摘要:

THE ANALYST. FEBRUARY, 19U4. PROCEEDINGS OF THE SOCIETY OF PUBLIC ANALYSTS. ON THE SALINITY OF WATERS FROM THE OOLITES. BY W. W. FISHER, M.A., F.I.C. (Read at the Meeting, November 4, 1903.) THE waters described in this paper are obtained from the several geological formations grouped together as ‘ I oolites,” and comprising the following main divisions down- wards : 1. Kimmeridge Clay. 2. Corallian Oolite. 3. Oxford Clay and Helloway Rock. 4. Cornbrash, Forest Marble, and Great Oolite. This group of deposits extends in a broad strip entirely across England from the south coast of Devon and Dorset to the north-east coast of Yorkshire, but the waters here described are mainly from the districts near Oxford and the counties adjacent. During the past twenty years a great variety of samples have been examined, and probably the types of waters found in the oolites of this district will be found under similar conditions in other localities.Great OoZiie.-From the great oolitic limestone beds of the Cotswolds rise many magnificent springs of a high degree of organic purity, forming the head waters of the river Thames and its tributaries. The general charactere of these waters are well known, and examples of oolitic spring-waters are shown in Table I. It will be seen that the total dissolved mineral and saline constituents are about 20 grains per gallon, or even less ; the chlorides are small ; there is little or no ammonia ; while the proportion of organic matter is extremely small. Nitrates, however, are variable in amount, according t s the cultivation of the land adjacent to the springs, and often reach a substantial quantity.Broadly speaking, these spring-waters resemble spring-waters from the chalk in composition and character, and for similar reasons, being derived from limestones porous in character, from which the more soluble constituents have long ago been washed out by percolation, the dissolved solids are mainly calcium carbonate, with small quantities of magnesium and alkaline sulphates and chlorides.TABLE I.-WATERS FROM GREAT OOLITE SERIFJS (UNCOVERED BEDS). (Analysis iiz Grains per Gallon; 1 G'allon = 70,000 Grains.) ininoid Ammonia. NO. 3,779 1,064 2,307 2,460 2,533 2,636 3,011 2,960 2,850 3,738 3,833 1,280 3,196 3,385 3,355 2,093 2,392 2,446 4,360 3,076 3,904 3,040 3,897 3,661 3,666 3,680 - absorbed, ctc.Three Hours. Locality. Near Bibury, Glos., Kitrbrook, Oxon Near Moreton-in-Marsh, Near Moroton-in-Marsh, Chipping Norton, Oxon Over Norton, Oxon Fullbrook, B u r f o r dy Burford, Oxon Brize Norton, Oxon Leafield, Oxon Brac kley , Nort hsn t s Charlbury, Oxon Bradwell, Burford, Oxoti Witney, Oxon Woodstock, Oxon Middleton, near Bices- Middleton, near Bices- Gowell, near Bicester, Bicester, Oxon Fringford, Oxon Stratton Audley, Oxon, Newport Pagnell, Bucks Stony Stratford, Bucks Buckingham, 1901 Upper Colne River Glouces ter Glouces ter Oxon $ 3 Y, ter, Oxon ter, Oxon Oxon new boring Depth in Feet. __ ~- Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring Spring 70 80 30 50 66 120 112 120 130 50 301 301 301 - - - Total Solids.19.0 18.0 18.2 19.8 21.0 18.0 20.1 20.4 25.5 32.0 37.5 21.0 21.3 22.1 54.0 22.1 26-0 32.0 26.6 26.8 25-0 36.4 32.2 38-9 60 0 68.7 30.0 Chlorine in Chlorides. 0.7 1.1 0.8 1.0 0.8 0.77 0.9 0-8 0.9 1 *1 1 .o 1.2 0.9 1.1 3.0 1.0 1.15 1.5 1.1 1.3 1.1 2-4 1.4 2.0 8.2 10-0 2.0 Saline Nitrogen 0.147 0.003 0.07 0.35 0.02 0-322 0.014 0.31 0-315 0.462 0.203 0.140 0014 0-35 0.25 0.05 0.08 0.014 0.021 0.014 0.04 0.07 0.02 0.203 0.45 0.014 0 014 0.014 0.001 0.001 0.001 0.002 0.001 0,004 0.002 0.002 0.001 0.008 0.019 0.0 0.001 0 a02 0.003 0.023 0.014 0.028 0.005 0.001 0.051 0.0 0.005 0,017 0.016 0.021 0.002 0.001 0.003 0.003 0-004 0.001 0.004 0.003 0.004 0.00 1 0.008 0.010 0.004 0.005 0.005 0.010 0-004 0.004 0.003 0.006 0.003 0.004 0.006 0.003 0 001 0.002 0.002 _____ 0.014 0.037 0.007 0.005 0.013 0-005 0-005 0.002 0 006 0.005 0.040 0.017 0.01 1 0.013 0.014 0.036 0.003 0.013 0-007 0.026 0.020 0.0 0.010 0 012 0-016 0.016 0.015 Remarks.Discharges 400 gallons per minute Part of town supply Village supply 9,000 gallons daily Northampton sands * Z b H L' New town supply 10 3 m Overflows at surface. New supply to town Overflows at surface Rises 17 feet above sur- face. See Table VII. Beginning of pumping Seven days later Seven days later, after continuous puniping testTABLE II.-WATERS FROM OOLITES BELOW OXFORD CLAY. (Analysis in Grains per Gallon.) No. 454 2,528 3,931 2,791 4,160 3,027 2,774 2,811 4,151 3,517 Locality. Witney Oxford City, new bor- ing, 1898 Inglesham, near Lech- lade Langford, near Bices- ter, 1898 Langford, near Bices- ter, February, 1903 Ambrosden, Oxon, ‘6 boiling well ’’ Oddington, Oxon, 1898 Merton, Oxon, new well, Marsh Gibbon 1899 Grendon Underwood Depth in Feet.270 400 290 87 87 over- flows 67 46 100 ? 20 ? Total Solids. ~- 308.0 672.0 1000*0 57.0 32.0 50.0 300.0 68.0 53.2 360.0 Chlprinc in :hlorides. 60.5 173.6 603.4 2.3 3.3 4.2 67.8 15.2 5-3 118-3 Nitrogen in Nitrat&. 0.025 0.0 0.0 0.05 0.02 0.07 0.014 0.21 0.014 0.021 Saline Ammonia. 0.063 0.101 0.462 0.042 0.023 0,007 0.089 0.008 0.020 0.042 Albu- niinoid Ammonia. 0.003 0.045 0.008 0.007 0.003 0.022 0.006 0.022 0.005 0.005 Oxygen ,hsorbed, etc., I‘hree Hours. 0-035 0.394 0.140 0.041 0-003 0.500 0.062 0.154 0,253 0.026 Total Hard- ness. Remarks. See Table VII. See Table VII. I3 El Overflows at surface.. ‘ 2 a1 k aline Overflows at surface. + F l-4 See Table VII. Water brown, peaty, m alkaline, nearly sterile. 9 See Table VII. Alkaline sulphates and carbonates Residue slightly alkaline. Water rises to surface Overflows. Peaty, alka- line, nearly sterile. See Table VII. Soft alkalinew Is TABLE III.-wATEHS FROM KELLOWAY BEDS AND OXFORD CLAY. (Analysis in Grains per GaZlon.) I Albu- / Oxy en minoid labsorbet etc., Ammonia. 1 Three Hours. Chlprine in Chlorides Total Hard- ness. Oxygen tbsorbed, etc. Three Hours. Nitrogen in Nitrates. Total Hard. ness. - - - - - - - Depth in Feet. 14 30 Spring 16 30 56 33 30 - hlbu- niinoid Ammonia. 0.007 0.018 0.032 0.010 0 GO4 0,044 0.020 0.005 0.021 0.015 Total Solids. 753.0 241.0 145.0 238.0 159.0 237.0 139.0 144 a 0 231.0 Saline Ammonia.0.005 0.07 0.127 0.015 0.057 0.035 0.074 0*001 0081 0.001 Remarks. Locality. No. 2,360 1,420 1,802 2,870 2,678 2,784 3,735 3,615 1,809 2,229 Woodham, Bucks Twyford, Bucks, trial Charndon, Bucks Clsydon, Bucks Little Chesterton, Oxon Oakley, Oxon Stratton Audley, Oxon Weston-on-Green, Oxon Newton Longville, Newton Longville, boring Oxon Oxon 90-3 23.4 7.0 5.9 2 *o 25.3 4.1 1.8 4.6 2.0 0 a064 0.133 0.221 0.030 0.024 0.222 0.177 0.038 0.046 0.099 See Table VIII. Much CaSO, 0,035 0-035 0.07 0.021 0.021 0-45 0.03 0.014 0.077 0.014 Much CsSO, See Table VII. Near edge of clay Trial boring I 44*0 I Trial boring M ?allon = 70,000 &aim. ) b --_--__-___ z TABLE IV.-WATERS FROM CORALLIAN OOLITE (UNCOVERED BEDS). (Analysis in Grains per Gallon ; 1 Depth in Feet.~- ~. Spring 16 - - - - 30 30 Spring 35 50 Spring 30 56 40 I NO. Remarks. Locality. I -~ I I 0 09 0.0 0.014 1 0.007 0.30 1 0.003 0.24 1 0.005 0.1 4 1 0.0 Hinksey, Berks Bofley, Berks Rodbourn, Berks Horton, Oxon Headington, Oxon Stanton St. John, Oxon Headington, Oxon Melksham , Wilts Near Littlemore, Oxon Shotover, Oxon Fariagdon, Berks Holton, Oxon Kingston, Berks Kennington, Berks Cowley, Oxon 0-013 0.006 0.012 0.0 0.015 0.037 0.024 0.006 0.019 0-002 0.002 0.004 0.006 0.007 0.003 0.010 0.003 0.006 1,385 I, 366 1,919 1,687 1,623 1,604 2,117 2,161 2,422 2,581 2,236 2,948 3,077 3,907 4,033 4,079 32-5 1 1.7 I 0.06 ' 0.006 32-0 63-0 29.4 31.0 27.7 35.0 30.0 47.0 41.0 31.0 0 -001 0.001 0.007 0.006 0.02 0.31 0.21 0.014 0-94 0.196 0.210 0.02 1 0.51 I 0.01 2.8 1.0 1.2 1.3 1 *8 1 2-3 j 1.4 1 1.2 1 2.0 0-004 0.020 18.8 New boring 0.005 I 0.004 0.007 0.003 1 0.006 0.014 0.001 I 0.006 0.035 0004 ' 0.005 0 014 0.011 , 0007 0.039 0.010 i 0.003 0.015 i - Hard.New well __-_ -___ Cumnor, Berks 30TABLE V.-WATERS FROM CORALLIAN OOLITE BELOW KIMMERIDGE CLAY. (Analysis in Grains per Gallon.) -~ NO. Depth in Feet. Chlorine in Chlorides, Nitrogen In Nitrates . 0.028 0.812 0.112 0.056 0.021 0-70 0.01 0.014 0-035 0.014 0.021 Albu- minoid Ammonia. Oxy en absorbei, etc., Three Hours. ~~ ~ _ _ _ 0.020 0.097 0.074 0.034 0.026 0.063 0.033 0.011 0,048 0.023 0.047 Total Solids. ___- 52.1 100.0 76.0 72.0 150.0 216-0 44.0 71-0 41.7 21.8 98.0 Saline Amnion ia. ~ - __ 0.04 0.004 0.002 0.055 0.077 0 ~005 0.070 0.004 0.005 0.017 0.061 Locality.Remarks. Burcote, Oxon W at bridge, Bucks Westcott, Bucks Near Cuddesdon, Oxon Bourton, Berks Near Swindon, Wilts Denchworth, Berks 190 16 185 265 70 180 50 190 260 230 - 5.8 6.6 1.4 3.3 43.4 7-5 4.2 1.4 2.8 1.3 26.0 2,339 2,361 2,907 2,940 3,624 3,408 3,372 3,195 4,112 4,045 4,199 0.001 0.021 0.010 0.006 0 *005 0.010 0.005 0.005 0.012 0.004 0.008 Alkaline residue Hard. CaSO, Hard. CaSO, Soft, alkaline residue See Table VII. Much CaSO, Alkaline carbonate and sulphate Hard. CaSO, Hard. See Table VII. See Table VII. See Table VII. Shrivenham, Berks Baldon, Oxon Cuddesdon, Oxon Swindon, Wilts TABLE VI.-WATERS FROM KIMMERIDGE CLAY. (Analgsis i i ~ Grains per Gallon,) .G Depth in Feet. Chlyrine in Chlorides. Nitrogen in Nitrates. Albn- n~ i iioid Ammonia. , Oxygen ~ Total absorbed, etc., ' Hard Three Hours.I ness. Total Solids. Saline Ammonia. 0,014 0 003 0.086 0.005 0.043 0.294 0.01 7 Locality. Remarks. NO. 25 12 77 12 43 22 - 1.0 10.1 8.8 1.2 1.6 16.0 17.7 0.006 0 -006 0.017 0.007 0.005 0.200 0.013 -- 0.04 0.42 0-035 0.014 0.014 0.028 0.021 0 -058 0.025 0.106 0.037 0.021 0.260 0.131 Baldon, Oxon Whitchurch, Bucks Garsington, Oxon Whitchurch, Bucks Garsington, Oxon Near Brill, Bucks Shotover, Oxon 37.0 174-0 140.0 96-0 134-0 292.0 213-0 1,267 2,833 2,959 3,682 3,190 3,814 3,869 Hard. CaSO, Hard. CaSO, Hard. CaSO MgSO,. See table VII. CaSO, cw CWw cp Witney, 1 Oxford, I Gowell, I TABLE VII. (In Grains per Gallon.) ' Lang- 1 Am- Stratton ford. brosden, Audley, 3,027. j 3,904. __~- Stra tton Audley, 3,735. __I Marsh Gibbon 4,151.5.3 6.05 14.01 2-31 0.73 ? - 8-73 10.74 27-44 - 1.53 4.13 ? -. Brill, 3,814. Swindon, 4,199. -- 26.0 3-65 3 8-63 1-40 1.01 -- - - 42.84 5.75 39-52 - 2.12 2.50 2.10 94-83 - Locality No. Bourton, 3,624. Baldor 4,112. -- 2-8 11.25 6-62 12.78 0.91 1 *oo - 4.61 5.69 2-73 I I 10.58 15 04 1.00 39.65 Cuddes don, 4,045. 1.3 2.83 6.16 7.35 1.05 1.33 - 2.13 5.03 0.06 - 1.54 11-72 1-38 21*81 - 454. 1 2,528. 4,360. 4,160. 3.3 3.3 10.78 I- -- 1.1 2.2 9.5 8.12 0.85 0.7 -- - 1.81 3.91 3.90 - 1-78 14.50 0.70 - Constituents E s t i - mated. Chlorine ... ... Sulphuric acid (SO,' Carbon dioxide (GO,: I 43.40 21.36 16-78 60.5 1 173.6 22.8 i 201.2 17*00 126.68 25-41 67-20 34.88 19.70 5.60 28.01 11 *08 104.64 - 86-16 56.64 5 *60 4.1 70.30 4.0 38.26 6-39 13.42 1.96 6.73 22-80 19.39 - I 75-41 12-87 1.96 12.32 5.5 6.1 2.1 2 *1 -- - 101.0 187.3 5.4.0.34 - - 10-7 2.1 Lime (CaO) ... Magnesia (MgO) . . . Soda (Na,O) . . . 20.4 6-0 1.19 - 286-0 323-9 18.0 - - 11-42 28.0 1-19 -- 5-1 8 1.61 - - 5.44 5.86 11.90 - 3.38 9.25 ? --- 0.98 27.16 ? - 4-31 2.14 0.70 - 1-19 0.90 74-40 0.91 71.51 37.91 34.14 - 1-88 2.12 0.91 - Silica' (Sid,) [and (Fe,O,)] . . . ... Calculated as Con- stitwnts in Com- banation. Sodium chloride . . . Sodium sulphate ... Sodium carbonate Magnesium sulphate Magnesium car- bonate ... ... Calcium sulphato . . , Calcium carbonate Silica (and Fe,O,) 7.41 11.18 29.65 - 3.95 5.89 13.70 4-49 7 -70 0.70 - Totals ... 306.84 35-83 49.99 I 36-43 52-57 139.56 - 148.47 192.13 ._TABLE VII1.-GREAT OOLITE AND OXFORD CLAY.Molecular Ratios of Chief Constituents in Grains per Gallon divided by the Molecular Weights. Woodhani, near Brill, 2,360. --- 1.272 3 a458 Locality : No : Chlorine (Cl,) . . . ... ... ... I 2.445 ' 0,0577 Sulphuric acid (SO,) . . . ... ... 1 2.515 0.8775 Carbonic acid (CO,) ... ... ... 0.280 1 0.0909 Lime (CaO) ... ... ' 0.364 1 0.6832 Magnesia (MgO j ' ... ... ... 0.150 1 0.1597 ... I 4.726 1 0,2164 I Soda* (Na,O) ... ... ... ~ Oxford, i Strattori I Audley, 2,628. 1 3,735. I Chwell, Hicester, 4,360. Locality : No : 0,0155 0.0275 0.2128 0.1450 0.0212 0.0958 ~.______ Rourton, Swindon, 3,624. 4,199. ---- Langford , Ricester, 4,160. Chlorine (Cl,) ... ... ... ... Sulphuric acid ( SOij ' . . . ... ... ... Carbonic aoid (GO,) . . . ... ... ... Magnesia (MgO) . . .... ... ... ... ... ... ... ... Lime (CaO) . . . Soda* (Na,O) ... ... ... ... ... ... 0.0465 0.0412 0.2540 0.0925 0.0402 0*2000 0 6112 0.2670 0.3813 0.0212 0.0223 1.2000 Ambrosden, Ricester, 3,027. 0.0634 0.0787 0.2973 0,0175 0.0 0.4380 TABLE VIII.-CORALLIAN AND KIMMERIDGE BEDS. Stratton Audley , 3,904. 0.0338 0.0415 0.2800 0.0770 0.0535 0-2255 Marsh Gibbon, 4,151. -- 0-0764 0.0756 0.3184 0.0413 0.0182 0.41 09 2.217 2.212 Molecular .Ratios of Chief Constitzceizts in Grains per Gallon divided by the Molecular Weights. +4 u3 0.3662 0.0456 0.4231 0.0250 0.0252 0.7847 Raldon, 4,112. 0.0394 0.1406 0.1504 0.2282 0.0227 0.0795 Cuddesdon, 4,045. - 0.0260 0.0506 0.2000 0.1674 0.0262 0- 051 5 - __ Brill, 3,814. -- 0.2394 1.5830 0,5775 1.200 0.872 0.318 9 SEA- RATER. 19.270 1.975 0.085 0.738 3.825 16.740 * Traces of potash are included.The figures in italics are calculated by difference.36 THE ANALYST. From w e b in the oolites, however, harder waters are obtained, especially from the deeper sinkings, of which a few examples are given in the same table. S E A LEVEL Taters below Ozford CEay.-The Great Oolite beds, with Forest Marble and Corn- brash, pass in this district below the Oxford Clay, dipping gradually in a south-eastTHE ANALYST. 37 or southerly direction, and when the waters which they contain are tapped by boring, the characters of the supplies are found to alter in a remarkable manner. As no downward percolation is possible through the superinoumbent clay, the waters must flow along the lines of the porous beds often for long distances, and, gathering more and more the soluble constituents, become increasingly saline in character. The waters in Table II., from Witney, Oxford City, and Inglesham, are typical examples of such salt waters, ell being probably derived from the Forest Marble beds.The amount of alkaline salts, indeed, is so great that the waters are quite useless for domestic or industrial purposes. A boring made in 1832 for a brewery at St. Clement’s, Oxford, and cwried to a depth of 420 feet, yielded a highly saline water, of which the chief constituents were found by the late Mr. W. F. Donkin to be 748 grains of common salt and 357 grains of sodium sulphate in the gallon, the total dissolved solids being 1,277 grains. (See Woodward, “Jurassic Rocks of Britain,” vol.iv., p. 514.) An interesting boring through the entire series of oolttes at Swindon to a depth of 736 feet is also described by Mr. Woodward, and an analysis of the water given. The amount of alkaline chlorides was at first 1,841 grains per gallon, with 279 grains of calcium and magnesium chlorides, the total solids being 2,131 grains per gallon. An analysis made in 1902 showed a diminution of chlorides to 1,673 grains. The bore-hole now being blocked in its lower part, the salt water cannot be obtained; but the sample inTable V. (4,199) was obtained from the upper part of the boring last year. Mr. Churchward, the engineer to the Great Western Railway, informs me that the salinity gradually increases beneath the clay. H e says: “ A year or two since 1 tested by borings the water from Swindon to Kemble (where the clay ends), and found the chlorine diminish all the way until it reached about 1.6 a mile this side of Kemble Station.” A gradual change of this character can be distinctly traced in two series of wells in the Bicester district. The Middleton water (2,392, Table I.) is an ordinary limestone water, while the waters from Gowell (4,360, Table I.), Langford (4,160, Table II,), and Ambrosden (3,027)) show a gradual transition to alkaline waters, con- taining only small amounts of calcium salts.These wells lie nearly in a straight line five miles in length. Another line of wells is from Fringford (3,076, Table I.), through Stratton Audley (3,904, Tables 11. and VII.), to Marsh Gibbon (4,151), in which the successive changes are similar, the distance being about four miles.It is probable the Grendon Underwood water (3,517) is a continuation of this series. The waters at Ambrosden and Marsh Gibbon are interesting from the fact that they contain some peaty matter in solution, which imparts to them a brownish tinge. The waters are soft and alkaline, and are in use for domestic purposes; one well, indeed, supplies a large part of the village with water conveyed by pipes to the public taps. The geological map of this district shows that the oolite beds, after passing below fhe clay, rise again to the surface, forming several patches or inliers of limestone, upon which the above-mentioned villages, with Oddington and Merton, are situated. This will be clear from the section and sketch-map.This is from the Corallian beds. See Table VII. for relative quantities of sodium salts.38 THE ANALYST. It should be remarked that saline waters from under clay normally contain free ammonia, with considerable quantities of organic matter, but only small proportions of nitrates, thus differing widely in type from ordinary limestone supplies. The presence of the peaty matter in the waters described has been difficult to explain ; but as the brown organic substance is precipitated when the waters are neutralized with acid, it clearly comes from the solvent action of the sodium carbonate upon some constituent in the oolitic beds. The recent boring at Gowell, near Bicester, affords information which may explain this peculiarity. Down to 90 feet the beds consisted of various rocky, shaly beds, with no water ; then water was reached in sandy deposits, and at 108 feet a layer of " peat " was met with in sand, from which the bulk of the water came.A specimen of this deposit proved to be a mixture of brown vegetable matter and sand, partly soluble in weak sodium carbonate, imparting to it a brownish tint. Similar peaty deposits may occur at. Ambrosden and Marsh Gibbon, and their presence would explain the origin of these brown waters. Oxford Clay.-Owing to their generally impervious character these beds do not yield water in any quantity; occasionally wells are dug, and the composition of the waters obtained is shown by some examples in Table 111. Many have been taken from trial wells sunk in attempting to provide water for public supply, but the exces- sive quantities of calcium and magnesium compounds and especially their sulphates render the waters unsuitable for domestic purposes.The presence of saline ammonia and somewhat large proportions of organic matters are worthy of note ; the nitrates are generally small in amount. Corallian Oolite.-The Corallian oolites rest on Oxford Clay, and are composed partly of calcareous grit and partly of coral rag limestone with occasional clay beds. Although much smaller in extent than the great oolite series and of no great thick- ness, they are important sources of supply for many villages in Oxfordshire and Berks, and numerous wells have been sunk in these deposits. Generally the waters obtained are rather hard, as will be seen on reference to Table IV., and the organic impurities are small; but the nitrates, as might be expected, are very variable, according to the state of the surroundings of the wells.Waters below Kimmeridge Clay.-When the Corallian beds pass in their turn below the overlying Kimmeridge Clays and can only be reached by borings, the characters of the waters found are widely different from those previously described. The increase of alkaline salts is very noticeable, and the waters are frequently soft and alkaline. The Burcote water (2,339, Table V.) is a typical example of the change, while the Bourton (3,624) and Swindon (4,199) waters may be compared with the Faringdon (2,236, Table IV.) from the same beds a short distance away. In the case of the Baldon (4,112) and Cuddesdon waters the change of type is less complete, but the proportion of alkaline salts has increased in both.Kimmeridge Clay. -Attempts are made occasionally to procure water from this clay, but with little success, as the waters are for the most part extremely hard, owing to the large amounts of calcium and magnesium salts. Some examples are described in Table VI., and the detailed analysis of the Brill water (3,814, Table VII.) shows a, remarkable excess of magnesium sulphate. It is only to be expected that the more saline waters would decrease in salinityTHE ANALYST, 39 after a time, and, indeed, this frequently happens to a greater or less degree, according to the quantity of water drawn. The Buckingham water, after fourteen days’ con- tinuous pumping, was very different in character from that first obtained from the boring : since 1901, however, it has remained fairly constant in composition.The Longford water altered considerably in five years, but the composition of the water a t Marsh Gibbon has not varied to any noticeable extent for nearly twenty years. The study of oolitic waters leads to the general conclusion that the uncovered beds of limestone yield calcareous waters of a hard character, while the deep beds, and especially the beds covered by clay, yield saline or alkaline supplies. In earlier papers (ANALYST, 1901, 1902) it has been shown that alkaline waters are similarly found in the Chalk below London Clay and in the Lower Greensand or Portland, beneath Gault Clay. Further instances may be adduced of alkaline supplies being obtained under similar conditions from beneath the Wealden Clay and also Upper Lias Clay.Thus we find in geological deposits of various ages and extending over an enormous period of time a general similazity in respect of the alkdine constituents of waters whenever the strata Eire covered by impervious deposits. Some general cause must be looked for to explain this general identity ; and the evidence clearly justifies the conclusion that the alkalies are normal constituents of the strata, from which the waters are obtained, and are not derived from any external source, which hitherto has been the general assumption. Among engineers the opinion prevails that chalk waters in the London basin derive their salt from the infiltration of sea-water, although this would not explain the alkaline sulphates and carbonates also present in quantity.If chalk under London and Essex communicates to any appreciable extent with the sea, the waters would become increasingly saline as pumping continues, but the constancy of com- position of the Trafalgar Square well, and of many others, is evidence to the con- trary. Further, the gradual fall of level of the wells shows there is no ready access for sea-water. I t must not be forgotten also that chalk water at Windsor contains very moderate quantities of alkali, while a few miles further, at Wokingham and other localities, large amounts are found. The water-levels of inland wells lend no support to the view mentioned above. In the case of the overflowing wells near Bicester the surface is 210 feet above ordnance datum, and at Swindon the water-level is 300 feet above sea-level.All the cases under discussion hang together, and my engineering friends will need to revise their opinion in respect of the alkaline chalk water under London. Among geologists the possibility of a connection between salt deposits in the Trias and the saline oolite waters is the hypothesis most in favour. The late Sir Joseph Prestwich, in his paper on the saline water from the deep well at St. Clement’s, Oxford, inclined to this view, suggesting the possible thinning out of the Lias near Oxford. But the borings at Swindon and Inglesham have since been made, and as the Lias presumably underlies the oolite in both localities, it seems hardly possible that any communication can exist with the Trias.Further, the Trias salt- beds would furnish sodium chloride, but neither the sodium sulphate nor sodium carbonate are characteristic of oolite supplies. The chemical argument appears absolutely destructive of the sea-water (or salt-40 THE ANALYST. beds) hypdhesis if the figures in Table VTII. are critically examined. The molecular ratios there calculated afford a ready means of comparing the quantities of each constituent of the oolite waters and sea-water. The chlorine in sea-water is sufficient to combine with all the alkali and part of the magnesia; the sulphuric acid is a tenth of the chlorine, and only suffices for part of the rnagneeia and a small quantity of lime. I n saline well-waters the proportion of soda is not only in excess of the chlorine, but sometimes greater than the sulphuric acid in addition, and a portion is found as carbonate.This excess of soda cannot be derived from sea-water, but must be a constituent of the rocks in which the waters are found. A suggestion has often been made that alkaline silicates, being decomposed by carbonic acid, may furnish the alkaline carbonates in some waters; but there is no evidence of any weight that such an action takes place either in the days or lime- stones under consideration. I venture to propose an entirely different hypothesis, and to suggest that the alkaline oarbonates owe their origin to the decay of organic matter originally deposited in and with the rock material, part of which still remains, and from which the products of decomposition have not been removed by the circulation of underground waters.I t is preciselyin situations where there is little or no move- ment possible that saline waters are met with. The abundance of fossil remains indicates a profusion of animal and vegetable life at the time of the formation of these deposits, and in them lignite, peat, and even animal matters, more or less fossilized, are still left in many places. The ashes of plants and animals are rich in alkaline salts, carbonates, sulphates, and phosphates, and it is reasonable to suppose that when the organic matters originally decayed, the products of decomposition not lost as gases would remain in part, at least, among the materials in which they were embedded.Further, unless washed away later by subsequent exposure of the beds and percolation of rain-water, such remains would continue even to the present time. I t seems probable that the ammonia normally present in saline waters, together with the somewhat larger quantities of organic matter, may have a common origin with the alkaline constituents. This part of the discussion must, however, be reserved for further experiment and investigation. I wish to thank Mr. A. E. Ellis for his help in the analyses of the mineral constituents of some of these waters. DISCUSSION. The CHAIRMAN (Mr. Sidney Harvey) said that in his own district the waters derived from the lower tertiary formations contained amounts of free ammonia which were relatively very large. Such waters had, indeed, occasionally been condemned a8 containing organic impurity, though the albuminoid ammonia and oxidizable organic matter were small in quantity.The figures for chlorine were generally high, and sodium carbonate was very frequently present. Mr. ALLEN said that in his experience calcium carbonate was soluble in water to the extent of about 1.3 grains per gallon, and magnesium carbonate to a, greater extent, so that the alkalinity of the residue would seem to be scarcely sufficientTHE ANALYST. 41 evidence in itself to enable one to regard it as fully demonstrated that what was present-especially when the quantity was small-w-as really sodium carbonate. Mr. W. T. BURUESS said that the change which had taken place ili the water from Langford after an interval of five years was rather curious.It did not seem to have been due to the washing out of the more impure water that might have got into the well at first, since, although the total solids had decreased, the quantity of chlorine in the later sample was greater than that in the earlier sample. A very remarkable change, too, was that which had taken place in the m e of the Bucking- ham well, in which the total solids, originally 60 grains per gallon, were a week later 68.7, but after another week had decreased to 30 grains per gallon. The water from Inglesham, again, was apparently entirely different from any of the others. From the proportion which the chlorine bore to the total solids, the latter must consist of little else but pure sodium chloride.It seemed a pity that the figures of water analyses were so often confined chiefly to those relating to the changes undergone by organic matter, for the possession of additional data, such as those which Mr. Fisher had given, and their study in relation to the geological formations in which the wells or springs were situated, would in many casefi afford valuable information that might not be otherwise obtainable. Mr. HEHNER said, while he was much inclined to accept Mr. Fisher’s suggestion that these alkaline salts, and especially the carbonates, were derived from organic remains, he could not help feeling that that theory-as Mr. Fisher had, in fact, mentioned-was beset by It was customary to look upon the nitrates in water from deep chalk wells as being obviously derived from the nitrogen of the animals that deposited the chalk.I t was no doubt easily imaginable that the ammonia which was found in such waters represented non-nitrified nitrogen, though it was often suggested the ammonia was the result of reduction of nitrates- not, however (as the old theory had it), by the action of iron pipes, but more probably by the action of micro-organisms. The chief difficulty appeared to be the fact that many strata which abounded in organically-derived substances did not yield alkaline waters. Kimmeridge Clay, for instance, was full of fossils belonging to comparatively recent periods, and yet water from the Kimmeridge Clay was never alkaline, but contained calcium sulphate. Of course, it might be said calcium sulphate pre- dominated in that formation, and whatever sodium carbonate might be formed would be precipitated as calcium carbonate, and overwhelmed and eliminated by the calcium sulphate.I t was difficult to see why, if that were so in the case oE the Kimmeridge Clay, it should be otherwise in the oolite and limestone beds. The presence of sodium salts could not well be due to sea-water in the oolitio beds of the South Midlands. On the other hand, in the South of England alkaline waters, undoubtedly from the chalk, were frequently met with when the chalk was overlapped by clay, and where the sea was only a few miles off, some, at any rate, of the salinity was due to sea-water. Mr. D. A. SUTHERLAND inquired whether the wells which Mr. Fisher referred to were iron cased, and, if so, whether the lining w a ~ continued through all the strata to the bottom ; and also whether any investigation had been made as to the presence of iodides or bromides, etc., in those waters in which the quantity of chlorides W ~ S great many difficulties.42 TEE ANALYST.high. It was interesting to note that on distilling Kimmeridge bituminous clay, mineral oil was yielded in copsiderable quantities, and the richness of that formation in nitrogenous matters was shown by the fact that in mme cmes it was capable of yielding as much as 30 pounds of sulphclte of ammonia, per ton when distilled in an ordinary shale retort. Mr. KITTO inquired whether, in advising that the peaty water from the ‘‘ boiling well” at Ambrosden might be used for drinking purposes, Mr.Fisher had considered it permissible to use the water as it came to the surface, or whether he had required the water to be pumped from below the peaty bed, when its condition would presumably be much better. Mr. SUTHERLAND said that the question of the water passing through a peaty bed had led to his inquiry as to the lining of the wells. It would be interesting to know if any examination had been made for the presence of sphagnum cr other characteristic matter. Mr. CHAPMAN thought that there could be little doubt as to the correctness of Mr. Fisher’s earlier explanation in regard to the occurrence of sodium carbonate in these waters from the chalk underlying the clay, and the explanation which he now suggested of the presence of appreciable traces of free ammonia in such waters certainly seemed probable. Free ammonia occurred, as was well known, in consider- able quantities in nearly all waters derived from any form of chalk bed underlying clay, and in London well-waters it sometimes occurred to the extent of very nearly $c grain per gallon.He (Mr. Chapman) had thought it not impossible that this formation of free ammonia might be explained by the increased activity of micro- organisms owing to the slight alkalinity of the water ; and it might be noted thti,t, as a general rule, the waters referred to by Mr. Fisher, which came from below the clay, contained less nitrates and more ammonia than those from the clay itself, which seemed to favour the denitrification theory. Of course, many of the organisms existing in water were oapable of reducing nitric acid and nitrous acid, and it seemed quite conceivable that in the case of theae waters such organisms might have been actively at work.He was iaterested in Mr. Fisher’s remark that the peaty water referred to was nearly sterile, because during the last few months he had had occasion to examine bacteriologically two or three peaty waters, and had found it extremely difficult to obtain the ordinary growths from such waters. Colonies formed on the ordinary gelatine medium, but they took from twenty-four to thirty-six hours longer to develop than usual, and were even then comparatively small and attenuated. It seemed as though some of the peaty or humus constituents exercised a paralyeing effect on the bacteria. The fact that, in the case of both the Oxford and the Kimmeridge Clays, the waters derived from the clay beds were altogether different from those derived from the underlying oolites seemed completely opposed to one of the alternative theories that had been suggested to account for the presence of sodium carbonate, free ammonia, and sodium sulphate-namely, that these were really the constituents of tertiary waters which had penetrated through the fissured chalk. From Table V.it would seem that, in the waters from below the Kimmeridge Clay, just as in those from below the London Clay, there was a fairly constant connection between the presence of alkaline carbonate and the presence of free ammonia.THE ANALYST. 43 Dr. DYER said that in reference to the organic remains present in deep deposits it might be interesting to mention that some few years previously the late Sir Henry Gilbert had made nitrogen determinations in a number of specimens of deep clay deposits taken from various places, which had been supplied to him partly through the Geological Survey, and on an average it had been found that these deep clay deposit3 contained as much aa from 0-03 to 0.04 per cent.of nitrogen aa the survival of the organic remains which must have been originally deposited with them. The quantity of nitrogen seemed remarkably constant, and in the deep clay subsoils at Rothamated as far down as 9 or 10 feet, and beyond the influence of surface vege- tation, the proportion of nitrogen was about the same-namely, 0.04 per cent. Taking into account, therefore, the large surface of clay with which a water travelling underground must come into contact, there must be opportunities for its taking up nitrogen in some form or other.Mr. FISHER, in reply, said that he had not been able to make any detailed examination of the peaty material from the Ambrosden well, as the quantity at his disposal was only very small, but he hoped to be able to obtain some more of it, With regard to the important point raised by Mr. Hehner as to the absence of alkaline carbonate in waters from the clay itself, even when the latter-as was the case in the Kimmeridge beds-abounded in organic remaina, he expected to find, when he should be able to examine that part of the subject more minutely, that these clays did contain carbonates of the alkalies; but it must be borne in mind that the water in any clay bed was necessarily in contact with a comparatively limited quantity of material, the reason why the waters from porous beds showed alkaline carbonates, while those from clay beds did not, being that the water could move in the porous beds along the lines of stratification or through the material itself, while the clay was so impervious that the water could not travel any great distance through it.He had noticed sometimes, in water from wells in the clay, that at first the quantities of dissolved solids were so large as to render ihe water almost unusable, but that if pumping were continued for some time water was obtained containing a good deal less dissolved matter. With regard to the sodium carbonate question, he thought there could be no doubt that sodium carbonate did actually exist in the chalk, and its much greater solubility would account for its preponderance over calcium and mag- neEium carbonates in the water.It was certainly the case that, on evaporating to dryness a water containing magnesium carbonate, some of this was decomposed, leaving a feebly alkaline residue of magnesia and a basic carbonate, but in really alkaline waters the alkalinity of the residue was so marked that there could be no question as to its origin. He could only explain the change in the character of the Langford water by the supposition that during the interval of five years-probably owing to the larger flow of water-there was less soluble matter in the beds than there used to be.He had, however, had occasion qnite recently to examine a further sample of it, which showed the water to be substantially the same in character as the last sample referred to in Table I. The Swindon well, in particular, he believed to have been very carefully made, and it was probably lined, though he did not actually know this to be the case. The last analysis in Table V. The Buckingham water was certainly a remarkable one. In some cases the wells were lined, in others not.44 THE ANALYST. represented the water at present obtainable from the Swindon well. He had not looked for either iodine or bromine in any of the waters, having been obliged some- what to limit the scope of the investigation. The question of the peaty water had been puzzling him for several years, his attention having been first drawn to it by Sir Henry Acland. On investigating the matter at the time he had been thoroughly convinced that there was no infiltration from the outside, He had had one of the we[ls emptied to the bottom and the bore-hole plugged, and it was found that some of the water taken as it came out of the bore-hole was of exaotly the same character &S that which overflowed from the top. Even, however, if the walls of the well had been defective, it would be very difficult for any impurity to make its way in against the pressure from the inside. This water gave bacteriological results similar to those described by Mr. Chapman. Practically no organisms developed for three days, and after that the colonies were very few in number and doubtful in character. With regard to the ammonia, it seemed to be of little moment whether this had once been in the form of nitrates, or whether it had always been ammonia. The main point wag that, practically speaking, all the products of decomposition of organic matter were present. Of course, the chloride of sodium might be a residuum of sea-water if no washing out had taken pIace, but he thought that that was only part of the story. The presence of the sodium carbonate and also of phosphates were the points that needed explanation. He had been much interested in Dr. Dyer’s mention of Sir Henry Gilbert’s work, and hoped himself to have some opportunity of trying to add a little to existing knowledge in regard to the materials obtained from clays.

ISSN:0003-2654    

DOI:10.1039/AN9042900029

出版商:RSC    

年代:1904

数据来源: RSC

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44 THE ANALYST. THE MICROSCOPIC EXAMINATION O F AXERZCAN COTTONSEED CAKE. BY A. L. WINTON. IN a recent issue of this journal, Dr. Voelcker has described a number of methods, partly chemical, partly physical, and partly mechanical, for discriminating between Egyptian and Bombay cottonseed cake. This paper was of special interest to me, its I have attempted to solve a similar problem-namely, the discrimination of upland from Sea Island cottonseed cake as produced in the Southern States of my'own country. Although my work has been largely microscopic, the conclusions reached bear a close relation to those of Dr. Voelcker. The upland or short-staple cotton growing in the United States is commonly c1a.ssed as Gossypium herbaceurn, although quite possibly some of the varieties were obtained by crossing with other species.It yields the great bulk of the American cotton fibre. After ginning, the seed is still clothed, like Bombay seed, with a dense mat of ground-fibre, which can be removed only with great difficulty. This fibre, however, is of no serious detriment to the cake, plrovided, as has been almost universally the custom, the seed is decorticated before expressing the oil. In this connection it may be interesting to note that the cotton hulls thusTHE ANALYST. 45 separated were long used as fuel under the boilers of the oil mills, and the ashes regarded as waste. Almost twenty years ago, however, the Connecticut Agricultural Experiment Station pointed out that these ashes contained something like 25 per cent. of potash (&O), largely in the form of carbonate, and that they were admirably adapted for tobacco fertilizers.A lively traffic in these ashes at prices ranging from 25 to 50 dollam per ton was at once created, and continued until recently, when the recognitioq of the value of cotton hulls for feeding led to the abandonment of the former wasteful practice. Upland cottonseed cake has been placed on the home market in the form of cottonseed meal, a rich yellow product of high value, both as a cattle food and fertilizer. I t has usually been guaranteed to contain 7 per cent. of nitrogen (equiva- lent to 43.75 per cent. of protein), and often has contained 7.50 or even 8 per cent. Of late, however, meal containing a large amount of hulls and much less nitrogen (as little as 4 per cent.), has appeared on the market, and in some instances has been fraudulently substituted for prime meal.While it is a well-recognised fact that cotton hulls can be fed to advantage in conjunction with the meal, and that undecorticated meal is preferred by English feeders, it must be admitted that meal containing or adulterated with a considerable amount of hulls should command a lower price than the concentrated product. This is especially true when, as is often the case, the meal is purchased solely as a source of nitrogen for fertilizing purposes. Frequently manufacturers and jobbers in these inferior and adulterated products have chimed that the product was Sea Island meal, and the hulls were normal constituents. Sea, Island cotton, G. barbadense, is grown on the coast of South Carolina and Georgia, and yields the highly-prized long-staple cotton. The seed is dead black, without ground-fibre, and for mechanical reasons is not decorticated.It is stated that a large share of this Sea Island cake finds a, market in England. From Dr. Voelcker's description, I infer that the Egyptian cake mentioned by him was from this or a related species. Although Sea Island cake, because of the absence of ground-fibre, is superior to undecorticated upland cake, it is obviously inferior to prime decorticated cake from the latter variety. I t was partly with the hope of finding some means of refuting the claims that low grade meals were Sea Island products that I made a comparative study of the microscopic structure of the two seeds.The most striking elements are the thick-walled epidermal cells with dark con- tents, the colourless cells, the palisade cells, each with a globular cavity one-third the distance from the outer to the inner end, and the fringed cells of the perisperm. The outer brown layers and the inner testa also, with brown contents, are not so clearly defined, but of great importance in diagnosis. In the Sea, Island I found that the outer epidermis was not only free from hairs, but the epidermal cells proper were narrower and higher than in the upland seed; also that the colourless cells of the third layer were thicker, and more often in two rows or divided by tangential walls, and that the cells of both the outer brown layer and the inner testa were thicker, more strongly developed (or, rather, less completely My first work was with single samples of both varieties of seed.46 THE ANALYST.obliterated), and contained mwe abundant brown contents. Not being content to accept these results as final, I procured from a seedsman and others in the South samples of eight leading varieties of upland cotton and three of Sea Island. On examining these, it appeared that all of the distinctions named could not be depended on in diagnosis; but those based on the presence of ground-wool in upland and its absence in the Sea Island varieties, and on the difference in the thickness and amount of coloured substa,nce in the outer brown layer and the inner testa, are of considerable value. These are much the same distinctions as Dr. Voelcker has brought to notice in his paper.As for the ground-fibre, while all the seeds in upland cotton are clothed with a, dense wool after passing through the gin and linter, some are largely deprived of this coat in grinding, so that the presence or absence of hairs on the ground husk is not an absolutely sure criterion as to the origin of the seeds. On the other hand, all Sea Island seeds are not entirely denuded of fibres, and the meal made from them usually contains a little fibre, although never so much as an' upland meal ground with the hulls. The means of distinction based on the amount of brown colouring matter in the two layers appeared to be most valuable, but was not found infallible. While in all the Sea Island cotton-seeds I have examined both brown layers contained a pro- nounced amount of brown matter, some upland varieties exhibit the same charac- teristics, although in a lesser degree.As a rule, however, the distinction was well msrked, and should prove of no little value when, as in the cake on the English market, the hulls are in large fragments. But the meal on the American market-noti only the prime article, but especially that containing large amount of hulls-is sold in a finely-ground condition. The manufacturers appear to have learned that by fine grinding they secure a brighter yellow appearance, not only because of the fine division of the particles-although this unquestionably plays an important part-but because the light-coloured sides of the palisade cells are brought into view, whereas in the commly-ground hulls only the brown outer and inner coats are exposed.This fine pulverization both deceives the purchaser and renders the microscopic test described by Dr. Voelcker valueless ; it also embarrasses the microscopist, as he is unable to find fragments large enough for cutting sections. The chemical test found efficient by Dr. Voelcker does not aid us, as the hulls cannot be separated from the meal. Furthermore, I find that our Sea Island cotton hulls give a more distinct colour by this test than the upland. It thus appears that in many cases the problem in question is more difficult than that encountered by the English analyst, and cannot be solved with the mme degree of certainty. So far as concerns the mere detection of excessive amounts of hulls or starchy adulterante, mimoscopic examination, especially if coupled with determinations of nitrogen and fibre, is all that could be desired. The following results are interesting as showing the extremes in chemical composition :THE ANALYST. 47 Prime Cotton- seed Per Cent. 8.98 6.18 48.19 5.54 22.46 8.65 ------ 100.00 / Water . . . ... ... . . I Ash ... ... Fibre ... ... ... ... Fat ... ... ... ... Protein (N-x 6.25). . ... ... Nitrogen-free extract . . . . . I Cottm-seed Meal Adulterated with Cotton Hulls. Per Cent. 10-48 4-70 25-50 18-95 34.27 6.10 100*00 Total Cotton Hulls, it Average of Four Analyses. Per Cent. 10.41 2.59 4.04 44-42 36.52 2.02 100*00 CONNECTICUT AGRICULTURAL EXPERIMENT STATIOK, NEW HAVEN, CONK., U.S.A.

ISSN:0003-2654    

DOI:10.1039/AN9042900044

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年代:1904

数据来源: RSC

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THE ANALYST. 47 ABSTRACTS OF PAPERS PUBLISHED IN OTHER JOURNALS. FOODS AND DRUGS ANALYSIS. Detection of Methyl Alcohol in Ethyl Alcohol. L. D. Haigh. (Pharm. Review, 1903, xxi., 404; through Chenz. Zeit. Rep., 1903, 300.)-This is a modifica- tion of a process recently described by Prescott (Pharm. Arch., 1903, iv., 86). One C.C. of the sample is diluted with such a quantity of water that the liquid contains 10 per cent. by volume of alcohol. I t i g poured into a, test-tube which is supported in a vessel containing cold water. A spiral of copper wire, about 3 centimetres long, is heated to redness, dipped into the spirit, and held there for a moment, this opera- tion being repeated five or six times till most of the alcohol has been oxidized. The liquid is next filtered into another tube, and gently boiled until the odour of acetalde- hyde has entirely or almost disappeared.It is then cooled and transferred to a porcelain basin, where it is mixed with 5 drops of an alkaline solution of phloro- glucinol. If methyl alcohol was present in the spirit, a, bright red colour is immediately produced, which persists for two or three minutes; but if the ethyl alcohol were free from methyl alcohol, only a faint reddish tint may appear, which will vanish rapidly. F. H. L. A Reaction of Cryogenin. G. Eetein. (Journ. Pharm. Chim., 1903, xviii., 593, 594.)--In addition to the colour reactions of oryogenin, or metabenzylamido- ssmiarbazide, described by BarraJ, the author describes a characteristic reaction * Jenkins and Winton : Compilation of Analyses of American Feeding-Stuffs, U.S.Dept. Api- culture Office of Experiment Stations, Bulletin XI., Washington, 1892, 146.48 THE ANALYST. which it gives with formaldehyde. On adding 1 C.C. of formalin (40 per cent.) to a solution of 1 gramme of cryogenin in the smallest possible quantity of alcohol, diluting the liquid with water, and shaking it with 2 or 3 drops of hydrochloric acid, the cryogenin is quantitatively precipitated in the form of a white powder. The compound is only very slightly soluble in alcohol, ether, and chloroform, and is insoluble in water. It begins to melt about 205" C., becoming coloured. The reaction can be used for the quantitative determination of cryogenin in aqueous solutions. For its determination in urine, however, the method has not given satisfactory results ; and as a qualitative test the reaction is regarded as less sensitive than the reactions with copper sulphate (green colour) and Fehling's solution (reduction on boiling).C. A. M. Estimation of Resin in Jalap. Q. Weigel. (Pharnz. ZentraZh., 1903, xliv., 791; through Chem. Zeit. Rep., 1903, 302.)-Five grammes of jalap in moderately fine powder are mixed with about an equal weight of weshed sand, and boiled for an hour on the water-bath with 50 or 60 C.C. of 96 per cent. alcohol in a flask fitted with an inverted condenser. The resin solution is filtered into a tared 150 C.C. beaker, the residue being washed with hot 96 per cent. spirit till the washings are practically colourless (about 30 C.C. being required.) The alcohol is then expelled on tbe water- bath, and the resin is stirred wifh a glass rod under hot water to wash it. When the water has become cold and the resin has settled, the liquid is poured off, and the solid matter dried and weighed. F. H. L.

ISSN:0003-2654    

DOI:10.1039/AN9042900047

出版商:RSC    

年代:1904

数据来源: RSC

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48 THE ANALYST. TOXICOLOGICAL ANALYSIS. Notes on the Detection of Phosphorus. A. Fischer. (Arch. PhysioL, 1903, xcvii., 578 ; through Chem. Zeit. Bep., l903,298.)-The author has examined various methods of detecting phosphorus by the flame test in presence of substances that usually interfere. When volatile substances of this kind are present, if the amount of phosphorus is not too small the Hilger-Nattermann modification of the Mitscher- lich test succeeds; but should this fail, the Dussard-Blondlot distillate may be submitted to the same modified Mitscherlich process. If this does not give the green flame, the gas should be led into EL solution of silver nitrate or copper sulphate, and, after the precipitate has baen collected, it should be tested once again. The filtrate should be oxidized, and the phosphorus in it estimated.When non-volatile inhibitory substances are present, the residue of the distillation, or preferably the original material, should be examined as above by the Dussard-Blondlot method. The author does not consider that '' turpentine-phosphorous acid " is a mixture of phosphorus with resinified oil of turpentine; the proportion of phosphorus in it varies because it is a mixture of several different acids, as Busch has already stated. I n forensic work, phosphorus should always be sought in the brain and spinal cord ; in cases of poisoning, there is no need to look for it in the urine or the muscular tissue. The author k unable to corroborate Stick's statement that & gas containingTHE ANALYST. 49 phosphorus can be obtained from putrid potatoes, or from fresh potatoes by the action of nascent hydrogen.Similarly, he has been unable to obtain a phosphorus-con- taining gas from putrescent brain matter. F. H. L. Phenolphthalin as a Test for Blood. Utz. (Ckem. Zeit., 1903, xxvii., 1151.)- Phenolphthalin, the colourless reduction product obtained by acting upon phenol- phthalein with zinc in alkaline solution, has already been suggested as a reagent for the detection of oxydases by Kastle and Shedd, and as a test for pus and blood by Meyer. Phenolphthalin can be very easily and quickly prepared; it is readily soluble in water, its solution remains perfectly colourless when made alkaline, and the liquid keeps excellently. As a reagent for blood, its aqueous solution is rendered alkaline by means of sodium carbonate ; 0.5 to 1 C.C.of it is mixed with a little of the suspected substance, allowed to stand for few minutes, then shaken, and finally treated with 2 or 3 drops of 0.1 per cent. hydrogen peroxide. Presence of blood is shown by a pink 'colour developing almost instantaneously. Utz has tested the reaction upon blood-stains on fabrics, wood, and iron, some of them being fresh, others more than eighteen months old. The test exceeds in delicacy those proposed by Van Deen and Rossel : 2 square millimetros of a fabric will give it. If the stain is on iron, the powder may be scraped off and digested for 8ome time with the reagent; it is then filtered quickly, and the hydrogen peroxide is added t o the filtrate, Bust is thus separahed, and does not interfere. Artificial wmming of the liquids should be avoided in all cases, and care must be taken that the alkalinity of the solution is not destroyed. Insolated oil of turpentine may be employed instead of the hydrogen peroxide. Like guaiacum tincture, phenolphthalin naturally gives a similar reaction with pus and all animal secretions which contain leucocytes. It may be possible to devise some means of distinguishing between blood itself and such other substances in a manner resembling that which Vitali (ANALYST, 1902, xxvii., 329) has described for use with guaiacum. Experiments in this direction are in progress. F. H. L.

ISSN:0003-2654    

DOI:10.1039/AN9042900048

出版商:RSC    

年代:1904

数据来源: RSC

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THE ANALYST. 49 ORGANIC ANALYSIS. Para-nitrophenylhydrazine as a Microchemical Reagent for Acrolein and Acetone. H. Behrens. (Chem. Zezt., 1903, xxvii., 1105.)-If an aqueous solution of the hydrochloride of p-nitrophenylhydrazine is mixed with a little liquid containing acrolein, star-shaped crystalline aggregates of orange-coloured needles are formed, which, when viewed under the microscope, will be found to have a length of 150 ,u. The product should not be recrystallized before examination. In order to employ the reaction as a test for glycerin, the liquid should be evaporated with some potas- sium bisulphate and a tuft of long-fibre asbestos. By working in this way, the last portions of the water (containing some acrolein) can be distilled off without fear of frothing. The analogous reaction with aoetone is of some value for the identification uf50 THE ANALYST.denaturing materials which may contain that substance. The hydrszone obtained from acetone forms lemon-yellow crystals up to 500 ,u long, the crystals having the shape of rods with oblique ends. Acetaldehyde yields crystals of identical size and colour, but they form needles with pointed ends. This difference in appearance is so conspicuous that a denaturing agent containing acetone may be detected even in a spirit contaminated with the aldehydes of the first runnings. F. H. L. Notes on Poppy Oil. Utz. (Chew. Zed., 1903, xxvii., 1176.)-It has been recently shown by several writers (cj. ANALYST, 1902, xxvii., 363) that arachis oil is frequently contaminated with oil of sesame.Investigation of the poppy oil, which is sold for dietetic purposes as '' salad oil " proves that the same contamination occurs with this oil. Utz has examined fifteen samples of poppy oil, obtained through the German retail trade, and has observed that all give the Soltsien and the Baudoin tests for sesame. Owing to the fact that the price of sesame is higher than that of poppy (both the seeds and 88 oils), this is not a, case of intentional adulteration ; but inquiries put to manufacturers, and investigations of their methods, indicate that it is due to a want of care in the factories. Poppy and sesame seeds are usually expressed in the same plant, and the consequence is that the one oil may become oontsminated with the other. In order to ascertain what the " constants " of absolutely genuine poppy oil should be, Utz has extracted the oil by means of petroleum ether from a sample of Indian seed, light gray in colour, which contained 53.93 per cent.of oil, from a pale brown Levant (Smyrna) sample which contained 47.77 per cent., and from an undescribed sample of German seed. The iodine values of the oils, as determined by the Hubl-Waller method, were 153.48, 157.52, and 156.94 respectively. Utz's com- mercial specimens all gave figures ranging between 132 and 140-values that agree with those quoted in the books. One sample that probably contained less than 5 per cent. of sesame gave an iodine value of 151.65, another, which only showed faint indications with the Soltsien and Baudoin tests, gave 150.63.Pure poppy oil is optically inactive, as Bishop has already said ; the dextro-rotatory power of common samples is a sign of the sesame oil they contain. At 15" C. the refractive index of genuine Indian poppy oil is 1.4772, and its reading in the butter refractometer is 78.1. The corresponding figures for both Smyrna and German oils are 1.4774 and 78.4. Commercial specimens give 1.4764 and 76.7. According to Behrens, when 10 grammes of poppy oil are mixed with 10 grammes of a mixture of equal parts of nitric and sulphuric acids, a brick-red colour is produced, sesame giving a grass-green. This is not correct, for both oils, as well as several other vegetable products, yield a rapid play of colours which finally become brick-red, F. H. L. The Composition and Analysis of Linseed Oil Fatty Adds. W.Fahrion. (Zeit. mgew. Chem., 1903, xvi., 1193-1201.)-A method of separating solid and liquid fatty acids, devised by the author (Chem. Zeit., 1893, 522), was based on the oxida- tion of the unsaturated acids by means of d k a h e permanganate and the supposedTHE ANALYST. Salt. - Lithium stearate (290-38 grammes) . . . Lithium palmitate (262.38 grammes) 51 Water. I 18" C. ' 25" C. 2903.5 %32~.~ 2388-0 insolubiIity of the oxidation products in petroleum spirit. Further experiments have shown that the aolid fatty acids are also oxidized with the formation of insoluble derivatives, whilst, on the other hand, the unsaturated fatty acids yield about 2 per cent. of products soluble in petroleum spirit. These two sources of error nearly compensate one another, and the method applied to the fatty acids of linseed oil yielded (1) 8.7 per cent. and (2) 9.7 per cent.of solid fatty acids, a result in approxi- mate agreement with the results calculated from other factors. The author concludes from his experiments that in Hazura's method a large proportion of oleic acid escapes oxidation, but that the linolic, linolenic, and isolinolenic acids are almost quantita- tively attacked by the permanganate. He confirms the conclusion of Hehner and Mitchell (ANALYST, xxiii., 312), that the yield of linolenic hexabromide found by Hazura (40 per cent.) was too high, and that the precipitate contained tetrabromide, but criticises their method on the ground that the hexabromide is soluble in ether.* The melting-point of the author's hexabromide was 177" C., and he attributes the higher figure (180" to 181° C.) found by Hehner and Mitchell to too rapid heating.From these experiments and calculations drawn from tho results of other well-known methods, he concludes that the specimen of linseed oil under examination had the following approximate composition : Unsaponifiable matter, 0.8 ; palmitic and myristic acids, 8.0; oleic acid, 17.5 ; linolic acid, 26.0 ; linolenic acid, 10.0 ; isolino- lenic acid, 33-5; and glycerin radicle (C,H,), 4-2 per cent. C. A. M. New Methods of Separating Fatty Acids. A. Partheil and F. Ferie. (Archiv der Pharrn., 1903, ccxli., 545-570.)- It is shown that in Farnsteiner's method of separating solid and liquid fatty acids by treatment of their lead salts with benzene (ANALYST, xxiii., 285) part of the oleic acid i s precipitated in the form of a double stearate and oleate of lead.To obviate this, experiments were made with different monovalent metals, of which lithium was found to be the most suitable, whilst rubidium acetate only effected a partial precipitation of stearic and palmitic acids from an alcoholic solution. The solubility of the different lithium salts in water and alcohol is shown in the following table, which gives the number of litres required to dissolve the different molecular weights in grammes : Alcohol. Specific Gravity 0.797. 18" C. 708.3 329-5 127.4 49-3 31-74 25" c. 545.6 274.5 110.5 46.62 I 28.57 The method eventually adopted was to dissolve 0.25 gramme of the fatty acid in 50 C.C.of absolute alcohol, to neutralize the solution with alcoholic potassium * NOTE BY AnsTRACTOR.-specia~ stress was laid on this point by Hehner and Mitchell, and a means of obviating the error devised.52 THE ANALYST. hydroxide, and after dilution with 50 O.C. of water to add an excess of a, 10 per cent. alcoholic solution of lithium acetate. The precipitate was collected on a weighed filter, washed with 50 per cent. alcohol, dried, and weighed. I n this way the following results were obtained with pure fatty acids : Found. Gramme. Gramme. Lithium stearate . . . ... 0-2552 0.2495 Lithium palmitate . . . ... 0.2558 0.2525 Lithium myristate . . . ... 0.2565 0.2347 No trace of precipitate was given by the lithium laurste or oleate. The author therefore concludes that stearic and palmitic acids are quantitatively precipitated and myristic acid nearly so in this method, For the separation of the lauric acid and residual myristic acid in the solution, Farnsteiner's method (Zoc.cit.) can be employed, for the author has proved that these acids, unlike st-earic and palmitic acids, are precipitated f-rom a benzene solution as lead salts quite free from lead oleate. I n calculating the composition of the solid fatty acids separated by these methods, they were converted into barium salts and their molecular equivalent determined (cf. ANALYST, xxi., 318). The fatty acids recovered from the benzene solution of the lead s d t s were dissolved in alcohol, and the solution neutralized and treated with a 10 per cent. alcoholic solution of barium acetate.The barium salts were dried and extracted with ether containing some water, which was found to dissolve the barium salts of the more unsaturated fatty acids. The following results, agreeing well in duplicate determinations, were obtained by these combined methods with the mixed fatty acids of different fats : Calculated. Fat. Butter, A _.. ... ,, B ... . . I Margarine . . . ... American lard (iodine . . . Human fat, A ... ? ? €3 ... value = 65.8) Stearic Acid. Per Cent. 6-54 10.33 19.75 8.16 12-30 12.46 Palmitic Acid. Per Cent. 17.9 14-23 6.22 4.36 29.25 27.12 Myristic Acid. Per Cent. 10.65 12.25 13.72 14.03 None found. ?, Lauric Acid. Per Cent. 17.08 14.44 6.83 13.08 None found. ? 9 Unaatur- $ted Acids Per Cent. 30.08 33.03 46.91 53.75 49.07 52.93 Highly Un- saturated Acids in Unsaturated Acids.Per Cent. 5.40 4-15 20.3 10.03 - - Seven specimens of human fat of different origin gave the following resuIts : Iodine value, 57-21 to 66.30 ; Reichert-Meissl value, 1.38 to 2-19 ; saponification value, 194.2 to 198.1; and Hehner value, 93.92 to 96.0 (cf. ANALYST, xxi., 171). C. A. M.THE ANALYST, 53 Pheephomolybdic Acid as a Reagent for the Identification of Vegetable Oils. F. Seiler and A. Verda. (Chem. Zeit., 1903, xxvii., ll2l.)-The authors hold that the Welmann reaction is not capable of distinguishing vegetable fats with certainty from oils of animal or mineral origin. I t does not seem that alkaloids or glucosides in the oils are the sources of the colours which vegetable materials give ; indeed, as Welmann himself has admitted, the quantity of alkaloidal matter in such vegetable oils is so small that other reagents (which are not lacking in delicacy) fail to show it.Amides of the aliphatic and aromatic series (e.g., anilides, toluides, and naphtha- lides) give no precipitates with phosphomolybdic acid. Derivatives in which an acid radicle has entered the NH, group (urea, asparagine, etc.) give neither colour nor pre- cipitate. Amines yield precipitates and a dyestuff which varies in colour from blue to green; on adding ammonia, the precipitate generally dissolves, and the colour changes to a pure blue. F. H. L. Determination of Caoutchouc in Rubber Goods. C. 0. Weber. (Ber., 1903, xxxvi., 3103 ; through Chem. Zeit. Rep., 1903, 3OO.)-For the purpose of estimating the amount of true rubber in rubber articles, the author prepares the addition com- pound of caoutchouc with nitrogen dioxide, a body having the empirical formula C,,H,,N,O,, and containing 59.65 per cent.of its organic constituent. A weighed quantity of the sample is dissolved in benzene. Nitrogen dioxide is prepared by heating lead nitrate, about 20 grammes being needed for each analysis. The gas is passed through a drying cylinder charged with glacial phosphoric acid, and led into the solution until its colour becomes red-brown. The product is allowed to rest for an hour, and the benzene is run off through a filter, any solid matter being returned to the flask, which is then laid on its side, and dried at a temperature of 50" C. The dry residue is dissolved in acetone, and after a short time the gray solid matter (consisting of the mineral matters and albuminous constituents of the sample) which separates out of the deep yellow solution is collected on a tared filter, washed with warm acetone, dried, and weighed.The filtrate and washings are poured into eight times their volume of water, when the pure caoutchouc derivative is precipi- tated as a somewhat flocculent yellow substance. This is brought on to a tared paper, washed with lukewarm water, dried at a temperature not exceeding 90" C., and weighed. I t may be considered to contain 60 per cent. of caoutchouc. In the original article Weber gives a method for the examination of vulcanized rubber, and for the estimation of the various substancas it contains.F. H. L. Estimation of Nitrogen in Creatine by the Kjeldahl Process. C. Beger, G. Fingerling, and A. Morgan. (Zeits. Physiol. Chem., 1903, xxxix., 329 and 467; through Chem. Zeit. Rep., 1903, 282,)-Kutscher and Steudel have stated that the nitrogen in creatine, creatinine, uric acid, lysin, and histidin cannot be estimated by the Kjeldahl process. This, however, is quite incorrect so far as creatine is concerned, and the authors of this paper therefore assume it to be equally incorrect54 THE ANALYST. in the case of the other substances mentioned, since, when employing the method prescribed by the Verband der landwirtschaftlichen Versuchsstationen, they alwayB obtain perfectly accurate results. Malfatti (loc. cit., 282) agrees with Beger, Fingerling, and Morgan, more espe- cially in the case of the compound of creatine with zinc chloride.He heats the substance with sulphuric acid, but without copper sulphate or mercury, till he obtains a brown liquid that boils sm9othly. He then cools it, adds a sufficient quantity of potassium permanganate in solution, and heats again till the water is driven off and the residue is colourless. For all purposes Malfatti prefers to use the permanganate as a solution rather than as a solid, even when mercury or copper sulphate is also employed. F. H. L. The Behaviour of Methyl Violet and Tropceolin with Certain Acids. Schumacher-Kopp. (Chem. Zeit., 1903, xxvii., 1176.)-It is usually stated in text- books that methyl violet changes to a green or blue in presence of mineral.acids.This is true for hydrochloric, sulphuric, nitric, and phosphoric acids, but not for boric acid, which produces no effect. The colour of methyl violet is changed to blusgreen by oxalic, tartaric, and lactic acids, to blue by citric acid, while acetic acid is perfectly inert. The colour of tropEolin is altered to red-violet by hydrochloric, sulphuric, nitric, and phosphoric acids ; like methyl violet, it is not affected by boric acid. Oxalic and tartaric acids turn it red-violet, citric acid orange, lactic acid rose colour, and acetic acid cherry red. F. H. L. A New Indicator obtained from Meta-toluidine. J. Troger and W. Hille. (J. Prakt. Chem., 1903, lxviii., 297 ; through Chem. Zed. Rep., 1903, 282.)-Meta- toluidine is dissolved in sulphuric or hydrochloric acid, the solution is diazotized, thoroughly cooled, and either treated with a current of sulphur di-oxide or mixed with an aqueous solution thereof. The red product is purified by boiling it with water, after which it is treated with 8 warm, strong, aqueous solution of potassium acetate, and the warming is continued till a dark yellow potassium compound is obtained. This is converted into the corresponding sulphonic acid, which crystallizes in ruby red prismatic needles having the formula HS0,.C7H,.N:N.C7H,(NH,),. The alkali salts of this acid form indicators which in colour and general properties resemble helianthin, but they are very much more sensitive. F. H. L.

ISSN:0003-2654    

DOI:10.1039/AN9042900049

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年代:1904

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54 THE ANALYST. INORGANIC ANALYSIS. Behaviour of Cacodylic Acid in the Marsh Apparatus. D. Vitali. (Boll. c7im. farm., 1903, xlii., 641; through Chem. Zeit. Rep., 1903, 300.)--Referring to his previous work in the same direction, Vitali again finds that cacodylic acid is not reduced in the Marsh apparatus if some platinic chloride has been added to assist in the evolution of the hydrogen. I€, however, the platinum is omitted, black flakesTHE ANALYST. of arsenic and the characteristic mirror are both produced. Presumably a com- pound between the cacodylic acid and the platinum salt is formed which is not decomposed in the conditions obtaining within the flask. F. H. L. Action of Saline Solutions upon Metallic Iron. P. N. Raikow and 0. Goworuchin-Georgiew. (Chem. Zeit., 1903, xxvii., 1192.)--All ammonium compounds are decomposed by iron at ordinary temperatures, a ferrous salt being produced, and ammonia liberated.At the boiling-point the action is much more rapid. No iron compound soluble in water is produced when the powdered metal is boiled with a nitrite, chlorate, bromate, iodate, or chromate; nor when the acid radicle of the salt forms a compound with iron which is not soluble in water. No iron compound is formed when the metal is boiled with any normal salt of the alkali or alkaline earth metals; nor with any of their hydrogen (acid) salts which have a distinctly alkaline* reaction. A soluble ferrous compound is produced when the metal is boiled with a normal salt of a heavy metal (Zn, Cd, Ag, Cu, etc.), and also when it is boiled with such hydrogen (acid) salts as exhibit an acid? reaction.Inasmuch as 0.01 milligramme of ferrous chloride can be detected by means of potassium ferricyanide, very minute traces of a compound of a heavy metal are easily recognised in the nominally pure salts of the alkalies or alkaline earths which do not act upon iron powder ; but it is necessary to observe that tihe presence of a nitrite, chlorste, or chromate may impede or prevent the success of the test. On a large scale, the rules laid down are worth considering in relation to the corrosion of steam boilers-that portion of the corrosion which is due to (‘ auto- oxidation ” being set aside. I t will be seen that the normal and alkaline salts of the “light ” metals should not attack the plates; while their acid salts, and all the soluble compounds of the c L heavy ” metals (among which Mg stands), should be detri- mental.This agrees with Ost’s work, except that he has found potassium chloride, potassium sulphate, and calcium chloride (though not the sodium salts) to be injurious. It is probable that the salts Ost examined were contaminated with compounds of the heavy metals, which gave them th4 solvent power he noticed. F. H. L. The Separation of Barium, Strontium, and Calcium. L. Robin. (Ann. de Chim. anal., 1903, viii., 445-447.)-The solution containing these metals in the form of chlorides or nitrates is rendered slightly alkaline with ammonia, and then treated with about 2 per cent. of ammonium chloride (free from sulphate), followed by acetic acid in slight excess. It is next heated to the boiling-point, treated with a consider- able excesg of potassium bichromate and cooled, and the barium chromate collected on a weighed filter, washed successively with a 0.5 per cent.solution of ammonium acetate (rendered alkaline with ammonia), and with dilute alcohol (95 per cent. alcohol, 10 parts; water, 90 parts), dried for two hours at 100” to 110” C., and weighed. * For example, K,HP04. t KHSO, NaHSO,, KH,PO,, NaH,PO,.56 THE ANALYST. The filtrate is made alkaline with ammonia, boiled, treated with 3 to 4 per cent. of pure crystalline ammonium sulphate, and kept at 100" C. for fifteen minutes, the evaporated ammonia being replaced from time to time. After cooling, the strontium sulphate is collected, washed with hot ammoniacal water containing 0.5 to 1 per cent.of ammonium sulphate, and with 10 per cent. alcohol, dried, ignited, and weighed. The filtrate is heated to about 80" C. and the calcium precipitated as calcium oxalate. A test series of determinations are given to show that the method yields very accurate results in a very short time. C. A. M. Solubility of Magnesium Ammonium Phosphate in Ammonium Citrate Solu- tion. A. Bolis. (Chem. Zeit., 1903, xxvii., 1151.)-By allowing some specially prepared MgNH,PO;6H20 to remain in contact for twenty-four hours at ordinary tempera- tures with a solution of ammonium citrate containing 400 grammes of citric acid per litre, then filtering off the undissolved portion, washing it with ammoniacal water, and igniting it, the author has found the degree of solubility of the precipitate to be from 0.30 to 0.59 (mean 0.457) gramme per 100 C.C.of the liquid. A t a temperature of 50°C. the solubility is from 0.575 to 0.60 gramme per 100 C.C. F. H. L. Behaviour of Normal Ammonium Salts towards Litmus. C. Reichard. (Chem. Zeit., 1903, xxvii., 1105.).-It is stated in many of the text-books that an aqueous solution of pure ammonium chloride reddens blue litmus paper or tincture. This, however, is an error. If a piece of blue litmus paper is immersed in a solution (of any degree of concentration) of ammonium chloride in previously boiled water, it retains its blue colour for more than twenty-€our hours; only when it is taken out and allowed to dry naturally in the air does it turn red.This reddening is evidently due to the action of the atmospheric oxygen upon the ammonium compound in presence of moisture, a certain amount of dissociation taking place, which leads to the production of free acid. It is interesting to notice that if the paper which has become red is immersed once again in the original solution it resumes its blue colour. The nitrate, sulphate, and oxdate of ammonium behave similarly towards blue litmus ; in the case of the bromide, reddening occurs almost immediately the paper is withdrawn from the liquid. F. H. L. Estimation of Selenium. G. Pellini and E. Spelta. Quantitative Separation of Selenium and Tellurium. (Gazx. chiin. ital., 1903, xxxiii., [2], 89 and [l}, 515 ; through Chem. Zeit. Rep., 1903, 298 and 281.)-For the determination of selenium Pellini and Spelta propose to make use of the reaction between selenious anhydride and hydrazine sulphate or hydrochloride- NgE4 + SeO, = Se + 2H,O + N2 ; but instead of weighing the reduced selenium, they measure the nitrogen, 201.83 C.C.G. Pellini.THE ANALYST. 57 of which are equivalent to 1 gramme of SeO,. The original solution, rendered faintly acid with hydrochloric acid if desired, is brought into a flask, diluted to 50 C.C. with water, and mixed with a few grammes of sodium chloride in order to prevent loss of selenious anhydride on boiling. The flask is fitted with a cork and leading tube, its contents are boiled till all the air is expelled, and a boiling solution containing about 2 grammes of hydrazine sulphate or .hydrochloride and some hydrochloric acid is introduced.The nitrogen is led through previously boiled water, and is collected preferably in the Schultze and Tiemann apparatus. Pellini's process for the separation of selenium from tellurium depends on the fact that if a solution of selenious and tellurous anhydrides containing a little free hydrochloric acid is mixed with saturated solutions of ammonium hydrogen tartrate, tartaric acid, and hydrazine sulphate (not the hydrochloride), the selenium is reduced and precipitated whiIe the tellurium remains dissolved. The reaction is complete in the cold, but it proceeds more smoothly at a temperature between 50" and 60" C., and is ended in one or two hours. The liquid is then warmed rather more strongly in order to cause the precipitate to cohere, a, little more hydrazine sulphate is added to see whether the selenium has been wholly thrown down, and finally it is collected on a tared paper or in a Gooch crucible, washed with warm water and absolute alcohol, dried at 105" C., and weighed.The filtrate is treated with sulphuretted hydrogen, and the preoipitate is brought on to a paper and washed with water. The filter with its contents are transferred to a crucible and mixed with fuming 1-52 nitric acid; the excess of acid is evaporated on the water-bath, and the residue is dissolved in hydrochloric acid. The sulphuric acid derived from the oxidation of the sulphur is next removed by mean8 of barium chloride, and from the filtrate the tellurium is precipitated with hydraaine hydrochloride.The tellurium is finally washed rapidly with water, and further treated as above described. The results are accurate; but if hydrazine hydrochloride is employed for the precipitation of the selenium, it will be found contaminated with tellurium. F. H. L. Determinationof Sulphur in Coal aad Coke. R. Nowicki. (Stahl und Eisen, 1903, xxiii., 1141; through Chm. Zed. Wep., 1903, 281.)-One gramme of the powdered sample is mixed with 2 grammes of a mixture of one part of sodium carbonate and two of m&gnesia. The mass is arranged in a platinum crucible in such a way that a vertical and cylindrical air-space is left in the centre. The lower part of the crucible is raised to dull redness, and a current of oxygen is intro- duced into the upper part by means of the lid of a Rose crucible.The material is stirred up every five minutes, the air-space being always restored ; and after twenty or thirty minutes' incineration will be found to be complete. The residue is treated in the usual manner. F. H. L. The Separation of Coal from Earthy Impurities. P. Nyssens. (Bull. de Z'Ass. belge, 1903, 317, 318.)-Since the specific graviby of coal ranges from 1.16 t o 1.60, whilst clay varies in density between 1-70 and 2-20, and the other earthy58 THE ANALYST. impurities are usually still more dense, it is possible to effect a rapid separation by treating the finely-divided powder with a solution of ferric sulphate of specific gravity 1.50. The coal rising to the surface is collected on a filter, washed with water, dried at 100" C., and analysed by the usual methods.C. A. M. Determination of Free Phosphorus. J. Katz. (Oesterr. Chem. Zezt., 1903, vi., 515.)-This is a modification of a method suggested by Straub, which the author has found to be very tedious. The liquid containing the phosphorus is shaken with a solution of copper nitrate until a permanent black emulsion of copper phosphide is formed, then ether is added, and the whole agitated again. A sufficient quantity of hydrogen peroxide is next introduced till, after much shaking, the black colour dis- appears. The ethereal liquid is separated and repeatedly extracted with water ; the combined aqueous liquids are treated with a few drops of hydrochloric acid, and concentrated on the water-bath to a volume of 10 or 20 C.C. After filtration ammonia is added until the precipitate which first forms is redissolved, and the phosphoric acid is finally estimated with magnesia mixture in the usual manner. F.H. L. A Method for the Estimation of Chlorides, Bromides, and Iodides. Stanley Benedict and J. F. Snell. (Journ. Amer. Chem. Soc., xxv., 1138.)-The author makes use of the difference in behaviour of chlorides, bromides, and iodides towards potassium iodate (ANALYST, xxviii., 305) to determine these salts quantitatively when present together. The total halogens present in the mixture are first determined by any suitable method; iodine and chlorine are next determined as described below, and bromine is found by difference. To determine iodine, a quantity of the sub- stance, containing not more than 0-5 gramme iodine and 0.15 gramme chlorine, is dissolved in 50 C.C.water in a, stoppered 100 C.C. cylinder, About twice the theoretical quantity of neutral potassium iodate is added, and the solution acidified with 4 or 5 C.C. of 30 per cent. acetic acid. The liberated iodine is removed from the aqueous liquid by shaking with 30 to 40 C.C. carbon bisulphide, the carbon bisulphide being then separated by filtration through a wet filter-paper. After washing the carbon bisulphide solution with cold water on the filter, it is transferred to a beaker and covered with 20 to 25 C.C. of 75 per cent. alcohol, the filter-paper also being washed with some alcohol of this strength. The iodine is then titrated with sodium thiosulphate without using starch. For the determination of chlorine, the aqueous filtrate from the carbon bisulphide is treated with 5 C.C.nitric acid (specific gravity 1.18) and boiled till the whole of the bromine set free has been expelled. The excess of iodate added is next destroyed by adding a small excess of potassium iodide and boiling the liquid till colourless, 2 or 3 C.C. more nitric acid being added if all the iodine has not been driven off after ten or fifteen minutes' boiling. The liquid is then exactly neutralized with sodium carbonate, a little calcium carbonate being added at first to act as indicator, and chlorine determined by titration with silver nitrate, using potassium chromate as indicator. From the test analyses quoted it appears that the method is satisfactory. A. G. L.THE ANALYST.59 The Estimation of Carbon Dioxide in the Presence of Chlorine. C. Offer- haus. (Zeit. f. angew. Chem., 1903, xliii., 1033.)-This problem is of some importance in view of the fact that electrolytic chlorine contains varying and con- siderable quantities of carbon dioxide. In the first the gaseous mixture to be examined is led through two Bunte burettes in succession until all the air has been displaced. In one burette chlorine is estimated by absorbing in potassium iodide solution and titrating in the usual way. In the other burette the carbon dioxide and chlorine are estimated by absorbing both in dilute caustic soda solution of one-fifth normal strength and observing the diminution in volume, making due correction for the moisture in the gas. From the difference between the results given by the two burettes the percentage of carbon dioxide can be calculated.In the second method use is made of a standard solution of caustic soda about one-fifth normal, in which the carbonic acid has been determined by adding barium chloride and titrating with oxalic acid in the presence of phenolphthalein, according to Winkler’s method. As before, a known volume of the gas is collected in a Bunte burette, 45 C.C. of the caustic soda solution are added and shaken with it ; then 5 or 10 C.C. of pure 3 per cent. hydrogen peroxide solution are introduced, and the burette is again shaken. The liquid is then made up to exactly 200 c.c., of which 50 are taken for the determination of carbon dioxide by Winkler’s method. It is claimed that both methods give satisfactory results.Two methods are recommended. A. M. The Gasometric Determination of Bromates. Max Schlotter. (Zeits. Anorg. Chm., xxxvii., 172.)-The author shows that alkali-metal bromates are quantitatively reduced by hydrazine sulphate according to the equation : 2NaBr0, + 3NH, - NH, = 2Na;Br + 6H,O + 6N. He consequently bases a method for the determination of bromates on the quantity of nitrogen evolved on treating them with hydrazine sulphate in the apparatus shown in the figure. The 200 C.C. flask A contains the alkali bromate, and the flask B three times its weight of hydrazine sulphate ; both flasks are filled to about two-thirds their capa- city with water, and are con- nected together as shown. At the commencement of a deter- mination the pinch-cock h, is closed, h opened, the exit of the tube r being immersed in water.and both flasks heated until only 30 or 40 C.C. water remain in each in order‘to expel the air completely. Towards the end of the boiling h is opened and h, closed in order to fill the tube r with steam; h is then also closed, the flasks are allowed to cool, and h, is opened, when the hydrasine solution will60 THE ANALYST. pass over into B from A ; h, is closed as soon as air begins to enter the tube rl ; A is then heated, h opened as soon as there is an excess pressure in the flask due to evolved nitrogen, and the heating continued until no more gas-bubbles pass into the measuring tube. The volume of the gas is then read off as usud. In carrying out determinatione by the above method, the author found that in every ctwe the quantity of nitrogen found exceeded the theoretioal by an amount which is independent of the quantities of bromste and hydrazine sulphate used, provided only that the latter is in excess.The excess volume found appears to depend only on the apparstus used, and if it is determined once for all and subtracted from the volumes found, good results are obtained. A. G. L. APPARATUS. A Nitrometer for the Estimation of Uric Acid and Urea in Urine. A. Jolles. (Oesterr. Chem. Zed., 1903, vi., 509.)-As shown by the accompanying illustration, the decomposing vessel in this apparatus is a flask having a long neck, the advantage of which is that it can be st lagged,” and the flask shaken without danger of communicating the warmth of the hand to the liquid inside. The inner recep- tacle for the bromine is fused into the neck of the flask proper, and it is bent t o one side at its lower end in order to render it a more efficient agitator of the liquid in the flask. This inner receptacle is charged with the bromine reagent-preferably by means of a long funnel-through the upper mouth of the flask, while the urine is introduced through the lateral aperture thereof. The lateral aperture of the inner receptacle is made somewhat large, so that the reagent can be added quickly when the flask is suitably tilted. For exact work, the flask is supported inside a vessel containing water in the manner shown, but a water- jacket round the measuring tube is not really required. The side cock on the tube leading from the flask serves for The apparatus is made by Gockel of a preliminary adjustment of the pressure. Berlin. F. H. L.

ISSN:0003-2654    

DOI:10.1039/AN9042900054

出版商:RSC    

年代:1904

数据来源: RSC

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60 THE ANALYST. REPORT OF THE ROYAL COMMISSION ON ARSENICAL POISONING I N FOOD. THE final Report of the Royal Commission which was appointed in February, 1901, to inquire into the subject of arsenical poisoning from the consumption of beer and other articles of food or drink was issued last month, and constitutes a document of the highest interest and importance. The members of the Royal Commission were tho Right Ron. Lord Kelvin, G.C.V.O., D.C.L., F.R.S. (Chairman) ; the Right Hon. Sir William Hart Dyke, Bart.,THE ANALYST. 61 M.P.; Professor T. E. Thorpe, C.B., LL.D., F.R.S., Principal Chemist of the Govern- ment Laboratories ; Mr. H. Cosmo Bonsor ; Sir William s. Church, Bart., M.D., F.R.C.P. ; and Dr. B. A. Whitelegge, F.R.C.P. ; with Dr. G. S. Buchanan, of the Local Government Board, as Secretary.The Commission explain that in the Report they use for convenience the general term LLfood” to include also articles of drink, and observe that where quantities of arsenic are stated the figures given refer to arsenic reckoned as arsenious oxide. The Report is signed by 911 the members of the Commission, but there is a memorandum by Dr. Thorpe, in which he explains his reason for dissenting from the views expressed by his colleagues as to the composition of the suggested “ Board of Reference.” The Report is divided for the sake of clearness into eight sections, the first of which deals with the epidemic of arsenical poisoning which occurred in the North of England in 1900, and contains some very important observations regarding the medical and public health aspects of the evidence given in connection with arsenic in beer and food.Part 11. deals with the disease known as ‘‘ beri-beri,” the information collected by the Commission tending to negative the idea that there is any essential connec- tion between that disease and the ingestion of arsenically contaminated food. In Part I. the causation of the 1900 epidemic is briefly discussed, and the steps taken to check the outbreak are reviewed. As showing the extent of the epidemic, the statement that the number of persons who suffered was certainly 6,000, and probably very considerably greater, is interesting. Seventy deaths were certified as having been caused by arsenical poisoning, but, as the Commission remark, I t is evident that deaths thus certified do not represent the total number of cases in which death resulted from or was accelerated by poisoning due to arsenic in beer.” The facts in connection with the minor outbreak of arsenical poisoning which occurred in Halifax in 1902 are next recounted.This epidemic was of especial interest, since the incriminated beer (some of which contained as much as & grain arsenic per gallon) was proved in many instances to have been brewed from malt alone. Analysis of the malt, which had been dried over local gas coke, revealed contamination to the extent of grain per pound in one case, and demonstrated in a striking manner the need for constant care and watchfulness in the malthouse. Many highly interesting observations in reference to the therapeutics of arsenic are to be found in this section.I t also contains the conclusions of the Commission as to the cumulative or non-cumulative character of this poison. “From the clinical data obtained it would appear that arsenic can only be termed a non-cumulative poison in a restricted and comparative sense, this element having been detected in the excretion in one exceptional case fifty-nine days after the ingestion of arsenical beer had ceased.” The excretion of arsenic by hair appeared to be of such special interest to the Commission that they instituted experiments which showed that the hair of male patients who had been taking about & grain of arsenic daily contained as much as + to In concluding this section the Commission refer to the importance of excluding small quantities of arsenic from food and drink, pointing out that this question is of greater importance than might at first sight be They say : grain of arsenic per pound.62 THE ANALYST.supposed, and calls for more attention than it has hitherto received. They adhere, in fact, to the view expressed in the first Report that it would be unwise for them to express an opinion that any quantity of arsenic, however small, is to be regarded as admissible in any articles of food. Part 111. deals with the question of testing for arsenic in food and substances used in the preparation or manufacture of food. The Commission, after referring to the value of the large amount of work on the subject which had been undertaken by individual chemists and to the reports issued by the Committee appointed by the Manchester Brewers’ Association and by the Joint Committee appointed by the Societies of Chemical Industry and Public Analysts, proceed to review the informa- tion thus obtained.As the conclusions of the Committee on this matter are of such interest to analysts generally, we deal somewhat fully with this portion of the Report. The information obtained by the Commission is reviewed under three headings : Estimation of Arsenic by comparison of Mirrors obtained by the Marsh-Berzelius Method with Zinc and Acid ; Estimation by comparison of Mirrors obtained Electro- lytically ; Estimation by other Quantitative Methods. COMPARISON OF MIRRORS OBTAINED BY THE MARSH-BERZELIUS METHOD. The evidence shows that it is now recognised that a satisfactory estimation of the arsenic in a given substance can be made by comparing mirrors obtained by the Marsh-Berzelius method, after the substance examined has been subjected to appro- priate treatment, by which any arsenic present is obtained in a solution suitable for the proper application of the test.Attention is called to the various causes which may operate against the accuracy of this process, but chemists are now in general agreement as to the main sources of error, and have but little difficulty in avoiding them. The Committee remark that they do not attempt to pronounce for or against particular modifications of the Marsh-Berzelius method which are preferred by one or another analyst. ( 6 We are satisfied that careful analysts who estimate arsenic by this method can obtain results sufficiently exact and comparable for practical purposes, although the details of their procedures may differ.Were it possible to secure for the future the uniform adoption by analysts of one and the same method with the same detail in all respects, the determinations would become still more closely comparable, with obvious advantage. The work of the committees and chemists to which we have above referred, and in particular the important recommendations of the Board of Inland Revenue Departmental Committee as to tests for arsenic in various sub- stances used in the preparation of beer, materially advance this object, but do not lead to the conclusion that at this stage any single detailed routine can be said to be applicable to all cases without exception.” It is pointed out that as regards detection of arsenic by the above method the evidence shows that when various substances are taken in quantities which have been found practically convenient, the presence of arsenic will be detected when in amounts well below --inn grain per pound, or (in the case of a liquid) well below & grain per gallon.They say :THE ANALYST. 63 The Commissioners recognise that the personal equation is of some importance in connection with the carrying out of this test, but they point out that the differences likely to be met with between careful and experienced operators would be so slight a8 to be practically negligible, and that in particular instances, where close approxima- tion is desired, the difficulty can be met by making more than one estimation, or, if need be, by repeating the experiment with a solution corresponding to a larger or smaller amount of the substance.Referring to the various forms of preliminary treatment which may be applied to different substances prior to the actual estimation by the Marsh-Berzelius method, the Commissioners remark that in the case of unground malt and a few other sub- stances a satisfactory estimation can be made without the destruction of organic matter, but that in such cases it is desirable that comparison should be made with standards prepared by the addition of known quantities of arsenious oxide to arsenic- free specimens of the material examined. In the case of organic substances which are liable to cause frothing, or in which the arsenic may possibly exist in the form of an organic compound, destruction of the organic matter by an “acid” or by a ‘‘ basic ” method is necessary, and in the case of brewers’ worts it is recommended to effect the destruction in all cases.“Several chemists who have given close attention to the subject prefer to destroy the organic matter in beer as a matter of routine before employing the Marsh- Berzelius test ; and the Departmental Committee of the Board of Inland Revenue also recommend this course. It appears to us that this plan should be uniformly adopted. ” I n the examination of fuel it is recommended either to employ the method of burning the fuel with lime or other base, or to adopt the process recently recom- mended by the Board of Inland Revenue Committee (ANALYST, vol.xxviii., 344). The electrolytic method recently recommended by the above Committee (ANALYST, vol. xxviii., 349) is also referred to, and some of the’ advantages which it appears to possess over the zinc method are enumerated. Other quantitative methods than the Marsh-Berzelius method are briefly referred to, but in view of the general use by analysts of the latter process, and to which such precision has been given by the work of the last few years, chemists are exhorted to acquaint themselves as to the extent to which their determinations correspond with or differ from those made by a comparison of mirrors. Part IV. deals with the various ways in which faods are liable to become con- taminated by arsenic.Among the principal ingredients of food or substances used in the preparation of food which are liable to contain arsenic, and which therefore ought to receive the special attention of the food chemist, the following are dealt with : sulphuric acid, hydrochloric acid, glucose, invert sugar, glycerine, colouring matters, caramel, phosphoric acid, phosphates, borates, and boric, tartaric and citric acids. Beer ‘‘ regenerators,” hardening materials, yeast foods, and other preparations employed by brewers are also referred to. The liability of malt. to be seriously contaminated by arsenic, whioh had been so amply demonstrated to the members of the Commission, and the difficulty of ex- Speaking of beer, the Commissioners remark :64 THE ANALYST. cluding small quantities of that element during manufacture, cause this food material to assume far greater importance than those above enumerated, and it is consequently dealt with at some length in the Report.The precautiona which maltsters should adopt in regard to the selection of fuel, the cleansing of kilns, and the screening and brushing of malt, are clearly set forth, and the Commission report to the effect that : ‘( All our evidence goes to show that it is now commercially practicable to produce malt which either may be considered free from arsenic, or in which the amount of arsenic present is certainly less than grain per pound (0.57 parts per million), and that most of the malt prepared during the past two years has been of this c haract er. ” The following finished foods, in the order in which they appear in the Report, are mentioned as being lisble to arsenical contamination through the use of the above ingredients or in other ways, in the absence of sufficient precautions : beer, golden syrup and treacle, jams, artificial honey, sweets and other foods containing glucose, vinegar, Demerara sugar (rarely), and food preparations made from malt and yeast.Foods containing colouring matters or preservatives may also, of course, contain small quantities of arsenic derived from those substances. Gelatine and liquorice are mentioned as food substances liable to be contaminated, and two samples of dried chicory contained about & grain per pound of arsenic. Part V. deals with the precautions which should be taken by manufacturers to exclude arsenic from foods, and is deserving of the most careful study by all who are engaged in the manufacture of food products.Reference is made in this section to such of the above-named substances as are also included in the British Pharmacopoeia. The Report says : ‘‘ At present the tests for arsenic which the British Pharmacopceia directs to be employed are qualitative, and the quantity of substance to which the qualitative tests are to be applied is in nearly every case undefined. The Pharmacopceial Committee of the General Medical Council has now under consideration the question of revising the Pharmacopoeia1 tests for arsenic, with the objeot of giving them a quantitative value, and of adding to the list of drugs which are required to be tested for arsenic.” Parts VI.and VII., which may be considered together, deal with the present means of official control over purity of food in relation to arsenic, and recommenda- tions as to improvements in official control over the purity of food, I t is pointed out that at present, save in a few special cases, the control which can be exercised over manufacturers of food becomes available only after the manufacture of the food is completed and it is on sale to the public. In this connection the existing Sale of Food and Drugs Acts come in for a considerable amount of discussion, and attention is directed to tne fact that for reasons well known prosecutions under Section 3 of the ,1875 Act are comparatively seldom instituted, and that in practice nearly all prosecutions are taken under Section 6, and the Commissioners remark : ‘‘ Even in the case of foods contaminated by arsenic in such ways as we have described in Part IV.of this Report, it would appear that a prosecution would in most instances have greater chance of success if taken under Section 6, and this view was held almost wiihout exception by the local authoritiee which decided to institute prosecu- tions with regard to arsenical beer in consequence of the 1900 epidemic.”THE ANALYST. 65 The evidence which was presented to the Commiesion by various official witnesses showed that the Sale of Food and Drugs Acts as at present interpreted and administered are unsatisfactory for the purpose of protecting the consumer against arsenic or other deleterious substances in food, partly on account of the difficulties involved in the question of warranty, and partly because the authorities have no means of knowing what particular foods are most liable to contain deleterious sub- stances.The Commissioners remark : ‘‘ As a rule, Public Analysts receive samples in order that they may pronounce upon their genuineness or otherwise, knowing nothing of the local circumstances which led to their being taken, of their origin, or of the reasons for sending them. The term ‘genuine’ in this sense means that the analyst has not detected such objectionable substances ES he has considered it necessary to look for in the sample submitted to him. Obviously, the value of the statement that a sample is ‘ genuine ’ depends upon the extent to which the analyst has means of knowing what are the objectionable substances which it is liable to contain.I n present circumstances he has not sufficient information on this point. Different analysts may thus pronounce upon the genuineness of identical samples on widely different data.” It is also pointed out that ‘‘ the application of the Sale of Food and Drugs Acts to prevention of contamination of foods by deleterious substances iR materially hindered by want of an official authority with the duty of dealing with the various medical, chemical, and technical questions involved,” and that the absence of official standards also militates against the efficiency of the existing Acts. After some reference to the Public Health Acts, the Report of the Commission proceeds to deal with several important ‘recommendations as to improvements in official control over the purity of food, and the necessity for more extended administration by the Local Government Board is referred to.I t is recommended that to this end the Local Government Board should have the assistance of a special officer, with suitable scientific knowledge,” who should be in relation with the Government Laboratory, and who would be able to institute the necessary chemical inquiries, and obtain, from various sources, such information as would in turn enable the Board to advise and direct the work of local authorities in the matter of securing the greater purity of food supplies. The Commissioners state that they are of opinion that official standards must be prescribed if the Sale of Food and Drugs Acts are to be satis- factorily applied to control the purity of food, and for reasons given they prefer to term these ‘‘ standards for the purpose of the Sale of Food and Drugs Acts ” rather than “ standards of purity.” I t is considered that the Local Government Board (under advice as indicated above) should be the authority to prescribe, and from time to time to vary, standards for the purpose of the Sale of Food and Drugs Acts.The Commission are of opinion that a Board or Court of Reference, such as has been recommended by the Committees on Food Products Adulteration and on Preserva- tives and Colouring Matterg in Foods, should be established. They further express the opinion that such should not be an administrative but a consultative Board, available on the application of the Government Department concerned to pronounce on specific points which are specially referred to them.The responsibility of manu- facturers or intermediate vendors under the existing Acts is referred to, and the66 THE ANALYST. Report says : ‘‘ If, in a prosecution instituted under the Sale of Food and Drugs Acts, it is-alleged by defendent A that the article was sold in the condition in which it was supplied to him by B (e.g., the manufacturer, importer, or giver of warranty), or that the contamination is due to an ingredient supplied by C, it should be possible for A to attach B (or C, as the cage may be) to the prosecution. The sama principle should apply to the person thus associated in the defence, if he in his turn alleges that a third party is responsible, by breach of warranty or otherwise, for the adultera- tion or contamination of the final product.” The last paragraph of the Report deals with the proportions of arsenic in food which would constitute an Gffence under the Sale of Food and Drugs Acts, and is as follows : ‘‘ Pending the establishment 0: oflicial standards in respect of arsenic under the Sale of Food and Drugs Acts, the evidence we have received fully justifies us in pro- nouncing certain quantities of arsenic in beer and in other foods as liable to be deleterious, and at the samo time capable of exclusion, with comparative ease, by the meful manufaoturer.In our view, it would be entirely proper that penalties should be imposed under the Sale of Food and Drugs Acts upon any vendor of beer or any othor liquid food, or of m y liquid entering into the composition of food, if that liquid is shown by sn adequate test to contain &$h of a grain or more of arsenic in the gallan; and with regard to solid food-no matter whether it is habitually con- sumed in large or in small quantities, or whether it is taken by itself (like golden syrup) or mixed with water or other substances (like chicory or ‘carnos’)-if the substance is shown by an adequate test to contain grain of arsenic or more in the pound.” In this final Report there is a memorandum by Dr.Thorpe, who differs from his colleagues as to the composition of the suggested Board of Reference. Dr. Thorpe says : ‘( I venture to think, therefore, that instead of creating a permanent committee consisting of a small number of scientific men, as the authority to prescribe the standardswhich should be fixed for the purposesof the Sale of Food and Drugs Acts, it would be preferable to follow the procedure of the Board of Agriculture, and to entrust the consideration of the propriety of fixing a, standard, or stmdards, in the case of particular groups of allied substances, to specially constituted committees in which manufacturers and technical experts in the trade concerned were represented. Considering the very large and legitimate commercial interests involved, I am of opinion that no other course would be satisfactory.” The Report may be obtained from Messrs. Eyre and Spottiswoode, of London ; Messrs. Oliver and Boyd, of Edinburgh ; or Mr. E. Ponsonby, of Dublin ; and is issued at the price of Qd. The two volumes of evidence are published at 49. and 3s. l l d .

ISSN:0003-2654    

DOI:10.1039/AN9042900060

出版商:RSC    

年代:1904

数据来源: RSC

摘要:

THE ANALYST. 67 DEPARTMENTAL COMMITTEE ON BUTTER REGULATIONS. THE final Report of the Departmental Committee appointed by the Board of Agriculture to inquire and report upon the desirability of regulations under Section 4 of the Sale of Food and Drugs Act, 1899, has recently been issued The Committee consisted of the following gentlemen: The €tight Hon. H. C. Plunkett (Chairman); Sir Charles A. Cameron, C.B., M.D., Medical Officer of Health and Public Analyst for Dublin; Professor T. E. Thorpe, C.B., LL.D., F.R.S., Principal Chemist of the Government Laboratories; Major P. G. Craigie, an Assistant-Secretary of the Board of Agriculture; Mr. R. A. Anderson, Secretary of the Irish Agricultural Organization Society ; Mr. Christopher Dunn, J.P., Chairman of the Trustees of the Cork Butter Market; Mr.George Gibbons; Mr. John Gilchrist ; Mr. Hudson E. Kearley, M.P. ; Professor J. Millar Thomson, LL.D., F.R.S., President of the Institute of Chemistry; and Mr. Patrick Hickey ; with Mr. A. E. Balleine, of the Board of Agriculture, as Secretary. The queetion of water in butter having been dealt with in a former Report, the present Beport deals with the results of the inquiries of the Committee as to what regulations, if any, might with advantage be made for determining what deficiency in any of the normal constituents of butter, or what addition of extraneous matter, other than water, should raise a presumption, until the contrary is proved, that the butter is not genuine. Twenty-six witnesses were examined, including eleven representatives of various butter-producing countries (Holland, Norway, Denmark, United States of America, Germany, Sweden, Russia, and France), twelve analysts, two magistrates, and one inspector of the Board of Agriculture.After discussing the evidence (which at the time of going to press is not yet published), the Report ends with the following recommendations : 1. That the figure 24 arrived at by the Reichert-Wollny method should be the limit below which a presumption should be raised that butter is not genuine. 2. That the use of 10 per cent. of sesame oil in the manufacture of margarine should be made compulsory. 3. That steps should be taken to obtain international co-operation. Mr. Dunn and Mr. Gilchrist agree with the main report, except that they recommend a limit of 23 for the Reichert-Wollny figure.Major Craigie, however, appends a note, in which, in view of the evidence, he expresses his inability to regard the moment opportune, or the information even yet sufficient, to warrant the immediate issue of official regulations in this matter, as suggested in the Committee's Report, although, should it hereafter become necessary to prescribe the particular proportion of volatile acids which should raise a legal presumption that the butter is not genuine by reason of the addition of foreign fat, he is disposed to concur in the recommendation that the figure of 24 arrived at by the analytical method referred to is open to less objection than either a higher or a lower number. In view of the fact that the Report urges the recewal on a more extensive scale of the special inquiry into the relative influence of the numerous factors other than the addition of68 THE ANALYST. foreign fat which affect the normal proportions of volatile acids in genuine butter made within the United Kingdom, Major Craigie desires to urge the wisdom of obtaining the results of this new inquiry before imposing a statutory limit which would raise, irrespective of the origin or history of a particular sample, a legal presumption that the article is not genuine. Mr. Hickey does not sign the Report of the Committee, but makes a dissentient minority report expressing the conclusion that the evidence does not afford solid grounds for fixing a limit for the proportion of volatile acids. The Report may be obtained from Messrs. Eyre and Spottiswoode, of London ; Messrg. Oliver and Boyd, of Edinburgh ; or Mr. E. Ponsonby, of Dublin, and is issued at the price of 3d.

ISSN:0003-2654    

DOI:10.1039/AN9042900067

出版商:RSC    

年代:1904

数据来源: RSC

摘要:

68 THE ANALYST. INSTITUTE OF CHEMISTRY OF GREAT BRITAIN AND IRELAND. PASS LIST OF THE EXAMINATIONS IN JANUARY, 1904. Of fifteen candidates who entered for the Intermediate Examination the following eleven passed : Stanley Winter Collins, David Cowan Crichton, Harold Deane, B.Sc. (Lond.), Cyril Dickinson, B.Sc. (Vict.), John hugustus Goodson, Henry Ward Good- win, Alfred George Holborow, Charles James, Harry Edwin Laws, Robert Park, and Edwin Rhodes, B. Sc. (Vict.). In the Final Examination for the Associateship (A.I.C.) in Mineral Chemistry, of six who entered the following four passed : Denison Benzs- ville Byles, Arthur Charles Carter, James Gray, and Arthur Hopwood, Assoc.R.C.Sc. (Lond.). I n Organic Chemistry, of the eleven who entered the followjng six passed : Marmaduke Barrowcliff, Edwin Jesse Fairhall, A.C.G.I., William Oswald Littlebury, Miss Frances Mary Gore Micklethwait, Ass0c.R.C.Sc. (Lond.), Fred Schole~field, B. Sc. (Lond. and Vict.), and Harold Stevenson. Of four who entered in the Branch of the Analysis of Food and Drugs and of Water, including the Examinations in Thera- peutics, Pharmacology, and Microscopy, the following three passed : James Handby Ball, B.Sc. (Vict.), Herbert Sutcliffe Shrewsbury, and Henry Edgar Watt, M. Sc. (Durham). For the Fellowship (F.I.C.) three candidates were examined, two passed : in Branch D (Organic Chemistry), Harold Hibbert, M.Sc. (Vict.); in Branch E (Analysis of Food and Drugs, etc.), Edward William Lucas. The Examiners in Chemistry were Mr. Walter W. Fisher, M.A., F.I.C., and Professor W. Palmer Wynne. Dr. Arthur P. Luff conducted the Examination in Therapeutics, Pharma- cology, and Microscopy. ESANINATION IN APRIL, 1904. A Final Examination in all branches except that of Biological Chemistry will be held at the Laboratories of the Institute, commencing on Tuesday, April 12, 1904, provided that a sufficient number of candidates enter their names for the same. Applications should be forwarded not later then Tuesday, February 23, 1904.

ISSN:0003-2654    

DOI:10.1039/AN9042900068

出版商:RSC    

年代:1904

数据来源: RSC