2 pollution (heavy metals)w

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  • 48 tons of mercury emitted from the 11,000 coal burning power plants. But another 65 tons could be deposited by manufacturing of chlorine products. About 10 million tons of SO2 emitted each year down from over 17 million tons in 1980.
  • Tributyltin is being phased out following the recommendation for a world-wide ban by the IMO.
  • Alarming increase in the number of fish advisories to limit or avoid consumption of contaminated fish. Mercury mostly from the burning of fossil fuels, primarily coal and the incineration of medical waste. PCBs from past use and found leaching from landfills and other waste dumps. Dioxins from the manufacturing and improper disposal of plastics, primarily PCP. Also is one of the strongest carcinogens known. Used in the pulping of paper. Natural Resource Defense Council
  • Yellowfin tuna are pelagic and have lower levels of Hg. Blackfin tuna are primarily near-shore species and show elevated Hg concentrations.
  • Alarming increase in the number of fish advisories to limit or avoid consumption of contaminated fish. Mercury mostly from the burning of fossil fuels, primarily coal and the incineration of medical waste. PCBs from past use and found leaching from landfills and other waste dumps. Dioxins from the manufacturing and improper disposal of plastics, primarily PCP. Also is one of the strongest carcinogens known. Used in the pulping of paper. Natural Resource Defense Council
  • 2 pollution (heavy metals)w

    1. 1. MARINE POLLUTION: Heavy Metals M. Nadeem Ashraf
    2. 2. What is marine pollution?According to the UN Group of Experts on the Scientific Aspects of Marine Pollution (GESAMP): Marine pollution is the introduction by man, directly or indirectly, of substances or energy to the marine environment resulting in deleterious effects such as: hazards to human health; hindrance of marine activities, including fishing; impairment of the quality for the use of seawater, and reduction of amenities.
    3. 3. What is contamination?Contamination is caused when an inputfrom human activities causes the increaseof a substance in seawater, sediments, ororganisms above the natural backgroundlevel for that area and for thoseorganisms.
    4. 4. Measuring contamination?Contamination is usually measured asparts (of pollutant) per million (ppm) = µg.g-1or parts per billion (ppb) = ng.g-1 = µg.kg-1it is measured as “wet weight”(e.g. contamination in moist water containing tissues)or as “dry weight”(e.g. contamination in dehydrated tissues)as water content can vary a lot – dry weight is a better measure
    5. 5. Heavy metal pollution High atomic weight metals (mercury, lead etc.) Sometimes the term trace elements is used to include non-metal and lower atomic weight elements Many of these elements are essential to the body in very low concentrations: Iron – essential for hemoglobin Copper - essential for hemocyanin (in invertebrates) Cobalt – in vitamin B 12 Zinc – essential component of many enzymes
    6. 6. Heavy metal pollutionBut in high concentrations these can betoxic.e.g. one asprin tablet is a useful medicine but 100 tablets are lethalSome heavy metals have no essentialfunction in the body (e.g. mercury, lead)and any concentrations can be harmful
    7. 7. Clark (2001) Toxicity of metals can vary according the their valency (e.g. 2+ or 3+) and their combination with other elements LC50: contaminant concentration level required for 50% of the test species to die
    8. 8. BioaccumulationPollutants like heavy metals are CONSERVATIVEpollutants – i.e. they aren’t broken down by bacteria etcand are effectively permanentMost plants and animals can regulate their metalcontent to a certain point – but metals that can’tbe excreted build up in an organism over itslifetime= BIOACCUMULATION
    9. 9. BiomagnificationAnimals feeding on bioaccumulators take in a higherlevel of contaminants, which bioaccumulate withinthemselvesThose animals feeding on them gain even higherinputs of contaminants, and bioaccumulate evengreater concentrationsand so on… with animals at the highest trophiclevel obtaining highest concentrations = BIOMAGNIFICATIONi.e. long-living, top predators bioaccumulate andbiomagnify the highest contaminant levels
    10. 10. Sources of heavy metal pollutionATMOSPHERIC Forest fires Volcanic activity Dust particles Anthropogenic emissions  coal fired power stations  car exhausts
    11. 11. Clark (2001)
    12. 12. Sources of heavy metal pollutionATMOSPHERIC Metals can be transferred by the atmosphere in gas or particle form (aerosol) Particles can fall from the atmosphere onto the land or sea = dry deposition Also precipitation can carry particles or dissolved gases = wet deposition Gaseous state elements (Boron, Mercury, Selenium) can also dissolve at the surface of water bodies (gaseous exchange) Bubbles breaking the surface of the sea can release salt particles containing metals– can travels from sea to atmosphere as well as atmosphere to sea
    13. 13. Clark (2001)
    14. 14. Sources of heavy metal pollutionRIVERS Erosion of rocks containing metals Surface runoff sweeps up naturally formed and anthropogenic metal particles Metals often bind with sediments and are deposited on the seabed – but these can enter the marine environment again is there is:  Dredging  Trawling  Severe weather
    15. 15. Sources of heavy metal pollutionGROUNDWATER SEEPAGE Dissolved substances are carried via ground water movement – contamination in soil may be picked up by the moving watersDELIBERATE DISCHARGE Contaminated waste dumping Industrial discharges Sewage
    16. 16. Clark (2001)
    17. 17. Clark (2001)
    18. 18. Islam & Tanaka (2004).
    19. 19. MERCURY (Hg)
    20. 20. Toxic effects of mercury Mercury can cause neurological damage, immune system suppression and can cause fetal abnormalities in mammals [Clarkson (1987); von Burg and Greenwood (1991) ] In humans it has been associated with various neurological effects, abnormal development and heart damage [Guallar et al., (2002); Clarkson et al., (2003); Murata et al. (2004); Grandjean et al. (2004) ]
    21. 21. Mercury toxicity In human adults mercury toxicity symptoms include:  Visual field constriction  Behavioral changes, memory loss, headaches  Tremor, loss of fine motor control, spasticity  Hair loss If fetuses / infants are exposed to mercury: •Mental retardation •Seizures •Cerebral palsy •Blindness and deafness •Disturbances of swallowing, sucking, and speech •Hypertonia - muscle rigidity [Clarkson et al., (2003)]
    22. 22. Toxic effects of mercury Mercury in the marine environment identified as a health risk for humans – Minamata disease In 1952 a factory in Minamata Japan was using mercury as a catalyst – mercury washed into bay In 1953 fishermen and farmers showed symptoms – neurological damage and fetal deformity etc.
    23. 23. Minamata disease  Disease diagnosed in 1956 – linked to fish consumption  1957 fishing banned in area  1959 – mercury identified as cause 1960 source identified  – factory effluent 2000 cases – 41 deaths and 700 permanent disabilities fish: 10-55 ppm (dry weight); bivalves 10-39 ppp (dry weight)
    24. 24. Toxic effects of mercury In the US an estimated 650,000 newborns a year are at risk from developmental and neurological damage due mercury [Mahaffey (2004)] The source of this mercury is contaminated seafood Around the world seafood with mercury levels over 0.5 to 1.0 ppm are considered unsafe for human consumption
    25. 25. Mercury in fish Most fish species have mercury levels of approximately 0.15 ppm in muscle tissue However cod have been found with levels of 1.29 ppm in Sweden and Denmark Tuna highly contaminated [Adams (2004)]  Blackfin tuna (Thunnus atlanticus) up to 2ppm  81% more contaminated than 0.5 ppm health regulation  Little tunny (Euthynnus alletterus) up to 3.4ppm  75% more contaminated than 0.5 ppm health regulation  Recreational fish - Red drum (Scaenops ocellatus) also contaminated: up to 3.6 ppm; 95% >0.5 ppm health limit [Adams & Onorato (2004)]
    26. 26. Adams (2004)Yellowfin tuna are pelagic and have lower levels of Hg.Blackfin tuna are primarily near-shore species and show elevated Hg concentrations
    27. 27. Mercury in marine mammals As long-lived top predators marine mammals accumulate very high concentrations of mercury Indo-Pacific humpback dolphins (Sousa chinensis) 900 ppm dry weight [Parsons (1999)] Striped dolphins (Stenella coeruleoalba) 485 ppm wet weight (~ 1600 ppm dry weight) [Honda et al., (1983)] Bottlenose dolphins (Tursiops truncatus) 13,156 ppm dry weight [Leonzio et al., (1992)]
    28. 28. Mercury in marine mammals Toxic effects reported in marine mammals include:  Lesions in the liver and other tissues; decrease nutritional state and fatty degeneration [Rawson et al., (1993); Siebert et al., (1995)]  High mercury (and other heavy metal) levels have also been associated with disease -induced mortality i.e. mercury may damage the immune system [Bennett et al., (2001)]
    29. 29. Mercury in whale meat Recent research has shown that cetacean meat being sold in Japan for human consumption had extremely high levels of mercuryMean contamination levels in cetacean red meat were 22 and 18 timeshigher than levels permitted by the Japanese government for total mercury(0.4 ppm)Levels were exceeded by up to 200xMercury levels in boiled liver were even higher: 1,980 ppm (wet weight).Rats fed contaminated meat showed signs of kidney abnormalities after asingle dose Endo et al., (2002; 2003a; 2003b; 2004)
    30. 30. Mercury in whale meat Another study in the Faeroe islands looked at the effects on the population of eating contaminated long- finned pilot whale meatEffects linked with mercury contamination included mental retardation,neurological abnormalities and brain stem damage in childrenAbnormal heart activity also linked to mercury contaminationPrenatal exposure to mercury was believed to be causing irreversibleneurological damage [ Murata et al. (2004); Grandjean et al. (2004) ]
    31. 31. Imputs of Mercury 6000-7500 tons a year
    32. 32. Clark (2001)
    33. 33. U.S. Anthropogenic Mercury Emissions ~ 158 Metric Tons Sources  87% combustion MercuryEmissions Mercury emissions  33% coal fired power  19% burning municipal Global 6% waste US  10% burning medical waste Mercury production  10% manufacturing Mercury Production 1996  3% all other sources 15%• 2/3 deposited outside US•~53 tons deposited inside US Data & Images: Moore (2002)+ 35 tons deposited in US from outside sources
    34. 34. Mercury trends Over past 100 years there’s been a 20 x increase in the deposition of mercury 70% of this mercury has been from anthropogenic sources Over past 10 years – deposition has declined – BUT deposition rate is still 11x higher than in the pre-industrial era Schuster (2002)
    35. 35. Schuster (2002)
    36. 36. CONTROVERSIAL: Mercury and US Policy During the Clinton Administration the Environmental Protection Agency conducted research on the impacts of mercury and the role of coal-fired power plants in mercury emissions. The EPA introduced a plan in which mercury emissions from coal-fired power plants would be reduced by 90% by 2008. The Bush Administration altered these plans: emissions would be lowered by only 70% by 2018. “Under the Bush plan, you will have seven times more mercury released into the waters than if we just simply followed the Clean Air Act as it is written today. There will be no overall reduction in mercury. Every other major source of pollution has been subject to the requirements of the Clean Air Act, until now. The Bush Administration has simply decided that the coal-fired power industry will be exempt.” Felice Stradler of the National Wildlife Federation Several states decided the Bush Administration plan is insufficient and are attempting to follow the original Clinton Administration plan is too lenient and they will follow the original.
    37. 37. CADMIUM (Cd) Cadmium was used in: Electroplating, solder and as a pigment for plastics But less frequently now due to health concerns Main sources of current production: By product of zinc mining Nickel-Cadmium battery production Other sources: Burning coal (0.25-0.5 ppm) and oil (0.3ppm) Wearing down of car tyres (20-90 ppm) Corrosion of galvanised metal (impurity: 0.2% Cd) Phosphate fertilisers (phosphate rock 100 ppm Cd) Sewage sludge (30 ppm) Input of Cadmium into oceans: 8000 tons/year - 50% anthropogenic
    38. 38. CADMIUM (Cd)TOXIC EFFECTS High cadmium levels can lead to:  depressed growth,  kidney damage,  cardiac enlargement,  hypertension,  foetal deformity, [Kostial (1986); Stoeppler (1991)]  cancerIn humans cadmium concentrations above 200-400ppm in kidney tissue can lead to renal damage Piotrowski & Coleman (1980)
    39. 39. Kidney dysfunction hasbeen reported incetaceans when liverconcentrations ofcadmium exceed 20ppm wet weight. Fujise et al. (1988)
    40. 40. LEAD (Pb) Lead is used in: Battery casings, pipes, sheets etc 43 million tons produced a year 10% of lead production is for lead-based additives for gas (e.g. tetraethyl lead) High levels of lead have been found in marine life near areas of high car density - e.g. 10 ppm in fish caught 300 miles off California coast - High levels of lead in UK cetaceans were attributed to lead additives in fuel (up to 4.3 ppm wet weight ~ 14 ppm dry weight) [Law et al., (1992)]
    41. 41. LEAD (Pb) The toxic effects of lead include:  anaemia,  kidney damage,  hypertension,  cardiac disease,  Immune system suppression (antibody inhibition) neurological damage Quaterman (1986)
    42. 42. OTHER HEAVY METALS OF CONCERN Aluminium Arsenic Copper chromium Iron Silver Nickel Zinc – linked with decreasing health in porpoises (Das et al., 2004) Tin….
    43. 43. Superfund site in Tacoma: a copper smelter deposited slag containing leadand arsenic along the shoreline from 1890 to 1985.In 1980 (Carter Administration) the Superfund system wasestablished to cleanup old waste sites that may pose anenvironmental or human health threat – including heavy metalcontaminated sites- over 900 sites have been cleaned to date.
    44. 44. References Clark, R.B. 2001. Metals. In: Marine Pollution. 5th Ed., pp. 98-125. Oxford University press, Oxford.Adams, D.H. 2004. Total mercury levels in tunas from offshore waters of the Florida Atlantic coast. Marine Pollution Bulletin 49: 659-663Adams, D.H. and Onorato, G.V. 2005. Mercury concentrations in red drum, Sciaenops ocellatus, from estuarine and offshore waters of Florida. Marine Pollution Bulletin 50: 291-300.Bennett, P.M., Jepson, P.D., Law, R.J., Jones, B.R., Kuiken, T., Baker, J.R., Rogan, E. and Kirkwood, J.K. 2001. Exposure to heavy metals and infectious disease mortality in harbour porpoises from England and Wales. Environmental Pollution 112: 33-40.Clarkson, T. 1987. Mercury. In: Trace Metals in Human and Animal Nutrition. Vol. 1 (Ed. W. Mertz). Academic Press, Florida.Clarkson, T.W., Magos, L. and Myers G.J. 2003. The toxicology of mercury - current exposures and clinical manifestations. New England Journal of Medicine 349: 1731-1737.Das, K., Siebert, U., Fontaine, M., Jauniaux, T., Holsbeek, L., and Bouquegneau, J.-M. 2004. Ecological and pathological factors related to trace metal concentrations in harbour porpoises Phocoena phocoena from the North Sea and adjacent areas. Marine Ecology Progress Series 281: 283-295.Endo, T., Haraguchi, K., Cipriano, F., Simmonds, M.P., Hotta, Y. and Sakata, M. 2004. Contamination by mercury and cadmium in the cetacean products from the Japanese market. Chemosphere 54:1653-1662.Endo, T., Hotta, Y., Haraguchi, K. and Sakata, M. 2003a. Mercury contamination in the red meat of whales and dolphins marketed for human consumption in Japan. Environmental Science and Technology 37: 2681-2685.Endo, T., Haraguchi, K., and Sakata, M. 2003b. Renal toxicity in rats after oral administration of mercury-contaminated boiled whale livers marketed for human consumption. Archives Environmental Contamination and Toxicology 44:412-416.
    45. 45. Endo, T., Haraguchi, K., and Sakata, M. 2002. Mercury and selenium concentrations in the internalorgans of toothed whales and dolphins marketed for human consumption in Japan. Science of theTotal Environment 300: 15-22Fujise, Y., Honda, K., Tatsukawa, R. and Mishima, S. 1988. Tissue distribution of heavy metals inDall’s porpoise in the northwestern Pacific. Marine Pollution Bulletin 19: 226-30.Grandjean, P., Murata, K., Budtz-Jørgensen, E. and Weihe, P. 2004. Cardiac autonomic activity inmethylmercury neurotoxicity: 14-year follow-up of a Faroese birth cohort. Journal of Pediatrics144:169-176.Guallar, E,, Sanz-Gallardo, M.I., vant Veer, P., Bode, P., Aro, A., Gomez-Aracena, J., Kark, J.D.,Riemersma, R.A., Martin-Moreno, J.M. and Kok, F.J. 2002. Mercury, fish oils, and the risk ofmyocardial infarction. New England Journal of Medicine 347: 1747-1754.Honda, K., Tatsukawa, R., Itano, K., Miyazaki, N. and Fujiyama, T. 1983. Heavy metal concentrationsin muscle, liver and kidney tissue of Striped dolphin Stenella coeruleoalba and their variations withbody length, weight, age and sex. Agricultural and Biological Chemistry 47: 1219-1228.Islam, M.S. and Tanaka M. 2004. Impacts of pollution on coastal and marine ecosystems includingcoastal and marine fisheries and approach for management: a review and synthesis Marine PollutionBulletin 48: 624-649.Kostial, K. 1986. Cadmium. In: Trace Elements in Human and Animal Nutrition. 5th Ed. Vol. 2. (Ed. W.Hertz). Academic Press. Orlando.Leonzio, C., Focardi, S and Fossi, C. 1992. Heavy metals and selenium in stranded dolphins of thenorthern Tyrrhenian (NW Mediterranean). Science of the Total Environment 119: 77-84.Mahaffey, K.R. 2004. Methylmercury: epidemiology update. Presentation at the National Forum onContaminants in Fish, San Diego, January 28, 2004.Murata, K., Weihe, P., Budtz-Jørgensen, E., Jørgensen, P.J., Grandjean, P. 2004. Delayed brainstemauditory evoked potential latencies in 14-year-old children exposed to methylmercury. Journal ofPediatrics 144 177-183.Parsons, E.C.M. 1999. Trace metal concentrations in the tissues of cetaceans from Hong Kong’sterritorial waters. Environmental Conservation 26: 30-40.Piotrowski, J.K. and Coleman. D.O. 1980. Environmental hazards of heavy metals: summaryevaluation of lead, cadmium.and mercury – a general report. UNEP, Nairobi.
    46. 46. Quaterman, J. 1986. Lead. In: Trace metals in human and animal nutrition. Vol. 2 (Ed. W. Mertz).Academic Press, Florida.Rawson, A.J., Patton, G.W., Hofmann, S., Pietra, G.G. and Johns, L. 1993. Liver abnormalitiesassociated with chronic mercury accumulation in stranded Atlantic bottlenose dolphins. Ecotoxicologyand Environmental Safety 25: 41-47.Rawson, A.J., Patton, G.W., Hofmann, S., Pietra, G.G. and Johns, L. 1993. Liver abnormalitiesassociated with chronic mercury accumulation in stranded Atlantic bottlenose dolphins. Ecotoxicologyand Environmental Safety 25: 41-47.Schuster, P.F., Krabbenhoft, D.P., Naftz, D.L., Cecil, L.D., Olson, M.L., Dewild, J.F., Susong, D.D.,Green, J.R. and Abbott, M.L. 2002.Atmospheric mercury deposition during the last 270 years: a glacial ice core record of natural andanthropogenic sources. Environmental Science and Technology 36: 2303-2310.Siebert, U., Joiris, C., Holsbeek, L., Benkes, H., Failing, K., Frese, K. and Petzinger, E. 1999.Potential relation between mercury concentrations and necropsy findings in cetaceans from Germanwaters of the North and Baltic Seas. Marine Pollution Bulletin 38: 285-295.Steuerwald, U., Weihe, P., Jorgensen, P.J., Bjerve, K., Brock, J., Heinzow, B., Budtz-Jorgensen, E.and Grandjean, P. 2000. Maternal seafood diet, methyl mercury exposure, and neonatal neurologicfunction. Journal of Pediatrics 136: 599-605.Stoeppler, M. 1991. Cadmium. In: Metals and their compounds in the environment. (Ed. E. Merian).VCH Publishers, Weinheim, Germany.Von Burg, R. and Greenwood, M.R. 1991. Mercury. In: Trace Metals and their Compounds in theEnvironment (Ed. by E. Merian). VCH Publishers, Weinheim, Germany. SLIDE IMAGES: Moore, C. 2002. Historical background of mercury in the environment. Paper presented at the Mercury Forum, Mercury Forum, May 20-21, 2002, Mobile, TX. <http://www.masgc.org/mercury/ppt/Moore-ppt_files/frame.htm>

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