Determination of total N-nitroso compounds by chemical denitrosation using CuCl

A method for the determination of total N-nitroso compounds (NOC) by chemical denitrosation and subsequent chemiluminescence detection of evolved NO is described. Denitrosation was accomplished with CuCl in HCl at 70 degrees C. The detection limit for N-nitrosoproline (NPRO) was 1 pmol. NO formation from NPRO was linear (R(2) = 0.999) from 4 pmol to 2 nmol. Among the possible interfering compounds tested, only S-nitroso compounds contribute any significant interference. This method had several advantages over other similar methods: (1) A commercially available one-piece reaction vessel and a NO analyzer with software were used. (2) NO release occurred rapidly and was easily measured and quantified. (3) Compared to HBr or HI, CuCl was more convenient to work with and safe. (4) CuCl was suitable for samples in aqueous and most organic solvents. The application of this method to food, personal care products, and human body fluids demonstrates its utility.     

Gas-phase Diffusive Tracer Test for the In-Situ Measurement of Tortuosity in the Vadose Zone

Robust measurements of porous-medium tortuosity are one of the many components needed for accurate characterization and prediction of fluid flow and contaminant transport in the subsurface. A gas-phase diffusive tracer-test method is evaluated for the in-situ measurement of tortuosity in the vadose zone. This technique presents an alternative to employing widely-used correlations to estimate tortuosity. A small-scale field study was conducted using a single well and a non-reactive gas-phase tracer (sulfur hexafluoride; SF₆). Gas samples were collected from the injection point periodically after tracer injection into the soil matrix. An effective radius of influence of 50 cm was determined for the tests. An analytical solution was calibrated to the measured temporal concentration distribution, producing a fitted value for tortuosity. The value obtained from the tracer tests was compared to values estimated with several widely-used correlations. The value obtained from the tracer tests was generally larger than the values estimated with the correlations, which spanned a relatively wide range. The tracer-test method provides a means by which to determine in-situ measurements of tortuosity, allowing for better characterization of contaminant transport in the vadose zone.     

Effect of Cadmium(Ii) and Anion Type on the Ageing of Ferrihydrite and its Subsequent Leaching under Neutral and Alkaline Conditions

The effect of cadmium(II) on the transformation of ferrihydrite[with Cd(II):Fe(III) ratios ranging from 0 to 5 mole %] in neutral and alkaline media (pH 7-11), combined with the effects of electrolyte type (NO₃ ^-, Cl^-, and SO₄ ^-2), was investigated at 20 °C over a period of 1 yr. The presence of Cd(II) strongly retards the conversion of ferrihydrite into hematite and/or goethite at pH 7–10, with decreases in the rate of transformation dependent on the amountof Cd(II). At a Cd(II):Fe(III) mole ratio of 1%, the transformation rate is NO₃ ^- > Cl^- > SO₄ ^-2, which correlates with the relative affinitiesof the anions for the ferrihydrite surface. The presence of Cd(II) promotes hematite formation at pH 9 and 10, whereas atpH 11 goethite is almost the sole product. With increasinginitial Cd(II) concentrations, increasing incorporationof Cd(II) into the products is observed. For 5 mole %Cd(II), ～ 2.5 mole % of Cd(II) is included in thetransformation products, principally hematite, while at pH 11, with 1 mole % Cd(II), all of the Cd(II) incorporates into thegoethite lattice. Transmission electron micrographs show that the presence of Cd(II) leads to a reduction in size and promotesthe twinning of goethite crystals, and can result in ellipsoidal-shaped hematite crystals. Leachability of Cd(II) fromfresh and aged coprecipitated Cd(II)-ferrihyrdite is dependent onthe extent of transformation of the ferrihydrite, with 70–90% of the Cd(II) leachable from ferrihydrite, while goethite is ableto incorporate and remove more Cd(II) than hematite.     

At-sea distribution of breeding Tristan albatrosses Diomedea dabbenena and potential interactions with pelagic longline fishing in the South Atlantic Ocean

The endangered Tristan albatross Diomedea dabbenena is restricted to Gough and Inaccessible Islands. The species is killed as bycatch by longline fisheries in the South Atlantic, but the impact of this mortality is unknown. We satellite tracked 38 breeding Tristan albatrosses and assessed the seasonal and annual at-sea distribution of these birds in relation to reported pelagic longline fishing effort. These birds ranged across the South Atlantic from 50°W to 15°E with most (97%) daytime satellite fixes between latitudes 30°S and 45°S. Considerable fishing effort occurred within the same latitudes. Although there was no correlation between their at-sea distributions, there was a broad overlap between birds and fishing effort. Estimated bycatch rates for Tristan albatross and other Diomedea species in the South Atlantic, and the spatio-temporal overlap between birds and hooks, yield a predicted annual mortality of 471-554 birds, sufficient to cause population decreases of 3.6-4.3% per year. An index of bird × hook interactions (proportional density of birds multiplied by number of hooks by decadal period for each 5° square of longitude and latitude) indicated that 47% of annual interactions occurred in areas around Gough Island, and 11% and 15% of interactions in areas of the west and east Atlantic, respectively. There were also within seasonal differences in the key areas of overlap. The fishing fleets of Taiwan and Japan are likely to be responsible for most interactions based upon the reported magnitude of effort expended in the South Atlantic by these fleets. Ensuring that licensed fishing vessels within the Tristan da Cunha Exclusive Economic Zone (EEZ) operate using best-practise mitigation measures and with fisheries observer programs, could reduce the potential bycatch mortality of breeding Tristan albatrosses in this region by nearly one third. Thorough implementation of international agreements is required in areas of the high seas where most remaining interactions are predicted to occur.     

Comparison of breeding bird and vegetation communities in primary and secondary forests of Great Smoky Mountains National Park

We compared breeding bird communities and vegetation characteristics at paired point locations in primary (undisturbed) and mature secondary forest (70-100 years old) sites in Great Smoky Mountains National Park, USA to understand how sites logged prior to creation of the park compare to undisturbed sites following 70 years of protection from human disturbance. We found that bird and vegetation communities are currently similar, but retain some differences in species composition. Rank abundance curves for primary and secondary forest bird communities showed very similar patterns of species dominance. Species composition was also similar on the two sites which shared 24 of the 25 most frequently recorded species. Nonetheless, comparisons of density estimates derived from distance sampling showed three bird species were more abundant on primary forest sites and that one bird species was significantly more abundant on secondary forest sites. Notably, comparisons based on raw counts (unadjusted for potential differences in detectability) produced somewhat different results. Analyses of vegetation samples for the paired sites also showed relative similarity, but with some differences between primary and secondary forests. Primary forest sites had more large trees (trees greater than 50 cm diameter at breast height) and late successional species. Primary forest sites had a denser tall shrub layer while secondary forest sites had a denser canopy layer. Nonetheless, tree species richness, basal area of live trees and number of standing snags did not differ between primary and secondary forest sites. Results indicate that breeding bird communities on sites within the park that were logged commercially 70 years ago are currently quite similar to bird communities on sites with no history of human disturbance. Similarities between the bird communities on previously disturbed and undisturbed sites in Great Smoky Mountains National Park may exceed those on more fragmented landscapes because large patches of primary forest, adjacent to commercially logged sites, remained in the park when it was established in 1935. These patches of primary forest may have served as source areas for commercially logged sites.     

Decrease of heat shock protein levels and cell populations by wine phenolic extracts

The effect of red and white wine total extracts and phenolic fractions on heat shock protein (Hsp) levels in tumor cells and on tumor and endothelial cell populations in vitro has been investigated. Total extracts of red wines decreased Hsp70 and Hsp27 levels and the numbers of tumor and endothelial cells. Several red and white wine fractions significantly decreased Hsp27 levels, and some of them had also an effect on Hsp70 levels. A red wine fraction rich in polymeric flavanols and a white wine one rich in phenolic acids, flavonols, and tyrosol strongly lowered Hsp27 levels. Some red and white wine fractions strongly reduced tumor cell numbers, whereas most of them decreased endothelial cell numbers to variable extents. The present results indicate that wine phenolics decrease Hsp levels in tumor cells and tumor and endothelial cell populations. These properties may be important in the potent anticarcinogenic action of wine phenolics.