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Risk Management for Hazardous Chemicals

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MATERIAL SAFETY DATA SHEET


CHEMICAL NAME

CRC PRESS/LEWIS PUBLISHERS DISCLAIMER: THE INFORMATION AND RECOMMENDATIONS


PRESENTED HEREIN ARE BASED ON SOURCES BELIEVED TO BE RELIABLE. CRC MAKES NO REPRESENTATION ON
ITS COMPLETENESS OR ACCURACY. IT IS THE RESPONSIBILITY OF THE USER TO DETERMINE THE CHEMICAL'S
SUITABILITY FOR ITS INTENDED USE, THE CHEMICAL'S SAFE USE, AND THE CHEMICAL'S PROPER DISPOSAL. NO
REPRESENTATIONS AND/OR WARRANTIES, EITHER EXPRESSED OR IMPLIED, OF THE MERCHANTABILITY OR
FITNESS FOR A PARTICULAR PURPOSE, OR OF ANY OTHER NATURE, ARE MADE WITH RESPECT TO THE INFORMATION PROVIDED IN THIS MSDS OR TO THE CHEMICAL TO WHICH INFORMATION MAY REFER. CRC
NEITHER ASSUMES NOR AUTHORIZES ANY OTHER PERSON TO ASSUME FOR IT, ANY OTHER ADDITIONAL RESPONSIBILITY OR LIABILITY FOR THE USE OF, OR RELIANCE UPON, THIS INFORMATION.

TETRAMETHYL LEAD

HAZARD WARNING INFORMATION


HEALTH

FIRE

REACTIVE

OTHER

DEGREE OF HAZARD
0 = Minimum Hazard
1 = Slight Hazard
2 = Moderate Hazard
3 = Serious Hazard
4 = Severe Hazard

COLOR CODING

OTHER CODES

HEALTH = BLUE
FIRE = RED
REACTIVITY = YELLOW
OTHER = WHITE

OX = Oxidizer
ACID = Acid
ALK = Alkali
COR = Corrosive
W = Use No Water

SECTION I - GENERAL INFORMATION


Characterization

RCRA Number

Metal Alkyl

EPA Class

D008 (as Lead)

DOT Proper Shipping Name

Characteristic (T) Waste

Chemical Abstract Service (CAS) Number

Flammable Liquid, Poisonous, N.O.S.

75-74-1

DOT Hazard Class and Label Requirements

DOT Emergency Guide Code

Flammable Liquid and Poison

56

DOT Identification Number

Chemical Symbol

UN 1992

Pb(CH3)4

Synonyms

Lead tetramethyl; TML; tetramethylplumbane.

SECTION II - HAZARDOUS INGREDIENTS AND IDENTITY INFORMATION


Hazardous Components (specific identity)

OSHA Exposure Criteria

Tetramethyl lead [derivation: By


alkylation of lead-sodium alloy with methyl
chloride; by electrolysis of a methyl Grignard reagent with an anode of lead pellets].

PEL (as Pb):


0.075 mg/m3
(skin)

1 ppm = 11.11 mg/m3

STEL:
Not
Established

NIOSH Exposure Criteria

Immediately Dangerous to
Life and Health (IDLH)

PEL (as Pb):


0.075 mg/m3
(skin)

ACGIH Exposure Criteria

TLV (as Pb):


0.15 mg/m3
(skin)
40 mg/m3
(as Pb)

STEL:
Not
Established

STEL:
Not
Established

SECTION III - PHYSICAL AND CHEMICAL CHARACTERISTICS


Boiling Point

Specific Gravity (H2O = 1)

212F (100C) Decomposes

2.00

Vapor Pressure (mm Hg)

Molecular Weight

23 at 68F (20C)

267.3

Vapor Density (Air = 1)

Melting Point

-15F (-26C)

9.2
Solubility

Insoluble in water (decomposes first to trimethyl salt, then dimethyl salt, finally inorganic lead). Soluble
in alcohol, benzene, and petroleum ether. Slightly soluble in ethyl ether. Miscible in fats and oils.
Appearance and Odor

Colorless liquid that may be dyed red, orange, blue, or other color, with a pleasant, fruity, sweet odor.

SECTION IV - FIRE AND EXPLOSION HAZARD DATA


Flash Point (method used)

Explosive Limits in Air % by Volume

100F (38C) closed cup


NFPA Classification

LEL: 1.8%

UEL: Not Determined

Autoignition Temperature

Class II Combustible Liquid

Not Reported

Extinguishing Media

Use dry chemical, carbon dioxide, water spray, fog, or regular foam.
Special Fire Fighting Procedures

Poisonous gases are produced in fire. Wear self-contained breathing apparatus (SCBA) and special protective clothing. Use cool water spray to cool the sides of fire-exposed containers. Stay clear of the
ends of tanks and evacuate 1500 feet if rising sound is heard coming from venting device.
Unusual Fire and Explosion Hazards

A boiling liquid expanding vapor explosion (BLEVE) can occur when the liquid in containers adjacent to
a fire begins to boil. May explode in contact with friction or oxidizers, or above 194F (90C).

1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

Page: 2

SECTION V - REACTIVITY DATA


Conditions to Avoid

Tetramethyl lead is normally stable at room temperature under routine conditions of handling and storage. However, it decomposes in sunlight and peroxides may accumulate upon prolonged storage or in
air.

Stability
Stable

Unstable

Strong oxidizers (chlorine, fluorine, bromine), sulfuryl chloride, and potassium permanganate. Explodes
on contact with tetrachlorotrifluoromethyl phosphorane.

X
Hazardous
Polymerization
May Occur

Incompatibility (materials to avoid)

Will Not Occur

Conditions to Avoid

Under normal conditions of temperature and pressure, hazardous polymerization of tetramethyl lead will
not occur. Avoid exposure to sunlight and air.
Hazardous Decomposition or By-products

Thermal decomposition of tetramethyl lead will produce toxic and irritating smoke and fumes, including
highly toxic fumes of lead and carbon dioxide.

SECTION VI - HEALTH HAZARD DATA


Primary Route(s) of Entry:

Inhalation?

Absorption (skin)?

Ingestion?

Health Hazards

INHALATION: Primary effects on the brain and central nervous system (CNS). Effects can range from
mild to moderate to severe. Symptoms range from anxiety, irritability, insomnia, lurid
dreams, vomiting, metallic taste, pallor, cerebellar ataxia, diarrhea, disorientation, tremors, hyperexcitability, chorea, slow heart beat, hypotension, hypothermia, delusions,
hallucinations, mania, convulsions, cerebellar edema, coma, tinnitus, impaired vision,
elevated liver enzymes, anemia, lassitude, and death.
ABSORPTION: Eye and skin irritation and rapid absorption. Symptoms of inhalation are possible.
INGESTION:

Easily absorbed when ingested. If it enters the bloodstream, it can have many of the
same of effects as inhalation. It is a systemic poison that accumulates in body organs.

Carcinogenicity

NTP Listed?

Unknown Human
Unknown Animal

No

IARC Cancer Review Group?

OSHA Regulated?

Target Organs?

No3

29 CFR 1910.1000
Table Z-1 (as Pb)

Eyes, liver, CNS, CVS, kidneys.

Medical Conditions Generally Aggravated by Exposure

Mental disorders, nervous system dysfunction, kidney diseases, hypertension, and sickle-cell anemia.
Emergency and First-aid Procedures

Eye contact: Flush immediately with water for 15 minutes (minimum); seek medical attention. Skin contact: Remove all contaminated clothing. Wash contaminated skin with soap and water. For inhalation:
Remove the person from exposure. Provide respiratory assistance and CPR. Transfer to medical facility. If swallowed: Never attempt to give anything by mouth to an unconscious or convulsing person. If
large quantities are ingested, induce vomiting with Syrup of Ipecac and call physician.

SECTION VII - PRECAUTIONS FOR SAFE HANDLING AND USE


Steps to be Taken in Case Material is Released or Spilled

Remove all sources of ignition. Restrict those not involved in cleanup from entering area. Absorb liquids in vermiculite or other material and deposit in sealed drums. Use non-sparking tools.
Preferred Waste Disposal Method

No citation.
Precautions to be Taken in Handling and Storage

Containers should be protected against physical damage. Store in tightly closed containers in a cool,
dry, well-ventilated area away from incompatible materials and direct sunlight.
Other Precautions and Warnings

Wherever tetramethyl lead is used, handled, manufactured, or stored, use explosion-proof electrical
equipment and fittings.

SECTION VIII - CONTROL MEASURES AND PERSONAL PROTECTIVE EQUIPMENT


Respiratory Protection (specify type)

Exposure level is low and difficult to monitor. Use a respirator with particulate (dust/fume/mist) filter;
otherwise use a supplied-air respirator or self-contained breathing apparatus in continuous flow mode.
Ventilation

Local exhaust or general mechanical systems recommended.


Protective Gloves

Suitable to protect from skin contact

Eye Protection

Other Protective Clothing

Chemical Goggles

Protective Apron

Work/Hygiene Practices

Always wash hands thoroughly after working with tetramethyl lead powders and dusts; never bring
food, drink, or smoking materials into vicinity of tetramethyl lead.
1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

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TETRAMETHYL LEAD
Pb(CH3)4

CAS: 75-74-1

3
3

IDENTIFICATION AND TYPICAL USES


Tetramethyl lead is a colorless liquid with a pleasant,
sweet odor. It may be dyed orange, red, blue, or other
color. Used as anti-knock agent in gasoline aviation
fuel. It was used as a replacement for tetraethyl lead
during the 1960s before it was replaced by methyl tert
butyl ether (MTBE).

RISK ASSESSMENT: HEALTH


General Assessment
Tetramethyl lead is an organic compound, unlike lead
which is inorganic. Tetramethyl lead is lipid-soluble
and can easily enter the brain (encephalopathy). Systemic human poison through inhalation of vapors or
mists, ingestion either of foods or liquids containing
tetramethyl lead, or by dermal absorption. It is an experimental teratogenic and reproductive effects have
been reported. There are no data on its carcinogenic
or mutagenic effects in humans or animals. Because
tetramethyl lead must first be metabolized to triethyl
lead, then dimethyl lead, and then to inorganic lead
before toxicity results, it has a latency period (time
from exposure to onset of symptoms) which can create
a false sense of security with regard to health exposure
risk. Lead is eventually deposited in bone.
The primary effects of tetramethyl lead are on the
brain and the central nervous system. Exposure by
inhalation and absorption can cause effects ranging in
toxicity from mild to moderate to severe. Initially,
there can be anxiety, irritability, insomnia, lurid
dreams, vomiting, metallic taste, pallor, cerebellar
ataxia, and diarrhea. Symptoms can progress to disorientation, hyperexcitability, tremors, chorea, bradycardia (slow heart beat), hypotension (low blood pressure), and hypothermia (decreased body temperature).
Advanced indications of serious exposure include delusions, hallucinations, mania, convulsions, cerebellar
edema (fluid in the brain), coma, tinnitus (ringing in
the ears), impaired vision (disturbances to the optic
nerve, retina, lens, and visual cortex), elevated liver

enzymes, anemia, and death. Tetramethyl lead metabolizes to inorganic lead which has an experimental
half-life in the human body of 1460 days.

1 Acute Health Effects


The following acute (short-term) health effects may
occur immediately or shortly after exposure to tetramethyl lead:
Skin:

Tetramethyl lead can dry to a powder which


can irritate the skin. The liquid also irritates
the skin's surface and absorption is likely.

Eye:

Irritation with redness and swelling.

Lung: Possible irritation of the nose, throat, lungs


and air passages with sneezing, coughing, and
other symptoms of pulmonary irritation.
CNS:

A variety of effects including insomnia,


strange dreams, personality changes, tremors
or "shakes," stupor, hallucinations, delirium,
parasthesia, headaches, convulsions and seizures, coma, and death.

0 Chronic Health Effects


The following chronic (long-term) health effects may
occur at some time after exposure to tetramethyl lead
and can last for months or even years:
Cancer Hazards: According to information presented
in the references, tetramethyl lead has not been adequately tested for its ability to cause cancer in test
animals. However, mutation data have been reported
and many scientists believe that exposure to mutagenic
compounds may pose a cancer risk in the long-term.
Reproductive Hazard: According to information presented in the references, tetramethyl lead has been
shown to adversely affect reproduction in test animals.
There may be a decreased sex drive, impotence, sterility in males, decreased fertility and abnormal menstrual cycles in females and possible spontaneous fetal
abortions in females. It may damage the testes and
reduce sperm production.

1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

Other Chronic Effects: Tetramethyl lead is more


volatile and more slowly absorbed than tetraethyl lead.
Long-term exposure to tetramethyl can lead to appetite
loss, nausea, anemia, weakness, insomnia, muscle and
joint pain, and colic accompanied by severe abdominal
pain. Kidney damage may occur, especially with repeated or high exposure. Symptoms may persist for
weeks or months after exposure. Some loss of vision
may occur after an eye splash or with severe, repeated
exposures. Lead can cause increased blood pressure
and can accumulate in the body with repeated exposures taking months or years for the body to purge itself of the contamination. Since tetramethyl lead is
eventually metabolized into lead in the body, these
effects may also occur with repeated exposure.

Recommended Risk-Reduction Measures


Personnel should avoid direct contact with tetramethyl
lead. It is considered more hazardous than elemental
lead because of its rapid solubility. If a less toxic material cannot be substituted for a hazardous chemical,
then engineering controls are the most effective
method of reducing exposures. The best protection is
to enclose operations and/or provide explosion-proof,
local exhaust ventilation at the site of chemical release.
While not always operationally feasible, isolating operations can also reduce exposure. Using respiratory
protection is less effective than the controls mentioned
above, but is still advisable whenever working with or
around tetramethyl lead. The exposure level is extremely low (0.075 mg/m3) and difficult to accurately
monitor. A supplied-air respirator operated in continuous flow mode or a self-contained breathing apparatus (SCBA) with full facepiece in pressure demand
mode will provide the best respiratory protection. If a
full facepiece respirator is not available, then splash
goggles or safety glasses with side shields attached
should be worn to protect the eyes. To prevent hand
and skin exposures, suitable gloves should be used.
Glove manufacturers should be contacted and permeation studies obtained before final glove selections are
made.
Administrative controls should also be in place to
minimize the potential for human exposures. These
may include written procedures or policies which
specify the methods and techniques that will be practiced whenever personnel are to work with tetramethyl
lead.
All personnel should receive training on the use,
hazards, protective measures, emergency actions, and
other precautions per 29 CFR 1910.1200 (Hazard

Page: 4

Communication), prior to the first assignment in an


area where tetramethyl lead is used or stored.
Before beginning employment with tetramethyl
lead, and at regular intervals thereafter (e.g., annually),
the following medical tests are recommended:
; Blood lead levels and blood pressure (baseline).
If symptoms develop or overexposure is suspected, the
following additional tests may be useful:
; Blood lead levels and blood pressure (compare to
baseline).
; Complete blood count for microcytic anemia and
basophilic stippling, blood urea nitrogen (BUN) of
creatinine, and zinc protoporphyrin (ZPP).
; Examination of the central and peripheral nervous
systems.
; Urine test for lead (levels of 0.1 mg per liter of
urine indicate increased exposure).
Also, pregnant women, especially those undergoing
lithium psychotherapy may be at increased risk of adverse health effects on exposure to tetramethyl lead.
Other methods to reduce exposure include:
;

Where possible, enclose operations and use local


exhaust ventilation at the site where tetramethyl
lead is worked. If local exhaust ventilation or enclosure is not used, respiratory protection should
be mandatory.

Always ensure that proper protective clothing is


worn when working with tetramethyl lead.

Wash thoroughly immediately after exposure to


tetramethyl lead and at the end of the work shift
or before eating, drinking, or smoking. Clothing
contaminated with tetramethyl lead should not be
taken home.

Hazard warning information should be posted in


the work area. In addition, as part of an on-going
education and training program, all information
on the health and safety hazards of tetramethyl
lead should be communicated to all exposed
workers.

Additional exposure control measures and engineering controls are provided by OSHA in 29
CFR 1910.1025 (Lead).

RISK ASSESSMENT: ENVIRONMENT


General Assessment
The environment is still at risk of exposure during
transportation, storage, disposal, or destruction of tetramethyl lead. In almost every scenario, the threat of

1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

environmental exposure is contingent upon the proper


handling of tetramethyl lead materials, especially the
dusts and powders. Accidental contact with a variety
of incompatible materials can result in fire, explosion,
and possible contamination of the surrounding environmental mediums (water, soil, air).
Tetramethyl lead is considered a Class II Combustible Liquid (per OSHA 29 CFR 1910.106). Its
vapors can form explosive mixtures in air. It is incompatible with oxidizing agents and contact can
cause fire or explosion. These characteristics require
special consideration during any emergency situation
involving a leak or spill of tetramethyl lead. Should
tetramethyl lead ever come into contact with incompatible substances such as oxidizers, (perchlorates,
peroxides, permanganates, chlorates, nitrates) and
chemically active metals (potassium, sodium, magnesium, zinc), during transportation or storage, violent
reactions are extremely possible.
Lead and its compounds are among the metals
known and used since ancient times. It is one of the
most abundant metals in the Earths crust and can be
dissolved from rocks and minerals into surface waters.
It is used extensively across a broad spectrum of industries for a large variety of purpose. Because of its
frequent use and common occurrence, lead enters the
environment from point and non-point sources.

1 Acute Ecological Effects


Acute (short-term) toxic effects may include the death
of animals, birds, or fish and death or low growth rate
in plants. Acute effects are seen 2 to 4 days after animals or plants are exposed to tetramethyl lead.
Toxicity to aquatic life is affected by water hardness, the softer the water, the greater the toxicity.
Lead and its compounds have high acute toxicity to
aquatic life. Insufficient data are available on the
short-term effects of tetramethyl lead and its compounds to plants, birds, or land animals.

0 Chronic Ecological Effects


Chronic (long-term) toxic effects may include shortened life span, reproductive problems, lower fertility,
and changes in appearance or behavior in exposed
animals. These effects can be seen long after first exposure(s) to toxic chemicals.
Lead and its compounds have high chronic toxicity in aquatic life. Lead causes nerve and behavioral
effects in humans and could cause similar long-term
effects in birds and land animals. Insufficient data are
available on the long-term effects of lead to plants.

Page: 5

6 Water Solubility
Lead and its compounds range in their respective water solubilities from highly soluble to practically insoluble. Tetramethyl lead is considered insoluble in
water.

 Persistence in the Environment


Lead and its compounds are highly persistent in water,
with a half-life greater than 200 days. The half-life of
a pollutant is the amount of time it takes for one half
of the chemical to be degraded.

O Bioaccumulation in Aquatic Organisms


Some substances increase in concentration, or bioaccumulate, in living organisms as they breathe contaminated air, drink contaminated water, or eat contaminated food. These chemicals can become concentrated in the tissues and internal organs of animals
as well as humans.
The concentration of tetramethyl lead found in the
edible tissues of fish is expected to be much higher
than the average concentration of tetramethyl lead
found in the water from which the fish was taken.

Recommended Risk-Reduction Measures


Proper training of all transporters will reduce the likelihood of a mishap or accident resulting in the contamination of the environment. The correct use of
DOT labeling (per the MSDS) on all containers,
trucks, and rail cars will enable emergency responders
to react properly and quickly to any disaster thereby
reducing the potential risk to the environment and to
personnel.
Storage of tetramethyl lead should be segregated
from incompatible chemicals to minimize the risk of
cross-contamination or contact. Buildings designated
for storage should be equipped with appropriate fire
protection systems (alarms, sprinklers, emergency
lighting, portable extinguishers).
If a spill or leak to the environment has occurred,
fire department, emergency response and/or hazardous
materials spill personnel should be notified immediately. Cleanup should be attempted only by those
trained in proper spill containment procedures using
non-sparking tools. Contaminated soils should be removed and replaced with clean soil. When environmental contamination occurs, the local and/or state
emergency response authorities may require notification. A comprehensive emergency response or disaster preparedness/recovery plan should be in place prior

1996 by CRC Press, Inc.

Risk Management for Hazardous Chemicals

to any operations involving the use, transportation,


storage, or disposal of tetramethyl lead.
If tetramethyl lead is spilled or leaked, the following specific steps are recommended:

Page: 6

Burrell, R., D. K. Flaherty, and Leonard J. Sauers. 1992. Toxicology of the


Immune System. New York: Van Nostrand Reinhold.
Cothern, C. R. 1995. Handbook for Environmental Risk Decisionmaking.
New York: CRC Press/Lewis Publishers.

Restrict persons not wearing protective clothing


from area of spill or leak until cleanup is complete and area can be opened for normal work.

Danse, I. R. 1991. Common Sense Toxics in the Workplace. New York:


Van Nostrand Reinhold.

Remove all ignition sources and ventilate area.

Gardner, R. W. 1994. Chemical Intolerance.


Press/Lewis Publishers.

Absorb liquids in vermiculite or other absorbent


material and place in sealed drums for disposal.
Use non-sparking tools during cleanup.

It may be necessary to dispose of tetramethyl lead


as a hazardous waste. The responsible state
agency or the regional office of the federal Environmental Protection Agency (EPA) should be
contacted for specific recommendations.

New York:

CRC

Howard, P. H., et. al. 1991. Handbook of Environmental Degradation


Rates. New York: CRC Press/Lewis Publishers.
Keith, L. H. and M. M. Walker. 1995. Handbook of Air Toxics. New
York: CRC Press/Lewis Publishers.
Lauwerys, R. R., P. Hoet. 1993. Industrial Chemical Exposure. New
York: CRC Press/Lewis Publishers.
Lewis, R. J., Sr. 1993. Hawley's Condensed Chemical Dictionary, 12th
Edition. New York: Van Nostrand Reinhold.
Lewis, R. J., Sr. 1992. Sax's Dangerous Properties of Industrial Materials, Volumes 1, 2, and 3, 8th Edition. New York: Van Nostrand
Reinhold.

RISK ASSESSMENT: BUSINESS


General Assessment
Accidents or mishaps involving tetramethyl lead can
present a significant threat to business operations. The
loss or damage of equipment or facilities due to explosion or fire can significantly affect fiscal viability.
Lawsuits that may result from personnel injury/death,
public exposures, and/or environmental contamination
will also require a serious expenditure of resources.
Media attention surrounding an injury, death, or environmental damage can also result in a loss of profits
and loss of current as well as future business.

Recommended Risk-Reduction Measures


Company attorneys, safety and health professionals,
and environmental specialists should be involved in
the development of any procedures for dealing with
safety or emergency response. A company official
should be pre-designated as a public relations officer
with specific training in dealing with the press. Corporate plans and policies should be developed, approved, and implemented long before any need for
such arises.

Manahan, S. E. 1992. Toxicological Chemistry, 2nd Edition. New York:


CRC Press/Lewis Publishers.
Meyer, E. 1990. Chemistry of Hazardous Materials. Englewood Cliffs,
NJ: Prentice Hall.
Patnaik, P. 1992. A Comprehensive Guide to the Hazardous Properties of
Chemical Substances. New York: Van Nostrand Reinhold.
Rea, W. J. 1995. Chemical Sensitivity, Vol. I-III. New York: CRC
Press/Lewis Publishers.
Richardson, M. 1995. Dictionary of Substance and Their Effects, Vol. IVI. New York: CRC Press/Lewis Publishers.
Sacarello, H. L. A. 1994. The Comprehensive Handbook of Hazardous
Materials. New York: CRC Press/Lewis Publishers.
Sherman, J. D. 1988. Chemical Exposure and Disease. New York: Van
Nostrand Reinhold.
U.S. Department of Health and Human Services, National Institute for
Occupational Safety and Health. 1994. NIOSH Pocket Guide to
Chemical Hazards. Washington, D.C.: U.S. Government Printing
Office.

REFERENCES
American Conference of Governmental Industrial Hygienists. 1988.
Documentation of the Threshold Limit Values and Biological Exposure Indices, 5th Edition (with updates). Cincinnati: ACGIH
Bloom, A. D. and F. J. DeSerres. 1995. Ecotoxicity and Human Health.
New York: CRC Press/Lewis Publishers.
Brusick, D. J. 1994. Methods for Genetic Risk Assessment. New York:
CRC Press/Lewis Publishers.

1996 by CRC Press, Inc.

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