Analysis of PFCs in water - QUASIMEME - Home L. - PFC water... · 14.-15. October 2009 QUASIMEME workshop, Amsterdam Lutz Ahrens Analysis of PFCs in water Lutz Ahrens GKSS Research

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: [email protected]


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


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‘


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!


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?


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


Extraction

of the Particulate

Phase

••

GFF: Sonication 2x 100 mL methanolGFF: Sonication 2x 100 mL methanol


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


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


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


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


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)


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)


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


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)


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..


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


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


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


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


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


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


Thank you for your attention!

Documents

Analysis of PFCs in water - QUASIMEME - Home L. - PFC water... · 14.-15. October 2009 QUASIMEME workshop, Amsterdam Lutz Ahrens Analysis of PFCs in water Lutz Ahrens GKSS Research