This study analyzed contaminants in sediments from fiber bank areas in the northern Baltic Sea. The objectives were to understand bioaccumulation and biotransformation of contaminants like PCBs, understand how sediment properties affect these processes, and determine the effects of species-specific traits on bioaccumulation. Sediments and biota were sampled from three locations and analyzed for contaminant concentrations and profiles. Results showed the fiber bank sediments had high PCB concentrations and acted as the primary source for bioaccumulation in invertebrates. Chiral PCB analysis provided evidence of enantioselective biotransformation occurring in some species. The findings improve understanding of contaminant fate in fiber bank sediments and food webs in the northern Baltic Sea

1. 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, Sweden
2Umeå Marine Research Center, Hörnefors, Sweden
3Department of Ecology and Environmental Science, Umeå University, Sweden
*E-mail: darya.kupryianchyk@umu.se

2. 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-Piteaa
2. http://www.vinnova.se/upload/EPiStorePDF/va_14_08.pdf 2
• requires the availability of water
• concentrated along the coast of northern Sweden
(Norrland)

3. 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

4. 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

5. Sampling locations
Norrbyn
(reference)
Örnsköldsvik
5
Kramfors

6. Bioaccumulation experiment
Kramfors
No biota
Macoma
balthica
Marenzelleria
spp
T=28 days
Climate controlled room
6
Örnsköldsvik
Norrbyn (ref)

7. 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

8. Chemical analysis
20
40
60
80
Csed,ng/g
SedimentCB180
CB153
CB138
CB118
CB101
CB52
CB28
5
10
15
20
Cpw,pg/L
Pore waterCB180
CB153
CB138
CB118
CB101
CB52
CB28
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;
0
NOR KRA ORN
0
NOR KRA ORN
0
200
400
600
800
1000
1200
NOR KRA ORN NOR KRA ORN
Mar Mac
Cbiota,ng/glipids
Biota
CB180
CB153
CB138
CB118
CB101
CB52
CB28
• good agreement between PCB profiles in sediment and
invertebrates -> sediment is a primary source of PCBs;

9. 4
6
8
10
LogKd,L/kg
Log Kd vs Log Kow
Örnsköldsvik
Sorption
1
2
3
4
5
6
7
talorganicandinorganic
carbon,%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
LogKow
Kramfors
Norrbyn
92
4
6
8
10
12
5,0 5,5 6,0 6,5 7,0 7,5 8,0
LogKoc,L/kg
LogKow
Log Koc vsLog Kow
Örnsköldsvik
Kramfors
Norrbyn
0
1
TOC TIC
Tota

10. Lignin and cellulose
0
5
10
15
20
Relativeabundance,%
Lignin
20
40
60
80
100
Relativeabundance,%
Cellulose
10
0
2
4
6
8
Önrsköldsvik Kramfors Norrbyn
Cellulose/lignin
Cellulose/lignin
Önrsköldsvik Kramfors Norrbyn 0
Önrsköldsvik Kramfors Norrbyn

11. y = 0,7603x + 2,7033
R² = 0,408
y = 1,2456x + 0,6421
R² = 0,7337
4
5
6
7
8
9
10
LogBAF,LogKoc
Örnsköldsvik
LogBAF
LogKoc
Sorption to sediment OC and biota lipids
y = 1,7028x - 3,648
R² = 0,7134
y = 1,1707x + 0,202
R² = 0,583
4
5
6
7
8
9
10
LogBAF,LogKoc
Kramfors
LogBAF
LogKoc
4
5,0 5,5 6,0 6,5 7,0 7,5 8,0
Log Kow
11
LogKoc exceeded LogBAF
by 1-1.5 orders of
magnitude in Örnsköldsvik,
however LogKoc were
comparable to LogBAF in
Kramfors and Norrbyn
sediments.
y = 1,809x - 4,2942
R² = 0,7633
y = 1,6897x - 3,8155
R² = 0,8151
4
5
6
7
8
9
10
5,0 5,5 6,0 6,5 7,0 7,5 8,0
LogBAF,LogKoc
Log Kow
Norrbyn
LogBAF
LogKoc
4
5,0 5,5 6,0 6,5 7,0 7,5 8,0
Log Kow

12. Sorption to sediment OC and biota lipids
y = 1,0485x + 0,2138
R² = 0,5556
y = 1,3948x - 0,393
R² = 0,8358
4
5
6
7
8
9
10
LogBAF,LogKoc
Örnsköldsvik
LogBAF
LogKoc
y = 1,1042x + 0,3527
R² = 0,572
y = 1,2151x - 0,1794
R² = 0,7177
4
5
6
7
8
9
10
LogBAF,LogKoc
Kramfors
LogBAF
LogKoc
12
4
5,0 5,5 6,0 6,5 7,0 7,5 8,0
Log Kow
4
5,0 5,5 6,0 6,5 7,0 7,5 8,0
Log Kow
y = 1,0577x + 0,3857
R² = 0,6529
y = 1,6949x - 3,9442
R² = 0,9659
4
5
6
7
8
9
10
5,0 5,5 6,0 6,5 7,0 7,5 8,0
LogBAF,LogKoc
Log Kow
Norrbyn
LogBAF
LogKoc
Similar results for
Marenzelleria spp but no
difference between the
species

13. 0
1
2
3
LogBSAF
BSAF vsLog Kow. Macoma balthica
Örnsköldsvik
Kramfors
Norrbyn
Biota to sediment accumulation factor
-1
5,0 5,5 6,0 6,5 7,0 7,5 8,0
LogKow
13-2
-1
0
1
2
3
4
5,0 5,5 6,0 6,5 7,0 7,5 8,0
LogBSAF
LogKow
BSAF vsLog Kow. Marenzelleria spp
Örnsköldsvik
Kramfors
Norrbyn

14. 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

15. 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
0,3
CB95 CB91 CB136 CB149 CB176
sediment pore water
Macoma balthica Marenzelleria spp
0,3
CB95 CB91 CB136 CB149 CB176
sediment pore water
Macoma balthica Marenzelleria spp
15
0,3
0,4
0,5
0,6
0,7
CB95 CB91 CB136 CB149 CB176
EF
Norrbyn
sediment pore water
Macoma balthica Marenzelleria spp

16. 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 balthica
samples -> enantioselective metabolism
16

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