Endocrine disrupting potential of total and bioaccessible extracts of dust from seven different types of indoor environment.

Information on the indoor environment as a source of exposure with potential adverse health effects is mostly limited to a few pollutant groups and indoor types. This study provides a comprehensive toxicological profile of chemical mixtures associated with dust from various types of indoor environments, namely cars, houses, prefabricated apartments, kindergartens, offices, public spaces, and schools. Organic extracts of two different polarities and bioaccessible extracts mimicking the gastrointestinal conditions were prepared from two different particle size fractions of dust. These extracts were tested on a battery of human cell-based bioassays to assess endocrine disrupting potentials. Furthermore, 155 chemicals from different pollutant groups were measured and their relevance for the bioactivity was determined using concentration addition modelling. The exhaustive and bioaccessible extracts of dust from the different microenvironments interfered with aryl hydrocarbon receptor, estrogen, androgen, glucocorticoid, and thyroid hormone (TH) receptor signalling, and with TH transport. Noteably, bioaccessible extracts from offices and public spaces showed higher estrogenic effects than the organic solvent extracts. 114 of the 155 targeted chemicals were detectable, but the observed bioactivity could be only marginally explained by the detected chemicals. Diverse toxicity patterns across different microenvironments that people inhabit throughout their lifetime indicate potential health and developmental risks, especially for children. Limited data on the endocrine disrupting potency of relevant chemical classes, especially those deployed as replacements for legacy contaminants, requires further study.

Accessibility investigation of semi-volatile organic compounds in indoor dust estimated by multi-ratio equilibrium passive sampling.

Many semi-volatile organic compounds (SVOCs) accumulate in indoor dust, which serves as a repository for those compounds. The presence of SVOCs in indoor environments is of concern because many of them are suspected to have toxic effects. Total SVOC concentrations in the dust are generally used for exposure assessment to indoor contaminants, assuming that 100% of the SVOCs is accessible for human uptake. However, such an assumption may potentially lead to an overestimated risk related to dust exposure. We applied a multi-ratio equilibrium passive sampling (MR-EPS) for estimation of SVOC accessibility in indoor settled dust using silicone passive samplers and three particle size dust fractions, <0.25 mm, 0.25-0.5 mm, and 1-2 mm in dry and wet conditions. Equilibrations were performed at various sampler-dust mass ratios to achieve different degrees of SVOC depletion, allowing the construction of a desorption isotherm. The desorption isotherms provided accessible fractions (FAS), equivalent air concentrations (CAIR), dust-air partition coefficients (KDUST-AIR) and organic carbon-air partition coefficients (KOC-AIR). The highest FAS were observed in the <0.25 mm dust fraction in wet conditions which is relevant for exposure assessment via oral ingestion. The highest CAIR were estimated for several organophosphorus flame retardants (OPFRs), polycyclic aromatic hydrocarbons (PAHs) and synthetic musks. The logKOC-AIR did not differ between dust particle sizes in dry and wet conditions but within compound groups, different relationships with hydrophobicity were observed. Equivalent lipid-based concentrations (CL⇌DUST) calculated using available lipid-silicone partition coefficients (KLIP-SIL) were compared with lipid-based concentrations (CL) measured in human-related samples collected from Europeans. For hexachlorobenzene (HCB), CL⇌DUST, and CL were similar, indicating equilibrium attainment between environment and human samples. Lipid-based concentrations for persistent legacy contaminants were also similar but lower for PBDEs in human samples. Overall, accessibility estimation using MR-EPS in dust further contributes to human risk assessment.

Application of equilibrium passive sampling to profile pore water and accessible concentrations of hydrophobic organic contaminants in Danube sediments.

Total concentrations of hydrophobic organic contaminants (HOCs) in sediment present a poor quality assessment parameter for aquatic organism exposure and environmental risk because they do not reflect contaminant bioavailability. The bioavailability issue of HOCs in sediments can be addressed by application of multi-ratio equilibrium passive sampling (EPS). In this study, riverbed sediment samples were collected during the Joint Danube Survey at 9 locations along the Danube River in 2013. Samples were ex-situ equilibrated with silicone passive samplers. Desorption isotherms were constructed, yielding two endpoints: pore water (CW:0) and accessible (CAS:0) concentration of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers in sediment. CW:0 concentrations of DDT and its breakdown products exhibited elevated levels in the low Danube, with the maximum in the river delta. Other investigated HOCs did not show any clear spatial trends along the river, and only a moderate CW:0 variability. CAS:0 in sediment ranged from 10 to 90% of the total concentration in sediment. CW:0 was compared with freely dissolved concentration in the overlaying surface water, measured likewise by passive sampling. The comparison indicated potential compound release from sediment to the water phase for PAHs with less than four aromatic rings, and for remaining HOCs either equilibrium between sediment and water, or potential compound deposition in sediment. Sorption partition coefficients of HOC to organic carbon correlated well with octanol-water partition coefficients (KOW), showing stronger sorption of PAHs to sediment than that of PCBs and OCPs having equal logKOW. Comparison of CW:0 values with European environmental quality standards indicated potential exceedance for hexachlorobenzene, fluoranthene and benzo[a]pyrene at several sites. The study demonstrates the utility of passive sampling as an innovative approach for risk-oriented monitoring of HOCs in river catchments.

Unraveling the Relationship between the Concentrations of Hydrophobic Organic Contaminants in Freshwater Fish of Different Trophic Levels and Water Using Passive Sampling.

The concentrations of hydrophobic organic compounds (HOCs) in aquatic biota are used for compliance, as well as time and spatial trend monitoring in the aqueous environment (European Union water framework directive, OSPAR). Because of trophic magnification in the food chain, the thermodynamic levels of HOCs, for example, polychlorinated biphenyl congeners, dichlorodiphenyltrichloroethane, and brominated diphenyl ether congeners, in higher trophic level (TL) organisms are expected to be strongly elevated above those in water. This work compares lipid-based concentrations at equilibrium with the water phase derived from aqueous passive sampling (CL⇌water) with the lipid-based concentrations in fillet and liver of fish (CL) at different TLs for three water bodies in the Czech Republic and Slovakia. The CL values of HOCs in fish were near CL⇌water, only after trophic magnification up to TL = 4. For fish at lower TL, CL progressively decreased relative to CL⇌water as KOW of HOCs increased above 106. The CL value decreasing toward the bottom of the food chain suggests nonequilibrium for primary producers (algae), which is in agreement with modeling passive HOC uptake by algae. Because trophic magnification and the resulting CL in fish exhibit large natural variability, CL⇌water is a viable alternative for monitoring HOCs using fish, showing a twofold lower confidence range and requiring less samples.

Investigating levels of organic contaminants in Danube River sediments in Serbia by multi-ratio equilibrium passive sampling.

The Danube River is a large transboundary river with many tributaries. Pollution from industries, municipal wastewater and navigation is discharged into the river directly or via its tributaries. These discharges can adversely contribute to the water and sediment quality, posing a risk to aquatic life. Contaminants with low water solubility tend to accumulate in suspended solids, which deposit in riverbed sediments. Subsequently, their levels in sediment represent a time integrated sample indicating the pollution in the watercourse. However, total concentrations in sediment do not directly represent the exposure risk to aquatic life as accumulation in sediment heavily depends on its properties, i.e. the amount of organic material and its composition, which is difficult to characterize as any natural material. To provide contaminant concentrations on a defined basis, surface layer riverbed sediment samples collected at eleven locations along the Danube stretch in the territory of Serbia in 2012, were ex-situ (in the laboratory) equilibrated with silicone passive samplers of constant accumulative properties, using the multi-ratio equilibrium passive sampling approach. Contaminant's equilibrium concentrations in passive samplers are mutually comparable in time and space and are better measure for bioavailability than total sediment concentrations. Uptake in the passive sampler converted to equivalent freely dissolved (pore-) water concentrations agreed well with those obtained from surface water passive sampling carried out within the Joint Danube Survey 3 in 2013. Furthermore, equilibrium passive sampler PCB concentrations, converted to lipid-based concentrations, agreed well with concentrations measured in fish sampled in the Danube several years earlier. Out of eleven priority substances, only fluoranthene exceeded the EU EQS in water, while the EQS for biota was exceeded or approached for fluoranthene and benz[a]pyrene, and hexachlorobenzene.

Chasing equilibrium passive sampling of hydrophobic organic compounds in water.

We investigated a combination of approaches to extend the attainment of partition equilibria between silicone passive samplers (samplers) and surface or treated waste water towards more hydrophobic organic compounds (HOC). The aim was to identify the HOC hydrophobicity range for which silicone sampler equilibration in water is feasible within a reasonable sampler deployment period. Equilibrium partitioning of HOC between sampler and water is desirable for a simpler application as a "chemometer", aiming to compare chemical activity gradients across environmental media (e.g. water, sediment, biota). The tested approaches included a) long sampler exposure periods and high water flow to maximize mass transfer from water to sampler; b) the use of samplers with reduced sheet thicknesses; and c) pre-equilibration of samplers with local bottom sediment, followed by their exposure in surface water at the same sampling site. These approaches were tested at three sites including a fish pond with a low level of pollution, a river impacted by an urban agglomeration and an effluent of municipal wastewater treatment plant. Tested compounds included polychlorinated biphenyls (PCB), polycyclic aromatic hydrocarbons (PAH), DDT, its metabolites and their isomers, hexachlorobenzene (HCB) and polybrominated diphenyl ethers (PBDE). The study shows that samplers with a surface area of 400-800 cm2 consisting of thin (100-500 µm) silicone sheets exposed at sampling rates of 10-40 L d-1 for a time period of up to four months reach partition equilibrium with water for compounds with log Kow ≤ 5.5. Nevertheless, for compounds beyond this limit it is challenging, within a reasonable time period, to reach equilibrium between sampler and water in an open system where water boundary layer resistance controls the mass transfer. For more hydrophobic HOC (log Kow > 6), the kinetic method using performance reference compounds is recommended instead.

Mobile dynamic passive sampling of trace organic compounds: Evaluation of sampler performance in the Danube River.

A "dynamic" passive sampling (DPS) device, consisting of an electrically driven large volume water pumping device coupled to a passive sampler exposure cell, was designed to enhance the sampling rate of trace organic compounds. The purpose of enhancing the sampling rate was to achieve sufficient method sensitivity, when the period available for sampling is limited to a few days. Because the uptake principle in the DPS remains the same as for conventionally-deployed passive samplers, free dissolved concentrations can be derived from the compound uptake using available passive sampler calibration parameters. This was confirmed by good agreement between aqueous concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) derived from DPS and conventional caged passive sampler. The DPS device enhanced sampling rates of compounds that are accumulated in samplers under water boundary layer control (WBL) more than five times compared with the conventionally deployed samplers. The DPS device was deployed from a ship cruising downstream the Danube River to provide temporally and spatially integrated concentrations. A DPS-deployed sampler with surface area of 400cm2 can reach sampling rates up to 83Ld-1. The comparison of three passive samplers made of different sorbents and co-deployed in the DPS device, namely silicone rubber (SR), low density polyethylene (LDPE) and SDB-RPS Empore™ disks showed a good correlation of surface specific uptake for compounds that were sampled integratively during the entire exposure period. This provided a good basis for a cross-calibration between the samplers. The good correlation of free dissolved PAHs, PCBs and HCB concentration estimates obtained using SR and LDPE confirmed that both samplers are suitable for the identification of concentration gradients and trends in the water column. We showed that the differences in calculated aqueous concentrations between sampler types are mainly associated with different applied uptake models.

Advancing the Use of Passive Sampling in Risk Assessment and Management of Sediments Contaminated with Hydrophobic Organic Chemicals: Results of an International Ex Situ Passive Sampling Interlaboratory Comparison.

This work presents the results of an international interlaboratory comparison on ex situ passive sampling in sediments. The main objectives were to map the state of the science in passively sampling sediments, identify sources of variability, provide recommendations and practical guidance for standardized passive sampling, and advance the use of passive sampling in regulatory decision making by increasing confidence in the use of the technique. The study was performed by a consortium of 11 laboratories and included experiments with 14 passive sampling formats on 3 sediments for 25 target chemicals (PAHs and PCBs). The resulting overall interlaboratory variability was large (a factor of ∼10), but standardization of methods halved this variability. The remaining variability was primarily due to factors not related to passive sampling itself, i.e., sediment heterogeneity and analytical chemistry. Excluding the latter source of variability, by performing all analyses in one laboratory, showed that passive sampling results can have a high precision and a very low intermethod variability (

Effect-based monitoring of the Danube River using mobile passive sampling.

Many aquatic pollutants can be present at low concentrations, but their mixtures can still affect health or behavior of exposed organisms. In this study, toxicological and chemical analyses were combined for spatial contamination profiling using an innovative passive sampling approach. A novel Dynamic Passive Sampler (DPS) was employed as a mobile sampler from a ship cruising along 2130km of the Danube river during the Joint Danube Survey 3 (JDS3). The sampling was performed in eight subsequent river stretches with two types of complementary passive samplers: silicone rubber sheets (SR) used for non-polar chemicals and SDB-RPS Empore™ disks (ED) for more hydrophilic compounds. Besides extensive chemical analyses, the bioactivity of samples was characterized by a battery of reporter gene bioassays. Cross-calibration of the employed passive samplers enabled robust estimation of water concentrations applicable for compounds with a wide range of physicochemical properties. DPS was suitable for sampling of water contaminants even at pgL-1 levels, with 209 of 267 analyzed compounds detected in the samples. Biological effects were detected in both ED and SR extracts across all river stretches by bioassays focused on xenobiotic metabolism mediated by the aryl hydrocarbon and pregnane X receptors, endocrine disruptive potential mediated by estrogen and androgen receptors and the oxidative stress response. The bioassay responses expressed as bioanalytical equivalent concentrations (BEQbio) were comparable with data obtained from large volume active sampling. The extracts of the ED samplers were more biologically active than extracts of SR samplers. Except of estrogenicity, where the analyzed chemicals explained on average 62% of the effects in ED samples, the detected chemicals explained <8% of BEQbio values. The study shows the utility of the combination of the innovative passive sampling approach with effect-based tools for efficient and fast monitoring even in water bodies with relatively low levels of contamination.

Investigation of cosolvent application to enhance POPs' mass transfer in partitioning passive sampling in sediment.

The freely dissolved concentration of persistent organic pollutants (POPs) is one of the most important parameters for risk assessment in aquatic environments, due to its proportionality to the chemical activity. Chemical activity difference represents the driving force for a spontaneous contaminant transport, such as water-aquatic biota or water-sediment. Freely dissolved concentrations in sediment pore water can be estimated from the concentrations in a partition-based passive sampler equilibrated in suspensions of contaminated sediment. Equilibration in the sediment/passive sampler system is slow, since concentrations of most POPs in the water phase, which is the main route for mass transfer, are very low. Adding methanol to sediment in suspension increases the POPs' solubility and, consequently, the permeability in the water phase. The resulting higher aqueous concentrations enhance POPs mass transfer up to three times for investigated POPs (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorine pesticides) and shorten equilibrium attainment to less than 6 weeks. The addition of methanol to the aqueous phase up to a molar fraction of 0.2 changed the POPs equilibrium distribution ratio between sediment and passive sampler by less than a factor of two. As a result, the pore water concentrations of POPs, calculated from their amounts accumulated in a passive sampler, are affected by methanol addition not more than by the same factor.

Equilibrium Passive Sampling of POP in Lipid-Rich and Lean Fish Tissue: Quality Control Using Performance Reference Compounds.

Passive sampling is widely used to measure levels of contaminants in various environmental matrices, including fish tissue. Equilibrium passive sampling (EPS) of persistent organic pollutants (POP) in fish tissue has been hitherto limited to application in lipid-rich tissue. We tested several exposure methods to extend EPS applicability to lean tissue. Thin-film polydimethylsiloxane (PDMS) passive samplers were exposed statically to intact fillet and fish homogenate and dynamically by rolling with cut fillet cubes. The release of performance reference compounds (PRC) dosed to passive samplers prior to exposure was used to monitor the exchange process. The sampler-tissue exchange was isotropic, and PRC were shown to be good indicators of sampler-tissue equilibration status. The dynamic exposures demonstrated equilibrium attainment in less than 2 days for all three tested fish species, including lean fish containing 1% lipid. Lipid-based concentrations derived from EPS were in good agreement with lipid-normalized concentrations obtained using conventional solvent extraction. The developed in-tissue EPS method is robust and has potential for application in chemical monitoring of biota and bioaccumulation studies.

Partitioning of hydrophobic organic contaminants between polymer and lipids for two silicones and low density polyethylene.

Polymers are increasingly used for passive sampling of neutral hydrophobic organic substances (HOC) in environmental media including water, air, soil, sediment and even biological tissue. The equilibrium concentration of HOC in the polymer can be measured and then converted into equilibrium concentrations in other (defined) media, which however requires appropriate polymer to media partition coefficients. We determined thus polymer-lipid partition coefficients (KPL) of various PCB, PAH and organochlorine pesticides by equilibration of two silicones and low density polyethylene (LDPE) with fish oil and Triolein at 4 °C and 20 °C. We observed (i) that KPL was largely independent of lipid type and temperature, (ii) that lipid diffusion rates in the polymers were higher compared to predictions based on their molecular volume, (iii) that silicones showed higher lipid diffusion and lower lipid sorption compared to LDPE and (iv) that absorbed lipid behaved like a co-solute and did not affect the partitioning of HOC at least for the smaller molecular size HOC. The obtained KPL can convert measured equilibrium concentrations in passive sampling polymers into equilibrium concentrations in lipid, which then can be used (1) for environmental quality monitoring and assessment, (2) for thermodynamic exposure assessment and (3) for assessing the linkage between passive sampling and the traditionally measured lipid-normalized concentrations in biota. LDPE-lipid partition coefficients may also be of use for a thermodynamically sound risk assessment of HOC contained in microplastics.

Air and seawater pollution and air-sea gas exchange of persistent toxic substances in the Aegean Sea: spatial trends of PAHs, PCBs, OCPs and PBDEs.

Near-ground air (26 substances) and surface seawater (55 substances) concentrations of persistent toxic substances (PTS) were determined in July 2012 in a coordinated and coherent way around the Aegean Sea based on passive air (10 sites in 5 areas) and water (4 sites in 2 areas) sampling. The direction of air-sea exchange was determined for 18 PTS. Identical samplers were deployed at all sites and were analysed at one laboratory. hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs) as well as dichlorodiphenyltrichloroethane (DDT) and its degradation products are evenly distributed in the air of the whole region. Air concentrations of p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) and o,p'-DDT and seawater concentrations of p,p'-DDE and p,p'-DDD were elevated in Thermaikos Gulf, northwestern Aegean Sea. The polychlorinated biphenyl (PCB) congener pattern in air is identical throughout the region, while polybrominated diphenylether (PBDE)patterns are obviously dissimilar between Greece and Turkey. Various pollutants, polycyclic aromatic hydrocarbons (PAHs), PCBs, DDE, and penta- and hexachlorobenzene are found close to phase equilibrium or net-volatilisational (upward flux), similarly at a remote site (on Crete) and in the more polluted Thermaikos Gulf. The results suggest that effective passive air sampling volumes may not be representative across sites when PAHs significantly partitioning to the particulate phase are included.

Calibration of silicone rubber passive samplers: experimental and modeled relations between sampling rate and compound properties.

Sampling rates (Rs) for silicone rubber (SR) passive samplers were measured under two different hydrodynamic conditions. Concentrations were maintained in the aqueous phase by continuous equilibration with SR sheets of a large total surface area which had been spiked with polycyclic aromatic hydrocarbons and/or polychlorinated biphenyls. Test sheets made of the same SR but of much smaller surface area were used to measure the uptake rate. Measured Rs values decreased with increasing passive sampler-water partition coefficient (Kpw) according to Rs approximately Kpw(-0.08) under both hydrodynamic conditions. This decrease is not significantly different from modeled values if the uncertainty of the diffusion coefficients in water is included. Modeling also confirmed that uptake of the test compounds under the experimental conditions was entirely controlled by diffusion in the water phase. A model using Rs approximately M(-0.47) is suggested for extrapolation of Rs estimated from the dissipation of performance reference compounds to target compounds in a higher hydrophobicity range.

Polymer selection for passive sampling: a comparison of critical properties.

Next to the bi-phasic semipermeable membrane devices (SPMDs), single-phase passive samplers are becoming more popular for the sampling of hydrophobic contaminants. We therefore evaluated some critical properties of 13 polymers: low-density polyethylene (LDPE), polyoxymethylene (POM), silicone rubbers (SRs), including polydimethylsiloxane, and ethylene/octene co-polymer (EXACT). Polymer comparison included four critical properties: release of oligomers, swelling in solvents (dichloromethane, hexane, ethyl acetate, acetone and methanol), contaminant diffusion coefficients and partition coefficients for naphthalene, fluoranthene, benzo[a]pyrene and dibenz[a,h]anthracene. Amounts of extracted oligomers ranged from 2% to 4% for SRs and LDPE, to about 1% for EXACT. No oligomer release was observed for POM. Diffusion coefficients were higher in all SRs compared with LDPE and EXACT. No measurable diffusion was observed in POM after 24h of exposure. Differences in polymer-water partition coefficients spanned two orders of magnitude, with the lowest values observed for POM and the highest values observed for LDPE and EXACT. For the ten tested SRs, this range was less than 0.4 log units. Transport resistances estimated on the basis of diffusion coefficients and partition coefficients were generally lower for SRs than for LDPE and EXACT.