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Application of passive sampling for the analysis of hormones in drinking water
Remerová, Martina ; Mravcová, Ludmila (referee) ; Čáslavský, Josef (advisor)
The thesis focuses on the use of passive sampling during an analysis of hormones in drinkable water. In the theoretical part there are described selected passive samplers and the sample of the type of POCIS is described at fuller length. The next chapter engages with steroid hormones and an input of estrogenic hormone into the environment. The thesis contains chapters dealing with possibilities of the determination of hormones in water. It is specialized on the analysis of drinkable and surface water. In the last chapter of the theoretical part there are introduced water works where samples for an experimental assessment were collected from. The experimental part of the thesis presents the specification of the extraction of analytes and an adjustment of used device. In the thesis there are specific calibrations for individual assessment of hormones. The results of the assessment for each collection point are ordered to a well-arranged table. Increased levels of targeted estrogens were not approved in most of sampling points.
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Passive sampling of polar organic pollutants from water
Vítková, Libuše ; Mravcová, Ludmila (referee) ; Čáslavský, Josef (advisor)
This thesis deals with the passive sampling of polar compounds from water using passive samplers POCIS (Polar Organic Chemical Integrative Sampler). These devices were exposed for 4 weeks in the waste water at the inflow of municipal waste water treatment plant in Brno – Modřice, and also at the outflow of the treated water. After exposition sequestered compounds were released by extraction with a mixture of methanol, toluene and dichlormethane. Extracts were analysed by liquid chromatography/mass spectrometry with electrospray ionization. Further, methylated and trimethylsilylated extracts were analysed by orthogonal comprehensive two-dimensional gas chromatography with mass spectrometric detection. Separated compounds were identified on the base of their retention and mass spectra.
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Perfluorované látky ve vodním životním prostředí
TLAČILOVÁ, Hana
Perfluorinated and polyfluorinated substances (PFAS) are synthetic compounds with a wide range of applications due to their specific properties. PFAS are highly stable substances not subject to biochemical, chemical, thermal, or photochemical degradation. They are in most cases persistent and bioaccumulative. This work deals with detecting the occurrence of 33 PFAS representatives in benthos, juvenile fish, muscle samples of adult fish, and water using POCIS passive samplers. The 27 sites selected for sampling were profiles operated by the CHMI for surface water monitoring, located on some of the major rivers of the Czech Republic The obtained samples were analyzed using high-resolution mass spectrometry with high-performance liquid chromatography (HPLC-HESI-HRPS). The concentrations of the monitored substances were evaluated using TraceFinder 3.3 software (Thermo Fisher Scientific, USA). The analysis detected 13 PFASs out of the 33 monitored substances, namely PFOS, FOSA, PFDoA, FHpPA, H4PFUnA, PFBS, PFHxS, PFTeDA, PFTrDA, PFHpS, 6:2FTS and PFHpA. At the Ohře - Želina site, the highest concentrations were measured in juvenile fish samples, with total PFAS concentrations reaching up to 887.7 ng×g-1, specifically 620 ng×g-1 PFHxS, 260 ng×g-1 PFOS and 7.7 ng×g-1 PFTrDA, and in benthic samples, with total PFAS concentrations of 147 ng×g-1, specifically 120 ng×g-1 PFHxS and 27 ng×g-1 PFOS. The highest concentration in the muscle samples was measured at the Elbe - Obříství site, 200 ng×g-1 sum PFAS. In the POCIS samples, the highest sum PFAS was estimated at the Elbe - Litoměřice site, with a concentration of 29 ng×g-1. The results of the analyses demonstrated the necessity of combining multiple sample types to obtain the vast range of captured compounds.
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Výskyt (anti-)thyroidní aktivity ve vodním prostředí České republiky
SMĚŠNÁ, Tereza
Xenobiotics present in the aquatic environment can exhibit hormonal activity and thus they have potential to disrupt endocrine system of aquatic organisms. The aim of this study was to perform the first monitoring of the occurrence of (anti-)thyroid activity in samples from surface waters from the Czech Republic and subsequently identify potential hot-spots of the occurrence of (anti-)thyroid activity. Samples were taken using passive samplers of the POCIS type from 21 localities in 17 rivers from the Czech Republic. Detection of (anti-)thyroid activity was performed using the (anti-)TRbeta-CALUX in vitro bioassay in which cells were exposed to reference substances and dilutions of extracts from passive samplers. Triiodothyronine was used as reference compound for thyroid activity, while deoxynivalenol was used as reference compound for anti-thyroid activity. Thyroid activity was not found in any of the surface water samples. Anti-thyroid activity was found in 38 % of the tested samples and ranged from 89 to 310 micrograms/l equivalents of deoxynivalenol. In this study, eight localities with anti-thyroid activity were identified in surface waters of the Czech Republic. The strongest anti-thyroid activities were found in the rivers Bílina, Odra a Svratka. In addition, samples from Texas (USA) were tested in this study. Samples were collected using passive samplers of the POCIS type from 12 localities in 4 rivers from Texas. Neither thyroid nor anti-thyroid activity was found in any of the surface water samples. Further research is needed to determine the compounds responsible for the detected anti-thyroid activities in Czech surface waters and to assess potential risk that the compounds responsible for these activities may pose to aquatic organisms.
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Mapování výskytu (anti-)progestagenních aktivit v povrchových vodách České republiky
KRULOVÁ, Jana
The aim of the bachelor thesis was to map the occurrence of substances with (anti-)progestagenic activity in surface waters of the Czech Republic. Samples were taken at 21 localities using POCIS samplers. Localities included the so-called closure profiles (end of the river basin) and significant sampling points along the profile of the river Elbe. The samples were transported to the laboratory, where they were extracted. (Anti-)PR-CALUX in vitro bioassay was used to detect (anti-)progestagenic activity. First, the cells were plated on a microtiter plate and, after 24 hours of incubation, exposed to a calibration series of the reference substance ORG 2058 for progestagenic activity or the reference substance mifepristone for anti-progestagenic activity and a series of diluted surface water extracts. After 24 hours of exposure, cell luminescence was measured in relative light units. The resulting hormonal activity was expressed in ng/l equivalents of the reference substance (ORG 2058 or mifepristone). Progestagenic activity was below the limit of quantification in the samples from all 21 sampling sites (<6-11 ng/l ORG 2058 equivalents) sampled in the year 2017. Anti-progestagenic activity was detected at 6 localities, ranging from 12 to 33 ng/l mifepristone equivalents. For comparison, 3 samples from the year 2016 were analysed. Anti-progestagenic activity was detected in the range from 14 to 48 ng/l mifepristone equivalents. Progestagenic activity was below the limit of quantification at all 3 localities. The occurrence of anti-progestagenic activity was detected mainly at localities where the chemical industry is in the vicinity. There are companies that can use certain substances with anti-progestagenic activity in the production of their products, such as polycyclic musk compounds, brominated flame retardants or bisphenols. The occurrence of anti-progestagenic activity in these localities could indicate the insufficient ability of industrial wastewater treatment plants to degrade substances exhibiting anti-progestagenic activity. The occurrence of anti-progestagenic activity in surface waters may have a negative impact on aquatic organisms, especially vertebrates. Exposure of these organisms to substances with anti-progestagenic activity could lead to reduced fertility and impaired gonad development.
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New sampling approaches for evaluation of real remediation studies
Kroupová, Kristýna ; Cajthaml, Tomáš (advisor) ; Innemanová, Petra (referee)
This diploma thesis has been carried out as a part of the project Utilization of long term (passive) sampling methods combined with in situ microcosms for assessment of (bio)degradation potential (PASSES). In the frame of the project groundwater remediation took place in the premises of Farmak a.s. in Olomouc using a pilot photooxidation unit and efficiency of the remediation was monitored through passive and active sampling methods. Pilot photooxidation unit is a technology based on the H2O2/UV-C photochemical oxidation of organic pollutants. In this work optimization tests of the pilot photooxidation unit were performed. The residence time of the groundwater in the photoreactors, required for its sufficient decontamination from pharmaceuticals and aromatic hydrocarbons, was 2.5 hours. 91% degradation of the pharmaceuticals and 80% degradation of aromatic hydrocarbons were reached during this interval. Although the removal efficiency of the pharmaceuticals by the photooxidation unit was high, the pilot photooxidation unit was not able to effectively remove the pharmaceuticals at the studied locality. By comparing the results of the pharmaceuticals from active and passive groundwater sampling during the remediation attempt, passive Polar Organic Chemical Integrative Sampler (POCIS) was found to be...
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Monitoring of the pharmaceuticals and pesticides occurrence in the upper part of Blanice river using passive sampling approach
VLK, Pavel
The goal of this thesis was to determine the occurrence of pharmaceuticals and pesticides at the upper part of Blanice river. The spring of the river is located in the Military area Boletice. In this area is minimal incidence of people and minimal land use. It was assumed minimum level of pollution at this part of the monitored area. Higher pollution level was supposed in the downstream part of the monitored area relating to higher population density and agriculture. POCIS passive samplers were used for collecting samples. Analysis were performed by liquid chromatography. There were 201 substances (127 pharmaceuticals, 74 pesticides). The concentrations of 27 substances (18 pharmaceuticals, 9 pesticides) were above the limit of quantification. The lowest level of pollution was found at Spalenec site with total pharmaceuticals and pesticides concentration 83.9 ng. POCIS-1. The highest level of contamination was found at the site Černý stream - 618.9 ng. POCIS-1. However this is only a small stream. The second highest contamination was found in the Rechle site close to the inlet to Husinec drinking water reservoir. Total level of pharmaceuticals and pesticides at this site was amounted to 482 ng. POCIS-1. In the upper part of the monitored catchment area is relatively low level of settelment and use of landscape. There is also low level of pharmaceuticals and pesticides pollution. At the Řepešín mill is forestry landscape changing to agricultural landscape and number of inhabitant is rising up. From this site pollution increases considerably in the landscape. This effect was then reflected in our results. Some substances in the environment change its chemical properties and become persistent. Therefore they are present in the landscape long time after their prohibition for using (e.g. hexazinone, DEET). The Husinec water reservoir reduces the amount of contaminants in the water of Blanice river. This effect was more pronounced for pharmaceuticals than pesticides.
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Nové postupy biomonitoringu cizorodých látek ve vodním prostředí
ČERVENÝ, Daniel
Within the presented work, several approaches of biomonitoring were studied. A well-established method for human health risk assessment was applied to evaluate the quality of fish from open waters in the Czech Republic. As this work is targeted on sport fishermen, who frequently consume their own catches, besides the publication in scientific journal, a brochure with results of this study was distributed via the Czech Fishing Union. Health risks for consumers related to the consumption of wild fish were found strongly species and locality dependent. As there is no risks related with the consumption of carp (Cyprinus carpio) at all investigated sites, frequent consumption of predatory fish should be avoided at some fishing grounds. The use of passive samplers has become more and more attractive in the last two decades. As these devices are able to mimic the biological uptake of chemicals, their potential for replacing fish as bioindicators in routine biomonitoring programmes is evident. In our study, the comparison between analysis of fish tissues and POCIS extracts from selected sampling sites confirms this idea about interchangeability of these indicators in the case of PFASs as target pollutants. Moreover, no metabolic transformation of contaminants present in water take place in passive samplers contrary to living organisms, thus these reflect the actual contamination at the locality more precisely. The use of passive samplers completely fulfils the internationally accepted principles of Replacement, Reduction, Refinement (the three R´s). Another promising approach using YOY fish as bioindicators was evaluated within the present study. Multispecies samples of YOY fish homogenate was found as a better indicator for wide range of pollutants than muscle tissue of adult fish within one species from the same locality. As all inner organs and tissues are presented in analysed samples, more target pollutants in higher concentrations are detected compared to the muscle of adults. Besides the higher sensitivity in pollutants detection and quantification, practical and economic benefits are of concern in the case of the YOY fish approach. The YOY fish approach also particularly fulfil the three R´s strategy, as sampling of this age group of fish has a smaller impact on the environment than the sampling of adults. In case of mercury, that was found as a limiting contaminant for the consumption of fish from open waters in the Czech Republic, a nonlethal method of finclips sampling can be used for the monitoring of this compound in aquatic environments. Besides the monitoring, our optimised method for the estimation of muscle tissue concentrations could be used for human health risk assessment as well. The difference between real muscle concentrations and concentrations estimated using our method differs less than 10% in most of the investigated localities. Benthic organisms are an important part of the food web in aquatic environments, but insufficient information about its contamination is available. In another study included in this thesis, first evidence about bioaccumulation of certain pharmaceuticals in benthic organisms was described. Although, pharmaceuticals are generally considered to be not accumulative in organisms, our study proved that certain pharmaceuticals have bioaccumulation potential. From this finding, it is evident that not only the concentrations of pharmaceutical dissolved in water but also the diet represents an important exposure pathway of contamination by these compounds for organisms (fish) inhabiting aquatic environments.
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Application of passive sampling for the analysis of hormones in drinking water
Remerová, Martina ; Mravcová, Ludmila (referee) ; Čáslavský, Josef (advisor)
The thesis focuses on the use of passive sampling during an analysis of hormones in drinkable water. In the theoretical part there are described selected passive samplers and the sample of the type of POCIS is described at fuller length. The next chapter engages with steroid hormones and an input of estrogenic hormone into the environment. The thesis contains chapters dealing with possibilities of the determination of hormones in water. It is specialized on the analysis of drinkable and surface water. In the last chapter of the theoretical part there are introduced water works where samples for an experimental assessment were collected from. The experimental part of the thesis presents the specification of the extraction of analytes and an adjustment of used device. In the thesis there are specific calibrations for individual assessment of hormones. The results of the assessment for each collection point are ordered to a well-arranged table. Increased levels of targeted estrogens were not approved in most of sampling points.
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Passive sampling of polar organic pollutants from water
Vítková, Libuše ; Mravcová, Ludmila (referee) ; Čáslavský, Josef (advisor)
This thesis deals with the passive sampling of polar compounds from water using passive samplers POCIS (Polar Organic Chemical Integrative Sampler). These devices were exposed for 4 weeks in the waste water at the inflow of municipal waste water treatment plant in Brno – Modřice, and also at the outflow of the treated water. After exposition sequestered compounds were released by extraction with a mixture of methanol, toluene and dichlormethane. Extracts were analysed by liquid chromatography/mass spectrometry with electrospray ionization. Further, methylated and trimethylsilylated extracts were analysed by orthogonal comprehensive two-dimensional gas chromatography with mass spectrometric detection. Separated compounds were identified on the base of their retention and mass spectra.
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