Historic, archived document Do not assume content reflects current scientific knowledge, policies, or practices. b 6 UNITED STATES DEPARTMENT OF AGRICULTURE Washington, D. C. v LOSS OF NICOTINE FROM NICOTINE DUSTS DURING STORAGE By C. C. McDonne tu, Chief, and H. D. Youne, Assistant Chemist, Insecticide and Fungicide Laboratory, Miscellaneous Division, Bureau of Chemistry CONTENTS Page Page Purpose of investigation__......_.--.-.------ 1 | Volatility of nicotine sulphate selution and Review. olliterature.o ge: _ eee ere ee 2 free nicotine solution_----.--_-..-.-_< 13 Outline of experiments__________--_-_-------- 24: Sunmmary=:333 9p oS LEP ES ed Pee 14 Experimental results._.........-----.-----.-- 3 I-Literature: cited... 2... 2.4. Xa 14 PURPOSE OF INVESTIGATION “Nicotine dusts,’’ since their introduction in 1917 by Smith of California (6)', have come into extensive use for the control of certain insect pests. Campbell (1) estimated that about 2,000 tons of such preparations were produced in 1923. These dusts consist of finely powdered fuller’s earth, kaolin, hydrated lime, dolomitic lime, calcium carbonate, gypsum, sulphur or other absorbent material, with which nicotine sulphate or free nicotine solution isincorporated. One seri- ous objection to such products from the standpoint of the consumer, as well as from that of the manufacturer, is that they are not stable and must be used comparatively soon after they have been made. The nicotine is lost more or less rapidly, depending principally upon the form of nicotine used, the chemical and physical nature of the absorbent, and the type of container. Under the Federal insecticide and fungicide act, all such prepara- tions entering interstate commerce must be labeled to show the percentage of nicotine present and the total percentage of inert ingredients, or, in lieu of this, the name and percentage of each inert ingredient present. The first form of statement is the more feasible and the one generally adopted. Owing to the loss of nicotine from these preparations as now manufactured and packed, it is difficult for the manufacturer to market a product that will remain stable. The consumer, therefore, may unknowingly use a product that has lost its strength to such an extent as to be worthless. The investigation here reported was undertaken in January, 1922 (Annual Report of the Insecticide and Fungicide Board for 1922, p- 6), for the purpose of obtaming definite information on these 1 Italic numbers in parentheses refer to the Literature Cited, page 14. 13432°—24f 2 BULLETIN 1312, U. S. DEPARTMENT OF AGRICULTURE points and to devise methods of preparation and packing which would make possible a more ee product. The relation of killing soles to the rate and extent of the liberation of nicotine when applied to the plants, a very important point, is not considered here, REVIEW OF LITERATURE Smith (6) describes the introduction of nicotine dusts and gives the history of their early manufacture. He mentions the reaction of lime with nicotine sulphate to form free nicotine. In his dis- cussion of fillers and carriers, he comments on kaolin (which he ranks very high), hydrated lime, quicklime, talc, sulphur, tobacco dust, gypsum, kieselguhr, and lime carbonate. His statement that “‘lime carbonate” has no effect on nicotine sulphate does not agree with the findings of others. De Ong (2) suggests that the results obtained by Smith may have been due to the kind of carbonate of lime he used. Headlee and Rudolfs (3) and Rudolfs (6) published data on the liberation of nicotine from various types of dusts. Most of these results are included in their later publication (4), which gives also a report of their thorough studies on the volatilization of nicotine, both under field conditions and in the laboratory, by passing air under definitely controlled conditions through the nicotine dusts, and on the relation of the rate of volatilization to insect toxicity. De Ong (2) presents data showing the difference in toxicity of non- volatile nicotine sulphate and volatile nicotine. He states that the toxicity of a dust varies in proportion to the change from the salt to the free alkaloid. Thatcher and Streeter (7) conducted a thorough study on the loss of nicotine from nicotine dusts. Their investigation included work on the loss of nicotine from nicotine sulphate dusts during storage very similar to that done in the Bureau of Chemistry. Although the two studies were carried on at the same time, each was conducted entirely independently of the other. Thatcher and Streeter divide fillers or carriers for nicotine sulphate into three groups: (a) Colloidal substances, like kieselguhr and kaolin, that tend to prevent volatili- zation; (6) crystalline substances, such‘as sulphate and gypsum, that are inert; and (c) all the common hydroxides and carbonates which are ‘‘active;” that is, change the nicotine sulphate into the more volatile free nicotine. In studying the effect of storage on nico- tine dusts, they found significant losses from the calcium carbonate and calcium hydroxide dusts, especially the carbonate dust, even in sealed containers. They suggested that this might be due to some chemical change in the nicotine. Campbell (1)presents a historical review of nicotine dusting, which ncludes a complete bibliography. OUTLINE OF EXPERIMENTS In preparing the mixtures used in the investigation here reported, two commercial nicotine solutions, a 40 per cent solution of nicotine sulphate and a 40 per cent solution of free nicotine, were used. Kiesel- guhr, kaolin, talcum, calcium hydroxide, calcium carbonate, and plas- ter of Paris were the carriers or absorbents. Grades of the usual com- mercial purity and degree of fineness were used, so that the results might be comparable with those obtained in commercial practice. ? rs #; - a LOSS OF NICOTINE FROM NICOTINE DUSTS | B The dust mixtures were made up as follows: A quantity of the nicotine solution sufficient to produce a dust of the highest nicotine content employed in the tests was added to the carrier. After putting this mixture through a suitable mixing and sifting machine, a portion was reserved for the highest strength, and two other portions were di- luted with the carrier and again put through the sifter and mixer. The mixtures were then analyzed and packed in the following types of containers: Pasteboard boxes made of two thicknesses of cardboard, with a slip cover of the same material; heavy cylindrical paraffined boxes, having close-fitting covers of the same material, a type much used commercially for semiliquid materials; glass jars with screw top and rubber ring; and small canvas bags. They were stored at room temperature. The samples were analyzed at definite intervals covering a period of a year or longer. In the earlier part of the work all Saeieers were made by the official silicotungstic-acid method (Official and Tenta- tive Methods of Analysis, Association of Official Agricultural Chemists (1920), p- 65). As the number of samples increased and the time involved in the steam distillations became great, experiments were made to determine whether or not the nicotine could be washed out of the dusts and precipitated directly without undue loss in accuracy. It was found that by direct extraction with water prac- tically the same results were obtained as by steam distillation. This procedure therefore was adopted for the later work. EXPERIMENTAL RESULTS The results of the analyses of the nicotine dusts are given in Tables 1 to 10, inclusive. Three strengths ‘of nicotine sulphate-kieseleuhr dust (Table 1) were used in the first series reported. TABLE 1.—WNicotine in nicotine sulphate-kieselguhr dust Strength 1 Strength 2 Strength 3 ae Hs P Paraf. C Paste-| Paraf Cc Paste-| Paraf- C analysis aste-| Paraf- an- aste-| Paraf- an- aste-| Paraf- an- board | fined ee vas || board | fined See vas || board] fined a vas box | box | ! bag || box | box | J bag || box | box | J bag 1922 Per ct.| Per ct. | Per ct.| Per ct.|| Per ct. | Per ct.| Per ct. | Per ct. || Per ct.| Per ct.| Per ct.| Per ct. Mar iS 442. 4aNG Ce 7.1 CAT 5. 12 5. 12 5-12 Oo D2 2. 24 2. 24 2. 24 YS ees ce To 29 E56! | len® |a= oes = 5. 26 5. 23 5-09-|-2 see 2. 25 2. 28 2. 26 220 Is 8 a a Fy eC Pilea as nl a fa Us 7.14 5. 20 5.28 | 5.14 5. 05 2. 28 Dy Ppcer shales eae WURO psa | OD 1640) |.9 4. 09) 7.32 520) || 5.39) Satie. 30 2.30} 2.31] 2.24 2. 28 SOR b oe see eee ee so |[Seeiwes 5. O01 5. 01 5. 14 2.25 2.-38-|-- 2: 25 2. 34 INO Vs S22 o-). tee G84 122 6.80 | 6.64 4.84 | 4.86] 4.76] 4.98 2.08 | 2.10] 2.14 2. 23 1923 INOW. S2eeeoees GO dee ee 6.18 | 5.78 3.89 | 4.03] 4.46] 3.89 1.85} 1.92] 1.90 1. 74 The results in Table 1 show that the rate of liberation of nicotine from kieseleuhr is slow. No loss had occurred at the end of three months.2 Even in the canvas bag, the change in nicotine content 2 The higher strengths show, in some cases, an increase in the nicotine content after three months, which may be accounted for, partially at least, by the loss of moisture from the samples and consequent relative concentration of nicotine in the samples. 4 BULLETIN 1312, U. S. DEPARTMENT OF AGRICULTURE in the strongest mixtures was only from 7.17 to 5.78 per cent after 20 months. In other words, 80.6 per cent of the nicotine originally present remained at the end of 20 months, a loss of only 1 percent per month. Two strengths only were made up with kaolin, because it is such a poor absorbent that even the 5 per cent strength was too damp for use as a dust. TaBLE 2.—Nicotine in nicotine sulphate-kaolin dust Strength 2 Strength 3 Date of analysis Paste Par De P aste- ar- aste- ar- board |affinea | Glass | Canvas) }oard | affinea| Glass | Canvas box | box uae ag box box Jar ag 1922 Per cent| Per cent| Per cent| Per cent|| Per cent| Per cent| Per cent| Per cent NG GY eh Wi 3 MEI i 1 ae eS a i AS ca Sh De 20 Doo 5. 25 Ds2o 2. 49 2. 49 2. 49 2. 49 Maiyios eee go. epee ee oe 4.92 5.17 9B} 5. 02 2. 48 2. 50 2. 50 2. 50 FRING (Soa ee et see le oe 5. 03 5. 08 5. 07 5. 06 2. 44 2. 46 2. 45 2. 47 Septembertsats oes ee a eee ess 4.92 5. 00 5. 08 4.93 2. 33 2. 43 2. 38 2.37 December 3s2ts2222 2 ae ae 4, 80 AOS asc Fp7 4,81 231 2.39 2. 40 2. 39 1923 November 32222 Se he 4,71 4.75 4,92 4, 57 211 2.17 2. 23 2. 03 The kaolin dusts also showed practically no loss after storage for twomonths. (Table2.) At the end of 19 months the loss from the stronger dust packed in the canvas bag was 13 per cent of the total uantity originally present; the loss from the same dust packed in the glass jar was 6 per cent. As talcum proved to be the poorest absorbent of the materials tested, a dust of the lowest concentration only was prepared with it. TABLE 3.—WNicotine in nicotine sulphate-talcum dust Strength 3 Date of analysis Paste- Paraf- Glass board box| fined box jar 1922 Per cent | Per cent | Per cent 12) OF Nese geen OE TAR, eS aL Ue Sal ad Nek eC: st EEA ie oN TG 1.79 1.79 1.79 Ms PEW G7 fp tate aS SGP AN <3 De a Ea RR FS a oe ee a se RTA! 1. 67 1. 79 ASD Try 20 23g ON he SF ea, IE ps 2 SE ie a eR ee 1. 65 1. 67 1. 78 UPTO 20 oe se ee! ee eae ee be ee ces 8 Rt 1. 41 Te Gizé 1.61 SOP GM 20S Bek es he teas ces Pee eT pe Se SE ae L 0 I eae 1.18 1. 34 1. 64 1923 TB) 20 Scars ee cine St ie 8 EE aE eres Sah 2 en eG a ee er 1.10 1.16 1, 54 ahaliy: 20 eee s Les pea le i OSE etl) eek ee ae a eae ee 1. 00 1.10 1. 45 PEC 3120 Rete eae eS LP Rey. Meee a tha” _ CR ca vee ea 94 1.00 1.33 Talcum, dust lost nicotine more rapidly than either the kieselguhr or kaolin dust. (Table 3.) The maximum loss was 47 per cent of the quantity originally present after 22 months. As calcium hydroxide, calcium carbonate, and plaster of Paris were very active in liberating nicotine, they will be considered together. (Tables 4, 5, and 6.) LOSS OF NICOTINE FROM NICOTINE DUSTS 5 TABLE 4.—WNicotine in nicotine sulphate-calcium hydroxide dust Strength 1 Strength 2 Strength 3 eb is f C P Paraf: Cc P Paraf. analysis Paste-| Paraf- an- aste-| Paraf- an- aste-] Paraf- Can- board | fined aes vas || board | fined os vas || board } fined CE vas box | box | bag || box | box | / bag || box | box | J bag 1922 Per ct. | Per ct. | Per ct. | Per ct. || Per ct. | Per ct. | Per ct. | Per ct. || Per ct. | Per ct.| Per ct. | Per ct. Apres 1225 ose ali (404 7. 04 7. 04 7.04 5. 04 5. 04 5. 04 5. 04 2. 41 2. 41 2.41 2. 41 Nay; bes =|) 6,08, toad [iv 22 | 6.50 4.95] 5.32] 5.24] 486 2.34] 2.36] 2.52 1. 88 Jue 12) F228 6.24] 6.92] 7.24] 6.00]} 4.40; 4.82] 5.18] 4.56 2.09} 2.11] 2.48 1. 91 Sept. 12¢-<.2_-| 5.08.) 6.03.| .7.07_} 3.06 3.401) 4. 1 aeeo Oeil, 2490 1.54] 181] 2.50 1,14 1923 ebro S09) leoee cee 6.75 | 2.76 2.43 | 3.80] 5.42] 1.73 Aas i daoo ie 245 81 Detel2-=2s2e25 1.78 | 3.26] 6.40) 1.81 137-1) 2:60) 4.938 | 1.06 |. -.81 }.1.00 | 1.99 67 TABLE 5.—WNicotine in nicotine sulphate-calcium carbonate dust Strength 1 Strength 2 Strength 3 sae _ Paste-| Paraf. C Paste-| Paraf. C Paste-| Paraf C analysis aste-| Paraf- . an- || Paste-| Paraf- an- ||} Paste-| Paraf- an- board | fined | 41985] “Vas || board | fined | WS} vas |} board| fined | S985] vas box | box | J bag || box | box | / bag || box | box | ! bag 1922 Per ct.| Per ct. | Per ct.| Per ct. || Per ct.| Per ct.| Per ct.| Per ct. || Per ct.| Per ct.| Per ct. | Per ct. ADE Oho ce COPPA BPO | By AVP EW BOF 4.99 |} 4.99] 4.99 | 4.99 IBS a8 3? 2. 33 2. 33 June 8 222... 5. 86 6. 36 6. 53 4, 02 3. 46 4. 06 4, 56 3. 22 1.31 1. 61 1.98 1. 08 Sept. 10-24 -22- 4.32 | 5.54 | 6:31 2. 45 2.22) oS. 257 442671 2 42 -82| 1.01 1. 56 60 1923 heb: sss Fost | oly] Rapes 6.49 | 1.90 1.90] 3.19 | 4.64] 1.29 -97 |} 1.16} 1.79 96 INOVO- ee 1 es 25} 6. 27 1. 02 1.16 1.66} 4.08 75 .70 Sitt 1.63 52 TABLE 6.—Nicotine in nicotine sulphate-plaster of Paris dust Strength 1 Strength 2 Strength 3 aoe oe Paste-| Paraf: Cc Paste-| Paraf. C Paste-| Paraf. Cc analysis aste-| Paraf- an- || Paste-| Paraf- an- || Paste-| Paraf- an- board | fined Gass vas || board] fined Ces vas || board| fined Ges vas box | box | J bag || box | box | / bag || box | box | J bag 1922 Per ct. | Per ct. | Per ct.' Per ct. || Per ct.| Per ct.| Per ct.| Per ct. || Per ct. | Per ct.| Per ct.| Per ct FADE, 16822 5.5 + 6. 70 6. 70 6. 70 6. 70 4. 65 4. 65 4, 65 4. 65 2. 02 2. 02 2. 02 2. 02 May 1682.2 2 6. 12 6. 50 6. 31 5. 98 4,22 4. 28) (hers. 4. 08 1. 66 1.82 1. 82 1. 55 gune 16 -2-= =. 5. 88 6. 09 6. 40 5. 03 3. 70 4. 08 4. 38-|b o> 22 1. 56 1.85 98 Sept. 16__...__ 5.18 | 5.56] 6.78] 4.88 2. 84 3.05 | 4.57 25 51 69 1. 23 1.81 59 1923 Hens-16.22. = 3.77 | 5.88 | 6.49] 4.08 2.17 3.08 | 4.41 2.12 . 63 76} 1.67 42 INGW.162 <2 "2 ary eee 6.30 | 3.78 2.24) 2.31) 4.11 1,99 | 49 a0: |) 2.30 39 Both calcium hydroxide and calcium carbonate react with nicotine sulphate, freeing the alkaloid, which is volatile. Analysis of the plaster of Paris showed that it was alkaline enough (equivalent to 15 per cent calcium carbonate) to react with the nicotine sulphate in the weaker dusts, but not alkaline enough to react completely with the nicotine sulphate in the stronger dusts. For this reason, dusts of this material in different strengths do not behave alike. The strongest, containing originally 6.7 per cent nicotine, lost, from the canvas bag, 44 per cent of its nicotine content after 19 months, while the sample with 2.02 per cent nicotine lost during the same period over 80 per cent of its nicotine. The maximum loss from 6 BULLETIN 1312, U. S. DEPARTMENT OF AGRICULTURE the calcium hydroxide dust was 80 per cent and the minimum loss from the dust of highest nicotine content, packed in the glass container, was less than 10 per cent during storage for 20 months. The calcium carbonate dust lost more than any of the other nicotine sulphate dusts, the loss ranging from a maximum of 86 per cent to a minimum of 13 per cent during the 19-month storage period. Tables 7, 8, 9, and 10 give the results of analyses of dusts prepared and packed in the same manner as the dusts already considered, except that free nicotine solution was substituted for nicotine sulphate These results cover a maximum period of storage of 12 months except in the case of free nicotine-kieselguhr dust, which ran solution. for 19 months. used. Date of analysis Date of analysis Date of analysis Kaolin and talcum, being poor absorbents, were not TABLE 7.—WNicotine in free nicotine-kieselguhr dust Strength 1 pie | Paraf- Can- board | fined ae vas box box J bag Per ct.| Per ct. | Per ct. | Per ct. 8.06} 8.06] 8.06] 8.06 ho Odale Ao Oiled) a SOE. 6. 90 4.541 5.30] 7.20] 3.7 3.86 | 4.65 | 6.99 | 3.42 2.87 | 3.71] 6.39] 2.66 Can- vas bag Strength 2 Paste-| Paraf- | board | fined Ss box | box | J Per ct. | Per ct.| Per ct. 5. 56 5. 56 5. 56 5.05 | 5.30] 5.41 4.00 | 4.52] 5.00 3.39 | 4.07 | 4.72 2:83 | 3.00.1 - 4.18 TABLE 8.—WNicotine in free nicotine-calcium carbonate dust Strength 1 Paste-} Paraf- Can- board | fined Glass vas box | box J bag Per ct. |Perct. | Per ct. | Per ct. 7.43 | 7.43 | 7.48 | 7.48 6.50 | 6.55! 7.00] 5.04 4, 27 4.14 6. 87 4.09 O02 |e 6. 55 3. 11 2.97 3. 54 6. 26 1. 94 Strength 2 Paste- | Paraf-| 4, | board | fined Clas box box J Per ct. | Per ct. | Per ct. 4.70 | 4.70] 4.70 3.40 | 3.42] 4.48 2°51 | = 2782 || 39 2.02 | 2.06] 4.02 1.40 1.58 3. 56 TABLE 9.—WNicotine in free nicotine-plaster of Paris dust Strength 1 Paste-| Paraf- Can- board | fined ee vas box box J bag Per ct.| Per ct. | Per ct. | Per ct. 6.18 | 6.18] 6.18] 6.18 5. 49 6. 05 6.12 3. 52 4.50} 518) 6.04] 3.11 3.08] 441] 5.91 ].2.18 15 724i FR 55 WES. SB .35 —E—— SS sss SSS SS ES SSS Se Strength 2 Glass fined | F box Jar Per ct. | Per ct. 3.80 | 3.80 ayy fs wea 3.20} 3.70 2.48 | 3.51 1.84 | 3.12 Strength 3 Paste Paraf- Can- board | fined | G85 | Vas box | box J bag Per ct.| Per ct.| Per ct. | Per ct. 3.94] 3.94] 3.94 3. 94 2.81 | 3.44] 3.88 3.17 2 26"| “ 2°36:)\_ 3:-72 pee) 1.96 2. 28 3. 66 1.42 1.34] 1.49] 3.09 . 65 Strength 3 Paste-} Paraf- Can- board | fined Ges vas box | box | J bag Per ct. | Per ct. | Per ct. | Per ct. 2.05 | 205] 2.05 2. 05 a estryg fen Beit a Sr ES 1.35 4993 4 4 SO lard es 1. 04 1.05 | 1.08] 1.70 .95 . 64 43 1. 55 ai) | Strength 3 Pp | Cc 4 aste- Paraf- an- board | fined a vas box box Ja bag Per ct.| Per ct.| Per ct. | Per ct. 1.62] 1.62] 1.62 1. 62 f. $3. | 250s oF . 68 1.09 agit 1. 38 . 74 . 68 3 10-1-, 4a26 . 51 S22 L22 1. 03 13 LOSS OF NICOTINE FROM NICOTINE DUSTS TABLE 10.—Nicotine in free nicotine-calcium hydroxide dust a a a ee ee ee eee CT Strength 1 Strength 2 Strength 3 pclens | [Baas | Base Can- || Paste- | Parat Can- || Paste-| Paraf-| C analysis as araf- an- e- | Paraf- an- || Paste-} Paraf- | e an- board | fined Ses vas || board | fined ae vas || board | fined wes | vas box | box J bag box | box J bag {| box | box jar | bag SYAD comeuatone: xi | i | 1922 Per ct. | Per ct.| Per ct.| Per ct.|| Per ct.| Per ct.| Per ct.| Per ct.|| Per ct.| Per ct.| Per ct.| Per ct. Dec, 28......-_| .7.80,| 7.80] 7.80] 7.80 5.46 | 5.46] 5.46] 5.46 3. 31 3. 31 3. 31 3. 31 1923 Feb: 28_--. 3. 6.39} 7:45) 7.75 [-331 459] 5.30] 5.45] 2.85 A oe 10'}: KDA 2. 29 Apr 28223 5.42 | 6.43 7.60 | 2.83 3. 80 | 4.48 | 5.20] 2.40 2.41 2. 88 3. 10 1. 80 Sept. 28...._.- 5p C0 rs es ey A oe 2.04; 3.63] 4.92 1. 53 1. 23 2. 23 2.95 1.10 Dee 30-224 2.00} 4.52 7.18 1.79 1. 26 3.24 | 4.74 ah . 68 1.59 2. 72 . 92 The results obtained by calculating the percentage of nicotine lost from each sample and averaging for the three strengths are shown in Figures 1 to 10. The figures, therefore, show the percentage of nicotine lost from the samples, while the tables show the percentage of nicotine in the samples at the time of analysis. 30 PASTE LAIRD LOX CIVZAIIS AIG 20 ai tect te \ (Beas CLASS LAL ; . Wiiuiam A. Taytor, Chief. GRP SEOS CIN TEr ee ee ee ee W. B. GREELEY, Chief. ERR DTT CE (OES a i ee C. A. Browne, Chief. PUTCO OPS OH Smee ee ee! Mitton WHITNEY, Chief. Bureau of Entomology__------------------ L. O. Howarp, Chief. Bureau of Biological Survey___--__----_--- E. W. Netson, Chief. Bureau of Pabre-negts—_ 2 Tuomas H. MacDonatp, Chief. Bureau of Home Economics_-__------------ Louise STANLEY, Chief. BY APETV ICTS Cod DIT) PT 7 = C. W. Larson, Chief. Fized Nitrogen Research Laboratory __------ F. G. Cottre.y, Director. _ Office of Experiment Stations __------- Bi Page EK. W. ALuen, Chief. Office of Cooperative Extension Work ______- C. B. Situ, Chief. MO yice oF F wuleenions. L. J. Haynes, Director. LOE PATS Ps a a CLARIBEL R. Barnett, Librarian. Federal Horticultural Board_____---------- C. L. Maruatt, Chairman. _ Insecticide and Fungicide Board_-_-__------- J. K. Haywoop, Chairman. Packers and Stockyards Administration__-_--- CHESTER MorRIi.u, Assistant to the _ Grain Futures Administration__----------- Secretary. This bulletin is a contribution from Peart Oy ucmestrayy- = = C. A. Browne, Chief. Miscellaneous Division _.._..-.-------- J. K. Haywoop, Chief. 15 ae {p-weant ae ee i a SE 2 asians are I a: = Res ye: cot Se = ahaa ae SEN VHeck PSs FFAS a S| ae pee Rs aD ; See tet ee Owe Fe ih mt Ts Lae is ini ob ae meee Harps a kh ‘eh 4 ace TTHaaole RaTAS tah f se ne <_ peerin’ ay ap veces B chyinpteelS AA FW . et xe ls rate’ Fm - . - : + as Is | o> -aiech alias Rei $3 Ne ciataniel i. : ‘ a ol 7 i % i.e scgete =e iat cei: theo ea at rupotins antl ro Tha) Rue onc. .f BB Pane t : x Bnecce +a } .