Kinetics of uranium(VI) lability and solubility in aerobic soils.

Uranium may pose a hazard to ecosystems and human health due to its chemotoxic and radiotoxic properties. The long half-life of many U isotopes and their ability to migrate raise concerns over disposal of radioactive wastes. This work examines the long-term U bioavailability in aerobic soils following direct deposition or transport to the surface and addresses two questions: (i) to what extent do soil properties control the kinetics of U speciation changes in soils and (ii) over what experimental timescales must U reaction kinetics be measured to reliably predict long-term of impact in the terrestrial environment? Soil microcosms spiked with soluble uranyl were incubated for 1.7 years. Changes in UVI fractionation were periodically monitored by soil extractions and isotopic dilution techniques, shedding light on the binding strength of uranyl onto the solid phase. Uranyl sorption was rapid and strongly buffered by soil Fe oxides, but UVI remained reversibly held and geochemically reactive. The pool of uranyl species able to replenish the soil solution through several equilibrium reactions is substantially larger than might be anticipated from typical chemical extractions and remarkably similar across different soils despite contrasting soil properties. Modelled kinetic parameters indicate that labile UVI declines very slowly, suggesting that the processes and transformations transferring uranyl to an intractable sink progress at a slow rate regardless of soil characteristics. This is of relevance in the context of radioecological assessments, given that soil solution is the key reservoir for plant uptake.

Elemental composition of aquaculture fish from West Bengal, India: nutrition versus food safety.

Aquaculture production continues to grow in West Bengal, where on average people consume 8.2 kg capita-1 of fish each year, and an extensive mosaic of aquaculture ponds has developed along the River Hugli as clay pits are repurposed. The adjacent brickworks and industry (especially tanneries) are a source of environmental pollution, with potential for bioaccumulation of potentially harmful elements (PHEs) in fish farmed in these ponds. Fish from aquaculture present an opportunity to meet food sufficiency in West Bengal; however, an investigation to assess their effectiveness for micronutrient supply balanced against food safety is required. Five ponds close to industrial brick manufacture (urban) and three from rural areas were assessed for the degree of pollution within their pond sediments and waters. Fish were also sampled from each location including a subset from the market in Kolkata to determine the concentrations of PHEs in their fish muscle tissue. Dietary intake and PHE loading were calculated for four fish species to evaluate their nutrient content with respect to recommended daily intakes for adults, e.g. calcium (Ca), potassium (K), magnesium (Mg), iron (Fe), zinc (Zn) and selenium (Se), and to establish whether the provisional maximum tolerable intakes (PMTIs) are exceeded for PHEs, e.g. aluminium (Al), arsenic (As), mercury (Hg), chromium (Cr), tin (Sn), copper (Cu) and lead (Pb). Preliminary results suggest that aquaculture is making an important contribution to nutrition, with fish being a good source of Se. However, in contrast to small wild-caught fish, aquaculture fish in the present study were poor sources of Fe, Ca and Zn. The fish also made substantial contributions (> 10%) to the PMTI of Hg and As. Therefore, there is an urgent need for ongoing monitoring and an expanded sampling programme, as well as research into approaches which might improve the nutritional quality of the farmed fish.

Kinetic study of time-dependent fixation of UVI on biochar.

Biochar, a by-product from the production of biofuel and syngas by gasification, was tested as a material for adsorption and fixation of UVI from aqueous solutions. A batch experiment was conducted to study the factors that influence the adsorption and time-dependent fixation on biochar at 20°C, including pH, initial concentration of UVI and contact time. Uranium (UVI) adsorption was highly dependent on pH but adsorption on biochar was high over a wide range of pH values, from 4.5 to 9.0, and adsorption strength was time-dependent over several days. The experimental data for pH>7 were most effectively modelled using a Freundlich adsorption isotherm coupled to a reversible first order kinetic equation to describe the time-dependent fixation of UVI within the biochar structure. Desorption experiments showed that UVI was only sparingly desorbable from the biochar with time and isotopic dilution with 233UVI confirmed the low, or time-dependent, lability of adsorbed 238UVI. Below pH 7 the adsorption isotherm trend suggested precipitation, rather than true adsorption, may occur. However, across all pH values (4.5-9) measured saturation indices suggested precipitation was possible: autunite below pH 6.5 and either swartzite, liebigite or bayleyite above pH 6.5.

Assessment of trace elements in the shell layers and soft tissues of the pearl oyster Pinctada radiata using multivariate analyses: a potential proxy for temporal and spatial variations of trace elements.

Concentrations of trace elements (Cd, Cu, Ni, Pb, V, and Zn) were determined in the soft tissues (adductor muscle and gills) of the pearl oyster Pinctada radiata and surficial sediments from two sampling sites located in the northern part of the Persian Gulf by Graphite Furnace Atomic Absorption Spectrophotometer (GFAAS). Moreover, the levels of Li, Mg, Al, Mn, Fe, Cu, Sr, Ba, Pb, and Zn were measured in two shell layers (prismatic and nacreous) using Laser Ablation Inductively Coupled Plasma Mass Spectrometer (LA-ICP-MS). There were significant differences between the sampling sites with regard to mean concentrations of Cu, Mn, and Al in the prismatic layers of the shells. But in terms of the soft tissues, only in the case of Ni accumulation in the muscle significant differences between the sites could be observed. No significant differences could be found between the sites from the elements concentrations in the sediments point of view. The levels of Cd, Cu, Ni, and Zn in the gills were markedly higher than those in the muscle. Concentrations of Mn, Mg, Li, and Cu in the prismatic layer were significantly higher than in the nacreous but the reverse case could be found for Sr. The patterns of metal occurrence in the selected tissues, shell layers, and sediments exhibited the following descending order: Zn, Ni > Cd, Cu > V, and Pb and Zn, Ni, Cd > Cu, V, and Pb for muscle and gills, respectively; Zn > Cu, Ni, Pb, Cd, and V for sediments; Mg > Sr, Mn, Li, Al, Fe, Ba, Cu, Pb, and Zn for the prismatic layer; and Sr, Mg > Mn, Al, Fe, Li, Ba, Cu, Pb, and Zn for the nacreous layer. In most cases, the temporal variations of the elements levels in the prismatic layer were clearer than those in the nacreous layer (especially for Li, Mg, Mn, Pb, and Fe). Comparison of the gained data from this study with the other relevant researches shows that in most cases the levels of the elements in this investigation either fell within the range for other world areas or were lower. Generally, it can be concluded that the shell (especially prismatic layer) of P. radiata can be considered as a suitable proxy for temporal and spatial variations of the trace elements (and probably some environmental parameters) in the study area.

Sources, lability and solubility of Pb in alluvial soils of the River Trent catchment, U.K.

Alluvial soils are reservoirs of metal contaminants such as Pb that originate from many different sources and are integrated temporally and spatially through erosional and depositional processes. In this study the source, lability and solubility of Pb were examined in a range of alluvial soils from the middle and lower River Trent and its tributary the River Dove using Pb isotope apportionment and isotopic dilution. All samples were collected within 10 m of the river bank to represent the soil that is most likely to be remobilised during bank erosion. Paired samples were taken from the topsoil (0-15 cm) and subsoil (35-50 cm) to assess differences with depth. Lead concentrations in soil ranged from 43 to 1282 mg/kg. The lability of soil Pb varied between 9 and 56% of total metal concentration whilst Pb concentrations in pore water varied between 0.2 and 6.5 µg/L. There was little difference in the % Pb lability between paired top and sub soils, possibly because soil characteristics such as pH, iron oxides and clay content were generally similar; a result of the recycling of eroded and deposited soils within the river system. Soil pH was found to be negatively correlated with % Pb lability. Source apportionment using (206)Pb/(207)Pb and (208)Pb/(207)Pb ratios showed that the isotopic ratios of Pb in the total, labile and solution pools fitted along a mixing line between Broken Hill Type ('BHT') Pb, used as an additive in UK petrol, and the local coal/Southern Pennine ore Pb. Various anomalies were found in the Pb isotopes of the bankside alluvial soils which were explained by point source pollution. Statistically significant differences were found between (i) the isotopic composition of Pb in the total soil pool and the labile/solution pools and (ii) the isotopic composition of Pb in the labile and solution pools, suggesting an enrichment of recent non-Pennine sources of Pb entering the soils in the labile and solution pools.

Soil-plant interactions and the uptake of Pb at abandoned mining sites in the Rookhope catchment of the N. Pennines, UK--a Pb isotope study.

This paper examines Pb concentrations and sources in soil, grass and heather from the Rookhope catchment in the North Pennines, UK, an area of historical Pb and Zn mining and smelting. Currently, the area has extensive livestock and sports shooting industries. Risk assessment, using the source-pathway-receptor paradigm, requires the quantification of source terms and an understanding of the many factors determining the concentration of Pb in plants. A paired soil and vegetation (grass and heather) geochemical survey was undertaken. Results showed no direct correlation between soil (total or EDTA extractable Pb) and vegetation Pb concentration. However, regression modelling based on the Free-Ion Activity Model (FIAM) suggested that the underlying mechanism determining grass Pb concentration across the catchment was largely through root uptake. Spatial patterns of (206/207)Pb isotopes suggested greater aerosol deposition of Pb on high moorland and prevailing wind facing slopes. This was evident in the isotopic ratios of the heather plants. Pb isotope analysis showed that new growth heather tips typically had (206/207)Pb values of ~1.14, whilst grass shoots typically had values ~1.16 and bulk soil and peat ~1.18. However, the (206/207)Pb ratio in the top few cm of peat was ~1.16 suggesting that grass was accessing Pb from a historical/recent pool of Pb in soil/peat profiles and consisting of both Pennine ore Pb and long-range Pb deposition. Isotope Dilution assays on the peat showed a lability of between 40 and 60%. A simple source apportionment model applied to samples where the isotope ratios was not within the range of the local Pennine Pb, suggested that grass samples contained up to 31% of non-Pennine Pb. This suggests that the historical/recent reservoir of non-Pennine Pb accessed by roots continues to be a persistent contaminant source despite the principal petrol Pb source being phased out over a decade ago.

Chemical signatures of the Anthropocene in the Clyde estuary, UK: sediment-hosted Pb, (207/206)Pb, total petroleum hydrocarbon, polyaromatic hydrocarbon and polychlorinated biphenyl pollution records.

The sediment concentrations of total petroleum hydrocarbons (TPHs), polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), Pb and (207/206)Pb isotope ratios were measured in seven cores from the middle Clyde estuary (Scotland, UK) with an aim of tracking the late Anthropocene. Concentrations of TPHs ranged from 34 to 4386 mg kg(-1), total PAHs from 19 to 16,163 µg kg(-1) and total PCBs between less than 4.3 to 1217 µg kg(-1). Inventories, distributions and isomeric ratios of the organic pollutants were used to reconstruct pollutant histories. Pre-Industrial Revolution and modern non-polluted sediments were characterized by low TPH and PAH values as well as high relative abundance of biogenic-sourced phenanthrene and naphthalene. The increasing industrialization of the Clyde gave rise to elevated PAH concentrations and PAH isomeric ratios characteristic of both grass/wood/coal and petroleum and combustion (specifically petroleum combustion). Overall, PAHs had the longest history of any of the organic contaminants. Increasing TPH concentrations and a concomitant decline in PAHs mirrored the lessening of coal use and increasing reliance on petroleum fuels from about the 1950s. Thereafter, declining hydrocarbon pollution was followed by the onset (1950s), peak (1965-1977) and decline (post-1980s) in total PCB concentrations. Lead concentrations ranged from 6 to 631 mg kg(-1), while (207/206)Pb isotope ratios spanned 0.838-0.876, indicative of various proportions of 'background', British ore/coal and Broken Hill type petrol/industrial lead. A chronology was established using published Pb isotope data for aerosol-derived Pb and applied to the cores.

The distribution of depleted uranium contamination in Colonie, NY, USA.

Uranium oxide particles were dispersed into the environment from a factory in Colonie (NY, USA) by prevailing winds during the 1960s and '70s. Uranium concentrations and isotope ratios from bulk soil samples have been accurately measured using inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) without the need for analyte separation chemistry. The natural range of uranium concentrations in the Colonie soils has been estimated as 0.7-2.1 microg g(-1), with a weighted geometric mean of 1.05 microg g(-1); the contaminated soil samples comprise uranium up to 500+/-40 microg g(-1). A plot of (236)U/(238)U against (235)U/(238)U isotope ratios describes a mixing line between natural uranium and depleted uranium (DU) in bulk soil samples; scatter from this line can be accounted for by heterogeneity in the DU particulate. The end-member of DU compositions aggregated in these bulk samples comprises (2.05+/-0.06) x 10(-3)(235)U/(238)U, (3.2+/-0.1)x10(-5)(236)U/(238)U, and (7.1+/-0.3) x 10(-6)(234)U/(238)U. The analytical method is sensitive to as little as 50 ng g(-1) DU mixed with the natural uranium occurring in these soils. The contamination footprint has been mapped northward from site, and at least one third of the uranium in a soil sample from the surface 5 cm, collected 5. 1km NNW of the site, is DU. The distribution of contamination within the surface soil horizon follows a trend of exponential decrease with depth, which can be approximated by a simple diffusion model. Bioturbation by earthworms can account for dispersal of contaminant from the soil surface, in the form of primary uranium oxide particulates, and uranyl species that are adsorbed to organic matter. Considering this distribution, the total mass of uranium contamination emitted from the factory is estimated to be c. 4.8 tonnes.