POCIS
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Polar organic compound integrative samplers (POCIS) in combination with instrumental techniques such as LC-MS-MS were previously used to monitor environmental pollutants but the performance of alternative immunochemical methods such as ELISA (enzyme-linked immunosorbent assay) has been explored less. In the present study, POCIS technology was applied to surface water sampling in the Czech Republic, and ELISA was used as a detection technique for the herbicide atrazine. In the first study, 28 samples from streams around small municipal waste water treatment plants (WWTPs) were collected using two different devices (POCISpest and POCISpharm) over the course of 21 days. Elevated atrazine concentrations (up to 25 ng per POCIS) were found in samples down-stream of WWTPs. This observation was also confirmed in another two year study (4 sampling periods) investigating 7 river sites around a major city of Brno as well as the inlet and outlet of the city's WWTP. High atrazine levels were systematically determined at the outlet from the WWTPs (120-605 ng per POCIS). A decreasing trend in the atrazine concentrations in rivers around the city of Brno has been observed, with the highest levels observed within the first sampling period in spring 2007 (100-600 ng per POCIS, with an extreme value of 2760 ng per POCIS). Results of the atrazine ELISA were closely correlated with LC-MS/MS, which confirmed good applicability of ELISA as a cost-effective screening tool.
- MeSH
- atrazin analýza MeSH
- chemické látky znečišťující vodu analýza MeSH
- chemické znečištění vody statistika a číselné údaje MeSH
- ELISA MeSH
- herbicidy analýza MeSH
- monitorování životního prostředí přístrojové vybavení metody MeSH
- sladká voda chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem 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
- antibakteriální látky analýza MeSH
- chemické látky znečišťující vodu analýza MeSH
- chemické znečištění vody statistika a číselné údaje MeSH
- ELISA MeSH
- monitorování životního prostředí metody MeSH
- odpad tekutý - odstraňování metody MeSH
- sulfonamidy analýza MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Geografické názvy
- Česká republika MeSH
POCIS is the most widely applied passive sampler of polar organic substances, because it was one of the first commercially available samplers for that purpose on the market, but also for its applicability for a wide range of substances and conditions. Its main weakness is the variability of sampling performance with exposure conditions. In our study we took a pragmatic approach and performed in situ calibration for a set of 76 pharmaceuticals and their metabolites in five sampling campaigns in surface water, covering various temperature and flow conditions. In individual campaigns, RS were calculated for up to 47 compounds ranging from 0.01 to 0.63 L d-1, with the overall median value of 0.10 L d-1. No clear changes of RS with water temperature or discharge could be found for any of the investigated substances. The absence of correlation of experimental RS with physical-chemical properties in combination with the lack of mechanistic understanding of compound uptake to POCIS implies that practical estimation of aqueous concentrations from uptake in POCIS depends on compound-specific experimental calibration data. Performance of POCIS was compared with grab sampling of water in seven field campaigns comprising multiple sampling sites, where sampling by both methods was done in parallel. The comparison showed that for 25 of 36 tested compounds more than 50% of POCIS-derived aqueous concentrations did not differ from median of grab sampling values more than by a factor of 2. Further, for 30 of 36 compounds, more than 80% of POCIS data did not differ from grab sampling data more than by a factor of 5. When accepting this level of accuracy, in situ derived sampling rates are sufficiently robust for application of POCIS for identification of spatial and temporal contamination trends in surface waters.
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
- biotest MeSH
- chemické látky znečišťující vodu analýza toxicita MeSH
- chemické znečištění vody statistika a číselné údaje MeSH
- dioxiny analýza toxicita MeSH
- endokrinní disruptory analýza toxicita MeSH
- estrogeny analýza toxicita MeSH
- hydrofobní a hydrofilní interakce MeSH
- monitorování životního prostředí MeSH
- odpad tekutý - odstraňování statistika a číselné údaje MeSH
- odpadní voda analýza statistika a číselné údaje MeSH
- pesticidy analýza toxicita MeSH
- řeky chemie MeSH
- sladká voda MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Geografické názvy
- Česká republika MeSH
The applicability of a polar organic chemical integrative sampler (POCIS) for detection and determination of perfluorinated acids and sulfonates in water was studied under field conditions. Standard POCIS configurations (i.e., pharmaceutical and pesticide) were deployed in effluent from a wastewater treatment plant for 1, 2, and 3 weeks. Ten of 15 target compounds were found in POCIS, five of which were quantified in wastewater. Pest-POCIS appeared more effective for the sampling, while Pharm-POCIS had a more rapid uptake kinetic, which leads to faster saturation or equilibrium. The results showed that the pesticide configuration is probably more suitable for the sampling of this class of compounds. Based on average concentration in water over the sampling period and amount of compound adsorbed in the POCIS, we calculated sampling rates for five studied compounds and obtained values of 0.034 to 0.222 L day(-1).
- MeSH
- alkylsulfonany analýza MeSH
- chemické látky znečišťující vodu analýza MeSH
- fluorokarbony analýza MeSH
- monitorování životního prostředí přístrojové vybavení metody MeSH
- odpadní voda analýza MeSH
- plynová chromatografie s hmotnostně spektrometrickou detekcí MeSH
- polymery analýza MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
Synthetic musk compounds are extensively used in personal care and cosmetic products all over the world. Afterwards, they are discharged into the environment mainly because they are not completely removed in wastewater treatment plants. The aim of this study was to investigate if a passive sampler is applicable for the monitoring of tonalide, a polycyclic musk compound, in the aquatic environment and to compare the levels of tonalide in pesticide-polar organic chemical integrative sampler (POCIS) and biota. For this purpose, four sampling localities on the three biggest rivers in the Czech Republic were selected. Tonalide was determined in POCIS at all sampling sites in the concentration ranging from 9 ng/POCIS (Labe River, Hradec Králové) to 25 ng/POCIS (Morava River, Blatec). The locality with the most frequent occurrence of tonalide in biota samples was the Morava River which well corresponded with the highest tonalide concentration in POCIS among sampling sites. The highest number of positive tonalide detections among all studied biota samples was found in fish plasma. To the best of our knowledge, this is the first evidence that tonalide bioaccumulates in fish blood. Tonalide levels were below the limit of quantification in benthos samples at all sampling sites.
- MeSH
- chemické látky znečišťující vodu analýza MeSH
- kosmetické přípravky analýza MeSH
- limita detekce MeSH
- monitorování životního prostředí přístrojové vybavení metody MeSH
- odpadní voda chemie MeSH
- pesticidy analýza MeSH
- řeky chemie MeSH
- společenstvo MeSH
- tetrahydronaftaleny analýza MeSH
- vodní organismy chemie MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Česká republika MeSH
Endocrine-disrupting chemicals (EDC) are manmade or natural chemicals that have the ability to interfere with the endocrine system of animals. They have not been monitored systematically in the Czech Republic. The goal of the present study was the characterization of aquatic environmental pollution from the Brno (Czech Republic) city agglomeration focusing on EDC. Passive sampling devices, as well as semipermeable membrane devices (SPMD) and polar organic chemical integrative samplers (POCIS), were used for the pilot assessment of EDC. They were deployed for 21- to 28-d periods at nine locations in the Svratka and Svitava Rivers, Brno, Czech Republic, including at the inlet and outlet of Brno's wastewater treatment plant. The SPMDs were used to monitor nonpolar compounds such as polychlorinated biphenyls (PCBs), polynuclear aromatic hydrocarbons (PAHs), and organochlorinated pesticides (OCP). The POCIS were used to monitor polar compounds such as pesticides and their metabolites, perfluoro-organic compounds (PFOC), and pharmaceuticals. The passive samplers allowed very low detection limits for soluble (bioavailable) fractions of pollutants. The contribution of PAH, PCB, and HCB in sewage water to pollution of the Svratka River was low. The Brno wastewater treatment plant was identified as the main source of pharmaceuticals, triclosan, methyl triclosan, and some polar pesticides.
- MeSH
- chemické látky znečišťující vodu analýza MeSH
- čištění vody MeSH
- endokrinní disruptory analýza MeSH
- fluorokarbony analýza MeSH
- léčivé přípravky analýza MeSH
- monitorování životního prostředí metody MeSH
- odpad tekutý - odstraňování MeSH
- pesticidy analýza MeSH
- polychlorované bifenyly analýza MeSH
- polycyklické aromatické uhlovodíky analýza MeSH
- řeky chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Geografické názvy
- Česká republika MeSH
In situ extraction of steroid hormones from waste water using adsorption-based integrative passive samplers represents a promising approach for their monitoring in water at ultra-trace concentrations. Three passive samplers, namely a POCIS, a Chemcatcher fitted with an Empore SDB-RPS disk, and an Empore SDB-RPS disk-based sampler with enhanced water flow, were calibrated in situ in treated municipal wastewater for the purpose of monitoring five estrogens (17-β-estradiol, 17-α-estradiol, 17-α-ethinylestradiol, estrone and estriol) at sub ng per litre concentrations. Uptake of steroids to samplers during 14-day exposure in wastewater was compared with steroid concentrations in daily collected composite water samples. Sampling rates were obtained from a numerical solution of first order uptake kinetics equations describing the uptake of compounds into a passive sampler over time. Mass transfer of steroids in the Chemcatcher fitted with naked Empore disks was more than two times faster than in the POCIS sampler. The uptake capacity of the applied Empore disk was not sufficient for integrative uptake of all tested steroids during the entire 14-day exposure. Time-weighted average concentrations of steroids estimated at concentrations in units of ngL-1using the in situ-calibrated samplers were within a factor of two from values obtained using composite water samples.
In the present study, we have evaluated the effectiveness of a passive sampler for polar organic chemicals to accumulate a group of widespread and hazardous tumor-promoting toxins produced in cyanobacterial water blooms-microcystins (MC). The previously optimized configuration of the sampler based on polycarbonate membrane and Oasis HLB sorbent (2.75 mg/cm(2)) was validated under various exposure scenarios in laboratory and field. Calibration of the passive sampler conducted under variable conditions and concentrations of MC revealed linearity of the sampling up to 4 weeks. The sampling rates of microcystins for two different exposure scenarios were derived (e.g., MC-LR: R (s) = 0.017 L/day under static and 0.087 L/d under turbulent conditions). R (s) values were further used for calculations of time-weighted average concentrations in natural water. Improved sensitivity and selectivity of the in-house-made sampler was observed in comparison with the commercially available Polar Organic Compound Integrative Sampler (POCIS). Comparisons of grab and passive sampling methods were performed during cyanobacterial water bloom season in the Brno reservoir, Czech Republic in 2008. Data obtained by passive sampling provided a more relevant picture of the situation and enabled better assessment of potential risks. The present study demonstrated that the modification of POCIS is suitable for monitoring of occurrence and retrospective estimations of microcystin water concentrations, especially with respect to the control of drinking water quality.
- MeSH
- bakteriální toxiny izolace a purifikace MeSH
- kalibrace MeSH
- membrány umělé MeSH
- mikrocystiny izolace a purifikace MeSH
- monitorování životního prostředí přístrojové vybavení MeSH
- mořské toxiny izolace a purifikace MeSH
- sinice chemie MeSH
- Publikační typ
- časopisecké články MeSH
- hodnotící studie MeSH
- práce podpořená grantem MeSH
Passive and composite sampling in combination with in vitro bioassays and identification and quantification of individual chemicals were applied to characterize pollution by compounds with several specific modes of action in urban area in the basin of two rivers, with 400,000 inhabitants and a variety of industrial activities. Two types of passive samplers, semipermeable membrane devices (SPMD) for hydrophobic contaminants and polar organic chemical integrative samplers (POCIS) for polar compounds such as pesticides and pharmaceuticals, were used to sample wastewater treatment plant (WWTP) influent and effluent as well as rivers upstream and downstream of the urban complex and the WWTP. Compounds with endocrine disruptive potency were detected in river water and WWTP influent and effluent. Year-round, monthly assessment of waste waters by bioassays documented estrogenic, androgenic and dioxin-like potency as well as cytotoxicity in influent waters of the WWTP and allowed characterization of seasonal variability of these biological potentials in waste waters. The WWTP effectively removed cytotoxic compounds, xenoestrogens and xenoandrogens. There was significant variability in treatment efficiency of dioxin-like potency. The study indicates that the WWTP, despite its up-to-date technology, can contribute endocrine disrupting compounds to the river. Riverine samples exhibited dioxin-like, antiestrogenic and antiandrogenic potencies. The study design enabled characterization of effects of the urban complex and the WWTP on the river. Concentrations of PAHs and contaminants and specific biological potencies sampled by POCIS decreased as a function of distance from the city.
- MeSH
- androgenní receptory metabolismus MeSH
- androgeny analýza farmakologie MeSH
- biotest MeSH
- chemické látky znečišťující vodu analýza farmakologie MeSH
- čištění vody MeSH
- dioxiny analýza farmakologie MeSH
- endokrinní disruptory analýza farmakologie MeSH
- estrogeny analýza farmakologie MeSH
- krysa rodu rattus MeSH
- monitorování životního prostředí MeSH
- nádorové buněčné linie MeSH
- odpadní voda chemie MeSH
- pesticidy analýza farmakologie MeSH
- polychlorované dibenzodioxiny analýza farmakologie MeSH
- polycyklické aromatické uhlovodíky analýza farmakologie MeSH
- receptory aromatických uhlovodíků metabolismus MeSH
- receptory pro estrogeny metabolismus MeSH
- řeky chemie MeSH
- skládková zařízení MeSH
- velkoměsta MeSH
- zvířata MeSH
- Check Tag
- krysa rodu rattus MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Geografické názvy
- Česká republika MeSH
- velkoměsta MeSH
