NITRITE CURING OF MEAT The N-Nitrosamine Problem and Nitrite Alternatives RONALD B. PEGG, Ph.D. Saskatchewan Food Product Innovation Program Department of Applied Microbiology and Food Science University of Saskatchewan, Saskatoon, SK, S7N 5A8 Canada and FEREIDOON SHAHIDI, Ph.D. FACS, FCIC, FCIFST, FRSC University Research Professor Department of Biochemistry Memorial University of Newfoundland St. John's, NF, A1B 3x9 Canada FOOD & NUTRITION PRESS, INC. TRUMBULL, CONNEXTICUT 06611 USA NITRITE CURING OF MEAT The N-Nitrosamine Problem and Nitrite Alternatives F PUBLICATIONS IN N~ FOOD SCIENCE AND NUTRITION Books NITRITE CURING OF MEAT: N-NITROSAMINE PROBLEM, R.B. Pegg & F. Shahidi DICTIONARY OF FLAVORS, D.A. DeRovira FOOD SAFETY: THE IMPLICATIONS OF CHANGE, J.J. Sheridan et al. FOOD FOR HEALTH IN THE PACIFIC RIM, J.R. Whitaker et al. DAIRY FOODS SAFETY: 1995-1996, A COMPENDIUM, E.H. Marth OLIVE OIL, SECOND EDITION, A.K. Kiritsakis MULTIVARIATE DATA ANALYSIS, G.B. 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No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means: electronic, electrostatic, magnetic tape, mechanical, photocopying, recording or otherwise, without permission in writing from the publisher. Library of Congress Catalog Number: 00 132300 ISBN: 0-917 678-50-8 Front cover photo courtesy of the Saskatchewan Food Product Innovation Program, Research & Development for the Meat Industry, Department of Applied Microbiology and Food Science, University of Saskatchewan, 5 1 Campus Drive, Saskatoon, SK, S7N 5A8, Canada. Printod in tho Tlnitod Ctntor /If Amorirn PREFACE Meat has been treated for centuries with rock salt as a means of preserva- tion. However, only one century has passed since the German researchers, Polenske in 1891, Kisskalt in 1899 and Lehmann in 1899 discovered that the active component in the curing process was nitrite. It is interesting to look back over this century to see what actually transpired in a hundred years. How much more do we really know about nitrite, its chemistry and its preservative effect on meat than we did a century ago? What were the milestones achieved, if any? Have we learned things about nitrite that perhaps we didn’t want to know, and has technical advancement in terms of processing by meat packers resulted in the loss of certain traditional old-world meat products? In the beginning, the role of nitrite as a meat curing agent was revealed and shortly thereafter, government regulators placed guidelines on the level of nitrite and nitrate permitted for use in cured meat formulations. The importance of salt in combination with nitrite as an antibotulinal agent and the limited understand- ing of its mode of action was a key event during this century. In the late 1960s and early 1970s, the development of the so-called “nitrite problem” surfaced on account ofthe detection of N-nitrosamines in processed meats. The industry was in an uproar, and the issue rose to the very pinnacle of interest, for both the public and research scientist. A major technical advance in the analytical technique for N-nitrosamine detection was achieved when Thermo Electron of Waltham, Massachusetts introduced the thermal energy analyzer (TEA). This unit was a watershed in N-nitrosamine research because it became possible to screen a large number of samples with only a minimum preparation. As an analytical tool, the selectivity ofthe instrument for detecting sub pg/kg quantities of N-nitroso compounds in complex biological materials and foodstuffs without the elaborate clean-up procedures was far beyond anything else available. Today the TEA is recognized as a cornerstone for analytical N-nitrosamine detection. In terms of nitrite chemistry, the controversy over the identity of the pigment of thermally processed nitrite-cured meat raged on for decades. Early studies suggested that the pigment of cooked cured-meat was a dinitrosyl protoheme complex. Yet, a number of scientists were able to unravel some of the earlier conclusions presented in the scientific literature and provide compelling evidence to support their hypothesis that the pigment of nitrite-cured meat was indeed a mononitrosyl ferrohemochrome. The role of nitrite in revealing the desired and unique flavor of cured products, perhaps by suppressing the formation of lipid oxidation products, was another development in revealing other properties of nitrite. Above all, the antimicrobial role of nitrite, together with salt, had a major influence on the popularity of nitritehitrate in food preservation. V vi PREFACE This book presents a review of the desirable attributes that sodium nitrite confers to meat during processing, as well as drawbacks of nitrite usage, i.e., the presence of N-nitroso compounds, particularly N-nitrosamines. Furthermore, the book provides solutions with regard to curing of meat without the use of nitrite. An examination of a multicomponent nitrite-free curing system entailing the color, tlavor, and microbial protection of such a system is presented in Chapter 9. The book has been divided into the following chapters. Chapter 1 begins with a general introduction of what cured meats are, followed by an overview of the main benefits and drawbacks nitrite affords meat and meat products. Chapter 2 contains a review of the history of the curing process. Issues on how curing began, techniques used then and today, and the discovery of nitrite as the active agent are addressed. This chapter will also introduce the character- istic attributes which nitrite affords meat and will lay the foundation for the remainder of the book. Chapter 3 deals with the color characteristics of meat and meat products with particular emphasis placed on the chemistry of muscle pigments. The color of fresh meats, how nitrite modifies it and the color of the product after thermal processing will be described. A review of the controversy surrounding the exact chemical structure of the cooked cured-meat pigment is reported, as well as evidence which supports the view that the cooked cured-meat pigment is a mononitrosylheme complex. Chapter 4 begins with a brief introduction on what is meant by the oxidative stability of meat lipids and further details how lipid oxidation in uncured frozen and cooked meat proceeds. Nitrite’s role in curbing meat flavor deterioration (MFD), previously referred to as warmed-over flavor (WOF), and the proposed mechanism(s) of nitrite’s antioxidative efficacy are addressed. A review of the classical 2-thiobarbituric acid (TBA) test, used for assessing the extent of lipid oxidation in meats, follows. The difficulties raised by nitrite in the TBA test is accounted, and an alternative approach for assessing the oxidative status of cured meat systems is furnished. Chapter 5 deals with the flavor of uncured cooked meat and places particular emphasis on the volatile flavor compounds mainly responsible. The relationship between nitrite and cured-meat flavor is explored and the chapter concludes with a simplistic view on how the basic flavor of cooked meat, species differentiation and MFD may be interrelated. Chapter 6 discusses the microbial status of cooked meat with concerns over possible contamination by Clostridium botulinum spores. A general review of the microbiology of Closfridium botulinum, with regard to how it proliferates and how nitrite exerts a concentration-dependent antimicrobial action in combination with added sodium chloride and adjuncts is recounted. A more detailed review of the bacteriostatic properties of nitrite follows. PREFACE vii Chapter 7 explores the fate of nitrite in the meat matrix. The reactive nitrite anion exists in various forms in meat; it may be converted to nitrogen gas, nitrate, nitrous acid, its anhydride dinitrogen trioxide, or it may react with heme-based muscle pigments, protein, lipid and sulfhydryl-containing com- pounds in the meat matrix. Chapter 8 deals with the potential hazards of nitrite usage in meat. A review of the N-nitrosamine story is reported and covers how N-nitrosamines are formed, and their prevalence in various nitrite-cured meat and meat products. A discussion on current meat industry regulations for nitrite usage, which includes why nitrite usage in fish is banned, as well as various means to prevent and retard N-nitrosamine formation, follows. This chapter also includes N-nitrosamine inhibitors which are available to the meat processor, and the impact of a nitrite-ban to the industry. Finally, Chapter 9 considers possible substitutes for nitrite with regard to the use of a multicomponent nitrite-free curing system. This chapter considers color characteristics, antioxidant properties, flavor characteristics and antimicro- bial choices for nitrite alternatives. The section on color attributes of nitrite-free meats deals with various food-grade dyes and pigments available for addition to meat with a review of their advantages and limitations. A discussion of why the cooked cured-meat pigment itself, performed outside of the meat matrix, is the only appropriate alternative for nitrite-free curing of meat is described in detail. The section on antioxidant properties deals with synthetic and natural antioxi- dants available for use in meat to mimic the effect of nitrite. A discussion on these antioxidants, as well as chelators and synergism noted between combina- tions is reported. The section on flavor characteristics of nitrite-free meat considers sensory studies already performed on such systems, as well as the role of salt and smoking to the flavor. The last section in this chapter reviews the various food-grade antimicrobial agents available for use in nitrite-free curing of meat and evaluates those which have been tested, those which are promising, and those which are not. A concluding section on the multicomponent nitrite-free curing package and its usefulness to the industry is provided. The book thus presents a state-of-the-art account of nitrite, the N-nitrosa- mine problem and nitrite-free meat curing alternatives which would be of interest to meat scientists, government regulators and the industry. Food scientists, nutritionists and biochemists would also find this book informative and useful for inclusion as materials to be covered in a graduate meat science or food chemistry course. RONALD B. PEGG FEREIDOON SHAHIDI
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