Dichloro-diphenyl-trichlorethane (DDT) is a chemical used in malaria control through indoor residual spraying (IRS) and has saved numerous lives in the past six decades. DDT use is restricted/banned under the Stockholm Convention on Persistent Organic Pollutants. Passive air sampling using polyurethane foam was conducted in South Africa to evaluate the presence and trends of DDT and its metabolites. Three sampling sites were used, namely, Barberspan Nature Reserve (rural agricultural), Vanderbijlpark (urban industrial) and Molopo Nature Reserve (isolated nature reserve). Sampling was conducted for a period of one year in 2008. Back trajectories from the three sampling sites were generated using HYSPILT to determine the sources of DDT metabolites to the sampling areas. Forward trajectories were also generated to determine the movement, distribution, and fate of DDT from the areas under Indoor residual spray of DDT for malaria control in South Africa and Swaziland. Chemical analysis was conducted by the RECETOX (Mazaryk University) in the Czech Republic. DDT metabolites (o,p’-DDE, p’p’-DDE, o.p’-DDD, p,p’-DDD, o,p’-DDT p,p’-DDT) were analysed using a GC-ECD (HP 5890). Vanderbijlpark had the highest concentrations of DDT metabolites throughout the year. Barberspan had the second highest concentration and Molopo the least. Seasonal changes in concentration were much the same at the three sites. %p,p’-DDT of ΣDDT is consistent with IRS spraying months in South Africa and Swaziland. A combinations of backward and forward trajectories, together with the temporal pattern of change of the %p,p’-DDT of ΣDDT support the deduction that DDT sampled from the three study sites (to some degree) came from IRS areas in South Africa and Swaziland. The presence of DDT in Molopo Nature Reserve and Barberspan is evidence of long-range transportation over dry semi-desert areas. Back-trajectories indicate the possible source of DDT were the IRS areas in the provinces of Limpopo, Mpumalanga, and KwaZulu-Natal. Some air masses to the sampling sites came from the sprayed areas. The forward trajectories also revealed that the DDT sprayed during IRS could undergo LRT. The DDT metabolites were able to travel to neighbouring countries such as Mozambique, Namibia, Zimbabwe and Botswana. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2013

Dichloro-diphenyl-trichlorethane (DDT) is a chemical used in malaria control through indoor residual spraying (IRS) and has saved numerous lives in the past six decades. DDT use is restricted/banned under the Stockholm Convention on Persistent Organic Pollutants. Passive air sampling using polyurethane foam was conducted in South Africa to evaluate the presence and trends of DDT and its metabolites. Three sampling sites were used, namely, Barberspan Nature Reserve (rural agricultural), Vanderbijlpark (urban industrial) and Molopo Nature Reserve (isolated nature reserve). Sampling was conducted for a period of one year in 2008. Back trajectories from the three sampling sites were generated using HYSPILT to determine the sources of DDT metabolites to the sampling areas. Forward trajectories were also generated to determine the movement, distribution, and fate of DDT from the areas under Indoor residual spray of DDT for malaria control in South Africa and Swaziland. Chemical analysis was conducted by the RECETOX (Mazaryk University) in the Czech Republic. DDT metabolites (o,p’-DDE, p’p’-DDE, o.p’-DDD, p,p’-DDD, o,p’-DDT p,p’-DDT) were analysed using a GC-ECD (HP 5890). Vanderbijlpark had the highest concentrations of DDT metabolites throughout the year. Barberspan had the second highest concentration and Molopo the least. Seasonal changes in concentration were much the same at the three sites. %p,p’-DDT of ΣDDT is consistent with IRS spraying months in South Africa and Swaziland. A combinations of backward and forward trajectories, together with the temporal pattern of change of the %p,p’-DDT of ΣDDT support the deduction that DDT sampled from the three study sites (to some degree) came from IRS areas in South Africa and Swaziland. The presence of DDT in Molopo Nature Reserve and Barberspan is evidence of long-range transportation over dry semi-desert areas. Back-trajectories indicate the possible source of DDT were the IRS areas in the provinces of Limpopo, Mpumalanga, and KwaZulu-Natal. Some air masses to the sampling sites came from the sprayed areas. The forward trajectories also revealed that the DDT sprayed during IRS could undergo LRT. The DDT metabolites were able to travel to neighbouring countries such as Mozambique, Namibia, Zimbabwe and Botswana. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2013

Our understanding about the presence, behavior, and toxicities of atmospheric persistent organic pollutants is limited by our ability to accurately measure them. This dissertation details the development and characterization of a model for the determination of an accurate sampling rate (Rs), and effective sampling volume (Veff), for polyurethane equipped passive air samplers (PUF-PAS), and the subsequent application of PUF-PAS sampling methods towards novel applications studying polychlorinated biphenyls (PCBs). The user friendly mathematical model resulting from this work, published as a Matlab script, predicts Rs and Veff as a function of local hourly meteorology and the physical-chemical properties of the target analytes. The model was first developed using active sampling methods in urban Chicago, where good agreement was found between the PUF-PAS and high volume active samplers: Active/Passive = 1.1 ± 1.2. The model was then expanded and calibrated globally using the dataset from the Global Atmospheric Passive Sampling (GAPS) network. After this global calibration we found acceptable agreement between modelled and depuration-determined sampling rates for an independent dataset, with several compounds having near zero mean percent bias (±6%). The globally applicable model is the best alternative for locations experiencing low average wind speeds or cold temperatures, and is particularly useful for the interpretation of samples with long deployments, deployments conducted under warming conditions, and compounds with high volatility. An interactive web-based graphical user interface for the sampling rate model was developed. Users input sampler locations, deployment dates, and target chemicals, in the web-interface and are provided with a sample and compound specific Rs and Veff. The sampling rate model was examined for use in the indoor environment and it was found that both the experimentally calibrated (1.10 ± 0.23 m3 d-1) and modeled (1.08 ± 0.04 m3 d-1) Rs agreed with literature reports. Correlating sample specific wind speeds with uptake rates, it was determined that variability of wind speeds throughout the room significantly (p-value < 0.001) affected uptake rates. Despite this, the PUF-PAS concentration measurements using modelled Rs values were within 27% of the active sampling determined concentration measurements. Using PUF-PAS samplers, PCBs 47, 51, and 68 were found to account for up to 50% of measured indoor sum PCB concentration (2700 pg m-3). Direct surface measurements were conducted to identify finished cabinetry to be a major source, as a result of the decomposition of 2,4-dichlorobenzoyl peroxide used as an initiator in free-radical polymerization of polyester resins. While this phenomenon has been detected at trace levels in other polymer products, it has never been shown to be a significant environment source of PCBs. PUF-PAS samplers were similarly used to study the presence of airborne hydroxylated polychlorinated biphenyls (OH-PCBs) and PCBs in the metropolitan Chicago area. While OH-PCBs have been hypothesized to be an important removal mechanism for atmospheric PCBs, they were not directly measured in the air until recently. The two most frequently detect OH-PCB congeners in this study, 2OH-PCB2 and 6OH-PCB2, were detected at levels comparable to a previous report of atmospheric OH-PCBs utilizing active sampling methods, suggesting the viability of PUF-PAS methods to study atmospheric OH-PCBs. One sampling site detected as many as 50 OH-PCBs but uncertainties with sampling and laboratory methods prevent any strong conclusions from being drawn.

The presence of complex mixtures of compounds in ambient air, many of which are either unknown or uncharacterised makes an assessment of risk associated with these exposures problematic. Bioanalytical methods can provide an integrative assessment of complex mixture potency for specific mechanisms of toxicity within these contexts. The aim of this study was to evaluate the suitability of monitoring ambient air exposures as sampled by (polyurethane foam) PUF passive air samplers (PAS) using effect based techniques (bioanalytical methods). Passive samplers have the advantage of offering a low-tech inexpensive monitoring strategy which can thereby increase sampling capacity across a broader range of scenarios simultaneously. One challenge posed by the application of passive samplers in particular for these assessments has been the expression of potency estimates in relatively non-comparable terms specific to a given dose of the sampler or for a specific deployment period. The project was therefore designed in order to address these aims and previously identified challenges by investigating the applicability of these techniques for: monitoring in both indoor and outdoor air, the determination of seasonal exposure gradients; the determination of exposure gradients in different locations (urban capitals, regional centres, background); and the application of in-situ calibration to provide comparable effect measurements in terms of equivalent reference compound air concentrations. Air sampled using PUF PAS was monitored for its capacity to induce biological responses which are mechanistically relevant to critical health endpoints in these scenarios. The mechanisms assessed included genotoxicity (DNA damage – umuC assay), Aryl hydrocarbon receptor (AhR) activity (CAFLUX assay), and estrogenicity (ESCREEN assay). The findings from this effect based monitoring revealed that the level of biological response measured changes with the exposure scenario (indoor vs. outdoor; summer vs. winter; urban capital cities vs. background locations). Estrogenicity for example assessed as estradiol equivalent air concentrations (E Eq BIO) averaged 54 pg.m-3 (1.5 - 185 pg.m-3) in indoor air, while samples from ambient air were found to be not estrogenic. Total aryl hydrocarbon receptor (AhR) activity assessed as 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalent air concentrations (TCDD Eq BIO) averaged 4.1 pg.m-3 (1.3 – 7.2 pg.m-3) in indoor air while samples from ambient air averaged 15 pg.m-3 (1.5 – 46 pg.m-3)in summer and 53 pg.m-3 (2.2 – 251 pg.m-3) in winter. The relationship for both direct (-S9) and indirect (+S9) acting genotoxicity and AhR activity were found to be relatively consistent with respect to both season (elevated in winter) and location (elevated in urban capital cities). Overall suitable techniques were developed for combining passive sampling with multiple end-point toxicity testing and it was demonstrated that these techniques may be applied across different exposure scenarios. During the course of this method development and interpretation process a range of limitations were identified relating to: the use and application of effect based techniques to monitor environmental samples; the use of passive samplers within this context specifically; and also with the application of in-situ calibration techniques to passive samplers to improve the comparability of these assessments.

No description available.

Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants in a number of common household and commercial products around the world. PBDEs enter the environment in a variety of ways, such as through emissions, leaching from end-of-life electronics in landfills, and incineration. While many countries have phased out the manufacturing of penta-, octa-, and deca-PBDEs or have banned the manufacture and use of these congeners altogether, these persistent organic pollutants (POPs) continue to be detected in humans and the environment. This study investigates spatial and temporal variations of selected PBDEs in the air of the Nandamojo watershed area in Costa Rica by comparing air concentrations of PBDEs in the dry winter vs. wet summer seasons and rural vs. urban areas and also investigates the impact of anthropogenic activities on air concentration of PBDEs. This study is significant to the field, because there are no baseline studies nor are there currently any monitoring programs to assess the environmental levels of PBDEs or other POPs for this region of the Guanacaste province. Baseline information is needed to track spatial and temporal trends as well as evaluate the effectiveness of control measures employed nationally and internationally. Samples obtained from passive air sampling devices were analyzed via GC/MS for a number of congeners. PBDE-47 and -99 were found to be the congeners present in greatest concentration in air samples from the Nandamojo watershed area. Air concentrations were estimated assuming an average sampler uptake rate of 3.5 m3/day and ranged as follows: ΣPBDE5 35.20-1549.25 pg/m3 over the entire study. The presence of PBDEs in remote and pristine environments indicates that PBDEs are now a global concern. This study suggests that the spatial and temporal distribution patterns observed are strongly related to anthropogenic activities and presence of a population similar to that observed in other studies. The presence of PBDEs has become a global issue and, as such, these results provide background information on air concentrations of PBDEs for use in a global-scale multimedia model. In order to monitor PBDEs globally, it is imperative to implement and/or expand surveillance programs internationally.

No description available.

Diploma thesis deals with the assessment of volatile organic compounds contamination of selected working environment in Gumotex, joint stock company using passive sampling. The theoretical part contains description of these compounds and their reactions in the atmosphere, practical use of these substances and their effect on human health. The possibilities of passive sampling and determination of these substances are described as well. The experimental part contains analysis of volatile organic compounds at two selected workplaces in Gumotex, joint stock company using passive samplers Radiello. Final determination by gas chromatography with flame ionization detector was preceded by adsorption surface extraction of sampler with carbon disulfide. In conclusion, obtained data are compared with the permissible exposure limits and maximum allowable concentrations, which are defined by the National Health Institute.

Les matériaux actuellement utilisés comme capteurs passifs de polluants atmosphériques, la mousse de polyuréthane et la résine XAD®-2, ne sont optimisés ni pour l'adsorption de composés polaires ni pour le captage de particules. Pour remédier à ces limitations, la mousse de carbure de silicium (SiC) est proposée comme alternative. Plusieurs campagnes de mesures ont été mises en place pour comparer SiC et XAD®-2. Les composés recherchés étaient des HAP, des PCB et des pesticides.Une méthode d'analyse combinant ASE, SPE et SPME a été développée et optimisée pour ces polluants. Celle-ci permet d'atteindre de faibles limites de détection et quantification pour les composés recherchés.Les campagnes réalisées montrent que la mousse de SiC est toujours plus efficace que la résine XAD®-2 pour le piégeage de composés particulaires et polaires. De plus, la SiC peut être greffée avec du carbone ou des nanotubes de carbone pour augmenter sa surface spécifique, ce qui la rend également plus performante pour l'adsorption de composés volatils. Les débits d'échantillonnage moyens de la mousse ont été calculés et sont comparable aux valeurs rapportées dans la littérature pour la résine XAD®-2. / Materials currently used as passive samplers for atmospheric pollutants, polyurethane foam and XAD®-2 resin, are not suited ta trapping polar compounds nor particles. Ta overcome these limitations, silicon carbide (SiC) foam is presented as an alternative. Several sampling campaigns monitoring PAH, PCB and pesticides were done ta compare SiC and XAD®-2. An analytical method coupling ASE, SPE and SPME was developed and optimised for these pollutants. lt allowed low limits of detection and quantification ta be reached for all compounds of interest.Sampling campaigns showed that SiC foam is consistently more efficient than XAD®-2 resin at trapping particulate and polar compounds. Moreover, SiC foam can be grafted with carbon or carbon nanotubes ta increase its specific surface area, which also makes it better at adsorbing volatile compounds. Average sampling rates were calculated for SiC foam and they are comparable ta the values reported in the literature for XAD®-2 resin.

Dans le but d’évaluer la contamination des atmosphères intérieures et extérieures induite par les usages non agricoles de pesticides, deux approches complémentaires ont été mises en oeuvre : l’utilisation de capteurs passifs de type Tenax TA pour réaliser des prélèvements d’air, et l’utilisation de cheveux employés comme biomarqueurs d’exposition. Des campagnes de mesures ont été menées sur plusieurs sites à la suite de traitements de désherbage ou de désinsectisation ainsi quedans des logements. Les échantillons d’air et de cheveux ont été extraits respectivement par thermodésorption et par extraction solide-liquide, avant d’être analysés en chromatographie gazeuse couplée à la spectrométrie de masse (GC-MS). Une augmentation du niveau de contamination de l’air extérieur et intérieur et l’existence de transferts entre ces deux milieux ont pu être observées après l’application de pesticides. Dans les logements, des pesticides actuellement employés mais aussi des pesticides interdits et persistants ont été détectés. Plusieurs pesticides ont également été détectés dans les cheveux, mais l’exposition humaine à ces derniers n’a pas pu toujours être corrélée à une contamination de l’air. / In order to evaluate indoor and outdoor air contamination resulting from non-agricultural uses of pesticides, two complementary approaches were applied: passive samplers based on Tenax TA used for air sampling and hair used as biomarkers of exposure. Sampling campaigns were conducted on several sites after weeding and pest control treatments as well as in accommodations. Air samples and hair samples were respectively extracted by thermal desorption and solid-liquid extraction prior to their analysis by gas chromatography combined with mass spectrometry (GC-MS). An increase of the indoor and outdoor air contamination levels and the existence of transfers between these two environments could be observed after pesticides applications. In accommodations, pesticides currently used and banned but persistent ones were detected. Several pesticides were also detected in hair samples but human exposure to these pesticides cannot be correlated with air contamination in all cases.