Selectivity in the complexation of actinides by humic substances

The interactions of a range of actinide elements (Th, U, Np, Pu, Am) with humic substances from the Needle's Eye natural analogue site were studied by gel permeation chromatography. Bulk humic substances were isolated by ammonia extraction, followed by dialysis against distilled water and freeze-drying. The gel permeation results suggest that Needle's Eye humic substances can be fractionated into three incompletely resolved fractions with average molecular weights determined by analytical ultracentrifugation around 49 000 for Fraction 1, around 14 700 for Fraction 2 and around 8000 for Fraction 3. Although there are significant differences between the organic matter elution patterns in individual gel permeation experiments, presumably due to differences in column packing, these are much smaller than the differences between metal ions. The uranium that is naturally present in these humic substances is largely bound in the late-eluting fraction. Spikes of the early actinides, including Np and Pu in controlled valency states, have been added to the humic substances, and gel permeation of the spiked humic substances shows that the three humic fractions vary greatly in their effectiveness and selectivity as ligands for early actinides.     

Mass Spectrometric Detection and Identification of Polar Pesticides and their Degradation Products - A Comparison of Different Ionization Methods

Due to increasing use of polar pesticides, they are found together with their degradation products in ground- and surface waters serving for drinking water treatment. The triazine derivatives acetamido-atrazine, ametryne, atrazine, cyanazine, deethylatrazine, deethyldeisopropyl-hydroxyatrazine, deethyl-hydroxyatrazine, deisopropyl-atrazin, deisopropyl-hydroxyatrazine, desmetryn, hydroxyatrazine, prometryne, propazine, simazine, terbumeton, terbutryne and terbutylazine, and the pesticides 2,4-D, dichlorprop, isoproturon, diuron, metolachlor, glyphosate, metsulfuronmethyl and dalapon, all of them belonging to this type of pesticides, have been studied. For determination of triazine derivatives UV detection by means of diode array detector (DAD) as well as mass spectrometric (MS) detection coupled by thermospray interface (TSP) have been used successfully after liquid chromatoraphic (LC) separation. Interfaces like thermospray (TSP), electrospray (ESP) and atmospheric pressure chemical ionisation (APCI) were examined with regard to their suitability for substance-specific detection of polar pesticides by flow injection analysis (FIA) with MS- and tandem mass spectroscopic detection (MS/MS) without preceding LC separation. Optimised detection conditions for these pesticides using FIA are presented, and solutions for occurring problems are offered.     

Evidence for the remobilisation of transuranic elements in the terrestrial environment

The transuranium elements, Np, Pu and Am discharged from the BNFL fuel reprocessing plant at Sellafield have accumulated in the local environment. The processes responsible for their dispersal rely both on physical transportation and their chemical reactivity. The transuranics have a complex chemistry, with multiple oxidation states and a strongly polarising character. In the environment, the particle active III/IV and more mobile VNI oxidation state groups are important and govern their geochemical behaviour and subsequent dispersal. Studies of the behaviour of the transuranics, particularly Pu, in the Irish Sea, have shown that the majority of the radionuclides in the liquid effluent discharged from Sellafield, quickly becomes associated with the marine sediments. Their dispersal and distribution in the environment is then governed primarily by the movement of particulate material and for some sites it has been suggested that sediment profiles preserve the historical record of discharges from the plant. In tidally inundated soils, radionuclide levels are greatly enhanced. These soils are water-logged for long periods of the year, are strongly anoxic and accretion rate are very low. The distribution of Np, Pu and Am in the soil suggests that simple sedimentary accumulation mechanism cannot provide an adequate explanation for the profiles observed. From preliminary studies of soil pore water composition and detailed analysis of the variation of isotopic ratios in the soil cores, it is apparent that a small but significant component of the radionuclide inventory is mobile. In addition, it is clear that the mechanisms responsible for this mobility allows differentiation between the transuranium nuclides.     

X-ray absorption spectroscopy studies of reactions of technetium, uranium and neptunium with mackinawite

Technetium, uranium and neptunium may all occur in the environment in more than one oxidation state (IV or VII, IV or VI and IV or V respectively). The surface of mackinawite, the first-formed iron sulfide phase in anoxic conditions, can promote redox changes so a series of laboratory experiments were carried out to explore the interactions of Tc, U and Np with this mineral. The products of reaction were characterised using X-ray absorption spectroscopy. Technetium, added as TcO4(-), is reduced to oxidation state IV and forms a TcS(2)-like species. On oxidation of the mackinawite in air to form goethite, Tc remains in oxidation state IV but in an oxide, rather than a sulfide environment. At low concentrations, uranium forms uranyl surface complexes on oxidised regions of the mackinawite surface but at higher concentrations, the uranium promotes surface oxidation and forms a mixed oxidation state oxide phase. Neptunium is reduced to oxidation IV and forms a surface complex with surface sulfide ions. The remainder of the Np coordination sphere is filled with water molecules or hydroxide ions.     

A review of radionuclides in tide-washed pastures on the Irish Sea coast in England and Wales and their transfer to food products

Close to the Sellafield Reprocessing Plant activity concentrations of many radionuclides including the long-lived 137Cs and actinides on tide-washed pastures bordering the Irish Sea are high compared with other terrestrial ecosystems in the United Kingdom. Despite the comparatively high deposition of radionuclides, contamination of agricultural products from tide-washed pastures is lower than would be predicted from studies in terrestrial ecosystems. This is because the main source of contamination in tide-washed pasture, radionuclides associated with sedimentary particles, has low availability for uptake by plant roots and in the gut of ruminants. Generalised Derived Limits (GDLs), published by the National Radiological Protection Board (NRPB) are estimates of environmental radioactivity concentrations which would potentially be radiologically significant. These provide a benchmark against which environmental measurements can be assessed. In the past, several comparisons of radioactivity concentrations in tide-washed pastures with GDLs have been made, but only some of these comparisons are valid since current approaches used to assess doses are not always strictly appropriate to these ecosystems. Directly applicable GDLs are needed, and are currently being developed by the NRPB.     

Predicted Climate‐Driven Bird Distribution Changes and Forecasted Conservation Conflicts in a Neotropical Savanna

Abstract: Climate‐change scenarios project significant temperature changes for most of South America. We studied the potential impacts of predicted climate‐driven change on the distribution and conservation of 26 broad‐range birds from South America Cerrado biome (a savanna that also encompass tracts of grasslands and forests). We used 12 temperature or precipitation‐related bioclimatic variables, nine niche modeling techniques, three general circulation models, and two climate scenarios (for 2030, 2065, 2099) for each species to model distribution ranges. To reach a consensus scenario, we used an ensemble‐forecasting approach to obtain an average distribution for each species at each time interval. We estimated the range extent and shift of each species. Changes in range size varied across species and according to habitat dependency; future predicted range extent was negatively correlated with current predicted range extent in all scenarios. Evolution of range size under full or null dispersal scenarios varied among species from a 5% increase to an 80% decrease. The mean expected range shifts under null and full‐dispersal scenarios were 175 and 200 km, respectively (range 15–399 km), and the shift was usually toward southeastern Brazil. We predicted larger range contractions and longer range shifts for forest‐ and grassland‐dependent species than for savanna‐dependent birds. A negative correlation between current range extent and predicted range loss revealed that geographically restricted species may face stronger threat and become even rarer. The predicted southeasterly direction of range changes is cause for concern because ranges are predicted to shift to the most developed and populated region of Brazil. Also, southeastern Brazil is the least likely region to contain significant dispersal corridors, to allow expansion of Cerrado vegetation types, or to accommodate creation of new reserves.     

Chemical reactions of metals with humic material

Humic substances are chemically very complex materials whose structure and reactions are not fully understood. They are believed to be macromolecules, spanning a wide range of molecular weights, which are formed from quinones and phenolic compounds. They contain a wide variety of functional groups, which may react with metals. Many different physical and chemical procedures have been used to study these interactions, and numerous different reaction mechanisms and products have been postulated. The colloidal properties of humic materials also affects their interactions with metals. Reaction with humic substances profoundly affects the environmental behaviour of metals. Solubility, plant availability and even volatility are all greatly influenced and can be either enhanced or reduced by these reactions.     

Residential Water Consumption,Motivation for Conserving Water and the Continuing Tragedy of the Commons

This paper explores the effect of the perception of externalities (PE) on residential water consumption. Externalities occur when individuals make decisions that harm others, without concern for the impact or feeling a need to compensate for the harm. The aim of this study was to investigate whether PE affects people's motivation to conserve water, and, consequently, the practice of residential water consumption. Two hundred eighty Mexican citizens responded to a questionnaire investigating how they perceived that other individuals in their community wasted water. Respondents were also asked about their motives to conserve water, and direct observations of individual water consumption were recorded. Results were processed within a structural equations model, which revealed that motives to conserve water significantly inhibit water consumption. Since the perception of externalities also inhibits conservation motives, the resulting effect of PE on water consumption is positive. This result means that the more people perceive that others waste water, the less their conservation motives, and, therefore, the more their own water consumption.     

Plutonium solubility in sediment pore waters

Using in situ porous cup samplers, dissolved Pu concentrations have been measured over a year in the pore waters from two contrasting sites in the valley of the River Esk, North West England. In saltmarsh sediments, dissolved Pu represents approximately 1 part in 10(6) of the total inventory. The Pu concentration in solution is in the range 1.1-3.5 mBq l-1, varying by a factor of 3 in the course of the year. Most of the changes in dissolved Pu coincide with changes in dissolved Fe and Mn concentrations, with Pu being low in the summer months when Fe and Mn are high. Nevertheless, there are a number of factors which make it unclear as to whether these patterns might be related to seasonal redox changes in the saltmarsh. At the highly organic, reducing reedbed site, the proportion of Pu in solution is typically around 1 part in 10(3), proportionately much higher than in the saltmarsh, giving concentrations ranging between 9.0 and 28.5 mBq l-1, and are apparently maintained by complexation to dissolved organic matter. There is no obvious seasonal pattern at the reedbed site nor is there any relation to any of the dissolved species measured (Fe, Mn, Na, DOC).