1362 .I. G . TVOODMXK :IXD H. P. T A L B O T

n s i u 111 carbonate, and find strong support in observations made else- where. Where calcium carbonate instead of riiagiiesiuni carbonate is preseiit in the cultiire solutioiis, the process of iiitrificatioii is niodified, and tlie presence of uiiosidized aiiiiiiotiia does n o t seem to inhibit the de\.elopnient of the nitric ferments. Gilder actual soil conditions the forination of nitrites and nitrates may not only occur a t tlie same time, bnt tile nitrites n i ay be oxidized as fast as they are loriiml, and the sctiv- ity of the nitrous ferments inny thus be coiiccaled. It should be iioted here. however, that organisms may exist in the soil, which have the poircr of coiiwrting aniiiioiiia directly iiito nitrate without the iiiternie- d i n k formation of nitrites. Such, a t least, is the claim made by Kase- rer, ' atid there are observations mxde by others, which would lend sup- port to this claini.

THE FLUORINE CONTENT OF MALT LIQUORS. 1 3 ~ .I G . ~ V O O I I S I A K .%SI) 11. P l.11 ImT.

I n a previous paper' the authors outlined a method for the approximate estiniatioii of fliioricles when present in niitiute quaiitities, such as might occur in food products. At that time the hope mas expressed that i t might be possible to esaiiiitie l ~ y inearis of the niethod, various classes of food products with a view to :!eteriiiiriing the limiting values for their fluorine content. For obvious reasons, iiialt liquors seemed excellent material for beginning such an investigation, arid i t is the purpose of the present paper to summarize the results obtained in tlie examination of a number of the brands of malt liquor 011 the market, as well as the materials used in brewing.

Mct/lod.--The method used was similar to that already described, ex- cept that on accoant of the large amounts of carbonic acid in the beers, it was found necessary in every case to add a soniewliat greater quantity of barium acetate, enough being used to ensure an excess iii the filtrate from the barium sulphate and fluoride. For the same reason more sul- phuric acid (3-4 cubic centimeters instead of 2-3 as previously directed) is iiecessary during the etcliing. Ai insufficient amount of either of these would occasion negative results, eveu if an appreciable amount of fliioride were present.

In extracting the fluoride from malts and barleys it was found inad- visable to grind the sample and extract with hot water, as would be done in the brewery operation of mashing, because the large amount of sugary and starchy matters extracted interfere with the subsequent precipitation of the fluoride. Satisfactory results were obtained in the case of malt by

Centr. Bakt., Parasitenk., 11, 16, 6S1 ;itid j69 (1906). This Journal, 28, 1437, (1906).

FLUORINE CONTENT O F hlALT LIQUORS 1363

digesting the unground sample with boiling water for three or four min- utes, pouring off the water and repeating the operation. In the extract thus obtained fluorides were precipitated i n the usual manner. 1x1 the case of barley, where reducing sugars were practically absent, the extrac- tion was made on the ground sample but the digestion was carried out for half an hour at 40°-500, a temperature below the gelatinizing point of starch.

Reszdts.-The results obtained with a number of commercial malt liq- uors and with the principal raw materials of brewing are shown in the following tables. T h e results are stated in milligrams of fluorine per liter, or per kilogram in the case of solids. For convenience, the table of amounts of fluorine corresponding to the different " etching temperatures " given in the earlier paper' is here stated again in this form.

T h e values taken are based in each case upon the use of 150 cc. of the samp1.e. With solids, the values will depend upon the weight taken and can be found readily by a simple calculation. Differences due to varia- tions in specific gravity are so slight as to be neglected.

T h e samples of beers and ales represented about 50 different brands. T h e samples of malt and barley included both Eastern and Western growths.

TABLE I. ~ \ ~ I L L I G R A M S O F FLUORINE PER LITER ( O R PER KILO) CORREsPONDINC TO THE

ETCHING TEMPERATdRES " It'HEK 150 CC. (I50 GRAMS) ARE USED. Temperature

79O-S2' IO to 40 113O I to I O

I 36' 0 .2 to I O

173'-178' 0 . ~ 4 to 0.2

213~-21S~ Less than 0.04 TABLE 2.

FLUORINE IN M A L T LIQUORS AND BREWING MATERIALS. &IILLIGRAMS PER LITER (PER KILO).

L B O V I

................ ............ .... . . . . . . . . Barley. 15 I 4 I 9

Domestic Ale a c d Beer .34 ........ 4 . . . . . . . . g .... 21 . . . . . . . . Imported Ale and Beer.. 15 3 .... 5 . . . . . . . . 2 .... 5 . . . . . . . .

Malt. .................. 15 .... 2 .... 13 . . . . . . . . . . . . . . . . . . . . . . . . Brewing Sugar. ........ g . . . . . . . . . . . . . . . . I . . . . . . . . . . . . . . . . Y

A sample of beer was brewed in the laboratory from materials which had been previously examined and had been found, with the exception of the malt, to be free from fluorides. This was done to determine if, under

Loc. cit.

11-ort After .-\cltiitioii of Yeast. (l .<,J

n'ort 3 days after addiiig yeast . . . . . . . . . . . . . . . . . . ( I .o ) ' ' 6 " < ' < c .................... ( : , o )

' / ................ . . ( 1 . 0 ) " 9 " ' ( ' , 1 ' I2 ' I " " ' 1 .................. ( 1.0)

Wort after 5 (lays in storage ...... ( 10.0)

I n examining this table is should be borne in iniiid that the great differ- ence shown it1 the beer before and after the period of five days storage is more apparent than actual. Owing to the limitations of the method it is inipossible to follow closelj- gradual changes in the fluoride content until the amount present approaches one of the litnits fixed by tlie etching temper a t LI re.

I t is no doubt true that the content of fluoride was steadily iiicreasing during the fernieiitatioii aiid that not tinti1 the final test was enough pre-

FLUORINE CONTENT O F MALT LIQUORS 1365

sent to show at the IO milligram point, although it had passed the I milli- gram point some time before.

I t is also true that the presence of sugary matter prevents to some ex- tent the precipitation of the fluoride, even when the latter is present. It is highly probable that the apparent increase in fluoride content is due rather to the decrease in sugar as the fermentation proceeded, and the consequent availability of the fluoride for precipitation.

Through the cooperation of a large malting establishment we were en- abled to go one step further back and follow the malting process in its effect on the fluoride content of the grain. Samples were sent u s of the barley, the water used for steeping, and dried samples of the malt a t var- ious stages from the steeping tank to the finished product. On these samples the following results were obtaiiied:

Milligrams per kilo

Hard steep water. ............................. 10.0

Soft " I ' .............................. Kone ......................... Barley before steeping. 3.0

Steeped barley.. 3.0 Malt 2 days old. . 3.0

............................... ..............................

................................ 3.0 ' I as put on ki ln . . ........................... 3.0 ' ( from kiln ................................. 8.0

" 4 ' I "

Summary. First ,

that the preseiice of a slight amount of fluoride in malt liquors is the rule rather than the exception, and second, that the principal source of this fluoride is the malt itself. I n the majority of cases it is undoubtedly true that the proportion of fluoride in the beer is entirely accounted for by the malt.

This amount may be slightly increased in some cases by smaller quan- tities introduced through the use of brewing sugars, from the water, es- pecially if artificially hardened by the use of gypsum containing fluoride, or from the yeast.

I t is of course possible that fluorine was present in all the samples of barley and that the simple method used for the extraction failed to re- move it, especially that present as insoluble calcium fluoride. A more probable explanation, however, is to be sought in natural geographical variations in the soil. the use of commercial fertilizers, such for instance as phosphate rock, notoriously rich in fluoride, and other primary agri- cultural factors. Judging from the results obtained on a considerable variety of samples, it would seem that one part of fluoride in ~oo,ooo ( I O

mgs. per 1iter)was not too severe a standard to set for the maximum limit of permissible fluoride in malt liquors.

From the results obtained two things are strikingly apparent.

I 366 J O H N WIKI<LEK

T h e greater portion of the domestic saniplcs esainiiiecl did not coiitaiii over r:j,Goo,ooo 1 0 . 2 I I I K . : ) i r i i t s r ) .

Testing n malt liquor bj- tlic nietiiod described. then, we should think that if I jo cc. coiitaiiied eiiougli iiuoritle to gise a r%il>lv ttchiiig at Soo, the sniiipie was open to suspicion as contnitiing added fluoride.

111 coi;ciusioii, the authors take pleasure iii ackiio\\.ledgiiig their in- dei)!c-dnc..;; t o Miss 1:lizahetli ilniisoti for i!ittcli paiiist:tking aiid careful anai !: t i c ;; i x( I ? 1:.

. ~ I . ~ s s . ~ c I ~ L - s I : i r,s INSTITL'TI: OF Julie. I<;O;,

FACTORS I N BORIC ACID MANUFACTURE. DY J O I I s TV 1 9 IC Lli l l .

Oiie who may he interested in the subject of boras will find the phase relating to i ts occurrence, productioii aiid uses, in the U. S. Miiieral Resources for any year from 1900 to 1905 ; the phase relating to its physiological action i i i Dr. H. LV. IL-iley's Report, Bull. 84 or Cir. 15 ; arid the phase relating to i ts detectioii and estimation in niinute quantity iii foods in this Journnl, Ju ly , 1906. For tlie analytical phase aiiioiig tlie best referenccs a r e : J . SOC. Cheni. Iiicl., July, 1904; Sutton Vol. Analysis ; Zeitscli anal. Cliemie., 34, (1900); Chemiker-Zeituiig, Jan. 16, 1901. Ancl for the geological phasc the best work.; are those of Kenip, C. W. hIiller. "lie C:!lif. State Miriiiig Report I S ~ Z . 'The "Saliue Ikposit:; of California" 1 ) ~ . G. 6. I3,iiley ( Cal. State Mining Bureau S. F.).

These authorities seem to agree with the practical inen in the borax fields that the origiri of the borates must haye been emanations from volcanic vents and hot springs ; and likely in the form of boric acid car- ried by the steaiii and other p s r s : :1.iic! :hat sub5equently such borates as colemanite (which is horatc of lime wilh LY2tt.r of cr)-st:illization), slid others must ha re crystallized from lakes and springs on evapora:ion, and. of course, were deposited as strata. .Is n rule these strata are found associated I-,-it11 secondary clays, which clays may also be impregnated with horate.

X number of analyses of these borate clays sliow them to have the fol- lon4ng general co i i~pos i t io~~:

Keceived June 4, go;.

Borate formation appears distinctive.

SiO,

FeO and Fe,O, CaO

A1203

YgO Tlie borates are

inmufacture much

4j-55 per cent. N3,Oalid K,O $ - 2 J < per cent. 1 g . 0 ' 8 ' I , < - - I ( I '

j - I j ' i " B,O,, 0 - 3 c ' ' ( ' I - 4 ' ' Ory. matter moisture, considerab!e.

mixed ~vi t l i gypsuin and carhonates, which niakes niorc expensive. "lie sodium carbonate is mixed

5-15 " ' I CO, , - J

4-12 " I ' SO, , - .>