CARRAGEENAN TYPES & TECHNOLOGY FOR PROCESSED MEATS & POULTRY This primer on carrageenan was prepared by the Technical Staff of ISI. It tries to strike a balance between in-depth and accurate technical information for scientists working in the laboratory with carrageenan and an overview for a wider audience. Dr. Harris “Pete” Bixler, Founder Kevin Johndro, Lab Mgr Scott Rangus, CEO & President Ingredients Solutions, Inc.

PRESENTATION OUTLINE What is carrageenan, and how is it “made”. It’s a family, not one gum? How does it function in processed meats? Why is it so cost effective in processed meats? How do you select and use it for your meat plant? The presentation has been structured to answer a series of general questions most encountered by ISI’s Technical Staff. Interspersed with answers to these very general questions will be answers to more specific questions relating to use of carrageenan in particular applications and the most frequently encountered problems in using carrageenan in a food and other applications.

WHAT IS CARRAGEENAN? A long chain, water soluble polymer or vegetable gum. Occurs naturally in the cell walls of certain red seaweeds. Gelling types are of most interest in meats: kappa and iota. Gel with themselves and with myosin. Gels are thermally reversible; melt and reuse. Carrageenan is first of all a long chain, water soluble polymer. Even though it is of natural origin, it differs from other natural polymers like proteins in that it just not have just one chain length or molecular weight, but has a distribution (albeit narrow) of molecular weights similar to that of a synthetic condensation polymer. Food grade carrageenan has an average molecular weight of about 550,000 Daltons with a range from about 80,000 to 2,000,000 Daltons. The repeat unit has an MW of about 520, so the average degree of polymerization (DP) is about 2,000. However, the repeat unit is about twice as long as it is wide, so the length of an average chain relative to its width or diameter (L/D) is about 2,000.

KEY PROPERTIES OF GELLING CARRAGEENANS IN MEATS Elastic (iota) to brittle (kappa) gels (controlling texture) Myosin/cgn networks (homogeneous texture) Myosin/cgn networks (water binding to reduce cook loss and package purge) Starch/cgn networks (cost savings while retaining texture and water binding) Other important characteristics of carrageenan gels are their elasticity and syneresis depending on type, and the effect of added galactomannan on gel properties.

MYOSIN/CARRAGEENAN FORM A BETTER WATER BINDING & TEXTURING NETWORK The most famous synergy between carrageenans and proteins takes place between kappa carrageenan and kappa casein. The positively charged regions of casein micelles interact with the negatively charged regions of carrageenan. Even though kappa casein carries a net negative charge at milk pH, there are significant region of positive charge scattered on the micelle surface. All carrageenans show some interaction with kappa casein, but the strongest and most useful is with kappa casein. Even though the kappa carrageenan forms a network in the milk serum, the concentration is so low (ca. 200ppm) that a mechanical gel is not formed. Nevertheless the carrageenan/casein network is “strong” enough to impart significant “mouthfeel” to the milk and suspension of particulates like cocoa powder. The interaction of casein with carrageenan is enhanced by the divalent calcium ions in milk that help bridge the two polymers. The carrageenan likewise responds to the potassium and calcium ions in the serum to enhanced double helix and aggregate formation.

MEAT USES LEAD THE $90,000,000 U.S. MARKETS FOR CARRAGEENAN MARKET SHARE MEAT 46% DAIRY 36% TOOTHPASTE 4% OTHER (PUDDING, SOUP, DRESSING, PET FOOD) 14% A rough breakdown of the U.S. markets for carrageenan are shown in this slide. The markets are clearly dominates by meat and dairy applications. In the case of the meat, the use has been driven by the injection of carrageenan into whole or comminuted muscle meat before cooking. This applies to products such as deli poultry (roasted turkey breast) and ham. The purpose of the carrageenan is to prevent significant cook loss of moisture and enhances the texture of the finished product. The carrageenan also suppresses purge in the packaged products. Dairy applications in the U.S are dominated by low fat chocolate milk (to suspend cocoa and improve mouthfeel) and ice cream (to prevent whey-off in ice cream mixes prior to freezing). While carrageenan is more expensive than other toothpaste binders like CMC, it has the advantage of improved texture and enzyme resistance in tropical climates. In the “other” category, pet food has already been discussed. In puddings, soups, etc. Carrageenan is added in very small amounts for mouthfeel improvement, particle suspension, or texture modification. These markets have been growing at 3 to 5% annually (in pounds), and show every indication of continuing this trend.

HOW CARRAGEENAN IS “MADE” Dry Seaweed Solid-State Extraction (45% Cgn) Liquid Extraction (1% Cgn) Filtration/ Concentration Washing Carrageenan can be extracted from seaweeds by two general processes. The oldest process involves dissolving the carrageenan in an alkaline solution to yield a solution containing about 1.0% carrageenan. The non-carrageenan components are removed by filtration followed by a 2 or 3 to 1 concentration by evaporation or ultrafiltration. This concentrate is then precipitated with isopropanol or strong KCl. The resulting coagulum is squeezed to remove as much liquid as possible followed by drying, milling and blending. An alternate process gaining favor is solid-state extraction where the seaweed is contacted with concentrated alkali to remove impurities but prevent dissolution of the carrageenan. The carrageenan concentration in the solid state is about 45%. After extensive washing, the rest of the two processes are quite similar. The products of the two processes, referred to as semi-refined or SRC and refined carrageenan, are quite similar in all respects except that the SRC contains 8 to 15% algal cellulose while the refined carrageenan contains a comparable amount of KCl or NaCl. Because of significant energy savings with the SRC process, resulting from the higher carrageenan concentration throughout the process, the cost of producing SRC is significantly less than it is for refined carrageenan. This cost saving has been the driving force for strong growth in SRC sales over the last decade. Drying Milling/Blending KCl pptn Gel pressing Drying Milling/Blending IPA pptn IPA recovery Drying Milling/Blending Market Cost Kappa-NGC@$7.50/lb Kappa-GPR@$9.50/lb Kappa-APRC@$10.50

SOURCES OF CARRAGEENAN SEAWEEDS

VIEW OF A SEAWEED FARM ON A PHILIPPINE REEF This photo shows a more popular farming techniques adopted by families tending larger farms on somewhat deeper reefs. Monofilament line is submerged 2 to 3 meters below the water surface and supported on mangrove poles. Otherwise the techniques is the same as in the previous photo. Harvesting with this farming technique is a simple matter. One end of the nylon line is detached from its supporting pole and the seaweed is stripped off of it into the farmer’s“pump boat” barely visible at the left of the photo.

TURNING TO SPECIFIC MEAT AND POULTRY APPLICATIONS Deli meats: Turkey Ham Chicken roll Beef Marinated products: Rotisserie chicken Case-ready raw marinated meats Whole smoked turkey

A FULL RANGE OF DELI PRODUCTS CONTAINING CARRAGEENAN

INJECTED ROAST TURKEY BREAST Carrageenan’s Function: Reduces cook loss and package purge Improves texture, slicing NGC dominates application Reduced cost ($3.50 vs $6.00/lbcgn) Less needle clogging Fewer unsightly stretch marks (“tiger striping”) Formulation (40%pump) Injection Finished Brine Turkey Water 85.1% 23.8% TSPP 1.7% 0.5% Salt 5.7% 1.6% Dextrose 5.7% 1.6% Kappa Carrageenan 1.8% 1.6% Turkey meat 72.0% This application was outlined earlier. This slide shows a typical brine formulation and pumping level being used by poultry processors. There is obviously improved profitability for the processor resulting from improved water retention. There is no question that higher moisture retention in this product would by itself change its texture, but the presence of the carrageenan gel (and some myosin/carrageenan gel) returns the texture to a more familiar bite. Pumping this product would tend to cause stretch marks (areas of carrageenan gel where the muscle has been separated) if there was any interruption to brine flow through the injection needle assembly. The use of SRC (besides for cost saving) gives more uniform distribution of carrageenan particles in meat muscle. SRC (versus refined carrageenan) swells less in brine, thus resulting in less needle clogging and less interruption of distribution in the meat muscle. This will be explained in the next slide.

CHICKENS BEING INJECTED WITH AN IOTA CARRAGEENAN BRINE BEFORE THE COOK

INJECTED RAW CHICKEN FOR IN-STORE OR HOME COOKING Carrageenan’s Function: Used in case-ready and rotisserie Reduces cook loss improves texture, slicing NGC dominates application by reducing cost, reducing needle clogging NGC also has required cold water swelling Formulation (25%pump) Injection Finished Brine Chicken Water 81.5% 16.5% STPP 2.5% 0.5% Salt 7.5% 1.5% Iota Carrageenan 1.25% 0.25% Flavoring As Needed Chicken meat 80.0% This application was outlined earlier. This slide shows a typical brine formulation and pumping level being used by poultry processors. There is obviously improved profitability for the processor resulting from improved water retention. There is no question that higher moisture retention in this product would by itself change its texture, but the presence of the carrageenan gel (and some myosin/carrageenan gel) returns the texture to a more familiar bite. Pumping this product would tend to cause stretch marks (areas of carrageenan gel where the muscle has been separated) if there was any interruption to brine flow through the injection needle assembly. The use of SRC (besides for cost saving) gives more uniform distribution of carrageenan particles in meat muscle. SRC (versus refined carrageenan) swells less in brine, thus resulting in less needle clogging and less interruption of distribution in the meat muscle. This will be explained in the next slide.

BRINE/MARINADE PUMPED CHICKEN BEING ROTISSERIE COOKED IN LOCAL SUPERMARKET

Increase Yields in Case-Ready Poultry Increase Yields in Case-Ready Poultry! 15-30% Possible w/ISI Iota Carrageenan

HOW TO USE CARRAGEENAN IN THE PROCESSING PLANT Use low dusting (narrow particle size distribution) NGC carrageenan known to disperse easily in brine and to swell slowly Dry blend carrageenan with rapidly soluble salts and sugars Dissolve slowly soluble salts like phosphates in cold H2O Disperse carrageenan blend in this cold solution Use an intensive mixer for dispersing carrageenan blend Heat only after all large powder lumps are dispersed 200 mesh carrageenan powders are preferred for applications requiring wet dispersion such as meat pumping. This chart gives a step-by-step procedure for obtaining a good dispersion of the carrageenan powder in a solution of brine components. It is sometimes beneficial to add a small amount of xanthan to the powder blend to serve as a suspending agent for the partially swollen carrageenan particles. This prevents their settling out in the meat pumping equipment.

HOW TO USE CARRAGEENAN IN THE PROCESSING PLANT (Cont’d) Disperse dry carrageenan blend in this cold solution Use an intense mixer for dispersing carrageenan blend Heat only after all large powder lumps are dispersed Continue slow stirring in brine tank while injecting is in progress. 200 mesh carrageenan powders are preferred for applications requiring wet dispersion such as meat pumping. This chart gives a step-by-step procedure for obtaining a good dispersion of the carrageenan powder in a solution of brine components. It is sometimes beneficial to add a small amount of xanthan to the powder blend to serve as a suspending agent for the partially swollen carrageenan particles. This prevents their settling out in the meat pumping equipment.

ONE OF THE MORE HI-TECH BRINE TANKS ON THE MARKET

WHAT CARRAGEENAN WORKS BEST AND WHY Injecting Turkey Breast (Kappa Application.) NGC gives less needle clogging, easier brine makeup and lower cost NGC gives more natural texture and better masking of gel pockets Refined only needed when more gel strength is needed. Massaging of Ham & Turkey (Kappa Application) Refined outperforms NGC where high brine pickup is needed Injecting Whole Chicken Marinade or Case-Ready (Iota Application) NGC iota works fine up to 30% pump; Above 30% Refined is better

Carrageenan A Natural Ingredient? Currently, a great deal of interest in the “Natural” label The FDA has not defined the term “Natural” to date The USDA has offered a rather subjective definition of; “A product containing no artificial ingredient or added color and is only minimally processed (a process which does not fundamentally alter the raw product) may be labeled natural. The label must explain the use of the term natural (such as - no added colorings or artificial ingredients; minimally processed.)" “Natural-Grade” Carrageenan is most “natural” of carrageenan types. ISI has drafted a statement of “Natural Ingredient” and it is available upon request.

CONCLUDING REMARKS Carrageenan continues to be one of the most effective food gums for meat applications (texture control and water binding) Carrageenan, especially Natural Grade (NGC) is accepted as a “Natural” ingredient While much can and has been written about carrageenan, these three bullet points satisfy me as a brief summary of what I’ve tried to teach you. No, carrageenan is not all things to all food scientists, but it has found some niches where it is virtually irreplaceable. We understand a lot of the science of carrageenan which helps us move forward in applications work as well as improving manufacturing steps. Nevertheless, our models are still fragile and much work remains to be done. Ingredients Solutions is a strong booster of SRC, not just because we played a role in its development. Properly used it has and will continue to save the food processing industry a lot of money.

CONCLUDING REMARKS Carrageenan continues to be one of the most effective food gums for meat applications (texture control and water binding) It also remains one of the most complex hydrocolloid systems to understand technically, so seek help from your supplier Natural Grade Carrageenan (NGC) is the most cost effective carrageenan type for meat and poultry applications While much can and has been written about carrageenan, these three bullet points satisfy me as a brief summary of what I’ve tried to teach you. No, carrageenan is not all things to all food scientists, but it has found some niches where it is virtually irreplaceable. We understand a lot of the science of carrageenan which helps us move forward in applications work as well as improving manufacturing steps. Nevertheless, our models are still fragile and much work remains to be done. Ingredients Solutions is a strong booster of SRC, not just because we played a role in its development. Properly used it has and will continue to save the food processing industry a lot of money.

AND LET’S NOT FORGET THE CONSUMER Pumped, cooked products give the consumer: More uniform texture from package to package A juicier product that still slices easily A purge-free packaged product Cost savings and uniform pricing NGC supports “Natural” food label