Scientific American Supplement No. 531, 6.3.1886

By William Lawson.

The subject which I have the honor to bring shortly before your notice this evening is one that formed the basis of some instructive remarks by Dr. Redwood in November, 1855, and also of a paper by Dr. Hassall, read before the Society in London in January, 1856, which latter gave rise to an animated discussion. The work detailed below was well in hand when Mr. MacEwan drew my attention to these and kindly supplied me with the volume containing reports of them. Unfortunately, they deal principally with the adulterations, while I was more particularly desirous to learn the composition in a general way, and especially the percentage of coloring resin, the important constituent in commercial annatto. Within the last few years it was one of the articles in considerable demand in this part of the country; now it is seldom inquired for. This, certainly, is not because butter coloring has ceased to be employed, and hence the reason for regretting that the percentage of resin was not dealt with in the articles referred to, so that a comparison could have been made between the commercial annatto of that period and that which exists now. In case some may not be in possession of literature bearing on it - which, by the way, is very meager - it may not be out of place to quote some short details as to its source, the processes for obtaining it, the composition of the raw material, and then the method followed in the present inquiry will be given, together with the results of the examination of ten samples; and though the subject doubtless has more interest for the country than for the town druggist, still, I trust it will have points of interest for both.

Annatto is the coloring matter derived from the seeds of an evergreen plant, Bixa Orellana, which grows in the East and West Indian Islands and South America, in the latter of which it is principally prepared. Two kinds are imported, Spanish annatto, made in Brazil, and flag or French, made mostly in Cayenne. These differ considerably in characters and properties, the latter having a disagreeable putrescent odor, while the Spanish is rather agreeable when fresh and good. It is, however, inferior to the flag as a coloring or dyeing agent. The seeds from which the substance is obtained are red on the outside, and two methods are followed in order to obtain it. One is to rub or wash off the coloring matter with water, allow it to subside, and to expose it to spontaneous evaporation till it acquires a pasty consistence. The other is to bruise the seeds, mix them with water, and allow fermentation to set in, during which the coloring matter collects at the bottom, from which it is subsequently removed and brought to the proper consistence by spontaneous evaporation. These particulars, culled from Dr. Redwood's remarks, may suffice to show its source and the methods for obtaining it.

Dr. John gives the following as the composition of the pulp surrounding the seeds: Coloring resinous matter, 28; vegetable gluten, 26.5; ligneous fiber, 20; coloring, 20; extractive matter, 4; and a trace of spicy and acid matter.

It must be understood, however, that commercial annatto, having undergone processes necessary to fit it for its various uses, as well as to preserve it, differs considerably from this; and though it may not be true, as some hint, that manufacturing in this industry is simply a term synonymous with adulterating, yet results will afterward be given tending to show that there are articles in the market which have little real claim to the title. I tried, but failed, to procure a sample of raw material on which to work, with a view to learn something of its characters and properties in this state, and thus be able to contrast it with the manufactured or commercial article. The best thing to do in the circumstances, I thought, was to operate on the highest priced sample at disposal, and this was done in all the different ways that suggested themselves. The extraction of the resin by means of alcohol - the usual way, I believe - was a more troublesome operation than it appeared to be, as the following experiment will show: One hundred grains of No. 8 were taken, dried thoroughly, reduced to fine powder, and introduced into a flask containing 4 ounces of alcohol in the form of methylated spirit, boiled for an hour - the flask during the operation being attached to an inverted condenser - filtered off, and the residue treated with a smaller amount of the spirit and boiled for ten minutes. This was repeated with diminishing quantities until in all 14 ounces had been used before the alcoholic solution ceased to turn blue on the addition to it of strong sulphuric acid, or failed to give a brownish precipitate with stannous chloride. As the sample contained a considerable quantity of potassium carbonate, in which the resin is soluble, it was thought that by neutralizing this it might render the resin more easy of extraction. This was found to be so, but it was accompanied by such a mass of extractive as made it in the long run more troublesome, and hence it was abandoned. Thinking the spirit employed might be too weak, an experiment with commercial absolute alcohol was carried out as follows: One hundred grains of a red sample, No. 4, were thoroughly dried, powdered finely, and boiled in 2 ounces of the alcohol, filtered, and the residue treated with half an ounce more. This required to be repeated with fresh half ounces of the alcohol until in all 7½ were used; the time occupied from first to last being almost three hours. This was considered unsatisfactory, besides being very expensive, and so it, also, was set aside, and a series of experiments with methylated spirit alone was set in hand. The results showed that the easiest and most satisfactory way was to take 100 grains (this amount being preferred, as it reduces error to the minimum), dry thoroughly, powder finely, and macerate with frequent agitation for twenty-four hours in a few ounces of spirit, then to boil in this spirit for a short time, filter, and repeat the boiling with a fresh ounce or so; this, as a rule, sufficing to completely exhaust it of its resin. Wynter Blyth says that the red resin, or bixin, is soluble in 25 parts of hot alcohol. It appears from these experiments that much more is required to dissolve it out of commercial annatto.

The full process followed consisted in determining the moisture by drying 100 grains at 212 deg. F. till constant, and taking this dried portion for estimation of the resin in the way just stated. The alcoholic extract was evaporated to dryness over a water-bath, the residue dissolved in solution of sodium carbonate, and the resin precipitated by dilute sulphuric acid (these reagents being chosen as the best after numerous trials with others), added in the slightest possible excess. The resin was collected on a tared double filter paper, washed with distilled water until the washings were entirely colorless, dried and weighed.

The ash was found in the usual way, and the extractive by the difference. In the ash the amount soluble was determined, and qualitatively examined, as was the insoluble portion in most of them.

The results are as follows:

| 1. | 2. | 3. | 4. | 5. | 6. | 7. | 8. | 9. | 10.
Moisture | 21.75| 21.60| 20.39| 69.73| 18.00| 18.28| 15.71| 38.18| 19.33| 22.50
Resin | 3.00| 2.90| 1.00| 8.80| 3.00| 1.80| 5.40| 12.00| 5.90| 9.20
Extractive | 57.29| 59.33| 65.00| 19.47| 58.40| 65.67| 26.89| 20.82| 23.77| 28.50
Ash | 17.96| 16.17| 13.61| 2.00| 20.60| 14.25| 52.00| 29.00| 51.00| 39.80
Ashes: | | | |Almost| | | | | |
Soluble | 13.20| 12.57| 7.50|wholly| 10.0| 11.75| 18.5 | 20.0 | 15.0 | 13.8
Insoluble| 4.76| 3.60| 6.11| NaCl.| 10.6| 2.50| 33.5 | 9.0 | 36.0 | 26.0

The first six are the ordinary red rolls, with the exception of No. 4, which is a red mass, the only one of this class direct from the manufacturers. The remainder are brown cakes, all except No. 7 being from the manufacturers direct. The ash of the first two was largely common salt; that of No. 3 contained, besides this, iron in some quantity. No. 4 is unique in many respects. It was of a bright red color, and possessed a not disagreeable odor. It contained the largest percentage of moisture and the lowest of ash; had, comparatively, a large amount of coloring matter; was one of the cheapest, and in the course of some dairy trials, carried out by an intelligent farmer, was pronounced to be the best suited for coloring butter. So far as my experience goes, it was a sample of the best commercial excellence, though I fear the mass of water present and the absence of preserving substances will assist in its speedy decay. Were such an article easily procured in the usual way of business, there would not be much to complain of, but it must not be forgotten that it was got direct from the manufacturers - a somewhat suggestive fact when the composition of some other samples is taken into account. No. 5 emitted a disagreeable odor during ignition. The soluble portion of the ash was mostly common salt, and the insoluble contained three of sand - the highest amount found, although most of the reds contained some. No. 6 was a vile-looking thing, and when associated in one's mind with butter gave rise to disagreeable reflections. It was wrapped in a paper saturated with a strongly smelling linseed oil. When it was boiled in water and broken up, hairs, among other things, were observed floating about. It contained some iron. The first cake, No. 7, gave off during ignition an agreeable odor resembling some of the finer tobaccos, and this is characteristic more or less of all the cakes. The ash weighed 52 per cent., the soluble part of which, 18.5, was mostly potassium carbonate, with some chlorides and sulphates; the insoluble, mostly chalk with iron and alumina. No. 8 - highest priced of all - had in the mass an odor which I can compare to nothing else than a well rotted farmyard manure. Twenty parts of the ash were soluble and largely potassium carbonate, the insoluble being iron for the most part. The mineral portions of Nos. 9 and 10 closely resemble No. 7.

On looking over the results, it is found that the red rolls contained starchy matters in abundance (in No. 4 the starch was to a large extent replaced by water), and an ash, mostly sodium chloride, introduced no doubt to assist in its preservation as well as to increase the color of the resin - a well known action of salt on vegetable reds. The cakes, which are mostly used for cheese coloring, I believe, all appeared to contain turmeric, for they gave a more or less distinct reaction with the boric acid test, and all except No. 8 contained large quantities of chalk. These results in reference to extractive, etc., reveal nothing that has not been known before. Wynter Blyth, who gives the only analyses of annatto I have been able to find, states that the composition of a fair commercial sample (which I take to mean the raw article) examined by him was as follows: water, 24.2; resin, 28.8; ash, 22.5; and extractive, 24.5; and that of an adulterated (which I take to mean a manufactured) article, water, 13.4; resin, 11.0; ash (iron, silica, chalk, alumina, and common salt), 48.3; and extractive. 27.3. If this be correct, it appears that the articles at present in the market, or at least those which have come in my way, have been wretched imitations of the genuine thing, and should, instead of being called adulterated annatto, be called something else adulterated, but not seriously, with annatto. I have it on the authority of the farmer previously referred to, that ¼ of an ounce of No. 4 is amply sufficient to impart the desired cowslip tint to no less than 60 lb. of butter. When so little is actually required, it does not seem of very serious importance whether the adulterant or preservative be flour, chalk, or water, but it is exasperating in a very high degree to have such compounds as Nos. 3 and 6 palmed off as decent things when even Nos. 1, 2, and 5 have been rejected by dairymen as useless for the purpose. In conclusion, I may be permitted to express the hope that others may be induced to examine the annatto taken into stock more closely than I was taught to do, and had been in the habit of doing, namely, to see if it had a good consistence and an odor resembling black sugar, for if so, the quality was above suspicion.

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