Specialty Chemicals by BASF

Odour Control and Chemical Sanitation

BASF Biocides

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BASF Biocides - protecting the worldThe biocide business for Specialty Chemicals, BASF AG

BASF is one of the world’s leading suppliers ofspecialty biocides. We create products that makelife safer, simpler and more comfortable formillions of people worldwide.

Our high performance biocides are used in everyaspect of life. From toiletries, to air conditionersused in both industry and home, from Iceland toEquador our technology spans the globe inpreservation and disinfection. We help to protectthe lives of millions of people across the worldevery day.

Through our product range, marketing expertise,technical and regulatory knowledge, BASF’sinnovative biocides approach positions thebusiness at the very forefront of antimicrobialtechnology. The marketing, technical and researchand development headquarters for BASF’sspecialty biocide business is located inNottingham.

Our products are made in ‘state of the art’manufacturing facilities at Cramlington, Englandand Ludwigshafen, Germany. In each of ourplants, the expert integration of process andenergy requirements leads to manufacturingefficiencies and quality production.

To demonstrate our commitment to our customers,we have made significant investment in long termdedicated biocide resources within Europe, AsiaPacific and the USA.

In 2000, we established a direct presence in theUSA with a new dedicated marketing andtechnical centre based at BASF Corporationheadquarters in Mount Olive, New Jersey. Productis supplied through an integrated BASFwarehousing facility in Charlotte, North Carolina.Our US operation is part of BASF Corporation’sChemical Division, situated in Mount Olive, NewJersey.

How we work for you

BASF’s biocides are sold through BASF’sestablished network of sales offices worldwide. Inthis way, we aim to offer valuable local supportand the highest standards of customer excellence.

Working with BASF provides access to manyessential regulatory approvals. For example ourEPA registrations allow products and customerformulations to be sold in the USA and ourapprovals ensure supply to the paper industry inthe Nordic area. We are also well positioned tosupport our actives under the European BiocidalProducts Directive.

We believe in long-term commitment to ourproducts and customers and this is reflected inour substantial registrations and the data requiredto obtain them. To this end many of our productsare supported with extensive safety andenvironmental data packages.

In addition, BASF is committed to providing thehighest standard of health, safety andenvironmental protection as part of ourcommitment to Responsible Care. We continuallyresearch and innovate to produce the mostadvanced products on the market.

At BASF, we are also constantly reviewing ways inwhich we can improve our products and servicesto ensure that we keep pace with the rapidlychanging developments in information technology.BASF is harnessing these changes and ensuringthat we are aligned with our customer’srequirements, making it more efficient andconvenient for you to do business with us.

BASF’s specialty biocide products are marketedunder the Myacide® and Protectol® trade names.

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Introduction

In many industrial applications, the problemsassociated with microbial contamination manifestthemselves as biofilm formation or as productspoilage and degradation. However, in someother sectors, the ability of microorganisms togenerate noxious or unpleasant odours can be anequally negative consequence of their presence.

Every aspect of life, from travel to leisure activities,places demands for increasing levels of comfortand hygiene. The provision of toilet facilities onaircraft, trains and buses has created problems indealing with waste, away from normal sewagedisposal systems. Similar difficulties are faced inthe camping, caravaning and boating industries.Controlling odours in these temporary installations,or chemical toilets, has involved a primarystrategy of odour masking with perfume additives.However, an important secondary approach isbased on antimicrobial additives that inhibit themicroorganisms responsible for generating thefoul odours. These additives can also provideprotection against pathogenic organisms that maymultiply in the chemical toilet and be a potentialsource of infection for users.

A related application has developed in recentyears involving domestic pets. Various absorbentmaterials have been offered to the consumer as ameans of providing indoor toilet facilities for pets,principally cats and, to a lesser extent, otherdomestic pets. Concerns over the odoursassociated with soiled “Cat Litter” trays and alsothe related hygiene issues, have led to theincorporation of antimicrobials into absorbentlitters.

The use of sumps or lagoons as waste settlementareas in some manufacturing industries can alsogive rise to odour problems due in part tomicrobial activity. In some instances, potentiallytoxic gases may be generated under anaerobicconditions and this can present a significantsafety hazard. These specific occurrences may berare but they can be controlled by appropriate useof antimicrobials that have broad-spectrumantibacterial activity, including activity againstanaerobic species.

BASF’s biocides are ideally suited to controllingodours associated with bacterial contamination ina range of application areas.

CONTENTS

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Myacide® AS / S2 biocide 6

Protectol® GA 50 / Protectol GA 24 biocide 10

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Myacide AS biocide is the industrial grade of 2-Bromo-2-nitropropane-1,3-diol or Bronopol and issupplied as a crystalline solid (Myacide AS) or asa liquid formulation, Myacide S2. This choiceprovides the formulator with a flexible approach tothe control of microbial growth.

Bronopol is a broad-spectrum bactericide that ishighly effective at inhibiting the growth of odourgenerating bacteria and enteric pathogens(disease-causing bacteria found in the gut).

This factor is important in both eliminating badodours and preventing the spread of disease inchemical toilet treatments and absorbent clayformulations, including cat litter.

QUALITY

Myacide AS

Myacide AS is a white to pale yellow, free flowing,crystalline solid. The product contains a minimum98% 2-Bromo-2-nitropropane-1,3-diol althoughtypical purity values may be higher. As supplied itis stable for a minimum of 3 years when keptunder good storage conditions.

Myacide S2 is a 50% w/v solution of Bronopol indipropylene glycol monomethyl ether and water.Myacide S2 allows for ease of handling and isideal for use in systems where automatic dosing ispractised. It has a shelf life of 2 years.

ANTIMICROBIAL ACTIVITYBronopol is one of the most advancedbactericides available in the market for odourcontrol. It operates through a unique dual actionmechanism. Firstly, it has a powerful biocidalaction that controls the microorganisms (e.g.E.coli) that are present in human waste. Secondly,it reacts with thiol containing groups that causebad odours e.g. hydrogen sulphide, mercaptansand organic sulphides to form more complex, lessodorous compounds.

The Minimum Inhibitory Concentrations (M.I.C.) ofBronopol are typically 12.5 –25ppm for a widerange of Gram negative and Gram positivebacteria, including Staphylococcus epidermidis,Klebsiella aerogenes, and Escherichia coli.

USAGE RECOMMENDATIONS

Solubility, Stability, Compatibility.

Bronopol is readily water-soluble and solutionscontaining up to 28% w/v are possible at ambienttemperature. The compound also shows a highaffinity for polar solvents (e.g. up to 50% w/v inpropylene glycol) which allows a flexible approachto formulating solution concentrates for ease ofapplication. In complex environments, Bronopolpartitions preferentially into the polar (usuallyaqueous) phase. Since microorganisms growprimarily in the aqueous phase Bronopol can exertmaximum effect at the site of contamination.

Chemical toilet preparations generally fall into oneof three categories, dry powder blends (oftenpacked into soluble sachets), liquids and liquidconcentrates. For optimum stability, liquidproducts should be formulated below pH6. Solidformulations and absorbent granules should avoidthe use of alkaline fillers. At alkaline pH, Bronopolis less stable but efficacy is not affected. In thiscase Bronopol reaches equilibrium with itsbreakdown products which are alsomicrobiologically active. To obtain maximum shelfstability, it is recommended that all formulationconcentrates be maintained at a pH range of 4-5.

Myacide® AS / S2 Biocide

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In common with other biocides, strong oxidisingand reducing agents should be avoided. Bronopolis compatible with a large variety of fragrances,dyes and surfactants used in chemical toiletformulations.

Bronopol or its concentrated solutions can becorrosive to mild steel, cast iron, galvanised ironand aluminium. For the formulation of toilettreatments for aircraft systems, recommendationsare available concerning appropriate corrosioninhibitors. Further details are available from BASFMicroCheck Limited.

Recommended Dose Rates.

It is important that appropriate levels of MyacideAS or S2 are added to each chemical sanitationformulation and that subsequent dosing regimesaccommodate in-use variables such as volume ofwaste load, temperature, pH and formulationingredients. In laboratory evaluations, a level of200ppm Myacide AS has proven highly effectivein odour and bacterial control.

Some suggestions for typical liquid and powderconcentrates are provided in the table below.

The above formulations are then diluted to give aneffective level of biocide.

For absorbent granule formulations, typicalcarriers are Fuller’s earth, attapulgite and pumice,although others can be used.

The suggested application rate for absorbentclays is 25-200ppm Myacide AS (25 – 200g /tonne of carrier or 0.04-0.32 oz/a.i. per 100lbs ofcarrier).

Ingredient Regular Concentrate Powder% % %

Buffer Salts (pH4) 1 5 10

Dye 0.1 0.5 1

Fragrance 0.3 1.5 3

Surfactant/Solubiliser 2 10 20

Myacide AS 3 15 30

Water/Filler(e.g. Sodium Sulphate) To 100 To 100 To 100

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CASE STUDY

Chemical Toilets

Deodorant concentrates were prepared based onnonionic surfactant, fragrance, buffer, dye andwater. Biocides were added at appropriate levelsto provide two formulations, one containingMyacide AS and the other Formaldehyde - acommon toilet fluid biocide. These products werethen diluted to achieve in-use concentrations of200ppm (Myacide AS) and 1875ppm(Formaldehyde) respectively. The dilutions werechallenged initially with Escherichia coli at 109

colony forming units (cfu)/ml. Thereafter, dailychallenges were continued at 105 cfu/ml. At eachchallenge, tryptic soy broth was added as asimulated organic loading. All samples werestored at 37˚C throughout the 2-week test. Atsuitable intervals, samples were removed andassessed using standard plate count methods.The results are presented in Figure 1 below.

Figure 1- Efficacy of Myacide AS in asimulated chemical toilet fluid

The above results indicate that Myacide AS at200ppm was superior in activity to Formaldehydeat 1875ppm.

SAFETY CHARACTERISTICSA considerable data package has beenassembled on Bronopol, to support a wide rangeof end-use applications, covering bothmammalian and environmental toxicity. Thisprovides the information needed to obtain andretain registrations world-wide.

Bronopol is moderately toxic by ingestion. Inconcentrated form it is irritant to the skin but notirritant at normal use levels. Bronopol is one of theleast sensitising of all commonly used biocidesand sensitisation is unlikely to occur in people withnormal healthy skin. Both acute and chronicstudies have shown Bronopol to be non-carcinogenic, non-mutagenic, non-embryotoxicand non-teratogenic.

Bronopol is toxic to some algal species and istherefore potentially dangerous for theenvironment. However, its inherentbiodegradability, rapid hydrolysis and photolysisin water and low bioaccumulation characteristicsindicate that it is unlikely to cause significant, longterm adverse effects in the aquatic environment.

Bronopol is rapidly broken down at concentrationstypically found in the environment.Biodegradation, hydrolysis and photolysis play animportant part in this process.

Disposal of effluent from chemical toilets treatedwith Bronopol should pose no problems withregard to sewage treatment processes. In tests onactivated sludge carried out by the NorthWestWater Authority in England, Bronopol at 40ppmshowed no suppression of oxygen uptake. Infurther tests, Bronopol at up to 15ppm had nosignificant effect on the anaerobic digestion ofsewage sludge. More recently, the EC50 ofBronopol to activated sludge respiration wasestimated at 43mg/l (OECD 209).

Bronopol is classified in the EU Council Directive -67/548 EEC as harmful, irritant and dangerous forthe environment.

Myacide® AS / S2

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REGISTRATIONSNORTH AMERICA

USABASF’s Bronopol has EPA registrations for manufacturing andend use application in chemical toilet deodorants and absorbentclays, to inhibit the growth of odour causing bacteria.

CANADAPermanent registration for industrial uses and householdproducts.

EUROPE (EU)

FRANCEBronopol is approved for use as a preservative under theRepression des Fraudes (July 1988).

AUSTRALIABronopol is on the chemical substances lists of Australia (AICS).

JAPANMITI Reg. No. 2-325: industrial applications.

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BASF’s biocides business suppliesGlutaraldehyde formulations under the trademarksProtectol GA 50 and GA 24 biocide for the controlof microbial growth and foul odours in chemicaltoilet fluids.

QUALITYThe products are clear, colourless aqueoussolutions based on Glutaraldehyde as the activeingredient. Protectol GA 50 has an active contentof 50% Glutaraldehyde and GA 24 is based on24% Glutaraldehyde. Under recommendedstorage conditions the solutions have a shelf life ofat least six months.

ANTIMICROBIAL ACTIVITYThe Glutaraldehyde products are extremelyeffective antimicrobial agents. They are activeagainst a broad range of microorganisms,including Gram positive and Gram negativebacteria and fungi commonly found ascontaminants in chemical sanitation systems. Theability of Glutaraldehyde to reduce the level ofcontamination and control bad odours at low doserates makes it extremely cost effective.

The table below illustrates the Minimum InhibitoryConcentration (M.I.C.) of Glutaraldehyde requiredto inhibit growth of a range of test organisms. TheM.I.C. figures are expressed as ppm of the 50%active product. It should be noted thatGlutaradehyde can react with the mediacomponents used in the M.I.C. tests. As a result,the figures obtained in these tests may be higherthan the effective doses required in-use.

USAGE RECOMMENDATIONS

Solubility, Stability and Compatibility

Protectol GA 50 and GA 24 are soluble in waterand a wide range of polar organic solvents suchas alcohols and glycols. This enables it to be usedeasily in the vast majority of water-based systemsand ensures maximum effect at the site ofcontamination. Glutaraldehyde shows optimumstability under normal processing and formulatingconditions in industrial applications. The ideal pHlevel is between 3.2 and 4.2. Its stability isreduced above pH 7 and at high temperatures(>30˚C).

Protectol GA 50 and GA 24 are corrosive to mildsteel, galvanised iron, tinplate and aluminium butthere are no compatibility problems at normal uselevels. Glutaraldehyde is compatible with a widerange of raw materials used in formulated toilettreatment concentrates. However, it is notcompatible with Propylenel glycol and, in commonwith many other biocides, strong reducing andoxidising agents should be avoided.

Recommended Dose Rates

It is important that the appropriate levels ofProtectol GA 50 / GA 24 are incorporated intoeach treatment concentrate formulation to achievea final dose level of 100-500ppm (100 – 500g / m3)based on the toilet fluid volume.

Test Organism M.I.C. (ppm)

Staphylococcus spp. 50

Bacillus spp. 1250

Klebsiella spp. 150

Pseudomonas spp. 150

Candida spp. 1250

Aspergillus spp. 500

Protectol® GA 50 / Protectol GA 24 Biocide

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SAFETY CHARACTERISTICSIn order to support the safe use of Glutaraldehyde,a wide range of toxicology studies have beencarried out. The extensive nature of this databaseis particularly helpful in supporting productregistrations and answering any concerns onproduct safety. Glutaraldehyde is toxic ifswallowed or inhaled and is corrosive to the skinand eyes. It may cause skin sensitisation and hasbeen classed as a respiratory sensitiser in the EU.Glutaraldehyde is not teratogenic or carcinogenicand is not mutagenic in animal studies.

Glutaraldehyde is readily biodegradable in theenvironment and has a low potential tobioaccumulate. Under normal use conditions, itwill not cause problems either to effluent treatmentplants or to the environment following dischargeinto wastewater. Glutaraldehyde is harmful to fishand Daphnia (LC50 10 - 100mg/l) and is very toxicto algae (LC50 0.1-1mg/l).

REGISTRATIONSNORTH AMERICA

USABASF has EPA end–use approvals for Glutaraldehyde forindustrial uses.

CANADABASF’s Glutaraldehyde is approved for the manufacture ofindustrial biocides

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BASF Belgium S.A.

Specialty Chemicals

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