ENVIRONMENTAL

TOXICOLOGY:
Heavy Metals
 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.
 What is contamination?

Contamination is caused when an input

from human activities causes the increase
of a substance in seawater, sediments, or
organisms above the natural background
level for that area and for those organisms.
 Measuring contamination?

Contamination is usually measured as

parts (of pollutant) per million (ppm) = µg.g-1

or parts per billion (ppb) = ng.g-1 = µg.kg-1

it 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
 Heavy metal

 Heavy metal are chemicals elements with a specific gravity

that is at least 5 times the specific gravity of water
 Arsenic 5.7; cadmium 8.65; lead 11.34; mercury 13.54
 A metal having an atomic weight greater than Na, a density
greater than 5 g/cm3
 Physical properties
 High reflectivity, electrical and thermal conductivity, strength
 Easily traced and measured and fate determined
 Some notion of toxicity
 Usually includes lead, cadmium and mercury
Periodic Table
Alkali metals
Alkaline earth metals

Transition metals

‘Heavy metals’
Density > 5
 Metals in workplace

 Metals are extensively used in industrial operation thus resulting in a high risk of
exposure to workers and environment
 Welding
 Grinding
 Soldering
 Painting
 Smelting
 Storage battery
 Recycling
 Industries with high potential of lead exposures include construction work, most
smelter operations, radiator repair shops, and firing ranges.
 Cadmium is found in industrial workplaces, particularly where any ore is being
processed or smelted.
 Common sources of mercury exposure include mining, production, and transportation
of mercury, oil and gas industry as well as mining and refining of gold and silver ores.
 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 B12
 Zinc – essential component of many enzymes
 Heavy metal pollution

But in high concentrations these can be

toxic.
e.g. one asprin tablet is a useful medicine
but 100 tablets are lethal
Some heavy metals have no essential
function in the body (e.g. mercury, lead)
and any concentrations can be harmful
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
 Understanding Metal Toxicity

Fundamental concepts of : -

1. Classification of Metal
2. Absorption, storage and excretion of metal
3. Mode of action of metal toxicity
Classification of naturally-occurring metals according to toxicity & availability in the
hydrologic environment. Wood (1974)

Non-toxic Low Toxicity Mod-high Tox.

Aluminium Gold Cadmium

Iron Tin Chromium
Manganese Copper
Lead
Mercury
Nickel
Zinc
 Toxicity rating
B>Intermediate>A

• Class B most effective at binding withS-H groups, N-containing

groups
• Displace Intermediate/Class A metals
• Can form organometals

• Intermediates displace other intermediates/Class A metals

• Class A – displace other Class A metals

• Metals do not metabolize, change by binding to other molecules

• Metals regarded as ‘essential’ or ‘non-essential’
SOURCES & SINKS OF METALS IN THE ENVIRONMENT

Erosion

Biological & Chemical

transformations
Volatilization

Attachment/release in Uptake
sediment

Settling/resuspension

Storage
Anthropogenic Enrichment Factor (AEF)

Indicates extent to which human activity contributes to

global metal cycles

Metal Anthropogenic Natural Total (T) AEF

Source (A) source ([A/T] x 100)

Cadmium 8 1 9 89%
Lead 300 10 310 97%
Manganese 40 300 340 12%
Mercury 100 50 150 66%

(All values 106 kg per year)

 Bioaccumulation
Pollutants like heavy metals are CONSERVATIVE
pollutants – i.e. they aren’t broken down by bacteria etc
and are effectively permanent
Most plants and animals can regulate their metal
content to a certain point – but metals that can’t be
excreted build up in an organism over its lifetime

= BIOACCUMULATION
 Biomagnification
Animals feeding on bioaccumulators take in a higher level
of contaminants, which bioaccumulate within themselves

Those animals feeding on them gain even higher

inputs of contaminants, and bioaccumulate even
greater concentrations

and so on… with animals at the highest trophic

level obtaining highest concentrations
= BIOMAGNIFICATION

i.e. long-living, top predators bioaccumulate and

biomagnify the highest contaminant levels
 Absorption

Respiratory Absorption
 Metal may be inhaled as vapor or aerosol (fume or dust
particulate)
 Fume or vapor of some metals & compound are readily absorbed in
from alveolar space (cadmium, mercury, tetraethyl lead)
 Large particles trapped in upper respiratory tract, cleared
by mucociliary transport to pharynx and swallowed
(equivalent to oral exposure)
 Small particles may reach alveolar/gas exchange. Water soluble
metal aerosols are rapidly absorbed from alveoli into the blood
 Excretion

 Kidney - Important route of excretion

 Metals in blood plasma are bound to plasma proteins and amino acids
 Metals bound to low molecular weight proteins and amino acids are
filtered in glomerulous into fluid of the renal tubule
 Some metals (Cd & Zn) are effectively resorbed by tubular epithelia
before they reach the urinary bladder where very little resorption
occur
 Sources of heavy metal pollution
ATMOSPHERIC
 Forest fires
 Volcanic activity
 Dust particles
 Anthropogenic emissions
 coal fired power stations
 car exhausts
Clark (2001)
 Sources of heavy metal pollution
ATMOSPHERIC
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
Clark (2001)
 Sources of heavy metal pollution
RIVERS
 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
 Sources of heavy metal pollution
GROUNDWATER SEEPAGE
 Dissolved substances are carried via
ground water movement – contamination in
soil may be picked up by the moving
waters
DELIBERATE DISCHARGE
 Contaminated waste dumping
 Industrial discharges
 Sewage
Clark (2001)
Clark (2001)
Islam & Tanaka (2004).
MERCURY (Hg)
 MERCURY

Was used as “cure” for almost every ailment in the

past
Incident of methyl mercury
 Minimata Bay 1953 – 1960
 Methylmercury - The highly toxic compound bioaccumulated in fish and
shellfish when eaten by the people living around the bay, gave rise to
Minamata disease
 On grain in Iraq 1971 – 1972
Metabolism – Three form
 Elemental – Hgo
 Inorganic : Hg+ and Hg 2+
 Organic
 Toxic effects of mercury
 Mercurycan cause neurological damage,
immune system suppression and can
cause fetal abnormalities in mammals
[Clarkson (1987); von Burg and Greenwood (1991) ]

 Inhumans 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) ]
 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)]
 Toxic effects of mercury
 Mercury in the marine environment
identified as a health risk for humans –
Minamata disease

 In1952 a factory in Minamata Japan was

using mercury as a catalyst
– mercury washed into bay
 In1953 fishermen and farmers showed
symptoms – neurological damage and fetal
deformity etc.
 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 ppb (dry weight)
 Toxic effects of mercury
 Inthe 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
 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
 Recreationalfish - Red drum (Scaenops ocellatus) also
contaminated: up to 3.6 ppm; 95% >0.5 ppm health limit
[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 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)]
 Bottlenosedolphins (Tursiops truncatus)
13,156 ppm dry weight [Leonzio et al., (1992)]
 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)]
Imputs of Mercury

6000-7500 tons a year

Hg(II)
(via precipitation) Hg(0) →Hg(II)
photochemical

Microbes
 Biomagnification of methyl-Hg
Bacteria Algae Copepod

HgCl2 CH3HgCl 5 ng/g

0.010 ng/L 30 ng/g

Large fish Small fish

Humans 5000 ng/g
1000 ng/g 180 ng/g
 Bioaccumulation of methyl-Hg
• Accumulates in tissues over time
• Concentrates in the muscle tissue of fish
• Accumulates in the envelopes of nerve cells
• 100x more toxic than Hg0 and Hg2+
• Destroys muscle proteins and enzymes essential to
cell function
 The mercury resistance (mer) system in
microbes

CH3Hg(I)

Lin et al., In: Environmental Chemistry and Toxicology of Mercury, in press

• Common among bacteria in soils and natural waters

• Applications in bioremediation and in monitoring of mercury in the
environment
Clark (2001)
 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
he pre-industrial era

Schuster (2002)
Schuster (2002)
 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
 CADMIUM (Cd)
TOXIC EFFECTS
High cadmium levels can lead to:
 depressed growth,
 kidney damage,
 cardiac enlargement,
 hypertension,
 foetal deformity,
[Kostial (1986); Stoeppler
 cancer (1991)]

In humans cadmium concentrations above 200-400

ppm in kidney tissue can lead to renal damage

Piotrowski & Coleman

Kidney dysfunction has
been reported in
cetaceans when liver
concentrations of
cadmium exceed 20
ppm wet weight.

Fujise et al. (1988)

 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)

 Highlevels 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)]
 LEAD (Pb)
 The toxic effects of lead include:
 anaemia,
 kidney damage,
 hypertension,
 cardiac disease,
 Immune system suppression (antibody inhibition)
neurological damage
Quaterman (1986)
(Micrograms
per decilitre)
BIO-
ACCUMULATION
Absorbed into blood

Deactivates enzymes that

make haemoglobin
Pb
Precursor ALA builds up Inhibits

Paralyses gut,
Fluid on brain,
Affects reproductive
system
Anaemia
OTHER HEAVY METALS OF
CONCERN
 Aluminium
 Arsenic
 Copper
 chromium
 Iron
 Silver
 Nickel
 Zinc – linked with decreasing health in porpoises
(Das et al., 2004)
 Tin….
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.
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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>