Ministry of Ecology and Natural Resources of Ukraine
Ukrainian Scientific Centre of Ecology of Sea
Polycyclic aromatic hydrocarbons in bottom
sediments of the Danube estuarine coast
K.K. Tsymbaliuk, Y.M. Denga, N.A. Berlinsky, V.P. Antonovich
Actuality of determination of polycyclic
aromatic hydrocarbons
According to the different international agreements around
60 chemicals were included in the lists limiting their
distribution and the mandatory control of the content in the
environment. A group of persistent organic pollutants
(POPs) was called as a "dirty dozen", in particular: aldrin,
endrin, dieldrin, mirex, DDT, hexachlorobenzene,
heptachlor,
toxaphene,
chlordane,
polychlorinated
biphenyls, dibenzo-p-dioxins and dibenzofuranes. United
Nations Organization/UN in 2003 , within the project aimed
at the assessing the POP’s threat to the environment and
human health, recommended 16 priority polycyclic aromatic
hydrocarbons (PAHs) as well as six esters of phthalate
acid be included in the list of controlled chemicals.
Polycyclic aromatic hydrocarbons
PAHs are limited volatile
persistent
organic
pollutants
which
are
featured by carcinogenic,
mutagenic,
teratogenic
and hepatotoxic effects.
They are able to be
accumulated
in
lipid
tissues
of
living
organisms and to provoke
various serious diseases..
Determination of PAHs in sediments
For PAHs determination in sediments was used our advanced
liquid-extraction procedure for extraction of target compounds in the
Soxhlet extractor. Determination of PAHs was by gas
chromatography with mass selective detection using selective ion
monitoring at GC / MS Agilent 7890A/5975C.
Procedure of PAHs determination
GC-MS
Sediment sampling
Freeze drying
Sohxlet extraction with the
addition of elemental copper
Fractionation on column with
SiO2 and Al2O3
Evaporation of eluate to
1 cm3 under nitrogen flow
Conditions of GC/MS
Injector
splitless
Injection volume
1 µl
Injector temp.
300°С
Velocity
1,0 см3/min
Column
HP-5MS (30m, 0.25mm 0.25 µm)
First temp.
Heating rate
Isotherm
Heating rate
Isotherm
Oven program
70°С, 1 min
10°С∙min-1
120°С, 1 min
7°С∙min-1
270°С, 10 min
MSD parameters
Ionization
E+, 70 eV
method of data acquisition SIM
Interface temp.
280°С
Ion source temp.
230°С
Chromatogram of real sample
Quality control
The international standard sample of bottom sediments SRM IAEA – 383 with the
certified content of PAHs was used to confirm the accuracy control of the obtained
results.
Scheme of stations for the sampling of
sediments at the Danube estuarine coast
The results of GC/MS determination of PAHs in bottom
sediments of estuarine coast of Danube
Ratio of 16 PAHs in the bottom sediments of Danube estuarine by
the number of rings in molecule (the number of stations is located
along the vertical axis; the PAHs percentage of on the number of
rings is located along abscissa)
Levels of bottom sediments pollutions from the Danube
estuary, the sum of 16 PAHs, by 7 carcinogenic PAHs and
total B(a)Peqv.
Values of the ratio Fl/Fl +Py, BaA/228, IP / IP+ BghiP, An/178 for stations of
estuarine coast of Danube
Comparison of PAH content with the maximum
allowable concentration (Netherlands)
Conclusions
 The results of research can be indicators of anthropogenic press to
the shalom waters in The Danube area as an emission of industrial
and municipal waste and economic activity of the ports and
dumping.
 Obtained ratio of Fl / Fl+Py, An/178, IP/IP+BghiP, BaA/228 typical for
anthropogenic PAHs, except for stations 7 and 9.
 At station number 8 ratio Fl / Fl+Py, An/178, IP/IP+BghiP, BaA/228
and total PAHs index differ significantly from those values for other
stations that may indicate another source of contamination at this
station.