SETAC Europe, Barcelona, May 2015

Branislav Vrana1, Foppe Smedes1, Tatsiana Rusina1,

Krzysztof Okonski1, Ian Allan2, Merete Grung2, Klára

Hilscherova1, Jiří Novák1, Peter Tarábek3,

Roman Grabic4, Jaroslav Slobodník5 1Research Centre for Toxic Compounds in the Environment (RECETOX), Masaryk

University, Brno, Czech Republic 2Norwegian Institute for Water Research (NIVA), Oslo, Norway 3Water Research Institute, Bratislava, Slovakia 4University of South Bohemia, České Budějovice, Czech Republic 5Environmental Institute, Slovakia

Passive sampling in the Joint Danube Survey 3

installation of an “active” passive sampler system on board of the expedition

ship (August-September 2013)

temporally- and spatially- integrative sampling approach - pollution situation in

defined stretches

passive samplers for hydrophobic and for polar compounds

Target analysis for priority substances + relevant river basin specific compounds

Non-target screening analysis (GC-TOF-MS; HPLC-HR-MS(MS))

Toxicity profiling – set of bioassays

Design of an “active” passive sampler

pump exposure chamber

2 x lid

Passive

samplers

water in

Passive samplers: Silicone rubber (SR), LDPE, SDB-RPS Empore discs

The “active” passive sampler

The Argus JDS3 sampling ship

passive samplers

“active” passive sampling device

Sampler in operation

( lifted above water for the photo)

Passive sampling

Mobile „active“ passive sampling device operation

Riverbed

pump

600 l

stainless

steel

barrel

CHEM

BOX

Flow and navigation direction

Water in

Water out

pump

water in

water out

Argus

Passive sampling on board of JDS3 ship Argus

River stretches sampled with passive samplers

Stretch

number Stretch start and end River km

Dates of

cruise

Mean water

temperature

[°C]

Exposure

time

[d]

Volume

extracted

by SR [L]a

1 Passau-Bratislava 2203-1852 17.8.-22.8. 21.3 2.0 169

2 Bratislava-Budapest 1852-1632 22.8.-26.8. 22.0 1.2 84

3 Budapest-Vukovar 1648-1297 26.8.-2.9. 21.9 1.7 139

4 Vukovar-Belgrade 1297-1154 2.9.-6.9. 22.8 1.6 133

5 Belgrade-Turnu-Severin 1154-930 6.9.-10.9. 22.1 2.0 139

6 Turnu-Severin-Ruse 930-495 11.9.-17.9. 21.9 2.0 129

7 Ruse-Braila 495-170 17.9.-21.9. 19.2 1.4 79

8 Braila-Tulcea 170-71 21.9.-26.9. 18.7 1.3 72

aVolume of water extracted by the SR sampler during exposure; it is

calculated for a model compound with molecular mass of 300.

Analysis of passive samplers

Type of analysis

Compound

class

Passive

sampler

Target analysis Non-target

screening

Toxicity

profiling

Specimen

bank

Nonpolar

compounds Silicone rubber

sheet (SR) RECETOX/ GC/MS

SOLUTIONS

bioassay battery

Later use in

FP7

SOLUTIONS log Kow >3

Low density

polyethylene

sheet (LDPE)

NIVA / GC/MS NIVA / GC/TOF

Polar

compounds

SDB-RPS

Empore discs

RECETOX/ Waters

XEVO TQ-S

RECETOX/ Agilent

6550 QTOF

SOLUTIONS

bioassay battery

Later use in

FP7

SOLUTIONS log Kow < 3

University of South

Bohemia /

Thermo Qexactive

RECETOX/ AB

SCIEX 5500 Q Trap

Result

Absolute or

relative

concentrations

of compounds in

the dissolved

phase

List of

compounds

subject to

prioritisation

for

identification

of RBSP

Response

and effect

pattern of

pollutants in

water

Parameters to calculate water concentration

from silicone rubber data

PRC list:

BIP-D10, PCB001, PCB002,

PCB003, PCB010, PCB014,

PCB021, PCB030, PCB050,

PCB055, PCB078, PCB104,

PCB145, PCB204

0.0

0.2

0.4

0.6

0.8

1.0

1.2

3 4 5 6 7 8 9

fraction P

RC

reta

ined

log(Kpw/M-0.47)

Regensburg-Passau

f-measured

f-calc

Rs=82.8 ( 6.2)

L/d

River stretches sampled with passive samplers

Stretch

number Stretch start and end River km

Dates of

cruise

Mean water

temperature

[°C]

Exposure

time

[d]

Volume

sampled

by SR [L]a

1 Passau-Bratislava 2203-1852 17.8.-22.8. 21.3 2.0 169

2 Bratislava-Budapest 1852-1632 22.8.-26.8. 22.0 1.2 84

3 Budapest-Vukovar 1648-1297 26.8.-2.9. 21.9 1.7 139

4 Vukovar-Belgrade 1297-1154 2.9.-6.9. 22.8 1.6 133

5 Belgrade-Turnu-Severin 1154-930 6.9.-10.9. 22.1 2.0 139

6 Turnu-Severin-Ruse 930-495 11.9.-17.9. 21.9 2.0 129

7 Ruse-Braila 495-170 17.9.-21.9. 19.2 1.4 79

8 Braila-Tulcea 170-71 21.9.-26.9. 18.7 1.3 72

aVolume of water extracted by the SR sampler during exposure; it is

calculated for a model compound with molecular mass of 300.

Vsampled = Rs x t Caged sampler (in 2days): 32

Spatial contaminant profiles measured

by silicone rubber: PAHs

0

2000

4000

6000

8000

10000

12000

14000

16000

Con

cen

trat

ion

[p

g/l]

Passau-Bratislava

Bratislava-Budapest

Budapest-Vukovar

Vukovar-Belgrade

Belgrade-Turnu-Severin

Turnu-Severin-Ruse

Ruse-Braila

Braila-Tulcea

Report: www.icpdr.org/main/activities-projects/jds3

Spatial contaminant profiles

measured by silicone rubber samplers

0

100

200

300

400

500

600

700

800

900

1000

PeCB HCB b-HCH p,p'DDT (x 10) ΣDDT

Co

nce

ntr

ati

on

[p

g/l]

Passau-Bratislava

Bratislava-Budapest

Budapest-Vukovar

Vukovar-Belgrade

Belgrade-Turnu-Severin

Turnu-Severin-Ruse

Ruse-Braila

Braila-Tulcea

Report: www.icpdr.org/main/activities-projects/jds3

Organochlorine pesticides Musk compounds

0

500

1000

1500

2000

2500

3000

3500

Cashmeran Celestolide Phantholide Traseolide Galaxolide / 10

Tonalide

Co

nce

ntr

atio

n [p

g/L

]

Passau-Bratislava

Bratislava-Budapest

Budapest-Vukovar

Vukovar-Belgrade

Belgrade-Turnu-Severin

Turnu-Severin-Ruse

Ruse-Braila

Braila-Tulcea

0.0

2.0

4.0

6.0

8.0

10.0

4-tert-octylphenol 4-nonylphenol

Co

nce

ntr

atio

n [

ng

/l]

Passau-Bratislava

Bratislava-Budapest

Budapest-Vukovar

Vukovar-Belgrade

Belgrade-Turnu-Severin

Turnu-Severin-Ruse

Ruse-Braila

Braila-Tulcea

Alkylphenols

0

20

40

60

80

100

120

140

160

180

200

PCB 28 PCB 52 PCB 101 PCB 118 PCB 153 PCB 138 PCB 180

Co

nce

ntr

atio

n [

pg

/l]

Passau-Bratislava

Bratislava-Budapest

Budapest-Vukovar

Vukovar-Belgrade

Belgrade-Turnu-Severin

Turnu-Severin-Ruse

Ruse-Braila

Braila-Tulcea

PCBs

Comparison with older data from „classical“ passive sampling

PAH concentrations: Stretch Passau-Bratislava

ACE

FLE

FEN

ANT

FLU

PYR

BAA

CHR

BbF

BkF

BAP

INP

DBAHABGHIPE

STATIC (2011) log C [pg/l]

1.0 1.5 2.0 2.5 3.0 3.5 4.0

JDS

3 M

OB

ILE

(2013)

log C

[pg/l]

1.0

1.5

2.0

2.5

3.0

3.5

4.0

* * *

* based on data < LOQ

Sampled using SPMD (summer 2011)

Sam

ple

d u

sin

g S

ilicone R

ubber

During J

DS

in 2

013

Danube

Comparison of „mobile“ with „static“passive sampling

POPs in water column at Bratislava

Static

„active“

passive:

Static

„classic“

passive:

Mobile „active“ passive

Passau-B

ratisla

va

log C [pg/l] STATIC

1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4

log

C [

pg/l]

MO

BIL

E

1.0

1.2

1.4

1.6

1.8

2.0

2.2

2.4

log C [pg/l] STATIC

1.0 1.5 2.0 2.5 3.0 3.5 4.0

log C

[pg/l] M

OB

ILE

1.0

1.5

2.0

2.5

3.0

3.5

4.0

"Active" passive 19.-23.8.

"Active" passive 23.-28.8.

"Classic" passive, 28.8.-1.10.

PAHs PCBs

Comparison of passive samplers: Silicone rubber vs. LDPE

Surface specific uptake

LDPE:112 cm2 SR:392 cm2

Chrysene – a compound in linear uptake phase in both samplers.

Silicone rubber [ng/cm2]

0.00 0.05 0.10 0.15 0.20 0.25 0.30

LD

PE

[n

g/c

m2]

0.00

0.05

0.10

0.15

0.20

0.25

0.30

Chrysene

Spatial contaminant profiles

measured by Empore RPS samplers

0

100

200

300

400

500

600

700

Alachlor Atrazine Diuron Isoproturon Simazine

ng/s

ampl

er

Passau-Bratislava

Bratislava-Budapest

Budapest-Vukovar

Vukovar-Belgrade

Belgrade-Turnu-Severin

Turnu-Severin-Ruse

Ruse-Braila

Braila-Tulcea

0

200

400

600

800

1000

1200

caffeine carbamazepine diclofenac

ng

/sa

mp

ler

Passau-Bratislava

Bratislava-Budapest

Budapest-Vukovar

Vukovar-Belgrade

Belgrade-Turnu-Severin

Turnu-Severin-Ruse

Ruse-Braila

Braila-Tulcea

Report: www.icpdr.org/main/activities-projects/jds3

Polar pesticides Pharmaceuticals

Comparison of passive samplers: Silicone rubber vs. Empore

Surface specific uptake

Empore:173 cm2 SR:392 cm2

n-nonylphenol

Silicone rubber [ng/cm2]

0 1 2 3 4 5 6 7

Em

po

re d

iscs [

ng

/cm

2]

0

1

2

3

4

5

6

7

caged sampler

deployment at

Bratislava,

43 days

X

Silicone rubber [ng/cm2]

0 1 2 3 4 5 6 7

Em

pore

dis

cs [ng/c

m2]

0

1

2

3

4

5

6

74-nonylphenol

caged sampler

deployment at

Bratislava,43 days

during JDS3

4-nonylphenol – a compound (likely) in linear

uptake phase in both samplers.

Conclusions

Mobile passive sampling enabled to clearly identify spatial profiles of a

broad range of organic pollutants in the water column of Danube

• POPs: PCBs, organochlorine pesticides, PAHs, brominated flame

retardants

• Alkylphenols, alkylphosphates, musks

• polar pesticides, pharmaceuticals

„Active“ vs. „caged“ passive sampling: cca. 5-fold increase of

sampling rate

• Measurement down to pg l-1 levels in only 2 days of sampling

A good comparability of various passive sampling approaches

• mobile and static sampling (concurrent and historical data)

• co-deployed passive samplers (SR and LDPE)

Sampling rates in the SDB-RPS Empore-disk sampler can be estimated

from the correlation with uptake to co-deployed silicone rubber

Current research: the combination of passive samplers with bioassays

for identification of areas of concern for further investigation

Report: www.icpdr.org/main/activities-projects/jds3

Acknowledgements

NORMAN association www.norman-network.net

The FP7 SOLUTIONS project has received funding from the European

Union’s Seventh Framework Programme for research, technological

development and demonstration under grant agreement no. 603437)

Ian Allan and Merete Grung acknowledge NIVA funding through the

RivScreen project (2013-2014), project O-13036

Collaborators from UFZ, INERIS, RWTH, WRI, EI, RECETOX,

University of South Bohemia are acknowledged for participating in

sampling, chemical and toxicological analysis.