F.3 SUBPROGRAMME - Marine Environmental Studies Laboratory

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Monitoring and Study of Marine
Pollution Activities at the IAEA - Marine
Environmental Studies Laboratory
Stephen de Mora Marine Environmental Studies
Laboratory (MESL) International Atomic Energy
Agency (IAEA) Marine Environment Laboratory 4,
Quai Antoine 1er MONACO
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Monitoring and Study of Marine Pollution

• Introduction
• MEL and MESL
• Facilities and Capabilities
• 11 laboratories in MESL
• Supporting Regional Seas Programmes
• Research
• The Future

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The only Marine Laboratory in the UN System

• 1961 - Laboratory established in the
  Oceanographic Museum
• 1988 -Temporary facilities in the Louis II
  Football Stadium
• 1998 - Permanent facilities on the Port of Monaco

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Marine Environment LaboratoryOrganizational Chart
Marine Environment Laboratory Department of
Nuclear Sciences and Applications International
Atomic Energy Agency
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Mission of MESL
Interactions between Environmental Quality and
Marine Resources
Effect of Non-nuclear Pollutants on the Marine
Environment
Safe and Sustainable use of Marine Resources
People
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Marine Environmental Studies Laboratory

• MESL has expertise in
• Marine analytical chemistry
• Marine pollution monitoring and assessment
• Chemical oceanography marine biogeochemistry
• Within the IAEA
• Laboratory responsible for the study of
  non-nuclear marine pollution
• Manages the H.3 subprogramme entitled Monitoring
  and Study of Marine Pollution
• Within the UN System
• MESL co-ordinates the Inter-agency Programme on
  Marine Pollution
• Interacts with various Regional Seas Programmes
  MED POL, ROPME, BSEP, CEP

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IAEA H.3 Subprogramme Projects

• Environmental Analytical Chemistry in Support of
  Marine Pollution Monitoring Programmes
• Marine Pollution Assessment in Coastal Regions
  and Bioresources, including support to UN
  Inter-Agency Activities
• Nuclear Techniques in Studies of Marine
  Antifoulants in Coastal Environments
• Isotopic Applications in Non-radioactive Marine
  Contaminant Studies

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Ongoing Support to UN Inter-agencyMarine-Related
Activities
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Analysis of Inorganic Contaminants

• Inorganic pollutants includes heavy metals and
  organometallic species such as methylmercury and
  tributyltin
• Instruments
• aas (flame, cold vapour, hydride generation,
  graphite furnace)
• atomic fluorescence detectors for mercury
  analyses
• ICP-MS

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Analysis of Mercury and Methylmercury

• Determination of mercury and methylmercury
• water, sediments and biota
• Instruments
• aas (cold vapour)
• atomic fluorescence
• AMA 254 Mercury Analyzer

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Isotopic Analyses using ICP-MS

• Finnigan Element High Resolution ICP-MS
• Multi-element technique
• Isotopic analyses (uranium isotopes in tap water)
• High sensitivity sub-fg detection limits (U-234
  is 30 fg/mL in domestic water)
• High resolution for resolving problematic
  spectral interferences
• Speed most analyses require a scan of lt2 minutes

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Analysis of Organic Contaminants

• Organic contaminants analysed
• petroleum hydrocarbons, including PAHs
• pesticides (DDT, lindane, etc)
• other chlorinated contaminants, such as PCBs

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Analysis of Organic Contaminants

• Gas chromatographs with various
• detectors FID, ECD, NPD, FPD

GC-MS
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Isotopic Analyses using GC-C-IRMS
Variations of ? 13C in POC and biomarkers in
particulate matter vs CO2 in sea water
? 13C ()

• Gas Chromatography-Combustion-Isotope Ratio Mass
  Spectrometry is used to measure the ?13C in
  individual organic components for
• source apportionment assessments
• investigate carbon cycling and behaviour
• reconstructing the atmospheric CO2 concentrations
  from the sedimentary record as an indicator of
  global change

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Supporting Regional Seas Programmes

• Technique development in marine analytical
  chemistry
• Formulation of reference methods and guidelines
• Intercomparison exercises
• Production of reference materials (RMs)
• Education and training in analytical techniques
• Capacity building
• Monitoring programmes
• Research activities

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Reference Methods for Marine Pollution Studies

• Formulation of reference methods and guidelines
• Sanitary quality of coastal waters
• Analysis of chemical contaminants in organisms,
  sea water and sediments
• Effects of pollutants on organisms and ecosystems
• 56 reference methods and 2 technical bulletins
• All are available in English, some have been
  translated into French and / or Spanish

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Large Scale Sample Preparation

• Large-Sale sample preparation for
• intercomparison exercises and the
• production of reference materials

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Intercomparison Exercises

• Marine samples (sediment or biota) are
  periodically distributed free of charge
• Results are reported to MESL and evaluated
  statistically
• Intercomparison exercises offer analysts means
  to
• Test analytical methods
• Control laboratory performance
• Assess accuracy of results

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Global Participation in IntercomparisonExercises
for Trace Metals
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Data Reporting in Intercomparison Exercises

• 245 laboratories world-wide participated in
  IAEA-142.
• 84 labs provided organochlorine data
• For these 84 labs
• 25 of the results were outliers
• 50 fell outside the range of acceptable
  precision
• only 11 identified the POPs shown on the right.

Graphical presentation of z-scores easily shows
the relative performance of laboratories
(IAEA-408).
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Reference Materials (RMs)

• RMs are vital for training programmes,
  intercomparison studies and for laboratories to
  maintain their own Analytical Quality Control
  procedures
• MESL is one of the few producers worldwide of
  marine RMs
• MESL has produced gt20 RMs
• a range of environmental matrices (sediment
  biota)
• certified with respect to various organic and
  metallic pollutants
• MESL provides RMs free to laboratories
  participating in Regional Seas Programmes

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Some available Reference Materials
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REFERENCE MATERIAL IAEA-405 Trace Elements and
Methylmercury in Estuarine SedimentRecommended
Values (dry weight basis)
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Capacity Building

• Undertake quality assurance missions to regional
  laboratories
• assessment of infrastructure and training needs
• technical assistance to laboratories
• Provide advice to prioritise purchase and
  capacity building to suit the regional targets
  set
• Arrange purchase of laboratories supplies
• Purchase instruments
• Install and maintain equipment
• Remote monitoring of instruments via modem
  (troubleshooting, update method files)

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Education and Training in Analytical Techniques

• Training courses run regionally and in Monaco
• MED POL
• Black Sea
• Caspian Sea
• ROPME
• Course subjects
• sampling procedures
• analysis of heavy metals
• analysis of persistent organic polutants
• use of nuclear and isotopic techniques in
  pesticide research

Visiting scientists and fellows work in Monaco
with access to sophisticated instrumentation such
as ICP-MS and GC-C-IRMS
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Monitoring of Marine Contaminants

• Active collaboration with laboratories in Member
  States assisting with
• Project design
• Sample collection and handling
• Analyses of contaminants (i.e. heavy metals and
  persistent organic pollutants)
• Organization of Quality Assurance
• Data interpretation
• Assessment of pollution

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Research at MESL

• Methodology development
• Organotin analyses
• Organophosphorus analyses
• Biogeochemistry
• 13C biomarkers
• Mercury cycling
• Marine antifoulants (Organotins)
• Pollution Assessment Studies
• ROPME Sea Area
• Black Sea
• Caspian Sea

Rock oysters along the shore at Masirah Island,
Oman
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Analysis of Organotin Species 1

• Organotin Speciation Analyses in Marine Biota
  using NaBEt4 Ethylation and GC-FPD
• Optimised to overcome the most common matrix
  effect problems (especially colloidal interfaces)
  with biological samples
• A strict quality control system using three
  internal standards was implemented
• Tripropyltin to assess the derivatisation
  reaction
• Tetraoctyltin to check the overall extraction
  efficiency
• Tetrabutyltin was used to verify the GC-FPD
  performance
• Successfully applied to different biological
  matrices
• Fish
• Mussels
• Oysters
• Barnacles

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Analysis of Organotin Species 2
Blank
Oyster Sample
Mussel RM BCR 477
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Analysis of Organotin Species 3
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Biogeochemical Cycling of Mercury

• Mercury and methylmercury are notable marine
  pollutants
• Speciation analyses are necessary to understand
  environmental mobility and bioavailability
• Studies have been undertaken in the ROPME Sea
  Area, Black Sea, Laptev Sea, and Adriatic Sea

Total and Methylmercury Profiles in Sediment
Cores of the Laptev Sea
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Research in the MED POL Programme
Marine biocides in waters from marinas along the
south of France
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Field Studies in the ROPME Sea Area

• Countries within the ROPME Sea Area Bahrain,
  Iran, Iraq, Kuwait, Oman, Qatar, Saudi Arabia and
  the United Arab Emirates
• Contaminant Screening Project surveys of
  contaminants in water, sediments and biota for a
  suite of inorganic and organic pollutants.
• Tar washing ashore at Mina Al Fahal, Oman

• MESL undertakes a quality assurance programme
  with Member States in the region involving
• site visits
• training courses
• capacity building
• split sample analyses
• intercomparison exercises

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Persian Gulf Hot-Spots for As in Shellfish
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Black Sea Environment Programme

• Map showing the distribution of PAHs in marine
  sediments from the Black Sea

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Caspian Environment Programme

• At Sea Training Programme
• Contaminant Screening Campaign
• Transboundary Diagnostics Analysis

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Analyses of Sediment Samples

• Metals
• Hydrocarbons
• Polycyclic Aromatic Hydrocarbons (PAHs)
• Chlorinated Pesticides (lindane, DDT, etc.)
• Polychlorinated Biphenyls (PCBs)
• Other parameters
• Grain size distribution
• Total Organic Carbon (TOC)
• carbonate content
• Extracted Organic Matter (EOM

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Tree Diagram 25 elements _at_ 61 Stations
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Co Pb versus Al in Sediments
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Nickel

• Ni displays very high levels in sediments
  throughout the central and southern Caspian Sea.
• NOAA ERL (21 mg g-1) was always exceeded and the
  ERM (52 mg g-1) values at several sites.
• The highest concentrations were found near the
  mouth of the Kura River, but the Ural River
  influence is also evident.
• The elevated content reflects a high natural
  background, but could be augmented though mining
  activities. Similar behaviour was apparent for Cr
  and As.

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Mercury

• The mercury content is low in the northern sector
  having sediments that are relatively coarse or
  composed mostly of carbonates.
• Mercury concentrations are high at a number of
  sites in Azerbaijan, where Hg content exceeds the
  NOAA ERL value of 0.15 mg g-1.
• In particular, the sediments to the south of Baku
  Bay are polluted.

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Total Petroleum Hydrocarbons

• The concentrations of total petroleum
  hydrocarbons range from 29 to 1820 µg g-1 in
  Azerbaijan, where generally the highest amounts
  were found.
• Sediments from Turkmenistan were not available.
• Compared to other global locations, the levels of
  petroleum hydrocarbons in the most contaminated
  of these sediments just south of Baku Bay are
  relatively high.

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Unresolved Complex Mixture

• Unresolved aliphatic hydrocarbons are also known
  as the unresolved complex mixture (UCM).
• Concentrations of UCM lt10 µg g-1 are common in
  coastal environments distant from hydrocarbon
  inputs.
• The levels in Azerbaijan are generally quite high
  and indicative of pollution, especially near Baku
  Bay.

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Lindane in Sediments

• Lowest values were found in the Iranian and
  Kazakhstan sectors.
• Several stations in the Russian coastal zone had
  elevated levels.
• The maximum concentration 609 pg g-1, exceeded
  the ISQG value of 320 pg g-1.
• As lindane degrades rapidly in the environment,
  elevated levels reflect ongoing usage.

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Endrin in Sediments

• Low levels were found in Kazakhstan and Russia.
• Highest values were observed in the coastal zone
  of Azerbaijan (85 pg g-1) and Iran (81 pg g-1).
• Maximum concentrations did not exceed the ISQG
  value of 267 pg g-1.

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Total DDTs inCaspian Sea Sediments

• NOAA ERL is 1600 pg g-1.
• Total DDT levels exceed this quality standard at
  a number of locations, especially in Azerbaijan
  and Iran.
• The maximum value (13400 pg g-1) shows a strong
  signal from the Kura River.
• The lowest concentrations were found in the North
  Caspian Sea, particularly in the north-eastern
  shallow area.

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Relative Contributions of DDT and Degradation
Products DDD DDE

• Relatively high proportions of DDT indicate
  recent influxes and, by implication, ongoing DDT
  usage throughout the region.

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The Future New Priorities

• Strengthened co-ordination with national
  institutes and regional organisations
• Broadening of activities in response to the
  changing needs of UN bodies
• Global Programme of Action for the protection of
  the marine environment from land based activities
• Tracers to characterise sewage and ground water
  discharges
• IMO regulations on the use of tributyltin (TBT)
  as a marine antifoulant
• Environmental chemistry and ecotoxicology of
  alternative marine biocides

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Thank You