Biocides Preservatives Dow Ph Range.pdf

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Conventional vs. Natural Preservatives Green aspirations must be tempered with practical realities—an environmentally preferable product is not a success if the formulation falls apart or is overrun with potentially pathogenic microorganisms due to the lack of an effective preservative Beth Ann Browne

Phil Geis

Tony Rook

Dow Microbial Control

AdvancedTesting Laboratories

The Sherwin-Williams Company

• CSPA Preservative Defense Task Force

T

of commercial products is compatibility, regulatory compliance, safety, cost, and supamong the most important elements of product quality. ply security. A summary of the points of difference between Nevertheless, it is an element that has not demanded a conventional preservatives, organic acids and essential oils is hyper-vigilant focus due to the compositions of consumer and shown in Table 1 (p. 78). industrial products that have prevailed during the past several Consumer and industrial product manufacturers face enordecades. The use of a conventional chemical preservative along mous pressure to offer effective and innovative products at with some innate capacity of the formulation to resist spoilage an economical price. Concurrently, consumers and environ(due to the high level of solvents and low water content), was mental groups are demanding that products be more “envipreviously sufficient to protect the product during manufactur- ronmentally-preferable” in addition to maintaining the same ing and throughout its lifetime of use by the consumer. However, standard of effectiveness at the lowest possible price. With relmodern product formulations with eco-compliant ingredients are evant changes such as reduced volatile organic content (VOC), under increased pressure by ecolabeling organizations1,2 to aban- elimination of heavy metals and replacement of solvents with don the use of conventional preservatives in favor of alternative water, products may be perceived as more “green,” but the very substances that are seen by various groups to be more “natural.” real consequence of increased microbial susceptibility must be Examples of these substances include organic acids, such acknowledged. The removal of ingredients, which once creas citric, lactic, sorbic and benzoic, as well as essential oils and ated an inhospitable environment for bacteria and fungi, has plant extracts, including a significant impact on thyme and rosemary oils.  product quality. The maThe pursuit of environjority of consumer and inmental responsibility is to dustrial products ranging be praised, but there refrom architectural paint to mains a difference between household cleaners to faba reactive sustainability ric softeners to dishwashstrategy that merely reing liquids are now highly acts to these market trends susceptible to microbial and a workable practice spoilage. Ineffective presfor the effective preservaervation of these products tion of consumer and inand the raw materials used dustrial products. Organic to produce them can have acids and essential oils detrimental results includare not currently suitable ing significant changes in direct replacements for viscosity, pH drift, color conventional preservachange and foul odor, all tives for a variety of reaof which can occur while sons including microbial destroying the perforefficacy profiles, product Household cleaning products demand effective preservation systems. mance of the product.4     he microbiological quality

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CONVENTIONAL VS. NATURAL PRESERVATIVES

Microbial Efficacy It is important to specify the positive attributes of conventional preservatives to understand the practical challenges facing natural preservative alternatives. Preservatives are often referred to as biocides, and biocides are by definition toxic and usually lethal to bacteria and fungi. A non-toxic alternative, that is still effective in controlling a broad spectrum of microorganisms, may at best be deemed an unrealistic expectation. A successful preservative must be broadly effective against a variety of bacterial and fungal (including molds and yeasts) species, or alternatively a combination of an effective bactericide and an effective fungicide may be used. Consumer and industrial product formulations with a pH range of 2 to12 can be susceptible to both bacteria and fungi. To the extent that organic acids are effective, their effectiveness is limited within a pH range of 2 to 6 and primarily against fungi and a subset of bacteria. If organic acids were the only preservatives permitted for use in consumer and industrial products, a large gap would exist for products with neutral and alkaline pH, such as laundry detergents and household cleaners, and those subject to the more common spoilage bacteria such as the Pseudomonads.

Rosemary oil is not a direct replacement for traditional preservatives.

Factors to Consider

Manufacturing conditions and product compatibility factors must be considered when comparing conventional preservatives to natural alternatives. Some manufacturers require the use of a rapid-acting biocide for the decontamination of products, raw materials, and equipment in order to ensure product quality. If a point is reached when only natural alternatives may be used in consumer and industrial products, the ability to use a rapid-acting biocide will be eliminated. Interestingly, the use of rapid-acting biocides is viewed as environmentally and TABLE 1. COMPARISON OF PRESERVATIVES FOR HOUSEHOLD fiscally responsible by preventing disposal of large volumes of finished products and AND INDUSTRIAL PRODUCT APPLICATIONS raw materials that are contaminated with Preservative Type microorganisms. The reduction of bioburCriteria den resulting from the use of rapid-acting Conventional Organic acids Plant Extracts/Oils biocides also reduces the stress on a longterm preservative. It also potentially lowEffective use levels ers the amount of long-term preservative Less than 0.1% 1-10% 10-20% against microorganisms required to effectively protect the product from spoilage.  Antimicrobial range Bacteria and fungi Fungi, some bacteria Fungi, some bacteria Beyond preserving consumer and industrial products, biocides must be compatible Range of efficacy - pH Broad (pH 2 to 12) Acidic (pH 2 to 6) Acidic (pH 2 to 6) with other ingredients in the formulations. Fortunately, conventional biocides are usuFIFRA status Compliant Some are compliant Non-compliant ally added at less than 0.1% active ingredient, and compatibility issues are infrequent. In contrast, non-traditional (natural alterToxicological data Expansive Moderate None native) preservatives are typically used at Established concentrations greater than 1% to achieve Safety GRAS3 Unknown per US EPA antimicrobial efficacy and they may significantly alter other properties of formulations Commercial source Established Established None such as viscosity, odor, color, pH and product performance. For example, in a comCommercial Supply Commercial quantities Not established parison study,5 a household cleaner at pH quantities 10 required 1.0% of an organic acid for efRange of formulations fective antibacterial efficacy which reduced Broad Limited Unknown that can be preserved the cleaner’s pH to 7.5. This pH shift would Compatibility with Infrequent pH shift, viscosity pH shift, viscosity alter the product performance to the point of product formulations compatibility issues changes changes, odor being an ineffective cleaner. A conventional 70 • happi

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CONVENTIONAL VS. NATURAL PRESERVATIVES

The majority of consumer and industrial products are now highly susceptible to microbial spoilage.

preservative at 0.05% (one twentieth the amount of the organic acid) provided the same level of antibacterial efficacy without altering the pH of the cleaner.5 To achieve potentially the same level of efficacy, organic acids and essential oils are generally required at concentrations of 20 to 50 times and 20 to 200 times greater than the conventional biocides, respectively.5

Sustainable Supply The global commercial supply for conventional biocides is well established. However, preservatives containing organic acids or essential oils are typically used in small niche product applications due to limited efficacy and therefore are only sold in small volumes (when compared to conventional biocides). A drastic shift to preservatives from agricultural sourcing will not satisfy even a portion of the consumer and industrial markets whose products are made continuously in tens to hundreds of tons per batch. This will require significantly increased percentage levels of natural alternatives for effective preservation. Even if expanded agricultural production of natural preservatives could be accomplished to satisfy a limited portion of the consumer and industrial product demand, there would be substantial environmental, social and sustainability impacts.6 The authors are currently unaware of existing relevant assessments of these impacts. Additionally, the natural preservative supply would likely be variable,7,8 from crop to crop, and rigorous analysis would be required to determine a consistent active ingredient level from one supply to the next to prevent overdosing or underdosing of a preservative.              

Regulatory Compliance Perhaps the most significant points for this discussion are the regulatory compliance and data reporting requirements for US EPA registration of preservatives for consumer and industrial products. Each preservative used within these products requires EPA registration as an antimicrobial pesticide under the Federal Insecticide, Fungicide, Rodenticide Act (FIFRA) first enacted in 1947 and amended in 1996 (7 U.S.C § 136 et seq.). The EPA states, “All pesticides distributed and sold in the United States must be registered by the EPA based on scientific data showing that they will not cause unreasonable risks to human health, worker, or the environment when used as directed on product labeling.”9 To obtain a registration for a preservative, the preservative supplier must generate an extensive data package including toxicology, environmental fate, exposure, product chemistry 72 • happi

and efficacy studies. The EPA evaluates the data and conducts risk assessments. Costs associated with the registration process and data generation can reach $10 million for a new preservative product containing a new active ingredient. A US EPAapproved preservative product label is a company’s license to sell the product, and the label includes specific application areas as well as usage levels.                                                  EPA-registered products are subject to periodic reviews by the Agency, which may result in additional data requirements for the registrant. Suppliers of non-traditional/natural preservative alternatives claiming to control bacteria and/or fungi in a consumer or industrial product that have not obtained a FIFRA registration are in violation of Federal law, unless these natural alternatives qualify as Minimum Risk Pesticides per the criteria for FIFRA 25(b) Exemption.10  Product manufacturers that use non-FIFRA-registered ingredients as preservatives within their products, would also be considered non-compliant with Federal law. Currently, only a fraction of FIFRA-registered products contain organic acids or essential oils as the active ingredients.11 All natural products cannot be considered de facto “safe” because some of these materials have been shown to elicit allergic reactions in humans which may be amplified at the high use levels of 1 to 10% required for sufficient antimicrobial performance.12

The Big Picture The evolution of consumer and industrial product formulations with an increased focus on human and environmental health is a noble effort that is supported by the authors. However, green aspirations must be tempered with practical realities—an environmentally preferable product is not a success if the formulation falls apart or is overrun with potentially pathogenic microorganisms due to the lack of an effective preservative. Current registered preservatives have been thoroughly tested with rigorous regulatory demands not only as to product efficacy but also to ensure adequate protection of human health, proper use and handling, and appropriate consideration of environmental fate. It is not evident that products generally presumed to be more environmentally-preferable would be regarded as such if put to the same scrutiny as a US EPA registered pesticide. The reality today is there are very few effective preservative materials available for formulators to use.       According to some product manufacturers, an eco-label symbol on a product package is required to be competitive in some consumer markets. Conventional biocides are added to final formulations at less than 0.1% (often 0.0015% to 0.05%) active ingredient, yet ecolabel groups judge preservatives by the same criteria as components that are added at significantly higher concentrations, some as high as 60%. These organizations or ecolabels would be restricting certification to product formulations that are compatible with preservation with organic acids or essential oils, or to neutral or alkaline pH products that are inherently resistant to microbial spoilage. 

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CSPA PRESERVATIVE DEFENSE TASK FORCE

10.  US EPA Reregistration Eligibility Decision (RED) Flower and Vegetable Oils. EPA 738-R-93-031. Dec 1993.

•The CSPA Microbiology/Preservation Subcommittee is committed to establishing best practices and acceptable standards to address the increasing concern for microbiological quality within consumer and industrial products. To support these goals, a Preservative Defense Task Force was commissioned to address the need of communicating the necessity of effective preservation strategies within consumer and industrial products. More info: CSPA Microbiology/Preservation Subcommittee,

11.  US EPA Minimum Risk Pesticides – Criteria for FIFRA 25(b) Exemption.  http://www.epa.gov/oppbppd1/biopesticides/regtools/25b_list.htm 12.  Bleasel, N., Tate, B., and Rademaker, M. 2002.  Allergic contact dermatitis following exposure to essential oils. Australasian Journal of Dermatology 43(3): 211-213.

Tel: 202-872-8110; Website: www.cspa.org

It is clear that efficacy, cost, regulatory compliance and supply have and will constrain application of organic acid and essential oil preservation to niche, if not boutique, products. If market forces or regulatory changes demand the use of only organic acids and essential oils as preservatives, then some categories of products will need to be withdrawn from the market. This would be necessary because the products cannot be made in a way to achieve effective preservation with such materials. Therefore, it is essential that programs intended to establish more environmentally preferable preservation consider products on a case-by-case basis. In summary, the use of natural alternatives for preservation is not as simple as an ingredient substitution; there are many practical issues to consider in maintaining safe, effective, and stable consumer products that are free from microbial contamination. •

References: 1. United States Environmental Protection Agency’s Design for the Environment (DfE), www.epa.gov/dfe. 2. Natural Products Association.  Natural Home Care Standard 020910v01.doc www.NPAinfo.org. 3.     Generally Regarded as Safe (GRAS) Substances (SCOGS) Database. http:// www.fda.gov/Food/FoodIngredientsPackaging/GenerallyRecognizedasSafeGRAS/ GRASSubstancesSCOGSDatabase/default.htm 4.     American Chemistry Council Biocides Panel. 2010. Benefits of Antimicrobial Pesticides in Public-Health and Industrial Uses. 5.     Browne, B.A. 2010.“The Influence of Global Regulatory Requirements and Pressures on Preservative Choices for Consumer Products.”  May 6, 2010. Consumer Specialty Products Association Mid-year Meeting.  Chicago, IL. 6.     United Nations Industrial Development Organization (UNIDO).  2005. Herbs, spices and essential oils. Post-harvest operations in developing countries. http://www.unido.org/fileadmin/user_media/Publications/Pub_free/Herbs_spices_ and_essential_oils.pdf 7.     Barra A. 2009. Factors affecting chemical variability of essential oils: a review of recent developments. Nat Prod Commun. 4:1147-54. 8.     Viljoen, A.M., Subramoney, S., van Vuuren, S.F., Baxter, K.H.C. and Demirci, B. 2005. The composition, geographical variation and antimicrobial activity of Lippia javanica (Verbenaceae) leaf essential oils.  J Ethnopharm  96:271-7. 9. US EPA Registration Review.  http://www.epa.gov/oppsrrd1/registration_review/

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