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U. S. DEPARTMENT OF LABOR
JAMES J. DAVIS, Secretary
BUREAU OF LABOR STATISTICS
ETHELBERT STEWART, Commissioner
BULLETIN OF THE UNITED STATES \
B U R E A U OF LA BO R S T A T I S T I C S / ’ ‘ ‘
INDUSTRIAL
ACCIDENTS
A ND
j
* | ilO t
HYGIENE
OQA
£ 0 U
SERIES
INDUSTRIAL POISONING IN
MAKING COAL-TAR DYES
AND DYE INTERMEDIATES
By ALICE HAMILTON, M. A., M. D.
APRIL, 1921
W ASHINGTON
GOVERNMENT PRINTING OFFICE
1921
CONTENTS.
Page.
Introduction______________________________________________
5-7
Bemzene, toluene, and xylene_________________________________ 7-11
Benzene derivatives________________________________________ 11-36
The nitro compounds___________________________________ 18-25
Nitrobenzenes______________________________________ 18-20
Mfcrotoluenes______________________________________ 20-22
Nitronaphthalenes__________________________________
22
Nitranisols________________________________________
22
Dinitrophenol 1-2-4__________________________________22-25
Anilin and other amido compounds_________________________ 25-34
Toluidins__________________________________________28-30
Xylidins__________________________________________
30
Diamines: Toluylendiamine, phenylendiamines, quinone dichlordiamine_________________________________________ 30, 31
Diphenylamine______________________________________
31
Nitranilins________________________________________ 31, 32
Methyl and ethyl anilin______________________________ 32, 33
Anilin hydrochloride. Sulfanilic acid____________________
33
Paraamidophenol___________________________________
33
Naphthylamines____________________________________ 33, 34
Amidoazotoluene____________________________________
34
Ohlor compounds______________________________________ 34, 35
Chlorbenzene______________________________________
34
Nitrochlorbenzene_______________ - ___________________
35
Dinitrochlorbenzene________________________________ _
35
35
Benzyl chloride, benzal chloride, chlorinated toluene_________
Hydroxy compounds____________________________________
36
Pyridins_____________________________________________
36
Phosgene or carbonyl chloride________________________________ 30, 37
Aliphatic or fatty compounds_________________________________ 37-41
Methyl alcohol or wood alcohol____________________________
38
Formaldehyde_________________________________________ 38, 30
Acetone______________________________________________
30
Dimethyl sulphate______________________________________30-41
Methyl chloride________________________________________
41
Inorganic compounds______________________________________ 42—46
Hydrochloric, sulphuric, and nitric acids____________________ 42, 43
Hydrogen sulphide or sulphuretted hydrogen_________________ 43, 44
Hydrogen arsenide or arseniuretted hydrogen_________________ 44-46
Caustics_____________________________________________
46
Records of sickness in German dye manufacture__________________
47
Records of sickness in American dye works______________________ 48-50
Processes in dye manufacture-_______________________________ 50-58
1. Sulphonation_______________________________________
51
2. Caustic fusion______________________________________51, 52
3. Nitration__________________________________________52, 53
4. Reduction__________________________________________53-56
56
5. Chlorination_______________________________________
6 . Alkylation_________________________________________ 56,57
7. Oxidation__________________________________________
57
8. Carboxylation______________________________________
57
9. Lim ing___________________________________________
57
10. Condensation_______________________________________
57
11. Diazotizing and coupling______________________________ 57, 58
3
4
CONTENTS.
Page.
Color manufacture----------------------------------------------------------------------------- 58-61
Prevention oi: occupational poisoning___________________________ 61-69
Appendix 1.— Structure of the benzene ring and its principal deriva
tives, isomeric forms, etc__________________________________ 70-74
Appendix 2.— Diagram of the products derived from coal and some of
their uses______________________________________________
74
Appendix 3.— Massachusetts: Rules and regulations suggested for safety
in the manufacture of benzene derivatives and explosives__________ 74-77
Appendix 4.— New Jersey and Pennsylvania: Safety standards for the
manufacture of nitro and amido compounds____________________77-85
Appendix 5.— Great Britain: Regulations for the manufacture of nitro
and amido derivatives of benzene and of explosives with the use of
dinitrobenzol or dinitrotoluol_______________________________ 85-87
BULLETIN OF THE
U. S. BUREAU OF LABOR STATISTICS.
N O . 280.
WASHINGTON.
A p r il, 19 2 1
INDUSTRIAL POISONING IN MAKING COAL-TAR
DYES AND DYE INTERMEDIATES/
INTRODUCTION.
The making of coal-tar dyes and dye intermediates in the United
States has grown enormously since 1914, and during this time the
industry has passed through many phases. The author’s first ac
quaintance with it was in 1916-17, when, in the course of an investi
gation of plants manufacturing and loading explosives, a number
that were also manufacturing dye intermediates w^ere visited. More
over, some compounds are used for both purposes; for instance,
dinitrotoluene, dinitrobenzene, diphenylamine, and anilin. At that
time the methods used were sometimes crude and decidedly dangerous,
because it was only in a few old plants that the nature of these com
pounds was well understood, the risks known, and the proper pre
cautions taken. It was generally believed that vapors were the
greatest danger; that men became poisoned by breathing fumes of
volatile liquids, and when preventive measures were undertaken they
W'ere based on this idea. It w^as only later that, as a result of sad ex
perience, certain solids, such as dinitrobenzene and paranitranilin,
were discovered to be quite as troublesome as a volatile liquid like
anilin, or even more so. It was also found that one could not revive a
man with anilin poisoning by taking him out in the fresh air; one must
also get rid of the anilin on his skin by stripping and bathing.
Gradually the results of experience became known and conditions
improved more or less. The improvement w^as hastened by the closing
of the smaller works and b}^ the concentration of dye intermediate
manufacture in a few large plants. While in 1916 anilin and nitro
benzene were made in dozens of places, they are now made in only
a few, and there has been a very decided falling off in the cases of
a This report is based on 36 inspections of American plants producing crudes, inter
mediates, and colors, made during the years 1916 to 1919, and on visits to the following
foreign works during the summer of 1919: British Dyes (Ltd.), Huddersfield; Levinstein
(Ltd.), Manchester; Claus & Co. (Ltd.), Clayton, Manchester; Clayton Aniline Co. (Ltd.),
Clayton, Manchester ; Mersey Chemical Co., near Liverpool ; Poiret & Cie., St. Denis, near
Paris ; Allgemeine Chemische Gesellschaft, Basel; Leopold Casella, Mainkur, near Frankfort-on-the-Main.
5
6
IN D U ST R IA L PO ISO N IN G IN' M A K IN G CO AL-TAR DYES.
intoxication from these compounds. There has also been a great im
provement in the care given to the employees. The larger plants
have safety or welfare superintendents, whose duty is to provide
against accidents and accidental poisoning. Physicians are em
ployed to attend such cases, and these physicians acquire skill in
diagnosis and treatment which can not be obtained by the ordinary
practitioner. In the best American plants the physicians also do
very valuable preventive work. The competent physician is familiar
with the different processes and the dangers inherent in them, and
keeps watch for the earliest symptoms of occupational intoxication
among the men. The manufacture of dyes and intermediates in the
United States has undergone great improvement and is improving
from day to day, but it can not be said that this improvement is at
all uniform or that there are not still some unnecessarily dangerous
departments even in the best plants, and a few are, still far from
what they should be, both in the matter o f construction and operation
and in the personal care of the force. It is because of this great
variation, this lack of standardization of the safety work in the in
dustry, that it seems useful to present the results of an investigation
carried on at intervals during the last three years, so that the dif
ferent manufacturers may learn of the methods used in places other
than their own and the experience gathered in one place may be
made available for all places doing similar work.
It seems valuable also to publish in convenient form the informa
tion that can be gathered from the literature, especially of Germany^
concerning the action on the human body of the great variety of
compounds used in this complicated industry. Germany has for
years conducted elaborate animal experiments with these compounds,
and in addition an enormous human experiment has gone on in her
dye works. It seems a pity not to avail ourselves of the results
rather than to go on and repeat such human experiments ourselves.
O f late, American observers have added their contribution to this
branch of industrial toxicology, and wherever possible the Ameri
can publications have been used. The compounds that are dealt
with in this report are not by any means all that the color worker
comes in contact with. Others, whose chemical composition leads
one to suspect that they possess toxic properties, may later on prove
to be quite as dangerous as those about which we already have
sufficient data to indicate their poisonous character. The only ones
taken up in this report are those which have been found to cause
actual poisoning in human beings.
One advantage the American industry possesses when compared
with the European is the absence of women in the working force.
During 1918 plans were under way to substitute women for men in a
few plants, and some women were actually employed, but as soon
as the armistice was signed the women were discharged and there is
no intention now of ef&ploying them in any plant. This is a matter
for congratulation because it is believed by all authorities that the
employment of women in work exposing them to any poison should
be discouraged as much as possible, not because they are necessarily
more susceptible to poison than men, but because if they do suffer
from the effects they may pass the injury on to their offspring.
The report is not presented as a complete one in any sense, cer
tainly not as a complete description of the processes used in dye and
INTRODUCTION.
7
dye intermediate manufacture. Only the barest outline of these
processes is attempted, and this merely because the dangers of the
work can not be described without some such slight outline of the
chief reactions and their resulting compounds.
The making of dyes has necessitated the production and use not
only of benzene, nitrobenzene, and anilin, but also of an enormous
number of derivatives, many of which have a toxic action on the
skin, on the central nervous system, on the blood, or on all three.
The crude compounds of the coal-tar series that serve as starting
points for the production of dyes are benzene, toluene, xylene,
naphthalene, anthracene, and phenanthrene, the first three of which
are decidedly toxic. Naphthalene was tested by Eulenberg1 who
says that it causes in animals nothing worse than an irritation of
the mouth, nose, and eyes, with salivation and lachrymation. Men em
ployed with hot naphthalene may suffer from headache and confu
sion caused by the fumes. Eulenberg found the same effect from
hot anthracene, and also occasionally an eczema.
BENZENE (CeHe), TOLUENE (C0H5CH3), AND XYLENE
(C6H4(CH3) 2).
Benzene is obtained in this country in the manufacture of coke
and of illuminating gas. In coke works the coal is roasted and the
lighter vapors, benzene, toluene, and xylene, are absorbed in heavier
oils with a higher boiling point, and are then subjected to fractional
distillation. Benzene and its homologues are also recovered from
coal-gas residuals in gas works. In making gas the tar left in the
mains and scrubbers is allowed to stand till the gas liquor separates
out, a source for the obtaining of ammonia, then the tar is distilled.
The first bodies to pass over are benzene, toluene, and xylene; next
come crude carbolic acid and naphthalene “ dead oil,” then anthra
cene, leaving a residue of coal-tar pitch.
In well-constructed and well-managed plants for the production
of these bodies there is practically no danger of fumes or contact
with the volatile poisonous substances except when it is necessary to
repair or clean the apparatus. When this is done extraordinary pre
cautions must be taken to protect the men, and sometimes in spite
of these precautions very serious accidents occur. The same thing
is true of the use of the light coal-tar distillates in making dye in
termediates; the cases of industrial poisoning follow almost always
some accident or an unusual exposure in the course of a job of clean
ing or repairing.
Benzene is a fairly new industrial poison in the United States, for
its use before the war was decidedly restricted, since it was imported
from Germany and therefore expensive. The petroleum products,
naphtha, benzine, and gasoline, were used as solvents for fats, gums,
and rubber, because they were obtainable in large quantities in this
country. After the outbreak of the war there was a sudden demand
for toluene for the manufacture of trinitrotoluene and of benzene for
the manufacture of picric acid and tetrvl, and at the same time the
coal-tar dye industry, which was growing with great rapidity, added
1 Q uoted by K o e lsc h in M u n chen er m edizin isch e W o c h e n s c h rift, J u ly 2 4 , 1 9 1 7 .
8
IN D U ST R IA L PO ISO N IN G IN
M A K IN G COAL-TAR DYES.
its demand for these two compounds, and the rubber industry, which
had become dependent upon German anilin, was obliged to procure
benzene and manufacture anilin. At present large quantities of tar
distillates are produced in the United States and used, not only in the
manufacture of dyes, drugs, and perfumes, but also, because of their
powerful solvent properties, in rubber manufacture and in the mak
ing of shellacs, varnishes, varnish and paint removers, and dope for
airplanes. They are also coming into increasing use as fuel for motor
cars. In consequence of this large production and use we have had
during the last five years a much larger number of cases of industrial
poisoning from benzene and toluene than were reported in the whole
of American medical literature up to 1914.
In describing the effects of these bodies the three— benzene, toluene,
and xylene— may be treated together, since they differ only in degree.
Toluene is benzene with one methyl2, CH S, group taking the place of
one H atom in the benzene ring, and xylene has two such groups.
The entrance of the methyl group lessens toxicity and xylene is said
to be distinctly less poisonous than benzene, but the difference betAveen benzene and toluene is not great; in fact, there are experi
menters who claim to have found toluene the more toxic of the two.
These bodies are poisonous to the central nervous system, producing
loss of consciousness, lowered temperature, and disturbance of res
piration and pulse rate. In mild cases there is a condition resembling
early alcoholic intoxication, with excitement, pleasurable or com
bative, headache, and dizziness. This is followed by depression, a
feeling of general illness, loss of appetite, and nausea, sometimes
vomiting. I f the exposure is greater, if the fumes are heavier, the
effect is very rapid and the stage of excitement may take the form of
acute delirium; the man shouts and sings and may be so unmanage
able that his would-be rescuers find it impossible to get him out of
liis dangerous situation before it is too late. Loss of consciousness
succeeds the delirium. The respiration is rapid and shallow, the pulse
weak and rapid, and convulsions may precede death. A more exces
sive exposure may cause immediate collapse and death within a few
minutes, from paralysis of the nerve center controlling respiration.
In the manufacture of explosives, chiefly of picric acid from car
bolic acid, which in its turn was made from benzene, there were
during a year’s time, 1915-16, 14 serious cases of industrial benzene
poisoning officially reported, seven of which were fatal. All of these
but two were men who were employed in some unusual piece of work—
pipe fitting, repairing stopcocks, cleaning stills and tanks. Germany
has had a similar experience. The German factory inspection reports
for almost every year mention cases of severe or fatal poisoning from
benzene in men who were repairing or cleaning benzene receptacles.
These cases, however, are rare, and so are the British cases.
We have
still in the United States an excessively large number of deaths from
benzene poisoning, and a study of the records shows that in some in
stances the necessary precautions are still slighted in spite of the
growing number of casualties.
2 For those unfamiliar with these chemical terms a short description is given in the
appendix of the structure of the benzene ring and the principal derivatives of the ring,
an explanation of isomeric forms, etc. The author is much indebted to Dr. W. Kritchewsky,
of the Sunbeam Chemical Co., Chicago, for his assistance in preparing the chemical parts
of this report.
BEN ZEN E, TOLUENE, AND XYLENE.
9
I f the poisoning takes place, not through a single exposure but
through repeated exposures, the action of benzene is characteristic
and easily recognized. It acts on the blood-forming organs, espe
cially the marrow of the bone, and as a result, there is a fall in the
number of both red cells and white cells. In one of the cases de
scribed by Selling,3 of Baltimore, the red cells, just before death,
numbered only 640,000 and the white cells 600. This was in a girl
of 14 who had been using a cement of rubber and benzene to seal
cans. Harrington,4 of Massachusetts, reported five cases of chronic
benzene poisoning in rubber-boot makers. One of these, a man who
had worked for 11 months, died in coma with convulsions. Before
death the red cells had fallen to 1,616,000 and the whites to 850. The
second striking effect of benzene is on the capillary blood vessels,
which rupture, allowing blood to escape under the skin and from
the mucous membranes. The skin is covered with purplish spots
like bruises, there is bleeding from the gums, sometimes severe nose
bleed or hemorrhage from stomach or intestines, and in girls men
strual hemorrhage.
The tissues attacked by benzene are those which must be depended
upon for the production of the so-called antibodies which defend
the body against infection by the germs of disease. As a consequence,
poisoning by benzene, and to a less extent by toluene, lowers the re
sistance to infections. In animals injection of benzene has been
shown to favor the development of an acute infection and also the
lighting up of a latent infection. This fact is of great importance
in connection with industrial poisoning from benzene.
The susceptibility to benzene poisoning varies very much, a fact
which must be borne in mind in connection with industrial cases.
Not long ago a report was made on the death of a pipe fitter from
benzene fumes. The man was changing coils in a benzene tank which
had been thoroughly blown out with steam before he enteied. There
was another man in the tank with him who was not affected, and
the company doctor therefore insisted that it was the physical condi
tion of the former that really caused his death. In a way that was
true; oversusceptibility to poison is certainly a physical condition,
yet no one would think of giving such an explanation for the deaths
from typhoid fever, which occur as a result of drinking infected
water, although there are always a large number of people who have
drunk the same water and yet escaped an attack of typhoid fever.
Individual susceptibility plays just as large a part in epidemics of
infectious disease as in poisoning from compounds used in industry.
An instance of the varying resistance to benzene is related by the
manager of a coke by-products plant. There was an overflow of
benzene through some accident, and two men who were working in
the room collapsed and fell in a faint. Two others who went in to
rescue them were also overcome, and so were two more. After the
six men had collapsed, there was a panic among the other workmen,
but finally an Italian offered to go in, saying that he never minded
the fumes. He did go in, not even protected by a helmet, and dragged
out the six men, one after the other, himself apparently quite unaf
fected by the benzene. Plainly it would be unfair to take the Italian
3 Selling, L. Johns-H opkins H ospital B u lletin . 1910, X X I, 33.
4 H arrin gton , T. F. B oston M edical and S u rgical Journal. 10 17, C L X X V II, 203.
10
INDUSTRIAL, PO ISO N IN G IN M A K IN G COAL-TAR, DYES.
as the normal type; indeed, his lack of susceptibility was a deviation
from the normal.
In the manufacture of dyes the only cases of benzene poisoning
so far reported have been of the acute type, resulting from a single
exposure to more or less heavy fumes. One instance will be sufficient
to illustrate this sort of accident, for all the reports read very much
alike. A man wras sent to the top of the benzene washer to change
the piping on the spray nozzle. He was told not to go into the
washer, which was empty bat had not been cleaned. He ignored this
order, took off the manhole cover, placed a ladder dow7n into the
washer and w^ent in, one of his helpers following him. The moment
he got to the bottom of the ladder he felt that he w^as going to faint,
started to climb up, but would have fallen if two helpers above had
not caught him and dragged him out. As they did so they saw the
other man fall on the bottom of the washer, but they were obliged
to help the pipe fitter down from the washer before they could return
for the helper, and by the time they got him out he was dying.
In this case no attempt had been made to render the washer safe
because the man was not supposed to go in, but there are repeated
instances recorded of severe and even fatal poisoning in men who
have not been allowed to enter the tank or still until it has been
emptied and steamed out repeatedly. Even a helmet of the Draeger
type is not always sufficient for protection. Not long ago a man who
wore one of these helmets fainted inside the tarfk and died soon after
he was removed. The only explanation that could be offered was
that the helmet had not entirely prevented him from breathing
through his nose.
Several cases on record in Germany show how" dangerous may be
the work of cleaning and repairing receptacles that have held ben
zene. Lewin5 in 1907 reported a case of fatal poisoning in a work
man who had tried to rescue a man overcome with benzene fumes.
A benzene kettle had stood empty for 22 hours, then it was washed
out three times with cold water and twice with steam and was
allowed to stand all night filled with cold water. The man w .ho was
sent in to make repairs took with him a pipe through which was blow
ing a strong current of compressed air. Nevertheless, he fainted and
fell to the bottom of the kettle. Several men tried to get him out,
but all grew dizzy and confused and had to give up, when an engi
neer, with a diver’s helmet succeeded in dragging him out. He was
revived, but one of the men who had tried to rescue him died 10
minutes after climbing out of the kettle.
The German factory inspection report for 1913 contains an account
of a similar case. Here, also, the tank wras supposedly thoroughly
cleaned, for it was boiled out three times, but the workman who went
in lost consciousness; and although the two men who had been set
to watch him dragged him out promptly he never came to.
There is far less fatal benzene poisoning in Great Britain than in
the United States, and one explanation for this fact was given by
the manager of a dye works. He said that it was not safe to send
a man into a benzene tank or still, no matter how carefully it had
been cleansed, till it had aired out for fully two days, for accidents
were very likely to occur if the men were allowed to enter at once.
5 Lewin.
Munchener medizinische Wochensehrift.
1907, LIV, 2377.
B E N Z E N E , T O L U E N E , AN D X Y L E N E .
U
He believed that the metal absorbs benzene and this must first be
allowed to evaporate.
The use of solvent naphtha, which is really an impure mixture of
toluene and xylene, in making naphthionic acid and in making benzidin, provides another source of poisoning from these coal-tar dis
tillates. Naphthalene is nitrated with Chili saltpeter and sulphuric
acid, then the nitronaphthalene is reduced with iron fillings and
hydrochloric acid and the resulting alphanaphthylamine is removed
from the iron sludge with the aid of solvent naphtha heated with
steam. The naphtha is later recovered for further use by distilla
tion. In one method of benzidin, and tolidin production, reduction
is brought about by zinc dust and solvent naphtha.
BENZENE DERIVATIVES.
The most important compounds used in the manufacture of dyes
are derivatives of benzene. The number and complexity of these
compounds is very bewildering to the ordinary investigator, but it
is not necessary that he should be familiar with all of them in detail,
because their action on the human body is much the same, although
it is modified somewhat by differences in chemical structure. The
following is a brief statement of what is known as to the relation
of chemical constitution to physiological action in the coal tar or
aromatic series.6
The phenols are hydroxy (H O ) derivatives; for instance, carbolic
acid is hydroxy-benzene; cresol is hydroxy-toluene; naphthol, hydroxy-naphthalene. The entrance of this hydroxy nucleus renders
the naphthols, alpha and beta, more irritating in their effect than
is naphthalene. An increase in the number of hydroxy groups in
creases toxicity, thus pyrogallol, trihydroxyhenzene, is stronger than
phenol, commonly called carbolic acid, which is monohydroxy ben
zene. But phenol is not nearly so dangerous an industrial poison
as benzene, for it is far less volatile. Severe burns may be caused
by phenol, although even this is not common, but systemic poison
ing is practically unknown in industry.
Pyrogallol, commonly called pyrogallic acid, is used in at least
one plant in the United States to produce gallocvanine. German
reports tell of poisoning by this compound, but no such case has as
yet come to light in this country.
The entrance of the sulphonic group ( S 0 2H 0 ) into a benzene de
rivative removes toxicity, thus anilin is rendered harmless by sulphonation, so is phenol. The entrance of COOH often has the same
effect; nitrobenzoic acid is harmless, although nitrobenzene is very
poisonous. The acetyl group (CO C H 3) lessens toxicity; acetanilid
is less poisonous than anilin. The introduction of an alkyl group,
methyl (C H S) or ethyl (C 2H 4) lessens toxicity, dimethylanilin be
ing less poisonous than anilin. This is, however, only when the
replacement is in the side chain,7 taking the place of H in the N H 2
group. I f the replacement takes place within the ring, toluidin is
formed, which is quite as toxic as anilin. The toxicity of the
0 Fraen kel, Sigm und. Die A rzn cim ittel S yn th ese a u f GrundTlage der P>eziehung zwiS'Ciien
ohem ischer A u fb a u und W irkung, B erlin , .19.12.
7 See Appendix fo r an explan ation .
12
IN D U ST R IA L PO ISO N IN G IN
M A K IN G COAL-TAK DYES.
diamines is greater than that of compounds with a single amine
(JSTH2) ; phenylendiamine is more ttixic than anilin.
Chlorine entering an aromatic compound changes it very little,
certainly does not increase its toxicity, in fact, chlorbenzene seems
to be less toxic than benzene. The nitroso group (NO) and the
nitro group ( N 0 2) increase toxicity always whether they enter the
ring or a side chain. All aromatic compounds with nitrogen are
more toxic than those without, but there is no rule as to increas
ing toxicity with an increasing number of X 0 2 groups. For in
stance, the 1-2-4 isomer 7 of dinitrophenol is much more poisonous
than trinitrophenol (picric acid). Mononitrobenzene is more poi
sonous to the central nervous system than dinitrobenzene, but the
latter has a more destructive action on the blood.
There is no rule as to the toxicity of the polymerides, but usually,
according to Fraenkel,6 the para position is more toxic than the
ortho. This is the general opinion of practical men with regard to
ortho and para toluidin, the latter of which is generally regarded as
much more troublesomec Usually, paranitranilin is considered more
dangerous than meta, and ortho less dangerous, but animal experi
ments carried on by Lewis, of the Sprague Memorial Laboratory
in Chicago, showed that for rabbits meta was more toxic than para.
In the case of the nitrochlorbenzenes the ortho isomer stands at the
head, then the para, and last the meta. As to the phenylendiamines,
there is a great difference of opinion among the men in the dye
industry, some holding that the para position is the worst, others the
meta.
Substitution products formed by replacement of the hydrogen of
the ring are decidedly more toxic than substitution products formed
by replacement of the hydrogen of a side chain. The toluidins are
very toxic; benzylaiftine is harmless.
The physiological effect of the nitro and amido derivatives pro
duces, in general, much the same clinical picture, differing in some
details and with a few striking exceptions. According to Curschmann 8 there is an important difference between the nitro and amido
compounds in that the latter are simply blood poisons and all of the
symptoms produced by them may be referred to their action on the
blood, while the nitro compounds have in addition a direct action on
the central nervous system. That this is true with regard to the
nitro compounds is undeniable, but according to Heubner9 it is true
of all the benzene derivatives, the amido as well as the nitro. Heub
ner succeeded in his experiments on rabbits in producing a narcotic
effect with collapse and paralysis before blood changes had had time
to take place, and he holds that not only nitrobenzene but phenol
and anilin affect the lower centers, those of respiration, vasomotor
control, and heat regulation.
In a light case of poisoning from one of these aromatic compounds
the face is flushed, there is a sense of fullness and throbbing in the
head, burning in the throat, tightness in the chest, then a violent
throbbing headache comes on, with dizziness, roaring in the ears,
6 F raen kel, Sigm und. Die A rzn eim ittel Svnthese a u f G rundlage der B ezieh u n g zw isehen
chem ischer A u fb au und W irkung, B erlin , 1912.
7 See Appendix fo r an exp lan ation .
8 Curschm ann, F . D eutsche V ic rte lja h rs se lirift fiir oflfentliche G esundheitspflege, 1 9 1 1 .
X L I I I , 225.
0 Heubner. Z e n tra lb la tt fiir G ew erbehygiene, 1914. II, 409.
BENZENE DERIVATIVES.
13
and some disturbance of sight. The flushing of the face subsides
and the color becomes livid, with bluish lips and tongue, while the
whites of the eyes are often tinged with yellow. I f prompt treat
ment is given, which means removal from all contact with the poison,
the attack may last only a few hours, and the man is able to return
to work on the following day. But even in so mild a case as this the
bluish color of the lips and tongue may persist for several days. In
severer cases, the color of the face is gray-blue, the lips and tongue
more deeply cyanosed, the muscles tremble, the man staggers and
feels as if his knees were caving in. He is nauseated and may vomit
and complain of cramps in the abdomen and extreme weakness.
Sometimes, usually a few hours after the onset of the attack, con
sciousness is lost. The respiration is shallow and quick; the pulse is
small, fluttering, irregular, and enormously accelerated; the skin is
cold and the blood pressure is usually low. I f coma persists the
respiration and pulse grow slower and slower, there is involuntary
defecation and urination, and convulsions usually occur just before
death. It is a characteristic feature of all these poisons that the at
tack seldom takes place while the man is at work, almost always
while he is on his way home, or even some hours later.
Blood.— Many studies have been made of the blood in poisoning
from benzene derivatives, and the changes in acute intoxication seem
to occur in the following order. Methemoglobin is formed early in
the course of intoxication, and probably coincidently with it is a
destruction of red blood cells. (Curschmann,8 Lehmann,10 Mohr.11)
The blood count and the hemoglobin fall. Microscopic examination
shows that the red cells are altered in size, shape, and staining prop
erties. The cells are pale, there is some fragmentation and polychromatophilia (abnormal reaction to staining fluid). Early in
the attack the blood becomes chocolate colored and thicker than nor
mal, and spectroscopic examination may reveal lines which are said
to be those of methemoglobin (M ohr11), or rather, lines situated
between the methemoglobin and the oxyhemoglobin, and therefore not
quite typical (Price-Jones and Boycott,12 Brat13). If, however,
the spectroscopic test is not made till later in the attack, it is usually
impossible to detect these lines. Indeed Curschmann says that by
the time cyanosis is fully developed methemoglobin can no longer
be demonstrated.
The evidence of the destruction of red corpuscles is succeeded in
a few days, from the second to the fifth, by evidence of active re
generation, and the blood picture then may be very much like that
of pernicious anemia, with variations in staining and in size and
with the appearance of stippled cells and nucleated cells. The
changes in the white cells are not so characteristic, but during an
acute attack there is usually a polymorphonuclear leucocytosis.
Later, as also in chronic poisoning, there is a lessened number of
these cells and a relative increase of lymphoc}^tes (Hudson14). In
8 Curschm ann, F . D eutsche V ie rte lja h rssc h rift fu r offentliche Gesundheitspflege.
X L II I , 225.
10 Lehm ann, K . B. A rc h iv fu r H ygiene. 1912. L X X V , 1.
11 Mohr. D eutsche m edizinische W och en sch rift. 1902. X X V I I I, 73.
12 Price-Jones and B oycott. G u y’s H ospital R eports. 1901. L X I I I , 309.
13 B ra t. D eutsche m edizinische W ochenschrift. 1901. Nrs. 19 and 20.
14 Hudson, W. G. M edical Record. 19 17 . X C I, 89.
19 11.
14
IN D U ST R IA L PO ISO N IN G IN M A K IN G COAL-TAR DYES.
the slower forms of poisoning the destruction of red cells acts as a
stimulus to further cell production on the part of the bone marrow,
and an increased red cell count may be found. Malden15 examined
the blood of 13 men employed in an English factory where anilin
and nitrobenzene were made. Six of the 13 had a high red cell count
with a low hemoglobin, and many imperfectly developed red cells.
Loss of hemoglobin ran from 5 to 50 per cent, The cells showed
great variations in size, the large predominating, but more note
worthy was the appearance of stippled cells, which Malden considers
quite as characteristic of the early stages of anilin poisoning as it is
of lead poisoning. Malden summarizes the changes in the blood
caused by small repeated doses of anilin thus; Ked cells increased
in number with loss of hemoglobin; low color index; degeneration
and imperfect regeneration of red cells, increase of lymphocytes,
decrease of polymorphonuclear leucocytes.
Urine.— Yery vaiying results are reported from the analysis of
the urine in cases of acute poisoning. Hay h produced symptoms in
himself of intoxication with marked cyanosis by rubbing dinitro
benzene on his skin, but his urine showed no abnormality. Sugar
and casts are commonly absent in the urine, although there are oc
casional instances of reduction of Fehling’s solution. Albumen is
usually not found, except perhaps for a trace, in acute intoxication
of moderate degree, even when the urine is a dark browTn color.
This brown color is very common and is often the first warning the
workman has that he is beginning to experience the effects of the
poison. A chemist who once had had a severe attack of anilin
poisoning from drawing a quantity into his mouth while siphoning,
told me that always after that if he came in contact with anilin he
would notice this change in the color of the urine, although he might
feel no subjective symptoms at all.
In severe poisoning the urine may be a dark brown or the color of
port wine, or a smoky red, and in such cases methemoglobin or un
changed hemoglobin or blood pigment, bile pigment, hematoporphyrin, may be detected. Albumen can sometimes be demonstrated, but
not always, even in severe cases (Mohr11). Some observers insist
that bile pigment is never found in the urine; others that bilirubin
can be detected in the majority of cases. Mohr found hydrobilirubin
frequently after dinitrobenzene and chlorbenzene poisoning. No
thorough study has as yet been made of the reduction of Fehling’s
solution, although the occurrence of this phenomenon is reported
fairly frequently. Six such cases were described in a personal
communication by Dr. Kessler, of Marcus Hook, in men who had
been working with dinitrobenzene and anilin. Their urine was dark
brown, contained bile pigment, and had reducing properties. A
seventh case was one of fairly severe poisoning from mononitro
benzene.
Dr. Sutherland, of the du Pont Co., who has some 1,200 men under
his care, says that he finds not infrequently urines reducing Fehling’s
in men who show signs of poisoning from nitro or amido compounds.
Muller reported a case of anilin poisoning, in which the urine
contained no sugar, no blood, nor albumen, but had strongly reducing
6 W h ite and H ay. L an cet. 1901. II, 582.
11 Mohr. D eutsche m edizinische W och en sch rift. 1902.
15 M alden. Jou rn al of H ygiene. 1907. V II, 672.
X V I II , 73.
15
B E N Z E N E DERIVATIVES.
properties. According to von Jaksch,16 a substance which reduces
copper sulphate and is also lsevorotatory was found in the urine of a
man suffering from nitrobenzene poisoning. This urine smelt
strongly of oil of mirbane, contained a trace of sugar and an increase
of ammonia and acetone.
Neubauer17 says that in severe anilin poisoning anilin may be
found unchanged in the urine, but this is rare. Usually it is changed
by oxidation and conjugation to paraamidophenol— sulphuric ester.
Nitrobenzene and the nitranilins are also excreted as paraamido
phenol, while the reduction product of dinit rophenol, which appears
in the urine after poisoning from this substance, is amido 2 nitro 4
phenol.
Bladder tumors.— In the early years of the present century the phy
sicians attached to the great color works at Hoechst noticed that
workmen in this plant were to an unusual degree victims of tumors
of the bladder, sometimes cancerous, sometimes benign. In 1904
they began to ask information from 18 other German dye works con
cerning the occurrence of bladder tumors and of inflammation of the
bladder, cystitis, and the responses to these inquiries brought to
light 38 cases, 18 of which were fatal. This report attracted great
attention and was followed by others from time to time until, in 1920,
the number of known instances of bladder tumor in German dye
works reached 177.
At a meeting of industrial physicians in Germany in 1913 Leuenberger spoke on this subject, pointed out the fact that it was un
doubtedly an amido, not a nitro body, which must be held responsible
for bladder tumor formation and urged the physicians attached to
dye works to tabulate their cases and discover which were the danger
ous departments and what was the compound eliminated in the urine
that acted as an irritant to the bladder. The answers to these ques
tions are now appearing in the Zentralblatt f iir Gewerbehygiene.
Schwerin, of the Hoechst factory, studied the histories of 99 of
the 177 cases and found that they were distributed ifi the following
departments:
Cases.
Fuchsin and rubin_________________________________
Benzidin and naphtliionic acid________________________
Naphthylamins___________________________________
A n ilin __________________________________________
Other bases, not specified____________________________
Palatine black____________________________________
B lu e___________________________________________
Patent blue______________________________________
21
28
30
8
8
1
1
1
A later report by Curschmann discusses 28 recent cases— included
among the 177— of which 15 were malignant, 12 benign, and one
mixed. These cases wTere distributed as follows:
Cases.
8
Fuchsin and rubin_________________________________
Benzidin and naphthionic acid________________________
Betanaphthylamin and naphthol______________________
A n ilin __________________________________________
Other bases______________________________________
B lu e ___________________________________________
3
10
5
3
4
18 v. Jaksch, R. Klin. Diagnostik innerer Krankheiten. 6th ed. Berlin-Vienna. 1907.
17 Nenbaner. Analyse des Hams. 11th ed. Hupperts’s Lehrbuch. Wiesbaden. 1913.
Vol. 2, 1479.
16
IN D U ST R IA L PO ISO N IN G IN
M A K IN G COAL-TAR DYES.
The age at which the growth made its appearance was over 50
years for 14 of the 28, between 40 and 50 years for 8, and between
30 and 40 for 6. The 12 men who had only benign tumors had
worked for a shorter time in the industry than had those with can
cerous growths. Five had been employed in dye works for 10 to 15
years, 5 more for 15 to 30 years, and 2 for more than 30 years, but
of the 15 with cancer, only 2 had worked less than 15 years. The
histories of many of these cases show that a tumor which is at first
only a papilloma may later undergo cancerous degeneration.
Curschmann says that although anilin may give rise to these
tumors yet there is no apparent connection between ordinary anilin
poisoning and bladder tumors.
Leuenberger, at the conference of industrial physicians in 1913,
expressed the view that the amido compounds which seem to be re
sponsible for tumor growth in the bladder undergo hydrolysis (in-'
troduction of HO into the ring) in the body and suggested that it
might be possible to ascertain which of the amido bodies are elimi
nated in this particular form, as paraamidophenol, and then see
whether they are actually the ones which are associated with the
tumor cases. It is true, as Schmiedeberg found years ago, that ani
lin and several other aromatic amido compounds are changed in
the body to paraamidophenol and excreted in the urine as paraamidophenol-sulphuric-ester. But this is not true of some compounds
which are apparently very important sources of tumor cases. Paratoluidin is one; others are alpha and beta naphthylamin, both of
which latter are excreted in the urine unchanged.
Kuchenbacker, arguing that such a body as paraamidophenol,
having a free amido group, should be capable of diazotizing in acid
solution with nitrate and produce an azo color, tested the urines of
men in a benzidin-naphthionic department and found that those espe
cially of men who were exposed to dusts produced a reddish azo dye,
varying in intensity according to the degree of dust exposure. He
could also obtain an azo color from the urine of dogs fed with anilin,
and with orthotoluidin, but not after feeding with paratoluidin nor
with benzidin, nor tolidin, nor alpha nor beta naphthylamin.
It seems, therefore, that paraamidophenol is not the only com
pound responsible for the cystitis and the later papillomatous tumors
which occur in these dye makers, and for the present the matter
rests here. The work of determining just what does take place in
the elimination of these various aromatic bodies and what resulting
compound sets up the cystitis which precedes tumor formation is
going forward in the German laboratories with the hope that it will
be possible some day by means of urinary tests to discover when such
a condition is threatened. Meantime they have at least ascertained
which are the departments in which bladder difficulties are to be
looked for and are in a much better position to guard against this
form of occupational poisoning than hitherto.
In England the dye industry is not yet old enough to have pro
duced more than a very small number of bladder tumors. The phy
sician connected with the oldest of the English plants has1known of
two cases, although he believes that there may have been more
which escaped detection. Since only exceptional cases in Germany
have developed after less than 10 years’ exposure, it is highly im
BENZENE DERIVATIVES.
17
probable that American dye works have as yet been responsible for
any eases, and our great labor turnover will probably serve to protect
the greater number of dye workers from it. However, skilled work
men and foremen and chemists are not shifting, and it will be well
for American dye makers and industrial physicians to bear in mind
the German experience and be on their guard against similar occur
rences in their plants.
Industrial poisoning from these compounds, especially from the
amido compounds, is rarely fatal. I f death occurs it is preceded by
coma, increasing paralysis of heart and respiration, convulsions, and
sometimes edema of the lungs. These compounds do not usually
produce any very characteristic changes in the organs with the ex
ception of a few, such as, for instance, trinitrotoluene, which causes
a very characteristic degeneration of the liver. The usual findings
consist in slight degenerative changes in liver, heart, and kidneys
and sometimes pneumonia or edema of the lungs, or hemorrhages
into the lungs and stomach and intestines.
Mode of entrance.— The volatile compounds of this group may be
inhaled, but even with the volatile compounds absorption through
the skin is more important, and it is probably the only mode of
poisoning for the solid compounds.
The more volatile a compound the more rapid the poisoning.
Cyanosis is greater in poisoning by amido derivatives; the effect on
the central nervous system is more pronounced in poisoning by nitro
derivatives. In Hay’s &experiment on himself, a few hours after a
second application of 0.1 gram of dinitrobenzene in ointment his
lips became a vivid blue color, his skin leaden, his pulse was 120,
with high tension, and there was a sense of fullness and throbbing
in his head. Curschmann8 produced fatal poisoning from paranitranilin in cats by rubbing a few grams on the skin, and the same
result was obtained with phenylene diamine. Skin absorption is
favored by intimacy of contact, pressure, or rubbing, a hot atmosphere
which flushes the surface blood vessels and causes sweating, by per
sonal idiosyncracy (probably dependent on the character of the
sweat), and finally by the ability of the compound to dissolve fatty
acids and pass rapidly through the skin.
Although there is no doubt that skin absorption is very much the
most important factor in industrial poisoning, symptoms may also
be produced by the inhalation of fumes and dust, as was shown,
for instance in the British studies in trinitrotoluene poisoning dur
ing the war. Most of the TNT poisoning in the ammunition works
followed direct contact with the substance, but there was also evi
dence that fumes and dust were not negligible. The same thing
was found to be true in American TN T manufacture and loading,
where the greater part of the trouble came from contact, but fumes,
especially when mixed with steam, gave rise to unmistakable absorp
tion of the poison.18 Several instances have been reported of un
complicated fume poisoning from anilin and other compounds in
b White and Hay. Lancet. 1901. II, 582.
8 Curschmann, F. Deutsche Vierteljahresschrift fur offentliche Gesundheitspflege.
XLIII, 225.
18 Practical points in the prevention of TNT poisoning. M o n t h l y L a b o r R
United States Bureau of Labor Statistics. January, 1919, p. 248.
1911.
e v ie w
,
18
INDUSTRIAL POISONING IN M A K IN G COAL-TAR DYES.
dye works. For instance, a poisoning occurred on the second story
of a reduction building from anilin fumes which passed through the
cracks in the wooden floor from the story below. The apparatus
was very poor in this reduction department, and it was often neces
sary to open up the reducers and dig out the caked iron filings, so
that the fumes of anilin were often quite heavy. In another case,
a man was working a machine like a cream separator for separating
anilin from water. He did not come in contact with the anilin at
all, but he was taken ill and was under treatment for eight days.
The installation of a suction fan to draw away the fumes made
it possible for him to go back to his work with no further trouble.
From another plant comes the history of a man who was set to
make repairs above a reducer where monochloranilin was being made
from nitrochlorbenzene. Seduction was over and fumes were com
ing off from the hot open reducer. The man was working at the
ceiling just over it, and after 45 minutes he had to be carried down,
overcome by the fumes. He was dangerously ill for several days,
and could not return to work for some weeks. Cases of fume poison
ing also occur among men engaged in centrifuging (called “ wring
ing” or “ spinning” ) the mixed toluidins to separate para crystals
from the oily ortho. Even when the centrifuges are out of doors
very heavy fumes are given off during the process and apparently
severe poisoning may occur without any contact at all.
The above is a description of typical poisoning from most of the
nitro and amido derivatives of benzene. It is necessary, however,
to take up the more important compounds in greater detail, because
they differ from one another more or less with regard to the promi
nence of one or the other symptom and they differ in degree of
toxicity, and in at least one instance (dinitrophenol 1-2-4) there
is a decided divergence from the usual type.
TH E NITRO COMPOUNDS.
Mononitrobenzene (C6H 5JJ(X) and ?netadvnitro 'benzene (C8H 4
(ET02) 2) are very important in the dye industry. Mononitrobenzene
is a yellow oily fluid, smelling like oil of bitter almonds, insoluble
in water but readily soluble in fats. It therefore passes easily
through the skin and may cause poisoning in this way or through
the inhalation of fumes. In animals death is brought about more
quickly by the liquid mononitrobenzene than by the solid dinitro,
and this is also probabty true in human beings. Occasionally mono
nitrobenzene is spilled or splashed on the skin and then the symp
toms of poisoning come on very quickly. The blood may turn choc
olate color and the urine dark within a few hours after a slight
accident o f this sort. I f the clothing is soaked with nitrobenzene
the resulting collapse may be very sudden and severe.
A n account of a fatal case of nitrobenzene intoxication may be
found in the records of the Massachusetts General Hospital for July,
1916. The patient, an elderly man, was at work in a soap factory,
carrying a 5-gallon can of oil of mirbane. He seems to have spilled
some of the fluid on his trousers, and was seen to grow rather shaky
and then suddenly collapsed, spilling more of the fluid on himself.
It is evident from the record that his mirbane-soaked clothing was
T H E NITRO CO M POU NDS.
19
not removed but that he was sent to the hosptal as he was, so that
it is no wonder that by the time he reached there his condition was
serious. He was unconscious, breathing slowly and irregularly, but
the heart was regular with good action. His pupils were small,
irregular, and did not react. The skin was of a dark gray-blue
color. Some blood was withdrawn from the arm vein and it was
chocolate colored. Respiration failed, becoming more irregular and
shallow, but the heart action was good till just before death, which
occurred one hour after he reached the hospital.
Dinitrobenzene (meta) is a solid, which, however, volatilizes
slightly at room temperature. By universal agreement it is pro
nounced the most troublesome compound that is used in anilin-dye
manufacture. This does not mean that it is mo.re poisonous than
mononitrobenzene, but that the requirements of manufacture are
such that men are necessarily brought in contact with it far more,
and therefore industrial poisoning is much harder to control. The
symptoms of acute poisoning are the same as those of nitrobenzene
poisoning, but in addition to acute intoxication there is a more
chronic form, which has been described by the British and the
Germans, both of whom have had ample opportunity to observe it
among the workers in factories making roburite, an explosive much
used before the war, consisting of dinitrobenzene and ammonium
nitrate. Prosser W hite19 describes a severe form of anemia in
dinitrobenzene workers, with a dusky yellow skin, jaundiced sclera,
an appearance of partial asphyxia, wasted muscles, dulled sensi
bility, partial paralysis of the hand, defects of vision. Dr. Rox
burgh, of Manchester, England, told of a symptom he had observed
as an aftereffect of dinitrobenzene poisoning in two men, which
consisted in ataxic gait, the men staggering as if from drunkenness.
This came on intermittently during more than a week’s time.
R ohl20 saw 60 cases of dinitrobenzene poisoning in a roburite
factory at Witten. The men were emaciated and weak, the skin
was dirty yellow, the pulse weak, the spleen enlarged, there was
dizziness, narrowing of the field of vision, and disturbances of sen
sation, especially a feeling of cold and weight in the legs. In the
worst cases the blood was chocolate colored.
In American dye works DNB, as it is called, is much dreaded.
Often it is the only substance that causes real alarm. There is much
more exhaustion, more weakening of the heart, than in poisoning
from anilin, and the effects of an acute attack last much longer,
dragging on sometimes for days or weeks. The anemia may be
extreme and persistent. Acute poisoning from a single large dose
is exceptional and is usually the result of an accident. In one plant
16 men were poisoned, several of them being unconscious for 6 to 8
hours, and one had convulsions at intervals for 12 hours. They
were tearing out bricks and rafters in an old room which had been
used for the production of DNB.
It is not only in the production of DNB but in its use as an inter
mediate, especially for reduction to metaphenylendiamine and for
reduction to metanitranilin, that the danger arises. Formerly DNB
19 Prosser White. In Oliver’s Dangerous Trades. London, 1902, p. 475.
20 Rohl. Ueber akute und chronische Intoxikationen durch Nitrokorper der Benzolreihe.
Inaugurations Dissertation Rostock, 1S90.
20
IN D U ST R IA L PO ISO N IN G IN
M A K IN G COAL-TAR DYES.
used to be run out into open pans, where it caked, and men were sent
to chop up the cake and shovel the fragments into trucks, in the
course of which work a great deal of poisoning occurred. One man
was interviewed in a hospital, where at the end of a week he was
still somewhat cyanotic. He had worked for nine days in an open
shed breaking up and shoveling solid DNB. On the ninth day
he had a severe one-sided headache and was so dizzy that he was
obliged to go home. The next day he came back to work, but after
a little while he became very ill and deeply cyanosed. He was sent
home, but the cyanosis persisted, and the company sent him to the
hospital for a week. Another man from the same department had
to be sent to the hospital after only one day’s work. Later on this
method of handling DNB was generally abandoned because of the
effect on the men, and the molten DNB is now usually run out to
meet a stream of cold water, which granulates it. However, even
the shoveling and dumping of the granulated material may expose a
man to sufficient fumes to poison him. Before the introduction of
the pelleting method it was found in one plant that 50 per cent of
all the sickness was among the DNB men, although they numbered
only 24 in a force of 1,500. A history of 27 cases of acute poisoning
in men breaking, screening, and washing DNB shows the duration
of incapacity was from 1 to 12 days.
Nitrotoluenes.— Ortho and paramononitrotoluene (C6H 4CH 3N 0 2)
are used to produce by reduction the important intermediates
ortho and paratoluidin. During the war dinitrotoluene (C6H 3CH 3
( N 0 2) 2) was produced as a stage in the manufacture of TNT. In
the dye industry it is used for the production of toluylendiamine.
According to Dambleff21 and Jaffe22 the ortho is the more poisonous
of the mononitrotoluenes, at least for animals, but neither ortho nor
para is as toxic as mononitrobenzene. They act more slowly and ap
parently only upon susceptible subjects, for many men can handle
them with seeming impunity. They are absorbed through the un
broken skin and in susceptible persons they produce symptoms re
sembling those of nitrobenzene poisoning. Zieger23 says that the pa
thology and symptoms of mono and dinitrotoluene are the same, en
largement and tenderness of the liver, cyanosis, gastric disturbance,
painful, scanty urination, destruction of red blood cells, methemoglobin, and the symptoms pointing to oxygen starvation. There is a
record of a typical case, with cyanosis, shortness of breath, and head
ache, in a man who was sent into a tank which had contained mononitrotoluene, but which was supposed to be quite clean.
The French committee on munition poisons found DNT toxic to
animals, the deadly dose being 0.5 gram per kilogram of weight. A
marked effect on kidneys and liver was noted. DNT seems to differ
in its action from TN T in several ways. Dambleff quotes Zieger as
emphasizing the eye symptoms in DNT workers, a venous congestion
of the retina and disk. Cases of multiple neuritis have been described
in DNT workers differing from anything observed as a result of the
21 Dambleff. Beitrage zur Kenntniss der giftigen Wirkung nitrierter Benzole, Toluole,
etc. Inaugurations Dissertation Wurzburg, 1908.
22 Jaffe. Quoted by Robert. Lehrbuch der Intoxikationen. Stuttgart, 1911, p. 804.
23 Zieger. Inaugurations Dissertation Wurzburg, 1913.
T H E N IT R 0 COM POU NDS.
21
action of TNT. For instance, Hamilton and Nixon24 give the fol
lowing history of an interesting case: The man was a foreman, 39
years old, whose health had always been good, with no history of
family idiosyncrasy or of alcoholism or venereal disease. He had
worked for two years in contact with DNT. At the end of the first
year he had numbness and prickling in the feet which, after five
months, spread to the knees. There was no pain, but a sensation like
the prickling of an electrical current. He was changed to outside
work and improved, but when he went back to the old work the
numbness increased in feet and legs. Then his sight began to fail,
and examination showed 20/40ths in the right eye, and 20/70ths*in
the left. There was slight cyanosis, anemia, and numbness in the tips
of the fingers. Four months later his sight failed so that he was
obliged to quit work. Some time after that, the authors found the
sight to be 6/200ths in each eye. The man could find his way about,
but could not recognize faces. His physical condition was practically
normal except for the loss of 8 pounds and he complained of loss of
strength.
Examination of the fundus showed well-developed
atrophy, with pale disk, some swelling of the veins, and contraction
of the arteries. Vibration sense and joint sensibility were lost in the
toes; touch was impaired but not pain; there was impairment of
touch sense in the fingers. Coordination was impaired in the legs;
not in the hands. He complained of a pulling up or jerking of the
muscles of the legs like an electric shock. The only reflex affected
was the patella, which was diminished. He was anemic, the red
cells numbering 4,900,000, hemoglobin 80 per cent, whites 8,000, with
a normal differential count. He improved under rest with sweating,
and 10 months later had 20/40ths vision in his right eye, 20/60ths
in his left. Another man in the same plant quit work at the end of
six months because of numbness in his feet and swelling so that he
could not put on his shoes. Two other men complained of numbness
in the feet, with tingling, difficulty in walking, and headache.
Koelsch 25, in Germany, and the experts of the French commit
tee on munition poisons hold that the poisoning experienced in con
nection with DNT manufacture is due not to the DNT itself but
to tetranitromethane and perhaps to certain isomers of DNT and
TNT. The pure substances they hold to be very slightly toxic.
Certainly it is true that the worst place in a nitrating department
for D N T is the centrifuge for the separation of DNT from other
products of nitration, and the men engaged in such work believe
that the oily liquid which separates off and is rejected is the source
of the trouble.
The effects of trinitrotoluene were closely studied during the
war. It is a slowly acting poison and affects about one-third of the
people who are exposed to it. Injury to the bone marrow causes a
great destruction of red blood cells and as a result a hematogenous
jaundice develops. Among the British munition workers there were
360 known cases of toxic jaundice from TN T poisoning, with 96
deaths. Much more rarely an aplastic anemia of extreme type de
veloped without the typical degeneration of the liver. Both forms
were found also in American munition works. Trinitrotoluene is not
24 Hamilton, Arthur S., and Nixon, C. E. Journal of American Medical Association, 1918.
LXX, 2004.
25 Koelsch. Mimchener medizinische Wochenschrift. July 24, 1917.
22
IN D U ST R IA L PO ISO N IN G IN
M A K IN G COAL-TAR DYES.
used in dye manufacture and it is important in this connection only
because its method of action has been so thoroughly studied that
the literature of TN T poisoning may serve as a guide to us in the
understanding of similar compounds that are used in dye manu
facture.
Nitronaphthalenes (C10H 7NO2, C10H 6(NO2) 2, etc.).— The nitronaphthalenes have been found by German observers, Silex26 and
others, to have an effect upon the eye. It is very gradual and not
painful, consisting in very small transparent vesicles on the cornea
which cloud it and diminish vision. Industrially these bodies are
pfacticaily harmless because they have a low volatility and slight
solubility.
In animals, R ohl20 found that he could produce
methemoglobin with nitronaphthalenes.
Anisol (C6H 5CH 30 ) . — Anisol is phenol with one methyl group
displacing the H of the hydroxyl group. Orthonitranisol is a dark
brown liquid of strong penetrating odor. Dambleff 21 found that
he could produce death in a rabbit, with hemorrhage into the lungs,
by rubbing into the skin a quantity representing 0.5 gram per
kilogram. Trinitranisol was apparently used by the Germans dur
ing the war as an explosive; at least it is mentioned among the
compounds studied by Koelsch in his inquiry into munition poisons.
He found that it seemed to cause no general symptoms but an affec
tion of the skin to which practically all workmen were susceptible.
An eruption came on very quickly after only a few hours’ exposure,
spread all over the body, with very painful swelling of the eyes,
swelling of the lymph glands, edema of the skin, superficial abscesses
and secondary symptoms from the acute inflammation.
The French committee on munition poisons found dinitranisol to
be one of the two worst toxic compounds among those that were
tested on animals.
Dwbitrophenol (C6H 3H 0 ( N 0 2) 2) .— Before leaving the nitro com
pounds it is important to mention one which is used in dye manu
facture to a limited extent, and is not in itself important, but its
physiological action should be studied in detail because it differs
so radically from the action of all the other known nitro deriva
tives of the benzene ring which have thus far been studied. Before
the war this compound was not known to differ in any way from
the others, but during the war it was manufactured on a large scale
in France and entered into the composition of the mixture used by
them for loading high explosive shells. The enormous human experi
ment carried on in the French munition plants showed this com
pound to be possessed of striking peculiarities, and it is important
to call attention to these because obviously it is possible that other
nitro bodies may, as they come into more extended use, prove to have
similar characteristics.
The compound in question is dinitrophenol, but only one isomer,
the one having the HO group, which changes benzene to phenol,
occupying position 1 in the ring, while the two nitro groups occupy
80 Rohl. Ueber akute und chronische Intoxikationen dureh Nitrokorper der Renaolreihe.
Inaugurations Dissertation Rostock. 1890.
21 Dambleff. Beitr&ge zur Kenntniss der giftigen Wirkung nitrierter Benzole, Toluole,
etc. Inaugurations Dissertation Wiirzburg, 1908.
26 Silex.
B erlin er klinische W o c h e n s c h rift, 1 9 0 0 , p. 1 1 9 1 .
T H E N IT R 0 COM PO U N DS.
23
positions 2 and 4.27 It is therefore known as dinitrophenol 1-2-4.
The method of manufacture used by the French and in two Ameri
can plants which were manufacturing for the French starts with
monochlorbenzene, which is nitrated to dinitrochiorbenzene. The
hydroxide of calcium or sodium displaces the chlorine and then is
removed as a soluble chloride by hydrochloric acid, leaving dinitro
phenol. This was used together with trinitrophenol, picric acid,
usually in the proportion of 40 DNP to 60 TNP. The French did
not expect any serious trouble from occupational poisoning in this
work because they had long been familiar with picric acid and as
sumed that dinitrophenol would resemble it very closely. So much
illness, however, developed in connection with the handling of
dinitrophenol and exposure to fumes and dust that the Government
ordered a thorough inquiry into the action of this compound, and
the result of the inquiry, together writh the clinical reports of actual
cases of poisoning, have been abstracted for American readers by
Roger G. Perkins,28 of Western Reserve University, consultant in
hygiene of the United States Public Health Service.
Briefly stated, the essential facts are these: Three varieties of in
toxication are described: First, mild, subacute, which serves as a
warning to the physician to remove the workman from danger in
time. The man complains of loss of appetite, nausea, sometimes
vomiting, colic, and diarrhea. There is general weakness, with
headache and dizziness and moderate sweating, especially at night.
The tongue is white and furred, and there is decided loss of weight.
The urine shows the presence of a reduction product, amido-2-nitro4—phenol, which test is depended upon to indicate absorption of
dinitrophenol. The second form is an acute intoxication which usu
ally is preceded by the type just described. The onset is sudden, a
complaint of extreme weariness in the limbs, painful constriction at
the base of the chest, and a burning thirst. The face is pale, with
slight cyanosis of the lips. The man sweats abundantly and shows
an agitation and anxiety which is quite characteristic. Another very
characteristic sign is short, difficult respiration, the difficulty being
greater on inspiration, while in an asthmatic attack it is expiration
which is hardest. There is only a slight rise of temperature, the
pulse is regular and the lungs usually clear. There is a decided
diminution in the quantity of urine, and the reaction for the detec
tion of the reduction product, known as the Derrien reaction, in
creases in intensity. Removal from work, with a rest cure, is usu
ally followed by an increase in the amount of urine passed and a
rapid recovery, but no immunity follows the attack, and these men
require special watching. The third form is fulminating intoxica
tion. This is especially noted among alcoholics or persons with
renal or hepatic troubles; death may take place in a few hours. The
onset is sudden, with an attack of weakness or, less often, violent
colics and diarrhea. A feAV hours later there is fever up to or over
no
/ \
\
28Perkins, R. G.
NOa
/
nq2
U. S. Public Health Reports, 1919.
Vol. 344, p. 2335.
24
IN D U ST R IA L PO ISO N IN G IN
M A K IN G CO AL-TAR DYES.
40° C. (104° Fahrenheit), abundant sweats which stain the skin
yellow, even over the parts where there has been no exposure to the
chemicals. There is intense thirst, the pupils are contracted, the
patient is frightened and excited, and there may be partial or gen
eral convulsions. This is followed by unconsciousness, coma, and
death in a few hours. It is the clinical picture of a fatal case of
uremia. The symptoms in the severe cases which get well are much
the same at first, but the second or third day shows marked im
provement, with rapid recovery. Some very rapid cases are de
scribed, developing while the workman was on his way home. He is
found somewhere along the road breathing with difficulty, covered
with sweat, with a temperature of 41° C. or even 43° C. (105.8° or
109.4° Fahrenheit), and he dies before anything can be done. Some
times there is a rise of several degrees of temperature after death.
Urine obtained by catheter shows an intense Derrien.
Perhaps the most interesting feature of the post-mortem examina
tion is that no characteristic lesions are found. There may be edema
of the lungs, at times a fatty infiltration of the liver, but the micro
scopic lesions in the liver and kidney cells are inconstant. The blood
and organs always contain DNP, or its derivatives, but this is also
true of the organs of workmen who die from accidental causes while
employed on DNP.
The French experimenters found that the action of dinitrophenol
1-2-4 is highly specific. None of the above symptoms are produced
by ortho or meta mononitrophenol while paramononitrophenol, which
produces similar results, does so only in heavy doses and transiently.
The same thing is true of the 1-3-4 isomer of dinitrophenol. The
other isomers have a different effect, causing the formation of methemoglobin. Dinitrophenol 1-2-4 is a specific poison, causing in all
warm-blooded animals an exaggeration, of the heat radiation activi
ties with progressive elevation of the temperature which ma}^ rise to
45° C. (113° F.) at death. The basis of these phenomena is an
increase of cellular combustion, oxidation, which has no relation
to muscular work, nor to any action on any special organ, nor to a
stimulation of the nervous system, for it occurs even in cold-blooded
animals.
The compounds tested by the French committee included the nitrotoluenes, the nitroxylenes, nitranisols, nitrophenols, and chlorbenzenes, and they found that the most toxic compound of all was dini
trophenol 1-2-4, with the corresponding isomer of dinitranisol com
ing next and chlorbenzene last.
There were four deaths from dinitrophenol 1-2-4 in the two Ameri
can factories which manufactured melenite for the French. Three of
these, who were handling the compound dry, developed symptoms
very suddenly and died within 24 hours. From the meager report
obtainable it seems that these cases were like those described by the
French. The fourth case, which occurred in another factory, was not
typical. The man died after an illness lasting several days, and
autopsy showed that he was suffering from a toxic jaundice such as
occurred in men poisoned by trinitrotoluene. It may be that in this
instance some other isomer was present, not the 1-2-4. From a state
ment made by Leymann29 in 1902, sudden and severe poisoning may
29 Leymann.
Vierteljahrssehrift fiir gerichtliche Medizin, 1902.
Supplement, p. 311.
TH E N ITRO COM POU NDS.
25
develop in dye works from the dinitrophenol used in making sulphur
black. Leymann describes three such cases. One man, who had been
cleaning some washing tanks, collapsed suddenly with pain in his
chest, vomiting, then fever, and convulsions, and died in two hours.
The second case had a similar history. The third is not described.
The dinitrophenol used in the making of sulphur dyes is, it is said,
the 1-2-4 isomer, and certainly the history of Leymann’s cases re
sembles very strongly those reported from the French munition
works.
It is not likely, however, that poisoning from this compound should
occur in dye works except as the result of some accident, leakage, or
something necessitating the interruption of the process and repair
wrork, for the dinitrophenol that is formed is not isolated, it is at
once fused with sulphur to form sulphur black, and workmen would
not come in contact with it in the ordinary procedure of the reaction.
ANILIN AND OTHER AMIDO COMPOUNDS.
The symptoms of the amido derivatives of the benzene ring are
less serious than those caused by the nitro derivatives. While cyano
sis is deeper with an amido compound, it is not accompanied with
as severe prostration as follows poisoning with a nitro compound.
A case of dinitrobenzene poisoning does not present as alarming a
color as one of anilin poisoning, but the symptoms of involvement of
the central nervous system, changes in pulse, respiration, and body
temperature are much more grave. Convalescence is also slower.
Typically a case of anilin poisoning does not incapacitate a man for
more than a day or two, although it is a question whether he should
be allowed to return to work unless a blood examination shows his
hemoglobin not much lower than normal. But after dinitrobenzene
poisoning a workman is likely to be ill for a fortnight or more.
A typical case of anilin poisoning, selected at random from a large
number of similar records, has the following history: An Irish pipe
fitter, a fairly heavy drinker, had worked for two weeks in an anilin
reduction department, his work bringing him every now and then
in direct contact with anilin-smeared apparatus. He would come
back from work w^eak and tired, complaining of the fumes in the
plant. His wife said that his face looked dusky and his eyes un
natural. He did not complain of pain, but of feeling sick all over.
On the fifteenth night he lost consciousness and was taken to the hos
pital. The hospital record reads: Skin all over body steel gray color;
face, scalp, and hands blue; unconscious; pupils normal; sclera jaun
diced ; respiration somewhat labored, 30 to 39; temperature 97.2°;
pulse 130 to 140, shallow; lungs normal; heart normal in size and
sounds; abdomen normal; hemoglobin 75 per cent; urine dark brown;
albumen. He vomited twice on the first day, on the second his mind
was clear, his pulse of good quality, but still rapid, 112; respirations
29; temperature 98.4° ; no albumen in the urine. By the seventh day
he could be discharged, but on the tenth day he was still weak and
his sclera still jaundiced.
A severer poisoning results in intensification of all these symptoms.
A workman engaged in experimental work which involved exposure to
contact and fumes was seen July 24,1915. He was in profound coma,
IN D U ST R IA L PO ISO N IN G IN
26
M A K IN G COAL-TAR DYES.
his breathing was stertorous, and his puLe was irregular and of very
poor quality. He was so cyanosed that the skin over his whole body
was a deep plum color. That morning at 7 he had gone to work feel
ing perfectly wTell in every way and, according to the history ob
tained, he was exposed to fumes of anilin for an hour and forty
minutes before he began to notice any S3rsmptoms of depression.
First came throbbing in the head and increasing nausea, which he
thought were due to the hot weather and the poorly ventilated room.
He next noticed palpitation of the heart, and then a violent headache
came on, increasing in intensity and accompanied by vertigo. As he
said, “ I felt as if I had been standing on my head for a long time
and that every ounce of blood in my body had rushed to my brain.”
The dizziness increased and he lost consciousness completely about
45 minutes after the onset of the first symptoms. He was picked up
by the other workmen and hurried to the hospital, where oxygen was
administered as well as heart stimulants, but apparently with little
effect. The cyanosis persisted, the heart action was very feeble and
remainded so for over 16 hours, and he did not regain consciousness
till the morning of July 25, a period of about 22 hours.
A catheterized specimen of urine obtained on admission showed
nothing of note, but a second examination was made 18 hours later,
when the urine was found to be smoky, specific gravity 1.022, there
was a trace of albumin, no sugar, and the presence of hemoglobin
was detected by the Heller test and by the Schonbein-Almen turpentine-guaiac test. This hemoglobinuria persisted for five days.
A blood examination made on entrance gave normal findings in
all respects except for a slight eosinopliilia, but four days later there
were stippled red cells and some irregularity in the size and shape
of the cells. The hemoglobin then was 75 per cent. (Sahli.)
The patient suffered from severe headache for five days and com
plained of weakness and exhaustion for at least two weeks longer,
after which he improved slowly.
Friedlancler30 reported from the municipal insane hospital in
Frankfort-on-the-Main a case of acute maniacal delirium in a man who
had loosened a rubber pipe leading into an anilin receptacle and had
received a splash in the face and mouth, swallowing about a mouthful.
He became delirious about four hours later and was brought to the
hospital in a strait jacket and deeply cyanosed. His mania lasted
until the next day, when he was rational but excited. On the third
day he was still irritable and restless, his heart still weak and rapid,
but cyanosis had vanished, and by the fourth day he was mentally
sound. A similar history comes from an American dye works. The
man was a pipe fitter and was working at some pipe in the ceiling
over the anilin reducers. Suddenly he became maniacal and ran
amuck over the plant, and it was six hours before he came to himself.
This case was reported as one of fume poisoning, but it seems pos
sible that the steam from the reducers, which does carry some anilin
with it, had gradually soaked the ceiling of the room and that in
working there the man’s hands had become saturated with it.
Another American case was also attributed to fumes of anilin.
A foreman was seriously affected by heavy fumes and was sent to the
30
Fricdi&nder.
Neuro.logisehes Centralblatt, 1900.
X I X , 155 and 294.
A N IL IN AND O TH ER AMIDO COM POU N DS.
27
plant hospital and given oxygen inhalations, whereupon he became
delirious, and did not recover from the attack till the following
morning.
It is recognized by American anilin workers that long exposure
to this body is likely to make men irritable, hard to deal with,
“ grouchy,” and that they are really not up to a full day’s work.
Their appetite is likely to be poor and they complain a good deal of
headache. A chronic form of anilinism was described by an early
German observer, Hirt, as characterized by disturbances of sensi
bility and of the motor nerves, inertia, headache, digestive disorders,
skin eruptions, and roaring in the ears. A few years ago men ex
posed to anilin were not infrequently treated by their physicians
for chronic valvular heart disease because the cyanosis, the altered
pulse, and the complaint of weakness, breathlessness on exertion,
palpitation of the heart, and indigestion seemed to point to such a
diagnosis. A typical case of this sort was reported in 1914, when
the importance of cleanliness in anilin work was not generally known.
The man had worked with anilin for nine months. He complained
especially of muscular weakness and fatigue. Palpitation of the
heart came on when he had any unusual exertion or simply at the
end of the day’s wTork, and he had frequent headaches while at work,
sometimes severe and accompanied by nausea and dizziness. He
was never cyanosed and examination showed no physical abnormality
except a rapid pulse, 94. While the number of red corpuscles in the
blood was increased to 5,400,000, the hemoglobin was only 68 per cent.
Curschmann lays great stress on this slowly developing form of
poisoning, especially from the solid amido compounds, the result
of repeated tiny doses, with a cumulative effect. He says that in
typical cases the first sign of this form of chronic poisoning is a loss
of hemoglobin, and therefore a blood examination is of great practical
importance, because any workman who has lost from 15 per cent to
20 per cent hemoglobin is facing the risk of an acute attack, and
should be suspended from work. A slight cyanosis is likely to appear
at this stage, but no typical microscopic changes in the blood till a
later stage. One of his cases had an almost typical neurasthenia, and
the only thing that pointed to anilin poisoning was the loss: of hemo
globin and a rise in blood pressure. Curschmann found that the
average blood pressure by the Riva-Rocci in 100 workmen not ex
posed to anilin was between 110 and 120, but in men intoxicated with
anilin it ran from 135 to 165. In cases of pronounced anemia with
cyanosis there may be a rise of 40 in pressure, and with it there is
always a slowed pulse, down to 48. In these cases there is a slight
jaundice and the urine is brown.
Older men do not endure, exposure to these compounds so w7ell as
younger men. Dr. Raymond Bugbee, of Providence, has given the
histories of two men, one between 50 and 60, the other 66 years old,
both of whom were severely poisoned with anilin after no great ex
posure, and in addition suffered from pain in the precordium, which
persisted longer than any other symptom. According to Dr. Suther
land of the du Pont Co. negroes have no immunity as compared with
whites, but suffer just as intensely from just the same symptoms.
The fact that in anilin workers cuts are likely to inflame and sup
purate and that sores are slow in healing and may go on to abscess
28
IN D U ST R IA L PO ISO N IN G IN
M A K IN G COAL-TAR DYES.
formation has been observed by men in charge of anilin works.
(See Adamson31.)
Several instances are on record of an intercurrent attack of in
fluenza affecting the course of a case of poisoning. For instance, a
chemist who was working with metanitranilin went home ill with
what proved to be an attack of influenza. This was on a Saturday.
On the following Tuesday he suddenly developed an attack of
jaundice with cyanosis. Relapses, without any further exposure to
the poison are also related. A workman, 31 years old, had had an
attack of anilin poisoning several months before in another factory.
He was overcome in the second factory on April 2, went home, and
apparently recovered, but on April 5, while he was still at home,
he suddenly became violently ill, lost consciousness, and was taken
in this condition to the hospital, where for two hours he had attacks
of projectile vomiting. When he regained consciousness he suffered
from headache and dizziness. He was in the hospital for six days.
In the German literature there are frequent references to dis
turbances of vision in the course of anilin poisoning, but there is
no mention of this complication in American literature, so far as
the writer knows. An article by Senn32 deals with a serious affec
tion of the eye among dyers in a Swiss factory. It consisted in a
loosening of the epithelial covering of the cornea, with subsequent
inflammation, cloudiness, discoloration, and therefore loss of vision.
This was found among men who were working over vats of steaming
anilin black, which is essentially a mixture of anilin and hydro
chloric acid, and Senn attributed it to the effect of the oxidation
products of anilin, the quiiiones, which cause a painful smarting of
the eyes so that the man rubs them vigorously and detaches the sur
face cells, leaving the cornea exposed to further cauterization.
Toluidins (C2H 4CH 3N H 2) .— The toluidins, ortho and para, are
considered by some to be more toxic than anilin itself. Posner and
Liebreich33 say that crude anilin is more poisonous than pure be
cause of the presence of toluidins, and von Jaksch34 makes the same
statement. Treitenfeld35 finds that they work very much as anilin
does, having the same effect on the central nervous system, but caus
ing rather less cyanosis, but in a case described by Starck36 the man
was not only comatose for 29 hours, but so deeply cyanosecl as to be
almost black. Rambousek37 says that the toluidins act like anilin
but have a stronger effect on the urinary system, causing strangury
and hematuria more than does anilin, and Dr. Kessler, of the Anilin
Products Co., says that his experience confirms this. Strangury
(suppression of urine) is also noted by Friedlander30 in toluidin
poisoning.
Gibbs and Hare38 tested the three isomers, para, ortho, and meta
toluidin, on animals, and found that all destroy red blood cells, lower
30 Friedlander. Neurologisches Centralblatt, 1900. XIX, 155 and 294.
31 Adamson, George. Journal of Industrial and Engineering Chemistry. 1916. VIII.
1058.
32 Correspondenzblatt fur Schweizer Aertze, 1897, p. 161.
33 Posner and Liebreich. Quoted by Robert, Lehrbuch der Intoxikationen. Stuttgart,
1911. P. 790.
84 v. Jaksch, R. Die Vergiftungen. Vienna, 1912, p. 325.
ss Treitenfeld. Quoted by Robert, Lehrbuch der Intoxikationen. Stuttgart; 1911, p.
790.
86 Starck, M. Therapeutische Monatshefte. 1892. VI, 376.
37 Rambousek. J. Industrial Poisoning. Translated by T. M. Legge. London, 1913.
38 Gibbs and Hare. Quoted by Robert, Lehrbuch der Intoxikationen. Stuttgart, 1911.
A N IL IN AND OTH EE AMIDO COM POU NDS.
29
the temperature, and lame the spinal cord. The fatal dose per kilo
gram of weight is: For para, 0.1 gram; for meta, 0.125 gram; and
for ortho, 0.208 gram. Meta is not used in dye manufacture, and
most of the Americans who have had practical experience with para
and ortho confirm the statement of Gibbs and Hare that para is
more toxic than ortho, although it is crystalline while ortho is an
oily liquid. One industrial physician, however, believes that ortho
is distinctly more poisonous than para, because it is more easily ab
sorbed. In several large plants the toluidins are said to give more
trouble than the fumes of anilin, not necessarily because they are
more poisonous but because there is not any process in anilin manu
facture except repairing and cleaning which necessitates as much
exposure to fumes and contact as does the centrifuging or “ spin
ning of the two toluidins. A man with a case of paratoluidin
poisoning, chronic, with acute exacerbation, came recently to the
occupational disease clinic of the Massachusetts General Hospital.
He had been poisoned by fumes from the sulphur fusion of para
toluidin for primuline. He had the symptoms typical of chronic
poisoning with unusually distressing breathlessness on exertion. A
large plant reported seven cases of poisoning within a short time in
the research department in men who were separating ortho from
paratoluidin.
Even acute mania may develop as a result of toluiclin poisoning.
One of the cases reported by Friedlander30 was in a man who had to
repair a toluidin pump and splashed some on his face and chest. He
did not change his clothes, and two hours later he was found on the
ground outside apparently sleeping. When he was roused he became
maniacal and had to be taken to the asylum. He was cyanosed, res
piration rapid and labored, pulse very irregular, gait staggering.
He was in delirium with convulsions for some 14 hours, and his
mind was not entirely clear till the third day after. This case also
displayed the characteristic urinary symptoms, very scanty, painful
micturition, only 100 cc. of urine passed, with agonizing pain, on the
first day. This persisted and the quantity did not reach 1,000 cc.
till the ninth day. There was albumen in the urine, but no blood.
The man was in the hospital three weeks.
Starck’s 36 case is another very striking one. The man got his
clothing soaked while dipping mixed toluidins from an open recep
tacle, and did not receive proper treatment till more than 24 hours
later, so that the poison had full opportunity to work. He began
to feel the effect at 5 in the morning— he was on the night shift— but
finished his shift, working on till 7. At 11 he lost consciousness, at
6 that evening he lay in coma, motionless, eyes half open, mouth
tightly closed, a little foam on his lips. He was still in his soaked
clothing and was given cognac as a remedy. The next morning he
was extremely cyanosed, his lips and mouth almost black, and there
was some trismus, but he wTas conscious, complaining of severe head
ache. His pulse was small, his respiration slow and labored, his
breath smelled strongly of anilin, so did the feces. Very severe
strangury developed, the urine was bloody and passed only in drops.
This increased until he became delirious with the pain, and it was
3° Friedlander. Neurologisches Centralblatt. 1900. XIX, 155 and 294.
36 Starck, M. Therapeutische Monatshefte. 1892. VI, 376.
30
INDUSTRIAL POISONING IN M A K IN G COAL-TAR DYES.
not till the fifth day that it lessened, but the urine remained bloody
till the tenth day. He had distress in the abdomen, great thirst, but
loathing for food, After all symptoms cleared up there remained
pronounced weakness and he was not fit for work for five weeks.
The case was undoubtedly greatly aggravated by neglect and mal
practice.
Xylidin (C6H 3(CH 3) 2N H 2).— Very little is written of the action
of the xylidins, but they are undoubtedly less poisonous than anilin
and toluidin. Acetyl-para-toluidin was found in use in one plant,
and was said to be toxic.
Diamines (C6H 3CH 3(N H 2} 2).—The diamines are notoriously
toxic. Toluylencliamine has long been regarded as a typical blood
poison. Stadelmann39 experimented with toluylendiamine on dogs
and found extensive destruction of red blood corpuscles and severe
hematogenous jaundice. Dragendorff40 found methemoglobin, de
struction of liver cells, and a loss of alkalinity of the blood, which was
brownish black.
The two pkenylendiamines (CGH 4(N H 2) 2), para and meta, are very
important intermediates in dye manufacture. Para was used as a
hair dye until its dangerous nature was discovered. It is still used
for dyeing furs, under the name of ursol, and is the cause of very
severe eczema with swelling of the eyelids and sometimes ulcers and
cellulitis in fur dyers and even in furriers and women who wear furs
dyed with this compound. When used as a hair dye and rubbed into
the roots of the hair, paraphenylendiamine has been known to set
up not only a dermatitis but severe symptoms of nervous disturbance,
sleeplessness, dizziness, weakness of the legs, even epileptiform con
vulsions, loss of consciousness, and death. (Knowles41.) According
to Blaschko42, however, the irritating effect of hair dyes and fur
dyes containing paraphenylendiamine is not caused by this com
pound but by the presence of a mid product, quinone dichlordiamine,
which has a much more irritating effect on the skin. Olson43 also
attributes the skin eruptions to quinone dichlordiamine and savs that
when oxidation is complete phenylendiamine is not irritating to the
skin. This probably explains the contradictory statements about
this compound, which are made by the men who handle it, for in one
factory it will be said to give a great deal of trouble from skin erup
tions and in another it is handled with no difficulty at all. Paraphenyldiamine is also used as an intermediate for sulphur dyes.
Criegem44 has described asthmatic attacks in paraphenylendiamine
workers and the files of the New York Labor Department contain the
report of a case of eczema, bronchitis, and asthma in a man who
mixed ursol for dyeing furs.
Meta is used as an intermediate for Bismarck brown, Manchester
brown, and many azo dyes. It causes skin eruptions and the steam
from filter presses is said to cause systemic poisoning. It is usually
considered more dangerous than para, but since it is made by the
39 Stadelmann. Quoted by Malden. Journal of Hygiene, 1907. VII, 672.
40 Dragendorff. Quoted by Robert. Lehrbuch der Intoxikationen. Stuttgart, 1911,
p. 782,
41 Knowles, F. C. Medical Record, 191ft, p. 217.
42 Blaschko. Deutsche medizinische Wochenschrift, 1913, II, 2406.
43 Olson, G. M. Journal of American Medical Association. 1916. LXVI, 864.
44 Criegem. Quoted by Kobert. Lehrhudi der Intoxikationen. Stuttgart, 1911, p.
653.
A N IL IN AND O TH ER AM IDO CO M POU NDS.
31
reduction of dinitrobenzene it is quite possible that traces of unre
duced D N B may be responsible for effects attributed to phenylendiamine.
Diphenylamine (C6H 5) 2N H ).— Diphenylamine, which may be
regarded as ammonia (N H S) with two hydrogen atoms replaced by
phenyl (C6H 5) groups, is said by Harnack 45 to cause in cold-blooded
animals a slow paralysis, probably from chronic blood changes.
Kobert46 says that warm-blooded animals can tolerate large doses,
but later on they die of marasmas, although he is uncertain how far
this is due to the effect on the blood. Large quantities of diphenylamine were manufactured in the United States during the war and
dissolved in ether alcohol with nitrocotton and then incorporated
with the nitroglycerin powders. There was no evidence of any
poisoning among the men manufacturing and packing diphenylamine; and if it had any effect on the workers in smokeless powder
and mixed powder manufacture, it was masked by the other toxic
substances— ether-alcohol, nitroglycerin, and amyl acetate. In dye
manufacture diphenylamine is used for the production of metanil
yellow and azo yellow.
Nitranttin (C6H 4N H 2N 0 2) .— Of the three isomers of nitranilin, two
are important, para and met a. Kobert4e and Rambousek37 both think
that paranitranilin is more toxic than meta. Gibbs and Hare38 say
that both cause formation of methemoglobin and laming of the central
nervous system and heart. They find para the most toxic, then ortho,
tast meta. Lewis, of the Sprague Memorial Institute, experimenting
on animals, found meta more toxic than para.
Paranitranilin is distinctly important in dye manufacture not only
as an intermediate for sulphur dyes and for azo dyes, but also because
of its use, together with beta-naphthol, for the production on the
fabric of a bright red dye, u para red.” The most conspicuous action
of para is on the skin, for it causes a very distressing, burning, itch
ing eruption, and extraordinary precautions are necessary to protect
the men employed iri grinding and packing it. It is also capable of
producing serious and even fatal systemic poisoning. Bachfeld47
reported nine cases of poisoning, four of which were serious, with
frequent scanty micturition, burning pain, but no blood or albumen in
the urine. A fatal case was reported by Lewin from the Hochst
factory. The man had been working for five hours in paranitranilin
dust. A t least one fatal case has occurred in the United States. A
27-year-old white man was employed for 12 days in the paranitranilin
department of a color works, never having before been brought in
contact with any of these compounds. The day of the accident he
had been wTorking about an hour in the drying room where parani
tranilin is dried on trays. The nature of the accident was not re
ported, but he was said to have been poisoned by dust, perhaps from
tipping over a tray of the powder. J3e was sent to the bathroom and
took a bath, remaining there for about an hour. Then he went to
the works doctor, and after he had been in the office about 20
^ Harnack. Quoted by Kobert. Lehrh^eh der Intoxifeationen. Stuttgart. 1911, p.
787.
46 Kobert. Lehrbueh der Intoxikatronen. Stuttgart, 1911.
37 Rambousek, J. Industrial Poisoning. Translated by T. ML Legge. London, 191 &
38 Gibbs and Hare. Quoted by Robert. Lehrbuch der Intoxikationen. Stuttgart, 1911.
47 Baclifeld. Vierteljakreschrift fiir gericbtliche Medizin, 1898. XV, 396.
32
IN D U ST R IA L PO ISO N IN G IN
M A K IN G COAL-TAR DYES.
minutes he lost consciousness. He was given stimulants and the lung
motor was used, but he died two and a half hours after, the accident.
Metanitranilin is made from dinitrobenzene, and reports of indus
trial poisoning from this department are sometimes dubious, be
cause it is impossible to be sure which compound is the cause. Never
theless, clear cases of metanitranilin poisoning do occur in work in
which no DNB is present. For instance, a workman 22 years old
was told to clean out a tub in which metanitranilin had been “ proc
essed.” Soon after, he complained of acute frontal headache, then
he vomited and lost consciousness. He was f&ken to the hospital and
the record reads: Vomiting; fainting attacks; headache; rapid heart;
very profound cyanosis; lips and mucous membranes almost black.
A similar case is reported by the New York Department of Labor
from another American plant. Here, too, the man was sent to clean
out a munjer in which metanitranilin had been made. He worked
off and on from 9 in the evening to midnight. At midnight he went
off for half an hour for supper and when he returned he told the
foreman that he was faint and nauseated, but nevertheless, he was
allowed to go back to work. At half past 4 in the morning he was
found unconscious and was taken to the hospital, deeply cyanosed,
respiration rapid and shallow, pulse rapid and of poor quality.
Eight ounces of venous blood were removed, the color was dark and
it coagulated slowly. He was given saline infusions, but he did not
improve, and in the morning transfusion of blood (500 cc.) was made.
Under this treatment and the administration of oxygen and stimu
lants he gradually improved, but did not regain consciousness till
6.30 that evening. His convalescence was very slow.
In one of the ordnance plants during the war metanitranilin was
manufactured on a large scale for use together with DNB as an
explosive in high-explosive shells. There was much ill health
among the men working in this department, from contact and from
the steam in the course of washing. The men in charge said that
the poisoning was cumulative, that each attack lasted longer than
the previous one. The symptoms were those characteristic of an
amido compound, with very irritating effect on the skin.
Methyl and ethyl anttm (C6H 5N (C H 3) 2, C6H 5N (C 2H 5) 2).— The
alkyl derivatives of anilin, dimethylanilin and cliethylanilin, are dis
tinctly less poisonous than anilin, and when poisoning does occur it is
possible that the substance responsible is really unchanged anilin. One
case that was reported came from direct contact. A stopcock came
off and a mechanic, in trying to screw it on, received a spurt of
dimethylanilin in his face. Another case was caused apparently by
dimethylanilin fumes in the earlier days of American dye manu
facture, in 1916.48 A man of 22 years had been at work only two
weeks on the night shift. A t half past 10 he climbed a ladder to
inspect a vat of dye which was said to be crude violet made from
carbolic acid, dimethylanilin, and other substances. He lifted the
lid, breathed the fumes, and lost consciousness, not recovering his
senses till eight hours later. The cyanosis in this case was so deep
that the doctor summoned to the plant thought he must have fallen
into the violet dye. The next day he was taken to the hospital com
plaining of impaired vision, noise in the ears, and intense pain in
the abdomen. He was in the hospital seven days.
—
— --------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
48 From the records, of the New York State Department of Labor.
A N IL IN AN D O TH ER AMIDO COM POU NDS.
33
A second man 48 treated in the same hospital had been told to bail
dimethylanilin from one container to another, in the course of which
he probably got some of the liquid on his hands. He worked from
8 in the morning to 3 in the afternoon, when he told one of the
chemists that he felt twitching in his toes and feet, gradually spread
ing up his legs, and he was faint and nauseated. The chemist made
him sit down in the open air for an hour, but he did not wash his
hands nor change his clothes. He was then taken home, where he
grew weaker and finally lost consciousness, in which condition he
was taken to the hospital, where they found him deeply cyanosed
and with a weak and rapid pulse. Two weeks later he was still
weak and his mind somewhat confused.
Anilin hydrochloride.— This compound of anilin produces exactly
the same symptoms as anilin and there may be a good deal of poison
ing in the course of its manufacture unless, as is usual, the work is
carried on in an open shed or in a room abundantly supplied with
artificial ventilation. In one department the man in charge said that
once during a month of hot weather all the men in his department
were cyanosed. He said that the wrorst cases came from letting the
hot hydrochloride splash on the skin, for it is quickly absorbed.
The fatal case of anilin poisoning reported by White and Sellers
at the Brussels Congress of Industrial Hygiene in 1910 was in a
man working with anilin hydrochloride, but it was caused by the
anilin itself, which splashed over the man’s hands and face and body.
He died within 24 hours’ time. However, it must be remembered
that anilin hydrochloride is capable of producing typical anilin
poisoning. Price-Jones and Boycott used it in their experiments
instead of anilin and brought about all the blood changes char
acteristic of anilin.
Less important is sulfanilic acid, which is produced in the same
way, only by the use of sulphuric instead of hydrochloric acid. The
same risks attend its: production, but as to the toxicity of the finished
product there seems to be no information in the literature.
Benzaldehyde (C6H 5C H O ), or oil of bitter almonds, is an im
portant intermediate which, so far as present evidence goes, has no
toxic effect. Robert46 found it harmless to animals, and there is
no report of its ever having caused any trouble in the color industry.
Paraamidophenol (C6H 4O H N H 2).— Paraamidophenol, which re
sults from the reduction of paranitranilin, is an important inter
mediate, especially for sulphur dyes. The real danger in connection
with this process comes from the paranitranilin, which is distinctly
the more poisonous of the two. Indeed, the excretion of both nitro
and amido compounds from the body is preceded by their reduction
to paraamidophenol, which is found in the urine as an alkaline salt
of paraamidophenol-ether-sulphuric acid.
Paraamidophenol is one of the substances that causes troublesome
dermatitis. Nitrosodimethylanilin (C6H 4N O N (C H 3) 2) also causes
dermatitis. The naphthylamines (C10H 7N H 2), alpha and beta, are
capable of producing symptoms characteristic of the amido com
pounds. Alphanaphthylamine does not, so far as appears from the
48 From the records of the New York State Department of Labor.
40 Robert. Lehrbuch der Intoxikationen. Stuttgart, 1011.
25431°— 21-------3
34
IN D U ST R IA L PO ISO N IN G IN
M A K IN G C O AL-TA R DYES.
literature and from the testimony of practical men, set up a serious
form of poisoning, but one of the earliest cases recorded in American
literature of cyanosis from an amido compound was Apfelbach’s 40
second case, a man working in a dry color factory mixing various
compounds, one of which was alphanaphthylamine. Betanaphthylamine is apparently distinctly more toxic than alpha and in one
large American plant, where the men come in contact with it in
the crude naphthionic department, it is said to cause not only
cyanosis but frequent micturition, perhaps from over-acidity of the
urine. This same plant has no trouble at all with the alpha com
pound. A case of hematuria from betanaphthylamine is noted in the
German Factory Inspection Report for 1912.
There are a few more compounds containing the amido group
which should be mentioned: Anthranilie acid, used for lake colors
and for the pigment scarlet B, the dye used for postage stamps, is
benzoic acid with one N H 2 group added to the ring, ortho-amidobenzoic acid (C6H 4CO O H NH 2). It is only slightly poisonous to man,
although in frogs it causes paralysis. Kleist46 took 2 grams within
two hours’ time and noted discomfort in the stomach, salivation, and
sweating, but nothing else. The methyl ester of anthranilie acid is
perfume of orange blossoms. None of the derivatives of anthranilie
acid seem toxic to warm-blooded animals.
Amidoazotoluene.— Amidoazotoluene, called scarlet red, is known
to physicians as a stimulant for tissue growth, and therefore useful
in severe burns to hasten healing. As a rule its use for this purpose
has not been followed by any untoward symptoms, but two cases are
recorded of severe poisoning after the application of scarlet red
ointment to deep burns. Cyanosis, dizziness, headache, pain, slight
rise of temperature, rapid pulse, and albuminuria came on after the
application of scarlet red. The symtoms disappeared when the
dressing was removed and recurred when a second application was
made. Amidoazotoluene is derived from orthotoluidin and is used
for alizarin color manufacture.
Phenylhydtoxylamine is said to be formed in making benzidin, and
when this occurs a bad case of blistering may result from contact
with it.
CHLOR COMPOUNDS.
Chlorbenzene, etc. (C6II5C1) .— The chlorine compounds of the ben
zene ring are considered less toxic than those which do not contain
chlorine. Experiments made by Mayer and his colleagues for the
French Government28 showed that chlorbenzene is less toxic than
benzene itself. Nevertheless it is possible to have severe poisoning
from chlorbenzene, as can be seen in the cases reported by Mohr.11
Ten instances of severe and typical poisoning are described* by Mohr
in men who, after exposure to chlorbenzene and DNB or in three
instances to chlorbenzene alone, developed the symptoms after drink
ing a few glasses of beer.
11 Mohr. D eutsche medizinifuche W oehen sch rift. 1902, X X V I I I, 78.
rs Perkins, R. G. U n ited S la te s Public H ealth Reports, 1919. Vol. 344, p. 2835.
49 A pfelbach, G. L. B u lletin of D epartm en t of F a cto ry Inspection of Illin ois, 19 13 ,
p. 55.
40 Kobert.
Lehrbueh der Inioxikatlouen.
Stuttgart, 1911.
O H LOU COM POU NDS,
35
Nitrochlorbenzene (C6H 4C1N02) . — The nitrochlorbenzenes are
very much more poisonous than the chlorbenzenes. Systemic symp
toms from paranitrochlorbenzene have been observed in connection
with the reduction of this compound to paranitrochloranilin.
Sturm50 found orthonitrochlorbenzene very volatile and the fumes de
cidedly toxic to animals when present in less than 2-10 mg. per
liter of air. It is more toxic than para. Para is an intermediate
for sulphur blue, ortho for anisidin.
Dinitrochlorbenzene (C 6H 3C i(M 02) 2), used in the manufacture of
sulphur blacks, has proloably caused more dermatitis than any other
compound used in color manufacture. In one American plant every
man employed was more or.less affected in this way, and for a while
in summer the place had to close down for lack of labor. One of
the men described the symptoms as beginning with itching behind
the knees and at the bend of the elbow and along the inner surface
of the thighs. Little red points appeared, which later coalesced to
form a swollen mass, which itched and burned unbearably. Some
times the face was involved and the eyes swollen shut. In another
plant the chemists suffered so severely from dinitrochlorbenzene itch
that they were forced to take prolonged alkaline baths.
Benzyl chloride (C6H 5CH 2Cl) is toluene with 1 atom of chlorine
taking the place of an atom of hydrogen in the CH 3 group, and
benzol chloride is similar, only with 2 such atoms of chlorine
(€ 6H 5CH (C l) 2), These are therefore side chain products and not
so toxic as the so-called chlorinated, toluenes in which the hydrogen
of the ring is replaced by chlorine (C6H 4CH 3C1). Benzyl chloride,
which is used for green dyes, is one of the many “ tear gases,” pro
ducing rapid and intense irritation of the eyes with blinding tears.
Benzal chloride, which is used to produce the important intermediate
benzaldehyde, is still more irritating to the eyes. In the only place
in which the author saw benzyl chloride manufactured chlorine gas
is passed into toluene and the resulting benzyl chloride, carrying
doubtless chlorinated toluenes with it, is poured out and washed in
an open shed; otherwise the fumes would be unbearable.
A case of mixed poisoning, probably from chlorinated toluenes,
benzyl chloride, and toluene is the following: A chemist was em
ployed in the production of benzyl chloride and was working in an
atmosphere which at times was heavy with fumes. During the nine
months he worked in the laboratory he lost some 25 or 30 pounds,
his color changed to a cyanotic hue, he suffered from insomnia and
so great a loss of. strength that toward the end he found himself
unable to perform the simplest sort of physical work. Mis eyes were
affected, but transiently, and he traced it to the benzyl chloride, for
the inflammation varied according to presence of benzyl chloride
fumes in the air. He also seemed to have some injury to the liver,
for he complained of pain and tenderness in the liver region. No
physical examination was ever made in this case, and we have only
the history to go by, but it seems pretty clear that this was a case of
poisoning from chiortoluenes and benzyl chloride.
60 Sturm . Q uoted by Curschm ann.
heitspfiege, 1 9 1 1 . X L I1 I , 225.
D eutsche V ie rte lja h rssc h rift fu r offcntlieh e Gesund-
36
IN D U ST R IA L PO ISO N IN G IN
M A K IN G CO AL-TAR DYES.
HYDROXY COMPOUNDS.
Phenol, hydroxy benzene, has already been mentioned. Naphthol
(C10H 7H O ), which bears the same relation to naphthalene as phenol
does to benzene, resembles phenol in its action but is less soluble
and less corrosive. Alphanaphthol is more strongly antiseptic
than beta and probably more poisonous. The use of beta-naphthol in industry seems to give rise to little if any trouble, except
for its effect on the skin. Even the fumes are said to be irritating to
the skin, but the caustic soda used in the production of beta-naphthol
is responsible for more trouble than the beta-naphthol itself. Nitrosobeta-naphthol formed in the production of H acid gives rise to derma
titis.
Dinitronaphthol (C10H 6O (N O 2) 2) is the dye called Martius yellow
and also Manchester yellow. It has the usual action of a nitro deriva
tive of the benzene ring on the blood and on the nervous system, but
it is one of the weaker members of this group.
PYRIDINS.
The pyridins used in the making of anthraquinone and in other
processes for indanthrene dyes are said to make the men “ dopy,” to
give them headache, dizziness, and dulling of the intelligence. They
have also a peculiar effect on the skin similar to that which has been
described in England as a result of the handling of tarry substances
in briquette factories. The skin is raw and sensitive as if from sun
burn, and the man suffers, especially after washing his face and
hands and forearms and then going out into the open air.
PHOSGENE OR CARBONYL CHLORIDE (COCi).
Phosgene was first made by John Davy in 1812 by exposing a
mixture of equal parts of chlorine and carbon monoxide to sunlight,
and he gave it the name because of the part played by light in its
formation. It was used for some years before the war in clye
manufacture, especially in the production of Michler’s ketone, and
it was responsible for some industrial poisoning, but its use in gas
warfare led to a thorough study of the toxic properties, and we know
now very clearly what happens when phosgene is inhaled.51
It owes its poisonous,, action to the fact that it decomposes readily
in the presence of water to hydrochloric acid and carbon dioxide.
This decomposition takes place within the body when the gas reaches
the finer bronchioles and the alveoli of the lungs and is acted on by
the watery vapor there, and also probably when the gas is absorbed
and readies the tissues of various organs, undergoing slow decom
position. The effect of phosgene differs from the effect of hydro
chloric acid because it is not immediately caustic, therefore while the
latter attacks the upper respiratory passages and produces violent
inflammation of the larynx, trachea, and bronchi, phosgene does
not produce its effect till it has penetrated deeply into the lungs.
In men dying from phosgene gas the lungs are found deeply con
gested and filled with fluid. Around the fine bronchioles there are
51 Collected Studies on the Pathology of War Gas Poisoning. Medical Science Section
of the Chemical Warfare Service. M. C. Winternitz, Major, M. C., U. S. A. Yale Univer
sity Press, 1920.
PH O SG EN E OR CARBO N YL CH LO RID E.
37
islands of inflammation which form broncho-pneumonic areas and
may spread if life is prolonged, become infected, and result in
miliary abscesses. The edema and the fibrin which obstruct the
circulation in the lungs lead to heart strain and dilatation, which
may be the immediate cause of death, especially if the victim has had
to exert himself after gassing.
The German factory inspection reports for the year 1913 mention
three cases of poisoning from phosgene, but none of the men died.
The treatment that was given consisted in the administration of
fumes of alcohol mixed with oxygen. So far no fatal cases of poison
ing from this substance have been reported from English dye works,
although several have occurred in the United States. It is impos
sible to say how many there have been in the years since 1914, for a
great deal of secrecy has been observed with regard to them, and posi
tive statements concerning only three have been obtained. One of
these, which should really be attributed to the gas warfare industry
rather than to the dye industry, is worthy of special mention, because
it shows the extent of the danger of an accident which allows phos
gene gas to escape.
In a plant which was manufacturing phosgene for use in the war
something went wrong and a quantity of gas escaped at a moment
when about 180 men were in the vicinity and were supposed to
have breathed more or less of the fumes. They were all put under
medical treatment at once, and 20 developed symptoms, fairly serious
in some cases, but not fatal. An Italian teamster, who is said to
have been more than 1,000 yards away, was not thought to have
been exposed and was allowed to go on with his work. He went
home at the end of the day and complained of breathlessness. A
doctor who was summoned said he was developing pneumonia, but
by 5 in the morning he was dead, and the case was pronounced to
be one of phosgene poisoning. One of the physicians in charge of
the other men said that they suffered from intense headache which
lasted about 72 hours, a strangling, exhausting cough without sputum,
exhaustion, and a weak heart. One man, a Negro, developed edema
of the lungs but recovered.
ALIPHATIC OR FATTY COMPOUNDS.
The compounds of this series that are used in dye manufacture
are methyl and ethyl alcohol, acetates, chlorides, aldehydes, and
ketones.
According to Fraenkel,0 the members of the methane series are
less toxic than those of the ethylene or acetylene series. The toxicity
increases as the number of carbon atoms increase, but there is an
important exception to this rule— methyl alcohol is less rapidly toxic
than ethyl, but its effects are more serious because it is so much less
rapidly oxidized. The ethyl series have a special affinity for the
central nervous system, and most of the ethyl substitution products
are more poisonous than the methyl. Chlorine increases the nar
cotic effect of all fatty compounds and also the depressant effect on
heart and blood vessels. As a general rule the toxicity increases with
the increase of Cl atoms, carbon tetrachloride being more toxic than
0 Fraenkel, Sigmund. Die Arzneimittel Synthese auf Grundlage der Beziehung zwischen
chemischer Anfbau und Wirkung, Berlin, 1912.
38
IN D U ST R IA L PO ISO N IN G IN
M A K IN G CO AL-TAR DYES.
chloroform. Introduction of the HO group lessens toxicity increas
ingly, changing alcohols to glycolls and glycerines. The displace
ment of an HO group by a methyl or ethyl group increases toxicity,
especially the hypnotic effect. -Esters, ethyl acetate, and amyl ace
tate have a different effect from alcohol, increasing respirations and
benumbing the central nervous system without-any exciting effect.
Methyl or wood alcohol (C H 2OH) .— Industrially, ethyl alcohol
can be disregarded. One hears tales of workmen having been made
drunk in the early days of dye manufacture when they went in to
clean out the stills, but the work of still cleaning has been much im
proved of late years; air is blown in or Draeger helmets provided.
Methyl alcohol is more of a danger. One case of serious systemic
poisoning, but without effect on the eyes, occurred as the result of a
boil-over, the man inhaling the fumes. Two cases of mixed poison
ing are on record in the files of the New York Department of Labor.
The men wTere dipping wood alcohol and anilin from receptacles and
mixing them.
It is usually assumed that the use of denatured alcohol is free from
danger, but this is far from being true. According to the regula
tions of the United States Revenue Service, revenue-free denatured,
grain alcohol can be produced by the addition of methyl alcohol to
grain alcohol in quantities from 2 to 20 per cent. There is also a
small quantity, about one-half of 1 per cent of pyridin, a nauseous,
ill-smelling coal tar distillate. The denatured alcohol generally
used in industry contains 2 per cent or 4 per cent of wood alcohol,
but in dye manufacture the 10 per cent formula is often used because
the Government imposes less rigid restrictions on the use of this
variety of denatured alcohol. In one color works it was this 10 per
cent methyl alcohol mixture that was held responsible for ill health
in the making of metanil yellow by coupling metanilic acid to diphenylamine m denatured alcohol containing 10 per cent of methyl
alcohol. There are also cases of suspected methyl alcohol poisoning
in connection with the making of methyl anilin and in producing
anisidin from nitroanisol.
Experience in Germany and in Austria has shown that denatured
alcohol which contains only 2 per cent methyl alcohol may cause
symptoms of poisoning in susceptible workers. 'The variation in
individual susceptibility to methyl alcohol is very striking, as was
shown in the famous poisoning in the Berlin lodging house in 1911,
when more than a hundred men were made sick by drinking adul
terated brandy. It was shown then that the same amount of brandy
which had produced death in one man and permanent blindness in
another, produced only trifling symptoms in a third. Recently a
case of complete blindness, resulting from the use of denatured alco
hol with 4 per cent of methyl alcohol, was reported by J. M. Robin
son,52 of Duluth.
O f the aldehydes of this series, formaldehyde is the important one
in dye manufacture. It is used in the production of synthetic indigo.
Iwanoff53 tested it on animals, and found that if he exposed them to
heavy fumes, or to lighter fumes for eight or nine hours, they devel
oped purulent bronchitis and edema of the lungs. Loeb 54 describes
52 Robinson. Jou rn al of A m erican M edical A ssociation , 1018. L X X , 148.
53 Iw anoff. A rc h iv fiir H ygiene, 1 9 1 1 . L X X I II , 307.
M Loeb. Arch, fiir exp erim cn telle P a th o lo gic und P h arm akologie, 1912 .
X L IX , 114 .
A L IP H A T IC OR P A T T Y CO M POU N DS.
39
also affections of the Lungs, but in addition he finds that all the alde
hydes of the fatty series cause destructive changes in the coats of the
arteries, with loss of elasticity and the formation of aneurisms.
The ketones, of which acetone is the best known, seem to be harm
less, at least no harmful effect on human beings has so far been re
ported, During the war a good deal of acetone was used in making
smokeless powder, but no harm resulted. Kobert46 believes that in
dustrial poisoning from acetone is impossible, although there is a non
industrial case on record which resulted from the application of a
celluloid dressing which had been softened by acetone. This would
tend to show that if the skin is in contact for a long time with ace
tone, poisoning may occur. Archangelsky55 has tested acetone on
animals and has found that it is possible to recover it from the brain
and to a less extent from blood and liver. It seems to have a special
affinity for the central nervous system. It is narcotic, but only
slightly toxic. Large quantities can be given and can accumulate in
the body without causing death. In large doses a narcosis is pro
duced like that of alcoholic intoxication, from which recovery is
rapid unless excessive quantities; have been given, when it may per
sist for hours. This narcosis can also be produced by the breathing
of acetone fumes.
Dimethyl sulphate { (C H 3) 2S 0 4) is used in dye works in England,
Germany, and the United States to methylate anilin. It is not essen
tial for this reaction and its use is not by any means universal, for dimethylanilin can be produced by the use of methyl chloride or methyl
alcohol, provided the reaction is carried on in an autoclave with heat
and pressure. But it is cheaper to use dimethyl sulphate because
heat with pressure is not required. The poisonous properties of
this compound are well known and in many of the plants visited
here and abroad it was considered too dangerous to use, but in others
it was freely used, and the management insisted that the dangers
had been greatly exaggerated. It is hard to believe this when we
are told that it was one of the gases selected by the Germans for use
in trench warfare.56
The cases of industrial poisoning which aroused the German dj^e
manufacturers to a realization of the danger of dimethyl sulphate
were described in 1902 by Weber,57 of Schmiedeberg’s laboratory in
Strassburg. There were three, two of them fatal, and they had
occurred in the Bochringer factory, near Mannheim, and in the
Ludwig Casella factory, near Hanau. The first case was in a
laborer 48 years old, who worked for four hours over a kettle from
which heavy gray fumes of dimethyl sulphate were arising. At
the end of this time he felt a severe burning pain in his throat and
chest. He went to the doctor and 48 hours later was sent to the hos
pital in a dying condition with pneumonia of both lower lobes and
distinct evidence of a local caustic action on the throat. The mucous
membrane of the pharynx and uvula was destroyed and there were
also burns covered with scabs on the eyelids. He died that same
day. The autopsy showed destruction of the mucous membrane in
40 R obert. L<hrbuch der In toxlk atio n en . S tu ttg a r t. 19 1 1.
55 A rch an g elsk y.
A rc h iv fiir experim entelle P ath o logie und Ph arm akologie, 1901.
X L V I, :U7.
50 Auer. P ioceed in gs o f Society for E xperim en tal P>iology and M edicine, 1918. XV,
104 and 106.
57 Weber. Arch, fiir experim entelle ra tlio lo g ie und P harm akologie, 1902. X L V II, 113 .
40
IN D U ST R IA L PO ISO N IN G IN
M A K IN G COAL-TAR DYES.
larynx, trachea, and bronchi, small hemorrhages into the serous cov
ering of brain, lungs, and heart, cloudy swelling of liver and kidneys,
double pneumonia.
The second case occurred at the same time and in the same room.
Another laborer, 19 years old, was working at a distance from the
dimethyl sulphate kettle. He was obliged to stop work because of
burning in the chest, constant cough, and running in the eyes. For
a week he suffered from hoarseness and painful cough, pain in swal
lowing, difficulty in breathing, burning in the chest. On the third
day the cough began to produce a very abundant purulent bloody
sputum and he also vomited mucus. He had a slow recovery, the
hoarseness lasting three wreeks, abundant sputum four weeks. His
lungs were not normal till the tenth week, and the inflammation of
the eyes persisted for three months. He lost 12 pounds in weight.
The third was a chemist who broke a receptacle containing di
methyl sulphate and spilled about 20 cc. over his clothes. This hap
pened in the morning. In the evening he began to have severe pains
in his bod}^, especially the legs, pain in his eyes and burning in the
chest. Early the next morning the physician who was summoned
found that he had burns of the first to the third degree on the abdo
men, genitals, and thighs. He had severe inflammation of the throat,
bronchitis with an incessant painful cough, edematous swelling of
the eyelids, and his eyes could not stand the light. There was no
involvement of the lung tissue, of the heart, or the nervous system.
The burns improved, but the secretion from the bronchi grew more
profuse. Inflammation of the lungs set in, then jaundice and albu
minuria, with a high fever, a rapid pulse, and death on the fourth
day. There was no autopsy.
Dimethyl sulphate is an oily colorless fluid which boils at 188° C.
(370.4° F .), but vaporizes at room temperature, giving off gray
fumes at 50° C. (122° F.) which consist of dimethyl sulphate itself.
Weber found that its toxicity depends on the whole molecule, not on
any group which may be split off, such as methyl alcohol or sulphuric
acid. The striking peculiarity of dimethyl sulphate is the intensely
caustic effect on all tissues, not only by direct contact with the skin
but by the action of the vapors on the lung tissue. In animals it pro
duces also coma and convulsions. There is no possible antidote for i t ;
prevention is the only cure.
Recently experiments have been carried on by Auer,56 of the Rocke
feller Institute, testing the effect on cats of exposure to the fumes of
dimethyl sulphate, which he calls a war gas. Auer reviews a Rus
sian article by Naiding, published in May, 1917, in which the anes
thetic effect of certain war gases was mentioned. Naiding found that
soldiers gassed with chlorine and phosgene had lost pain sensation
in the skin. Auer brought about a very marked generalized loss of
sensation to pain in cats by exposing them to dimethyl sulphate
fumes, and this was so pronounced that severe operations could be
performed without any sign of pain. I f the animal survived the
analgesia was sometimes still well marked six months afterward. The
effect on the respiratory tract was like that which has been described
in man, a diphtheritic inflammation of large and small bronchi and
bronchials followed by edema of the lungs.
"6 Auer.
and 106.
Proceedings of Society for Experimental Biology and Medicine, 1918.
XV, 104
A L IP H A T IC OR P A T T Y COM POU N DS.
41
In factories in which dimethyl sulphate was found in use, the only
precautions taken are against a caustic action on the skin. The men
are given goggles and rubber gloves, but in one plant they were not
using even those and were handling it with less care than they gave
to caustic soda. It was said in this plant that only one really bad
case of blistering had occurred and that burns on the skin or in
flammation of the eyes were the worst accidents that could be ex
pected.
The surgeon in charge of the National Aniline and Chemical Co.,
Buffalo, Dr. Ferdinand D. Mohlau, has recently published58 an ac
count of two cases of dimethyl sulphate poisoning, the first reported
in America. Two men, aged 53 and 55 years, were exposed on May
26, 1920, to contact with liquid dimethyl sulphate and to the fumes.
They did not notice any effect at first beyond a slight irritation of
the throat and eyes, but during the evening of that day the irritation
of the eyes and throat became intensified, and inflammation of the
bronchi developed. Cyanosis appeared. A physician was summoned
to see one of the men, C., that night, but Dr. Mohlau did not see the
case till the afternoon of the following day. He found him “delirious,
with a severe congestion of the throat, symptoms of bronchitis, a
severe inflammatory condition of the eyes, intense pain, photophobia,
and a severe migraine.” The second man, S., was then visited and
found in a similar condition, but later on his symptoms became much
aggravated, acute congestion of both lungs, edematous condition of
throat and larynx, and considerable cyanosis. S. passed into a coma
tose state, and during recovery from his pneumonia he relapsed sev
eral times with an aggravation of all symptoms. C. had a quick
crisis and recovered promptly, but at the time of writing, some six
weeks later, both men were still suffering from photophobia and from
the damage to throat and larynx. S. has also complete loss of color
vision and his visual field is reduced to one-tenth. His optic nerve
shows pale outer edges but no degenerative changes are discernible.
The urine examination showed in both case£ an increase in the
phosphates and sulphates, with a faint trace of albumin, an occasional
hyaline cast, and no sugar.
In this same article is given the result of experiments on a rabbit,
carried on by Charles A. Bentz and R. L. Cameron, both of Buffalo.
The animal was exposed to the fumes of dimethyl sulphate under a
bell jar and died promptly. The blood was dark and fluid and gave
the characteristic bands of methemoglobin, the liver and kidneys were
congested and had undergone intense degeneration, and the lungs
were edematous.
The use of methyl chloride or chlormethyl is not unattended with
danger, as the Germans have found. Kobert says it is one-fourth as
poisonous as chloroform. It is very volatile, and in a report by
Gerbis59 histories of two cases are given of poisoning by fumes of
methyl chloride in machinists who had to clean from time to time a
gasometer through which methyl chloride passed. Both were elderly
men, which may explain their susceptibility. They had attacks of
somnolence, once preceded by delirium, and both had marked im
pairment of sight.
58 Journal of Industrial Hygiene, November, 1920, vol. 2, No. 7, p. 238.
50 Gerbis. Miinchener medizinische Wochenschrift, 1914. LXI, 879.
42
IN D U ST R IA L PO ISO N IN G IN M A K IN G CO AL-TAR DYES.
INORGANIC COMPOUNDS,
The heavy acids, hydrochloric, sulphuric, and nitric, are used
in dye manufacture in large quantities, and the fumes from these
acids or from their anhydrides form one of the most difficult prob
lems of factory management. Hydrochloric acid and chlorine fumes
are encountered especially in the making of anilin hydrochloride, of
benzidin sulphate from benzidin hydrochloride and the making
of nigrosin and indulin, Nitrous fumes are given off in all nitration
processes and must always be removed through fume pipes. As a
usual thing such pipes are not provided with exhaust suction and
are efficient only when everything works well. I f the wind is in the
wrrong direction, and still more if the nitrator is overheated, these
fumes may escape. There are records of serious poisoning from
nitrous fumes in making dinitrotoluene, mononitrobenzene, parani
tranilin and nitroso-beta-naphthoL The fumes of sulphur dioxide
may be given off in all sulphonation processes, and during the early
stages especially these fumes may be very distressing.
All these compounds except sulphur trioxide have a very caustic
irritating action on the respiratory tract. It is characteristic of them
that the effects do not show themselves in their full intensity till
some hours after, usually when the man has left work and gone home.
There is always more or Jess strangling, with burning of the throat,
at the time the gas is being breathed in, but usually these symptoms
can be controlled by simple treatment, The man apparently recovers
and then, some 6 to 12 hours later, he exhibits the symptoms of
acute congestion of the lungs.
Sulphur dioxide may be formed, but rarely, at high temperatures
in certain reactions. In moist air or in contact with the mucous
membranes of the throat and nose it takes up water and changes
to sulphurous acid, which is very caustic. Irritation from S 0 2 be
gins at as low a point as 0.01 in 1,000 parts of air, and a new work
man may be made ill by 0,03 part, but tolerance is quickly estab
lished, and men can work in an atmosphere much more highly
contaminated than that. Sulphur trioxide is irrespirable. It is
very disagreeable and choking, but not harmful, for it can not com
bine with water and is breathed out again unchanged.
The fumes of hydrochloric acid are very caustic to lips and tongue
and throat. The danger limit is said to be between 0.1 and 0.2
part per 1,000 parts of air. Chlorine, which is almost two and a
half times as heavy as air, is asphyxiating, paralyzing to the cen
tral nervous system, and irritating to the respiratory tract. There
is an abundant literature on chlorine poisoning because of the use
of this gas in chemical warfare. Fortunately, both hydrochloric
acid and chlorine fumes are so immediately strangling in their
effect that workmen exposed to them get away as quickly as pos
sible and so escape the severer effects.
The most serious effects result from nitrous fumes. Both chlo
rine and sulphur dioxide are more immediately painful and chok
ing than nitrogen oxide fumes, and therefore a man makes more
effort to escape from them and seldom is so severely poisoned.
Nitrous fumes can be breathed more freely, and in many industrial
INQBGANIC COMPOUNDS.
43
cases these poisonous gases reach the whole of the lung surface
so that when inflammation develops there is no normal tissue left,
and death is inevitable.
More than one industrial physician employed in dye works has
said that he dreaded nitrous fume cases more than any other.
According to Haldane, exposure to 0.5 part per 1,000 parts of air
for half an hour is enough to kill mice, death coming on after 24
hours,
In dye manufacture the really serious cases of nitrous fume poison
ing result usually from an accidental leak of fuming nitric acid, or a
job of cleaning or repairing in an acid tank. A typical case of the
latter was related recently. The man went into a tank which had
contained nitric acid, but which was supposed to be empty. There
was, however, a small amount of residue at the bottom. He “ choked
up ” several times, and when his work was finished he was coughing
and had a burning pain in his chest. On his way home he stopped
in to consult his doctor, but the latter found no signs in the chest
except a slight bronchitis. Early in the morning the doctor was sum
moned to see him and found him dying of edema of the lungs.
The cases &£ industrial poisoning from nitrous fumes that have
been reported are usually severe acute poisoning, and if the man re
covers it is assumed that his recovery was complete. The physician
does not follow up his later history. Therefore we have little in
formation about the permanent damage to the lung tissue which may
be produced by such an accident, even when the man has apparently
recovered from the acute symptoms. There is one report from an
American source of an accident involving 20 men whose subsequent
history was followed up for nine months. (Hall and Cooper.60)
Four of them died of pulmonary inflammation, but only two from
an acute attack developing immediately, the other two were not
affected till several weeks after the accident. There were relapses
in one-third of the survivors, with symptoms like the original attack.
Eight recovered their health practically entirely, after periods run
ning from 90 to 210 days, but the others suffered loss of weight,
44nervousness,9’ stomach troubles, cough, pleuritic pain, difficulty in
breathing, especially if the air was smoky. The loss of weight among
these men was from 20 to 40 pounds.
Hydrogen sulphide or sulphuretted hydrogen.—hi the making
of sulphur dyes, when sulphur and sodium sulphide are fused
with various amido compounds, hydrogen sulphide may be evolved
in gaseous form. The danger of this is greatest in connection
with the sulphur browns and khaki, less in connection with
sulphur black, least with sulphur blue. It is poisonous in very
small quantities, danger to life beginning at 0.75 per 1,000 parts and
1 to 1.5 per 1,000 is rapidly fatal. It is very much dreaded in the
dye industry, not because many fatalities have resulted from it, nor
because it gives rise to a great deal of ill health, but because of its
startlingly rapid action. It seems to be the general opinion that
sulphuretted hydrogen is either rapidly fatal or does little damage.
Men who are “ knocked out ” by the gas either die without recovering
consciousness or they come to after an hour or two and seem none the
eo H a ll and Cooper.
Jo u rn a l o f A m e ric a n M ed ica l A sso cia tio n ,
1905.
XLV,
396.
44
IN D U ST R IA L PO ISO N IN G IN
M A K IN G COAL-TAR DYES.
worse for it, although a careful physician does not allow them to go
back to work for a day or so. Many instances have been given of
the rapid action of this gas. One man went into an empty pressure
tank in a sulphur brown department too soon after it was emptied
and was completely knocked out in five minutes. A second man who
bent over the manhole to help him was also overcome, but neither
died. The physician who told of this thought it dangerous to let a
man go into a receptacle which had an opening no larger than a
manhole. Several cases have been reported of pipe fitters or car
penters who were working on a platform in sulphur dye depart
ments being overcome by the fumes so that they fell from the plat
form and were injured. One pipe fitter who was affected by these
fumes was sick for four days, although he did not suffer from any
accident. Rumors of fatal poisoning have been heard, but have not
been substantiated.
Hydrogen arsenide or arseniuretted hydrogen.— There is a very
general impression in the minds of the public that arsenic is
used in the manufacture of anilin dyes and that some of them
are poisonous because they contain arsenic. This belief, which
is also held by many physicians, is founded on old knd long dis
carded methods of manufacture. In an early article, written by
Sonnenkalb in 1864, there is a description of the original methods
used to produce fuchsin and the colors derived from it. As at pres
ent, anilin was made by the reduction of nitrobenzene with iron
filings and acid; only acetic acid was used, instead of hydrochloric.
Rosanilin, which is colorless, was then formed by oxidation and was
the starting point for the colors, which were pvoduced by the action
of organic and inorganic acids. The oxidizing substances used were
the oxide and nitrate of mercury, red lead, arsenious acid, and other
less poisonous compounds. Fuchsin was made with arsenious acid
(H 3A s 0 4), and its poisonous qualities were due to its arsenic content.
This method is, of course, no longer used.
The arsenical poisoning which occurs now in the manufacture of
anilin dyes is caused by the accidental evolution of hydrogen arsenide
(A sH 3) which may occur in connection with certain processes, espe
cially acid reduction, and alkaline reduction when followed by acidi
fication. These processes are described fully in a later section (see
p. 53). It is a subtle and powerful poison, causing extensive destruc
tion of the elements of the blood and, as a consequence of this, an
acute degeneration of liver and kidneys. When the exposure to the
fumes is great enough to set up acute poisoning, the man is seized
with symptoms which may suggest, and, in fact, probably often do
suggest, acute anilin poisoning. He is nauseated, complains of
cramps in the stomach, vomits, complains of headache, dizziness, and
faintness. The urine is dark, another resemblance to anilin poison
ing. But the condition lasts longer than that caused by anilin, or
even by dinitrobenzene. The case does not clear up, but grows worse,
the urine becomes bloody, anemia is profound, jaundice appears, and
signs of inflammation of the liver. The man may pass into a typhoid
condition lasting for days, or he may die within a few days, deeply
jaundiced, with constant vomiting ot greenish fluid, with strangury
and bloody urine. Autopsy then shows hemorrhagic inflammation
of liver and kidneys.
IN O RG AN IC CO M POU NDS.
45
This form of poisoning has been recognized in Germany for a
good many years and carefully guarded against. It has also been
studied recently by physicians of the British Factory Inspection De
partment and by physicians attached to the British works. Accord
ing to these authorities, it is only prudent to take into consideration
the possibility of arsenical poisoning in any case of supposed poison
ing by a nitro or amido compound when the symptoms do not clear
up, but profound anemia or jaundice appear. In such cases the
urine should be tested for arsenic. A record of 16 such tests was
shown by one of these physicians. In almost all, traces of arsenic
were found in the urine, but only five had enough to be of signifi
cance. Four of these five men were working in the benzidin de
partment, where most of the accidents from hydrogen arsenide fumes
have taken place. The fifth was also engaged in a reduction process,
producing amidodiphenylamine by the use of zinc dust, iron filings,
and hydrochloric acid. No symptoms were complained of by two of
the men, but their color was livid and their urine dark. The symp
toms of the other three might easily have passed for anilin poison
ing, jaundiced skin, dark colored urine, headache, and abdominal
pains. Obviously it is very important to distinguish this low-grade,
chronic, arsenical poisoning from poisoning by a nitro or amido
compound. It is distinctly more serious, because arsenic is a cumu
lative poison in a sense in which no organic compound can be.
To illustrate this sort of accident in dye manufacture, three Ameri
can cases which occurred in a small plant in New Jersey' are selected.
This factory was making naphthionic acid from alphanaphthylamine and sulphuric acid, and also benzidin base and sulphate by a
reduction process involving contact between hydrochloric acid and
zinc dust. The construction of the plant was crude, and fumes from
the different processes were allowed to escape into the room. One
night five men were at work in the benzidin department, and when the
acid was added at the end of reduction there was a “ boil over.” The
fumes affected all of the men so that they were obliged to quit work.
Their subsequent history was obtained partly by personal interview
with one of them and partly from the records of the hospital to which
two were sent.
The first man, C, had been employed in the plant for 18 months,
and had often suffered from the fumes in the benzidin department.
On this night he went home feeling very ill, so that he could not even
get into bed, but dropped down on the floor. He did not send for
a doctor, thinking it no worse than former attacks until he saw that
his urine was the color of blood, when he became alarmed, for this
had never happened before. He was ill for about three months,
suffering from pains in the kidney region, a band-like feeling around
the lower part of his abdomen, intense pain in the back of his head
and neck, vomiting, poor appetite, depression, and loss of strength.
During this time his wife said that he looked like 44a yellow corpse.”
When seen about 18 months later he still had pains in the kidneys,
headache and buzzing in the head, and his strength had not returned.
The second man, D, was treated at home for about two weeks for
supposed typhoid fever, and no details as to this part of his history
can be obtained, but probably, judging from the diagnosis, he had
symptoms of abdominal distress of an aggravated kind. When he
46
IN D U ST R IA L PO ISO N IN G IN M A K IN G COAL-TAPv DYES.
was finally brought to the hospital the Widal test disposed of the
typhoid-fever theory. He was then, on the fifteenth day after the
accident, in a semiconscious condition; there were ulcers in mouth,
throat, and tongue; he had diarrhea and vomiting, and his body was
shaken with tremors of the muscles. Albumin was found in the
urine, but no blood. There was a very marked anemia, the red
blood corpuscles being reduced to 1,780,000. Both spleen and liver
were enlarged. In spite of his partial delirium he showed great pain
and difficulty on urination, and this symptom increased, together
with retention of urine, diarrhea, and frequent vomiting, during the
two days in the hospital. He died on the third day, but no autopsy
was made.
E went to the hospital 48 hours after the accident. He was then
jaundiced, complaining of great pain in the lower chest and over
the bladder, vomiting greenish fluid, voiding blood-red urine. There
was also pain and difficulty in urination. These symptoms per
sisted for two days, then slowly improved, and he was discharged on
the sixth day, a cured ” according to the hospital record, but accord
ing to O he has never recovered his health since then nor been able
to do a full day’s work. No blood count was made in this case, but
hemoglobin was found in the urine.
As for the other two, one never reported back to the plant, and C
knew nothing of his history. The fifth, a cousin of C, recovered
completely.
There seems little doubt that these were cases of poisoning from
the escape of hydrogen arsenide when acid and zinc dust, one or the
other containing arsenic, came together in the process of making
benzidiiio That the diagnosis of anilin poisoning should have been
made is natural, for anilin also is a blood poison, one that destroys
the red corpuscles, thus causing the appearance of hemoglobin in the
urine and later possibly jaundice. Anilin poisoning is also accom
panied by more or less pain in the abdomen and by vomiting, but all
these symptoms were more accentuated and persistent in the cases in
question than they are in anilin poisoning. No case of the latter is
on record in which the victim passed into a typhoid condition lasting
for days and terminating in death. On the other hand, the histories
of all these cases are very typical of arseniuretted hydrogen poisoning.
Gamtios.— The caustics used in dye manufacture are sodium hy
drate, or caustic soda, N allO , which is used in so-called hydrolyzing
or caustic fusion (see p. 5 1 ); sodamid, NaNH 2, used to change phenylglycine to indoxyl, in the course of which reaction fumes of ammonia
may be given .off .; and monochloraeetic acid, which is used in the
manufacture of indigo.
It is not necessary to describe the effect of caustic soda upon the
skin and mucous membranes of nose and throat and on the conjunc
tiva, for this effect is familiar to every one. Sodamid is not so pow
erful a caustic. In contact with a sweating skin it changes to NaHO,
and therefore it acts more slowly than caustic soda, Monochloracetic
acid causes severe blistering and extensive desquamation, the skin
coming off in sheets, but if the bum is treated promptly and not
allowed to become infected, there is almost no pain connected with it,
Fumes of ammonia have given rise to two cases of serious inflam
mation of the lungs, with edema, in the dye industry, in connection
with the manufacture of indigo and of aurantia.
SICKNESS IN GERMAN DYE MANUFACTURE.
47
RECORDS OF SICKNESS IN GERMAN DYE MANUFACTURE.
A careful search through German factory inspection reports for
the seven years j ust preceding the war shows the following substances
to be responsible for occupational poisoning in the color industry:
Anilin.
Nitrobenzene.
Paranitranilin.
Toluidins, ortho, and para.
Paranitrotoluene.
Alpha and beta naphthylamine.
Di nitrobenzene.
Hydroquinone and other quinones.
Ohloranthracene.
Dimethyl sulphate.
Hydrogen sulphide.
Chlorine gas.
Phosgene.
Nitrous fumes.
Pyrogallic acid.
Potassium bichromate.
Monochloriodide.
Phosphorus pentachloride, and oxychloride.
Methyl chloride or chloromethyl.
Several detailed studies have been made of sickness in certain
German plants. For instance, such a report is given of a factory
employing 251 men, in which there were during a year’s time 33
cases of industrial poisoning, with 500 days of sickness. For
the workmen not employed in the anilin department the average
was 0.97 attack of illnfess per man, each attack averaging 14.6 days.
For the anilin department the average was 1.74 attacks of illness,
wTith 23.48 days. Ten per cent of the cases in the nonanilin depart
ments wTere skin diseases; 41.8 per cent of those in the anilin depart
ment were skin diseases. Digestive troubles made up 17.4 per cent
of the nonanilin workers; 45.4 per cent of the anilin workers, Some
unusual cases are described. One was a boiler tender who was using
water from an anilin still. Some of it boiled over and soaked the
floor and the coal, and he had a severe attack of anilin poisoning. A
case of bloody urine occurred in a man* making naphthol, and an
other in a man making u fuchsin melt.” There was one death from
benzene poisoning. A workman went into a room which he had been
warned not to enter because benzene had run out on the floor.
Grandhomme,61 who was for many years physician to one of the
great German dye works, analyzed 1,163 cases of sickness in the
force in five years, 1874 to 1879. In the manufacture of anilin colors
there was an average of 60 per cent of sickness, in making alizarin
colors 46 per cent, and in the mechanical department 40 per cent.
But the average length of disability was greater among the men in
the alizarin department than in the anilin because there was a
greater proportion of skin affections, and these are notoriously slow
to heal. There is far less sickness shown in the more recent reports,
as indicated in the next paragraph.
In the report for the year 1913 a factory with 9,376 men had 12
cases of anilinism, with 98 days of sickness. The two serious cases
in this factory were caused, one by the spilling of anilin, the other
by repair work in an imperfectly cleaned apparatus. The first man
got his clothes soaked with anilin, was made to strip at once and
take a thorough bath, but in spite of that half an hour later he became
cyanosed. The second man was a lead burner working in a receptacle
which had contained nitrobenzene and had not been thoroughly
cleaned. He was ill with nitrobenzene poisoning for eight days.
61
280.
Grandhomme.
Vierteljahrsschrift ifiir gerichtliche Medizin, 1880.
XXXII, 120 and
48
IN D U ST R IA L PO ISO N IN G IN
M A K IN G COAL-TAR DYES.
RECORDS OF SICKNESS IN AMERICAN DYE WORKS.
Cases of poisoning have occurred in the United States from the
following substances used in the making of dyes and dye inter
mediates :
Benzene.
Toluene.
Mononitrobenzene.
Dinitrobenzene.
Paranitrochlorbenzene.
Orthonitrochlorbenzene.
Dinitrochlorbenzene.
Anilin.
Paranitranilin.
Metanitranilin.
Dimethylanilin.
Diethylanilin.
Anilin hydrochloride.
Paranitrochloranilin.
Nitroso dimethylanilin.
Paranitrotoluene.
Dinitrotoluene.
Orthotoluidin.
Paratoluidin.
Paranitrotoluidin.
Orthonitrotoluidin.
Acetylparatoluidin.
Benzylchloride.
Chlorinated toluene.
Paranitrophenol.
Paraamidophenol.
Dinitrophenol 1-2-4.
Paraphenylendiamine.
Metaphenylendiamine.
Nitrosobetanaphthol.
Alphanaphthylamine.
Betanaphthylamine.
Benzanthrene.
Anisols.
Quinones.
Phenylcarbylamine.
Pheny lhy droxy lamine.
Solvent naphtha.
Pyridin.
Nitric acid and nitrous oxides.
Sulphuric acid and sulphur dioxide.
Hydrochloric acid and chlorine.
Hydrogen sulphide.
Hydrogen arsenide.
Monochloracetic acid.
Sodamid.
Sodium hydroxide.
Ammonia.
Methyl alcohol.
Phosgene.
Cyanosis from the handling of nigrosin has been reported, but
probably should be attributed to anilin. Cases of dermatitis are
said to occur among men making azo colors, and the condition is
called “ azo itch.” It is doubtful whether the cause is to be found in
the finished colors. It would seem more probable that it should be
attributed to one of the nitroso intermediates.
In treating dimethyl anilin with sodium nitrite the nitroso com
pounds of the corresponding bases are formed and these are known
to be very irritating. It is possible that in making azo dyes some
nitroso might be formed, as, for instance, when the amine to be
treated with the nitrite is impure and contains phenols or secondary
or tertiary amines.
In an industry so new as the anilin color industry, it is very im
portant to know not only which are the possible dangers which
threaten the wTorkmen, but which are really serious and which are
only exceptionally serious. We have records from three large Ameri
can factories which throw some light on this question. In one of
these the different processes have been classified according to their
danger, so that the examining physician may decide, on the basis of
the physical condition of the applicant for work, in which depart
ment he can be safely placed. There are three classes of processes.
Class 1 includes operations or processes in which nitro or amido
compounds are used and which experience has shown involve risK
of poisoning to the workman. Under this classification come the
following departments: Naphthionic crudes, dinitrobenzene, the dia
mines, the so-called “ anilin dyes ”— rosanilin, magenta, fuchsin, anilin
49
SICKNESS IN AMERICAN DYE WORKS.
blue, alkali blue— phenylglycin drying, anthraquinone, pyridin, indanthrene yellow.
Class 2 includes operations or processes involving the handling
of nitro or amido compounds, but which are attended with less risk,
either because the poisoning set up is less severe, or because the equip
ment is so arranged that there is no contact with the poisonous sub
stances. In this class come paranitranilin purification, betanaphthylamine, anilin reduction, benzidin manufacture, auramine, and
benzanthrene.
Class 3 includes operations which do not involve handling nitro or
amido compounds, or in which such compounds are present but no
ill effects have thus far resulted from such work. This class is, large
and includes the ortho and paratoluidin department, sulphonating
processes of all kinds, all low-pressure autoclave work, naphthionic
purification, picramic acid, benzoic acid, chloracetic acid, salicylic
acid, chlorine, hydrochloric acid, chlorbenzene, benzaldehyde, sodium
sulphide, nitranisol, eosin, victory green, malachite green and sulphur
black and indigo.
The record of a plant in which about 850 process men are em
ployed and about 400 laboratory men is as follows for one month of
hot summer:
Cases.
Poisoning from nitro and amido compounds, new cases________ 29
Poisoning from nitro and amido compounds, old cases still
under treatment___ ________________________________________ 26
Acid burns of cornea_________________________________________ 20
Acid burns of cornea with conjunctivitis_____________________ 29
Dermatitis___________________________________________________ 122
Alkali in eye, inflammation_________________________________
26
Alkali burns_________________________________________________
82
Chlorine fumes______________ _________________________________
1
The improvement that has taken place in this plant within the
last year is shown by the record of days lost on account of occupa
tional disease in relation to the output of the plant. There was at
first a great deal of trouble in the ortho and paratoluidin area, and
for a time the cases of poisoning were very frequent. Then exhaust
ventilation was installed to remove fumes not only from the liquids
but from the solids also. The men were given rubber boots and
gloves and they were strictly watched and sent to the hospital for
treatment at once if the slightest sign of illness appeared. The days
lost on account of poisoning, which in December had been 61 for an
output of 125,000 pounds, had reached zero in June with an output
of 340,000 pounds.
For a second plant the records for six months in 1918, from Janu
ary to July, are available.
The number employed at this time was about 1,600, something over
TOO of whom were process men and about 100 engaged in laboratory
work. The company considered only cases of acute fume poisoning
or of injury to skin or eyes by acids and caustics as “occupational”
in character, so in order to get at the amount of illness in the dif
ferent departments one must look through the list entitled “non25431°—21
4
50
INDUSTRIAL POISONING IN M A K IN G COAL~TAR DYES.
occupational.” This gives the number of cases among 1,640 men in
six months as follows:
C a ses.
Gastro-intestinal diseases_____________________________________
Colds, catarrh, coughs, grippe________________________________
Lumbago, rheumatism, etc____________________________________
H eadache____________________________________________________
Abscesses, boils, etc__________________________________________
Skin eruptions_______________________________________________
Conjunctivitis and sundry eye diseases___________ __________
Unclassified------------------ -------------------------------------------------------
03
69
12
13
27
37
72
43
T o t a l__________________________________________________338
The different classes of employees suffered in the following pro
portions during the six months:
Class.
Mechanical and yard.....................................................................................
Office force, police, etc...................................................................................
Labora lory ..................................................................................................
Intermediates..................................................................................................
Colors.................................................................................................................
Raw materials.................................................................................................
‘Number o:
employees.
’CCISos of
sickness.
627
116
97
300
270
146
18
85
73
33
200
11
Per cent
sick.
IS. 5
5. 5
18.6
28.3
27.0
22.6
During the same period a record of accidents was kept, both those
involving loss of working time and those needing treatment but with
out loss of time— minor accidents.
Character of injury.
Acid burns................................... ...................................................................
Caustic soda burns.........................................................................................
Steam and liquid burns................................................................................
Burns from explosions....................
............................................
Sundry burns. . . .............................................................................................
Anilin poisoning..............................................................................................
Nitrous fumes..................................................................................................
Sundry fumes............... .................................................................................
Injuries to eye (not mechanical):
From acids.................... ..........................................................................
From caustics and lime..........................................................................
Total...................................................................................................
Accidents
causing loss Days lost.
of time.
Minor
accidents.
1
3
4
3
4
37
1,605
13
15
5
74
2
2
6
5
10
28
1,779
103
1
6
21
20
16
34
3
2
1
2
15
It is impossible to read these figures and not see the influence of
the occupation on even the supposedly nonoccupational diseases
given in the second table. The workmen who come in contact with the
raw material, intermediates, and colors, have a decidedly higher
sickness rate than have the workmen not so exposed.
PROCESSES IN DYE MANUFACTURE.
It is not the purpose of this report to describe the very compli
cated processes of dye manufacture except so far as it must be done
in order to point out the possible dangers to the workmen. Only a
bare outline is presented of the principal reactions, in connection
wTith the consideration of the special risks involved in each. It is
impossible to generalize about the dangers of the color industry, the
various departments of which differ so much in character.
PR O C ESSES
IN
DYE
M ANUFACTURE.
51
There are certain fundamental chemical processes that are used
in dye production and that carry with them dangers which are some
times constant, inherent, and well recognized; others that are acci
dental and perhaps quite unforeseen by all but very experienced men.
These processes are as follows:
1. Sulphonation, or treatment with fuming sulphuric acid, usually
added in excess. This very common procedure results in the re
placement of an H atom in an organic compound by the sulphonic
acid ( S 0 2H G) group, and often the change from a toxic to a non
toxic or weakly toxic body. The troublesome features of sulphona
tion lie in the nature of the body to be suiphonated, anilin, toluidins,
etc., and in the fumes of S 0 2 that may be given off if a good fume
pipe system has not been installed or if sulphonating tubs are left
partially uncovered. These fumes may be very disagreeable, espe
cially during the early stages of the reaction, In one plant the fore
man remarked that when the sulphonators were charged they ex
pected “ a gas attack lasting about five minutes, during which time
everyone takes to cover.” S 0 3 is not dangerous, but at a high tem
perature it may, through the oxidation of organic matter, change to
S 0 2, as when anilin sulphate is heated. Then sulphonation and
partial oxidation result in the formation of sulfanilic acid and S 0 2.
2. Caustic fusion, or caustic melting or hydrolyzing.— It is usu
ally a suiphonated product that is fused with sodium hydroxide,
and the S 0 20 H group is replaced by a hydroxyl (OH ) group. In
this way benzene monosuiphonic acid yields hydroxy-benzene or
phenol, and naphthalene monosuiphonic acid yields alpha and beta
naphthol. The danger here is from the sodium hydroxide, not only
from contact with the solid or liquid form but even from exposure
to steam which carries it. Caustic burns, sometimes very severe, are
fairly common in connection with this process, and even in the bestmanaged factories the danger has not been entirely done away with.
I f the sodium hydrate is added to a liquid in the kettle there is great
danger of splashing; it should always be put in first, Methods of
handling the caustic differ much in different plants: sometimes it is
handled in solid form, shoveled or scooped, but this gives trouble
with dust, especially in hot weather when it dissolves on the sweat
ing bodies and causes a great deal of irritation. Or the container
is heated and the liquid contents are blown to the hydrolyzer. This
is much safer if all goes well, but productive of more serious acci
dents if anything goes wrong and the liquid caustic splashes about.
Another disastrous accident is the blowing up of an autoclave used
for caustic fusion, scattering the hot caustic and causing terrible
burns of skin and eyes.
In the making of betanaphthol, which is always disagreeable
work, hot, sloppy, steaming, ill smelling, it is chiefly the use of
caustic soda that gives trouble. Naphthalene is suiphonated, the
resulting alpha and beta salts are separated by liming (treatment with
calcium to form the soluble alpha and insoluble beta salt), the
calcium is replaced by sodium, and the sodium salt of betanaphthalene sulphonic acid is fused with caustic soda. It is here that
the escaping steam may carry caustic with it.62
62The most recent pi’ocess for making betanaphthol is without liming. Naphthalene is
suiphonated, the sulphonation mixture is neutralized with soda ash and salted out, the
beta salt is filtered out and fused to betanaphthol.
52
INDUSTRIAL POISONING IN M A K IN G COAL-TAR DYES.
In boiling p-nitracetanilid with sodium hydrate, if the boiling is
carried too far decomposition may take place and anilin and am
monia be given off. There is always an effort made to provide for
the possible escape of fumes here.
3.
Nitration .— A mixture of nitric and sulphuric acids is used
for nitration, the latter being added to take up the water liberated
in the reaction, which would otherwise result in too great a dilu
tion of the nitric acid. The most usual nitration process in dye
manufacture results in the production of a mononitro compound,
a single N 0 2 group replacing one hydrogen atom in the benzene
ring. For dinitro and trinitro compounds further nitrationl is
carried on in successive steps usually. The danger in this process
is that which always attends the use of nitric acid, Not only may
severe burns result from splashed acid, but the fumes of mixed
nitrogen oxides that are given off when nitric acid is exposed to
the air or when it is added to the organic substances to be nitrated
constitute one of the gravest risks to which the workman in the dye
industry is exposed.
It must also be remembered that the product resulting from ni
tration is more toxic than the original compound and, requires
great care in handling. Reference has already been made to the
difficulty encountered with the making and use of dinitrobenzene,
nitranilins, dinitrophenol, to mention only the worst of these com
pounds. The waste acid from the nitrators is also a source of danger,
for it often carries enough of the product of nitration to cause
poisoning. In making DNB, the first waste acid may contain as
much as 20 per cent DNB, and must be used again and again to
recover it. The manufacture of DNB from mononitrobenzene is
almost always the most troublesome department of all, and in some
plants this one place, with only an insignificant force of men, may
send as many cases of occupational poisoning to the physicians
as all the rest put together. This is when the DNB is allowed to
flow out and solidify in open pans or on a filtrose bed, and then is
broken up and shoveled or scooped up into trucks or barrels.
The best arrangement of this kind seen allows the product from
the nitrators to flow into a covered hot washing tank with an air
exhaust, then out into a cold-water tank outside the building under
a shed, where it is pelleted by the cold water. This, then, is car
ried by a screw conveyor to the barrels. The worst one seen had
admittedly so much poisoning among the DNB men that sometimes
it seemed as if the plant must shut down for want of help. The
nitrated product ran out into open pans and solidified there; the
men then broke up the solid mass, shoveled the fragments into
trucks, and emptied them into a crystallizer, heated, where the
DNB was melted and crystallized. This was inclosed. The crys
tallized DNB was then screened, and although the screen was in
closed a fine powder escaped in quantities when the screened prod
uct was poured into barrels through a canvas chute, for this leaked
badly. Near the screen stood open barrels of lumpy DNB, which
had been dug out of the crystallizer through an opening and which
was fed into the screen with a shovel.
In a German plant visited in the summer of 1919 the DNB is
never transported in the open; it is melted and blown through
PR O C ESSES
IN
DYE
M ANUFACTURE.
53
pipes. When it is packed a false cover is used, with two openings—
one connected with the hopper of D N B 9 the other with the dustcollecting system. In this way all dusty shoveling and scooping
and all direct contact are avoided. Even the packed and closed
barrels are regarded as a source of possible danger, for DNB
volatilizes at ordinary temperature, and still more on a hot day;
so the Germans store these barrels in an open shed, lest the fumes
from them affect men working in that department.
4.
Reduction.— Acid reduction is carried on with the aid of hydro
chloric acid and iron filings; alkaline reduction, with zinc dust and
usually caustic soda; neutral reduction, with zinc dust alone. The
former is used in the production of anilin from nitrobenzene,
ortho and para toluidin from nitrotoluene, alpha naphthyiamine
from nitronaphthalene. It is also used in the reduction of dinitro
benzene to phenylendiamine, dinitrotoluene to toluylendiamine, nitronaphthodisulphonic acid to amidonaphthodisulphonic acid, nitrophenol to amidophenol, and so on. Since reduction begins with a
nitro compound and ends with an amido compound; it follows that
there is a decided risk in connection with the reaction, a risk more
or less recognized and more or less guarded against in every plant.
When the process goes forward normally, without any hitch, there is
little trouble with sickness among the men. To be sure, the taking
of samples from time to time, if carelessly done so that the liquid
spills on the hands, may give rise to mild poisoning or fairly serious,
according to the compound undergoing reduction, and in hot, heavy
weather, especially on the night shift, the fumes, which escape from
the feed hole, may cause enough discomfort to force a man to quit
work for that shift though he is able to return for the next one.
But frequent and serious cases of acute poisoning and a general con
dition of anemia among the men in the reduction department is
found only when the mechanical arrangements for reduction are
faulty. It is when, for some reason, poor construction of the reducer,
poor charging, failure of motive power, or some other defect, the iron
filings fall and cake around the paddles and the reaction has to be
interrupted, the manhole opened, and the “ sludge ” cleaned out for
a fresh start, it is then that serious poisoning occurs. There is a
wide variation between anilin reduction departments in different
plants, it being a matter of ordinary observation that while in some
of them the caking of a reducer is a rare accident, which may not
happen oftener than once in three months, in others it seems to be
an ordinary occurrence. The first kind of a plant has a scrupulously
clean reduction department, with only a slight odor of anilin, or,
perhaps, it is quite free from odor; the second is an untidy, some
times filthy, spot, the floor covered with a wet mass of black iron
filings, which are tracked over the floor by the men’s feet; the anilin
water runs partly through the gutters in the floor, but some of it
spreads over and lies about in pools. The men work through the
open manhole, prodding the caked mass with iron rods and hoes and
then drag it out. Their hands and clothing show the contact with
this anilin-laden sludge, which their work necessitates. In such a
place anilin poisoning is looked upon as a serious thing and one very
hard to control, while in well-managed plants it is considered a
rarity unless in very slight form.
54
INDUSTRIAL POISONING IN M A K IN G COAL-TAR DYES.
In the reduction of dinitrobenzene to phenylendiamine the danger
is much greater than in reducing mononitrobenzene to anilin, and,
unless the charging is done with great care, trouble inevitably re
sults sooner or later. This is also true, although to a less extent, with
the reduction of dinitrotoluene to toluylendiamine. The English and
the Germans know much more about the dangers of these compounds
than we do and use special precautions in handling them. A good
device for charging the reducer with dinitrobenzene was seen in an
English factory. The covered truck had an opening just on a level
with the feed door of the reducer, and when the lid of this opening
was dropped down it formed a bridge between truck and reducer
over which the DNB could be pushed without scooping or dropping.
In contrast to this was the method used in one of the American
plants visited, where the DNB was shoveled from an open truck
into a pail and this dumped into the reducer. It is impossible for
a man doing work like that to keep from contact with the stuff, and,
aside from the contact, there is the continual volatilization.
In making phenylendiamine by reduction of DNB in one Ameri
can plant there was much poisoning among the men so long as the
product was filtered hot, but this has been avoided by sending in a
stream of cold water which prevents fumes from’the filter press and
also from the sludge. The sludge contains only I per cent of DNB,
but enough to give trouble if it is hot.
The usual dangers of acid reduction are well known and under
stood, but there is one possible danger in connection with it and still
more in connection with alkaline reduction, which is not generally
recognized in American plants, although it has long been known in
Germany and has recently attracted a good deal of attention in
England. This is the evolution of fumes of hydrogen arsenide,
spoken of in the former section of this report.
There are several processes in dye manufacture in which the con
ditions may occur which give rise to the formation of hydrogen
arsenide, namely, the contact of an arsenic-bearing metal, zinc or
iron, with hydrochloric acid or sulphuric, or the contact of an arsenicbearing acid with one qf these metals. In one of the cases reported
from England a plumber went into an empty acid tank to repair it.
That is, the tank was technically empty, it had been washed out
and only about a bucketful of fluid was left at the bottom. But
the acid, chamber acid, contained enough arsenic to poison him and
he died of hemorrhagic nephritis two days later. A similar but even
more disastrous accident took place not long ago in New Jersey.
Here three men went into an iron tank that had contained chamber
acid but was supposed to be empty and clean. A ll were quickly
overcome by fumes of A sH 3 and two died from its effects. It does
not take much arsenic in this form to cause severe poisoning. Ac
cording to Rambousek an amount corresponding to about one-hun
dredth of a milligram of arsenic is sufficient.
The other sources of hydrogen arsenide in the dye industry are
reduction processes, both acid and alkaline. In reducing nitrobenzene
to anilin, nitrotoluene to toluidin, etc., this gas may be given off and
therefore it is dangerous to send cleaners or pipe fitters into the
reducer, aside from the danger of the nitro and amido bodies. The
arsenic may be contained in the iron but is more likely to be in the
PROCESSES IN DYE M ANUFACTURE.
55
acid. One English manager said that he had had four men, on sick
leave at once as a result of such an accident as this. The same risk
must be thought of in connection with the reduction of nitro to
amido naphthosulphonic acid.
But it is especially in the making of benzidin, as this is done
in English plants and in some American plants, that precautions
against arsine poisoning must be taken, for it is here that a
large number of English workmen have recently been found to be
suffering from mild or severe poisoning. This method of making
benzidin is as follows: Nitrobenzene is reduced to hydrazobenzene
by means of zinc dust and caustic soda. One of .the Home Office
experts believes that at this point hydrogen arsenide may be given
off, but the industrial chemists are skeptical. There is no doubt,
however, as to the danger of the next stage, when hydrochloric acid
is used to dissolve out the zinc dust and leave hydrazobenzene. This
process must be carried out in the cold, for otherwise some of the
hydrazobenzene might be converted to benzidin, pass into solution
and be lost, and therefore it is customary in these factories to open
up the acidifying tub and drop chunks of ice into the acid. This
is the point at which the accidents have usually arisen, for if arsenic
is present in the zinc dust, or in the acid, there may be a sudden
evolution of A sH 3 when they meet and the liquid may “ boil over,”
as the men say. Usually the zinc is the substance at fault in the most
serious accidents, for the acid seldom carries as much arsenic as may
be carried by the zinc. Since the latter is in powder form, the
conditions are ideal for the production of the gas; and since the tub
must be opened to admit the ice, its escape is easy.
The next stage is also attended with some danger, and here, too,
cases of poisoning have developed. The contents of the tub with
the zinc chloride in solution and the crystals of hydrazobenzene are
sent into a filter press and if A sH 3 is present, bubbles may be given
off from the liquid and from the paste. In one of these English
plants it was evident that just this had happened and the chemist
in charge spoke with much emphasis of the necessity of providing
good drains under the filter press and thoroughly flushing the floor
from time to time, never letting any of the fluid lie about in pools*.
He said that the use of compressed air to blow out the filter press
was an advantage also because this served to carry off whatever
fumes might be left. In the last stage, when the hydrazobenzene
is heated to boiling by steam to convert it into benzidin, it is pos
sible that some unchanged azobenzene may be given off with the
steam and this compound is decidedly poisonous.
In consequence of the accidents which have occurred, the English
factory inspectors are insisting on changes in the equipment of ben
zidin departments, provision of fume pipes for the reduction, acidi
fying, and final conversion pans, proper drains for the filter presses,
and so on. In one, the management has put in a long sluiceway to
the manhole of the acidifying pan, with a valve at the end and the
ice is sent down this sluice by the workmen, who can thus stand at
a distance from the manhole, too far to inhale whatever fumes might
escape. This was the plant that had the most trouble in its ben
zidin department. In another, the cases of hydrogen arsenide poi
soning had occurred in connection with the reduction of nitro to
amido naphthosulphonic acid and since then they have used arsenic-
56
INDUSTRIAL POISONING IN M A K IN G COAL-TAR DYES.
free acid (contact acid) for this reaction, but even so the iron may
contain arsenic, so they test the fumes from time to time with mer
curic chloride paper.
This way of making benzidin is rather crude and is not used in
our largest plants, It is perfectly possible to produce the proper
degree of cold by means of brine coils and so avoid the opening of
the acidifier for ice. This is done in one of our plants. It does not,
however, do away with the risk of escaping fumes if for any other
reason the manhole is opened or if there is a leak, nor does it pre
vent fumes at the filter press, nor the risk of poisoning the men who
repair or clean the acidifying kettle. The process in use in the bet
ter American plants does not require the use of acid and is quite free
from any danger of arsenic at any stage. By this method the zinc
dust is not changed to the chloride and dissolved out, but is sepa
rated by passage through a very fine screen which catches the crys
tals of hydrazobenzene and lets the dust through.
In smaller American plants the procedure may be the same as that
in England, and carried on without any precautions. In going
through the records of a hospital in a New Jersey town, histories of
two men poisoned while on a night shift were found; both were
made very ill, and one of them died some three weeks later.® They
had been employed in a plant which was making napthionic acid
from alphanaphthylamine and sulphuric acid, and also benzidin
base and sulphate by the process just described. The company had
installed a fume pipe but had never completed it and it was never
used. According to the information obtained, the men in the hos
pital were two out of five affected on the same night shift by some
gases of unknown nature. The diagnosis given was, very naturally,
u anilin or alphanaphthylamine poisoning.”
Quite different dangers attend reduction by means of sodium sul
phide as in the making of sulphur dye intermediates. Paranitrophenol is reduced to paraamidophenol, picric acid— which is trinitrophenol— is reduced to picramic acid—amido-dinitro phenol— by
means of sodium sulphide, and if the reaction is acid, fumes of hy
drogen sulphide may be given off.
In making 1-2-4 amidonaphthosulphonic acid, reduction and sulphonation are brought about simultaneously by the use of sodium
sulphide and sulphuric acid and here the fumes of sulphur dioxide
may be bad.
5. Chlorination.— The introduction of the chlorine atom may take
place in the benzene ring or in a side chain. The resulting product
may be inert, or highly poisonous, or it may resemble closely the
nonchlorinated compound, as anilin hydrochloride differs from ani
lin only in being a solid instead of a liquid. The escape of fumes of
hydrochloric acid used for the production of chlorine gas and of the
gas itself constitute a danger and it is always necessary to provide
a vent or an absorbent chamber for the gas, which is best taken up
in water and neutralized. It is especially in the making of anilin
hydrochloride and of nigrosin that these fumes are troublesome.
The use of cylinder chlorine in the manufacture of pyrone dyes is
hardly ever troublesome, for only small quantities are needed.
6. Alkylation.— This consists in the introduction of methyl or
ethyl groups into a hydroxy or amido group. The important ex
a See page 45.
PROCESSES IN DYE M ANUFACTURE.
57
amples of this class of compounds are dimethylanilin and diethylanilin. The latter is made by treating anilin with ethyl alcohol. Di
methylanilin may be made by the action of methyl alcohol or methyl
chloride on anilin under heat and pressure, or by the action of di
methyl sulphate without pressure. The trade poisoning that has
occurred in the usual processes of alkylation is to be attributed to the
anilin rather than alkyl derivatives, which are less toxic. When di
methyl sulphate is used for methylation, a new danger is introduced
which has already been discussed.
In making methylanilin, some trouble has been experienced from
the methyl alcohol used. Methyl alcohol is also employed to bring
about alkylation of fuchsin to form other triphenylmethane colors.
7. Oxidation.— The substances used as oxidizers are usually in
organic salts, such as sodium dichromate, sodium chlorate, or per
manganate, manganese dioxide, lead peroxide with a mineral acid.
Anthraquinone, the intermediate for alizarin dyes, is produced by
oxidizing anthracene with sodium dichromate. In making fuchsin,
orthonitrotoluene may be used as an oxidizer, or mononitrobenzene.
In this case, fumes from these compounds must be guarded against.
The use of sodium and potassium dichromate has led to serious
chrome ulcers in England, but apparently, from the literature, it is
in using it as a mordant that the trouble is encountered, not in the
production of dyes. Certainly in the United States chrome ulcers
are practically unknown in alizarin dye works. Nor does the use of
red lead seem to give rise to enough lead poisoning to make itself
known. Oxidation may result in the production of poisonous quinones, and this is a danger not generally recognized.
8. Carboxylation.— This is generally effected by the action of
caustic soda and pure carbon dioxide gas upon a phenol as a result of
which the CQOH group is introduced into the ring. For instance,
carboxylation of phenol yields salicylic acid, which is much used in
the dye industry. This process is not so dangerous as caustic fusion,
because it does not require nearly so much free alkali and the result
ing compound is less poisonous than the original compound.
9. Liming.— Lime or chalk, or sometimes caustic lime, may be
added, usually to a sulphonated product to separate one salt from
another. For instance, in the production of betanaphthol the sepa
ration of the alphanaphthalene sulphonic acid from the beta is
brought about by adding lime, because the lime salt of the alpha
acid is very soluble in cold water and that of the beta acid is only
slightly so.
10. Condensation.—-This process consists in the union of two com
pounds, or two molecules of the same compound to form a new com
pound by the loss of water or HC1 or ILN. Sometimes hydro
chloric or sulphuric acid is used with phosphorus, zinc, sulphur, or tin
to bring about this reaction. There is no special danger involved ex
cept in the liberation of the volatile substances if the apparatus is
faulty, or in the case of accident allowing the workmen’s hands or
clothes to become splashed with such a substance.
11. Diazotizing and coupling.— An arnido compound on treatment
with nitrous acid (sodium nitrite and hydrochloric acid are gener
ally used) yields a compound called diazo. This is then coupled with
an aromatic amine or phenol to form an azo compound. Although
58
INDUSTRIAL POISONING IN M A K IN G COAL-TAR DYES.
the compounds that are diazotized are toxic, the fact that the reaction
of diazotizing or coupling is carried on in the cold lessens very much
the danger of both fumes and contact. An instance of the many
dyes that are made in this way is chrome brown, which is made by
diazotizing picramic acid (dinitroamidophenol) and coupling with
betanaphthol.
The making of intermediates is on the whole attended with more
risk of poisoning than the making of finished colors, and the benzene
intermediates are much more dangerous than the naphthalene and
anthracene intermediates. Toluene and xylene are included with
benzene in this statement.
COLOR MANUFACTURE.
The azo dyes are made with a primary amine, anilin or toluidin or
toluylendiamine or benzidin or some similar body, which is treated
with nitrous acid in the cold. The diazo compound produced is then
coupled with an aromatic amine or phenol to form an azo compound.
Diazotizing is done at about zero, centigrade. The making of azo
dyes is the safest branch of the color industry, and a plant which
does not make its own intermediates and makes only azo dyes may
probably be kept practically free from occupational disease. Typi
cally, the work is carried on in one high building with three levels,
the coupling tanks into which the intermediates are blown being on
the top level, so that whatever fume escapes is taken care of up there
and does not contaminate the air on the other levels. It is said that
if the sodium nitrite used for diazo production is run in too quickly
nitrous fumes may be given off.
Anthracene dyes may be produced also without much risk of
trouble. The most important of these dyes is alizarin, which is
synthetic madder. To produce this, anthracene is oxydized usually
with potassium or sodium bichromate to anthraquinone, and this is
sulphonated and then fused with caustic soda and chlorate of potash
to form alizarin, or dioxyanthraquinone. Indanthrene is produced
from anthracene by oxidation to anthraquinone, sulphonation, amidation (with ammonia and catalytic copper), caustic fusion. Indan
threne blue is formed by air oxidation; greens and violets are pro
duced by the use of chlorine gas, nitrobenzene, and nitric acid. Ob
viously, there are decided risks in the making of indanthrene colors,
especially from chlorine, nitrous fumes, and nitrobenzene, for al
though during the uninterrupted reaction no fumes may escape, any
accidental interference with the process, and these are not uncommon,
may result in a very bad state of things. Benzanthrene causes
dermatitis.
Indigo is made in three large plants which were visited, the process
differing slightly in each. In two, formaldehyde and anilin are used
and sodium cyanide is either added to or formed in the course of the
reaction. In the course of this ammonia fumes may be given off.
This reaction is followed by hydrolysis, usually with caustic potash,
to phenylglycine. It is in the filtering, drying, and transporting of
phenylglycine that most of the illness among the workmen occurs.
It is a very light and fluffy powder, and although it is usually said to
contain no more than 1 per cent of anilin, it may set up very serious
COLOR MANUFACTURE.
59
acute and chronic anilism if unusual precautions are not taken, espe
cially in emptying the filters and drying, dumping, transporting,
and barreling the powder.
In the third plant anilin and monochloracetic acid are used to form
phenylglycine. During this process the fumes that are given off
contain anilin, hydrochloric acid, and chlorine. Monochloracetic acid
is strongly caustic.
In one of the three plants the filter press stands in a separate
building, which is really a shed, with ample ventilation. While the
air is being blown through the press the vapor is bad, but usually it
is not necessary to have anyone inside the shed at that time. The
presses are then opened, the crystals dumped and scraped up and
shoveled into barrels. For this work rubber aprons, gloves, and
respirators are provided. From the filter the crystals go to a tank
with caustic potash, the temperature being kept as low as possible
to prevent too much ammonia fumes, A second filtration to remove
dirt follows, and then evaporation in an inclosed badger, The
liquor falls over great hot metal rolls, on which a thin layer of pow
der forms, which scrapes off and falls into a box. The powder is
kept from flying about by heavy canvas curtains, This dryer is in
a separate room writh a high, windowed roof, and only one operator
works on each shift. He is required to spend all but 15 minutes of
each hour in a little sheltered porch just outside the room, for it is
extremely dusty, and everything is covered with wThite powder like
a flour mill. He is given gloves and a respirator. Boxes of the
powder go to the next room, and are emptied into a barrel packer
of a good mechanical type, but nevertheless there is a great deal of
white powder in this room.
The second plant has a better method. The phenylglycine is evap
orated in a vacuum dryer, and a traveling screw carries the dry pow
der to an inclosed hopper, from which it falls into a barrel, stand
ing underneath. A canvas chute connects hopper and barrel, and
there is an exhaust with an opening right beside the top of the barrel.
A t the time when visited no dust was visible anywhere around this
apparatus.
The third plant was very bad. The synthetic indigo department
was well housed in a great new building, amply ventilated for or
dinary purposes, but the air was full of fumes and dust, so that a
short stay there was enough to affect one’s head quite noticeably.
Two of the men at work there were quite livid, one of them startlingly so.
The di and tri phenylmethane dyes are often called anilin dyes,
others are called toluidin dyes. The intermediates used are deriva
tives of benzene, toluene, and xylene, and there is probably more
typical nitro and amido poisoning in connection with this class of
dyes than any other. The only diphenylmethane color of importance
is auramine, in the course of the manufacture of which strong fumes
of ammonia may be given off, and also sulphuretted hydrogen. The
waste water from the auramine building may carry a good deal of
H 2!S.
The triphenylmethane dyes are very important, and require the
use of large quantities of nitrobenzene, nitrotoluene, anilin, the tolui
dins, especially para, the anisidins and methyl and ethyl derivatives
60
INDUSTRIAL POISONING IN M AKIN G COAL-TAR DYES.
of anilin. The malachite green series belong in this group. Mala
chite green is made from benzaldehvde and dimethylanilin, Victoria^ green from benzaldeliyde and diethylanilin. Fuchsin, the
starting point for so many colors, is made with anilinhydrochloride,
or formaldehyde, ortho and para toluidin and anilin oil. This forms
what is called the 44red oil mix.” I f formaldehyde is used instead
of anilin hydrochloride there is risk of a boil over, and this may also
happen with anilin hydrochloride if it is added too fast, The red
oil mix is oxydized with nitrobenzene or orthonitrotoluene and
44 fuchsin melt ” is formed. This department is frequently men
tioned in German factory inspection reports as the place in which
a case of intoxication occurred. The fuchsin melt is treated with
caustic soda to make fuchsin base, and this is phenolated by means
of anilin and benzoic acid to opal blue, oil-soluble, which is changed by
sulphonation to water-soluble alkali blue. Fuchsin can also be alky
lated to other colors of this same group by displacement of the II
atoms in the amido nucleus by ethyl or methyl groups, but it is
simpler to start with an alkylated amine. For instance, methyl violet
can be made with dimethylanilin, sodium chloride and chloride of
copper, cresol and phenol, and then treatment with hydrogen sulphide.
Eosins and fluoresceins are closely allied to the so-called 44anilin”
dyes (the tripheylmethane dyes), and are sometimes classified with
them, sometimes called pyrone dyes, sometimes resorcin dyes. Chlo
rine, bromine, and iodine are used, also fuming sulphuric acid and
caustic soda, but the gases are provided in cylinders and not enough
are used to give any trouble.
Nigrosin and indulln are made by melting anilin and nitrobenzene,
ferric chlorid and h3rclrochloric acid. This fc4melt” is ground, then
washed. Fumes of anilin and of hydrochloric acid, especially of the
latter, may be quite heavy in these departments.
The nitro or nitroso dyes are in themselves poisonous. It is only
recently that a man in Germany was poisoned by handling aurantia,
which is hexanitrodiphenylamine. The greatest risk of industrial
poisoning, however, is in the manufacture, which involves nitration
processes and the possible escape of nitrous fumes. Aside from
aurantia, the best-known nitro colors are picric acid, trinitrophenol,
and Martius yellow or dinitronaphthol, and naphthol yellows.
There is probably more risk of occupational poisoning in the
making of sulphur dyes than any other class of colors, for the
introduction of sulphur and sodium sulphide may result in the
liberation of sulphuretted hydrogen fumes, The preparation and
use of the intermediates also involve exposure to compounds which
have decidedly toxic properties, and set up not only very trouble
some skin eruptions but systemic poisoning as well. ’ For instance,
chlorbenzene is nitrated, during which process nitrous fumes may be
given off. The resulting ortho and para nitrochlorbenzene must be
separated, the para crystals from the ortho liquid. This operation
was seen done in an open centrifuge, and although the centrifuge was
in a small compartment with a strong suction fan drawing away the
fumes, it was necessary to provide a current of fresh air directly
beside the man who was obliged to go in from time to time and
empty the centrifuge. Even with these precautions the vapors were
strong beside the centrifuge. The paranitrochlorbenzene is washed
PREVENTION OF OCCUPATIONAL POISONING.
61
and saponified to paranitrophenol, which is a prolific source of
dermatitis unless it is handled with great care. Reduction of para
nitrophenol to paraamidophenol is done for sulphur blue. For
sulphur black, dinitrochlorbenzene is used, and the production and
use of this compound in the early days of American dye manufacture
gave rise to so much distressing skin disease as to necessitate changes
in method or it would have been impossible to keep the men at work.
Sulphur browns and yellows result from the treatment of phenylendiamine with sulphur and benzidin. Phenylendiamine results
from the reduction of paranitranilin, one of the most dangerous of
the nitro and amido compounds made from anilin through acetanilid
and paranitracetanilid. The process of saponifying or hydrolizing
paranitracetanilid is often attended with the liberation of fumes.
Primulin is made from paratoluidin, wrhich is fused with sulphur
to a “ melt,” then ground and suiphonated. Sulphuretted hydrogen
is sometimes evolved in making the melt and a typical case of toluidin poisoning was reported in a man who was in charge of the mak
ing of the melt.
The danger from fumes of hydrogen sulphide is greatest in the
manufacture of khaki and sulphur browns and yellows, less in con
nection with sulphur black, and very slight in making sulphur blue.
As a usual thing an effort is made to burn the H 2S to a mixture of
sulphur oxides. In one plant powerful suction carries H 2S to an iron
column where it is absorbed by caustic soda.
PREVENTION OF OCCUPATIONAL POISONING.
It is true in the anilin dye industry, as in every American industry,
that no generalizations can be made about the protection that is
^iven to the workmen against the dangers inherent in his occupation.
This differs widely, not only in completeness but in character. In
one plant the emphasis will be placed on rigid cleanliness of the
premises and removal of fumes, while less stress will be laid on the
medical department. In another there is much less effort made to
prevent the men from coming in contact with different toxic com
pounds, but there is a very complete, admirably equipped plant dis
pensary. It seems that no American plant as yet has developed
both these sides as thoroughly as possible, although one of the older
companies has come very near it.
Perhaps it may be w^ell to begin the consideration of the care
which should be given to anilin dye workers by a description of the
methods used in some of the German factories. That of Meister,
Lucius & Briining, in Hoechst, was described as follows by Grandhomme back in 1880. At that time this factory employed 1,000
men, 40 superintendents, and 25 chemists. It manufactured anilin
colors; resorcin colors (eosins) ; naphthol colors, yellows, reds, and
browns; and alizarin colors. The buildings were one-storied with
saw-tooth roofs, the windows in the roof being kept open. Fumes
were carried off in underground flues; the floors were of brick laid
in cement, impermeable to moisture, and furrowed with many cementlined gutters to carry off fluids. In all rooms where steam or other
vapors were formed ihe walls were whitewashed twice a year. Each
room had at least one large door to the outside, usually two. In the
62
INDUSTRIAL POISONING IN M A K IN G COAL-TAR DYES.
anilin department everything was inclosed. The sludge was driven
out with compressed air and discharged through pipes to a distant
field where, after thorough drying, the iron was recovered.
In the factory inspection report for 1910-11 a description is given
of the welfare work in the Aktiengeselischaft fur Anilmfabrikation.
The plant dispensary held clinics twice a day, with two physicians
and two nurses. There were also two visiting nurses for the work
men's families. The bathhouse wras available for the use of the
families twice a week. There was an infant welfare station, and
milk was provided at cost. Free care was given in a maternity
home to the women employees and the wives of the workmen during
confinement and for three weeks after. The mother was given 3 to
5 marks a week if she nursed her baby. There were illustrated
lectures on hygiene, and the medical care included light baths,
electric treatments, vibrations, massage, ultra-violet rays. Coffee was
provided free, and also milk if the man would pledge himself to
drink no alcohol during work time. The report states that “ anilism
has been practically abolished by a closed system for mixing, grind
ing, transporting, and for producing nitro and amido compounds;
by excellent ventilation, scrupulous cleanliness and rigid insistence
on baths.”
Ivoelsch, one of the principal authorities on industrial hygiene in
Germany, gives the following advice to manufacturers of anilin
dyes and intermediates: Medical examination must be made of all
applicants for work, and men must be rejected who are weakly,
anemic, or with affections of heart or kidneys. Nobody under 20
years of age or over 50 should be accepted. Persons with skin dis
eases should be rejected, and it is better not to employ women be
cause of their greater tendency to hemorrhage and because of the
possible effect on their offspring. The hours should not be too
long. He advises alternation of employment unless the ideal can
be attained of a selected force of trained and immune workers. It
is important to prevent heat and humidity as much as possible, for
experience shows that there is always more poisoning on hot, wind
less days, and the same condition is brought about by allowing steam
to escape into the workroom.
The rules in force should be made to fit the different compounds.
It is not necessary, for instance, to make the men working with the
toluene compounds bathe daily and have a clean suit of working
clothes every day. He believes that medical inspection for these
men need not come oftener than once in six or eight weeks, and
there is no reason why they should not work 10 or 12 hours. For
men working with benzene compounds far greater precautions
must be taken. They must have proper working clothes and caps,
frequently changed; they must bathe daily; they should not work
more than six hours, and in hot weather this period should be di
vided, three hours in the early morning and three in the late after
noon. It is very important to provide thick, impervious footwear
and to see that the feet are kept clean, especially if the man per
spires much. Koelsch objects to gloves, especially if the work is
greasy, for their use simply results in keeping the hands in more
intimate contact with the substance to be avoided than they would
be if no gloves were used. It is wrong to place dependence upon
PREVENTION OF OCCUPATIONAL POISONING.
63
respirators; dust and fumes must be removed at the point of origin.
No eating in workrooms should be allowed, and it is well to provide
a big cup of hot coffee at the end of the day’s work.
In case of poisoning, Koelsch advises removing the man to fresh
air, butjnot walking him up and down. He must be made to lie
down. His clothes must be removed and he must be given a thor
ough bath. I f there is dyspnea, oxygen inhalation with artificial
respiration is advised. I f there is marked blood destruction, it
may be well to bleed and give saline injections, but this is not nec
essary if the pulse is good. Make the man drink abundance of milk
or hot black coffee or weak tea, and give him mild laxatives. During
convalescence give him milk, iron, and arsenic, but no alcohol.
Curschmann insists on the value of cool sponging or douches as a
stimulant to heart and respiration. He also advises the adminis
tration of abundant quantities of milk.
In a large German dye works visited in July, 1919, the preven
tion of occupational poisoning had been carried to a much higher
point than that seen elsewhere. It is not extravagant to say that
the passageways between buildings and the roadways through the
grounds were cleaner than are the floors in some American factories,
There was no odor anywhere. One could not have guessed what
was being produced in the anilin reduction room. It was explained
that each department was under the charge of a chemist who was
responsible for all the sickness occurring there. No fluid was ever
allowed to drip or spill on the floor. I f an accidental case of poison
ing should occur, the chemist would be called to account, not be
fore the heads of the plant, but before a committee of the associated
anilin industries, the “Berufsgenossenschaft,” for it is they who
have to pay the sickness compensation, and they make a strict in
quiry into every case. This system seems to result in a more rigid
control of the sources of industrial accident and disease than is ob
tained when each establishment carries its own insurance and is alone
responsible for the cases which occur in it. Naturally an associa
tion of all the members of a branch of industry can exert pressure
upon one member which will result in a more careful supervision on
the part of the chemists and physicians than is to be expected when
what happens in the plant is known only to that one plant and the
loss falls only on it. Merely to save his face and avoid the disagree
able experience of examination at the hands of his colleagues the
man in charge will do all he can to keep off accidents and accidental
poisoning. After all, the criticism of one’s own class is the criticism
most to be dreaded, and it is probable that the influence of the
“Berufsgenossenschaft” is more potent than the authority of the
factory inspection department.
The freedom from odors and the striking cleanliness of the plant
were the result of this strict supervision. No apparatus which was
wet with any sort of fluid was placed on the floor. Near the opening
of the manhole of each kettle or autoclave was a smooth metal shelf
upon which the workman was instructed to lay any wet piece of ma
chinery as well as the lid of the manhole. The chemist in charge was
responsible for the cleanliness of this metal shelf. All vapors, even
plain steam, were removed by fume pipes, which could be connected
up with the air exhaust system, and always before opening an auto-
64
INDUSTRIAL POISONING IN M A K IN G COAL-TAR DYES.
clave or kettle the exhaust must be turned on and left on so long as the
receptacle was open. It was explained that this rule was based
on experience, for in processes of this kind it is impossible to be sure
of all the reactions, and the only safe thing is to guard against the pos
sible escape of such fumes as hydrogen arsenide and hydrogen sul
phide.
The dust prevention was excellent, every effort being made to catch
even the color dust, so that the men engaged in color packing showed
very little color on their clothes and faces. The small packages were
filled under glass and an exhaust provided at that point. Barrel
packing was done in the open room, but through a lid with two open
ings, one connected with the dust recovery system and the other with
a hopper containing the ground color.
This particular German factory had a lavish supply of basins and
showers, 1,200 for 3,000 men, and also several bath tubs. It is not
compulsory in Germany for the employer to provide overalls for the
men, but in this place good two-piece suits of blue denim were pro
vided, mended, and laundered. At the end of three to six months, ac
cording to the process in which the man was employed, a new suit
was provided and the old one given to the man for his own. The guide
said that this inclined the man to take good care of his overalls. The
men employed there are decidedly high-grade workmen, as is shown
by one little significant item— the absence of doors to the lockers.
The locker room has open compartments for the men’s street clothing,
one for each man. It was said that it was much more healthful to
let the clothing air and dry than to shut it up behind doors, and that
there was no danger of the men stealing each other’s clothing.
The new applicants for employment in Germany are examined by
a physician and doubtful cases rejected, but there seems to be at pres
ent no routine examination of the working force, such as is carried
on in England and in some American plants. All cases of occupa
tional illness are strictly investigated, as explained above,
The rules for the control of the dye industry in Great Britain are
those which were passed in 1908, but the factory inspection depart
ment of the Home Office is preparing a new code which will be more
detailed and comprehensive. Already the local inspectors have issued
orders supplementing the rules of 1908 as new dangers came to light
with the great increase of the industry. On the whole, the construc
tion and management of the British plants is about on a level with the
American, if one leavei out of consideration our worst specimens. As
is invariably true in every industry studied, the United States con
tains some factories which are dirtier and more neglected than any in
England. This is partly because of the arming standards for factory
inspection in our different States. The provision of working clothes
for the men in the English factories is, as it is in ours, sometimes
ample, sometimes inadequate. The provision of washing facilities in
the best English factories is quite as lavish as in the best American,
but the worst is not nearly so bad as our worst. Shower baths are
required in England, but at least one American dye works which
manufactured phenol during the war, is now manufacturing dye inter
mediates as well as dyes, and employs 2,000 men, has not a single
shower bath.
No American dye works has yet reached the point of doing every
thing possible to protect the workers from the dangerous compounds
P R E V E N T IO N
OF
O C C U P A T IO N A L
P O IS O N IN G .
65
which are used or produced, or which may be accidentally evolved in
the course of production. The faults in these plants depend in the
first place on the construction of the buildings and here, curiously
enough, some of the newest are most at fault. Of two factories ob
served, one has been running for years and is situated in a large city;
the other is hardly more than two years old and is out in the country,
with practically unlimited space to spread over. The first is excellent
in construction, the buildings are high and well ventilated, the floors
of concrete or some similar substance, properly drained. The second
consists of small buildings, often with low ceilings, huddled together
so that they shut off light and air from each other, the floors are
chiefly of wood already rotting and roughened, and the walls and
windows look as if the plant were 20 years old instead of 2.
Even if the construction is good, the method of carrying on the
different processes may result in a continual leakage of vapors or
fluids, or dusts, or the frequent need for repairs, which always means
untidiness and sometimes a dangerous state of affairs. To compare
two anilin reduction plants: In one, the smooth concrete floors are
clean and dry; the high ceiling and open windows insure good air
because the only source of fumes is the occasional taking of a sample
or perhaps a puff from the feed opening. The sludge is run out into
the open and the reducers do not have to be opened and cleaned out
oftener than about once in three months. In the other plant the
notes taken at the time of the visit read as follows: “ The reduction
building is dirty, and it is plain that there is a good deal of trouble
with the working of the apparatus. It seems to be a common occur
rence to have a reducer stop and then the iron falls on the paddles
and cakes them, and they have to be dug out. They take certain pre
cautions to lessen the danger of this work; they drive in steam, but
it is admitted that the steam can reach only the upper layers of the
iron filings, and as soon as the man begins to dig he reaches the
anilin. One reducer had just been opened up because the iron was
caked, and the door at the bottom, about 4 feet by 2J, was open. A
man must climb in through this door to finish the cleaning, and al
though he is allowed to stay in only 10 minutes, it is admittedly a
bad job, for, of course, he can get very thoroughly smeared with
anilin sludge in that time. Another reducer had just been cleaned
out. The sludge from the two lay in heaps on the floor and little
rivulets of anilin water ran from the heaps. The fumes were quite
strong, although the building is big and high and well provided with
windows. According to the physician, there is trouble every time a
reducer is cleaned out, even though compressed air is driven in while
the man is at work inside. Various improvements were discussed,
such as making an opening in the bottom of the reducer and passing
in an air hammer to break up the caked filings and then running the
sludge out with water, but it seems obvious that what they need is
some way of keeping the paddles of the reducers running and pre
vent caking.”
The cleanliness of the plant also depends on the standards of the
men in charge. This sounds like a truism, but it is really worth
repeating. There are perhaps two plants among those visited in
which one can go dry shod through every department, but it is need2 5 4 3 1 0— 2 1 ------- 5
66
IN D U S T R IA L P O IS O N IN G I N
M A K IN G
C O A L -T A R
DYES.
less to say that this is an exception and that ordinarily one must be
prepared to wade through puddles on almost all the ground floors.
The statement is commonly made that most of the cases of anilin
poisoning come from the anilin water that has soaked through the
men’s boots, and several superintendents have said with pride that
they provide wooden-soled boots for their men. It seems not to
have occurred to them to try to provide dry floors instead.
In German factories the rule seems to be to prevent the escape of
any fumes or vapors, no matter how harmless—a rule based upon long
experience. In the United States each factory seems to be acquiring
its own experience, rather at the expense of the workmen. I f a case
of sickness develops in connection with a given process, the matter
is investigated more or less promptly, and the dangerous fumes are
prevented, not always immediately, but eventually. In a few rare
instances the scientific knowledge which is so abundantly available
in these factories has been taken advantage of and those fumes which
are known to be poisonous are carried off by suction, even though
there may never have been an actual case of poisoning from them in
that plant.
In Great Britain the centralized control and the presence o f ex
perts in the factory inspection department make it possible to apply
in all the factories the experience which has been gained in one. For
instance, the occurrence of hydrogen arsenide poisoning in one benzidin department resulted in precautions being installed against such
an accident in all the other works which made benzidin.
The actual care taken of the individual workman differs very
widely in our American dye factories. The matter of providing
working clothes for the men is admittedly important, for all prac
tical men, as well as physicians, know that these poisons are absorbed
through the skin, and that clothing impregnated with a nitro or
amido compound acts like a poisonous poultice. Yet one of the
largest plants in the country, employing over 1,200 men in process
work and laboratory work, has never made any provision of overalls
for the men, although the safety expert says that plans have been
made to do so. Another plant for the manufacture of intermediates
and dyes employs 2,000 men and provides neither overalls nor ade
quate washing facilities. In contrast to this are several factories
where the provision is ample and generous. In one large plant clean
clothes are provided for the DNB and DNT men daily; for the anilin
men twice a week. A plant making printer’s inks and employing 380
men provides not only the usual denim overalls but clean underwear,
shirts, socks, and heavy boots with wooden soles an inch and a quarter
thick. The clothing is repaired and two suits a week are provided.
In the paranitranilin department of another plant, since closed, the
men were given underwear as well as overalls and socks, a clean
supply every day. These men were required to bathe at the end of
the day’s work, and if any man was engaged in an unusually dusty
job he was made to bathe as soon as it was over and change all his
clothes. One of the oldest plants, and probably the cleanest of all,
which employs between 1,500 and 1,600 men, supplies working clothes,
but makes the men pay for the first suit. The process men have a
clean suit every other day, unless after a cleaning or repairing job,
in which case they change at once. Color men wear theirs until they
are badly torn or worn out.
P R E V E N T IO N
OF
O C C U P A T IO N A L
P O IS O N IN G .
67
There is a decided difference of opinion as to the wearing of gloves.
Some foremen hold that the men get on much better without them
when working in nitro and amido compounds; that it is impossible
to prevent leaks, and a leaking glove is much worse than none at all.
They maintain that the men are much better protected if they are
encouraged to wash their hands frequently during the day than they
are by wearing gloves. This can, of course, be done only if there is
a supply of hot water and soap in the department itself, which is not
always the case. No experienced man depends on respirators to pro
tect his employees from poisoning. To exhibit with pride a collec
tion of rubber sponge respirators is a mark of inexperience. On the
other hand, an abundant supply of warm water at different points in
the plant is an evidence of experience. Even if warm water can not
be provided, there must be a supply of cold water readily acces
sible in every department where caustics are handled, or where the
mineral acids are handled, for severe burns can be prevented only by
prompt and thorough washing with water.
The great majority of American dye works have good and well
equipped wash rooms and bathrooms and shower baths for their
process men. This is required by law in the States in which most
of these plants are situated (Massachusetts, New York, New Jersey,
Pennsylvania, Illinois), but, unfortunately, it seems not to be required
in Wisconsin. Usually soap or some washing powder is also pro
vided ; less often, towels. There is a great difference in the degree to
which the employees of the different plants avail themselves of these
facilities. For instance, in one factory 90 per cent of the men use
the shower baths; in another only 25 per cent. The difference prob
ably comes back to the personality of the welfare manager, or per
haps of the individual foreman.
It is not so important in this industry to provide against the men
eating their lunch in their workrooms as it is in connection with lead
work. Nevertheless it is desirable to have rooms provided in which
no work is carried on, and in which hot food or at least hot drinks
may be bought by the employees. Factories which are situated far
from town are usually obliged to have a cafeteria for the men, but
the provision is not as general as it should be, and the whole matter
of proper feeding of the process men should be taken more seriously
than it is in American factories.
Much more attention is paid in Europe to the proper feeding of
men in all the dangerous trades than is true over here, and in the dye
industry it i$ recognized that a poor dinner and an inadequate
breakfast may have an important influence on industrial poisoning
among those employed. The English have long laid stress on the
necessity for proper feeding in the lead trades, and they have now
applied the same principles to the coal-tar industries. They look
on the dinner pail, so common in our factories, as distinctly bad,
with its cold, soggy sandwiches and pie. A hot digestible meal in
the middle of the day or night is considered essential, and therefore
all these plants are provided with kitchens, simply but sufficiently
equipped with a stove for boiling water for tea and an oven to keep
food hot. Opening one of these ovens, one finds them filled with
bowls of meat and vegetable stew, or the meat pie the English are so
fond of. I f they wish, the men may bring a rasher of ham or bacon
68
IN D U S T R IA L
P O IS O N IN G
IN
M A K IN G
C O A L -T A R D Y E S .
and a couple o f eggs and have them cooked at noon. All day long tea
may be brewed, and it is customary to allow 10 or 15 minutes in the
middle of the afternoon for this; sometimes also in the middle of
the morning. Nobody can deny the refreshing and restful effect of a
cup of hot tea with milk and sugar in the course of the afternoon.
Aside from the other effects of indigestion, one must not forget that
it lessens elimination of a poison, makes it harder for the system
to rid itself of what has been absorbed.
The conviction that industrial poisoning is greatly facilitated by
poor and insufficient breakfasts has made these English employers
provide milk for their workers in the morning as soon as they go on.
A pint apiece is the allowance, and it is given free. The Germans are
not so liberal since the war, but they provide hot coffee in the morn
ing and afternoon, coffee and soup at noon, for one-tenth the usual
price. Hot milk as an antidote for anilin poisoning holds a high
place in English estimation. One manager said he had treated a man
overcome from having his hands in anilin water—he was a bricklayer
and had mixed his mortar with wash water that had a little anilin in
it—by pouring hot milk and porridge down his throat till the man
could hold no more. Hot coffee with milk is also used and is doubt
less a good stimulant in such cases.
There is one American factory which gives the men in the dinitro
benzene department all the milk they will drink.
The need for continual, careful medical supervision in the manu
facture of dyes and intermediates is greater now than it will be in a
few years5time, for so long as the industry is still new and unfamiliar,
so long as it is still in the experimental stage, it will be necessary to
have the men’s physical condition constantly under the observation
of a doctor experienced in detecting the early signs of intoxication.
All of the American plants employing large forces of men have some
medical service, not always adequate, but some of the smaller ones
dispense with medical supervision altogether. A plant in Massa
chusetts employing 90 men has not even a part-time doctor. As for
the larger ones, it would be hard to explain the difference one finds
in the proportion of doctors and nurses to the numbers employed in
the different plants. Certainly it does not depend on the compara
tive dangers nor on the cleanliness or filthiness of the premises. In
a dye and chemical works employing 1,600 men there are three nurses
and one part-time doctor. In another employing 1,600 men there
are five nurses and one full-time doctor with an assistant. A plant
with 2,000 men manages to get on with the services ,of one doctor
for two hours daily, one nurse, and one visiting nurse, while another
with the same number of men has five full-time physicians and seven
men nurses.
It must be remembered that a large part of the physician’s time,
sometimes almost all of it, is taken up with the examination of new
applicants for work, so that unless he has ample assistance, he has
little time to give to the very necessary work of protecting the men
who are actually employed. The enactment of workmen’s compensa
tion laws in the different States has made the employer feel that he
must protect himself against claims for physical disabilities which
possibly may have been present when the man entered his employ
ment, and therefore he insists on this preliminary examination. That
P R E V E N T IO N
OF
O C C U P A T IO N A L
P O IS O N IN G .
69
this may involve an enormous amount of medical work can be seen
by the record of one plant in which 420 to 470 new men are examined
each month in order to keep up a force of 2,000.
There are several companies that maintain a high standard of
medical work. This means that the physician does not confine him
self to office work, but makes frequent trips through the plant,
familiarizing himself with the various processes, and learning just
where the dangers are. Routine blood examinations are made of
men wjio are in the more dangerous processes and who show slight
signs of poisoning, and a fall in hemoglobin is the signal for sus
pension from work. In connection with this it is well to remember
that the usual method of estimating hemoglobin does not give satis
factory results when the blood has a brownish tint, for then it is diffi
cult to match it up with the color standard.
It should be a rule to suspend from process work any man whose
hemoglobin is as low as 85 per cent, and not to return him to process
work till he has gained at least 5 per cent. Sometimes extravagant
claims are made by industrial physicians with regard to the improve
ment of men under treatment. One physician said that a man whose
hemoglobin had been 98 per cent when he was employed and had
fallen to 72 per cent, as a result of acute poisoning, had, under treat
ment, brought his hemoglobin back to 91 per cent in four days, the
treatment consisting in light outdoor work and proper food. This
seems perhaps not impossible, but certainly unexpectedly rapid. As
a usual thing the return to a normal hemoglobin content is slow. Of
course the man should always be removed from contact with the
poison, but it is not enough for the doctor to order him out of doors.
Sometimes the outdoor job is heavier and more fatiguing than his
former work, and he is only telling the truth when he comes to the
doctor complaining that he feels worse than he did when he was on
his own job.
The question of rejections is very important. The procedure car
ried on in one large dye works already referred to is recommended—
that is, a careful classification of work according to the risks in
volved. Here the men accepted for employment are assigned to one
of the three classes o f occupations, according to the doctor’s findings.
The blood pressure is taken and an examination is made of the urine
as well as the usual physical examination. Men with slight abnor
malities are not admitted to the more dangerous work, nor are any
men under 18 or over 48 years of age. This classification also permits
the doctor to shift a man from a dangerous job into a safe one with
ease. It must be remembered that the mechanical department often
contains the most dangerous work of all, cleaning and repairing, and
that these men are usually less on their guard against dangerous
compounds than are the process men, because they are not familiar
with the nature of the compounds with which they come in contact.
APPENDIXES,
A PPEN DIX 1.— STRUCTURE OF THE BENZENE RING A N D ITS PRIN
C IPA L D E R IV A T IV E S, ISOMERIC FORMS, ETC.
The benzene molecule is for convenience represented by a “ ring ” or hexagon
CH
HO
,CH
HC
'CH
which, if unmodified, stands for C6H6, or
Usually the carbon
CH
and hydrogen elements in a graphic formula are not written out, for it is
understood that all replacements for the formation of new compounds take
place at the expense of the hydrogen atoms and that no matter how compli
cated a series of such replacements may be, the original 6 carbon atoms o f
the ring remain unaltered. To illustrate, the formula for picric acid, trinitroHO
X X ,N 0 2
phenol, is usually written thus,
the unoccupied angles of the hexagon
\/
no
no
2
2
are understood to be taken by the original hydrogen atoms.
Benzene is C6H6. Toluene is methy 1-benzene, CeHsCHa. Xylene is dimethyl
benzene, C6H4 (CH3) 2. The graphic formulas are these:
CH*
/ \
ch3
X \
/ \ »
\
\
/
/
In naphthalene two benzene rings are joined directly together, at the expense of two hydrogen atoms, which results in the formula C10H 8or
Anthracene is three such rings joined together, or CwHio.
\ /\ /
Phenanthrene has the same number of atoms as anthracene and its formula
is also CwHio, but the three rings are differently grouped.
A P P E N D IX
71
1.
When the hydrogen of the benzene ring is displaced by HO, phenols result:
C6H 6-i-H O =C 6H 5HO, hydroxybenzene, or phenol or carbolic acid.
C6H 6-i-2 H O = C 6H 4(H O ) 2, dihydroxybenzene or resorcin.
CeHe+B H O = C 6H 3(H O )3, trihydroxybenzene or pyrogallic acid.
C6H5CH3+HO=C6H4CH3HO, hydroxytoluene or cresol.
The introduction of the nitro group into the ring produces nitro compounds,
such as nitrobenzene, CeH5N02T and dinitrobenzene, CeH4(N02)2; nitrotoluene,
C6H 4CH 3N 02 , and trinitrotoluene, C6H 2CH3(N 0 2)3 ; nitronaphthalene, C10H 7NO2,
and dinitronaphthol, CioH5H O (N 0 2) 2.
Reduction of a nitrocompound changes the N 02 radical to NH2 and produces
amido compounds. From nitrobenzene conres amidobenzene or anilin, C6H5NH2.
From dinitrobenzene, diamidobenzene, or phenylendiamine, C6H4(NH2)2. From
nitrotoluene comes amidotoluene or toluidin, C6H 4CH 3NH 2. From nitroxylene
comes amidoxylene or xylidin, C^HstCHshNEL. The reduction may be partial,
as when dinitrobenzene is reduced to nitranilin, thus:
no
2
nh
no
2
2
no
2
\/
and this may be further hydrolyzed to nitrophenol :
HO
NO
\/
and then reduced to amidophenol:
Ho
/\
\
NH*
/
For convenience the angles of the benzene hexagon have been numbered in
the order of the figures on the face of the clock.
When only one hydrogen atom is replaced by a new atom or radical it is
no importance which of the six is replaced, but when more than one is sub
stituted several so-called isomers or isomeric forms are produced, bodies which
have the same number of the same atoms, but are differently grouped and
differ decidedly from each other in physical properties and in toxicity. For
instance there are three xylenes, or dimethylbenzenes, C6H4(CH3)2.
ch3
ch3
CH3
/\
ch3
,CH3
Orthoxylene.
Metaxylene.
\/
CH3
Paraxylene.
72
IN D U S T R IA L
P O IS O N IN G
IN
M A K IN G
C O A L -T A R
DYES.
There are three dihydroxybenzenes, C«H4(HO)a.
HO
/\
HO
HO
/\
HO
\/
\ /
ortho, or pvrocateehin.
roca
/ \
HO
meta, or resorcin.
V
para, or hydroquinone.
C
_
CH3
/\
nh
Orthotoluidin, J
2
|
is an oily liquid at a temperature at which paratoluidin
\/
is crystalline.
The prefixes commonly used, ortho, meta, and para, refer then to the different
forms which result from the displacement of two of the hydrogen atoms of
the ring. When there are more than two substitutions a much greater num
ber of isomeric forms is possible, and these are designated by the numbers of
the angles, 1-2-3, 1-2-4, 1-3-5, etc. Dinitrophenol 1-2-4 is th is:
HO
/\
no
2
\ n o/ 2
It differs toxicologically from all the other isomers.
When two or more benzene rings are joined, as in naphthalene, two mono
substitution products are formed, according as the substituting atom or radical
is combined with a carbon atom, which is in direct union with one of the
common carbon atoms, or not. These two forms, known as alpha and beta,
may be illustrated as follow s:
HO
alpha-naphthol.
/\ /\
HO
w
beta-naphthol.
NHa
/\ /N
-
alpha-naphthylamine.
;NH,
beta-naphthylamine.
S 0 3H
SOsH
beta-naphthalene-sulphonie acid.
APPENDIX 1.
73
The compounds thus far described are all substitution products formed
by replacement of the hydrogen of the ring. They differ in chemical and physi
cal properties and in their effect on human beings from the substitution
products, which are formed by displacement of hydrogen from a side chain,
such as the radical CHS. Thus if the hydrogen of the ring in toluene is dis
placed by NH2, amidotoluene or toluidin, is formed, while if the replacement
takes place in the CH3 radical, we have benzylamine. A third compound, with
the same elementary composition, results when the replacement is in the NH2
group of amidobenzene, or anilin, and a CH 3 radical enters. This last is methyl
anilin. These three compounds are very different in action and in properties.
Toluene.
CH3
Orthotoluidin.
Benzylamine.
CH3
CH2NH2
/\
y \ NHj
\/
\/
Methyl anilin.
NHCH3
/\
\/
This distinction is very important, for the ring substitutions have in gen
eral the physiological action of benzene, while many of the products formed by
replacement of hydrogen in the methyl group act like the alcohols. The fol
lowing are some instances of these two kinds of products
Benzyl alcohol.
CHaHO
Orthocresol.
CH3
/\
HO
Chlortoluene, formed by chlorine gas in toluene with heat.
CH3
/ \ cfi
\/
Benzyl chloride, formed by chlorine gas in toluene with cold.
CH2CI
Bodies similar to benzene substitution products may be formed from ammonia,
BLN, by substitution of one of the hydrogen atoms. Anilin is C6H 5NH 2. Di
phenyl amine is NHCCeHsH
These ammonia substitution products are slightly toxic if at all.
An instance of a body which is both a substitution and an addition product
is nitrosodimethylanilin
N(CH3)2
V
When an amido compound of the benzene ring is acted on by nitrous acid,
HNO2, there results a series o f intermediate compounds known as diazo com
1
Substitution products of toluene are usually called tolyl or toluyl compounds. Toluylendiamine is C6H 3CH3(N H 2) 2.
Side-chain products are called benzyl.
Benzaldehyde is
CeHbCHO.
74
IN D U S T R IA L
P O IS O N IN G
IN
M A K IN G
C O A L .-T A R
pounds which contain two nuclei bound together by— Na— .
zene is
DYES.
Diazoamidoben-
C6H5^
" > n2
NHCeHs
.Anilin, para and meta phenylendiamine, etc., yield these diazo compounds, and
the latter unite with other amido compounds or with phenols to form azo color
ing matters. For instance, the diazo compound of benzidin acting on alphanaphthylamine and sulphuric acid forms Congo red.
A L IP H A T IC , F A T T Y , P A R A F F IN SERIES.
These bodies are hydrocarbons derived from petroleum. They form the
methane or marsh gas series, beginning with CEL and adding successive radicals
of CH2; the ethylene series, beginning with C2H4 and adding CEL; and the acety
lene series, beginning with C2H 2. Substitution products formed with HO are
alcohols; with COOH, acids; with Cl,Br.I, chlorides, bromides, iodides. Alco
hols may be oxidized to aldehydes. Amines are ammonia substitution products.
To illustrate :
CH4, marsh gas or methane.
CH 2OH, methyl or wood alcohol.
CHOH, formaldehyde.
CHsCl, methyl chloride.
CHCls, chloroform.
CH 2COOH, acetic acid.
C2H6, ethane.
C2H bHO, ethyl or grain alcohol.
C2H 4O, acetaldehyde.
C2H 5NH 2, ethylamine.
The combinations of CH3,C2H 5, etc., with the benzene ring, have already been
spoken of.
Methylanilin.
Dimethylanilin.
Diethylanilin.
CeHsNHCHs
CeH5N (CHS) a
C6H 5N (C2H5) 2
A PPE N D IX 2.— PRODUCTS DERIVED FROM COAL.
The diagram facing this page and showing the products derived from coal and
some of their uses is reproduced by permission of the Barrett Co., of New York
City, by whom it was prepared.
A PPE N D IX 3.— M ASSACH U SETTS: RULES AND REGULATIONS SUG
GESTED FOR SAFE TY IN THE M ANUFACTURE OF BENZENE DE
R IV A T IV E S AN D E X P L O S IV E S .2
Evidence of the danger to the life and to the health of persons employed in
the manufacture and use of various benzene derivatives has accumulated in
this State during the past year. The experience of countries where manufac
turing processes have been carried on in an extensive way for many years
shows that the industry can be regulated without hindrance to its development
and with comparative safety to the workers engaged in the manufacturing
processes.
The State Board of Labor and Industries presents the following regulations
to insure safety to the workers in this State, and will welcome any observations
manufacturers or employees may desire to make on these proposals.
CLASSIFICATION.
The following substances shall come within these regulations:
Nitrobenzol.
Dinitrobenzol.
Dinitrotoluene.
Trinitrophenol (picric acid).
Trinitrotoluene.
Anilin hydrochloride.
Anilin oil.
Also all compounds in which any of the foregoing is a part of the manufac
turing process.
2
M assachusetts.
Boston, 1916.
State Board of Labor and Industries.
Industrial Bulletin No. 11.
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APPENDIX 3.
75
DANGERS.
In the various processes of manufacture in which any of the foregoing sub
stances are used, a danger to health arises in three ways, viz:
1. From the inhalation of fumes before the process of crystallization is com
pleted.
2. From the inhalation of dust given off in the breaking up or crushing of the
crystallized mass.
8. From the absorption through the skin by contact with the material in
either the liquid or solid state.
PREVENTION.
The danger to health can be reduced to a minimum by—
1. The removal o f fumes and dust.
2. The prevention of absorption of the poisonous material through the skin.
To make prevention effective the fumes and dust must be removed at or very
near to the point where they are produced, and the following means employed:
A. VEN TILATIO N .
1. Every vessel containing any substance included in these regulations shall,
if steam is passed into or around it, or if the temperature of the contents be
at or near the temperature of boiling water, be covered in such a way that no
steam or vapor may be discharged into the open air at a less height than 25
feet above the heads of the workers.
2. In every room in which fumes from any of the substances included in these
regulations are evolved in the process of manufacture and are not removed as
provided in section 1 there shall be provided and maintained thorough ventila
tion by means of a fan or other exhaust system.
3. No substances mentioned in these regulations shall be crushed, ground,
mixed, or packed in a crystalline condition except with an efficient exhaust sys
tem, so arranged as to carry away the dust as near as possible at its point o f
origin.
4. No substances mentioned in these regulations shall be broken by hand in a
crystallizing pan, nor shall any liquid containing it be agitated by hand, except
by means of an implement at least 6 feet long that shall prevent the workers’
hands and faces from coming into close proximity with the substances used.
5. In the filling of cartridges with any of the substances mentioned in these
regulations, the process shall not be done by hand except by means of suitable
scoops.
6. Drying stoves shall be efficiently ventilated to the outside air in such
a manner that hot air from the stoves shall not be drawn into the workroom.
No person shall be allowed to enter a stove to remove the contents until a free
current of air has been passed through it. All openings in stoves, retorts,
vats, etc., for the admission of workmen into the interior of such stoves, vats,
etc., shall be sufficiently large to permit the easy passage of the body of such
workmen.
B. W A SH IN G FACILITIES.
There shall be provided and maintained in a cleanly state, in good repair,
and properly lighted for the use of all persons employed on the substances
mentioned in these regulations—
1. At least one washbowl, sink, or other appliance for every five persons,
and provided with running hot and cold water.
The number of bowls, sinks, or other appliances required shall be based
upon the maximum number of persons entitled to use the same at any one
time. Twenty inches o f sink will be considered as equivalent to one
washbowl.
2. A lavatory within reasonable access and under cover, with a sufficient
supply of clean towels and of soap, and nail brushes.
3. Sufficient and suitable bath accommodations (shower or other) with hot
and cold water, and a sufficient supply of soap and towels.
C, TOILET FACILITIES.
Rules and regulations for toilet facilities adopted by the State Board of Labor
and Industries shall prevail in all establishments where the manufacturing
processes concerned in these special regulations are carried on.
76
IN D U S T R IA L
P O IS O N IN G
IN
M A K IN G
C O A L -T A R
DYES.
D. SPECIAL CLOTHING.
There shall be provided and maintained for the use of all persons employed
in the manufacturing processes included in these regulations—
1. Suitable overalls or suits of working clothes. Overalls included in these
regulations shall be washed or renewed at least once every week.
2. India-rubber gloves, which shall be collected, examined, and cleansed at
the close of the day’s work and shall be repaired or renewed when defective.
Equivalent protection for the hands, when they come in contact with the sub
stances mentioned in these regulations, may be substituted for gloves.
3. Clogs or other suitable protection for footwear that shall guarantee against
contact with the substances mentioned in these regulations.
4. A suitable clothes room for changing and for keeping clothing put off
during working hours.
5. A suitable locker, separate from the clothes room and meal room, for
the storage of overalls and other work clothes.
E. DINING ROOM.
1. In establishments included in these regulations a suitable meal room
shall be provided unless the establishment is closed during the meal hours.
This dining room shall be separated from any room in which a process using
materials mentioned in these regulations is carried on.
2. Suitable provisions shall be made for the keeping of food brought by
persons employed.
3. Adequate washing facilities, equipped with running hot and cold water,
shall be provided in or adjacent to the meal room.
4. No person shall introduce, keep, prepare, or partake of any food, drink,
or tobacco in any room in which a process using substances mentioned in these
regulations is carried on.
MEDICAL REQUIREMENTS.
Each establishment in which manufacturing processes using materials men
tioned in these regulations are carried on shall employ and keep in employ
ment one or more duly qualified physicians to act as medical officer or officers,
who shall be in attendance at all necessary times while such work is in progress,
so as to guarantee constant medical supervision and care of workers engaged
in these processes o f manufacture.
Such medical officer shall also be charged with the duty of enforcing the
following regulations:
L Examine every person employed in these processes of manufacture either
before said person begins employment, or within seven days after beginning said
employment.
2. Reexamine every person employed in these processes at least once in each
calendar month, or at such other intervals as may be necessary to insure pro
tection to the workman against poisoning from the substances used in the
process of manufacture; also before permitting a workman to return to work
after absence or suspension on account of illness.
3. The medical officer shall have the power o f suspension because o f physical
unfitness of any person employed on any of these processes of manufacture,
and no person, after such suspension, shall be reemployed without written
sanction of the medical officer.
4. The medical officer shall give such instruction to employers and to em
ployees concerning the danger to health from the particular process o f manu
facture being carried on in the establishment as will best qualify such persons
to—
(a) Recognize the signs of poisoning.
(&) Apply suitable first-aid treatment to workmen taken ill upon the
premises.
5. The medical officer shall keep a full and complete record o f all examina
tions made by him, which record shall contain the date on which examinations
are made, name, address, age, height, weight, physical condition of heart and
lungs of all persons examined by him ; also a full and complete record of all
illnesses, accidents and deaths occurring among the employees under his charge.
These records shall be open to the inspection of the State board of labor and
industries or its representatives, and a copy thereof shall be forwarded to said
APPENDIX 4.
77
board within 48 hours following the occurrence of the accident, illness, or death,
stating as fully as possible the cause of said illness, accident, or death o f
employees.
No statement contained in any such report shall be admissible as evidence
in any action arising out of said accident, illness, or death herein reported.
6.
There shall be provided a suitable medieal or hospital room for the care
and treatment of workmen taken ill upon the premises. This room shall be
conveniently located, properly lighted, heated, and ventilated, and shall con
tain the following minimum equipment:
(a ) A couch or bed.
(&) Pair of blankets.
(e) Two hot-water bottles.
( d ) Tank of oxygen, with apparatus for using the same.
(e) A lungmotor.
( / ) An oxygen helmet for rescue work.
(#) Suitable ropes for rescue work.
( h ) Medical and surgical chest as prescribed by the rules of the State board
of labor and industries.
PRINTED NOTICE POSTED.
A printed notice in language intelligible to all the workers, and in type
sufficiently large to be legible to all workers, labeled “ CAUTION,” shall be
conspicuously posted and maintained in all departments where any of the sub
stances mentioned in these regulations are used in any processes carried on
therein. Said notice shall contain the following:
1. In large conspicuous type the common name of the poisonous substance in
use in that particular room.
2. That the substance named is capable of causing poisonous symptoms if
precautions are not observed.
S.
Signs and symptoms of poisoning, viz, throbbing of blood vessels, giddi
ness, dizziness, headache, weakness of legs, palpitation of heart, nausea, blue
ness, cyanosis, unconsciousness.
4. First-aid treatment, viz. :
(a) Remove poisoned person to the fresh air. Keep him quiet and warm.
( b) Do not let person walk home until advised by physician.
(c) Use hot coffee as stimulant.
id) If person is unconscious, apply artificial respiration; lungmotor; oxygen
inhalation; keep patient warm.
5. Prevention:
{a) Avoid dust, fumes, and chemical compounds on hands, feet, and clothes.
(&) Wash hands before eating and after day’s work is finished.
(e) Do not eat food nor chew tobacco in workroom.
{d) Do not wear same clothes in workroom and at home.
( e ) Use extra protection on hands, feet, and clothes while at work on any
o f the substances mentioned in these regulations.
( f ) Bathe regularly.
iff) Consult a physician if losing color or weight.
(h) Do not enter stoves, vats, or retorts for repair work unless in the pres
ence of another workman.
(i) Have emergency appliances ready for use in all dangerous repair work.
(j ) Watch for leaky joints in pipes, ducts, valves, etc., carrying the gas or
chemical compounds.
APPE N D IX 4.— SAFE TY STANDARDS FOR THE M ANUFACTURE OF
NITR O A N D AM IDO COM POUNDS A D O P T E D BY N EW JERSEY
A N D P E N N SY L V A N IA .
S ection 1. For the purpose o f these regulations the following nitro and amido
compounds shall be considered injurious to health.
(d ) The nitro compounds o f benzol, toluol, xylol, etc., as well as their chlo
rine derivatives.
(&) The nitro compounds o f naphthaline.
(a) The twice or higher nitrated compounds o f phenol and naphthol.
(<Z) Aniline and its homologues (toluidine, xylidine, cumidine, etc.), anisifline, phenetidine and their chlorine, nitro, and alphyl derivatives, as dimethyl
and diethyl aniline, diphenylamine, etc. The salts of these compounds are com
paratively innocuous and do not come under these regulations.
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(e) Phenylenediamine, tolylenediamine.
( f ) Benzidine, tolidine, dianisdine.
( g ) The naphthylamines. The salts of these compounds are comparatively in
nocuous and do not come under these regulations.
( h ) Phenyl and tolyl hydrazin.
Factories in which the above compounds are regularly recovered in con
siderable quantities are mainly :
Fuchsin, aniline blue, violet, and nigrosin factories.
Sec. 2. B uildings .— The buildings in which nitro and amido compounds are
manufactured or are regularly recovered in considerable quantities shall be
properly ventilated.
Buildings in which twice or more nitrated compounds o f benzol or o f toluene
or of phenol are manufactured shall be of fire-resisting material or shall be
separated from other buildings.
S ec. 3. P latforms .— In the above buifdings, operating platforms may be
erected, provided they do not cover more than three-fourths o f the ground floor.
In buildings constructed after the adoption of these regulations, the distances
of platforms (under which workingmen may be required to work) from the
floor and from each other shall be at least 9 feet. In buildings already con
structed this distance shall be at least 7 feet. (It is recommended to leave be
tween platforms and the outer walls either a free space or a space covered by
slats 18 inches to 3 feet w id e; and the area o f this space is to be added to the
free space in calculating the latter.)
On top of melting kettles and distilling apparatus, only such platforms shall
be built as are absolutely necessary for the proper handling o f the apparatus,
and care should; be taken that all apparatus be so constructed that vapors and
gases can not escape, and thereby injure those obliged (by reason of their
duties) to be upon said platforms.
Platforms on which work is regularly carried on with nitro and amido com
pounds shall be light and easy to clean; covered with sheet lead where advisable.
Platforms shall be equipped with railings and toe boards, in accordance with
the safety standards on these subjects o f the department of labor.
S ec. 4. F loors.— The floor o f the workrooms and the storage room shall be
nonabsorbent, smooth, and easy to clean. Where necessary, wooden or cement
floors are permissible.
S ec. 5. W a lls .— The walls o f the workroom shall be kept clean. I f painted
with calcimine they shall be repainted at least once a year. Windows which
can be opened shall be provided on at least two sides o f the room.
S ec. 6. R oof.— The roof shall have a sufficient number of ventilators or other
appliances, which allow sufficient ventilation o f the workroom, and which can
be kept open, even if it rains. Windows or skylights shall be so constructed
that they can be operated from the floor or platform. Skylights in the roof
shall be constructed o f wTire glass.
Sec. 7. M anufacture .— The work in the above factories shall be regulated in
such manner that the men do not come in direct physical contact with nitro and
amido compounds. It is therefore recommended, when practicable, that liquid
nitro and amido compounds be transported through closed pipe lines either by
pumping, blowing, suction, or by gravity.
As a general rule gravity or suction is to be preferred, because in the use of
compressed air fine parts o f the compounds go off with the air. It is also neces
sary that spent compressed air be vented outside. If, in the latter case, this
is obnoxious to the neighborhood, it is suggested that the spent air shall be
purified before being expelled. The same refers to the air which is expelled
from vacuum pumps of distilling apparatus, as it frequently contains small
quantities of anilin, etc.
Liquid nitro and amido compounds shall be kept and stored only in covered
vessels. Wherever the above nitro and amido compounds are handled in such
a manner that dust, gases, or vapors are generated (especially in powdering,
sifting, and packing operations), the work shall be carried on as far as practi
cable in covered or closed apparatus. The vapors from receivers of distillates
shall be excluded from work buildings.
Chiseling out of solid nitro and amido compounds, which are explosive, is
strictly forbidden; and, when these are poisonous, is permitted only if proper
precautions are taken.
Drying should be done in separate buildings used for drying only, or in
properly constructed apparatus.
APPENDIX 4.
79
Frequently drying can be avoided by melting the nitro and amido compounds,
and breaking them up when cold.
Where boilers are fed with water containing aniline the boiler shall be fitted
with suitable safety valves and water glasses, which absolutely prevent the
entering of steam or water containing aniline into the workroom.
Nitrating apparatus.— In nitrating benzol and similar compounds, which are
readily inflammable or generate inflammable or explosive vapors, the following
precautions must be observed:
(a) The service pipe from the acid container to the nitrating vessel, where
possible, shall be o f such a diameter that at no time can an excessive amount
of acid be conducted into the nitrating tank. The diameter of this pipe must,
of course, depend entirely on the size of the container which it supplies; with
acid.
(&) The nitrating tank shall be fitted with a safety device so that the faucet
of the acid tank can not be opened until the stirring apparatus o f the nitrating
tank has been put in motion. This rule is due to the fact that if a large
quantity of acid accumulates in the bottom o f the nitrating vessel (due to its
not being constantly stirred) a powerful chemical reaction will occur when the
stirrer suddenly starts up, and there is sudden combination with the benzol.
(c) The protruding end of the shaft of the stirring apparatus shall be fitted
with a pendulum or similar device, so that persons in charge may, from a dis
tance, know that the stirring apparatus is actually in motion and keeping the
mixture constantly agitated, thus preventing undue generation o f heat.
(d ) The nitrating vessel must be equipped with a large pipe (which is to act
in the capacity of a safety valve) extending through the roof, and provided on
top with a suitable arrangement, which, while keeping the pipe closed ordi
narily, will open when a dangerous pressure developes in the nitrating vessel.
When, in the judgment of the commissioner of labor or his authorized repre
sentative, it is deemed necessary, all apparatus and machinery in which nitro
and amido compounds are manufactured, transported, treated, distilled, centri
fuged, filtered, dried, ground, mixed, etc., packed or filled, shall be fitted with
reliable attachments to remove such dust, gases, or vapors as may be generated.
Special care shall be taken so that all vapors generated in the opening, disrcharging, and filling o f dry rooms, melting kettles, autoclaves, and other pres
sure vessels will be harmlessly disposed of, when in the judgment of the com
missioner of labor or his authorized representative it is deemed necessary to
do so.
Sec. 8. C lean lin ess .— The workroom shall be kept as free from nitro and
amido compounds as possible. I f any o f the above compounds are spilled they
shall be removed as soon as possible. The floor shall be cleaned at least once
every 24 hours.
Sec. 9. H ealth precautions .— The employer shall inform the workingmen
employed in the manufacture, etc., o f the above nitro and amido compounds
as to the poisonous quality of these products and the necessity of strictly
observing the following precautions:
Shirts, overalls, caps, stockings, shoes, gloves, and other wearing apparel
which have become saturated with poisonous nitro or amido compounds in such
manner that the skin comes in immediate contact with them shall be imme
diately taken o ff; the skin washed first with vinegar and then with w ater; and
the employee must then put on clothing which has not been in contact with
these substances.
Employees shall be warned that the use o f alcoholic liquors and chewing
tobacco is harmful to their health. Smoking in the workroom is strictly for
bidden.
Food shall be neither kept nor eaten in the workroom. A suitable dining
room, absolutely separate from the workroom, shall be provided. Employees
shall not be allowed to enter this room until they have washed both face and
hands. For this purpose wash and dressing rooms and bathrooms, absolutely
separate from the workroom, shall be provided. These rooms shall be suit
ably fitted up, kept clean, and properly heated. Nobody shall be allowed to
keep any wearing apparel in the workroom. All process men shall dress in
the dressing or wash room provided. Each process man shall be provided with
two lockers, one for his working and one for his street clothing, or a properly
divided double locker, or such other method for storing clothing as shall be
approved by the commissioner o f labor or his authorized representative. An
approved number of washing appliances shall be provided. Soap and towels
shall be furnished in suitable number and free of charge.
80
INDUSTRIAL POISONING IN M A K IN G COAL-TAR DYES.
It is recommended that every working man who comes in contact with the
above nitro and amido compounds shall take a bath daily before he leaves the
factory.
Men who suffer from inflammation of the bladder should not be employed in
the above factories.
Men who' are addicted to the use of alcoholic liquors must not be employed,
and no employee upon whom the odor of alcoholic liquor is detected shall be
allowed to enter the factory.
It is recommended that process men be between the ages of 22 and 50 years.
It is also recommended that applicants for employment presenting evidences
of anemia or of emaciation should not be employed as process men by reason
o f their increased susceptibility.
The employment of females except in the office, or works hospital, or welfare
room or building, is prohibited.
Toilets shall be provided in accordance with the sanitary code of the depart
ment of labor.
The employer shall provide and maintain a sufficient number of sanitary
drinking fountains, readily accessible, for the use of all employees.
All process men should be cautioned of the danger of commencing work on an
empty stomach.
It is recommended that those who suffer from excessive perspiration should
not be employed as process men.
Bodily cleanliness is essential to good health. It is recommended that those
employees who do not take frequent baths be not employed as process men.
Process men are those employees whose work brings them in immediate con
tact with nitro and amido compounds, either in the manufacture of these com
pounds or in the repair of apparatus used in their manufacture. The term
does not include employees whose duty is in the power plants or other em
ployees whose work does not bring them in such contact.
Sec. 10. R epairs .— All repairs and changes on the machinery, apparatus, and
pipes for nitro and amido compounds shall be made only after they have been
thoroughly cleaned.
All work in the inside of apparatus, vessels, boilers, etc., shall be done in
accordance with the following rules of procedure:
If it is necessary for an employee to enter vats, tanks, or other containers
in which there have been used, stored, or manufactured gases, fumes, or vapors
of an asphyxiating or poisonous nature, or materials which give off gases,
fumes, or vapors of an asphyxiating or poisonous nature, the following pro
cedure shall be pursued:
(a) Empty containers. Disconnect and blank off all connections.
(&) Clean containers thoroughly by repeated washings with water, soda
water, steam, compressed air or other suitable means.
(e)
I f the person in charge then considers conditions satisfactory, employees
may enter such containers. They must use an approved type o f helmet, and
have attached to their bodies a life line or rope if the person in charge con
siders it necessary.
( d ) The life line or rope shall be under the control of one or more fellowworkmen, who shall remain outside o f the container in order that they may
render assistance if necessary.
(e) A fter the work is finished the men should take, at once, a bath and
change their clothing, including shoes, if the foreman or other person in charge
shall deem it necessary. Facilities for taking such baths shall be provided.
The superintendent o f the plant shall be held responsible for the enforce
ment o f these regulations.
A copy of the rules for procedure as given above will be furnished by the
department of labor and shall be conspicuously posted at every place in each
plant where asphyxiating or poisonous fumes, gases or vapors may be found.
Sec. 11. R esuscitation .— For every 50 process men or less employed in such
plant and exposed to such risk there shall be present at all times at least 2
persons who are trained or competent to apply means of resuscitation by the
prone pressure or Shaeffer method, or by mechanical devices approved by
the commissioner o f labor.
A sufficient number o f helmets o f a type approved by the commissioner o f
labor shall be kept at each plant, in order that they may be available for use
by every employee who has occasion to enter places where there may be asphyx
iating or poisonous gases, fumes or vapors.
APPENDIX 4.
81
All employees who are required by the employer to wear helmets in making
repairs or in maintenance work shall be thoroughly instructed in the use of
such apparatus; and be physically examined by a licensed physician at least
once in ninety days or after absence from work due to either sickness or
accident. The physician shall certify to the proper physical condition of the
men so employed; and no employee shall be permitted to do such repair work
unless so examined and certified. The examining physician shall report the
results of these examinations, within 48 hours after each examination, to the
commissioner of labor, upon blanks which will be furnished upon request.
Oxygen inhalation apparatus shall be kept on hand and the foremen and
authorized employees shall be instructed in its use. In all cases in which the
apparatus has been used, a physician shall at once be called or the sick em
ployee removed to a hospital. A supply of oxygen or the means for its produc
tion must be kept on hand.
I f oxygen tanks are used at least two must be kept on hand at all times, one
of which shall be full.
Sec. 12. P h y s ic a l e x a m in a t io n .— All applicants for employment as process
men shall be physically examined by a licensed physician, either before com
mencing work, or before the expiration of 24 hours after their employment.
All process men shall be physically reexamined by a licensed physician at
least once every 30 days, and before resuming work after an absence due to
sickness or to accident or to any other cause.
These examinations shall each consist in the determination and recording
of the following facts, either in a book or upon a ca rd :
Name ______________________________________________________ Age_
A dd ress_______________________________________________ Process____
Height ____________________________________________ Weight______
Examination of urine: Reaction______________ Specific gravity___
Pulse______________ Blood pressure_______________ Hemoglobin_____
Albumen__________________ Sugar__________________ Casts________
The records of these examinations shall at all times be open for inspection
by the commissioner of labor or his authorized representative.
The examining physician shall report the results of these examinations to
the commissioner of labor within 48 hours after such examinations, upon
blanks which will be furnished upon request.
It shall be the duty of the examining physician to request the factory man
ager or superintendent to suspend from work any process man whom he be
lieves to be suffering from poisoning; and it shall be his further duty to report
such case to the department of labor upon the following blank:
2 5 4 3 1 ° — 2 1 --------6
STATE O F ____________________ ____
D epartm ent
B ureau
of
of
H ygiene
and
Sanitation .
Report of case of occupational disease.
Name of patient____________
Address, street, and number.
_City or village______________________ County_
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F. Date of diagnosis..
G. Date of this report.
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Signed_______________________________M. D.
Address, street and number_____________
City or village____________________
DYES.
E. Additional facts.
COAL-TAE
1.
2.
3.
F. Previous illness, if any, due to occupation
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3.
G. Employer’s name
H. Employer’s address, street and number
City or village _
I. Employer’s business _ _
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MAKING
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C. Date first symptoms appeared D. Complicating diseases_______
IN
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Present trade, profession, or
Exact occupation in this trad
Date of entering this trade
Date of commencing this wor
Previous occupations
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OCCUI
A.
B.
C.
D.
E.
A. Diagnosis of present illness.
B. Chief symptoms___________
Nativity
POISONING
Sex__________Age___________Co lor
S. M. W. D. Number of dependerits
to
INDUSTRIAL
Please mail this report in all cases of either suspected or diag
nosed industrial disease to Bureau of Hygiene and Sanitation,
Department of L a b o r,------------------ , which will furnish additional
copies of this blank upon request.
L abor,
APPENDIX 4.
83
When in the judgment of the commissioner of labor it is necessary, it will
be the duty of the employer to provide, without expense to the employee, a
hospital room or dispensary, separate and apart from the workroom or room s;
which room shall be equipped wTith a couch, bed, 01* surgical table, two pairs
of woolen blankets, two hot-water bottles, two tanks (one completely full) of
oxygen, and the necessary apparatus for administering the same; an oxygen
helmet for rescue w ork ; such device or devices for artificial respiration as are
approved by the department of labor; and a shower bath with hot and cold
water; and a toilet, which toilet shall comply with the sanitary code of the
department of labor.
At least one stretcher shall be provided.
It shall be the further duty of all employers to keep in a book or on a card
a record of all employees, showing their exact employment and all changes to
other w ork ; which record shall at all times be open for inspection by the com
missioner of labor or his authorized representative.
TRINITROTOLUOL.
Section 13. S cope.— Beyond the regular regulations for the erection and con
ducting of factories in which poisonous nitro and amido compounds are manu
factured, or regularly recovered in considerable quantities, the following addi
tional regulations shall govern the manufacture of trinitrotoluol and ammuni
tion derived from it.
Sec. 14. B uildings .— T rinitrotoluol shall be manufactured in a special plant
which is an approved distance from other factories or portions of factories.
Buildings in which twice or more nitrated compounds of benzol, or twice or
more nitrated compounds of toluol are manufactured, shall be of fire resisting
material or shall be separated from other buildings.
Trinitrotoluol factories which are not on the land of an explosives factory
shall be surrounded by a fence, which prevents the entrance o f outsiders. At
the gates proper signs shall be provided, which prohibit the entrance of unau
thorized outsiders. Smoking upon the premises shall be prohibited.
Sec. 15. N itration .— Nitration shall be performed in high airy rooms, allow
ing easy escape of vapors, and in which no nitrated product is stored or han
dled in a dry condition. There shall be an approved number of easily accessible
exits.
Sec. 16. S torage of acids .— Spent acids shall be stored in tanks, standing in
the open air and only roofed over.
S ec. 17. W a s h in g and centrifuging .— All washing and centrifuging opera
tions shall be performed in a building in which no nitrated product is stored.
Ample ventilation shall be provided.
Sec. 18. R ecrystallization .— The recrystallizing of the crude trinitrotoluol
with easily inflammable solvents, such as alcohol, benzol, or toluol, shall take
place in a building standing alone. All solution tubs, crystallizing vessels,
centrifuges, and conveying apparatus, shall be closed in such manner that
vapors in dangerous quantities can not escape into the workroom. Proper ven
tilation of the workroom shall be provided. All platforms in this building shall
have an exit into the open air.
S ec. 19. D r ying .— The drying of the trinitrotoluol shall be carried on in a
building standing alone. The separation of the pure trinitrotoluol from the
solvent may be done in the building for the recrystallizing, if the apparatus
provided avoids accumulation.
Sec. 20. P ac k in g .— All packing shall be done in separate packing houses.
Sec. 21. S torage.— Trinitrotoluol shall be stored in separate stock rooms,
protected by an approved type of barricade. The location of the stock rooms
from the nearest manufacturing building shall be at an approved distance.
Sec. 22. Storage of in f lam m ab le solvents .— The storage of tanks of inflam
mable solvents or of toluol shall be constructed in such a manner that the con
tents of the tanks, in case of leakage, can not run over the surroundings. Wher
ever practicable storage vessels should be below ground. I f the above solvents
are stored above ground they shall be stored in an approved manner. Storage
in open air in iron drums in a suitable place is permissible.
Earth embankments of sufficient height to hold the contents of tanks in case
of leakage shall be placed around all tanks o f inflammable materials when
such tanks are located above ground.
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Sec. 23. Manufacture of ammunition.— The manufacture o f ammunition
from trinitrotoluol shall be conducted in a separate building or plant. For
the storage of the ammunition the same regulations govern as for the storage
o f the trinitrotoluol.
Sec. 24. D oors.—All doors which lead into the open air shall open outward.
Sec. 25. Nitrating apparatus.— All nitrating vessels shall have reliable ap
pliances for stirring and for the regulation of the temperature, as well as
ventilating apparatus for the removal of the vapor.
Sec. 26. Drying apparatus.— If the drying is done on small drying hand
trays the heating elements shall be arranged in such a manner that the mate
rial to be dried, or the dust, can not come in direct contact with them. The tem
perature in the drying chambers shall not exceed 60° centigrade [140° Fahren
heit]. All drying apparatus shall be constructed in such manner that the gases
can escape easily without dangerous pressure, if the trinitrotoluol should ignite.
I f the drying is done in large drying pans, hot water or low-pressure steam, at
not over 20 pounds pressure per square inch, shall be employed for heating.
The contents shall be kept in constant motion, and the apparatus shall be con
structed so as to prevent the escape of vapors into the workroom.
Sec. 27. Dust.— The drying and sifting apparatus shall be so constructed as
to prevent as far as practical the escape of dust. All walls, floors, radiators,
electric bulbs, etc., shall be kept free from the accumulation of trinitrotoluol
dust. All employees shall be provided without cost with respirators, cloths,
or sponges, for their protection against dust.
Sec. 28. Fire prevention.— In rooms in which there are easily inflammable
solvents or dried TNT (trinitrotoluol), electric motors, electric bells, or other
sparking apparatus shall not be employed. Centrifugals shall neither have a
brake, nor shall it be allowed to brake them in any improvised manner. Oily
waste shall be kept outside the workroom in safety cans, which shall be cleaned
frequently. In all drying, breaking, and sifting operations the friction of
iron against iron shall not be permitted.
Sec. 29. Refuse.— Impure trinitrotoluol shall be refined and purified before
being used. All refuse from the nitration or recrystallizing rooms which is
still useful shall be removed from the above rooms, and shall be kept in a
special room until it is refined. It shall not be permissible to bury any refuse
which contains trinitrotoluol. Such refuse shall be placed in containers, and
shall be destroyed from time to time under the supervision of an experienced
foreman.
S ec. 30. R epairs .— Repairs on apparatus and other tools which have been
in contact with trinitrotoluol are permissible only after they have been
thoroughly cleaned. The remelting of old vessels, lead pipe, etc., is permis
sible only after they have been burned off on an open fire. All other vessels,
etc., which have become useless, shall be treated in the same manner or shall
be destroyed by explosion.
Sec. 31. Nitric acid.— In view of the danger to the worker from inhalation
o f nitrous fumes in case of fire or of the breakage of carboys, carboys contain
ing nitric acid shall be stored in detached sheds, with sandstone, brick, or
other suitable flooring; and in quantities not to exceed 100’ carboys placed in
not more than four rows. Nitric acid in carboys may be stored in the open in
unlimited quantities.
The following notice will be supplied by the department o f labor on applica
tion, and shall be posted at all places in plants where there is danger o f poison
ing by acid fum es:
ACID FUMES— WARNING.
THE INHALATION OF DENSE ACID FTJMES MAY CAUSE DEATH.
Employees are strictly prohibited from entering buildings where dense acid
fumes exist, or tanks or confined spaces which are not entirely clear o f acid
fumes, unless they wear a helmet.
Employees working in such places shall, in addition to the helmet, wear a life
line, which is at all times in the hands of an assistant stationed outside o f the
tank.
Employees who have been exposed to acid fumes and who feel weak, sick,
short o f breath, or who are attacked with cramps or coughing, shall report this
condition to their foremen, or to the works dispensary, or hospital, at once, so
that proper treatment can be given. They must not wait to get home. Delay
nray be fatal.
A P P E N D IX
85
5.
Responsibility for complying with these regulations shall rest with the fore
man or other person designated for that purpose by the management o f the
plant.
By order of—
»
Commissioner of Labor.
Water shall always be available for use in case of evolution of nitrous fumes
caused by breakage or other accident to carboys, and all workers handling such
acid shall be warned against sprinkling sand, sawdust, earth, or anything other
than water or alkalies upon any spilled nitric acid.
At all places where there is danger of an employee becoming burned by con
tact with acid there shall be a shower bath.
S ec. 32. A voidance of a ccu m u lation s .—No more trinitrotoluol shall be kept
in the workroom than is necessary for concurrent use.
CHEMICALS.
S ection 33. S cope.— The handling and storage of all acids and other chemicals
necessary for the operation of plants not herein provided for, shall be governed
by regulations as set forth in the code governing the operation of chemical
works.
S ec. 34. H eating .— The workrooms, when desirable, shall be heated by an
approved system of steam, indirect hot air radiation, or hot water. The tem
perature of the steam shall not exceed 120° Centigrade [248° Fahrenheit].
The radiators shall be at least 1 inch distant from all wooden walls or other in
flammable material, and shall be attached in such a manner that they can be
easily inspected and cleaned.
A P P E N D IX 5.— GREAT B R IT A IN : R EG U LATIO N S FOR THE M A N U
FACTURE OF NITRO AND AMIDO DERIVATIVES OF BENZENE
AND OF EXPLOSIVES W ITH USE OF DINITROBENZOL OR DINIT RO TO LU O L.3
Whereas the manufacture of nitro and amido derivatives of benzene, and the
manufacture of explosives with use of dinitrobenzol or dinitrotoluol, have been
certified in pursuance of section 79 of the factory and workship act, 1901, to be
dangerous;
I hereby, in pursuance of the powers conferred on me by that act, make the
following regulations, and direct that they shall apply to all factories and work
shops in which the said manufactures are carried on.
Provided that regulations 1 (a ), 2, 3, 4, and 14 (c) shall not apply to any
process in the manufacture of explosives in which dinitrobenzol is not used.
DEFINITIONS.
“ Employed ” means employed in any process mentioned in the schedules.
“ Surgeon ” means the certifying factory surgeon of the district or a duly
qualified medical practitioner appointed by written certificate of the chief in
spector of factories, which appointment shall be subject to such conditions as
may be specified in that certificate.
“ Suspension ” means suspension by written certificate in the health register,
signed by the surgeon, from employment in any process mentioned in the
schedules.
DUTIES.
It shall be the duty of the occupier to observe Part I of these regulations.
It shall be the duty of all persons employed to observe Part II of these
regulations.
FART I.— DUTIES OF OCCUPIERS.
1.
(a) Every vessel containing any substance named in schedules A or B
shall, if steam is passed into or around it, or if the temperature of the contents
be at or above the temperature of boiling water, be covered in such a way that
no steam or vapor shall be discharged into the open air at a less height than 20
feet above the heads of the workers.
8 G r e a t B r it a in .
H o m e O ffice .
S t a tu to r y R u le s a n d O rd e rs, 1 9 0 8 .
N o. 1310.
86
IN D U S T R IA L
P O IS O N IN G
IN
M A K IN G
C O A L -T A R
DYES.
(6)
In every room in which fumes from any substance named in schedules A
or B are evolved in the process of manufacture and are not removed as above,
adequate through ventilation shall be maintained by a fan or other efficient
means.,
2. No substance named in schedule A shall be broken by hand in a crystalliz
ing pan, nor shall any liquor containing it be agitated by hand, except by means
of an implement at least 6 feet long.
3. No substance named in schedule A shall be crushed, ground, or mixed in the
crystalline condition, and no cartridge filling shall be done, except with an
efficient exhaust draught so arranged as to carry away the dust as near as
possible to the point of origin.
4. Cartridges shall nort be filled by hand except by means o f a suitable scoop.
5. Every drying stove shall be efficiently ventilated to the outside air in such
manner that hot air from the stove shall not be drawn into any workroom.
No person shall be allowed to enter a stove to remove the contents until a free
current of air has been passed through it.
6. A health register, containing the names of all persons employed, shall be
kept in a form approved by the chief inspector of factories.
T. No person shall be newly em-ployed for more than a fortnight without a cer
tificate of fitness granted after examination by the surgeon by signed entry in
the health register.
8.
Every person employed shall be examined by the surgeon once in each
calendar month (or at such other intervals as may be prescribed in writing by
the chief inspector of factories) on a date o f which due notice shall be given to
all concerned.
9., The surgeon shall have power of suspension as regards all persons em
ployed, and no person after suspension shall be employed without written sanc
tion from the surgeon entered in the health register.
10. There shall be provided and maintained for the use of all persons em
ployed—
(a) Suitable overalls or suits of working clothes which shall be collected at
the end of every day’s work, and (in the case of overalls) washed or renewed
at least once every w eek; and
(&) A suitable meal room, separate from any room in which a process men
tioned in the schedules is carried on, unless the works are closed during meal
hours; and
(c) A suitable cloakroom for clothing put off during working hours; and
( d ) A suitable place, separate from the cloakroom and meal room, for the
storage of the overalls.
For the use of all persons handling substances named in the schedules—
( e ) India-rubber gloves, which shall be collected, examined, and cleansed, at
the close of the day’s work, and shall be repaired or renewed when defective,
or other equivalent protection for the hands against contact.
For the use o f all persons employed in processes mentioned in schedule A—
( f ) Clogs or other suitable protective footwear.
11. There shall be provided and maintained in a cleanly state and in good
repair for the use of all persons employed—
A lavatory under cover, with a sufficient supply of clean towels, renewed
daily, and of soap and nail brushes, and with either—
{a) A trough with a smooth impervious surface, fitted with a waste pipe
without plug, and of such length as to allow at least 2 feet for every five such
persons, and’having a constant supply of warm wTater from taps or jets above
the trough at intervals of not more than 2 fe e t; or
( b) At least one lavatory basin for every five such persons, fitted with a
waste pipe and plug or placed in a trough having a waste pipe, and having either
a constant supply of hot and cold water or warm water laid on, or (if a con
stant supply of heated water be not reasonably practicable) a constant supply
of cold water laid on and a supply of hot water always at hand when required
for use by persons employed.
For the use of all persons employed in processes mentioned in schedules A
and B—
(c ) Sufficient and suitable bath accommodation (douche or other) with hot
and cold wTater laid on and a sufficient supply of soap and towels. Provided
that the chief inspector may in any particular case approve o f the use of public
baths, if conveniently near, under the conditions (if any) named in such
approval.
APPENDIX 5.
87
12. No person shall be allowed to introduce, keep, prepare, or partake of
any food, drink, or tobacco in any room in which a process mentioned in the
schedules is carried on.
PART II.— DUTIES OF PERSONS EMPLOYED.
13. Every person employed shall—
(a) Present himself at the appointed time for examination by the surgeon as
provided in regulation 8;
(b) Wear the overalls or suit of working clothes provided under regulation
10 ( a ) and deposit them, and clothing put off during working hours, in the
places provided under regulation 10 (c) and (d) ;
(c) Use the protective appliances supplied in respect of any process in which
he is engaged;
(d) Carefully clean the hands before partaking of any food or leaving the
premises;
(e) Take a bath at least once a week, and when the materials mentioned in
the schedules have been spilt on the clothing so as to wet the skin. Provided
tlnit (e) shall not apply to persons employed in processes mentioned in schedule
C, nor to persons exempted by signed entry o f the surgeon in the health register.
14. No person employed shall—
(a) After suspension, work in any process mentioned in the schedules with
out written sanction from the surgeon entered in the health register;
(&) Introduce, keep, prepare, or partake of any food, drink, or tobacco in any
room in which a process mentioned in the schedules is carried o n ;
(c ) Break by hand in a crystallizing pan any substance named in schedule
A or agitate any liquor containing it by hand, except by means of an imple
ment at least 6 feet lon g;
( d) Interfere in any way, without the concurrence of the occupier or man
ager, with the means and appliances provided for the removal of the fumes
and dust, and for the carrying out of these regulations.
SCHEDULES.
A. Processes in the manufacture of—
Dinitrobenzol.
Dinitrotoluol.
Trinitrotoluol.
Paranitrochlorbenzol.
B. Processes in the manufacture of—
Anilin oil.
Anilin hydrochloride.
C. Any process in the manufacture o f explosives with use of dinitrobenzol or
dinitrotoluol.
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