With the Compliments of the Author. 
I. 
ON THE FORMATION OF VOLATILE COMPOUNDS OF 
ARSENIC FROM ARSENICAL WALL PAPERS. 
IT. 
ON CHRONIC ARSENICAL POISONING 
FROM 
WALL PAPERS AND FABRICS. 
BY 
CHARLES ROBERT SANGER. 
[Reprinted from the Proceedings of the American Academy 
of Arts and Sciences, Vol. XXIX.] 
1894. 112 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
IV. 
ON THE FORMATION OF VOLATILE COMPOUNDS OF 
ARSENIC FROM ARSENICAL WALL PAPERS. 
Charles Robert Sanger. 
Received November 9, 1893. 
In cases of chronic poisoning from arsenical wall papers, the form 
in which the arsenic leaves the paper has been a long disputed ques- 
tion. Certain well defined symptoms were easily attributable to the 
local irritant action of arsenical dust in the form of arsenious oxide, 
the copper greens, etc., and the extension of these symptoms to the 
digestive organs could be referred to the same cause. Yet, on the 
other hand, under conditions unfavorable to the separation of arseni- 
cal dust, as, for instance, where an arsenical paper underlay one that 
was perfectly free, cases of poisoning have been very frequent, and to 
explain them the formation of a gaseous or volatile arsenical compound 
was assumed. 
Experiments to decide this point have been numerous since chronic 
arsenical poisoning by wall papers was recognized, but none of them 
until recently have been decisive, as they were with few exceptions 
carried on under unfavorable conditions and by methods that in point 
of exactness left much to be desired. Each side has had its adherents, 
the one asserting that chronic poisoning must be due entirely to dust, 
the other declaring that the cause lay in the absorption of an arsenical 
gas, or in the combined action of gas and dust. Many, not believing 
that the absorption of dust could alone lead to the numerous extreme 
or obscure cases that have been observed, have used the lack of proof 
of gas formation as an argument against the possibility of chronic 
poisoning from arsenical surroundings, although they admitted the 
local action of dust in certain cases. Further, those who denied the 
possibility of arsenical poisoning from wall paper under any circum- 
stances considered their position strengthened by the failure to establish 
definitely the formation of a gaseous compound. 
It was in this doubtful state that the question lay at the time when 
this investigation was begun, some seven years ago. My work was SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
113 
frequently interrupted and delayed, but about two years ago, I arrived 
rather reluctantly at results which seemed to show the improbability 
of the formation of an arsenical gas, though the possibility was as 
clear as ever. But the extension of bacteriological methods to the 
investigation has thrown a new light on the matter, and during the 
past year I have been able to satisfy myself of the correctness of the 
investigations which have shown that a volatile arsenical comppund 
can be formed by action of certain moulds on organic matter contain- 
ing arsenic. The nature of the compound is still unknown, and will 
require extended investigation before it is determined; but it certainly 
does not seem to be arseniuretted hydrogen, which was the compound 
commonly supposed to be formed. 
Historical. 
The danger from arsenical colors in living rooms seems to have 
been to some extent foreseen before cases of chronic poisoning actu- 
ally arose, for an order of the Prussian government of January 12, 
1815,* directed that the color should be rubbed from green walls when 
wet, and not when dry. 
Gmelin,f in 1839, was the first to call attention to the danger from 
arsenical wall papers, and considered that the arsenic might be volatil- 
ized as some product of the fermentation of the organic matter with 
which it was mixed. 
Riedel,t in 1844, says that "air can take up arsenic acid and 
hydrogen can form arseniuretted hydrogen." 
Von Basedow,§ in 1846, considered that the arsenic might be liber- 
ated in the form of kakodyl. lie gives some cases of poisoning in 
rooms painted with an arsenical green on a lime ground, and lays 
stress on the peculiar garlic odor which he notices. This he com- 
pares to the odor obtained by boiling arsenious oxide with acetic acid, 
and says it is similar to that which arises from stuffed birds. The 
occupants of the room noticed no such odor. Von Basedow notes 
that the arsenic decreases in the paper by decay, but no analyses are 
given in support of this assertion. 
Krahmer,|| in 1852, was the first to institute experiments to deter- 
* Krahmer, Deutsche Klinik, 1852, XLIII 481. 
f Ref. by Eulenberg, Die Lehre v. d. schddl. u. gift. Gasen, 1865, p. 413, to 
Karlsruher Zeitung, November, 1839. 
t Ref. by Krahmer, loc. cit., to Ann. der Staatsarzneikunde, X. 407. 
§ Preuss. Med. Zeitung, 1846, X. 43. 
|| Loc. cit. 
VOL. XXIX. (n. S. XXI.) 8 114 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
mine whether a volatile arsenical compound was liberated. He 
ridiculed the ideas of Riedel and v. Basedow, and considered that the 
arsenic could not even leave the walls as dust. His experiments were 
as follows. Four grams Neuwieder green were mixed with paste and 
lime taken from a damp part of a ground floor wall, and placed in a 
two-necked Woulff bottle. After 19 days he observed no odor of garlic, 
nor indeed could he observe any in the five years that elapsed before 
his results were published, during which time the mixture remained 
in the bottle. Five hundred litres of air were then drawn through 
the bottle for 21 days, the air first passing through alcoholic potassic 
hydroxide. The solution was then neutralized by hydrochloric acid, 
and, "on treatment with arsenic free zinc, gave no arsenic." We have 
here no idea of the delicacy or accuracy of the test used. 
Next, a solution of argentic nitrate was substituted for the potassic 
hydroxide and air drawn through for fifteen days. No change was 
observed in the silver solution, but it was not tested for arsenic. He 
then passed the air from the bottle for five days through a hard glass 
tube heated in two places and obtained no mirror of arsenic. He 
next thinks that the arsenic compound, if formed, should be mixed with 
hydrogen before absorption, and so places a hydrogen generator in front 
of the bottle. The hydrogen generated from 133 grams of zinc, after 
filtration by cotton wool, was passed through the bottle, then through 
a solution of alcoholic potassic hydroxide, then silver solution, and 
finally through the hot tube. He found no trace of arsenic in the 
solutions or in the tube. The test is not given. During the whole 
time there was no evidence of mould in the bottle. 
Krahmer states that he had lived for eight years in a dry and airy 
room, the walls of which had received during that time three coats of 
Neuwieder green, probably five pounds at a time. He never felt any 
trouble from its presence. He repeatedly examined the dust for 
color, but never found any. To decide the question as to arsenic in the 
dust, he drew fifty litres of the air of the room through nitric acid, and 
added to it the dust that had fallen on a piece of paper during that 
time. The acid was then neutralized with sodic carbonate, evapo- 
rated, and the sodic nitrate melted. The residue was dissolved in 
water, filtered, and the filtrate tested with zinc and hydrochloric acid. 
He found no arsenic, which is hardly to be wondered at in the 
presence of so much nitric and nitrous acids. He could not find 
copper in the filtrate, but this was probably lost by ignition and 
filtration. 
If Krahmer's experiments had been otherwise properly conducted, SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
115 
the method of examination for arsenic would alone have deprived 
them of value. Not finding, by his unskilful test, any arsenic in the 
dust, he concludes at once that arsenic cannot be liberated at all, and 
uses the result as an argument against the possibility of arsenical 
poisoning from wall papers. 
Arnd,* in 1855, offers the following remarkable explanation: " Ar- 
seniates are decomposed by carbon dioxide, setting free arsenious 
oxide which is volatilized. By evaporation of the water from the 
paste, arsenical particles are carried off. Sulphide of arsenic on a 
lime ground is decomposed with evolution of arseniuretted hydrogen, 
as the lime takes away the sulphur, forming calcic sulphide." 
Eulenbergf mentions the following experiment made in 1857 by 
Halley and Williams, but I can find no account of it or reference to 
it elsewhere. Several sheets of filter paper were soaked in ammonia- 
cal argentic nitrate and hung up in a closed room of which the paper 
contained Schweinfurth green. Gas lights were kept burning ten 
hours, and after they were put out the room was kept closed ten 
hours longer. The papers, which were blackened, were digested with 
hydrochloric acid for thirty minutes, and a piece of copper was laid in 
the solution. A gray deposit was formed on the copper, and the 
latter, after being washed and dried, was heated in a bulb tube. 
A white ring was obtained and said to be arsenic, though no further 
proof was given. Yet, if it were arsenic, which is not decided, it 
might have had its source in the dust of the room, as well as from a 
volatile compound. 
Halley, in 1858, in a letter to the London Times, t tests the air 
of a room containing an arsenical wall paper by merely hanging up 
sheets of paper soaked in ammoniacal argentic nitrate, in which he 
observes after some time the formation of numerous "well defined 
crystals of arsenious oxide, visible under a low power microscope." 
I am inclined to think that this experiment is merely the foregoing, 
subjected to a newspaper condensation, which has omitted essential 
details. 
Campbell,§ in 1858, made the following experiment. Strips of arsen- 
ical paper, about one square foot in all, were placed in a bottle contain- 
ing a thermometer and fitted with a double bored cork. Through one 
* Verhandl. d. Verein f. Staatsarzneiwissensch. in Berlin, 1855,1. 47. 
t Loc. cit., p. 416. 
J Pharmac. Journ. and Transactions, 1858, p. 428. 
§ Ibid., p. 520. 116 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
boring passed a right-angled hard glass tube, terminating in a spiral, 
which could be heated by a broad burner. The other boring held an 
exit tube passing to a solution of potassic hydroxide. Gas jets were 
kept burning in the room, and air, at a temperature from 16 to 60°, 
was drawn from the bottle through the solution. Several trials were 
made, each lasting one hour, and in no case was arsenic detected. 
How the arsenic was tested for is not stated, but it is not surprising 
that none was found. The absurdity of the experiment was shown by 
Taylor * a week or so later. 
Abel,t in the same year, made the following experiments at the 
instance of the British government. A room was selected having a 
green unglazed paper containing one fifth of a grain of arsenious oxide 
per square inch (20 grams per square meter). 
1. The room was closed for 36 hours, and then the air was led 
between four and five hours through a solution of argentic nitrate, and 
then through a tube containing asbestos soaked in ammoniacal argen- 
tic nitrate. No arsenic was found in solution or tube. 
2. Five gas flames were burned in the room for several hours, and 
at the end the air was led through the same reagents with the same 
negative result. The method used in testing is not given. 
3. A glass tube, 3.5 ft. long and 2 in. in diameter, was filled with 
small pieces of arsenical paper, warmed to 32°, and connected with 
the reagents as above. The air of the room was led through for a 
week, and from time to time gas burners were lighted. 
4. The air was passed through a strong solution of sulphurous acid 
and then led for 24 hours through the apparatus. 
5. The products of combustion of a gas burner were concentrated 
by a funnel and led through the apparatus for three days, and again 
(6) for four days. 
7. The paper was roughened by friction and hot air led through 
for nine days. 
8. Strips of arsenical paper with decomposing paste were placed in 
the same tube, and hot air led over for nine days, with products of 
gas combustion also. In none of Experiments 3 to 8 was arsenic 
found in either silver solution or tube. Yet as the method of test- 
ing for arsenic is not given, and we do not know its accuracy, the 
experiments are thus deprived of considerable value. 
* Pharmac. Journ. and Transactions, 1858, p. 553. 
t Ibid., p. 556 ; also British Review, October, 1858, and Schmidt's Jahrbuch, 
1859, XLV. 20. SANGER. VOLATILE COMPOUNDS OF ARSENIC. 
117 
9. 600 grains (39 grains) of emerald-green were distributed in a 
lot of cotton wool and placed in a jar, into which a tube was plunged 
containing cotton wool and connected with the silver solution. Air 
was drawn through at 32° for some time, but no arsenic was detected 
in the solution. 
Phillips,* in 1858, repeated the experiment of Halley. Two clos- 
ets were used, one containing 48 sq. ft. (4.46 sq. m.) of a paper 
containing 11.8 grains arsenious oxide, as Schweinfurth green, to 
the square foot (8.3 grams per square meter), and another containing 
53 sq. ft. (4.92 sq. in.) of the same paper. In each closet were placed 
two dishes, one containing a solution of potassic hydroxide and the 
other ammoniacal argentic nitrate, besides a sheet of paper saturated 
with the latter. The closets were closed 72 hours and gas was 
burned 45 hours in one, the temperature being about 25°. No ar- 
senic was found in the solutions by Marsh's test, but the method of 
preparing the solutions for the test is not given. The paper also 
contained no arsenic, but was of course dark, and contained crystals 
of argentic nitrate. Phillips considered that his test proved the 
absence of the vapor of arsenious oxide, but he has apparently proved 
the absence of any arsenical dust. The use of the Marsh test is suf- 
ficient to account for this, as the amount of dust that might fall in 72 
hours from such a paper would quite possibly show no arsenic by the 
simple Marsh test. As a test for the presence of a gaseous compound 
like arseniuretted hydrogen, such an experiment is of no value. 
Paul,f in the same year, thinks that Campbell's and Abel's work 
disproves the idea that arsenic is volatilized, and concludes from the 
negative results that the arsenic cannot leave the paper at all, paying 
no attention to the possibility of the detachment of arsenical dust. 
Oppenheimer,$ in 1859, was the first to show the presence of arsenic 
in the dust of a room. 
Schmidt and Bretschneider,§ in 1859, placed a mixture of Schwein- 
furth green, meal, and water in a large flask closed by a double bored 
cork, through one boring of which a tube led to an argentic nitrate 
solution protected from the light, the other hole being presumably 
fitted with a tube reaching under the mixture. In three similar 
flasks the same mixture was placed, and to them were added, respect- 
* Jour. Franklin Inst., [3], XXXVI. 397 ; also Lond. Civ. Eng. and Arch. 
Journ., 1858. 
t Pharmac. Jour, and Transactions, 1858, p. 616. 
t Ref. by Eulenberg, Zoo. oft., to Heidelberger Jahrb. d. Lit., 1859, p. 810. 
§ Untersuch. z. Naturlehre d. Mensch, u. Thier. v. Moleschott, VI. 146. 118 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
ively, putrid cheese, putrid blood, and yeast, and each flask was con- 
nected with an argentic nitrate solution as before. All four flasks 
were kept at 32° for six weeks, and air from them was passed through 
the silver solutions. A slight black precipitate was formed in each, but 
the liquid on being tested in the Marsh apparatus showed no arsenic. 
No odor was observed, and Schmidt and Bretschneider considered the 
fermentation to have been stopped. They decide that poisoning can- 
not take place in damp rooms from a volatile arsenical compound, and 
that it is more likely that the trouble comes from the detachment of 
dust in dry rooms. These experiments are more in line with recent 
work than those preceding, and they are the first that are worthy of 
much consideration. Certain conditions, not then understood, might 
have operated against the formation or detection of a gaseous com- 
pound. Although the Berzelius-Marsh test may have been used, we 
do not know the limit in Schmidt and Bretschneider's hands, and the 
treatment of the silver solution is not given. 
Wittstein,* in 1860, advances the idea that the arsenites in the 
coloring matter are changed to arseniates at the cost of part of 
their oxygen (5 As2O3 - 3 As2O. + As4), and that metallic arsenic is 
volatilized. 
Sonnenschein,f in 1869, made the following experiment in a damp 
room on the ground floor in which the paper was very arsenical, the 
occupant of which was affected by symptoms attributable to arsenical 
poisoning. The air of the room after passing through a wash-bottle 
was led through a hard glass tube heated to redness. After many 
hours' heating there appeared a perceptible mirror, which Sonnen- 
schein concluded to be arsenic, but he was unable to determine the 
nature of the volatile compound. The deposit, however, received no 
confirmatory test. 
Fleck, J in 1872, conducted the following series of experiments. 
1. A five-litre tubulated bell jar resting on a ground-glass plate 
was covered on the inside with paper smeared with Schweinfurth green 
(about 15 mgr. arsenious oxide per sq. cm.). The paper was fastened 
by a paste of potato starch. Through the tubulus passed a cork 
carrying one right-angled tube reaching to the bottom of the bell jar, 
and another to just below the cork. The jar was closed and allowed 
to stand. 
* Quoted by Eulenberg, loc. cit., p. 414; also Schmidt's Jahrb., CX. 88. 
t Handbuch d. gericbt. Chemie, 1869, p. 153. 
t Zeitsclir. f. Biologie, VIII. 444; also, Dingl. Polyt. Jour., CCVII. 146. SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
119 
2. A glass flask fitted with tubes like the bell jar was covered 
on the inside with a paste of gelatine and Schweinfurth green, closed, 
and allowed to stand. 
3. In a bell jar, fitted as in Exp. 1, was placed a dish containing a 
paste of Schweinfurth green and water. 
4. In a similar bell jar was placed a dish containing arsenious oxide 
and water. 
Experiments 1 and 2 should decide whether an arsenical gas could 
be given off* by decomposition of an arsenic compound with organic 
matter and moisture, while Experiments 3 and 4 would show if any 
came from an arsenic compound and water alone. In Experiment 1 
there was soon a formation of mould and odor of mould, and in Ex- 
periment 2 an odor of decaying gelatine. No garlic smell was noticed 
in either. The temperature was 17 to 18°. 
Jar No. 1 and flask No. 2 having been closed for three weeks, 
at the end of that time the air from the former was led for 24 hours 
through an absorption bottle containing 150 c. c. water, the air in the 
jar being renewed about a hundred times. The water was then intro- 
duced into a flask containing zinc and acid, from which hydrogen had 
been passing into argentic nitrate for one hour without result. The 
silver solution was discolored in 15 minutes, and after an hour was 
completely black. The filtrate became cloudy on addition of ammonia, 
but was not tested further for arsenic, the black precipitate being 
considered sufficient indication of the formation of arseniuretted hy- 
drogen. The same result was obtained from Experiment 2. 
Jars 3 and 4 were closed for eight days and the air from them drawn 
through water as before. The solution from No. 3 gave a very weak 
action on the argentic nitrate, while that from No. 4 gave none at all. 
The first jar and the flask were again closed for some time and the 
air led through 150 c.c. of argentic nitrate (1-100). The air, before 
entering the two vessels, passed through a tube of calcic chloride, and 
between the jar and the argentic nitrate was placed an empty tube to 
catch dust or anything that might be condensed. No dust or moisture 
was noticed in this tube. A slight gray deposit was formed in the 
silver solution and the filtrate gave a turbidity with ammonia. 
From the fact that the color of the paper was not lessened, Fleck 
concludes that the Schweinfurth green was not decomposed, but that 
the formation of arseniuretted hydrogen was due to decomposition of 
arsenious oxide. From the amount of silver precipitated he reckons 
the amount of hydride formed at 0.01 c. c. in the five litres. 
Fleck also mixed five grams arsenious oxide with two grams starch 120 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
to a paste in a 500 c.c. flask, and noticed formation of mould and crys- 
tals of metallic arsenic! Testing this as before, he found arsenic. 
No proof of the formation of an arsenical gas is given by these 
experiments. The fermentation, which was greater in the first series 
of experiments, undoubtedly produced enough volatile organic matter 
to reduce the silver solution in the light. The failure to test the 
silver solutions for arsenic deprives the results of value, though it is 
quite possible, in the light of recent work, that a volatile compound 
was formed. 
Hamberg,* in 1874, tested the air of a room for the presence of a 
volatile arsenic compound. He used a large dry room which had 
been papered for 25 to 30 years with a paper of which 1 sq. cm. 
gave, in the Berzelius-Marsh tube, a thick opaque crust of arsenic 
6 cm. long. Arsenic and arsenious acids were found in the coloring 
matter. The persons who let the room had not perceived any injury 
to themselves or to others. 
A series of tubes was hung on the wall opposite the windows, and 
the air of the room was drawn through them for a month, the door 
and windows being closed. During the experiment an alliaceous 
odor was occasionally observed. The first four tubes were U tubes, 
of which the first was empty and the next three contained cotton wool. 
Next came two Liebig bulb tubes with a solution of argentic nitrate 
in each, and between these and the aspirator was an empty guard 
U tube. 2,160 litres of air were drawn through the system. After 
a week a black precipitate appeared in the first silver solution, and 
later in the second. 
The tests were made by the Berzelius-Marsh method. From the 
first U tube a slight film of arsenic was obtained, in the second (con- 
taining cotton) likewise a trace, while the third and fourth contained 
none. The silver solution was filtered and the precipitate found to be 
silver, with some sulphide of silver. Ammonia gave a faint yellow 
precipitate in the filtrate. The latter was precipitated with hydro- 
chloric acid, and the filtrate after evaporation with sulphuric acid intro- 
duced into the Marsh flask. In ten minutes a brown film appeared, 
which increased after an hour to an opaque brown crust. The second 
silver solution, treated similarly, gave but a faint film. 
Hamberg is the first from whose results a definite conclusion can 
be drawn, and his work is of particular value from having been done 
* Pharmac. Journ. and Transactions, [3], V. 81; also, Nord. Med. Archiv, 
VI. No. 3. SANGER. VOLATILE COMPOUNDS OF ARSENIC. 
121 
on the air of a room. The methods of the experiment are only open 
to criticism in that the freedom of reagents and apparatus from arsenic 
is not stated. 
Selmi,* in 1875, investigated the question of the formation of 
hydrogen by the action of mould. After showing that sulphuretted 
hydrogen was developed in decaying organic matter over which 
sulphur had been sprinkled, he reasoned that arseniuretted hydrogen 
would be formed by the action of moulds on arsenical organic matter. 
He accordingly sprinkled very finely powdered metallic arsenic over 
a mixture of horse dung and flour, on which mould was growing 
vigorously, and placed the preparation in a tubulated bell jar. Strips 
of paper moistened with argentic nitrate were hung from the top of 
the jar. The tubulus at the top was closed by a stopper with two 
holes, carrying tubes for ingress and egress of the air that was drawn 
through by an aspirator. After five days during which time the bell 
jar was in the dark, the paper was found to be slightly reddened. It 
was then treated in a dish with potassic hydroxide, which set free, 
besides ammonia, a peculiar disagreeable odor. The alkaline residue 
was then neutralized with nitric acid, evaporated with sulphuric acid 
to destroy organic matter, and introduced into the Marsh apparatus. 
After an hour a distinct metallic ring was obtained which, after solu- 
tion in nitric acid and evaporation, gave a red color with argentic 
nitrate. 
A second trial under the same conditions resulted similarly. In a 
third and fourth, mouldy lemons were spread with arsenic dust and 
covered by a funnel from the top of which hung strips of argentic 
nitrate paper. After 38 hours the organic matter of the paper was 
destroyed by nitric and sulphuric acids, and the residue, introduced 
into the Marsh apparatus, gave a well defined ring. Five other trials 
were made under varying conditions, and in every case a ring of 
arsenic was obtained. In a tenth experiment arsenious oxide was 
sprinkled on mouldy starch paste, and placed under a bell jar through 
* Ber. d. deutsch. chem. Gesells., VII. 1642 (Corresp.); Schmidt's Jahrbuch, 
1875, CLX VIII. 60; Just, Botan. Jahresber., 1876, p. 116. All of these refer to 
a paper of Selmi's published in the Aceademia delle Scienze of Bologna, entitled 
"Nuovo Processo Generale per la Ricerca delle Sostanze Venefiehe," in which, 
however, the above work does not appear. I have recently obtained a reprint 
of this article (Bologna, 1875) with which is incorporated "Osservazioni sullo 
Sviluppo d' Idrogeno Nascente dalle Muffe," and the extract given above is from 
the latter paper. The abstracters have evidently referred to this separate 
monograph, and all fail to note the bearing of it upon the question of the 
formation of a volatile arsenical compound. 122 
PROCEEDINGS OP THE AMERICAN ACADEMY. 
which air was drawn. Strips of argentic nitrate paper hung in the 
bell jar acquired in eight days a red tint, and yielded in the Marsh 
apparatus a ring of arsenic. 
Selmi considered that the results pointed to the formation of an 
arsine, and that the formation of hydrogen by moulds was confirmed 
conclusively. 
In the light of recent work there may have been a volatile arsenical 
compound formed in Selmi's experiments. Yet we cannot accept 
them as conclusive because of the neglect to provide against the pos- 
sible reduction of the silver paper by the dust particles in the bell jar. 
Had the filtered air given the above results, they would have been of 
more value. Besides this the freedom of the reagents from arsenic is 
not shown. No mention is made of any alliaceous odor from the 
decomposing matter. The odor from the silver paper after adding 
alkali may be analogous to that noticed later by Hamberg, Gosio, and 
myself, but it is not sufficiently characterized by Selmi to draw any 
definite conclusion in regard to it. 
The results of Fleck and Hamberg were accepted by many as 
conclusive, and more recently the evidence of Selmi has been con- 
sidered corroborative. It was some time before Selmi's results 
became generally known. His paper did not obtain wide circulation, 
and the abstracts quoted above treated his work as bearing only on the 
general question of the development of hydrogen by moulds, and not 
on the formation of a volatile arsenical compound. 
Professor Chandler of Columbia, in the course of his testimony 
before a committee of the Massachusetts Legislature in March, 1886, 
stated that two of his students, Messrs. Morewood and Drummond 
had, in 1879, under his directions, passed the air from a vessel con- 
taining Paris green and paste into an argentic nitrate solution for a 
number of days, and failed to find any arsenic. The mixture was 
then allowed to decompose in a warm place and the air was tested for 
arsenic with the same result. They then covered a square yard of 
paper with Paris green and paste, placed it in a vessel, and drew air 
over it into argentic nitrate for many days. The result of this was 
also negative. As no further details were given, and the work has 
not, to my knowledge, been published, no conclusion can be drawn as 
to the possibility of finding small amounts of arsenic by the method 
used, whatever that might have been. 
Bartlett,* in 1880, tried the following experiments. He first 
* The Analyst, 1880, p. 81. SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
123 
passed a stream of hydrogen from sodium amalgam over a quantity of 
wall paper, free from arsenic and antimony, contained in a large glass 
vessel, and directed the stream against paper moistened with argentic 
nitrate and screened from light. There was no action after 12 hours, 
nor did the addition of ammonia to the hydrogen cause any blacken- 
ing. He then passed ammoniacal hydrogen from sodium amalgam 
over moist paper containing a large quantity of arsenic, and obtained 
what he calls "characteristic reactions " for arsenic, probably a reduc- 
tion of the silver paper. Of course the blackening of paper cannot be 
taken as proof of the presence of arseniuretted hydrogen, nor is the 
formation under these conditions to be expected. Bartlett notes that 
he intends to pass ammoniacal hydrogen over 20 sq. yd. of paper for 
a long time in the hope of collecting the resulting argentic arsenite, 
but he has not, to my knowledge, published anything further on this 
subject. 
Forster,* in 1880, tried the following experiments to ascertain 
whether arsenious oxide was volatilized from Scheele's green, and 
whether arseniuretted hydrogen could be given off from a paint con- 
taining this pigment. Air was drawn through a bottle filled with glass 
covered with Scheele's green, and, after filtration by cotton wool, was 
passed into a solution of potassic hydroxide. One experiment lasted 
one day, two lasted two days each, and a fourth seven days, the tem- 
perature of the bottle being from 45 to 50°. In each case the potassic 
hydroxide was neutralized by sulphuric acid, and by the Marsh method 
gave no arsenic. In a second series the bottle was filled with shavings 
smeared with a paint of linseed oil, turpentine, and Scheele's green. 
The air was not filtered and passed through two U tubes containing 
potassic hydroxide and argentic nitrate respectively. Two trials were 
made for five days and two for six days, at a temperature of 14° ; a 
fifth lasted nine days. The potassic hydroxide solution, treated as 
before, gave no arsenic. The silver solution was precipitated by 
hydrochloric acid, and sulphuretted hydrogen led through the filtrate 
for twelve hours. Not getting a precipitate, Forster concludes the 
absence of arsenic, but tests further by the Marsh method with a 
negative result. 
Giglioli,f in 1880, after a series of experiments lasting eight 
months, declared himself opposed to the theory of Selini, and favored 
* Proceedings Med. Soc. of London, V. 41; Chemical News, 1880. 
t Ann. d. R. Scuola sup. d'Agricoltura di Portici, II. 165; Gazz. chim. Ital., 
1881, p. 249. 124 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
the assumption that chronic arsenical poisoning was due to dust alone. 
He used moist bread and saccharine liquids, to which arsenious oxide 
had been added. The preparations were exposed to the air, and, 
after the mould had formed, were placed in a vessel through which a 
current of air was passed into an absorbent. Argentic nitrate and 
auric chloride were used, and in some experiments the air was led 
through a hot Berzelius-Marsh tube. No arsenic could be detected 
in the air above the mould, nor was there any odor. 
Bischoff,* in 1882, during the examination of some fodder with 
which arsenic had been mixed with intention of poisoning, placed a 
part of it, while still moist, in a covered glass dish. After some 
weeks he observed that mould had collected in the mass, and, on 
opening the dish, noticed an odor which, from its garlic nature, he 
concluded to be due to arseniuretted hydrogen. Strips of paper 
moistened with argentic nitrate were at once turned brown. This 
was considered by Bischoff to confirm the theory of the formation of 
arseniuretted hydrogen during fermentation. It is greatly to be 
regretted that this experiment, which has actually furnished a clue to 
the recent successful investigations, should not have been carried out 
properly. There was undoubtedly a volatile arsenic compound pres- 
ent, yet one cannot, in such an important question as this, accept 
an odor or a blackening of silver paper as indicative of arsenic. 
Hamberg,f in 1886, published the result of an investigation, extend- 
ing over nearly nine years and a half, on the change produced in ar- 
senious oxide in contact with decaying animal matter. I give the 
experiment in some detail, because an incorrect and misleading idea of 
it seems to have been obtained from the abstract quoted. 
In a twelve-litre flask were placed portions of a body; lungs, liver, 
kidneys, and intestines, mixed with broken glass and sand. The mix- 
ture was moistened with a solution (it is not stated whether it was 
acid or alkaline) of one gram of arsenious oxide, covered with sand and 
aluminous earth, and the whole saturated with water. The flask was 
connected with (1) a tube containing cotton wool, (2) a tube con- 
taining test paper, (3) an absorption tube with a solution of 
argentic nitrate, (4) a U tube to catch any of the silver solution 
which might be mechanically carried over, and to the last was attached 
a Finkener aspirator. Air was drawn from outside the laboratory 
* Vierteljahr. f. gericht. Med., N. F., XXXVII. 163. 
t Pharm. Zeitschr. f. Russland, XXV. 779; Behang t. k. svensk. vetenskabs- 
akad. Handl., Bd. 12, II., No. 3; Fres. Zeitschr. f. analy t. Chem., XXVI. 788, Ref. SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
125 
through the flask and system of tubes at the rate of 15-23 litres daily. 
Mould was noticed in 16 days. From June 4, 1876, to November 21, 
1885, the air of the flask was tested at irregular intervals, as detailed 
below, and the presence of arsenic in the silver solutions determined. 
In every solution except the first, reduction of the silver was noticed, 
and very often a yellowish sediment was formed. The odor of the 
air in the flask was very disagreeable, and in one case brought to 
mind the odor of either arseniuretted hydrogen or kakodyl. Sometimes 
the silver solution had a strong odor. Argentic nitrate paper, hung 
in the flask, turned dark very quickly, but plumbic acetate paper was 
not affected. Auric chloride paper was introduced in the last year, 
but was not reduced. Ammonia was given off freely, especially 
towards the last. 
November 21, 1885, as the last silver solution tested gave but a 
faint deposit in the reduction tube, and an argentic nitrate paper 
hung in the flask was not blackened, it was concluded that the action 
had ceased. The residue in the flask was then examined for arsenic. 
An aqueous extract yielded 149 mgr. arsenious sulphide and the 
residue from this, extracted with very dilute acetic acid gave 67 mgr. 
The remainder of the mass, consisting of organic matter, earth, sand, 
etc., was treated with hydrochloric acid and potassic chlorate, and 
from the filtered solution 469 mgr. arsenious sulphide were obtained, 
making 685 mgr. in all, corresponding to 551 mgr. arsenious oxide. 
The residue from the treatment with hydrochloric acid and potassic 
chlorate was not examined further, and it is quite possible that the 
extraction was not complete. 
The arsenic was found in the first two extracts as arseniate, but a 
similar condition could not from the method of extraction be shown 
in the residue. Undoubtedly the lower oxide was to a great extent 
changed to the higher. Hamberg concluded that the remaining 449 
mgr. had passed away as some gaseous compound, though it is not to 
my mind certain that these figures are not too large by the amount 
which may have remained in the last residue. 
A consideration of the amount actually absorbed is interesting, and 
throws some light on the nature of the volatile compound. In the 
interval between two successive examinations of silver solutions, 
or when the flask was opened to test odor or action on test paper, 
much of the gas may have escaped, yet it can. be fairly assumed that 
most of it came in contact with the absorbents. In the first examina- 
tion (after a run of five months) there were found 1.1 mgr. of arsenious 
sulphide, corresponding to 0.88 mgr. of the oxide. In the second test 126 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
(additional run of three months) the presence of arsenic in sediment 
and solution was confirmed qualitatively by different reagents, and I 
assume that the precipitate of arsenious sulphide was not weighable. 
In the third test (ten months additional run) the sediment gave 
0.8 mgr. of sulphide (0.64 mgr. oxide) while the solution gave a " weak 
reaction." Here again the precipitate seems to have been too small 
to weigh. In the succeeding determinations the attempt to estimate 
gravimetrically was abandoned, and the Berzelius-Marsh method was 
used. Eighteen months had elapsed during which time the action had 
apparently been at its height, as after sixteen months more the sedi- 
ment in the fourth test gave no arsenic and the solution an amount 
much less than the preceding. The rest of the tests gave diminishing 
amounts from the solutions, while none of the sediments, except the 
last, contained any arsenic. The silver solutions were precipitated 
with hydrochloric acid, filtered, and the filtrate, after evaporation 
with sulphuric acid, was added to the Marsh apparatus. 
Unfortunately, the quantitative estimation of arsenic by the Berze- 
lius-Marsh method was unknown to Hamberg, but I have placed the 
most accurate estimate possible on the mirrors from his description of 
them, and tabulate the results of the absorption tests on the opposite 
page. 
In the interval between the third and fourth tests, the argentic 
nitrate solution was one day replaced by a tube containing fused 
calcic chloride, and the air led through a glowing tube for eight 
hours. No deposit of arsenic was found. From January (15?), 
1882, to March 28, 1882, a second argentic nitrate solution was placed 
after the first, and, on examination at the same time, contained no ar- 
senic. After this, although a second solution was used, there is no 
record of its having been tested beyond the statement that the sedi- 
ment formed was very slight. From July 14, 1885, to October 28, 
1885, the argentic nitrate was replaced by a tube containing nitric 
acid (strength not given), and for most of the time there was an 
argentic nitrate solution after it. This acid yielded over a gram of 
ammonic nitrate which was not arsenical. The argentic nitrate solu- 
tion was kept in a month longer and gave only a faint deposit. This 
was the last test. 
Making allowance for the second test there were found from 2 to 
3 mgr. of arsenic as arsenious oxide in the air passed into the argentic 
nitrate, if we assume that each deposition of an arsenical mirror was 
carried to completion. This is, however, only from 0.44 to of 
the 449 mgr. which are supposed to have escaped as a gaseous com- SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
127 
No. 
Date of 
Examination. 
Duration of run 
in Months. 
Character of Mirror. 
Estimate of Mir- 
ror by Standard 
in Mgr. As2O3.* 
1 
1876, Nov. 10. 
5 
Estimated from As2S3. 
0.88 
2 
1877, Feb. 12. 
3 
Qualitative determination. 
- 
3 
1877, Dec. 21. 
10 
Estimated from As2S3. 
0.64 
4 
1879, Apr. [15?] 
16 
2 cm. long in 20 min.; "nearly opaque." 
0.08 
5 
1880, May 11. 
13 
2 cm. long in 35 min.; " slightly transparent." 
0.05 
6 
1880, Sept. [5 ?] 
4 
2 cm. long; " partly opaque." 
0.05 
7 
1881, Apr. 13. 
7 
2 cm. long in ten min.; " nearly opaque." 
0.06 
8 
1882, Mar. 28. 
11 
" Distinct." 
0.03 
9 
1882, May 11. 
2 
" Weak deposit." 
0.02 
10 
1883, Feb. 9. 
9 
" Only weak." 
0.02 
11 
1883, Sept. [15?] 
7 
"Only weak." 
0.02 
12 
1885, July 14. 
22 
" Only weak, transparent." 
0.02 
13 
1885, Oct. 28. 
3 
From nitric acid ; no mirror. 
0.00 
14 
1885, Nov. 21. 
1 
From solution; " faint, scarcely perceptible." 
0.01 
From sediment; ditto. 
0.01 
Total ........ 
1.89 
pound, and from 0.2 to of the total amount in the flask. 
Hamberg states that by addition of all the amounts separated from 
the silver solutions, partly as sulphide, partly as metallic arsenic, he 
finds that the greater part of the arsenical gas was not absorbed, and 
he thinks that possibly the silver solution was only partially able to 
decompose the gas. Whatever estimate he may have made from the 
mirrors is not stated ; hence we cannot know what amount he thinks 
was recovered. As my own experiments have shown the inadequacy 
of 2% argentic nitrate for absorption of the volatile compound and 
the chance for loss in preparing the solution in the above manner 
for analysis, the cause of loss is quite clear. The quantitative esti- 
* According to the method described by me in these Proceedings, XXVI. 24. 128 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
mation of the amount of volatile compound formed in this experiment 
is subject to too many chances for error to make it of any value except 
as a means of throwing light on subsequent work. The main fact of 
the formation of a volatile compound is proved, though the mode of 
formation is not shown, and its applicability is not extended to the 
particular question at issue. 
Here again has Hamberg given us results which are trustworthy, 
and his two experiments are the only ones thus far in this historical 
sketch against which valid objection may not be raised, though in 
regard to the second I can only repeat what I have said of the first as 
to absence of detail in the method. 
Hamberg, assuming the volatilization to be proved, concludes that 
in the corpses of persons poisoned by arsenic a similar change takes 
place, that in the course of years arsenic is given off as a gaseous 
compound, and that this explains the disappearance of arsenic which 
has been observed or conjectured by many toxicologists in the exami- 
nation of parts of exhumed bodies. 
Stokes,* in 1888, during an examination of wall papers, fabrics, 
and domestic articles for arsenic, placed about 300 sq. inches (about 
0.19 sq. m.) of arsenical muslin in a glass tube connected with a 
smaller heated tube. Air was drawn through for six hours, and 
passed from the hot tube into an argentic nitrate solution. No ar- 
senic was detected in the hot tube or in the solution. The large tube 
was then heated to 38° and air passed through the system for six 
hours more, but with the same result. This experiment would only 
determine whether the arsenical color was itself volatilized, but the 
duration is so short and the test for arsenic so indefinite that the 
experiment is of little or no value. 
My friend Professor Kinnicutt, of Worcester, Mass., has very 
kindly allowed me to include here some experiments which he con- 
ducted about six years ago but has never published. 
1. A room 18 by 20 feet was selected, with a wall paper contain- 
ing 0.1 grain of arsenic per sq. yd. (7 8 mgr. per sq. m.). The win- 
dows and door were closed, and the air of the room was drawn at the 
rate of about 120 bubbles per minute through a chloride of calcium tube 
filled with cotton wool and then through 5% argentic nitrate solution. 
After seven days neither the cotton nor the silver solution contained 
any arsenic. The latter had a slight black deposit. The method of 
analysis was essentially the same as in my first series of experiments. 
2. A number of pieces of cardboard were covered, by means of 
* Chem. News, LVIII. 190. SANGER. VOLATILE COMPOUNDS OF ARSENIC. 
129 
starch paste, with wall paper containing arsenite of copper, so that 
in the surface exposed there were about 400 mgr. of arsenious oxide. 
These cardboards were then placed in a specially constructed tight 
box with glass windows, arranged so that air could be drawn from 
end to end. The air entering the box passed through a dilute solu- 
tion of sodic hydroxide. On leaving it passed through a chloride of 
calcium tube filled with cotton wool, next through a Liebig bulb tube 
with 5% argentic nitrate protected from the light, and finally through 
bulbs filled with nitric acid (sp. gr. 1.12). Air was drawn through 
the system for two and a half months, averaging seven hours per 
day. At the end of this time a large amount of mould had formed 
on the paper. The cotton wool gave a marked test for arsenic, but 
the silver solution did not show the slightest trace. The nitric acid 
evaporated with sulphuric acid was also free from arsenic. 
3. The box used in No. 2 remained over four years in the cellar 
of the laboratory, and had become filled with mould, the windows 
being covered with moisture. A similar series of absorbents was con- 
nected, and air was drawn through the system for a week, night and 
day. The cotton wool, silver solution, and nitric acid were tested as 
in No. 2, but in no case was any arsenic found. 
The evidence presented above, with the exception of the experi- 
ments of Fleck and the earlier work of Hamberg, was collected after 
my first series of experiments was completed. These, which were 
intended to repeat the work of Fleck and Hamberg, and which were 
based on the assumption that the volatile compound, if formed, would 
be arseniuretted hydrogen, are given below. On account of the nega- 
tive results they are not presented in as much detail as originally 
intended, for the conclusion derived from them at that time was 
shown to be erroneous by the results of the second series. 
First Series of Experiments. 
Fermentation in Solution. - Experiment 1. - 20 grams potassic ar- 
senite dissolved in water were mixed with syrup, flour, and part of a 
yeast cake, and placed in a large flask fitted with a double bored cork. 
Through one hole reaching to the bottom of the flask, passed a right- 
angled tube connected with the tubulus of a side-neck test-tube (A) 
the latter being half filled with a solution of argentic nitrate and 
fitted with a cork through which passed a right-angled tube to the 
bottom of the test-tube. In the second hole of the stopper of the 
VOL. XYIX. (n. S. XXI.) 9 130 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
flask was placed an empty Kempff washing bottle (B), reaching just 
below the stopper and serving as a safeguard against back pressure 
as well as to catch any of the arsenical mixture that might be mechan- 
ically carried up. Through the rubber stopper of the first washing 
bottle was passed a second (C), containing about 50 c.c. of the same 
argentic nitrate solution to absorb the volatile compound. This bottle 
was connected with the right-angled tube of a side-neck test-tube (D), 
similar in arrangement to A, and serving as a guard against contami- 
nation of the silver solution in C from this end. To the tubulus of D 
was attached the water-pump. The flask was kept at 30° for 36 
days and the fermentation was marked, air being drawn through 
nearly all the time. At the end there was no perceptible change in 
the solution in the bottle C. This solution was tested as follows. A 
clean new evaporating dish was heated with about 3 c. c. strong sul- 
phuric acid, and the acid after cooling was diluted with about eight 
parts of water and introduced into the Marsh reduction flask.* No 
mirror appeared in 45 minutes, at the end of which time was added 
the solution obtained from the argentic nitrate. This had been heated 
to boiling, and precipitated with hydrochloric acid, the filtrate being 
evaporated with the addition of a few drops of nitric and sulphuric 
acids until it fumed strongly. Water was then added, and the cold 
solution put into the reduction flask. No mirror appeared although 
the action continued for 45 minutes, thus showing no absorption by 
the silver solution of any volatile compound of arsenic from the 
fermenting mixture. 
Experiment 2. - In the following two experiments the dilution 
was made very great, in case this condition should affect the forma- 
tion of the volatile compound. The arrangement of the flask and 
rear guard tube (A) was as in Exp. 1. Next to the flask was 
placed a short straight tube filled with fused calcic chloride (B), 
and to this was connected a washing bottle (C) with 2% argentic 
nitrate. Diluted syrup solution and yeast were placed in the flask, 
and to it were added 10 c. c. of a standard solution of arsenious oxide 
equivalent to 10 mgr. As2O3. The apparatus closed at A was left for 
nine days at the ordinary temperature. Fermentation set in at once 
and continued until the end. The silver solution was somewhat 
darkened, probably by the action of light and some volatile organic 
compound. Air was drawn through the system until the air in the 
* The method used in all the experiments was the modification of the 
Berzelius-Marsh described by me in these Proceedings, XXVI. 24. SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
131 
flask had been several times replaced. The silver solution, treated as 
before, gave no arsenic. 
Experiment 3. - The arrangement of flask and tubes, contents of 
flask, etc., were as in Exp. 2, except that a tube containing cotton 
wool was used instead of calcic chloride. The action went on for 16 
days, and at the end of that time there was a slight grayish black 
precipitate in the silver solution. The latter, however, yielded no 
arsenic. 
Fermentation on Paper. - Experiment 4. - A large bell jar, having 
a tubulus at the top and standing on a well greased ground-glass plate, 
was fitted with a system of tubes and absorbents similar to those of 
Exps. 1-3. In the jar were placed several pieces of a wall paper con- 
taining 110 mgr. As2O3 per sq. m., giving a total amount of 67 mgr. 
over a surface of about 0.6 sq. m. The back of the paper was 
smeared with a paste of flour and syrup, to which part of a yeast cake 
had been added. Air was drawn through the system for fifteen days. 
There was apparently considerable reduction of the silver solution 
and a quantity of black precipitate. This was filtered off, and the 
filtrate treated as previously described. After a 45 minutes' test of 
the apparatus, the solution gave, after an hour's run, a scarcely 
perceptible deposit, which did not look like arsenic, and could not be 
proved to be arsenic. 
Experiment 5. - The apparatus was the same as in Exp. 4. 
Another wall paper was taken, having a surface of about 0.89 sq. in. 
and containing in itself about 45 mgr. As2O3. To the flour paste 
smeared on the back were added about 7 grams arsenious oxide. Air 
was passed through for 19 days, and at the end of that time the reduc- 
tion of the silver solution was more marked than in Exp. 4. The fil- 
tered solution was treated as before, and gave, after 30 minutes, a very 
slight deposit, not resembling arsenic, and giving no confirmatory test. 
Experiment 6. - This was a continuation of Exp. 5 with the same 
apparatus and prepared paper, but instead of the silver solution a 
small quantity of strong sulphuric acid was used as perhaps a better 
means of absorbing the volatile arsenical compound. Air was drawn 
through for 15 days. The acid was darkened and sulphur dioxide 
had been formed. The acid was evaporated with a little nitric acid, 
diluted, and added to the reduction flask, but no mirror of arsenic 
appeared in 30 minutes. 
Experiment 7. - This was a continuation of Exp. 5 in exactly the 
same manner, the sulphuric acid of Exp. 6 being replaced by a silver 132 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
solution. Air was passed for eight days, and the reduction was some- 
what less than before. The test of the solution was entirely negative. 
Experiment 8. - In order to try the effect of alkaline fermentation 
about 0.5 sq. m. of brown wrapping paper was smeared with flour 
paste containing 8.5 grams arsenious oxide and a quantity of lime, 
and placed in the same bell jar without removing the preparation used 
in Exps. 5-7. The total amount of arsenious oxide was therefore 
about 15.5 grams. Air was passed for 17 days. There was much 
mould in the bell jar, and the silver solution was slightly reduced. 
No arsenic, however, was found in it. 
Experiment 9. - In this and in the following experiment the main 
deviation from the previous trials was in the amount and character of 
the arsenic compound, and the duration of fermentation. In a large 
bell jar, fitted with a similar system of absorbents to that of Exp. 1, 
was placed about 1 sq. m. of a wall paper containing only a small 
amount of arsenic, and on this was smeared a paste of flour and syrup, 
to which had been added 10 grams arsenious oxide and part of a yeast 
cake. After action for 36 days, during which time air was drawn 
through slowly, the silver solution was examined but gave no arsenic. 
Very slight reduction had taken place, the light not being as strong as 
in the previous experiments. 
Experiment 10.-The conditions of this experiment were exactly 
the same as in the preceding, with the substitution of 10 grams of 
Paris green for the arsenious oxide. The result was also the same. 
Direct Experiments on the Air of Rooms. - Experiment 11. - The 
room in which this experiment was performed was a large attic 
chamber. The surface of paper exposed was about 60-70 sq. m., each 
containing 280 mgr. arsenious oxide. The frieze and ceiling con- 
tained traces only, 0.8 mgr. and 1.0 mgr. respectively, so that the total 
amount of arsenic may be estimated at about 18 grams. The occupant 
of the room spent much of his time in it, and showed symptoms attrib- 
utable to chronic arsenical poisoning. The room was at about 25°. 
In order to absorb the volatile compound, if present, a washing 
bottle similar to those used in the previous experiments was partly 
filled with a 2% solution of argentic nitrate and connected with an 
aspirator. In order to free the air from arsenical dust, it passed, 
before reaching the silver solution, through two tubes filled with 
cotton wool. In four days, the room being closed, about 750 litres of 
air were drawn through the bottle. There were then a few black 
specks in the solution. This, after filtration, was analyzed as before, SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
133 
the apparatus having been shown to be free from arsenic, and gave no 
mirror in 40 minutes. 
Experiment 12. - The paper in this room had a surface of about 
32 sq. m., each containing 30 mgr. arsenious oxide, making a total of 
about one gram, a rather small amount for the experiment and the 
size of the room, but the paper was not quantitatively analyzed until 
afterward. The room was warm, and was kept closed during the trial. 
No complaint had ever been made by the occupant of symptoms of 
arsenical poisoning. The apparatus was set up as in Exp. 11, and 
air was drawn through it rapidly for five days. No reduction of the 
silver solution was visible. The latter, after treatment in the usual 
manner, gave no indication of arsenic. 
Experiment 13. - This room was considerably smaller than the 
other two. The total amount of arsenic in it was about 3.6 grams. 
No symptoms of arsenical poisoning were ever noticed by the occu- 
pant, a boy in vigorous health, who occupied the room only at night. 
The room was closed and kept at 25°. The apparatus was set up 
as in the previous experiments and 6,720 litres of air were drawn 
through the system. There was no perceptible darkening of the sil- 
ver solution, and, on analysis by the same method as in the previous 
trials, it was found to be free from arsenic. 
Experiment 14. -The conditions under which this experiment was 
performed were, as regards warmth and dampness, more favorable to 
the formation of a volatile arsenical compound than those of the three 
previous trials. The occupant of the room suffered from symptoms 
which were clearly due to arsenic.* The total amount of arsenic 
present in paper and curtains was about 3.9 grams. During the ex- 
periment the room was closed, and the air was at about 30° and damp. 
The apparatus was similar to that used before, except that between 
the guard tubes of cotton wool and the silver solution was placed a 
small quantity of strong sulphuric acid, just as in Exp. 6, as an 
additional means of absorption. Air was drawn through the system, 
at intervals for 22 days, the total amount being 1,323 litres. The acid 
had increased in volume considerably by absorption of moisture, but 
there was no evidence of reduction as in Exp. 6. The silver solution 
was slightly darkened and contained a slight black precipitate. Nei- 
ther sulphuric acid nor silver solution gave any test for arsenic. 
In none of the above trials was any alliaceous odor observed, either 
from the fermenting material or in the air of the rooms. 
* This case (2) is described in the following article. 134 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
The result of these fourteen experiments was entirely negative, 
though they were carried on under widely varying conditions, and by 
a method better adapted to detect small quantities of arsenic than any 
before used. On referring to the previous work cited above, the evi- 
dence seemed to be greatly in favor of the conclusion reached by my 
own results, the work of Hamberg being the only positive evidence 
in favor of the formation of a volatile arsenical compound. Yet there 
were two points that still gave hope of the correctness of the volatile 
compound theory : first, the clinical evidence of undoubted poisoning 
where there was no chance for absorption of dust; and secondly, the 
fact that in none of the experiments had any quantity of air been 
tested which approached the amount daily inhaled by an average 
man.* The amounts used would have perhaps sufficed if the volatile 
compound were arseniuretted hydrogen, but, supposing it to have been 
a compound not completely absorbed by argentic nitrate, (as it turns 
out to be,) a very small amount might have escaped absorption, which 
as arseniuretted hydrogen would have been easily found. 
Though I did not consider the question fully settled, I thought the 
evidence against the volatile compound theory sufficiently good to 
warrant the publication of the results thus far obtained. This I 
was preparing for when notice of the preliminary paper f of Gosio 
reached me. I wrote to Dr. Gosio at Rome, who after the com- 
pletion of his work sent me, in September, 1892, copies of the two 
monographs cited below, and at the same time, with the greatest 
kindness and consideration, placed at my disposal an admirably pre- 
pared set of tube cultures of Penicillium brevicaule. 
The Work of Gosio. 
Gosio's classic monograph t has received little attention from the 
abstracters, and I therefore present his results here in considerable 
detail. I judge that much of the work mentioned in my historical 
sketch has escaped his notice, since he cites Selmi as the most reliable 
authority for the volatile compound theory, and refers to the very 
insufficient results of Forster as the basis for support of the dust 
* Estimated to be about 12,000 litres in 24 hours, from the statement of Fos- 
ter, Textbook of Physiology, 5th ed., p. 551, that the amount of tidal air is 
500 c.c., and that the number of respirations is 17 per minute. 
t Science, XIX. 104, abstract from a preliminary communication to the Con- 
gress of Hygiene held in London in 1891. 
1 "Azione di Alcune Muffe sui Composti fissi d'Arsenico," Ministero dell' 
Interno, Laboratori Scientific! della Direzione di Sanita, Roma, 1892. SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
135 
theory. He does not mention Hamberg's first paper, and has appar- 
ently seen only the wretched abstract of the second quoted above, for 
he is unaware of some important points in that paper which were 
similar to his own experience, fie quotes the work of Fleck and of 
Giglioli, and that of Johannson * and Binz f on the tolerance of arsenic 
by saprophytes. But the most important result he considers to have 
been obtained by Bischoff, though his judgment is influenced undoubt- 
edly by the fact that his own results have shown the odor to be a 
positive indication of the presence of the volatile compound, whereas, 
in Bischoff's experiment it was only an assumption, and not backed 
by experimental proof. Other investigators than the above are not 
mentioned. 
Gosio at the inception of his work considered that a volatile com- 
pound could be formed by the action of mould on arsenical organic 
matter, though positive proof was wanting, and the mechanism of the 
reaction was entirely inexplicable. He set himself the following plan 
of work : - 
1. To show whether from arsenical culture ground, exposed to 
spontaneous inoculation from various surroundings, there could be 
developed a volatile arsenical compound. 
2. If so, to isolate the germs which could effect this transformation 
and to characterize them. 
3. To discover in what arsenical compounds the activity of the 
organisms manifests itself most markedly; whether this is to be 
extended to products used in the arts; and to find out what condi- 
tions favor and what retard the action. 
4. To study the volatile compound. 
5. To describe the mechanism by which this gas is produced 
through the biological energy of micro-organisms. 
The first question was answered by an experiment similar to Bis- 
choff's. Potato pulp containing from 0.5 to 1 % of arsenious oxide was 
exposed to the air of a cellar. Abundance of mould appeared in a 
short time, and at the end of a week an intense alliaceous odor was 
developed. The pulp was then placed in a glass vessel, through 
which air was drawn for two weeks into a hot solution of argentic 
nitrate, the air being filtered by cotton wool. The usual blackening 
took place, on which Gosio very properly lays little stress, and the 
solution, freed from silver by hydrochloric acid and filtration, gave 
" characteristic reactions for arsenic." 
* Archiv f. exper. Pathol., II. 503. t Ibid., XL 200; XIV. 345. 136 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
A similar experiment, in which 120 mgr. arsenic oxide were used, 
was completed quantitatively, and by the Berzelius-Marsh method a 
ring of arsenic was obtained weighing 2.8 mgr., corresponding to 
4.3 mgr. As2O5, or 3.6% of the amount taken. This is unfortunately 
the only quantitative work in the paper, and I cannot place much 
reliance on it owing to the inaccuracy of the gravimetric Berzelius- 
Marsh method with such small amounts. 
Pure cultures were now made of some of the moulds developed 
in the above experiments, and there were isolated Penicillium glau- 
cum, Aspergillum glaucum, and Mucor mucedo. Cultivations were also 
made of Bacillus radiciformis, B. prodigiosus, B. subtilis, and Sarcina 
lutea. All were then cultivated separately on sterilized arsenical 
preparations. The odor was noticed only from A. glaucum and Mucor 
mucedo. The latter, being a widespread and easily cultivated mould, 
was selected for further experiments. 
Ten Erlenmeyer flasks were fitted with two-holed rubber corks and 
two right-angled tubes, one passing to the bottom of the flask, the 
other to just below the cork, each outer end being plugged with 
cotton wool. Potato pulp containing arsenious oxide and a little tar- 
taric acid was placed in the flasks, which were sterilized, inoculated 
with a pure culture of mucedo in agar, and connected in series. In 
the rear was placed a wash bottle of water, in front a 5% solution 
of argentic nitrate, and a Bunsen pump drew air through the system. 
The temperature was that of ordinary summer heat. After 28 days 
the presence of arsenic was established in the filtered solution. 
The solution before filtration contained a considerable quantity of 
a yellow crystalline substance which quickly darkened. This Gosio 
evidently hoped to connect with the compound 3AgNO3.AsAg3 of 
Poleck and Thummel,* overlooking the fact that the latter is formed 
only in very concentrated solution. On testing the substance no arse- 
nic was found. 
The activity of Mucor mucedo was further shown by varying the 
methods of culture, the nutritive soil, and the quality and quantity of 
the arsenic compounds. Scheele's and Schweinfurth green, in pro- 
portions varying from 0.001 to 0.1% of the pulp, gave reactions, but 
realgar and orpiment gave no odor. Yet, if the action on the sul- 
phides was protracted through many months, there was a slight 
development. After chemical analysis had confirmed the odor, the 
latter alone was considered a sufficient indication of arsenic in most 
* Archiv d. Pharm., CCXXII. 8. 137 
SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
of the succeeding experiments. To try the action on paper, a tight 
box was lined with sterilized paper colored by Schweinfurth green 
and fastened by sterilized starch paste which had been inoculated 
with mucedo. Air was drawn through the box for 39 days into 
argentic nitrate which then gave a positive test for arsenic. 
The sensibility of the mucedo varies with different conditions: 
humidity, amount of oxygen present (the formation of gas ceases if 
air be lacking), and the quantity and quality of the arsenic compounds. 
The best results were obtained in ground containing 0.01 to 0.05% of 
substance, while 4 to 5% distinctly retarded the growth. Arsenic acid, 
arseniates, or alkaline arsenites gave the best results. There can be 
a tolerance for high doses established, however, if the mould is habit- 
uated to a progressive increase. The action goes on better in solid 
ground than in liquid, and the best nutritive material is a carbohy- 
drate. In albuminoid matter there was but little action, whereas in a 
mixture of albumen and glucose, it was intense. Whenever the 
mucedo showed intolerance, other moulds grew which do not decom- 
pose arsenical matter, e. g. P. glaucum. This explains the failure of 
other observers (including myself), who used large amounts of arsenic 
and yet obtained a quantity of mould. 
The action of other moulds was examined in the same way, but it 
was necessary in certain cases to lessen the amount of arsenic. By 
this means a mould corresponding to the properties of Aspergillum 
virens was found to react. Very slight effects were obtained from 
Sterigmatocystis ochracea, Cephalothecium roseum, and Mucor ramosus. 
Finally, from a piece of carrot left in the open air, a new mould was 
isolated which proved to be identical with the Penicillium brevicaule 
discovered by Saccardo on decaying paper. Experiments on this 
mould showed it to be capable of more intense action than any other. 
With milk culture Gosio claims to recognize the odor from 0.02 mgr. 
of sodic arsenite and thinks it may be still more delicate. In the 
experiments with P. brevicaule, the absorbent was an acid solution of 
potassic permanganate, but the strength as well as the subsequent 
treatment is not given. The extreme sensibility of this mould led 
Gosio to propose its use as a means of testing for arsenic in toxico- 
logical work, and the second of his papers is devoted to the working 
out of this method. 
The power of decomposing arsenical organic matter is proposed as 
a means of distinguishing between two moulds of similar properties. 
As " arsenio-bacteria " Gosio specifies those which have a prompt, 
intense, and lasting action. He thinks that all micro-organisms may 138 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
have a slight action in the course of months or years, being led to 
this conclusion partly by Hamberg's work, though he has no data of 
his own to prove the theory. 
The investigation of the chemical nature of the volatile compound 
was begun on the assumption that arseniuretted hydrogen was formed, 
as the silver solution was reduced and arsenic found in the solution. 
On attempting, however, to precipitate argentic arsenite from solution 
by ammonia, it was found that the excess of alkali liberated a vola- 
tile substance with an intense garlic odor. The following examina- 
tion was then made. The filtered silver solution was treated with 
excess of potassic hydroxide in a flask, and the product of the action 
led over lime and caustic potash to free it from carbon dioxide. The 
gas then passed over hot cupric oxide and the combustion product, 
led into baric hydroxide, caused a turbidity. The residue in the 
cupric oxide tube was digested for two days in cold dilute potassic 
hydroxide, filtered and washed. The solution was precipitated by 
sulphuretted hydrogen and the filtrate acidified with hydrochloric acid. 
The precipitate from the latter oxidized with nitric acid gave reac- 
tions for arsenic in the Marsh apparatus. We shall have to take it 
for granted in the above experiments that the carbon dioxide was 
all held back by the absorbents, and that the cupric oxide was 
non-arsenical. 
Another filtered silver solution was made alkaline with potassic 
hydroxide, and air passed from it into platinic chloride for two days. 
The air from a series of flasks was also passed into this absorbent for 
ten days. In both cases no satisfactory results were obtained. 
In the solution after treatment with alkali, arsenic was looked for, 
but only faint traces were found. This would be against the forma- 
tion of arseniuretted hydrogen, yet Gosio inclines to the belief that 
there may be traces of it formed. 
Considerable space is given to discussing the mechanism of the 
reaction, yet, in view of the fact that the compound has not been 
isolated, such discussion is purely speculative. Gosio refers to the 
work of Pollaci,* Selmi,f and Fitz and Mayer J on the formation of 
hydrogen by action of lower organisms, and quotes the statement of 
Nencki § that bacteria may decompose water into II and OH, which 
would cause a hydrogenization and a hydroxylization, a double action 
* Reference not given by Gosio. 
t Presumably the same reference as given by me above, 
t Ber. d. deutsch. chem. Gesells., XI. 1880; XII. 474. 
§ Ibid., XII. 474. SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
139 
which he evidently thinks may take place in this case, giving rise to 
arseniuretted hydrogen and an arsenical compound of carbon with the 
hydroxyl group. On the other hand, he refers to the work of 
Missaghi,* which opposes the formation of hydrogen by moulds. 
The second paperf of Gosio need be referred to very briefly. The 
action of P. brevicaule proved so sensitive as to suggest a very delicate 
method for the detection of arsenic in presence of large amounts of 
organic matter. The method is carried out as follows. A test-tube 
is constricted about 20-30 mm. from its lower end, and the bulb thus 
formed filled with moist cotton wool. A strip of paper is cut in halves 
and the suspected substance placed between the slices, which are then 
put into the test-tube and sterilized. Inoculation is then made, and in 
a day or two the characteristic odor is developed. The temperature is 
best about 37°. Should further proof be desired, a rubber stopper 
with right-angled tubes may be inserted in the test-tube, and air 
drawn slowly through it into a sulphuric acid solution of potassic per- 
manganate kept at 60 to 70°. This solution after proper treatment is 
introduced into the Marsh flask. 
Undoubtedly in cases where the amount of arsenic is very small, and 
in contact with a large amount of organic matter, this method would 
be excellent, but I cannot see that in general medico-legal work it 
has any advantage over the common methods, particularly as it 
requires much time and cannot be made quantitative. It is simply a 
very interesting micro-biological method. The exceedingly great 
delicacy claimed for it (1 part of sodic arsenite in 1,000,000 being 
detected in a milk culture) is not surprising when we consider the 
amount of substance that can be recognized by the sense of smell, 
E. Fischer and Penzoldt,J for instance, claiming to have detected one 
four hundred and sixty millionth of a milligram of mercaptan. 
The correctness of Gosio's work is unquestionable, and to him is 
due the credit of settling this much vexed question. Yet it seemed 
to me that the importance of the matter demanded a substantiation of 
his results by repetition of his work, particularly as so many observers 
beside myself had obtained opposite results, and would be better satis- 
fied to know that the action of the moulds had been confirmed by 
another investigator in another country. I have therefore made 
some experiments similar both to those of my first series and to those 
* Gazz. chim. Ital., V. 419. 
t " Sul Riconoscimento dell' Arsenico per Mezzo di alcune Muffe," Roma, 
1892. 
t Ann d. Phys. u. d. Chem., CCXXXIX. 131. 140 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
of Gosio, using the material from the culture tubes sent me by him, 
which were five in number and contained P. brevicaule in potato 
strips to which had been added different preparations of arsenic. 
Second Series of Experiments, using P. brevicaule. 
Experiment 15. - One gram arsenious oxide was mixed in a litre 
flask with flour and water which, without sterilization, was inoculated 
from the tube marked " patata esente di arsenico." A similar system 
of tubes to that described in Exp. 3 was attached to this flask, including 
the usual absorption bottles filled with 2% argentic nitrate, and air was 
drawn through the system for about two weeks, during which time the 
formation of mould was abundant and fermentation marked. The 
reduction of the silver solution was slight. On opening the flask no 
odor was noticed except that characteristic of mould. Although there 
was little evidence of the formation of a volatile compound, the silver 
solution was tested in a similar manner to that described in Exp. 1, 
but with entirely negative result. 
Experiment 16. - One gram arsenious oxide was mixed with un- 
sterilized flour paste, and, after inoculation with the same preparation 
as in Exp. 15, smeared on a large sheet of filter paper. This was 
placed in a bell jar over a ground-glass plate, and the jar fitted with 
a system of tubes and absorbents similar to that described in Exp. 4. 
Air was drawn through for about two weeks. The formation of 
mould was abundant, but no alliaceous odor was observed. The sil- 
ver solution was but slightly reduced and gave no test for arsenic. 
In these two experiments, the P. brevicaule could not tolerate the 
amount of arsenic under the conditions as well as the common moulds, 
hence the latter flourished to the entire exclusion of the former. 
This was shown by Mr. Roscoe Pound, of Lincoln, Nebraska, who 
very kindly examined the sheet in Exp. 16 and found the only 
Penicillium present to be P. crustaceum. 
The conditions of Exps. 15 and 16 are not unlike those of the 
previous negative experiments. 
Experiment 17 a. - In this the method of Gosio was quite closely 
followed. Three 250 c. c. Erlenmeyer flasks were fitted with rubber 
stoppers through which passed two right-angled tubes, one reaching 
nearly to the bottom of the flask, the other to just below the cork. 
The outer end of each tube was plugged with cotton wool. Sufficient 
potato pulp was placed in each flask to make a layer of about half an 
inch, and it was moistened with a solution of sodic arseniate contain- 
ing about 0.5 gram to 100 c. c. Each flask contained about 100 mgr. SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
141 
As2O5. They were then heated for two hours in a steam sterilizer 
and allowed to stand 24 hours. This was twice repeated. Each 
flask was then inoculated with a sterilized platinum point from the 
tube marked " patata bagnata in una soluzione di As2O5." The 
three flasks were then connected together and in the rear was joined 
a side-neck test-tube containing 2% argentic nitrate. In front was 
placed an additional layer of cotton wool in a chloride of calcium tube, 
then two silver solutions of the same strength as the first. The joints 
of the apparatus were wired and were tight. A current of air was 
drawn very slowly through the system day and night, the amount 
being measured. In one day the growth at the points of inoculation 
began, and in three days there was a patch half an inch in diameter 
around each spot. The silver solution had darkened slightly. The 
temperature during the trial was about 25°. 
At the end of twelve days, as it became necessary to change the 
place of Experiment, the flasks were disconnected and packed for trans- 
portation. Up to this time no difference could be noted between this 
experiment and the many preceding, except that the mould was in 
smaller quantity and apparently more homogeneous. The first silver 
solution was somewhat reduced, there being a slight black deposit, but 
the second was not changed. But as soon as the flasks were discon- 
nected (they were not uncorked) an alliaceous odor could plainly be 
perceived at the tubes, a point that I had never observed in any pre- 
vious experiment. The silver solutions were then tested, the method 
being for certain special reasons slightly modified. The unfiltered 
solution was precipitated by a very slight excess of sodic chlo- 
ride, and the filtrate evaporated with sulphuric acid until it fumed 
strongly. The diluted residue was boiled with a very little sodic 
sulphite, and the excess of sulphur dioxide expelled. The cooled 
solution was then introduced into the Marsh flask which had been 
running one hour without sign of a mirror in the deposition tube. 
Here may it be said that all reagents used had been subjected to the 
most rigid test, the stream of hydrogen from the generator not giv- 
ing any arsenic whatever in a seven-hour run. Twenty-five minutes 
after introduction of the prepared solution a clearly defined mirror of 
arsenic was deposited which was the first that I had obtained in my 
experiments on this subject. The amount was small, about 0.01 mgr., 
but, taken in connection with the odor, it was very satisfactory con- 
sidering the small amount of mould and the duration of its action. 
One hundred and five litres of air had been drawn through. The 
second silver solution treated in precisely the same way gave no 
mirror. 142 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
b. Three weeks elapsed before the experiment could be con- 
tinued, during which time the flasks remained sealed by the cotton 
wool. In two of them the growth did not seem to have increased 
much, but in the third the ground was completely filled with mould, 
which did not seem, however, to be entirely homogeneous. I am not 
sure that the stopper of this flask may not have been slightly loosened. 
The odor of garlic was very strong. 
The flasks were connected with silver solutions as before, and air 
led through each day for 17 days. In four days there appeared on 
the lower end of the entrance tube of the first silver solution a dark 
mirror, which increased slightly and was apparently the only deposit 
formed. The temperature during the first week was about 20°, but 
afterwards about 25°. At a very rough estimate 170 litres of air 
were passed through the system. 
The first silver solution was poured out of the bottle, and the latter 
merely rinsed with water. The solution was heated nearly to boiling, 
and excess of hydrochloric acid was added. At this point I was 
struck by the strong odor coming from the warm mixture, it being 
noticeable at a distance of two feet from the beaker. It strongly 
resembled the garlic odor of arsenic, and also recalled the odor from a 
solution of iron in dilute acid. My assistant, in making the previous 
precipitation with sodic chloride, noticed no odor. The odor grew 
weaker as the mixture was kept warm, but the argentic chloride was 
filtered before it had entirely disappeared. The filtrate, after addition 
of a little more nitric acid, was evaporated with sulphuric acid to 
fuming, diluted, and added to the Marsh flask which had been run- 
ning for forty minutes without a trace of arsenic. In ten minutes a 
mirror began to appear, was very heavy in thirty minutes, and at its 
maximum in fifty. It was clear and well defined, but too heavy 
for accurate estimation. I placed it at 0.07 mgr., which is a low 
estimate. 
Besides the mirror of silver (?) on the end of the tube in the absorp- 
tion bottle, there was evident on closer inspection a small amount of 
a nearly colorless (perhaps slightly yellow) gelatinous-looking sub- 
stance adhering to the bottom and walls of the bottle. This dissolved 
easily in the few drops of strong nitric acid added to dislodge the 
heavier black deposit, though the action of the acid upon it was 
masked by the nitrous fumes from the solution of the mirror. The 
solution was precipitated with hydrochloric acid, evaporated to fum- 
ing with sulphuric acid, diluted, and added to a Marsh flask which had 
been running for 30 minutes without evidence of arsenic. A mirror 143 
SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
appeared in 30 minutes which was at its maximum in 60. The 
amount formed was 0.025 mgr., making 0.095, or probably 0.1 mgr. 
in all, from this solution. 
It was possible that the first silver solution had not absorbed all 
the volatile compound, as was conjectured in Hamberg's case. Bear- 
ing in mind the probable volatilization of arsenic in the method 
employed in the first solution, the second, which contained little or no 
deposit, was evaporated with considerable nitric acid to incipient 
fusion, during which no alliaceous odor was noticed. The residue 
was taken up with dilute nitric acid, precipitated with hydrochloric 
acid, and the filtrate, after evaporation with sulphuric acid and dilu- 
tion, added to a Marsh flask in which the absence of arsenic had 
been shown by a 40-minute run. After an hour, the mirror, which 
appeared slowly, was at its maximum, and was estimated at 0.015 
mgr. This shows conclusively that argentic nitrate in such dilution 
does not absorb the volatile compound with any degree of completeness. 
To prove that no arsenic could have entered from the air of the 
room, the rear solution of silver was treated in the same manner, and 
gave no trace of arsenic. 
The total amount of arsenic (as As2O3) obtained from this series 
of flasks was 0.12 mgr. No further satisfactory quantitative result 
can be adduced for many reasons. During the interval between Exps. 
17 a and 17 5, much of the compound may have escaped; the silver 
solutions did not absorb all of the compound, and the method of 
treating the first solution at least was incorrect, being based on the 
old assumption that arseniuretted hydrogen was the product. Hence 
0.12 mgr. does not represent by any means what may have been 
formed. Yet if one reckons 300 mgr. of arsenic (as As2O3) to the 
flasks, the amount recovered is 0.04% of this, a proportion which for 
all we know may be 100 times too small. 
The flasks were now uncorked. The odor, though fainter, was 
distinctly perceptible and was confirmed by others in the laboratory. 
Dr. W. G. Farlow has had the kindness to examine the growth for 
me, and reports that the first two flasks contained only P. brevicaule 
" fruiting and in good condition," while the third, which I suspected 
was not homogeneous, contained also P. glaucum, though the amount 
" as compared with the P. brevicaule is less than one would suppose 
on looking at the flask without examining microscopically." 
Though the above experiment confirmed the results of Gosio to my 
complete satisfaction, the following trial is of great interest on account 
of the small amount of arsenic and its source. 144 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
Experiment 18.-Three 200 c.c. Erlenmeyer flasks were fitted as 
in Exp. 17, with rubber stoppers and tubes, the latter plugged with 
cotton wool. A wall paper was selected having 115 mgr. arsenious 
oxide per square meter, the color, a dark red, suggesting an aniline com- 
pound mordanted with an arseniate. 3 square decimeters of this were 
cut into strips and placed between several slices of potato, which were 
put into each flask. The total amount of arsenic used was 3.45 mgr., 
reckoned as As2O3. The flasks, after addition of a little water, were 
sterilized for two and a half hours at 100-105°, and showed no evi- 
dence of mould for six days afterward. The potato, which was still 
moist and impregnated with the red coloring matter, was then inocu- 
lated with the culture in the tube marked " patata contenente una 
striscia di tappezzeria arsenicale," and the flasks were connected with 
a series of absorbents similar to that of Exp. 17. The current of air 
was not drawn through the system until the flasks had stood for a 
week, the temperature being from 20 to 25°. No mould appeared for 
four days, and the growth was then very slow, was confined to the first 
two flasks, and the amount was very small. Indeed, after 17 days 
had passed without much apparent action, the silver solution being 
but slightly affected, I disconnected the flasks, not intending to pursue 
the experiment further. Yet on opening the flasks the alliaceous 
odor though faint, was perfectly plain, and I proceeded to test the 
first silver solution. This was poured out, and the very slight deposit 
removed with a little nitric acid was added to the solution. The latter 
was evaporated with nitric acid nearly to fusion, taken up with dilute 
nitric acid, desilverized, and prepared as usual for the Marsh flask. 
This had been in action 40 minutes, and was free from arsenic. At 
the end of an hour after introducing the solution there was a small but 
perfectly plain mirror, which I estimated at 0.005 mgr. The second 
silver solution was not examined. 
Dr. Farlow kindly examined the first flask of the series, and found 
" P. brevicaule in good condition but not pure, for there was another 
species of Penicillium present not in very good fruit. The second 
species may have been a small form of P. glaucum, but I do not 
think I can say certainly from the material examined, which was too 
young." 
The amount of the volatile compound determined in this experi- 
ment is 0.14% of the total present. This estimate is more accurate 
than in Exp. 17, and the chief error is in the absorbent, though the 
amount is only a part of what might have been formed in the course 
of time. SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
145 
The reagents used in Exps. 17 6 and 18, being in another labora- 
tory, were subjected to the same rigid tests, and the absence of arsenic 
was proved. The dishes and utensils were proved free by blank 
tests. 
Discussion. 
The scope of this paper has gone far beyond my original intention, 
which, as stated above, was simply to repeat the work of Fleck and of 
Hamberg. As the important results of Hamberg and of Gosio have 
not been given the publicity due to them, not to speak of the compara- 
tive obscurity into which the work of many of the other investigators 
has fallen, I feel that the somewhat protracted review of the work 
that I have here presented will make the subject clearer, and will 
serve to place more surely beyond cavil the fact that a gaseous or 
volatile compound of arseuic may be generated from decaying ar- 
senical matter; hence the possibility of chronic poisoning from the 
presence of such a compound in the air of rooms papered with arseni- 
cal paper. 
Of the experiments mentioned in the historical sketch, those of 
Schmidt and Bretschneider, Fleck, Hamberg, Selmi, Bischoff, Gigli- 
oli, and Kinnicutt are the most important. The others need not be 
considered, either because there was little or no chance in them for 
decomposition by mould, or on account of imperfect methods of ex- 
perimentation or analysis. In the cases of Hamberg and Bischoff 
there was undoubtedly a volatile compound formed, though Hamberg 
proved it and Bischoff did not. Fleck and Selmi do not show con- 
clusively that it was present. 
The adverse results of the other four investigators, as well as those 
of my first series, are very easily explained. There was either too 
much arsenic for the arsenio-bacteria to tolerate, or else the latter 
were not present. It is worthy of note that, with the exception of 
Hamberg's experiments, whenever the unsterilized matter was allowed' 
to decompose in a closed vessel, no arsenical "compound was evolved, 
while exposure to spontaneous inoculation in the air developed an odor. 
This would seem to point to a tolerance when fresh germs can gain 
access to the material. In my own case I am inclined to think that 
absence of the specific bacteria was the chief reason for failure, though 
in many cases I used large amounts of arsenic. As to my experiments 
on the air of rooms, it is quite possible to explain the negative results 
by the choice of reagents and the amount of air aspirated. We have, 
however, sufficient evidence from Hamberg on this point. 
VOL. XXIX. (n. S. XXI.) 10 146 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
The conditions necessary for the action of the moulds, especially 
the amount of arsenic and the quality of the culture ground, explain 
why the action has not been earlier discovered. Though it is not 
certain but that many moulds decompose arsenical matter, yet the 
intense action is thus far confined to four, Penicillium brevicaule, 
Mucor mucedo, Aspergillum glaucum, and Aspergillum virens. Fur- 
ther research may succeed in finding others. It is worthy of note 
that the most active mould is that which was discovered on decaying 
paper, and it must not be forgotten that a small amount of arsenic in 
a wall paper may be quite as good a source of the volatile compound 
as a very large amount. 
I have not made any investigation into the nature of the compound, 
as such work would be trespassing on Gosio's field. I think the 
chances are that no arseniuretted hydrogen is formed, but that we 
have to deal solely with an organic compound of arsenic. This may 
perhaps form a "molecular " compound with the argentic nitrate, 
which, when the latter is acted on by hydrochloric acid or an alkali is 
set free. The odor of the solution was noticed by Hamberg, Gosio, 
and myself. Hamberg does not say whether it appeared after adding 
hydrochloric acid or in neutral solution. Gosio obtained it on adding 
alkali, and did not apparently detect it in the acid solution, while I 
discovered it in the desilverizing. Hamberg's yellow deposit may be 
identical with that noticed by Gosio and me, although Gosio does not 
agree with us in the finding of arsenic. 
Hamberg and Gosio infer that the dilute argentic nitrate solutions 
absorbed only a part of the compound, and my experiments confirm 
this inference. Potassic permanganate probably oxidizes it com- 
pletely. The non-absorption of the silver solution is an argument 
against the compound being arseniuretted hydrogen, for I have satis- 
fied myself by experiment that a 2% argentic nitrate solution absorbs 
that gas completely when in small amounts, even when the gas is very 
greatly diluted with air.* 
The use of argentic nitrate may partially account for some of the 
negative results of former investigators. With such an absorbent 
and the use of the simple Marsh test a comparatively large amount 
of the compound might have escaped notice. 
* Although the argentic nitrate absorbs the arseniuretted hydrogen com- 
pletely, yet when small quantities of arsenic are used, the amount recovered 
from the solution is rarely over 50% of the amount taken. Some rather odd 
results were obtained in investigating this question, the consideration of which 
is reserved for another paper. 147 
SANGER. - VOLATILE COMPOUNDS OF ARSENIC. 
In considering the nature of the compound, the only definite facts 
obtained are that it is formed in presence of oxygen, that the develop- 
ment is best from carbohydrates, and that arsenious or arsenic acid 
and their salts are best suited to the development. The only conclu- 
sion that may be drawn is that the volatile compound is an organic 
derivative of arsenious or arsenic acids. Yet the properties are such 
that it has little resemblance to any of these derivatives thus far 
isolated. Much work remains to be done before the composition can 
be determined, and Gosio is continuing his research to that end. 
In this connection the researches of Selmi * are interesting. From 
a corpse, in which the presence of arsenic was established, he isolated 
a ptomaine in small quantity, but the test for arsenic in it was nega- 
tive. In the stomach of a hog,f saturated with an arsenic solution 
and left to decompose, he was able to isolate two bodies containing 
arsenic. The first was obtained by distillation with steam, and had 
an intensely poisonous action like strychnine. The second was found 
in the residue from distillation, and the action of this resembled that 
of the ptomaines. In the urine of a dog $ poisoned by arsenic Selmi 
finds a volatile arsenic compound with tetanizing action, and considers 
it identical with the first of the two previously described. In no case 
were these compounds found in quantity sufficient to make an attempt 
at determining their composition. Husemann,§ referring to Selmi's 
work, thinks that an arsenical ptomaine could be generated from 
arsenical paper and paste, yet the properties of the volatile compound 
and the fact that it is best formed in non-nitrogenous ground seem 
to be against the formation of a ptomaine from these materials. 
Washington University Chemical Laboratory, 
Saint Louis, September, 1893. 
* Atti della R. Accad. dei Lincei, [3], II., June 2, 1878. 
t Mem. d. Accad. d. Scienze, Bologna, [4], I. 299. 
t Ibid., [4]. II- 3. 
§ Arch. d. Pharm., CCXIX. 415. 148 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
V. 
ON CHRONIC ARSENICAL POISONING FROM WALL 
PAPERS AND FABRICS. 
Charles Robert Sanger. 
Received November 9, 1893. 
During the spring of 1886, while assistant in the Harvard Labora- 
tory, several cases of chronic arsenical poisoning from wall papers 
were brought to my notice, as the suspected papers and fabrics were 
sent to me for analysis. In many cases an examination of the urine 
for arsenic was made, this being done under the supposition that the 
elimination of arsenic in cases of chronic poisoning had been well stud- 
ied. I was surprised to find, however, that analyses of the urine in 
such cases had been comparatively rare, and that little or nothing was 
known at that time of the elimination of arsenic under the conditions 
of chronic poisoning from wall papers. 
Some of the results of my work were read, by invitation, at a meet- 
ing of the South Middlesex (Massachusetts) Society for Medical Im- 
provement in the summer of 1886, but were not published, as so much 
reference and analytical work remained to be done before the paper 
could be presented in proper form. I was then called from Cam- 
bridge, and for three or four years the completion of the paper was 
continually prevented by other duties. In the mean time the analysis 
of the urine became recognized as a necessary step in the diagnosis 
of chronic arsenical poisoning from wall papers, and the records of 
such analyses have been frequent, chief among them being the paper 
of Putnam,* in March, 1889. In nine of the cases cited in this article 
the analyses had been made by me, and were sent to Dr. Putnam at 
his request. 
Although so much time has elapsed since my work was undertaken, 
and the cases, as far as the actual poisoning goes, are merely additions 
to the already long list, yet many facts brought out during the prepara- 
tion of the paper make it still worthy of publication. Two years ago 
* Bost. Med. Surg. Journ., CXX. 235. SANGER. - CHRONIC ARSENICAL POISONING. 
149 
I was about to present the results I had so far obtained, as my nega- 
tive experiments on the decomposition of arsenical organic matter by 
mould had enabled me, as I thought, to suggest a possible explanation 
of the source of wall paper poisoning, if we had to rely on arsenical 
dust alone as a mode of causation. 
The same reasons that led to my postponing the publication of that 
paper have delayed the appearance of this, and the later results of 
the former investigation have given a far closer insight into this much 
vexed question. 
I propose first to give the record of cases that I have found which 
include analytical work, then the cases that came to my notice in 
which analytical results on wall paper and urine may be compared, and 
then to discuss the cause of wall paper poisoning in the light of the 
chemical and biological facts brought out both by this paper and the 
foregoing. 
I have hesitated to introduce the medical side of the cases, but have 
considered it necessary to the completeness of the paper. The cases 
are stated, however, either as I found them or as they were given to 
me. I have further endeavored not to venture any opinion but what 
might be advanced from the chemical evidence. Whatever may be 
said of the suggestions offered, the facts are laid before the medical 
profession for its information and consideration. 
Historical. 
Previous to 1886, the cases of chronic poisoning from wall paper 
in which arsenic has been found in the urine are as follows. 
Lorinzer * of Vienna, in 1859, gives the following cases, the analy- 
tical work being done by Kletzinsky : - 
1. A girl of seventeen had occupied for two years a room of which 
the walls were colored by Mitis green. The symptoms were loss of 
appetite, headache, nausea, unquiet sleep, pains in the shoulder, erup- 
tion in the knee joint, constipation. The patient was always pale, 
with sunken cheeks and dark rings under the eyes. She was removed 
to another room and given potassic iodide, six grains daily, with warm 
bath twice a week. In two months she was restored to her normal 
health. The urine was not examined for arsenic. 
2. A woman fifty-four years old had occupied for some years a 
room which was found to have a paint or wash containing quantities 
* Wiener Med. Wochenschrift, 1859, Ileften 43 and 44. 150 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
of arsenic and copper. In previous years, she had no especial trouble 
except occasional pains in shoulder joints and back, but in the winter 
in question these increased, and she began to lose appetite and flesh, 
and her health was generally bad until she went away for the summer. 
After her return in improved health, she continued well at first, but 
came down after a while with fever, with severe pain in the neck and 
shoulders. The latter left her with the fever, but there remained a 
peculiar unpleasant feeling, accompanied by pain in the abdomen. 
She was also troubled by insomnia, which, oddly enough, appeared to 
be intermittent, a sleepless night being followed by one of compara- 
tive rest. Her appetite was poor, but there was no marked symptom 
of digestive disturbance, and the tongue was not coated. There was 
dryness and burning in the throat. Constipation was marked. The 
spleen was not enlarged. 850 c.c. of the urine, after treatment with 
potassic chlorate and hydrochloric acid, were evaporated to 20 c.c., 
and the solution, free from chlorine, was introduced into the Marsh 
apparatus previously tested (time not given) for absence of arsenic. 
After thirty minutes, a very slight mirror was obtained, which looked 
like arsenic. The patient was then removed to another room and ten 
grains potassic iodide given daily. After ten days, the urine was an- 
alyzed again, and a much larger and more characteristic mirror was 
found. The iodide was continued for some time, until the patient 
grew better and suffered no return of the symptoms. The freedom 
of the urine from arsenic was not then determined. 
3. A woman forty-five years old had had typhus, from which she 
recovered very slowly, the convalescence being retarded by certain 
symptoms which were inexplicable. She had no appetite and suffered 
great distress before meals. The tongue was, however, clean. She 
had pain in the head, insomnia, was irritable and peevish. Pulse 
normal. After the patient had been nine weeks in bed and was get- 
ting no better, the covering of the wall was analyzed, and arsenic and 
copper were found in quantity. Fifteen grains of potassic iodide were 
given daily, and, after some days, the urine was analyzed. The appa- 
ratus was carefully tested and the urine residue gave a slight but un- 
mistakable mirror which gave reactions for arsenic. The patient was 
removed to another room and the iodide continued. The symptoms 
began to disappear, and in four weeks the patient was entirely well. 
4. A girl twenty-four years old had typhus in the autumn of 1857, 
from which she was recovering. Pulse was normal and tongue clear. 
Constipation marked. Appetite did not return and patient did not 
recover strength, but was confined to her bed most of the time. She SANGER. - CHRONIC ARSENICAL POISONING. 
151 
was troubled by a ringing in the ears which disturbed her sleep. On 
removal to the country, her health improved, but on return to 
Vienna in the following autumn, some of the symptoms returned. 
There was now some nausea. The throat was red and irritated. The 
girl had slept for several years in the room, and had apparently not 
been affected by the arsenic, which was found, together with copper, 
in quantity on the walls. Twenty grains of potassic iodide were given, 
and after several days the urine was found to contain a trace of arsenic, 
as well as a trace of copper. The green coloring matter was removed 
from the walls. After continuing the doses of iodide, together with 
warm baths and exercise, the patient in a few weeks recovered. 
5. A woman seventy-eight years old had lived for some time in a 
room the walls of which were colored by Mitis green, which could be 
easily rubbed off. In the spring of 1858 she was troubled by period- 
ical recurrence of ringing in the ears and tightness in the head, ac- 
companied by digestive disturbance and constipation, and a feeling of 
oppression in the stomach. On going to the country she became better, 
but on return in the autumn was necessarily confined to the house, 
and the symptoms returned. The ringing in the ears was intensified. 
There was pain in the abdomen, which was distended and painful to 
the touch. Pulse and respiration normal, skin dry, tongue clean. 
Nights sleepless and anxious. April 29, 1859, arsenic and copper 
were found in the urine in traces. Ten grains of potassic iodide were 
prescribed daily, and for the first few days the symptoms decreased. 
The ringing in the ears was less and the nights were better. Patient 
then became feverish, with dry cough and metallic taste. May 15, no 
arsenic or copper could be found in the urine. During the following 
days the metallic taste increased, and there was excessive flow of 
saliva. The iodide was given up and an astringent wash applied, 
stopping the flow of saliva. May 29, there was again no arsenic in 
the urine. During this time pleuritis had come on, and it developed 
into pneumonia, from which the patient died on June 3. Some days 
before death, the ringing in the ears had stopped, but there was a 
burning sensation in the stomach day and night, and the patient 
vomited mucus. The intestines and brain were examined for arsenic, 
but none could be detected with certainty. 
In these five cases, although the details of the analyses are not given 
as carefully as could be desired, it is probable that a small amount of 
arsenic was found in the urine, though it was impossible to estimate it 
with the means then at hand. It is safe, however, from the descrip- 
tion of the mirrors, to set a limit of 0.05 mgr. arsenious oxide per 152 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
litre. The elimination was apparently increased by the potassic iodide, 
but the rate of elimination was not sufficiently studied. 
Muller,* of Augsburg, in 1860, considers Kletzinsky's results to 
have been not well established, and gives the following cases, which 
are also detailed by Fabian,f who performed the analytical work. 
1. Man, aged 37. Symptoms: headache, loss of appetite, excess of 
saliva, eructation, oppression after eating and vomiting, tongue slightly 
coated, constipation. Medicine gave no relief, but absence from home 
improved his general health. On return symptoms increased, and, in 
addition, patient complained of pressure on brain and dizziness. The 
wall paper had been sold as free from arsenic, but contained a large 
quantity, and the color could be easily rubbed off. Fabian predicted a 
negative result when asked to analyze the urine. December 13, 
1859, after finding his reagents free from arsenic, he established the 
presence of arsenic in 912 grams of urine. He went over his reagents 
again with the same result, and an examination of a fresh quantity 
of urine showed arsenic again. The urine was treated with potassic 
chlorate and hydrochloric acid, evaporated, precipitated by sul- 
phuretted hydrogen, and the precipitate thus obtained tested in the 
Marsh apparatus. The wall paper was removed, and potassic iodide 
prescribed (dose not stated). December 23, 812 grams of urine were 
analyzed, and a greater quantity of arsenic was found than before, the 
amounts in both cases being comparatively small. January 19, 1860, 
912 grams of urine were found to be completely free from arsenic. 
This in 37 days after taking the potassic iodide. Recovery followed 
the removal of the paper. 
2-3. A woman, aged 27, and her child, 18 months, had lived for 
some time in a room which was covered by a green unglazed paper, 
in which arsenic and copper were found. The mother complained of 
recurrent headache and pressure in the head. Both were extremely pale 
and suffered from indigestion. January 28, 720 grams of the mother's 
urine showed a trace of arsenic, after which the wall paper was removed 
and potassic iodide prescribed. February 10, 692 grams showed an 
increased amount. February 27, 716 grams showed a less amount, 
and on March 27, 62 days after taking the iodide, the complete absence 
of arsenic was proved. 
550 grams of the child's urine, examined January 28, yielded 
no arsenic. This may perhaps find explanation in the fact that, 
* Wiener Wochenschrift, 1860, Heften 18, 19, 20, 21. 
t Dingier, Polyt. Journ., CLVII. 212. SANGER. - CHRONIC ARSENICAL POISONING. 
153 
shortly before the examination, the physician had prescribed a powder 
of lactate of iron, magnesia, and phosphate of lime, which may have 
had some effect on the elimination. The physician did not dare 
to try the effect of potassic iodide, owing to the child's constitution. 
Both mother and child improved after the paper was removed. 
This investigation is accurate, and the results reliable. It is unfor- 
tunate that no method was known to Fabian which would have per- 
mitted the determination of such small amounts of arsenic. From the 
description of the mirrors, I cannot place the amounts at over 0.05 
mgr. per litre. 
Kirschgasser,* in 1868, published twenty-one cases of chronic poison- 
ing, chiefly from arsenical wall paint, in which are the most complete 
details of symptoms that have ever been presented. I need not refer 
to these cases at any length, as they are well known, and are com- 
mented upon especially in Dr. Putnam's paper, above referred to. I 
note, however, the following. The rooms were partly on the ground 
floor, partly on the first or second story, and were not damp, though 
some were badly aired. There was no apparent opportunity for 
miasma. Occasionally a garlic odor was observed. The children 
appeared less affected than the elders. In one case, the intermittent 
character of the symptoms noticed by Lorinzer f was confirmed. 
The urine was examined in eight of the cases, with a positive result 
in six. In one of the two negative tests the urine was not collected 
until six weeks after the removal of the arsenical color. The work 
was done very carefully by Ilolthof. Large amounts of urine (6 to 
18 pounds, and in one case 25 pounds) were taken, and the reagents 
examined in quantities larger than would be used in one analysis. 
The method of analysis in seven of the cases was as follows. The 
urine was acidified with hydrochloric acid, and sulphuretted hydrogen 
was led in for eight days, occasionally warming. The precipitate 
was collected on a filter, dried, removed from tlie filter, and evap- 
orated repeatedly with nitric acid. The acid was neutralized by sodic 
carbonate, and the solution evaporated and melted to destroy all 
organic matter. The sodic nitrate was then decomposed by sulphuric 
acid, and the clear solution put into the Marsh apparatus. The 
reduction tube was heated for 30 minutes, and the mirror examined 
for arsenic. In the eighth analysis, 25 pounds of urine were acidified 
with nitric acid and evaporated to dryness on the water bath. The 
residue was treated with fuming nitric acid and heated until the mass 
* Vierteljahr. f. gericht. Med., N. F., IX. 96. 
t Loc. cit. 154 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
melted quietly, after which it was dissolved in a little water, filtered, 
and the filtrate heated with excess of sulphuric acid until the nitric 
acid was expelled. The diluted acid solution was then added to the 
Marsh apparatus and gave no mirror in 30 minutes. After establish- 
ing the absence of arsenic in the urine of the case where six weeks 
had elapsed before collection of the urine, an analysis was made, two 
weeks later, of ten pounds of faeces. These were heated two days 
with dilute potassic hydroxide, and chlorine led in. The brown mix- 
ture was decanted from the sediment, saturated with hydrochloric 
acid, and chlorine passed until quite clear. After driving out excess 
of chlorine, the solution was treated with sulphuretted hydrogen, and 
thereafter as in the urine analyses. A heavy mirror was obtained. 
This is interesting as showing the elimination by the faeces after the 
elimination by the urine had ceased. 
In no other case, however, was there any attempt to show elimina- 
tion of the arsenic, on removal of the cause of poisoning and cessation 
of the symptoms. The results of the analyses agree with those of 
Kletzinsky and Fabian in that only small quantities of arsenic were 
found. The quantitative determination was impossible as before. 
Clarke,* in 1873, gives the case of a woman living in a badly 
ventilated room papered with a highly arsenical paper, who had 
symptoms which he said might be attributed to a mild case of typhoid 
fever; great prostration, headache, wakefulness, great nervous excite- 
ment, irritable stomach, and coated tongue. An analyst found the 
dust of the room to contain about 0.2% of arsenic, and in 48 oz. 
(1,700 c. c.) of urine he obtained 0.26 grain (16.8 mgr.). The sputa 
contained a trace. Unfortunately, the method of analysis is not given, 
and we have no means of accounting for the great difference between 
this amount of arsenic (9.2 mgr. per litre) and the amounts in all the 
other cases we have to deal with. Yet, in the ordinary quantitative 
methods, which were the only ones available, 16.8 mgr. is a small 
amount to determine accurately, and it is quite possible that a serious 
error was made. This view is supported by the amount of arsenic 
found in the dust, which is, comparatively, very large. 
On removal, the patient grew better, but no further test of the 
urine was made. 
Mdrner,f in 1876, gives some analyses of urine which are open to 
* British Med. Journ., June 21, 1873. 
t Upsala lakareforen. Forhand., XL 527 ; also, ref., Virchow-Hirsch, Jahresb., 
XI. 405. 155 
SANGER. - CHRONIC ARSENICAL POISONING. 
criticism from the method of analysis used. In one case, the wall 
papers were in several layers, all containing arsenic, the inner more 
than the outer. The reagents were all tested by a run of 45 minutes, 
but gave no mirror resembling arsenic. In the first case, four litres 
of urine were treated with potassic chlorate and hydrochloric acid, but, 
as the destruction of the organic matter was slow, Schneider's method 
of distillation with salt and sulphuric acid was resorted to, though no 
attempt was made, apparently, to reduce the arsenic acid before dis- 
tillation. The distillate was precipitated by sulphuretted hydrogen, 
and the precipitate dissolved in ammonia. One half of this solution 
was evaporated, and the residue examined, according to Fresenius 
and Babo, by mixing with sodic carbonate and potassic cyanide, and 
heating in a stream of carbon dioxide. A white mirror was obtained, 
which on refusion and reheating gave a dark mirror, partially soluble 
in sodic hypochlorite. In another case, Morner obtained a " large " 
mirror. The patient in whose urine this was found went into a room 
containing no arsenic, and one month later there was no arsenic in 
the urine. Two other cases gave "smaller" mirrors, another a 
" doubtful," and in one case there was none. In the urine of people 
living in rooms containing no arsenic, there was no arsenic found. 
All the analyses after the first were made by Schneider's method 
directly. 
One cannot help, on reading Mbrner's paper, distrusting the results 
obtained, as the course of analysis would not only allow arsenic to 
creep in, but might result in the loss of arsenic, if not carefully con- 
ducted. As W. Fresenius* has shown, the Fresenius-Babo method 
is capable of very delicate work in careful hands, but, in general, it 
does not give as good results as the Berzelius-Marsh. 
Jolin,f in 1880, gives the case of a man occupying a badly venti- 
lated room with an arsenical wall paper, who suffered from recurrent 
gastric catarrh, conjunctivitis, and great weariness. The urine was 
treated with potassic chlorate and hydrochloric acid, and evaporated 
to dryness on the water bath. Potassic nitrate was then added, and 
the mass warmed with sulphuric acid until nitrous fumes ceased. 
Into the solution was then passed sulphuretted hydrogen (from calcic 
sulphide and hydrochloric acid), and the resulting precipitate event- 
ually introduced into the Marsh apparatus. A mirror was obtained 
2 cm. long, equally translucent over the entire length, and was 
judged to be between 0.05 and 0.01 mgr. The reagents were care- 
* Fresen. Zeitschr., XX. 522. 
t Hygeia, Stockholm, XLII. 235. 156 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
fully tested, but no mirror resembling arsenic was obtained. Jolin 
regrets that the amount could not be accurately estimated, but the 
approximation is probably quite near the correct amount. It is to be 
regretted that such a long method of treatment was used, as the addi- 
tion of unnecessary reagents adds to the chances of error. 
Welander,* in 1880, reports the case of a man and wife who had 
been for some time depressed and out of health, especially the woman, 
who suffered from gastric catarrh. She lost appetite, and became 
emaciated. Complained of a disagreeable garlic taste, and even imag- 
ined that the urine smelled of garlic.f Her depression increased to 
such an extent that she became hysterical. The papers and hangings 
were found to be arsenical and were removed, and four days after- 
ward 1,500 grams urine were examined. This was evaporated to the 
consistency of syrup on the water bath, fuming nitric acid and sul- 
phuric acid were added, and the whole heated on the water bath for 
twelve hours. The solution was then filtered, and the filtrate saturated 
with sulphuretted hydrogen (from calcic sulphide and hydrochloric 
acid) for twelve hours. The precipitate was charred with sulphuric 
and nitric acids, and the extract added to the Marsh apparatus. After 
some hours (sic) a mirror of arsenic was obtained, mixed with some 
sulphur. After the removal of the papers, the patient recovered, and, 
some weeks after, the urine was found to be free from arsenic. 
The length of time which elapsed before the mirror appeared ren- 
ders the result somewhat doubtful, unless there was organic matter or 
a large quantity of nitric acid in the extract, in which case the reduc- 
tion of the arsenic would have been retarded. Yet Welander does 
not say that the reagents received the same long test to assure their 
freedom from arsenic. 
Kjellberg,t in 1881, gives the case of a healthy woman, who suf- 
fered during the winter of 1878-79 from headache, loss of appetite, 
and frequent diarrhoea. The wall paper was found to be arsenical. 
In the summer of 1879 she was restored to health by a journey, and 
came back to a new house. As the symptoms returned, the surround- 
ings were examined, and the mattress cover was found to contain 
arsenic. Arsenic was found in the urine, but two months after recov- 
ery it was absent. 
* Hygeia, XLII. 238. 
t This may, of course, be purely imaginary, but one is reminded of Selmi's 
claim (see previous paper, page 147) of the discovery Of a volatile arsine in the 
urine of a dog poisoned by arsenic. 
t Hygeia, XLIII. 456; ref., Virchow-Hirsch, Jahresb., XVII. 398. SANGER. - CHRONIC ARSENICAL POISONING. 
157 
Reichardt,* in 1883, mentions a case in which a certain room had 
been covered for twenty years with a slightly arsenical paper. The 
occupant had felt no ill effects, but on calcimining over the paper 
with a green, which proved to contain a quantity of arsenic, symp- 
toms were felt which were attributable to arsenical poisoning. The 
calcimining was done in damp autumn weather, and the room was 
used as a work-room until late at night. A garlic odor was noticed. 
The urine, slightly acidified with nitric acid, was treated with sulphu- 
retted hydrogen for 24 hours, and the resulting precipitate eventually 
introduced into a Marsh reduction flask. By a method proposed by 
Reichardt f himself, the gas from the flask was led into argentic 
nitrate. The latter was then treated with bromine water, the argen- 
tic bromide filtered off, and the arsenic acid in the filtrate precipitated 
by magnesia mixture. A precipitate of ammonio-magnesic arseniate 
could be detected, but not in sufficient amount to estimate. It must, 
however, have been less than a milligram, as Reichardt claims to 
be able to determine that amount by his method. 
I am unable to find any other detailed cases in which arsenic was 
found in the urine up to the beginning of my own work in 1886, 
although Wood t mentions the fact that he found arsenic in the urine 
in a case of wall paper poisoning, and I do not know that others had 
not done the same. In none of the cases, except that of Clarke, has 
there been any quantitative analysis possible. Yet, with this same 
exception, the amounts found have been exceedingly small, and in this 
respect confirm the results obtained by me. 
Cases and Analytical Work. 
From the results above and my own, it is evident that the amount 
of arsenic to be looked for in the urine is very small; hence the 
method of analysis becomes of the greatest importance. Every one 
knows the wide distribution of arsenic, and unless we can, by the ut- 
most care, shut out the possibility of its getting into our analysis, ex- 
cept through the urine, the value of the analysis is nothing. Not only 
must the reagents be most carefully tested in quantity greater than 
likely to be used, but as few reagents as possible must be employed. 
Dishes and other utensils must be scrupulously clean. 
The treatment of the urine in the cases below was as follows. To a 
* Archiv d. Pbarm., [3], XXL 271. 
t Ibid., [3], XVII. 291. 
{ Mass. State Board of Health Report, 1884. 158 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
measured quantity was added about one tenth of the amount of con- 
centrated nitric acid, and the whole evaporated to dryness over a free 
flame. As the mass nears dryness, the flame is lowered. More acid 
may be added if necessary, care being taken to have an excess, in order 
to avoid carbonization of the mass at the end. Deflagration often 
ensues, but loss of arsenic is not to be feared in presence of an excess 
of nitric acid. The organic matter is nearly all destroyed by this 
treatment, but, to eliminate all, the residue is transferred to a smaller 
dish, a little more nitric acid and strong sulphuric acid are added, and 
the whole heated until a clear white melt is obtained, which fumes 
strongly. After cooling, water is added, and the contents of the dish 
added to the reduction flask of the Marsh apparatus. The detection 
and determination of the arsenic are conducted by a modification of 
the Berzelius-Marsh method, published by me two years ago.* It 
is only by such an optometric process that the extremely small 
amounts of arsenic can be quantitatively estimated, the principle of 
the modification being the comparison of the mirrors with those 
obtained from definite amounts of a standard solution of arsenious 
oxide. 
Thus the reagents used are sulphuric acid, zinc, distilled water, 
and nitric acid, all of which have been repeatedly tested in larger 
quantities than would be used in one analysis. The utensils: 
evaporating dishes of Berlin porcelain, stirring rods, funnels, beakers, 
and measuring cylinders have been used for this purpose alone. The 
filter paper has been tested in quantity. Fearing that the glaze of 
the dishes might contain arsenic, and that the glaze would be dissolved 
by the acid sulphates, I kept a quantity of melted acid potassic 
sulphate in a dish for some time, stirring also with the glass rod used. 
No arsenic was found in the solution, showing that there was no dan- 
ger from this source. Finally, blank trials with non-arsenical urine, 
conducted exactly like the others, confirmed the purity of the reagents 
and the cleanliness of the utensils. In collecting samples of urine, 
care has been taken to guard against accidental introduction of arsenic 
from unclean bottles. 
The reduction tube of the apparatus is drawn out so as to give 
two heating places. Before introducing the solution to be tested, 
the apparatus is run for one hour with the lamp under the first 
heating place, and the absence of arsenic in the apparatus fully 
determined. One half, or any aliquot part, of the solution is then 
* These Proceedings, XXVI 24. SANGER. - CHRONIC ARSENICAL POISONING. 
159 
added. After 30 minutes, the lamp is moved back to the second 
heating place, the rest of the solution added, and the heat maintained 
for 30 to 60 minutes longer. Of the two mirrors thus obtained, one 
has been used to confirm the presence of arsenic by solution in sodic 
hypochlorite, or, when possible, by the odor on heating, while the 
second has been retained for reference. In case the amount of arsenic 
is too small to divide, the whole may be collected in one mirror. 
I have found the careful destruction of the organic matter to be 
necessary, as a comparatively small quantity of organic matter in the 
reduction flask is of decided hindrance to the reduction of the arsenic 
and deposition of the mirror. That this is the case seems to be the 
general opinion, although Chittenden and Donaldson* state that their 
results are not affected by the presence of organic matter. They were 
able to recover from 50 c. c. urine, introduced into the flask directly 
with a few drops of olive oil to prevent frothing, the original amount 
of arsenic added, besides getting a distinct mirror from 0.01 mgr. It 
would, however, be impossible to work with the concentrated solution 
of a large quantity of urine without destroying the organic matter 
partially, and I have taken the precaution to destroy it thoroughly, 
particularly as the use of the method as a quantitative one depends on 
the uniformity of deposit of the arsenic mirror, and this cannot be 
assured in the presence of organic matter. 
The cases in which the analytical work fell to me are as follows: - 
Case 1. In the autumn of 1883, Mr. A. and wife took a house in 
Cambridge, of which four rooms, parlor, dining-room, study, and bed- 
room had been recently papered. In the spring of 1885 the halls of 
the house were covered, and either in 1883 or 1885 the other rooms. 
These papers contained the following amounts of arsenic calculated 
as arsenious oxide. 
* Amer. Chem. Journ., II. No. 4. 160 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
Mgr. per Sq. Meter. 
Grains per Sq. Yard. 
Parlor. 
64.9 
0.830 
Hall. 
104.5 
1.340 
" border. 
Very large amount, 
not estimated. 
Dining-room. 
479.0 
6.130 
Bedroom walls. 
96.1 
1.230 
" ceiling. 
1.0 
0.013 
Study walls. 
255.0 
3.260 
" ceiling. 
3.0 
0.040 
" border. 
153.1 
1.960 
Another bedroom, walls. 
0.0 
0.000 
" " ceiling. 
2.0 
0.026 
" " " border. 
596.0 
7.630 
" " wall " 
115.4 
1.480 
" " frieze. 
552.6 
7.130 
Servants room. 
72.8 
0940 
Storeroom. 
25.2 
0.330 
The rear hall and bathroom contained small amounts, and were not 
quantitatively examined. For several months after taking the house 
no trouble was experienced, but toward the summer of 1884 Mr. A. 
and his wife, together with a gentleman who occupied the house with 
them, began to feel some discomfort. This disappeared during the 
absence of the family from the house in the summer, but began again 
soon after they returned in the autumn. The plumbing was in good 
condition and the furnace was a new one. From the fact that the 
discomfort was worse when the latter was in action, the source of the 
trouble was attributed to it. No immediate increase of the symptoms 
followed the papering of the halls, but the health of the family grew 
worse during the spring of 1885. The chief symptoms were trouble 
with the digestive organs and insomnia. The tongue was heavily 
coated, and the food seemed to " sour " in the stomach. Nausea was 
frequent. There was much languor and dizziness and the eyelids 
were badly inflamed. In July the family went away to the sea-shore, SANGER. - CHRONIC ARSENICAL POISONING. 
161 
and there was marked improvement; but on going back to the house 
for August the symptoms appeared again, while return to the sea-shore 
for September brought immediate relief. In the early autumn the 
symptoms returned, but were not at their height until the furnace was 
used. This was again thoroughly overhauled and the air of the house 
tested for carbon monoxide with negative results. Mr. A.'s symp- 
toms increased to a greater extent than those of the others, and were 
accompanied by soreness of the abdomen and abdominal pains at 
night. 
During the last week of December, 1885, the source of the trouble 
was discovered by a qualitative analysis of the papers. Pending the 
removal of the papers, the family left the house and experienced 
immediate relief, especially in sleeping, but many of the symptoms 
continued for some time afterward. January 7, 1886, a week after 
leaving the house, 1,750 c.c. of Mr. A.'s urine were analyzed by the 
method detailed above, and contained 0.01 mgr. arsenious oxide per 
litre. The papers were replaced by absolutely non-arsenical paper, 
and the health of the family gradually came to its normal condition, 
although there was occasional digestive disturbance. The elimination 
of arsenic from the system was apparently very slow. 800 c.c. of 
urine, analyzed March 31 (84 days), contained about as much as be- 
fore, and 820 c.c., analyzed May 26 (140 days), contained 0.007 mgr. 
per litre. Some time after this another sample of urine was sent to me 
at Annapolis, and was set aside with several others until I should find 
time to take up the subject again. So much time elapsed, however, 
before the analyses could be made, that I do not consider the results 
worthy of record. 
Case 2. Mr. C., aged 25, had for some years slept in a large room, 
the paper of which contained from 10 to 15 mgr. arsenious oxide per 
sq. m. (0.13 to 0.20 gr. per sq. yd.). The temperature was low, and 
there was a good circulation of air in the room. At all events, no ill 
effects were felt, and the urine, examined during January, 1886, con- 
tained no arsenic. July 7, 1886, Mr. C. went to a house at the sea- 
shore and occupied a small room, of which the paper contained 
146 mgr. per sq. m. (1.88 gr. per sq. yd.). The area of paper was 
about 22 sq. m. (26.3 sq. yd.). In addition the windows were hung 
with red curtains about 4 sq. m. (4.8 sq. yd.) in surface, containing 
151 mgr. per sq. m. (1.95 gr. per sq. yd.). Soon after taking the 
room he began to suffer from indigestion with occasional bowel pains. 
A qualitative analysis of the paper showing arsenic, the urine was 
examined on July 15, and contained 0.042 mgr. per litre. Mr. C. 
VOL. XXIX. (N. S. XXI.) 11 162 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
continued to occupy the room, but the pain in the bowels became 
more frequent, and on July 27 diarrhoea set in. July 28, the room 
was changed for one in which the paper contained 46.8 mgr. per sq. m. 
(0.6 gr. per sq. yd.), and on the next day Mr. C. was called away. 
Returned in a day or two, and occupied the second room with 
marked improvement, which continued. August 3(19 days), the urine 
contained 0.021 mgr. per litre. During the rest of the month there 
was no recurrence of indigestion except on one day, August 19. The 
urine of this day was collected, and a sample was also taken some time 
after leaving the house. Both shared the fate of those mentioned in 
the previous case. 
Though the second room was arsenical, the apparent exemption 
from its effect was perhaps due to the lesser amount, perhaps to the 
difference in the compound of arsenic on the walls. The second room 
was also better aired than the first. 
Case 3. Mr. D., after living in a room which contained no wall 
paper, removed to another house and occupied a room in which the pa- 
per, a dark red, contained 110.4 mgr. per sq.m. (1.42 gr. per sq. yd.). 
About a month after moving, Mr. D. began to be troubled with 
severe headaches, which were attributed by one physician to change of 
locality. These headaches continued for some weeks, and in addition 
there was trouble with the eyes and throat. Another physician sus- 
pecting arsenical poisoning, the paper was examined. Other papers 
in the house contained arsenic but were only qualitatively analyzed, 
and contained less than that of the room in question. February 12, 
1886, the urine contained 0.015 mgr. arsenious oxide per litre. The 
paper was removed and a non-arsenical paper substituted. Im- 
provement began at once, and the headaches soon disappeared. Here 
again was an apparently very slow elimination as on June 18 (127 
days) the urine contained 0.003 mgr. per litre. 
Case 4. Miss E. occupied a room with a light blue paper contain- 
ing 842 mgr. per sq. m. (10.78 gr. per sq. yd.). The windows were 
hung with blue cretonne curtains, with flowers and leaves in red, 
yellow, and green, containing 309 mgr. per sq. m. (3.9 gr. per sq. yd.). 
No symptoms of this case have been given to me except a long con- 
tinued inflammation of the eyes, continual lassitude and weakness, 
and trouble with the throat. The patient, a girl in robust health, 
became weak and nervously prostrated. The urine examined March 
10, 1886, contained 0.02 mgr. arsenious oxide per litre. Miss E. was 
sent away and rapidly improved in general health. The arsenical 
paper and hangings were removed and replaced by non-arsenical SANGER. - CHRONIC ARSENICAL POISONING. 
163 
material. No recurrence of the symptoms was experienced on return 
to the house. Samples of the urine could not be obtained immedi- 
ately after removal of the paper, or during convalescence, but in 
October the urine was free from arsenic. 
Case 5. Mr. F., for six years previous to 1886, had occupied a 
large, dry, sunny room, and generally spent sixteen to eighteen hours 
each day in it. Two or three years before the report of the case, 
several stuffed birds and animals, preserved by the free application of 
arsenious oxide, were placed in the room. The wall paper contained 
5.7 mgr. per sq. m. (0.073 gr. per sq. yd.), and the border 0.4 mgr. 
(0.005 gr.). The paper of an adjoining bedroom contained 23.1 mgr. 
per sq. m. (0.3 gr. per sq. yd.). The analysis of the last was made 
from a sample taken from the wall, with portions of an old, adhering, 
underlying paper. Mr. F., for nine months prior to April, 1886, 
" noticed perceptibly a train of nervous disturbances, as occasional 
attacks of dizziness and unsteadiness, a feeling of depression, and loss 
of muscular power. He suffered also from a constant coryza, and a 
dry cough. He had no gastric or intestinal disturbance." The pres- 
ence of the birds suggesting a possible explanation of the symptoms, 
1,500 c.c. urine were analyzed April 12, 1886, and contained 0.03 mgr. 
arsenious oxide per litre. The birds were removed and the walls and 
room cleaned, but the papers were left on the walls. April 26 (14 
days) 1,350 c.c. showed 0.026 mgr. per litre. Mr. F. improved in 
general health after removal of the preparations, but the elimination 
of arsenic was apparently slow. June 1 (50 days), 1,220 c.c. gave 
0.002 mgr. per litre. June 14, Mr. F. began to take five grains potassic 
iodide three times daily, which seemed, as in the above cases of Lo- 
rinzer and Muller, slightly to increase the elimination, as on June 21 
(71 days) the amount from 1,320 c.c. was at the rate of 0.006 mgr. 
per litre. Yet on July 16 (96 days) there was still a trace, 1.270 c.c. 
giving 0.002 mgr. per litre. This is possibly explained by the pres- 
ence of the wall papers, or by the fact that the carpets had not been 
shaken. The iodide was discontinued, and Mr. F. went away for two 
months, returning " feeling very well physically, the symptoms al- 
luded to having mainly disappeared." 
Case 6. This is Case 13, reported by Dr. S. W. Driver of Cam- 
bridge, in Putnam's paper.* " The case was one of severe and 
painful inflammation in the abdominal cavity, with constipation and 
loss of strength, . . . but it was difficult to say what symptoms, if any, 
were to be attributed to its [the arsenic] influence." 
* Zoc. cit. 164 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
The only wall paper in the house was in the room where the patient 
spent a great deal of his time, and the amount was 690 mgr. per sq. m. 
(8.8 gr. per sq. yd.). The urine, analyzed May 18, 1886, contained 
0.016 mgr. per litre, and June 16 (29 days), after removal of the 
paper, 0.002 mgr. per litre. 
Case 7. This is one of the group reported in Putnam's paper by 
Dr. J. T. G. Nichols of Cambridge, but the analysis of the urine 
was not given. Dr. Nichols sends the following facts to me : " The 
girl was about four years of age. She had indigestion, constipation, 
and occasional vomiting. Insomnia was a marked symptom. She 
had frequent attacks of sore throat, and was much troubled by eczema 
of the vulva and anus. She was easily tired and very irritable. She 
did not lose flesh nor color." The wall papers were examined by Pro- 
fessor II. B. Hill. In the child's room was a blue frieze about six 
inches wide containing 710 mgr. to the sq. m. (9.09 gr. per sq. yd.). 
One of the other papers in the house contained 153 mgr. per sq. m. 
(1.96 gr. per sq. yd.), another 83 mgr. (1.06 gr.), while the rest were 
but slightly arsenical. 
April 6, 1886, 250 c.c. urine gave an amount of arsenic equivalent 
to 0.015 mgr. per litre. The papers were removed,and "gradual but 
steady improvement soon began." The elimination was slow, but 
I cannot say that all arsenical surroundings were removed. On 
June 29 (84 days), 200 c.c. urine gave 0.012 mgr. per litre, and on 
July 15 (100 days), 930 c.c. gave 0.008 mgr. per litre. The child had 
no return of the symptoms after removal of the papers. 
The following cases are accompanied by analyses of the papers and 
a single analysis of the urine. 
Case 8. This is Case 10, reported by Dr. Driver, in Putnam's 
paper. Patient, N. J., a girl aged 17, and her sister (Case 9), occu- 
pied a room of which the walls were covered by an old-fashioned 
paper, with red flowers and green leaves, and bordered with a strip of 
dark green two inches wide. The green was probably Scheele's or a 
similar one. The paper contained 116.7 mgr. per sq. m. (1.48 gr. per 
sq. yd.), and the border 1,200 mgr. per sq. m. (15.36 gr. per sq. yd.). 
The health of both girls had been impaired for two years. Dr. 
Driver noted to me the following in N. J.'s case : " Puffed and swollen 
face, reminding one of the effects of ivy poisoning, anaemia, quick 
pulse, 80 to 90, dizzy head, nausea, no appetite, dyspepsia. Slight 
trace of albumen that soon disappeared. Grew better under diuretics 
and tonics." The urine was analyzed May 5, 1886, and contained 
0.068 mgr. per litre. On removal of the paper, recovery ensued. SANGER. - CHRONIC ARSENICAL POISONING. 
165 
Case 9. (Case 11, Driver-Putnam.) M., aged 19, sister of N. J., 
occupied same room, but was away from home during the day, while 
her sister N. remained at home, made the beds daily, and swept and 
dusted the room once or twice each week. Dr. Driver notes symp- 
toms : " Dyspepsia, irritated eyes for which she went to the eye and 
ear infirmary, poor appetite, recurring pustules in outer meatus of ear. 
Would feel wretchedly for two or three days at a time." The urine, 
examined May 5, contained 0.028 mgr. per litre. The difference in 
amounts is interesting, from the fact that M. spent less time under the 
influence of the paper than N. did, and that she was less affected. As 
in the case of her sister, recovery followed the removal of the paper. 
Case 10. Miss G., aged 30, occupied a small room in a seaside 
hotel, the paper of which contained 185 mgr. per sq. m. (2.37 gr. 
per sq. yd.), and the border 134 mgr. per sq. m. (1.72 gr. per sq. yd.). 
The areas of paper and border were, respectively, 27.7 sq. m. (33.08 
sq. yd.) and 1.86 sq. m. (2.22 sq. yd.). Connecting with this room 
was another, on which was 23.4 sq. m. (27.95 sq. yd.) of the same 
paper and 1.86 sq. m. (2.22 sq. yd.) of the same border. For about 
a month after taking the room, the occupant was never free from 
indigestion. There were occasional severe pains in the bowels with 
constantly recurring diarrhoea. The first room had but one window 
and the circulation of air was poor. The occupants of the second 
room were apparently not affected, but it must be taken into account 
that this room had three windows and was well aired. The walls of 
both rooms were covered with a glue " size," and the symptoms soon 
began to abate. The urine was not obtained until six days after the 
size was put on. It then contained 0.054 mgr. per litre. During the 
rest of the summer no return of symptoms occurred except occasional 
slight indigestion. 
Case 11. S. H., a girl aged six, had occupied for over a year a room 
of which the paper contained arsenic, but the amount was not deter- 
mined. During the spring of 1886 the child began to show a capri- 
cious appetite, with signs of digestive disturbance. The family took a 
house at the seashore on July 3, and S. occupied with her brother 
(Case 12) a room on the lower floor, the paper of which contained 
313.5 mgr. per sq. m. (4.01 gr. per sq. yd.), the border containing 
128 mgr. (1.63 gr.). No other symptoms were developed, but 
the indigestion became more marked. August 7, 860 grams of the 
urine contained 0.019 mgr. per litre. On this day both children were 
removed to a communicating room, merely for a change, the differ- 
ence in the amount of arsenic not then being established. Little PROCEEDINGS OF THE AMERICAN ACADEMY. 
166 
or no improvement resulted. The paper in this room contained 
109 mgr. per. sq. m. (1.41 gr. per sq. yd.), and the border had 24 mgr. 
(0.31 gr.). August 12, both rooms were sized with glue. The effect 
was soon noticed and the child improved rapidly. 
Case 12. T. H., brother of S. H., aged four, had occupied a room 
which contained but a trace of arsenic in the wall paper, and on 
coming to the sea-shore house was perfectly well. Occupied same 
room as his sister (Case 11), but no signs of a similar digestive dis- 
turbance showed themselves. August 7, he was removed with his 
sister to the communicating room. About this time he had been 
playing during the day with a red flag which was afterwards found to 
contain 336 mgr. per sq. m. (4.08 gr. per. sq. yd.), and he kept it 
with him for several days. August 9, he was attacked with diarrhcea, 
accompanied by fever, which lasted for three days. The urine con- 
tained 0.008 mgr. per litre. August 12, as mentioned above, both 
rooms were glue sized, and for the rest of the summer there was no 
further trouble. 
The other papers in the house were, with one or two exceptions, 
highly arsenical. 
Case 13. Mr. J., a clergyman in good health, lived in a house 
which was papered in the spring of 1885. Three of the papers con- 
tained arsenic in considerable quantity; study, 40.6 mgr. per sq. m. 
(0.5 gr. per sq. yd.) ; bedroom, 31.2 mgr. (0.4 gr.), and the third, which 
I believe covered the hall, 14.4 mgr. (0.18 gr.). Not long after the 
rooms were papered, Mr. J. began to suffer from extreme languor and 
diarrhcea, for which he could discover no satisfactory cause, either in 
diet or daily habits. These continued until he left home for his vaca- 
tion, and for six weeks he was in perfect health. On return, the 
symptoms came back, accompanied by insomnia, dyspepsia, and swell- 
ing of the hands and feet. Neither his local physician nor a New 
York physician whom he consulted could assign a cause for what 
seemed to them to be a case of poisoning. The analysis of the urine, 
February 25, 1886, showed 0.01 mgr. to the litre. The walls were 
stripped and the patient " treated for arsenical poisoning." Mr. J. 
reported his health to me afterward as being improved, but, as he was 
unwilling to pursue the matter further on account of publicity, the 
record ceases here. 
Case 14. This case was reported to me by Dr. A. P. Clarke, of 
Cambridge, and mentioned by him at the meeting of the South 
Middlesex Society above referred to. Mrs. L., aged 51, occupied for 
seven years a tenement, of which the papers, most of them quite old- 
fashioned, contained the following amounts of arsenic, SANGER. - CHRONIC ARSENICAL POISONING. 
167 
Mgr. per Sq. Meter. 
Grains per Sq. Yard. 
Bedroom. 
4.5 
0.06 
Room next bedroom, where ) 
patient occasionally sat. ) 
611.7 
7.83 
Front and back parlor. 
87.2 
1.12 
Kitchen. 
51.0 
0.65 
Hall. 
7.8 
0.10 
Dining-room. 
23.1 
0.30 
For several months Mrs. L. had suffered with severe neuralgic 
pains, " accompanied, from time to time, by a good deal of constitu- 
tional disturbance." There was much gastric disturbance, with fre- 
quent attacks of nausea and vomiting. On removal to another house 
she began to improve and was getting much better, until, contrary to 
the physician's advice, she occupied a room of which the paper was 
arsenical (not sent to me for analysis). A return of the symptoms 
followed. When she finally took a room in which the papers were 
examined and found free from arsenic, she began to get better again, 
and since then had not shown any signs of a relapse. The urine, 
taken 60 days after removal from the first house, contained 0.01 mgr. 
per litre. 
In the following cases the wall papers were not submitted to me 
for analysis: 
Case 15. (Drs. Putnam and Driver, Case 14.) "The patient, 
being a lady of 58, showed, besides the more common symptoms of 
impaired nutrition and digestion, numbness of the hands at times and 
weakness in walking. In the presence of these symptoms, it is fair to 
suspect that a searching physical examination of the muscles, and of 
the sensibility of the skin might have justified a diagnosis of neuritis. 
Without that, the numbness of the hands at least can only be counted 
as a corroborative symptom. The source of the arsenic was not 
traced, but the patient improved on leaving home and relapsed on 
her return." 370 c. c. urine were analyzed July 14, 1886, and 
the amount of arsenic found was 0.005 mgr. per litre. 
Case 16. (Drs. Putnam and Driver, Case 15.) "The patient 
suffered from 'epileptic vertigo,' which was not, however, attributed 
to the arsenic. She had also obscure digestive and nervous symp- 168 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
toms. The suspected paper was not removed, and the patient did not 
recover." 750 c. c. urine, July 1, 1886, gave 0.005 mgr. to the litre. 
Case 17. (Drs. Putnam and Driver, Case 16.) "A variety of 
serious symptoms were present, referable to the nervous system and 
general nutrition, but Bright's disease was present, and for this reason 
it would not have been thought worth while to report the case, but 
that it is a question to be investigated whether arsenic may not occa- 
sionally set up a chronic nephritis. The source of the arsenic was 
not discovered." 1,080 c. c. urine, July 1, 1886, gave 0.055 mgr. 
per litre. 
Case 18. (Drs. Putnam and Driver, Case 17). "Was that of a 
school teacher, thirty-six years old, and in a rather nervous and debili- 
tated state through her work, without, at first, any distinctly char- 
acteristic signs of arsenical poisoning. During the summer months 
immediately following this period, she spent most of her time out of 
doors, and also changed her room, and seemed on the high road to 
recovery. In October, she returned to her former room, and immedi- 
ately her old symptoms came back, and she was obliged to keep her 
bed, suffering from ringing in the ears, sleeplessness, attacks of colic 
at night, followed by diarrhoea, bad taste in the mouth, flatulent dys- 
pepsia, irritation of the eyes and throat, and numbness of the hands. 
On account of the character of the symptoms, and because they became 
worse after the house was closed for a time and the furnace lighted, 
arsenic was suspected and sought for. The paper in the room was 
found to contain only a trace, but a frieze 20 inches wide and extend- 
ing through three stories, gave 15 grains per square yard, and it was 
observed that the hallway formed a sort of shaft through which the 
heated air was conducted to the patient's bedroom, which was protected 
only by a portiere, with an open space at the top. Furthermore, a 
small trunk room, the door of which opened next to hers, and which 
was used, with its window open, to ventilate her room, had an old 
paper with border and figure of Paris green. . . . The paper has 
been removed and the patient's gastric symptoms and sleeplessness are 
much relieved, though she is still under treatment." July 25, 1886, 
760 c.c. of the urine contained 0.018 mgr. arsenious oxide per litre. 
Case 19. (Drs. Putnam and Driver, Case 12). "Was interesting 
from the fact that here also were periodic attacks of gastralgia, 
occurring this time at night, but in addition occasional outbreaks of 
colic and diarrhoea. Insomnia and debility were also present. There 
were no other especially characteristic symptoms." May 26, 1886, 
960 c.c. urine gave 0.01 mgr. per litre. SANGER.- CHRONIC ARSENICAL POISONING. 
169 
Case 20. This case was also reported to me by Dr. Clarke. Mrs. 
D., aged 66, had lived in her tenement for nine years. During 
this time the rooms were papered in different years with papers 
which, in eight cases, were arsenical (not sent to me for analysis). 
" General weakness and nervous prostration have been pronounced 
symptoms of her case. The mouth and throat have been sore. The 
parts smart and sting, and the sensations extend into the trachea and 
oesophagus. The tongue is red, especially at the tip, the follicles are 
large, red, and protrude, and are very sensitive." On leaving the 
house for a short time, relief was immediate, but the symptoms reap- 
peared on return to the house. July 2, 1886, the urine contained 
0.005 mgr. per litre. 
Discussion. 
Tn all these cases the amount of arsenic eliminated by the kidneys 
is extraordinarily small, varying from 0.002 mgr. to 0.068 mgr. per 
litre. Tn the cases quoted in the historical sketch, the amounts could 
not have been much in excess of this, and in the analyses of Worcester 
given in Putnam's paper below, the quantity varied from 0.005 to 0.1 
mgr. per litre. 
I have been able to find but one quantitative determination of the 
rate at which small amounts of arsenic are eliminated. Hubbard,* in 
1882, gives the following experiments. grain (3.87 mgr.) of arse- 
nious oxide was given to a man, in pill form, for five days, and the 
urine of the last three days collected. On the third day no arsenic 
was found, on the fourth, 0.01 grain (0.65 mgr.), and on the fifth, 
"traces." Continuing,grain (7.74 mgr.) was given for two days, 
then grain (5.16 mgr.) for two days. On the eighth day, 
grain (1.12 mgr.), and on the ninth, grain (0.78 mgr.), was 
recovered. During this time the man was indoors and took no exer- 
cise. In the second case grain (6.45 mgr.) was given for six 
days to a man who took sufficient exercise each day to induce fatigue. 
On the fifth day grain (0.59 mgr.), and on the sixth day T|7 
grain (0.35 mgr.), was recovered, the urine of the first four days 
not being examined. In the third case, the person was in feeble 
health and suffered from indigestion due to gastric catarrh. grain 
(3.24 mgr.) was given for six days, and on the sixth day no arsenic 
* Physician and Surgeon, Ann Arbor, IV. 348 ; also, Contrib. Chem. Lab. 
Univ. Mich., I., Part 1. 170 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
could be found. Then grain (6.48 mgr.) was given for six days 
more, and on the twelfth day grain (0.52 mgr.) was recovered. 
No attempt was made in any of the trials to follow the elimination 
until it stopped. 
When we consider that the determination of the arsenic was made 
by weighing the mirror obtained, and that the amounts varied from 
0.35 mgr. to 1.12 mgr., the chances for error in weighing will be seen 
to be very great. Furthermore, the evaporated urine was added 
directly to the reduction flask, and Hubbard himself thinks that the 
organic matter is apt to interfere with the reduction and accurate 
deposition of the arsenic. 
This, besides being the only quantitative series of experiments that 
I can find, concerns only the elimination when the arsenic is taken as 
arsenious oxide. 
As to the rate of elimination, then, in cases of chronic wall paper 
poisoning, there are, so far as I know, no other data than in my ex- 
periments or in those of the historical sketch. Wood* has, however, 
recently made an investigation into the length of time required for 
elimination in cases where the poisoning occurred from other causes. 
His results are not quantitative. Two of the cases were chronic (from 
Fowler's solution), the third being acute (from arsenious oxide). In 
the first two, 58 and 82 days were required, and in the third 93 days. 
Wood also refers to a chronic case by Gaillard f (Fowler's solution), 
in which 53 days were required. In the cases given above, though 
the elimination was not examined to completion, the time after which 
arsenic still appeared varied from 19 days to 140 days. 
But neither Wood's nor Hubbard's work enables us to draw 
an inference as to the rate of elimination from such minute doses as 
would come from a wall paper, and we have no parallel work what- 
ever on the amount or rate when the arsenic is in the form of a deriv- 
ative of arsenic acid. 
In discussing the source of chronic wall paper poisoning, we have 
to consider in what state the arsenic compounds exist in the air of the 
room. The possibilities are two: a gaseous or volatile compound, 
and the solid particles mechanically detached from the paper. In 
addition to the action of the arsenical dust in the air, we are now in a 
position to consider the action of a volatile arsenical compound. The 
formation of a volatile compound from decaying arsenical matter, first 
* Bost. Med. Snrg. Journ., CXXVIII. 414. 
t Ann. d' Hygiene, October, 1874. 171 
SANGER. - CHRONIC ARSENICAL POISONING. 
discovered by Hamberg,* is now assured beyond question by the 
results of Gosio,f which I have confirmed, as shown in the foregoing 
paper. We have, then, either or both of these sources from which 
the arsenic can enter the system. Let us now consider the first of 
these. 
As the amount of arsenic eliminated is so small, the amount 
ingested must be also small. As far as I can discover, no experiments 
have been made to investigate the action of minute quantities of 
arsenic when taken into the stomach, nor do I know of any work on 
the effect of inhaling air charged with minute particles of an arsenic 
compound. Furthermore, I have found no information on the ac- 
tion of minute quantities absorbed through the skin and mucous 
membranes. Thus we have no data to guide us to any conclusion 
as to the effect of minute quantities, however ingested. Yet, as in 
the case of larger quantities, the toxic effect is better known when 
taken into the stomach, we may use this channel as a basis of 
comparison while considering the reason for the action of minute 
quantities. 
But little thought has been given to the compound, or to the state 
of oxidation in which the arsenic exists in the paper. We may divide 
the compounds into the trioxide and its derivatives, the pentoxide 
and derivatives, and the sulphides. Of the former the basic arsenite 
(Scheele's green) and the aceto-arsenite of copper (Schweinfurth, 
Paris, Mitis green) were formerly very common, but are now rare in 
wall paper, though they may appear in domestic fabrics. We may 
have also the trioxide itself, and possibly a few other arsenites. The 
sulphides may occur occasionally. But in a very large number of 
the papers of to-day which contain arsenic the higher oxidation state 
is found. The use of arsenic acid in the manufacture of rosaniline is 
liable to leave arsenic in the color as an arseniate, as well as arsenite, 
while the use of the arseniates as mordants is very common, especially 
in fabrics. 
The effect of arsenious oxide and its derivatives may be inferred to 
a certain extent from the well known action of larger amounts, but 
in the case of the action of minute amounts of the sulphides and 
arseniates we have little to guide us. I have found a few cases 
of poisoning from arseniates, but, with one exception, a case of 
* Pharm. Journ. and Transactions, [3], V. 81 ; Pharm. Zeitschr. f. Russland, 
XXV. 779. 
t Azione di Alcune Muffe sui Composti Fissi d' Arsenico, Roma, 1892. 172 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
poisoning by potassic arseniate,* the chemical tests show the sub- 
stance to have been an arsenite. 
The difference in action between arsenious and arsenic acids was first 
studied by Wohler and Frerichsf in 1848, arsenic acid previous to 
that time having been considered more poisonous than arsenious acid. 
They concluded that the arsenic acid was less active than the arseni- 
ous, following the analogy of the phosphoric and phosphorous acids. 
They thought that the arsenic acid was reduced in the organism to 
arsenious acid. They also proved the poisonous quality of calcic 
arseniate, although it is insoluble. This is also shown by Schmidt and 
Bretschneider.t Schroff,§ in 1852, experimented more carefully than 
Wohler and Frerichs, and came to the conclusion that arsenic acid 
was not very much less poisonous than arsenious acid. Marme,|| 
in 1875, quotes Savitsch,T who found that the poisonous qualities 
stood in the same ratio as the percentage of metallic arsenic in each. 
Marine, however, in a carefully conducted series of experiments, was 
able to show that arsenic acid is much the less energetic. Reichardt** 
remarks the necessity of determining the state of the arsenic, in order 
to know whether it is injurious or not. He considers that arsenic acid 
may be combined with iron in ochres, and supposes ferric arseniate to 
be harmless. Yet if calcic arseniate is poisonous, why not ferric ? 
If arseniates are less poisonous in large doses, is it because they are 
less of an irritant ? If less irritating, could they be accumulated more 
easily if in minute doses ? 
This leads to the consideration of the localization of arsenic in 
chronic cases. Scolusuboff,tf in 1875, found the deposition, when taken 
as arsenious oxide and sodic arsenite, to be chiefly in the brain, " from 
which it is carried by the circulation to other organs." Ludwig.tt in 
1881, finds this assertion to be wrong as far as arsenious oxide is 
concerned, the brain containing comparatively little, while the liver con- 
* Bouley, jeune, Mem. Acad. Roy. de Med., Paris, 1835, IV. 298-307. 
t Ann. d. Chem. u. Pharm., LXV. 345. 
1 Moleschott's Untersuchungen, 1859, VI. 146. 
§ Archiv f. phys. u. path. Chem. u. Mikr., Wien, V. 241. 
|| Nachr. v. d. konig. Gesells. d. Wissens. a. d. Georg. Aug. Univ., Gottingen, 
1875, p. 614. 
If Dissertation, Dorpat, 1854. 
** Loc. cit. 
ft Archiv Phys. norm, et path., 1875; also, Ann. d'Hygiene publ. et de 
Me'd. legale, Jan., 1876. 
ft Jour, de Pharm. etde Chemie, [5], VI. 198 ; also, Chem. Centralblatt, 1881, 
p. 90. SANGER. - CHRONIC ARSENICAL POISONING. 
173 
tained the most and held it longest. This view is confirmed by Gua- 
reschi,* Bergeron, Deiens, and L'Hote,f and Johnson and Chittenden.J 
Chittenden § gives an exhaustive analysis of a body, with quantitative 
results as far as he could go by his method. The largest amount of 
arsenic was in a muscle from the back, next in the intestines, and 
next in the liver. The kidneys contained very little, the brain some- 
what more than the kidneys. Chittenden was of the opinion that a 
marked difference was made in the distribution according to whether 
the arsenic was given in one dose or in several. 
All this work, however, with the exception of ScolusubofFs, has to 
do with arsenious oxide alone. There is no evidence to show that the 
same rate or place of distribution holds good for other compounds of 
arsenic, especially for the arseniates, and we also have no means of 
knowing where the arsenic goes when ingested in minute, continued 
doses. 
Schmidt and Bretschneider || investigated the question whether the 
urine contained arsenious or arsenic acid when the arsenic was taken 
as the trioxide. Their method was somewhat unsatisfactory. Arsenic 
acid was found and no arsenious, but possibly with a better method 
they would have found arsenious acid also. Yet the arsenic acid was 
undoubtedly in excess. Would a minute quantity of an arseniate pass 
eventually into the urine with less acute disturbance ? In the same 
investigation the above authors examined the effect of metallic arsenic 
when taken in a perfectly pure state, and found it to cause no acute 
poisoning. Metallic arsenic was found in fteces and urine. This work 
was a repetition of that of Schroff,H who, using impure material had 
found metallic arsenic to be poisonous. 
A statement of the facts we now possess in regard to the volatile 
compound is in order here. A brief resume of Gosio's work on this 
subject has been recently given by Shattuck.** 
The compound is generated by the action on arsenical organic mat- 
ter of the following moulds : Penicillium brevicaule, Mucor mucedo, 
Aspergillum virens, and Aspergillum glaucum, a few others having 
been found which have a slight action. Of these the most intense 
* Gazzeta Cliim. Italiana, XIII. 176. 
t Ann. d'Hygiene publ. et de Med. legale, [3], III. 23. 
f Amer. Cheni. Journal, II. 232. 
§ Ibid., V. 8. 
|| Loc. cit. 
IT Zeitschr. der Wiener Aerzten, 1858, I. 4. 
** Bost. Med. Surg Journ., CXXVIII. 540. 174 
PROCEEDINGS OF THE AMERICAN ACADEMY. 
action is caused by the first, a mould discovered on decaying paper, 
though Mucor mucedo, which is more widespread than the first, is 
only a little less active. The conditions for development of the com- 
pound by these moulds are moisture, a temperature from 15 to 35° C. 
(60-95° F.) and a supply of oxygen, without which no action takes 
place. A large amount of arsenic retards the growth, which goes 
on best in a ground containing 0.01 to 0.05%. The best nutritive 
material is a carbohydrate. The development may take place in pres- 
ence of arsenious oxide or its derivatives, or of arseniates, though the 
latter seem to me to have given the best results. Little or no action 
is obtained from the sulphides. 
As to the nature of the volatile compound it was thought from the 
work of Hamberg and the speculations of others to be arseniuretted 
hydrogen, an assumption that has been very misleading. Certainly 
very little, and I think none, is formed. As far as the results go, the 
compound seems to be a neutral organic derivative, and my opinion 
is that the results favor its being an organic derivative of arsenic 
pentoxide. No definite properties beyond its peculiar alliaceous odor 
and volatility have been found, except that the yellow compound 
noticed by Hamberg, Gosio, and myself may be a " molecular " com- 
pound with argentic nitrate. 
It may be remarked in passing that the proof of the formation of a 
volatile compound is a complete explanation of the poisoning in many 
cases where an arsenical paper underlies one that is free from arsenic. 
Also, though the effect of an arsenical paper may be temporarily 
lessened by a varnish or size, that the danger is not removed. 
With the volatile compound we have to consider the question not 
only of more minute doses than in the case of dust, but of a form 
which permits the arsenic to enter the system more easily by the 
lungs and in a state differing greatly from any dust. Whether we 
have a derivative of arsenious or arsenic acid, the fact that the mole- 
cule contains carbon is a very important one. 
The experiments of Schrbter * on the poisonous action of p-benz- 
arsenic acid, C6H4(CO2H) . AsO(OH)2, are interesting here, though 
it is not likely that the volatile compound is an aromatic derivative. 
Schrbter found that the amount of arsenic in a fatal dose of benzar- 
senic acid was somewhat larger than in a fatal dose of either arsenic 
or arsenious acids, but that death followed after a much longer inter- 
val than with either of the others. The early symptoms were refer- 
able to benzoic acid, the later to arsenical poisoning. 
* Inaug. Dissert., Erlangen, 1881. SANGER. - CHRONIC ARSENICAL POISONING. 
175 
Tn chronic poisoning a tolerance was established to such an extent 
that five times as much could be given as would be fatal to an animal 
not accustomed. In the urine immediately after ingestion an arseni- 
cal organic acid other than benzarsenic acid was found, but could not 
be detected afterward, though the urine was arsenical. 
Schrbter ascribes the difference in action between benzarsenic and 
the two inorganic acids to the carbon in the molecule, a separation 
into benzoic acid and arsenic acid having to be made before the latter 
can act. 
Selmi * claims to have isolated from decaying arsenical animal 
matter an arsenical alkaloid and a ptomaine, and Husemann,f on the 
strength of this, thinks that an arsenical ptomaine may be formed by 
the decomposition of arsenical paste by mould. There is no evidence, 
however, to show that the volatile compound is of the nature of a 
ptomaine. 
An important contribution to the knowledge of chronic wall paper 
poisoning was made about three years ago by Putnam,! who collected 
a number of samples of urine mainly from hospital patients, selecting 
chiefly those cases in which there were no symptoms referable to ar- 
senical poisoning. These samples, 48 in number, were analyzed by 
Dr. C. P. Worcester, and traces of arsenic found in 21 (44%). A 
year later,§ Putnam added to this list, making the total number of 
samples 150, of which Worcester found over 30% arsenical. The 
method of analysis used was similar to that described in this paper. 
These results prove the wide distribution of arsenic in articles of house- 
hold use, and show also that the system is evidently capable, in many 
cases, of absorbing and eliminating minute quantities of arsenic where 
a large quantity would act as an irritant. 
The following facts may now be noted : - 
1. The distribution of arsenic in articles of domestic use is very 
wide, and it has been shown that it finds its way into the system in 
many cases where there is no poisonous effect. 
2. It is now pretty conclusively shown that arsenic may be in some 
cases accumulated, instead of always being readily eliminated. 
3. The amount of arsenic absorbed in chronic wall paper poison- 
ing may be very minute, but it is in continued doses. 
* Mem. d. Accad. d. Scienze, Bologna, [4], I. 299. 
t Arch. d. Pharm., CCXIX. 415. 
t Bost. Med. Surg. Journ., CXXII. 421. 
§ Ibid., CXXIV. 623. 176 
PROCEEDINGS OF THE AMERICAN ACADEMY 
4. The elimination of the arsenic by the kidneys in wall paper poi- 
soning is very slow and the amount eliminated very small. 
5. The absorption of the volatile compound, though in smaller 
amounts, is more direct than that of the dust particles, and the action 
is modified by the presence of carbon in the compound. 
6. The effect of minute doses of any compound of arsenic, in what- 
ever way ingested, has not been studied. 
7. The effect of any quantity whatever of many compounds of 
arsenic that occur in wall papers and fabrics, notably arseniates, is 
not well known, whether the arsenic compound be taken at once or 
in continued doses. 
8. The localization of any compound of arsenic and particularly of 
the arseniates, when taken in minute continued doses, has not been 
studied. 
9. The salts of arsenic acid seem to be less irritating than those 
of arsenious acid. Is this because the state of oxidation permits its 
readier accumulation ? 
My position does not permit me to advance any decided opinion on 
the source of chronic wall paper poisoning, and I can only submit the 
above facts for consideration. From the facts, however, that have 
come to my notice during the preparation of these two papers, I 
cannot help making the following suggestion: - 
Chronic arsenical poisoning from wall papers and fabrics may be 
chiefly due to the ingestion of minute continued doses of arsenic as a 
derivative of arsenic pentoxide, which from its state of oxidation is 
likely to be accumulated in the system, from which it is slowly 
eliminated. The absorption may be from an inorganic arseniate in 
the form of dust, or from a volatile organic derivative of arsenic acid, 
or from both. 
The remark of Dragendorff,* that a part of the arsenic acid may go 
into the bones in place of phosphoric acid, should be remembered 
here. It seems quite possible that calcic arseniate, being isomorphous 
with calcic phosphate, should replace a part of the latter. This may 
be confirmed by Ludwig f and Gibb,J both of whom found arsenic in 
the bones, Ludwig finding that it was held there long after the doses 
ceased. Evidently a large field of investigation must be cleared 
before a definite conclusion can be reached as to the cause of chronic 
wall paper poisoning. 
* Ermittelung v. Giften, 1876, p. 326. 
t Loc. cit. 
| Trans. Pathol. Soc. London, 1858, IX. 442. SANGER. CHRONIC ARSENICAL POISONING. 
177 
In conclusion, it must be remarked that both Gosio's and my work 
have shown that a very small amount of arsenic may be quite as good 
a source of the volatile compound as a very large amount. Hence the 
limit that can be set as a dangerous amount of arsenic in a wall paper 
is a matter which should be very carefully considered. It has been 
thought by many that a paper containing under 0.1 gr. per square yard 
(8 mgr. per sq. m.) was harmless. If the arsenic were given off as 
dust alone, perhaps this limit would be sufficient, but, with the chance 
for the formation of the volatile compound, we cannot, I think, say that 
0.1 gr. per square yard is harmless. The matter of limit emphasizes 
the need of a quantitative analysis of the paper. By the process I 
have described and referred to here, this is a simple matter, and every 
paper should be reported, not in the indefinite " traces," " large 
amounts," " dangerous quantity," etc., but with the approximate fig- 
ures, so that the physician may himself decide as to whether the paper 
should be rejected or not. 
Washington University Chemical Laboratory, 
Saint Louis, September, 1893. 
VOL. XXIX. (N. S. XXI.) 
12