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.

Determining the Mass Transfer Coefficient of the Water Boundary Layer at the Surface of Aquatic Integrative Passive Samplers.

Passive sampling devices (PSDs) offer key benefits for monitoring chemical water quality, but the uptake process of PSDs for hydrophilic compounds still needs to be better understood. Determining mass transfer coefficients of the water boundary layer (kw) during calibration experiments and in situ monitoring would contribute toward achieving this; it allows for combining calibration data obtained at different temperature and hydrodynamic conditions and facilitate the translation of laboratory-derived calibration data to field exposure. This study compared two kw measurement methods applied to extraction disk housings (Chemcatcher), namely, alabaster dissolution and dissipation of performance reference compounds (PRCs) from silicone. Alabaster- and PRC-based kw were measured at four flow velocities (5-40 cm s-1) and two temperatures (11 and 20 °C) in a channel system. Data were compared using a relationship based on Sherwood, Reynolds, and Schmidt numbers. Good agreement was observed between data obtained at both temperatures, and for the two methods. Data were well explained by a model for mass transfer to a flat plate under laminar flow. It was slightly adapted to provide a semi-empirical model accounting for the effects of housing design on hydrodynamics. The use of PRC-spiked silicone to obtain in situ integrative kw for Chemcatcher-type PSDs is also discussed.

Kinetic Passive Sampling: In Situ Calibration Using the Contaminant Mass Measured in Parallel Samplers with Different Thicknesses.

The use of single-phase passive samplers is a common method for sampling bioavailable concentrations of hydrophobic aquatic pollutants. Often such samplers are used in the kinetic stage, and in situ calibration is necessary. Most commonly, exchange kinetics are derived from the release rates of performance reference compounds (PRCs). In this study, a complementary calibration approach was developed, in which measuring the contaminant mass ratio (CMR) from two samplers with different thicknesses allows the dissolved concentrations to be determined. This new CMR calibration was tested (1) in a laboratory experiment with defined and constant concentrations and (2) in the field, at a storm water retention site. Silicone passive samplers with different thicknesses were used to sample a range of dissolved polycyclic aromatic hydrocarbons. In the laboratory study, the concentrations derived from the CMR calibration were compared with those from water extraction and passive dosing and differences below a factor 2 were found. In the field study, CMR-derived concentrations were compared to those from PRC calibration. Here, differences ranged by only a factor 1 to 3 between both methods. These findings indicate that the CMR calibration can be applied as a stand-alone or complementary calibration method for kinetic passive sampling.

Aquatic Global Passive Sampling (AQUA-GAPS) Revisited: First Steps toward a Network of Networks for Monitoring Organic Contaminants in the Aquatic Environment.

Organic contaminants, in particular persistent organic pollutants (POPs), adversely affect water quality and aquatic food webs across the globe. As of now, there is no globally consistent information available on concentrations of dissolved POPs in water bodies. The advance of passive sampling techniques has made it possible to establish a global monitoring program for these compounds in the waters of the world, which we call the Aquatic Global Passive Sampling (AQUA-GAPS) network. A recent expert meeting discussed the background, motivations, and strategic approaches of AQUA-GAPS, and its implementation as a network of networks for monitoring organic contaminants (e.g., POPs and others contaminants of concern). Initially, AQUA-GAPS will demonstrate its operating principle via two proof-of-concept studies focused on the detection of legacy and emerging POPs in freshwater and coastal marine sites using both polyethylene and silicone passive samplers. AQUA-GAPS is set up as a decentralized network, which is open to other participants from around the world to participate in deployments and to initiate new studies. In particular, participants are sought to initiate deployments and studies investigating the presence of legacy and emerging POPs in Africa, Central, and South America.

Passive Sampling in Regulatory Chemical Monitoring of Nonpolar Organic Compounds in the Aquatic Environment.

We reviewed compliance monitoring requirements in the European Union, the United States, and the Oslo-Paris Convention for the protection of the marine environment of the North-East Atlantic, and evaluated if these are met by passive sampling methods for nonpolar compounds. The strengths and shortcomings of passive sampling are assessed for water, sediments, and biota. Passive water sampling is a suitable technique for measuring concentrations of freely dissolved compounds. This method yields results that are incompatible with the EU's quality standard definition in terms of total concentrations in water, but this definition has little scientific basis. Insufficient quality control is a present weakness of passive sampling in water. Laboratory performance studies and the development of standardized methods are needed to improve data quality and to encourage the use of passive sampling by commercial laboratories and monitoring agencies. Successful prediction of bioaccumulation based on passive sampling is well documented for organisms at the lower trophic levels, but requires more research for higher levels. Despite the existence of several knowledge gaps, passive sampling presently is the best available technology for chemical monitoring of nonpolar organic compounds. Key issues to be addressed by scientists and environmental managers are outlined.

Multi-ratio equilibrium passive sampling method to estimate accessible and pore water concentrations of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in sediment.

The freely dissolved concentration (C(w,0)) in the pore water and the accessible (releasable) concentration in the sediment (C(as,0)) are important parameters for risk assessment. These parameters were determined by equilibrating contaminated sediments and passive samplers using largely differing sampler­sediment ratios. This method is based on the principle that incubations at low sampler/sediment ratios yield the concentration in the pore water (minor depletion of the sediment phase) and incubations at high sampler/sediment ratios yield the accessible concentration in the sediment (maximum depletion of the sediment phase). It is shown that equilibration was faster in dense suspensions and at high sampler/sediment ratios when compared to low sampler/sediment ratios. An equilibrium distribution model was used to estimate C(w,0) and C(as,0) by nonlinear least-squares regression. The method was evaluated for three sediments (harbor, estuarine, marine). Accessible concentrations of 13 PAHs were 2 (low K(ow)) to 10 (high K(ow)) times lower than the total concentrations (three sediments). By contrast, the accessible concentrations of 15 PCBs were about 1.2 times lower than the total concentrations and displayed no trend with K(ow) (one sediment). Implications for risk assessment and considerations for application of multi-ratio equilibrium passive sampling with other sediments are discussed.

Development and calibration of a passive sampler for perfluorinated alkyl carboxylates and sulfonates in water.

Perfluorinated chemicals (PFCs) are emerging environmental contaminants with a global distribution. Due to their moderate water solubility, the majority of the environmental burden is assumed to be in the water phase. This work describes the application of the first passive sampler for the quantitative assessment of concentrations of perfluorinated alkylcarboxylates (PFCAs) and sulfonates (PFSAs) in water. The sampler is based on a modified Polar Organic Chemical Integrative Sampler (POCIS) with a weak anion exchange sorbent as a receiving phase. Sampling rates were between 0.16 and 0.37 L d(-1), and the duration of the kinetic sampling stage was between 2.2 and 13 d. A field deployment in the most urbanized estuary in Australia (Sydney Harbour) showed trace level concentrations from passive samplers (0.1-12 ng L(-1)), in good agreement with parallel grab sampling (0.2-16 ng L(-1)). A separate field comparison of the modified POCIS with standard POCIS suggests the latter may have application for PFC sampling, but with a more limited range of analytes than the modified POCIS which contains a sorbent with a mixed mode of action.

Method for the in situ calibration of a passive phosphate sampler in estuarine and marine waters.

Passive samplers for phosphate were calibrated in the laboratory over a range of flow velocities (0-27 cm s(-1)) and ionic strengths (0-0.62 mol kg(-1)). The observed sampling rates were between 0.006 and 0.20 L d(-1). An empirical model allowed the estimation of these sampling rates with a precision of 8.5%. Passive flow monitors (PFMs), based on gypsum dissolution rates, were calibrated for the same range of flow velocities and ionic strength. Mass loss rates of the PFMs increased with increasing ionic strength. We demonstrate that this increase is quantitatively accounted for by the increased gypsum solubility at higher ionic strengths. We provide a calculation scheme for these solubilities for an environmentally relevant range of temperatures and salinities. The results imply that co-deployed PFMs can be used for estimating the flow effect on the in situ sampling rates of the phosphate samplers, and we expect that the same may hold for other passive samplers.

Identification of components of the female sex pheromone of the Simao pine caterpillar moth, Dendrolimus kikuchii Matsumura.

The pine caterpillar moth, Dendrolimus kikuchii Matsumura (Lepidoptera: Lasiocampidae), is a pest of economic importance on pine in southwest China. Three active compounds were detected during analyses of solvent extracts and effluvia sampled by solid phase microextraction (SPME) from virgin female D. kikuchii using gas chromatography (GC) coupled with electroantennographic (EAG) recording with antennae from a male moth. The compounds were identified as (5Z,7E)-5,7-dodecadien-1-yl acetate (Z5,E7-12:OAc), (5Z,7E)-5,7-dodecadien-1-ol (Z5,E7-12:OH), and (5Z)-5-dodecenyl acetate (Z5-12:OAc) by comparison of their GC retention indices, mass spectra, and EAG activities with those of synthetic standards. Microchemical reactions of gland extracts provided further information confirming the identifications of the three components. Solvent extractions and SPME samples of pheromone effluvia from virgin calling females provided 100:18:0.6 and 100:7:1 ratios of Z5,E7-12:OAc:Z5,E7-12:OH:Z5-12:OAc, respectively. Field behavioral assays showed that Z5,E7-12:OAc and Z5,E7-12:OH were essential for attraction of male D. kikuchii moths. However, the most attractive blend contained these three components in a 100:20:25 ratio in a gray rubber septa. Our results demonstrated that the blend of Z5,E7-12:OAc, Z5,E7-12:OH, and Z5-12:OAc comprise the sex pheromone of D. kikuchii. The optimized three-component lure blend is recommended for monitoring D. kikuchii infestations.

Passive Sampler Exchange Kinetics in Large and Small Water Volumes Under Mixed Rate Control by Sorbent and Water Boundary Layer.

Exchange kinetics of organic compounds between passive samplers and water can be partly or completely controlled by transport in the sorbent. In such cases diffusion models are needed. A model is discussed that is based on a series of cosines (space) and exponentials (time). The model applies to mixed rate control by sorbent and water boundary layer under conditions of fixed aqueous concentrations (open systems, infinite water volumes, in situ sampling) and fixed amounts (closed systems, finite water volumes, ex situ sampling). Details on the implementation of the model in computational software and spreadsheet programs are discussed, including numerical accuracy. Key parameters are Biot number (ratio of internal/external transfer resistance) and sorbent/water phase ratio. Small Biot numbers are always indicative of rate control by the water boundary layer, but for large Biot numbers this may still be the case over short time scales. Application to environmental monitoring of nonpolar compounds showed that diffusion models are rarely needed for sampling with commonly used single-phase polymers. For determining sorption coefficients in batch incubations, the model demonstrated a profound effect of sorbent/water phase ratio on time to equilibrium. Application of the model to sampling of polar organic compounds by extraction disks with or without a membrane showed that moderate to major sorbent-controlled kinetics is likely to occur. This implies that the use of sampling rate models for such samplers needs to be reconsidered. Environ Toxicol Chem 2021;40:1241-1254. © 2021 SETAC.

An improved method for estimating in situ sampling rates of nonpolar passive samplers.

The quality of passive sampling methods for measuring concentrations of dissolved hydrophobic contaminants relies on accurate knowledge of in situ sampling rates. In currently used methods for estimating these sampling rates from the dissipation rates of performance reference compounds (PRCs), the PRCs that show either insignificant or complete dissipation are ignored. We explored the merits of nonlinear least-squares (NLS) methods for estimating sampling rates, aiming to retain the information stored in PRC data that is neglected in the traditional methods. To this end, we examined the error structure of weighted NLS, unweighted NLS, and the traditional methods, using model simulations. The results show that sampling rates are best estimated using unweighted NLS. Uncertainties in the sampler-water partition coefficients may result in biased estimates that only weakly depend on the number of PRCs being used. The major advantage of unweighted NLS over the traditional method is that sampling rate estimates and uncertainties are available where the traditional method fails, and that the variability of sampling rate estimates is smaller.

Short-term exposure testing of six different passive samplers for the monitoring of hydrophobic contaminants in water.

Passive sampling devices are increasingly relied upon for monitoring non-polar organic contaminants in water. While many types of devices are available they have seldom been evaluated alongside each other. We tested six passive sampling devices namely: Chemcatcher, two modified versions of the membrane enclosed sorptive coating (MESCO I (m) and MESCO II), silicone rod and strip and semipermeable membrane device (SPMD). Samplers spiked with a range of performance reference compounds (PRCs) were exposed (5 days) in a continuous flow-through tank using Meuse river water fortified with fluctuating concentrations (20-700 ng L(-1)) of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, hexachlorobenzene and p,p'-DDE. Dissipation rates of PRCs appeared to provide reliable information on exchange kinetics even under these short-term exposure conditions. They accounted for differences between masses of contaminants accumulated by replicate samplers, indicating that the variability between replicates was in part due to differences in water turbulences and hence boundary layer thickness. In this system, resistances in the membrane and boundary layers are likely to be in the same order of magnitude for PRCs. Sampler performance was evaluated by comparing masses accumulated in the devices only for analytes for which uptake was linear (integrative) and limited by transport across the boundary layer. Consistent data were obtained across the range of samplers despite their different configurations, and the analysis being conducted in three separate laboratories. The pattern in analyte masses accumulated by Chemcatcher and MESCO II data could be explained by the extraction and analysis being conducted only on the receiving phase of the samplers and a significant impact of the lag-phase prior to obtaining a steady flux of contaminants across the polyethylene membranes.

POCIS Calibration for Organic Compound Sampling in Small Headwater Streams.

Field-based atrazine sampling rates (Rs ) obtained by the polar organic chemical integrative sampler (POCIS) method were measured in 9 headwater streams over 3 yr covering 5 to 6 exposure periods of 2 to 3 wk/site/yr. Rates were best in line with the model Rs = 148 mL/d, with a standard deviation of 0.17 log units (factor 1.5). The POCIS canisters reduced mass transfer coefficients of the water boundary layer by a factor of 2 as measured by alabaster dissolution rates. A mechanistic model that accounts for flow and temperature effects yielded a fair estimate of the effective exchange surface area (12.5 ± 0.8 cm2 ). This model could only be tested for higher flow velocities because of uncertainties associated with the measurement of flow velocities <1 cm/s. Pictures of sorbent distributions in POCIS devices showed that the effective exchange surface area varied with time during the exposures. Error analysis indicated that sorbent distributions and chemical analysis were minor error sources. Our main conclusion is that an atrazine sampling rate of 148 mL/d yielded consistent results for all 3 yr across 9 headwater streams. Environ Toxicol Chem 2020;39:1334-1342. © 2020 SETAC.

Prediction of deoxynivalenol content in Dutch winter wheat.

Predictive models for the deoxynivalenol (DON) content in wheat can be a useful tool for control authorities and the industry to avoid or limit potential food and/or feed safety problems. The objective of this study was to develop a predictive model for DON in mature Dutch winter wheat. From 2001 to 2007, the concentration of DON was measured in winter wheat samples taken just before harvest from 264 fields throughout The Netherlands. Agronomic and climatic variables were obtained for each field for a 48-day period, centered on the heading date. Multiple regression was used to determine the most important variables and to construct the predictive model. The first model (model 1) was based on 24-day pre- and postheading periods, while the second model (model 2) was based on eight time blocks of 6 days around the heading date. Although both models showed good statistical evaluations and predictive performance, model 1 showed the highest performance (R(2) of 0.59 between observed and predicted values, fraction samples correctly below or above the 1,250 microg/kg threshold of 92%, and sensitivity of 63%). With both models, the predicted DON level increased with a higher average temperature, increased precipitation, and higher relative humidity, but decreased with increased number of hours with the temperature above 25 degrees C. We observed a strong regional effect on the levels of DON, which could not be explained by differences in the recorded agronomic and climatic variables. It is suggested that future model improvement might be realized by indentifying and quantifying the mechanism underlying the region effect.

Passive samplers to quantify micropollutants in sewer overflows: accumulation behaviour and field validation for short pollution events.

Contaminants in sewer overflows can contribute to exceedances of environmental quality standards, thus the quantification of contaminants during rainfall events is of relevance. However, monitoring is challenged by i) high spatiotemporal variability of contaminants in events of hard-to-predict durations, and ii) a large number of remote sites, which would imply enormous efforts with traditional sampling equipment. Therefore, we evaluate the applicability of passive samplers (Empore styrene-divinylbenzene reverse phase sulfonated (SDB-RPS)) to monitor a set of 13 polar organic contaminants. We present calibration experiments at high temporal resolution to assess the rate limiting accumulation mechanisms for short events (<36 h), report parameters for typical sewer conditions and compare passive samplers with composite water samples in a field study (three locations, total 10 events). With sampling rates of 0.35-3.5 L/d for 1 h reference time, our calibration results indicate a high sensitivity of passive samplers to sample short, highly variable sewer overflows. The contaminant uptake kinetic shows a fast initial accumulation, which is not well represented with the typical first-order model. Our results indicate that mass transfer to passive samplers is either controlled by the water boundary layer and the sorbent, or by the sorbent alone. Overall, passive sampler concentration estimates are within a factor 0.4 to 3.1 in comparison to composite water samples in the field study. We conclude that passive samplers are a promising approach to monitor a large number of discharge sites although it cannot replace traditional stormwater quality sampling in some cases (e.g. exact load estimates, high temporal resolution). Passive samplers facilitate identifying and prioritizing locations that may require more detailed investigations.

Comparison of semipermeable membrane device (SPMD) and large-volume solid-phase extraction techniques to measure water concentrations of 4,4'-DDT, 4,4'-DDE, and 4,4'-DDD in Lake Chelan, Washington.

Semipermeable membrane devices (SPMDs) spiked with the performance reference compound PCB29 were deployed 6.1 m above the sediments of Lake Chelan, Washington, for a period of 27 d, to estimate the dissolved concentrations of 4,4'-DDT, 4,4'-DDE, and 4,4'-DDD. Water concentrations were estimated using methods proposed in 2002 and newer equations published in 2006 to determine how the application of the newer equations affects historical SPMD data that used the older method. The estimated concentrations of DDD, DDE, and DDD calculated using the older method were 1.5-2.9 times higher than the newer method. SPMD estimates from both methods were also compared to dissolved and particulate DDT concentrations measured directly by processing large volumes of water through a large-volume solid-phase extraction device (Infiltrex 300). SPMD estimates of DDD+DDE+DDT (SigmaDDT) using the older and newer methods were lower than Infiltrex concentrations by factors of 1.1 and 2.3, respectively. All measurements of DDT were below the Washington State water quality standards for the protection of human health (0.59 ng l(-1)) and aquatic life (1.0 ng l(-1)).

Review of atrazine sampling by polar organic chemical integrative samplers and Chemcatcher.

A key success factor for the performance of passive samplers is the proper calibration of sampling rates. Sampling rates for a wide range of polar organic compounds are available for Chemcatchers and polar organic chemical integrative samplers (POCIS), but the mechanistic models that are needed to understand the effects of exposure conditions on sampling rates need improvement. Literature data on atrazine sampling rates by these samplers were reviewed with the aim of assessing what can be learned from literature reports of this well-studied compound and identifying knowledge gaps related to the effects of flow and temperature. The flow dependency of sampling rates could be described by a mass transfer resistance model with 1 (POCIS) or 2 (Chemcatcher) adjustable parameters. Literature data were insufficient to evaluate the temperature effect on the sampling rates. An evaluation of reported sampler configurations showed that standardization of sampler design can be improved: for POCIS with respect to surface area and sorbent mass, and for Chemcatcher with respect to housing design. Several reports on atrazine sampling could not be used because the experimental setups were insufficiently described with respect to flow conditions. Recommendations are made for standardization of sampler layout and documentation of flow conditions in calibration studies. Environ Toxicol Chem 2018;37:1786-1798. © 2018 SETAC.

Effects of hydrodynamic conditions and temperature on polar organic chemical integrative sampling rates.

The effects of changing hydrodynamic conditions and changing temperatures on polar organic chemical integrative sampler (POCIS) sampling rates (Rs ) were investigated for 12 crop protection chemicals. Exposure concentration was held constant in each laboratory experiment, and flow velocities were calculated from measured mass transfer coefficients of the water boundary layer near the surface of POCIS devices. At a given temperature Rs generally increased by a factor of 2 to 5 between a stagnant condition and higher flow velocities (6-21 cm/s), but Rs for most compounds was essentially constant between the higher flow velocities. When temperature was varied between 8 and 39 °C for a given flow condition, Rs increased linearly. In general, Rs increased by a factor of 2 to 4 and 2 to 8 over this temperature range under flow and stagnant conditions, respectively. An Arrhenius model was used to describe the dependence of POCIS sampling rates on temperature. Adjustments of Rs for temperature did not fully explain observed differences between time-weighted average concentrations of atrazine determined from POCIS and from composite water sampling in a field setting, suggesting that the effects of other competing factors still need to be evaluated. Environ Toxicol Chem 2018;37:2331-2339. © 2018 SETAC.