PLETENEV S.S., LAPSHIN V.B., GONCHARUK V.V.*, KOLESNIKOV M.V., SMIRNOV A.N., SYROESHKIN A.V .

1. PLETENEV S.S., LAPSHIN V.B., GONCHARUK V.V.*, KOLESNIKOV M.V., SMIRNOV A.N., SYROESHKIN A.V. THE GLOBAL NOVEL TRANSBOUNDARY SOURCE OF COASTAL ECOSYSTEMS’ POLLUTION: METHODS OF MONITORING AND MINIMIZATION OF DAMAGE TO HUMAN HEALTH OF THE SEA MEGAPOLISES State Oceanographic Institute Moscow Russia

2. Contents of Presentation • Overview of State Oceanographic Institute • Noveltransboundary source of coastal ecosystems’ pollution • The mechanisms of marine aerosols formation • The mechanisms of SML enrichments by pollutants • Pollution of marine aerosols by heavy metals, arsenic and oil hydrocarbons (Russian part of Black sea) • The methods (routine and new ones) for monitoring of noveltransboundary source of coastal ecosystems’ pollution • The methods and approaches for minimization of damage to human health of the sea megapolises

3. State Oceanographic Institute (SOI) • Total staff number – 140 persons. Total scientists / engineers number – 120 persons. • The Year of establishment – 1943. • Main research technologies fields: marine and costal environmental monitoring (including monitoring of pollution), marine hydrology and marine hydrometeorology, mouth and estuary hydrochemistry and hydrology monitoring, satellite observation. • SOI is the head marine institute in the research and environmental control system of the Russian Federal Service for Hydrometeorology and Monitoring of the Environment.

4. Excellent research achievements of SOI • The discovery of the novel global transboundary source of coastal ecosystems’ pollution (the theme – “Toxicity of marine aerosols”) and development of the new approaches for monitoring for minimization of damage to human health of the sea megapolises • The unabridged edition of in many volumes the full descriptions of Russian sea (meteorology, hydrology, hydrochemistry, pollution, conditions for marine bioproductivity) • The discovery of existing in water solutions the giant heterophase clusters of water • The creation of methods for frog condensation and dissipation • The creation of approaches for prevention of the icing up of roves • The observation of the new aspects of solar corpuscular radiation influence on Earth global climate • The development and application of new model for description of evolution of marine and coastal oil spills.

5. Structure of SOI Director Academic council Deputy Director Deputy Director Lab of applied hydrochemistry and analytical chemistry Deputy Director Lab of pollution databases Depart. of metrology Lab of marine estuary Lab of satellite and subsatellite observation Lab of ebb and flow Lab of hydrology Group of Anal. Chem. “Water” Group Engineer. service Lab of waves Group of marine aerosols Group of fogs and icing Lab of monograph’s preparation Group of water toxicity Council for Ph.D. thesis and thesis for a Doctor's degree (oceanology, geoecology)

6. Chemical Lab of SOI Collaboration in Black sea researches (2002-2005)Financial supporting: Russian Foundation for Basic Researches (RFBR), Federal programme “World Ocean” (through IORAS), UNDP projects Institute of Oceanology, RAS RPFU, Medical faculty State Centre for hydrometeorology (SOCHI, “ЦГМС ЧАМ”) Research centre for Toxicology, Russian ministry of health (Serpuhov)

7. Noveltransboundary source of coastal ecosystems’ pollutionReverse flux column water - sea surface microlayer (SML) - aerosols

11. Heavy metals, Al, As in marine aerosols of Black, Mediterranean and White sea ng per m3

12. Heavy metals, Al, As in marine aerosols of Black, Mediterranean and White sea

13. The mechanisms of marine aerosols formation:1) bubbles breaking,2) direct wind-waves interaction,3) spontaneously aerosols generation by undisturbed water’s surface

15. Surface microlayer (SML) • Gas emissions from bottom sediments • Gas emissions from living organisms • Waves breaks and “wind’s capture” • Chemical composition of aerosols is similar to SML • A large drop return to surface • Small drops (aerosols) may be captured by wind flow

16. The mechanisms of SML enrichments by pollutants

17. Mechanisms of SML chemical composition formation • Routine Langmuir enrichment of phase boundary (water-air) by SAC and hydrophobic compounds including detergents and oil hydrocarbons • Enrichment due to convections of particle matter. The type of convection is depended on type of particles (size, form, charge etc). Particles usually contain different toxicant (heavy metals, As, biotoxins, oil etc.) • These processes result in high • *concentration of pollutants in SML • *non-stationary multilayers structure

18. The main types of convections in SMLRayleigh’s convection Anisotropy heterogeneous convection “Driving forces”of convections: DT DE Thermal neutrons flux

21. The structure of column water The visualization of water structure (mode 2 of the laser device) 2x2 mm • The fundamentals of new LALS application – the existence of giant clusters of water The image of water The image of ddw Size spectra of giant clusters of water

23. The example of Sea Surface Microlayer (SML) fine structure analyzes and toxic marine aerosols generation

24. Fine structure of SML and some pollutants localization Pb, Cd, As 0-200 m “Old” emulsion of oil hydrocarbons 0-1000 m Colum water

25. 4 miles 2 miles 0,5 miles 0-200 m 200-1000 m oil hydrocarbons column water bottom

28. Pollution of marine aerosols by heavy metals, arsenic and oil hydrocarbons (Russian part of Black sea)

29. Azov Sea Expedition’s region Black Sea

30. Heavy metals, Al, As in marine aerosols of Black, Mediterranean and White sea

31. Heavy metals in marine aerosols near Sochi before and after storm(maximum permissible concentration (MPC) for air of plants - red arrows)

36. Oil hydrocarbon in aerosols of different originmg/m3 Marine aerosols - 0-40 (Black sea - very seldom event, Mediterranean and Finland Gulf - every day) City aerosols (Moscow) - 0 (0 = < 0,5 mg/m3 ) Terrestrial aerosols (russian coastal zone of Black sea, Neva bay, Caucasian mountains) - 0

37. Time-dependent variation of heavy metals and Al in marine aerosols (coastal sampling, 2 m alt., Golubaya bay (Geledzshik))

38. Spatial distribution of heavy metals and Al in marine aerosols from Novorossiysk to Adler (<10 miles from coast)

39. Spatial distribution of heavy metals and Al in marine aerosols from Gelendzshik to open sea (south direction) 0-100 miles f

40. Toxicity of marine aerosols1) Medical trace element studies2) Cell biosensor assay3) Direct inhalation of SML probe in aerosol’s camera4) Monitoring of adenoviruses as markers of air pollution

41. Relative (normalized to Al) element profiles in different aerosols and human blood terrigenous

43. Conclusions • All artificial and nature pollutants in the sea may to return in human beings with marine aerosols • Very dangerous (!): Destruction of marine biocenosis lead to increase of marine aerosols toxicity due to biotoxins concentrations in SML (US programme “Marine biotoxins”) • The men with asthma, allergic diseases, tuberculosis may to rest in marine coastal zone only after expert estimation of marine aerosols’ toxicity

44. The methods for monitoring of noveltransboundary source of coastal ecosystems’ pollution

45. Aerosols sampling – up to 20 m3 per hour, transmission factor of filters <1.0% for 0,17 m particles • SML sampling – capillary sampler (fixed thickness SML sampling) and Garret sampler • Element assay – graphite Zeeman AAS with acid microwaves probe’s preparation • Oil hydrocarbons assay - gas-liquid capillary chromatography, IR-spectrometer, UV-fluorometer • Express water quality control: LALLS and laser interferometer • Size spectra control – laser diffraction particle sizer

46. Marine aerosols Terrestrial aerosols

47. terrestrial

50. The new technology of the surface marine water express monitoring using LALS and new data on the water structure • Key technologies, methods and equipment Know-how – the new technology for LALS image analyzes for computation of size spectra, the new technology for giant water structure visualization Methods of quantitative water structure (size spectra of giant water’s clusters – chemical composition relation Own pre-production model of LALS equipments with own original software Own patent SML sampler for sampling of the fixed thickness layer • Strong points of SOI in the project: more than 20 years experience in practical marine pollution’s monitoring experience, 15 years - in SML researching, 5 years - in water structure investigation participation in creation of Russian metrology standard for dispersed system (suspensions, emulsion, aerosols etc)