Performance Reference Compounds Research Articles

Measuring bioavailable PAHs in estuarine water using semipermeable membrane devices with performance reference compounds

Bioavailable polycyclic aromatic hydrocarbon (PAH) concentrations in the estuarine water of Kaohsiung Harbor were measured using XAD-2 resin and semipermeable membrane devices (SPMDs) calibrated with performance reference compounds (PRCs). The sum of the PAH concentrations from XAD-2 resin (Cw) in the surface and bottom water samples was 6.63 and 9.58ngL−1, respectively. The variation in PAHs was higher in surface water. Cubic polynomial regressions using the sampling rate for five PRCs (Rs-PRC) provided estimated in situ sampling rates (Rs). The turbulent condition in the surface water was important in enhancing Rs; however, diffusion was relevant to the bottom water, which was less turbulent and showed decreasing Rs at high MW PAHs. The sum of the dissolved PAH concentrations estimated with the SPMDs (CSPMD) was 5.87 and 9.15ngL−1 in the surface and bottom water samples, respectively. The surface and bottom water PAHs were derived from different sources.

Internal and external transport significance for predicting contaminant uptake rates in passive samplers

A critical element in the application of passive sampling devices for estimating in situ the concentrations of contaminants in pore water of sediments is predicting the rate of uptake within the device. Herein, we demonstrate the relative importance of internal and external mass transport processes for sampling devices and show that external processes control the kinetics in many instances. As such uptake rates are closely related to the surface area to volume ratio of the sampling device and site-specific transport conditions. Models based on sorption-related molecular diffusion provide an upper bound on equilibrium times. The essential model parameters and corresponding kinetics at a site with more substantial mixing can be inferred using time series of sampler concentrations, concentrations in samplers with different geometry, or concentrations of performance reference compounds.

Passive sampling of nonpolar contaminants at three deep-ocean sites

Concentrations of polychlorinated biphenyls, polyaromatic hydrocarbons, hexachlorobenzene, and DDE were determined by passive sampling (semipermeable membrane devices) with exposure times of 1–1.5 years at 0.1–5 km depth in the Irminger Sea, the Canary Basin (both North Atlantic Ocean), and the Mozambique Channel (Indian Ocean). The dissipation of performance reference compounds revealed a pronounced effect of hydrostatic pressure on the sampler-water partition coefficients. Concentrations in the Irminger Sea were uniform over the entire water column (0.1–3 km). At the Canary Basin site, concentrations were 2–25 times lower near the bottom (5 km) than at 1.4 km. Concentrations in the Mozambique Channel (0.6–2.5 km) were lower than at the other two locations, and showed a near-bottom maximum. The data suggest that advection of surface waters down to a depth of about 1 km is an important mechanism of contaminant transport into the deep ocean.

Effect of water velocity on the uptake of polychlorinated biphenyls (PCBs) by silicone rubber (SR) and low-density polyethylene (LDPE) passive samplers: An assessment of the efficiency of performance reference compounds (PRCs) in river-like flow conditions

One aim of this study is to determine the impact of water velocity on the uptake of indicator polychlorinated biphenyls (iPCBs) by silicone rubber (SR) and low-density polyethylene (LDPE) passive samplers. A second aim is to assess the efficiency of performance reference compounds (PRCs) to correct for the impact of water velocity. SR and LDPE samplers were spiked with 11 or 12 PRCs and exposed for 6weeks to four different velocities (in the range of 1.6 to 37.7cms−1) in river-like flow conditions using a channel system supplied with river water. A relationship between velocity and the uptake was found for each iPCB and enables to determine expected changes in the uptake due to velocity variations. For both samplers, velocity increases from 2 to 10cms−1, 30cms−1 (interpolated data) and 100cms−1 (extrapolated data) lead to increases of the uptake which do not exceed a factor of 2, 3 and 4.5, respectively. Results also showed that the influence of velocity decreased with increasing the octanol–water coefficient partition (logKow) of iPCBs when SR is used whereas the opposite effect was observed for LDPE. Time-weighted average (TWA) concentrations of iPCBs in water were calculated from iPCB uptake and PRC release. These calculations were performed using either a single PRC or all the PRCs. The efficiency of PRCs to correct the impact of velocity was assessed by comparing the TWA concentrations obtained at the four tested velocities. For SR, a good agreement was found among the four TWA concentrations with both methods (average RSD<10%). Also for LDPE, PRCs offered a good correction of the impact of water velocity (average RSD of about 10 to 20%). These results contribute to the process of acceptance of passive sampling in routine regulatory monitoring programs.

Picogram per liter detections of pyrethroids and organophosphates in surface waters using passive sampling

Pyrethroids and organophosphates are among the most toxic insecticides for aquatic organisms, leading to annual-average environmental quality standards (AA-EQS) in the picogram per liter range in surface waters. For monitoring purposes, it is therefore crucial to develop very sensitive analytical methods. Until now, it is very difficult to reach detection limits at or below given AA-EQSs. Here, we present a passive sampling method using silicone rubber (SR) sheets for the sampling of ten pyrethroids and two organophosphates in surface waters. An analytical method was developed, optimized and validated for the extraction of the insecticides from the SR sheets by accelerated solvent extraction followed by clean-up on C18 and silica gel and detection with GC–MS/MS in positive ionization mode. Good precision (<20%) and absolute recovery (>50%) was observed for all substances, accuracy was between 66% and 139%. Limits of detection between 6 and 200 pg/L were achieved for all substances in surface waters using average sampling rates for PCBs and PAHs. The lack of substance-specific sampling rates and missing performance reference compounds led to an uncertainty in the concentration estimation of factor three in both directions. In a large field study, comprising 40 environmental samples from nine Swiss rivers, eight out of 12 substances were detected (most frequently: chlorpyrifos, cypermethrin). Most of the estimated organophosphate concentrations were between 0.1 and 1 ng/L, most pyrethroid detections below 0.1 ng/L. Four substances (chlorpyrifos-methyl, cypermethrin, deltamethrin and lambda-cyhalothrin) showed exceedances of their respective AA-EQS in multiple samples, also when the uncertainties in the concentration estimation were considered. As pyrethroid and organophosphate detection by SR passive sampling is very practicable and allows sensitive analysis, it has the potential to become a new tool in the monitoring of non-polar pesticides.

Validating the use of performance reference compounds in passive samplers to assess porewater concentrations in sediment beds.

Hydrophobic organic compounds (HOCs) like polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) tend to accumulate in sediment beds when they are released into aquatic environments. Due to this buildup of HOCs in the sediment, the highest water concentrations are often in the pore water. Passive samplers can be used in the field (i.e., in situ) to measure freely dissolved porewater concentrations if target contaminants diffusing through the sediment and into the sampler exhibit the same diffusive retardation factors as performance reference compounds (PRCs) that are diffusing out of the sampler and into the sediment. To test this assumption, polyethylene (PE) passive samplers were placed in an organic- and black- carbon-rich sediment bed in the laboratory with samplers removed every 30 days for 4 months. The concentrations of target contaminants in the PE at each time point, corrected using measures of the losses of PRCs, were in good agreement with separately measured equilibrium concentrations in a well-mixed system. Concentrations in the PE passive samplers, normalized by their polyethylene-water partition coefficients, were also in good agreement with directly measured porewater concentrations. Finally, PE-deduced porewater concentrations were compared with the traditional equilibrium partitioning models and showed that considering sorption to only organic carbon substantially overestimated porewater concentrations. However, predictions improved greatly if sorption to black carbon was also considered.

Application of the triolein-embedded cellulose acetate membrane passive sampler for monitoring of polycyclic aromatic hydrocarbons in water.

Triolein-embedded cellulose acetate membrane (TECAM) can be used as a passive sampler to measure hydrophobic organic contaminants in water. Uptake constant rates (k u ) for polycyclic aromatic hydrocarbons (PAHs) by TECAM sampling were measured under different hydrodynamic conditions. The measured k u values were modeled to enable the quantification of time weighed average (TWA) concentrations of PAHs in the field. An empirical relationship that enables the calculation of in situ k u values of chemicals using performance reference compounds (PRCs) was derived and its application was demonstrated in a field study. The results showed that freely dissolved concentrations of hydrophobic organic compounds (HOCs) can be accurately measured in the field using TECAM method based on empirical uptake models calibrated with PRCs.

Polar organic chemical integrative samplers for pesticides monitoring: Impacts of field exposure conditions

This study focuses on how Polar Organic Chemical Integrative Samplers (POCIS) work in real environmental conditions. A selection of 23 polar pesticides and 8 metabolites were investigated by exposure of triplicates of integrative samplers in two rivers in France for successive 14-day periods. The pesticides and metabolites were trapped not only in Oasis HLB sorbent but also in the polyethersulfone (PES) membrane of the POCIS. The distribution of pesticides depended on the molecular structure.The use of the Performance Reference Compound (PRC) is also discussed here. The impact of some environmental parameters and exposure setup on the transfer of pesticides in POCIS sorbent was studied: river flow rate, biofouling on membranes, sampler holding design and position in the stream. Results show a significant impact of river flow velocity on PRC desorption, especially for values higher than 4cm·s−1. Some fouling was observed on the PES membrane which could potentially have an impact on molecule accumulation in the POCIS. Finally, the positioning of the sampler in the river did not have significant effects on pesticide accumulation, when perpendicular exposures were used (sampler positioning in front of the water flow). The POCIS with PRC correction seems to be a suitable tool for estimating time-weighted average (TWA) concentrations, for all the molecules except for one of the nine pesticides analyzed in these two French rivers.

Optimization of the polar organic chemical integrative sampler for the sampling of acidic and polar herbicides

This paper presents an optimization of the pharmaceutical Polar Organic Chemical Integrative Sampler (POCIS-200) under controlled laboratory conditions for the sampling of acidic (2,4-dichlorophenoxyacetic acid (2,4-D), acetochlor ethanesulfonic acid (ESA), acetochlor oxanilic acid, bentazon, dicamba, mesotrione, and metsulfuron) and polar (atrazine, diuron, and desisopropylatrazine) herbicides in water. Indeed, the conventional configuration of the POCIS-200 (46 cm(2) exposure window, 200 mg of Oasis® hydrophilic lipophilic balance (HLB) receiving phase) is not appropriate for the sampling of very polar and acidic compounds because they rapidly reach a thermodynamic equilibrium with the Oasis HLB receiving phase. Thus, we investigated several ways to extend the initial linear accumulation. On the one hand, increasing the mass of sorbent to 600 mg resulted in sampling rates (R s s) twice as high as those observed with 200 mg (e.g., 287 vs. 157 mL day(-1) for acetochlor ESA). Although detection limits could thereby be reduced, most acidic analytes followed a biphasic uptake, proscribing the use of the conventional first-order model and preventing us from estimating time-weighted average concentrations. On the other hand, reducing the exposure window (3.1 vs. 46 cm(2)) allowed linear accumulations of all analytes over 35 days, but R s s were dramatically reduced (e.g., 157 vs. 11 mL day(-1) for acetochlor ESA). Otherwise, the observation of biphasic releases of performance reference compounds (PRC), though mirroring acidic herbicide biphasic uptake, might complicate the implementation of the PRC approach to correct for environmental exposure conditions.

Atrazine contamination at the watershed scale and environmental factors affecting sampling rates of the polar organic chemical integrative sampler (POCIS)

Polar organic chemical integrative samplers (POCIS) were used to estimate atrazine contamination at 24 stream/river sites located across a watershed with land use ranging from 6.7 to 97.4% annual crops and surface water nitrate concentrations ranging from 3 to 5404 μg/L. A gradient of atrazine contamination spanning two orders of magnitude was observed over two POCIS deployments of 28 d and was positively correlated with measures of agricultural intensity. The metabolite desisopropyl atrazine was used as a performance reference compound in field calibration studies. Sampling rates were similar between field sites but differed seasonally. Temperature had a significant effect on sampling rates while other environmental variables, including water velocity, appeared to have no effect on sampling rates. A performance reference compound approach showed potential in evaluating spatial and temporal differences in field sampling rates and as a tool for further understanding processes governing uptake of polar compounds by POCIS.

Calculating the Diffusive Flux of Persistent Organic Pollutants between Sediments and the Water Column on the Palos Verdes Shelf Superfund Site Using Polymeric Passive Samplers

Passive samplers were deployed to the seafloor at a marine Superfund site on the Palos Verdes Shelf, California, USA, and used to determine water concentrations of persistent organic pollutants (POPs) in the surface sediments and near-bottom water. A model of Fickian diffusion across a thin water boundary layer at the sediment-water interface was used to calculate flux of contaminants due to molecular diffusion. Concentrations at four stations were used to calculate the flux of DDE, DDD, DDMU, and selected PCB congeners from sediments to the water column. Three passive sampling materials were compared: PE strips, POM strips, and SPME fibers. Performance reference compounds (PRCs) were used with PE and POM to correct for incomplete equilibration, and the resulting POP concentrations, determined by each material, agreed within 1 order of magnitude. SPME fibers, without PRC corrections, produced values that were generally much lower (1 to 2 orders of magnitude) than those measured using PE and POM, indicating that SPME may not have been fully equilibrated with waters being sampled. In addition, diffusive fluxes measured using PE strips at stations outside of a pilot remedial sand cap area were similar to those measured at a station inside the capped area: 240 to 260 ng cm(-2) y(-1) for p,p'-DDE. The largest diffusive fluxes of POPs were calculated at station 8C, the site where the highest sediment concentrations have been measured in the past, 1100 ng cm(-2) y(-1) for p,p'-DDE.

Passive sampling methods for contaminated sediments: scientific rationale supporting use of freely dissolved concentrations.

Passive sampling methods (PSMs) allow the quantification of the freely dissolved concentration (Cfree) of an organic contaminant even in complex matrices such as sediments. Cfree is directly related to a contaminant's chemical activity, which drives spontaneous processes including diffusive uptake into benthic organisms and exchange with the overlying water column. Consequently, Cfree provides a more relevant dose metric than total sediment concentration. Recent developments in PSMs have significantly improved our ability to reliably measure even very low levels of Cfree. Application of PSMs in sediments is preferably conducted in the equilibrium regime, where freely dissolved concentrations in the sediment are well-linked to the measured concentration in the sampler via analyte-specific partition ratios. The equilibrium condition can then be assured by measuring a time series or a single time point using passive samplers with different surface to volume ratios. Sampling in the kinetic regime is also possible and generally involves the application of performance reference compounds for the calibration. Based on previous research on hydrophobic organic contaminants, it is concluded that Cfree allows a direct assessment of 1) contaminant exchange and equilibrium status between sediment and overlying water, 2) benthic bioaccumulation, and 3) potential toxicity to benthic organisms. Thus, the use of PSMs to measure Cfree provides an improved basis for the mechanistic understanding of fate and transport processes in sediments and has the potential to significantly improve risk assessment and management of contaminated sediments. Integr Environ Assess Manag 2014;10:197–209. © 2014 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of SETAC.

Use of passive stir bar sorptive extraction as a simple integrative sampling technique of pesticides in freshwaters: Determination of sampling rates and lag-phases

Passive sampling represents a cost-effective approach and is more representative than grab sampling for the determination of contaminant concentrations in freshwaters. In this study, we performed the calibration of a promising tool, the passive stir bar sorptive extraction (SBSE), which has previously shown good performances for semi-quantitative monitoring of pesticides in a field study. We determined the sampling rates and lag-phases of 18 moderately hydrophobic to hydrophobic agricultural pesticides (2.18<log Kow<5.11) from different chemical classes including triazines, substituted ureas, triazoles and organophosphate compounds. We also realised an elimination experiment to identify a performance reference compound (PRC). A flow-through calibration experiment was realised for 7 days at constant concentrations of target pesticides in tap water, under controlled temperature (20°C) and flow velocity (2.5cms−1). Sampling rates were between 1.3 and 121mL d−1 with satisfactory RSD for most pesticides (9–47%), and poor repeatability for 3 hydrophobic pesticides (59–83%). Lag-phases for all target pesticides were shorter than 2h, demonstrating the efficiency of passive SBSE for the integration of transient concentration peaks of these contaminants in surface waters. The role of flow velocity on pesticide uptakes was investigated and we assumed a water boundary layer-controlled mass transfer for 5 pesticides with log Kow>3.3. Among these pesticides, we selected fenitrothion to evaluate its elimination, along with its deuterated analogue. Results showed 82% elimination of both compounds over the 7-day experiment and isotropic exchange for fenitrothion, making fenitrothion-d6 a promising PRC candidate for in situ applications

Response to “Letter to the Editor Concerning the Viewpoint; ‘Recognizing the Limitations of Performance Reference Compound (PRC)-Calibration Technique in Passive Water Sampling’”

Response to “Letter to the Editor Concerning the Viewpoint; ‘Recognizing the Limitations of Performance Reference Compound (PRC)-Calibration Technique in Passive Water Sampling’”

In Situ Measurement of Time-Weighted Average Concentrations of Cylindrospermopsin and Microcystin LR-YR-RR-LY in Natural Waters Using Silicone-Membrane/Γ-Fe2O3-Nanoparticle-Sorbent Passive Sampling Device

Preliminary use of performance reference compounds (PRC) spiked into the silicone-membrane/γ-Fe2O3 sampler for in situ calibration has been demonstrated to improve the quantitative nature of water concentration estimates. Hydrophobic polycyclic aromatic hydrocarbons (PAHs), though they occur at significant levels in the environment, were used as PRC because of their relatively high fugacity from the silicone membrane and evidence of their isotropic exchange kinetics. In situ calibrations of silicone-membrane/γ-Fe2O3 sampler spiked with 16 PAHs and the resulting time weighted average (TWA) concentration estimates were compared with similar values of SPE extracts from grab samples. Calibration studies were successfully done and variable environmental conditions (e.g. effects of hydrodynamics and temperature) were found to affect their elimination rates from silicone-membrane/γ-Fe2O3 sampler. A significant increase of elimination rates with change of hydrodynamic conditions from static to turbulent was observed for all compounds under investigation. The technique has also been successfully applied to the detection of freshwater cyanobacterial toxins such as microcystins and cylindrospermopsin.

Field calibration of low density polyethylene passive samplers for gaseous POPs

A field calibration study of low density polyethylene (LDPE) for measuring atmospheric concentrations of persistent organic pollutants (POPs) was performed in East Providence (RI), USA. LDPE samplers were collected after 3, 7, 10, 14, 17 and 21 days of exposure along with samples from a co-deployed high volume sampler. Uptake kinetics of POPs by LDPEs were confirmed both by using an uptake study over time and the inclusion of performance reference compounds (PRCs). Results indicated that only POPs with log sampler-air partitioning coefficient (KPE-A) ≤ 7.6 were approaching equilibrium by the end of the deployment period, whereas all the other POPs were still in the linear uptake rate. Sampling rates (1.0-80 m(3) per day) were higher for some POPs when compared to literature values possibly due to the open sampler housing design used. Derived KPE-As for the detected POPs in field calibration study were correlated against the compounds' octanol-air partitioning coefficients (log KOA): [log KPE-A = 0.88 ± 0.02 × log KOA + 0.40 ± 0.21 (R(2) = 0.96; n = 59; SE = 0.23)], and their subcooled liquid vapour pressures (log PL/Pa): [log KPE-A = -0.82 ± 0.02 × log PL + 6.22 ± 0.05 (R(2) = 0.96; n = 59; SE = 0.22)] to predict values for all POPs. PL was generally found to be a better predictor of KPE-A for all POPs.

Passive sampling of perfluorinated chemicals in water: In-situ calibration

Perfluorinated chemicals (PFCs) have been recognised as environmental pollutants that require monitoring. A modified polar organic chemical integrative sampler (POCIS) is able to quantify aqueous PFCs. However, with varying external water velocity, PFC sampling rates (Rs) may change, affecting accuracy of derived water concentrations. To facilitate field deployment of this sampler, two methods of in-situ calibration were investigated: performance reference compounds (PRCs) and passive flow monitors (PFMs). Increased Rs's (by factors of 1.2–1.9) with PFM loss rate (g d−1) were observed for some PFCs. Results indicate PFMs can be used to correct PFC specific Rs's for more reliable estimates of environmental concentrations with a precision of about 0.01 L d−1. Empirical models presented provide an improved means for aquatic monitoring of PFCs. The PRC approach was unsuccessful, confirming concern as to its applicability with such samplers.

Polyethylene passive samplers to determine sediment–pore water distribution coefficients of persistent organic pollutants in five heavily contaminated dredged sediments

Pore concentration and partition coefficients of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined in sediments from five distinct contaminated sites in France (marine harbour, rivers canals and highway sedimentation tank). The assessment of the risk caused by such micropollutants requires, in most cases, the measurement of their availability. To assess this availability, low density polyethylene (LDPE) membrane samplers were exposed to these sediments under constant and low-level agitation over a period of 46days. Freely dissolved pore water contaminant concentrations were estimated from the concentration at equilibrium in the LDPE membrane. The depletion of contaminants in the sediments was monitored by the use of performance reference compounds (PRCs). Marked differences in freely dissolved PAH and PCB concentrations and resulting sediment–pore water partition coefficients between these five sediments were observed. Data set was tested onto different empirical and mechanistic models. As final findings, triple domain sorption (a total organic carbon, black carbon and oil phase model) could model PCB data successfully whereas the best fitting for PAH partitioning was obtained by Raoult's Law model.

Letter to the Editor Concerning the Viewpoint; “Recognizing the Limitations of Performance Reference Compound (PRC)-Calibration Technique in Passive Water Sampling”

Letter to the Editor Concerning the Viewpoint; “Recognizing the Limitations of Performance Reference Compound (PRC)-Calibration Technique in Passive Water Sampling”

Comparison of five integrative samplers in laboratory for the monitoring of indicator and dioxin-like polychlorinated biphenyls in water

This study aimed at evaluating and comparing five integrative samplers for the monitoring of indicator and dioxin-like polychlorinated biphenyls (PCBs) in water: semi-permeable membrane device (SPMD), silicone rubber, low-density polyethylene (LDPE) strip, Chemcatcher and a continuous-flow integrative sampler (CFIS). These samplers were spiked with performance reference compounds (PRCs) and then simultaneously exposed under constant agitation and temperature in a 200 L stainless steel tank for periods ranging from one day to three months. A constant PCB concentration of about 1ng·L−1 was achieved by immersing a large amount of silicone rubber sheets (“dosing sheets”) spiked with the target PCBs. The uptake of PCBs in the five samplers showed overall good repeatability and their accumulation was linear with time. The samplers SPMD, silicone rubber and LDPE strip were the most promising in terms of achieving low limits of quantification. Time-weighted average (TWA) concentrations of PCBs in water were estimated from uptake of PCBs using the sampling rates calculated from the release of PRCs. Except for Chemcatcher, a good agreement was found between the different samplers and TWA concentrations ranged between 0.4 and 2.8 times the nominal water concentration. Finally, the influence of calculation methods (sampler-water partition coefficients, selected PRCs, models) on final TWA concentrations was studied.