Post on 11-Feb-2017
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)