IMAGE EVALUATION TEST TARGET (MT-3) -**- 1.0 I.I 1.25 2.8 Ui 1.4 !M 120 1.6 m. m ^^ "^ / ^'^'4^ V' ^ o/l /A Photographic Sciences Corporation 23 WEST MAIN STREET WEBSTER, N.Y. 14S80 (716) 873-4503 : tumen is much more abundant; Eaton long since described petroleum as exuding from the Niagara limestone, and this formation throughout Mon- roe county in western New York is described by Mr. Hall as a granular crystalline dolomite including small laminae of bitumen, which give it a resinous lustre. When the stone is burned for hy Dr. T. Sterry Hunt. 5 lime the bitumen is sometimes so abundant as to flow like tar from the kiln. In the Corniferous limestone, at Black Rock on the Niagara Kiver, petroleum is described as occurring in cpvities, generally in the cells of fossil corals, from which, when broken, it flows in considerable quantities. It also occurs in similar condi- tions in the Cliff limestone (Devonian) of Ohio. Higher still in the series, at the base of the Hamilton group, occur what in New York have been called the Marcellus shales ;' these enclose septaria or concretionary nodules which contain pe- troleum, while at the summit of the same group similar con- cretions holding petroleum are again met with. The sandstones of the Portage and Chemung group in New York are in many places highly bituminous to the smell, and often contain cavi- ties filled with petroleum, and in some places seams of indurated bitumen. A calcareous sandstone from this formation at Laona near Fredonia in Chatauque county contains more than two per cent of bituminous matter. At RockviUe in Alleghany county, according to Mr. Hall, the same standstones are highly bitumin- ous and give out a strong odor when handled, and in the counties of Erie, Seneca and Cataraugus abundant oil springs rise from the sandstones and have been known to the Seneca Indians from an- cient times. In the northern part of Ohio, according to Dr. New- berry, petroleum is found to exude in greater or 'ess quantity from these sandstones wherever they are exposed, and the oil wells of Pennsylvania and Ohio are sunk in these Devonian sand- stones, often through the overlying carboniferous conglomerate, and m some cases apparently, ac. rding to Newberry, through the sandstones themselves, which are supposed by him to be only reservoirs in which the oil accumulates as it rises through fissures from a deeper source, in proof of which he mentions that in boring wells near to each other, the most abundant flow of oil is met with at variable depths. In some instances the petroleum appears to filter slowly into the wells from the porous strata around, which are satu- rated with it, while at other times the bore seems to strike upon a fissure communicating with a reservoir which furnishes at once great volumes of oil. An interesting fact is mentioned in this connection by Mr. Hall. In the town of Freedom, Catarragus Co., New York, is a spring which had long been known to furnish considerable quantities of petroleum. On making an ex- cavation about six yards distant, to the depth of fourteen feet, a copious spring of petroleum arose, and for some time aff-orded large 6 Notes on Petroleum ■ quantities of oil, after which the supply diminished in both the old and new springs, so that it is now less than at the first set- tlenaent of the country. Notwithstanding its general distribution throughout a considerable region in the adjacent portions of New York, Pennsylvania and Ohio, it is only in a few districts that it has been feund in quantities sufficient to be wrought with profit. The wells of Mecca in Trumbull Co., Ohio, have been sunk from 30 to 200 feet in a sandstone which is saturated with oil ; of 200 wells which have been bored, according to Dr. Newberry, a dozen or more are successfully wrought, and yield from five to twenty barrels a day. The wells of Titusville on Oil Creek, Pennsylva- nia, vary in depth from TO to 300 feet, and the petroleum is met with throughout. The oil from diflferent localities varies con- siderably in color and thickness, and in its specific gravity, which ranges from 28° to 40° Baume, (from -890 to 'SSO.) The valley of the Little Kenawha in Virginia, which is to be looked upon as as an extension of the same oil-bearing region, contains petroleum springs, which so long ago as 1836, according to Dr. Hildreth, yielded from fifty to a hundred barrels yearly. It here rises through the carboniferous strata, and as elsewhere is accompanied by great quantities of inflammable gas. The black inflammable shales of the Devonian series in western Canada which were formerly referred to the Hamilton group, and are now considered to belong to the base of the overlying Portage and Chemung, appear at Kettle Point on Lake Huron and in portions of the region southward to Lake Erie, but the oil wells sunk in Enniskillen show that the source of the oil is really below the horizon of these shales, inasmuch as the underlying argilla- ceous shales and limestones of the Hamilton group are there found near the surface, and have been penetrated 120 feet, at which depth oil is still met with, leaving but little doubt that it is derived from the limestones beneath, which both in New York, and in Canada are impregnated with petroleum. A some- what slaty brownish-black bituminous dolomite belonging to the Corniferous limestone from ""' " "i 1 i Mmi, in Fincnr dine, gave me not less than 12.8 per cent, of bitumen, fusible and readily soluble in benzole, and another from the Grand Mani- toulin Island, which was a brown crystalline dolomite, yielded from 7.4 to 8.8 per cent, of similar bitumen. The solid form of this bitumen at the outcrop of the rocks, is probably due to the action of the air. hy Dr. T. Slerry Hunt. f The existence of liquid bitumen in the Corniferous limestone in western Canada was pointed out as long ago as 1844 by Mr. Murray, who tells us that this rock is generally bituminous, and that cavities in it are often filled with petroleum ; the quarries near Gravelly Bay in Wainfleet are cited as an example, (Report of Geol. Survey, 1846, p. 87). In the Report for 1850 we find a notice of what are called oil springs, in which petroleum rises to the surface of the water near the right bank of the Thames in Mosa, and in two places on Bear Creek in Enniskillen, Subse- quently Mr. Murray described a considerable deposit cf solid bitu- men or mineral tar, which occurs in the same township, extending over about half an acre, and in some places two feet in thickness, doubtless formed by the drying-up of petroleum springs (Report for 1851, p. 90.) I had already in the Report for 1849, p. 99, described this bitumen from specimens in the Museum of the Geological Survey, and called attention to its economic applica- tions, remarking that " the consumption of this material in Eng- land and on the continent for the construction of pavements, for paying the bottoms of ships, and for the manufacture of ilium inating gas is such that the existence of these deposits in the country is a matter of considerable importance." At this time solid bitumen was thus employed, but in the liquid form of petro- leum its use was chiefly confined in Europe to medicinal purposes. Under the names of Seneca oil and Barbadoes tar it had long been known and employed medicinally by the native tribes of America. Its use for burning, as a source of light or heat, in modern times has been chiefly confined to Persia and other parts of Asia, although in former ages the wells of the island of Znnte described by Herod otus furnished large quantities of it to the Grecian Archipelago,, and Pliny and Dioscorides describe the petroleum of Agrigentum in Sicily, which was used in lamps under the name of Sicilian oil. The value of the naphtha annually obtained from the springs at Bakoum in Persia on the Caspian sea was some years since estir mated by Abich at about 600,000 dollars, and the petroleum wells of Rangoon in Burmah are said to furnish not less than 400,000 hogsheads yearly. In the last century the petroleum or naphtha obtained from springs in the Duchy of Parma was employed for lighting the streets of Genoa and Amiano. But the thickness, coarseness and unpleasant odor of the petroleum from most sources were such *hat it had long fallen into disuse in Europe, when in 1847, the attention of Mr. Young, a manufacturing ■ 8 Notes on Petroleum chemist of Glasgow, was called to the petroleum which had just • been obtained in considerable quantities from a coal mine at Riddings in Derbyshire, from which by certain refining processes he succeeded in preparing a good lubricating oil. This source however soon becoming exhausted, he turned his attention to the somewhat similar oils which Reichenbach and Selligue had long before showed might be economically obtained by the distilla- tion of coal, lignite, peat and pyroschista. To this new in- dustry Mr. Young gave a great impetus, and in connection with it attention was again turned to the refining of liquid and solid bitumens, it being found that the latter by distillation gave great quantities of oils identical with those from petroleum. About the year 1853 the attention of speculators was turned to the de- posits of bitumen in Enniskillon just described, but it was not till 1857, that Mr. W. M. Wiliiama of Hamilton, with some asso- ciates undertook the distillation of this tarry bitumen, when they soon found that by sinking wells in the clay beneath, it was pos- sible to obtain great quantities of the material in a fluid state. Large numbers of wells were subsequently sunk by Mr. Williams and others in the southern part of the township of Enniskillen along the borders of Black Creek, and also about ten miles farther north on Bear Creek. Nearly one hundred wells had been sunk when I visited the place in December last, and many more have since been bored. Of these but a small proportion furnish available quantities of oil, but the whole amount already obtained from the district is perhaps "ot less than 300,000 or 400,000 gallons. Owing to the diflBculties of communication and of procuring casks suflScient for the oil, these wells have not yet been wrought in a coutinuous manner; large quantities of oil are however taken out at intervals of some days, and it is probable that if continuously worked Ae supply would be still greater. Here aa in Pennsylvania considerable variations are found in the qual- ity of the oil ; that from the wells on Black Creek is more liquid and less dense than the oil from Kelly's wells on Bear Creek, an-', it is said that wells recently sunk to a considerable depth in the rock have yielded an oil still thinner, lighter colored and loss dense, which is prized as being more profitable for refining. The present wholesale price of the crude oil from Kelly's wells, deliv- ered at the Wyoming station on the Grand Trunk Railway, is about thirteen cents a gallon. The oil obtained by Mr. Williams is refined in Hamilton, while that from the northern \ hy Dr. T. Sterry Hunt. 9 part of the township has hitherto been sent to Boston, though refining works are now being erected at the wells. The process of refining consists in rectifying by repeated distillations, by which the oil is separated into a heavier part employed for lubricating machinery, and a lighter oil, which after being purified and deod- orized by a peculiar treatment with sulphuric acid, is fit for burning in lamps. These wells occur along the line of a low broad anticlinal axis which runs nearly east and west through the western peninsula ofCanada, and brings to the surface in Enniskillen the shales and limestones of the Hamilton group, which are there covered with a i&\: feet of clay. The oil doubtless rises from the Corni- ferous limestone, which as we have seen contains petroleum ; this being lighter than the water which permeates at the same time the porous strata, rises to the higher portion of the formation, which is the crest of the anticlinal axis, where the petroleum of a "onsi- derable area accumulates and slowly finds its way to the surface through vertical fissures in the overlying Hamilton shr'.js, giving rise to the oil springs of the region. The oil is met with at various depths ; in some cases an abundant supply is obtained at forty feet, while near by it ia only met with at three or four times thatdepth,and sometimes only in small quantities. Everything points to the existence of separate fissures communicating with a deep- seated source. At Kelly's wells however,it would appear that a reser- voir has been formed much nearer the surface, where in a bed of gravel and boulders, underlying tbe superficial clays, the oil rising from the rocks beneath has accumulated. The inflammable gas which issues from the wells is not necessarily connected with the petroleum, inasmuch as it is an almost constant product of the decomposition of organic matters, and is copiously evolved from rocks which are destitute of bitumen. It is similar to the gas of marshes and to the fire damp of coal mines. A curious cir- cumstance is however noticed by Mr. Robb ; the gas which accu- mulates in the oil pits, becomes charged with vapors which pro- duces upon the workmen a sor^ of intoxication like nitrous oxyd.* This is not surprising when we remember that volatile hydrocar- • Mr. Charles Robb, C.E., has published in ^he Canadian Journal for July an interesting paper on the oil wells of Enniskillen, to which, as also to a paper by Prof. E. B. Andrews of Ohio, in Billiman's Journal for July I am indebted for several facts. 10 Notes on Petroleum I bons like amylene, closely related to the hydrocarbons of petro- leum, produce similar efFects when their vapor is respired. The oil wells of the United States are for the most part sunk m the sandstones which form the summit o? the Devonian series, b«t the oils of western Virginia and southern Ohio rise through the coal measures which overlie the Devonian strata, whrle the wells of EnniskiUen are situated much lower, and are sunk in the Hamilton shales, which immediately overlie the Corniferous or Devonian limestone. It is not impossible that in Ohio some of the higher strata, such as the sandstone, were originally impregnated with bitumen, but in Canada from the absence of this substance diffused through the shales in question, we are forced to assign it to a lower horizon, which is doubtless that of the bituminous De- voman limestone. This view I have for some time maintained in opposition to those who conceive the bitumen to be derived from the black pyroschists ; see my lecture before the Board of Arts rerouted in the Montreal Gazette of March 1, where I asserted that the source of the petroleum was to be sought in the bitu- minous Devonian and Silurian limestones; besides the Corni- ferous limestone (Devonian,) we have shown that both the Niagara and the Trenton, (of Upper and Lower Silurian age,) contain petroleum. The question of the extent of the supply of pe- troleum is not easily answered ; the oil now being vvroucrht 13 the accumulated drainings of ages, concentrated along certain lines ot elevation, and the experience of other regions has shown that these sources are sooner or later exhausted ; but thouo-h the springs of Agrigentum, like those of Derbyshire, have nearly ceased to flow, those of Burmah and Persia still furnish, as they have for ages past, immense quantities of oil; nothing but experience can toll us the richness of the subteiranean reservoirs. It is not probable that the Devonian limestone is equally rich in petroleum through- out Its whole distribution, but the exposures of it in the west Ire too few to enable us as yet to say in what portions the petroleum predominnates; as however this rock underlies more than one-half of the western peninsula, we may look for petroleum springs much farther east than EnniskiUen. A well yielding considerable quan- tities of petroleum is said to occur in the township of Dereham, about a quarter of a mile S. VV. of Tilsonburg, and we may reasonably expect to find others along the line of the anticlinal, or of the folds which are suboidiiiute to it. by Dr. T. Sterry Hunt. 11 It is now many years since Sir William Logan described the occurrence of petroleum springs in Gaspe, and collected specimens of the oil, which are preserved in the Geological Museum. One of these, near Gasp6 Bay, is described as occurring on the south side of the St. John's River about a mile and a half above DougJastown, where it may be collected by digging pits in the mud on the' beach. Another locality is about 200 yards up a small fork of the Silver Brook, which falls into the Southwest Arm six or seven milos above Gaspe Basin. The oil collects in pools along the stream, and may be gathered in considerable quantities. The cavities in a greenstone dyke on Gaspe Bay were also found to be filled with petroleum, and the odor of it from the rock was perceived at a considerable distance. The dyke, which marks a fold in the stratification, runs in the direction of the petroleum springs, and the evidences of the distribution of petroleum are thus, as Sir William Logan has remarked, visible along a line of twenty miles (Report for 1844, p. 41.) Attention has recently been drawn to these indications, and a company formed with a view of exploring this region for petroleum. Here, as well as in western Canada and the United States, the connection is evident between the rM-ings and undulations of the strata which favor the accumulation of the petroleum. Supplementary Note. We have stated in the preceding paper that the different mineral combustibles have been derived from the transformations of vegetable matters, or in some cases of animal tissues analogous to these in composition. The composition of woody fibre or cel- lulose, in its purest state, maybe represented byC3 4H3o03o or as a compound of the elements of water with carbon • the -n- crusting matter of vegetable cells, to which the name of lignine has been given, contains however a less proportion of oxygen and more carbon and hydrogen than cellulose, so that the mean com- position of recent woods, as deduced from numerous analyses of various kinds, may be represented by Cu^Ux.aOx,,, We may conceive of four different modes of transformation of woody fibre, all of which probably intervene to a greater or less degree m the production of mineral combustibles; and in considering 12 Notes on Petroleum these changes we shall for greater simplicity adopt for the com. position of woody fibre the first named formula, Ca 4Ha oOa o I. When wood is exposed to the action of moist air, oxygen is absorbed, and carbonic acid and water are evolved in the proportion of one equivalent of the first for two of the last. We may sup- pose that for H. which is oxydised by 0, from the air, the wood loses COa.so that while the carbon increases in amount the pro- portions of oxygen and hydrogen are unchanged. In this way an equivalent of cellulose, by absorbing sixteen equivalents of oxygen and losing eight of carbonic acid, (8 COa) and sixteen of water. (16 HO) would leave C, aH«04. Such is the nature of the de- cay of wood when exposed to the air, and the process, could it be carried out, would leave a residue of carbon only. If however the wood 18 deeply buried and excluded from the oxygen of the air two reactions are conceivable. II. The whole of the oxygen of the wood may be given ofi" in the form of carbonic acid, while the hydrogen remains with the resid- ual carbon The abstraction of ten equivalents of carbonic acid from one of woody fibre, would leave a hydrocarbon, Ci 4Ha o. III. Instead of combining exclusively with the carbon, a part of the oxygen of the wood may be set free as water, in com- bination of the hydrogen. The abstraction from an equivalent of woody fibre of four equivalents of carbonic acid and twelve of water would leave a hydrocarbon CaoHa. IV. These decomj,ositions are however never so simple as we have supposed in II and III, for a portion of hydrogen is at the same devolved m combination with carbon, chiefly as marsh gas, CaH4. The amount of this gas evolved from decaying plants submerged in water, and the immense quantities of it condensed m coal beds and other rocky strata, (forming fire damp,) shew the great extent to which this mode of decomposition prevails In nature these various modes of decomposition often go on together, or intervene at difi-erent stages in the decomposittn of the same mass; they are besides seldom so complete as we have represented them. The first process results in the formation of vegetable mould, which always retains portions of carbon and hydrogen ; while the incomplete operation of the processes II 111 and IV gives rise to peat, lignite, brown coal, bituminous coal and pyroschists, in all of which the proportion of the oxygen is much less than the hydrogen, so that their composition may be hy Dr. T. Sterry Hunt. 13 approximately represented by mixtures of hydrocarbons with ve- geiable fibre. The following results have been selected from a great number of analyses by various chemists, and are for the most part taken from Bischof's Chemical Geology, (Vol. i. cap. XV.) The nitrogen, which in most cases was included with the oxygen in the analysis, has been disregarded, and the oxygen and hydrogen for the sake of comparison, have been calctilated for twenty-four equivalents of carbon. 1. 2. 3. 4. 6. 6. 1. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. Vegetable fibre or cellulose, n TT n Wood, mean composition, Og,Hi8.,Oi6 « ^!^*' (Vaux,) C, H,,.,Oio ^^° ; (Regnault,) C^.H^.^O^.g Brown cOal, (Schrotter,) C24H,,. 30,0.6 ^^' <^o (Woskresensk7,).Cii4Hi30r.6 ^'f^*''---. (Vaux,) C,,H,,.30e.« do. passing into mineral resin,. (Regnault,) Cs,4Ej503. Bituminous coal, do f! n n f- f e ^cii) the general C^-^ formula being CnHn+a, so that oils like CisHao and CaeHas contain nearly the maximum quantity of hydrogen, and a body like Ci4Hao, whose formation we have supposed above, could not ex- ist, but must break up into marsh gas and some less hydrogenous oil like petroleum. We do not know the precise conditions which in certain strata favor the production of petroleum rather than of lignite or coal, but in the fermentation of sugar, to which we may compare the transformations of woody fibre, we find that under diflferent con- ditions it may yield either alcohol «nd carbonic acid, or butyric and carbonic acids with hydrogen, and even in certain modified fermentations the acetic, lactic and propionic acids, and the higher alcohols, like Ci oHiaOa. These analogies furnish sug- gestions which may lead to a satisfactory explanation of the pe- culiar transformation by which, in certain sedimentary strata, organic matters have been converted into bitumen.