Historic, archived document Do not assume content reflects current scientific knowledge, policies, or practices. Bro ee resin . S. DEPARTMENT OF AGRICY BUREAU OF CHEMISTRY—BULLETIN No. 113 (R A H. W. WILEY, Chief of Bureau, ess a ECEIVED. 4 we JULSS 1910 4 U. &. Department of Asricuitare J 2@eeeres tac OFS 8 Oe sw igen +“ *#+ hoes INJURY TO VEGETATION AND ANIMAL LIFE 4 ad BY SMELTER WASTES. as coe Ce : i} eS es By eee J. K. HAYWOOD, e~ Be eS CHIEF OF THE MISCELLANEOUS DIVISION 5 NX ASSSSSSs WASHINGTON: | eS GOVERNMENT PRINTING OFFICE. ; a ROAD i | ee . : : : Issued July 7, 1910, a >. DEPARTMENT..OF AGRICULTURE, ° BUREAU OF CHEMISTRY—BULLKTIN No. 113 (Revised). H. W. WILEY, Chief of Bureau. 4 6 INJURY TO VEGETATION AND ANIMAL LIFE 7 BY SMELTER WASTES. By J. K. HAYWOOD, CHIEF OF THE MISCELLANEOUS DIVISION WASHINGTON: GOVERNMENT PRINTING OFFICE. ROEOF ORGANIZATION OF BUREAU OF CHEMISTRY. H. W. Witey, Chemist and Chief of Bureau. F. L. DunLAP, Associate Chemist. W. D. Bicretow, Assistant Chief of Bureau. F. B. Linton, Chief Clerk. A. L. Pierce, Editorial Clerk. M. W. Taytor, Librarian. Divisior of Foods, W. D. BiacELow, Chief. Food Inspection Laboratory, L. M. Totman, Chief. . Food Technology Laboratory, E.M. Cuace, Chief and Assistant Chief of Division. Oil, Fat, and Wax Laboratory, H. 8. BarLey, Chief. Division of Drugs, L. F. Keser, Chief. Drug Inspection Laboratory, G. W. Hoover, Chief. Synthetic Products Laboratory, W. O. Emery, Chief. Essential Oils Laboratory, under Chief of Division. Pharmacological Laboratory, WM. SaLant, Acting. Chief Food and Drug Inspector, W. G. CAMPBELL. Miscellaneous Division, J. K. Haywoop, Chief. Water Laboratory, W. W. SKINNER, Chief. Cattle-Food and Grain Laboratory, G. L. BIpwELL, Acting Chief. Insecticide and Fungicide Laboratory, C. C. McDoNNELL, Chief. Trade Wastes Laboratory, under Chief of Division. Contracts Laboratory, P. H. WALKER, Chief. Dairy Laboratory, G. E. Patrick, Chief. Food Research Laboratory, M. E. PEnnineGTOoN, Chief. Leather and Paper Laboratory, P. P. Verrcn, Chief. Microchemical Laboratory, B. J. Howarp, Chief. Sugar Laboratory, A. H. Bryan, Chief. Sections: Animal Physiological Chemistry, F. C. WEBER, in Charge. Bacteriological Chemistry, G. W. StTiLxEs, in Charge. Enological Chemistry, W. B. Atwoon, in Charge. Nitrogen, T. C. TrEscot, 7n Charge. Vegetable Physiological Chemistry, J. A. Le CLrerc, in Charge. Food and Drug Inspection Laboratories: Boston, B. H, Smiru, Chief. Buffalo, W. L. DuBois, Acting. Chicago, A. L. Winton, Chief. Cincinnati, B. R. Hart, Acting. Denver, A. E. Leacu, Chief. Detroit, H. L. ScHunz, Acting. Galveston, T. F. Pappr, Acting. Honolulu, Hawaiian Islands, R. A. Duncan, Acting. Kansas City, Mo., A. V. H. Mory, Chief. Nashville, R. W. Batcom, Acting. New Orleans, C. W. Harrison, Chief. New York, R. E. Doourrrie, Chief. Omaha, 8S. H. Ross, Acting. Philadelphia, C. 8. Brinton, Chief. Pittsburg, M. C. ALBrEcu, Chief. Portland, Oreg., A. L. Knisety, Chief. St. Louis, D. B. BisBExr, Acting. St. Paul, A. S. Mircuett, Chief. San Francisco, R. A. GouLp, Chief. Savannah, W. C. BurNeEt, Acting. Seattle, H. M. Loomis, Acting. 2 LETTER OF TRANSMITTAL UNITED STATES DEPARTMENT OF AGRICULTURE, BUREAU OF CHEMISTRY, Washington, D. C., February 15, 1910. Str: I have the honor to submit for your approval the results of a series of investigations made by the chief of the miscellaneous division of this bureau in regard to the injury to vegetation and ani- mal life observed in the vicinity of certain smelters, particularly one located at Anaconda, Mont. The original report was issued in May, 1908, and has now been revised to include a second investigation subsequently conducted at Anaconda. These studies have been made in this bureau from time to time during the past eight years in coopera- tion with the Bureau of Forestry in the preservation of the forests and the protection of the farming interests. I recommend that this report be published as Bulletin 113, Revised, of the Bureau of Chemistry. Respectfully, H. W. WILeEy, Chief of Bureau. Hon. JAMES WILSON, Secretary of Agriculture. CONE NEES: duction. i Ss M8: Process of exiting euetale rong ORES eae aes. eae SRR Rein ouae sR ten ae ta re Sula mE mWASt@ Rees emcuari me renga ae Cie meCrs sve cesialnne c Sas WM! Ue eh ahaa ey Experimental investigations relating to the action of sulphur dioxid on vege- Organs of plants through which injury takes place.-......-.....----.----- Amount of suiphumdioxid that may cause 1mjury. 2+ .2.-.2--...- 252-2... Sulphur trioxid content of the foliage of fumigated and unfumigated Field investigations of the action of sulphur dioxid fumes on vegetation . ....- A California smelter and certain foreign smelters.......:.....---.---.-- MOMenmesseeysmeliersetes cna Ratc nckee esse ace dete ges eae ee First investigation of injury by smelter wastes around Anaconda, Mont., 1906-7. Location of smelter and appearance of surrounding vegetation.......-.-..- Sulphur trioxid in foliage of trees around Washoe smelter.......-..------ Injury to cattle by arsenic in the vicinity of Washoe smelter . : Injury to crops and soil by tailings and slag from the iealnne Peaaerion FPA Cc oS Eg Bes Gg eet Stet fears he er ai ee ce ea Second investigation of injury by smelter wastes around Anaconda, Mont., WOOD) ge RE Ee Nee cy a ye ge ea Appearance of vegetation surrounding smelter......-....-.--..--------- Sulphur trioxid in foliage of trees around Washoe smelter........-..----- Arsenic content of forage crops around Washoe smelter...-.......-------- Menioadsoranalysis used 1m imvestigations!. .-... 2252... .4. 02.25.22 <..0-22 52 Ria eRe OMAPUCE SMe. co ier Fe YE Seapets 9 Meek Bos Ure oo Slee TER 2 na no Dat oe al ce erat a a Incite el eC a Ee aE PLate I. JOE Talal: Ve V. Walk . Fig. 1.—View of a mountain side about 24 miles west of Washoe VILL. ILLUST KAT Os: PLATES. Keswick smelter near Redding, Cal., in operation .............-..-- Fumigation chamber for testing effects of sulphur dioxid on young [hoo ee ee ee re LO NaN A Ui ioe ele oe silo Gd oon View about 2 miles south of Keswick smelter near Redding, Cal... -- View about 3 miles west of Keswick smelter near Redding, Cal--.-- Washoe smelter at Anaconda, Mont., in operation............-..-- Map of region around Anaconda, Mont. (folder)...................- smelter—formerly covered with timber toward the summit, but now bare. Fig. 2.—View of a mountain side about 3 miles west from Washoe smelter—red firs killed and junipers apparently uninyured: 20.2250). 2 ee Re ee Ae Fig. 1.—View of a mountain side about 104 miles west from Washoe smelter—red firs killed and lodgepole pines injured.Fig. 2.—View of mountains about 11 miles west from Washoe smelter........-- . Fig. 1—Uninjured mountain side about 2 miles south of divide and 10 miles south of smelter beyond range of apparent damage. Fig. 2.—Uninjured mountain side up Dry Cottonwood Creek be- yond ranger’s cabin, about 14 miles ENE of smelter, beyond range of apparent.damage. 2.144.558 sss aes eee 24 24 38 INJURY TO VEGETATION AND ANIMAL LIFE BY SMELTER WASTES. INTRODUCTION. PROCESS OF EXTRACTING METALS FROM ORES. Before considering the injurious effects which wastes from plants smelting sulphid copper ores may have on vegetation and animal life, a brief account will be given of the process generally used to extract the metal from the ores. For this purpose an outline of the process followed at Anaconda, Mont., will be given, which, though differing in some details from the process used at other plants, is based on the same general principles and produces similar waste products. The ores when they arrive at the plant are graded as first and second class, the former being sent to the bins of the blast furnaces and the latter to the concentrator bins. The second-class ores are next sampled, crushed, and passed over jigs, by which process a product richer in copper, known as the * concentrates,” 1s obtained. The reject from the jigs is crushed again and passed over jigs fitted with finer screens, ‘ concentrates ” being again obtained. After ex- tracting all that can be taken out by the jigs, the ore is again crushed and passed over the Wilfley tables, thus giving rise to the “ table con- centrates.” The concentrates are sent to a bin at the foot of the concentrator. There remain in the water used for concentration some fine particles of valuable material, and this is allowed to flow into ponds outside the plant, where the fine particles settle out in the form of “slimes” and the water is finally drawn off. The slimes are briquetted and blast-smelted. The waste products from the con- centration are known as “ tailings.” These tailings, consisting princi- pally of silica, iron, ete., with small quantities of copper and arsenic, in case the latter is present, are discharged on the dump heap. The concentrates are dumped into roasting furnaces, where large quantities of sulphur and arsenic are driven off, the former as sulphur dioxid and trioxid and the latter in volatile form. The residue, now known as “ calcine,’ is transferred to reverberatory furnaces. This process yields (1) a slag consisting principally of silicates of iron and calcium with very small quantities of copper; (2) a product richer in copper known as “ matte;” and (3) volatile i 8 INJURY BY SMELTER WASTES. arsenic and sulphur products which are carried to the flue. The slag — is granulated in water and passed to the dump. The “matte” is carried to the converters, where it is treated in the same way as “ matte ” from the blast furnaces. The blast furnace receives a charge consisting essentially of the high-grade ores, converter slag, briquettes of siliceous fines and slimes from the concentrator, limestone, and coke. A large part of the sulphur passes off to the flue as sulphur dioxid and trioxid, and large amounts of arsenic are volatilized. The iron and silica in the ore, together with the lime, form a slag (containing a very small amount of copper) which is granulated in water and carried to the dump; the copper forms a “ matte” consisting principally of a combination of copper, iron, and sulphur. This, together with the “ matte ” from the reverberatory furnaces, is next carried to the | converters, the lining of which is a siliceous material that lasts for several runs. In the converter the sulphur which is present in the “ matte” is oxidized to sulphur dioxid and trioxid and escapes up the flue, the remaining arsenic is volatilized and also goes up the flue, while the iron unites with the siliceous ning to form a slag which is returned to the blast furnaces, since it is a good flux and also contains con- siderable quantities of copper. The copper obtained by this ‘process is carried to the preliminary refining apparatus, where air is passed over the molten mass to remove traces of sulphur and the small amount of slag which was not taken out in the converters is also eliminated. During this process some copper oxid is formed, but upon stirring this is again reduced to copper by the carbon of the converter poles. In this condition the copper is cast into ingots, which are sold to refineries not situated at Anaconda. The fumes from these processes are passed through long cooling chambers in order to condense the volatilized compounds of arsenic as far as possible, but in spite of this precaution large amounts of arsenic escape from the top of the chimney. No attempt is made to recover any of the sulphur compounds. ¢ RESULTANT WASTES. From this brief description of the process used at Anaconda, it will be evident that four wastes arise which may be injurious to plant or animal life. (1) The sulphur contained in the ore is gradually given off dur- ing the various processes of smelting, as sulphur dioxid and a little sulphur trioxid, which would have their injurious action on vegeta- tion. PLATE lI. Bul. 113 (Revised), Bureau of Chemistry, U. S. Dept. of Agriculture. KESWICK SMELTER, NEAR REDDING, CAL., IN OPERATION, CHARACTER OF WASTES. 8) (2) In case arsenic is present in the ores, as it often is and notably at Anaconda, it is given off in the fumes from the smelter in volatile form and deposited on the surrounding land and crops, where it may be present in sufficient amounts to poison cattle browsing on exposed ranges, or living on hay cut from such pasture. (3) The tailings from the water concentration of the ore and the slag, in a finely divided condition, are discharged on a dump heap through which the water from the plant is constantly percolating on its course to adjacent streams and the “slimes” are left in piles in the open air. Both the slime heap and the dump are also exposed to the percolating action of the rain. In consequence, the streams re- ceiving the waste water from concentrating and smelting plants con- tain a comparatively large amount of copper in suspension and are apt to hold some copper in solution. If these streams are used for irrigating purposes there is a possible source of injury to growing crops due to the action of the copper present. (4) Finely divided particles of the ore are discharged from the smelter stack and settle on the surrounding country. These fine par- ticles of flue dust may contain sufficient amounts of copper, lead, and zinc to injure vegetation, because of their toxic action through the medium of the soil and because of their caustic action on the foliage. While it is believed- by some” that the action of this so-called flue dust gives rise to the principal damage caused by smelter smoke, the writer is inclined to the opinion ? that such injury is not of great sig- nificance except in a very limited area about the smelter, and that an investigation of it is in most cases unnecessary, as the owners of smelt- ers are usually perfectly willing to admit damage, even beyond the area likely to be affected by the solid particles of copper, lead, and zine in the flue dust. In the first case of this kind studied by the writer in the vicinity of Redding, Cal. (see Pl. I), and in the laboratory at Washington during 1903 and 1904, no complaint had been made of the injury from arsenic or from copper, so that the only problem considered was the action of sulphur dioxid and trioxid fumes on the surround- ing vegetation. The results of this study and the original investiga- tions connected therewith have been published,° but a résumé will be given, together with certain results obtained since the publication of the Redding investigations, in order that the reader may under- stand the present status of the work. @Hbaugh, J. Amer. Chem. Soc., 1907, 29: 951. 5 Haywood, Science, 1907, 26: 476. © U. S. Dept. Agr., Bureau of Chemistry, Bul. §9, Injury to Vegetation by Smelter Fumes, 1905. 38816—Bull. 118—10 2 10 INJURY BY SMELTER WASTES, EXPERIMENTAL INVESTIGATIONS RELATING TO THE ACTION OF SULPHUR DIOXID ON VEGETATION. ORGANS OF THE PLANT THROUGH WHICH INJURY TAKES PLACE. In carrying on an investigation of this kind it was first necessary to ascertain whether or not sulphur dioxid was injurious to plant life, how small a quantity was injurious, and through what organs of the plant such injury took place. Light is thrown on this subject by the work of foreign chemists. Freytag ® showed that sulphur dioxid and trioxid do not injure the plant through the roots. His experiment consisted in watering wheat, oats, and peas with large amounts of dilute sulphurous acid in one case and sulphuric acid in another. The plants neither wilted nor reduced their yield. Von Schroeder and Schmitz-Dumont? made an investigation on pines, firs, hndens, and Norway maples in 1896, in which they treated (1) the aerial parts of the plants with sulphur dioxid, (2) the aerial parts of the plant and the earth with sulphur dioxid, and (3) the earth in which the plant was growing with dilute sulphurous acid. They also showed that the injury to vegetation by sulphur dioxid is not through the roots, but through the medium of the leaves, and that even extremely minute quantities of sulphur dioxid are injurious. : Wieler in his work entitled “ Untersuchungen tiber die Einwir- kung schwefliger Siure auf die Pflanzen,” which has been published since the work at Redding was done, also gives numerous experi- ments to show that minute amounts of sulphur dioxid injure plants through the leaves, but he’ also states that in the course of time the sulphur dioxid and trioxid present in smelter smoke injuriously affect the soil and so indirectly injure the plant through the roots. He is further of the opinion that soils subjected to the action of sulphur dioxid suffer from a reduction in the lower forms of animal and plant life which are so necessary to the series of natural changes taking place in normal soils. He is also of the opinion that such soils suffer a loss in bases, which eventually causes them to become acid, as not enough bases are present to form humates with the humic acid. In proof of the latter point, he has taken soil samples from the vicinity of several smelters and found that all of them contained free humic acid. ) Wieler’s conception of this additional injurious action of sulphur dioxid on the soil has been published so recently that the writer has not been able to investigate the subject sufficiently to express a defi- @ Mitt. d. konig). landw. Akad., Poppelsdorf, 1869. ® Thar. forstl. Jahrb., 1896, 46: 1. INJURIOUS AMOUNTS OF SULPHUR DIOXID. Th nite opinion in regard to its merits. It would appear, however, from the work done that Wieler lays too much stress on the sulphur dioxid injury to the soil, as compared with the injury caused by the sulphur dioxid acting on the foliage. In support of this opinion several soils from the vicinity of a smelter were tested by the author. These soils were taken from forest land where certain trees were practically annihilated by smelter fumes, as proved by chemical analysis, and yet all of the soils gave an alkaline reaction, showing that there had evidently not been such a loss of bases as to give rise to free humic acid. ~ On the whole, then, the work done undoubtedly points to the fact that sulphur dioxid injures vegetation through the leaves, but whether it injures the soil, and so indirectly injures the plant through the roots, is a problem which must be studied further before a definite conclusion can be reached. \ AMOUNT OF SULPHUR DIOXID THAT MAY CAUSE INJURY. In regard to the amounts of sulphur dioxid in the atmosphere that may injure vegetation, Stockhardt* showed that 1 part of sulphur dioxid to 1,000,000 parts of air injured potted pines seriously after 865 fumigations. Freyag* cast doubt on Stockhardt’s data by his investigations, and St6ckhardt’s work was repeated by Von Schroeder and Schmitz-Dumont,* who showed that great injury was inflicted by fumigating pines 109 times with 1 part of sulphur dioxid to 100,000 parts of air and that injury was to be noted on fumigating pines 583 times with 1 part of sulphur dioxid to 1,000,000 parts of air. The details of the work done by the writer in relation to injury to pimes and young cowpeas? by sulphur dioxid show the following results: : (1) Pine trees fumigated ¢ 6 times with 1 part of sulphur dioxid to 100 parts of air showed marked injury. All of the needles were drooping, and nearly all had turned yellow or brown. (2) Pine trees fumigated 9 times with 1 part of sulphur dioxid to 1,000 parts of air were greatly injured in the same manner as the plants just described. (3) Pine trees fumigated 50 times with 1 part of sulphur dioxid to 10,000 parts of air were badly injured. (4) Cowpeas fumigated 18 times with 1 part of sulphur dioxid to 10,000 parts of air lost all their leaves and could not be revived, al- though carefully watered and tended outside the fumigation chamber. * Haselhoft and Lindau, Die Beschidigung der Vegetation durch Rauch, pp. 58-66. ®U. S. Dept. Agr., Bureau of Chemistry, Bul. 89. © Each fumigation lasted for one hour. 19 INJURY BY SMELTER WASTES. (5) Pine trees fumigated 50 times with 1 part of sulphur os to 30,000 parts of air Dread decided inj ury. Since the above work was performed in connection with the in-- vestigation of 1903-4, described in Bulletin 89, the writer has con- ducted further experiments (during 1907) to test the effect of sulphur cioxid on vegetation. A fumigation chamber was used consisting of a wooden frame 3 feet broad, 3 feet deep, and 4 feet in height, with glass panes, as shown in Plate II. On the side was a removable door which could be tightly closed. This chamber was placed over various trees about 3 feet in height, just as they grew in the open. The sul- phur dioxid was prepared by burning carbon bisulphid, in an alco- holic solution, in such amounts as would give definite amounts of sulphur dioxid in relation to the space within the chamber. A fan, run by dry batteries from the outside, was used.to mix the sulphur dioxid and the air. Each fumigation was continued for one hour, when the chamber was removed and the plant allowed to stand in the open from fifteen minutes to an hour. The chamber was entirely removed from the plants at night. Another fumigation chamber of exactly the same construction and size was placed over a control plant. In this chamber the same amount of aleohol was burned as was used in the case of those plants which were subjected to the action of sulphur dioxid. A fan was also used to mix the products of combustion of the alcohol with the air present, and the periods of fumigation were the same in both ‘cases. In this way the control plants were subjected to the same con- ditions as the treated plants except for the presence of a definite quantity of sulphur dioxid. Following are the results obtained on fumigating several cen trees which were growing in their natural state in the open: No. 5282. Black oak.—Fumigated 4 times July 8 and 9 with sulphur dioxid 1:1,000. After 1 fumigation the leaves were wilted and streaked. After 4 fumigations the leaves were dry and brown. The control plant was uninjured. No. 5284. White oak.—Fumigated 5 times July 10 and 11 with sulphur dioxid 1:1,000. After 3 fumigations the leaves looked gray and withered. After 5 fumigations the leaves were gray and dry. The control plant was uninjured. No. 5286. Cedar.—Fumigated twice on July 13 with sulphur dioxid 1: 1,000. After 2 fumigations the leaves looked brown and drooped. On standing over July 14 the leaves appeared brown and dry. The control plant was uninjured. No. 5288. Chestnut.—Fumigated 5 times on July 15 with sulphur dioxid 1:1,000. After 2 fumigations the leaves began to turn yellow. After 5 fumi- gations the leaves were yellow and dry. The control plant was uninjured. No. 5290. Black oak.—Fumigated 14 times from July 16 to July 19 with sul- phur dioxid 1: 10,000. After 11 fumigations the leaves were turning brown and new leaves and sprouts had died. After 14 fumigations all leaves were brown and dry. The control plant was uninjured. : Bul. 113 (Revised), Bureau of Chemistry, U. S. Dept. of Agriculture. PLATE |I. FUMIGATION CHAMBER FOR TESTING EFFECTS OF SULPHUR DIOXID ON YOUNG TREES. SULPHUR-TRIOXID CONTENT OF FOLIAGE. k3 No. 5292. White oak.—Fumigated 16 times from July 20 to »wy 24 with sul- phur dioxid 1: 10,000. After 2 fumigations brown spots appeared on the leaves. After 5 fumigations the top leaves were dry and brown. After 16 fumigations all the leaves were dry and brown. The control plant was uninjured. No. 5294. Scrub pine—Fumigated twice on July 25 with sulphur dioxid 1:10,000. After 2 fumigations all the leaves were brown, dry, and dead. The control plant was uninjured. No. 5296. Black oak.—Fumigated 100 times from August 5 to August 30 with sulphur dioxid, 1: 50,000. After 29 fumigations the gloss disappeared from the leaves and the young leaves took on a grayish tint. After 100 fumigations all the end buds were killed. The younger leaves were bleached and dotted with brown spots. The old leaves had lost their gloss and were bleached in spots. This tree was observed for three weeks after its removal from the fumigation chamber and no new growth took place. The control plant was uninjured. No. 5298. Scrub pine.—Fumigated 34 times from September 5 to September 10 with sulphur dioxid 1: 50,000. After 9 fumigations the top needles were somewhat bleached. After 19 fumigations the top needles were entirely killed and the lower needles were killed at the ends. After 34 fumigations all leaves were brown and dry. The control plant was uninjured. No. 5300. Scrub pine.—Fumigated 96 times from September 12 to October 7 with sulphur dioxid 1:100,000. After 49 fumigations the ends of the young needles were turning brown. After 96 fumigations all the leaves were badly affected, the young needles were brown and dead, the older needles dead at the ends. The control plant was uninjured. The investigation of the effect of fumigation on plants growing in the open was discontinued at this point on account of a pressure of other work, but will probably be resumed later and even greater dilutions than 1: 100,000 will be used. SULPHUR-TRIOXID CONTENT OF THE FOLIAGE OF FUMIGATED AND UNFUMIGATED PLANTS. It was next necessary to determine whether treating plants with sulphur dioxid increased the sulphur-trioxid content of the leaves so that it was present in larger quantities in the leaves of the treated plants than in those of the untreated ones. Asa necessary consequence of such an increase, the sulphur-trioxid content of the ash of the fumi- gated plants would be apt to be higher than that of the ash of the unfumigated plants. In the work of Von Schroeder and Schmitz-Dumont, previously mentioned, when different parts of the plants were treated with vary- ing strengths of sulphur dioxid, the sulphur-trioxid content of the treated plants was in excess of that of the control plants in every case, and the percentage of sulphur trioxid in the ash of the treated plants was higher than that in the ash of the control plants. The same was found to be true on making analyses of the pines and cow- peas fumigated by the writer.* Analyses of fumigated plants grown @ Haywood, U. S. Dept. Agr., Bureau of Chemistry, Bul. 89, p. 14. 14 | INJURY BY SMELTER WASTES. in the open, made during 1907 since Bulletin 89 was published, give the following results: TABLE 1.—Effect of fumigating trees growing in the open with varying strengths of sulphur dioxid, as shown by the sulphur trioxid determined in the foliage. [Caleulated to dry basis.] : Ashin | Sulphur trioxid— Serial Description. dry . leaves. jIn leaves.| In ash. Per cent.| Per cent.| Per cent. 5282 | Black oak treated with sulphur dioxid 1:1,000_____-__________ 3.89 0.70 17.99 5283 4|2 BlackcOak- used: aS COREL ae ae ee ae ee ee eee 3.68 .59 16.03 5284 | White oak treated with sulphur dioxid 1:1,000________________ 6.49 2.01 30.97 5285: | =Wihite7Oak: Sed aS | COn ERO ts ete eer = ieee 5.94 57 9.59 5286 | Cedar treated with sulphur dioxid 1:1,000____________________ 5.46 48 8.79 5286) (Cedar USCAAS 160 TVET O Pane ee aoe aa eae Pe 6.06 35 5.77 5288 | Chestnut treated with sulphur dioxid 1:1,000_________________ 4.49 1.44 32.07 5289 fChestnutased.as controln ae ee n 4.60 56 EASES 5290 | Black oak treated with sulphur dioxid 1:10,000_______________ 4.00 73 18.25 529¢ || “Black. oakvused :as Control 3222 Bo ee ee ee ee eee | 5.30 .06 10.09 5292 | White oak treated with sulphur dioxid 1:10,000______________. 5.02 .69 1 5293)" White oaksused asiCOuGrOl fo) =. ese te eee eee ee 6.41 56 8.73 5294 | Serub pine treated with sulphur dioxid 1:10,000______________ 2.39 .48 20.08 5295S CLUD PIE SCE iS COTE Oe ae ee 2.25 42 18.66 5296 | Black oak treated with sulphur dioxid 1:50,000_______________ 3.64 .56 15.38 520 fl: Black Oak USed aS iCONERO l= 22 ee ee ee ee 3.98 -50 1257 5298 | Serub pine treated with sulphur dioxid 1:50,000______________ Ye ASA -47 18.72 5299 | (Serubipine Used sas(COn Ci Ol2 == = eee ee 2.69 .30 13.01 5300 | Serub pine treated with sulphur dioxid 1:100,000_____________ 1.96 43 21.94 5301-1 Scrub pine used as COntEO)] an ee ee ee eee 2.05 ol 15242 It will at once be seen from the foregoing table that all of the plants growing in the open which were treated with sulphur dioxid contained more sulphur trioxid in their leaves than the control plants, and that the percentage of sulphur trioxid in the ash of fumigated plants is higher than it is in those not fumigated. These results at once suggest a method for determining whether trees around a smelter were killed by the fumes or died from other causes. FIELD INVESTIGATIONS OF THE ACTION OF SULPHUR DIOXID FUMES ON VEGETATION. A CALIFORNIA SMELTER AND CERTAIN FOREIGN SMELTERS. The next step in the investigation was to determine whether the dead and badly injured trees around the smelting works near Red- ding, Cal., usually contained more sulphur trioxid than trees of the same species which stood close by in the same soil, but were not killed. Of 25 pairs of trees examined in various directions from the smelter 80 per cent contained more sulphur trioxid in the leaves of the injured trees than in the leaves of the uninjured ones, while 20 per cent showed the reverse. It was further shown that in 80 per cent of the cases the injured trees contained a larger percentage of sulphur trioxid in the ash of the leaves than did the uninjured trees.? 7@U. 8. Dept. Agr., Bureau of Chemistry, Bul. 89. PLATE III. Bul. 113 (Revised), Bureau of Chemistry, U. S. Dept. of Agriculture. View ABouT 2 MILES SOUTH OF KESWICK SMELTER, NEAR REDDING, CAL. PLATE IV. Bul. 113 (Revised), Bureau of Chemistry. U. S. Dept. of Agriculture. View AsouT 3 MILES WEST OF KESWICK SMELTER, NEAR REDDING, CAL. TENNESSEE SMELTERS. 15 In a similar investigation in the vicinity of a zinc smelter at Lethmathe, Germany,* one especially conclusive examination was made of the foliage of the surrounding vegetation. The investi- gator, instead of selecting the trees in groups of two from the same location, one injured and the other uninjured, used injured trees from points near the smelter and uninjured trees for comparison at points farther distant from the smelter, but in the same direction. (When this can be done the results are even more conclusive than those obtained by the writer by the method just outlined, but, un-— fortunately, the rugged nature of the country in the vicinity of the smelter at Redding made such a procedure impracticable.) Of nine eroups of trees examined 89 per cent contained more sulphur trioxid both in the leaves themselves and in the ash of the leaves of the injured trees than in the uninjured ones. Three or four years later the same region around the zinc smelter was again examined, and it was found that in nineteen groups of trees the leaves of all of the injured trees contained more sulphur trioxid than those of the uninjured ones. From the work done in the vicinity of Redding, Cal., the following important conclusions are drawn: (1) Sulphur dioxid when present in very minute amounts in the air kills vegetation. (2) The injury is accompanied by an increased sulphur trioxid content of the foliage. (3) The vegetation around the smelter for at least 34 miles north, 9 miles south, 24 miles east, and 5 to 6 miles west, is greatly injured, and less severe injury extends even beyond these limits for a consid- erable distance (Pls. III and IV). TWO TENNESSEE SMELTERS. The next investigation of injury to vegetation by smelter fumes, conducted by the writer, was made in 1905 and the summer of 1906 in the mountainous country of Tennessee, North Carolina, and Geor- gia, surrounding two Tennessee smelters, and in the laboratory at Washington. The following counties were examined in the various trips made in the vicinity of the smelters: Polk, Tenn.; Fannin and Gilmer, Ga., and Cherokee, N. C. Again, the only injury studied was that due to the action of sulphur dioxid and trioxid on vegetation. The chemist in this investigation was accompanied by one of the for- esters of the Department of Agriculture. Samples of soil and foli- age were collected for chemical examination, but the foliage came only from those trees which the forester was reasonably sure had not died from insect pests, forest fires, crowding, or other conditions. * Haselhoft and Lindau, Die Beschiidigung der Vegetation durch Rauch. 16 INJURY BY SMELTER WASTES. 4 Sf commonly causing the destruction of forests. These samples of foliage were classified by the forester and forwarded to the Bureau of Chemistry for analysis. For purposes of investigation samples of the dead and injured trees surrounding the smelters were examined, as well as of the unin- — jured trees of the same species beyond the range of apparent injury. The sulphur trioxid content of the foliage and ash of the two sets of samples was then compared. The soils beneath the injured trees were compared with those from beneath the uninjured trees to de- termine whether any increase in the sulphur trioxid content of the injured trees might be due to an increased amount of sulphur trioxid in the soil. If the sulphur trioxid content of the uninjured trees, situated much farther away from the smelters, is less than that of the injured trees situated near the smelters, and yet the sulphur trioxid content of the soils in which the trees grow is the same, or nearly the same, in both cases, this increase of sulphur trioxid must have been absorbed from the air and must be responsible, wholly or partly, for the death of the trees, since it is known that small amounts of sulphur dioxid and trioxid, when absorbed by the leaves of trees, do kill them. In the absence of insect pests in sufficient numbers to cause great injury, of forest fires, or other ordinary causes for the death of trees, it must be concluded that it was the sulphur dioxid and trioxid alone that caused the damage. Attention is again called to the fact that this method of comparing injured trees with uninjured trees at a greater distance from the smelter is better than the method followed by the writer at Redding, Cal.,¢ and should undoubtedly be followed in all cases where such a comparison is possible. The country around the Tennessee smelters easily lent itself to carrying out the investigation in this way, while in the country around Redding, Cal., such a method of working out the problem would have been extremely difficult. In Table II are given the results obtained by examining the foliage of the injured and uninjured trees for sulphur trioxid and ash. Ina northerly, easterly, and westerly direction the writer collected and examined samples from beyond the range of apparent significant in- jury. Ina southerly direction a few such samples were collected, but unfortunately they were very wet when gathered and molded during transit. However, since the samples collected beyond the apparent range of injury in an easterly direction grew in a soil containing practically the same amounts of sulphur trioxid as the soils south of the smelters, and also since the examined area to the south is near the area over which the samples were collected east of the smelters, it @U. S. Dept. Agr., Bureau of Chemistry, Bul. 89. RESULTS OF INVESTIGATION, TENNESSEE. iG is believed that the injured trees to the south can be compared with the uninjured trees beyond the range of significant damage in an easterly direction with perfect satisfaction, and that the results of such a comparison will be just as accurate as though such uninjured samples had been taken beyond the smoke range to the south. It should be borne in mind that two smelters were involved in the above investigation, which were situated so close to one another that it was impossible to say which probably was causing the damage. Hence a point midway between the two was chosen as the most con- venient point from which to reckon all of the distances given in Table IL. TABLE II.—Sulphur trioxid in foliage, in ash, and in soils around smelters. [Caleulated to dry basis. ] NORTH OF SMELTERS. Approximate Ash in Suna trioxid— Field| Serial waves : distance and leaves SE ec No No. Beseuip vio oteam ple. direction from and eniGamecclaharach Tmeaoal smelters. | needles. : : aa : Per cent.| Per cent.| Per cent.| Per cent. 51 2797 | Foliage, black oak, injured_| 7 miles NNW__- 4.13 0.91 29.2035 | See ees 60 S806 |== a= (6 oes Sak OS bse eee eer Ome TUETe 4.62 1.05 DOR Die \ Weert eee 61 DEO (|| ene Cae ek ra ees Ng (Op eee a 4.98 1.10 22 08% Sane. ae 79 2825 | Foliage, black oak, unin- | 134 miles NNE_. 4.04 .41 TOROA eae 2 Sere ey. jured. | 59 2805 | Soil beneath Nos. 51, 60, Gi rear eae Ul er SEED aes a Me pee at gt 0.05. 80 28 7.6R lS OLDEN eC At NMINIO cei Qe a os |e ee eee eS Bee eee 2 | a .03 63 2809 | Foliage, scrub pine, muted 63 miles NNE__ 2.83 .87 SOS Cpl eee See 64 Don Om aa G OY Sa a ae OES eS ae ee ea S po Mi UR Baie 2.34 .69 PRA iui ser es eee 65 Mew b ea = 0 SS en Pee Sa ae] GN Ee en 2.99 .93 Sl Pal O): | eee eee 78 2824 | Foliage, scrub pine, “i | 133 niles NNE_| 2.06 .36 SAG | Meee ees jured. 67 21S TIS Ol beneathUNOs® 6364,65a)-. 2 ee ce eg ee ee 07 80 2826 | Soil beneath No. 78_---___- | peeeetne: eanneeme nel) See meee | ee ee Pe ee ae 03 68 2814 | Foliage, white pine, in- | 8 miles NNE___- 2.46 66 26. 82a) ec eS jured. 77 2823 | Foliage, white pine, un- | 133 miles NNE_. 1.74 36 20569 )n| eae meas injured. Tk 2817 | Soil beneath No. ce eee cet Is Ae & SES IS 0 i Yi pee aca (Pa || ee apa A 06 80 PASASS {FSS Ol bel OVEIOVSPERB ay INO Affect I EN EIR pal Se Sie aes peg Dy | ee ee .03 69 2815 | Foliage, black on injured.| 8 miles NNE___- 5.20 .95 SSO Gt |e ee 79 2825 | Foliage, black oak, unin- | 133 miles NNE_. 4.04 41 LOPS | Se ee jured. 71 PAS tal OLD GIG aula NO) 9 OO sete ek stereos ee le LE as PS Ree | 06 80 2826 | Soil beneath No. 79_______- |e co ele EE ES Se et 8 AOR Ti eS ole eo -03 100 2846 | Foliage, white pine, in- | 83 miles NNE__. 1.97 .06 DEA 0 Pes een jured. | 77 2823 | Foliage, white pine, un- | 133 miles NNE-. 1.74 36 2056974. ee injured. | | 98 2844 | Foliage, black oak, injured. 91 miles NNE_-_- 4.41 75 UAO0U == Sates 79 2825 Foliage, black oak, unin-» 134 miles NN E-- 4.04 1 OS 4a eee ees jured. | 81 2827 olan: black oak, injured _| 124 miles N. by 4,55 .59 PROG) be oases E. 83 QSZOE Aen Osean es ape ke ale Qa esa a | 4,96 .67 Se On| a eae 79 2825 Tolace’ black oak, unin- | 133 ailes NNE_ 4.04 41 OTA ete itiee Scere jured. | 89 2835 | Soil beneath Nos. Bt Qos | Ohiertecens Parr eee eee Oe ae ene | oe ee Ih SX he 8 .03 80 BISIXGS hj ~ SO Me] OVS N AW EHS vty OWT ICO 7h are ee RL Ee ee | | ees 03 90 2836 | Foliage, scrub pine, injured~ 124 miles N. by | 3.07 51 TWO | | Ei. 78 2824 | Foliage, scrub pine, unin- | 133 miles NNE_| 2.06 .36 se (0 Ie see jured. | 89 PRIS (b Sion | Ovaaveea yey avedN ays CO 0) eee eae ee LE Gee Le (ee .03 80 2826 | Soil beneath No. 78_______-. opt Seah Sp OS Oe Eas cater se |e eg ee | eee es 08 92 2838 | Foliage, white pine, in- | 123 miles N. by | Zeon .49 I9K0G3 S22 jured. qe 93 283 OM esa Cot sey aS ee eae Se, CORE 2.39 .50 209 21y eee ee 94 2RAQ eee (5 KG yes ae Nalin Seat Soe Bae ic be hs COS E iar 2.65 .50 1SeS6g| Sea 77 2823 | Foliage, white pine, un- | 133 miles NNE_- 1.74 .36 20269) 22 ee injured. | 38816—Bull. 118—10——3 13 INJURY BY SMELTER WASTES. TABLE I1.—Sulphur trioxid in foliage, in ash, and in soils around smelters— Continued. EAST OF SMELTERS. Approximate | Ash in Sulphur trioxid— Field} Serial ae distance and leaves No. No. Description of sample. direction from and Tristan I . Sere. needles, |/2 Jeaves.| In ash. | In soil. Per cent.| Per cent.| Per cent.| Per cent. 149 2895 | Foliage, white oak, in- | 3 miles ENE___- 3.74 0.85 22 cif2u| ae i jured. 158 2904 | Foliage, white oak, un-| 83 miles E___-__- 4.78 .08 [213 y Peo eae injured. | 153 2899 | Foliage, shortleaf pine, | 43 miles E_______ 3.53 61 Lis28 0 een eee injured. 154 2900) |Saeae GO SHE Reis 2a een een aI OMe ena wre 3.28 .70 PAB 4) NS eee 153 2899 | Foliage, slortleaf pine, | 83 miles E______- 2.82 -40 14185 ae ee uninjured. ; 156 29025)| “SOibe IDEM ACW EIN si, We ee ee eee ee | 0.04 154, 161 9907" SOlLbDenGath NOs V5 Gs Sa eee eee tee ee | ee | ee ee eee 04 171 2917 | Foliage, shortleaf pine, | 53 miles NE____. 4,16 -80 NGL OS): Saas Ree injured. 157 2903 | Foliage, shortleaf pine, | 83 miles E______- 2.82 -40 14 Si Sig es ere uninjured. 175 9991 | -Soilibeneath NOs ie ae soe ee aaa a ee ee |e ee | ee .06 161 2907 VSO: Were aCe HNO ee eu a re | a ER ea aa | ee 04 164 2910 | Foliage, shortleaf pine, | 5 miles E_______. 3.53 .83 Pao) Wp nee ee injured. | 157 2903 | Foliage, shortleaf pine, ; 84 miles E___-__-. 2.82 40 LENS eee ee uninjured. | . 166 2912 | Foliage, black oak, in- | 5 miles E______-. | 5.14 ATA PSS Tin Shee ae ars jured. | | 159 2905 | Foliage, black oak, un- | 8% miles E____~_-- 3.15 49 15.255) (ooo ees injured. | 168 2914 | Soik- beneath cNOS:) 164,722 a ee ee eee ene eee .06 166. 161 9907 eS oil’ beneath Nosel57;. 159% | eo ee ee eee eee .04 176 2922 | Foliage, black oak, in- | 6 miles NE__-_-. 5.34 94 17.560 4| 2a ee jured. | | 162 2908s | Same GO eae Sry ae ea 5s milessh es 4.10 .63 L523 7A ee eae 159 2905 | Foliage, black oak, un-| 83 miles E_____.. ! Sale .49 Los5a7| sees injured. | SOUTH OF SMELTERS. | Per cent.) Per cent.) Per cent.| Per cent. 103 2849 | Foliage, white oak, in- | 2 miles SSW___.| 6.48 0.92 4330 a|Se eee jured. 158 2904 | Foliage, white oak, un- | 83 miles E_____-_. 4.78 58 12:13. === eee injured. 105 2851 | Soil beneath No. 103____-_- Yap st ned go TENA Stee ALG SET 2 0 a 0.05 161 2907 | Soil beneath No. 158______- [ee RU ie Ae Pap) CS, eee ee On ee 04 106 2852 | Foliage, white oak, in- | 3 miles SSW_--.'| 3.63 .49 13.496) S ees jured. 158 2904 | Foliage, white oak, un-! 83 miles E_-____- 4.78 58 Naa EAD ae injured. | | 143 2889 | Foliage, shortleaf pine, | 3 miles S___-__. ; 2.97 .66 22) O00 aie k ema eee injured. 144 28905 eee CO Sted ce eee eA eee CLO eee ae aes 2.91 0 20-61" |-3 =e 145 2.89 [ex eee GOS a SEN ee ee Paes a dose ts 2.83 Sul 25 08a ae eee 157 2903 | Foliage, shortleaf pine, | 83 miles _-__--. 2.82 40 145134 )55e uninjured. 148 ISGe | Sol beneath: NOs: < Wass yess oe ee ee 2 ee ee es ee LE eee .05 144, 145. 161 2906, SOs Dene atl AN. Wa 7 eae es ee Bs a ae Pa ae se | 04 138 2884 | Foliage, white oak, in-| 4 miles S___----. 5.46 1.03 18.8652 eee jured. 158 2904 | Foliage, white oak, un- | 83 miles E_____- 4.78 -08 Losses eee injured. 142 2888 | Soil beneath No. 138_------ ba fy ea EE Sn illim Sale Oe) RS ee ee .04 161 29075 2S Oil DENA tl NO Ss ee a ae | See ST ee |e a | Caen .04 136 2882 | Foliage, white oak, in- |; 64 miles SSE_-_- 4,58 clit U6 8) ts = ee eee jured. 158 2904 | Foliage, white oak, un- | 83 miles E_--__-- 4,78 -58 12 SS eee injured. TABLE II.—Sulphur trioxid in foliage, in ash, and in soils around RESULTS OF INVESTIGATION, TENNESSEE. Continued. SOUTH OF SMELTERS—Continued. 19 smelters— Approximate | Ash in Sulphur trioxid— Field} Serial eet distance and leaves No No Description of sample. | direction from and Tulenvecdiciaiach Taeoil smelters. needles. : . Sou | Per cent.| Per cent.| Per cent.| Per cent. 134 2880 | Foliage, black oak, in- | 63 miles SSE___ 4,52 0.73 G1 5s | Sess jured. 159 2905 | Foliage, black oak, unin- | 83 miles E______- 3.15 .49 15 R55 ae jured. 120 2866 | Foliage, black oak, in- | 9 miles SSW___- 3.58 .39 AOE 89> aban jured. | | 159 2905 | Foliage, black oak, unin- 83 miles E____--- 3.15 .49 SD 5p |e ee jured. | 128 2874 | Foliage, black oak, in- | 93 miles SSE___ 4.69 63 13249 0s|2 Seka as dured 129 5, Oe | eee CL a I Ti TRE ae (6 (see 4.32 Sf 13e19) | Saaeaee 159 2905 Foliage, black oak, unin- | 83 miles E______- | 3115) .49 DUES) | ee ees Ss jured. 131 2877 Soil Deneath, Nioss1285 129s |50er ee eee [See eS Petes el De een | 0.05 161 250s Olibeneathy NO wI59= 22 alias Se sea ee ee ee Ee a ae ee CEA | 04 124 2870 | Fojiage, searlet oak, in- | 103 miles S____-. Dei: .67 DAAG Ti |e eee. jured. | 160 2906 | Foliage, scarlet oak, un- | 84 miles E_____-. | DoH 50 TS205i | Gee eek injured. | | 126 2872 | Foliage, black oak, in- | 103 miles S____-. 3.59 .41 MAD eee ee jured. 159 2905 | Foliage, black oak, unin- | 83 miles E______. | Srall5 .49 IGG, ea jured. WEST OF SMELTERS. : | u | Per cent.| Per cent.| Per cent.| Per cent. 1 2747 | Foliage, post oak, injured_; 24 miles WNW_-.- 4.53 1.31 285921) | Racca ee eee 3 FAQ: ee Fi OS ae ee SS ae ee 3 zales WNW--, 4.60 1.02 DOUG alent ea 5 26 oe | a COM Eee ca eee | ee OP ae se 5.386 Lae} DANA VS eee oh ea 24 2770 | Foliage, post oak, unin- | i3i miles WNW. 5.48 aby 10.40 | ob jured. | 7 2753 | Foliage, white oak, in- | 3 miles WNW_-. 4.46 1.09 DAW AA | erence UEC sar | | 25 2771 | Foliage, white oak, unin- | 133 miles WN W_ 6.11 79 12898) | ae ee jured. | 9 2755 | Soil beneath No. ie FE pla ok Re eal [ole RET ES) ee eee | Cee 0.06 27 CiSa| eS Ollebene acy NO)c Zoe ses eee See ROR SESE |S 2 ee eRe ee ee eee} 04 10 275 Foliage, See cat pine, . 5 miles WNW-- 3.47 .84 PAGO Ge eee anne annneds 15 27 Ole ps! ae C1 Ose soe tee ea Rep eet 0 (0 ae eee ee ee 4.18 .86 20 ED (pe | eee 23 2769 Holiaces shortleaf pine, . 133 miles WNW. 4.40 AY NP F4O 5 ie | a ete ace uninjured. | 12 2758 | Foliage, white oak, in- 5 miles WNW_-. 4.47 | 92 20258 ul Sate Bes \ jured. 3 25 2771 | Foliage, white oak, unin- | 133 miles WNW- 6.11 .79 L2EOS'S |e eee jured. 14 Pr60s las OllabeneathareNOsitd OMe Moyes es eae ee Pe S| ae a aa Ee 04 IDs | 27 2773 | Soil beneath Nos. 28, 25__-.'__--- a ee ee eee ee ee 04 17 2763 | Foliage, white pine, in- 6 miles WNW_-. 2.98 3783 DAE) | eee a jured. | 18 VTS ee 51) OE eee ees (6 Ko ease ea 2.36 73 305930 eee ae 28 2774 | Foliage, white pine, unin- | 133miles WNW- 3.08 PATE | 5G ae ee jured. | 20 2766 | Foliage, Spanish oak, in- | 6 miles WNW_-. 4.29 ° MEST SN) sj | eee jured. 26 2772 Foliage, Spanish oak, un- ; 133milesWNW- 4.58 .69 BS O fii es eee ae injured. | 22 2768 Soll Deneath ENOSsaliis 1824) See eee ee eee ae | ee | ee eee -06 27 2773 Soil beneath Nos. 28, 26_-_.|----- ene eee sees oe sy ee 04 180 2926 | Foliage, white pine, in- ; § miles W_-_----- 2.48 5 fal PSE 63h es jured. 28 2774 | Foliage, white pine, unin- | 133 miles WN W-_ 3.08 47 5226" |e aeoee eee jured. 184 29304 eS oilibenecath No. 18022-4202 ees eres pect ee sto Barer tel eee 04 27 Pisales O1lmpeneath NOx 2822222.) /B2 See (OE 32 ag SE OO os ee ee 04 29. 2775 | Foliage, white pine, in- | 94 miles WNW-. 1.90 04 QQvAD ieee Se ae jured. 28 2774 | Foliage, white pine, unin- | 133miles WNW-_ 3.08 47 52267 || aa ee jured. 20 INJURY BY SMELTER WASTES. In this table, with possibly two or three exceptions, it will be noted that the soils close to the smelters contain very nearly the same amounts of sulphur trioxid as those farther away, so that in comparing injured trees situated near the smelter with uninjured trees at a greater distance the soils in which they grew may be con- sidered identical. Out of 49 such comparisons it will be noted that 46 times, or in 94 per cent of the cases examined, the sulphur trioxid content of the injured trees is larger than that of the uninjured trees of the same species situated beyond the range of the. seemingly significant dam- age and that in 40 cases, or 82 per cent of the number examined, the sulphur trioxid content of the ash of such injured trees is larger than that of similar uninjured trees situated beyond the range of apparent damage. | In a northerly direction in 100 per cent of the cases examined the leaves of the injured trees contain a larger percentage of sulphur trioxid than the leaves of the uninjured trees and in 81 per cent of the examinations the ash of such injured trees contains a larger per- centage of sulphur trioxid than the ash of the uninjured trees. In an easterly direction in 100 per cent of the cases examined the leaves of the injured trees contain a larger percentage of sulphur trioxid than those of the uninjured trees and in 75 per cent of the cases examined the ash of such injured trees contains a larger per- centage of sulphur trioxid than the ash of those uninjured. In a southerly direction in 77 per cent of the cases examined the leaves of the injured trees contain a larger percentage of sulphur trioxid than the leaves of the uninjured trees and in 69 per cent of the examinations the ash of such injured trees contains a larger per- centage of sulphur trioxid than the ash of those uninjured. In a southerly direction, if only those trees are considered which were within a distance of 64 miles from the smelters, it appears that in 88 per cent of the cases examined the leaves of the injured trees contain a larger percentage of sulphur trioxid than those of the uninjured trees and in 100 per cent of the examinations the ash of such injured trees contains a larger percentage of sulphur trioxid than the ash of those that are uninjured. In a westerly direction in 100 per cent of the examinations both the leaves and the ash of the injured trees show a larger content of sulphur trioxid than do the leaves and the ash of the uninjured trees. From this investigation the following conclusions are drawn in regard to the distribution of the injury by smelter fumes: (1) The vegetation around the smelters appears from actual chem- ical analysis to be injured for at least 12 to 124 miles north of the smelters, 64 miles south, 54 to 6 miles east, and 94 miles west. INVESTIGATION AT ANACONDA, MONT. alt (2) There can be but little doubt that the injury extends beyond the limits mentioned in the preceding paragraph, but this can not be shown by chemical analysis, since the difference in sulphur trioxid content between injured and uninjured trees becomes so small as to be within the limits of experimental error. FIRST INVESTIGATION OF INJURY BY SMELTER WASTES AROUND ANACONDA, MONT., 1906-1907. A third extremely important study of injury to vegetation and ani- mal life by smelter wastes was conducted by the writer in the country surrounding Anaconda, Mont., and at Washington during the latter part of 1906 and the whole of 1907. In the immediate vicinity of Anaconda the huge Washoe smelter is situated, roasting, when run- ning at full head, from 8,000 to 10,000 tons of ore per day, which ore is said to contain quite large quantities of arsenic. (See Pl. V.) The plant is situated in a semiarid country, where irrigation is vracticed, and discharges its tailings and slags into certain of the streams that are used for irrigation purposes. There are therefore three distinct problems to be worked out in connection with the injury caused by the smelter: (1) Whether or not the vegetation is injured by reason of the sulphur dioxid and trioxid set free. (2) Whether enough arsenic is set free to settle on the surround- ing forage plants to make them unfit for stock. (3) Whether the waste when discharged into the irrigation streams renders the water unfit for irrigation purposes and injures the soil to which such water is apphed. All of these problems were studied, and definite data bearing thereon obtained. The chemist in this investigation was accompanied by one of the foresters of the Department of Agriculture. Samples of soil, foliage of trees, forage plants, irrigation waters, ores, and of the dump heap were collected and forwarded to the Bureau of Chemistry for chem- ical examination. As in the Tennessee investigation, samples of foliage were collected from those trees which the forester was certain had not died from insect pests, forest fires, crowding, or other com- mon causes of forest destruction. A few paragraphs of introduction are necessary in regard to the situation of the smelter and the appearance of the surrounding country. LOCATION OF SMELTER AND APPEARANCE OF SURROUNDING : VEGETATION. The Washoe smelter is situated on a high hill toward the southern end of Deer Lodge Valley, which is about 35 miles long and from 4 to 6 miles wide. (See Pl. VI.) It is located about at the junction yy INJURY BY SMELTER WASTES. of Deer Lodge Valley and Warm Springs Creek Valley, and is near the Hell Gate and Helena National Forests and certain other public lands. To the north, south, east, and west of this valley are quite high ridges of mountains which are cleft here and there by the val- leys of small creeks, of which Warm Springs Valley is one of the largest. Down the center of Deer Lodge Valley runs the river of that name, into which is carried part of the tailings and slag from the plant and the wash from the dumps and slime heaps. As before mentioned, this river is used for irrigation purposes, although a large number of the farmers say that it is injurious and prefer to get their water from small creeks coming down from the mountains on either side, only using the river water when it is absolutely necessary. It is only near the tops of ridges and beyond them and along the val- leys of the various small streams that the land is forested to any extent. Besides this, forest fires have swept over certain of the mountains in the past, so that all dead timber can not be ascribed to sulphur dioxid from the smelter. However, enough trees remain within a radius of 10 to 15 miles from the smelter, which have not been injured in any way by the forest fires, crowding, insect pests, etc., to enable one to observe the damage caused by sulphur dioxid. The three principal kinds of trees in the neighborhood of the smelter are the lodgepole pine, juniper, and red fir. The difference in their resistance to sulphur dioxid fumes is very marked and can easily be observed. ; Immediately surrounding the smelter practically all trees are either dead or severely injured. F y : =) DR ot, goed YASS AIA FOR? fr. bel eS 7 “Ye, Mi VAG LYEG a, S S55 we WER OY AS Yi HAW a ala “i Wy g £2 \ Bis 3 Gronarowne GYL iY AKET ON UAE OLE 404 oY AP Vi ibe ees \S , 7 VAAN WY) OKA ot OR f AOA Vi UA A / BO | Bl Via S| as Pi me NS Bix a K \ 1 aR — 2 RUE. IS a5, m3 a an Se ee bel Ne ga iAH Ls gle ba i g =) wet Tt Tt dij ION ‘SX y 4 “sr ig kd ri | ve +: Fe I: amnm Set pc \ ES Tt | es WY, CS N Ni NY we poet SS AND SAE AX > SN NS Sere ny RS ce nef s 4 NS WN Re Fr Sete kh (TEA CONS 5 Zara Ww Za WY hg, © A ce Uf, Yi O77 BZ y % %y ‘My (BANG? vee he C7 ae SGI EE| SS We fe | R wB ; BNA mS = x SS Sila PAL i 0. “if Pcl 1 1h ree ee NAS Cn, O° 1 ih te yy 7% Wh iF + “i oo GY Nill SHIASE le Ww q i 1i\\ Yan C XZ R.12W. R.1LW. R.10W. R.9 W. R. 8 W. SCALE IN) MIEES “= . 7 National Forest Boundary ——= 3 $ 2 _ Public land REG) PSION AROUND ANACONDA, MONTANA, SHOWING NATIONAL FOREST BOUNDARY AND PUBLIC LANDS IN R. 8 W., R. 9 W., R. 10.W., TPe 3) 4 01 01 me, ee MAO UNORUrE wasescion oc EACH RANGE; R. 11 W., TPS. 4 AND 5 N.; AND R. 12 W., T. 5 N i = nevis taut io ba ae Lapel "ae rk eae ‘ ie Gee ee seonvod tesro) ler INVESTIGATION AT ANACONDA, MONT. 3 were badly spotted and injured for several miles from the smelter, and down as far as Race Track the crops did not appear to grow as luxuriantly as those around Deer Lodge. The trees growing in the valley were so few in number that it was nearly impossible to judge what their injury might have been. In several places examined south of Race Track the soil that had been irrigated by Deer Lodge River water appeared to be injured, especially near the irrigation ditches. This injury was shown by bare spots in various fields, such spots often showing a blue-tinted crust that evidently contained copper. This was especially true in fields along the river in the vicinity of Race Track. Beyond this point no serious injury to the few trees remain- ing was noted. The crops of alfalfa, potatoes, clover, etc., examined beyond Race Track did not show any evidence of having been at- tacked by smelter fumes. A trip was next made from Anaconda along the western side of Deer Lodge Valley until Lost Creek was reached, the valley of this creek being followed for about 7 miles. Samples of cattle-food materials, soils, and foliage were collected and observations were made on the general appearance of the vegetation. In Lost Creek Val- ley the junipers were absolutely uninjured, and the lodgepole pines were badly injured at the lower end of the valley, but the damage gradually grew less until it became practically insignificant at a dis- tance of about 5 miles up the valley. Throughout the entire 7 miles of the valley the red firs were almost all killed, although an occa- sional live one, or a group of them, would be found. A trip was made from Anaconda along the western side of Deer Lodge Valley until Modesty Creek was reached. The valley of this ereek was followed for about 5 miles. Samples of cattle-food ma- teriais, soils, and foliage were collected and observations were made en the general appearance of the vegetation. The lodgepole pines throughout this valley were injured to only a very slight degree, this distance evidently being near the extreme limit of injury for this species of tree. About 50 per cent of the red firs were dead or badly injured and those remaining did not appear to be healthy. Another excursion was made from Deer Lodge up the valley of Tin Cup Joe Creek for 2 or 3 miles. The lodgepole pines were un- Injured and reforesting was taking place. The red firs were hardly touched, only the older ones showing any injury at all, while young red firs were rapidly springing up. On the whole it appears that this valley is beyond the limit of injury to lodgepole pines amd at the extreme limit of injury to red firs. EAST OF THE SMELTER. The only trip made to the east of the smelter was in connection with the return trip from Deer Lodge, already described. As far as the writer examined east (which was to J. R. Perdee’s place, a dis- 24 INJURY BY SMELTER WASTES. tance of about 6 miles), the few trees and crops that existed appeared to be considerably damaged. It is possible, however, that this was due partly to lack of attention on the part of the ranchers. No at- tempt was made to examine the mountains on the east side of the Deer Lodge Valley, as it would have been impossible to tell whether any injury that was found was due to the smelter at Anaconda, or to those in the vicinity of Butte. SOUTH OF THE SMELTER. Going south from Anaconda, a trip was made along the road which first runs to the east and then turns southwest until it crosses the divide. The point reached was 9 or 10 miles southwest of the smelter and about 2 miles beyond the divide. Samples of soils and foliage and dump and slime samples from the smelter were collected, and observa- tions made on the general appearance of the vegetation. Three miles south of the smelter the trembling aspens were badly injured, spots appearing all over the leaves. Four miles south some of the lodgepole pines were dead, while the remainder were badly injured; practically all red firs were dead. Five miles southwest of the smelter the lodge- pole pines were damaged less, but still showed injury to a considerable extent; again, the red firs were practically all dead. For from 6 to 8 miles southwest of the smelter, to the divide, the lodgepole pines were living, but most of them showed more or less injury to the ends of needles; again the red firs were nearly all dead, or seriously injured. Two miles beyond the divide the forest did not appear to be damaged. WEST OF THE SMELTER. A trip was made in a westerly direction from Anaconda up Warm Springs Creek to Silver Lake and back. Samples of cattle-food ma- terials, soils, and foliage were gathered and observations on the gen- eral appearance of the vegetation were made. None of the junipers observed on the western trip were injured in the shghtest degree. The lodgepole pines were all killed in the vicinity of the smelter, but the injury to this species gradually grew less, until, at about 10 miles west of the smelter or slightly beyond this, it ceased entirely, and beyond this point they were apparently uninjured. The damage to red firs was exceedingly great for a distance of 13 miles west, grad- ually growing less beyond this point, until on the shore of Silver Lake, 15 miles west of the smelter, it apparently nearly ceased. (See Piss Véliisand? VE: ) On the whole it may be said that the injury to red firs around the Washoe smelter extends for a distance of about.15 to 19 miles north, an indefinite distance east, 8 miles south, and 15 miles west. The injury to lodgepole pines, however, only extends for a distance of 9 to 10 miles north, an indefinite distance east, 8 miles south, and about 10 miles west. Bul. 113 (Revised), Bureau of Chemistry, U. S. Dept. of Agriculture. PLATE VII. Fic. 1.—VIEW OF MOUNTAIN ABouT 2.5 MILES WEST FROM WASHOE SMELTER—FORMERLY COVERED WITH TIMBER TOWARD THE SUMMIT, BUT NOW BARE. Fic. 2.—VIEW OF MOUNTAIN SIDE ABouT 3 MILES WEST FROM WASHOE SMELTER—RED FIRS KILLED AND JUNIPERS APPARENTLY UNINJURED. SULPHUR TRIOXID IN FOLIAGE ABOUT ANACONDA. 5 2 SULPHUR TRIOXID IN THE FOLIAGE OF TREES AROUND WASHOE SMELTER. The samples of injured foliage near the smelter and of uninjured foliage of the same species of trees beyond the apparent range of smoke damage, collected on the trips enumerated, were examined for sulphur trioxid and ash and the results were compared, as in the Ten- The soils beneath the injured and uninjured nessee investigation. trees were examined for sulphur trioxid, to determine whether any increase in the sulphur trioxid of the injured leaves could be due to an increased amount of this constituent in the soil. table are given the results obtained: In the following Taste III.—Sulphur trioxid in foliage, in ash, and in soils around Washoe smelter. [Calculated to dry basis. ] NORTH OF SMELTER. Serial No. 4168 | 38816—Bull. 118—10——4 Ashin Sulphur trioxid— ahene | Location and approximate | leaves = | Description of sample. | F | | | distance from smelter. | Re In leaves., In ash. | In soil. | | Per cent. | Per cent.| Per cent. | Per cent. Foliage, injured red | 5 miles N, 2} miles up Lost | 4.39 | ayy | 25 29M aye eee fir. Creek Gulch. | Foliage, uninjured red | 18-19 miles N, 13 miles up Tin | 4.52 | 84 | SRS stash aN Ca fir. | Cup Joe Gulch, seemingly | beyond range of damage. eee GOP ieee Sera Oge cecinen? see eser eee ue 4.57 86 IS Re soda tease JOVI RE a in somal Goeeeioae hoe ap OSB eooesooeeasrs se Seoesaeeae .89 | TS at OW eres eta DOMHCNCACHRNOm 4 Osu Seer Suen tans pean. Narre m tis [Sees Cte ee 0.08 SOUsMeM eat MIN Ost48)7. OR | Meee erie ees ae se oe RE ere el Soe ete) od He Meee aie 02 SoisbenesthyNors4So2 slant eA seo a Seren eee a ie pet bee .013 Foliage, injured red | 5 miles N, 2} miles up Lost 4.43 125 DAS Ad is Oe os ee ae fir. Creek Gulch. | Foliage, uninjured red, 18-19 miles N,1} miles up Tin 4.52 | .84 | TRESS ahaa eee fir. Cup Joe Gulch, seemingly beyond range of damage. bases BVO ses SoGie ey SCE STE HAO | 0) a eg see eee a ea 4.57 .86 IR teyA. segeiaoeac AOU Be Sa Bele ee ee te aes neta = es 2 eee [ee ee .85 SHO) eee eee were SOUL ESSA INO 2 BUY A a a ete [a Sm Lee ae) ey an ee 08 SOMBMCMEAL BIN O48 (0 ml tema Me set ceth ae shey Ret ay Nike oye cree [Spies etna | APES ge NN i Se 02 SOIT OSTACR HAD INIOs Zia Ee el a oe ee ee [peek esos | Shaca aeerances [eae 013 Foliage, injured. 10 miles N,3 milesup Mod- 2.61 LOC PAO ese ee lodgepole pine. esty Creek Gulch. Foliage, uninjured | 18-19 miles N, 13 miles up Tin 2.45 49 | 202 00g Stee lodgepole pine. Cup Joe Gulch, seemingly beyond range of damage. ee si GO te ph Ss SSS Cee SEO Oe a ae ae eee rae 2.87 | 61 PAN PAY | een ene INSTT es UN aoe Ae ren apes |e Ceo | 5 DOROS |e eee SO! Sea W IN@¢O272e | nese seer seep Booares seacenel ocbes nae Beeet aaa oe ae | .02 Sollocoen wel INO. Oral ba cececase be seoukoeoosecelocesd Geom aisene Es asaeeeae Soa men seem | 02 SOIMOCLTO DLN BIN OAS Tie epee ee oa sec ne ee ms See et |e ee eM aN he 2a | hae Foliage, injured | 10miles N, 3 miles up Mod- 2.82 74 | 26):248 lie. eae lodgepole pine. esty Creek Gulch. Foliage, uninjured | 18-19miles N, 1} miles up Tin | 2.45 49 | 20°00) |e aeeee lodgepole pine. Cup Joe Gulch, seemingly beyond range of damage. | Mae CD Pee ee oa lies Ones See a eysheaen hee en 2.87 61 | D1 267 | eee ey. ARVO TD Owe Sica vos Nuseareveerate sis yt oy erates Mech oie UyMee ee tea ESTRELA 155 20638 =e eee 9 os 6 INJURY BY SMELTER WASTES. TABLE II1.—Sulphur trioxid in foliage, in ash, and in soils, ete.—Continued. NORTH OF SMELTER—Continued. Ashin Sulphur trioxid— Serial saat Location and approximate | leaves 2 O. Description ofsample. distance from smelter. and inlGesee) Ter I : | needles. : : n soil. Per cent.| Per cent.| Per cent.| Per cent. 4168" | Soil beneath ING 4223 4 css nae. a Se ee = arrears | pe enero | ee 0.02 (SoilsbenecatheNowas ier = ss. eer Ss ewes ee ee ee \ 38597) Soil beneath Now AsiSiie tl) fa ee oe 02 4295 | Foliage. injured red | 10 miles N, 3 miles up Mod- 4.85 1.04 21.J44;, | yee fir. esty Creek Gulch. 4879 | Foliage, uninjured red | 18-19 miles N, 1} miles up Tin 4.52 .84 18.585 |eeeseeeeee fir. Cup Joe Gulch, seemingly beyond range of damage. ASS2y ewe Ne COLT ye a ae oe ae GOA eee ee Beye 4.57 86 18:82 |" aes AVCLA BS ce cic iee AiR acorns Sere ee ete ae eee | eee enn 85 18). '70:| 2.2 ALG3iisSoil bemea Gh Nio | 422 53 ee Be ph eee eS ee aes ere tm face ene | a er .02 4883" ("Soll benestheNos 4879 2] oso oe eee ee et ec oes rel epee Aas n= pera ae [ig aga a 02 4884 | Soil beneath No. 4882.|...... ASO A SEBO Sacre tuer aot cc (see seeeol ee eedcece |e acagsoce 013 4296 | Foliage, injured red | 10 miles N, 3 miles up Mod- 4.73 - 90 19: \03)*|s 22 eee jp fas. | esty Creek Gulch. 4879 | Foliage, uninjured red ; 18-19 miles N, 1} miles up Tin 4. 52 84 18) O89 eee eee fir. Cup Joe Gulch, seemingly beyond range of damage. A882 nea G Koy renee Saari eerie (6 Lo eae ee eases ee 4. 57 . 86 TSO ise eee ASV OCTASC. ce Sok sala oaes SSO See Tee eee ea Semen 85 aOR sees AGS a Soil beneath NO s42264l eh. aos niagara csi Sore ae erate [es en re etre | epee re | re . 02 48832 "Soiltoenea th’ No: 4879.5) sorte ce yes eek Steere tee eae pele ronan ae |e ee | ee . 02 A884.) Soil beneath, NOx4882 joi 5 Soca See eae Ae eye eager [Re cae Pe me yl ee | . 0138 SOUTH OF SMELTER. | Per cent. | Per cent. |Per cent. Per cent. 4070 | Foliage, injured lodge-| 4 to 44 miles a little W of S-- Bee al 0.95 30:00:22 eee pole pine. ‘ - = ic 10 miles SW; 2 miles beyond 4080 1) Foliage, uninjured iardolineciinelorGevond 2. 68 51 19°03 -| 22 ee 4081 f lodgepole pines. Pee pidaniiee., 3°. 2. 69 73 OF 1 ee VASVICT AOL... Sea eee hE ae. oe ere at ore Cee ool cee ie .62 23,0902 A161 Sothibenea- th Nox 40 COs sess See esa mya eee ae ell eee eae tet | | a 0.03 4163. Soil beneath No. 40803 s eee ee eo ares eps ree al | ree Pete pegeve tel ees oes | ee 02 INSoilsbeneatheINo:. A081) 255s se yee er Ne mel | ee : 4071 | Injured lodgepole pine| 4 to 4} miles W of S.......--- 2.69 76 PAPA IU Bie ah abe : he 10 miles SW; 2 miles beyond 4080 || Foliage, uninjured Avmniellccentan 2.68 Si 19: 035 )Seeee: Z vide, gly beyond ps 4081 { lodgepole pines. range of damage. 2.69 13 PA feel tc: Sal ore ee gaNQ YG 2s re a Pel A em, oe Met iS AeA Nel ee aameee 62 23:09 5) =e AlGIe| Soil beneuthy No 407Ia|s8\ ae eee ene meee EN Dasenire eee .03 poilibenesath- No. 4080.) 232 eh ie ae Oe ee Wea | ws les ey re ee ee |e 4163 {Soil beneath: No: 4081 2) 2:23 52 ieee es ae ne oe ec 5 | See | \ Ue 4074 | Foliage, injured lodge-| 5milesSW......----------.-- 3.51 82 Bas el eters es See pole pine. >: 4 ———_— |— — — == ; ar 10 miles SW; 2 miles beyon 4080 || Foliage, uninjured | digideulceoniticle 2.68 5 192033); ss eres | oa ; gly beyond = z 4081 |f lodgepole pines. range of damage. 2.69 73 D1 V4 | eee INVOTASO MSS co HOSE wis's aie, ae tetera eee Pe | ee 62 2a: O9T| aap erie AL620| \Soibbenea th: NO« 40742) 2222 cee ca weseele cece ee ee ee ee eto ae eae rea : .02 Soilsbenesth NiO 4080 | eesa2 See arcs ec i eet eee ere re eet ee eee 4163 1 Soil beneath Noz 4081s is oe se Sees oe a ae a ee RE es ree a Ss cen | ree eee I A 4075 | Foliage, injured lodge-| 5 miles SW__.......--.-.--.-- 3.43 1.02 293 74a eee pole pine. | P Amie, 10 miles SW; 2 miles beyond 4080 || Foliage, uninjured | diviiolccariin 2.68 sol 1920322 ses ese ; : 3 ; gly beyond " é 4081 { lodgepole pines. range of damage. | 2.69 43 ZEA so eee IAVCTA SO a8 cn oe Ro eemee Senet eee ee eer pee eT . 62 232093 Bence sete eS ed — TABLE III.—Sulphur trioxid in foliage, in ash, and in SULPHUR TRIOXID IN FOLIAGE ABOUT ANACONDA. ’ SOUTH OF SMELTER—Continued. soils, etc.—Continued. Ashin Sulphur trioxid— Serial ee Location and approximate | leaves Description of sample. : No: ULSUDINES MOV LNG ete: ane In leaves.; In ash. In soil. Per cent.| Per cent. | Per cent. | Per cent. Ale ome Smilanencathe No: 40755 )s0 ee Cease kee ee ee ees [ee acta Ae Sade 0.02 4162 |sSoil beneath No. 4080. .|........--.--------------- +--+ +]. +--+ +222 +/--- 2-2-2 - +) 222-22 --- | 02 PAN RSIOHUTL Toye ere RET OY INNO LTS A 2) Ie i elo | ieee a geet [oe ea if cae 4077 | Foliage, injuredlodge-| 6 miles SW..........--.-..--- 2.53 0. 90 | SUD OY [dee tooade pole pine. aes (10 miles SW; 2 miles beyond | : 4080 Hewrectes peur ane’ | divide, seemingly beyond 5 & 2 cae Hite gine 4081 pe scho-> pines: | range of damage. : ; aM ake, og earls Ayera gen 422 I eats BIG Ts Bess See ea hs ea i ee =a T62U i oenes OO lst ee canes Soulibeneartinw Nox ira see se cre cree ee etre eeepc eR te ata oe hee a cee ge ROK | TE a a SOW eae UN INO. CUR liao obese ooosebebsendesbecosEedd|eaacsornacs | Saeeea es ele Pa eeeeer SS NE SoililbemeaiGheNo yaOs Vers ase eat seals Bye eee NEE oy Sega eta ue ce iapelerl otllleapatc Suche oat ce ore ayelee ioe i Hae tees y 4078 | Foliage, injured lodge-| 6 miles SW..-..--..---.----- 2.54 59 D328 O 3M tose hats pole pine. I: | ia Si 10 miles SW; 2 miles beyond 4080 |\Foliage, uninjured divi NOE 2. 68 Ol IQR OS |Raeeeee : ivide, seemingly beyond a | 4081 \ lodgepole pines. range of damage. 2.69 | WS | DAT Se nae BAG OTC eg a hres Seat nye a Se yc EIN Pattee Bra cra Pies See et | . 62 Pav UO) Ws sBen onic Saubencathy NowTeasneesanice nie ao ee cena: eee is ae ee SorldbemeaithnwNos 4080 sahara eee oa ee eae VOW) | VOVEROVS HT AVI ays UNM SHEN eS I haere ee pea Pela ere all arta aoa a 7 her ee to ane ae WEST OF SMELTER. Per cent.| Per cent.| Per cent.| Per cent. 4089 | Foliage, injured lodge-| 6 miles W...................- 2.91 0.75 PAE as Sah ee pole pine. 4152 | Foliage, uninjured | 15 miles W; shore of Silver 2. 61 . 30 DEA OY ie Reine tere lodgepole pine. Lake, seemingly beyond range of damage. Soildbeneat HyNos4a0 ses eavarer ween ees seein es eee Sra eea cee |e Sea ae eee eo reteta wa. iS oe SorldbemeatMeINnoyAls 26s meses co See eer toe ie ee araie cyarorel| Sees iets aoc ow cies aro leisy sacs oll rete oteaeieteie 4090 | Foliage, injured lodge-| 6 miles W.......----.--.---- | 2. 68 69 PUD Woacancuade pole pine. 4152 | Foliage, uninjured | 15 miles W; shore of Silver 2. 61 . 30 TAL FAG sis eee nere lodgepole pine. Lake, seemingly beyond range of damage. Soll lnsmenidoy IN@. 40M cease vee aa coe seep seopaseseeoonee VAs lie onvale cron aperereraletaterkict aoc Senility eer SoljbencatheNos4g2 | aes so eso ae aa ae ce ets een Ieeceoeeaiey = Cle aI ic, aml dl co Rs at Me aan ue 4086 | Foliage,injured lodge-| 7 miles W......-.-.-.---.--- 3:15 153 NG CS he codaoocos pole pine. 4152 | Foliage, uninjured | 15 miles W; shore of Silver 2. 61 . 30 MAGE |e seo a eae lodgepole pine. Lake, seemingly beyond range of damage. Al Giles OUlgbene ihe NOMAUSOS [snes sms eee ics Mtr ya edie Bt Shei oe ae evens nats che 0. 02 ANG og BOOUSMON EAT OW NOrAlo Dae meer Bot. Gaz., 1896, 22: 125. INJURY TO CROPS AND SOIL BY WASHOE PLANT. 30 seedlings are killed in a solution containing 1 part of copper per 808,846 parts of water. Johnson, in his work entitled How Crops Grow, says: * The soluble compounds of copper, arsenic, and lead are very injurious to plant life, unless very highly diluted.” Other plant physiologists in their works confirm Johnson’s statement. Harter® says: “In the case of many plants one of the most toxic substances known is copper, and it is more than likely that it is present in much of the water which experimenters have found to be injurious. Coupin states that one part of copper to 700,000,000 of water is sufficient to retard the root growth of wheat seedlings. A mere trace of copper is sufficient to retard growth in many cases.” The writer is now conducting some experiments to determine what amount of soluble copper in soils is injurious to the growth of certain plants. The work has not yet been completed, but the preliminary data indicate that the growth of wheat and rye is interfered with by the presence of 2.1 parts of soluble copper per million parts of earth in one soil and by 3.5 parts of soluble copper per million parts of earth in another soil. It would appear, therefore, from these data that the Deer Lodge River, even at a distance of 16 to 18 miles below where the tailings are discharged, is not fit for irrigation purposes, and will eventually, if not at once, seriously injure land to which it is apphed. It has been suggested that the Deer Lodge River already contained so large a quantity of alkali salts that it was injurious to soil and crops, even if the smelter wastes were not present. To determine this question, a sample of the water was subjected to an irrigation- water analysis with the following results: TABLE I[X.—Composition of Deer Lodge River water (Serial No. 4244) about 1.5 miles below where smelter waste enters. Determinations. Hypothetical combination. Parts per | Parts per million. | million. IBicaArpOnicnacid jonas (Suse pCaleiumibicarbonate a ae 104.59 Sulphurnicwcidsons a 22D 2eele C1 CLUIMES Up la Gem gee ne 138.00 CHOW ON geal ee aa 19.00 | Magnesium sulphate__.______________ 97.34 @arhonmie acidhion= =e." 2 None) Sodium sulphates s= wa awa ae | 69.93 CGT GIT Se eee ee tty ase GOE49F eS odiumrchlorid= 225 81.35 Winine@siiine sae Ns ss oh oe 19.69 | otha es ie eee | 35.03 | TRO Aa a a ee 441.21 || SING {ran eee are mea ene | 441,21 This analysis shows that the Deer Lodge River does not contain such a quantity of alkali salts as would render it unfit for irrigation purposes. @The Variability of Wheat Varieties in Resistence to Toxic Salts, U. S. Dept. Agr., Bureau of Plant Industry, Bulletin 79, p. 40. 34 INJURY BY SMELTER WASTES. To further prove that the Deer Lodge River water when applied _to the land adds excessive amounts of copper thereto, the soil irri- gated by said water was sampled at various distances from the smelter to determine both the soluble and insoluble copper present. To further demonstrate that any large amount of copper found was not naturally present in the soil, samples not irrigated by the Deer Lodge River and not exposed to the action of the flue dust (Nos. 4163 and 4165) were also subjected to analysis. Following are the results obtained by the examination of the samples gathered in the summer of 1906: TABLE X.—Copper content of surface foot of soils collected in 1906. [Caleulated to dry basis. ] es Origin and description of sample. eee poe Parts per | Parts per million. million. 4185____| 84 miles NE of smelter; irrigated by Deer Lodge River___-___-__- 1,549.4 20.4 4183____| 9 miles NE of smelter; irrigated 12 years by Deer Lodge River_- 458.4 3.4 4184____| 12 miles NE of smelter; irrigated by Deer Ledge River______-_-__ 1,451.6 118.2 4182____| 12 miles NE of smelter; irrigated hy Deer Lodge River________-__ 2,790.8 118.2 4186____| 14 miles NE of smelter; irrigated 16 years by Deer Lodge River-_- 870.4 ell 4165____| 15 miles W of smelter; not irrigated by Deer Lodge River________ Trace. None. 4163____| 10 miles SW of smelter and about 2 miles beyond divide; not Mea ecReol) lone IDYsvere Ibpoxolkexsy TRohweies Ss 13.0 Trace. Bo ee OME ee See eee ers : =a ieee ae ee = It is evident from the preceding table and what has been said of | the action of copper on plants that the soils irrigated from the Deer Lodge River contain very large quantities of copper, enough of which is in a soluble condition to interfere seriously with the growth of many forms of vegetation. It is also evident that the soils beyond the range of flue dust and not irrigated by Deer Lodge River water contain very small quantities of copper, practically none of which is in a soluble condition. The analyses given in Table X show such excessive amounts of copper in the soils irrigated by Deer Lodge River water that the writer was not willing to publish the results until they had been confirmed by collecting and examining new samples. The results given in Table XI were obtained on samples collected in 1907. TABLE XI.—Copper content of surface foot of soils collected in 1907. [Caleulated to dry basis. ] Serial Insoluble Soluble No. Origin and description of sample. copper. copper. Parts per | Parts per million. million. 4871__--| 8 miles NE of smelter; flooded by Deer Lodge River; no sam- JOEY Te eaal TaeOaN HOV) sl wha WOW see 10,018.9 esi 4872____| 82 miles NE of smelter; irrigated by Deer Lodge River; sample fron same field (CNo. 4185) ke¢aken in) 1906222222 ee ee ee 979.9 Us 4873___-| 98 miles NE of smelter; irrigated twelve years by Deer Lodge River; sample from same field (No. 4183) taken in 1906_______- 312.9 Qal 4874___-| 12 miles NE of smelter; irrigated by Deer Lodge River; sample ; from same feld’@Nos 4184) mtaken ansl90622 sae eee a eee 98.7 ell 4875_---| 12 miles NE of smelter; irrigated by Deer Lodge River; sample af from same field (No. 4182) taken im 1906-__---=_---_---2=) 3 624.6 10.4 4876_--_| 14 miles NE of smelter; irrigated sixteen years. by Deer Lodge River; sample from same field (No. 4186) taken in 1906__-_---- 739.8 5.2 TO CROPS AND SOIL BY INJURY WASHOE PLANT. 35 While this table does not give the same results for either total or soluble copper as were obtained in 1906, it does show that all of these soils contain very large quantities of copper, enough of which is present in a soluble form to be dangerous to, if not prohibitive of, many forms of plant growth. It would hardly be expected that the results obtained on copper, either soluble or insoluble, would be the same for any two years, since it is very unevenly distributed over the field and furthermore is constantly changing in its proportions according to the rainfall, irrigation, amount of oxidation, season, ete. It would only be expected that any two years would show the same general condition, and this 1s what these analyses show. It has been suggested that the soils irrigated by the Deer Lodge River are already so alkaline that they are unfit for growing crops, and therefore the addition of copper to the soil can not make matters worse. To test this point the samples of soils collected in 1906 were examined for the soluble salts usually present in alkali land and a determination of black alkali was made by the Skinner ¢ method with the following results: TABLE XII.—Soluble salt content of surface foot of soils irrigated by Deer Lodge River. [Caleulated to dry basis. ] ACTUAL DETERMINATIONS. No. 4182;|No. 4183;|No. 4184:|No. 4185;|No. 4186; : | 12 miles | 93 miles | 12 miles | 83 miles | 14 miles Constituents. | NEoft | NEof | NEof | NEot | NEot | smelter. | smelter. | smelter. | smelter. | smelter. | Per cent.| Per cent.| Per cent.| Per cent.| Per cent. IBICARDONI CAC CaO Nes sas See ee ere ees Es] 0.034 0.101 0.018 0.165 0.107 Sul phariesacidh Onset ee B55 .027 .197 .892 .031 COG ORE a Ss = es ee gn ohn a a .005 .028 005 030 . 006 @arhomi cial delOMe a= et ee ee None. None. None None. None. OP CTO Ha ees es =k eg Se ee Oe ee ee pee ee Cee eres . 100 .048 .050 .215 034 Miaion CS riasstet raeines e h S et l .029 012 .012 .079 .0095 BS GIT nee a a re EOLGin| See RE 025 lis - 002 RO Gay aes alee eee ee ee Fo eee 539 .216 307 1.494 .190 HYPOTHETICAL COMBINATION Galelumebicanbonates. = see 0.045 0.134 6.024 ().219 0.137 WHEAT ESHTTATA, [SHO YE] TL ONAN CCS ae | | ee | ee -005 Walciumeysmliplwatets se ws ewe Wh ee ee ee .303 .038 .149 EYE (| ee Se MAS TNESTIMESU Dae ae ese eS Sa ee eee ule Sy] eae ae kas 039: .390 . 039 CalenimarchlO Gi dessa ee ee ee (TUT | ree cu se So NOP ta Se VE oneSlumMmechlOnige===- 222252. Ne Dreier eae a (2 Os |e eee ae || See pe Se .002 SOGdiIMIMESUphiaitie= as Sas es ee ee ee SAO) | See ae 067 230 oi eis tee Nea SOc hihi Cel nt ase Fa ee ene OUSFieo See .008 .049 .007 UB BY | See Se ee ee ee ee .539 PAL 007 1.494 .190 EST keoraa) izeaal ieee SP Se eae ee ee None. None. None. None None From these results it is evident that none of the soil samples ex- amined contains any black alkali or a sufficient amount of white alkali to be injurious to ordinary farm ¢ rops. aJ. Amer. Chem. Soe., 1906, 28: 77. 36 . INJURY BY SMELTER WASTES. From all the work done in the vicinity of Anaconda the following definite conclusions can be drawn: (1) The forests around the smelter appear from actual cherniedl analysis to be injured for at least 10 miles north of the smelter, 6 | miles south of the smelter, and 13 miles west of the smelter. (2) This injury to forests by sulphur dioxid undoubtedly extends to a distance of 15 to 19 miles north of the smelter, 8 miles south of the smelter, 15 miles west of the smelter, and perhaps even farther in certain localities, although not proved by chemical analysis. (3) The junipers are very resistant to smelter fumes and are able to grow close to the smelter; the red firs are susceptible to the fumes and are badly damaged at distances of about 15 miles or perhaps even farther; the lodgepole pines are intermediate between the other two species of trees, but show damage for at least 10 miles. (4) Large quantities of arsenic are discharged from the smelter on the surrounding country, this poison being found in forage crops in large enough quantities to poison cattle. (5) The waste from the reduction plant discharged into the Deer Lodge River renders it unfit for irrigation purposes. (6) The land irrigated by the Deer Lodge River, containing the waste from the reduction plant, is greatly injured by the copper present in the irrigation water. (7) The soils irrigated by the Deer Lodge River which were studied by the writer do not contain enough alkali salts to be in- jurious to ordinary farm crops. SECOND INVESTIGATION OF INJURY BY SMELTER WASTES AROUND ANACONDA, MONT., 1908-9. A fourth study of injury to vegetation and animal life by smelter fumes was conducted at Anaconda, Mont., during the summer of 1908, and continued at Washington, D.C., during 1908 and 1909. Nearly all the samples taken were from public domain, some within and some outside the bounds of the National Forests. As in the former investigation at Anaconda, the chemist was accompanied by a forester and the samples were taken in the same way and with the same precautions as have been described. Observations of injury to vegetation were made even more thoroughly than on the previous inspection of this locality and special attention was given to the in- jury to forests on public domain. APPEARANCE OF VEGETATION AROUND ANACONDA, 37 APPEARANCE OF VEGETATION SURROUNDING SMELTER. Following is a description of the appearance of the forests situated in various directions from the smelter: NORTH OF THE SMELTER. A trip was made from Anaconda to Lost Creek, following the valley of this creek for about 5 miles from the Deer Lodge-Anaconda road. A trip was then made to the top of the bluff running along the north side of Lost Creek and following the bluff toward the head of the creek for about a mile. From this commanding position observations of the forests farther up the creek were also made. The lodgepole pines were badly injured at the lower end of the valley proper. The damage gradually grew less and at the 5-mile point, previously mentioned, there was a considerable growth of these pines, some of which were injured while others apparently were not. At this place in the valley the old red firs were practically annihilated, large numbers of the younger red firs showed a destruction of the 1908 growth, and on the slopes of the hills on each side of the valley the red firs were practically all killed or badly injured. On the bluff running north of Lost Creek, previously mentioned, all of the old -red firs were dead and the young ones were badly injured. Many of the lodgepole pines showed a marked discoloration of the needles and a considerable number had been killed. There were no signs of recent fires on this bluff to account for this condition. Observa- tions made from high points on this bluff indicated that the injury to lodgepole pines ceased about a mile beyond the farthest point reached on the trip, while the injury to red firs continued as far as one could see. Another trip was made from Anaconda to Antelope Gulch. The basin of this gulch was followed approximately to sec. 3, T.5 N., R. 11 W., which is about 7 miles from the smelter, and the mountains at the end of the gulch approximately in sec. 34, T. 6 N., R. 11 W., and about 74 miles from the smelter, were climbed. At the entrance to Antelope Gulch the trembling aspens had their leaves badly spotted and withered; a few red firs were living, but farther up in the valley the red firs on the mountain sides were practically all killed, indicating that these few live red firs were either protected by the hills in some way or were very resistant individuals. In sec. 3, T. 5 N., R. 11 W., the young red firs in the basin were nearly all injured severely and the large firs on the ridges, at the sides of the gulch, were all killed or dying. Here, too, the needles of the lodge- pole pines, both in the basin and on the slopes at its sides, were badly discolored. In sec. 34, T. 6 N., R. 11 W., all of the old red firs were dead and the young ones were badly injured. A careful 38 INJURY BY SMELTER WASTES. investigation showed that a fire swept over this part of the country about forty-two years ago, but thousands of trees that were dying in the summer of 1908 had grown up after the fire. An mspeckion was made up Modesty Creek Valley for a distenes Ons about 24 miles inside the National Forest, which is approximately at sec. 23, T. 6N., R. 11 W., and about 10 miles from the smelter. From this point observations were made for about a mile in a gulch which runs south from Modesty Creek Valley and is said to be designated as Dry Gulch. The return to Modesty Creek was made by way of a bluff which runs to the east of Dry Gulch and to the south of Modesty Creek. The lodgepole pines in the bottom of Modesty Creek Valley were apparently uninjured, but on the bluffs at the sides of the valley the needles were much discolored as far as sec. 23, T. 6 N., R. 11 W. In the bottom of this valley large numbers of young firs were partially killed, and on the bluffs at each side of the creek all of the red firs appeared to be dead or severely injured. On the bluff which ran east of Dry Gulch the lodgepole pines were discolored and injured to a considerable extent. Practically all of the red firs were dead or dying and from the death of the 1908 growth of these trees it appeared that the injury from the fumes had been recent. An examination for fires showed that none of any great intensity had occurred in this forest for approximately forty years. On the whole, the damage to both lodgepole pines and red firs in and around this valley was much ereater than it was in 1906, when a former examination was made. Another inspection was made, going from Deer Lodge up the valley of Tin Cup Joe Creek for a short distance inside the National Forest, about 19 miles from the smelter. At the entrance to the valley large numbers of young red firs in good condition were growing. As the trip up the valley was continued to the National Forest large numbers of red firs and lodgepole pines in good condition were seen in the bot- tom of the valley. On the ridges on each side of the valley the lodge- pole pines were uninjured, but some of the older red firs were dying. Nearly all of the red firs, especially the younger ones, were in first- class condition. On the whole it appeared that this valley was beyond the limit of injury to lodgepole pines and at the extreme limit of injury to red firs. EAST OF THE SMELTER. The route taken extended from Anaconda across the northern six sections of T. 4 N., R. 9 W., to a point about 114 miles east of the Washoe smelter. At the National Forest boundary (sec. 2,T.4N., R. 9 W.) only red firs were growing at the foot of the mountains, no lodgepole pines being seen. The young red firs at this point showed considerable injury, the 1908 growth having been killed, but the older trees were in fairly good condition. As the journey was con- Bul. 113 (Revised), Bureau of Chemistry, U. S. Dept. of Agriculture. PLATE |X. Fic. 1.—UNINJURED MOUNTAIN SIDE ABOUT 2 MILES SOUTH OF DIVIDE AND 10 MILES SOUTH OF SMELTER, BEYOND RANGE OF APPARENT DAMAGE. Fig. 2.—UNINJURED MOUNTAIN SIDE UP DRY COTTONWOOD CREEK BEYOND RANGER’S CABIN, ABOUT 14 MILES ENE. oF SMELTER, BEYOND RANGE OF APPARENT DAMAGE. a me 2 APPEARANCE OF VEGETATION AROUND ANACONDA. 39 tinued east in the National Forest toward the top of the mountains, it was noticed that practically all of the red firs, both young and old, _ were either killed or dying. Toward the top of the mountain lodge- pole pines were found, but they were apparently uninjured. No note- worthy fire had swept over this region for approximately forty-five years, and yet the red firs were dying. Since the country in secs. 1 and 2, T. 4 N., R. 9 W., is just about as close to the Butte smelters as to the Washoe smelter, it is of course impossible to say which one was responsible for the damage; probably all contributed to it. The road that runs from Anaconda along the east side of the Deer Lodge Valley, and up Dry Cottonwood Creek, was followed to secs. 6 and 7, T.5 N., R. 8 W., about 14 miles from the smelter. The lodge- pole pines along the creek and in secs. 6 and 7 were not injured or dis- colored. In Dry Cottonwood Valley proper the red firs were in excellent condition. (See Plate IX.) On the bluff bounding Dry Cottonwood Creek on the south, approximately in sec. 7, T. 5 N., R. 8 W., quite a number of old red firs were dead, but since there were hundreds of others, as well as of young red firs, in perfect condition erowing around the dead trees, it is hardly possible that fumes were causing injury at this point to any great extent during the summer of 1908. That fumes were reaching this region, however, was shown by the fact that small amounts of arsenic were found on the range grass. On the whole it appears, then, that this region was at the extreme limit of injury to red firs under the conditions existing in the summer of 1908. It is of course possible, even probable, that the considerable number of old red firs that were dead had been killed a number of years before by the fumes from the Butte smelters. SOUTH OF THE SMELTER. A trip was made south of the smelter over a large portion of the counbin covered ‘by secs. 13, 14, 15, 22, 28, 24, 25, 26, 27, T. 4 N., R.11 W. While all of these sections were not visited, they could be plainly observed from commanding positions. All over the flat cov- ered by the sections named, which runs from a point a little south of the smelter to about a mile beyond Mill Creek (about 4 miles south of smelter), the large trees had been cut off and a fire had passed over the country about eighteen or twenty years before, as was shown by the scars on a few older trees and the lack of scars on young 18 to 19 year old lodgepole pines, which evidently grew after the fire. All of these young pines were dead or very badly injured, their needles were all badly discolored, and about three-fourths of them were entirely dead. No red firs were growing on this flat. An inspection tour was also made up Willow Creek approximately to sec. 13, T. 3 N., R. 11 W., a point about 74 miles south of the smelter; Oleson Gulch was also visited and Fourth of July Gulch 40 INJURY BY SMELTER WASTES. observed. In Willow Creek Valley, by reason of the protection offered by the hills, a considerable amount of green and seemingly uninjured timber was to be observed nearly to the National Forest boundary line. Here it was observed that practically all red firs had been killed, a condition which continued the remainder of the way up Willow Creek. In Oleson Gulch the red firs were nearly all dead or dying, and the lodgepole pines growing on the bluffs at the side of this gulch were much discolored and otherwise injured. In Fourth of July Gulch, which opens into Willow Creek Valley, all of the timber in the upper end was swept by fire. At the lower end, however, there was no indication of a recent fire, yet nearly all of the red ns were killed or dying. A trip was then made westward from Gregson up Gregson Canyon and on the mountains surrounding it, covering, approximately, secs. A Be Oe ay Ike i. IE By IN IR, IO) W.. from 6 to 8 miles from the smelter. In the bottom of Gregson Canyon none of the trees seemed to be injured, but on the top of the ridges surrounding the canyon a large percentage of the red firs were injured and gradually dying. The lodgepole pines did not appear to be affected. Since no fire of any importance, except a recent small outbreak covering about 5 acres, had swept over this country for from fifty to sixty years, the dead red firs observed could not possibly be ascribed to that source. South from Anaconda a road was followed that runs first southeast and then southwest across the divide and thence by a branch road to the neighborhood of Allen’s Camp.