Understanding bioaccumulation and biotransformation processes of high priority contaminants in fiber banks sediments in the northern Baltic Seasediments in the northern Baltic Sea

Darya Kupryianchyk1,*, Channa Yath1, Terry Bidleman1, Henrik Larsson2, Per Liljelind1, Agneta Andersson3, Owen Rowe3, Johan Wikner2,3, Peter Haglund1, Mats Tysklind1

1Department of Chemistry, Umeå University, Sweden2Umeå Marine Research Center, Hörnefors, Sweden

3Department of Ecology and Environmental Science, Umeå University, Sweden*E-mail: darya.kupryianchyk@umu.se

Pulp and paper industry in Sweden

1. http://www.isover-technical-insulation.co.za/About-ISOVER/Reference-project/Industry-insulation-for-south-africa/Smurfit-Kappa-Kraftliner-Mill-Piteaa2. http://www.vinnova.se/upload/EPiStorePDF/va_14_08.pdf 2

• requires the availability of water• concentrated along the coast of northern Sweden

(Norrland)

Fiber banks areas

• Rich in fiber, cellulose/lignin• Contaminated with PCBs,

PAH, and other POPs• Effect of sediment properties

on sorption?• What are biodegradation and

”primary source”

• What are biodegradation and biotransformation processes in fiber banks sediments?

3

Secondary source

Objectives

• sediment-to-water exchange of POPs in fiber banks sediment,

• how differences in properties of contaminated • how differences in properties of contaminated sediments affect bioaccumulation and biodegradation of POPs,

• Effect of species-specific traits on bioaccumulation

4

Sampling locationsNorrbyn(reference)

Örnsköldsvik

5

Kramfors

Bioaccumulation experiment

Kramfors

No biota

Macomabalthica

Marenzelleriaspp

T=28 daysClimate controlled room

6

Örnsköldsvik

Norrbyn (ref)

Chemical analysis

Extraction

• Sediment and biota –with toluene by accelerated solvent extractor

• Pore water – with polyoxymethyene (76um) – extraction with heptane/acetone 80/20– extraction with heptane/acetone 80/20

Instrumental analysis: GC - high resolution MS with columns specific to the task: • DB5ms for quantitative work and• the cyclodextrin stationary phase CP-Chiral-

Dex-CB for enantiospecific analysis. 7

Chemical analysis

20

40

60

80

Csed

, n

g/

g

SedimentCB180CB153CB138CB118CB101CB52CB28

5

10

15

20

Cp

w,

pg

/L

Pore waterCB180CB153CB138CB118CB101CB52CB28

CB180

• Sediment – Kramfors and Ö-vik are class V according to the Swedish classification of contaminated sediments;

• pore water - high abundance of low molecular congeners, e.g. CB28, 52 and 101;

0NOR KRA ORN

0NOR KRA ORN

0

200

400

600

800

1000

1200

NOR KRA ORN NOR KRA ORN

Mar Mac

Cb

iota

, n

g/

g l

ipid

s

BiotaCB180CB153CB138CB118CB101CB52CB28

• good agreement between PCB profiles in sediment and invertebrates -> sediment is a primary source of PCBs;

4

6

8

10

Log

Kd,

L/k

g

Log Kd vs Log Kow

Örnsköldsvik

Sorption

1

2

3

4

5

6

7

tal o

rgan

ic an

d in

orga

nic

carb

on, %

d.w

.

Total organic and inorganic

Örnsöldsvik

Kramfors

Norrbyn

2

4

5,0 5,5 6,0 6,5 7,0 7,5 8,0

Log Kow

Kramfors

Norrbyn

92

4

6

8

10

12

5,0 5,5 6,0 6,5 7,0 7,5 8,0

Log

Koc

, L/k

g

Log Kow

Log Koc vs Log Kow

Örnsköldsvik

Kramfors

Norrbyn

0

1

TOC TI C

Tot

a

Lignin and cellulose

0

5

10

15

20

Rel

ativ

e ab

unda

nce,

%

Lignin

20

40

60

80

100

Rel

ativ

e ab

unda

nce,

%

Cellulose

10

0

2

4

6

8

Önrsköldsvik Kramfors Norrbyn

Cel

lulo

se/li

gnin

Cellulose/lignin

Önrsköldsvik Kramfors Norrbyn 0

Önrsköldsvik Kramfors Norrbyn

y = 0,7603x + 2,7033R² = 0,408

y = 1,2456x + 0,6421R² = 0,7337

4

5

6

7

8

9

10

LogB

AF,

Log

Koc

Örnsköldsvik

LogBAF

LogKoc

Sorption to sediment OC and biota lipids

y = 1,7028x - 3,648R² = 0,7134

y = 1,1707x + 0,202R² = 0,583

4

5

6

7

8

9

10

LogB

AF,

Log

Koc

Kramfors

LogBAF

LogKoc4

5,0 5,5 6,0 6,5 7,0 7,5 8,0Log Kow

11

LogKoc exceeded LogBAFby 1-1.5 orders of magnitude in Örnsköldsvik, however LogKoc were comparable to LogBAF in Kramfors and Norrbynsediments.

y = 1,809x - 4,2942R² = 0,7633

y = 1,6897x - 3,8155R² = 0,8151

4

5

6

7

8

9

10

5,0 5,5 6,0 6,5 7,0 7,5 8,0

LogB

AF,

Log

Koc

Log Kow

Norrbyn

LogBAF

LogKoc

45,0 5,5 6,0 6,5 7,0 7,5 8,0

Log Kow

Sorption to sediment OC and biota lipids

y = 1,0485x + 0,2138R² = 0,5556

y = 1,3948x - 0,393R² = 0,8358

4

5

6

7

8

9

10

LogB

AF,

Log

Koc

Örnsköldsvik

LogBAF

LogKoc

y = 1,1042x + 0,3527R² = 0,572

y = 1,2151x - 0,1794R² = 0,7177

4

5

6

7

8

9

10

LogB

AF,

Log

Koc

Kramfors

LogBAF

LogKoc

12

45,0 5,5 6,0 6,5 7,0 7,5 8,0

Log Kow

45,0 5,5 6,0 6,5 7,0 7,5 8,0

Log Kow

y = 1,0577x + 0,3857R² = 0,6529

y = 1,6949x - 3,9442R² = 0,9659

4

5

6

7

8

9

10

5,0 5,5 6,0 6,5 7,0 7,5 8,0

LogB

AF,

Log

Koc

Log Kow

Norrbyn

LogBAF

LogKoc

Similar results for Marenzelleria spp but no difference between the species

0

1

2

3

Log

BSA

F

BSAF vs Log Kow. Macoma balthica

Örnsköldsvik

Kramfors

Norrbyn

Biota to sediment accumulation factor

-15,0 5,5 6,0 6,5 7,0 7,5 8,0

Log Kow

13-2

-1

0

1

2

3

4

5,0 5,5 6,0 6,5 7,0 7,5 8,0

Log

BSA

F

Log Kow

BSAF vs Log Kow. Marenzelleria spp

Örnsköldsvik

Kramfors

Norrbyn

Chiral PCBs as tracers of transport and accumulation processes

Primary emisions (racemic

chemicals)

Mix

Sediment, water

chemicals)

Secondary emisions

(nonracemic chemicals

Non-racemic enantiomer proportions -> biological degradation, metabolism in soil water, organisms

0,3

0,4

0,5

0,6

0,7

EF

Kramfors

0,3

0,4

0,5

0,6

0,7

EF

Örnsköldsvik

Chiral PCBs as tracers of transport and accumulation processes

0,3CB95 CB91 CB136 CB149 CB176

sediment pore waterMacoma balthica Marenzelleria spp

0,3CB95 CB91 CB136 CB149 CB176

sediment pore waterMacoma balthica Marenzelleria spp

15

0,3

0,4

0,5

0,6

0,7

CB95 CB91 CB136 CB149 CB176

EF

Norrbyn

sediment pore waterMacoma balthica Marenzelleria spp

Chiral PCBs as tracers of transport and accumulation processes• Most chiral PCBs in sediments were racemic -> recent

pollution or lack of enantioselective microbial degradation

• nonracemic EFs of PCB 136 in Örnsköldsvik and 91 in Kramfors indicate metabolism for these PCBs, so other PCBs may also be degrading, but not enantioselectivelymay also be degrading, but not enantioselectively

• EFs in pore water should be the same as in sediment due to dynamic contaminant exchange among them

• Nonrecemic EF of PCB 95 and 136 in Macoma balthicasamples -> enantioselective metabolism

16

Acknowledgments

The research was supported by the Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning (Formas)