Download - 2 pollution (heavy metals)w
What is marine pollution?What is marine pollution?
According to the UN Group of Experts on the According to the UN Group of Experts on the Scientific Aspects of Marine Pollution Scientific Aspects of Marine Pollution (GESAMP):(GESAMP):
Marine pollution is the introduction by man, Marine pollution is the introduction by man, directly or indirectly, of substances or energy to directly or indirectly, of substances or energy to the marine environment resulting in deleterious the marine environment resulting in deleterious effects such as: effects such as: hazards to human health; hazards to human health; hindrance of marine activities, including fishing;hindrance of marine activities, including fishing;impairment of the quality for the use of seawater, impairment of the quality for the use of seawater, and reduction of amenities.and reduction of amenities.
What is contamination?What is contamination?
Contamination is caused when an input Contamination is caused when an input from human activities causes the increase from human activities causes the increase of a substance in seawater, sediments, or of a substance in seawater, sediments, or organisms above the natural background organisms above the natural background level for that area and for those level for that area and for those organisms. organisms.
Measuring contamination?Measuring contamination?
Contamination is usually measured as Contamination is usually measured as parts (of pollutant) per million (ppm) = parts (of pollutant) per million (ppm) = µµg.gg.g-1-1
or parts per billion (ppb) = or parts per billion (ppb) = nng.gg.g-1-1 = = µµg.kgg.kg-1-1
it is measured as “wet weight” it is measured as “wet weight” (e.g. contamination in moist water containing tissues)(e.g. contamination in moist water containing tissues)
as water content can vary a lot as water content can vary a lot – dry weight is a better measure – dry weight is a better measure
or as “dry weight” or as “dry weight” (e.g. contamination in dehydrated tissues)(e.g. contamination in dehydrated tissues)
Heavy metal pollutionHeavy metal pollution
High atomic weight metals (mercury, lead etc.)High atomic weight metals (mercury, lead etc.)Sometimes the term trace elements is used to Sometimes the term trace elements is used to include non-metal and lower atomic weight include non-metal and lower atomic weight elementselementsMany of these elements are essential to the Many of these elements are essential to the body in very low concentrations: body in very low concentrations:
Iron – essential for hemoglobinIron – essential for hemoglobin Copper - essential for hemocyanin Copper - essential for hemocyanin (in invertebrates)(in invertebrates) Cobalt – in vitamin BCobalt – in vitamin B1212
Zinc – essential component of many enzymesZinc – essential component of many enzymes
Heavy metal pollutionHeavy metal pollution
But in high concentrations these can be But in high concentrations these can be toxic.toxic.e.g. one asprin tablet is a useful medicinee.g. one asprin tablet is a useful medicine
but 100 tablets are lethalbut 100 tablets are lethal
Some heavy metals have no essential Some heavy metals have no essential function in the body (e.g. mercury, lead) function in the body (e.g. mercury, lead) and any concentrations can be harmfuland any concentrations can be harmful
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
Clark (2001)
BioaccumulationBioaccumulation
Pollutants like heavy metals are CONSERVATIVE Pollutants like heavy metals are CONSERVATIVE pollutants – i.e. they aren’t broken down by bacteria etc pollutants – i.e. they aren’t broken down by bacteria etc and are effectively permanentand are effectively permanent
Most plants and animals can regulate their metal Most plants and animals can regulate their metal content to a certain point – but metals that can’t content to a certain point – but metals that can’t be excreted build up in an organism over its be excreted build up in an organism over its lifetimelifetime
= = BIOACCUMULATION BIOACCUMULATION
BiomagnificationBiomagnification
Animals feeding on bioaccumulators take in a higher Animals feeding on bioaccumulators take in a higher level of contaminants, which bioaccumulate within level of contaminants, which bioaccumulate within themselvesthemselves
Those animals feeding on them gain even higher Those animals feeding on them gain even higher inputs of contaminants, and bioaccumulate even inputs of contaminants, and bioaccumulate even greater concentrationsgreater concentrations
= = BIOMAGNIFICATIONBIOMAGNIFICATION
and so on… with animals at the highest trophic and so on… with animals at the highest trophic level obtaining highest concentrationslevel obtaining highest concentrations
i.e. long-living, top predators bioaccumulate and i.e. long-living, top predators bioaccumulate and biomagnify the highest contaminant levelsbiomagnify the highest contaminant levels
Sources of heavy metal pollutionSources of heavy metal pollution
ATMOSPHERICATMOSPHERIC Forest firesForest fires Volcanic activityVolcanic activity Dust particlesDust particles Anthropogenic emissions Anthropogenic emissions
coal fired power stationscoal fired power stations car exhaustscar exhausts
Sources of heavy metal pollutionSources of heavy metal pollution
ATMOSPHERICATMOSPHERICMetals can be transferred by the atmosphere in gas or Metals can be transferred by the atmosphere in gas or particle form particle form (aerosol)(aerosol)
Particles can fall from the atmosphere onto the land or sea = Particles can fall from the atmosphere onto the land or sea = dry depositiondry deposition
Also precipitation can carry particles or dissolved gases = Also precipitation can carry particles or dissolved gases = wet depositionwet deposition
Gaseous state elements Gaseous state elements (Boron, Mercury, Selenium)(Boron, Mercury, Selenium) can also dissolve can also dissolve at the surface of water bodies (gaseous exchange)at the surface of water bodies (gaseous exchange)
Bubbles breaking the surface of the sea can release salt Bubbles breaking the surface of the sea can release salt particles containing metals particles containing metals
– – can travels from sea to atmosphere as well as atmosphere to seacan travels from sea to atmosphere as well as atmosphere to sea
Sources of heavy metal pollutionSources of heavy metal pollution
RIVERSRIVERS Erosion of rocks containing metalsErosion of rocks containing metals Surface runoff sweeps up naturally formed Surface runoff sweeps up naturally formed
and anthropogenic metal particlesand anthropogenic metal particlesMetals often bind with sediments and are Metals often bind with sediments and are deposited on the seabeddeposited on the seabed
– – but these can enter the marine environment but these can enter the marine environment again is there is:again is there is: DredgingDredging TrawlingTrawling Severe weatherSevere weather
Sources of heavy metal pollutionSources of heavy metal pollution
GROUNDWATER SEEPAGEGROUNDWATER SEEPAGE Dissolved substances are carried via Dissolved substances are carried via
ground water movement – contamination ground water movement – contamination in soil may be picked up by the moving in soil may be picked up by the moving waterswaters
DELIBERATE DISCHARGEDELIBERATE DISCHARGE Contaminated waste dumping Contaminated waste dumping Industrial dischargesIndustrial discharges SewageSewage
Toxic effects of mercuryToxic effects of mercury
Mercury can cause neurological damage, Mercury can cause neurological damage, immune system suppression and can immune system suppression and can cause fetal abnormalities in mammals cause fetal abnormalities in mammals
[Clarkson (1987); von Burg and Greenwood (1991)[Clarkson (1987); von Burg and Greenwood (1991) ] ]
In humans it has been associated with In humans it has been associated with various neurological effects, abnormal various neurological effects, abnormal development and heart damage development and heart damage
[Guallar et al., (2002); Clarkson [Guallar et al., (2002); Clarkson et al.,et al., (2003); Murata (2003); Murata et al.et al. (2004); Grandjean et al. (2004) (2004); Grandjean et al. (2004) ] ]
Mercury toxicityMercury toxicity
Visual field constriction Visual field constriction Behavioral changes, memory loss, headaches Behavioral changes, memory loss, headaches Tremor, loss of fine motor control, spasticity Tremor, loss of fine motor control, spasticity Hair loss Hair loss
In human adults mercury toxicity symptoms include:In human adults mercury toxicity symptoms include:
If fetuses / infants are exposed to mercury: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 [Clarkson et al.,et al., (2003) (2003)]]
Toxic effects of mercuryToxic effects of mercury
Mercury in the marine environment Mercury in the marine environment identified as a health risk for humans –identified as a health risk for humans –
Minamata diseaseMinamata disease
In 1952 a factory in Minamata Japan was In 1952 a factory in Minamata Japan was using mercury as a catalyst using mercury as a catalyst – mercury washed into bay – mercury washed into bay
In 1953 fishermen and farmers showed In 1953 fishermen and farmers showed symptoms – neurological damage and symptoms – neurological damage and fetal deformity etc.fetal deformity etc.
Minamata diseaseMinamata disease Disease diagnosed in 1956 Disease diagnosed in 1956
– linked to fish consumption – linked to fish consumption
1957 fishing banned in area1957 fishing banned in area
1959 – mercury identified as cause1959 – mercury identified as cause
1960 source identified 1960 source identified – factory effluent– factory effluent
2000 cases –2000 cases – 41 deaths and 700 permanent disabilities41 deaths and 700 permanent disabilities
fish: 10-55 ppm fish: 10-55 ppm (dry weight)(dry weight); bivalves 10-39 ppp ; bivalves 10-39 ppp (dry weight)(dry weight)
Toxic effects of mercuryToxic effects of mercury
In the US an estimated 650,000 newborns a In the US an estimated 650,000 newborns a year are at risk from developmental and year are at risk from developmental and neurological damage due mercuryneurological damage due mercury [[Mahaffey (2004)Mahaffey (2004)]]
The source of this mercury is The source of this mercury is contaminated seafoodcontaminated seafood
Around the world seafood with mercury Around the world seafood with mercury levels over 0.5 to 1.0 ppm are considered levels over 0.5 to 1.0 ppm are considered unsafe for human consumptionunsafe for human consumption
Mercury in fishMercury in fish Most fish species have mercury levels of Most fish species have mercury levels of
approximately 0.15 ppm in muscle tissueapproximately 0.15 ppm in muscle tissue However cod have been found with levels of However cod have been found with levels of
1.29 ppm in Sweden and Denmark1.29 ppm in Sweden and Denmark Tuna highly contaminated Tuna highly contaminated [Adams (2004)][Adams (2004)]
Blackfin tuna (Blackfin tuna (Thunnus atlanticusThunnus atlanticus) up to 2ppm) up to 2ppm 81% more contaminated than 0.5 ppm health regulation81% more contaminated than 0.5 ppm health regulation
Little tunny (Little tunny (Euthynnus alletterusEuthynnus alletterus) up to 3.4ppm) up to 3.4ppm 75% more contaminated than 0.5 ppm health regulation75% more contaminated than 0.5 ppm health regulation
Recreational fish - Red drum Recreational fish - Red drum ((Scaenops ocellatusScaenops ocellatus) ) also also contaminated: contaminated: up to 3.6 ppm;up to 3.6 ppm; 95% >0.5 ppm health limit95% >0.5 ppm health limit
[Adams & Onorato (2004)][Adams & Onorato (2004)]
Adams (2004)
Yellowfin tuna are pelagic and have lower levels of Hg. Blackfin tuna are primarily near-shore species and show elevated Hg concentrations
Mercury in marine mammalsMercury in marine mammals As long-lived top predators marine mammals As long-lived top predators marine mammals
accumulate very high concentrations of mercuryaccumulate very high concentrations of mercury
Striped dolphins Striped dolphins ((Stenella coeruleoalbaStenella coeruleoalba)) 485 ppm 485 ppm wet weightwet weight (~ 1600 ppm (~ 1600 ppm dry weightdry weight))
[Honda [Honda et alet al., (1983)]., (1983)]
Indo-Pacific humpback dolphinsIndo-Pacific humpback dolphins ((Sousa chinensisSousa chinensis)) 900 ppm 900 ppm dry weightdry weight [Parsons (1999)][Parsons (1999)]
Bottlenose dolphins Bottlenose dolphins ((Tursiops truncatusTursiops truncatus)) 13,15613,156 ppm ppm dry weightdry weight [Leonzio[Leonzio et alet al., (1992)]., (1992)]
Mercury in marine mammalsMercury in marine mammals Toxic effects reported in marine mammals Toxic effects reported in marine mammals
include:include:
High mercury (and other heavy metal) levels High mercury (and other heavy metal) levels have also been associated with disease have also been associated with disease -induced mortality -induced mortality i.e. mercury may damage the immune i.e. mercury may damage the immune systemsystem [Bennett [Bennett et alet al., (2001)]., (2001)]
Lesions in the liver and other tissues; decrease nutritional Lesions in the liver and other tissues; decrease nutritional state and fatty degenerationstate and fatty degeneration
[Rawson [Rawson et alet al., (1993); Siebert ., (1993); Siebert et al.,et al., (1995)] (1995)]
Mercury in whale meatMercury in whale meatRecent research has shown that cetacean meat being sold in Japan for human consumption had extremely high levels of mercury
Mean contamination levels in cetacean red meat were 22 and 18 times higher than levels permitted by the Japanese government for total mercury (0.4 ppm)
Levels were exceeded by up to 200x
Mercury levels in boiled liver were even higher: 1,980 ppm (wet weight).
Rats fed contaminated meat showed signs of kidney abnormalities after a single dose Endo et al., (2002; 2003a; 2003b; 2004)
Mercury in whale meatMercury in whale meatAnother study in the Faeroe islands looked at the effects on the population of eating contaminated long-finned pilot whale meat
Effects linked with mercury contamination included mental retardation, neurological abnormalities and brain stem damage in children
Abnormal heart activity also linked to mercury contamination
Prenatal exposure to mercury was believed to be causing irreversible neurological damage
[ Murata [ Murata et al.et al. (2004); Grandjean (2004); Grandjean et al.et al. (2004) (2004) ] ]
U.S. Anthropogenic Mercury U.S. Anthropogenic Mercury EmissionsEmissions
~ 158 Metric Tons~ 158 Metric Tons Sources Sources 87% combustion 87% combustion
33% coal fired power33% coal fired power 19% burning municipal 19% burning municipal
waste waste 10% burning medical 10% burning medical
waste waste
10% manufacturing 10% manufacturing 3% all other sources 3% all other sources
Mercury Emissions
Global
US
• 2/3 deposited outside US
•~53 tons deposited inside US+ 35 tons deposited in US from outside sources
Mercury emissions
Mercury Production 1996Mercury production
6%
15%
Data & Images: Moore (2002)
Mercury trendsMercury trends Over past 100 years there’s been a 20 x Over past 100 years there’s been a 20 x
increase in the deposition of mercuryincrease in the deposition of mercury 70% of this mercury has been from 70% of this mercury has been from
anthropogenic sources anthropogenic sources Over past 10 years – deposition has declined Over past 10 years – deposition has declined
– – BUT deposition rate is still 11x higher than in BUT deposition rate is still 11x higher than in the pre-industrial erathe pre-industrial era
Schuster (2002)
CONTROVERSIAL: CONTROVERSIAL: Mercury and US PolicyMercury and US Policy During the Clinton Administration the Environmental During the Clinton Administration the Environmental
Protection Agency conducted research on the impacts of Protection Agency conducted research on the impacts of mercury and the role of coal-fired power plants in mercury mercury and the role of coal-fired power plants in mercury emissions. emissions.
The EPA introduced a plan in which mercury emissions from The EPA introduced a plan in which mercury emissions from coal-fired power plants would be reduced by 90% by 2008. coal-fired power plants would be reduced by 90% by 2008.
The Bush Administration altered these plans: emissions The Bush Administration altered these plans: emissions would be lowered by only 70% by 2018. 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 Felice Stradler of the National Wildlife Federation
Several states decided the Bush Administration plan is insufficient and Several states decided the Bush Administration plan is insufficient and are attempting to follow the original Clinton Administration plan is too are attempting to follow the original Clinton Administration plan is too lenient and they will follow the original. lenient and they will follow the original.
CADMIUM (Cd)CADMIUM (Cd) Cadmium was used in:Cadmium was used in:
Electroplating, solder and as a pigment for plasticsElectroplating, solder and as a pigment for plasticsBut less frequently now due to health concernsBut less frequently now due to health concerns
Main sources of current production:Main sources of current production:By product of zinc miningBy product of zinc mining
Nickel-Cadmium battery productionNickel-Cadmium battery production
Other sources:Other sources:Burning coal (0.25-0.5 ppm) and oil (0.3ppm)Burning coal (0.25-0.5 ppm) and oil (0.3ppm)
Wearing down of car tyres (20-90 ppm)Wearing down of car tyres (20-90 ppm)
Corrosion of galvanised metal (impurity: 0.2% Cd) Corrosion of galvanised metal (impurity: 0.2% Cd)
Phosphate fertilisers (phosphate rock 100 ppm Cd)Phosphate fertilisers (phosphate rock 100 ppm Cd)
Sewage sludge (30 ppm)Sewage sludge (30 ppm)
Input of Cadmium into oceans: 8000 tons/yearInput of Cadmium into oceans: 8000 tons/year- 50% anthropogenic- 50% anthropogenic
CADMIUM (Cd)CADMIUM (Cd)
TOXIC EFFECTSTOXIC EFFECTS
High cadmium levels can lead to: High cadmium levels can lead to: depressed growth, depressed growth, kidney damage, kidney damage, cardiac enlargement, cardiac enlargement, hypertension, hypertension, foetal deformity,foetal deformity, cancercancer
In humans cadmium concentrations above 200-400 In humans cadmium concentrations above 200-400 ppm in kidney tissue can lead to renal damageppm in kidney tissue can lead to renal damage
[Kostial (1986); Stoeppler (1991)]
Piotrowski & Coleman (1980)Piotrowski & Coleman (1980)
Kidney dysfunction has been reported in cetaceans when liver concentrations of cadmium exceed 20 ppm wet weight.
Fujise et al. (1988)
LEAD (Pb)LEAD (Pb) Lead is used in:Lead is used in:
Battery casings, pipes, sheets etcBattery casings, pipes, sheets etc
43 million tons produced a year43 million tons produced a year
10% of lead production is for lead-based 10% of lead production is for lead-based additives for gas (e.g. tetraethyl lead)additives for gas (e.g. tetraethyl lead)
High levels of lead have been found in marine life High levels of lead have been found in marine life near areas of high car densitynear areas of high car density- e.g. 10 ppm in fish caught 300 miles off California coast- e.g. 10 ppm in fish caught 300 miles off California coast
- High levels of lead in UK cetaceans were attributed to lead - High levels of lead in UK cetaceans were attributed to lead additives in fuel additives in fuel
(up to 4.3 ppm wet weight ~ 14 ppm dry weight)(up to 4.3 ppm wet weight ~ 14 ppm dry weight) [Law [Law et alet al., (1992)]., (1992)]
The toxic effects of lead include:The toxic effects of lead include: anaemia, anaemia, kidney damage, kidney damage, hypertension, hypertension, cardiac disease, cardiac disease, Immune system suppression Immune system suppression (antibody inhibition)(antibody inhibition)
neurological damage neurological damage Quaterman (1986) Quaterman (1986)
LEAD (Pb)LEAD (Pb)
AluminiumAluminium ArsenicArsenic CopperCopper chromiumchromium IronIron SilverSilver NickelNickel Zinc – Zinc – linked with decreasing health in porpoises linked with decreasing health in porpoises
(Das (Das et alet al., 2004)., 2004)
Tin….Tin….
OTHER HEAVY METALS OF OTHER HEAVY METALS OF CONCERNCONCERN
Superfund site in Tacoma: a copper smelter deposited slag containing lead and arsenic along the shoreline from 1890 to 1985.
In 1980 (Carter Administration) the Superfund system was established to cleanup old waste sites that may pose an environmental or human health threat – including heavy metal contaminated sites
- over 900 sites have been cleaned to date.
ReferencesReferences
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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>