Uranium speciation in moorland river water samples: a comparison of experimental results and computer model predictions

An on-line method has been developed for separating inorganic and organic bound uranium species present in river water samples. The method utilised a small chelating resin (Hyphan) column incorporated into the sample introduction manifold of an ICP-MS instrument. The method was evaluated for samples from rivers on Dartmoor (Devon, UK), an area of granite overlain with peat bogs. The results indicate that organic-uranium species form a major proportion (80%) of the total dissolved uranium present. Further work with synthetic water samples indicated that the level of dissolved organic carbon played a greater role in determining the level of organic-uranium species than did sample pH. Computer models for the water samples were constructed using the WHAM program (incorporating uranium data from the Nuclear Energy Agency Thermochemical Database project) in order to predict the levels of organic-uranium species that would form. By varying the proportion of humic and fulvic acids used in the humic component, predictions within 10% of the experimental results were obtained. The program did exhibit a low bias at higher pH values (7.5) and low organic carbon concentrations (0.5 microg ml(-1)), but under the natural conditions prevalent in the Dartmoor water samples, the model predictions were successful.     

The effect of thermodynamic data on computer model predictions of uranium speciation in natural water systems

Computer models have found widespread application in order to help elucidate and predict changes in environmental systems. One such application is the prediction of trace metal speciation in aqueous systems. This is achieved by solving a set of non-linear equations involving equilibrium constants for all the components in the system, within mass and charge balance constraints. In this study a comparison of the predicted uranium speciation from two computer programs, WHAM and PHREEQCI, is used to illustrate the effect variations in thermodynamic data can have on the models produced. Using the original thermodynamic data provided with the models, WHAM predicted the UO2(2+) ion as the major species (84%) while PHREEQCI predicted UO2(HPO4)2(2-) as the major species (86%). Substituting uranium data from the Nuclear Energy Agency Thermochemical Database project (NEA-TDB) into both programs produced similar results from each program, with UO2F+ predicted to dominate (68%) in a groundwater sample. Natural water samples often contain humic substances. The possible interaction of such substances with uranium was also modelled. The WHAM program includes a discreet site electrostatic humic substance model, however in order to use the PHREEQCI program to model humic substance interactions, a 'model fulvic acid' dataset was added to the program. These models predicted 85 to 98% uranium-humic substance species at neutral pH. This indicates that humic substances do need to be taken into account when modelling uranium speciation in natural water samples.     

Metals, Boron, and Selenium in Neosho Madtom Habitats in the Neosho River in Kansas, U.S.A.

In 1991 and 1992 we determined the levels of metals, arsenic, boron, and selenium in the Neosho River drainage in southeastern Kansas, the primary habitat for the threatened Neosho madtom (Noturus placidus). We evaluated concentrations in sediments, mussels (Quadrula pustulosa and Q. metanevra), and fish(Percina phoxocephala, Cyprinus carpio,and Ictiobus bubalus) from three sites on theNeosho River and one site on the Cottonwood River. We also evaluated contaminant concentrations in C. carpio composite samples collected by theKansas Department of Health and Environment (KDHE)at two additional locations on the Neosho River in1990–92. Sediments were contaminated by lead. Concentrations of selenium, boron, and most metalsin mussels were low to normal for biota. Arseniclevels in mussels and fish suggest low-levelcontamination of biota. Aluminum, barium, manganeseand strontium concentrations were much higher inmussels than in fish. Five fish composite sampleshad cadmium concentrations that indicate chronicdeleterious effects on biota. Lead concentrationsin six fish samples were elevated. Mercuryconcentrations in most large fish compositesexceeded concentration for protection of animalsthat might consume them. We believe that reductionsin cadmium, lead, and mercury contamination, inparticular, would benefit aquatic life in theriver.     

Dependence of home outdoor particulate mass and number concentrations on residential and traffic features in urban areas

The associations between residential outdoor and ambient particle mass, fine particle absorbance, particle number (PN) concentrations, and residential and traffic determinants were investigated in four European urban areas (Helsinki, Athens, Amsterdam, and Birmingham). A total of 152 nonsmoking participants with respiratory diseases, not exposed to occupational pollution, were included in the study, which comprised a 7-day intensive exposure monitoring period of both indoor and home outdoor particle mass and number concentrations. The same pollutants were also continuously measured at ambient fixed sites centrally located to the studied areas (fixed ambient sites). Relationships between concentrations measured directly outside the homes (residential outdoor) and at the fixed ambient sites were pollutant-specific, with substantial variations among the urban areas. Differences were more pronounced for coarse particles due to resuspension of road dust and PN, which is strongly related to traffic emissions. Less significant outdoor-to-fixed variation for particle mass was observed for Amsterdam and Birmingham, predominantly due to regional secondary aerosol. On the contrary, a strong spatial variation was observed for Athens and to a lesser extent for Helsinki. This was attributed to the overwhelming and time-varied inputs from traffic and other local sources. The location of the residence and traffic volume and distance to street and traffic light were important determinants of residential outdoor particle concentrations. On average, particle mass levels in suburban areas were less than 30% of those measured for residences located in the city center. Residences located less than 10 m from a street experienced 133% higher PN concentrations than residences located further away. Overall, the findings of this multi-city study, indicated that (1) spatial variation was larger for PN than for fine particulate matter (PM) mass and varied between the cities, (2) vehicular emissions in the residential street and location in the center of the city were significant predictors of spatial variation, and (3) the impact of traffic and location in the city was much larger for PN than for fine particle mass.     

Phytoremediation of arsenic contaminated paddy soils with Pteris vittata markedly reduces arsenic uptake by rice

Arsenic (As) accumulation in food crops such as rice is of major concern. To investigate whether phytoremediation can reduce As uptake by rice, the As hyperaccumulator Pteris vittata was grown in five contaminated paddy soils in a pot experiment. Over a 9-month period P. vittata removed 3.5-11.4% of the total soil As, and decreased phosphate-extractable As and soil pore water As by 11-38% and 18-77%, respectively. Rice grown following P. vittata had significantly lower As concentrations in straw and grain, being 17-82% and 22-58% of those in the control, respectively. Phytoremediation also resulted in significant changes in As speciation in rice grain by greatly decreasing the concentration of dimethylarsinic acid (DMA). In two soils the concentration of inorganic As in rice grain was decreased by 50-58%. The results demonstrate an effective stripping of bioavailable As from contaminated paddy soils thus reducing As uptake by rice.     

The risk of harmful algal blooms (HABs) in the oyster-growing estuaries of New South Wales, Australia

The spatial and temporal variability of potentially harmful phytoplankton was examined in the oyster-growing estuaries of New South Wales. Forty-five taxa from 31 estuaries were identified from 2005 to 2009. Harmful species richness was latitudinally graded for rivers, with increasing number of taxa southward. There were significant differences (within an estuary) in harmful species abundance and richness for 11 of 21 estuaries tested. Where differences were observed, these were predominately due to species belonging to the Pseudo-nitzschia delicatissima group, Dinophysis acuminata, Dictyocha octonaria and Prorocentrum cordatum with a consistent upstream versus downstream pattern emerging. Temporal (seasonal or interannual) patterns in harmful phytoplankton within and among estuaries were highly variable. Examination of harmful phytoplankton in relation to recognised estuary disturbance measures revealed species abundance correlated to estuary modification levels and flushing time, with modified, slow flushing estuaries having higher abundance. Harmful species richness correlated with bioregion, estuary modification levels and estuary class, with southern, unmodified lakes demonstrating greater species density. Predicting how these risk taxa and risk zones may change with further estuary disturbance and projected climate warming will require more focused, smaller scale studies aimed at a deeper understanding of species-specific ecology and bloom mechanisms. Coupled with this consideration, there is an imperative for further taxonomic, ecological and toxicological investigations into poorly understood taxa (e.g. Pseudo-nitzschia).