Hydrogen phosphide as a fumigant for foods, feeds and processed ...
Hydrogen phosphide as a fumigant for foods, feeds and processed ...
Hydrogen phosphide as a fumigant for foods, feeds and processed ...
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L<br />
erween their<br />
Health Bull.<br />
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stol on live.<br />
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t <strong>and</strong> Estern<br />
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tsphorylation<br />
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arbor pestic<br />
determinanew<br />
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199 (1965) .<br />
hemists 47,<br />
iod <strong>for</strong> esd-<br />
<strong>Hydrogen</strong> <strong>phosphide</strong> <strong>as</strong> a <strong>fumigant</strong> <strong>for</strong> <strong>foods</strong>, <strong>feeds</strong><br />
<strong>and</strong> <strong>processed</strong> food product s<br />
By<br />
W. H. DIETERIcH', GERO MAYR" *, KARL HILD' • ,<br />
J. B. SULLIVAN*, <strong>and</strong> J . MURPHY'<br />
Contents<br />
1. Introduction . . . . . . . . . . . . . . . 135<br />
a) Applications . . . . . . . . . . . . . . . 135<br />
b) Historical . . . . . . . . . . . . . 137<br />
II. Phosphine residues in food products . . . . . . . . . . . 139<br />
a) Direct analysis . . . . . . . . . . . . . . . 139<br />
b) Indirect analysis . . . . . . . . . . . 139<br />
c) Effect of phosphine on vitamins '. . . . . . . . . . . 143<br />
111 . Discussion . . . . . . . . . . . . . . . . . 143<br />
Summary . . . . . . . . . . . . . . . . . . . 146<br />
Resume . . . . . . . . . . . . . . . . . . . 146<br />
Zussamenf<strong>as</strong>sung . . . . . . . . . . . . . . . . . 147<br />
References . . . . . . . . . . . . . . . . . . . 147<br />
1. Introductio n<br />
<strong>Hydrogen</strong> <strong>phosphide</strong> or phosphine (PHa), a colorless, toxic, inflammable<br />
g<strong>as</strong> with an odor like carbide, h<strong>as</strong> been used <strong>for</strong> the fumigation of insect<br />
pests of stored grain <strong>for</strong> many years . The development of a tablet, <strong>and</strong> more<br />
recently a pellet, composed of aluminum <strong>phosphide</strong> <strong>and</strong> ammonium carbamate<br />
(Phostoxin©t) which decomposes upon exposure to the atmosphere<br />
<strong>and</strong> slowly liberates the g<strong>as</strong>, h<strong>as</strong> practically eliminated the danger of spontaneous<br />
combustion,<br />
a) Application:<br />
A Phostoxin Tablet weighs about three grams <strong>and</strong> produces, approximately<br />
• Hazleton Laboratories, Inc., Falls Church, Virginia.<br />
• • Deutsche Gesellschaft His Scbadiiagsbekiimpfung (Degetcb), Frankfurt am<br />
Main, West Germany .<br />
I Produced by Degescb ; distributed also by the Hollywood Ternsire Coarrol Co .,<br />
Inc.. Alhambra, Cali<strong>for</strong>nia . .<br />
7<br />
http://legacy.library.ucsf.edu/tid/mjq66a99/pdf
136 W. H. DiarBRIcH, GRRo MAYR, KARL HILw, J . B . SULLIVAN, <strong>and</strong> J . MURPHY<br />
one gram of phosphine ; a Phostoxin Pellet weighs 0.6 gram <strong>and</strong> yields 0 .2<br />
gram of g<strong>as</strong> . Tablets or pellets are added to grain <strong>as</strong> it is being loaded into<br />
barges, boxcars, or storage bins, or they can be inserted with special equipment<br />
later, Depending upon local practice <strong>and</strong> the temperature of the material<br />
to be fumigated, from three to six tablets are used <strong>for</strong> each 1,000 kg.<br />
of grain ; the fumigation period is from three to five days . The phosphine<br />
g<strong>as</strong> which is generated rapidly spreads throughout the grain or other commodiry,<br />
moving in all directions . Although noticeable levels of g<strong>as</strong> can be<br />
maintained <strong>for</strong> up to 28 days in a tightly dosed container, all residues will<br />
disappear after 48 hours' normal aeration . After the fumigation, the undisturbed<br />
tablet residue consists of aluminum hydroxide with possibly a<br />
small amount of undecomposed <strong>phosphide</strong> ; the latter decomposes with the<br />
turning or h<strong>and</strong>ling of grain or with the usual leaning me<strong>as</strong>ures .<br />
For the fumigation of <strong>feeds</strong> <strong>and</strong> <strong>processed</strong> <strong>foods</strong> which may have, a<br />
minimum of h<strong>and</strong>ling prior to consumption, the recommended dosage<br />
is 45 to 60 tablets or 165 to 200 pellets per 1,000 cubic feet of space. The<br />
tablets or pellets are confined in a g<strong>as</strong>-permeable envelope or are spread<br />
on trays near the material to be fumigated ; the whole lot is then sealed in the<br />
room or covered with a g<strong>as</strong>-tight cover <strong>for</strong> the necessary time . In this way,<br />
neither the tablets not their residues come into contact with the food; yet<br />
the phosphine g<strong>as</strong> effectively spreads throughout the material <strong>and</strong> kills<br />
the insects, after which it is rapidly removed by natural aeration .<br />
The effectiveness of phosphine derived from aluminum <strong>phosphide</strong> against<br />
various insect pests in many countries of the woildd, together with its safet y<br />
in use, h<strong>as</strong> been reported by NEITZERT (1953), VAN DEN BRUEL <strong>and</strong> BOL-<br />
LAF .RTS (1956), FREEMAN (1957), HESELTINE <strong>and</strong> THOMPSON (1957),<br />
RAUSCHER (1957), SMIT (1957), LINDGREN et at (1958), GUNN (1959),<br />
STRONG <strong>and</strong> LINDGREN (1960), MONRO (1960), MCGREGOR (1961),<br />
TURTLE (1961), HARADA (1962), HUBERT (1962), RAI at a! . (1962 <strong>and</strong><br />
1964), COGBURN <strong>and</strong> TILTON (1963), coTroN (1963), LISCOMBB (1963),<br />
PINGALE et a! (1963), MONRO (1964), PREY (1965), <strong>and</strong> REYNOLDS at al .<br />
(1967). There is no continent where Phostoxin h<strong>as</strong> not been used effectively<br />
<strong>for</strong> fumigation of indigenous pests of stored grain.<br />
The acute toxicology of phosphine h<strong>as</strong> been discussed by KLIMMER (1958,<br />
1964, <strong>and</strong> 1966/67), the American Conference of Government Industrial<br />
Hygienists (1963 at .req.), <strong>and</strong> COURVILLE (1964) . SCHULEMANN <strong>and</strong><br />
KLIMMER (1953) reported that subacute studies on rats indicated that no<br />
effect could be detected from the feeding of fumigated, uncleared grain .<br />
Although evidence cited herein indicates that residues of g<strong>as</strong> are completely<br />
dissipated after 48 hours' aeration <strong>and</strong> there is no physical or chemical<br />
combination of phosphine with the fumigated materials which would<br />
alter them significantly, the joint FA0/WHO Committee on Pesticide<br />
Residues (1965) h<strong>as</strong> recommended long-term studies in two species of<br />
animals, together with research on the fate of the compound in food <strong>and</strong><br />
its biochemical mechanism of action in animals .<br />
The an<br />
under var<br />
ported by<br />
POPP<br />
fumigate<br />
under sea<br />
analysis . 7<br />
of phosph<br />
Lion, the r<br />
of phosph<br />
averaging<br />
aeration .<br />
BRUCI<br />
tablets/to i<br />
WAGN<br />
gated wit<br />
hours aft(<br />
DRUCI<br />
fumigatio<br />
fumigated<br />
<strong>for</strong> differs<br />
Some san<br />
<strong>for</strong> aberr4<br />
ton, resid<br />
to 14 day<br />
tablets/to<br />
to 0.004 1<br />
is best d(<br />
dosages 1<br />
by aerati (<br />
ALESS<br />
fumigatio<br />
http://legacy.library.ucsf.edu/tid/mjq66a99/pdf
1N, <strong>and</strong> J . MURPHY<br />
im <strong>and</strong> yields 0.2<br />
being loaded into<br />
ith special equiprarure<br />
of the ma.<br />
or each 1,000 kg .<br />
s. The phosphene<br />
.in or other comels<br />
of g<strong>as</strong> can be<br />
, all residues will<br />
aigation, the unwith<br />
possibly a<br />
)mposes with the<br />
ie<strong>as</strong>ures.<br />
rich may have a<br />
amended dosage<br />
eet of space. The<br />
pe or are spread<br />
:hen sealed in the<br />
ime. In this way,<br />
ith the food; yet<br />
iaterial <strong>and</strong> kills<br />
-ration .<br />
)hosphide against<br />
er with its safety<br />
BRUEL <strong>and</strong> BOL-<br />
'MPSON (1957) ,<br />
GUNN (1959),<br />
,REGOR (1961),<br />
old. (1962 <strong>and</strong><br />
SCOMBE (1963),<br />
REYNOLDS et al .<br />
a used effectively<br />
KLIMMER (1958,<br />
amens Industrial<br />
iULEMANN an d<br />
ndicated that no<br />
cleaned grain,<br />
of g<strong>as</strong> are comiysical<br />
or chemids<br />
which would<br />
ee on Pesticide<br />
two species of<br />
tad in food <strong>and</strong><br />
<strong>Hydrogen</strong> <strong>phosphide</strong> <strong>as</strong> a <strong>fumigant</strong> 137<br />
b) Histori<strong>as</strong>l<br />
The amount of residue in different products fumigated with Phostoxin<br />
under varying conditions <strong>and</strong> after differing aeration periods h<strong>as</strong> been reported<br />
by a number of researchers ,<br />
POPP (1953) reported that 1,000 g. of Phostoxin tablets were used to<br />
fumigate 45 tons of cereal grains (15 mg./kg.) . The grain w<strong>as</strong> fumigated<br />
under sealed conditions <strong>for</strong> five days after which samples were taken <strong>for</strong><br />
analysis. The air swept from 10 treated samples ranged from 0 to 0.5 mg.<br />
of phosphine/kg. of grain with an average of 0.126. After two hours' aeration,<br />
the sample with the highest phosphine level w<strong>as</strong> reduced to 0.023 mg.<br />
of phosphine/kg. of grain. Five other samples with phosphine residue levels<br />
averaging 0.2 mg./kg. were without detectable residues after three days'<br />
aeration.<br />
BRUCE (1958) fumigated milo with Phostoxin at a dosage rate of 10<br />
tablets/ton of grain. Phosphine residues were <strong>as</strong> shown is Table I .<br />
Sample<br />
Table I. Phosphine residue: in milo, 10 Pbostoxin<br />
Tabletslton of grain (BRUCE .1958 )<br />
Days after<br />
treatment PHs residue (p.p.m. )<br />
I 0.43 6<br />
16 0 .029<br />
2 7 0 .28 6<br />
11 0.08 5<br />
WAGNER <strong>and</strong> FOGLEMAN (1962) reported that commercial flour fumigated<br />
with Phostoxin contained no detectable residues of phosphine 24<br />
hours after completion of the fumigation.<br />
BRUCE et al. (1962) conducted extensive studies of laboratory <strong>and</strong> field<br />
fumigation of various grains with Phostoxin . Residues of phosphine in grain<br />
fumigated with the exaggerated doses shown, both without <strong>and</strong> with aeration<br />
<strong>for</strong> different periods, were <strong>as</strong> collated in Table II .<br />
Some samples included portions of undecomposed tablets which account<br />
<strong>for</strong> aberrant results. Under field conditions, with doses of 2.9 to 10 tablets/<br />
ton, residues of phosphene ranged from 0.029 to 0 p .p.m. following one<br />
to 14 days--,fumigation . Another group of samples fumigated at two to six<br />
tablets/ton followed by turning <strong>and</strong>/or aeration had residues of from 0 .046<br />
to 0.004 p.p .m. The effectiveness of aeration in reducing phosphine residues<br />
is best demonstrated by the 57 tablets/ton dosage where these exaggerated<br />
dosages produced early residues of 3 .03 p.p.m, which were then reduced<br />
by aeration <strong>for</strong> seven days to 0.004 p.p .m .<br />
ALESSANDRINI <strong>and</strong> WHCITEMORB (1965) reported that usual Phostoxin<br />
fumigation dosages <strong>for</strong> grain were six tablets/ton in India, 10 in Sweden,<br />
http://legacy.library.ucsf.edu/tid/mjq66a99/pdf
138 W. H . Din78R1CH, Gnno MAYR, KARL Hn.n, J . B. SULLIYAN1 <strong>and</strong> J . MURPHY<br />
0<br />
w<br />
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phosphine .<br />
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KLIMMER<br />
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in the fury<br />
meable tar_<br />
products a<br />
In spit.<br />
Lion wheth<br />
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http://legacy.library.ucsf.edu/tid/mjq66a99/pdf
Hydtogen <strong>phosphide</strong> <strong>as</strong> a <strong>fumigant</strong> 139<br />
<strong>and</strong> three to 10 in Australia . Residues of phosphine from these treatments<br />
were shown to be less than 0.1 p.p .m .<br />
The' Netherl<strong>and</strong>s Committee on Phyropharmacy (1965) reported that,<br />
using a method sensitive to 0 .01 p.p.m. of phosphine, 99 samples of cereals<br />
imported into The Netherl<strong>and</strong>s during 1964 were analyzed <strong>for</strong> residues of<br />
phosphine. One sample showed a level of 0.3 p.p .m .; levels in the others<br />
were all 0.04 p .p.m. or below . In the 1966 report of the same committee,<br />
28 products fumigated with phosphine had residues ranging from < 0.01<br />
to 0.3 p .p.m.; one had the 0.3 level, another 0.1 p.p.m., <strong>and</strong> the remainder<br />
were 0.05 p.p.m. or below .<br />
. The Codex Committee (1966) reported, that wheat fumigated in The<br />
Netherl<strong>and</strong>s at dosages of three to six tablets of Phostoxin/cubic meter of<br />
grain, aerated <strong>for</strong> 48 hours, <strong>and</strong> analyzed after 12 days showed no residues<br />
above 0.005 p.p.m. They concluded that "Through turning <strong>and</strong> aerating,<br />
phosphine disappears rapidly from cereals treated in the conventional manner,"<br />
<strong>and</strong> that "Baking studies showed that no 'significant residues of<br />
phosphine could be found in the bread made from fumigated flour or grain. "<br />
Phostoxin* h<strong>as</strong> been registered in the United States since 1958 <strong>for</strong> the<br />
fumigation of raw agricultural commodities on a no-residue b<strong>as</strong>is . Regulations<br />
were issued in 1965 authorizing the use of Phostoxin' <strong>for</strong> the fumigation<br />
of certain animal <strong>feeds</strong> <strong>and</strong> <strong>processed</strong> <strong>foods</strong>, provided residues of phosphine<br />
did not exceed 0 .1 p .p.m. after 48 hours" aeration following fumigation .<br />
In Canada, Phostoxin® h<strong>as</strong> been registered <strong>for</strong> raw agricultural commodities,<br />
<strong>processed</strong> <strong>foods</strong>, <strong>and</strong> pet <strong>foods</strong>' on the b<strong>as</strong>is that any remaining residues would<br />
be negligible. Phostoxin' is registered in 70 countries.<br />
II. Phosphine residues in food products<br />
I<br />
I<br />
I<br />
a) Direct analysis<br />
Early experimental work with Phostoxin in the fumigation of grains<br />
had indicated that there were trace amounts of unreacted aluminum <strong>phosphide</strong><br />
present among the decomposition products of the Phostoxin Tablets . It<br />
w<strong>as</strong> shown that these amounts would rapidly disappear when the grain w<strong>as</strong><br />
b<strong>and</strong>ied (sauce at al. 1962) <strong>and</strong> that, even if the grain were fed to rats<br />
without cleaning, no harm could be demonstrated (SCHULEMANN <strong>and</strong><br />
KLIMMER 1953) . It is recommended that, <strong>for</strong> the fumigation of <strong>processed</strong><br />
<strong>foods</strong>, the tablets or pellets be enclosed in an envelope or otherwise contained<br />
in the fumigation chamber (whether a sealed room or under a g<strong>as</strong>-impetmeable<br />
tarpaulin) in such a way that the Phostoxin or its decomposition<br />
products can not possibly come in contact with the food products .<br />
J<br />
b) Indirect analysis<br />
In spite of its negligible solubility in water <strong>and</strong> oil, there w<strong>as</strong> a question<br />
whether phosphine g<strong>as</strong> would be absorbed by or adsorbed onto fumigated<br />
food products in such a way that residues would remain or that<br />
http://legacy.library.ucsf.edu/tid/mjq66a99/pdf
Table III. Phosphine residues (p.p.m.) in <strong>processed</strong> <strong>foods</strong> fumigated with pbosphine generated from Pbostoxin Tablets or<br />
Pellets at the dosage levels <strong>and</strong> after the aeration times indicated (SULLIVAN <strong>and</strong> MURPHY 1966 )<br />
0<br />
Control<br />
Fumigation dosage/11,000 cu. ft.<br />
Recommended<br />
Enggrrued<br />
t7<br />
Food samples<br />
Containers<br />
None<br />
No<br />
aeration<br />
165<br />
Pellets<br />
48 hr.<br />
aeration<br />
2 hr.<br />
aeration<br />
45<br />
Tablets<br />
48 hr.<br />
aeration<br />
2 hr.<br />
aeration<br />
450<br />
Tablets<br />
48 hr .<br />
aeration<br />
Corn Flakes Waxed carton < 0.003 < 0.003<br />
Rice Krispies Waxed carton < 0 .003 < 0 .003<br />
Shredded Wheat Waxed carton < 0 .003 < 0.003<br />
Concentrate Waxed carton < 0.003 < 0.003<br />
Malted barley<br />
flour Paper bag < 0.003 0.004<br />
Institutional<br />
donut mix Paper bag < 0 .003 < 0.003<br />
Pie crust mix Paper bag < 0.003 < 0 .003<br />
Oat floor Paper bag 0.005 < 0.003<br />
Vito glute n<br />
concentrate Papa h<strong>as</strong> 0.003 0.00 3<br />
Soy flour (high<br />
fat) paper h<strong>as</strong> < 0.003 0.003<br />
Rice flour Paper bag 0.005
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http://legacy.library.ucsf.edu/tid/mjq66a99/pdf
142 W. H. D1ErER1CH, GERO MAYR, KARL HILA, ) . B. SULLIVAN, <strong>and</strong> J . MURPHY<br />
toxic byproducts would be <strong>for</strong>med by chemical reaction . The first approach<br />
toward the solution of this problem w<strong>as</strong> the use of a method shown to be<br />
practicable with raw agricultural commodities. This w<strong>as</strong> described by BRUCE<br />
of al. in 1962 <strong>and</strong> w<strong>as</strong> shown to be sensitive in the range of parts per billion<br />
(p.p.b.) ; apparent phosphene residues in flour <strong>and</strong> bread were in the<br />
range of less than 60 p.p.b. A limiting factor in this method w<strong>as</strong> the concentration<br />
of phosphorus in the analytical reagents used, including the<br />
water; <strong>for</strong> this re<strong>as</strong>on the authors emph<strong>as</strong>ized the need <strong>for</strong> funning control<br />
or blank samples.<br />
In an attempt to incre<strong>as</strong>e the overall sensitivity of the original method,<br />
SULLIVAN <strong>and</strong> MURPHY (1966) modified BRUCE's procedure ; specific details<br />
of this new procedure are to be published at a later date .<br />
Utilizing this modified procedure, SULLIVAN <strong>and</strong> MURPHY (1966)<br />
analyzed the following products <strong>for</strong> phosphine residues following fumigation<br />
<strong>and</strong> aeration according to the recommended schedule : green coffee beans,<br />
cocoa powder, nonfat instant dry milk powder, malted barley flour, institu .<br />
tional doughnut mix, pie crust mix, oat flour, gluten concentrate, high fat<br />
soy flour, rice flour, gluten flour, bran buds, primary ye<strong>as</strong>t, beet pulp, cornstarch,<br />
deer pellets, mink conditioner, raisins, dried apples <strong>and</strong> apricots, pecan<br />
pieces, <strong>and</strong> Kellogg's Corn Flakes, Rice Krispies, Concentrate, Special K,<br />
Apple Jacks, <strong>and</strong> Shredded Wheat. After fumigation at the recommended<br />
level with 48 hours' aeration, the highest level of phosphine found in any<br />
product w<strong>as</strong> 0 .017 p .p.m. (see Table III) . Data from a shorter aeration<br />
interval <strong>and</strong> at an exaggerated dosage level indicate the rapidity with which<br />
phosphine disappears .<br />
Because of the trace levels of phosphorus <strong>and</strong> related compounds which<br />
might normally be found in <strong>foods</strong>tuffs, <strong>as</strong> previously mentioned, an indirect<br />
method <strong>for</strong> the analysis of phosphine residues w<strong>as</strong> developed by MAYR <strong>and</strong><br />
HILD (1966). By demonstrating that all of the phosphine which had been<br />
generated by a me<strong>as</strong>ured amount of Phostoxin could be recovered at some<br />
period following the completion of fumigation, they excluded the possibility<br />
of any reaction with or adsorption by the fumigated <strong>foods</strong>tuffs. Accuracy<br />
of the method w<strong>as</strong> ± 0.07 percent . A description follows :<br />
The fumigation chamber (desiccator) is connected with the equipment <strong>for</strong><br />
the phosphine determination, which consists of two bubble towers; the first is<br />
filled with dilute sulfuric acid <strong>and</strong> the second with mercuric chloride . The<br />
final connection is to a vacuum pump. A stream of nitrogen is drawn through<br />
the desiccator with a speed of eight 1./fir. to w<strong>as</strong>h the phosphine into the mercuric<br />
chloride. Precautions are taken to retain every trace of phosphine <strong>and</strong><br />
to p<strong>as</strong>s the nitrogen stream slowly enough to allow the total absorption of the<br />
phosphine. In order to remove the g<strong>as</strong> from the interstitial spaces of the treated<br />
commodity, the latter is stirred during the nitrogen w<strong>as</strong>h . Nitrogen can be replaced<br />
in this method by air, either hot or cold .<br />
Should there be tablet residues in the fumigated commodity, dilute sulfuric<br />
acid is added to the latter <strong>and</strong> boiled; the phosphine is completely driven out<br />
<strong>and</strong> absorbed in the mercuric chloride .<br />
Phosphine reacts with the mercuric chloride to <strong>for</strong>m free hydrochloric<br />
M<br />
1<br />
i<br />
acid ; d-<br />
The co<br />
Potenti'<br />
Usi<br />
from t<br />
either<br />
flour, o<br />
dried a<br />
tea, su;<br />
chives,<br />
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http://legacy.library.ucsf.edu/tid/mjq66a99/pdf
1RPHY <strong>Hydrogen</strong> <strong>phosphide</strong> <strong>as</strong> a <strong>fumigant</strong> 14 3<br />
roach<br />
to be<br />
RUCK<br />
r bill<br />
the<br />
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<strong>and</strong><br />
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t <strong>for</strong><br />
at is<br />
The<br />
)ugh<br />
met<strong>and</strong><br />
the<br />
.aced<br />
rc-<br />
(uric<br />
out<br />
loric<br />
acid; determination is by titration with O .1N pot<strong>as</strong>sium or sodium hydroxide .<br />
The color change from light green to light blue must be carefully observed .<br />
Porentiornetric titration is <strong>for</strong> more exact <strong>and</strong> can be used without filtration .<br />
Using this method, MAYn <strong>and</strong> HILD (1966) analyzed phosphine residues<br />
from the following products which had been fumigated with Phostoxin<br />
either at the recommended or at exaggerated dosage rates, barley, wheat<br />
flour, oat flakes, noodles, rice, wheat bran, semolina, macaroni, dried apples,<br />
dried apricots, raisins, prunes, almonds, hazelnuts, peanuts, walnuts, coffee,<br />
tea, sugar lumps, cottonseed cake, a variety of dog <strong>foods</strong>, pe<strong>as</strong>, spinach,<br />
chives, beans, lettuce, lentils, ground red <strong>and</strong> black pepper, curry powder,<br />
turmeric, marjoram, <strong>and</strong> potato flour . Although fresh vegetables are not<br />
customarily fumigated, these items were included <strong>for</strong> the study of any<br />
possible effects of the fumigation . Recovery of all of the phosphine w<strong>as</strong><br />
repeatedly demonstrated. There w<strong>as</strong> no evidence of absorption by or adsorption<br />
on any of the <strong>foods</strong> studied (Table IV) .<br />
c) Effect of phosphine on vitamins<br />
MAYR <strong>and</strong> HILD (1966) conducted further studies to determine whether<br />
vitamins might be altered or destroyed by the fumigation, even if all the<br />
phosphine w<strong>as</strong> apparently recovered . Organic compounds of high molecular<br />
weight <strong>and</strong> with it large number of unsaturated double bonds are considered<br />
to be particularly susceptible to this type of reaction ; since Vitamins A <strong>and</strong><br />
Ba have these characteristics, they were studied in detail . Vitamin A w<strong>as</strong><br />
examined in whole milk powder; provitamin A (beta-carotene) w<strong>as</strong> studied<br />
in brussels sprouts, cabbage, red cabbag ee, whole meal flour, <strong>and</strong> peco nuts,<br />
Vitamin B2 w<strong>as</strong> analyzed be<strong>for</strong>e <strong>and</strong> after`fumigation of wheat germs, spinach,<br />
garden lettuce, peanuts, walnuts, <strong>and</strong> whole meal flour . No influence w<strong>as</strong> found<br />
on any of these vitamins .<br />
III. Discussion<br />
The data available on residues of phosphene found in grains fumigated<br />
with Phostoxin <strong>as</strong> reported by earlier workers <strong>and</strong> levels more recently reported<br />
in fumigated grains <strong>and</strong> <strong>processed</strong> <strong>foods</strong>-but determined by more<br />
sophisticated analytical techniques-are in general agreement. The occ<strong>as</strong>ional<br />
reports of finding residue levels to be higher after longer periods of<br />
fumigation or aeration---contrary to the reduction to be expected--have<br />
been attributed by 7situc et 41. (1962) to particles of disintegrated pellets<br />
of Phostoxin either coating the kernels of grain or accidentally picked up<br />
by the sampler.<br />
Discounting these aberrant results, analysis of a wide variety of products<br />
which had been fumigated with considerably differing dosages of<br />
Phostoxin tablets or pellets indicated that residues would normally be less<br />
than 1 .0 p .p.im immediately upon completion of fumigation <strong>and</strong> 0.02 pp.in<br />
after h<strong>and</strong>ling or aeration <strong>for</strong> 48 hours.<br />
i<br />
http://legacy.library.ucsf.edu/tid/mjq66a99/pdf
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http://legacy.library.ucsf.edu/tid/mjq66a99/pdf
146 W. H. btaratuctr, Gaao MAYa, KARL I-IILD, J. D. SULLtvAN, <strong>and</strong> J . MURPHY<br />
Summary<br />
Phostoxin0 Tablets <strong>and</strong> Pellets have gained worldwide acceptance <strong>as</strong> a<br />
source of phosphine (PHa) <strong>for</strong> effective fumigation of cereal grains <strong>and</strong><br />
other agricultural commodities. The toxicity to all stages of insect life,<br />
safety in use, <strong>and</strong> absence of residue make it ideally suited <strong>for</strong> this purpose.<br />
Repeated fumigation, if required by reinfestation, does not cause a problem<br />
with cumulative residue.<br />
More recently, widespread interest in using Phostoxin <strong>for</strong> fumigation<br />
of <strong>processed</strong> <strong>and</strong> packaged food <strong>and</strong> feed h<strong>as</strong> resulted in the conduct of research<br />
to provide data on possible residues <strong>and</strong> other <strong>as</strong>pects of this process .<br />
Two methods have been used to determine residue levels, if any, in <strong>processed</strong><br />
<strong>foods</strong>. The first is a direct, practicable method <strong>for</strong> analyzing the fumigated<br />
food per se. The second is an experimental "recovery" or indirect method,<br />
whereby the phosphine generated is used to fumigate the food <strong>and</strong> is then<br />
recovered . By' either or both of these methods, many samples representing<br />
cereal grains <strong>and</strong> related products, fruits <strong>and</strong> nuts, beverage products, animal<br />
<strong>foods</strong>, vegetables, spices, <strong>and</strong> miscellaneous food products have been fumigated<br />
<strong>and</strong> subsequently analyzed . There h<strong>as</strong> been no evidence of absorption<br />
of phosphine by or adsorption onto any of the <strong>foods</strong> studied .<br />
Analysis of vitamins A <strong>and</strong> B2 be<strong>for</strong>e <strong>and</strong> after fumigation with phosphene<br />
h<strong>as</strong> shown no evidence of any changes . These results, uni<strong>for</strong>mly in.<br />
dicating negligible residues of approximately 0 .01 p .p.m. or less, indicate<br />
the suitability of Phostoxin <strong>as</strong> a <strong>fumigant</strong> fdr <strong>processed</strong> <strong>foods</strong> <strong>and</strong> <strong>feeds</strong>,<br />
<strong>as</strong> well <strong>as</strong> <strong>for</strong> taw agricultural commodities .<br />
R6sum6 *<br />
Les tablettes et les comprimes de Phostoxin®x ont ..cquis une tres gr<strong>and</strong>e<br />
faveur comme source d'hydrogene phosphors (PHa) pour une fumigation<br />
efficace des grains de cereales et autres produits agricoles . La toxicit6<br />
ii tous les sages de la vie de 1'insecte, Is s6curit6 de 1'emploi et l'absence<br />
de r6sidu le rendent ideal pour cer usage. Une fumigation repetee, si elle<br />
est exigee par une reinfestation ne souleve p<strong>as</strong> de probleme de residus<br />
cumularifs.<br />
Plus r6cemment, un int6ret accru daps 1'emploi du Phostoxin pour les<br />
fumigations d'aliments prepares a result6 de recherches ex6cut6es afin de<br />
r6unir des donn6es sur les residus 6ventuels et d'autres <strong>as</strong>pects de cette technique.<br />
Deux m6thodes ont • 6t6 utilisees pour determiner les teneurs en<br />
residus, s'il en existe, dans les aliments prepares. La premiere est une<br />
m6thode directe et pratique pour doser 1'hydrogene phosphor6 dans les<br />
aliments trait6s. La seconde est une m6thode indirecte dans laquelle est dose<br />
l'hydrogene phosphor6 non absorb6 par les aliments . Par Tune ou 1'autre<br />
de ces m6thodes oar 66 analyses, apr2s fumigation, de nombreux 6chantillons<br />
de graines de cereales et de produits voisins, des fruits at des noix, de s<br />
• Traduit par R. biesT S.<br />
boissons, des<br />
Il n'a ete of<br />
aucun des al<br />
L'analyse<br />
gene phospi<br />
paraitre des<br />
que le Pho.,<br />
prepares quq<br />
Phostoxi<br />
als Phosphi<br />
<strong>and</strong>eren Ian<br />
Entwickluni<br />
d<strong>as</strong> Fehlen<br />
Mittel. Wif<br />
wendig ist,<br />
Ruckst<strong>and</strong>el<br />
Neuerdi<br />
bei der Bey<br />
Mitteln zu<br />
uber moglit<br />
Bestimmun.<br />
Nahrungsm<br />
beg<strong>as</strong>ten N<br />
gewinnung~<br />
benutzt urn<br />
viele Probt<br />
Getranke, I<br />
Nahrungsm<br />
keinerlei H<br />
untersuchte<br />
Analyse<br />
ergaben kei<br />
Diese I<br />
st<strong>and</strong>s von<br />
Eignung vi<br />
<strong>and</strong> Futter<br />
ALESSANDRI<br />
phosphk<br />
• Oberst<br />
http://legacy.library.ucsf.edu/tid/mjq66a99/pdf
VAN, <strong>and</strong> J . MURPHY<br />
ide acceptance <strong>as</strong> a<br />
cereal grains <strong>and</strong><br />
ges of insect life,<br />
d <strong>for</strong> this purpose.<br />
or cause a problem<br />
:in <strong>for</strong> fumigation<br />
the conduct of reets<br />
of this process.<br />
if any, in <strong>processed</strong><br />
ing the fumigated<br />
r indirect method ,<br />
food <strong>and</strong> is then<br />
nples representing<br />
e products, animal<br />
have been fumi-<br />
!nce of absorption<br />
died .<br />
gation with phos.<br />
ilts, uni<strong>for</strong>mly in .<br />
or less, indicate<br />
<strong>foods</strong> <strong>and</strong> <strong>feeds</strong>,<br />
is une tres gr<strong>and</strong>e<br />
r une fumigation<br />
soles. La toxicit6<br />
;tploi et l'absence<br />
n rdpht6e, si elle<br />
,lime de r6sidus<br />
tostoxin pour Its<br />
ax&ut6es afin de<br />
,cts de cette techr<br />
les teneurs en<br />
'remiire est une<br />
tsphor6 dans les<br />
laquelle est dose<br />
l'une ou l'autre<br />
•reux 6chantillons<br />
cc des noix, des<br />
<strong>Hydrogen</strong> <strong>phosphide</strong> <strong>as</strong> a <strong>fumigant</strong> 14 7<br />
boissons, des produits animaux, des legumes, des 6pices et des aliments divers.<br />
11 n'a dtd observe ni absorption, ni adsorption d'hydrogene phosphork sur<br />
aucun des aliments 6tudiis.<br />
L'analyse des vitamines A et B2, avant et apres fumigation avec l'hydrogene<br />
phosphor6 n'a p<strong>as</strong> r6v616 de modifications . Ces r6sultats faisant apparaitre<br />
des r6sidus negligeables de l'ordre de 0,01 ppm, ou moins, montrent<br />
que le Phostoxin convient aussi bien pour les fumigations des aliments<br />
priparis que pour celles des denr6es agricoles brutes .<br />
Zusammenf<strong>as</strong>sung*<br />
Phostoxin®-Tabletten und -Kugelchen haben weltweite Anerkennun g<br />
als Phosphin-Quelle bei der wirkungsvollen Beg<strong>as</strong>ung von Getreide und<br />
<strong>and</strong>eren l<strong>and</strong>wirtschaftlichen Produkten gefunden . Seine Toxizitat fur alle<br />
Entwicklungsstadien der Insekten, seine Sicherheit bei der Anwendung, und<br />
d<strong>as</strong> Fehlen von Riickstiinden machen es fur diesen Zweck zu einem idealen<br />
Mittel. Wiederholte Beg<strong>as</strong>ung, sofern these bei erneuter Infektion notwendig<br />
ist, schafft keine Probleme hinsichtlich der Akkumulation von<br />
Ruckstiinden.<br />
Neuerdings hat this breite Interesse fur die Verwendung von Phostoxin®<br />
bei der Beg<strong>as</strong>ung von verarbeireten und verpackten Nahrungs- <strong>and</strong> Futter .<br />
Mitteln zu Untersuchungen Anstoss gegeben, die zu experimentellen Daten<br />
fiber mogliche Ruckst<strong>and</strong>e luhren sollten. Zwei Methoden wurden bei der<br />
Bestimmung des evtl. vorh<strong>and</strong>enen Ruckst<strong>and</strong>sspiegels in verarbeiteten<br />
Nahrungsmatiteln angew<strong>and</strong>t. Die erste, indirekte Methode untersucht die<br />
beg<strong>as</strong>ten Nahrungsmittel selber. Die zweite ist eine experimenteIle "R6ckgewinnungs"-<br />
oder indirekte Methode, bei der d<strong>as</strong> Phosphin rur Beg<strong>as</strong>ung<br />
benutzt und Bann zuruckgewonnen wird . Mit beiden Methoden wurden<br />
viele Proben, u.a. Getreide und Getreide-Produkte, Fruchte und Nusse,<br />
Getranke, Futtermittel, Gemiise, Gewurze sowie zahlreiche verschiedenartige<br />
Nahrungsmittel beg<strong>as</strong>t und anschliessend analysiert. Dabei ergab sichkeinerlei<br />
Hinweis <strong>for</strong> die Absorption von oder die Adsorption an eines der<br />
untersuchten Nahrungsmictel.<br />
Analysen von Vitamin A <strong>and</strong> B2 vor und nach Beg<strong>as</strong>ung mit Phosphin<br />
ergaben keine Hinweise fur irgendwelche Anderungen.<br />
Diese Ergebnisse, die ubereinstimmend auf zu vernacbl<strong>as</strong>sigende Riickst<strong>and</strong>e<br />
von etwa 0,01 ppm oder weniger hinweisen, zeigen sowohi die<br />
Eignung von Phostoxin® *Is Beg<strong>as</strong>ungsmirtel fur verarbeitete Nahrungsund<br />
Futtermittel, als such seine Verwendbarkeit unter Praxisbedingungea.<br />
References<br />
ALRSSANDRINI, M . E., <strong>and</strong> F. W. WHrrrsuoRs . Working paper lOc, on aluminum<br />
<strong>phosphide</strong>. joint FAO/WHO Meeting, Rome (1965) .<br />
• Obetsetst von H. P. LINSxEN&<br />
http://legacy.library.ucsf.edu/tid/mjq66a99/pdf
148 W. H. DienitiCH, GERO MAYR, KARL HILD, J. B. SULLIVAN, <strong>and</strong> J. MURPHY<br />
American Con/erence of Government Industrial Hygienists : Threshold Limit Values<br />
<strong>for</strong> 1963, et seq. (Pamphlet 1963) .<br />
BRUCE, R . B .; Unpublished reports from Hazleton•Nuclear Science Corp . to Hollywood<br />
Termite Control Co ., Inc. (Apr. 30, June 19, <strong>and</strong> Oct. 17, 1958) .<br />
-,A. J. Roann.S, <strong>and</strong> T. 0. TW'T : Phosphine residues from Phostoxin® treated<br />
grain . _J- ._Agr. Food Chem . 10, 18 (1962) .<br />
Codex Alimentariur Commission, Committee on Pesticide Residues : Working paper<br />
on residue tolerances of hydrogen <strong>phosphide</strong> <strong>as</strong> derived from aluminum <strong>phosphide</strong>,<br />
in grain <strong>and</strong> grain products . The Hague, The Netherl<strong>and</strong>s (Jan . 17.22, 1966) .<br />
COGBURN, R. R ., <strong>and</strong> E. W. TILTON, Studies an phosphine <strong>as</strong> a <strong>fumigant</strong> <strong>for</strong> sacked<br />
rice under g<strong>as</strong>-tight tarpaulins. J. Econ, Eatomol . 66, 706 (1963) .<br />
Committee on Pbytophermacy, Ministries of Social Affairs, Public Health, <strong>and</strong> Agriculture,<br />
The Netherl<strong>and</strong>s : Residues of insecticides in cereals imported In The<br />
Netherl<strong>and</strong>s, 1965 . Preliminary report (Mar. 1965) .<br />
--- Residues of insecticides in cereals imported in The Netherl<strong>and</strong>s, 1964/65. Second<br />
report (Jan . 1965) .<br />
COTTON, ṚT.: Pests of stored grain <strong>and</strong> grain products. Minneapolis, Minn . :<br />
Burgess (1963) .<br />
CouRVILLE, C. B. : Confusion of presumed toxic g<strong>as</strong> poisoning <strong>for</strong> fatal granulomatous<br />
meningo-encephalitis resulting in a severe progressive arteritis <strong>and</strong><br />
gross cerebral hemorrhages (Report of a fatal c<strong>as</strong>e <strong>as</strong>sessed <strong>as</strong> hydrogen <strong>phosphide</strong><br />
(phosphine) poisoning. Bull. L. A . Neural. Soc. 29, 76 (1964) .<br />
PAO/WHO Committee on Pesticide Residues : Evaluation of the hazard to consumer<br />
resulting from the use of <strong>fumigant</strong>s in the protecting of food . Report of Joint<br />
Meeting (1965) .<br />
FREEMAN, J. A.: Stored products infestation <strong>and</strong> its control in Turkey. (Pamphlet<br />
1957) .<br />
FREY,W.: Bericht fiber die 10. Sitrung des "Stindigen Ausschusses fits Vorratshaltung<br />
cod Schidlingsbeklmpfung." Nachtbl. d. D . Pflanienachutzdienstes (Braunschweig)<br />
17, 26 (1965) .<br />
GUNN, J . W.: Report on mild fumigation. Pamphlet, Hollywood Termite Control<br />
Co., Inc. (1959) .<br />
HARADA, T.: A study on a new <strong>fumigant</strong>-Phostoxin. Authorized translation, originally<br />
published by the Japanese Agriculture--Forersry Department, Food Research<br />
Institute (1962) .<br />
HESEL77NE, H ., <strong>and</strong> R. H. THOMPSON : The use of aluminum <strong>phosphide</strong> tablets <strong>for</strong><br />
the fumigation of grain . Milling, Part I CXXIX (24), 676 (1957) ; Part 2<br />
CXXIX (25), 730 (1957) ; Part 3 CXXIX (26), 774 (1957) .<br />
HUBERT, F. P. : Emergency fumigation operation combines heat, humidity, <strong>and</strong><br />
Phostoxin&. Agr. Chemicals 17, 20 (1962) .<br />
KLIMMER, O. R.: Toxicology of phosphine (German) . Unpublished report to<br />
Degetch (July 6, 1958) .<br />
-- Toxicology of phosphine. Supplement (July 16, 1958) .<br />
-- Plianzenschutz-und Schidlingsbekimpfungsmittel---Abriss einer Toxicologic rind<br />
Therapie von Vergifrungen. Hattingen (Ruhr) : Hundt-Verlag (1964) .<br />
--- Chronic poisoning with phosphine. Unpublished report to Degetch (Sept. 28,<br />
1964) .<br />
-- On the toxicology of phosphine. In press. Arcbiv fiir Toxikologie (1966/67) .<br />
LINDGREN, D. I. ., L. E. VINCENT, <strong>and</strong> R . G . STRONG : Studies on hydrogen <strong>phosphide</strong><br />
<strong>as</strong> a <strong>fumigant</strong>. J. Econ . Entomol. 61, 900 (1958) .<br />
LISCOMBE, E. A. R .: <strong>Hydrogen</strong> <strong>phosphide</strong> in tablet <strong>for</strong>m <strong>as</strong> a grain <strong>fumigant</strong>. Research<br />
<strong>for</strong> Farmers, Can. Dept. Agr. (Summer 1963) .<br />
MAYR, G., <strong>and</strong> K. Han : Unpublished data (1966) .<br />
McGREGOR, It E.: Evaluation of phosphine g<strong>as</strong> <strong>as</strong> a <strong>fumigant</strong> <strong>for</strong> shelled yellow tors<br />
stored in concrete silo-type storage. NW Millet 265, 13 (1961) .<br />
MUNRO, I-<br />
Publi c<br />
-- Manual<br />
NEITZERT,<br />
report<br />
PINGALE,<br />
in Indi<br />
Bull . G<br />
POPP, H . :<br />
to Deg<br />
RAT, L. J.<br />
hydrog'<br />
II), 3<br />
J. N .<br />
drogen<br />
Bull . (<br />
RAUSCHER<br />
Praktis#<br />
REYNOLDS<br />
granari<br />
phosph<br />
SCHULEMI<br />
toxin-ti<br />
SMtr, B . .<br />
Africa<br />
STRONG, I<br />
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<strong>Hydrogen</strong> <strong>phosphide</strong> <strong>as</strong> it <strong>fumigant</strong> 149<br />
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Public Health Inspectors, Engl<strong>and</strong> (1960) .<br />
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report to Degetcb (Jan. 19, 1953) .<br />
PINGALE, S. V., L. RAJ, J . N . SARID, <strong>and</strong> I . P . KAPOOR : Fumigation of food grains<br />
iti India with hydrogen <strong>phosphide</strong> . Series 11. Rail-wagons fumigated in transit .<br />
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POPP, H .: Phosphine residues in fumigated wheat (German) . Unpublished report<br />
to Degetcb (March 16, 1953) .<br />
RAI, L, J. N . SARID, <strong>and</strong> S. V. PINGALE : Fumigation of food grains in India with<br />
hydrogen <strong>phosphide</strong> . Series 1. Tests in concrete bins. Bull . Grain Technol . I (I <strong>and</strong><br />
11), 3 (1962) .<br />
-,J. N . SARID, <strong>and</strong> T. RAMASNAN : Fumigation of food grains in India with by<br />
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Praktische Schadlingsbekampfer (Dez . 1-3, 1957) .<br />
REYNOLDS, E. It, J. M . ROBINSON, <strong>and</strong> C. HOWELLS : The effect on Sitophilur<br />
granaries (L .) (Coleoptera, Curculionidae) of exposure to low concentrations of<br />
phosphine. J. Stored Prod. Research 2, 177 (1967) .<br />
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grain (German) . Unpublished report to Degetcb (July 15, 1953) .<br />
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Africa Dept. Age. (1957) .<br />
STRONG, R. G., <strong>and</strong> D . L LINDGREN : Germination of cereal, sorghum, <strong>and</strong> small<br />
legume seeds after fumigation with hydrogen <strong>phosphide</strong> . J. Econ. Entomol . 63,<br />
1 (1960) .<br />
SULLIVAN, J. B., <strong>and</strong> J . MURPHY: Unpublished data (1966) .<br />
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Kingdom. The Sanitarian 70, 1945 (1961) .<br />
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provided FAO Working Party on Pesticide Residues, Rome (May 1965) .<br />
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une technique nouvelle trouvant un large champ d'application . Par<strong>as</strong>itic, XII,<br />
No. 2 (1956) .<br />
WAGNER, R. M., <strong>and</strong> R. W . FoGLEMAN : Determination of <strong>phosphide</strong> residues in<br />
commercial wheat flour. Unpublished report from Hazleton-Nuclear Science Carporarion<br />
to Hollywood Termite Control Co ., Inc. (Jan. 9, 1962) .<br />
. report to<br />
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