Mendeleev Table

Toxic metals (non-essentials) in the

environment
( Cd, Hg, Pb - heavy metals + Al )
 „Heavy metals” – term used for toxic metals contaminating the
environment, having density >5g/cm3)

Heavy metals

Essentials - necessary in trace Non-essentials - no biological

amounts, toxic in too big amounts function - xenobiotics

• Cu • Cd
• Zn • Pb
• ….. • Hg
• Al
Al – density only 1,5g/cm3 – light,
but also non-essential (Wang,2019)
Anthropogenic sources of toxic metals in the environment

combustion in metal smelting and metallurgical industry

(40% Cd emission, Al )

combustion of coal in energy production sector (50% Hg in

Poland)

processess in various industries – production of batteries, dyes,

bulbs (26% Hg, 58% Pb, 35% Cd)

waste incineration (Hg, Pb, Cd about 3%)

road transport (Pb, Cd about 3%)

phosphorus fertilizers use - cadmium containing phosphates

(0,06% Cd)
The degree of human contribution to global metal
circulation in the environment

Anthropogenic Enrichment Factor

Emission 106kg/year
Anthrop.sources (AS) Natural (NS) Total (T) AEF=AS/T x 100
cadmium,
lead,

mercury

AEF (Percentage of AS in Total Emission)

is high for cadmuim, lead and mercury

Metals are not degradable, once released they

circulate in the environment (changing form)
Cadmium containing products
+ rechargeable batteries (Ni/Cd) 83%
+ pigments 8% (print dyes) Cd red and yellow
+ coating of other metals 7%
+ stabilizers for plastics (1,2%)
+ alloys 0,8%
Lead containing products
+ car batteries
+ pigment in ceramic glazes
+ easy molded and shaped alloys
+ artistic glass
+ ammunition

White lead pigment in

paints - history
Mercury containing products
+ fluorescent tubes
+compact fluorescent light bulbs CFLs
+ Hg containing button cell batteries
+ thermometers ( not in sale but still in
use)
 Emission of lead in 1990-2011 in Poland
Źródło: Krajowy
(spadek Ośrodek
o 60% Bilansowania
w latach – benzyna
i Zarządzania
1990-2005 bezołowiowa)
Emisjami KOBIZE, 2013

2005 2011

(60% decrease) - unleaded gasoline

Emission of cadmium and mercury in 1990-2011 in Poland
Źródło: Krajowy Ośrodek Bilansowania i Zarządzania Emisjami KOBIZE, 2013

2005 2011

Cd (50% decrease), Hg (40% decrease)

Heavy metals are

• mainly emitted to the air

in combustion processes

• attached to PM, and deposited

not far from the emission source

• accumulated in soils and sediments

 Heavy metal contamination of agricultural soils in
Poland is not a general problem
97% agricultural soils
have natural or slightly
increased content of
h.m.,

but locally - fields

adjacent to heavy
traffic highways may
be strongly
contaminated
Metal contaminated soils in urban areas
(concentrated sources of emission)

V degree of
contamination

Górny Śląsk
Forms of metals in soil (soluble and insoluble)
Copper example (essential h.m.)

Soil
solution
Not soluble
forms

May be released to soil

solution
Plant metal uptake
(Kabata-Pendias, 1993)

Other route from air through leaves

Deposition of metal containing particulate
matter on the leaf surface, translocation to
the inner parts

Main route from soil through roots

The most available form are cations from
the water phase of soil, less availbale are the
dissolved organic and inorganic complexes,
then from the soil exchange complex
(mostly Me are accumulated in roots)
 Plants introduce toxic metals into the food chain
Plant contamination from soil depends on:

A. Concentration of toxic metals in soil

B. Their availability for plant (forms)
which is influenced by:
– capacity of the ion exchange complex of soil
– pH of soil (acidity)
– content of competitive ions (for example Zn,
for Pb and Cd)
C. Species and variety of plant
A. Concentration of toxic metals in soil/medium

The increase of plant metal uptake in the increasing metal

concentration in solutions

Cadmium content grows quickest – the most mobile

in soil and in plant and most toxic
Cd, Pb content in plant roots in the increasing distance
from heavy traffic road

Cd more mobile in soils

 B. Metal availability for plants as an effect
of ion exchange complex capacity
Metal Grupa Degree of metal Stopień
contamination gleb (total content)
of soils
zanieczyszczenia
gleb mg/kg
0 I II III IV V
a 30 70 100 500 2500 >2500
Ołów (Pb) b 50 100 250 1000 5000 >5000
c 70 200 500 2000 7000 >7000
a 50 100 300 700 3000 >3000
Cynk (Zn) b 70 200 500 1500 5000 >5000
c 100 300 1000 3000 8000 >8000
a 15 30 50 80 300 >300
Miedź (Cu) b 25 50 80 100 500 >500
c 40 70 100 150 750 >750
a 10 30 50 100 400 >400
Nikiel (Ni) b 25 50 75 150 600 >600
c 50 75 100 300 1000 >1000
a 0,3 1 2 3 5 >5
Kadm (Cd) b 0,5 1,5 3 5 10 >10
c 1,0 3 5 10 20 >20

a- light, sandy soils, low capacity of IEC

=highly available for plants
b- medium
Limits much lower
c- heavy soils, high capacity of IEC
for Cd than Pb =limited availability for plants
 B. The effect of soil pH on the availability of metals for plants
Concentration of water
soluble forms

(below pH 6 soluble forms of metals are v. significantly increased)

 C. Cadmium uptake in various vegetables
(Gruca-Królikowska i Wacławek, 2006)

The transfer coefficient is the metal concentration in plant tissues

aboveground divided by the total metal concentration of soil.

Cd Transfer coefficient Vegetable

uptake [TC]
Weak 0,1-0,5 Peas, beans

Moderate >0,5-1,0 Carrot, cabbage

Strong >1,0-3,0 Leek, radish, lettuce

The higher coefficient the higher uptake in similar conditions

A plant is considered an accumulator of a metal when TC > 1
(Rodriguez-Villa et. Al.., 2014)

Indian mustard Brassica juncea is a good

phytoextractor of metals from contaminated
soils (Ni, Pb, Cd, Cr)

TC Ni for mustard - over 4

(Rodriguez-Villa, 2014)
Sensitivity of different species to toxic metals
(example of cadmium contamination)
80, 40 i 20 mg Cd/kg d.w. beans

As a rule:
Monocots Me sensitivity < dicots

(but oat v. sensitive!) 80 40 20 0

wheat
peas

80 40 20 0
Diversed reactions of plants to cadmium in soil
(da Rosa Correa i in., 2006)

oat chinese
[sensitive] cabbage
[resistant]
LOEC 12,5 50
(biomass) mg Cd/kg d.w. soil mg Cd/kg d.w. soil

LOEC 50 200
(germination) mg Cd/kg d.w. soil mg Cd/kg d.w. soil
 Mechanisms of metal resistance in plants :

• Accumulating Me in cell walls

• and vacuoles (complexes with organic acids)

• Binding Me with phytochelatins (proteins)

_
• Creating specific conditions in the rhyzosphere
to restrict the uptake of metal (pH regulation)

+
 Metal contamination of food
Cadmium example
(ATSDR, 2003)

0,045
0,04
0,035
0,03
0,025
ppm

ppm=mg/kg 0,02
0,015
0,01
0,005
0

mięso i
ziemniaki

owoce
zboża

mleko
w.liściowe

potato leafy veg cereals fruits meat milk

ryby
Max levels for Cd: meat – 0,05; cereals – 0,1 leaf vegetables 0,2 ppm
 Cadmium content in fresh fruits and vegetables in Poland and
acceptable limits according to Commission Regulation EU488/2014

Average content Cd Maximum

mg/kg f.w acceptable limits
mg/kg f.w. (ppm)
Berry fruits 0,02 0,05

Other fruits 0,004 0,05

Leafy vegetables 0,050 0,20

Root and stem 0,056 0,10

vegetables

Other vegetables 0,01 0,05

(fruits, seeds)
Max Acceptable limits are
highest for leafy
vegetables!
 Main mechanisms of toxic activity of heavy metals
in organisms

• Protein denaturation - Me ions bind easily to -SH, -OH, or

NH groups (changes in molecule structure)

• Substitution of a proper metal with the toxic metal in

enzymes (zinc with cadmium)

• Acceleration of lipid peroxidation (mercury, iron)

• Elimination of calcium ions (by eg. cadmium) – cell

membrane disfunction

• Forming DNA adducts (carcinogenic Cd, Hg)