UNIVERSITY OF CALIFORNIA PUBLICATIONS COLLEGE OF AGRICULTURE AGRICULTURAL EXPERIMENT STATION BERKELEY, CALIFORNIA THE ECONOMIC VALUE OF PACIFIC COAST KELPS BY JOHN S. BURD BULLETIN No. 248 February, 1915 UNIVERSITY OF CALIFORNIA PRESS BERKELEY 1915 Benjamin Ide Wheeler, President of the University. EXPERIMENT STATION STAFF HEADS of divisions Thomas Forsyth Hunt, Director. Eugene W. Hilgard, Agricultural Chemistry (Emeritus). Edward J. Wickson, Horticulture. Herbert J. Webber, Director Citrus Experiment Station ; Plant Breeding. Hubert E. Van Norman, Vice-Director; Dairy Management. William A. Setchell, Botany. Myer E. Jaffa, Nutrition. Robert H. Loughridge, Soil Chemistry and Physics (Emeritus). Charles W. Woodworth, Entomology. Ralph E. Smith, Plant Pathology. J. Eliot Coit, Citriculture. John W. Gilmore, Agronomy. Charles F. Shaw, Soil Technology. John W. Gregg, Landscape Gardening and Floriculture. Frederic T. Bioletti, Viticulture and Enology. Warrbn T. Clarke, Agricultural Extension. John S. Burd, Agricultural Chemistry. Charles B. Lipman, Soil Chemistry and Bacteriology. Clarence M. Haring, Veterinary Science and Bacteriology. Ernest B. Babcock, Genetics. Gordon H. True, Animal Husbandry. Arnold V. Stubenrauch, Pomology. Fritz W. Woll, Animal Nutrition. James T. Barrett, Plant Pathology. William G. Hummel, Agricultural Education. Walter Mulford, Forestry. Frank Adams, Irrigation Practice. David N. Morgan, Assistant to the Director. Mrs. D. L. Bunnell, Librarian. DIVISION OF AGRICULTURAL CHEMISTRY John S. Burd. Paul L. Hibbard. Guy R. Stewart. Walter H. Dore. Dennis R. Hoagland. Harold E. Billings. THE ECONOMIC VALUE OF PACIFIC COAST KELPS BY JOHN S. BUKD' A great deal has been written in the past few years in reference to the commercial utilization of certain seaweeds or kelps growing in the waters of the Pacific Coast of North America. Several species, notable for their extraordinary size and commonly called "giant kelps," are to be found in scattered beds along the coast of California. Of these, the kelp known as Nereocystis Luetkeana occurs in occasional beds from the northern boundary of the state to Point Conception, the more abundant stands south of that point consisting largely of Macrocystis pyrifera. The present paper embodies a portion of the results obtained in this laboratory in an extensive series of studies on the chemistry of kelps. Some of these studies have more scientific interest than imme- diate practical importance. It is thought desirable to. reserve these latter for publication elsewhere and to consider here only such data and conclusions as have bearing on the commercial utilization of kelp. The results presented hereafter furnish the following general con- clusions : 1. The giant kelps contain potassium, iodine and nitrogen in amounts which will possibly justify commercial recovery. 2. Estimates of potash yields which are based on analyses of leaves and stems and do not take into account the larger proportion of leaf to stem in the growing plant are likely to be higher than can be expected in the average run of commercial recovery. 3. Exact determinations of the moisture content of the more com- mon of the giant kelps, here presented for the first time, show that weight for weight of fresh kelp Macrocystis pyrifera contains more of each important constituent than does Nereocystis Luetkeana. * Grateful acknowledgment is made to Professor Wm. A. Setchell of the University of California for helpful advice and assistance in collecting material; to Professor Frank M. McFarland of the Leland Stanford Junior University for the use of the Marine Biological Laboratory at Pacific Grove, and to Dr. W. W. McKay of the United States Marine Hospital Service for the use of wharf and drying sheds at San Diego. Acknowledgment is also made to the following members of this staff: G. E. Stewart, D. R. Hoagland, P. L. Hibbard, and W. H. Dore for the large amount of analytical work and other assistance involved in this studv. [183] 184 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION 4. The efflorescence of potash salts when kelps are slowly dried cannot be utilized to advantage in the commercial preparation of potash if a large yield of high grade salts is desired. 5. No technological difficulties are involved in preparing high grade potash salts and iodine from kelp, but exact costs of production can only be arrived at from data obtained on a large scale, as in actual factory practice. Apparently, however, extraordinary profits are not to be expected owing to the limited value of the product and the large amount of manipulation involved in the various methods of recovery. 6. Air-dried kelp will furnish a low grade potash fertilizer com- parable to kainit and containing in addition over 1 per cent of nitrogen and 50 per cent of organic matter capable of furnishing humus to the soil. 7. Objections to the use of dried kelp because of the presence of sodium and chlorine are untenable, because this material contains less sodium and chlorine than most of the commercial potash salts now being used and is but little inferior in this respect to the highest grades of muriate. The pioneer work of Balch 1 has shown that the giant kelps of the Pacific Coast, notably Macrocystis pyrifera, Pelagophycus porra, and Nereocystis Luetkeana, contain extraordinary quantities of potassium salts, largely in the form of potassium chloride. Turrentine 2 and his co-workers 3 have much enlarged our information in this field and presented valuable data as to the magnitude and variations in compo- sition of these and other species of marine algae. Based on this work, some interesting speculations have been published as to the possibility of founding an industry for the recovery of potash salts, iodine and other substances from kelp. The affirmative view 4 expressed by some of these has not been without contradiction, 5 and it is evident that further information is essential to a determination of the economic status of these curious plants. 1 On the Chemistry of Certain Algae of the Pacific Coast, by David M. Balch, Journal of Industrial and Engineering Chemistry, Vol. 1, No. 12, December, 1909. 2 The Composition of the Pacific Kelps, by J. AV. Turrentine, Journal of Industrial and Engineering Chemistry, Vol. 4, No. 6, June, 1912. 3 Analyses of Certain of the Pacific Coast Kelps, by E. G. Parker and J. R. Lindemuth, Journal of Industrial and Engineering Chemistry, Vol. 5, No. 4, April, 1913. * Potash from the Pacific Kelps, by F. K. Cameron, Journal of Industrial and Engineering Chemistry, Vol. 4, No. 2, February, 1912. » The Business Aspect of the Kelp Proposition, by F. P. Dewey, Journal of Industrial and Engineering Chemistry, Vol. 4, No. 4, April, 1912; Seaweed, Pot- ash and Iodine, a Criticism, by Henrik Knudsen, Journal of Industrial and Engineering Chemistry, Vol. 4, No. 8, August, 1912. Bulletin 248 PACIFIC COAST KELPS 185 A careful search of the literature indicates that the kelps from which the most is to be expected are those heretofore mentioned. In collecting material for this investigation stations were established at San Diego and Pacific Grove, as being both representative and con- venient. All photographing, measurement of dimensions and weights and preliminary drying of plants was conducted in the field. The observations of G. R. Stewart, who performed the field work, confirm those of other observers in that for Southern California the Macro- cystis pyrifera is the most abundant species, Pelagophycus porra being "only sparsely distributed over limited areas"; 6 while for the central Californian coast both Microcystis and Nereocystis occur in beds of considerable size. The botanical structure, habitat, method of reproduction, etc., have been described for all of the important species of kelp. 7 The photo- graphs herewith will perhaps illustrate better than further description Macrocystis pyrifera, complete plant of small size, holdfast attached to rock; sample taken off Point Loma at the mouth of San Diego Bay. (Photograph inverted to show habit of growth.) e The Kelps of the Southern Californian Coast, by W. C. Crandall, Fertilizer Resources of the United States, Senate Document No. 190, p. 211. 7 The Kelps of the United States and Alaska, by Wm. A. Setchell, Fertilizer Resources of the United States, Senate Document No. 190; Ecological and Economic Notes on Puget Sound Kelps, by George B. Rigg, Fertilizer Resources of the United States, Senate Document No. 190; The Kelps of the Central Cali- fornian Coast, by Frank M. McFarland, Fertilizer Resources of the United States, Senate Document No. 190. 186 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION the mode of growth and suggest some of the problems to be expected in harvesting the plants. It should be noted that all of these are attached to the bed of the ocean, usually on rocks, and that the entire plant is only harvested with difficulty. In Pelagophycas and Nereo- cystis the pneumatocyst (hollow bulb and adjacent portion of stem) tend to float and support the leaves near the surface of the water. In Pelagophycus porra, mature plant taken near Point Loma. Macrocystis, however, the arrangement of the leaves and relatively smaller bulbs with reference to the stems is such that a considerable proportion of the plant will always be beyond the depth of convenient harvesting. In this work the entire plant was harvested wherever possible and divided into so-called ' ' harvestable " and "non-harvest- able" portions. The former comprising all of that portion within twelve feet of the surface of the water, and the latter including the Bulletin 24S PACIFIC COAST KELPS 187 remainder of the plant, exclusive of holdfast, hapteres and adhering leaves. Further, the leaves (laminae) were carefully severed from the stemlike portions (stipes and pneumatocysts). Specimens were thus segregated into four portions, designated herein as harvestable leaves, harvestable stems, non-harvestable leaves and non-harvestable stems. The advantage of this procedure is that all data subsequently Nereocystis Luefkeana, complete old plant, taken off Point Cypress. obtained may be computed either to structurally distinct portions of the plant (leaves and stems) or to economically distinct portions (har- vestable and non-harvestable). RELATIVE PROPORTIONS OF LEAVES AND STEMS IN FRESH KELP Macrocystis pyrifera. — The samples of this species varied in weight (exclusive of holdfast) from 27 to 300 pounds, and 25 to 80 per cent of the entire plant was harvestable. In general, the greater percent- ages of harvestable portion are to be found in the larger plants. Of 188 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION ■JSBJ-piOq JO 9AIS oj ^ oo ^ uo t- -npxa juefd ajt^ua in co cm i-j n< o ui uoijaod 9[qu t-' h n r-i in in -}S9A.i«q jo ;uao .id£ th oo m ci ci ci ci t> nt co o suia;s . -. . . . 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Some of the estimates of the potash content of kelps have not taken into account the dispro- portion between the amounts of leaf and stem and have tended to assign values to the plants as a whole which they do not possess. Pelagophycus porta. — These plants varied in weight from 16 to 71 pounds, from 85 to 96 per cent of the entire plant being harvestable. Of the harvestable portion, from 57 to 73 per cent consisted of leaves. Nereocystis Laetkeana. — It was not found possible to harvest entire plants, but practically all was obtained in each case, the very small stipe anchoring the plant to the ocean bed being negligible and prob- ably not amounting to more than 1 or 2 per cent by weight. The maximum weight of any plant was 56 pounds at the season sampled (fall). Of the harvestable portion, from 50 to 77 per cent consisted of leaves. MAJOR ECONOMIC CONSTITUENTS OF KELP While a considerable number of partial analyses of the various parts and of entire kelps have been published heretofore, the methods of sampling and arrangement of data have not been such as to justify exact conclusions as to what is to be expected in the average run of commercial recovery. It is believed that the results here reported are free from this objection owing to the extreme precautions which were taken in sampling and to the fact that the initial weighings were made almost immediately after harvesting. Sampling of Kelps. — In this operation plants as drawn from the water were immediately covered with a tarpaulin to prevent evapor- ation. As soon as a sufficient number of specimens had been collected they were taken ashore, weighed, placed on a smooth floor under cover, measured and dissected into the four portions heretofore mentioned. The samples for analysis were obtained by cutting up each portion into small segments, mixing and withdrawing grab samples. Weighed portions of each sample were air dried, placed in glass containers, sealed and forwarded to the laboratory. Samples in practically all cases consisted of two kilograms of material. All were dried immedi- ately on reaching the laboratory, usually within two or three days after taking from the water. In no case was any putrefaction observed. Character of Data. — The results shown in Table 2 indicate that kelps, like land plants, are subject to variation in composition, and it may be contended that conclusions as to the average composition should be based on a very much larger number of specimens than represented Bulletin 248 PACIFIC COAST KELPS 191 ss2q &gM 4 tf *- o rH 4£ S^ •J *6 '53 oa w p o w u o o - h => co 4 4 -M-- ^ ?s 4 " "w " rH CM i-t rH rH O H © CI © 00 o o CO o o o 00 CI CO CO t- o CM co r " 1 CM H H CM CM H CO o CO o OS o CD O t- c o co 00 CO 00 00 00 Per ent o K.0 CM o" co 05 o" u «2°" 03 01 +a h rH 1-1 c .'— cfj ^H ,_i CM ,-H r-{ CO rH ° £ n o m OJ H CO 00 OJ co o rH 00 on *"J CM o T* rH CM 1— t lO co CM o CM u 1-1 ■*- co CM 00 co O 03 o co ^5 "* 05 o g o d OJ 00 CO © © OJ OJ OJ OJ q co' q 00 I- rH OJ 00 "^ CO iH OJ rH ,-H o CO OJ CO © ci C7Q 6 o £ n e3 CO o 0) > ft 'fi CO r 2 TO CO - o o M CD a rC 41 3 o CO fc t> Sz; a u s 4) 01 y. rH OJ 4J g r= 33 rH P>1 c3 CO > > cu t> 41 a ^ g^ 2 1> 4> 4> 4) 41 > ^ftaiftccft^ft CO "S O^,Oflp0pSHpr M t>4 rO 93 u ■S"E s ft co ft tu ft > CO g£ js d3 art OJ c3 co O O = .- fl P U s a s a rH i-H 0J 192 UNIVERSITY OF CALIFORNIA — EXPERIMENT STATION o £ Pug' *-■ i— i rH O iH rH O ,- -H O i-l CD ^_^ 3 c3 O .2 i»o 0) >i £ 1_ O V > bD ft— " £3 H OQ CD +3 N Pm cCm V. ° © C O +3 £ CD £_, rt."S CJC fcggW, O rH « O r-l ■<* 00 Tfl m iH TO iH CI U * 2 ^ T> £ £ fc £ > £ £ fc cfl „ cd ert crt 35 - Sh CD CD - >> >> — - - X ft r. - 03 i— ■ m ' ~* h cdgO' a> 'E += 'Z ~ 'Z >° ft ,2 ft ,2 ft "S S "S p c 5 g +=" -*S -w v< o > w > o , o O M o £ p c c £ -c S c o £ Z c ^ c •„ o y cd H cd £► CD p 5v > - f> 'S. cS .2 0) "5 eS '£ - cc 'Z _i CO ft » ft CD ft ft ft > — -O - rQ _ - - crt X cd CD & o C o O o o o i. c C y z JZ -fi cS X — § 5 — s Bulletin 248 PACIFIC COAST KELPS 193 fH ft © a c _, ,_, CO c ^tf a> -tf 1-1 w (M Cl Cl H Cl Cl C-l © rf © o a. o O o © 00 o O cc o LO o t- a. o o ft ft<< = §a o g ° Pm c^ o h °o Ah £Ph O rH Cl r-i 75 a 2 DO 3 -d * O - 1- ' - ^3 3 o C fl CD > II .. 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SH it OS -M C6 CO CO CO o C » o o <* o 21 £ ^ o CM O CI to "tf CO CM CQ Jz; O rH rH J ^ - i3 2 q o '5 o cc .i-T -d to cS c CD ft CD Bj 73 2 * -+- N -i_> N ^ CD ^ o | 'a s "So a 'So s .6 £ 9v60&C6fie3 £ H w H J 5 & 198 UNIVERSITY OF CALIFORNIA — EXPERIMENT STATION here. It seems to the writer, however, that there is sufficient uni- formity in most of the determinations to justify a fairly definite opinion as to the value of kelps from the data here presented, for while there is occasionally an aberrant figure the variation of most of the determinations from the average is not large. A remarkable uni- formity of the moisture content of analagous portions of plants is particularly noticeable. The summary on page 199 indicates the distribution of important constituents. The nitrogen, phosphoric acid and iodine content of the leaves is uniformly higher than that of the stems of the same species. The potash content of the stems is very much greater than that of the leaves, being nearly two to one in Macrocystis. The moisture content of the stems is invariably slightly greater than that of the leaves. The striking differences in composition between the leaves and stems of kelps might perhaps suggest the possibility of a segregation of leaves and stems in commercial production. To any one who handles these plants, however, it becomes evident that such segre- gation is out of the question, and it would seem therefore that estimates as to the value of the plants must be based upon the composition of the harvestable leaves and stems taken together rather than individ- ually. The data included in Table 4 are presented with this in mind. The figures for the non-harvestable portion are included merely because of their general interest, and it is not contended that they are of any particular value for our present purpose. Some inconsist- ency will perhaps be noticed, however, in that the figures for indi- vidual constituents in the harvestable portion are sometimes higher and sometimes lower than the corresponding figures for the non- harvestable portion. This is not a real inconsistency, but is due to differences in the relative amounts of leaf to stem, both in harvestable and non-harvestable parts. The summary of the average composition of the harvestable por- tions presented in the table on page 204 is of particular interest. Of the giant kelps, Macrocystis is the only one growing on both the southern and central Californian coast. The analyses indicate that the specimens from the north are distinctly superior in nitrogen, phosphoric acid and potash, but slightly inferior in iodine content. Comparing all plants on the water-free basis, it is evident that Pelagophycus is the most valuable species, in as much as it contains the most potash and iodine and comparable quantities of nitrogen and phosphoric acid. Nereocystis is next because of high potash, even though distinctly inferior in iodine content. At this point, however. Bulletin 248 PACIFIC COAST KELPS 199 M l_J M M ,_, i— » No. rep senl 07 Ol' CO co VT OS CO 5C OS CO - CD p K cd p" QTQ 3 !2j g g 1 K s fc»j g 2 Q CD >-* CD 5 CD i-i CD p P £ Ca p ca p P ca - ca P S3 p ca CD CD O O c O' 3 o £_> c o o o Pj o w K C /c O i CD g " QTQ O ^ hd -^v 3" CD ^t>g ^ o '- ^i « o cc ? o s |- s CO GO O to GO GO GO GO 00 GO g CO ^— ' GO ^^ M GO P GO pi OS rf- 2. C5 CO GO «o CO bi LO to bs *o bs Zfi C O GO -^ GO ^J f© ?o OX Ol os 6 CD CD Q o 5 - o f— i J— i [— i o I— i b to CO Lj d O CD o' «3 -^1 O GO «o to co ^4- Ol O or=3 y>% en c CD H P J-. o hd CD c^ hj W° CD — — sr - o o o o OS 'O o o o o o co i-> GO' 200 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION ^ Oh m ° a 03 O cfi z°, A, CO " o o U,& « c8 C3 P W to o» o> > at ■** m co fc?,W Cd M .faS «y w fl rt^ o a o> u ° C .2 ft o ■g c3 ftrQ o<° h •m 1 o o Pn o b- t- (M c C". o C3 CO CO 03 rt cc N "* O .-1 a to o °s • « OS O" «_ o O c3 C o o> - phSw 5 fiO Pngp;' !_ ©_(£ O) £ c£ S3 * °6" fc Sen m ci i-l c h ici o ci o o c o o ft X. o p fc ■r. £ a; - X o> > ce o> ^ t-t ~ Si cr « T- c a* .* « 3 £ o 5z; U g J- ~ Jh 0> £ 0) -© 0> Si h Si * Si v. ci £ W |-4 ft "■; o> d 2 55 g © ■ ft > ft p > p ■ p > o> ci "£ d oi d 2 £ o £ 2 fc cS . ft _ 03 « "Jj^ 03 o> 03 "£ 03 £ Si J S: £ Si « !j « M !; I p > p ■ p a u a S in 3 <« £ «Q 25 § W >i o ** o g '-S o "^ o O in >. F-i o o> ;>-. a> >> - o -^ oj c ^° ft -a 15 a * o o — < gco gw P^ggM CC — oc O 05 GO ci -f co M O ^ g:3"B r^ s-i oj w £ o o s'd ,d oj o CO o^ 1 ;l «H •_ ° 03 03 0-1 M U z 00 rH rH o ^ *-* u ° fl O £* 'oQ " oj o | s^ rQ ej H-i ^H M "S oj C^gW ej ^ « - <1 ■*> 03 He 08 H o* 1h O S«o 11 CD S3 o J2 3 - <=> O - ft,o 63 S-sJg s « as o u ££ 00 05 t- a co" s os" O Ci 3 ft 3 o r" o o oj O £ O £ 3 £ o y, — ! ^ ; ft ft 03 S3 03 03 » (>. ;>> 0) 63 ft > Ph > ft ft > T3 03 03 ,|ij o .rt cS "K ^ 17! ^a % fl m -2 >> 0J ^ OJ OJ OJ 0) O '- 03 3 O a o ■g o 3 .2 — ' .2 CO .~ I- .X Z 2 £ 2 Z «w 03 t-> e3 *j -r -w o .S « ,S « o cj fn o si ? --G «, ^ ° o ° ,» ft^ 03" ® 08 ft £ ft £ ft 2 W) tJ M « M - 03 C e; C rt C ^-. tu — : qj — eg Ol CO OJ P4 PM pn -J-J bB +; c8 T) 03 S a bJD h if, •- >■ > CO 01 - u - 0J hJ 0J J i, ft -c 2 6X E >. iM CM -* 0J QO Oi OS tJ T3 73 •„ 2 fl f3 C o - 03 03 03 202 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION Vh o ."2 ^ co ^ 'o fc-c I 5 ' ro 05 ^h i-J 10 c-i r-i O rH C z n-r c = * ill ;3 s -o, c Pm S^ S sO gfc in LO OJ oc CM -r OS CM OS OJ CM 05 OJ 5^3 - 03 o ta O O P4 «M'' ^l£ ^ lO CM LO CO CO w oa 00 CM H CM TH C lo c CO C t~ o o c 55 O £ p S3 03 ■— - - o 5 « p c £ c £ c £ ~ £ o ci a CD >i >-. 4) >* .C P »>»>&>&> PH'ft^ft'jGJc^pJp^Pi-^ CD >» CD >» CD ^ CD 2 CD ct; co O co OS CO O CO CO CO CO CO •- CO SO ,P CD - CO o o P CD co >. o o — co >> K O P. CD CO >. - CD - CO O - CD CO CD U CO P. - ft CD ft CD o o c C CD E CD CD CD CD CD OJ 00 Gi O iH CM CO LO CM LO -r r=s Bulletin 248 PACIFIC COAST KELPS 203 o 10 %2 w © o u,a e3 ? W"K ^3 °o 0> > r?-s ^Q, "Hi: z ^'o ^ fW Gr3 (J - T3 U u -1 "£ *> "S s JH ft §.2 Is n ° ?> ti S||8 o o 3sp £"£ S ©^ •- ,0 to •- re © S !t!(H. a go o* Snd !*£ ^ © cc to o uo io lo n S_i°G -h rn o o ^h o o o o CO © -g S ° o o O O O O O C rH C ^;o .43—. y-i CO t- lO rH OS CO CO CO (O Ifi ScV C3 t- to co co o co m w n t hSi4 - * H rH rH H rH H - H • ^■Srf '° =o t- t- t~ & - 1 t~ cm co i< © « ( %. O O O O O O CM rH (M rH r-i ^ ©P^" < ° 2 C N CO C5 C5 LO lO CO CI kO CM 1" > -*f +j © rH rH iH rH -r-i rH -f ■*+< ^ Li L: •Is m ss^ CO -t Ci OS t- m c eo X CO o t- 00 o +a o T > © ^ ffi ~£ H -5 < -4, C Eh c£ C cC "■£ -*" c c PH+" . O * Pm flrd b5o! *> ■£ z © PM ££ W> C CM cm' cm' rrj .„' r~j U © ■z a; © CO © pa X 08 © ,- — - - h1 = h-1 c l_l P3 r-1 £ © *jj © +^ - CO 8j CO « CO as CO " CO - z. © ■- to s o P. © CO c © co o o © to © lie © © eg Tr, © © ft R = © a © = © © © = © © © © © © © © © QJ © if © © O S C rS 204 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION i-H O o o r- CM CO to r-i o GO o ^H ^ -*i GO (M OS CD 3 ft ft. S3 _ ■H CO no *£ rt CD 'bJD 03 0) O ^ fcl '3 cu > CO" PI g =3 bJO S3 ft s £ CO O f- 1 O CD 03 s ft O ft ft ca ft 0) 5 > ts £ -r fl ci fl co ^ a " > © S © fH CO t- © ft 3 © « ■!) (12 Bulletin 248 PACIFIC COAST KELPS 205 it should be accentuated that the cost of harvesting and drying- fresh kelp are important economic factors in the production of dried kelp, so that estimates of the relative value of these materials should be based on the fresh material rather than the dried. On this basis, Pelagophycus continues to hold first place, but Nereocystis drops below Macrocystis, being distinctly inferior to the latter in every respect. To obtain one ton of water-free Nereocystis would require the har- vesting and drying of 11.9 tons of the fresh plants as against 7 A tons of Macrocystis. The superiority of dried Nereocystis over dried Macrocystis is not sufficient to overcome the handicap of the large amount of water in the fresh material. In view of the comparative sparseness of Pelagophycus and the inferiority of Nereocystis it would seem that Macrocystis would be the most important source of raw material if it is found practicable to utilize kelps for manufacturing purposes. RECOVERY OF POTASH AND IODINE Leaving out of consideration, for the present, the possibility of obtaining economically valuable substances from the organic (non- salt) portions of kelp, it is evident that the separation of potash and iodine are of the first importance. It has been shown elsewhere 8 that when kelps are dried slowly there is always a tendency to form a crust or coating (efflorescence) on the surface of the plant. In some cases this apparently amounts to a considerable proportion of the salts present. The table on page 206 indicates what is to be expected in this respect. In the case of Macrocystis leaves only a slight efflorescence occurred and the salts formed a thin, closely adherent layer, preventing separ- ation. The percentages of salts effloresced by the Macrocystis stems, Nereocystis leaves and Nereocystis stems Avere respectively 15, 24 and 43. These contained no iodine, but carried extraordinary percentages of potash. If it is borne in mind that muriate of potash contains 63.1 per cent of potash (K 2 0), it appears that the potash in the effloresced salts (60.85 to 61.92 per cent) represents muriate of a high degree of purity (over 95 per cent). In spite of this, the fact that the potash effloresced never exceeds 58.7 per cent of the total present in an} T sample (see Nereocystis stems) indicates that further extraction of the residual kelp presumably by water would be necessary, if the remaining potash salts are to be separated and iodine recovered. If s On the Chemistry of Certain Algae of the Pacific Coast, by David M. Balch, Journal of Industrial and Engineering Chemistry, Vol. 1, No. 12, December, 1909. 206 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION o o o © © d ,G - CO OS t^ c3 O Ph °" d i—i 06 CO oc 10 c Tji CM LO CM 00 GC w Phs§ O TJH CO -1 ,— fe *= fi^ O L- LO CM O CM 00 OS CO cc i CD J>s '-£ CD O CD ft c3 C c3 O CD CD O CD CD S S^ £ £ Oj ,__, CM 1— 1 CM g d d r- 1 r-.' H CM CM CM CM Bulletin 248 PACIFIC COAST KELPS 207 the highly absorbent tissues of the plants have to be again saturated with water it would appear that the preliminary drying, incident to causing efflorescence to occur, would be an unnecessary step. Such a step would only be justified in case the subsequent treatment of the residual kelp is by a dry process, and any dry process would involve either the loss of organic matter, as in burning to obtain kelp ash, or loss of iodine if the residue is merely dried, ground and used as a low grade potash fertilizer. In attempts to separate a complex mixture of colloidal and crystal- lizable material such as the tissues of kelp the method of water ex- traction is the first to suggest itself. The possibilities of this method are indicated by a study of the table on page 208. Potash. — A large proportion of the potash (70.1-84.8 per cent) was extracted in every case from the fresh kelp, and still more (90.6- 95.4 per cent) from the dried and ground material. Iodine. — In all cases but one most of the iodine was extra ctable from fresh kelp and the yield from the dried and ground kelp was materially greater in five out of the six samples. Organic Matter. — Considerable quantities of organic matter appear in the extract from fresh kelp and these are greatly increased when the dried and ground kelp is used. There is evidently no difficulty in dissolving in water the potash and iodine constituent in kelp. "When the kelp has been previously dried and ground the extraction is, as might be expected, much more efficient. Doubtless if the method of multiple extraction were used practically all of the potash and iodine would be removed from the tissues. Unfortunately large percentages of organic matter also dis- solve whenever extraction of salts is at all efficient. These discolor the solutions and seriously interfere with the subsequent crystallization of the potash salts. Salts obtained from such solutions are always dark in color and difficult to separate. To secure clean, white potash salts either by fractional crystallization or by complete evaporation of the solutions is impossible without burning off the organic matter present. The salts remaining after incineration have a fairly high purity, corresponding to 60-80 per cent muriate of potash. For Macrocystis they would contain about 41 per cent of potash equivalent to muriate of 64 per cent purity. The procedure involves a loss of one-sixth to one-third of the organic matter of kelp and leaves the remaining organic matter (practically free from potash and iodine) saturated with water. This residuum represents approximately one hundred pounds of organic matter and three pounds of nitrogen for every ton of fresh kelp. Its utilization will necessarily depend upon 208 UNIVERSITY OF CALIFORNIA — EXPERIMENT STATION £ £ X " CO 05 q b- eo q CI OS q ci — TO CO CO co LO rH 35 H; h- PC c IX) 'X' 30 b- & SO cm Cl GO I- co DO 3 CO L- c CM 05 kC c co b- .2 M m rH — CM 00 CO CI CO — CM CD 3 Cfl 35 TJH -h c. CI o OS O •* l> 00 H Eh to ^ Tti H* Tji hh fcO t> CO H M CO OS CO OO (O H » N GO CO CO C5 O CO O O O O CO o rt £'-§ -t- in b- OS CO IT Cl '"I CM CO . Cl lO 35 o b- 10 Cl H" Cl CO — CO r-J iq CO 05* H4* rH © tH b" LO 35 CO CO "* CO b- lO b- CO* CO CO CO ^ CO CO 35 CM b- CO '- rl ^i b O C5 © M 35 35 LO IT © Cl rH 35 CO rH 35 CO CO CO 00 6" CC CD rH b- 35 lO rH — i b- CO 55 LO CO cc b- CO CO L^ rH CT r-i rH _ CXI © TH "cH t>- 35 n co' co* © hh° t-' id ^ H CM N (M H CM o3 42 o"aS t> CO O0 CM CO 35 CO b* LO CM 35 rH ^ ^ lO lO "* o CO H^ CO CO b- O C5 CO CO H* 35* r-i' CO CO CO CO CO CO PPh 00 lO b- CO rH P* 35 CO b- CM •<*• CO „ HH CM CO CO CO CO O tH W b CO CO CO* A N b- 00 b- b- b- 35 CO O b- CM rH H^ Jz; N CD* ■*' H O0 CO* CM CM CM CO i— I CM CO rJH CO CO rH -tf co id d ^' cm' id 35 35 35 35 35 35 -g~ co co £ 3 35 35 co co iq co' CO cm" q CO CO ^ 35 -tf CO CO rH 35* 35* CO* T^ CO CM "CM CO CO co m S2 LO CO 00 LO CD* l>* H* rH CO CO CO CO CM CO CO CM CM CO >y CO* CD 35* b* CO* CO ^ CO CM rH CM r-i CM rH O rH rH CO 35 S oo CO LO CM CM LO O 0"3 O i-* LO* CO* CD LO* EH oa oo 00 co co b- b- oq b- cq © co lo co id rH co' cd ©* CM rH rH r-l CM CM 02 o £ t cu c3 CO r— I CO CO CO CO r>» >* CO CO o o a> co CO CO ^J P •"•HOC) CO 02 ^» £» CD ri rt ^ Jz; ^ g ^ p^ Ph 0) s_i *aja rH CM rH CM r-J CM S g id lO 6 CO b b CSS Tf Tf Tjf ^ •* ^ &c - TO .A cd C ■— cp G. r^3 TO O b£ o ^= CO CCS H-» > CD -= ? ^ b£ CD '5 5£ ^ CD +3 ^ IS c *"^H ^^ £ rd CD * M rH "tO CD CD CT+-i CD rH "3 X 3 ® So S Si? rS Oj " co > H Scs cu ^ "** o r? a - :: - o o o o Mb() 2 2 S S SS be futile. Estimates of the value of the product, however, are useful as indicating the obvious limitations to which commercial production will be confined. The maximum value of the constituents obtainable from kelp are indicated in the following table : Composition of Kelp (Microcystis) Maximum Recovery Pounds , A -^ Price per Total Percentage per ton Per cent Pounds pound value Moisture 86.41 1728.2 Nitrogen 19 3.8 80 3.04 15c $0.46 Potash 1.82 36.4 100 36.4 3%c $1.36 Iodine 03 .6 80 .48 $3.00 $1.44 The commodities obtainable are iodine, high grade muriate of potash and fertilizer filler comprising the bulk of the organic matter of kelp freed from all soluble constituents (salts) and carrying 8 per cent of nitrogen. It is not believed commercially possible to manufacture sulfate of ammonia from kelp, because it has been shown by Turrentine 12 that in the destructive distillation of kelps a large proportion of the nitrogen is evolved as such and not as ammonia. Again Hoagland has shown the same thing and, furthermore, gives data 13 indicating 12 Note on the Distillation of Kelp, by J. W. Turrentine, Proceedings of the Eighth International Congress of Applied Chemistry, Vol. 15, p. 313. 13 Unpublished manuscript, by D. E. Hoagland. Bulletin 248 PACIFIC COAST KELPS 211 that there are no special by-products from the destructive distillation of such a character as to justify the expectation that a part of the cost of the necessary distillation could be defrayed by profits from such other products. The commercial value of the potash is unques- tionably equal to that of the potash obtainable from high grade muriate of potash, and the market quotation for this commodity is used in the above estimate. The commercial value of the nitrogen is taken at approximately the cost of nitrogen in nitrate of soda. The third commodity, iodine, is taken to have a value equal to that of recent market quotations for this substance as obtained from other sources. It has been pointed out that it is hardly reasonable to expect that the iodine price will be maintained in the case of a large production from kelp, so that current market prices unquestionably represent the maximum value which could be expected from this source. It will be seen from the figures given that the value of the various commodities, assuming the maximum recovery of each constituent is $3.26 per ton of wet kelp. If we assume that market conditions will not permit of the sale of iodine in competition with that obtained from other sources of supply, the maximum value of the remaining constituents is $1.82 per ton of wet kelp. The data heretofore given indicate that the production of manu- factured products from kelp is unquestionably a relatively compli- cated process. The estimates show that the gross income derivable from the various products is not great. It would seem, therefore, that expectations of enormous profits from the development of a kelp industry are not likely to be realized. On the other hand, the data do not exclude the possibility of some profit. DRIED AND GROUND KELP AS A COMMERCIAL PRODUCT The remaining procedure for the manufacture of kelp which would seem to offer commercial opportunity is the drying and grinding of kelp and selling it as such. The manipulation and equipment involved is of the simplest character and the method as a whole would seem to offer fair opportunities for success. The objections urged are that it involves the loss of iodine and the possibility that the product obtained will be of less commercial value per unit of potash and nitrogen than that of high grade manufactured products. Further- more, that there is a prejudice against this material on account of the fact that it contains a certain proportion of sodium chloride. Finally, that manufactured products would yield a higher price and 212 UNIVERSITY OF CALIFORNIA EXPERIMENT STATION lower freight rate per unit of potash than does dried kelp. Of all of the objections urged, the last, namely, that the cost of transpor- tation of high grade manufactured products would be less than that of the comparatively low grade dried kelp would appear to be the only valid one. This latter objection will disappear if the cost of manufacturing the high grade product is sufficiently great to offset the benefit of a low freight rate. The difficulties of making exact estimates of the cost of manufacturing high grade products have been set forth. It would seem, however, that no such comparisons are necessary, provided the low grade material actually has sufficient value as compared with commodities of similar potash content carrying equal freight rates. It is frequently stated that the value of dried and ground kelp will be materially diminished because of its content of sodium chloride, and attempts have been made to remove this salt from the kelp by washing with water. No such method is practicable because of the large quantities of potassium chloride relatively to sodium chloride in the principal varieties of kelp. The only possible method of separ- atum the sodium salts from the potassium salts is that of fractional crystallization heretofore outlined. All attempts to wash sodium chloride out of either the fresh or dried and ground kelp will simply result in the removal of both potassium and sodium salts in amounts commensurate with their solubilities and relative quantities. The following table of analyses by P. L. Hibbard of this laboratory indicates the composition of the various salts found in kelp. TABLE 8 Percentage Composition of the Ash of the Harvestable Portions of Macrocystis Pyrifera, Nereocystis Luetkeana, and Pelagophycus Porra Macrocystis pyrifera Nereocystis Luetkeana Pelagophycus porra Ca 4.96 2.10 2.09 Mg 2.24 1.55 1.71 Na 10.52 11.05 8.63 K 29.46 32.66 34.73 FeX^ A1 2 CU .43 .17 .26 CI 34.93 40.89 40.83 so 4 7.92 4.63 4.84 co 3 4.44 3.10 1.66 P0 4 2.30 97.20 1.91 2.18 98.06 96.93 rotal ash in water- free materia], 35.62 50.57 52.66 Bulletin 248 PACIFIC COAST KELPS 213 o Q CO hj & < =5 pi tr 1 32 B T. — 1 > 33 QQ 5' H- o Hs o D Hs H Ha ►1 £r* pa H m H go" r-t- 3' 3_ c - cd S. pi CD CD CD pi 1—1 3 CD - o O O O 5^ CO Ms Ha Hs Ha O Ha Ha K 5- CO 3 30 O 5 5 B3 3 3 pi DO — o TO. TQ S3 B3 p £ pj 3 pa QQ w it: 5 CD 71 CD 30 30 — CD CD K" n' CD b - pr C W - ** 4- so 01 en Ul r. 00 LO 30 O O ^1 3 ~ OS ~i M O "-<| — OS LO f_» bo to -1 bo so CO 5 O O OS SO rf*. tf- 1—1 00 OX 01 53 C5 O 00 01 CO M © rfx p ;c p 10 l-t» Ct>" M ^ ^ -1 M 'tO bi CO tfx ox OX -1 00 CD O to SO 01 O 2 Ha O p- |> •=51 on? O rfx CO Li -i ox rf*. -1 H_ O ;0 QO oc 10 O — * © to — i rfs. OS 5" g ^ CO ~1 bi bl to Lc OS be "en '-] h-i ^ -1 3_ g OO rfx 00 ZJ\ C+- w Pi fo H fa n ^— > B? 3 rf> M — 1 rf*. — co to to 5' P^ > CO pi -1 ^ 1^" to pi _— 10 — to-- o3 pi p vf r 1 co bo '+- LO b J— 1 bo CO OS OS b b b pf co . ^J Ol M — 3 g B k g O O O 2 05 J -1 i-3 **■ H^ [0 to rfx CO co B' > LO O M CO Ox pi 00 01 10 to p bo bo -1 OS to b OS cog- o3 pj M P M J— 1 z O H* a 3 2 CO 1-1 M M CO M LO M — 3 c 5 LO O M Ox ^ be ^i os LO 4^ LO M tO bO g' ffk bl O CO *tfx bo S-- CO OS 00 00 to p p • to M CO 1 ■- to ox i •^ so 00 M M bi so '^ bi f-» bi : b bo rfx LO w QO tO rfx bo co rfi. ox to £*. CO LO p to tO p M bi bo bo ^1 b rf^ 'co bi 214 UNIVERSITY OF CALIFORNIA— EXPERIMENT STATION The ions here present which might tend to lower the agricultural and hence the commercial value of dried and ground kelp are limited to sodium and chlorine, but these same ions are to be found in large quantities in all of the high grade commercial potash salts with the exception of sulfate of potash. Relative Potassium, Sodium and Chlorine Context of Various Commodities Potassium Sodium Chlorine Microcystis pyrifera 100 35.7 118.6 Nereocystis Luetkeana '. 100 33.8 125.2 Pelagophycus porra 100 24.8 117.6 Muriate of potash, 90-95% basis 100 5.8 99.9 Muriate of potash, 80-85% basis 100 13.0 111.2 Muriate of potash, 70-75% basis 100 21.5 123.2 Potash manure salts, 20% minimum 100 90.5 248.3 Potash manure salts, 30% minimum 100 40.4 165.2 Kainit 100 128.5 294.2 Carnallit 100 108.0 454.7 Sylvinit 100 154.3 337.8 It is at once evident that few of the commercial salts are in any way superior to dried and ground kelp in the matter of sodium and chlorine content. Of all of these commodities, it is seen that only the 90-95 per cent and the 80-85 per cent muriate are appreciably superior to kelps in that they are lower in their relative sodium content. Muriate of potash, 70-75 per cent, has a potassium-sodium ratio of the same order of magnitude as that of kelp, and all of the lower grades of commercial salts are distinctly inferior in this respect. The results of the comparison when we turn to chlorine are even more striking. The ratio of chlorine to potassium in the highest grade of muriate is of the same order of magnitude as that of kelp, and all of the other commercial potash salts contain a larger proportion of chlorine to potassium. About one-half million tons of kainit are used in this country annually, to say nothing of the other grades of potassium salts containing sodium and chlorine. Any objection to the use of kelp on the basis of sodium and chlorine could certainly be urged with more force against the use of kainit and with almost equal force against the use of the ordinary grades of muriate. In so far as its sodium and chlorine content is concerned, dried and ground kelp, therefore, is superior in agricultural value to the potassium salt, which is most largely used in this country. If we abandon the comparative method and consider the chlorine content of kelp on its own merits, it may be stated that there is little evidence to show that potash in the form of muriate is inferior to other salts as a potash fertilizer when applied to crops in general, and data is also available tending to show that the same thing is true in Bulletin 248 PACIFIC COAST KELPS 215 the case of potatoes, which have been largely cited as a crop which is injured by the presence of chlorine. 14 Evidently the only condition under which danger is to be anticipated from the use of kelp as a potash fertilizer is on those soils the soluble salt content of which already approaches the toxic limit. All such cases must of course be considered on their merits. The agricultural value per unit of the potash contained in dried and ground kelp must be considered to be superior to that of most of the commercial potash salts and but little inferior to those of the highest potash content. Considered strictly from the plant food content, the following figures are of interest as indicating what is to be expected from kelp in various conditions of moisture content : Average Composition of Harvestable Kelp (Microcystis Pyrifera) Percentage of Percentage Percentage Percentage Phosphoric of of of Acid Potash Moisture Nitrogen (P 2 °5) ( K 2 °) Fresh 86.41 .19 .10 1.82 Water free 1.41 .75 13.63 Air dry 16.0 1.18 .63 11.45 The air-dried kelp should contain on the average about 16 per cent of moisture. This is of course subject to fluctuations in the hygro- scopic content of the atmosphere. Under highly unfavorable condi- tions in damp weather when the dry kelp is spread out it may absorb as high as 30 per cent of moisture, but loses this again as soon as the moisture content of the atmosphere falls. Air-dried kelp, therefore, contains approximately the same amount of potash as kainit, slightly more than 1 per cent of nitrogen, and about .6 of 1 per cent of phosphoric acid. Little is to be expected from kelp in so far as its phosphoric acid content is concerned. The value and limitations of the nitrogen have been studied by Stewart of this laboratory and reported elsewhere. 15 In view of all existing information, it seems fair to assign a commercial value to the constituents of kelp of about $3 per unit for nitrogen and 75 cents per unit for potash. The com- mercial value of air-dried kelp, then, should approximate $12 per ton arid justify additional charges for freight at least equal to transpor- tation charges on kainit. This requires that approximately 6.2 tons of fresh Macrocystis be harvested to furnish one ton of kelp worth approximately $12. Where this can be done at a profit the utilization of kelp will be a commercial success. I* The Use and Value of Seaweed as Manure, by James Hendrick, Trans- actions of the Highland and Agricultural Society of Scotland, 5th Series, Vol. 10. is Studies on the Availability of the Nitrogen in Pacific Coast Kelps, by G. R. Stewart, unpublished manuscript. STATION PUBLICATIONS AVAILABLE FOR DISTRIBUTION REPORTS 1897. Resistant Vines, their Selection, Adaptation, and Grafting. Appendix to Yiticultural Report for 1896. 1902. Report of the Agricultural Experiment Station for 1898-1901. 1903. Report of the Agricultural Experiment Station for 1901-03. 1904. Twenty-second Report of the Agricultural Experiment Station for 1903-04. 1914. Report of the College of Agriculture and the Agricultural Experiment Station, Julv, 1913-June, 1914. BULLETINS No. 116. 168. 169. 170. 174. 177. 178. 182. 183. 184. 185. 186. 195. 197. 198. 203. 207. No. 46. 62. 65. 68. 69. 70. 75. 76. 79. 80. 82. 83. 84. 87. The California Vine Hopper. Observations on Some Vine Diseases in Sonoma County. Tolerance of the Sugar Beet for Alkali. Studies in Grasshopper Control. A New Wine-Cooling Machine. A New Method of Making Dry Red Wine. Mosquito Control. Analysis of Paris Green and Lead Arsenate. Proposed Insecticide Law. The California Tussock-moth. Report of the Plant Pathologist to July 1, 1906. Report of Progress in Cereal Investi- gations. Odium of the Vine. The California Grape Root-worm. Grape Culture in California ; Im- proved Methods of Wine-making; Yeast from California Grapes. The Grape Leaf-Hopper. Report of the Plant Pathologist to July 1, 1909. The Control of the Argentine Ant. No. 208. The Late Blight of Celery. 211. How to Increase the Yield of Wheat in California. 212. California White Wheats. 213. The Principles of Wine-making. 215. The House Fly in its Relation to Public Health. 216. A Progress Report upon Soil and Climatic Factors Influencing the Composition of Wheat. 224. The Production of the Lima Bean. 225. Tolerance of Eucalyptus for Alkali. 227. Grape Vinegar. 230. Enological Investigations. 234. Red Spiders and Mites of Citrus Trees. 240. Commercial Fertilizers. 241. Vine Pruning in California. Part I. 242. Humus in California Soils. 243. The Intradermal Test for Tuber- culosis in Cattle and Hogs. 244. Utilization of Waste Oranges. 245. Commercial Fertilizers. 246. Vine Pruning in California, Part II. 247. Irrigation and Measuring Devices. CIRCULARS No. OS. 100. 101. 102. Suggestions for Garden Work in Cali- fornia Schools. The School Garden in the Course of Study. The California Insecticide Law. The Prevention of Hog Cholera. The Extermination of Morning-Glory. Observation of the Status of Corn Growing in California. A New Leakage Gauge. Hot Room Callusing. List of Insecticide Dealers. Boys' and Girls' Clubs. The Common Ground Squirrels of California. Potato Growing Clubs. Mushrooms and Toadstools. Alfalfa. Advantages to the Breeder in Test- ing his Pure-bred Cows for the Register of Merit. Disinfection on the Farm. Infectious Abortion and Sterility in Cows. Plowing and Cultivating Soils in California. Pruning Frosted Citrus Trees. Codling Moth Control in the Sacra- mento Valley. The Woolly Aphis. 106. Directions for using Anti-Hog-Cholera Serum. 107. Spraying Walnut Trees for Blight and Aphis Control. 108. Grape Juice. 109. Community or Local Extension Work by the High School Agricultural Department. 110. Green Manuring in California. 111. The Use of Lime and Gypsum on California Soils. 112. The County Farm Adviser. 113. Announcement of Correspondence Courses in Agriculture. 114. Increasing the Duty of Water. 115. Grafting Vinifera Vineyards. 116. Silk Worm Experiments. 117. The Selection and Cost of a Small Pumping Plant. 118. The County Farm Bureau. 119. Winery Directions. 120. Potato Growing in the San Joaquin and Sacramento Deltas of Cali- fornia. 121. Some Things the Prospective Settler Should Know. 122. The Management of Strawberry Soils in Pajaro Valley. 123. Fundamental Principles of Co-opera- tion in Agriculture.