3. Curing agents Nitrite (sodium or potassium)….. and sometimes nitrate – functions only by conversion to nitrite first – useful only in dried products such as dry sausage or country cured/prosciutto hams – 7 lbs per 100 gal of pickle; 3 1/2 oz per 100 lbs meat for dry cure; 2 3/4 oz per 100 lbs of meat when used for chopped – when nitrate is used, microbial conversion to nitrite is required – Micrococcus sp. (now Kocuria sp.) have catalase to convert NO3- to NO2– sometimes included in starter cultures as a cured color promoting agent –now often part of “naturally cured” products labeled “Uncured”! Nitrite – definitely magic - distinctive, absolutely no substitute – permitted at 2 lbs per 100 gal of pickle (10% pump); 1 oz. per 100 lbs of meat for dry cure; 1/4 oz per 100 lbs of chopped meat. Cannot exceed 200 ppm in finished product – except bacon 120 ppm nitrite plus maximum (550 ppm) ascorbate or erythorbate – defines a “cured” product --- almost always includes salt as well when “cured” – not permitted in baby foods (sterilized) Functions of nitrites (NO2-) in curing 1. color – due to nitric oxide (NO) from nitrite NO2– promoted by acid conditions – accelerated by reductants, pigments (Fe) and salt 2. microbial inhibition – very effective against Clostridium botulinum but is inhibitory toward many organisms both pathogens and spoilage organisms 3. antioxidant – very effective for preventing rancidity particularly preblends 4. flavor – likely produces a unique “cured” flavor but this has never been chemically identified 5. texture – nitrite reacts with sulfur-containing amino acids to form crossbridges between proteins So: an absolutely critical step in meat curing is forming nitric oxide (NO) from nitrite (NO2-) Conditions which increase nitric oxide formation 1. pH 2NO2- + 2H+ 2HONO NO + NO3- + 2H+ nitrous acid nitric oxide nitrate – decreases pH by 0.2 - 0.3 pH will double the production rate of NO – may add sodium acid pyrophosphate or glucono delta lactone to decrease product pH 2. reductants sodium ascorbate or erythorbate, ascorbic acid or erythorbic acid – react directly with nitrite to produce nitric oxide 3. meat pigments myoglobin-Fe++ + NO2- myoglobin-Fe+++ + NO myoglobin-Fe++ | NO reductants myoglobin-Fe+++ | NO 4. proteins – sulfhydryl amino acids SH SH + NO2 - S S + NO 5. salt NaCl + NO2- NOCl- NO + Cl- Nitrite is very reactive and reacts with many things in a meat system – most are positive reactions --- but --nitrite can also react with secondary amines NH + NO2 N – NO nitrosamine – a definite carcinogen at ppb concentrations –formerly a problem in bacon Nitrosamines are controlled by: – low residual nitrite when bacon is fried – presence of reductants to encourage other nitrite reactions Related problem with rubber nettings used to hold hams for smoking – butyl-amine in rubber reacted with nitrite in hams to produce butylnitrosamine Concerns for nitrite a. toxicity – very reactive, toxic – lethal dose is about 1 g (14 mg/kg body weight) – relaxes smooth muscle and reduces blood pressure – methemoglobinemia – human exposure to nitrite/nitrate is about 80% -vegetables, 10-15% - water, ~ 5% or less - cured meat – ingested nitrate is absorbed and secreted in saliva ( ~ 25% of that is absorbed) and about 20% of that is converted to nitrite by oral - cavity microorganisms – must maintain records of use for USDA when making products – most processors use “Modern Cure”, “Prague Powder”, “Legg Cure” - brand names for curing mixture: 6.25% sodium nitrite 93.75% sodium chloride pink dye because: pure nitrite is a white crystal very similar to sodium chloride – Germany and European Community countries do not permit use of pure nitrite, only salt/nitrite mixtures b. nitrosamine formation – controlled by controlling residual nitrite Sidelight: – nitric oxide has become an important topic in human physiology – involved with brain cell communications, control of smooth muscle contraction and immune system attacks on invading bacteria, wound healing, etc. Non-meat ingredients 4. Reductants – sodium ascorbate or erythorbate, – permitted up to 7/8 oz per 100 lbs (547 ppm); 87.5 oz per 100 gal pickle (10% pump) ascorbic acid or erythorbic acid – permitted at 3/4 oz per 100 lbs of meat; 75 oz per 100 gal of pickle (10% pump) – ascorbate/erythorbate most common because acid forms can be too reactive with nitrite – ascorbic acid, ascorbate Vitamin C – erythorbic acid, erythorbate - optical isomer, not biologically active – ascorbate/erythorbate are equivalent in terms of meat curing Primary function is to increase nitrite curing reaction NO2- NO but also helps to maintain cured color during storage (reductant) – 10% solution may be used to spray surface of cured products prior to packaging - treatment cannot result in significant added water – very effective for improving stability of fresh meat color but not permitted --- too effective! Reductants – for brines/injection curing – should be dissolved immediately after the phosphates --- otherwise may remain undissolved and result in weak or uneven curing reactions – brines for injection should be made up: 1. phosphates 2. ascorbate/erythorbate 3. salt, sugar, etc. 4. nitrites Non-Meat Ingredients 5. Acidulants – acid compounds to reduce pH and accelerate nitric oxide (NO) production --- trade-off with WHC – objective is 0.2-0.3 pH change – also permitted as spray to improve peeling of frankfurters (5% citric acid or 35-40 grain vinegar) For cure acceleration: 1. sodium acid pyrophosphate (SAPP) – acid phosphate – permitted at 0.5% 2. glucono delta lactone (GDL) – permitted at 0.5% as a cure accelerator – may also be used at up to 1% in dry sausage to simulate fermentation Acidulants may also be added in encapsulated form for slow release to simulate fermentation – lactic acid or citric acid