From: E.J. Wright, M.C. Webb and E. Highley, ed., Stored grain in Australia 2003. Proceedings of the Australian Postharvest Technical Conference, Canberra, 25–27 June 2003. CSIRO Stored Grain Research Laboratory, Canberra.
Carbonyl sulﬁde (COS) as a fumigant for stored
products: progress in research and commercialisation
Stored Grain Research Laboratory, CSIRO Entomology, GPO Box 1700, Canberra, ACT 2601
Carbonyl sulﬁde (COS) is a potential new fumigant for stored products, patented worldwide by CSIRO Aus-
tralia. It may replace methyl bromide for many applications on durable commodities and be used as an alternative to
phosphine when there is a signiﬁcant problem with insect resistance. Laboratory and ﬁeld studies have shown that
COS is effective on a wide range of pests at all life stages, at reasonable concentrations (<100 g/m3) and exposure
times (1–5 days) at 10–25˚C. Quality studies indicated no adverse effects on canola oil composition or colour, quality
of bread, noodles or sponge cake made from wheat, malting or brewing characteristics of barley, or germination or plu-
mule length of wheat, oats, barley or canola. Sorption, penetration, desorption, decay of residues to natural levels, and
interaction with other materials have all been shown to be consistent with being a practical fumigant for most commod-
ities. Because COS in naturally present in a great variety of raw and processed foodstuffs, and is produced in mammals
during the metabolism of some sulfur-containing compounds, it is argued that the low residues of COS remaining post-
fumigation do not appear to pose a risk to human health. Similarly, the widespread and abundant natural occurrence of
COS in the air, soil, and live and decaying vegetation suggests that COS does not present a tangible environmental haz-
ard. COS has been trademarked in Australia as COSMIC®, and a global licence agreement has been signed for manu-
facture and distribution of COS.
ties are midway between those of carbon disulﬁde (CS2)and carbon dioxide (CO2), both of which have been
Carbonyl sulﬁde (COS) is a potential new fumigant for
stored products. It was patented worldwide in 1992 byCSIRO Australia (Banks et al. 1993) and ﬁrst announcedto the scientiﬁc community at the 6th International
Performance as a fumigant
Working Conference on Stored Product Protection inCanberra, Australia in 1994 (Desmarchelier 1994).
Laboratory studies on toxicity
Carbonyl sulﬁde has the potential to replace methylbromide in several of its applications for durable
Laboratory studies have shown that COS is effective
commodities, and also to be used as an alternative to
on a wide range of pests in all stages, including the
phosphine when there is a signiﬁcant problem with
common stored-product species, at reasonable concentra-
insect resistance. This paper summarises research
tions (<100 g/m ) and exposure times (1–5 days) at 10–
results, primarily from the fumigant research group
25˚C (Desmarchelier 1994; Plarre and Reichmuth 1996;
within the Stored Grain Research Laboratory (SGRL),
Zettler et al. 1997; Xianchang et al. 1999; Weller 1999).
and CSIRO’s progress towards commercialisation of this
Of the stored-product pests tested, Sitophilus oryzae
is the most naturally tolerant and in-depth studies weretherefore conducted on this species at CSIRO. Thesestudies provided a range of exposure time/concentration
What is carbonyl sulﬁde (COS)?
regimes to give disinfestation level mortalities. Theyshowed concentrations of 20 g/m3 for an exposure time of
Ferm (1957) and Svoronos and Bruno (2002) have
5 days to be a particularly good combination, although
reviewed the chemistry of carbonyl sulﬁde (COS). Pure
there are other possible combinations (Weller and Morton
COS is a colourless and odourless gas with a low
boiling point. Carbonyl sulﬁde is present in nature,including air, soils, oceans, vegetation, cereals and
Haritos (2001) has shown the acute toxicity of COS is
foods (Sze and Ko 1980; Ren 1997; Ren and Desmarch-
dependent on carbonic anhydrase metabolism of COS to
elier 2001). Many of its chemical and physical proper-
hydrogen sulﬁde, the toxic agent of COS.
Carbonyl sulfide (COS) as a fumigant for stored products
sponge cake processed from fumigated wheat (Desmarch-
Trials were undertaken to start the formal path towards
registration, to validate laboratory predictions in the ﬁeld,
Malting and brewing trials were carried out on malting
to demonstrate compliance with occupational health and
barley fumigated with carbonyl sulﬁde in the ﬁeld trials
safety (OH&S) standards, to produce industry-sized
mentioned above, by an independent laboratory in
parcels of grain to allow industry assessment of quality
Australia. Residues in products showed that COS was
(baking, malting, brewing and residues), and to assess the
present in malt at 0.0033 mg/kg (ppm, w/w), and in spent
time required for killing insects, venting and clearing
grain at 0.0007 mg/kg, but was not detectable in wort or
beer made from either fumigated or unfumigated barley.
Trials on wheat (Desmarchelier et al. 1998), oats,
These results indicate that COS residues in malting and
barley, canola and ﬁeld peas (Ren et al. 2002, 2003) have
brewing products were comparable with levels present in
been conducted in 50 t silo bins with COS (20–25 g/m3),
products made from unfumigated barley from the same
for 3–5 days of exposure over a range of grain tempera-
source (Ren et al. 2003). These results are consistent with
tures (10–27˚C) and on hay (Weller 2003b) in shipping
those obtained using fate of 14C-labelled COS applied on
containers. These studies showed complete control of
grains and grain fractions (Annis et al. 2000). Finally,
mixed-age cultures of Rhyzopertha dominica
there was no effect of COS on malting and brewing char-
philus oryzae, Oryzaephilus surinamensis
acteristics of barley, and commercial testing of the beer
(Herbst), Tribolium castaneum
made from fumigated barley showed that it was no
Val, Ephestia cautella
(Walker), Trogoderma variabile
different from beer made from unfumigated barley.
Ballion, Cryptolestes ferrugineus
There was no signiﬁcant effect of fumigation with
Badonnel, Liposcelis decolor
COS on either germination (7-day count) or plumule
(Enderlein) and Ephestia kueh-
length of wheat, oats, barley and canola (Ren et al. 2002).
Zeller. The results from the ﬁeld trials were consis-
The work on germination parallels an observed lack of
tent with the laboratory data regarding toxicity to insects.
effect of COS on wheat at higher doses than required for
The trials have not shown any actual or potential
fumigation and the lack of effect on plumule length (Ren
problems in the large-scale use of COS. In fact, they have
It is worth noting that at least one fumigant,
shown that safe and effective fumigation should be well
hydrogen cyanide, affects plumule length without
within the competency of a skilled fumigator. Larger-scale
reducing germination (Ren et al.
trials of >500 t parcels of wheat, barley and canola arecurrently being conducted, primarily to optimise applica-
Sorption and penetration
tion methods and to conﬁrm worker/environmental safetyduring application, fumigation and aeration.
Of 32 different commodities investigated, including
cereals, pulses, oilseeds, dried fruit, spices, nuts, and
Effects on grain quality and viability
beverage crops, only 2 (kidney beans and sunﬂower seeds)
Fumigation of canola with COS does not adversely
had sorption rates incompatible with the use of COS as a
affect either oil content or oil colour (Ren et al. 2002). This
fumigant (Weller 2003a). Paddy rice and rice products
is in agreement with Ren et al. (1997), who showed that
have been looked at in detail, with paddy rice and rice
fumigation in vitro
of canola oil with COS at 100 g/m3 had
ﬂour sorbing COS at a higher rate than either brown rice
no effect on lipid composition as assessed by Fourier trans-
or white rice (Reuss and Annis 2002).
form infrared (FTIR) or ultraviolet spectroscopy. The result
An increase in moisture content of a commodity
was also consistent with that from a 14C-labelled COS
results in an increase in the rate of sorption, however
grains fumigated within the normal storage range (up to
Detailed quality tests from the ﬁeld trials on wheat
15% moisture content) displayed relatively low rates of
showed no adverse effect on quality of bread, noodles or
sorption (Weller 2003a). A reduction in the rate of
Chemical and physical properties of carbonyl sulﬁde compared to other fumigants.
sorption has been observed with increasing age of wheat
obvious effect on the material or on the concentration of
and on repeated fumigation (Weller 2003a).
COS remaining in, or available to, the gas space. Loss of
In the ﬁeld trials mentioned above, the distribution of
COS on fresh concrete was rapid, but loss on aged
COS in each trial became fairly even in less than one day.
concrete was minimal, similar to the sorption of CO2
At the end of the fumigation, compared with the initial
described by Banks and McCabe (1988) (Y.L. Ren, pers.
concentrations, approximately two-thirds of the intergran-
Interactions between COS and copper have been
studied in both Australia and Germany (Plarre and Reich-
Desorption and decay of residues to natural levels
muth 1996; Ren et al. 2000). These studies have found
Desorption of COS from fumigated grains is quicker
that pure COS or COS with <0.1% contamination by
than that of methyl bromide or phosphine. Laboratory
hydrogen sulﬁde (H2S) does not corrode copper, but COS
data showed that the accumulated levels of COS, which
signiﬁcantly contaminated with H2S does. This indicates
desorbed from grain fumigated at 45 mg/L, were <0.1
that the COS used for commercial fumigations must be
ppm after 24 hours of airing (Ren et al. 2003). This level
substantially free of H2S. This is now an important speci-
was 100 times lower than the Australian experimental
ﬁcation for the commercial production of COS.
threshold limit value (TLV) of 10 ppm. The experimentalTLV for carbonyl sulﬁde was based on that of hydrogensulﬁde (10 ppm; ACGIH 2001), as it is assumed that the
effects of COS are due to the action of hydrogen sulﬁderesulting from partial decomposition of COS in the lungs
COS is naturally present in a variety of raw and processed
and after adsorption into the blood stream (Braker and
foodstuffs, including cheddar cheese, cereals and oilseeds.
Mossman 1971). The TLV for hydrogen sulﬁde has
The natural levels of COS in grains and oilseeds were
subsequently been reduced to 5 ppm (ACGIH 2001).
found to be 0.02–0.07 mg/kg (Ren 1997; Desmarchelier et
The ﬁeld trials on barley showed that after 6 h of
al. 1998; Ren and Desmarchelier 2001). Levels of COS
forced ventilation (1 air change per hour), the in-bin
varied with commodity, moisture content, temperature
concentrations of COS were reduced from 3500 ppm to
and the period of storage. The levels of COS ranged from
<1 ppm. Similar results were obtained for wheat, oats and
0.02–1 mg/kg at harvest, increased during the ﬁrst 4–5
canola, in that in-bin concentrations were reduced to low
months of storage, and then began to decline, particularly
levels by a combination of aeration and ventilation (Ren et
at grain temperatures greater than 20˚C and moisture
contents greater than 9.5% (Ren and Desmarchelier
Post-fumigation residues of COS in the above trials
were found to be below the Australian experimental
COS has been shown to be produced in cheese from
maximum residue limit (MRL) of 0.2 mg/kg after 4 h of
either ascorbic acid or riboﬂavin at pH of 5.5 and temper-
airing. In other work, COS residues in fumigated paddy
ature of 24˚C, with more COS produced with increased
rice, brown rice, white rice and rice ﬂour were well below
levels of cysteine (Aston and Douglas 1983). As a result,
the MRL following fumigation for 5 days at an applied
COS is likely to be present, or produced, in any proteina-
dose of 20 g/m3, and subsequent airing (Reuss and Annis
ceous food at acid pHs, and therefore likely to be ubiqui-
2002). Therefore, the ﬁeld trials conﬁrmed that COS can
be ‘aired-off’ rapidly from the commodity after fumiga-
COS is produced in mammals during the metabolism
tion and, thereafter, that COS levels in fumigated grains
of some sulfur-containing compounds (Peeples and Dalvi
and seeds are indistinguishable from the levels in
1978; Johannson 1989) and is in turn metabolised by
untreated commodities. This is both due to the fast desorp-
carbonic anhydrase to hydrogen sulﬁde (Klason 1887).
tion of COS from commodities after fumigation and to the
COS is also produced by hydroxyl radical attack on the
very low, but natural, presence of COS in grains and seeds
sulfur-containing amino acids cysteine and methionine
(around 0.05–0.1 mg/kg). However, it is worth noting that
(Giroux and Lacroix 1998). Reactive oxygen species such
for commodities with high sorption, a slight increase in
as hydroxyl radicals are a normal by-product of respira-
the sulfur levels of the commodity is apparent by X-ray
tion (White and Coon 1980), and are generated as a part of
ﬂuorescence (Weller 2003a); this is being examined more
normal inﬂammatory processes (Conner and Grisham
closely to determine the exact fate of these sulfur residues.
1996). Because of the ubiquitous nature of hydroxyl radi-cals, all human tissues are exposed to COS at some level.
Interaction with materials
Thus, COS is a naturally occurring compound to which allplants and animals are already constantly exposed. There-
A number of materials, including hard and soft timbers,
fore, one can conclude that low-level residues resulting
paper, iron, steel and galvanised sheet, polyvinyl chloride
from the fumigation of grain with COS, and any reaction
(PVC), polyethylene, and brick, were exposed to high
products remaining as residues, are identical to those to
concentrations (>45 g/m3) of COS at high temperature
which humans are naturally exposed both through their
(45–60˚C) and relative humidity (65–100%) without
food supply and through normal biological processes.
Carbonyl sulfide (COS) as a fumigant for stored products
Consequently, such residues, at low levels, do not appear
tion of COS. The ﬁrst commercial-scale manufacture is
expected to begin shortly. It is hoped that COS will beregistered for use on grain in Australia by 2005, with othercountries following.
COS, together with other biogenic volatile sulfur
compounds, is produced naturally in soils (Staubes et al.
1989), marshes (Steudler and Peterson 1985), the roots
The work presented here was a joint effort by many
and shoots of plants (Piluk et al. 2001), manure (Clanton
people over 10 years, particularly by Jim Desmarchelier,
and Schmidt 2000), compost (Derikx et al. 1991), and
YongLin Ren, Peter Annis, Victoria Haritos, Jonathan
micro-organisms (Blezinger et al. 2000). The natural
Banks, Sylvia Allen, Le Vu, Gaye Weller and Daphne
occurrence of COS is linked to that of carbon disulﬁde
Mahon. I thank YongLin Ren, Andrew Bartholomaeus,
and the environmental sulfur cycle. The primary natural
Victoria Haritos, Gaye Weller, Colin Waterford and
sources of atmospheric sulfur are the oceans (primarily
Michael Tichon for assistance in preparation of this paper.
The work on COS was supported ﬁnancially by the
CSIRO, the Grains Research and Development Corpora-
tion, AWB Ltd, Grainco Australia, GrainCorp Operations,
importance, the major sulfur compounds released into the
Ausbulk Ltd., Co-operative Bulk Handling of WA and
atmosphere as a result of biological processes are
CH3SCH3 (dimethyl sulﬁde, or DMS), H2S, CS2, COS,CH3SH, and CH3SSCH3. Biogenic and anthropogenic
production of COS is not a major source of atmosphericsulfur in comparison to H2S, DMS and CS2, however
ACGIH (American Conference of Governmental Industrial
COS is the major sulfur moiety in the atmosphere (Turco
Hygienists) 2001. 2001 TLVs® and BEIs®, threshold limit
et al. 1980; Khalil and Rasmussen 1984; Kjellström
values for chemical substances and physical agents and bio-
1998). Ambient COS levels have been determined to be of
logical exposure indices, 2001. Cincinnati, ACGIH.
the order of 0.5 ppb (Sze and Ko 1980). COS is also
Annis, P.C., Ren, Y.L., Desmarchelier, J.M. and Johnston, F.M.
actively taken up by some plants and converted to CS
2000. Fate of C-labeled carbonyl sulﬁde on grains and
grain fractions. Journal of Agriculture and Food Chemicals,
the reverse of the atmospheric pathways (Ren 1999), and
soils may act as both a net source or a net sink for COS,
Aston, J.W. and Douglas, K. 1983. The production of volatile
depending on the concentration of COS and the character-
sulphur compounds in cheddar cheeses during accelerated
istics of the soil (Conrad and Meuser 2000).
ripening. The Australian Journal of Dairy Technology, June
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occurring and widely distributed chemical found or
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produced in the air, soils, live and decomposing vegeta-
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(AU9333389). Priority Date 15 January 1992. Patent
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sphere (Sze and Ko 1980), of the total annual production
Banks, H.J. and McCabe, J.B. 1988. Uptake of carbon dioxide
of approximately 3 million t, less than 10% is attributable
by concrete and implication of this process for grain storage.
to anthropogenic sources (Kelly and Smith 1990), with the
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remainder being produced naturally. Also, unlike the prin-
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Medications For Rheumatoid Arthritis Although there is no actual treatment for RA or rheumatoid arthritis to this day, there are a range of availablemedications in pharmacies that are meant to relieve its symptoms and ultimately improve the condition. Overall, medications for rheumatoid arthritis can be grouped into distinctive types, as discussed later in thisarticle. Doctors will design a pr
Security Council Resolution 1454 (2002) Adopted by the Security Council at its 4683rd meeting, on 30 December 2002 Recalling its previous relevant resolutions, including resolution 661 (1990) of 6 August 1990, 986 (1995) of 14 April 1995, 1284 (1999) of 17 December 1999, 1352 (2001) of 1 June 2001, 1360 (2001) of 3 July 2001, 1382 (2001) of 29 November 2001, 1409 (2002) of 1