Post on 07-Feb-2018
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Analysis of PFCs in water
Lutz AhrensGKSS Research Centre Geesthacht Institute for Coastal ResearchDepartment of Environmental ChemistryGermany
Contact: Lutz.Ahrens@gkss.de
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Outline
•
Analysis of PFCs in water-
Target
analytes
-
- Sampling-
-
Filtration
-
-
Extraction-
-
Instrumental analysis
-
-
Quantification
•
PFCs in the aqueous environment•
-
WWTPs and river
water
•
-
North Sea and Baltic
Sea-
Atlantic Ocean
•
Summary
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
What
are the Analytical
Challenges
for
PFCs?
•
Unique
physicochemical properties–
Persistent
to heat, acids, and bases, as well as reducing and
oxidising agents–
Lipophilic
•
Fluorinated
material are used
everywhere–
Possibly
blank contaminations
from
sampling
to analysis
•
Occurrence
of PFCs in all kind
of aqueous sample in very
low
concentration levels
and
hydrophilic
characteristics
→ ‘super
surfactants‘
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Target
Analytes
* mass-labelled
standards
(IS) are used
•
For the future…
•
Decomposed
very
fast in the presence
of oxygen
to
perfluoroalkyl sulfonates13C4
-PFOSi → 13C4
-PFOS!
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Sampling
Sample Type•
Preciptation
•
Groundwater•
Seawater
•
River water•
Wastewater
•
…
Sampling
method•
Bucket
•
Sampler
(bottle or
glass
bowl)
•
Rosette-type sampler
•
Ship
inlet
system•
…
mat
rixef
fect
s
→ Are the results
comparable?
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Filtration
+
No blocking
of the SPE cartridges
+
Calculation
of the partitioning
–
Sorption
to the filtration equipment
–
Source
for
blank contamination
• Low volume•
Check blanks
•
Rinse
with
methanol
after
filtration(max
5% methanol
in the water) •
PFOA blank
GFF
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Extraction
of the Particulate
Phase
••
GFF: Sonication 2x 100 mL methanolGFF: Sonication 2x 100 mL methanol
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Extraction
of the Aqueous Phase
ConditioningConditioning0.1% NH0.1% NH44
OH/MeOH 4 mLOH/MeOH 4 mLMeOHMeOH
4 mL4 mL
MilliMilli--Q water 4 mLQ water 4 mLLoad sample (add Load sample (add ISIS
before loading!)before loading!)
Sample vol.: 100Sample vol.: 100––1000 mL (1 drop/sec)1000 mL (1 drop/sec)
ElutionElutionFr.1: Fr.1: MeOHMeOH
4 mL4 mL
Fr.2: Fr.2: 0.1% NH0.1% NH44
OH/MeOH 4 mLOH/MeOH 4 mLConcentrationConcentration
Nitrogen purge: 0.2Nitrogen purge: 0.2––2 mL2 mL
••
Cartridge: WAX (Waters, 150 mg, 6cc, 30 Cartridge: WAX (Waters, 150 mg, 6cc, 30 µµm) (ISO 25101)m) (ISO 25101)
PP
HPLCHPLC--ESI(ESI(--))--MS/MSMS/MS
NHNH44
OAc buffer (pH 4), then dryingOAc buffer (pH 4), then dryingWashWash
Taniyasu et al. J. Chr. A 2005, 1093, 89-97
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Instrumental Analysis
HPLC•
HPLC column
•
Synergi Hydro-RP Mercury (20 x 2 mm, 2µ) Synergi Hydro-RP 80A (150 x 2 mm, 4µ)
•
Eluent•
A = Millipore Water + 10 mM NH4
OAc•
B = Methanol + 10 mM NH4
OAc•
Injection volume: 10 µL
•
Flow: 200 µL/min•
Equilibration time + run time: 8 + 40 min Chromatogram
PFC-Standardmix
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Reduction
of Blank Contamination
at the HPLC
No degasser
Septum
with
Silicone/ aluminium
Polypropylen tubings
Guard
column: Gemini 5u C18 Mercury (20 x 2 mm)
Guard
column: Synergi 2u Hydro-RP Mercury (20 x 2 mm)
Column: Synergi 4u Hydro-RP (150 x 2 mm)
Before
HPLC modifications After HPLC modifications
Stainless
solvent inlet
filter
Degassing
of the solvent using
sonication
7000 2300PFOA
HPLC
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Instrumental Analysis
HPLC•
HPLC column
•
Synergi Hydro-RP Mercury (20 x 2 mm, 2µ) Synergi Hydro-RP 80A (150 x 2 mm, 4µ)
•
Eluent•
A = Millipore Water + 10 mM NH4
OAc•
B = Methanol + 10 mM NH4
OAc•
Injection volume: 10 µL
•
Flow: 200 µL/min•
Equilibration time + run time: 8 + 40 min
ESI(-)-MS/MS (API 3000)•
Optimization
of source-
and
gas-parameter•
Optimization
of ion source-
voltages
for
parent-
and daughter-masses
HPLC-ESI(-)-MS/MS
Chromatogram
PFC-Standardmix
API 3000
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Quantification
•
Standard addition quantification
•
Solvent-based
calibration curve
quantification
•
Quantification
of the linear isomer
and estimation
of the contribution
of the branched
isomers
→ Different respond
factors of the linear and branched
isomers!
•
Use
of
standards
with
high purity
(> 99%)→ Report
the concentration of the anion!
•
Application
of mass-labelled
standards
(if
possible
for
each
analyte)
•
Control
method
and instrumental
blanks, recoveries, matrix
effects,…
•
Improvement
of comparability
(e.g. interlaboratory studys)
Ahr
ens
et a
l. M
arP
oll B
ull,
2009
in p
ressBSH
GKSS
WaterVolume
10 L
2 L
SPE
Chromabond
WAX cartridgeHR-P resin
Instrument API 2000
API 3000
→ Good comparability
(R = 0.96)
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Water
Analysis: Analytcal
challenge
for
the future
•
Using
of the ISO 25101
(comparability)•
Standard method
for
filtration!?
•
Reduction
of blank contamination
(solvent,…)•
Using
of more
IS
(if
possible
for
each
analyte)
•
Development
of analytical
methods
for
new
PFCs-
branched
isomers
-
PFPrA (C3
-PFCA) and TFA (C2
-PFCA) -
perfluoroalkyl phosphonates
- …•
Passive sampling
for
the aqueous environment
•
High volume
injection
(no sample
treatment)
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Outline
•
Analysis of PFCs in water-
Target
analytes
-
- Sampling-
-
Filtration
-
-
Extraction-
-
Instrumental analysis
-
-
Quantification
•
PFCs in the aqueous environment•
-
WWTPs and river
water
•
-
North Sea and Baltic
Sea-
Atlantic Ocean
•
Summary
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
How
did
PFCs Reach
Remote
Regions?
Indirect long-range transport via the atmosphere
• Volatile PFCs have been detected in the atmosphere(Martin et al. 2002; Jahnke et al. 2007)
Direct transport via ocean currents and/or sea-spray
• Detected in sea- and river water and precipitation (Yamashita et al. 2005)
• Ocean currents transport (Yamashita et al. 2005, 2008; Prevedouros et al. 2006) • Precursor compounds can be
decomposed to PF-Acids (Ellis et al. 2004)• Sea spray transport (McMurdo et al. 2008)
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Environmental Fate of PFCs
Production and usage of PFCs in
products
WWTPs
Landfill
Sludge Soil
River
Plants
Sediment
Groundwater
Ocean
Aquatic
animals
Land animals©
Ahrens L..
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
PFCs in WWTP Effluents
and the River Elbe
•
WWTP effluents are potential sources for PFCs in the aqueous environment, but also other sources must exist
•
Riverine
Transportation
of PFCs into
the marine
environment (Riverine
discharge: Elbe: ~800 kg/year, Rhein: ~8600 kg/year)
Ahrens et al. Marine Poll. Bull. 2009, 58, 1326-1333
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
0
5
10
15
20
Ocean Data
View
ng/L
∑PFC Concentration in the North and Baltic
Sea
• Conc. of ∑PFCs decrease
towards
the North Sea by
a factor
of over
100• Homogeneous
distribution
of PFCs in the Baltic
Sea
Ahrens et al. Chemosphere, 2009, 76, 179-184
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
PFBA
Concentration in the North and Baltic
Sea
• PFBA
was transported
from
the River Rhine
into
the German Bight
Ocean Data
View
Ahrens et al. Chemosphere, 2009, 76, 179-184
0
2
3
4
1
ng/L
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
PFCs River Rhine
0
50
100
150
200
250
300
36 35 34 33 32 31 30 29 28 27 26 25 24 23 22 21 20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1sampling site
others
PFOA
PFHpA
PFHxA
PFPA
PFBA
PFOS
PFHxS
PFBS
Dutch-German border
Lake Constance0,4165362443591705838 775
conc
entra
tion
[ng/
L]
[Rhine - km]
TWK precautionary value 0.1 µg/L
277
2237
105297
Dutch - GermanBorder
LakeConstance
179
80
276
25
275
39
502 11117057132
Aare
Ill
Neckar
Main
Ruhr
Sieg
Lahn
Moselle
MoehneLippe
2368
1567
1206
1303
1858
1609
1878 2235
Basel
Konstanz
Mainz
Strasbourg
Cologne
Duesseldorf
Leverkusen
Mannheim
Karlsruhe
Neuhausen
Koblenz
Rees
Bonn
•
Increasing
concentrations
of
PFHxS between sampling
station
4 and 5
•
Strong
increasing
concentrations
of
PFBA
and PFBS
between
Leverkusen and Duesseldorf
∑PFC mass
flow
in g per day
PFCs along
the River Rhine
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Benguela C.
EquatorialCounter C.
Cana
ryC.
N. Atlantic C.
N. Equatorial C.
S. Equatorial C.
PFCs in the Atlantic Ocean (46°N-26°S)
Ahrens et al. ES&T, 2009, 43, 3122-3127
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Summary
for
PFCs in the aqueous environment
•
Different sources of PFC contamination in the aqueous environment
•
Short chain
PFCs (→ PFBA and PFBS) and PFOA dominated
(>20 PFCs were
detected!)•
Riverine
transportation
into
the marine
environment
(e.g. Elbe, Rhine)•
Different spatial
distribution
in the
North and Baltic
Sea•
Long-range
transportation
via the ocean
currents
Lutz AhrensQUASIMEME workshop, Amsterdam14.-15. October 2009
Thank you for your attention!