The development of automated methods for the determination of trace concentrations of carbomate pesticides in water using solid sorbent pre-concentration methods and high performance liquid chromatography /

Several automated reversed-phase HPLC methods have been developed to determine trace concentrations of carbamate pesticides (which are of concern in Ontario environmental samples) in water by utilizing two solid sorbent extraction techniques. One of the methods is known as on-line pre-concentration'. This technique involves passing 100 milliliters of sample water through a 3 cm pre-column, packed with 5 micron ODS sorbent, at flow rates varying from 5-10 mUmin. By the use of a valve apparatus, the HPLC system is then switched to a gradient mobile phase program consisting of acetonitrile and water. The analytes, Propoxur, Carbofuran, Carbaryl, Propham, Captan, Chloropropham, Barban, and Butylate, which are pre-concentrated on the pre-column, are eluted and separated on a 25 cm C-8 analytical column and determined by UV absorption at 220 nm. The total analytical time is 60 minutes, and the pre-column can be used repeatedly for the analysis of as many as thirty samples. The method is highly sensitive as 100 percent of the analytes present in the sample can be injected into the HPLC. No breakthrough of any of the analytes was observed and the minimum detectable concentrations range from 10 to 480 ng/L. The developed method is totally automated for the analysis of one sample. When the above mobile phase is modified with a buffer solution, Aminocarb, Benomyl, and its degradation product, MBC, can also be detected along with the above pesticides with baseline resolution for all of the analytes. The method can also be easily modified to determine Benomyl and MBC both as solute and as particulate matter. By using a commercially available solid phase extraction cartridge, in lieu of a pre-column, for the extraction and concentration of analytes, a completely automated method has been developed with the aid of the Waters Millilab Workstation. Sample water is loaded at 10 mL/min through a cartridge and the concentrated analytes are eluted from the sorbent with acetonitrile. The resulting eluate is blown-down under nitrogen, made up to volume with water, and injected into the HPLC. The total analytical time is 90 minutes. Fifty percent of the analytes present in the sample can be injected into the HPLC, and recoveries for the above eight pesticides ranged from 84 to 93 percent. The minimum detectable concentrations range from 20 to 960 ng/L. The developed method is totally automated for the analysis of up to thirty consecutive samples. The method has proven to be applicable to both purer water samples as well as untreated lake water samples.

VOCATIONAL INTERESTS: CONSTRUCT VALIDITY AND MEASUREMENT

This dissertation addressed several questions relevant to vocational interests and personality characteristics, examining (a) the roles of personality, vocational interests, and sexual fantasies in defining a general factor of Masculinity/Femininity (M/F) (Study 1), (b) the validity of a new measure of vocational interests (Study 2), and (c) the individual difference characteristics that discriminate between students in various academic majors, and that predict academic outcomes (Study 3). In Study 1, vocational interests, personality, and sexual fantasies were examined to find whether these variables would yield a general Masculinity/Femininity (M/F) factor, and whether that factor would still emerge when controlling for participant sex. The results of Study 1 revealed that a general factor of M/F did emerge. When sex was removed, the loadings of vocational interests decreased from high to very low, suggesting that the link of vocational interests with other indicators of M/F is mainly due to sex differences in these variables. The purpose of Study 2 was to validate the Oregon Vocational Interest Scales (ORVIS), a new public domain vocational interests questionnaire designed to measure eight vocational interest scales. ORVIS scores obtained in a college and community sample were compared with those of two personality measures and two cognitive ability tests. Results from this study showed that the ORVIS scales were reliable and showed good construct validity. The purpose of Study 3, using the ORVIS along with the HEXACO-PI and tests of cognitive ability, was to examine the individual difference characteristics of students in different academic majors, and to use the congruence between a student's academic major and vocational interests as a predictor of academic outcomes, such as GPA, academic major change, and satisfaction with major. The results of Study 3 revealed that students in different academic majors show theoretically meaningful differences in personality, abilities, and interests. Conscientiousness and math ability were found to be the best predictors of academic outcomes. However, congruence between major and interests did not add significant predictive validity to any of these outcomes beyond personality and ability. Together, these three studies show the role of vocational interests in defming MlF and in predicting various academic outcomes.