Passive-Sampler-Derived PCB and OCP Concentrations in the Waters of the World─First Results from the AQUA-GAPS/MONET Network.

Persistent organic pollutants (POPs) are recognized as pollutants of global concern, but so far, information on the trends of legacy POPs in the waters of the world has been missing due to logistical, analytical, and financial reasons. Passive samplers have emerged as an attractive alternative to active water sampling methods as they accumulate POPs, represent time-weighted average concentrations, and can easily be shipped and deployed. As part of the AQUA-GAPS/MONET, passive samplers were deployed at 40 globally distributed sites between 2016 and 2020, for a total of 21 freshwater and 40 marine deployments. Results from silicone passive samplers showed α-hexachlorocyclohexane (HCH) and γ-HCH displaying the greatest concentrations in the northern latitudes/Arctic Ocean, in stark contrast to the more persistent penta (PeCB)- and hexachlorobenzene (HCB), which approached equilibrium across sampling sites. Geospatial patterns of polychlorinated biphenyl (PCB) aqueous concentrations closely matched original estimates of production and use, implying limited global transport. Positive correlations between log-transformed concentrations of Σ7PCB, ΣDDTs, Σendosulfan, and Σchlordane, but not ΣHCH, and the log of population density (p < 0.05) within 5 and 10 km of the sampling sites also supported limited transport from used sites. These results help to understand the extent of global distribution, and eventually time-trends, of organic pollutants in aquatic systems, such as across freshwaters and oceans. Future deployments will aim to establish time-trends at selected sites while adding to the geographical coverage.

Identification of polystyrene nanoplastics from natural organic matter in complex environmental matrices by pyrolysis-gas chromatography-mass spectrometry.

Due to the flux of plastic debris entering the environment, it becomes urgent to document and monitor their degradation pathways at different scales. At the colloidal scale, the systematic hetero-association of nanoplastics with the natural organic matter complexifies the ability to detect plastic signatures in the particle collected in the various environments. The current techniques used for microplastics could not discriminate the polymers at the nanoscale from the natural macromolecules, as the plastic mass in the aggregate is within the same order. Only a few methods are available concerning nanoplastics identification in complex matrices, with the coupling of pyrolysis with gas chromatography and mass spectrometry (Py-GC-MS) as one of the most promising due to its mass-based detection. However, natural organic matter in environmental samples interferes with similar pyrolysis products. These interferences are even more critical for polystyrene polymers as this plastic presents no dominant pyrolysis markers, such as polypropylene, that could be identified at trace concentrations. Here, we investigate the ability to detect and quantify polystyrene nanoplastics in a rich phase of natural organic matter proposed based on the relative ratio of pyrolyzates. The use of specific degradation products (styrene dimer and styrene trimer) and the toluene/styrene ratio (RT/S) are explored for these two axes. While the size of the polystyrene nanoplastics biased the pyrolyzates of styrene dimer and trimer, the RT/S was correlated with the nanoplastics mass fraction in the presence of natural organic matter. An empirical model is proposed to evaluate the relative quantity of polystyrene nanoplastics in relevant environmental matrices. The model was applied to real contaminated soil by plastic debris and literature data to demonstrate its potential.

Passive Samplers vs Sentinel Organisms: One-Year Monitoring of Priority and Emerging Contaminants in Coastal Waters.

Temporal monitoring of pollutants in aquatic systems impacted by human activities is mandatory for a correct assessment on their environmental impact and later management. The aim of this work was to study the suitability of using silicone rubber passive samplers and caged organisms (Ruditapes philippinarum), simultaneously, to examine the spatial and temporal variability of priority and emerging contaminants in a coastal environment (Cadiz Bay, SW Spain) over the course of an entire year. Seasonal trends were observed for some classes of compounds, such as UV filters and fragrances, and attributed to fluctuations in their sources and changes in the hydrodynamic conditions, respectively. Up to 42 out of 48 (in seawater) and 27 out of 37 (in biota) target analytes were detected, the highest concentrations being observed for synthetic fragrances and UV filters in both biota (136.9-159 ng g-1) and the dissolved phase (3322.2-265.7 ng L-1). Conversely, spatiotemporal differences in the concentrations of target contaminants in clam tissues were minimal. Higher field bioaccumulation factors (log BAF > 5) were found for priority substances. Overall, silicone rubber passive samplers proved to be more sensitive than sentinel organisms for monitoring spatiotemporal changes in the dissolved aqueous concentrations of contaminants, whereas the latter allowed for a more realistic evaluation of the potential uptake and bioaccumulation of each compound.

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.

PAH Accessibility in Particulate Matter from Road-Impacted Environments.

Snowmelt, surface runoff, or stormwater releases in urban environments can result in significant discharges of particulate matter-bound polycyclic aromatic hydrocarbons (PAHs) into aquatic environments. Recently, more-specific activities such as road-tunnel washing have been identified as contributing to contaminant load to surface waters. However, knowledge of PAH accessibility in particulate matter (PM) of urban origin that may ultimately be released into urban surface waters is limited. In the present study, we evaluated the accessibility of PAHs associated with seven distinct (suspended) particulate matter samples collected from different urban sources. Laboratory-based infinite sink extractions with silicone rubber (SR) as the extractor phase demonstrated a similar pattern of PAH accessibility for most PM samples. Substantially higher accessible fractions were observed for the less-hydrophobic PAHs (between 40 and 80% of total concentrations) compared with those measured for the most-hydrophobic PAHs (<5% of total concentrations). When we focused on PAHs bound to PM from tunnel-wash waters, first-order desorption rates for PAHs with log Kow > 5.5 were found in line with those commonly found for slowly or very slowly desorbing sediment-associated contaminants. PAHs with log Kow < 5.5 were found at higher desorbing rates. The addition of detergents did not influence the extractability of lighter PAHs but increased desorption rates for the heavier PAHs, potentially contributing to increases in the toxicity of tunnel-wash waters when surfactants are used. The implications of total and accessible PAH concentrations measured in our urban PM samples are discussed in a context of management of PAH and PM emission to the surrounding aquatic environment. Although we only fully assessed PAHs in this work, further study should consider other contaminants such as OPAHs, which were also detected in all PM samples.

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.

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.

Measurement of environmental pollutants using passive sampling devices--a commentary on the current state of the art.

Passive sampling devices have been used since the 1970s to measure time-weighted average (TWA) or equilibrium concentrations of pollutants in various environmental matrices (e.g. air, soils and sediments and water). In recent years the popularity of using such samplers has increased and the technology in now well established for the measurement of atmospheric pollutants. This sector has a long experience of using passive samplers in the short- and long-term assessment of air quality in the local environment and on a global scale (e.g. within the United Nations Stockholm Convention on the trans-boundary movement of persistent organic pollutants (POPs) where large networks of samplers on a continental scale have been established). In comparison, the use of passive samplers for monitoring the aquatic environment has been slower to take off. There has, however, been a recent research drive to develop devices for measuring the wide range of pollutants that can be found in environmental waters (e.g. ground, surface, and marine). It is now being recognised that passive samplers can play a valuable role in monitoring water quality within a legislative framework such as the European Union's Water Framework Directive (WFD). The data from these devices can be used alongside the results obtained from conventional spot or bottle sampling to improve risk assessments and to inform decisions on undertaking potentially expensive remedial actions. Such monitoring techniques may have uses within the European Registration, Evaluation, Authorisation & restriction of CHemicals (REACH) Directive and the forthcoming European Marine Strategy Directive. It is expected that the aquatic monitoring sector will follow a transition similar to that which occurred in air monitoring where data obtained from passive samplers can use used within a legal framework. There has also been increased interest in extending the role of passive samplers to both the measurement of equilibrium concentrations and investigating the movement and release of the dissolved fraction of various pollutants in the pore water of sediments and soils.

Assessment of marine sediment remediation efficiency with SPME-based passive sampling measurement.

Passive sampling has been shown to be a suitable procedure to assess the risk of contaminated sediments through the measurement of freely dissolved concentrations (CFree) and remedial actions involving amendments such as activated carbon (AC). Here we report results of the application of simple, solvent-free solid phase micro extraction methodology (SPME) to assess the performance of different materials for the remediation of selected Norwegian harbour sediments contaminated with polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). AC amendments enabled a reduction of the availability of PAHs and/or PCBs by a factor of ten to over one hundred in Aker Brygge sediments (Oslo) and sediments from Elkembukta, impacted by industrial emissions of PAHs with/from coal tar pitch. Another material, anthracite, slightly less effective in this set of experiment than AC, showed nonetheless great promise as capping material. The SPME data are put in perspective with equilibrium measurements of CFree for PAHs and organochlorines with silicone rubber in other Elkembukta sediments collected in the vicinity of those used for the remediation experiments. A reduction of sediment Cfree for pyrene, benzo[a]pyrene and benzo[ghi]perylene in inner Elkembukta sediment from on average 407, 6.3 and 0.82 ng L-1 to values of/or below 1.3, 0.15 and 0.076 ng L-1, respectively can be expected upon remediation with AC. For the outer, less contaminated Elkembukta sediment, Cfree would reduce from 36, 0.81 and 0.13 ng L-1 to value of or below 0.06, 0.03 and 0.005 ng L-1 for these three compounds, respectively. Differences in pattern of PAH and organochlorine contamination of inner and outer Elkembukta sediments are discussed.

Partitioning of persistent hydrophobic contaminants to different storage lipid classes.

Lipids generally represent the major matrix contributing to the absorptive capacity for hydrophobic organic contaminants in aquatic ecosystems. The aim of the present study was to determine whether contaminants partition to a different degree to the different storage lipid classes: wax ester (WE) and triacylglycerol (TAG). This was undertaken by studying experimentally the partitioning of organochlorine compounds between lipids (WE or TAG) and silicone rubber phase. Our results indicate that hydrophobic compounds have a slightly higher affinity for WE than for TAG. The findings thus corroborate earlier suggestions that contaminants accumulate to a greater extent in food webs with a higher reliance of on WE, such as in the Arctic. This knowledge is of interest since it implies that possible changes in planktonic community species composition, and thereby possible changes in the lipid composition, may have consequences for accumulation of hydrophobic contaminants in apex predators. However, the magnitude of these consequences remains unknown, and there may well be other factors of importance for previously observed higher accumulation of contaminants in Arctic systems. Thus, we have here identified aspects regarding partitioning of contaminants to lipids that need further scrutiny, and there is a need for further quantitative estimates of the suggested difference in absorptive capacities for hydrophobic contaminants between WE and TAG.

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.

Chemcatcher and DGT passive sampling devices for regulatory monitoring of trace metals in surface water.

This work aimed to evaluate whether the performance of passive sampling devices in measuring time-weighted average (TWA) concentrations supports their application in regulatory monitoring of trace metals in surface waters, such as for the European Union's Water Framework Directive (WFD). The ability of the Chemcatcher and the diffusive gradient in thin film (DGT) device sampler to provide comparable TWA concentrations of Cd, Cu, Ni, Pb and Zn was tested through consecutive and overlapping deployments (7-28 days) in the River Meuse (The Netherlands). In order to evaluate the consistency of these TWA labile metal concentrations, these were assessed against total and filtered concentrations measured at relatively high frequencies by two teams using standard monitoring procedures, and metal species predicted by equilibrium speciation modeling using Visual MINTEQ. For Cd and Zn, the concentrations obtained with filtered water samples and the passive sampling devices were generally similar. The samplers consistently underestimated filtered concentrations of Cu and Ni, in agreement with their respective predicted speciation. For Pb, a small labile fraction was mainly responsible for low sampler accumulation and hence high measurement uncertainty. While only the high frequency of spot sampling procedures enabled the observation of higher Cd concentrations during the first 14 days, consecutive DGT deployments were able to detect it and provide a reasonable estimate of ambient concentrations. The range of concentrations measured by spot and passive sampling, for exposures up to 28 days, demonstrated that both modes of monitoring were equally reliable. Passive sampling provides information that cannot be obtained by a realistic spot sampling frequency and this may impact on the ability to detect trends and assess monitoring data against environmental quality standards when concentrations fluctuate.

Detection of tris(2,3-dibromopropyl) phosphate and other organophosphorous compounds in Arctic rivers.

The flame-retardant tris(2,3-dibromopropyl) phosphate (TDBrPP) was in the 1970s banned for uses in textiles that may be in contact with the skin, owing to strong suspicions that the substance was a human carcinogen. The substance is looked for but rarely detected in samples from the built and natural environments, but there are indications that TDBrPP is still in use. Here, we report the measurement of a polymer-water partition coefficient (Kpw) for two types of silicone rubber (SR), allowing quantitative estimation of freely dissolved concentrations of TDBrPP by passive sampling in water. We found levels of 100 to 200 pg/L in two Arctic rivers that were sampled during a 2014-2015 survey of contamination using passive samplers in Norwegian and Russian rivers draining into the Barents Sea. We also report the widespread presence of other organophosphorus flame retardants in this survey of eight rivers that drain into the Barents Sea.

Comparison of caged and native blue mussels (Mytilus edulis spp.) for environmental monitoring of PAH, PCB and trace metals.

Contaminant bioaccumulation was studied in blue mussels (Mytilus edulis spp.) using the harbor waters of Kristiansand (Norway) as a case study. A suite of chemical contaminants (trace metals, PAHs and PCBs) was analyzed in caged and native mussels as well as in passive samplers (Diffusive Gradients in Thin films (DGT)-devices and silicone rubbers) placed alongside the mussels for estimation of contaminant concentrations in water and uptake rates and bioaccumulation factors (BAFs) in mussels during a six-months deployment period. Estimated logBAFs were in the ranges 2.3-5.5, 3.8-5.2 and 3.2-4.4 for metals, PCBs and PAHs, respectively. Contaminant levels in caged mussels increased rapidly to stable levels for trace metals, whereas for hydrophobic organic contaminants the increase was steady but slow and for many compounds did not reach the levels observed in native mussels. Some key issues related to mussel caging design, such as mussel deployment time and confounding influence from seasonal fluctuations, are discussed herein.

Identification of non-regulated polycyclic aromatic compounds and other markers of urban pollution in road tunnel particulate matter.

A combination of silicone rubber extraction and non-target and suspect screening by gas chromatography coupled to high-resolution time-of flight mass spectrometry was used for the identification of compounds in particulate matter (PM). Tunnel PM is a proxy for local road pollution that constitutes a hazard to the urban environment and human health. The use of silicone rubber for the extraction of PM allowed the pre-concentration of a wide range of compounds for non-target analysis while minimising the effects of the sample matrix. As expected, polycyclic aromatic compounds (PACs) constituted the major group of compounds identified, but only 5 of 50 PACs identified were amongst those regularly monitored and many of them were alkylated or contained a heteroatom. Urban markers of contamination such as organophosphate flame-retardants, phthalates, benzothiazoles, musk compounds and a plasticiser were also identified. The level of confidence for the identifications was high based on accurate mass, the pattern of fragmentation and retention. The unequivocal identification of 16 compounds, from all groups, was confirmed by co-chromatography with standards and the compounds semi-quantified. Most of the PACs identified are not regularly monitored, and the hazards they pose are therefore unknown. Some of these PACs are known to be more persistent and mobile in the environment than the EPA PAH16.

Blue mussels (Mytilus edulis spp.) as sentinel organisms in coastal pollution monitoring: A review.

The blue mussel (Mytilus spp.) is widely used as a bioindicator for monitoring of coastal water pollution (mussel watch programs). Herein we provide a review of this study field with emphasis on: the suitability of Mytilus spp. as environmental sentinels; uptake and bioaccumulation patterns of key pollutant classes; the use of Mytilus spp. in mussel watch programs; recent trends in Norwegian mussel monitoring; environmental quality standards and background concentrations of key contaminants; pollutant effect biomarkers; confounding factors; particulate contaminants (microplastics, engineered nanomaterials); climate change; harmonization of monitoring procedures; and the use of deployed mussels (transplant caging) in pollution monitoring. Lastly, the overall state of the art of blue mussel pollution monitoring is discussed and some important issues for future research and development are highlighted.

Prediction of mono- and polycyclic aromatic hydrocarbon degradation in spiked soils using cyclodextrin extraction.

In this study, an aqueous-based hydroxypropyl-beta-cyclodextrin (HPCD) extraction technique was assessed for its capacity to determine the microbially degradable fraction of mono- and polycyclic aromatic hydrocarbons in four dissimilar soils. A linear relationship (slope=0.90; R2=0.89), approaching 1:1 between predicted and observed phenanthrene mineralization, was demonstrated for the cyclodextrin extraction; however, the water only extraction underestimated the microbially available fraction by a factor of three (slope=3.35; R2=0.64). With respect to determining the mineralizable fraction of p-cresol in soils, the cyclodextrin extraction (slope=0.94; R2=0.84) was more appropriate than the water extraction (slope=1.50; R2=0.36). Collectively, these results suggested that the cyclodextrin extraction technique was suitable for the prediction of the mineralizable fraction of representative PAHs and phenols present in dissimilar soils following increasing soil-contaminant contact times. The assessment of the microbial availability of contaminants in soils is important for a more representative evaluation of soil contamination.

Photodegradation of PAHs in passive water samplers.

Losses of deuterated polycyclic aromatic hydrocarbons (PAHs) used as performance reference compounds (PRCs) in semipermeable membrane devices deployed at fifteen coastal sampling sites near Harstad harbour in Northern Norway were used to investigate photodegradation of these photosensitive compounds. Unusual PRC dissipation profiles, especially for samplers exposed <5m below the water surface are indicative of photodegradation. A strong correlation between loss rates for d12-chrysene and d12-benzo[e]pyrene with consistently higher losses of the latter was found. The observed photodegradation rates may be sufficiently high to impact PAH masses absorbed by a factor of two. This study demonstrates that photodegradation during exposure of passive water samplers needs to be taken into account, particularly with deployments close to the water surface, when using SPMD canisters, or when sampling in the Arctic.

Implications of observed PBDE diffusion coefficients in low density polyethylene and silicone rubber.

A film-stacking technique was used to estimate diffusion coefficients of polybrominated diphenyl ethers (PBDEs) in low density polyethylene (LDPE) and silicone rubber. Substantially higher PBDE diffusion coefficients were observed for silicone rubber (AlteSil™) than for LDPE. A much steeper decrease in LDPE diffusion coefficients was found with increasing PBDE molecular weight than that for silicone rubber. From a passive sampling point-of-view, this means that for equivalent polymer-water partition coefficients for these two materials, the mass transfer resistance for these substances in the LDPE will be significantly higher than that for silicone rubber. Boundary layer control of the uptake process for silicone rubber can be expected for PBDEs. With a microplastic perspective, the low diffusion coefficients of PBDEs and in particular of decabromo diphenyl ether (BDE 209) in LDPE imply that the polymer diffusion coefficients for these plastic additives used as flame retardants need to be taken into account when considering the risk posed by microplastic particle ingestion by marine organisms.