Effects of forest vegetation on spatial variability of surface mineral soil pH,soluble aluminum and carbon

The purpose of this study was to examine spatial variability in forest soils at several levels including variability due to soil structure, to the presence of individual trees and to populations of different species of trees. Both classic statistical and geostatistical methods were used. Soil chemical properties measured include pH and Al and C in solution which was in equilibrium with the surface mineral soil. Results indicated that soil cores 1.8 cm in diameter were as effective as larger cores in incorporating variability in surface mineral soil pH. There was no spatial correlation in soil pH in samples separated by a distance of 20 to 360 cm. The presence of individual Norway spruce and red pine trees affected soil in their vicinity. Soil pH was depressed and soluble Al elevated. in soil near the base of the tree compared to soil 120 cm from the tree, independent of direction. In addition, in soil sampled at least 100 cm from the base of trees, pH was lower in Norway spruce compared to sugar maple plantations and soluble C was greater in red pine compared to Norway spruce plantations. It is concluded that in less than 50 yr the presence of individual trees and populations of different tree species can affect chemical properties of surface mineral soils. These effects should be considered in the design and interpretation of experiments.     

Pro-oxidative characteristics of trout hemoglobin and myoglobin: a role for released heme in oxidation of lipids

The molecular mass of trout myoglobin was 16017 Da based on electrospray ionization mass spectrometry. A Root effect (low oxygen affinity at pH 6.3) was determined in trout hemoglobin but not myoglobin. At pH 6.3, myoglobin autoxidized more rapidly (3.5-fold) as compared to anodic hemoglobin. Anodic hemoglobin was a better catalyst of lipid oxidation in washed cod muscle as compared to myoglobin at pH 6.3. This suggested that some process other than met heme protein formation was the rate-limiting step in lipid oxidation processes. Heme loss rates were determined using the apomyoglobin mutant H64Y prepared from sperm whale. Anodic hemoglobin released its heme group much more rapidly than myoglobin. In comparisons of anodic and cathodic hemoglobins, heme loss rate better predicted the onset of lipid oxidation than autoxidation rate. These studies collectively suggest that heme dissociation has a primary role in the ability of different heme proteins to promote lipid oxidation processes.     

Preparation of stable isotope-labeled 2-nitrobenzaldehyde derivatives of four metabolites of nitrofuran antibiotics and their comprehensive characterization by UV, MS, and NMR techniques

A convenient method is presented for the preparation of the carbon-13-labeled 2-nitrobenzaldehyde derivatives of the nitrofuran metabolites 3-amino-2-oxazolidinone (AOZ), semicarbazide (SC), 1-aminohydantoin (AH), and 3-amino-5-morpholinomethyl-2-oxazolidinone (AMOZ), with the purpose of using them as internal standards for the quantification of trace levels of nitrofuran residues by liquid chromatography-tandem mass spectrometry in foods of animal origin. The synthesis encompasses the nitration of [1,2,3,4,5,6-(13)C(6)]toluene prior to chromyl compound-mediated oxidation of the methyl group into the corresponding aldehyde. The four metabolites of nitrofuran antibiotics were derivatized independently with the resulting ring-labeled 2-nitrobenzaldehyde (NBA) to obtain the target compounds. Both the isotopically enriched and native substances were used to perform a comprehensive fragmentation study by electrospray ionization (ESI) collision-induced dissociation (CID) mass spectrometry (MS). Full characterization of the nitrofuran derivatives was accomplished with ultraviolet (UV) and exhaustive nuclear magnetic resonance (NMR) analysis. A major advantage of the described procedure is that it can be extended to the preparation of other carbon-13-labeled derivatives of metabolites of nitrofuran antibiotics.     

The relationship between the physicochemical properties of antioxidants and their ability to inhibit lipid oxidation in bulk oil and oil-in-water emulsions

Chain-breaking antioxidants differ in their effectiveness at inhibiting lipid oxidation because of their chemical properties and physical location within a food. Our objective was how the physicochemical properties of four structurally related lipid-soluble antioxidants were related to their antioxidant activity. Antioxidants differed in the number of methyl (alpha-tocopherol and delta-tocopherol) or hydroxyl (butylated hydroxytoluene (BHT) and 4-hydroxymethyl-2,6-ditertiarybutylphenol) groups. Surface activity of the antioxidants was in the order of delta-tocopherol > alpha-tocopherol approximately 4-hydroxymethyl-2,6-ditertiarybutylphenol > BHT. Free-radical scavenging activity was similar between alpha-tocopherol and delta-tocopherol as well as BHT and 4-hydroxymethyl-2,6-ditertiarybutylphenol. In bulk menhaden oil, BHT was a more effective antioxidant than 4-hydroxymethyl-2,6-ditertiarybutylphenol while alpha-tocopherol was more effective than delta-tocopherol. In menhaden oil-in-water emulsions, BHT was a more effective antioxidant than 4-hydroxymethyl-2,6-ditertiarybutylphenol while delta-tocopherol was more effective than alpha-tocopherol. These results indicate that the surface activity and polarity of lipid-soluble antioxidants were not the only determinants of their antioxidant effectiveness in food lipids.     

Defoliation and fertiliser influences on the soil microbial community associated with two contrasting Lolium perenne cultivars

The influence of repeated defoliation on soil microbial community (SMC) structure and root turnover was assessed in two contrasting Lolium perenne cultivars (AberDove and S23) grown in fertilised (+F) and non-fertilised (NF) soil. BiOLOG sole carbon source utilisation profiles (SCSUPs) indicated consistently greater potential carbon utilisation in defoliated (+D) compared to non-defoliated (ND) soils regardless of cultivar and fertiliser, and was accounted for in a variety of substrate groups (sugars, carboxylic, amino and phenolic acids). Potential carbon utilisation was also stimulated in +F compared to NF soils, primarily through increased potential utilisation of carboxylic acids. PLFA indicators for the bacterial biomass did not significantly differ between cultivar, soil fertilisation, or defoliation. Defoliated swards grown in fertilised soil (+F+D) had a higher fungal:bacterial ratio and a greater bacterial stress index (cy19:0/18:1w7c), compared to that of +F ND, NF ND and NF+D, and regardless of cultivar. Overall SMC structure (canonical variate (CV) analysis of PLFAs) discriminated based on cultivar, defoliation and soil fertilisation. Primary discrimination of the SMCs could be related to differences in root density and total plant biomass, and in the case of NF soils, secondary community shifts, evident with defoliation, related to root disappearance over the growing season. Despite the strong common effects of defoliation, and to a lesser extent soil fertilisation, cultivar specific drivers of the soil microbial community were maintained, resulting in consistent, but subtle, discrimination of the SMC associated with the contrasting L. perenne cultivars.     

Can sodium regulation be used to predict the relative acid-sensitivity of various life-stages and different species of aquatic fauna?

Fishes, Zooplankton, insect larvae, and benthic invertebrates differ in their sensitivity to acidic waters. Some species are able to survive and complete their life-cycle below pH 3.5 while others are eliminated once the pH drops below 5.5. Generally, acid-sensitive fauna are highly water permeable and have difficulty regulating osmotically essential ions, such as sodium and chloride, at low pH. Increased permeability during certain stages of a life-cycle (post-molt crayfish, for example) are often associated with increased acid-sensitivity. Special adaptations, including enlarged anal papillae in Chironomids and the number and morphology of chloride cells in such diverse organisms as crustaceans, insect larvae, and fishes, may enhance acid-tolerance. To test the hypothesis that Na⁺ regulation can be used to predict relative acid-sensitivity of aquatic fauna we will need a mechanism for standardizing Na⁺ regulatory capability.     

Hydrogen ion speciation in the acid precipitation of the northeastern United States

The acidity of precipitation in rural, forested areas of the northeastern United States is dominated by the strong mineral acids: H₂SO₄ and HN0₃. Weak acids have a negligible effect on the measured acidity (pH) of precipitation. These conclusions are based on total acidity titrations and detailed analysis of organic and inorganic components in precipitation.     

Ability of surfactant micelles to alter the physical location and reactivity of iron in oil-in-water emulsion

The purpose of this research was to determine how surfactant micelles influence iron partitioning and iron-promoted lipid oxidation in oil-in-water emulsions. Lipids containing ferric ions were used to produce oil-in-water emulsions, and continuous-phase iron concentrations in emulsions were measured as a function of varying continuous-phase polyoxyethylene 10-lauryl ether (Brij) concentrations. Continuous-phase iron concentrations increased with increasing surfactant micelle concentrations (0.1-2.0%) and storage time (1-7 days). At pH 3.0, the concentration of continuous-phase iron was higher than at pH 7.0. Similar trends in iron solubilization by Brij micelles were observed when either hexadecane or corn oil was used as the lipid phase. Lipid oxidation rates, as determined by the formation of lipid hydroperoxides and headspace hexanal, in corn oil-in-water emulsions containing iron decreased with increasing surfactant concentrations (0.5-2.0%). These results indicate that surfactant micelles could alter the physical location and prooxidant activity of iron in oil-in-water emulsions.