SYSTEMS AND METHODS FOR MAINTAINING PERISHABLE FOODS
CROSS REFERENCE TO RELATED APPLICATIONS
[001] This application claims the benefit of U.S. Provisional Patent Application Serial
No. 61/___,___, which is converted from U.S. Utility Application Serial No. 12/610,126
filed October 30, 2009, and U.S. Provisional Patent Application Serial No. 61/256,868
filed on October 30, 2009, both of which are incorporated herein by reference in their
entirety.
FIELD OF THE INVENTION
[002] This invention relates to systems and methods for increasing the storage-life of
oxidatively-degradable foodstuffs such as fresh fish.
BACKGROUND
[003] The storage-life of oxidatively-degradable foodstuffs such as fish, meat, poultry,
bakery goods, fruits, grains, and vegetables is limited in the presence of a normal
atmospheric environment. The presence of oxygen at levels found in a normal
atmospheric environment leads to changes in odor, flavor, color, and texture resulting in
an overall deterioration in quality of the foods either by chemical effect or by growth of
aerobic spoilage microorganisms.
[004] Modified atmosphere packaging (MAP) has been used to improve storage-life
and safety of stored foods by inhibition of spoilage organisms and pathogens. MAP is the
replacement of the normal atmospheric environment in a food storage pack with a single
gas or a mixture of gases. The gases used in MAP are most often combinations of oxygen
(O2), nitrogen (N2), and carbon dioxide (CO2). In most cases, the bacteriostatic effect is
obtained by a combination of decreased O2 and increased CO2 concentrations. Farber, J.
M. 1991. Microbiological aspects of modified-atmosphere packaging technology: a
review. J. Food Protect. 54:58-70.
[005] In traditional MAP systems, the MAP gas composition is not manipulated after
the initial replacement of the normal atmospheric environment. Thus, the composition of
the gases present in the food pack is likely to change over time. Changes in the gas
portion of the packaging can be due to diffusion of gases into and out of the product,
diffusion of gases into and out of the food pack, and the effects of microbiological
metabolism. In certain cases, the foodstuff will absorb carbon dioxide (CO2) reducing the
amount of CO2 in the gas portion of the packaging with a concomitant increase in the
relative amounts of other gases such as oxygen. Carbon dioxide absorption can lead to a
negative pressure in the tote creating a "vacuumizing" situation which could potentially
damage the foodstuff by, e.g., reducing the carbon dioxide concentration below levels
effective for inhibiting microbial spoilage of the foodstuff with corresponding increases in
residual oxygen concentrations. Vacuumization caused by CO2 absorption can also cause
leakage, especially in rigid totes, resulting in failures.
[006] The use of MAP systems and related technologies has been in use for shipping
and storage of foodstuff. However, these systems imposed significant limitations on the
delivery of food stuffs that are sensitive to oxidative degradation, such as fish. First and
most important, the cooling and oxygen removal processes of these systems were
integrated into a single sealed container (typically a refrigerated freight container - a
refeer unit) such that upon opening the entire shipment was exposed to the ambient
atmospheric conditions. This limited the ability to split the foodstuff into different
delivery sites and typically required that the vendee acquire the entire product upon
opening. Second, the integration of the oxygen removal process into the container
dictated that inadvertent or premature breakage of the seal in the sealed container put the
entire product at risk. Third, the integration of the oxygen removal processes into the
freight container did not permit separate atmospheric conditions within the container
during storing and/or transporting thereby limiting the flexibility of the process. Fourth,
sealing of a freight container posed difficulties especially when the atmospheric pressure
within the container became less than that outside of the container. The most common
MAP applications employ a bag-in-box architecture whereby the perishable is contained
inside a bag/package that is contained inside a box/carton. The bag/package is gas
flushed one or more times to create the desired modified atmosphere before the
bag/package is heat sealed and the box closed. This system may or may not employ
excess headspace to allow for overfilling of gases such as CO2 that are absorbed by many
perishables. The typical constraint on how much excess headspace can be employed is
the requirement that these MAP packages be unitized (stacked) for transport and
handling. This architectural constraint dictates an external carton or box that can be
closed around the bag/package and stacked and easily handled throughout the supply
chain. Consequently, the "excess" headspace designed into these architectures is
inadequate to prevent a decrease in CO2 partial pressures over time with a corresponding
increase in oxygen.
[007] In addition to traditional MAP systems as discussed above, systems for
transporting perishable foodstuffs using an external fuel cell to remove oxygen have been
developed, such as disclosed by US Patent No. 6,179,986. This patent does not describe
the use of a fuel cell but instead it discloses the use of a proton exchange membrane
(PEM) stack based solid polymer electrolyte (EOC) electrochemical oxygen control
system which is operated differently than a fuel cell and requires the application of DC
power. The PEM is operated external to the sealed container to the extent that it required
venting of at least one of the products of the fuel cell reaction to the outside of the sealed
container. Additionally, the system described in the '986 patent required the use of a
dedicated power supply to provide power to the fuel cell.
[008] The systems described above have many disadvantages that make them
undesirable for long-term transporting or storing of foodstuff that is oxidatively
degradable. Thus, the need exists for an improved system that would increase the
storage-life of oxidatively-degradable materials during transport and storage that avoids
the disadvantages of conventional shipping and storage techniques. Additionally, it
would be advantageous to have the ability to transport and then remove modular packages
of the transported foodstuff at various destinations without compromising the preserving
environment of the packages.
[009] Further these architectures, which are usually small in size, generally dictate a
one-time (multiple gas flush event) as they do not have any valves or fittings to facilitate
the initial or additional gas flushes after the initial gas flush process. Furthermore,
multiple gas flushes are not economically viable due to the necessity of reasonable
production throughput requirements. Since these architectures are generally small, easily
handled packages (usually 40 pounds or less) the cost per pound to employ the MAP
process is very high and resulting MAP gas mixture less than ideal for maximum shelf
life extensions.
[0010] An improvement to the above is disclosed in U.S. Serial No. 11/769,944 where a
fuel cell is integrated with a tote comprising oxidatively degradable foodstuffs and an
internal hydrogen source. The fuel cell operates to convert excess oxygen in the tote to
water by reaction with hydrogen.
[0011] Thus, the art to date can be generally characterized as sealed systems which
either do or do not remove residual oxygen from the interior of the system by chemical,
electrical or catalytic processes.
[0012] It would be beneficial to avoid the functional and economic deficiencies of
existing processes for removing oxygen from such storage systems. And there is a need
to remove residual oxygen from such storage systems.
SUMMARY OF THE INVENTION
[0013] In one aspect, this invention provides for totes, packaging modules, systems, and
methods useful in extending the storage-life of carbon dioxide absorbing foodstuff such as
fresh fish. One aspect of the invention provides for a pressure-stable sealable tote of
limited oxygen permeability useful in transporting and/or storing of oxidatively-
degradable foodstuffs. The tote comprises one or more fuel cells, contained internal to
the tote, that are capable of converting hydrogen and oxygen into water. The tote further
optionally comprises a holding element suitable for maintaining a hydrogen source
internal to the tote. The holding element for the hydrogen source in the tote preferably is
a box or bladder configured to hold the hydrogen source and, in some embodiments, the
fuel cell. In preferred embodiments, the tote is selected from the group consisting of a
tote comprising a flexible, collapsible or expandable material which does not puncture
when collapsing or expanding. In other embodiments, the one or more fuel cells and/or
the hydrogen source may be external to the tote. When external to the tote, the fuel cells
are in gaseous communication with the tote.
[0014] This aspect of the invention is based on the discovery that carbon dioxide
absorbing foodstuffs such as fresh fish can significantly and detrimentally affect the gas
composition of the atmosphere above the fish. In such embodiments, initially acceptable
low levels of e.g., oxygen, will increase as more and more carbon dioxide is absorbed
leading to higher oxygen levels in the remaining gas. It can also create a "vacuumizing"
situation which could potentially damage the product, and the tote causing structural
damages, or reducing the carbon dioxide concentration below levels effective for
inhibiting microbial spoilage.
[0015] In the extreme, sufficient amounts of carbon dioxide are absorbed that little or
no head space remains after storage or shipping leaving a detrimental vacuum situation.
[0016] This aspect of the invention is further based on the discovery that the above
problem can be addressed by a packaging module useful in transporting and/or storing
carbon dioxide absorbing foodstuffs which comprises a pressure-stable sealed tote of
limited oxygen permeability and a defined headspace wherein the tote consists of a
flexible, collapsible or expandable material which does not puncture when collapsing or
expanding, an oxidatively-degradable, carbon dioxide absorbing foodstuff, a fuel cell
used in conjunction with the tote that is capable of converting hydrogen and oxygen into
water, a hydrogen source contained, preferably contained internal to the tote and further
wherein the initial headspace occupies at least 30 volume percent of the tote and the gas
in the headspace comprises at least 99 vol. percent gases other than oxygen. In one
embodiment, the headspace is at least 50 vol. percent of the tote. In one embodiment, the
headspace is about or at least 69 vol. percent of the tote. In one embodiment, the gas in
the headspace comprises at least 60 vol. percent carbon dioxide. In another embodiment,
the gas in the headspace comprises at least 90 vol. percent carbon dioxide.
[0017] In this embodiment, the carbon dioxide initially in the head space greatly exceeds
the amount of carbon dioxide which will be absorbed by the foodstuff thereby providing
compensation for its absorption. The amount of carbon dioxide which can be absorbed by
the foodstuff during storage and/or transportation can be determined empirically or is
known in the art.
[0018] Another aspect of the invention provides for a system useful in transporting
and/or storing of carbon dioxide absorbing oxidatively-degradable foodstuffs which
comprises one or more totes. Each packing module comprises a pressure-stable sealed
tote of limited oxygen permeability wherein the tote consists of a flexible, collapsible or
expandable material which does not puncture when collapsing or expanding, an
oxidatively-degradable, carbon dioxide absorbing foodstuff, a fuel cell that is capable of
converting hydrogen and oxygen into water, a hydrogen source, and further wherein the
initial headspace occupies at least 30 volume percent of the tote. In one embodiment, the
initial headspace is at least 50 vol. percent of the tote. In another embodiment, the initial
headspace is about or at least 69 vol. percent of the tote. In some embodiments, the gas in
the headspace comprises at least 99 vol. percent gases other than oxygen. In one
embodiment, the gas in the headspace comprises at least 60 vol. percent carbon dioxide.
In another embodiment, the gas in the headspace comprises at least 90 vol. percent carbon
dioxide.
[0019] In some embodiments, the fuel cell and/or the hydrogen source are internal to the
tote. In some embodiments, the packaging module further comprises a holding element
suitable for maintaining a hydrogen source internal to the tote; preferably the holding
element for the hydrogen source in the tote is a box or bladder configured to hold the
hydrogen source and optionally the fuel cell. In some embodiments, the fuel cell and/or
the hydrogen source are external to the tote. When the fuel cell is external to the tote, it is
in gaseous communication with the tote and one fuel cell may be in gaseous
communication with one or multiple totes and the product of the fuel cell may be internal
or external to the tote.
[0020] In some embodiments, the oxidatively-degradable, carbon dioxide absorbing
foodstuffs to be transported and/or stored are preferably fish. More preferably, the fish is
fresh fish selected from the group consisting of salmon, tilapia, tuna, shrimp, trout,
catfish, sea bream, sea bass, striped bass, red drum, pompano, haddock, hake, halibut,
cod, and arctic char. Most preferably, the fresh fish to be transported and/or stored is
salmon or tilapia. Fresh cooked perishable food would also benefit in the low oxygen
environment
[0021] Additionally, in some embodiments, the hydrogen source is either a bladder
hydrogen source, a rigid container hydrogen source, or a gaseous mixture comprising
carbon dioxide and less than 5% by volume hydrogen. In some embodiments the
packaging module further comprises a fan. In some embodiments, the fan is powered by
the fuel cell. In some embodiments, the fan is powered by another power source.
[0022] The system, in some embodiments, further comprises a temperature control
system which may be internal or external to the packaging module to maintain the
temperature inside the module at a level sufficient to maintain freshness of the foodstuff.
[0023] Another aspect of the invention provides for a method for transporting and/or
storing of oxidatively-degradable foodstuffs using the packaging modules described
above. The method comprises the steps of removing the oxygen in a packaging module
containing an oxidatively-degradable, carbon dioxide absorbing foodstuff to generate a
reduced oxygen environment within a packaging module, filling the tote with low oxygen
gas to provide an initial gaseous headspace wherein the initial headspace occupies at least
30 volume percent of the tote and the gas in the headspace comprises at least 99 vol.
percent gases other than oxygen, sealing the tote, operating the fuel cell during transport
or storing such that oxygen in the tote is converted to water by reaction with hydrogen to
maintain the reduced oxygen environment within the tote, and transporting or storing the
material in the tote. The packaging module comprises a pressure-stable scalable tote of
limited oxygen permeability wherein the tote consists of a flexible, collapsible or
expandable material which does not puncture when collapsing or expanding, a fuel cell,
and a hydrogen source. In one embodiment, the gas in the headspace comprises at least
60 vol. percent carbon dioxide. In another embodiment, the gas in the headspace
comprises at least 90 vol. percent carbon dioxide.
[0024] In one embodiment, the oxygen removal process occurs before adding the
foodstuff to the tote; in another embodiment it occurs after adding the foodstuff to the
tote. In some embodiments, the tote comprises plumbing valves and fittings within the
tote for use to flush the tote with a low oxygen gas source to fill the headspace. In some
embodiments, the tote is flushed prior to turning on the fuel cell. The fuel cell then
continues to remove residual oxygen.
[0025] The method can be used in the transporting or storing the foodstuff for a time
period up to 100 days. For example, the time period for storage is from between 5 and 50
days, or alternatively, from between 5 and 45, or between 15 and 45 days. In some
embodiments, the method further comprises mamtaining a temperature in the tote
sufficient to maintain freshness of the material during transport or storage.
[0026] In preferred embodiments, the method is performed so that the reduced oxygen
environment comprises less than 1% oxygen, or alternatively, the reduced oxygen
environment comprises less than 0.1% oxygen, or alternatively, the reduced oxygen
environment comprises less than 0.01% oxygen.
[0027] The reduced oxygen environment comprises carbon dioxide and hydrogen;
comprises carbon dioxide and nitrogen; comprises nitrogen; or comprises carbon dioxide,
nitrogen, and hydrogen.
[0028] Yet another aspect of this invention provides for methods for removing oxygen
internal to a tote comprising an oxidatively degradable foodstuff without the need for the
use of any chemical, electrical and/or catalytic processes.
[0029] In particular, this aspect of the invention is predicated on the discovery that totes
having appropriate architecture will permit flushing of the tote with a low oxygen gas
source such that any oxygen accumulating in the tote is flushed from the tote prior to
reaching concentration levels that adversely affect the foodstuff. Accordingly, in one of
its method aspects, there is provided a method for removing oxygen from a tote having
oxidatively degradable foodstuff(s) which method comprises:
a) a tote having a sealable gas inlet port and a sealable gas outlet port both ports
being positioned in the head space of the tote wherein the tote comprises a
flexible, collapsible or expandable material which does not puncture when
collapsing or expanding;
b) adding oxidatively degradable foodstuff(s) to said tote in an amount such that
the inlet and outlet ports are not obstructed;
c) sealing the tote;
d) conducting one or more initial flushings of the tote with a low oxygen gas
source by injecting a sufficient amount of such gas source into the tote through
the inlet port while emitting gas through the outlet port so as to provide a low
oxygen atmosphere in the tote and a gaseous head space of sufficient volume
to permit absorption of gas into the foodstuff without increasing oxygen
content in remaining gaseous head space in the tote to a level of above about
1500 ppm;
e) sealing the inlet and outlet ports; and
f) optionally periodically flushing the tote with a low oxygen gas source such
that after flushing there remains a sufficient gaseous head space to compensate
for gas absorption into the foodstuff such that the oxygen concentration in the
remaining gaseous head space does not exceed 1500 ppm at any given time.
[0030] In preferred embodiments, the tote does not contain any internal components to
remove oxygen from the tote such as a fuel cell, a catalyst, and the like.
[0031] The oxidatively-degradable foodstuffs to be transported and/or stored are
preferably fish. More preferably, the fish is fresh fish selected from the group consisting
of salmon, tilapia, tuna, shrimp, trout, catfish, sea bream, sea bass, striped bass, red drum,
pompano, haddock, hake, halibut, cod, and arctic char. Most preferably, the fresh fish to
be transported and/or stored is salmon or tilapia.
[0032] The vertical architecture of the totes disclosed herein facilitates minimizing
horizontal space requirements for shipping the maximum number of pallets side-by-side.
Embodiments that spread the headspace out horizontally may not be as economically
viable at a large scale in addition to not enjoying the leak resistance as long as the
headspace remains positive. In certain embodiments, no more than about 20% of the
expansion of the tote is in the horizontal direction, with the remainder of the gaseous
expansion being in the vertical direction thus creating the "head pressure" and head space
height of the totes. The tote is configured to expand in a vertical manner creating an
initial "head pressure". Initial tote head pressures can range from about 0.1 to about 1.0
inches of water column or more above atmospheric pressure. The flexible tote can be
made more flexible in the vertical direction than in the horizontal by conventional
methods, such as using more flexible material in the vertical direction.
[0033] Additionally, in some embodiments, the low oxygen gas source is any external
gas source that can be adapted to provide the gas source to the inlet port of the tote.
Preferably, the gas source is carbon dioxide and, more preferably, the carbon dioxide
contains less than about 1500 ppm of oxygen. Still more preferably, the carbon dioxide to
be injected into the tote contains less than about 100 ppm oxygen.
[0034] The tote, in some embodiments, further comprises a temperature control system
external to the packaging module to maintain the temperature inside the module at a level
sufficient to maintain freshness of the foodstuff.
[0035] Another aspect of the invention provides for a method for transporting and/or
storing of oxidatively-degradable foodstuffs within the totes described above. The
method comprises the steps of flushing oxygen from the tote with carbon dioxide
containing less than 1500 ppm oxygen wherein the tote contains an oxidatively-
degradable foodstuff thereby generating a reduced oxygen environment within the tote,
sealing the tote, and optionally periodically flushing the tote with carbon dioxide to
maintain the reduced oxygen environment within the tote, and transporting and/or storing
the foodstuff in the tote wherein the tote comprises a flexible, collapsible or expandable
material which does not puncture when collapsing or expanding.
[0036] In one embodiment, the oxygen removal process occurs before adding the
foodstuff to the tote; in another embodiment it occurs after adding the foodstuff to the
tote. In one embodiment, oxygen removal can be achieved by employing a gas flush via
inlet and outlet ports preferably installed positioned in the head space of the tote. In some
embodiments, multiple periodic gas flushes can be employed. The inlet and outlet ports
are sealable such that after the tote is flushed with a low oxygen gas source, the interior of
the tote is isolated. In one embodiment, the inlet and outlet ports are holes wherein one
can simply cover and uncover the holes when gas flushing is required. In such an
embodiment, the holes (inlet and outlet ports) can be covered using tape. This allows for
the inlet and outlet ports to be sealed and unsealed periodically. This architecture
facilitates the economical practice of employing multiple gas flushes over time to remove
oxygen and elevate levels of the low oxygen gas, such as nitrogen and/or CO2.
[0037] The method can be used in the transporting and/or storing the foodstuff for a time
period up to 100 days. In certain embodiments, the method can be used for transporting
and/or storing the foodstuff for a time period of more than 100 days. For example, the
time period for storage is from between 5 and 50 days, or alternatively, from between 15
and 45 days. In some embodiments, the method further comprises maintaining a
temperature in the tote sufficient to maintain freshness of the material during transport or
storage.
[0038] In preferred embodiments, the method is performed so that the reduced oxygen
environment comprises less than 2% oxygen, or alternatively, the reduced oxygen
environment comprises less than 1.5% oxygen, or alternatively, the reduced oxygen
environment comprises less than 1% oxygen, or alternatively, the reduced oxygen
environment comprises less than 0.1% oxygen, or alternatively, the reduced oxygen
environment comprises less than 0.01% oxygen. The level of oxygen can be monitored.
[0039] The reduced oxygen environment comprises carbon dioxide, or in some cases,
comprises carbon dioxide and nitrogen.
BRIEF DESCRIPTION OF THE DRAWINGS
[0040] This invention will be further described with reference being made to the
accompanying drawings.
[0041] Figure 1 is a schematic of a packaging module used to transport or store
oxidatively-degradable material.
[0042] Figure 2 is a schematic of a system comprising a plurality of the packaging
modules in a container.
[0043] Figure 3 is a schematic of a fuel cell embodiment of the oxygen remover.
[0044] Figure 4 is a graph showing the increased duration of low oxygen levels using the
packaging module as compared to a standard MAP system.
[0045] Figure 5 is a photograph of fresh Chilean Atlantic farmed salmon stored in the
packaging module as compared to a standard MAP storage system.
[0046] Figure 6 is a schematic of a fuel cell embodiment of the oxygen remover with a
carbon dioxide remover.
[0047] Figure 7 is a photograph of a packing module embodiment before transporting.
[0048] Figure 8 is a photograph of a packing module embodiment after transporting.
[0049] Figure 9 shows an exemplifying tote.
[0050] Figure 10 is a schematic of a tote used to transport or store oxidatively-
degradable material.
[0051] Figure 11 is a schematic of a system comprising a plurality of the totes connected
to a low oxygen gas source in a shipping freighter.
[0052] Figure 12 is a picture of totes loaded with oxidatively-degradable material in a
shipping freighter.
DETAILED DESCRIPTION
[0053] The present invention encompasses systems and methods useful for transporting
and storing oxidatively-degradable foodstuffs. The systems and methods described herein
allow for the removal of oxygen, for example, periodic or continuous, from the
atmospheric environment surrounding an oxidatively degradable foodstuff which is stored
in an individual tote within a shipping container. In some embodiments, the food stuff is
carbon dioxide absorbing oxidatively-degradable foodstuff.
[0054] The totes or packaging modules used in this invention, as described more
completely below, preferably do not incorporate an integrated temperature control system
but rather rely upon the temperature control system of the shipping container in which
they are shipped. In addition, the tote or packaging module is designed to withstand or
compensate for the internal pressure loss (or gain), such as non-oxygen (carbon dioxide)
gas absorption by the foodstuff, during transport and/or shipment, for example, by
employing a flexible, collapsible or expandable material which does not puncture when
collapsing or expanding and by further employing a gaseous head space within the tote
that compensates for such absorption without creating a vacuum condition and/or
permitting the oxygen content of the gas in the tote to exceed 1500 ppm.
[0055] The periodic or continuous removal of oxygen during transport and/or storage
allows for a controlled reduced oxygen environment that is suitable to maintain the
freshness of the material for a prolonged period. As a result, oxidatively-degradable
materials can be transported and/or stored for longer periods of time than are currently
possible using conventional shipping and storage techniques. The methods described
herein allow, for example, the use of shipping freighters to transport oxidatively-
degradable materials, such as carbon dioxide absorbing oxidatively-degradable foodstuffs,
for example fish, to markets that would normally only be served by more expensive air
shipping.
[0056] In one embodiment, this invention provides systems and methods useful for
extending the storage life of oxidatively-degradable foodstuffs. In a preferred
embodiment, the oxidatively-degradable foodstuff is nonrespiratory. Nonrespiratory
foodstuffs do not respire. That is to say that these foodstuffs do not take in oxygen with
an associated release of carbon dioxide. Examples of nonrespiratory foodstuff include
fresh or processed fish, meat (such as beef, pork, and lamb), poultry (such as chicken,
turkey, and other wild and domestic fowl), and bakery goods (such as bread, tortillas, and
pastries, packaged mixes use to generate bread and pastries, and grain-based snack foods).
Preferred nonrespiratory foodstuff to be transported/and or stored by the systems and
methods of this invention include fresh or processed fish, such as salmon, tilapia, tuna,
shrimp, trout, catfish, sea bream, sea bass, striped bass, red drum, pompano, haddock,
hake, halibut, cod, arctic char, shellfish, and other seafood. More preferably, the
nonrespiratory foodstuff is fresh salmon or fresh tilapia, and most preferably the
nonrespiratory foodstuff fresh Chilean Atlantic farmed salmon.
[0057] In general, the systems and methods of the invention involve a tote, the
oxidatively-degradable foodstuff to be transported and/or stored, and a low oxygen gas
source that periodically flushes the tote with a low oxygen gas, such as carbon dioxide,
thus removing any available oxygen from inside the tote so as to control the gaseous
environment surrounding the foodstuff at least for a portion of the storage and/or
transportation period. In a preferred embodiment, the reduced oxygen environment
within the tote is created by flushing the environment within the tote via application of a
vacuum and/or introduction of a low oxygen gaseous source via an inlet port while the
gas present in the interior of the tote is expelled through the outlet port. After flushing of
the tote, the inlet and outlet ports are sealed, and the environment within the tote is a
reduced oxygen environment. Optionally, the tote is then periodically flushed with
carbon dioxide oxygen as needed throughout the duration of the transport and/or storage
when oxygen is present to maintain the reduced oxygen environment within the
packaging module, thus maintaining the freshness of the oxidatively-degradable material.
In certain embodiments, an oxygen sensor is present internal to the tote in order to signal
the need for flushing with carbon dioxide.
[0058] In some embodiments, the systems and methods of the invention involve a
packaging module comprising a tote, the carbon dioxide absorbing oxidatively-degradable
foodstuff to be transported and/or stored, and a device that continuously removes any
available oxygen from inside the tote when oxygen is present so as to control the gaseous
environment surrounding the foodstuff at least for a portion of the storage and/or
transportation period. This device is also referred to as an oxygen remover. In some
cases, it will be desirable to employ more than one oxygen remover to more effectively
remove oxygen from the tote environment. The carbon dioxide absorbing oxidatively-
degradable foodstuff is inserted into the tote and the environment in the tote is
manipulated to create a reduced oxygen environment in the tote. In a preferred
embodiment, the reduced oxygen environment within the tote is created by flushing the
environment within the tote via application of a vacuum and/or introduction of a low
oxygen gaseous source. After flushing of the tote, the environment within the tote is a
reduced oxygen environment. The tote is filled with the low oxygen gas to provide a
gaseous headspace such that the volume of gaseous headspace is greater than the volume
of gas which is absorbed by the carbon dioxide absorbing oxidatively-degradable
foodstuff. In one embodiment, the tote is filled with carbon dioxide such that the gaseous
head space occupies at least 30 vol. percent of the total volume of the tote and the gas in
the head space comprises at least 99 vol. percent carbon dioxide. The tote is then sealed.
The oxygen remover operates throughout the duration of the transport and/or storage
when oxygen is present to maintain the reduced oxygen environment within the
packaging module, thus maintairiing the freshness of the carbon dioxide absorbing
oxidatively-degradable material. However, as the amount of carbon dioxide employed is
significantly greater than the amount which will be absorbed by the foodstuff, the amount
of oxygen in the headspace on a vol. percent basis is limited as is the likelihood of tote
collapse if the gaseous head space is insufficient to account for carbon dioxide absorption.
[0059] The term "low oxygen gas source" refers to gas sources containing less than a
1000 ppm oxygen; preferably, less than 100 ppm oxygen; and more preferably, less than
10 ppm oxygen. The low oxygen gaseous source is preferably comprised of CO2 or
mixture of gases containing CO2 as one of its components. CO2 is colorless, odorless,
noncombustible, and bacteriostatic and it does not leave toxic residues on foods. In one
embodiment, the low oxygen gaseous source is 100% CO2. In another embodiment, the
low oxygen gaseous source is a mixture of CO2 and nitrogen or other inert gas. Examples
of inert gases include, but are not limited, to argon, krypton, helium, nitric oxide, nitrous
oxide, and xenon. The identity of the low oxygen gaseous source can be varied as
suitable for the foodstuff and is well within the knowledge and skill of the art. For
example, the low oxygen gaseous source used for transport and storage of salmon is
preferably 100% CO2. Other fish, such as tilapia are preferably stored or shipped using
60% CO2 and 40% nitrogen as the low oxygen gaseous source.
[0060] As described above, the pressure-stable sealable tote of limited oxygen
permeability comprises a flexible, collapsible or expandable material which does not
puncture when collapsing or expanding or a tote comprising a rigid material. These totes
are, in general, constructed of flexible cast or extruded plastic sheeting.
[0061] The flexible, collapsible or expandable tote materials for use in this invention are
those having limited oxygen permeability. Materials of limited oxygen permeability
preferably have an oxygen transmission rate (OTR) of less than 10 cubic centimeters/100
square inch/24 hours/atm, more preferable materials of limited oxygen permeability are
materials having an OTR of less than 5 cubic centimeters/100 square inch/24 hours/atm,
even more preferably materials of limited oxygen permeability materials having an OTR
of less than 2 cubic centimeters/100 square inch/24 hours/atm; most preferably materials
of limited oxygen permeability are materials having an OTR of less than 1 cubic
centimeters/100 square inch/24 hours/atm. .A non-exhaustive list of materials that can be
used to make the flexible, collapsible or expandable tote is shown in Table 1.
[0062] The tote may further comprises one or more low oxygen gas sources exterior and
in gaseous contact with the tote via an inlet port to periodically flush the tote, thus
removing any oxygen from the environment within the tote via one or more outlet ports.
Oxygen may accumulate in the tote during use by, for example, diffusion through the tote
through the material of limited oxygen permeability or at the seal of the tote. Oxygen
may also be released by the oxidatively-degradable foodstuff within the tote or from
containers in which the foodstuff is packaged. In a preferred embodiment, the carbon
dioxide is a carbon dioxide gas having less than 10 ppm oxygen.
[0063] In some embodiments, the tote further comprises one or more oxygen removers
to continuously remove oxygen from the environment within the tote as long as oxygen is
present. The oxygen remover maintains the reduced oxygen environment within the tote
by continuously removing any oxygen that may be introduced into the system after the
tote is sealed. For example, oxygen may be introduced by diffusion through the tote
through the material of limited oxygen permeability or at the seal of the tote. Oxygen
may also be released by the carbon dioxide absorbing oxidatively-degradable foodstuff
within the tote or from containers in which the foodstuff is packaged.
[0064] In a preferred embodiment, the oxygen remover is a molecular oxygen-
consuming fuel cell. Preferably the fuel cell is a hydrogen fuel cell. As used herein, a
"hydrogen fuel cell" is any device capable of converting oxygen and hydrogen into water.
In a preferred embodiment, the complete fuel cell is internal to the tote. This can be
achieved by having a hydrogen source internal or external to the tote or packaging
module. The anode of the fuel cell is in communication with the hydrogen source. This
hydrogen source permits generation of protons and electrons. The cathode of the fuel cell
is in communication with the environment in the tote (the oxygen source). In the
presence of oxygen, the protons and electrons generated by the anode interact with the
oxygen present at the cathode to generate water. In a preferred embodiment, the fuel cell
does not require an external power source to convert oxygen and hydrogen into water. In
a further embodiment, the fuel cell is connected to an indicator that indicates when the
fuel cell is operating and when hydrogen is available.
[0065]- In another embodiment, the physical fuel cell is external to the tote but in direct
communication with the gaseous environment of the tote in such a manner that the
products produced at the anode and cathode are maintained internal to the tote. One fuel
cell may be in gaseous communication with one or multiple totes. In such an
embodiment, the fuel cell is construed as internal to the tote since its products are
maintained internal to the tote. When the fuel cell is physically positioned outside the
tote, water produced by the fuel cell may be released outside the tote.
[0066] In a preferred embodiment, the hydrogen source is a pure hydrogen gas. The
hydrogen source is preferably contained within a bladder and the bladder is contained
internal to the tote so that the entire process is contained within the tote. The hydrogen
source is preferably ia direct communication with the anode of the hydrogen fuel cell in
such a manner as to provide hydrogen for the duration of the transporting or storage time.
The bladder is made of any material that is capable of containing the hydrogen gas. For
example, the materials listed in Table 1 can be used as bladder material.
[0067] In a preferred embodiment, the bladder contains an uncompressed hydrogen
source although compressed sources of hydrogen can be used as long as the compressed
source can be contained in the bladder.
[0068] In another embodiment, the hydrogen source is contained within a rigid
container, such as a gas cylinder, contained internal to the tote so that the entire process is
contained within the tote. In this embodiment, the hydrogen source is a compressed or
uncompressed hydrogen source. The rigid container is m direct communication with the
anode of the hydrogen fuel cell in such a manner as to provide hydrogen for the duration
of the transporting or storage time. Compressed hydrogen sources are preferably are
maintained at a pressure of no greater than 10,000 psia. Preferably, the hydrogen source
is uncompressed, which, for example, has a pressure of not greater than 40 psia.
[0069] In further embodiments, the hydrogen source is generated by a chemical reaction.
Examples of methods of chemically generating hydrogen are well known in the art and
include generation of hydrogen by an electrolytic process, including methods using PEM
electrolyzers, alkaline electrolyzers using sodium or potassium hydroxide, solid oxide
electrolyzers, and generation of hydrogen from sodium borohydride. In each case, the
hydrogen is generated so that the hydrogen is made available to the anode of the fuel cell.
[0070] In another embodiment, the hydrogen source is a gaseous mixture comprising
hydrogen present in the environment of the tote. In this embodiment, the gaseous mixture
preferably comprises carbon dioxide and hydrogen. In other embodiments, the gaseous
mixture comprises nitrogen and hydrogen. In further embodiments, the gaseous mixture
comprises hydrogen, carbon dioxide, and nitrogen. It is contemplated that other inert
gases such can be present in the gaseous mixture. The amount of hydrogen present in the
gaseous mixture is preferably less than 10% hydrogen by volume, more preferably less
than 5% hydrogen by volume, most preferably less than 2% hydrogen by volume. This
gaseous mixture is introduced into the tote before, during, or after the introduction of the
oxidatively-degradable material and prior to the sealing of the tote.
[0071] In some embodiments, the fuel cell comprises a carbon dioxide remover in direct
communication with the sealed anode component of the fuel cell. Carbon dioxide has the
potential to permeate across the PEM to anode plate, thereby interfering with hydrogen
access to the anode plate. Removal of some or all of the carbon dioxide from the anode
plate of the fuel cell by the carbon dioxide remover allows increased access to the fuel
cell by hydrogen and thus increasing the fuel cells ability to remove oxygen from the tote
environment.
[0072] There are numerous processes known in the art that can be utilized in the carbon
dioxide remover. These methods include absorption processes, adsorption processes,
such as pressure-swing adsorption (PSA) and thermal swing adsorption (TSA) methods,
and membrane-based carbon dioxide removal. Compounds that can be used in the carbon
dioxide removers include, but are not limited to, hydrated lime, activated carbon, lithium
hydroxide, and metal oxides such as silver oxide, magnesium oxide, and zinc oxide.
Carbon dioxide can also be removed from the anode by purging the anode with a gas,
such as hydrogen gas or water vapor.
[0073] In one embodiment, the carbon dioxide remover comprises hydrated lime, hi
this embodiment, for example, the hydrated lime is contained in a filter cartridge that is in
vapor communication with the fuel cell anode so that the carbon dioxide present at anode
plate of the fuel cell comes into contact and with and is absorbed to the hydrated lime. A
particular embodiment comprises two hydrated lime filter cartridges, each in vapor
communication with an anode outlet. The hydrated lime filters facilitate removal of
carbon dioxide from the anode plate of the fuel cell (Figure 6).
[0074] The tote can be configured to provide access for tubes, wires, and the like such
that the external gases, such as carbon dioxide, can be introduced via an inlet port. The
inlet port is provided using fittings that are sealable and can maintain the low oxygen
environment within the tote. In some embodiments, an external power source can be used
to operate fans and oxygen remover. In one particular embodiment, the tote is configured
to permit introduction of hydrogen from an external source into the internal fuel cell
hydrogen supply system. In a further embodiment, the external hydrogen source is
directed to assist with purging the fuel cell with hydrogen.
[0075] Oxygen removers other than hydrogen fuel cells can be used to remove oxygen in
the tote. For example, oxygen absorbers, such as iron containing absorbers, and oxygen
adsorbers, can be used. Oxygen absorbers and adsorbers are known in the art and are
commercially available. Oxygen removers also include removers utilizing pressure swing
adsorption methods (PSA) and membrane separation methods.
[0076] Catalytic systems, such as those utilizing elemental metal such as platinum or
palladium catalysts, can be used as oxygen removers but the use of powders necessary to
provide high catalytic surface area runs the risk of contamination. Nevertheless, when
appropriate safeguards are used, these can be employed. Such safeguards include
embedding the metal catalysts into a membrane electrode assembly such as present in
PEM fuel cells.
[0077] The tote preferably further comprises a holding element suitable for maintaining
the hydrogen source so as the hydrogen source is held stably within the tote. In a
preferred embodiment, the holding element is a box configured to stably hold the
hydrogen source. In a further preferred embodiment, the holding element is configured to
hold both the hydrogen source and the fuel cell. In other embodiments, the holding
element is a sleeve affixed to an internal wall of the tote. This sleeve is capable of
holding a bladder-containing hydrogen source or rigid container hydrogen source as well
as other containers suitable for containing a hydrogen source. In either event, the
hydrogen source is in direct communication with the anode of the fuel cell,
[0078] When the oxygen remover used in the packaging module is a hydrogen fuel cell,
there will be an amount of water, in either liquid or gaseous form, generated as a result of
the reaction of hydrogen and oxygen. In some embodiments, the water thus generated is
released into the tote. It may be desirable to include within the tote a means for
containing or removing the water. For example, the tote may further comprise a water-
holding apparatus, such as a tray or tank, configured to collect the water as it is generated
at the fuel cell. Alternatively, the tote may contain desiccant or absorbent material that is
used to absorb and contain the water. Suitable desiccants and absorbent materials are
well known in the art. The water may alternatively be vented outside of the tote, thus
providing a suitable environment for the storage and transportation of goods that are
optimally stored in dry environments.
[0079] The tote is configured to maintain a reduced oxygen environment surrounding the
material. The reduced oxygen environment allows for the material to be stored and/or
transported for a prolonged period while maintaining freshness of the material.
Subsequent to or after the introduction of the material but prior to the sealing of the tote,
the environment within the tote is optionally flushed via application of a vacuum and/or
introduction of a low oxygen free gaseous source. At this point, the environment within
the tote is a reduced oxygen environment. In a particular embodiment, the level of
oxygen in the reduced oxygen environment is less than 1% oxygen, or alternatively, the
level of oxygen in the reduced oxygen environment is less than 0.1% oxygen, or
alternatively, the level of oxygen in the reduced oxygen environment is less than 0.01%
oxygen.
[0080] After a period of time, the oxygen levels present in the tote or packaging module
remain at a reduced level because gaseous exchange between the foodstuff and the tote
environment reached a natural mmirnization or cessation. At this point, the fuel cell will
cease operating. In one embodiment, the fuel cell can be programmed to cease operation
after an initial period time that is sufficient to allow a natural minimization or cessation of
gaseous exchange. Preferably, the fuel cell is programmed to cease operation after a
period of between around 0.5 and 50 hours, more preferably, the fuel cell is programmed
to cease operation after a period of between around 1 and 25 hours; more preferably, the
fuel cell is programmed to cease operation after a period of between around 2 and 15
hours; even more preferably, the fuel cell is programmed to cease operation after a period
of between around 3 and 10 hours.
[0081] In some embodiments, a low oxygen gaseous source is introduced into the tote
before the tote is sealed. The low oxygen gaseous source is preferably comprised of CO2
or mixture of gases containing CO2 as one of its components. CO2 is colorless, odorless,
noncombustible, and bacteriostatic and it does not leave toxic residues on foods. In one
embodiment, the low oxygen gaseous source is 100% CO2. In another embodiment, the
low oxygen gaseous source is a mixture of CO2 and nitrogen or other inert gas. Examples
of inert gases include, but are not limited, to argon, krypton, helium, nitric oxide, nitrous
oxide, and xenon. The identity of the low oxygen gaseous source can be varied as
suitable for the foodstuff and is well within the knowledge and skill of the art. For
example, the low oxygen gaseous source used for transport and storage of salmon is
preferably 100% CO2. Other fish, such as tilapia are preferably stored or shipped using
60% CO2 and 40% nitrogen as the low oxygen gaseous source.
[0082] In order to compensate for the pressure differential that occurs during a
prolonged transport or storage, the tote contains an initial headspace volume that allows
for absorption of gases, such as oxygen, the low oxygen gaseous source, for example
carbon dioxide. The term "initial headspace" is intended to refer to the amount of excess
gaseous volume of the tote after the tote is filled with carbon dioxide absorbing
oxidatively-degradable foodstuff. In some embodiments, the initial headspace is from
about 30% to about 95% the internal volume of the tote. In other embodiments, the initial
headspace is from about 35% to about 40% of the internal volume of the tote, or
alternatively, the initial headspace is about 30% to about 35% of the internal volume of
the tote, or alternatively, the initial headspace is about 35% of the internal volume of the
tote.
[0083] Ultimately, the tote is filled with enough low oxygen gas to provide an initial
gaseous headspace such that the volume of gaseous headspace is greater than the volume
of gas which is absorbed by the oxidatively-degradable foodstuff to compensate for the
pressure differential that occurs during a prolonged transport or storage. The result of the
pressure differential can be seen in Figures 7 and 8. Figure 7 shows a flexible tote of the
invention which has been filled with a sufficient amount of carbon dioxide to .
accommodate the absorption of carbon dioxide into the foodstuff throughout the transport
and handling cycle of the totes and to prevent negative pressure from being created by the
oxygen removal process. Figure 8 shows the same totes of figure 7 after 17 days of
transport with a decreased amount of gaseous headspace. Although the photo of Figure 8
shows that the right tote appears to be inflated more (or deflated less) than the one on the
left, both totes were in fact deflated the same when viewed from all sides. The amount of
headspace remaining after transport should be sufficient such that a negative pressure is
not created as this "vacuumizing" could potentially damage the product, reducing the
carbon dioxide concentration below levels effective for inhibiting microbial spoilage
and/or increases in residual oxygen concentrations and increased potential for leakage. In
certain embodiments the concentration of carbon dioxide in the tote after transport or
storage is at least 90%.
[0084] The tote is configured such that the internal tote environment is in
communication with oxygen remover permitting the continuous removal of molecular
oxygen from the internal tote environment as long as there is oxygen present in the tote
environment. The oxygen remover in the tote is configured to remove oxygen from the
internal tote environment such that the oxygen level remains below a level that would
result in a reduction of freshness or spoilage of the material. This reduced level of
oxygen is maintained by the oxygen remover for the duration of the transport and/or
storage. The level of oxygen in the reduced oxygen environment is less than 1% oxygen,
more preferably less than 0.1%, most preferably less than 0.01% oxygen.
[0085] The efficiency of the oxygen removers can be enhanced through the use of a fan
to circulate the air within the tote thus facilitating contact between the oxygen remover
and the oxygen in the tote environment. When using a fuel cell, the fan, in certain
embodiments, can be configured to run from the energy created when the fuel cell
converts the hydrogen and oxygen to water.
[0086] In the event of a breach in the integrity of the tote wherein an unexpectedly large
amount of oxygen-containing air is introduced into the tote environment, the oxygen
remover would not be able to remove all of the introduced oxygen. In a preferred
embodiment, the tote further comprises an oxygen indicator which would alert one to the
fact that the oxygen level in the tote had exceeded the levels described as a reduced
oxygen environment.
[0087] In some embodiments, it is contemplated that multiple flushes with the low
oxygen gas would allow for gas absorption by the foodstuff, thus alleviating the need for
as much initial headspace. However, it is also contemplated that with a large scale
shipment (i.e. 2,000 pounds foodstuff packaged in multiple cartons) a headspace may be
necessary as gas absorption requires too many days to be practical for shipping purposes.
[0088] In certain embodiments, the totes are able to accommodate a very large
headspace (primarily to accommodate CO2 absorption and protect against/delay air
leakage), such that the headspace in combination with multiple initial gas flushes would
require no continuous oxygen monitoring or further periodic gas flushing beyond the
initial multiple gas flushes. It is contemplated that the initial gas flushes can proceed
periodically during the first 72 hours of the tote being sealed with the oxidatively
degradable foodstuff. Alternatively, the initial gas flushes can proceed during the first 72
hours or less of the tote being sealed, or alternatively, the first 60 hours, or alternatively,
the first 48 hours, or alternatively, the first 24 hours.
[0089] The vertical architecture of the totes disclosed herein facilitates minimizing
horizontal space requirements for shipping the maximum number of pallets side-by-side.
Embodiments that spread the headspace out horizontally may not be as economically
viable at a large scale in addition to not enjoying the leak resistance as long as the
headspace remains positive. In certain embodiments, no more than about 20% of the
expansion of the tote is in the horizontal direction, with the remainder of the gaseous
expansion being in the vertical direction thus creating the "head pressure" and head space
height of the totes. The tote is configured to expand in a vertical manner creating an
initial "head pressure". Initial tote head pressures can range from about 0.1 to about 1.0
inches of water column or more above atmospheric pressure.
[0090] In certain embodiments, the low oxygen gas source is programmed to flush the
interior environment of the tote at predetermined time intervals throughout the duration of
the transport and/or storage. In other embodiments, the low oxygen gas source is
programmed to flush the interior environment of the tote when the oxygen level of the
internal tote environment exceeds a level which is detrimental to the foodstuff. In the
beginning of the transport and/or storage, oxygen may be released by the oxidatively-
degradable foodstuff within the tote or from containers in which the foodstuff is
packaged.
[0091] In a preferred embodiment, the tote further comprises an indicator which would
alert one to the fact that the oxygen level in the tote had exceeded the levels described as a
reduced oxygen environment. In certain embodiments, low oxygen gas source is
programmed to flush the interior environment of the tote when the level of oxygen in the
reduced oxygen environment is about 2% oxygen, more preferably about 1.5%, more
preferably about 1%, more preferably about 0.1%, most preferably about 0.01% oxygen,
or when the level of oxygen exceeds about 1500 ppm oxygen. In a particular
embodiment, a oxygen sensor, for example, a trace oxygen sensor (Teledyne), is used to
monitor the level of oxygen present in the tote environment.
[0092] The tote optionally contains monitors to monitor oxygen levels, hydrogen levels,
fuel cell operation, and temperature. In a particular embodiment, an oxygen sensor, for
example, a trace oxygen sensor (Teledyne), is used to monitor the level of oxygen present
in the tote environment.
[0093] In some embodiments, the tote comprises a box (see Figure 9) comprising
devices which include the fuel cell, the oxygen indicator which alerts one when the
oxygen level in the tote exceeds the levels described as a reduced oxygen environment,
and/or monitors to monitor oxygen levels, hydrogen levels, fuel cell operation, and
temperature. The box further optionally comprises a visible indicator, such as an LED
light, which indicates problems of the devices in the box so that the problematic device or
the box can be immediately replaced before sealing the tote. This facilitates rapid
detection of any failure by unskilled labor and allows for rapid turn-around of boxes into
service with minimal testing. The box also alerts users on arrival of system if oxygen or
temperature (time and temperature) limits are exceeded, preferably, using wireless
communication, such as radio frequency transmission, along with a visible indicator, such
as a red LED light.
[0094] Another aspect of the invention provides for a packaging module useful for
transporting and/or storing of oxidatively-degradable material. The packaging module
comprises a tote configured as described above. In the packaging module the tote is
sealed and contains the carbon dioxide absorbing oxidatively-degradable material to be
transported and/or stored, and a device that continuously removes oxygen from the
environment surrounding the material as long as there is oxygen present. The device is
located within the sealed tote. Temperature control means such as air conditioning,
heating and the like are preferably not integrated into the packaging module and the size
of the module is such that the freight container comprising a single temperature control
means can contain multiple modules. In such cases, it is possible for each tote to have
different gaseous environments and different packaged materials.
[0095] Another aspect of the invention provides for a system for transporting and/or
storing carbon dioxide absorbing oxidatively-degradable foodstuff. The system
comprises one or more of the packaging modules, each packaging module comprising a
tote, a carbon dioxide absorbing oxidatively-degradable foodstuff and an oxygen remover.
The packaging module and components thereof are described above.
[0096] The system or totes are configured so as to be suitable for transporting and/or
storing in a shipping freighter. A shipping freighter means any container that can be used
to transport and/or store the system including, but not limited to, an ocean shipping
freighter, a trucking shipping freighter (such as a tractor-trailer), a railroad car, and an
airplane capable of transporting cargo load. In some embodiments, the tote further
comprises a device for monitoring and/or logging the temperature of the system or
container. Such devices are commercially available from manufacturers including
Sensitech, Temptale, Logtag, Dickson, Marathon, Testo, and Hobo.
[0097] As noted above, one or more totes or packaging modules can be used in a single
shipping freighter and, accordingly, each can be configured to have a different gaseous
environment as well as a different foodstuff. Further, at delivery, opening of the shipping
freighter does not result in disruption of the internal atmosphere of any tote or packaging
module and, accordingly, one or more of the totes or packaging modules can be delivered
at one site and the others at different site(s). The size of each tote or packaging module
can be configured prior to shipment to correspond to the quantity of foodstuff desired by
each vendee. As such, the totes or packaging modules can preferably be sized to contain
as little as a few ounces of foodstuff to as much as, or greater than, 50,000 pounds, or 1
ton of foodstuff. In addition, the vertical architecture facilitates minimizing horizontal
space requirements for shipping the maximum number of pallets side-by-side.
Embodiments, that spread the headspace out horizontally may not be as economically
viable at a large scale in addition to not enjoying the leak resistance as long as the
headspace remains positive. The number of packaging modules per system depends both
on the size of the shipping freighter used to transport and/or store the system and the size
of the packaging modules. Specific examples of the number of packaging modules per
system is set forth in the description of specific embodiments below.
[0098] The size of each packaging module can be sufficiently large such that a shipment
of about 500 pounds or more of carbon dioxide absorbing oxidatively-degradable
foodstuff can be packaged into a single tote. In some embodiments, about 500 pounds of
carbon dioxide absorbing oxidatively-degradable foodstuff can be packaged into a single
tote, or alternatively, about 1000 pounds, or alternatively, about 2000 pounds, or
alternatively, more than about 2000 pounds. This large size permits a shipping freighter
to be filled to capacity without the need for stacking of the totes, thus allowing for the
gaseous headspace. If the packaging modules are smaller than the internal dimensions of
the shipping freighter, a scaffolding may be employed to house the packaging modules
and allow stacking.
[0099] In another embodiment, the system comprises one or more totes, each tote
containing a carbon dioxide absorbing oxidatively-degradable foodstuff. In this
embodiment, the totes are detachably connected to a separate module that contains the
oxygen remover. The separate module also contains a hydrogen source when the oxygen
remover is a hydrogen fuel cell. The oxygen remover acts to remove the oxygen from all
of the totes to which the separate module is connected. In this embodiment, the physical
fuel cell is external to the tote but in direct communication with the gaseous environment
of the tote. In some embodiments, the products produced at the anode and cathode are
maintained internal to the tote. In such an embodiment, the fuel cell is construed as
internal to the tote since its products are maintained internally to the tote. In another
embodiment, the water produced by the fuel cell is released external to the tote. In
another embodiment, the tote is a rigid tote and the separate module further contains a
gaseous source to maintain positive pressure in the connected totes. The container
optionally contains monitors to monitor oxygen levels, hydrogen levels, and temperature
within the totes as well as an indicator that indicates fuel cell operation. In one
embodiment, the module is a box that is of similar size to the packaging modules. In
another embodiment, the module is affixed to wall, lid, or door of the shipping freighter
used to transport and/or store the system.
[00100] In some embodiments, the system and/or the shipping freighter also comprises a
cooling system for maintaining a temperature of the packaging modules sufficient to
preserve the freshness of the carbon dioxide absorbing oxidatively-degradable foodstuff.
The temperature required to preserve the freshness of the carbon dioxide absorbing
oxidatively-degradable foodstuff is dependent on the nature of this foodstuff. One of skill
in the art would know, or would be able to determine, the appropriate temperature
required for the material being transported or stored in the system or shipping freighter.
For the transport and/or storage of foodstuffs the temperature would generally at about 30
°F (Fahrenheit). The temperature is generally maintained in a range of 32-38°F, more
preferably in a range of 32-35°F, most preferably in a range of 32-33°F or 28-32°F. For
example, the appropriate temperature to preserve fish during transport or storage is
between 32-35°F. Variation in the temperature is allowed as long as the temperature is
maintained within a range to preserve the foodstuff. In some embodiments, the tote
further comprises a device for monitoring and/or logging the temperature of the system or
container. Such devices are commercially available from manufacturers including
Sensitech, Temptale, Logtag, Dickson, Marathon, Testo, and Hobo.
[00101] In one embodiment, the system is capable of maintaining the packaging module
at a foodstuff-preserving refrigerated temperature. Alternatively, the shipping freighter
used to transport and/or store the system is a refrigerated shipping freighter capable of
maintaining packaging module at a foodstuff-preserving refrigerated temperature.
[00102] It is contemplated that it may be desirable to limit the exposure of the foodstuff to
excess hydrogen during transport or storage. Accordingly, in some embodiments, the tote
or system is configured to minimize the exposure of the foodstuff to hydrogen present in
the tote environment. This can be achieved by removing the excess hydrogen in the tote
or system by mechanical methods, chemical methods, or combinations thereof. Examples
of chemical methods of removing hydrogen include the use a hydrogen sink comprised of
polymers or other compounds that absorb hydrogen. Compounds suitable for use as
hydrogen absorbers are known in the art and are commercially available ("Hydrogen
Getters" Sandia National Laboratories, New Mexico; REB Research & Consulting,
Ferndale, MI.) The compounds can be present in the tote or can be in direct
communication with the cathode of the fuel cell.
[00103] Excess hydrogen can be limited by employing mechanical means, including the
use of shut off valves or flow restrictors to modulate or shut down the flow of hydrogen
into the tote environment. The modulation of hydrogen can be controlled by using an
oxygen sensor connected to the hydrogen source such that hydrogen flow is minimized or
eliminated when the level of oxygen falls below a minimum set point.
[00104] A further aspect of the invention provides for methods for transporting and
storing carbon dioxide absorbing oxidatively-degradable foodstuff. The methods utilize
the packaging modules and system as described above. In a preferred embodiment, the
method comprises removing the oxygen in a packaging module after insertion of a carbon
dioxide absorbing oxidatively-degradable foodstuff to generate a reduced oxygen
environment within the packaging module. In addition to the carbon dioxide absorbing
oxidatively-degradable foodstuff, the packaging module comprises a pressure-stable
sealable tote of limited oxygen permeability and oxygen remover. The reduced oxygen
environment within the packaging module is created, for example, by flushing the
environment within the tote via application of a vacuum and/or introduction of a low
oxygen gaseous source to flush the tote. After flushing of the tote, the environment
within the tote is a low oxygen environment. The tote is filled with the low oxygen gas to
provide an initial gaseous headspace such that the initial headspace occupies at least 30
volume percent of the tote and the gas in the headspace comprises at least 99 vol. percent
gases other than oxygen. The tote is then sealed.
[00105] In another aspect, the invention provides for methods for transporting and/or
storing oxidatively-degradable foodstuff. This aspect provides methods described herein
allow for the optional periodic removal of oxygen from the atmospheric environment
surrounding an oxidatively degradable foodstuff which is stored in an individual tote
within a shipping container.
[00106] In a preferred embodiment, the invention comprises a method for removing
oxygen from a tote having oxidatively degradable foodstuff(s) which method comprises:
a) a tote having a sealable gas inlet port and a sealable gas outlet port both ports
being positioned in the head space of the tote wherein the tote comprises a
flexible, collapsible or expandable material which does not puncture when
collapsing or expanding;
b) adding oxidatively degradable foodstuff(s) to said tote in an amount such that
the inlet and outlet ports are not obstructed;
c) sealing the tote;
d) conducting one or more initial flushings of the tote with a low oxygen gas
source by injecting a sufficient amount of such gas source into the tote through
the inlet port while emitting gas through the outlet port so as to provide a low
oxygen atmosphere in the tote and a gaseous head space of sufficient volume
to permit absorption of gas into the foodstuff without increasing oxygen
content in remaining gaseous head space in the tote to a level of above about
1500 ppm;
e) sealing the inlet and outlet ports; and
f) optionally periodically flushing the tote with a low oxygen gas source such
that after flushing there remains a sufficient gaseous head space to compensate
. for gas absorption into the foodstuff such that the oxygen concentration in the
remaining gaseous head space does not exceed 1500 ppm at any given time.
[00107] The low oxygen gaseous source is preferably comprised of CO2 or mixture of
gases containing CO2 as one of its components. In one particular embodiment, the low
oxygen gaseous source is 100% CO2. In another embodiment, the low oxygen gaseous
source is a mixture of CO2 and nitrogen or other inert gas. Examples of inert gases
include, but are not limited, to argon, krypton, helium, nitric oxide, nitrous oxide, and
xenon. The identity of the low oxygen gaseous source can be varied as suitable for the
foodstuff. For example, the low oxygen gaseous source used for transport and storage of
salmon is preferably 100% CO2. Other fish, such as tilapia are preferably stored or
shipped using 60% CO2 and 40% nitrogen as the low oxygen gaseous source.
[00108] The oxygen remover in the packaging module is operated during the transport
and/ or storage as long as oxygen is present such that the oxygen level remains below a
level that would result in a reduction of freshness or spoilage of the material. This
reduced level of oxygen may be maintained by the oxygen remover for the duration of the
transport and/or storage. The level of oxygen in the reduced oxygen environment is less
than 1% oxygen, more preferably less than 0.1%, most preferably less than 0.01%
oxygen.
[00109] After a period of time, the oxygen levels present in the tote remain at a reduced
level because gaseous exchange between the foodstuff and the tote environment reached a
natural minimization or cessation. In one embodiment, the low oxygen gas source can be
programmed to cease operation after an initial period time that is sufficient to allow a
natural minimization or cessation of gaseous exchange. Preferably, the low oxygen gas
source is programmed to cease operation after a period of between around 0.5 and 50
hours, more preferably, the low oxygen gas source is programmed to cease operation after
a period of between around 1 and 25 hours; more preferably, the low oxygen gas source is
programmed to cease operation after a period of between around 2 and 15 hours; even
more preferably, the low oxygen gas source is programmed to cease operation after a
period of between around 3 and 10 hours.
[00110] Alternatively, the low oxygen gas source can be programmed to cease operation
when the oxygen level reaches and is maintained below a predetermined level. In one
embodiment, the oxygen level reaches and is maintained below 5% oxygen v/v, or
alternatively, the oxygen level reaches and is maintained below 1% oxygen v/v, or
alternatively, the oxygen level reaches and is maintained below 0.1 % oxygen v/v, or
alternatively, the oxygen level reaches and is maintained below about 1500 ppm oxygen.
[00111] In some embodiments, the initial flush with the low oxygen gas source is
sufficient to maintain the low oxygen environment during the transportation and/or
storage of the oxidatively-degradable foodstuffs.
[00112] In embodiments where the fuel cell is present in a module that is external to the
totes, the module can be removed after an initial period of time that is sufficient to allow a
natural minimization or cessation of gaseous exchange or when the oxygen level reaches
and is maintained below a predetermined level according to the parameters discussed
above. Any external source of gas used to maintained the positive pressure within the tote
can be removed as well after the gaseous exchange between the foodstuff and the tote
environment reaches a natural minimization or cessation because the need compensate for
a change in pressure within the tote is minimized.
[00113] In a preferred embodiment, the method relates to the system for transporting or
storing carbon dioxide absorbing oxidatively-degradable material as described above.
Thus, in a preferred embodiment, the method comprises transporting or storing one or
more of the packaging modules in a single freight container. In this embodiment, the
individual packaging modules or totes are separately removable from the system. This
feature allows for the delivery of individual packaging modules, or the totes of the
packaging modules, without disturbing the integrity of the packaging modules or totes
remaining in the system.
[00114] The totes, packaging modules and/or the system are then used to transport and/or
store the oxidatively-degradable material, for example the carbon dioxide absorbing
oxidatively-degradable foodstuff, for an extended time period. Preferably, the extended
time period is from between 1 and 100 days; more preferably the extended time period is
from between 5 and 50 days, even more preferably the extended time period is from
between 15 and 45 days.
[00115] The methods described herein allow for the oxidatively-degradable material to be
transported or stored for a prolonged period of time not possible using standard MAP
technology or other standard food storage methods. The prolonged period will vary
according to the nature of the oxidatively-degradable material. It is contemplated that
using the methods disclosed herein, fresh salmon can be stored or transported in a
preserved manner for a prolonged period of at least 30 days. In contrast, fresh salmon can
only be stored or transported in a preserved manner for a period of from between 10-20
days in the absence of a reduced oxygen environment. (See the Examples).
Description of Specific Embodiments
[00116] The following description sets forth a specific embodiment that can be used in the
present invention. The specific embodiment is but one of the possible configurations and
uses of the present invention and should not be construed in any manner as a limitation of
the invention.
[00117] The present invention is particularly suited for the transport and storage offish,
such as salmon. In particular, the invention allows farmed Chilean salmon to be shipped
via shipping freighter to destinations in the United States. The length of this transport
(approximately 30 days) requires the use of the present invention to preserve the freshness
of the salmon. Traditionally, Chilean salmon must be shipped via air freight in order to
reach destinations in the United States before the salmon would spoil.
[00118] The salmon is prepackaged in cases. Each case contains about 38.5 pounds of
salmon. Sixty four of these cases are placed into one tote. The tote is sized at
approximately 50" X 42" X 130", 42" X 50" X 130" or 48" X 46" X 100" and is made of
a poly/Nylon blend material. The tote is oversized by about 35 % or 50% to provide
sufficient gaseous headspace and allow for CO2 (and oxygen) absorption. The tote has
one presealed end and one sealable end. The tote is placed presealed end down on a
pallet. The pallet is preferably covered with a protective sheet to protect the tote and
provide stability to the tote. Fifty four cases of the salmon are stacked in the tote. A
schematic of a tote is shown in Figure 1.
[00119] Another box, ideally with the same dimension as a salmon case is added to the
tote. This box contains one or multiple hydrogen fuel cells and a hydrogen source. The
hydrogen source is a bladder that contains pure hydrogen. The bladder is configured to be
in direct communication with the anodes of the fuel cells to allow the hydrogen fuel cells
to convert any oxygen present in the tote into water for the duration of the transport
and/or storage.
[00120] The box also contains a fan to circulate the air within the tote thus facilitating
contact between the oxygen remover and the oxygen in the tote environment. The fan is
powered from the energy created when the fuel cells convert oxygen to water or by a
separated battery.
[00121] Furthermore, the box contains a temperature recorder so that a record of
temperature changes can be made for the duration of the transport and/or storage.
Similarly, the box contains an oxygen level recorder so that a record of oxygen levels can
be made for the duration of the transport and/or storage. The box also contains an
indicator that provides a warnings as to when the oxygen levels within the tote exceeds a
specified maximum level or the temperature reaches a specified maximum level. In this
specific embodiment, the indicator would warn if the oxygen level exceeded 0.1% oxygen
and if the temperature exceeds 38 °F. The box may further contain monitors to monitor
hydrogen levels and fuel cell operation. The box further optionally comprises a visible
indicator, such as an LED light, which indicates problems of the devices in the box and
alerts users on arrival of system if oxygen or temperature limits are exceeded, preferably,
using wireless communication, such as radio frequency transmission, along with a visible
indicator, such as an LED light.
[00122] The salmon cases and the box are then unitized (cornered and strapped) and the
tote is pulled up around all four sides of the unitized stack with the open end of the tote
gathered into a heat sealer. A gas flush of up to 100% carbon dioxide is performed until
the residual oxygen is less than about 5% v/v, and preferably less than about 1% v/v. The
tote is over-filled with carbon dioxide such that the initial headspace occupies about 50 or
30 volume percent of the tote. After the environment in the tote has been so modified, a
heat seal cycle is initiated and the tote is sealed, forming the packaging module. The fuel
cell operates for the duration of the transport and storage to remove any oxygen
introduced into the packaging module by diffusion through the tote material or at the seal
of the tote. Small amounts of oxygen may also be released by fish or packaging materials
within the packaging module. The type of fuel cell used is a PEM fuel cell that does not
require any external power source in order to convert the oxygen and hydrogen into
water. See Figure 3.
[00123] The packaging module is loaded into a refrigerated shipping freighter along with
additional packaging modules configured as described. See Figure 2. This system of
packaging modules is loaded onto a refrigerated ocean shipping freighter. The shipping
freighter transports the salmon from Chile to the United States. After reaching the first
destination in the United States, a certain number of the packaging module are removed
from the shipping freighter. Because each of the totes contains fuel cells to remove
oxygen, the packaging modules remaining on the freighter can be transported to other
destinations, via the ocean shipping freighter or by secondary land or air shipping
freighters, under reduced oxygen conditions.
EXAMPLE 1
[00124] Two bench top rigid containers were constructed, one with and one without a fuel
cell. Two nine-liter plastic food storage containers with sealable lids were modified so
that gases could be flushed and continuously introduced (at very low pressure) into each
container. A commercially available fuel cell (hydro-Genius™ Dismantable Fuel Cell
Extension Kit, purchased through The Fuel Cell Store) was installed into the lid of one
nine liter rigid container such that hydrogen could also be introduced from the outside of
the rigid container directly into the (dead ended) anode side of the fuel cell. The cathode
side of the fuel cell was fitted with a convection flow plate allowing for container gases to
freely access the fuel cell cathode. Sodium borohydride was purchased from the Fuel
Cell Store as a chemical source of hydrogen gas (when mixed with water). A sodium
borohydride (NaBHU) reactor was constructed from two plastic bottles such that
hydrostatic pressure could be applied for constantly pushing the hydrogen into the fuel
cell and adjusting for excess hydrogen production and consumption. This allowed
unattended hydrogen production and introduction into the fuel cell for extended periods
(days).
[00125] Carbon dioxide cylinders (gas), regulators, valves and tubing were purchased
along with a large home refrigerator. The refrigerator was plumbed to allow for external
carbon dioxide to be continuously introduced into the rigid containers and hydrogen to the
fuel cell.
[00126] The bench top system was tested by flushing the initial oxygen level down to
near 1% with CO2, closing off the outflow valves leaving the inflow valves opened,
maintaining both containers under a very low constant pressure of CO2. The oxygen and
CO2 concentrations were measured over time using a (Dansensor) CCVOxygen analyzer
while the fuel cell consumed the remaining oxygen from the one container. It was
determined that the container with fuel cell was capable of maintaining oxygen levels
below 0.1% while the container without a fuel cell was unable to hold oxygen levels
below 0.3%.
[00127] On Day 1, Fresh Chilean Atlantic Salmon filets were purchased directly from a
local (Sand City, CA) retail store. The salmon was taken from a Styrofoam container
with a label that indicated that the (loins without fat) were packed in Chile six days
previously. The retail outlet personnel placed 6 fillets (2 each) into retail display trays,
stretch wrapped, weighed and labeled each of the three trays.
[00128] These three packages were transported on ice to the lab where each tray was cut
in half so that half of each package could be directly compared to the other half in a
different treatment. The package halves were placed into three treatment groups; 1.) Air
Control, 2.) 100% C02, No Fuel Cell oxygen remover, 3) 100%. C02 with Fuel Cell
oxygen remover. All three treatments were stored in the same refrigerator at 36 degrees F
for the duration of the experiment: Oxygen and CO2 levels were monitored daily and
sensory evaluations were conducted as described below. After initial removal of oxygen,
the oxygen levels remained at a level undetectable by the instrumentation. The results are
shown in Table 2.
[00129] The levels of oxygen for the duration of the experiment are shown graphically in
Figure 4.
Sensory Evaluations:
[00130] Seven days after placing the three treatments in the refrigerator, the air controls
were judged marginally spoiled by odor and unacceptably spoiled on the 8th day at 36°F.
This established a total shelf life of approximately 13 days from production for the air
control fillets and 7 days at 36 °F (after the first 6 days at unknown temperatures).
[00131] After 22 days in the high CO2 environment (plus 6 days before the test began)
fillets from the fuel cell and non-fuel cell treatments were removed from the containers
and evaluated by 4 sensory panelists. The evaluation scale was 5 = Freshest, 4 = Fresh, 3
= Slightly Not Fresh, 2 = Not Fresh, 1 = Unacceptable. The raw sensory results are
shown in Table 3.
[00132] After an additional 6 days of storage in air at 36 °F, the remaining samples were
photographed raw and the "No Fuel Cell" samples were deemed inedible due primarily to
rancid off odors (not microbial spoilage) and a very yellowish flesh color. The "Fuel
Cell" samples were rated fresh (4) in raw color and odor. These samples were then
cooked and evaluated by the 4 panelists for flavor and texture and rated Fresh (4) in both
attributes. A visual comparison of the salmon samples is presented in Figure 5.
[00133] In summary, the "Fuel Cell" samples were still rated fresh after a total of 34 days
of fresh shelf life while the "No Fuel Cell" samples were unacceptable.
EXAMPLE 2
[00134] Figure 7 shows flexible totes (as disclosed hereinabove) shortly after gas flushing
with carbon dioxide having an initial headspace of about 30 volume percent. Each of the
totes are approximately 42" x 50" x 130" and contain approximately 2,000 to 2,200
pounds offish contained in 54 individual cartons. Other sizes of totes can also be used,
for example, totes having the size of 50" X 42" X 130" or 48" x 46" x 100". The totes
were initially flushed with nitrogen (via valves & plumbing). After about 8 or more
hours, the totes were flushed with carbon dioxide to achieve a very low oxygen level
before turning on the fuel cell. It is contemplated that the nitrogen flush can be replaced
using only a single C02 flushing episode and a fuel cell. Holes were cut (in-flow and out-
flow) (or plumbing can be used) to initially flush the CO2 into the tote to arrive at greater
than 90% CO2. In addition, a nitrogen flush can be employed to reduce the oxygen level
to about 1 % oxygen after which the valves are closed and wait for at least 9 hours to
allow trapped oxygen to evolve from the packaging and product. At that point (after 9
hours) oxygen has generally risen to 1.5 to 2% and the totes are flushed with CO2 up to at
least 90% (less than 1,500 ppm oxygen) and close the valves for shipment. The fact that
we are dealing with a 2,000 pound package (instead of a 40 pound package) combined
with the fact that this process is done "offline" where most MAP processes are done "in
line" makes the multiple gas flushes over a longer period of time economically viable.
[00135] Figure 8 shows the same flexible totes 17 days later after transport and storage.
The totes permitted an initially high volume of CO2 inside the totes in order to
accommodate the absorption of CO2 into the fish throughout the transport and
handling/storage of the totes. In addition, the initial gaseous headspace prevented
negative pressure from being created by oxygen removal. It is important to note that these
totes were not leaking and that the degree of deflation seen in Figure 8 (as compared to
Figure 7) is primarily due to CO2 absorption during the 17 days of transport. CO2 levels
remained above 90% throughout the transport and storage. The fish was then assessed for
freshness.
[00136] Figure 9 illustrates a tote comprising about 1 ton offish, a hydrogen bladder and
a box which comprises a fuel cell, an oxygen indicator indicating whether the oxygen
level in the tote exceeds the levels described as a reduced oxygen environment, and
monitors to monitor oxygen levels, hydrogen levels, fuel cell operation, and temperature.
The box further comprises an LED light, which indicates problems of any of the devices
in the box and a wireless alerting system to alert users on arrival of the system if oxygen
or temperature (time and temperature) limits are exceeded.
[00137] In summary, each tote comprised an initial carbon dioxide containing headspace
of about 30 volume percent. The gas in the totes remained between 90 to 100% CO2
throughout transport and handling, resulting in the inhibition of microbial spoilage.
EXAMPLE 3
[00138] Reference is made to Figure 10, wherein tote 1 comprises a flexible oxygen
impermeable barrier layer 3, inlet port 5 and outlet port 7, wherein the inlet port 5 is
connected to a low oxygen gas source 9. Tote 1 contains foodstuff (e.g. fish) 11 and head
space 13. Headspace 13 provides for a significant oversizing of the tote relative to the
foodstuff 11 contained therein. In one embodiment, the oversizing provides for a head
space of up to 40% volume percent of the tote.
[00139] This unique architecture disclosed herein includes major over-sizing of the tote 1
and head space 13 (see Figure 12), in-flow (inlet) and vent (outlet) openings and gas
flushing (as opposed to vacuum, followed by gas injection). Also, the tote is loaded by
placing oxidatively degradable foodstuffs inside the tote with the tote positioned on a
pallet with the factory sealed end (closed end) on the bottom (as opposed to having the
factory seal is the top as the tote is placed over the top of the foodstuffs). The tote is then
be heat sealed across the top of the tote (above the foodstuffs) after the foodstuffs are
stacked or positioned "inside" the tote, sitting on a pallet. In-flow (Inlet) and vent (outlet)
openings are employed in the tote to facilitate gas flushing through the tote to lower
oxygen. The in-flow of gas is positioned to be at the bottom of the pallet with the out-
flow at the top on the opposite side (to encourage top to bottom flushing). Valves or
holes (taped over) can be used for in-flow and/or out-flow. When CO2 is used, which is
much heavier than air, one can flow CO2 slowly into the bottom of the tote such that the
tote fills up much like a swimming pool with the CO2 pushing the air up and out the vent.
The last step after flushing is to inflate the head space area of the tote to maximize the
head pressure and the head space of the tote before closing the vent (outlet port) and
shutting off the in-flow (inlet) of low oxygen gas(es). After the CO2 level reaches 90+%,
the gas flow is stopped and the tote held for several hours up to a day or more to allow for
trapped oxygen to diffuse out of the packaging and perishable contents such that a
subsequent flush/fill will remove the majority of that residual oxygen. The major
oversized headspace remains necessary due to the long duration of complete CO2
absorption and the extra reservoir (and slight positive pressure) created by the extra
headspace to discourage leakage of air into the tote (should a leak exist).
[00140] As shown in Figure 12, the tote 1 also utilizes a "head pressure", which is created
by the maximized head space 13 height of the flexible tote. It is believed that the height
of C02 confined in the vertical tote creates positive pressure, much like an inflated
balloon. Although in Figure 12 the tote is not literally pressurized via stretching, it could
be by constructing the tote from a suitable material. In one example, the tote is inflated to
a pressure of about 2.2 inches of water column or more above atmospheric pressure and
the decay down to about 1.8 inches of water column is timed to detect leaks. After the
tote passes the leak test (6 minutes or more) the tote is then gas flushed and it is
contemplated that the final gas flush results in about 0.5 or less inches of water column.
The tote is "ballooned" at that point. The plastic is configured to expand in a vertical
manner and such methods and materials are known in the art. Initial tote head pressures
can range from about 0.1 to about 1.0 inches of water column or more above atmospheric
pressure. In addition, the vertical architecture facilitates rmnirnizing horizontal space
requirements for shipping the maximum number of pallets side-by-side. No more than
20% of the expansion of the tote is in the horizontal direction, with the remainder of the
gaseous expansion being in the vertical direction thus creating the "head pressure" and
head space height.
[00141] In certain embodiments, the totes are able to accommodate a very large
headspace (primarily to accommodate CO2 absorption and protect against/delay air
leakage), such that the headspace in combination with multiple initial gas flushes would
require no continuous oxygen monitoring or further periodic gas flushing beyond the
initial multiple gas flushes. It is contemplated that the initial gas flushes can proceed
periodically during the first 72 hours of the tote being sealed with the oxidatively
degradable foodstuff. Alternatively, the initial gas flushes can proceed during the first 72
hours or less of the tote being sealed, or alternatively, the first 60 hours, or alternatively,
the first 48 hours, or alternatively, the first 24 hours.
WHAT IS CLAIMED IS:
1. A packaging module useful in transporting and/or storing of carbon
dioxide absorbing oxidatively-degradable foodstuffs which comprises:
a) a pressure-stable sealed tote of limited oxygen permeability and
a defined headspace, wherein said tote consists of a flexible, collapsible or
expandable material which does not puncture when collapsing or expanding;
b) a carbon dioxide absorbing oxidatively-degradable foodstuff;
c) a fuel cell capable of converting hydrogen and oxygen into
water;
d) a hydrogen source; and
e) further wherein the initial headspace occupies at least 30
volume percent of the tote and the gas in the headspace comprises at least 99 volume
percent gases other than oxygen, and no more than about 20% of the initial headspace
of the tote is in the horizontal direction, with the remainder of the initial headspace
being in the vertical direction.
2. The packaging module of claim 1, wherein the gaseous headspace
comprises at least about 90% carbon dioxide.
3. The packaging module of claim 1, wherein the gaseous headspace
comprises from about 30% to about 35% of the internal volume of the tote.
4. The packaging module of claim 1, wherein the gaseous headspace
comprises about 35% to about 60% of the total internal volume of the tote.
5. The packaging module of claim 1, which further comprises a holding
element suitable for maintaining a hydrogen source internal to the tote.
6. The packaging module of claim 5, wherein the holding element for the
hydrogen source in the tote is a box configured to hold the hydrogen source and the
fuel cell.
7. The packaging module of claim 1, wherein the packaging module does
not contain a gaseous source to maintain positive pressure within the packing module
during transport or storage.
8. The packaging module of claim 1, wherein the foodstuff is fish.
9. The packaging module of claim 8, wherein the fish is fresh fish
selected from the group consisting of salmon, tilapia, tuna, shrimp, trout, catfish, sea
bream, sea bass, striped bass, red drum, pompano, haddock, hake, halibut, cod, and
arctic char.
10. The packaging module of claim 9, wherein the fresh fish is salmon or
tilapia.
11. The packaging module of claim 1, wherein the hydrogen source is
selected from the group consisting of a bladder hydrogen source or a rigid container
hydrogen source.
12. The packaging module of claim 1, wherein the hydrogen source is a
gaseous mixture comprising carbon dioxide and less than 5% by volume hydrogen.
13. The packaging module of claim 1, further comprising a fan.
14. The.packaging module of claim 12, wherein the fan is powered by the
fuel cell.
15. A system useful in transporting and/or storing of carbon dioxide
absorbing oxidatively-degradable foodstuffs which comprises one or more packaging
modules, each packing module comprising:
i) a pressure-stable sealed tote of limited oxygen permeability
and a defined headspace, wherein said tote consists of a flexible,
collapsible or expandable material which does not puncture when
collapsing or expanding;
ii) a carbon dioxide absorbing oxidatively-degradable
foodstuff;
iii) a fuel cell capable of converting hydrogen and oxygen into
water;
iv) a hydrogen source; and
v) further wherein the initial headspace occupies at least 30
volume percent of the tote and the gas in the headspace comprises at
least 99 volume percent gases other than oxygen, and no more than
about 20% of the initial headspace of the tote is in the horizontal
direction, with the remainder of the initial headspace being in the
vertical direction.
16. The system of claim 15, wherein the initial gaseous headspace
comprises at least about 90% carbon dioxide.
17. The system of claim 15, wherein the initial gaseous headspace
comprises from about 30% to about 35% of the internal volume of the tote.
18. The system of claim 16, further comprising a temperature control
system external to the packaging module wherein said system maintains the
temperature inside the module at a level sufficient to maintain freshness of the
foodstuff.
19. The system of claim 16, wherein the packaging modules further
comprise a holding element suitable for maintaining a hydrogen source internal to the
tote.
20. The system of claim 16, wherein the holding element for the hydrogen
source in the tote is a box configured to hold the hydrogen source and the fuel cell.
21. The system of claim 16 wherein the packaging module does not
contain a gaseous source to maintain positive pressure within the packing module
during transport or storage.
22. The system of claim 16, wherein the foodstuff is fish.
23. (Original) The system of claim 22, wherein the fish is fresh fish selected
from the group consisting of salmon, tilapia, tuna, shrimp, trout, catfish, sea bream,
sea bass, striped bass, red drum, pompano, haddock, hake, halibut, cod, and arctic
char.
24. The system of claim 23, wherein the fresh fish is salmon or tilapia.
25. The system of claim 15, wherein the hydrogen source is a bladder
containing hydrogen.
26. The system of claim 15, wherein the hydrogen source is a gaseous
mixture comprising carbon dioxide and less than 5% by volume hydrogen.
27. The system of claim 15, wherein the packaging modules further
comprise a fan.
28. The system of claim 27 wherein the fan is powered by the fuel cell.
29. A method for transporting and/or storing of carbon dioxide absorbing
oxidatively-degradable foodstuffs which comprises:
a) removing the oxygen in a packaging module containing an
carbon dioxide absorbing oxidatively-degradable foodstuff to generate a reduced
oxygen environment within a packaging module, the packaging module comprising a
pressure-stable sealable tote of limited oxygen permeability and a defined headspace
wherein said tote consists of a flexible, collapsible or expandable material which does
not puncture when collapsing or expanding, a fuel cell, and a hydrogen source;
b) flushing the tote with an inert gas such that the tote comprises
an initial gaseous headspace wherein the initial headspace occupies at least 30 volume
percent of the tote and the gas in the headspace comprises at least 99 volume percent
gases other than oxygen, and no more than about 20% of the initial headspace of the
tote is in the horizontal direction, with the remainder of the initial headspace being in
the vertical direction;
c) sealing the tote;
d) operating the fuel cell during transport or storing such that
oxygen is converted to water by the hydrogen present in the tote to maintain the
reduced oxygen environment within the tote; and
e) transporting or storing the material in the tote.
30. The method of claim 29, wherein the initial gaseous headspace
comprises at least about 90% carbon dioxide.
31. The method of claim 29, wherein the initial gaseous headspace
comprises from about 30% to about 69% of the total internal volume of the tote.
32. The method of claim 29, wherein the transporting or storing is for a
time period from between 5 and 50 days.
33. The method of claim 32, wherein the transporting or storing is for a
time period from between 15 and 45 days.
34. The method of claim 32, further comprising maintaining a temperature
in the tote sufficient to maintain freshness of the material during transport or storage.
35. The method of claim 29, wherein the packaging module further
comprises a holding element suitable for maintaining a hydrogen source internal to
the tote.
36. The method of claim 35, wherein the holding element for the hydrogen
source in the tote is a box configured.to hold the hydrogen source and the fuel cell.
37. The method of claim 29, wherein the reduced oxygen environment
comprises less than I % oxygen.
38. The method of claim 37, wherein the reduced oxygen environment
comprises less than 0.1% oxygen.
39. The method of claim 29, wherein the reduced oxygen environment
comprises carbon dioxide.
40. The method of claim 29, wherein the reduced oxygen environment
comprises carbon dioxide and hydrogen.
41. The method of claim 29, wherein the reduced oxygen environment
comprises nitrogen.
42. The method of claim 29, wherein the reduced oxygen environment
comprises carbon dioxide, nitrogen, and hydrogen.
43. The method of claim 29, wherein the foodstuff is fish.
44. The method of claim 43, wherein the fish is fresh fish selected from the
group consisting of salmon, tilapia, tuna, shrimp, trout, catfish, sea bream, sea bass,
striped bass, red drum, pompano, haddock, hake, halibut, cod, and arctic char.
45. The method of claim 44, wherein the fresh fish is salmon or tilapia.
46. The method of claim 29, wherein the hydrogen source is a bladder
containing hydrogen.
47. The method of claim 29, wherein the hydrogen source is a gaseous
mixture comprising carbon dioxide and less than 5% by volume hydrogen.
48. The method of claim 29, wherein the fuel cell is programmed to cease
operation after an initial period time that is sufficient to allow a natural minimization
or cessation of gaseous exchange.
49. The method of claim 48, wherein the initial period of time is between
about 0.5 and 50 hours.
50. The method of claim 48, wherein the fuel cell is programmed to cease
operation when the oxygen level reaches and is maintained below a predetermined
level.
51. The method of claim 50, wherein the predetermined level of oxygen is
below 5% oxygen v/v.
52. The method of claim 50, wherein the predetermined level of oxygen is
below 1% oxygen v/v.
53. A method for transporting and/or storing of carbon dioxide absorbing
oxidatively-degradable foodstuffs which comprises:
a) obtaining a pressure-stable sealed tote of limited oxygen
permeability and a defined headspace containing a carbon dioxide absorbing
oxidatively-degradable material, wherein the initial headspace occupies at least 30
volume percent of the tote and the gas in the headspace comprises at least 99 volume
percent gases other than oxygen, and no more than about 20% of the initial headspace
of the tote is in the horizontal direction, with the remainder of the initial headspace
being in the vertical direction, further wherein the tote consists of a flexible,
collapsible or expandable material which does not puncture when collapsing or
expanding, and further wherein the tote is connected to a module comprising a fuel
cell and a source of hydrogen such that the anode of the fuel cell is in direct
communication with the environment of the tote;
b) operating the fuel cell during transport or storing such that
oxygen in the tote is converted to water by the fuel cell; and
c) transporting or storing the material in the tote.
54. The method of claim 53, wherein the initial gaseous headspace
comprises at least about 90% carbon dioxide.
55. The method of claim 53, wherein the initial gaseous headspace
comprises from about 30 to about 35% of the internal volume of the tote.
56. The method of claim 53, wherein the module is disconnected from the
tote after an initial period time that is sufficient to allow a natural minimization or
cessation of gaseous exchange.
57. The method of claim 56, wherein the initial period of time is between
about 0.5 and 50 hours.
58. The method of claim 53, wherein the module is disconnected from the
tote when the oxygen level reaches and is maintained below a predetermined level.
59. The method of claim 58, wherein the predetermined level of oxygen is
below 5% oxygen v/v.
60. The method of claim 59, wherein the predetermined level of oxygen is
below 1% oxygen v/v.
61. A method for removing oxygen from a tote having oxidatively
degradable foodstuff(s) which method comprises:
g) a tote having a sealable gas inlet port and a sealable gas outlet port
both ports being positioned in the head space of the tote wherein
the tote comprises a flexible, collapsible or expandable material
which does not puncture when collapsing or expanding;
h) adding oxidatively degradable foodstuffs) to said tote in an
amount such that the inlet and outlet ports are not obstructed;
i) sealing the tote;
j) conducting one or more initial flushings of the tote with a low
oxygen gas source by injecting a sufficient amount of such gas
source into the tote through the inlet port while emitting gas
through the outlet port so as to provide a low oxygen atmosphere in
the tote and a gaseous head space of sufficient volume to permit
absorption of gas into the foodstuff without increasing oxygen
content in remaining gaseous head space in the tote to a level of
above about 1500 ppm;
k) sealing the inlet and outlet ports; and
I) optionally periodically flushing the tote with a low oxygen gas
source such that after flushing there remains a sufficient gaseous
head space to compensate for gas absorption into the foodstuff such
that the oxygen concentration in the remaining gaseous head space
does not exceed 1500 ppm at any given time.
62. The method of claim 61, wherein the headspace of the tote comprises
from about 20 to about 69% of the internal volume of the tote.
63. The method of claim 61, wherein the tote further comprises an oxygen
sensor.
64. The method of claim 61, wherein the low oxygen gas comprises carbon
dioxide.
65. The method of claim 61, wherein the reduced oxygen environment
comprises carbon dioxide.
66. The method, of claim 61, wherein the reduced oxygen environment
comprises nitrogen.
67. The method of claim 61, wherein the reduced oxygen environment
comprises carbon dioxide and nitrogen.
68. The method of claim 61, wherein the foodstuff is fish.
69. The method of claim 68, wherein the fish is fresh fish selected from the
group consisting of salmon, tilapia, tuna, shrimp, trout, catfish, sea bream, sea bass,
striped bass, red drum, pompano, haddock, hake, halibut, cod, and arctic char.
70. The method of claim 69, wherein the fresh fish is salmon or tilapia.
71. The method of claim 61, wherein the low oxygen gas source is
programmed to cease operation after an initial period time that is sufficient to allow a
natural minimization or cessation of gaseous exchange.
72. The method of claim 71, wherein the initial period of time is between
about 0.5 and 50 hours.
73. The method of claim 61, wherein the tote comprises an initial "head
pressure" from about 0.1 to about 1,0 inches of water column above atmospheric
pressure.
74. A method for transporting and/or storing of oxidatively-degradable
foodstuffs which comprises:
a) removing the oxygen in a tote containing an oxidatively-
degradable foodstuff to generate a reduced oxygen environment, the tote comprising a
flexible, collapsible or expandable material which does not puncture when collapsing
or expanding of limited oxygen permeability, a sealable gas inlet port and a sealable
gas outlet port both ports being positioned in the head space of the tote and a low
oxygen gas source in gaseous communication with the tote;
b) sealing the tote;
c) optionally periodically flushing the tote with a low oxyge gas
source such that after flushing there remains a sufficient gaseous head space to
compensate for gas absorption into the foodstuff such that the oxygen concentration in
the remaining gaseous head space does not exceed 1500 ppm at any given time; and
d) transporting or storing the foodstuff in the tote.
75. The method of claim 74, wherein the transporting and/or storing is for
a time period from between 5 and 50 days.
76. The method of claim 74, wherein the transporting and/or storing is for
a time period from between 15 and 45 days.
77. The method of claim 74, wherein the tote comprises an initial "head
pressure" from about 0.1 to about 1.0 inches of water column above atmospheric
pressure.
78. The packaging module of claim 1, or the system of claim 15, or the
method of claim 29 or 53, wherein the headspace is up to 69 volume percent of the
tote.
79. The packaging module of claim 1, or the system of claim 15, or the
method of claim 29 or 53, wherein the headspace is from 40 to 69 volume percent of
the tote.
80. The packaging module of claim 1, or the system of claim 15, or the
method of claim 29 or 53, wherein the headspace is at least 50 volume percent of the
tote.
81. The packaging module of claim 1, or the system of claim 15, or the
method of claim 29 or 53, wherein gaseous headspace comprises 60% CO2 and 40%
nitrogen.

ABSTRACT

Disclosed are packaging systems and methods useful in extending the storage-life of foodstuff such as fresh fish.
The packaging systems and methods can be used to transport or store the foodstuff for an extended period of time. The packaging
systems preferably employee a high headspace and flexible architecture and may use a fuel cell to maintain a reduced oxygen level
in a high carbon dioxide environment surrounding the foodstuff. Also disclosed are methods useful in extending the storage-life of
foodstuff such as fresh fish. The methods can be used to transport or store the foodstuff for an extended period of time. The methods
preferably use a low oxygen gas source to maintain a reduced oxygen level in the environment surrounding the foodstuff