Fate of Volatile Organic Compounds

(VOC) in the Environment

Norhaima P. Dibaratun
CHEM289 – Environmental Chemistry
Under Prof. Ma.Cecilia Almeda
 Quick Review
Air Pollution
Chemicals
Health Effects

Pollutants Natural Man-made

Lung Heart Eye
Cancer
disease disease Irritation

Lead,
VOCs CO NOx SO2 PM
Mercury etc.
Primary

Smog O3 HNO3 H2SO2 Secondary

Acid Deposition
What are VOCs?
What are VOCs?
“… substances, including hydrocarbons and their
derivatives, that readily vaporize into the air are called
volatile organic compounds, or VOCs, many of which
react in photochemical smog.”

“Volatile organic compounds (VOCs) are emitted as gases

from certain solids or liquids. This is a very broad set of
chemicals. VOCs include a variety of chemicals, some of
which may have short and long-term adverse health
effects. Concentrations of many VOCs are consistently
higher indoors (up to ten times higher) than
outdoors.”
“VOCs as categorized by the World Health Organization
(WHO) are compounds with a boiling point less than 250°C
measured at a standard atmospheric pressure of 101.3 kPa”
SOURCE
VOCs are introduced into the atmosphere through
anthropogenic or biogenic activities and add to problems in
the formation of tropospheric ozone and particles lower
than 2.5 micrometers in large cities. (Montero-Montoya,
2018)
LIST OF COMMON VOCs AND THEIR SOURCE

• Acetone (nail polish remover, furniture polish and wallpaper)

• Acetic Acid (vinegar)
• Butanal (candles, barbecues, gas stoves)
• Carbon Disulfide (chlorinated tap water)
• Ethanol (many cleaning products, glass cleaners, dishwashers detergents)
• Alcohol (disinfecting agent)
• Formaldehyde (plastics, lacquers)
• Methylene Chlorine (paint removers, aerosol solvent, flame retardant
chemicals)
• 4-phenylcyclohexane, 4-PC (new carpet)
 Benzene and some of its organic derivatives, like Toluene,
Ethylbenzene and Xylene (o-, m- and p-) or BTEX,
• most abundant VOCs in the environment, 60%
• found in natural form in crude oil, diesel and gasoline (they are released into the
environment whether or not these fuels are burned.)
• highly used in the industry as additives and precursors of other substances:

benzene is used in the manufacturing of synthetic materials and consumer products,

including plastics, nylon, insecticides and paints;

toluene is used as solvent for paints, coatings, rubbers, oils and resins;

ethylbenzene may be found in paints, plastics and pesticides, and it is also

used as additive for aviation fuel; and

xylenes are used as solvent in the printing, rubber and leather industries
Chemical structure
of BTEX

Upper line:
benzene, toluene and
ethylbenzene
Lower line:
orto-, meta and
para-xylene.
Types of VOCs
The EPA categorizes VOCs by their volatility.

1. Very Volatile Organic Compounds (VVOC)

boiling point range of <0 to 50-100 degrees centigrade
Exist as gas

Ex:

Propane
Butane
Methyl Chloride
Types of VOCs
The EPA categorizes VOCs by their volatility.

2. Volatile Organic Compounds (VOC)

boiling point range of 50-100 to 240-260 degrees centigrade.

Ex:
Formaldehyde
D-Limonene
Toluene
Acetone
Ethanol (Ethyl Alcohol)
2-propanol (Isopropyl Alcohol)
Hexanal
Types of VOCs
The EPA categorizes VOCs by their volatility.

3. Semi-Volatile Organic Compounds (SVOC)

SVOCs have a boiling point range of 240-260 to 380-400 degrees centigrade.

Ex:

Pesticides (DDT, Chlordane, Plasticizers (Phthalates)

Fire retardants (PCBs, PBB)
EFFECTS ON THE ENVIRONMENT

▪ O3 and PANs (Peroxyacyl

nitrates) can damage
crops and decrease
yields
▪ Photochemical Smog
▪ Temperature Inversion
Acetone in the upper troposphere
Methane in the upper troposphere
Temperature Inversion
Temperature Inversion
Temperature Inversion
Temperature Inversion
HEALTH

https://www.health.state.mn.us/communities/environment/air/toxins/voc.htm
VOCs in water
Among the various micropollutants, volatile organic compounds
(VOCs) are primarily recognized as atmospheric pollutants, yet water
pollution caused by these compounds is also gaining increasing
interest

Paint and coatings, oil, solvents, agricultural and municipal

wastewater, urban and rural effluents, and atmospheric deposits are
the primary sources of anthropogenic VOCs in aquatic ecosystems

Also, oil spills.

VOCs Removal in
Water
Wastewater effluent that
is contaminated with
VOCs, e.g., the water
emanating from
chemical or
petrochemical plants, is
commonly treated by a
two-step process:

1. The VOCs are

removed from the
wastewater by air
stripping.
2. The resulting VOCs, now present in low concentration in
a contained mass of humid air, are destroyed by a process
of catalytic oxidation.

the air, heated to 300–500°C, is passed for a short time

over platinum, or, depending upon the VOC, some other
precious metal, that is supported on alumina.
 Effects of VOCs in aquatic organisms.
Adverse effects of toluene on survival, growth, and reproduction in
other aquatic species, including algae, daphnia, and fathead
minnow, have also been reported previously (Im, J.-K., 2021)
What are safe levels of VOCs in water?
The Environmental Protection Agency (EPA) has established safe drinking water
standards. The standards for many of the VOCs commonly found in water,
measured in parts per billion (ppb), are listed in the table to the right.
VOCs in Land
Micropollutants present in MSW leachate include common volatile
organic compounds such as toluene and dichloromethane.

Engineering is needed to control the leachate from a landfill.

Otherwise the liquid can flow out the bottom of the landfill, and
percolate through porous soil and contaminate the groundwater below
it.
The general categories of technologies currently
available for the remediation of contaminated sites
are:

• containment or immobilization
• mobilization (thermal desorption)
• destruction (incineration and bioremediation)
Sanitary landfill,
The biggest bioremediation project in history before the 2010 Gulf
of Mexico oil spill was the treatment of some of the oil spilled by the
Exxon Valdez tanker in Alaska in 1989. The bioremediation
consisted of adding nitrogen-containing fertilizer to more than 100
km of the shoreline that had been contaminated, thereby
stimulating the growth of indigenous microorganisms, including
those that could degrade hydrocarbons. Both surface and
subsurface oil was biodegraded in this operation. Some of the
aromatic components in crude oil in marine spills become more
susceptible to biodegradation once they are photooxidized by
sunlight into more polar species.
 How do VOCs enter into the food chain?
They are rather inert lipophilic compounds capable of passing through
biological membranes, with a toxicity that basically depends on their
biotransformation within the body
Recent concentration limits of VOC
● No standards have been set for VOCs in non industrial settings. There are thousands of
VOC compounds. Some of the compounds have been recognized as a specific health risk
and have specific guidelines.

● When the USEPA built their own building, they used a Maximum Allowable Air
Concentration Standard of <0.20 mg/m3 Total Volatile Organic Compounds (TVOCs).

● Occupational Safety and Health Administration (OSHA) regulates formaldehyde, a specific

VOC, as a carcinogen. OSHA has adopted a Permissible Exposure Level (PEL) of .75 ppm,
and an action level of 0.5 ppm.

● US Department of Housing and Urban Development (HUD) has established a level of 0.4
ppm for mobile homes.

● Based upon current information, it is advisable to mitigate formaldehyde that is present at

levels higher than 0.1 ppm.
[REPUBLIC ACT NO. 8749]
AC ACT PROVIDING FOR A COMPREHENSIVE AIR POLLUTION CONTROL
POLICY AND FOROTHER PURPOSES
Polynuclear Aromatic Hydrocarbons (PAHs)
six-membered
benzene-like rings
connected by the
sharing of a pair of
adjacent carbon
atoms between
adjoining fused
rings

As a compound, naphthalene is a volatile solid whose vapor is toxic to

some insects. It has found use as one form of “moth balls,” the other being
1,4-dichlorobenzene.
PAH pollutants arising from incomplete combustion, especially of wood and coal.
They are also released into the environment from the dumpsites of industrial
plants that convert coal into gaseous fuel, and from the refining of petroleum and
shale. In rivers and lakes, they are found mainly attached to sediments rather
than dissolved in the water; both are subsequently partially incorporated by
fresh-water mussels.
Formation of PAHs During
Incomplete Combustion

The mechanism of PAH formation during combustion of organic materials

is complex, but is due primarily to the repolymerization of hydrocarbon
fragments that are formed during the cracking (i.e., the splitting into
several parts) of larger fuel molecules in the flame.

C2 - fragment

C2 + C 2 = C 4
C4 + C2 = C6 (Six-carbon ring ex. benzene)
PAHs as Air Pollutants
PAHs are introduced into the environment from a
number of sources:
Human activities:
• Exhaust of gasoline and especially diesel combustion engines
• “Tar’ of ciggarrette smoke
• Oil refinery process
• Burning garbage/incinerate medical and industrial waste
• Surface of charred or burned food
• Smoke from burning wood or coal

Natural:
• Forest and grassland fire
• Volcanic eruption
• Fossil fuels
The physical state and average airborne lifetime of PAHs
depends significantly on their mass and on the ambient
temperature, since their lifetime is determined largely by
their vapor pressure:
• PAHs containing four or fewer rings usually exist as gases if they are
released into air, since the vapor pressures of their liquid form is relatively
high. After spending on average less than a day in outside air, such PAHs are
degraded by a sequence of free-radical reactions that begin by the addition of
the OH radical to a double bond.
• In contrast to their smaller analogs, PAHs with more than four benzene rings
do not exist for long in air as gaseous molecules. Owing to their low vapor
pressure, large PAHs condense and become adsorbed onto the surfaces of
suspended soot and ash particles. In winter, even small PAHs adsorb onto
particles, since their vapor pressures decrease sharply at lower temperatures.
PAHs adsorb mainly on particles of submicron, i.e., respirable size;
consequently, they can be transported into the lungs by breathing.
PAHs as Water Pollutants

PAHs enter the aquatic environment as a result of:

• Oil spills from tankers

• Refineries
• Offshore oil drilling sites
• coal-tar derivatives as creosote (85% of the 200 compounds in creosote are
PAHs)

Cause a threats to the marine life

How are we exposed to PAHs?

1. Ingestion (eating) ex. Grilled Foods

2. Dermal (Skin Contact)
3. Inhalation ex. Stoves at home, smoking, candles
Health effects

1. Cancer
2. Reproductive effect
THANK YOU. =)
References:

Baird, C., & Cann, C. (2012). Environmental Chemistry 5th Ed. 41 Madison Avenue, New York. H.
Freeman and Company

Montero-Montoya R, López-Vargas R and Arellano-Aguilar O. Volatile Organic Compounds in Air:

Sources, Distribution, Exposure and Associated Illnesses in Children. Annals of Global Health. 2018;
84(2), pp. 225–238. DOI: https://doi.org/10.29024/aogh.910

Kim Preshoff on TedED YT

Im, J.-K.; Cho, Y.-C.; Noh, H.-R.; Yu, S.-J. Geographical Distribution and Risk Assessment of Volatile
Organic Compounds in Tributaries of the Han River Watershed. Agronomy 2021, 11, 956.
https://doi.org/10.3390/agronomy 11050956

Lesa A. Thompson, Wageh S. Darwish, “Environmental Chemical Contaminants in Food: Review of

a Global Problem”, Journal of Toxicology, vol. 2019, Article ID 2345283, 14 pages, 2019.
https://doi.org/10.1155/2019/2345283