ABSTRACT
Foam fractionation is becoming increasingly popular as a treatment technology for water contaminated with per- and polyfluoroalkyl substances (PFAS). At many existing wastewater treatment facilities, particularly in aerated treatment steps, foam formation is frequently observed. This study aimed to investigate if foam fractionation for the removal of PFAS could be integrated with such existing treatment processes. Influent, effluent, water under the foam, and foam were sampled from ten different wastewater treatment facilities where foam formation was observed. These samples were analyzed for the concentration of 29 PFAS, also after the total oxidizable precursor (TOP) assay. Enrichment factors were defined as the PFAS concentration in the foam divided by the PFAS concentration in the influent. Although foam partitioning did not lead to decreased ∑PFAS concentrations from influent to effluent in any of the plants, certain long-chain PFAS were removed with efficiencies up to 76%. Moreover, ∑PFAS enrichment factors in the foam ranged up to 105, and enrichment factors of individual PFAS ranged even up to 106. Moving bed biofilm reactors (MBBRs) were more effective at enriching PFAS in the foam than activated sludge processes. Altogether, these high enrichment factors demonstrate that foam partitioning in existing wastewater treatment plants is a promising option for integrated removal. Promoting foam formation and removing foam from the water surface with skimming devices may improve the removal efficiencies further. These findings have important implications for PFAS removal and sampling strategies at wastewater treatment plants.
ABSTRACT
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).
Subject(s)
Air Pollutants , Polycyclic Aromatic Hydrocarbons , Polycyclic Compounds , Animals , Humans , Environmental Monitoring , Seasons , Polycyclic Aromatic Hydrocarbons/analysis , Europe , Air Pollutants/analysisABSTRACT
Polycyclic aromatic hydrocarbons (PAHs), oxygenated PAHs (oxy-PAHs) and nitrogen heterocyclic polycyclic aromatic compounds (N-PACs) are persistent and semi-volatile organic compounds primarily formed due to incomplete combustion of organic material or, in the case of the derivatives, through transformation reactions of PAHs. Their presence in the environment is ubiquitous and many of them have been proven carcinogenic, teratogenic, and mutagenic. These toxic pollutants can therefore pose a threat to both ecosystem and human health and urges for remediation strategies for PAHs and derivatives from water bodies. Biochar is a carbon-rich material resulting from the pyrolysis of biomass resulting in a very porous matter with high surface area for an enhanced interaction with chemicals. This makes biochar a promising alternative for filtering micropollutants from contaminated aquatic bodies. In this work, a previously developed and validated methodology for the analysis of PAHs, oxy-PAHs and N-PACs in surface water samples was adapted for its utilization in biochar treated stormwater with special emphasis on scaling down the solid-phase extraction as well as including an additional filtering step for the removal of particulate matter in the media.â¢Optimized extraction method for PAHs, oxy-PAHs and N-PACs from stormwater treated with biochar.â¢Biochar strongly impacts the stormwater matrix and, therefore, additional steps are required in the extraction methodology.â¢Solid-phase extraction combined with GC-MS have been used to analyse PAHs, oxy-PAHs and N-PACs in stormwater treated with biochar.
ABSTRACT
Deposits of contaminated wood fiber waste (fiberbanks), originating from sawmills and pulp and paper industries, have been found in the aquatic environment in boreal countries. In-situ isolation capping has been proposed as a remediation solution because it has the potential to prevent dispersal of persistent organic pollutants (POPs) from this type of sediment. However, knowledge about the performance of such caps when placed on very soft (unconsolidated), gaseous organic rich sediment is scarce. We investigated the effectiveness of conventional in-situ capping to limit POPs fluxes to the water column from contaminated fibrous sediments that produce gas. A controlled, large-scale laboratory column (40 cm diameter, 2 m height) experiment was performed over 8 months to study changes in sediment-to-water fluxes of POPs and particle resuspension before and after capping the sediment with crushed stones (≥4 mm grain size). Two different cap thicknesses were tested (20 and 45 cm) on two types of fiberbank sediment with different fiber type composition. Results showed that capping fiberbank sediment with a 45 cm gravel cap reduced the sediment-to-water flux by 91-95% for p,p'-DDD, o,p'-DDD, by 39-82% for CB-101, CB-118, CB-138, CB-153, CB-180 and by 12-18% for HCB, whereas for less hydrophobic PCBs, capping was largely ineffective (i.e. CB-28 and CB-52). Although cap application caused particle resuspension, the long-term effect of the cap was reduced particle resuspension. On the other hand, substantial sediment consolidation released large volumes of contaminated pore water into the overlying water body. Importantly, both sediment types produced large amount of gas, observed as gas voids forming inside the sediment and gas ebullition events, which increased pore water advection and affected the structural integrity of the cap. This may limit the practical applicability of this method on fiberbank sediments.
Subject(s)
Environmental Pollutants , Water Pollutants, Chemical , Persistent Organic Pollutants , Geologic Sediments/chemistry , Environmental Pollutants/analysis , Water , Water Pollutants, Chemical/analysisABSTRACT
PER: and polyfluoroalkyl substances (PFAS) are ubiquitously distributed in wastewater, due to their numerous uses in industry and consumer products, but little is known of PFAS mass flows in municipal wastewater network systems and within wastewater treatment plants (WWTPs). This study assessed mass flows of 26 PFAS in a wastewater network and WWTP, to provide new insights into their sources, transport, and fate in different treatment steps. Wastewater and sludge samples were collected from pumping stations and the main WWTP in Uppsala, Sweden. PFAS composition profiles and mass flows were used to identify sources within the sewage network. Wastewater from one pumping station showed elevated concentrations of C3-C8 PFCA, likely caused by an industrial source, and two stations had elevated concentrations of 6:2 FTSA, probably originating from a nearby firefighter training facility. Within the WWTP, short-chain PFAS dominated in wastewater, whereas long-chain PFAS dominated in sludge. The ratio of perfluoroalkyl sulfonates (PFSA) and ethylperfluorooctanesulfonamidoacetic acid (EtFOSAA) to ∑26PFAS decreased during the WWTP process, likely due to sorption to sludge, but also transformation (EtFOSAA). Overall, PFAS were not efficiently removed in the WWTP, with mean removal efficiency of 10 ± 68% for individual PFAS, resulting in discharge of 7000 mg d-1 ∑26PFAS into the recipient. This shows that conventional WWTPs are inefficient in removing PFAS from wastewater and sludge, so advanced treatment techniques are needed.
Subject(s)
Fluorocarbons , Water Pollutants, Chemical , Water Purification , Wastewater , Sewage , Sweden , Fluorocarbons/analysis , Water Pollutants, Chemical/analysisABSTRACT
Per- and polyfluoroalkyl substances (PFAS) are persistent synthetic contaminants that are present globally in water and are exceptionally difficult to remove during conventional water treatment processes. Here, we demonstrate a practical treatment train that combines foam fractionation to concentrate PFAS from groundwater and landfill leachate, followed by an electrochemical oxidation (EO) step to degrade the PFAS. The study combined an up-scaled experimental approach with thorough characterization strategies, including target analysis, PFAS sum parameters, and toxicity testing. Additionally, the EO kinetics were successfully reproduced by a newly developed coupled numerical model. The mean total PFAS degradation over the designed treatment train reached 50%, with long- and short-chain PFAS degrading up to 86 and 31%, respectively. The treatment resulted in a decrease in the toxic potency of the water, as assessed by transthyretin binding and bacterial bioluminescence bioassays. Moreover, the extractable organofluorine concentration of the water decreased by up to 44%. Together, these findings provide an improved understanding of a promising and practical approach for on-site remediation of PFAS-contaminated water.
ABSTRACT
Persistent, mobile, and toxic (PMT) substances have recently garnered increased attention by environmental researchers, the water sector and environmental protection agencies. In this study, acute and chronic species sensitivity distributions (SSDs) were retrieved from literature data for previously quantified contaminants of emerging concern (CECs) in Swedish surface waters (n = 92) and risk quotients (RQ) were calculated. To better understand the characteristics of the detected CECs in non-urban lake sites (n = 71), these compounds were checked against established criteria for potentially toxic PMs (PM(T)s) and occurrence in the aquatic environment, respectively. For the CECs with missing SSDs (n = 15 [acute], n = 41 [chronic]), ecotoxicity data were extracted for eight taxonomic groups, and if data were sufficient (n ≥ 3), SSDs were derived. The retrieved and newly developed SSDs were then used in an environmental hazard assessment (EHA) in the investigated Swedish rivers and lakes. In the rivers, 8 CECs had RQ> 1 in at least one location, and 20 CECs posed a moderate risk (0.01 < RQ < 1). In total, 21 of the 71 detected substances had already been identified as PM(T)/vPvM substances. Our study shows the importance of studying field data at large spatial scale to reveal potential environmental hazards far from source areas.
Subject(s)
Environmental Monitoring , Water Pollutants, Chemical , Lakes , Sweden , Water Pollutants, Chemical/toxicity , Water Pollutants, Chemical/analysis , RiversABSTRACT
Tropical estuaries are threatened by rapid urbanization, which leads to the spread of thousands of micropollutants and poses an environmental risk to such sensitive aqueous ecosystems. In the present study, a combination of chemical and bioanalytical water characterization was applied to investigate the impact of Ho Chi Minh megacity (HCMC, 9.2 million inhabitants in 2021) on the Saigon River and its estuary and provide a comprehensive water quality assessment. Water samples were collected along a 140-km stretch integrating the river-estuary continuum from upstream HCMC down to the estuary mouth in the East Sea. Additional water samples were collected at the mouth of the four main canals of the city center. Chemical analysis was performed targeting up to 217 micropollutants (pharmaceuticals, plasticizers, PFASs, flame retardants, hormones, pesticides). Bioanalysis was performed using six in-vitro bioassays for hormone receptor-mediated effects, xenobiotic metabolism pathways and oxidative stress response, respectively, all accompanied by cytotoxicity measurement. A total of 120 micropollutants were detected and displayed high variability along the river continuum with total concentration ranging from 0.25 to 78 µg L-1. Among them, 59 micropollutants were ubiquitous (detection frequency ≥ 80 %). An attenuation was observed in concentration and effect profiles towards the estuary. The urban canals were identified as major sources of micropollutants and bioactivity to the river, and one canal (Ben Nghé) exceeded the effect-based trigger values derived for estrogenicity and xenobiotic metabolism. Iceberg modelling apportioned the contribution of the quantified and the unknown chemicals to the measured effects. Diuron, metolachlor, chlorpyrifos, daidzein, genistein, climbazole, mebendazole and telmisartan were identified as main risk drivers of the oxidative stress response and xenobiotic metabolism pathway activation. Our study reinforced the need for improved wastewater management and deeper evaluations of the occurrence and fate of micropollutants in urbanized tropical estuarine environments.
Subject(s)
Water Pollutants, Chemical , Water Quality , Environmental Monitoring , Estuaries , Ecosystem , Xenobiotics , Rivers/chemistry , Biological Assay , Water Pollutants, Chemical/toxicity , Water Pollutants, Chemical/analysisABSTRACT
Foam fractionation has recently attracted attention as a low-cost and environmentally benign treatment technology for water contaminated with per- and polyfluoroalkyl substances (PFAS). However, data on the mass balance over the foam fractionation process are scarce and when available, gaps in the mass balance are often identified. This study verified the high treatment efficiency of a pilot-scale foam fractionation system for removal of PFAS from industrial water contaminated with aqueous film-forming foam. ΣPFAS removal reached up to 84 % and the removal of perfluorooctane sulfonic acid (PFOS) up to 97 %, but the short-chain perfluorobutanoic acid (PFBA) was only removed with a mean efficiency of 1.5 %. In general, mobile short-chain PFAS were removed less efficiently when the perfluorocarbon chain length was below six for carboxylic acids and below five for sulfonic acids. Fluctuations in treatment efficiency due to natural variations in the chemistry of the influent water were minor, confirming the robustness of the technology, but significant positive correlations between PFAS removal and influent metal concentration and conductivity were observed. Over all experiments, the mass balance closure did not differ significantly from 100 %. Nonetheless, PFAS sorption to the walls of the reactor was measured, as well as high PFAS emissions by the air exiting the reactor. PFAS emissions in aerosols correlated positively with mass balance closure. The elevated aerial PFAS concentrations measured in the experimental facility have implications for worker safety and prevention of PFAS-emissions to the atmosphere, and demonstrate the importance of installing appropriate filters on the air outlet of foam fractionation systems.
ABSTRACT
Identification of bioaccumulating contaminants of emerging concern (CECs) via suspect and non-target screening remains a challenging task. In this study, ion mobility separation with high-resolution mass spectrometry (IM-HRMS) was used to investigate the effects of drift time (DT) alignment on spectrum quality and peak annotation for screening of CECs in complex sample matrices using data independent acquisition (DIA). Data treatment approaches (Binary Sample Comparison) and prioritisation strategies (Halogen Match, co-occurrence of features in biota and the water phase) were explored in a case study on zebra mussel (Dreissena polymorpha) in Lake Mälaren, Sweden's largest drinking water reservoir. DT alignment evidently improved the fragment spectrum quality by increasing the similarity score to reference spectra from on average (±standard deviation) 0.33 ± 0.31 to 0.64 ± 0.30 points, thus positively influencing structure elucidation efforts. Thirty-two features were tentatively identified at confidence level 3 or higher using MetFrag coupled with the new PubChemLite database, which included predicted collision cross-section values from CCSbase. The implementation of predicted mobility data was found to support compound annotation. This study illustrates a quantitative assessment of the benefits of IM-HRMS on spectral quality, which will enhance the performance of future screening studies of CECs in complex environmental matrices.
Subject(s)
Dreissena , AnimalsABSTRACT
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 â¼5.2 and â¼3.7 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.
Subject(s)
Drinking Water , Fluorocarbons , Water Pollutants, Chemical , Water Purification , Environmental Monitoring , Fluorocarbons/analysis , Rivers , Seasons , Water Pollutants, Chemical/analysisABSTRACT
Use of per- and polyfluoroalkyl substance (PFAS)-containing aqueous film-forming foams (AFFF) at firefighting training sites (FFTS) has been linked to PFAS contamination of drinking water. This study investigated PFAS transport and distribution in an urban groundwater aquifer used for drinking water production that has been affected by PFAS-containing AFFF. Soil, sediment, surface water and drinking water were sampled. In soil (n = 12) at a FFTS with high perfluorooctane sulfonate (PFOS) content (87% of ∑PFAS), the ∑PFAS concentration (n = 26) ranged from below detection limit to 560 ng g-1 dry weight. In groundwater (n = 28), the ∑PFAS concentration near a military airbase FFTS reached 1000 ng L-1. Principal component analysis (PCA) identified the military FFTS as the main source of PFAS contamination in drinking water wellfields >10 km down-gradient. Groundwater samples taken close to the military FFTS site showed no ∑PFAS concentration change between 2013 and 2021, while a location further down-gradient showed a transitory 99.6% decrease. Correlation analysis on PFAS composition profile indicated that this decrease was likely caused by dilution from an adjacent conflating aquifer. ∑PFAS concentration reached 15 ng L-1 (PFOS 47% and PFHxS 41% of ∑PFAS) in surface river water (n = 6) and ranged between 1 ng L-1 and 8 ng L-1 (PFHxS 73% and PFBS 17% of ∑PFAS) in drinking water (n = 4). Drinking water had lower PFAS concentrations than the wellfields due to PFAS removal at the water treatment plant. This demonstrates the importance of monitoring PFAS concentrations throughout a groundwater aquifer, to better understand variations in transport from contamination sources and resulting impacts on PFAS concentrations in drinking water extraction areas.
Subject(s)
Alkanesulfonic Acids , Drinking Water , Fluorocarbons , Groundwater , Water Pollutants, Chemical , Alkanesulfonic Acids/analysis , Drinking Water/analysis , Fluorocarbons/analysis , Soil , Sweden , Water Pollutants, Chemical/analysisABSTRACT
The Spanish Mediterranean basin is particularly susceptible to climate change and human activities, making it vulnerable to the influence of anthropogenic contaminants. Therefore, conducting comprehensive and exhaustive water quality assessment in relevant water bodies of this basin is pivotal. In this work, surface water samples from coastal lagoons or estuaries were collected across the Spanish Mediterranean coastline and subjected to target and suspect screening of 1,585 organic micropollutants by liquid chromatography coupled to ion mobility separation and high resolution mass spectrometry. In total, 91 organic micropollutants could be confirmed and 5 were tentatively identified, with pharmaceuticals and pesticides being the most prevalent groups of chemicals. Chemical analysis data was compared with data on bioanalysis of those samples (recurrent aryl hydrocarbon receptor (AhR) activation, and estrogenic receptor (ER) inhibition in wetland samples affected by wastewater streams). The number of identified organic contaminants containing aromatic rings could explain the AhR activation observed. For the ER antagonistic effects, predictions on estrogenic inhibition potency for the detected compounds were used to explain the activities observed. The integration of chemical analysis with bioanalytical observations allowed a comprehensive overview of the quality of the water bodies under study.
Subject(s)
Water Pollutants, Chemical , Water Quality , Environmental Monitoring , Human Activities , Humans , Wastewater/chemistry , Water Pollutants, Chemical/analysisABSTRACT
Per- and polyfluoroalkyl substances (PFAS) are of concern for their ubiquity in the environment combined with their persistent, bioaccumulative, and toxic properties. Landfill leachate is often contaminated with these chemicals, and therefore, the development of cost-efficient water treatment technologies is urgently needed. The present study investigated the applicability of a pilot-scale foam fractionation setup for the removal of PFAS from natural landfill leachate in a novel continuous operating mode. A benchmark batch test was also performed to compare treatment efficiency. The ΣPFAS removal efficiency plateaued around 60% and was shown to decrease for the investigated process variables air flow rate (Q air), collected foam fraction (%foam) and contact time in the column (t c). For individual long-chain PFAS, removal efficiencies above 90% were obtained, whereas the removal for certain short-chain PFAS was low (<30%). Differences in treatment efficiency between enriching mode versus stripping mode as well as between continuous versus batch mode were negligible. Taken together, these findings suggest that continuous foam fractionation is a highly applicable treatment technology for PFAS contaminated water. Coupling the proposed cost- and energy-efficient foam fractionation pretreatment to an energy-intensive degradative technology for the concentrated foam establishes a promising strategy for on-site PFAS remediation.
ABSTRACT
Anaerobic digestate based on food waste is increasingly used as fertilizer in food production. This study examined the characteristics of anaerobic digestate based on food waste from three biogas plants in Sweden. The characterization included measurements of heavy metals (n = 7), chemicals of emerging concern (CECs), such as currently used drugs and pesticides (n = 133), and an extended range of food-borne pathogens, including two notable sporeformers and some widespread antibiotic-resistant bacteria. The amounts of Escherichia coli, enterococci, and Salmonella and the concentrations of the target heavy metals were all below the maximum accepted levels at all three locations studied. However, the spore-forming Bacillus cereus was found to be present at high levels in samples from all three biogas plants. Among the 133 CECs investigated, 48 were detected at least once, and the highest concentrations were found for pyroxidine, nicotine, caffeine, theobromine, and nicotine. The biofertilizers from the different biogas plants had similar CEC profiles, which indicate similarities in household waste composition and thorough mixing in the biogas plants. If this profile is found to be spatially and temporally consistent, it can help regulators to establish priority lists of CECs of top concern. Assuming increasing use of biofertilizers for food production in the future, it would be beneficial to have concentration limits for CECs Risk estimation based on risk quotients (RQs) indicated generally low environmental risks associated with application of biofertilizer to soils for food crop production. However, the toxicity of CEC mixtures needs to be considered when estimating the risks from application of biofertilizers on agricultural land or in other production systems.
Subject(s)
Metals, Heavy , Refuse Disposal , Anaerobiosis , Biofuels , Food , Nicotine , Sewage/chemistryABSTRACT
Per- and polyfluoroalkyl substances (PFAS) are known to be persistent, bioaccumulative, and have adverse health effects, but very little is known about PFAS in the terrestrial environment and factors influencing their distribution. This paper presents one of the first comprehensive studies investigating PFAS (n = 28) in background forest soils (n = 27) on national scale across Sweden. The results showed that 16 of 28 target PFAS were present and all sites contained at least three PFAS compounds, with total concentrations ranging between 0.40 ng/g dry weight (dw) and 6.6 ng/g dw. Perfluorooctanesulfonic acid (PFOS) showed the highest detection frequency of 89% and a median concentration of 0.39 ng/g dw. The PFOS loads (ng/m3) showed a distinct spatial distribution, with a significant exponential increase from north to south (R2 = 0.55; p < 0.001) and west to east (R2 = 0.35; p < 0.01). In some parts of Sweden, the compound 6:2 fluorotelomer sulfonate (6:2 FTSA) had a higher median concentration (1.4 ng/g dw), but was in comparison to PFOS more impacted by local sources. Partial least squares discriminant analysis (PLS-DA) showed regional clustering of PFAS compositional profiles, indicating that PFAS soil background concentrations are functions of spatial variations at local, regional, and countrywide scale. Such spatial trends have not been observed previously and it could not be deduced whether they are indicative of trends on a global scale, or country-specific and better explained by proximity to densely populated urban areas. An interpolation and extrapolation raster map created from the results was used to calculate the average total PFAS load on Swedish soils. Estimated total load in the top 10-cm soil layer was 2.7 ± 2.4 tons for PFOS and 16 ± 14 tons for ∑PFAS, indicating that soil carries a considerable legacy of past PFAS release.
Subject(s)
Alkanesulfonic Acids , Fluorocarbons , Water Pollutants, Chemical , Alkanesulfonic Acids/analysis , Environmental Monitoring , Fluorocarbons/analysis , Soil , Sweden , Water Pollutants, Chemical/analysisABSTRACT
Most environmental monitoring studies of contaminants of emerging concern (CECs) focus on aquatic species and target specific classes of CECs. Even with wide-scope target screening methods, relevant CECs may be missed. In this study, non-target screening (NTS) was used for tentative identification of potential CECs in muscle tissue of the terrestrial top predator Eurasian lynx (Lynx lynx). Temporal trend analysis was applied as a prioritisation tool for archived samples, using univariate statistical tests (Mann-Kendall and Spearman rank). Pooled lynx muscle tissue collected from 1969 to 2017 was analysed with an eight-point time series using a previously validated screening workflow. Following peak detection, peak alignment, and blank subtraction, 12,941 features were considered for statistical analysis. Prioritisation by time-trend analysis detected 104 and 61 features with statistically significant increasing and decreasing trends, respectively. Following probable molecular formula assignment and elucidation with MetFrag, two compounds with increasing trends, and one with a decreasing trend, were tentatively identified. These results show that, despite low expected concentration levels and high matrix effects in terrestrial species, it is possible to prioritise CECs in archived lynx samples using NTS and univariate statistical approaches.
Subject(s)
Lynx , Water Pollutants, Chemical , Animals , Environmental Monitoring , Muscles/chemistry , Water Pollutants, Chemical/analysisABSTRACT
Environmental monitoring studies based on target analysis capture only a small fraction of contaminants of emerging concern (CECs) and miss pollutants potentially harmful to wildlife. Environmental specimen banks, with their archived samples, provide opportunities to identify new CECs by temporal trend analysis and non-target screening. In this study, archived white-tailed sea eagle (Haliaeetus albicilla) muscle tissue was analysed by non-targeted high-resolution mass spectrometry. Univariate statistical tests (Mann-Kendall and Spearman rank) for temporal trend analysis were applied as prioritisation methods. A workflow for non-target data was developed and validated using an artificial time series spiked at five levels with gradient concentrations of selected CECs (n = 243). Pooled eagle muscle tissues collected 1965-2017 were then investigated with an eight-point time series using the validated screening workflow. Following peak detection, peak alignment, and blank subtraction, 14 409 features were considered for statistical analysis. Prioritisation by time-trend analysis detected 207 features with increasing trends. Following unequivocal molecular formula assignment to prioritised features and further elucidation with MetFrag and EU Massbank, 13 compounds were tentatively identified, of which four were of anthropogenic origin. These results show that it is possible to prioritise new CECs in archived biological samples using univariate statistical approaches.
Subject(s)
Eagles , Environmental Pollutants , Animals , Environmental Monitoring , Environmental Pollutants/analysis , Mass Spectrometry , Muscles/chemistryABSTRACT
Soil samples from a contaminated site in Sweden were analyzed to identify the presence of 78 polycyclic aromatic compounds (PACs) using gas chromatography coupled with mass spectrometry (GC-MS). The target analysis revealed large contributions not only from polycyclic aromatic hydrocarbons (PAHs), but also from alkylated- and oxygenated-PAHs (alkyl- and oxy-PAHs, respectively), and N-heterocyclics (NPACs). PAC profiles indicated primarily pyrogenic sources, although contribution of petrogenic sources was also observed in one sample as indicated by a high ratio of alkylated naphthalene compared to naphthalene. The aryl hydrocarbon receptor (AhR)-activity of the soil extracts was assessed using the H4IIe-pGudluc 1.1 cells bioassay. When compared with the calculated total AhR-activity of the PACs in the target list, 35-97% of the observed bioassay activity could be explained by 62 PACs with relative potency factors (REPs). The samples were further screened using GC coupled with Orbitrap™ high resolution MS (GC-HRMS) to investigate the presence of other PACs that could potentially contribute to the AhR-activity of the extracts. 114 unique candidate compounds were tentatively identified and divided into four groups based on their AhR-activity and environmental occurrence. Twelve substances satisfied all the criteria, and these compounds are suggested to be included in regular screening in future studies, although their identities were not confirmed by standards in this study. High unexplained bio-TEQ fractions in three of the samples may be explained by tentatively identified compounds (n = 35) with high potential of being toxic. This study demonstrates the benefit of combining targeted and non-targeted chemical analysis with bioassay analysis to assess the diversity and effects of PACs at contaminated sites. The applied prioritization strategy revealed a number of tentatively identified compounds, which likely contributed to the overall bioactivity of the soil extracts.