Turkish J. Marine Sciences 3 (3): 137-148
Identification of Phthalate Esters Pollution in the
Bosphorus and Dardanelles
istanbul ve <;anakkale Bogazmda Ftalat Esterleri
Kirliliginin Tayini
Kas1m Cerna! Giiven, Selma Unlii, Erdogan Oku~,
Ertugrul Dogan and Tuncay Gezgin
University of Istanbul, Institute of Marine Sciences and Management,
Vefa 34470 Istanbul, Turkey
Abstract
Pthalate esters are used in various industries. They are toxic for marine organisms and are
general contaminants. Phthalate esters were investigated in seawater of the Bosphorus and
Dardanelles during 1995 and 1996. The detections were made by using GC/MS analysis
and identified phthalate esters were: DEP, BP, DBP and DEHP. The same phthalate esters
were found at the entrance and exit of both straits with some variations in months.
Keywords: Phthalate esters, Bosphorus, Dardanelles, seawater
Phthalic acid is a benzene dicarboxylic acid. Its ortho (o-), meta (m-) and
para (p-) derivativees are very important for many industries. They are
used as alkyd resins, polymeric polyesters, drying/non- drying oils,
plasticizers for dyes and fibers etc. The largest amounts of the a-phthalic
acid esters are: di methyl (DMP), diethyl (DEP), di-n-butyl (DBP), di (2ethylhexyl) ester (DEHP), di amyl, diallyl. They are used as plasticizers,
parfume fixatives and alcohol denaturants, in preparation of various
classes of dyes and intermediates and also as insecticides. m-Derivatives
of phthalic acid esters are used in alkydresins, dyes, fibers, sheet, surface
coating, film and molding industries. p-Derivative, terephtalic acid esters
are used synthetic textiles, polyster films and plasticizing industries.
Industries produce approximately more than billion tonnes of over 25
different phythalete compounds. The increase in utilization of these esters
has resulted in widespread contamination of natural and human
environment and therefore the conceq1 of investigator has been focussed
on the topic. They have been found complexed with the fulvic acid
components of humic substances in seawater. Fulvic acid apparently
137
functions as solubilizer for other insoluble phthalate esters and thus serves
to mediate the mobilization, transport and immobilization of these
compounds in soil and water.
Phthalate esters were detected in sea water (Giam et a/.1978; Preston and
AI-Omran 1986; Sullivan et a/.1982; Sullivan eta/., 1982; Ernst. 1983;
Tan 1995; Waldock 1983) DEHP in surface water ranged from 4.9-!30
ng/L, DBP ranged from a nondetectable level to 95 ng/L. The amount of
phthalate esters found in sea were fish (3.2 mg/kg) (Stalling eta/. 1973).
in Atalla (Morris, 1970) and shrimp, (Laughlin et a/.1978)
The toxicity and carcinogenicity of phthalates were discussed by various ·
authors. Phthalic acid causes allergic symptoms in humans. Its anhydride
causes corneal burns, from which eyes must be protected. Its odor is
found to be disagreable and have a choking effect.
Mutagenecity (Kozumbo et al., 1982), teratogenicity and fetotoxicity
(Tomita et a/., 1982; Dullingan and Austian, 1973), effect on the
reproduction of Daphnia magma (Brown and Thompson 1982)
physiological disturbance on fresh water amphipod, Gammarus pulex
(Thuren and Voin, 1991) reduce hatching success from brine shrimp
(Giam eta/. 1978).
The first record on the pollution of phthalate in Turkish coasts was the
findings of terephthalic acid dimethyl ester (DMT) in the Black Sea algae
(Giiven et at., 1990).
Thus phthalate esters are recognized as general contaminants of water
ecocystems.
Various methods were used for the determinaiton of phthalate esters as:
GC (Tan, 1995; Takeshita et al., 1977), GC/MS Sjoberg and Bondenson,
1985); GC/MS (Sherma, 1991; Leung and Giang, 1993; Waldeck, 1983
and HPLC (Anon.).
A comprehensive account on the phtha1ates determination was published
by Fichbein and Albro ( 1972).
This paper reports the pollution of the Bosphorus and Dardanelles
seawater by phthalate esters in 1995 and 1996.
138
Material
Seawater samples were taken at the northern entrance and southern exit of
Bosphorus (B I ,B2) and Dardanelles (D I ,D2) (Fig. I).
2.8 L seawater sample was taken in brown a bottle and 25 ml
dichloromethane (DCM) was added for preservation.
0
0 1 2 3 4 5 k;n
139
Methods
I. Seawater
4x700 ml, totaling 2.8L, seawater samples were extracted with 25m!
DCM. The extracts were combined and distilled under vacuum. The
residue was taken with hexane and analysed by GC/MS.
2. GC-MS analyses
GCIMS analyses were run on a HP 6890 capillary GC connected to a
Hewlett Packard Mass Selective Detector (MSD), contolled by a HP
Chemstation. Operating conditions were; 50.0 mx0.50J.tm i.d. fused HP
PONA, Methyl siloxane, glass capillary column; oven temperature
programme: 40°C at 7 min, from 40-150°C at !5°C min, 150°C at 5 min,
from 150-280°C at !5°C min, 280°C at 5 min, from 280-290°C at l0°C
min, 290°C at 15 min. Splittless injector temperature 250°C, carrier gas
helium, flow 1.0 ml!min, 29.4 psi. press.
Results and Discussion
The detected phthalates in seawater are ; DEP: diethyl phthalate, BP: nbutyl!lsobutyl phthalate, DNP: di-n-butyl phthalate, DEHP: di-ethylhexyl
phthalate and tabulated in test stations in Table I.
GCIMS apparatus was controlled with hexane (HPLC grade) before each
test. Thus the mistake on the phthalates that might come from the septum
was discarded.
There seems to be no regularity in the presence of phthalates in samples
regarding the stations and times indicating that the pollution by phthalates
is irregu Jar.
The selected GC/MS chromatograms of examined seawater are shown in
Fig.2-6. GC/MS spectra of the samples and the related spectra taken from
the memory of the instrument are shown in Fig.?-10.
Some phthalate esters were found at the entrance and exit of both straits,
with some variations in months.
The phthalate pollution at 10m depth of the Bosphorus were found higher
than at surface water.
Similar phthalates were found in the southern exit of the Bosphorus as in
the n01them entrance of the Dardanelles. This fact is considered
significant and will be wade a point for further investigation.
It is hereby concluded that the Turkish Straits are also victim of pollution
by phthalates as the world seas are in general.
140
BP
DEP
Phthalates
~
DEHP
DNP
! .
e
n
May 1995
June 1995
Juily 1995
Sept. 1995
Oct. 1995
Dec. 1995
April 1996
June 1996
Agust 1996
Oct. 1996
Nov. 1996
Dec. 1996
Bl
-
Bl
Dl
D2
Bl
D2
-
X
X
B2
+
D2
X
Bl
+
Dl
X
82
+
Dl
-
X
X
X
X
-
-
X
X
+
+
X
X
-
+
+
+
+
-
-
+
+
+
+
-
-
+
+
X
Bl
+
B2
+
Dl
D2
X
X
X
X
-
-
+
+
+
+
X
X
-
-
X
X
-
-
X
X
-
-
X
X
X
X
+
+·
X
X
+
+
X
X
+
+
X
X
+
-
-
-
+
-
-
+
+
+
-
+
X
X
-
-
-
X
+
-
+
X
X
-
-
X
X
-
-
X
X
-
-
X
X
+
+
X
X
+
+
X
X
-
-
X
-
X
X
X
+
X
X
X
+
X
X
X
X
-
-
-
+
+
+
+
+
+
+
+
X
X
X
X
+
+
+
+
+
+
+
+
+
+
-
+
+
+
+
-
+
+
+
+
X
X
+
-
-
-
X
-
-
-
-
Table 1. Phthalate pollution of surface water of the Bosphorus and Dardanelles
B I Northern entrance of the Bosphorus, 82: Southern exit ofthe Bosphorus
Dl: Northern entrance of the Dardanelles, D2: Southern exit of the Dardanelles
DEP: diethyl phthalate, BP: n-butylilsobutyl phthalate, DNP: di-n-butyl phthalate, DEHP: di-ethylhexyl phthalate
.
+ : detected, - : Not detected, x : Not tested
-
fj
DEP
Phthalates
~
BP
DNP
DEHP
e
n
July 1995
Agust.l995
Sept. 1995
Oct. 1995
Nov. 1995
Sept. 1996
Oct. 1996
Nov. 1996
Bl
B2
X
X
Dl
+
D2
+
Bl
B2
X
X
Dl
+
D2
+
Bl
B2
X
X
Dl
+
D2
+
Bl
B2
X
X
Dl
+
D2
+
+
X
X
X
-
X
X
X
-
X
X
X
-
X
X
X
X
+
X
X
X
+
X
X
X
+
X
X
X
-
X
X
+
X
+
+
-
X
+
+
-
X
+
+
-
X
+
+
X
+
X
X
X
+
X
X
X
+
X
X
X
+
X
X
X
X
-
X
X
-
X
X
-
X
-
X
X
X
X
X
X
X
X
X
X
X
+
+
+
+
X
+
+
-------------
+
+
X
-
+
+
X
X
X
X
X
-
X
X
-
-
Table 2. Phthalate pollution of on l 0 m depth of the Bosphorus and Dardanelles
B l Northern entrance of the Bosphorus, B2: Southern exit of the Bosphorus
Dl: Northern entrance of the Dardanelles, D2: Southern exit of the Dardanelles
DEP: diethyl phthalate, BP: n-butyll!sobutyl phthalate, DNP: di-n-butyl phthalate, DEHP: di-ethylhexyl phthalate
+ : detected, - : Not detected, x : Not tested
-----
+
+
X
4
3
3
JO ..... 22 00.
Fig.~:
24.00
26.00
.??00 ... }OC
GC/MS chromatogram of B 1
station at surf<tcc water in 1995.
Fig.3. GC/MS chromatogram of B2
station at surface water in 1995.
4
3
J.oo ..
Fig.4. GC/MS chromatogram of B2
Station at surface water in 1996.
1-DEP, 2-BP, 3-DNP. 4-DEHP
143
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32:
Fig.6. GC/MS chromatogram of D2 station at surface water in 1995.
1-DEP. 2-BP, 3-DNP, 4-DEHP
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Fig.?. GC/MS spectra of DEP in surface water at station D2.
(a) Spectrum for sample, (b) Spectrum taken from HP memory.
144
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Fig.8. GC/MS spectra of BP in surface water at station B2.
(a) Spectrum for sample, (b) Spectrum taken from HP memory.
145
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Fig.9. GC/MS spectra of DBP in surf~cc water at station B I.
(a) Spectrum for sample, (b) Spectrum taken from HP memory.
146
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(a) Spectrum for sample, (b) Spectrum taken from HP memory.
Ozct
Fta!atlar degi~ik sanayidc kul!anllan 1\alik asit dcrivclcridir. Bunlar yaygm olarak
kullanlidtklanndan ycvrc i\!in kirlctici rQl oynarlar. Bu maddclcr can!Jiar i.izcrine degi~ik
toksik ctkiyc sahiptirlcr. Bunlann dcniz suyunda ve canlllannda tcspitinc ait bir 90k yaym
var(l!r. Bu <;ah~n1ada 1995-1996 y!lmda istanbul Bogazt ve <;anakkale Bogazt deniz
suyunda lialat estcr!crinin tcspitinc ait bu!gular veri!mi~tir. Tayinlcr GC/MS aktindl':
yaptl!m~tlr. Tcsbit edilen Jlalat csterlcri
DEP. BP. DBP. DEI·JP'dir. Farkh aylarda baz1
degi~melerlc her iki bogazm giri:;; vc ytkl_~mda ay111 na!at csterlcrinc rastlanmt~t1r.
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disposable extraction column. J. Baker. U.S.A.
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i111
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Received 3.2.1997
Accepted 17,3,1997
148
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