Kyra SpaanPhD student
Research projects
Publications
A selection from Stockholm University publication database
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High Concentrations of Unidentified Extractable Organofluorine Observed in Blubber from a Greenland Killer Whale (Orcinus orca)
2020. Lara Schultes (et al.). Environmental Science and Technology Letters 7 (12), 909-915
ArticleRead more about High Concentrations of Unidentified Extractable Organofluorine Observed in Blubber from a Greenland Killer Whale (Orcinus orca)It is generally accepted that per- and polyfluoroalkyl substances (PFASs) occur primarily in protein-rich tissues such as blood and liver, but few studies have examined the occurrence of legacy and novel PFASs in lipid-rich tissues such as blubber. Here we report the distribution of 24 PFASs, total fluorine, and extractable organic fluorine (EOF) in eight different tissues of a killer whale (Orcinus orca) from East Greenland. The sum of target PFAS concentrations was highest in liver (352 ng/g of wet weight) and decreased in the following order: blood > kidney approximate to lung approximate to ovary > skin approximate to muscle approximate to blubber. Most of the EOF consisted of known PFASs in all tissues except blubber, which displayed the highest concentration of EOF, almost none of which was attributed to targeted PFASs. Suspect screening using high-resolution mass spectrometry revealed the presence of additional PFASs but is unlikely to explain the high concentrations of EOF in blubber. While the identity of this unknown organofluorine and its pervasiveness in marine mammals require further investigation, this work suggests that exposure of killer whales to organofluorine substances may be underestimated by determination of legacy PFASs exclusively in liver or blood.
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Fluorine Mass Balance and Suspect Screening in Marine Mammals from the Northern Hemisphere
2020. Kyra M. Spaan (et al.). Environmental Science and Technology 54 (7), 4046-4058
ArticleRead more about Fluorine Mass Balance and Suspect Screening in Marine Mammals from the Northern HemisphereThere is increasing evidence that the similar to 20 routinely monitored perfluoroalkyl and polyfluoroalkyl substances (PFASs) account for only a fraction of extractable organofluorine (EOF) occurring in the environment. To assess whether PFAS exposure is being underestimated in marine mammals from the Northern Hemisphere, we performed a fluorine mass balance on liver tissues from 11 different species using a combination of targeted PFAS analysis, EOF and total fluorine determination, and suspect screening. Samples were obtained from the east coast United States (US), west and east coast of Greenland, Iceland, and Sweden from 2000 to 2017. Of the 36 target PFASs, perfluorooctane sulfonate (PFOS) dominated in all but one Icelandic and three US samples, where the 7:3 fluorotelomer carboxylic acid (7:3 FTCA) was prevalent. This is the first report of 7:3 FTCA in polar bears (similar to 1000 ng/g, ww) and cetaceans (<6-190 ng/g, ww). In 18 out of 25 samples, EOF was not significantly greater than fluorine concentrations derived from sum target PFASs. For the remaining 7 samples (mostly from the US east coast), 30-75% of the EOF was unidentified. Suspect screening revealed an additional 37 PFASs (not included in the targeted analysis) bringing the total to 63 detected PFASs from 12 different classes. Overall, these results highlight the importance of a multiplatform approach for accurately characterizing PFAS exposure in marine mammals.
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Can determination of extractable organofluorine (EOF) be standardized? First interlaboratory comparisons of EOF and fluorine mass balance in sludge and water matrices
2021. Anna Kärrman (et al.). Environmental Science (10)
ArticleRead more about Can determination of extractable organofluorine (EOF) be standardized? First interlaboratory comparisons of EOF and fluorine mass balance in sludge and water matricesThe high proportion of unidentified extractable organofluorine (EOF) observed globally in humans and the environment indicates widespread occurrence of unknown per- and polyfluoroalkyl substances (PFAS). However, efforts to standardize or assess the reproducibility of EOF methods are currently lacking. Here we present the first EOF interlaboratory comparison in water and sludge. Three participants (four organizations) analyzed unfortified and PFAS-fortified ultrapure water, two unfortified groundwater samples, unfortified wastewater treatment plant effluent and sludge, and an unfortified groundwater extract. Participants adopted common sample handling strategies and target lists for EOF mass balance but used in-house combustion ion-chromatography (CIC) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods. EOF accuracy ranged from 85-101% and 76-109% for the 60 and 334 ng L-1 fluorine (F) - fortified water samples, respectively, with between-laboratory variation of 9-19%, and within-laboratory variation of 3-27%. In unfortified sludge and aqueous samples, between-laboratory variation ranged from 21-37%. The contribution from sum concentrations of 16 individual PFAS ( n-ary sumation PFAS-16) to EOF ranged from 2.2-60% but extended analysis showed that other targets were prevalent, in particular ultra-short-chain perfluoroalkyl acids (e.g. trifluoroacetic acid) in aqueous samples and perfluoroalkyl acid-precursors (e.g. polyfluoroalkyl phosphate diesters) in sludge. The EOF-CIC method demonstrated promising accuracy, robustness and reporting limits but poor extraction efficiency was observed for some targets (e.g. trifluoroacetic acid).
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Pharmaceuticals Account for a Significant Proportion of the Extractable Organic Fluorine in Municipal Wastewater Treatment Plant Sludge
2023. Kyra M. Spaan (et al.). Environmental Science and Technology Letters 10 (4), 328-336
ArticleRead more about Pharmaceuticals Account for a Significant Proportion of the Extractable Organic Fluorine in Municipal Wastewater Treatment Plant SludgeFluorine mass balance studies have shown that monomeric per- and polyfluoroalkyl substances (PFAS) with perfluoroalkyl chain lengths of ∼5–14 carbon atoms (i.e., “conventional” PFAS) account for a fraction (∼2%) of the extractable organic fluorine (EOF) in municipal wastewater treatment plant (WWTP) sludge. The identity of the remaining EOF has thus far been unclear but may be partly attributable to fluorine-containing pharmaceuticals and pesticides used throughout society. To test this hypothesis, we applied high resolution mass spectrometry-based suspect screening to samples of municipal WWTP sludge which had been previously subjected to a fluorine mass balance. Sixteen pharmaceutical substances (including transformation products [TPs]), one pesticide, and thirteen conventional PFAS were confirmed at confidence levels 1–4 and (semi)quantified, revealing concentrations ranging from 0.07 to 155 ng/g dw. Notably, eight pharmaceutical substances did not meet the OECD definition of PFAS. When converted to fluorine equivalents, the newly detected organofluorine substances increased the percentage of known EOF from ∼2% to ∼27%, of which ∼22% was attributed to pharmaceutical and pesticide substances, with the greatest contributions from ticagrelor TP (4.0%), ezetimibe (3.9%), and bicalutamide (3.5%). These data highlight the importance of considering both unconventional and non-PFAS organofluorine substances in addition to conventional PFAS when closing the organofluorine mass balance in WWTP sludge.
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Per- and polyfluoroalkyl substances (PFAS) in white-tailed sea eagle eggs from Sweden: temporal trends (1969-2021), spatial variations, fluorine mass balance, and suspect screening
2023. Faiz Haque (et al.). Environmental Science 25 (9), 1549-1563
ArticleRead more about Per- and polyfluoroalkyl substances (PFAS) in white-tailed sea eagle eggs from SwedenTemporal and spatial trends of 15 per- and polyfluoroalkyl substances (PFAS) were determined in white-tailed sea eagle (WTSE) eggs (Haliaeetus albicilla) from two inland and two coastal regions of Sweden between 1969 and 2021. PFAS concentrations generally increased from ∼1969 to ∼1990s–2010 (depending on target and site) and thereafter plateaued or declined, with perfluorooctane sulfonamide (FOSA) and perfluorooctane sulfonate (PFOS) declining faster than most perfluoroalkyl carboxylic acids (PFCAs). The net result was a shift in the PFAS profile from PFOS-dominant in 1969–2010 to an increased prevalence of PFCAs over the last decade. Further, during the entire period higher PFAS concentrations were generally observed in coastal populations, possibly due to differences in diet and/or proximity to more densely populated areas. Fluorine mass balance determination in pooled samples from three of the regions (2019–2021) indicated that target PFAS accounted for the vast majority (i.e. 81–100%) of extractable organic fluorine (EOF). Nevertheless, high resolution mass-spectrometry-based suspect screening identified 55 suspects (31 at a confidence level [CL] of 1–3 and 24 at a CL of 4–5), of which 43 were substances not included in the targeted analysis. Semi-quantification of CL ≤ 2 suspects increased the identified EOF to >90% in coastal samples. In addition to showing the impact of PFAS regulation and phase-out initiatives, this study demonstrates that most extractable organofluorine in WTSE eggs is made up of known (legacy) PFAS, albeit with low levels of novel substances.
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Characterizing the Organohalogen Iceberg: Extractable, Multihalogen Mass Balance Determination in Municipal Wastewater Treatment Plant Sludge
2023. Kyra M. Spaan (et al.). Environmental Science and Technology 57 (25), 9309-9320
ArticleRead more about Characterizing the Organohalogen IcebergThe large number and diversity of organohalogen compounds(OHCs)occurring in the environment poses a grand challenge to analyticalchemists. Since no single targeted method can identify and quantifyall OHCs, the size of the OHC iceberg may be underestimated.We sought to address this problem in municipal wastewater treatmentplant (WWTP) sludge by quantifying the unidentified fraction of theOHC iceberg using targeted analyses of major OHCs together with measurementsof total and extractable (organo)halogen (TX and EOX, respectively;where X = F, Cl, or Br). In addition to extensive method validationvia spike/recovery and combustion efficiency experiments, TX and/orEOX were determined in reference materials (BCR-461 and NIST SRMs2585 and 2781) for the first time. Application of the method to WWTPsludge revealed that chlorinated paraffins (CPs) accounted for most(similar to 92%) of the EOCl, while brominated flame retardants and per-and polyfluoroalkyl substances (PFAS) accounted for only 54% of theEOBr and 2% of the EOF, respectively. Moreover, unidentified EOF innonpolar CP extracts points to the existence of organofluorine(s)with physical-chemical properties unlike those of target PFAS.This study represents the first multihalogen mass balance in WWTPsludge and offers a novel approach to prioritization of sample extractsfor follow-up investigation. A multihalogenmass balance experiment in WWTP sludge revealedhigh levels of unidentified organofluorine and organobromine. Organochlorinewas characterized mainly by chlorinated paraffins.