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

Contents of Presentation Overview of State Oceanographic Institute Novel transboundary 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 novel transboundary source of coastal ecosystems pollution The methods and approaches for minimization of damage to human health of the sea megapolises

State Oceanographic Institute (SOI) Total staff number – 140 persons. Total scientists / engineers number – 120 persons. The Year of establishment – 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.

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.

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

Chemical Lab of SOI Collaboration in Black sea researches ( ) 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)

Novel transboundary source of coastal ecosystems pollution Reverse flux column water - sea surface microlayer (SML) - aerosols

Heavy metals, Al, As in marine aerosols of Black, Mediterranean and White sea ng per m 3

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

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

1.Gas emissions from bottom sediments 2.Gas emissions from living organisms 3.Waves breaks and winds capture 1.Chemical composition of aerosols is similar to SML 2.A large drop return to surface 3.Small drops (aerosols) may be captured by wind flow Surface microlayer (SML)

The mechanisms of SML enrichments by pollutants

Mechanisms of SML chemical composition formation 1.Routine Langmuir enrichment of phase boundary (water-air) by SAC and hydrophobic compounds including detergents and oil hydrocarbons 2.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.) 3.These processes result in high *concentration of pollutants in SML *non-stationary multilayers structure

The main types of convections in SML Rayleighs convection Anisotropy heterogeneous convection Driving forces of convections: T E Thermal neutrons flux

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

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

Fine structure of SML and some pollutants localization Colum water Pb, Cd, As Old emulsion of oil hydrocarbons

column water bottom oil hydrocarbons 0,5 miles4 miles2 miles

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

Expeditions region Black Sea Azov Sea

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

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

Oil hydrocarbon in aerosols of different origin g/m 3 Marine aerosols (Black sea - very seldom event, Mediterranean and Finland Gulf - every day) City aerosols (Moscow) - 0 (0 = < 0,5 g/m 3 ) Terrestrial aerosols (russian coastal zone of Black sea, Neva bay, Caucasian mountains) - 0

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

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

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

Toxicity of marine aerosols 1) Medical trace element studies 2) Cell biosensor assay 3) Direct inhalation of SML probe in aerosols camera 4) Monitoring of adenoviruses as markers of air pollution

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

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

The methods for monitoring of novel transboundary source of coastal ecosystems pollution

1.Aerosols sampling – up to 20 m 3 per hour, transmission factor of filters <1.0% for 0,17 particles 2.SML sampling – capillary sampler (fixed thickness SML sampling) and Garret sampler 3.Element assay – graphite Zeeman AAS with acid microwaves probes preparation 4.Oil hydrocarbons assay - gas-liquid capillary chromatography, IR-spectrometer, UV-fluorometer 5.Express water quality control: LALLS and laser interferometer 6.Size spectra control – laser diffraction particle sizer

Marine aerosols Terrestrial aerosols

terrestrial

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 waters 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 pollutions 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) The new technology of the surface marine water express monitoring using LALS and new data on the water structure

Application Areas Complex marine waters pollution monitoring Sweet waters pollution monitoring Monitoring of the novel transboundary source of air pollution in coastal zone and open sea (the reverse way – sea column water – SML – marine aerosols) Determinations of identity and quality control of water solutions like as springs, drinks or drugs Trivial particle sizers analysis

Technology Description Technology target: The determination of sea water quality using size spectra and relaxation times of the giant heterophase water clusters Expected results: The technology will allow to provide express monitoring of surface marine water with possibilities to obtain advanced data on SML structure Output: The model of new two-mode laser device with original software and new technology for express monitoring of water pollution including with such consequence as marine aerosols pollution

Scheme of Technology Sampling of the sea SML of fixed thickness Analyzes the probe for description of suspensions using LALS (1 st mode of the device) and laser projector (2 nd mode of the device) for obtaining of particless size spectra, concentration and their hydrophilic behavior Analyzes the probe using laser projector (2 nd mode of the equipment) for description of suspensions The filtering of the probes and using 1 st or 2 nd mode of the device for obtaining of size spectra of giant water clusters and image analysis of their arrangement The comparison of obtained results with normal standard sea water, standards for different salinity, temperature etc and computer database of changing in the presence of different pollutants

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

Technology Description The mode 1 of the laser device - LALS

Technology Description The examples of size spectra of giant waters clusters in different probes of sea water

Technology Description The mode 2 of the laser device – laser projector/ 2D laser refractometer 1 – laser. 2 – lens. 3- water solution. 4 – подставка. 5 – oobject. 6 – screen. 7 – objects image.

Technology Description The examples of 2 nd mode of the laser device application 1) for particle hydrophilic behavior analysis 2) for analysis of arrangement of giant waters clusters in SML and column water

The methods and approaches for minimization of damage to human health of the sea megapolises 1) Routine monitoring with system of forecasting and operative tracking cleanliness of air [Bugaev S.N. et al., 2003] of coastal ecosystems and megapolises 2) National and international regulation of maximum permissible sea and river burials (new Russian rules for seas have made by SOI), including dispersed matter 3) Monitoring and information system (in progress) 4) International co-operation (for example Black sea aerosols (possible) 5) Direct prevention of very dangerous aerosols flux in local area (device for aerosols dissipation (and condensation) was created in SOI and worked in airport Bykovo and on japan mountains road)

Routine monitoring with system of forecasting and operative tracking cleanliness of air [Bugaev S.N. et al., 2003] of coastal ecosystems and megapolises 1) The system of verification of the source of aerosols origin (marine, terrestrial, city) based on element profiles (Al and d-element) (fig. 2), size spectra and data of marine bacteria transfer (PCR-detecting). 2) The new approaches for sea surface microlayer sampling using as Carret screen as new capillary multiplayer sampler with sampling of fixed thickness of SML. 3) Complex of laser methods for estimation of water and aerosols dispersions. 4) The complex of models about water surfaces aerosol generation and aerosols transfer.

The main components of monitoring system developing by SOI of the novel transboundary source of pollution of the coastal ecosystems and the diminution of damage to human health of sea megapolises are: The information monitoring system filled up in real time behind sources of receipt of hazard substances in the sea environment (river drains, sewage and city waste-water, bottom sediments, marine biotoxins etc.). 2. Information and analytical system of tracking for the processes of receipt, mixture and dilution the hazard substances, including the hydrodynamic description of evolution of the pollutants in the sea environment of coastal zones. 3. Information system of tracking filled up in real time for the utilizations of hazard substances (volital, mechanical evaporation (marine aerosols), precipitation (bottom sediments), biological consumption, etc.) 4.Development of the subsystem about the accumulation of volumetric hazard substances in subsurface layer taking into account hydrodynamical, physical, hydrochemical and hydrobiological processes (gravity and capillary and heterogeneous convections, describing the subsurface layers enrichment due to the new transfer mechanism). The quasi-stratified structure of subsurface layer with the differentiated level-by- level separately accumulation of hazard substances will be quantitatively described. Based on the data on 2-D laser refractometry the coupled processes of mass and energy across interface of ocean and atmosphere will be first described. 5.The development of the subsystem describing the mechanism of marine aerosols generation due to wind-wave interaction of atmosphere and ocean (the main source of the marine aerosols is the 1-mm subsurface layer enriched by hazard substances). 6.Information and analytical system of tracking for the processes: transport and mixing of marine aerosols with terrestrial ones (with additional enrichment by hazard substances due to water evaporation from aerosol particles). 7. The subsystem for the estimation of toxicity of the polluted marine aerosols on coastal ecosystems and human health of sea megapolises (sanitary and medical aspects).

Thank you for attention!