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NTNU Open
Master thesis . 2023
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Non-target Screening of Emerging Organic Pollutants in Siberian Sediments

Authors: Haraldsvik, Martin;

Non-target Screening of Emerging Organic Pollutants in Siberian Sediments

Abstract

Despite its remoteness, the Arctic is increasingly threatened by pollution, notably chemical runoff. In response, this study examines both targeted and non-targeted analytical methods, employing these techniques to evaluate sediment samples from Siberia's coastline. Two extraction methods were assessed, one intended for the analysis of polar substances and the other for non-polar substances, and their potential use in non-target screening applications was evaluated. Both methods were tested with spiked and un-spiked sediment samples from the Barents Sea, followed by their application to analyze sediment samples from the Kara Sea. The method for non-polar substances was analyzed with direct injection into a quadrupole time-of-flight mass spectrometer (Q-TOF) and tested with a spiking mixture encompassing a wide range of chlorinated paraffins (CPs). The method displayed reasonable recoveries (57-70%) across all compounds tested and thus shows promise as an extraction method for use in non-target screenings of non-polar compounds in sediments. The method for polar substances was analyzed using two different mass spectrometers coupled to an ultra-performance liquid chromatograph (UPLC). The mass spectrometers used were a Q-TOF mass spectrometer and a triple quadrupole (QqQ) mass spectrometer. The method was tested with a spiking mixture containing 40 per- and polyfluoroalkyl substances (PFAS) encompassing a wide range of physiochemical properties. The method exhibited excellent recoveries (85-130%) for smaller (C<9) perfluoro sulfonic acids (PFSAs) and fluorotelomer sulfonates (FTSs), while also being able to detect 29 of the 40 compounds in the spiking mixture in concentrations of 1 ng/g when analyzed using non-target screening methods. Therefore, the extraction method demonstrates potential for both targeted analysis of smaller PFSAs and FTSs, and non-target analysis of polar compounds in sediments. Following this, the polar extraction method was used to perform both a targeted and a non-targeted analysis of samples taken from six diverse locations in the Kara Sea, ranging from the coastline to more remote offshore sites. The targeted screening yielded identifications of eleven PFAS compounds and semi-quantitative results for three of these. The compounds identified in the samples were PFPeS, PFHxS, PFHpS, PFOS, PFNS, PFDS, PFECHS, 4:2 FTS, 6:2 FTS, 8:2 FTS, and ADONA. Notably, PFOS was found in concentrations of 0.1 to 0.45 ng/g of wet sediment, 4:2 FTS was found in concentrations of up to 0.4 ng/g of wet sediment, and 6:2 FTS was found in concentrations of up to 0.3 ng/g of wet sediment. The non-targeted screening of the Kara Sea sediments yielded data on 60 features, 29 of which were given possible identifications. The trends of the 12 features with the highest responses were examined, and it was discovered that three of the compounds showed no spatial trends, three showed significantly higher responses in the samples from the Yenisei and Ob River plume, and six showed the highest response in a sample from shallow waters in the middle of the Kara Sea.

Til tross for sin avsidesliggende beliggenhet, er Arktis i økende grad truet av forurensning, særlig fra kjemisk avrenning. I lys av dette undersøker denne studien både målrettede og ikke-målrettede analytiske metoder, og anvender disse teknikkene for å evaluere sedimentprøver fra Sibirs kystlinje. To ekstraksjonsmetoder ble vurdert, en beregnet for analyse av polare stoffer og den andre for ikke-polare stoffer, og deres potensiale for bruk i ikke-målrettede analyser ble evaluert. Begge metodene ble testet med fra Barentshavet med og uten tilsatte test-stoffer, etterfulgt av deres anvendelse for å analysere sedimentprøver fra Karahavet. Metoden for ikke-polare stoffer ble analysert med direkte injeksjon i et kvadrupol time-of-flight massespektrometer (Q-TOF) og testet med en stoffblanding som omfattet et bredt spekter av klorerte parafiner (CP). Metoden viste rimelige utvinningsrater (57-70 %) av alle testede forbindelser og virker derfor lovende som en ekstraksjonsmetode for bruk i ikke-målrettede analyser av ikke-polare forbindelser i sedimenter. Metoden for polare stoffer ble analysert ved bruk av to forskjellige massespektrometre koblet til en ultra-ytelses væskekromatograf (UPLC). De anvendte massespektrometrene var et Q-TOF massespektrometer og et trippelt kvadrupol (QqQ) massespektrometer. Metoden ble testet med en stoffblanding inneholdende 40 per- og polyfluoralkylsubstanser (PFAS) som omfattet et bredt spekter av fysiokjemiske egenskaper. Metoden viste utmerket utvinning (85-130%) for mindre (C<9) perfluorsulfonsyrer (PFSA) og fluortelomersulfonater (FTS), samtidig som den var i stand til å påvise 29 av de 40 forbindelsene i stoffblandingen i konsentrasjoner på 1 ng/g når analysert ved bruk av ikke-målrettede analyse metoder. Derfor viser utvinningsmetoden potensiale for både målrettet analyse av mindre PFSAer og FTSer, og ikke-målrettet analyse av polare forbindelser i sedimenter. Videre ble den polare utvinningsmetoden brukt til å utføre både en målrettet og en ikke-målrettet analyse av prøver tatt fra seks forskjellige lokasjoner i Karahavet, alt fra kystlinjen til mer avsidesliggende offshore-steder. Den målrettede analysen resulterte i identifikasjon av elleve PFAS-forbindelser, og semikvantitative resultater for tre av disse. Forbindelsene identifisert i prøvene var PFPeS, PFHxS, PFHpS, PFOS, PFNS, PFDS, PFECHS, 4:2 FTS, 6:2 FTS, 8:2 FTS og ADONA. PFOS ble funnet i konsentrasjoner på 0,1 til 0,45 ng/g vått sediment, 4:2 FTS ble funnet i konsentrasjoner på opptil 0,4 ng/g vått sediment, og 6:2 FTS ble funnet i konsentrasjoner på opptil 0,3 ng/g vått sediment. Den ikke-målrettede analysen av sedimentene fra Karahavet ga data om 60 mulige forbindelser, hvorav 29 ble gitt mulige identifikasjoner. Trendene til de 12 forbindelsene med høyest respons ble undersøkt, og det ble oppdaget at tre av forbindelsene ikke viste romlige trender, tre viste signifikant høyere respons i prøvene fra Jenisej- og Ob-elven, og seks viste høyest respons i en prøve fra grunt vann midt i Karahavet.

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Norway
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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
0
Average
Average
Average
Green