The Influence of Microbial Contamination on the Quality of Printing Paper

By Linda R. Robertson, Nalco Company

Reprint R-670

Uncontrolled growth of bacteria and fungi in the papermaking process adversely affects machine runnability. How this growth influences factors in the finished sheet and sheet print properties is often overlooked, even though it can have a profound effect on printing characteristics. Many of the materials used in making paper coatings are excellent microbial nutrients. In addition to being nutrients, these compounds are critical to performance. For example, coatings made of poorly preserved clays can form a surface that has fine scratches caused by microagglomeration of the clay particles. This may be caused by microbial degradation of the dispersants in the clays. This paper will explore these issues and discuss steps that can be taken to minimize these problems.

BIOFILMS
When microorganisms grow, they typically attempt to attach to a surface to form a biofilm or, in papermakers terms, a deposit. Characklis and Marshall5 state that attachment to surfaces is a competitive advantage for microbes because they can reproduce and are not washed away with the fluids. Nutrient availability increases because of fluid flow patterns. In addition, highly varied oxygen gradients are present within the biofilms, which permits the growth of micoorganisms with varied oxygen requirements. Furthermore, in the attached state, organisms are less sensitive to the effects of antimicrobial agents.

INTRODUCTION
Paper is used every day for everything from reading the morning news, filling out purchasing forms, writing checks, to bags for carrying out the garbage at night. While paper is one of the most familiar products a person encounters, how that sheet of paper is formed remains a mystery to the average consumer. The fact that microbial growth causes major problems in making quality paper is usually not considered. In addition to cellulose fibers, there are numerous materials used in the papermaking process. These include water, starch, alum, carbonates, polymers, proteins, clays, latexes and other materials used to aid in paper formation or to produce the coatings that form the printing surface. These compounds support the growth of a wide variety of microorganisms, including many species of both aerobic and anaerobic bacteria, algae, nematodes, protozoa, and many types of fungi.1, 2, 3, 4 Microbial degradation problems in paper machines can be roughly grouped into two broad types: biofilm formation and spoilage. How these problems affect the quality of the finished sheet are quite different.
Figure 1 Microbiological slime deposit on machine frame. Samples from deposit show high levels of bacteria, calcium carbonate, and fibers.

The biofilm or deposit can further increase in size as it entraps the wood fibers, carbonates, clays and other particles normally used in the papermaking process. At times, a sticky or polymeric matrix may be present. The origins of the sticky materials may include the production of exo-polymeric materials by bacteria, pitch, or even upsets in the chemistry of the paper machines that would result in, for example, gelled alum. The biofilms in paper machines form massive slime deposits that can be an inch or more in thickness (Figure 1). It is not uncommon for

Presented at the 1st International Symposium of Interactive Paper, Guadalajara, Mexico, October 1996

Figure 2 Stringers on a wire return, fresh water shower. Microscopy of stringers shows evidence of high level of filamentous bacteria.

long stringers, caused by filamentous bacteria, to form around fresh water showers (Figure 2). When these deposits break loose and fall into the paper furnish, they result in end product imperfections such as holes and defects (Figure 3) or even paper sheet breaks.1, 6 When this occurs, the paper with the defects must be used as broke and re-pulped or downgraded.7 If the paper containing these holes makes it to a new high speed coater, massive problems may result.
Figure 3 Collection of sheet defects formed by sloughed deposits.

SPOILAGE
FIBER STOCK SYSTEM In addition to problems with deposits, microbial activity can also cause spoilage of pulp and furnish, or chemical additives.2, 8, 9 For example, in a case brought to our attention, uncoated free sheet paper used for copy machines gave off an unpleasant odor when it was heated as it went through the copier. The problem was traced to improperly preserved fiber chests that allowed anaerobic bacteria to flourish and produce volatile fatty acids such as butyric and proprionic. Anaerobic spoilage of chests has also been implicated in the formation of hazardous and explosive gases such as hydrogen and hydrogen sulfide.2,10 This type of spoilage caused the death of Canadian welders who ignited explosive gases while doing hot work.10 Papermakers understand the economic benefits associated with the control of microbial growth on machine surfaces. Unfortunately, many papermakers overlook the problem of microbial growth in additives because it can be difficult to detect. Often such growth is accompanied by changes in viscosity, decreased pH values, and off-odors.11 Microbial contamination of additives and coatings can come from a number of sources. These may include poorly treated makeup or quench water, incoming product containing a heavy loading of spoilage microbes (Table 1), and/or the heel from a previous batch or shipment. Although there are differences between the additives, there are many similarities in the way they spoil.

Starch Starch is an ideal food source. Microorganisms enzymatically convert the starch components, amylose and amylopectin, into sugar for growth. Spoiled starch will not give optimum performance as either a strength additive or as a binder for coating formulations. An indication of a microbiological problem may be a drop in pH accompanied by viscosity loss. Many mills reduce or eliminate preservative treatment of starch

ADDITIVES Typical chemical additives may include starch, clay, protein, titanium dioxide, CaC03, size, defoamers, etc. Each of these can potentially become microbiologically contaminated during the manufacturing process, transport or storage.

Table 1 Lot by lot variation microbial counts in colony forming units/gm in dry starch from several manufacturers. Plating done on Difco Starch agar. Incubation at 37C for 3 days. Manufacturer A aerobic bacteria Lot A Lot B Lot C Lot D 15,000 7,000 18,000 30,000 aerobic bacterial spores 1,280 290 100 200 fungi Manufacturer B aerobic bacteria 310 1,400 530 310 aerobic bacterial spores 210 440 500 600 fungi Manufacturer C aerobic bacteria 2,800 13,000 aerobic bacterial spores 20 40

<1 <1 <1 <1

40 <1 40 70

in the mistaken belief that the cooking process will sterilize the slurry, or they assume that the incoming starch is sterile. Neither is true (Table 1). Recycling of starch from the machine back to the run tank from a size press application can contaminate the cooked starch by bringing actively growing bacteria into a fresh food source. As the bacteria grow, they produce acidic by-products that reduce the pH. Papermakers may try to recover the starch by adding caustic to increase the pH. Although biocide can be added to stop further microbiological growth, the damage has been done. To eliminate a poor sizing response, the batch must be discarded.

Dyes Dye metering can be impeded due to contamination of the dye by microbes. The ensuing biofilm can cause plugging of feed lines and uneven addition of tinting dyes. Biodegradation of papermaking tinting dyes does not seem to be a significant problem. However, degradation could be a more significant problem with the azo dyes13 used to make colored paper grades.

Fillers In order to simplify the discussion, clays, precipitated and ground calcium carbonate, and titanium dioxide (which is more typically added as a brightener) will be discussed simultaneously. These are used as fillers for the sheet and as components of coatings. Unlike starch and proteins, these materials do not serve as nutrients in their own right. However, they contain dispersants that are critical to performance. If the dispersants are degraded, viscosity changes may result. Fine scratches in coating surfaces have been traced to microagglomeration of the particles caused by degradation of dispersants in the fillers. Anaerobes, such as sulfate reducing bacteria, can even cause a darkening of the filler and production of hydrogen sulfide. This is often seen with improperly preserved clays that must then be returned to the manufacturer for re-bleaching and treatment.

Proteins Protein binders are often used with other binders such as starch in coating formulations. Microorganisms readily degrade the large protein molecules in order to utilize the amino acids for growth.12 A very large drop in viscosity is normally accompanied by only a slight decrease in pH. Lutey and May11 state that not long after the initial pH drop, the precipitation of protein occurs. This is accompanied by the production of malodors and product discoloration.

Synthetic Binders Styrene-butadiene, vinyl acetates and acrylates are synthetic binders often used in conjunction with starch and proteins.12 Organisms can break down the dispersing and stabilizing components in latex formulations. It is more difficult to detect this degradation since it is usually not accompanied by pH or viscosity decreases. Instead, poor adhesion of the coating to base sheet, low pigment holding capability, and undesirable supercalendering properties may be the only indicators of microbial degradation.11

Coating Formulations Each of the materials listed above may be in a coating formulation. Spoilage of individual chemicals can impact the final formulation. The formulations present a particular challenge because carbon and nitrogen are present in ratios that enhance microbial growth. Often, the separate components are pre-

served with biocides that are antagonistic. When the coating components are mixed, the preservatives may actually counteract each other. Furthermore, common coating practices increase the likelihood of spoilage. In a manner similar to cooked size press starch, coatings are recirculated from the machine back to run tanks.

12. Holt, D. M. Microbiology of Paper and Board Manufacture, Proceedings of the 7th Int. Biodegradation Symposium 1987. Elsevier Appl. Sci. Publ. Co. 493-506. (1988). 13. C. H. Martin, TAPPI Proceedings, Papermakers Conference, Chicago, Illinois. Identification and Implications of Troublesome Slime-forming Bacteria Found in Paper Mill Systems, 91-95 (1988). 14. O. W. May, TAPPI Proceedings, Papermakers Conference, Atlanta, Georgia. Slime Control, 257 (1982). 15. W. G. Characklis and K. C. Marshall, Biofilms: A Basis for an Interdisciplinary Approach, in Characklis and Marshall, (Eds.), Biofilms, John Wiley & Sons Inc., 3-16 (1990). 16. Robertson, L. R. The Use of Phase-Contrast Microscopy to Assess and Differentiate the Microbial Population of a Paper Mill, TAPPI Journal 76:3 83-87. (1993). 17. Sorelle, P. H. and W. E. Belgard. The Effect of Recycled Fiber Use on Paper Machine Biological Control, TAPPI Papermakers Conf. Proceedings. 560-575. (1991). 18. Hughes-van Kregten, M. C. Slime Flora of New Zealand Paper Mills, Appita 41:6 470-474. (1988). 19. Purkiss, B. E. Bacterial and Fungal Problems in the Paper Industry, Papper och Tra. Erickoisnemero 4a: 207-218. (1970). 10. R. S. Rowbottom, Bacteria Cause Fatal Explosion at Corrugating Medium Mill, Pulp and Paper Canada 90(4) 75-81 (1989). 11. R. W. Lutey and O. W. May, Preservatives, in Paper Coating Additives, TAPPI Press Atlanta, Georgia. 106-125 (1978). 12. S. Goldstein and R. Cade, Preservatives 1, in Paper Coating Additives, TAPPI Press Atlanta, Georgia. 125-140 (1995). 13. H. Matanic, et al. Microbial Decolorization of Chromium-Azomethine Dye UnderA e r o b i c Conditions, J. Soc. Dyers Colour 112 (5/6):158161 (1996).

PREVENTION Paper Machine Surfaces Microbial colonization of the paper machine is reduced when a good deposit control program is in place. Traditionally, a deposit control program has included the following items: proper housekeeping to keep surfaces free of splashed stock, anti-microbial treatment of fresh water and additives, the use of biocides to reduce microbiological growth on the machine, and scheduled boil-outs to remove the deposits that do form. This allows the mill to avoid the cost of unscheduled downtime caused by sloughing of deposits and product quality loss.

Additives The control of microbial growth in additives reaps economic benefits both in terms of optimum additive performance and in the elimination of runnability problems. Steps for the prevention of microbial growth in additives include acceptance of only adequately preserved chemicals from additive manufacturers, good housekeeping practices to keep tanks spotlessly clean, makeup of additives with treated fresh water, and addition of compatible preservatives to slurries or formulations. These steps will help the mill achieve good control of the machine system and help to eliminate problems that could interfere with the quality of the finished sheet.

REFERENCES
11. Caulkins, D. and J. Wildman. Changes in Paper Process Causing Problems in Controlling Deposits, Pulp and Paper. 62(6), 89-93 (1988).

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