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Odor in Recycled Packaging Grades. Identifying the Cause and Finding the Solution.

David R Jones – Industry Specialist, Buckman

ABSTRACT

Odor can be an issue in all grades of pulp and paper. The problem tends to be more in operations that use recovered
paper rather than virgin pulps. This includes 100% recycled packaging mills. Odor problems will be in two main
areas, product odor causing customer complaints or odor from the mill site causing complaints from neighbors.
Odors can be caused by a variety of mechanisms but they fall into two main areas, microbial and chemical. Along
with odor in some cases the gases that cause the odor have safety implications.

When dealing with an odor issue it is an important first step to clearly identify the source and/or cause of the odor.
This presentation will discuss odor issues in 100% recycled packaging operations. The various odor causing
mechanisms will be reviewed. The methodology used to identify the type and cause of odor will be presented.

The solution to an odor issue will vary depending on the cause of the odor. In some cases a change in operation will
help mitigate the issue, and in others an additive will need to be used. The various solution options will be discussed.

INTRODUCTION

Odor in pulp and paper operations is a very broad subject. While this paper is focused on recycled packaging grades
the issues, troubleshooting techniques and solutions can be applied to any grade or operation. Odor can first be
broken into two main sources, chemical and microbiological. In both areas there are a variety of possible causes.
Understanding the possible sources is the first step in solving an odor issue.

Odor identifying techniques will be discussed and how these are an important part of the solution. What is the
nature of the odor, is it a site issue or a product. Neighbor complaints or customer complaints. Once the source or
sources of odor have been determine then the possible solutions are discussed. Once the problem is solved then
regular monitoring is an important aspect of making sure the problem does not reoccur.

ODOR

Chemical

While most odor issues in pulp and paper operations tend to be caused by microorganisms it is important to
understand chemical causes of odor. The two main categories are chemicals that have an odor naturally such as
solvents or oils and odor that comes from a chemical reaction.

In the first case the cause might be easy to determine, a spill or leak of a chemical that results in an issue. The
chemical reaction can be much harder to determine. One class of chemical used extensively in pulp and paper is the
various forms of chlorine. Chlorine can react by oxidation or substitution. It can react with various other compounds
such as phenols or aldehydes to produce an odorous compound.

Note here that we are not discussing odor that is an inherent part of the process, for example a kraft mill.

Microbial

This is the main cause of odor in pulp and paper operations. There are many different microorganisms that cause
odor. They can be bacteria, fungi or algae. In the case of microbes it is known what odors are caused by the various
organisms. Trends in the packaging industry include factors that have led to the increased chance of an odor problem
occurring. First is the increased use of recycled fiber. Single stream recycling results in more food material being in
the paper. These contain microbes and serve as a food source. In addition as mills move to save water and energy by
closing up the water system the microbial population will increase. A more closed system means there is more
chance of low oxygen conditions (anaerobic). Many of the odor causing bacteria are anaerobic.
Table I below shows many but not all of various microorganisms and the type of odor they can produce.

Table I – Odor causing microorganisms

Pseudomonas aeruginosa trimethylamine


P. reptilovorus putrid
P. putida trimethylamine
P. putrefaciens putrid
P. ichthyosmia fishy
Escherichia coli fecal
Enterobacter aerogenes fecal
Erwinia dissolvens decaying vegetables
Erwinia ananas molasses
Serratia marcescens trimethylamine
Serratia plymuthicum strong fecal
Serratia piscatorum trimethylamine
Proteus vulgaris putrefactive
Proteus mirabilis putrefactive
Clostridium sp. vomit-like
Desulfovibrio ssp. hydrogen sulfide
Desulfotomaculum spp. hydrogen sulfide

Woodward, Stoner (1) are a good reference on microorganisms and the various odor they can produce.

ODOR PROBLEMS

Odor can causes a variety of problems, some extremely critical while others are more of a nuisance. The critical
issues first start with safety. Some odor comes from hazardous gases. This can be a toxic or an explosive gas. This
paper will not focus on this area, the industry has a comprehensive protocol for this type of issue. These include gas
monitors, area based or personal and operational procedures such as gas testing for confined space entry.

Another critical issue is when the product has an odor and customers complain. In some cases it is the converter but
in others the converter has received complaints from the consumer or end user. The reason this is in the critical list is
a problem of this nature can result in loss of business and may be so extreme as to threaten the long-term viability of
a pulp or paper operation. In some cases the odor is not detected in the mill. This can be due to the fact that the odor
is being produced in the paper in storage or that when it is in use by a consumer the odor becomes apparent. In most
cases this is from heat, examples would be in a copier or in a hot food container such as a coffee cup.

The other type of odor is the nuisance type odor. This can be from neighbours in the mill area or workers in the mill.
The reaction to various odors varies widely from person to person. An odor that one person finds objectionable
another person will not really notice. In addition with many odors the human nose quickly becomes used to the odor
and stops “smelling” or detecting it. In these cases time away from the odor will make the nose to once again smell
the odor. An example of this is geosmin. This is a compound produced by a number of different microorganisms that
has an earthy musty smell. The nose can detect geosmin at very low levels but it quickly becomes used to the odor.

IDENTIFING CAUSE OF ODOR

The first step in troubleshooting and solving an odor issue is identifying the type of odor and where it is occurring.
Questions to ask include:
• Location of odor, in one area, in paper, everywhere?
• Is the odor there all the time?
• For product odor, is it at the reel or occurs after storage in the warehouse?
• Is there a converting or end use (heat for example) parameter that makes the odor apparent?
• Is the odor more of an issue on certain grades or time of year?
• Do operators smell the odor at start of shift but then after a while no longer detect the odor?
• What does it smell like?, earthy, vomit, rotten eggs, as examples

As noted above the source can be easy to determine or can be more difficult to identify. An example would be
neighbour complaints from an effluent plant in the mill, odor from sludge for example. In this case identifying the
source may be easy but coming up with an economically viable solution may be more difficult.

There are various tools that can be used in identifying the odor. There are various tests that can be done by
independent labs. There are handheld gas (odor) monitors that can be programed to detect certain odors and in some
cases can learn an odor profile and remember it. It is not the purpose of this paper to endorse specific monitors or
labs but a simple google search will give a comprehensive list. There are also “professional smellers”, these are
people who have trained themselves to be able to identify different odors. Jung, Kappen (2) and Cook, Hoy (3) both
have good discussions on the various lab methods.

In the case where microbial growth is considered to be a possibility a good understanding of microbial testing
protocol is important. It is important to understand the various types of microorganisms that can cause odor and the
various test methods to be used to detect and enumerate them. Table I contained a long list of microbes and it
definitely was not a complete list. There is no one test that will detect or remunerate all microbes. An example of
this is a test is what is commonly called the standard bacterial plate count. This method counts aerobic (oxygen
required to grow) bacteria that will grow at 36 C (97 F) on nutrient agar. It will not count or detect anaerobic
bacteria (grow in the absence of oxygen) or fungus. While the “smell” will help indicate the type of microbe it is
important to complete a range of tests so all possibilities are investigated. This range should include:

• Standard bacterial plate count


• Thermophilic bacteria plate count (grows at higher temperature)
• Standard fungal plate count
• Actinomycetes plates
• Blue green algae media
• Clostridium test (anaerobic bacteria)
• Sulfate reducing bacteria test (anaerobic bacteria)

For an odor issue the microbial enumeration methods that have a broad range may have only limited usefulness. An
example is the ATP method. ATP is adenosine triphosphate. ATP is the energy molecule in living creatures. The
ATP microbial method measures the ATP in a sample. It is assumed that in a white water sample for example all of
the ATP measured would come from microbes. The ATP method is a quick way to determine over-all microbial
contamination. When searching for an odor cause then the more specific test must be used. ATP made be a good
method for monitoring the general population after the odor problem has been solved.

It is also important to perform the various tests throughout the process. It is possible that the microbial growth that is
generating the odor is mainly growing in one area of the process but is being detected or smelled in a different area.

SOLUTIONS

Starting with chemical caused odors in some cases it will just be a housekeeping issue or possibly added ventilation
to a storage area. When the odor is being caused by a chemical reaction then steps must be taken to prevent or block
that reaction. This could involve removing a compound from the process or adding a blocker.

An example was a fine paper mill that started to receive customer complaints on their paper. Heat from use in a
copier produced an odor. This odor was also present on the paper machine floor when this grade was being made.
After a few months of investigation by a team that included mill personnel, suppliers and consultants it was
determined that chlorine being used in one part of the mill was reacting with organic compounds to produce the
odor. While the investigation was a long process once the cause was determined the solution was easy. Bi-sulfate
was added to scavenge the free chorine and the odor was eliminated.

Microbial caused odor issues can be solved with process changes and with micro control programs. In most cases
both are required. Much depends on the type of microorganism that is causing the odor. With the anaerobic bacteria,
process changes such as mixing to increase oxygen content in the stock and white water can be a very cost effective
way to reduce the anaerobic bacterial population. In the same way making sure tanks of stock and white water do
not stand stagnant will help. Good housekeeping is always a benefit in all aspects of microbial control. If stock tanks
build a sludge layer in the bottom of the tank then the aerobic bacteria will use up all of the oxygen in this layer.
You then get anaerobic conditions and the odor causing anaerobic bacteria such as the clostridia can start to flourish.

An example is a 100% recycled packaging mill that started to receive customer complaints about their paper. In
addition odor was occurring in mill areas. An analysis of the odor found volatile fatty acids (VFA) such as
Propionate, Butyrate and Acetate acids. These would indicate that the problem was from anaerobic bacteria of the
clostridia genus. A micro survey found high levels of clostridia especially in some poorly agitated tanks. The
solution was a combination of better agitation and housekeeping, opening up the water system from 5 to 8 M3/tonne
and the application of a biocide program.

In many microbial odor issues the solution will involve the use of microbicides. This can take the form of an organic
based product or an inorganic. The organic products contain an active that is toxic to microbes. It is important to
choose the right active for the type of microbe that needs to be controlled. The various actives on the market can
have a wide range of minimum inhibitor concentrations (MIC). The MIC is the concentration of the active that is
required to produce a 90% kill. These MIC’s are determined in the lab for specific species of microbes. A biocide
active that is very effective at reducing an aerobic bacteria population may have little effect in reducing the
population of an anaerobic bacteria. Thus it is important to choose the right active or actives for the type of microbe
that needs to be controlled. Application program design is also important. Flow rates have to be set so that the MIC
is reached. In addition some actives require more contact time to be effective and this needs to be reflected in the
biocide application strategy. Buckman has the required information for all of the actives in our biocide product line
and uses computer models to determine cycling up of the product to ensure that the MIC is reached.

Inorganic products are oxidizers. They include the various forms of chlorine; gas, chlorine dioxide and hypochlorite.
These are indiscriminate in their action in that they oxidizer any organic matter. This will include microbes but will
also include other compounds such as plant material and lignin. For a given system there will be a chlorine demand
that needs to be met for micro control to be effective. This varies from operation to operation. A bleached kraft fine
paper mill may have a relatively low demand but in the case of recycled packaging mills the fiber is unbleached and
the demand will be higher. In this category the newest product group are the products that when mixed with
hypochlorite produce monochloramine (MCA). This can be considered one of the most effective products in the
oxidizer range. MCA, being already reacted does not need to satisfy the total demand and so acts more directly to
control the microbes. MCA and the other oxidizers also have a broader range of action against different bacteria.
While there are some bacteria who can tolerate some level of oxidizer they are relatively rare.

Unlike the organic products oxidizers work on testing for free or total chlorine residual depending on the product.
You do not run to a MIC but run to a residual chlorine demand. In the case of hypochlorite you run to a free chlorine
residual. A MCA program will run to a total chlorine level.

A 100% recycled packaging mill had odor that was coming from the effluent plant. The issue was complaints from
people who worked and lived in the mill area. It was identifies as VFA’s. In this case a MCA program is providing
excellent control of the bacteria that produce the VFA’s and the odor complaints have been greatly reduced.

The last example is 100% recycled packaging mill that received customer complaints of odor in the paper. In this
case it was a musty earthy odor. The odor was identified as coming from geosmin. Geosmin is produced by a
number of microbes that include bacteria, fungi and algae. In this case the solution was to start treating the incoming
fresh water, treat the white water and stock system with an inorganic biocide and an organic biocide. They also
added additional agitation to chests and tanks. There have been no odor complaints for over 8 years.

Odor problems are made more difficult as many of the odor compounds can be detected by the nose at very low
levels. Also reducing the microbial population can result in the release of the odor compounds. In some cases it will
take some time from the odor to be removed.

MONITORING AND MAINTAINING CONTROL

Once the problem has been solved it is important to have a monitoring program in place. This may involve regular
microbial testing to ensure that the population remains in control. Regular product testing may be done if that was
the issue. In the case of the oxidizer programs there are online meters that can be used to ensure that changes in
flows etc. do not result in the under or over use of the control agent. The monitoring program will vary depending on
the control program but is an important part of ensuring that the problem does not reoccur.

CONCLUSION

Odor issues can occur in many forms, odor in the end product, neighbour complaints or can be the indication of the
build-up of a hazardous or explosive gas. An understanding of the possible causes of these issues is important in the
solution. Odor can be chemical or microbial in nature. Additionally in both areas there are multiple possible causes.

First step is identifying the type of gas producing the odor and then the source. Understanding the possible causes
will help lead to what tests and lab studies need to be completed to identify the cause and the location of the issue.
Once the cause is identified the proper control program can be implemented. In many cases this will include process
changes in addition to using a microbicide.

Finally a regular monitoring program will help ensure that the problem does not reoccur.

REFERENCES

(1) Woodward, J.H.; Stoner, M.T., Minimizing Odors in the Papermaking Process, TAPPI PaperCon 2006

(2) Jung, H; Kappen J., Odor Control in Papermaking, PaperAge, July/August 2010

(3) Cook, D.L.; Hoy, D. Analytical Techniques for Investigating Odors at Pulp and Paper Facilities: Preliminary
Results, TAPPI International Environmental Conference 2003
Odor in Recycled Packaging Grades.
Identifying the Cause and Finding the
Solution.

David R Jones - Buckman


Agenda
• Introduction
• What is the problem?
• Sources of odors
• Control options
• Summary
What is the Problem?
• Customer
• End product, complaints
• Product quality – limit on VFA
• Mill
• Neighbors
• Workers
• Safety
• Odor can be from hazardous gas
Problem Solving
• Source of odor
• What does it smell like?
• Important first step
• Lab testing, water, pulp, paper
• Independent lab
• In mill testing - VFA
• Micro enumeration
• Not just a standard plate count
• Location?
• Immediate or takes time to develop?
Sources of Odors

• Two main sources


• Chemical
• Microbial
Chemical Odors

• INDUSTRIAL CHEMICALS
Chlorine compounds
Aromatic solvents
Ozone
Organic biocides
• OIL odors
Recycled paper (inks, etc.)
• PERFUME odors
Perfumes in coatings, Recycled fiber
• REACTION BETWEEN COMPOUNDS
Chemical Odors
• Control involves identifying source and/or
reaction and removing it from the system

• For example, free chlorine combining with


organics
• Solution - scavenge chlorine
Chemical Odor - Example
• Odor in paper
• Smell in machine room
• Customer complaints
• Cause
• Chlorine reacting with organics to produced
odorous compounds
• Solution
• Scavenge chlorine
Microbial Odors

• A growing problem
• Recycled fiber
• Single stream
• Food waste
• White water closure
• Less being “washed out” of system
Recycled fiber
• Higher micro population compared to virgin fiber
• Use and collection contaminates the fiber
• Single stream recycling
• More food waste in fiber
• Outside storage
Closure - Microbiological Implications

• Higher microbial population


• Increase in dissolved nutrients
• Increase in temperature
• Increased aerobic growth
• Leads to anaerobic (low oxygen) conditions
• Population shift to anaerobic bacteria
• Production of explosive gases
• Production of corrosive and toxic H2S
• Increased incidence of odors in finished product
Microorganisms
 Many different species produce odor
 Aerobic bacteria
 Geosmin

 Anaerobic bacteria
 Volatile fatty acids
 Hydrogen sulfide

 Yeast and molds, algae


 Geosmin
ODOR PRODUCING BACTERIA

•Pseudomonas aeruginosa •trimethylamine


•P. reptilovorus •putrid
•trimethylamine
•P. putida •putrid
•P. putrefaciens •fishy
•P. ichthyosmia
•fecal
•Escherichia coli •fecal
•Enterobacter aerogenes •decaying vegetables
•Erwinia dissolvens •molasses
•Erwinia ananas •trimethylamine
•Serratia marcescens •strong fecal
•Serratia plymuthicum •trimethylamine
•Serratia piscatorum •putrefactive
•putrefactive
•Proteus vulgaris •vomit-like
•Proteus mirabilis
•vinegar
•Clostridium sp. •putrid
•hydrogen sulfide
•Desulfovibrio and Desulfotomaculum spp.
Sources of Odor
 Fresh Water
 Microbes, odorous compounds

 Additives
 Bacteria in clay etc.
 Fermentative smells from bacteria and yeasts in starch

 White Water
 Decayed or Rotten Pulp
 Effluent recycled back into process
 Sludge

 Effluent system
Solutions
• Chemical odor
• Find source
• Remove odor chemical
• Prevent reaction that produces odorous
compound
Solutions
• Micro odor
• Control microbes
• Look for hot spots
• Process changes
• Agitation and aeration will help control
anaerobes
• Remove dead spots in system where
possible
• Regular cleaning
• Drain tanks and chest as often as possible
Micro Control Programs
• Program design critical
• Application points
• Rates
• Micro control products
• Inorganics
• Hypochlorite
• Sodium bromide
• Busan® 1215 (Microbicide B)
• Organic
• Many actives
• Need to be chosen correctly to control target microbe
• Target application concentration varies with product
Microbial Odor – Example 1
• Recycled board
• Customer complaints of musty earthy odor
• Cause - geosmin producing microbes
• Solution
• Treat fresh water, inorganic microbicide
• Treat white water, inorganic microbicide
• Treat stock, organic microbicide
• Process changes to remove geosmin hot spots
from system
• Added agitation
• Removal of secondary sludge from furnish
Microbial Odor – Example 2
• Mill board – limit on VFA level in sheet
• Regular testing on the sheet
• Volatile fatty acids (Propionate, Butyrate, Acetate)
• A Microbicide B program was started
• Pulp and white water are treated
• Tenfold decrease in microbial population
• Result
• VFA in sheet well below limit
Microbial Odor - Example 3

• Issue
• Packaging mill, odor from effluent
• Complaints from neighbors
• Source
• Volatile fatty acids being produced by microorganisms
• Solution
• Control micro population with a Microbicide B program
• Result
• Marked reduction in complaints over a one year period
Microbial Odor - Example 4

• Issue
• Packaging mill needed to reduce VFA in final product
• Odor in mill
• Source
• Volatile fatty acids being produced by microorganisms
• Solution
• Control micro population with a Microbicide B program
Microbial Odor - Example 4 - Results
1800

1600

Busan 1215 start B start


Microbicide
1400

1200

1000
VFA mg/L

800

600

400

200

0
Hazardous Gas
• Safety issue
• Many microbes produce potential explosive and
toxic gases
• Hydrogen sulfide
• Methane
• Gas testing and monitors are industry standard
A Point to Remember
• Killing most of the organisms does not kill the
already produced odor agents
• May take some time for odor to be eliminated
• Dilution won’t help you much
• Low levels of organisms can add enough odors
to maintain the concentrations at trouble levels
• Depending on issue, may need to control
program always
Monitoring
• Scheduled testing
• Micro population
• ATP, plate counts, etc.
• VFA
• In mill – simple test kit
• Independent lab
• Product testing
• Stock, board
• Gas monitors and testing
Thank You
Questions?