Bureau of Labor Statistics, U.S. Department of Labor

DANGERS IN THE MANUFACTURE OF PARIS GREEN AND SCHEELE'S GREENSource: Monthly Review of the U.S. Bureau of Labor Statistics, Vol. 5, No. 2 (AUGUST, 1917),pp. 78-83Published by: Bureau of Labor Statistics, U.S. Department of LaborStable URL: http://www.jstor.org/stable/41829377 .

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78 MONTHLY REVIEW OF THE BUBEAU OF LABOR STATISTICS.

will be sufficient temporarily to incapacitate the person so exposed. "From an industrial hygienist's standpoint the air of any place where men work which contains 0.01 per cent of carbon monoxide is dangerous, and such a condition should be immediately remedied."

As the first step in reducing othe carbon monoxide hazard in steel plants it is suggested that a survey should be made to determine whether the gas is escaping into the atmosphere, and that some system of periodical inspection should be instituted whereby places where gas may escape could be watched and carbon monoxide pollution guarded against. A system of regular air sampling is recommended, followed by an effort to determine the source of the gas, and, if a leak, make the pipe, etc., gas-tight, or if the result of an industrial process change the method of operation or construction. There should be provision for ample ventilation.

Finally, where none of these methods is applicable or, if instituted, fails to prevent the pollution of the air by carbon monoxide, operating conditions should be so altered as not to require men to remain in such hazardous places for more than short periods of time.

DANGERS IN THE MANUFACTURE OF PARIS GREEN AND SCHEELE'S GREEN.

The division of industrial hygiene of the New York State Indus- trial Commission has recently completed an investigation into the manufacture of paris green. The inquiry was made by Chemical Engineer John H. Vogt and Acting Medical Inspector Lester L. Roos, M. D., and their report, as it appears in the Bulletin of the Industrial Commission for June, 1917 (pp. 181 to 183), is here re- produced : 1

Paris green * * * is now entirely used as an insecticide for destroying potato bugs and other insects, and on account of the cost of raw material it is little used for any other purpose. Fully 1,000 tons of paris green are annually produced in New York State, and additional precautions are necessary in its manufacture beyond those given in the labor law to guard against cases of industrial poisonings. Considerable illness has been found to exist among many of the workers engaged in this production, due in a measure to lack of knowl- edge on the part of those engaged in its preparation and disregard for the ex- treme poisonous qualities which this salt possesses. t

Inasmuch as the workers are unacquainted with its dangerous and poisonous properties many cases of arsenical poisoning are not discovered, because as soon as a slight irritation of the skin develops, or nausea occurs, men leave the industry, and so the labor engaged therein is a constantly shifting one.

1The final report, modified and revised, has appeared as Special Bulletin No. 83, issued by the New York State Industrial Commission in July, 1917. Albany, 1917. 17 pp. Illustrated.

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MONTHLY REVIEW OF THE BUREAU OF LABOR STATISTICS. 79

According to Desamle and tierron, paris green was first discovered in the year 1712 by Russ and Sattler in Schweinfurt, Bavaria, Germany, from basic- verdigris and arsenic. According to others, Voumitis, of Vienna, Austria, was the first manufacturer. Liebig published the manufacturing process in 1822, and in 1872 its manufacture was undertaken in Brooklyn, N. Y.

The striking bright shade and popularity of this material led to its manu- facture by nearly all color makers at that time, which circumstance is the cause of the various names under which it is known besides that of paris green ; such names as " Emperor Green," " New Green," " Mineral Green," " Original Green," and "Patent Green," were given to it by the various makers. The object of this, no doubt, was to lead the public to believe that the so-called colors were not of a poisonous nature. "These colors, or tints, were produced by mixing paris green with barytes,

chromáte of lead, china clay, and other white mixtures, thus lowering the cost of manufacture. " Scheele's Green " is the name given to the commercial product used as an insecticide, which is manufactured in one establishment in the State. The original method of its manufacture was kept a strict secret.

In an attempt to manufacture paris green it was discovered by C. W. Scheele in 1742, a native German chemist who resided in Sweden, that a sub- stance could be produced which greatly resembled paris green and manufac- tured at less cost. To this substance the name " Scheele's Green " was ap- plied, by which it is still known.

Paris green and Scheele's green are manufactured by 10 firms in the United States, of which 7 firms are located in the State of New York, only 6 of which were actually making the materials when the investigation was conducted. Five of the firms were located in the borough of Brooklyn, city of New York, and one at Beacon, N. Y., the latter confining its product to Scheele's green and kalso- mines. All of the factories engaged in the production of these substances manu- factured other compounds, such as dry colors, paints, crayons, bleaching solu- tions, dyes, and other chemicals, no factory being entirely devoted to the exclu- sive production of these articles. The amount manufactured varies with the demand. The largest factories turn out about 200 tons each during their sea- son, which is principally a period of about six months during the fall and winter months.

The process of paris green, also known as Schweinfurter Green," " Meadow Green," " Parrott Green," and " English Green " is a cupric aceto arsenite, having the formula CU (CkHiOaKSCUAsiO«, is an exceedingly poisonous double salt insoluble in water ; in contact with organic matter it changes somewhat. Many micro-organisms and fungi act upon the compound and produce arseniu- retted hydrogen, which, no doubt, causes' the arsenical ulcers met with by workers engaged in preparing the material. The gas evolved being soluble in water readily attacks the skin, also the eyes, nose, throat, and lungs, being more susceptible to its action than the simple mechanical action of the pigment. The fine powder attacks the skin, but its most intense effect is found in those regions of the body where perspiration is present at most times.

Scheele's green, known as "Arsenite o£ Copper," also " Hydro Cupric Arsenite," " Mineral Green," and u Swedish Green," is composed of acid arsenite of copper and is represented by the formula CuHAsO*. It has a strikingly fine light green color, formerly used in calico printing, and as a pigment for green wall paper. It is insoluble in water, but dissolves in excess of alkalies or Acids. It is very poisonous and like paris green capable of producing severe ulcers on the skin, severe irritation of the mucous membranes of the eyes, nose, throat, and gastro intestinal irritation. Its use is principally as an insecticide.

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80 MONTHLY REVIEW OF THE BUREAU OF LABOR STATISTICS.

Chronic arsenical poisoning is a condition to which most of the men are ex- posed ; acute pains in the abdomen, and nausea and intense thirst are first noticed. This is followed later by gastritis, enteritis, jaundice, and diarrhre, followed by constipation. Nails drop off, large ulcers develop, and the skin appears somewhat mummified. In intense cases, death sometimes results.

Paris green is manufactured by dissolving In wooden tubs a quantity of sulphate of copper in hot or cold water, adding to it acetic acid, heating the solution to form cupric acetate. In another tub arsenious acid is dissolved in a boiling solution of sodium carbonate, which usually takes about an hour to carry out, the proportions added in such an amount as to obtain arsenite of soda. These tanks are usually hooded to carry away the vapors formed, outside of the factory. This solution is added to the cupric acetate solution and stirred while hot. Mechanical means are used in some cases, while the old style hand method is principally practiced. An olive-green precipitate of cupric aceto arsenite results. Should a yellow-green precipitate be produced in the course of boiling, a little acetic acid is added, the solution is boiled a little longer and íhe liquid allowed to settle. The water solution is run off and the precipitate washed with several changes of water. (This last step is not practiced by .some firms.) The resultant precipitate is shoveled out on filters and allowed to drain; when the draining is finished, it" is again shoveled on drying trays. These are placed in a drying room or drying closet, and when dried dumped into chutes or hoppers which convey it to crushing rolls; then it is sifted, trans- - f erred to the bolter, and finally filled into kegs, barrels, or cans, either by hand . filling with a shovel or scoop, from a hose-spout from the bolter, and in the case of small cans in one factory by means of an automatic weighing machine.

Scheele's green is manufactured by adding to a solution of sulphate of copper, v. solution of arsenite of soda as long as the green precipitate forms, washed with water and the water solution drained off. The material is shoveled from the vat onto drying trays, placed in a wooden dryer and, when dry, placed into a bin and shoveled out into a tumbler with other ingredients to make the patent insecticide, in which but 1 per cent of the pigment is an active part. The manufacture of this substance is practiced in but one factory. The pack- ing is performed in a separate room by an obsolete method of scooping up from the large receptacles into the smaller boxes. The room in which this work is performed is not provided with any means of mechanical ventilation.

The method of production in each factory varies somewhat in handling. For instance, one factory does not wash the finished precipitate of paris green, while another performs this task; drying is done in one factory in a large room which takes more than three to four days, while in another it is done in 24 hours. Employees are obliged to enter the dry room, which often has a temperature of 140° F., to carry in and out the trays containing the product ; another has separate drying ovens, each arranged with a damper so that the How of hot air can be stopped which circulates through the oven, thus preventing the heat and dust being blown into the workroom.

The dumping of the trays, containing material, into the chute leading to a bolter is done in one factory without a hood inclosure to occlude the fine paris green dust, while in another it is placed on the tumbler, which is turned upside down and surrounded by a hood or a closet, to which is attached a pipe with an exhaust, which has a static suction of one-half inch ; while another has no pipe but a sliding door in the inclosure, which is closed by the operator before turning over the trays to be dumped. Paris green, in the last case sifts out of the door when it is opened for the next tray, and workmen usually inhale a considerable amount of the dust.

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MONTHLY REVIEW OF THE BUREAU OF LABOR STATISTICS. 81

Filling boxes by hand is resorted to in most all the factories. The material is scooped out of the receptacles or barrels with small shovels. Barrel filling is performed directly from the tumbler through a hose connection, reliefs being provided from the barrel by a small pipe back to the tumbler, in which the dust and air contained within the barrel is led back, thus preventing same from entering the workroom; some of the firms do not take this precaution. Mechanical weighing and filling of one and two pound boxes are performed in one factory with good results. The machine, made by an automatic weighing machine company, has attached to it exhaust pipes, so placed to remove the greater part of the dust generated.

Label pasting is done under small hoods in one factory, but in all others no hoods are provided.

It appears to be the prevailing opinion that the fine dust of paris green can not be controlled and that it will continue to be liberated at all points. Another important factor is the lack of knowledge possessed by the workers of its poisonous properties.

It is useless to provide a well-equipped room in which employees may take tlieir meals, if the material is tracked into the room on shoes of workmen and the floor seldom cleaned.

In some factories single lockers are provided for employees, old clothing and street clothing are hung together in these, and dust from the working clothes is shaken into the street clothes.

If walls, though whitewashed in accordance to law, are allowed to contain paris green powder, if a disregard is shown in placing trays containing paris green and Scheele's green near windows through which a draft blows, whereby material is scattered to all parts of the factory, if respirators are provided by the firms which are allowed to get dirty and the meshes clogged with the paris green powder, or if the underclothes which the men wear are dried in rooms with paris green, such methods as these show the necessity of stringent education methods with the workmen and proprietors which will greatly re- duce the number of cases of arsenical poisoning.

Factory N&. 1. - The manufacture of paris green in this establishment is con- ducted entirely in the basement of a six-story fireproof building. It is well ventilated by natural means, windows being located on two sides of the factory. The floors are kept in a fairly good condition. The men are provided with a linen headpiece and face piece, together with cotton waste and overalls, which are made to tie at the wrist and ankles. All men use gloves and high shoes, which they provide themselves. No hot water, soap, nor towels were furnished.

In the method of drying this factory obviates the necessity of men entering the dry room by the use of the American blower system. The drying racks are placed on cars and pushed into a tunnel, which is heated by surplus steam /rom the boilers. As each car is brought in it moves the other ahead, and at the end of seven days the first car reaches the end of the tunnel where it is placed on a transfer car and prepared for bolting.

The bolting, sifting, and packing are carried on in the same room ; the floors, walls, and ceiling of the room were thickly covered with paris green. An ex- haust system located under the packing table disposed only of small quantities of the dust. Within the bolting room there is an engine with a swiftly run- ning belt. This belt serves to keep large quantities of paris green dust in con- stant motion.

To place the dry pigment in the tumbler, the worker is required to mount six steps of a movable platform carrying the tray above his head and then throwing it into the dumper. This operation is also accompanied by large quantities of

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82 MONTHLY REVIEW OF THE BUREAU OF LABOR STATISTICS.

dust entering the atmosphere. In barreling and package filling much dust is also created.

Ten men were employed, of which seven were examined : S. P., 24 years of age, engaged for three years in the industry, showed a

marked conjunctivitis. S. C., 27 years old, engaged in the industry for three years, showed a con-

junctivitis and scars of ulcers on legs and hands. J. D., 29 yèars of age, negative. W. S., 24 years old, one month in the industry; this man showed a large,

nasty-looking ulcer, located on the right side of the lip and extending into the nasal cavity. The septum was involved, and this will probably cause a per- foration.

F. B., 24 years old, four years in the industry ; negative. M. O., 50 years old, one month in the industry, shows a slight nasal irrita-

tion. E. W., 41 years old, five years in the industry, shows a marked conjunctivitis

and slight anemia. Factory No. 2. - This factory is a four-story nonfireproof building, devoted

almost entirely to the manufacture of paris green. It is ventilated by doors and windows. In this plant little can be said in favor of the conditions toward guarding the health of the employees. The floors, walls, ceiling, stairs, and halls of the building are covered with deep layers of paris green dust. Each footstep raised a quantity of dust from either the floor or the stair tread. In the vat room and package-filling room, owing to poor drainage, paris green in connec- tion with water formed a pasty mass covering the greater part of the floor.

The pigment in pulp form is taken in barrels from the tank room on the ground to the fourth floor and then placed in the drying room. The worker must pass through the drying room each time he goes to the tumbler, and while batches are being tumbled the door between the dry room *tnd the tumbling room is always open. The drying tray is dumped in and large quantities of dust result. In this plant the bolting is carried out in the same room as the tumbling, and while the bolter is in motion large clouds of dust are produced completely enveloping the worker at the tumbling machine.

Men were found eating in a small wash room which had no window and which was in a very dirty condition. These men, who were not provided with any headpieces, overalls, masks, hot water, soap, or towels, had no realization of the dangerous material handled or its means of entry into the body.

Barrel and package filling also gave rise to large quantities of dust; women were engaged in labeling and no protective clothing was provided for them. Fifteen men and two women were employed in this factory and seven were examined:

K. S., age (?), employed 25 years, showed a marked anemia due to arsenic. M. C., (?) employed two months; negative. Wm. L., 36 years old, employed about six weeks, has attack of furunculosis

due to paris green. J. W., 30 years, employed four months; negative. O. C., 22 years old, employed two weeks, has had an attack of furunculosis

on arm and ulcers on fingers. E. G., 26 years old, employed two months, shows scars of ulcerations on thé

arms. J. S., age (?), employed nineteen years, has recurrent attacks of furunculosis. In these plants for all conditions which were found to be detrimental to health

and whereby the law could be applied orders were issued. These orders related

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MONTHLY REVIEW OF THE BUREAU OF LABOR STATISTICS. 83

to the prohibition of eating within the factory ; cleanliness of floors, walls, and ceilings; providing running hot water, soap, and individual towels; installing exhaust systems to dispose of the dust created in the process of manufacture; suitable place in which to eat meals ; and suitable means to remove dust from the floors.

Analytical determinations. - A chemical analysis was maae of air of one of the packing rooms, where filling of boxes from barrels was performed; 305 milligrams of the paris green were found per cubic meter of air at 60° F. This material in the air was generated in the process of hand filling, blown off the walls and ceiling, and stirred up from the floor in the act of walking. A proper method of weighing and filling under inclosed hoods, clean walls,* and floors would have eliminated this large amount of dust.

Samples of underclothing were analyzed and found to contain 1.1 milligrams of paris green in a piece measuring six square inches. Printed notices furnished by the Department of Labor of the State Industrial

Commission, to read as follows, should be posted in every room where paris green is handled:

" Paris green is a dangerous poison and sickness results from the breathing of air containing it, through broken skin, and through the mouth. " Don't hang any clothes to be dried in the dry room.

" Don't leave the factory in the clothes in which you work. " Don't place your factory clothes in the same locker with street clothes, when provided for you. " Don't eat in or about the factory, only in provided lunch room.

" Don't eat before you have washed your face and hands with hot water and soap. " Don't scratch or touch any part of your body before you have washed your hands.

" Don't sweep the floor with a broom. " Don't plug your nose with cotton ; tie clean cotton waste over nose and mouth.

" Keep your gloves clean on the inside. "Take a complete wash at home -daily. " Drink milk instead of beer or whiskey. "Tie clean cotton waste, twice daily, over nose and mouth, as this is the

easiest and best respirator. " Try and keep down dust as much as possible by closing doors carefully and keeping the dust off the floor as much as possible. " Keep your hair, mustache, and finger nails short, to prevent the paris green from settling in them."

Recommendations to employer . - Provide double lockers for men engaged in paris green manufacture.

Sweep all floors and keep ceiling and walls of workroom, halls, stairs, and lunch room free from paris green dust by using a vacuum sweeper.

Provide periodical medical examinations for men engaged in the production of paris green and Scheele's green.

Provide overalls, head and neck pieces of unbleached muslin, and gloves for paris green workers, and have same washed weekly.

Provide clean cotton waste as respirators for all paris green workers. Not less than one hour should be permitted for the noonday meal. It is suggested to the State industrial commission that the recommendations

which are made and are not covered by law be enacted into a code in order that this industry be freed from the many dangerous conditions which now sur- round it.

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