Polar Organic Chemical Integrative Samplers Research Articles

Novel extraction methods and compound-specific isotope analysis of methoxychlor in environmental water and aquifer slurry samples

Multi-element compound-specific stable isotope analysis (ME-CSIA) allows monitoring the environmental behavior and transformation of most common and persistent contaminants. Recent advancements in analytical techniques have extended the applicability of ME-CSIA to organic micropollutants, including pesticides. Nevertheless, the application of this methodology remains unexplored concerning harmful insecticides such as methoxychlor, a polar organochlorine pesticide usually detected in soil and groundwater. This study introduces methods for dual carbon and chlorine compound-specific stable isotope analysis (δ13C-CSIA and δ37Cl-CSIA) of both methoxychlor and its metabolite, methoxychlor olefin, with a sensitivity down to 10 and 100 mg/L, and a precision lower than 0.3 and 0.5 ‰ for carbon and chlorine CSIA, respectively. Additionally, three extraction and preconcentration techniques suitable for ME-CSIA of the target pesticides at environmentally relevant concentrations were also developed. Solid-phase extraction (SPE) and liquid-solid extraction (LSE) effectively extracted methoxychlor (107 ± 27 % and 87 ± 13 %, respectively) and its metabolite (91 ± 27 % and 106 ± 14 %, respectively) from water and aquifer slurry samples, respectively, with high accuracy (Δδ13C and Δδ37Cl ≤ ± 1 ‰). Combining CSIA with polar organic chemical integrative samplers (POCISs) for the extraction of methoxychlor and methoxychlor olefin from water samples resulted in insignificant fractionation for POCIS-CSIA (Δδ13C ≤ ± 1 ‰). A relevant sorption of methoxychlor was detected within the polyethersulfones membranes of the POCISs resulting in temporary carbon isotope fractionation depending on the sorbed mass fraction during the first deployment days. This highlights the critical role of the interactions of polar analytes with POCIS sorbents and membranes in the performance of this method. Altogether, this study proposes a proof of concept for ME-CSIA of methoxychlor and its metabolites, opening the door for future investigations of their sources and transformation processes in contaminated sites.

Identification of hot spots and co-occurrence patterns of activities on thyroid hormone receptor and transthyretin binding in passive samplers from Czech surface waters

One of the less studied in vitro biological activities in the aquatic environment are thyroid hormone receptor beta (TRβ)-mediated agonistic and antagonistic activities and transthyretin (TTR) binding activity. They were measured mostly using active sampling methods, but rarely found. It is unclear if these activities co-occur, and the drivers of the (anti-)TRβ activity are mostly unknown. Therefore, the main aim of the study was to determine (anti-)TRβ activities as well as transthyretin (TTR) binding activity in passive samplers from Czech surface waters in combination with the search for the effect drivers based on liquid chromatography-high resolution mass spectrometry (LC-HRMS) analysis by applying suspect screening. Passive samplers (polar organic chemical integrative samplers, POCIS) were deployed at twenty-one sites (all ends of watersheds and other important sites in Elbe River) in the Czech rivers. The (anti-)TRβ and TTR binding activity were measured using (anti-)TRβ-CALUX and TTR-TRβ-CALUX bioassays. Anti-TRβ activity was found at eight sites, and TTR binding activity co-occurred there at six of these sites. The co-occurrence of TRβ-mediated antagonistic activity and TTR binding indicate that they may have common effect drivers. No sample exhibited TRβ agonistic activity. The extract from the site Bílina River, the most burdened with anti-TRβ activity, was further successfully fractionated, and this activity was revealed in the fraction, where mid-polar compounds prevailed. However, the suspect LC-HRMS analysis did not reveal the chemical effect drivers. Our results showed that anti-TRβ activity can be found in surface waters by employing passive sampling and frequently co-occurs with TTR binding activity. Overall, the fractionation procedure and non-target data acquisition used in this study can serve as a basis for searching the effect drivers in future research.

Ongoing Laboratory Performance Study on Chemical Analysis of Hydrophobic and Hydrophilic Compounds in Three Aquatic Passive Samplers.

The quality of chemical analysis is an important aspect of passive sampling-based environmental assessments. The present study reports on a proficiency testing program for the chemical analysis of hydrophobic organic compounds in silicone and low-density polyethylene (LDPE) passive samplers and hydrophilic compounds in polar organic chemical integrative samplers. The median between-laboratory coefficients of variation (CVs) of hydrophobic compound concentrations in the polymer phase were 33% (silicone) and 38% (LDPE), similar to the CVs obtained in four earlier rounds of this program. The median CV over all rounds was 32%. Much higher variabilities were observed for hydrophilic compound concentrations in the sorbent: 50% for the untransformed data and a factor of 1.6 after log transformation. Limiting the data to the best performing laboratories did not result in less variability. Data quality for hydrophilic compounds was only weakly related to the use of structurally identical internal standards and was unrelated to the choice of extraction solvent and extraction time. Standard deviations of the aqueous concentration estimates for hydrophobic compound sampling by the best performing laboratories were 0.21 log units for silicone and 0.27 log units for LDPE (factors of 1.6 to 1.9). The implications are that proficiency testing programs may give more realistic estimates of uncertainties in chemical analysis than within-laboratory quality control programs and that these high uncertainties should be taken into account in environmental assessments.

Wastewater and seawater monitoring in Antarctica: Passive sampling as a powerful strategy to evaluate emerging pollution

The Ross Sea, among the least human-impacted marine environments worldwide, recently became the first marine protected area in Antarctica.To assess the impact of the Italian research station Mario Zucchelli (MZS) on the surrounding waters, passive sampling – as well as spot sampling for comparison – took place in the effluent of the wastewater treatment plant (WWTP) and the receiving surface marine waters. Polar Organic Chemical Integrative Samplers (POCIS) were deployed for six consecutive 2-week periods from November to February in a reservoir collecting the wastewater effluent. Passive samplers were also deployed at shallow depth offshore from the wastewater effluent outlet from MZS for two separate 3-week periods (November 2021 and January 2022). Grab water samples were collected alongside each POCIS deployment, for comparison with passive sampling results.POCIS, used for the first time in Antarctica, demonstrated to be advantageous to estimate time-averaged concentrations in waters and the results were comparable to those obtained by repeated spot samplings. Among the 23 studied ECs – including drugs, UV-filters, perfluorinated substances, caffeine – 15 were detected in both grab and passive sampling in the WWTP effluent and followed similar concentration profiles in both types of sampling. High concentrations of caffeine, naproxen and ketoprofen in the dozens of μg L−1 were detected. Other compounds, including drugs and several UV filters, were detected down to sub- μg L−1 concentrations. In marine waters close to the effluent output, only traces of a drug (4.8 ng L−1) and two UV filters (up to 0.04 μg L−1) were quantified.

Pharmaceutical and pesticide mixtures in a Mediterranean coastal wetland: comparison of sampling methods, ecological risks, and removal by a constructed wetland

Pharmaceuticals and pesticides can be considered hazardous compounds for Mediterranean coastal wetland ecosystems. Although many of these compounds co-occur in environmental samples, only a few studies have been dedicated to assessing the ecotoxicological risks of complex contaminant mixtures. We evaluated the occurrence of 133 pharmaceuticals and pesticides in 12 sites in a protected Mediterranean wetland, the Albufera Natural Park (ANP), based on conventional grab sampling and polar organic chemical integrative samplers (POCIS). We assessed acute and chronic ecological risks posed by these contaminant mixtures using the multi-substance Potentially Affected Fraction (msPAF) approach and investigated the capacity of a constructed wetland to reduce chemical exposure and risks. This study shows that pharmaceuticals and pesticides are widespread contaminants in the ANP, with samples containing up to 75 different compounds. POCIS samplers were found to be useful for the determination of less predictable exposure profiles of pesticides occurring at the end of the rice cultivation cycle, while POCIS and grab samples provide an accurate method to determine (semi-)continuous pharmaceutical exposure. Acute risks were identified in one sample, while chronic risks were determined in most of the collected samples, with 5–25% of aquatic species being potentially affected. The compounds that contributed to the chronic risks were azoxystrobin, ibuprofen, furosemide, caffeine, and some insecticides (diazinon, imidacloprid, and acetamiprid). The evaluated constructed wetland reduced contaminant loads by 45–73% and reduced the faction of species affected from 25 to 6%. Our study highlights the need of addressing contaminant mixture effects in Mediterranean wetlands and supports the use of constructed wetlands to reduce contaminant loads and risks in areas with high anthropogenic pressure.

De facto Water Reuse: Investigating the Fate and Transport of Chemicals of Emerging Concern from Wastewater Discharge through Drinking Water Treatment Using Non-targeted Analysis and Suspect Screening.

Wastewater is a source for many contaminants of emerging concern (CECs), and surface waters receiving wastewater discharge often serve as source water for downstream drinking water treatment plants. Nontargeted analysis and suspect screening methods were used to characterize chemicals in residence-time-weighted grab samples and companion polar organic chemical integrative samplers (POCIS) collected on three separate hydrologic sampling events along a surface water flow path representative of de facto water reuse. The goal of this work was to examine the fate of CECs along the study flow path as water is transported from wastewater effluent through drinking water treatment. Grab and POCIS samples provided a comparison between residence-time-weighted single-point and integrative sample results. This unique and rigorous study design, coupled with advanced analytical chemistry tools, provided important insights into chemicals found in drinking water and their potential sources, which can be used to help prioritize chemicals for further study. K-means clustering analysis was used to identify patterns in chemical occurrences across both sampling sites and sampling events. Chemical features that occurred frequently or survived drinking water treatment were prioritized for identification, resulting in the probable identification of over 100 CECs in the watershed and 28 CECs in treated drinking water.

Polar Organic Chemical Integrative Sampler to Predict Changes in Bioavailability of Oxytetracycline and Sulfamethoxazole from Soil

Polar Organic Chemical Integrative Sampler to Predict Changes in Bioavailability of Oxytetracycline and Sulfamethoxazole from Soil

Proposal of a new empirical model with flow velocity to improve time-weighted average concentration estimates from the Polar Organic Chemical Integrative Samplers

It is now widely recognized that the sampling rate of Polar Organic Chemical Integrative Samplers (POCIS) is significantly affected by flow velocity, which can cause a consequent bias when determining time-weighted average concentrations (TWAC). We already observed the desorption of deisopropylatrazine (DIA) over time when added to the receiving phase of a POCIS. This desorption rate was particularly influenced by flow velocity, in an agitated water environment in situ. In the method presented here, we calibrated 30 pesticides under controlled laboratory conditions, varying the flow velocity over four levels. We simultaneously studied the desorption rate of DIA-d5 (a deuterated form of DIA) over time. An empirical model based on a power law involving flow velocity was used to process the information from the accumulation kinetics of the compounds of interest and elimination of DIA-d5. This type of model makes it possible to consider the effect of this crucial factor on exchange kinetics, and then to obtain more accurate TWACs with reduced bias and more acceptable dispersion of results.

Combined pollution characteristics and ecological risks of multi-pollutants in Poyang Lake

Poyang Lake, the largest freshwater lake in China, faced severe ecological degradation in the past decade. Combined pollution of multi-pollutants may be one of the contributing factors. However, the characteristics of combined pollution and the ecological risks are still not clear. In this study, we used Polar Organic Chemical Integrative Sampler (POCIS), In Situ Bioassay Passive Sampling Device (ISBPSD) and conventional sampling methods, to study the toxic pollutants levels and the combined biological toxicity effects. The results showed that high levels of organochlorine pesticides (OCPs, averaged 162 ng/g) and polycyclic musk (PCM, averaged 53.6 ng/g) residues, as well as some metals such as nickel (Ni), lead (Pb) concentrations exceeded the relevant standard level in the sediment. The risk of combined pollution in the water was relatively low, but high risk was found in the sediments. According to the ISBPSD studies, the survival rates of species in the water and sediments were only 10.0–45.0% and 1.67–11.7% respectively, which was much lower than that reported in other typical basins of China. OCPs, PCMs, and certain metals such as Pb and Ni may be the key toxic pollutants causing biological toxicity effects in Poyang Lake.

Performance comparison of three passive samplers for monitoring of polar organic contaminants in treated municipal wastewater

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.

Risk assessment of a Brazilian urban population due to the exposure to pyrethroid insecticides during the COVID-19 pandemic using wastewater-based epidemiology

Pyrethroids are synthetic insecticides commonly used in agriculture and homes due to their low toxicity to mammals and effectiveness at low doses. However, exposure to pyrethroids can cause various symptoms, depending on the route of exposure. To measure human exposure to pyrethroids, researchers used wastewater-based epidemiology (WBE) with polar organic chemical integrative samplers (POCIS) sampling. This approach is a cost-effective and efficient way to assess exposure to pyrethroids. The study aimed to evaluate the exposure of an urban population in Brazil to pyrethroids during the COVID-19 pandemic using WBE with POCIS sampling. Researchers analyzed 3-phenoxybenzoic acid (3-PBA) in wastewater using passive sampling with POCIS, which was extracted with methanol and analyzed using UPLC-MS/MS. The range of CTWA concentrations of 3-PBA in wastewater was 24.3–298.2 ng L−1, with a mean value of 134 ± 76.5 ng L−1. The values were used to estimate the exposure of the population to pyrethroid insecticides. Three different conversion factors were applied to determine the range of exposure to at least 20 different pyrethroid insecticides. The exposure values ranged from 18.08 to 1441.49 mg day−1 per 1000 inhabitants. The toxicological risk posed to the exposed population was evaluated by calculating the WBE toxicological level (WBE-TL). Lambda-cyhalothrin was used as a reference for risk assessment, and the WBE-TL values for lambda-cyhalothrin ranged from 0.5 to 8.29 (considering the high CF). We compared mobility trends to 3-PBA exposure during the COVID-19 pandemic. The study highlighted the effectiveness of POCIS sampling in WBE and provided useful information for policymakers and regulatory agencies. POCIS sampling has practical advantages, including analyte pre-concentration, low operational cost, and ease of use. Overall, the study shows the importance of monitoring and understanding the exposure of the population to pyrethroid insecticides, especially during the pandemic when people may be spending more time at home.

Compatibility of polar organic chemical integrative sampler (POCIS) with compound specific isotope analysis (CSIA) of substituted chlorobenzenes

Compound specific isotope analysis (CSIA) is a powerful technique to demonstrate in situ degradation of traditional groundwater contaminants when concentrations are typically in the mg/L range. Currently, an efficient preconcentration method is lacking to expand CSIA to low aqueous concentration environmental samples. Specially for the H- and N-CSIA of heteroatom-bearing non-traditional compounds, the CSIA analytical detection limits are significantly higher than that of the C-CSIA. This work demonstrates the compatibility of polar organic chemical integrative sampler (POCIS) with C-, H-, and N-CSIA using four nitro- and amino-substituted chlorobenzenes that are common industrial feedstocks for numerous applications and are commonly detected in the environment at mg/L to μg/L range. Using lab experiments, we showed isotopic equilibrium in POCIS was achieved after 30 days with either a negligible (<0.5 ‰) or a constant shift for C (<1 ‰) and N (<2 ‰). Similar negligible (<5 ‰) or constant shift (<20 ‰) was evident for H isotope except for 3,4-dichloroaniline. The method quantification limits for the combined sorbent and membrane of one POCIS were comparable to that of the solid phase extraction (SPE) using 10 L water. Next, we demonstrated the field applicability of POCIS for C- and N-CSIA after a 60-day deployment in a pilot constructed wetland by showing <1 ‰ difference between the δ13C and δ15N obtained from POCIS and SPE. Finally, we evaluated whether the biofilm development on POCIS membrane could affect the isotope signature of the sampled compounds during field deployment. Although a diverse microbial community was identified on the membrane after a 60-day deployment, we did not observe significant isotope fractionation. This was likely due to either slower diffusion in the biofilm or microbial degradation of the sampled compounds. This work demonstrates the potential of using POCIS-CSIA as a simple, fast, and sensitive method for low-concentration contaminants, such as pesticides, pharmaceuticals, and flame-retardants.

Development of ceramic membranes with controllable PFAS mass transfer for passive sampling applications

Polar organic chemical integrative sampler (POCIS) represents a promising passive sampling approach for the monitoring of per- and polyfluoroalkyl substances (PFAS) in water. However, the use of polymer membranes has limited the long-term application of conventional POCIS in the field. This work aimed to develop ceramic membranes with controllable PFAS diffusion and mass transfer suitable for PFAS passive sampling applications. Our results showed that PFAS diffusion through ceramic membranes was strongly dependent on membrane structures and properties, particularly membrane porosity. Through controlling membrane fabrication conditions, including particle size and morphology of the membrane material and sintering temperature, ceramic membranes with a range of PFAS diffusivities and mass transfer rates were obtained that varied by over two orders of magnitude, which substantially expanded the limits of polyethersulfone (PES) membranes. Further, modification of ceramic membranes with a thin TiO2 layer did not influence the PFAS mass transfer. Integrative passive samplers consisting of ceramic membranes and a sorbent receiving phase were then developed and assessed through calibration studies. The passive samplers showed linear uptake of PFAS over an extended period of time up to 25 days, and the PFAS sampling rates were affected by both the type of ceramic membranes and the PFAS structures. Results of this study demonstrated the proof-of-concept of the use of ceramic membranes in PFAS passive sampling applications.

Tracing the attenuation of fipronil and its transformation products from a rice paddy field to receiving rivers using polar organic chemical integrative samplers

Irrational use of fipronil for rice pest control often occurred, resulting in high concentrations of fipronil and its transformation products (TPs) (collectively termed fiproles) in aquatic sediment, calling for a better understanding of the migration and transformation of fipronil in surface water as well as efficient methods for source identification. Herein, the fate and transport of fiproles from a paddy field to receiving rivers were assessed in Poyang Lake basin, Jiangxi, China using polar organic chemical integrative samplers with mixed-mode adsorbents (POCIS-MMA). Average concentrations of fiproles in water were 6.16 ± 6.32 ng/L, with median, minimum, and maximum values being 2.99 ± 0.67, 0.40 ± 0.08, and 18.6 ± 3.1 ng/L, respectively. In all samples, over half of fiproles (55.9 %–90.8 %) presented in the form of TPs and fipronil desulfinyl was the dominant TP. Two approaches were applied for source identification, including the change of molar concentration ratios of fipronil to its TPs and the relative attenuation values of fiproles normalized to a reference compound (acetamiprid) that was stable in aquatic environment. While the paddy field upstream was the main source of waterborne fiproles, additional input sources in the downstream region were identified. The present study indicated that the combination of attenuation of molar concentration ratios of micro-pollutants to their respective TPs and relative attenuation values of micro-pollutants' concentrations normalized to a reference compound measured by POCIS is an effective means to study the migration and transformation of micro-pollutants in field.

Analysis of a Passive Sampling Device to Assess the Behavior of Per- and Polyfluoroalkyl Substances in Sediments.

Per- and polyfluoroalkyl substances (PFAS) are an emerging class of compounds that cause health and environmental problems worldwide. In aquatic environments, PFAS may bioaccumulate in sediment organisms, which can affect the health of organisms and ecosystems. As such, it is important to develop tools to understand their bioaccumulation potential. In the present study, the uptake of perfluorooctanoic acid (PFOA) and perfluorobutane sulfonic acid (PFBS) from sediments and water was assessed using a modified polar organic chemical integrative sampler (POCIS) as a passive sampler. While POCIS has previously been used to measure time-weighted concentrations of PFAS and other compounds in water, in our study, the design was adapted for analyzing contaminant uptake and porewater concentrations in sediments. The samplers were deployed into seven different tanks containing PFAS-spiked conditions and monitored over 28 days. One tank contained only water with PFOA and PFBS, three tanks contained soil with 4% organic matter, and three tanks contained soil combusted at 550 °C to minimize the influence of labile organic carbon. The uptake of PFAS from the water was consistent with previous research using a sampling rate model or simple linear uptake. For the samplers placed in the sediment, the uptake process was explained well using a mass transport based on the external resistance from the sediment layer. Uptake of PFOS in the samplers occurred faster than that of PFOA and was more rapid in the tanks containing the combusted soil. A small degree of competition was observed between the two compounds for the resin, although these effects are unlikely to be significant at environmentally relevant concentrations. The external mass transport model provides a mechanism to extend the POCIS design for measuring porewater concentrations and sampling releases from sediments. This approach may be useful for environmental regulators and stakeholders involved in PFAS remediation. Environ Toxicol Chem 2023;00:1-13. © 2023 SETAC.

Examining the applicability of polar organic chemical integrative sampler for long-term monitoring of groundwater contamination caused by currently used pesticides

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.

Uptake of Per- and Polyfluoroalkyl Substances by Fish, Mussel, and Passive Samplers in Mobile-Laboratory Exposures Using Groundwater from a Contamination Plume at a Historical Fire Training Area, Cape Cod, Massachusetts.

Aqueous film-forming foams historically were used during fire training activities on Joint Base Cape Cod, Massachusetts, and created an extensive per- and polyfluoroalkyl substances (PFAS) groundwater contamination plume. The potential for PFAS bioconcentration from exposure to the contaminated groundwater, which discharges to surface water bodies, was assessed with mobile-laboratory experiments using groundwater from the contamination plume and a nearby reference location. The on-site continuous-flow 21-day exposures used male and female fathead minnows, freshwater mussels, polar organic chemical integrative samplers (POCIS), and polyethylene tube samplers (PETS) to evaluate biotic and abiotic uptake. The composition of the PFAS-contaminated groundwater was complex and 9 PFAS were detected in the reference groundwater and 17 PFAS were detected in the contaminated groundwater. The summed PFAS concentrations ranged from 120 to 140 ng L-1 in reference groundwater and 6100 to 15,000 ng L-1 in contaminated groundwater. Biotic concentration factors (CFb) for individual PFAS were species, sex, source, and compound-specific and ranged from 2.9 to 1000 L kg-1 in whole-body male fish exposed to contaminated groundwater for 21 days. The fish and mussel CFb generally increased with increasing fluorocarbon chain length and were greater for sulfonates than for carboxylates. The exception was perfluorohexane sulfonate, which deviated from the linear trend and had a 10-fold difference in CFb between sites, possibly because of biotransformation of precursors such as perfluorohexane sulfonamide. Uptake for most PFAS in male fish was linear over time, whereas female fish had bilinear uptake indicated by an initial increase in tissue concentrations followed by a decrease. Uptake of PFAS was less for mussels (maximum CFb = 200) than for fish, and mussel uptake of most PFAS also was bilinear. Although abiotic concentration factors were greater than CFb, and values for POCIS were greater than for PETS, passive samplers were useful for assessing PFAS that potentially bioconcentrate in fish but are present at concentrations below method quantitation limits in water. Passive samplers also accumulate short-chain PFAS that are not bioconcentrated.

Determination of the pyrethroid inseticide metabolite 3-phenoxybenzoic acid in wastewater using polar organic integrative samplers and LC-MS/MS analysis

Wastewater-based epidemiology (WBE) is a methodological approach that aims to obtain epidemiological information through wastewater analysis, by identifying endogenous metabolism products. Pyrethroid insecticides are commonly used but just a few studies evaluated concentrations of pyrethroid metabolites in wastewater. A cost-effective and efficient sampling strategy for WBE studies is the use of polar organic chemical integrative samplers (POCIS). This study aimed to develop and evaluate a method for estimating the concentration of the pyrethroid insecticide 3-phenoxybenzoic acid (3-PBA) using POCIS sampling and liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. The sampler sorbent was extracted with methanol, followed by a double solid phase extraction (SPE) clean-up. The extraction procedure had yields in the range of 95.7–100.4 %. There were 27 collection cycles, with POCIS samplers changed every 14 days. The analyte 3-PBA was measured in all collections. The concentration of 3-PBA in the POCIS sorbent was 208.6–2456.9 ng g−1. The sampling rate was 0.096 L/day and the resulting estimated concentration in wastewater was 24.3 to 335.2 ng/L. This is the first study evaluating POCIS sampling to measure a pyrethroid metabolite in water or wastewater samples.

Mass transfer characteristics of chiral pharmaceuticals on membrane used for polar organic chemical integrative sampler

Passive sampling technology has good application prospects for monitoring trace pollutants in aquatic environments. Further research on the sampling mechanism of this technology is essential to improve the measurement accuracy and extend the application scope of this approach. In this study, adsorption and permeation experiments were performed to investigate the sorption and mass transfer properties of five chiral pharmaceuticals at the enantiomeric level on polyethersulfone (PES) and polytetrafluoroethylene (PTFE) membranes used in a polar organic chemical integrative sampler. Batch adsorption experiments showed that the PES membrane had an adsorption phenomenon for most selected pollutants and an insignificant sorption behavior was observed for all selected pharmaceuticals on the PTFE membrane except for R(S)-fluoxetine. The diffusion coefficients of selected pharmaceuticals onto the PTFE membrane were approximately one order of magnitude higher than those onto the PES membrane. The permeation experiment indicated that under different hydraulic conditions, the change of the relative pollutant concentration through the PTFE membrane for the composite pollutant system was more obvious than that for the single pollutant system, and mass transfer hysteresis exists for both contaminant systems through PES membranes. Using the first-order equation or 3-component model to estimate the overall mass transfer coefficients, the results showed that the overall mass transfer coefficient values of pollutants in the composite pollutant system onto both membranes were higher than those in the single pollutant system. This parameter was mainly influenced by the synergistic effects of the multi-analyte interaction and diminished water boundary layers during the mass transfer process.

Interest of a new large diffusive gradients in thin films (L-DGT) for organic compounds monitoring: On-field comparison with conventional passive samplers

In this work, the performances of a Large Diffusive Gradients in Thin films (L-DGT, i.e., a DGT based on a Chemcatcher® holder with a 5-fold larger sampling area) were compared on-field with the conventional DGT and the Polar Organic Chemical Integrative Sampler (POCIS) for the monitoring of a wide range of organic contaminants (i.e., 65 pesticides and metabolites, 53 pharmaceuticals and 12 hormones). These three passive samplers were simultaneously deployed in four rivers during 14 days. Their performances were then evaluated according to their detection and quantification capacities and their physical robustness. The results obtained confirm the advantages of the L-DGT over the conventional DGT regarding its sensitivity but also its robustness during field deployment. The POCIS provides the higher sensitivity, allowing the detection of more organic compounds compared to the DGT and, to a lesser extent, the L-DGT. However, both L-DGT and DGT reduces the uncertainty on the determination of the time-weighted average concentrations (CW), mainly due to the narrow range of variation of their calibration parameters. Indeed, for a given compound, CW can vary up to only a 3-fold factor with DGT and L-DGT compared to a 2 to 10-fold factor (up to 50) with POCIS. Thus, the L-DGT appears to be more suitable than DGT in low-contaminated contexts, which require higher sensitivity, or than POCIS when a CW determination is needed. For a qualitative evaluation however, the POCIS remains the most suitable passive sampler.