SF 767 AI^aaiTIGAL CATTL:^ DIP3 U.S.D.A. iSul, 603 By :^. M. Ghapin August 1914 ..,i.,i,ili;;: -5^75 7 .^^.o.-^-^""^- Mai« uteM, LIBRARY G U.S.DEPARTMENT OF AGRICULTURE 603 Contribution from the Bureau of Animal Industry, A. D. Melviri, Chief. August 14. 1914. ARSENICAL CATTLE DIPS: METHODS OF PREPARATION AND DIRECTIONS FOR USE. By Robert M. Chapin, ,, Senior Biochcntist, Biochemic Division. INTRODUCTORY. This bulletin is intended to be a handbook for the user of arsenical cattle dips. It aims to include in brief but ample form general in- formation, formulas, tables, and practical hints bearing on the prepa- ration and management of [arsenical dipping solutions, kit to this field it is strictly limited. Those who Hesire a popular account of [the life history of the [Texas- fever tick and of its Irelation to cattle are re- ferred to a previous bulle- |in (Farmers' Bulletin 498) |issued by the department, 'he same, as well as an- )ther previous publication [(Bureau of Animal -Industry Circular 207), contains plans and speci- Ications for the construction of dipping vats, together with directions for the management of cattle in connection with dipping. PROPERTIES OF SUBSTANCES USED IN MAKING DIPS. Making a dip is simply a manufacturing j^roposition. Xo manu- facturer can expect to get the best results unless he is somewhat icquainted with important facts regarding his raw materials. White arse?iic, also known as arsenic trioxid, arsenious or arsen- )us oxid or anhydrid, should always be purchased in the form of fine powder, and under a g-uaranty of 99 per cent purity. Water, iven when boiling, will dissolve only a little of it, and that slowly, )ut by the use of certain other chemicals white arsenic may be readily md abundantly brought into solution. White arsenic is a violent poison, and users of it must never allow familiarity to beget carelessness. It may be absorbed into the system and cause injury or death, either through the mouth, the 47702°— 14 487^60 (S^^ \^^ Fig. 1. — Map of the United States, the shaded area showing the territory to which this bulletin applies. 2 farmers' bulletin 608. lujigs, or the/.ski.n; tl'ontfwj't 'neither the dry powder nor the solution should be allV)\vVd t?)*rei^i':ii*n*oii.thc skin. The breathing in of dust arising froijrrrltiP,*;Tp\-.;6o\Ttl'i»r. (firing handling must be avoided, while, if'caftle Vre iJeiiig s'prayed, neither the operator nor the cattle should inhale any of the spray. Moreover, from a boiling solution arsenic may be thrown out as a fine spray and also, under certain conditions, as the very poisonous gas " arsin.'' Hence, concentrated dips should be prepared only in thoroughly ventilated places, while all work should be done on the windward side of the kettle and as far from it as practicable. If arsenic in any form has been swallowed, medical attention is to be obtained as soon as possible; but since promptness of action is of very great importance and medical attention is not always readily available, it is best for all who use arsenical dips to be familiar ^ith first-aid treatment. The United States Dispensatory (nineteenth edition) has the following to say in this matter: If the antidote * * * be not directly at band, free voinitinp sbould be induced by tbe finger, tbe featber part of a quill, and the aduiinistratiou of an emetic; * ♦ * Demulcent drinks sbould be freely given, .such as milk, wbite of eggs and water, or flour and water, which serve to encourage the vomiting and to envelop the poison. The antidote having been faithfully applied, tbe subsequent treatment con- sists in the administration of mucilaginous drinks and the treatment of symptoms as they arise. * ****** The antidote above referred to is * * * ferric hydrodUl with mnuncsium oxid in the moist or pulpy state. As soon as it is ready it must be given in doses of a tablesi>oonful to an adult, of a dessertspoonful to a child, every five or ten minutes until the urgent symptoms are relieved. * * * Its efficacy is, of course, greater the sooner it is administered after the ingestion of the poison; but even after delay its use will prove advantageous so long as any portion of the p(nson still remains in the stomach. ♦ ♦ ♦ It should be an invariable rule to prepare the antidote at the time It is waiittnl from materials always kejit at hand. • ♦ ♦ 'phe best antidote known is the combination of ferric hydroxid with magne.sium oxid now recognized by the U. S. Pharmacopoiia. The materials for the antidote referred to can be supplied by any prescribing jjharmacist, contained in two l)ottles. In this separated form the antidote keeps well, and when an emergency calls for its u.so all that is necessiuy is to mix thoroughly (he contents of the two bottles and to administer as directed. But in any case medica^ attention must be obtained as soon as possible. Sodium carhonate. — Also known as sal soda or washing soda, when fresh consists of colorless trans|>»irent crystals. On keeping, unless lightly closed from the air, it tends to lose its crystalline apix-aranc*". and to fall to a white powder. This change is due morcly to the fact that the crystals carry a large amount of com- bined water (water of crystallization), and on exposure to the air ARSENICAL CATTLE DIPS. 'S much of this water may evaporate with consequent destruction of the crystalline form. The soda itself is in no way affected by this loss of water, except that it really becomes stronger, weight for weight. Another form of sodium carbonate, called " monohydrated sodium carbonate," also occurs in commerce in the form of a white crystalline granular powder. It contains only a small amount of water of crystallization and is practically unaffected bj^ exposure to air. This form of soda from a manufacturing point of view is far preferable to sal soda, as it is of constant and permanent composition, and being much stronger, weight for weight, it is less expensive to handle. When using monohydrated soda it is necessary to remember that only 4rJ pounds are needed to do the same work as 10 pounds of sal soda. Pine tar. — Pine tar when fresh is semiliquid, but with age becomes granular and nearly solid, in which condition it is of less value. Mixed with it is always more or less water of decidedly acid prop- erties (pyroligneous acid), which on standing tends to float on the surface and should be dipped or poured off before the tar is used. Tar is heavier than water and when stirred with it usually forms a very poor mixture from which most of the tar rapidly settles out, but when the water is of just the right temperature and somewhat alkaline a fairly stable suspension may generally be obtained. Wlien previously treated with an amount of caustic alkali sufficient to com- bine with a considerable proportion of the tar acids, or when blended with soap, the tar easily mixes with water and then forms a good and permanent emulsion. Caustic soda. — Also known as sodium hydroxid, or sodium hydrate, on account of its wide range of application by chemists, pharmacists, and manufacturing industries occurs commercially in a number of different forms, as powder, flakes, solid masses, or broken fragments ; m color ranging from pure white to grayish or brownish tints. For the use of chemists and pharmacists it is put up in glass bottles; for industrial purposes it is supplied in various sized cans or drums of thin sheet iron. The latter is the variety that should be purchased for making dip. Its large output and wide use render it easily obtainable almost everywhere — far more so than white arsenic. The 10-pound can is the best size to buy for home use in preparing dips ; larger consumers can probably handle the material in larger drums conveniently and of course more economically. The purchaser must make sure that the contents of the drum he contemplates buying are in fragmentary form, or granulated, for much caustic soda is run into drums in a melted condition and on cooling forms a single solid cake, which, though satisfactory for factory use, is not adapted for the present purpose. It should always be purchased under a guaranty of not less than 85 per cent actual caustic soda. 4 farmers' BFLLETTX 603. Caustic soda is an intensely active and pr>\vt'rful substance. When exposed to the air it strongly attracts moisture, increasing in weight and becoming pasty, while at the same time it becomes contaminated with sodium carbonate through ab.sorption of carbon dioxid. Hence it must always be purcliased in original containers, never in bulk; the container mu.st not be opened until just before the material is to be used; the substance must not be allowed to stand exposed to the air, and if any is left over which is to be kept for subsequent use it must be immediately transferred to a tin pail provided with a tightly fitting cover, such as a lard pail, or, best of all. a paint pail with a friction top. Owing to the intense chemical activity of caustic soda it is ex- tremely corrosive in its effect upon .skin or clothes, and upon the lungs if dust from it is inhaled. Therefore it is necessaiy to handle it gently to avoid the raising of dust and to wash off at once with wat^r any which may touch the skin or clothing. Caustic potash. — Also known as potassium hydroxid or hydrate, is very similar in its properties to caustic soda. It is not, however, so widely used industrially, and is decidedly more expensive without being any better for the present purpose. Therefore it should be purchased only when caustic soda happens not to be available. In its use one must remember that, weight for weight, it is less efficient than caustic soda, so that for every pound of the latter there must be employed 1.4 pounds of caustic potash. Like caustic soila. it must be guaranteed at least 85 per cent pure. Lye. — This is a term employed to designate a grade of caustic soda put up primarily for domestic use, such as making soap from waste grease and for general cleansing. Since ordinarj' buyers of this grade of goods are not apt to be able to judge closely of its quality, it is sometimes of very inferior grade, though not necessarily so. If any guaranty regarding its purity can be obtained, it may be used for dip making, in case of necessity, in the same proportions as caustic soda. THE GENERAL COMPOSITION OF DIPS. All arsenical cattle dips contain arsenious oxid as the active tick- killing agent. But since straight ai"senious oxid, that is, M'hite ar- senic, is so slightly and slowly soluble in water, it is necessary to use some other chemical agent, such as sodium carbonate or hydroxid, to bring the arsenious oxid into solution. In this way the white arsenic is changed to sodium arsenite if either sodium hydroxid or sodium carbonate is employed, oi- to potassium ai'senite if the corresponding potassium compounds are used. Starting with a given weight of white arsenic, whether it is converted to sodium arsenite or to potas- sium arsenite appears to make no difference in the action of the finished dip. ARSENICAL CATTLE DIPS. 5 After the white arsenic has been brought into sohition, a variety of substances, such as tar, soap, oils, etc., may be added with one or more of the following objects in view: (1) To increase the effective- ness of the bath against ticks, either through greater penetrating power or better adhesion, or through repellent action ; (2) to render milder the effect of the bath upon cattle; (3) to denature the bath so that cattle will not drink it. Proprietary concentrated dips differ from each other and from home-made dips essentially only in the nature and amount of such added substances. MAKING THE BOILED DIP. The boiled dip has been recommended for use in two strengths, the baths corresponding to which will be termed here " low-strength bath " and " high-strength bath.''' The low-strength bath is com- monly used for ordinary tick-eradication work on the range, the cattle being dipped regidarly every two weeks for possibly several months. The high-strength bath is used to treat cattle which are undergoing transportation to a tick-free region, the treatment being usually limited to only two dippings, 5 to 10 days apart. To make 500 ^ gallons low-strength bath provide : Sal soda* 24 pounds. White arsenic, 99 per cent pure, in fine powder 8 pounds. Pine tar 1 gallon. Put 25 gallons of water in a kettle or tank of 40 to 50 gallons capacity, heat to boiling, and add the sal soda. When this has dis- solved add the white arsenic, then boil and stir for 15 minutes or longer, until the white arsenic has entirely disappeared. If intended for immediate use cool to 140° F. (by the addition of cold water if desired), then pour in the pine tar in a thin stream while constantly and vigorously stirring the solution. Immediately empty the liquid into the dipping vat, which has already been three-fourths filled with water, and stir thoroughly. For a stock solution to be kept on hand and used when needed, add no tar, but, after the solution of arsenic and soda has become entirely cold, make it up to 25 gallons (see method on page 7), stir well, let settle, and draw off into containers which can be well closed. This constitutes " low-strength boiled arsenic stock," and its use in a diluted dipping bath calls for a "tar stock," the preparation of which is described on page 7. High-strength bath or high-strength boiled arsenic stock is pre- pared in exactly the same way, except that for 500 gallons of diluted bath there is used 10 pounds of white arsenic and 25 pounds of sal soda (or 11 pounds monohydrated sodium carbonate). ^ The number of pounds of white arsenic needed to make any number of gallons of bath of any strength may be obtained from Table 1, on page 11. *0r monohydrated sodium carbonate, lOJ pounds. 6 farmers' bulletin 603. A by-prcKluct of the action of sodium c:«rl»oiuile vn white arsenic is the gas carbon dioxid. The esonjie of this gas is attende,'es in llic .stieiiKtli of arwinlcal batliH, tonelher willi luetliod.s > It In VPi-y llkoly tlint till' l.iin'iui will Ihsuo pin-nilsalon for oortnln proprlrtary prepii rations to bo iihmI In oITlrliil dlppInK'. Any such product will bpur a statemeiit ou tlio label to till- i-ITcct tlint the prcliict Iiiih l.o.-n cMiiiiInod by tin- buroiiu nud has bcj-n por- milted for use In olllclnl dipping id: ii ^Iven dilution. AKSENICAL CATTLE DIPS. 9 of chemical analysis, have beeu elsewhere discussed by the writer,' Here it is sufficient to note that even if all precautions are taken against leakage, either in or out, against evaporation, and against mistakes In measurements, etc., still the bath is likely to change its strength owing to the action of micro- organisms which grow therein in si:)ite of the presence of the poisonous arsenic. As already mentioned, the active ingredient of the bath is an arsenite, either of sodium or i)otassium. One species of microorganism is able»to take oxygen from the air and to combine it with the arsenite, thus forming an arsenate, a distinctly different compound of arsenic, and one which is much les^ poisonous to ticks. This species of microorganism appears to flourish in nearly all dip- ping baths under ordinary conditions of use and operates to gradually weaken the bath. There is, however, another si^ecies of microorganism which occa- sionally makes itself manifest in baths through which cattle are passed in ex- ceptionally large numbers or at frequent intervals, and which operates in pre- cisely the opposite manner, namely, to reduce any arsenate which may be present to arsenite, thus rendering the bath stronger. The chemical analysis of arsenical baths with sufficient accuracy for practi- cal purposes is not a difficult matter. It does, however, require some chemical training and equipment If State officials concerned with dipping can not make provision for the execution of analyses, it should not be difficult to find someone — physician, veterinarian, pharmacist, instructor in school or college, or even a student — who. for a fee. which might be comparatively small if a sufficient number of samples' from various sources could be counted on, would find it worth while to undertake this work. It is desirable to have the " actual arsenious oxid " — that is, the amount of arsenic existing as arsenite — determined at least once a month, and the " total arsenious oxid " — that is, the amount of arsenic existing as both arsenite and arsenate — determined at least every two months. To avoid danger of poisoning cattle, it is safer to discard the bath entirely whenever the "total arsenious oxid" would rise above 0.25 per cent for the low-strength bath or above 0.30 per cent for the high-strength bath after the bath had been adjusted to contain the proper amount of " actual arsenious oxid." In taking samples for analysis certain precautions are necessary. First, the bath must be well stirred; next, the sample is filled at the vat side into the bottle in which it is to be sent to the analyst. The bottle should hold not less than 4 fluid ounces (one-fourth, pint) and should be filled up to the neck. Unless the sample can be placed in the hands of the analyst in a very few hours it should be treated with formaldehyde to preserve it from the action of microorganisms which may affect the arsenic and which may work very rapidly in the sample after its removal from a comparatively cool location under- ground and exposure to hot summer weather. A little concentrated formalde- hyde solution (37 per cent) may be cheaply obtained from the druggist, to- gether with a medicine dropper. The formaldehyde is to be carefully added to the sample with the medicine dropper, in the proportion of exactly .5 drop-s to each 4 ounces of sample (20 drops to a pint). The bottle is then to be immediately corked, the cork and lip of bottle wiped dry and completely covered with melted sealing wax, rosin, or some similar material, in order to exclude air. A few matches will furnish the heat necessary for melting the sealing material. The analyst should be informed of exactly what steps were taken in preparing the samples, and the latter should be shipped to him without delay. ' 1 Department of Agriculture Bulletin 76. 10 FAKMERS' BULLETIN 603. There are two methods of attacking the problems of rejilenishing a bath and of correcting its strength — (1) method by weight and (2) method by volume. The method hy weight. — This method bases all calculations upon the weight of white arsenic which actually is in the vat and the weight which ought to be in the vat. Table 1 * gives the weight of white arsenic which is actually present in baths of various volumes and of varying percentages of arsenious oxid. When the quantity of bath in the vat lies outside the range of the figures given in Table 1 it will only be necessary to multiply or to divide by 2. For example, if the bath amounts to 750 gallons it must evidently hold only half as much arsenic as if it amounted to 1,500 gallons. If, on the other hand, it is desired to more accurately employ figures which lie between those given in the table, either for volume of bath or for percentage or weight of arsenic, it is only necessary mentally to split the difference between the figures actually given. The manner in which Table 1 is used may be illustrated as follows : Suppose one needs to replenish and correct a bath which is containetl in a vat holding 1,500 gallons to the full water line. He finds that he has in the vat 1,050 gallons of bath which his analyst informs him contains 0.14 per cent actual arsenious oxid. Looking up these figures in the table, he finds that they indicate 12^ pounds of arsenious oxid in the vat. What he wants is a vat filled with solution of proper dipping strength, we will say, of the low- strength formula. Now, the low-.strength formula calls for 0.19 per cent actual arsenious oxid, and, as before stated, his vat holds 1,500 gallons to the* full water line. Looking up these figures in the table, he finds that his vat when filled with solution of proi^er strength must contain 23| pounds of arsenious oxid. Therefore, in filling his vat to the full water line he must introduce 23f less 12i pounds of white arsenic, or 11^ i>ounds. Having found from Table 1 the weight of white arsenic necessary to add to the vat, subsequent procedure depends upon the kind of dip used. In the case of boiled dip prepared on the spot, it is simply necessary to weigh out the proper amount of arsenic and to boil it with the corresponding amount of sodium carbonate, water, etc. In case the low-strength boiled arsenic stock is to be employed, it is necessary to remember that it carries 1 pound of arsenious oxid in every 3^ gallons. Therefore, multiply the number of pounds of white arsenic needed by 3^ in order to find the number of gallons of low-strength boiled arsenic stock to be added. In C4ise of the S-B ar.senic stock, there is present 2 pounds of arsenious oxid in every gallon. Therefore, divide the number of pounds of white arseni(; desired by 2 in order to obtain the corresponding numlM?r of gallons of S-B arsenic stock. The high-strength lM)iled ai^senic stock, of course, carries 1 ])onnd of white arsenic in each 2 A gallons. 1 Credit for this form of UI>1o 1b due (o Dr. G. A. Ilandloj', votorlnnry Inspector In this burcuu. ABSENIOAL CATTLE DIPS. 11 Table 1. — Table for finding pounds of ivhite arsenic in vat. Liquid in vat. Per cent actual arsenious oxid in bath. Gallons. 1,000.... 1,050.... 1,100„... 1,150.... 1,200.... 1,250.... 1,300.... 1,350.... 1,400.... 1,450.... 1,500.... 1,600.... 1,700.... 1,800.... 1,900.... 2,000.... Lbs. 10 m 11 Hi 12 12i 13 m 14 Hi 15 16 17 18 Lbs. Hi 12 13 13J 14 Ui 15 15i 16i 17i 18i 191 21i Lbs. Hi m 12f 14 14i 15 15i 16i m 19f 21 22 231 Lbs. 14 14i 15i 16i 17 m m 19 19i m 211 22i 24 25J 26| 281 Lbs. 20f 21J 22f 24 25 26 27 1 This column may be taken as representing, nearly enough, correct weights of white arsenic for the low- strength bath. ' This column represents correct weights of white arsenic for the high-strength bath. The method by volume. — This method naturally applies only to the use of stock solutions, not to cases where the desired amount of white arsenic is to be weighed out and dissolved on the spot. The facts needed to start on are exactly the same in both methods; that is, one must know the capacity of the vat at the full water line, the amount of bath actually in the vat, and its strength expressed as per cent of actual arsenious oxid. The problem really resolves itself into correcting the strength of the bath already in the vat, for when this has been done it is simply necessary to fill up the remaining space in the vat with bath of the regular strength. Calculations are simplified by the use of Table 2. Table 2.— Amount of arsenic stock necessary to correct each 100 yaUon.s bath. I Per cent actual arsenious oxid m bath. For low-strength bath- For high-strength bath- Add low- strength boiled arsenic stock. Add S-B arsenic stock. Add high- strength boUed arsenic stock. Add S-B arsenic stock. Per cent.^ Qallons. GaJhyns. QaUons. Gallons. 0.10 2.46 0.38 G) G) .11 2.18 .34 (') G) .12 1.91 .29 2.62 0.50 .13 1.64 .25 2.40 .46 .14 1.36 .21 2.18 .42 .15 1.09 .17 1.96 .38 .16 .82 .13 1.74 .34 .17 .55 .08 1.53 .29 .18 .27 .04 1.31 .25 .19 .20 .21 1.09 .87 .65 .21 .17 .13 .22 .44 .08 .23 .22 .04 1 A bath less than half the desired strength should be discarded entirely. 12 farmers' bulletin 603. To show the manner uf usiug Tiible ~, the same example may be taken as served to illustrate Table 1, namely, a 1,500-gallon vat that contains 1,050 gallons of hath ;inaly7.iiig 0.14 per cent actual arseuious oxid. which is to be brought to the full water line with standard low-strength bath. Supix)se that low-strength boiled arsenic stock is to be employed. From Table 2 it will be found that each ItJO gallons of 0.14 i>er cent bath requires 1.30 gallons of low-strength boiled ar.senic stock to bring it to the right strength, so for 1,050 gallons there is needed 104X1.36=14.28 gallons of stock, which would bring the whole volume to 1,050+14=1,064 gallons of proper strength bath. There is then left 1.5