Quantifying constraints imposed by calcium and iron on bacterial reduction of uranium(VI)

Uranium is a redox active contaminant of concern to both human health and ecological preservation. In anaerobic soils and sediments, the more mobile, oxidized form of uranium (UO(2)(2+) and associated species) may be reduced by dissimilatory metal-reducing bacteria. Despite rapid reduction in controlled, experimental systems, various factors within soils or sediments may limit biological reduction of U(VI), inclusive of competing electron acceptors and alterations in uranyl speciation. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite, and hematite) varying in free energies of formation. Observed pseudo first-order rate coefficients for U(VI) reduction vary from 12 +/- 0.60 x 10(-3) h(-1) (0 mM Ca in the presence of goethite) to 2.0 +/- 0.10 x 10(-3) h(-1) (0.8 mM Ca in the presence of hematite). Nevertheless, dissolved Ca (at concentrations from 0.2 to 0.8 mM) decreases the extent of U(VI) reduction by approximately 25% after 528 h relative to rates without Ca present. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Ferrihydrite, in contrast, acts as a competitive electron acceptor and thus, like Ca, decreases uranium reduction. However, while ferrihydrite decreases U(VI) in solutions without Ca, with increasing Ca concentrations U(VI) reduction is enhanced in the presence of ferrihydrite (relative to its absence)-U(VI) reduction, in fact, becomes almost independent of Ca concentration. The quantitative framework described herein helps to predict the fate and transport of uranium within anaerobic environments.     

Assessment of pesticide residues in army cutworm moths (Euxoa auxiliaris) from the Greater Yellowstone Ecosystem and their potential consequences to foraging grizzly bears (Ursus arctos horribilis)

During summer, a grizzly bear (Ursus arctos horribilis) in the Greater Yellowstone Ecosystem (GYE) (USA) can excavate and consume millions of army cutworm moths (Euxoa auxiliaris) (ACMs) that aggregate in high elevation talus. Grizzly bears in the GYE were listed as threatened by the US Fish and Wildlife Service in 1975 and were proposed for delisting in 2005. However, questions remain about key bear foods. For example, ACMs are agricultural pests and concern exists about whether they contain pesticides that could be toxic to bears. Consequently, we investigated whether ACMs contain and transport pesticides to bear foraging sites and, if so, whether these levels could be toxic to bears. In 1999 we collected and analyzed ACMs from six bear foraging sites. ACMs were screened for 32 pesticides with gas chromatography with electron capture detection (GC-ECD). Because gas chromatography with tandem mass spectrometry (GC-MS/MS) can be more sensitive than GC-ECD for certain pesticides, we revisited one site in 2001 and analyzed these ACMs with GC-MS/MS. ACMs contained trace or undetectable levels of pesticides in 1999 and 2001, respectively. Based on chemical levels in ACMs and numbers of ACMs a bear can consume, we calculated the potential of chemicals to reach physiological toxicity. These calculations indicate bears do not consume physiologically toxic levels of pesticides and allay concerns they are at risk from pesticides transported by ACMs. If chemical control of ACMs changes in the future, screening new ACM samples taken from bear foraging sites may be warranted.     

Toxicity of copper to acetoclastic and hydrogenotrophic activities of methanogens and sulfate reducers in anaerobic sludge

Heavy metals could potentially negatively impact microorganisms in anaerobic sulfate reducing bioreactors. The objective of this is study was to evaluate the inhibitory effect of copper to acetoclastic and hydrogenotrophic activities of methanogens and sulfate reducers in sludge obtained from a full-scale sulfate reducing bioreactor. The 50% inhibiting concentration (50%IC) of Cu(2+) to acetoclastic and hydrogenotrophic methanogens was 20.7 and 8.9 mg l(-1), respectively. The 50%IC of Cu(2+) to acetoclastic sulfate reduction was 32.3 mg l(-1). The hydrogenotrophic sulfate reducers were only inhibited by 27% at the highest concentration of Cu(2+) tested, 200 mg l(-1), indicating a high level of tolerance. The soluble Cu(2+) was observed to decrease rapidly in both the methanogenic and sulfate reducing assays. The highest level of decrease was observed in the hydrogenotrophic sulfate reducing assay which was over 99% in 5h. The results of this study indicate that sulfate reducing biotechnologies would be robust at relatively high inlet concentrations of Cu(2+).     

Interaction of metabolites with R. rhodochrous during the biodegradation of di-ester plasticizers

The commonly used plasticizers di-ethylhexyl phthalate (DEHP) and di-ethylhexyl adipate (DEHA) are known to partially degrade in the presence of soil microorganisms, such as Rhodococcus rhodochrous, releasing persistent and toxic metabolites. The metabolites adipic acid and 2-ethylhexanol were both shown to inhibit growth of the degrading microbe. 2-Ethylhexanol enhanced the activity of ethanol dehydrogenase - an enzyme involved in its metabolism - but the activity of this enzyme was inhibited by adipic acid. The metabolite usually seen in the highest concentrations - 2-ethylhexanoic acid - did not exhibit any evidence of inhibition. It was shown that the high concentration of this metabolite was due to the inability of R. rhodochrous to degrade it. Comparisons with other small carboxylic acids supported the argument that the ethyl branch was the reason for the resistance of 2-ethylhexanoic acid to degradation. The hydrophobicity of the cell surface was shown to be a factor in plasticizer degradation. The primary carbon source could be either water-soluble or hydrophobic and a hydrophobic substrate led to a cell surface that attracted the plasticizer and facilitated degradation. The most hydrophobic of the plasticizers, DEHP, was particularly sensitive to this effect.     

Sources of errors in assessing ozone visible symptoms on native vegetation

This paper aims to identify the problems regarding the evaluation of ozone (and ozone-like) symptoms, by examining the results of the 4th UN/ECE ICP-Forests Intercalibration Course for the assessment of ozone-induced visible symptoms. Trees, shrubs and herbaceous species were evaluated in a tree nursery, at Lattecaldo (Switzerland) and under open field conditions at Moggio (Italy). The main findings were: (i) the most expert surveyors tended to be grouped in the same cluster and, during the field exercises, they tended to assess in a more conservative manner compared to the less trained participants; (ii) the agreement was greater in assessing the absence rather than the presence of symptoms; (iii) typical interveinal stippling on the upper leaf surface was more accurately evaluated than discoloration; (iv) uncertainties resulted mainly for species which showed greater variability in their symptom manifestation, and for certain herbaceous species.     

Presence of plutonium contamination in soils from Palomares (Spain)

More than 30 years after the occurrence of an aircraft accident which involved the detonation of two nuclear weapons in the surrounding area of the village of Palomares (Spain), the affected terrestrial area has been investigated for remaining transuranic contamination. Evidence from the presence of this contamination was initially found through the analysis of the 241Am inventories in superficial soil samples collected in the region, and was confirmed through the analysis of the (239+240)Pu inventories and their associated 238Pu/(239+240)Pu activity ratios in the same samples. However, it was also observed that a considerable fraction of the remaining contamination in the area was present in particulate form, i.e. as "hot particles". The work performed in our laboratory for identification, isolation and characterisation of these "hot particles" as well as some conclusions obtained from these analyses are outlined in this paper.     

Pyrimethanil residues on table grapes Italia after field treatment

Residues of the pyrimidine fungicide pyrimethanil [N-(4,6-dimethylpyrimidin-2yl)aniline] were determined in table grapes "Italia" by gas chromatography nitrogen-phosphorus detector (GC-NPD). Pesticides were extracted from grapes with ethyl acetate and hexane solution (1:1 v/v), and were analyzed without any further clean up. Pyrimethanil was confirmed by high-performance liquid chromatography (HPLC) fitted with a diode array detector (DAD) and electrospray ionization mass spectrometry (ESI-MS) in the select ion-monitoring mode (SIM). The residue of pyrimethanil was under the legal limit immediately after treatment, and showed a half-life time, calculated as a reaction of pseudo first order, of 12 days, with a regression coefficient of 0.9954. Recoveries from fortified grapes ranged between 90 and 113% with a maximum coefficient of variation (CV) of 11%. The calculated limits of detection and quantitation for pyrimethanil were 0.005 and 0.01 mg/kg, respectively.