FINAL
DRUM HANDLING PLAN (REVISED)
TANK 21 AREA COMBUSTION, INC. DENHAM SPRINGS, LOUISIANA
Prepared for Combustion, Inc. Denham Springs, Louisiana September 1993 WCC File 92B059C
Woodward-Clyde Consultants ~~ \_il__ _ : ' ConsultingEngineers,'Geologists, and Environmental Scientists ,- 14454-} ' '^ L--^--^^?^:^y^-.i.^^^^i^^<'^-L^ 70856, /T '"..'"v.;" Woodward-ClydEngineering & science applied to the earteh & its environment
August 16, 1993 AUG I 8 1993 Mr. Tim B. Knight LA, DEFT. OF Inactive and Abandoned Sites Division ENVIRONMENTAL QUALITY Louisiana Department of Environmental Quality IAS DIVISION Post Office Box 82282 Baton Rouge, Louisiana 70884-2282 LOG Attention: Mr. Todd Thibodeaux ' Re: Combustion, Inc. Expedited Removal Action (ERA) Agreement Tank 21 Area Drum Handling Plan WCC File 92B059C Dear Mr. Knight: Attached for your review and approval is the revised Drum Handling Plan for the Tank 21 Area, at the Combustion, Inc. site, Denham Springs, Louisiana. The plan has been revised to incorporate the comments from LDEQ dated August 5, 1993. If you have any questions, please call. Very truly yours,
William R. Hurdle Field Representative
S. Russell Killebrew, P.E. Project Coordinator CCW:kdl Attachment DRUMQ59R.CVL COMBUSTN
Woodward-Clyde Consultants - A Subsidiary of Woodward-Clyde Group, Inc. 2822 O'Neal Lane (70816) • P.O. Box 66317 (70896) • Baton Rouge, Louisiana (504)751-1873 • Fax (504) 753-3616 FINAL
DRUM HANDLING PLAN (REVISED)
TANK 21 AREA COMBUSTION, INC. DENHAM SPRINGS, LOUISIANA
Prepared for Combustion, Inc. Denham Springs, Louisiana September 1993 WCC File 92B059C
Woodward-Clyde Consultants Consulting Engineers. Geologists, and Environmental Scientists 2822 O'Neal Lane. Baton Rouge. LA 70896 TABLE OF CONTENTS Woodward-Clyde
TABLE OF CONTENTS
Section 1.0 SITE INFORMATION 1 1.1 INTRODUCTION 1 1.2 SITUATION 1 1.3 HAZARD ASSESSMENT 2 2.0 GENERAL HEALTH AND SAFETY REQUIREMENTS 5 2.1 AUTHORITY AND RESPONSIBILITY 5 2.2 WORK ZONES 5 23 PROTECTIVE EQUIPMENT 6 3.0 PROCEDURES 7 3.1 EXCAVATION 7 3.2 DRUM HANDLING PROCEDURES 8 3.3 DISPOSAL 10 3.4 CONFIRMATION SAMPLING AND SITE RESTORATION 11 4.0 AIR MONITORING 12 4.1 SUPPLEMENTAL AIR MONITORING 12 4.1.1 Worker Monitoring 12 4.1.2 Fenceline Monitoring 12 4.2 ACTION LEVELS 13 4.3 RESPONSE TO TDI AIR CONCENTRATIONS EXCEEDING 0.02 PPM 13 5.0 SAMPLING AND ANALYSIS 15 5.1 CHARACTERIZATION SAMPLING AND ANALYSIS 15
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TABLE OF CONTENTS (Continued) LIST OF FIGURES Figure 3-1 Approximate Air Monitoring Locations LIST OF APPENDICES Appendix A Material Safety Data Sheets Appendix B Checklist of Activities to be Completed Prior to Excavation or Drum Handling Appendix C Equipment List for Excavation and Drum Handling Appendix D Confined Space Entry Permit Appendix E OSHA 42 Air Monitoring Method Appendix F NIOSH 2535 Air Monitoring Method
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1.0 SITE INFORMATION
1.1 INTRODUCTION This addendum to the Work Plans for the Expedited Removal Action (ERA) at the Combustion, Inc. site has been developed to provide additional safety precautions for work conducted in the Tank 21 area. This addendum describes drum handling procedures, supplemental air monitoring for the additional compounds of concern, and other additional details necessary to complete excavations of affected soil in the Tank 21 area. While the original Work Plan specifies the original site-wide chemicals of concern, physical hazards, emergency information, and other general and specific health and safety procedures, this addendum is to be followed in the Tank 21 area in conjunction with and as a supplement to the existing Work Plan. It will be reviewed and approved by Louisiana Department of Environmental Quality (LDEQ) prior to the continuation of excavation in the Tank 21 area. 1.2 SITUATION Tank 21 was an underground storage tank discovered in the southeast quadrant of the Process Area at the Combustion, Inc. site in Livingston Parish, Louisiana. The contents of Tank 21 were removed and the tank itself was then removed in accordance with the approved Work Plans. While excavating affected soils from beneath the location previously occupied by Tank 21, drums containing unknown materials were discovered. Although Tank 21 has been removed, the area where the drums were discovered will continue to be referred to as the Tank 21 excavation or the Tank 21 area throughout this plan to distinguish it from other portions of the Process Area. The area inside the excavation was made safe by replacing a protective soil blanket over the drums and work in the Tank 21 area was suspended. The Tank 21 area, specifically addressed in this plan consists primarily of a sludge-like soil containing the same chemical compounds found in the soil elsewhere on-site, with a few drums and drum contents distributed at random in the soil. In addition to the
92BOS9C-D/DRUM059R.TXT COMBUSTO 1 08-16-93 Woodward-Clyde sitewide compounds of concern addressed in the original Work Plan; site history, observations of characteristics of the contaminated soil, and air monitoring results indicate the presence of toluene diisocyanate (TDI) and related compounds (see Section 1.3). 1.3 HAZARD ASSESSMENT A liquid suspected of containing TDI was observed in the Tank 21 area while excavating. Additional chemicals may also be present. A review of past interviews with former employees at the site has disclosed the possible presence of drums containing toluene and methyl ethyl ketone. The suspected presence of TDI raises the possibility 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 TDA production. These compounds may present health hazards under certain exposure conditions. Dinitrotoluene (DNT) is another chemical associated with TDI and TDA production. During the Remedial Investigation, 2,4-DNT was detected in two soil samples 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 minimize exposure to workers and residents around the Tank 21 pit. A summary of toxicity for each of the suspected chemicals is presented below. Refer to the MSDSs in Appendix A for more details. Toluene: Toluene is a volatile organic compound exhibiting irritating effects upon skin, eye, and respiratory tract. Toluene is absorbed through the skin. The Occupational Safely and Health Administration (OSHA) permissible exposure levels (PEL) for toluene is 100 ppm 8-hour time-weighted average exposure with a short term limit of 150 ppm. On site monitoring and protection for toluene will be accomplished by applying action levels found in the original health and safety plan and utilizing protective equipment to include tyvek outer suits and rubber gloves. Monitoring will continue to be accomplished with an organic vapor analyzer (OVA) or a photoionization detector (PID). An action level of 2000 Mg/m3 for toluene has previously been established for this site and will remain in effect.
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Toluene diisocyanate: TDI is a clear to yellow liquid at room temperature exhibiting a sweet odor. TDI vapors are severe respiratory irritants and can cause asthma-like reactions in certain individuals. The OSHA PEL for TDI is .005 ppm as an 8-hour time-weighted average with short term exposure limit of 0.02 ppm. The odor threshold for TDI is approximately 0.2 ppm. These poor warning properties are the reason supplied air respiratory equipment is required for protection against TDI vapor exposure. Special instrumentation and monitoring techniques are required to evaluate low concentrations of TDI in air. Methyl ethyl ketone: MEK is a low boiling point, flammable liquid (flash point 35° F) with an explosive range of 12 to 20 percent. MEK is irritating to the nose and eyes at 100 to 200 ppm. The OSHA PEL for an 8-hour exposure is 200 ppm. Level B protective equipment will provide ample protection from MEK concentrations anticipated on-site. The use of spark resistant tools and monitoring with explosion meters and an OVA or PID will continue to be used for management of MEK hazards. Toluene diamine: TDA has a high boiling point, low vapor pressure, and is solid at room temperature. It has a black to purple color hi the environment after exposure to air. The 2,4 isomer is classified by EPAs weight-of-evidence as a B2 carcinogen. It may be absorbed through the skin. While handling TDA, care must be taken to avoid skin exposure. Exposure minimization is accomplished by restricting access to contaminated areas, wearing impervious garments if one maybe exposed (saranex suits, nitrile or butyl gloves, and chemical-resistant boots), decontamination with soap and water, and an awareness of the permeability of TDA through protective equipment. Awareness may be accomplished by training employees to observe the inside of boots and gloves for the presence of a brown-stain indicative of TDA penetration. Because the 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 dust contaminated with TDA Toluidine: All the physical characteristics and exposure management precautions associated with TDA apply to toluidine. In addition, toluidine can cause severe eye
92B059C-D/DRUM059R.TXT COMBUSTN 3 08-16-93 Woodward-Clyde irritation and skin irritation. Some isomers have been considered to be probable human carcinogens. Dinitrotoluene; DNT is a mixture of isomers presenting themselves as a solid at room temperature. DNT is a yellow solid with a melting point,around 70° C to 80° C. DNT at normal temperatures presents little inhalation exposure hazard. It may be absorbed through the skin so the precautions discussed earlier for TDA and toluidme apply equally to DNT. DNT exposure can cause anoxia by reacting with the hemoglobin to block oxygen transport by the hemoglobin. The OSHA PEL is 1.5 mg/m3. Care should be taken with construction activity to avoid dust and protect from skin exposure. Refer to the MSDS's attached in Appendix A for more details on the above listed chemicals.
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2.0 GENERAL HEALTH AND SAFETY REQUIREMENTS
2.1 AUTHORITY AND RESPONSIBILITY The procedures outlined in this plan will be implemented in addition to existing health and safely procedures. Where they must be implemented in place of existing procedures, they are more stringent Nothing in this plan shall be construed to lessen or reduce existing health and safety requirements. Procedures for decontamination, medical examination, protective equipment, site safety meetings, and site entry control remain as described in approved Work Plans and health and safety plans. Responsibilities of Project Managers and Site Safety Officers remain as described in the original Health and Safety Plans. Emergency notification numbers continue to be per the existing plan. If necessary, emergency evacuation of the community will be conducted per the Community Emergency Response Plan. However, some limited precautionary evacuation of the downwind residences immediately adjacent to the Process Area may be implemented based on air monitoring results. If so, the residents affected will be notified 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 Tank 21 excavation. Because portions of the Tank 21 excavation are less than 50 feet from the fenceline in the southeast corner of the Process Area, delineation of the 50-foot radius will continue outside of the fenceline into Mr. Darby's pasture. This extension of the Exclusion Zone will only occur during periods that actual excavation is in progress. At night and during other periods when activity is suspended, the fenceline will serve as the Exclusion Zone boundary on the south and east sides. During periods when work is in progress, an individual will be posted as a monitor to ensure that the Exclusion Zone is not entered except by personnel in the appropriate protective
92B059C-D/DRUM059R.TXT COMBUSTN 5 08-16-93 Woodward-Clyde equipment. The Contamination Reduction Zone and Support Zone for the Process Area will remain in effect per the approved Work Plan. A berm will be constructed around the perimeter of the Tank 21 excavation area to prevent wastewater from contacting clean areas. 2.3 PROTECTIVE EQUIPMENT All personnel entering the Exclusion Zone during excavation or drum handh'ng activities will employ U. S. EPA Level B personal protective equipment. This will include: • Pressure demand self contained breathing apparatus (SCBA) or pressure demand supplied 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 safety meetings, and site entry control remain as described in approved Work Plans and health and safety plans.
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3.0 PROCEDURES
3.1 EXCAVATION The Tank 21 area will be excavated with a trackhoe. Affected soils will be stabilized with fly ash for transportation and disposal at a hazardous waste landfill. When a drum is exposed, the trackhoe will stop work and field personnel will attempt to identify the drum's condition. In most cases, it is anticipated that such drums will be found to be drum fragments rather than intact, sealed drums. Such drum fragments will be excavated and shipped as debris with the stabilized soil. Should damage occur to drums during the excavation process resulting in a spill of liquid, all liquids and affected soils will be excavated, stabilized with fly ash and transported for disposal together with the originally affected soils. Any sealed, intact drums encountered will be handled in accordance with the procedures described below. Checklists for these operations are included as Appendices B and C. Only intact (non-leaking) drums will be removed from the excavation to the roll-off box. If a leaking drum is sufficiently intact such that it can be held in an upright position that prevents or stops liquid leakage, it will be removed from the excavation and transferred to the roll-off box and processed in the same manner as the intact drums. Leakage of liquids from damaged drums within the excavation will not have a significant impact on the already contaminated soil in the excavation. In the brief period of time after a leaking drum is discovered until soils are excavated, stabilized, and transported off site for disposal as hazardous waste, infiltration of spilled liquids will be minimal. Of more importance, the possibility of air emissions would be increased if liquid is allowed to leak from drums while they are suspended in mid-air such that small drops
92B059C-D/DRUM059R.TXT COMBUSTN 7 08-16-93 Woodward-Clyde come in contact with circulating air above ground level. Such drops expose the maximum liquid surface area to the air, allowing the greatest possible transfer of chemical from the liquid to the vapor state. Leaks within the excavation would be below ground level and thus shielded from circulating air by the sides of the excavation. This shielding together with the smaller surface area exposed by the upper surface of a liquid pool (in comparison to liquid dispersed as individual drops) would result in less potential for air emissions. In addition, treating liquid drums within the excavation will help prevent the spread of contamination to clean surface soils and will facilitate the rapid application of vapor suppressing foam if needed. 32 DRUM HANDLING PROCEDURES Intact drums will be carefully uncovered in the trench and lifted with a drum grappling device attached to the trackhoe. The drum will be placed inside a steel roll off container located adjacent to the trench, which will serve as a protective shield for personnel at the site. Th^s roll off container will be lilted such that any leakage would be held in the back of the container, at the end away from the door. Since leaking drums will not be transferred to the roll-off box, this should not occur. However, if drum liquids collect hi the roll-off box, these liquids would be treated in the same manner as dram liquids. Drum chime tongs will then be used to lift the drum and place it inside an overpack already placed in the roll off trailer. All personnel will then vacate the roll off box while 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 and secure the top on the overpack. Personnel collecting these samples must wear supplied air units and fully enclosed saranex suits, and ensure compliance with Section 2.1.12 of the Work Plan specifying confined space safety procedures. A confined space entry permit (Appendix 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 following actions: • If the drum has already been placed in the steel container, it will be dealt with in that container (by either the application of a vapor suppressing foam or, if possible, overpacMng the drum). • If the drum is still in the original excavation, water or a 5 percent solution of isopropyl alcohol in water will be added to submerge the drum. A vapor suppressing foam will be added to the surface of the water to prevent vapors from escaping. Moving drums while they are reacting will be avoided since the transportation activities delay the application of vapor emission controls such as vapor suppressing foam and increase the possibility to spread contamination to clean areas. Continuous air monitoring with both hand held monitors and the fixed monitors will focus specific attention on evaluation of the potential need to evacuate the downwind residences until the reaction has stopped. In the event that drums which are removed and sampled without incident are found to contain water reactive materials (TDI) based on the sample results, it may be necessary to react the material on site prior to shipment for disposal. This will become necessary if only a few drums of reactive material are discovered, and is because disposal facilities must reconfigure their operations to accept reactive material, a major undertaking which is not practical for small quantities of waste. Two alternatives exist for reacting the material:
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• The material may be reacted on site following the procedures just described except that the drum will be placed in a tank with the water solution rather than placing the water solution into the excavation to provide a more controlled and contained reaction. The tank will contain approximately 5,000 gallons (roughly 100 times the volume of the dram) of water containing a 5 percent solution of isopropyl alcohol (to help promote a complete reaction). Once immersed in water the overpack drum will be opened using the punch as previously described. • The liquid TDI may be repacked in smaller containers and absorbed with sawdust or a similar material to meet the requirements of the disposal facility. Acid Vapors. In the event acid vapors are encountered while excavating the Tank 21 area, a dense cloud would be expected. The presence of an acid cloud will be addressed as follows: • If the cloud appears to be leaving the fenced property, evacuation will be initiated by activating the "community response plan." • Work will stop at the excavation and all efforts will be made to alleviate the source of the vapor cloud. • Monitoring of the cloud will be accomplished using acid sensitive colorimetric detector tubes. 3.3 DISPOSAL Sampling and characterization of the soils will be completed prior to excavation. It is anticipated that the soils will be sufficiently similar to the pond sludges to be disposed of using currently established waste streams. Affected soils, drum fragments, and debris will be transported to the permitted hazardous waste landfill operated by Chemical Waste Management (CWM) at Carlyss, Louisiana for disposal. This is based on 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 facilities which accept LDR wastes is included in the Combustion, Inc. Superfund Site ERA Phase I Work Plan. If disposal of LDR wastes from the site are required, one of these approved facilities will be utilized. Intact drums will be sampled and characterized, and the disposal determination will be made based on the results obtained. Decontamination water, water from the excavation, and water used to react TDI as described above will be collected, transported by vacuum truck to the Pond Area, and treated through the activated carbon treatment unit prior to testing and discharge in accordance with the approved "Implementation Plan for Effluent Treatment System" dated June 24, 1992. 3.4 CONFIRMATION SAMPLING AND SITE RESTORATION Following removal of the affected soils and drums (or drum fragments/debris), the excavation 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 cleanup criteria 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 left in place so that they can be addressed (if necessary) in subsequent phases of the RI/FS process. The excavation will then be backfilled in accordance with the procedures in Section 4.2 of that plan.
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4.0 AIR MONITORING
4.1 SUPPLEMENTAL AIR MONITORING The approved "Air Monitoring Plan" dated June 30,1992 (Appendix G under separate cover of the "Work Plan for Removal Action - Phase 1") will remain in effect and samples will be collected and analyzed as required by that plan (see Table 3.2 of the aforementioned plan). Additional lead samples as required in the letter from LDEQ dated October 7,1992 will also continue to be collected. In response to the suspected presence of TDI, additional monitoring will be conducted to help prevent exposure to workers and the immediate public around this facility while excavating in the Tank 21 area. 4.1.1 Worker Monitoring Continuous monitoring will be conducted by a hand held instrument specific for TDI vapors (TLD1 MDA Scientific or equivalent). This instrument will be used by a qualified user to assure all workers exposed to .005 ppm or greater will be in Level B protection. In addition, this monitor will be used to adjust the size of the Exclusion Zone 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 equipment passing through decontamination has had the TDI removed. Any detectable level above background will require additional decontamination. 4.1.2 Fenceline Monitoring A continuous monitor sensitive to TDI (GMD-RIS catalog number 720010 or equivalent) will be utilized to evaluate TDI vapors at the Combustion, Inc. fenceline during excavation activities. This monitor will be located in the downwind position and will provide an alarm at .005 ppm. If the wind direction shifts, the monitor will be relocated to maintain its downwind position. If sustained readings exceed the .005 ppm PEL, 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 being initiated. Residences applicable to these evacuations are labeled as sample locations A 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 will be 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 will be taken using OSHA Method 42 or NIOSH Method 2535. The sampling will begin prior to beginning each day's work in the Tank 21 area and will end at the conclusion of each day's work in the Tank 21 area. These samples will submitted to an American Industrial Hygiene Association (AIHA) accredited laboratory for analysis. 4.2 ACTION LEVELS The action levels listed below are to be followed in the Exclusion Zone in addition to those found in Table 3-1 of the approved "Air Monitoring Plan":
TABLE 3-1 (Supplemental) Sample Meter Type Frequency . Parameter Action Level Response TDI Continuous TDI > .005 ppm Evacuate all nonworkers. Exclusion < .020 ppm Zone workers in Level B. TDI Continuous TDI > .020 ppm Take action to reduce air levels. Remain in Level 8. The senior Woodward-Clyde field inspector in consultation with the LDEQ representative on site will be responsible for initiating the responses on Table 3-1.
4.3 RESPONSE TO TDI AIR CONCENTRATIONS EXCEEDING 0.02 PPM Per the revised action level table that includes TDI the following actions are appropriate 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 the excavation until the liquid level is above the level of the TDI. • Dispense vapor suppressing foam until a layer of the foam is continuous over the surface of the excavation. • Continue to evaluate air concentrations around the excavation and expand the Exclusion Zone as appropriate. • Dispense more foam as necessary to minimize vapor dispersion to the atmosphere. A curtain and mist system was one of the systems considered to control vapor migration off-site. The curtain and mist system was not selected for the following reasons: (i) foam is more effective than a curtain and mist system for stopping emissions and (ii) a curtain and mist system would create contaminated runoff water which would require treatment and would not contain the TDI to the immediate drum burial area. A vapor suppressing foam has been selected to be utilized if real tune air monitoring shows the need to minimize the amount of vapors able to migrate off-site. The foam can be applied quickly if vapors are detected and is effective in stopping emissions from migrating off site. Air monitoring will continue each day following the end of activities until readings have returned to background. Based on current experience with the material, this should occur fairly rapidly (approximately 30 minutes). If problems persist, the sources of air emissions will be covered with polyethylene or a protective soil blanket.
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5.0 SAMPLING AND ANALYSIS
5.1 CHARACTERIZATION SAMPLING AND ANALYSIS Samples from any intact drams will be collected and analyzed for characterization for disposal. Details of analytical methods, preservation, shipping, and holding times are provided in Section 4.4.2.7 of the "Work Plan for Removal Action - Phase I". In general, characterization sampling will include: • Flash point for ignitability • pH and NACE corrosiviry test for corrosivity • Reactivity (to include total cyanide and sulfide) TCLP for Toxicity • GC/MS 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 to consider it a RCRA "listed" waste. Therefore, the waste must be profiled based on its characteristics: Ignitability (D001), Corrosiviry (D002), Reactivity (D003), and Toxicity (D004-43). The other parameters (BTU, ash, etc) are anticipated additional analytical requirement from the disposal facilities. They are required for other technical reasons and for pricing, but are not part of the waste identification.
92B059C-D/DRUMQ59R.TXTCOMBUSrN 15 08-16-93 FIGURES Woodward-Clyde
FIGURES IfCEHO N8250 _.._ SURFACE WATER ORAINACE PATHWAY/OUCH —— —— RNCC UNE r^-i HOUSE/aOMHNO „ <^ POND/JVIRTACC WATER BOOT lOi-i——! IMPROVED ROAD • HIGH VOLTAOE POWER UNE SUPPORT $ APPROXIUATE AIR SAMPUNO LOCATIONS
. NOTES; r ! 1)''$nGRIDE COORDINATE. S ARE BASED ON A LOCALLY OEflNED Dirf h "L
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» ERH-SoathwestHOUSTON • NEW ORLEANS • AUSTIN, • OAUA3 Inc• CLPAS PAO.S APPROMUATE AJnouRR UONITORINc O LOCATIONS MUM. nan tmttwj vug HUM. wtnm oo. we. *n nanavftH ON MOMOI t, nbPROCESu S AREA I Woodward-Clyde I I I I I I I I APPENDIX A I MATERIAL SAFETY DATA SHEETS I I I I I I I I I Woodward-Clyde
Toluene Diisocyanate (TDI) Material Safety Data Sheet No. 331 From Genium's Reference Collection TOLUENE-2,4-DnSOCYANATE Genium Publishing Corporation (Revision D) Schenectady.N1145 YCataly 12303-183n Street 6 USA Issued: November 1978 _____(518)377-8855______GEMUH MIBUaMNC CORP. Revised: April 1989 Material: TOLUENE-2.4-DIISOCYANATE Description (Origin/Uses): Usually prepared from toluene-2,4-diamine and phosgene. Used widely in the manufacture of polyurethane foams, elastomers, and coatings, all of which have extensive commercial and industrial applications. HMIS NFPA H 3 Other Designations: TDI; 2,4-Diisocyanate-l-Methylbenzene; 2,4-Diisocymatotoluenc; F 1 R 1 2,4-Tolylene Diisocyanate; CJlfipj CAS No. 0584-84-9 R 1 I 4 Manufacturer: Contact your supplier or distributor. Consult the latest edition of Chanicahveek PPG* S 3 Buyers' Guide (Genium ref. 73) for a list of suppliers.______^ *Seesect8 K 1 SEOiaOE»2iJiKGKEDlfeWl;SJft^^ Toluene-2,4-Diisocyanatc, ca 100%
OSHA PELs ACGIHTLVs, 1988-89 NIOSHRELs,1978 1 8-hrTWA: 0.005 ppm, 0.04 mg/m' TLV-TWA: 0.005 ppm, 0.04 mg/m' 10-hr TWA: 0.005 ppm, 0.036 mg/m 1 15-min STEL: 0.02 ppm, 0.15 mg/m' TLV-STEL: 0.02 ppm, 0.15 mg/rn' 20-min Ceiling: 0.02 ppm, 0.14 mg/m Toxicity Data* Human, Inhalation, TC : 0.5 ppm *See NIOSH, RTECS (CZ6300000), for additional data on toxicity with references to irritative, tumorigenic, and mutagenic effects.
Boiling Point: 482 T (250 "C)* * Volatile by Vctame: ca 100 Melting Point: ca 54 T (12 'Q Vapor Density (Air = 1): 6.0 MoleculaSpecific rGravit Weighty :08, 0174g/mo = 1): lL22 at 77 T (25 *Q* Vapor Pressure: 0.025 Torr Solubility 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 are representavailable s inove thre followin95% ofg currenthreet ratiosindustria: (1l ) usages100%. 2,4; (2) 80% 2,4:20% 2,6; (3) 65% 2,4:35% 2,6. The 80% 2,420% 2,6 commercial mixture "Specific to the 80% 2,4:20% 2,6 product !^ FlashPolnt; 266T(130'C)OC | Autolgnitlon Temperature; Not Found I LEL: 0.9% v/v {UEL: 9.5% v/v Extinguishing Media: This highly combustible liquid can be dangerous during fires; it is often mixed with flammable, volatile solvents. Use carbon dioxide (CO)and water spray to extinguish toluene-24-diisocyanate fires. Unusual Fire or Explosion Hazards: Containers of TDI can rupture violentl2 y when heated; cool exposed containert s or tanks of mis material with water spray. Special Fire-lighting Procedures: Wear a self-contained breathing apparatus (SCBA) with a full facepiece operated in the pressure-demand or positive- pressure mode. SECTION Stability /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-amine compounds. Chemkal Incompatibilities: 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 carbon dioxide. Conditions to Avoid: Prevent exposure to incompatible chemicals, sources of ignition, and ultraviolet light (yellow discoloration is otherwise likely). Hazardous Products of Decomposition: During fires, thermal oxidative degradation of toluene-2,4-diisocyanate can produce toxic gases such as carbon monoxide (CO), carbon dioxide (CO,), and oxides of nitrogen (NOM). SECTION €. HEALTH HAZARD INFORMATiQN Carcinogenicity: Toluene-2,4-diisocyanate is not listed as a carcinogen by the NTP, IARC, or OSHA. Summary of Risks: TDI exhibits low oral toxicity; however, inhalation of very small amounts of it causes severe irritation of the respiratory system. Skin contact with TDI causes redness, swelling, and blistering, leading to allergic eczema and skin sensitization to future TDI exposure. Ingesu'on causes corrosive damage to the gastrointestinal tract Medical Conditions Aggravated by Long-Term Exposure: Existing asthma, allergies, or respiratory problems. Primary Entry: Inhalation, skin contact Acute Effects: Severe irritation of the mucous membranes, respiratory tract, and eyes; acute asthmatic attacks; a choking sensation, chest pain, waves of productive coughing (if breathing-zone concentration reaches 0.5 ppm, the possibility of respiratory response is imminent with latent periods (canfd.) C I989 fry Crania Futitatuaf GorpOHUOd No. 331 TOLUENE-2.4-DIISOCYANATE 4/89 r:SECM'IONeiHEAL^HiHAZARPlNFX>RMAXIQN, continued j of 4 to 8 hours; abdominal distress, nausea, and vomiting; and skin irritation. Chronic Effects: 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 effects or sensitization, even at low exposure of 0.02 ppm and below and may take 6 months to 20 years to develop. Skin sensitization is another possibility. Once sensitized, reactions can occur to concentrations of 0.005 ppm or less. FIRST AID: Eyes. Immediately flush eyes, including under the cyeBds, gently but thoroughly with flooding amounts of running water for at least 15 minutes. Skin. Rinse the affected area with a flooding amount of water; wash it with soap and water. Inhalation. Remove the (exposed person to fresh air; restore and/or support his or her breathing as needed. Have qualified medical personnel administer oxygen as required. Keep him or her warm and at rest until medical help is available. Ingestion. Unlikely. Should accidental ingestion occur, give the t exposed person 2 to 3 glasses of water to drink and induce vomiting. Get fa-plant, paramedic, or community medical help for all exposure. Sect prompt mcdiral MlHf**""* *"• fatflier tMtmMit, nh«erv«tinn, and mppait after first «?d. Nate to Physician; If severe inhalation exposure is suspected, i«««M««te hospitalization with careful monitoring for the delayed (up to 72 hours) onset of pulmonary edema is suggested. Steroids may be useful in decreasing or controlling the mflammatory response of the lungs if administered on a short- f 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. Spill/Leak: Notify safety pi el, eva ry p el. sources of ignition, and provide adequate ventilation in the event of a toluenc-2,4-diisocyanate spill or leak. Cle up person l 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 it into appropriate containers suitable for eventual disposal or reclamation. Waste Disposal: Contact your supplier or a licensed contractor for detailed recommendations. Follow Federal, state, and local regulations. Neutralize TDI residue in drums before they are disposed of or reused. Contact your supplier for neutralizing instructions. OSHA Designations Listed as an Air Contaminant (29 CFR 1910.1000 Subpart Z) EPA Designations Listed 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 apply to your facility; see 40 CFR 372.85 for instructions] I SEG11QN & SFfcUJAk ra Goggles: Always wear protective eyeglasses or chemical safety goggles. Wear a full face shield where splashing of toluene-2,4- diisocyanate or its solutions is possible. Follow OSHA eye- and face-protection regulations (29 CFR 1910.133). Respirator: Wear a NIOSH-approved respirator per Genium reference 88 for the maximum-use concentrations and/or the exposure limits cited in section 2. Follow OSHA respirator regulations (29 CFR 1910.134). For emergency or nonroutine operations (leaks or cleaning reactor vessels and storage tanks), wear an SCB A. Warning: Air-purifying respirators will not protect workers in oxygen-deficient atmospheres. Other: Wear impervious butyl rubber gloves, boots, aprons, and gauntlets to prevent skin contact with TDI. Ventilation: Install and operate general and local maximum explosion-proof ventilation systems powerful enough to maintain airborne TDI concentrations below the OSHA PEL standard cited in section 2. Local exhaust ventilation is preferred because it prevents dispersion of the contaminant into the general work area by eliminating it at its source. Consult the latest edition of Genium reference 103 for detailed recommendations. Safety Stations: Make emergency eyewash stations, safety/quick-drench showers, and washing facilities available in work areas. Contaminated Equipment: Contact lenses pose a special hazard; soft lenses may absorb irritants and all lenses concentrate mem. Do not wear contact lenses in any work area. Remove and launder contaminated clothing before wearing it again; clean this material from your shoes and equipment. Comments: Practice good personal hygiene; always wash thoroughly after using this material and before eating, drinking, smoking, using the toilet, or applying cosmetics. Keep it off your clothing and equipment. Avoid transferring it from your hands to your mouth while eating, drinking, or smoking. Do not eat, drink, or smoke in work areas. Do not inhale TDI vapor. Storage/Segregation: Store toluene-2,4-diisocyanate in closed containers in a cool, dry, well-ventilated area away from sources of heat or 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 or dry 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 of the workplace level of TDI and the workers' responses to it is suggested. Transportation Data (49 CFR 172.101-2) DOT Shipping Name: Toluene Diisocyanate IMO Shipping Name: Toluene Diisocyanate DOT Hazard Class: Poison B IMO Hazard Class: 6.1 DOT ID No.: UN2078 IMO Label: Poison DOT Lable: Poison IMDG Packaging Group: D DOT Packaging Requirements: 49 CFR 173.346 DOT Packaging Exceptions: 49 CFR 173345 References: 1, 6, 26. 38, 84-94, 100, 116, 118, 119. 122 Prepared by: PJ Igoe. BS; Industrial Hygtene Review; DJ Wilson, Cffl; Medical Review: W Silverman, MD I Capjmf M C 1989 by Gaum Pobtabmj Caponom. Anjr O e or nprcHKOoo wnhool d r Mcciurily OK puchner 't mpanbfliqr. Altto c are h» fc-cn feken te the pnpmtao at mO> kl Publiibiilt Copontiooc>
Toluidine JUL-02--93 FRI 14:14 ID:INDHYB 3006 «375 Pll MAftKlAL OCEAN' liNetwornk EMERGENCY PHONE 1-800-OLIN-91SAFET1Y DATA SECTION I - IDENTIFICATION CHEMICAL NAMo-ToluidineE • *VNON«tfj f2 amtno-toluene; 2 methyl aniline ' "" CHEMICAL. . FAMIlAnilin* e (FORMUL| A n-M.CiHgX M TRADo-ToluidinE NAMi! e '— DESCRIPTION CA* HO. ————— Colorless to pale yellow liquid 95-53-4 SECTION II - NORMAL HANDLING PROCEDURES PRECAUTIONS TO BE TAKEN 1*9 KAMOLINO AMD STORAGE May be fatal if swallowed. Avoid contact with eyes, skin or clothing. Upon contect with skin or eyes, wash off with water. Avoid breathing mist or vapor. Store in a cool, dry, well-ventilated place away from alLsources of ignition. Avoid contact with .oxidizers..
PROTECTIVE EQUIPMENT VENTILATION RBOUIftEMENT* EyOO Goggles Glov«a Impervious gloves As required to keep airborne Impervious coveralls and boots concentrations, below TLV.
SECTION III - HAZARDOUS INGREDIENTS A a»f 1C KATEIM&L , °**|PIv LOSO '. LC'SU. SIGWFICAI3T *PI-«CTC o-Toluldine Sppm . 670 mg/kg L l Damage to liver, kidney, (skin) .... (oral-rat) • IZfS mg/n°, v• blood* and CN8. Anoxia, Z(F»- . . . ..(human) . headache, -nausea, &-H-H..TVIA • exhilaration, hematuria, . - cyanosis, convulsions. SECTION IV. FIRE AND EXPLOSION HAZARD DATA FIASM POINT OSNA CLASSIFICATION FOMMABLC LOWER UPPER METHOO 185°F CC Combustible liquid LIMITEXPLOSIVS E 1.5% No data KXTINGUISMINWateO MEDIr sprayA , dry chemical, foam or carbon dioxide. SPECIAL FINK HAZARD « FIRE PIOHTINQ PROCEDURE* water spray snouio DO useo to cooi lire exposeo containers and/or to disperse unignited vapors. Use NIOSH/MSHA approved positive ncii any 15 mvuwea in a SECTION V - HEALTH HAZARD DATA THRESHOLD LIMIT VALUCo-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. EMCRQEMCV FIRST-AID PROCEDURES SKIN Immediately flush with water for 15 minutes, call a physician. Immediately flush with water for IS minutes, call a physician. EVES Immediately drink large quantities of water, induce vomiting by sticking fing*r INGCSTION d>wn ths.-o.it. - Call a physician. MHALAT.Ott InmeiiHtuly remove victim to fiesh a r, call a physician. JUL-02-'93 FRI 14:15 ID:INDHYB 300S «375 P12 o-Tolu;c;ne CHEMICAL NAUC SEaiON VI - TOXICOLOGY (Product) rat) cAftciKOOEKicrrt Suspect carcinogen 570 mg/*3 < I-.IIT/OEKICITV Positive Ames Test «: -«,» f-«t»hirt KYSmwTATiou Severe irritant 'sssss.ic.rreiUHALMiOMLCSo O sw^sr---"—— "•"-' 9llNCI*Ai_ Inhalationinnamimn. JCOUTC, ,* Oj-%,.skiP nABSOMFTIO . ^_-.-contact_ H_, . ingestion., , eye____ contact p"~a iCYHeadacheS Of ACUT, E vomitingEXPOSURE, low blood pressure, cyanosis, convulsions, dermatitis, hematuria j EFFECTAnemiaS OP CMfiOWl', dermatitis: EXPOSUN. E Damage to liver, kidney, blood, and CMS. Suspect earinogen. ___ SECTION VH .SPILL AND LEAKAGE PROCEDURES (Contro- l - Procedure*• . __*) Wear: r\»lr i KATFKIANIOSH/M5HL KELKASAt OMapprove »«U. d positive pressure supplied air respirator. Follow OSHA regulnttons Cor respirator use* (5ee 29 CFR 1910.134). Wear goggles, impervious, coveralls, gloves and boots. Remove all sources of ignition. Isolate area o£ spill by diking. Stop source of leak- Transfer- contents to non-leaking container, or storage vessel. Add non- combustible dry absorbent, shovel or sweep up. Place In an. appropriate container end seal. Wash all contamintted clothing before reuse. In the event of a large spill, call the emergency telephone number shown on the front of this sheet. : RMCftGRKCY. CONTACT CHEMTREC 800-424-9300 'WASTDisposE o«sv£i3/.ie o. f BCTHOcontaminateQ d product, empty containers and materials used in cleaning up spills or ,..* leaks in a manner approved for this material. Consult appropriate federal, state and local regulatory agencies to ascertain.proper disposal procedures. SECTION VIU • SHIPPING DATA .I Intermediate: AcrmTY DATA I MAZAHOOU* I POt-YBERIZATIOK
Carbon monoxide^earbon dioxide, oxides of nitrogen SECTION X • PHYSICAL DATA mmHgQ20°C SOLO»IUTTINWAT|« V»POK DENSITY (Air • SPECIFIC O*fc»MTV (U,O AT : runr-rissjEo av: anEnvironmentad Toxicology l DepartmenHygiene t ° (202) f 8? -5.436 Ow.rtm.nl ei en»,ro»m.n,.l Hy9" CORPORATJOK Long f n«*9» R**a Sia-.^ra C-«-.n,«.cui 0-.M4 OCEAU-SKS Networl-Y PHON.E t BOO-OUN-*1 1 Woodward-Clyde
Toluene Diamine (TDA) JUL-02-'93 FRI 14:16 ID:INDHYG 3006 8375 P13
720Air1 ProductHamilto* n mdBoulevar Chemicalsd , Me. PRODUCTSAIR TelephonAllentowne . (215PA) 18195-150481-49111 MATERIAL SAFETY DATA SHEET SECTION l: PRODUCT IDENTIFICATION MATERIAL NAME (TRADE NAME)* Meta-Toluenediamine, 99X MANUFACTURER Air Products and Chemical*, Inc. Allantown, PA 18195 CHEMICAL NAME 2,4-and 2,6-Toluanediemine Matatalylenadiamina 2,4-and 2,6-diaminotoluena 4-Methyl-l,S-benzenediamine 2-Methyl-l,S-benzenediaaine TDA 2,4 and 2,6-TDA nr-TDA CHEMICAL FAMILY: Aromatic amines EMERGENCY TELEPHONE NUMBERS SALES a PRODUCT INFO PHONE 1-800-525-9374 1-800-345-3148 1-215-481-4911 Coutsida U.S.A.) MSDS NUMBER* 6202-08 EFFECTIVE DATEi November 199REVISION0 i 08 REVISION NOTEt Updated Health Hazard Data
SECTION 22 HAZARDOUS INGREDIENTS Components) of the product ara: 2,4 - Toluanediamine, approx. 80X (Toxic) 2,6 - Toluenadiamine, approx. 202C (Toxic) Trace 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 for 2.6-TDA. Experimentally, toluanadiamine has been shown to cause cancer in laboratory animals.* It may enter the body via insertion, inhalation or skin contact. KS*e RafarencM 1 and 3.
SECTION 31 PHYSICAL DATA BOILING POINT 541 F (28.3 C) a 760 mm Hg (80/20 TDA) MELTING POINT 210.2 F (99 C); (pure 2,4-isomer) DENSITY 8.68 Ih./gal. a 221 F (105 C)| 1.Q JUL-02-'93 FRI 14:16 ID:INDHYG 3006 8375 P14
Air Product* «nd Chemical*. Inc. All? A AlhMWovvn7201 Mammo. PAn 1B195-150Boulevard 1 P0fH9 TtfMphone (215) 411-4911 SOLUBILITY IN HATER * Soluble in hot water, alcohol, ether, and many polar organic solvents. VAPOR PRESSURE Com Hg) ' 0.3* x 10-3 mm Hg 3 100 F C37.8 C>; 1 mm Ho 3 223 F C106.5 Oj 100 mm Hg 3 413.6 F C212 C) VAPOR DENSITY : Not Applicable X VOLATILE BY VOLUME ' : Not Applicable PH Not Applicable APPEARANCE/ODOR = Solid, light yellow to tan, darkens on storage and exposure to air/Slight ammonia-like SECTION As FIRE AND EXPLOSION DATA FLASH POINT » 284 f (140 C) ASTM 092 AUTOIGHITION TEMP. 842 F C4SO C) FLAMMABLE LIMITS (*> > No Data EXTINGUISHING MEDIA : water, carbon dioxide, or foam. SPECIAL FIREFIGHTING PROCEDURES: Potentially toxic products of combustion suggest that surrounding areas should be evacuated. Due to the biological properties of TDA, an attempt should be made to contain water used to extinguish a fire. The chemical structure of TDA suggests that toxic ammonia* carbon monoxide and nitrogen oxides may be liberated when TDA is heated to high temperatures or pyrolyzed. Since materials of combustion may be toxic, full body protection (constructed of butyl rubber or its equivalent) including a self-contained breathing apparatus, should be worn when fighting fires. FIRE AND EXPLOSION HAZARD: Down-wind personnel must be evacuated.
SECTION 5: HEALTH HAZARD INFORMATION/FIRST AZD Toxicology* o Mild irritant to the ayes and skin of a rabbit, o Oral LD50 Crat): 212 mg/kg o Dermal LD50 (rabbit): >5750 mg/kg o Inhalation LC50 (rat): >5.3 mg/l/4H or >180 ppm o Reproductive effects, methemoglobinemia, hepatotoxicity, thyroid and bone marrow hyperplasia have been reported in exposed laboratory animals. Routes of Entry* o Ingestion o Skin absorption o Inhalation JUL-02-'93 FRI 14:17 ID:INDHYB 3006 «375 P15
Air Product* and Chemicals, ine. —._.—.«. ,. . Telephone (215) 4B1-491 1 PRODUCTS r SECTION 6: REACTIVITY DATA STABILITY* The product is stable and do ax not undergo spontaneous polymerization. TDA undergoes oxidation when exposed to air with tha production of color bodias and tars. This reaction procaads most rapidly at high temperature, for example, when in the moltan state. Oxidation products have not been fully characterized and should be treated as toxic materials. INCOMPATIBILITY C SPECIFIC MATERIALS TO AVOID): TDA i* weakly basic and reacts with mineral acids to form water soluble amine salts. Thesa are more stable to oxidation than the basic amine. HAZARDOUS DECOMPOSITION PRODUCTS! See stability comments above. HAZARDOUS POLYMERIZATION « Hill not occur SECTION 7s SPILL. LEAK AND DISPOSAL PROCEDURES The product is shipped in the molten or solid state. If a spill occurs, the area should be evacuated until the TDA solidifies. Spill clean-up should be done by personnel wearing complete body protection Csee Section 8). Following removal of solidified TDA* the area should ) be cleaned thoroughly with hot water to remove all residual TDA from surfaeas. Contaminated water should be contained to prevent surface and ground water contamination. Solid TDA should be scooped into disposal containers constructed of corrosion-protected carbon -steal or of stainless steel. Disposal containers should bear warning of Toluenediamine* a toxic substance Csee label in Section 9) and warning against skin contact or inhalation of vapors. DISPOSAL '• Haste material may be incinerated or disposed in a Class I hazardous chemical landfill where permitted by local authorities. Drums containing TDA should not be re-used but should be buried in a Class I hazardous chemical landfill. Disposal should be completed by an authorized, licensed disposal agent. Care should be taken to assure propar container sealing to prevent ground and surface water contamination. Incineration of TDA at controlled rates in a properly designated chemical waste incinerator is the preferred method of disposal. Toxic nitrogen oxide emissions may increase as a result of burning.
SECTION 8: SPECIAL PROTECTION INFORMATION VENTILATION: Work areas need to be well ventilated. For respiratory protection, a half-face mask of the cartridge type* j National Institute for Occupational Safety and Health CNIOSH) approved for organic vapors, is recommended. If dust or mist particulate is to ba removed/ a dust filter in series with the organic vapor filter is required. JUL-02--93 FRI 14:17 ID:INDHYG 3006 8375 P16
Ai720r 1Product Hamilto* n widBoultvar ClwmiMhtd . Inc. TelephonAHtmtowne . (215)481-491PA 18195-15011 PRODUCTS l£l
EYE PROTECTION* Hrar safety alms*** with side shields or chemical splash goggles. When molten IDA is being handled, a full-face shield should be worn in conjunction with safety glasses or goggles. HAND PROTECTION '• Wear gloves made of butyl rubber or its equivalent. OTHER: Wear overshoes made of butyl rubber or its equivalent and a long sleeved shirt. When molten TDA is handled, « lab apron or coat made of butyl rubber or its equivalent should be worn in conjunction with gloves and overshoes. SECTION 9$ SPECIAL PRECAUTIONS AND HANDLING INPORHATION HANDLINO' TOLUENEDIAMINE CAUSES CANCER IN LABORATORY ANIMALS WARNING. HARMFUL IF SWALLOWED, INHALED OR ABSORBED THROUGH SKIN MAY CAUSE CHEMICAL CYANOSIS Avoid breathing dust or vapor. Avoid contact with eves, skin or clothing. Use only with adequate ventilation. Keep containers closed. Hash thoroughly after handling. Use protective clothing, butyl rubber gloves, boots and goggles. Discard contaminated clothing and shoes. Molten material will cause skin and eye burns. First Aid' If swallowed, induce vomiting. If patient is eyanotic (blue color of skin), give oxygen. CALL A PHYSICIAN. If inhaled, remove victim to fresh air. In case of skin contact, remove clothing, take a body shower in lukewarm water. Clean under fingernails. DO NOT USE HOT WATER. In case of eye contact, flush with large quantities of water for at least 15 minutes. Spill or leak' Evacuate area. Contain spill with earth dikes and allow to solidify. Scoop into drums by personnel with full body protection. Rinse down area with water. Haste material may be incinerated or used as landfill if permitted by local authorities. HANDLINO AND STORAGE REQUIREMENTS: The product oxidizes in the presence of air. Exposure to air should be minimized. Melt should be transferred in leak-free systems (pumps, pipe and coupling).
SECTION lOt ADDITIONAL INFORMATION JUL-02-'93 FRI 14:18 ID:INDHYE 3006 «375 P17
AII9 Air ProductHamilto* n anBoulevard Chemiealad . me. PRODUGlSoofint ir»re Telephone" (215) 481-4911 Exposure Standards' o No standards established a Maintain air concentrations in tha workplace at the lowest feasible levels. Health MilHazardsd irritan! t to tha eyes and skin. Toxic CANSI 2129.1,1988) by ingestion Carcinogen (a) XARC CbJ NTP Cc> OSHA Blood toxin Hapatotoxin or Liver toxin Reproductive hazard Signos anContacd Symptomt wits h othf e Exposureyas eor skin causes irritation and discomfort. o Repeated and/or prolonged contact with the skin may cause o sensitizationProduct is .absorbed through the skin and may cause nausea, headache and general discomfort, o Inhalation of dust may cause respiratory irritation and may cause o cyanosisIngestio.n may causa headache, nausea and/or vomiting, a Repeated and/or prolonged exposure at low levels may result in* o liver disorders o blood chemistry changes o reproductive disorders Medical Conditions Generally Aggravated by Exposure o Liver disorders FIRST AID: EYFlusE h CONTACTaye fo* r at least 15 minutes with large quantities of water. SKIN CONTACT' Remove material from skin with soap and warm water. General contamination of the body or limbs requires a full body shower with special attention to hair and fingernails. Hot water should be avoided as it may enhance absorption. Discard contaminated clothing and shoes. For burns of the skin, cover the affected area with a sterile dressing or clean sheeting and transport for medical care. Control shock. INHALATIONi Remove victim to fresh air. Administer artificial respiration and oxygen if victim is not breathing. If breathing is difficult administer oxygen. CALL A PHYSICIAN. IINGESTIONf ingested' , empty stomach by aspiration or induced vomiting. CALL A PHYSICIAN. JUL-02-'93 FRI 14:18 ID:INDHYE 3006 8375 P18
Air Products mfitl Chemical*. Inc. Alft „/•• TAWpnonSSKSTSfflftSSe (at5> 481.4911 i PRODUCTS fc= REGULATORY CONCERNS: The proper shipping description for Toluenediamine according to tha Department of Transportation COOT) is RQ, Toluenediamine. ORN-A/ NA1709. All components ara included in the E.P.A. Toxic Substance Control Act Chemical Substanea Inventory. OSHA Hazard Communication Standard C29CFR1910.1200) hazard class: ) toxic by ingestion, b> carcinogen, c) raproductive toxin and d> live r a toxin. EPA SARA Title III hazard class' a) immediate health hazard and b) delayed health hazard. SubstanceCs) listed by California under the "Safe Drinking Water and Toxic Enforcement Act of 1986" CProposition 65)» 2,4-diareinotoluene. EPA SARA Title III Section 313 C40CFR37Z) Toxic Chemicals present in quantities greater than the "de minimis" level are* Diaminotoluane Cmixed isomers) 1DOX). EPA Reportabla Quantity Under CERCLA for Toluenediamine is 1 pound . (0.454 kg). J Canadian WHMIS Controlled Products Classification*- Class D Divisions IB and 2A. References' 1. N. Ito. Y. Hiasa, Y. Knoshi and M. Marugami, Cancer Research, 29: 1137-45 (1969). 2. Air Products and Chemicals, Inc., data. Report available upon request. 3. R. H. Cardy, J. of National Cancer Institute. 26(4) 1107-1115, (1979), EEC Risk and Safety Phrases= R 12, 20, 21, 22, 36, 37, 38 S 24, 25, 26, Z8, 36, 37, 39, 46 Woodward-Clyde
Dinitrotoluene (DNT) JUL-02-'93 FRI 14:09 ID:INDHYG 300S «375 P02
Air Products and Cheimcils. inc. AIR 720Altentown1 Hamilto. PnA 18195-150Boulevard 1 FTfUWUUBOOfW IT*T^f CO Telephone (215) 481-4911 MATERIAL SAFETY DATA SHEET
SECTION 1 - MATERIAL IDENTIFICATION PRODUCT NAME DXNITROTOLUENE PRODUCT CODE _DNT MSDS REVISION NUMBER* 6200-07 MANUFACTURER Air Products and Chemicals, Ino 7201 Hamilton Blvd., Allentown, PA 18195-1501 EMERGENCY TELEPHONE NUMBERCS) 800-523-9374 (Continental U.S.) 215-481-7711 (Outside Continental U.S.) 800-322-9092 (Pennsylvania only) DATE PREPARED SEPTEMBER 1992 REVISION NOTES* New MSDS Format C.A.S. CHEMICAL NAME121-14-2 2,4-Dinitrotoluane with 606-20-2 2,6-Dinitrotoluene SYNONYMS None CHEMICAL FAMILY: Aromatic Nitro Compound EMPIRICAL FORMULA Mixture INTENDED USE Chemical Intermediate SECTION 2 - INGREDIENTS CAS Number and Chemical Name X OSHA AC6IH PEL/TLV-TWA STEL-TWA ppm morm3 PPM morm3 121-14-2 2,4-Dinitrotoluene 80 N/E N/E 606-20-2 2,6-Dinitrotoluene 20 NXE N'E NXE = Not Established TVS = Trade Secret -S = Skin SECTION 3 - HEALTH HAZARDS
EJ EMERGENCY OVERVIEW HMIS HEALTH RATING 3 FLAMMABILITY 1 REACTIVITY 0 Solid, Yellow, Penetrating Toxic (ANSI Z129.1, 1988) by ingestion and inhalation. 121-14-2 2,4-Dinitrotoluene listed as a carcinogen by NIOSH CIS 144. Ignition will give rise to a Class A fire. In case of fire use Mater Spray. XKKKKXXXXXKKKXKKXKXKXXKKKXKKKKKKKKKXKKKKKXXXXKXXXKXXKKXXKXXXXKXXKKXXXXKKXX ROUTES OF EXPOSURE jUL_02-'93 FRI 14:10 ID:INDHYB 3006 8375 P03
720Ai1r ProductHamilto* n wnBoulevard Chemicalsd , Inc. PIRODC/CTC ±~1 TbtophonAllentowna. (215PA )18195-150 481-49111 Ingoction Skin Absorption Inhalation EXPOSURE STANDARDS OSHA PEL-THA 1.5 mg'm3| ACGIH TLV-TWA 1.5 mg/m5. HEALTH HAZARDS: Toxic (ANSI 2129.1, 1988) by ingastion and inhalation. 1Z1-14-Z 2,4~Dinitrotoluene listed as a carcinogen by NXOSH CIB §44. TARGET ORGANS Blood Heart Liver or the hepatic system Kidney Central nervous system Reproductive system SIGNS AND SYMPTOMS OF EXPOSURE CAcute effects) Product is absorbed through the skin and may cause nausea, headache and general discomfort. Systemic effects may include fatigue, lassitude, irritability, headache, nausea, vomiting and/or diarrhea. SIGNS AND SYMPTOMS OF EXPOSURE (Possible Longer Term Effects) Repeated and/or prolonged exposures may result in liver disorders (such as jaundice or liver enlargement); kidney disorders (such as edema, or protainuria); nervous system disorders (such as narcosis, behavioral changes or decrease in motor function); blood chemistry changes (such as cyanosis or loss of consciousness); reproductive disorders (such as birth defects or sterility) and/or muscular dysfunction. MEDICAL CONDITIONS GENERALLY AGGRAVATED BY EXPOSURE Heart disease Kidney disorders Liver disorders IRRITATION EFFECTS DATA No irritation data are known for this product. ACUTE TOXICITY EFFECTS DATA Oral LD50 (rat)< 790 mg/kg Dermal LD50 Crabbit): 1000 mg/kg Inhalation LC5D (rat): 2 mg/L OTHER ACUTE EFFECTS No Data CHRONICXSUBCHRONIC DATA Results from a battery of short term genotoxic tests on this material indicate mutagenie activity. Component has caused cancer in laboratory animals. JUL-02-'93 FRI 14:10 ID:INDHYB 3006 «375 P04
Air Products mnd Chemicals. Inc. Atl> f 720Allentown1 Hamilto. PnA 18195-150Boulevard 1 PRODUCTSnnj-tnf §f*w£ +Z— —<•»' Tolsphorw (216) 4B1-4&11 Component has caused reproductive affects in lab animal* SECTION 4 - FIRST AID
EYE CONTACT Hold eyelids apart and immediately flush eyes with plenty of water for at least 15 minutes. Call a physician. SKIN CONTACT Nash affected area with soap and water. INHALATION Move patient to fresh air. If breathing has stopped or is labored give assisted respiration (e.g. mouth-to-mouth). Supplemental oxygen may be indicated. Call a physician. There has been no clinical experience with overexposure via the respiratory route. INGESTION If swallowed* call a physician immediately. Induce vomiting or remove stomach contents by gastric suction only as directed by medical personnel. Never give anything by mouth to an unconscious person. SECTION 5 - FIRE AND EXPLOSION DATA CHARACTERISTICS! Flash Point 404F C207C) C2, 4 isomer) Upper Explosion Limit (UEL) No Data Lower Explosion Limit (LED No Data Autoignition Temperature No Data Flash Point Method(s) Not specified Fire Hazard Classification Combustible Liquid, Class IIIB COSHA/NFPA) EXTINGUISHING MEDIA Ignition will give rise to a Class A fire. In case of fire use Hater Spray. SPECIAL FIRE FIGHTING PROCEDURES Fire-fighters should wear butyl rubber boots, gloves/ and body suit and a self-contained breathing apparatus. Retain expended liquids from fire fighting for later disposal. Mater spray is also useful in cooling fire-exposed tanks and in dispersing vapors. UNUSUAL FIRE AND EXPLOSION HAZARDS May generate toxic or irritating combustion products. SECTION 6 - REACTIVITY HAZARD DATA JUL-02--93 FRI 14:11 ID:INDHYB 3006 «375 P0S
730Air 1 ProductHamiltot n anBoulevard Chemicalsd , Inc. AIR Alleniown. PA 18106-1501 Telephone (215) 481-4911 CHEMICAL STABILITY Stable at ambient temperatures. CONDITIONS TO AVOID (if Unstable) Admixture with organic chemicals or combustibles. INCOMPATABILITY CMaterials to Avoid) None known. HAZARDOUS DECOMPOSITION PRODUCTS Cfrom burning, heating, or reaction with other materials) Carbon Monoxide in • fire Carbon Dioxide in a fire Nitrogen Oxides in a fire Irritating and toxic fumes at elevated temperatures. HAZARDOUS POLYMERIZATION Hill not occur. CONDITIONS TO AVOID (if may occur) NFPA Reactivity Rating SECTION 7 - SPILL, LEAK AND WASTE DISPOSAL INFORMATION CONTAINMENT TECHNIQUES tRemoval of ignition sources, diking etc) Ventilate the space involved. CLEAN-UP PROCEDURES Shovel spilled chemical product into empty, dry container for later disposal or recovery. Flush area with hot water spray. OTHER EMERGENCY ADVICE Hear protective clothing, boots, gloves, and aye protection. Evacuate the area until the product solidifies. Prevent spilled product from entering streams or drinking water supplies. Notify local health authorities and other appropriate agencies if such contamination should occur. Potential for carbon monoxide and/or nitrous oxides generation in a fire must be recognized. HASTE DISPOSAL' Comply with all Federal, State and Local Regulations. Dilute with organic solvent and incinerate using effluent gas scrubber. For small quantities: Incinerate in suitable combustion chamber. Incinerate in an open container. ENVIRONMENTAL EFFECTS 2,4- and 2,6-DNT are assigned RCRA Hazardous waste numbers U105 and U106 respectively; banned from landfill except with special permit. JUL-02--93 FRI 14:11 ID:INDHYG 3006 8375 P06
T«MAir MProduct U*tfM:ttA«s i anR««>.lAd Chemicals*vH , Inc. __ ^ _ _ _ _^^*TAIR* 7201 Hamilton bomevnru g mar*r«* M^*r^ TelephonAllentowne . (215PA )18195-150 481-49111 JWLJfJtJl^f0
SECTION 8 - PERSONAL PROTECTXON'EXPOSURE CONTROLS EYE PROTECTION: Chemical safety glasses or Splash-proof eye Boggles. Nhen molten product is being handled' Full face shield with goggles underneath. HAND PROTECTION* Rubber gloves. RESPIRATORY PROTECTION In poorly ventilated areas, a cartridge mask National Institute for Occupational Safety and Health (NIOSH) approved for organic vapors is recommended. PROTECTIVE CLOTHING Rubber apron; Rubber boots ENGINEERING CONTROLS Maintain air concentrations in work spaces in accord with standards outlined in Sections 2 and 3. WORK AND HYGIENIC PRACTICES Hash at the end of each workshift and before eating? smoking or using the toilet. Launder or discard contaminated clothing. SECTION 9 - STORAGE AND HANDLING STORAGE Keep in cool/ dry, ventilated storage and in closed containers. Protect containers against physical damage. Keep container closed. HANDLING Avoid contact with skin or ayes. Avoid contact with skin, eyes, or clothing. OTHER PRECAUTIONS Emergency showers and eye wash stations should be readily accessible. Adhere to work practice rules established by government regulations (e.g. OSHA). SECTION 10 - PHYSICAL AND CHEMICAL PROPERTIES PHYSICAL FORM Solid COLOR Yellow ODOR Penetrating TYPICAL PHYSICAL DATA pH No Data JU_-02-'S3 FRI 14:12 IB:INDHYB 3006 8375 P07
720Air1 ProductHamilto* n anBoulevard Chftmtoafsd , Inc. AIR TelephonAllemowne . (215PA 18195-150} 481-43111 PRODUCTS VAPOR PRESSURE Cna H0> 1 a 106C VAPOR DENSITY CAir =15 6,3 BOILING POINT 515-57ZF (267-300C) a 769 MmHy FREEZINGXMELTING POINT 133-140F C56-6QCJ SOLUBILITY IN WATER 0.05^X1000 solution SPECIFIC GRAVITY CHater = 1) 1.346 a 151F Cmoltan) 1.31 a 176F tmolten} EVAPORATION RATE CButylacetata i) No Data VISCOSITY CCPSX No Data MOLECULAR HEIGHT Mixture SECTION 11 - TRANSPORTATION INFORMATION UN No. DOT SHIPPING NAME CNonbulk) Hazardous Substance, solid, N.O.S.; Dinitrotoluenes; ORM-E, NA9188; Chamieals N.O.I. IMO SHIPPING NAME Dinitrotoluenes, Solid; Poison; Poison B; UNZ038; INDG CODE PAGE* 6137; Packaging Group II IATA SHIPPING NAME Dinitrotoluenes, Solid; Poison; Poison B; UN2035; IMDG CODE PAGE' 6137; Pnckaoinn Group II SECTION 12 - U.S. FEDERAL REGULATIONS TOXIC SUBSTANCES CONTROL ACT CTSCA)- All components are included in the EPA Toxic Substances Control Act CTSCA) Chemical Substanca Inventory OSHA Hazard Communication Standard C29CFR1910.1200) hazard class(es) Carcinogen Toxic by inhalation and insestion. EPA SARA Title III Section 312 C40CFR370) hazard class Immediate Health Hazard Delayed Health Hazard EPA SARA Title III Section 313 C40CFR372J toxic chemicals above "do minimis" level are 121-13-2 2>4~Dinitrotoluena at no more than SQJf 606-20-2 2,6-Dinitrotoluene at no more than 20* SECTION - STATE REGULATIONS Proposition 65 substaneefs) listed by the state of California under the "Safe Drinking (later and Toxic Enforcement Act of 1986" 121-14-2 2,4-Dinitrotoluene JUL-02-'93 FRI 14:12 IBsINDHY5 3006 8375 P08
Air Product* and Chemical*. Inc. AIR Allentown7201 Hamilto. PnA 18195-150Boulevard 1 fTCUUIrtrDDSinf HT'f CO Telephone (215) 481-4911 New Jersey Trad* Secret Ragictry NumberCic) Nona SECTION 14 - INTERNATIONAL REGULATIONS CANADA REGULATORY DSL Included on Inventory WHMIS Hazard Classification Class D Division IB Class D Division 2A WHMIS Trade Secret Registry NumberCs) WHMIS HAZARDOUS INGREDIENTS Included in Section 2 LABELING HHMIS Symbol Skull and Crossbonas, Stylized T EUROPEAN ECONOMIC COMMUNITY IEEC) REGULATORY EINICS Master Inventory Included on Inventory LABELING EEC SYMBOL Harmful EEC Council Directives relating to the classification, packaging and labeling of dangerous substances and preparations Risk CR) and Safety tS) phrases Harmful by inhalation, in contact with skin and if swallowed. May cause cancer. May cause heritable genetic damage. Avoid contact with skin. After contact with skin, wash immediately with plenty of water. Hear suitable protective clothing* gloves and ayefface protection. Woodward-Clyde
APPENDIX B CHECKLIST OF ACTIVITIES TO BE COMPLETED PRIOR TO EXCAVATION OR DRUM HANDLING Woodward-Clyde
APPENDIX B CHECKLIST OF ACTIVITIES TO BE COMPLETED PRIOR TO EXCAVATION OR DRUM HANDLING
_WCC - Notify residents immediately adjacent to the site of activities to be conducted that day and estimated completion time. Determine which will be home. Eagle - Set up fenceline and off site air monitors as required in the "Air Monitoring Plan" (real time, integrated sampling, and particulates). __Eagle - Set up supplemental air monitoring equipment to collect integrated air samples at off-site 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 monitor for TDI. (See Section 4.2) __GDC - Calibrate and begin monitoring with OVA and TDI air monitors. (See Section 4.1 of this plan and Sections 2.1.5 and 2.1.7 of the GDC Health and Safety Plan.) __GDC - Establish Exclusion Zone, to include the portions which may extend outside of the site fence where appropriate. __Security - Place an individual to monitor those portions of the Exclusion Zone which may be outside of the site fence to prevent entry by anyone not in Level B protective equipment. __GDC - Ensure that all required equipment is on hand and functional. (See Appendix C)
92BQ59C-D/DRUM059.A-B COMBUSTN 07-09-93 Woodward-Clyde
APPENDIX C EQUIPMENT LIST FOR EXCAVATION AND DRUM HANDLING Woodward-Clyde
APPENDIX D CONFINED SPACE ENTRY PERMIT HS-513.12 WOODWARD-CLYDE CONFINED SPACE ENTRY PERMIT Page I of 3
PROJECT NAME/NUMBER ______• EXACT LOCATION OF PERMIT REQUIRED CONFINED SPACE
PURPOSE OF ENTRY AND DESCRIPTION OF WORK
POSSIBLE HAZARDS
HAZARD CONTROL MEASURES E.G. (ISOLATION, VENTILATION)
NAMES OF AUTHORIZED ENTRANTS
NAMES OF ELIGIBLE ATTENDANTS (OUTSIDE)
INDIVIDUALS ELIGIBLE TO BE IN CHARGE I Pace 2 of 3 I INITIAL ATMOSPHERIC SAMPLING I• .^TES™ T LOCATION READING ACCEPTABLE
'sssuSSn == _J»PM sf- -"s^**g- JLPPM I _PPM TESTS PERFORMED BY 9 SIGNED TIME DATE • FOR CONTINUOUS OR PERIODIC MONITORING, RECORD RESULTS IN W-C HEALTH AND I SAFETY REPORT I RESCUE SERVICE INFORMATION I RESPONDING TEAM ADDRESS I PHONE NUMBER •LIST OF RESCUE EQUIPMENT REQUIRED ON SITE I 'COMMUNICATION PROCEDURES AND EQUIPMENT i 1———————————— PERSONAL PROTECTIVE EQUIPMENT REQUIRED
L—— ______
I Woodward-Clyde
APPENDIX E OSHA 42 AIR MONITORING METHOD MCO FORMULA: ^ ; CgHgN^ .______TOLUENE-2.4-OIISOCYANATE M MIOSH METHOD: 2535 M.H.: 174.16______ISSUED; 8/15/87 OSHA: 0.02 ppm (ceiling) PROPERTIES: liquid; HP 19.5-21.5 «C; BP 251 *C; NIOSH: 35 vg/knVlO hrs; 140 pg/m»/10 nrin density 1.2244 g/M. f 20 *C; ACGIH: TIM 0.005 ppm; 3 STEL 0.02 ppm VP ca. 1.3 Pa (0.01 nm Hg ; 0.96 (1 ppm = 7.12 mg/w * NTP) mg/m*) « 20 *C SYNONYMS: 2,4-TOI; 2,4-bis(carbonylamino)to1uene; CAS *584-84-9. SAMPLING i MEASUREMENT SAMPLER: TUBE WITH REAGENT-COATED GLASS WOOL {TECHNIQUE: HPLC, UV DETECTION (N-[(4-nitrophenyl)methyl]- ! 1 propylamine on glass wool) iANALYTE>: 3,3 -bis[(4-nitroDheny1)methy1]- ! 3,3 -dipropyl-1,r-(4-fflethyl-1,3- FLOW RATE: 0.2 to 1 L/srin ! 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 yL SHIPMENT: protect fron light ! {MOBILE PHASE: 55:45 (v/v) CHgCftHjgO with SAMPLE STABILITY: at least 14 days 9 25 °C [1] ! 0.08X EtN and 0.16X HTO; ! 1.0 nL/fcin 3 3 4 STABILITY OF REAGEN 0T ON GLASS WOOL: ! < 7 days 9 25 C; > 4 weeks 9 -21 °C i{DETECTOR: UV 9 254 m FIELD BLANKS: 10X of samples iCOLUMN: 25 cm x 4.6 m; octadecylsilylated ______! silica, 5-i*i particle size ! ______ACCURACY______{CALIBRATION: standard solutions of 2,4-TDIU in CH30H RANGE STUDIED: 0.039 to 0.53 ng/ffl*[l] ! (67-L samples) i{RANGE: 0.3 to 25 yg 2,4-TOI per sample BIAS: none found [1] {ESTIMATED LOO: 0.1 fig 2,4-TDI per sample • OVERALL PRECISION (sr): 0.033 [1] {PRECISION (sr): 0.067 [1] ______•______APPLICABILITY: The working range is 0.004 to 0.35 ppm (0.03 to 2.5 mg/ta*) for a 10-L air sample. This method is applicable to isocyanate vapors (2,4-TOI vapor, 2,6-TOI vapor, and hexamethylene diisocyanate (KOI) vapor) [2,3], but not aerosols because of inefficient collection of aerosols and incomplete reaction of aerosol isocyanates with reagent.______INTERFERENCES: The reagent is slightly unstable in the dark at 25 °C. Tailing during HPLC, a result of reagent deterioration, may raise detection limits .______OTHER METHODS: This revises P&CAM 326 [4]. Sango used similar HPLC conditions [5]. Melcher reviewed methods for isocyanates [6].______8/15/87 2535-1 MIOSH Manual of Analytical Methods I TOLUENE-2.4-OIISOCYANATE METHOD: 2535 EQUIPMENT: I REAGENTS: 1. 2,4-TDI* (see APPENDIX A). 1. Sampler: glass tube, 4 cm x 6 nm ID, containing 2. N-[(4-nitrophenyl)methyl]- two sections of reagent-coated glass wool (see propylaorine hydrochloride. APPENDIX C); front section, 7 mm long; back I 3. 2,4-TOIU (see APPENDIX B). section, 5 mm long. Reagent-coated glass wool is 4. Methanol, chronatographic quality. compressed tightly. Seal ends of sampler with 5. Calibration stock solution, plastic caps. Wrap midsection of sampler with I 10 mg/mL. Dissolve 50 ng black tape. Protect sampler from light. Sampler 2.4-TDIU in methanol to make 5 ml may be stored at -21 °C in the dark for at least solution. four weeks. Limit period of storage of sampler at 6. Mater, distilled. 25 °C in the dark to seven days. I 7. NaOH. 1 M. 2. Separatory funnels, 125-mL. 8. Toluene, reagent grade. 3. Beakers, 50- and 125-mL. 9. Dichloromethane, reagent grade. 4. Aluminum foil. I 10. Hexane, reagent grade.* 5. Glass wool, silanized. 11. Nitrogen, purified, compressed. 6. Glass rod, 15 on x 4 nm. 12. Mobile phase. Mix 0.8 mL 7. Tweezers. I triethylamine and 1.6 mL 8. Glass tube with right-angle bend, 4.5 cm x 6 HUD ID, with 1 L 55:45 wrapped with black tape. H20 (v/v).* 9. Rubber tubing, opaque 1.5 cm x ca. 8 am ID. 13. Oibutylamine, 99X pure. 10. Personal sampling pump, 0.2 to 1 L/min, with I 14. Tetrahydrofuran, reagent grade.* flexible connecting tubing. 15. Branocresol purple indicator 11. High pressure liquid chromatograph, 254-nm UV solution. detector, integrator, and column (page 2535-1). I 16. HC1, 0.05 M, standardized. 12. Vials, glass, 2-mL, caps lined with PTFE. 17. 2,4-TDI stock solution. 13. Pipets. 2-, 15-, and 25-mL. 100 mg/mL. Dissolve 500 ng 14. Ultrasonic bath. 2,4-TDI in dichloromethme to 15. Syringes, 100-jiL, readable to 1 pL. I make 5 mL solution. 16. Syringes, 10-yL, readable to 0.1 jiL. 17. Volumetric flasks, 5-mL. *See SPECIAL PRECAUTIONS. 18. Buret, 50-mL. I 19. U-tube, glass, 25 on x 15 HI ID, glass stopcocks. 20. Sorbent tube, glass, 7 cm x 6 mw, coconut shell charcoal, ca. 150 mg. I SPECIAL PRECAUTIONS: 2,4-TOI can irritate the eyes and skin, and can cause bronchial asthma and allergic eczema. Flash points of hexane, tetrahydrofuran and triethylamine are -26 *C, -17 I °C, and -6 °C, respectively. I SAMPLING: 1. Calibrate each personal sampling pump with a representative sampler in line. 2. Remove plastic caps from sampler. Attach one end of glass tube with right-angle bend I directly to inlet of sampler with short piece of opaque rubber tubing. 3. Sample 2 to 170 L of air at 0.2 to 1 L/min. Seal ends of sampler with plastic caps. SAMPLE PREPARATION: I 4. Transfer front and back sections of reagent-coated glass wool to separate vials, Add 2mL methanol. Seal vials. 5. Place vials into ultrasonic bath for 3 min. I 8/15/87 2535-2 MIOSH Manual of Analytical Methods I METHOD; 2535 ______TOLUENE-2. 4-0 I ISOCYANATE CALIBRATION AND QUALITY CONTROL: 6. Calibrate daily with at least five working standards over the range 0.3 to 80 pg 2,4-TOIU per 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 (steps 8 and 9). c. Prepare calibration graph (peak area vs. yg 2,4-TOIU). 7. Determine recoveries from samplers in the range 0.3 to 25 tig 2,4-TDI per sample. Prepare three samples at each of three levels plus three media blanks. NOTE: Recoveries should be quantitative. If recoveries are not quantitative, attempt to determine the reason for error. a. Prepare a series of standard solutions of 2,4-TDI in dicnlorometnane in the range 0.06 to 5mg/mL. 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 or reaction on the inside wall of the tubing. c. Connect charcoal soroent tube to inlet of U-tube (charcoal can adsorb contaminants of air which would react with 2,4-TDI). d. Draw ambient air through the charcoal tube, U-tube, and sampler with a sampling pump at 1 L/min. e. Place 5 iiL of a standard solution of 2,4-TDI into the U-tube. f. Allow 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). MEASUREMENT: 8. Establish chromatographic conditions indicated on page 2535-1. 9. Inject sample aliquot manually or with autosampler. Measure peak area. CALCULATIONS: 10. Determine the mass dig) 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 % > Hf/10. report breakthrough and possible sample loss. 11. Calculate concentration, C, of 2,4-TDI in the air volume sampled, V (L):
where 0.310 = M.W. of 2,4-TDI/R.H. of 2,4-TOIU. EVALUATION OF METHOD: A variation of this method which involved normal-phase HPLC (Method P&CAN 326} was tested with fortified samplers and atmospheres generated with a diffusion cell [1,4]. Average recoveries of 2,4-TOIU from front sections of reagent-coated glass wool were 0.97 to 0.99 after applications of 1.0-, 2.1-, 9.9-, and 20.0-pg quantities of 2,4-TDI from a U-tube; s was 0.067 (21 samples, pooled). s was 0.033 (29 samples, pooled) for 67-L samples at 0.03r 9 to 0.53 mg/m*. The independent methor d used for evaluation was that of Meddle 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. Breakthrougs h volume was 71 L (0.53 mg/m*. 1 L/min); breakthrough volume was 279 L (0.14 mg/m, 1 L/min). 2,4-TOIU was stable on coated glass wool at room temperature in the dark for 14 days. The reagent, N-[(4-nitrophenyl)methy1]propylamine, is unstable [1].
8/15/87 2535-3 NIOSH Manual of Analytical Methods I TOLUENE-2.4-01ISOCYANATE METHOD: 2S3S I Evaluation of samplers with 2,4-TDI aerosols was not performed. However, samplers were inefficien> t collectors when aerosol particles were present in an atmosphere of 4,4 -fflethylenediphenylisocyanate (HOI). The collection efficiency of each sampler for HDI was about 90* (flow rate, 1 L/nin; total concentration of HOI in vapor and aerosol forms, about I 0.52 mg/ra*; mass median diameter of HOI particles, about 0.6 JJTO; geometric standard deviation, about 2.2) [1]. I REFERENCES: [1] Tucker, S. P., and J. E. Arnold. Anal. Chem.. 54, 1137-1141 (1982). [2] Swinehart. G., K. Mulligan, C. Rice, R. HcKay, N. Gener, and G. E. Burroughs. I "Hexamethylene Oiisocyanate Honomer and Prepolymer Characterization," presented at the American Industrial Hygiene Conference, Dallas, TX (Hay 20, 1986). [3] Carson, K. A. "Isocyanate Monitoring Using M-p-nitrobenzyl-N-propylamine glass fiber sampling tube," OEHL-82-022EH163HAE, Air Force Occupational Environmental Health I Laboratory, Brooks AFB. TX (1982); report (No. AO-A119901) available from NTIS, Springfield, VA 22161. [4] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 6, P&CAH 326, U.S. Department of Health I and 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] Meddle, 0. U., and R. Wood. Analyst (London). 95, 402-407 (1970). I [8] Hastings 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. I APPENDIX A: Determination of Purity of 2,4-TDI Dissolve 480 yL (365 mg. 0.00282 mole) dibutylamine in 10 mL tetrahydrofuran. Add 100 jiL (122 mg, 0.000701 mole) 2,4-TOI. Stir the mixture and allow to stand 6 min. Add a few drops, I of bromocresol purple indicator solution. Prepare two additional samples in this manner. Titrate excess dibutylamine with 0.05 H HC1. Calculate percent purity, P, of 2,4-TDI for each sample: B I P = < -=^5> • 100. where: B = Molar quantity of dibutylanine before reaction (0.00282) I V = Volume of 0.05 H HC1 (L) M = Concentration of HC1 (0.05M) 2 = Number of moles of dibutylamine required to react with 1 mole of 2,4-TDI I H = Molar quantity of 2,4-TDI added to tetrahydrofuran solution (0.000701) APPENDIX B: Preparation of 2,4-TDIU [8] I Dissolve 1.03 g (0.00446 mole) N-[(4-nitropheny1)methy1]-propylamine hydrochloride in 25 ml water in a 125-mL separator? funnel. Add 15 mL 1 M NaOH and shake the mixture. Extract the I f*-C(4-nitrophenyT)methyl]propy1amine with 50 mL toluene, and separate the phases. Add a solution of 262 til- (321 mg, 0.00184 mole) 2,4-TDI in 30 mL toluene to the solution of N-[(4-nitrophenyl)methyl]propylamine. Collect the precipitate by filtration. Purify the I product by dissolving it in a small volume of dichloromethane and precipitating it with hexane. Dry the product rn vacua (MP = 136 to 139 °C). 8/15/87 2535-4 M10SH Manual of Analytical Hetfwds I METHOD: 2535______TOLUEME-2.4-OIISOCY/WATE APPENDIX C: Preparation of Reagent-Coated Glass Wool Dissolve 300 ng (0.00130 mole) R-C(4-nitrophenyl)nethyl]propylamine hydrochloride in 25 nL water in a 125-mL separatory funnel. Add 15 nL 1 « NaOH and shake the mixture. Extract the N-[(4-nitrophenyl)methyl]propy1amine with 50 mL hexane. Transfer 40 aL of the hexane solution to a 50-fliL beaker which is wrapped with aluminum foil and contains 1.82 g silanized glass wool. Under .dim light, evaporate hexane from the beaker with the aid of a stream of nitrogen. Knead the glass wool with a glass rod to produce a uniform coating. Continue to evaporate hexane until the glass wool appears dry. Protect the coated glass wool from bright light. The quantity of coated glass wool is sufficient for the preparation of the front and back sections for twenty samplers.
8/15/87 2535-5 KIOSK Manual of Analytical Methods Woodward-Clyde
APPENDIX F NIOSH 2535 AIR MONITORING METHOD DIISOCYANATES 1,6-HEXAMETHYLENE DTTSOCYANATE (HOT) TOLUENE-2,6-DIISOCYANATE (2,6-TDI) TOLUENE-2,4-DIISOCYANATE (2,4-TDI)
Method no.: 42 Matrix: Air Procedure: Samples are collected by drawing a known vol- ume of air through glass fiber filters coated with 0.1 mg of l-(2-pyridyl)piperazine (1-2PP) which are contained in open-face cassettes. Samples are extracted with 90/10 (v/v) aceto- nitrile/dimethyl sulfoxide (ACN/DMSO) and ana- lyzed by high performance liquid chromato- graphy (HPLC) using an ultraviolet or fluo- rescence detector. (The coated filters used in Method 47 for MDI are also acceptable for this procedure. Those filters are coated with 1 mg instead of 0.1 mg of 1-2PP.) Recommended air volume and sampling rate: 15 L at 1 L/min Special requirements: It is recommended that coated glass fiber fil- ters be stored at reduced temperature until used for sampling. Status of method: Evaluated method. This method has been sub- jected to the established evaluation proce- dures of the Organic Methods Evaluation Branch. Date: February 1983 Chemist: Donald Burright March 1989 (Revised) Carcinogen and Pesticide Branch OSHA Analytical Laboratory Salt Lake City, Utah Analyte______2,6-TDI____HDI_____2,4-TDI Target concentration, ug/m3(ppb): 140(20) 140(20) 140H20)
Detection limit of the 3 overall procedure, ug/m (ppb): 1.6(0.23) 2.3(0.32) 1.3(0.17)
Reliable quantitatio3 n limit, ug/m (ppb): 2.3(0.32) 2.9(0.43) 2.5(0.36) Standard error of estimate at target concentration, %: 7.63 7.79 6.89 (Section 4.9.) 'OSHA PEL (Air concentrations are based on 15-L air sample volume.)
1. General Discussion 1.1. Background 1.1.1. History Some of the earliest procedures to determine atmospheric diisocyanate concentrations were developed by Ranta and Marcali (Ref. 5.1.). Both of these procedures are incon- venient because they use a bubbler for sampling and their colorimetric analyses are non-specific. A later sampling procedure uses p-nitrobenzyl-N-n-propylamine (nitro rea- gent) in toluene bubblers (Ref. 5.2.). While this method is specific for diisocyanates, it still retains the use of the bubbler and nitro reagent which is unstable when stor- ed for long periods of time, even if it is kept at reduced temperature. The past couple of years have seen several new derivatizing reagents being used; they include N-meth- yl-1-naphthalenemethylamine (Ref. 5.3.), 9-(n-methylamino- methy1)-anthracene (Ref. 5.4.) and l-(2-pyridyl)piperazine (1-2PP) (Refs. 5.5.-5.7.). The collection procedure of these new studies all involve the use of toluene bubblers. The purpose of this study was to find a collection system that does not use a bubbler, yet retains the sensitivity, precision and accuracy of the nitro reagent method. 1-2PP is a suitable derivatizing reagent, when coated on a glass fiber filter, for several reasons: 1) The high boiling liquid is retained on a glass fiber filter and stability is not a problem. 2) The rapid and exothermic reaction vith both aromatic and aliphatic diisocyanates results in derivatization on the filter (Ref. 5.7.). 42-1 I 3) The derivatives have higher molar absorptivities in the UV region than those formed with nitro reagent which allows the extraction volume to be larger without loss I - of sensitivity (Ref. 5.5.). This procedure compares favorably when tested side-by-side I with the nitro reagent method by Cummins (Ref. 5.10.) for 2,4-TDI. {Section 4.10.) Additional work is being done to study 4,4'-methylenediphenylisocyanate and isophorone di- isocyanate using 1-2PP as the derivatizing reagent. I Additional work was performed on this procedure to reflect to change in Title 29 CFR 1910.10003 , Table Z-l-A in 1989. I The Ceiling PEL of 0.14 mg/m fo3 r 2,4-TDI was replaced with an 8-h TWA PEL of 0.04 mg/m . The sampling time can be increased to 240 min at a sampling rate of 1 L/min. (Sections 4.6. and 4.12.) I 1.1.2. Toxic effects (This section is for information only and should not be taken as a basis for OSHA policy.) I Continued inhalation of diisocyanate vapors or mists can cause nausea, headache, coughing, irritation of the nose I and throat, shortness of breath and chest discomfort. Massive exposure can cause severe coughing spasms, bron- chitis and chemical pneumonitis. Some people can become sensitized to isocyanates and may suffer asthmatic attacks I and respiratory distress when subsequently exposed to very low concentrations (Ref. 5.9.). Recent studies have pro- duced conflicting results about the mutagenicity of TDI I (Refs. 5.1. and 5.9.). No data has been found to indicate that diisocyanates are carcinogenic or teratogenic (Refs. 5.1. and 5.9.). I 1.1.3. Operations where exposure may occur The manufacture of polyurethane foams, coatings, and elas- I tomers potentially exposes a minimum of 100,000 workers to diisocyanates (Ref. 5.2.). Diisocyanates can be found in paints, insulation, adhesives, automobile bumpers, shoe I soles, and hundreds of other applications (Refs. 5.2. and 5.8.). Over 700 million pounds of diisocyanates were produced in 1975 {Ref. 5.2.). I 1.1.4. Physical properties analyte 2,6-TDI HDI 2,4-TDI I CAS no. : 91-08-7 822-06-0 584-84-9 Mtf: 174.16 168.20 174.16 I bp, °C(mm Hg): 96(1.5) 213(760) 251(760) mp, °C: 8 1 -55 22 sp gr(75°C): NA1 1.05 1.22 vp, mm Hg: NA 0.05 0.025 I 42-2 I color: all colorless to pale yellow odor: all sharp pungent flash point(closed 1 cup), °C: NA 140 127 synonyms and structures: Figure 1.1.4. 'not available 1.2. Limit defining parameters (the analyte air concentrations listed through this method are based on an air volume of 15 L and an extraction volume of 2 mL.) 1.2.1. Detection limit of the analytical procedure The detection limit of the analytical procedure is the mass of analyte per injection which will result in a peak whose height is about 5 times the amplitude of the base- -• • line noise. (Section 4.1.) Analytical Detection Limit analyte_____2,6-TDI HDI 2,4-TDI ng/injection 0.18 0.18 0.18 1.2.2. Detection limit of the overall procedure The detection limit of the overall procedure is the amount of analyte spiked on the sampling device which allows re- covery of an amount of analyte equivalent to the detection limit of the analytical procedure. (Section 4.2.) Detection Limit of the Overall Procedure analyte 2,6-TDI HDI 2,4-TDI
ng/sampl3 e - 24 33 19 ug/m 1.6 2.3 1.3 ppb 0.23 0.32 0.17 1.2.3. Reliable quantitation limits The reliable quantitation limit is the smallest amount of analyte which can be quantitated within the requirements of at least 75% recovery and a precision (1.96 SD) of ±25% or better. The reliable quantitation limits are higher than the detection limits of the overall procedure to satisfy the precision requirement. (Section 4.3.) 42-3 I Reliable Quantitation Limits analyte 2,6-TDI HDI 2,4-TDI I ng/ sampl3 e 34 44 39 ug/m 2.3 2.9 2.5 ppb 0.32 0.43 0.36 I * I The reliable quantitation limit and detection limits reported in the method are based upon optimization of the instrument for the smallest possible amount of analyte. When the target concentra- I tion of an analyte is exceptionally higher than these limits, they may not be attainable at the routine operating parameters._____ 1.2.4. Sensitivity The sensitivity of the analytical procedure is determined by the slope of the calibration curve over a concentration range 0.5 to 2 times the target concentration. The sensi- tivity will vary somewhat with the particular instrument I used in the analysis. (Section 4.5.) Sensitivity of the Analytical Procedure I analyte 2,6-TDI HDI 2,4-TDI I area units per ug/mL 85600 84300 159000 I 1.2.5. Recovery The recoveries of the analytes from samples used in the I 18-day storage tests remained above the values presented below. These values are determined from the calculated regression lines of the storage graphs. (Section 4.9.) I The recovery of analyte from the collection medium after storage must be 75% or greater. I Recovery, % temp,°C 2,6-TDI HDI 2,4-TDI I -25 86.3 81.1 81.3 22 86.4 83.0 80.3 I I 42-4 I I 1.2.6. Precision (analytical method) The pooled coefficients of variation obtained from repli- cate determinations of analytical standards at 0.5, 1 and 2 times the target concentration are presented below. (Section 4.4.) Pooled Coefficients of Variation 2,6-TDI______HDI______2,4-TDI 0.009 0.013 0.009 1.2.7. Precision (overall procedure) The overall procedure must provide results at the target concentrations that are ±25% or better at the 95% confi- dence level. The precisions at the 95% confidence level for the 18-day storage test are presented below. (Section 4.9.) The reported values each include an additional ±5% for sampling error. Precision at the 95% Confidence Level, % 2,6-TDI HDI 2,4-TDI 14.9 15.2 13.5 1.2.8. Reproducibility Five samples, prepared by vapor spiking, and a draft copy of this procedure were given to a chemist unassociated with this evaluation. The samples were analyzed after 6 days of storage at -25°C. The data listed below are cor- rected for extraction efficiency (Section 4.8.). Recovery % 2,6-TDI HDI 2,4-TDI X 101.5 100.4 105.4 SD 1.6 2.0 2.4 1.3. Advantages 1.3.1. The sampling and analytical procedures are specific and sensitive for several diisocyanates employed in industry (Ref. 5.7.). 1.3.2. The collection system is less cumbersome than the use of a bubbler. 42-5 I 1.3.3. 1-2PP is more stable and less expensive than p-nitroben- zyl-N-n-propylamine (nitro reagent). I 1.4. Disadvantages The use of peak ratios to confirm low concentrations of diisocy- I anates is impractical due to the small response at 313 nm. 2. Sampling Procedure I 2.1. Apparatus 2.1.1. Samples are collected by use of a personal sampling pump I that can be calibrated to within ±5% at the recommended flow rate with the sampling device in line. I 2.1.2. A three-piece styrene cassette containing a glass fiber filter coated with 0.1 mg of 1-2PP and a backup pad. (Fig- ure 2.1.2.) I 2.1.3. Coated filters are prepared by applying 0.5 mL of a solu- tion of 0.2 mg/mL 1-2PP in methylene chloride to each glass fiber filter. The wet filters are allowed to air I dry before placing them in a jar. Vacuum is applied to the jar to remove residual methylene chloride. (The coat- ed filters used in Method 47 for MDI are also acceptable for this procedure. These filters are coated with 1 mg of I 1-2FP and are prepared as above except a 2.0 mg/mL solu- tion of 1-2PP in methylene chloride is used.) I 2.1.4. Coated filters should be stored at reduced temperature as a precaution. I 2.2. Reagents None required. I 2.3. Sampling technique 2.3.1. Remove the inlet cover from the three-piece cassette. I Save the cover for installation after sampling. 2.3.2. Attach the cassette in the breathing zone of the employee I to be monitored. 2.3.3. The recommended flow rate is 1 L/min with a recommended total air volume of 15 L. A longer 240-min sampling time I is permissible to comply with the 1989 change of the PEL. 2.3.4. After sampling for the appropriate time, remove the sam- I pling device and reinstall the small plug and inlet cover. 2.3.5. Wrap each sample end-to-end with an OSHA Form 21 seal. I 42-6 I 2.3.6. With each set of samples, submit at least one blank sam- ple. The blank should be subjected to the same handling as the samples except that no air is drawn through it. 2.3.7. Bulk samples submitted for analysis must be shipped in sealed vials and in a separate container. 2.4. Retention efficiency 2.4.1. Experimental design Due to present laboratory limitations, controlled test atmospheres of diisocyanates cannot effectively be gen- erated. However, the following procedure using a vapor spiking technique was used as an alternative to study analyte retention. This was done to approximate the rec- ommended open-face collection of diisocyanates. A glass syringe barrel equipped with a Luer taper tip was silanized and silanized glass wool was placed into the syringe. The Luer tip was inserted into the inlet part of a cassette so that the tip was flush with the inside sur- face of the cassette. The other end of the syringe was attached to a sampling port. The outlet of the cassette was attached to a vacuum pump. A critical orifice between the cassette and the pump maintained a constant 1 L/min ...... - flow rate. Dry air samples were prepared by attaching a dry air source to a manifold inlet. Humid air samples were gen- erated by passing air through water in a controlled tem- perature water bath. The humidity was monitored in the sampling manifold via a humidity probe. The glass wool was spiked with diisocyanate in methylene chloride. The .,. , desired quantity of air was then drawn through the glass wool, at a flow rate of 1 L/min, and onto the coated fil- ter, which was analyzed to determine analyte loss. 2.4.2. Retention results Humidity affects the ability of a glass fiber filter to retain derivatized diisocyanates. When a sample ten times the target concentration is vapor generated and 200 L of dry air (12% humidity) is drawn through the filter, an average of 95.4% of the diisocyanates is found on the coated filter. Only 1.2% is found on the backup pad. When higher relative humidity (R.H.) is added to the samp- ling system, a different result is obtained. After samp- les were vapor spiked at the target concentration using 20 L of dry air, several known volumes of humid air (78% R.H.) pulled through them. The samples showed increasing losses of diisocyanate derivative with increasing volumes of humid air. (Section 4.6.) 42-7 2.5. Extraction efficiency The average extraction efficiency for each of the analytes spiked at the target concentration on a coated glass fiber filter is presented below. (Section 4.7.) Average Extraction Efficiencies, % 2,6-TDI______HDI______2,4-TDI 91.2 93.3 90.8 2.6. Recommended air volume and sampling rate 2.6.1. The recommended air volume is 15 L for the OSHA Ceiling PEL. 2.6.2. The recommended air sampling rate is 1 L/min. 2.6.3. To comply with the 1989 PEL changes, the air volume can be increased to 240 L to sample for the OSHA TVA-PEL. 2.7. Interferences (sampling) Any compound, that could be collected on the glass fiber filter that could react with the 1-2PP or compete with it in the reaction to derivatize the diisocyanate, should be considered as an inter- ference. Potential interferences include anhydrides, amines, alcohols and carboxylic acids. 2.8. Safety precautions (sampling) The sampling equipment should be attached to the worker in such a manner that it will not interfere with work performance or safety. 3. Analytical Procedure 3.1. Apparatus 3.1.1. High performance liquid chromatograph equipped with UV detector, manual or automatic sample injector, and chart recorder. 3.1.2. HPLC stainless steel column capable of separating diiso- cyanate derivatives. The column employed in this study was a 25-cm x 4.6-mm i.d. All tech C (10 urn) stainless steel column. g 3.1.3. An electronic integrator, or some other suitable method of determining peak areas. 3.1.4. Vials, 4-mL with Teflon-lined caps. 42-8 3.1.5. Syringes, of convenient sizes for sample and standard preparations and injections. 3.1.6. Volumetric pipettes and flasks for preparation of stan- dards . 3.1.7. Suitable glassware for preparation of diisocyanate urea derivatives. 3.1.8. Micro-analytical balance used to weigh standard prepara- tions. 3.2. Reagents 3.2.1. Methylene chloride, hexane, acetonitrile, and dimethyl sulfoxide, HPLC grade. 3.2.2. Vater, HPLC grade. Our laboratory employs a commercially available water filtration system for the preparation of HPLC grade water. 3.2.3. l-(2-Pyridyl)piperazine, Aldrich, Milwaukee, VI. 3.2.4. 2,6-TDI, Carbolabs, Inc., New Haven, CT. 3.2.5. HDI, Aldrich, Milwaukee, WI. 3.2.6. 2,4-TDI, Eastman Chemicals, Rochester, NY. 3.2.7. Ammonium acetate, HPLC grade. 3.2.8. Glacial acetic acid. 3.3. Standard preparation 3.3.1. A solution containing 3.5 g of 2,4-TDI in 25 mL of meth- ylene chloride is slowly added to a stirred solution 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 methylene chloride to about 10 mL with a stream of dry nitrogen. The product is precipitated with hexane, (precipitation may start without adding hexane), filtered, redissolved in a minimal volume of methylene chloride and reprecipitated. The precipitate is filtered and washed with hexane (approximate yield is 9 g of the derivative after being dried by vacuum). This preparation is a modi- fication of the procedure reported by Goldberg et al (Ref. 5.7.). Derivatives of the two other diisocyanates are prepared by a similar procedure. 3.3.2. Preparation of working range standards A stock standard solution is prepared by dissolving the diisocyanate derivatives into DMSO. To express the deriv- 42-9 I ative as free diisocyanate, the amount of 2,4-TDI and • 2,6-TDI ureas weighed is multiplied by the conversion V factor 0.3479. TDI 174.16 M.«•W» urea~ ~ — 500.6.- f\t^^^7^^1 I Similarly, the conversion factor for HDI urea is 0.3400. • MV HDI 168.20 , TTT=—————MV urea —494.6 = 4 Tn~i—TT" n /n= nO.J4UU All dilutions of the stock solutions are made vith aceto- I nitrile to arrive at the working range. 42-11 I Table 4.2.1. Recoveries Near the Detection Limit analyte 2,6-TDI HDI 2,4-TDI I spiked found spiked found spiked found ng/sample 16.9 3.5 33.9 3.9 19.3 12.6 I 25.4 14.0 44.2 44.9 29.0 21.1 33.8 27.8 66.2 61.0 38.6 39.0 42.2 33.9 88.2 82.6 57.9 61.8 I 67.6 54.2 132.4 133.7 77.2 68.7 84.5 61.9 96.6 93.8 101.4 85.8 115.8 120.8 I 4.2.2. Graphical presentation of the above data are shown in I Figures 4.2.1.-4.2.3. The detection limits of the overall procedure determined from the Figures were 24.4 ng/sample for 2,6-TDI, 33.3 ng/sample for HDI, and 19.2 ng/sample I for 2,4-TDI. 4.3. Reliable quantitation limit I The following data were obtained by vapor spiking the analytes onto sampling devices. An injection size of 25 uL was used to de- termine the reliable quantitation limits. I Table 4.3. Extraction Efficiency at the Reliable Quantitation Limit I analyte 2,6-TDI HDI 2,4-TDI ng/sample 33.8 44.2 38.6 I % recovery 117.4 124.8 82.9 103.6 114.7 74.6 103.6 96.8 70.8 I 103.6 114.7 82.9 103.6 114.7 74.6 103.6 114.7 70.8 I 103.6 96.8 82.9 103.6 96.8 74.6 X 105.3 109.3 76.8 I SD 4.9 10.9 5.3 1.96 SD 9.6 21.4 10.4 I 4.4. Sensitivity and precision (analytical method only) I The following data were obtained from multiple injections of ana- lytical standards. I 42-12 I 1 Table 4.4.1. 0.5x Target Concentration analyte 2,6-TDI HDI 2,4-TDI Ug/mL 0.700 0.722 0.704 area 69054 70015 127935 counts 69310 70643 127591 69380 70996 127408 68824 70340 125457 68117 68751 124953 67271 68445 124032 68701 69385 126054 68643 69036 125588 67196 68454 124185 X 68499.6 69562.8 125911.4 SD 811 967 1454 CV 0.0118 0,0139 0.0115 Table 4.4.2. Ix Target Concentration analyte 2,6-TDI HDI 2,4-TDI yg/mL 1.400 1.443 1.407 area 127643 129539 236004 counts 126872 130474 235664 126332 128313 233651 127445 128379 234337 126896 129521 234274 126037 128186 231355 127077 129882 234258 126384 125878 229449 127033 128370 234524 X 126857.7 128726.9 233723.7 SD 526 1346 2076 CV 0.0041 0.0105 0.0089 42-13 I Table 4.4.3. 2x Target Concentration I analyte 2,6-TDI HDI 2,4-TDI ug/mL 2.800 2.886 2.814 area 249771 252219 459331 I counts 244922 249296 457553 248641 259363 458572 246677 252678 461448 I 246986 252581 461119 245615 250940 457897 252601 247011 463557 I 248169 249906 460536 248014 251679 459259 X 247932.9 251741. 4 459919.1 I SD 2309 3396 1925 CV 0.0093 0.0135 0.0042 I Table 4.4.4. Fooled Coefficients of Variation I 2, 6-TDI HDI 2,4-TDI I 0.0090 0. 0127 "" 0.0087 I 4.5. Sensitivity The data in Tables 4.4.1.-4.4.3. are presented graphically in I Figures 4.4.1.-4.4.3. 4.6. Retention efficiency I 4.6.1. Two retention studies were conducted, the first at 12% relative humidity and the second at 78% relative humidity. I The samples were vapor spiked and removed from the sample generator after a known volume of air had passed through the cassette. I I 42-14 I Table 4.6.1.1. Percent Retention at lOx Target Concentration with 200-L Air Volume (12% R.H.) analyte 2,6-TDI HDI 2,4-TDI tig/sample 27.92 36.44 31.84 filter 96.9 97.2 94.4 backup 1.0 2.0 0.8 filter 95.6 95.6 92.9 backup 0.9 1.8 0.6 Table 4.6.1.2. Percent Retention at Ix Target Concentration (782 R.H.) air volume, L 2,6-TDI HDI 2,4-TDI 5.25 90.8 91.5 85.1 5.25 90.3 88.4 84.0 10.5 91.2 89.8 84.5 15.75 89.7 92.0 82.6 15.75 89.7 86.7 78.9 21.0 89.8 90.0 82.3 21.0 85.1 88.4 77.4 26.25 88.8 93.8 81.7 26.25 84.0 92.4 78.2 31.5 84.5 87.5 77.1 36.75 84.7 89.1 80.0 42.0 86.8 90.3 80.1 42.0 85.9 90.0 79.7 47.25 84.9 84.7 79.2 47.25 84.0 84.4 75.7 52.5 87.4 90.9 80.8 52.5 86.4 87.2 79.4 4.6.2. The following data are presented to show that the diiso- cyanate derivatives, liquid spiked, are retained on the coated glass fiber filter at the recommended air volume. 42-15 I Table 4.6.2. Percent Retention at Ix Target Concentration with 20-L Air Volume (80% R.H) I analyte 2,6-TDI HDI 2,4-TDI ug/sample 2.792 3.644 3.184 I % recovery 83.7 79.6 76.0 93.1 81.4 88.5 90.1 81.1 86.3 I 95.8 81.7 91.4 89.4 80.8 86.5 83.6 78.9 78.9 I 78.9 75.0 73.0 88.6 82.3 82.7 X 87.9 80.1 82.4 I SD 5.5 2.3 6.4 I 4.6.3. Ten liters of 802 R.H. air were drawn through a filter to moisten it and then it was vapor spiked with 20 L of dry air to observe the retention of the derivative on the wet I filter. Table 4.6.3. I Recoveries From a Wet Filter analyte 2,6-TDI HDI 2,4-TDI I ug/sample 2.792 3.644 3.184 % recovery 100.5 91.6 84.4 99.6 90.6 79.4 I 97.8 88.8 77.8 104.2 , 95.9 84.4 97.8 89.7 81.7 I X 100.0 91.4 81.5 SD 2.6 2.8 3.0 I 4.6.4. Retention efficiencies at the 1989 TWA-PEL 1 The following data are presented to show that the diiso- cyanate derivatives, liquid spiked, are retained on the I coated glass fiber filter at the recommended air volume when sampling for the long periods of time needed to de- termine the TWA exposure. No isocyanate derivative was I detected on any of the glass fiber filters placed 0.25 in. behind the coated filters. I 42-16 I Table 4.6.4. Percent Retention at Ix 1989 TWA PEL with 240-L Air Volume (71% R.H) analyte 2,6-TDI HDI 2,4-TDI yg/ sample 8.412 8.240 8.376 % recovery 103.1 103.5 106.6 100.3 103.1 106.1 102.7 102.3 105.9 98.7 102.6 106.6 97.1 102.0 105.3 96.7 102.0 105.4 X 99.8 102.6 106.0 SD 2.7 0.6 0.6 4.7. Extraction efficiency The following data represent the analysis of coated glass fiber filters vapor spiked with the analytes at 0.05 and 1 times the target concentrations. Table 4.7.1. Extraction Efficiency at 0.05x Target Concentration analyte 2,6-TDI HOI 2,4-TDI yg/ sample 0.1396 0.1822 0.1592 % recovery 86.0 93.9 98.6 92.8 90.0 102.1 80.2 91.7 98.5 84.2 92.2 100.9 69.3 91.3 100.1 89.4 104.9 111.3 91.7 96.1 96.1 95.1 91.7 95.6 77.4 85.6 87.7 91.7 96.6 101.6 103.2 107.6 108.2 94.6 99.6 100.0 X 88.0 95.1 100.1 42-17 I Table 4.7.2. Extraction Efficiency at Ix Target Concentration analyte 2,6-TDI EDI 2,4-TDI I ug/sample 2.792 3.644 3.184 % recovery 92.0 92.2 93.0 I 95.6 98.9 98.1 92.6 94.1 92.9 92.4 92.9 94.4 I 91.8 92.9 92.0 93.7 94.9 93.9 , 88.3 94.5 85.8 89.6 92.8 85.5 I 90.2 94.3 88.6 90.8 91.5 90.5 87.7 88.6 87.5 I 89.9 92.3 87.6 X 91.2 93.3 90.8 I 4.8. Reproducibility data I Five samples were spiked with the three diisocyanates and had 20 L of humid air drawn through the cassettes. The samples were ana- I lyzed by a chemist unassociated with this evaluation after being stored for 6 days at -26°C. The results are corrected for extrac- tion efficiencies. I Table 4.8. Reproducibility Results, % Recovery I analyte 2,6-TDI HDI 2,4-TDI ug/sample 2.792 3.644 3.184 I 102.5 101.3 106.2 98.8 97.0 103.4 102.7 102.0 108.6 102.5 101.3 106.2 I 101.2 100.6 102.6 X 101.5 100.4 105.4 I SD 1.6 2.0 2.4 I 4.9. Storage data The data in Tables 4.9.2.-4.9.4. show the effects of storage at I ambient (22°C) and reduced (-20°C) temperatures on vapor spiked cassettes, which were generated with 20 L of dry air followed by 3 L of humid air to moisten the system. Except for day zero, I 42-18 II three samples for each of the two storage conditions were analyzed at intervals over an 18-day period. The results are not corrected for extraction efficiency. The data are also presented graphic- ally in Figures 4.9.1.-4.9.6. Table 4.9.1. Amount Vapor Spiked, yg/Cassette 2,6-TDI HDI 2,4-TDI 2.792 3.644 3.184 Table 4.9.2 Storage Tests for 2,6-TDI storage time % recovery (days) (refrigerated) (ambient) 0 77. 8 83. 5 90. 9 77 .8 85 .5 90.9 0 89. 5 84. 2 87. 8 89.5 84 .2 87.8 4 84. 5 88. 3 83. 5 89 .8 89 .0 91.0 7 91. 0 92. 4 99. 0 94 .6 86 .5 90.5 11 80. 9 85. 7 81. 4 95 .1 97 .1 87.3 14 89. 6 83. 7 94. 6 103 .7 99 .4 103.9 18 75. 7 85. 2 89. 7 95 .3 95 .5 102.0 Table 4.9.3 Storage Tests for HDI storage time % recovery (days) (refrigerated) (ambient) 0 75.9 82.3 89.7 75.9 82.3 89.7 0 91.2 81.9 83.8 91.2 81.9 83.8 4 79.6 80.8 79.3 84.4 83.9 81.1 7 86.9 86.2 95.4 82.1 75.1 81.9 11 76.4 80.0 75.4 82.2 82.5 77.7 14 87.5 81.7 91.2 85.9 82.8 88.4 18 71.4 81.1 83.0 81.8 84.4 85.0 42-19 I Table 4.9.4. Storage Tests for 2,4-TDI storage time % recovery 1 (days) (refrigerated) (ambient) 0 74.6 78.6 84.7 74.6 78.6 84.7 I 0 87.7 81.3 82.9 87.7 81.3 82.9 4 80.5 87.8 79.5 83.6 82.7 81.7 7 83.3 84.0 89.3 80.4 72.9 78.6 I 11 75.1 80.9 76.4 81.4 79.8 72.1 14 83.9 78.4 88.4 84.2 78.4 82.3 18 73.8 82.6 86.2 79.8 82.0 82.9 I 4.10. Side-by-side sampling I A simple experiment vas designed which allowed a bubbler contain- ing nitro reagent and a glass fiber filter coated with 1-2PP to be I simultaneously vapor spiked from the same 2,4-TDI atmosphere. This was accomplished by leaching a known amount of 2,4-TDI off a glass wool plug contained in a glass tube with dilution air which is then passed through a "Y" to each sampler. The air flow was I controlled by calibrated orifices of similar flow rate down stream from the samplers. I Each sample was analyzed twice and its average was plotted in Figure 4.10. The differences between the bubbler samples and the filter samples appear to be random with no discernible bias be- tween them. The amount of scatter observed in both collection I systems was not expected and probably can be attributed to the experimental design. The average line plotted in Figure 4.10. represents the average of all the collected samples and the data I is presented below. Table 4.10. 3 I Analysis of Side-By-Side Samples, ug/m collection collection I spike average system average system 1 192 F 207 F 2 197.5 F 209.5 F I 3 164.5 B 162.5 B 4 172.5 B 179 B I 5 208.5 F 224.5 B 6 231 F 181 B 7 230 F 244.5 B I 8 222.5 F 223 B 9 233.5 F 216 B continued I 42-20 I Table 4.10. (continued) collection collection spike average system average system 10 226 F 250.5 B 221.5 F 146.5 B 112 226.5 F 199.5 B 13 212 F 240.5 B 14 212 F 218.5 B 15 223.5 F 245 B 16 225 F 296.5 B 17 202.5 B 230 B 18 219.5 B 176.5 B 19 174 F 248 F 20 331.5 F 269 F F = Glass Fiber Filter with 1-2PP B = Toluene Bubbler with nitro reagent 4.11. UV Spectra Figures 4.11.1.-4.11.3. are the UV spectra of the 1-2PP deriv- atives of the diisocyanates used in this study. The three com- pounds are named below: CAS no. name - '. 2,6-Bis(4-(2-pyridyl)-l-piperazinylcarbamyl) toluene 72375-27-0 l,6-Bis(4-(2-pyridyl)-l-piperazinylcarbamyl) hexane 72375-21-4 2,4-Bis(4-(2-pyridyl)-l-piperazinylcarbamyl) toluene 4.12. Capacity of an 1-mg coated glass fiber filter A coated glass fiber filter was challenged with a 65/35 mixture of 2,4-TDI/2-6,TDI. The glass fiber filter coated with 1 mg of 1-2PP was suspended on an adapter ring of a standard 37-mm cassette. Another coated filter was placed on a backup pad in the bottom of the cassette. Four more adapter rings were placed in front of the suspended filter to allow the incoming isocyanate to cover the entire filter face and not just hit the center of the filter. The isocyanate mixture was liquid spiked onto glass wool that had been placed inside a 13-mm stainless steel filter holder. The metal filter holder was inserted into the Luer-Lok fitting of the cas- sette top. The glass wool was then spiked with 8.52 ug of the TDI mixture. Air was pulled through the cassette and holder at 1 L/min (72% relative humidity). After 15 min, the air flow was stopped and the rear filter was changed and replaced with a new 42-21 I The glass wool was spiked again with 8.52 vg of the TDI mixture. This procedure was repeated until a total of 10 rear filters had been removed and a total of 85.2 ug of isocyanate had been spiked I onto the glass wool. When the rear filters were analyzed, none of the showed the pre- sence of any TDI. The front filter, which was not changed during I the sampling, had collected a total of 66.1 ug of TDI. The other 19.1 ug of TDI was probably lost on the sides of the adapter rings of the cassette. The 66.1-ug collected represents 7.9 times the I 1989 TWA-PEL when sampling for 4 h. A second cassette containing filters was also tested in the same manner and again none of the rear filters contained any isocyan- I ate. In this test the front filter collected 59.4 ug of TDI or 7.1 times the 1989 TWA-PEL. I I I toluene-2,6-diisocyanate; 2,6-toluene diisocyanate; 2,6-diisocyanato-l- methylbenzene; isocyanic acid, 2-methy1-1,3-phenylene ester; 2,6-TDI I I 1,6-hexaraethyiene diisocyanate; HDI I H3C toluene-2,4-diisocyanate; 2,4-toluene diisocyanate; 2,4-diisocyanato-l- I methylbenzene; isocyanic acid,4-methyl-l,3-phenylene ester; 2,4-TDI Figure 1.1.4. Structures and synonyms of the diisocyanates. I 42-22 I BACKUP PAD iTED OFF SPACER TOP BOTTOM Figure 2.1.2. A drawing of a sample cassette. « MINUTE. S e Figure 3.5.1. Chromatogram of standards of the three diisocyanates. 42-23 I 1I PEAK A- 2.4-TDI PEAK B- I.e-HDI I PEAK C- 2.6-TOI «lu «c I O Io- I 2O O TIME.UIN I Figure 4.1. Analytical detection limit for the diisocyanates. I I 2,6-TDI I ra Ul a: 43 I u S4 O> O I cr« 2? I te .OVERALL DETECTION LIMIT I 33 ng SPIKE55 D 77 114 I Figure 4.2.1. Detection limit of the overall procedure for 2,6-TDI. I 42-24 I 140 112 1 ,6-HDI LJ C£ L«J 84 o 70 LJ 5« 42 ao 14 OVERRLL DETECTION LIMIT 14 28 42 nSg6 SPIKE70 D84 98 112 126 140 Figure 4.2.2. Detection limit of the overall procedure for HDI. OVERflLL DETECTION LIMIT .4n8 g SPIKE68 7D2 •183 120 Figure 4.2.3. Detection limit of the overall procedure for 2,4-TDI. 42-25 II 300000 I 27998O CflLIBRfiTIOH CURVE 24000O I 2 210000 x £ 180000 I »~- isoeoo §»* 129000 210000 I laeeoo I isoeoe § 120000 SLOPE* 34333 9000O I 60090 I 1,6-HBI .6 1.2 l.S 1.8 Z.I 2.4 Z.r 3.0 UCXHU I Figure 4.4.2. Calibration curve for HDI. I 42-26 I 500900 . 4COOOQ . CfiLIERflTIOH CURVE 2 350009. x SLOPE- IS86SI §200090. V a 150008. 100000 . 59990. 2,4-TDI 0.0 .3 .9 1.2 UC/mI.S. 1.8 2.1 2.4 2.7 Figure 4.4.3. Calibration curve for 2,4-TDI. 120 I OS »* 84 72 o «6 48 36 24 AHIICHT SRHPLCS LIHCflR CURVE 12 TOTRL STPMD. ERROR Of CST.«6.63 2,6-TDI 9SV-COMF1DEHCE LIMIT- *or-(l. SS* COHriOCHCC LIWIT« »or- 12.9 1.8 3.6 S.4 7.2 9.0 18.8 14.4 e.e BRVS !H STORflCE 12.6 16.2 18.0 Figure 4.9.1. Ambient storage test for 2,6-TDI. 42-27 1 1 120 I ice • 1 96 .._._-_._._._._-_._._._._._-_-_-_._-_-—-_._-—-—-—. a — u B§ H M " " 72 fl 1 u0 2 66 . o "" 1 u*• a* . 24 AM&ICMT SAHPLCS 1 1 • t« "~ H D I LINEAR CURVE 12 f TOTA96V 'COHriDCHCL STAND. CRRORC OHHITF CST.-fc.4- *or-2 U .9«*«.42> 6 .0 1 e. 0 1.8 3.6 S.4 7.2DAY S IH9. STORAG0 E te.8 12.6 14.4 16.2 I* Figure 4.9.2. Ambient storage test for HDI. 1 1 120 1 tee •• . . 1 11 B u Ha "n A > ?2 A fl o ••~"~"~- — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — - — i " 60 t— 1 <4c:l 24 _ AHBICHT SAMPLES |MM ^••T~"TDI • LIMCflR CURVE " '• 12 • : TOTAL STAND . CRROR OF CST.-6.3S ' 9S*< 'COHriDEHCE LIMIT- »or-U .96*6 .36J O 9S% COHriBCIICC LIMIT" *or- 12. H 1 0. 0 1.3 3.6 S.4 7.2DAY S IH 9.STORAG0 E J6.8 12.6 14.4 16.2 18.0 Figure 4.9.3. Ambient storage test for 2,4-TDI. 1 42-28 I 1 120 l OS 96 a 84 ua: u> 72 uo 60 0 46 i*j a. 36 24 SflHPUES LINEAR CURVE 12 TOTQL STflHB. ERROR OF EST.-7.63 2,6-TDI 959G'%< CGNFIUCHCCOHnDEUCE LIMITC LIMIT- +of- *or-l- 14.l ,96»7.639 ) 0 1.3 3.6 5.4 7.2 BAYS IK9. 0STORR6 C te.e 12.6 14.4 16.2 16.6 Figure 4.9.4. Refrigerated storage test for 2,6-TDI 120 toe ?e R R 64 72 o•_• u 60 48 if U a. 36 24 REFRIGERflTEP SflHPtES LIHEftlTOTIM* . CUEVSTOimE . ERROR OF EST.-7.79 12 *6'! COHFIPEHCE LIMIT- *oi-(l .<*««7.79J 1 ,6-HDI JS^ COttriBCHCt t-IMlIT« *<>«— t»_.t U-i 0 14.4 16. Z 18.0 9.6 1.8 3.6 S.4 7.2 BflVS II9.I8 STOftOG E 19.8 12.6 Figure 4.9.5. Refrigerated storage test for HDI. 42-29 I I 1 120 1 103 • 1 R * R A *4 D R ou: R S 72 , * 8 1 C. • * ^» * « • ^™ * •• * •* • «"• • ^B V ^B B *M • VIW « MB —— «» V ^B • ____ . ^M • ^^ • ^H • .^ . ^^ __ ^w . __• __ 1^ . ^K * ^B • ... Ul « £0• »- 46 ' I u i . 36 24 REFRlCERflTED SAMPLES .«.—.-.— 1 LINEAR CURVE £. ^ 4 "" " 1 U JL 12 9S-tTQTO LCONFIDENC STOIID. 'CRROE LIHITR OP EST.-t.8« +or-( 9 1.96*6.89) ? • 95% COMFIDEHCE LIMIT- +or- 13.6 _ , _ ...... i 1 6 1.8 3.6 5.4 7.2 9.0 19.8 12.6 14.4 16.2 I.0S e. DAYS IN STORAGE Figure 4.9.6. Refrigerated storage test for 2,4-TDI. 1 1 F-f,cr 1 •wo • 1 32«j> r B <"_ 28O 1 I _.- RVEKOCE PIE COIICEHTRBTIOH F .§ 24O E f F • .- ' _F r r ,F F r F B «-c- r * F » • 6 * * t_ r B_ p 1 F ^c 200- / r 7^ "* .E "" 160 B t 1 ... " • i I 2 3 4 5 6 7 8 9 10 11 12 13 14 IS 16 17 18 19 29 1 SPIKE NUMBER Figure 4.10. Side-by-side comparison of coated filters and bubblers. 42-30 1 1 0.0 oUI 0.6 ome O 4a9 1 .O KMVATXVE OF Z.C-TVI III Ac* 1.6 200 260 3OO 360 400 WAVELENGTH(NM) Figure 4.11.1. UV spectrum of 2,6-TDI derivative in acetonitrile. o.o o 0.6 1 .0 1 .6 2OO S6O 80O 36O 4OO WAVELENQTH(NM) Figure 4.11.2. UV spectrum of HDI derivative in acetonitrile 42-31 I 0.0 I oIII 0.6 I CD CC O I 1.0 I MBIVATZVE or 2.4-m n *e» I 1 .» 200 260 3 OO 360 400 WAVEUEMOTH(HM) I Figure 4.11.3. UV spectrum of 2,4-TDI derivative in acetonitrile. I I I I I 42-32 I 5. References 5.1. "Criteria for a Recommended Standard...Occupational Exposure to Toluene "Diisocyanate", Department of Health, Education and Wel- fare, National Institute for Occupational Safety and Health: Cincinnati, OH, 1973? HMS 73-11022. 5.2. "Criteria for a Recommended Standard...Occupational Exposure to Diisocyanates"; Department of Health, Education and Welfare, National Institute for Occupational Safety and Health: Cincinnati, OH, 1978; DHEW (NIOSH) Publ. (U.S.), No. 78-215. 5.3. Kormos, L.H.; Sandridge, R.L.; Keller, Anal. Chem. 1981, 53, 1125. 5.4. Sango, C.; Zimerson, E. J. Liq. Chromatogr. 1980, 3_, 971. 5.5. Hardy, H.L.; Walker, R.F. Analyst 1979, 104, 890. 5.6. Ellwood, P.A., Hardy, H.L.; Walker, R.F. Analyst 1981, 106, 85. 5.7. Goldberg, P.A.; Walker, R.F.; Ellwood, P.A.; Hardy, H.L. J. Chromatogr. 1981, 212, 93. 5.8. Hosein, H.R.; Farkes, S. Am. Ind. Hyg. Assoc. J. 1981, 42, 663. 5.9. Woolrich, P.P. Am. Ind. Hyg. Assoc. J. 1982, 43, 89. 5.10. Cummins, K., Diisocyanates, 2,4-TDI and MDI (Method 18, Organic Methods Evaluation Branch, OSHA Analytical Laboratory, Salt Lake City, Utah) unpublished (2-80). 42-33