HEAVY METAL

Contaminants
 METAL
• An element whose atoms are packed
closely together by strong forces of
attraction with free electrons moving
around

• Physical Properties:
- Good conductor of electricity
- High melting point
- High thermal conductivity
- High density
- Malleable
- Ductile
 P Group**
Periodic Table
 
er         18
1                              
io   VIII
IA
d A
1A 17
1 2 13 14 15 16 8A
2
VII He
1 H IIA                     IIIA IVA VA VIA
A 4.00
1.008 2A 3A 4A 5A 6A
3 4
5 6 7 8 7A
9 3
10

2 Li Be                     B C N O F Ne
10.8 12.0 14.0 16.0 19.0 20.1
6.941 9.012
7 8 9 10 1 1 1 0 0 8
13 14 15 16 17 18
11 12 3 4 5 6 11 12
VII Al Si P S Cl Ar
3 Na Mg IIIB IVB VB VIB IB IIB
B 26.9 28.0 30.9 32.0 35.4 39.9
22.99 24.31 3B 4B 5B 6B ------- VIII ------- 1B 2B
7B 8 9 7 7 5 5
21 22 23 26------- 27
8 -------28 30 31 32 33 34 35 36
19 20 24 25 29
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
44.9 47.8 50.9 55.8 58.4 58.6 65.3 69.7 72.5 74.9 78.9 79.9 83.8
39.10 40.08 52.00 54.94 63.55
6 8 4 5 7 9 9 2 9 2 6 0 0
39 40 41 42 44 45 46 47 48 49 50 51 52 53 54
37 38 43
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
88.9 91.2 92.9 95.9 101. 102. 106. 107. 112. 114. 118. 121. 127. 126. 131.
85.47 87.62 57 (98)
1 2 1 4 1 9 4 9 4 8 7 8 6 9 3
72 73 74 75 76 77 78 79 80 81 82 83
55 56 La 84 85 86
6 Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3
* 178. 180. 183. 186. 190. 190. 195. 197. 200. 204. 207. 209.
(210) (210) (222)
138.
89 5 9 9 2 2 2 1 0 5 4 2 0
87 88 9 104 105 106 107 108 109 110 111 112 114 116 118
7 Ac      
Fr Ra Rf Db Sg Bh Hs Mt --- --- --- --- --- ---
(223) (226) ~ (257) (260) (263) (262) (265) (266) () () () () () ()
(227)
 
                                 
62   69
58 59 60 61 63 64 65 66 67 68 70 71
Lanthanide
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu    
Series* 140. 140. 144. 152. 157. 158. 162. 164. 167.
168.
173. 175.
1 9 2 150. 0
95 3
96 9 5 9 3
100 101 0 0
90 (147) 9
4
Actinide 91 92 93 94
Am Cm
97 98 99
Fm Md
102 103
Th Pa U Np Pu Bk Cf Es No Lr    
Series~ 232.
(231) (238) (237) (242) (247) (249) (254) (254) (257)
0
(243) (247) (253) (256)
 Heavy Metal
• Refer to several elements
beginning with beryllium &
actinides
• Generally having an atomic
numbers 22 to 92 in all groups
from period 3 to 7 in the periodic
table
• MARC definition – metals of atomic
weight higher than sodium and
having a specific gravity of more
than 5g/cm3
• Over 70 metallic elements
 Toxicity
• Cause catastrophic effect on
normal metabolic function even
when present in small amounts
• Change biological structures &
systems, leading to deformity or
finally death
• Almost all metals are toxic at
higher concentrations & some are
lethal even at low concentrations
 Why are heavy metals
toxic???
• Have a great affinity for sulphur attack,
e.g –SH bonds in enzymes, thereby
immobilising it
• Attack protein carboxylic acid groups
(-COOH) & amino groups (-NH2)
• Involve binding to the metabolically
active groups such as amino-,
sulphydryl-, carboxyl-, phenolic- or
phosphoryl-
• Progressive accumulation of metals
through food chain, causing
biomagnification, especially in fish
Toxicity to Humans & Aquatic
Organisms
Meta Toxicity To
l
Huma Fish Invertebrat Plant
n e
As Very- Very- Variable Variabl
High High e
Cd Medium Medium High Low-
Mediu
High Medium Medium m
Low-
Pb
Mediu
High High Variable m
High
Hg
 Arsenic (As)
• Best known of the toxic trace
metals
• No known biological function & is
highly toxic
• Exists in organic & inorganic forms
• Inorganic forms are more harmful
but there are great differences in
toxicity of different arsenic
compounds
• Common effects: skin cancer &
dermatitis
 Toxicity of As
• Depends on:
- valence states (0, +3 & +5)

- organic & inorganic forms

- physical aspects (absorption &
elimination)
• Inorganic arsenic & +3 arsenic are more
toxic than organic & zero-valent or +5
arsenic
• Under Food Act, the limit of As presence
for fish, crustaceans & molluscs should
be
 Presence of As
• Widely distributed in nature in number
of minerals
• Industrial sources: by-product in the
smelting of copper, lead & nickel ores
• Methylated arsenic exists due to
conversion of As by microorganism
• Organic As is the predominant form
accumulated in aquatic species
• As compounds (pesticide, herbicides)
used in agricultural purposes get wash
into the marine environment
 As poisoning
• Black food disease cause by the
chronic ingestion of inorganic As
• Incidence of massive As poisoning:
nearly 50 million in Bangladesh are
reported to be victims of the
poisoning due to the drinking
water that had been found with
80% contaminated with As beyond
the safe limit
 Cadmium (Cd)
• No essential biological functions
• Extremely toxic to human due to
the absence of homeostatic control
for the metal in the body
• Common effects: Bronchitis,
Kidney damage, skeletal damage,
carcinogenic, affects heart & liver
 Toxicity of Cd
• Inhibition of various enzyme
systems e.g. inactivating enzymes
containing sulphydryl groups
• Can compete with other metals
such as Zn & Se for inclusion into
metallo-enzymes as well as Ca for
binding sites for regulatory
proteins
 Presence of Cd
• Widely distributed in the earth crust
• Released from volcanic activity
• Widespread use in the metal plating &
smelting of nonferrous metal ores
• Commonly found in metallic form as
sulphites & sulphates
• Contamination arises from mine
drainage water, waste water from
processing of ores leading to pollution
of aquatic environment
 Cd Poisoning
• “Itai-itai” disease (“ouch-ouch”) caused
by chronic ingestion of Cd
• Incidence of massive Cd poisoning:
In 1965, Japan reported ~100 deaths by
consuming rice contaminated with Cd
for several years
 Lead (Pb)
• An element of particular interest to the
food analyst as it is highly toxic
• A bluish or silvery-grey soft metal
• Exist in both organic & inorganic forms
• Organic lead is more poisonous than
inorganic lead
• Common effects: anaemia, cardiac
disease, kidney damage, reduced
antibody synthesis optical atrophy,
tremors & wrist drop.
 Toxicity of Pb
• Elemental Pb & inorganic Pb are
absorbed by ingestion or inhalation
while organic Pb is absorbed by skin
contact
• Has an affinity for cell membranes,
affecting sodium, potassium & calcium
ATP-ase pumps, impairing enzyme
protein kinase C in the brain & also
altering gene expression
• Under Food Act, the limit of Pb
presence for fish, crustaceans &
molluscs should be
 Flow Diagram of the effects
of lead in the body
Entry of lead into the body

Enters the blood & is absorbed rapidly into the blood plasma. Progressively 
taken up by red blood cells where it binds to haemoglobin & other molecules

Equilibrates rapidly with extra-cellular fluid

Crosses membranes in the body including the blood-brain barrier & the 
placents / accumulates in soft & hard tissue especially in calcium sites

Obstructing the utilisation of oxygen & glucose for life sustaining 
energy production, causing kidney dysfunction & brain damage / 
replacing calcium in bones
 Presence of Pb
• Occurs through releases (directly
or through atmospheric deposition)
from smelting & refining of Pb, the
burning of petroleum fuels
containing lead additives
• Metallic lead deriving from shotgun
cartridges, storage battery, solder,
pipe, brass or used as fishing
weights thus washing into the
aquatic environment
 Mecury (Hg)
• Extremely toxic trace metal
• Exist in 3 oxidation states (0, +1,
+2)
• Exists in inorganic & organic forms
• Organic Hg is more toxic,
particularly in the form of methyl
mercury
• Common effects: loss of vision,
hearing & intellectual abilities &
nervous disorders
 Toxicity of Hg
• A potent inhibitor of some enzymes &
blocks the transport of potassium into
cells & the transport of sugars
• Vapour Hg is easily absorbed by the
lungs
• Inorganic Hg can be absorbed through
the GI tract & also through the skin
• Organic Hg undergo pulmonary
absorption & are well absorbed by
ingestion
• Long-term effect: accumulation in the
kidney & brain for years
 Presence of Hg
• Natural Hg arises from the degassing of the
earth’s crust through volcanic gases & by
evaporation from the oceans
• Atmospheric poluution from industrial
production, water pollution by mine tailings,
burning of fossil fuels, chloralkali & wood
pulping industry & as fungicides in agriculture
• Dissolved Hg has a strong affinity for organic
matter & suspended sediment. Hg can
undergo methylation to produce
methylmecury
 Hg poisoning
• Ingestion of mercuric chloride (in disinfectant) &
from contaminated illegal drugs eg,
amphetamines
• Industrial accidents in which Hg vapour was
inhaled
• Environmental discharge of industrial waste thus
contaminating the marine lives
• Incidences of massive poisoning:
- “Minimata disease” - In 1953, 52 persons in
Japan were killed by chronic poisoning after
consuming shellfish contaminated with Hg
containing effluent from a nearby plastic industry
- In 1972, 450 Iraqi villagers died after consuming
grain treated with Hg containing pesticides
Internationally accepted safe levels
of exposure to metals

Metal Standard Reference

Inorganic 15ug/kg body weight per week WHO 1989
As
Cd 7ug/kg body weight per week WHO 1989
Pb 25ug/kg body weight per week WHO 1998
Hg 5ug/kg body weight per week WHO 1972
Reference dose of 0.1ug/kg of body USEPA
weight per day 1995
 Methodology

• A lot of methods for quantification or

qualification of heavy metals
• Qualification – Wet Chemistry
• Quantification – Atomic Spectroscopy (Flame
AAS, Furnace AAS, ICP-OES and ICP-MS)
• In Marine Fisheries Research Department,
accredited methods under ISO/IEC 17025
were adopted for the determination of the four
heavy metals
Analysis of Total Hg
Sample Preparation

Dried Fish Sample Wet Digestion

Conc HNO3 + H2SO4

NaBH4

Hg Vapour
Analysis

Flow injection
AAS
 Analysis of Total As
Sample Preparation

Dried Fish Sample Wet Digestion

Conc HNO3 + H2SO4 + HClO4

Pre-Reduction ( Conc HCl + KI + Ascorbic Acid)

NaBH4

AsH Vapour
Analysis

Flow injection
AAS
 Flow Injection Atomic
Absorption Spectrometer
 Analysis of Total Pb & Cd

Dried Fish Sample 1st Ashing 2nd

Ashing
450oC/ 16hrs Conc HNO3 (450oC/ 2hrs)

6M HCl
+ 0.1M HNO3

Sample Solution

Analysis
Matrix Modifier
Graphite Furnace
AAS
Graphite Furnace Atomic
Absorption Spectrometer
 Conclusion
• Stop Marine Pollution

• Maintain a well-balanced diet to

avoid excessive exposure to
contaminants from a small range
of food items
Thank You