3M TechUpdate
Phosphine and Respiratory Protection
Phosphine is commonly used as a fumigant in agriculture. Phosphine gas is generated when calcium phosphide, alu-
minum phosphide or magnesium phosphide comes in contact with moisture. Occupational exposure may occur when
workers apply pellets or strips, etc. or enter closed areas or from open containers after the treatment. Phosphine expo-
sure may also occur in semiconductor manufacturing, phosphine fires and explosions and as a byproduct of illicit
methamphetamine manufacturing.
The published odour threshold for phosphine is 0.14 ppm. This is lower than the occupational exposure limit in Aus-
tralia and New Zealand (0.3 ppm Time Weighted Average (TWA), 1 ppm Short Term Exposure Limit) but odour
threshold varies widely between individuals so it is not a reliable indicator of exposure. AS/NZS 1715 recommends a
cartridge change schedule be developed instead of relying on contaminant warning properties.
RESPIRATOR OPTIONS
Exposure to phosphine should be minimized in as much as possible by replacement of phosphine with a less hazard-
ous material, engineering controls such as ventilation, and administrative controls such as restricting access to areas
where phosphine may be present. Respiratory protection may be used to help reduce exposure if these methods are
not adequate, or while they are being implemented.
At this time 3M is not aware of any regulatory test method or approval for respirator cartridges used for phosphine for
industrial purposes. The US National Institute for Occupational Safety and Health (NIOSH) does have a 1500 ppm
phosphine test method and approval for respirator large capacity canisters. These canisters may be used to escape
from environments that are immediately dangerous to life or health (IDLH). Users may object to the size and weight
of certain full facepiece canister respirators or the use of mouth-bit type canister respirators.
NIOSH also includes 300 ppm phosphine test for air-purifying respirators certified specifically for chemical, biologi-
cal, radiological, nuclear (CBRN) applications. CBRN respirators are designed to filter a variety of gases and vapours
and withstand permeation of chemical warfare agents. Therefore, CBRN respirators are often expensive and subject
to export control regulations making them unavailable to industrial application users.
3M has traditionally recommended supplied air respirators if worker exposure to phosphine is higher than applicable
occupational exposure limit of 0.3 ppm. However, supplied air systems are not always practical due to the need for a
compressed air source and use of phosphine fumigants at remote locations. Also, a worker’s movement is restricted
due to being tethered to a supplied air hose.
3M has received numerous requests for simpler types of respirators that may be used to help reduce exposure to
phosphine during pesticide application. Specifically, users claim that their exposure levels are minimal for these
tasks, but they still wish to wear a simple respirator to further reduce exposure. As previously mentioned, there is no
phosphine test method or approval for standard respirator cartridges.
TESTING OF 3M CARTRIDGES
In principle, test conditions should be at or beyond potential use conditions. The maximum use concentration is either
the occupational exposure limit (OEL) times the respirator protection factor, or concentrations that are immediately
dangerous to life or health (ILDH); whichever is lower. The OEL in Australia and New Zealand is 0.3 ppm TWA.
Respirator protection factor given by AS/NZS 1715 are 10 for half masks and 50 for full facepieces. The NIOSH
1990 IDLH level set for phosphine is 50 ppm. So, for example, the ANZ exposure limit is 0.3 ppm and the half face
respirator protection factor applied by Australian/New Zealand Standard AS/NZS 1715 is 10, then the respirator could
be used for exposure levels up to 3 ppm phosphine. Full facepieces with a protection factor of 50 could potentially be
used in higher concentrations - up to 15 ppm of phosphine TWA and allows brief excursions above this level.
March 2013
3M TechUpdate
Phosphine and Respiratory Protection
The following tests were performed with the 3M 6096 A1HgP3 cartridge at various phosphine concentrations. A flow
rate of 32 L/min was used (representing 64 L/min for a pair of cartridges) to approximate a heavy work rate. Tempera-
ture in the lab was approximately 250C. Service life to 0.3 ppm breakthrough was measured. The 30 ppm and 60 ppm
tests were intermittent: 8 hour exposure and then 16 hours no exposure. This intermittent pattern was repeated for 5
days for a total of 40 hours exposure.
Concentration Relative Service life
(ppm) Humidity (minutes) Comments
300 85% 466 No visible effect on cartridge.
300 25% 290 Cartridge front cover melted and carbon leaked out.
No phosphine detected. During the test, temperature air exiting
cartridge was ~30 0C and cartridge body barely warm to touch.
300 25% > 600 After removal from testing, cartridge heated up rapidly, the front
cover melted and carbon leaked out.
60 / 0 No phosphine detected. During the test, temperature air exiting
25% > 2400
(intermittent) cartridge was about 270C, but no cartridge warming or melting.
30 / 0 No phosphine detected above 0.3 ppm limit. 0.05 ppm phosphine
50% > 2400
(intermittent) briefly observed at the end of one of the 8 hr challenge cycles.
DISCUSSION
A small amount (0.05 ppm) of phosphine briefly came through the cartridge at the end of one of the intermittent tests. It
is thought that since phosphine is removed via a catalytic processes, very small amounts may come through the cartridge
until steady-state conditions are re-established in the carbon bed.
The front cover of the cartridge melted during or after the 300 ppm test at 25% RH, but not at 85% RH. It is possible
that some un-reacted phosphine built up in the carbon bed and began to react as more humid room air entered the car-
tridge inlet. This suggests that cartridges should not be used at high phosphine (>300 ppm) concentrations.
Cartridges should not be used for scrubbing phosphine from process or waste streams. The potentially high vapour con-
centrations that can occur in these applications could cause ignition of the carbon sorbent as a result of the highly exo-
thermic oxidation of phosphine.
RECOMMENDATION
The 3M 6096 A1HgP3 cartridge filter may be used with any of the 3M 6000, 7500 and FF-400 Series half and full
facepieces to help reduce exposure to low ambient levels of phosphine (e.g. up to 15 ppm Time Weighted Average on a
full facemask or 3 ppm TWA on a half facemask).
Service life is expected to be at least 40 hours in-use time for maximum concentrations less than 60 ppm phosphine and
at a normal breathing rate. Cartridges must be discarded and replaced earlier if taste, smell or irritation is noted, or if the
cartridge is physically damaged.
Personal Safety Division Personal Safety Division
3M Australia Pty Ltd 3M New Zealand Ltd
Bld A, 1 Rivett Road 94 Apollo Drive
North Ryde NSW 2113 Rosedale, Auckland 0632
Phone: 136 136 Tech Helpline: 0800 364 357
TechAssist Helpline: 1800 024 464 Customer services: 0800 252 627
E-mail: techassist@[Link] E-mail: innovation@[Link] March 2013
Website: [Link]/au/ppesafety Website: [Link]/nz/ppesafety © 3M 2013. All rights reserved.
