final drum handling plan (revised) tank 21 area combustion ...

F I N A L

DRUM HANDLING PLAN( R E V I S E D )

TANK 21 AREAC O M B U S T I O N , I N C .

D E N H A M S P R I N G S , L O U I S I A N A

Prepared forCombustion, Inc.

Denham Springs, LouisianaSeptember 1993

WCC F i l e 92B059C

Woodward-Clyde Consultants~~ \ _ i l _ _ L _ ' C o n s u l t i n g E n g i n e e r s , ' G e o l o g i s t s , and Environmental Sc i en t i s t s ; ,-14454-} ' ' ^ --^--^^?^:^y^-.i.:^^^^i^^<'^-L^ 70856, / T ' " . . ' " v . "

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Appendix Not Included

Woodward-ClydeEngineering & science a p p l i e d to the earth & its environment

August 16, 1993

Mr. Tim B. KnightInactive and Abandoned Sites DivisionLouisiana Department of Environmental QualityPost O f f i c e Box 82282Baton Rouge, Louisiana 70884-2282

AUG I 8 1993LA, DEFT. OF

E N V I R O N M E N T A L Q U A L I T YI A S D I V I S I O N

LOG

Attention: Mr. T o d d Thibodeaux 'Re: Combustion, Inc. Expedited Removal Action (ERA) Agreement

Tank 21 Area Drum Handl ing PlanWCC F i l e 92B059C

Dear Mr. Knight:Attached for your review and approval is the revised Drum Handl ing Plan for the Tank21 Area, at the Combustion, Inc. site, Denham Springs, Louisiana. The plan has beenrevised to incorporate the comments from LDEQ dated August 5, 1993.If you have any questions, please call.Very truly yours,

Will iam R. HurdleFie ld Representative

S. Russell Killebrew, P.E.Project CoordinatorCCW:kdlAttachmentDRUMQ59R.CVL COMBUSTN

W o o d w a r d - C l y d e Consul tants - A S u b s i d i a r y of W o o d w a r d - C l y d e G r o u p , Inc.2822 O'Neal Lane (70816) • P.O. Box 66317 (70896) • Baton Rouge, Loui s iana(504)751-1873 • Fax (504) 753-3616

F I N A L

DRUM HANDLING PLAN( R E V I S E D )

TANK 21 AREAC O M B U S T I O N , I N C .D E N H A M S P R I N G S , L O U I S I A N A

Prepared forCombustion, Inc.

Denham Springs, LouisianaSeptember 1993

WCC F i l e 92B059C

Woodward-Clyde ConsultantsC o n s u l t i n g Engineers. G e o l o g i s t s , and Environmental S c i e n t i s t s2822 O'Neal Lane. Baton Rouge. LA 70896

T A B L E O F C O N T E N T S

Woodward-Clyde

TABLE OF CONTENTS

Section1.0 SITE INFORMATION 11.1 INTRODUCTION 11.2 SITUATION 11.3 H A Z A R D ASSESSMENT 22.0 GENERAL HEALTH AND SAFETY R E Q U I R E M E N T S 5

2.1 AUTHORITY AND RESPONSIBILITY 52.2 WORK ZONES 523 P R O T E C T I V E E Q U I P M E N T 6

3.0 PROCEDURES 73.1 EXCAVATION 73.2 DRUM HANDLING PROCEDURES 83.3 DISPOSAL 103 .4 CONFIRMATION SAMPLING AND SITE

R E S T O R A T I O N 114.0 AIR M O N I T O R I N G 124.1 S U P P L E M E N T A L AIR MONITORING 12

4.1.1 Worker Monitoring 124.1.2 Fenceline Monitoring 12

4.2 ACTION LEVELS 134.3 RESPONSE TO TDI AIR C O N C E N T R A T I O N S

E X C E E D I N G 0.02 PPM 135.0 SAMPLING AND ANALYSIS 15

5.1 CHARACTERIZATION SAMPLING AND ANALYSIS 15

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TABLE OF CONTENTS (Continued)

LIST OF F I G U R E SFigure 3-1 Approximate Air Monitoring LocationsLIST OF A P P E N D I C E SAppendix A Material S a f e t y Data SheetsA p p e n d i x B Checklist of Activities to be Completed Prior to Excavation or DrumHandl ingA p p e n d i x C Equipment List for Excavation and Drum Handl ingA p p e n d i x D Confined Space Entry PermitAppendix E OSHA 42 Air Monitoring MethodA p p e n d i x F NIOSH 2535 Air Monitoring Method

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1.0S I T E I N F O R M A T I O N

1.1 INTRODUCTION

This addendum to the Work Plans for the Expedited Removal Action (ERA) at theCombustion, Inc. site has been developed to provide additional sa f e ty precautions forwork conducted in the Tank 21 area. This addendum describes drum handlingprocedures, supplemental air monitoring for the additional compounds of concern, andother additional details necessary to complete excavations of a f f e c t e d soil in the Tank21 area. While the original Work Plan spec i f i e s the original site-wide chemicals ofconcern, physical hazards, emergency information, and other general and sp e c i f i c healthand sa f e ty procedures, this addendum is to be f o l l owed in the Tank 21 area inconjunction with and as a supplement to the existing Work Plan. It will be reviewedand approved by Louisiana Department of Environmental Quality (LDEQ) prior to thecontinuation of excavation in the Tank 21 area.

1.2 SITUATION

Tank 21 was an underground storage tank discovered in the southeast quadrant of theProcess Area at the Combustion, Inc. site in Livingston Parish, Louisiana. Thecontents of Tank 21 were removed and the tank it se l f was then removed in accordancewith the approved Work Plans. While excavating a f f e c t e d soils from beneath thelocation previously occupied by Tank 21, drums containing unknown materials werediscovered. Although Tank 21 has been removed, the area where the drums werediscovered will continue to be referred to as the Tank 21 excavation or the Tank 21area throughout this plan to distinguish it from other portions of the Process Area.The area inside the excavation was made sa f e by replacing a protective soil blanketover the drums and work in the Tank 21 area was suspended.

The Tank 21 area, s p e c i f i c a l l y addressed in this plan consists primarily of a sludge-likesoil containing the same chemical compounds found in the soil elsewhere on-site, witha few drums and drum contents distributed at random in the soil. In addition to the

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sitewide compounds of concern addressed in the original Work Plan; site history,observations of characteristics of the contaminated soil, and air monitoring resultsindicate the presence of toluene diisocyanate (TDI) and related compounds (seeSection 1.3).

1.3 H A Z A R D ASSESSMENT

A liquid suspected of containing TDI was observed in the Tank 21 area whileexcavating. Additional chemicals may also be present. A review of past interviewswith former employees at the site has disclosed the possible presence of drumscontaining toluene and methyl ethyl ketone. The suspected presence of TDI raises thepos s ib i l i ty that toluene diamine (TDA) or isomers of toluidine may also be present,since TDA is a raw material for TDI production and toluidine is a by product of TDAproduction. These compounds may present health hazards under certain exposureconditions. Dinitrotoluene (DNT) is another chemical associated with TDI and TDAproduction. During the Remedial Investigation, 2,4-DNT was detected in two soilsamples from this area at concentrations of 9.6 mg/kg and 37 mg/kg.

Protective measures and techniques described in this plan were developed to minimizeexposure to workers and residents around the Tank 21 pit. A summary of toxicity foreach of the suspected chemicals is presented below. Refer to the M S D S s inA p p e n d i x A for more details.

Toluene: Toluene is a volatile organic compound exhibiting irritating e f f e c t s upon skin,eye, and respiratory tract. Toluene is absorbed through the skin. The OccupationalS a f e l y and H e a l t h Administration (OSHA) permissible exposure levels (PEL) fortoluene is 100 ppm 8-hour time-weighted average exposure with a short term limit of150 ppm. On site monitoring and protection for toluene will be accomplished bya p p l y i n g action levels found in the original health and sa f e ty plan and utilizingprotec t ive equipment to include tyvek outer suits and rubber gloves. Monitoring willcontinue to be accomplished with an organic vapor analyzer (OVA) or aphotoionization detector (PID). An action level of 2000 M g / m 3 for toluene haspreviously been established for this site and will remain in e f f e c t .

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Toluene diisocyanate: TDI is a clear to yellow liquid at room temperature exhibitinga sweet odor. TDI vapors are severe respiratory irritants and can cause asthma-likereactions in certain individuals. The OSHA PEL for TDI is .005 ppm as an 8-hourtime-weighted average with short term exposure limit of 0.02 ppm. The odor thresholdfor TDI is approximately 0.2 ppm. These poor warning properties are the reasonsupplied air respiratory equipment is required for protection against TDI vaporexposure. Special instrumentation and monitoring techniques are required to evaluatelow concentrations of TDI in air.

Methyl ethyl ketone: MEK is a low boiling point, f lammable liquid ( f la sh point 35°F) with an explosive range of 12 to 20 percent. MEK is irritating to the nose and eyesat 100 to 200 ppm. The OSHA PEL for an 8-hour exposure is 200 ppm. Level Bprotective equipment will provide ample protection from MEK concentrationsanticipated on-site. The use of spark resistant tools and monitoring with explosionmeters and an OVA or PID will continue to be used for management of MEKhazards.

Toluene diamine: TDA has a high boiling point, low vapor pressure, and is solid atroom temperature. It has a black to purple color hi the environment af t er exposureto air. The 2,4 isomer is classi f ied by EPAs weight-of-evidence as a B2 carcinogen.It may be absorbed through the skin. While handling T D A , care must be taken toavoid skin exposure. Exposure minimization is accomplished by restricting access tocontaminated areas, wearing impervious garments if one maybe exposed (saranex suits,nitrile or butyl gloves, and chemical-resistant boots), decontamination with soap andwater, and an awareness of the permeability of TDA through protective equipment.Awareness may be accomplished by training employees to observe the inside of bootsand gloves for the presence of a brown-stain indicative of TDA penetration. Becausethe vapor pressure is so low, at normal temperatures vapor exposure is not a hazard.During construction activities care must be taken to not generate airborne dustcontaminated with TDA

T o l u i d i n e : All the physical characteristics and exposure management precautionsassociated with TDA a p p l y to toluidine. In addition, toluidine can cause severe eye

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irritation and skin irritation. Some isomers have been considered to be probablehuman carcinogens.

Dinitrotoluene; DNT is a mixture of isomers presenting themselves as a solid at roomtemperature. DNT is a yellow solid with a melting point,around 70° C to 80° C.DNT at normal temperatures presents l i t t l e inhalation exposure hazard. It may beabsorbed through the skin so the precautions discussed earlier for TDA and toluidmea p p l y equally to D N T . DNT exposure can cause anoxia by reacting with thehemoglobin to block oxygen transport by the hemoglobin. The OSHA PEL is1.5 mg/m3. Care should be taken with construction activity to avoid dust and protectfrom skin exposure.

Refer to the MSDS's attached in A p p e n d i x A for more details on the above listedchemicals.


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2.0GENERAL H E A L T H A N D S A F E T Y R E Q U I R E M E N T S

2.1 AUTHORITY AND RESPONSIBILITY

The procedures outlined in this plan will be implemented in addition to existing healthand s a f e l y procedures. Where they must be implemented in place of existingprocedures, they are more stringent Nothing in this plan shall be construed to lessenor reduce existing health and sa f e ty requirements. Procedures for decontamination,medical examination, protective equipment, site sa f e ty meetings, and site entry controlremain as described in approved Work Plans and health and s a f e t y plans.

Responsibilities of Project Managers and Site S a f e t y Of f i c er s remain as described inthe original Heal th and S a f e t y Plans. Emergency notification numbers continue to beper the existing plan.

If necessary, emergency evacuation of the community will be conducted per theCommunity Emergency Response Plan. However, some limited precautionaryevacuation of the downwind residences immediately adjacent to the Process Area maybe implemented based on air monitoring results. If so, the residents a f f e c t e d will beno t i f i ed individually rather than by sounding the siren.

2.2 WORK ZONES

An extended Exclusion Zone with a 50-foot radius will be established around the Tank21 excavation. Because portions of the Tank 21 excavation are less than 50 f e e t fromthe fenceline in the southeast corner of the Process Area, delineation of the 50-footradius will continue outside of the fenceline into Mr. Darby's pasture. Thi s extensionof the Exclusion Zone will only occur during periods that actual excavation is inprogress. At night and during other periods when activity is suspended, the fencelinewill serve as the Exclusion Zone boundary on the south and east sides. During periodswhen work is in progress, an individual will be posted as a monitor to ensure that theExclusion Zone is not entered except by personnel in the appropriate protective


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equipment. The Contamination Reduction Zone and Support Zone for the ProcessArea will remain in e f f e c t per the approved Work Plan.

A berm will be constructed around the perimeter of the Tank 21 excavation area toprevent wastewater from contacting clean areas.

2.3 P R O T E C T I V E E Q U I P M E N T

All personnel entering the Exclusion Zone during excavation or drum h a n d h ' n gactivities will employ U. S. EPA Level B personal protective equipment. This willinclude:

• Pressure demand self contained breathing apparatus (SCBA) orpressure demand suppl ied air respirator

• Chemical resistant clothing with hood; disposable Saranex or equal

• Gloves (outer), chemical resistant, butyl, nitril, or neoprene

• Gloves (inner), chemical resistant, latex, butyl, or PVC

• Boots, chemical resistant, neoprene, butyl, or PVC

Procedures for decontamination, medical examination, protective equipment, site s a f e t ymeetings, and site entry control remain as described in approved Work Plans andheal th and s a f e t y plans.


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3.0PROCEDURES

3.1 E X C A V A T I O N

The Tank 21 area will be excavated with a trackhoe. A f f e c t e d soils will be stabilizedwith fly ash for transportation and disposal at a hazardous waste l a n d f i l l . When adrum is exposed, the trackhoe will stop work and f i e l d personnel will attempt toid en t i fy the d r u m ' s condition. In most cases, it is anticipated that such drums will befound to be drum fragments rather than intact, sealed drums. Such drum fragmentswill be excavated and shipped as debris with the stabilized soil. Should damage occurto drums during the excavation process resulting in a spill of liquid, all liquids anda f f e c t e d soils will be excavated, stabilized with fly ash and transported for disposaltogether with the originally a f f e c t e d soils.

Any sealed, intact drums encountered will be handled in accordance with theprocedures described below. Checklists for these operations are included asAppendi c e s B and C.

Only intact (non-leaking) drums will be removed from the excavation to the ro l l -o f fbox. If a leaking drum is s u f f i c i e n t l y intact such that it can be held in an uprightposition that prevents or stops liquid leakage, it will be removed from the excavationand transferred to the r o l l - o f f box and processed in the same manner as the intactdrums.

Leakage of liquids from damaged drums within the excavation will not have asignif icant impact on the already contaminated soil in the excavation. In the briefperiod of time af t er a leaking drum is discovered until soils are excavated, stabilized,and transported off site for disposal as hazardous waste, inf i l trat ion of sp i l l ed liquidswill be minimal.

Of more importance, the pos s ibi l i ty of air emissions would be increased if liquid isallowed to leak from drums while they are suspended in mid-air such that small drops

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come in contact with circulating air above ground level. Such drops expose themaximum liquid surface area to the air, allowing the greatest possible transfer ofchemical from the liquid to the vapor state. Leaks within the excavation would bebelow ground level and thus shielded from circulating air by the sides of theexcavation. This shielding together with the smaller surface area exposed by the uppersurface of a liquid pool (in comparison to liquid dispersed as individual drops) wouldresult in less potential for air emissions. In addition, treating liquid drums within theexcavation will help prevent the spread of contamination to clean surface soils and willfa c i l i ta t e the rapid application of vapor suppressing foam if needed.

32 DRUM HANDLING PROCEDURES

Intact drums will be careful ly uncovered in the trench and l i f t e d with a drum grappl ingdevice attached to the trackhoe. The drum will be placed inside a steel roll offcontainer located adjacent to the trench, which will serve as a protective shield forpersonnel at the site. Th^s roll off container will be lilted such that any leakage wouldbe held in the back of the container, at the end away from the door. Since leakingdrums will not be transferred to the ro l l -o f f box, this should not occur. However, ifdrum liquids collect hi the ro l l -o f f box, these liquids would be treated in the samemanner as dram liquids.

Drum chime tongs will then be used to lift the drum and place it inside an overpackalready placed in the roll off trailer. All personnel will then vacate the roll off boxwhile the drum is punctured using a spark proof spike attached to a trackhoe bucket.Personnel will then re-enter the roll off box to obtain a sample from the dram andsecure the top on the overpack. Personnel collecting these samples must wear suppl iedair units and f u l l y enclosed saranex suits, and ensure compliance with Section 2.1.12of the Work Plan spec i fying confined space sa f e ty procedures. A confined space entrypermit ( A p p e n d i x D) must be completed before each entry.


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Contingency Plan

Reactivity. Any unusual activity occurring from the drum (reacting, fuming, smoking,etc.) while any of the above procedures are in progress will require the f o l l owingactions:

• If the drum has already been placed in the steel container, it will bedealt with in that container (by either the application of a vaporsuppressing foam or, if possible, overpacMng the drum).

• If the drum is still in the original excavation, water or a 5 percentsolution of isopropyl alcohol in water will be added to submerge thedrum.

A vapor suppressing foam will be added to the surface of the water to prevent vaporsfrom escaping.

Moving drums while they are reacting will be avoided since the transportation activitiesdelay the application of vapor emission controls such as vapor suppressing foam andincrease the poss ibi l i ty to spread contamination to clean areas.

Continuous air monitoring with both hand held monitors and the f i x ed monitors willf o cu s s p e c i f i c attention on evaluation of the potential need to evacuate the downwindresidences until the reaction has s topped.

In the event that drums which are removed and sampled without incident are foundto contain water reactive materials (TDI) based on the sample results, it may benecessary to react the material on site prior to shipment for disposal. Thi s will becomenecessary if only a few drums of reactive material are discovered, and is becausedi spo sa l f a c i l i t i e s must reconfigure their operations to accept reactive material, a majorundertaking which is not practical for small quantities of waste. Two alternatives existfor reacting the material:


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• The material may be reacted on site f o l l owing the procedures justdescribed except that the drum will be placed in a tank with the watersolution rather than placing the water solution into the excavation toprovide a more controlled and contained reaction. The tank willcontain approximately 5,000 gallons (roughly 100 times the volume ofthe dram) of water containing a 5 percent solution of isopropyl alcohol(to help promote a complete reaction). Once immersed in water theoverpack drum will be opened using the punch as previously described.

• The liquid TDI may be repacked in smaller containers and absorbedwith sawdust or a similar material to meet the requirements of thedisposal fac i l i ty.

Acid Vapors. In the event acid vapors are encountered while excavating the Tank 21area, a dense cloud would be expected. The presence of an acid cloud will beaddressed as fo l lows:

• If the cloud appears to be leaving the fenced property, evacuation willbe initiated by activating the "community response plan."

• Work will s top at the excavation and all e f f o r t s will be made toalleviate the source of the vapor cloud.

• Monitoring of the cloud will be accomplished using acid sensitivecolorimetric detector tubes.

3.3 DISPOSAL

S a m p l i n g and characterization of the soils will be completed prior to excavation. It isant i c ipated that the soils will be s u f f i c i e n t l y similar to the pond sludges to be disposedof using currently established waste streams. A f f e c t e d soils, drum fragments, anddebris will be transported to the permitted hazardous waste l a n d f i l l operated byChemical Waste Management ( C W M ) at Carlyss, Louisiana for disposal. This is basedon the concentration of PCBs in a composite sludge sample collected from the Tank

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21 area. A regulatory agency approved list of fac i l i t i e s which accept LDR wastes isincluded in the Combustion, Inc. Super fund Site ERA Phase I Work Plan. If disposalof LDR wastes from the site are required, one of these approved faci l i t i e s will beutilized.

Intact drums will be sampled and characterized, and the disposal determination will bemade based on the results obtained.

Decontamination water, water from the excavation, and water used to react TDI asdescribed above will be collected, transported by vacuum truck to the Pond Area, andtreated through the activated carbon treatment unit prior to testing and discharge inaccordance with the approved "Implementation Plan for E f f l u e n t Treatment System"dated June 24, 1992.

3 .4 CONFIRMATION SAMPLING AND SITE R E S T O R A T I O N

Following removal of the a f f e c t e d soils and drums (or drum fragment s /debr i s), theexcavation will be sampled in accordance with the procedures in Section 3.7 of the"Phase II Removal Action Work Plan" for confirmation that the Table 3-2 soil cleanupcriteria have been met. The soil samples will also be analyzed for TDI, TDA, MEK,DNT, and toluidine to document what concentration of each constituent is l e f t in placeso that they can be addressed (if necessary) in subsequent phases of the RI/FS process.The excavation will then be back f i l l ed in accordance with the procedures in Section 4.2of that plan.

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4.0A I R M O N I T O R I N G

4.1 S U P P L E M E N T A L AIR M O N I T O R I N G

The approved "Air Monitoring Plan" dated June 30,1992 (Appendix G under separatecover of the "Work Plan for Removal Action - Phase 1") will remain in e f f e c t andsamples will be collected and analyzed as required by that plan (see Table 3.2 of theaforementioned plan). Additional lead samples as required in the letter from LDEQdated October 7,1992 will also continue to be collected. In response to the suspectedpresence of TDI, additional monitoring will be conducted to help prevent exposure toworkers and the immediate public around this fa c i l i ty while excavating in the Tank 21area.

4.1.1 Worker Monitoring

Continuous monitoring will be conducted by a hand held instrument spec i f i c for TDIvapors (TLD1 MDA Scient i f i c or equivalent). This instrument will be used by aqual i f i ed user to assure all workers exposed to .005 ppm or greater will be in Level Bprotection. In addition, this monitor will be used to adjust the size of the ExclusionZone such that all areas outside the Exclusion Zone are below .005 ppm, as necessary.The hand held instrument will additionally be utilized to assess whether equipmentpassing through decontamination has had the TDI removed. Any detectable levelabove background will require additional decontamination.

4.1.2 Fenceline Monitoring

A continuous monitor sensitive to TDI (GMD-RIS catalog number 720010 orequivalent) will be utilized to evaluate TDI vapors at the Combustion, Inc. fencelineduring excavation activities. This monitor will be located in the downwind position andwill provide an alarm at .005 ppm. If the wind direction sh i f t s , the monitor will berelocated to maintain its downwind position. If sustained readings exceed the .005 ppmPEL, the residents in the immediate downwind area will be notified and asked to evacuate.

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Evacuation will be immediate and will be initiated by a personal visit to the residence.An explanation will be given to the resident, concerning why evacuation is beinginitiated. Residences applicable to these evacuations are labeled as sample locationsA through F on Figure 3-1 of the Air Monitoring Plan.

Each day excavation activities occur in the Tank 21 area, an integrated air sample willbe taken at the designated sample points on Figure 3-1 of the Air Monitoring Plan.The sample points are located adjacent to each of the residences. These samples willbe taken using OSHA Method 42 or NIOSH Method 2535. The sampling will beginprior to beginning each day's work in the Tank 21 area and will end at the conclusionof each day's work in the Tank 21 area. These samples will submitted to an AmericanIndustrial Hygiene Association (AIHA) accredited laboratory for analysis.

4.2 ACTION LEVELS

The action levels listed below are to be fo l lowed in the Exclusion Zone in addition tothose found in Table 3-1 of the approved "Air Monitoring Plan":

TABLE 3-1 (Suppl ementa l)

Meter T y p eTDI

TDI

SampleFrequency .Continuous

Continuous

ParameterTDI

TDI

Action Level> .005 ppm< .020 ppm> .020 ppm

ResponseEvacuate all nonworkers. ExclusionZone workers in Level B.Take action to reduce air levels.Remain in Level 8.

The senior Woodward-Clyde f i e l d inspector in consultation with the LDEQ representative on site will beresponsible for initiating the responses on Table 3-1.

4.3 R E S P O N S E TO TDI AIR CONCENTRATIONS E X C E E D I N G 0.02 PPM

Per the revised action level table that includes TDI the f o l l o w i n g actions areappropr ia t e to reduce vapor concentrations of TDI to below 0.02 ppm.

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• Dispense a mixture of water and 5 percent isopropyl alcohol in theexcavation until the liquid level is above the level of the TDI.

• Dispense vapor suppressing foam until a layer of the foam iscontinuous over the surface of the excavation.

• Continue to evaluate air concentrations around the excavation andexpand the Exclusion Zone as appropriate.

• Dispense more foam as necessary to minimize vapor dispersion to theatmosphere.

A curtain and mist system was one of the systems considered to control vapormigration of f- s i t e . The curtain and mist system was not selected for the f o l l owingreasons: (i) foam is more e f f e c t i v e than a curtain and mist system for s t oppingemissions and (ii) a curtain and mist system would create contaminated runof f waterwhich would require treatment and would not contain the TDI to the immediate drumburial area. A vapor suppressing foam has been selected to be utilized if real tune airmonitoring shows the need to minimize the amount of vapors able to migrate o f f - s i t e .The foam can be app l i ed quickly if vapors are detected and is e f f e c t i v e in s toppingemissions from migrating off site.

Air monitoring will continue each day f o l l ow ing the end of activities until readings havereturned to background. Based on current experience with the material, this shouldoccur fa i r ly rapidly (approximately 30 minutes). If problems persist, the sources of airemissions will be covered with polyethylene or a protective soil blanket.

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5.0S A M P L I N G A N D A N A L Y S I S

5 . 1 C H A R A C T E R I Z A T I O N S A M P L I N G A N D A N A L Y S I S

Sample s from any intact drams will be collected and analyzed for characterization fordisposal. Details of analytical methods, preservation, shipping, and holding times areprovided in Section 4.4.2.7 of the "Work Plan for Removal Action - Phase I". Ingeneral, characterization sampling will include:

• Flash point for ignitability• pH and N A C E corrosiviry test for corrosivity• Reactivity (to include total cyanide and s u l f i d e )

T C L P for Toxici ty• G C / M S with library search

PCB• BTU value and ash content

The waste will be only analyzed for parameters necessary to characterize it for disposal.Since we have no knowledge of the source of the waste, it is not appropriate toconsider it a RCRA "listed" waste. Therefore , the waste must be pro f i l ed based on itscharacteristics: Ignitabi l i ty (D001), Corrosiviry (D002), Reactivity (D003), and Toxici ty(D004-43). The other parameters (BTU, ash, etc) are anticipated additional analyticalrequirement from the disposal faci l i t ie s . They are required for other technical reasonsand for pricing, but are not part of the waste identification.

92B059C-D/DRUMQ59R.TXTCOMBUSrN 15 08-16-93

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A P P E N D I X AI M A T E R I A L S A F E T Y D A T A S H E E T SIIIIIIIII

Woodward-Clyde

Toluene Diisocyanate (TDI)

Material S a f e t y Data SheetFrom G e n i u m ' s Reference CollectionGenium Publishing Corporation1145 Catalyn StreetSchenec tady.NY 12303-1836 USA_____(518)377-8855_________ G E M U H M I B U a M N C CORP.

No. 331T O L U E N E - 2 , 4 - D n S O C Y A N A T E(Revision D)Issued: November 1978Revised: April 1989

Material: TOLUENE-2.4-DIISOCYANATEDescription (Origin/Uses): Usually prepared from toluene-2,4-diamine and phosgene. Used widely inthe manufacture of polyurethane foams, elastomers, and coatings, all of which have extensive commercial andindustrial applications.Other Designations: TDI; 2,4-Diisocyanate-l-Methylbenzene; 2,4-Diisocymatotoluenc;2,4-Tolylene Diisocyanate; CJlfipj CAS No. 0584-84-9Manufacturer: Contact your supplier or distributor. Consult the latest edition of ChanicahveekBuyers' Guide (Genium ref. 73) for a list of suppliers.___________________^

H M I SH 3F 1R 1PPG**Seesect8

N F P AR 1I 4S 3K 1

S E O i a O E » 2 i J i K G K E D l f e W l ; S J f t ^ ^Toluene-2,4-Diisocyanatc, ca 100%OSHA PELs8 - h r T W A : 0.005 ppm, 0.04 mg/m'15-min STEL: 0.02 ppm, 0.15 mg/m'

ACGIHTLVs, 1988-89TLV-TWA: 0.005 ppm, 0.04 mg/m'TLV-STEL: 0.02 ppm, 0.15 mg/rn'N I O S H R E L s , 1 9 7 810-hr T W A : 0.005 ppm, 0.036 mg/m 1

20-min Ceiling: 0.02 ppm, 0.14 mg/m 1

Toxici ty Data*Human, Inhalation, TC : 0.5 ppm

*See NIOSH, RTECS (CZ6300000), for additional data on toxicity with references to irritative, tumorigenic, and mutagenic e f f e c t s .

Boiling Point: 482 T (250 "C)*Mel t ing Point: ca 54 T (12 'QVapor Density (Air = 1): 6.0Vapor Pressure: 0.025 Torr* Volat i l e by Vctame: ca 100Molecular Weight: 174g/molS p e c i f i c Gravity 08,0 = 1): L22 at 77 T (25 *Q*Solubi l i ty in Water (%): TDI reacts exothermically(produces heat) with water to form carbon dioxide (CO2).

Appearance and Odor: A clear, colorless liquid (darkens upon exposure to sunlight); a sharp, irritating, pungent odor.Comments: Toluene diisocyanate is commercially available as the two isomers 2,4-TDI and 2,6-TDI. Commeicial mixtures of TDI areavailable in the f o l l ow ing three ratios: (1) 100% 2,4; (2) 80% 2,4:20% 2,6; (3) 65% 2,4:35% 2,6. The 80% 2,420% 2,6 commercial mixturerepresents over 95% of current industrial usages."Spec i f i c to the 80% 2,4:20% 2,6 product

!F l a s h P o l n t ; 2 6 6 T ( 1 3 0 ' C ) O C | Autolgni t lon Temperature; Not Found I LEL: 0.9% v/v {UEL: 9.5% v/vExtinguishing Media: This highly combustible liquid can be dangerous during f ire s; it is o f t en mixed with f lammable, volatile solvents.Use carbon dioxide (CO2)and water spray to extinguish toluene-2 t4-diisocyanate fires. Unusual Fire or Explosion Hazards: Containersof TDI can rupture violently when heated; cool exposed containers or tanks of mis material with water spray. Special Fire-lightingProcedures: Wear a self-contained breathing apparatus (SCBA) with a f u l l facepiece operated in the pressure-demand or positive-pressure mode.

S E C T I O NS t a b i l i t y /Polymerization: Toluene-2,4-diisocyanatc is stable in closed containers during routine operations at room temperature. , <Hazardous polymerization can occur if it is exposed to concentrated alkaline compounds such as sodium hydroxide (NaOH) or to fert-aminecompounds. Chemkal Incompat ib i l i t i e s : Hazardous reactions can occur between TDI and certain compounds containing active hydrogen(such as water, ammonia, amines, alcohols, and caustics such as sodium hydroxide, etc.). The reaction with water produces heat and carbondioxide. Conditions to Avoid: Prevent exposure to incompatible chemicals, sources of ignition, and ultraviolet light (yellow discolorationis otherwise likely). Hazardous Products of Decomposition: During fires, thermal oxidative degradation of toluene-2,4-diisocyanate canproduce toxic gases such as carbon monoxide (CO), carbon dioxide (CO,), and oxides of nitrogen (NOM).S E C T I O N € . H E A L T H H A Z A R D I N F O R M A T i Q NCarcinogenicity: Toluene-2,4-diisocyanate is not listed as a carcinogen by the NTP, IARC, or O S H A .Summary of Risks: TDI exhibits low oral toxic i ty; however, inhalation of very small amounts of it causes severe irritation of therespiratory system. Skin contact with TDI causes redness, swelling, and blistering, leading to allergic eczema and skin sensitization tofuture TDI exposure. Ingesu'on causes corrosive damage to the gastrointestinal tract Medical Conditions Aggravated by Long-TermExposure: Existing asthma, allergies, or respiratory problems. Primary Entry: Inhalation, skin contact Acute E f f e c t s : Severe irritationof the mucous membranes, respiratory tract, and eyes; acute asthmatic attacks; a choking sensation, chest pain, waves of productivecoughing (if breathing-zone concentration reaches 0.5 ppm, the pos s ib i l i ty of respiratory response is imminent with latent periods (canfd.)

C I989 fry Crania Futitatuaf GorpOHUOd

No. 331 TOLUENE-2.4-DIISOCYANATE 4/89r : S E C M ' I O N e i H E A L ^ H i H A Z A R P l N F X > R M A X I Q N , continued j

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of 4 to 8 hours; abdominal distress, nausea, and vomiting; and skin irritation. Chronic E f f e c t s : Allergic, asthmatic respiratory sensitivity to•future TDI exposure is likely unless present exposure to it is strictly limited or controlled. The hypersensitivity of certain individuals to this•material can result in long-term e f f e c t s or sensitization, even at low exposure of 0.02 ppm and below and may take 6 months to 20 years todevelop. Skin sensitization is another possibility. Once sensitized, reactions can occur to concentrations of 0.005 ppm or less.( FIRST AID: Eyes. Immediately f l u s h eyes, including under the cyeBds, gently but thoroughly with f l o o d i n g amounts of running water forat least 15 minutes. Skin. Rinse the a f f e c t e d area with a f l o o d i n g amount of water; wash it with soap and water. Inhalation. Remove theexposed person to fresh air; restore and/or support his or her breathing as needed. Have qualified medical personnel administer oxygen asrequired. Keep him or her warm and at rest until medical help is available. Ingestion. Unlikely. Should accidental ingestion occur, give theexposed person 2 to 3 glasses of water to drink and induce vomiting. Get fa-plant , paramedic, or community medical help for allexposure. Sect prompt mcdiral MlHf**""* *"• f a t f l i e r tMtmMit, nh«erv«tinn, and mppait a f t er f irs t «?d. Nate to Physician; If severeinhalation exposure is suspected, i«««M««te hospitalization with careful monitoring for the delayed (up to 72 hours) onset of pulmonaryedema is suggested. Steroids may be useful in decreasing or controlling the mflammatory response of the lungs if administered on a short-I term basis (2 to 4 days). Detailed preplacement and annual medical exams win special attention to pulmonary function studies, heart, lungs,I and allergic responses or symptoms are recommended for workers who may be exposed to TDI.

el, evaS p i l l / L e a k : Not i fy sa f e ty p ievent of a toluenc-2,4-diisocyanate spill or leak. Cle ry pup person el. sources of ignition, and provide adequate ventilation in thel must wear protective respiratory equipment to prevent inhalation of TDI(see sect 8); skin or eye contact must also be prevented. Absorb the spilled TDI with material such as vermkulite or sawdust and place itinto appropriate containers suitable for eventual disposal or reclamation. Waste Disposal: Contact your supplier or a licensed contractor fordetailed recommendations. Fol low Federal, state, and local regulations. Neutralize TDI residue in drums before they are disposed of orreused. Contact your supplier for neutralizing instructions.OSHA DesignationsListed as an Air Contaminant (29 CFR 1910.1000 Subpart Z)EPA DesignationsListed as RCRA Hazambus Waste No. U223 (40 CFR 261.33)Listed as a CERCLA Hazardous Substance* (40 CFR 302.4), Reportable Quantity (RQ): 100 Ib (45.4 kg), f *per RCRA, § 3001]Listed as a SARA Extremely Hazardous Substance (40 CFR 355), Threshold Planning Quantity (TPQ): 500 Ib •Listed as a SARA Toxic Chemical* (40 CFR 372.65) [*EPA Form R may a p p l y to your fac i l i ty; see 40 CFR 372.85 for instructions]

I SEG11QN & SFfcUJAk raGoggles: Always wear protective eyeglasses or chemical sa f e ty goggles. Wear a f u l l face shield where splashing of toluene-2,4-diisocyanate or its solutions is possible. Fol l ow OSHA eye- and face-protection regulations (29 CFR 1910.133). Respirator: Wear aN I O S H - a p p r o v e d respirator per Genium reference 88 for the maximum-use concentrations and/or the exposure limits cited in section 2.F o l l o w OSHA respirator regulations (29 CFR 1910.134). For emergency or nonroutine operations (leaks or cleaning reactor vessels andstorage tanks), wear an SCB A. Warning: Air-purifying respirators will not protect workers in oxygen-deficient atmospheres. Other: Wearimpervious butyl rubber gloves, boots, aprons, and gauntlets to prevent skin contact with TDI. Ventilation: Install and operate general andlocal maximum explosion-proof ventilation systems powerful enough to maintain airborne TDI concentrations below the OSHA PELstandard cited in section 2. Local exhaust ventilation is preferred because it prevents dispersion of the contaminant into the general workarea by eliminating it at its source. Consult the latest edition of Genium reference 103 for detailed recommendations. S a f e t y Stations: Makeemergency eyewash stations, safety/quick-drench showers, and washing faci l i t i e s available in work areas. ContaminatedEquipment: Contact lenses pose a special hazard; sof t lenses may absorb irritants and all lenses concentrate mem. Do not wear contactlenses in any work area. Remove and launder contaminated clothing before wearing it again; clean this material from your shoes andequipment. Comments: Practice good personal hygiene; always wash thoroughly af t er using this material and before eating, drinking,smoking, using the toilet, or app ly ing cosmetics. Keep it off your clothing and equipment. Avoid transferring it from your hands to yourmouth while eating, drinking, or smoking. Do not eat, drink, or smoke in work areas. Do not inhale TDI vapor.

Storage/Segregat ion: Store toluene-2,4-diisocyanate in closed containers in a cool, dry, well-ventilated area away from sources of heator ignition, incompatible chemicals, and strong oxidizing materials. Shade the containers from direct sunlight Outside, isolated, detached,or remote storage is recommended for bulk quantities. TDI that is stored in tanks should be blanketed with an inert gas such as nitrogen ordry air.Engineering Controls: Properly ventilate all work areas. Electrically ground and bond all containers used in shipping, receiving, transfer-ring, or sampling operations to prevent static sparks.Other Precautions: Sensitized workers must be kept away from virtually all exposures to toluene-2,4-diisocyanate. Careful monitoring ofthe workplace level of TDI and the workers' responses to it is suggested.

Transportation Data (49 CFR 172.101-2)DOT S h i p p i n g Name: Toluene DiisocyanateDOT Hazard Class: Poison BDOT ID N o . : UN2078DOT Lable: PoisonDOT Packaging Requirements: 49 CFR 173.346DOT Packaging Exceptions: 49 CFR 173345References: 1, 6, 26. 38, 84-94, 100, 116, 118, 119. 122

IMO S h i p p i n g Name: Toluene DiisocyanateIMO Hazard Class: 6.1IMO Label: PoisonIMDG Packaging Group: D

Prepared by: PJ Igoe. BS; Industrial Hygtene Review; DJ Wilson, Cffl; Medical Review: W Silverman, MDI C a p j m f M C 1989 by Gaum Pobtabmj Caponom. Anjr O

r Mcciurily O K puchner ' t mpanbfl iqr. A l t t oe or nprcHKOoo wnhool dc are h» fc-cn feken te the pnpmtao at mO> klDot,, UK: uimnn no rapornibiliiy u lo Hie icouvy at xttkiiqr ol such tnfonmuoo fat tpftiCMUao to tbc p u r c h u e r ' a mtcottcpuptxeat laPubliibiilt Copontiooc><ci»«i»wnnotit>. nstn DOirpmcnu

Woodward-Clyde

Toluidine

JUL-02--93 F R I 14:14 I D : I N D H Y Blin 3006 «375 PllM A f t K l A LS A F E T Y D A T AO C E A N ' NetworkE M E R G E N C Y P H O N E 1-800-OLIN-911

S E C T I O N I - I D E N T I F I C A T I O NC H E M I C A L N A M E • * V N O N « t f f ' ""o - T o l u i d i n e j 2 amtno-toluene; 2 methyl anilineC H E M I C A L . F A M I l * ( F O R M U L A n-M.M. Aniline | CiHgXD E S C R I P T I O NColorless to pal e yellow liquid

T R A D E N A M i ! ' —o-ToluidineC A * H O . — — — — —95-53-4

S E C T I O N I I - N O R M A L H A N D L I N G P R O C E D U R E SP R E C A U T I O N S TO BE TAKEN 1*9 KAMOLINO AMD S T O R A G E

May be f a t a l if swallowed. Avoid contact with eyes, skin or clothing. Upon contect wi thskin or eyes, wash off with water. Avoid breathing mist or vapor. Store in a cool, dry,well-ventilated place away f rom alLsources of ignition. Avoid contact with .oxidizers..

P R O T E C T I V E E Q U I P M E N T V E N T I L A T I O N R B O U I f t E M E N T *EyOOGlov«a GogglesI m p e r v i o u s glovesImpervious coveralls and boots

As required to keep airborneconcentrations, below TLV.

S E C T I O N I I I - H A Z A R D O U S I N G R E D I E N T Sa » f 1 C K A T E I M & L ° * * | A LOSO ' . L C ' S U . S I G W F I C A I 3 T *PI-«CTC, PIv

o-Toluldine S p p m .(skin) ....Z(F»- .&-H-H..TVIA

670 m g / k g(oral-rat). . .

•

I f L ° l , •• ZS mg/nv.(human) .-

Damage to liver, kidney,blood* and CN8. Anoxia,headache, -nausea,exhilaration, hematuria, .cyanosis, convulsions.S E C T I O N I V . F I R E A N D E X P L O S I O N H A Z A R D D A T A

F I A S M P O I N TM E T H O O 1 8 5 ° F C C O S N A C L A S S I F I C A T I O NCombustible liquidK X T I N G U I S M I N O M E D I AW a t e r spray, dry chemical, f oam or carbon dioxide.

F O M M A B L CE X P L O S I V EL I M I T S

L O W E R1.5%

U P P E RNo data

SPECIAL FINK HAZARD « FIRE PIOHTINQ PROCEDURE* water spray snouio DO useo to cooi lire exposeocontainers and/or to disperse unignited vapors. Use NIOSH/MSHA approved positivencii any 15 mvuwea in a

S E C T I O N V - H E A L T H H A Z A R D D A T AT H R E S H O L D L I M I T V A L U C ~o-Toluidine: 2 ppm skin (ACGIH 1987-88> -SYMPTOM* OF OVER fcxposuR* Damage to liver, kidney, blood, and CMS. Anoxia, headache,nausea, exhilaration, hematuria, cyanosis, convulsions.

S K I N

EVES

I N G C S T I O NM H A L A T . O t t

E M C R Q E M C V F I R S T - A I D PROCEDURESI m m e d i a t e l y f l u s h with water for 15 minutes, call a physician.I m m e d i a t e l y f l u s h with water for IS minutes, call a physician.I m m e d i a t e l y drink large quantities of water, induce vomitingd>wn ths.-o.it. - Call a physician.I n m e i i H t u l y remove victim to f i e s h a r, call a physician.

by sticking fing*r

J U L - 0 2 - ' 9 3 F R I 14:15 I D : I N D H Y B 300S «375 P12C H E M I C A L N A U C

S E a i O N V I - T O X I C O L O G Y ( P r o d u c t )570 mg/*3 < r a t )

o-Tolu;c;ne

c A f t c i K O O E K i c r r t S u s p e c t carcinogenI - . I I T / O E K I C I T V P o s i t i v e A m e s T e s t«: -«,» f-«t»hirt KYSmwTATiou Sever e irri tant'sssss.ic.o sw^sr---"—— "•"-'r r e i U H A L M i O M L C S O9 l l N C I * A i . J C O U T C * O P A B S O M F T I O H_ Inhala t i on , skin contac t , inges t ion, eye contact"~

innamimn, j-%,.. ^_-.-_ _ . ., ____i C Y S O f A C U T E E X P O S U R Epa H e a d a c h e , vomi t ing , low blood pressure, cyanosis, convulsions, d e r m a t i t i s , hematuria

j E F F E C T S O P C M f i O W l ' : E X P O S U N EAnemia, d e r m a t i t i s . Damage to liver, kidney, blood, and CMS. S u s p e c t earinogen.- - • . __*_ _ _ S E C T I O N V H . S P I L L A N D L E A K A G E P R O C E D U R E S ( C o n t r o l Procedure*)r: r\»li KATFKIAL K E L K A S t OM »«U.Wear N I O S H / M 5 H A approved p o s i t i v e pressure s u p p l i e d a i r respirator. F o l l o w O S H Aregulnt tons Cor re spirator use* (5ee 29 CFR 1910.134). Wear gogg l e s , impervious , c ov era l l s ,gloves and boots. Remove all sources of ignit ion. I s o l a t e area o£ sp i l l by diking. S t o p sourceof leak- T r a n s f e r - contents to non-leaking container, or storage vessel. Add non- combus t ib l edry absorbent, shovel or sweep up. Place In an. appropriate container end seal. Wash allcontamint t ed c lo thing b e f or e reuse. In the event of a large s p i l l , call the emergencyte l ephone number shown on the f r o n t of this sheet.

: R M C f t G R K C Y . C O N T A C T C H E M T R E C 800-424-9300' W A S T E o«sv£i3/.i. B C T H O QDispose of contaminated produc t , e m p t y containers and materials used in cleaning up s p i l l s orleaks in a manner approved for this material. Consult a p p r o p r i a t e f e d e r a l , s ta t e and local

regulatory agencies to ascertain.proper disposal procedures.,..*.I

S E C T I O N V I U • S H I P P I N G D A T AI n t e r m e d i a t e :A c r m T Y D A T A

I M A Z A H O O U *I P O t - Y B E R I Z A T I O K

Carbon monoxide^earbon diox ide , oxides of ni trogenS E C T I O N X • P H Y S I C A L D A T Am m H g Q 2 0 ° C

S O L O » I U T T I N W A T | « V»POK D E N S I T Y ( A i r •S P E C I F I C O * f c » M T V (U,O

: r u n r - r i s s j E o a v : Environmental H y g i e n e ° A T

and T o x i c o l o g y Department(202) f 8? -5.436 Ow.rtm.nl ei en»,ro»m.n,.l Hy9"

C O R P O R A T J O KLong n«*9» R**a Sia-.^ra C-«-.n,«.cui 0-.M4

O C E A U f Networl-.-SKSY P H O N E t BOO-OUN-*1 1

Woodward-Clyde

Toluene Diamine (TDA)

J U L - 0 2 - ' 9 3 F R I 14:16 I D : I N D H Y G 3006 8375 P13

Air Product* md Chemicals, Me.7201 H a m i l t o n BoulevardAllentown. PA 18195-1501Telephone (215) 481-4911

M A T E R I A L S A F E T Y D A T A S H E E T

AIRPRODUCTS

SECTION l: PRODUCT IDENTIFICATIONM A T E R I A L N A M E ( T R A D E N A M E ) * Meta-Toluenediamine, 9 9 XM A N U F A C T U R E RC H E M I C A L N A M E

Air Products and Chemical*, Inc. A l l a n t o w n , PA 181952,4-and 2,6-Toluanedi emineM a t a t a l y l e n a d i a m i n a2,4-and 2,6-diaminotoluena4-Methyl- l ,S-benzened iamine2-Methyl-l ,S-benzenediaaineT D A2,4 and 2 , 6 - T D Anr-TDA

C H E M I C A L F A M I L Y : Aromat i c aminesE M E R G E N C Y T E L E P H O N E N U M B E R S1-800-525-93741-215-481-4911 Cout s ida U . S . A . )

S A L E S a PRODUCT I N F O P H O N E1-800-345-3148

M S D S N U M B E R * 6202-08 E F F E C T I V E D A T E i November 1990R E V I S I O N N O T E t U p d a t e d H e a l t h Hazard Data

REVISIONi 08

S E C T I O N 2 2 H A Z A R D O U S I N G R E D I E N T SComponen t s) of the product ara:

2,4 - T o l u a n e d i a m i n e , approx . 80X ( T o x i c )2,6 - T o l u e n a d i a m i n e , a p p r o x . 202C ( T o x i c )T r a c e amounts of tha 2*3; 2,5; 3,4 and 3,5 isomars may be present.The Chemical Abstract Numbers are 95-80-7 for 2,4-TDA and 823-40-5 for2 . 6 - T D A .E x p e r i m e n t a l l y , t o luanadiamine has been shown to cause cancer inlaboratory animals.* It may enter the body via insertion, inhalationor skin contact.K S * e RafarencM 1 and 3.

S E C T I O N 3 1 P H Y S I C A L D A T AB O I L I N G P O I N TM E L T I N G P O I N TD E N S I T Y

541 F (28.3 C) a 760 mm Hg (80/20 TDA)210.2 F (99 C); (pure 2,4-isomer)8.68 I h . / g a l . a 221 F (105 C)| 1.Q

J U L - 0 2 - ' 9 3 FRI 14:16 ID:INDHYG 3006 8375 P14

Air Product* «nd Chemical*. Inc. All? A7201 Mammon Boulevard 0f9AlhMWovvn. PA 1B195-1501 PHT t f M p h o n e (215) 411-4911

SOLUBILITY IN HATER * S o l u b l e in ho t water, a l c o h o l , ether, andmany p o l a r organic so lvent s .

VAPOR P R E S S U R E Com Hg) ' 0.3* x 10-3 mm Hg 3 100 F C37.8 C>;1 mm Ho 3 223 F C 1 0 6 . 5 Oj100 mm Hg 3 413.6 F C212 C)

V A P O R D E N S I T Y : N o t A p p l i c a b l eX V O L A T I L E B Y V O L U M E ' N o t A p p l i c a b l eP H : N o t A p p l i c a b l eA P P E A R A N C E / O D O R = S o l i d , l i g h t y e l l o w to tan, darkens on

storage and exposure to a i r / S l i g h tammonia-l ike

S E C T I O N A s F I R E A N D E X P L O S I O N D A T AF L A S H P O I N T » 2 8 4 f (140 C )

A S T M 0 9 2A U T O I G H I T I O N T E M P . 8 4 2 F C 4 S O C )F L A M M A B L E L I M I T S ( * > > N o DataE X T I N G U I S H I N G M E D I A : water, carbon d i o x i d e , o r f oam.S P E C I A L F I R E F I G H T I N G P R O C E D U R E S :P o t e n t i a l l y toxic p r o d u c t s of combustion suggest that surrounding areasshould be evacuated.Due to the b i o l o g i c a l p r o p e r t i e s of TDA, an a t t e m p t should be made tocontain water used to ex t ingui sh a f i r e .The chemical s tructure of TDA suggests that toxic ammonia* carbonmonox ide and n i t rogen oxides may be l i b e r a t e d when TDA is heated toh i g h t empera tur e s or p y r o l y z e d . S i n c e ma t e r ia l s of combustion may bet ox i c , f u l l body p r o t e c t i o n (con s t ruc t ed of butyl rubber or i t se q u i v a l e n t ) i n c l u d i n g a s e l f - c o n t a i n e d brea th ing a p p a r a t u s , should beworn when f i g h t i n g f i r e s .F I R E A N D E X P L O S I O N H A Z A R D :Down-wind personnel must be evacuated.

S E C T I O N 5 : H E A L T H H A Z A R D I N F O R M A T I O N / F I R S T A Z DT o x i c o l o g y *

o M i l d i r r i t an t to the ayes and skin of a rabb i t ,o Oral L D 5 0 C r a t ) : 212 m g / k go Dermal L D 5 0 ( r a b b i t ) : >5750 m g / k go I n h a l a t i o n L C 5 0 ( r a t ) : >5.3 m g / l / 4 H or >180 ppmo R e p r o d u c t i v e e f f e c t s , m e t h e m o g l o b i n e m i a , h e p a t o t o x i c i t y ,

thyroid and bone marrow h y p e r p l a s i a have been reported inexposed labora tory animals .

Routes of Entry*o I n g e s t i o no S k i n ab sorp t i ono I n h a l a t i o n

J U L - 0 2 - ' 9 3 FRI 14:17 ID:INDHYB 3006 «375 P15

Air Product* and Chemical s , ine. —._.—.«. , . .PRODUCTS rTelephone ( 2 1 5 ) 4B1-491 1

S E C T I O N 6 : R E A C T I V I T Y D A T ASTABILITY* The product is s t a b l e and do ax not undergo spontaneousp o l y m e r i z a t i o n . TDA undergoes ox ida t i on when exposed to air with thap r o d u c t i o n of color bodias and tars. T h i s reaction procaads mostr a p i d l y at high t empera ture , for example , when in the mol tan state.O x i d a t i o n p r o d u c t s have not been f u l l y characterized and should betreated as toxic mater ial s .I N C O M P A T I B I L I T Y C S P E C I F I C M A T E R I A L S T O A V O I D ) : T D A i * weakly basic a n dreacts with mineral acids to f o r m water s o l u b l e amine salt s . The sa

are more s tab l e to o x i d a t i o n than the basic amine.H A Z A R D O U S D E C O M P O S I T I O N P R O D U C T S ! S e e s t a b i l i t y comments above.H A Z A R D O U S P O L Y M E R I Z A T I O N « H i l l n o t occur

S E C T I O N 7 s S P I L L . L E A K A N D D I S P O S A L PROCEDURESThe produc t i s s h i p p e d in the mo l t en or so l id state. If a s p i l loccurs, the area should be evacuated until the TDA s o l i d i f i e s . S p i l lc l e a n - u p should be done by personnel wearing c ompl e t e body pro t e c t i onCsee S e c t i o n 8). F o l l o w i n g removal o f s o l i d i f i e d TDA* the area should )be cleaned t h o r o u g h l y with hot water to remove all residual TDA f r o ms u r f a e a s . Contaminated water should be contained to prevent surfaceand ground water con taminat i on . S o l i d TDA should be scooped intod i s p o s a l containers cons tructed of corros ion-protec ted carbon -steal orof s t a in l e s s s t e e l . Dispo sa l containers should bear warning ofT o l u e n e d i a m i n e * a toxic substance Csee label in S e c t i o n 9) and warningagainst skin contact or i n h a l a t i o n of vapors.D I S P O S A L ' •H a s t e mat er ia l may be inc inerated or d i s p o s e d in a Cla s s I hazardouschemical l a n d f i l l where p e r m i t t e d by l o ca l au thor i t i e s . Drumsc o n t a i n i n g TDA shou ld not be re-used but should be buried in a Cla s s Ihazardous chemical l a n d f i l l . Dispo sa l s h ou ld be c o m p l e t e d by ana u t h o r i z e d , l i c ensed d i s p o s a l agent . Care should be taken to assurep r o p a r container s e a l i n g to prevent ground and s u r f a c e waterc on tamina t i on . I n c i n e r a t i o n of TDA at c o n t r o l l e d rates in a p r o p e r l yd e s i g n a t e d chemical waste incinerator is the p r e f e r r e d method ofd i s p o s a l . T o x i c n i t r o g e n oxide emissions may increase as a result ofburning.

S E C T I O N 8 : S P E C I A L P R O T E C T I O N I N F O R M A T I O NV E N T I L A T I O N : W o r k areas need t o b e wel l v e n t i l a t e d .For r e s p i r a t o r y p r o t e c t i o n , a h a l f - f a c e mask of the car tr idge type* jN a t i o n a l I n s t i t u t e f o r O c c u p a t i o n a l S a f e t y a n d H e a l t h C N I O S H ) a p p r o v e dfor o rgan i c vapors , is recommended. If dust or mist p a r t i c u l a t e is toba removed/ a dust f i l t e r in series wi th the organic vapor f i l t e r isrequired.

JUL-02--93 FRI 14:17 ID:INDHYG 3006 8375 P16

Air Product* wid ClwmiMht. Inc.7201 H a m i l t o n BoultvardAHtmtown. PA 18195-1501T e l e p h o n e (215)481-4911 PRODUCTS l£l

EYE PROTECTION* Hrar s a f e t y alms*** with side s h i e l d s or chemicalsp la sh gogg l e s . When mol t en IDA is being hand l ed , a f u l l - f a c e shieldshould be worn in conjunc t ion with s a f e t y glasses or goggle s .HAND PROTECTION '• Wear gloves made of butyl rubber or its equivalent.OTHER: Wear overshoes made of butyl rubber or its equivalent and along sleeved shirt. When mol ten TDA is hand l ed , « lab apron or coatmade of butyl rubber or its equivalent should be worn in conjunc t i onwith gloves and overshoes.

S E C T I O N 9 $ S P E C I A L P R E C A U T I O N S A N D H A N D L I N G I N P O R H A T I O NH A N D L I N O '

T O L U E N E D I A M I N EC A U S E S C A N C E R I N L A B O R A T O R Y A N I M A L SW A R N I N G .

H A R M F U L I F S W A L L O W E D , I N H A L E D O R ABSORBED T H R O U G H S K I NM A Y C A U S E C H E M I C A L C Y A N O S I S

Avoid breathing dust or vapor. Avoid contact with eves, skin orc l o t h i n g . Use only with adequate v en t i la t i on . K e e p containersclosed. Hash thoroughly a f t e r h a n d l i n g . Use pro t e c t iv e c l o th ing ,butyl rubber g love s , boots and g o g g l e s . Discard contaminated c l o t h i n gand shoes. M o l t e n material w i l l cause skin and eye burns.F i r s t A i d ' I f s w a l l o w e d , induce vomi t ing . I f pat i ent i s eyanotic( b l u e co lor o f s k in), give oxygen. C A L L A P H Y S I C I A N .If i n h a l e d , remove victim to f r e s h air. In case of skin contact,remove c l o t h i n g , take a body shower in lukewarm water. Clean underf i n g e r n a i l s . D O N O T U S E H O T W A T E R .In case of eye contact, f l u s h with large quantit ies of water for atleast 15 minutes.S p i l l or l e a k ' Evacuate area. C o n t a i n s p i l l with earth dikes anda l l o w to s o l i d i f y . S c o o p into drums by personnel with f u l l bodyprotect ion. Rinse down area with water. Has t e material may beincinerated or used as l a n d f i l l if p e r m i t t e d by local authori t i e s .H A N D L I N O A N D S T O R A G E R E Q U I R E M E N T S :The produc t oxidizes in the presence of air. Exposure to air should beminimized . M e l t shou ld be t rans f erred in l eak- fr e e systems ( p u m p s , p i p eand c o u p l i n g ) .

S E C T I O N l O t A D D I T I O N A L I N F O R M A T I O N

J U L - 0 2 - ' 9 3 FRI 14:18 ID:INDHYE 3006 «375 P17

AII9Air Product* and Chemieala. me. oofint ir»reH a m i l t o n Boulevard PRODUGlSTelephone" (215) 481-4911

Exposure S t a n d a r d s 'o No standards establisheda Maintain air concentrations in tha workplace at the lowestf e a s i b l e levels.

H e a l t h Hazards!M i l d irritant to tha eyes and skin.T o x i c C A N S I 2129.1,1988) b y ingestionCarcinogen ( a ) X A R C C b J N T P C c > O S H ABlood toxinH a p a t o t o x i n or Liver toxinReproductive hazard

S i g n s and Symptoms of Exposureo Contact with the eyas or skin causes irritation and d i s comfor t .o Repeated a n d / o r pro l onged contact with the skin may cause

sensitization.o Product is absorbed through the skin and may cause nausea,headache and general d i s c o m f o r t ,o I n h a l a t i o n of dust may cause respiratory irri tat ion and may causecyanosis.o I n g e s t i o n may causa headache, nausea a n d / o r vomiting,a Repeated a n d / o r p r o l o n g e d exposure at low l eve l s may result in*o l iver disorderso blood chemistry changeso reproduc t ive disorders

Medica l C o n d i t i o n s G e n e r a l l y Aggrava t ed by Exposureo Liver disorders

F I R S T A I D :E Y E C O N T A C T *F l u s h aye for at least 15 minutes with large quantit ies of water.S K I N C O N T A C T 'Remove material f r o m skin with soap and warm water. Generalcon taminat i on of the body or limbs requires a f u l l body shower withspecial a t t e n t i o n to hair and f i n g e r n a i l s . Hot water should be avoidedas it may enhance ab s orp t i on . Discard contaminated c l o t h i n g andshoes. For burns of the skin, cover the a f f e c t e d area with a s t eri ledressing or clean shee t ing and transport for medical care. Controlshock.I N H A L A T I O N iRemove v i c t im to f r e s h air. A d m i n i s t e r a r t i f i c i a l respiration andoxygen i f vic t im i s no t breathing. If breathing i s d i f f i c u l tadmini s t er oxygen. C A L L A P H Y S I C I A N .I N G E S T I O N 'If i n g e s t e d , empty stomach by aspirat ion or induced vomiting. CALL AP H Y S I C I A N .

J U L - 0 2 - ' 9 3 FRI 14:18 ID:INDHYE 3006 8375 P18

Air Products mfitl Chemical*. Inc. Alft „/••S S K S T S f f l f t S S i PRODUCTS f c =T A W p n o n e (at5> 481.4911

R E G U L A T O R Y C O N C E R N S :T h e p r o p e r s h i p p i n g d e s c r i p t i o n f o r T o l u e n e d i a m i n e according t o t h aDepartment o f T r a n s p o r t a t i o n C O O T ) i s R Q , T o l u e n e d i a m i n e . O R N - A /N A 1 7 0 9 .All component s ara in c luded in the E . P . A . T o x i c Subs tance Control ActChemical Subs tanea I n v e n t o r y .O S H A H a z a r d Communica t i on S t a n d a r d C 2 9 C F R 1 9 1 0 . 1 2 0 0 ) hazard class: a )toxic by inge s t i on , b> carc inogen, c) raproduc t ive toxin and d> l ivertoxin.E P A S A R A T i t l e I I I hazard c l a s s ' a ) immediate h e a l t h hazard a n d b )de layed h e a l t h hazard.S u b s t a n c e C s ) l i s t ed by C a l i f o r n i a under the " S a f e Drinking W a t e r andT o x i c Enfor c ement Act o f 1986" C P r o p o s i t i o n 6 5 ) » 2 ,4-diare ino to luene .E P A S A R A T i t l e I I I S e c t i o n 3 1 3 C 4 0 C F R 3 7 Z ) T o x i c Chemica l s present i nquant i t i e s greater than the "de minimis" level are* Diaminoto luaneC m i x e d i somers) 1 D O X ) .EPA R e p o r t a b l a Quant i ty U n d e r C E R C L A for T o l u e n e d i a m i n e i s 1 pound .(0.454 k g ) . JCanadian W H M I S C o n t r o l l e d P r o d u c t s C l a s s i f i c a t i o n * - Cla s s DDivisions IB and 2A.R e f e r e n c e s '1 . N . I t o . Y . H i a s a , Y . K n o s h i a n d M . M a r u g a m i , Cancer Research, 2 9 :

1137-45 ( 1 9 6 9 ) .2. Air P r o d u c t s and C h e m i c a l s , I n c . , da ta . Report a v a i l a b l e upon

request.3 . R . H . C a r d y , J . o f N a t i o n a l Cancer I n s t i t u t e . 2 6 ( 4 ) 1107-1115,

( 1 9 7 9 ) ,EEC Risk and S a f e t y Phrases= R 12, 20, 21, 22, 36, 37, 38

S 24, 25, 26, Z8, 36, 37, 39, 46

Woodward-Clyde

Dinitrotoluene ( D N T )

J U L - 0 2 - ' 9 3 FRI 14:09 ID:INDHYG 300S «375 P02

Air Products and Cheimcils. inc. AIR7201 H a m i l t o n Boulevard BOOfW IT*T^CAltentown. PA 18195-1501 F T f U W U U f OT e l e p h o n e (215) 481-4911M A T E R I A L S A F E T Y D A T A S H E E T

S E C T I O N 1 - M A T E R I A L I D E N T I F I C A T I O NP R O D U C T N A M E D X N I T R O T O L U E N EPRODUCT CODE _ D N T M S D S R E V I S I O N N U M B E R * 6200-07M A N U F A C T U R E R A i r Produc t s a n d Chemica l s , I n o

7201 H a m i l t o n B l v d . , A l l e n t o w n , PA 18195-1501E M E R G E N C Y T E L E P H O N E N U M B E R C S ) 800-523-9374 ( C o n t i n e n t a l U . S . )

215-481-7711 (Outs ide Continental U . S . )800-322-9092 (Pennsy lvania o n l y )D A T E P R E P A R E D S E P T E M B E R 1992R E V I S I O N N O T E S * N e w M S D S F o r m a tC . A . S . C H E M I C A L NAME121-14-2 2 ,4-Dinitroto luane with 606-20-2

2,6-Dini tro to lueneS Y N O N Y M S N o n eC H E M I C A L F A M I L Y : A r o m a t i c N i t r o CompoundE M P I R I C A L F O R M U L A MixtureI N T E N D E D U S E Chemical I n t e r m e d i a t eS E C T I O N 2 - I N G R E D I E N T S

CAS Number and Chemical N a m e

121-14-2 2 , 4 - D i n i t r o t o l u e n e606-20-2 2 , 6 - D i n i t r o t o l u e n e

X

8020

O S H AP E L / T L V - T W Appm morm3N / EN X E

A C 6 I HS T E L - T W APPM morm3N / EN ' E

NXE = Not Es tab l i sh ed TVS = T r a d e Secret -S = S k i nS E C T I O N 3 - H E A L T H H A Z A R D S

E JE M E R G E N C Y O V E R V I E W

H M I S H E A L T H R A T I N G 3 F L A M M A B I L I T Y 1 R E A C T I V I T Y 0S o l i d , Y e l l o w , P e n e t r a t i n gT o x i c ( A N S I Z 1 2 9 . 1 , 1988) b y inge s t ion a n d i n h a l a t i o n .121-14-2 2 , 4 - D i n i t r o t o l u e n e l i s t e d as a carcinogen by NIOSH CIS 144.I g n i t i o n w i l l give rise to a Cla s s A f i r e . In case of f i r e use MaterS p r a y .X K K K K X X X X X K K K X K K X K X K X X K K K X K K K K K K K K K X K K K K K X X X X K X X X K X X K K X X K X X X X K X X K K X X X X K K X X

R O U T E S O F E X P O S U R E

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Air Product* wnd Chemicals, Inc.7201 H a m i l t o n BoulevardAllentown. PA 18195-1501Tbtophona (215) 481-4911

I n g o c t i o nS k i n A b s o r p t i o nI n h a l a t i o n

E X P O S U R E S T A N D A R D SO S H A P E L - T H A 1 . 5 m g ' m 3 | A C G I H T L V - T W A 1 . 5 m g / m 5 .

H E A L T H H A Z A R D S :T o x i c (ANSI 2129.1, 1988) by ingast ion and i n h a l a t i o n .1Z1-14-Z 2,4~Dinitroto luene l i s t ed as a carcinogen by NXOSH CIB §44.

T A R G E T O R G A N SBloodH e a r tLiver or the h epa t i c systemK i d n e yCentral nervous systemReproduc t iv e system

S I G N S A N D S Y M P T O M S O F E X P O S U R E C A c u t e e f f e c t s )Produc t is absorbed through the skin and may cause nausea, headacheand general d i s c o m f o r t .Syst emi c e f f e c t s may i n c l u d e f a t i g u e , la s s i tude , i r r i t a b i l i t y ,headache, nausea, vomi t ing a n d / o r diarrhea.

S I G N S A N D S Y M P T O M S O F E X P O S U R E ( P o s s i b l e Longer Term E f f e c t s )Repeat ed a n d / o r p r o l o n g e d exposures may result in liver disorders(such as j a u n d i c e or l iver e n l a r g e m e n t ) ; kidney disorders (such asedema, or p r o t a i n u r i a ) ; nervous system disorders (such as narcosis,behavioral changes or decrease in motor f u n c t i o n ) ; b lood chemistrychanges (such as cyanosis or loss of consciousness); reproduct ivedi sorder s (such as b ir th d e f e c t s or s t e r i l i t y ) a n d / o r musculard y s f u n c t i o n .

M E D I C A L C O N D I T I O N S G E N E R A L L Y A G G R A V A T E D B Y E X P O S U R EH e a r t diseaseK i d n e y d i sorder sL i v e r d i s order s

I R R I T A T I O N E F F E C T S D A T ANo i r r i t a t i o n data are known for this p r o d u c t .A C U T E T O X I C I T Y E F F E C T S D A T A

Oral L D 5 0 ( r a t ) < 7 9 0 m g / k gDermal L D 5 0 C r a b b i t ) : 1000 m g / k gI n h a l a t i o n L C 5 D ( r a t ) : 2 m g / L

O T H E R A C U T E E F F E C T SNo Data

C H R O N I C X S U B C H R O N I C D A T AResul t s f r o m a ba t t ery of short term genotoxic tests on this materiali n d i c a t e mutageni e a c t iv i ty .Component has caused cancer in laboratory animals .

PIRODC/CTC ±~1

J U L - 0 2 - ' 9 3 FRI 14:10 ID:INDHYB 3006 «375 P04

Air Products mnd Chemicals. Inc. Atl> f7201 H a m i l t o n Boulevard nnj-tnf §f*w£ + <•»'Allentown. PA 18195-1501 PRODUCTS Z——T o l s p h o r w (216) 4B1-4&11

Component has caused reproduc t ive a f f e c t s in lab animal*SECTION 4 - FIRST AID

E Y E C O N T A C TH o l d eye l id s apart and i m m e d i a t e l y f l u s h eyes with p l e n t y of waterfor at least 15 minutes. C a l l a physician.

S K I N C O N T A C TNash a f f e c t e d area with soap and water.

I N H A L A T I O NMove pa t i en t to f r e sh air. If breathing has s t opped or is laboredgive assisted respiration (e .g . mouth-to-mouth). S u p p l e m e n t a l oxygenmay be i n d i c a t e d . C a l l a physic ian.T h e r e has been no cl inical experience with overexposure via therespiratory route.

I N G E S T I O NIf swal lowed* ca l l a physic ian immedia t e ly . I n d u c e vomit ing orremove stomach contents by gastric suction only as directed bymedical personnel . N e v e r give anything by mouth to an unconsciousperson.

S E C T I O N 5 - F I R E A N D E X P L O S I O N D A T A

C H A R A C T E R I S T I C S !F l a s h Point 404F C 2 0 7 C ) C2, 4 isomer)U p p e r E x p l o s i o n L i m i t ( U E L ) N o DataLower E x p l o s i o n L i m i t ( L E D N o DataA u t o i g n i t i o n T e m p e r a t u r e N o DataF l a s h Point M e t h o d ( s ) N o t s p e c i f i e dF i r e H a z a r d C l a s s i f i c a t i o n C o m b u s t i b l e L i q u i d , Cla s s I I I BC O S H A / N F P A )E X T I N G U I S H I N G M E D I A

I g n i t i o n w i l l give rise to a Class A f i r e . In case of f i r e use HaterS p r a y .

S P E C I A L F I R E F I G H T I N G P R O C E D U R E SF i r e - f i g h t e r s s hou ld wear butyl rubber boots, g l o v e s / and body suitand a s e l f - c o n t a i n e d b r ea th ing a p p a r a t u s . Retain expended l i q u i d sf r o m f i r e f i g h t i n g f or l a t e r d i s p o s a l . Mater spray i s also u s e fu l inc o o l i n g f i r e - e x p o s e d tanks and in d i sp e r s ing vapors.

U N U S U A L F I R E A N D E X P L O S I O N H A Z A R D SMay generate toxic or i r r i t a t i n g combustion produc t s .

S E C T I O N 6 - R E A C T I V I T Y H A Z A R D D A T A

JUL-02--93 FRI 14:11 ID:INDHYB 3006 «375 P0S

Air Productt and Chemicals, Inc. AIR7301 H a m i l t o n BoulevardAlleniown. PA 18106-1501T e l e p h o n e (215) 481-4911

C H E M I C A L S T A B I L I T YS t a b l e at ambient temperatures.

C O N D I T I O N S T O A V O I D ( i f U n s t a b l e )A d m i x t u r e with organic chemicals or combustibles.

I N C O M P A T A B I L I T Y C M a t e r i a l s t o A v o i d )N o n e known.

H A Z A R D O U S D E C O M P O S I T I O N P R O D U C T S C f r o m burning, heat ing, o r reactionwith other m a t e r i a l s )

Carbon Monox ide in • f i r eCarbon Dioxide in a f i r eN i t r o g e n Oxides in a f i r eI r r i t a t i n g and toxic fumes at elevated temperatures .

H A Z A R D O U S P O L Y M E R I Z A T I O NH i l l not occur.C O N D I T I O N S T O A V O I D ( i f m a y occur)N F P A Reac t iv i ty Rat ingS E C T I O N 7 - S P I L L , L E A K A N D W A S T E D I S P O S A L I N F O R M A T I O N

C O N T A I N M E N T T E C H N I Q U E S tRemoval o f i g n i t i o n sources, d i k i n g e t c)V e n t i l a t e the space involved.

C L E A N - U P P R O C E D U R E SShove l s p i l l e d chemical produc t into empty, dry container for la terd i spo sa l or recovery.F l u s h area wi th hot water spray.

O T H E R E M E R G E N C Y A D V I C EHear pro t e c t ive c l o t h i n g , boots, gloves, and aye protect ion.Evacuate the area unt i l the produc t s o l i d i f i e s .Prevent s p i l l e d p r o d u c t f r o m enter ing streams or dr ink ing waters u p p l i e s . N o t i f y local h e a l t h authori t i e s a n d other a p p r o p r i a t eagencie s i f such contaminat ion should occur.Poten t ia l for carbon monoxide a n d / o r nitrous oxides generation in af i r e must be recognized.

H A S T E D I S P O S A L 'C o m p l y with a l l F e d e r a l , S t a t e a n d Local R e g u l a t i o n s .D i l u t e with organic solvent and incinerate using e f f l u e n t gasscrubber.For smal l quant i t i e s : I n c i n e r a t e in su i tab l e combustion chamber.I n c i n e r a t e in an open container.

E N V I R O N M E N T A L E F F E C T S2,4- and 2 , 6 - D N T are assigned RCRA H a z a r d o u s waste numbers U105 andU106 r e s p e c t i v e l y ; banned f r o m l a n d f i l l except with special permit.

JUL-02--93 FRI 14:11 ID:INDHYG 3006 8375 P06

Air Products and Chemicals, Inc. AIRT«MM U * t f M : t t A « i R««>.lAu*vH __ _ _ _ _^^*T*7201 Hami l t on bomevnrg mar*r«* M *rAllentown. PA 18195-1501 J W L J f J t J l ^ f 0Telephone (215) 481-4911

S E C T I O N 8 - P E R S O N A L P R O T E C T X O N ' E X P O S U R E C O N T R O L S

E Y E P R O T E C T I O N :Chemical s a f e t y glasses or S p l a s h - p r o o f eye Boggle s .Nhen mol t en product i s being h a n d l e d ' F u l l f a c e shie ld with g o g g l e sunderneath.

H A N D P R O T E C T I O N *Rubber gloves.R E S P I R A T O R Y P R O T E C T I O N

In p o o r l y v en t i la t ed areas, a car tr idge mask N a t i o n a l I n s t i t u t e f orOccupat ional S a f e t y a n d H e a l t h ( N I O S H ) approved f o r organic vapors i srecommended.

P R O T E C T I V E C L O T H I N GRubber apron; Rubber boots

E N G I N E E R I N G C O N T R O L SM a i n t a i n air concentrations in work spaces in accord with s tandardsou t l ined in S e c t i o n s 2 and 3.

W O R K A N D H Y G I E N I C P R A C T I C E SH a s h at the end of each work sh i f t and b e f o r e eat ing? smoking or usingthe t o i l e t .Launder or discard contaminated c l o t h i n g .

S E C T I O N 9 - S T O R A G E A N D H A N D L I N G

S T O R A G EK e e p in c o o l / dry, v en t i l a t ed s torage and in closed containers.Protect containers against physical damage.K e e p container closed.

H A N D L I N GAvoid contact with skin or ayes.Avoid contact with skin, eyes, or c l o t h i n g .

O T H E R P R E C A U T I O N SEmergency showers and eye wash s tat ions should be r ead i ly accessible.A d h e r e to work prac t i c e rules e s tabl i shed by government regulat ions( e . g . O S H A ) .

S E C T I O N 1 0 - P H Y S I C A L A N D C H E M I C A L P R O P E R T I E SP H Y S I C A L F O R M S o l i dC O L O R Y e l l o wODOR P e n e t r a t i n gT Y P I C A L P H Y S I C A L D A T ApH No Data

J U _ - 0 2 - ' S 3 F R I 14:12 I B : I N D H Y B 3006 8375 P07

Air Product* and C h f t m t o a f s , Inc.7201 Hamil ton BoulevardAllemown. PA 18195-1501Telephone (215} 481-4311

V A P O R P R E S S U R E Cna H0>VAPOR D E N S I T Y C A i r = 1 5B O I L I N G P O I N TF R E E Z I N G X M E L T I N G P O I N TS O L U B I L I T Y I N W A T E RS P E C I F I C G R A V I T Y C H a t e r = 1 )

E V A P O R A T I O N R A T E C B u t y l a c e t a t aV I S C O S I T Y C C P S XM O L E C U L A R H E I G H T

AIRPRODUCTS

i )

1 a 106C6,3515-57ZF (267-300C) a 769 M m H y133-140F C 5 6 - 6 Q C J0.05^X1000 so lu t ion1.346 a 151F C m o l t a n )1.31 a 176F t m o l t e n }No DataNo DataMixture

SECTION 11 - TRANSPORTATION INFORMATION

UN No.D O T S H I P P I N G N A M E C N o n b u l k ) H a z a r d o u s Subs tance , s o l i d , N . O . S . ;

Dini tro to luene s; ORM-E, N A 9 1 8 8 ; Chamieals N . O . I .I M O S H I P P I N G N A M E

I A T A S H I P P I N G N A M E

SECTION 12 - U . S . FEDERAL REGULATIONS

Dini tro to luene s , S o l i d ; Poison; Poison B; U N Z 0 3 8 ;I N D G CODE P A G E * 6137; Packaging Group I IDini t ro t o lu ene s , S o l i d ; Poison; Poison B;U N 2 0 3 5 ; I M D G CODE P A G E ' 6137; Pnckaoinn Group I I

T O X I C S U B S T A N C E S C O N T R O L A C T C T S C A ) -All components are included in the EPA T o x i c Substances ControlA c t C T S C A ) Chemical Substanca Inventory

O S H A H a z a r d Communica t ion S t a n d a r d C 2 9 C F R 1 9 1 0 . 1 2 0 0 ) hazard c la s s(e s)CarcinogenT o x i c by i n h a l a t i o n and insestion.

E P A S A R A T i t l e I I I S e c t i o n 3 1 2 C 4 0 C F R 3 7 0 ) hazard classImmedia t e H e a l t h HazardDelayed H e a l t h Hazard

E P A S A R A T i t l e I I I S e c t i o n 3 1 3 C 4 0 C F R 3 7 2 J toxic chemicals above " d ominimis" level are

121-13-2 2>4~Dinitrotoluena at no more than SQJf606-20-2 2 , 6 - D i n i t r o t o l u e n e at no more than 20*

S E C T I O N - S T A T E R E G U L A T I O N S

Propo s i t i on 65 s ub s t ane e f s) l i s ted by the state of C a l i f o r n i a under the" S a f e D r i n k i n g (later and T o x i c Enforcement Act of 1986"

121-14-2 2 ,4-Dini t ro t o lu ene

J U L - 0 2 - ' 9 3 FRI 14:12 IBsINDHY5 3006 8375 P08

Air Product* and Chemical*. Inc. AIR7201 Hamil ton Boulevard DDSinf H T ' CAllentown. PA 18195-1501 f T C U U I r t r f OTelephone (215) 481-4911

New Jersey Trad* Secret Ragictry N u m b e r C i c )Nona

SECTION 14 - INTERNATIONAL REGULATIONS

C A N A D AR E G U L A T O R YDSL I n c l u d e d on Inventory

W H M I S Hazard C l a s s i f i c a t i o n Class D Division I BClass D Division 2A

W H M I S T r a d e Secret Registry N u m b e r C s )W H M I S H A Z A R D O U S I N G R E D I E N T S I n c l u d e d i n Sec t ion 2

L A B E L I N GHHMIS Symbol S k u l l and Crossbonas, S t y l i z e d T

EUROPEAN E C O N O M I C C O M M U N I T Y I E E C )R E G U L A T O R YEINICS Master Inventory I n c l u d e d on Inven toryL A B E L I N GEEC SYMBOL H a r m f u lEEC Council Directives r e l a t ing to the c l a s s i f i c a t i o n , packaging

and l a b e l i n g of dangerous substances and preparat ions Risk CR) andS a f e t y t S ) phrases

H a r m f u l by inha la t i on , in contact wi th skin and if swal lowed.May cause cancer. May cause heritable genetic damage.A v o i d contact with skin. A f t e r contact with skin, washimmed ia t e ly with p l e n t y of water. Hear su i tab l e protect ivec lo th ing* glove s and a y e f f a c e pro t e c t i on .

Woodward-Clyde

A P P E N D I X BC H E C K L I S T OF ACTIVITIES TO BE COMPLETED

PRIOR TO E X C A V A T I O N OR DRUM HANDLING

Woodward-Clyde

APPENDIX B

CHECKLIST OF ACTIVITIES TO BE COMPLETEDPRIOR TO EXCAVATION OR DRUM HANDLING

_WCC - N o t i f y residents immediately adjacent to the site of activities to beconducted that day and estimated completion time. Determine which will be home.

Eagle - Set up fenceline and off site air monitors as required in the "AirMonitoring Plan" (real time, integrated sampling, and particulates).

__Eagle - Set up supplemental air monitoring equipment to collect integrated airsamples at o f f - s i t e sample locations A-F shown on Figure 3-1. (See Section 4.2)

Eagle - Set up supplemental real time air monitor(s) at the fenceline to monitorfor TDI. (See Section 4.2)

__GDC - Calibrate and begin monitoring with OVA and TDI air monitors. (SeeSection 4.1 of this plan and Sections 2.1.5 and 2.1.7 of the GDC Heal th and S a f e t yPlan.)

__GDC - Establish Exclusion Zone, to include the portions which may extend outsideof the site fence where appropriate.

__Security - Place an individual to monitor those portions of the Exclusion Zonewhich may be outside of the site fence to prevent entry by anyone not in Level Bprotective equipment.

__GDC - Ensure that all required equipment is on hand and functional. (SeeA p p e n d i x C)

92BQ59C-D/DRUM059.A-B C O M B U S T N 07-09-93

Woodward-Clyde

A P P E N D I X CE Q U I P M E N T L I S T F O R E X C A V A T I O N

A N D DRUM H A N D L I N G

Woodward-Clyde

A P P E N D I X DC O N F I N E D SPACE E N T R Y PERMIT

HS-513.12WOODWARD-CLYDEC O N F I N E D SPACE E N T R Y PERMIT

Page I of 3

PROJECT N A M E / N U M B E R __________________•EXACT L O C A T I O N OF PERMIT REQUIRED CONFINED SPACE

PURPOSE OF E N T R Y AND DESCRIPTION OF WORK

POSSIBLE H A Z A R D S

H A Z A R D CONTROL MEASURES E.G. ( I S O L A T I O N , V E N T I L A T I O N )

NAMES OF A U T H O R I Z E D ENTRANTS

NAMES OF ELIGIBLE ATTENDANTS (OUTSIDE)

INDIVIDUALS ELIGIBLE TO BE IN CHARGE

II Pace 2 of 3I N I T I A L A T M O S P H E R I C S A M P L I N G

I . ™ A C C E P T A B L E• TEST LOCATION READING

'sssuSSn == sf- -"s **g-TESTS PERFORMED BY

I9II RESCUE SERVICE I N F O R M A T I O NI

_J»PMJ L P P M_PPM

S I G N E D T I M E DATE

• FOR CONTINUOUS OR PERIODIC MONITORING, RECORD R E S U L T S IN W-C HEALTH ANDSAFETY REPORT

R E S P O N D I N G T E A MADDRESSPHONE NUMBERI

• L I S T OF RESCUE E Q U I P M E N T REQUIRED ON SITE

I' C O M M U N I C A T I O N P R O C E D U R E S A N D E Q U I P M E N Ti1 — — — — — — — — — — — —

P E R S O N A L P R O T E C T I V E E Q U I P M E N T REQUIREDL—— ________ _ ______________________________________

I

W o o d w a r d - C l y d e

A P P E N D I X EO S H A 42 AIR M O N I T O R I N G M E T H O D

MCOFORMULA: ^ ; C g H g N ^ ._____________TOLUENE-2.4-OIISOCYANATEM MIOSH METHOD: 2535M . H . : 174.16____________________________________________ISSUED; 8/15/87OSHA: 0.02 ppm ( c e i l i n g ) PROPERTIES: l i q u i d ; HP 19.5-21.5 «C; BP 251 *C;NIOSH: 35 vg/knVlO hrs; 140 p g / m » / 1 0 nrin densi ty 1.2244 g/M. f 20 *C;ACGIH: TIM 0.005 ppm; STEL 0.02 ppm VP ca. 1.3 Pa (0.01 nm Hg ; 0.96(1 ppm = 7.12 mg/w 3 * NTP) mg/m*) « 20 *C

SYNONYMS: 2 , 4 - T O I ; 2,4-bis(carbonylamino)to1uene; CAS *584-84-9.S A M P L I N G M E A S U R E M E N Ti

S A M P L E R : T U B E W I T H R E A G E N T - C O A T E D G L A S S W O O L { T E C H N I Q U E : H P L C , U V D E T E C T I O N( N - [ ( 4 - n i t r o p h e n y l ) m e t h y l ] - !propylamine on glas s woo l) iANALYTE: 3,3 1 -b i s[(4-ni troDheny1)methy1]-! 3 ,3 > -d ipropy l-1 , r-(4- f f l e t hy l-1 ,3-FLOW RATE: 0.2 to 1 L/ s r in ! phenylene) diurea (2,4-TDIU)i•VOL-MIN: 2 L 9 0.14 mg/m« 'RECOVERY: 2 fflL CHJOH; ultrasonic bath, 3 min

-MAX: 170 L !!INJECTION VOLUME: 50 yLSHIPMENT: protect fron l i g h t !{ M O B I L E P H A S E : 55:45 ( v / v ) C H g C f t H j g O with

SAMPLE STABILITY: at least 14 days 9 25 °C [1] ! 0.08X Et3N and 0.16X H 3TO 4;! 1.0 n L / f c i nSTABILITY OF REAGENT ON GLASS WOOL: !< 7 days 9 25 0C; > 4 weeks 9 -21 °C {DETECTOR: UV 9 254 mi

FIELD BLANKS: 10X of samples iCOLUMN: 25 cm x 4.6 m; o c tade cy l s i ly la t ed___________________________ ! s i l i c a , 5-i*i par t i c l e size

!___________ACCURACY__________ {CALIBRATION: standard solutions of 2 ,4-TDIU in

CH30HRANGE STUDIED: 0.039 to 0.53 ng/ffl*[l] !(67-L s a m p l e s ) {RANGE: 0.3 to 25 yg 2,4-TOI per sampleiBIAS: none found [1] {ESTIMATED LOO: 0.1 f ig 2,4-TDI per sample

•O V E R A L L P R E C I S I O N ( s r ) : 0.033 [ 1 ] { P R E C I S I O N ( s r ) : 0.067 [ 1 ]_______________________________________________________________•______________________________________________ __APPLICABILITY: The working range is 0.004 to 0.35 ppm (0.03 to 2.5 m g / t a * ) for a 10-L airsample. T h i s method is a p p l i c a b l e to isocyanate vapors (2,4-TOI vapor, 2,6-TOI vapor, andhexamethylene dii socyanate (KOI) vapor) [ 2 , 3 ] , but not aerosols because of i n e f f i c i e n tc o l l e c t i on of aerosols and incomplete reaction of aerosol isocyanates with reagent._______INTERFERENCES: The reagent i s s l i g h t l y unstable in the dark a t 25 °C. T a i l i n g during HPLC, aresult of reagent deterioration, may raise detection l i m i t s .___________OTHER METHODS: T h i s revises P&CAM 326 [ 4 ] . Sango used s i m i l a r HPLC condit ions [ 5 ] . Melcherreviewed methods for isocyanates [6].__________________________________

8/15/87 2535-1 MIOSH Manual of A n a l y t i c a l Methods

T O L U E N E - 2 . 4 - O I I S O C Y A N A T E METHOD: 2535R E A G E N T S :1. 2,4-TDI* (see APPENDIX A).

2. N - [ ( 4 - n i t r o p h e n y l ) m e t h y l ] -propylaor ine hydrochloride.3. 2 , 4 - T O I U (see APPENDIX B).4. Methanol , chronatographic quality.5. C a l i b r a t i o n stock solut ion,

10 mg/mL. Dis so lve 50 ng2.4-TDIU in methanol to make 5 mlsolut ion.6. Mater, d i s t i l l e d .7. NaOH. 1 M.8. T o l u e n e , reagent grade.9. Dichloromethane, reagent grade.10. Hexane, reagent grade.*11. N i t r o g e n , p u r i f i e d , compressed.12. M o b i l e phase. Mix 0.8 mLtriethylamine and 1.6 mL

with 1 L 55:45H20 (v/v).*13. Oibutylamine, 99X pure.14. Tetrahydro furan , reagent grade.*15. Branocresol p u r p l e indicatorsolution.

16. HC1, 0.05 M, standardized.17. 2,4-TDI stock solution.100 mg/mL. Dissolve 500 ng2,4-TDI in dichloromethme tomake 5 mL solution.*See S P E C I A L P R E C A U T I O N S .

E Q U I P M E N T :1. Sampl er: g l a s s tube, 4 cm x 6 nm ID, containingtwo sections of reagent-coated glass wool (seeAPPENDIX C); front section, 7 mm long; backsection, 5 mm long. Reagent-coated glas s wool iscompressed t i g h t l y . Seal ends of sampler withp l a s t i c caps. Wrap midsection of sampler withblack tape. Protect sampler from l i g h t . S a m p l e rmay be stored at -21 °C in the dark for at leastfour weeks. Limi t period of storage of sampler at25 °C in the dark to seven days.2. Separatory f u n n e l s , 125-mL.3. Beakers, 50- and 125-mL.4. Aluminum f o i l .5. Glas s wool, s i lanized.6. G l a s s rod, 15 on x 4 nm.7. Tweezers.8. Glas s tube with right-angle bend, 4.5 cm x 6 HUD ID,wrapped with black tape.9. Rubber tub ing, opaque 1.5 cm x ca. 8 am ID.10. Personal s a m p l i n g pump, 0.2 to 1 L / m i n , withf l e x i b l e connecting tubing.11. High pressure l i q u i d chromatograph, 254-nm UVdetector, integrator, and column (page 2535-1).12. V i a l s , g la s s , 2-mL, caps l ined with PTFE.13. P i p e t s . 2-, 15-, and 25-mL.14. Ultrasonic bath.15. Syringe s , 100-jiL, readable to 1 pL.16. Syringes , 10-yL, readable to 0.1 j i L .17. Volumetric f l a s k s , 5-mL.18. Buret, 50-mL.19. U-tube, g la s s , 25 on x 15 HI ID, glass stopcocks.

20. Sorbent tube, glass, 7 cm x 6 mw, coconutsh e l l charcoal, ca. 150 mg.

SPECIAL PRECAUTIONS: 2,4-TOI can irri tate the eyes and sk in, and can cause bronchial asthmaand a l l e r g i c eczema. F l a s h po in t s of hexane, te trahydrofuran and tr ie thylamine are -26 *C, -17° C , a n d - 6 ° C , respectively.

S A M P L I N G :1. C a l i b r a t e each personal s a m p l i n g pump wi th a representative sampler in line.2. Remove p l a s t i c caps from sampler. Attach one end of g la s s tube wi th right-angle benddire c t ly to inlet of sampler with short piece of opaque rubber tubing.3. S a m p l e 2 to 170 L of air at 0.2 to 1 L / m i n . Seal ends of sampler wi th p l a s t i c caps.S A M P L E P R E P A R A T I O N :4. T r a n s f e r f ront and back sections of reagent-coated g la s s wool to separate v ia l s ,

methanol. Seal vials .5. Place vial s into ultrasonic bath for 3 min.

Add 2mL

8/15/87 2535-2 MIOSH Manual of Analy t i ca l Methods

IIIIIIIIIIIIIIIIIII

METHOD; 2535 _______________________________________ T O L U E N E - 2 . 4-0 I ISOCYANATEC A L I B R A T I O N A N D Q U A L I T Y C O N T R O L :

6. Cal i b ra t e d a i l y with at least f i v e working standards over the range 0.3 to 80 pg 2,4-TOIUper sanple (equivalent to 0.1 to 25 jig 2,4-TDI per sample).a. Prepare a series of standard solutions of 2,4-TOIU in methanol over the range of 0. 15 to

40 tig/M..b. Analyze together with samples and blanks ( s t ep s 8 and 9).c. Prepare cal ibration graph (peak area vs. yg 2 , 4 - T O I U ) .7. Determine recoveries from samplers in the range 0.3 to 25 tig 2,4-TDI per sample. Preparethree samples at each of three level s p l u s three media blanks.NOTE: Recoveries should be quantitative. If recoveries are not quantitative, attempt todetermine the reason for error.a. Prepare a series of standard solutions of 2,4-TDI in dicnlorometnane in the range 0.06to 5 m g / m L .b. Connect a U-tube to the inlet of a sampler with a short piece of tubing.NOTE: The length of tubing should be minimal to prevent losses of TOI by adsorption orreaction on the inside wal l of the tubing.c. Connect charcoal soroent tube to inlet of U-tube (charcoal can adsorb contaminants ofair which would react with 2 , 4 - T D I ) .d. Draw ambient air through the charcoal tube, U-tube, and sampler with a sampl ing pump at1 L/min.e. Place 5 iiL of a standard solution of 2,4-TDI into the U-tube.f. A l l o w operation of the pump to continue for 20 min.g. Analyze the sampler for 2,4-TOIU (steps 6 and 7 and 10 through 12).

M E A S U R E M E N T :8. Es tab l i s h chromatographic conditions indicated on page 2535-1.9. I n j e c t sample aliquot manually or with autosampler. Measure peak area.C A L C U L A T I O N S :10. Determine the mass d ig) of 2,4-TOIU found on the sample front (Mf) and back

sections and in the average media blank front (Bf ) and back (85) sections.NOTE: If % > H f / 1 0 . report breakthrough and possible sample loss.11. Calcu la t e concentration, C, of 2,4-TDI in the air volume sampled, V (L):

where 0.310 = M.W. of 2 , 4 - T D I / R . H . of 2,4-TOIU.EVALUATION OF METHOD:A variation of th i s method which involved normal-phase HPLC (Method P&CAN 326} was tested withf o r t i f i e d samplers and atmospheres generated with a d i f f u s i o n cell [1 ,4]. Average recoveriesof 2,4-TOIU from front sections of reagent-coated glass wool were 0.97 to 0.99 af t era p p l i c a t i o n s of 1.0-, 2.1-, 9.9-, and 20.0-pg quantities of 2,4-TDI from a U-tube; sr was0.067 (21 sample s , p o o l e d ) . sr was 0.033 (29 samples , p o o l e d ) for 67-L samples at 0.039 to0.53 mg/m*. The independent method used for evaluation was that of M e d d l e and Wood [ 7 ] .Average concentrations ranged from 0.054 to 0.46 mg/m* by the independent method £1}.Conclusive evidence for bias in the reagent-coated glass wool method was not found.Breakthrough volume was 71 L (0.53 mg/m*. 1 L / m i n ) ; breakthrough volume was 279 L (0.14m g / m s , 1 L / m i n ) . 2 ,4-TOIU was s table on coated glass wool at room temperature in the darkfor 14 days. The reagent, N - [ ( 4 - n i t r o p h e n y l ) m e t h y 1 ] p r o p y l a m i n e , is unstable [ 1 ] .

8/15/87 2535-3 NIOSH Manual of A n a l y t i c a l Methods

T O L U E N E - 2 . 4 - 0 1 I S O C Y A N A T E METHOD: 2S3SEvaluation of samplers with 2,4-TDI aerosols was not performed. However, samplers werei n e f f i c i e n t col lectors when aerosol par t i c l e s were present in an atmosphere of4 , 4 > - f f l e t h y l e n e d i p h e n y l i s o c y a n a t e (HOI). The co l l ec t ion e f f i c i e n c y of each sampler for HDI wasabout 90* ( f l o w rate, 1 L / n i n ; total concentration of HOI in vapor and aerosol forms, about0.52 mg/ra*; mass median diameter of HOI p a r t i c l e s , about 0.6 JJTO; geometric standarddeviation, about 2.2) [ 1 ] .R E F E R E N C E S :[1] Tucker, S. P., and J. E. Arnold. A n a l . Chem.. 54, 1137-1141 (1982).[2] Swinehart. G., K. M u l l i g a n , C. Rice, R. HcKay, N. Gener, and G. E. Burroughs."Hexamethylene Oiisocyanate Honomer and Prepolymer Characterization," presented at theAmerican I n d u s t r i a l Hygiene Conference, D a l l a s , TX (Hay 20, 1986).[3] Carson, K. A. "Isocyanate Monitor ing U s i n g M-p-nitrobenzyl-N-propylamine glass f i b ers a m p l i n g tube," OEHL-82-022EH163HAE, Air Force Occupational Environmental H e a l t hLaboratory, Brooks AFB. TX (1982); report (No. AO-A119901) available from NTIS,

S p r i n g f i e l d , VA 22161.[4] NIOSH Manual of Analyt i ca l Methods, 2nd ed., V o l . 6, P&CAH 326, U.S. Department of H e a l t hand Human Services. Publ. (NIOSH) 80-125 (1980).[5] Sango, C. J. Lig. Chromatogr.. 2, 763-774 (1979).

[6] Melcher, R. G. Anal. Chem.. 55,~40R-56R (1983).[7] M e d d l e , 0. U., and R. Wood. Analyst (London). 95, 402-407 (1970).[8] H a s t i n g s Vogt. C. R., C. Y. Ko and T. R. Ryan. J. Chroroatoqr.. 134. 451-458 (1977).METHOD REVISED BY: Samuel P. Tucker, Ph.D., NIOSH/DPSE.

APPENDIX A: Determination of Purity of 2,4-TDIDissolve 480 yL (365 mg. 0.00282 mole) dibutylamine in 10 mL tetrahydrofuran. Add 100 jiL(122 mg, 0.000701 mole) 2,4-TOI. S t i r the mixture and al low to stand 6 min. Add a few drops,of bromocresol p u r p l e indicator solution. Prepare two addi t ional samples in this manner.T i t r a t e excess d ibu ty lamine with 0.05 H HC1. Cal cu la t e percent puri ty, P, of 2,4-TDI for eachsample:

P = <B-= 5> • 100.where: B = Molar quant i ty of d i bu ty lan ine before reaction (0.00282)

V = Volume of 0.05 H HC1 (L)M = Concentration of HC1 (0.05M)2 = Number of moles of d i bu ty lamine required to react with 1 mole of 2,4-TDIH = Molar quantity of 2,4-TDI added to tetrahydrofuran solution (0.000701)

APPENDIX B: Preparation of 2 ,4-TDIU [8]Disso lve 1.03 g (0.00446 mol e) N-[(4-ni t ropheny1)methy1]-propylamine hydrochloride in 25 mlwater in a 125-mL separator? f u n n e l . Add 15 mL 1 M NaOH and shake the mixture. Extract thef * - C ( 4 - n i t r o p h e n y T ) m e t h y l ] p r o p y 1 a m i n e with 50 mL toluene, and separate the phases. Add as o lu t i on of 262 til- (321 mg, 0.00184 mole) 2,4-TDI in 30 mL toluene to the so lut ion ofN - [ ( 4 - n i t r o p h e n y l ) m e t h y l ] p r o p y l a m i n e . C o l l e c t the p r e c i p i t a t e by f i l t r a t i o n . P u r i f y theproduct by d i s s o l v i n g it in a smal l volume of dichloromethane and p r e c i p i t a t i n g it withhexane. Dry the product rn vacua (MP = 136 to 139 °C).8/15/87 2535-4 M10SH Manual of Analyt i ca l H e t f w d s

IIIIIIIIIIIIIIIIIII

METHOD: 2535______________________________________TOLUEME-2.4-OIISOCY/WATEAPPENDIX C: Preparation of Reagent-Coated Gla s s WoolDissolve 300 ng (0.00130 mol e) R - C ( 4 - n i t r o p h e n y l ) n e t h y l ] p r o p y l a m i n e hydrochloride in 25 nLwater in a 125-mL separatory f u n n e l . Add 15 nL 1 « NaOH and shake the mixture. Extract theN - [ ( 4 - n i t r o p h e n y l ) m e t h y l ] p r o p y 1 a m i n e with 50 mL hexane. Trans f e r 40 aL of the hexane solut ionto a 50-fliL beaker which is wrapped with aluminum f o i l and contains 1.82 g s i lanized glas swool. Under .dim l i g h t , evaporate hexane from the beaker with the aid of a stream of nitrogen.Knead the glas s wool with a glas s rod to produce a un i f orm coating. Continue to evaporatehexane until the glas s wool appears dry. Protect the coated glas s wool from bright l i g h t . Thequantity of coated glass wool is s u f f i c i e n t for the preparation of the front and back sectionsfor twenty samplers.

8/15/87 2535-5 KIOSK Manual of A n a l y t i c a l Methods

W o o d w a r d - C l y d e

A P P E N D I X FNIOSH 2535 AIR MONITORING M E T H O D

D I I S O C Y A N A T E S1 , 6 - H E X A M E T H Y L E N E D T T S O C Y A N A T E ( H O T )

T O L U E N E - 2 , 6 - D I I S O C Y A N A T E ( 2 , 6 - T D I )T O L U E N E - 2 , 4 - D I I S O C Y A N A T E ( 2 , 4 - T D I )

M e t h o d no.: 42

M a t r i x :

Procedure:

A i r

S a m p l e s are c o l l e c t e d by drawing a known vol-ume o f a ir through glas s f i b e r f i l t e r s coatedw i t h 0.1 mg of l - ( 2 - p y r i d y l ) p i p e r a z i n e ( 1 - 2 P P )which are contained in o p e n - f a c e c a s s e t t e s .S a m p l e s a r e e x t rac t ed w i t h 90/10 ( v / v ) aceto-n i t r i l e / d i m e t h y l s u l f o x i d e ( A C N / D M S O ) a n d ana-lyzed by high p e r f o r m a n c e l i q u i d chromato-graphy (HPLC) using an u l t r a v i o l e t or f l u o -rescence d e t e c t o r . ( T h e coated f i l t e r s usedin M e t h o d 47 for MDI are also a c c e p t a b l e fort h i s procedure . T h o s e f i l t e r s a r e coated w i t h1 mg ins tead of 0.1 mg of 1 - 2 P P . )

Recommended air volumeand s a m p l i n g rate: 15 L at 1 L / m i n

S p e c i a l requirements: I t i s recommended that coated g la s s f i b e r f i l -ters be stored at reduced t e m p e r a t u r e un t i lused f or s a m p l i n g .

S t a t u s o f me thod: E v a l u a t e d m e t h o d . T h i s method has been sub-j e c t e d to the e s t a b l i s h e d eva lua t i on proce-dures o f the Organic M e t h o d s Eva lua t i onBranch.

Date: F e b r u a r y 1983March 1989 ( R e v i s e d ) C h e m i s t : Donald Burright

Carcinogen and P e s t i c i d e BranchO S H A A n a l y t i c a l Labora toryS a l t Lake C i t y , U t a h

Analyte_______________________2,6-TDI____HDI_____2,4-TDIT a r g e t c oncen tra t i on , u g / m 3 ( p p b ) : 140(20) 140(20) 1 4 0 H 2 0 )D e t e c t i o n l i m i t o f t h eoverall proc edure , u g / m 3 ( p p b ) : 1 . 6 ( 0 . 2 3 ) 2 . 3 ( 0 . 3 2 ) 1 . 3 ( 0 . 1 7 )Rel iab l e q u a n t i t a t i o nl i m i t , u g / m 3 ( p p b ) : 2 . 3 ( 0 . 3 2 ) 2 . 9 ( 0 . 4 3 ) 2 . 5 ( 0 . 3 6 )S t a n d a r d error o f e s t i m a t eat targe t c onc en tra t i on , %: 7.63 7.79 6.89( S e c t i o n 4 .9 .)'OSHA PEL ( A i r c oncentra t ions are based on 15-L air s a m p l e v o l u m e . )

1. General Discussion1.1. Background

1.1.1. H i s t o r ySome of the earl i e s t procedure s to d e t e rmine a t m o s p h e r i cd i i s o c y a n a t e concentrat ions were deve l oped by Ranta andM a r c a l i ( R e f . 5.1.). Both of these procedures are incon-venient because they use a bubb l er for s a m p l i n g and the irc o l or ime t r i c analyses are n o n - s p e c i f i c . A la t e r s a m p l i n gprocedure uses p - n i t r o b e n z y l - N - n - p r o p y l a m i n e ( n i t r o rea-g e n t ) in toluene bubblers ( R e f . 5 .2 .). W h i l e t h i s methodi s s p e c i f i c f or d i i s o c y a n a t e s , i t s t i l l r e ta ins the u s e o fthe bubbler and n i t r o reagent which is un s tab l e when stor-ed for long p e r i o d s of t ime , even if it is kep t at reducedt empera ture . The pas t c o u p l e of years have seen severalnew d e r i v a t i z i n g reagents being used; they in c lude N - m e t h -yl-1-naphthalenemethylamine ( R e f . 5 . 3 . ) , 9-(n-methylamino-methy1)-anthracene ( R e f . 5 .4 .) and l - ( 2 - p y r i d y l ) p i p e r a z i n e( 1 - 2 P P ) ( R e f s . 5.5.-5.7.). T h e c o l l e c t i o n procedure o fthese new s t u d i e s all involve the use of to luene bubblers .The purpo s e of th i s s t u d y was to f i n d a c o l l e c t i o n systemthat does not use a bubb l er , yet retains the s e n s i t i v i t y ,p r e c i s i o n and accuracy of the n i t r o reagent me thod .1-2PP is a s u i tab l e d e r i v a t i z i n g reagent, when coated on aglas s f i b e r f i l t e r , f o r several reasons:1) The high b o i l i n g l i q u i d is r e ta ined on a glas s f i b e rf i l t e r and s t a b i l i t y is not a prob l em.2) The r a p i d and exo thermic reac t ion v i t h bo th aromat i c

and a l i p h a t i c d i i s o c y a n a t e s r e s u l t s in d e r i v a t i z a t i o non the f i l t e r ( R e f . 5 .7 .).42-1

3) The der ivat ive s have higher molar a b s o r p t i v i t i e s in theUV region than those formed w i t h n i t r o reagent whichallows the e x t ra c t i on volume to be larger wi thou t loss- of s e n s i t i v i t y ( R e f . 5.5.).T h i s procedure compares favorably when tested side-by-sidewi th the n i tro reagent method by Cummins ( R e f . 5.10.) for2 , 4 - T D I . { S e c t i o n 4.10.) A d d i t i o n a l work is being done tos t u d y 4 , 4 ' - m e t h y l e n e d i p h e n y l i s o c y a n a t e and isophorone di-i socyanate using 1-2PP as the d e r i v a t i z i n g reagent.A d d i t i o n a l work was p e r f o r m e d on th i s procedure to r e f l e c tto change in T i t l e 29 CFR 1910.1000, T a b l e Z-l-A in 1989.The C e i l i n g PEL of 0.14 m g / m 3 for 2 , 4 - T D I was replacedwith an 8-h TWA PEL of 0.04 m g / m 3 . The s a m p l i n g time canbe increased to 240 min at a sampl ing rate of 1 L / m i n .( S e c t i o n s 4.6. and 4.12.)

1.1.2. T o x i c e f f e c t s ( T h i s s ec t ion i s for i n f o r m a t i o n only andshould not be taken as a basis for OSHA p o l i c y . )Continued inha la t i on of d i i s o cyanat e vapors or mi s t s cancause nausea, headache, coughing, i r r i t a t i o n of the noseand t h r o a t , shortness of breath and chest d i s c o m f o r t .Massive exposure can cause severe coughing spasms, bron-chi t i s and chemical p n e u m o n i t i s . Some p e o p l e can becomes ens i t ized to isocyanates and may s u f f e r a s t h m a t i c a t tacksand re sp ira tory d i s t r e s s when subsequently exposed to verylow concentrations ( R e f . 5.9.). Recent s t ud i e s have pro-duced c o n f l i c t i n g result s about the mutageni c i ty of TDI( R e f s . 5.1. and 5.9.). No data has been found to ind i ca t ethat di i socyanates are carcinogenic or teratogenic ( R e f s .5.1. and 5.9.).

1.1.3. Operations where exposure may occurThe manufacture of polyurethane f o a m s , coatings, and elas-tomers p o t e n t i a l l y exposes a minimum of 100,000 workers tod i i s o cyanat e s ( R e f . 5 .2.). Diisocyanates can be f o u n d inp a i n t s , i n s u l a t i o n , adhesives, automobi l e bumpers, shoesoles, and hundreds of other a p p l i c a t i o n s ( R e f s . 5.2. and5.8.). Over 700 mi l l i on pounds of diisocyanates wereproduced in 1975 { R e f . 5 .2 .).

1.1.4. Physi ca l p r o p e r t i e sanaly t eCAS no. :M t f :b p , ° C ( m m H g ) :m p , ° C :s p g r ( 7 5 ° C ) :vp, mm Hg:

2 , 6 - T D I91-08-7174.169 6 ( 1 . 5 )8N A 1

N A 1

HDI822-06-0168.20213(760)-55

1.050.05

2 , 4 - T D I584-84-9174.162 5 1 ( 7 6 0 )22

1.220.025

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IIIIIIIIIIIIIIIIIII

color: all co lor l e s s to p a l e ye l lowodor: all sharp pungentf l a s h p o i n t ( c l o s e dc u p ) , ° C : N A 1 1 4 0 1 2 7synonyms ands t ruc ture s : F i g u r e 1.1.4.' n o t a v a i l a b l e

1.2. L i m i t d e f i n i n g parameter s ( t h e a n a l y t e a i r c onc en tra t i on s l i s t e dthrough th i s method are based on an air volume of 15 L and ane x t ra c t i on volume of 2 m L . )1.2.1. D e t e c t i o n l i m i t o f the ana ly t i ca l procedure

The d e t e c t i o n l i m i t o f th e a n a l y t i c a l procedure i s th emass of ana ly t e per i n j e c t i o n which wi l l result in a peakwhose he ight is about 5 t imes the a m p l i t u d e of the base--• • line noise. ( S e c t i o n 4.1.)

A n a l y t i c a l D e t e c t i o n L i m i tanalyte_____2,6-TDI HDI 2 , 4 - T D In g / i n j e c t i o n 0.18 0.18 0.18

1.2.2. D e t e c t i o n l i m i t of the overall procedureThe d e t e c t i o n l i m i t o f the overall procedure i s the amountof analyte spiked on the s a m p l i n g device which allows re-covery of an amount of ana ly t e equivalent to the d e t e c t i o nl i m i t o f t h e ana ly t i ca l procedure . ( S e c t i o n 4.2.)

D e t e c t i o n L i m i tof the Overall Procedureanaly t en g / s a m p l eu g / m 3

p p b

2 , 6 - T D I- 241.60.23

H D I33

2.30.32

2 , 4 - T D I191.30.17

1.2.3. Rel iab l e q u a n t i t a t i o n l i m i t sThe re l iable q u a n t i t a t i o n l i m i t i s the smal le s t amount ofanalyt e which can be q u a n t i t a t e d w i t h i n the requirementsof at least 75% recovery and a pr e c i s i on (1.96 SD) of ±25%or b e t t e r . The r e l i ab l e q u a n t i t a t i o n l i m i t s are higherthan the d e t e c t i o n l i m i t s o f the overall procedure tos a t i s f y t h e p r e c i s i o n requirement. ( S e c t i o n 4 .3 .)

42-3

Reliable Quant i t a t i on Limit sanalyt eng/ s ampl eu g / m 3

p p b

2 , 6 - T D I34

2.30.32

HDI44

2.90.43

2 , 4 - T D I39

2.50.36

*

The reliable q u a n t i t a t i o n l imi t and d e t e c t i on l i m i t s reported inthe method are based upon o p t i m i z a t i o n of the instrument for thesmalle s t p o s s i b l e amount of analyte. When the target concentra-tion of an analyte is e x c e p t i o n a l l y higher than these l i m i t s , theymay not be a t t a i n a b l e at the routine o p e r a t i n g parameters._____

IIIII1.2.4. S e n s i t i v i t y

The s e n s i t i v i t y of the analyt ical procedure is determinedby the s l op e of the ca l i b ra t i on curve over a concentrationrange 0.5 to 2 times the target concentration. The sensi-t i v i t y will vary somewhat w i t h the p a r t i c u l a r instrumentused in the analysis. ( S e c t i o n 4.5.)S e n s i t i v i t yof the A n a l y t i c a l Procedure

analytearea unit sper ug/mL

2 , 6 - T D I HDI 2,4-TDI

85600 84300 159000

1.2.5. RecoveryThe recoveries of the analytes f r o m samples used in the18-day storage t e s t s remained above the values pre s entedbelow. These values are determined f r o m the calculatedregression lines of the s torage graphs. ( S e c t i o n 4.9.)The recovery of analyte f r o m the c o l l e c t i on medium a f t e rstorage must be 75% or greater.

Recovery, %t e m p , ° C

-2522

2 , 6 - T D I86.386.4

HDI81.183.0

2 , 4 - T D I81.380.3

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IIIIIIIIIIII

1.2.6. Prec i s i on ( a n a l y t i c a l m e t h o d )The pooled c o e f f i c i e n t s o f variation obtained f r o m r ep l i -cate d e t e r m i n a t i o n s of ana ly t i ca l s t a n d a r d s at 0.5, 1 and2 t imes the targe t c onc en t ra t i on are pr e s en t ed below.( S e c t i o n 4.4.)

Pool ed C o e f f i c i e n t s o f V a r i a t i o n2,6-TDI________HDI________2,4-TDI

0.009 0.013 0.009

1.2.7. Prec i s i on (overa l l p r o c e d u r e )The overall procedure must p r o v i d e r e s u l t s at the targe tconcentrat ions that are ±25% or b e t t e r at the 95% c o n f i -dence level. The preci s ions at the 95% c o n f i d e n c e levelfor the 18-day s torage te s t are p r e s e n t e d below. ( S e c t i o n4.9.) The r e p o r t e d values each inc lude an a d d i t i o n a l ±5%f or s a m p l i n g error.

Preci s ion at the 95% C o n f i d e n c e L e v e l , %2 , 6 - T D I H D I 2 , 4 - T D I

14.9 15.2 13.5

1.2.8. R e p r o d u c i b i l i t yF i v e s a m p l e s , p r e p a r e d by vapor s p i k i n g , and a d r a f t copyof t h i s procedure were given to a chemist unassoc iatedw i t h th i s evaluat ion. The sample s were analyzed a f t e r 6days o f s torage at -25°C. The d a t a l i s t e d below are cor-rected f o r e x t r a c t i o n e f f i c i e n c y ( S e c t i o n 4.8.).

Recovery %

XS D

2 , 6 - T D I101.5

1.6

H D I100.4

2.0

2 , 4 - T D I105.4

2.4

1.3. A d v a n t a g e s1.3.1. The s a m p l i n g and a n a l y t i c a l procedures are s p e c i f i c ands ens i t ive for several d i i s o c y a n a t e s employed in i n d u s t r y( R e f . 5 .7.).1.3.2. The c o l l e c t i o n sy s t em is less cumbersome than the use of abubbler.

42-5

1.3.3. 1-2PP is more s t ab l e and less expensive than p-nitroben-z y l - N - n - p r o p y l a m i n e ( n i t r o reagent).

1.4. DisadvantagesThe use of peak rat io s to c o n f i r m low concentrat ions of d i i s o cy-anates is imprac t i ca l due to the small response at 313 nm.

2. S a m p l i n g Procedure2.1. A p p a r a t u s

2.1.1. S a m p l e s are co l l e c t ed by use of a personal s a m p l i n g p u m pthat can be calibrated to within ±5% at the recommendedf l o w rate wi th the sampl ing device in line.2.1.2. A three-piece styrene cas se t t e containing a glass f i b e rf i l t e r coated wi th 0.1 mg of 1-2PP and a backup pad. ( F i g -ure 2.1.2.)2.1.3. Coated f i l t e r s are prepared by a p p l y i n g 0.5 mL of a solu-t ion of 0.2 mg/mL 1-2PP in methylene chloride to each

glass f i b e r f i l t e r . The wet f i l t e r s are allowed to airdry b e f or e p l a c i n g them in a j a r . Vacuum is a p p l i e d tothe jar to remove residual methylene chloride. ( T h e coat-ed f i l t e r s used in Method 47 for MDI are also a c c e p t a b l efor this procedure. These f i l t e r s are coated with 1 mg of1-2FP and are prepared as above except a 2.0 m g / m L solu-tion of 1-2PP in methylene chloride is u sed.)

2.1.4. Coated f i l t e r s should be stored at reduced temperature asa precaution.2.2. Reagents

None required.2.3. S a m p l i n g technique

2.3.1. Remove the inlet cover f r o m the three-piece ca s s e t t e .Save th e cover for i n s t a l l a t i o n a f t e r s a m p l i n g .

2.3.2. A t t a c h the ca s s e t t e in the brea th ing zone of the employeeto be monitored.2.3.3. The recommended f l o w rate is 1 L / m i n w i t h a recommended

t o t a l air volume of 15 L. A longer 240-min sampl ing timeis p ermi s s i b l e to comply w i t h the 1989 change of the PEL.

2.3.4. A f t e r s a m p l i n g for the a p p r o p r i a t e time, remove the sam-p l i n g device and r e in s ta l l the small p l u g and inlet cover.2.3.5. W r a p each sampl e end-to-end wi th an OSHA F o r m 21 seal.

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IIIIIIIIIIIIIIIIIII

2.3.6. W i t h each set of s a m p l e s , submit at least one blank sam-p l e . The b l a n k s h o u l d be s u b j e c t e d to the same h a n d l i n gas the s ampl e s e x c ep t that no air is drawn through it.

2.3.7. Bulk s a m p l e s s u b m i t t e d for ana ly s i s must be s h i p p e d insealed vials and in a s e p a r a t e container.

2.4. R e t e n t i o n e f f i c i e n c y2.4.1. E x p e r i m e n t a l d e s i g n

Due to pre s ent l a b o r a t o r y l i m i t a t i o n s , c o n t r o l l e d t e s ta t m o s p h e r e s of d i i s o c y a n a t e s cannot e f f e c t i v e l y be gen-era t ed . However , the f o l l o w i n g pro c edure using a vapors p i k i n g t e chnique was used as an a l t e r n a t i v e to s t u d ya n a l y t e r e t e n t i o n . T h i s was done to a p p r o x i m a t e the rec-ommended o p e n - f a c e c o l l e c t i o n o f d i i s o c y a n a t e s .A g la s s syringe barrel e q u i p p e d w i t h a Luer t a p e r t ip wass i l an i z ed and s i l a n i z e d g la s s wool was p l a c e d i n t o thesyringe. The Luer t ip was inser ted in t o the in l e t par t o fa c a s s e t t e so that the tip was f l u s h w i t h the in s ide sur-f a c e of the ca s s e t t e . The o ther end of the syringe wasattached to a s a m p l i n g por t . The o u t l e t of the cas s e t t ewas a t t a c h e d to a vacuum p u m p . A c r i t i c a l o r i f i c e betweenthe c a s s e t t e and the p u m p maintained a constant 1 L / m i n

. . . ... - f l o w rate.Dry air s a m p l e s were p r e p a r e d by a t t a c h i n g a dry airsource to a m a n i f o l d i n l e t . H u m i d air s ampl e s were gen-erated by p a s s i n g air through water in a c o n t r o l l e d tem-perature water bath. The h u m i d i t y was monitored in thes a m p l i n g m a n i f o l d v ia a h u m i d i t y probe. The g la s s woolwas s p i k e d w i t h d i i s o c y a n a t e in me thy l ene c h l o r i d e . The.,. , des ired q u a n t i t y of air was then drawn through the g la s swool , at a f l o w rate of 1 L / m i n , and onto the coated f i l -t er , which was analyzed to d e t e rmine ana ly t e loss.

2.4.2. R e t e n t i o n r e s u l t sH u m i d i t y a f f e c t s t h e a b i l i t y o f a g las s f i b e r f i l t e r t ore tain d er iva t i z ed d i i s o c y a n a t e s . When a s a m p l e ten t imesthe targe t c o n c e n t r a t i o n is vapor generated and 200 L ofdry air (12% h u m i d i t y ) is drawn through the f i l t e r , anaverage of 95.4% of the d i i s o c y a n a t e s is f o u n d on thecoated f i l t e r . Only 1.2% is f o u n d on the backup pad .When higher r e la t iv e h u m i d i t y ( R . H . ) i s added to the samp-l i n g s y s t e m , a d i f f e r e n t re sul t i s o b t a i n e d . A f t e r samp-les were vapor s p i k e d at the targe t c onc en tra t i on us ing 20L of dry air, several known volumes of humid air (78%R . H . ) p u l l e d through them. T h e s a m p l e s showed increas inglo s s e s o f d i i s o c y a n a t e d e r i v a t i v e w i t h increasing volumeso f humid air. ( S e c t i o n 4 . 6 . )

42-7

2.5. E x t r a c t i o n e f f i c i e n c yThe average ex trac t i on e f f i c i e n c y for each of the analyte s sp ikedat the target concentration on a coated glass f i b e r f i l t e r ispresented below. ( S e c t i o n 4.7.)

Average Ex t ra c t i on E f f i c i e n c i e s , %2,6-TDI_______HDI_______2,4-TDI

91.2 93.3 90.8

2.6. Recommended air volume and s a m p l i n g rate2.6.1. The recommended air volume is 15 L for the OSHA C e i l i n gPEL.2.6.2. The recommended air s a m p l i n g rate is 1 L / m i n .2.6.3. To comply wi th the 1989 PEL changes, the air volume can be

increased to 240 L to sample for the OSHA T V A - P E L .2.7. I n t e r f e r e n c e s ( s a m p l i n g )

Any compound, that could be c o l l e c t e d on the glass f i b e r f i l t e rthat could react wi th the 1-2PP or compete wi th it in the reactionto der ivat ize the d i i s o cyana t e , should be considered as an inter-ference. P o t e n t i a l in t e r f e r enc e s include anhydride s , amines,alcohol s and carboxylic acids.2.8. S a f e t y precautions ( s a m p l i n g )

The s a m p l i n g equipment should be a t tached to the worker in such amanner that it will not i n t e r f e r e wi th work per formance or s a f e t y .3. A n a l y t i c a l Procedure

3.1. A p p a r a t u s3.1.1. H i g h p e r f o rmanc e l i q u i d c h r o m a t o g r a p h e q u i p p e d w i th UVde t e c t or , manual or automatic sample i n j e c t o r , and chartrecorder.3.1.2. HPLC s ta in l e s s steel column capable of s e p a r a t i n g dii so-cyanate derivat ives . The column employed in thi s s t u d ywas a 25-cm x 4.6-mm i.d. All tech Cg (10 urn) s ta in l e s ssteel column.3.1.3. An electronic i n t e g r a t o r , or some other su i tab l e method ofd e t e rmin ing peak areas.3.1.4. V i a l s , 4-mL with T e f l o n - l i n e d caps.

42-8

3.1.5. Syringe s , of convenient sizes for sample and s tandardp r e p a r a t i o n s and i n j e c t i o n s .

3.1.6. V o l u m e t r i c p i p e t t e s and f l a s k s f o r p r e p a r a t i o n o f stan-dards .

3.1.7. S u i t a b l e glassware for p r e p a r a t i o n o f d i i s o cyanat e ureaderivat ive s .

3.1.8. Micro-analyt i ca l balance used to weigh s tandard prepara-tions.

3.2. Reagents3.2.1. M e t h y l e n e c h l o r i d e , hexane, a c e t o n i t r i l e , and d i m e t h y l

s u l f o x i d e , H P L C grade.3.2.2. V a t e r , HPLC grade. Our laboratory employs a commercially

avai lab l e water f i l t r a t i o n sys t em f o r t h e p r e p a r a t i o n o fHPLC grade water.

3.2.3. l - ( 2 - P y r i d y l ) p i p e r a z i n e , A l d r i c h , Milwauke e , V I .3.2.4. 2 , 6 - T D I , C a r b o l a b s , I n c . , N e w Haven, C T .3.2.5. H D I , A l d r i c h , Milwaukee , W I .3.2.6. 2 , 4 - T D I , Eastman Chemica l s , Rochester, N Y .3.2.7. Ammonium a c e ta t e , HPLC grade.3.2.8. G l a c i a l acetic acid.

3.3. S t a n d a r d p r e p a r a t i o n3.3.1. A so lu t i on containing 3.5 g of 2 , 4 - T D I in 25 mL of meth-ylene ch lor id e is s l owly added to a s t i rred s o l u t i o n of

7.25 g of 1-2PP in 100 mL of methylene chloride. The sol-ution is then heated to 35°C for 10 min. Reduce the vol-ume of me thyl ene ch l o r id e to about 10 mL w i t h a stream ofdry n i t rogen. The produc t i s p r e c i p i t a t e d w i t h hexane,( p r e c i p i t a t i o n may s tart wi thout adding hexane), f i l t e r e d ,redi s so lved in a minimal volume of methylene c h l o r i d e andr e p r e c i p i t a t e d . The p r e c i p i t a t e i s f i l t e r e d and washedw i t h hexane ( a p p r o x i m a t e y i e ld is 9 g of the d e r i v a t i v ea f t e r being dried by vacuum). T h i s p r e p a r a t i o n is a modi-f i c a t i o n of the procedure r epor t ed by G o l d b e r g et al ( R e f .5 .7 .). Derivat ive s of the two other d i i s o cyana t e s areprepared by a s imi lar procedure.

3.3.2. P r e p a r a t i o n of working range s tandard sA s t o ck s tandard s o l u t i o n is p r e p a r e d by d i s s o l v i n g thedii socyanate derivat ive s into D M S O . To express the deriv-

42-9

TDI 174.16.«•» ~ ~ — .- f\t^^^7^^MW urea 500.61

MV HDI 168.20 n , / n nTTT=—————— = Tn~i—TT" = O . J 4 U UMV urea 494.64

dards.

42-10

Iative as f r e e d i i s o c y a n a t e , the amount of 2 ,4-TDI and •2 , 6 - T D I ureas weighed is m u l t i p l i e d by the conversion Vf a c t o r 0.3479.

IS i m i l a r l y , the conversion f a c t o r for HDI urea is 0.3400. •

IAll d i l u t i o n s of the stock so lu t ions are made v i th aceto-n i t r i l e to arrive at the working range. <m3.4. S a m p l e pr epara t i on

3.4.1. The styrene cas s e t t e is opened and the glass f i b e r f i l t e r •is placed into a 4-mL vial so that the f i l t e r is f l a t •against the ins ide sur face of the vial, not f o l d e d orcrumpled. •3.4.2. Two m i l l i l i t e r s o f the e x t r a c t i n g s o lu t ion, 90/10 ( v / v )

ACN/DMSO, are added. M3.4.3. A cap equipped with a T e f l o n liner is in s ta l l ed .3.4.4. The vial is shaken to remove large air bubbles f r o m be- tttween the f i l t e r and the glass. Let the vial set for 1 h. •

3.5. Analys i s •3.5.1. Reverse phase HPLC condi t i on s

column: 25-cm x 4.7-mm i.d. s ta in l e s s steel column •packed with 10-um A l l t e c h Cg or su i tab l e "equivalent ,mobile phase: 0.01 M ammonium acetate in 37.57 62.5 fiA C N / w a t e r ( v / v ) a d j u s t e d t o pH 6.2 w i t h •acetic acidf l o w rate: 1 m L / m i n •

UV d e t e c t o r : 254 and 313 nm gf luore scenced e t e c t o r : 240 nm e x c i t a t i o n _

370 nm emission •i n j e c t i o n size: 10-25 yL ™chromatogram: F i g u r e 3.5.1.3.5.2. An external s tandard procedure is used to prepare a cali- Pbrat ion curve using at least 2 stock so lu t ions f r o m whichd i l u t i o n s are made. The cal ibrat ion curve is prepared amd a i l y . The samples are bracketed wi th analyt ical stan- •j _ _ » _ •

II

3.6. I n t e r f e r e n c e s ( a n a l y t i c a l )3.6.1. Any compound having the same r e t e n t i o n t i m e as the a n a l y t e

is a p o s s i b l e i n t e r f e r e n c e . B e n z a l d e h y d e is an i n t e r f e r -ence for 2 ,4-TDI urea using the a f o r e m e n t i o n e d ana ly t i ca lc o n d i t i o n s but is not normal ly e x p e c t e d to be f o u n d . Gen-e r a l l y , c h r o m a t o g r a p h i c c o n d i t i o n s can be a l t ered to sep-arate an i n t e r f e r e n c e .

3.6.2. R e t e n t i o n t ime on a s i n g l e column is not p r o o f of chemicali d e n t i t y . A n a l y s i s by an a l t e r n a t e column sy s t em, ratio-ing of wave l eng th r e spons e , and mass s p e c t r o m e t r y area d d i t i o n a l means o f i d e n t i t y . ( U V s p e c t r a f o r d i i s o c y a n a t ed e r i v a t i v e s are shown in F i g u r e s 4.11.1.-4.11.3.)

3.7. C a l c u l a t i o n sThe c oncentra t i on in u g / m L of d i i s o c y a n a t e present in a s a m p l e isde t e rmined f r o m the area response of the analyt e s as measured byan e l e c t ron i c i n t e g r a t o r or peak h e i g h t s . Compari son of s a m p l eresponse w i t h a least squares curve f i t f or s t a n d a r d s a l l ows th eanalys t to d e t e r m i n e the c onc en t ra t i on of d i i s o c y a n a t e in u g / m Lfor the sample . S i n c e the s a m p l e volume is 2 mL, the r e su l t s iny g / m 3 of air are expres sed by the f o l l o w i n g equation:

U g / m 3 = ( u g / m L ) ( 2 m L ) / ( m 3 o f a i r s a m p l e d ) ( E x t r a c t i o n E f f . )3.8. S a f e t y precautions ( a n a l y t i c a l )

3.8.1. Avoid skin contact wi th all so lvent s .3.8.2. Vear s a f e t y g la s s e s at all t imes.3.8.3. Avoid exposure to the d i i s o cyanate s s tandards .

4. Backup Data4.1. D e t e c t i o n l i m i t of the a n a l y t i c a l procedure

The d e t e c t i o n l imi t of the a n a l y t i c a l procedure was 0.18 n g / i n j e c -t i o n for a l l three analy t e s . T h i s amount p r o d u c e d a peak whosehe igh t was about 5 t imes the h e i g h t of the base l ine noise. Ani n j e c t i o n size of 10 uL was used in the d e t e r m i n a t i o n of the de-t e c t i o n l i m i t s f o r t h e ana ly t i ca l proc edure . ( F i g u r e 4 .1 .)

4.2. D e t e c t i o n l i m i t o f the overall proc edure4.2.1. The f o l l o w i n g d a t a were o b ta in ed by vapor s p i k i n g increas-

ing amounts of the a n a l y t e s onto s a m p l i n g devices. Ani n j e c t i o n size- of 25 uL was used to de t ermine the de t ec-t i on l i m i t s o f t h e overall procedure .

42-11

T a b l e 4.2.1.Recoveries N e a r the D e t e c t i o n L i m i tanalyte

n g / s a m p l e

2 , 6 - T D Isp iked f o u n d16.925.433.842.267.684.5

101.4

3.514.027.833.954.261.985.8

HDIsp iked f ound33.944.266.288.2132.4

3.944.961.082.6133.7

2 , 4 - T D Ispiked found19.329.038.657.977.296.6

115.8

12.621.139.061.868.793.8120.8

4.2.2. G r a p h i c a l p r e s e n t a t i o n of the above d a t a are shown inF i g u r e s 4.2.1.-4.2.3. The d e t e c t i o n l i m i t s o f the overallprocedure de termined f r o m the F i g u r e s were 24.4 n g / s a m p l ef o r 2 , 6 - T D I , 33.3 n g / s a m p l e f o r H D I , a n d 19.2 n g / s a m p l ef o r 2 , 4 - T D I .

4.3. Rel iab l e q u a n t i t a t i o n l i m i tThe f o l l o w i n g d a t a were obtained by vapor s p i k i n g the analyte sonto s a m p l i n g devices. An i n j e c t i o n size of 25 uL was used to de-termine the re l iable q u a n t i t a t i o n l i m i t s .

T a b l e 4.3.Extrac t i on E f f i c i e n c y a t the Rel iab l e Q u a n t i t a t i o n L i m i tanalyten g / s a m p l e% recovery

XS D1.96 SD

2 , 6 - T D I33.8

117.4103.6103.6103.6103.6103.6103.6103.6105.3

4.99.6

HDI44.2124.8114.7

96.8114.7114.7114.7

96.896.8109.310.9

21.4

2 , 4 - T D I38.682.974.670.882.974.670.882.974.676.85.310.4

4.4. S e n s i t i v i t y and preci s ion ( a n a l y t i c a l method o n l y )The f o l l o w i n g d a t a were obtained f r o m m u l t i p l e i n j e c t i o n s o f ana-l y t i c a l s t andard s .

42-12

IIIIIIIIIIIIIIIIIII

1T a b l e 4.4.1.0.5x T a r g e t C o n c e n t r a t i o n

a n a l y t eU g / m Lareacounts

XSDCV

2 , 6 - T D I0.70069054693106938068824681176727168701686436719668499.6

8110.0118

HDI0.72270015706437099670340687516844569385690366845469562.89670,0139

2 , 4 - T D I0.704

127935127591127408125457124953124032126054125588124185125911.414540.0115

T a b l e 4.4.2.

analyteyg/mLareacounts

XSDCV

I x Target2 , 6 - T D I

1.400127643126872126332127445126896126037127077126384127033126857.7

5260.0041

Concentra t ionH D I1.443

129539130474128313128379129521128186129882125878128370128726.913460.0105

2,4-TDI1.407

236004235664233651234337234274231355234258229449234524233723.7

20760.0089

42-13

T a b l e 4.4.3.2x Targe t Concentrationanalyteu g / m Lareacounts

XSDCV

2,6-TDI2.800

249771244922248641246677246986245615252601248169248014247932.923090.0093

T a b l e

HDI2.886

252219249296259363252678252581250940247011249906251679251741.

33960.0135

4.4.4.

2,4-TDI2.814

459331457553458572461448461119457897463557460536459259

4 459919.119250.0042

Fooled C o e f f i c i e n t s o f Variat ion2,0

6-TDI HDI.0090 0. 0127 ""

2,4-TDI0.0087

4.5. S e n s i t i v i t yThe data in Tabl e s 4.4.1.-4.4.3.F i g u r e s 4.4.1.-4.4.3.

4.6. Retent ion e f f i c i e n c y

are presented graphi ca l ly in

4.6.1. Two re t en t ion s t u d i e s were c o n d u c t e d , the f i r s t at 12%relative h u m i d i t y and the second at 78% relative humidi ty .The sample s were vapor sp iked and removed f r o m the samplegenerator a f t e r a known volume of air had passed throughthe ca s s e t t e .

42-14

IIIIIIIIIIIIIIIIIII

T a b l e 4.6.1.1.Percent R e t e n t i o n at lOx T a r g e tC o n c e n t r a t i o n w i t h 200-L A i r V o l u m e (12% R . H . )a n a l y t et i g / s a m p l ef i l t e rbackupf i l t e rbackup

2 , 6 - T D I27.9296.9

1.095.60.9

H D I36.4497.22.095.6

1.8

2 , 4 - T D I31.8494.40.8

92.90.6

T a b l e 4.6.1.2.Percent Ret en t i ona t I x T a r g e t Concen tra t i on (782 R . H . )air volume, L

5.255.2510.5

15.7515.7521.021.026.2526.2531.536.7542.042.047.2547.2552.552.5

2 , 6 - T D I90.890.391.289.789.789.885.188.884.084.584.786.885.984.984.087.486.4

HDI91.588.489.892.086.790.088.493.892.487.589.190.390.084.784.490.987.2

2 , 4 - T D I85.184.084.582.678.982.377.481.778.277.180.080.179.779.275.780.879.4

4.6.2. The f o l l o w i n g da ta are pre sented to show that the dii so-cyanate d e r i v a t i v e s , l i q u i d s p i k e d , are retained on thecoated glas s f i b e r f i l t e r at the recommended air volume.

42-15

T a b l e 4.6.2.Percent R e t e n t i o n a t I x T a r g e tConcen tra t i on w i t h 20-L Air Volume (80% R.H)

analyteu g / s a m p l e% recovery

XSD

2 , 6 - T D I2.792

83.793.190.195.889.483.678.988.687.9

5.5

H D I3.64479.681.481.181.780.878.975.082.380.1

2.3

2 , 4 - T D I3.18476.088.586.391.486.578.973.082.782.46.4

4.6.3. Ten l i t e r s of 802 R . H . air were drawn through a f i l t e r tomoisten it and then it was vapor sp iked w i t h 20 L of dryair to observe the re tent ion of the derivative on the wetf i l t e r .T a b l e 4.6.3.

Recoveries F r o m a W e t F i l t e ranalyteu g / s a m p l e% recovery

XSD

2 , 6 - T D I2.792100.5

99.697.8

104.297.8

100.02.6

H D I3.644

91.690.688.8

, 95.989.791.42.8

2 , 4 - T D I3.18484.479.477.884.481.781.53.0

4.6.4. Ret en t i on e f f i c i e n c i e s at the 1989 TWA-PELThe f o l l o w i n g d a t a are pr e s en t ed to show that the d i i s o-cyanate der ivat ive s , l iquid s p i k e d , are retained on thecoated glas s f i b e r f i l t e r at the recommended air volumewhen sampl ing for the long per iods of time needed to de-termine the TWA exposure. No i socyanate d e r i v a t i v e wasd e t e c t e d on any of the g las s f i b e r f i l t e r s p laced 0.25 in.behind the coated f i l t e r s .

42-16

IIIIIIIIIIIII1IIIII

T a b l e 4.6.4.Percent R e t e n t i o n at Ix 1989

TWA PEL w i t h 240-L Air Volume (71% R . H )analyteyg/ s a m p l e% recovery

XSD

2 , 6 - T D I8.412103.1100.3102.798.7

97.196.799.82.7

H D I8.240103.5103.1102.3102.6102.0102.0102.60.6

2 , 4 - T D I8.376106.6106.1105.9106.6105.3105.4106.00.6

4.7. E x t r a c t i o n e f f i c i e n c yT h e f o l l o w i n g d a t a represent t h e analys i s o f coated glas s f i b e rf i l t e r s vapor sp iked w i t h the analyt e s at 0.05 and 1 t imes thetarget concentrat ions .

T a b l e 4.7.1.Extra c t i on E f f i c i e n c y a t 0.05x T a r g e t C o n c e n t r a t i o nanalyteyg/ sampl e% recovery

X

2 , 6 - T D I0.1396

86.092.880.284.269.389.491.795.177.491.7

103.294.688.0

HOI0.1822

93.990.091.792.291.3104.996.191.785.696.6107.699.695.1

2 , 4 - T D I0.1592

98.6102.1

98.5100.9100.1111.396.1

95.687.7

101.6108.2100.0100.1

42-17

T a b l e 4.7.2.E x t r a c t i o n E f f i c i e n c y a t I x T a r g e t C o n c e n t r a t i o nanaly t eu g / s a m p l e% recovery

,

X

2 , 6 - T D I2.792

92.095.692.692.491.893.788.389.690.290.887.789.991.2

EDI3.644

92.298.994.192.992.994.994.592.894.391.588.692.393.3

2 , 4 - T D I3.18493.098.192.994.492.093.985.885.588.690.587.587.690.8

4.8. R e p r o d u c i b i l i t y d a t aF i v e sample s were sp iked w i t h the three d i i s o cyanat e s and had 20 Lof humid air drawn through the cassettes. The samples were ana-lyzed by a chemist unassociated w i t h th i s evaluat ion a f t e r beings tored for 6 days at - 2 6 ° C . The r e su l t s are corrected for extrac-tion e f f i c i e n c i e s .

T a b l e 4.8.R e p r o d u c i b i l i t y R e s u l t s , % Recoveryanalyteu g / s a m p l e

XSD

2 , 6 - T D I2.792102.5

98.8102.7102.5101.2101.5

1.6

H D I3.644

101.397.0102.0101.3100.6100.4

2.0

2 , 4 - T D I3.184106.2103.4108.6106.2102.6105.42.4

4.9. S t o r a g e d a t aThe d a t a in T a b l e s 4.9.2.-4.9.4. show the e f f e c t s o f s torage atambient ( 2 2 ° C ) a n d reduced ( - 2 0 ° C ) t e m p e r a t u r e s o n vapor sp ik edc a s s e t t e s , which were generated w i t h 20 L of dry air f o l l o w e d by3 L of humid air to mo i s t en the sys tem. E x c e p t for day zero,

42-18

IIIIIIIIIIIIIIIIIII

three s a m p l e s for each of the two s torage c o n d i t i o n s were analyzedat in t e rva l s over an 18-day p e r i o d . The r e s u l t s are not correctedf o r e x t r a c t i o n e f f i c i e n c y . T h e d a t a a r e also pr e s en t ed graph i c -a l l y in F i g u r e s 4.9.1.-4.9.6.

T a b l e 4.9.1.Amount V a p o r S p i k e d , y g / C a s s e t t e2 , 6 - T D I H D I 2 , 4 - T D I

2.792 3.644 3.184

T a b l e 4.9.2S t o r a g e T e s t s f o r 2 , 6 - T D I

s torage time( d a y s )

004711

1418

%( r e f r i g e r a t e d )77.89.84.91.80.89.75.

8550967

83.84.88.92.85.83.85.

5234772

90.87.83.99.81.94.89.

recovery ( a m b i e n t )9850467

77 .889.5899495

10395

.8

.6

.1

.7

.3

85848986979995

.5.2.0

.5

.1

.4.5

90.987.891.090.587.3103.9102.0

T a b l e 4.9.3S t o r a g e T e s t s f o r H D I

s torage time( d a y s )0047111418

% recovery( r e f r i g e r a t e d ) ( a m b i e n t )

75.991.279.686.976.487.571.4

82.381.980.886.280.081.781.1

89.783.879.395.475.491.283.0

75.991.284.482.182.285.981.8

82.381.983.975.182.582.884.4

89.783.881.181.977.788.485.0

42-19

T a b l e 4.9.4.S t o r a g e T e s t s f o r 2 , 4 - T D Is torage time % recovery( d a y s ) ( r e f r i g e r a t e d ) ( a m b i e n t )

004711

1418

74.687.780.583.375.183.973.8

78.681.387.884.080.978.482.6

84.782.979.589.376.488.486.2

74.687.783.680.481.484.279.8

78.681.382.772.979.878.482.0

84.782.981.778.672.182.382.9

4.10. S i d e - b y - s i d e s a m p l i n gA s i m p l e experiment vas d e s igned which allowed a bubbler contain-ing n i t r o reagent and a g la s s f i b e r f i l t e r coated w i t h 1-2PP to bes imul taneous ly vapor sp iked f r o m the same 2 , 4 - T D I atmosphere.T h i s was a c c ompl i sh ed by l eaching a known amount of 2 , 4 - T D I off aglas s wool p l u g contained in a glas s tube w i t h d i l u t i o n air whichis then passed through a "Y" to each sampler. The air f l o w wasc o n t r o l l e d by ca l i bra t ed o r i f i c e s o f s imi lar f l o w rate down streamf r o m the sampler s .Each s a m p l e was analyzed twice and its average was p l o t t e d inF i g u r e 4.10. The d i f f e r e n c e s between the bubbler s ampl e s and thef i l t e r sample s a p p e a r to be random w i t h no d i s c e r n i b l e bias be-tween them. The amount of s c a t t e r observed in bo th c o l l e c t i o nsystems was not expected and probably can be a t t r i b u t e d to theexper imenta l des ign. The average line p l o t t e d in F i g u r e 4.10.r epr e s en t s the average of all the c o l l e c t e d s ampl e s and the d a t ais presented below.

T a b l e 4.10.A n a l y s i s o f S i d e - B y - S i d e S a m p l e s , u g / m 3

s p ik e123456789

c o l l e c t i o n c o l l e c t i o naverage sy s t em average sy s t em

192197.5164.5172.5208.5231230222.5233.5

FFBBFFFFF

continued

207209.5162.5179224.5181244.5223216

FFBBBBBBB

42-20

I1IIIIIIIIIIIIIIIII

T a b l e 4.10. ( c o n t i n u e d )c o l l e c t i o n c o l l e c t i o n

sp ike average system average system1011121314151617181920

226221.5226.5212212223.5225202.5219.5174331.5

FFFFFFFBBFF

250.5146.5199.5240.5218.5245296.5230176.5248269

BBBBBBBBBFF

F = G l a s s F i b e r F i l t e r w i th 1-2PPB = T o l u e n e Bubbler w i t h n i t ro reagent

4.11. UV S p e c t r aF i g u r e s 4.11.1.-4.11.3. are the UV sp e c t ra of the 1-2PP deriv-at ive s of the d i i s o cyana t e s used in th i s s t udy . The three com-pounds are named below:CAS no. name

- '. 2 , 6 - B i s ( 4 - ( 2 - p y r i d y l ) - l - p i p e r a z i n y l c a r b a m y l )toluene72375-27-0 l , 6 - B i s ( 4 - ( 2 - p y r i d y l ) - l - p i p e r a z i n y l c a r b a m y l )hexane72375-21-4 2 , 4 - B i s ( 4 - ( 2 - p y r i d y l ) - l - p i p e r a z i n y l c a r b a m y l )toluene

4.12. C a p a c i t y of an 1-mg coated glas s f i b e r f i l t e rA coated glas s f i b e r f i l t e r was chal l enged w i t h a 6 5 / 3 5 mix ture o f2 , 4 - T D I / 2 - 6 , T D I . The glas s f i b e r f i l t e r coated w i t h 1 mg o f 1-2PPwas su spended on an a d a p t e r ring of a s tandard 37-mm ca s s e t t e .A n o t h e r coated f i l t e r was p laced on a backup pad in the b o t t o m ofthe ca s s e t t e . F o u r more a d a p t e r rings were p l a c e d in f r o n t of thes u sp ended f i l t e r to a l l ow the incoming i socyanate to cover theent ire f i l t e r f a c e and no t j u s t h i t the center o f the f i l t e r . Theisocyanate mixture was l i q u i d sp iked onto glas s wool that had beenp la c ed in s i d e a 13-mm s t a i n l e s s s teel f i l t e r h o l d e r . The metalf i l t e r h o l d e r was in s er t ed in to the Luer-Lok f i t t i n g o f the cas-s e t t e t o p . The glass wool was then spiked w i th 8.52 ug of the TDImixture . Air was p u l l e d through the c a s s e t t e and ho ld er at 1L / m i n (72% r e l a t i v e h u m i d i t y ) . A f t e r 15 min, the a ir f l o w wass t o p p e d and the rear f i l t e r was changed and replaced w i t h a new

42-21

The glass wool was spiked again wi th 8.52 vg of the TDI mixture.T h i s procedure was r epea t ed u n t i l a t o t a l of 10 rear f i l t e r s hadbeen removed and a t o t a l of 85.2 ug of i socyanate had been sp ikedonto the glass wool.When the rear f i l t e r s were analyzed, none of the showed the pre-sence of any TDI. The f r o n t f i l t e r , which was not changed dur ingthe s a m p l i n g , had co l l e c t ed a t o t a l of 66.1 ug of TDI. The other19.1 ug of TDI was probably lost on the sides of the adap t er ringsof the cassette. The 66.1-ug col lec ted represents 7.9 times the1989 TWA-PEL when s a m p l i n g for 4 h.A second casset te containing f i l t e r s was also tes ted in the samemanner and again none of the rear f i l t e r s contained any isocyan-ate. In thi s test the f r o n t f i l t e r c o l l e c t ed 59.4 ug of TDI or7.1 times the 1989 TWA-PEL.

to luene-2,6-di i socyanate; 2 ,6- to luene d i i s o cyana t e ; 2 ,6-di i so cyanato- l-methylbenzene; isocyanic ac id, 2-methy1-1,3-phenylene es ter; 2 , 6 - T D I

1,6-hexaraethyiene d i i s o cyanate; HDI

H 3 Ctoluene-2,4-dii socyanate; 2,4-toluene d i i socyanate; 2,4-diisocyanato-l-methylb enzene; isocyanic ac id,4-methyl- l ,3-phenylene ester; 2,4-TDIF i g u r e 1.1.4. S t r u c t u r e s and synonyms of the d i i s o cyanate s .

42-22

IIIIIIIIIIIIIIIIIII

BOTTOM

BACKUP PADiTED OFF

SPACER

TOP

F i g u r e 2.1.2. A drawing of a sample cassette.

« . eM I N U T E S

F i g u r e 3.5.1. Chromatogram of s t andard s of the three d i i s o cyanat e s .

42-23

«lu«cOI-o

P E A K A - 2 . 4 - T D IP E A K B - I . e - H D IP E A K C - 2 . 6 - T O I

2O OT I M E . U I N

F i g u r e 4.1. Analy t i ca l d e t e c t i on l imi t for the diisocyanates.

Ula:u>OO

cr«

ra43S4

2?

te

2 , 6 - T D I

. O V E R A L L D E T E C T I O N L I M I T

33 55 77 114n g S P I K E DF i g u r e 4.2.1. Detec t ion l i m i t of the overall procedure for 2 , 6 - T D I .

42-24

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140

112

LJC£L«J 84ooLJ

70

5«

42ao14

1 , 6 - H D I

O V E R R L L D E T E C T I O N L I M I T14 28 42 S6 70 84n g S P I K E D 98 112 126 140

F i g u r e 4.2.2. Detec t ion l imi t o f the overall procedure for HDI.

O V E R f l L L D E T E C T I O N L I M I T.48 68 72n g S P I K E D •183 120

F i g u r e 4.2.3. Dete c t i on l imi t o f the overall procedure for 2 , 4 - T D I .

42-25

300000

27998O

24000O

2 210000x£ 180000

~ isoeoo»-»*§ 129000<r* 90000cc

60000

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2.7 3.0

Figure 4.4.1. Calibration curve for 2 , 6 - T D I .

sooeoo2700OO

210000

laeeooisoeoe

§ 1200009000O

60090

C f i L I E R f l T I O H C U R V E

SLOPE* 34333

1 , 6 - H B I.6 1.2 l.S 1.8 Z.I 2.4 Z.rU C X H U 3.0

F i g u r e 4.4.2. Cal ibra t ion curve for HDI.

42-26

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500900 .4COOOQ .

2 350009.x

§200090.Va 150008.a

100000 .59990.

0.0 .3

C f i L I E R f l T I O H C U R V E

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2 , 4 - T D I.9 1.2 I . SU C / m . 1.8 2.1 2.4 2.7

F i g u r e 4.4.3. Cal ibrat ion curve for 2 , 4 - T D I .

oo

120I OS

»*84

72

«6

48

36

24

12 2 , 6 - T D I A H I I C H T S R H P L C SL I H C f l R C U R V ET O T R L S T P M D . ERROR O f C S T . « 6 . 6 39 S V - C O M F 1 D E H C E L I M I T - *or-(l .S S * C O H r i O C H C C L I W I T « »or- 12.9

e.e 1.8 3.6 S.4 7.2 9.0 18.8BRVS !H STORflCE 12.6 14.4 16.2 18.0

F i g u r e 4.9.1. Ambient s torage test for 2 , 6 - T D I .

42-27

120ice96

u" 720u2 66

o ""u*• a*

24

12

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120tee

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24

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F i g u r e

•. . _ . _ - _ . _ . _ . _ . _ - _ . _ . _ . _ . _ . _ - _ - _ - _ . _ - _ - — - _ . _ - — - — - — . —

§ aB H M "f l

.

.A M & I C M T S A H P L C S

1 • t« "~ H D I LINEAR CURVEf TOTAL STAND. CRROR OF C S T . - f c . 4 29 6 V ' C O H r i D C H C C H H I T - *or-U .9«*«.42>

0 1.8 3.6 S.4 7.2 9.0 te.8 12.6 14.4 16.2 I*D A Y S I H S T O R A G E

4.9.2. Ambient storage test for HDI.

•• . .

11 a n BH " AA fl

••~"~"~- — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - —

_ A H B I C H T S A M P L E S^ • • T ~ " T D I • L I M C f l R CURVE " ' •• TOTAL STAND . CRROR OF C S T . - 6 . 3 S: ' 9S*< ' C O H r i D E H C E L I M I T - »or-U .96*6 .36J9S% C O H r i B C I I C C LIMIT" *or- 12. H

0 1.3 3.6 S.4 7.2 9.0 J 6 . 8 12.6 14.4 16.2 18D A Y S I H S T O R A G E

4.9.3. Ambient s torage test for 2 , 4 - T D I .

42-28

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9684

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S f l H P U E SL I N E A R CURVET O T Q L S T f l H B . ERROR O F E S T . - 7 . 6 39 G ' < C G N F I U C H C C L I M I T - *or-ll ,96»7.63)9 5 % C O H n D E U C E L I M I T - +of- 14.9

2 , 6 - T D I7.2 9.0 te.eB A Y S I K STORR6C

F i g u r e1.3 3.6 5.4

4.9.4. Refr ig era t ed storage test for 2,6-TDI12.6 14.4 16.2 16.6

o•_•u

ifUa.

120toe?e64

72

60

48

36

24

12

09.6

R E F R I G E R f l T E P S f l H P t E SL I H E f t l * CUEVETOTIM. S T O i m . ERROR OF E S T . - 7 . 7 9* 6 ' ! C O H F I P E H C E L I M I T - *oi-(l .<*««7.79JJ S ^ C O t t r i B C H C t t - I M l I T « *<>«— t»_.t

1.8 3.6 S.4 7.2

RR

1 , 6 - H D IU-i

9.8 19.8B f l V S I I I S T O f t O G E 12.6 14.4 16. Z 18.0

F i g u r e 4.9.5. R e f r i g e r a t e d s torage test f o r H D I .

I42-29

120103

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F i g u r e

•

R * RD R* 8 R

,• * » * « • ™ * •• * •* • «"• • B V ^B B *M • VIW « MB —— «» V ^B • ____ . ^M • ^ • H • . . ^ __ w . __• __ 1 . ^K * ^B • ...

•

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.

R E F R l C E R f l T E D S A M P L E S . « . — . - . —LINEAR C U R V E £. ^ 4 "" " 1 U JLT Q T O L STOIID. 'CRROR OP E S T . - t . 8 9 ? •9S-t C O N F I D E N C E L I H I T « +or-( 1.96*6.89)95% C O M F I D E H C E LIMIT- +or- 13.6 _ , _ ..... ............. .i

6 1.8 3.6 5.4 7.2 9.0 19.8 12.6 14.4 16.2 ISD A Y S I N S T O R A G E

4.9.6. Refrigerated storage test for 2 , 4 - T D I .

F-f,cr•

rB

1

R V E K O C E P I E C O I I C E H T R B T I O H F_.-

• .- ' E , B * F •_ F r f F r « - c - »* r* t_ F r F B_ r F p- / rF 7^ "*

. ""E B t" • i

I 2 3 4 5 6 7 8 9 10 11 12 13 14 IS 16 17 18 19 29S P I K E N U M B E R

4.10. Side-by- s id e comparison of coated f i l t e r s and bubblers.

42-30

I1111I11

.0

1111I111

11

0.0

UIomoeO49a

0.6

1 .O

1.6

K M V A T X V E OF Z . C - T V I III Ac*

200 2 6 0 3 O OW A V E L E N G T H ( N M )

360 400

F i g u r e 4.11.1. UV spectrum of 2 , 6 - T D I derivative in ac e toni tr i l e .o.o

0.6oz<

1 .0

1 .6 2 O O S 6 O 8 0 OW A V E L E N Q T H ( N M )

F i g u r e 4.11.2. UV spe c t rum of HDI der iva t iv e in a c e t o n i t r i l e

3 6 O 4 O O

42-31

0.0

I I IoCDCCO

0.6

1.0

1 .»

MBIVATZVE or 2.4-m n *e»

200 260 3 OOW A V E U E M O T H ( H M )

360 400

F i g u r e 4.11.3. UV spec trum of 2,4-TDI derivative in a c e t on i t r i l e .

42-32

IIIIIIIIIIIIIIIIIII

5. References5.1. "Cri t e r ia for a Recommended S t a n d a r d . . . O c c u p a t i o n a l Exposure toToluene "Diisocyanate", Depar tmen t o f H e a l t h , Educa t i on and W e l -

f a r e , N a t i o n a l I n s t i t u t e f o r Occupat ional S a f e t y a n d H e a l t h :C i n c i n n a t i , OH, 1973? HMS 73-11022.5.2. " C r i t e r i a for a Recommended S t a n d a r d . . . O c c u p a t i o n a l Exposure toDiisocyanates"; Department o f H e a l t h , Educat ion and W e l f a r e ,N a t i o n a l I n s t i t u t e f o r Occupat ional S a f e t y a n d H e a l t h : C i n c i n n a t i ,

O H , 1978; D H E W ( N I O S H ) Publ. ( U . S . ) , N o . 78-215.5.3. Kormos , L . H . ; S a n d r i d g e , R . L . ; K e l l e r , A n a l . Chem. 1981, 53 , 1125.5.4. S a n g o , C.; Z i m e r s o n , E. J. L i q . C h r o m a t o g r . 1980, 3_, 971.5.5. H a r d y , H . L . ; Walker , R . F . Analy s t 1979, 104, 890.5.6. E l l w o o d , P . A . , H a r d y , H . L . ; W a l k e r , R . F . A n a l y s t 1981, 106, 85 .5.7. G o l d b e r g , P . A . ; W a l k e r , R . F . ; E l l w o o d , P . A . ; H a r d y , H . L . J .Chromatogr. 1981, 212, 93.5.8. H o s e i n , H . R . ; F a r k e s , S . A m . I n d . H y g . Assoc . J . 1981, 4 2 , 663.5.9. W o o l r i c h , P . P . Am. I n d . H y g . Assoc . J. 1982, 43, 89.5.10. Cummins , K., Di i s o cyana t e s , 2 , 4 - T D I and MDI ( M e t h o d 18, OrganicM e t h o d s Evaluat ion Branch, OSHA A n a l y t i c a l Laboratory, S a l t LakeC i t y , U t a h ) unpub l i sh ed (2-80).

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