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POPs Health

Persistent Organic Pollutants


(POPs) & The Stockholm Convention
on POPs

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Persistent Organic Pollutants

POPs are chemical substances that


persist in the environment,
bioaccumulate through the food
web, and pose a risk of causing
adverse effects to human health and
the environment.

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Recall Organic Chemistry:
• Aliphatic Hydrocarbons • Aromatic Hydrocarbons
– Open chain – Closed loop electrons
hydrocarbons (linear/ – Structure has a ring like
branched) that of benzene
– Volatile – Semi-volatile
– Low flashpoints – Thermodynamically stable
(flammable)

POPs are chlorinated aromatic/polycyclic hydrocarbons.

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The 12 Priority POPs

1.Aldrin1 7.Hexachlorobenzene1,2
2.Chlordane1 8.Mirex1
3.DDT1 9.Toxaphene1
4.Dieldrin1 10.PCBs1,2 (209 congeners)
5.Endrin1 11.Dioxins2 (75 congeners)
6.Heptachlor1 12.Furans2 (135 congeners)
1 - Intentionally Produced
2 - Unintentionally Produced

“Congener - something of the same kind”


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POPs CHARACTERISTICS
• Persistence
– Ability to resist degradation through physical,
chemical and biological processes

Half Life – is the time it takes for half of the amount of a substance to
decay. C = Co(1/2)t/T1/2

For a substance to be considered as persistent:


• Half life of the chemical in water is greater than two months
• Half life in soil and in sediment is greater than six months
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POPs CHARACTERISTICS
• Bioaccumulation
– Ability to bioaccumulate in
fatty tissues of plants,
animals and human due
to its high affinity to fats
and low solubility in water.

POPs are lipophilic and hydrophobic. 6


POPs CHARACTERISTICS
• Capability for long
range transport
– Ability to travel to
long distances
through the action of
wind, migratory
animals, and through
natural processes
such as evaporation
and precipitation.

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POPs CHARACTERISTICS
• Toxicity
– POPs have been link to various diseases and
disorders such as cancer, hormonal
dysfunction and reproductive disorders.

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Effects of POPs to Wildlife & Human

 Birth defects
 Tumors and cancers
 Compromised immune systems
 Behavioral abnormalities
 Dysfunctional reproductive systems
including feminization of males and
masculinization of females
 Abnormally functioning thyroids and
other hormone system malfunctions 11
Endocrine Disrupters

FEMINIZATION OF MALES
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Aldrin and Dieldrin

• Closely related organochlorine chemicals used on fruit,


soil, seeds, and insect vectors of disease
• Aldrin readily breaks down to dieldrin
• Dieldrin half-life in soil is five years; in humans, 9-12
months
• High levels found in infants and amniotic fluid of fetuses
• Still used as termiticide in some countries in Asia,
South America and Africa

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Aldrin and Dieldrin

• Acute toxicity mainly on the liver and the


nervous system
• Occupational exposure associated with high
rates of psychological illness
• Had been associated with Parkinson’s disease
• Associated with primary liver and biliary tract
cancers both in animals and humans
• Can also cause reproductive toxicity and fetal
anomalies

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Endrin

• More toxic than aldrin and dieldrin


• Used as rodenticide and insecticide
• Half-life in soil as long as 12 years
• Has similar acute and chronic toxicity profile as
aldrin and endrin causing primarily liver and
kidney damage, neuro-behavioral effects,
reproductive toxicity, developmental anomalies,
and other adverse effects

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Chlordane
• Used to control fire ants and termites
• Persist in soil for more than 20 years
• In 1976, 90% of Americans had chlordane
residues in their bodies
• Inuit mother’s milk had levels 10 times higher
than Southern Canadian residents
• Increased rates of respiratory illness, and
migraine in people residing in houses treated
with chlordane
• Occupational exposure associated with cerebro-
vascular disease at rates twice than expected
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Chlordane
• Causes benign and malignant tumors in mice
and rats
• Had been associated with cancer in humans;
classified as probable human carcinogen
• Abnormalities in neurologic, behavioral,
psychomotor, and cognitive function
• Endocrine disruptor
• Reproductive and immune system dysfunction

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DDT
• Mainly used to combat insect vectors of
diseases such as malaria and typhus
• DDT and metabolites have been found in
virtually every breast milk sample tested
• Still found in soils and freshwater sediments in
the US despite 20 yr ban
• Causes reproductive toxicity and developmental
abnormalities
• Nervous system disorders observed in both
acute and long term exposure in humans
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DDT

• Liver damage and immuno-suppression


observed in animals
• Classified as probable human carcinogen;
positive correlation with breast cancer has
been shown
• Has anti-androgenic effects on the fetus and
breast-feeding infant
• Low doses in neonatal animals shown to
cause permanent hyperactive condition,
tremors and paralysis
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Heptachlor

• Used for fire ant control, as termiticide and as


insecticide in seeds and crops
• In a 1996 study in Australia, 100% of breast-fed
infants sampled had high levels of heptachlor
• Causes hyper-excitation of the nervous system
and liver damage
• Symptoms may reappear due to mobilization of
body stores
• Found to have endocrine disrupting effects
• Classified as probable human carcinogen
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Hexachlorobenzene (HCB)
• Has been used as both pesticide and an
industrial chemical; produced as a by-product in
the manufacture of chlorinated chemicals and in
incinerators
• Associated with liver toxicity (porphyria cutanea
tarda)
• Enlarged thyroid glands,scarring, and arthritis
observed in offspring of exposed women
• Classified as probable human carcinogen
• Shown to cause neurologic, immunologic,
reproductive and developmental abnormalities 23
Mirex
• Used as bait insecticide and as fire retardant
in plastics, paints and electronics and
electrical equipment
• Breakdown product under sunlight is more
toxic
• Half-life of up to 10 yrs in sediment
• High levels found in Inuit mother’s milk
• Causes reproductive toxicity and
developmental disorders
• Suppresses the immune system
• Associated with liver cancer
• Reduction in germination and emergence of
several plant species has been observed 24
Toxaphene
• Mainly used as an insecticide especially against
maggots and cotton pests
• Half-life in soil as long as 12 years
• Toxic effects on the liver, kidney, thyroid,
neurologic and immune systems
• Acute exposure also shown to cause damage to
the lungs
• Associated with liver and thyroid cancers
• Exhibited endocrine disrupting effects
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Regulatory Status of POPs
Pesticides in the Philippines
• In 1978, FPA issued a Pesticide Circular restricting the
use of DDT to vector malaria control, with only the DOH
as the authorized importer and user. And an FPA
Resolution Banning DDT was issued on Nov. 16, 2005.
• In 1983, FPA has banned Endrin.
• Aldrin, dieldrin, heptachlor and toxaphene was banned in
1989.
• Chlordane was banned through FPA Pesticide
Resolution No. 01 Series of 1999
• Mirex and HCB were never registered nor imported in
the country.

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POPs Pesticides Issues in the Philippines
• Alternatives to POPs – pesticides are already available.
However, based on the initial inventory conducted,
there are alleged illegal importation of POPs Pesticides
and use of these POPs – pesticides.

• Recent cases of POPs poisoning incidents were also


reported by the National Poison Control Center to have
occurred even after years of banning these POPs –
pesticides.

• Measurable levels of pesticides, which include those


that are POPs, such as aldrin, dieldrin, DDT and
heptachlor, are found in various bodies of water in the
country, as reported by the Natural Sciences Research
Institute (NSRI) of the University of the Philippines for
their UN University project. 28
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WHAT ARE PCBs
• PolyChlorinated Biphenyls
• 209 chlorinated biphenyl compounds
(congeners)
2’ 1’ 1 2
• Synthetic organic chemicals
• No known natural sources
3’ 3

4’ 5’ 5 4

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PCBs world production
USSR
179500
Germany France
116700 SR 21500
144000

Japan
59300

Other
205200 UK 66800

Spain
USA 29000
647000 Italy
28000
Poland >1000

World production: cca 1,5 mil. t 32


PCBs commercial products
• Apirolio • Pyranol
• Aroclor • Pyroclor
• Askarel • Phenochlor
• Clophen • Santotherm
• Delor • Sovol
• Hydelor • Sovtol
• Elaol • others
• Fenchlor

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PHYSICAL PROPERTIES

• Oily liquids, clear crystalline


solids to hard black resins
• PCB liquids are colorless to
light yellow
• No unique odor or taste
• Low vapor pressure (PCBs
don’t evaporate easily)

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CHEMICAL PROPERTIES

• Lipophilic
• Very stable
• High thermal and electric
resistance

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Hazardous Decomposition
By-Products

• Dioxins and Furans


– Belong to the Dirty Dozen POPs
– 2,3,7,8 – TCDD is confirmed human
carcinogen.
• Chlorinated quarterphenyls
– highly toxic and carcinogenic
substance

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HISTORY
• PCBs were discovered over 100 years ago, as
by-product in the synthesis of certain
chlorinated hydrocarbons.
• Produced commercially in U.S. from 1929 -1977
by Monsanto Corp. in U.S.
– Maximum production 1970: 38,000 metric tons
– From 1929-1977, Monsanto has produced 1.1 billion
pounds of PCBs
• Japan, Germany, Italy … have also produced
PCBs for commercial application.
• World production volume is not known
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HOW WERE THEY USED?

• ‘Closed’ applications: transformers,


capacitors, heat transfer, hydraulic fluids,
switches, voltage regulators and other
electric equipment

• ‘Open’ applications: plasticizers, surface


coatings, inks, adhesives, flame retardants,
paints, pesticide extenders.

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Historical Concern Over PCBs

• 1966 – A research in Sweden revealed a high


level of PCBs in soil and water samples being
screened for DDT.
• Further study confirmed that the rate of
biodegradation was very slow for some PCB
congeners.
• PCBs were also found to be present in fishes at
a concentration that is much higher than the
background levels.

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How Did PCBs Get Into The Environment?
• Discharges of PCB-laden wastes into rivers,
streams, and open landfills.

• PCBs were used as extenders to some


pesticide formulations.

• PCBs were used to reduce dust emissions from


dirt roads.

• PCBs were also released via leaking of


transformers and capacitors.
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The Yusho Incident
• 1968 - A widespread human poisoning episode in
Western Japan, which was attributed to the consumption
of rice bran oil that became contaminated with PCBs
during processing
• Yusho - “oil disease”
• Acute effects have been manifested to 1300 people in
1968: Chloracne, fatigue, nausea, swelling of arms and
legs and liver disorders.
• Within 15 years – excess mortality from liver cancer was
observed among the Yusho patients.
• Some newborns of exposed mothers exhibited
discoloration of skin and nails and pre-mature eruption of
teeth.
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The Yu-Cheng Incident
• 1978 – Yu-Cheng Incident in Taiwan
• Rice bran oil was contaminated by heat degraded
PCBs and ingested by over 2000 people.
• Effects among the victims were similar to those in
the Yusho.
• Offspring of Yu-Cheng mothers also exhibited
acute toxicity.
• Increased mortality from liver diseases were
observed within three (3) years after the
poisoning incident.

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EFFECTS OF PCBs TO HUMAN HEALTH

Liver damage
Hormonal effects

Chloracne

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Status of PCBs Use in the Philippines

• PCBs are still broadly used as dielectric fluid in


transformers and other electric equipment.
• Stockpiles of PCB wastes have been accounted during
the Initial National Inventory.
• Users/handlers have limited understanding on the
hazards and risks of PCBs, as such storage, handling,
management & treatment/disposal practices need to be
improved.
• A Chemical Control Order for PCBs was issued in Feb.
2004 to address the PCBs management issues.

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Dioxins & Furans

• Dioxins and Furans are


produced unintentionally
from combustion and
through chemical
processes involving
chlorine and organic
compounds.

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Before

During

After
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• Ukrainian president Viktor Yushchenko suffered from extremely prominent
facial chloracne after being diagnosed with dioxin poisoning in late 2004. His
diagnosis of chloracne was claimed by prominent toxicologist John Henry.
• Viktor Yushchenko as he appeared in July 2004 (left), and as he appeared
in November 2004 after the supposed dioxin - poisoning (right).
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Status of Dioxins and Furans Release -
Reduction Measures
• Among the Dirty Dozen POPs, D & F is the least understood.
• There are limited studies on D & F:
– The ITDI - DOST Study using the UNEP Standardized Toolkit
for the Quantification of D & F releases (534 g TEG/a - Y1999)
– The ITDI – DOST Study on the Presence of D & F in human
breast milk.
• RA 8749 or the Philippine Clean Air Act of 1999
– Section 20 requires the ban on incineration and the promotion
on the use of an environmentally sound and safe non-burn
technologies for the management of wastes.
– Section 32 of the Act requires the establishment of an inventory
list of the sources of POPs in the country and the establishment
of a short and long term national government programs on the
reduction and elimination POPs.
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Status of Dioxins and Furans Release -
Reduction Measures

• RA 9003 or the Ecological Solid Wastes


Management Act of 2000 prohibits the open
burning of solid wastes, importation of toxic
wastes misrepresented as recyclable or with
recyclable content and the transport and
dumping in bulk of collected domestic, industrial,
commercial and institutional wastes in non-
prescribed areas

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THE STOCKHOLM
CONVENTION ON
PERSISTENT ORGANIC
POLLUTANTS

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Industrial
Chemicals
AIR
By –
Products
Pesticides

WATER

LAND
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THE STOCKHOLM CONVENTION ON POPs

• An international treaty, which aims to


protect human health and the environment
from POPs by eliminating production
and use and by minimizing releases of
the Dirty Dozen, 12 POPs chemicals
initially covered by the Convention.

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The Stockholm Convention on POPs

• Adopted on May 23, 2001 by 91 countries, including the


Philippines, in response to an urgent need for global
action on POPs.
• Entered into force 90 days after 50th ratification
(17 May 2004)
– Signatories = 151
– Parties = 112
– Philippines is the 51st Party
– Signed SC on May 23, 2001
– Ratified SC on Feb. 17, 2004 by the Philippine Senate
– Became a Party on Feb. 27, 2004
– SC entered into force in the Philippines on 27May 2004
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Stockholm Convention on POPs

1. Evaluation and regulation of new


and existing chemicals

Existing chemicals
• Parties must eliminate certain chemicals from
production and use and lays down POPs
screening criteria for assessing other chemicals
for possible inclusion
New chemicals
• Parties with regulatory and assessment schemes
are required to prevent production and use of
new pesticides or new industrial chemicals that
exhibit POPs characteristics 61
Stockholm Convention on POPs

2. Import and export controls


Restricts import and export of POPs
• It will prohibit their improper transport
across international boundaries
• Allows import/export for environmentally
sound disposal or for an exempted use or
production that is permitted for the importing
party

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Stockholm Convention on POPs

4. Environmental releases
Aims to reduce and/or eliminate releases of
POPs from:
• intentional production and use
• unintentional production
• stockpiles and wastes

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Stockholm Convention on POPs

3. Waste management
• Develop and implement strategies for identifying
stockpiles, products and articles containing POPs
and manage them in a safe, efficient, and
environmentally sound manner
• Prevent the creation of POPs in waste management
practices; their toxic content needs to be destroyed
and will not allow recovery, recycling, reclamation,
direct reuse or alternative uses of POPs
• Concepts of Best Available Technique (BAT) and Best
Environmental Practices (BEP)

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Sample BAT & BEP
• Use of low-waste technology
• Use of less hazardous substances
• Promotion of the recovery and recycling of waste and of
substances generated and used in a process
• Replacement of feed materials which are POPs or where
there is a direct link between the materials and releases of
POPs from the source
• Good housekeeping and preventive maintenance programs
• Improvements in waste management with the aim of the
cessation of open and other uncontrolled burning of wastes,
including the burning of landfill sites
• Minimization of these chemicals as contaminants in products
• Avoiding elemental chlorine or chemicals generating 67
elemental chlorine
Stockholm Convention on POPs

5. Hazard communication and


replacement
• Requires parties to communicate hazard
information to the secretariat, other
parties, and/or the public

• Calls on governments for information exchange and


updates, research on alternatives, public awareness,
educational programs, technology transfer, and
provision of financial aid

• Calls on governments to report and advise regularly on


BAT and BEP as experience is gained and shared and as
technology advances 68
Stockholm Convention on POPs
• The convention allows countries that belong to it
to add more chemicals to the list of substances
to be banned or restricted in member countries.

• POPRC (Nov 7 – 10, 2005)


– Pentabromodiphenyl ether (PBDE)
– Chlordecone
– Hexabromobiphenyl
– Lindane
– Perfluorooctane sulfonate
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SC Financial Mechanism
• Developing countries that are Parties to the SC
will be provided with Financial Assistance in order
to meet the requirements of the Convention.
• As one of the early signatories to the Convention,
the Philippines was able to avail of the GEF grant
to develop a National Implementation Plan (NIP).
• The Project, PHI/01/G32- Philippine Enabling
Activity Project: Initial Assistance to the
Philippines to meet its Obligations Under the
Stockholm Convention on POPs is being
executed by UNDP and implemented by DENR-
EMB.
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Thank you for
listening!

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