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Pesticides
(WHO) definition: chemical compounds used to kill pests, including insects, rodents, fungi, and unwanted plants
(US EPA): any substance or mixture of substances intended for preventing, destroying, repelling or mitigating any pest
chemical pesticides are used for agricultural purposes
General Characteristics of Pesticides
Lipophilic - soluble in fat
sometimes slow to degrade in the environment and in the body (bioaccumulation)
Commercial pesticides: mixtures containing the active ingredient and by-products, propellants, surfactants, etc
Combined properties of the components can affect toxicity and other characteristics of a pesticide (e.g synergism: 1 + 1 = 5)
Types of Pesticides
Systemic: absorbed and distributed throughout the plant, providing protection from pests that feed on various parts of the plant
works from roots up
Contact: applied directly to the surface of plants, soil, other substrates to control pests on contact
Broad-spectrum: targets and controls a wide range of pests
downside?: non-target animals & plants are also affected
Narrow-spectrum: specific to particular types of pests
Organophosphates
Developed during WWII for use as chemical (nerve gas) weapons
mode of action: irreversibly inactivating acetylcholiine-esterase which regulates acetylcholine, leading to an increased accumulation of acetylcholine. This disturbs transmission of impulses at the nerve & muscle endings
small amounts can be detected in food and drinking water
Carbamates
used for insecticides
mode of action: reversibly inactivates acetylcholine-esterase
e.g carbaryl
Organochlorines
insecticides
Mode of action: opening sodium channels in axonal membranes leading to spontaneous depolarization
persistent in the environment and many have been banned by the US EPA and the WHO
Pyrethroids
synthetic form of pyrethrins
typically insecticides used for agricultural and household purposes
majority of household insecticides are composed of pyrethroids
Neonicotinoids
high degree of selectivity toward insects
chemically similar to nictotine
Herbicides
most COMMONLY used pesticides
weed killers - stunt or kill unwanted plants
product usually contains side products (emulsifiers, dispersants) in addition to the herbicide —> increases toxicity to humans
General toxicity: dermal irritation, allergy, asthma
chronic low dose exposure related to hormonal/reproductive/genotoxic/carcinogenic effects
Glyphosate
most WIDELY used herbicide in the world today
used on millions of acres of crop land, and in urban/home application
works (in plants) by inhibiting synthesis of some amino acids
Dissipation Pathways
The way pesticides can be transported by wind, water, and through soil
Pathways:
spray drift (by the wind)
surface run-off and wash-off (by water)
volatilization (influenced by temperature)
Scorption/retention and microbial/chemical transformations (in the soil)
leaching (through the soil)
foliar interception and plant uptake (by plants)
Effects on the Environment
Soil:
biodiversity loss in the soil —> less nitrifying micro-organisms leading to less fertile soil
less organic matter: less retention of water, more build up of pesticides
creates vicious, degradation cycle of less fertile soils needing increased use of fertilizer
Environmental Effects on Wildlife
disturbs symbiotic relationship between nitrogen fixing bacteria and plants
affects plant growth and indirectly animals
direct effect on animals through dietary exposure (ingesting contaminated food and water)
Adverse Health Effects
Acute: poisoning leading to dizziness, headaches, convulsions, loss of consciousness
Chronic: occupational (farmers), dietary exposure leading to neurological/neurodegenerative diseases (Alzheimer, Parkinson)
Children are vulnerable to pesticides b/c of curious behavior and less physiological size —> slower metabolism of toxicants
some pesticide classes have properties mimicking hormones and affecting multiple organ systems and functions (reproductive health and cancer risk)
Exposure to toxicological insecticides can affect the central nervous system
General Properties of Metals
Metallic: metal atoms bonded to each other
e.g copper wire
Ionized: the metal atoms are charged, and bonded to a non-mental element
e.g NaCl
Organic: bound to carbon-containing molecules
e.g methyl-group added to a metal
The “Good” of Metals
Intra and intercellular communications
maintaining electrical charges (proper functioning of nerve cells, muscle cells, brain & the heart)
maintains DNA integrity by participating in various biochemical processes involved in DNA repair/stabilization/protection against oxidative damage/regulation of DNA-binding proteins
Lead Exposure
naturally occurring, exposure mostly due to human activities
Lead - sources of exposure
drinking water: lead water service lines, lead connections, lead-based plumbing materials
Food: contaminated water bodies, wild birds & game containing lead shot
cosmetics
lead-based paint (seen in older homes & buildings)
Lead - Biologic Fate
Distribution to:
bones and teeth (half life: 25 years)
where most of lead is found in adults
distributed to other parts of the body, but very slow; faster in times of physiological stress (pregnancy, fasting, starvation)
total lead in the body determines the burden
Lead - Exposure Routes
Ingestion: absorption from G-I tract to distribution to other organs and excretion
increased absorption during pregnancy, fasting, childhood & mineral nutritional status
Inhalation: can be absorbed up to 100%
humans mostly exposed to INORGANIC PB which DOES NOT metabolize in the body
ORGANIC lead compounds METABOLIZE in the liver
generally considered less toxic due to higher bioavailability
Lead - adverse health effects
low levels primarily affect the nervous system
unborn child, neonates, infants, and children most sensitive to neruotoxic effects
have a more permeable blood-brain barrier
Pregnant women: lead is released from the mother’s bones along with calcium, has detrimental effects on developing fetus & infant
Adults: relatively LOW lead concentrations affect central nervous system (CNS); causes:
fatigue
poor concentration
behavioral changes
Peripheral nervous system (PNS) effects:
affects nerves transmitting signals to muscles
“wrist drop” —> extensive exposure to lead paint
cardiovascular effects, increased blood pressure & hypertension, decreased kidney function, reproductive problems (in men + women)
Mercury
naturally-occuring, found in earth’s crust and in deposits of of coal
found in 3 forms: elemental (metallic), inorganic (mercury salts), organic (methylmercury)
methylmercury bioaccumulates in organims
the form of Hg determines the distribution and effects in the body
Mercury Sources
natural: volcanic activity
anthropogenic: burning of fossil fuels; coal fired power plants
Mercury Uses
used in veterinary and human medicine as topical antiseptics
Thimerosal: used as antibacterial preservative to prevent growth of dangerous bacteria and fungus
is an ORGANIC form used in vaccines w/ more than one dose
low concentration doesn’t have any adverse health effects
Mercury: acute vs chronic exposure
Acute: primarily occurs with vapors from elemental Hg
rare acute exposure with ingestion of inorganic or methyl mercury
Chronic toxicity: more common
consumption of fish containing Hg
Disruption and effects on health of Mercury
Ionic form: MOST toxic, but don’t cross membranes well
Hg vapor: absorbed by inhalation & readily diffuses across lipid membranes of cells
Methyl Hg: 95% absorbed by oral route
Concerns of Methyl Hg
common environmental contaminant
Minamata Bay, Japan —> abundance of fish high in methyl-Hg
effects on health: reproductive, developmental, renal, and neurotoxic effects and death
Iraq: Hg-treated grain (against pests) that was intended to be planted, was consumed
Arsenic
naturally occurring element widely distributed in the earth’s crust
CANNOT be destroyed in the environment, only changes form
inorganic and organic
INORGANIC FORM IS HIGHLY TOXIC
exposure routes: ingestion - water & rice, dermal - contaminated soil, dust
Organic form - less to non-toxic
exposure through seafood consumption
Sources of Arsenic Exposure
Anthropogenic:
mining
burning of fossil fuels
pesticide fertilizers
industrial waste
Natural:
volcanic eruptions
forest fires
soil
rock weathering
groundwater
Arsenic & Adverse Health Effects
breathing high levels of inorganic arsenic cause sore throat/irritated lungs
Chronic toxicity: neurotoxicity, hepatotoxicity, cancers
Benzene
Volatile Organic Compound
primarily ANTHROPOGENIC
widely used in the U.S for production volume
Benzene Exposure
breathing in airborne benzene
skin contact with gasoline and other liquids containing benzene
drinking benzene-contaminated water
Benzene ADME and Toxicology
Absorption: inhalation, ingestion, dermal
Body Distribution: bone marrow and high lipid content tissues
causes CNS and Hematologic effects
Benzene Exposures
Outdoor air levels are less than indoor air levels in terms of benzene levels
outdoor emits from tobacco smoke, gas stations, motor vehicle exhaust, industrial emissions
indoor emits are from glues, paints, furniture wax, detergents
also leaks from underground storage tanks that can contaminate well water
Those most at risk:
steel workers
gas station employees
workers in petrochemical/coal/rubber tire companies
tobacco smoke
Benzene Neurological Effects
Acute: solvent effect
CNS neurodepression
Chronic - repeated long-term exposures
e.g Painters syndrome (sniffing)
Chronic toxicity in the hematopoietic system
damage of pluripotent stem cells of the bone marrow
Cadmium
soft, malleable, bluish white metal
found in tiny amounts in air, water, soil, food
used in paints, batteries, electronics, by-product of smelting, tobacco
contaminant of grains (e.g rice), and in seafood from contaminated water bodies
Cadmium Toxicity
low uptake from gut & very slow excretion rate
classical nephrotoxic agent (kidney disease)
recognized as a carcinogen
Chromium
naturally occurring
used in metal plating, paints, electronics, steel making
+3 and +6 valences are common
+6 forms are genotoxic (toxic to genetic material)