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Diffuse transfers of pesticides from agricultural land to ground and surface waters can lead to significant drinking water quality issues. This thesis describes the development and application of a parameter-efficient, numerical model to predict pesticide concentrations in raw water sources within an integrated hydrological framework. As such, it fills an unoccupied niche that exists in pesticide fate modelling for a computationally undemanding model that contains enough process complexity to be applicable in a wide range of catchments and hydrogeological settings in the UK and beyond. The model represents the key processes involved in pesticide fate (linear sorption and first-order degradation) and transport (surface runoff, lateral throughflow, drain flow, percolation to the unsaturated zone, calculated using a soil water balance) in the soil at a daily time step. Soil properties are derived from the national soil database for England and Wales and are used to define the boundary conditions at the interface between the subsoil and the unsaturated zone. This is the basis of the integrated hydrological framework which enables the application of the model to both surface water catchments and groundwater resources. The unsaturated zone model accounts for solute transport through two flow domains (accounting for fracture flow and intergranular matrix flow) in three hydrogeological settings (considering the presence and permeability of superficial deposits). The model was first applied to a small headwater sub-catchment in the upper Cherwell. Performance was good for drainflow predictions (Nash Sutcliffe Efficiency > 0.61) and performed better than the MACRO model and as well as the modified MACRO model. Surface water model performance was evaluated for eight pesticides in five different catchments. Performance was generally good for flow prediction (Nash Sutcliffe Efficiency > 0.59 and percentage bias below 10 %, in the validation period for all but two catchments). The 90th percentile measured concentration was captured by the model in 62 % of catchment-pesticide combinations. In theremaining cases predictions were within, at most, a factor of four of measured 90th percentile concentrations. The rank order of the frequency of pesticides detected over 0.1 μg L-1 was also predicted reasonably well (Spearman’s rank coefficient > 0.75; p < 0.05 in three catchments). Pesticide transport in the unsaturated zone model was explored at the point scale in three aquifers (chalk, limestone and sandstone). The results demonstrate that representing the unsaturated zone processes can have a major effect on the timing and magnitude of pesticide transfers to the water table. In comparison with the other catchment scale pesticide fate models that predict pesticide exposure at a daily time-step, the model developed stands out requiring only a small number of parameters for calibration and quick simulation times. The benefit of this is that the model can be used to predict pesticide exposure in multiple surface and groundwater resources relatively quickly which makes it a useful tool for water company risk assessment. The broad-scale approach to pesticide fate and transport modelling presented here can help to identify and prioritise pesticide monitoring strategies, to compare catchments in order to target catchment management and to highlight potential problems that could arise under different future scenarios.

Farmworkers and their families may experience increased levels of agricultural pesticides in their homes due to both (1) take-home/soil track-in on shoes, clothes and skin, and (2) air infiltration from nearby agriculture fields via agricultural pesticide drift in the vapor phase or adhered to resuspended soil particles. This dissertation estimates the relative contributions o the take-home/soil track-in and air infiltration pathways of agricultural pesticides into homes, as well as identifies the risk factors for increased in-home agricultural pesticide levels for farmworkers and their families living near agriculture fields. Samples of outdoor air, yard soil, and house dust from 21 farmworkers' homes in Yuma County, Arizona were collected and analyzed for a suite of agricultural pesticides. To capture household information, such as behaviors, demographics, and housing structure, a participant questionnaire was administered at the time of the sampling. A pesticide transport model was developed, evaluated, and applied to quantify relative contributions of the air infiltration and the take-home/soil track-in pathways of agricultural pesticides into the house dust of the farmworkers' homes. To explore a wide-range of potential risk factors for increased agricultural pesticide levels in the homes, traditional statistical methods and Classification and Regression Tree (CART) analyses were used. The results of this study, found that the air infiltration pathway contributes to over 90% of some agricultural pesticides in the house dust found in the farmworkers' homes. In addition, among the influential risk factors for increased in-home agricultural pesticide levels was the home being a closer distance to an agricultural field, as well as the home having carpeted floors, more farmworkers per square footage of the home, and less months of heating and cooling the home. It is suggested that future intervention efforts to reduce in-home agricultural pesticide levels put more emphasis on targeting the air infiltration pathway, and take into consideration relevant risk factors for increased pesticide levels in the home.

Les pesticides appliqués par pulvérisation dans les cultures sont dispersés à la surface des plantes où ils peuvent être transformés sous l'effet de la lumière solaire. Nous avons montré dans ce travail que les herbicides mésotrione et sulcotrione, et les insecticides cypermétrine et deltaméthrine sorbés à la surface des cires cuticulaires, sont photosensibles. Cette propriété est modifiée par l'ajout d'additifs présent dans les formulation commerciales ? Ces derniers peuvent accélèrer ou ralentir la photolyse des principes actifs. Cependant, il ne semble pas y avoir de règle générale permettant de prévoir l'importance de la phototransformation pour chaque matière active. D'autre part, alors qu'en laboratoire la dissipation des pesticides étudiés est uniquement due à la phototranformation ; sur les plantes entières, d'autres phénomènes interviennent. La diffusion dans la cuticule et les pertes dues au lessivage par la pluie ou la rosée peuvent devenir prépondérantes devant la phototransformation.

The study was conducted to monitor pesticide residues in groundwater of two agriculturally intensive regions of Alberta, to determine the occurrence of pesticide residues in soil and groundwater of an experimental plot in southern Alberta, and to investigate the influence of land management factors and soil depth on pesticide residues in soil. A total of 440 groundwater samples were collected in three years (2013-2015) and analyzed for the presence of 142 pesticides using Liquid-liquid Extraction (LLE) in combination with Gas Chromatography- Mass Selective Detector (GC-MSD) and Gas Chromatography - Tandem Mass Spectrometry (GC-MS/MS). Ten herbicides, seven insecticides, and six fungicides were detected. Herbicides 2,4-D, MCPA, and clopyralid were the most frequently detected, and the only pesticides consistently detected every year in both regions. Pesticides were detected more frequently in summer and fall compared to spring. 4.5% of the samples were contaminated with more than one pesticides. No pesticides exceeded the Guidelines for Canadian Drinking Water Quality. Similarly, a total of 213 groundwater samples (December 2014-November 2015) and 61 soil samples (in December 2014) in duplicates were analysed from the experimental plots in Lethbridge. Soil samples were collected at various depths (0-75 cm) and analyzed for the presence of 130 pesticides. A linear mixed effect model was fitted to determine the effect of soil depth, cropping systems and manure amendments on pesticide concentration in soil. In groundwater, bentazone, 2,4-D, and MCPA occurred most frequently and pesticide detection frequency varied seasonally with greater detections in July and September compared to other months. 37 different pesticide compounds were detected, and DDT isomers, 2,4-D, difenoconazole, MCPA and trans-heptachlor epoxide accounted for 85% of all detections. p,p’-DDE, 2,4-D, p,p-DDT, difenoconazole and MCPA occurred throughout the soil column and all of these except p,p-DDT were detected in underlying groundwater. Bentazone was found in groundwater throughout the year but not in soil. A greater number and higher concentrations of pesticides were found in soil. However, not all of them leached to groundwater. Soil depth and cropping system were significantly associated with total pesticide and total DDT concentration in the soil. Manure amendments had no affect pesticide concentrations. / May 2017

Detection and identification of pesticide residues on objects of cultural heritage is a serious and urgent challenge that currently faces many museums, Native American communities, and private collections worldwide. Organic artifact materials, such as wood, animal hide, basketry, textiles, paper, horn and bone, have traditionally been treated with pesticides to eradicate and prevent infestation by insects, rodents, and mold. These poisonous substances can persist for years in the controlled environment of a museum storeroom and present a potential poisoning risk to people who come in contact with the objects. Surface-enhanced Raman spectroscopy (SERS) has the potential to detect volatile organic pesticides in this context. The technique can overcome the insensitivity of normal Raman spectroscopy and fluorescence interference, and make possible detection of many organic compounds in parts per million concentration. This investigation is aimed at evaluating SERS for the detection and identification of volatiles in museums, with emphasis on naphthalene vapor. The potential of several SERS-active materials; Tollens mirrors, gold film over nanosphere arrays, citrate-stabilized colloidal silver, and nanoporous gold; to detect Rhodamine B and naphthalene is investigated. The research also highlights the mechanisms that underlie SERS, and the relationship between substrate nanostructure and SERS performance.

Abstract 1 – A Geographic Information System for Evaluating Residential Pesticide Exposure and Prostate Cancer Incidence Agricultural pesticide exposure is hypothesized to be a risk factor for prostate cancer, and such exposures are of particular concern for men living in farming communities where large-scale pesticide applications occur. Prostate cancer incidence data were obtained from the State Health Registry of Iowa for the years 1996 through 2006, and county and census tract level age-adjusted incidence rates were calculated. Historical crop-specific land use records and pesticide sales data for the state of Iowa during 1990 were integrated into a geographic information system (GIS), where estimates of predicted exposure to the four most commonly used pesticides in Iowa (atrazine, metolachlor, cyanazine, alachlor) were produced. Ecological correlation between pesticide exposure and prostate cancer incidence was evaluated using Spearman’s (rank) correlation coefficient and linear regression analysis. Statistically significant associations between prostate cancer incidence and percent of acres of corn and soybean crops were found at both the county (r=0.22, p=.031 and r=0.33, p=.001, respectively) and census tract (r=0.10, p=.007 and r=0.13, p<.001, respectively) level. The associations between percent of land exposed to the specific pesticides and prostate cancer were not statistically significant. Our findings suggest that residential proximity to corn and soybean fields, and by association the pesticides used on those crops, is correlated with increased prostate cancer risk, but that the increase in risk is not correlated with exposure to the four most commonly used pesticides in Iowa in 1990. Findings from this study underscore the need for continued investigation of the association between agricultural exposures and prostate cancer incidence. Abstract 2 – Spatial Analysis of Prostate Cancer Incidence and Residential Pesticide Exposure in Iowa A statistically significant positive association between prostate cancer incidence and residential proximity to corn and soybean fields in Iowa exists. Research suggests that exposure to pesticides used on these crops increases prostate cancer risk. The objective of this study was to investigate clustering of prostate cancer risk in the presence of potential exposure to pesticides in Iowa. Prostate cancer incidence data (1996-2006) were obtained from the State Health Registry of Iowa. Using SaTScan software, clusters of high and low prostate cancer risk were identified. Ecological correlation between exposure to the four most commonly used pesticides (atrazine, metolachlor, cyanazine, alachlor) in Iowa during 1990 and residence in a cluster of relatively high or low prostate cancer incidence was evaluated using Pearson’s chi-square test statistic and logistic regression analysis. Clusters of increased prostate cancer risk were associated with a greater percentage of land used for all crops of interest (i.e., corn and soybean farming (p <0.001), corn farming (p <0.001), soybean farming (p <0.001)) and low exposure to alachlor (p =0.032) than did clusters with decreased risk of prostate cancer. After adjustment for percent of land used for each crop type, no association between pesticide exposure and prostate cancer risk was observed. Residence in or near agricultural communities increases prostate cancer risk. Our findings suggest that residential proximity to exposures specific to corn and soybean farming increases prostate cancer risk. Evaluation of exposure to less commonly used pesticides and those used in lower quantities is needed.   Abstract 3 – Multilevel Analysis of Residential Pesticide Exposure and Prostate Cancer Incidence An association between residential exposure to factors specific to corn and soybean farms in Iowa exists. The objectives of this study were to statistically assess spatial autocorrelation in prostate cancer incidence in Iowa and to evaluate the effect of residential exposure to the most commonly used pesticides for corn and soybean farms in Iowa in 1990 on prostate cancer incidence. Prostate cancer incidence data were obtained from the State Health Registry of Iowa for the years 1996 through 2006. Spatial patterning of age-adjusted incidence rates was assessed via Moran’s I global index of spatial autocorrelation. A hierarchical regression modeling approach with an assumed Poisson distribution was used to characterize the relationship between census tract level prostate cancer incidence and exposure to pesticides. Statistically significant spatial patterning of prostate cancer incidence, corn and soybean fields and pesticide use (p<.001 for all variables) was observed. After adjustment for individual and area level characteristics, prostate cancer risk increased by approximately 25% for each percentage point increase in percent of land used for corn and soybean crops. Prostate cancer risk was approximately 25% higher for Black men exposed to corn and soybean fields compared to white men exposed to corn and soybean fields. Results from this study support the need for further evaluation of residential exposure to environmental hazards specific to corn and soybean farming.

La thèse met en évidence, dans le cas de la France, une forme de régulation composite des risques sanitaires et environnementaux liés aux usages des pesticides par les jardiniers amateurs, qui comporte trois principales dimensions. (1) Intimement articulée aux mécanismes de marché, cette forme de régulation impute l’essentiel de la responsabilité à l’utilisateur considéré en tant que consommateur à responsabiliser, alors que les autorités publiques considèrent les firmes de pesticides comme des opérateurs économiques dont les avantages compétitifs sont à valoriser, veillant donc à respecter la dynamique de l’offre et de la demande tout en se chargeant d’encadrer ce marché par l’homologation des produits. (2) Elle épouse les principes de la société singulariste où l’individu serait la référence centrale de la dynamique des sociétés contemporaines et le régulateur des problèmes collectifs par ses choix de consommation et ses prises de positions individuelles. (3) Elle s’opère dans un contexte où l’État a per¬du sa centralité sous la double influence de l’européanisation et de la décentralisation et où les modes de régulations politiques sont caractérisés par des formes moins dirigistes de gouvernement pouvant être définies comme des « politiques sans politique ». La régulation composite des pesticides domestiques est porteuse d’un postulat implicite qui impute la responsabilité des risques aux usagers et qui, si elle laisse ouverte la voie à une po¬ten-tielle réduction de l’usage des produits, tend à limiter leur exclusion et réduit les possibilités d’une transition vers un jardinage sans pesticides. / In 2008, the amount of pesticides used by amateur gardeners in the approximately fifteen million private gardens which exist in France and which represent a total area of a million hectares, rose to 3500 tons. Within the framework of a highly growing social awareness regarding health and environment problems and whilst the cut back on the use of pesticides in agriculture represents one of the main political objectives in the field of environmental protection, and Europe defines its chemical substances control policies (REACH), a study on the use of pesticides in gardening practices represents a good observation point to understand representations, dispositions and social practices linked to the use of pesticides in private gardens, to question the announced “greening” of life styles, to appreciate the capacity of the commercial production-distribution chain to manage such problems, and finally to evaluate the impact and direction of public policies to prevent health and environment risks.The results of the thesis are supported by sociological investigations carried out with amateur gardeners, by means of questionnaires (N=900) and interviews (N=24), with producers and distributors of phytosanitary products and with the press specialized in gardening (N=17) in France. The analysis of the pesticides code of management applied since 2003 in Quebec and which constitutes a regulation which prohibits the use and sale of a series of pesticides recognized as the most hazardous health-wise in municipal and private gardens, represents a counterpoint of the French situation.In the case of France, the thesis underlines a sort of composite regulation regarding the sanitary and environmental risks linked to the use of pesticides by amateur gardeners, involving three dimensions. (1) Intimately linked to the marketing mechanisms, this type of regulation attributes the core of the responsibility to the user, considered as the consumer to be blamed, while public authorities consider the firms which produce the pesticides as economic operators whose competitive advantages must be considered, seeking to respect the dynamics of offer and demand as well as controlling this market based on product certification. (2) It adopts the principles of the one-man society where the individual would be the main reference of the dynamics of contemporary societies and the regulator of collective problems based on his consumer choices and his individual position-taking. (3) It is located in a context where the State has lost its central position under the double influence of “Europeanization” and “decentralization” and where the types of political regulations are characterized by less interventionist forms of government, which can be defined as “politics without politics”. The composite regulation of domestic pesticides has an implicit postulate which attributes the responsibility of the risks involved to the users and which , in case of leaving an open door to the potential reduction of the use of products, tends to limit their exclusion as well as the possibilities of a transition towards pesticide free gardening.

Master of Science / Department of Entomology / Kun Yan Zhu / Raymond A. Cloyd / Protected environments, such as greenhouses and interior plantscapes provide optimal conditions for arthropod (insect and/or mite) pests to survive, develop, and reproduce. Two commonly encountered insect pests in protected environments include the citrus mealybug (CMB), Planococcus citri, and the western flower thrips (WFT), Frankliniella occidentalis. It is difficult to mitigate CMB and WFT populations due to the behavioral characteristics of the insects and few pesticides that are registered for use in protected environments. This research involved two distinctly different studies. The objectives of the first study were to determine the efficacy and residual activity of systemic insecticides registered for use against CMB and to quantify CMB feeding locations. The objectives of the second study were to determine the compatibility and efficacy of commonly used binary pesticide mixtures against the WFT under both laboratory and greenhouse conditions. To determine the efficacy of systemic insecticides against CMB, greenhouse experiments were conducted in which coleus, Solenstemon scutellarioides, plants were artificially infested with CMB. Drench applications of each designated treatment were applied to each plant. Results associated with drench applications of the systemic insecticides against CMB indicated minimal CMB mortality (<30%) for both preventative and curative drench applications of azadirachtin and spirotetramat. Thiamethoxam, a neonicotinoid-based insecticide, at the labeled and twice the labeled rate provided the highest CMB mortality; however, not until 21 days after treatment was this observed, and CMB mortality was <80%. In all cases, significantly more CMB were located on the stem of green coleus plants compared to the leaf top and bottom. Pesticide mixture compatibility was determined using jar tests. In addition, phytotoxicity and efficacy of pesticide mixtures against WFT was determined through a series of laboratory and greenhouse experiments for each individual pesticide, and the mixtures to determine synergism, antagonism, or no effect. Results associated with the jar tests indicated that all the mixtures were compatible. Furthermore, the mixtures were not phytotoxic to the horticultural plant species evaluated. Laboratory results indicated that mixtures containing spinosad + bifenazate were antagonistic against WFT. Greenhouse experiments demonstrated significantly reduced efficacy associated with the abamectin + azadirachtin mixtures; however, each binary mixture provided approximately 80% mortality of WFT.

A crescente utilização do controle químico para o manejo de pragas na cultura dos citros tem afetado significativamente a dinâmica populacional de inimigos naturais como os ácaros predadores que são importantes no controle biológico de pragas como o ácaro-da-leprose Brevipalpus phoenicis (Geijskes). Dentro desse contexto, a integração dos controles químico e biológico, seja pela utilização de produtos seletivos ou linhagens de ácaros predadores resistentes a pesticidas, poderia resultar em uma forma de manejo racional de ácaros fitófagos. Sendo assim, a presente pesquisa foi desenvolvida para avaliar a suscetibilidade de diferentes espécies de ácaros fitoseídeos (Amblyseius chiapensis De Leon, Euseius concordis (Chant) e Iphiseiodes zuluagai Denamark & Muma) a dicofol e deltametrina, em populações coletadas em pomares de citros. Não houve variabilidade interespecífica na suscetibilidade ao dicofol. E também, não foi constatada variabilidade intraespecífica na suscetibilidade das populações de E. concordis testadas. Por outro lado, E. concordis apresentou-se aproximadamente 50 vezes mais tolerante do que I. zuluagai à deltametrina. Foi detectada variabilidade intraespecífica na suscetibilidade à deltametrina nas populações de E. concordis e I. zuluagai, sendo que a razão de resistência estimada foi maior do que 14 vezes para as populações de E. concordis e de 18 vezes para as populações de I. zuluagai testadas. E por último, verificou-se diferenças significativas quanto a respostas de repelência apresentadas pelas populações de E. concordis a resíduos de deltametrina. / The increase in the use of chemical control for managing pests of citrus has significantly affected the population dynamics of natural enemies such as predator mites that are important in the biological control of phytophagous mites such as Brevipalpus phoenicis (Geijskes). Within this context, the integration of chemical and biological control through the use of selective pesticides or strains of predator mites resistant to pesticides could be a more rational way to manage phytophagous mites. Thus, the objective of this research was to evaluate the susceptibility to dicofol and deltamethrin in populations of different phytoseiid species (Amblyseius chiapensis DeLeon, Euseius concordis (Chant) e Iphiseiodes zuluagai Denamark & Muma) collected in citrus groves. There was no interespecific variability in response to dicofol. And also, no intraespecific variability in the susceptibility to dicofol in E. concordis populations was detected in this study. On the other hand, E. concordis was 50 times more tolerant than I. zuluagai to deltamethrin. Intraespecific variability in the susceptibility to deltamethrin was detected for both E. concordis and I. zuluagai populations. A resistance ratio of > 14- fold and 18- fold was detected to deltamethrin in E. concordis and I. zuluagai populations, respectively. And finally, there was a significant difference in the repellency of E. concordis populations in deltamethrin residues.