Accurate solubility measurements for the pesticide l-naphthyl-N-methylcarbamate (carbaryl) in water, natural and artificial seawater, NaCl, Na2SO4, CaCl2 and (CH3)4NBr, at different temperatures covering the range 5-45 °C, were obtained using a combination of the generator column method and absorption spectroscopy techniques. As a rule, it was found that the solubility of carbaryl in water and in the electrolyte solution increased with an increase in temperature. The thermodynamic parameter ΔG°, ΔH°, ΔS°, and ΔC°p at 298.15 K, for the dissolution process carbaryl(s) to carbaryl(aq) and carbaryl(s) to carbaryl(aq. elect.), were calculated by fitting the solubility information to the Clarke and Glew equation. The results were consistent with the model which considers carbaryl and (CH3)4NBr to be solvent-structure-promoters and the rest of the electrolytes used in this work as solvent-structure-breakers. The salt-effect as a function of temperature on the nonelectrolyte pesticide was obtained by calculating the Setchenov constants for each one of the electrolyte solutions mentioned above. Salting-out was observed in solutions prepared with NaCl, Na2SO4, and CaCl2 was well as in natural and artificial seawater, while salting-in was obtained with (CH3)4NBr solutions. Pseudo-first order rate constants and half-life times for carbaryl in water were determined for different pH values ranging from 9.70 ± 0.02 to 11.60 ± 0.02 and covering the temperature range 25.5 ± 0.2 to 34.7 ± 0.2 °C. A direct relationship between SDS concentration and pesticide solubility was found by showing that the presence of micelles increased the solubility of an otherwise sparingly soluble molecule like carbaryl. Under high pressures (1356±34, 1797±34, and 2203±34 atm) and using NaCl as cosolute, carbaryl was readily degraded at 30 °C, giving deprotonated l-naphthol as one of the final products, in agreement with previous observations reported in the literature with esters and substituted phenols. Pseudo-first order high-pressure rate constants were calculated and, according to the results, it was found that there was a direct relationship between these constants and pressure.

The aim of this diploma thesis is detailed characterization of new diol-based column, i.e. Torus DIOL designed for supercritical fluid chromatography, in hydrophilic interaction liquid chromatography. This stationary phase contains diol ligands bonded on BEH ("bridged ethylene hybrid") particles. The BEH sorbent is more stable at high pH, pressure and temperature than conventional silica sorbents. Five fluorinated pesticides were successfully separated on Torus DIOL column. Retention mechanism and effect of different parameters were tested by analysis of small polar compounds (nucleobases, uridine and its derivatives, acidic, neutral and basic compounds). Both partitioning of analytes between an aqueous layer deposited on the surface of the stationary phase and the mobile phase and adsorption of analytes on the stationary phase participate in the retention mechanism. Effect of the mobile phase aqueous part pH was investigated with the following buffering solutions: formic acid (pH = 2.1), 10mM ammonium acetate (pH = 4.7 and pH = 9.5). Obtained results showed that aqueous part pH significantly affects retention of acidic compounds according to their pKA values. Retention of all tested analytes on Torus DIOL column slightly increased with increasing ionic strength of mobile phase. The retention...

Pesticides are a growing concern around the world as they are widely increasing in use and not as highly regulated as some health and environmental hazards. As agricultural, home, and other pesticide applications continue to rise, the need for analytical testing and removal of these pesticides from our rivers, streams, and other runoffs is becoming more and more significant. Glyphosate, an active ingredient in the herbicide Roundup, is an amine compound that has a maximum contamination level of 700 ppb. This work studied the use of water soluble Iron (II) tetrasolfophthalocyanine in amine detection that could be further applied to glyphosate. Also included in this study is a glimpse of removal possibilities combining phthalocyanines with traditional adsorption media for enhanced extraction and capacity.

Accra Metropolis is the major recipient of agricultural produce in Ghana, with almost the entire population depending on rural agricultural activities for subsistence. To increase agricultural produce, various forms of pesticides are normally used in fruits and vegetable farming. The consequence is that several cases of pesticide poisoning have been observed. In this preliminary study, a field survey was carried out to assess the knowledge, attitudes, and peoples' perception concerning the use of pesticides by farmers in fruit production. The residual concentrations of selected pesticides in pawpaw, imported apples and tomato samples and the potential health risks associated with the exposure to these pesticides were also assessed. The field survey data indicated that more than 70% of the participants reported one or more poisoning upon fruits consumption resulting in pesticide-related illnesses. Pesticide residues in the various environmental samples were determined by gas chromatography with electron capture detector (GC-ECD). The results showed that, the levels of pesticide residues varied from <0.01 μg/g to as high as 0.11 μg/g depending on the pesticide monitored. The analysis of health risk estimates revealed heptachlor, heptachlor epoxide, endrin aldehyde, and endrin ketone levels exceeded the reference dose, suggesting a great potential for systemic toxicity in children considered the most vulnerable population subgroup. Lastly, the public is in the know of pesticide residues in fruits and calls for the curtailing of pesticide use on fruits and vegetable production via educational programmes for farmers on control and safer use of pesticides.

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A process for disposing of pesticide rinsewater generated from the rinsing of application equipment is being developed at Virginia Polytechnic Institute and State University. This process involves the sorption of pesticides onto an organic matrix followed by degradation in a composting environment. We are now evaluating the hazards that might be associated with land-applying composted pesticide waste. Diazinon was the first pesticide selected for evaluation, which consisted of two studies. The first used the earthworm species Eisenia foetida to evaluate the toxicity of soil amended with composted diazinon waste. The second study determined the bioavailability of delta-2-14C-diazinon and its degradation products to E. foetida in soil amended with composted delta-2-14C-diazinon. Results from the first study indicate that uncomposted diazinon sorbent and 30-day composted diazinon sorbent were toxic to E. foetida at sublethal and lethal levels. However, E. foetida exposed 60-day composted diazinon sorbent did not experience mortality or demostrate sublethal effects commonly associated with acetylcholinesterase inhibition. Earthworms exposed to diazinon that was uncomposted or composted for 30 days in the radiolabelled study experienced higher mortality than in the field study. After 30 and 60 days of composting 14C-diazinon became unextractably incorporated into organic matter and very little was mineralized. Earthworms were shown to accumulate radioactivity when exposed to soil amended with 60- day composted delta-2-14C-diazinon. The majority of this radioactivity was unextractably bound to earthworm tissue and that which was extractable contained only trace levels of delta-2-14C-diazinon. Based on the absence of toxicity in the field study and the low levels of 14C-diazinon present in earthworm tissues, 60 days of composting appears to greatly reduce the hazard that diazinon rinsate poses to E. foetida. / Master of Science

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