välkommen till det 7:e nätverksmötet kring högfluorerade ämnen · pdf...
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Välkommen till det 7:e Nätverksmötet kring
högfluorerade ämnen
Agenda för det 7:e Nätverksmötet kring högfluorerade ämnen
10.00 Välkommen, och en kort presentation av deltagarna
10.20 Hur optimera PFAS terminologin för alla PFAS på marknaden? Stefan Posner, Swerea
10.45 Mass flows of per- and polyfluoroalkyl substances (PFASs) in Uppsala’s wastewater network and sewage treatment plant. Lutz Ahrens, SLU
11.10 Total organofluorine analysis of sewage samples from Swedish sewegetreatment plants. Leo Yeung, Örebro universitet
11.40 Är per- och polyfluorerade etrar nästa miljöproblem? Robin Vestergren, IVL12.10 Lunch
13.00 Vad händer på lagstiftningsområdet, samt information om ’myndighetsplattformen’. Jenny Ivarsson, Kemikalieinspektionen
13.15 Information om Naturvårdsverkets nya regeringsuppdrag om miljöövervakning. Karl Lilja, Naturvårdsverket
13.30 Naturvårdsverkets arbete med vägledning om PFAS. Jonny Riise, Naturvårdsverket
14.00 Presentation PFAS-problematiken i Barkarby, Anneli Åstebro & Kjersti Wik, Järfälla kommun
14.30 Fika
15.00 Diskussion utifrån Barkarbyfallet.
Overview of the current PFAS chemistry and terminology of polymers and non polymers
4
OECD/UNEP Global PFC Group, Synthesis paper on per- and polyfluorinated chemicals (PFCs) (2013)
A PFAS regulatory terminologyInvestigation for KEMIWHAT
• Broader understanding• A more “regulatory friendly” PFAS terminology
NOT• Fully revise the whole current terminology• At least revise “abnormalities” to be as consistent as possible to the
"traditional” organic and polymer chemistry.
HOW• An assessment of structural similarities and differences compared to
scientific and legal definitions
5
PFAS; chemicals that contain one or more perfluoroalkyl moieties, –CnF2n+1 (linear or branched) or CnF2n (cyclic)NOTE: In the past, PFASs were often referred to as “PFCs” (per- and polyfluorinated chemicals)
A minor part of the family of PFAS:
• PFAA; Perfluoroalkyl acids• PFCA; Perfluoroalkyl carboxylic acid• PFSA; Perfluoroalkane sulfonic acids• Compounds derived from perfluoroalkane sulfonyl fluoride (PASF) • Fluorotelomer (FT)-based compounds• Per- and polyfluoroalkyl ether (PFPE)-based compounds
6
Abbreviations and genericsPer and polyfluorinated substances
(PFAS)
The fluoro chemistryStructures
• Diverse uses in industrial and consumer products for a vast number of substances with various chemical structures and technical performance
• The carbon–fluorine bond is the strongest in organic chemistry
PFAS if • the perfluoroalkyl moiety, –CnF2n+1, linear and branched or• CnF2n for cyclic PFAS
NOT PFAS if• not contain any perfluorinated moiety but instead partly fluorinated (e.g
–CHF-) or moieties without covalently bound fluorine
7
• Surfactants• extremely low surface tension
• Side chain fluorinated polymers • extremely low surface energy
• Fluoropolymers e.g PTFE - another chemistry
8
The fluoro chemistryLong/short/oligomers/polymers/…….
Fluorinated ”tail” Spacer Hydrofilicgroup
Perfluorinated polymer chain (extremely long chains)
F
F F
F F F
F F F F
F FF
FS
F F
O3-
F
F F
FF
F
F
F
F
F FFFFF
FFFFFF
H(CH2)nSO2F (n = 4, 6, 8 , 10)
F(CF2)nSO2F
F(CF2)nSO2NH2
F(CF2)nSO3M
F(CF2)nSO2N(R)CH2CH2OH
F(CF2)nSO2N(R)CH2CH2CH2N(CH3)2
ECFe- + HF
Perfluoroalkyl sulfonyl fluoride
Perfluoroalkyl sulfonamide
Perfluoroalkyl sulfonate
N-Alkyl Perfluoroalkyl sulfonamido alcohol
Surfactants• Amide• Ethoxylate• Oxazolidinone• Phosphate• Silane• Sulfate
(Meth)acrylate monomer
OligomericSurfactants
Surfactants• Betaine• Sulfobetaine• Cationic
R = H, Me, Et, Bu
M = H, NH4, K, Na, …
F(CF2)nSO2NH2Perfluoroalkyl sulfonamide
Surfactants• Adipate• Fatty acid ester• Phosphate
F(CF2)nSO2N(R)CH2CH2OC(O)CR=CH2
R = H, CH3
Transor
mation
Output PFAS
Input PFAS
Final degradation productsare perfluorinated sulfonic acids (PFSA)
n = 4 formation to PFBSn = 6 formation to PFHxSn = 8 formation to PFOSn = 10 formation to PFDS
9
Electrochemical fluorination - ECF
Current definitionsn > =6 so called long chainn < 6 so called short chain
Transfor
mation
(n = 4, 6, 8, 10, …)
F(CF2)nCH2CH2OH
F(CF2)nCH2CH2SO2N(R)CH2CH2CH2N(CH3)2
Perfluoroalkyl iodide
Surfactants• Ethoxylate• Phosphate• Sulfate
(Meth)acrylatemonomer
OligomericSurfactants
Surfactants• Betaine• Sulfobetaine• Cationic
CF3CF2-I + CF2=CF2
F(CF2)nI F(CF2)n-1CO2M
F(CF2)nCH2CH2I
Fluorotelomer iodide
Fluorotelomer alcohol
F(CF2)nCH=CH2
F(CF2)nCH2CH2SO2Cl
Fluorotelomer olefin
F(CF2)nCO2M
Silane
Fluorotelomer sulfonyl chloride
F(CF2)nCH2CH2Si(OR)3
M = H, NH4, K, Na, …
F(CF2)nCH2CH2OC(O)CR=CH2
R = H, CH3
Input PFAS Output PFAS
Final degradation productsare perfluorinated carboxylic acids (PFCA)
n = 4 formation to PFBAn = 6 formation to PFHxAn = 8 formation to PFOAn = 10 formation to PFDA
10
Telomerization
Current definitionsn > =7 so called long chainn < 7 so called short chain
11
Sector Use Type of alternative
Metal plating (hard metal plating) only in closed-loop systems
Anti –corrosion treatment 6:2 Fluorotelomer sulfonate (6:2 FTS) 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctane-1-sulphonate potassium salt 1,1,2,2,-tetrafluoro-2-(perfluorohexyloxy)-ethane sulfonate 2-(6-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyloxy)-1,1,2,2-tetrafluoroethane sulfonate Non chemical: Physical covers (netting, balls) for metal plating baths (Cr VI) to diminish hydrogen burst and reduce misting need to be further investigated
Fire fighting foams
(Class B, flammable liquids fires)
Fire fighting Dodecafluoro-2-methylpentan-3-one
C6 fluorotelomer-based surfactants. Carboxymethyldimethyl-3-[[(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfonyl]amino]propylammonium hydroxide
Chemically driven oil and mining production
Oil and mineral extraction in the bedrock PFBS derivatives, fluorotelomer-based fluorosurfactants, perfluoroalkyl-substituted amines, acids, amino acids, and thioether acids.
Carpets, leather and apparel, textiles and upholstery.
Standard performance requirements (e.g. standard clothing)
Short-chain fluorinated products (e.g. C6-based); Non-fluorine containing products (e.g. paraffins); Non-chemical alternatives
High performance requirements (e.g. protective textiles)
Not available
Polymer manufacturing Polymerization processing aid Substances with ether linkage(s) between perfluoroalkyl moieties (e.g. ADONA)
Fire-fighting foams Fighting against liquid fires Short-chain fluorinated products (e.g. C6-based)
Paper and food packaging Food packaging Short-chain fluorinated products (e.g. C6-based); Non-fluorine containing products (e.g. high-density paper)
Imaging and printing industry Manufacture of conventional photographic products
No information
Semiconductor industry Constituent in process chemical formulations (e.g. for photolithographic applications)
Telomer-based products of various perfluoroalkyl chain length C3- and C4-perfluorinated compounds. Hydrocarbon surfactants, Silicon products, Non chemical: Digital techniques Digital techniques
Numerous uses with (sometimes) unspecific alternatives
The original purpose of PFAS Extremely efficient surfactants
• Can lower aqueous surface tension to less than 16 dynes/cm and function at very low concentrations (e.g., 100–500 mg/L).
• Effective in both basic and acidic aqueous media, organic solvents including esters, alcohols, ethers, and solvent-based resin systems.
• The critical micelle concentration (CMC) of a fluorinated surfactant is close to that of an ordinary hydrocarbon surfactant whose chain length is about 1.5 times longer than a fluorocarbon chain.
• Fluorinated surfactants with longer fluorinated hydrophobic/oleophobic chains (i.e. >8 fluorinated carbon atoms) have reduced water solubility which limits their reduction.
• This means that eight perfluorinated carbons have optimal functionality from a surfactant perspective on low surface tension, where the critical CMC is at its minimum with the best stability.
12
γSA γSL
So called short versus long chain PFAS
13
5
10
15
20
25
0 2 4 6 8 10 12 14
γc (
mN
/ m
)
n ( chain length of fluorochemical backbone )
Surface energy of fluorochemical acrylic polymers with variable chain length
Current view on PFAS• C6 better than C8.(telomerization) • C4 better than C8 (ECF)
BUT
NO from a performance perspective
Short chain are claimed by the industry to have less impact on environment (B and T) than the long chain BUT recent research gives a different view.
AND
All are: Persistence (P) is extreme, whether these are so called short or longchain.
Polymers that contain fluorineAre all PFAS really polymers?
Polymers are in general exempted from regulatory actions.
Criteria that are discussed• Scientific polymer defintion
• Including “Normal foreseeable use/conditions” from a legal perspective• Legal polymer defintion according to REACH
Three categories of PFAS are discussed• Fluoropolymers• Side chain fluorinated polymers• Polyfluorinated ethers
14
Polymer defintions
• A high relative molecular mass where the addition or removal of one or a few of the units has a negligible effect on the molecular properties.
• Multiple repetitions of monomer units, either the same monomer units (homo polymer) or different monomer units (co polymers).
• Not bioavailable• Not mobile in environment• Transformation under normal foreseeable conditions e.g waste phase
15
Possible polymers that contain fluorine
16
Fluoropolymers AbbreviationPolytetrafluoreethylene PTFEPerfluoroalkoxy polymer PFACo-polymer of tetrafluoroethylene TFAPerfluoromethylvinylether (PMVE) MFAFluorinated ethylenepropylene polymer FEPEthylenetetrafluoroethylene copolymer ETFEEthylene chlorotrifluoroethylene copolymer ECTFECo-polymer of ethylene (E), tetrafluoroethylene (TFE) and hexafluoropropylene (HFP)
EFEP
Terpolymer of Tetrafluoroethylene TFE3,3,3-TriFluoroPropylene TEHHexafluoropropylene (HFP) and Vinylidene Fluoride (VF2/VDF)
THV
Polychlorotri- fluoroethylene PCTFEPolyvinylidene fluoride PVDFPolyvinyl fluoride PVF
Normal foreseeable use/conditions in a life cycle perspective?
17
Polymer Typical meltingtemperature
(ºC)
Typical continuous use temperature (ºC)
Typical processing temperature (ºC)
Starting decomposition
temperature (ºC)
PTFE 330 260 380 450PFA 305 260 380 400MFA 280 249 360 N/AFEP 260 205 360 400ETFE 220-270 150 310 350ECTFE 230 140-150 280-310 500THV 120-230 70-130 171-310 400TEH 160-210 105-150 200-290 N/AEFEP 158-195 100-150 220-260 400PCTFE 215 120 265 250PVDF 170 150 232 375PVDF co-polymer
115-170 100-150 232-249 375
Possible polymers that contain fluorineSide chain fluorinated polymers
• Scientific: fluorinated side chains are probably lost and consequentlytheir to liquid repellent properties (ageing, environmental….)*
• Legal: fulfilled, more than three units (monomers)
18
Fluorocarbons(FCs)
Attack
*Russel et al, 2010*Washington et al, 2009*SUPFES, www.SUPFES.eu
Coming slides indicate an
PFSAs4, 6, 7, 8
F
S
F
F
F
F
F F
F F F FF F
F FF F O
O
OH
PFCAs4-14
F
F
F
F
F
F
F F F
F
F
F FF
F
C
O
OH
F
S
F
F
F
F
F F
F F F FF F
F FF F O
O
NH2
FOSA(n:2) FTSAs4:2, 6:2, 8:2
F
S
F
F
F
F
F F
F F H HF F
F HF H O
O
OH
PFASs analysed before and after ageing in textile samplesIonic PFASs Volatile PFASs
Department Environment and Health
(n:2) FTOHs 4:2, 6:2, 8:2, 10:2
F
F
F F
F
F F
F F
H
F F
FF
H H
H
OH
(n:2) FTACs6:2, 8:2, 10:2
F
F
F
F
F
F
F F FF
F FF O
O
(n:2) FTMACs6:2, 8:2, 10:2
F
F
F
F
F
F
F F FF
F FF O
O
CH3
SUPFES
PFASs detected in textile samples before ageing
Department Environment and Health
SUPFES
Results in µg/m2
before after
before after
Effect of ageing on concentration of PFASs
Ionic PFASs
Volatile PFASs
Department Environment and Health
SUPFES
Polyfluorinated etherspolymers or non polymers?
22
•Per- and poly- fluorinated ether-based fluorinated surfactants (PFECAs) , typically have 1, 2, or 3 perfluorinated carbon atoms separated by an ether oxygen. •Unclear if polymers, oligomers or non polymers
•Perfluoropolyethers (PFPEs), in whose backbone -CF2-, -CF2CF2-, and possibly -CF(CF3)CF2- units are separated by oxygen atoms.• Currently considered as polymers
•It is still unclear due to lack of specific structural information from chemicals producers whether polyfluorinated ethers are covered by the current scientific and legal definitions of polymers or not.
Cyclic PFAS
23
Chemical name Abbreviation CAS No Relative Content (%)
Potassium perfluroethyl cyclohexyl sulfonate
PFECHS 67584-42-3 66 - 70
Potassium perfluoromethyl cyclohexyl sulfonate
PFMeCHS 68156-07-0 18 - 22
Potassium perflurocyclohexyl sulfonate
68156-01-4 9 - 13
Potassium perfluorocyclohexyl sulfonate
3107-18-4 1 - 3
Residual organic fluorochemicals Mixture 0.1 - 0.5
3M, FC-98, a mix of cyclic perfluorinated surfactants used asan erosion inhibitor in aircraft hydraulic fluids
Generic formula CnF2n , that bypass EU regulation (REACH, POP) and the Stockholm Convention on PFOS
Cyclic PFAS
• Perfluoro (cycloaliphatic methyleneoxyalkylene) carbonyl fluoride and derivatives.
• Patents until late 1980s and were (or are) considered as useful intermediates for the preparation of many derivatives
• They have been (or is) used utility for various applications, such as surfactants, elastomers, coatings, lubricants, heat transfer and cooling fluids, hydraulic fluids, vapor phase heating, and in the treatment of fibrous substrates to impart oil and water repellency theretof.
• If still used, they bypass EU regulation (REACH) due to their generic formulaCnF2n .
24
Conclusions• So called short chain PFAS versus so called long chain PFAS• Are less effective than so callled the long chain C8 PFAS as surfactants• Have critical health and environmental properties and are likely not ”good” in this
perspective compared to so called long chain PFAS
• Fluoropolymers• Unclear ; normal forseeable use/conditions in context to the polymer defintions on
their stability and consequently emissions of degradation products in a life cycleperspective.
• Side chain fluorinated polymers• Probably lose side chains and repellent properties through ageing and environmental
degradation. Therefore doubts if these are polymers.
• Per- and poly- fluorinated ether-based fluorinated surfactants (PFECAs) and Perfluoropolyethers (PFPEs)
• Polymers or non polymers is unclear due to lack of specific structural information from chemicals producers.
• Cyclic PFAS• If still used, they bypass EU regulation (REACH) due to
their generic formula CnF2n
25
Polytetrafluoroethylene (PTFE),Polyvinylidene fluoride (PVDF),Fluorinated ethylene propylene (FEP),Perfluoroalkoxyl polymer (PFA),Polyvinyl fluoride (PVF), etc
Fluorinated (meth)acrylate polymers*Fluorinated urethane polymers*Fluorinated oxetane polymers
*These polymers are basedon monomers derived from PASFs or fluorotelomer-based raw materials
PFAS
Withoutfunctionalgroups
PolymersFluoropolymers (FPs)
Side-chain fluorinatedpolymers
Perfluoropolyethers (PFPEs) e.g. HOCH2O-[CmF2mO-]nCH2OH, n>2
Perfluoroalkyl acids(PFAAs) CnF2n+1-R
Perfluoroalkyl carboxylic acids (PFCAs), CnF2n+1-COOH
Perfluoroalkyl sulfonic acids (PFSAs), CnF2n+1-SO3H
Perfluoroalkyl phosphonic acids (PFPAs), CnF2n+1-PO3H2
Perfluoroalkyl phosphinic acids (PFPiAs), (CnF2n+1)(CmF2m+1)-PO2H
Withfunctionalgroups
Perfluoroalkane sulfonylfluoride (PASF)
CnF2n+1SO2F
PASF-based substancesCnF2n+1SO2-R, R=NH, NHCH2CH2OH, etc
Perfluoroalkyl iodides(PFAIs) CnF2n+1I
Fluorotelomer iodides(FTIs)
CnF2n+1CH2CH2I
Fluorotelomer-based substancesCnF2n+1CH2CH2-R, R=NH,
NHCH2CH2OH, etc
Per- and polyfluoroalkyl ether-based substances
Per- and polyfluorether carboxylic acids (PFECAs), e.g. C2F5OC2F4OCF2COOH
Per- and polyfluorether sulfonic acids (PFESAs), e.g. C6F13OCF2CF2SO3H
Per- and poly-fluorinated polyether-based fluorinated surfactants (PFECAs)
Cyclic PFASCnF2n
Perfluorocyclohexanesulfonates
Perfluoro (cycloaliphatic methyleneoxyalkylene) carbonyl fluoride and derivativesLinear (CnF2n+1) , branched (CnF2n+1) and/or cyclic (CnF2n)
Non-polymers …
Mono-ethers
Poly-ethers
Suggested PFAS terminology
27
http://chm.pops.int/Implementation/NationalImplementationPlans/Guidance/GuidancefortheinventoryofPFOS/tabid/3169/Default.aspx : inventering
http://chm.pops.int/Implementation/NationalImplementationPlans/Guidance/GuidanceonBATBEPforPFOS/tabid/3170/Default.aspx : BAT BEP
http://chm.pops.int/Implementation/NIPs/Guidance/guidanceonsampling,screeningetcofPOPs/tabid/5333/Default.aspx : analys av POPs såsom PFOS
MASS FLOWS OF PER- AND POLYFLUOROALKYL SUBSTANCES (PFASs) IN UPPSALA’s WASTEWATER NETWORK AND SEWAGE TREATMENT PLANTLinda Glimstedt1, Jesper Olsson2, Lutz Ahrens1
1Department of Aquatic Sciences and Assessment, SLU, Uppsala, Sweden2 Uppsala Vatten
Objectives1) To examine the mass flow
of PFASs in a wastewater network
2) To investigate the mass flow and removal efficiency of PFASs in a wastewater treatment plant
3) To assess the fate of PFASs in Lake Mälaren and a drinking water treatment plant
12
3
Lutz Ahrens
x
FF
FF F
SO
NC
OR
COH
H H
H H
n
FF
FF F
SO
NH
OR
Perfluorooctane sulfonamidoethanols(FOSEs)
Perfluorooctane sulfonamides (FOSAs)
CF2 CF
FF
OH
On
CF2 SF
FF
O
OOH
n
Perfluoroalkyl carboxylic acids(PFCAs) Perfluoroalkane sulfonic acids (PFSAs)
n:2Fluorotelomersulfonicacids(FTSAs)F
FF
F F
SO
OOH
H H
HH
n
n
FF
FF F
SO
NC
OR
C
H HOH
O
Perfluoroalkane sulfonamidoacetic acids (FOSAAs)
Per- and Polyfluoroalkyl Substances (PFASs)
n:2Fluorotelomersulfonicacids(FTSAs)
x
FF
FF F
SO
NC
OR
COH
H H
H H
n
FF
FF F
SO
NH
OR
Perfluorooctane sulfonamidoethanols(FOSEs)
Perfluorooctane sulfonamides (FOSAs)
CF2 CF
FF
OH
On
CF2 SF
FF
O
OOH
n
Perfluoroalkyl carboxylic acids(PFCAs) Perfluoroalkane sulfonic acids (PFSAs)
Per- and Polyfluoroalkyl Substances (PFASs)
FF
FF F
SO
OOH
H H
HH
n
n
FF
FF F
SO
NC
OR
C
H HOH
O
Perfluoroalkane sulfonamidoacetic acids (FOSAAs)
PFBSPFHxSPFOSPFDS
FOSAAN-MeFOSAAN-EtFOSAA
6:2 FTSAFOSAN-MeFOSAN-EtFOSA
N-MeFOSEN-EtFOSE
PFBAPFPeAPFHxAPFHpA
PFOAPFNAPFDAPFUnDA
PFDoDAPFTriDAPFTeDAPFHxDA
PFOcDA
Sampling Locations
1. STP Kungsängsverket2. Flogsta PST3. Seminaregatan PST4. Sågargatan PST5. Norra Librobäck PST6. Bärby hage PST7. Ekeby bruk PST8. Skarholmen PST9. Sävja PST10. Seglarvägen PST11. Kumlagatan PST12. Falebro PST13. Ultuna PST14. Sundby PST15. Tullgarn PST16. Strandbod-gatan PST
© Lantmäteriet [I2014/00764]
Uppsala
Summary Point sources were identified in Uppsala’s wastewater
network ⇨ 6:2 FTSA (north of Uppsala) ⇨ PFPeA, PFHxA, PFHpA, PFOA (Sågargatan PST)
PFASs are not removed in the wastewater treatment plant⇨ Accumulation of Long-chained PFCAs and PFOS in
sludge⇨ Increase of PFASs after biological treatment
Tranport of PFASs into the drinking water source area of Lake Mälaren PFASs are not removed in the drinking water treatment
plant
Lutz Ahrens
Diskussion utifrån Barkarbyfallet.
Hur rena länshållningsvatten resp. ytvatten? Rena till vilken nivå och hur förhålla sig till
riktvärden? Hur balansera kostnad mot nytta? Vilka PFAS ska analyseras? Vilken ny kunskap behövs?
Hur påverkas spridningen av PFAS vid olika markarbeten och vattenförändringar?
Total organofluorine analysis of sewagesamples from Swedish sewage treatment plants
Leo W.Y. YEUNGMTM Research Centre
Örebro University
1Yeung et al., 2006 ES&T 40: 715 2Yeung et al., 2008 ES&T 42: 8140
Not very long time ago…
39
Japan – National Institute ofAdvanced Industrial Science and Technology (AIST) -Prototype
Canada – University of Toronto – Commercialized
Sweden – MTM Research Centre – first CIC in Sweden for environmental analysis
Combustion ion chromatography (CIC)
IFUOFNEOF PFASs
TF
TF = IF + OF
OF
EOF
TF - Total Fluorine:
OF - Organic Fluorine
EOF - Extractable Organofluorine
PFASs
UOF - Unidentified Organofluorine
NEOF - Non Extractable Organofluorine
IF - Inorganic Fluorine
Mass balance analysis of fluorine
Combustion ion chromatography (CIC) for TF and EOF.
MTM Research Centre
Combustion module• Sample is set onto the
quartz boat• Two stage processes
• Pyrolysis between1000-1100oC with Ar
• Followed by thermaloxidation with O2
• Solid, liquid, paste-like and viscous samples
Acquity UPLC (Waters) and Waters XeVo-TQ S MS-MS for PFASs
Total organofluorine Combustion ion chromatography (TOF-CIC) for TF and EOF.
IFUOFNEOF PFASs
TF
TF = IF + OF
OF
EOF
TF - Total Fluorine:
OF - Organic Fluorine
EOF - Extractable Organofluorine
PFASs
UOF - Unidentified Organofluorine
NEOF - Non Extractable Organofluorine
IF - Inorganic Fluorine
Mass balance analysis offluorine
Extractable organofluorine(EOF)
Ion pair extraction Solid phase extraction(SPE)
S
OO
N
R
FF
F
F F
F F
F F
F F
F F
F F
F F OH
O
SO
OF
F F
OHx
OF
F F
OHx
-
-
Total fluorine• Organofluorine
• PFASs• Inorganic fluoride
CIC
IC
CICLC-MS/MS
Conversion of data - ng/mL to ng F/mL
ng/mLSample Code PFOS
SC03-1 23SC03-2 21
PFOSMW 499
the number of F 17Fluorine content (-) 0.647294589
ng-F/mL ng-F/mLResults from LC-MSMS Results from CIC
PFOS EOF % PFOS/EOFSC03-1 15.1 108 14.0SC03-2 13.7 108 12.7
Cf = 17 x 19 x 23499
=15.1
Conversion of data - ng/mL to ng F/mL
ng/g
1.
2.
3.
4.
2017-05-23 47
48
Münster Halle
1982198319841985198619871988198919901991199219931994199519961997199819992000200120022003200420052006200720082009
0 20 40 60 80 100 0 20 40 60 80 100
24.823.815.912.314.817.328.0
20.110.6
16.79.42
11.010.9
18.024.019.021.039.314.925.9
32.533.6
29.3
30.8
23.424.1
42.5
23.3
21.128.127.021.515.1
23.414.519.115.822.619.7
23.5
13.0
14.0
ng F/mL ng F/mL
%%
PFOS precursor PFCA precursor PFCA PFPiAPFSA Unidentified
Our interestsSewage treatment plants have been suggested to be one of the major sources of poly- and perfluoroalkyl substances (PFASs) to the aquatic environment (Filipovic & Berger 2015).
Analysis of sewage samples1. influent
• may indicate how much unidentified PFAS humans are using2. effluent
• may provide an estimate how much unidentified PFAS are released into the environment.
3. sludge • may be applied to agricultural field as fertilizer; may enter the
environment. 4. analysis of archived samples
• may provide data on temporal usage of unidentified PFAS.
2017-05-23 49Filipovic & Berger, 2015 Chemosphere 129,74
Sewage treatment plant location, size and source
2017-05-23 50
Prof Peter Haglund, Umeå UniversityMiljöövervakning av utgående vatten and slam från svenska avloppsreningsverkEnvironmental monitoring of outgoing water and sludge from Swedish sewage treatment plants
Sewage treatment plant location, size and source
2017-05-23 51
• The Ön WWTP serves 92,000 people (129,000 p.e.) and a hospital.
• The Henriksdal WWTP serves 737 000 people (656 000 p.e.) receives municipal wastewater from industries and hospitals.
• The Gässlösa WWTP serves 82,000 people (73,000 p.e.) and has textile and chemical industries as well as a hospital connected.
Population equivalent (p.e.), in waste-water treatment is the number expressing the ratio of the sum of the pollution load produced during 24 hours by industrial facilities and services to the individual pollution load in household sewage produced by one person in the same time.
All three WWTPs have mechanical, chemical, biological, and anaerobic digestion treatment.
Perfluoroalkyl/polyfluoroalkyl substances (PFASs)
F
F F
SO
O OHx
OF
F F
OHx P
O
HOF
F F
OHx
PO
HOF
F F
x F
FFy
SO
OF
F F
OHx
Fluorotelomer sulfonates (FTSAs)
Perfluorinated phosphinates (PFPiAs)
Perfluorinated phosphonates (PFPAs)
Perfluorinated carboxylates (PFCAs)
Perfluoroalkane sulfonates (PFSAs)
F
F
F F
F F
F F
F F
O
O
PO
OH
x
y
Polyfluoroalkyl phosphate esters (PAPs)
F
F F
F F
O
HO
P
O
OH
x
OS
O
N P
O
O
OO
SON
OF
F
FF F
FF
F F
FF
F F
FF
F FF F
FF
F F
FF
F F
FF
F FF
FF
S
OO
N
R
FF
F
F F
F F
F F
F F
F F
F F
F F OH
O
S
OO
N
R
FF
F
F F
F F
F F
F F
F F
F F
F F OH
O
Perfluorooctanesulfonamidoacetate (FOSAA)
Perfluorooctanesulfonamide (FOSA)
N-ethyl perfluorooctanesulfonamideoetha
nol-based polyfluoroalkylphosphate diester (SAmPAP)
52
Perfluoroalkyl/polyfluoroalkyl substances (PFASs)
F
F F
SO
O OHx
OF
F F
OHx P
O
HOF
F F
OHx
PO
HOF
F F
x F
FFy
SO
OF
F F
OHx
Fluorotelomer sulfonates (FTSAs)
Perfluorinated phosphinates (PFPiAs)
Perfluorinated phosphonates (PFPAs)
Perfluorinated carboxylates (PFCAs)
Perfluoroalkane sulfonates (PFSAs)
F
F
F F
F F
F F
F F
O
O
PO
OH
x
y
Polyfluoroalkyl phosphate esters (PAPs)
F
F F
F F
O
HO
P
O
OH
x
OS
O
N P
O
O
OO
SON
OF
F
FF F
FF
F F
FF
F F
FF
F FF F
FF
F F
FF
F F
FF
F FF
FF
S
OO
N
R
FF
F
F F
F F
F F
F F
F F
F F
F F OH
O
S
OO
N
R
FF
F
F F
F F
F F
F F
F F
F F
F F OH
O
Perfluorooctanesulfonamidoacetate (FOSAA)
Perfluorooctanesulfonamide (FOSA)
N-ethyl perfluorooctanesulfonamideoetha
nol-based polyfluoroalkylphosphate diester (SAmPAP)
53
A total of 75 PFASs included for target analysis
MethodsFor sludge samples1-3
• freeze-dried• digested with NaOH, • followed by MeOH extraction.• cleanup
• SPE-WAX - samples collected from 2016
• Ion pair - samples collected between 2004 and 2015
For water samples1
• were filtered with GF/B glass fiber filters before extraction (Whatman)
• SPE using WAX sorbents, according to ISO/DIS 25101 (ISO, 2009) with some modifications.
2017-05-23 541ISO, 2009. ISO25101. Water quality — Determination of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) — Method for unfiltered samples using solid phase extraction and liquid chromatography/mass spectrometry.2Yeung, et al. 2013. Environ. Int. 59, 389–397.3Yeung and Mabury, 2016. Environ. Chem. 13, 102.
Quality control and assurance (QA/QC)
PFAS• Procedural blank and a spike QA sample; samples were extracted in
duplicate;• Quantified using internal calibration with mass-labelled standards.
2017-05-23 55
RecoveriesSewage
Water sludgePFCA 25-85 20-81PFSA 47-87 31-81FTCA/FTUCA 30-87 52-79FTSA 46-78 41-93FOSAAs 21-115 36-115FOSAs/FOSEs 27-73 25-76diPAP 22 36-115
PFCA: C4-C12, C14; PFSA: C4, C6, C8; FTUCA: 6:2, 8:2, 10:2, FTSA: 6:2, 8:2; FOSAA: Ethyl-, Methyl-; FOSA/FOSE: Ethyl-, Methyl-; diPAP: 6:2, 8:2
Quality control and assurance (QA/QC)
TOF• Combustion of procedural blank• Combustion of a QA sample; Combustion of 100 ng and 500 ng of SRM
2143 – p-Fluorobenzoic (NIST) resulted in recoveries of between 90 -98%.
• Combustion of 500 ng of PFOS resulted in recoveries ranging from 89 to 92% and combustion 500 ng of PFOA resulted in 85 to 90% recoveries.
• Quantification of sample was based on the external calibration curve after the peak area of the sample had been subtracted from the previous combustion blank and extraction blank.
2017-05-23 56
Quality control and assurance (QA/QC)
TOF• Prior to actual sample analysis, removal of inorganic fluoride
experiment on SPE was performed. • The washing step using 20 mL 0.01% NH4OH in MilliQ
followed by 30 mL of Milli-Q water showed 100% removal of 1000 ng F during SPE.
• Attempt to measure inorganic fluoride using capillary electrophoresis (CE) was also made to ensure no inorganic fluoride present in the sample extract for TOF analysis.
• Due to the presence of significant amounts of other ions that inferred with the fluoride signal during CE analysis, identification and quantification of fluoride ion in sample extracts could not be made.
2017-05-23 57
2017-05-23 58
Ön (Umeå)Medium, hospital
Henriksdal(Stockholm)Large, Industrial
Gässlösa(Borås)medium, Hospital, Industrial (textile, chemicals)
24.6
49.5
51.2
51.8
82.0
126.9
Conc.ng/LComposition %
PFCA PFSA FTSA FTCA FTUCA FOSA FOSAA diPAP PFPA PFPiA
Composition (%) and concentration (ng/L) in influent (I) and effluent (E) samples
Samples collected in 2016
2017-05-23 59
Ön (Umeå)Medium, hospital
Henriksdal(Stockholm)Large, Industrial
Gässlösa(Borås)medium, Hospital, Industrial (textile, chemicals)
Composition (%) and concentration (ng/g d.w.) in sludge samples
PFCA PFSA FTSA FTCA FTUCA FOSA FOSAA diPAP PFPA PFPiA
Conc.ng/gComposition %
145.9
162.1
166.0
Samples collected in 2016
2017-05-23 60
Ön (Umeå)Medium, hospital
Henriksdal(Stockholm)Large, Industrial
Gässlösa(Borås)medium, Hospital, Industrial (textile, chemicals)
268
484
217
819
473
345
Conc.ng F/LComposition %
Composition (%) and concentration (ng F/L) in influent (I) and effluent (E) samples
I
E
I
E
I
E
Targeted Unidentified
96
96
91
98
93
87
Samples collected in 2016
2017-05-23 61
Ön (Umeå)Medium, hospital
Henriksdal(Stockholm)Large, Industrial
Gässlösa(Borås)medium, Hospital, Industrial (textile, chemicals)
Composition (%) and concentration (ng F/g d.w.) in sludge samples
Conc.ng F/gComposition %
<50
154
55.7
Targeted Unidentified
58
82
42
Samples collected in 2016
Temporal study on PFAS in sludge samplescollected from Henriksdal
2017-05-23 62
0
50
100
150
200
250
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
2004 2005 2007 2008 2009 2010 2011 2012 2013 2014 2015
Con
cent
ratio
n(n
g/g
d.w.
)C
ompo
sitio
n(%
)
PFCAPFSAFTSAFTCAFTUCAFOSAFOSAAdiPAPPFPAPFPiA
Henriksdal(Stockholm)Large, Industrial
Temporal study on PFAS in sludge samplescollected from Henriksdal
2017-05-23 63
Henriksdal(Stockholm)Large, Industrial
Com
posi
tion
(%)
0%
20%
40%
60%
80%
100%
2004
2005
2007
2008
2009
2010
2011
2012
2013
2014
2015
81 87 88 87 90 92 91 91 92 9093
TargetedU
nidentified
Temporal study on PFAS in sludge samplescollected from Henriksdal
2017-05-23 64
Con
cent
ratio
n(n
gF/
g d.
w.)
0
200
400
600
800
1000
1200
020406080
100120140160
2003
2004
2005
2006
2007
2008
2009
2010
2011
2012
2013
2014
2015
2016
Target PFAS
Unidentified PFAS
Henriksdal(Stockholm)Large, Industrial
Current projects
• Sewage samples• Influent and effluent• Sludge
• Human blood sample• Drinking water sample
2017-05-23 65
Acknowledgements
2017-05-23 66
Dr. Karl Lilja and Dr. Linda Linderholm
Prof. Peter Haglund
Dr. Ylva Lind
Mr. Ezra Tibbelin
Our Contacts
2017-05-23 67
Ulrika Eriksson, [email protected]
Anna Kärrman, [email protected]
Leo Yeung
Är per- och polyfluorerade etrar nästa miljöproblem?
Robin Vestergren
ÖverblickIntroduktion till per- och polyfluorerade eterämnen
PBT egenskaper
Förekomst i miljön
Slutsatser och rekommendationer
Övergripande trender i produktion och användning av PFAS
Långkedjiga perfluoroerade sulfonsyror (PFHxS och längre), karboxylsyror (PFOA och längre) och deras precursors har till stor del fasats ut i EU, Nordamerika och Japan
Kortkedjiga PFAS har i många fall använts som ersättningsämnen
Ökande produktion och användning av PFAS i Ryssland, Kina och Sydostasien
PFOA PFHxA
PFBS
8:2 FTOH
PFOS
6:2 FTOH
Alternativ till långkedjiga PFAS
Bland ersättningsämnena för PFOA och PFOS finns också en mängd olika perfluorerade syror med eter bindningar
Många syntesprocesser och patent är över 30 år gamla
Vad vet vi om miljöriskerna med dessa ämnen?
Wang et al. Environ Int 2016, 60, 242-248
Hög persistens (OECD 301D)
Toxisk i sötvattensorganism (OECD 203)
Relativt höga halter i ytvatten kring förkromningsanläggningar
Wang et al. Environ. Sci. Technol. 2013, 47, 10163-10170
Bioackumulationsfaktor och vävnadsfördelning av F-53B i fisk (Carassius carassius)
F-53B kunde detekteras i 100% av alla fiskprover från två vitt skilda provtagningsplatser i Kina
Mediankoncentrationer i blod var 20.9 ng/ng (Tangxun Lake) och 41.9 (Xiaoqing river)
Liknande vävnadsfördelning som PFOS
Shi et al. Environ. Sci. Technol. 2015, 49, 14156-14165.
Bioackumulationsfaktor och vävnadsfördelning av F-53B i fisk (Carassius carassius)
F-53B är ackumuleras effektivt i fisk
BAF är signifikant högre än PFOS
Shi et al. Environ. Sci. Technol. 2015, 49, 14156-14165.
Förekomst av F-53B homologer i human serum från KinaDe två vanligaste F-53B homologerna kunde detekteras i >98% av alla blod- och serumprover (n=72) från Kina
Höga halter i högkonsumenter av fisk och anställda vid en förkromningsfabrik
OS
O-
F
FF
F
F
F
FF
F
F
F
F
F
FF
FO
O
F
F
F
Cl
F
OS
O-F
Cl
FF
F
F
F
FF
F
F
F
F
F
FF
FO
O
Halveringstider i människa (år)
Study population ReferenceMean Median Min Max Mean Median Min Max17,2 14,3 9,4 52,5 7,2 6,2 2,8 17,8 Predominantly male (58 m/14 f) This study
5,4 4,6 2,4 21,7 Predominantly male (24 m/2 f) Olsen et al. 20075,5 Male Wong et al. 20144,9 Female Wong et al. 2014
445 280 7,1 4230 46,7 81,9 4,5 696 Predominantly male (58 m/14 f) This study6,7 6,6 3,1 11 Young females (<50 years) Zhang et al. 201134 25 1,5 182 Males and older females (>50 yeaZhang et al. 201222 44 6 2183 Predominantly male Gao et al. 2015
C8 Cl PFESA n-PFOS
Total elimination
Renal clearence
Olsen et al. 2007 EHP 115, 1298-1305, Wong et al. 2014 ES&T 48, 8807−8814, Zhang et al. 2013 ES&T 47, 10619−10627, Gao et al. 2015 ES&T 49, 6953−6962
Shi et al. Environ. Sci. Technol. 2016, 50, 2396-2404.
Cl-PFESAs i naglar, hår och urin från Kina
Wang et al. unpublished
Liknande halter av F-53B och PFOS i bakgrundsbefolkningen från Hebei provinsen
Cl-PFESAs i nyföddaDe två vanligaste F-53B homologerna kunde detekteras i >92% av blodproverna från nyfödda spädbarn från Wuhan provinsen
Cl-PFESAs överförs till fostret med på liknande sätt som PFOS
Pan et al. Environ. Sci. Technol. 2017, 51, 634-644.
Cl-PFESAs i Arktis
Har påträffats säl, isbjörn och späckhuggare från Grönland
Betydligt lägre halter än PFOS
De globala transportmekanismerna är inte kartlagda
Gebbink et al. Chemosphere 2016, 144, 2384–2391
PFECAs i fluoropolymerproduktion
Gen-X är en av de främsta ersättarna till PFOA i produktion av PTFE/PVDF
Höga halter har påträffats i ytvatten nedströms från produktionsanläggningar i USA och Nederländerna
Heydebreck et al. Environ. Sci. Technol. 2015, 14, 8386–8395Sun et al. Environ. Sci. Technol. Lett. 2016, 3, 415-419
Gen-X i Kina
Stora utsläpp av HFPO-DA ”Gen-X” (5 kol), men även HFPO-TrA (7 kol, 2 eterbindningar)
PFCAs och PFECAs har använts tillsammans med PFCAs vid produktion av PTFE/PVDF
Troligtvis stora historiska utsläpp av både HFPO-DA och HFPO-TrA
Song et al. unpublished
PFECAs/PFESAs med okända användningsområden
Strynar et al. Environ. Sci. Technol. 2015, 49, 11622-11630
Persistens och bioackumulerbarhet skiljer sig inte nämnvärt från PFCAs/PFSAs av motsvarande kedjelängd
Troligtvis liknande toxicitet
Miljöövervakning från Kina visar relativt höga halter och emissioner av PFECAs/PFESAs
Vi vet fortfarande inte så mycket om spridningen av PFECAs/PFESAs i Europa
Det finns troligtvis en mängd per- och polyfluorerade eter ämnen som vi inte lyckats identifiera än
Är per- och polyfluorerade etrar nästa miljöproblem?
Diskussion & rekommendationer
Forskning och miljöövervakning på kända PFECA/PFESAs
Utökad non-target screening
Identifiera ämnen som uppfyller kriterier för POPs och påskynda den regleringsprocessenMinska användningen och utsläppen av PFAS som grupp och arbeta mot en total utfasning i icke-essentiella tillämpningar
Anamma ett livscykelperspektiv på produkter som importeras från Asien och sätt mer press på nedströms användare av t.ex. PTFE/PVDF
Stort tack tillFormas (mobilitetsstöd 2015-914)
Yali Shi, Yaqi Cai, Yuan Wang, Song Xiaowei, Ian Cousins och Zhanyun Wang
