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L<br />

erween their<br />

Health Bull.<br />

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stol on live.<br />

in different<br />

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 />

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KLIMMER<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 />

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MA'<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 />

conthe<br />

•ntro l<br />

thod,<br />

- de-<br />

)66)<br />

nigacans,<br />

stitut<br />

fat<br />

:orn-<br />

'ecan<br />

.1 K,<br />

nde d<br />

any<br />

aeon<br />

•hic h<br />

hich<br />

irect<br />

<strong>and</strong><br />

been<br />

:ame<br />

rility<br />

Tracy<br />

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 />

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<strong>Hydrogen</strong> <strong>phosphide</strong> <strong>as</strong> it <strong>fumigant</strong> 149<br />

MtVNRO, H. A. U. : Modern <strong>fumigant</strong>s <strong>for</strong> the control of pests . Ann . Coof. Assoc.<br />

Public Health Inspectors, Engl<strong>and</strong> (1960) .<br />

Manual of fumigation <strong>for</strong> insect control. FAO (1964) .<br />

NErrZERT, K.: Influence on the baking quality of wheat by Phostox . Unpublished<br />

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 />

Bull . Grain Tcchnol. I (111), 43 (1963) .<br />

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 />

drogen <strong>phosphide</strong> . Series III . Sacked wheat fumigated under g<strong>as</strong>proof covers .<br />

Bull. Grain Technol . II (11I), 3 (1964) .<br />

RAUSCHER, H .: Bekampfung von Getreideschidliogen mit Phosphorw<strong>as</strong>serstoE . Der<br />

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 />

SCHULEMANN, W., <strong>and</strong> O. R . KLIMMBR : Expert opinion on oral toxicity of Phostoxin-treated<br />

grain (German) . Unpublished report to Degetcb (July 15, 1953) .<br />

SMIr, B .: The control of stored grain insects in South Africa . Bull. No. 355, S .<br />

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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http://legacy.library.ucsf.edu/tid/mjq66a99/pdf

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