Some issues relating to the use of perfluorooctanesulfonate (PFOS) samples as reference standards

Samples of potassium perfluorooctanesulfonate (PFOSK) from three suppliers were analyzed by LC-ESI-MS/MS for purity and by LC-ESI-MS for the percentage of linear isomer present. Our data indicated that the purity ranged from 80% to 98% and the percentages of linear isomer from 67% to 79%. The proportion of branched isomers present in the samples was also estimated using (19)F NMR. These results agreed quite closely with those found by LC-ESI-MS indicating that there is essentially no difference in overall SIM response factor for the branched isomers vs. that of the linear isomer. Several further observations relevant to the use of standards when analyzing for PFOS were encountered during this study. It appears unlikely that matrix effects attributable to the cation (sodium or potassium) present in PFOSNa or PFOSK internal standards is an issue. In seeking potential matrix effects, it was found that the chromatography was improved substantially when the standard was injected as a solution in 80:20 methanol/water rather than 100% methanol. Notably, in concert with the improvement in chromatography, an increase of about 10% in response was observed. In some closely related studies, when (18)O(2) mass-labeled perfluorohexanesulfonate was used as an internal standard, the actual and theoretical concentration ratios matched closely those for related native sulfonates as long as they did not co-elute. However, when they did co-elute, the peak intensities of the native species were enhanced by about 5%, while those of the labeled compound were suppressed by a similar amount. If this effect were not taken into account, the concentration of the native would be inflated by 10%.     

Structure characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane

1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. 1H NMR spectroscopy and an X-ray structure determination have revealed that a technical mixture consists largely of two (of the four possible) diastereomers, rac-(1R,2R)-1,2-dibromo-(4S)-4-((1S)-1,2-dibromoethyl)cyclohexane (alpha-TBECH) and rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethyl)cyclohexane (beta-TBECH), in a mole ratio of approximately 1:1. The two other possible isomers, gamma- and delta-TBECH, were not detected in a technical mixture. The TBECH isomers are thermally sensitive and can easily interconvert at temperatures of 125 degrees C. A thermal equilibrium mixture of alpha-, beta-, gamma- and delta-TBECH consists of approximately 33%, 33%, 17% and 17% of these isomers, respectively. Separation of all four TBECH diastereomers, with minimal thermal interconversion of the isomers, was achieved by careful selection of GC-capillary column length and injector temperature. Although technical TBECH does not contain the gamma- and delta-isomers, they may still be relevant environmental contaminants since manufacturing processes utilize thermal processes which may induce their formation.     

Effects of a selenium-enriched diet on antioxidant response in adult crayfish (Procambarus clarkii)

Many diets employed in aquaculture are enriched with selenium to improve the diet quality and its conservation. The aim of the study was to investigate the effects of a diet enriched in selenium (1.21 mg kg(-1)) on the antioxidant response of Procambarus clarkii (Girard, 1852). Crayfish fed a diet with lower selenium content (0.30 mg kg(-1)) were the control. Selenium accumulation, enzymatic activities, and total glutathione were evaluated in hepatopancreas of adults of both sexes fed with both diets for 50 days at two experimental times (T(30), T(50) days). Treated females exhibited the highest selenium bioaccumulation during both experimental times, while treated males displayed the highest selenium concentration after 30 days, compared to control crayfish. A sex-related difference was found for the response of the analyzed enzymes in the selenium diet-treated specimens. In fact, superoxide dismutase, glutathione peroxidase and glyoxalase I activities in males were more sensitive compared with females, showing depleted activities in both experimental times. Catalase activity was induced in females (T(50)), while glutathione S-transferase activity was the highest in treated females and the lowest in treated males, compared with own controls. Only glutathione reductase activity and glutathione content showed the same trend in both sexes, which were both lowered in treated specimens, when compared with control crayfish. This result might be due to the effect of selenium toxicity on this freshwater species. Males and females of P. clarkii showed a different susceptibility to the prooxidant effects in a Se-enriched diet.     

Anti-sense expression of putrescine N-methyltransferase confirms defensive role of nicotine in Nicotiana sylvestris against Manduca sexta

Summary. Several lines of evidence support the defensive function of nicotine production in the Nicotiana genus against a range of herbivores, but the evidence is largely correlative. To suppress nicotine production in planta and to test its defensive function, we expressed DNA of putrescine N-methyl transferase in an anti-sense orientation (AS-PMT) in N. sylvestris and fed leaf material from two lines of transformed and wild type plants to Manduca sexta larvae. Larvae consumed more leaf area and gained more mass on the foliage of plants with low PMT expression and low nicotine levels as compared to plants with high PMT expression and high nicotine levels and wild type plants. Overall, larval consumption and performance were negatively correlated with constitutive nicotine levels. We conclude that nicotine decreases the palatability of N. sylvestris leaves to the nicotine-resistant M. sexta larvae.     

N-nitrosodimethylamine and trihalomethane formation and minimisation in Southeast Queensland drinking water

This study assesses the prevalence of disinfection by-product (DBP) precursors in some Southeast Queensland drinking water sources by conducting formation potential experiments for the four regulated trihalomethanes (THMs), and the potent carcinogen, N-nitrosodimethylamine (NDMA). NDMA formation potentials were consistently low (<5-21 ng/L), and total THM (tTHM) formation potentials were consistently below the Australian Drinking Water Guideline (250 μg/L). NDMA concentration of finished drinking waters was also monitored and found to be <5 ng/L in all cases. The effect of coagulation and advanced oxidation on the formation of NDMA and THMs is also reported. UV/H(2)O(2) pre-treatment was effective in producing water with very low THMs concentrations, and UV irradiation was an effective method for NDMA degradation. H(2)O(2) was not required for the observed NDMA degradation to occur. Coagulation using alum, ferric chloride or poly(diallyldimethylammonium chloride) (polyDADMAC) was ineffective in removing DBPs precursors from the source water studied, irrespective of the low dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) attained. Rather, coagulation with polyDADMAC caused an increase in NDMA formation potential upon chloramination, and all coagulants led to an increased tTHM formation potential upon chlorination due to the high bromide concentration of the source water studied.     

Consistency of defoliation data of the national training courses for the forest condition survey in Germany from 1992 to 2012

The consistency of visual assessment of tree defoliation, which represents the most widely used indicator for tree condition, has frequently been in the focus of scientific criticism. Thus, the objective of the present study was to examine the consistency of the defoliation data from the annual national training courses for the forest condition survey in Germany from 1992 to 2012. Defoliation assessments were carried out in stands of beech (Fagus sylvatica), oak (Quercus robur and Quercus petraea), Norway spruce (Picea abies), and pine (Pinus sylvestris). Among the observer teams, the absolute deviation from the observer mean of all years was ±4.4 % defoliation and the standard deviation of defoliation was ±5.5 %. On average, 94 % of the assessments were located within the ±10 % interval of deviation from the mean. Tree species-specific differences did not occur when all years were considered. A trend towards increasing consistency was observed from 1992 to 2012, in particular for oak and spruce. The deviation of defoliation assessments depended non-linearly on the level of defoliation with highest deviations at intermediate defoliations. In spite of high correlations and agreements among observers, systematic errors were determined in nearly every year. However, within-observer variances were higher than between-observer variances. The present study applied a three-way evaluation approach for the assessment of consistency and demonstrated that the visual defoliation assessment at the national training courses in general produced consistent data within Germany from 1992 to 2012.     

Impacts after four years of experimental trampling on alpine/sub-alpine environments in western Tasmania

Experimental trials were undertaken over four years to assess the impact of recreational trampling in undisturbed alpine and sub-alpine vegetation communities in the Western Arthur Range, western Tasmania. Data on 'pad' formation due to human trampling were collected using vegetation cover assessments, biomass estimates and detailed cross-sectional surface profiles. In sub-alpine buttongrass and alpine herbfield, prolonged and sustained damage may occur after 100 passes by walkers. The environmental threshold of the flat alpine herbfield site was breached after 200 passes. Plant morphology was one determinant of resistance and resilience, with upright woody shrubs and tall tussock graminoids most vulnerable to sustained trampling damage. Cushions are susceptible to trampling impacts at 500 passes. Loss of vegetation cover peaks 6-12 months after trampling. Our results show that pads formed with as few as 30-100 passes per annum and tracks form at between 100 and 500 passes per annum. Two years after the cessation of trampling, there is some small recovery in vegetation cover after 30 and 100 passes per annum applied for three years, but no evidence of recovery at the 500 pass treatments. The low trampling threshold and slow recovery rates in western Tasmania suggest that concentrating walkers on a minimal number of sites may be the best management option for these untracked alpine and sub-alpine environments.