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.     

Patterns of soil copper contamination and temporal changes in vegetation in the vicinity of a copper rod rolling factory

Patterns of soil copper contamination have been examined in the vicinity of a copper rod rolling plant in Prescot, Merseyside, UK. The site, established in 1975, was found to possess clear patterns of soil copper contamination, with the highest levels of HNO3 and water-extractable fractions encountered in the factory grounds adjacent to the location of the furnace chimney. The majority of the copper had accumulated in the upper soil horizons. The site is surrounded by planted lawns, established at different times after the commissioning of the plant. The species composition of the extant grassland communities, found at sites with differing soil copper levels, was compared to the composition of the original seed mixtures sown at each of ten sites. These surveys clearly showed that different levels of soil copper contamination had produced significant changes in grassland composition with time. At the most polluted site, copper tolerant Agrostis capillaris clones were the main grasses present only two years after the area was sown with a four-species mixture of non-tolerant grass seed. Lolium perenne possessed extreme sensitivity to copper. A number of dicotyledonous species, normally considered sensitive to elevated copper levels, were found to be unaffected where such conditions had arisen after plants had established from seed.     

The influence of particle surface characteristics on pollutant metal uptake by cells

The phosphatic mineral, hydroxyapatite, and two ion exchange resins have been used as artificial sediment particles. The surface properties of these materials have been studied using the Langmuir adsorption isotherm to calculate the binding capacity (B(max)) and the adsorption constant (K(L)) for zinc and cadmium ions. Mussels (Mytilus edulis) were fed on the particles and their digestive glands were subsequently removed and subjected to cell fractionation. The supernatant fraction was used to determine cytosol metal levels as a measure of the materials absorbed from the ingested particles. The level of cytosol zinc and cadmium was correlated with the K(L) values of the artificial sediments. It is suggested that phagocytosis of sediment particles plays an important part in transferring pollutants into benthic organisms and that the efficiency of this process is related to the adsorption coefficient of the particle surfaces.     

Distribution of Organochlorine Pesticides in the Chao Phraya River, Thailand

Water samples from the Chao Phraya River, the main river in Thailand were collected and analyzed during 1988–1994. Organochlorine pesticides such as HCHs, DDTs, aldrin, dieldrin and chlordanes were determined. Aldrin and dieldrin had high frequencies of occurrence in water samples. The concentration median of the pesticides was approximately one order of magnitude higher than those of total HCHs and DDTs. Levels of aldrin were relatively high in the upstream while levels of DDTs were high in the urban area of Bangkok during 1989–1990. p,p-DDE levels were relatively higher in 1992. No clear trends in the levels of pesticides were observed.     

Enzymatic degradation of poly([R,S] β-hydroxybutyrate)

The synthetic analogue of a bacterially produced polyester, poly(-hydroxybutyrate) (PHB) was synthesized from racemic -butyrolactone using anin situ trimethyl aluminum-water catalyst. The polymer was fractionated into samples differing in molecular weight and isotactic diad content. The latter was closely related to degree of crystallinity. The biodegradation of these fractions were examined by monitoring mass loss over time in the presence of anAlcaligenes faecalis T1 extracellular bacterial poly(-hydroxybutyrate) depolymerase. The fraction with high isotactic diad tacticity content showed little or no degradation over a 50 hour incubation period, whereas the fraction of intermediate isotactic diad content degraded in a continuous steady fashion at a rate that was less than that for bacterial PHB. The low isotactic diad fraction underwent a rapid initial degradation, followed by no further mass loss. The presence of stereoblocks in the polymer structure of the various fractions was an influence on the degree of susceptibility towards degradation and is related to sample crystallinity.     

The impact of constituent ions of acid mist on assimilation and stomatal conductance of Norway spruce prior and post mid-winter freezing

Norway spruce seedlings were sprayed twice weekly with one of a range of artificial mists at either pH 2.5, 3.0 or 5.6, for three months. The mists consisted of either (NH4)2SO4 (pH 5.6), NH4NO3 (pH 5.6), water (pH 5.6), HNO3 (pH 2.5), H2SO4 (pH 2.5). In late December 1988 and early January 1989 the light response of assimilation and stomatal conductance were assessed in the laboratory following a 4-day equilibration period at 12 degrees C. The intact trees were then subjected to a mild (-10 degrees C), brief (3 h) frost in the dark and the recovery of light saturated assimilation (Amax) was followed during the subsequent light period. The same trees were then subjected to a second 3 h (-18 degrees C) frost. The recovery of Amax during the next day was followed. All ion-containing mists stimulated Amax and apparent quantum yield relative to control trees, irrespective of pH. The mists containing SO4 made stomatal conductance unresponsive to light flux density and caused the stomata to lock open. Frosts of -10 degrees C and -18 degrees C did not inhibit the Amax of control trees for longer than 200 min into the light period. In contrast, the ion-containing mists exerted a significant inhibitory effect upon the recovery of Amax. Nitric acid inhibited Amax to 35% of the pre-frost value, whilst the remaining treatments inhibited Amax between 15% and 40% of the pre-frost value. It is concluded that SO4 causes increased mid-winter frost sensitivity and NO3 ameliortes this effect. The results are discussed in relation to forest decline.     

The fate of endosulfan in aquatic ecosystems

Endosulfan, one of the major pesticides used in cotton-growing, is of environmental concern because of its toxicity to fish and its apparent persistence in the environment. This study examines the distribution and degradation pathways for endosulfan in an aquatic system and the processes by which it is removed. In the alkaline waters of the cotton region, hydrolysis is the dominant degradation process. By this mechanism alone, the expected half-lives for the alpha- and beta-endosulfan isomers were found to be 3.6 days and 1.7 days, respectively. Partitioning studies showed, however, that the major proportion of endosulfan would associate with the sediments (log Koc(alpha) 3.6 and log Koc(beta) 4.3). Field studies confirmed the presence of high concentrations in sediments. Microcosm experiments showed that loss of endosulfan was slower than predicted from hydrolysis rates. Models are presented to explain how desorption from sediment limits the loss of endosulfan from a system.     

Response of hydrogen peroxide scavenging system in two soybean cultivars exposed to SO2: experimental evidence for the detoxification of SO2 by enhanced H2O2 scavenging components

The impact of SO(2) on superoxide dismutase (SOD) and the ascorbate-glutathione cycle was investigated in a tolerant (cv. Punjab-1) and a sensitive (cv. JS 7244) cultivar of soybean (Glycine max (L.) Merr.). In spite of SO(2) stimulated SOD activities in both the cultivars, only cv. JS 7244 has significantly enhanced Malondialdehyde (MDA) contents. This differential response was attributed to the ability of cv. Punjab-1 to enhance glutathione reductase (GR) activity and to maintain high GSH/GSSG and ASA/DHA ratios. Post-fumigation analysis indicated the ability of cv. Punjab-1 to maintain SO(2)-enhanced antioxidants, whilst they declined in cv. JS 7244 the moment fumigation was terminated. Exposure of SO(2)-acclimated plants (cv. Punjab-1) with their enhanced antioxidants to 250 microg m(-3) SO(2) for 6 h exhibited no enhanced cellular injury (MDA content) when compared to that of control plants with their normal antioxidant levels. These results indicate a relation between the ability of a plant to maintain reduced glutathione (GSH) and ascorbate (ASA) and SO(2) tolerance, and they also present evidence for the ability of plants, with elevated antioxidants, to tolerate SO(2)-induced oxygen-free radical toxicity.     

The response of Lemna trisulca L. to cadmium

Lemna trisulca was grown, using aseptic culture techniques in a filter-sterilized medium, a portion of which was replaced regularly during experiments. L. trisulca responded to the addition of 0.64 microM Cd with a reduction in multiplication rate (MR) 2 +/- 1 days after exposure. The internal Cd content reached 1000 +/- 140 microg Cd/g (dry wt) within 2 days exposure to 0.64 microM Cd. The final yield was reduced by an average of c.8% for each day of exposure to 0.64 microM Cd in a 14 day experiment. This implies that an equilibration period should be used for short-term bioassay tests before the effect of a toxicant is determined. Pretreating L. trisulca with 0.08 or 0.32 microM Cd for 6 weeks had no significant effect on MR or Cd uptake when plants were subsequently exposed to a range of Cd concentrations or grown in a control medium. This suggests that L. trisulca does not become acclimated to elevated Cd concentrations. The MR of L. trisulca fluctuated over a period of almost 600 days and the doubling time ranged from 1.6 to 2.4 days. This produced more than a fivefold difference in final yield in experiments of 14 days duration. The reduction in MR in response to 0.32 microM Cd during this same 600 days period averaged 24% with a coefficient of variation of 38%, and varied with the MR of control cultures. Fluctuations in the intrinsic growth rate and the effect of a toxicant on L. trisulca could potentially confound the assessment of toxicity and must be carefully considered when designing test protocols for aquatic plants.     

Reproduction of mallards following overwinter exposure to selenium

Forty pairs of mallards (Anas platyrhynchos) were fed 15 ppm selenium as selenomethionine for about 21 weeks during winter. Twenty pairs served as controls. At the end of 21 weeks, which coincided with the onset of the reproductive season, selenium treatment was ended. Four birds died while on selenium treatment. Treated females lost weight, and their egg-laying was delayed. Hatching success of some of the first eggs laid by selenium-treated females was lower than that of controls, and a few of these early eggs contained deformed embryos, but, after a period of about two weeks off the selenium-treated diet, reproductive success returned to a level comparable with that of controls. The return to normal reproductive success was the result of a corresponding decrease in selenium concentrations in eggs once selenium treatment ended.