Seasonal trends and retention of polycyclic aromatic compounds (PACs) in a remote sub-Arctic catchment.

Atmospheric deposition is the most dominant source of polycyclic aromatic hydrocarbons (PAHs) in remote and pristine areas. Despite low bioaccumulation potential, PAHs and their persistent transformation products (PAH-derivatives) are chemicals of concern as they can harm human and animal health through chronic low dose exposure. In this study, atmospheric deposition fluxes of polycyclic aromatic compounds (PACs) were measured on a seasonal basis (3-month periods) from 2012 to 2016 in a remote subarctic forest catchment in northern Europe. The target PACs included 19 PAHs and 15 PAH-derivatives (oxygenated, nitrogenated, and methylated PAHs). The deposition fluxes of Æ©PAHs and Æ©PAH-derivatives were in the same range and averaged 530 and 500 ng m2 day-1, respectively. The fluxes were found to be higher with a factor of 2.5 for Æ©PAHs and a factor of 3 for Æ©PAH-derivatives during cold (<0 °C) in comparison to warm (>10 °C) periods. PAHs and PAH-derivatives showed similar seasonal patterns, which suggests that these two compound classes have similar sources and deposition mechanisms, and that the source strength of the PAH-derivatives in air follows that of the PAHs. The terrestrial export of PACs via the outlet of the catchment stream was estimated to be 1.1% for Æ©PAHs and 1.7% for Æ©PAH-derivatives in relation to the annual amounts deposited to the catchment, which suggests that boreal forests are sinks for PACs derived from the atmosphere. Some individual PACs showed higher export than others (i.e. chrysene, cyclopenta(c,d)pyrene, carbazole, quinoline, and benzo(f)quinoline), with high export PACs mostly characterized by low molecular weight and low hydrophobicity (2-3 benzene rings; log Kow<6.0).

Seasonal trends of per- and polyfluoroalkyl substances in river water affected by fire training sites and wastewater treatment plants.

Fire-fighting training areas and wastewater treatment plants (WWTPs) are potential sources of per- and polyfluoroalkyl substances (PFASs) to the nearby aquatic environment. This study investigated seasonal variations of PFAS levels in two river catchments in Sweden; one impacted by Stockholm Arlanda Airport (Sites 1 and 2), and the other by WWTPs and a military airport (Uppsala) (Sites 3 and 4). Æ©PFAS concentrations were up to 61 (Sites 1 and 2) and 4 (Sites 3 and 4) times higher compared to the reference site. Distinct different seasonal trends were observed in the two catchments with higher ∑PFAS concentrations during the high water flow season at Site 1 compared to the low water flow season, whereas Sites 3 and 4 showed an inverse seasonal trend. This demonstrates that the pollution is mobilized during periods of high flow in the first catchment (Stockholm Arlanda Airport), while it is diluted during high flow in the second catchment (Uppsala). Average annual loads for ∑PFASs were estimated at ∼5.2 and ∼3.7 kg yr-1 for the catchment in Uppsala and Stockholm Arlanda Airport, respectively. Thus, both catchments add PFASs to Lake Mälaren, which is Sweden's most important source area for drinking water production.

Comprehensive chemical characterization of indoor dust by target, suspect screening and nontarget analysis using LC-HRMS and GC-HRMS.

Since humans spend more than 90% of their time in indoor environments, indoor exposure can be an important non-dietary pathway to hazardous organic contaminants. It is thus important to characterize the chemical composition of indoor dust to assess the total contaminant exposure and estimate human health risks. The aim of this investigation was to perform a comprehensive chemical characterization of indoor dust. First, the robustness of an adopted extraction method using ultrasonication was evaluated for 85 target compounds. Thereafter, a workflow combining target analysis, suspect screening analysis (SSA) and nontarget analysis (NTA) was applied to dust samples from different indoor environments. Chemical analysis was performed using both gas chromatography and liquid chromatography coupled with high resolution mass spectrometry. Although suppressing matrix effects were prominent, target analysis enabled the quantification of organophosphate/brominated flame retardants (OPFRs/BFRs), liquid crystal monomers (LCMs), toluene diisocyanate, bisphenols, pesticides and tributyl citrate. The SSA confirmed the presence of OPFRs but also enabled the detection of polyethylene glycols (PEGs) and phthalates/parabens. The combination of hierarchical cluster analysis and scaled mass defect plots in the NTA workflow confirmed the presence of the above mentioned compounds, as well as detect other contaminants such as tetrabromobisphenol A, triclocarban, diclofenac and 3,5,6-trichloro-2-pyridinol, which were further confirmed using pure standards.

Seasonal trends of legacy and alternative flame retardants in river water in a boreal catchment.

Boreal forests store large amounts of atmospherically deposited (semi-)persistent organic pollutants (POPs). The terrestrial POPs may be exported to streams and rivers through processes that are heavily impacted by seasonality. In this screening study, concentrations of 4 legacy and 45 alternative flame retardants (FRs) were determined in the dissolved and particulate phase in streams within a relatively pristine boreal catchment in northern Europe (Krycklan Catchment Study; 3 sites) and in rivers more impacted by human activities further downstream towards the Baltic Sea (3 sites). The sampling included the main hydrological seasons (snow-free, snow-covered, and spring flood) and was conducted during two consecutive years (2014-2016). Of the 49 analyzed FRs, 11 alternative halogenated FRs (HFRs), 13 alternative organophosphorus FRs (OPFRs), and 4 legacy polybrominated diphenyl ethers (PBDEs) were detected in at least one sample. The average bulk (dissolved + particulate) concentrations of ∑FRs (including all sites) were highest for ∑HFRs (38 ±â€¯70 ng L-1), followed by the ∑OPFRs (3.9 ±â€¯4.9 ng L-1) and the ∑PBDEs (0.0040 ±â€¯0.016 ng L-1). Bulk concentrations of HFRs, OPFRs, and PBDEs were highly variable with season and sampling location, e.g., during spring flood, bulk concentrations were up to 600 times, 3.7 times, and 4.9 times higher for HFRs, OPFRs and PBDEs, respectively, than during periods of lower flow. Bulk concentrations of ∑OPFRs, were elevated at all sites ~6 days before the actual start of the spring flood in 2015, suggesting that hydrophobicity fractionation had occurred within the snowpack. Similar to previous studies of other POPs in the same headwater catchment, there was a general trend that levels of ∑FRs were higher at the mire site than at the forested site. Annual fluxes of FRs were found to be ~15 times higher downstream the city of Umeå compared to at the outlet of the pristine catchment. This study should be regarded as a screening study considering the large number of diverse FRs analyzed and variability in the results.

Screening of organic flame retardants in Swedish river water.

Alternative flame retardants (FRs) have now replaced legacy FRs (such as polybrominated diphenyl ethers, PBDEs), but little is known about their fate in the aquatic environment. In this study, a range of legacy FRs (n=10) and alternative FRs, including halogenated FRs (HFRs, n=32) and organophosphorus FRs (OPFRs, n=19), were screened in water samples collected from 23 rivers covering the whole latitudinal range of Sweden. Of the 61 targeted FRs, 26 were detected in at least one of the river samples, with ΣFR concentrations ranging up to 170ngL-1 (mean 31±45ngL-1). In general, higher concentrations and a larger variety of FRs were detected in southern Sweden (ΣFR=60±56ngL-1) compared with the north (ΣFR=9.0±16ngL-1). In the south, HFRs were dominant, constituting on average 59% of ∑FRs, whereas in the north, OPFRs were dominant, constituting on average 82% of ∑FRs. This difference was best explained by higher population density in the south. The total daily flux of FRs into the Baltic Sea was estimated to be ~31kg and comprised mainly tetrabromobisphenol-A (TBBPA), 3,4,5,6-tetrabromophthalic anhydride (TEBP-Anh), and 2,4,6-tribromophenol (TBP). To the best of our knowledge, this is the first report of environmental occurrence of TEBP-Anh, which was detected in two rivers and is suggested to originate from airports located near the sampling sites.

The Role of Spring Flood and Landscape Type in the Terrestrial Export of Polycyclic Aromatic Compounds to Streamwater.

Concentrations of polycyclic aromatic compounds (PACs), including 19 polycyclic aromatic hydrocarbons (PAHs) and 15 PAH-derivatives (oxygenated and nitrogen heterocyclic PAHs), were measured in streams in a remote headwater catchment in northern Europe and in more urbanized, downstream areas. Sampling was conducted during 2014 to 2016 and included the main hydrological seasons (snow-free, snow-covered, and spring flood) at six sampling sites. Levels of the targeted PACs varied substantially over time and space and were up to 110-fold (on average 17-fold) and 7000-fold (on average 670-fold) higher for PAHs and PAH-derivatives, respectively, during spring flood compared with preceding snow-covered and snow-free seasons. Higher levels of ∑PACs were generally found in a headwater stream draining a mire than at an adjacent forested site, with up to 20 times and 150 times higher levels for ∑PAH and ∑PAH-derivatives, respectively. The particle-bound PAC levels were positively correlated to surface runoff in the mire stream (∑PAHs: p = 0.032; ∑PAH-derivatives: p = 0.040) but not in the corresponding forest stream, during snowmelt and winter base flow. In more urbanized downstream areas, particle-bound PACs were instead strongly associated with suspended particulate matter ( p < 0.05; ∑PAHs and ∑PAH-derivatives except one site). Levels of ∑PACs in the streamwater were on average 3-fold higher downstream of the most densely populated area than at the outlet of the headwater catchment. The higher PAC levels in the downstream water compared to the remote headwater were clearer when normalized to SPM amounts (instead of water volume), with a gradual downstream trend between the sites.

Influence of natural organic matter on the extraction efficiency of flame retardants from surface waters.

The influence of natural organic matter (NOM) on the solid-phase extraction (SPE) efficiency was investigated for legacy and emerging flame retardants (FRs; n=26) in surface water. Three different groups of FRs were analyzed: polybrominated diphenyl ethers (PBDEs), halogenated flame retardants (HFRs), and organophosphorus flame retardants (OPFRs). In addition, five sorbents (Amberlite XAD-2, Amberlite IRA-743, Oasis HLB, Chromabond HR-P, and Chromabond HR-X) were evaluated for the extraction of FRs (n=33) in water, of which Oasis HLB eluted with dichloromethane and acetone:n-hexane (1:1, v/v) provided the highest overall recoveries. In subsequent NOM experiments, where FRs were extracted from water containing different NOM concentrations, both increased and decreased extraction efficiency with increasing NOM level were observed. Physicochemical and semi-empirical quantum chemistry properties were calculated for the FRs and used for analyzing relations between FRs. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) showed that the FRs separated into four different groups based on their properties. The FRs within each group responded similarly to increasing NOM, while differences in behavior were observed between the groups. This suggests that the structural properties of micropollutants highly influence NOM-FR interaction mechanisms. For instance, at high NOM levels, recoveries decreased substantially for FRs containing a moiety that can form strong hydrogen bonds (such as the double-bonded oxygen in e.g., OPFRs). Many of the compounds showed maximum extraction efficiency at higher levels of NOM. This suggests that binding of NOM to the sorbent and subsequent interaction between sorbent-bound NOM and FRs is an important mechanism for extraction of micropollutants from surface waters.

Spatial distribution and source tracing of per- and polyfluoroalkyl substances (PFASs) in surface water in Northern Europe.

The impact of point and diffuse sources for 26 per- and polyfluoroalkyl substances (PFASs) in northern Europe were investigated by studying Swedish rivers (n = 40) and recipient seawater (Baltic Sea and Kattegat; n = 18). Different composition profiles were observed in the rivers, with ten rivers having a remarkably high fraction of perfluoroalkane sulfonic acids (PFSAs; 65% of the Æ©PFASs) as compared to other rivers (19%) suggesting major impact of one or several source types dominated by PFSAs. Population density and low latitude (south) were strongly correlated to the widely used perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA) as well as to perfluorohexanesulfonic acid (PFHxS). Significant relationships between several PFCAs and PFSAs (i.e. perfluorobutanoic acid (PFBA), perfluoroheptanoic acid (PFHpA), PFOA, perfluorobutanesulfonic acid (PFBS), and PFHxS) and dissolved organic carbon (DOC) were detected (p < 0.05), indicating chemical binding and co-transport with DOC in fresh water and seawater. Partial least squares regression analysis showed that perfluoroalkyl carboxylic acids (PFCAs) were related to latitude according to their perfluorocarbon chain length (C3, C7, C8, C9, C10 and C11), with longer chains associated with higher latitudes. This suggests the presence of mechanisms promoting higher prevalence of longer chained PFCAs in the north, e.g. precursor degradation, and/or aerosol associated stabilization of PFCAs and their precursors.

Development and comparison of gas chromatography-mass spectrometry techniques for analysis of flame retardants.

The restrictions on the use of legacy flame retardants (FRs) have increased the need of alternative FRs to comply with fire safety legislations. In this study, the feasibility of three different gas chromatography-mass spectrometry (GC-MS) techniques were investigated for the analysis of 102 legacy and alternative FRs including polybrominated diphenyl ethers (PBDEs, n=27), halogenated FRs (HFRs, containing bromine and/or chlorine, n=46), and organophosphorous FRs (OPFRs, n=29). The tested techniques included GC-single MS with (i) electon impact (EI) ionization and (ii) negative chemical ionization (NCI), and (iii) GC-tandem MS (MS/MS) with EI ionization. Out of the tested FRs, 90 could be detected under the used conditions on at least one of the three instrument setups. Later experiments included a selection of these FRs. For the majority of tested PBDEs (5 out of 6) and HFRs (24 out of 26), EI-MS/MS provided the highest detectability (i.e. the lowest detection limits), while for most tested OPFRs (8 out of 13), EI-MS performed better. The influence of matrix components on the analysis of FRs (n=45) was investigated by analyzing a fortified surface water sample with the technique with the lowest selectivity, EI-MS. Both peak enhancement and suppression were observed, and significant correlations between matrix effects and several physico-chemical properties (e.g., retention time and boiling point) were found for PBDEs. In a separate clean-up experiment using natural water spiked with legacy and alternative FRs (n=30), alumina provided the highest mean recovery (90%) in comparison to acidified silica (67%) and Florisil (78%). This study provides new knowledge on analysis of FRs including a wide range of alternative FRs, and it will aid in the efforts of FR monitoring in the environment.