Recent Progress in Insecticides and Fungicides - ACS Publications

fight against these enemies, from the attack of which prac- tically nothing is immune, ... greater intensity than ever before if he hopes to survive t...
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October, 1924

INDUSTRIAL A N D ENGINEERING CHEMISTRY

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Recent Progress in Insecticides and Fungicides' By C. C. McDonnell BUREAUOF CHEMISTRY,WASHINGTON, D. C.

HE manufacture of insecticides and fungicides was, in former years, carried on largely in connection with some other manufacturing enterprise. The industry has largely outgrown this condition, however, and a number of firms are now engaged exclusively in the manufacture of these materials. It has become a n industry of vast importance to the comfort and welfare of mankind. Intensive culture, which accompanies civilization, encourages the multiplication of insects and fungi, and man's fight against these enemies, from the attack of which practically nothing is immune, must of necessity be waged with greater intensity than ever before if he hopes to survive their onslaughts. This fight is and will doubtless coqtinue to be primarily one of chemical warfare. When we consider the many factors involved in the application of insecticides and fungicides-such as light, temperature, moisture, the gases of the atmosphere, compounds secreted by the plant, etc., in relation to their effect both on the living plant and on the insect or disease to be controlledit is easy to realize that many of the problems encountered will tax the ingenuity of the most expert scientists. A number of noteworthy contributions, and many of lesser importance, have recently been made. Only a limited number of these, however, can be briefly summarized here.

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INSECTICIDES

ARSENICALS WHITE ARSENICAXD CALCIUM ARSENATE-The rapid increase in the use of calcium arsenate and other arsenical insecticides, particularly lead arsenate, has resulted in a great increase in the consumption of white arsenic, and this compound, which was formerly despised and damned by the smelting industry and by agriculturists surrounding the smelters, has risen t o a place of great economic importance. New arid more efficient methods of recovery are being devised, and ores formerly discarded as worthless on account of their high arsenic content are now being eagerly sought. Any factor which bears on the production of white arsenic directly affects the insecticide industry, since this compound is the basis of all arsenical insecticides. A marked advance in the manufacture of arsenic acid was the substitution of large nitrating kettles made of high-silicon iron,],* which is very resistant to the action of the nitric acid used in the oxidation, for the old-style earthenware pots in which the white arsenic was oxidized. This substitution has made possible the production of the. material in much larger batches and the introduction of mechanical feeding of the arsenic. Another advance has been the substitution of acid-proof brick masonry towers for terra-cotta tile towers for the recovery of the nitric acid. I n the oxidation of white arsenic with nitric acid, manufacturers have always experienced more or less difficulty, many Latches reacting very slowly and some of them practically not a t all. Some have attributed this to chemical impurities, while others considered that it was due to the physical condition of the white arsenic, and frequently entire shipments of such sluggish acting arsenic have been 1 Received

* Numbers

August 30, 1924. refer to bibliography at end of article.

rejected or diverted to other uses. Smith and Miller2 have shown that the cause of the great variation in the facility with which arsenious oxide is acted upon by nitric acid in the oxidation process is the presence of small amounts of mercury in the arsenic. An amount of mercury as small as one part in several thousand is sufficient to interfere seriously with the reaction. They have also shown that this can be counteracted by the addition of very small amounts of hydrochloric acid (or sodium chloride). A patent has recently been issued to B e h ~ e covering ,~ the use of hydrochloric acid, in certain definite proportions, for hastening this reaction. Several new methods for the manufacture of calcium arsenate have been devised. One of these, which is being operated, utilizes a deposit of ferric arsenate, occurring near Salt Lake, Utah, as the source of arsenic. The method consists briefly in decomposing the iron arsenate with caustic soda solution, filtering from the ferric hydroxide, treating the filtrate with lime, and removing the precipitated calcium arsenate by filtration. The filtrate containing the liberated caustic soda is concentrated and used again. A process by which calcium arsenate is produced in one step has recently been ~ a t e n t e d . It ~ consists in mixing pulverized quicklime with a concentrated solution of arsenic acid in such proportions that the heat generated is sufficient to drive off what little water is present, producing a dry product which requires no further heating. A patent has been issued to Dickey,j covering the use of salt (sodium chloride) to hasten the reaction between the lime and arsenic acid and claiming to produce a product containing little water-soluble arsenic, and Drefahl and Sakryd6 have obtained a patent covering a process for making a more stable calcium arsenate by working a t certain definite temperatures. Ellis and Stewart' have obtained a patent for making calcium arsenate by passing chlorine into an aqueous suspension of white arsenic to form arsenic acid, and reacting on the arsenic acid with hydrated lime. Some objections to the chlorine oxidation process in an acid solution are pointed out by M. N. and P. K.Dvornikoff,*and they propose the use of chlorinated lime (bleaching powder) on arsenious oxide, or on sodium or calcium arsenite. Tartar, Wood, and HinerQhave worked on the preparation of basic arsenates of calcium. They describe the preparation, by hydrolysis of tricalcium arsenate or calcium ammonium arsenate, of a basic calcium arsenate of the formula 3Ca3(AsOd)z.Ca(OH)z. Smith and Hendricks'o have developed a method for determining free lime in commercial calcium arsenate, and McDonnell, Smith, and Coadl' have investigated the chemical changes that take place in calcium arsenate when packed and stored under different conditions. Fernald and BourneI2 present data on the results of experiments with calcium arsenate to determine the relation of weather conditions to foliage injury on peach, pear, plum, cherry, apple, and elm trees. The report includes foliage injury studies with lead arsenate, magnesium arsenate, and zinc arsenite. An extensive investigation of the factors influencing arsenical injury to plants has been made by Swingle, Morris, and Burke.l3 Their work included experiments with cal-

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cium arsenate, lead arsenate, zinc arsenite, and other arsenicals, and mixtures of these with soap, gelatin, lime-sulfur solution, tobacco extract, and lime. Smith14 has determined that the salts exuded from the leaves of the cotton plant may, in the presence of moisture from dew or rain, have a marked influence on the action and effect of calcium arsenate on the plants and perhaps also on its toxicity to the weevils. This factor in the application of insecticides and fungicides is one that has not been recognized hitherto. LEADARSENATE-New processes for the manufacture of lead arsenate are electrolytic processes described by Tartar and Grant,15 and by Cullen and Harper,’6 and a process described by McDougall and Howlesl7 in which colloidal lead oxide is made in a Plauson colloid mill and arsenic acid added, the iemperature being maintained a t 80” to 100” C., until combination takes place, which is completed in a few minutes. A method for the preparation of a basic lead arsenate of definite composition is given by Streeter and Thatcher.l 7 O Brinleyls describes a method of preparing colloidal arsenate of lead by mixing solutions of lead nitrate and disodium arsenate in the presence of a protective colloid, such as gelatin. Pinckneylg investigated the action of soaps made from stearic and oleic acids on commercial dilead and trilead arsenates. Both soaps dissolved arsenic from the lead arsenates, but the dilead arsenate was more readily attacked and sodium stearate was much more active as a solvent than sodium oleate. A chemical study of the reactions between lead arsenate and lime sulfur solution, with particular reference to the protective action of colloids, has been made by Thatcher and Streeter.lga PARIS GREEN-Paris green has been used in recent experiments for the control of the malarial mosquito, applied as a dust by means of airplanes, in swampy land and bayous near Mounds, La.20 MAGNESIUMARSENATE-Barstow and CottringerZ1 describe a process for making magnesium arsenate from arsenic acid and magnesium hydroxide, or other magnesium compounds, by autoclaving the mixture a t a temperature above 100” c. Investigations by Howard22on methods of control of the Mexican bean beetle have shown that magnesium arsenate gives the best results. MISCELLANEOUS ARsEruIcALs-Much ‘work has been done by Parker,23Swenk and Wehr,24and Corkins25on the use of various arsenic compounds as grasshopper poisons, and they also investigated the effectiveness of a number of essential oils and other compounds as attractants or baits for these insects. Cook and McIndoo26 have conducted an investigation of the chemical, physical, and insecticidal properties of arsenicals, including the compatability of certain combinations of insecticides and of insecticides and fungicides, the adhesive and suspension properties of calcium and lead arsenates and Paris green, and the toxicity of various arsenicals to different insects.

OILEMULSIONS The most important advance in the field of oil emulsion sprays has been the development of emulsions made from heavy mineral oils, usually called lubricating oil emulsions, and their application to the control of San Jose scale. The use against San Jose scale of lubricating oil emulsions, of the type found by Yothem27 to control the citrus scale and the orange white fly, was first suggested by Quaintance28because of the fact that for several years prior to 1922 the San Jose

Vol. 16, No. 10

scale had been unusually destructive and its control by limesulfur had not been satisfactory. Investigations by Haseman and Sullivan,29A ~ k e r m a nFlint,s1 , ~ ~ and have demonstrated the value of this product for the control of San Jose scale. Weigel and Broadbent33 successfully employed it as a control for Florida red scale on palms and other ornamental plants, and C ~ m p t o nalso ~ ~ investigated its use for greenhouse scale insects. Burroughs,36and Burroughs and Grube36 describe a method of making lubricating oil emulsions without heating and without the use of soap. They employed as emulsifying agents freshly made Bordeaux mixture, iron sulfate-lime mixture, calcium caseinate, and saponin. They state that such emulsions have an advantage in that they do not break down with hard water, and that they are somewhat cheaper and easier to prepare than oil-soap emulsions. O’Byrne37discusses the preparation and application of Bordeaux-oil emulsions as a combined insecticide for scale insects and as a fungicide. Winston, Bowman, and Y o t h e r P also recommend the use of a combination of Bordeaux mixture and oil emulsion for citrus trees as a fungicide, and for scale insects and the white fly. A study of the constitution of oil emulsions by Griffin39~40 showed that the soap forms a very thin (unimolecular) film around the droplets of oil in the emulsion, thus preventing them from coalescing. Excess alkali prevents hydrolysis of the soap on dilution and aids in stabilizing the emulsion.

PLANT INSECTICIDES NIcoTIm-The most important advance in the use of nicotine preparations in recent years was the introduction by R. E. Smith,41in 1917, of so-called nicotine dusts. These dusts consist of a finely powdered inorganic carrier, kaolin being the material first employed, with which is incorporated nicotine sulfate or free nicotine solution. Kaolin was found to be objectionable in that it adsorbed and held back too much of the nicotine. Various other ‘carriers were tried, among them hydrated lime, quicklime, refuse sugar-beet lime, powdered calcium and magnesium carbonate, finely ground sulfur, gypsum, talc, and diatomaceous earth. These were found to vary in effectiveness, but the reasons were not understood, and it soon became evident that there were a number of factors in connection with the preparation and use of these materials which must be investigated before they could become a commercial success. The dust that volatilizes the largest percentage of its nicotine content within a certain time is the most effective as an insecticide. Extensive work has been done by Headlee and Rudolphs42343 on the effect of the chemical and physical nature of the carrier, the influence of alkalinity, moisture, and temperature on the rate of evolution of the nicotine and on the relation of the killing power to the rate and extent of the liberation of the nicotine when applied to the plants. They state that for carriers impregnated with nicotine sulfate the evolution of nicotine is mainly dependent upon chemical reactions (decomposition of the nicotine sulfate), but that physical factors, such as surface tension, are involved also, and in the case of dusts with free nicotine only physical factors are involved. They recommend magnesium limestone (dolomite) and hydrated lime containing 10 to 30 per cent of dolomite as effective carriers for nicotine sulfate. Practically the same conclusions are reached by Thatcher and S t r e e t e ~ - . They ~ ~ divide the materials that may be used commercially as carriers for solutions of nicotine sulfate into three groups: “adsorbent” substances such as kaolin, kieselguhr, and talc, which tend to prevent volatilization; “inert” substances which have no effect other than the exposure of large surfaces to evaporation; and “active” substances, which increase the volatility of the nicotine by changing the

October, 1924

INDUSTRIAL A N D ENGINEERING CHEMISTRY

sulfate into a more volatile form, such as hydrate and carbonate of lime. Carriers for solutions of free nicotine they divide into two groups, “adsorbent” and “inert,” the latter being the more desirable for the preparation of active dusts. They stress the importance of the presence of water, stating that some free water is necessary in the case of nicotine sulfate dusts to permit the reaction by which nicotine is liberated, but that water in excess of this amount is objectionable in that the volatility of the nicotine is decreased owing to its solution in the surplus water. Some work on the loss of nicotine from nicotine dusts during storage is included. De Ong46 concludes, as a result of his work on the relation between the volatility and toxicity of nicotine in sprays and dusts, that “the volatilization curve of nicotine is almost an exact parallel of the curve of toxicity both of fumigation and spraying.. Dust carriers follow this same law.’, An investigation of the rate of loss of nicotine from nicotine dusts (prepared from nicotine sulfate and free nicotine solutions with various carriers and packed in different types of containers) has recently been completed by McDonnell and The products were stored for periods ranging from one to two years, and analyses were made a t intervals. The results showed that: (1) the loss of nicotine from dusts containing nicotine sulfate was in the following order, beginning with the lowest: kaolin, kieselguhr, talc, calcium sulfate (gypsum), calcium hydrate, and calcium carbonate; ( 2 ) dusts made up with free nicotine solution lost nicotine more rapidly than those conta’ining nicotine sulfate, but the effects of the carriers were in about the same order; and (3) canvas bags, pasteboard boxes, and paraffined boxes are unsatisfactory containers for nicotine dust preparations and should not be used. Airtight metal or glass containers only should be employed for the commercial packing of these materials. White47 and Campbell4* describe the preparation of nicotine dusts and combinations of nicotine dusts with other insecticides and with fungicides, and the action of nicotine dusts on insects. Cory and P o t t ~report ~ ~ on the various factors that influence dusting, including types of dusters, and Smith and Martin60 have devised a combined mixing and dusting machine which they state possesses a number of advantages in the preparation and application of nicotine dusts. Commercial soap preparations containing nicotine have often shown great deterioration through loss of nicotine on storage. A study of this question by McDonnell and Nealon6I showed that this loss was not the result of volatilization of the nicotine, but that it was due to the formation of an insoluble resinous compound which bound the nicotine. This investigation also showed that this change in the nicotine was apparently dependent upon the physical condition of the soaps-hard soaps decomposing rapidly while soft soaps, whether potash or soda soaps, retained practically their original nicotine content for a period of four years. True nicotine soaps (nicotine oleate, nicotine coconut fatty acid soap, and nicotine castor fatty acid soap) have been prepared by Hoyt,62and a number of their chemical and physical properties determined. PYRErrHRUM-The use of pyrethrum flowers for the manufacture of insect powder has increased markedly in recent years, and much work has been done by chemists to determine the active principles of the species commonly employed for this purpose (Chrysanthemumcinerariaefolium). Yamarnot0,5~ who had already shown that it contained a high atomic alcohol, an aromatic oily substance, a liquid acid, and a solid acid, has continued his work. He purified and analyzed the liquid acid (pyrethronic acid) and suggested a structural formula for it. La Forge64isolated and determined the empirical formula of an active principle of pyrethrum which was shown

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by Richardson to be somewhat more toxic than nicotine to the insects against which it was tested. The most complete and successful work has been that of Staudinger and Ruzi ~ k awho , ~ isolated ~ from Dalmation insect powder two toxic compounds, Pyrethrin I and Pyrethrin 11, and determined their structural formulas. They are esters of the same alcohol with acids of slightly different formulas. The total amount of these compounds in insect powder was found to be from 0.2 to 0.3 per cent, in the proportions of 40 per cent of the first and 60 per cent of the second. Both have about the same toxicity as nicotine, I being slightly more toxic than 11. The authors made repeated efforts to synthesize these compounds, but were unsuccessful. Many synthetic compounds similar in structure were prepared, some of which were slightly toxic, but most of them were entirely inactive. Large quantities of insecticides, mainly for use against flies and certain other household insects, are now being prepared commercially by extracting powdered pyrethrum flowers with the lighter fractions of mineral oil (kerosene), in which the active principles are soluble. An extended monograph by JuilleP has recently been published, which covers all phases of pyrethrum, including the botany of the plant, its culture, the preparation and uses of the powder, chemical researches on its active principles, etc. DERRIs-Tattersfield and Roacho7 investigated the toxic constituents of Derris elliptica and found the most important ones to be tubatoxin, a white crystalline substance, and a resin or series of resins identical with derrid and tubain. These appear to be interrelated and to contain methoxy groups. It is suggested that the roots may be evaluated by a determination of the methoxy content of the ether extract by the method of Zeisel. These writers with Fryer and Stenton68 have studied the insecticidal properties of the toxic constituents of derris, and state that tubatoxin and the resin derrid have the same order of toxicity to certain caterpillars as has nicotine. Methods of preparing and applying these extracts as insecticides are given. Karigone and A t ~ u m i ,and ~~ TakeiGO have further investigated the chemical properties of tubatoxin, but have not definitely determined its constitution. Wells, Bishopp, and Laakeol have found derris po;vder to be very effective against fleas on dogs and cats, also against Anoplura on cattle and dogs and Mallophaga on chickens and cattle, although apparently not quite so effective as sodium fluoride on the cattle. McIndoo, Sievers, and Abbott,G2 and McIndoo and SieverP have made extended tests with derris extracts and state that it is a promising insecticide. White,6*and de One; and White,65found that dust containing 20 per cent of ground derris root controlled certain lice. LARKsPuR-In an investigation on the isolation and properties of the alkaloids and oil of larkspur seed (Delphinium consolida), Markwood66 found the seed to contain 25 per cent of oil and determined some of its physical and chemical properties. He also isolated three alkaloids in crystalline form and determined the composition and certain physical constants of two of these, for which he proposes the names “delcosine” and “delsoline,” The first named has a melting point of 198’ to 199’ C., and the empirical formula C ~ I H ~ ~ N O S , and the other a melting point of 207’ to 208’ C., and the emHe was unable to purify the pirical formula C~SH~INOB. third sufficiently to determine its formula or physical constants. An alkaloid corresponding to the first named had previously been reported by Keller,67 but the others are new. “CuBE’J-McIndoo and S i e v e d 3 tested the toxicity of the powdered roots and root extracts of a Peruvian plant, called locally in Peru “cube” or “barbasco,” and found it effective against potato beetle larvae, four species of aphids, and certain other insects. They state that it is a promising

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Vol. 16, No. 10

but sufficient tests have not as yet been made to definitely establish its value. ETHYL ACETATE-CARBON TETRACHLORIDE-A noninflammable fumigant, for the destruction of insects in insectinfested wheat and other grains, has been developed by Roark ORGANICCOMPOUKDS and Back and their co-workers87 to take the place of carbon I n addition to the organic insecticides already considered, disulfide, the use of which is very much restricted because a study of the effect of a number of organic compounds as con- of its high inflammability. This new fumigant consists tact insecticides for certain species of aphis has been made by of a mixture of ethyl acetate and carbon tetrachloride in Richardson and Smith.eS Pyridine, a-picoline, and commer- the proportions of two volumes of the former and three cial pyridine containing the higher homologs of pyridine were volumes of the latter. Of the more than two hundred and of little value as contact insecticides. The alkaloids tested, fifty compounds and mixtures tested this preparation was the with the exception of nicotine, were of low toxicity. Smith69 most satisfactory. It is effective against the more common has made an investigation of the preparation of dipyridyls insects infesting stored grains, is noninflammable, leaves no from pyridine, which he undertook primarily to discover odor or taste in the fumigated grain or products-including chemical comRounds toxic to insects. Tests of these com- bread-made therefrom if the ingredients are of sufficient pounds by Richardson showed that some of them possess purity, is readily obtainable a t a price that is not prohibitive, is nontoxic to man, and can easily be applied. The cost of high toxicity to certain plant lice. treatment with this mixture is greater than with carbon diFUMIGANTS sulfide, but the fact that it is not accompanied by risk of HYDROCYANIC ACID-Great progress has recently been fire or explosion will permit its use where that of carbon dimade in the use of hydrocyanic acid gas for insect control. sulfide would be dangerous. CHLOROPICRIN-chloropicrin has shown some promise as For citrus fumigation, liquid hydrocyanic acid has replaced hydrocyanic acid generated in the field from cyanide and a fumigant for cereal products, and its possibilities and limitasulfuric acid to the extent of 90 per cent, according to Wog- tions have been investigated by Chapman and Johnson.88 Roark and Bishopp (unpublished results) have determined, l~m.~O It is also being used to some extent in the vacuum fumigation of cotton, developed by Sasscer and Hawkins,T1 by their work on repellents for flies, more especially for the and S a s ~ c e to r ~prevent ~ the introduction into this country of screw-worm fly and other blow flies which cause great damthe pink boll worm, and in one of the fumigating plants of the age to cattle, sheep, and goats in the Southwest, that chloroFederal Horticultural Board on the Mexican border. These picrin, mixed with lubricating oil in the ratio of 1 to 100, tests have shown that it is as effective as the gas generated effectually prevents flies from visiting meat on which it has by the old method. I n the vacuum fumigation process it is been smeared. While pure chloropicrin is very corrosive in necessary, during the cold winter months, to pass the liquid its action, causing deep burns on contact with the skin, when through a volatilizer in order to be sure that the product is mixed in the oil it can be applied to extensive wounds on goats, gasified. Sasscer and Weige173 tested liquid hydrocyanic animals recognized as quite sensitive to poisons, without inacid in greenhouses and found it effective against certain juring them in any way. Furthermore, wounds treated with insects. They state, however, that “it cannot yet be safely this mixture heal quickly, indicating that chloropicrin probably has some bactericidal action. While this use of chlororecommended for use by the average florist.” Much work has been done on the fumigation of food prod- picrin is still in the experimental stage, the results obtained ucts with hydrocyanic acid gas. Simmons74 fumigated cheese to date have been very promising. More than two hundred and reported that cyanide fumigation of cheese in general chemicals have been tested by Bishopp, Cook, Parman, and should not be recommended because it may absorb the fumi- Laakesg in this investigation on attractants, repellents, and gant. Griffin and Back75reported on the amount of hydro- larvicides for the control of the screw-worm fly, black blow cyanic acid absorbed by dried fruits and various confectioners’ fly and green bottle fly. The most effective bait for use in materials packed in different ways, and on the effect of cold traps around slaughterhouses, on ranches, etc., was found to be dried egg material, mixed with water and a small amount storage on the retention of the fumigant. The U. S. Public Health Service76177has developed and of sodium carbonate, so as to cause the development of proadopted a mixture of hydrocyanic acid and cyanogen chloride tein decomposition. For practical use on animals a mixture of 1 part furfural to 4 parts pine tar oil was found to be a very for the fumigation of ships. CALCIUM CYANIDE-A recent development in fumigation effective repellent. Benzene was found to be an effective has been the introduction of a calcium cyanide product as a larvicide for application to wounds. CARBON DIsuLFrDE-Experiments by Fleminggohave shown dust. This material, according to Moore,7b contains cyanogen equivalent to 48 to 50 per cent of sodium cyanide, and is made that carbon disulfide is effective in destroying Japanese beetle by fusing calcium cyanamide with sodium chloride in an elec- larvae in the soil by introducing the material through holes tric furnace. It owes its activity, apparently, to the fact made in the soil. The treatment is not effective when the soil that in the presence of moisture it breaks down and free hy- is wet. Leach and Johnsongl controlled infestations of Japanese drocyanic acid is liberated. Quayle79.80 was apparently the beetle larvae in golf greens by applying to the turf a n emulfirst to test this product on citrus trees by blowing the finely sion of carbon disulfide, fish oil soap, and water. They state divided powder under the tented trees infested with certain that the turf will not be injured if the material is properly citrus scales. Flint,sl and Flint and Baldufs2 tested it for applied. Leach, Fleming, and Johnson,g2 as the result of the control of chinch bugs, Sasscer and Weige173 against four years’ study of soil insecticides, have developed an emulgreenhouse insects, Sullivans3against certain fleas on animals sion of carbon disulfide and wormseed oil which has proved and in closed buildings, and Wagoners4 against the rosy apple satisfactory for the control of the soil stages of the Japanese aphis. Cory and P o t t report ~ ~ ~ favorable results from its use beetle, a method which is being used commercially for the “on some crops under favorable conditions,” but state that treatment of certain nursery and greenhouse stock before “when applied to tender foliage injury is likely to ensue.” shipment. Dietz and Sngder,g3 Snyder,94 and Snyder and Zetek,96 It has also been tested as a soil fumigant by Quayleso and by Horsfal,s6 and as a barrier by Haseman and Bromley.86 have investigated methods fbr protecting wood against damage The results obtained have been in general very favorable, from termites or white ants, and suggest methods for destroycontact insecticide. They also report the results of tests with many other plants and plant products, some of which were somewhat toxic, but few of them gave promise of having much value commercially.

October, 1924

INDUSTRIAL A N D ENGINEERING CHEMISTRY

ing these insects and also for the chemical treatment of wood to prevent its being attacked. These include fumigation with hydrocyanic acid gas and volatile arsenical combinations, and the application of kerosene emulsion containing sodium arsenite, to kill the insects, and impregnation of the wood with chemicals (zinc chloride, bichloride of mercury, sodium fluoiide, and chlorinated naphthalene) to prevent insect attack. Crude carbolic acid and coal-tar creosote are recommended as effective poisons to be added to wood pulp products during manufacture. FUNGICIDES

COPPERCOMPOUNSD The outstanding work in connection with copper compounds in the control of fungous diseases has been that on the use of copper carbonate (basic copper carbonate) dust as a seed treatment of wheat for smut contr0l.g6-~~~. It has also been tested against smut on oats,100d108, but the results were not always favorable, particularly in the case of hull oats. A new fungicide, copper soap dust, prepared from copper sulfate and resin fish-oil soap, has been tested by Pritchard and Porte'og against tomato leaf spot in comparison with Bordeaux mixture, and found to be equally satisfactory. They state that it is cheaper than liquid Bordeaux, considering the greater ease and rapidity of application, and "because of its excellent chemical, physical, and fungicidal properties, it offers promising possibilities." Butler and Smith'lo have investigated the acetates of copper as fungicides and report that they "are excellent fungicides and deserve special consideration when a colorless deposit is required." These investigators also state that the basic acetate adheres better than the neutral acetate, and that the addition of gelatin markedly increases the adhesiveness. Butler111.1i2has also studied the chemistry and physical properties of Bordeaux mixture and its physiological effects when sprayed on plants. Cook113 investigated the influence of copper sprays on the yield and composition of Irish potato tubers, and showed that a larger yield of potatoes was secured from copper sprayed plants (in the absence of late blight) than from nonsprayed vines. Doranl'4 has studied the toxicity of various copper fungicides, and Hookerl'5 has made a colloidal copper hydroxide which he states shows promise of being an effective fungicide in very low concentrations.

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Seigler and DanielP4 give directions for the home manufacture of concentrated lime-sulfur solution, including specifications for lime-sulfur cooking plants, and directions for the use of this product for spraying purposes. SPREADERS AND STICKERS

While spreaders and stickers cannot be classed as either insecticides or fungicides, they are so closely related to the effectiveness of insecticides and fungicides and have been the subject of so much discussion that some reference should be made to them. Calcium caseinate, in particular, has received much attention, and investigators have shown that it increases the evenness with which spray materials coat the leaves; but there is some difference of opinion as to its effectiveness as an aid in the control of the insects. Other spreaders and stickers tested, with more or less success, include soap, saponin, glue, and flour paste. For the results of investigations on this subject see the work of Moore,lZ6 Stearns and Hough,126and Smith.12' Robinson12*suggests the use of skim milk or skim milk powder and hydrated lime as a substitute for calcium caseinate. APPLICATION

The tendency in recent years has been to substitute dusting for wet spraying wherever possible, mainly because this method of application is cheaper and very much more rapid. The most radical change in the mode of application of insecticides has been the use of airplanes in the application of dust preparations. The first airplane experiment was made by the Ohio State Experiment Station in cooperation with the U. S. Air Service, and was reported by H o u ~ e r . ' ~It~ consisted in the application of lead arsenate dust to catalpa trees for the control of the catalpa sphinx. The results were highly successful. Extensive experiments have since been made on the use of airplanes for the application of calcium arsenate to cotton for the control of the cotton leafworm and the boll weevil. A full account of this work is given in a recent report by Coad, Johnson, and M ~ K e i l . ~ These ~o writers are of the opinion that under certain conditions the commercial application of this process for boll weevil control is not improbable. The airplane has also been used in the application of Paris green for the control of the malarial mosquito.20 Work on the relation of hard and of alkaline waters to the preparation and dilution of sprays and dips has been reported by de Ong.1311132 He points out that hard and alkaline MERCURY COMPOUNDS waters may form dangerous combinations with certain inA number of organic compounds of mercury (mostly deriv- secticides and that softening hard waters with chemicals is atives of phenol or phenol homologs) have been investj- only partially successful, and gives directions for installing gated in connection with the treatment of seed wheat and a water softening plant. of the particles of insectiother grains for smut ~ 0 n t r o 1 , with ~ ~ generally ~ ~ ~ ~fa-~ ~ The ~ - effect ~ ~ of ~ the ~ ~electrification ~ ~ ~ cides applied as sprays and the influence of the negative vorable results. electric charge exhibited by wet leaf surfaces has been conSULFURAND LIME-SULFUR SOLUTION sidered by M 0 0 r e . l ~ ~He also describes methods of preparing a p e r i m e n t s on the fungicidal action of sulfur by Doran121 certain arsenical insecticides so that the particles will carry have shown that sulfur is toxic only in the presence of oxygen, a positive charge, with the idea of producing a material that that the! active principle is volatile, and that precipitated will adhere better. are being made by CoadL30and his co-workers sulfur is more toxic than finely ground sulfur. Y o ~ n g , ~ ~ ~ ~Experiments ~23 a t Tallulah, La., on the effect of the electrification of dust as a result of his extensive researches on the toxic property of sulfur, concludes that toxicity is exhibited only when oxygen particles on distribution and adherence to the plants. and water are present and is due to the formation of pentaBIBLIOGRAPHY thionic acid, a volatile oxidation and hydration compound of sulfur. Finely divided sulfur is more readily oxidized to 1-Ambruster, Chem. Met. Eng., 27, 159 (1922). 2-Smith and Miller, paper presented a t the 67th Meeting of t h e pentathionic acid than flowers of sulfur-a fact which explains the greater effectiveness of colloidal sulfur. A con- American Chemical Society, Washington, D. C., April 21 t o 26, 1924. U. S. Patent 1,493,798 (May 13, 1924). 3-Behse, siderable amount of work was done both on the making of 4-Ellis and Stewart, U. S. Patent 1,447,938 (March 6, 1923). colloidal sulfur and on its use as a fungicide. U. S. Patent 1,434,650 (November 7, 1922). 5-Dickey, '

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6-Drefahl and Sakryd, U. S. Patent 1,475,545 (November 27, 1923). 7-Ellis and Stewart, U. S. Patent 1,447,203 (March 6, 1923). M. N. and P. N., Chem. Met. Eng., 29, 1058 (1923). 8-Dvornikoff, g-Tartar, Wood, and Hiner, J . A m . Chem. Soc., 46, 809 (1924). 10-Smith and Hendricks, Ind. Eng. Chem., 16, 950 (1924). 11-McDonnell, Smith, and Coad, U.S. Dept. Agr., Bull. 1116 (1922). 12-Fernald and Bourne, Mass. Agr. Expt. Sta.; Bulls. 207 and 210 (1922). 13--Swingle, Morris, and Burke, J . Agr. Research, 24, 501 (1923). 14-Smith, Ibid., 26, 191 (1923). 15-Tartar and Grant, J. Ind. Eng. Chem., 14, 311 (1922). 16-Cullen and Harper, Ibid., 14, 651 (1922). 17-MeDougall and Howles, British Patent 204,223 (September 27,1923). 1 7 e S t r e e t e r and Thatcher, Ind. Eng. Chem., 16, 941 (1924). 18-Rrinley, J . Agr. Research, 26, 373 (1923). Ibid., 24, 87 (1923). 19-Pinckney, lQa-Thatcher and Streeter, N. Y.Agr. Expt. Sta., Bull. 621 (1924). 20-Anonymous, U.S. Dept. A g r . , ,O$icial Record, 3, No. 10, p. 2; No. 13, p. 6 (1924). 21-Barstow and Cottringer, I J . S. Patent 1,466,983 (September 4, 1923). U.S. Dept. Agr., Bull. 1407, 8 (1924). 22-Howard, 23--Parker, Mont. Agr. Expt. Sta., Bull. 148 (1922). 24-Swenk and Wehr, Nebr. Agr. Expt. Sta., Bull. 183 (1923). 25-Corkins, Col. Agr. Expt. Sta., Bull. 280 (1923). 26-Cook and McIndoo, U. S. Dept. Agr., Bull. 1147, Rev. (1924). 27-Yothers, Ibid., Farmers’ Bull. 933, Rev. (1922). Ibid., Clip Sheet 193 (1922). 28-Quaintance, . 29-Haseman and Sullivan, Mo. Agr. Expt. Sta., Circ. 109 (1923). U. S. Deet. Agr., Circ. 263 (1923). 30-Ackerman, J . Econ. Entomol., 16, 209 (1923). al-Flint, 32-Davis, Ibid., 17, 285 (1924). 33-Weigel and Broadbent, Ibid., 17, 386 (1924). 34-Compton, Ibid., 17, 225 (1924). 3 b B u r r o u g h s , Mo. Agr. Expt. Sta., Bull. 206 (1923). 36-Burroughs and Grube, J. Econ. Entomol., 16, 534 (1923). 37-O’Byrne, Flu. Plant Board Quarterly Bull. 6 (1922). 38-Winston, Bowman, and Yothers, U.S. Dept. Agr., Bull. 1178 (1923). 39--Griffin, J. A m . Chem. Soc., 46, 1648 (1923). 40-Griffin, J . Econ. Entomol., 16, 430 (1923). 41-Smith, Calif. Agr. Expt. Sta., Bzdl. 336 (1921). 42-Headlee and Rudolphs, J. Econ. Entomol., 15, 75, 421 (1922). 43-Headlee and Rudolphs, N . J. Agr. Expt. Sta., Bull. 381 (1923). 44-Thatcher and Streeter, N. Y. Agr. Expt. Sta., Bull. 601 (1923). 45-De Ong, J. Econ. Entomol., 16, 486 (1923). 46-McDonnell and Young, U. S. Dept. Agr., Bull. 1812 (1924). 47-White, Ibid., Circ. 224 (1922). 4&Campbell, Ibid., Farmers’ Bull. 1282 (1922). 49-Cory and Potts, Md. Agr. Expt. Sta., Bull. 261 (1924). 50-Smith and Martin, Calif. Agr. Expt. Sta., Bull. 367 (1923). 51-McDonnell and Nealon, Ind. Eng. Chem., 16, 819 (1924). 52-Hoyt, paper presented a t the 67th Meeting of the American Chemical Society, Washington, D. C., April 21 t o 26, 1924. 53-Yamamoto, J . Chem. Soc. ( J a p a n ) , 44, 311 (1923). 54-La Forge, U.S. Dept. of Agr., Oficial Record, S, No. 22, p. 4 (1924). 56-Staudinger and Ruzicka, Heluetica Chim. Acta, 7, 177, 377 (1924). 56-Juillet, “Le Pyrethre Insecticide de Dalmatie,” RoumCgous et Dehan, Montpellier, France, 1924. 57-Tattersfield and Roach, Ann. Applied Biol., 10, 1 (1923). 58-Fryer, Stenton, Tattersfield, and Roach, Ibid., 10, 18 (1923). 59-Karigone and Atsumi, J . Pharm. Soc. (Japan), 491, 10 (1923). 60-Takei, Bull. Inst. Phys. Chem. Research ( J a p a n ) , 2, 485 (1923). 61-Wells, Bishopp, a n d Laake; J. Econ. Entomol., 16, 90 (1922). 62-McIndoo, Sievers, and Abbott, J. Agr. Research, 17, 177 (1919). 63-McIndoo and Sievers, U. S. Dept. Agr., Bull. 1201 (1924). 64-White, University of California Agr. Expt. Sta., Rep. 1922-23, 132. 65-De Ong and White, J. Econ. Entomol., 17, 499 (1924). J . A m . Pharm. Assoc., lS, 696 (1924). 66-Markwood, 67--KeIler, Arch. Pharm., 248, 468 (1910). 68-Richardson and Smith, U. S. Dept. Agr., Bull. 1160 (1923). 69-Smith, J. A m . Chem. Soc., 46, 414 (1924). 7&Woglum, J. Econ. Entomol., 16, 518 (1923). 71-Sasscer and Hawkins, U.S. Dept. Agr., Bull. 186 (1915). 72-Sasscer, Federal Horticultural Board Service and Regulatory Announcements, 21, 82 (1916). 73-Sasscer and Weigel, J. Econ. Entomol., 17, 214 (1924). 74-Simmons, Ibid., 17, 416 (1924). 75-Gri5n and Back, U. S. Dept. Agr., Bull. 1307 (1924). ’?B-Anonymous, Ind. Eng. Chem., 16, 267 (1924). S. Quarantine Regulations, Public Health Service, Amendment 77-U. No. 6, January 16, 1923. 78-Moore, J . Econ. Entomol., 17, 104 (1924). 79-Quayle, Calif. Cultivator, 61, N o . 1, p. 3 (1923). J . Econ. Entomol., 16, 327 (1923). BO-Quayle, 81-Flint, Ibid., 16, 328 (1923). 82-Flint and Balduf, 111. Agr. Expt. Sta., Bull. 249 (1924). J . Econ. Entomol., 17, 230 (1924). 83-Sullivan,

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84-Wagoner, Ibid., 17, 417 (1924). 85-Horsfal, Ibid., 17, 160 (1924). 86-Haseman and Bromley, Ibid., 17, 324 (1924). 87-Roark and Back, U. S. Dept. Agr., Bull. 1313 (1924). 88-Chapman and Johnson, paper presented a t the 67th Meeting of the American Chemical Society, Washington, D. C., April 21 to 26, 1924. 89-Bishoppp, Cook, Parman, and Laake, J. Econ. Entomol., 16, 222 (1923). 90--Fleming, N. J. Agr. Expt. Sta., Bull. 380 (1923). 91-Leach and Johnson, Bull. Green Section U. S. Golf Assoc., 3, 262 (1923). 92-Leach, Fleming, and Johnson, J. Econ. Entomol., 17, 361 (1924). 93-Dietz and Snyder, J . Agr. Research, 16, 279 (1923). U. S. Dept. Agr., Bull. 1231 (1924). 94-Snyder, 95-Snyder and Zetek, U.S. Dept. Agr., Bull. 1131 (1924). 96-NKackie and Briggs, Phytopathology, 11, 38 (1921). 97-Mackie and Briggs. Calif. Agr. Expt. Sta., Bull. 364 (1923). 98-Heald and Smith, Wash. Agr. Expt. Sta., Bull. 171 (1922). 99-Barss, Ore. Agr. Expt. Sta., Circ. 30 (1922). 100-Lambert and Bailey, Phytopat+ology, 12, 36 (1922). 101-Lambert and Bailey, Ibid., 13, 169, 293 (1923). 102-Coons, Ibid., 18, 37 (1923). 103-Heald, Zundel, and Boyle, Ibid., 18, 169 (1923). 104-Fraser and Simmonds, Ibid., 13, 293 (1923). Ibid., 14, 42 (1924). 105-Kirkby, 106-Tisdale, Taylor, and Lenkel, Ibid., 14, 43 (1924). 107-Howitt and Stone, I b i d . , 14, 346 (1924). lOS-Dickson, Summerby, and Coulson, Ibid., 14, 350 (1924). 109-Pritchard and Porte, Ibid., 11, 229 (1921). 110-Butler and Smith, Ibid., 12, 279 (1922). 111-Butler, N. H. Agr. Expt. Sta., Tech. BUZZ.21 (1922). 112-Butler, Ind. Eng. Chem., 16, 1039 (1923). U.S. Dept. Agr., Bull. 1146 (1923). Il3-Cook, Phytopathology, 13, 532 (1923). 114-Doran, 115-Hooker, Ind. Eng. Chem., 16, 1177 (1923). 116-Tisdale and Taylor, Phytopathology, 13,38 (1923). Il7-Tisdale, Taylor, and Griffiths, Ibid., 13, 153 (1923). 118-Johnson, Linkel, and Dickson, Ibid., 14, 42 (1924). 119-Johnson and Melchers, Ibid., 14, 44 (1924). 120-Reddy and Halbert, Ibid. 121-Doran, N. H. Agr. Expt. Sta., Tech. Bull. 19 (1922). 122-Young, Annals Mo. Bot. Garden, 9, 403 (1922). 123-Young, paper presented a t the 07th Meeting of the American Chemical Society, Washington, D. C., April 21 to 26, 1924. 124-Seigler and Daniels, U. S. Dept. Agr., Farmers’ Bull. 1286 (1922). 125-Moore, University of Minnesota Agr. Expt. Sta., Tech. Bull. 2 (1921). 126-Stearns and Hough, J . Econ. Entomol., 16, 198 (1923). 127-Smith, Ibid., 16, 201 (1923). 128-Robinsor1, Ibid., 17, 386 (1924). 129-Houser., I b i d . , 16, 241 (1923). 130-Coad, Johnson, and McNeil, U.S. Dept. Agr., Bull. 1204 (1924). 131-De Ong, Calif. Agr. Expt. Sta., Bull. 338, 301 (1921). 132-De Ong, J . Econ. Entomol., 16, 339 (1922).

Explosives Bulletins A series of bulletins on the safest and most efficient methods for using explosives, based on the experience of its experts, has been issued by E. I. du Pont de Nemours & Company of Wilmington, Del. These are known as Explosives Service Bullftzns and aim to give to explosives consumers the most thorough information on how to secure the best results in blasting. The bulletins issued to date include : Safety Fuse. Some suggestions for its handling and use t o insure best results in blasting. Some Practical Pointers on Blasting Cod. An Aid for Tunnel Driving. An easy method for prGperly directing the holes for V cuts. 9 Firing Quarry Shots. Some practices which will increase breakage and prevent misfires. Getting the Best Results with Permissible Explosives. Velocity of Detonation of Various Types of Explosives. Brands of d u Pont Explosives a n d Use to Which They Are Adapted. Danger in Using Permissible Explosives for Mudcapping in Dry and Dusty Coal Mines. Advantageous Practices in Tunneling. Some practical ways of securing greater progress in tunnel operation and lower costs. The Production of More Merchantable Coal. Some important factors in blasting coal with permissibles which can be controlled by mine officials Springing Bore Holes. Recommendations for increasing the efficiency and safety of this operation. Tamping Bore Holes in Metal Mines. Some arguments in favor of a practice too little used. Care of Explosives from Storage Magazine to Bore Hole.