GLUTARALDEHYDESafe Handling and Storage Guide

2003 Revision

Important: The Dow Chemical Company, has compiled the information contained herein fromwhat it believes are authoritative sources and believes that it is accurate and factual as of the dateprinted. It is offered solely as a convenience to its customers and is intended only as a guideconcerning the products mentioned. Since the user’s product formulation, specific use application,and conditions of use are beyond Dow’s control, Dow makes no warranty or representationregarding the results that may be obtained by the user. It shall be the responsibility of the user todetermine the suitability of any products mentioned for the user’s specific application. Thisinformation is not to be taken as a warranty or representation for which Dow assumes legalresponsibility nor as permission to practice any patented invention without a license.

No chemical should be used as or in a food, drug, medical device, or cosmetic, or in a product orprocess in which it may contact a food, drug, or cosmetic, until the user has determined the safetyand legality of the use. Since government requirements and use conditions are subject to change, itis the user’s responsibility to determine that the information contained herein is appropriate undercurrent, applicable laws and regulations.

Dow requests that the customer study this product information booklet and current Material SafetyData Sheets and become aware of product characteristics. The customer should furnish the informa-tion in this product information booklet to its employees, contractors, and customers for the prod-ucts and request such contractors and customers for the products to notify their employees andcustomers of the information in this booklet.

Dow offers a broad line of glutaraldehyde-basedsolutions, which are useful in a wide range ofindustrial and microbiocidal applications. Theyare produced and sold as aqueous solutions ofglutaraldehyde, a linear, five-carbon dialdehyde,containing up to 50 percent active by weight.

Health studies of our glutaraldehyde workers haveshown that good work practices prevent allergicskin reactions, respiratory, or eye problems attrib-utable to glutaraldehyde. Employees at our pro-duction and blending facilities around the worldfollow specific procedures that help avoid expo-sure to the product.

This booklet describes environmentally acceptabletechniques for the safe handling, storage, anddisposal of glutaraldehyde-based solutions. Foradditional information on products, specifica-tions, and Material Safety Data Sheets, contact ourCustomer Information Office.

Glutaraldehyde IdentificationCommon Name . . . . . . . . . . . . . . . . . . . . .Glutaraldehyde

Chemical Name . . . . . . . . . . . . . . . . . . . . .1,5-Pentanedial

Chemical Family . . . . . . . . . . . . . . . . . . . .Aldehyde

CAS Registry Number . . . . . . . . . . . . . . .111-30-8

Molecular Formula . . . . . . . . . . . . . . . . . .C5H8O2

Molecular Weight . . . . . . . . . . . . . . . . . . .100.12

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1 Introduction

2 Safety Considerations

2 Glutaraldehyde Stability

2 Liquid and Vapor Contact

2 Inhalation

3 Skin Contact

4 Eye Contact

6 Spills, Disposal & Deactivation

6 Spills

7 Disposal

8 Chemical Deactivation

9 References

10 Procedures for Safe Handling & Storage

10 Personnel Training

10 Drums

11 Tank Trucks

12 Intermediate Bulk Containers

13 Labeling Precautionary Statements

14 European Product ClassificationInformation

15 Storage

15 Storage Stability

16 Storage Design

19 Product Safety

20 Emergency Service

CONTENTS INTRODUCTION

Glutaraldehyde StabilityGlutaraldehyde-based solutions are stable undernormal storage conditions. Although heating theproduct will result in color formation and slowpolymer formation, it does not represent a safetyconcern. However, if water is evaporated fromaqueous glutaraldehyde solutions, the residualmaterial will rapidly polymerize in a non-hazardous reaction producing residue thatwill burn. In case of a fire, carbon dioxide, drychemical, alcohol-type, or universal-type foams,applied according to the manufacturers’ recom-mended technique, are suitable extinguishers.Self-contained breathing apparatus should beavailable to fire fighters since glutaraldehydevapor is irritating at very low concentrations.

Contamination of concentrated solutions ofglutaraldehyde with strongly acidic or alkalineimpurities can result in exothermic polymeriza-tion of the contained glutaraldehyde via aldolcondensation reactions. If this occurs, addition ofwater to dilute the solution is recommended.

Liquid and Vapor ContactWhen handling glutaraldehyde-based solutions,avoid contact with the liquid and inhalation ofthe vapor. Protective gloves (see page 3), splash-proof monogoggles, or both safety glasses with sideshields and a wraparound full-face shield, andprotective clothing should be worn. Many faceshields alone do not offer total protection againsteye contamination, and their use should beconsidered an adjunct to protect facial skin. Eyebaths and shower facilities should be provided.

Inhalation(1)

Exposure to glutaraldehyde vapor above 0.3 ppmvwill cause irritation to the respiratory tract. Thesesymptoms are temporary. However, there havebeen a few reports of asthmatic-like symptomsand signs in those with hyper-reactive bronchioles.The currently available information is inconclu-sive as to whether the asthma is due to respiratorysensitization or a simple irritant-induced effect.

If the product is handled in closed equipment,general (mechanical) room ventilation should besatisfactory. Vapor levels should not exceed therecommended or stipulated Threshold Limit Value(TLV)(2) or Occupational Exposure Limit (OEL)(2) inthe country of use. Glutaraldehyde has a recogniz-able odor with a detection threshold of < 1 ppbv.The threshold for odor perception is more than100 times below the Threshold Limit Value (TLV)of 0.05 ppmv recommended by the AmericanConference of Governmental IndustrialHygienists (ACGIH). Thus, because human beingsperceive glutaraldehyde in air well below the airconcentration that causes irritation to mucousmembranes, the smell of glutaraldehyde may haveno health significance. If, however, the odor ofglutaraldehyde is accompanied by irritation to thenose and eyes, then the ceiling limit may havebeen exceeded, and improved ventilation or respi-ratory protection may be required.

Because glutaraldehyde vapor exposure limits aredefined differently from country to country, werecommend maintaining levels at or below theapplicable requirements of your locale. In theabsence of any requirements, we currently recom-mend maintaining vapor exposure levels at orbelow 0.1 parts per million ceiling.

If the odor of glutaraldehyde persists in the work-place, industrial hygiene studies should beemployed to form a practicable basis for thedesign of both engineered and personal protec-tion safeguards against potential overexposure.

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SAFETY CONSIDERATIONS

In areas of high glutaraldehyde vapor concentra-tion, self-contained breathing apparatus is recom-mended. For temporary service in areas of lowvapor concentrations of glutaraldehyde, a full-face, cartridge-type respirator may be useful.Specifically, Dow has experienced satisfactory per-formance with the use of Mine Safety Appliances’organic vapor cartridges (Part #464031) and an“Ultra Twin” Respirator(4). If, in addition to vapor,exposure to aerosols and/or spray mists is possible,the respirator should be equipped with a pre-filter.This is recommended because the capacity of thecartridge to protect against the breakthrough ofvapors will be depleted much more rapidly if itbecomes wetted with liquid droplets. (Note: thisproduct in its undiluted form must not be used ina spray or aerosol application.)

If a full-face, cartridge-type respirator is used,instruct personnel to leave the work area andreplace the cartridges if they begin to detect theodor of glutaraldehyde. If odor continues to bedetected with fresh cartridges, the mask may notbe fitted properly, or the mask may be defective,or the concentration of glutaraldehyde may be toohigh for this type of mask and the use of a self-contained breathing apparatus is required.

Concentrated solutions of glutaraldehyde-basedsolutions should be handled at or near room tem-perature to avoid excessive vapor. If glutaralde-hyde solutions must be added to warm solutions,addition via a dip tube placed below the surface isrecommended to minimize vapor development.

Skin Contact(1)

Glutaraldehyde can cause irritation if in contactwith the skin, and in a small percentage ofexposed individuals, skin sensitization has beenreported. Glutaraldehyde at concentrations of10 percent and less is known not to be absorbedacross the skin in harmful amounts.

Aqueous glutaraldehyde solutions containing45% and greater may be corrosive to the skin.Prolonged contact with concentrations higherthan 5% cause mild-to-moderate local redness andswelling. Low concentrations of glutaraldehyde,e.g., 2-4%, may cause minor irritation with localitching and possible slight local redness. At 0.2%,less than 3% of tested human volunteers hadbarely perceptible redness of the skin. Concentra-tions of glutaraldehyde below 0.1%, typical ofmost industrial applications, have not demon-strated allergic skin reaction.

To prevent skin contact with glutaraldehyde, pro-tective gloves, a wrap-around full-face shield, andprotective clothing should be worn. (Caution: toprevent eye contact, it is essential to follow the safetyinformation outlined in “Precautions” on page 5.)

Protective Gloves(5)

A variety of commercially available protectivegloves were evaluated for permeability of aqueous,non-formulated glutaraldehyde solutionsaccording to the American Society for TestingMaterials F739-81 Permeation Test Protocol. Testresults indicated that nitrile and butyl rubber aresuitable for use with up to 50% glutaraldehyde.While polyethylene gloves are acceptable for usewith low concentrations of glutaraldehyde(≤3.4%), they are not recommended for use withhigher concentrations of glutaraldehyde(15–50%). Neoprene and polyvinyl chloride (PVC)gloves, although acceptable for other applications,are not recommended for use with glutaraldehydebecause they retain or absorb glutaraldehyde.

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It is important that the proper size, length, type,and quality of glove be worn when working withglutaraldehyde. Gloves should be long enough toextend up the arm to protect the forearm orclothing from splashes and seepage. Prior to use,gloves should be inspected for tears or holes.Do not use an imperfect glove.

Glutaraldehyde in occluded contact with skin ismore likely to cause irritation. Thus, if it is sus-pected that glutaraldehyde has seeped through orsplashed between the glove and the skin, removethe glove immediately and wash thoroughlybefore putting on a new pair of gloves.

Using the proper type of glove in the correct man-ner is important for adequate hand protection.Penetration of glutaraldehyde through a glove isa function of both chemical compatibility andquality of the glove, and hence, generalizationscannot be made from one manufacturer to another.Always check, and comply with manufacturerrecommendation on the suitability of a glove forits intended use.

Eye Contact(1)

Liquid Contact With Eyes

Glutaraldehyde solutions of 2% and greater willproduce severe, irreversible eye injury.

Solutions of 1% glutaraldehyde in water, ifsplashed on the eye, can cause moderate-to-severeirritation to the eye, which is experienced as dis-comfort or pain, excess blinking, and tear produc-tion, with marked excess redness and swelling ofthe conjunctiva. Contact can cause minor-to-severecorneal injury that may persist if not adequatelyand promptly treated.

Studies have shown that the lowest concentrationcausing minor corneal injury and conjuctivalirritation was 0.25% glutaraldehyde, and theno-effect concentration was 0.1%.

Vapor Contact With Eyes

Glutaraldehyde has a peripheral sensory irritanteffect, i.e., it is capable of reversibly interactingwith sensory nerve-endings in exposed body sur-faces such as the skin or covering/lining mem-branes of the eye and respiratory tract. As a result,there is a local sensation or discomfort wherecontact with the vapor occurs, together with thedevelopment of certain reflex effects. For example,exposure of the eye to airborne glutaraldehydecauses a stinging sensation in the eye accompaniedby excess tearing and blinking. This is an entirely

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normal biological response to sensory irritantmaterials and gives warning of exposure to suchmaterials together with some degree of protection;both blinking and excess tearing will limitexposure.

Furthermore, such effects are generally experi-enced at concentrations below those producingany inflammation or injury. For glutaraldehyde, astudy with a volunteer panel has shown that forthe eyes the threshold for sensory irritation byvapor exposure is 0.3 ppmv for humans. [The odorthreshold for glutaraldehyde is <1 ppbv and is thefirst indication that glutaraldehyde vapor isescaping into the workplace. This is an early indi-cator that attention should be given to improvingventilation or workplace practices.]

Precautions◆ Always wear splashproof monogoggles, or

both safety glasses with side shields and awraparound full-face shield, when workingaround glutaraldehyde solutions. Manyface shields alone do not offer total protec-tion against eye contamination, and theiruse should be considered an adjunct toprotect facial skin.

◆ If a glutaraldehyde solution comes incontact with the eyes, wash immediatelyand continuously with flowing water for atleast 30 minutes. Remove contact lensesafter the first 5 minutes and continuewashing. Obtain prompt medical consul-tation preferably from an ophthalmologist.

◆ Suitable eyewash units should be availablein all glutaraldehyde usage locations.

◆ Glutaraldehyde solutions should be usedonly in properly ventilated areas in whichatmospheric glutaraldehyde vapor concen-trations are maintained below the pre-scribed or recommended Threshold LimitValue (TLV) or Occupational ExposureLimit (OEL). Vapor exposure levels shouldbe monitored to assure healthy and safeworking conditions as well as compliancewith applicable governmental require-ments. Caution should be exercised andadditional monitoring is recommendedwhen there is a major change in operatingprotocol, workplace ventilation systems,workload, or any complaint of eye discom-fort. Immediate action should be taken ifthe vapor level is above the TLV or OEL.

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SpillsPrompt and appropriate attention to drips,splashes, and spills is important to reducethe potential for unnecessary exposure toglutaraldehyde, especially to vapor concentrationsabove the applicable TLV or OEL.

Avoid making contact with spilled material, takingcare not to step in spills since glutaraldehyde will beabsorbed by most shoes. When cleaning up a spill,always wear the correct protective equipment, con-sisting of splashproof monogoggles, or both safetyglasses with side shields and a wraparound full-faceshield, appropriate gloves (see Protective Gloves,page 3), and protective clothing. A self-containedbreathing apparatus or respirator and absorbentsmay be necessary, depending on the size of the spilland the adequacy of ventilation.

Consult local regulatory requirements for additionalguidance on spill prevention and cleanup.

Spill Containment Plan

A spill containment plan for glutaraldehydeshould be in place and should include easy accessto equipment for cleaning up a spill, as well asprocedures for alerting personnel, avoidingglutaraldehyde contact, and, if necessary,evacuating non-essential personnel until the spillhas been neutralized and disposed of. Type ofventilation, air turnover rate, the size andtemperature of the room, and the quantity spilledare important considerations.

Cleanup of Spills

Small SpillsTo clean up small spills, wear the correct protec-tive equipment and cover the liquid withabsorbent material. Collect and seal the material inpolyethylene bags and place in a drum for transitto an approved disposal site.

Dirt that has absorbed the spilled material shouldalso be collected and similarly discarded.

The remaining spilled material may be rinsedaway with water to reduce odor. However, it isimportant to ensure that the rinsate is dischargedinto a municipal or industrial sewer, not into anatural waterway.

Large SpillsLarge spills that cause nasal and respiratory irrita-tion indicate that the area should be evacuatedand cleaned up by a trained team. The appropriatesafety and governmental personnel should benotified immediately.

If tearing of the eyes and nasal or respiratory irrita-tion occur with a spill, then the room ventilationis inadequate to handle the spill. The room shouldbe vacated immediately until a team equipped tohandle a larger spill is on the scene.

Personnel cleaning up a larger spill should betrained and equipped with a self-containedbreathing apparatus, or, if not available, an officiallyapproved or certified full face respirator equippedwith an organic vapor cartridge, gloves, andclothing impervious to glutaraldehyde, includingrubber boots or shoe protection.

Pour an appropriate deactivation compound (seepage 8) into the spilled glutaraldehyde. Collectthe neutralized liquid and, if appropriate, flush itdown the drain with large amounts of fresh water.Depending on the quantity spilled, absorbentsmay be needed. Large spills should be containedand deactivated before disposal.

Although the methods listed below will deactivateglutaraldehyde, there may be other componentspresent in a particular formulation that must alsobe considered before effective and safe cleanup isinitiated. Please consult the manufacturer of theother chemical components in the formulationfor further details and precautions. (See alsopage 18 for spill control of bulk storage tanks.)

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SPILLS, DISPOSAL & DEACTIVATION OFOF GLUTARALDEHYDE

DisposalDisposal of Concentrate

Glutaraldehyde-based solutions should not bedischarged into lakes, streams, ponds, estuaries,oceans, or other waters unless in accordance withlocal regulatory procedures [e.g., U.S. NationalPollutant Discharge Elimination Systems (NPDES)permit]. Do not discharge effluent containingglutaraldehyde to sewer systems withoutpreviously notifying the local sewage treatmentplant authority. For guidance, contact your local water board, regional office of theEnvironmental Protection Agency, or appropriateregulatory authority.

In unusual circumstances, when you have largequantities of concentrated glutaraldehyde to dis-pose of (those containing greater than 5% active),high-temperature incineration is an acceptablepractice. Under these conditions, glutaraldehydeburns cleanly to carbon dioxide and water.

Disposal of Diluted Product

Two environmentally acceptable methods existfor disposing of solutions of glutaraldehyde. Thesimpler method involves further dilution to anessentially nonmicrobiocidal concentration(less than 5 ppm active) in order to allow theglutaraldehyde to biodegrade. The secondprocedure requires chemical inactivation priorto natural disposal (see Chemical Deactivation,page 8). When disposing of the dilutedglutaraldehyde, consult local authorities forregulations. It is not advisable to dischargediluted glutaraldehyde into septic systems.

Bio-oxidation of GlutaraldehydeIn the laboratory, the potential rate at which achemical can degrade is often measured by theBiochemical Oxygen Demand (BOD) test. Thisstandard test involves exposing a test material toan unacclimated sewage seed and measuring theoxygen demand of the system. Calculations ofpercent bio-oxidation are correlated to theamount of oxygen required to degrade the chemi-cal completely to carbon dioxide and water.Glutaraldehyde exhibits a Chemical OxygenDemand (COD) of 1.88 mg O2, per mg active,as compared to a Theoretical Oxygen Demand(ThOD) of 1.92 mg O2, per mg active. In astandard BOD test(7), more than 50% ofglutaraldehyde was degraded in less thanfive days.

The effect of glutaraldehyde on the respirationand growth of sewage microorganisms wasassessed in two separate tests. In the OECD 209respiration inhibition test, the EC-50concentration (i.e., the concentration thatreduces the respiration rate of the bacteria by50%) after a 30-minute contact time wasdetermined to be greater than 50 ppm. The NoObserved Effect Concentration (NOEC) wasdetermined to be 16 ppm in the same study.These results are consistent with a separate studythat determined the EC-50 values for inhibition ofbacterial growth after a 16 hour contact time –to be 25 ppm – for sewage microorganisms and17 ppm for a commercial product containing abroad spectrum of bacteria. The NOEC forglutaraldehyde in this study was 5 ppm.

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Chemical DeactivationIf dilution to below 5 ppm active is not practical,glutaraldehyde can be deactivated chemicallyby adding a suitable amount of alkalinizingor reducing agents. Two options are available,depending on the concentration ofglutaraldehyde to be deactivated.

With Sodium Bisulfite (NaHSO3)

An effective chemical method that can be used todeactivate concentrations of glutaraldehyde (up to5%) is by addition of sodium bisulfite (NaHSO3).In order to assure rapid, complete deactivation,it is recommended that 2–3 parts (by weight)of NaHSO3 be added per part of activeglutaraldehyde. Addition of 2-3 parts NaHSO3 will rapidly reduce the concentration ofglutaraldehyde in solution to less than 2 ppmactive within five minutes at room temperature.The remaining solution can then be disposedof by appropriate means.

The following table illustrates the amounts of NaHSO3 needed for different concentrations ofglutaraldehyde.

Water GlutaraldehydeVolume, Active Level, NaHSO3 Required,

gallon (L) ppm ounce (g)

100 (380) 20 0.53–0.8 (15–23)

500 (1900) 100 13.3–20 (380–570)

5 (19) 20,000 (2%) 26.7–40 (760–1140)

Note: NaHSO3 reacts readily with other aldehydes andketones. If other aldehydes or ketones are present, moreNaHSO3 may be necessary for complete deactivation.There may be other components present in yoursolution that will not be deactivated by NaHSO3. Fora complete summary of the chemistry and toxicologyassociated with NaHSO3 deactivation ofglutaraldehyde, see reference 6, page 9.

With Sodium Hydroxide (Caustic Soda)

Glutaraldehyde concentrations up to 2% activemay be deactivated by the addition of aqueoussodium hydroxide (caustic soda). Adding a suffi-cient amount of sodium hydroxide solution tomaintain a pH of 12 will reduce the concentrationof glutaraldehyde to approximately 20 ppm or lesswithin 8 hours at room temperature. Maintainingthe pH at 12 or higher is critical, since a lower pHwill result in a significantly slower deactivation ofglutaraldehyde. The treated solutions, which nowcontain a low level of residual glutaraldehyde,should be returned to neutral pH by the carefuladdition of an inorganic acid (e.g., hydrochloricacid) before disposal by appropriate means.

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(1) For more detailed toxicology information referto: “Toxicology of Glutaraldehyde: Review ofStudies and Human Health Effects,” revised1995 and available from The Dow ChemicalCompany. Prepared by Bryan Ballantyne, M.D.,D.Sc., Ph.D., former Director of Applied Toxi-cology for Union Carbide.

(2) The Threshold Limit Value (TLV) refers to thetime-weighted average concentration for aconventional 8-hour workday and a 40-hourworkweek, to which it is believed that nearly allworkers may be repeatedly exposed, day afterday, without adverse effect. 2002 TLVs and BEIs,Threshold Limit Values for ChemicalSubstances and Physical Agents & BiologicalExposure Indices, 2002, ACGIH.

The Occupational Exposure Limit (OEL) refersto the airborne concentration of a substancethat should not be exceeded. OELs forglutaraldehyde vary among countries but aregenerally in the 0.05 to 0.2 ppmv range.OELs are sometimes expressed in mg/liter.For glutaraldehyde, the value in mg/literdivided by 4 gives the value in ppmv. Note: Thisvalue is a ceiling limit which should never beexceeded.

For many substances, the TLV or OEL isexpressed as a time-weighted average over aneight-hour working day (TWA8). For others, it isexpressed as a TWA8 qualified by a Short-TermExposure Limit (STEL), which is a 15-minuteTWA that should not be exceeded at any time.Exposures above the TWA8 up to the STELshould be no longer than 15 minutes, shouldnot occur more than four times a day, and thereshould be at least 60 minutes between successiveexposures in this range. For glutaraldehyde, theTLV or OEL is often expressed as a Ceiling (C)value, which is the concentration that shouldnot be exceeded during any part of the working

exposure. The ACGIH TLV-C value forglutaraldehyde is 0.05 ppmv. There is noassociated qualifying TWA8, but sampling may beover a 15-minute period.

(3) When a workplace exposure guideline (TLV orOEL) has not been established, or if it isbelieved that the recommended guideline isinappropriate, Dow has a formal review processto establish a value to be applied to its work-places; this is referred to as an Industrial HygieneGuideline (IHG). This is a compliance limit,applicable worldwide within Dow. IHGs arereviewed periodically to ensure that they pro-vide adequate protection. IHGs are expressed asa TWA8, sometimes qualified by a STEL, or as aCeiling value.

(4) Mine Safety Appliances Co., 121 Gamma Drive, Pittsburgh, PA 15238-2937. Tel: 1-800-MSA-2222, 412-967-3000. Internet: www.msanet.com.

(5) Jordan, S.L.P.; Stowers, M.F.; Trawick, E.G.;Theis, A.B. “Glutaraldehyde Permeation:Choosing the Proper Glove,” Am. J. Infect.Control, 1996, 24: 67-69.

(6) Jordan, S.L.P. et al. 1996, “Inactivation ofGlutaraldehyde by Reaction with SodiumBisulfite,” J. Tox. Envir. Health, 47: 299-309.

(7) Standard Methods for the Examination of Waterand Waste Water, 14th ed., American PublicHealth Assoc., 1976, Parts 507 and 508.

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REFERENCES

Glutaraldehyde-based solutions are shipped bybarge, deck tank, tank truck, intermediate-sizedbulk container (IBC), drum, and other smallercontainers. The handling procedures and precau-tions noted in the section on Safety and Environ-mental Considerations should be followed for allshipping methods.

Personnel Training When working with any chemical, including glu-taraldehyde, it is important that personnel betrained in the properties of the material, possibleadverse effects resulting from overexposure, anduse and procedures appropriate for the chemical.Therefore, a formal training program should be inplace in which new users are educated in properprocedures and experienced users are informed ofissues regarding glutaraldehyde use.

With suitable training and understanding,workers can minimize their own exposure byfollowing basic work guidelines. In addition,access to glutaraldehyde solutions should belimited to those trained in its use.

Employees should be aware of safety proceduresthat go into effect in case of a spill. All employeesshould be familiar with the Material Safety DataSheet (MSDS) that comes with each product.This sheet should be accessible to all users.It contains information regarding emergencymedical treatment and spill cleanup. Accessibilityis particularly important to physicians who maybe treating acute overexposure (e.g., a splash inthe eye).

To minimize contact with glutaraldehydesolutions, tight-fitting lids should be used on allstorage containers. These lids should be in place atall times. When mixing and pouring solutions, careshould be taken to minimize splashes and to reduceaccidental spills.

DrumsHandling and Storage

When a truckload of drums is received, ventilatethe truck before entering to remove any poten-tially irritating vapors of glutaraldehyde. Allpersonnel handling drums should wear protectivegloves, splashproof monogoggles, or both safetyglasses with side shields and a wraparound full-faceshield, and protective clothing. A well-drained con-crete pad is recommended for the storage area.Preferably, the storage area should be indoors or ina shaded area to avoid temperature-related qualityproblems and should be well ventilated.

Emptying Drums

Before drums are opened, they should be at orbelow room temperature. This will minimizepersonnel exposure and air emissions.

When removing plugs or emptying drums, theoperator should wear protective gloves, splash-proof monogoggles, or both safety glasses withside shields and a wraparound full-face shield, andprotective clothing. A bung or plug wrenchshould be used. The operator should place thebung-end up, stand to one side, and face awayduring the operation. After the plug starts toloosen, it should not be given more than one fullturn. Since drum contents may be under pressure,care must be exercised to prevent productsplashing. If internal pressure exists, it should beallowed to escape to the atmosphere. Avoidinhaling this vapor. Once the pressure hasequalized, the operator should loosen the plugfurther and remove it.

Pumping is the preferred drum-emptying method.Air pressure and gravity methods can cause exces-sive spillage. Use of a pump with flexible hose anda downpipe to the bottom of the drum is pre-ferred. The pump, hose, and pipe should be con-structed of the materials listed in the section onStorage Design (page 16).

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PROCEDURES FOR SAFEHANDLING & STORAGE

When being emptied, drums should be in awell-ventilated location. Special caution shouldbe taken when removing the downpipe, since thegreatest potential for exposure occurs duringdownpipe removal. Respiratory equipment, aneye bath and a safety shower should be locatedin the area.

Disposal

Drums used to store concentrated solutions ofglutaraldehyde may be (a) resealed and offered forreconditioning, or (b) triple-rinsed (or equivalent)and offered for recycling, reconditioning, orpuncture and disposal in a sanitary landfill, orother procedures approved by national or localauthorities.

Drum Filling

In drum-filling operations, the primary concern isadequate personnel protection. Operators shouldbe wearing protective gloves, splashproof mono-goggles, or both safety glasses with side shieldsand a wraparound full-face shield, and protectiveclothing. A drum lance or pipe that fills from thedrum bottom should be used. Filling should bedone in a well-ventilated area. Vapors should bedrawn away from operating personnel. Respira-tors, safety showers, and eye baths should belocated in the area.

All filling lines and equipment should be con-structed of materials listed in the sections onMaterials of Construction and Gasket Materialsunder Storage Design.

Tank Trucks

Unloading

Unload by pumping, air pressure, or gravity. Opera-tors should first put on protective clothing, pro-tective gloves, and splashproof monogoggles, orboth safety glasses with side shields and a wrap-around full-face shield. Only then should thehatch be opened to vent the tank. It is not neces-sary to keep nitrogen over the truck; air displace-ment is adequate.

If unloading is done by pumping, a stainless steelcentrifugal pump and stainless steel flexible hoseare recommended for unloading. If pressure isused, air pressure is recommended. Connect theunloading valve and proceed to unload.

The storage vessel or drum being filled can bevented back to the truck or scrubber system ifnecessary to avoid odor and exposure to vapor.

Loading

Trucks can be loaded from bulk storage tanks ifappropriate piping configurations are available.Personnel should wear protective gloves, splash-proof monogoggles, or both safety glasses withside shields and a wraparound full-face shield, andprotective clothing. It is recommended that vaporbe drawn away from operating personnel with ahood or fan during the loading operation.

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Intermediate Bulk ContainersDow can fill customer-owned IBCs withglutaraldehyde-based solutions providing thefollowing conditions are met:

◆ Tanks must be approved UN Intermediate BulkContainers (IBCs). The manufacturer andmodel must be approved by Dow.

◆ Gaskets must be of Teflon,™ Grafoil,™ silicone,or Kalrez.™

◆ Tanks must be within retest limits for filling.

In the United States:◆ Tanks, fittings, piping, valves, and accessories

must be of stainless steel.

◆ Total dimensions must not exceed 48 inches(122 cm) in diameter and 62 inches (157 cm)in height.

◆ Gross weight must not exceed 10,000 lb(4540 kg).

◆ Tanks must be thoroughly cleaned, drained,and dried prior to shipment to Dow.

Further details on the Intermediate BulkContainer Program are available from yourDow Sales Representative or the Dow CustomerInformation Group.

First Aid Information for all Glutaraldehyde Products

If Swallowed:◆ Call a poison control center or a doctor

immediately for treatment advice.

◆ DO NOT INDUCE VOMITING.

◆ Do not give anything to drink.

If in Eyes:◆ Wash immediately and continuously with

flowing water for at least 30 minutes.

◆ Remove contact lenses after the first 5 min-utes and continue washing.

◆ Obtain prompt medical consultation,preferably from an ophthalmologist.

If on Skin or Clothing:◆ Take off contaminated clothing.

◆ Rinse skin immediately with plenty of waterfor 15-20 minutes.

◆ Call a poison control center or a doctor fortreatment advice.

If Inhaled:◆ Move person to fresh air.

◆ If person is not breathing, call emergencyservices and then give artificial respiration,preferably mouth-to-mouth if possible.

◆ Call a poison control center or a doctor forfurther treatment advice.

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GLUTARALDEHYDE LABELINGSTATEMENTS – NORTH AMERICA

All Products Containing >5% Glutaraldehyde

◆ DANGER! Corrosive. Causes irreversible eyedamage.

◆ Prolonged or frequently repeated skincontact may cause allergic reactions in someindividuals.

◆ Causes asthmatic signs and symptoms inhyper-reactive individuals.

◆ Do not get in eyes, on skin, on clothing.

◆ Avoid breathing vapor.

◆ Do not swallow.

◆ Wear goggles, protective clothing and gloves.

◆ Wash thoroughly with soap and water afterhandling.

◆ Remove contaminated clothing and washbefore reuse.

◆ Keep container closed.

◆ Use with adequate ventilation.

Additional Statements for:

Products Containing >5% but <25% Glutaraldehyde

◆ Causes skin irritation.

◆ Harmful if inhaled.

◆ Harmful if swallowed.

Products Containing 25% Glutaraldehyde

◆ Causes skin irritation.

◆ Harmful if inhaled.

◆ Harmful if swallowed.

◆ Harmful if absorbed through skin.

Products Containing >25% but <45% Glutaraldehyde

◆ Causes skin irritation.

◆ Harmful if inhaled.

◆ May be fatal if swallowed.

◆ Harmful if absorbed through skin.

Products Containing 45% to 50% Glutaraldehyde

◆ Causes skin burns.

◆ Harmful if inhaled.

◆ May be fatal if swallowed.

◆ Harmful if absorbed through skin.

◆13

Products containing glutaraldehyde are classifiedas “dangerous” according to the EuropeanDangerous Substance Directive (67/548/EEC), theDangerous Preparations Directive (88/379/EEC),and their amendments. The applicable DangerSymbols, Risk phrases (R-phrases), and SafetyAdvice phrases (S-phrases) are listed below:

Products Containing

Equal to orgreater than Less than Danger Symbol R Phrases S Phrases

0.5% 1% Xi 36/37/38, 43 24, 37

1% 2% Xn 36/37/38, 42/43 23, 24/26, 37

2% 10% Xn 20/22, 37/38, 41, 42/43 23, 24/26, 37/39

10% 25% C 20/22, 34, 42/43 23, 26, 36/37/39, 45

25% 50% T, N 22, 23, 34, 42/43, 50 23, 26, 36/37/39, 45, 61

50% T, N 23/25, 34, 42/43, 50 23, 26, 36/37/39, 45, 61

◆14

EUROPEAN PRODUCTCLASSIFICATION INFORMATION

Transport ClassificationsProducts containing ≥ 42.5% glutaraldehyde areconsidered dangerous for transport and have thefollowing classifications:

ADR/RID IMDG ICAO42.50% 50 42.50% 50 42 50

Corrosive Liquid, Corrosive liquid, Corrosive Liquid, Corrosive liquid, Corrosive Liquid, Corrosive liquid,toxic, n.o.s. acidic, toxic, n.o.s. acidic, toxic, n.o.s. acidic,(contains organic, n.o.s. (contains organic, n.o.s. (contains organic, n.o.s.

glutaraldehyde) (glutaraldehyde solution) glutaraldehyde) (glutaraldehyde solution) glutaraldehyde) (glutaraldehyde solution)

Class 8 8 8 8 8 8

Label 8,6.1 8 8,6.1 8 8,6.1 8

Pack Group I I I I I I I I I I I I

UN Number 2922 3265 2922 3265 2922 3265

Kemmler Number 86 80 — — — —

EmS Number — — F-A, S-B F-A, S-B — —

ProperShippingName

STORAGE

Storage StabilityUnder proper conditions, aqueous glutaraldehydesolutions may be stored for extended periods oftime without adverse effects. The rate of loss ofactivity will be determined principally by thefollowing conditions of storage:

◆ Temperature

◆ pH

◆ Product contamination

The most important factor affecting the usefulstorage lifetime of glutaraldehyde solutions istemperature. The material should be stored at orbelow room temperature whenever possible inorder to minimize decomposition. Glutaraldehydesolutions show no change in concentration afterone year of storage at 25°C and 37°C. However,storage at elevated temperatures for extendedperiods will shorten the shelf life.

Freezing will normally have no impact on theactivity of glutaraldehyde-based solutions. Evenrepeated cycles of freezing and thawing will notcause any significant degradation of the material.However, when glutaraldehyde solutions arefrozen relatively slowly, as might occur in largecontainers or at temperatures only slightly belowthe freezing point, stratification may be observed.The resulting solution will be more concentratedat the bottom of the container than at the top.This effect is more pronounced with solutions con-taining lower concentrations of glutaraldehyde(15 percent), but does not seem to grow worsewith repeated freeze-thaw cycles. When possible,freezing should be prevented. If freezing doesoccur, drums should be slowly thawed (avoidinglocalized hot spots) and mixed until homoge-neous. Bulk storage tanks should likewise bethawed slowly and then recirculated to counteractstratification.

The pH of glutaraldehyde-based solutions will alsohave a major impact upon their useful lifetimes.The active material is most stable at a pH around4.0 and is shipped in this condition. Concentratedsolutions tend to become more acidic upon stor-age, particularly at elevated temperatures. This pHdecrease will not have any significant effect onthe stability of the solutions. Addition of alkalinematerials to concentrated solutions should beavoided, since the lifetime of the material isdecreased at an elevated pH.

Contamination of concentrated solutions ofglutaraldehyde with substantial quantities ofother materials may adversely affect productstability. In particular, high concentrations ofammonia, amines, or products containing thesesubstances should be carefully avoided, since theywill react readily with glutaraldehyde. As with allchemicals, storage containers of glutaraldehydeshould be tightly closed and protected from othermaterials when not in use.

In addition, trace levels of iron will adverselyimpact the storage stability of glutaraldehyde.Therefore, all product transfers should avoid eventransient contact with mild steel.

When kept under optimal conditions, glutaralde-hyde-based solutions may be stored in sealed con-tainers for over two years. Under more adverseconditions encountered in the field, storage livesof over one year are commonly observed. How-ever, to minimize or prevent polymer buildup, werecommend a storage time of no longer than6-12 months.

◆15

Storage DesignMaterials of construction, temperature control,and handling procedures are important considera-tions in maintaining high-quality glutaraldehydeproducts.

Materials of Construction

Solutions of glutaraldehyde are in general equal toor slightly less corrosive than water at an equiva-lent pH. Since the pH of these solutions is rela-tively low (3.1 to 4.5), materials such as carbonsteel, aluminum, iron, copper, and monel shouldnot be used for bulk storage facilities. In additionto equipment damage from corrosion, thesematerials of construction will lead to productcontamination.

Suitable materials of construction for tanks,pumps, and piping are listed below.

Recommended Materials of Construction

Stainless steel types 304 and 316

Nickel

Fiberglass-reinforced plastics: Polyester (e.g., “Atlac” 382)

Vinylester (e.g., “Derakane” 411 or 470)

High Density Polyethylene

Lined steel containers are not recommended forbulk storage, since pinhole leaks could causeproduct contamination. Rubber linings are alsounsuitable because of the potential for swelling.

Gasket Materials

Gasket materials should be chosen carefully, sincethe use of incompatible materials may lead toproduct leakage or material failure. Silicone,Teflon,™ Kalrez,™ or Grafoil™ are recommended forall gaskets.

Nitrogen Blanketing/Venting

Dow stores glutaraldehyde-based solutions innitrogen-blanketed atmospheric tanks to main-tain quality. Tanks are pressurized to 0.13–0.5 psi(6.4–26 mm Hg), depending on vent unit type.Storage under nitrogen is preferred but not manda-tory; comparison of glutaraldehyde-based solu-tions stored under air and under nitrogen has notshown significant product quality differences. Dowrecommends using a vapor-tight vent unit, insteadof an open vent, to reduce odor and minimizeemissions.

Temperature

As outlined in the section on Storage Stability (seepage 15), temperature control is the most impor-tant variable in maintaining high-quality solu-tions of glutaraldehyde. Bulk storage tanks shouldbe insulated to prevent freezing or overheating.The recommended storage temperature range isbetween room temperature and the freezing pointof the glutaraldehyde solution. Provisions shouldbe made for heating bulk storage tanks in cold cli-mates or for cooling in hot climates.

Freezing glutaraldehyde-based solutions may leadto product stratification and should, therefore, beavoided. If the product freezes, it should bethawed gradually in order to minimize hot spots.Heating should be carried out slowly with hotwater coils or electrical tracing, and the elementtemperature should be less than 60°C. The thawedmaterial should then be thoroughly mixed, inorder to return the solution to homogeneity.

◆16

Storage of glutaraldehyde-based solutions atelevated temperatures may cause formation ofpolymers and concomitant loss of monomericmaterial. While storage at temperatures as high as37°C may have little or no effect on productactivity, color formation may be appreciable.Therefore, storage for extended periods at elevatedtemperatures is not recommended.

pH

The recommended pH for storage of glutaralde-hyde-based solutions is 3.1 to 4.5. Although thepH of the material may become more acidic overtime, this normally will cause no decrease in stor-age stability. Solutions containing glutaraldehydewill polymerize under alkaline conditions andshould not be stored in concentrated form abovepH 4.5.

Typical Bulk Storage System

Figure 1 illustrates Dow’s typical storage tank forglutaraldehyde-based solutions. Dow prefers tostore these solutions in insulated, stainless steelvessels that are tall in relation to their diameter.Round-bottomed tanks on legs with bottom draw-down are generally used. Stainless steel centrifugalpumps are used for transfer service.

◆17

Figure 1 – Bulk Storage Tank forGlutaraldehyde-Based Solutions

ReceivingLine

FromNitrogen

Supply

ToProcess

PI

LI

NOTES:

1. Insulate tank and lines if storage is outdoors.Provide electric or warm water 60°C (140°F) (max.)heating if extended ambient temperatures belowsolution freezing point are expected.

2. Nitrogen blanketing is preferred but not essential.

Polymerization Prevention

Additional design practices are available to mini-mize or prevent polymer buildup or plugging. Arecirculation system will keep the contents of thetank well mixed during drawdown and preventpump dead-heading. The piping system should bedesigned with the shortest possible storage linebetween the pump suction and the tank. Checkvalves should be avoided. Bulk storage tanks shouldbe constructed so that the entire volume of the tankis consumed in normal operation every six totwelve months (depending on storage conditions).This will minimize storage time and will thusensure that fresh material is available on acontinual basis. Note that it is therefore undesirableto continually top off a single bulk storage tank. Ifthis is done on a routine basis, it is likely that poly-mer buildup will occur (as aged glutaraldehyde col-lects at the bottom of the tank) and will worsen asthe period between complete emptying of the tanklengthens. Ideally, dual bulk storage tanks would beemployed so that one can be completely emptiedbefore it is refilled and still maintain an adequateinventory of glutaraldehyde-based solutions.

Spill Control

Bulk storage tanks should be diked to contain thefull volume of the largest storage tank. The dikedarea should be provided with independent drainsto the clean and process sewers. The sewers shouldbe valved shut during normal operation. Theclean sewer drain can be opened during rain-storms and the process drain can be valved openas needed. Alternatively, any spills can beremoved by vacuum truck and trucked to a treat-ment plant.

Large spills that cause eye, nasal, and respiratoryirritation indicate that the area should beevacuated and cleaned up by a trained team. Theappropriate safety and governmental personnelshould be notified immediately.

Avoid making contact with spilled material,taking care not to step in it since glutaraldehydewill be absorbed by most shoes. To clean up smallspills, wear the appropriate protective equipmentand cover the liquid with absorbent material.Collect and seal the material in polyethylene bagsand place in a drum for transit to an approveddisposal site.

Dirt that has absorbed the spilled material shouldalso be collected and similarly disposed.

The remaining spilled material may be dilutedwith water to reduce odor, but only if this wouldnot cause a large amount of glutaraldehyde to feedinto a natural waterway. (See page 6 for additionalspill clean up information.)

Equipment Cleanup

Tanks can be cleaned with water. High-pressurewater can be used if polymerization has occurred.This is a physical cleaning method. Glutaralde-hyde polymer is not soluble in water. If water pres-sure does not adequately cleanse the tank, moreaggressive physical or chemical cleaning methodsmay be required. Tank cleaning should be aninfrequent requirement.

◆ 18

When considering the use of any glutaraldehydeproduct in a particular application, you shouldreview the latest Material Safety Data Sheets andensure that the use you intend can be accom-plished safely. For Material Safety Data Sheets andother product safety information, contact the DowCustomer Information Office. Before handling anyother products mentioned in the text, you shouldobtain available product safety information andtake necessary steps to ensure safety of use.

No chemical should be used as or in a food, drug,medical device, or cosmetic, or in a product orprocess in which it may contact a food, drug,medical device, or cosmetic until the user hasdetermined the suitability and legality of the use.Since government requirements and use condi-tions are subject to change, it is the user’s respon-sibility to determine that this information isappropriate and suitable under current, applicablegovernment requirements.

Dow requests that the customer read, understand,and comply with the information contained inthis publication and the current Material SafetyData Sheet(s). The customer should furnish theinformation in this publication to its employees,contractors, and customers or any other users ofthe product(s), and request that they do the same.

Dow offers a broad line of trademarkedglutaraldehyde-based solutions for use in micro-biocidal applications. These products are regis-tered with the U.S. Environmental ProtectionAgency and regulated by the Federal Insecticide,Fungicide and Rodenticide Act (FIFRA) in theUnited States, and by similar legislation in manyother countries or international organizations.Be sure to understand and comply with anygovernmental requirements applicable to youruse of glutaraldehyde.

For additional information on available products,specifications, and Material Safety Data Sheets, con-tact the Dow Customer Information Office.

◆ 19

PRODUCT SAFETY

For emergency service: Mainland United States and Puerto Rico, call:1-989-636-4400.

For further information visit our website:www.dowbiocides.com or call…United States 1-800-447-4369 (phone)

and Canada: 1-989-832-1560 (phone)1-989-832-1465 (fax)

Europe: 800-3-694-6367 (phone)32-3-450-2240 (phone)32-3-450-2815 (fax)

Pacific: 603-7958-3392 (phone) 603-7958-5598 (fax)

Latin America: 55-11-5188-9555 (phone)55-11-5188-9937 (fax)

Other Global 1-989-832-1560 (phone)Areas: 1-989-832-1465 (fax)

EMERGENCY SERVICE

Printed in U.S.A. Form No. 253-01338-06/01/03*Trademark of The Dow Chemical Company