The temporal and spatial trends in sediment of 22 poly- and perfluorinated (PFAS) compounds were investigated in the southern Great Lakes Erie and Ontario as well as Lake St. Clair. Surface concentrations measured by Ponar grab samples indicated a trend for greater concentrations near to urban sites. Mean concentrations ∑22PFAS were 15.6, 18.2 and 19 ng g-1 dm for Lakes St. Clair, Erie and Ontario, respectively. Perfluoro-n-butanoic acid (PFBA) and Perfluoro-n-hexanoic acid (PFHxA) were frequently determined in surface sediment and upper core samples indicating a shift in use patterns. Where PFBA was identified it was at relatively great concentrations typically >10 ng g-1 dm. However as PFBA and PFHxA are less likely to bind to sediment they may be indicative of pore water concentrations Sedimentation rates between Lake Erie and Lake Ontario differ greatly with greater rates observed in Lake Erie. In Lake Ontario, in general concentrations of PFAS observed in core samples closely follow the increase in use along with an observable change due to regulation implementation in the 1970s for water protection. However some of the more water soluble PFAS were observed in deeper core layers than the time of production could account for, indicating potential diffusion within the sediment. Given the greater sedimentation rates in Lake Erie, it was hoped to observe in greater resolution changes since the mid-1990s. However, though some decrease was observed at some locations the results are not clear. Many cores in Lake Erie had clearly observable gas voids, indicative of gas ebullition activity due to biogenic production, there were also observable mussel beds that could indicate mixing by bioturbation of core layers.
- MeSH
- Water Pollutants, Chemical analysis MeSH
- Water Pollution, Chemical statistics & numerical data MeSH
- Fluorocarbons analysis MeSH
- Lakes MeSH
- Environmental Monitoring * MeSH
- Publication type
- Journal Article MeSH
- Geographicals
- Great Lakes Region MeSH
- Ontario MeSH
Changes in pollutant loads in relatively dynamic river sediments, which contain very complex mixtures of compounds, can play a crucial role in the fate and effects of pollutants in fluvial ecosystems. The contamination of sediments by bioactive substances can be sensitively assessed by in vitro bioassays. This is the first study that characterizes detailed short- and long-term changes in concentrations of contaminants with several modes of action in river sediments. One-year long monthly study described seasonal and spatial variability of contamination of sediments in a representative industrialized area by dioxin-like and endocrine disruptive chemicals. There were significant seasonal changes in both antiandrogenic and androgenic as well as dioxin-like potential of river sediments, while there were no general seasonal trends in estrogenicity. Aryl hydrocarbon receptor-dependent potency (dioxin-like potency) expressed as biological TCDD-equivalents (BIOTEQ) was in the range of 0.5-17.7 ng/g, dry mass (dm). The greatest BIOTEQ levels in sediments were observed during winter, particularly at locations downstream of the industrial area. Estrogenicity expressed as estradiol equivalents (EEQ) was in the range of 0.02-3.8 ng/g, dm. Antiandrogenicity was detected in all samples, while androgenic potency in the range of 0.7-16.8 ng/g, dm dihydrotestosterone equivalents (DHT-EQ) was found in only 30 % of samples, most often during autumn, when antiandrogenicity was the least. PAHs were predominant contaminants among analyzed pollutants, responsible, on average, for 13-21 % of BIOTEQ. Longer-term changes in concentrations of BIOTEQ corresponded to seasonal fluctuations, whereas for EEQ, the inter-annual changes at some locations were greater than seasonal variability during 1 year. The inter- as well as intra-annual variability in concentrations of both BIOTEQ and EEQ at individual sites was greater in spring than in autumn which was related to hydrological conditions in the river. This study stresses the importance of river hydrology and its seasonal variations in the design of effective sampling campaigns, as well as in the interpretation of any monitoring results.
- MeSH
- Biological Assay MeSH
- Water Pollutants, Chemical analysis MeSH
- Water Pollution, Chemical statistics & numerical data MeSH
- Dioxins analysis MeSH
- Endocrine Disruptors analysis MeSH
- Geologic Sediments chemistry MeSH
- Environmental Monitoring * MeSH
- Polychlorinated Dibenzodioxins analysis MeSH
- Polycyclic Aromatic Hydrocarbons analysis MeSH
- Receptors, Aryl Hydrocarbon MeSH
- Rivers chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
Seasonal removal efficiency of 16 pharmaceuticals and personal care products was monitored in a wastewater treatment plant in České Budějovice, Czech Republic, over a period of 1 year (total amount of samples, n = 272). The studied compounds included four UV filters, three analgesics/anti-inflammatory drugs and nine anti-hypertensive/cardiovascular drugs. In most cases, elimination of the substances was incomplete, and overall removal rates varied strongly from -38 to 100%. Therefore, it was difficult to establish a general trend for each therapeutic group. Based on the removal efficiencies (REs) over the year, three groups of target compounds were observed. A few compounds (benzophenon-1, valsartan, isradipine and furosemide) were not fully removed, but their REs were greater than 50%. The second group of analytes, consisting of 2-phenylbenzimidazole-5-sulfonic acid, tramadol, sotalol, metoprolol, atenolol and diclofenac, showed a very low RE (lower than 50%). The third group of compounds showed extremely variable RE (benzophenon-3 and benzophenon-4, codeine, verapamil, diltiazem and bisoprolol). There were significant seasonal trends in the observed REs, with reduced efficiencies in colder months.
- MeSH
- Anti-Inflammatory Agents, Non-Steroidal analysis MeSH
- Antihypertensive Agents analysis MeSH
- Water Pollutants, Chemical analysis MeSH
- Water Pollution, Chemical statistics & numerical data MeSH
- Chromatography, Liquid MeSH
- Filtration instrumentation MeSH
- Mass Spectrometry MeSH
- Cardiovascular Agents analysis MeSH
- Waste Disposal, Fluid * MeSH
- Wastewater analysis MeSH
- Seasons * MeSH
- Ultraviolet Rays MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Geographicals
- Czech Republic MeSH
Aims: Impact of potentially toxic elements (PTE) on the health status of population of the Slovak Republic has been studied in two historical mining areas with ore extraction from Middle Ages (the Middle Slovak Neovolcanics, the Slovak Ore Mts.) and one historical mining area with more than hundred years brown coal mining (Upper Nitra region). Methods: The contents of PTE were analysed in groundwater/ drinking water and soils. The health status of resident population was evaluated based on 43 health indicators classified according to the international classi- fication of diseases (ICD, 10th revision), including mainly those indicators characterizing mortality on cardiovascular and oncological diseases. In these areas the health status of population living in municipalities with increased PTE contents (As, Pb, Zn, Cu, Cd, Hg and Sb) was compared with that in adjacent municipalities showing low PTE contents.
- MeSH
- Water Pollution, Chemical analysis statistics & numerical data MeSH
- Geological Phenomena MeSH
- Geologic Sediments MeSH
- Mining * MeSH
- Cardiovascular Diseases mortality MeSH
- Soil Pollutants analysis MeSH
- Water Pollutants analysis MeSH
- Humans MeSH
- Neoplasms mortality MeSH
- Drinking Water chemistry MeSH
- Groundwater chemistry MeSH
- Industrial Waste MeSH
- Coal Mining MeSH
- Health Status Indicators MeSH
- Environmental Exposure * MeSH
- Environmental Pollution * analysis statistics & numerical data MeSH
- Check Tag
- Humans MeSH
- Publication type
- Research Support, Non-U.S. Gov't MeSH
- Comparative Study MeSH
- Geographicals
- Slovakia MeSH
Dissolved waterborne polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed over a period of one year at five sampling sites in a model industrial region in the Czech Republic using silicone rubber passive samplers. The spatial variability of POPs in the studied region in water was small and diffusive pollution sources predominate. Concentrations of the most volatile PAHs decreased with increasing water temperature in the whole region, which reflects the seasonality in atmospheric deposition. The dissolved concentrations of more hydrophobic PAHs, PCBs and OCPs in and downstream the industrial zone are related to desorption from suspended particles. Upstream the industrial area, a positive correlation of dissolved and particle-bound contamination was observed only for DDT metabolites and hexachlorobenzene. Calculated fugacities in water and bottom sediment indicated a fair degree of equilibrium between these compartments for OCPs and PCBs, whereas sediment represented a potential source of PAHs.
- MeSH
- Water Pollutants, Chemical analysis MeSH
- Water Pollution, Chemical statistics & numerical data MeSH
- Hydrocarbons, Chlorinated analysis MeSH
- Hydrophobic and Hydrophilic Interactions MeSH
- Environmental Monitoring instrumentation methods MeSH
- Pesticides analysis MeSH
- Polychlorinated Biphenyls analysis MeSH
- Polycyclic Aromatic Hydrocarbons analysis MeSH
- Rivers chemistry MeSH
- Silicone Elastomers chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Geographicals
- Czech Republic MeSH
- MeSH
- Aconitine analysis MeSH
- Atropine analysis MeSH
- Water Pollution, Chemical analysis statistics & numerical data MeSH
- Mercuric Chloride analysis MeSH
- Enzyme Assays methods statistics & numerical data MeSH
- Fenitrothion analysis MeSH
- Conductometry methods statistics & numerical data MeSH
- Potassium Cyanide analysis MeSH
- Hazardous Substances analysis MeSH
- Saccharomyces cerevisiae chemistry MeSH
- Sensitivity and Specificity MeSH
- Statistics as Topic MeSH
- Toxicity Tests methods instrumentation statistics & numerical data MeSH
- Cell Survival MeSH
- Military Medicine instrumentation MeSH
- Research Design MeSH
Sulfonamide antibiotics coming from both human and veterinary medicine are among the most common emerging pollutants in freshwater. The present paper shows the successful application of passive sampling using POCIS in combination with an immunochemical ELISA technique and HPLC/MS/MS analysis to study the distribution of sulfonamides in streams around small towns in the Czech Republic, as well as around a major agglomeration of the city of Brno, including its waste water treatment plant (WWTP). Results indicated the presence of sulfonamides at most studied sites with concentrations ranging from <20 up to 736 ng of sulfamethoxazole equivalents per POCIS. Very high levels were detected in both the influent and effluent of the Brno WWTP with maxima > 8000 ng SMX per POCIS. All samplers collected down-stream of the studied towns and WWTPs clearly showed an increase in sulfonamide drug residues. Higher concentrations were determined in rivers at the city of Brno agglomeration. In agreement with other available studies, these findings indicate low efficiency of conventional WWTPs to eliminate polar pharmaceuticals such as sulfonamides. Good performance and correlation with the LC/MS results, as well as ease of use, indicate good potential for the immunochemical ELISA technique to become the screening tool for sulfonamide determination in surface waters including passive samplers.
- MeSH
- Anti-Bacterial Agents analysis MeSH
- Water Pollutants, Chemical analysis MeSH
- Water Pollution, Chemical statistics & numerical data MeSH
- Enzyme-Linked Immunosorbent Assay MeSH
- Environmental Monitoring methods MeSH
- Waste Disposal, Fluid methods MeSH
- Sulfonamides analysis MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Geographicals
- Czech Republic MeSH
This manuscript reports, for the first time, a monitoring study analysing wastewater and associated suspended particulate matter (SPM) to determine the concentration of drugs of abuse and metabolites in wastewater influent. The monitoring of SPM is crucial for target analytes because, depending on their physico-chemical properties, they may partition to particulates; thus, analysis of wastewater only will result in under-reporting of the concentration of target analytes in the sample. A daily one week monitoring study was carried out at a WWTP serving one of the largest cities in the Czech Republic; representing the first comprehensive application of the sewage epidemiology approach in the Czech Republic. In total, 60 analytes were targeted in the monitoring programme including stimulants, opioid and morphine derivatives, benzodiazepines, antidepressants, dissociative anaesthetics, drug precursors and their metabolites. Analysis of SPM determined that significant proportions of some compounds were present on the solids. For example, 21.0-49.8% of the total concentration of EDDP (2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine) in the sample was determined on SPM and 11.2-19.6% of methadone. The highest proportion on SPM was determined for fluoxetine in the range 68.1-79.6%, norfluoxetine 46.6-61.9% and amitriptyline 21.8-51.2%. In contrast, some compounds presented very little partitioning to SPM. Less than 5% was determined partitioned to SPM over the week period for analytes including cocaine, benzoylecgonine, cocaethylene, amphetamine, methamphetamine, MDMA (3,4-methylenedioxymethamphetamine), codeine, dihydrocodeine, tramadol, nortramadol, oxazepam and ephedrine. Determined concentrations in wastewater influent were subsequently utilised in the sewage epidemiology approach to estimate drug consumption, in the community from which the wastewater was derived. This back-calculation was updated for the first time to include the concentration of analytes present on SPM. The consumption of methamphetamine and MDMA was determined to be especially high in the studied community in relation to other European countries, while cocaine and methadone consumption was relatively low. This manuscript shows that in order to apply the sewage epidemiology approach, SPM analysis is required for some compounds; whereas for others the partitioning is small and one may regard this as negligible.
- MeSH
- Water Pollutants, Chemical analysis MeSH
- Water Pollution, Chemical statistics & numerical data MeSH
- Cocaine analogs & derivatives analysis MeSH
- Methamphetamine analysis MeSH
- Environmental Monitoring MeSH
- N-Methyl-3,4-methylenedioxyamphetamine analysis MeSH
- Wastewater chemistry statistics & numerical data MeSH
- Sewage chemistry MeSH
- Substance-Related Disorders epidemiology MeSH
- Pyrrolidines analysis MeSH
- Illicit Drugs analysis MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Geographicals
- Czech Republic MeSH
Endocrine-disruptive potential and concentrations of polar organic contaminants were measured in seven headwaters flowing through relatively unpolluted areas of the Czech Republic. Towns with Wastewater Treatment Plant (WWTP) discharges were the first known sources of anthropogenic pollution in the areas. River water was sampled several kilometers upstream (US) and several tens of meters downstream (DS) of the WWTP discharges, by use of Pesticide and Pharmaceutical Polar Organic Integrative Samplers (POCIS-Pest, POCIS-Pharm). Extracts of passive samplers were tested by use of a battery of in vitro bioassays to determine overall non-specific cytotoxicity, endocrine-disruptive (ED) potential and dioxin-like toxicity. The extracts were also used for quantification of polar organics. There was little toxicity to cells caused by most extracts of POCIS. Estrogenicity was detected in all types of samples even though US locations are considered to be background. At US locations, concentrations of estrogen equivalents (EEq) ranged from less than the detection limits (LOD) to 0.5 ng EEq/POCIS. Downstream concentrations of EEqs ranged from less than LOD to 4.8 ng EEq/POCIS. Concentrations of EEq in POCIS extracts from all DS locations were 1 to 14 times greater than those at US locations. Concentrations of EEq measured in extracts of POCIS-Pest and POCIS-Pharm were in a good agreement. Neither antiestrogenic nor anti/androgenic activities were detected. Concentrations of 2,3,7,8-TCDD equivalents (TEq(bio)) were detected in both types of POCIS at concentrations ranging from less than the LOD to 0.39 ng TEq(bio)/POCIS. Nearly all extracts of POCIS-Pharm contained greater concentrations of TEq(bio) activity than extracts of POCIS-Pest. Concentrations of pesticides and pharmaceuticals in extracts of POCIS were generally small at all sampling sites, but levels of some pharmaceuticals were significantly greater in both types of POCIS from DS locations. Chemical analyses along with the results of bioassays documented impacts of small towns with WWTPs on headwaters.
- MeSH
- Biological Assay MeSH
- Water Pollutants, Chemical analysis toxicity MeSH
- Water Pollution, Chemical statistics & numerical data MeSH
- Dioxins analysis toxicity MeSH
- Endocrine Disruptors analysis toxicity MeSH
- Estrogens analysis toxicity MeSH
- Hydrophobic and Hydrophilic Interactions MeSH
- Environmental Monitoring MeSH
- Waste Disposal, Fluid statistics & numerical data MeSH
- Wastewater analysis statistics & numerical data MeSH
- Pesticides analysis toxicity MeSH
- Rivers chemistry MeSH
- Fresh Water MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Geographicals
- Czech Republic MeSH
A method employing solid phase extraction followed by gas chromatography-mass spectrometry with negative chemical ionization has been developed for determination of ultratrace concentrations of perfluoroalkyl carboxylic acids in river water. The effects of the experimental parameters, such as the pH, additions of NaCl and an ion-pairing agent (tetraethylammonium bromide) and the kind of the elution agent, on the efficiency of the test acid extraction have been studied. The analyte extraction recoveries and the limits of detection and determination have been found. The method developed has been tested on determinations of perfluoroalkyl carboxylic acids in the waters of the two largest Czech rivers, Vltava and Labe (Elbe). The best extraction results have been attained without any alteration of the sample pH, with an addition of tetrabutylammonium bromide (a concentration of 50 μg mL(-1) in the sample) and using methanol as the elution agent. Under these conditions, the recoveries of the test acids in the spiked real samples are within ranges from 60% to 104% and 53% to 111% for analyte concentration levels of 1.40 ng mL(-1) and 0.14 ng mL(-1), respectively, depending on the lengths of the perfluorinated chains of the acids. In general, the recovery decreases with increasing length of this chain. The method developed exhibits very low limits of detection and determination and the results are fully comparable with those obtained when using more expensive HPLC-MS/MS instrumentation. Typical values amount to tenths to tens of pg mL(-1) and units to one hundred pg mL(-1) for the limits of detection and determination, respectively; the measuring sensitivity increases with increasing length of the analyte chain. The analyzes of real samples from the Vltava and Elbe rivers have demonstrated that the results obtained are similar to the values published for contamination of the Elbe and other rivers in western and central Europe. The concentrations determined are of the order of units to tens of pg mL(-1) and the C(8)-C(10) acids occur most often.
- MeSH
- Water Pollutants, Chemical analysis MeSH
- Water Pollution, Chemical statistics & numerical data MeSH
- Solid Phase Extraction MeSH
- Fluorocarbons analysis MeSH
- Carboxylic Acids analysis MeSH
- Environmental Monitoring methods MeSH
- Gas Chromatography-Mass Spectrometry MeSH
- Rivers chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Geographicals
- Czech Republic MeSH
