Search

The composition of vehicle fuels has changed since 2018 due to the reduction obligation, which requires that an increasing proportion of bio-based content is mixed into fossil fuels. Since properties such as odour and ecotoxicity are complex and depend on the composition of substances' mixtures, information based on older studies is not applicable. Odour properties are essential for drinking water producers, and ecotoxicity is vital for prioritising remediation efforts in the event of spillage. The objectives of this study have therefore been to 1) quantify the composition of standard diesel and petrol fuels sold in Sweden, 2) quantify odour thresholds for these fuels in drinking water, 3) investigate the ecotoxicity from HVO (hydrogenated vegetable oil) and diesel with RME additive (rapeseed methyl ester), and 4) investigate whether it is possible to predict odour in water based on concentrations in a fuel/water mixture.In the study, a total of eight fuels were tested, of which four were diesel fuels (HVO 100, MK1 diesel with HVO, MK1 diesel with RME and MK1 diesel) and four contained petrol/ethanol to varying degrees (E85, E05, E10 with bio-petrol and E10). HVO 100 and MK1 diesel with RME were used for ecotox tests on alga, bacteria, and crustaceans, as well as for degradation tests.Petrol/ethanol fuels were more efficiently dissolved in water than diesel fuels. This is because they contain a higher proportion of more water-soluble substances, such as ethers and light aromatic compounds, and the mixture of ethanol in the fuels. The E85 fuel resulted in the highest concentrations of hydrocarbons in the water mixture, even though the proportion of petrol is only 15%. A similar effect on solubility could be observed for RME in diesel fuels, although not to the same extent.The amounts of dissolved ether determined the odour properties of fuels in water. The 98 octane E05 fuel had the highest ether concentration in the fuel product, while the ether content of E85 was most effectively dissolved in water due to the high ethanol content. The odour thresholds were at 0.0017% in a water/fuel mixture for the E05 fuel and 0.0042% for E85. The ethers so dominated the odour that the methyl tert-butyl ether (MTBE) concentration could accurately predict the smell in an aqueous solution.Overall, the ecotoxicological tests showed mild or no effect from the fuels on the tested organisms. The exception was for the reproduction of crustaceans that were disturbed by MK1 diesel with RME. The low solubility of the two tested diesel fuels in water resulted in too low concentrations of hydrocarbons in the fuel/water mixture for valid degradation tests. Sammansättningen av fordonsbränslen har förändrats sedan 2018 beroende på reduktionsplikten, som innebär att en ökande andel biobaserat innehåll måste blandas in i fossila bränslen. Eftersom egenskaper såsom lukt och ekotoxicitet är komplexa och beror av hur blandningar av ämnen är sammansatta, betyder det att gamla data inte är tillämpliga. Luktegenskaper är viktiga för dricksvattenproducenter, medan ekotoxiciteten är viktig för prioriteringen av saneringsinsatser vid spill. Målen för den här studien har därför varit att: 1) kvantifiera innehållet i ett antal vanliga diesel- och bensinbränslen som säljs i Sverige, 2) kvantifiera lukttrösklar för dessa bränslen i dricksvatten, 3) undersöka ekotoxiciteten från HVO (hydrogenated vegetable oil) och diesel med RME-tillsats (rapsmetylester), samt 4) undersöka om det är möjligt att prediktera lukt i vatten baserat på koncentrationer i en bränsle/vatten-blandning. I studien har sammanlagt åtta bränslen testats, varav fyra stycken var dieselbränslen (HVO 100, MK1 diesel med HVO, MK1 diesel med RME och MK1 diesel) och fyra stycken innehöll bensin/etanol i olika omfattning (E85, E05, E10 med biobensin och E10). HVO 100 och MK1 diesel med RME användes för ekotoxtester på alger, bakterier, kräftdjur och nedbrytningstest. Bensin/etanol-bränslen löstes effektivare i vatten än dieselbränslen. Detta beror på att de innehåller en högre andel ämnen som är mer vattenlösliga, exempelvis etrar och lätta aromatiska föreningar, men också på inblandningen av etanol i bränslena. E85-bränslet gav de högsta koncentrationerna i vattenblandningen, trots att andelen bensin bara är 15 %. En liknande effekt på löslighet kunde obserververas för RME i dieselbränslena, om än inte i lika hög utsträckning. Luktegenskaperna hos bränslen i vatten bestämdes till absolut största delen av hur mycket etrar som lösts i vatten. I det 98 oktaniga E05 bränslet fanns högst koncentration i bränslet och den eter som fanns i E85 löstes effektivast i vatten, vilket gjorde att lukttrösklarna för dessa låg vid 0,0017 % inblandning av vatten/bränsleblandning i rent vatten för E05-bränslet och 0,0042 % för E85. Etrarna var så drivande för lukten att koncentrationen av dessa kunde prediktera lukten i en vattenlösning med god precision. De ekotoxikologiska testerna visade i regel mild eller ingen effekt från bränslena på de testade organismerna. Undantaget var för reproduktionen hos kräftdjur som stördes av MK1 diesel med RME. Den låga lösligheten hos de två testade dieselbränslena i vatten gav för låga koncentrationer av kolväten i bränsle-/vattenblandningen för att genomföra giltiga nedbrytningstester

Additional file 1. Additional materials S1 (Sects. 1–7), additional tables S1, S2 and additional figures S1–S10.

Wastewater treatment plants (WWTPs) can be considered a water pollution point source as all potential pollutants from household as well as from certain industry production passes the WWTPs. Therefore, sludge from WWTPs may be enriched with pollutants and is a relevant matrix for screening for both known and hitherto unknown potential hazardous chemicals. If the sludge from municipal WWTPs is to be used as a source of nutrient or other purposes, then it could be necessary to employ methods for removal of micropollutants in the sludge. The present study constitutes an addition to a large-scale experiment focusing on the reduction of pharmaceuticals, antibiotics and hormones in sewage sludge stored over a period of a year. The objective of the present study was to analyse the presence of per- and polyfluoroalkyl substances (PFAS), organophosphate esters, phthalates and alternative plasticizers and their potential degradation/reduction in mesophilic anaerobic digested sludge in different treatments. This study is part of a larger on-going project on reduction of pharmaceuticals and organic pollutants in sludge. Extracts of sludge samples were analysed using three instrumental methods: liquid chromatography coupled to both tandem mass spectrometry (LC-MS/MS) and high-resolution mass spectrometry (LC-HRMS) and gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Target analysis of several compounds (PFASs, organophosphate esters, phthalates and alternative plasticizers), analysis of total oxidizable precursors of PFASs and a suspect-screening of more than 1000 PFAS were performed at IVL. Extractable organic fluorine (EOF) was also performed on combustion ion chromatography at Stockholm University for quantification of potential unknown fluorinated compounds in the sludge. Decreasing trends for concentrations of organophosphate esters, phthalates, alternative plasticizers and PFAS could be observed in composted sludge over the storage time while the non-composted showed variable time trends for different substance classes. For PFAS, the sum concentrations of target analytes increased by almost an order of magnitude during 12 months of storage in the non-composted sludge. Furthermore, the results from TOP and EOF furthermore suggested that the sludge from both treatment experiments contained a significant fraction PFAS that could not be quantified by the targeted analysis. Avloppsreningsverk kan betraktas som en viktig punktkälla för föroreningar i vatten. Slam från avloppsreningsverk kan anrika föroreningar som har en huvudsaklig fördelning till slammet, och är således en relevant matris för screening för både kända och potentiella farliga kemikalier. Om slammet från kommunala avloppsreningsverk skall användas som en källa för näringsämnen eller andra syften kan det vara nödvändigt att avlägsna eller bryta ned potentiellt farliga mikroföroreningar i slammet. Denna studie utgör ett tillägg till ett storskaligt experiment som fokuserar på minskning av läkemedel, antibiotika och hormoner i avloppsslam som lagrats ett år. Kompakt eller poröst slam som rötats antingen termofilt eller mesofilt har i ovan nämnda experimentet lagrats under flera olika betingelser: täckt eller öppet, med och utan tillsats av urea, samt med och utan kompostering. I denna studie har endast poröst mesofilt rötat slam, som antingen har lagrats öppet eller med kompostering, studerats. Syftet med den här studien var att studera om per- och polyfluoralkylsubstanser (PFAS), organofosfatestrar samt ftalater och alternativa mjukgörare bryts ned under lagring. Extrakt av slamprover har analyserats med tre instrumentella metoder: vätskekromatografi kopplad till både tandemsmasspektrometri (LC-MS / MS) och högupplösta masspektrometri (LC-HRMS) samt gaskromatografi kopplad till tandemsmasspektrometri (GC-MS / MS). Förutom riktad kvantitativ analys av flera föreningar har analys av totala oxiderbara prekursorer av PFAS-ämnen och en sk suspect screening av mer än 1000 PFAS genomförts. Andelen extraherbart organiskt bunden fluor (EOF), dvs den totala fluormängden bundet till organiska ämnen, har också bestämts av Stockholms Universitet med förbränningsjonkromatografi för att kvantifiera andelen av potentiellt okända PFAS. Minskande trender för koncentrationer av organofosfatestrar, ftalater och alternativa mjukgörare samt PFAS kunde observeras i slam med kompostbehandlingen medan slammet som lagrats öppet inte visade någon tydlig trend för de ämnen som mättes i denna studie. För PFAS ökade summan av analyserade ämnen med nästan en tiopotens under 12 månaders lagring i det icke-komposterade slammet. Resultaten från TOP och EOF visade även på en betydande andel (91-97%) av hittills oidentifierade PFAS i slam från båda försöken.

Projektet ”Kemikaliesmarta åtgärder i förskola” har kartlagt och bedömt förändring i förekomsten av farliga kemikalier i förskolemiljö. Tre kemikaliesmarta tillvägagångssätt har tillämpats: nybyggnation enligt fastighetsägarens miljöstyrningsrutiner som bland annat innefattar val av byggmaterial som är godkända enlig Byggvarubedömningen, ombyggnation med tillämpning av samma rutiner samt genomförandet av kemikaliesmarta åtgärder på nivå 1 i enlighet med dokumentet Vägledning för kemikaliesmart förskola som innebär utfasning av föremål som misstänkt innehålla de farliga kemikalierna från förskolan innemiljö.

Children are exposed to a wide range of chemicals in their everyday environments, including the preschool. In this study, we evaluated the levels of phthalates, non-phthalate plasticizers and bisphenols in dust from 100 Swedish preschools and identified important exposure factors in the indoor environment. In addition, children's total exposure to these chemicals was determined by urine analysis to investigate their relation with dust exposure, and to explore the time trends by comparing with children who provided urine fifteen years earlier. The most abundant plasticizers in preschool dust were the phthalates di-isononyl phthalate (DiNP) and di-(2-ethylhexyl) phthalate (DEHP) with geometric mean levels of 450 and 266 μg/g dust, respectively, and the non-phthalate plasticizers bis(2-ethylhexyl) terephthalate (DEHT) and diisononylcyclohexane-1,2-dicarboxylate (DiNCH) found at 105 and 73 μg/g dust, respectively. The levels of several substitute plasticizers were higher in newer preschools, whereas the levels of the strictly regulated phthalate di-n-butyl phthalate (DnBP) were higher in older preschools. The presence of foam mattresses and PVC flooring in the sampling room were associated with higher levels of DiNP in dust. Children's exposure from preschool dust ingestion was below established health based reference values and the estimated exposure to different phthalates and BPA via preschool dust ingestion accounted for 2–27% of the total exposure. We found significantly lower urinary levels of BPA and metabolites of strictly regulated phthalates, but higher levels of DiNP metabolites, in urine from the children in this study compared to the children who provided urine samples fifteen years earlier. Keywords: Dust, Preschool, Exposure assessment, Plasticizer, Phthalate, Bisphenol A

Organophosphate esters (OPEs) are a group of chemicals that have been used for more than a century. OPEs are widely used as flame retardants, plasticizers, anti-foaming agents and as additives in lubricants and hydraulic fluids. The results of a screening assessment carried out by Umeå University in 2004 showed that OPEs can be found in for example air, deposition and snow, both near and far from emission sources. That the atmosphere is an important route of transportation for these substances has also been shown in later studies showing that several OPEs occur in Arctic air and biota. However, they have never been part of the regular environmental air monitoring program in Sweden. The aim of this study was to get an idea of the levels of OPEs in background air and the importance of air transportation of these chemicals in Sweden and northern Finland. Sample extracts from the regular environmental monitoring program of organic pollutants in air were used for the analyses and the results were evaluated in order to propose future measurement programs. The measured OPEs were TEP, TiBP, TnBP, TCEP, TCPP, TDCP, TBEP, TEHP, TPhP, EHDPP, ToCrP and TCrP mix. TCEP, TCPP and EHDPP were measured in the highest concentrations. Unfortunately, TPhP and TCrP mix were excluded from the results due to the detection of contamination from the polyurethane plugs used as adsorbents. To get an idea of the regional distribution, air samples were taken from the three stations, Råö at the Swedish west coast, Norunda at the east of Sweden and Pallas in northern Finland. Generally, the highest levels of OPEs were measured in Pallas and the lowest in Norunda. For TCEP and EHDPP, a geographical variation could be distinguished with highest concentrations in the north and lowest in the south. To get information about seasonal variations, sample extracts for the OPE-analyses were taken from the ordinary measurements for one year (2018), from January to December. Seasonal variations were observed for TCPP and TCEP at Råö, where higher levels were measured during the summer. In Pallas, the highest concentrations of some OPEs were instead detected in late summer. The measurements at Norunda did not show any clear seasonal variations. The results of the measurements in this study were compared with literature data, which showed good agreement levels as well as similar relationships among different OPEs. Production figures of different OPEs were difficult to find. Although, TEP, which is reported to be produced in large quantities, was not detected in high concentrations in air at any of the stations. Based on the results of this study, we conclude that the existing network of measurement stations, monitoring frequency, sampling and analysis procedures used within the environmental monitoring, can be used to measure organophosphates in air as well. However, the material used for the PUF adsorbent and the extraction method should be further evaluated to ensure the quality of the measurements. Organofosfatestrar (OPEs) är en grupp kemikalier som har använts under lång tid. OPEs används i stor utsträckning som flamskyddsmedel och mjukgörare i plaster, men de används även som bl.a. antiskummedel och som tillsatser i smörjmedel och hydraul-vätskor. Resultaten från ett screeninguppdrag som utfördes av Umeå Universitet redan 2004 visar att OPEs återfinns i bl.a. luft, deposition och snö, både nära och långt ifrån källor. Att luft är en viktig spridningsväg för dessa ämnen har visats även i senare studier då man sett att ett antal OPEs förekommer i luften i arktiska områden där de också har påträffats i biota. Trots detta har inte OPEs tidigare ingått i den reguljära miljöövervakningen av luft i Sverige. Syftet med denna studie var att få en uppfattning om halter av OPEs i bakgrundsluft och betydelsen av spridning av OPEs via luft i Sverige och norra Finland. Provextrakt från ordinarie mätprogram av organiska föroreningar i luft användes för analyserna, och resultaten av mätningarna utvärderades i syfte att föreslå framtida mätprogram. De OPEs som mättes var TEP, TiBP, TnBP, TCEP, TCPP, TDCP, TBEP, TEHP, TPhP, EHDPP, ToCrP och TCrP-mix. Högst halter uppmättes av TCEP, TCPP och EHDPP. Tyvärr fick TPhP och TCrP-mix exkluderas från resultaten på grund av upptäckt kontaminering från materialet av de polyuretanpluggar som användes som adsorbenter. För att få uppfattning om regional spridning togs luftprover från de tre stationerna, Råö på svenska västkusten, Norunda på östra sidan av Sverige och Pallas i norra Finland. Generellt uppmättes de högsta halterna OPEs i Pallas och de lägsta halterna i Norunda. För TCEP och EHDPP kunde en geografisk variation urskönjas, med högst halter i norr och lägst i söder. För att studera en möjlig årstidsvariation togs provextrakt för OPE-analyser från ordinarie mätningar under ett år (2018), från januari till december. De tydligaste årstidsvariationerna observerades för TCPP och TCEP i Råö där högre halter uppmättes under sommarhalvåret. I Pallas uppmättes högst värden av vissa OPE istället under sensommaren. Mätningarna på Norunda visade inga tydliga årstidsvariationer. I utvärderingen jämfördes resultaten av mätningarna med litteraturdata. Denna undersökning visade god överensstämning av OPE-koncentrationer och liknande relationer mellan olika OPEs. Det var svårt att finna produktionssiffror av olika OPEs. Dock visade en grov jämförelse att TEP som uppges produceras i stora mängder, inte detekterades i höga koncentrationer i luft på någon av stationerna. Utifrån resultaten från denna studie drar vi slutsatsen att det existerande nätverket av mätstationer och mät- och analysprocedurer, som idag används inom miljöövervakningen (EMEP), även kan användas för att mäta organofosfater i luft. Dock rekommenderar vi att PUF-materialet och extraktionsmetoden vidare utvärderas för att säkerhetsställa mätningarnas kvalité.

We analysed floor dust samples from 65 children's bedrooms in Finland collected in 2014/2015 for 62 different per- and polyfluoroalkyl substances (PFASs) with a simple and highly efficient method. Validation results from the analysis of standard reference material (SRM) 2585 were in good agreement with literature data, while 24 PFASs were quantified for the first time. In the dust samples from children's bedrooms, five perfluoroalkyl carboxylic acids (PFCAs) and perfluorooctane sulfonic acid (PFOS) were detected in more than half of the samples with the highest median concentration of 5.26 ng/g for perfluorooctanoic acid (PFOA). However, the dust samples were dominated by polyfluoroalkyl phosphoric acid esters (PAPs) and fluorotelomer alcohols (FTOHs) (highest medians: 53.9 ng/g for 6:2 diPAP and 45.7 ng/g for 8:2 FTOH). Several significant and strong correlations (up to p = 0.95) were found among different PFASs in dust as well as between PFASs in dust and air samples (previously published) from the same rooms. The logarithm of dust to air concentrations (log K-dust/air) plotted against the logarithm of the octanol-air partition coefficient (log K-oa) resulted in a significant linear regression line with R-2 > 0.88. Higher dust levels of PFOS were detected in rooms with plastic flooring material in comparison to wood (p

Phthalate esters (PEs) are plasticiser additives imparting durability, elasticity and flexibility to consumer products. The low migration stability of PEs along with their ubiquitous character and adverse health effects to humans and especially children has resulted in their classification as major indoor contaminants. This study assesses inhalation exposure to PEs via indoor dust using an in vitro inhalation bioaccessibility test (i.e. uptake) for of dimethyl phthalate (DMP), diethyl phthalate (DEP) and di-(2-ethylhexyl) phthalate (DEHP) and the alternative non phthalate plasticisers bis(2-ethylhexyl) terephthalate (DEHT) and cyclohexane-1,2-dicarboxylic acid diisononyl ester (DINCH), exposure. Using artificial lung fluids, which mimicktwo distinctively different pulmonary environments, namely artificial lysosomal fluid (ALF, pH = 4.5) representing the fluid that inhaled particles would contact after phagocytosis by alveolar and interstitial macrophages within the lung and Gamble’s solution (pH = 7.4), the fluid for deep dust deposition within the pulmonary environment. Low molecular weight (MW) PEs such as DMP and DEP were highly bioaccessible (> 75 %) in both artificial pulmonary media, whereas highly hydrophobic compounds such as DEHP, DINCH and DEHT were < 5 % bioaccessible via the lung. Our findings show that the in vitro pulmonary uptake of PEs is primarily governed by their hydrophobicity and water solubility, highlighting thus the need for the establishment of a unified and biologically relevant inhalation bioaccessibility test format, employed within the risk assessment framework for volatile and semi-volatile organic pollutants.

Phthalate esters (PEs) and alternative plasticizers used as additives in numerous consumer products are continuously released into the environment leading to subsequent human exposure. The ubiquitous presence and potential adverse health effects (e.g. endocrine disruption and reproductive toxicity) of some PEs are responsible for their bans or restrictions. This has led to increasing use of alternative plasticizers, especially cyclohexane-1,2-dicarboxylic acid diisononyl ester (DINCH). Human exposure data on alternative plasticizers are lacking and clear evidence for human exposure has previously only been found for di(2-ethylhexyl) terephthalate (DEHTP) and DINCH, with increasing trends in body burdens. In this thesis, a study population of 61 adults (age: 20–66; gender: 16 males and 45 females) living in the Oslo area (Norway) was studied for their exposure to plasticizers. Information on sociodemographic and lifestyle characteristics that potentially affect the concentrations of PE and DINCH metabolites in adults was collected by questionnaires. Using the human biomonitoring approach, we evaluated the internal exposure to PEs and DINCH by measuring concentrations of their metabolites in urine (where metabolism and excretion are well understood) and using these data to back-calculate daily intakes. Metabolite levels in finger nails were also determined. Since reference standards of human metabolites for other important alternative plasticizers apart from DINCH (e.g. DEHTP, di(2-propylheptyl) phthalate (DPHP), di(2-ethylhexyl) adipate (DEHA) and acetyl tributyl citrate (ATBC)) are not commercially available, we further investigated the urine and finger nail samples by Q Exactive Orbitrap LC-MS to identify specific metabolites, which can be used as appropriate biomarkers of human exposure. Many metabolites of alternative plasticizers that were present in in vitro extracts were further identified in vivo in urine and finger nail samples. Hence, we concluded that in vitro assays can reliably mimic the in vivo processes. Also, finger nails may be a useful non-invasive matrix for human biomonitoring of specific organic contaminants, but further validation is needed. Concentrations of PEs and DINCH were also measured in duplicate diet, air, dust and hand wipes. External exposure, estimated based on dietary intake, air inhalation, dust ingestion and dermal uptake, was higher or equal to the back-calculated internal intake. By comparing these, we were able to explain the relative importance of different exposure pathways for the Norwegian study population. Dietary intake was the predominant exposure route for all analyzed substances. Inhalation was important only for lower molecular weight PEs, while dust ingestion was important for higher molecular weight PEs and DINCH. Dermal uptake based on hand wipes was much lower than the total dermal uptake calculated via air, dust and personal care products, but still several research gaps remain for this exposure pathway. Based on calculated intakes, the exposure risk for the Norwegian participants to the PEs and DINCH did not exceed the established tolerable daily intake and reference doses, and the cumulative risk assessment for combined exposure to plasticizers with similar toxic endpoints indicated no health concerns for the selected population. Nevertheless, exposure to alternative plasticizers, such as DPHP and DINCH, is expected to increase in the future and continuous monitoring is required. Findings through uni- and multivariate analysis suggested that age, smoking, use of personal care products and many other everyday habits, such as washing hands or eating food from plastic packages are possible contributors to plasticizer exposure. At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.