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
- Atrazine analysis MeSH
- Water Pollutants, Chemical analysis MeSH
- Water Pollution, Chemical statistics & numerical data MeSH
- Enzyme-Linked Immunosorbent Assay MeSH
- Herbicides analysis MeSH
- Environmental Monitoring instrumentation methods MeSH
- Fresh Water chemistry MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Names of Substances
- Atrazine MeSH
- Water Pollutants, Chemical MeSH
- Herbicides 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
- Names of Substances
- Anti-Bacterial Agents MeSH
- Water Pollutants, Chemical MeSH
- Sulfonamides 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.
- Keywords
- Aquatic pollution, Passive sampling, Polar organic contaminants, Sampling rate,
- MeSH
- Water Pollutants, Chemical * analysis MeSH
- Calibration MeSH
- Pharmaceutical Preparations * MeSH
- Environmental Monitoring MeSH
- Organic Chemicals MeSH
- Publication type
- Journal Article MeSH
- Names of Substances
- Water Pollutants, Chemical * MeSH
- Pharmaceutical Preparations * MeSH
- Organic Chemicals MeSH
The possibilities of expanding a groundwater quality monitoring scheme by passive sampling using polar organic chemical integrative sampler (POCIS) comprising HLB sorbent as the receiving phase were explored. Passive sampling and grab sampling were carried out simultaneously in the regions with vulnerable groundwater resources in Slovakia, between 2013 and 2021. For 27 pesticides and degradation products detected both in POCIS and the grab samples, in situ sampling rates were calculated and statistically evaluated. The limited effectiveness of the receiving phase in POCIS for sampling polar or ionized compounds was confirmed through a comparison of the medians of compound-specific sampling rates. For the majority of the monitored compounds the median sampling rates varied between 0.01 and 0.035 L/day. In some cases, the actual in situ values could be confirmed by parallel exposure of POCIS and silicone rubber sheet employed to obtain a benchmark for maximum attainable sampling rate. Sampling site and sampling period appear to have also some influence on the sampling rates, which was attributed in part to the groundwater velocity varying in both space and time. The influence of physico-chemical parameters (temperature, pH, electrolytic conductivity) remains mostly questionable due to the naturally limited ranges of recorded values over the entire duration of the study. Concentrations of pollutants in POCIS could be used for predicting time weighed average concentrations in water, provided the sampling rates were known and relatively constant. Generally, the compound-specific sampling rate cannot be considered constant due to a combination of naturally varying environmental factors that influence the actual in situ sampling rate. The relative standard deviation of concentration data from POCIS exposed in triplicates varied between approx. 5 %-50 %. Utilizing exploratory data analysis approach and tools enabled us to obtain a relatively complex picture of the situation and progress regarding pesticide pollution of groundwater in the monitored areas.
- Keywords
- POCIS, Passive sampling, Sampling rate, Water framework directive, Water quality monitoring,
- Publication type
- Journal Article MeSH
Over the past decades, several types of passive samplers have been developed and used to monitor polar organic compounds in aquatic environments. These samplers use different sorbents and barriers to control the uptake into the sampler, but their performance comparison is usually not well investigated. This study aimed to directly compare the performance of three samplers, i.e., the Polar Organic Chemical Integrative Sampler (POCIS), the Hydrogel-based Passive Sampler (HPS, an upscaled version of o-DGT), and the Speedisk, on a diverse suite of pharmaceuticals, per- and polyfluoroalkylated substances (PFAS), and pesticides and their metabolites. The samplers were deployed side-by-side in the treated effluent of a municipal wastewater treatment plant for different exposure times. All samplers accumulated a comparable number of compounds, and integrative uptake was observed for most compounds detected up to 28 days for POCIS, up to 14 days for HPS, and up to 42 days for Speedisk. In the integrative uptake phase, consistent surface-specific uptake was observed with a significant correlation between samplers (r ≥ 0.76) despite differences in sampler construction, diffusion barrier, and sorbent material used. The low sampling rates compared to the literature and the low estimated overall mass transfer coefficient suggests that the water boundary layer was the main barrier controlling the uptake for all samplers. Although all devices provided comparable performance, Speedisk overcomes POCIS and HPS in several criteria, including time-integrative sampling over a long period and physical durability.
- Keywords
- Mass transfer, O-DGT, POCIS, Pesticides, Pharmaceuticals, Speedisk,
- Publication type
- Journal Article 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.
- Keywords
- Benthos, Bioaccumulation, Fish, Musk, Mussel, POCIS, Plasma,
- MeSH
- Water Pollutants, Chemical analysis MeSH
- Cosmetics analysis MeSH
- Limit of Detection MeSH
- Environmental Monitoring instrumentation methods MeSH
- Wastewater chemistry MeSH
- Pesticides analysis MeSH
- Rivers chemistry MeSH
- Biota MeSH
- Tetrahydronaphthalenes analysis MeSH
- Aquatic Organisms chemistry MeSH
- Animals MeSH
- Check Tag
- Animals MeSH
- Publication type
- Journal Article MeSH
- Geographicals
- Czech Republic MeSH
- Names of Substances
- acetyl methyl tetramethyl tetralin MeSH Browser
- Water Pollutants, Chemical MeSH
- Cosmetics MeSH
- Waste Water MeSH
- Pesticides MeSH
- Tetrahydronaphthalenes MeSH
The goal of this study was to assess the bioavailable concentrations of analgesics, psycholeptics, antidepressants and illicit drugs in the surface waters of the Czech Republic. All of the sampling sites are located within the most important water quality monitoring profiles at the Czech Hydrometeorological Institute. The total concentrations of the compounds ranged from 463 to 6,447 ng POCIS(-1) (Polar Organic Chemical Integrative Sampler). Carbamazepine (196-2,690 ng POCIS(-1)) and tramadol (160-2,250 ng POCIS(-1)) were the most abundant compounds at every site. The most polluted sites were those that received communal wastewater effluent and had a low dilution factor (ratio of wastewater effluent and river flow). The aqueous concentrations of the target compounds were estimated using sampling rate values obtained during a field calibration experiment. Patterns in the aqueous concentrations of the compounds (after back calculation from POCIS extracts) and the POCIS concentrations are different, possibly leading to discrepancies between the toxicity assessments conducted using POCIS extracts and those conducted using grab samples of water from the same location.
- Keywords
- Field calibration, POCIS, Psychoactive compounds, Sampling rate, Surface water,
- MeSH
- Analgesics analysis MeSH
- Antidepressive Agents analysis MeSH
- Water Pollutants, Chemical analysis MeSH
- Environmental Monitoring methods MeSH
- Substance Abuse Detection methods MeSH
- Waste Disposal, Fluid MeSH
- Wastewater chemistry statistics & numerical data MeSH
- Fresh Water chemistry MeSH
- Illicit Drugs analysis MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Geographicals
- Czech Republic MeSH
- Names of Substances
- Analgesics MeSH
- Antidepressive Agents MeSH
- Water Pollutants, Chemical MeSH
- Waste Water MeSH
- Illicit Drugs 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-1 using the in situ-calibrated samplers were within a factor of two from values obtained using composite water samples.
- Keywords
- Chemcatcher, POCIS, Passive sampling, Steroid hormones, Waste water, Water monitoring,
- MeSH
- Water Pollutants, Chemical analysis MeSH
- Estrogens analysis MeSH
- Calibration MeSH
- Estradiol Congeners analysis MeSH
- Environmental Monitoring instrumentation MeSH
- Wastewater analysis MeSH
- Publication type
- Journal Article MeSH
- Names of Substances
- Water Pollutants, Chemical MeSH
- Estrogens MeSH
- Estradiol Congeners MeSH
- Waste Water MeSH
Aquaculture is increasing at the global scale, and beneficial reuse of wastewater is becoming crucial in some regions. Here we selected a unique tertiary treatment system for study over a one-year period. This experimental ecosystem-based approach to effluent management included a treated wastewater pond (TWP), which receives 100% effluent from a wastewater treatment plant, and an aquaculture pond (AP) that receives treated water from the TWP for fish production. We examined the fate of a wide range of pharmaceutically active compounds (PhACs) in this TWP-AP system and a control pond fed by river water using traditional grab sampling and passive samplers. We then employed probabilistic approaches to examine exposure hazards. Telmisartan, carbamazepine, diclofenac and venlafaxine, exceeded ecotoxicological predicted no effect concentrations in influent wastewater to the TWP, but these water quality hazards were consistently reduced following treatment in the TWP-AP system. In addition, both grab and passive sampling approaches resulted in similar occurrence patterns of studied compounds, which highlights the potential of POCIS use for water monitoring. Based on the approach taken here, the TWP-AP system appears useful as a tertiary treatment step to reduce PhACs and decrease ecotoxicological and antibiotic resistance water quality hazards prior to beneficial reuse in aquaculture.
- Keywords
- Biological pond, POCIS, Pharmaceutical fate, Probabilistic hazard assessment, Tertiary treatment,
- MeSH
- Water Pollutants, Chemical * analysis toxicity MeSH
- Ecosystem MeSH
- Pharmaceutical Preparations * MeSH
- Environmental Monitoring MeSH
- Wastewater analysis MeSH
- Ponds MeSH
- Water MeSH
- Aquaculture MeSH
- Animals MeSH
- Check Tag
- Animals MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Names of Substances
- Water Pollutants, Chemical * MeSH
- Pharmaceutical Preparations * MeSH
- Waste Water MeSH
- Water MeSH
The concentrations of seven perfluoroalkyl substances (PFASs) were investigated in 36 European chub (Squalius cephalus) individuals from six localities in the Czech Republic. Chub muscle and liver tissue were analysed at all sampling sites. In addition, analyses of 16 target PFASs were performed in Polar Organic Chemical Integrative Samplers (POCISs) deployed in the water at the same sampling sites. We evaluated the possibility of using passive samplers as a standardized method for monitoring PFAS contamination in aquatic environments and the mutual relationships between determined concentrations. Only perfluorooctane sulphonate was above the LOQ in fish muscle samples and 52% of the analysed fish individuals exceeded the Environmental Quality Standard for water biota. Fish muscle concentration is also particularly important for risk assessment of fish consumers. The comparison of fish tissue results with published data showed the similarity of the Czech results with those found in Germany and France. However, fish liver analysis and the passive sampling approach resulted in different fish exposure scenarios. The total concentration of PFASs in fish liver tissue was strongly correlated with POCIS data, but pollutant patterns differed between these two matrices. The differences could be attributed to the metabolic activity of the living organism. In addition to providing a different view regarding the real PFAS cocktail to which the fish are exposed, POCISs fulfil the Three Rs strategy (replacement, reduction, and refinement) in animal testing.
- Keywords
- Biomonitoring, European chub, Liver, Muscle, PFOS, POCIS,
- MeSH
- Water Pollutants, Chemical analysis MeSH
- Cyprinidae metabolism MeSH
- Fluorocarbons analysis MeSH
- Liver chemistry MeSH
- Alkanesulfonic Acids analysis MeSH
- Environmental Monitoring methods MeSH
- Muscles chemistry MeSH
- Animals MeSH
- Check Tag
- Animals MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Geographicals
- Czech Republic MeSH
- Names of Substances
- Water Pollutants, Chemical MeSH
- Fluorocarbons MeSH
- Alkanesulfonic Acids MeSH
