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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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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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Occurrence of polycyclic aromatic hydrocarbons PAHs in aquatic ecosystem of the Yangtze River. Comparison of data from passive samplers SPMD with the literature.
HEMERKOVÁ, Kristýna
The aim of this study was to process results of the analysis of polycyclic aromatic hydrocarbons (PAHs) in SPMD samplers and to compare obtained data with published data sampled the same way. The devices were deployed for 10 days at sampling sites in the middle part of the Yangtze River in august 2013. Instrumental analysis was based on GC-MS/MS method. Time weighted average concentrations of PAHs were calculated using performance reference compounds (PRC) approach. In the area of interest, freely dissolved concentrations of PAHs in water ranged from 7.5 to 31 ng×l-1. The detected concentrations were in the same range or even lower compared to other European rivers probably because of dilution. Domination of 2-3 rings indicated fresh inputs of pollution. By applying diagnostic ratios of certain PAHs, identification of possible sources was performed. These ratios were generally inclined towards pyrogenic sources of pollution by PAHs in all study sites except Jiang Li where these ratios indicated mixture of both petrogenic and pyrogenic sources.
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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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Vliv chemikálií přítomných ve výtocích z čistíren odpadních vod na ryby
GRABICOVÁ, Kateřina
There are many compounds that are used or produced by humans, e.g. pharmaceuticals and personal care products (PPCPs) which are used in large quantities around the world. These compounds end up in waste waters and enter sewage treatment plants (STPs). But not all of these compounds are removed during the treatment processes in STP and they enter the aquatic environment via sewage effluents. The thesis is focused especially on evaluation of presence and potential toxicological effects of PPCPs in aquatic environment. The risk assessment for a single compound is usually based on laboratory experiments. The first tested compound was verapamil, a pharmaceutical for lowering blood pressure and treatment of cardiac diseases. Two types of tests were carried out, an acute one with high concentration levels and a sub-chronic one with levels that included environmentally relevant concentration. After the exposure, common carp larvae and embryos showed malformation and edemas and the heart rate was decreased. According to 96hLC50, the verapamil could be classified as a harmful or toxic substance. The second tested substance was UV filter 2 phenylbenzimidazole-5-sulfonic acid which was found at relatively high concentrations in south Bohemian surface waters. In spite of very low bioconcentration of PBSA in fish, activities of 7-ethoxyresorufin-O-deethylase, 7-methoxyresorufin-O-deethylase and 7-penthoxyresorufin-O-deethylase in exposed rainbow trout were increased which indicate that activity of cytochromes P450 were affected even in environmentally relevant concentration. In a real aquatic system, fish are exposed to waters which contain not only a single pollutant but a mixture of them. A consequent experiment was carried out on rainbow trout caged in effluent for 13 days from STP in Gothenburg, the second biggest STP in Sweden. The concentration of selected antidepressants was measured in different fish tissues and plasma. Citalopram, sertraline and venlafaxine were found in fish brain and liver. As these antidepressants are used for the treatment of psychical disorders, behavior of fish could be affected. The limitations of these experiments, even with real water with a mixture of chemicals, are that fish are stressed in aquaria or cages and the exposure via the food chain is not included. Benthic organisms are an important part of fish diet. The impact of pollution on benthic organisms is often studied. However, there is limited knowledge about the bioaccumulation of pharmaceuticals in the benthos and consequently in fish. Therefore bioaccumulation in Hydropsyche and Erpobdella was studied. These organisms were collected in non-polluted and in effluent affected localities. Antibiotics azithromycin and clarithromycin, cardio-vascular drug verapamil, antifungal drug clotrimazole and antidepressants citalopram and sertraline were found in Hydropsyche. Cardio-vascular drug valsartan, antidepressant sertraline, anti-inflammatory drug diclofenac and antifungal drug clotrimazole were found in Erpobdella. Passive sampling is an integrative sampling method which allows the obtaining of time average concentration over period of few weeks. POCIS (Polar Organic Chemical Integrative Samplers) are used for sampling of polar compounds. It also can mimic bioconcentration. Based on the field experiments, the sampling rate for individual pharmaceuticals and illicit drugs was calculated. Twenty-one localities in the Czech Republic were sampled by POCIS and the water concentration of psychoactive drugs was estimated. Further research is necessary to make POCIS passive sampling a more precise tool for monitoring pharmaceutical and drug contents in aquatic environments.
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Osud polárních organickýxh polutantů ve vodním prostředí
FEDOROVA, Ganna
In this thesis occurrence of emerging pollutants in different compartments of aquatic environment was studied. Different environmental matrices were covered: wastewater, surface water and fish tissues with the focus on pharmaceuticals, illicit drugs and perfluorinated compounds. Although numerous pharmaceuticals have been already detected in aquatic environment all over the world, still there is need for new reliable methods for their detection and quantification. The output of the study is three multi-residue methods for the analysis of pharmaceuticals and illicit drugs in water and fish samples. Their main advantage is that wide range of compounds from different classes is covered, which enables obtaining maximum information with minimum analytical effort. All the methods were validated including such key parameters as limits of quantification, selectivity, recovery and repeatability, and showed excellent performance allowing determination of target compounds at trace levels. Consequently, the methods were applied for the monitoring of POCs in different environmental samples. Wide occurrence of pharmaceuticals in Swedish WWTP effluents was shown. Rather high concentrations for the representatives of anti-hypertension drugs, some antibiotics and anti-depressants were detected. This fact stresses the importance of WWTP´ effluent monitoring as it is the main source of PPCPs in the aquatic environment. Passive sampling approach was tested for the monitoring of POCs in wastewater. Both standard configurations of POCIS were calibrated under the field conditions for a broad range of contaminants. Sampling rate values were calculated for the case of wastewater effluent. This is a significant contribution to the potential widespread application of POCIS for environmental monitoring programs. Analysis of biota samples is an essential part in the assessment of pollutants? fate in aquatic environment. Therefore, the screening of antibiotics in fish available at the Czech market was carried out. Thirty-two antibiotics from different classes were analyzed. The fish and shrimp samples were bought from the three biggest supermarkets in České Budějovice, which belong to a network of shops covering the whole Czech Republic. In total 97 samples were obtained. Found concentrations did not exceed MRL values established in the European Union. No antibiotics were detected in the fish of Czech origin. Still, presence of antibiotic residues in edible fish tissues could be a matter of concern and the sign of improper use of antibiotics in aquaculture industry, what consequently can cause adverse effects for the environment and human health.
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