roscoff and Wimereux stations, where the ⁹⁹Tc content of the seaweed varies by a factor of 2–3 between winter and summer periods, could be correlated with seasonal changes both in the metabolic state of F. serratus and in the currents to the south-west of Cap de La Hague. ⁹⁹Tc, which here has no radiological impact on man, would thus appear to be a radioactive label for sea waters and one which is particularly sensitive to variations in environmental conditions.     

Indoor air pollution and inter-room pollutant transport due to unvented kerosene-fired space heaters

Two kerosene-fired space heaters, one white-flame convective and one blue-flame radiant, were operated in the master bedroom and living room of an unoccupied house (elevation: 1800 m) under several simulated use conditions. Tests were conducted in the master bedroom with the bedroom door and bedroom window open and closed. The heaters were operated until an 8 °C temperature rise was achieved in the room. Increases in bedroom concentrations of CO, CO₂, NO, NO₂, and O₂ are reported. The increases in CO₂ levels ranged from 2440 to 5440 mL/m³ (ppm) while the increases in NO₂ levels ranged from 0.12 to 0.60 mL/m³ (ppm). The NO₂ emission rate from the convective heater was reduced at the high altitude location as compared with previous emission rate measurements conducted near sea level with the same heater. In addition, inter-room pollutant transport rates are reported for bedroom tests conducted with the window closed. While inter-room pollutant transport rates were less than 10 m³ with the bedroom door closed (opening area less than 100 cm²), they ranged from 16 m³/h to 53 m³/h with the bedroom door open 2.5 cm (opening = 520 cm²), and ranged from 190 to 3400 m³/h with the door fully open (opening area = 15,000 cm²). Continuous emission rate data are reported for tests conducted with the heater in the living room.     

Radon, helium and CO2 measurements in soils overlying a former exploited oilfield, Pechelbronn district, Bas-Rhin, France

The Pechelbronn oilfield (Rhine Graben, France), where mining activity ended in the 1960s, has been used for waste disposal for twenty years. Since the wastes are varied, work is underway to identify the discharged materials and their derivatives, as well as to locate and quantify potential discharge sites. Two major goals were assigned to the present work. The first was to identify or refine the location of hidden structures that could facilitate gas emanation up to the surface, by studying soil gas concentrations (mainly ²²²Rn, CO₂, CH₄ and helium) and carbon isotope ratios in the CO₂ phase. The second was devoted to examining, from a health and safety viewpoint, if the use of the oilfield as a waste disposal site might have led to enhanced or modified gas emanation throughout the area.It appeared that CO₂ and ²²²Rn evolution in the whole area were similar, except near some of the faults and fractures that are known through surface mapping and underground observations. These ²²²Rn and CO₂ anomalies made it possible to highlight more emissive zones that are either related to main faults or to secondary fractures acting as migration pathways. In that sense, the CO₂ phase can be used to evaluate ²²²Rn activities distant from tectonic structures but can lead to erroneous evaluations near to gas migration pathways. Dumping of wastes, as well as oil residues, did not appear to have a strong influence on soil gaseous species and emanation. Similarly, enhanced gas migration due to underground galleries and exploitation wells has not been established. Carbon isotope ratios suggested a balance of biological phenomena, despite the high CO₂ contents reached. Other monitored gaseous species (N₂, Ar, H₂ and alkanes), when detected, always showed amounts close to those found subsurface and/or in atmospheric gases.     

Relationship between morphological disparity and taxonomic diversity in rodent communities in the zone of influence from the Eastern Ural Radioactive Trace in the Southern Urals

To test the hypothesis that morphological disparity increases while taxonomic diversity decreases in a radioactively contaminated environment, the relationship of these parameters was studied in communities (taxocenes) of rodents living in the Southern Urals in the zone of influence from the Eastern Ural Radioactive Trace (EURT) (2003–2008). Young of the year of six rodent species (98 samples) were examined in the background (control) area (0.2 Ci/km²) and in the impact area polluted with radionuclides from the EURT (750 Ci/km²). The dynamics of morphological disparity (MD), assessed with regard to average values of five exterior characters, was compared between the control and impact taxocenes. Taxonomic (taxocenotic) diversity was estimated with the Shannon index (H). Morphological disparity was found to increase significantly at low rodent abundance (in conditionally unfavorable years) and decrease at high abundance, with the value of MD in the impact taxocene being significantly higher. A negative correlation between MD and H was revealed (r = −0.70), in conformity with the above hypothesis. Discordance (difference in direction) of annual changes in the test parameters, with H increasing while MD decreases (or vice versa) was observed in unfavorable years; it can be used as an indicator of conditions unfavorable for rodent taxocenes.     

Elevated radioxenon detected remotely following the Fukushima nuclear accident

We report on the first measurements of short-lived gaseous fission products detected outside of Japan following the Fukushima nuclear releases, which occurred after a 9.0 magnitude earthquake and tsunami on March 11, 2011. The measurements were conducted at the Pacific Northwest National Laboratory (PNNL), (46°16′47″N, 119°16′53″W) located more than 7000 km from the emission point in Fukushima Japan (37°25′17″N, 141°1′57″E). First detections of ¹³³Xe were made starting early March 16, only four days following the earthquake. Maximum concentrations of ¹³³Xe were in excess of 40 Bq/m³, which is more than ×40,000 the average concentration of this isotope is this part of the United States.     

Using sequential extraction techniques to assess the partitioning of plutonium and neptunium-237 from multiple sources in sediments from the Ob River (Siberia)

Sequential extraction techniques have been developed to assess partitioning of anthropogenic radionuclides (²⁴⁰Pu, ²³⁹Pu, and ²³⁷Np), originating from a variety of sources, as identified by using bulk sediment isotopic composition. Sediments were leached sequentially with a series of six chemical treatments designed to approximate different environmental processes that may occur or to selectively extract trace metals contained in different solid phases of the sediments (i.e., exchangeable, reducible, carbonate, organic, acid leachable, and refractory). Results indicate the majority of Pu and Np is similarly distributed within many of the extracted fractions, with the largest percentage (66–97%) of both elements being observed in sediments treated with buffered citrate dithionite (CDB), which targets easily reduced constituents such as Mn and Fe hydrous oxides. While these results do indicate an association of Pu and Np with redox sensitive elements, the environmental implications are unclear given that the CDB treatment is more extreme than naturally occurring conditions. Minor amounts of Np partition differently from Pu in sediments. The NH₄-acetate treatment, which is designed to liberate trace metals that are loosely adsorbed onto the surfaces of sedimentary materials such as hydrated iron oxides and humic substances, or present at exchangeable sites in clay minerals, mobilized ∼12% of the total Np while Pu levels were below detection. The H₂O₂ treatment, which is designed to liberate trace metals bound to organic matter, mobilized ∼8 and ∼1% of Np and Pu, respectively. These results indicate that a minor portion of the total Np may be affected by environmental conditions that have little or no effect on Pu. Between 7 and 24% of the Pu was observed in treatments designed to liberate Pu and Np that are tightly bound to lithogenic phases or refractory silicates. The ²⁴⁰Pu/²³⁹Pu observed in accessible and refractory fractions ranged between 0.11 and 0.18. With the exception of one sample, the ²⁴⁰Pu/²³⁹Pu isotope ratios measured in the refractory fractions are essentially identical having a mean ratio value of 0.123 ± 0.001 (1σ). The ²⁴⁰Pu/²³⁹Pu ratios provide isotopic evidence that suggests a portion of non-fallout contamination has a refractory nature. The presence of similarly low ²⁴⁰Pu/²³⁹Pu ratios in refractory fractions of sediments from the Ob and Irtysh Rivers suggests the existence of a source of refractory Pu which is consistent with refractory “hot particles” derived from surface tests at the Semipalitinsk test site.     

Collection characteristics of a double stage scrubber to eliminate the paint mist from a spray booth

A 4.5 m³/min laboratory paint spray booth was built adopting a double-stage scrubber with heavy oil as the scrubbing liquid. The relationship between the collection efficiency E and the pressure drop ΔP was studied using a cylindrical paper tilter and a Digital Dust Counter. Experimental results indicated that the collection efficiency in this system is in accordance with the collection efficiency equation based on the theory of inertial impaction. With water used as the scrubbing liquid, the factor K is about 0.5 for single-stage scrubbing, while it is 0.6 for double-stage scrubbing. At a pressure drop of 60 mm of H₂O, heavy oil used as the scrubbing liquid gained about 2.0% more in collection efficiency than water. The zigzag baffler equipped for removing heavy oil mist was also effective for the paint mist collector, and 99.1% of E was gained at a pressure drop of 135 mm H₂O.     

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.     

Dendrochronology of bristlecone pine, Pinus longaeva

Since 1953 the Laboratory of Tree-Ring Research has conducted dendrochronological studies of bristlecone pine (Pinus longaeva D.K. Bailey, sp. nov.) in the White Mountains of California. This research resulted in the establishment of a continuous tree-ring sequence of 8253 yr. The millennia-old pines have emerged as a unique source of chronological data and the precisely dated wood is essential to certain paleoenvironmental and geophysical investigations. Over 1000 dendrochronologically dated decade samples of bristlecone pine supplied to three C-14 laboratories have been used to calibrate the radiocarbon time scale for the past seven millennia, a development of far reaching consequences in the fields of archaeology and geology. In addition, recent advances in other methods of analyzing past climatic variability — techniques involving stable isotope ratios, amino acid racemization, remanent magnetism, and trace element abundances — have greatly increased the demand for wood of known age and, hence, for chronology development. Spanning the past 7500 yr, 1138 prepared decade samples, with a total weight of nearly 16 kg are available for study.     

Pulmonary function changes in Chinese hamsters exposed six months to diesel exhaust

Chinese hamsters were exposed for eight hours per day to automotive diesel exhaust emissions which were diluted with air (18 to 1) and had a particulate level of 6.4 mg/m³. Pulmonary function measurements were made after six months exposure. Body weight (BW), lung weight (LW), vital capacity (VC), residual volume by water displacement (RV_w) and by gas dilution (RV_D), alveolar volume (V_A), and carbon monoxide transfer factor (D_LCO) were measured. LW showed a significant increase in the diesel exposed animals (P < 0.01) while VC, RV_W, and D_LCO showed decreases (P < 0.01). Static deflation volume-pressure curves showed depressed deflation volumes for diesel exposed animals when volumes were corrected for body weight and even greater depressed volumes when volumes were corrected for lung weight. However, when volumes were expressed as percent vital capacity, the diesel exposed animals had higher lung volumes at 0 and 5 cm H₂O. Results of the pathological examination of the lung tissue will be necessary for final analysis of our findings. However, preliminary interpretation indicates possible emphysematous changes which are compatible with the observed decrease in D_LCO.     

Halotolerant bacteria of the genus <Emphasis Type="Italic">Arthrobacter</Emphasis> degrading polycyclic aromatic hydrocarbons

Eight strains of bacteria capable of degrading polycyclic aromatic hydrocarbons have been isolated from soils and bottom sediments sampled in the region of Verkhnekamskoe potash deposit (Berezniki, Perm krai) and classified with the genus Arthrobacter on the basis of phylogenetic analysis (16S rRNA genes) and morphological and chemotaxonomic characters. According to the results of 16S rDNA sequence alignment, strains B905, SMB11, SMB145, SF27, and DF14 show the highest sequence homology to the type strain of A. crystallopoietes (99.7%), and strain SN17, to the type strain of A. arilaitensis (99.8%). The isolated strains are capable of growing on naphthalene and phenanthrene (as the sole sources of carbon and energy) in the presence of 60 mg/l NaCl. Their cells contain large plasmids ranging in size from 85 to 130 kb. Plasmid elimination from Arthrobacter sp. SF27 has proved to result in the loss of capacity for growing on naphthalene and phenanthrene, suggesting a plasmid localization of genes responsible for degradation of these compounds.     

Stable nitrogen isotope ratio in wood substrates and xylotrophic fungi in forest ecosystems of Western Siberia

It has been shown that wood substrates are the main source of nitrogen for xylotrophic fungi, which have almost the same isotopic signature as their substrate. This fact and a strong positive correlation in nitrogen isotope composition between the substrates and fungi provide evidence for a closed type of nitrogen turnover in the wood-fungus system that is based on retention and repeated utilization of this element. Its isotope composition in the fungi depends on that in the substrate, which is enriched in the heavy isotope in deciduous wood and in the light isotope in coniferous wood. The nitrogen isotope composition in the fungi and wood substrates does not depend on the degree of wood mineralization or climatic conditions, and δ¹⁵N is not an indicator of fungal physiological activity or wood decomposition rate but rather a marker of the isotopic composition of nitrogen sources for the fungi.     

Assessing the fate of radioactive nickel in cultivated soil cores

Parameters regarding fate of ⁶³Ni in the soil–plant system (soil: solution distribution coefficient, K_d and soil plant concentration ratio, CR) are mostly determined in controlled pot experiments or from simple models involving a limited set of soil parameters. However, as migration of pollutants in soil is strongly linked to the water migration, variation of soil structure in the field and seasonal variation of evapotranspiration will affect these two parameters. The aim of this work was to explore to what extent the downward transfer of ⁶³Ni and its uptake by plants from surface-contaminated undisturbed soil cores under cultivation can be explained by isotopic dilution of this radionuclide in the pool of stable Ni of soils. Undisturbed soil cores (50 cm × 50 cm) were sampled from a brown rendzina (Rendzic Leptosol), a colluvial brown soil (Fluvic Cambisol) and an acidic brown soil (Dystric Cambisol) using PVC lysimeter tubes (three lysimeters sampled per soil type). Each core was equipped with a leachate collector. Cores were placed in a greenhouse and maize (DEA, Pioneer^®) was sown. After 44 days, an irrigation was simulated at the core surfaces to supply 10 000 Bq ⁶³NiCl₂. Maize was harvested 135 days after ⁶³Ni input and radioactivity determined in both vegetal and water samples. Effective uptake of ⁶³Ni by maize was calculated for leaves and kernels. Water drainage and leaching of ⁶³Ni were monitored over the course of the experiment. Values of K_d in surface soil samples were calculated from measured parameters of isotopic exchange kinetics. Results confirmed that ⁶³Ni was strongly retained at the soil surface. Prediction of the ⁶³Ni downward transfer could not be reliably assessed using the K_d values, since the soil structure, which controls local water fluxes, also affected both water and Ni transport. In terms of ⁶³Ni plant uptake, the effective uptake in undisturbed soil cores is controlled by isotope dilution as previously shown at the pot experiment scale.     

Investigation of equilibria involving carbon dioxide, carbonates and water

Several laboratory techniques are reviewed in this paper, which yield reliable data on carbonate equilibria. In particular, it is emphasized that pco₂ variation is necessary in order to potentiometrically distinguish between hydrogen carbonato and caronato complexes. The essential features of reliable solubility measurements of carbonate phases are summarized. A neglected autoclave technque is described which has been successfully applied for the synthesis of pure, crystalline, MnCO₃, FeCO₃ and CoCO₃. Details of a continuously operating solubility cell for experiments at 5–95°C are also given.Solubilty constants for different ionic media are related by the respective equilibrium vapor pressure of H₂O and the standard potentials of the respective metal electrodes. It is shown that a thermodynamic cycle can be exploited for an indirect determination of the Fe²⁺/Fe standard potential. The application of solubility data is discussed using the pco₂ control in the recent geologic past an an example.     

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.