The fast atom bombardment mass spectrometric analysis of the carbamate pesticide carbaryl

The carbamate pesticide, carbaryl, was quantitatively studied using fast atom bombardment mass spectrometry (FAB-MS). Mass spectra were obtained in the positive ion-mode using both 2-nitrophenyloctyl ether (NPOE) and 3-nitrobenzyl alcohol (NBA) as matrix liquids. The sample was applied by three different techniques; simple mixing, solvent mixing and surface precipitation. Smaller volumes of matrix liquid were found to produce more favourable ion currents. Detection limits were largely independent of the matrix or application technique used. The relationship between ion current and the mass of analyte was found to be intricately related to the choice of matrix liquid.

The role of physical activity and perceived adequacy on cardiorespiratory fitness in children with developmental coordination disorder

Evidence suggests that children with developmental coordination disorder (DCD) have lower levels of cardiorespiratory fitness (CRF) compared to children without the condition. However, these studies were restricted to field-based methods in order to predict V02 peak in the determination of CRF. Such field tests have been criticised for their ability to provide a valid prediction of V02 peak and vulnerability to psychological aspects in children with DCD, such as low perceived adequacy toward physical activity. Moreover, the contribution of physical activity to the variance in V02 peak between the two groups is unknown. The purpose of our study was to determine the mediating role of physical activity and perceived adequacy towards physical activity on V02 peak in children with significant motor impairments. This prospective case-control design involved 122 (age 12-13 years) children with significant motor impairments (n=61) and healthy matched controls (n=61) based on age, gender and school location. Participants had been previously assessed for motor proficiency and classified as a probable DCD (p-DCD) or healthy control using the movement ABC test. V02 peak was measured by a progressive exercise test on a cycle ergometer. Perceived adequacy was measured using a 7 -item subscale from Children's Selfperception of Adequacy and Predilection for Physical Activity scale. Physical activity was monitored for seven days with the Actical® accelerometer. Children with p-DCD had significantly lower V02 peak (48.76±7.2 ml/ffm/min; p:50.05) compared to controls (53.12±8.2 ml/ffm/min), even after correcting for fat free mass. Regression analysis demonstrated that perceived adequacy and physical activity were significant mediators in the relationship between p-DCD and V02 peak. In conclusion, using a stringent laboratory assessment, the results of the current study verify the findings of earlier studies, adding low CRF to the list of health consequences associated with DCD. It seems that when testing for CRF in this population, there is a need to consider the psychological barriers associated with their condition. Moreover, strategies to increase physical activity in children with DCD may result in improvement in their CRF.

From protest to powerlessness : a Marxist analysis of the Ontario NDP /

Using Marxist state theory as an analytical framework, this thesis explains the problems faced by the Ontario New Democratic Party government (1990-1995) in implementing a social democratic agenda. Not only was the government constrained in its ability to implement progressive policy, but it was also pushed to implement a Social Contract (involving legislated wage cuts to public sector employees) that alienated the party's base of support, making it more difficult for the party to organize in the future. Although this study relies predominantly on a reinterpretation of existing research on the topic, some primary research is used in the analysis, including interviews with members of the labour movement and former MPPs and analysis of the news media's treatment of the party/ government. Historical and class analytical perspectives are used to explain the evolution of the ONDP's structure and policies, as well as to assess the relative strength of the working class and its ability to support a social democratic political agenda. It was found that the ONDP' s unwillingness to develop a long term plan for social democracy, and its inability to act as a mass party or to build a strong working class movement, made it more difficult for the party to succeed when it formed the government. Moreover, the class nature of the capitalist state, along with pressure exerted by a well mobilized capitalist class, worked to limit the government' s options.

Legitimacy in question : elite-mass relations, constitutional reform and Canadian democracy /

During the 1980s and 1990s, Canadian political authority orientations underwent a significant transformation. Canadians are no longer deferential towards their political elites. Instead, they are autonomous, challenging, and increasingly participatory, and this continuing trend has brought the procedural legitimacy of the Canadian political process into question. The following study of elite-mass relations within Canadian democracy attempts to provide insight into the meaning of this change and how it should be addressed. An attitudinalbehavioural analysis ofthe electorate presents evidence that popular cynicism and alienation is rooted more deeply in a dissatisfaction with political institutions and traditions than with politicians. A structural analysis of the elected political elite reveals the failure of consociational traditions to provide effective representation as well as the minimal impact which the aforementioned orientation shift has had upon this elite. An event-decisional analysis, or case study, ofelite-mass relations in the arena of constitutional politics augments these complementary profiles and illustrates how the transformed electorate has significantly restricted the elected political elite's role in constitutional reform. The study concludes that the lack ofresponsiveness, representativeness, and inclusiveness ofCanada's elected political elite, political institutions, and political traditions has substantially eroded the procedural legitimacy of Canadian democracy during the 1980s and 1990s. Remedying these three deficiencies in the political system, which are the objects of increasing public demand, may restore legitimacy, but the likelihood that such reforms will be adopted is presently uncertain in the face of formidable difficulties and obstacles.

Teaching media literacy skills about commercials: a comparative analysis of media literacy instruction /

In this study, methods of media literacy instruction including analytic activities, production activities, and a combination of analytic and production activities were compared to determine their influence on grade 8 students' knowledge, attitudes, and behaviours towards commercials. The findings showed that media literacy instruction does improve media literacy skills. Specifically, activities that included an analytic component or an analytic and production component were significantly better than activities that included a production component. Participants that completed analytic or analytic and production activities were able to discern media-related terms, target audience, selling techniques, social values, and stereotypes in commercials better than participants that completed only production activities. The research findings also showed obstacles when teaching media literacy. When engaged in analytic activities, the difficulties included locating suitable resources, addressing the competition from commercials, encouraging written reflection, recognizing social values, and discussing racial stereotypes. When engaged in production activities, the difficulties were positioning recording stations, managing group work, organizing ideas, filming the footage, computer issues, and scheduling time. Strategies to overcome these obstacles are described.

Fast atom bombardment mass spectrometry studies of ruthenium (II) polypyridy coordination complexes and of group V Triptycenes and related complexes

In order to investigate the use of Fast Atom Bombardment Mass Spectrometry (FAB-MS) as a tool for structural characterization, two groups of complexes are analyzed. The first group is a set of ruthenium(II) coordination complexes containing bidentate polypyridyl ligands. The positive and negative ion FAB-MS spectra are found to be sufficient to allow for an almost complete characterization of the central metal atom, the ligands and the counter anions contained in the intact complex. An unusual observation of mUltiply charged ions in the positive ion FAB-MS spectra (i.e. [RUL 3 ]2+) is explained to be as a result of the oxidative quenching of the excited state of the doubly charged ion by the matrix, 3-nitrobenzyl alcohol. An analysis of a mixture shows that the technique is a good one for identifying components therein. A group of triptycene and related complexes containing Group V elements is also analyzed by FAB-MS and the results. in terms of relative abundances of fragment ions, are found to be consistent with known metal-carbon bond strengths.

Investigations into the extraction and the determination of polycyclic aromatic hydrocarbons (PAHs) from water by solid-phase extraction and capillary gas chromatography/ mass spectrometry

Factors affecting the detennination of PAHs by capillary GC/MS were studied. The effect of the initial column temperature and the injection solvent on the peak areas and heights of sixteen PAHs, considered as priority pollutants, USillg crosslinked methyl silicone (DB!) and 5% diphenyl, 94% dimethyl, 1% vinyl polysiloxane (DBS) columns was examined. The possibility of using high boiling point alcohols especially butanol, pentanol, cyclopentanol, and hexanol as injection solvents was investigated. Studies were carried out to optimize the initial column temperature for each of the alcohols. It was found that the optimum initial column temperature is dependent on the solvent employed. The peak areas and heights of the PAHs are enhanced when the initial column temperature is 10-20 c above the boiling point of the solvent using DB5 column, and the same or 10 C above the boiling point of the solvent using DB1 column. Comparing the peak signals of the PAHs using the alcohols, p-xylene, n-octane, and nonane as injection solvents, hexanol gave the greatest peak areas and heights of the PAHs particularly the late-eluted peaks. The detection limits were at low pg levels, ranging from 6.0 pg for fluorene t9 83.6 pg for benzo(a)pyrene. The effect of the initial column temperature on the peak shape and the separation efficiency of the PARs was also studied using DB1 and DB5 columns. Fronting or splitting of the peaks was obseIVed at very low initial column temperature. When high initial column temperature was used, tailing of the peaks appeared. Great difference between DB! and.DB5 columns in the range of the initial column temperature in which symmetrical.peaks of PAHs can be obtained is observed. Wider ranges were shown using DB5 column. Resolution of the closely-eluted PAHs was also affected by the initial column temperature depending on the stationary phase employed. In the case of DB5, only the earlyeluted PAHs were affected; whereas, with DB1, all PAHs were affected. An analytical procedure utilizing solid phase extraction with bonded phase silica (C8) cartridges combined with GC/MS was developed to analyze PAHs in water as an alternative method to those based on the extraction with organic solvent. This simple procedure involved passing a 50 ml of spiked water sample through C8 bonded phase silica cartridges at 10 ml/min, dried by passing a gentle flow of nitrogen at 20 ml/min for 30 sec, and eluting the trapped PAHs with 500 Jll of p-xylene at 0.3 ml/min. The recoveries of PAHs were greater than 80%, with less than 10% relative standard deviations of nine determinations. No major contaminants were present that could interfere with the recognition of PAHs. It was also found that these bonded phase silica cartridges can be re-used for the extraction of PAHs from water.

Residues in soils : a gas chromatography - mass spectrometry study

Combined gas chromatography and mass spectrometry has been used to identify unknown residues in soils (especially pesticides). The effect of U.V. light on DDT and linuron and quantitative estimation of elemental sulfur in different soils has also been carried out.

"The whole earth as village" : a chronotopic analysis of Marshall McLuhan's "Global Village" and Patrick McGoohan's The Prisoner

Marshall McLuhan's "global village", and his theories on communications and technology, in conjunction with Patrick McGoohan's television series The Prisoner (ATV, 1967-1968) are explored in this thesis. The Prisoner, brainchild of McGoohan, is about the abduction and confinement of a British government agent imprisoned within the impenetrable boundaries of a benign but totalitarian city -state called "The Village". The purpose of his abduction and imprisonment is for the extraction of information regarding his resignation as a government spy. Marshall McLuhan originally popularized the phrase "the global village" in The Gutenberg Galaxy: The Making o/the Topographic Man (1962), asserting that, "The new electronic interdependence recreates the world in the image of a global village" (p. 31). This thesis argues that valid parallels exist between McGoohan's conception of "village", as manifested in The Prisoner, and McLuhan's global village. The comprehensive methodological stratagem for this thesis includes Marshall McLuhan's "mosaic" approach, Mikhail Bakhtin's concept ofthe "chronotope", as well as a Foucauldian genealogicallhistorical discourse analysis. In the process of deconstructing McLuhan's texts and The Prisoner as products of the 1960s, an historical "constellation" (to use Walter Benjamin's concept) of the same present has been executed. By employing this synthesized methodology, conjunctions have been made between McLuhan's theories and the series' main themes of bureaucracy as dictatorship, the perversion of science and technology, freedom as illusion, and the individual in opposition to the collective. A thorough investigation of the global village and The Prisoner will determine whether or not Marshall McLuhan and/or Patrick McGoohan visualize the village as an enslaving technological reality.

Application of thermal ion-molecule reactions in tackling spectroscopic inferences in inductively coupled plasma mass spectrometry

Part I: Ultra-trace determination of vanadium in lake sediments: a performance comparison using O2, N20, and NH3 as reaction gases in ICP-DRC-MS Thermal ion-molecule reactions, targeting removal of specific spectroscopic interference problems, have become a powerful tool for method development in quadrupole based inductively coupled plasma mass spectrometry (ICP-MS) applications. A study was conducted to develop an accurate method for the determination of vanadium in lake sediment samples by ICP-MS, coupled with a dynamic reaction cell (DRC), using two differenvchemical resolution strategies: a) direct removal of interfering C10+ and b) vanadium oxidation to VO+. The performance of three reaction gases that are suitable for handling vanadium interference in the dynamic reaction cell was systematically studied and evaluated: ammonia for C10+ removal and oxygen and nitrous oxide for oxidation. Although it was able to produce comparable results for vanadium to those using oxygen and nitrous oxide, NH3 did not completely eliminate a matrix effect, caused by the presence of chloride, and required large scale dilutions (and a concomitant increase in variance) when the sample and/or the digestion medium contained large amounts of chloride. Among the three candidate reaction gases at their optimized Eonditions, creation of VO+ with oxygen gas delivered the best analyte sensitivity and the lowest detection limit (2.7 ng L-1). Vanadium results obtained from fourteen lake sediment samples and a certified reference material (CRM031-040-1), using two different analytelinterference separation strategies, suggested that the vanadium mono-oxidation offers advantageous performance over the conventional method using NH3 for ultra-trace vanadium determination by ICP-DRC-MS and can be readily employed in relevant environmental chemistry applications that deal with ultra-trace contaminants.Part II: Validation of a modified oxidation approach for the quantification of total arsenic and selenium in complex environmental matrices Spectroscopic interference problems of arsenic and selenium in ICP-MS practices were investigated in detail. Preliminary literature review suggested that oxygen could serve as an effective candidate reaction gas for analysis of the two elements in dynamic reaction cell coupled ICP-MS. An accurate method was developed for the determination of As and Se in complex environmental samples, based on a series of modifications on an oxidation approach for As and Se previously reported. Rhodium was used as internal standard in this study to help minimize non-spectral interferences such as instrumental drift. Using an oxygen gas flow slightly higher than 0.5 mL min-I, arsenic is converted to 75 AS160+ ion in an efficient manner whereas a potentially interfering ion, 91Zr+, is completely removed. Instead of using the most abundant Se isotope, 80Se, selenium was determined by a second most abundant isotope, 78Se, in the form of 78Se160. Upon careful selection of oxygen gas flow rate and optimization ofRPq value, previous isobaric threats caused by Zr and Mo were reduced to background levels whereas another potential atomic isobar, 96Ru+, became completely harmless to the new selenium analyte. The new method underwent a strict validation procedure where the recovery of a suitable certified reference material was examined and the obtained sample data were compared with those produced by a credible external laboratory who analyzed the same set of samples using a standardized HG-ICP-AES method. The validation results were satisfactory. The resultant limits of detection for arsenic and selenium were 5 ng L-1 and 60 ng L-1, respectively.