166 THE ANALYST. AN EXAMINATION OF MUSTARDS MANUFACTURED AND SOLDIN NEW PORK CITY. BY E, WALLER AND E. W. MARTIN. WE bave bad occasion recently to make an examination of samples of mustard manu- faotured in New Yoi*k City, and have presumed to believe that a statement of our results may not be without interest to the members of the Society of Public Analysts. Many interesting points have been suggested by the results of the examination, but we are at present too closely occupied with other mattem to follow up the lines of inquiry so attraotivoly suggested, The samples of dry mustard (Table I) represent the lowest pa$m of mustard put upon the market by &Ven different rnunufaaturers, while the samples of mustard pastes TABLE I,-(DRY) MUSTARD MANUFACTURED AND SOLD IN NEW YORK CITY.6-84 6-78 4.92 2-05 16-05 NO. - 197 204 206 207 208 209 213 214 216 217 218 219 294 215 7 Mar tins Y. Turmeric Ma&ns Y. ~ u ~ n e r i c Moisture, 1 Fixedoil. Gout’s stmch CaSO, present ,, Ash fused CaSO, present i: 9 9 i- 6.15 8.03 7-36 8.23 8.50 7.24 7-65 7.60 7.15 5.45 6-60 8.45 6-62 9-86 21-17 12-79 12.54 8-42 10’92 6.81 13.32 7.74 9.09 20.57 8.59 14-59 .22*56 6-21 I I ,, ,, I ” [Mrtrtins Y. Soluble, CaSO, present :: CaSO, present CaSO, present N: starch 0-30 1-39 0.23 0-15 2.90 0.10 0.64 1.53 0.20 0.15 1.52 2 15 1.62 1-16 NO. 221 222 237 242 244 Asb , Ash. Common Other Or- Moisture. iz!,~ oil, Salt, 77*02 2-76 2.56 14*18 2.51 093 3.4s 2-11 81.52 1-98 3.50 10.67 1.77 0.56 2.33 1.63 77.62 2‘43 8-90 12-60 2.52 0-97 3’49 76-54 3.69 4-57 11-53 2-89 0.98 3-67 1:k6 81.45 2.94 3.73 9.09 2-14 O*G6 2-79 1.77 Insoluble.)il on dried 5’54 45-39 4-69 1-90 13.15 3.55 5.17 1*69 2-91 6-12 5-65 G*65 4-86 3.54 Netallic Copper (per cent.) Colouring Remarks, &o. Total. 21.24 19-51 23-14 22-44 I I trace 0.009 0*003 trace Ckwman mustards,” (Table 11) as they are termed here in the trade, represent four TABLE II,-MUSTARJI PASTE, b 1 GERMAN MUSTARD,” MANUFACTURED IN N.Y. (YITY. different manufacturers, Nos. 231 and 242 being from the same. Ask-Ignition of the dried residue from the above at as low a temperature as possible, after weighing, boiling with water, filtering and weighing tho undissolved residue to get rJoluble and insoluble ash.TEE ANALYST. 167 - No. HzO Oil. Pixed oil.-Extraction in a modified form of Soxhlet apparatus with ether.The modification was only of such a nature as to render the apparatus more durable, tmd had no effect on the principle or method of extraction of the Soxhlet apparatus. For the German mustards the method followed had only those modifications which the pasty condition of the material required. In extracting the oil some 15 or 20 gms. mere dried in the air bath unhl the material ceased to lose weight, when it was ground up in a mortar, a portion weighed out and extracted with ether in the Soxhlet apparatus. The results so obtained are given in the column headed '( Oil on ,dried mustard," and by calculation the figures in the third column (Table 11) were determined. The cccctic acid was determined by washing a weighed quantity of the paste on a filter with cold water, until the filtrate was neutral, adding coralline and titrating with half normal sulphuric acid.The acetic acid-so calculated was deducted from the loss by drying, which was assumed to represent moisture and acetic acid together. Copper was determined by destroying the organic matter so far as possible by heating with fuming nitric acid, finally fusing with potassium nitrate, and subjecting tho solution (converted into sulphates) to the action of a-battery, In heating for this purpose, burners constructed of glass and cork were used. As a guide in these examinations samples of mustard purporting to be pure wer obtained from manufacturers in the City, and specimens of mustard seed were also obtained, which after repeatedly grinding in n coffee mill were submitted to the same tests.Through the kindness of Mr. Wigner we reoeived also samplea of mustard flour and seed from the liondon market, the results on which are also given in Tables 111 and lV. Ash, Soluble. Ihsoluble.1 Total. Remarks. TABLE III.-(BoLTED) MUSTARD FLOUR PURPORTJNG TO BE PURE. From New Yor& Nm2cfactztrers. 201 6.10 2642 0.21 6'92 6.21 220 6.60 26.70 0-86 4-80 5.66 273 6-85 36.67 0.176 3.725 3.900 274 4*75 41.70 0.126 4.435 4.550 Bnglieh Samples. Trieste and Bombay Seed, mixed. Whiteseed. Brownseed. Ash fused. TABLE IV,---GROUND MUSTARD SEEDS. NO Hind of Seed. H80. Oil. AXEMCAN MARKET. 23 1 Bombay .. .. 7-52 36*96 232 Trieste .. 6-35 36-45 233 California diiow , , 4-96 34-00 234 EnglishYellow 6-10 35*46 271 White * * *, 7.10 34.45 272 Brown ..7.30 34'71 ENGLISH MABKET. Ash. .- Sohble. Insoluble. Total.' 1.26 4.37 5-62 0-70 3.70 4.40 0*60 4-40 4.90 0.26 4.55 4.80 0.7 3*9 4.60 0-85 3-9 4-15168 THE ANALYST. The results obtained for 08 on NOS. 201 and 220 led to inquiry, the result of which was the discovery that it is the regular practice of the mustard manufacturers here to express a portion of the oil from the pound mustard seed, before working it up into the condiment sold as mustard. In these samples, as well as in No. 219, which was sold under guarantee of being pure mustard without admixture, no starch, colouring material, or other material known to be foreign to the mustard seed, was found. If we calculate, then, that these musttwds had been made up from mustard flour containing 25 per cent of oil, by multiplying the percentages of oil given in Table I by four, we would get; approximately the proportions of mustard flour present in per- centages.I n justice to the manufacturer of No. 214, it may be stated that the package was labelled as consisting of a mixture of mustard and staiwh. On none of the other samples, however, did there appear any such intimation. we were told that a man who formerly worked under one of the well-known English manufacturers of mustard had asserted that the practice of extracting a portion of the oil before making the condiment was used in England, and that in order to evade the vigilance of the ’Public Analysts, that starch or flour, saturated with some inferior fat or oil, was mixed in with the mustard flour.An assertion coming in so roundabout 8, manney would have received no attention, had it not been that samples bearing the name of that manufacturer, were submitted to examination at the same time with those above enumerated. Notwithstanding a high percentage of oil, the samples con- tained starch when examinod by the microscope, and by the iodine test, and the oil extracted was decidedly more fluid than that extracted from any of the other samples. These points gape Borne colour to the statement quoted. AS yet, however, we have been rinslble to verify the actual presence of any oil Mr. Wigner also kindly sent us a sample of The oil extracted from that did not; have 80 foreign to mustard in the extracts. mustard from the same manufacturer. marked a fluidity.The results were as follows :- Ash 7- No. H,O Oil. Soluble. Inaoliible. Total 199 35-15 0.34 3.64 3.98 1 Ash fused in dl cases. 230 4- 92 35.13 0.25 3.80 4-09 All contained Turmeric 275 5,175 32-01 0-25 3*62 3-87 and Starch. Nos. 199 and 230 were of the ~ a r m brand, though purchased at different times and in different places, No. 275 was the sample sent by Mr. Wigner, So far as the results of the teats on genuine mustards (flour and seed) go, some modific8tion seems necessary for Dr. Blyth’s statement (Foods, p. 491) that 30 per cent. of the ash of mustard is rJoluble in water. The fusibility of the ash of some of the specimens was an unlooked-for phenomenon, and what tests we have made have been insufficient to decide the point. It is apparently not due to presence of an excess of carbonates of the alkalies, as the reaction of the solution of the ash was only very faintly alkaline.Noreover, even after boiIing ~ t h water the fusible portion was not removed. Remarks.THE ANALYST. 169 ~ On a few of the samples the experiment of removing the oil by the use of CS2 in the Boxhlet apparatus was tried ; the results were found to be lower in every case than when ether waa used. As witness : Sample No. Oil by ether. Oil by CS,. . 197 21.17 19*73 207 842 6'36 213 13.32 10.90 220 25.70 25.0s We have not yet decided as to the aipifiotmce of this fact. Nos, 197, 20'1, 213, and 294, were found to be coloured with Hartins yellow (di- nitronaphthol), a specimen of which was handed us at the same time with the samplm of mustard.The sample had apparently been made from the sulpho compound, as it gave reactions with barium salts, after fusion with potassium nitrate. After purification by solution in alcohol, filtering and rec+ystallising the product failed to give this reaction, The sample was the calcium compound, and was found to contain :- CaO H20 POURd. Theory for Ca(C,,H,N2O6),6H2O. 998 9.12 17-00 per cent. 17*59 The calciam, sodium, and ammonium salts are moderately soluble in hot water, In these solutions, potassium chloride produced precipitates of red tufted crystals, not very soluble in water or alcohol. In the solution of the ammonium salt, concentrated solution of ammonium chloride produced a precipitate. I n any of the aqueous solutions precipitates soluble in alcohol mere produced by soluble barium, lead, and silver salts ; the colours of these precipitates ranged from orange to almost a vermillion shade.The addition of acids ( HUl,H4S04) to the aqueous solutions gave lemon yellow precipitates of the acid €using at 135O.7 C. (Recorded fusion point of pure acid 138" C.) By pro- longed heating with strong nitric acid, phthalic acid was obtained, proved by obtaining from it fluorescein by heating with resorein. The acid was readily soluble in chloroform. All of the compounds deflagrated violently on ignition. The calcium salt, when crystallised rapidly from its solution, gave crystalline plates ; when allowed to separate more alowly, it formed needles. By drying in the air bath its colour was deepened to red. It was found that qualitative tests for the presence of this oolour in the mustard could be made by pouring alcohol of 93 to 95 per cent, upon the mustard, allowing it to act for a few minutes (cold), stirring occasionally, and filtering.Moat of the colour, with some of the oil, wm thus extracted: By evaporatingoff the alcbhol and treating the residue with water, a solution was obtained in which wool could be readily dyed a brilliant yellow, The water solution, nevertheless, contained some gummy or oily substance, which presented some difficulties in the way of obtaining crystals of the colouring matter, for examination by the mioroscope, and the more thorough the extrac- tion with alcohol, and subsequent treatment with water, the greater this difficulty. We have 8s yet been unable to effect a satisfactory quantatitive separation of the colour in consequence, but atill hope to perfect some plan for that purpose.170 THE ANALYST. ~~ - ._ __ _ . ~ ~ Statements regarding the physiological effects of this colouring matter when swallowed, are few and far between. Eulenberg, in his Handbuck de Qewerbliche Hygiene, states, that the dinitronaphthol is non-poisonous. Experiments made upon dogs by Dr, 0, Edson, of the Health Department, in connection with this investigation, went to show that it was a strongly irritant poison. Four dogs, each weighing about 50 lbs., were killed by doses of 15 to 40 grains of this colour. The autopsy showed acute gastero-enteritis as the cause of death.