Fractionation of natural radionuclides in soils from a uranium mineralized area in the south-west of Spain

A new version of a classical method was applied to study the distribution of natural radionuclides (238U, 230Th, and 226Ra) in the soil fractions obtained by a sequential extraction procedure. The potential significance of the fractions obtained with this method was tested on two very similar soils but with very different contents of the three radionuclides, collected in the proximity of a disused uranium mine located in the Extremadura region in the south-west of Spain. The results confirmed that, if only non-residual fractions are considered, the sequential method applied shows a characteristic speciation pattern of these natural radionuclides in this soil matrix, i.e., the distribution of each of the three radionuclides was very similar for the two soil samples.     

Dynamics of aluminum speciation in forest-well drainage waters from the Rhode River watershed, Maryland

This paper reports an investigation of the dynamics of aluminum (Al) speciation in the forest-well waters from study site 110 of the Rhode River watershed, a representative sub-unit of Chesapeake Bay. Seasonal changes of Al speciation are evaluated by a modified MINEQL computer model using chemical equilibrium calculation. It was found that Al-F and Al-Org complexes were the dominate forms, whereas toxic forms of Al3+ and Al-OH were not significant. This indicates that Al toxicity is not very serious in the Rhode River area due to the high concentrations of fluoride and organic materials, even though sometimes pH is very low (approximately 4). Increased H+ or some other associated factors may be responsible for the decline in fish and amphibian population on the watershed.     

Preparation and characterization of diesel exhaust particles for biological experiments

Bioassays of diesel engine exhaust components are being conducted at IITRI to determine toxic and carcinogenic potentials of the exhaust. The bioassay method, intracheal instillation of saline suspensions of test materials in hamsters, requires preparation of stable suspensions of test materials. A method to prepare suspensions of whole particle diesel exhaust in saline has been developed. The diesel exhaust particle material was supplied to IITRI as a dry, loose powder by the U.S. EPA from a light duty diesel test engine. Preliminary characterizations of the powders indicated aggregation of exhaust particles had occurred both before and during capture on collection substrates. Flake-like sheets and hollow spheres of aggregated particles up to 150 μm in sie present in the powders. Therefore, the powder were ball-milled to geometric particle sizes more amenable to the animal administration technique to be employed. Grinding, suspension preparation and particle concentration assaying methods have been developed. Particle (geometric) size and morphological characterizations have also been performed on the as-received powders and prepared suspensions. A method to prepare emulsions (liquid-liquid suspensions) of the dichloromethane extracts of whole particle diesel exhaust has also been developed.     

Variation of the distribution coefficient (Kd) of selenium in soils under various microbial states

This study aimed to (i) evaluate whether the K(d) value of selenium is dependent upon the soil microbial activity and (ii) define the limitation of the use of the K(d) concept to describe selenium behaviour in soils when assessing the long-term radiological waste disposal risk. K(d) coefficients, as well as information on selenite speciation in the soil-solution, were derived from short- and long-term batch experiments with a calcareous silty clay soil in various microbial states. Soil microbial activity induced (i) an increase of the K(d) value from 16 l kg(-1) in sterile conditions to 130 l kg(-1) when the soil was amended with glucose and nitrate, and (ii) changes in selenium speciation both in the solution (presence of seleno-species other than free Se(IV)) and in the solid phase (Se linked to microorganisms). Although the K(d) coefficient adequately reflects the initial fractionation between soil-solid and soil-solution, it does not allow for speciation and microbial processes, which could affect reversibility, mobility and the long-term accumulation and uptake into crops.     

Stakeholder engagement in social learning to resolve controversies over land-use change to plantation forestry

Rapid land-use change arising from incentives for afforestation has created tensions in rural communities previously dominated by agricultural enterprises. This paper reports on an innovative experiment with social learning that incorporated participatory modelling to resolve community concerns in a case study of plantation forestry in the Upper Clarence catchment of north-eastern NSW Australia. The development of a diagnostic framework helped identify socioeconomic and environmental issues within the community for investigation by a self-selected participatory advisory committee (PAC) representing a diversity of views. Implementation of a social learning exercise offered empathetic and intellectual engagement among PAC members that maintained interest, built confidence, and improved problem-solving capacity while fostering group ownership over decision making. A shared understanding of dynamic landscape problems helped empower participants to collaboratively develop solutions for improved management and operational practices, and cooperate to explore further options for plantation industry development under existing policy guidelines which are presented in this paper. As a result of frank discussions between diverse stakeholders in a mutually respectful learning environment that combined local, scientific and expert knowledge, concerns dissipated and participants developed a more favourable view of plantation forestry activity.     

Oxygen demand, nitrogen and copper removal by free-water-surface and subsurface-flow constructed wetlands under tropical conditions

This study was conducted to: (1) assess the role of wetland vegetation in the removal of oxygen demand and nitrogen under tropical conditions, (2) estimate the uptake of nitrogen and copper by wetland plants and (3) investigate the speciation of Cu in wetland media among four operationally defined host fractions, namely exchangeable, carbonate, reducible and organically bound. Four laboratory-scale wetland units, two free-water-surface (FWS) and two subsurface-flow (SF) with one of each planted with cattails (Typha augustifolia), were fed with primary-treated sewage and operated at nominal retention times of 0.6-7 days. The influent and effluent BOD/COD and nitrogen concentrations were monitored to assess the performance of the wetland units for various mass loading rates. At the end of the study, all cattail plants were harvested and analyzed for total Kjeldahl nitrogen (TKN). Four other wetland units, which were identical to the first four, were fed with domestic wastewater spiked with copper in increasing concentrations. Copper speciation patterns in the sand layer were determined at the end of the study. The results showed that wetland vegetation did not play an important role in oxygen demand removal but were capable of removing about 22% and 26% of the nitrogen input in the FWS and SF wetland units, respectively. Mass balance analysis indicated that less than 1% of copper introduced was taken up by the cattails. Copper speciation patterns in the sand media showed that the exchangeable fraction contributed 30-57% and 63-80% of the nonresidual copper in the planted and unplanted FWS wetlands, respectively. For SF units, the percentages were 52-62% and 59-67%, respectively. This indicates that large amount of copper in the media were potentially remobilizable.     

Speciation and hydrological transport of metals in non-acidic river systems of the Lake Baikal basin: Field data and model predictions

The speciation of metals in aqueous systems is central to understanding their mobility, bioavailability, toxicity and fate. Although several geochemical speciation models exist for metals, the equilibrium conditions assumed by many of them may not prevail in field-scale hydrological systems with flowing water. Furthermore, the dominant processes and/or process rates in non-acidic systems might differ from well-studied acidic systems. We here aim to increase knowledge on geochemical processes controlling speciation and transport of metals under non-acidic river conditions. Specifically, we evaluate the predictive capacity of a speciation model to novel measurements of multiple metals and their partitioning, under high-pH conditions in mining zones within the Lake Baikal basin. The mining zones are potential hotspots for increasing metal loads to downstream river systems. Metals released from such upstream regions may be transported all the way to Lake Baikal, where increasing metal contamination of sediments and biota has been reported. Our results show clear agreement between speciation predictions and field measurements of Fe, V, Pb and Zn, suggesting that the partitioning of these metals mainly was governed by equilibrium geochemistry under the studied conditions. Systematic over-predictions of dissolved Cr, Cu and Mo by the model were observed, which might be corrected by improving the adsorption database for hydroxyapatite because that mineral likely controls the solubility of these metals. Additionally, metal complexation by dissolved organic matter is a key parameter that needs continued monitoring in the Lake Baikal basin because dependable predictions could not be made without considering its variability. Finally, our investigation indicates that further model development is needed for accurate As speciation predictions under non-acidic conditions, which is crucial for improved health risk assessments on this contaminant.

     

The effects of FeCl3 on the distribution of the heavy metals Cd, Cu, Cr, and Zn in a simulated multimetal incineration system

Recognizing that waste-derived chlorine can enhance heavy metal emissions by forming volatile metallic chlorides during municipal solid waste (MSW) combustion, and that in Taiwan, FeCl3-containing sewage sludge may either be landfilled or coincinerated with other MSW, this study thus investigated the effects of FeCl3 on the speciation and partitioning of heavy metals in a multimetal incineration system by using a tubular furnace and FeCl3-spiked simulated wastes. The molar ratio of chlorine content to heavy metal content (referred to as the Cl/ M ratio), ranging from 3 to 200, was used as a parameter to evaluate the effects of chlorine on the movement of heavy metals between the incinerator discharges. Results indicate that speciation and partitioning were related to the affinity between the chlorine and the heavy metals and between chlorine and hydrogen in the combustion system. The effectiveness of increasing the Cl/M ratio to the formation potential of metallic chlorides and on the shift of heavy metals from the bottom ash to the fly ash and/or the flue gases was found to have in increasing order as follows: Zn>Cu>Cr, a phenomenon basically reflecting the volatility of the heavy metals and their chlorides formed during combustion.     

Aquatic arsenic: Toxicity,speciation, transformations,and remediation

This paper reviews the current knowledge on the toxicity, speciation and biogeochemistry of arsenic in aquatic environmental systems. The toxicity of arsenic is highly dependent on the chemical speciation. The effects of pH, E_h, adsorbing surfaces, biological mediation, organic matter, and key inorganic substances such as sulfide and phosphate combine in a complex and interwoven dynamic fashion to produce unique assemblages of arsenic species. The number of different arsenic species found in environmental samples and an understanding of the transformations between arsenic species has increased over the past few decades as a result of new and refined analytical methods. Changes in arsenic speciation and in total arsenic content of foods upon processing have suggested possible risks associated with processed and unprocessed food. Arsenic removal from water using adsorbents, chemical oxidation, photolysis and photocatalytic oxidation techniques is also reviewed.     

乌江流域石灰土中铀等元素形态与铀活性

以中国西南乌江流域石灰土为例,运用逐级提取(Sequential Extraction,SEE)技术,并结合化学成分和相关参数数据,研究了石灰土中铀(U)等元素的形态,并在此基础上探讨了石灰土中U的活动性及释放潜力,旨在增进对U等元素生物地球化学循环的了解,同时也为流域U污染防治提供科学依据。研究结果表明：①石灰土中Mn主要存在于锰(氢)氧化物中,Ca主要存在于碳酸盐和硅酸盐矿物中,P主要存在于硅酸盐矿物和有机质中,U主要赋存于硅酸盐等残留部分中,其次赋存于有机质结合部分和碳酸盐矿物中;②石灰土剖面中活动态U所占的比例为10%~30%,平均17%,说明石灰土中的部分U在酸性和氧化-还原界面等条件下具有一定的迁移活性,即在上述条件下,石灰土中的部分U可释放进入周围水体或植物中;③石灰土中U的潜在释放量为036~150 g/t,平均U潜在释放量为076 g/t,因此,在酸雨和侵蚀等作用下,石灰土U释放可显著提高乌江河水U通量。     

Selection of a suitable mobile phase for the speciation of four arsenic compounds in drinking water samples using ion-exchange chromatography coupled to inductively coupled plasma mass spectrometry

The performance of two mobile phase buffers, phosphate and TRIS, were compared for the speciation of four arsenic species: arsenate (As(V)), arsenite (As(III)), mono methylarsonic acid (MMA), and dimethyl arsinic acid (DMA) in drinking water, using ion-exchange chromatography inductivelycoupled plasma mass spectrometry (IEC-ICP-MS). The mobile phase containing TRIS acetate buffer ("TRIS") demonstrated superior perfomance in baseline separation of all four arsenic species and the internal standard. It is also applicable to high-throughput sample analysis as it minimized the frequency required to clean the sampling interface due to salt build-up when compared to the phosphate mobile phase. The method was evaluated for its precision, accuracy, linearity and detection limits. The method was successfully applied for the analysis of drinking water samples.     

Speciation patterns of actinides in natural waters: a laboratory investigation

The results of laboratory investigations of actinide speciation in ground waters of varying compositions are summarized, re-evaluated and further interpreted, with the inclusion of additional data. Actinide speciation (solubility, oxidation state distributions) in these water samples exhibits great variability at 10⁻¹⁰ to 10⁻⁸ M total actinide concentrations. Americium solubility appears to be controlled by the formation of radiocolloids. neptunium is predictably oxidized and soluble in these water samples, with only a few exceptions. Plutonium exhibits widely varying oxidation state distributions—and hence solubility— despite the presence of 6 mg liter⁻¹ dissolved oxygen in all experiments. Plutonium solubility is enhanced by carbonate and fluoride but is diminished by sulfate in reducing waters. In general, these results are compatible with the limited information available for actinide speciation from previous in-situ investigations but they emphasize the paucity of accurate thermodynamic data to describe these systems.     

Primary and secondary components of PM2.5 in Milan (Italy)

In sampling campaigns--carried out by means of a high-volume gravimetric sampler--performed between August 2002 and December 2003, 24-h PM2.5 samples have been collected at an urban background site in downtown Milan and analyzed for elemental and organic carbon, ionic species (i.e., chloride, nitrates, sulfates and ammonium) and some elemental species. Chemical speciation data are evaluated also in terms of primary and secondary components of fine particulate matter: in particular, the contribution of secondary organic aerosols (SOA) and of the primary contribution from traffic to observed PM2.5 concentration levels are evaluated by means of the EC tracer method.     

Validating riverine transport and speciation models using nuclear reactor-derived radiocobalt

Risk assessment of intentional or accidental discharges of toxic substances into river systems requires combined hydraulic and chemical modeling. Periodic discharges of known volumes with low radioactivity by the Beznau nuclear reactor (Switzerland) serve as validation tracers for both river flow and chemical speciation simulation. Validation of the former has been achieved by comparison of modeled and measured arrival times of radiocobalt along a 65 km transect with a maximum reaction period of 24 hours. Modeled breakthrough curves coincide well with measurements collected during three field campaigns, in spite of the fact that sorption and sedimentation processes were not activated during simulation. This gives indirect evidence of inefficient cobalt sorption. Particle/solution distribution measurements carried out during breakthrough allow further validation of our speciation approach, which is based on Tableau setup of inorganic reactions combined with sorption and organic complexation. Modeled and measured speciation results confirm recent observations of enhanced complexation of cobalt with dissolved organic substances, which significantly reduces particle sorption. The large variability of conditional stability constants for sorption and complexation reactions, for sorption site densities, and for organic ligand concentrations explains the variability of published particle-solution distribution coefficients.     

Chloride - a precursor in the formation of volatile organochlorines by forest plants?

Two plants, a fern (Athyrium filix-femina) and a moss (Polytrichum commune Hedw.), both commonly occurring in Northern Temperate forests, were exposed in a laboratory study to a solution of (36)Cl-chloride. The uptake of (36)Cl-chloride by the plants was investigated and the emission of volatile chlorine 36 by the plants was determined. Furthermore, speciation of the emitted volatile organochlorine compounds (VOCls) was investigated. For the fern and the moss a rapid uptake of (36)Cl-chloride was observed within a 1-h exposure period. The uptake rates for the fern and the moss, respectively, were 16 mug (36)Cl-chloride g(-1) fresh weight (FW) h(-1) and 3.0 mug (36)Cl-chloride g(-1) FW h(-1), respectively. The study also suggested that after uptake by the plants (36)Cl-chloride is incorporated into VOCls, which were emitted by the plants into the atmosphere. Speciation analysis of the VOCls revealed the emission of chloroform, tetrachloromethane and 1,1,1-trichloroethane.     

Kinetics of dissolution of Chernobyl fuel particles in soil in natural conditions

Kinetic of fuel particles dissolution under natural environmental conditions has been investigated using the data on (90)Sr speciation in soils collected from 1995 to 1997 within the Chernobyl nuclear power plant 50 km zone. The dependency of fuel particles dissolution constants on the soil acidity (pH = 4-7) has been obtained on the basis of large and statistically reliable experimental data. Results show that between 2 and 21% of (90)Sr activity is associated with weathering resistant fuel particles. Therefore, these particles would not influence the radiological situation in the near future. The map of the main agrochemical characteristics and the map of the fuel particles dissolution constants have been created for the 30-km zone territory. According to the prognosis of dynamics of fuel particles dissolution in the investigated zone, a radiological situation along the fuel paths of radioactive fallout in present time reached a stable state. An increasing in absolute contents of (90)Sr mobile forms in neutral soils will be observed in the next 10-20 yr. However, the difference between the maximum level of mobile forms contents and their existing contents will not exceed 20%.     

Simulating potential vegetation distribution in a mountainous region of the Eastern Tibetan Plateau:A case study of Barkam County

The main objective of this study is to simulate the potential vegetation types on the basis of environmental parameters.The paper took Barkam County in a mountainous region of the Eastern Tibetan Plateau as the study area.The vegetation distribution was mapped in 1994 and 2007 based on TM remote sensing images by object-oriented interpretation method.We overlaid the two maps to find out the vegetation patches which have not changed,and took them as stable types.Fifty per cent of the stable patches were randomly sampled to operate the logistic regression with related environmental parameters;others were used as test data of simulated results.Seven environmental parameters were mapped,including elevation,slope,aspect,surface curvature,solar radiation,temperature and precipitation,based on DEM data and meteorological site data by GIS technology.The relationship between the spatial distribution of vegetation and environmental variables were quantified by logistic regression.The distribution probabilities of each vegetation type were calculated.Finally,the spatial distribution of potential vegetation was simulated.This research can provide a scientific basis for vegetation restoration and ecological construction in this area.     

Seasonal changes of redox potential and microbial activity in two agricultural soils of tropical Australia: some implications for soil-to-plant transfer of radionuclides

Very little is known of the factors controlling soil-to-plant transfer of radionuclides in tropical environments. As part of an IAEA/FAO coordinated research project (CRP) designed to elucidate some of those factors, near-surface samples of two agricultural red-earth soils (Blain and Tippera) were collected from a study site in the Northern Territory. The climate is tropical monsoonal with crops being grown over the wet season from December to March/April. It is important to understand soil variables that may be related to this dramatic seasonality. In this investigation, soil redox state and microbial populations were assessed before and after the growing season with a view to generating hypotheses for future evaluation. The X-ray absorption near edge structure (XANES) technique was used to determine overall changes in the solid-state redox speciation of Fe and Mn in soils across the growing period. Fe speciation did not change but approximately 10% of the total Mn was oxidised from Mn(II) to Mn(III) and Mn(IV) in both soils between October 1999 and April 2000. An apparent disconnect between Fe and Mn was not unexpected given the >10 times higher concentration of Fe in the soils compared with Mn. These results have implications for the bioavailability of redox sensitive radionuclides such as Tc and Pu. Similarly, microbial population estimates were derived before and after the growing period. Total bacterial populations did not vary from 10(6) to 10(7) colonies per gram. Fungal populations increased over the growing season from 3-6 x 10(5) to 1-4 x 10(6) colonies per gram of soil. Fungi have the potential to decrease soil pH and hence increase the bioavailability of radionuclides such as Cs. In addition, fungi act to facilitate plant nutrition. This could lead to enhanced accumulation of nutrient analogues (e.g. Sr and Ra for Ca; Tc for Mn), but this effect may be masked by improved biomass production.     

Environmental risk assessment of metals: tools for incorporating bioavailability

In this paper, some of the main processes and parameters which affect metal bioavailability and toxicity in the aquatic environment and its implications for metal risk assessment procedures will be discussed. It has become clear that, besides chemical processes (speciation, complexation), attention should also be given to physiological aspects for predicting metal toxicity. The development of biotic ligand models (BLMs), which combine speciation models with more biologically oriented models (e.g. GSIM), has offered an answer to this need. The various BLMs which have been developed and/or refined for a number of metals (e.g. Cu, Ag, Zn) and species (algae, crustaceans, fish) are discussed here. Finally, the potential of the BLM approach is illustrated through a theoretical exercise in which chronic zinc toxicity to Daphnia magna is predicted in three regions, taking the physico-chemical characteristics of these areas into account.     

Association of plutonium with sediments from the Ob and Yenisey Rivers and Estuaries

The present study applied sequential extraction techniques to investigate the binding and mobility of plutonium (Pu) in sediments from the rivers and estuaries of the Ob and Yenisey. As a study site, the Ob and Yenisey are particularly interesting as both rivers have weapons-grade Pu sources in their catchment areas, including the Russian Pu production and reprocessing plants at Mayak, Tomsk-7 and Krashnoyarsk, and the Semipalantinsk nuclear weapons testing site in Kazakhstan. Plutonium activity and ²⁴⁰Pu/²³⁹Pu ratios were determined using accelerator mass spectrometry (AMS). Sequential extractions showed that between 47 and 80% of the Pu in Yenisey River sediments and 35–53% of the Pu in soils around the Techa River are mobilized with weak oxidising agents, which can indicate that Pu is bound to organic material. In contrast, Pu in Ob and Yenisey Estuarine sediments was more strongly bound, with 60–100% being found in the HNO₃-extractable fraction. This change in speciation could reflect either that Pu bound to organic material in the Techa and Yenisey River sediments becomes more fixed to the sediments with time, or that organic-bound Pu is mobilized and released to the water when the sediments encounter the more saline water of the Ob and Yenisey estuaries. In general, ²⁴⁰Pu/²³⁹Pu ratios were relatively consistent between different extraction fractions, although, in whole sediments, an increase in ratio was observed with distance from the source. This reflects the increased influence of weapon fallout from catchment runoff within the river systems, as compared to the weapons-grade sources close to the production and reprocessing plants. Knowledge of Pu speciation in the Ob and Yenisey Rivers, and the processes controlling its behaviour in estuarine systems, can improve predictions of its transfer and subsequent environmental impact to Arctic Seas.