This month our example is
Formaldehyde, which has a chemical formula of
H2CO. Formaldehyde is listed under the UN #
(United Nations Number) by the US Department of
Transportation: UN 2209 (formalin) and has a CAS # of
50-00-0.
Persons exposed only to formaldehyde
vapor do not pose substantial risks of secondary
contamination. Persons whose clothing or skin is
contaminated with a solution of formaldehyde in water or
methanol can cause secondary contamination by direct
contact or through off-gassing vapor. Formaldehyde is a
colorless, highly toxic, and flammable gas at room
temperature that is slightly heavier than air. It has a
pungent, highly irritating odor that is detectable at
low concentrations, but may not provide adequate warning
of hazardous concentrations for sensitized persons. It
is used most often in an aqueous solution stabilized
with methanol (formalin). Most formaldehyde exposures
occur by inhalation or by skin or eye contact.
Formaldehyde is absorbed well by the lungs,
gastrointestinal tract, and, to a lesser extent, skin.
Formaldehyde is a nearly colorless
gas with a pungent, irritating odor even at very low
concentrations (below 1 ppm). Its vapors are flammable
and explosive. Because the pure gas tends to polymerize,
it is commonly used and stored in solution. Formalin,
the aqueous solution of formaldehyde (30% to 50%
formaldehyde), typically contains up to 15% methanol as
a stabilizer.
Most formaldehyde exposures occur by
inhalation or by skin/eye contact. Formaldehyde vapor is
readily absorbed from the lungs. In cases of acute
exposure, formaldehyde will most likely be detected by
odor; however, persons who are sensitized to
formaldehyde may experience headaches and minor eye and
airway irritation at levels below the odor threshold
(odor threshold is 0.5 to 1.0 ppm; OSHA PEL is 0.75
ppm). For sensitized persons, odor is not an adequate
indicator of formaldehyde’s presence and may not provide
reliable warning of hazardous concentrations. Odor
adaptation can occur. Low-dose acute exposure can
result in headache, rhinitis, and dyspnea; higher doses
may cause severe mucous membrane irritation, burning,
and lacrimation, and lower respiratory effects such as
bronchitis, pulmonary edema, or pneumonia. Sensitive
individuals may experience asthma and dermatitis, even
at very low doses. Formaldehyde vapors are slightly
heavier than air and can result in asphyxiation in
poorly ventilated, enclosed, or low‑lying areas.
Children exposed to the same levels
of formaldehyde as adults may receive larger doses
because they have greater lung surface area:body weight
ratios and increased minute volumes:weight ratios. In
addition, they may be exposed to higher levels than
adults in the same location because of their short
stature and the higher levels of formaldehyde found
nearer to the ground.
Ocular exposure to formaldehyde
vapors produces irritation and lacrimation. Depending on
the concentration, formaldehyde solutions may cause
transient discomfort and irritation or more severe
effects, including corneal opacification and loss of
vision. Formaldehyde is absorbed through intact skin and
may cause irritation or allergic dermatitis; rapid
metabolism makes systemic effects unlikely following
dermal exposure.
Children are more vulnerable to
toxicants absorbed through the skin because of their
relatively larger surface area:body weight ratio.
Ingestion of as little as 30 mL (1
oz.) of a solution containing 37% formaldehyde has been
reported to cause death in an adult. Ingestion may cause
corrosive injury to the gastrointestinal mucosa, with
nausea, vomiting, pain, bleeding, and perforation.
Corrosive injuries are usually most pronounced in the
pharyngeal mucosa, epiglottis and esophagus. Systemic
effects include metabolic acidosis, CNS depression and
coma, respiratory distress, and renal failure.
Sources/UsesFormaldehyde
is synthesized by the oxidation of methanol. It is among
the 25 most abundantly produced chemicals in the world
and is used in the manufacture of plastics, resins, and
urea‑formaldehyde foam insulation. Formaldehyde or
formaldehyde containing resins are used in the
manufacture of chelating agents, a wide variety of
organic products, glass mirrors, explosives, artificial
silk, and dyes. It has been used as a disinfectant,
germicide, and in embalming fluid. In the agricultural
industry, formaldehyde has been used as a fumigant,
preventative for mildew in wheat and rot in oats, a
germicide and fungicide for plants, an insecticide, and
in the manufacture of slow-release fertilizers.
Formaldehyde is found in construction materials such as
plywood adhesives. Formaldehyde also is or has been used
in the sugar, rubber, food, petroleum, pharmaceuticals,
and textiles industries.
Physical Properties
Description:
Nearly colorless gas with a pungent, irritating
odor.
Warning
properties: Odor is detectable at less than 1 ppm,
but many sensitive persons experience symptoms below the
odor threshold.
Molecular
weight: 30.0 daltons
Melting
Point: -134°F(-92°C)
Boiling
point: (760 mm Hg): - 6°F (-21°C)
Vapor
pressure: 3883 mm Hg at 77°F (25°C)
Gas
density: 1.07 (air = 1)
Water
solubility: 55% at 68°F (20°C)
Flammability:
Flammable gas between 7% and 73% at 77°F (25°C) (concentration
in air); combustible liquid (formalin).
Synonyms include Methanal,
Methyl Aldehyde, and Methylene Oxide.
Standards
and Guidelines
OSHA PEL (permissible exposure limit) = 0.75
ppm (averaged over an 8-hour workshift)
OSHA STEL
(short-term exposure limit) = 2 ppm (15 minute exposure)
NIOSH IDLH
(immediately dangerous to life or health) = 20 ppm
AIHA ERPG-2
(emergency response planning guideline) (the maximum
airborne concentration below which it is believed that
nearly all individuals could be exposed for up to 1 hour
without experiencing or developing irreversible or other
serious health effects or symptoms which could impair an
individual’s ability to take protective action) = 10 ppm
IncompatibilitiesFormaldehyde
reacts with strong oxidizers, alkalis, acids, phenols,
and urea. Pure formaldehyde has a tendency to
polymerize.
The systemic effects of formaldehyde
are due primarily to its metabolic conversion to
formate, and may include metabolic acidosis, circulatory
shock, respiratory insufficiency, and acute renal
failure.
Formaldehyde is a potent sensitizer
and a probable human carcinogen.
Acute
ExposureFormaldehyde vapor produces immediate local
irritation in mucous membranes, including eyes, nose,
and upper respiratory tract. Ingestion of formalin
causes severe injury to the gastrointestinal tract. The
exact mechanism of action of formaldehyde toxicity is
not clear, but it is known that it can interact with
molecules on cell membranes and in body tissues and
fluids (e.g., proteins and DNA) and disrupt cellular
functions. High concentrations cause precipitation of
proteins, which results in cell death. Absorption from
the respiratory tract is very rapid; absorption from the
gastrointestinal tract is also rapid, but may be delayed
by ingestion with food. Once absorbed, formaldehyde is
metabolized to formic acid, which may cause acid-base
imbalance and a number of other systemic effects.
Children
do not always respond to chemicals in the same way that
adults do. Different protocols for managing their care
may be needed.
CNS
Malaise, headache, sleeping disturbances,
irritability, and impairment of dexterity, memory, and
equilibrium may result from a single, high level,
exposure to formaldehyde.
Respiratory
Even fairly low concentrations of formaldehyde can
produce rapid onset of nose and throat irritation,
causing cough, chest pain, shortness of breath, and
wheezing. Higher exposures can cause significant
inflammation of the lower respiratory tract, resulting
in swelling of the throat, inflammation of the windpipe
and bronchi, narrowing of the bronchi, inflammation of
the lungs, and accumulation of fluid in the lungs.
Pulmonary injury may continue to worsen for 12 hours or
more after exposure. Previously sensitized individuals
can develop severe narrowing of the bronchi at very low
concentrations (e.g., 0.3 ppm). Bronchial narrowing may
begin immediately or can be delayed for 3 to 4 hours;
effects may worsen for up to 20 hours after exposure and
can persist for several days.
Exposure
to certain chemical irritants can lead to Reactive
Airway Dysfunction Syndrome (RADS), a chemically- or
irritant-induced type of asthma.
Children
may be more vulnerable to corrosive agents than adults
because of the relatively smaller diameter of their
airways. Children may be more vulnerable because of
relatively increased minute ventilation per kg and
failure to evacuate an area promptly when exposed.
Metabolic
Accumulation of formic acid can cause an anion-gap
acid-base imbalance. If formalin is ingested, absorption
of the methanol stabilizer may contribute to the
imbalance and can result in an osmolal gap, as well as
an anion gap.
Immunologic
In persons who have been previously sensitized,
inhalation and skin contact may cause various skin
disorders, asthma-like symptoms, anaphylactic reactions
and, rarely, hemolysis. The immune system in children
continues to develop after birth, and thus, children may
be more susceptible to certain chemicals.
Gastrointestinal
Ingestion of aqueous solutions of formaldehyde can
result in severe corrosive injury to the esophagus and
stomach. Nausea, vomiting, diarrhea, abdominal pain,
inflammation of the stomach, and ulceration and
perforation of the oropharynx, epiglottis, esophagus,
and stomach may occur. Both formaldehyde and the
methanol stabilizer are easily absorbed and can
contribute to systemic toxicity.
Ocular
Exposure to low concentrations of formaldehyde vapor
can cause eye irritation, which abates within minutes
after exposure has ended. Formalin splashed in the eyes
can result in corneal ulceration or cloudiness of the
eye surface, death of eye surface cells, perforation,
and permanent loss of vision; these effects may be
delayed for 12 hours or more.
Dermal
Exposure to formaldehyde vapor or to formalin
solutions can cause skin irritation and burns. In
sensitized persons, contact dermatitis may develop at
very low exposure levels.
Potential
Sequelae In survivors of inhalation injury,
pulmonary function usually returns to normal. Eye
exposure to high concentrations of formaldehyde vapor or
formalin can eventually cause blindness. Narrowing of
the esophagus and severe corrosive damage to the stomach
lining can result from ingesting formalin.
Chronic
ExposureThe major concerns of repeated formaldehyde
exposure are sensitization and cancer. In sensitized
persons, formaldehyde can cause asthma and contact
dermatitis. In persons who are not sensitized, prolonged
inhalation of formaldehyde at low levels is unlikely to
result in chronic pulmonary injury. Adverse effects on
the central nervous system such as increased prevalence
of headache, depression, mood changes, insomnia,
irritability, attention deficit, and impairment of
dexterity, memory, and equilibrium have been reported to
result from long-term exposure. Chronic exposure may be
more serious for children because of their potential
longer latency period.
Carcinogenicity
The Department of Health and Human Services has
determined that formaldehyde may reasonably be
anticipated to be a carcinogen. In humans, formaldehyde
exposure has been weakly associated with increased risk
of nasal cancer and nasal tumors were observed in rats
chronically inhaling formaldehyde.
Reproductive
and Developmental Effects There is limited evidence
that formaldehyde causes adverse reproductive effects.
The TERIS database states that the risk of developmental
defects to the exposed fetus ranges from none to
minimal. Formaldehyde is not included in Reproductive
and Developmental Toxicants, a 1991 report published
by the U.S. General Accounting Office (GAO) that lists
30 chemicals widely acknowledged to have reproductive
and developmental consequences.
There have
been reports of menstrual disorders in women
occupationally exposed to formaldehyde, but they are
controversial. Studies in experimental animals have
reported some effects on spermatogenesis. Formaldehyde
has not been proven to be teratogenic in animals and is
probably not a human teratogen at occupationally
permissible levels. Formaldehyde has been shown to have
genotoxic properties in human and laboratory animal
studies producing sister chromatid exchange and
chromosomal aberrations.
Special
consideration regarding the exposure of pregnant women
is warranted, since formaldehyde has been shown to be a
genotoxin; thus, medical counseling is recommended for
the acutely exposed pregnant woman.<
In using the PEAC application we
access information for the chemical by first locating
Formaldehyde in the database. The following figures show
the screens displayed for chemical properties, Figure 1
for the PEAC-WMD for Windows application and
Figure 2-5 for the PEAC‑WMD for the Pocket PC
application.
Figure 1 - Using
the Lookup By: Name for Formaldehyde using the PEAC-WMD
for Windows application
Review of the information displayed
in the chemical properties screen whether in Figure 1
(above) or Figures 2-4 (below), show chemical properties
values discussed earlier at the top of this discussion.
As you can see below, the published toxicity values,
e.g., IDLH, ERPGs, and the TEELs (Temporary Emergency
Exposure Limits) published by Department of Energy are
provided. We will use the IDLH as the Level of Concern
when we develop the PAD a little later.
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Figure 2 – Selecting Formaldehyde
using the PEAC-WMD for Pocket PC application
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Figure 3 – The top portion of the
Chemical Properties Data Display Screen
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Figure 4– The bottom portion of
the Chemical Properties Data Display Screen
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A benefit of using the PEAC tool is
assistance in the development of an evacuation zone for
those chemicals that produce a toxic vapor cloud. If
transported as a compressed liquefied vapor it will be
released from a container as a vapor or aerosol or a
liquid that will rapidly vaporize. As with all of our
examples, AristaTek creates a scenario for a spill or
release of the specific chemical, and then we work
through the development of a PAD (Protective Action
Distance) to demonstrate how the PEAC system works.
For our hypothetical scenario using
Formaldehyde as the involved chemical we’ll set the
location to be an urea‑formaldehyde foam insulation
facility located in Miami, FL. The date is October 13,
2003, about 12:30 PM with a temperature of 85°F, a wind speed of 10 mph with a
partly cloudy sky for the daytime release. The release
involves a portable tank that has a 1” transfer valve
knocked off by a forklift. The PEAC tool can provide
guidance with regards to toxic vapor cloud that is
released.
If you decide to follow along as we
proceed through these examples, remember to set the
location to Miami and set the date and time to the
proper values, otherwise you’ll compute different
values. Also it should be understood that the examples
shown below assume that no explosion or fire is
involved, otherwise the Formaldehyde would ignite.
As seen at the top of the data
display screens, there is a yellow icon displayed; this
is the PEAC icon for notifying the user that a
Protective Action Distance can be calculated. Clicking
or tapping on the PAD icon will display a screen as
shown in Figure 5. Following through the screens, we
provide information on the Meteorology, Container Size,
and Type of Release (Source). The following figures
demonstrate how we would work through our scenario to
see what our Protective Action Distance should be.
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| Meteorology
It’s Miami in October and the
temperature about 85°, wind is set for 10 mph,
partly cloudy skies and the terrain is
Urban/Forest since it’s an industrial
setting. |
Container
We have selected from our list
of container sizes the Portable Tank
selection; this gives some quick dimensions
that should get us close to the right size.
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Source
We have selected a Hole or
Pipe Release for the type of release with a
1” Hole Diameter.
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Figure 5 – Calculating a PAD using the
PEAC‑WMD System for October 13th
By pressing the right arrow at the
top of the screen, the PEAC system will display a screen
as shown in Figure 6. This calculates a PAD
(Protective Action Distance) based on the default
Level of Concern the IDLH of 20 ppm. This
evacuation or standoff distance is based on the toxicity
of Formaldehyde.
Figure 6 – Default PAD for Formaldehyde
using the IDLH of 20 ppm
If we felt that the IDLH was not a
conservative enough concentration to provide adequate
protection to the public, we can quickly compute another
PAD using another Level of Concern concentration. For
instance, we could select the ERPG-2 value from the
pop-up list as shown in Figure 7. The results of the new
calculations are shown in Figure 8.
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Figure 7 – Selecting another Level
of Concern from the pop-up list |
Figure 8 – The PAD calculated
based on the ERPG-2 LOC of 10 ppm.
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Substantial portions of this
discussion were adapted from the Agency for Toxic
Substances and Disease Registry (ATSDR) Web site for
Medical Management Guidelines at: http://www.atsdr.cdc.gov/.