Heavy Metals

TOXIC HEAVY
METALS
Presented by: MS. NOROLAYN K. SAID
Presented to: Chem 289 Class

Heavy Metals
 metals or metalloids (elements that have
both metal and non-metal characteristics)
 persistent in all parts of the environment,
 generally, have densities above 5 g/cm3,
 cannot be degraded or destroyed.
 to a small extent they enter our bodies
via food, drinking water and air
Presented to Chem 289, Summer Class 2014
2

 as trace elements, some heavy metals (e.g.
copper, selenium, zinc) are essential to
maintain the metabolism of the human body
 however, at higher concentrations they can
lead to poisoning
heavy metal poisoning could result, for
instance, from drinking-water contamination
(e.g. lead pipes), high ambient air
concentrations near emission sources, or
intake via the food chain
3

 Human activity affects the
natural geological and
biological redistribution of
heavy metals through
pollution of the air, water,
and soil.
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Heavy metals enter the environment from natural and
anthropogenic sources.
The most significant natural sources are weathering
of minerals, erosion and volcanic activity while
anthropogenic sources include mining, smelting,
electroplating, use of pesticides and (phosphate)
fertilizers as well as biosolids in agriculture, sludge
dumping, industrial discharge, atmospheric
deposition, etc. (Modaihsh et al., 2004; Chehregani
and Malayeri, 2007; Fulekar et al., 2009; Sabiha-
Javied et al., 2009; Wuana and Okieimen, 2011).
6

• Soils are significant sinks for metals,
while water represents an important
pathway for the dispersion of metals
over extremely large areas (Gibler et
al., 1997, Gerber et al., 1991).
• The mobility of a metal in soil and
water depends significantly on the
chemical form and speciation of the
metal.
7

• The mobility of metals in ground-water systems
is hindered by reactions that cause metals to
adsorb or precipitate, or chemistry that tends to
keep metals associated with the solid phase and
prevents them from dissolving.
• These mechanisms can retard the movement of
metals and also provide a long-term source of
metal contaminants.
• While various metals undergo similar reactions in
a number of aspects, the extent and nature of
these reactions varies under particular conditions
(Gerber et al., 1991, Levine et al., 2006).
8

• Studies on the mobility of heavy metals in
soils have shown that the mobility is
strongly influenced by several factors, e.g.
pH redox potential, clay mineral content,
organic matter content and water content.
• Various processes, e.g., adsorption-
desorption, complex and ion-pair
formation or activities of micro organisms
are also involved (Gibler et al., 1997).
9

• Simple and complex cations are the most
mobile, exchangeable cations in organic
and inorganic complexes are of medium
mobility and, chelated cations are slightly
mobile (Catherine et al., 2001, Gibler et
al., 1997).
• Metals in organic particles are only mobile
after decomposition or weathering.
Precipitated metals are mobile under
dissolution conditions (e.g. change in pH)
(Catherine et al., 2001).
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Mercury
• Mercury is the only common metal which
is liquid at ordinary temperatures. It rarely
occurs free in nature and is found mainly
in cinnabar ore (HgS)
• It alloys easily with many metals, such as
gold, silver, and tin - these alloys are called
amalgams. Its ease in amalgamating with
gold is used in the recovery of gold from
its ores.
13

Environmental Effects
• Acidic surface waters can contain significant
amounts of mercury
• When the pH values are between five and seven,
the mercury concentrations in the water will
increase due to mobilisation of mercury in the
ground
• Once mercury has reached surface waters or soils
microorganisms can convert it to methyl mercury,
a substance that can be absorbed quickly by most
organisms and is known to cause nerve damage
14

• Fish are organisms that absorb great
amounts of methyl mercury from
surface waters every day (mercury can
accumulate in fish and in the food
chains)
• The effects that mercury has on
animals are: kidneys damage, stomach
disruption, damage to intestines,
reproductive failure and DNA
alteration
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Cadmium
•a bluish-white element used
in batteries, pigments, and
protective plating
17

Human uptake of cadmium takes
place mainly through food
Foodstuffs that are rich in
cadmium can greatly increase the
cadmium concentration in human
bodies (liver, mushrooms,
shellfish, mussels, cocoa powder
and dried seaweed)
18

• Cadmium can be transported over great distances when it is
absorbed by sludge
• This cadmium-rich sludge can pollute surface waters as well as
soils
• Cadmium strongly adsorbs to organic matter in soils
• When cadmium is present in soils it can be extremely
dangerous, as the uptake through food will increase
• Soils that are acidified enhance the cadmium uptake by plants
• This is a potential danger to the animals that are dependent
upon the plants for survival – Cadmium can accumulate in
their bodies, especially when they eat multiple plants
• Cows may have large amounts of cadmium in their kidneys
due to thisPresented to Chem 289, Summer Class 2014
19

• In aquatic ecosystems cadmium can
bioaccumulate in mussels, oysters,
shrimps, lobsters and fish
• The susceptibility to cadmium can
vary greatly between aquatic
organisms
• Salt-water organisms are known to be
more resistant to cadmium poisoning
than freshwater organisms
20

Chromium
• Chromium(VI) is a danger to
human health, mainly for people
who work in the steel and textile
industry
21

• People who smoke tobacco also have a
higher chance of exposure to chromium
• Hexavalent Chromium – Chromium (VI) is
a species of chromium that is forbidden to
use in electrical & electronic industry
22

• When it is a compound in leather products, it can
cause allergic reactions, such as skin rash
• After breathing it in, chromium(VI) can cause
nose irritations and nosebleeds
• Upset stomachs and ulcers
• Respiratory problems
• Weakened immune system
• Kidney and liver damage
• Alteration of genetic material
• Lung cancer
• Death
23

• Most of the chromium in air will eventually settle
and end up in waters or soils
• Chromium in soils strongly attaches to soil
particles and as a result it will not move towards
groundwater
• In water chromium will absorb on sediment and
become immobile
• Only a small part of the chromium that ends up in
water will eventually dissolve
24

• Chromium(III) is an essential element
for organisms that can disrupt the
sugar metabolism and cause heart
conditions, when the daily dose is too
low
• Chromium(VI) is mainly toxic to
organisms - it can alter genetic
materials and cause cancer
25

Lead
• a bluish-white color after being
freshly cut, but it soon tarnishes to
a dull grayish color when exposed
to air. Lead has a shiny chrome-
silver luster when it is melted into
a liquid.
26

•Foods such as fruit, vegetables,
meats, grains, seafood, soft
drinks and wine may contain
significant amounts of lead
•Cigarette smoke also contains
small amounts of lead
27

• Disruption of the biosynthesis of hemoglobin and
may lead to anemia
• A rise in blood pressure
• Kidney damage
• Miscarriages
• Disruption of nervous systems
• Brain damage
• Declined fertility of men through sperm damage
• Diminished learning abilities of children
• Behavioral disruptions of children, such as
aggression, impulsive behavior and hyperactivity
28

• Lead can enter a foetus through the
placenta of the mother
• Because of this it can cause serious
damage to the nervous system and the
brains of unborn children
• That is why women in pregnancy can not
work with lead.
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• Soil functions are disturbed by
lead intervention, especially near
highways and farmlands, where
extreme concentrations may be
present
• Also soil organisms are suffered
from lead poisoning
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Current Researches
1. Castaneds, et. al. Determination of Some
Heavy Metals Possibly Present in
Drinking Stations Found in the Vicinity of
a University in Manila, Philippines.
(2012)
 The student researchers conducted a
descriptive-exploratory analysis of water
coming from student-accessible drinking
stations in the different colleges in a well-
known university in Manila, Philippines.
33

 These water samples were acid digested and
were qualitatively and quantitatively tested for
the heavy metals possibly present. Qualitative
testing of the sampled water yielded negative
results. Quantitave testing of the sampled water
for lead and cadmium, however, resulted to
concentrations higher than the standard limit for
drinking water set by the Environmental
Protection Agency (EPA). It was shown in this
study that water from these sources are not safe
for drinking due to higher than normal levels of
lead and cadmium.
34

2. Solidum, et. al. (2012) Assessment and
Identification of Heavy Metals in Different Types
of Cooked Rice Available in the Philippine Market.
 Quantitative test using Flame Atomic
Absorption Spectroscopy indicate cadmium
levels (0.0127-0.043 μ/g; safety limit: 0.2μ/g or
0.004-0.027 mg/day) and chromium levels
(0.0006-0.0007 μ/g; safety limit: 0.05-0.2
mg/day). This may result to a major health
concern, especially in countries that treat rice as
the staple food source, for cadmium accumulates
chronically and the levels detected was relatively
high despite the fact that it passed the safety limit
set by World Health Organization (WHO).Presented to Chem 289, Summer Class 2014
35

36

3. Cortez, et. al. (2014) Heavy Metal Concentration of
Dumpsite Soil and Accumulation in Zea mays (corn)
Growing in a Closed Dumpsite in Manila, Philippines
 Soils and plants were sampled and analysed using atomic
absorption spectrophotometer (AAS). Concentrations of
the metals in the dumpsite soil and plant parts were found
to be in higher concentrations compared to normal
farmland which served as the control.
Significant differences of heavy metals accumulations
were observed per plant parts. Traces of metals were
found in highest concentrations in the roots of all studied
plants.
Pb was found to be the only metal in plant parts
exceeding the permissible limit given by WHO/FAO.
37

4. Cruz, et. al. (2009) ANALYSIS OF TOXIC HEAVY
METALS (ARSENIC, LEAD, AND MERCURY) IN
SELECTED INFANT FORMULA MILK
COMMERCIALLY AVAILABLE IN THE PHILIPPINES
 Three types of infant formula milk were subjected to
testing and results were collated.
All of the infant formula milk samples tested were
negative for both Lead and Arsenic;
however, two of these milk samples were positive for
Mercury (sample X = 0.6333 ppm; sample Z =0.8333
ppm) in amounts above the maximum allowable limit, as
stated by the Food and Agriculture Organization/World
Health Organization Joint Expert Committee on Food
Additives (JECFA).
38

5. Fernandez, G. 2004. Accumulation of Mercury and Other
Heavy Metals in Some Edible Marine Mollusks in Sibutad,
Zamboanga del Norte
 Results of analyses showed that all the sampling sites in
the bay exceeded the allowable Hg limit for seawater
(2ppb).
Stations nearest in proximity to the mining area tend to
acquire higher concentrations in all the compartments.
Among the species, Modiolus philippinarum, Nerita
planospira and Trachycardium flavum were within the
allowable limit of 0.5 ppm.
Tectus fenestratus, Strombus sp, Placuna ephippium and
Circe scripta had as much as a factor of 5 more than the
allowable limit. From regression analysis, this study has
shown that mercury concentration in tissues of 3 out of 4
species studied correlated with dissolved mercury and
suspended particles or sediments.Presented to Chem 289, Summer Class 2014
39

6. Sahu, et. al.
(2014) Heavy
Metals in
Cosmetics.
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7. Lam, et. al. 2009. TOTAL ARSENIC AND TOTAL
MERCURY CONCENTRATIONS OF THE WATERS
AND JANITOR FISHES (PTERYGOPLICHTHYS SPP.)
IN THE MARIKINA RIVER, PHILIPPINES
 The study assessed the total arsenic and total mercury
concentrations of the waters obtained and janitor fishes
(Pterygoplichthys spp.) caught from the upstream and
downstream areas of the Marikina River in June 2008.
Results of the study showed that the waters of the
Marikina River had mean total arsenic and total mercury
concentrations of 0.001 and 0.084 mg L-1, respectively,
and the fishes examined had mean total arsenic and total
mercury concentrations of 0.015 and 0.012 mg kg-1,
respectively.
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49

 There were no significant differences in
the total arsenic and total mercury
concentrations of both the upstream and
downstream areas of the Marikina River,
as well as of the janitor fishes caught from
both areas. Continuous water quality and
biota monitoring is encouraged to
effectively analyze the impact of these
heavy metals to the environment and
human health.
50

8. Usman, E. Heavy Metals in Fruit Juices.
2013.
 The Philippine Council for Health
Research and Development (PCHRD),
without naming brands, said cadmium and
lead contaminants were found in 17 fruit
juices, five bottled ice teas, and 18
condiment samples found in local
supermarket. They also “detected Cd and
Pb in fruit juices and condiment samples
but not in tea samples.”
51

MSU-Science High School
Current Researches ON THM
1. Macaronsing, S. A. D. Mercury
Content Among Selected Brands
of Eye Mascaras. Unpublished
Research (2014)
 conducted in DOST Region 10
 Brands: Avon Super Extend, Avon
Super Shock, LM Cool Eyes
Angels, Aifeiya Volume Glamour,
Aifeiya Full Lashes Natural Look
 LM Cool Eyes Angels (highest
content); Avon Super Shock
(lowest content)
 all brands fall within tolerable
amountPresented to Chem 289, Summer Class 2014
52

2. Bedoya, S. J. Determination of Heavy Metals
on Lato Sold at Palao Iligan Market.
Unpublished Research Paper (2014).
 conducted in FAST CDO
 Cd showed concentrations less than 0.02
mg/kg in all stalls, falls within the tolerable
amount
 Pb showed concentrations 9.6 mg/kg, 1.0
mg/kg and 6.1 mg/kg in stalls 1, 2, 3
respectively
 Hg found to have 0.05 ug/g in stalls 1 and 2,
0.07 ug/g in stall 3; above tolerable amount
53

3. Darimbang, G. Cadmium Content from
Kangkong (Ipomoea aquatica) on Selected Areas
from Nazareth, Cagayan de Oro. Unpublished
Research Paper (2014).
 all samples with less than 0.01 ppm
 within the tolerable amount
4. Goling, S. Lead Determination from Kangkong
Sold in Marawi Markets. Unpublished Research
Paper (2013).
 samples contained more than 100x the tolerable
amountPresented to Chem 289, Summer Class 2014
54

5. Saripada, S. Lead Content among Selected
Brands of Face Paints. Unpublished
Research Paper (2014)
 Face paint Z (Sports Fans Faces) showed
highest lead content (238 mg); beyond the
tolerable amount
 Face paint X (Lucky art Face Paints)
showed the lowest content (0.4744 mg);
55

6. Basman, N. Mercury Content in Teether
Toys. Unpublished Research Paper (2013).
 samples selected randomly from Iligan stores
 all contained mercury
 within tolerable amount
 with significant relationship between price
and mercury content
 the higher the mercury, the cheaper the
teether
56

7. Dalidig, J. Lead Content of Selected Enamel
Paints. Unpublished Research Paper (2012)
 conducted in CSM, Chem Dept MSU IIT
 lemon yellow color
 all contained Pb
 Island Enamel with the highest amount
 Boysen with the least amount
 all beyond the tolerable amount
 with significant relationship between the price
and lead content
 the higher the price, the lower the lead content
57

8. Bantuas (2010) found out that all low cost lip
glosses on study showed positive result for lead;
Habib (2009) found out that not all lipsticks were
free from lead
9. Saranggani, H. (2012) found out that among the
common low cost whitening creams, Mena
contained the highest
10. Macasundig, S. (2013) found out that Ponds
cream and other common facial creams contained
mercury; within the tolerable amount
58

11. Hussein, M. Lead Content of
Selected Low-Cost Slippers.
Unpublished Research Paper (2011)
 conducted in Chem Dept MSU-IIT
 Sport brand contained the highest
 Blue brand contained the least
 Xingao and Logo brands showed
negative results
59

12. Abdullah, S. 2012. Determination of
Aluminum from Cooked Rice in Different
Brands of Cooking Pots
 conducted in Chem Dept, MSU-IIT
 some samples contained aluminum
beyond the tolerable amount
60

Government Action
The government is strengthening its
control on the use of lead and its compounds
in the local production of consumer
products, as well as its importation, sale,
distribution and disposal following the
issuance of a chemical control order (CCO)
for lead and lead compounds by the
Department of Environment and Natural
Resources (DENR).
61

The DENR chief added that the new
regulation on lead is consistent with Republic
Act No. 6969, otherwise known as the Toxic
Substances and Hazardous and Nuclear
Wastes Control Act of 1990, as it also
addresses the transport and treatment of lead-
containing wastes prior to disposal. RA 6969
was issued by the government in response to
the Basel Convention on the Control of
Transboundary Movements of Hazardous
Wastes and their Disposal.
62

Other agencies involved in the
toxic heavy metal regulation
 Food and Agriculture Agency (FAO)
 World Health Organization (WHO)
 Joint Expert Committee on Food
Additives (JECFA)
63

Remediation
64

Microbes effectively sequester heavy metals:
• Microbes are the primary means of heavy
metal deposition in terrestrial/aquatic
environments.
• Tolerant of high heavy metal concentrations.
• High heavy metal binding capacity.
• Synthesize high-affinity, heavy metal binding
proteins inresponse to toxic heavy metal
concentrations.
• Bioimmobilization
65

Applications in terrestrial/aquatic
environments:
• Easily grown and harvested.
• Unicellular, high surface to volume
ratio.
• Can be genetically engineered to
potentially improve metal recovery.
66

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LIMITATIONS OF BIOREMEDIATION
• Contaminant type and concentration
• Environment
• Soil type
• Condition and proximity of groundwater
• nature of organism
• Cost/benefit ratios: cost versus overall environmental
impact
• Does not apply to all surface
• Length of bioremediation process
• Capabilities of bioremediation
69

70

Things we can do
1. Buy THM-Free
2. Discard products safely
3. Conserve Energy
4. Avoid exposure to THM
5. Be aware of the sources of foods and
be conscious of the goods and
products sold.
71

References
1. http://www.biotec.or.th/en/images/stories/news/banner/b
ioremediation_by%20dr.surasak.pdf
2. http://www.hrpub.org/download/201307/eer.2013.01010
2.pdf
3. http://wiredspace.wits.ac.za/bitstream/handle/10539/581
8/Phele%2520dissertation.pdf
4. http://www.sciencedirect.com/science/journal/00456535
/91/7
5. http://www.icsu.org/future-earth/events/documents/1-3-
11-heavy-metals-in-the-environment
72

6. http://www.veterinaryworld.org/2008/January/Toxic.pdf
7.
http://www.cseindia.org/userfiles/Heavy_Metals_in_Cosme
tics_Report.pdf
8.
http://www.eisrjc.com/documents/Analysis_Of_Toxic_Hea
vy_Metals_1325932478.pdf
9. http://www.ipcbee.com/vol37/007-ICEAE2012-
A00018.pdf
10. http://warponline.org/uploads/contents/51-content-3.-
Determination-of-Some-Heavy-Metals-Possibly-Present-in-
Drinking-Stations-Found-in-the-Vicinity-of-a-University-
in-Manila,-Philippines.pdf
73

11. http://www.mb.com.ph/dost-warns-of-heavy-metals-in-
fruit-juices/
12.
http://www.ijesd.org/index.php?m=content&c=index&a=sh
ow&catid=49&id=759
13.
http://www.eisrjc.com/documents/Analysis_Of_Toxic_Hea
vy_Metals_1325932478.pdf
14.
http://cvisc.pshs.edu.ph/files/Researches/2013/assessment-
of-heavy-metals-in-the-municipal-solid-wastes-and-deep-
well-water.pdf
15.
http://www.nscb.gov.ph/ncs/9thncs/papers/environment_Ac
cumulation.pdf
74

16.
http://www.safecosmet
ics.org/downloads/Pret
tyScary_Oct2709.pdf
17.
http://www.denr.gov.p
h/news-and-
features/latest-
news/1643-denr-
prohibits-use-of-lead-
in-local-production-of-
food-packaging-
paints-toys-other-
consumer-products-
.html
18. MSU-SHS
Researches (as
enumerated in the
previous slides) from
ISED Library
75

The End…Presented to Chem 289, Summer Class 2014
76

Heavy Metals

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