Ikke-spesifikk karakterisering av organiske forbindelser av økende miljørelevans i luft og biota

Persistent organic pollutants (POPs) and other regulated organic chemicals are being monitored in the environment to evaluate the effectiveness of regulations and conventions, spatial and temporal trends as well as a compound`s environmental fate. However, there are hundreds of thousands of chemicals in commerce and new chemicals are continuously being developed. Some of these new chemicals have similar physical-chemical properties as known POPs or regulated chemicals, but their environmental fate is not well documented. Therefore, it is important to screen environmental samples for new potential chemicals of emerging concern (CECs) to detect such CECs at an early stage, preferably before reaching toxic or harmful concentrations for humans and/or the environment. The scientific work of this thesis aims to provide new methods to screen simultaneously for large number of compounds within a wide range of polarity and to identify new potential CECs in air and biota. One specific aim of the research of this thesis was the development and evaluation of new clean-up methods omitting the use of destructive or very selective clean-up processes in order to keep as many as possible compounds of interest in the clean extract. For high-volume air samples a three-layer liquid chromatography method was established. For biota, this new clean-up method was combined with additional wide scope clean-up steps due to the complexity of biological samples. The evaluation of the new clean-up method found that it could provide sample extracts of similar cleanness and quality, compared to the traditional method using concentrated sulphuric acid, but also including a broader range of compounds (i.e. also acid-labile compounds). Another aim of the research was the development of data processing workflows for the detection, identification and prioritisation of new potential CECs as well as the development of a wide-scope instrumental method for comprehensive two-dimensional gas chromatography (GC×GC) combined with low-resolution mass spectrometry (LRMS). The combination of new clean-up methods, comprehensive detection methods, and new data processing workflows, could reveal several new potential CECs in air and biota which were detected for the very first time. It was found that some of the CECs detected in air may undergo long-range atmospheric transport, due to the detection in southern Norway and the Arctic. Furthermore, it was found that some of the detected CECs in biota may have a bioaccumulation potential. This highlights the importance of screening studies for the early detection of new CECs in the environment. Further research is necessary to evaluate the environmental fate of these found CECs for possible regulatory actions.Persistente organisk miljøgifter (POPer) og andre regulerte organiske forbindelser blir overvåket i miljøet for å evaluere effektiviteten av reguleringer og konvensjoner, romlig og temporale trender så vel som forbindelsers miljøskjebne. Det er likevel hundre tusenvis av kjemikalier i handel og nye kjemikalier blir utviklet for bruk i industrien og daglig bruk. Noen av disse forbindelser har like fysikalsk-kjemiske egenskaper som kjente tungt-nedbrytbare organiske forbindelser (for eksempel POPer) eller regulerte kjemikalier, men deres miljøskjebne er ofte ikke godt nok dokumentert. Det er derfor viktig å kartlegge miljøprøver etter nye potensielle forbindelser av økende miljørelevans (CECer). Dette er også viktig for å oppdage slike CECer på et tidlig stadium, helst før de når toksiske eller skadelige nivåer for mennesker og/eller miljøet. Det vitenskapelige arbeidet i denne avhandlingen har til hensikt å utvikle nye metoder for å analysere et stort antall kjemiske sporstoffer innen et vidt polaritetsområde og identifiserer nye CECer i luft og biota. Ett mål med dette forskningsarbeidet var også å utvikle og evaluere nye opprensnings-metoder for å unngå bruk av destruktive og veldig selektive opparbeidelsesprosesser. Dette ble gjort for å beholde flest mulig forbindelser i prøveekstrakten. En kolonnekromatografisk metode bestående av tre ulike adsorbentlag ble utviklet for luft prøver med stort volum. Denne nye væske kromatografiske metoden ble kombinert og utvidet med flere ikke-spesifikke opparbeidelsesskritt på grunn av kompleksiteten i de biologiske prøvene. Gjennom evalueringen av den nye opparbeidelsesmetoden vle det bekreftet at metoden produserer ekstrakter med tilsvarende renhet og kvalitet, sammenlignet med den tradisjonelle metoden som benytter konsentrert svovelsyre. Dette gjelder også tilsvarende opparbeidelsesmetoder for analyser av syrelabile sporstoffer. Basert på denne studien ble det utviklet en standard analyse protokoll (SOP) for detektering, identifisering og prioritering av nye potensielle CECer. Videre ble det utviklet en ikke-spesifikk instrumentell metode for omfattende todimensjonal gass-kromatografi (GC×GC) i kombinasjon med lav oppløsende masse spektrometri (LRMS). Kombinasjonen av de nye prøveopparbeidelsesmetodene, den omfattende deteksjonsmetoden og databearbeidelsesmåten, avslørte flere nye potensielle CECer i luft- og biota-prøver. Det ble oppdaget at noen av CECene som ble detektert i luft muligens hadde vært utsatt for atmosfærisk langtransport siden de ble detektert i Sør Norge og på Svalbard. I tillegg ble det funnet at noen av de oppdagede CECene i biota kan ha et bioakkumuleringspotensial. Dette påpeker viktigheten av ikke-spesifikke kartlegging av miljøprøver for CECer er ett viktig ledd for en tidlig oppdagelse av nye CECer i miljøet. Videre forskning er nødvendig for å evaluere miljøskjebnen til de oppdagede nye CECene for mulige regulatoriske handlinger

Tiltaksorientert overvåking i henhold til vannforskriften for Glencore Nikkelverk AS i Kristiansandsfjorden. Undersøkelse av blåskjell i 2022.

Prosjektleder: Merete SchøyenNIVA har gjennomført tiltaksorientert overvåking i sjøområdet utenfor Glencore Nikkelverk AS i Kristiansandsfjorden i 2022 i henhold til vannforskriften. Ved fem blåskjellstasjoner har det blitt analysert for et utslippsrelevant utvalg av de prioriterte stoffene dioksiner, dioksinliknende PCB, bly (Pb) og nikkel (Ni). Det har også blitt analysert for de vannregionspesifikke stoffene arsen (As), kobber (Cu) og sink (Zn). I tillegg ble det analysert for sølv (Ag), kobolt (Co), jern (Fe), palladium (Pd), selen (Se), thorium (Th) og uran (U). Et utvalg triklor-trimetylbenzener (KAB) ble også analysert. For de prioriterte stoffene i blåskjell ble det ikke målt konsentrasjoner som overskred miljøkvalitetsstandarder (Environmental Quality Standard, EQS), og alle de fem blåskjellstasjonene var derfor i «god kjemisk tilstand». For de vannregionspesifikke stoffene er det ikke oppgitt EQS-verdier i biota i Veileder 02:2018. Det var signifikante oppadgående tidstrender for Co i blåskjell ved Glencore kai, og for As ved Dvergsøya. Det var signifikante nedadgående tidstrender for Cu i blåskjell ved Glencore kai og Hanneviksbukta, for Ni, Pb, Zn, Co og Fe ved Hanneviksbukta, og for dioksiner og dioksinliknende PCB ved Myrodden. Det ble påvist triklor-trimetylbenzener (sum KAB) på fire av de fem blåskjellstasjonene.Glencore Nikkelverk ASpublishedVersio

Screening program 2014: Fosfitter, utvalgte PBT stoffer og hypotesefri miljøscreening

The occurrence and environmental risk of a number of phosphites and selected PBT substances are reported for wastewater effluents and leachates, as well as sediments and biota from Oslofjord and Lake Mjøsa. In addition a suspect and non-target screening approach was applied to approximatley half of the biota samples.publishedVersio

Ongoing Laboratory Performance Study on Chemical Analysis of Hydrophobic and Hydrophilic Compounds in Three Aquatic Passive Samplers

The quality of chemical analysis is an important aspect of passive sampling-based environmental assessments. The present study reports on a proficiency testing program for the chemical analysis of hydrophobic organic compounds in silicone and low-density polyethylene (LDPE) passive samplers and hydrophilic compounds in polar organic chemical integrative samplers. The median between-laboratory coefficients of variation (CVs) of hydrophobic compound concentrations in the polymer phase were 33% (silicone) and 38% (LDPE), similar to the CVs obtained in four earlier rounds of this program. The median CV over all rounds was 32%. Much higher variabilities were observed for hydrophilic compound concentrations in the sorbent: 50% for the untransformed data and a factor of 1.6 after log transformation. Limiting the data to the best performing laboratories did not result in less variability. Data quality for hydrophilic compounds was only weakly related to the use of structurally identical internal standards and was unrelated to the choice of extraction solvent and extraction time. Standard deviations of the aqueous concentration estimates for hydrophobic compound sampling by the best performing laboratories were 0.21 log units for silicone and 0.27 log units for LDPE (factors of 1.6 to 1.9). The implications are that proficiency testing programs may give more realistic estimates of uncertainties in chemical analysis than within-laboratory quality control programs and that these high uncertainties should be taken into account in environmental assessments

Non-target and suspect characterisation of organic contaminants in ambient air, Part I: Combining a novel sample clean-up method with comprehensive two-dimensional gas chromatography

Long-term monitoring of regulated organic chemicals, such as legacy persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs), in ambient air provides valuable information about the compounds' environmental fate as well as temporal and spatial trends. This is the foundation to evaluate the effectiveness of national and international regulations for priority pollutants. Extracts of high-volume air samples, collected on glass fibre filters (GFF for particle phase) and polyurethane foam plugs (PUF for gaseous phase), for targeted analyses of legacy POPs are commonly cleaned by treatment with concentrated sulfuric acid, resulting in extracts clean from most interfering compounds and matrices that are suitable for multi-quantitative trace analysis. Such standardised methods, however, severely restrict the number of analytes for quantification and are not applicable when targeting new and emerging compounds as some may be less stable under acid treatment. Recently developed suspect and non-target screening analytical strategies (SUS and NTS, respectively) are shown to be effective evaluation tools aimed at identifying a high number of compounds of emerging concern. These strategies, combining highly sophisticated analytical technology with extensive data interpretation and statistics, are already widely accepted in environmental sciences for investigations of various environmental matrices, but their application to air samples is still very limited. In order to apply SUS and NTS for the identification of organic contaminants in air samples, an adapted and more wide-scope sample clean-up method is needed compared to the traditional method, which uses concentrated sulfuric acid. Analysis of raw air sample extracts without clean-up would generate extensive contamination of the analytical system, especially with PUF matrix-based compounds, and thus highly interfered mass spectra and detection limits which are unacceptable high for trace analysis in air samples. In this study, a novel wide-scope sample clean-up method for high-volume air samples has been developed and applied to real high-volume air samples, which facilitates simultaneous target, suspect and non-target analyses. The scope and efficiency of the method were quantitatively evaluated with organic compounds covering a wide range of polarities (logP 2–11), including legacy POPs, brominated flame retardants (BFRs), chlorinated pesticides and currently used pesticides (CUPs). In addition, data reduction and selection strategies for SUS and NTS were developed for comprehensive two-dimensional gas chromatography separation with low-resolution time-of-flight mass spectrometric detection (GC × GC-LRMS) data and applied to real high-volume air samples. Combination of the newly developed clean-up procedure and data treatment strategy enabled the prioritisation of over 600 compounds of interest in the particle phase (on GFF) and over 850 compounds in the gas phase (on PUF) out of over 25 000 chemical features detected in the raw dataset. Of these, 50 individual compounds were identified and confirmed with reference standards, 80 compounds were identified with a probable structure, and 774 compounds were assigned to various compound classes. In the dataset available here, 11 hitherto unknown halogenated compounds were detected. These unknown compounds were not yet listed in the available mass spectral libraries

Non-target and suspect characterisation of organic contaminants in ambient air, Part I: Combining a novel sample clean-up method with comprehensive two-dimensional gas chromatography

Long-term monitoring of regulated organic chemicals, such as legacy persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs), in ambient air provides valuable information about the compounds' environmental fate as well as temporal and spatial trends. This is the foundation to evaluate the effectiveness of national and international regulations for priority pollutants. Extracts of high-volume air samples, collected on glass fibre filters (GFF for particle phase) and polyurethane foam plugs (PUF for gaseous phase), for targeted analyses of legacy POPs are commonly cleaned by treatment with concentrated sulfuric acid, resulting in extracts clean from most interfering compounds and matrices that are suitable for multi-quantitative trace analysis. Such standardised methods, however, severely restrict the number of analytes for quantification and are not applicable when targeting new and emerging compounds as some may be less stable under acid treatment. Recently developed suspect and non-target screening analytical strategies (SUS and NTS, respectively) are shown to be effective evaluation tools aimed at identifying a high number of compounds of emerging concern. These strategies, combining highly sophisticated analytical technology with extensive data interpretation and statistics, are already widely accepted in environmental sciences for investigations of various environmental matrices, but their application to air samples is still very limited. In order to apply SUS and NTS for the identification of organic contaminants in air samples, an adapted and more wide-scope sample clean-up method is needed compared to the traditional method, which uses concentrated sulfuric acid. Analysis of raw air sample extracts without clean-up would generate extensive contamination of the analytical system, especially with PUF matrix-based compounds, and thus highly interfered mass spectra and detection limits which are unacceptable high for trace analysis in air samples. In this study, a novel wide-scope sample clean-up method for high-volume air samples has been developed and applied to real high-volume air samples, which facilitates simultaneous target, suspect and non-target analyses. The scope and efficiency of the method were quantitatively evaluated with organic compounds covering a wide range of polarities (logP 2–11), including legacy POPs, brominated flame retardants (BFRs), chlorinated pesticides and currently used pesticides (CUPs). In addition, data reduction and selection strategies for SUS and NTS were developed for comprehensive two-dimensional gas chromatography separation with low-resolution time-of-flight mass spectrometric detection (GC × GC-LRMS) data and applied to real high-volume air samples. Combination of the newly developed clean-up procedure and data treatment strategy enabled the prioritisation of over 600 compounds of interest in the particle phase (on GFF) and over 850 compounds in the gas phase (on PUF) out of over 25 000 chemical features detected in the raw dataset. Of these, 50 individual compounds were identified and confirmed with reference standards, 80 compounds were identified with a probable structure, and 774 compounds were assigned to various compound classes. In the dataset available here, 11 hitherto unknown halogenated compounds were detected. These unknown compounds were not yet listed in the available mass spectral libraries

Screening programme 2014: Phosphites, selected PBT substances and non-target screening

The occurrence and environmental risk of a number of phosphites and selected PBT substances are reported for wastewater effluents and leachates, as well as sediments and biota from Oslofjord and Lake Mjøsa. In addition a suspect and non-target screening approach was applied to approximatley half of the biota samples

Screening programme 2014: Phosphites, selected PBT substances and non-target screening

The occurrence and environmental risk of a number of phosphites and selected PBT substances are reported for wastewater effluents and leachates, as well as sediments and biota from Oslofjord and Lake Mjøsa. In addition a suspect and non-target screening approach was applied to approximatley half of the biota samples

Microplastics in Norwegian coastal areas, rivers, lakes and air (MIKRONOR1)

Prosjektleder Bert van BavelThe Norwegian Environment Agency (Miljødirektoratet, NEA) tasked the Norwegian Institute for Water Research (NIVA) to initiate Norway’s National microplastic monitoring program. The program “Microplastics in Norwegian coastal areas, rivers, lakes and air (MIKRONOR)”, was designed to target the multitude of environments in the Norwegian coastal, freshwater and terrestrial ecosystems. The primary aim is to provide information on levels and types of microplastics in aquatic environments as well as in air and build on the baseline data already generated for a number of these environments on previous assignments by NEA. This report contains the first results of coastal sites, open marine waters, lakes, rivers and air including high-volume water samples (freshwater and marine, n=48), Ferrybox samples (marine, n=20), blue mussels (marine, n=71), vertical plankton net samples (marine, n=29) and 24 air samples (precipitation n= 12 and active air sampling n = 12).Norwegian Environment AgencypublishedVersio

Målinger av miljøgifter i luft ved Franzefoss Eide på Sotra og Husøya ved Kristiansund

NILU har gjennomført måleprogram for konsentrasjoner i luft ved Franzefoss Gjenvinning AS sine anlegg ved Eide på Sotra og ved Husøya ved Kristiansund. Ved Eide ble det tatt prøver i luft og analysert for prioriterte miljøgifter som dekloraner, fenoler, ftalater, PFAS, benzotriazoler, organiske tinnforbindelser, samt VOC inkludert D6, ammoniakk (NH3), gassfase HCl og hydrogensulfid (H2S). For de prioriterte miljøgiftene var de fleste prøvene under deteksjonsgrensen. De høyeste verdiene ble observert ved Lokasjon 11 Vannrenseanlegget. Ved Husøya ble det tatt prøver i luft og analysert for VOC inkludert D6, ammoniakk (NH3) og gassfase HCl. Verdiene ved Husøya var lavere enn ved Eide