Annika Jahnke

Analysis of per- and polyfluorinated alkyl substances in air samples from Northwest Europe

Air samples were collected from 4 field sites in Europe: 2 sites from the UK, Hazelrigg (semi-rural) and Manchester (urban); 1 site from Ireland: Mace Head (rural); and 1 site from Norway: Kjeller (rural). Additionally, air samples were taken from indoor locations in Tromsø, Norway. Air samples were collected using high-volume air samplers employing sampling modules containing glass-fibre filters (GFFs, particle phase), and glass columns with a polyurethane foam (PUF)-XAD-2-PUF sandwich (gaseous phase). Typical outdoor air volumes required for the determination of per- and polyfluorinated alkyl substances (PFAS) ranged from 500-1800 m3. GFFs and PUF-XAD columns were analysed separately to obtain information on phase partitioning. All air samples were analysed for volatile, neutral PFAS, with selected GFF samples halved for analysis of both neutral and airborne particle-bound ionic PFAS. Volatile PFAS were extracted from air samples by cold-column immersion with ethyl acetate, and were analysed by gas chromatography-mass spectrometry in the positive chemical ionisation mode (GC-PCI-MS). Ionic PFAS were extracted from GFFs by sonication in methanol, and were analysed by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) using electrospray ionisation in the negative ion mode (ESI-). Perfluorooctanoate (PFOA) was often the predominant analyte found in the particulate phase at concentrations ranging from 1-818 pg m(-3), and 8:2 fluorotelomer alcohol (FTOH) and 6:2 FTOH were the prevailing analytes found in the gas phase, at 5-243 pg m(-3) and 5-189 pg m(-3), respectively. These three PFAS were ubiquitous in air samples. Many other PFAS, both neutral and ionic, were also present, and levels of individual analytes were in the 1-125 pg m(-3) range. Levels of some PFAS exceeded those of traditional persistent organic pollutants (POPs). In this study, the presence of 12:2 FTOH and fluorotelomer olefins (FTolefins), and ionic PFAS other than perfluorooctane sulfonate (PFOS) and PFOA, are reported in air samples for the first time. Concentrations of neutral PFAS were several orders of magnitude higher in indoor air than outdoor air, making homes a likely important diffuse source of PFAS to the atmosphere. Our repeated findings of non-volatile ionic PFAS in air samples raises the possibility that they might directly undergo significant atmospheric transport on particles away from source regions, and more atmospheric measurements of ionic PFAS are strongly recommended.

Future water quality monitoring - Adapting tools to deal with mixtures of pollutants in water resource management

Environmental quality monitoring of water resources is challenged with providing the basis for safeguarding the environment against adverse biological effects of anthropogenic chemical contamination from diffuse and point sources. While current regulatory efforts focus on monitoring and assessing a few legacy chemicals, many more anthropogenic chemicals can be detected simultaneously in our aquatic resources. However, exposure to chemical mixtures does not necessarily translate into adverse biological effects nor clearly shows whether mitigation measures are needed. Thus, the question which mixtures are present and which have associated combined effects becomes central for defining adequate monitoring and assessment strategies. Here we describe the vision of the international, EU-funded project SOLUTIONS, where three routes are explored to link the occurrence of chemical mixtures at specific sites to the assessment of adverse biological combination effects. First of all, multi-residue target and non-target screening techniques covering a broader range of anticipated chemicals co-occurring in the environment are being developed. By improving sensitivity and detection limits for known bioactive compounds of concern, new analytical chemistry data for multiple components can be obtained and used to characterise priority mixtures. This information on chemical occurrence will be used to predict mixture toxicity and to derive combined effect estimates suitable for advancing environmental quality standards. Secondly, bioanalytical tools will be explored to provide aggregate bioactivity measures integrating all components that produce common (adverse) outcomes even for mixtures of varying compositions. The ambition is to provide comprehensive arrays of effect-based tools and trait-based field observations that link multiple chemical exposures to various environmental protection goals more directly and to provide improved in situ observations for impact assessment of mixtures. Thirdly, effect-directed analysis (EDA) will be applied to identify major drivers of mixture toxicity. Refinements of EDA include the use of statistical approaches with monitoring information for guidance of experimental EDA studies. These three approaches will be explored using case studies at the Danube and Rhine river basins as well as rivers of the Iberian Peninsula. The synthesis of findings will be organised to provide guidance for future solution-oriented environmental monitoring and explore more systematic ways to assess mixture exposures and combination effects in future water quality monitoring.

Trace analysis of per- and polyfluorinated alkyl substances in various matrices - how do current methods perform?

Per- and polyfluorinated alkyl substances (PFAS) are a group of industrial chemicals, some of which have been produced for over 50 years. Scarcely one decade ago, their ubiquity in wildlife, humans and the global environment was discovered. This urged the need for robust and reliable, yet very sensitive analytical methods allowing for their determination in various matrices. This article reviews the state-of-the-art in trace analysis of ionic and neutral PFAS in humans as well as environmental samples such as wildlife, water, solid matrices and air. Analytical protocols for PFAS determination in food and consumer products are also included. The methods are critically discussed in terms of their advantages, shortcomings, possibilities, limitations, and potential for further development.

Do complex matrices modify the sorptive properties of polydimethylsiloxane (PDMS) for non-polar organic chemicals?

The partitioning of non-polar analytes into the silicone polydimethylsiloxane (PDMS) is the basis for many analytical approaches such as solid phase microextraction (SPME), stir bar sorptive extraction (SBSE) and environmental passive sampling. Recently, the methods have been applied to increasingly complex sample matrices. The present work investigated the possible effect of complex matrices on the sorptive properties of PDMS. First, SPME fibers with a 30 microm PDMS coating were immersed in 15 different matrices, including sediment, suspensions of soil and humic substances, mayonnaise, meat, fish, olive oil and fish oil. Second, the surface of the fibers was wiped clean, and together with matrix-free control fibers, they were exposed via headspace to 7 non-polar halogenated organic chemicals in spiked olive oil. The fibers were then solvent-extracted, analyzed, and the ratios of the mean concentrations in the matrix-immersed fibers to the control fibers were determined for all matrices. These ratios ranged from 92% to 112% for the four analytes with the highest analytical precision (i.e. polychlorinated biphenyls (PCBs) 3, 28, 52 and brominated diphenyl ether (BDE) 3), and they ranged from 74% to 133% for the other three compounds (i.e. PCBs 101, 105 and gamma-hexachlorocyclohexane (HCH)). We conclude that, for non-polar, hydrophobic chemicals, the sorptive properties of the PDMS were not modified by the diverse investigated media and consequently that PDMS is suited for sampling of these analytes even in highly complex matrices.

Equilibrium sampling: Partitioning of organochlorine compounds from lipids into polydimethylsiloxane

Polydimethylsiloxane (PDMS) can be used for equilibrium sampling of environmental pollutants in a large variety of matrices including biota. For comparison with lipid-normalized concentrations e.g. from biota monitoring programmes, reliable lipid to PDMS partition ratios (K(Lipid,PDMS)) are required. Additionally, K(Lipid,PDMS) facilitate comparison of equilibrium sampling data obtained in various environmental media and can be helpful to convert equilibrium sampling data into a more informative form. This work investigated the equilibrium partitioning of polychlorinated biphenyls (PCBs) and selected organochlorine pesticides (OCPs) between lipids from biota of different trophic levels and PDMS. One vegetable oil, a fish oil and seal oil were investigated. The lipid to PDMS partition ratios were compound-specific and ranged from 14.5 to 62.9 g/g with correction for lipid uptake into the PDMS and from 13.0 to 54.8 g/g without correction. Additionally, PDMS served as a reference partitioning phase for the accurate determination of lipid to lipid partition ratios, which for all analytes were close to unity. Evaluating the results in a bioaccumulation context, they indicate that the equilibrium partitioning of neutral lipophilic environmental contaminants into the lipids of the three investigated species will be very similar, although they represent three distinct trophic levels.

Sensitive Equilibrium Sampling To Study Polychlorinated Biphenyl Disposition in Baltic Sea Sediment

An equilibrium sampling approach using glass jars with μm thin coatings of the silicone polydimethylsiloxane (PDMS) was validated and applied to background sediment samples from a >50 km transect in the Stockholm Archipelago. Equilibrium between the sediment and the PDMS was demonstrated using different coating thicknesses. From the concentrations of polychlorinated biphenyls (PCBs) in the PDMS, we assessed (i) freely dissolved concentrations in the sediment interstitial porewater (C(Sediment_free)); (ii) the equilibrium status between sediment and water; (iii) the equilibrium status between sediment and biota; and (iv) site-specific sediment/water distribution ratios (K(D)). The results showed that (i) Stockholm was a source of PCBs to the Baltic Sea as evidenced by significantly higher C(Sediment_free) in Stockholm Harbor; (ii) the fugacity in sediment exceeded that in water (monitoring samples collected in February) by an average factor of 4.0; (iii) the fugacity in sediment exceeded that in herring by an average factor of 5.2; and (iv) K(D) near Stockholm Harbor was 0.3-1.7 log units greater than in the outer archipelago. The coated glass jar method with its high precision and built-in QA/QC opens new possibilities to study the disposition of hydrophobic chemicals at trace levels (C(Sediment_free) down to 1.06 fg/L) in background environments.

Possibilities and limitations of equilibrium sampling using polydimethylsiloxane in fish tissue.

Polydimethylsiloxane (PDMS) has been used for passive equilibrium sampling in numerous abiotic environmental matrices. Recently, this approach was extended to lipid-rich tissue. This work investigated the possibilities and limitations of using PDMS thin-film extraction for in tissue equilibrium sampling in fish species of varying lipid content. Polychlorinated biphenyls (PCBs) were used as model lipophilic organic pollutants. PDMS thin-films were inserted in intact fish tissue for differing time periods (1h up to 1 week). The thin-films were then solvent-extracted and the extracts were analyzed using gas chromatography coupled to mass spectrometry. Whether equilibrium had been established was investigated either by using PDMS thin-films of multiple thicknesses (140-620 microm) or by assessing kinetics by means of time series. Equilibration was found to be rapid (i.e. in the range of hours) in lipid-rich fish whereas equilibrium was not achieved within one week in tissues with low or medium lipid content (i.e. up to 2% lipids). Regarding lipid-rich fish, the newly developed method was found to be sufficiently sensitive to determine equilibrium partitioning concentrations of PCBs in lipids of samples from the Baltic Sea, and it is a promising approach for any kind of fatty tissue.

Equilibrium sampling of environmental pollutants in fish: Comparison with lipid‐normalized concentrations and homogenization effects on chemical activity

Equilibrium sampling of organic pollutants into the silicone polydimethylsiloxane (PDMS) has recently been applied in biological tissues including fish. Pollutant concentrations in PDMS can then be multiplied with lipid/PDMS distribution coefficients (D(Lipid,PDMS) ) to obtain concentrations in fish lipids. In the present study, PDMS thin films were used for equilibrium sampling of polychlorinated biphenyls (PCBs) in intact tissue of two eels and one salmon. A classical exhaustive extraction technique to determine lipid-normalized PCB concentrations, which assigns the body burden of the chemical to the lipid fraction of the fish, was additionally applied. Lipid-based PCB concentrations obtained by equilibrium sampling were 85 to 106% (Norwegian Atlantic salmon), 108 to 128% (Baltic Sea eel), and 51 to 83% (Finnish lake eel) of those determined using total extraction. This supports the validity of the equilibrium sampling technique, while at the same time confirming that the fugacity capacity of these lipid-rich tissues for PCBs was dominated by the lipid fraction. Equilibrium sampling was also applied to homogenates of the same fish tissues. The PCB concentrations in the PDMS were 1.2 to 2.0 times higher in the homogenates (statistically significant in 18 of 21 cases, p < 0.05), indicating that homogenization increased the chemical activity of the PCBs and decreased the fugacity capacity of the tissue. This observation has implications for equilibrium sampling and partition coefficients determined using tissue homogenates.

From the exposome to mechanistic understanding of chemical-induced adverse effects

The exposome encompasses an individuals exposure to exogenous chemicals, as well as endogenous chemicals that are produced or altered in response to external stressors. While the exposome concept has been established for human health, its principles can be extended to include broader ecological issues. The assessment of exposure is tightly interlinked with hazard assessment. Here, we explore if mechanistic understanding of the causal links between exposure and adverse effects on human health and the environment can be improved by integrating the exposome approach with the adverse outcome pathway (AOP) concept that structures and organizes the sequence of biological events from an initial molecular interaction of a chemical with a biological target to an adverse outcome. Complementing exposome research with the AOP concept may facilitate a mechanistic understanding of stress-induced adverse effects, examine the relative contributions from various components of the exposome, determine the primary risk drivers in complex mixtures, and promote an integrative assessment of chemical risks for both human and environmental health.

Strategies for Transferring Mixtures of Organic Contaminants from Aquatic Environments into Bioassays

Mixtures of organic contaminants are ubiquitous in the environment. Depending on their persistence and physicochemical properties, individual chemicals that make up the mixture partition and distribute within the environment and might then jointly elicit toxicological effects. For the assessment and monitoring of such mixtures, a variety of cell-based in vitro and low-complexity in vivo bioassays based on algae, daphnids or fish embryos are available. A very important and sometimes unrecognized challenge is how to combine sampling, extraction and dosing to transfer the mixtures from the environment into bioassays, while conserving (or re-establishing) their chemical composition at adjustable levels for concentration-effect assessment. This article outlines various strategies for quantifiable transfer from environmental samples including water, sediment, and biota into bioassays using total extraction or polymer-based passive sampling combined with either solvent spiking or passive dosing.