Classes of toxic substances - 2:

(Heavy) metals
 Ia IIa IIIb IVb Vb VIb VIIb VIII Ib IIb IIIa IVa Va VIa VIIa O
1 2
H He
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 13 14 15 16 17 18
Na Mg <------------------------------------d-block---------------------------------------> Al Si P S Cl Ar
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 16
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
87 88 89 104 105 <-------------------p-block--------------------->
Fr Ra Ac# Rf Ha
<--s-block--> 58 59 60 61 62 63 64 65 66 67 68 69 70 71
* lanthanides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90 91 92 93 94 95 96 97 98 99 100 101 102 103
# actinides Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

Metals: in bold lines; Heavy metals: underlined

Metalloids: grey (have properties of both metals and non-metals)
Essential elements: in italics
 What are heavy metals?

Metals with > 5 g/cm3 in metal form

Positive charge when present as free ion (cat ion)

Usually different valences

Binding to O-, N- and S-containing groups in

macro molecules (e.g. proteins/enzymes)

At low concentrations present in the environment

(trace elements)
Concentrations of lead in human bones
related to human activities involving the
use of Pb
Period Lead
content
(mg/kg)
Pre-Roman 36
Roman 251
9th 12th century 73
Middel ages 200
th
20 century 1700
 Sources of metals

consequence of human activity

- unintended release (e.g. mining operations, shipwrecks,
nuclear accidents)
- disposal of wastes (e.g. sewage, industrial effluents)
- pesticide use (e.g. Cu, Sn, As)

natural sources
- weathering of rocks (metals, inorganic anions)
- volcanic activity
 Essential and
non-essential
metals

Essential:
Fe, Mn, V, Cu, Zn,
Ni, Co, Mo

Non-essential:
Ti, Sr, Pb, Sn, Cd
 Are metals xenobiotic?

Xenobiotic = comes from humans activities,

strange to live

All metals circulate through the human body

Some are necessary (essential), others are

not

Essentiality is species specific

 Biochemical roles of metals

Iron Haemoglobin, cytochromes ( respiration)

Zinc Co-factor in many enzymes, DNA-

binding peptides, stabilisation of
membranes and proteins

Copper Superoxide dismutase ( oxidative stress)

Molybdenum Xanthine-oxidase ( N metabolism)

Chromium Activating insulin receptor ( metabolism)

 Toxicity at the biochemical level

Inhibition of enzymes (Pb, Hg, Cd, Cu)

Binding to proteins (Hg, Cd, Cu, Zn)
Blocking ion channels (Cd)
Binding to DNA (Cr, Cd)
Catalysing radical reactions (Fe, Cu)
Peroxidation of membrane lipids (Fe, Cu)
Replacement of essential metals (Cd)
 Pb

(Lead)
 Toxicity of lead
System Effects

Nervous Mental retardation

system among children
Arterial Disruption of haem
system synthesis, anaemia
Bones Accumulation
Kidneys Kidney damage
among workers in
metal industry
 Pb poisoning in children in China

Lead poisoning cases spark riots in China

Thousands of children living near smelting plants in China have
been found with unsafe levels of lead in their blood in the latest
health scandal to hit the country. Jonathan Watts reports.

More than 140 children have been treated in hospital.

Blood Pb levels > 100 g/l; highest level recorded 239 g/l

The Lancet Vol 374 September 12, 2009

 As

(Arsenic)
 Unintended release

Arsenic in Bangladesh:
- > 75 million at risk from As
contaminated drinking water from
wells dug (1980s-early 1990s).
- Problem not noticed until victims
began showing external
symptoms of As poisoning:
calluses on palms and soles of
feet, leading to skin cancers.

http://www.sos-arsenic.net/ http://bicn.com/acic/
http://www.unesco.org/courier/2001_01/uk/planet.htm
Contamination of drinking-water by arsenic in Bangladesh: a public health
emergency. AH. Smith, EO. Lingas, & M Rahman
Bulletin of the World Health Organization, 2000, 78 (9)
 Arsenic in Bangladesh: situation description

- Arsenic-rich groundwater found in entire Bengal delta

- Mainly natural (geogenic), little human influence
- Probably introduced by sulphur-rich sediments, deposited
by Rivers Ganges, Brahmaputra and Meghna (Himalaya)

- Arsenopyrite (FeAsS) main As containing mineral

weathered through pitticide ([Fe, SO4, AsO4, H2O] and

scorolite [FeAs4, 2H2O] to form ferric arsenate (FeAsO4)
 Arsenic speciation
in groundwater

At pH < 7:

FeAsO4 + 2H2O + O
HAsO42- + Fe(OH)3
(Singh, 2006)

Solubilisation of As in ground
water enhanced by input of
organic carbon (e.g. from
leaching of OC to wells)
(Harvey et al., 2002, 2006)
(Cullen & Reimer, 1989)
 Hg

(Mercury)
 Four different chemical species of Hg

Metallic mercury (Hg0): not toxic

Insoluble mercury salts, e.g. HgS: not toxic

Free mercury ion (Hg2+): toxic, but will hardly be

taken up

Alkylated mercury compounds:

CH3Hg+, (CH3)2Hg, C2H5Hg+ en (C2H5)2Hg

Very toxic, easily taken up, accumulate in brain

air

Fate of mercury in
the environment:
biological
water
fish
methylation by
bacteria in
sediment and
bioaccumulation in
fish
bacteria

bacteria

bacteria bacteria

sediment bacteria
 Minamata Bay
Japan 1932-1970

Chisso factory
produced
fertilizer and plastics

Inorganic mercury = catalyst in production of vinyl chloride

Methyl mercury (by-product) was discharged into sea
 Minamata disease (mercury story)

- Between 1932 and 1970 huge amounts of Hg

discharged into Minamata bay (Japan)
- Methyl mercury (lipophilic) accumulated in
human and feral food chain
- 1st: birds dropped from the sky, animals
behaved strangely, cats died
- 1956s local people became ill, CNS affected (convulsions,
salivation, staggering), death
- 1968 official recognition of the disease;
production vinyl chloride stops
17000 affected
1200 died
 Lessons learned from Hg cases

By far greatest part of global mercury pollution is

present in chemical forms (species) that are not
toxic (not biologically available)

Biological activity may lead to formation of active

and very toxic compounds

The chemical form in which mercury reaches

humans is quite different from the form in which it
is emitted to the environment
 Bioavailability of metals

Speciation = distribution over different chemical

species (e.g. Pb0, PbO, PbCl2, Pb2+)

Free ion biologically available for uptake across

ion channel

Alkylated metals may be taken up by diffusion

(like organic molecule)

Major part of metal load in the environment not

available (oxides, salts of sulphide or carbonate)
Factors reducing metal uptake from food

Zinc Phytate (inositol hexaphosphate)

+ Ca, milk

Copper Much iron and zinc

Chromium Oxalate

Cadmium Much calcium

Lead Phytate + calcium

 Thresholds for metal uptake

Dose

Recommended Recommended
minimum maximum
Lower limit Upper limit
for for toxicity
deficiency
Recommended doses of essential
metals (adult, 60 kg)

Metal Minimum Maximum

(mg/day) (mg/day)
Zn 9.4 40
Cu 1.35 12
Mo 0.024 10
Cr 0.033 0.25
 General lessons on metals in the
environment

Total concentration not indicative of risk

Risk determined by distribution of metals over different

chemical species (speciation)

Only some species taken up and may be toxic (usually

free ion, e.g. Cd2+ taken up, CdCl2 and CdO not)

Body may produce toxic species (e.g. methylation)

Speciation depends on conditions (e.g. pH)

Some metals essential; lower limit may prevent deficiency