21.01.2014 Views

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 ...

SHOW MORE
SHOW LESS

You also want an ePaper? Increase the reach of your titles

YUMPU automatically turns print PDFs into web optimized ePapers that Google loves.

L<br />

erween their<br />

Health Bull.<br />

19) .<br />

enate. Anal.<br />

stol on live.<br />

in different<br />

t <strong>and</strong> Estern<br />

1. Proc . Nat .<br />

tsphorylation<br />

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

,lism of the<br />

i the use of<br />

arbor pestic<br />

determinanew<br />

method<br />

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 />

1111131111 1<br />

I I 1 4 1 1<br />

1 o 9 -VQ I I 1 I<br />

<strong>and</strong> three t-<br />

were showr<br />

The NF<br />

using a men<br />

imported it<br />

phosphine .<br />

were all 0 .(<br />

28 product:<br />

to 0.3 p .p.n<br />

were 0 .05 I<br />

The Co<br />

Netherl<strong>and</strong>:<br />

grain, aerat<br />

above 0 .00<br />

phosphine<br />

ner, <strong>and</strong><br />

phosphine t<br />

Phostox<br />

fumigation<br />

Lions were<br />

tion of ceri<br />

phine did n<br />

In Canada,<br />

<strong>processed</strong> fe<br />

be negligi b<br />

II<br />

~Ig Ig II~I<br />

O O O O O<br />

IIIINIII1 10 11<br />

O o<br />

a o i I I- I I -4 I I<br />

o O O O<br />

I o l t a t t I l I p<br />

I I I I I I I Q I<br />

O O N O<br />

0 a 0 0 , , . r '' a a a a<br />

Early e<br />

had indicat .<br />

present art<br />

w<strong>as</strong> shown<br />

h<strong>and</strong>led (t<br />

without ci<br />

KLIMMER<br />

<strong>foods</strong>, the t<br />

in the fury<br />

meable tar_<br />

products a<br />

In spit.<br />

Lion wheth<br />

gated foot<br />

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


A A AA AAAAAAA AA A<br />

A O0<br />

A<br />

O<br />

0<br />

A A AAAAAAAAAA A A<br />

O 0 0 O O O O O O O O O Q O 0 0 0<br />

IIIO 000s~s0s$0$00$ ~<br />

W W W W W W W W W W W W $ b. W W W<br />

O O O O<br />

~~! IIIIIIIIIIIIIIII I<br />

I<br />

A A<br />

O O O 0<br />

$ a b l I IIIIIIIII IJIIIII<br />

%M -4<br />

I<br />

0 00 0<br />

$ -Mll 1111{1111111{1111<br />

w ... w a-<br />

A<br />

0 0 0 O<br />

00_ I IIIIIIIillllll .I l l<br />

IPI<br />

MOP4 R a aprgdtogd aaeo3IH<br />

A ild<br />

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 />

turmeri<br />

custom:<br />

possibh<br />

repeate,<br />

sorptio t<br />

MA'<br />

vitamin<br />

phosphi<br />

weight<br />

to be p<br />

Ba. haw<br />

examint<br />

in br<strong>as</strong>:<br />

Vitamit<br />

garden I<br />

on any<br />

The<br />

with P1<br />

ported<br />

sophisti,<br />

sional r<br />

fumigat<br />

been at'<br />

of Phos<br />

by the<br />

Disc<br />

ucts wl<br />

Phostox<br />

than 1 .0<br />

after ha<br />

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


I I I I i ti I 1 06 I 3addad pai p°~ I! 10066548 8<br />

96'66 I'0 8<br />

26'66 1'0 8<br />

~ 05 ms<br />

001 scava<br />

00 'D!U<br />

ooZ<br />

O0Z<br />

oot<br />

rtonids p<strong>as</strong>s(i<br />

salads PWp a<br />

001<br />

08'66 TV 8 001 6" 390<br />

001 c3woo t<br />

1 001 t0oao'ytj<br />

58.66 I'0 B 00 snog nwgdd<br />

16'66 I'0 8 f oo f°~R ~*gdti<br />

l1 o0<br />

00'0 00.0 10'0 0't OZ AOZ (POP=) 'ooo<br />

00'0 00'0 O(o 0'1 0Z oot (pap'dun) '0303<br />

00'0 00'0 00.0 0£'0 0'T OZ ooc (aSg3 d p s )<br />

00'o 00.0 00'0 L0'o SZro 0•T OZ 005<br />

s 3=q&<br />

(p"an )<br />

nmu 3*ag&<br />

I<br />

•sg w •sg pZ 'sg Zi 'q 9 •sq 0 ('g)Dix0I5oq (1) sagmsip ('8) 70n0mv diipoiamv3<br />

s0J UO<br />

3 p303' 6saeo3<strong>as</strong> IW3ij nopeH!amd<br />

(9961 aTIH pln IUVyq) p<strong>as</strong>vnpus squat xoss<strong>as</strong>aa aqs wt{a PUP rta4s1<br />

azatop aqt !a sta19a,L sssxotrogd suns{ pat<strong>as</strong>aua1 ausgdtoq¢ qs <strong>as</strong> pataZiusuf spoof patra3os4 -01 1 ausgdrogd /0 ,f~saosag u 21961<br />

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


10066548 9<br />

0<br />

*6pA=*dtaJ '6sp of PP '01 '6 `r<br />

JOI UOI drmnj MP lpiTPaa<br />

9-- 09£'0 or<br />

r6'66 LLS'£ or<br />

Z6'66 Lice or<br />

• 26766 0'£ or<br />

u 96'66 886'r or<br />

v<br />

s<br />

£666 0'E<br />

S<br />

or<br />

86'66 0'1 or<br />

a<br />

2$66 i'0 or<br />

£6'66 1'0 a<br />

90'00I 260'0 i t<br />

06'66 1`0 8<br />

)-=-Id L6'66 P° `ZO'001 `08'66 'L666.<br />

ON<br />

ooz<br />

001<br />

001<br />

~OOT<br />

OOT<br />

001<br />

001<br />

001<br />

001<br />

oor<br />

ON<br />

ooz<br />

Got<br />

00 5<br />

06<br />

09<br />

06<br />

Jnog Jtagm<br />

Jaym<br />

i°Rom<strong>as</strong><br />

W"OD<br />

S" J .p<br />

Thou<br />

=TV 390<br />

Jltpa<br />

mu 's2uuJ J<br />

SMWJ<br />

3i<br />

Jape<br />

Jaddad fiqq pUUQJ J<br />

saddad par pnnojq<br />

9666 1'0 8<br />

i 0 5<br />

{ 100 1<br />

Got<br />

WOOD<br />

Oor<br />

Z6'66 1'0 8 oor tswudIQ<br />

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 />

legume<br />

1 (19,<br />

SULLIVAN,<br />

TURTLE, I<br />

Kingdc<br />

United<br />

provide<br />

VAN DEN<br />

une te'<br />

No. 2<br />

WAGNER,<br />

comme<br />

po►atio<br />

r-A<br />

f<br />

I<br />

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


♦'<br />

r<br />

J. MURPHY<br />

.imit Values<br />

). to Holly.<br />

58) .<br />

;in® treate d<br />

rking paper<br />

t <strong>phosphide</strong>,<br />

•22, 1966) .<br />

t <strong>for</strong> sacke d<br />

t, <strong>and</strong> Agri.<br />

red in The<br />

165. Secon d<br />

rlis, Mina . :<br />

Fatal grans .<br />

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

a <strong>phosphide</strong><br />

ao consumer<br />

set of join t<br />

(Pamphlet<br />

rratshaltung<br />

,unschweig)<br />

rite Control<br />

lation, orig-<br />

, Food Re.<br />

t tablets <strong>for</strong><br />

7) ; Part 2<br />

nidity, <strong>and</strong><br />

<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 />

TURTLE, E. E.: The control of infestation in commodities in ports in the United<br />

Kingdom. The Sanitarian 70, 1945 (1961) .<br />

- United Kingdom in<strong>for</strong>mation on the occurrence of residues in cereals. Report<br />

provided FAO Working Party on Pesticide Residues, Rome (May 1965) .<br />

VAN nEN BRUEL, W. E., <strong>and</strong> D. BOLLAERTS : La fumigation i I'hydrogcne phosphors,<br />

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 />

:ologie <strong>and</strong><br />

4) .<br />

(Sept. 28 ,<br />

(1966167) .<br />

i <strong>phosphide</strong><br />

migant. Reyellow<br />

emu<br />

It<br />

..r<br />

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

Hooray! Your file is uploaded and ready to be published.

Saved successfully!

Ooh no, something went wrong!