Kelp derived feeds containing sequestered trace minerals
United States Patent I 91 1111 3,876,810  
 Carbonniere 1 1 Apr. 8, 1975 [54] KELP DERIVED FEEDS CONTAINING 3.403.471 10/1968 Clement 4711.4  
 SEQUESTERED TRACE MINERALS John G. Carbonniere, Gardena. Calif.  
 Assignee: Ocean Labs Inc.. San Pedro. Calif.  
 Filed: Sept. 24, 1970 Appl. No.: 75,213  
 Inventor:  
 US. Cl. 426/74; 426/210. 426/220; 426/271; 426/807 Int. Cl A23k 1/175 Field of Search 99/2. 14. 2 R, 2 LD. 2 ND; 47/l.4; 426/74, 210. 218. 220, 271. 807  
 References Cited UNITED STATES PATENTS 12/1955 Myers 47/l.4 11/1961) Cardon 99/2 8/1968 Miller 99/2 OTHER PUBLICATIONS Scientific American. Weiss. Vol. 187, No. 6, December 1952. page l5. l6 and 17.  
 Algal Culture by Burlew, Carnegie Inst. of Washington Publication 600. 1953, pages 90, 92. 94. 95. 98. 100. 101. 214. 215. 217. 218.  
 Primary Examiner-Norman Yudkoff Assistant Examiner-Curtis P. Ribando Attorney. Agent. or Firm-White and Haefliger 6 Claims, 2 Drawing Figures 4 Fess/(Lu cz/r Mae-20m 77: pwe/psep 6 c/mP E/e C MILL 0- HOLDING rp/wa E KELP 1 M/Naem. BLEND filik c7 MINER/7L 44/):  
 d- ,1 I l/OLDl/VG Tau/e 1 DEA/SDRDTO/Q 2- MILL.  
 5 SC/EEE/V 4 PKG.  
 5- lNVE/VTOQV KELP DERIVED FEEDS CONTAINING SEQUESTERED TRACE MINERALS SUMMARY OF THE INVENTION This invention relates to feeds produced from freshly cut raw Macrocystis pyrifera (giant brown kelp), typically as harvested from Pacific ocean waters, the specific compositions of which may vary depending upon particular ocean sources, e.g. Pacific vs. Atlantic. Hereinafter this specie will be referred to simply as kelp.  
  The invention has for its general object to produce a kelp-derived product containing added trace minerals which, along with natural values in the kelp, become sequestered in the product by reason of certain peculiar properties of the kelp. The latter contains a high level of polysaccharides by virtue of which, along with other components of the kelp, give the latter unique properties for the sequestration and stabilization of natural and added trace mineral values productive of high quality feeds for consumption as by ruminants, swine and poultry.  
  Procedurally the product results from converting rapidly the freshly cut kelp (which ferments readily and therefore loses effectiveness), into slurry of pulp or paste-like consistency, adding to the slurry trade mineral sources, and dehydrating and grinding the resulting mixture.  
  Trace minerals are prepared by the addition of water soluble sulfates of the group consisting of zinc sulfate, manganese sulfate, ferrous sulfate, copper sulfate, cobalt sulfate and ethylene diamine dihydriodide (as iodine source) in quantities and proportions subject to variation according to the desired trace mineral content in the end product. That content may take into consideration components of the kelp itself such as potassium chloride, sodium chloride, magnesium sulfate, iodine and added or natural vitamins. The mineral solution is introduced to the kelp slurry in the proper predetermined proportions, uniformly mixed and then fed into a suitable dehydrator, preferably under conditions of controlled flow, heat and time.  
  When adequate moisture has been removed the product which is in small flake form as removed from the dehydrator, is passed through a mill or grinder and then screened and bagged. The product can be made available in regular and extra fine grinds, the latter being useable to advantage in liquid application because it will readily go into and remain in suspension.  
  The product is characterized by virtue of its polysaccharide content in its capacity to surround and isolate the metallic ions. Sequestration and derivation of added mineral elements and iodine results from reaction of the ionized mineral sulfate salts and ethylene diamine dihydriodide (EDDI) with the polysaccharides in the kelp. The water soluble product having a pH in water solution in the range of about 3.5 to 5.0, releases its metallic ions when digested by enzymatic action or exposure to the level of acidity existing in the consuming animal or fowl. The sequestering process appears to be physical rather than chemical in that the inorganic metallic cations and even the anions in the trace minerals are separated in their consumable condition.  
  Analysis of the product may vary widely as to mineral content so long as the kelp content is sufficient to sequester the total minerals added. Minimum kelp content may range from as low as about e.g. as in a swine formulation, with the kelp content for e.g. ruminant formulas, ranging as high as The details of an illustrative method for making the product will be explained by reference to the accompanying drawing.  
 BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is a diagrammatic illustration of the process in flow sheet form; and  
  FIG. 2 is a fragmentary sectional enlargement showing an illustrative dehydrator system.  
  In reference first to FIG. 1, the freshly harvested kelp enters the system at tank A from which, with or without the addition of water, the kelp passes successively through chopper B and mill C both of which may be of any suitable or conventional type. The resulting slurry enters holding tank D from which the slurry flows to a suitable blender E for admixture with the mineral sulfate mixture.  
  The latter is prepared by the formation in any suit able sequences of dilute aqueous sulfate solutions with ethylene diamine dihydriodide in mixers a, b and c followed by delivery of the combined sulfate solutions to holding tanks d and e from which the mineral solution passes to the blender E for intimate and uniform mixing with the kelp slurry.  
  The admixture then enters the dehydrator 1 wherein its moisture content is reduced to a predetermined amount generally in the range of 10 to 4 weight percent of the final product, and as a specific example to about 8% moisture content. Broadly contemplated is the use of any suitable dehydrator, typically as depicted in FIG. 2. Here the slurry feed is shown to be introduced through line 10 into a revolving tube or drum ll equipped with lifting fins 12 to maintain the slurry in a state of agitation and exposure as it undergoes progressive dehydration. Air is supplied from blower 13 through ducts I4 and 15 into chamber 16 receiving combustible gas from jet 17 so that the entering air and combustion gases are premixed to a temperature of about 300350F before entering the dehydrator drum 1] and prior to admixture with the slurry being discharged into the drum from line 12. The dehydrator may have any suitable known means for separately withdrawing the hot and heated gas and air mixture from the discharge and of the drum and for passage of the dehydrated product to suitable disintegration means such as successively a grinding mill 2, screening facility 3 and packaging stage 4 from which the screened product or products goes to inventory 5.  
  The selection and proportion of the added elements may vary and somewhat widely depending upon the intended use of the feed product. Thus the individual element contents expressed as mineral elements in the product may range within about the following limits:  
 zinc 20 to 0 percent manganese l S to 0 percent iron I 2 to 0 percent copper l 3 to 0 percent cobalt l 2 to 0 percent iodine .5 to 0 percent In general the product will contain all of the elements within the percentage ranges indicated, although if for any reason desired in particular feeds some but not necessarily all of the added elements may be present in the product.  
  The dehydrated product normally will contain also the following:  
 potassium 7.0 to 2.0 percent sodium 40 to .5 percent sulfur 12.0 to 3.0 percent salt (NaCl) 2 I .0 to 4.0 percent The following study was performed to show solubility of the sequestered elements. Samples of the dehydrated product were taken, leached with water and then filtered. The samples investigated show solubilities ranging from a low of 98.7% to a high of 99.3%, thus demonstrating that solubility has been retained without the formation of insoluble complexed chemical entities.  
  Since the sequestering process is basically a very complex and undefinable phenomena, 1 will show through chemical data that the product exists as described. Three liquid trace mineral supplements were produced in the laboratory to simulate actual conditions. Number one contained trace minerals supplied as previously described; in number two the trace minerals supplied through the mineral sulfates; and the third was supplied through ethylene diamine tetra acetate (EDTA) chelated trace minerals. Then a chemistry procedure was developed to extract the soluble and available elements. The element thoroughly studied was iron since iron is one of the hardest of all the trace elements to retain without forming insoluble complexes.  
 DATA SUBMITTED TO SHOW THE RESULTS Liquid Supplements Trace element source as in present product Mineral element formula Element Iron 1.28 Zinc 3.20 Manganese 2.24 Iodine .45 Copper .35 Cobalt .l2  
 ***Product formula Element lron l.78 Zinc 9.00 Manganese 9.50 Iodine .IS Co per .32 Co alt .14  
  The liquid supplements were compounded and allowed to stand for 8 days at room temperature. Then the chemical analysis was begun. The chemical procedures employed were kept as simple as possible since the trace minerals employed were all completely water soluble. The samples were all analyzed for Iron because of its ability to form insoluble complexes.  
 Method The samples were extracted with Ammonium Acetate l.0 N at 4.8 pH. The ortho phenanthroline technique for the determination of iron was essentially employed. Detailed information about this method is given by Fortune and Mellon (1938). Bandemer and Schaible (I944).  
 Reagents l. Ammonium Acetate l N pH 4.8  
 2. Orthophenanthroline Reagent 3. Hydroxylamine Hydrochloride 10% Procedure 1.0 ml of each liquid supplement was taken and placed in separate 1 liter volumetric flasks and diluted Wuter Base No. I ll No. I /1 N0. 3 /r&#39; Water distilled 85.909 85.875 85.875 Phosphoric ncid 2.657 2.657 2.657 Salt 8.3l9 8.3l9 H.319 Urea 2.9l7 2.9[7 2917 Vitamin A. 400,000 L SP ujg. .032 .032 .032 Truce Minerals EDDP .200  
 Sulfutes* J66 As in product*** .200 l00.000 l00,000 l0(l.000  
 Chelated trace mineral reacted with citrate-EDTA rea- &#34;The sulfate salts of the trace minerals same sulfate formula as above. Added on a U5 dry sulfate mineral basis.  
 to vol. with distilled water. Then 10 ml are taken into a stopper flask to which 50 mls of Ammonium Acetate are added and agitated for a half hour. The material is then filtered through a whalman No. 4l filter. A l0 ml portion of each extracted sample is taken and placed into each of two photometric tubes plus a third tube into which is placed 10 ml of distilled water. Each original sample will then have 3 photometric tubes. To the first tube of each sample add 2 mls of Hydroxylamine hydrochloride and 2 mls of O phenanthroline. To the second tube add 2 mls of Hydroxylamine hydrochloride and 2 mls of distilled water. To the third tube add 2 mls of Hydroxylamine hydrochloride and 2 mls of 0 phenanthroline. Allow 15 minutes for the reddish color to develop and read in filter photometer using 510 mu wave length filter.  
 Results be used in variable proportions by weight ranging from TABLE 1 Fe Content Sulfate-s EDTA Sea-Ouestru-Min Sup No. l Sup No. 2 Sup No. 3 Reading Content /r Reading Content /r Reading Content &#39;14 Found Actual Found Actual Found Actual Tuhe No. I 69 L63 3.38 Tuhe No. 2 7] 127 L28 Tubc No. 3 63 1.69 1.72  
 The data shows that the supplement having the sulfate mineral has apparently lost the solubility of the free sulfate elements through insoluble complexes that could not be extracted by Ammonium Acetate. On the other hand both the EDTA Supplements No. 2 and the present product supplement No. 3 showed complete recovery.  
 about 0.007% to 0.05% of the feed.  
 The following are illustrative examples prepared in accordance with the invention respectively for rumi- This indicates that even though the raw materials for EXAMPLE 1 my product production are initially sulfates, mineral salts, a change has transpired to render these as sequessequestered Trace Mmefals Rummams tered chemically as the EDTA chelates. It appears Analys&#39;s therefore that this is brought about by the polysacchap ssi m it about 7.00% rides contained in the water soluble portion of the giant Sodium about 310% sea kel Zinc (Zn) about 3.20% Manganese (Mn) about 2.30% In add1t1on to the above data a study was conducted Iron (f about 12% to show the extreme solubility of the present product. Copper (cu) about 0.63% Procedure Magnesium (Mg) about 0.56% Sulfur (S) about 4.00% Four 2 g. dried samples were dlssolved In 250 mls of Iodine m abom 045% distilled water and filtered. The filter paper was previ- Cohan (go) about 0.40% ously dried and weighed. The results are shown in Salt (NaCl) about 17.00% Table 2. The extreme solubility of the mineral compo- Salt (N aCl) about 21.00%  
  (Chlorine expressed as NaCl) nents is apparent.  
 TABLE 2 Solubility Study 200 gm samples taken Weight Weight filler Dried Weight lost 9% /r Snmplc Paper Weight Solnbles Sol Carrier lnsol 1. 2.0 .500 .806] 1.6939 84.7 14% 1.3% 2. 2.0 .542 .8355 moss 85.3 14% .70. 3. 2.0 .505 .8120 l.6930 84.7 14% 1.3% 4. .0 .552 .8555 2.6965 84.8 14% 1.2% *Carricr represents the insoluble lihrous portion of the sen kelp used in processing. Bibliography Fortune. W. B. 21nd Mellonv M. (3. 1938 Determination of Iron with o-phcminthroline. lnd. Eng. Chem. Anal Ed. lUzfiO-h-J Bamdenicr. S. L. and Schinhlc, R. i944 Determination of Iron. A study ol the o-phcnnnthrolinc method. Ind. Eng. Chem. Annl Ed. lhz3l7-3l9 As previously indicated the product is found to have ingredients outstanding nutrient values by reason of the property of the kelp to sequester and maintain in stabilized condition all of these added trace elements as well as values including natural or added vitamins present in the kelp itself. The sequestration appears to result in some if not substantially complete deionization of the sul- Dehydrated kelp (Macrocystis pyrifera), Zinc Sulfate, Mangnaese Sulfate, Ferrous Sulfate, Copper Sulfate, Ethylene Diamine dihydriodide, Cobalt Sulfate.  
 Feeding Directions Beef Cattle Use in the proportion of 0.01% of finished feed.  
  Dairy Cattle Use in the proportion of 0.025% to 0.05% of finished feed.  
  Dehydrated kelp (Macrocystis pyrifera), Zinc Sulfate. Mangnanese Sulfate. Ferrous Sulfate, Copper Sulfate. Ethylene Diamine dihydriodide, Cobalt Sulfate.  
 Feeding Directions Poultry Use in the proportion of 0.03% of finished feed. Use in the proportion of 0.6 lbs/ton of finished feed.  
 EXAMPLE lll sequestered Trace Minerals for Swine Analysis Potassium (K) about 2.36% Sodium (Na) about 0.77% Zinc (Zn) about 8.20% Manganese (Mn) about 9.50% lron (Fe) about 1.78% Copper (Cu) about 0.32% Magnesium (Mg) about 0.18% Sulfur (S) about 10.80% Iodine (I) about 0.l% Cobalt (Co) about 014% Salt (NaCl) about 5.60% Salt (NaCl) about 7.00  
 (Chlorine expressed as NaCl) In gredients Dehydrated kelp (Macrocystis pyrifera), Zinc Sulfate, Manganese Sulfate, Ferrous Sulfate, Copper Sulfate, Ethylene Diamine dihydriodide. Cobalt Sulfate.  
 Feeding Directions Swine Use in the proportion of 0.03% of finished feed. Use in the proportion of 0.6 lbs/ton of finished feed.  
 1 claim:  
  1. Water dispersible feed product comprising dehydrated ground kelp containing added water soluble sequestered trace minerals of the group consisting of zinc, manganese, iron, copper and cobalt, said trace minerals being present in the product by the cation association of ionized sulfate salts of the minerals with polysaccharides in the kelp.  
  2. Feed product according to claim 1 in which the product contains also iodine.  
  3. Feed product according to claim 1 in which the dehydrated product contains about 4 to l0 weight percent moisture.  
  4. Feed product according to claim 1 in which all the named elements are contained in the product.  
  5. Feed product according to claim 1 in which said trace minerals are derived by cation association of ionized sulfate salts of the minerals and ethylene diamine dihydroxyiodide with polysaccharides in the kelp.  
  6. Feed product according to claim 1 added to a conventional ruminant, swine or poultry feed in a proportion of about 0.007 to 0.05 percent of the supplemented feed.