Thesis (Ph. D.)--Ohio State University, 2008. / Title from first page of PDF file. Includes bibliographical references (p. 96-107).

The aim of this study was to investigate effects of the triazine herbicide metribuzine on oxidative stress level and antioxidant enzymes activity in gills, muscle and hepatopancreas of signal crayfish (Pacifastacus leniusculus Dana) and also extension of knowledge about effect of metribuzine on the environment. The experiment took up 60 days. Crayfish were exposured to metribuzine concentrations of 0.52 micrograms.l-1 (real environmental concentration) and 3.06 mg.l-1 (10% 96hLC50) for the first 30 days. Then a second phase followed depuration without metribuzine (30 days). Changes in the oxidative stress level (TBARS), superoxiddismutase (SOD) activity and catalase (CAT) activity were observed in all examined tissues. Changes in glutathionreductase (GR) activity were observed only in hepatopancreas. Chronic exposure of metribuzine demonstrated an oxidative damage of cell lipids, proteins and also changes in antioxidant activity in examined crayfish tissues.The results of this study suggest that crayfish are a very suitable organisms for toxicological tests and simultaneously extend knowledge about effect of metribuzine on the environment.

A linear-log model to predict yield loss due to metribuzin injury was established by Love et. al. in 1993. Two experiments were conducted in 2016 and 2017 to evaluate and improve this model for application in North Dakota (ND). Metribuzin was applied (1.12 a.i./ha) when potato plants were 20-30 cm tall at Inkster, ND. The model did not accurately predict yield loss in 2016 but performed better in 2017. Foliar injury was more correlated with yield reduction than relative plant height. Results also indicated that new models that used foliar injury at 21 days after treatment (DAT) data and at 7 DAT data, most accurately predicted total yield loss and marketable yield loss, respectively. The new model performed similar to the previous model, but unlike previous model it can predict yield loss very early in growing season (21 DAT). / USDA Specialty Block Grant Program

The main aim of this research is to provide a low cost and sustainable biochar for the removal of organic pollutants from aqueous solution. Wastewater pollution by organic contaminants of emerging concern has become a subject of intense discussion. Removing these contaminants from aqueous solution is paramount to improve water quality for both humans and animal consumption. Traditional adsorption techniques using activated carbon are universal and fast, however, they are very costly. This dissertation therefore seeks to find an alternative low cost adsorbent which can be used to adsorb contaminants from aqueous solution. In chapter one, an overview of some of the selected organic contaminants of emerging concern is given. Pharmaceutical and pesticide entry into the environment, their fate and ecotoxicity are highlighted. Available techniques for the removal of contaminants from aqueous solution are also given. Chapter two is a study on the adsorption of some selected pharmaceuticals using a fast pyrolysis low cost biochar produced from pinewood feedstocks. The pinewood biochar used as the adsorbent in this study was made by fast pyrolysis in an augered reactor at a temperature of 425 oC and a residence time of 20-30 s during bio-oil production. In chapter three, switchgrass biochar has been tested for its potential for remediating water that is contaminated with two phenoxy herbicides, 2,4-dichlorophenoxyacetic (2,4-D) acid and 2-methyl-4-chloro-phenoxyacetic acid (MCPA). The adsorption capacity was remarkable when compared to commercial activated carbon per unit of measured surface area. Furthermore, in chapter four, magnetic and non-magnetic low cost biochars have been tested for the removal of the herbicide metribuzin from aqueous solution under different experimental conditions. The magnetic biochar synthesized from raw switchgrass biochar does not show a detrimental effect on the adsorption capacity. Additional value of this magnetic biochar is the ease of separation from contaminated solution following adsorption.

<p>U okviru ove doktorske disertacije, razvijene su elektroanalitičke metode za određivanje odabranih pesticida primenom hronopotenciometrije. Ispitana je mogućnost primene elektrode od staklastog ugljenika i tankoslojne živine elektrode kao radnih elektroda za određivanje insekticida imidakloprida i herbicida metamitrona i metribuzina. U cilju optimizacije uslova hronopotenciometrijske tehnike, za svaki ispitivani sistem (pesticid/radna elektroda) ispitan je uticaj najznačajnijih eksperimentalnih parametara na analitički signal pesticida, uključujući mehanizam generisanja analitičkog signala na radnoj elektrodi (oksidacija/redukcija), optimalnu metodu za uklanjanje rastvorenog kiseonika iz analiziranog rastvora, kao i vrstu, pH i koncentraciju pomoćnog elektrolita. Nakon toga definisan je optimalni opseg potencijala i struje redukcije. Pored toga, u okviru validacije metode za svaki ispitivani sistem, ispitan je i definisan opseg linearnosti, određena granica detekcije i granica kvantifikacije, ispitana preciznost, tačnost, robusnost i selektivnost metode. Dobijeni analitički signal za ispitivane pesticide bio je posledica ireverzibilne redukcije analita na radnoj elektrodi, a za svaki analit dobijen je jedan redukcioni pik. U slučaju određivanja metribuzina eksperimenti su pokazali da se analitički signal ne može detektovati na elektrodi od staklastog ugljenika uz kori&scaron;ćenje dostupne instrumentacije. Ispitivanja u model-rastvorima za svaki ispitivani sistem pokazala su dobre karakteristike u pogledu preciznosti, tačnosti, selektivnosti i robusnosti metode. Najveća osetljivost za sva tri pesticida postignuta je uz primenu tankoslojne živine elektrode, a vrednosti granice detekcije iznosile su 0,17 mg/l za imidakloprid, 0,07 mg/l za metamitron i 0,04 mg/l za metribuzin. Nakon optimizacije i validacije, razvijene hronopotenciometrijske metode primenjene su na komercijalne formulacije pesticida i uzorke vode. U cilju dodatne potvrde hronopotenciometrijskih rezultata na uzorcima vode izvedena su komparativna merenja uz primenu hromatografske LC-MS/MS analize.</p> / <p>Within this doctoral dissertation, electroanalytical methods for the determination of selected pesticides using chronopotentiometry are developed. The possibility of using glassy carbon electrode and thin film mercury electrode as a working electrode for determination of insecticide imidacloprid and herbicides metamitron and metribuzin is investigated. In order to optimize the conditions of the chronopotentiometric technique for each tested system (pesticide/working electrode), the influence of the most important experimental parameters on the analytical signal of the pesticides is investigated, including the generating mechanism of the analytical signal on the working electrode (oxidation/reduction), the optimal method for removal of dissolved oxygen from the analyzed solution, as well as type, pH, and concentration of the supporting electrolyte. Afterwards, the optimal range of potential and reduction current is defined. Additionally, within the validation of the method for each tested system, the linearity range is determined and defined, limit of detection and quantification are determined, and precision, accuracy, robustness and selectivity of the method are tested. The obtained analytical signal for the investigated pesticides is the result of irreversible reduction of the analyte on the working electrode, and for each analyte one reduction peak is obtained. In the case of metribuzin determination, the experiments have shown that by using the available instrumentation the analytical signal can not be detected on the glassy carbon electrode. Investigation in model solutions for each tested system shows good characteristics in terms of precision, accuracy, selectivity and robustness of the method. The highest sensitivity for all three pesticides was achieved by using thin film mercury electrode, and values of detection limit were 0.17 mg/l for imidacloprid, 0.07 mg/l for metamitron and 0.04 mg/l for metribuzin. After optimization and validation, the developed chronopotentiometric methods are applied to commercial pesticide formulations and water samples. In order to further confirm the chronopotentiometric results on the water samples, comparative measurements are performed using chromatographic LC-MS/MS analysis.</p>

Influence of triazine based pesticide (Sencor 70 WG - active substance metribuzine) was assessed via biochemical and hematological blood profile determination of experimental fish. As experimental fish we used common carp (Cyprinus carpio L.) and rainbow trout (Oncorhynchus mykiss ). Before rating the Sencor 70 WG pesticide influence on biochemical and hematological blood profile we accomplished a preliminary test to determine a concentration range and after that a basic acute toxicity test to determine 96hLC50 value. Both fish samples fingerlings were used for performing the tests. After 96hLC50 determination two groups of experimental fish (aged 1-2 years) were under this concentration and one control group without the substance. The test was processed according to the OECD methodology No. 203. Fish dissection was performed after the test. The increased amount of phlegm of water consistency on the body surface was found out. The fish were of dark colour in contrast with the control group. The ventricle was larger and containing transudate. An outstanding vascular profusion of internal organs in the ventricle was found out. Biochemical profile of the rainbow trout (Oncorhynchus mykiss ) experimental group under 96 hour acute operation of pesticide Sencor 70 WG (89,3mg.kg-1) proved significant lowering (p<0,01) of total proteins (TP), triglycerides (TRIG), aspartate aminotransferase (AST), amonnia (NH3), alcaline phosphatase (ALP) and Ca2+ in the blood plasma in contrast with the control group. Hematological profile of the same group proved significant lowering (p<0,05) of the number of erythrocytes (Er), haematocrit (PCV), and significant increase (p<0,05) of erythrocyte haemoglobin (MCH) value in contrast with the control group. Biochemical profile of the common carp (Cyprinus carpio L.) experimental group under 96 hour acute operation of pesticide Sencor 70 WG (250,2 mg.l-1) proved significant lowering (p<0,01) of total proteins (TP), triglycerides (TRIG), lactate dehydrogenase (LDH), Ca2+ and inorganic phosphate (PHOS) and significant increase (p<0,01) of glukose (GLU) and amonnia (NH3) concentration in the blood plasma in contrast with the control group. Hematological profile of the same group proved significant lowering (p<0,01) of the haematocrit (PCV), erytrocyte haemoglobin (MCH), mean erytrocyte volume (MCV) and number of leukocytes (Leuko) in contrast with the control group.

Ionisable pesticides can be partially ionised within the range of natural soil pH and this strongly influences their reactivity in soils. This group includes important, worldwide contaminants of groundwater and surface waters. It is essential that their specific behaviour is recognised within risk assessment procedures. Experiments were carried out with ten pesticides (six acids and four bases) and nine arable soils (range in pH, texture and organic matter content) to advance the understanding and prediction of the behaviour of ionisable pesticides in soils. The main conclusions can be summarised as follows:<br />• Adsorption of ionisable pesticides tends to be stronger in soils with lower pH and containing more organic carbon. A regression equation including Log D (lipophilicity corrected for pH), the soil organic carbon content and a pesticide descriptor was selected to predict the adsorption of acids. The behaviour of bases was more complex and approaches specific to each compound seem to be required.<br />• There were some marked differences between the soils in their ability to degrade the different ionisable pesticides. The lack of consistent behaviour renders a global approach to prediction of degradation unrealistic. Distinct types of behaviour could however be distinguished according to the main route of degradation.<br />• Significant correlations between sorption and degradation were only observed for three pesticides out of ten, with faster degradation in soils with stronger sorption.<br />• A centrifugation technique was used to measure adsorption at realistic soil moisture contents and provides a robust characterisation of the fraction of pesticide available for leaching. Time-dependent adsorption was also assessed.<br />The increase in adsorption between one and seven days was not directly related to the level of adsorption although it was more important in soils containing more organic carbon.<br />Although specific interactions between pesticides and soils are still not fully understood, these results provide the basis for a more robust analysis of the behaviour of ionisable pesticides in the environment.

Goosegrass [Eleusine indica (L.) Gaertn.] and smooth crabgrass [Digitaria ischaemum (Schreb.) Schreb. ex Muhl.] are problematic weeds in bermudagrass and creeping bentgrass turf. Increased incidences of herbicide resistant weed populations and severe use restrictions on formerly available herbicides have increased need for selective, postemergence control options for these weeds in creeping bentgrass and bermudagrass turf. This weed management exigency has led turf managers to utilize less effective, more expensive, and more injurious options to manage goosegrass and smooth crabgrass. Although potentially injurious, topramezone can control these weeds, especially goosegrass, at low doses. Low-dose topramezone may also improve bermudagrass and creeping bentgrass response. An initial investigation of three 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibiting herbicides in different turf types showed that Kentucky bluegrass, perennial ryegrass, and tall fescue were highly tolerant to topramezone, while creeping bentgrass and bermudagrass could tolerate topramezone doses that may control grassy weeds. Further investigation suggested that frequent, low-dose topramezone applications or metribuzin admixtures could enhance weed control and may conserve turfgrass quality. A novel mixture of topramezone at 3.7 g ae ha-1 and metribuzin at 210 g ai ha-1 controlled goosegrass effectively and reduced bermudagrass foliar bleaching associated with topramezone 10-fold compared to higher doses of topramezone alone in 19 field and 2 greenhouse trials. In an attempt to further enhance bermudagrass tolerance to topramezone, post-treatment irrigation was applied at various timings. When bermudagrass turf was irrigated with 0.25-cm water at 15 or 30 minutes after herbicide treatment, bermudagrass injury was reduced to acceptable levels when following low-dose topramezone plus metribuzin but not when following high-dose topramezone alone. Goosegrass control was reduced significantly by post-treatment irrigation in all cases, while irrigation reduced goosegrass control by low-dose topramezone plus metribuzin to below-commercially-acceptable levels. Novel, low-dose, frequent application programs containing topramezone or siduron were developed for season-long crabgrass or goosegrass control on creeping bentgrass greens. Greens-height creeping bentgrass quality was preserved following five biweekly treatments of siduron at rates between 3,400 to 13,500 g ai ha-1 and topramezone at 3.1 g ha-1. Siduron programs controlled smooth crabgrass and suppressed goosegrass while topramezone programs controlled goosegrass and suppressed smooth crabgrass. In laboratory and controlled-environment experiments, goosegrass absorbed three times more 14C than bermudagrass within 48 hours of 14C-topramezone treatment. Bermudagrass also metabolized topramezone twice as fast as goosegrass. Metribuzin admixture reduced absorption by 25% in both species. When herbicides were placed exclusively on soil, foliage, or soil plus foliage, topramezone controlled goosegrass only when applied to foliage and phytotoxicity of both bermudagrass and goosegrass was greater from topramezone than from metribuzin. Metribuzin was shown to reduce 21-d cumulative clipping weight and tiller production of both species while topramezone caused foliar discoloration to newly emerging leaves and shoots with only marginal clipping weight reduction. These data suggest that selectivity between bermudagrass and goosegrass is largely due to differential absorption and metabolism that reduces bermudagrass exposure to topramezone. Post-treatment irrigation likely reduces topramezone rate load with a concomitant effect on plant phytotoxicity of both species. Metribuzin admixture decreases white discoloration of bermudagrass by decreased topramezone absorption rate and eliminating new foliar growth that is more susceptible to discoloration by topramezone. / Doctor of Philosophy / Goosegrass and smooth crabgrass are problematic weeds in bermudagrass and creeping bentgrass turf. Increased incidences of herbicide resistant weed populations and severe use restrictions on formerly available herbicides have increased need for selective, postemergence control options for these weeds in creeping bentgrass and bermudagrass turf. Although potentially injurious, topramezone (Pylex™) can control these weeds, especially goosegrass, at low doses. Low-dose Pylex™ may also improve bermudagrass and creeping bentgrass response. An initial investigation evaluating tembotrione (Laudis®), Pylex™, and mesotrione (Tenacity®) in different turfgrass species showed that Kentucky bluegrass, perennial ryegrass, and tall fescue were highly tolerant to Pylex™ at rates ranging from 0.75 to 2.25 fl. oz./A, while creeping bentgrass and bermudagrass were low to moderately tolerant to Pylex™. Further investigation suggested that frequent, low-dose (less than 0.25 fl. oz./A) Pylex™ applications or metribuzin (Sencor®) admixtures could enhance weed control and may conserve turfgrass quality. A novel mixture of Pylex™ at 0.15 fl. oz./A and Sencor® at 4 oz. wt./A controlled goosegrass effectively and reduced bermudagrass injury to near acceptable levels and significantly less than Pylex™ applied alone at 0.25 fl. oz/A. In an attempt to further enhance bermudagrass tolerance to Pylex™, post-treatment irrigation was applied at different timings. When bermudagrass turf was irrigated at 15 or 30 minutes after herbicide treatment, bermudagrass injury was reduced to acceptable levels when following Pylex™ at 0.25 fl. oz./A plus Sencor® at 4 oz but not when following Pylex™ applied alone at 0.5 fl. oz./A. Goosegrass control was reduced significantly by post-treatment irrigation in all cases, while irrigation reduced goosegrass control by low-dose Pylex™ plus Sencor® to below-commercially-acceptable levels. Novel, low-dose, frequent application programs containing Pylex™ or siduron (Tupersan®) were developed for season-long crabgrass or goosegrass control in creeping bentgrass greens. Greens-height creeping bentgrass quality was preserved following five biweekly treatments of Tupersan® at rates between 6 and 24 lb./A and Pylex™ at 0.125 fl. oz./A. Tupersan® programs controlled smooth crabgrass and suppressed goosegrass while Pylex™ programs controlled goosegrass and suppressed smooth crabgrass. The data from these studies indicate that utilizing low-dose Pylex™ in combination with Sencor® can impart acceptable bermudagrass safety while also controlling goosegrass effectively. For creeping bentgrass greens, the low-dose, frequent application of Tupersan® is the safest legal option for golf course superintendents to control smooth crabgrass effectively, while having some ability to suppress goosegrass.

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