Transcript Ingen bildrubrik

DISSOLVED ORGANOCHLORINE AND PAH POLLUTION
PROFILES IN LITHUANIAN AND SWEDISH WATER
Umeå
Kaunas
Audrone Zaliauskiene, Ilona Jegorova, *Per-Anders Bergqvist
Environmental Engineering, Kaunas University of Technology,
Kaunas, Lithuania
*Environmental Chemistry, Umeå University, SE-901 87 Umeå, Sweden
Introduction
Results and discussion
The purpose of this work was to carry out a single three week
monitoring in Lithuanian and Swedish water using
semipermeable membrane devices (SPMDs) in order to
estimate and compare PCB, PAH and pesticide concentrations.
The results show, that the Lithuanian rivers – Neris and
Nemunas in general are more polluted than Swedish streams
Tvärån and Djupbäcken even comparing with Umeå river the
levels was elevated.
PAH From graphs below we can see that PAH concentrations in the Swedish streams is rather small compared with the two
investigated Lithuanian rivers. Nearly all PAH compounds analyzed was detected in Lithuanian rivers. Phenantrene showed the highest
concentration – 7,7 ng/L. It was also found elevated concentrations of fluoranthene and pyrene –5,2 ng/L and 3,2 ng/L, respectively.In the
Lithuanian rivers four rings PAH compounds dominates, and in Swedish streams dominated two and three ring compounds.
PCB Usually concentration of PCBs decrease going from PCB #28 to PCB #180, but looking on the profile of concentrations in
Neris and Nemunas we could see the dominating peaks for PCB #110 and PCB #118. Since the concentrations of PCB #28 was found to
be relatively higher, it indicates that the pollution could be more recent. PCB congeneres were detected at higher concentrations in the
Lithuanian rivers. In Swedish waters PCB congeners were detected only at Krokvagen and Millbridge (PCB #28, PCB #31, PCB #44,
PCB #110), and these concentrations were close to detection limit. The highest concentrations in Lithuanian rivers were observed for PCB
#28 – 0,43 ng/L, PCB #31 – 0,24 ng/L, PCB #110 – 0,33 ng/L.
When comparing the two Lithuanian rivers, we found that
Nemunas contains higher concentrations than Neris. Neris and
Nemunas surrounds the Kaunas city. The sampling sites were
located downstream industrial areas and upstream urbanized
areas. The Swedish streams were examined since no fish
spawning was observed during the last years. Large part of
these streams consist of storm water.
PAH concentrations in sampling places
PCB concentrations in sampling places
Materials and methods
0,45
8,0
0,25
ng/L
3,0
0,20
2,0
0,15
1,0
Nemunas
0,10
Neris
Hospital
Milbridge
0,05
Krokvagen
Upstream
0,0
0,00
8 1
#2 #3 #53#45 52 49 47 4 2
# # # #4 4 88 91 4 1
# # # #8 0 99 7 5
#1 # #9 #9 110118 05 46 3 8
# # #1 #1 15 16 38 8 8
# # #1 15 12 56 80
# # #1 1
#
Pesticides The pesticide concentrations in the samples displayed higher concentrations in the Lithuanian rivers. Only o,p-DDE
(2,1 ng/L), -HCH (0,54 ng/L) and p,p-DDE (0,66 ng/L) at the Upstream sampling site was higher in the Swedish streams investigated.
Before the sampling site Upstream agricultural land, forests and green houses were dominating and could be the reason of pesticides
leaking to stream. The highest concentrations in Lithuanian rivers were of the DDT metabolite DDMu – 1,17 ng/L, o,p-DDE – 1,57 ng/L,
p,p-DDD – 0,41 ng/L.
EXPOSURE SITE
upstream industrial area
downstream industrial area
downstream before Umeå river
different type of storm water
Lithuanian river (upstream industrial
area)
Lithuanian river (downstream industrial
area)
Pollution comparison In the last graph a comparison between the large rivers in Lithuania and one large river in Sweden
can be seen indicating that the concentration of sumPAH in Neris and Nemunas was also elevated compared to Umea river. Higher
concentrations were also identified for sumDDT and sumPCB. The dissolved water concentrations of -HCH (purified HCH products
which consist of at least 99% -isomers are marketed under the comercial name lindane.), hexa-CBz and sumCHL (chlordane, which
consist of a mixture of more than 140 different components) were similar in all three river sites.
The compounds were dialysed and then fractionated by gel
permeation chromatography (GPC) technique followed by a
silica column. PAHs, PCBs and pesticides were identified by
gas chromatography and mass spectrometry (GC/MS).
Interpretation of chromatograms and calculation of
concentrations was done using sixteen internal standard (IS).
SPMD technology are used to estimate ambient TWA (time
weighted average) dissolved or vapour phase chemical
concentrations.
Pesticide concentrations at sampling sites
Comparison of pollution in three rivers
2,25
2,00
RT: 0,00 - 34,99
RT: 0,00 - 34,99
NL: 2,48E5
m/z=
255,50-256,50+
11,68
100
4,15 6,31 10,20 10,70
0
100
18,58 19,68
0
100
Tri PCB
50
4,53 6,34
0
100
8,81
11,58
Tetra PCB
50
0
100
50
Penta PCB
0
100
m/z=
393,50-394,50+
395,50-396,50
Hexa
PCB
MS
50
01111621_01111
8010913
0
0
5
10
15
20
Time (min)
25
30
PC
B
su
m
C
D
T
(SIM) chromatograms of five homolog groups of PCB
from the Lithuanian river Nemunas at Kaunas and from
sampling site Krokvägen in Tvärån stream in Umea,
Sweden. For hexa-PCB (6 chlorine atoms in the
chlorinated biphenyl) only limited amounts are dissolved
in water.
From the figures we can see, that Nemunas is more
polluted than Tvärån stream. At sampling site Krokvägen
an un-known compounds were detected at high
concentration at 18,58 min reducing the visibility of diPCB (2 chlorine atoms), but this homolog group is visible
in Nemunas sample. Tri-PCB (3 chlorine atoms) pattern is
not seen because of the large un-known peak with
retention time 14,44 min. Tetra-PCB (4 chlorine atoms)
was easily identitied in both places. Penta-PCB (5 chlorine
atoms) was very close to detection limit in Sweden.
50
0
100
Relative Abundance
• Using SPMD it is possible to compare sampling sites in
different places and countries at the same time;
• data from Integrated sampling of bioavaible compounds
during 21 days was evaluated;
• Lithuanian rivers were generally more polluted than Umeå
streams and Umeå river.
•PAH concentrations were ten times higher in Lithuanian rivers
than in Umeå river;
• PCB concentrations were also higher in Lithuanian rivers. In
Umeå streams PCB concentrations were equal;
• the relatively higher concentration of low molecular weight
PCB (as PCB#28) indicates a recent pollution in Lithuania;
• DDT and lindane were detected before industrial area in Umeå
(in upstream site). DDT concentrations were higher in Nemunas
than in Neris;
Relative Abundance
Conclusions:
SIM In these figures we can see selected ion monitoring
NL: 3,13E6
m/z=
255,50-256,50+
257,50-258,50
MS
01111605_01111
7113951
4,77 6,20 7,22 10,70 11,68 14,44 18,26 18,97
NL: 5,29E6
14,44
m/z=
289,50-290,50+
291,50-292,50
MS
01111605_01111
7113951
4,08 5,72 6,85 8,63 10,37 11,59
15,53 17,41 19,93
NL: 9,77E4
22,58
m/z=
20,19
325,50-326,50+
327,50-328,50
MS
18,63 18,97 22,11 24,13 24,51 28,25 30,23 32,45
01111605_01111
7113951
20,66 21,52 23,58 24,45 28,24 29,16 31,50 34,77 NL: 2,28E4
m/z=
359,50-360,50+
361,50-362,50
MS
01111605_01111
7113951
NL: 2,23E4
22,63 24,04 26,45 28,25 30,13 32,45
m/z=
393,50-394,50+
395,50-396,50
MS
01111605_01111
7113951
18,58
50
16,57
MS
01111621_01111
8010913
NL: 1,01E7
14,45
m/z=
289,50-290,50+
291,50-292,50
MS
01111621_01111
8010913
15,06 17,42 19,96
NL: 8,37E5
20,24
m/z=
325,50-326,50+
327,50-328,50
MS
22,60
01111621_01111
18,53 18,98 20,41 24,14 26,44 28,37 29,84 32,53 34,15 8010913
NL: 3,59E4
21,53 22,21
m/z=
23,61 24,77
359,50-360,50+
20,68
28,59 29,21
34,47
361,50-362,50
MS
01111621_01111
8010913
22,67 24,05 25,08 28,70 30,20 33,07 34,75 NL: 2,18E4
14,45
13,66
100
Di
PCB
257,50-258,50
18,27
50
m
su
PCB from site Nemunas and from site Krokvägen
H
L
Nemunas
Neris
Umea
su
K
as
un
em
N s
i
er
N ital
p e
os
H ridg
ilb en
M äg
kv
ro
ab
is
Tr
aH
b- CH
H
g- CH
H
s- CH
H
C
e- H
H
C
D H
o, DM
p- u
p, DD
p- E
D
o, D
p- E
D
p, D
p- T
D
o, D
p- T
D
p D
t-C ,p-D D
H D
L D
c- (tr
C
H ans
L
)
(
c- cis
H )
C
O HL
xy
-C
H HL
ex
aC
Bz
0,00
D
0,25
m
0,50
Bz
0,75
su
1,00
aC
ng/L
20
18
16
14
12
ng/L 10
8
6
4
2
0
H
CH
1,25
H
ex
1,50
g-
1,75
PA
H
6 NEMUNAS
0,30
ng/L 4,0
m
PLACE
UPSTREAM
KROKVÄGEN
MILBRIDGE
HOSPITAL
NERIS
5,0
as
un
em
N
is
er
N ital
p
e
os
H i dg
r
ilb en
M äg
kv
ro
ab
is
Tr
1
2
3
4
5
0,35
6,0
K
As an alternative high volume sampling, semipermeable
membrane devices (SPMDs) in water, was performed during
21 days. 6 sampling places was choosen for investigation.
0,40
7,0
2m
1- et N
m hy ap
et ln ht
h a h
A yln ph ale
ce ap th ne
na ht ale
2
p h n
2, ,63, di A Bi hth ale e
5- m c ph y ne
tr et e en le
im hy na y ne
e ln p le
1- thy ap hth ne
l h e
m
et nap tha ne
hy
h l
lp Fl tha ene
h u l
Ph ena ore ene
en nt ne
B
en A an hre
z( nt thr ne
a) hr en
an ac e
th en
r
Fl Ch ace e
B
uo ry n
en
ra sen e
B zo
nt e
en (b
zo )fl P hen
(k uo yre e
B )flu ran ne
en o th
B zo ran en
en (e th e
zo )p en
B
(a yre e
en
)p n
z
D In o(g Pe yre e
ib de ,h ry ne
en n ,i) l
zo o( pe en
(a c,d ry e
,h )p le
)a y ne
nt re
hr ne
ac
en
e
Semipermeable membrane devices (SPMDs) are passive
samplers used for measuring the truly dissolved concentration
of Persistent Organic Pollutant (POPs) in water. SPMD
devices are new, versatile, non-destructive methods, without
any advanced or costly equipment requirements.
Semipermeable membranes filled with lipophilic solvent are
possible to use for the evaluation of bioavailability of organic
compounds. SPMD data can be used to study variation in
organic pollutant concentrations in space and time.
50
0
100
50
0
100
50
0
0
5
10
15
20
25
Time (min)
Acknowledgements – We wish to acknowledge Umea University, Socrates program and
Kaunas University of Technology for financial support.
30
SPMD sampling results in clean extract which is easy to
evaluate, and the clean-up procedure can include only nondestructive steps.