Ministry of Ecology and Natural Resources of UkraineMinistry of Ecology and Natural Resources of Ukraine

Ukrainian Scientific Centre of Ecology of SeaUkrainian 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 Actuality of determination of polycyclic aromatic hydrocarbonsaromatic 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 sedimentsDetermination of PAHs in sediments

For PAHs determination in sediments was used our advanced For PAHs determination in sediments was used our advanced liquid-extraction procedure for extraction of target compounds in the liquid-extraction procedure for extraction of target compounds in the Soxhlet extractor. Determination of PAHs was by gas Soxhlet extractor. Determination of PAHs was by gas chromatography with mass selective detection using selective ion chromatography with mass selective detection using selective ion monitoring at GC / MS Agilent 7890A/5975C.monitoring at GC / MS Agilent 7890A/5975C.

Procedure of PAHs determinationProcedure of PAHs determination

Sediment sampling

Freeze drying

Sohxlet extraction with the addition of elemental copper

Fractionation on column with SiO2 and Al2O3

GC-MS

Conditions of GC/MSInjector splitlessInjection volume 1 µlInjector temp. 300°СVelocity 1,0 см3/minColumn HP-5MS (30m, 0.25mm 0.25 µm)

Oven program First temp. 70°С, 1 minHeating rate 10°С∙min-1

Isotherm 120°С, 1 minHeating rate 7°С∙min-1

Isotherm 270°С, 10 min

MSD parametersIonization E+, 70 eVmethod of data acquisition SIMInterface temp. 280°СIon source temp. 230°С

Evaporation of eluate to1 cm3 under nitrogen flow

Chromatogram of real sampleChromatogram of real sample

Quality controlQuality 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 Comparison of PAH content with the maximum allowable concentration (Netherlands)allowable concentration (Netherlands)

ConclusionsConclusions

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 Obtained ratio of Fl / Fl+Py, An/178, IP/IP+BghiP, BaA/228 typical for anthropogenic PAHs, except for stations 7 and 9.anthropogenic PAHs, except for stations 7 and 9.

At station number 8 ratio Fl / Fl+Py, An/178, IP/IP+BghiP, BaA/228 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 and total PAHs index differ significantly from those values for other stations that may indicate another source of contamination at this stations that may indicate another source of contamination at this station.station.