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Bio-based fertilizers (BBFs) produced from organic waste contribute to closed-loop nutrient cycles and circular agriculture. However, persistent organic contaminants, such as per- and poly-fluoroalkyl substances (PFAS), polychlorobiphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), as well as polyaromatic hydrocarbons (PAHs) can be present in organic waste or be formed during valorization processes. Consequently, these hazardous substances may be introduced into agricultural soils and the food chain via BBFs. This study assessed the exposure of 84 target substances and extractable organic fluorine (EOF) in 19 BBFs produced from different types of waste, including agricultural and food industrial waste, sewage sludge, and biowaste, and through various types of valorization methods, including hygienization at low temperatures (<150 °C) as well as pyrolysis and incineration at elevated temperatures (150-900 °C). The concentrations in BBFs (ΣPFOS & PFOA: <30 μg kg -1 , Σ6PCBs: <15 μg kg -1 , Σ11PAHs: <3 mg kg -1 , Σ17PCDD/Fs: <4 ng TEQ kg -1 ) were found to be below the strictest thresholds used in individual EU countries, with only one exception (pyrolyzed sewage sludge, Σ11PAHs: 5.9 mg kg -1 ). Five BBFs produced from sewage sludge or chicken manure contained high concentrations of EOF (>140 μg kg -1 ), so monitoring of more PFAS is recommended. The calculated expected concentrations in soils after one BBF application (e.g. PFOS: <0.05 μg kg -1 ) fell below background contamination levels (PFOS: 2.7 μg kg -1 ) elsewhere in the literature. This was confirmed by the analysis of BBF-amended soils from field experiments (Finland and Austria). Studies on target legacy contaminants in sewage sludge were reviewed, indicating a general decreasing trend in concentration with an apparent half-life ranging from 4 (PFOS) to 9 (PCDD/Fs) years. Modelled cumulative concentrations of the target contaminants in agricultural soils indicated low long-term risks. Concentrations estimated and analyzed in edible plant part were low, indicating that exposure by plant consumption is well below tolerable daily intakes., (Copyright © 2024. Published by Elsevier B.V.)

Equilibrium passive sampling continues to find increasing use for performing in situ assessments and monitoring of hydrophobic organic compounds (HOCs). Although this method has been successfully used in several field studies including open surface waters and sediments, comparatively, their use in groundwater has been very limited. In this study, low-density polyethylene (LDPE) passive samplers were deployed for 80 days in three groundwater wells contaminated with polycyclic aromatic hydrocarbons (PAHs). Prior to deployment, LDPE was loaded with performance reference compounds (PRCs) consisting of deuterated PAHs and their release used to ascertain system equilibrium. Within the 80-day deployment period, LDPE-groundwater equilibrium was confirmed for PAHs with molecular weights (MWs) in the range of 178 to 228 (i.e. anthracene, chrysene). Measured freely dissolved concentrations (C w ) were between one to three orders of magnitude lower than the total filtered concentrations (C total ) in the studied wells. The sum of PAHs (ΣPAHs) measured based on C w and C total were 2.05, 0.07 and 29.2 μg L -1 and 197, 59.7 and 1010 μg L -1 , at wells 1, 2 and 3, respectively. A separate dataset, comprising long-term (2010 to 2022) concentrations of PAHs in total (i.e., unfiltered) groundwater, is also presented to provide insight into PAH contamination levels at the assessed groundwater wells based on conventional measurement. Estimated in situ LDPE daily clearance volumes (2.34 to 27.56 Ld -1 ) for the target analytes were far less than the daily turnover of ground water (144 to 348 Ld -1 ) encountered in the wells eliminating the possibility of depletive sampling of the groundwater by the passive samplers. These results represent the first published study on the practical application of equilibrium passive sampling using LDPE for monitoring and quantitatively assessing PAHs in groundwater. Also, this work demonstrates that LDPEs are a useful tool for measuring the C w of PAHs in groundwater, a critical contaminant in many ecological and human health risk assessments., (© 2024. The Author(s).)

Polycyclic aromatic hydrocarbons (PAHs), released from petrogenic, pyrogenic or diagenetic sources (degradation of wood materials), are of global concern due to their adverse effects, and potential for long-range transport. While dissolved PAHs have been frequently reported in the literature, there has been no consistent approach of sampling across water bodies. Passive samplers from the AQUA/GAPS-MONET initiative were deployed at 46 sites (28 marine and 18 freshwater), and analyzed for 28 PAHs and six polycyclic musks (PCMs) centrally. Freely dissolved PAH concentrations were dominated by phenanthrene (mean concentration 1500 pg L -1 ; median 530 pg L -1 ) and other low molecular weight compounds. Greatest concentrations of phenanthrene, fluoranthene, and pyrene were typically from the same sites, mostly in Europe and North America. Of the PCMs, only galaxolide (72% of samples) and tonalide (61%) were regularly detected, and were significantly cross-correlated. Benchmarking of PAHs relative to penta- and hexachlorobenzene confirmed that the most remote sites (Arctic, Antarctic, and mountain lakes) displayed below average PAH concentrations. Concentrations of 11 of 28 PAHs, galaxolide and tonalide were positively correlated ( P < 0.05) with population density within a radius of 5 km of the sampling site. Characteristic PAH ratios gave conflicting results, likely reflecting multiple PAH sources and postemission changes.

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 Σ 7 PCB, 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.

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 (R T/S ) are explored for these two axes. While the size of the polystyrene nanoplastics biased the pyrolyzates of styrene dimer and trimer, the R T/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., (© 2023. Springer-Verlag GmbH Germany, part of Springer Nature.)

Pharmaceutical deltamethrin (Alpha Max), used as delousing treatments in aquaculture, has raised concerns due to possible negative impacts on the marine environment. A novel approach combining different scientific disciplines has addressed this topic. Acute (mortality) and sublethal effects (i.e., fitness, neurological, immunological, and oxidative responses) of exposure of northern shrimp ( Pandalus borealis ) were studied in laboratory experiments. Passive water sampling combined with sediment analyses revealed environmental concentrations. Finally, dispersal modeling was performed to predict environmental concentrations. Ecotoxicological analyses showed mortality in shrimp after 1 h of exposure to 2 ng L -1 (1000-fold dilution of treatment dose), revealing a high sensitivity to deltamethrin. Sublethal effects included induction of acetylcholinesterase and acyl CoA oxidase activities and oxidative impairment, which may be linked to neurotoxic responses. Field concentrations of 10-200 ng L -1 in water (100 m from the pens) and -1 dw in sediment (0-400 m from pens) were measured. Ecotoxicological values were compared with measured and modeled concentrations. They showed that concentrations higher than those causing mortality could be expected up to 4-5 km from point of release, in an area of 6.4 km 2 , with lethal concentrations remaining up to 35 h in some areas. Hence, the study demonstrates that there is a considerable risk for negative effects on the ecologically and commercially important shrimp.

This study investigated the effect of polyethylene and polyvinyl chloride microplastics on the UV fluence response curve for the inactivation of multidrug-resistant E. coli and enterococci in ultrapure water at pH 6.0 ± 0.1. In the absence of microplastics, the UV inactivation of the studied bacteria exhibited an initial resistance followed by a faster inactivation of free (dispersed) bacteria, while in the presence of microplastics, these 2 regimes were followed by an additional regime of slower or no inactivation related to microplastic-associated bacteria (i.e., bacteria aggregated with microplastics resulting in shielding bacteria from UV indicated by tailing at higher UV fluences). The magnitude of the negative effect of microplastics varied with different microplastics (type/particle size) and bacteria (Gram-negative and Gram-positive). Results showed that when the UV transmittance of the microplastic-containing water was not taken into account in calculating UV fluences, the effect of microplastics as protectors of bacteria was overestimated. A UV fluence-based double-exponential microbial inactivation model accounting for both free and microplastic-associated bacteria could describe well the disinfection data. The present study elucidated the effect of microplastics on the performance of UV disinfection, and the approach used herein to prove this concept may guide future research on the investigation of the possible effect of other particles including nanoplastics with different characteristics on the exposure response curve for the inactivation of various microorganisms by physical and chemical disinfection processes in different water and wastewater matrices., (Copyright © 2022 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Hexachlorobenzene (HCB), listed on the Stockholm Convention on persistent organic pollutants and regulated as a hazardous priority pollutant by the Water Framework Directive (WFD), is ubiquitously distributed in the environment and assumed to mildly biomagnify in aquatic foodwebs. The proposal to include trophic magnification factors (TMFs) in the procedure for comparing contaminant levels in biota at different trophic levels (TLs) with WFD environmental quality standards requires adequate selection of TMFs. In the first step of our study, we compared two independently obtained datasets of pentachlorobenzene (PeCB) and HCB concentration ratios from passive sampling (PS) in water and in fish through routine monitoring programs in Norway to evaluate possible biomagnification. In this procedure, PeCB is used for benchmarking the bioconcentration in fish, and the observed HCB/PeCB ratios in fish are compared with ratios expected in the case of (i) HCB bioconcentration or (ii) biomagnification using published TMF values. Results demonstrate that it is not possible to confirm that HCB biomagnifies in fish species that would be used for WFD monitoring in Norway and challenges the proposed monitoring procedures for such compounds in Norwegian or European waters. In the second step, fish-water chemical activity ratios for HCB and PeCB as well as for polychlorinated biphenyls where biota and PS were conducted alongside were calculated and found to rarely exceed unity for cod ( Gadus morhua ), a fish species with a TL of approximately 4.

In an effort to support European Union Water Framework Directive goals, we have set up a national demonstrator project to identify the advantages and limitations of passive samplers for regulatory monitoring of polar contaminants in surface waters. Here we carried out successive 14 day-deployments of polar organic chemical integrative samplers (POCIS) for one year at three sites. In parallel, we used the passive sampler deployment/retrieval operations to collect spot water samples for comparative analysis. We observed that frequency of quantification was significantly higher in POCIS than spot samples for 29 contaminants, similar for 15, and lower for one, because POCIS lowered the limits of quantification for most contaminants (median value factor of 11). We built a database of sampling rates (Rs) according to quality indices to convert concentrations in POCIS to concentrations in water (23 contaminants with a high-quality median Rs value, 20 with an approximate Rs and two with no usable Rs). Several phenomena were observed over one-year monitoring period. For example, after a flood episode, dilution phenomenon in rivers is correctly observed by using POCIS sampling whereas significant concentration increased due to soil leaching is observed with both passive and spot sampling. Cases of episodic contamination that were missed by spot sampling were observed with POCIS as it was able to capture contamination of short duration but sufficient intensity. Contamination by pharmaceuticals was found to come from wastewater treatment plant discharges and showed relatively little variation over the course of the year in both POCIS and spot samples. POCIS enables more reliable annual monitoring of pesticide and pharmaceutical contamination than spot sampling. Furthermore, POCIS also improves the environmental quality standards based assessment of chemical status and on annual average concentrations compared to spot sampling. This study demonstrates the value and practicability of POCIS-based chemical monitoring for use in regulatory control networks., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

The identification and prioritisation of water bodies presenting elevated levels of anthropogenic chemicals is a key aspect of environmental monitoring programmes. Albeit this is challenging owing to geographical scales, choice of indicator aquatic species used for chemical monitoring, and inherent need for an understanding of contaminant fate and distribution in the environment. Here, we propose an innovative methodology for identifying and ranking water bodies according to their levels of hydrophobic organic contaminants (HOCs) in water. This is based on a unique passive sampling dataset acquired over a 10-year period with silicone rubber exposures in surface water bodies across Europe. We show with these data that, far from point sources of contamination, levels of hexachlorobenzene (HCB) and pentachlorobenzene (PeCB) in water approach equilibrium with atmospheric concentrations near the air/water surface. This results in a relatively constant ratio of their concentrations in the water phase. This, in turn, allows us to (i) identify sites of contamination with either of the two chemicals when the HCB/PeCB ratio deviates from theory and (ii) define benchmark levels of other HOCs in surface water against those of HCB and/or PeCB. For two polychlorinated biphenyls (congener 28 and 52) used as model chemicals, differences in contamination levels between the more contaminated and pristine sites are wider than differences in HCB and PeCB concentrations endorsing the benchmarking procedure.

Passive sampling has been shown to be a suitable procedure to assess the risk of contaminated sediments through the measurement of freely dissolved concentrations (C Free ) 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 C Free 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 C free 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Author(s). Published by Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

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.

Passive sampling is a powerful technique for the sampling hydrophobic organic contaminants present at trace level in water. A robust application of performance reference compounds (PRCs) for the estimation of in situ sampling rates, requires that dissipation of PRC and uptake of target compounds follow the same processes, i.e. the existence of isotropic exchange between the sampler and water. We report circumstantial evidence that in the presence of heavy fouling of samplers by suspended particulate matter (SPM) when deployed in a freshwater environment, SPM deposited on the surface of the sampler enhances the release of PRCs and reduces the uptake of target compounds. In this case, anisotropy of exchange resulted in on average a factor of 3.9 difference in estimate freely dissolved concentration in water., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

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 (K pw ) 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.

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., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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.

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., (Copyright © 2016 Elsevier B.V. All rights reserved.)

There is a growing interest in assessing the concentration and distribution of new nonregulated organic compounds (emerging contaminants) in the environment. The measurement of freely dissolved concentrations using conventional approaches is challenging because of the low concentrations that may be encountered and their temporally variable emissions. Absorption-based passive sampling enables the estimation of freely dissolved concentrations of hydrophobic contaminants of emerging concern in water. In the present study, calibration was undertaken for 2 polymers, low-density polyethylene (LDPE) and silicone rubber for 11 fragrances, 5 endocrine-disrupting compounds, 7 ultraviolet (UV) filters, and 8 organophosphate flame retardant compounds. Batch experiments were performed to estimate contaminant diffusion coefficients in the polymers (Dp ), which in general decreased with increasing molecular weight. The values for fragrances, endocrine-disrupting compounds, and UV filters were in ranges similar to those previously reported for polycyclic aromatic hydrocarbons, but were 1 order of magnitude lower for organophosphate flame retardant compounds. Silicone rubber had higher Dp values than LDPE and was therefore selected for further experiments to calculate polymer/water partition coefficients (KPW ). The authors observed a positive correlation between log KPW and log octanol/water partition coefficient values. Field testing of silicone rubber passive samplers was undertaken though exposure in the River Alna (Norway) for an exposure time of 21 d to estimate freely dissolved concentration. Some fragrances and UV filters were predominant over other emerging and regulated contaminants, at levels up to 1600 ng L(-1) for galaxolide and 448 ng L(-1) for octocrylene. Environ Toxicol Chem 2016;35:2162-2172. © 2016 SETAC., (© 2016 SETAC.)

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.

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., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

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.

Passive sampling devices (PS) are widely used for pollutant monitoring in water, but estimation of measurement uncertainties by PS has seldom been undertaken. The aim of this work was to identify key parameters governing PS measurements of metals and their dispersion. We report the results of an in situ intercomparison exercise on diffusive gradient in thin films (DGT) in surface waters. Interlaboratory uncertainties of time-weighted average (TWA) concentrations were satisfactory (from 28% to 112%) given the number of participating laboratories (10) and ultra-trace metal concentrations involved. Data dispersion of TWA concentrations was mainly explained by uncertainties generated during DGT handling and analytical procedure steps. We highlight that DGT handling is critical for metals such as Cd, Cr and Zn, implying that DGT assembly/dismantling should be performed in very clean conditions. Using a unique dataset, we demonstrated that DGT markedly lowered the LOQ in comparison to spot sampling and stressed the need for accurate data calculation., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

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.

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.

This paper details how activity-based passive sampling methods (PSMs), which provide information on bioavailability in terms of freely dissolved contaminant concentrations (Cfree ), can be used to better inform risk management decision making at multiple points in the process of assessing and managing contaminated sediment sites. PSMs can increase certainty in site investigation and management, because Cfree is a better predictor of bioavailability than total bulk sediment concentration (Ctotal ) for 4 key endpoints included in conceptual site models (benthic organism toxicity, bioaccumulation, sediment flux, and water column exposures). The use of passive sampling devices (PSDs) presents challenges with respect to representative sampling for estimating average concentrations and other metrics relevant for exposure and risk assessment. These challenges can be addressed by designing studies that account for sources of variation associated with PSMs and considering appropriate spatial scales to meet study objectives. Possible applications of PSMs include: quantifying spatial and temporal trends in bioavailable contaminants, identifying and evaluating contaminant source contributions, calibrating site-specific models, and, improving weight-of-evidence based decision frameworks. PSM data can be used to assist in delineating sediment management zones based on likelihood of exposure effects, monitor remedy effectiveness, and, evaluate risk reduction after sediment treatment, disposal, or beneficial reuse after management actions. Examples are provided illustrating why PSMs and freely dissolved contaminant concentrations (Cfree ) should be incorporated into contaminated sediment investigations and study designs to better focus on and understand contaminant bioavailability, more accurately estimate exposure to sediment-associated contaminants, and better inform risk management decisions. Research and communication needs for encouraging broader use are discussed., (© 2014 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of SETAC.)

Equilibrium passive sampling through in vivo implantation can help circumvent complex extractions of biological tissues, provide more accurate information on chemical contaminant burden based on the fugacity of a chemical in an organism rather than conventional normalization to lipid content, and improve the assessment of contaminant bioaccumulation potential. Here, we explored the feasibility of in vivo implantation for the passive sampling of neutral hydrophobic contaminants through the insertion of a silicone tag into brown trout (Salmo trutta). Implanted fish from the upper reaches of the River Alna (Oslo, Norway) were relocated to a polluted section of the river for a 28 day caged exposure. "Whole fish" lipid-silicone distribution coefficients (Dlip-sil) were calculated for chlorinated compounds measured in whole fish and in silicone tags of 13 fish. Dlip-sil ranged from 13.6 to 40.0 g g(-1) for polychlorinated biphenyl congeners 28-156 (CB28 and CB156), respectively, and are in close agreement with literature in vitro lipid phase and tissue-based lipid-silicone partition coefficients. After dissection a further of eight fish, muscle and liver samples were analyzed separately. Muscle-based Dlip-sil values similar to the whole fish data were observed. However, lipid-normalized concentrations in the liver tended to be lower than in muscle for most compounds (by up to 50%). Values of whole fish Dlip-sil for brominated diphenyl ethers determined for three fish were in the range of 8.6-51 g g(-1) and in agreement with chlorinated substances. Finally, fugacity ratios calculated from equilibrium concentrations in fish-implanted and water-exposed silicone provided information on the bioaccumulation for chlorinated compounds as well as for some polycyclic aromatic hydrocarbons. Equilibrium passive sampling through in vivo implantation can allow the comparison of a chemical's activity or fugacity in biotic as well as abiotic environmental compartments and at different trophic levels up to humans.

Persistent organic pollutant (POP) biomonitoring in humans is challenging and generally carried out using blood, breast milk or adipose tissue, with concentrations normalised to the lipid content of the sample matrix. The goal of this cross-sectional pilot study was to evaluate the validity and feasibility of explanted silicone prostheses as a matrix for persistent organic pollutant biomonitoring in humans. We postulate that pollutant concentrations in silicone prostheses inserted in the body will equilibrate with that in the body over time and provide a measure of the overall body burden. This study included silicone prostheses from 22 female patients of the Colosseum clinic (Oslo, Norway) collected between September 2010 and April 2012. Absorption of chlorinated and brominated POPs into silicone prostheses during implantation was observed. Relative levels of the different contaminants measured in prostheses were in agreement with those from serum and breast milk analyses from the general Norwegian population. The comparison of serum and breast milk-based literature data with prosthesis concentrations transposed into lipid-normalised concentrations supports the validity of the prosthesis measurements. The median of relative percent differences between measurements with replicate silicone prostheses from 11 patients was below 30%. Observed increases in prosthesis concentrations with patients' age were found to be very similar to literature data from studies of the Norwegian population. Silicone prostheses therefore represent a promising matrix for the biomonitoring of nonpolar and non-ionic pollutants in humans. Sample accessibility and body burden representativeness of the silicone prostheses suggest that specimen banking should be initiated., (© 2013.)

The applicability of silicone rubber and low-density polyethylene (LDPE) as passive sampling materials for target and nontarget analyses of moderately polar and nonpolar substances was assessed through a field deployment of samplers along a small, polluted stream in Oslo, Norway. Silicone and LDPE samplers of identical surface area (but different volumes) were deployed at 6 sites in the River Alna for 49 d. Quantitative target analysis by gas chromatography-mass spectrometry (quadrupole, single-ion monitoring mode) demonstrated that masses of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine compounds absorbed in the 2 polymeric materials were consistent with the current understanding of the control and mode of accumulation in these sampler materials. Some deviation was observed for decabromodiphenyl ether (BDE-209) and may be linked to the large molecular size of this substance, resulting in lower diffusivity in the LDPE. Target and nontarget analyses with gas chromatography coupled to high resolution time-of-flight mass spectrometry allowed the identification of a wide range of chemicals, including organophosphate compounds (OPCs) and musk compounds (galaxolide and tonalid). Semiquantitative analysis revealed enhanced quantities of the OPCs in silicone material, indicating some limitation in the absorption and diffusion of these substances in LDPE. Overall, silicone allows nontarget screening analysis for compounds with a wider range of log octanol-water partition coefficient values than what can be achieved with LDPE., (Copyright © 2013 SETAC.)

Many contaminants are recalcitrant against degradation. Therefore, when primary sources have been discontinued, contaminated sediments often function as important secondary pollution sources. Since the management and potential remediation of contaminated marine sediments may be very costly, it is important that the environmental risks of contaminants present in these sediments and benefits of remediation are evaluated as accurately as possible. The objective of this study was to evaluate the bioavailability of common organochlorine contaminants and polycyclic aromatic hydrocarbons (PAHs) in selected polluted sediments from Norway by simple generic sorption models (free energy relationships), as well as by pore water concentration measurements. Furthermore, the aim was to predict bioaccumulation from these bioavailability estimates for comparison with in vivo bioaccumulation assessments using ragworm (Nereis virens) and netted dogwhelk (Hinia reticulata). Predicted biota-to-sediment accumulation factors (BSAFs) derived from pore water concentration estimates were in better agreement with the bioaccumulation observed in the test organisms, than the generic BSAFs expected based on linear sorption models. The results therefore support that site-specific evaluations of bioaccumulation provide useful information for more accurate risk assessments. A need for increased knowledge of the specific characteristics of benthic organisms, which may influence the exposure, uptake and elimination of contaminants, is however emphasized., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Benthic trawling can cause the resuspension of large amounts of sediments. Such regular practice in the Grenland fjord system in the south of Norway has the potential to affect the fate, movement, and bioavailability of sediment-associated polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). A novel mode of exposing passive sampling devices consisting of towing semipermeable membrane devices attached to the trawl net was used to gauge in situ changes in the freely dissolved concentration of PCDD/Fs on benthic trawler-induced sediment resuspension. Significant accumulation of a number of PCDD/F congeners was observed despite the short (5 h) sampler exposure times. On average, a one order of magnitude increase in freely dissolved PCCD/F concentrations was seen within minutes of the sediment being resuspended. This observation was supported by similar changes in filtered PCDD/F concentrations measured by high-volume sampling prior to resuspension and in the sediment plume., (Copyright © 2012 SETAC.)

The implementation of strict environmental quality standards for polar organic priority pollutants poses a challenge for monitoring programs. The polar organic chemical integrative sampler (POCIS) may help to address the challenge of measuring low and fluctuating trace concentrations of such organic contaminants, offering significant advantages over traditional sampling. In the present review, the authors evaluate POCIS calibration methods and factors affecting sampling rates together with reported environmental applications. Over 300 compounds have been shown to accumulate in POCIS, including pesticides, pharmaceuticals, hormones, and industrial chemicals. Polar organic chemical integrative sampler extracts have been used for both chemical and biological analyses. Several different calibration methods have been described, which makes it difficult to directly compare sampling rates. In addition, despite the fact that some attempts to correlate sampling rates with the properties of target compounds such as log K(OW) have been met with varying success, an overall model that can predict uptake is lacking. Furthermore, temperature, water flow rates, salinity, pH, and fouling have all been shown to affect uptake; however, there is currently no robust method available for adjusting for these differences. Overall, POCIS has been applied to a wide range of sampling environments and scenarios and has been proven to be a useful screening tool. However, based on the existing literature, a more mechanistic approach is required to increase understanding and thus improve the quantitative nature of the measurements., (Copyright © 2012 SETAC.)

Sediments are sinks for contaminants in the world's oceans. At the same time, commercial bottom trawling is estimated to affect around 15 million km(2) of the world's seafloor every year. However, few studies have investigated whether this disturbance remobilises sediment-associated contaminants and, if so, whether these are bioavailable to aquatic organisms. This field study in a trawled contaminated Norwegian fjord showed that a single 1.8 km long trawl pass created a 3-5 million m(3) sediment plume containing around 9 t contaminated sediment; ie. 200 g dw m(-2) trawled, equivalent to c. 10% of the annual gross sedimentation rate. Substantial amounts of PCDD/Fs and non-ortho PCBs were released from the sediments, likely causing a semi-permanent contaminated sediment suspension in the bottom waters. PCDD/Fs from the sediments were also taken up by mussels which, during one month, accumulated them to levels above the EU maximum advised concentration for human consumption., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Freely dissolved pore water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), penta- and hexachlorobenzene (PeCB and HCB), octachlorostyrene (OCS), p,p'-DDE and p,p'-DDD were measured in bottom sediments from three sites in Norway. Sediments were from Aker Brygge, site of a former shipyard in the inner part of Oslofjord, Frierfjord in the Grenlandsfjord area, impacted during the 50 year-long activity of a magnesium smelter plant, and from Kristiansand harbour, site with high industrial activity. Low density polyethylene (LDPE) membrane samplers were exposed to these sediments in laboratory incubation under constant and low-level agitation for periods of 1, 2, 6, 13, 23 and 50 days. Freely dissolved pore water concentrations were estimated from contaminant masses accumulated and sampling rates obtained from the measurement of kinetics of dissipation of performance reference compounds (PRCs). Marked differences in freely dissolved PAH concentrations and resulting organic carbon-normalised sediment-pore water partition coefficients, logK(TOC), between these three sediments could be observed despite the generally similar total sediment concentrations. In contrast with the PAH data, partitioning of PCBs and other organochlorine compounds (OCs) was relatively similar in all three sediments. For sediments from Frierfjord and Kristiansand, logK(TOC) values were lower for PCBs/OCs than for PAHs, indicating higher availability. Similar partitioning of PAHs and PCBs/OCs was found for sediments from Aker Brygge. No simple logK(oc)-logK(ow) relationships could model these data successfully. These results support the notion that the assessment of the risk posed by these compounds present in sediments in most cases requires actual measurement of contaminant availability., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Integrative passive sampling with devices such as semipermeable membrane devices generally relies on rigs for month-long static exposures in water. We evaluate here whether mobile exposures of passive samplers can provide reliable estimates of dissolved contaminant concentrations. Mobile exposures were obtained by towing samplers fastened to the end of a benthic trawl net. Significant and reproducible absorption of polycyclic aromatic hydrocarbons during 5 h-long deployments was made possible by high sampling rates resulting from high water turbulences during towing at 1.2-1.5 knots. Sampling rates (72-215 L d(-1)) estimated from the dissipation of performance reference compounds were supported by in situ calibration with samplers exposed for a 30 days in the vicinity of the test site. Higher fluoranthene and pyrene absorption in samplers exposed to the trawling-induced sediment plume could be attributed to desorption from re-suspended sediments. This mode of exposure has the potential to be used in monitoring programmes., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Thirty two polychlorinated biphenyl congeners (PCBs), hexachlorobenzene (HCB) and pentachlorobenzene (PeCB) were analysed in passive sampler extracts from surface water-exposed semipermeable membrane devices (SPMDs) and in bed sediment samples from a small urban watercourse, the River Alna (Oslo, Norway). Performance reference compound-corrected data from the passive samplers deployed at three sites along the river were used to track PCB contamination in the overlying water. SPMDs were able to detect an increase in dissolved PCB concentrations at the site furthest downstream that was corroborated by bed sediment concentrations. In comparison, no major increase in concentration of HCB, PeCB or PAHs could be observed. Comparison of passive sampling-based overlying water concentrations with total concentrations measured in bed sediments supports the possibility of further PCB sources upstream of the study area. Diagnostic PAH ratios (from SPMDs) and PCB congener pattern (from sediments) were used in an attempt to identify possible contaminant sources to the Alna River. Selected PAH diagnostic ratios support a multiple emission source scenario and demonstrate the complexity of identifying specific sources of these compounds to surface waters. PCB congener patterns in sediments from all three sites tend to indicate a source of highly chlorinated PCBs (of the Archlor 1260 type) and either a source of lower chlorinated PCBs or the less-likely occurrence of dechlorination in sediment. Information collected during the present screening study also confirms the Alna River as a continuous source of PCBs to the Oslofjord.

Increasing demand for simple and reliable passive samplers for monitoring hydrophobic organic contaminants in water has led to increased frequency of use of single-phase polymeric sampling devices. In this study, we evaluate the effect of sampler material on the passive sampling of polycyclic aromatic hydrocarbons (PAHs) in two Norwegian rivers. Low density polyethylene membranes (LDPE), silicone strips and semipermeable membrane devices (SPMDs) with the exact same surface area and conformation were exposed in the Drammen River for overlapping exposures of 24 and 51 d, under identical hydrodynamic conditions. Dissipation rates of performance reference compounds (PRCs) spiked in all samplers were consistent and demonstrated no significant differences in sampler-water analyte exchange kinetics between the two exposures. The transition to fully boundary layer-controlled uptake shown by PRC dissipation rates was confirmed by investigating PAH masses absorbed by the samplers. Masses of analytes with log K(ow)>4.5 absorbed into the samplers were similar and independent of the sampler material used, generally indicating for these compounds that the boundary layer dominated the resistance to mass transfer. The very low variability in analyte masses absorbed across sampler types observed here indicates that much of the overall variability in dissolved contaminant concentrations seen in passive sampler intercomparison studies is likely the result of the uncertainty associated with sampler-water partition coefficients and PRC dissipation rates. PRC dissipation rates and ratios of masses absorbed over 51 and 24 d for these compounds demonstrated integrative sampling over 51 d and no major effects of biofouling on sampling. The equivalence of data obtained using silicone strips and SPMDs supports the use of single-phase polymeric passive sampling devices., ((c) 2010 Elsevier Ltd. All rights reserved.)

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.

The performance of seven passive sampling devices for the monitoring of dissolved concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), hexachlorobenzene, and p,p'-DDE was evaluated through simultaneous field exposures of 7-28 days in the River Meuse (The Netherlands). Data from the Chemcatcher, low density polyethylene membranes, two versions of the membrane-enclosed sorptive coating (MESCO) sampler, silicone rods, silicone strips and semipermeable membrane devices (SPMD) was assessed through rate of dissipation of performance reference compounds (PRCs), mass of analyte absorbed by the samplers and time-weighted average concentration (C(TWA)) data. Consistent PRC data throughout the range of samplers tested here confirmed the transition from membrane- to boundary layer-controlled exchange at log K(ow) 4.5-5.0. The comparison of sampler surface area-normalized masses absorbed for analytes under boundary layer-control showed some variability between samplers that can be attributed to the conformation and deployment of the various samplers and to the uncertainty associated with the analysis conducted in different laboratories. Despite different modes of calculation, relatively consistent C(TWA) were obtained for the different samplers. The observed variability is likely to be due to the uncertainty of sampler-water partition coefficients and the extrapolation of analyte uptake rates at the high log K(ow) range (under boundary layer-controlled exchange) from a narrow PRC data range, and these issues require further work. Finally, the usefulness of passive sampler-generated contaminant concentrations is demonstrated through the comparison with institutional monitoring and with European Water Framework Directive Environmental Quality Standards (EQS).

This study sought to extend validation of a cyclodextrin based extraction method for the assessment of PAH-biodegradation potential to complex multi-contaminant matrices. To this end, four reference materials (RMs) were produced by blending, in different proportions, soils impacted with diesel, lubricating oil and spent oxide. These reference materials had modest summation operatorPAH (16 US EPA) concentrations that ranged from 5.6+/-0.5 to 44.4+/-4.5 mg kg(-1). However, extractable petroleum hydrocarbon (EPH) concentrations were comparatively high (up to 2520+/-204 mg kg(-1)). To complement these RMs, two further soils from a municipal gas plant (MGP) with highly elevated concentration of PAHs ranging from 877+/-52 to 2620+/-344 mg kg(-1) were also tested. Results showed, regardless of matrix complexity, that PAH biodegradation within the four RM substrates, and two MGP soils correlated well with biodegradation predicted by hydroxypropyl-beta-cyclodextrin (HPCD) extraction.

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.

Biological early warning systems represent a set of tools that may be able to respond to certain chemical monitoring requirements of recent European legislation, the Water Framework Directive (WFD2000/60/EC), that aims to improve and protect water quality across Europe. In situ biomonitoring was performed along the rivers Meuse (NL), Aller (GER) and Rhine (F) within the frame of the European Union-funded Project SWIFT-WFD. Gammarus pulex was used as a test organism during the evaluation of the Multispecies Freshwater Biomonitor(R) (MFB), an online biomonitor to quantitatively record different behaviour patterns of animals. At the river Meuse G. pulex reacted to pulse exposure of either a mixture of trace metals or of several organic xenobiotics, by showing up to 20% decreased locomotory activity (already at the 1st pulse) and increased mortality (at 2nd or 3rd pulse only). G. pulex deployed within the MFB system were observed to survive well at the monitoring station on the Aller (100%) and monitoring did not result in the measurement of chemical irregularities. In contrast, deployment at the monitoring station on the Rhine river demonstrated that the test organism was able to detect chemical irregularities by up to 20% decreased locomotory activity in the animals. The MFB proved to be an alert system for water quality monitoring at sensitive sites and sites with accidental pollution.

This work aimed to evaluate the relative contribution of soil catabolic activity, contaminant bioaccessibility, and nutrient levels on the biodegradation of field-aged polycyclic aromatic hydrocarbons and phenolic compounds in three municipal gas plant site soils. Extents of biodegradation achieved, in 6 week-long soil slurry assays, under the following conditions were compared: (i) with inoculation of catabolically active PAH and phenol-degrading microorganisms, (ii) with and without hydroxypropyl-beta-cyclodextrin supplementation (HPCD; 100 g L(-1)), and finally (iii) with the provision of additional inorganic nutrients in combination with HPCD. Results indicated no significant (p < 0.05) differences between biodegradation endpoints attained in treatments inoculated with catabolically active microorganisms as compared with the uninoculated control. Amendments with HPCD significantly (p < 0.05) lowered biodegradation endpoints for most PAHs and phenolic compounds. Only in one soil did the combination of HPCD and nutrients consistently achieve better bioremediation endpoints with respect to the HPCD-only treatments. Thus, for most compounds, biodegradation was not limited by the catabolic activity of the indigenous microorganisms but rather by processes resulting in limited availability of contaminants to degraders. It is therefore suggested that the bioremediation of PAH and phenol impacted soils could be enhanced through HPCD amendments. In addition, the biodegradability of in situ and spiked (deuterated analogues) PAHs following 120 days aging of the soils suggested that this contact time was not sufficient to obtain similar partitions to that observed for field-aged contaminants; with the spiked compounds being significantly (p < 0.05) more available for biodegradation.

Passive sampling devices accumulate chemicals continuously from water and can provide time weighted average (TWA) concentrations of pollutants over the exposure period. Hence, they offer a number of advantages over other conventional monitoring techniques such as spot or grab sampling. The diffusive gradient in thin film (DGT) and the Chemcatcher passive samplers can be used to provide TWA concentrations of labile metals, but the approaches to their calibration differ. DGT uses diffusion coefficients of metals in the hydrogel layer, whereas Chemcatcher uses metal specific uptake rates, with both sets of values obtained under controlled laboratory conditions with constant aqueous metal concentrations. However, little is known of how such samplers respond to fluctuating concentrations. We evaluated the responsiveness of these two passive sampling devices to rapidly changing concentrations of Cd, Cu, Ni, Pb and Zn in natural freshwater, over a relatively short deployment time. Maximum metal concentrations in water were varied between 70 and 140 microg L(-1). Experiments were carried out in a tank with a rotating carousel system and filled with Meuse river water, allowing a degree of control over experimental conditions while using natural river water. Fluctuating concentrations were obtained by stepwise addition of standard solutions of the metals. The reliability and accuracy of the TWA concentrations measured by the samplers were assessed by comparison with concentrations of the metals in spot samples of water taken regularly over the deployment period. The spot samples of water were either unfiltered (total), filtered (0.45 microm) or ultrafiltered (5 kDa). Predictive speciation modelling using the visual MINTEQ programme was also undertaken. There was reasonable agreement between the TWA concentrations of Cd and Ni obtained with Chemcatcher and DGT and the total Cd and Ni concentrations measured in repeated unfiltered spot samples. For elements (i.e. Cu, Pb, Zn) that associate to a significant degree with suspended solids, colloids or dissolved organic carbon, or form complexes with large organic ligands, optimum agreement was with the filtered or ultrafiltered fractions and with the predicted inorganic and inorganic-fulvic acid associated fractions. While Chemcatcher-based TWA concentration ranges for Cu and Zn were in best agreement with the total filtered fraction, there was lack of agreement for Pb. The combined use of DGT devices with open pore (OP) and restricted pore (RP) gels allowed the labile fraction of metal associated with large organic ligands or DOC to be differentiated and quantified, since this is available to DGT OP but unable to diffuse into the DGT RP. This evaluation of the two sampling devices clearly demonstrated their ability to react reliably to transient peaks in concentration of metal pollutants in water and indicated where future efforts are needed to improve calibration data. Such samplers may prove valuable in responding to the monitoring requirements of the European Union's Water Framework Directive.

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.