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Phosphine
Phosphine or hydrogen phosphide gas, a product of
atmospheric moisture reacting with a metal phosphide to
release the gas PH3, is the easiest to use, readily available and
leaves little, if any, residue.
From:
Encyclopedia of Food Sciences and Nutrition (Second Edition), 2003

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Chapters and Articles

Agents
V.F. Garry, A.V. Lyubimov, in
Handbook of Pesticide Toxicology (Second Edition), 2001

86.1 IDENTITY, PROPERTIES, AND USES

Chemical Name: Hydrogen Phosphide

Structure: PH3.

Synonyms: Phosphoretted hydrogen, phosphorus hydride,

Phosphorus trihydride.

The CAS Registry No.: 7803-51-2.

Conversion factor: 1 ppm = 1.39 mg/m3.

The most common commercial fumigants generating phosphine are

aluminum phosphide and magnesium phosphide. Aluminum
Phosphide (AIP) is sold under the following trade names: Phostoxin,
Fumitoxin, Agtoxin, Weevilcide, Detia, Gastoxin, Max-Kill, Phosfume,
Fastphos. Common trade names for Magnesium Phosphide (Mg3P2) are
Fumi-Cel, Fumi Strip, Magtoxin, Magnaphos, Magphos.

86.1.1 PHYSICAL PROPERTIES

Pure phosphine is an odorless and colorless gas with a molecular
weight of 34.00 and density of 1.17 at 25°C. Commercial grade
phosphine derived from aluminum or magnesium phosphide can
contain to a variable degree higher molecular weight phosphines
including diphosphines. These higher phosphines give commercial
grade fumigants containing aluminum or magnesium phosphide odor
characteristics described as decaying fish or “garlic-like.” Commercial
grade phosphine containing diphosphines can ignite and form
explosive mixtures at concentrations exceeding 1.8% phosphine in air.
The rate of conversion of the phosphide to phosphine is temperature
and humidity dependent. Similarly, metal phosphides readily
hydrolyze in water to yield phosphine, which is poorly soluble in water.
Major products resulting from the oxidation of phosphine in water are
hypophosphorous and phosphoric acids (Van Wazer, 1958; WHO,
1988).

86.1.2 CHEMISTRY
Phosphine is a nucleophile and acts as a strong reducing agent (Lam et
al., 1991). Under standard conditions of temperature, pressure, and
humidity PH3 is stable and does not undergo autoxidation. Very early
work suggests that under conditions of increased atmospheric pressure

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and oxygen content autoxidation can occur (Van Wazer, 1958). Further,
in the presence of trace levels of diphosphine and perhaps other higher
phosphines in air, PH3 will undergo a branched chain oxidation
reaction (Green et al., 1984; Osadchenko and Tomilov, 1969), a form of
autooxidation. Similarly, under experimental conditions the reaction
can be induced photolytically by ultraviolet (UV) light or ammonia
(Buchanan and Hanrahan, 1970; Woller, 1965). The branched chain
reaction when it occurs is a generator and a good source of free radicals
(see below) (Green et al., 1984):

Propagation

O2 + PH2. ⇒ HPO + OH•

OH• + PH3 ⇒ PH2• + H2O

O2+PH2• ⇒ PH + HO2•

O2 + PH ⇒ HPO + O

Branching

O + PH3 ⇒ PH2• + OH•

Termination

O + O2 + M ⇒ O3+M

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Phosphine toxicology and mode of

action
Saad M. Alzahrani, Paul R. Ebert, in
Encyclopedia of Toxicology (Fourth Edition), 2024

Chemical profile
• Name: Phosphine
• Synonyms: Phosphane; Hydrogen phosphide; Phosphorus hydride;
Phosphorus trihydride

• CAS Number: 7803-51-2

• Molecular Formula: PH3
• Chemical Structure:

• Chemical properties: Phosphine at 1 atm pressure is a gas above

−87.7 °C. It has a density of 1.379 g/L at 25 °C and 1 atm.

• Other: Phosphine is a colorless gas that is odorless when pure. It is

slightly soluble in water (0.3% at 20 °C). Phosphine is extremely
flammable and explosive; it can ignite spontaneously on contact

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Aluminum phosphide
Mahshid Ataei, ... Mohammad Abdollahi, in
Encyclopedia of Toxicology (Fourth Edition), 2024

Abstract
Aluminum phosphide (AlP) is a highly effective outdoor and indoor
insecticide and rodenticide. Moisture in the air mixes with phosphide
grains and sets off phosphine (hydrogen phosphide, phosphorus
trihydride, PH3), which is the active form of AlP. Exposure occurs
mainly in cases of acute poisoning with suicidal intent. AlP inhibits
cytochrome oxidase, interferes with cellular respiration, and induces
severe oxidative stress. The main manifestations of AlP poisoning are
severe metabolic acidosis and severe and refractory cardiogenic shock.
There is no antidote available, and the treatment is mainly supportive.
However, new and novel treatment potentials are proposed. The
mortality rate in AlP-poisoning cases is 30–100%. Therefore, prognostic
factors to better indicate the risk of mortality have been studied.
Ecotoxicity is another crucial issue affecting environmental health, and
l AlP d i h lik ifi i l i lli dd d
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FUMIGANTS
R. Davis, in
Encyclopedia of Food Sciences and Nutrition (Second Edition),
2003

Physical, Chemical, and Biological

Characteristics
The primary factors that will increase or decrease the activity and
distribution of fumigants are temperature, atmospheric moisture,
application duration, fumigant formulation, dosage, application
procedure, storage structure or other fumigation containments,
pressure (vacuum), aeration, pest population characteristics and
habitat, commodity, and contamination (e.g. dockage in grain).

The safe and effective use of fumigants depends, in large part, on

knowledge of the fumigant's primary chemical and physical properties.
Table 1 below lists fumigants that are in common use, in limited use,
or, in some instances, banned from use in many countries. In the USA,
only methyl bromide, hydrogen phosphide (phosphine), and sulfuryl
fluoride, Vikane®, are in common use and are approved by the US
Environmental Protection Agency. In this presentation, only methyl
bromide and hydrogen phosphide will be discussed. Currently, sulfuryl
fluoride has very limited approval for use on foodstuffs.

Table 1. Common fumigants and their essential properties

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Fumigants
E.M. Thoms, J.D. Busacca, in Encyclopedia of Food and Health,
2016

Commodity Fumigation
Fumigation can be the most effective method for disinfesting
commodities when placed into storage after harvesting, which have
been in storage for long periods of time, and prior to shipment for
processing or export. Fumigation should be considered one tool in
managing pest infestations in stored commodities. Other methods to
control pest infestations include sanitation and application of approved
insecticide surface treatments to storage containers prior to refilling,
proper drying of commodities prior to storage, maintaining the
required temperature and moisture content of commodities by
aeration or other methods to prevent mold and insect growth,
monitoring of pest presence through inspection and trapping, and then
determining the best control strategy when pest activity reaches
actionable thresholds.

Phosphine, or hydrogen phosphide, is one of the most commonly used

fumigants globally for disinfestation of cereal grains, legumes, seeds,
dried fruit and tree nuts, other durable food commodities, and many
processed foods. Phosphine has the unusual property that it can be
generated from solid formulations of metallic salts of aluminum
phosphide and magnesium phosphide. These metallic phosphides react
with water vapor in the treatment environment to generate phosphine.
Metallic phosphides can be applied as pellets or tablets, which can be
mixed with the commodity as it is loaded for storage, probed into or
placed on the commodity, or placed on trays or paper adjacent to the
commodity. Metallic phosphides can be applied in a diversity of sites to
treat commodities in all types of storages, railcars, shipping containers,
stationary truck cargo containers, and other vehicles, and in ship holds
to treat grain during transit. Metallic phosphides are the fumigant of
choice for treating commodities stored on farms. These solid
formulations are simpler to apply compared to fumigants packaged as
liquids under pressure in cylinders (methyl bromide, sulfuryl fluoride,
or phosphine gas). The solid formulations, phosphine detection
equipment, and respiratory protection (cartridge mask for low
phosphine concentrations) are inexpensive compared to the cost of
other fumigants and cylinderized phosphine, the respiratory protection
(self-contained breathing apparatus) required for methyl bromide and
sulfuryl fluoride, and the detection equipment required for sulfuryl
fluoride.

Metallic phosphides leave a solid residue of either aluminum or

magnesium hydroxide and other inert ingredients. In bulk grains, this
residue is inconsequential due to dilution during subsequent grain
moving, handing, and processing. Metallic phosphides are available in a
variety of formulations, such as permeable bags or blister packs, which
allow for faster application of a premeasured dose and retrieval of
spent material. These prepackaged, retrievable formulations can be
applied to processed or ready-to-eat commodities where solid residues
are not permitted and for countries that do not permit solid residues in
raw commodities.

Phosphine can also be applied directly to a commodity as a gas from

metal gas cylinders or phosphine generators. Dosage accumulation
occurs more quickly because there is no delay in availability of
phosphine as in the metallic phosphides. Phosphine gas can be applied
at lower temperatures (0 °C) and to fresh commodities, such as certain
fruit and vegetables. Current research is evaluating reducing the

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fumigant exposure time required for phosphine by combination with
other gases, such as oxygen.

Globally, widespread and repeated fumigation of poorly sealed

commodities has resulted in sublethal exposure and selection of
resistance to phosphine. Phosphine resistance has been detected in key
stored-product insects in more than 45 countries. For more than three
decades, a monitoring and management program for phosphine
resistance, funded and executed by a coalition of industry and
government agencies, has been conducted in Australia. This program
has demonstrated that phosphine resistance can be effectively
managed by various methods, including intensive sanitation, use of
grain protectants, better sealing and monitoring of fumigations, and
increasing the phosphine dosage. Sulfuryl fluoride is used to treat
commodities infested by insects known or suspected to have high
levels of resistance to phosphine. Sulfuryl fluoride and phosphine have
different modes of action, and phosphine-resistant insects are not
cross-resistant to sulfuryl fluoride. The previously mentioned practices
minimize insect infestation and damage to stored commodities,
resulting in high-quality product available for use nationally and for
international trade.

Sulfuryl fluoride was developed in the 1950s as an alternative to

methyl bromide for control of drywood termites and other structure-
infesting insects. Due to the phaseout of methyl bromide part of the
Montreal Protocol, sulfuryl fluoride was further developed beginning in
the late 1990s as a fumigant for durable commodities, including cereal
grains, dried legumes, seeds, dried fruit and tree nuts, spices, and
cocoa. Extensive research was required to indentify dosages for control
of stored products pests, assess trace residues in fumigated
commodities and develop residue tolerance thresholds, and verify that
fumigation did not affect the taste of high-value commodities (dried
fruit, tree nuts, and cocoa) or wheat kernel quality, milling quality, or
properties of dough and baked goods (cookies, bread, and spaghetti).

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Related terms:
Sulfuryl Fluoride, Hydrogen Selenide, Bromomethane, Toxic Injury,

Solid Formulation, Fumigant, Adverse Event, Titanium Tetrachloride,

Nitrogen Dioxide, Aluminum Phosphide.

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