BRAZl L I AN OlLSEEUS 35 PROCEEDINGS OF THE SOCIETY OF PUBLIC ANALYSTS AND OTHER ANALYTICAL CHEMISTS. BRAZILIAN OILSEEDS. BY E. RICHARDS BOLTON F.I.C. AND DOROTHY G . HEWER B.Sc. (Read at the Meeting December 6 1916.) INTRODUCTION. THE question of the supply of fats and oils for edible purposes as well as for scap, glycerol and candle manufa'cture has always been a matter of the utmost economic importance. The present European crisis renders it of national importance that no source of supply should be overlooked. Our lack of enterprise in this direction in the past is exemplified by the fact tha%t various oleaginous PeedP tlhough well known for many years have only more or less recently been put to commercial use. It is an undisputed fact that there are vast quantities of oilseeds which have not yet been utilised to any extent although many of them have been shown to yield considerable quantities of oil often suitable for edible purposes leaving non-fatty residues of x-alue as cattle foods.There are many reasons why some of these oleaginous seeds have not been better iitilised in this country quite apart from the fact that the foreign manufacturer and the German in particular hats been ever more ready to crush a greater variety of different seeds than the British manufacturer who has been content to keep to the same products year after year. This has been brought home to us so clearly of late that it is unnecessary to enter into particulars but i t maybe worth while t 36 BOLTON AXD HEWER: consider briefly some of the less apparent reasons why new oilseeds have been SO sadly neglected.the market and samples are offered aU round to different. manufacturers. The manufacturer feeling that there is no competition for a product concerning which little is known usually offers a price very considerably below the true market value, and in so doing virtually defeats his own ends in that he gives the importer the impression that that particular product is not likely to prove a profitable export, and so it becomes neglected until its value is reabed by some enterprising foreigner. Further another very important point in connection with these small consign-ments ia that in order to crush any new or different type of seed the manufacturer must cleanse his entire plant from the product with which he has been previously working an operation which would not be worth his while for a small consignment.For this reason small parcels of even well-known oilseeds are less easily marketable than larger ones. Oil has been produced commercially from quite a number of the seede here mentioned and the oils more especially those from the various palms are finding their way into manufactured products. It therefore behoves the analyst to exercise the greatest care in identifying any special oil and we trust that the figures given below will be a guide in this difficult problem. The authors have examined in the past a very large variety of oilseeds many of which are likely to become of commercial importance in the future while some of them have already been used on a large scale; for example upwards of 6,000 tons of Babaasu kernela have been exported from Brazil during the past two years.Brazil offere a specially large variety of oil-bearing products and of these the twenty specimens dealt with in this paper have been selected as typical. The foregoing remarks may at first sight appear to deal with considerations beyond the scope of the analyst but the authors are of the opinion that the analyst cannot advise his clients to the best advanta,ge unless he surveys the commercial aepect when interpreting the results of his analysis. Our thanks are due to Messrs. Booth and Company (London) Limited for most of the specimens examined and for data L ~ E to the districts of origin and to Mr. J. Masters Hillier of the Royal Botanic Gardene Kew who has kindly identified some of the specimens botanically.From time t o time small consignments of 20 to 100 tons are sent over to " feel VARIOUS PALMS. (SEE PLATE I.) Of the many oleaginous seeds found in Brazil particularly up the Amazon, those of the palms are in general the most useful and deserve special attention for the following reaeons : (a) The kernels of thoee deecribed all yield oil which can be refined for edible purpoees such as margarine manufacture. (6) The kernels leave a non-fatty residue suitable for cattle-feeding. (c) The kernels have a high content of oil are easily shipped and do not readily decompose in transit, H See page 36 BRAZILIAN OTLSEEDS 37 (d) In the case of many of the palms quite a high percentage of oil is found in the pulp surrounding the shell which encloses the kernel and the pulp oil though not usually adaptable to edible purpoees finds many other uses-for example in soap manufacture.( e ) The similarity of the oils obtained from the kernels of the various paJms enables the manufacturer to mix the oils. There are however some disadvantages in the use of these oils and these are mainly : (1) The kernels are always enclosed in a more or less hard shell which in two or three cases would have to be cracked by special machinery. (2) The wide area of distribution causes difficulties in collection as well as in the choice of centres for shell removal and treatment of pulp but the possibility of mix-ing some of the kernels is t o a certain extent helpful in this connection.All those palms whose fruits are surrounded by an oily pericarp would have to be de-pericarped in the country 6f origin. This ia necessary on account of the delicate nature of the pericarp and hhe presence of the weighty shell surrounding the kernel. 1-3. Elaeis Guineensis. Nat. Order Palme; Tribe Cocoinem. The African oil palm is perhaps the best-known oil-bearing palm in the world, and its fruits need no description. This palm is also to be found in Brazil where it yields a fruit indistingu:ishable in appearance and structure from that of the tree which grows in Africa; but climatic soil and other conditions have caused the fruits to contain not only less fatty matter but fatty matter of a distinctly different constitution to that of the same palm when found in Africa.On the Amazon it is known under the name Caiauk and flourishes largely in Par& ManAos and the Amazon valley generally. for the African variety are cited for comparison. those of the African variefy: In the table of figures b t a are given for two Ppecirnens and The following table showa the proportion of pulp and kernel as Brazil. - Manaos. Amazon. Epicarp + mesocarp (pulp) . . 26 17 Endocarp (shell) . 58 58 Kernel 16 25 100 100 - -average figures compared with A fi-ica 38 47 15 100 Both the pulp oil and the kernel oil are suitable for the same purposes as the palm oil and palm kernel oil of commerce though the constants given by these oils are sufficiently different from those of the African producf fo call for special attention, and render it unwise to deliver the Brazilian oils in fulfilment of a contract for the African products.The buyer might take advantage of the different constants to put forward a grievance though in the opinion of the authors the Brazilian kernel oil is inclined to be of greater value than the African the African pulp oil (palm oil) on the other hand being more commercially serviceable 58 BOLTON AND HEWER : Lewkowitsch (“ Oils Fats and Waxes,” vol. ii. p. 533) refers to a species of palm Qhocc;srp melctrwcocca Gart. as cultivated in Brazil and from which the quantities of oil obtained are small. This palm should not be confueed with the palm here dealt with which appears to have owed its origin in Brazil to the planting of the seeds of Elmis guineensis by African settlers.4. Astroearyum Vulgare Mart. Nat. Order PaZma!; Tribe Cocoinee. The Tucum or Aouara Palm. Found in Maranham Par& and in the Amazon valley, where it grows to a height of 30 to 50 feet. Only small consignments amounting to some 600 tons of the kernels have The fruit bears a distinct relationship to that of the African hitherto been exported. oil palm and consists of-Outer Pulp . . 34 Shell . . . . 46 Kernel . . s . 20 Pulp Oil.-At normal temperatures this oil has a consistency like vaseline, but is slightly more granular and is of a pale straw colour with a faint and not un-pleasant smell. The solidity of the oil is chiefly due to free fatty acids as the neutlra.l oil is almost liquid. It is suitable for soap manufacture and if prepared from freph fruits so that the free fattyacids do not exceed 10 per cent.it could be refined for edible purposes-viz. margarine. Kernel Oil.-This is a solid firm and somewhat brittle creamy-white fat,, having a smell and appearance like the well-known palm kernel oil of commerce, which i t closely resembles in properties. It is suitable for the same purposes as palm kernel oil and makes an excellent edible oil when refined. Owing t>o its higher melting-point and larger content of “ stearine,” its commercial value should be greater than that of palm kernel oil. Its value is slightly below that of palm oil. 5. Astroearyum Species. Nat. Order Palma?; Tribe Gocoinem. Known as The fruit consists of a thin hard black woody shell eparsely covered with fibre, and loosely enclosing a cone-shaped kernel of similar texture to a palm kernel.The oil obtained from the kernels is hard white brittle and solid with little taste or smell. The hard and brittle coneistency of the fat is of some importance, in that it provides a natural product closely resembling coconut “ stearine,” which is made by pressing coconut oil by a somewhat expensive process. It will there-fore be suitable as a cocoa-butter substitute and for other purposes for which coconut “ stearine ” is used. The value of the oil for edible purposes ia so great as to render it unlikely that much would be left for other purposes for which however it is obviously suitable. Murumurzi. Found in Par&. 6. Acrocomia Selerocarpa Mart.Nat. Order Palm& ; Tribe Cocoinea?. The The tree grows to a height of 20 to 30 feet in Bahia and forms large forests in The fruits are of a somewhat similar structure to Tucum fruits but the Paraguay Palm. Paraguay BRAZILIAN OILSEEDS 39 outer pulp is enclosed in a> thick smooth shell. follows : The proportion of the parts is as Outer shell (epicarp) . . . . . . . . 28 Oily pulp . . . . . . 24 Inner shell (endocarp) . . . . 42 Mesocarp 1 Kernel . ,. . . . . . . 6 100 -Pulp &?.-This oil is analogous to commercial palm oil has a somewhat similar smell and congistency and is of a golden-yellow colour. The oil is suitable for soap manufacture and if obtained from fresh fruit2s so that there is not more than 10 per cent.of free fatty acids it could be refined for margarine-making. Its value is slightly below that of palm oil. Kernel Oil.-This oil is of a similar nature to palm kernel oil but of a much softer consistency. All the samples examined were free from any very pronounced smell, and were of a pure white to a pale creamy colour. The comparatively low melting-point of t,he oil renders it of less value than commercial palm kernel oil but the high content of oil in the kernel makes up for this deficiency and brings the value of the kernels above that of African palm kernels. The refined oil is specially suit-able for margarine-making while the crude oil would serve for soap manufacture. The exceptionally high content of protein in the non-fntt,y residue has been recorded by Bray and Elliott (~TALYST 1916 44 298).7. Maximiliana Regia,Mart. (N. martiana). Nat. Order PaErnem ; Tribe Cocoineg. The Anajd or Kokerite Palm. The specimens as received consisted of a hard woody oval-shaped shell, point.ed at one end in which are loosely embedded one to three kernels but more usually only two. The nuts are identical in appearance and description to those referred to by Bray and Elliott (ibid.) but the authors’ figures though indicating the fat to be of a similar type are not otherwise in agreement. The kernel oil is a firm white solid of lard-like consistency but exhibiting a tendency towards brittleness. It is practically odourfess and is very similar to African palm kernel oil being suitable for the same purposes more particularly as an edible fat.E’ound in CeaA and Par8 valley. The kernels amount to 124 per cent. by weight of the nut. 8. Cocos Syagrus. Nat. Order Palmem; Tribe Cocoinem Known as Piririma. Two distinct types have been examined the more common being a blunt form, which consists of a hard shell sparsely covered with fibre enclosing a tough white kernel covered by a brown woody skin. The pointed kernels are similar in every way except shape. The structure of both the long and blunt kernels is strikingly characteristic in that they have three points of attachment close together in the former and widely apart in the latter. Although the proportion of oil in the two types is very different (the blunt Found in the Par6 valley TABLE I. (Illustratim on Plate I . Palms.) I ________-___ -___-__ _-- ---I Weight of 100 fruits or fruits fruits fruits fruits fruits Percentage of kernel .16.7 1 26 15 20 I 46 --_________-_-- I--- -- - -__--seeds in grams . . GW 320 660 1,900 1,260 - --________ --- --- ---- -____-__. -- -I---'Kernel . . 34.7 36.7 46-83 1 43*6-82*5 '38*46404 Whole fru'ib I oil content I ~ u l p 46.9 19.7 55-75 37.5 portent* I or seed . . 17.7 12-3 20-25 1 21.4 1 17.9 I I I t 1 - 1 I-28*6 /32*5 ACROCOMIA SCLERO-CARPA. fruits 3,300 ___-______ 6 __-__-_-_-Grou-grou. Paraguay. I--53.4-64-8 63-7 @ Bray and Elliott (ibid.) suggest a diffcrcncc bctwccn Grou-grou and Paraguay kcrnele which is confirmed by tho t Mcuiis Littlc Coconut, and is slvo applicd to thc Coliuuc and othor nuts, lowcr saponification VRIUCK for ttic oil frotn tlu lattcr TABLE 11.(Hlustmtioihs on Ylccte II. V'cwious Oilseedu.) I------Weight of 100 seeds in grams Percentage of kernel . . ____-_-I- -_-_-_/I--Whole seed Analytic4 figures for oil. Solidifying-point "C. . . vmoLA MYRI~TICA PENTACLE-' pENTaCLETHRA BICUHYBA. I PLATY- FmA- M ~ ~ ~ eARY0CAXt SP. SPERMA. MENTOSA. Saponification value . . I Refractive index Zeiss at 44" c. * . . . . . Iodine value . . . . Free fatty acids as oleic Unsaponifiable matter . . -_.--_._-I---_-__---______I-- -PACHIRA 47.6 I--- 42 BOLTOS AND HEWER: containing the greater quantity) in their nature the two are practica,lly identical, and it is curious to note that the authors' analytical figures bear a striking resem-blance to those given by Bray and Elliott for Mnximiliana regia though clearlj- the nuts are not the same.The oil is suitable for the same purposes as AnajA oil. 9. Attalea Funifera Mart. Nat. Order PaZmB; Tribe Cocoinea. Known as This palm is very plentiful in the vast territory between lat. 3" to 10" south, and long. 40" t o 70" west (Greenwich). The fruit consists of one to four but more usually only three long narrow kernels enclosed in a hard woody shell surrounded by a fibrous pulp. This pulp only contains about 1 per cent. oil. The fruit may be regarded as one of the most difficult to crack and yet as mentioned before 6,000 tons of kernels have been exported in two years a oonsiderable proportion of which reached this country. The oil closely resembles coconut oil and although of similar melting-point, the higher proportion of unsaturated glycerides cause it to be of at somewhat softer consistency ; it is nevertheless an excellent margarine oil.Ba busslc. 10. CEhocarpus Batava. Nat. Order PaZmce ; Tribe Brecece. Known as Patad. The oil is prepared by the natives from t3he pulp and fhe specimens of de-pericarped seeds examined by the authors were found only to contain mere traces of oil. The native prepared oil varies from a pale green to a yellowish-green colour, and is almost odourless and tasteless. All the samples examined were found to be very low in acidity. The oil bears a striking resemblance to olive oil and save for a distinctly lower refractive index and a hardly appreciably lower iodine value the analytical constants are strikingly similar including its specific gravity of 0.9158.When subjected tlo Bellier's tsest as modified by Evers (ANALYST 1912 37 488) it behaves in a similar way to olive oil. Methods of rapidly distinguishing this oil from olive oil are specially needed in view of the fact that it' is eminently suitable as a salad oil and would prove an excellent edible oil generally. Found in Para and Maranham. SEEDS AND FRUITS OTHER THAN PALMS. (SEE PLATE 11.) 11. Virola Bicuhyba Humb. Nat. Order Jfyristicacece. Known as Ucuhuba. The seeds alone seem to be indistinguishable either by appearance or analysis from those of Virola wenezuelensis Warb. known under the name " Cuajo," and equally so from those of Myristicia surirmmensis t,hough the seeds of M . guate-mlensis (" Fatty Foods," p.272) usually have a lower content of fat which gives slightly different constants. Owing to the large variety of Myristica species there is some confusion due t o the overlapping of the botanical names given to the same member by different botanists, and the line of demarcation is neither botanically nor analytically clear. A?. mh-From Pars and Madeira River BRAZILIAN OILSEEDS 43 barica however may be distinguished by its long-shaped seeds while $1. canarica, a1so found in Brazil usually has a high content of resinous matter which is difficult to separate from the oil. AIl the above-named seeds have a more or less pronounced arillus which contains an essential oil producing a characteristic smell. In the case of Ucuhuba seeds the proportion of ethereal oil is very small and the fatty matter if not too acid may be refined to an almost odourless and neutral state and a valuable fat thereby obtained.Acid and decomposed fats provide an excellent candle material on distillation. 12. Myristica Piatysperma Spruce. Nat. Order Myristicacew. A sample of the de-pericarped seed was received from Manaos under the erroneous name of “rubber seed.” The appearance of the seed and the analytical constants prove it to be the same as the seed described by Jesson (Misc. Information Kew, No. 9 1914 p. 333) as a native of North-West Brazil. The seed has the characteristic structure of the Jfyristicacem-that is to say, when cut in section it shows the peculiar integumental ramifications of the inner seed coat into the endosperm giving an appearance resembling marble.The seed is made up of-Shell 45 The fat is of a pale creamy-white colour and very hard and brittle in nature and appears to consist chiefly of myristin. A fat of this description has many commercial uses and would command a high price. 13. Pentaalethra Filamentosa, Kernel (endosperm and spermoderm) . . 56 Nat. Order Leguminosem ; Sub-order Mimusee. The seeds or beans are disc-shaped and pointed at the end of attachment. They consist of a hard thin shiny brown shell enclosing a soft oily kernel. The oil is of a pale golden colour with a slight “ nutty ” taste and smell. At normal temperatures the oil is liquid but if maintained at 20” to 21” C . a definite separation of ‘‘ stearine ” takee place.The low acidity of the oil from this type of bean (see also Maboula panza;) is very striking. There is good reason t o suppose that the oil would prove suitable for edible purposes if refined. Pentaclethra oils are characterised by a high titer and are free from any unusual quantity of unsaponifiable matter; but although they saponify fairly readily they yield rather soft and poor-coloured soaps. The non-fatty portion of the kernel is very rich in protein and is probably edible. 14. Pentaclethra Maorophylla Benth. Nat. Order Leguminosem; Sub-order. Common in East and West Africa, The plant is closely related to P.JiEamentosa and the seeds are known under a great variety of names (nee Table IL) but more generally as Maboulcc panza beans. The oil may be described as practically identical in properties to those of P.Jilcbmentosa oil and behaves in a similar manner on saponification. It has a titer of 53” c. Known as Paroa-caq. From Par&. Mimmece. Known as Maboula panm. but not so common in Brazil 44 BOLTON AND HEWER: The beans are said to be edible and according to the Official Guide t'o NO. 1 Museum Kew they are often mixed with the seeds of the wild mango (Irvingia Burteri) to make the well-known Dika bread. 15. Caryocar Species probably C. nmygdccliferum or 6'. brasiliense. Kat. Order, Ternstrerniacece (Tea Order). Known as Sccchu AZmerdras. From Iquitos Peru. The seeds consist of a brown shell smooth and shiny inside and raised into irregular protuberances all over the out,side. This encloses an oily kernel white in colour and covered with a thin brown skin The kernels are edible and are described by Bentley as " probably the most agreeable of all the nut kind." The fat which is a firm brittle solid is snow-white in colour practically odour-less and with a very pleasant taste.It is an edible fat par ezcellence but owing to the fact that it does not " mould " well is unsuitable alone as a cocoa butter subst,it,ut$e ; but if mixed with softer fats the difficulty might be overcome. Needless to say. it would serve in admixture with suitable oils as a margarine fat lard substitute, or baking fat. 16. Marins from Maranham and Par&. Many attempts have been made t o trace the botanical origin of these seeds, but without success. The seeds consist of a thin canary-coloured outer shell enclosing a soft yellow, oily kernel.The oil which is liquid a t ordinary temperatures is of a deep golden-yellow colour and is almost as viscous as a " blown '' oil. The oil might serve as a lubricant if mixed with 4 or 5 volumes of mineral oil but experiments in this direction are needed. 1'7. Paehira Species. Mamurana from Pars. A number of specimens ha1.e been received from time to time inosf of t,hem con-sisting of kernels only while some included a thin brittle outer shell. The kernels which were always received in a very dirty condition are irregular in shape smelling like a mixture of liquorice and fenugreek. The oil which is solid at normal tempera-ture is of a very soft' oily nature though the solid portion does not meltl under 40" C.The smell of liquorice is tenaciously retained by t'he oil but t-his does not. prevent its utilisation for soap-making. It is possible in the event of the non-fatty portion proving edible that it' might, be relished by cattle in the same way as fenugreek which ha.s the same sort of smell. 18. Mahuba-rana. These seeds have not been botanically recognised. The fat bears a great resemblance to that of members of the Jlyristicaceae (11 and 12) but t'he structure of the kernel does not point to any relationship wit,h that Order. The fat obtained was very dark coloured which may have been partly due to the condition of the specimens. The dark colour on mponification detracts from the value of the oil for soap-making. The high content of hard fatty acids mggests its use as a candle material ERAZILTAN OILSEEDS 19.Carapa Guianensis Aubl. Xat. Order Meliacem There appears to be some confusion in botanical but it would appear that the names C. guianensis and Lewkowitsch (ANALYST 1908,33,184 and 1909,34,10). Par& and North Brazil generally. 45 Known as Andiroba. From literature on Carapa seeds, G . procera are synonymous. in dealing with C. guyanensis (C. procera) refers to the difficulty in correctly identifying the several specimens and although the analytical figures given here bear a distinct relationship to those ob-tained by Lewkowitsch a clear line of demarcation is still wanting. The confusion is still further added to by the fact that the authors have found several specimens of Andiroba oil to be optically active-(u)D in 100 mm.to 0-7 ang. deg.-whereas Lewkowitsch (ibid.) regards the oil of C. procera as not containing optically active substances in contradistinction to the oil of C. grandi$ora. Aiidiroba oil is prepared by the natives and a residual paste ie offered for sale. Both paste and oil are very bitter and have anthelmintic properties so that the oil cannot be used for edible purposes nor would the cake serve €or cattle-feeding. The oil is suitable for soap-making. The following figures for t’he oil have been obtained in addition to those given in Table 11. : Reichert-Meissl value . . . . 2.5 Polenske value . . . . . . 0-3 Kirschner value . . . . . . . . * . . I 2.1 Titer . . . . . . . . . . 36.2‘ C. 20. like Omphalea Megacarpa Hemel.Nat . Order Euphorbiacece. CayeW nut of The seeds consist of an iuuer yellow oily kernel which is coated with a pith-skin the whole being loosely enclosed in a fairly thin grey-brown friable shell. The oil is liquid at ordinary temperatures of a pale straw colour without any Manaos and Par&. very pronounced taste and with a slight but not unpleasant odour. Professor Cash (see Imp. Inst. Col. Rpf. No. 88 p- 4’73)-According to “ The oil probably increases peristalsis by stimulating the intramural nervous plexuses of the intestine. It also produces diuresis owing presumably to a stimulation of t,he kidney tissues but the exact mode of action is not yet determined. The dose of the oil is about 4 grams. The oily nature of the material apart from the purgative principle is considered to add slightly to the purgative effect by exerting a feeble mechanical action. The oil is regarded as a valuable non-irritant cathartic and its activity does not decrease appreciably with age. The dose required is much smaller t,han that of castolr oil and the taste is not unpleasant.” The physiological properties are said to be inherent in the oilitaself and not due to traces of impurity. The oil might find an outlet as a substitute for castor oil as it has a more pleasant tast,e and it can easily be distinguished from caetor oil as follows : (a;) It has; widely different analytical constants. ( b ) It is not optically active. (c) It is not very viscous. (d) It is only slightly soluble in alcohol. *c Caycte is the name of an Indian tribe