Polar Organic Chemical Integrative Sampler Sampling Research Articles

Comparison of chemical contaminant measurements using CLAM, POCIS, and silicone band samplers in estuarine mesocosms.

Discrete water samples represent a snapshot of conditions at a particular moment in time and may not represent a true chemical exposure caused by changes in chemical input, tide, flow, and precipitation. Sampling technologies have been engineered to better estimate time-weighted concentrations. In this study, we consider the utility of three integrative sampling platforms: polar organic chemical integrative sampler (POCIS), silicone bands (SBs), and continuous, low-level aquatic monitoring (CLAM). This experiment used simulated southeastern salt marsh mesocosm systems to evaluate the response of passive (POCIS, SBs) and active sampling (CLAM) devices along with discrete sampling methodologies. Three systems were assigned to each passive sampler technology. Initially, all tanks were dosed at nominal (low) bifenthrin, pyrene, and triclosan concentrations of 0.02, 2.2, and 100 µg/L, respectively. After 28 days, the same treatment systems were dosed a second time (high) with bifenthrin, pyrene, and triclosan at 0.08, 8.8, and 200 µg/L, respectively. For passive samplers, estimated water concentrations were calculated using published or laboratory-derived sampling rate constants. Chemical residues measured from SBs resulted in high/low ratios of approximately 2x, approximately 3x, and 1x for bifenthrin, pyrene, and triclosan. A similar pattern was calculated using data from POCIS samples (~4x, ~3x, ~1x). Results from this study will help users of CLAM, POCIS, and SB data to better evaluate water concentrations from sampling events that are integrated across time. Integr Environ Assess Manag 2024;20:1384-1395. © 2024 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Implications of polar organic chemical integrative sampler for high membrane sorption and suitability of polyethersulfone as a single-phase sampler

Polar organic chemical integrative sampler (POCIS) contains sorbent, which is typically enclosed between two polyethersulfones (PES) membranes. A significant PES uptake is reported for many contaminants, yet, aqueous concentration is mainly correlated with the sorbent uptake using first-order kinetics. Under high PES sorption, the first-order kinetics often provide erroneous sampling rate for the sorbent phase due to increased membrane resistance. This work evaluated the uptake of four high PES sorbing chemicals, i.e., three Cl- and CH3-substituted nitrobenzenes and one chlorinated aniline using POCIS and the potential of a single-phase PES sampler using laboratory experiments. POCIS calibration results demonstrated that both sorbent and membrane had similar affinity for the target compounds. A rapid PES sorption occurred in the earlier days (<7 days) followed by a gradual increase in the PES phase concentration (equilibrium not achieved after 60 days). Especially, the membrane was the primary sink for 3,4-dichloroaniline and 3,4-dichloronitrobenzene for up to 14 and 31 days, respectively. On the other hand, the single-phase PES sampler showed similar mass uptake as POCIS and reached equilibrium within 19 days under static condition, indicating its potential suitability in the equilibrium regime. PES-water partition coefficient of the target compounds was between 1.2 and 6.5 L/g. Finally, we present a poly-parameter linear-free energy relationship (pp-LFER) using published data to predict the PES-water partition coefficients. The pp-LFER models showed moderate predictability as indicated by R2adj values between 0.7 and 0.9 for both internal and external data set consisting of a wide range of hydrophobic and hydrophilic compounds (−0.1 ≤ logKOW ≤ 7.4). The proposed pp-LFER model can be used to screen high PES-sorbing chemicals to increase the reliability and accuracy of aqueous concentration prediction from POCIS sampling and to select the most appropriate sampling approach for new compounds.

Semi-continuous pharmaceutical and human tracer monitoring by POCIS sampling at the watershed-scale in an agricultural rural headwater river.

Pharmaceutical monitoring (37 pharmaceuticals and 3 human tracers) was conducted in a headwater streams in southwest France, an area characterized by a low population density with an elderly population (30% > 60 years old) and extensive agriculture (cow cattle breeding). Polar Organic Chemical Integrative Sampler (POCIS) were exposed for 14-day consecutive periods in 2016 at three sampling points. Three human wastewater tracers and 20 pharmaceuticals commonly used for human and/or cattle were quantified in headwaters. Succession of small Wastewater Treatment Plant (WWTP), non-collective sanitation, discharges of untreated effluents as well as the river ability to dilute discharged wastewater, mainly explain the pharmaceuticals and human tracers concentrations. Pharmaceutical loads were time-dependent and were higher during cold season due to increase of pharmaceutical consumption. In contrast, better degradation and/or sorption onto river biofilms in warm season induced the decrease of headwater pharmaceutical content. The headwaters streams were contaminated by compounds found in other type of watershed, but β-blocker were the compounds quantified in higher concentration with frequencies of 100%, which was consistent with the elderly population living in the watershed. Specific compounds (sulfamerazine and sulfamethoxazole) used to cattle medical care were detected in waters, but at a low content.

Can POCIS be used in Water Framework Directive (2000/60/EC) monitoring networks? A study focusing on pesticides in a French agricultural watershed

In this study, the main current limitations in the application of the Polar Organic Chemical Integrative Sampler (POCIS) in regulatory monitoring programmes were evaluated. POCIS were exposed from March to December by successive periods of 14days in the River Trec (Lot et Garonne, France) and analysed for 34 pesticides. The study of the uncertainty related to the POCIS data was performed and we concluded that it might be up to 138%, which is higher than European Union requirements but this issue was adequately counterbalanced by the gain of temporal representativeness. Comparison with data from the official monitoring programme from the French Water Agency showed that the POCIS is already suitable for both operational and investigative monitoring. The sampled fraction issue, and then compliance with Environmental Quality Standards, was also addressed. It was confirmed that POCIS samples only the dissolved fraction of dimethenamid and showed that for compounds like atrazine, desethylatrazine and metolachlor, the POCIS concentration is equivalent to the whole water concentration. For dimethenamid, which exhibited a tendency to adsorb on suspended matter, a method was suggested to assess the raw water concentration from the POCIS measure. Finally, an innovative procedure for using passive sampler data for compliance checks in the framework of surveillance monitoring is proposed.

Environmental occurrence and reproductive effects of the pharmaceutical fluoxetine in native freshwater mussels

The present study measured the occurrence, distribution, and bioaccumulation of fluoxetine in samples of water, polar organic chemical integrative sampler (POCIS), sediment, and caged freshwater mussels at stream sites near a municipal wastewater treatment facility effluent discharge. We assessed the relation of the environmental concentrations to reproductive endpoints in mussels in acute laboratory tests. Concentrations of fluoxetine in water and POCIS samples were similar (<20% difference) within each site and were greatest in the effluent channel (104-119 ng/L), and decreased at 50 m and 100 m downstream. Likewise, concentrations of fluoxetine in sediment and mussel (Elliptio complanata) tissue were greatest in the effluent channel (17.4 ng/g wet wt for sediment and 79.1 ng/g wet wt for mussels). In 96-h lab tests, fluoxetine significantly induced parturition of nonviable larvae from female E. complanata exposed to 300 microg/L (p = 0.0118) and 3,000 microg/L (p < 0.0001) compared to controls. Fluoxetine exposure at 300 microg/L (p = 0.0075) and 3,000 microg/L (p = 0.0001) also resulted in stimulation of lure display behavior in female Lampsilis fasciola and Lampsilis cardium, respectively. In male E. complanata, 3,000 microg fluoxetine/L significantly induced release of spermatozeugmata during a 48-h exposure. These results suggest that fluoxetine accumulates in mussel tissue and has the potential to disrupt several aspects of reproduction in freshwater mussels, a faunal group recognized as one of the most imperiled in the world. Despite the disparity between measured environmental concentrations of fluoxetine and effects concentrations in our short-term tests with these long-lived animals, additional tests are warranted to evaluate the effects of long-term exposure to environmentally relevant concentrations and critical lifestages (e.g., juveniles).