Environmental Chemistry

Unit 2b
Organic Contaminants
Pesticides

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Learning Objectives
• Organochlorine, Organophosphate and other
Pesticides
• main types
• chemical and physical properties
• how/when manufactured
• bioaccumulation/biomagnification
• fate and transport
• guidelines/regulations

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Releases into the Environment

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 Exposure to Pesticides
• Human (including agricultural workers)
• routes of entry
• manufacturing, spills, waste disposal
• Animals (including pets)
• Aquatic organisms

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Stockholm Convention
• Stockholm Convention on Persistent Organic
Pollutants (POPs)
• May 2001 - international treaty aimed at restricting
and ultimately eliminating the production, use, release
and storage of twelve (12) POPs
• nine (9) of the first twelve (12) POPs are pesticides:
aldrin, chlordane, DDT, dieldrin, endrin, heptachlor,
hexachlorobenzene, mirex, and toxaphene
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 Additional POPs
• The following four (4) pesticides were added to the
Stockholm Convention in 2009
• Lindane (gamma-hexachlorocyclohexane)
• alpha hexachlorocyclohexane
• beta hexachlorocyclohexane
• The α- and β-isomers of hexachlorocyclohexane are waste
chemicals that result from the manufacture of lindane
• Chlordecone
• The following pesticide was added to the Stockholm
Convention in 2011
• Endosulfan 6
Organochlorine Insecticides
• All of the pesticides covered by the Stockholm
convention to date (9+4+1=14) are organochlorine
insecticides
• CxHyClz

Aldrin
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Organochlorine Insecticides
• from about 1945 to 1965, organochlorines
were used extensively in all aspects of
agriculture and forestry, in protecting
wooden buildings and protecting humans
from a wide variety of insect pests

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Organochlorine Insecticides
• persistent in the environment
• virtually insoluble in water
• DDT half-life of 3-10 years in soil
• highly soluble in fats
• bioconcentrate in the food web (up to 356 ppm DDT in Bald
Eagles)
• well documented instances of wildlife mortality
• Mirex – manufactured by Hooker Chemical (Niagara River) 
high levels in Lake Ontario (“Love Canal”)
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Organochlorine Insecticides
• Current Status
• Banned in Canada (import, export and use)
• aldrin, chlordane, chlordecone, DDT, dieldrin, endrin,
heptachlor, hexachlorobenzene (HCB), mirex, toxaphene
• No longer registered under the Pest Control Product Act:
• lindane (registration expired in 2004) – still used in lice/flea
shampoos, methoxychlor (registration expired in 2005)
• Still registered under the Pest Control Product Act:
• endosulfan (registration expires December 31, 2016) and
pentachlorophenol (continued registration -
recommendations for safe handling only - 2011). 10
 Canadian Status on First 9 POPs
Chemical Legal/Administrative Measure Date
Aldrin, Chlordane,
Pesticide registration discontinued 31/12/1990
Dieldrin, Endrin
Pesticide registration discontinued
DDT 31/12/1985
Prohibition of Certain Toxic Substances Regulations, 15/02/05
Heptachlor Pesticide registration discontinued 31/12/1985
Pesticide registration discontinued 31/12/76 Prohibition of Certain
Hexachlorobenzene Toxic Substances Regulations, 20/03/2003 Prohibition of Certain 31/12/1976
Toxic Substances Regulations, 15/02/2005

Never registered in Canada for pesticide use,

Mirex Mirex Regulations, 24/11/78 Mirex Regulations, 1989 24/11/1978
Prohibition of Certain Toxic Substances Regulations

Toxaphene Pesticide registration discontinued 31/12/1982

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Organochlorine Insecticides
• Current Status
• levels in aquatic biota declining

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 DDT Levels in the Great Lakes 1970-2005

Note: Change in y axis scale

Source: “State of the Great Lakes, 2008. Indicator @121 –Contaminants in Whole Fish”
http://www.epa.gov/solec/sogl2009/0121wholefish.pdf
Organochlorines
• Other organochlorines (CxHyClz)
• dioxins
• PCBs

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 Hooker Chemicals
• “Love Canal”, Niagara Falls, New York
• Hooker Chemicals used a landfill from 1942-1952 to dispose of over
21,000 tons of various wastes (halogenated organics, pesticides,
chlorobenzenes and dioxin).
• Subsequently the landfill was covered and converted to residential use
(homes and an elementary school)
• In 1980, approximately 950 families were evacuated from a 10 block area
• Occidental Chemical ordered to reimburse the US EPA $129 million in 1995
to cover the clean-up costs
• Hooker Chemicals manufactured mirex (an organochlorine
pesticide) from 1957 to 1976
• estimated 1.5x106 kg of mirex were produced between 1959 and 1975
• resulted in elevated levels locally in the Niagara River and Lake Ontario 15
 Mirex Levels in the Great Lakes 1976-2005

Source: “State of the Great Lakes, 2008. Indicator @121 –Contaminants in Whole Fish”
http://www.epa.gov/solec/sogl2009/0121wholefish.pdf
Organophosphate Insecticides
• replaced organochlorine insecticides
• more powerful than organochlorines
• Examples: schradan, parathion, malathion
• Manufactured beginning in the 1940s
• schradan was discontinued in 1964
• CaHbOcPdSe

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Organophosphate Insecticides
• not very persistent in the environment
• decompose to phosphoric acid
• toxic to humans
• inhibit AChE (supress nerve impulses)
• extremely toxic to arthropods, fish, birds and
mammals

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Organophosphates
• Malathion
• In the US, it is the most commonly used
organophosphate insecticide
• mosquito larvacide
• West Nile – risk/benefit
• still used in Winnipeg for aerial spraying

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 Acute Toxicity (LD50)
the lethal dose (LD) required to kill 50% of a
population (e.g., laboratory rat)
TCDD (dioxin isomer) 0.01 mg/kg rat/oral
aldicarb (insecticide) 0.8
nicotine 50
lindane (insecticide) 88
DDT (insecticide) 200
2,4-D (herbicide) 370
malathion (insecticide) 2,000
salt 3,750
ethanol 13,700
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 carbaryl
Carbamates C12H11NO2

• First appeared in 1930 but began

large-scale use in mid-1950s
• Examples: carbaryl; methomyl; propoxur; aldicarb
• Uses: fungicide, insecticide, acaricide
• Although carbamates share a mode of action with
the organophosphates, their effects are reversible
• not persistent
• not very selective
• toxic to birds and fish

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Carbamates
• aldicarb - discontinued in Canada in 1964
• carbaryl – re-evaluation underway
• methomyl – re-evaluation underway
• propoxur
• Re-evaluation Decision RVD2014-01, Propoxur (April 2014)
• Registration Continued for the following uses:
• indoor crack and crevice applications of Commercial class products in
commercial areas and outdoor uses of Domestic and Commercial class
products, as well as bait trays.
• Registration Discontinued for the following uses:
• use to control biting flies including mosquitoes, black flies, gnats, sandflies and
punkies, use in pet collars, all indoor uses of Domestic class products except
bait trays, and indoor uses of Commercial class products in residential areas
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 Additional Pesticides
Other types of pesticides developed include:
• Phenoxy
• Pyrethroids
• Triazine
• Neonicotinoids (issues with dying honey bees)
• Ontario is taking action and the current plan is to have
restrictions on neonicotinoids by the 2016 growing season (corn
and soybean seeds)
• Example of how pesticides were approved in Canada, the U.S.
and the European Union using modern procedures still involve
risk (one of neonicotinoids implicated was approved in 2003)
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 Pesticide Risks
• December 3, 1984 – Bhopal, India
• pesticide manufacturing plant operated by Union
Carbide leaks methyl isocyanate (MIC) gas
• MIC is a precursor chemical of carbamate insecticides
• 8,000 people die and several thousand other
individuals experience permanent and partial
disabilities
• Memories of the Bhopal Disaster 25 years on
• http://news.bbc.co.uk/2/hi/south_asia/8392093.stm

• Accidental Poisonings
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 Pesticide Laws
• In Canada, the federal, provincial and municipal governments
share responsibility for regulating pesticide products.
• The federal government has the authority and responsibility to
register pesticides in a manner which minimizes risk to health
and the environment. Pesticides must be register in order to
be produced on imported into Canada
• The individual provinces govern the use, sale, handling, and
disposal of pesticide products, as well as administering
permits and certification measures for pesticide vendors and
applicators.
• In Ontario, municipal by-laws banning cosmetic use of
pesticides were replaced by a provincial regulation.

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 Pesticide Regulations
• The Health Canada Pest Management Regulatory
Agency (PMRA) was created in 1995 and is
responsible for pesticide regulation in Canada
• Under authority of the Pest Control Products
Act, Health Canada:
• registers pesticides after a stringent, science-based
evaluation that ensures any risks are acceptable;
• re-evaluates the pesticides currently on the market on a
15-year cycle to ensure the products meet current
scientific standards; and
• promotes sustainable pest management.
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 Re-Evaluation Example
• Diazanon
• Diazinon is an organophosphate insecticide used to
control a broad range of insect pests on a variety of
crops (2009-18)
• http://www.hc-sc.gc.ca/cps-spc/pubs/pest/_decisions/index-eng.php

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 Ontario Pesticides Act
• The Ontario Pesticides Act covers all sales, handling and use
of pesticide products.
• The provincial legislation provides a system of permits and
licenses as well as a list of products that can be used in
Ontario.
• Ontario Regulation 63/09 was passed into law on March 4, 2009
and took effect April 22, 2009 (Earth Day)
• Over 250 products banned for sale and more than 80 pesticide
ingredients banned for cosmetic uses.
• Does not apply to agricultural land
• Exemptions for golf courses and sports fields

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 Ontario Pesticide Classes
• The Ontario Pesticides Advisory Committee oversees the
classification and scheduling of pesticide products that are used
or sold in Ontario.
• Class 1 are pesticides designated under the PCPA as pesticides of the Manufacturing
Class
• Classes 2, 3 and 4 are pesticides designated under the PCPA as Commercial or
Restricted Class
• Classes 5, 6 and 7 are pesticides designated under the PCPA as pesticides of the
Domestic Class
• Class 8 pesticides are banned for sale in Ontario.
• Class 9 pesticides are banned for use in, on or over land unless their use is excepted.
• Class 10 pesticides are allowed for use under the promotion of public health or safety
exception.
• Class 11 pesticides can be used by any person or licensed exterminator for cosmetic or
other purposes 29
List of Class 8 – Banned Pesticides
• http://www.ontario.ca/environment-and-energy/class-8-pesticides

List of Class 11 – Approved Pesticides

• http://www.ontario.ca/environment-and-energy/class-11-pesticides

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 Information Sources
• Agency for Toxic Substances Disease Registry (ATSDR)
www.atsdr.cdc.gov

• TOXicology Data NETwork (TOXNET)

http://toxnet.nlm.nih.gov/

• World Health Organisation (WHO) - International Programme on Chemical Safety

http://www.who.int/ipcs/assessment/en/

• United Nations Environment Programme

http://www.unep.org/

• International Programme on Chemical Safety

http://www.inchem.org/
• Canada’s Pest Management Regulatory Agency
www.pmra-arla.gc.ca/english/index-e.html

• Environment Canada – Chemical Substances

http://www.chemicalsubstanceschimiques.gc.ca/index-eng.php

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