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Biomedical subjects

Martha J M Wells

Publications and source records attributed to Martha J M Wells.

6 recordsLinked to original sources

Establishing the feasibility of coupled solid-phase extraction-solid-phase derivatization for acidic herbicides.

The significance of this research is that it improves analytical methodology used for organic chemicals in aqueous solutions by establishing the feasibility of heterogeneous chemical derivatization at the liquid-solid interface (i.e., solid-phase reaction or solid-phase derivatization). A solid-phase derivatization method for determining chlorinated herbicide acids was developed. Solid-phase extraction was used to concentrate and retain analytes on sorbents for subsequent solid-phase derivatization. Background interferences were removed from the chromatograms by electronically subtracting the responses of blank, nonfortified analyses from spiked samples. Two extraction sorbents (octadecyl bonded silica and polystyrene-divinylbenzene) and two derivatizing reagents (BF3-MeOH and trimethylsilyldiazomethane) were investigated. Recovery of 13 chlorinated herbicide acids--including pentachlorophenol, dinoseb, and bentazon (having a derivatizable functional group, -OH or -NH, bonded directly to a phenyl group); dicamba, picloram, acifluorfen, 3,5-dichlorobenzoic acid, and dacthal (having a derivatizable functional group, -COOH, bonded directly to a phenyl group); and 2,4-D, 2,4,5-T, dichlorprop, 2,4,5-TP, and 2,4-DB (having a derivatizable functional group, -COOH, bonded directly to a sp3 carbon atom)--was tested. The analytical method developed was proven successful for determining acidic herbicides, except for the dacthal diacid metabolite, in aqueous samples.

Acids↗

Assessing the trihalomethane formation potential of aquatic fulvic and humic acids fractionated using thin-layer chromatography.

The significance of this research is the application of thin-layer chromatography (TLC) to fractionate well-characterized aquatic humic materials coupled with the novel evaluation of the trihalomethane formation potential (THMFP) of the fractionated materials. Disinfection by-products such as trihalomethanes (THMs) form when natural water is treated by chlorination. Nordic Aquatic and Suwannee River fulvic and humic acids, obtained from the International Humic Substances Society, were prepared at pH 6 and 9 and fractionated on silica gel plates using a mobile phase consisting of methanol and ethyl acetate (2:1, v:v). Based on retention factor (R(f)) values, three common fractions were identified in all substances examined. Additionally, other fractions were noted that were characteristic of specific humic substances. Each of the three primary fractions derived from Nordic Aquatic fulvic acid at pH 6 demonstrated the potential to contribute to formation of THMs. This research provides data to support the hypothesis that differences in the chemical structure and composition of natural organic matter (NOM) significantly affect the potential to react with chlorine to form THMs.

Benzopyrans↗

Identification of fatty acids in fishes collected from the Ohio River using gas chromatography-mass spectrometry in chemical ionization and electron impact modes.

Analyses of fatty acid (FA) composition in freshwater fishes promote understanding of the potential relationship between fish health or human nutrition and specific FAs. Therefore, the chemical identity of FAs in endemic fishes must be established. Paddlefish, sauger, and white bass were collected from the Ohio River. The structural identification of esterified FAs from fish-fillet lipids was conducted using gas chromatography-mass spectrometry (GC-MS). The same 13 FAs, composing more than 90% of the mass of FAs extracted by techniques used in this research, were found in all three species examined. Carbon chain length and degree and position of unsaturation were determined from the characteristic ionization and fragmentation of FA methyl esters (FAMEs) resulting from GC-MS electron impact (EI) and chemical ionization (CI) modes. Assignment of structure to the extracted FAs required complementary interpretation of both EI and CI MS. The EI spectra observed substantiate findings reported in the literature. The novelty of this research is in the thorough interpretation of CI spectra for which less data are available. The observations reported for analyses of fishes will be useful to all researchers studying FAs regardless of sample media.

Animals↗

Chemometric discrimination among wild and cultured age-0 largemouth bass, black crappies, and white crappies based on fatty acid composition.

The potential to distinguish juvenile wild from cultured fishes and to discriminate among juvenile fishes by species based on fatty acid composition was demonstrated. Statistical approaches to data evaluation included analysis of variance, correlation analysis, principal component analysis (PCA), and quadratic discriminant analysis (QDA). Differences were determined between wild and cultured fishes both within and between species and between hatcheries. Fatty acid compositions were compared among individual (not composited) specimens of wild and cultured, age-0, freshwater species: largemouth bass Micropterus salmoides, black crappies Pomoxis nigromaculatus, white crappies P. annularis, and black-nose crappies. Four fatty acids were investigated: linoleic acid (18:2n-6), linolenic acid (18:3n-3), arachidonic acid (20:4n-6), and docosahexaenoic acid (22:6n-3). Linoleic acid was the primary fatty acid used to differentiate juvenile wild from cultured fishes. Concentrations of linoleic acid were significantly different (p < 0.05) in cultured largemouth bass and black crappies from the wild counterparts. Linolenic acid concentrations were not significantly different (p < 0.05) between wild and cultured largemouth bass but were significantly different between wild and cultured black crappies. Wild largemouth bass contained higher concentrations of arachidonic acid than the cultured bass, and concentrations of docosahexaenoic acid were twice as high in wild black crappies than cultured black crappies. On the basis of four signature fatty acids, 90 of 91 juvenile fishes were correctly classified as wild or cultured; 32 of 37 wild juvenile fishes originating from the same reservoir were differentiated by species. Data from the training set were used to classify a test set of fishes as to species, source, or origin with 100% accuracy.

Analysis of Variance↗

Development of an analytical scheme for simazine and 2,4-D in soil and water runoff from ornamental plant nursery plots.

The transport and fate of pesticides applied to ornamental plant nursery crops are not well documented. Methodology for analysis of soil and water runoff samples concomitantly containing the herbicides simazine (1-chloro-4,6-bis(ethylamino)-s-triazine) and 2,4-D ((2,4-dichlorophenoxy)acetic acid) was developed in this research to investigate the potential for runoff and leaching from ornamental nursery plots. Solid-phase extraction was used prior to analysis by gas chromatography and liquid chromatography. Chromatographic results were compared with determination by enzyme-linked immunoassay analysis. The significant analytical contributions of this research include (1) the development of a scheme using chromatographic mode sequencing for the fractionation of simazine and 2,4-D, (2) optimization of the homogeneous derivatization of 2,4-D using the methylating agent boron trifluoride in methanol as an alternative to in situ generation of diazomethane, and (3) the practical application of these techniques to field samples.

2,4-Dichlorophenoxyacetic Acid↗

Preferential adsorption of fluorescing fulvic and humic acid components on activated carbon using flow field-flow fractionation analysis.

Activated carbon treatment of drinking water is used to remove natural organic matter (NOM) precursors that lead to the formation of disinfection byproducts. The innate hydrophobic nature and macromolecular size of NOM render it amenable to sorption by activated carbon. Batch equilibrium and minicolumn breakthrough adsorption studies were performed using granular activated carbon to treat NOM-contaminated water. Ultraviolet (UV) absorption spectroscopy and flow field-flow fractionation analysis using tandem diode-array and fluorescence detectors were used to monitor the activated carbon sorption of NOM. Using these techniques, it was possible to study activated carbon adsorption properties of UV absorbing, fluorescing and nonfluorescing, polyelectrolytic macromolecules fractionated from the total macromolecular and nonmacromolecular composition of NOM. Adsorption isotherms were constructed at pH 6 and pH 9. Data were described by the traditional and modified Freundlich models. Activated carbon capacity and adsorbability were compared among fractionated molecular subsets of fulvic and humic acids. Preferential adsorption (or adsorptive fractionation) of polyelectrolytic, fluorescing fulvic and humic macromolecules on activated carbon was observed. The significance of observing preferential adsorption on activated carbon of fluorescing macromolecular components relative to nonfluorescing components is that this phenomenon changes the composition of dissolved organic matter remaining in equilibrium in the aqueous phase relative to the composition that existed in the aqueous phase prior to adsorption. Likewise, it changes the composition of dissolved organic matter remaining in equilibrium in the aqueous phase relative to the adsorbed phase. This research increases our understanding of NOM interactions with activated carbon which may lead to improved methods of potable water production.

Adsorption↗