Milada Vávrová

Application of comprehensive two-dimensional gas chromatography with mass spectrometric detection for the analysis of selected drug residues in wastewater and surface water

Pharmaceutical residues have become tightly controlled environmental contaminants in recent years, due to their increasing concentration in environmental components. This is mainly caused by their high level of production and everyday consumption. Therefore there is a need to apply new and sufficiently sensitive analytical methods, which can detect the presence of these contaminants even in very low concentrations. This study is focused on the application of a reliable analytical method for the analysis of 10 selected drug residues, mainly from the group of non-steroidal anti-inflammatory drugs (salicylic acid, acetylsalicylic acid, clofibric acid, ibuprofen, acetaminophen, caffeine, naproxen, mefenamic acid, ketoprofen, and dicofenac), in wastewaters and surface waters. This analytical method is based on solid phase extraction, derivatization by N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and finally analysis by comprehensive two-dimensional gas chromatography with Time-of-Flight mass spectrometric detection (GCxGC-TOF MS). Detection limits ranged from 0.18 to 5 ng/L depending on the compound and selected matrix. The method was successfully applied for detection of the presence of selected pharmaceuticals in the Svratka River and in wastewater from the wastewater treatment plant in Brno-Modrice, Czech Republic. The concentration of pharmaceuticals varied from one to several hundreds of ng/L in surface water and from one to several tens of isg/L in wastewater.

Seasonal variations in municipal landfill leachate quality

Purpose – The aim of this work is to compare quality of leachates from regional municipal landfill in different seasons (dry, snowy/rainy) during a three-year monitoring period due to the fact that quality of landfill leachate can rapidly change under different conditions. Design/methodology/approach – Raw leachates were sampled prior to biological treatment at different periods of the year (November 2007, March 2008, May 2008, March 2009, and January 2010) to detect the changes in their composition due to different physico-chemical conditions at the site (temperature, moisture, etc.). Leachates were physico-chemically characterized and the toxicity of chosen leachates was assessed by a battery of biotests. Findings – Most of the investigated raw leachates exceed Slovenian effluent limits. Samples from March 2008 and March 2009 generally showed higher concentration of measured parameters and also higher toxicity. It has been confirmed that the physico-chemical parameters of leachates usually decrease duri...

Evaluation of the hazardous impact of landfill leachates by toxicity and biodegradability tests

The aim of our research was to assess the ecotoxicity and biodegradability of leachates originating from two parts of a municipal landfill before and after biological treatment in the existing treatment plant. Biotests represent important tools for adequate environmental characterization of landfill leachates and could be helpful in reliable assessment and monitoring of the treatment plant efficiency. For ecotoxicity testing of landfill leachate before and after biological treatment, different organisms were chosen: the bacteria Vibrio fischeri, a mixed culture of activated sludge, duckweed Lemna minor, white mustard Sinapis alba, brine shrimp Artemia salina, and water flea Daphnia magna. For assessment of biodegradability, the method for determination of oxygen demand in a closed respirometer was used. The investigated leachates were heavily polluted, and in some cases, effluent limits were exceeded even after treatment. Results indicated that toxicity tests and physico‐chemical parameters determined before and after treatment equivalently assess the efficiency of the existing treatment plant. However, the investigated leachates showed higher toxicity to Daphnia magna and especially to Lemna minor in contrast to Vibrio fischeri and Artemia salina (neither was sensitive to any of the leachates). No leachates were readily biodegradable. Experiments confirmed that the battery of toxicity tests should be applied for more comprehensive assessment of landfill leachate treatment and for reliable assessment of the treated leachates subsequent environmental impact. It was confirmed that treated leachate, in spite of its better physico‐chemical characteristics, still represents a potential environmental risk and thus should not be released into the environment.

PCBs in Samples from the Environment of the Southern Moravia Region, Czech Republic

The determination of polychlorinated biphenyls (PCBs) in water, sediment and fish samples from the Czech Republic was carried out using high resolution gas chromatography with electron capture detection. PCBs concentrations in water and sediment samples were rather low and corresponded with the findings from some prior studies. On the other hand, investigated samples of fish tissue were highly contaminated (on average 1.3–266 ng/g fat for individual PCBs), thus, a continuing contamination of fish species with PCBs was proved.

Preparation and ecotoxicity assessment of new biodegradable polyurethane foams

Flexible biodegradable polyurethane foams (BIO-PUR) were prepared by a one-shot process using commercially available coreactants and modified by substituting biodegradable additive based on the acetylated starch (AS), acetylcellulose (AC), 2-hydroxyethylcellulose (HEC) and carboxymethylcellulose sodium salt (CMC) for 5 or 10 wt% of commercial polyether polyol. The BIO-PUR foams were characterized by FTIR, TGA and polarization microscopy. Ecotoxicity of BIO-PUR foams freshwater extracts was evaluated using the alternative crustacean toxicity test Thamnotoxkit F. Values of toxicity were expressed as percentage mortality of the instars II–III larvae of freshwater fairy shrimps (Thamnocephalus platyurus) dependence on the effect criterion of the respective assay. The leaches of BIO-PUR foams modified with 5 or 10 wt% of HEC showed higher toxicity then other BIO-PUR foams, whereas leaches of BIO-PUR with 5wt% of AS and 10wt% of AC were even less toxic than REF. PUR foam.

Comparison of extraction techniques for the isolation of explosives and their degradation products from soil

A comparison of four extraction techniques used for the isolation of 14 explosive compounds (Method 8330-Explosives) from spiked soil samples is described. Soxhlet warm extraction (SWE), pressurized solvent extraction (PSE), microwave assisted extraction (MAE) and supercritical fluid extraction (SFE) were included. The effects of basic extraction conditions – i.e. type of extraction solvent, temperature, pressure, and extraction time – were investigated. The best extraction recovery of the monitored compounds from spiked soil was obtained using pressurized solvent extraction. Recoveries of explosives using the PSE technique were in the range from 65 to 112%. Extraction recoveries by Soxhlet warm extraction and supercritical fluid extraction reached 65–99% and 52–75%, respectively. The lowest extraction recoveries (28–65%) were obtained using microwave assisted extraction. A very low extraction recovery for tetryl was observed in all cases but the best results were achieved by pressurized solvent extraction (58%).

The Use of Methods of Environmental Analysis and Ecotoxicological Tests in the Evaluation of Wastewater

The term “new” environmental pollutant covers all anthropogenic contaminants that have been released in the environment over the last few decades. Research into their fate and impact on the environment has started relatively recently. The group of new environmental pollutants consists of persistent organic pollutants (POPs) including DDT, polychlorinated biphenyls, polycyclic aromatic hydrocarbons and a wide range of organic pesticides. This group has recently been expanded with polybrominated flame retardants, drugs, detergents, and personal hygiene products. Chemicals, used everyday in homes, industry and agriculture, can enter the environment in wastewater. According to the United Nations Organization 884 million people do not have access to safe drinking water, and over 2.6 billion people do not have access to proper sanitation systems. On July 28, 2010, the UN General Assembly passed a resolution supporting water as a human right and urging governments and international organizations to address this important human right. Interest in the presence of pharmaceuticals, personal care products, and endocrine disruptors in the environment has increased significantly over the last decade. Pharmaceuticals and synthetic musk compounds in personal care products (PPCPs), are groups of organic micropollutants which are routinely detected in surface water, ground water and even in drinking water (McClellan and Halde, 2010). Hundreds of tons of these compounds are dispensed in communities every year. PPCPs are regarded as being potentially hazardous compounds as some are ubiquitous, persistent and biologically active compounds with recognised endocrine disruption functions (Kasprzyk-Hordern et. al., 2002). Many pharmaceuticals, upon administration, are degraded in the body and may even become inactive, but others, often those applied externally, excreted or not absorbed fully, can leave the body in their active forms. (Roberts &Thomas, 2006). The others only slightly transformed or even unchanged often conjugated to endogenous substrate (e.g. glucuronic acid, sulfuric acid, acetic acid to polar molecules. (Roberts and Thomas, 2006). These conjugates are easily cleaved during sewage treatment and, thus, several pharmaceutically active compounds (PhACs) are discharged almost unchanged from municipal sewage treatment plants (STPs) into the receiving waters (Heberer, 2002). The wide range of trace chemical contaminants persisting in municipal wastewater after conventional treatment

Comparison of extraction techniques for isolation of steroid oestrogens in environmentally relevant concentrations from sediment

ABSTRACT The comparison of four extraction techniques for isolation of five native and one labelled steroid oestrogens from sediment was described. The three conventional extraction techniques Soxhlet warm extraction (SWE), accelerated solvent extraction (ASE), microwave-assisted extraction (MAE) and a promising technique QuEChERS were tested for isolation of low environmentally relevant oestrogen concentrations using different extraction conditions. The least expensive and time-consuming method QuEChERS provided the best extraction recoveries (53–84%) from all techniques. MAE achieved the highest recovery from conventional techniques for less polar oestrogens using dichloromethane: acetone 3:1 mixture as an extraction solvent (50–71%), but for extraction of the whole group of oestrogens including more polar estriol acetone or methanol must be used. ASE provided higher extraction recoveries using dichloromethane at 60°C (53–74%) for less polar oestrogens. However, the repeatability of results was unsatisfactory and recoveries using other extraction conditions were lower than for MAE. The most time-consuming SWE achieved the worst extraction recoveries and for isolation of low oestrogen concentrations from sediments, it is completely unsuitable.

A new method for macrolide antibiotics determination in wastewater from three different wastewater treatment plants

Abstract An effective and practical method for the determination of macrolide antibiotics azithromycin, clarithromycin, erythromycin and roxithromycin in wastewater samples has been developed. The analytical method combines solid phase extraction followed by a chromatographic separation by hydrophilic interaction liquid chromatography (HILIC) coupled with an ion trap mass spectrometer utilizing the electrospray ionization technique. Detection of positively charged ions was performed in full scan mode from 500 to 900 m/z. The method detection limits and method quantification limits obtained were in the range of 2.03-7.59 ng L-1 and 6.08-23.84 ng L-1, respectively. Recoveries of solid phase extraction were obtained using SupelTM-Select HLB cartridges ranging from 85.76 % to 92.54 %. All target antibiotics were detected in 100 % of the collected raw influent samples with concentrations varying from 15 ng L-1 to 1849 ng L-1. Azithromycin, clarithromycin and erythromycin were also detected in 100 % of the treated water samples and roxithromycin was present in 96 % of the samples. The highest determined concentration in the treated water samples was 1404 ng L-1 of azithromycin. Based on the determined macrolide concentrations, removal efficiencies of individual wastewater treatment plants were calculated to range from 13 % to 100 %.

Are Terrestrial Organisms Able to Live in Contaminated Soil after Fire-Fighting?

There was performed test of ecotoxicity with using earthworm Eisenia Fetida as chief representative of terrestrial organisms in the study. Soil matrix LUFA 2.3 was selected as a model of natural soil environment. Tested FEAs were follows: Sthamex F-15, Moussol-APS F-15 and Finiflam F-15. For experimental purposes, laboratory installation for infiltration was designed and compiled. Infiltration of three FEAs solutions was done before the ecotoxicity testing. Contaminated soil after infiltration was tested for semi-chronic ecotoxicity and reproduction ecotoxicity then. Introductory results indicates differences between each FEA, caused by various composition. Sthamex F-15 was determined as the most ecotoxic agent at all. Whilst Moussol-APS F-15 was evaluated as the agent with least ecotoxicity effect.