An international collaborative study on the use of passive ......CB145, CB204 After six weeks...

An international collaborative study on the use of passive samplers

in monitoring of emerging pollutants

B. Vrana, F. Smedes, R . Prokeš, R. Loos, N. Mazzella , H. Budzinski, C. Mieg e, A. Gravell,

T. Ocelka , E. Vermeirssen

Norman Expert Group Meeting “Linking Environmental Quality Standards and Passive Sampling”, 3.-4.7. 2012, Brno

Activities of NORMAN network in passive sampling 2009-2012

An expert group meeting in 2009

A position paper “Passive sampling of emerging pollutants in the aquatic environment: state of the art and perspectives” in 2010

An interlaboratory studyin 2011-2012

www.norman-network.net

Collaborative study

instrumental analysisanalysis of sampler matrixcomparison of samplerscomparison with spot sampling

A sampler comparison exercise

Assessment of steps in passive sampling process

Target compounds

• 7 polar pesticides• 7 pharmaceuticals• 5 steroid hormones• Bisfenol A• Triclosan• PFOA, PFOS• 6 brominated diphenyl ethers (BDEs)

I 1. Exposure of passive samplers from participants

Coordinator

Participant 1

Participant 2

Participant 3

Participant N

Sampler 3

Sampler 2

Sampler 1

for selected analyte/analytes

Sampling site -sampler exposure

Sampler 1 Sampler 2

Sampler 3 Sampler N

Sampler N…

…

…

Sampling site

Sampling site: discharge from WWTP Brno-Modřice

Sampler deployment

II 1. Recovery passive samplers from participants

Coordinator

Participant 1

Participant 2

Participant 3

Participant N

Sampler 3

Sampler 2

Sampler 1



Sampler 1Sampler 2

Sampler 3Sampler N

Sampler N

Database

Report:ng/sampler of compound X Surface area of sampler ng/L water of compound Xcalculation procedure for compound X

…

…

2a. Standard solution

Coordinator

Participant 1

Participant 2

Participant 3

Participant N

send to coordinatorCentral laboratory

S Standard solution

S S SS

purchase standardprepare a QC solutionprepare multiple vials (according to participant registration)check homogeneitysend to coordinator

S

S

S

S

distribute standards


Database

Report to databaseng/ml of compound X

…

2b. Provided passive samplers

Coordinator

Participant 1

Participant 2

Participant 3

Participant N

Sampling site -sampler exposureparalel to samplers of participants

ProvidedsamplerProvided

samplerProvidedsampler

Providedsampler

prep

ared

by

coor

dina

tor

Providedsampler

Providedsampler

Providedsampler

Providedsampler

Providedsampler

Providedsampler

Providedsampler

Providedsampler

Central laboratory Provided

sampler

Database

Report to databaseng/sampler of compound Xcm2 sampler surfaceng/L water of compound Xcalculation procedure

…

3. Water; continuous sampling

for selected analyte/analytesW water sample

Coordinator


Central laboratory

W

WWWW

Wanalysewater samples

collectwater samplesend to centrallaboratory

ProvidedsamplerSampler 3

Sampler 2

Sampler 1

Sampler 4

ProvidedsamplerProvided

samplerProvidedsampler

Database

Report to databaseng/L water of compound X

NOT APPLIED FOR PBDEs

Participating laboratoriesfrom Europe

• Polar pesticides – 19• Pharmaceuticals – 17• Steroid hormones – 15• Triclosan – 8• Bisphenol A – 11• PFOA, PFOS – 8• PBDE – 16

…and from the rest of the World

Pharmaceuticals: Categories of participant samplers

0123456789

10111213141516

Atenolol

Carbam

azepin

e

Diclofe

nac

Ibupro

fen

Naprox

en

Diazep

am

Alpraz

olam

Ketopro

fen

SPEEDEDPESSRCCPOLPOCIPEDPOCIS

Pharmaceuticals

Num

ber

of la

bora

torie

s

Sampler Abbreviation

POCIS pharmaceutical version POCIS

Empore Disk ED

POCIS, pesticide version POCIP

Chemcatcher (3rd generation) polar configuration

CCPOL

silicone rubber material SR

Empore SDB-RPS with PES-Membrane (0.1um)

EDPES

Speedisks SPEED

Up to 17 participants

SPEEDSR

POCIS POCIP EDPES CCPOL CCPOL ED

Standard solution, µg/mL

Alpraz

olam

Atenolo

lCarb

amaz

epin

Diazep

amDicl

ofena

cIbu

profen

Ketopro

fenNap

roxen

µg/m

L

0.9

2

3

456789

20

30

40

1

10

Study results: pharmaceuticals

Set value± expanded uncertainty (k = 2)


Provided sampler, ng/cm2

Alpraz

olam

Atenolo

lCarb

amaz

epin

Diazep

amDicl

ofena

cIbu

profen

Ketopro

fenNap

roxen

ng/c

m2

0.01

0.1

1

10

100

Participant sampler, Cw in ng/L

Alpraz

olam

Atenolo

lCarb

amaz

epin

Diazep

amDicl

ofena

cIbu

profen

Ketopro

fenNap

roxen

ng/L

0.1

1

10

100

1000


Weekly spot samples

LODin spotsamples

RESULTSExample: Carbamazepin

Provided sampler, ng/cm2

17 19 23 29 31 32 36 39 40 43 44 47 48 49 50 50a 51

503

126

31

7.9

2

Standard solution, µg/mL

17 19 23 29 31 32 36 39 40 43 44 47 48 49 50 50a 51

4.4

3.1

2.2

1.6

1.1

Participant sampler, Cw in ng/L

P

OC

IS

E

D

P

OC

IS

P

OC

IS

P

OC

IS

C

CPO

L

P

OC

IS

P

OC

IS

S

PEED S

R

P

OC

IS

P

OC

IS

E

DPE

S

P

OC

IS17 19 23 23a 29 31 32 36 39 40 43 43a 44 47 48 49 50 50a 51

6080

1520

380

95

24

S tan d.So lut io nµ g /m L

M ed ian 2.2 0s 1.2G e om ea n 2.7n 17O u tl ier s 2s e x c l. o ut l 0.2 8

R efv al ue 2.1 4E x p . U n c 0.1 3

Pr ov id edSa m p le ru pta k en g/c m 2

M ed ian 31 .4s 32G e om ea n 23n 17O u tl ier s 1s e x c l. o ut l 26

P ar ic ip an tSa m p le r

C wng /L

M ed ian 3 80s 2 30G e om M ea n 3 86n 14O u tl ier s 0

S po t s am ple sP er io d 1 7 78P er io d 2 7 94

medianvalue

± 2 × SD of log2transformed data

Set value± expanded

Uncertainty (k = 2)

water samplemean

Log 2

scal

e

Laboratory number

outliers

Variability of results at different procedure levels

0%

20%

40%

60%

80%

100%

120%

Standard

solut

ion

NPS amou

ntNPS w

ater c

oncentr

ation

PPS amount

PPS wate

r con

centr

ation

WithinlaboratoryMean

Betweenlaboratory

Coe

ffici

ent o

f var

iatio

n

Carbamazepine

0%

50%

100%

150%

200%

250%

300%

350%

Standard

solut

ion

NPS amou

ntNPS w

ater c

oncentr

ation

PPS amount

PPS wate

r con

centr

ation


Betweenlaboratory

Coe

ffici

ent o

f var

iatio

n

Diclofenac

0%

50%

100%

150%

200%

250%

Standard

solut

ion

NPS amou

ntNPS w

ater c

once

ntratio

n

PPS amount

PPS wate

r con

centr

ation


Betweenlaboratory

Coe

ffici

ent o

f var

iatio

n

Ibuprofen

0%

20%

40%

60%

80%

100%

120%

140%

Standard

solut

ion

NPS amou

ntNPS w

ater c

oncentr

ation

PPS amount

PPS wate

r con

centr

ation


Betweenlaboratory

Coe

ffici

ent o

f var

iatio

n

Naproxen

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Standard

solut

ion

NPS amou

ntNPS w

ater c

once

ntratio

n

PPS amount

PPS wate

r con

centr

ation


Betweenlaboratory

Coe

ffici

ent o

f var

iatio

n

Diazepam

0%

10%

20%

30%

40%

50%

60%

70%

80%

Standard

solut

ion

NPS amou

ntNPS w

ater c

oncentr

ation

PPS amount

PPS wate

r con

centr

ation


Betweenlaboratory

Coe

ffici

ent o

f var

iatio

n

Alprazolam

0%

20%

40%

60%

80%

100%

120%

140%

160%

Standard

solut

ion

NPS amou

ntNPS w

ater c

oncentr

ation

PPS amount

PPS wate

r con

centr

ation


Betweenlaboratory

Coe

ffici

ent o

f var

iatio

n

Ketoprofen

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

Standard

solut

ion

NPS amou

ntNPS w

ater c

oncentr

ation

PPS amount

PPS wate

r con

centr

ation


Betweenlaboratory

Coe

ffici

ent o

f var

iatio

n

AtenololNPS – provided passive samplerPPS – participant passive sampler

0%

20%

40%

60%

80%

100%

120%

Standard

solut

ion

NPS amou

ntNPS w

ater c

oncentr

ation

PPS amount

PPS wate

r con

centr

ation


Betweenlaboratory

Coe

ffici

ent o

f var

iatio

n

Carbamazepine

Variability of reported results

NPS – provided passive sampler; PPS – participant passive sampler

Pharmaceuticals Coefficient of variation (%)

Variability: Within laboratory Between laboratory Matrix analysed: Min. Max. Min. Max.

Standard solution 3% 8% 6% 35% Provided sampler

NPS amount 11% 14% 35% 133%

NPS water concentration

8% 13% 70% 333%

Participant sampler

PPS amount 10% 33% 13% 117%

PPS water concentration

9% 21% 68% 205%

Comparison: participant vs. provided samplers

Comparing samplers, Cw in ng/L

ED

CCPOL

SPEEDSR

32

64

128

256

512

1024

2048

32 64 128 256 512 1024 2048

Provided sampler

Par

ticip

ant s

ampl

er

Comparing samplers, uptake in ng/cm2

EDPES

SPEEDCCPOL

ED

128

64

32

16

8

412864321684

Provided sampler

Par

ticip

ant s

ampl

er

Composite water sample(2 week samples per exposure)

CARBAMAZEPINE

STUDY RESULTSAn acceptable within laboratory variability was observed for standard solution and samplers

Common compounds, e.g pesticides, showed lower varabilitythan new or rare ones

Between laboratory variation was roughly a factor 5 larger than within laboratory variability

However, individual laboratories found well comparable results for participant and provided sampler for uptake per surface area as well as the resulting water concentration

Passive sampling could be evaluated versus the spot sampling method with variable differences, but mostly within the range comprised by the passive sampling results

Conclusions

passive sampling process is not causing excessive variability - similar results were obtained for different passive samplers

between laboratory variability is likely related to difficulties with analysis in complex environmental matrices

in future, effort should be made to improve accuracy of analysis of complex samples

Acknowledgment

• NORMAN Association• European Commission – DG JRC• Organisers – steering committee• Water Research Institute, Slovakia• RECETOX, Masaryk university, Czech

republic• Deltares, The Netherlands• Participants

Continuous water sampling: for polar compounds only

PHARMACEUTICALS, POLAR PESTICIDESSTEROIDS, FLUORINATED SURFACTANTS,

BISPHENOL A, TRICLOSAN

Provided sampler: POCIS• OASIS HLB Sorbent

receiving phase• Polyethersulphone

membrane• Standard configuration

(200 mg sorbent; 45.8 cm2 surface area)

• For polar pesticides spiked with DIA-D5 – potential PRC

BROMINATED DIPHENYL ETHERS

Provided sampler: Altesil Silicone rubber

• Silicone rubber sheet consisting of 3 sheets (90x55 mm), ≈8.91 g

• Surface area: 297 cm2

• Performance reference compounds: 7.PRCs: D10-biphenyl, PCBs: CB001,

CB002, CB003, CB010, CB014, CB021, CB030, CB050, CB055, CB078, CB104, CB145, CB204

After six weeks exposure…

Sampler preparation for deployment

Sampler recovery

Onsite sampler cleaning and preparation

Target compoundsPOLAR PESTICIDES

Compound CAS Usage 1. Atrazine 1912-24-9 triazine herbicide 2. Carbendazim 10605-21-7 benzimidazole

fungicide 3. Desethylatrazine 6190-65-4 triazine metabolite4. Desethylterbutylazine 30125-63-4 triazine metabolite5. Diuron 330-54-1 phenylurea

herbicide 6. S-metolachlor 87392-12-9 chloroacetanilide

herbicides 7. Terbutylazine 5915-41-3 triazine herbicide

Target compoundsPHARMACEUTICALS

Compound CAS Usage 1. Alprazolam 28981-97-7 benzodiazepine

drug 2. Atenolol 29122-68-7 beta blocker drug 3. Carbamazepine 298-46-4 anticonvulsant

drug 4. Diazepam 439-14-5 benzodiazepine

drug 5. Diclofenac 15307-86-5 non-steroidal anti-

inflammatory drug 6. Ibuprofen 15687-27-1 non-steroidal anti-

inflammatory drug 7. Naproxen 22204-53-1 non-steroidal anti-

inflammatory drug

Target compoundsSTEROID HORMONES

Compound CAS Usage 1. 17-alpha-Estradiol 57-91-0 steroid hormone 2. 17-alpha-Ethinylestradiol 77538-56-8 contraceptive 3. 17-beta-Estradiol 82115-62-6 steroid hormnone 4. Estriol 50-27-1 steroid hormnone 5. Estrone 53-16-7 steroid hormnone

Target compoundsBISPHENOL A, TRICLOSAN, PFOA PFOS

Compound CAS Usage 1. Bisphenol A 80-05-7 monomer to make

plastics 2. Triclosan 3380-34-5 antibacterial and

antifungal agent

Compound CAS Usage 1. PFOA 335-67-1 fluorosurfactant 2. PFOS 1763-23-1 fluorosurfactant,

fabric protector

Target compoundsBROMINATED DIPHENYL ETHERS

Compound CAS Usage 1. BDE 28 41318-75-6 Flame retardant 2. BDE 47 5436-43-1 Flame retardant 3. BDE 99 60348-60-9 Flame retardant 4. BDE 100 189084-64-8 Flame retardant 5. BDE 153 68631-49-2 Flame retardant 6. BDE 154 207122-15-4 Flame retardant

An international collaborative study on the use of passive ......CB145, CB204 After six weeks...

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