The Use of Multi-Criteria Decision Analysis in Performing Alternatives Assessment and Comparative Risk Analysis: The Case Study of Codling Moth Pesticides

Thesis (Ph.D.)--University of Washington, 2016-08

Relations entre apports terrigènes et conchyliculture dans les Pertuis Charentais

This work presents interactions between quantitative and qualitative river freshwater inputs and the shellfish farming (oyster and mussel) in the Pertuis Charentais. The quantity of freshwater (i.e. salinity) seems to have a weak influence on the shellfish farming contrarily to its quality determined by particulate and dissolved matters contained in the water. In autumn and winter, large precipitations have a "globally positive" effect amending the coastal ecosystem. Associated dissolved nutriments and the organic matter largely determine the quality of the coming spring growth for bred shellfish, itself controlling in turn the annual yield efficiencies. However, in winter their effects are postponed because of strong mineral load, low luminosity and temperature, then limiting the primary production. The spring contributions, directly linked to territorial practices, agriculture and tourism are more variable in quantity and quality from one year to another. They often correspond to high-risk inflows since numerous substances from anthropogenic watersheds can be found diluted in the coastal zone as in the Pertuis Charentais. Their impacts on in situ estuarine ecosystems are still poorly known since these substances are mainly studied and estimated in laboratory in controlled conditions. Several studies showed anthropogenic contaminations (i.e. cadmium, pesticides) could have significant direct or indirect effects on shellfish farming. For instance, the "summer" mortalities between 1990 and 2000 in the South of the Marennes-Oléron bay (MOB), that induced environmental and physiological oyster disorders, could be linked to pesticide effects, measured during consecutive years on the oyster bed of Ronce Perquis in the South of the MOB. The weak results from the spring larval rearing of the IFREMER experimental hatchery in the South of the bay, and chromosomal abnormalities measured on the stocks of wild oysters of the Pertuis could confirm a high-risk spring environment for the shellfish farming. In summer terrestrial inputs are reduced by low precipitations, anthropogenic water removals (drinking water, irrigation) and by plant evapotranspiration. Consequently certain years, a significant salinity increase in water masses of the Pertuis Charentais is observed. However, based on long-term observations, the significant interannual variability noticed in freshwater contributions constitutes one of the most important facts of these last years. When contributions are weak (i.e. 1991 and 2011), the mean annual salinity is 34.5 in the MOB. To the contrary, other years (i.e. 1977, 1981, 1983 and 1988), the mean salinity reduced to 30.5 shows the significant freshwater contributions to the bay. Elsewhere, particularly in the mediterranean region, oyster breeding water conditions characterized by high salinity values show the freshwater does not seem to be necessary for biological functions of the Pacific oyster Crassostrea gigas. Indeed, the oyster embryonic life in particular is well adapted to high salinity values as long as trophic resources are substantial and temperatures remain high. These two factors firstly condition the embryonic survival before the water salinity. Besides, in the Pertuis Charentais, wind conditions and the geographical bloodstock position rather determine the success of the larvae capture than seawater physic-chemical conditions. Finally, a misunderstanding still remains on summer freshwater contributions to the oyster larvae food supply.

Multi-residue analysis of 39 pesticides in surface waters of Ria de Aveiro

A multi-residue gas chromatography-mass spectrometry method was developed in order to evaluate the presence of 39 pesticides of different chemical families (organophosphorus, triazines, imidazole, organochlorine), as well as some of their transformation products, in surface water samples from Ria de Aveiro. Ria de Aveiro is an estuarine coastal lagoon, located in the northern west region of Portugal, which receives inputs from agriculture, urban and industrial activities. The analytical method was developed and validated according international guidelines and showed good linearity, with correlation coefficients higher than 0.9949 for all compounds, adequate precision and accuracy, and high sensitivity. Pesticides were chosen from the priority pollutants list of the Directive 2008/105/EC of the European Parliament and of the Council (on environmental quality standards in the field of water policy), or were selected due their common use in agricultural practices. Some of these 39 pesticides are, or are suspected to be, endocrine disruptor compounds (EDCs), being capable of altering the endocrine system of wildlife and humans, causing form malfunction and ultimately health problems. Even those pesticides which are not EDCs, are known to be awfully toxic and have a recognised impact in human health. The aquatic environment is particularly susceptible to pollution due to intentional and accidental release of chemicals to water [3]. Pesticide contamination of surface water is a national issue as it is often used as drinking water. This concern is especially important in rural agricultural areas where population uses small private water supplies, regularly without any laboratory surveillance. The study was performed in seven sampling points and the results showed a considerable concern pesticide contamination of all samples.

Development of gene expression-based biomarkers of exposure to metals and pesticides in the freshwater amphipod Hyalella azteca

Ecological risk assessment (ERA) is a framework for monitoring risks of exposure and adverse effects of environmental stressors to populations or communities of interest. One tool of ERA is the biomarker, which is a characteristic of an organism that reliably indicates exposure to or effects of a stressor like chemical pollution. Traditional biomarkers which rely on characteristics at the tissue level and higher often detect only acute exposures to stressors. Sensitive molecular biomarkers may detect lower stressor levels than traditional biomarkers, which helps inform risk mitigation and restoration efforts before populations and communities are irreversibly affected. In this study I developed gene expression-based molecular biomarkers of exposure to metals and insecticides in the model toxicological freshwater amphipod Hyalella azteca. My goals were to not only create sensitive molecular biomarkers for these chemicals, but also to show the utility and versatility of H. azteca in molecular studies for toxicology and risk assessment. I sequenced and assembled the H. azteca transcriptome to identify reference and stress-response gene transcripts suitable for expression monitoring. I exposed H. azteca to sub-lethal concentrations of metals (cadmium and copper) and insecticides (DDT, permethrin, and imidacloprid). Reference genes used to create normalization factors were determined for each exposure using the programs BestKeeper, GeNorm, and NormFinder. Both metals increased expression of a nuclear transcription factor (Cnc), an ABC transporter (Mrp4), and a heat shock protein (Hsp90), giving evidence of general metal exposure signature. Cadmium uniquely increased expression of a DNA repair protein (Rad51) and increased Mrp4 expression more than copper (7-fold increase compared to 2-fold increase). Together these may be unique biomarkers distinguishing cadmium and copper exposures. DDT increased expression of Hsp90, Mrp4, and the immune response gene Lgbp. Permethrin increased expression of a cytochrome P450 (Cyp2j2) and decreased expression of the immune response gene Lectin-1. Imidacloprid did not affect gene expression. Unique biomarkers were seen for DDT and permethrin, but the genes studied were not sensitive enough to detect imidacloprid at the levels used here. I demonstrated that gene expression in H. azteca detects specific chemical exposures at sub-lethal concentrations, making expression monitoring using this amphipod a useful and sensitive biomarker for risk assessment of chemical exposure.

The Kinome of Pacific Oyster Crassostrea gigas, Its Expression during Development and in Response to Environmental Factors

Oysters play an important role in estuarine and coastal marine habitats, where the majority of humans live. In these ecosystems, environmental degradation is substantial, and oysters must cope with highly dynamic and stressful environmental constraints during their lives in the intertidal zone. The availability of the genome sequence of the Pacific oyster Crassostrea gigas represents a unique opportunity for a comprehensive assessment of the signal transduction pathways that the species has developed to deal with this unique habitat. We performed an in silico analysis to identify, annotate and classify protein kinases in C. gigas, according to their kinase domain taxonomy classification, and compared with kinome already described in other animal species. The C. gigas kinome consists of 371 protein kinases, making it closely related to the sea urchin kinome, which has 353 protein kinases. The absence of gene redundancy in some groups of the C. gigas kinome may simplify functional studies of protein kinases. Through data mining of transcriptomes in C. gigas, we identified part of the kinome which may be central during development and may play a role in response to various environmental factors. Overall, this work contributes to a better understanding of key sensing pathways that may be central for adaptation to a highly dynamic marine environment.

Changes in the annual harmful algal blooms of Alexandrium minutum : effects of environmental conditions and drainage basin inputs in the Rance estuary (Brittany, France)

Time series of physico-chemical data and concentrations (cell L-1) of the toxic dinoflagellate Alexandrium minutum collected in the Rance macrotidal estuary (Brittany, France) were analyzed to understand the physico-chemical processes of the estuary and their relation to changes in bloom development from 1996 to 2009. The construction of the tidal power plant in the north and the presence of a lock in the south have greatly altered hydrodynamics, blocking the zone of maximum turbidity upstream, in the narrowest part of the estuary. Alexandrium minutum occurs in the middle part of the estuary. Most physical and chemical parameters of the Rance estuary are similar to those observed elsewhere in Brittany with water temperatures between 15–18 °C, slightly lowered salinities (31.8–33.1 PSU), low river flow rates upstream and significant solar radiation (8 h day-1). A notable exception is phosphate input from the drainage basin which seems to limit bloom development: in recent years, bloom decline can be significantly correlated with the decrease in phosphate input. On the other hand, the chemical processes occurring in the freshwater-saltwater interface do not seem to have an influence on these occurrences. The other hypotheses for bloom declines are discussed, including the prevalence of parasitism, but remain to be verified in further studies.

Geoprocessing applied to the assessment of environmental noise: a case study in the city of Sorocaba, São Paulo, Brazil

Noise mapping has been used as an instrument for assessment of environmental noise, helping to support decision making on urban planning. In Brazil, urban noise is not yet recognized as a major environmental problem by the government. Besides, cities that have databases to drive acoustic simulations, making use of advanced noise mapping systems, are rare. This study sought an alternative method of noise mapping through the use of geoprocessing, which is feasible for the Brazilian reality and for other developing countries. The area chosen for the study was the central zone of the city of Sorocaba, located in So Paulo State, Brazil. The proposed method was effective in the spatial evaluation of equivalent sound pressure level. The results showed an urban area with high noise levels that exceed the legal standard, posing a threat to the welfare of the population.

Integrated pest management and the (un)sustainable use of pesticides

Doutoramento em Engenharia Agronómica - Instituto Superior de Agronomia - UL

Aqueous photochemistry of pesticides triadimefon and triadimenol

The photochemistry of pesticides triadimefon and triadimenol was studied in aqueous solution and in methanol/water mixtures, in controlled and natural conditions. The photodegradation kinetics and product distribution are strongly dependent on the solvent and on the irradiation wavelength. The degradation rates are faster at 254 nm than at 313 nm. The kinetics is faster in water than methanol. Direct photoreaction is an important dissipation pathway of triadimefon in natural water systems while triadimenol is stable in these conditions. 1,2,4-Triazole and 4-chlorophenol are two of the major photodegradation products. The formation of the 4-chlorophenoxyl radical was detected for both pesticides in methanol and methanol/water mixtures. In methanol/water mixtures the reaction of both pesticides also occurs with 4-chlorophenolate formation, which increases with the water content. The photochemical studies of pesticides and other pollutants should be made in conditions as similar as possible to those observed in environmental systems. (C) 2003 Elsevier Science B.V. All rights reserved.

Synthetic polymers blend used in the production of high activated carbon for pesticides removals from liquid phase

For the activated carbon (AC) production, we used the most common industrial and consumer solid waste, namely polyethyleneterephthalate (PET), alone or blended with other synthetic polymer such polyacrylonitrile (PAN). By mixing PET, with PAN, an improvement in the yield of the AC production was found and the basic character and some textural and chemical properties were enhanced. The PET–PAN mixture was subjected to carbonisation, with a pyrolysis yield of 31.9%, between that obtained with PET (16.9%) or PAN (42.6%) separately. The AC revealed a high surface area (1400, 1230 and 1117 m2 g−1) and pore volume (0.46, 0.56 and 0.50 cm3 g−1), respectively, for PET, PAN and PET–PAN precursors. Selected ACs were successfully tested for 4- chloro-2-methylphenoxyacetic acid (MCPA) and diuron removal from the liquid phase, showing a higher adsorption capacity (1.7 and 1.2 mmol g−1, respectively, for MCPA and diuron) and good fits with the Langmuir (PET) and Freundlich equation (PAN and PET–PAN blend). With MCPA, the controlling factor to the adsorption capacity was the porous volume and the average pore size. Concerning diuron, the adsorption was controlled essentially by the external diffusion. A remarkable result is the use of different synthetic polymers wastes, as precursors for the production of carbon materials, with high potential application on the pesticides removals from the liquid phase.

In Situ Observation of the Thermal Decomposition of Weddelite by Heating Stage Environmental Scanning Electron Microscopy

The morphological and chemical changes occurring during the thermal decomposition of weddelite, CaC2O4·2H2O, have been followed in real time in a heating stage attached to an Environmental Scanning Electron Microscope operating at a pressure of 2 Torr, with a heating rate of 10 °C/min and an equilibration time of approximately 10 min. The dehydration step around 120 °C and the loss of CO around 425 °C do not involve changes in morphology, but changes in the composition were observed. The final reaction of CaCO3 to CaO while evolving CO2 around 600 °C involved the formation of chains of very small oxide particles pseudomorphic to the original oxalate crystals. The change in chemical composition could only be observed after cooling the sample to 350 °C because of the effects of thermal radiation.