Dr. sc. Mladen Picer ASSESSMENT OF THE SELECTED POPs

Dr. sc. Mladen Picer ASSESSMENT OF THE SELECTED POPs

Rudjer Boskovic Institute (IRB)
Centre for Marine and Environmental Research (CMER)
Dr. sc. Mladen Picer
ASSESSMENT OF THE SELECTED POPs (PCBs,
PCDDs/Fs, OCPs) IN THE ATMOSPHERE AND WATER
ECOSYSTEMS FROM THE WASTE MATERIALS
GENERATED BY WARFARE IN FORMER
YUGOSLAVIA (APOPSBAL ICA2 - CT2002-10007)
„Persistent Toxic Substances Contamination
of the European Region“
Brno, Czech Republic, November 10-12, 2003
Plitvice detail - winter time
1991. THE WAR BEGAN
DETAILS OF DESTRYED E.T.S.
CROATIA
SARAJEVO
Kosovo
NATO ACTION 1999
KRAGUJEVAC
WAR
Bosnia - never again
Ourselves, our surroundings and help
Organisation Short name Mode of
contractor
name
RECETOX –
TOCOEN &,
Brno, Czech
Republic
RUDJER
BOSKOVIC,
Zagreb,
Croatia
Geological
Institute,
Zagreb,
Croatia
Main
investigator
Contractor
Prof.dr.
Ivan
Holoubek
RBIZ.CMR
Contractor
Dr. sc. M.
Picer,
Res.adv
GEOZGB
Dr. sc. S.
Subcontractor Kapelj, res.
assoc.
RECETOX
Institute of
Public Health,
Zadar, Croatia
University
Pristina, Faculty
of Science,
Pristina, Serbia
& Montenegro
IPHSZAD Subcontractor Z.Dmitrovic
B. Sc.
Dr. sc. T.
FSCPRI Subcontractor Arbneshi,
Docent
University of Novi
Sad, Faculty of
UNS.FS.IC Contractor Prof. dr. M.
Sciences Institute
Vojinovic
of Chemistry,
Serbia &
Miloradov
Montenegro
Univ. of Belgrade,
Faculty of Mining
FACMGBEO Subcontractor
and Geology,
Serbia &
Montenegro
Public Health
Institute of
Serbia, Centre for
Ecotoxicological PUBHIBEO Subcontractor
Diagnostic,
Belgrade, Serbia
& Montenegro
Geological survey, GEOSURV
Sarajevo, B&H
Dr. sc. I.
Matić
Dr.sc. D.
Djarmati,
Assoc.Prof
Contractor N. Miošić,
B.Sc
Environmental
Protection
IPHSI.EP.
Institute, Maribor,
HSA
Slovenia
Demokritos
University of
Thrace,
Faculty of
Engineering,
Xanthi Greece
Federal
Environment
Agency, Vienna,
Austria
Contractor Dr.sc. E.
Vončina
UTHR.DEE. Contractor Dr. sc. S.
Rapsomanikis
APL
UMB
Dr.sc. Martin
Contractor Kralik, Doc.
IPHSI.EP.HSA
RECETOX
UTHR.DEE.APL
UNI.FS.IC & SUB.
WP6
WP1
WP5
WP2
WP4
WP3
RBIZ.CMR & SUB
GEOSURV
UBM
IPHSI.EP.HSA
UMASA.RECETOX
WP2A
WP1
UMB
WP2B
RBIZ.CMR & SUBCONTRACTORS
GEOZGB
IPHSZAD
FSCPRI
WP2C
WP4A
GEOSURV
WP 5
UTHR.DEE.APL
WP6
UNS.FS.IC
IPHSI.EP.HSA
WP1
RECETOX
WP3A
WP3B
UNS.FS.IC &
SUBCONTRACTORS
FACMGBEO
PUBHIBEO
WP4A
RBIZ.CMR
WP 5
UTHR.DEE.APL
WORKPACKAGES AND COORDINATORS OF ACTIVITIES
• WP1: Intercalibration of some POPs
analysis in environmental samples (Phase
I and Phase II). Co-ordinator: Jana
Klanova, Czech Republic
Intercalibration crm nist standard
Fig ure 1: CRM NIS T
18,00
14,00
180
12,00
153
138
10,00
118
8,00
101
6,00
52
28
4,00
2,00
L.
CE
D
BH
EA
PU
UN
S.
FS
.
IC
AP
L
DE
E.
UT
HR
.
HS
A
IP
HS
I. E
P.
M
R
IS
.C
RB
SA
.R
EC
ET
O
X
UM
A
rti
fie
d
0,00
ce
ng/ml
16,00
Intercalibration crm SOIL
standard
Fig ure 2: CRM AS LAB
6000
p,p´-DDT
p,p´-DDE
Lindan
5000
180
153
138
101
52
28
3000
2000
1000
ce
rti
fie
d
SA
.R
EC
ET
O
X
RB
IS
.C
M
R
IP
HS
I.E
P.
HS
UT
A
HR
.D
EE
.A
PL
UN
S.
FS
.IC
PU
BH
EA
L.
CE
D
0
UM
A
ng/g
4000
WP2 : The level and hydrogeological fate of some
POPs in several Croatian, Bosnian & Herzegovina
and Kosovo areas as a consequence of war
damages: Co-ordinator: Mladen Picer, Croatia
• WP2a: The level and hydrogeological fate of
some POPs in several Croatian areas
• Co-ordinator: S. Kapelj, Croatia
• WP2b: The level and hydrogeological fate of
some POPs in several Bosnian & Herzegovina
areas: Co-ordinator: N. Miošić, Bosnia &
Herzegovina,
• WP2c: The level of some POPs in several
Kosovo areas. Co-ordinator: T. Arbneshi,
Kosovo
Soil sample points at Zadar electro trafostation
( 1 square is 1 m2:0 Zero point)
ETS ZADAR, ALL PCB data of samples without
sample from the hole
105
102
ZE
RO
30
25
20
15
18 16
14 12
10
10
8
DISTA
6
4
NCE F
2
ROM Z
0
ERO P
OINT (
m)
5
0
FR
O
M
101
PO
IN
T
(m
)
103
DI
ST
AN
CE
PCB (ng/g)
104
ETS Zadar, soil samples collected 2003 (7 + 6 +3)
RESEARCH
HOLE 2
C1
C2
C3
( 1,6 m depth)
RESEARCH 2 m
HOLE 1
4m
( 1,6 m depth)
1m
1,6 m
H1
H2
H3
LEVELS OF PCB IN SOIL SAMPLES FROM THE OUTER
RESEARCH HOLE
(ANALYSIS PERFORMED BY IPHSI.EP.HSA, MARIBOR)
1000
SUM 7 CONG.
PCB 28
PCB 52
LEVEL OF PCB CONGENERS
(mg/Kg) d.w.
100
10
1
0,1
0,01
0,001
0
0,2
0,4
0,6
0,8
DEPTH OF RESEARCH HOLE (m)
1
1,2
WP3: The level and hydrogeological fate of
some POPs in several FR Yugoslavian areas as
a consequence of war damages. Co-ordinator
I. Matić, Serbia and Montenegro
• WP3a :The level and hydrogeological fate of
some POPs in several Serbia areas. Co-ordinator
D. Djarmati, Serbia and Montenegro
• WP3b: The level and hydrogeological fate of
some POPs in several Vojvodina areas. Coordinator M. Vojinovic-Miloradov, Serbia and
Montenegro
PCBs
(ppm)
1 / 4,400
PCDD/Fs
(ppt)
74,000 / 10,200
4
3
2
1
A
• A-1
• B-4
• B-3
• B-2
• B-5
• C-1
Sewage collector
• B-1
B
C
D
Sampling locations : A-1(0.4 m), B-2(0.6 m), B1(0.2 m), B-4(0.4 m), B-3(0.2 m), B-5(1.0 m) and
C-1 (0.2 m)
Content of total PCBs in the sampling spots
4000
3500
3000
2500
ng/g
2000
1500
1000
500
0
(0.4 m) (0.2 m) (1.0 m) (0.2 m) (0.6 m) (0.2 m) (0.4 m)
A-1
B-1
B-5
C-1
B-2
Sampling spots
B-3
B-4
WP4 :The level and atmospheric transportation of some
POPs in Croatian, Bosnian & Herzegovina, and Serbian
& Montenegro areas as consequence of war damages.
Co-ordinator: Ivan Holoubek, Czech Republic
WP4a: The level and atmospheric transportation of
some POPs in Croatian, and Bosnian &
Herzegovina, areas. Co-ordinators: I. Holoubek
and M. Picer, Czech Republic and Croatia
• WP4b: The level and atmospheric transportation
of some POPs in FR Yugoslavian areas. Coordinators: S. Rapsomanikis and D. Djarmati,
Greece and Serbia&Montenegro
Air sampling campaign in Croatia
May 13-23, 2003, Zadar
Zadar – historical center
GPS: N 44°06’45,5“
E 15°13’43,3“
33 m
Zadar – Adria, industrial zone (kod CA)
GPS: N 44°05’47,6“
E 15°15’38,9“
1m
Zadar – transformer station between industrial and residential area
GPS: N 44°06’23,9“
E 15°15’48,9“
18 m
Zadar – meteorological station
GPS: N 44°07’48,3“
E 15°12’21,2“
6m
Air sampling campaign in Croatia
May 13-23, 2003, Zadar
PCBs levels in ambient air
0,250
3
7 PCB LEVEL(ng/m )
0,200
0,150
Zavizan
Meteo
Adria
Centre
0,100
0,050
-
1
2
3
4
DAYS
5
6
7
8
Centre
Adria
Meteo
Zavizan
9
10
Air sampling campaign in Croatia
May 13-23, 2003, Zadar
PCBs levels in ambient air
(ng/m3)
6,00
5,00
4,00
Zavizan
Meteo
Adria
Centre
Trafo
3,00
2,00
1,00
0,00
1
2
3
4
5
6
7
8
Trafo
Centre
Adria
Meteo
Zavizan
9
10
WP 5:
• Investigation of intake and some
ecotoxicological consequence of
exposure of living organisms to
POPs in some Serbian &Montenegro
and Croatian areas as consequence
of war damages. Co-ordinator: M.
Vojinovic-Miloradov, Serbia
&Montenegro
Interview questions
• Average consumption of total freshwater
fish (Kg/month) for all family
• Average consumption of total sea fish
(Kg/month) for all family
• Average consumption of total sea fish
hatched from Zadar coastal area
(Kg/month) for all family
• List three species of fish the most
consumables
• Name and profession of person who
made interview
FISH CONSUPTION OF 50 INTERVIEWED
FISHERMEN FAMILIES
7
CONS. T.F.
CONS. ZAD. F..
6
CROAT AVER.
5
4
3
2
1
NTERVIEWED FISHERMEN FAMILY
49
47
45
43
41
39
37
35
33
31
29
27
25
23
21
19
17
15
13
11
9
7
5
3
0
1
FISH CONSUPTION PER PERSON PER MONTH(kg)
8
Micro-EROD bioanalysis of soil samples (P-2, P-6) in primary
rat hepatocytes culture.
GC/ECD
PCBs:<0. 01
ppm
GC/ECD
PCBs:<0. 01
ppm
The EC25PCB126 value was calculated as the concentration giving 25% of the maximal induction caused by 10-8M of PCB126.
GC/ECD: according to six standard di-ortho congeners.
Induction potency of Pyralene (transformer oil) is given for comparison.
Significance: p*<0.05 vs control
Estimated EC25PCB126 and bioTEQ
EC25PCB126
Pyralene 0.84 µg / 0.1 ml
bio-TEQ
ng/g
107.84
P-2
64 mg / 0.1 ml
1.42
P-6
16 mg / 0.1 ml
5.71
Values were calculated using maximum
EROD activity in primary hepatocytes culture
induced by 10-8 M PCB 126
GC/ECD
PCBs: 4.5 ppm
GC/ECD
PCBs: 3.9 ppm
In spite that results obtained by
GC/ECD demonstrated absence of
PCBs in soil samples P-2 and P-6,
micro-EROD analysis indicates the
presence of relatively high amount
of EROD-inducing compounds in
the investigated samples (bio-TEQ
values 1.4 and 5.7 ng/g).
On the other hand, GC/ECD
demonstrated that sediment samples
(Z1-0.4, Z1-0.2) contained ppm
levels of PCBs, and in accordance
with that, micro-EROD analysis
indicate the presence of very high
amount of EROD-inducing
compounds in the investigated
samples. It suggest that besides
PCBs, some other dioxin-like
compounds are possible present in
the soil samples.
WP 6:
• Laboratory and field PCBs biotransformation
studies for remediation of soil contaminated by
transformer station oil-spill. Co-ordinator: D.
Hršak, Croatia
Enrichment of biphenyl-degrading
microbial communities
– microcosm enrichment approach was employed
– microbial growth was stimulated by incubating soil with
biphenyl
– top soil layer (0-5 cm) from PCB polluted sites were used:
- 7 samples at different positions of the transformer
station area
- 2 samples at Omišalj and Trogir airports, Croatia
– biphenyl-degrading bacteria were isolated on biphenyl-MM
agar plates
Figure 1.
Remaining congeners in PCB50 mixture (initial
concentration 50 ppm) after 14-day cultivation of
selected culture originated from airport soil,Trogir
AIR-TR
1.experiment 12.05.03
2.experiment 05.06.03.
100
90
% o f re main in g p e ak
80
70
60
50
40
30
20
10
0
1
2
3
4
5
6
7
8
9
10
11 12 13
14 15
16 17 18
19 20
21 22 23
24 25 26
p e ak
27 28
29 30 31
32 33
34 35 36
37 38
39 40 41
42 43
44 45 46
Figure 2.
Remaining congeners in PCB50 mixture (initial
concentration 50 ppm) after 14-day cultivation of
selected culture originated from power substation
soil, Zadar
TSZ7
2.experiment 05.06.03.
1.experiment 12.05.03.
100
90
80
70
60
50
40
30
20
10
0
1
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46
pe ak
LABORATORY REMEDIATION
EXPERIMENT- BOTTLES
LABORATORY REMEDIATION
1) CONTROL
(STERILIZED SOIL
TSZ)
2) BACT.TSZ-2
3) BACT.TSZ-6
4) BACT.TROGIR
5) BACT.OMIŠALJ
6) AUTOCHTONE
BACTERIES IN TSZ
SOILS
LABORATORY REMEDIATION
EXPERIMENT ON ETS ZADAR SOIL SPIKED
WITH 100 PPM AROCLOR 1248
140
100
EXT I
EXT II
SOXH
80
SUM(MEAN)
X
AROCLOR 1248 IN SOIL (mg/kg)
120
SUM
60
40
20
0
K I
K II
CONTROL
1 I
1 II
2 I
2 II
3 I
3 II
4 I
4 II
5 I
5 II
BACT.TSZ-2 BACT.TSZ-6BACT.TROGIR
BACT.OMIŠALJ
AUTOCHTONE
MODE OF LABORATORY REMEDIATION PROCESS
TAKE AWAY THE MOST POLLUTED
(WE HOPE) SOIL
EXPERIMENTAL FIELDS (PHASE
II –FILLING THE OPEN BOXES)