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.     

Surface complexation modeling of Yb(III) sorption and desorption on hematite and alumina

Sorption and desorption of Yb(III) were studied on hematite and on alumina using a surface complexation model. The experimental methodology was conceived to allow an analysis of the data using a constant capacitance model. The FITEQL code was used for the calculations.The experimental results tend to show reversibility of sorption when the surface loading is small, and irreversibility when the surface loading is high. Surface complexation modeling gives a good interpretation of these two phenomena, taking into account hydroxylation of the surface complexes. In these two cases, it is possible to describe sorption and desorption curves with the same surface stoichiometries and the same surface complexation constants. The existence of these surface complexes depends on the pH of the solution, surface loading, and reaction direction.     

Cationic surfactant as a sensitizer for the spectrophotometric determination of hydrogen sulphide in air and evaluation of a new absorbing medium containing triethanolamine-zinc acetate-sodium hydroxide

An extractive spectrophotometric method for the determination of trace amounts of hydrogen sulphide after fixing the gas in triethanolamine (TEA)-zinc acetate-sodium hydroxide solution is described. The method is based on the reaction of iodate with hydrogen sulphide in the presence of acid and excess chloride ion leading to the formation of ICl2- species which is used to iodinate 2',7'-dichlorofluorescein to form 2',7'-dichloro-4',5'-diiodofluorescein. The iodinated product formed is extracted into an organic solvent and sensitized by equilibrating with a cationic surfactant, cetrimide, in the presence of acetate buffer (pH 5.9 +/- 0.1). The colour system obeys Beer's law over the range 0-1 microg of hydrogen sulphide and the relative standard deviation is 2.4% for 10 determinations at 0.75 microg of hydrogen sulphide. The effect of interfering gases on the determination is discussed. The proposed absorbing solution has been evaluated using a hydrogen sulphide permeation device. This absorbing solution has an absorption efficiency of > 93% at a flow rate of 1.5 litre min(-1) for a sampling period of 2 h. The fixed H2S is stable for 40 days. The method has been applied to determine residual H2S levels in a laboratory fume hood and in the vicinity of sewage pumping station. The method can be used to determine as little as 0.05 microg of hydrogen sulphide.     

The impact of SO2 and SO2 + ascorbic acid treatments on growth and partitioning of dry matter in Trigonella foenum-graecum L

To study the impact of SO(2) and SO(2) + ascorbic acid on growth and partitioning of dry matter in Trigonella foenum-graecum L., two-week-old plants were exposed to SO(2) for 2 h daily over a 42 day period. One of the exposed sets was treated with ascorbic acid. Plants were grown in a wire house and unexposed plants were used as controls for comparison. The parameters measured, such as dry weights of leaf, stem and root per plant, were found to be lower in the exposed sets than in the controls. The reductions were greater in dry weights of stem and root as compared with weights of leaves, indicating that the partitioning of the dry matter was altered. Greater amounts of soluble sugars and starch in the leaves of exposed plants, compared with the stem, also revealed that translocation was hampered. Reductions were greater in fruiting than in flowering, suggesting that fruit abortion was high. Although ascorbic acid treatment could mitigate the effect of SO(2), the differences were not found to be statistically significant. Significant changes were seen in fruit yield, suggesting that the effect of ascorbic acid is cumulative. The impact of SO(2) and SO(2) + ascorbic acid on partitioning of dry matter to different 'sinks' is discussed.     

Radium-226 in cattails, Typha latifolia, and bone of muskrat, Ondatra zibethica (L.), from a watershed with uranium tailings near the city of Elliot Lake, Canada

Radium-226 concentrations were measured in the main food plants (cattails, Typha latifolia) and bone of adult muskrats (Ondatra zibethica (L.)), taken from a study area near Quirke Lake in the Serpent River drainage basin. This watershed receives drainage containing radionuclides from the U tailings near the City of Elliot Lake, Ontario, Canada. Two control sites (one local, one 130 km distant) were also sampled. Radium-226 levels in cattails varied by plant part and place of collection. Roots sampled in the study area had the highest mean (226)Ra level (1135.0 mBq g(-1)), stems and leaves had 284.2 and 275.9 mBq g(-1), respectively (dry-weight basis, n = 6 in all cases). Local and distant control cattails carried much lower (226)Ra levels (20.2 and 15.2 mBq g(-1) dry weight, respectively, using pooled equal portions of all plant parts, n = 3 in both cases). Muskrats from waters with mean total (226)Ra levels in the period, 1984-1987 greater than 75.0 mBq litre(-1) ('study-high' sites), near U tailings within 10 km of Quirke Lake, had a mean (geometric) bone level of (226)Ra of 344.9 mBq g(-1) (dry-weight basis, n = 36); those from nearby waters, containing < 75.0 mBq litre(-1) of (226)Ra ('study-low' sites), had a mean bone level (80.3 mBq g(-1), n = 9) similar to animals taken in unaffected local control areas 20 km from the tailings (79.1 mBq g(-1), n = 12); animals from the distant control area, near Sudbury, Ontario, had the lowest mean burden (11.5 mBq g(-1), n = 24). Levels were unrelated to age or sex of the animals. Dry-weight based (226)Ra concentration ratios (bone concentration/plant tissue concentration) were calculated to range from 0.3-1.4 in the study-high area to 2.4-6.3 in the local control area. Wet-weight based concentration ratios were about 4.3 times higher. Concentration ratios were similar to values calculated for other species and in general agreement with values calculated for humans. The muskrat is judged to be a useful indicator (biomonitor) of environmental (226)Ra levels as there is a highly significant positive correlation coefficient (r = 0.74) between bone and ambient (water) concentrations of the radionuclide (F79 = 95.04, P < 0.0001) Estimated yearly (226)Ra intake by people eating muskrats was calculated to be below the current allowable level set by Canadian regulatory authorities.     

U- and Th-series radionuclides in snowshoe hare (Lepus americanus) taken near U mill tailings close to Elliot Lake, Ontario, Canada

Snowshoe hare (Lepus americanus) trapped near U tailings had higher concentrations of (226)Ra in their bones (250 +/- 94 mBq g(-1) dry wt) than those from local control sites 3-15 km from the tailings (20-30 mBq g(-1) dry wt) and those from a distant control site 880 km away from the U mining area, which were below the detection limit (DL) (3.7 mBq g(-1) dry wt). Most chyme (stomach content) samples contained 226Ra below DL. Concentration ratios of 226Ra from tissues of local plants, considered important in the hare's diet, to bone ranged from 0.22 to 8.60. Concentrations of 210Pb and 210Po (95-245 mBq g(-1) dry wt) were not significantly different among tailings and control site populations. Disequilibrium between these isotopes and their precursors was noted. No significant accumulation of U and Th was noted at any site. Higher concentrations of 228Th compared to 232Th are attributed to accumulation of 228Ra in a manner similar to that of 226Ra. Based on bone 226Ra and 210Po contents, the maximum internal dose rates to the skeleton and the maximum life-time dose of hare living near tailings were 3.9 x 10(-5) Gy d(-1) and 4.2 x 10(-2) Gy, respectively. These rates were below the threshold required to produce osteosarcoma in other mammals and were considered unlikely to adversely affect hare during their lifetime. Radionuclide uptake by the animals was concluded to have no environmental significance in the transport of radionuclides from tailings to other locations.     

Effects of the phenylurea herbicide isoproturon on periphytic diatom communities in freshwater indoor microcosms

The toxic effects of the phenylurea herbicide Isoproturon -IPU: (3-(4-isopropylphenyl)-1, 1-dimethylurea)-were studied on the colonization of periphytic diatom communities, within indoor microcosms consisting of a mixed biotope (water column and natural sediment) and two biological species-rooted macrophyte cuttings (Elodea densa) and benthic bivalve molluscs (Corbicula fluminea). The periphyton, essentially composed of diatoms, was collected on artificial substrata (glass slides) in the upper layers of the water column, after two periods of exposure (34 and 71 days). IPU was initially added in the water or in the sediment compartment, at two nominal concentrations (L1 and L2 levels) for each contamination source-5 and 20 microg litre(-1) and 100 and 400 microg kg(-1) in sediment (w/w) respectively. The effects of IPU on the density and community structure of periphytic diatoms are described. A marked reduction in the diatom density was observed after 34 days exposure to the lower concentration of IPU in the water (5 microg litre(-1)). For the L2 levels, the very small number of live cells present did not permit quantification of the diatom density. After 71 days, recovery in community parameters occurred for the two contamination levels of the sediment and water column sources. Samples collected in the experimental units contaminated with the L2 levels were dominated by heterotrophic and smaller diatom species, such as Sellaphora seminulum. Data treatment based on factorial discriminant analysis enabled us to distinguish the different contamination conditions, with only 11 species from the 130 taxa identified.     

Effects of ethylenediurea (EDU) on ozone-induced acceleration of foliar senescence in potato (Solanum tuberosum L.)

Experiments were conducted to examine the effects of the anti-ozonant ethylenediurea (EDU) and chronic ozone (O3) exposure on leaf physiology and senescence in an O3-sensitive potato cultivar (Solanum tuberosum L. cv. Norland). A dose-response experiment showed that an EDU concentration of 15 mg l(-1) soil (given as a soil drench) provided complete protection from accelerated foliar senescence induced by exposure to 0.1 microl l(-1) O3 for 5 h day(-1) for 11 days. EDU doses of 45 and 75 mg active ingredient l(-1) soil also gave protection but were associated with symptoms of toxicity and delayed senescence. In further experiments, plants were given 0 or 15 mg EDU l(-1) soil and exposed to clean air or 0.1 microl l(-1) O3 for 5 h day(-1) for 14 days. Chronic O3 exposure in the absence of EDU resulted in accelerated foliar senescence, characterized by early declines in net photosynthesis and Rubisco quantity in O3-treated plants relative to controls. EDU in the presence of O3 gave complete protection against symptoms of accelerated senescence. Senescence was not delayed in plants that received EDU in the absence of O3, and no symptoms of EDU toxicity were evident. The results suggest that EDU-induced tolerance to O3 was not based on 'anti-senescent' properties of this anti-ozonant.     

The effect of chronic toxicity of copper on the activity of Balbiani rings and nucleolar organizing region in the salivary gland chromosomes of Chironomus ninevah larvae

The effect of copper on the activity of Balbiani rings (BR1 and BR2) and nucleolar organizing region (NOR) in chromosome IV of the salivary gland of the 4th instar larvae of Chironomus ninevah has been investigated. Sublethal concentrations, i.e. 0.02, 0.1, 0.15 and 0.2 mg litre(-1) suppress the activity of BR1, and are statistically significant. The same concentrations reduced the activity of BR2 and NOR, but without significant differences, except 0.1 mg litre(-1) which was significant. The purpose of this work was to evaluate the effect of chronic toxicity of Cu(2+) on the expression of gene activity of midge salivary gland chromosomes Although there may be many more aquatic organisms that are more sensitive to copper, this midge was selected as a biological indicator species because of its association with benthic sediments.     

Geochemical and Pb isotopic evidence for sources and dispersal of metal contamination in stream sediments from the mining and smelting district of Príbram, Czech Republic

Stream sediments from the mining and smelting district of Príbram, Czech Republic, were studied to determine the degree, sources and dispersal of metal contamination using a combination of bulk metal and mineralogical determinations, sequential extractions and Pb isotopic analyses. The highest metal concentrations were found 3-4 km downstream from the main polymetallic mining site (9800 mg Pb kg(-1), 26 039 mg Zn kg(-1), 316.4 mg Cd kg(-1), 256.9 mg Cu kg(-1)). The calculated enrichment factors (EFs) confirmed the extreme degree of contamination by Pb, Zn and Cd (EF>40). Lead, Zn and Cd are bound mainly to Fe oxides and hydroxides. In the most contaminated samples Pb is also present as Pb carbonates and litharge (PbO). Lead isotopic analysis indicates that the predominant source of stream sediment contamination is historic Pb-Ag mining and primary Pb smelting (206Pb/207Pb=1.16), while the role of secondary smelting (car battery processing) is negligible.