Дисертації з теми "Pesticides Environmental aspects Victoria"

The use of pesticides poses a serious threat to the limited water resources of South Africa. The amounts which are not taken up by crop plants, are often washed away by runoff into surface waters, or leached through the soil, causing groundwater pollution. The problem of pesticide pollution is often intensified by inappropriate usage, disposal and monitoring in agriculture and predictive models have proven to be an effective tool for improving management practices. Research, however, has focused mainly on surface water contamination and groundwater impacts are largely unknown. Furthermore, pesticide registration in South Africa is largely determined by international standards and there is a need for impact assessments to be carried out under local conditions. The aims of this study included the determination of priority pesticides in South Africa based on usage and properties, the determination of pesticide sorption in two selected South African soils, and an assessment of pesticide fate by modelling.

Amitraz is a formamide acaricide used predominantly in the control of ectoparasites in livestock and honeybees. Amitraz hydrolysis is rapid and occurs under acidic conditions, exposure to sunlight and biodegradation by microorganisms. The main hydrolysis product of amitraz, 2,4-dimethylaniline, is recalcitrant in the environment and toxic to humans. An electrochemical method for the determination of total amitraz residues and its final breakdown product, 2,4-dimethylaniline, in spent cattle dip, is presented. Cyclic voltammetry at a glassy carbon electrode showed the irreversible oxidation of amitraz and 2,4-dimethylaniline. A limit of detection in the range of 8.5 x 10⁻⁸ M for amitraz and 2 x 10⁻⁸ M for 2,4-dimethylaniline was determined using differential pulse voltammetry. Feasibility studies in which the effect of supporting electrolyte type and pH had on electroanalysis of amitraz and its degradants, showed that pH affects current response as well as the potential at which amitraz and its degradants are oxidised. Britton-Robinson buffer was found to be the most suitable supporting electrolyte for detection of amitraz and its degradants in terms of sensitivity and reproducibility. Studies performed using environmental samples showed that the sensitivity and reproducibility of amitraz and 2,4-dimethylaniline analyses in spent cattle dip were comparable to analyses of amitraz and 2,4-dimethylaniline performed in Britton-Robinson buffer. In addition, the feasibility qf measuring amitraz and 2,4-dimethylaniline in environmental samples was assessed and compared to amitraz and 2,4-dimethylaniline analyses in Britton-Robinson buffer. Amitraz and 2,4-dimethylaniline were readily detectable in milk and honey. Furthermore, it was elucidated that 2,4-dimethylaniline can be metabolised to 3-methylcatechol by Pseudomonas species and the proposed breakdown pathway is presented. The biological degradation of amitraz and subsequent formation of 2,4-dimethylaniline was readily monitored in spent cattle dip. The breakdown of amitraz to 2,4-dimethylaniline and then to 3-MC was monitored using cyclic voltammetry.

The effect of tillage practices on leaching and persistence of atrazine and metolachlor was evaluated in a field study in the Coastal Plain region of Virginia. Field data were also used to validate pesticide transport models, GLEAMS and PRZM. The study was conducted on two 18x27 m plots located in a field that was in the second year of a two-year no-till wheat-beaDs-com rotation. One plot was conventionally tilled using a moldboard plow and a disk harrow before planting of com and application of chemicals. Soil samples were collected on six sampling dates during the crop growing season at 20 randomly selected locations in each plot with the 0-150 cm sampling depth divided into eight increments. Bromide concentrations were analyzed to provide an estimate of solute movement. High rainfall following chemical application led to rapid leaching of bromide, with the chemical moving faster in the no-till profile. Pesticide concentrations also showed a greater potential for leaching in the no-till plot in the early stages of the study. Chemical concentrations were higher in the no-till profile initially, and were higher in the tilled profile toward the end of the season. Atrazine dissipation was higher in the no-till plot, but there was no marked difference in metolachlor dissipation between the two tillage treatments. Over 35% of atrazine mass remained in the soil profile in both plots at the end of the crop growing season. Pesticide concentrations were found to vary largely over the two plots. The field data were used to evaluate the ability of the pesticide transport models, GLEAMS and PRZM, to represent chemical concentration distribution, depth of solute center of mass, and pesticide mass in the no-till and the conventionally-tilled root zone. The models were evaluated in three sequential steps. The fast simulation was completely uncalibrated, using best available estimates for the input parameters. For the second simulation hydrology parameters were calibrated to minimize errors in the hydrology component so as to better evaluate the prediction of pesticide behavior in soil. The third stage of the evaluation used pesticide dissipation half-life calculated from the field data. Model performance was evaluated using both objective and subjective criteria. GLEAMS and PRZM predicted pesticide concentration in soils reasonably well when run without any calibration. Bromide concentrations were predicted closer to the observed values than pesticides. Overall predictions by both models were better in the conventional tillage plot than in the notill plot. The comparative effect of tillage on observed chemical concentrations was represented better by GLEAMS than by PRZM. The models underpredicted leaching of pesticides in the early sampling dates. Predicted pesticide mass in the root zone were reasonably close to the field measured values. Calibration of the hydrology component of the models did not improve the prediction of pesticide behavior in soils. The use of field pesticide half-life resulted in better prediction of pesticide persistence but did not improve the overall prediction of pesticide behavior in the two plots. The study identifies selection of input parameters and correct interpretation of results as important factors in the effective use of GLEAMS and PRZM as management tools.
Master of Science

The state of the environment is increasingly present as an urgent concern for contemporary political, social, cultural and physical life. Yet the roles of the mass media (radio, television and newspapers) in shaping and influencing crucial public awareness, debates and environmental decision-making remain inadequately understood. Positioned as a critical studies inquiry into media representations and audience reception, this study forms part of a wider project amongst media scholars and culture critics on the relationship between media textual production and consumption. It explores how one radio station in Uganda, Central Broadcasting Service (CBS) radio, represents and constructs the environmental crises faced by Lake Victoria, especially pollution and overfishing. The focus is on the Victoria Voice radio documentaries aired on CBS radio in the year 2005. The study further explores how three lakeside communities negotiate these issues as radio broadcasts. It recognises that while the mass media contribute significantly to creating public awareness about such social concerns, their likelihood of having a direct and predictable impact on social behaviour is slight. The context and the lived experiences at the reception stage where the decisions are made on whether to adopt an innovation are ultimately the factors which impact on how they are negotiated. The thesis is informed by the theoretical and analytical framework of Cultural Studies as well as the Participatory Approach to Communication for Development perspectives. The study is specifically informed by the theories of ‘discourse’ (Foucault, 1980a, 1981) and the ‘circuit of culture’ (du Gay et al., 1997 and Johnson, 1987) and these provided the conceptual framework for investigating the representations, the production and the consumption of media texts. Predominantly qualitative methods have been employed in data collection and analysis. In the first place, a Critical Discourse Analysis (CDA) (Fairclough, 1995a, 1995c) of the radio texts has interrogated the discourses and discursive practices of CBS’ Victoria Voice environmental radio programmes in order to consider its representations of particular issues and consequently the discourses it privileged. Qualitative methods of participant observation, in-depth interviews and focus group discussions were deployed to investigate the negotiation of the texts by the lakeside communities. This research establishes that the Victoria Voice radio texts foreground three contesting types of discourses: the discourse of basic economic survival and livelihoods is articulated largely by the ordinary people, the lakeside communities; the discourse of sustainable development, particularly the protection and sustainability of Lake Victoria, by scientists and environmental experts; and the discourse of modernisation and corporate investment by politicians and/or policy makers and industrialists. The texts, to a large degree, reaffirm the hegemonic relations of power in Ugandan society, and thus contribute to the maintenance of the status quo. The selection of an elite category of informers (scientists, experts, politicians, policy makers) serves to marginalise the less powerful ordinary people (the fisher folk, farmers and other eyewitnesses). The construction of the elite as active and speaking subjects within the various debates introduced in these programmes, for example, works both to obscure and endorse the unequal power relations. At the reception side, while the lakeside communities attest to the relevance of the programmes in providing information on the issues concerning Lake Victoria and other aspects of their livelihood, they also recognise the power relations that underpin the sets of representations. Amongst these sets is government’s complicity with industry, in line with their economic policies and the global capitalist economy, while espousing the rhetoric of nature conservation. The study argues that sustainable solutions for the crises on Lake Victoria should take into account the socio-historical and cultural contexts of the lakeside communities. For the Ugandan media, particularly radio, there is a need to rethink the nature of the coverage, which tends to neglect the contextual factors, such as local socio-economic and cultural factors within which environmental issues and problems occur and which, as this thesis establishes, greatly influences the way people make sense of environmental issues and problems. I posit that the Participatory Approach that seeks to address the communities’ most pressing concerns should be adopted – to include more of the communities’ voices and involve them in the production of radio programmes.

The effects of the insecticide diflubenzuron (DFB) on the growth characteristics of two gram negative soil bacterial isolates were examined. The bacterial isolates were grown in the presences of varying amounts of DFB and showed no apparent change in cell numbers, over time, when compared to control cultures. However, one of the two isolates tested showed a delayed response in chitinase production, over the same time period, as determined by radioisotopic methodology. Chitinase fractions obtained from cell free culture supernatants, concentrated by ultrafiltration and purified by affinity chromatography, were examined for activity in the presence of DFB. High performance liquid chromatography (HPLC) techniques were utilized in the identification and quantification of products from control and experimental samples. Due to the loss of overall chitinase activity in the supernatants, this technique proved ineffective in determining chitinase response to DFB.
Department of Biology

The sorption of unformulated (98% pure) and formulated (86% pure + adjuvants) metolachlor to peat, rubber, and steam-exploded wood was studied. The concentration of pesticide ranged from 50 mg/L to 400 mg/L. Equilibrium concentrations for the batch reactors were reached within 24 hr. The sorption data for both unformulated and formulated metolachlor were best described by the Freundlich isotherm model. Metolachlor was preferentially sorbed in the following order: rubber > peat > wood fibers, with removal efficiencies of 80-85%, 70-80% and 50-65%, respectively. Differences in slopes of the isotherm lines and K values were negligible for each sorbent-type tested for both unformulated and formulated metolachlor. These results suggest that the presence of surfactants did not affect the sorption capacity of the sorbents at the concentration levels tested. However, isotherm plots showed S-shaped curve behavior for all of the sorbents in the presence of unformulated metolachlor, while a C-shaped curve was seen when the sorbents were mixed with formulated metolachlor.

This suggests that different bonding mechanisms may be involved for the sorption of unformulated and formulated metolachlor to the sorbents.

Various procedures were studied to improve removal efficiencies of formulated metolachlor. Sorption of metolachlor to peat was enhanced by hydrating the peat and pre-treating the peat with HCI. Circulation of formulated metolachlor through a rubber-packed column showed the greatest removal, with only 6 mg/L of the initial 400 mg/L remaining in solution. Removal efficiencies of steamexploded wood fibers were not improved by any of the methods investigated.
Master of Science

Thesis (Ph.D)--Stellenbosch University, 2000.
ENGLISH ABSTRACT: Copper oxychloride is a fungicide that is extensively used in vineyards in the Western Cape to treat and prevent fungal diseases. It is however not clear what the effects are on soil organisms, which play an important role in soil fertility, in South African soils. There is paucity of data linking results obtained in the laboratory to effects observed in the field, which will only become useful if a clear relation can be demonstrated. The aims of this study were to: ~ Determine the effects of copper oxychloride on field populations of earthworms and simultaneously monitor lysosomal membrane stability, measured as neutral red retention time (NRRT). ~ Validate experimental field studies by doing inventories of earthworm populations in long-term sprayed vineyards. ~ Determine the LC50 of copper oxychloride and simultaneously measuring NRRT, and linking them to the experimental field studies. ~ Conduct bioassays, burrowing activity- and soil-avoidance experiments to investigate their relations to earthworm population responses in the experimental field studies. Earthworms were sampled by hand-sorting in the field tests on treated and untreated field plots in the Western- (October 1998 - July 1999) and Northern Cape (April 1998 - October 1999). Soil samples and worms were analysed for copper contents and coelomocytes of live earthworms were used to conduct the neutral red retention assays. Acute toxicity tests were conducted over a period of 28 days during which the earthworms (Eisenia fetiday were exposed to different concentrations of copper oxychloride. Change in biomass and mortality were measured as endpoints, as well as NRRT. Bioassays, burrowing activity and soil-avoidance were conducted by exposing Aporrectodea caliginosa to grassland- and vineyard soil as well as grassland soil spiked with 60 J.1g.g-1copper in the form of copper oxychloride. Growth and mortality were recorded in the bioassays as well as copper concentrations In earthworm body tissues and substrates used over a period of28 days. Burrowing activity and soil-avoidance were determined by measuring the length of tunnels burrowed by A. caliginosa in soil profiles over a period of 4 days under different exposure regimes. Results from the field tests showed that spraying of copper oxychloride had a negative effect on earthworm populations at the prescribed application rates. NRR T in earthworms from the exposure plots was significantly (p<0.05) lower after just one spraying application. It was concluded that spraying copper oxychloride at prescribed application rates caused a decrease in field populations of earthworms and that NRRT was an early and reliable biomarker since it was indicative of later effects observed at the population level. Results obtained from the field inventory of earthworms in vineyards at Nietvoorbij, Robertson end Worcester confirmed data from the two field studies. The calculated LC50 of 882.78 I1g.g-1 for copper oxychloride and 519.40 I1g.g-1 for copper was ecologically relevant if a safety factor of 10 was applied. NRRT which manifested earlier than effects on biomass change in the acute toxicity tests, were significant when viewed against the background of responses of field populations of earthworms. From the bioassay experiments it was found that A. caliginosa exposed to copper oxychloride spiked soil had significantly (p<0.05) higher weight loss and mortality than those in grassland- and vineyard soil. This indicated that changes in biomass and mortality were indicative of population responses in the field and can be considered as ecologically relevant. Burrowing activity of A. caliginosa was significantly (p<0.05) lower in vineyard and copper oxychloride spiked soil than in grassland soil. Similarly in the soil avoidance experiments it was found that A. caliginosa avoided vineyard- and copper oxychloride contaminated soil. It is therefore concluded that burrowing activity and soil avoidance were ecologically relevant endpoints since they corresponded with population responses in the field. The study thus revealed that the long-term usage of copper oxychloride could have negative effects on earthworm populations. The spraying of copper oxychloride can have important implications on the sustainable use of agricultural soils since earthworms and other soil organisms play such an important role in soil fertility. The use of biomarkers and other ecotoxicological indicators can provide an early warning that soil organisms are under environmental stress.
AFRIKAANSE OPSOMMING: Die fungisied koperoksichloried word wyd gebruik in die Wes-Kaap om swamsiektes in wingerde te beheer en te voorkom. Dit is egter nie bekend wat die effek daarvan op Suid Afrikaanse grondbiota, wat 'n belangrike rol speel in grondvrugbaarheid, is nie. Daar is ook 'n tekort aan inligting wat die resultate van laboratoriumondersoeke in verband bring met veldstudies. Die doelstellings van die studie was om: ~ Die effek van koperoksichloried op erdwurmpopulasies in die veld te ondersoek en terselfdertyd membraanstabiliteit, as moontlike biomerker, gemeet as neutraal rooi retensietye (NRRT), te monitor. ~ Die geldigheid van eksperimentele veldstudies te toets deur ook grondanalises te doen in wingerde wat oor langtermyn met koperoksichloried bespuit is. ~ Die LC50 van koperoksichloried vir erdwurms te bepaal en terselfdertyd NRR T te meet asook om dié gegewens in verband te bring met die resultate van seisoenale veldstudies oor die uitwerking op erdwurmpopulasies. ~ Bio-evaluerings ("bioassays"), tonnelaktiwiteit- en vermydingseksperimente te onderneem en die verband tussen die toksiteitstoetse en populasieresponse, soos waargeneem in die veld, te ondersoek. Erdwurms is versamel deur handsortering tydens die veldtoetse in die Wes- (Oktober 1998 - Julie 1999) en Noord-Kaap (April 1998 - Oktober 1999) op kontrole en bespuite persele. Grondmonsters en erdwurms is spektrofotometries geanaliseer om koperinhoude te bepaal. Die selomosiete van lewende wurms is gebruik om NRR T te bepaal. Akute toksisiteitstoetse is uitgevoer oor 'n tydperk van 28 dae waartydens Eisenia fetida blootgestel is aan verskillende koperoksichloried konsentrasies. Veranderinge in biomassa en mortaliteit is bepaal asook NRRT. Bioevaluerings ("bioassays"), tonnelaktiwiteit- en vermydingseksperimente IS uitgevoer deur Aporrectodea caliginosa bloot te stel aan grasveld- en wingerdgrond asook grasveldgrond wat met koperoksichloried gekontamineer is. Groei en mortalitiet is bepaal in die "bioassays" asook koperkonsentrasies in die grond en erdwurm liggaamsweefsels oor 'n tydperk van 28 dae. Tonnelaktiwiteit en grondvermyding is bepaal deur die lengte van tonnels wat deur A. caliginosa gegrawe is te meet oor 'n tydperk van vier dae vir die verskillende blootgestelde groepe. Die resultate het aangedui dat koperoksichloriedbespuiting 'n negatiewe invloed het op erdwurmpopulasies teen die voorgeskrewe toedieningsprogram. NRRT in erdwurms van die blootstellingperseel, was beduidend (p<0.05) laer na 'n enkele bespuiting. Daar is verder bevind dat NRR T 'n betroubare en vroeë biomerker is, aangesien dit 'n aanduiding gegee het van latere effekte wat op populasievlak na vore getree het. Veldopnames in Nietvoorbij, Robertson en Worcester het die geldigheid van data verkry uit die veldstudies ondersteun. Die berekende LC50 van 882.78 ug.g" vir koperoksichloried en 519.40 ug.g" VIr koper was ekologies relevant indien 'n veiligheidsfaktor van 10 toegepas is. NRRT se ekologiese relevansie is bevestig deur dit te vergelyk met response wat in die veldtoetse waargeneem is. Deur bioevalueringseksperimente is bevind dat gewigsverlies en mortaliteit van A. caliginosa beduidend hoër was in koperoksichloried gekontamineerde grond as in die grasveld- (kontrole) en wingerdgronde. Veranderinge in biomassa en mortalitiet was aanduidend van populasieresponse soos waargeneem in die veldstudies en kan dus as ekologies relevante eindpunte beskou word. Tonnelaktiwiteit van A. caliginosa was beduidend (p<0.05) laer in wingerd- en koperoksichloried gekontamineerde grond as in grasveldgrond. Dieselfde is gevind in die grondvermydingstoetse waar A. caliginosa wingerd- en koperoksichloried gekontamineerde grond vermy het. Dit kan dus afgelei dat tonnelaktiwiteit en grondvermyding ook ekologies bruikbare eindpunte is aangesien dit verband hou met populasieresponse soos waargeneem in die veldstudies. Hierdie studie het getoon dat die herhaalde gebruik van koperoksichloried 'n nadelige invloed kan hê op erdwurmbevolkings. In die lig van die belangrike rol wat erdwurms en ander grondorganismes speel in grondvrugbaarheid kan die oormatige gebruik van hierdie fungisied ernstige implikasies inhou vir volhoubare benutting van landbougronde. Die gebruik van biomerkers en ander ekotoksikologiese eindpunte kan egter as vroeë waarskuwingsmetode dien dat die grondorganismes onder omgewingstres verkeer.

The Trinity River passes through the Dallas-Fort Worth metroplex receiving point and non-point source contaminant loadings. Lepomis spp. were collected at twelve sampling locations in the Trinity River in August 1987 and September 1988 and analyzed for organochlorine pesticides and heavy metals. Results from the study were compared to existing U.S. FDA action and tolerance levels, LC50s, and historical data. Various longitudinal trends and some concentration patterns were observed. Continual study of pesticide and metal body burdens in fish allow testing for trends, and thereby, lead to a better understanding of the distribution of contaminants in the Trinity River.

In recent years there has been a great deal of scientific interest in processes that affect the fate of organic chemicals in the environment. one main reason for this increased interest is due to greater environmental concern over accidental or purposeful release of these chemicals into the environment by man. A major environmental concern is the increased use of pesticides over the last few years. In the thirty years prior to 1978 the use of pesticides has increased by a factor of forty (Ridgeway et al., 1978). Recently the use of herbicides has been increasing, but that of insecticides has stabilized (Willis, 1983). Detectable amounts of organic pesticides can be found in many areas of the biosphere. For toxic organic chemicals to be used safely, researchers must have a clear understanding of the fate and persistence of these chemicals when they are released into the environment. This understanding will also allow the development of new products that, when properly used, will not produce adverse effects to man or the environment (Weber, 1972). According to the Toxic Substance Control Act (TSCA) any new or expanded-use chemical that might be released into the environment must be tested for environmental hazard.

Thesis (MTech (Chemical Engineering))--Peninsula Technikon, Cape Town, 2003
The monitoring of pesticide contamination in surface and groundwater is an essential aspect of an assessment of the potential environmental and health impacts of widespread pesticide use. Previous research in three Western Cape farming areas found consistent (37% to 69% of samples) pesticide contamination of rural water sources. However, despite the need, monitoring of pesticides in water is not done due to lack of analytical capacity and the cost of analysis in South Africa. The Solid Phase Microextraction (SPME) sampling method has been developed over the last decade as a replacement for solvent-based analyte extraction procedures. The method utilizes a short, thin, solid rod of fused silica coated with an absorbent polymer. The fibre is exposed to the pesticide contaminated water sample under vigorous agitation. The pesticide is absorbed into the polymer coating; the mass absorbed depends on the partition coefficient of the pesticide between the sample phase and the polymeric coating, the exposure time and factors such as agitation rate, the diffusivity of the analyte in water and the polymeric coating, and the volume and thickness of the coating. After absorption, the fibre is directly inserted into the Gas Chromatograph (GC) injection port for analysis. For extraction from a stirred solution a fibre will have a boundary region where the solution moves slowly near the fibre surface and faster further away until the analyte is practically perfectly mixed in the bulk solution by convection. The boundary region may be modelled as a layer of stationary solution surrounded by perfectly mixed solution.

Increasing public awareness of toxic moieties in our environment has put pressure on regulatory agencies to improve testing methods so that these harmful agents can be identified and quantitated at lower and lower levels. The main objective of this work was to investigate analytical methodologies that would allow the sensitive, selective determination of pollutants to be routinely possible. Polar, thermally labile sulfur-containing pesticides and pollutants were our focus analytes. This objective was achieved in two ways: 1) the development of supercritical fluid extraction procedures suitable for these compounds and 2) the interface of a sulfur-selective detector to chromatographic techniques appropriate for thermally labile compound analysis. Supercritical fluids, particularly CO₂, have recently been shown to be suitable replacements for traditionally used organic solvents in extraction. However, due to the polarity of the sulfonyl urea herbicides and thiocarbamate insecticides studied, pure CO₂ was found to be an ineffective extractant. Polar SF mixtures (2 and 5 % methanol-modified CO₂) were investigated as alternative supercritical extraction fluids. Of the modified fluids, only 2% methanol-modified fluid could be used due to post-SFE trapping problems encountered with the 5% modified fluid. The quantitative extraction of two of these herbicides from water at the 50 ppb level was achieved using the former SF. This SF was also used to extract three thiocarbamates from apples at the 2 ppm level. In order to achieve the second objective, a sulfur-selective gas chromatographic detector, the ozone-based sulfur chemiluminescence detector (SCD), was successfully interfaced to both packed column supercritical fluid chromatography (SFC) and microcolumn high performance liquid chromatography (micro-HPLC). The packed column SFC/SCD system was shown to be compatible with both pure CO₂ and methanolmodified CO₂ mobile phases with a detector sensitivity (2 pg S/sec.) comparable to that found with capillary SFC/SCD despite the presence of more CO₂, an effective chemiluminescence quenching agent. The equimolar response of this detector to sulfur was shown to be only somewhat affected by the coelution of other organic species and improper analyte combustion conditions. For micro-column HPLC/SCD, the detector was found to be compatible with methanol/water mobile phases. Mobile phase composition, mobile phase flow rate, air flow rate, and hydrogen flow rate were found to affect the detector's sensitivity. The detector's linear dynamic range, response factor, and detection limits were determined to vary as a function of mobile phase composition. Optimum sensitivity (600 fg S/sec.) was achieved with a mobile phase of 40% methano1l60% water mobile phase compositions investigated. The analysis of polyaromatic sulfur-containing hydrocarbons (PASH's), total sulfur in diesel fuel, and sulfonyl urea herbicides was realized with the SFC/SCD system while thiocarbamate pesticides from an apple matrix were examined with the HPLC/SCD system.
Ph. D.

Thesis (MSc)--Stellenbosch University, 2005.
ENGLISH ABSTRACT: The agricultural sector in South Africa relies heavily on the use of pesticides to protect crops against pest organisms. Pesticides can affect non-target organisms such as the meso- and macrofauna in the soil detrimentally. Since these organisms play an important role in the processes of mineralization and decomposition in the soil and contribute to soil fertility, it is important that they are protected. A large amount of published literature exists on the biological importance of soil meso- and macrofauna and the effects that various agricultural practices have on them. The main aim of this study was to investigate the influence of agricultural practices on the abundance and diversity of meso- and macrofauna in different vineyard soils. A comparative study was conducted of an organically managed, conventionally managed and an uncultivated control soil. A secondary aim was to determine the effect of these agricultural management practices on the biological activity of these animals. Soil samples were taken, from which mesofauna (Collembola and Acari) were extracted with a modified Tullgren extractor, identified and counted. Earthworms were extracted from the soil using hand sorting methods. Soil parameters such as pH, water holding capacity, organic matter content, soil texture and soil respiration were determined. Bait lamina and litter-bags were also used to help determine the biological activity within the soil. The mesofauna diversity was quantified using the Shannon Weiner diversity index, as well as a diversity index described by Cancela da Fonseca and Sarkar (1996). Differences in abundance of both the meso-and macrofauna were statistically measured using ANOVA's. Biological activity results were also interpreted using ANOV A's. Results indicate that the abundance of the meso fauna was the highest at the organically treated vineyard soil and lowest in the conventionally managed soil where pesticide application took place. The earthworms also showed the same trend as the mesofauna, but were much more influenced by seasonal changes. Biological activity, according to the bait lamina and the litter-bag results, was higher in both the conventionally and organically managed soils than in the control, but no statistical significant differences were found between the two experimental soils. The soil respiration (C02-flux), also indicating biological activity, was highest in the organically treated soil and lowest in the conventionally treated soil. The different sampling techniques used gave variable results and although the organically managed soil proved to have higher abundances of both meso- and macrofauna, the biological activity did not show the same trends. In conclusion the data did not give enough evidence as to whether organic management practices were more beneficial than conventional management practices for the maintenance of soil biodiversity.
AFRIKAANSE OPSOMMING: Die Suid Afrikaanse Landbousektor steun hewig op die gebruik van verskillende chemiese pestisiede om oeste teen pes organismes te beskerm. Pestisiede kon ook verskeie ander nie-teikenorganismes soos die meso- en makrofauna in die grond negatief affekteer. Hierdie organismes behoort beskerm te word omdat hulle 'n belangrike rol speel in grondprosesse soos mineralisering, en die afbreek van organiese materiaal. Hierdie organismes dra ook by tot die vrugbaarheid van die grond. Daar is heelwat gepubliseerde literatuur beskikbaar wat verband hou met die biologiese belangrikheid van grond meso- en makrofauna en die effekte wat verskeie landbou behandelings op hulle het. Die primêre doel van hierdie studie was om vas te stel watter invloed konvensionele landboupraktyke op die hoeveelheid en diversiteit van meso- en makrofauna in verskillende wingerdgronde het. 'n Vergelykende studie is gedoen om wingerdgronde wat konvensioneel en organies behandel is sowel as 'n onbehandelde kontrolegrond met natuurlike plantegroei met mekaar te vergelyk. 'n Sekondêre doel van hierdie studie was ook om die effek van die verskillende boerderymetodes op die biologiese akitiwiteit in die grond te ondersoek. Grondmonsters is geneem, waaruit die meso fauna (Collembola en Acari) deur middel van 'n aangepaste Tullgren ekstraktor ge-ekstraheer, geïdentifiseer en getel. Die erdwurms is deur middel van handsorteringsmetodes versamel. Die volgende grond parameters is gemeet: pH, waterhouvermoë, organiese materiaal inhoud, grondtekstuur en grondrespirasie. "Bait lamina" en "litter bags" is ook gebruik om biologiese aktiwiteit in die grond te bepaal. Die diversiteit van mesofauna is bepaal met die Shannon Weiner diversiteitsindeks, as ook 'n diversiteitsindeks wat deur Cancela da Fonseca en Sarkar (1996) ontwikkel is. Die resultate van beide die meso- en makrofauna hoeveelhede in die verskillende wingerdgronde is met mekaar vergelyk deur van ANOV A's gebruik te maak. Die resultate van die biologiese aktiwiteit is ook deur middel van ANOVO's statisties met mekaar vergelyk. Die resultate het aangetoon dat die hoeveelheid mesofauna die hoogste in die organies behandelde grond en die laagste in konvensionele grond was. Die erdwurms het dieselfde patroon as die mesofauna getoon, maar is baie meer deur seisoenale faktore geaffekteer, bv. reënval. Volgens die resultate van die "bait lamina" en die "litter bags" was die biologiese aktiwiteit in die grond hoër in beide die eksperimentele grond as in die kontrolegrond. Die grondrespirasie (C02-puIs) was hoër in die kontrolegrond as in die ander eksperimentele gronde. Daar was groot variasie tussen die resultate wat met die verskillende tegnieke verkry is en alhoewel die organiese perseel hoër hoeveelhede van beide meso- en makrofauna gehad het, het die biologiese aktiwiteit nie dieselfde tendens gewys nie. Vanuit die data wat verkry is kon daar dus nie met sekerheid afgelei word dat organiese boerderymetodes beter vir die biodiversiteit van gronde,soos hier gemeet, is as konvensionele boerderymetodes nie.

A field scale model for predicting the surface losses of pesticides (Pesticide Losses In Erosion and Runoff Simulator, PLIERS) was developed. PLIERS accounts for pesticide losses by degradation and volatilization, the washoff of pesticides from plant canopy and surface residue, the adsorption and desorption of pesticides to and from soil particles, and the movement of pesticides in the dissolved and adsorbed phases. Hydrologic data are generated by the comprehensive watershed model, FESHM; which contains an extended sediment detachment and transport algorithrn. PLIERS uses first order rate equations to describe degradation and volatilization, and pesticide washoff. The adsorption of pesticides to individual particle size classes is estimated using the Freundlich equation.

Movement of atrazine and 2,4-D in runoff and sediment was measured on twelve field plots under simulated rainfall. The plots were treated with conventional or no-tillage in combination with one of three residue levels (0, 750, and 1500 kg/ha). Runoff and sediment losses were found to increase with decreasing residue cover for both tillage systems. No·till reduced sediment loss and total runoff volume by 98 and 92 percent, respectively, compared to conventional tillage. Concentrations of atrazine and 2,4-D ir1 runoff and sediment were greater from the no-till plots than from the conventional plots but the total losses were less. Both pesticides were carried predominately in the dissolved phase. Averaged over all plots, the atrazine losses were 2.9 percent of applied amount for conventional tillage and 0.3 percent for no-tillage. The corresponding values for 2,4-D were 0.3 percent and 0.02 percent.

PLIERS was validated using data from the rainfall simulator field plot studies. Agreement between predicted and observed data was very good for dissolved pesticide losses and satisfactory for adsorbed pesticide losses. In addition, the effects of tillage type and residue level were reflected in PLIERS predictions. PLIERS shows great potential as a flexible planning tool since it could be used with any comprehensive hydrologic model and is able to predict the losses of pesticides under various field conditions.

Master of Science

A watershed scale water quality evaluation system was developed for assessing spatial variation of subsurface pesticide movement. The system consists of a linked-transport model component for performing simulation and a GIS component for processing spatially-related data. The surface heterogeneity caused by agricultural activities, topographic, hydrologic, and soil type variations in a watershed was handled by partitioning the watershed into homogeneous subfields. The subsurface soil profile and aquifer heterogeneities were considered by dividing the subsurface domain into root zone, intermediate vadose zone, and saturated zone, respectively. On each of the homogeneous subfields, the physically-based models, PRZM and VADOFT, were linked to simulate pesticide transport in the root and intermediated vadose zones. Pesticide movement in groundwater underneath the watershed was simulated by linking the other two models with SUTRA. An irregular shape finite element mesh generator was developed for fitting the irregular shape watershed boundary and reducing the number of nodes of the finite element mesh. Either transient or steady state flow and transport simulation could be performed with the system. The system is able quantitatively to produce detailed spatial variation maps of pesticide concentrations at any desired depth in the unsaturated zone and in groundwater. The system requires spatially-distributed information as inputs. Management of large volumes of spatially-referenced data which represent the heterogeneous properties of the watershed were facilitated by a developed GIS component. The GIS data processing component was composed of spatial data manipulation and display, attribute database management, and model input information extraction subcomponents. The spatial data processing component consists of data format conversion, map registering, map editing, new information generation, and map display subcomponents.
Ph. D.

Thesis (MPhil)--Stellenbosch University, 2003.
Full text to be digitised and attached to bibliographic record.
ENGLISH ABSTRACT: This assignment is devoted to an in depth analysis of the pro- and the contra-positions in the long-standing and costly debate about the question whether to spray with DDT or not in the fight against malaria. I argue that the dilemma whether or not to spray with DDT is born out of a political agenda, hype, exaggeration and misinformation of the first order. Radical environmentalists appear to insist that DDT is a principal contributor of environmental degradation, and the major cause of death amongst wildlife and humans. Worse still, many Western people seem to be under the impression that mosquitoes cannot cause so much human misery as purported, and that malaria is caused by some kind of plant form of life, or even a virus. The proponents of DDT, on the other hand, appear to be convinced that DDT is a saviour of humankind, and argue that the horrors associated with DDT are exaggerated and baseless, as they are not backed by scientific inquiry. Proponents of DDT also believe that anything that is overused may kill, even ordinary table salt. Inthis assignment, both of these positions are scrutinized. On the basis of an historical overview in Chapter I of the history of the use of DDT, and the emergence of the debate about DDT in the wake of Rachel Carson's Silent Spring (1962), Chapter 2 is devoted to an evaluation of seven basic arguments against the use of DDT, while in Chapter 3 six arguments for the use of DDT are weighed. In Chapter 4 a resolution of the dilemma is proposed in which a case is made for a limited use of DDT only for indoor spraying of huts and houses against malaria mosquitoes until such time as a less dangerous alternative for DDT is found that can be used as effectively in the fight against malaria. As such, this case is informed by the strong moral conviction that we cannot allow poor people of colour to die because of a general ban on the use of DDT. Further research on this ethical debate is encouraged.
AFRIKAANSE OPSOMMING: Hierdie werkstuk is toegespits op 'n in-diepte analise van die pro- en kontra-posisies in die voortslepende, asook duur debat oor die gebruik van DDT al dan nie in die bekamping van Malaria. Ek argumenteer dat die dilemma rondom die vraag of DDT gebruik moet word of nie, aangewakker word deur politieke agendas, sensasie, oordrywing en foutiewe informasie van die eerste orde. Radikale omgewingsgesindes dring oënskynlik daarop aan dat die gebruik van DDT 'n hoof-oorsaak is van die agteruitgang van die omgewing, asook 'n primêre oorsaak van dood onder wild en mense. Erger nog, dit wil voorkom of heelwat Westerse mense onder die indruk is dat muskiete nie werklik soveel menslike lyding kan veroorsaak as wat voorgegee word nie, en dat malaria eerder veroorsaak word deur 'n sekere soort plantvorm van lewe, of selfs deur 'n virus. Die voorstaanders van DDT, aan die ander kant, is klaarblyklik oortuig dat DDT 'n redder van die mensdom is, en argumenteer dat die gruwels wat geassosieer word met DDT 'n grondelose oordrywing is, aangesien dit nie deur wetenskaplike ondersoek gesteun word nie. Voorstaanders van DDT glo verder dat enige stof wat in oormaat gebruik word, die dood kan veroorsaak, selfs gewone tafelsout. In hierdie werkstuk word albei hierdie posisies krities bestudeer en bespreek. Op grond van 'n historiese oorsig in Hoofstuk 1 oor die gebruik van DDT, en die ontstaan van die debat oor DDT na aanleiding van Rachel Carson se Silent Spring (1962), word Hoofstuk: 2 gewy aan 'n evaluasie van sewe basiese argumente teen die gebruik van DDT, terwyl in Hoofstuk 3 ses argumente vir die gebruik van DDT oorweeg word. In Hoofstuk 4 word 'n voorstel gemaak vir die resolusie van die dilemma deur 'n saak uit te maak vir die beperkte gebruik van DDT, nl. slegs vir binneshuise gebruik in hutte en huise teen malaria-muskiete tot tyd en wyl 'n minder gevaarlike alternatief vir DDT gevind word wat net so effektief sal wees in die stryd teen malaria. As sulks word hierdie studie gerugsteun deur die sterk morele oortuiging dat ons nie kan toelaat dat mense van kleur sterf as gevolg van 'n algemene verbod op die gebruik van DDT nie. Verdere navorsing oor hierdie etiese debat word aangemoedig.

This study employed geographic information systems (GIS) technology to evaluate the vulnerability of groundwater to pesticide pollution. The study area included three provinces (namely, Kanchana Buri, Ratcha Buri, and Suphan Buri) located in the western part of central Thailand. Factors used for this purpose were soil texture, percent slope, primary land use, well depth, and monthly variance of rainfall. These factors were reclassified to a common scale showing potential to cause groundwater contamination by pesticides. This scale ranged from 5 to 1 which means high to low pollution potential. Also, each factor was assigned a weight indicating its influence on the movement of pesticides to groundwater. Well depth, the most important factor in this study, had the highest weight of 0.60 while each of the remaining factors had an equal weight of 0.10. These factors were superimposed by a method called “arithmetic overlay” to yield a composite vulnerability map of the study area. Maps showing relative vulnerability of groundwater to contamination by pesticides were produced. Each of them represented the degree of susceptibility of groundwater to be polluted by the following pesticides: 2,4-D, atrazine, carbofuran, dicofol, endosulfan, dieldrin & aldrin, endrin, heptachlor & heptachlor epoxide, total BHC, and total DDT. These maps were compared to groundwater quality data derived from actual observations. However, only the vulnerability maps of atrazine, endosulfan, total BHC, and heptachlor & heptachlor epoxide showed the best approximation to actual data. It was found that about 7 to 8%, 83 to 88% and 4.9 to 8.7% of the study area were highly, moderately, and lowly susceptible to pesticide pollution in groundwater, respectively. In this study a vulnerability model was developed, which is expressed as follow: V = 0.60CW + 0.10CS + 0.10CR + 0.10CL + 0.10CSL. Its function is to calculate a vulnerability score for a certain area. The factor “V” in the model represents the vulnerability score of a certain area, whereas CW, CS, CR, CL, and CSL represent the values or classes assigned to well depth, soil texture, monthly variance of rainfall, primary land use, and percent slope in that area.

Dissertação composta por 3 artigos.
CAPES
O meio ambiente está em constante modificação, principalmente devido à influência antrópica. O monitoramento destes ambientes tem como objetivo caracterizar o meio, prever danos futuros e remediar possíveis impactos. No ambiente, as águas superficiais são dinâmicas, com constantes mudanças e crescente demanda, necessitando da garantia de qualidade para seu uso, realizada através de análises físico-químicas, microbiológicas e de compostos traço. Neste estudo, amostras de águas superficiais, de 12 pontos distintos da cidade de Apucarana-Paraná (Brasil), foram coletadas no período de um ano. As amostras foram submetidas às análises físico-químicas e microbiológicas, analisadas com base na quimiometria, a fim de demonstrar a influência do meio urbano e rural, e os fatores mais relevantes para a caracterização do ambiente. Considerando os ambientes de influência rural, foram analisadas a presença de pesticidas organoclorados, com a otimização do método de microextração líquido-líquido dispersiva, e uso instrumental da cromatografia gasosa acoplada a espectrometria de massa. Os dados apontam que os ambientes estão livres de contaminação e dentro dos padrões de aceitação, tanto para os parâmetros físico-químicos quanto microbiológicos. Os ambientes de interesse também apresentaram-se isentos de contaminação por pesticidas organoclorados no período de pesquisa.
The environment is constantly changing, mainly due to human influence. Environmental monitoring has object to environment, predict future damage and remedy potential impacts. Surface water is a dynamic medium, with constant changes and increasing demand, requiring quality assurance for their use, performed by physical-chemical, microbiological and analysis compounds traits. In this study, surface water samples of 12 different points of the city of Apucarana, Paraná (Brazil), were collected within one year. The samples were subjected to physical, chemical and microbiological analyzes, analyzed based on chemometrics in order to demonstrate the influence of urban and rural areas, and the most important factors to characterize the environment. Considering the influence of rural environments were analyzed the presence of organochlorine pesticides in the optimization of the method of liquid-liquid microextraction dispersive, and instrumental use of gas chromatography-mass spectrometry. Data indicates that the environments are free from contamination and within the acceptable standards for both the physical-chemical and microbiological parameters. The environments of interest also presented free of contamination by organochlorine pesticides in the research period.
5000

Organophosphates and carbamates are potent inhibitors of the neurotransmitter acetylcholinesterase. This inhibition results in the blocking of nerve signal transference into the post synaptic neuron leading to loss of muscle action and death. Because of the universal mechanisms of signal transduction in animals, these inhibitors have been widely used as agricultural pesticides as well as chemical warfare agents (nerve agents). Health issues associated with pesticide usage result from the fact that both the pesticides and their breakdown products often end up in water and food sources as well as in the soil. As a result, there has been an increase in the number of studies aimed at the detection of these pesticides in the environment. One popular research area is enzyme based biosensor construction. Some important criteria for consideration during the construction of biosensors are the importance of a suitable solid support as well as the enzyme immobilisation method. Recently, there has been increased interest in using nano-scale material e.g. using nanoparticles as enzyme support material. This is largely due to their advantages such as large surface area to volume ratio as well as reduced mass transfer resistance. Electrospinning is a straight forward and cost effective method for producing nanofibres from any soluble polymer(s). The applications of electrospun nanofibres have been reported in clinical studies, biofuel production as well as bioremediation. In this study two polymers were selected: nylon for its mechanical stability and chitosan for its biocompatibility and hydrophilicity, for the fabrication of electrospun nanofibres which would function as immobilisation support material for acetylcholinesterase. The first objective of this study was to electrospin nanofibres from a nylon-6 and chitosan blend solution. A binary solvent system consisting of formic acid and acetic acid (50:50) successfully dissolved and blended the polymers which were subsequently electrospun. Scanning electron microscopy characterisation of the nanofibres showed that (i) a nylon-6: chitosan ratio of 16%: 3% resulted in the formation of bead free nanofibres and (ii) the fibres were collected in non-woven mats characterised by different size nanofibres with average diameters of 250 nm for the main fibres and 40 nm for the smaller nanofibres. Fourier transform infra-red (FT-IR) analysis of the nanofibres indicated that a new product had been formed during the blending of the two polymers. The second aim of the study was to carry out a facile immobilisation of electric eel acetylcholinesterase via glutaraldehyde (GA) cross-linking. Glutaraldehyde solution 5% (v/v) resulted in the immobilisation of 0.334 mg/cm² of acetylcholinesterase onto the nanofibres. The immobilisation procedure was optimised with reference to acetylcholinestease and crosslinker concentrations, incubation time and the cross-linking method. A comparative investigation into the optimum pH and temperature conditions, pH and thermal stabilities, substrate and inhibition kinetics was then carried out on free and immobilised acetylcholinesterase. The final objective of this study was to determine the storage stabilities of the immobilised and free enzymes as well as the reusability characteristics of the immobilised acetylcholinesterase. Several conclusions were drawn from this study. Acetylcholinesterase was successfully immobilised onto the surface of nylon-6:chitosan nanofibres with retention of its activity. There was a shift in the pH optimum of the immobilised acetylcholineseterase by 0.5 units towards a neutral pH. Although both free and immobilised acetylcholinesterase exhibited the same optimum temperature, immobilised acetylcholinesterase showed enhanced thermal stability. In terms of pH stability, immobilised acetylcholinesterase showed greater stability at acidic pH whilst free acetylcholinesterase was more stable under alkaline pH conditions. Relative to free acetylcholinesterase, the immobilised enzyme showed considerable storage stability retaining ~50% of its activity when stored for 49 days at 4°C. Immobilised acetylcholinesterase also retained > 20% of its initial activity after 9 consecutive reuse cycles. When exposed to fixed concentrations of carbofuran or demeton-S-methyl sulfone, immobilised acetylcholinesterase showed similar inhibition characteristics to that of the free enzyme. The decrease in enzyme activity observed after immobilisation to the nanofibres may have been due to several reasons which include some enzyme molecules being immobilised in structural conformations which reduced substrate access to the catalytic site, participation of the catalytic residues in immobilisation and enzyme denaturation due to the reaction conditions used for acetylcholinesterase immobilisation. Similar observations have been widely reported in literature and this is one of the major drawbacks of enzyme immobilisation. In conclusion, nylon-6:chitosan electrospun nanofibres were shown to be suitable supports for facile acetylcholinesterase immobilisation and the immobilised enzyme has potential for use in pesticide detection. Future recommendations for this study include a comparative study of the GA cross-linking method for AChE immobilisation which will lead to more intensely bound enzyme molecules to prevent non-specific binding. An investigation into the effect of inhibitors on stored immobilised AChE, as well as reactivation and reuse studies, may also be useful for determining the cost-effectiveness of reusing immobilised AChE for pesticide detection in environmental water samples. Several models have been designed for the determination of the kinetic parameters for immobilised enzymes. These take into account the mass transfer resistance as well as the overall charge of the immobilisation matrix. The use of these models to analyse experimental data will give a clear understanding of the effects of immobilisation on enzyme activity

Thesis (MSc)--Stellenbosch University, 2001.
ENGLISH ABSTRACT: Runoff is generally regarded as one of the most important routes of nonpoint source pesticide pollution in agricultural surface waters. Of major concern is the fact that low, sub-lethal levels of pesticide exposure are responsible for negative ecotoxicological effects, stressing the need for methods capable of identifying problem areas where populations could be at risk. Predicted average losses of three pesticides in tributaries of nine sub-catchments of the Lourens River were calculated through use of a GIS-based runoff model. There was a significant (p < 0.005) positive correlation between the predicted average loss and mean measured concentrations of the insecticides both in water and suspended sediments (R2 between 0.75 and 0.9), indicating that the model could serve as a powerful tool for the risk assessment and management of surface waters in South African orchard areas. Based on field relevant exposure scenanos, the potential effects of azinphos-methyl on macroinvertebrate communities were evaluated in a combined microcosm and field approach. Microcosms were contaminated for 1 h with AZP (control, 0.2; 1,5and 20 ug/L; three replicates each) and acute effects on survival were evaluated 6 days after exposure. The sensitivity or tolerance of 12 core taxa was determined based on their response to the exposure scenarios and compared to field tolerance/sensitivity as was established by a field investigation at a control and contaminated site of the Lourens River. The sensitivity/tolerance of ten of the 12 taxa corresponded to that which was found in the field. Thus microcosm studies employing a field relevant design can be successfully linked to field studies and indicate that transient pesticide contamination affects the aquatic communities of the Lourens River.
AFRIKAANSE OPSOMMING Afloop word oor die algemeen beskou as een van die belangrikste roetes van niepuntbron pestisiedbesoedeling in landbou oppervlakwaters. Die feit dat lae, sub-letale vlakke van pestisiedblootstelling negatiewe ektoksikologiese gevolge kan hê, is van groot belang. Dit beklemtoon die behoefte aan metodes om probleemgebiede te kan identifiseer waar bevolkings aan risiko onderhewig is. 'n GIS-gebaseerde afloopmodel is gebruik om die gemidddelde verlies van drie pestisiede in die sytakke van nege sub-opvangsgebiede van die Lourensrivier te voorspel. Daar was 'n beduidende (p < 0.005) positiewe korrelasie tussen die voorspelde gemiddelde verlies en gemete konsentrasies van insektisiede in beide die water en sediment (R2 between 0.75 and 0.9) fases, wat aandui dat die model as 'n kragtige hulpmiddel vir risikobestuur van oppervlakwaters in Suid Afrikaanse boord-gebiede kan dien. Die potensiële gevolge van azinfos-rnetiel (AZP) op makroinvertebraat gemeenskappe is deur middel van 'n gekombineerde mikrokosmos (wat op veldrelevante blootstellings gebaseer is) en veldbenadering bepaal. Mikrokosmosse is vir 1 h met AZP gekontamineer (kontrole; 1; 0.2; 1; 5 en 20 ~g1L; drie replikate elk), en die akute gevolge op oorlewing is ge-evalueer na ses dae van blootstelling. Die sensitiwiteit of toleransie van 12 sleutel taksa is deur middel van hulle respons op die blootstellingsreeks bepaal, en met hulle veldtoleransie/sensitiwiteit vergelyk wat in 'n veldstudie by 'n kontrole- en gekontamineerde gebied in die Lourensrivier bepaal is. Die sensitiwiteit/toleransie van 10 van die 12 taksa in die mikrokosmos eksperimente het ooreengestem met die wat in die veld gevind is. Mikrokosmosstudies wat op 'n veldrelevante ontwerp gebaseer is, kan dus suksesvol aan veldstudies gekoppel word, en dui aan dat oorgedraagde pestisiedkontaminasie die akwatiese gemeenskap van die Lourensrivier beinvloed.

A study was conducted to measure pesticide concentrations from two tile-drained potato fields in Saint-Leonard d'Aston, Quebec. Soil and water samples were analysed for the pesticides metribuzin, fenvalerate and aldicarb in 1989, and for metribuzin and phorate in 1990.
Metribuzin concentrations up to 3.47 $ mu$g/l were detected in the tile drain water. Surface runoff samples had metribuzin concentrations up to 47.086 $ mu$g/l. Aldicarb was not detected in any of the water samples. Fenvalerate was detected in surface runoff at a level of 0.05 $ mu$g/l during the 1989 growing season. Phorate was not detected in subsurface drain water in the 1990 growing season.
Pesticide levels were higher in the surface soil layer (0-5 cm), than at 25 cm depth. Fenvalerate was detected at a level of 0.013 $ mu$g/g in the surface (0-5 cm) soil samples. Phorate concentrations of up to 0.020 $ mu$g/g were detected in soil samples. Aldicarb was not detected in the soil samples. Metribuzin was found mostly in the soil surface layer with concentrations of up to 0.23 $ mu$g/g during the 1990 growing season.

Orientador: Luiz Lonardoni Foloni
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Agricola
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Resumo: A utilização de produtos fitossanitários para o controle de plantas daninhas, pragas ou doenças têm sido muito difundido em função da necessidade crescente da oferta de alimentos, limitação de áreas agricultáveis e disponibilidade de mão-de-obra. Os problemas gerados com a aplicação de produtos fitossanitários, sem o devido conhecimento, podem causar riscos ao meio ambiente e à saúde humana. A tendencia é órgão fiscalizador é exigir que antes do lançamento de um novo produto no mercado e antes de sua aplicação em áreas agricultáveis seja feito estudo rigoroso de seu comportamento no meio ambiente. Quando existe um bom banco de dados, modelos matemáticos são desenvolvidos objetivando prever comportamento ambiental do produto fitossanitário. O conceito de fugacidade, embora não seja novo, praticamente não tem sido estudado no Brasil na áreadas ciencias agrárias. A fugacidade pode ser um novo caminho para quantificar o transporte, a biocumulação e transferência entre os compartimentos ambientais. Este trabalho teve por objetivos: (a) desenvolver uma metodologia preliminar de previsão de destino ambiental dos inseticidas carbosulfan e carbofuran no cultivo de arroz irrigado, através de modelo matemático baseado no conceito de fugacidade, para delimitar os compartimentos mais vulneráveis; (b) prever o comportamento e o destino ambiental das moléculas do carbosulfan e carbofuran no cultivo de arroz irrigado, aplicando o conceito de fugacidade; (c) verificar, em condições de campo, o comportamento e o destino ambiental do carbosulfan e do carbofuran, comparando-os com a previsão feita. A fase experimental foi desenvolvida na Fazenda Varjão, município de Bariri-SP, coordenadas (21º59'47¿S e 48º36'41¿LGr) em solo Gleissolos. A cultura foi implantada no dia 22/11/02, utilizando-se a cultivar IRGA-420. Para evitar possíveis contaminações, a área experimental foi locada em um tabuleiro de 2 ha a montante da propriedade. A propriedade foi dividida em tabuleiro com dimensões variáveis de 1,5 a 2,5 ha, totalizando 200 tabuleiros, separados por canais de irrigação e drenagem. Tradicionalmente, para o controle da larva da bicheira-da-raiz é recomendado o uso do inseticida carbosulfan, na dose de 400 g i.a. ha-1, no sistema de benzedura. Foram determinados 8 pontos ao acaso no tabuleiro estudado, para coleta de amostras. Os compartimentos amostrados foram água laminar, solução do solo e do próprio solo. As seqüências de tempo escolhidas para as coletas de amostras de água laminar e solução do solo foram de 0, 24, 48, 96, 192, 378 e 678 horas após a aplicação. As amostras de solo foram realizadas em 0, 24, 48, 96, 192, 378, 678, 1536 e 1656 horas após a aplicação. As cinéticas de degradação do carbofuran e do carbosulfan foram avaliadas em condições de campo através da análise dos resíduos das amostras coletadas. Utilizou-se da identificação e quantificação dos resíduos foi realizada através de um detector seletivo de massas, acoplado ao cromatógrafo. Este foi operado no modo de monitoramento de íons (SIM), sendo utilizados os fragmentos 160 e 164 para a quantificação de carbofuran e carbosulfan, respectivamente. Os dados experimentais e as equações diferenciais que descrevem a cinética do carbosulfan e do carbofuran permitiram estimar a meia-vida dos inseticidas na água e na solução do solo e no próprio solo. Os valores estimados das meias-vidas para o carbosulfan na água laminar, no solo e na solução do solo foram 1, 25 e 21 dias, respectivamente. Para o carbofuran as meias-vidas na água laminar e na solução do solo foram 3 e 10 dias, respectivamente. Os resultados indicam os compartimentos preferenciais do carbofuran, facilitando a tarefa de amostragens em programas do monitoramento da qualidade ambiental, e permite antecipar o destino ambiental do inseticida carbofuran. Experimentos de campo foram conduzidos para verificar a proximidade entre os valores simulados e os valores observados de concentrações do carbofuran na água e no solo
Abstract: Pesticide use to control pests, diseases and weeds is steadily increasing due to a general food demand increase, cropping area limitation, and manpower availability. Pesticide application without a sound knowledge may hazard environment and human health. Regulatory agencies enforces that, before a new product releasing to the market for agricultural use, intensive studies on its environment impacts ought to be developed. When a large and useful database is available, mathematical models are developed to estimate or predict product environmental behavior. In Brazil, although the available knowledge, practically there are no studies on fugacity concept applied to agricultural subjects. Fugacity in the proposed form might be a new tool in quantifying the movement, bioaccumulation and transfer of pesticides betweeen environment compartments. The objectives of this research work were: (a) to develop a preliminary method for predicting the environmental destination of carbosulfan and carbofuran insecticides applied to field irrigated rice, using a model based on the fugacity concept to delimit most vulnerable compartments; (b) to predict the behavior and environmental destination of carbosulfan and carbofuran molecules applied on field irrigated rice, using the fugacity concept; (c) to validate the prediction model by comparison with experimental data obtained under field conditions. The experimental data was obtained from a field irrigated rice experiment carried out at 'Varjão¿ Farm, district of Bariri, State of São Paulo, Brazil (21º59'47¿S and 48º36'41¿LGr) in a Gleissol type soil. Rice cv IRGA-420 was seeded in 11.22.2004, using the uppermost rice field area to avoid eventual contaminations. The property is divided in 1.5-2.5 ha-field areas, separated by rrigation or drainage channels. Traditionally, rice root weevil is controlled through carbosulfan application at the rate of 400 g a.i. ha-1. Eight sampling points were randomly located in the rice fields. The sampled compartments were: laminar water, soil solution and soil. The time sequence for water and soil solution samplings were 0, 24, 48, 96, 192, 378 and 678 hours after pesticide application, and for soil, 0, 24, 48, 96, 192, 378, 678, 1536 and 1656 hours after pesticide application. The carbofuran and carbosulfan degradation kinetics were evaluated through residue sample analysis. Residue identification and quantification were made through a mass selective detector (MSD) device coupled to a chromatograph. This equipment was operated in the system of ion monitoring mode (SIM), utilizing 160 and 164 fragments for the carbofuran and carbosulfan quantification, respectively. The experimental data and differential equations that describe the carbofuran and carbosulfan kinetics in the field rice water, allowed the insecticide half-life estimation in the three compartments: water, soil solution and soil. The estimated values for carbosulfan half-lives were: 1, 25 and 21 for water, soil and soil solution, respectively, and 3 and 10 days for carbofuran half-lives for the water and soil solution, respectively. The proposed model showed to be viable for the evaluation of insecticide behavior inthe irrigated field rice. High correlation was observed between data obtained by simulation and that from field experimentation, through residue analyses in the water and soil compartments. In an evaluation of environmental risks, the fugacity model level IV was adequate to estimate or predict the insecticide product destination
Doutorado
Agua e Solo
Doutor em Engenharia Agrícola

Thesis (MSc)--University of Stellenbosch, 2004.
ENGLISH ABSTRACT: Agricultural environments are usually contaminated with mixtures of antropogenically introduced chemicals as a result of pesticide spraying, which can affect beneficial, nontarget soil invertebrates, such as earthworms negatively. Most studies on mixture toxicity have focused on interactions of chemicals with similar structures and mechanisms. However, chemical mixtures may occur as conglomerates of diverse structures and toxicological mechanisms in the environment. This study was aimed at assessing the effects of pesticides singly, and in a mixture, on earthworms, using lifecycle parameters (growth and reproduction) and biomarkers (neutral red retention (NRR) assay and acetylcholinesterase (AChE) inhibition) as endpoints. Thus, to determine whether any interactions occurred between the pesticides as shown by the measured endpoints. Another aim was to validate the use of the chosen biomarkers for assessing mixture toxicity. The pesticides used were from three groups: organophosphates, heavy metal-containing pesticides and pyrethroids. From these three groups, four of the most commonly used pesticides in the orchards and vineyards of the Western Cape, South Africa, were chosen, namely chlorpyrifos (organophosphate), azinphos-methyl (organophosphate), copper oxychloride (heavy metal-containing fungicide) and cypermethrin (pyrethroid). Earthworms were exposed in the laboratory to a range of concentrations of chlorpyrifos and copper oxychloride singly, and in 1:1 mixtures of these pesticides in artificial soil, for four weeks. After the exposure period, the biomass change was determined as measure of growth, and cocoon production, hatching success and number of hatchlings per cocoon were determined as measures of reproduction. Growth (biomass change) and reproduction (cocoon production) were affected by the highest concentration treatment (20mg/kg) of chlorpyrifos, but copper oxychloride and the mixture of the two pesticides showed no observable effects on lifecycle parameters. Dose related effects on NRR times were however determined for both pesticides and the mixture. Dose related effects on AChE activity were found for chlopyrifos and the mixture of the two pesticides, but not for copper oxychloride. Short-term exposures (48 hours) of earthworms to the following pesticides in artificial groundwater: chlorpyrifos, copper oxychloride, azinphos-methyl, cypermethrin, chlorpyrifos-copper oxychloride, chlorpyrifos -azinphos-methyl and chlorpyrifos-cypermethrin, were done followed by the determination of AChE inhibition. Dose related effects were exhibited on the AChE activity of earthworms exposed to chlorpyrifos, a mixture of chlorpyrifos and copper oxychloride, azinphos-methyl, and a mixture of azinphos-methyl and chlorpyrifos. Copper oxychloride, cypermethrin and the mixture of chlorpyrifos and cypermethrin had no effect on AChE activity. Earthworms died at the highest exposure concentration of the mixture of chlopyrifos and cypermethrin. Results have shown that although the pesticides did not cause observable effects on lifecycle parameters, there were effects at subcellular and biochemical level, as shown by the biomarkers. Mixtures of pesticides, in some instances, affected earthworms differently from their single components, indicating interactions between the pesticides in mixtures, as shown by the measured endpoints. The NRR assay proved to be a good general biomarker of soil contamination, and the AChE activity could also be a valuable tool in assessing the effects of organophosphate mixtures and mixtures of organophosphates and pesticides from other groups.
AFRIKAANSE OPSOMMING: Nie-teiken organismes, soos erdwurms, word negatief beïnvloed deur mengsels van antropogeniese chemikalieë in landbou-omgewings. Die meeste studies wat handel oor die toksisiteit van chemiese mengsels het tot dusver gefokus op chemikalieë van dieselfde aard en met dieselfde meganismes van werking. Mengsels van chemiese stowwe kan egter as konglomerate van 'n verskeidenheid strukturele eienskappe en met verskillende toksiese meganismes in die omgewing aangetref word. Tydens die studie is gepoog om die effekte van enkel pestisiede sowel as mengsels daarvan op erdwurms te bestudeer, deur van lewensloop kenmerke (groei en voortplanting) en biomerkers (neutraalrooi retensietyd - NNR en inhibisie van asetielcholienesterase -AChE) as eindpunte gebruik te maak. 'n Verdere doel van die studie was om vas te stel of daar enige wisselwerkings tussen die verskillende pestisiede plaasvind, soos aangetoon deur die gemete eindpunte, en verder ook om die gebruik van die gekose biomerkers as maatstawwe van mengseltoksisiteit te evalueer. Die pestisiede wat gebruik is, is van drie verskillende groepe afkomstig: organofosfate, swaarmetale en piretroiede. Van hierdie drie groepe is vier van die pestisiede wat vry algemeen in boorde en wingerde in die Weskaap, Suid-Afrika, gebruik word, geïdentifiseer. Hierdie stowwe is chlorpyrifos (organofosfaat), azinphos-metiel (organofosfaat), koperoksichloried (swaarmetaalbevattende fungisied) en sipermetrien (piretroied). Erdwurms is in die laboratorium aan 'n reeks konsentrasies van chlorpyrifos en koperoksichloried as enkel toksikante en as 1:1 mengsels in kunsmatige grond, vir vier weke blootgestel. Voor en na die blootstellingsperiode is die biomassa van die wurms, as maatstaf van groei, bepaal en kokonproduksie, uitbroeisukses en getal nakomelinge per kokon bepaal as maatstawwe van voortplantingsvaardigheid. Groei (biomassaverandering) en voortplanting (kokonproduksie) is beinvloed deur behandeling met die hoogste konsentrasie (20 mg/kg) chlorpyrifos, terwyl geen effek van koperoksichloried of die mengsel van hierdie twee pestisiede gevind is nie. Daar is gevind dat beide die pestisiede, enkel en in die mengsel, die NRR tye beinvloed het. Die AChE aktiwiteit is beinvloed deur chlorpyrifos en die mengsel, maar nie deur die koperoksichloried nie. Korttermyn blootstellings van erdwurms (48 uur), in kunsmatige grondwater, van erdwurms aan chlorpyrifos, koperoksichloried, azinphos-metiel en sipermetrien as enkel toksikante en mengsels van chlorpyrifos-koperoksichloried, chlorpyrifos-azinphos-metiel en chlorpyrifos-sipermetrien, is gedoen en gevolg deur die bepaling van AChE inhibisie. Koperoksichloried, cypermetrien en die chlorpyrifos-sipermetrien mengsel het geen waarneembare effek op die AChE aktiwiteit gehad nie ?????. Die erdwurms wat blootgestel is aan die hoogste konsentrasie in die mengsel van chlorpyrifos-sipermetrien het doodgegaan. Die resultate het getoon dat die pestisiede nie in die korttermyn die lewensloopkenmerke in enige waarneembare mate geaffekteer het nie maar daar was effekte op sellulêre en biochemiese vlakke soos aangetoon deur die biomerkers. Sommige mengsels van die pestisiede het die erdwurms verskillend van die enkelstowwe geaffekteer. Daar het dus wisselwerking tussen sommige van die pestisiede wat in mengsels aangewend is, plaasgevind, soos aangetoon deur die gemete eindpunte. Die NRR toets, as breë-spektrum biomerker was 'n goeie maatstaf van kontaminasie in grond en daar is aanduidings dat die AChE aktiwiteit, as 'n spesifieke biomerker, 'n nuttige maatstaf kan wees om die effekte van organofosfaatmengsels en mengsels van hierdie chemiese groep en die van ander chemikalieë aan te toon.

Thesis (Masters Diploma (Technology)--Cape Technikon, Cape Town,1994
Pesticides are generally used in south-Africa for the control of various pests; from insects and fungi to weeds. The agricultural industry is probably the biggest user of pesticides and therefore workers in this part of the labour force have the biggest risk of being exposed to the hazards of these essential products. During the 1988/89 deciduous fruit season the deciduous fruit industry earned approximately R1000 million in foreign exchange. It is therefore very important for this industry to produce fruit of high quality in a very competitive market. Of the total deciduous exports, apples comprised approximately 62,5%. The EIgin-Grabouw area is the biggest producer of apples. This industry is clearly very dependant on pesticides to protect its crops against pests. From time to time farm - workers are exposed to pesticides, a study was therefore performed to access the levels of exposure of farm workers. Blood and urine samples were collected in a comprehensive biological monitoring program in the Elgin area to determine, uusing clinical tests, the level of exposure to pesticides. It was decided later that the determination of pesticide residues in blood would form part of this main study. Other tests included serum and red cell cholinesterase. Samples were collected during August (start of spraying season), November (midseason) and February (end of spraying season). A multi-residue method was developed to extract organophosphate and organochlorine pesticides in whole blood. Although various methods exist, they allow only for the extraction of either organophosphates or organochlorines and not multi-residue extractions. This multi-residue method is based on the liquid/liquid extraction of a blood/Celite/ethanol mixture to extract the following pesticides: Azinphos-methyl, Chlorpyrifos, Endosulfan, Methidathion and Prothiophos. The pesticide residue levels were determined on gas chromatographs equipped with DB-5 and DB-2I0 capillary columns and flame photometric-, electron capture- and nitrogen/phosphorous detectors. The results were confirmed on a gas chromatograph with mass-selective detector in selective ion mode. Of the 402 blood samples analysed, 23 samples showed positive for organophoshates and 29 for organochlorines, and were sent for analysis on the mass spectrometer. Of those samples only one could be positively identified. The presence of the pesticide Endosulfan-B was confirmed. The confirmation of the pesticides was complicated by interfering substances that leached from the rubber stoppers of the collection vessels into the blood. Although the study showed that for practical purposes no pesticides were present, other important information was obtained about the handling and analyses of blood samples for pesticides.

Orientador: Luiz Lonardoni Foloni
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Agricola
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Resumo: A utilização de pesticidas na agricultura é uma prática necessária no controle de pragas, doenças ou de plantas daninhas para se atingir altos índices de produtividade e conseguir desta forma atender a demanda crescente de alimentos. Alguns destes pesticidas aplicados podem apresentar propriedades físico-químicas perigosas, seja ao ambiente e aos próprios seres vivos, podendo causar danos ambientais e problemas de saúde ao homem. Muitas vezes isto ocorre devido à falta de estudos sobre o comportamento e destino destes produtos no ambiente e estudos toxicológicos. Uma ferramenta importante para procurar evitar estes tipos de danos são os modelos matemáticos que permitem antecipar para o qual ou quais compartimentos esta molécula tende a caminhar e também, auxiliar no desenvolvimento de pesquisa no campo, diminuindo os gastos e esforços. O objetivo deste projeto foi utilizar um modelo matemático de fugacidade (nível) I na análise de risco do comportamento, como auxílio na avaliação preliminar da distribuição ambiental, dos principais pesticidas registrados junto ao Ministério da Agricultura, usados e aplicados de acordo com as recomendações de seus fabricantes, nos sistemas de produção convencional e plantio direto, nas principais culturas brasileiras: algodão, arroz, café, cana-de-açúcar, citros, milho e soja. A metodologia utilizada foi baseada nas fórmulas matemáticas descritas por Mackay (1991). Como resultados, foram selecionados os 10 produtos que mais se distribuíram nos compartimentos ambientais (ar, água, solo, sedimento, biota, folhas das plantas, caule e raiz) aqui apresentados em ordem decrescente de preferência. Estes pesticidas foram para o compartimento ar: acetochlor> disulfuton> acephate> thiodicarb> quinclorac> thiram> tolifluanid> pendimenthalin> trifluralin> endosulfan; para a água: nicosulfuron> metsulfuron methyl> monocrotofós> bispyribac sodium> metamidofós> thiamethoxam> halosuluron methyl> chlorimuron etílico> imazapic> imidacloprid; para o solo: diquat> paraquat> hexythiazox> parathion metil> benomyl> tiofanato metílico> msma> iprodione> epoxiconazole> propargite; para o sedimento: diquat> paraquat> hexythiazox> parathion metil> benomyl> tiofanato metílico> msma> iprodione> epoxiconazole> propargite; para a biota: propanil> acetochlor> disulfoton> pendimenthalin> bifenthrin> carboxin> endosulfan> clorpirifós> tolyfluanid> thiram; para a folha: aldicarb> fluazifop-p-butil> metconazole> diflubenzuron> tolyfluanid> disulfuton> fludioxonil> difenoconazole> acetochlor> tebuconazole; para a raiz e caule: lambdacyhalothrin> zetacypermethrin> cypermethrin> alfacipermetrina> bifenthrin> acrinathrin> permethrin> lactofen> betacyflutrin> chlorfluazuron. Os pesticidas estudados também foram comparados pelo critério de GUS (índice de vulnerabilidade de águas subterrâneas). Os produtos que apresentaram potencial de lixiviação em ordem alfabética foram: acetochlor, aldicarb, atrazina, bispyribac-sodium, carbendazim, carbofuran, clorimuron, etílico, cyproconazole, difenoconazole, fipronil, flumioxazin, fomezafen, hexazinone, imazapic, imazaquim, imazetapir, metalacloro, metomyl, metribuzin, metsulfuron-methyl, monocrotofós, nicosulfuron, quinclorac, simazine, tebuthiuron, thiamethoxam e triclorfon. As conclusões deste trabalho permitiram verificar que o compartimento ambiental que apresentou maior vulnerabilidade na preferência da distribuição dos pesticidas foi o compartimento água. A avaliação preliminar do risco de contaminação por pesticidas de uma área agrícola pode ser feita a partir das características físico-químicas dos pesticidas utilizando o modelo de fugacidade Mackay nível I (1991). Este modelo pela simplicidade e rapidez nas respostas mostra ser uma excelente ferramenta, como fator de decisão na utilização do pesticida. O critério de GUS também se apresentou como mais um mecanismo para ser utilizado quando não se dispõe de todas as informações, como tomada de decisão na escolha da utilização de um pesticida visando monitorar ou até mesmo impedir a contaminação de águas subterrâneas
Abstract: The utilization of pesticides in agriculture is a necessary practice to control pests, diseases or weeds to reach an excellent index of productivity and get attend the increasing necessity of food. Some of this pesticides applied, show dangerous physical-chemical proprieties to the environmental and health human. Many times it happen because we haven¿t enough studies of the toxicity and behavior or destination of pesticides in the environmental. One of important tool to try avoid this type of damage are the mathematics models, which permit anticipated for which behavior of this molecule tend walk and also help in the development of field research reduce expense and effort. The goal of this project was use a mathematics calculus based on mathematics models of fugacity level 1, which help in the analysis of risk the main environmental behavior of all pesticides, registered in the Ministry of Agriculture, used and applied according to the recommendation of manufactures pesticides industry (WIN FIT; 2000), at the system of conventional production, and no till system of cotton, rice, coffee, sugar-cane, citrus, corn and soybean cultivation. The utilized methodology was mathematics formula describe by Mackay (1991) to figure out of fugacity (¿, Pa), capacity of fugacity (Z, mol m-3 Pa-1) , concentration (C, g mol-1) in the compartment air, water, soil, sediment, biota, leaves, root, stem of plant. It was used the physical-chemical parameters to each pesticides applied to each culture studied (cotton, rice, sugar-cane, coffee, citrus, corn and soybean) with data of each compartment: volume (m³), fraction organic (%) and density (?, g m-3) got from the Mackay (1991). As the results of mathematics calculus it were chose the 10 products which were more distributed in the compartment environmental present such as following the preference, where from the air compartment: acetochlor> disulfuton> acephate> thiodicarb> quinclorac> thiram> tolifluanid> pendimenthalin> trifluralin> endosulfan; from the water compartment: nicosulfuron> metsulfuron-methyl> monocrotofos> bispyribac-sodium> metamidofos> thiamethoxam> halosuluron methyl> chlorimuron etílico> imazapic> imidacloprid; from the soil compartment: diquat> paraquat> hexythiazox> parathion metil> benomyl> tiofanato metílico>msma>iprodione> epoxiconazole> propargite; from the sediment compartment: diquat> paraquat> hexythiazox> parathion metil> benomyl> tiofanato metílico> msma> iprodione> epoxiconazole> propargite; from the biota compartment: propanil> acetochlor> disulfoton> pendimenthalin> bifenthrin> carboxin> endosulfan> clorpirifós> tolyfluanid> thiram; from the leave compartment: aldicarb> fluazifop-p-butil> metconazole> diflubenzuron> tolyfluanid> disulfuton> fludioxonil> difenoconazole> acetochlor> tebuconazole; from the trunk and root compartments: lambdacyhalothrin> zetacypermethrin> cypermethrin> alfacipermetrina> bifentrhin> acrinathrin> permethrin> lactofen> betacyflutrin> chlorfluazuron. The pesticides studied too were also by the GUS (Groundwater Ubiquity Score) where the index is calculated through the half-life value of the compose on the soil and coefficient of adsorption and organic tissue of the soil. The products that showed lixiviation potential by GUS alphabetical order were: acetochlor, aldicarb, atrazina, bispyribac sodium, carbendazim, carbofuran, clorimuron, etilico, cyproconazole, difenoconazole, fipronil, flumioxazin, fomezafen, hexazinone, imazapic, imazaquim, imazetapir, metalacloro, metomyl, metribuzin, metsulfuron-methyl, monocrotofos, nicosulfuron, quinclorac, simazine, tebuthiuron, thiamethoxam and triclorfon. In conclusion, the environmental compartment showed more vulnerability in the preference of pesticide distribution in the compartment water. The preliminary evaluation of risk contamination in agriculture area by pesticides can be made based on physical-chemical pesticide characteristic used in the fugacity model Mackay level 1 (1991). This fugacity model Mackay level 1 (1991) is an excellent tool to be used as a factor of decision in the pesticides use. The GUS criteria showed itself as one more mechanism to be used dire the lack of information, as decision make skill in choice of a pesticide utilization aiming monitoring or even though avoiding groundwater contamination
Mestrado
Agua e Solo
Mestre em Engenharia Agrícola

In soils spiked with gamma-HCH & DDT, and transplanted with wheat, the differences of gamma-HCH between the rhizosphere and non-rhizosphere soils increased with time, reached the peak on 30th sampling day, and then decreased with time. In the rhizosphere and non-rhizosphere soils, pp'-DDE/SigmaDDTs, op'-DDD/SigmaDDTs and pp'-DDD/SigmaDDTs increased with time; whilst op'-DDT/SigmaDDT and pp'-DDT/SigmaDDT decreased with time. The wheat, corn and soybean rhizosphere soils differed greatly in soil properties, but it was hard to conclude the effect of crop roots on the variation in concentration of gamma-HCH, p,p'-DDE, p,p'-DDD and p,p'-DDT in the rhizosphere soils except for root accumulation and translocation.
In the control, wheat and corn rhizosphere soils, the n-hexane extracted fraction of gamma-HCH, DDE, DDD and DDT decreased with time whereas the hexane/acetone extracted fraction increased with time after the 20th sampling day. The n-hexane extracted forms were higher in the rhizosphere soils than those in the non-rhizosphere soils, while the hexane/acetone extracted forms were lower in the rhizosphere soils than in the non-rhizosphere soils.
In the wheat, corn rhizosphere soils and the control, the concentration of NO3-N showed a significant negative correlation with n-hexane extracted DDE, DDD and DDT residues and a significant positive correlation with hexane/acetone extracted residues. The concentration of ammonium nitrogen (NH4-N) showed a significant negative correlation with hexane extracted gamma-HCH, DDE, DDD and DDT residues in the control, corn and wheat rhizosphere soils: but only had significant positive correlation with the n-hexane/acetone extracted fraction in the corn rhizosphere soil. The positive correlations between the n-hexane extracted residues of the target pesticides and soil OC were seldom significant in the control, sometimes significant in the wheat rhizosphere soils, and always strong and significant in the corn rhizosphere soils. The correlation of the n-hexane/acetone extracted residues with soil OC was positive and sometimes significant in the wheat rhizosphere soils, and significant and negative in the corn rhizosphere soils. The results indicated that the concentrations of different OCPs extracted from were strongly influenced by nutritional conditions and soil organic carbon.
Organic carbon (OC), dissolved organic carbon (DOC) and cultivation period were tested to explore their potential effects on target OCPs in the rhizosphere soils. The concentration of the target OCPs in the wheat rhizosphere soils increased proportionally to soil OC, whilst the uptake of OCPs by wheat roots and further translocation to the aboveground part were inversely proportional to soil OC. DOC only showed a negative correlation with concentration of p,p'-DDE and p,p'-DDT in the corn rhizosphere soils. After a longer root-soil interaction, roots had a more significant effect on the concentration of OCPs in the rhizosphere soils closer to the root surface.
The variation of different forms of OCPs in rhizosphere soils and their relationships with nitrogen nutrients and organic carbon were studied.
Variations in concentrations of organochlorine pesticide (OCP) residues in the rhizosphere soils were evaluated using rhizoboxes. A sequential extraction method was developed to study the fractionation and extractability of OCPs in rhizosphere soils. The key findings are as follows:
Zhu Xuemei.
"September 2006."
Adviser: Kin Che Lam.
Source: Dissertation Abstracts International, Volume: 68-03, Section: B, page: 1532.
Thesis (Ph.D.)--Chinese University of Hong Kong, 2006.
Includes bibliographical references (p. 265-288).
Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web.
Abstracts in English and Chinese.
School code: 1307.

by Wai Lok Man.
Thesis (M.Phil.)--Chinese University of Hong Kong, 2003.
Includes bibliographical references (leaves 142-155).
Abstracts in English and Chinese.
Acknowledgements --- p.i
Abstracts --- p.ii
Contents --- p.vii
List of figures --- p.xiii
List of tables --- p.xvi
Abbreviations --- p.xviii
Chapter 1. --- Introduction --- p.1
Chapter 1.1 --- Pentachlorophenol
Chapter 1.1.1 --- Applications of pentachlorophenol --- p.1
Chapter 1.1.2 --- Characteristics --- p.3
Chapter 1.1.3 --- Pentachlorophenol in the environment --- p.3
Chapter 1.1.4 --- Toxicity of Pentachlorophenol --- p.6
Chapter 1.2 --- Treatments of Pentachlorophenol --- p.10
Chapter 1.2.1 --- Physical treatment --- p.10
Chapter 1.2.2 --- Chemical treatment --- p.11
Chapter 1.2.3 --- Biological treatment --- p.13
Chapter 1.3 --- Biodegradation --- p.14
Chapter 1.3.1 --- Biodegradation of PCP by bacteria --- p.14
Chapter 1.3.2 --- Biodegradation of PCP by white-rot fungi --- p.15
Chapter 1.4 --- Biosorption --- p.24
Chapter 1.5 --- Proposed Strategy --- p.28
Chapter 1.6 --- Spent Mushroom Compost
Chapter 1.6.1 --- Background --- p.28
Chapter 1.6.2 --- Physico-chemical properties of SMC --- p.29
Chapter 1.6.3 --- As a biosorbent --- p.29
Chapter 1.6.3.1 --- Factors affecting biosorption --- p.31
Chapter 1.6.3.2 --- Contact time --- p.31
Chapter 1.6.3.3 --- Initial pH --- p.32
Chapter 1.6.3.4 --- Concentration of biosorbent --- p.33
Chapter 1.6.3.5 --- Initial PCP concentration --- p.34
Chapter 1.6.3.6 --- Incubation temperature --- p.34
Chapter 1.6.3.7 --- Agitation speed --- p.35
Chapter 1.6.4 --- Modeling of adsorption --- p.36
Chapter 1.6.4.1 --- Langmuir isotherm --- p.36
Chapter 1.6.4.2 --- Freundlich isotherm --- p.36
Chapter 1.6.5 --- As a source of PCP-degrading bacteria --- p.38
Chapter 1.6.5.1 --- Identification of PCP-degrading bacterium --- p.40
Chapter 1.6.6 --- As a source of fungus --- p.42
Chapter 1.7 --- Objectives of this Study --- p.43
Chapter 2. --- Materials and Methods --- p.44
Chapter 2.1 --- Spent Mushroom compost (SMC) Production --- p.44
Chapter 2.2 --- Characterization of SMC --- p.46
Chapter 2.2.1 --- pH --- p.46
Chapter 2.2.2 --- Electrical conductivity --- p.46
Chapter 2.2.3 --- "Carbon, hydrogen, nitrogen and sulphur contents" --- p.46
Chapter 2.2.4 --- Infrared spectroscopic study --- p.47
Chapter 2.2.5 --- Metal analysis --- p.47
Chapter 2.2.6 --- Anion content --- p.47
Chapter 2.2.7. --- Chitin assay --- p.48
Chapter 2.3 --- Extraction of PCP --- p.49
Chapter 2.3.1 --- Selection of extraction solvent --- p.49
Chapter 2.3.2 --- Selection of desorbing agent --- p.49
Chapter 2.3.3 --- Extraction efficiency --- p.50
Chapter 2.4 --- Adsorption of Pentachlorophenol on SMC --- p.50
Chapter 2.4.1 --- Preparation of pentachlorophenol (PCP) stock solution --- p.50
Chapter 2.4.2 --- Batch adsorption experiment --- p.51
Chapter 2.4.3 --- Quantification of PCP by HPLC --- p.51
Chapter 2.4.4 --- Data analysis for biosorption --- p.51
Chapter 2.4.5 --- Optimization of PCP adsorption --- p.52
Chapter 2.4.5.1 --- Effect of contact time --- p.52
Chapter 2.4.5.2 --- Effect of initial pH --- p.52
Chapter 2.4.5.3 --- Effect of incubation temperature --- p.53
Chapter 2.4.5.4 --- Effect of shaking speed --- p.53
Chapter 2.4.5.5 --- Effect of initial PCP concentration and amount of biosorbent --- p.53
Chapter 2.4.6 --- Adsorption isotherm --- p.53
Chapter 2.4.7 --- Effect of removal efficiency on reuse of biosorbent --- p.54
Chapter 2.5 --- Biodegradation by Isolated Bacterium --- p.54
Chapter 2.5.1 --- Isolation of PCP-tolerant bacteria from mushroom compost --- p.54
Chapter 2.5.2 --- Screening for the best PCP-tolerant bacterium --- p.54
Chapter 2.5.3 --- Identification of the isolated bacterium --- p.55
Chapter 2.5.3.1 --- 16S ribosomal DNA sequencing --- p.55
Chapter 2.5.3.1.1 --- Extraction of DNA --- p.55
Chapter 2.5.3.1.2 --- Specific PCR for 16S rDNA --- p.56
Chapter 2.5.3.1.3 --- Gel electrophoresis --- p.57
Chapter 2.5.3.1.4 --- Purification of PCR products --- p.57
Chapter 2.5.3.1.5 --- Sequencing of 16S rDNA --- p.58
Chapter 2.5.3.2 --- Gram staining --- p.60
Chapter 2.5.3.3 --- Biolog Microstation System --- p.60
Chapter 2.5.3.4 --- MIDI Sherlock Microbial Identification System --- p.61
Chapter 2.5.4 --- Optimization of PCP degradation by PCP-degrading bacterium --- p.62
Chapter 2.5.4.1 --- Effect of incubation time --- p.63
Chapter 2.5.4.2 --- Effect of shaking speed --- p.63
Chapter 2.5.4.3 --- Effect of initial PCP concentration and inoculum size --- p.63
Chapter 2.5.4.4 --- Study of PCP degradation pathway by isolated bacterium using GC-MS --- p.64
Chapter 2.6 --- Biodegradation by Fungus Pleurotus pulmonarius --- p.64
Chapter 2.6.1 --- Optimization of PCP degradation by P. pulmonarius --- p.65
Chapter 2.6.1.1 --- Effect of incubation time --- p.65
Chapter 2.6.1.2 --- Effect of shaking speed --- p.65
Chapter 2.6.1.3 --- Effect of initial PCP concentration and inoculum size --- p.65
Chapter 2.6.2 --- Study of PCP degradation pathway by fungus using GC-MS --- p.65
Chapter 2.6.3 --- Specific enzyme assays --- p.66
Chapter 2.6.3.1 --- Extraction of protein and enzymes --- p.66
Chapter 2.6.3.2 --- Protein --- p.66
Chapter 2.6.3.3 --- Laccase --- p.67
Chapter 2.6.3.4 --- Manganese peroxidase (MnP) --- p.67
Chapter 2.6.4 --- Microtox® assay --- p.67
Chapter 2.7 --- Statistical Analysis --- p.68
Chapter 3. --- Results --- p.69
Chapter 3.1 --- Physico-chemical Properties of SMC --- p.69
Chapter 3.2 --- Extraction Efficiency and Desorption Efficiency of PCP --- p.69
Chapter 3.3 --- Batch Adsorption Experiments --- p.76
Chapter 3.3.1 --- Optimization of adsorption conditions --- p.76
Chapter 3.3.1.1 --- Effect of contact time --- p.76
Chapter 3.3.1.2 --- Effect of initial pH --- p.76
Chapter 3.3.1.3 --- Effect of shaking speed --- p.79
Chapter 3.3.1.4 --- Effect of incubation temperature --- p.79
Chapter 3.3.1.5 --- Effect of initial PCP concentration and amount of biosorbent --- p.79
Chapter 3.3.2 --- Reuse of SMC --- p.83
Chapter 3.3.3 --- Isotherm plot --- p.83
Chapter 3.4 --- Biodegradation by PCP-degrading Bacterium --- p.86
Chapter 3.4.1 --- Isolation and purification of PCP-tolerant bacteria --- p.86
Chapter 3.4.2 --- Identification of the isolated bacterium --- p.90
Chapter 3.4.2.1 --- 16S rDNA sequencing --- p.90
Chapter 3.4.2.2 --- Gram staining --- p.90
Chapter 3.4.2.3 --- Biolog MicroPlates Identification System --- p.90
Chapter 3.4.2.4 --- MIDI Sherlock Microbial Identification System --- p.90
Chapter 3.4.3 --- Growth curve of PCP-degrading bacterium --- p.90
Chapter 3.4.4 --- Optimization of PCP degradation by PCP-degrading bacterium --- p.97
Chapter 3.4.4.1 --- Effect of incubation time --- p.97
Chapter 3.4.4.2 --- Effect of shaking speed --- p.97
Chapter 3.4.4.3 --- Effect of initial PCP concentration and inoculum size of bacterium --- p.101
Chapter 3.4.5 --- Determination of breakdown products of PCP by PCP-degrading bacterium --- p.101
Chapter 3.5 --- Biodegradation by Fungus Pleurotus pulmonarius --- p.103
Chapter 3.5.1 --- Growth curve of P. pulmonarius --- p.103
Chapter 3.5.2 --- Optimization of PCP degradation by P. pulmonarius --- p.103
Chapter 3.5.2.1 --- Effect of incubation time --- p.103
Chapter 3.5.2.2 --- Effect of shaking speed --- p.103
Chapter 3.5.2.3 --- Effect of initial PCP concentration and inoculum size of fungus --- p.108
Chapter 3.5.3 --- Determination of breakdown products of PCP by P. pulmonarius --- p.108
Chapter 3.5.4 --- Enzyme assays --- p.108
Chapter 3.6 --- Integration of Biosorption by SMC and Biodegradation by P. pulmonarius --- p.112
Chapter 3.6.1 --- Evaluation of PCP removal by an integration system --- p.112
Chapter 3.6.2 --- Evaluation of toxicity by Micortox® assays --- p.112
Chapter 4. --- Discussion --- p.115
Chapter 4.1 --- Physico-chemical Properties of SMC --- p.115
Chapter 4.2 --- Extraction Efficiency and Desorption Efficiency of PCP --- p.116
Chapter 4.3 --- Batch Biosorption Experiment --- p.117
Chapter 4.3.1 --- Effect of contact time --- p.117
Chapter 4.3.2 --- Effect of initial pH --- p.118
Chapter 4.3.3 --- Effect of shaking speed --- p.120
Chapter 4.3.4 --- Effect of incubation temperature --- p.120
Chapter 4.3.5 --- Effect of initial PCP concentration and amount of biosorbent --- p.121
Chapter 4.3.6 --- Reuse of SMC --- p.122
Chapter 4.3.7 --- Modeling of biosorption --- p.122
Chapter 4.4 --- Biodegradation of PCP by PCP-degrading Bacterium --- p.124
Chapter 4.4.1 --- Isolation and purification of PCP-tolerant bacterium --- p.124
Chapter 4.4.2 --- Identification of the isolated bacterium --- p.125
Chapter 4.4.3 --- Optimization of PCP degradation by PCP-degrading bacterium --- p.126
Chapter 4.4.3.1 --- Effect of incubation time --- p.126
Chapter 4.4.3.2 --- Effect of shaking speed --- p.128
Chapter 4.4.3.3 --- Effect of initial PCP concentration and inoculum size of bacterium --- p.128
Chapter 4.4.4 --- PCP degradation pathway by S. marcescens --- p.129
Chapter 4.5 --- Biodegradation of PCP by Pleurotus pulmonarius --- p.130
Chapter 4.5.1 --- Optimization of PCP degradation by P. pulmonarius --- p.130
Chapter 4.5.1.1 --- Effect of incubation time --- p.131
Chapter 4.5.1.2 --- Effect of shaking speed --- p.131
Chapter 4.5.1.3 --- Effect of initial PCP concentration and inoculum size of fungus --- p.131
Chapter 4.5.2 --- Enzyme activities --- p.132
Chapter 4.5.3 --- PCP degradation pathway by P. pulmonarius --- p.133
Chapter 4.6 --- Comparison of PCP Degradation between S.marcescens and P. pulmonarius --- p.133
Chapter 4.7 --- Integration of Biosorption by SMC and Biodegradation by P. pulmonarius --- p.135
Chapter 4.8 --- Evaluation of toxicity by Microtox® assay --- p.135
Chapter 4.9 --- Comparison of PCP Removal by Integration System of Sorption and Fungal Biodegradation and Conventional Treatments --- p.136
Chapter 4.10 --- Further Investigations --- p.137
Chapter 5. --- Conclusion --- p.139
Chapter 6. --- References --- p.142

M.Sc.
The Johannesburg Metropolitan area drains sewage from approximately 1,3 million people which is treated at five different works. The Northern Works discharges approximately 50 Mt of effluent per day, which, together with 27 MX from Alexandria Works flows into the Jukskei River and hence to Hartebeespoort Dam ...

Groundwater contamination on irrigated land is of concern in this nation and around the world. In order to reduce the potential of groundwater contamination by agricultural practices such as irrigation, fertilizer and pesticide application, vadose-zone monitoring and sampling are needed. The main objective of this study was to evaluate impacts of current irrigation treatments and soil structures on the migration of pollutants to groundwater. Passive CAPillary wick pan Samplers (PCAPS) and suction cups were installed in two cracking clays and one sandy soil under the pear tree root zone. PCAPS and suction cups were used to collect nitrate-nitrogen and tracer samples. Tracers were applied to track the spatial and temporal patterns of compounds that mimic nitrate-nitrogen and pesticide movement. The observed magnitude of water leaching over 3 months differed between irrigation methods and soil structures and decreased in this order: flooding over 3 months in clay soil (22.8 cm) > micro-sprinkler in clay soil (16.1 cm) > over-head sprinkler in sandy soil (4.1 cm). Leaching patterns were varied spatially; soil structures, irrigation methods, preferential flow, and high water table may have been responsible for the spatial variation of leaching. Mass recovery of all three tracers, including bromide, blue dye, and rhodamine had the same decreasing order: flooding in clay soil > micro-sprinkler in clay soil > over-head sprinkler in sandy soil. Average blue dye and rhodamine concentrations had the following order: flooding in clay soil > micro-sprinkler in clay > over-head sprinkler in sandy soil. Since blue dye and rhodamine have similar properties to some moderately adsorbed pesticides, we may infer that the risk of pesticide movement in three sites should also decrease in this order. Presumably pesticide movement in clay soil would have been more pronounced for flooding than sprinkler irrigation. On the annual/seasonal basis, the total mass of nitrate-nitrogen leaching differed between irrigation methods and soil structures and decreased in the following order: over-head sprinkler in sandy soil > flooding in clay soil > micro-sprinkler in clay soil. The annual average nitrate-nitrogen concentration observed under over-head sprinkler in sandy soil was 15 mg/l over the maximum allowed concentration level (10 mg/l) by the EPA while seasonal nitrate-nitrogen concentration was low in clay soil under current irrigation practices. Strong evidence suggested the occurrence of preferential flow in this study. Preferential flow may contribute to high water leachate, nitrate and pesticide migration. High correlation coefficients between paired PCAPS indicated that PCAPS have similar responses to water and solute leaching. Several improvements in PCAPS are needed to obtain representative samples under severe flooding conditions. Limited data suggested that ultra-low rate irrigation devices could reduce the water leaching and the potential of pollutant migration to the groundwater because ultra-low rate application devices minimize the soil macropore flow.
Graduation date: 1995

Volatile loss rates of pesticides from turfgrass were measured using the Backward-Time Lagrangian Stochastic Dispersion model (Flesch et al., 1995). Solar radiation, ambient temperature, surface temperature, relative humidity, wind direction, and wind speed were monitored continuously. Growth regulator was applied to the turf plot several days before pesticide application to maintain a constant grass height and aerodynamic roughness length during the experiment. No irrigation occurred following application. Pesticides were applied as mixtures to allow direct comparison of evaporative loss. Mixtures studied were chlorpyrifos + triadimefon + ethofumesate and triclopyr (acetic acid) + propiconazole + cyfluthurin. Airborne flux estimates correlated with temperature, solar radiation, wind speed, time, and vapor pressure of the active ingredient. A log vapor pressure vs. 1/Temperature (K) relationship was observed between flux and surface temperature over a single day for most pesticides. An exponential attenuation of flux was observed over a period of several days and correlated with attenuation of dislodgeable surface residues for two of the pesticides. A fugacity-based model for predicting initial evaporative loss rates from turf grass is presented. Input parameters include pesticide vapor pressure, molecular diffusion coefficient, surface temperature, wind speed profile, atmospheric stability, surface roughness, and average upwind fetch. The GC retention method (Jensen, 1966) was used to estimate pesticide vapor pressures over an environmentally relevant temperature range. The model predicts fluxes that are an order of magnitude greater than measured values. This bias may be due, in part, to deviation from the assumption of pesticide saturated vapor density at the foliar surface. In addition, sensitivity analysis suggests improved estimates of leaf surface temperature and pesticide vapor pressures have the greatest potential to improve model performance.
Graduation date: 2003

by Law Wing Man.
Thesis (M.Phil.)--Chinese University of Hong Kong, 2001.
Includes bibliographical references (leaves 192-206).
Abstracts in English and Chinese.
Acknowledgments --- p.i
Abstract --- p.ii
List of Figures --- p.vi
List of Tables --- p.xii
Abbreviations --- p.xv
Chapter 1. --- Introduction
Chapter 1.1. --- Pesticides --- p.1
Chapter 1.1.1. --- Types and uses --- p.1
Chapter 1.1.2. --- Development of pesticides --- p.1
Chapter 1.1.3. --- The case against pesticides --- p.3
Chapter 1.2. --- Pentachlorophenol --- p.4
Chapter 1.2.1. --- Production --- p.4
Chapter 1.2.2. --- Toxicity --- p.4
Chapter 1.2.3. --- Persistency --- p.6
Chapter 1.3. --- Methyl-parathion --- p.9
Chapter 1.3.1. --- Production --- p.9
Chapter 1.3.2. --- Toxicity --- p.9
Chapter 1.3.3. --- Environmental fate --- p.12
Chapter 1.4. --- Conventional methods dealing with pesticides --- p.12
Chapter 1.5. --- Bioremediation --- p.15
Chapter 1.6. --- Spent mushroom compost --- p.17
Chapter 1.6.1. --- Background --- p.17
Chapter 1.6.2. --- "Physical, chemical and biological properties of SMC " --- p.19
Chapter 1.6.3. --- Recycling of agricultural residuals --- p.21
Chapter 1.6.3.1. --- Definition --- p.21
Chapter 1.6.3.2. --- Types of recycling --- p.22
Chapter 1.6.4. --- Potential uses of SMC as bioremediating agent --- p.23
Chapter 1.6.4.1. --- Use of microorganisms in SMC --- p.23
Chapter 1.6.4.2. --- Use of ligninolytic enzymes in SMC --- p.24
Chapter 1.7. --- Ligninolytic enzymes --- p.28
Chapter 1.7.1. --- Background --- p.28
Chapter 1.7.2. --- What are white rot fungi? --- p.29
Chapter 1.7.3. --- Why is lignin so difficult to degrade? --- p.29
Chapter 1.7.4. --- Three main ligninolytic enzymes --- p.32
Chapter 1.7.4.1. --- Lignin peroxidases (LiP) --- p.32
Chapter 1.7.4.2. --- Manganese peroxidase (MnP) --- p.36
Chapter 1.7.4.3. --- Laccase --- p.37
Chapter 1.8. --- Why SMC was chosen to be the bioremediating agent in my project? --- p.40
Chapter 1.9. --- Bioremediation of chlorophenols and PCP --- p.44
Chapter 1.9.1. --- Bacterial system --- p.44
Chapter 1.9.2. --- Fungal system --- p.45
Chapter 1.10. --- Bioremediation of methyl-parathion --- p.49
Chapter 1.10.1. --- Bacterial system --- p.49
Chapter 1.10.2. --- Fungal system --- p.51
Chapter 1.11. --- Proposal and experimental plan of the project --- p.51
Chapter 1.11.1. --- Study the removal of pesticides in both aquatic and soil system --- p.52
Chapter 1.11.2. --- Research strategy --- p.52
Chapter 1.11.3. --- Optimization of pesticide removal --- p.53
Chapter 1.11.4. --- Identification of breakdown products --- p.54
Chapter 1.11.5. --- Toxicity assay --- p.54
Chapter 1.11.6. --- Isotherm plot --- p.55
Chapter 1.12. --- Objectives of the study --- p.56
Chapter 2. --- Material and Methods --- p.58
Chapter 2.1. --- Material --- p.59
Chapter 2.2. --- Production of Spent Mushroom Compost (SMC) --- p.59
Chapter 2.3. --- Characterization of SMC --- p.60
Chapter 2.3.1. --- PH --- p.60
Chapter 2.3.2. --- Electrical conductivity --- p.60
Chapter 2.3.3. --- "Carbon, hydrogen, nitrogen and sulphur contents " --- p.60
Chapter 2.3.4. --- Ash content --- p.61
Chapter 2.3.5. --- Metal analysis --- p.61
Chapter 2.3.6. --- Anion content --- p.62
Chapter 2.3.7. --- Chitin assay --- p.62
Chapter 2.4. --- Characterization of soil --- p.63
Chapter 2.4.1. --- Soil texture --- p.63
Chapter 2.4.2. --- Moisture content --- p.64
Chapter 2.5. --- Basic studies on the removal capacity of pesticides by SMC --- p.65
Chapter 2.5.1. --- Preparation of pentachlorophenol and methyl- parathion stock solution --- p.66
Chapter 2.6. --- Experimental design --- p.65
Chapter 2.6.1. --- In aquatic system --- p.65
Chapter 2.6.2. --- In soil system --- p.68
Chapter 2.7. --- Extraction of pesticides --- p.68
Chapter 2.7.1. --- In aquatic system --- p.68
Chapter 2.7.2. --- In soil system --- p.69
Chapter 2.8. --- Quantification of pesticides --- p.69
Chapter 2.8.1. --- By high performance liquid chromatography --- p.69
Chapter 2.8.2. --- By gas chromatography-mass spectrometry --- p.71
Chapter 2.9. --- Optimization of pesticides degradation by SMC in both aquatic and soil systems --- p.72
Chapter 2.9.1. --- Effect of initial pesticide concentrations on the removal of pesticides --- p.72
Chapter 2.9.2. --- Effect of amount of SMC used on the removal of pesticides --- p.73
Chapter 2.9.3. --- Effect of incubatoin time on the removal of pesticides --- p.73
Chapter 2.9.4. --- Effect of initial pH on the removal of pesticides --- p.73
Chapter 2.9.5. --- Effect of incubation of temperature on the removal of pesticides --- p.74
Chapter 2.10. --- The study of breakdown process of pesticides --- p.74
Chapter 2.10.1. --- GC/MS --- p.74
Chapter 2.10.2. --- Ion chmatography --- p.74
Chapter 2.11. --- Microtox® assay --- p.75
Chapter 2.12. --- Assessment criteria --- p.75
Chapter 2.12.1. --- In aquatic system --- p.75
Chapter 2.12.2. --- In soil system --- p.76
Chapter 2.13. --- Statistical analysis --- p.77
Chapter 3. --- Results
Chapter 3.1. --- Characterization of SMC and soil --- p.78
Chapter 3.2. --- Quantification of pesticides by HPLC and GC/MS --- p.82
Chapter 3.3. --- Extraction efficiencies of pesticides with hexane --- p.82
Chapter 3.4. --- Stability of pesticides against time --- p.82
Chapter 3.5. --- Effect of sterilization of soil in the removal abilities of pesticides…… --- p.88
Chapter 3.6. --- Optimization of removal of pentachlorophnol --- p.88
Chapter 3.6.1. --- Effect of incubation time --- p.88
Chapter 3.6.1.1. --- In aquatic system --- p.88
Chapter 3.6.1.2. --- In soil system --- p.88
Chapter 3.6.2. --- Effect of initial PCP concentrations and amout of SMC used --- p.91
Chapter 3.6.2.1. --- In aquatic system --- p.91
Chapter 3.6.2.2. --- In soil system --- p.94
Chapter 3.6.3. --- Effect of pH --- p.97
Chapter 3.6.3.1. --- In aquatic system --- p.97
Chapter 3.6.3.2. --- In soil system --- p.97
Chapter 3.6.4. --- Effect of incubation temperature --- p.97
Chapter 3.6.4.1. --- In aquatic system --- p.97
Chapter 3.6.4.2. --- In soil system --- p.101
Chapter 3.6.5. --- Potential breakdown intermediates and products --- p.101
Chapter 3.6.5.1. --- In aquatic system --- p.101
Chapter 3.6.5.2. --- In soil system --- p.104
Chapter 3.7. --- Microtox® assay of PCP --- p.110
Chapter 3.7.1. --- In aquatic system --- p.110
Chapter 3.7.2. --- In soil system --- p.110
Chapter 3.8. --- Optimization of removal of methyl-parathion --- p.113
Chapter 3.8.1. --- Effect of incubation time --- p.113
Chapter 3.8.1.1. --- In aquatic system --- p.113
Chapter 3.8.1.2. --- In soil system --- p.113
Chapter 3.8.2. --- Effect of initial concentration and amount of SMC --- p.115
Chapter 3.8.2.1. --- In aquatic system --- p.115
Chapter 3.8.2.2. --- In soil system --- p.117
Chapter 3.8.3. --- Effect of incubation temperature --- p.120
Chapter 3.8.3.1. --- In aquatic system --- p.120
Chapter 3.8.3.2. --- In soil system --- p.120
Chapter 3.8.4. --- Potential breakdown intermediates and products --- p.121
Chapter 3.8.4.1. --- In aquatic system --- p.121
Chapter 3.8.4.2. --- In soil system --- p.124
Chapter 3.9. --- Microtox ® assay of methyl-parathion --- p.133
Chapter 3.9.1. --- In aquatic system --- p.133
Chapter 3.9.2. --- In soil system --- p.133
Chapter 4. --- Discussion
Chapter 4.1. --- Characterization of SMC and soil --- p.137
Chapter 4.2. --- Stability of pesticides against time in aquatic and soil system --- p.141
Chapter 4.3. --- Effect of sterilization of soil in the removal abilities of pesticides --- p.142
Chapter 4.4. --- Optimization of removal of PCP --- p.142
Chapter 4.4.1. --- Effect of incubation time --- p.142
Chapter 4.4.1.1. --- In aquatic system --- p.142
Chapter 4.4.1.2. --- In soil system --- p.143
Chapter 4.4.2. --- Effect of initial PCP concentrations and amount of SMC --- p.144
Chapter 4.4.2.1. --- In aquatic system --- p.144
Chapter 4.4.2.2. --- In soil system --- p.147
Chapter 4.4.3. --- Effect of pH --- p.149
Chapter 4.4.3.1. --- In aquatic system --- p.149
Chapter 4.4.3.2. --- In soil system --- p.150
Chapter 4.4.4. --- Effect of incubation temperature --- p.150
Chapter 4.4.4.1. --- In aquatic system --- p.150
Chapter 4.4.4.2. --- In soil system --- p.152
Chapter 4.4.5. --- Potential breakdown intermediates and products --- p.152
Chapter 4.4.5.1. --- In aquatic system --- p.152
Chapter 4.4.5.2. --- In soil system --- p.158
Chapter 4.5. --- Microtox® assay of PCP --- p.159
Chapter 4.5.1. --- In aquatic system --- p.159
Chapter 4.5.2. --- In soil system --- p.160
Chapter 4.6. --- Removal of PCP by the aqueous extract of SMC --- p.162
Chapter 4.7. --- Optimization of removal of methyl-parathion --- p.164
Chapter 4.7.1. --- Effect of incubation time --- p.164
Chapter 4.7.1.1. --- In aquatic system --- p.164
Chapter 4.7.1.2. --- In soil system --- p.165
Chapter 4.7.2. --- Effect of initial methyl-paration concentrations and amount of SMC used --- p.165
Chapter 4.7.2.1. --- In aquatic system --- p.165
Chapter 4.7.2.2. --- I in soil system --- p.166
Chapter 4.7.3. --- Effect of incubation temperature --- p.168
Chapter 4.7.3.1. --- In aquatic system --- p.168
Chapter 4.7.3.2. --- In soil system --- p.169
Chapter 4.7.4. --- Potential breakdown intermediates and products --- p.169
Chapter 4.7.4.1. --- In aquatic system --- p.169
Chapter 4.7.4.2. --- In soil system --- p.170
Chapter 4.8. --- Microtox® assay of Methyl-parathion --- p.173
Chapter 4.8.1. --- In aquatic system --- p.173
Chapter 4.8.2. --- In soil system --- p.174
Chapter 4.9. --- Removal of methyl-parathion by the aqueous extract of SMC --- p.174
Chapter 4.10. --- The ability of different types of SMC in the removal of organic pollutants --- p.176
Chapter 4.11. --- The storage of SMC --- p.178
Chapter 4.12. --- The effect of scale in the removal of pesticides --- p.180
Chapter 4.13. --- Cost-effectiveness of using SMC as crude enzymes sources --- p.180
Chapter 4.14. --- The effect of surfactant on the removal of PCP --- p.182
Chapter 4.15. --- Prospects for employment SMC in removal of pollutants --- p.185
Chapter 5. --- Conclusions --- p.186
Chapter 6. --- Future investigation --- p.190
Chapter 7. --- References --- p.192

A field study was conducted to determine the applicability of multivariate geostatistical methods to the problem of estimating and simulating pesticide concentrations in groundwater from measured concentrations of nitrate and pesticide, when pesticide is undersampled. Prior to this study, no published attempt had been made to apply multivariate geostatistics to groundwater contamination. The study was divided into two complementary aspects of geostatistics: estimation and simulation. The use of kriging and cokriging to estimate nitrate and the herbicide dimethyl tetrachloroterepthalate (DCPA) contaminant densities is described in Chapter I. Measured concentrations of nitrate and the DCPA were obtained for 42 wells in a shallow unconfined alluvial and basin-fill aquifer in a 16.5 km² agricultural area in eastern Oregon. The correlation coefficient between log(nitrate) and log(DCPA) was 0.74. Isotropic, spherical models were fitted to experimental direct- and cross-semivariograms with correlation ranges and sliding neighborhoods of 4 km. The relative gain for estimates obtained by cokriging ranged from 14 to 34%. Additional sample locations were selected for nitrate and DCPA using the fictitious point method. A simple economic analysis demonstrated that additional nitrate samples would be more beneficial in reducing estimation variances than additional DCPA samples, unless the costs of nitrate and DCPA analysis were identical. These estimates are by definition, the Best Linear Unbiased Estimates (i.e., the estimates with minimized estimation variance), however the requirement of minimized variance smoothes the variability of contaminant values. The application of conditional simulations to groundwater contamination is described in Chapter 11. Conditional simulation allows the degree of fluctuation of nitrate and DCPA between sample points to be assesed. With knowledge of both the 'best' estimates and the of the variability between sample points, nitrate and DCPA groundwater contamination in the study area can be characterized Based on the semivariogram models found in Chapter I, univariate and multivariate conditional simulations of nitrate and DCPA were generated using the turning bands method and the kriging or cokriging system. Kriging was used to condition the univariate simulations, while cokriging was used to cross-correlate and condition the multivariate simulations. The mean of 25 conditional and coconditional simulations at 8 different locations in the study area were generated and compared to kriging and cokriging estimates and 95% confidence intervals. Both conditional and coconditional simulation of the DCPA and nitrate contaminant densities showed large variations when values in different simulations were compared. The fluctuation in values demonstrate the uncertainties in the contaminant distributions when sample sizes are small. As a result of this unkown component, simulated values vary widely. Coconditional simulation displayed the cross-correlation imposed by using the cokriging system to condition the simulations. After 25 simulations, the mean remained unstable indicating that more simulations would be required to enable comparisons with kriging and cokriging estimates.
Graduation date: 1989

The purpose of this work was to determine if environmentally-relevant concentrations of chlorpyrifos and copper, two commonly detected chemicals in Western surface waters, can negatively impact the biological health of salmonids. Both compounds are highly neurotoxic to fish, but each with distinct biological target sites and mechanisms of action. We used common biochemical and physiological indicators of toxicity, and correlated these effects with potentially significant behavioral alterations. For chlorpyrifos, the mechanism of toxic action is the inhibition of acetylcholinesterase (AChE) throughout the peripheral and central nervous system. Here, we conducted biochemical assays of AChE activity in brain and muscle tissues after exposing steelhead trout (Oncorhynchus mykiss) and coho salmon (0. kisutch) to chlorpyrifos for 96 hours. We then correlated the AChE inhibition with behavioral impairment in swimming and feeding activities. In juvenile steelhead and coho exposed to 0.6-2.5 ��g/L chlorpyrifos, AChE activity was inhibited between ~10-65%. This biochemical indicator was significantly correlated with changes in behavioral patterns. Spontaneous swimming rates were reduced ~30-80% in the exposed fish, and strikes at food items (brine shrimp) were reduced ~10-70%. For copper and some other neurotoxicants, the olfactory nervous system is a sensitive target site in fish. The highly-developed olfactory system in salmonids is particularly susceptible to toxic insult by dissolved chemicals since receptor neurons are in direct contact with the aquatic environment. Here, we used electrophysiological techniques to record odor-evoked responses from the sensory epithelium and the olfactory bulb as direct measures of olfactory function in juvenile coho salmon. In fish exposed to copper, chlorpyrifos, or esfenvalerate for 7 days, field potentials recorded from the sensory epithelium and the olfactory bulb showed reduced or obscured olfactory responses to two classes of odorants, which activate non-overlapping populations of receptor neurons. To determine if this reduced sensory input can subsequently alter or diminish olfactory-mediated predator avoidance behaviors, paired physiological and behavioral tests were conducted on juvenile coho exposed to copper. In fish exposed to 2-20 ��g/L copper for 3 hours, olfactory sensitivity was reduced by ~50-9O%. When these fish were presented with a predatory alarm cue (conspecific skin extract), fish with reduced olfactory function increasingly failed to exhibit antipredator behavior. In the following experiments, we show that chlorpyrifos and copper can impair the biochemical and physiological biology of salmonids at environmentally-relevant concentrations, and that these sublethal effects can alter potentially important behavioral patterns.
Graduation date: 2004

M.Sc. (Zoology)
Viticulture is an important agricultural practice in many countries. The long term use of pesticides in vineyards has resulted in increased concentrations of such pollutants in sediments, water and other environmental compartments. Mitigation measures in agriculture, especially vineyard agriculture, are a prerequisite to the sustained integrity of the natural environment, and specifically the aquatic environment. Mitigation presents itself in the form of water bodies, riparian buffer strips, ground vegetation cover, grassed field paths, natural or artificial wetlands and modification of pesticide application rate. However, to our knowledge no studies exist which highlight the state of dams related to viticulture or the use of mitigation measures, in South Africa. The study aimed to quantify the cumulative risk posed to dams on wine farms and the effect of pesticides (fungicides, herbicides and insecticides) on aquatic ecosystems while evaluating the use of mitigation measures in South African viticulture. Epilithic diatom community structure assessment and frustule abnormalities; zooplankton and macroinvertebrate community structure assessment, and characterization of mitigation measures were carried out at nine representative study sites on wine farms in the Western Cape, South Africa. Pesticide risk assessment models PRIMET and PERPEST were employed to assess the risk that pesticides pose at each site from available data. The Relative Risk Model was used to assess the risk posed to identified Risk Regions. Different risk categories were observed across the sites from PRIMET and PERPEST, ranging from no risk to high risk for specific pesticides and relative risk among the risk regions was assessed. Diatom community structure displayed spatial and temporal variability between sites as well as observable diatom frustule abnormalities due to pesticide input. Zooplankton and macroinvertebrate communities displayed variability spatially as well as temporally and this was linked to the presence of pesticides confirming the predictions from PRIMET, PERPEST and the RRM.