Harmful substances in the marine environment

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Harmful substances in the marine environment

• Eugeniusz Andrulewicz
• Sea Fisheries Institute in Gdynia
• Department of Fisheries Oceanography and Marine
  Ecology

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Chemical compounds in use (US EPA)

• No. of known chemical compounds
• about 1 000 000
• No. of chemical compounds in daily use
• about 60 000
• No of man made chemical compounds introduced
  every year about 1 000
• No. of ma made chemical compounds in the marine
  environment
• thousends ?
• No. of chemical compounds monitored at sea tens?

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Main groups of toxic substances which are met at
sea

• Trace metals
• Radionuclides
• Halogenated hydrocarbons low
• and high molecular hydrocarbons, pesticides,
  herbicides,
• flame retardants
  
• Petroleum hydrocarbons
• aliphatic aromatic (PAHs)
  
• Dumped war gases
• Natural toxins H2S, PSP, DSP, etc.
•  Are they all classified as harmful substances ?

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Definition of harmful/hazardous substances

• Hazardous substance means any substance which
  is due to its intrinsic properties is persistent,
  toxic and liable to bio-accumulate(HELCOM,
  1974/1992)
• Synonyms
• harmful substances/compounds, hazardous
  substances/compounds,
• noxious substances)

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Main groups of harmful/hazardous substancesby
definition

• Trace metals and their compounds
• Halogenated hydrocarbons
• Polycyclic aromatic hydrocarbons
• Organno-metallic compounds
• Other (if toxic, persitant and bioaccumulative)

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Trace metals/haevy metals

• Hg, Pb Cd, Zn, Cr, Cu... and their compounds
• Illustrative example Hg (Hg0, Hg1, Hg2)
• Mercury (I) chloride Hg2Cl2
• Mercury (II) chloride HgCl2
• Methylated mercury CH3-Hg-Cl, (CH3)2-Hg

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Chlorinated (aliphatic) hydrocarbonsIllustrative
example of chlorination of chem. compound
methane
Tetra- chloromethane (Tetrachloride)
Di- chloromethane
Mono- chloromethane
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DDT Dichlorodiphenyltrichloroethanep,p- DDT
1,1,1-Trichloro-22-bis (p-chlorophenyl)

• Chemical formulas C14H9Cl5 (C6H4Cl)2CHCl3)
• Molecular mass 354.49 g/mol
• Melting point 108.5 C
• Boiling point 260 C
• CAS number (or CAS RN) 50-29-3

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Chlorinated hydrocarbons selected exampes
PCB Polychlorinated biphenyls
DDT Dichlorodiphenyl- trichloroethane

Pentachlorophenole
Chloronaphtalene
Chlorinated di-benzophuranes
Chlorinated di-benzodioxines
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Illustrative example number of possible isomers
of PCBs
No. of chlorine substitution in biphenyle

• Mono-3
• Di - 12
• Tri-24
• Tetra - 42
• Penta - 46

• Hexa - 42
• Hepta - 24
• Octa - 12
• Nona - 3
• Deca - 1

Total 209 isomeres
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Polychlorinated biphenyls (PCBs)

• Polychlorinated biphenyls (PCB's) are a family of
  209 chemicals with varying numbers of chlorine
  atoms attached in varying positions to two
  connected benzene rings
• However, statistically and mechanically, it is
  improbable that all are present in nature. Only
  about 130 are present in PCB mixtures
• The major global producer of PCB's was Monsanto
  Corp. (Aroclor's) which produced over half of the
  world's PCB's
• CAS No.1336-36-3

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Polycyclic aromatic hydrocarbons selected
examples

Naftalene
Phenantrane
Pyrene
Benzopyrene
Methyloethylo benzopyrene
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Orgnometallic compounds selected examples

• Methyl mercury
• CH3-Hg-Cl, (CH3)2-Hg
• Dibuthyltin (DBT)
• Tributhyltin (TBT) C12H27Sn

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Main sources of harmful substances

• Industry chemical, electrical, metalurgical
• Agriculture pesticides, herbicides
• Energy production combustion of coal, crude oil
  and crude oil derivatives
• Transport combustion of crude oil derivatives
• Households/Domestic sewage and garbage
• Lifestyles lack of awareness/lack of care/lack
  of legal regulations

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Assessment of transport from land to the sea
fallouts dicharges

• Atmospheric fallout (monitoring of wet dry
  precipitation, modelling)
• River discharges (monitoring)
• Direct discharges (estimates monitoring)
• Harmful substances originated at sea oil spills,
  dumping of dredge spoils
• (estimates/calculations, operational model
  forecasts of drifting oil slicks)

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Discharge of trace metals
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Transformation and fateat sea

• Forms of occurence dissolved, adsorbed,
  disperssed/suspended emulsified
• Physical-chemical processess
• volitalisation, dilution, sorption,
  dissperssion, partitioning (hydrophility/lipophili
  ty), photolyses, oxidation, hydrolysis
• Biological processes microbial
  biotransformation, bioaccumulation
• Deposition sedimentation, temporar and permanent
  deposition (diagenesis)
• For processes look at Coastal Lagoons

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Contamination of the food chain of the Baltic Sea
by PCBs(Swedish studies)
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Toxicity

• Acute toxicity (toxicity tests - LD50
• (lethal dose in 50 of animals)
• Chronic toxicity (long term exposures)
• Various biological effects (biomarkers) stress,
  immunosupression, reproductive disorders,
  carcinogenic effects, mutagenic effects, genetic
  toxicity

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Catastrophic episodes of metal poisoningsMercury
(Hg) - the Minamata disease

• Minamata, Japan 1953-1960 52 died, 130 sick
• Niigata, Japan 1964-1965 30 died, 59
  sick
• Sweden 1964 seed-eating bird died
• Irak 1972 50 000 died, 500 000 sick
• Ghana 1974 144 sick
• Amakusu, Japan 1974 59 sick

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Catastrophic episodes of metal poisoningsCadmium
(Cd) - the itai-itai disease

• Jintsu River, Japan 1947-1965 100 died

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Catastrophic episodes of metal poisoningsLead
(Pb) - the plumbism

• Greek Roman empires BC- 500 AD
• Australia 1929-1954 165 died, 352 sick
• Germany 1930 250 sick
• Honkong 1969 British military unit
  sick

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Harmful effects recorded in the Baltic Sea

• Effects of methyl mercury on human fetus and
  pregnant women (recorded in Sweden in 1960ies and
  70ies)
• Effects of PCBs on reproduction of seals and
  eagles (60ies,70ies 80ies)
• Documented genotxic effects in some oil spill
  areas (recent studies in oil spill site in
  Lithuania)
• High concentration of dibezodioxins
  dibenzofurans in fat fish present !
• Most of sublethal biological effects is not
  known !

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Effects (in the Baltic Sea) of ban on PCB use
(1978-2000)
After HELCOM
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Human health (Polish) standards for fish food
mg/kg w.w.

• Hg 0.1 muscle
• Hg 0.5 liver
• Cd 0.1 muscle
• Cd 0.5 liver
• Pb 0.20 muscle
• Pb 1.0 liver
• Zn 20 muscle
• Zn 100 liver
• Cu 2.0 muscle
• Cu 50.0 liver

• s-DDT 5.0
• s-PCB 2.00
• HCB 0.2
• g-HCH 0.2
• Chl.- dioxins - ?
• Chl.- furans - ?

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Chemical analyses

• Sampling water, sediments, biota
  
• Sample preparation filttering, extraction,
  cleaning, evaporation/condesing,
• Instrumental analyses accuracy, precission
• Trace metals emission absoption
  spectroscopy
• Chlorinated hydrocarbons gas chromatography
  (ECD detector), HPLC, mass spectrometry
• Peroleum hydrocarbons UVF, gas chromatography
  (FID detection), mass spectrometry
• Organo-metallic compounds AAS, HPLC

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Biological effects/Risk assessment/ Examples of
early warning biomarkers

• Contaminant-specific biomarkers
• EROD/Etoxyresorufin deethylase (PAHs and PCBs)
• GST/Glutamine-S-transferase (organic xenobiotics)
• Acetylocholinoesterase (AChE) inhibition
  (organophosphates)
• ALA-D inhibition (Pb)
• PAH metabolites in bile (PAHs)
• DNA adducts (genotoxic effects)
• Methallotioneins (MT) induction (Co Zn)

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Biological effects/Risk assessment/ Examples of
early warning biomarkers

• Reproductive disorder biomarkers
• Imposex in gastropods
• Intersex in gastropods
• Reproductive success in eelpout
• Gonad histopathology (fish and shellfish)
• Vitellogenin induction
• Histopathology in seal reproductive organs,
  bivalve soft body
• Shell thickness of guillemot eggs

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Biological effects/Risk assessment/ Examples of
early warning biomarkers

• BEC techniques for water and sediments
• Water bioassays
• Whole sediment bioassay
• Sediment pore water bioassay
• Sediment sea water elutriates

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BEC techniques for fish

• Externally visible desesaes (skeleton
  deformations, tumor)
• Early toxicopatic lesions, pre-neoplastic and
  neoplastic liver histopathology
• Reproductive success in fish
• Abnormalitiies in fish embryons and larvae
• Degenerative kill and kidney histopathology

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HELCOM LIST OF SELECTED SUBSTANCES FOR IMMEDIATE
PRIORITY ACTION

• Alkanes
• Chlorinated paraffins, short chained
• Chloroform
• Phenols
• Nonylphenolethoxylate and the degradation/transfor
  mation   products
• Nonylphenol, 4-
• Xylenes
• Musk xylene
• Organic oxygen compounds
• Diethylhexylphthalate
• Dibutylphthalate
• Metallic compounds
• 2,4,5-T

• Cadmium
• Lead
• Mercury
• Selenium
• Pesticides/Biocides
• 1,2-Dibromoethane Acrylonitrile
• Metallic compounds
• Aldrin
• Aramite
• beta-HCH
• Chlordane
• Chlordecone (Kepone)
• Chlordimeform

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HELCOM LIST OF SELECTED SUBSTANCES FOR IMMEDIATE
PRIORITY ACTION Ctd.

• Nitrophen
• Pentachlorophenol
• Quintozene
• Toxaphene
• Organotin Compounds
• Polycyclic halogenated aromatic compounds
• Hexabromobiphenyl
• PCB
• PCT (mixtures)
• TCDD, PCDD, PCDF
• Polycyclic aromatic hydrocarbons
• PAH

• DDT
• Dieldrin
• Drins
• Endrin
• Fluoroacetic acid and derivatives
• HCH
• Heptachlor
• Hexachlorobenzene
• Isobenzane
• Isodrin
• Kelevan
• Kepone (Chlordecone)
• Lindane
• Mirex
• Morfamquat

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OSPAR List of Chemicals for Priority Action

• Polychlorinated dibenzodioxins (PCDDs)
• Polychlorinated dibenzofurans (PCDFs)
• Polychlorinated biphenyls (PCBs)
• Polyaromatic hydrocarbons (PAHs)
• Pentachlorophenol (PCP)
• Short chained chlorinated paraffins (SCCP)
• Hexachlorocyclohexane isomers (HCH)
• Cadmium

• Mercury and organic mercury compounds
• Lead and organic lead compounds
• Organic tin compounds
• Nonylphenol/ethoxylates (NP/NPEs) and related
  substances
• Musk xylene
• Brominated flame retardants
• Certain Phthalates Dibutylphthalate and
  Diethylhexylphthalate

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OSPAR 1998 List of Candidate Substances

• Alkanes - 25
• Alkenes (Olefins) - 10
• Anilines - 8
• Benzenes - 20
• Hormones - 5
• Inorganic compounds - 1
• Metallic compounds - 8
• Organic nitrogen compounds - 11
• Organic oxygen compounds - 23

• Organic phosphorous compounds- 6
• Organic compounds - 5
• Organometallic compounds - 6
• Pesticides - 63
• Phenols- 22
• Polycyclic aromatic
• Compounds - 11
• Products- 1
• Toluenes and xylenes - 21
• Altogather 225 compounds

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Modelling opportunities

• Air transport/Fallout into the marine environment
• River transport/Discharge to costal and marine
  environment
• Transport and fate within the marine environment
• Transfer and bioaccummulation of harmful
  compounds (particularly those not monitored)
  along the food chain

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Management

• Reduction of discharges at source
• Integrated chemical and biological effects
  monitoring and early warning signals (biomarkers)
• Implementation of global conventions Convention
  on Long Range Transboundary Air Pollution (LRTAP)
  and Stockholm Convention on Persistant Organic
  Pollutants (POPs)
• Implementatio of regional conventions
  HELCOM,OSPAR, MAR POL etc.
• Applying Precautionairy Principle
• The only thing that society can do in the
  future is to be more restrictive with any release
  of anthropogenic substances in this susceptible
  sea
• Soren Jensen and Bo Janson

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Reccommended reading

• Organic Chemicals in Coastal Lagoons Ed. I.
  Ethem Gonenc and John P. Wolflin, Chapter 4.2,
  149-182.
• Go to relevant web pages
• AMAP, EEA, HELCOM, OSPAR, US EPA

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Thank you for your attention