Dynamic headspace analysis of the release of volatile organic compounds from ethanolic systems by direct APCI-MS

Static equilibrium headspace was diluted with a stream of nitrogen to study the stability of the volatile headspace concentration. The headspace dilution profile of 18 volatile compounds above aqueous and ethanolic solutions was measured in real time using atmospheric pressure chemical ionization-mass spectrometry. Under dynamic conditions the volatiles headspace concentration above water solutions decreased readily upon dilution. The presence of ethanol helped to maintain the volatile headspace concentration when the ethanol solution concentration was above 50 mL/L. This effect was such that under dynamic conditions the absolute volatile concentration above an ethanolic solution was higher than that above an aqueous solution, contrary to results observed in equilibrium studies. The ratio of the headspace concentration of volatiles above ethanolic 120 mL/L and water solutions was correlated to their air/water partition coefficient.     

Synthesis and phytotoxicity of new ionic liquids incorporating chiral cations and/or chiral anions

The aim of this work was to synthesize chiral ionic liquids as chiral solvents for organic synthesis and to evaluate the phyto(eco)toxicity of the new products and starting N-alkylimidazoles and their potential environmental influence on soil and plants. Chiral ionic liquids containing anions such as Cl-, Br-, TsO-, PF6(-), NO3(-), CF3SO3(-), and (+)- and (-)-C6H5CH(OH)C(O)O- were synthesized using (-)-(1R)-6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-ethyl [(-)-(1R)-nopyl] halides (X = Cl, Br) and tosylate in 62-100% yields. The chloride 7 and the nitrate 13 ionic liquids possessed a toxicity dependent on the applied concentration. The lowest concentration causing a distinct reduction in plant germination/growth was 100 mg/kg. Spring barley better tolerated the ionic liquids (200 mg/kg) than common radish (100 mg/kg). The nitrate liquid did not exhibit an inhibiting effect on the germination ability of seeds. The starting N-methylimidazole used in lower concentrations (1 and 10 mg/kg of soil dry weight) was not phytotoxic, in contrast to higher doses (>1000 mg/kg).     

Management strategies to increase stand structural diversity and enhance biodiversity in coastal rainforests of Alaska

Coastal rainforests of southeast Alaska have relatively simple species composition but complex structures with high diversity of tree ages, sizes and forest canopy layers, and an abundant understory plant community. Wildlife and fisheries resources also play an important role in the ecological functioning of forest and aquatic systems. Clearcutting has greatly altered these forest ecosystems with significant decreases in structural diversity of forest stands and greatly reduced wildlife habitat. This paper synthesizes information on management options in older forests that have never been actively managed, and in younger forests to increase diversity of stand structures and their associated effects on biodiversity. Light to moderate levels of partial cutting in old-growth forests can maintain the original diversity of overstory stand structures and understory plant communities. In younger forests that develop after clearcutting, mixed alder-conifer stands provide more heterogeneous structures and significantly higher understory biomass than in pure conifer forests. Research has shown that red alder increases diversity and abundance of understory plants, and provides forage for deer and small mammals. Results also show a clear linkage between alder and improved invertebrate diversity in aquatic systems. A combination of light partial cutting in older forests along with inclusion of red alder in conifer-dominated forests could provide the greatest amount of diversity and maintain the complex stand structures that are an important component of these forest ecosystems.     

Rapid sedimentological and biological assessment of hydrocarbon contaminated sediments

It is possible to rapidly detect the presence of high concentrations of sediment associated hydrocarbons using a sediment profile camera and simultaneously evaluate the general sedimentological and biological character of a contaminated area. In sediments that were heavily contaminated with hydrocarbons from spills and chronic long-term additions the presence of hydrocarbons was seen about 50% of the time in the sediment profile images as unique features, ‘H spots’. The presence of these features was related to the concentration of hydrocarbons in the sediment. In highly contaminated muddy sediments ‘H spots’ were found in images collected at stations that had from 270 to 610 ppt total hydrocarbons. Sedimentological and biological information obtained from the sediment profile images confirmed the impacted nature of Elizabeth River sediments. Sediment profile imaging provide a means of obtaining an overall evaluation of the quality of a habitat and impacts on that habitat from pollution related environmental disturbances. While qualitative, an advantage of sediment profile image data is that they can be evaluated in less than a day and used to quickly locate inclusions of hydrocarbons in the sediments for further quantitative chemical or biological sampling, or mapping of heavily contaminated areas.     

Soil amidase activity in polyacrylamide-treated soils and potential activity toward common amide-containing pesticides

 Polyacrylamide (PAM) is currently used as an irrigation water additive to significantly reduce the amount of soil erosion that occurs during furrow irrigation of crops. Elevated soil amidase activity specific toward the large PAM polymer has been reported in PAM-treated field soils; the substrate specificity of the induced amidase is uncertain. PAM-treated and untreated soils were assayed for their capacity to hydrolyze the amide bond in carbaryl (Sevin), diphenamid (Dymid), and naphthalene acetamide. Based on results obtained with a soil amidase assay, there was no difference between PAM-treated and untreated soils with respect to the rate of amide bond hydrolysis of any of the agrochemicals tested. It appears that under these assay conditions the PAM-induced soil amidase is not active toward the amide bonds within these molecules. However, carbaryl was hydrolyzed by a different soil amidase. To our knowledge, this is the first soil enzyme assay-based demonstration of the hydrolysis of carbaryl by a soil amidase. Received: 23 June 1999     

Characterization of the antioxidant activity of sugars and polyhydric alcohols in fish oil emulsions

Polyols have been incorporated into fish oil emulsions as a means for the inhibition of lipid oxidation and suppression of fishy flavor. However, the role of sugars and polyhydric alcohols as antioxidants has not been clearly established. Selected polyols were evaluated for their performance as antioxidants and modifiers of oxidation pathways in a model system. Oil/water (O/W) emulsions were prepared with freshly steam-deodorized menhaden oil. A layer of emulsion in aluminum pans held at 5 degrees C was exposed to 2550 lx fluorescent lights for 24 h before peroxide values and volatile flavor compounds were analyzed by GC headspace entrainment procedure. Antioxidant activity was confirmed for fructose, sucrose, raffinose, sorbitol, or mannitol when incorporated at 16% of the aqueous phase into model fish oil-in-water emulsions. Peroxide values were suppressed 10-18% in treated samples compared to control samples. Viscosity data did not exclude possible contributions from a restricted oxygen diffusion mechanism in the antioxidant activity, but revealed that emulsion viscosity did not govern fish oil oxidation rates. Combining polyols with phenolic antioxidants (alpha-tocopherol, BHT, or TBHQ) frequently diminished the antioxidant activity compared to that for individual phenolic antioxidants, which was interpreted as indicating that the H-donating activity of phenolic antioxidants was hindered by the H-bonding activity of polyols. A viscosity-based inhibition of the retroaldol conversion of (E,Z)-2,6-nonadienal to (Z)-4-heptenal with a high fructose concentration (67%) was attributed to a restriction of molecular mobility of reactants, but the conversion was only slightly inhibited by the concentration of fructose (16%) used in experimental emulsions. The data supported a hypothesis that either or both free radical scavenging and transition state metal chelation activities were provided by polyols in fish oil emulsions. Also, polyols retarded the water-requiring retroaldol decomposition of (E,Z)-2,6-nonadienal to (Z)-4-heptenal in the model systems and the reaction may be involved in some suppression of fishy flavors in emulsions.     

Use of adsorbent and supercritical carbon dioxide to concentrate flavor compounds from orange oil.

Orange oil is composed largely of terpene hydrocarbons but is a source of flavor and fragrance compounds (oxygenated) that are present in low concentrations. To increase the ratio of oxygenated compounds to terpene hydrocarbons, orange oil was partially fractionated by adsorption of the oxygenated compounds onto porous silica gel, with full utilization of its adsorbent capacity, and then further purified by desorption into supercritical carbon dioxide. The desorption of 24 compounds was monitored by GC and GC-MS. Adsorption alone removed three-fourths of the terpene hydrocarbons, and fractional extraction by supercritical carbon dioxide (SC-CO(2)) improved the separation further. Response surface methodology was used in the experimental design, and regression analysis was used to determine the effects of process variables. Extraction at low temperatures and flow rates improved separation by SC-CO(2). Decanal was concentrated to 20 times that of the feed oil by using SC-CO(2) at 13.1 MPa, 35 degrees C, and 2 kg/h. The systems were operating at close to equilibrium conditions because of the fine dispersal of the oils and the excellent mass transfer properties of supercritical carbon dioxide.     

Effects of soil pH and soil water content on prosulfuron dissipation

The sulfonylurea herbicide prosulfuron, 1-(4-methoxy-6-methyltriazin-2-yl)-3-[2-(3,3,3-trifluoropropyl)phenylsulfonyl]urea, is used for the selective control of broadleaf weeds in corn, sorghum, and cereal grains. To investigate its fate in soils, this study examined the effects of soil pH and water content on the rates of dissipation processes and the products formed under aerobic conditions. Radiometry and chromatography analyses were used to quantify the degradation products and bound residues formed in incubations of 10 different soils. The pH-dependent hydrolysis of the sulfonylurea bridge to form phenyl sulfonamide was the primary transformation process. Significant microbial degradation of prosulfuron occurred in 2 of the 10 soils, yielding (14)CO(2) and desmethyl prosulfuron among the major products. The time required for 50% dissipation of the herbicide (DT(50)) was determined for each soil and water content treatment. At equivalent water contents, prosulfuron DT(50) values were positively correlated with soil pH (P < 0.0001), varying from 6.5 days at pH 5.4 to 122.9 days at pH 7.9. Soil pH and water content strongly influence the fate of sulfonylurea herbicides in agricultural fields. Differences in the effect of soil water content on dissipation kinetics in a comparison of two soils were attributed to differences in soil pH, texture, and the ability of indigenous microorganisms to transform the herbicide.     

Competition for shifting resources in the southern Benguela upwelling: Seabirds versus purse-seine fisheries

In the southern Benguela upwelling ecosystem off the west coast of South Africa, seabird populations are decreasing dramatically because of reduced availability of pelagic fish. We tested the hypothesis that the west coast fishing industry is competing for the remaining stocks of anchovy and sardine with the largest colony of Vulnerable Cape Gannets (Morus capensis) along the Atlantic coast. Using GPS-tracking of the birds, echo-sounding of pelagic fish, and vessel log books, we located overlap areas between bird foraging ranges, pelagic fish distribution, and fishing activities. We then compared fish catches by gannets and vessels within their joint foraging zones. In October 2007, purse-seine fishing grounds and gannet foraging areas overlapped by only 13%. However, for a 1-month period, the amount of fish removed from this area by purse-seine boats amounted to 41% of the food requirements of the 72,000 gannets breeding on Malgas Island (25% of the world population). The fishery’s catch in this area is significant in terms of its potential impact on gannets, but comprises only 3.6% of total fishery catch. Based on this finding, the rapidly decreasing size of the gannet colony and the stated objectives of South Africa’s Marine Living Resources Act of 1998, the case for considering and experimenting with at-sea ‘no-take’ areas for the purse-seine fishery is strong. Efforts to establish whether ‘no-take’ fishing zones increase food availability for top predators is an important next step in conservation of the southern Benguela Ecosystem.     

The role of life-history and location of barriers to migration in the spatial distribution and conservation of fish assemblages in a coastal river system

Water resource development in coastal river catchments contributes to poor fish assemblage health due to the effects of barriers to migration and altered flow regimes. Impacts of migration barriers on fish assemblages depend primarily on the location of each barrier within the river network and migration needs of regional fish fauna. This study examined how temporal and spatial patterns in the distribution and composition of fish assemblages was associated with varying estuarine connectivity and migration barriers in higher altitude reaches in the eastern Hunter River catchment, temperate Australia. Species richness and abundances of diadromous species were expected to be greater in a tributary catchment with unrestricted connectivity to the Hunter River estuary when compared to a neighbouring tributary catchment with restricted connectivity. Six diadromous species were sampled only, or in greater abundances, in the unrestricted tributary when compared to the restricted tributary. As a consequence, assemblage composition in the restricted tributary was dominated by non-diadromous species. Greater abundances of the amphidromous Cox’s gudgeon (Gobiomorphus coxii) were sampled in the unrestricted tributary following their estuarine-freshwater upstream juvenile migration period when compared to the restricted tributary. Differences in the accumulations of migratory species immediately downstream of upland barriers between the two levels of estuary connectivity indicate that migration barriers in lowland reaches have significant effects throughout the entire catchment. Results of this study indicate that the location of each barrier to migration within river networks has varying consequences for catchment-scale connectivity loss and assessing the impacts of multiple barriers. Determining the effects and most appropriate management of migration barriers requires that all obstructions within a river network are recognised, as multiple barriers can have cumulative and interacting consequences for freshwater fish fauna, especially diadromous species.