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Water Soluble Arsenic in Spray Material

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Water Soluble Arsenic in Spray Material BULLETIN 448 IvlARCH, 1930 Water Soluble Arsenic in Spray Material H. C. Young OHIO AGRICULTURAL EXPERIMENT STATION Wooster, Ohio CONTENTS General Discussion of Spray Injury . • . • • 3 Water Soluble Arsenic in Lime-sulfur and Arsenate of Lead Mixtures. • . • 5 Water Soluble Arsenic in Lime-sulfur and Lead Arsenate Mixtures to Which Correctives Were Added .................................... 10 Water Soluble Arsenic in Dry Lime-sulfur-Lead Arsenate Mixtures to Which High Calcium Lime Was Added ............................. 14 Water soluble Arsenic in Lime-sulfur-Manganar M1xture ................ 14 Soluble Arsenic in Mild Sulfur Sprays With Lead Arsenate and Manganar.. 16 Effect of Wetting and Drying on Formation of Soluble Arsenic in Various Spray Mixtures . • . • • . • • . • • . • . • • . • • • • • • • . • • • • • • • • • . • • . 17 Effect of Temperature During Drying on Formation of Soluble Arsenic in Lime-sulfur and Arsenate of Lead Mixtures . • . • • • • • • • • • • . • • . • . 18 Effect of Period of Drying on Formation of Soluble Arsenic in Lime-sulfur and Lead Arsenate Mixture . 18 Discussion of Results . 18 Summary ........................................................... 21 Literature Cited . • . ................................. 22 (1) This page intentionally blank. WATER SOLUBLE ARSENIC IN SPRAY MATERIALS H. C. YOUNG Injury to fruit and foliage from spray materials is becoming exceedingly common. Too frequently the loss incurred by such injury is as large or larger than could have been expected from the pests to be controlled. For many years bordeaux mixture was the standard spray for most types of fruit but, today, it is used only when absolutely necessary. Its disuse has been brought about, not because of a lack of efficiency in controlling diseases, but because of the injury it produces. Upon demonstration of its usefulness lime-sulfur was promptly substituted for bordeaux and soon became the generally recom­ mended spray. It held this position, seemed to control well, and gave but little injury for a period of nearly 20 years. Then rather suddenly, it began to injure, and today in many fruit sections it is regarded as dangerous as bordeaux mixture. What has brought about this increasing injury by these two standard spray materials is difficult to answer. Possibly in former times much foliage injury was overlooked and a less exacting finish on fruit was demanded. Perhaps spraying was not so thoro. Many believe that trees gradually lose their tolerance to sprays, or that the injury becomes cumulative. Others think that the pres­ ent-day cultural practices and, possibly, gradually changing weather conditions are factors. At any rate, the spraying schedule of the present with its recommended standard materials is resulting in too much injury and a change is imperative. The margin of difference between tree tolerance to a fungicide or an insecticide and the killing concentration is small, making it difficult to develop materials which will be effective and yet will not injure. Possibly, this would not be so difficult if the weather did not exert its influence. In fact, a fungicide may be made up so that it will kill fungi and not injure the tree under normal temperature, say 18° C. (65° F.), but if the temperature be raised 10 degrees it may cause severe injury. On the other hand, if the temperature should drop 10 degrees the fungicide would be much less effective and no foliage injury would result. This is particularly true with sulfur sprays. The reverse occurs with bordeaux. (3) 4 OHIO EXPERilVIENT STATION: DULLETIN 448 The perfect fungicide or insecticide is one that will not injure foliage under any condition and will control under all conditions. This may be impossible, or at least very difficult to find, especially in the case of fungicides, since the parasite is a plant somewhat similar in general relations and chemical composition to the higher plant, its host. This problem was foreseen several years ago, and work was begun in this laboratory to determine chemical differ­ ences between fungi and their host plants with the object in view of finding compounds that occur in the fungus and not in the higher plant which would react to fungicides. Considerable progress has been made, but as yet no working hypothesis developed. Fruit growers, in an attempt to avoid spray injury, have used many types of substitutes. They have diluted both bordeaux and lime-sulfur. They have used many types of wettable sulfur sprays, as well as a great many proprietary remedies. Many so-called cor­ rective materials such as lime, calcium caseinate, ferrous sulfate, aluminum sulfate, zinc sulfate, and a host of others, have been used. This has resulted as a rule in poor control, not much reduction in injury, general dissatisfaction, and a large number of confusing recommendations. As far as the author is aware, there has been a somewhat limited amount of constructive study given to the problem of spray injury. Much of the work has been of the "cut and fit" nature, and little effort has been made to determine the underlying cause or causes. Part of the spraying schedule calls for a combination of some fungicide and an insecticide, and, for apples, this is usually lime-sulfur and arsenate of lead. When spray injury results, it is caused either by the fungicide or the insecticide, or a combination of both, brought about by an inter-reaction between the two. There are known cases where lime-sulfur alone has injured-Saffro (7), Wallace (13), Young and Walton (15), and others. There are also reports of arsenical injury-Fernald and Bourne (2), Smith (8), Swingle (10), Ginsburg (3), Haenseler and Martin (4), Stewart (9), and others. The combination sprays of wettable sulfur and arsenate of lead have been studied by Haenseler and Martin ( 4), and Ginsburg (3). They found the injury factor on peaches to be due to water soluble arsenic. Swingle (10) found that peaches sprayed with 0.01 percent solution of arsenic and arsenious acids were severely injured. He found that an arsenate of lead containing more than 0.5 percent water soluble arsenic would burn peach foliage, and that there was an accumulation of free arsenic in the leaf brought about by the gradual hydrolysis of the lead WATER SOLUBLE ARSENIC IN SPRAY MATERIAL 5 arsenate and its continuous absorption. Consequently, a lead arsenate containing much more than 0.5 percent water soluble arsenic may be expected to burn peach foliage. Fig. 1.-Spray injury on Jonathan apples sprayed in mid-July with 1-80 liquid lime-sulfur and 1 Y2 lbs. lead arsenate The combination spray of lime-sulfur and arsenate of lead has received less study, especially after the spray has been applied. It is well known that acid lead arsenate alone does not often burn apple foliage. An examination of this spray mixture before it is applied does not show an excessive amount of water soluble arsenic. Con­ sequently, most of the damage to apple foliage by this combination has been attributed to the lime-sulfur itself. This led to the idea that lime-sulfur should be diluted for the late sprays. However, when this was done injury was frequently even more severe, especially where lime was not added. A striking example of this 6 OHIO EXPERIMENT STATION: BULLETIN 448 occurred during the season of 1929, where a grower used a 1 to 80 liquid lime-sulfur and 11;2 pounds of lead arsenate to 50 gallons of spray. The results were disastrous, as is shown by the photo­ graphs in Figure 1. This spray was applied under moderate temperature and humidity conditions such as are considered safe for spraying, dur­ ing late July. In the same locality 2 pounds dry lime-sulfur, 2 pounds lime, and 11;2 pounds lead arsenate to 50 gallons of water caused severe injury. Upon close examination it was found that the injury in both cases was typically arsenical and not due to the action of lime-sulfur as is generally supposed. In this investigation an attempt was made to determine what happens when lime-sulfur and acid lead arsenate are mixed together before and after the material is sprayed on the tree; under what conditions arsenic becomes soluble in the mixture; also what effect is produced by such 'correctives' as calcium hydrate, calcium casei­ nate, ferrous sulfate, aluminum sulfate, and a large number of other materials that might be supposed to have corrective proper­ ties. The effects of temperature, length of time of drying, strength of material, and sulfur substitutes were tried. Manganese arsenate {Manganar) was tested as a substitute for lead arsenate. WATER SOLUBLE ARSENIC IN LIME-SULFUR AND ARSENATE OF LEAD MIXTURES Method of procedure.-The lime-sulfur-lead arsenate mixtures were made up in the usual way, by adding the lead arsenate to the dilute lime-sulfur. In all this work 1000 cc quantities of the mixture were prepared and shaken until samples were taken. Preliminary tests showed that thoro shaking was necessary for uniform results. After shaking for the required time the mixtures were :filtered and two 100 cc aliquots of the filtrate were used for each determination. The method adopted for the arsenic determi­ nations was a slight modification of those generally used and, for that reason, will be given in detail here. Aliquots of 100 cc of the :filtrate were digested with 5 cc of superoxol for 30 minutes in an autoclave with 1 to 2 pounds pres­ sure, then digested to fuming with 5 cc of concentrated sulfuric acid and filtered with as little water (30 cc) as possible. The :filtrate was diluted again to 100 cc with water and 1 gram of KI added and evaporated to about 50 cc, or until practically clear. It was next cooled, 200 cc of water added and decolorized with 1 to 2 drops of one-tenth normal sodium thiosulfate. Sodium carbOnate WATER SOLUBLE ARSENIC IN SPRAY l\'IATERIAL 7 was added to neutrality, then the mixture was slightly reacidified and made alkaline with an excess of sodium bicarbonate.
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