Sardine and Tuna Oils as Sources of Vitamin D ROGERW. ‘ h U E s D A I L
AND
HELENJ. CULBERTSON, Truesdail Laboratories, Inc., Los Angeles, Calif.
T
HE value of cod liver oil The antirachitic potency of four raw sardine EXPERIMENTAL PROCEDURE in human therapeutics is oils, four refined tuna oils obtained from comThe method proposed by the well known. The vitamercial lots, and one medicinal cod liver oil are V i t a m i n Assay Committee of min potencies of other fish liver quantitatitely determined. Three samples of the American Drug Manufacoils have been investigated, but turers’ Association (6) has been sardine oil are quite uniform in their vitamin D less research has been done upon employed in determining quantithe body oils of fish. Such biopotency, although slightly inferior to cod liver oil. tatively the vitamin D potencim logically tested fish oils have One is the equal of the cod liner oil as a source of of these nine oils. This method only recently found a substantial this factor. Two samples of tuna oil are slightly states: market in the fields of mammainferior to three samples of sardine oil, and two lian and avian nutrition, while The vitamin D potency of cod tuna oils are either equal or superior to the cod few, if any, such oils have been liver oil shall be expressed in placed on the market for human h e r oil as a source of zitamin D. units per gram of oil, the unit to c o n s u m p t i o n . Sardine a n d be the minimum average amount The suggestion is made that, with improved tuna oil are produced in sub(in milligrams) of cod liver oil refining practices, the edible tuna oil may find required to produce, in 60 per cent stantial quantities on the Pacific of the animals in any one group, a place as a source of vitamin D in human C o a s t . According t o Nela degree of r e c a l c i f i c a t i o n therapeutics. eon and Manning (6) approxirepresented by a narrow “line” m a t e l y 6,500,000 a n d 60,000 across the m e t a p h y s i s of t h e gallons, respectively, is the annual production of these oils. leg bones of the rats which have been kept and fed under the conditions as specified in the assay. The vitamin D content Bills (2), in comparing four samples of sardine oil with a per gram of cod liver oil is computed by dividing 1000 mg. medicinal cod liver oil, found them to be approximately (1 gram) by the determined minimum average daily amount of of the same vitamin D potency. Axhundson et al. (1) state oil, in milligrams, required t o induce the requisite degree of that pilchard (sardine) oils are variable in this factor and in recovery. The average daily dose is understood to be the total amount of cod liver oil given divided by the length of the test no case are as potent as either commercial or medicinal cod period, 10 days. liver oils. Brocklesby and Denstedt (4) indicate a high potency of vitamin D in pilchard oil although not as rich a The method further designates that “when so assayed the source of vitamin D as cod liver oil. Nelson and Manning oil shall contain a t least 100 vitamin D units per gram.” (6),in testing raw sardine and a raw tuna oil for vitamin Interpretations in this paper have been based upon the asD, found the former to be equal to, and the raw tuna oil sumption that the narrow continuous line corresponds to a superior to, a known, high-grade, medicinal, cod liver oil. 2+ degree of healing, as described by Bills and McDonald The purpose of this investigation was to determine the vita(3). Table I gives a summary of the experimental data. min D potencies of different commercial raw sardine oils and refined tuna oils. TABLE I. ANTIRACHITIC POTENCIES OF SARDINE AND TUNAOILS DAILY RATS ON DEQREE OF VITAMIN D SOURCES OF MATERIAL SUPPLEMENT SUPPLE-HEALINQ (Av. UNITS OIL (8 DAYS) MENT LINE TEST) PER QRAM The sardine oil is extracted from the California pilchard Mg. (Sardinia caeruka) or sardine, which are fished from the 1. Raw sardine 8 6 1.5f -155 vicinity of San Francisco to San Diego. This may be ob- 2. Raw sardine 14 2.1f 8 155 tained from either the whole fish, the fish offal, or both. 12 6 3.0+ , Tuna (Neothunnus macropterus) are k h e d in Mexico and 3. Raw sardine 8 10 2.2+ 155 10 11 2.7f Central America waters. They are delivered to the cannery 12 11 2.9+ and packed in ice 15 to 35 days after the catch. After clean- 4. Raw sardine 6 9 2.0+ 208 ing, the fish are cooked from 2.25 to 6 hours in direct steam 8 11 2.5+ 10 9 2.6f cookers a t a temperature of 105’ C. The white and dark 6 7 1.3f meat are separated after cooling. The former is canned, 5. Refined tuna 8 6 1.0f 10 8 2.Of 125 and the oil pressed from the dark meat and off-color white 12 2.3f 8 meat. The dark color and appreciable free fatty-acid con5 9 1.0f tent of raw tuna oil makes it unacceptable for use even in 6. Refined tuna 6 7 1.3f 8 7 1.3+ animal feeds. Thus, it must be refined before entering the 10 2.1+ 8 125 market and the possibility of vitamin destruction is a matter 12 7 1.7+ 15 8 2 . 4 + of concern. 12 6 2.6f f208 Four representative samples of raw sardine oil were ob- 7. Refined tuna 2.6+ 12 10 tained from three different fish oil producers. All are repre6 7 2.0+ 208 sentative of different commercial lots of oil. The four sam- 8. Refined tuna 10 6 2.7+ ples of refined tuna oil, representative of four distinct com- 9. Cod liver 6 2.2+ 6 208 6 3.5f 18 mercial lots, were received from the same concern during .. 30 Severe rickets ... a 2-year period. The U. S. P. medicinal cod liver oil was of Controls (preliminary) .. I 32 No healing Norwegian origin. Controls (exptl.)
...
563
5 64
INDUSTRIAL AND ENGINEERING CHEMISTRY
In general, results obtained here have been in fair accord with those reported by other workers upon sardine and tuna oil. The variation of antirachitic potencies of the sardine oils tested is not great. Only one of the oils proved as good a source of this factor as the medicinal cod liver oil, although all exceeded the requirement of the American Drug Manufacturers’ Association for cod liver oil. Two samples of refined tuna oil were slightly inferior to three samples of raw sardine oil, and two were the equal of one sardine oil and the medicinal cod liver oil. The greater variability of vitamin D in the refined tuna oils may be due to differences in refining processes, which would be one factor limiting the ultimate vitamin D potency of refined tuna oil. It is suggested that refined tuna oil, since
Vol. 25, No. 5
it is produced from edible portions of the fish and possesses a light yellow color and a mild fish flavor, may be acceptable as a source of vitamin D in human therapeutics. LITERATURE CITED (1) Amundson, Allardyce, and Biely, Sci. Agr. (Canada), 9, 594 (1929). (2) Bills, J. BioZ. Chem., 72, 751 (1927). (3) Bills and McDonald, Ibid., 68, 821 (1926). (4) Brocklesby and Denstedt, Can. Chem. Met., 14, 29 (1930). (5) Holmes, J. Am. Pharm. Assoc., 20, 588 (1931). (6) Nelson and Manning, IND. ENQ.CHEM..22, 1361 (1930). RECEIVED November 8, 1932. Presented before the Division of Medicinal Chemistry a t the 84th Meeting of the American Chemical Society, Denver, Colo., August 22 to 26, 1932.
Effect of Particle Size on Capacity of Zeolites PAULBIRD, FRANKCOLBURN,AND FRANKSMITH,Iowa State College, Ames, Iowa
I
N ORDER to make comparative tests for the matersoftening capacity of zeolites, it is essential that the size of the particles tested be stated. Fine materials have a greater area per unit of volume than coarse materials. As the action of zeolites is a function of the availabIe surface, it is apparent that comparable results can be obtained only
than the mesh size. The values given for the average length of side were taken from data prepared by the W. S. Tyler Company (2). The capacity of the zeolites is stated in terms of grams of calcium carbonate equivalent of hardness removed from water per liter of zeolite. Each point is the average of ten runs, and is calculated from results originally
from zeolites of the same size. SCREENSIZE The most common method of expressing particle size is by designating the sifting screen that will just pass the material, and that screen that will retain the material under investigation. Thus to state that a zeolite is of 30- to 40mesh size means that the zeolite will just pass through a screen having 30 openings per square inch (per 6.5 sq. cm.) and be retained on a screen having 40 openings per square inch. Even the statement of the mesh size is not sufficient, as there are several types of screens in use, and a screen of one series having 30 openings per square inch may not possess openings of the same size as a screen of another series having 30 openings per square inch. This is due to the fact that wires of different size may be used in making these two series of screens. Thus, it is also important to state the name of the series of screens used. I n this laboratory the Tyler Standard screen scale sieves are used (2).
EXPERIMENTAL PROCEDURE Four samples of different zeolites were carefully screened on Tyler screens, washed free of phenolphthalein alkalinity, and tested in miniature water softeners for capacity. The sizes of the screens used were the 8, 10, 14, 20, 28, 35, 48, and 65-mesh screens, which had openings of 2.362, 1.651, 1.168, 0.833, 0.589, 0.417, 0.295, and 0.208 mm., respectively. The method of testing has been described (1). The steps required are backwashing to loosen the bed, salting by allowing brine to flow downward through the bed, washing to remove the salt, and softening, During the softening period the hard water was passed downward through the bed at such a rate that 4 hours were required to exhaust the zeolite. A run was considered to be complete when the effluent water showed 17 p. p. m. of hardness. The water contained 376 p. p. m. of hardness. I n order to plot the values obtained (Figure 1) the average length of side, or dimension, of the particles was used rather
10
M
a4
1
LENGTH OF SIDE- mm. 0.6 0.8 1.0 L2
I
/.e
L6
A8
20
&?
FIGURE 1. RELATION BETWEEN CAPACITY AND PARTICLE SIZE
expressed as grains of calcium carbonate per cubic foot, using 2.31 grams per liter as equal to 1000 grams per cubic foot. The exchange capacities of four artificial zeolites were found to vary inversely with the particle size. LITERATURE CITED (1) Bird, P. G . ,IND. ENO.CHEM., 24,793(1932). (2) W.S. Tyler Company. Cleveland, CutaZog 53,37 (1927).
R~CEIVED October 17, 1932.
CORRECTION. An error has been found in the article on “Compression Stress Strain of Rubber” by J. R. Sheppard and W. J. Clapson [IND.ENQ. CHEM.,24, 783 (1932)l. In the second column, in the sentence directly under Equation 5, “Equation 4” should read “Equation 5,” and vice versa. The corrected sentence then becomes: “Equation 5 defines the compressive force as a function of the equivalent tensile and of the new (diminished) length in the direction of compression when the original (unstrained) specimen is a cube of unit length; Equation 4 defines the compressive force in terms of the equivalent tensile.* * *”
