T E E JOURNAL OF IIVDUSTRIAL A N D ENGINEERING CHEMISTRY
J a n . , 1914
TABLE11-RESULTS
ON THE COMPOSITION OF GIANT KELPS B y A. R . M E R Z ~ Received October 22, 1913
T h e d a t a presented i n this paper were obtained i n t h e course of t h e investigations directed by Dr. Frank K. Cameron, of t h e Bureau of Soils, looking t o t h e possibility of t h e utilization of t h e giant kelps of t h e Pacific coast as an economic source of potash salts and other useful products. During t h e summer of t h e present year, two parties were sent t o Alaska €or t h e purpose of surveying, mapping, sampling, and obtaining further information concerning t h e kelp beds of t h e Alaskan coast. One of these parties, under t h e leadership of Prof. G. B. Rigg, of t h e University of Washington, covered t h e beds of t h e Alaskan Peninsula; t h e other, headed by Dr. T. C. Frye, of Seattle, confined its operations t o the coast of Southeast Alaska. The samples obtained by TABLEI-(RIGG)
RESULTS IN PERCENTAGES fisfuluso; 4, 5, X, 9. 10-Nereocystis; Y-Porphyra; 1 1-Fucus T o t a l solNo. uble salts KzO Ash I N Locality l a. . . . . . . . . . . 1 5 . 4 4 2.27 4 . 4 1 None 2 . 4 4 l b . . . . . . . . . . 15.76 2 . 6 1 4 . 4 4 None 2.35 I C. . . . . . . . . . 1 5 . 1 6 3 . 0 8 4.72 N o n e 2.44 I d . . . . . . . . . . . 15.20 3 . 6 6 4.69 None 2 . 1 5 1, 2, 3, 8-Alaria
2 . . . . . . . . . . . 25.72
5.99
6.04
None 2 . 1 9
30 . . . . . . . . 2 5 . 3 6 3b . . . . . . . . . 2 0 . 1 4 8. . . . . . . . . . . 30.62
10.28 7.05 12.70
6.06 7.08 6.46
None 2.32 None 2 . 8 4 None 2.38
4 Stem.. . . . . 5 Leaves. . . . ( a ) .. . . . . . . . 9 Stem.. . . . . 10 L e a v e s . , . . 11 . . . . . . . . . . .
52.88 39.40 48.80 56.40 38.44 17.24 23.54
28.26 3.60 15.44 4 . 3 4 2 0 . 2 1 4.12 24.69 3 . 1 0 14.78 4.30 3.48 4.48 Y........... 7 . 3 3 4.22 ( a ) Whole young plant
.
0.06 0.14 None 0.06 None None None
1.06 2.27 1.87 1.15 2.02 1.12 5.21
{
~
~
Geese Isl. Geese Isl. N . of Hog Isl. Afognak Geese Isl. Geese Isl. Kodiak Port Graham Port Graham Seldovia Geese Isl. Str.
~
IN
PERCENTAGES
Genus a n d Species: , 4, 8, 11, 12, 13, 15, 19 Alavio fistuZosa;-20, 22, 235, 6, 7-Macrosystis; 18-Fucus; others-Nereocystis L = Leaves; S = Stems; Y P = Young P l a n t Locality T o t a l solSO. uble salts KzO Lat. Lmg. Ash I N 13:!O 57' 4 . . . . . . . . . . . . . 27.86 1 0 . 9 6 7 . 3 4 None 3 . 2 5 56' 12' 13.1' 12' 8 . . . . . . . . . . . . . 3 2 . 3 0 13.07 6 . 0 8 Iione 2 . 0 5 54O 58' 133' 39' 11 . . . . . . . . . . . . . 2 7 . 1 8 10.65 12.12 None 2 . 4 3 56O 07' 133' 07' 12 . . . . . . . . . . . . . 26.82 11.83 8 . 8 0 Trace 2 . 4 4 56' 17' 133' 22' 8.60 13 . . . . . . . . . . . . . 1 9 . 7 6 5 . 4 8 h-one 2.87 56' 20' 133' 54' 15 . . . . . . . . . . . . . 27.46 1 0 . 9 0 8 . 1 8 None 2 . 8 0 56' 08' 134' 20' 9.02 1 5 . 0 8 None 3 . 3 0 56' 54' 19 . . . . . . . . . . . . . 2 6 . 4 8 133' 36' 20.. . . . . . . . . . . . 21.80 8.63 5 . 9 6 None 2 . 6 8 56O 21' 133' 34' 22 . . . . . . . . . . . . . 1 9 . 4 6 6.92 6 . 5 8 Trace 2 . 6 9 57O 13' 134' 34' 23 . . . . . . . . . . . . . 1 9 . 8 4 7.30 6 . 9 2 None 2 . 1 9 57O 01' 132' 29' 5 . . . . . . . . . . . . . 45.76 22.48 2 . 6 4 54O 58' 5.22 0 . 3 0 1 . 0 8 Bet. D u k e Isl. a n d 6(a) . . . . . . . . . . 28.62 1 1 . 4 9 4.07 0 . 0 6 Bee Rocks 133O 16' 1 . 2 5 5 5 O 22' 7 . . . . . . . . . . . . . 3 1 . 5 0 13.26 4.14 0 . 1 0 1 I. . . . . . . . . . . . 3 4 . 3 8 12.74 5 . 1 2 S o n e 2 . 8 7 Pearse Canal s . . . . . . . . . . . 4 9 . 4 4 2 3 . 8 8 10.66 None 1 . 5 3 2 L . . . . . . . . . . . 4 0 . 1 0 15.12 3 . 0 6 Bet. Tangass and 4.34 0.07 K a n a g u n n t Isl. 1.07 S . . . . . . . . . . . 6 3 . 7 4 30.12 2.76 0 . 0 5 9 S . . . . . . . . . . . 5 8 . 8 6 27.02 3 . 2 2 None 0 . 8 1 Gulf of Esquibel I,... . . . . . . . . 4 7 . 2 6 1 9 . 6 3 3 . 4 6 None 1 . 0 4 55O 37' 133' 28' 1.52 Eagle i d . , David10 Y . P . . . . . . . . . 4 2 . 7 4 1 6 . 7 4 5.66 0.06 son Islet 133O 30' Y . P . .. . . . . . 6 4 . 4 4 2 8 . 7 6 2 . 9 0 None 0 . 5 9 5 5 O 54' 133' 40' 1.85 56O 12' 14 . . . . . . . . . . . . . 4 4 . 9 2 20.12 3.64 0.06 133" 54' 1 . 4 6 56' 08' 16 . . . . . . . . . . . . . 5 0 . 0 0 26.05 6.22 0 . 1 0 132' 57' 1 . 6 5 56O 36' 5.26 0.09 17 I,.& S . . . . . . 5 1 . 2 4 2 1 . 6 1 21 . . . . . . . . . 5 3 . 5 4 2 4 . 8 0 3 . 6 8 0 . 0 3 0 . 9 8 Wrangell Str. 133' 57' 2 . 0 1 56O 36' I. . . . . . . . . . . . 4 4 . 4 0 17.67 4 . 9 8 0.10 ~ ~ 2 2 . 7a3 . . . . . u. . . . 51.34 2~ 4.. . .~ 134" 34' 4y. 2 2 Trace 1 . 5 4 57' 01' 18 . . . . . . . . . . . . . 1 7 . 5 2 3.51 1 . 1 8 Wrangell S t r . 5.44 None
--.
s..
~
( a ) Upper 6 f t . of plant.
near
both parties were dried, and sent t h u s in bags t o t h e laboratories of t h e Bureau of Soils for analysis. T h e samples were r u n according t o t h e methods published b y T u n e n t i n e , * a n d results are given i n Tables I and 11. T h e nitrogen determinations in Tables I , I1 and I11 were made by T. C. Trescott, of t h e Bureau of Chemistry. An inspection of these results indicates t h a t t h e Nereocystis of Alaskan waters is, as respects potash content, of as great importance as a n economic source of potash salts as t h a t of t h e more southern waters. T h e Macrocystis contains a lower percentage of potassium t h a n does Nereocystis while t h e Alaria contains a decidedly lower percentage. T h e sea-weeds Fucus and Porphyra are evidently valueless as sources of potash on an economical scale, and t h e analyses are given merely because of t h e interest which may a t t a c h t o them otherwise. Since t h e publication of t h e author's joint article with J. R. Lindemuth upon t h e leaching effects of sea water on freshly cut kelp,3 a further set of analyses (Table 111) has been obtained confirming t h e conclusions of t h a t paper. A large sample of Macro-
* Scientist in Fertilizer Investigations. Bureau of Soils, U. S. Departm e n t of Agriculture. 2 THISJOURNAL, 4, 431 (1912). a I b i d . . 5, 729 (1913).
cystis was taken b y Prof. W. C. Crandall, of La Jolla, California, and sub-samples were taken of this as described in our previous paper, t h e wet samples being forwarded in jars t o Washington for analysis. Sample 2 2 , however, was dried and sent in a sack by mail. T h e anomalously high percentage of total solids in TABLE 111-RESULTS I N PERCENTAGES Sample No. 22, dried in sack; others, wet, in j a r Sampled August, 1913 Sample T o t a l solN Day Time No. uble salts K20 .4sh I 1.79 9 2.10P.M. 1 . . . . . . . . . . . . 5 4 . 5 4 10.47 4.72 0.07 0.53 9 2.10P.M. 4.48 0.13 1.26 9 5 . 0 0 P.M. 6.12 0.19 1.94 9 6 . 1 5 P.M. 8.08 0.05 3. . . . . . . . . . . .35.28 14.81 0.70 9 8 . 2 0 ~ . ~ . 5.36 0.06 0.90 9 1 0 . 1 5 P.M. 5 . . . . . . . . . . . . 31.74 13.29 5.40 0.05 0 . 8 0 10 5 . 3 0 A.M. 6 . . . . . . . . . . . . 3 2 . 9 0 14.32 5.64 0.07 1 . 5 7 10 10.00 A . M . 0.22 . . . 3 5 . 8 6 16.55 4 . 9 6 0 . 7 0 10 4.00p.~. 3.52 0.10 1 . 6 0 10 8.00p.ar. 5.12 0.19 1.07 11 1 2 . 1 0 a . ~ . . . . 2 9 . 4 4 12.67 3 . 9 6 0.10 0 . 8 6 11 4.00p.~. 5 . 1 8 N o t det. 1.01 12 7 . 0 0 ~ ~ . 5.58 0.16 12 . . . . . . . . . . . . 29.46 1 2 . 3 3 1 . 0 7 12 1 0 . 0 0 a . ~ . 5.96 0.13 13 . . . . . . . . . . . . 3 1 . 1 8 11.64 0 . 8 9 12 1.0Op.~. 0.13 14 . . . 3 0 . 6 4 11.87 5 . 8 6 1 . 1 1 12 4.00P.M. 6.82 0.16 15 . . . . . . . . . . . . 3 2 . 3 6 12.85 0 . 8 3 12 7 . 0 0 ~ . ~ . 6.44 0.16 16 . . . . . . . . . . . . 3 3 . 4 8 13.76 1.00 13 7.00A.M. 7.22 0.19 1 . 4 0 14 7.OOa.M. 13.32 0.13 0 . 9 7 15 7 . 0 0 ~ . ~ . 7.36 0.21 19 ............. 3 3 . 7 6 14.72 1 . 5 4 16 7.00A.M. 0.03 20 . . . . . . . . . . . . 29.44 1 0 . 2 4 17.44 1 . 5 5 17 7.00A.M. 21 . . . . . . . . . . . . 3 2 . 9 8 14.19 7.38 0.26
Sample I is possibly t o be explained by t h e presence of sea-water, the jar having considerable water therein and t h e sample itself being quite small. The manner of sending Sample 2 2 probably accounts for its comparatively low saline content.
16
T P E J O U R N A L O F I N D U S T R I A L A N D Eh‘GINEERIhtG C H E M I S T R Y
Vol. 6, No.
I
industry, there naturally arise new problems concerned with the analysis of mixtures containing t h e same. Such a new material is Cyanamid, now in its fourth season in the United States, though in much older use in Europe. That it is making remarkable headway in this country, is evidenced by the fact t h a t last year’s production will be doubled this year and some 60,000 tons will be placed upon the market next year. At present, this material is marketed in two forms, a finely powdered Cyanamid, so finely divided t h a t all will pass a 60-mesh screen, and 7 5 per cent or more will pass a loo-mesh screen; and a granulated form sizing between IO- and So-mesh. The chemical composition of t h e two varieties is approximately the same, carrying nitrogen equivalent t o 18.5 per cent ammonia, nearly all in the form of calcium cyanamide. This compound is a comparatively weak one, hydrolyzing instantly in an excess of water to cyanamide and its polymers, t o ammonia, t o urea, etc. The calcium salt is so unstable in the presence of watei t h a t i t has never been isolated frorh aqueous solution. Besides calcium cyanamide, the commercial product contains free calcium hydrate, graphite, and various TABLE IV-RESULTS IN PERCENTAGES other minor impurities. The product marketed last S = Stems; L = Leaves year averaged 40 per cent calcium content in t h e Sample Total solvarious forms enumerated above, which we are going No. K?O ublesalts Ash N t o assume as hydrate for the purposes of this dis0.51 S Coronado Id., 1 Macrocystis , 18.28 36.78 2 . 3 6 Lower Cal. cussion since t h a t is t h e form most probably assumed 0.84 L Geese Id., 2 Nereocystis . . . 9 . 9 0 25.94 3.88 by t h e lime as soon as mixed in t h e ordinary com28.26 52.88 3.60 1.06 S Alaska plete fertilizer, though later it may react t o various L 15.44 3 9 . 4 0 4 . 3 4 2 . 2 7 3 Nereocystis . . 24.69 5 6 . 4 0 3 . 1 0 1.15 S Port Graham, other forms. L Alaska 14.78 3 8 . 4 4 4 . 3 0 2 . 0 2 Abroad, t h e bulk of the annual production of some S Pearse Canal, 4 Nereocystis.. . 23.88 4 9 . 4 4 1 0 . 6 6 1 . 5 3 200,000 tons finds its way into t h e soil directly, due 12.74 3 4 . 3 8 5 . 1 2 2 . 8 7 L Alaska 5 Nereocystis.. , 3 0 . 1 2 63.74 2.76 1.07 S Bet. Tangass and t o the common European practice of using unmixed 15.12 4 0 . 1 0 4 . 3 4 3 . 0 6 .I Kanagunnt Isl.. fertilizers. Only small quantities get into complete Alaska S Gulf of Eiquibel 6 Nereocystis . . . 2 7 . 0 2 5 8 . 8 6 3 . 2 2 0 . 8 1 mixtures and no question of analysis seems t o have L Alaska 19.63 4 7 . 2 6 3 . 4 6 1.04 arisen regarding such mixtures, as it is a n assumed 7 Nereocystis. . . 2 8 . 7 6 6 4 . 4 4 2 . 9 0 0 . 5 9 S Eagle Isl., Davidfact t h a t there Cyanamid is incapable of transforming 16.74 4 2 . 7 4 5 . 6 6 1.52 L son Islet, Alaska S Wrsngell S t . , 8 Nereocystis . . . 2 4 . 8 0 5 3 . 5 4 3 . 6 8 0 . 9 8 acid phosphates into an unavailable form, irrespective L Alaska 17.67 4 4 . 4 0 4 . 9 8 2.01 of t h e results yielded by the usual methods of analysis. 9 Postelsia... . . . 2 0 . 0 41. 1 4.0 1 .01 S Neah Bay, Palmaeformis. 1 3 . 9 29.90 5 . 7 1.83 L Wash. I n this country where nearly all t h e Cyanamid 10 Postelsia ... . . . 2 2 . 8 44.5 3.2 0.94 S Montara P t . , enters into such complete mixtures which are sold L Cal. Palmaeformis. 9 . 7 29.7 4.3 1.40 on the basis of analysis by Official Methods, we have 1 1 Macrocystis.. . 1 8 . 7 40.3 5.3 1.24 S St. Nicholas. . . 12.4 28.3 6.9 l . O 4 S & L Cal. presented t o us a possibility of reactions being caused Samples 9, 10 and 1 1 are from Turrentine. t o t a k e place between t h e acid phosphate and t h e with their respective analyses. An attempt t o find Cyanamid by reasons of t h e manipulation as preuniformly constant variations between stem and scribed in these methods of analysis. Results obtained leaves in content of other constituents justified t h e two after such reaction has taken place are of course not representative of t h e material as sampled. following conclusions : We can here dismiss a discussion of t h e constitution ( I ) The ash content is almost invariably larger of t h e ordinary acid phosphate of commerce. We have in t h e leaves t h a n in t h e stem of the same plant. (11) The nitrogen content is almost invariably larger already discussed sufficiently the chemical constitution and behavior of Cyanamid, but it might be well t o i n t h e laminae t h a n in the stipe of the same plant. state here t h a t our future discussion will be limited BUREAUOF S O I L S U.s.DEPT. OF AORIC.,WASHINGTON t o the granulated form because of the present lack of a method of separating undccomposed Cyanamid from THE OF ‘OMPLETE a complete fertilizer mixture other t h a n b y picking ING CYANAMID2 i t out particle by particle. This granulated form of B y H. W. HILL AND W. S . LANDIS Cyanamid is designed t o present a minimum of reWith t h e advent of new materials into t h e fertilizer actinn surface for a u .. of material, the 1 Jour. Frank. Inst., 176, 364 (1913). mixture Of any addition to the Ordinary 2 Presented at the 48th Meeting of the A. C. S., Rochester, September 8-12, 1913. remaining inactive in the interior of t h e granule.
After the large sample was cut a t 2 . 1 0 P.M., i t was taken from t h e water and kept out. till 3.50 P . M . before re-immersion. It was cut off Pt. Vincente, California in t h e vicinity of the beds now being cut b y commercial organizations, Lat. 33 ’ 2 2’ 3 0 ” , Long. I 18’ 20’. Sub-samples 1-6 and 2 2 were taken where the large sample was c u t ; 7 , while steaming t o Pt. Vincente; 8-11, while steaming t o Avalon; 1 2 , on t h e way t o San Diego; and t h e others in San Diego Bay. During t h e course of analysis of the numerous samples of kelps which have been recently analyzed in this laboratory, it was observed t h a t in every instance, where stems and leaves of t h e same plant were separately analyzed, t h e total salt content, and similarly t h e potash content, in t h e stipe exceeded t h a t of t h e laminae. This observation is of particular importance since Dr. Cameron in a recent‘ review of the kelp work, and on t h e basis of the analytical d a t a then available for all stipes and all leaves, irrespective of the relations in individual plants, offered t h e opinion t h a t there were no characteristic differences in this respect. Table I V gives a list of such samples
1
