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Mass Balance of Perfluoroalkyl Acids in the Baltic Sea
Stockholm University, Faculty of Science, Department of Applied Environmental Science (ITM).
Stockholm University, Faculty of Science, Department of Applied Environmental Science (ITM).
Stockholm University, Faculty of Science, Department of Applied Environmental Science (ITM).
2013 (English)In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 47, no 9, 4088-4095 p.Article in journal (Refereed) Published
Abstract [en]

A mass balance was assembled for perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorodecanoic acid (PFDA), and perfluorooctanesulfonic acid (PFOS) in the Baltic Sea. Inputs (from riverine discharge, atmospheric deposition, coastal wastewater discharges, and the North Sea) and outputs (to sediment burial, transformation of the chemical, and the North Sea), as well as the inventory in the Baltic Sea, were estimated from recently published monitoring data. Formation of the chemicals in the water column from precursors was not considered. River inflow and atmospheric deposition were the dominant inputs, while wastewater treatment plant (WWTP) effluents made a minor contribution (<5%). A mass balance of the Oder River watershed was assembled to explore the sources of the perfluoroalkyl acids (PFAAs) in the river inflow. It indicated that WWTP effluents made only a moderate contribution to riverine discharge (21% for PFOA, 6% for PFOS), while atmospheric deposition to the watershed was 1-2 orders of magnitude greater than WWTP discharges. The input to the Baltic Sea exceeded the output for all four PFAAs, suggesting that inputs were higher during 2005-2010 than during the previous 20 years despite efforts to reduce emissions of PFAAs. One possible explanation is the retention and delayed release of PFAAs from atmospheric deposition in the soils and groundwater of the watershed.

Place, publisher, year, edition, pages
2013. Vol. 47, no 9, 4088-4095 p.
National Category
Earth and Related Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
URN: urn:nbn:se:su:diva-91529DOI: 10.1021/es400174yISI: 000318756000019OAI: oai:DiVA.org:su-91529DiVA: diva2:634634
Funder
Swedish Research Council
Note

AuthorCount;3;

Available from: 2013-07-01 Created: 2013-06-28 Last updated: 2017-12-06Bibliographically approved
In thesis
1. Mass balance of perfluoroalkyl acids in the Baltic Sea
Open this publication in new window or tab >>Mass balance of perfluoroalkyl acids in the Baltic Sea
2013 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

Perfluoroalkyl acids (PFAAs) are man-made chemicals. Their unique properties make them beneficial for a wide range of industrial and consumer applications, such as constituents in fire fighting foams, hydraulic oils and food packaging materials.PFAAs have shown to be highly persistent in the environment, and the toxicological potential of long chain PFAA homologues is of a concern. International regulation and voluntary actions by the industry have been implemented and led to reduced primary emissions of PFAAs to the environment. However, the concentrations of some PFAAs in e.g. birds from the Baltic Sea are still very high and of ecotoxicological concern. Measures to reduce the PFAA contamination require an understanding of the sources and how the PFAAs are being transported in the environment.In this licentiate thesis a mass balance was assembled for perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorodecanoic acid (PFDA) and perfluorooctane sulfonic acid (PFOS) in the Baltic Sea. A one-box model was used including the input pathways river inflow, atmospheric deposition, wastewater discharges and inflow from the North Sea via the Danish Straits, while the loss processes considered were sediment burial, transformation of the chemicals and outflow to the North Sea via the Danish Straits. Additionally, the inventories of the four target PFAAs in the Baltic Sea were estimated. Both chemical fluxes and inventories were estimated using recently published monitoring data (2005-2010).In order to obtain a detailed perspective on the current knowledge regarding PFAAs in the Baltic Sea, challenges and uncertainties in data selection were discussed for the most dominant input pathways. This included WWTP emissions and calculation of emission factors (EFs), atmospheric deposition and riverine inflow.River inflow and atmospheric deposition were the dominant inputs, while wastewater treatment plant (WWTP) effluents made a minor contribution. The input to the Baltic Sea exceeded the output for all 4 PFAAs, suggesting that inputs were higher during 2005-2010 than during the previous 20 years despite efforts to reduce emissions of PFAAs. Comparing the difference between PFAA input and output with the PFAA inventory, the doubling time for the concentration in the Baltic Sea was estimated to be 8-94 yr for PFHxA, 12-16 yr for PFOA, 3-5 yr for PFDA and 4 yr for PFOS. The surplus of the input can be an effect of retention and delayed release of PFAAs from atmospheric deposition in the soils and groundwater of the watershed.The licentiate thesis contributes to a holistic understanding of the major input and output pathways and inventories of PFAAs in the Baltic Sea. Furthermore, it points out current knowledge gaps in our understanding of sources and fate of PFAAs in the aquatic environment.

Place, publisher, year, edition, pages
Stockholm: Department of Applied Environmental Science (ITM), Stockholm University, 2013. 18 p.
Keyword
PFOA, PFOS, mass balance, Baltic Sea, PFOA, PFOS, massbalans, Östersjön
National Category
Environmental Sciences
Research subject
Environmental Chemistry
Identifiers
urn:nbn:se:su:diva-88779 (URN)
Presentation
2013-04-19, Högblomsalen, Geovetenskapens hus, Svante Arrhenius väg 12, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the defence the following papers were unpublished and had a status as follows: Paper 1: Manuscript

Available from: 2013-04-11 Created: 2013-03-27 Last updated: 2015-04-13Bibliographically approved
2. Fate of perfluoroalkyl acids in the aquatic environment with a focus on mass balance studies
Open this publication in new window or tab >>Fate of perfluoroalkyl acids in the aquatic environment with a focus on mass balance studies
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Perfluoroalkyl substances (PFASs) are man-made chemicals. Their unique properties make them beneficial for a wide range of industrial and consumer product applications, such as in aqueous film forming foam (AFFF), durable water repellent clothing, hydraulic oils and food packaging materials. Perfluoroalkyl acids (PFAAs), a class of PFASs, are highly persistent in the environment, and long chain PFAAs are bioaccumulative and toxic. International regulation and voluntary actions by the industry have been implemented and led to a recent reduction of primary emissions of PFAAs to the environment. However, point sources such as AFFF training sites as well as diffuse sources continue to contaminate water bodies, soil and biota. Reducing environmental pollution with PFAAs has therefore become a regulatory priority. Designing successful measures to reduce the PFAA contamination requires an understanding of the sources, transport and fate of PFAAs in the environment.

Four scientific publications are included in this PhD thesis, which aimed at increasing the holistic understanding of the fate of PFAAs in aquatic systems. This was achieved by chemical trace analysis combined with mass balance modeling. The following topics were covered: Dispersion and fate of PFAAs from an AFFF-impacted site (Paper I), recirculation of PFAAs in the aquatic environment with focus on waste water treatment plants (WWTPs, Paper II), mass balance of PFAAs in the Baltic Sea (Paper III) and transport and fate of PFAAs in two pristine boreal stream catchments (Paper IV).

Results from Paper I showed that AFFF-impacted sites at a former military airfield, which was abandoned for more than 30 years, continue to be point sources of PFAAs to recipients. The sum of PFAAs in the ground water and surface waters ranged from 740 to 51000 ng L-1 and <0.5 to 79 ng L-1, respectively. PFOS in muscle tissue of European perch from a nearby lake ranged from 77 to 370 ng g-1 wet weight, representing among the highest values reported worldwide for fish muscle. In Paper II the relative importance of environmental recirculation of PFAAs versus new releases from the technosphere was investigated for PFAAs in WWTP influents. It was shown that tap water can be an important source of PFAAs to WWTPs in areas with elevated environmental levels. This needs to be taken into account when calculating emissions via WWTP effluents. PFAA mass balances over the WWTPs suggested that PFHxA and PFOA were formed from precursor compounds within the plants. Assembled PFAA mass balances for the Baltic Sea (Paper III) showed that river inflow and atmospheric deposition were the dominant input pathways, while wastewater treatment plant (WWTP) effluents discharging directly into the Baltic Sea made a minor contribution. The inputs of PFAAs were estimated to be higher than the outputs, suggesting a current increase of the PFAA inventory in the Baltic Sea. Also the mass balance study of PFAAs in two remote stream catchments presented in Paper IV revealed that inputs dominated over outputs for both catchments, indicating that a considerable portion of the PFAAs deposited from the atmosphere is retained in soil or in deep ground water and may be released to surface and marine water environments in the future

Abstract [hr]

Perfluoralkilne tvari (PFASs) su umjetne kemikalije. Zbog svojih jedinstvenih svojstava široko su primjenjive u industriji i izradi proizvoda krajnje potrošnje kao što su pjena za gašenje požara (AFFF), vodootporna odjeća, hidraulična ulja i pakiranja za hranu. Perfluoralkilna kiselina (PFAAs) iz skupine perfluoralkilnih tvari iznimno je dugotrajna u okolišu, a dugolančane PFAAs su bioakumulativne i otrovne. Poduzeta međunarodna regulativa i dobrovoljne akcije vodile su nedavno smanjenoj primarnoj emisiji PFAAs u okoliš. Unatoč tome, primarni izvori, kao što su mjesta na kojima se provode treninzi za gašenje požara i difuzni izvori i dalje zagađuju vode, tlo i biotu. Zbog toga, smanjenje onečišćenja okoliša izazvanog PFAAs predstavlja regulatorni prioritet. Stvaranje uspješnih mjera kojima bi se smanjilo onečišćenje izazvano PFAAs zahtjeva razumijevanje izvora, prijenosa i sudbine tih tvari u okolišu.

U ovaj doktorat uključena su četiri znanstvena članka kojima je cilj povećati sveukupno razumijevanje sudbine PFAAs u vodenim sustavima. To je postignuto kemijskom analizom elemenata u tragovima u kombinaciji s modeliranjem masene ravnoteže. Obrađene su sljedeće teme: Širenje i sudbina PFAAs na područjima zahvaćenim AFFF (Članak I), ponovna cirkulacija PFAAs u vodenom okolišu s naglaskom na postrojenja za pročišćavanje otpadnih voda (Članak II), masena ravnoteža PFAAs u Baltičkom moru (Članak III) te prijenos i sudbina PFAAs u dva udaljena sjeverna vodena toka (Članak IV).

 

Rezultati iz Članka I pokazali su da su područja zahvaćena AFFF na bivšem vojnom aerodromu napuštenom prije 30 godina i dalje je glavni izvor PFAA zagadenja okolisa. Zbroj PFAAs u podzemnim i površinskim vodama kreće se u rasponu od 740 do 51000 ng L-1 i <0.5 do 79 ng L-1. PFOS u mišićnom tkivu grgeča iz obližnjeg jezera kreće se od 77 do 370 ng g-1 mokre težine, predstavljajući jednu od najviših vrijednosti u svijetu za riblje mišiće. Članak II istražuje relativnu važnost ponovne cirkulacije PFAAs imajući na umu novu emisiju PFAAs iz tehnosfere u postrojenjima za pročišćavanje otpadnih voda. Cirkulacija/kruženje u okolišu može se pojaviti kada PFAAs iz sustava pitke voda (rijeka, bunara i jezera) odlaze u otpadne vode.

Prikazano je kako voda iz slavine može biti važan izvor PFAAs sustavima za pročišćavanje otpadnih voda u područjima s povišenim razinama zaštite okoliša. To se treba uzeti u obzir pri računanju emisije putem strojeva koji se koriste za pročišćenje otpadnih voda. Masena ravnoteža PFAA u postrojenjima za pročišćavanje otpadnih voda upućuje na to da su PFHxA i PFOA stvoreni kao prethodni spojevi unutar postrojenja. Prikupljene masene ravnoteže PFAA za Baltičko more (Članak III) pokazale su da su pritoke rijeka i atmosfersko taloženje dominantni ulazni putovi, dok postrojenja za pročišćenje otpadnih voda pridonose tek u manjoj mjeri. Ulaz PFAAs je procijenjen višim od izlaza, što objašnjava trenutno povećanje sadržaja PFAA u Baltičkom moru. Masena ravnoteža PFAAs u dva udaljena riječna toka predstavljena u Članku IV otkriva da ulaz dominira nad izlazom za oba riječna toka, što upućuje na značajan udio PFAAs koji je iz atmosfere zadržan u tlu ili podzemnim vodama te može biti ispušten u područja površinskih voda i mora.

Abstract [sv]

Perfluorerade alkylsyror (PFAA) är kemikalier som är producerade av människan. Deras unika egenskaper gör att de kan användas i många olika industriella applikationer. PFAAs används i brandsläckningsskum, vattenavvisande kläder, hydrauliska oljor och matförpackningar.

PFAAs har visat sig vara persistenta i miljön, och långkedjiga PFAA-homologer har visat sig vara bioackumulerbara samt ha en toxisk verkan. Reglering på internationell nivå tillsammans med initiativ från industrin har lett till minskning av direkta utsläpp. Punktkällor som brandövningsplatser samt andra diffusa källor fortsätter att förorena omgivande vattendrag, jordlager och fauna. Den utbredda föroreningen av PFAAs har därför blivit prioriterad för reglering. För att förstå utsläppen av PFAAs i miljön, hur de transporteras samt deras öde i miljön, är det viktigt att utföra studier som belyser dessa områden.

 

Denna doktorsavhandling inkluderar fyra vetenskapliga publikationer. Syftet med de underliggande studierna var att öka den holistiska förståelsen av PFAAs rörelse i akvatiska system. Studierna gjordes genom att kombinera kemiska analysmetoder med modellering. Följande  studier genomfördes; Transport och spridning av PFAAs från en brandövningsplats (Paper I), recyklering av PFAAs i den akvatiska miljön med fokus på vattenreningsverk (Paper II), massbalans av PFAAs i Östersjön (Paper III), transport och öde av PFAAs i två pristina vattendrag (Paper IV).

 

Resultat från (Paper I) visade att brandövningsplatser vid en flygplats som inte har varit i bruk i mer än 30 år, fortfarande är punktkällor av PFAAs till omgivande vattendrag. Summan av PFAAs koncentrationer i grundvattnet och ytvattnet sträckte sig från 740 till 51000 ng L-1 och <0.5 till 79 ng L-1 i respektive vattendrag. Koncentrationen av PFOS i muskelvävnad från  aborre i en av sjöarna var 77 till 370 ng g-1 våtvikt. Dessa värden representerar några av de högsta uppmätta koncentrationerna i världen. I Paper II testades betydelsen av PFAAs från recirkulering i miljön i jämförelse med nya utsläpp från teknosfären. Recirkulering av PFAAs i miljön kan förekomma då PFAAs i inkommande vatten till reningsverk kommer från dricksvatten.

Denna studie visar att dricksvatten kan vara en påtaglig källa av PFAAs till vattenreningsverk i områden med förhöjda halter av PFAAs i miljön. Detta måste tas hänsyn till när man beräknar emissioner med utgående vatten från vattenreningsverk. Massbalanser av PFAAs i reningsverken visar att PFHxA och PFOA bildades av prekursorämnen i vattenreningsverken. I Paper III beräknades massbalanserna av PFAAs i Östersjön, beräkningarna visar att floder och atmosfärisk nedebörd var de viktigaste källorna medan utsläppen från vattenreningsverk var markant lägre. Importen av PFAAs estimerades vara högre än exporten, varför vi tror att PFAAs mängden I Östersjön kommer att öka över tid. Vidare gjordes en mass balans av PFAAs i två avlägsna avrinningsområden (Paper IV). Resultaten visar att importen av PFAAs dominerar över exporten från båda avrinningsområdena. Detta indikerar att en stor del av PFAAs som kommer ner via nederbörd kommer att ansamlas i jorden eller i grundvattnet. Dessa PFAAs kan vid senare tillfälle komma att släppas ut till floder som rinner ut i marina vatten.

Place, publisher, year, edition, pages
Stockholm: Department of Environmental Science and Analytical Chemistry, Stockholm University, 2015. 35 p.
Keyword
PFAA, PFOS, AFFF, tap water, ground water, WWTP, mass balance, atmospheric deposition, rivers, Baltic Sea
National Category
Natural Sciences
Research subject
Applied Environmental Science
Identifiers
urn:nbn:se:su:diva-116228 (URN)978-91-7649-153-9 (ISBN)
Public defence
2015-05-22, De Geersalen, Geovetenskapens hus, Svante Arrhenius väg 14, Stockholm, 09:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council Formas
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 2: Manuscript.

 

Available from: 2015-04-28 Created: 2015-04-15 Last updated: 2015-04-28Bibliographically approved

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