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.     

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.     

Thermal neutron fluence from ultra low-level γ-ray spectrometry of spoons activated during the JCO criticality accident at Tokai-mura in 1999

During the JCO-accident in Tokai-mura in 1999, the surrounding village was irradiated by an uncontrolled neutron flux. At some locations in that village, the thermal neutron flux was determined retrospectively by measurement of the very low activity of ⁵¹Cr and ⁶⁰Co in stainless-steel spoons using γ-ray spectrometry in underground laboratories. Activities determined in the HADES underground facility are presented here, together with calibrations performed using a well-defined thermal neutron flux to directly estimate the fluence of thermal neutrons independent of most assumptions. The results show measurable ⁵¹Cr in three samples and ⁶⁰Co in four samples taken from locations at distances of up to 430 m from the accident location despite the elapse of 4 half-lives of ⁵¹Cr before measurement. Effects of air transport of the samples were considered and shown to be negligible.     

Cadmium Concentration in Vegetables Grown on Urban Soils Irrigated with Untreated Municipal Sewage

Cadmium (Cd) is considered as a potential toxin that is principally dispersed in natural and agricultural environments through anthropogenic sources. Untreated municipal sewage, often a potential source of Cd, is generally used to irrigate urban agricultural soils in many developing countries. A study was carried out to determine Cd concentration in untreated municipal sewage and sewage-irrigated soils and vegetables. The metal ion concentration in municipal sewage was found 3-fold (0.03mgL^–1) its permissible concentration in irrigation water (0.01mgL^–1). Ammonium bicarbonate–diethylene triamine pentaacetic acid NH₄HCO₃–DTPA) extractable Cd concentration in top 0.15m soil ranged between 0.25 and 0.34mgkg^–1. Soil Cd concentration was significantly correlated with soil clay content, pH, electrical conductivity, and cation exchange capacity. Cadmium availability index (CDI) decreased with an increase in soil depth. The metal ion was found in leaf (0.17–0.24mgkg^–1 fresh weight) and fruit (0.07–0.18mgkg^–1 fresh weight) portions of all the sampled vegetables: bitter gourd (Momordica charantia L.), cauliflower (Brassica oleracea L.), eggplant (Solanum melongena L.), fenugreek (Trigonella foenumgraecum L.), okra [Abelmoschus esculentus (L.) Moench], onion (Allium cepa L.), pumpkin (Cucurbita pepo L.), and spinach (Spinacia oleracea L.). Leafy tissue accumulated Cd about twice that of the fruit portion. Our results suggest that prolonged ingestion of sewage-irrigated leafy vegetables can develop such Cd levels in human body that may cause a number of illnesses.     

Vertical distribution of anthropogenic radionuclides in cores from contaminated floodplains of the Yenisey River

The Mining and Chemical Industrial Combine, Zheleznogorsk (MCIC, previously known as Krasnoyarsk-26) on the River Yenisey has contaminated the surrounding environment with anthropogenic radionuclides as a result of discharges of radioactive wastes. The purpose of this study was to investigate the vertical distribution of anthropogenic contamination (¹³⁷Cs and plutonium) within floodplain areas at different distances from the discharge point. Sites were chosen that display different characteristics with respect to periodic inundation with river water. Cs-137 activity concentrations were in the range 23–3770 Bq/kg (dry weight, d.w.); Pu-239,240 activity concentrations were in the range <0.01–14.2 Bq/kg (d.w.). Numerous sample cores exhibited sub-surface maxima which may be related to the historical discharges from the MCIC. Possible evidence indicating the deposition of earlier discharges at MCIC in deeper core layers was observed in the ²³⁸Pu:^239,240Pu activity ratio data: a Pu signal discernible from global fallout could be observed in numerous samples. Cs-137 and Pu-239,240 activity concentrations were correlated with the silt fraction (% by mass <63 μm) though no significant correlation was observed between (grain-size) normalised ¹³⁷Cs activity concentrations and distance downstream from the MCIC.     

Behavior and analysis of Cesium adsorption on montmorillonite mineral

The adsorption of Cs by montmorillonite and the effects of experimental conditions on adsorption were investigated by using ¹³⁴Cs as a radioactive tracer. Additionally, the Cs-adsorbed and the modified montmorillonite were analyzed by X-ray Diffractometer System (XRD) and Scanning Electron Microscopy (SEM). The results showed that the adsorption of Cs by montmorillonite was efficient in the initial concentration (C₀) of 30 μg/L Cs nitrate solution with 20 g/L montmorillonite at room temperature. In this condition, more than 98% Cs⁺ ions could be adsorbed at pH 8. The adsorption equilibrium was achieved within 5 min and the relationship between the concentration of Cs⁺ in aqueous solutions and adsorption capacities of Cs⁺ can be described by the Langmuir adsorption isotherm. The adsorption rate would decrease when temperature increase from 0 °C to 50 °C or in presence of coexistent K⁺, Na⁺ and Ca²⁺, while modification by (NH₄)₂SO₄, [Ag(NH₃)₂]⁺, [Cu(NH₃)₄]²⁺ or 450 °C could improve the adsorption abilities of montmorillonite for Cs⁺. However, more than 89% of adsorbed Cs⁺ on montmorillonite could be desorbed by 2 mol/L HNO₃ solutions. The XRD and SEM analysis further showed that the structure of the Cs-adsorbed or modified montmorillonite were different from that of the original one.     

Agroecological Implications of the System of Rice Intensification (SRI) in Madagascar

A system of plant, soil, water and nutrient management for irrigated rice developed in Madagascar has been yielding 5, 10, even 15tha^–1 on farmers' fields where previous yields averaged around 2tha^–1. This is achieved using whatever variety of rice the farmer is already using and without having to utilize chemical fertilizer or other purchased inputs. This system, known as SRI, shows that alternative management practices, creating optimal growing conditions for plants, can bring out previously untapped genetic potential. It also shows that the practices farmers have used for centuries may not always be the best in agronomic terms.     

The influence of climate and dam construction on the Ibera wetlands, Argentina

The purpose of this work is to assess the impact on the Esteros del Ibera wetland ecosystem caused by the Yacyreta dam, a large hydroelectric power plant on the Parana River, Argentina, in comparison to other factors of environmental change. The project of the dam started around 1970. The power plant began operating in 1994. In 1989, the neighboring Ibera wetland ecosystem showed a substantial increase in the water level for which several different causes were conceivable, including climate change and the dam construction. We analyzed all existing hydrometeorological data and studied other changes that were observed in this ecosystem. A water balance model was used to analyze different scenarios. Increased groundwater inflow, generated since the construction of the dam, appears to be affecting the wetland more than any other factor. The study has implications for the assessment of global and regional consequences of building dams.

Farmworker children's residential non-dietary exposure estimates from micro-level activity time series

Farmworkers' children may have increased pesticide exposure through dermal absorption and non-dietary ingestion, routes that are difficult to measure and model. The Cumulative Aggregate Simulation of Exposure (CASE) model, integrates the complexity of human behavior and variability of exposure processes by combining micro-level activity time series (MLATS) and mechanistic exposure equations. CASE was used to estimate residential non-dietary organophosphate pesticide exposure (i.e., inhalation, dermal, and non-dietary ingestion) to California farmworker children and evaluate the micro-activity approach. MLATS collected from children and distributions developed from pesticide measurements in farmworkers' residences served as inputs. While estimated diazinon exposure was greater for inhalation, chlorpyrifos exposure was greater for the other routes. Greater variability existed between children (σ_B² = 0.22–0.39) than within each child's simulations (σ_W² = 0.01–0.02) for dermal and non-dietary ingestion. Dermal exposure simulations were not significantly different than measured values from dosimeters worn by the children. Non-dietary ingestion exposure estimates were comparable to duplicate diet measurements, indicating this route may contribute substantially to aggregate exposure. The results suggest the importance of the micro-activity approach for estimating non-dietary exposure. Other methods may underestimate exposure via these routes. Model simulations can be used to identify at-risk children and target intervention strategies.     

Benzo[a]pyrene metabolism in mice exposed to diesel exhaust: II. Metabolism and excretion

In this study we examined the effect of diesel exhaust (DE) exposure on in vivo metabolism of benzo[a]pyrene (BaP). DE-exposed and unexposed A/Jax mice of group B were instilled intratracheally with ³H-BaP. At each time point of 2, 24, and 168 h after instillation five mice were killed and the liver, lungs, and testes were removed and frozen. Aliquots of the organs were homogenized in 2 ml water and each received 3 volumes of cold ethanol. Radioactivity in supernatant and precipitate was measured. The supernatant extracts were subjected to HPLC analysis on ALOX-T and on Zorbax ODS. The ALOX-T method was a modification of Autrup's procedure for conjugate assay (Biochem. Pharmacol.28, 1727, 1979). Fractions were (a) free BaP; (b) nonconjugated primary metabolites; (c) sulfate conjugates; (d) glucuronides, glutathiones, and other conjugates. By 2 h after instillation primary metabolites were found in liver and lung, but very little was conjugated. The unconjugated BaP was mainly in the form of free BaP and phenolic metabolite(s). The lungs of DE-exposed mice had less capacity to dispose of “bound” BaP 1 week after instillation.     

Will progress in science and technology avert or accelerate global collapse? A critical analysis and policy recommendations

Industrial society will move towards collapse if its total environmental impact (I), expressed either in terms of energy and materials use or in terms of pollution, increases with time, i.e., dI/dt > 0. The traditional interpretation of the I = PAT equation reflects the optimistic belief that technological innovation, particularly improvements in eco-efficiency, will significantly reduce the technology (T) factor, and thereby result in a corresponding decline in impact (I). Unfortunately, this interpretation of the I = PAT equation ignores the effects of technological change on the other two factors: population (P) and per capita affluence (A). A more heuristic formulation of this equation is I = P(T)·A(T)·T in which the dependence of P and A on T is apparent. From historical evidence, it is clear that technological revolutions (tool-making, agricultural, and industrial) have been the primary driving forces behind successive population explosions, and that modern communication and transportation technologies have been employed to transform a large proportion of the world’s inhabitants into consumers of material- and energy-intensive products and services. In addition, factor analysis from neoclassical growth theory and the rebound effect provide evidence that science and technology have played a key role in contributing to rising living standards. While technological change has thus contributed to significant increases in both P and A, it has at the same time brought about considerable eco-efficiency improvements. Unfortunately, reductions in the T-factor have generally not been sufficiently rapid to compensate for the simultaneous increases in both P and A. As a result, total impact, in terms of energy production, mineral extraction, land-use and CO₂ emissions, has in most cases increased with time, indicating that industrial society is nevertheless moving towards collapse. The belief that continued and even accelerated scientific research and technological innovation will automatically result in sustainability and avert collapse is at best mistaken. Innovations in science and technology will be necessary but alone will be insufficient for sustainability. Consequently, what is most needed are specific policies designed to decrease total impact, such as (a) halting population growth via effective population stabilization plans and better access to birth control methods, (b) reducing total matter-energy throughput and pollution by removing perverse subsidies, imposing regulations that limit waste discharges and the depletion of non-renewable resources, and implementing ecological tax reform, and (c) moving towards a steady-state economy in which per-capita affluence is stabilized at lower levels by replacing wasteful conspicuous material consumption with social alternatives known to enhance subjective well-being. While science and technology must play an important role in the implementation of these policies, none will be enacted without a fundamental change in society’s dominant values of growth and exploitation. Thus, value change is the most important prerequisite for avoiding global collapse.

Effects of radionuclide and rainfall characteristics on field loss parameters of grass

The decrease of foliar activity in vegetation after its initial contamination by foliar deposition is termed “field loss” (Chamberlain, 1970). This work investigated further laboratory data concerning field loss of ¹³⁴Cs, ¹³⁷Cs, ⁸⁵Sr, ¹³³Ba and ^123mTe deposited on grassland (Madoz-Escande et al., 2005). Treatments consisted in rainfall scenarios cumulating 14 mm per week, combining two levels of intensity (8 or 30 mm/h) and two levels of frequency/precocity (late once or early twice-a-week). The time course of field loss was monitored in the edible tissues which were sampled by mowing between the rainfalls. Data were analyzed with an offset exponential loss model which is applicable to chronic contamination and is consistent with approaches adopted in radiological assessment models. Its parameters were estimated by the maximum-likelihood method, and their accuracy was determined by nonparametric boostrap. Radionuclide and rainfall conditions significantly affected the estimated rate (λ₁) and extent (A₁) of field loss. Field loss rate (λ₁) and nonentrainable fraction (1 − A₁) varied by a factor 1.5–3. Cesium was very mobile but persistent. On the contrary Tellerium was found less labile, but eventually was almost completely eliminated. Strontium and Barium had intermediate behaviors. Field loss was more efficient for moderate late once-a-week rainfalls (8 mm/h). Higher rainfall intensity reduced more the radionuclides losses than higher rainfall frequency/precocity. This paper reports statistically relevant effects that should be considered for more realistic assessments.     

Aggregated Estimation of the Basic Parameters of Biological Production and the Carbon Budget of Russian Terrestrial Ecosystems: 1. Stocks of Plant Organic Mass

The data presented were obtained at the first stage (1993–1999) of studies on evaluating the basic parameters of biological production in Russian terrestrial ecosystems in order to provide information for assessing and modeling the carbon budget of the entire terrestrial biota of the country. Stocks of phytomass (by fractions), coarse woody debris, and dead roots (underground necromass) were calculated by two independent methods, which yielded close results. The total amount of phytomass in Russian terrestrial ecosystems was estimated at 81800 Tg (=10¹² g = million t) dry matter, or 39989 Tg carbon. Forest ecosystems comprise a greater part (82.1%) of live plant organic matter (here and below, comparisons are made with respect to the carbon content); natural grasslands and brushwoods account for 8.8%; the phytomass of wetlands (bogs and swamps), for 6.6%; and the phytomass of farmlands, for only 2.5%. Aboveground wood contains approximately two-thirds of the plant carbon (63.8%), and green parts contain 9.9%. For all classes of ecosystems, the proportion of underground phytomass averages 26.7% of the total amount, varying from 22.0% in forests to 57.1% in grasslands and brushwoods. The average phytomass density on lands covered with vegetation (1629.9 million hectares in Russia) is 5.02 kg/m² dry matter, or 2.45 kg C/m². The total amount of carbon in coarse woody debris is 4955 Tg C, and 9180 Tg C are in the underground necromass. In total, the vegetation of Russian terrestrial ecosystems (without litter) contains 54124 Tg carbon.     

Environmental and lifestyle factors affect benzene uptake biomonitoring of residents near a petrochemical plant

Background

We monitored urinary benzene excretion to examine factors affecting benzene uptake in a sample of the general population living near a petrochemical plant.

Methods

Our study population included 143 subjects: 33 petrochemical plant workers (W) with low level occupational benzene exposure; 30 residents in a small town 2 km from the plant (2kmR); 26 residents in a second small town located 2 to 4 km from the plant (4kmR); and 54 urban residents 25 km from the plant (25kmR). Exposure to benzene was evaluated by personal air sampling during one work-shift for the W group, and from 8.00 to 20:00 for general population subgroups, and by urinary benzene (BEN-U).

Results

Median airborne benzene exposure was 25, 9, 7 and 6 μg/m³ benzene among the W, 2kmR, 4kmR, and 25kmR subgroups, respectively; the highest level was found among the workers, while there was no significant difference among the other groups. Median BEN-U was 2 to 14-fold higher in smokers compared to non-smokers; among non-smokers BEN-U was the highest in W (median 236 ng/L), and lower in the 2kmR (48 ng/L) and 4kmR (63 ng/L) subgroups than in the 25kmR (120 ng/L) subgroup. A multiple linear regression analysis, explaining up to 73% of BEN-U variability, confirmed that active smoking and airborne benzene most strongly affected BEN-U. Among the non-smoking, non-occupationally exposed study subjects, a positive association was found between BEN-U and the distance of residence from the plant. This association was explained by increased exposure to urban traffic emissions in the study group residing at a greater distance from the plant. Environmental tobacco smoke had a marginally positive role.

Conclusion

Among factors affecting benzene uptake in non-occupationally exposed individuals, urban residence contributes to benzene exposure more than residing in close proximity to a petrochemical plant.     

Levels and regional trends of persistent organochlorines and polybrominated diphenyl ethers in Asian breast milk demonstrate POPs signatures unique to individual countries

Human breast milk samples collected in 2007–2008 from four countries, Vietnam (Hanoi), China (Beijing), Korea (Seoul) and Japan (Sendai, Kyoto and Takayama), were analyzed for persistent organic pollutants (POPs) such as dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane-related compounds (CHLs), hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Comparing with previous surveys, the present study indicates that the DDTs in breast milk from China and Vietnam had gradually decreased during the last decade, but were still 5–10 times higher than those in other nations. The ratios of p,p′-DDE/p,p′-DDT and o,p′-DDT/p,p′-DDT were higher in Beijing than in the other countries, suggesting that there is less fresh intake of commercial DDT products and a possible exposure to dicofol in China. CHL and PCB levels were relatively higher in mothers from Japan, whereas β-HCH and HCB were more common in Chinese women. In Japan, it is suspected that mothers in the urban/coastal area (Sendai) were more continuously exposed to organochlorine pesticides (OCPs) than mothers in the rural/inland area (Takayama). In addition, OCP levels in primiparae were significantly higher than those in multiparae from Japan and Korea. These indicate that both parity and regional factors are major determinants of the levels of OCPs and PCBs in human milk. On the other hand, higher concentrations of PBDEs were observed in mothers' milk from Korea. The congener was dominated by BDE-47 (43–54%), followed by BDE-153 (23–33%) in all regions except for Beijing where BDE-28 (23%) was relatively abundant. In Japanese breast milk, regional and parity-dependent distributions were not observed for PBDEs. Among PBDE congeners, age-dependency was observed for BDE-153, which was negatively correlated (p < 0.05) to the age of mothers in Kyoto (17 participants were housewives), while it increased with age in Sendai (10 participants were clerks). No such correlation was seen for BDE-47, indicating that BDE-47 was ingested and assimilated via different kinetics or routes from BDE-153 in Japan.     

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.