Quantification of fatty acids in forages by near-infrared reflectance spectroscopy

Near-infrared reflectance spectroscopy (NIRS) was evaluated as a possible alternative to gas chromatography (GC) for the quantitative analysis of fatty acids in forages. Herbage samples from 11 greenhouse-grown forage species (grasses, legumes, and forbs) were collected at three stages of growth. Samples were freeze-dried, ground, and analyzed by GC and NIRS techniques. Half of the 195 samples were used to develop an NIRS calibration file for each of eight fatty acids, with the remaining half used as a validation data set. Spectral data, collected over a wavelength range of 1100-2498 nm, were regressed against GC data to develop calibration equations for lauric (C12:0), myristic (C14:0), palmitic (C16:0), stearic (C18:0), palmitoleic (C16:1), oleic (C18:1), linoleic (C18:2), and alpha-linolenic (C18:3) acids. Calibration equations had high coefficients of determination for calibration (0.93-0.99) and cross-validation (0.89-0.98), and standard errors of calibration and cross-validation were < 20% of the respective means. Simple linear regressions of NIRS results against GC data for the validation data set had r2 values ranging from 0.86 to 0.97. Regression slopes for C12:0, C14:0, C16:0, C18:0, C16:1, C18:2, and C18:3 were not significantly different (P = 0.05) from 1.0. The regression slope for C18:1 was 1.1. The ratio of standard error of prediction to standard deviation was > 3.0 for all fatty acids except C12:0 (2.6) and C14:0 (2.9). Validation statistics indicate that NIRS has high prediction ability for fatty acids in forages. Calibration equations developed using data for all plant materials accurately predicted concentrations of C16:0, C18:2, and C18:3 in individual plant species. Accuracy of prediction was less, but acceptable, for fatty acids (C12:0, C14:0, C18:0, C16:1, and C18:1) that were less prevalent.     

Adsorption of pesticides from water by functionalized organobentonites

Replacement of natural inorganic cations of clay minerals with organic cations has been proposed as a strategy to improve the adsorptive capacity of clay minerals for organic compounds, including pesticides. The organic cations most commonly used for this purpose have been quaternary ammonium ions containing alkyl or aryl chains without specific functional groups. In this work, we evaluated the ability of two bentonites (SWy-2 and SAz-1) exchanged with four natural organic cations containing diverse functional groups (L-carnitine, L-cysteine ethyl ester, L-cystine dimethyl ester, and thiamine) as adsorbents of pesticides varying in their chemical structures (simazine, hexazinone, triadimefon, alachlor, carbaryl, and imazethapyr). For comparison purposes, the adsorptive properties of two "classical" organobentonites, hexadecyltrimethylammonium- and phenyltrimethylammonium-exchanged bentonites, were also determined. Most organobentonites displayed higher affinity for the pesticides than the untreated bentonites, but the improvement in adsorption capacity varied depending on the characteristics of the pesticide and the interlayer organic cation. Triadimefon, carbaryl, and imazethapyr displayed the highest affinity for carnitine (K(f) = 229-2377)-, thiamine (K(f) = 83-354)-, and cystine (K(f) = 96-100)-treated bentonites, respectively, whereas alachlor was adsorbed similarly by all organobentonites. In general, pesticide adsorption-desorption hysteresis was greater for adsorbents with the highest adsorption capacities. The results demonstrate that selective modification of smectitic clay minerals with natural organic cations containing appropriate functional groups can be a useful strategy to improve their performance for the removal of specific pesticides from the environment.     

Metsulfuron methyl sorption-desorption in field-moist soils

Pesticide sorption coefficients (K(d)) are generally obtained using batch slurry methods. As a consequence, the results may not adequately reflect sorption processes in field-moist or unsaturated soil. The objective of this study was to determine sorption of metsulfuron methyl, a weak acid, in field-moist soils. Experiments were performed using low density (i.e., 0.3 g mL(-)(1)) supercritical fluid carbon dioxide (SF-CO(2)) to convert anionic metsulfuron methyl to the molecular species and remove it from the soil water phase only, thus allowing calculation of sorption coefficients (K(d)) at low water contents. K(d) values for sorption of the metsulfuron methyl molecular species on sandy loam, silt loam, and clay loam soil at 11% water content were 120, 180, and 320 mL g(-)(1), respectively. Using neutral species K(d) values, the pK(a) of metsulfuron methyl, and the pH of the soil, we could successfully predict the K(d) values obtained using the batch slurry technique, which typically has a predominance of anionic species in solution during the sorption characterization. This application of supercritical fluid extraction to determine sorption coefficients, combined with sulfonylureas' pK(a) values and the soil pH, will provide an easy method to predict sorption in soil at different pH levels.     

N-linked glycan profiling of mature human milk by high-performance microfluidic chip liquid chromatography time-of-flight tandem mass spectrometry

N-Linked glycans of skim human milk proteins were determined for three mothers. N-Linked glycans are linked to immune defense, cell growth, and cell-cell adhesion, but their functions in human milk are undetermined. Protein-bound N-linked glycans were released with peptidyl N-glycosidase F (PNGase F), enriched by graphitized carbon chromatography, and analyzed with Chip-TOF MS. To be defined as N-glycans, compounds were required, in all three procedural replicates, to match, within 6 ppm, against a theoretical human N-glycan library and be at least 2-fold higher in abundance in PNGase F-treated than in control samples. Fifty-two N-linked glycan compositions were identified, and 24 were confirmed via tandem mass spectra analysis. Twenty-seven compositions have been found previously in human milk, and 25 are novel compositions. By abundance, 84% of N-glycans were fucosylated and 47% were sialylated. The majority (70%) of total N-glycan abundance was composed of N-glycans found in all three milk samples.     

Rapid wetland functional assessment: Its role and utility in the regulatory arena

Section 404 of the dean Water Act (CWA) regulates the discharge of dredged or fill material, which is defined as a pollutant, into waters of the United States by requiring potential dischargers to obtain a permit for such activities. The Section 404(b)(1) Guidelines provide the substantive environmental criteria by which all dredge and fill permit applications are reviewed. The Guidelines consist of 4 basic steps: 1) evaluation of practicable alternatives; 2) evaluation of relation of discharge to other environmental standards; 3) assessment of significant degradation to waters of the U.S.; and 4) assessment of appropriate steps to minimize impacts. Wetland functional assessment is important in steps 1, 3, and 4. The use of wetland functional assessment techniques has typically been hindered by lack of time and resources, among other technical concerns, by the resource agencies implementing the Section 404 program. Functional assessment is critical to the Section 404 program since most decisions revolve around an assessment of wetland functions. The Hydrogeomorphic Classification for Wetlands (Brinson, 1993) and the developing functional assessment procedure shows potential for being rapid and inexpensive, scientifically-based and replicable. It is based upon functional indicators which can be recognized in the field and can form the basis for functional indices. The utility of the HGM procedure is illustrated using an example from West Kentucky.     

Landscape evaluation of female black bear habitat effectiveness and capability in the North Cascades, Washington

We used logistic regression to derive scaled resource selection functions (RSFs) for female black bears at two study areas in the North Cascades Mountains. We tested the hypothesis that the influence of roads would result in potential habitat effectiveness (RSFs without the influence of roads) being greater than realized habitat effectiveness (RSFs with roads). Roads consistently had a negative influence on black bear RSFs across seasons and study areas. Roads reduced habitat effectiveness during all seasons at both study areas and changes in the potential habitat values ranged from 1.7% to 16.9%. The greatest reduction in habitat values occurred during the early-season on the west-side study area due to high open road densities. These results support the hypothesis that roads reduce habitat effectiveness for black bears. The influence of roads could be reduced through road closures to reduce open road densities and limit traffic volumes. We then used the scaled RSFs in a habitat-based population model to assess the influences of timber harvest and roads on potential black bear population sizes. On the west-side study area the potential black bear population size was most influenced by moderate use roads and timber harvest during the early-season (41% reduction). On the east-side study area, low use roads had the greatest effect on potential black bear population during the early-season (10% reduction). During the late-season, in both study areas, roads had less influence on the potential population sizes as bears were able to access habitats away from roads. The habitat-population model provided reasonable estimates of bear densities compared to other study areas with similar habitats and could be extrapolated to estimate potential black bear populations in other areas with similar habitats. This approach may provide a useful link between the landscape ecology and population biology of black bears, and could eventually be useful in the development of habitat-based population viability analyses.     

Identification of proanthocyanidin dimers and trimers, flavone C-Glycosides, and antioxidants in Ficus deltoidea , a malaysian herbal tea

Phenolic compounds in an aqueous infusion of leaves of Ficus deltoidea (Moraceae), a well-known herbal tea in Malaysia, were analyzed by HPLC coupled to photodiode array and fluorescence detectors and an electrospray ionization tandem mass spectrometer. Following chromatography of extracts on a reversed phase C(12) column, 25 flavonoids were characterized and/or tentatively identified with the main constituents being flavan-3-ol monomers, proanthocyanidins, and C-linked flavone glycosides. The proanthocyanidins were dimers and trimers comprising (epi)catechin and (epi)afzelechin units. No higher molecular weight proanthocyanidin polymers were detected. The antioxidant activity of F. deltoidea extract was analyzed using HPLC with online antioxidant detection. This revealed that 85% of the total antioxidant activity of the aqueous F. deltoidea infusion was attributable to the flavan-3-ol monomers and the proanthocyanidins.     

Assessing landscapes: a case study of tree and shrub diversity in the seasonally dry tropical forests of Oaxaca, Mexico and southern Honduras

Tropical dry forests, with their distinct and economically important diversity, are acknowledged conservation priorities because of alarming rates of forest conversion. Whilst it is realised that terrestrial conservation requires an understanding of landscape level patterns of diversity, forests are rarely assessed accordingly. Here we demonstrate that, in the case of the seasonally dry tropical forests of the Pacific watershed of Mesoamerica, landscape level assessment of woody diversity can inform decision making relevant to both between-landscape and within-landscape prioritisation. We report floristic surveys of dry forest landscapes in Oaxaca, Mexico and southern Honduras. It is noted that these forests are floristically similar to other seasonally dry tropical forests in the neotropics. By calculation of Genetic Heat Indices, a relative measure of the concentration of restricted range species in a sample, we determine that the conservation of the tree diversity of the coastal lowlands of Oaxaca should be prioritised over that of southern Honduras. The current conservation status of forested areas in Oaxaca is briefly described. We suggest that the greater degree of anthropogenic disturbance in southern Honduras may explain the relative lack of restricted range species there. We argue that some forest fallows can act as analogues of mature forest and therefore landscape elements other than mature forest need to be included in forest conservation assessments. We conclude that diversity sampling of any forest type should not be limited to mature forests, but extended to other elements of forested landscapes.