Distribution of organotin compounds in aquatic environment

1
Distribution of organotin compounds in aquatic
environment
Hiroya Harino
Osaka City Institute of Public Health and
Environmental Sciences
2
Ph
Bu
Sn
Ph
X
Bu
X
Sn
Bu
Ph
X
X
Ph
Bu
(TPT)
(TBT)
Sn
Ph
X
Sn
Bu
X
Sn
Ph
X
Sn
Bu
X
X
X
X
X
(MBT)
(DBT)
(MPT)
(DPT)
Phenyltin compounds
Butyltin compounds
(Pts)
(Bts)
Organotin compounds
3
A9
Yodo R.
Osaka
A1
A2
Osaka City
A3
A4
A7
A6
Kizu R.
A5
A8
Osaka Bay
2
1
3km
0
Sampling sites (The Port of Osaka, Japan)
4
Aquatic organisms(1-10g)
Water (1L)
Sediment (10g)
HCl
HCl
HCl
Acetone
Acetone
Acetone
Benzene containing 0.1 tropolone
Extract
Homogenate
Centrifugation at 3000 r.p.m
Centrifugation at 3000 r.p.m
Extract
Supernatant
Supernatant
Concentration
Distilled water
Distilled water
Propyl magnesium bromide
Benzene containing 0.1 tropolone
Benzene containing 0.1 tropolone
Propylation
Distilled water
Extract
Extract
Hexane containing 10benzene
Tetrabutylhydrogen sulfate
Extract
Sodium sulfite
Desulfur
Frorisil column chromatography
GC - FPD
Analytical method of organotin compounds
5
Objects
Temporal trend of organotin compounds in water,
sediment and biological samples from the Port of
Osaka
Current status of organotin compounds in water,
sediment and biological samples from the Port of
Osaka
Partition of organotin between water and the
other compartments
6
Table Events for organotin compounds in Japan
Year
Events
Jan. 1990
TBTO was designated as a Class 1 Specified
Chemical Substance.
Seven TPT species were designated as Class 2
Specified Chemical Substances.
Thirteen TBT species were designated as a Class
2 Specified Chemical Substances.
Sep. 1990
Environment Agency set guideline. Ots
concentration in the area within 100m from source
on ones was under 0.1?g/l and that in the other
area was 0.01?g/l.
7
(?g/l)
()
0.3
100
A2
MBT
DBT
TBT
A2
80
max
0.2
1.04
60
Concentration of TBT
Composition of Bts
40
0.1
20
0
0
1992
1994
1996
1989
1990
1991
1992
1993
1994
1995
1996
1990
1991
1993
1995
1989
100
0.3
A4
A4
80
0.2
60
Concentration of TBT
40
Composition of Bts
0.1
20
0
0
1989
1990
1991
1992
1993
1994
1995
1996
1990
1992
1994
1996
1991
1993
1995
1989
0.3
100
A8
A8
80
0.2
60
Composition of Bts
40
Concentration of TBT
0.1
20
0
0
1990
1991
1992
1993
1994
1995
1996
1990
1992
1994
1996
1991
1993
1995
Year
Year
Temporal trend of butyltin compounds in water
8
(mg/kg dry wt)
()
100
2.5
A2
A2
MBT
DBT
TBT
80
2
60
Concentration of TBT
1.5
Composition of Bts
40
1
20
0.5
0
0
1990
1991
1992
1993
1994
1995
1996
1992
1994
1996
1990
1991
1993
1995
100
2.5
A4
A4
80
2
Composition of Bts
60
1.5
Concentration of TBT
40
1
20
0.5
0
0
1990
1991
1992
1993
1994
1995
1996
1994
1996
1990
1992
1991
1993
1995
Year
Year
Temporal trend of butyltin compounds in sediment
9
(mg/kg dry wt)
()
100
10
MBT
DBT
A4
A4
80
8
TBT
6
60
Concentration of TBT
Composition of Bts
40
4
2
20
0
0
1989
1990
1991
1992
1993
1994
1995
1996
1992
1994
1996
1990
1991
1993
1995
1989
100
10
A5
A5
80
8
60
Composition of Bts
6
Concentration of TBT
40
4
20
2
0
0
1989
1990
1991
1992
1993
1994
1995
1996
1994
1996
1990
1992
1991
1993
1995
1989
Year
Year
Temporal trend of butyltin compounds in plankton
10
( mg/kg wet wt)
()
100
1.5
Max 2.4
A2
MBT
DBT
TBT
A2
80
1
60
Concentration of TBT
Composition of Bts
40
0.5
20
0
0
1989
1990
1991
1992
1993
1994
1995
1996
1990
1992
1994
1996
1991
1993
1995
1989
100
1.5
A5
A5
80
1
60
Composition of Bts
Concentration of TBT
40
0.5
20
0
0
1989
1990
1991
1992
1993
1994
1995
1996
1990
1992
1994
1996
1991
1993
1995
1989
100
1.5
A8
A8
80
1
60
Composition of Bts
Concentration of TBT
40
0.5
20
0
0
1992
1994
1996
1990
1990
1991
1992
1993
1994
1995
1996
1991
1993
1995
Year
Year
Temporal trend of butyltin compounds in mussel
11
(mg/kg wet wt)
2.0
A2
1.5
1.0
Concentration of TPT
0.5
0
1990
1992
1994
1996
1989
1991
1993
1995
Year
2.0
A5
1.5
1.0
Concentration of TPT
0.5
0
1990
1992
1994
1996
1989
1991
1993
1995
Year
Temporal trend of triphenyltin in mussel
12
(mg kg-1 wet)
(mg kg-1 wet)
0.1
0.15
Phenyltins
Butyltins
0.08
0.1
Concentration
Concentration
0.06
0.04
0.05
0.02
0
0
1991
1993
1995
1997
1999
1991
1993
1995
1997
1999
1992
1994
1996
1998
1992
1994
1996
1998
Butyltin and phenyltin compounds in fish from the
Port of Osaka
Tri-
Di-
Mono-
13
(
µ
g/l)
(mg/kg dry)
0.05
5
Water
Plankton
0.04
4
0.03
3
Concentration of TBT
Concentration of TBT
0.02
2
0.01
1
A3
A4
A5
A6
A7
A8
A1
A2
A3
A4
A5
A6
A7
A8
A1
(mg/kg dry)
(mg/kg wet)
0.5
2.5
Mussel
Sediment
2
0.4
1.5
0.3
Concentration of TBT
Concentration of TBT
1
0.2
0.5
0.1
0
A3
A4
A5
A6
A7
A8
A1
A2
A8
A5
A2
Current status of tributyltin in the Port of Osaka
14
Plankton
Sediment
Water
A1
A1
A1
A3
A2
A2
A4
A3
A3
A5
A4
A4
A6
A5
A5
A7
A6
A6
A8
A7
A7
A8
A8
0
50
100
0
50
100
0
50
100
Mussel
A2
A5
A8
0
50
100
Composition of butyltin compounds in water,
sediment, plankton and mussel
MBT
DBT
TBT
15
A9
Yodo R.
Osaka
A1
A2
Osaka City
A3
A4
A7
A6
Kizu R.
A5
A8
Osaka Bay
2
1
3km
0
Sampling sites (The Port of Osaka, Japan)
16
(mg/kg wet wt.)
0.2
0.15
TBT
Concentration
0.1
TPT
0.05
0
File fish
Bluegill
Habitat
Tributyltin and triphenyltins in various fish
17
Phenyltin compounds
Butyltin compounds
MPT
DPT
TPT
MBT
DBT
TBT
Silver whiting
White croaker
Triped pufer
Japanese sea perch
Triped pufer
Bandfish
White croaker
Yellowtail
Silver whiting
Yellowtail
Butter fish
File fish
Japanese sea perch
Bandfish
Butter fish
File fish
Bluegill
Bluegill
Japanese barbel
Japanese barbel
Gray mullet
Gray mullet
50
100
0
50
100
()
0
()
Composition
Composition
Composition of butyltin and phenyltins in various
fish
18
(mg/kg wet wt.)
0.5
Japanese sea perch
TBT
0.4
Concentration
0.3
0.2
TPT
0.1
0
Spleen
Kidney
Muscle
Brain
Gonad
Gill
Heart
Stomach
Liver
Scale
(mg/kg wet wt.)
0.3
White croaker
Concentration
0.2
0.1
0
Liver
Brain
Muscle
Kidney
Spleen
Gill
Stomach
Skin
Gonad
Heart
Vertebra
Scale
(mg/kg wet wt.)
0.3
Yellowtail
Concentration
0.2
0.1
0
Liver
Brain
Muscle
Kidney
Stomach
Spleen
Heart
Gill
Scale
Skin
Vertebra
Body distribution of tributyltin and triphenyltin
in fish
19
()
()
100
100
MPT
MBT
DPT
80
80
DBT
TPT
TBT
60
60
Composition of PTs
40
40
Composition of BTs
20
20
0
0
Japanese sea perch
Yellowtail
Japanese sea perch
Yellowtail
White croaker
White croaker
Composition of butyltin and phenyltin compounds
in liver
20
Partition coefficients of Bts
0
2
4
6
10
10
10
10
MBT
DBT
Sediment
TBT
MBT
DBT
Plankton
TBT
MBT
Mussel
DBT
TBT
Partition of butyltin compounds
21
Table Bioconcentration factor of fish samples
Sampling
Number of
BCF
Specimen
locality
sample
(means)
Japanese sea perch
Station A5
3.7
2
White croaker
Station A5
3.7
2
Yellowtail
Station A5
3.8
2
Station A5
3.8
2
Bandfish
Silver whiting
Station A5
3.9
3
Butter fish
Station A5
3.7
3
Station A5
3.3
1
File fish
Station A5
3.8
1
Triped puffer
Gray mullet
Station A8
2.7
2
Japanese barbel
Station A8
3.0
3
Bluegill
Station A8
3.1
3
22
Conclusion
Temporal Trend of TBT
Waterdecreasing, Sedimentuniformity,
Planktondecreasing, Musseldecreasing,
Fishdecreasing
Current status of OTs
Water Concentration of TBT was above 1ng l-1.
Sediment Higher level of TBT was detected.
Fish TBT and TPT were detected.
Partition of TBT to sediment and biological
samples
Sediment 4.6, Plankton 5.2, Mussel 4.1,
Fish 3.7