October 1947
INDUSTRIAL AND ENGINEERING CHEMISTRY
I t is undissociated ammonia and not ammonium ion which brings about the stabilization. Apparently ammonium ion, as Fell as the ions of many other bases, is unable to penetrate the fiber. ACKNOWLEDGMENT
K e are indebted to P. J. Fynn of this laboratory for construction of the glass-feather manometers used in this work, and to Richard H. Robinson and C. L. Hoffpauir for sulfate analyses. LITERATURE CITED
(1) Bed, E., Rueff, G., and Carpenter, C. H., IWD.ENG.CHEM.. ANAL.E D . , 10, 219-24 (1938).
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(2) Davis, T. L., “Chemistry of Powder and Explosives,” vol. 11, p. 260, New York, John Wiley & Sons, Inc., 1943. (3) Hake, C., and Lewis, Reginald, Jr., J . SOC.Chem. Ind., 24,37481 (1905). (4) Hoffpauir, C. L., and Guthrie, J. D., IND.E h . CHEM.,ANAL. ED.. 16. 391-2 (1944). ( 5 ) Jacobs, M . HT, Cdld Spring Harbor Symposia on Quantitative Biology, Vol. V I I I , pp. 30-9 (1940). (6) Kullmen, Carl. Svensk Kem. Tid., 53, 233-41 (1941). (7) Reeves, R. E., and Giddens, J. E., IND.E m . CHEM., 39, 1303 (1947). (8) Taylor, John, British Patent 11,407(1846). (9) Treon, J. F.,and Crutchfield, W. E., Jr., IND. ENQ, CHEW, ANAL.ED.,14, 119 (1942). (10) Wiggam, D. R., J . Phys. Chem.,35,536-9 (1931).
Vitamin A and Oil Content of Fish Livers and Viscera FISHES OF THE OREGON COAST RUSSELL 0. SINNHUBER AND D. K. LAW Oregon Agricultural Experiment Station, Seafoods Laboratory, Astoria, Ore. T h e increasing demand for vitamin -4 in food and pharmaceutical fields has stimulated a search for new sources of this vitamin in the fishes that inhabit our coastal waters. The livers and viscera of a number of fishes were assayed for vitamin A and oil content in order to indicate potential supplies and to enable a more complete utilization of cannery waste. The report is a summation of approximately 400 samples.
D
U R I S G World War 11, imports of cod and halibut oil from Europe were severely reduced. With the scarcity of supplies of vitamin A and D and the uncertainty of future production abroad, research turned its attention to the fishes which inhabit our coastal waters, in order to meet the ever increasing demands for vitamin 4. The importance of vitamin A in animal nutrition, pharmaceuticals, and fortification of foods, especially margarine, has been the stimulus for the search of new sources of this vital compound. When research pointed out that some of the North Pacific sharks, dogfish and soup fin,contained livers which were many times richer in vitamin A content than the cod, a new industry was born on the West Coast. The soup-fin shark, once regarded as a nuisance and a destroyer of nets, has now become the quest of many fishermen. This fishery rapidly developed into a bonanza when the price of soup-fin shark livers rose to over nine dollars a pound. Oregon, along with the other two Pacific states, was soon contributing much to the vitamin A supplies of the United States. The supply of soup-fin shark, on close examination of the landing figures (II), apparently is on the decline; consequently conservation of this valuable natural reource is an important problem. I n order to meet the demands for vitamin A, considerable interest and research have been directed to the other species of fish, some of which are now adding to our supplies of vitamin A. In 1939 many Pacific fishes were examined for vitamin A and D (IO). Canada (1)has published a chart of the fishes common to that locality with their vitamin potency and oil content. ‘Hamm ( 6 ) has added another list of the vitamin A and D values of many species. Interest in new sources of vitamin A has prompted the work on the sharks and rays of Florida ( I S ) . In 1941 a paper appeared dealing with the chemical composition, physical properties, and vitamin content of a number of fish and body oils (6). Butler ( 2 ) recently compiled and published a list of fishes
with their vitamin A and D contents. This report is a survey of the vitamin A and oil content of some of the fishes which inhabit the Oregon coast. The presence of vitamin A9 and its occurrence in fresh water fish or fish of some fresh water history has been described by many authors (3,4,8). This compound has been described as having biological activity by several ivorkers (7, 1%’). In Oregon, fish which spend a portion of their life in fresh or brackish water, are frequently encountered. These species show the presence of vitamin Az as indicated by examination of the absorption spectra a t 350 millimicrons. No attempt was made to analyze for vitamin A 2 but the presence of this compound is indicated in this survey. Many factors have been observed to influence the vitamin A and oil content of fish livers. These factors are important since the monetary value of vitamin A is higher in oils of greater vitamin eoncentration. Size and age are factors which have a distinct bearing on the vitamin A content of the fish. Generally within a given species the larger and more mature fish have a greater vitamin A value. In certain species of fish, sex also has an effect on the vitamin A content. For example, in the male and female soup-fin shark of equal size, the male yields a liver oil of greater total vitamin A. Consequently, the livers of the s o u p fin shark are segregated according to sex. The season, the water temperature, and availability of food undoubtedly influence the vitamin A content of fish livers. Lovern, Edisbury, and Morton (9) presented evidence to show that seasonal fluctuation of halibut livers may be correlated with the abundance of plankton. The vitamin A analyses were performed according to the procedure adopted by the Vitamin Oil Producers’ Institute, and the vitamin determinations were carried out on suitable dilutions of the whole oil in isopropanol using the Beckman spectrophotometer. The commercial conversion factor, 2000, was used to convert at 328 millimicrons to International Units per gram of oil. The viscera samples in this report were the stomachs, caeci, and intestines; no livers or sex organs were included in the assays of the viscera. ACKNOWLEDGMENT
The authors are deeply indebted to Vernon E. Brock, now of the Division of Fish and Game, Territory of Hawaii, and Donald
INDUSTRIAL AND ENGINEERING CHEMISTRY
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TABLEI.
VITAMIN
2 %
AND O I L COXTENT O F LIVERS ASD VISCERA FRO41 FISHES O F OREGOX COAST
Common and Scientific S a m e Prickly bullhead (Cottus a s p e r ) Pink o r humpback salmon (Oncorhynchus gorbuscha) Great blue shark (Prionace glauca) Mackerel shark (Lamna nasus) Three-toothed lamprey ( E n t o s p h e n u s triden#",a,.\
BL&"c-;od,, sablefish ( A n o p l o p o m a f i m b r i a ) Pacific halibut (Hippoglossus stenolepis) Soup-fin shark (Galeorhinus zyopterus) Male
Female
Source of Oil
No. of Specimens or Wt.
Oil Content, %
Vitamin A , I. U./G. Oil
Liver
18
9.6
3,150
Liver
9
3.0
30,000
Liver Liver Liver
400 lb. 1 20
37.0 63.1 20-30
17,700 9,000 12,-20,000
Liver Liver Viscera
7 1000 lb. 1000 lb.
14-20 11-27 3.6
150,-200,000 17,-193,000 361,500
Liver
Many tons
45-65
48,-190,000
Liver
Several tons
51-70
10,-68,000
Dogfish or grayfish (Spualus suckleyi)
Liver
Many tons
61-81
5,-34,000
Ling cod (Ophiodon elongatus)
Liver
Many tons
9-23
50,-500,000
California pompano ( P e r i l u s s i m i l l i m u s ) Ocean sunfish ( M o l a mola) Basking shark (Cetorhinus m a z i m u s ) Lancetfish ( A l e p i s a u r u s f e r o x ) Columbia River chub (Mylocheilus c a u r i n u s )
Liver Liver Liver Liver Liver Viscera Liver Viscera Liver Liver Liver Liver
2 1 1 1 35 35 30 30 500 lb 30 lb. 1 1
8-14 49.8 8i.O 37.0 14.3 39.5 12.2 n ,3 ?2.8 07.7 9.67 15.9
8.-14,000 454 216 5,250 36,200 3,760 32,600 81,000 17,260 3,150 76,200 6,830
6 40 lb. 30 fish 900 lb. 17 Tons Tons
Black cod or sablefish ( A n o p l o p o m a fimbria)
Liver Liver Viscera Liver Viscera Liver Liver Gscera Liver Liver Viscera Liver
Pacific mackerel (Decapturus s p . ) Shad (Alosa sapidissima)
Viscera Liver Liver
Columbia River smelt (Thaleichthys pnci,iicus) Pacific hake (Merlucczus productus) Pacific tomcod ( M i c r o g a d u s proxamus) Blenny eel (Stzckaedae s p . ) Midshipman (Porzchthys notatus) Hagfish (Polistotrema stoutii) Chinook salmon (Oncorhynchus tshawytscha) Dover or slime sole ( M i c r o s t o m u s p a c i j c u s ) Petrale sole Eopsetta i o r d a n i ) Black rookfis6 (Scorpaenidae sp.) Red rockfish (Scorpaenidae 9p.) Olive-backed rockfish (Sebastodes sazicola)
1-24 8-10
6.5
2,-102,000
23,-40,000
7-19 0.5-1.5 13-22 9-24 9.35 10-16 5-10 2-7 9.40
21,000 5,-31,000 1 ,-3,000 22,-113,000 10,-230,000 103,400 93,-237,000 36,-115,000 7,-100,000 12,560
1 50
1.38 6.71 7.50
19,500 324,000 33,500
500 lb. Tons 28 28 3
3
Viscera
50
9.00
16,000
Turbot (Pleuronichthys decurrens) Thresher sbark (Alopaas v u l p i n u s )
Liver Liver
Tone
16-20 37-39
16,-37,000 1.-17,500
Green sturgeon (Acipenser acutirostris)
Liver Viscera Liver Yiscera Viscera Liver Lirer Liver Liver Liver
24.0 1.60 9-49 2-5.5 2.93 1.76 65.00 41.4 s3;y
1,610 8,500 10,-17,000 10,-28,000 3,260 13,760 670 3,250 600-900 71,800
White sturgeon ( I c i p e n s e r transmontanus) .4lbacore tuna (Germo alalunga) Eel pout ( A p r o d o n cortezianus) R o n i t o shark ( I s u r u s olaucus) gkiie
