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Ministry of Ecology and Natural Resources of Ukraine Ukrainian Scientific Centre of Ecology of Sea

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.

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Ministry of Ecology and Natural Resources of Ukraine Ukrainian Scientific Centre of Ecology of Sea

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  1. Ministry of Ecology and Natural Resources of UkraineUkrainian Scientific Centre of Ecology of Sea

  2. Polycyclic aromatic hydrocarbonsinbottomsedimentsoftheDanubeestuarinecoast K.K. Tsymbaliuk, Y.M. Denga, N.A. Berlinsky, V.P. Antonovich

  3. 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.

  4. Polycyclic aromatic hydrocarbons • PAHsarelimitedvolatilepersistentorganicpollutantswhicharefeaturedbycarcinogenic, mutagenic, teratogenicandhepatotoxiceffects. Theyareabletobeaccumulatedinlipidtissuesoflivingorganismsandtoprovokevariousseriousdiseases..

  5. 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.

  6. Procedure of PAHs determination Sediment sampling GC-MS 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) Oven program First temp. 70°С, 1 min Heating rate 10°С∙min-1 Isotherm 120°С, 1 min Heating rate 7°С∙min-1 Isotherm 270°С, 10 min MSD parameters Ionization E+, 70 eV method of data acquisition SIM Interface temp. 280°С Ion source temp. 230°С 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

  7. Chromatogram of real sample

  8. Quality control Theinternationalstandardsampleofbottomsediments SRM IAEA – 383 withthecertifiedcontentofPAHswasusedtoconfirmtheaccuracycontroloftheobtainedresults.

  9. Scheme of stations for the sampling of sediments at the Danube estuarine coast

  10. Theresultsof GC/MS determinationofPAHs inbottomsedimentsofestuarinecoastofDanube

  11. Ratioof 16 PAHsinthebottomsedimentsofDanubeestuarinebythenumberofringsinmolecule (thenumberofstationsislocatedalongtheverticalaxis; thePAHspercentageofonthenumberofringsislocatedalongabscissa)

  12. LevelsofbottomsedimentspollutionsfromtheDanubeestuary, thesumof 16 PAHs, by 7 carcinogenicPAHsandtotal B(a)Peqv.

  13. ValuesoftheratioFl/Fl +Py, BaA/228, IP / IP+ BghiP, An/178 forstationsof estuarinecoastofDanube

  14. Comparison of PAH content with the maximum allowable concentration (Netherlands)

  15. 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.

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