Review of challenges and advances in modification of food ...

Challenges and Advances in Development of Active Components 62

RESEARCH ARTICLE

PREFACE API 2015

Challenges and Advances in Development of Active Components to Modify Headspace Gases in Packaging of Fresh Produce and Muscle Foods

Ziynet BozUniversity of Florida

Jeffrey K. BrechtUniversity of Florida

Bruce A. Welt*University of Florida

William PelletierUniversity of Florida

ABSTRACT

Modified Atmosphere Packaging (MAP) has been widely used as an effective way to preserve foods. Fresh produce, meat and meat products, seafood, and dairy products can benefit from modified gaseous atmospheres, which are usually achieved by reducing oxygen and increasing carbon dioxide concentrations, within limits, defined by product tolerances. MAP of fresh produce is particularly challenging because products are living and respiring. Respiration rates depend on several factors including temperature, oxygen, and carbon dioxide concentrations. Balancing package permeation with respiration is challenging, often due to limited selection of practical packaging materials. Failing to remain within tolerance limits of products leads to rapid quality loss.Gas barrier properties of packages determined rate of gas exchange with the external environment and is a critical factor for achieving tolerable levels. Availability of packaging materials that meet requirement of specific produce is essential. Relative permeability of common films to carbon dioxide is about 3 to 6 times of that to oxygen, often leading to package collapse for package atmospheres that benefit from carbon dioxide. Films often fail to provide desired oxygen transmission rates, high carbon dioxide to oxygen selectivity and desired mechanical properties simultaneously.Despite advances, minimal availability and high cost of selective barrier films limit applications of MAP for fresh produce packaging. Therefore, active packaging components and films are being developed and designed to overcome these limitations. Inserts or films that contain active mixtures as gas emitters

Eric McLamoreUniversity of Florida

Greg KikerUniversity of Florida

Jason E. ButlerUniversity of Florida

Journal of Applied Packaging Research 63

RESEARCH ARTICLE

PREFACE API 2015

INTRODUCTION

The food industry has been shaped by changing consumer demands and availability of a wide variety of foods. Past decades have witnessed the increased consumption of products with proven advantages to human health and well-being. Fruits and veg-etables were demonstrated to have health benefits against chronic disease and cancer [1]. Fish and lean red meats provide essential macro and micro-nutrients [2], [3]. Muscle food products remain the main source of protein and nutrients [4]. Accel-erating consumption of fresh produce, meat and fish has led to improved post-harvest/post-mortem handling, processing, packaging, transportation, and retail practices. However, the perishable and variable aspect of natural, high-value products con-tinues to challenge industry to develop methods to preserve “freshness” without compromising safety. Improved preservation could mitigate loss of nearly one-third of foods produced [5]. Recent consumer preferences for minimally processed foods and overall “freshness” have led marketing efforts to switch focus from “shelf life extension” to “pres-ervation of preferred quality” Although shelf life is an important parameter, the main selling factor is quality as perceived by the consumers [6].

Packaging innovations have been mainly limited to barrier modifications as well as improved

ergonomic and aesthetic designs. Technologies such as active and intelligent packaging have been proposed, but have not yet been fully realized com-mercially [7]. Modified atmosphere packaging (MAP) can provide benefits by slowing deteriora-tive reactions. Sales volumes of advanced packag-ing technologies and MAP continue to grow and are anticipated to reach $6.4 billion by 2020 [8]. One of the most challenging aspects of MAP is the unique atmospheric requirements for the variety of products. In red meats, oxygen is necessary for the bright red color expected by consumers, but oxygen also contributes to degradative oxidation. There-fore, techniques to control oxygen exposure are of value to red meat products. Respiring fresh produce require distinct levels of oxygen and carbon dioxide. Typically, oxygen levels lower than atmospheric and carbon dioxide higher than atmospheric are needed. Great care is required to ensure that oxygen is not reduced to levels that result in anaerobic res-piration. For fish, the primary goal of MAP is pre-venting microbial growth. Relatively high carbon dioxide levels help to reduce pH via equilibrium of the dissolved gas with carbonic acid. Therefore, flushing packages with carbon dioxide as high as 100% by volume may prove useful [9].

Elevated carbon dioxide concentrations are often desirable in packaged foods anti-microbial effects, regardless of product type. Carbon dioxide is

and/or scavengers are now commercially available. “Clean label” trends are motivating alternative approaches using active packaging components.

KEY WORDS

modified atmosphere packaging, MAP, food, muscle, fresh, produce, respiring, respiration, active packaging

Bruce A. WeltCorresponding [email protected]

*


soluble in aqueous solutions, food tissues and packag-ing materials. Rate of permeation of carbon dioxide through polymers is three to seven times greater than for oxygen [10]–[12]. A comprehensive review on O2/CO2 diffusivity and solubility in a variety of foods and polymers was written by Chaix et al. [13].

Loss of gas from packages combined with sol-ubility of headspace gases in packaged products causes reductions in volume in flexible packaging, resulting in unattractive, deflated packages that may appear to be less than “fresh” [10], [14]–[16]. Defla-tion [17] causes misconceptions about defects related to products and/or packaging, such as inferior pack-aging materials or methods, microbiological activity or seal defects. Industry recognizes package volume changes as a problem and works to mitigate the problem by adjusting initial volumes of headspace gases and by considering shipping distances [18].

Understanding the distinct atmospheric requirements of foods drives research, process-ing and packaging innovation. MAP advances have been realized in mathematical modeling and computer simulation, materials development and properties analysis and measurement and gas gen-eration, mixing and handling. Modified package atmospheres may be obtained actively or passively. “Active” MAP involves injection of the desired atmosphere into packages so as to instantly arrive at the targeted atmosphere. “Passive” MAP relies upon interactions among product (e.g. product res-piration rate), package (i.e. gas transmission rates) and the environment (i.e. ambient gas composition and temperature) to arrive at target atmospheres sometime after packaging. Often, optimal modified atmospheres cannot be attained using commercially available packaging materials and/or gas flushing. For example, due to differences in permeation rates of gases, we may be able to achieve the desired level for oxygen or carbon dioxide, but not both at the same time. Additionally, carbon dioxide emitters may be used to prevent package collapse.

The European Commission Regulation (EC) No 450/2009 on active packaging defines active materials as “Materials and articles that are intended to extend the shelf-life or to maintain or improve the condition of packaged food; they are designed to deliberately incorporate components that would release or absorb substances into or from the packaged food or the environment sur-rounding the food can aid overcoming product-specific challenges”. Thus, active packaging is con-sidered a secondary level of packaging, but may play a role in primary functions, such as modified atmosphere [19]. Gas emitting or scavenging via active components comprises a significant portion of active packaging. Adjustment of package gas requires knowledge of effects on biochemical pro-cesses, physical interactions, microbial flora [20], and other variabilities. MAP and AP applications may be justified based upon value-added consumer convenience, new product opportunities that did not otherwise exist, branding opportunities, extended maintenance of quality, reduced waste, and/or higher margins. Increasingly, due to regulatory and/or consumer preference, chemical preserva-tives cannot be added in certain foods or package materials. For this reason, vacuum packaging, due to its simplicity and effectiveness, remains partic-ularly important [21]. For example, a recent trend of “clean-label” products creates an opportunity for food preservation through MAP and AP by elimi-nating artificial food-additives [22].

MAP AND PRODUCT CONSIDER-ATIONS

Map Considerations for Fresh Produce

Biological activity in fresh produce continues after detachment from the plant. Harvested produce draws resources from its own stores causing degra-dation. Deterioration rate is influenced by respiration


rate, ethylene sensitivity and exposure, genetics, physical injuries, microbiological activity and physi-ological disorders [23]. Generally, reduction of respi-ration rate is the primary objective of MAP for fresh produce. Respiration is a primary process for con-sumption of reserves of carbohydrates, lipids, and proteins. Depletion of nutrient resources and build-up of reaction by-products manifests as decreasing fresh-ness. Pectolytic enzyme activity causes changes in texture and aroma. Such changes are often associated with the rapid ripening processes referred to as senes-cence [24]. Enzyme mediated metabolic rates are affected by variety, harvesting time and processing conditions [25], [26]. MAP has been reported to help to preserve firmness of dried apricots and table grapes [27], [28]. Slowing metabolic activity with reduced oxygen and elevated carbon dioxide preserves fresh-ness [29]. However, benefits to texture and aroma depend on type of produce and specific MAP condi-tions such as minimum and maximum tolerable O2 and CO2 concentrations. Taking MAP beyond toler-able limits of produce results in increased softening and off-flavor development. Consumers distinguish subtle differences in aroma and texture associated with freshness so care must be taken to understand MAP design as well as environmental aspects of the supply chain [30]–[32].

Gas Concentrations

Understanding factors that cause variations in respiration rate is important for MAP design. Equi-librium atmospheres should be within a “window” of optimum gas concentrations for different produce [33]. Gas concentrations in packages depend on package gas transmission rates (GTR), respiration rate of produce, respiration quotient (carbon dioxide molecules liberated per oxygen molecule consumed) and ambient conditions. When the partial pressure of oxygen decreases within a package due to respiration or oxidative reactions, permeation of oxygen into the package, from the environment increases [34].

Oxygen serves as final electron acceptor in aerobic respiration reactions [35]. The typical goal of MAP is to reduce oxygen to the lowest possible level that supports aerobic respiration. When oxygen levels drop below this threshold, anaerobic respira-tion ensues, which rapidly diminishes quality. Use of other gases to promote quality retention, such as nitric and nitrous oxides, Sulphur dioxide, chlorine, ozone and propylene oxide have been used for a variety of reasons [36], [37]. Economic benefits and consumer value should be considered before imple-menting MAP for a given product [38].

Use of oxygen-enriched atmosphere (super-atmospheric oxygen) has also been studied for making produce less susceptible to thermal abuse. Degree of benefit appears to vary with commod-ity, maturity and ripeness [39]. Escalona et at. [40] reported that super-atmospheric oxygen was only beneficial when used with moderate levels of carbon dioxide. More work is needed to assess the value of super-atmospheric gas concentrations in MAP applications.

Effect of Intrinsic Properties and Processing

Variations in respiration rate are inevitable and due to both extrinsic and intrinsic factors. Intrin-sic factors include variety, maturity, composition, and size. Typically, ±10% deviation in respiration rate are observed in separate batches of the same produce [41]. Seefeldt, Løkke, and Edelenbos [26] observed respiration rate differences in produce harvested in early versus late summer as well as differences among four broccoli varieties. Respira-tion rate differences due to variety have been shown to be as large as 60% among three MAP packaged apricot varieties [25]. Such variations make design-ing MAP challenging.

Cutting, wound formation and mechanical injury tend to cause respiration rates to increase, leading to accelerated ethylene production, water loss, texture and color changes and increased


microbiological activity [42]. Therefore, respiration rates of fresh-cut commodities tend to be higher than intact produce. Heat treatments also cause res-piration rate differences depending on pre-harvest condition and exposure duration. Postharvest heat treatments are gaining attention due to reductions of respiratory and microbial activity and preven-tion of chilling injury [43]. Changes in respiration rate and quality were studied during heat treatment in combination with MAP of several commodi-ties including, asparagus, tomatoes and fresh cut melons [44]–[46]. A review of research on the com-bination of minimal processing and MAP was pre-sented by [47]. Table 1 summarizes recent research of processing conditions on respiration rate. Com-bining varieties in packages (i.e. salad mixes and fruit platters) has become popular. Since differ-ent varieties exhibit different respiration rates and typically require different gaseous atmospheres for optimal preservation of freshness, compromises in package design must be made. Typically, packages are designed to accommodate the highest respira-tion rate ingredient.

Microbial Consequences

Data from 2004 to 2013 show that the fresh produce is the primary source of outbreaks that caused human illness [48]. MAP conditions influ-ence microflora differently based on complex inter-actions with produce and environmental conditions in the supply chain [49]. Highly soluble CO2 offers antimicrobial activity but can damage produce tissue at high concentrations. Although the specific functioning mechanism is not known, suggested theories focus on the replacement of O2 for the bac-terial activity, reduction of pH, direct penetration into the cell and intracellular liquid , and direct/indirect inclusion of CO2 in the metabolic reac-tions [50]. Also, CO2 may not inhibit certain robust pathogens. Elevated carbon dioxide concentrations (changing from 5% to 12%) had no inhibitory effect

on L. monocytogenes [51], [52]. Physiochemical composition of products, such as low pH, repre-sents a hurdle for certain bacteria in foods, which can lead to proliferation of acid tolerant spoilage bacteria, yeasts, and molds.

Vegetables are susceptible to growth of patho-gens and spoilage microorganisms, which may be suppressed by MAP. Due to competition, spoilage bacteria tend to limit pathogenic microorganisms [53] causing food to spoil before becoming toxic. Concerns related to MAP of fresh produce are due to microorganisms that survive at cold storage tem-peratures (i.e. psychrotropic L. monocytogenes, Yersinia enterocolitica and Aeromonas hydrophila) and under anaerobic or low oxygen (fermentative) conditions such as Salmonella, E. coli O157:H7 and L. monocytogenes [54]. Clostridium botulinum is always a safety concern in low-acid foods (pH >4.6) due to possible liberation of deadly boltuli-num neurotoxin under anaerobic conditions [55]. Under chilled and modified atmosphere conditions, growth of pathogens suppresses growth of indige-nous microflora such as Pseudomonas spp. Entero-bacter spp. and lactic acid bacteria [51], [56].

Samonella causes the most illness among all pathogens in fresh produce [48]. Salmonella and facultative anaerobes are capable of growing with and without oxygen. Low oxygen conditions may promote growth of pathogens initially present on produce. Horev et al. [56] and V. Rodov et al. [57] demonstrated that Active MAP favored growth of Salmonella enterica in romaine lettuce whereas passive MAP had no apparent effect except for reductions in total bacterial counts. Vegetables at abusive temperatures promote growth of patho-gens [58]. Abusive temperatures have been demon-strated to increase the number of pathogens such as E. coli 0157:H7, Salmonella and L. monocytogenes in MAP produce [52], [59], [60].

Spoilage microorganisms play an important safety role by causing detectable spoilage before


pathogens liberate toxins [36], [61], [62]. However, spoilage may not always occur prior to pathogen growth. Aesthetic quality and consumer accept-ability did not change for MAP stored butternut squash and onions even after liberation and detec-tion of botulinum toxin for products stored under different temperatures including 5oC [63]. Simi-larly, botulinum toxin appeared in ultraviolet radi-ation treated fresh-cut cantaloupes and honeydew melons before visual quality changes were observed at 15oC [62]. Hintlian and Hotchkiss, [62] developed the “Safety Index,” which represents the ratio of spoilage microorganisms to pathogens, which helps to predict likelihood of spoilage prior to danger from pathogens before consumption. The major challenge is assessment of food safety by considering these complex microbial interactions under MAP and cold storage throughout the supply chain. Recent studies published on microbiological aspects of atmosphere modification demonstrate effects of vegetable and packaging type, varying gas concentrations and temperatures on growth and survival of several pathogens [52], [56], [57], [65]–[67]. Extensive reviews on microbiological aspects of MAP in fresh and fresh-cut produce have also been available [14], [36], [49], [55], [58], [68].

Map Considerations For Muscle Foods and Products

Preparation and packaging of muscle products transitioned from separate, in-store operations to centralized processing facilities using con-sumer-ready packages. This has paved the way for implementation of MAP technologies [85]. MAP is among the most convenient technologies to maintain and extend the shelf life of muscle products without food additives [86]. Similar to fresh produce, extending the shelf life of fish by atmosphere modification depends on the nature of product such as fat content and microbial flora and load, and external factors including temperature,

gas composition and form of packaging [87]. High postmortem water activity (0.65-0.8), pH (>6) and non-protein nitrogen compounds render fish and fish products susceptible to the microbial spoilage, although changes in sensory characteristics usually appear before the spoilage occurs [88].

Meat Products

Meat quality is characterized by its color, water holding capacity/exudate, microbial activity and lipid composition [89], [90]. Consumers are mostly influenced by color. Discoloration causes economic loses [91]. Color changes can also induce other deteriorative reactions. For example, interaction of meat discoloration and lipid autoxidation in a ran-cidity producing catalytic cycle has been shown [92]. Changes in red color of meat by oxidation are promoted by the ferrous associated blood protein, myoglobin. Oxidation of myoglobin is promoted by a variety of factors including increasing tempera-tures and light exposure [93]. In this process, oxy-genation of purple deoxymyoglobin forms red oxy-myoglobin, which may be oxidized to form brown metmyoglobin [91]. Brown colored metmyoglobin formation from deoxymyoglobin is not desired in fresh red meat, therefore its formation is delayed by keeping myoglobin in the deoxygenated pur-ple-color form via MAP, Vacuum Packaging (VP), Vacuum Skin Packaging (VSP) and active packag-ing (AP) technologies.

Protecting deoxymyoglobin from oxygen is achieved by combining high and low barrier packag-ing films with vacuum and/or oxygen-free gas. For retail display, high oxygen barrier film is removed, exposing a high oxygen transmission layer, causing meat to “bloom” red. This approach is referred to “master-packs,” and “tray-in-sleeve.” Trays, lidding films, master-pack barrier films, Vacuum Skin Packaging (VSP) trays made of materials with high oxygen barrier such as polyvinylidene chloride (PVDC) or polyethylene vinyl alcohol copolymer


Physical Factors Biological Factors

Parameter Produce Reference

UV-C processing effects N/A RR, microbial growth,sensory and quality parameters

Red Oak Leaf lettuce (Lactuca sativa L.)

[69]

Temperature, packaging filmsElectron-beam irradiation N/A

N/A RR, color variationRR, microbial growth,sensory and quality parameters

Iceberg and Romaine lettuce [70]Fresh-cut cantaloupes (Cucumis melo Linnaeus, cv. Magellan and Acclaim)

[71]

Temperature, MAP storage time,cutting type

N/A RR, RQ, Ea Carrots (Daucus carota L.) [72]

Temperature, transient O2 and CO2 concentration changesTemperature, O2, CO2 Biological

composition

N/A RR

RR, RQ

Green banana (Musa paradisiaca L) [73]

Agaricus mushrooms [38]

Gelatin coating, Temperature N/A RR, RQ, Ea minimally processed organic carrots (Daucus carota L. cv. Brasília)

[74]

Ar, He, N2, O2 in combination with two sanitation treatments

N/A RR, ethylene production, storage time, quality parameters, bioactive compounds color, microbial quality

Aragula salad (Eruca vesicaria Mill.) [75]

Temperature Variety, Harvest Time

RR Broccoli species (Brassica oleracea, Italica Group) and Wild Rocket Salad Diplotaxis tenuifolia L.)

[26]

Cut size, blade-sharpness, dipping process

Origin, physiological age, seasonality

RR Fresh-cut pineapple (MD2) [76]

Temperature, MAP N/A RR, RQ, quality parameters

Fresh cut apple (Malus domestica, Borkh) CV Gala

[77]

Temperature Seasonal variations, Maturity state

Ethylene production, RR, RQ

Plums, (Prunus domestica L.) [78]

O2, CO2, storage time Harvest time, Maturity stage, Cultivar, Volatiles

Off odors, RR, ethanol, acetaldehyde, weight, edge browning

Fresh-cut iceberg lettuce (Lactuca sativa L.)

[79]

Critical O2, low temperature storage, CO2 absorber

N/A RQ, RR, chilling injury Cucumbers (Cucumis sativus L.) [80]

Cold plasma treatment and O2, CO2, N2 mixtures

N/A RR, microbial reduction, quality parameters

Strawberries [81]

Changing mixing proportions of the produce

Overall RR, Ethylene production

Fresh-cut pineapple, apple and melon mixtures

[82]

Packaging types and corresponding MAP environment

N/A RR, quality parameters, physiological loss

Green chillies (Capsicum annuum L.) [83]

Active MAP, Passive MAP N/A RR, sensory and quality parameters, physio-chemical parameters, microbial quality

Pomegranate arils (cv. Wonderful) [84]

Temperature (Heat treatment), Active MAP

N/A RR, visual quality, decay development

Fresh Cut Melons (Cucumis melo L.) [46]

RQ = Respiratory Quotient, RR = Respiration Rate, Ea = Activation Energy, N/A = Not Available

Table 1: Recent literature on assessment of intrinsic and extrinsic factors on respiration rate and different parameters of fresh and fresh-cut produce.


(EVOH) nylon, as well as high oxygen transmitters such as polypropylene, polystyrene and polyethyl-ene are used in MAP of meat. Red meat products not suitable for immediate sale, such as primal-cut, ground beef are stored in atmospheres with less than 0.1% oxygen [94].

For shelf-ready products, MAP is usually achieved with elevated oxygen and carbon dioxide [95]. On the other hand, high oxygen MAP can also cause color degradation. Super-atmospheric oxygen in MAP affected color stability by triggering oxida-tion and myoglobin oxidation in chilled fresh beef [96]. Color stability can be improved by low levels of carbon monoxide (CO), which binds to myoglo-bin preferentially to, protecting the molecule from oxidation. Carbon monoxide treatment stabilizes color to such an extent that it can also be disadvan-tageous because uncooked color may persist even after cooking. The “fresh” uncooked appearance may also hide indications of spoilage. Venturini et al. [97] assessed optimal anoxic gas mixtures on microbial, color and sensory attributes of fresh beef muscles and concluded an optimal mixture of 39.8% N2, 60% CO2 and 0.2% CO for maintaining color without growth of L. monocytogenes or S. aureus. In another study 99.6% CO2 and 0.4% CO mixture enabled growth of Listeria species in master-pack-aged pork while preserving the color quality.

Aerobic storage of meat facilitates fast-grow-ing microflora Pseudomonas, Psychrobacter and Moraxella [98]. Spoilage often originates on product surfaces by aerobic microorganisms resulting in decomposition of proteins such as collagen with consequent production of proteinaceous slime and off-odors [95]. Shelf life extension is achieved by limiting aerobic, Gram-negative microorganisms to promote Gram-positive and slow growing microor-ganisms such as lactic acid bacteria and Micrococ-caceae. Vacuum packaging, when combined with muscle-based chemical reactions can create low oxygen and elevated carbon dioxide concentrations

(10-30%). Despite extended shelf life, carbon dioxide tolerant lactic acid bacteria produce acidic off-flavors and aromas, representing the main cause of spoilage in vacuum packaged products. Typical concentrations for MAP of packaged meat are 10-40% and 60-90% carbon dioxide. Due to bacteriostatic effects, 100% carbon dioxide may be used [98]. High carbon dioxide levels result in package collapse through permeation and dissolv-ing in products. Product to gas ratios should at least be equal to two and dissolved gas should be compensated for with excess amounts of gas [99], which can be provided by gas emitters. In a recent study, a gas mixture containing the highest carbon dioxide ratio tested (20:50:30% of O2:CO2:N2) showed the most inhibitory effects on Enterobac-teriaceae in minced meat containing pork and beef [100]. Detailed microbiological aspects of meat and poultry products can be found in [101].

Fish Products

Quality degradation in fish and fish products may stem from microbial spoilage, enzyme activity, and lipid oxidation. Microbial spoilers responsible from degradation in texture, flavor and appearance in seafood include Pseudomonas spp., Shewanella putrefaciens, Photobacterium phosphoperum, Vib-rionaceae and Enterobacteriaceae. These microbes are referred to as seafood specific spoilage organisms (SSO) and represent only a small portion of initial microflora present. Conditions such as gas compo-sition, temperature, high water content and addi-tives such as sodium chloride (NaCl), create selec-tive environments promoting growth of SSO relative to the broader population of microflora. SSO growth leads to off-flavors limiting shelf life of fish. Trimeth-ylamine (TMA) is a key contributor to fishy odors. Low molecular weight off-flavors such as hydrogen sulfide (H2S) and other sulfur compounds, ammonia, biogenic amines, acetic acid and hypoxanthine con-tribute to spoiled aroma [102]. TMA is produced from


trimethylamine oxide (TMAO) primarily through the action of trimethylamine oxidase enzyme from spoilage bacteria, which can even be produced under chilled and oxygen-free conditions. This reaction is responsible for fish spoiling relatively faster than other muscle foods [103]. MAP has the capacity to increase shelf life by inhibiting growth of SSO as well as limiting the lipid oxidation.

There are several criteria when selecting optimal gas concentrations in MAP for fish and fish products. Skura [104], [9] reviewed MAP in fish and fish products including cod, salmon, haddock, catfish, tilapia, swordfish, snapper, herring, shrimp and trout. The typical approach was minimizing oxygen and increasing carbon dioxide to 60-100%, exploiting antimicrobial effects of carbon dioxide.

Due to high solubility of carbon dioxide in organic materials such as polymer packaging films and tissues of the packaged products, initial head-space volumes and concentrations cannot be pre-served throughout the shelf life without a source of new gas. Carbon dioxide emitters represent a relatively new active component for packaging in order to stabilize soluble gases. This are referred to as soluble gas stabilization (SGS). However, even after opening a package enriched with carbon dioxide, residual gas was shown to be sufficient to suppress spoilage microflora and provide for addi-tional shelf life [105]–[107]. Due to Henry’s law, headspace gas seeks equilibrium with gas dis-solved in products. Equilibrium concentrations of dissolved gas depend upon partial pressure of gas in the headspace and product composition. As headspace gas dissolves in products, flexible packages deflate. Product to gas ratio should be at least 2:1 to 3:1 by volume for effective microbial preservation and maintenance of package integrity [9]. However, increased headspaces lead to higher package volumes, which consume precious volume within the supply chain. Carbon dioxide emitters and soluble gas stabilization techniques mitigate

this problem. Above certain concentrations, dis-solved carbon dioxide creates a carbonated “fizzy” mouthfeel for cooked and raw fish. Fletcher et al. [108] developed a model to correlate product to gas ratio and carbonated flavors in fresh salmon. They found the optimum ratio of 0.5-1 mL carbon dioxide per gram of product.

Since dissolved carbon dioxide forms an equilibrium with carbonic acid, which reduces pH, carbon dioxide may denature water-holding proteins resulting in increased drip-losses [9]. Fish packaged under MAP or vacuum in pre-rigor is more susceptible to increased drip losses as compared to fish packaged in post-rigor [109]. Even though benefits of MAP often exceed drawbacks, one risk associated with MAP in fish is growth of toxin producing anaerobic pathogens at oxygen concentrations lower than 4-8%. The primary pathogen of concern is the obligate anaerobe Clos-tridium botulinum. Inclusion of oxygen should be able to prevent toxin production [110]. Additionally, response of anaerobes can vary in fish. Addition of oxygen does not necessarily guarantee elimination of risk of botulism. Maintaining cold chain tem-peratures (<3.5oC) from harvest to retail prevents growth of C. botulinum [111]. L. monocytogenes, Yersinia enterocolitica and Aeromonas spp. are also pathogens of concern at low temperature and oxygen conditions. Typically, increasing carbon dioxide concentrations leads to delayed toxin pro-duction. Higher carbon dioxide levels represents one possible hurdle among a number of hurdles (e.g. temperature, preservatives, water activity, etc.) that together protect consumers from patho-gens [110]. Regulators such as FDA, prefer that spoilage bacteria grow unimpeded so that products present clearly as spoiled before toxin is produced. In an imprecise world, there is always a risk of toxin production before spoilage. Therefore, temperature control is the most essential factor in ensuring food safety with and without MAP or AP.


Temperature control validation can be done with smart packaging technologies such as time-temperature integrators (TTI) [9]. Food safety verification can be done by coupling the response reaction of the TTI’s with practically meaningful properties, such as initiation point for the toxin production. However, many end-point indicators are rather “programmed” to respond to tempera-ture kinetics directly. Welt et al. [112] designed an improved performance TTI to adjust responses according to a well-known empirical relation-ship presented by [113]. The same principle can be applied to design novel TTIs including effects of other definitive parameters for an increased selec-tion based on product type. For example, Gunvig et. al. [114] developed a model to predict growth of C. botulinum with changing external conditions of temperature, pH, NaCl, sodium nitrite and sodium lactate in meat products.

Reduction of quality through autolytic enzymes and chemical reactions begins immediately after harvest and manifest even before evidence of dete-rioration due to microbial growth. Oxidation of polyunsaturated fatty acids is the main concern for non-microbial spoilage in fish. Changes in flavor, odor and color caused by such reactions leads to reductions in shelf life and sales [115]. High-fat fish such as salmon, herring and cod are more suscep-tible to oxidation. Therefore, oxygen is removed through vacuum or MAP with elevated carbon dioxide and balanced with nitrogen to help mitigate oxidation in such products, but oxygen perme-ation into packages results in persistent residual levels. Oxygen scavengers have been shown to be capable of reducing headspace oxygen to less than 0.1% from atmospheric concentrations [116]. Antioxidant compounds have been incorporated in packaging materials in combination with MAP for a variety of products. Table 2 shows synergis-tic effects of MAP with other preservation methods for muscle products.

Poultry Products

MAP has been shown to be able to double shelf life of poultry products [117]. However, literature related to poultry MAP is limited. Since microbial spoilage is the primary concern, elevated carbon dioxide concentrations have been applied. Typical carbon dioxide concentrations vary between 40-100% by volume balanced with nitrogen [118]. Under anaerobic conditions, Pseudomonas spp. can be suppressed, however, acid tolerant anaerobic and facultative microorganisms such as lactic acid bacteria and Enterobacteriaceae cause spoilage via slime and off-odors [119]. Meredith et al. [118] demonstrated shelf life extension benefits using 40:30:30% (CO2:O2:N2) on Campylobacter, 50% and 70% of carbon dioxide on lactic acid bacteria and Pseudomonas, respectively. High oxygen con-centration MAP in turkey breast has shown slightly better retention of color and sensory characteristics than low oxygen concentrations [120].

Importance of External Factors

Reducing temperature and oxygen levels reduces reaction rates that use oxygen, such as aerobic res-piration in fresh produce. Among these, temperature is the most important external factor [15]. Tempera-ture does not only influence respiration rate, but vir-tually all reactions that influence safety and quality. Gas transmission rates of package materials and sol-ubility of gases in packaged products are also influ-enced by temperature. Ideally, storage temperature should be kept at the lowest level that does not cause chill damage for the purpose of slowing reactions as much as possible. Maintaining temperature through the supply chain is often referred to as the “cold chain management,” and it involves temperature control during handling, transportation, distribution and retail [65]. Mathematical models used to design MAP assume exposure to specific temperatures. Deviations from assumed temperatures cause devia-tions in packages and when excessive, may result in


undesirable and/or unsafe conditions. For respiring produce, predicted equilibrium/steady-state gas con-centrations in MAP packages can only be expected when products are stored within assumed temper-ature ranges. Tano et al. [128] studied atmosphere and quality changes of mushrooms, broccoli and tomatoes under abusive temperatures and reported that fluctuating temperatures promoted anaerobic respiration, resulting in off-flavors, ethanol and acet-aldehyde development. They also showed that anaer-obic conditions develop based on the highest tem-perature reached and headspace of the package.

Though controlled, temperature is rarely constant throughout the cold chain [129]. Ninety percent of produce that benefit in relatively low temperatures (<4oC) encounter retail temperatures higher than the recommended. Moreover, deviations from optimum storage temperatures vary with seasonal changes by as much as 87% and 93% in summer and winter, respec-tively [130]. Distribution centers and retail outlets cause most temperature abuse due to convenience, marketing

purposes and human interactions. Business prac-tices cause extra storage days at distribution centers and wholesale markets under non-optimum condi-tions, which leads to decreased shelf life, especially for delicate, temperature-sensitive crops like bananas, cucumbers and tomatoes [131]. Therefore, many labo-ratory experiments and recommendations based on optimum temperature conditions fail to reflect the “non-optimal” shelf life realized commercially [132]. Slight temperature deviations cause a stronger response on respiration rates than packaging gas transmission rates [15], [26]. Understanding practical ranges of conditions is helpful to successful design of MAP. A common approach adopted to select the appropriate temperature is the “approximate achievable temperature,” which is calculated by considering optimum and prospective abusive temperatures in the calculations. For example, if the produce has the optimum storage temperature of 0oC and the highest expected temperature abuse during handling and display in the supermarket of 15oC, the approximate average of these temperatures (7oC) is

Table 2: Examples of recent studies on combination of MAP and hurdles.Products MAP

ConcentrationsAdditional hurdle Remarks Reference

Ready to use peeled shrimp

MAP Thymol essential oil 9 days of shelf life increase when MAP and thymol combined. MAP alone or thyme oil at high concentration could not provide shelf life extension.

[121]

Bluefin tuna filletsPacific white shrimp 75:10:15%

(CO2:O2:N2)

N2 flushing α-tocopherolControlled freezing point temperature (-0.8 oC)

Reduced lipid and hemoglobin oxidation [122]Shelf life extended to 11- 12 days. [123]

Gilthead se bream 5:95% (O2:CO2) Grape fruit seed extract, thymol, chitosan

Extended microbial and sensory qualities for 8-10 and 20 days, respectively.

[85]

Catfish slices

Poultry sausages 100% CO2

35:5:60%(CO2:O2:N2)

Tannic acid

High Hydrostatic Pressure

Reduced lipid oxidation and suppressed growth of psychrophilic and mesophilic bacteria

[124]

When combined with 100% CO2, lower pressures can be used for inactivation of L. carnosum, B. thermosphacta, L. innocua

[125]

Ground beef 20:80% (CO2:O2) Tannic acid Better color stability, psychrophilic bacteria and limited lipid stability were obtained with incorporation of tannic acid in high O2 MAP

[126]

Beef Varying mixtures Clove oil, cinnamon oil, illicium verum oil

Patent that claims a shelf life increase up to 24 days

[127]


chosen as the basis. This approach may fail to achieve desired equilibrium concentrations in packages.

Microbial and non-microbial spoilage are tem-perature-dependent, therefore temperature is the most important factor to control muscle foods as well [9]. Even psychrophilic bacteria (i.e. Pseudo-monas spp.) have a reduced growth rate at tempera-tures below 10oC [9]. Solubility of carbon dioxide increases with decreased temperatures, which can be advantageous due to its pH lowering bacterio-static effects or disadvantageous regarding package collapse. Dual-function carbon dioxide emitters, such as citric acid and sodium bicarbonate contain-ing absorbent pads may be useful [133].

Temperature fluctuations also affect relative humidity (RH%). Storage studies are often per-formed without RH% control, especially at high RH% conditions where most of the fresh produce is stored [132]. However, at low temperature storage, even slight temperature differences can cause large swings in RH%. When temperatures fall below dew points water condenses on colder surfaces. Result-ing availability of liquid water facilitates microbial growth and related spoilage [134]. This can be miti-gated by sufficient aeration during storage, but that is mostly effective for unpackaged produce. Linke and Geyer [135] investigated condensation inten-sity under changing temperature conditions of packaged plums and demonstrated that in-package and produce condensation is separately affected by environmental air flow, amplitude of the varying temperature, package headspace and cycle time. Lower RH% values cause accelerated moisture and associated weight loss of products, as well as losses in firmness, texture, and color. Open storage appli-cations are relatively easier to control by mechani-cal systems. Packaging films typically do not have adequate water vapor transmission rate (WVTR), resulting in condensation and unsightly fogging on the inner layer of the package [136]. Reduction of water from packages translates into economic

losses for the sellers [42] since produce is mostly sold by weight. Packaging films tend to trap water vapor in packages, which may be mitigated with anti-fogging polymer additives and/or perforations. However, perforated films do not have the same gas/vapor transmission characteristics as non-perforated films [137]. Resistance to transfer of water vapor in perforated packaging depends on the number and size of perforations [134]. However, increasing the number and/or size of perforations leads to loss of benefits related to MAP. Industry has been devel-oping solutions for monitoring environmental con-ditions during cold chain operations. Recent devel-opments include advancements in time temperature indicators/integrators (TTI’s) including programma-ble digital TTI’s, smart labels and enhanced commu-nication systems with cloud based storage and real-time alerts with smart phone applications. Figure 1 shows indicators that can monitor the tempera-ture abuse as well as time spent at those conditions. In timestrip® TTI’s, two migration mediums are brought in contact with rupture activation to produce a color change as a function of temperature. Table 3 shows a summary of related commercial solutions.

Fresh produce packaged with transparent films are exposed to varying light conditions in the supply chain. Proper lighting in retail displays is impor-tant for consumer perception. In addition to other metabolic activities, photosynthesis plays a role in gas composition changes for green and leafy veg-etables due to presence of chlorophyll. Quality of baby spinach was reported to increase when stored under low light conditions along with increases in carbon dioxide. Increasing light intensity tends to reduced quality such as leaking of solutes from leaves and declines in ascorbic acid [138]. Baby spinach stored under MA conditions caused less cell damage with varying light conditions [139]. Mar-tínez-Sánchez et al. [140] demonstrated reductions of browning and increase in visual quality of cut romaine lettuce under dark conditions. However,


Fig. 1: Finger-pressure activated time indicators timestrip® PLUS ™ and timestrip® for displaying the time elapsed at the specified temperature threshold (Timestrip UK Ltd.).

Table 3: Summary of the commercial products to display temperature and humidity deviations for fresh produce storage and packaging.

due to the development of high carbon dioxide and low oxygen concentrations, anaerobic respiration was triggered in their samples. Higher permeability films were recommended for low light conditions. Beef and ham were shown to be affected negatively

by photooxidation of lipids [141]. Light was found to be destructive to color in cooked and sliced ham, however, and color was more stable in 30% CO2 and 70% N2 MAP packages [142].

Commercial Name Function Reading Device Company

UltraContact and Ultra Wireless Labels

Smart labels with temperature sensors with the option of real time monitoring of the ambient or surface temperatures

Ultra Contact or Wireless

PakSense™ Inc.

Thinfilm Smart Label™

Monitor Mark® Time Temperature Indicator (TTI) with information on exposure time

Printed label with programmable upper and lower limits of the allowable temperatures and indicates exceeded limit on the label

N/A

N/A

Thin Film and PST Sensor

3M

Tectrol® Check Sticker MAP Pallet Indicator for berries with a switch of color when accumulation of time exceeds the critical limit at abuse temperatures.

N/A Trans Fresh and Insignia Technologies

RF Wireless Temperature Sensors

ThermoTrace TTI Label for Temperature control

Placing the sensors in different locations and food simulators in refrigerated systems and real time communications on cloud based sharing.

Wireless

Laser Scanner

FreshLoc Technologies Inc.

DeltaTrak® Inc.

Xsense® HiTags RF Sensor Tags for real time temperature and RH control and Cold Chain Logistics evaluations and cloud based data from producer to retail end user

Wireles communication units

BT9 Ltd.

Timestrip® TTI Label for monitoring temperatures customized for varying thresholds from 3oC-10oC up to 4 hours of abuse conditions.

N/A TimeStrip®

Fresh Check® TTI Label for Consumer Use N/A TempTime Corporation

N/A = Not Available


ACTIVE PACKAGING COMPONENTS TO MEDIATE MODIFIED ATMO-SPHERES

Modified atmospheres can be supported or facil-itated through scavengers, emitters, and integral components of packaging materials. Depending on specific requirements of products, active packag-ing (AP) systems are designed to emit, scavenge, or maintain gas and/or vapor (e.g. moisture, aroma). Active components are provided in a variety of forms including sachets, sheets, film coatings, closure liners or embedded in package materi-als as laminates. Committing to use active compo-nents leads to concerns related to accidental inges-tion by consumers, leaks or release from broken inserts into foods and/or failures to add components to packages during manufacture [116]. Regardless of the form, moisture-activated active components will not function if required moisture levels are not reached in packages. Additionally, permeable layers should be aligned with active components to enable active exchange with package environments [143]. The most widely used absorbers can actively modify oxygen, carbon dioxide, ethylene and moisture, acet-aldehyde, sulfide, bitterness, lactose and UV-light [144]. One problem related to active compounds is their own storage stability, since they are active. This is especially problematic after incorporation into film structures [145]. When possible, an ini-tiation mechanism (e.g. U.V. triggered) should be included. Current commercial oxygen, ethylene and carbon dioxide absorbers/emitters and their use for packaging is provided in Table 4.

Gas Absorbers

Absorbers, when used in combination with MAP, enables higher production speeds and better performance than vacuum or gas flushing alone [21]. Oxygen scavengers in packaging of muscle foods offers potential to reduce dependency on

complex and costly film technologies. Due to increasing consumer demand for high quality and minimally processed foods, global revenue of oxygen scavengers including sachets, films and food products are expected to reach $2.5 billion by 2020 with a five year compounded annual growth rate of 3.1% [8]. The purpose of oxygen scaven-gers is to minimize product exposure to oxygen that is initially dissolved as well as oxygen that enters packages via permeation, diffusion and leaks. Oxygen scavengers have been shown to be capable of reducing residual levels to less than 0.01%, (Rooney, 1995b). Oxygen scavengers use a variety of agents including iron, enzymes (i.e. glucose oxidase and alcohol oxidase), photosen-sitive dyes, ascorbic acid and unsaturated fatty acids. Effectiveness is defined by overall capacity and rate of absorption [146]. In iron-based scaven-gers, presence of acids such as malic acid, tartaric acid, acetic acid, potassium bitartrate, alum, benzoic acid, and citric acid promote accelerated oxidation [147]. Additional chemical systems used are Metal/Acid Nylon MXD6, catechol, ferrous sulfate, salt-copper sulfate carbonate. Oxygen scavengers are selected based on cost, packag-ing format, shelf-life extension required, water activity of food, initial and required final oxygen levels [20] and storage temperature.

The most widely used oxygen scavengers are individual sachets, inserts, labels or strips contain-ing iron and/or ferrous salts that are oxidized in the presence of moisture, which is typically provided from moist products. Electron transfer during oxi-dation is accelerated by aqueous solutions and elec-trolytes which is explained by the primary mecha-nism of oxidizing iron to ferric oxides and hydrox-ides with the presence of water. Thus, perfor-mance of moisture dependent scavengers depends on product water activity and their scavenging rates can be adjusted for specific %RH condi-tions. For example, for dry products, water must be


introduced to activate the scavenger. [144] reported that iron containing labels should not be used with acidic foods (e.g. tomato sauce) where rapid iron migration may exceed the maximum tolerable limit of 48 mg per kg of food. Iron migration is negligi-ble for dry and low water activity foods. However, films should be separated from food contact to minimize migration [148]. Sachet-type absorbers are often packaged in a separate paper-polyethyl-ene packages. While iron-based oxygen scaven-gers are safe, it is difficult to determine whether sachets are fresh or have already been depleted. Sachet contents appear black when fresh and red (i.e. rusty) when depleted [149].

Use of enzymes are challenging due to temper-ature and pH sensitivity, aqueous medium required and price. Alcohol oxidase does not require water and is suitable for low water activity products, although storage stability may be affected when embedded in polymer [150]. This is due to the sensitivity of enzymes to pH, temperature, water presence. There are methods to increase storage stability of enzymes in the polymeric matrix such as preserving the water monolayer around the embedded enzymes, immobilization to solid struc-ture and reduced mobility with increased glass transition temperatures. However, immobilization has disadvantages like reduced enzyme activity per volume of film and higher costs [151] Sulfite salts can also be used to reduce oxygen while produc-ing sulfates. Such organic-based active substances including ascorbic acid, unsaturated fatty acids and enzymes do not interfere with metal detectors on production lines. Due to sensitivity of some fresh produce to carbon dioxide its accumulation from product respiration can be reduced using absorb-ers. Components used for absorbing carbon dioxide include calcium hydroxide (involving water depen-dent absorption to produce calcium carbonate), sodium hydroxide, potassium hydroxide, calcium oxide and adsorption on silica gel.

Ethylene is a growth and maturation hormone in plants and can be removed from fresh produce packages by absorbers containing active ethylene-oxidizing reactants. Commonly used scavengers are in forms of sachets and polymer films con-taining potassium permanganate. Potassium per-manganate is first oxidized to acetaldehyde and then to acetic acid. When there is enough potas-sium permanganate, carbon dioxide and hydrogen are produced, and intermediate reactants, such as potassium hydroxide, are formed irreversibly.

Gas Emitters

Carbon dioxide emitting systems usually include dual function (i.e. simultaneous O2 scaveng-ing and CO2 emitting). Especially for products such as fresh produce benefiting from high CO2 levels, but required high permeability films to maintain a certain level of O2 to prevent anoxia. CO2 emitters include sodium bicarbonate, fumaric acid, calcium chloride, fumed silica [152], ascorbic acid, citric acid and ferrous carbonate. Metal halides generate carbon dioxide when exposed to water. A novel, moisture initiated O2 emitting and CO2 absorbing technology was awarded a patent by the United Kingdom, which includes a mixture containing carbonate peroxyhydrate component placed in O2 permeable laminate pouch [153]. Such technology can be included in packages designed for super-atmospheric O2 packages, to keep the O2 concen-trations at beneficial higher levels due to O2 lost via package permeation.

Multi-Function Absorbers and Emitters

Muscle foods and high carbon dioxide tolerat-ing fresh produce require elevated carbon dioxide and lower oxygen, which can lead to package defla-tion. Exudates and/or condensed water may need to be removed in order to avoid formation of envi-ronments favorable for microorganisms. Multiple function absorbers/emitters serve these purposes.


For example, a moisture activated mixture of sodium bicarbonate, fumaric acid, sodium erythorbate, ferrous sulfate, calcium chloride and fumed silica is contained in absorbent and microporous layers absorbing oxygen and exudates while releasing carbon dioxide [143]. Calcium hydroxide and iron powder are combined to absorb oxygen and carbon dioxide [154]. Dual function ethylene and oxygen absorbers are effective in limiting microbial growth and reducing respiration rate [155]. Figure 2 illus-trates a multi-function CO2 emitter and moisture absorber active pad application for salmon.

Other Absorbers and Emitters

Moisture absorbers

Due to high moisture of fresh produce and fresh muscle foods, condensation is often an issue under variable temperature conditions [21]. Exudates are controlled via absorbent pads, pouches, or mats. Condensation is mitigated by anti-fogging addi-tives in polymers, but these promote droplet for-mation, which then drip downward in packages. The most common moisture absorbing/adsorb-ing agents are silica gel, propylene glycol, polyvi-nyl alcohol, modified starch, clay etc. [21], [111], [156]. Polyacrylate salts and copolymers grafted by starch are examples of commonly used polymers [21]. Ethylene, sulfur dioxide and chlorine dioxide

emitters also serve for color stability, postharvest ripening for green-picked climacteric produce and antimicrobial purposes. Due to their toxicity, release of such chemicals should be controlled.

Active Absorbers and Emitters in Fresh Produce and Muscle Foods

Fresh Produce

Oxygen, carbon dioxide and ethylene absorb-ers in fresh produce were shown to be effective in preventing color and texture changes caused by non-enzymatic reactions. Charles et al. [157] dem-onstrated use of a commercially available, iron-based oxygen absorber (ATCO® LH100, Standa Industies, France) in tomatoes packaged in low density polyethylene (LDPE) film, helped to reduce time required to reach optimal oxygen concentra-tions, which limited respiration rate and prevented excess carbon dioxide production. Charles et al. [158] demonstrated a reduced transitional period of 50 versus 100 hours with the reduced iron-based oxygen scavenger (ATCO® LH-100) and with carbon dioxide absorber containing sodium hydroxide (ATCO® CO-450). Charles et al. [159] observed a delayed greening and browning with the LDPE packages with LH-100 oxygen scav-engers on fresh endives compared to the micro-perforated Oriented Propylene (OPP) and LDPE

Fig. 2: Multi-function active pads with exudate capturing and CO2 emitting capabilities to provide prolonged shelf life for muscle products.

Absorbent/Active Pad

Tray

Lidding film


Table 4: Commercial gas regulating AP components used in fresh produce and muscle foods.

Company Commercial name Function / Form Product Examples

Mitsubishi Gas Chemical Co.,Japan

Ageless® type ZP and ZPT Iron powder oxidation

Dried meats, beef jerky, processed meats, fish, and seafood

Type

Fast reacting type, self-reactingOrganic non-iron type suitable for metal detectors.Water dependent (initiated) iron oxidationIron-based film for aseptic and retort processing applications

Ageless® type GLSAgeless® type SS

Ageless® type FX-LAgeless® OMAC®

Standa Industrues, France Distr. by Emco Packaging Systems, UK ATCO® Iron powder oxidation, iron-based labels with Meat, fish, poultry and

seafood products.

Toppan Printing Co., Japan Freshlizer™ Iron powder oxidation sachetAscorbic acid oxidation

Chevron Phillips OSP® Multilayer polymer with ethylene methyl acrylate, cyclohexane methyl acrylate Wet and dry food

Multisorb Technologies Inc.,USA

FreshPax®

Sliced meats, smoked and cured meatsJerkyFresh®

FreshCard®

Fresh Max®

O-BUSTER® (importedfrom Taiwan)

Iron powder oxidation sachetsMultifunctional O2 absorbing cards

O2 absorbing packets and strips

O2 absorbing adhesive labels

Iron powder oxidation by absorbing packets and strips

Processed and dried meatsDesiccare, Inc., USA

OxySorb® Multilayer polymer filmPillsburry Co., USA

IRON FREE® Non-iron type Processed and dried meats

Cryovac® OS 2000 ™ Multilayer polymer activated by ionizing radiationSealed Air Corp. (Cryovac Div.),USA

Dried or smoked meat products, processed meats

O2 A

bsor

bers

Diamond Clear® PET resins for containers and bottlesPlastipak Packaging Inc.Tea, tomato products, vitamin enhanced products

Shelfplus® O2, Shelfplus®

O2 3200 Oxygen absorbing film and high barrier filmAlbis Plastic, Germany

OXYGUARD™ SachetsClairant International,Switzerland Processed meat

H Type, S Type, P Type SachetsAmelco Dessicants Inc. Dried fruits and nuts, bakery products, snacks

CO2 A

bsor

bers

Standa Industrues, France andEmco Packaging Systems, UK ATCO®CO2 Carbon dioxide absorber bags Products with CO2

sensitivity

CELOX® 210, 210B, 210W, 300, 2002, 2003

Oxygen scavenging closure sealant and masterbatch, non-PVC scavengers with polyolefins fo

GCP Applied technologies PET and bottle applications

OxyVac® Enzyme based oxygen scavengerNutricepts, Inc. MAP foods with aw>0.65 and cheeseproducts

DryPak Oxygen Absrober Oxygen absorbing sachetsDrypak Dry and solid foods

TOMATSU®Active carbon and oxygen absorbing component contained in green tea. Suitable for metal detectors

OhE Chemicals, Inc., Japan

Dried laver, sardines, ham, confectionery

SEQUL

CRISPER HF

Iron-based scavenger

Ethylene absorbing sachets

Confectioneries, dried fish

Apples, Japanese pears, persimmons,kiwi, broccoli, melon


Table 4 cont’d: Commercial gas regulating AP components used in fresh produce and muscle foods.

Company Commercial name Function / Form Product Examples

Peakfresh®, USA Produce retail bags containing minerals and household-type sachets

Type

Produce retail bags containing minerals, sachets containing minerals for ethylene and CO2 absorptionEthylene absorbing sachetsepax

Evert-Fresh Green Bags™

Dri-Loc® Moisture absorbing pads, oven-safe and compost-able absorbent meat pads, pouches and mats

Ethy

lene

Abs

orbe

rsM

ultip

le F

unct

ion

Abs

orbe

rs a

nd E

mitt

ers

Vartdal Plastindustri AS SUPERFRESH CO2 emitting, fluid absorbing system embedded into the bottom tray. Salmon, Cod, Chicken

Evert-fresh Corporation, USA

IMPAK Corporation, USASealed Air Corp. (Cryovac Div.),USA

Fresh produce and flowers

Fresh produce and flowers

Fresh produce and flowersFresh produce and fresh meat, fish, poultry

CSP Technologies Activ-Pak CO2 emitting polymer material with carbonates or bicarbonates Bottles and cap liners

Co2 Technologies CO2® Fresh PadsCitric acid and sodium bicarbonate containing moisture absorbent and CO2 emitter pads

Strawberries, tomatoes, broccoli, washed lettuce and muscle foods including meat, seafood, fish and poultry.

Paper Pak Industries UltraZap® Xtenda PakMoisture absorber, CO2 and antimicrobial emitter containing citric and sorbic acid mixtures in form of cellulose pads

Fresh meat and poultry, fresh cut produce(e.g. fresh cut tomatoes)

OhE Chemicals, Inc., Japan CRISPER NK Carbon dioxide and moisture absorbing sachetsPersimmons, bamboo shoots, kiwi fruit, citrus fruits and pickles

Mitsubishi Gas Chemical Co.,Japan Ageless ® type GT O2 absorbing and CO2 emitting sachets

Solution for package shrinking in severalproducts e.g. fresh and processed meat, poultry, fish and fresh produce

Ageless ® type E O2 and CO2 scavenging sachets Coffee and products that are sensitive to O2 and CO2

Nutricepts, Inc. OxyVac®-S Enzyme based O2 scavenger and CO2 emitter.Fresh whole, divided, cooked muscle foods (aw>0.65)

Emco Packaging Systems, UK OxyFresh® O2 emitting with CO2 scavenging technologySuper-atmospheric O2 packaging of fresh produce

Moi

stur

e Abs

orbe

rs

Boveda®

Varying RH% from 32% to 84%. Each package has various salt solutions for appropriate humidity conditions. E.g. 84% RH includes water, xanthan gum, potassium chloride and potassium sorbate

Boveda®, Inc., USADried fruits, popcorn, sugar, spices and herbs, tobacco, herbal medicine

Dri-Fresh® Moisture absorbing pads and linersSirane Ltd., UKFresh meat, fish, poultry, fresh produce including asparagus and berries

Freund Corporation, Japan Negamold®

Moisture dependent and self-reaction type oxygen absorbers, controlling the yeast and B. subtilis by ethanol vapor.

TenderPac® Dual-compartment vacuum pack to separate exudatesSEALPAC® Fresh meat

Fresh-R-Pax® Absorbent trays and padsMaxwell Chase Technologies, LLC

Fresh-cut fruits and vegetables

MeatGuard Absorbent pads with superabsorbent fibersMacAirlaid Inc. Fresh meat, fish, poultry

Ageless® type GEPreventing the package shrinkage by O2 absorbing and CO2 emitting

Mitsubishi Gas Chemical Co.,Japan Rice cakes, nuts, dried fish


packages without scavengers. Jayathunge and Illeperuma [160] analyzed color, percent weight loss, ethanol and carbon dioxide production and consumption of oxygen of oyster mushrooms packaged with varying amounts of magnesium oxide as carbon dioxide scavenger. They dem-onstrated increased shelf life from 6 to 12 days. A carbon dioxide absorber based on sodium car-bonate peroxyhydrate, sodium carbonate, sodium chloride and bentonite clay mixed in two dif-ferent combinations (EMCO-A and EMCO-B, EMCO Packaging Systems, UK) were shown to be effective in preserving quality of strawberries by maintaining equilibrium carbon dioxide levels in packages [161]. An ethylene absorber based on palladium chloride and charcoal was dem-onstrated to be beneficial for limiting ethylene exposure and texture loses in kiwifruits, bananas and chlorophyll degradation in spinach leaves [162]. Home-use ethylene absorbing bags incor-porating sodium permanganate (Blueapple®, Aureus Products Innovations Inc., UT, USA), and potassium permanganate with zeolite (ExtraL-ife®, Dennis Green Ltd., CO, USA). [163], evalu-ated carbon dioxide absorbing characteristics of four chemicals including calcium oxide, magne-sium hydroxide, sodium carbonate and calcium hydroxide in high density polyethylene sachets of kimchi. They demonstrated enhanced carbon dioxide absorption rate when sodium carbonate and zeolite were combined in active sachet film. [164] developed a moisture regulating tray with sodium chloride and ionomer mixed as a hygro-scopic active layer and determined absorption kinetics in different salt solutions, and separately in tomatoes and strawberries. They demonstrated effectiveness of trays with 12% by weight NaCl in tomatoes, however, moisture loss in strawberries was observed. Wang et al. [165] developed an agar based biofilm as sodium carbonate and sodium glycinate as active moisture and carbon dioxide

absorber. They showed labels manufactured from active biofilm could preserve quality of shiitake mushrooms for five days by preventing moisture and carbon dioxide accumulation in packages.

Muscle Foods

Carbon dioxide emitters prepared with sodium bicarbonate and citric acid mixtures contained in moisture absorbent pads were demonstrated to be more effective in increasing shelf life and reducing headspace to product ratio than vacuum packag-ing of pre-rigor fillets and loins of Atlantic cod [166], [167] and Atlantic salmon [168]. Packages with oxygen absorbers or carbon dioxide emitters limited growth of L. monocytogenes, Enterobac-teriaceae and total aerobic bacteria in ready-to-eat meat product, whereas antimicrobial compound, allyl isothiocyanate, was only effective on L. mono-cytogenes [169]. Carbon dioxide emitters included in chicken fillet packages were shown to be ben-eficial in extending shelf life and decreasing drip losses caused by high carbon dioxide storage, however, package collapse was observed [170].

Essential oils and natural antioxidants are some-times used as reducing agents to prevent oxidation in muscle food products. Inclusion of oregano oil in combination with iron-based absorbing sachets were shown to increase shelf life of rainbow trout fillets from 4 days to 17 days via microbial and sensory analyses [171]. Rosemary extract was found to be more efficient than a commercial oxygen scaven-ger in preventing High Pressure Processing (HPP)-induced lipid oxidation in pork patties [172]. Sirocchi et al. [173] demonstrated 15-day increased shelf life of refrigerated beef when stored at high oxygen con-centrations in packages containing active polyeth-ylene sheets sprayed with rosemary essential oil. Emitters can include chemicals and natural compo-nents to release oxygen, carbon dioxide, nitrogen, ethylene, antioxidant, antimicrobials, sulfur dioxide, chlorine dioxide and flavor [144].


ADVANCEMENTS AND FUTURE WORK

Mathematical Modeling Approach

Estimation of gas concentration changes with different package and produce parameters is nec-essary before a successful MAP application can be designed. The “Pack and Pray” approach rarely achieves desired outcomes [174]. Mathematical models combined with computer simulation can predict transient and equilibrium gas composi-tions as they are affected by mass transfer (i.e. dif-fusion, gas and water vapor permeation through the package material and plant tissue), physio-chemical reactions due to the plant metabolism (i.e. respiration, transpiration) and heat transfer (i.e. external cooling and internal heat genera-tion by the produce respiration). For food pack-aging, the majority of these models are based on macroscopic balances. Increasing computational power has led to improved models that help us to understand the complex mechanisms and bio-chemical processes occurring in MAP products. Structures at smaller scale such as cells and inter-cellular spaces are responsible for macro-level changes such as gas exchange. Therefore, multi-scale modeling may prove to be useful in MAP. Multiscale modeling has recently been applied to postharvest research in attempts to relate macro-scopic attributes such as diffusion parameters to microscopic structures [175]. Ho et al. [176], [177] evaluated gas exchange mechanisms by diffusion laws and calculated diffusion coefficients as well as partial pressure differences of carbon dioxide and oxygen using 2D pear and 3D intact apple micro-structures. They found that variations in gas permeation values are caused by distributions of micro structures and selectivity of gas diffusion (i.e. different paths for oxygen and carbon dioxide) through these structures (i.e. intracellular liquid

or void spaces that are resistant to the diffusion). Scales in multiscale modeling can be at various levels. For example, Defraeye et al. [178] inves-tigated effects of micro parameters (i.e. surface cracks, lenticels and water droplets) on gas and heat exchange dynamics of apples (i.e. convec-tive heat and mass transfer coefficients) in a microscale computational fluid dynamics (CFD) modeling approach, where they also assessed modeling parameters. CFD at single scale is also an efficient tool to predict dynamic changes with various conditions in MAP. Bonis et al. [179] used CFD to predict average temperatures and oxygen and carbon dioxide concentrations in the package headspace coupled with microbiological load and moisture distributions for the MAP truffles and cactus pears. No literature was found on multiple scale models focusing on gas releasing/absorbing AP components. Predictive gas kinetics of AP-mediated MAP were studied by [158], [180]–[182]. Parameter uncertainties through interval analysis were modeled in fresh produce package design [183], for which applications can be expanded.

Trends and Challenges

Adopting recent active packaging technology depends on economics, preferences of producers, retailers and consumers. Particularly, costs related to advanced packaging methods and correspond-ing willingness by consumers to pay a premium or to realize cost savings from these technologies that offset investments are required. Moreover, consumer viewpoints for enhanced quality via pack-aging is limited [184]. Packaging materials should be developed to meet the functions of a packag-ing system and should be able to inform consumers about the product contents such as nutritional values [185]. Regional differences play an important role. For example, the North American market is more “consumer/packer” oriented, whereas the European market is determined mainly by retailers [186].


The use of bio-based and biodegradable mate-rials in active as well as passive packaging has been gaining popularity over the recent years. Scarfato et al. [187] demonstrated a biodegradable oxygen scavenger with alpha-tocopherol and poly(lactic)acid (PLA) formulation. Pant et al. [188] developed a bio-based oxygen scavenging film with extrusion and lamination of bio-based layers of adhesive, Gallic acid and sodium carbonate mixture as the active layer, a food contact layer, and PLA. Junior et al. [189] developed a linear low density polyeth-ylene-starch based film with increased biodegrad-ability, which was incorporated with citric acid to provide active packaging properties in beef pack-aging. Similarly Stoll et al. [190] demonstrated the effect of starch based film incorporated with anti-oxidants from wine grape pomace on the quality of extra virgin olive oil. Domenek et al. [191] inves-tigated the antioxidant and mechanical properties of biodegradable PLA-lignin films. Even though consumer preference towards bio-based materials increase, there are drawbacks associated with PLA films, poor barrier properties for O2, CO2 and N2 [192], and high costs [193].

Active and intelligent packaging patents associ-ated with meat packaging from early 2000’s to 2014 were reviewed by [194]. Some recent patents are also included in this section. Novel approaches include incorporation of active agents into the packaging film, maintaining refrigerated temperatures and improvements to existing package configurations. A recent patent was issued for an oxygen emitter for meat packaging [195] that involves a single layer film incorporating an iron-based oxygen scaven-ger and a moisture regulating agent that functions at refrigerated temperatures [196]. Another patent involves a potassium permanganate/polymer blend that can absorb oxygen and ethylene produced by fresh produce [197]. N-hydroxyimide derivates and transition oxygen scavenger metals such as cobalt, nickel or copper in transparent polyolefin films for

food packaging applications was recently patented [198]. A multilayer oxygen absorbing film contain-ing a scavenging layer of ethylene/methyl acrylate/cyclohexene methyl acrylate copolymer (EMCM) was also recently patented [199].

Besides benefits, there are challenges to consider when designing MAP with active pack-aging. Chemical-containing active packaging may have the disadvantage of rejection by health-con-scious, natural product-oriented consumers, espe-cially when used as external parts such as pouches or sachets. Accidental ingestion or rupture of the sachets are among the primary concerns [200], [201]. Hence, recent efforts to incorporate active components into package films are becoming popular in order to reduce interactions of active components with consumers [19].


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