# Draft Final Occupational and Consumer Exposure and

Environmental Release Assessment of Formaldehyde in Urea-Formaldehyde Resin
Manufacture and of Certain Chemicals for Substitute Technologies to Reduce Emissions from Composite Wood Products

U.S. Environmental Protection Agency

Office of Pollution Prevention and Toxics Chemical Engineering Branch and Exposure Assessment Branch 1200 Pennsylvania Avenue NW Washington, DC 20460

Draft Deliberative – Do not cite or quote - October 2011i Executive Summary

This assessment was conducted to support a rulemaking under the Toxic Substances Control Act (TSCA) Title VI, which includes examining substitute technologies to reduce formaldehyde emissions from composite wood products (CWPs). The scope of the assessment includes occupational exposures to and environmental releases of formaldehyde in ureaformaldehyde (UF) resin manufact ure and of some chemicals in substitute technologies intended to reduce formaldehyde emissions from CWPs thr oughout their life cycle. Inclusion in this life cycle is the end product usage by commercial wo rkers and consumers, such as home hobbyists and building/home occupants who may be exposed during and after product installation. . This report will refer to these chemicals as “substitute chemicals” or “substitutes”. For the purpose of this assessment, CWPs include hardwood pl ywood (HWPW), medium-density fiberboard (MDF), and particleboard (PB). The life cycle stages analyzed in this report include resin manufacturing, CWP manufacturing, downstrea m product manufacturing, and commercial/

consumer use.

The scope of this assessment, presented in Se ction 2.0, includes subst itute chemicals with toxic effects ranging from medium to high depending on the endpoint. Substitutes include

monomers of resins that are alternatives to ur ea-formaldehyde (UF) resi ns, additives to UF and alternate resins, and treatment chemicals

.

Inhalation exposure monitoring data for the s ubstitute chemicals and exposure scenarios in the scope of work were obtained from OSHA’ s Integrated Management Information System (IMIS), European Union (EU) Risk Assessmen ts, and other chemical-specific monitoring studies. These monitoring data were used to as sess exposures to formaldehyde and the substitute chemicals during relevant stages in the CWP lif e cycle. Where data were not available, OSHA Permissible Exposure Limits (PELs) were used to estimate “what-if” type inhalation exposures. Dermal exposures were primarily determined using standard EPA models. The exposure

assessment results are summarized in Table ES-1 , while discussions for each industrial and commercial/ consumer sector are provided in the report. A discussion of the occupational assessment methods is presented in Section 3.0. This report was developed in advance of a hazard report for the substitutes, so inhalation and dermal exposures were assessed regardless of potential toxic effects (e. g., cancer or non-cancer).

Daily inhalation exposure concentrations a nd dermal exposures, expressed as potential doses, are generally highest in the preliminary life cycle stages in which the substitute chemicals are introduced (primarily resin manufacture) an d generally are expected to decrease throughout subsequent life cycle stages as the substitute s are reacted, immobilized in resin matrices, volatilized, or reduced to very lo w concentrations. An exception to this general expectation is

where inhalation concentrations of several of the volatile chemicals increase in the CWP manufacturing stage as compared to the resin manufacturing stage.

The daily worker exposure inhalation concentr ations generated in th is report are highly uncertain and present significant limitations for thei r use. The air concentration parameters used to estimate the associated daily exposure concen trations come from a variety of sources, and their representativeness of actual air concentratio ns in workplaces in the CWP life cycle chain is not known. The daily exposure c oncentrations are most suitabl e for a qualitative overview of worker exposure issues and identification of data gaps.ii Inhalation monitoring data were generally spar se, and it is uncertain whether these data sets may represent exposures to substitute chemi cals in the various CWP life cycle stages in the

U.S. The characterizations of inhalation concen trations (e.g., average, 95th percentile, single point value, assumed high-end) were not consistent among th e substitute chemicals.

These uncertainties and limitations, as relate d to worker inhalati on exposures in this report, indicate that direct quantitative comparison between va rious chemicals and life cycle stages is likely to be im precise and is not recommended.

A preliminary data search for releases of substitute chemicals was commenced for this report using one primary source. EPA then determin ed that releases would not be used for other EPA analyses, so no further data searches or anal yses were conducted. This report presents the preliminary data search approach and da ta found for informational purposes only.

Table ES-2 presents a summary of release data found for each chemical and life cycle stage. Release data were obtained from the Toxi c Release Inventory (TRI), which is the main

literature source for release data and is desc ribed in Section 4.0. These data only include quantities that are released or transferred off site for treatment in wastewater or incineration units, in quantities greater than 25,000 pounds in specific regulated sector s. These data do not include facilities generating less than 25,000 pounds of each chemical or employing less than 10 full-time employees, chemicals not subject to the TRI (of th e substitute chemicals, only melamine is not subject to TRI reporting), chem icals manufactured in a sector not regulated by TRI, or quantities sent to on- and off-site waste management such as recycling and reuse. These release data are not analy zed and are presented for informational purposes only.

Section 5.0 of this assessment presents an uncertainty analysis. Section 6.0 presents

information and data related to facilities and wo rkers in the CWP lifecycle. Section 7.0 presents exposure and release data and estimates for the s ubstitutes during the lifecycle steps. Section 8.0 summarizes the data gaps, uncertainti es, and limitations of this work.iii Table ES-1. Summary of Estimated Average Inhalation Concentrations and Dermal Potential Doses for Assessed Chemicals by Life Cycle Stage

Formaldehyde

and Substitute

Chemicals Life Cycle Stage Average Daily

Concentration ( μ g/m 3 ) Lifetime Average Daily

Concentration ( μ g/m 3 ) Dermal Potential

Dose (mg/kg/day) a

Formaldehyde UF Resin Manufacturing 18 10 <0.15

Methanol UF Resin Manufacturing 7,300 c 4,200 c Not estimated g

CWP Manufacturing 59,000 b 34,000 b Not estimated g

Downstream Product Manufacturing Negligible f Negligible f Not quantifiable h

Commercial/ Consumer Use Negligible f Negligible f Not quantifiable h

Melamine MUF and Other Melamine-Based Resin Manufacturing 23-260 13-150 <44

CWP Manufacturing Negligible f Negligible f <7.6

Downstream Product Ma nufacture Negligible f Negligible f Not quantifiable h

Commercial/ Consumer Use Negligible f Negligible f Not quantifiable h

Epichlorohydrin Polyamine Epichlorohydrin Manufacturing 170 99 Not estimated g

PureBond Manufacturing Negligible f Negligible f Not quantifiable h

CWP Manufacturing (HWPW) Negligible f Negligible f Not quantifiable h

Downstream Product Manufacturing Negligible f Negligible f Not quantifiable h

Commercial/ Consumer Use Negligible f Negligible f Not quantifiable h

Polymethylene Diphenyl Diisocyanate pMDI Resin Manufacturing 2.3-46 1.3-26 <25

CWP Manufacturing (PB and MDF) 3.4 2.0 <25

Downstream Product Manufacturing Negligible f Negligible f Not quantifiable h

Commercial/ Consumer Use Negligible f Negligible f Not quantifiable h

Vinyl Acetate

Monomer PVA Resin Manufacturing 16-11,000 9.1-6,000 Not estimated g

CWP Manufacturing (HWPW) Negligible f Negligible f Not estimated g

Downstream Product Manufacturing Negligible f Negligible f Not quantifiable h

Commercial/ Consumer Use Negligible f Negligible f Not quantifiable h

Chromium (III) Addition of Chromium(III) Salts to

PVA Resin Negligible f Negligible f <25

CWP Manufacturing Negligible f Negligible f <2.5

Downstream Product Manufacturing Negligible f Negligible f Not quantifiable h

Commercial/ Consumer Use Negligible f Negligible f Not quantifiable h

Ammonia CWP Manufacturing 8,000 b 4,600 b Not quantifiable i

Downstream Product Manufacturing Negligible f Negligible f Negligible j

Commercial/ Consumer Use Negligible Negligible f Negligible j

Phenol PF Resin Manufacturing <9.4-270 d <5.3-160 d <3.8

CWP Manufacturing <230-460 d <130-260 e <<<3.8

Downstream Product Manufacturing Negligible f Negligible f Not quantifiable h

Commercial/ Consumer Use Negligible f Negligible f Not quantifiable h

μ g/m 3 – micrograms per cubic meter mg/kg/day – milligrams per kilogram (body weight) per day UF – Urea-formaldehyde PF – Phenol-formaldehyde MUF – Melamine-urea-formaldehyde CWP – Composite wood productiv PB – Particleboard MDF – Medium density fiberboard HWPW – Hardwood plywood pMDI - polymethylene diphenyl diisocyanate PVA – Polyvinyl acetate a – Based on EPA/OPPT dermal models (see Section 3.2.2) b – No data available – results based on “what-if” concentrations at the OSHA Permissible Exposure Limit (PEL)

level.

c – 95 th percentile value. d – Monitoring data reported minimum concentrations as zero. For this assessment, minimum concentrations were assumed to be equal to the limit of detection for pheno l, as specified in OSHA Analytical Method No. 32.

e – 50 th to 90 th percentile range. f – Negligible inhalation exposures are defined as < 0.01 mg/m 3 TWA. g – The dermal model used for estimates in this report could not be adjusted to account for the higher volatility of formaldehyde, methanol, epichlorohydrin, and vinyl acetate when the chemical is expected to be handled in nearly pure forms or in highly concentrated and volatile mixtures. See Section 3.2.2 for an explanation.

h – Some surface contact with solids containing the chemical may occur (s imilar to cast solids as indicated in Section 3.2.2, Table 3-2). i – Dermal exposures to gases are not quantifia ble. See Section 3.2.2 for an explanation. j – Ammonia is expected to be volatilized during CWP curing and not present during downstream product manufacturing and commercial/ consumer (e.g., home hobbyists, home occupants, etc.) use.vTable ES-2. Summary of Releasesof Formaldehyde and Substitute Chemicals by Life Cycle Stage asReported in TRI for Reporting Year 2008PrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers for Release (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotal AirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWateraIncinerationFORMALDEHYDEUF Resin Manufacturing325211(64 sites)Plastics Material andResin Mfg 205,136 44,885 250,021 7,687 289,757 547,465 117,780 13,984 131,764 679,229 3,055,017 277,085METHANOLUF Resin Manufacturing325211(111 sites)Plastics Material andResin Mfg 1,824,256 1,622,898 3,447,15554,452 1,748,854 5,250,4612,835,660 46,413 2,882,0738,132,534 5,794,872 7,388,398CWP Manufacturing321211(2 sites)Hardwood Veneer andPlywood Mfg 43,449 6,332 49,781 0 0 49,781 0 0 0 49,781 0 0321219(73 sites)Reconstituted WoodProduct Mfg 4,542,783 103,440 4,646,223390 18 4,646,631 565 0 565 4,647,196 267 24EPICHLOROHYDRINPolyamine Epichlorohydrin / PureBond Manufacturing325211(13 sites)Plastics Material andResin Mfg 9,086 58,957 68,043 1,413199 69,655 1 0 1 69,656 22,437 171,530325998(13 sites)All Other Misc. Chem.Product and PreparationMfg 2,000 7,419 9,419 0 429,734439,153 66 69 135 439,288 250 2,000DIISOCYANATE CATEGORY (includes MDI)pMDI Resin Manufacturing325211(68 sites)Plastics Material andResin Mfg 858 2,936 3,793 0 25 3,81844,551 58,338 102,889 106,707 602 213,152CWP Manufacturing321219(30 sites)Reconstituted WoodProduct Mfg 7,789 1,236 9,025 0 0 9,025 0 0 0 9,025 0 0viTable ES-2. Summary of Releasesof Formaldehyde and Substitute Chemicals by Life Cycle Stage asReported in TRI for Reporting Year 2008PrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers for Release (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotal AirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWateraIncinerationDownstream Product Manufacturing321911(8 sites)Wood Window and DoorMfg 0 5 5 0 0 5 0 0 0 5 0 0321918(1 site)Other Millwork(including Flooring) 0 0 0 0 0 0 0 0 0 0 0321991(63 sites)Manufactured Home(Mobile Home) Mfg 0 0 0 0 0 0 0 57 57 57 0 0321992(2 sites)Prefabricated WoodBuilding Mfg 0 0 0 0 0 0 0 0 0 0 0337211(4 sites)Wood Office FurnitureMfg 0 0 0 0 0 0 0 0 0 0 0337212(1 site)Custom ArchitecturalWoodwork andMillwork Mfg 0 23 23 0 0 23 0 0 0 23 0 0337122(1 site)Nonupholstered WoodHousehold FurnitureMfg 0 0 0 0 0 0 0 0 0 0 0 0337127(2 sites)Institutional FurnitureMfg 0 13 13 0 0 13 0 0 0 13 0 0VINYL ACETATE MONOMERPVA Resin Manufacturing325211(43 sites)Plastics Material andResin Mfg 297,366 355,341 652,707 18 54 652,7792,655 0 2,655 655,434 380,204 5,717,362CHROMIUMAddition of Cr (III) salts to PVA resin325211(3 sites)Plastics Material andResin Mfg 9 250 259 0 70 329 14 186 200 529 0 0viiTable ES-2. Summary of Releasesof Formaldehyde and Substitute Chemicals by Life Cycle Stage asReported in TRI for Reporting Year 2008PrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers for Release (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotal AirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWateraIncinerationDownstream Product Manufacturing337127(4 sites)Institutional FurnitureMfg 5 255 260 0 0 260 501 0 501 761 250 0337212(3 sites)Custom ArchitecturalWoodwork andMillwork Mfg 0 2 2 0 0 2 182 72 254 256 0 0337215(4 sites)Showcase, Partition,Shelving, and LockerMfg 0 250 250 1 0 251 0 0 0 251 0 0CHROMIUM COMPOUNDSAddition of Cr (III) salts to PVA resin325211(10 sites)Plastics Material andResin Mfg 605 392 997 13,000 407,379421,376 77,901 322 78,223 499,599 10 0Downstream Product Manufacturing321911(2 sites)Wood Window and DoorMfg 22 0 22 0 0 22 826 7,191 8,017 8,039 252 0337127(1 site)Institutional FurnitureMfg 6 4 10 0 0 10 0 0 0 10 16 0AMMONIACWP Manufacturing321211(1 site)Hardwood Veneer andPlywood Mfg 0 5 5 0 0 5 0 0 0 5 0 0321219(7 sites)Reconstituted WoodProduct Mfg 272,885 1,285 274,1701,295 751 276,216 314 0 314 276,530 0 0PHENOLResin Manufacturing325211(52 sites)Plastics Material andResin Mfg 139,001 137,432 276,433 2,149 286 278,868826,294 167,525 993,8191,272,687 153,012 2,582,288CWP Manufacturing321219(10 sites)Reconstituted WoodProduct Mfg305,8142,472308,28621155308,46257057308,519 0 0viiiSource: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedor transferred off site for treatment in wastewater and incineration units. It does not includequantities sent to on- and off-site waste management such as recycling and reuse.a - Off-site water transfer includes Publicly Owned TreatmentWorks (POTWs) and Waste Water Treatment Plants (WWTPs).T ABLE OF C ONTENTS

Page

E XECUTIVE S UMMARY

.................................................................................................................... I

L IST OF F IGURES

.......................................................................................................................... XII

L IST OF T ABLES

.......................................................................................................................... XIII

1.0 I NTRODUCTION AND P URPOSE ........................................................................................... 1

2.0 S COPE OF THE A SSESSMENT .............................................................................................. 1

2.1 Life Cycle Stages .................................................................................................... 2

2.1.1 Resin Manufacturing ................................................................................... 3

2.1.2 Composite Wood Product (CWP) Manuf acturing (Primary Manufacturing)

3

2.1.3 Downstream Product Manufacturing .......................................................... 3

2.1.4 Commercial/ Consumer Use ....................................................................... 3

2.2 NAICS Codes Associated with Life Cycle Stages ................................................. 4

3.0 O CCUPATIONAL E XPOSURE A SSESSMENT M ETHOD ......................................................... 6

3.1 Data Collection ....................................................................................................... 6

3.1.1 OSHA IMIS Data ........................................................................................ 6

3.1.2 International Reports and Assessments ...................................................... 7

3.2 Approach for Assessing O ccupational Exposures .................................................. 7

3.2.1 Inhalation Exposures ................................................................................... 7

3.2.2 Dermal Exposures ....................................................................................... 8

3.3 Approach for Assessing Consumer Exposures..................................................... 12

4.0 R ELEASE D ATA C OLLECTION AND P RESENTATION ........................................................ 12

5.0 L IMITATIONS OF A SSESSMENT M ETHOD AND U NCERTAINTY A SSOCIATED WITH

R ESULTS

.............................................................................................................................. ......... 13

5.1.1 Amount of Exposure Data Available ........................................................ 13

5.1.2 Applicability of Exposure or Release Data ............................................... 14

5.1.3 Representativeness of Monitoring Data and Models ................................ 14

5.1.4 Sources of Exposure ................................................................................. 14

5.1.5 Frequency and Duration of Exposure ....................................................... 15

5.1.6 Number of Sites and Workers ................................................................... 15

5.1.7 Post-CARB Rule Exposures ..................................................................... 15

6.0 G ENERAL P ROCESS D ESCRIPTIONS AND F ACILITY E STIMATES ..................................... 16

6.1 Resin Manufacturing ............................................................................................. 16

6.1.1 General Resin Manufacturing Process ...................................................... 17

6.1.2 Number of Establishments, Worker s, Production Hours, and Work Day

Estimates ............................................................................................................... 17

6.2 Composite Wood Product Manufacturing ............................................................ 19

6.2.1 Potential Exposure Activities .................................................................... 19Page x

T ABLE OF C ONTENTS (Continued)

Page

x 6.2.2 Number of Establishments, Worker s, Production Hours, and Work Day

Estimates ............................................................................................................... 19

6.3 Downstream Product Manufacturing .................................................................... 22

6.3.1 Potential Exposure Activities .................................................................... 22

6.3.2 Number of Establishments, Worker s, Production Hours, and Work Day

Estimates ............................................................................................................... 23

6.4 Commercial Use.................................................................................................... 25

6.5 Consumer Use.....................................................................................25

7.0 E XPOSURE A SSESSMENT BY C HEMICAL .......................................................................... 26

7.1 Formaldehyde Exposure during UF Resin Manufacturing ................................... 26

7.1.1 Process Description ................................................................................... 26

7.1.2 Exposure Assessment for Formaldehyde in UF Resin Manufacturing ..... 28

7.1.3 Uncertainty in Exposure Assessment ........................................................ 29

7.1.4 Environmental Releases of Formal dehyde during UF Resin Manufacturing

.......................................................................................29

7.2 Methanol ............................................................................................................... 31

7.2.1 Manufacture of UF Resin.......................................................................... 31

7.2.2 Methanol in CWP Manufacture ................................................................ 35

7.2.3 Downstream Product Manufacture and Commercial/ Consumer Use ...... 38

7.3 Melamine .............................................................................................................. 39

7.3.1 Manufacture of MUF and Other Melamine-Based Resins ....................... 39

7.3.2 Melamine in CWP Manufacturing ............................................................ 40

7.3.3 Melamine Resins in Downstream Product Manufacturing and

Commercial/ Consumer Use ................................................................................. 41

7.4 Epichlorohydrin .................................................................................................... 42

7.4.1 Manufacture of Polyamine Epichlorohydrin Resin .................................. 42

7.4.2 Manufacture of PureBond, HWPW, Downstream Product Manufacture,

and Commercial/ Consumer Use .......................................................................... 47

7.5 Polymethylene Diphenyl Diisocyanate (pMDI) ................................................... 48

7.5.1 pMDI Resin Manufacture ......................................................................... 49

7.5.2 PB and MDF Manufacture ........................................................................ 52

7.5.3 Downstream Product Manufacture and Commercial/ Consumer Use. ..... 55

7.6 Vinyl Acetate Monomer (VAM) a nd Polyvinyl Acetate (PVA) .......................... 57

7.6.1 Manufacture of PVA resin ........................................................................ 57

7.6.2 HWPW Manufacturing ............................................................................. 63

7.6.3 Downstream Product Manufacture and Commercial/ Consumer Use ...... 63

7.7 Chromium (III) ...................................................................................................... 65

7.8 Ammonia............................................................................................................... 69

7.8.1 Ammonia in CWP Manufacture ............................................................... 69

7.8.2 Downstream Product Manufacture and Commercial/ Consumer Use ...... 71

7.9 Phenol ................................................................................................................... 73

7.9.1 Manufacture of Phenol-Formaldehyde Resin ........................................... 73

7.9.2 Phenolic Resins in CWP Manufacturing .................................................. 78

7.9.3 Downstream Product Manufacturing a nd Commercial/ Consumer Use ... 82Page xi

T ABLE OF C ONTENTS (Continued)

Page

xi 8.0 K EY U NCERTAINTIES AND L IMITATIONS OF W ORKER E XPOSURE E STIMATES ............ 83

9.0 R EFERENCES ..................................................................................................................... 85xii L IST OF F IGURES Page

Figure 7-1. Process flow diagram for UF re sin manufacturing (Kirk-Othmer, 2002a) ................ 27

Figure 7-2. Typical Phenolic Resin Production Unit (Kirk-Othmer, 2003a) ............................... 74L IST OF T ABLES

Page

Table 2-1. Assessed Chemicals, Functions, and Applicable Life Cycle Stages ............................. 2

Table 2-2. NAICS Industry Sectors for Each Life Cycle Stage in the Exposure Assessment ....... 5

Table 3-1. Standard EPA Default Values for Use in the Worker Dermal Exposure Models ....... 11

Table 3-2. EPA Default Qualitative Assessments for Screening-Level Estimates of Dermal Exposure ............................................................................................................... 12

Table 6-1. Index Entries within NAICS C ode 325211 (Plastics Material and Resin Manufacturing) Matched with Corres ponding Resin Manufacturing Life Cycle Stages .................................................................................................................... 17

Table 6-2. Summary of 2002 Economic Census Data and Parameters Calculated from these Data for Resin Manufacturing Sites .............................................................................. 18

Table 6-3. Number of U.S. Hardwood Plywood Mills ................................................................. 21

Table 6-4. Number of U.S. Rec onstituted Wood Product Mills ................................................... 21

Table 6-5. Summary of 2002 Economic Census Data and Parameters Calculated from these Data for CWP Manufacturing Sites ............................................................................... 21

Table 6-6. Summary of 2002 Economic Census Data and Parameters Calculated from this Data for Potential Downstream Product Manufacturing Sites ...................................... 24

Table 7-1. Occupational Exposure Limits for Formaldehyde ...................................................... 26

Table 7-2. Surrogate Inhalation Mo nitoring Data from OSHA IMIS Database used to represent Formaldehyde Concentrations duri ng UF Resin Manufacturing .......................... 28

Table 7-3. Estimated Average Daily Concentrati ons for Data Representing Formaldehyde during UF Resin Manufacturing....................................................................................... 28

Table 7-4. Environmental Releases of Formal dehyde during Plastics Material and Resin Manufacturing as Reported in TRI for Reporting Year 2008 ............................... 30

Table 7-5. Occupational Exposure Limits for Methanol (CASRN 67-56-1) ................................ 31

Table 7-6. Surrogate Inhalation Monitoring Data from OECD used to represent Methanol Concentrations during UF Resin Manufacturing .................................................. 32

Table 7-7. Estimated Average Daily Concentrations for Data Representing Methanol during UF Resin Manufacturing ............................................................................................. 32

Table 7-8. Environmental Releases of Meth anol during Plastics Material and Resin Manufacturing Reported in TRI for Reporting Year 2008 ................................... 34L IST OF T ABLES (Continued)

Page

xiv Table 7-9. Estimated “What-If” Average Daily Concentrations of Methanol During CWP Manufacturing, based on the OSHA PEL ............................................................. 35

Table 7-10. Environmental Releas es of Methanol during CWP Manufacturing Reported in TRI for Reporting Year 2008 ....................................................................................... 37

Table 7-11. Estimated Average Daily Concentrati ons of Surrogate Inhalation Monitoring Data from OECD used to represent Melamine Concentrations during Melamine-Based Resin Manufacturing ............................................................................................. 40

Table 7-12. Occupational Exposure Limits for Epichlorohydrin ................................................. 42

Table 7-13. PPE Considerations dur ing Use of Epichlorohydrin ................................................. 43

Table 7-14. Inhalation Monitoring Data from OS HA IMIS Database for Epichlorohydrin during

PAE Production .................................................................................................... 44

Table 7-15. Estimated Average Daily Concentrati ons of Epichlorohydrin during Manufacture of

PAE Resin ............................................................................................................. 44

Table 7-16. Environmental Releas es of Epichlorohydrin during Plastics Material and Resin Manufacturing (NAICS Code 325211) and All Other Miscellaneous Chemical Product and Preparation Manufacturing (NAICS Code 325998) Reported in TRI for Reporting Year 2008 ....................................................................................... 46

Table 7-17. Occupational Exposure Limits for MDI and pMDI .................................................. 48

Table 7-18. Inhalation Monitoring Data from EU Risk Assessment for MDI/ pMDI Concentrations during pMDI Resin Manufacturing ............................................. 49

Table 7-19. Estimated Average Daily Concentrati ons for Data Representing MDI/ pMDI during pMDI Manufacturing ............................................................................................ 50

Table 7-20. Releases of MDI Duri ng Plastics Material and Resi n Manufacturing Reported in TRI for Reporting Year 2008 a ...................................................................................... 51

Table 7-21. Inhalation Monitoring Data from EU Risk Assessment for MDI/ pMDI Concentrations during PB Manufacturing ............................................................ 52

Table 7-22. Estimated Average Daily Concentrati ons for Data Representing MDI/ pMDI during PB and MDF Manufacturing ................................................................................ 52

Table 7-23. Releases of MDI during Reconsti tuted Wood Product Manufacturing Reported in TRI for Reporting Year 2008 a .............................................................................. 54

Table 7-24. Releases of MDI in Various Downstream Product Manufacturing Industries Reported in TRI for Reporting Year 2008 a ........................................................... 56

Table 7-25. Occupational Exposure Limits for Vi nyl Acetate Monomer (CASRN 108-05-4) .... 57L IST OF T ABLES (Continued)

Page

xv Table 7-26. VAM Permeation Time s for Various PPE Materials a ............................................... 59

Table 7-27. Surrogate Inhalation Mo nitoring Data from Data Repr esenting VAM Concentrations during PVA Resin Manufacturing a ...................................................................... 60

Table 7-28. Estimated Average Daily Concentra tions for Data Representing VAM during PVA Production using Surrogate Data fro m the EU Risk Assessment ......................... 61

Table 7-29. Releases of VAM dur ing Plastics Material and Re sin Manufacturing Reported in TRI for Reporting Year 2008 ................................................................................ 62

Table 7-30. Occupational Exposure Limits for Chromium (III) (CASRN 16065-83-1) .............. 65

Table 7-31. Release of Chromium and Chromi um Compounds during Plas tics Material and Resin Manufacturing Reported in TRI for Reporting Year 2008 ......................... 67

Table 7-32. Releases of Chromium and Ch romium Compounds during Downstream Product Manufacturing Reported in TRI for Reporting Year 2008 ................................... 68

Table 7-33. Exposure Limits for Ammonia (CASRN 7664-41-7) .............................................. 69

Table 7-34. Estimated “What-If” Average Dail y Concentrations of Ammonia Based on the

OSHA PEL............................................................................................................ 70

Table 7-35. Environmental Releases of A mmonia during Hardwood Veneer and Plywood Manufacturing (NAICS Code 321211) and Reconstituted Wood Product Manufacturing (NAICS Code 321219) Repor ted in TRI for Reporting Year 2008 a

............................................................................................................................... 72

Table 7-36. Occupational Exposure Limits for Phenol (CASRN 108-95-2) ................................ 73

Table 7-37. Inhalation Monitoring Data from 2006 EU Risk Assessment for Phenol during Phenolic Resin Manufacturing .............................................................................. 75

Table 7-38. Estimated Average Daily Concentra tions for Data Representing Phenol during Phenolic Resin Manufacturing .............................................................................. 75

Table 7-39. Environmental Re leases of Phenol during Pl astics Material and Resin Manufacturing Reported in TRI for Reporting Year 2008 ................................... 77

Table 7-40. Inhalation Monitoring Data from 2006 EU Risk Assessment for Phenol during Phenolic Resin Processing .................................................................................... 78

Table 7-41. Estimated Average Daily Concentrati ons for Data Representing Phenol during CWP Manufacturing ....................................................................................................... 79

Table 7-42. Environmental Re leases of Phenol during Reconstituted Wood Product Manufacturing Reported in TRI for Reporting Year 2008 ................................... 81Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 1

1.0 I NTRODUCTION AND P URPOSE

In a rulemaking under the Toxic Substances Control Act (TSCA) Title VI, the Environmental Protection Agency (EPA) is regul ating formaldehyde emissions from composite wood products (CWPs), which include ha rdwood plywood (HWPW), medium-density fiberboard (MDF), and particleboard (PB). As part of this rulemaking, EPA is reviewing substitute technologies to reduce formaldehyde emissions from CWPs. This report presents information about the potential for occupational exposures to and environmental releases of formaldehyde in urea-formaldehyde (UF) resins and some chemicals involved in the substitute technologies. This report will refer to these chemicals as “substitute chemicals” or “substitutes”. The report presents worker exposure estimates fo r the set of chemicals and workplaces discussed in the Scope section below. Available release data related to the sc ope are presented for informational purposes only. Appendix A includes definitions of key technical terms used in this section and throughout the remainder of this report.

2.0 S COPE OF THE A SSESSMENT

The scope of this assessment includes subst itute chemicals with toxic effects ranging from medium to high depending on the endpoint (U SEPA, 2011a). Substitu tes include monomers

of resins that are alternatives to urea-formalde hyde (UF) resins, additive s to UF and alternate resins, and treatment chemicals

. The life cycle stages included w ithin the scope of this report vary for each substitute chemical and depend on th e function of the substitute chemical in the specific type of composite wood product for which it is used. The life cycl e stage for a specific substitute chemical begins at re sin manufacture or at the next ear liest stage in the CWP life cycle

into which the substitute chemical is intr oduced. The possible life cy cle stages are resin manufacturing, CWP manufacturing, downstrea m product manufacturing and commercial/ consumer use. In this case, exposures during consumer use include not only exposures that would occur to home hobbyists, but secondary exposure to the consumers who purchase and use articles, such as book shelves, entertainment centers, etc. composed of CWPs made with substitute chemicals. All of these steps excep t resin manufacturing are de scribed in detail in “Assessment of Occupational Exposure to Fo rmaldehyde from Composite Wood Products” (USEPA, 2011b), and their processes will only be su mmarized in this report. Table 2-1 lists the substitute chemicals, their functi ons, and the applicable life cycle stages for each included in this

report.

Additionally, occupational e xposures to and environmenta l releases of formaldehyde

from UF resin manufacture were not included in the scope of “Assessment of Occupational Exposure to Formaldehyde from Composite Wood Products” (USEPA, 2011b). However,

because resin manufacture was included in the scope of substitutes’ analyses, occupational exposures to and environmental releases of fo rmaldehyde in UF resin manufacture are included in this report to provide ba lance of coverage between form aldehyde and the substitutes.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 2

Table 2-1. Assessed Chemicals, Function s, and Applicable Life Cycle Stages

Assessed Chemicals Function of Chemical Applicable Life Cycle Stages

Formaldehyde

CASRN: 50-00-0 - Monomer for urea-formaldehyde (UF) resin - UF resin manufacturing

Methanol

CASRN: 67-56-1 - Additive to urea-formaldehyde (UF)

resin - UF resin manufacturing CWP manufacturing

- Downstream product manufacturing

- Commercial/ Consumer use

Melamine

CASRN: 108-78-1 - Monomer for melamine-ureaformaldehyde (MUF) resin

- Additive to other resins used in CWP

manufacturing - MUF and other resin manufacturing

- CWP manufacturing

- Downstream product manufacturing

- Commercial/ Consumer use

Epichlorohydrin

CASRN: 106-89-8 - Component in PureBond resin - Polyamine epichlorohydrin resin manufacturing

- PureBond manufacturing

- CWP manufacturing

- Downstream product manufacturing

- Commercial/ Consumer use

Polymethylene Diphenyl Diisocyanate (pMDI)

CASRN: 9016-87-9 - Resin (polymethylene diisocyanate (pMDI) resin) - pMDI resin manufacturing

- CWP manufacturing

- Downstream product manufacturing

- Commercial/ Consumer use

Vinyl Acetate Monomer (VAM)

CASRN: 108-05-4 - Monomer in polyvinyl acetate (PVA)

resin - PVA resin manufacturing

- CWP manufacturing

- Downstream product manufacturing

- Commercial/ Consumer use

Chromium (III)

CASRN: 16065-83-1 - Additive in polyvinyl acetate (PVA)

resin - Addition of Cr(III) salts to PVA resin

- CWP manufacturing

- Downstream product manufacturing

- Commercial/ Consumer use

Ammonia

CASRN: 7664-41-7 - Additive (reacted into resin molecule)

- Additive (added in CWP process);

- Post-pressing treatment agent. - CWP manufacturing

- Downstream product manufacturing

- Commercial/ Consumer use

Phenol

CASRN: 108-95-2 - Monomer for phenol-formaldehyde (PF) resin - PF resin manufacturing

- CWP manufacturing

- Downstream product manufacturing

- Commercial/ Consumer use

2.1 Life Cycle Stages

Subsections 2.1.1 through 2.1.4 briefl y describe the life cycle st ages within the scope of this report.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 3

2.1.1 Resin Manufacturing

Resin manufacturing refers to th e use of the substitute to pr oduce resins that may be used in the manufacture of HWPW, MDF, and PB. Th e life cycles for chemicals that are resin monomers begin during their use in the appropriate resin manufacturing step.

2.1.2 Composite Wood Product (CWP) Manufac turing (Primary Manufacturing)

The terms “composite wood product manufacturing” and “primary manufacturing” in this report refer specifically to the ma nufacture of HWPW, MDF, and PB.

NAICS code 321219 - Reconstituted Wood Pr oduct Manufacturing includes both the

manufacture of PB and MDF. It also includes the manufact ure of composite products not included in the scope of this assessment, su ch as hardboard, orie nted strandboard, and waferboard (U.S Census Bureau, 2002a).

NAICS code 321211 - Hardwood Veneer a nd Plywood Manufacturing includes the manufacture of hardwood plywood. It also includes the manufacture of hardwood veneers, which are not included in the scope of this assessment (U.S Census Bureau, 2002a).

2.1.3 Downstream Product Manufacturing

After CWP manufacturing, HWPW , MDF, and PB may be converted into articles or other downstream products. For example, HWPW may be pressed into panels and plywood components (e.g. curved HWPW, seat backs, chair arms, etc) or used for furniture, cabinets, architectural millwork, paneling for commercial buildings, floo ring, store fixtures and doors (OAQPS, 2000a). Similarly, MDF and PB are used in the manufacture of many products including virtually every applica tion where interior panels or st rips are required, especially in furniture and cabinetry. PB is used as floor decking in manufactured homes, underlayment in conventional homes, shelving, door cores, stair st epping, door frames, and a host of other uses that require small flat parts as a starting point. On the other hand, MDF is not used as floor underlayment or decking except on special request. A small portion of PB is also extruded or molded into furniture parts, brush ba ses and toilet seats (Kirk-Othmer, 2000a).

2.1.4 Commercial/ Consumer Use

The commercial/ consumer use of CWPs in cludes (1) the use of CWPs in on-site construction and (2) the utilization by office workers of work-place buildings (commercial buildings) containing CWPs and downstream produc ts constructed of CWPs (such as furniture and cabinets). Home hobbyists who construct their own furniture may be exposed to the same type of CWP boards as commercial furniture bu ilders. Also, new furniture is generally purchased by consumers in boxes and assembled in homes. Such boxed furniture may be constructed of CWP boards made using the same subs titute chemicals that are the subject of this report. Furniture that contains CWPs include: entertainment cen ters, book shelves, baby cribs, baby changing tables, etc. Secondary exposure to home occupants may occur (as in the caseFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 4

with formaldehyde), if the chemicals are volatile . In the chemistry evaluation of substitute chemicals conducted by EPA for this effort, all vo latile chemicals are exp ected to be released earlier during the manufacturing/ processing stage of th e life cycle, therefore, exposures are generally expected to be negligible. (USEPA. 2011c)

2.2 NAICS Codes Associated with Life Cycle Stages

For formaldehyde and each of the substitutes, each of the life cycle stages discussed above was matched with appropriate North Amer ican Industry Classification System (NAICS) codes. NAICS codes are used to identify particular industries and are essen tial in retrieving data from the OSHA Integrated Management Informa tion System (IMIS), Toxic Release Inventory (TRI), and the U.S. Economic Census which ar e discussed in Sections 3.0, 4.0, and 6.0 below.

Table 2-2 lists the NAICS codes used for each life cycle stage, which are discussed further in

Section 6.0.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 5

Table 2-2. NAICS Industry Sectors for Each Life Cycle Stage in the Exposure Assessment

NAICS Corresponding

1987 SIC a Description

Resin Manufacturing

325199 2869, 2899 All Other Basic Organic Chemical Manufacturing

325211 2821 Plastics Material and Resin Manufacturing

325998 2819, 2899, 3952, 3999,

7389 All Other Miscellaneous Chemical Product and Preparation Manufacturing

Primary Manufacturing (Composite Wood Products)

321219 2493 Reconstituted wood product manufacturing

321211 2435 Hardwood veneer and plywood manufacturing

Downstream Product Manufacturing

321911 2431 Wood window and door manufacturing

321918 2431 Other millwork (including flooring)

321991 2451 Manufactured home (mobile home) manufacturing

321992 2452 Prefabricated wood building manufacturing

337110 2434 Wood kitchen cabinet and counter top manufacturing

337121 2512 Upholstered household furniture manufacturing

337122 2511 Nonupholstered wood household furniture manufacturing

337127 2541 Institutional furniture manufacturing

337129 2517 Wood television, radio, and sewing machine cabinet manufacturing

337211 2521 Wood office furniture manufacturing

337212 2541 Custom architectural woodwork and millwork manufacturing

337215 2541 Showcase, partition, shelving, and locker manufacturing

Commercial/ Consumer Use

N/A N/A N/A

N/A – Not applicable – there are no NAICS codes applicable to the use of CWP products during building construction or for workers using commercial buildings. Likewise, there are no NAICS codes associated with consumer or home hobbyist use. a – Standard Industrial Classification (S IC) codes were replaced by the NAICS sy stem in 1997. SIC codes were also

searched in the OSHA IMIS database.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 6

3.0 O CCUPATIONAL AND C ONSUMER E XPOSURE A SSESSMENT M ETHODS

The data collection efforts, the methods utilized for estimating occupational and consumer exposures and the use of these methods are discussed in this section.

3.1 Occupational Data Collection

It was outside the scope of the assessment to obtain primary data through direct sampling methods. Therefore, this exposure assessment relied on the use of a limited number of sources of readily available secondary data, such as prior research studies and reports, to characterize occupational exposures from substitute chemicals during their life cycle in the CWP industry. A comprehensive review of readily available government, industry and academic sources was conducted, including: EPA, OSHA, NIOSH, Organization for Economic Co-operation and Development (OECD), industry websites, academic journals, and publications. The information and data were compiled according to the data preference criteria, which are presented in Appendix B of this report. The following subsections discuss the major sources of data used in

this assessment.

3.1.1 OSHA IMIS Data

Inhalation monitoring data were primarily obt ained from OSHA’s IMIS database. IMIS is an online data entry and information retrieval sy stem designed to collect, process, retrieve, and communicate penalty assessment, arbitration, and collection information regarding OSHA inspections. The monitoring data in this databa se were collected during OSHA inspections that were conducted between January 1979 and April 2010 in the US (OSHA, 2010). For each data point, the database contained info rmation on the inspection date, id entity of inspected facility, inspection type (e.g., inspection in response to a co mplaint, referral, or as part of a program), worker job description, exposure concentration level, exposure concentration measurement type (personal or area measurement), exposure type (i.e., time weighted average (TWA), ceiling, short-term, etc.), frequency or duration of e xposure, number of employees at the inspected facility, and the number of employees expose d. IMIS was searched by NAICS code query. OSHA IMIS data were obtained through requests to OSHA made on April 23, 2010 and September 23, 2010.

The main types of monitoring data availa ble in the OSHA IMIS database are TWA, ceiling, short-term or not found (NF). 1 Only TWA data were used in this assessment because only TWA data can be used to calcul ate average daily concentrations.

Short-term or ceiling values present the highest concentration at the time of the measurement, but do not specify the duration of e xposure. This level of exposure may be much lower when averaged over an 8-hour period. Measur ements that resulted in a non-detected (NF) formaldehyde concentration did not include their measurement type in the OSHA IMIS database

1 Not found (NF) indicates that the chemic al was not detected during monitoring.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 7

(i.e., TWA or STEL measurement type). Therefor e, it is unknown whethe r a non-detected value was measured over an eight hour duration or a fifteen minute duration. For this reason, nondetected and not-found results were also excluded.

3.1.2 International Reports and Assessments

The other main sources of monitoring data were OECD SIDS reports and EU Risk Assessments. These sources typically summarized th e monitoring data as a range of values and often did not indicate the sampling method or lim its of detection. Additionally, mean and median values were typically not reporte d. Canadian reports and assessmen ts were also researched, but no data directly relevant to this assessment were found.

3.2 Approach for Assessing Occupational Exposures

This report was developed in advance of a h azard report for the substitutes, so inhalation and dermal exposures were assessed regardless of potential toxic effects (e.g., cancer or noncancer). The following subsections describe th e methods for assessing inhalation and dermal occupational exposures.

3.2.1 Inhalation Exposures

Due to data limitations, this exposure a ssessment characterizes overall chemical exposures at a site; therefore, the data presente d in this assessment re present total chemical exposures at sites in each speci fic life cycle stage. For each subs titute chemical and relevant life cycle stage, inhalation exposures were assessed by determining th e Average Daily Concentration (ADC) and Lifetime Average Daily Concentr ation (LADC), using Equation 3-1 (USEPA, 2009b):

A T ED EF ET CA EC ) (   

 (3-1)

Where: EC = Exposure concentration ( μ g/m 3 ) CA = Contaminant concentration in air ( μ g/m 3 ) ET = Exposure time (hr/day; default: 8 - see Sections 6.1.2, 6.2.2, and 6.3.2) EF = Exposure frequency (days/yr; default: 250 - see Sections 6.1.2, 6.2.2, and 6.3.2) ED = Exposure duration (yea rs; ADC and LADC: 40 years) AT = Averaging time (lifetime in years x 365 days/yr x 24 hours/day; ADC: 40 years, LADC: 70 years)

In the instances where monitoring data were not available but expos ure were considered possible, inhalation exposure assessments we re made using the OSHA PEL values, which are characterized as ”what-if” type estimates (USE PA, 1997a). The use of OSHA PELs as "what-if"Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 8

assume that the workplaces using the substitute chemical are at least in OSHA compliance with regard to the PEL for the substitute chemical. Where chemicals were monomers that had been reacted or additives that would not likely to be released from a resin matrix, inhalation exposures are characterized as negligible. Negligible inhalation exposures are defined as < 0.01 mg/m 3

TWA.

3.2.2 Dermal Exposures

Dermal exposure data and estimates were t ypically not available from most of the literature sources used for this report. Some EU Risk Assessments estim ated dermal exposures using the European Estimation and Assessment of Substance Exposure (EASE) model. These EASE model estimates are presented in this report only to allow co mparison to EPA model estimates (see Section 3.2.2).

EPA has two general categories of assessing dermal exposure when measurements are not available: 1) quantitative dermal exposure models and 2) qualitative dermal exposure assessments. Both categories of dermal e xposure assessments are discussed below.

EPA has developed a series of standard m odels for quantitatively estimating worker dermal exposures to liquid and solid chemicals during various types of activities. To estimate dermal exposure, all of these dermal exposure m odels assume a specific surface area of the skin that is contacted by a material containing the chem ical of interest, as we ll as a spec ific surface density of the material on the skin. The models also assume no use of controls or gloves to reduce the exposure. These assumptions and defau lt parameters are defined based on the nature of the exposure (e.g., one hand or two hand, immersion in material, contact with surfaces). The standard EPA dermal model equation is show n in Equation 3-2 (USEPA, 1991a; USEPA, 2000). Equation 3-2 uses unique default values based up on the nature of the c ontact and the physical

form of the chemical material. These defa ult values are summarized in Table 3-1.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 9

event chem n remain_ski surface dermal 

### N F Q AREA EXP     (3-2)

Where:

EXP dermal = Dermal exposure to the liquid or solid chemical per day (mg chemical/worker-day)

AREA surface = Surface area of the skin that is in contact with liquid or solid material containing the chemical (cm 2 ; see Table 3-1 for appropriate EPA default values) Q remain_skin = Quantity of the liquid or solid material containing the chemical that remains on the skin after contact (mg/cm 2 -event; see Table 3-1 for appropriate EPA default values)

F chem = Weight fraction of the chemical of interest in the material being handled in the activity (dimensionle ss; refer to the ESD discussion for guidance on appropriate default value)

N event= Frequency of events for the activity (EPA default = 1 event/workerday 2 )

Dermal dose in this report are estimate d in units further normalized by worker body weight, as indicated in Equation 3-3:

worker dermal dermal_bw 

### BW / EXP EXP  (3-3)

Where:

EXP dermal_bw = Dermal exposure to the liquid or solid chemical per day normalized by worker body weight (mg chemical/kg-day)

EXP dermal = Dermal exposure to the liquid or solid chemical per day (mg chemical/worker-day)

BW worker = Body weight of an average worker (kg; EPA default value = 70 kg (USEPA, 1997b))

For several categories of exposure, EPA uses qualitative assessments to estimate dermal exposure. Table 3-2 summarizes these categories and the resulting qualitative dermal exposure

assessments. Where chemicals were monomers that had been reacted or additives that would not likely to be released from a resin matrix, dermal exposures are characterized as not quantifiable. Dermal exposures to vapors and gases such as ammonia are not quantifia ble and are not included in this report.

2 Only one contact per day (N event = 1 event/worker-day) is assumed because Q remain_skin , with few exceptions, is not expected to be significantly affected either by wiping excess chemical material from skin or by repeated contacts with additional chemical material (i.e., wiping excess from the skin does not remove a significant fraction of the small layer of chemical material adhering to the skin and additional contacts with the chemical material do not add a significant fraction to the laye r). Exceptions to this assumption may be considered for chemicals with high volatility and/or with very high rates of absorption into the skin.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 10

Several of the other substitute chemicals also have volatility that, if the chemical is handled in nearly pure forms or in highly concen trated and volatile mixtures, cause exception to the default assumption N event = 1, noted for Equation 3-2 (see associated footnote). These chemicals include formaldehyde, methanol, ep ichlorohydrin, and vinyl acetate, with vapor pressures of 51, 96, 13, and 83 mmHg, respec tively (NIOSH, 2005). B ecause there is not enough information to determine altern ative values to the default for N event , dermal exposures to these chemicals are not estimated in this report wh en the chemical is expected to be handled in nearly pure forms or in highly c oncentrated and volatile mixtures.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 11Table 3-1. Standard EPA Default Values for Use in the Worker Dermal Exposure ModelsDefault ModelExample ActivitiesAREAsurfacea(cm2)Qremain_skinb(mg/cm2-event)Resulting ContactAREAsurface× Qremain_skin(mg/event)Physical Form: LiquidsEPA/OPPT 1-Hand Dermal Contactwith Liquid ModelLiquid sampling activitiesLadling liquid/bench-scale liquid transfer420(1 hand mean)Low: 0.7High: 2.1Low: 290High: 880EPA/OPPT 2-Hand Dermal Contactwith Liquid ModelMaintenanceManual cleaning of equipment and containersFilling drum with liquidConnecting transfer line840(2 hand mean)Low: 0.7High: 2.1Low: 590High: 1,800EPA/OPPT 2-Hand DermalImmersion in Liquid ModelHandling wet surfacesSpray painting840(2 hand mean)Low: 1.3High: 10.3Low: 1,100High: 8,650Physical Form: SolidsEPA/OPPT 2-Hand Dermal Contactwith Container Surfaces ModelHandling bags of solid materials (closed or empty)No defaults No defaults < 1,100cEPA/OPPT 2-Hand Dermal Contactwith Solids ModelSolid sampling activitiesFilling/dumping containers of powders, flakes,granulesWeighing powder/scooping/mixing (i.e., dyeweighing)Cleaning solid residuesfrom process equipmentHandling wet or dried material in a filtration anddrying processNo defaults No defaults < 3,100ca - These default values were adopted in the 2000 EPA report onscreening-level dermal exposureestimates (USEPA, 2000) and arethe mean values for mentaken from the EPA Exposure Factors Handbook, 1997 (USEPA, 1997b).b - These default values were adopted in the 2000 EPA report onscreening-level dermal exposureestimates (USEPA, 2000). The report derived the selectedranges of values for liquid handling activities from: U.S. EPA. ALaboratory Method to Determine the Retention of Liquids on the Surface of Hands. U.S.Environmental Protection Agency, Office of Pollution Prevention and Toxics, Exposure Evaluation Division. EPA 747-R-92-003. September 1992.c - These default values were adopted in the 2000 EPA report onscreening-level dermal exposureestimates (USEPA, 2000). The report derived values fordermal contact for solids handling activities from: Lansink, C.J.M., M.S.C. Breelen, J. Marquart, and J.J. van Hemmen: Skin Exposure to Calcium Carbonate inthe Paint Industry. Preliminary Modeling of Skin Exposure Levelsto Powders Based on Field Data (TNO Report V 96.064). Rijswijk, The Netherlands: TNONutrition and Food Research Institute, 1996.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 12

Table 3-2. EPA Default Qualitative Assessments for Screening-Level Estimates of Dermal Exposure

Category Dermal Assessment

Corrosive substances (pH>12, pH<2) Negligible

Materials at temperatures >140  F (60  C) Negligible

Cast Solids (e.g., molded plastic parts, extruded pellets) Non-Quantifiable (Some surf ace contact may occur if manually transferred)

“Dry” surface coatings (e.g., fiber spin finishes, dried paint) Non-Quantifiable (If manual handling is necessary and there is an indication that the material may abrade from the surface, quantify contact with fi ngers/palms as appropriate)

Gases/Vapors Non-Quantifiable (Some contact may occur in the absence of protective clothing)

Source: (USEPA, 1991a).

3.3 Qualitative Consumer Exposure Method

Consumers include home hobbyists, the purchaser of an article, the user of the article, and in a broader sense, the people who occupy the same space as the article. In this case the articles, for example, entertainment centers or bo ok cases, are made of the CPWs that contain the substitute chemicals of interest in this report. Consumer and commercial use will be similar in

nature but the commercial user will have a much higher exposure frequency to new products. In general new products are considered to provide the highest exposur e levels of volatile chemical

as volatile chemicals emission over time have b een shown to decline exponentially. In the commercial setting, workers will continually wo rk with new boards, while most consumers will install a limited number of new products over a greater amount of time. Therefore, only qualitative estimates are provided for consumer s and are generally based on the conclusion

drawn about commercial users.

4.0 R ELEASE D ATA C OLLECTION AND P RESENTATION

A preliminary data search for releases of substitute chemicals was begun for this report using one main source. EPA then determined th at releases would not be used for other EPA analyses, so no further data sear ches or analyses were conducte d. This report presents the preliminary data search approach and data found for informationa l purposes only. This section describes the preliminary data search approach.

Release estimates were determined by us ing EPA’s Toxic Release Inventory (TRI) database. TRI is a program created under th e Emergency Planning and Community Right-toKnow Act (EPCRA) that collects information on multi- media (e.g., land, water, air, etc.) releases and waste management activities for toxic chemi cals in the U.S. Pursuant to Section 313 of EPCRA, TRI data are gathered on a reporting-year basis and can be divided by industry sectors (NAICS codes). The data for this analysis were collected from reporting year 2008.

EPA requires all federal facilities and TRI-regulated facilities, based on the “manufacturing sector” (based on SIC codes 20 thr ough 39) to report releases to TRI. FacilitiesFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 13

are required to report to TRI if the facility manuf actures (which includes imports), processes, or otherwise uses any EPCRA Section 313 chemical in quantities greater than the established threshold (typically 25,000 pounds, but far less for persistent, bioaccumulative and toxic chemicals) in the course of a reporting year a nd has greater than a certa in number of employees (10). There are several caveats a ssociated with TRI release data:

 There can be chemical manufacturers and pro cessors that are not s ubject to TRI based on many criteria, and therefore TRI w ill underestimate overall releases.

 TRI does not have a specific line item for “ quantity sent to incineration”. However, there are TRI data elements that require facilities to identify quantities sent to on-site and to off-site treatment and to identify the “typ e” of treatment via a TRI-specific code. There are many “types” that correspond to thermal destruction (e.g., codes for incinerators, flares, thermal oxidizers, energy recovery, etc.). Releases to incineration were determined based on the appropriate codes.

 TRI requires estimates for all release and wa ste management quanti ties, including those associated with “remedial actions, catastroph ic and one-time events”. Therefore, some TRI releases are atypical and are not expected on a recurring basis.

 There is no method of determining the producti on volume or use volume associated with the facility. Submission of a TRI report is recognition that at l east one threshold was exceeded; however, the facility does not provide the quantity associated with any activity.

 Facilities must identify whether they manuf acture, process, and/ or otherwise use the chemical. However, if they identify multiple activities it is not possible to distinguish the quantity associated with each. For example, if a facility manufactur es and processes the chemical, the reported release amounts are a combination of all releases from the manufacturing and also th e processing steps.

 Use of TRI data, much like OSHA PELs, assumes a generally compliant and welloperated facility, and therefore does not take into account atypical scenarios, or those under, for example, EPA Enforcement.

5.0 L IMITATIONS OF A SSESSMENT M ETHOD AND U NCERTAINTY A SSOCIATED WITH

R ESULTS

This section discusses the lim itations of the assessment me thods presented above and the general uncertainty associated with the results.

5.1.1 Amount of Exposure Data Available

A constraint in this assessment is the amount of exposure monitoring data available in the

literature. In almost all data se ts, there are not enough da ta to establish a di stribution of exposure

concentrations or to determin e a basis for outliers. Additiona lly, the type of inhalationFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 14

concentrations (average, 95th percentile, singl e point value, assumed high-end) were not consistent for the each chemical. This uncertainty and variability, as related to worker inhalation exposures in this report, indicat e that direct quantitative comp arison between various chemicals and life cycle stages is li kely to be imprecise.

5.1.2 Applicability of Exposure or Release Data

OSHA IMIS monitoring data and TRI release data were obtained using the NAICS codes associated with the life cycle stage of interest. However, it is impossible to further refine the data to the level required for this assessment. For example, there are many types of resin manufacturing facilities that can be classi fied under the Plastics Material and Resin Manufacturing NAICS code, but there is no way to identify the specific type of facility within the NAICS code. Therefore, all OSHA IMIS and TR I data are considered to be surrogate data unless otherwise specified.

5.1.3 Representativeness of Monitoring Data and Models

OSHA IMIS data are only collected at a facility in response to a complaint, referral, or as part of a voluntary/elective program. Therefore, monitoring data is obtained from a limited number of sites, and the facili ties that were selected to obt ain this information may not be representative of the overall i ndustry, as they are either a pa rt of a complaint/referral (e.g., alleged non-compliance) or a voluntary/elective program (e.g., “beyond compliance”).

OECD SIDS and EU Risk Assessment data are typically collected from other countries. Worker conditions may be drastically different than those in the U.S. and may not properly represent U.S. occupational exposur es and environmental releases.

Much of the exposure data used in this asse ssment were not measured in the past five years. Facility conditions may ha ve changed with the addition of new chemical technologies, process technologies, engin eering controls, or PPE.

Modeling inhalation exposures due to lack of data sometimes employs the assumption of compliance with the OSHA PEL and therefore a concentration at or below the PEL. EPA

conducted an informal review of a limited set of monitoring data for some substances with OSHA PELs, and the review indicated that use of such modeling tends to generally overestimate exposure concentrations, and sometimes very significantly (e.g., orders of magnitude).

Modeling dermal exposures has a number of lim itations and uncertainties. For example, the EPA models are intended for use in screening- level assessments and provide an estimate of potential dermal exposure and do not take into account the protection from the possible use of gloves. Hand exposure only is assumed because available data indica tes that hand exposure constitutes the majority of the total body exposur e. (USEPA, 2000)

5.1.4 Sources of Exposure

In many cases, monitoring data are collected and presented for a general area or for particular worker activities. However, these m onitoring data do not indicate the specific sourceFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 15

of exposure. For example, monitoring data do no t distinguish whether th e source of measured chemical exposure is from the resin, the w ood or adjacent processes unrelated to CWPs. Therefore, it is not possible to determine what portion of the measured concentration can be

attributed to the CWPs.

5.1.5 Frequency and Duration of Exposure

The OSHA IMIS database includes some data on the frequency and duration of worker exposure, but many sites did not provide data. For th e data available, there is variability in the

various worker activities and sites. These worker activities typically ca nnot be matched between sites; therefore the frequency and duration of worker exposures also cannot be compared directly. Monitoring data found in EU Risk Assessments and OECD SIDS reports typically did not report the average duration and frequency of exposures.

For the purpose of calculating exposures, the duration and frequency of exposure was assumed to be 8 hours per day and 250 days per year where better assumptions for duration of exposure were not available. Economic census data are presented in Sect ion 6.0 that support the use of this assumption.

5.1.6 Number of Sites and Workers

Specific information on the number of CWP ma nufacturing sites was provided from trade associations. However, these estimates under-re present the number of sites and workers in existence, because trade associations represen t only a segment of industry, and may exclude

smaller facilities.

Although there is some current informati on on the number of CW P manufacturing sites from the trade associations, limited information is available to describe resin manufacturing, downstream product manufacturing, and commercial use industries. The U.S. Economic Census provides representative estimates of the num bers of chemical ma nufacturers, resin manufacturers, and downstream product manufactu rers for each relevant industry and the respective number of production worker s or employees in each industry.

However, as stated previously, the Economic Census reports information according to NAICS codes, which may encompass facilities that may not be involved in the manufacture, distribution, or use of the composite wood products of interest. Additionally, each site within the industries may or may not use the particular chemi cal of interest. Furthermore, the census data were taken in 2002, which is prior to the data quality preference year of 2005. Therefore, these

factors indicate that a limited level of detail and accuracy are possible for these parameters.

5.1.7 Post-CARB Rule Exposures

In 2007, the California Air Resources Bo ard (CARB) adopted a regulation that established maximum formaldehyde emissions from the three types of CWPs. EPA was petitioned in March 2008 under TS CA Section 21 to adopt similar regulations. This petition spurred the development of several analys es, including this exposure assessment.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 16

A significant limitation of the data and methods in this report is the lack of a method to further extrapolate the estimat ed inhalation exposure concentr ations (LADCs and ADCs) from pre-CARB levels to several post-CARB e xposure concentrations of interest.

EPA has a particular interest in two sets of exposure concentrations : pre-rule baseline and post-rule. Pre-rule baseline corr esponds to expected exposures im mediately prior to the rule’s implementation. Post-rule corresponds to expected exposures following the rule’s implementation.

Exposure monitoring data gathered for this report were genera ted prior to CARB regulatory implementation. The effects of implem entation of the CARB rule and of this federal rule on worker exposures cannot be simply determin ed because the data is not yet available. The effects of these rules on worker exposures to fo rmaldehyde in UF resin ma nufacture could be to decrease one or a combination of the following parameters (as compared to pre-CARB formaldehyde regulation): expected exposure co ncentrations of formaldehyde, numbers of workers exposed, exposure frequency (days/yr), exposure duration (hours/ day). The effects of these rules on worker exposures to the substitute chemicals (o ther than formaldehyde) in the various life cycle stages noted in this report coul d be to increase one or a combination of the following parameters (as compared to pre-CARB) : expected exposure concentrations of the chemical, numbers of workers exposed, expos ure frequency (days/yr), exposure duration (hours/day).

The complexities of the CARB regulation a nd proposed federal rules’ effects on these sets of parameters could not be quantified for this report.

6.0 G ENERAL P ROCESS D ESCRIPTIONS AND F ACILITY E STIMATES

This section presents general facility es timates for resin manufacturing, primary manufacturing, and downstream manufacturing for the substitute chemicals and composite wood products. General facility estim ates include NAICS industry s ectors, census estimates on the number of establishments and production work ers, and average production hours per worker. This section also compares census-derived e xposure durations and exposure frequencies with assumptions used for exposure duration (eight ho urs per day) and exposur e frequency (250 days per year).

6.1 Resin Manufacturing

NAICS codes have index entries that list th e specific types of industries that are applicable to the particular NAICS code. 3 The index entries were searched for the various types of resin manufacturing. Severa l types of resin manufacturing we re classified under NAICS code

3 NAICS code search is available on the U.S. Census Bureau Web Site: http://www.census.gov/cgibin/sssd/naics/naicsrch?chart=2007Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 17

325211 – Plastics Material and Resin Manufacturing. Table 6-1 presents th e index entries that were matched with the life cycle st ages assessed in this report.

Table 6-1. Index Entries within NAICS Co de 325211 (Plastics Material and Resin Manufacturing) Matched with Corresponding Resin Manufacturing Life Cycle Stages

Index Entries within NAICS Code 325211 (Plastics Material and Resin Manufacturing) Corresponding Li fe Cycle Stage

Urea-formaldehyde resins manufact uring UF Resin Manufacturing

Vinyl acetate resins manufacturing PVA Resin Manufacturing

Melamine resins manufacturing MF and MUF Resin Manufacturing

Phenol-formaldehyde resins manufacturing PF Resin Manufacturing

Diisocyanate resins manufacturing pMDI Resin Manufacturing

It is unclear where polyamine epichlor ohydrin (PAE) resin manufacturing may be classified, but based on TRI reporting by Hercules, Inc. 4 , a known PAE manufacturer, PAE manufacturing may possibly fa ll under NAICS codes 325211 - Plas tics Material and Resin Manufacturing, 325199 - All Other Basic Organi c Chemical Manufacturing, or 325998 - All

Other Miscellaneous Chemical Produc t and Preparation Manufacturing.

6.1.1 General Resin Manufacturing Process

In general, resins are made via batchwis e processes. For example, UF resin is manufactured by charging formaldehyde and othe r reactants to a kettle. A variety of posttreatment processes may be applied, and the pr oduct is drummed for sale (Kirk-Othmer, 2002a). More detailed process descripti ons are described in the respectiv e sections for each chemical in Section 7.0, where applicable.

6.1.2 Number of Establishments, Workers, Production Hours, and Work Day Estimates

Estimates for the total number of worker s and aggregate production hours for resin manufacturing were obtained from the 2002 Econo mic Census for the NAICS codes discussed above in Table 2-2 (U.S. Census Bureau, 2002a). Using these data, an average production days per year per worker (assuming eight hours per day) and averag e production hours per day per worker (assuming 250 days per year) were calculat ed. The results are given in Table 6-2. The calculated days per year and hours per day fo r each NAICS industry code associated with chemical and resin manufacturing deviate from th e assumed values for frequency of exposure of 250 days per year and duration of exposure of 8 hours per day by less than 10 percent (USEPA. 1992b). Therefore, this assessment uses the assu med values for exposure duration and frequency for resin manufacturing.

4 TRIFIDs 31401HRCLSOLDLO, 01013HRCLS1111G, 39401HRCLSWEST7, 53209HRCLS5228N, and

97210HRCLS3366N.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 18Table 6-2. Summary of 2002 Economic CensusData and Parameters Calculated fromthese Data for Resin ManufacturingSites2002 Economic Census DataParameters Calculated from theCorresponding 2002 Economic CensusDataNAICSDescriptionCompaniesNumber ofEstablishmentsProductionWorkersAggregateProductionHoursWorked(1,000hours)AverageProductionWorkersper SiteAverageProductionDays perYear(assuming8 hr/day)aAverageProductionHours perDay(assuming250days/yr)b325199All Other Basic Organic ChemicalManufacturing 539 700 40,771 84,466 58 259 8.29325211Plastics Material and ResinManufacturing 794 1,059 48,002 99,003 45 258 8.25325998All Other Miscellaneous ChemicalProduct and Preparation Manufacturing 1,079 1,223 21,950 44,356 18 253 8.08Source: US Census Bureau, 2002a.a – OPPT’s standard default estimate for frequency of exposure is 250 days per year (USEPA, 1992b).b – OPPT’s standard default estimate for duration of exposure is 8 hours per day (USEPA, 1992b).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 19

6.2 Composite Wood Product Manufacturing

According to an NAICS index entry search 3 , HWPW, MDF, and PB are divided between two industrial categories. HW PW manufacturing is classi fied under NAICS code 321211 – Hardwood Veneer and Plywood Manufacturing, while MDF and PB manufactur ing are classified

under NAICS Code 321219 – Reconstitu ted Wood Product Manufacturing.

6.2.1 Potential Exposure Activities

The manufacturing processes for com posite wood products generally include a combination of raw material processing (e.g. l og debarking, chipping, screening), wood drying, resin application or resi n blending, forming, pressing, cooling, cutting, and finishing. Detailed process descriptions can be found in the “Assessment of Occ upational Exposure to Formaldehyde from Composite Wood Products” (USEPA, 2011b). According to this reference, workers may be exposed to formaldehyde through one or more of the following activities during CWP manufacturing:

 Dermal contact with resins;

 Emissions of volatile chemicals from resi ns during resin application, blending, forming, and conveying;

 Sampling of resinated materi al prior to pressing;

 Assembly of the composite wood pr oduct after resin application;

 Hot-pressing;

 Finishing activities; and

 Emissions in work areas where stacks of CWPs are cooled, finished, and stored.

Exposures to the substitutes that are re sin monomers or additives would likely occur during similar types of activities, depending on the physical properties of the substitutes (volatility, corrosivity, etc.). The level of exposure may also differ depending on the composition of the resin, use of the substitute chemical, and the type of engineering controls in place.

6.2.2 Number of Establishments, Workers, Production Hours, and Work Day Estimates

The assessed numbers of sites for the manuf acture of the three CWPs are given in Table

6-3 and Table 6-4. Alternative values for th e number of sites are available from the 2002 Economic Census and are given in Table 6-5. The number of sites re ported by the Composite Panel Association (CPA) and the U.S. International Trade Commission (USITC) is much lower than in the Economic Census data. This is primar ily due to the fact that the NAICS codes used for the Economic Census data, NAICS code 321211 (hardwood veneer and plywood manufacturing) and NAICS 321219 (reconstitute d wood product manufacturing), encompass

additional industrial manufacturi ng sites outside of HWPW, MDF and PB, while at the same time, estimates provided by trad e associations do not include non- members or small businesses.

Similar to the Economic Census analysis done in Section 6.1.2, the average production days per year per worker (assuming eight hours per day) and average pr oduction hours per day per worker (assuming 250 days per year) we re calculated for composite wood product manufacturing industries. As seen in Table 6- 5, the frequencies of exposure and productionFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 20

hours per day do not deviate by more than 10 percent from the assumed values for frequency of exposure of 250 days per year (assuming a five day work week and 50 weeks per year) and duration of exposure of 8 hours per day (assumed as a normal shift dura tion). Therefore, the frequency and production hours per day for HWPW , MDF and PB manufacturing are assumed to be 250 days per year, over 8 hours per day, respectiv ely. These values are also assumed to apply generally to all workplaces in the CWP lifecycle for the pur pose of assessing exposures to

substitutes.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 21Table 6-3. Number of U.S. Hardwood Plywood MillsHardwood Veneer and Plywood MillComposite Wood Product TypeNumber of U.S. MillsHardwood Plywood Mills Hardwood Plywood 24Source: USITC, 2008a.Table 6-4. Number of U.S. Reconstituted Wood Product MillsReconstituted WoodProduct Mill TypeComposite Wood Product TypeNumber of U.S. MillsParticleboard Mills Particleboard 34Medium-Density Fiberboard Mills Medium-Density Fiberboard 27Source: AWFS, 2009a. Note: The number of MDF mills is a high-endestimate that may include some hardboard mills: the presentation did not differentiatebetween non-CPA-member MDF and hardboard mills.Table 6-5. Summary of 2002 Economic CensusData and Parameters Calculated from these Data for CWP ManufacturingSites2002 Economic Census DataParameters Calculated from theCorresponding 2002 Economic CensusDataNAICSDescriptionCompaniesNumber ofEstablishmentsProductionWorkersAggregateProductionHoursWorked(1,000hours)AverageProductionWorkersper SiteAverageProductionDays perYear(assuming8 hr/day)aAverageProductionHours perDay(assuming250 days/yr)b321211Hardwood veneer and plywoodmanufacturing 303 337 16,861 34,298 50 254 8.14321219Reconstituted wood productmanufacturing 177 282 17,967 38,383 64 267 8.55Source: US Census Bureau, 2002a.a – OPPT’s standard default estimate for frequency of exposure is 250 days per year (USEPA, 1992b).b – OPPT’s standard default estimate for duration of exposure is 8 hours per day (USEPA, 1992b).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 22

6.3 Downstream Product Manufacturing

Downstream product manufacturing may be cl assified under a numb er of different NAICS codes, as listed in Table 2-2. The NAICS codes were iden tified by first obtaining HWPW, PB, and MDF market data from th e Hardwood Plywood and Veneer Association (HPVA) and CPA (HPVA, 2009a; CPA, 2008a). The end market data descriptions for HWPW, PB, and MDF were then matched to appropriate NAICS codes, based on engineering judgment. Downstream product manufacturing comprises an amalgam of different composite wood products, which in turn may also be made usi ng different types of re sins or adhesives.

6.3.1 Potential Exposure Activities

A general description of the manufacturi ng process is presented below. Detailed information on the manufacture of specific dow nstream products was re searched, but was not

found in the limited data review used for this report. The Office of Enforcement and Compliance Assurance (OECA) sector notebook provides a ge neral process descript ion for wood furniture

and fixtures constructed from raw lumber . Activities involved in downstream product manufacturing processes include drying the raw wood; sawing into appropriate sizes, planing, and bending (i.e., machining); assembling the w ood material into part s; applying veneers; sanding; prefinishing (watering, sanding, derosi nation, bleaching); coating by spraying, brushing, or dipping; and finishing (OECA, 1995a). A similar process may be used to produce furniture and fixtures using composite wood products (see below for a di scussion of activities during wood product manufacturing). Solvent-based form ulations, hot melts, and polyvinyl acetate are

common adhesives used in the furn iture industry. Therefore, these adhesives may also contain or emit formaldehyde substitutes.

The following representative activities (unit operations) are typically required during wood product manufacturing based on survey re sults of manufacturers (GDNR, 1996a). Although the reference does not identify the raw materials used by manufacturers included in the survey (e.g. composite wood products or ra w lumber), it does state that wood product manufacturers may produce different products using similar processes. Therefore, it is possible

that the cited activitie s may be applicable to composite wood products in downstream product manufacturing. The cited activities include the following:

 Laminating;

 Assembly;

 Glues and adhesives;

 Spray application;

 Painting and coating;

 Water-based coating;

 Solvent-based coating;

 Staining;

 Sealing;

 Water-based cleaning; and

 Solvent-based coating.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 23

These process activities apply to the following downstream product manufacturing sectors: millwork, cabinet makers, trusses, prefabricated construction, wood furniture, miscellaneous furniture, exhibits and showr ooms (GDNR, 1996a). Composite panel products typically have decorative finishes or overlays that may be applied at a “sister” facility of the primary manufacturer or at an unaffiliated finishing site (C PA, 2009a). However, there is no specific NAICS code related to laminating facilities.

Although worker activities specific to co mposite wood products in the downstream product manufacturing industries have not been described, workers are potentially exposed to formaldehyde and its substitutes from the unfinished composite wood products during storage and handling. Process operations where exposur e may occur include laminating with decorative veneer, cutting, sanding, assembling, and fini shing operations. Workers are also potentially exposed to emissions from finished, coated or laminated composite wood products, although emissions rates from the coated and laminated pr oducts are generally lower than those from the unfinished products (Battelle, 1996a).

6.3.2 Number of Establishments, Workers, Production Hours, and Work Day Estimates

As was done in Sections 6.1.2 and 6.2.2, th e average production days per year per worker (assuming eight hours per day) and average prod uction hours per day per worker (assuming 250 days per year) were calculated for composite wood product manufacturing industries, using the 2002 Economic Census data (U.S. Census Bureau, 2002a). As seen in Table 6-6, the frequency of exposure and production hours per day do not de viate from the OPPT default values for frequency of exposure of 250 days per year and duration of exposure of 8 hours per day by more than 10 percent (USEPA. 1992b). Therefore, th e frequency and producti on hours per day for downstream product manufacturing are assessed to be 250 days per year, over 8 hours per day, respectively.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 24Table 6-6. Summary of 2002 Economic CensusData and Parameters Calculated fromthis Data for Potential DownstreamProduct Manufacturing Sites2002 Economic Census DataParameters Calculated from theCorresponding 2002 Economic CensusDataNAICSDescriptionCompaniesNumber ofEstablishmentsProductionWorkersAggregateProductionHoursWorked(1,000)AverageProductionWorkersper SiteAverageProductionDays perYear(assuming8 hr/day)aAverageProductionHours perDay(assuming250 days/yr)b321911 Wood window and door manufacturing 1,326 1,443 55,566 106,720 39 240 7.68321918 Other millwork (including flooring) 2,016 2,071 35,989 69,325 17 241 7.71321991Manufactured home (mobile home)manufacturing 237 416 40,290 75,296 97 234 7.48321992 Prefabricated wood building manufacturing 667 739 18,472 36,193 25 245 7.84337110Wood kitchen cabinet and counter topmanufacturing 9,457 9,561 100,210 195,053 10 243 7.79337121Upholstered household furnituremanufacturing 1,686 1,911 77,284 145,105 40 235 7.51337122Non-upholstered wood household furnituremanufacturing 3,975 4,114 95,890 184,861 23 241 7.71337127 Institutional furniture manufacturing 687 731 24,557 48,944 34 249 7.97337129Wood television, radio, and sewing machinecabinet manufacturing 201 205 2,827 5,767 14 255 8.16337211 Wood office furniture manufacturing 547 570 19,230 36,877 34 240 7.67337212Custom architectural woodwork andmillwork manufacturing 1,543 1,568 23,080 45,310 15 245 7.85337214Office furniture (except wood)manufacturing 260 312 24,357 48,918 78 251 8.03337215Showcase, partition, shelving, and lockermanufacturing 1,795 1,891 53,283 102,777 28 241 7.72Source: US Census Bureau, 2002a.a – OPPT’s standard default estimate for frequency of exposure is 250 days per year (USEPA, 1992b).b – OPPT’s standard default estimate for duration of exposure is 8 hours per day (USEPA, 1992b).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 25

6.4 Commercial Use

Workers are potentially exposed to formaldehyde or its substitutes during construction of a building, installation of cabinets, vanities, a nd flooring, or while working within a commercial building. However, no general use volumes, nu mber of establishments, employees, employed hours or work days estimates were identified. This can be expected as al l construction projects are different, and there is a wide variation in th e sizes and scopes of cons truction projects. In addition, no exposure data during commercial use were identified; therefore commercial use has not been assessed in this report.

6.5 Consumer Use

Consumer use, such as home hobbyists, Do-I t-Yourselfers (DIY), home occupants, are potentially exposed to formaldehyde or its s ubstitutes during construction of a building, installation of cabinets, vanities , and flooring, or while working indoors in a home or work shop. However, no general use volumes, number of ho mes, hobbyist or work days estimates were identified. This can be expected as DIY projects are different, and th ere is a wide variation in the sizes and scopes of DIY projects. In addition, no exposure data were identified for consumers using CWP boards made with substitute chemi cals; therefore consumer use has not been assessed quantitatively in this report. It is a ssumed in this report that consumer use does not include any manufacture of CWPs, such as gluing wood veneers onto platforms.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 26

7.0 E XPOSURE A SSESSMENT BY C HEMICAL

This section assesses occ upational exposure and environmental release during each relevant life cycle stage. This section is orga nized according to chemical and life cycle stage. Definitions of occupational valu es are given in Appendix A.

7.1 Formaldehyde Exposure during UF Resin Manufacturing

This section provides an exposure assessmen t for formaldehyde dur ing the manufacture of UF resin. UF resin manufacturing is classi fied under NAICS code 325211 – Plastics Material and Resin Manufacturing. Table 7-1 presents es tablished occupational e xposure limits (OELs) for formaldehyde.

Table 7-1. Occupational Exposu re Limits for Formaldehyde

Source Limit Type Exposure Limit a

OSHA PEL 8-hour TWA 0.75 ppm (0.92 mg/m 3 )

15-minute STEL 2 ppm (2.5 mg/m 3 )

NIOSH REL 8-hour TWA 0.016 ppm (0.020 mg/m 3 )

ACGIH TLV Ceiling 0.3 ppm (0.37 mg/m 3 )

Sources: OSHA. 2008; NIOSH, 2005; ACGIH, 2009. a - The formaldehyde concentration in mg/m 3 was calculated from the provided concentration in ppm by multiplying the concentration in ppm by 1.229 mg/m 3 /ppm (i.e., 1 ppm = 1.229 mg/m 3 ).(NIOSH, 2005)

7.1.1 Process Description

Amino resins, such as UF, are usually made via batchwise processes. These reactions are controlled through the mole ratio of reactants, ca talyst (pH of reaction mixture), reaction time, and temperature. Formaldehyde and other reactants are charged to a kettle, adjusted for pH, and then heated. After condensation is complete, there are often post-treatment processes to evaporate excess water and formaldehyde or a dd additional urea to de crease the ratio of formaldehyde to urea. The final resin syrup produ ct may have formaldehyde concentrations of 0.59% or less (Fink, 2005a) and can either be loaded for sale to downstream customers or processed further into other resin products de pending on the application (Kirk-Othmer, 2002a). Feedstock formaldehyde for UF resin production is typically in the form of formalin, an aqueous mixture with formaldehyde percentages ra nging from 37 to 50 percent. (Fink, 2005a)

During the manufacture of amino resins, every effort is made to recover and recycle the raw materials; however, there may still be some losses of formaldehyde during tank or reactor venting (Kirk-Othmer 2002a). A repres entative process flow diagra m of UF resin manufacturing is provided below in Figure 7- 1; although, the figure also in cludes optional steps of molding compound manufacture and spray-dr ied resin manufacture after the resin syrup is formed. No information was found on engineering controls or PPE used when handling formaldehyde during UF resin manufacturing.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 27Figure 7-1. Process flow diagram for UFresin manufacturing (Kirk-Othmer, 2002a)Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 28

7.1.2 Exposure Assessment for Formaldehyde in UF Resin Manufacturing

Inhalation monitoring data for formaldehyde sp ecifically during UF resin manufacturing were not found. The most recent surrogate da ta found in the OSHA IMIS database was under NAICS code 325211 (Plastics Material and Resi n Manufacturing), which would include UF resin manufacturing facilities. Tabl e 7-2 presents this surrogate inhalation monitoring data from

the OSHA IMIS database. Note that the monito red concentration in Table 7-2 does not exceed the OSHA PEL of 0.75 ppm (8-hr TWA).

Table 7-2. Surrogate Inhalation Monitoring Da ta from OSHA IMIS Database used to represent Formaldehyde Concentrations during UF Resin Manufacturing

Industry Worker Activity Description Number

of Sites

Monitored Monitored Formaldehyde

Concentration (ppm) Monitored Formaldehyde

Concentration (mg/m 3 ) a Monitoring Type Year Concentration

Level / # of

Data Points

Plastics

Material and

Resin Manufacturing (NAICS 325211) Lead Man 1 0.064 0.079 Personal (TWA) 1980 1 Data Point

Source: OSHA, 2010. a - The formaldehyde concentration in mg/m 3 was calculated from the provided concentration in ppm by multiplying the concentration in ppm by 1.229 mg/m 3 /ppm (i.e., 1 ppm = 1.229 mg/m 3 ).(NIOSH, 2005)

Table 7-3 presents the estimated ADC a nd LADC of formaldehyde during UF resin manufacturing. As discussed in Section 6.1.2 fo r general resin manufactur ing, the frequency of exposure is assessed to be 250 da ys per year and the duration of exposure is assessed to be 8 hours per day.

Table 7-3. Estimated Average Daily Concentrat ions for Data Representing Formaldehyde during UF Resin Manufacturing

Industry Worker Activity Description Concentration

Level Monitored Formaldehyde

Concentration (mg/m 3 ) Average Daily

Concentration ( μ g/m 3 ) Lifetime Average Daily

Concentration ( μ g/m 3 )

Plastics Material

and Resin Manufacturing (NAICS 325211) Lead Man 1 Data Point 0.079 18 10

The dermal model used for estimates in this report could not be adjusted to account for the higher volatility of the formalin raw materi al containing formaldehyde - see Section 3.2.2 for an explanation. However, free formaldehyde may exist at about 0.59% or less in the non-volatile resin (Fink, 2005a). Based on this concentra tion and the EPA/OPPT 2-Hand Dermal Contact with Liquid Model (see Section 3.2.2), the dermal exposure dur ing activities where workers contact or handle liquid UF resin product is estimated to be 0.05 to 0.15 mg/kg/day formaldehyde.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 29

7.1.3 Uncertainty in Exposure Assessment

Because no data were available for formal dehyde in UF resin manufacturing surrogate data were used. However, the extent that this surrogate data is actually representative of formaldehyde in UF resin manufacturing is unknow n. Additionally, there is only one data point available, making it difficult to characterize the data. Overall data limitations and uncertainties

are discussed in Section 5.0.

7.1.4 Environmental Releases of Formaldehy de during UF Resin Manufacturing

Table 7-4 presents releases of form aldehyde under NAICS code 325211 (Plastics

Material and Resin Manufacturin g) reported to the TRI for re porting year 2008. In 2008, the majority of releases were sent for off-site wate r treatment, with the remainder split between air, landfill, or incineration.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 30Table 7-4. Environmental Releases of Formaldehyde during Plastics Material and Resin Manufacturing as Reported in TRI forReporting Year 2008PrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers for Release (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotalAirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWateraIncineration325211(64 sites)Plastics Material andResin Manufacturing 205,136 44,885 250,021 7,687 289,757 547,465 117,780 13,984 131,764 679,229 3,055,017 277,085Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedor transferred off site for treatment in wastewater and incineration units. It does not include quantitiessent to on- and off-site waste management such as recycling and reuse.a - Off-site water transfer includes Publicly Owned TreatmentWorks (POTWs) and Waste Water Treatment Plants (WWTPs).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 31

7.2 Methanol

Methanol is used to manufacture formalde hyde, which is subsequently used in the production of UF resins for use in the CWPs industry. Feedstock formaldehyde for UF resin production is typically in the form of form alin, an aqueous mixture with formaldehyde percentages ranging from 37 to 50 percent (Fink, 2005a). Formalin may also contain methanol in varying concentrations, although typical concentr ations are approximately 10 percent (Kiernan, 2000a). This can result in exposure to methanol during the UF resin manufacturing process. Residual methanol in the resin may lead to ad ditional exposures during downstream composite wood product production and subsequent industria l and commercial use. Table 7-5 lists

established OELs in the U.S.

Table 7-5. Occupational Exposure Li mits for Methanol (CASRN 67-56-1)

Source Limit Type Exposure Limit

OSHA PEL 8-hour TWA 200 ppm (260 mg/m 3 )

NIOSH REL a TWA for up to a 10-hour workday

and a 40-hour workweek 200 ppm (260 mg/m 3 )

Short-term exposure limit 250 ppm (325 mg/m 3 ).

ACGIH TLV a, b TWA for up to an 8-hour workday

and a 40-hour workweek 200 ppm (260 mg/m 3 )

Short-term exposure limit 250 ppm (325 mg/m 3 )

Sources: OSHA, 2006; NIOSH, 2005; ACGIH, 2009. a – NIOSH and ACGIH also assign a "Skin" notation to methanol.

b – The ACGIH TLV for methanol is ba sed, among other things, upon the pote ntial for sensitization and meant to protect workers from induction of this effect.

This section provides the exposure assessm ent for methanol during the following life cycle stages: UF resin manufacturing, CWP manu facturing, downstream product manufacturing,

and commercial/consumer use.

7.2.1 Manufacture of UF Resin

The manufacture of UF resins is typically achieved in basic stages starting with methylolation, then condensation, and finally pos t treatment. This is typically done in a batch process and can involve several types of processing equipment (Fink, 2005a).

Process Description

The UF manufacturing process has been previ ously described in Section 7.1. A modifiedUF resin was made for PB by adding extra methanol to the process (cappi ng the methylol urea as methyl ethers), thereby reducing the formalde hyde emissions (USEPA, 2011c). No specific

information was found in the literature concerni ng the amount of methanol added, nor was any

information found about where in the process the methanol is added.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 32

The NIOSH international chemical safety card for methanol recommends the use of protective gloves, protective clothing, safety goggles, and lo cal exhaust ven tilation when handling methanol (NIOSH, 1994a). Specific PPE a nd engineering controls regarding methanol use during UF resin manufactur e were not available.

Exposure Assessment for Methanol in the Manufacture of UF Resin

Inhalation monitoring data for methanol e xposures during UF resin manufacturing were not found. Additionally, surrogate data were no t found in the OSHA IMIS database for any relevant NAICS codes. The OECD SIDS report for methanol indicated that the major sources of methanol include: 1) production, storage, and use as a solvent, 2) use as a chemical intermediate, and 3) as a trace constituent from vehicle e ngines (OECD, 2004a). The OECD SIDS report presented the 95 th percentile value of general inhalati on monitoring data taken from several workplaces at BASF AG in Ludwigshafen, Germany, but did not specifically present monitoring data for UF resin manufacturing. Table 7-6 presen ts the general workplace inhalation monitoring data that were used as surrogate data for UF resin manufacturing processes.

Table 7-6. Surrogate Inhalation Monitoring Da ta from OECD used to represent Methanol Concentrations during UF Resin Manufacturing

Type of Monitoring Dates Worker Activities Number of Samples Values (mg/m 3 )

8-hr TWA 1998-2003 Production, processing, quality control, pilot plant, research laboratories, filling stations, etc. 950 32 (95 th percentile) a

Source: OECD, 2004a. a – The OECD SIDS report only provided the 95 th percentile data.

Table 7-7 presents the calculated ADC and LADC (see Section 3.2.1). Note that the 95 th
percentile concentration provided by OECD is well below the OSHA PEL of 260 mg/m 3 . As discussed in Section 6.1.2 for general resin manuf acturing, the frequency of exposure is assessed to be 250 days per year and the duration of e xposure is assessed to be 8 hours per day.

Table 7-7. Estimated Average Daily Concentr ations for Data Representing Methanol during UF Resin Manufacturing

Industry Worker Activity Description Concentration

Level Monitored

Methanol

Concentration (mg/m 3 ) Average Daily

Concentration ( μ g/m 3 ) Lifetime Average Daily

Concentration ( μ g/m 3 )

Unknown Production, processing, quality control, pilot plant,

research laboratories, filling stations, etc. 95 th percentile (of 950 samples) 32 7,300 4,200

The dermal model used for estimates in this report could not be adjusted to account for the higher volatility of methanol - s ee Section 3.2.2 for an explanation.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 33

Uncertainty in Exposure Assessment

There is a lack of monitoring data for me thanol during UF resin manufacturing. The OECD SIDS data provides one data point representing a 95 th percentile of 950 data points for methanol exposures, but does not specifically targ et UF resin manufactur ing. Additionally, these samples were taken from areas in Germany, wh ere the conditions may not be indicative of the conditions in the U.S. However, these samples we re taken in industrial settings and may provide some insight into methanol exposures at UF re sin manufacturing plants. Overall data limitations

and uncertainties are discussed in Section 5.0.

Environmental Releases of Methanol during UF Resin Manufacturing

Table 7-8 presents releases of methanol under NAICS code 325211 (Plastics Material and Resin Manufacturing) reported to the TRI for repor ting year 2008. The main media of release is off-site incineration, followed by off-site water treatment.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 34Table 7-8. Environmental Releases of Methanol during Plastics Material and Resin Manufacturing Reported in TRI forReporting Year 2008PrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers for Release (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotal AirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWateraIncineration325211(111 sites)Plastics Material andResin Manufacturing 1,824,2561,622,898 3,447,155 54,452 1,748,854 5,250,461 2,835,660 46,4132,882,073 8,132,534 5,794,872 7,388,398Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedor transferred off site for treatment in wastewater and incineration units. It does not includequantities sent to on- and off-site waste management such as recycling and reuse.a - Off-site water transfer includes Publicly Owned TreatmentWorks (POTWs) and Waste Water Treatment Plants (WWTPs).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 35

7.2.2 Methanol in CWP Manufacture

Methanol may be available for exposure duri ng the use of UF resins in CWP manufacture and is expected to be volatilized du ring the curing process (USEPA, 2011c).

Process Description

Manufacture of composite wood products is expe cted to be identical to the general CWP manufacturing process description described in Section 6.2.1. No data on engineering controls and PPE during the use of methanol in CWP manufacturing were found.

Exposure Assessment for Methanol in CWP Manufacturing

Because of volatilizatio n of methanol during the curing pr ocess, inhalation exposures are expected to be higher during CWP manufacturing than during the UF resin manufacturing. However, no inhalation monitoring data were found for methanol durin g CWP manufacturing. Therefore, formaldehyde monitoring data were used as a model to estimate methanol exposures, because both have similar vapor pressures.

In Section 7.1.2, a formalde hyde air concentration of 79 μ g/m 3 was assessed during the UF resin manufacturing process. EPA’s expos ure assessment of formaldehyde in CWPs presented formaldehyde air concentrations up to 1,900 μ g/m 3 at potential CWP manufacturing sites (USEPA, 2011b). The formaldehyde conc entration during CWP manufacturing is approximately 24 times higher than during UF resin manufacturing.

Section 7.2.1 assessed a metha nol concentration of 32 mg/m 3 during UF resin manufacturing. Applying the multiplier of 24, calculated from the increase in formaldehyde concentrations, results in an estima ted methanol concentration of 777 mg/m 3. Note that this

calculated is well above the OSHA PEL of 260 mg/m 3 . Therefore, the OSHA PEL value is used as the “what-if” type estimate. Table 7-9 presents the calculat ed ADC and LADC for methanol (see Section 3.2.1).

Also as discussed in Section 6.2.2 fo r composite wood product manufacturing, the frequency of exposure is assesse d to be 250 days per year an d the duration of exposure is assessed to be 8 hours per day.

Table 7-9. Estimated “What-If” Average Daily Concentrations of Methanol during CWP Manufacturing, based on the OSHA PEL

Source Limit Type Methanol Exposure Limit (mg/m 3 ) Average Daily

Concentration ( μ g/m 3 ) Lifetime Average Daily Concentration ( μ g/m 3 )

OSHA PEL 8-hour TWA 260 59,000 34,000

The dermal model used for estimates in this report could not be adjusted to account for the higher volatility of methanol - s ee Section 3.2.2 for an explanation.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 36

Uncertainty in Exposure Assessment

There is a lack of monitoring data for me thanol during CWP manu facturing. Inhalation exposures estimates were assume to be below the OSHA PEL, which is cons idered as a “what-if” type estimate. Dermal exposures could not be es timated, due to the volatile nature of methanol.

Overall data limitations and uncertainties are discussed in Section 5.0.

Environmental Releases of Methanol during CWP Manufacturing

Table 7-10 presents releases of me thanol during NAICS codes 321211 and 321219 (Hardwood Veneer and Plywood Manufactur ing and Reconstituted Wood Product Manufacturing, respectively) re ported to the TRI for reporting year 2008. The majority of

releases are to stack air in both industries.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 37Table 7-10. Environmental Releases of Methanol during CWP Manufacturing Reported in TRI for Reporting Year 2008PrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers for Release (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotal AirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWateraIncineration321211(2 sites)Hardwood Veneer andPlywood Manufacturing 43,449 6,332 49,781 0 0 49,781 0 0 0 49,781 0 0321219(73 sites)Reconstituted WoodProduct Manufacturing 4,542,783 103,440 4,646,223 390 18 4,646,631 565 0 565 4,647,196 267 24Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedor transferred off site for treatment in wastewater and incineration units. It does not includequantities sent to on- and off-site waste management such as recycling and reuse.a - Off-site water transfer includes Publicly Owned TreatmentWorks (POTWs) and Waste Water Treatment Plants (WWTPs).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 38

7.2.3 Downstream Product Manufacture and Commercial/ Consumer Use

Methanol is expected to be volatilized during curing in the CW P manufacture process (USEPA, 2011c). Therefore, exposures and releases of trace residual methanol are expected to be negligible or non-quantifiable for downstream product manufacturing and commercial use. Since consumer use would be in this set of life cy cle stages, consumer exposure is expected to be negligible as well.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 39

7.3 Melamine

The major demand for melamine (CASRN 108-78- 1) in the U.S. is for surface coatings and laminating resins (Mannsville, 2006a; Kirk -Othmer, 2002a). Melamine currently does not have any occupational exposure limits esta blished by OSHA, NIOSH, or ACGIH (USEPA, 2009d). The vapor pressure of melamine is 4.7 x 10 -8 Pa (3.5 x10 -10 mm Hg) at 20 degrees Celsius (OECD, 1998a).

This section provides the complete expos ure assessment for melamine during the following life cycle stages: MUF and other melamine-based resin manufacturing, CWP manufacturing, downstream product manufactur ing, and commercial/ consumer use.

7.3.1 Manufacture of MUF and Othe r Melamine-Based Resins

Melamine-based resins can be used for a pplications requiring co mposite wood products with low formaldehyde emissions. Melamine-fortifi ed resins are also used in applications requiring high mechanical strength and low thickness swelling because pure UF resins are too weak for these purposes. The content of melamine in these resins can vary depending on required formaldehyde emissions, as well as the required properties of the board (Kirk-Othmer 2005a). Exposures to melamine during MUF manufacture ve rsus other melamine-based resins cannot be distinguished with the available information; th erefore all melamine-based resins are assessed together. General melamine resin manufactur ing is classified under NAICS code 325211 –

Plastics Material a nd Resin Manufacturing.

Process Description

Co-condensation of MF resins with urea, phe nols, and other compone nts is possible in many ways, although two independent, interpenetra ting networks may be formed instead. The production of MUF resins of various melamine c ontents can follow various paths (Kirk-Othmer, 2005a):

1. Direct co-condensation of melamine, urea, and formaldehyde in a multistep reaction with varying sequences of addition of the components;

2. Direct mixing of an MF resin with a UF resin;

3. Addition of melamine in various forms ( pure melamine, MF/MUF-powder resin) to a UF resin during the application of the resin; or

4. Melamine can also be added in the form of melamine salts, such as acetates, formiates, or oxalates, which decompos e in the aqueous resin mix at higher temperatures. It has been reported that usi ng this procedure with melamine salts, the

amount of melamine needed is much lower than in other MUF resins.

No information on engineering controls or PPE were found.

Exposure Assessment for Melamine in Resin ManufacturingFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 40

No inhalation monitoring da ta were found for melamine in resin manufacturing settings, nor were surrogate monitoring data available in the OSHA IMIS database. The OECD SIDS report for melamine included inhalation data for melamine processing, indicating that a concentration of 0.1 to 1.14 mg/m 3 of pure melamine particulate was monitored in two melamine processing plants (OECD, 1998a). Table 7-11 assesses melamine inhalation exposures using the exposure information from the OECD SIDS report.

Table 7-11. Estimated Average Daily Concentrat ions of Surrogate Inhalation Monitoring

Data from OECD used to represent Melamin e Concentrations during Melamine-Based Resin Manufacturing

Industry Worker Activities Concentration of

Melamine Particulate in Air (mg/m 3 ) Average Daily

Concentration ( μ g/m 3 ) Lifetime Average Daily

Concentration ( μ g/m 3 )

Melamine Processing Unknown 0.1 – 1.14 23-260 13-150

Source: OECD, 1998a

Dermal exposures were calculated using th e EPA/OPPT 2-Hand Dermal Contact with Solids Model, which estimates a dermal exposur e of <44 mg/kg/day (see Section 3.2.2) for unloading of solids. EPA assumes up to 100% by weight melamine in solids, resulting in up to 44 mg/kg/day exposure to melamine.

As discussed in Section 6.1.2 for general re sin manufacturing, the frequency of exposure is assessed to be 250 days per year and the durat ion of exposure is assessed to be 8 hours per day.

Uncertainty in Exposure Assessment

The only available data are from a 1998 OE CD document and may be outdated or not applicable to U.S. manufacturing facilities. In addition, the description of “melamine processing” is vague and may not refer to resin manufacturing. Overall data limitations and uncertainties are

discussed in Section 5.0.

Environmental Releases of Melamine from Resin Manufacturing

Melamine was not on the TRI list of regulated chemicals in 2008, nor were any additional sources of release data found. Therefore, no release estimates are presented.

7.3.2 Melamine in CWP Manufacturing

The use of melamine resins in CWP manufact uring are expected to be similar to the process described in Section 6.2.1. A dditional details are described below.

Process Description

In gluing, the adhesive must not saturate the veneers or wo od chips, but must remain on the surface of the chips or betw een the plies; therefore, the adhesives are generally of high viscosity. Thickeners and extenders, such as powdered pecan shells a nd wheat flour, are alsoFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 41

often used. Rapid cures may be achieved by usin g microwave radiation. Hot pressing may be conducted in a hydraulic press comprising a larg e number of steam-heated platens usually 5 centimeters thick. Pressures usually range fr om 1 to 2 MPa (150 to 300 psi). Hot press temperatures for urea and melamine–urea are usually 115 to 1,328 degrees Celsius (KirkOthmer, 2002a). Melamine content in the resins can vary between a few percent to more than 30% (Kirk-Othmer, 2005a). Occupational exposu re may occur during mixing, unloading or application of the resin. No information on engineering controls or PPE were found.

Exposure Assessment for Melamine in CWP Manufacturing

No workplace monitoring data were availabl e for melamine in CWP manufacturing. The vapor pressure of melamine is 5 x10 -7 mmHg at 25 degrees Celsius, and melamine is a component of a liquid resin; i nhalation exposures from volatil ization are expected to be negligible due to its low vapor pressure.

As stated in the process description, melami ne may comprise more than 30% of the resin (Kirk-Othmer, 2005a). Based on this concentra tion and the EPA/OPPT 2-Hand Dermal Contact with Liquid Model (see Section 3.2. 2), the maximum dermal exposure is expected to be from 2.5 to 7.6 mg/kg/day melamine.

Also as discussed in Section 6.2.2 fo r composite wood product manufacturing, the frequency of exposure is assesse d to be 250 days per year an d the duration of exposure is assessed to be 8 hours per day.

Uncertainty in Exposure Assessment

Literature indicates that the melamine cont ent can vary between a few percent to more than 30%. A “typical” melamine concentrati on is unknown; therefore the estimated dermal exposures may be overestimated or underestimat ed. .Overall data limitations and uncertainties

are discussed in Section 5.0.

Environmental Releases of Melamine from CWP Manufacturing

Melamine was not on the TRI list of regulated chemicals in 2008. Additional sources of

release data were not f ound; therefore, no release estimates are presented.

7.3.3 Melamine Resins in Downstream Product Manufacturing and Commercial/ Consumer

Use

The processes for downstream product manufact uring and commercial use are expected to be identical to the processes described in Se ction 6.3.1 and 6.4. No workplace monitoring data were found for melamine in downstream product manufacturing or commercial use. Melamine will likely be entrained in cured resin; theref ore, inhalation exposures from volatilization of residual melamine are expected to be negligib le due to its low vapor pressure, and dermal exposures cannot be quantified. Consumer exposure is expected to be neglig ible as well, for the same reasons as given above.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 42

7.4 Epichlorohydrin

Epichlorohydrin is supplied commercially as a pure liquid and is primarily used as an

intermediate in the manufacture of a variety of epoxy resins. Most commonly, it is reacted with bisphenol-A to produce bisphenol-A diglycidal et her, a liquid epoxy resin used in a variety of adhesive and coating applications . Epichlorohydrin is also used in the synthesis of glycerin, wet strength resins, and epichlorohydr in elastomers. Table 7-12 summ arizes the current OELs for epichlorohydrin established by OSHA, NIOSH, and ACGIH.

Table 7-12. Occupational Exposu re Limits for Epichlorohydrin

Source Limit Type Exposure Limit d

OSHA PEL a 8-hour TWA 5 ppm (19 mg/m 3 )

NIOSH REL b Ca

ACGIH TLV c TWA for a normal 8-hour workday

and a 40-hour workweek. 0.5 ppm (1.9 mg/m 3 )

Source: OSHA, 2006; NIOSH, 2005; ACGIH, 2009.

a - The OSHA PEL also bears a "Skin" notation, which indicates that the cutaneous route of exposure (including mucous membranes and eyes) contributes to overall exposure. b - NIOSH considers epichlorohydrin to be a carcinogen. NIOSH policy for RELs for most carcinogens, including epichlorohydrin, were non-quantitative values labeled "low est feasible concentration (LFC)". See Appendix A - NIOSH Potential Occupational Carcinogens (http://www.c dc.gov/niosh/npg/nengapdxa.html) for more details. c - ACGIH also assigns a "Skin" notation to epichlorohydrin. d - The concentration in mg/m 3 was calculated from the provided concentration in ppm by multiplying the concentration in ppm by 3.78 mg/m 3 /ppm (i.e., 1 ppm = 3.78 mg/m 3 ).(NIOSH, 2005)

Wet-strength resins such as polyamine epic hlorohydrin (PAE) are typically used in the paper industry as an additive to enhance the wet- strength of paper produ cts. A particular PAE resin product produced by Hercules Incorporated is currently bei ng used in the formulation of PureBond, a formaldehyde-free wood adhesive used by Columbia Forest Products in the production of HWPW. Information from Hercules provided in a Universi ty of Massachusetts study on formaldehyde alternatives suggests that epichlorohydrin is fully consumed in the reaction to make the PAE resin (UMass, 2006a). Ba sed on this information, it is assumed that occupational exposures to epichl orohydrin will be negligible during all downstream processes after PAE resin production includ ing the formulation of PureBond, the use of PureBond in HWPW manufacturing, and the subsequent downs tream and commercial/ consumer use of the products.

This section provides the complete exposur e assessment for epichlorohydrin during the following life cycle stages: polyamine epichl orohydrin resin manu facturing, PureBond manufacturing, HWPW manuf acturing, downstream product ma nufacturing and commercial/

consumer use.

7.4.1 Manufacture of Polyamine Epichlorohydrin Resin

PAE resins are primarily used as a coating for paper fibers to e nhance its wet-strength properties. However, Columbia Forest Products uses a PAE resin manufactured by HerculesFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 43

Incorporated to formulate PureBond, a soy-based wood adhesive. As stated previously in Section 6.1, PAE manufacturing may fall under NAICS codes 325211 - Plastics Material and Resin Manufacturing, 325199 – All Other Basic Organi c Chemical Manufacturing, or 325998 - All Other Miscellaneous Chemical Product and Prep aration Manufacturing, based on TRI reporting by Hercules, Inc.

Process Description

The manufacture of PAE resins involves a two-step reactio n sequence. The first reaction

involves the condensation of a di basic acid with diethylene tria mine to yield a water-soluble polyamide. The available amine groups are then alkynated with epichlorohydrin to form an amino chlorohydrin. These amino chlorohydrin s can undergo crosslinking between polymer chains or stabilize by forming a cyclic struct ure (NZIC, 2008a). The PAE resin manufactured by Hercules Incorporated is performed in a batch process where all of the epichlorohydrin is fully

consumed in the irreversible reaction to form the resin (UMass, 2006a). Based on this information, occupational exposures are most likely to occur during the unloading of the epichlorohydrin into the reactor. Additional exposures are possible from sampling of the reaction for completion and during container and e quipment cleaning activities where residual epichlorohydrin may be present.

Information on the specific use of PPE and engineering controls during the manufacture

of PAE resins was not available in the reviewed literature. A product st ewardship manual for the safe handling and storage of epichlorohydrin was developed by Dow Chemical for its customers. The manual states that in all operations i nvolving epichlorohydrin, workers should wear chemical goggles, safety hats, impervious boots, gl oves, and outer clothing . Table 7-13 contains a summary of PPE information provided by Dow Ch emical. The use of closed process systems, ventilation, and automatic sampling is al so stressed in the manual (Dow, 2007a).

Table 7-13. PPE Considerations during Use of Epichlorohydrin

Item Considerations

Clothing, Gloves, Boots Boots - Butyl rubber appears to provide the best inherent barrier properties.

Laminate constructions containing SARANTM Resins or polyvinyl alcohol can be designed to provide various levels of barrier.

Nitrile and neoprene rubber are penetrated more readily.

Respiratory Protection Where low short-term exposures are antic ipated, use full face respirator with organic vapor or organic vapor/acid gas cartridges.

For unknown concentrations to those substantially above the occupational exposure guide, use positive pressure supplied ai r or self-contained, positive pressure breathing apparatus (SCBA).

For emergency situations use self-contained, positive pressure breathing apparatus.

Eye Protection Chemical workers’ goggles, if splashing is unlikely to occur.

Full-face shield if splashes may occur.

Alternatively, a full-face respirator can be used.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 44

Source: Dow, 2007a.

Exposure Assessment for Epichlorohyd rin in PAE Resin Manufacturing

Table 7-14 presents inhalation monitoring da ta from the OSHA IMIS database, which specifically indicates that the worker activity is for a Kymene operator. Kymene is the PAE resin used in the formulation of PureBond. The data point is from 1986, which does not meet the data preference criteria described in Appendix B. Ho wever, this concentration is similar to a maximum concentration reported in a University of Massachusetts study of 0.15 ppm, which was

measured in 1978 from Hercules facilities that manufacture Kymene (UMass, 2006a). The values reported from OSHA IMIS and from the Hercules facilities do not excee d the OSHA PEL of 5

ppm.

Table 7-14. Inhalation Monitoring Data from OSHA IMIS Database for Epichlorohydrin during PAE Production

Industry Worker Activity Description Number

of Sites

Monitored Monitored Epichlorohydrin

Concentration (ppm) Monitored Epichlorohydrin

Concentration (mg/m 3 ) a Monitoring Type Year Concentration

Level / # of

Data Points

All Other Basic Organic

Chemical Manufacturing (NAICS 325199) Kymene Operator 1 0.2 0.76 Personal (TWA) 1986 1 Data Point

Source: OSHA, 2010. a - The epichlorohydrin concentration in mg/m 3 was calculated from the provided concentration in ppm by multiplying the concentration in ppm by 3.78 mg/m 3 /ppm (NIOSH, 2005)

Table 7-15 estimates the ADC and LADC of epichlorohydrin during PAE resin manufacturing, based on monitoring data from the OSHA IMIS Database. As discussed in Section 6.1.2 for general resin manufacturing, th e frequency of exposure is assessed to be 250 days per year and the duration of exposu re is assessed to be 8 hours per day.

Table 7-15. Estimated Average Daily Concen trations of Epichlorohydrin during

Manufacture of PAE Resin

Industry Worker Activity Description Concentration

Level Monitored Epichlorohydrin

Concentration (mg/m 3 ) Average Daily

Concentration ( μ g/m 3 ) Lifetime Average Daily

Concentration ( μ g/m 3 )

All Other Basic Organic Chemical Manufacturing (NAICS 325199) Kymene Operator 1 Data Point 0.76 170 99

The dermal model used for estimates in this report could not be adjusted to account for the higher volatility of epichlorohydrin - see Section 3.2.2 for an explanation.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 45

Uncertainty in Exposure Assessment

There were limited exposure monitoring data available for the use of epichlorohydrin during PAE manufacturing. Only one data point prior to reporting year 1986 was available, which may not be applicable to or representative of present industrial cond itions. In addition, it is unclear whether the only use of epichlorohydrin at this facility is to manufacture PAE resin.

Overall data limitations and uncertainties are discussed in Section 5.0.

Environmental Releases of Epichl orohydrin during PAE Manufacturing

Table 7-16 presents releases of epic hlorohydrin during NAICS codes 325211 and 325998 (Plastics Material and Resin Manufacturi ng and All Other Miscellaneous Product and Preparation Manufacturing, re spectively) reported to the TRI for reporting year 2008.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 46Table 7-16. Environmental Releases of Epichlorohydrin duringPlastics Material and Resin Manufacturing (NAICS Code325211) and All Other Miscellaneous Chemical Product and Preparation Manufacturing (NAICS Code 325998) Reported inTRI for Reporting Year 2008PrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers for Release (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotal AirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWateraIncineration325211(13 sites)Plastics Material andResin Manufacturing 9,08658,957 68,043 1,413 199 69,6551 0 1 69,656 22,437 171,530325998(13 sites)All Other Misc. Chem.Product and PreparationManufacturing 2,000 7,419 9,419 0429,734 439,153 66 69 135 439,288 250 2,000Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedor transferred off site for treatment in wastewater and incineration units. It does not includequantities sent to on- and off-site waste management such as recycling and reuse.a - Off-site water transfer includes Publicly Owned TreatmentWorks (POTWs) and Waste Water Treatment Plants (WWTPs).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 47

7.4.2 Manufacture of PureBond, HWPW, Do wnstream Product Manufacture, and

Commercial/ Consumer Use

Hercules Incorporated uses PAE in the form ulation of PureBond. Based on the University of Massachusetts study, epichlorohy drin is expected to be fully consumed in the reaction to produce PAE resin (UMass, 2006a). Therefore, e xposures and releases are expected to be negligible or non-quantifiable downstream of PAE resin manufact uring. Consumer exposure is expected to be negligible as well, for the same reasons as given above.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 48

7.5 Polymethylene Diphenyl Diisocyanate (pMDI)

Methylene diphenyl diisocyanate (MDI) is the general name for a set of isomers with the empirical formula C 15 H 10 N 2 O 2 . MDI isomers exist as 4,4’-MDI, 2,4’-MDI, and 2,2’-MDI. The 4,4’-MDI isomer is considered the pure form of MDI and most easily isolated during the manufacturing process. Manufact ured MDI typically comprises over 97 percent pure MDI and 3 percent or less of the other isomeric forms and exis ts as a white, waxy solid at room temperature. The polymeric form of MDI (pMD I) also exists as a co-product during the manufacture of

monomeric MDI. It exists as a dark viscous liquid at room temp erature and typically comprises 40 to 50 percent 4-4’-MDI, 2.5 to 4 percent 2-4’ -MDI, 0.1 to 0.2 percent 2,2’-MDI, and 40 to 50 percent homologues. (EU, 2005b) Because MDI is a significant component of pMDI, both MDI and pMDI are examined in this report. Table 7-17 presents the OELs for MDI; there are no OELs established for pMDI.

Table 7-17. Occupational Exposu re Limits for MDI and pMDI

Source Type MDI

CASRN 101-68-8 pMDI

CASRN: 9016-87-9

OSHA PEL Ceiling 0.2 mg/m 3 (0.02 ppm) None currently listed.

NIOSH REL TWA for up to a 10-hour workday during a 40-hour

workweek 0.05 mg/m 3 (0.005 ppm)

None currently listed.

Ceiling (any 10-minute period) 0.2 mg/m 3 (0.02 ppm)

ACGIH TLV a TWA for a normal 8-hour workday and a 40-hour

workweek. 0.05 mg/m 3 (0.005 ppm) None currently listed.

Source: OSHA, 2006; NIOSH, 2005; ACGIH, 2009. a - The ACGIH TLV for MDI is based, among other things, u pon the potential for sensiti zation and meant to protect

workers from inductio n of this effect.

pMDI is used in the composite wood produc ts industry in the production of various products including oriented strand board (OSB), particleboard (PB), and medium-density fiberboard (MDF). It can be used as a component in binders added to wood chips before pressing

into boards or used as an adhesive to adhere multiple wood boards together (EU, 2005a). MDI is not typically used in HWPW.

This section provides the assessment for pM DI during the following life cycle stages: pMDI resin manufacturing, CWP manufactur ing, downstream product manufacturing and

commercial/ consumer use.

The EU Risk Assessment for MDI indicated that worker exposures are primarily mitigated by the use of closed processing system s. Additionally, general PPE includes chemicalprotective suits, gloves, aprons, safety shoes, overalls and self-containe d breathing protection if no adequate local exhaust is installed. The risk assessment also indicated that eye protection should be worn at all times when handling and operating machines using MDI (EU, 2005a).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 49

7.5.1 pMDI Resin Manufacture

MDI and pMDI are manufactured using the same general process, which yields a crude mixture of MDI isomers and pMDI that requires subsequent sepa ration processes to yield the desired products. MDI and pMDI (diisocyanate) resin manufacturing are cl assified under NAICS

code 325211 – Plastics Material and Resin Manufacturing.

Process Description

The production of MDI and pMDI involves a thr ee-step process. The first step involves the production of methylenedianiline (MDA). MDA is synthesized by the reaction of aniline with formaldehyde in the presence of hydrochloric acid to yield an isomeric mixture of 4,4’-MDA, 2,4’-MDA, and 2,2’-MDA. In the next step of the process, the MDA product is charged to a reactor with phosgene where the MDA is converted to a mixture of pure MDI, pMDI, and mixed MDI isomers. The composition can be manipulated based on adjustment of process conditions. The final step involves the separation of the va rious components to pure, crude, and polymeric MDI product for various uses. The separation can be done through techniques such as vacuum distillation or crystallization (EU, 2005a).

The manufacture of MDI and pM DI are done in closed system s and may be automatically

controlled from an outside central control room. The final MDI pr oducts are stored in tanks and transferred to use facilities via pipelines or road tanks. Occupational exposures may occur intermittently through various routine worker ac tivities such as sampling, filter changing,

connection and disconnection of pipelines, drumming or product, loading and unloading of road tankers, equipment cleaning, and acc idental spill cleanup (EU, 2005a).

Exposure Assessment from MDI/pMDI in pMDI Resin Manufacturing

The EU Risk Assessment for MDI provided some workplace measurements from the chemical industry for MDI/ pMDI manufacturin g. The measurements from 1994 to 1996 range between 0.01 and 0.2 mg/m 3 , as summarized in Table 7-18.

Table 7-18. Inhalation Monitoring Data fr om EU Risk Assessm ent for MDI/ pMDI Concentrations during pMDI Resin Manufacturing

Worker Activities Year of

Measurement Number

of Samples Range of

Values (mg/m 3 ) Techniques/Sampling

Used

pMDI Production 1994 6 0.01-0.2 Not known

1995 6 0.01-0.2 Not known

1996 6 0.01-0.2 Not known

Source: EU, 2005a.

Table 7-19 estimates the ADC and LADC for MDI/ pMDI during pMDI resin manufacturing based on the EU Risk Assessment data.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 50

Table 7-19. Estimated Average Daily Concentrat ions for Data Representing MDI/ pMDI during pMDI Manufacturing

Industry Worker Activity Description Concentration

Level Monitored MDI / pMDI

Concentration (mg/m 3 ) Average Daily

Concentration ( μ g/m 3 ) Lifetime Average Daily

Concentration ( μ g/m 3 )

pMDI

Production unknown Maximum 0.2 46 26

Minimum 0.01 2.3 1.3

Dermal exposure may occur to MDI and pM DI during resin manufacturing. As a conservative estimate, the EPA/OPPT 2-Hand Derm al Contact with Liquid Model estimates a dermal exposure of 8.4 to 25 mg/kg/day for MD I/ pMDI at 100 percent concentration (see Section 3.2.2).

As discussed in Section 6.1.2 for general re sin manufacturing, the frequency of exposure is assessed to be 250 days per year and the durat ion of exposure is assessed to be 8 hours per day.

Uncertainty in Exposure Assessment

The quality of the monitoring data presented in the EU Risk Assessment is unclear. The data were obtained from 1994 to 1996 in European workplaces and may not be representative of conditions in the U.S. In addition, the sampling method was not discussed; therefore, it is not known whether these values are time weighted averages. Overall data limitations and

uncertainties are discussed in Section 5.0.

Environmental Releases of MDI from pMDI Manufacturing

Table 7-20 presents diisocyanates releas es during Plastics Material and Resin Manufacturing (NAICS code 325211) reported to the TRI for reporting year 2008.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 51Table 7-20. Releases of Diisocyanates DuringPlastics Material and Resin ManufacturingReported in TRI for Reporting Year 2008aPrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers for Release(lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotalAirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWaterbIncineration325211(68 sites)Plastics Material andResin Manufacturing 858 2,936 3,793 0 25 3,818 44,551 58,338 102,889 106,707 602 213,152Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedor transferred off-site for treatment in wastewater & incineration units. It does not include quantitiessent to on- and off-site waste management such as recycling and reuse.a - Table is based on TRI release data for the diisocyanates category (N120), which includes MDI and 19 other diisocyantes.b - Off-Site water transfer includes Publicly Owned Treatment Works (POTWs) and Waste Water Treatment Plants (WWTPs)Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 52

7.5.2 PB and MDF Manufacture

In their proposed Airborne Toxic Control Measure, CARB indicated that pMDI can be used in MDF or PB (CARB, 2007a). It can be added during the blending of wood chips prior to pressing operations (EU, 2005a). As stated previous ly, pMDI is not believed to be widely used in HWPW production.

Process Description

The MDF and PB production processes using pM DI are expected to be similar to the general production processes describe d in Section 6.2.1, except that pMDI resins are expected to be introduced during the blende r operation. Information on the specific PPE and engineering controls used during the use of pMDI resi ns in CWP manufactur e was not available.

Exposure Assessment from MDI in PB and MDF Manufacturing

The EU Risk Assessment provided some data provided by industry for the use of MDI in PB and MDF manufacturing, as shown in Table 7-21.

Table 7-21. Inhalation Monitoring Data fr om EU Risk Assessm ent for MDI/ pMDI Concentrations during PB Manufacturing

Application Worker Activity Description Number of Samples Monitored MDI / pMDI Concentration (mg/m 3 ) Monitoring Type Year

PB (chipboard) Blending 1 <0.015 Personal + Static (Area) 1998

Source: EU, 2005a. Note: The monitoring method used measures total isoc yantates and does not distinguish between pMDI and pure

MDI.

Table 7-22 estimates the ADC and LADC for MDI/ pMDI during PB and MDF manufacturing based on the EU Risk Assessment da ta for PB manufacturing assuming that MDF workplace concentrations will be simila r to PB workplace concentrations.

Table 7-22. Estimated Average Daily Concentrat ions for Data Representing MDI/ pMDI during PB and MDF Manufacturing

Industry Worker Activity Description Monitored MDI / pMDI

Concentration (mg/m 3 ) Average Daily

Concentration ( μ g/m 3 ) Lifetime Average Daily

Concentration ( μ g/m 3 )

PB or MDF blending <0.015 3.4 2.0

Dermal exposure may occur to MDI and pMDI during CWP manufacturing. As a conservative estimate, the EPA/OPPT 2-Hand Derm al Contact with Liquid Model estimates a dermal exposure of 8.4 to 25 mg/kg/day for pM DI at 100 percent con centration (see Section 3.2.2).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 53

As discussed in Section 6.2.2 for general CWP manufacturing, the frequency of exposure is assessed to be 250 days per year and the durat ion of exposure is assessed to be 8 hours per day.

Uncertainty in Exposure Assessment

Only one potentially relevant data point fo r MDI/ pMDI was available in the EU Risk Assessment for PB and MDF, but it is unclear whethe r the data is representative of conditions in

the U.S. Overall data limitations and un certainties are discussed in Section 5.0.

Environmental Releases of MDI from PB and MDF Manufacturing

Table 7-23 presents releases of diisocya nates, including MDI, during Reconstituted Wood Product Manufacturing (NAI CS code 321219) reported to th e TRI for reporting year

2008.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 54Table 7-23. Releases of Diisocyanates during Reconstituted Wood Product Manufacturing Reported in TRI for ReportingYear 2008aPrimaryNAICSCodeNAICSDescriptionOn-Site Releases (lb)Off-Site Transfers forRelease (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotalAirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWaterbIncineration321219(30 sites)Reconstituted WoodProductManufacturing 7,789 1,236 9,025 0 0 9,025 0 0 0 9,025 0 0Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedor transferred off site for treatment in wastewater and incineration units. It does not includequantities sent to on- and off-site waste management such as recycling and reuse.a - Table is based on TRI release data for the diisocyanates category (N120), which includes MDI and 19 other diisocyanates.b - Off-site water transfer includes Publicly Owned TreatmentWorks (POTWs) and Waste Water Treatment Plants (WWTPs).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 55

7.5.3 Downstream Product Manufacture and Commercial/ Consumer Use

MDI/ pMDI exposures and releases are expe cted to be negligible or non-quantifiable during downstream product manufacture and commerc ial use because MDI/ pMDI is consumed during the CWP manufacture pro cess (USEPA, 2011c). Consumer e xposure is expected to be negligible as well, for the same reasons as given above.

Table 7-24 presents releases of diisocyana tes, including MDI, for several downstream product manufacturing industries re ported to the TRI for reporting year 2008. Of the industries that reported diisocyanates releases, these releases were to fugitive air or transferred off site for disposal. Many industries did not report any releases, although th is may be due to the reporting threshold not being met. Additi onally, MDI is also used as a component in wood glues for downstream uses of CWP products such as furn iture assembly and building construction. The use of these glues may be the source of releases (EU, 2005a).Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 56Table 7-24. Releases of Diisocyanatesin Various Downstream Product Manufacturing Industries Reported in TRI forReporting Year 2008aPrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers forRelease (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotalAirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWaterbIncineration321911(8 sites)Wood Window andDoor Manufacturing 0 5 5 0 0 5 0 0 0 5 0 0321918(1 site)Other Millwork(including Flooring) 0 0 0 0 0 0 0 0 0 0 0 0321991(63 sites)Manufactured Home(Mobile Home)Manufacturing 0 0 0 0 0 0 0 57 57 57 0 0321992(2 sites)Prefabricated WoodBuildingManufacturing 0 0 0 0 0 0 0 0 0 0 0 0337211(4 sites)Wood Office FurnitureManufacturing 0 0 0 0 0 0 0 0 0 0 0 0337212(1 site)Custom ArchitecturalWoodwork andMillworkManufacturing 0 23 23 0 0 23 0 0 0 23 0 0337122(1 site)Nonupholstered WoodHousehold FurnitureManufacturing 0 0 0 0 0 0 0 0 0 0 0 0337127(2 sites)Institutional FurnitureManufacturing 0 13 13 0 0 13 0 0 0 13 0 0Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedor transferred off site for treatment in wastewater and incineration units. It does not includequantities sent to on- and off-site waste management such as recycling and reuse.a - Table is based on TRI release data for the diisocyanates category (N120), which includes MDI and 19 other diisocyanates.b - Off-site water transfer includes Publicly Owned TreatmentWorks (POTWs) and Waste Water Treatment Plants (WWTPs).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 57

7.6 Vinyl Acetate Monomer (VAM) and Polyvinyl Acetate (PVA)

Vinyl acetate monomer (VAM) (CASRN 108-05-4 ) is used almost exclusively as an

intermediate for manufacturi ng polyvinyl acetate (PVA) (C ASRN 9003-20-7) (SCHER, 2008a)

. These PVA polymers are used as ingredients in a variety of products, which include CWP adhesives. Vinyl acetate exists as a colorl ess, flammable liquid (K irk-Othmer, 2005b). Table 7-25 presents the occupational exposure limits for VAM. There are no OELs established for

PVA.

Table 7-25. Occupational Exposure Limits for Vinyl Acetate Monomer (CASRN 108-05-4)

Source Limit Type Exposure Limits

OSHA PEL None currently listed None currently listed

NIOSH REL 15-Minute ceiling 4 ppm, 15 mg/m 3

ACGIH TLV TWA 10 ppm, 35 mg/m 3

STEL 15 ppm, 53 mg/m 3

Source: OSHA, 2006; NIOSH, 2005; ACGIH, 2009.

This section provides the complete exposur e assessment for VAM during the following life cycle stages: PVA manufacturing, CWP manu facturing, downstream product manufacturing,

and commercial/ consumer use.

7.6.1 Manufacture of PVA resin

PVA adhesives are primarily used for pack aging and wood gluing. PVA adhesives are stable and can accept many types of modifying add itives without being damaged. In addition, the adhesives can be adapted to any type of machin e operation, such as spray guns, rollers, extrudertype devices, etc. (Kirk-Othmer, 2005b). PVA re sin manufacturing is classified under NAICS

code 325211 – Plastics Material and Resin Manufacturing.

Process Description

PVA is principally manufactured through the polymerization of VAM by bulk, solution, suspension, and emulsion processes. However, 90 percent of PVA or VAM copolymers are made by emulsion techniques. Various fi nishing techniques are used to reduce the residual monomer in the emulsion polymer, such as raising the temperat ure, adding a more concentrated initiator, or using mechanical means such as stripping. Typi cal industrial polymerizations are carried out to over 99 percent conversion; theref ore, there is no need to re duce the unreacted monomer unless very low levels are required to meet regulator y, product, or workplace requirements. Most PVA emulsions contain less than 0.5 weight perc ent unreacted vinyl acetate, which minimizes development of acetic acid and acetaldehyde byproducts by monomer hydrolysis during a long storage (Kirk-Othmer, 2005b).

Typically, in PVA production processes, only a portion of the monomer and the catalyst is charged to the reactor, with the remainder slow ly added over the course of the reaction. This allows for better control of the polymerization rate , which is particularly important in large-scale operations where heat-transfer capacity may be limited (Kirk-Othmer, 2005b).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 58

The EU Risk Assessment for VAM indicate s that workers normally use gloves and eyeglasses. During cleaning activities, workers al so use respiratory prot ection (EU, 2008a). The Vinyl Acetate Council (VAC) states that for routine operations where vapor exposure is below established exposure limits, PPE will typica lly consist of the following (VAC, 2010a):

 Flame retardant clothing, splash goggle s, hard hat and safety shoes; and

 Gloves are also recommended fo r handling hoses or drums.

For routine operations with pot ential for minor liquid exposur e (from splashes, drips or minor spills) and where vapor exposure is belo w established exposure limits, PPE typically would consist of (VAC, 2010a):

 Impervious gloves, clothing, boots and a face shield; and

 Protective clothing made of chemical- and fire -resistant materials in process areas. When both are needed, the chemical resistant cl othing should be worn over flame retardant clothing.

Respiratory Protection

High-level exposures to VAM may occur during emergency situ ations; equipment cleaning and repairs; decontamination of areas after a spill; or during failure of piping or equipment containing VAM (VAC, 2010a). For these situations, VAC recommends that workers use full protective suits and full-face self-cont ained or supplied-air respiratory protection.

Skin Protection

Materials suitable for preventing exposures to VAM are shown in the following table.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 59

Table 7-26. VAM Permeation Times for Various PPE Materials a

Material Common Use Results b

Barricade Suits > 8 hours

Teflon Suits > 8 hours

Responder Suits > 4 hours

North Butyl B161 (16 mil or equivalent) Gloves 5 hours

North Butyl B324R (32 mil or equivalent) Gloves > 8 hours

Ansell Edmont Laminate (2.5 mil or equivalent) Gloves > 6 hours

North Silver Shield/4H (2.7 mil or equivalent) Gloves > 8 hours

Source: VAC, 2010a a - Testing conducted according to the American Society for Testing and Materials (ASTM), Standard Test Method for Resistance of Protective Clothing Materials to Permeation by Liquids or Gases Under Conditions of Continuous Contact. ASTM F 739-99a. Annual Book of ASTM Standards, Vol. 11.03. b - Results are given as resistance time to breakthrough after continuous contact.

Eye Protection

Full eye and face protection is preferred and s hould include face shields (full length, 8 in. (20 cm) minimum) with forehead protecti on in addition to chemical splash goggles. Eye protection can be provided through the use of a full face masks and appropriate respiratory protection if vapor or mist e xposure is expected (VAC, 2010a).

Exposure Assessment for VAM in PVA Manufacturing

Inhalation monitoring data were not f ound for VAM in PVA resin manufacturing. Table 7-27 provides surrogate workplace monitoring data compiled in the EU Risk Assessment for VAM during various worker ac tivities in the adhesives pro duction industry. The EU Risk Assessment notes that the majority of the monitoring data provided are not shift averages, and the period of exposure is not provided for several of the data ranges.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 60

Table 7-27. Surrogate Inhalation Monitoring Data from Data Representing VAM Concentrations during PVA Resin Manufacturing a

Adhesives Production Industry Year of

Measurements Number of Samples Range of

Measurement Data (mg/m 3 )

Non 8-hr Time Weighted Averages

Formulation 1997-2000 60 0.07-32

1995-2000 100 10.3-14.6

1996, 2000 2 1.8-3.9

1998, 1999 N/A 3.2-46

Pumping monomer into tanks 1998, 1999 N/A 39-46.8 (over 30 min)

Pre-emulsion preparation 1998, 1999 N/A < 3.6 (over 30 min)

Pumping pre-emulsion into reactor 1998, 1999 N/A 18 (over 60 min)

8-hr Time Weighted Averages

Filling, cleaning, opening of vessels 1996-2002 23 3.1 (50 th percentile)

14.6 (90 th percentile)

Source: EU, 2008a.

N/A – Not Available a –Monitoring data is likely not a shift average.

Table 7-28 calculates inhalation exposure to VAM during PVA manu facturing based on monitoring data from the EU Risk Assessment fo r VAM. The general facility estimate in Section 6.1.2 for general resin manufacturing is 45 workers per site. As also discus sed in Section 6.1.2, the frequency of exposure is assessed to be 250 da ys per year and the dur ation of exposure is assessed to be 8 hours per day.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 61

Table 7-28. Estimated Average Daily Concentr ations for Data Representing VAM during PVA Production using Surrogate Data from the EU Risk Assessment

Industry Worker Activity Description Concentration

Level Monitored VAM

Concentration (mg/m 3 ) Average Daily

Concentration ( μ g/m 3 ) Lifetime Average Daily

Concentration ( μ g/m 3 )

Adhesives

Production Formulation Maximum 46 a 11,000 6,000

Minimum 0.07 a 16 9.1

Pumping

monomer into

tanks Maximum 2.9 b 660 380

Minimum 2.4 b 550 310

Pre-emulsion preparation 1 Data Point <0.2 b 46 26

Pumping preemulsion into

reactor 1 Data Point 2.3 b 530 300

Filling, cleaning, opening of vessels 90 th percentile 14.6 3,300 1,900

50 th percentile 3.1 710 400

a –Based on monitoring data that is likely not a shift av erage (EU, 2008a); therefore, average daily exposures may

be overestimated. b- These exposures were calculated by converting the monitoring data over the period of exposure to an 8-hour average. For example, a measurement of 46.8 mg/m 3 over 30 minutes was converted to 2.9 mg/m 3 over 8 hours.

The dermal model used for estimates in this report could not be adjusted to account for the higher volatility of VAM - see S ection 3.2.2 for an explanation.

Uncertainty in Exposure Assessment

As noted above, most of the monitoring data provided in Table 7-27 are not shift averages and the period of exposure was not prov ided. Therefore, some exposure calculations may be overestimated. Additionally, the data prov ided in the EU Risk Assessment may not be representative of current conditions in the U. S. Overall data limitations and uncertainties are

discussed in Section 5.0.

Environmental Releases of VAM from PVA Resin Manufacturing

Table 7-29 presents releases of VAM from Plastics Material and Resin Manufacturing (NAICS Code 325211) as reported to the TRI for reporting year 2008. The majority of VAM is disposed of by off-site incineration (>5 million pounds). On-site releases are primarily divided between stack air and fugitive air.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 62Table 7-29. Releases of VAM during Plastics Material and Resin Manufacturing Reported in TRI for Reporting Year 2008PrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers for Release (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotal AirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWateraIncineration325211(43 sites)Plastics Material and ResinManufacturing 297,366 355,341 652,707 18 54 652,779 2,655 0 2,655 655,434 380,204 5,717,362Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedor transferred off site for treatment in wastewater and incineration units. It does not includequantities sent to on- and off-site waste management such as recycling and reuse.a - Off-site water transfer includes Publicly Owned TreatmentWorks (POTWs) and Waste Water Treatment Plants (WWTPs).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 63

7.6.2 HWPW Manufacturing

CARB indicated in their rulemaking that PVA is typically used in HWPW production (CARB, 2007a). Section 7.6.1 i ndicated that typical industrial polymerizations, such as the polymerization of VAM to PVA, are carried out to over 99 percent conversion. Similarly, according to the EU Risk Assessment, there is no rmally no direct use of VAM in CWP facilities. The VAM is converted to PVA, which contains small amounts of resi dual VAM (ranging from less than 2 ppm to 3000 ppm) (EU, 2008a).

Process Description

The general processes for HWPW manufacturing and downstream product manufacturing are expected to follow the general processes desc ribed in Sections 6.2.1 and 6.3.1. No specific information on engineering c ontrols and PPE were found.

Exposure Assessment for VAM during HWPW Manufacturing

Inhalation exposure information on the manuf acture and use of composite wood products containing VAM was not found. VAM is typically polymerized into PVA resin at over 99 percent conversion. Additionally, the process of applying PVA to the wood veneers is not expected to generate mists; th erefore, inhalation exposures to residual VAM are expected to be negligible.

The dermal model used for estimates in this report could not be adjusted to account for the higher volatility of VAM - see S ection 3.2.2 for an explanation.

As discussed in Section 6.2.2 for composite wood product manufacturing, the frequency of exposure is assessed to be 250 days per year a nd the duration of exposure is assessed to be 8 hours per day.

Uncertainty in Exposure Assessment

Overall data limitations and uncertainties are discussed in Section 5.0.

Environmental Releases of VAM durin g HWPW Manufacturing and Downstream Product Manufacturing.

No release data for VAM were found in CWP manufacturing and downstream product manufacturing.

7.6.3 Downstream Product Manufacture and Commercial/ Consumer Use

The processes for downstream product manufacturi ng and commercial use are expected to be identical to the processes described in Section 6. 3.1 and 6.4. No workplace monitoring data were found for VAM in downstream product manufacturing or commercial use. VAM will be polymerized in the cured PVA; therefore, inhala tion exposures to residual VAM are expected to be negligible, and dermal exposures cannot be qu antified during these life cycle stages. SinceFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 64

consumer use would be in this set of life cycl e stages, consumer exposure is expected to be negligible as well.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 65

7.7 Chromium (III)

Certain chromium (III) metal salts have been ad ded to PVA resin formulations to create water-resistant bonds, which have application in CWP manufacture (Brabetz et al., 1978a). The exposure assessment encompasses the following li fe cycle stages: addition of Cr(III) salts to PVA resin; CWP manufacture; downstream produc t manufacture; and commercial/ consumer use. Table 7-30 presents exposure limits for chromium (III) compounds.

Table 7-30. Occupational Exposure Limits for Chromium (III) (CASRN 16065-83-1)

Source Chemical Limit Type Exposure Limit

OSHA PEL Chromium (II) and chromium (III) compounds 8-hour TWA 0.5 mg Cr/m 3

NIOSH REL Chromium metal and chromium (II) and chromium (III) compounds 8-hour TWA 0.5 mg Cr/m 3

ACGIH TLV Metal and Cr(III) compounds,

as Cr a 8-hour TWA 0.5 mg/m 3

Source: OSHA, 2006; NIOSH, 2005; ACGIH, 2009. a - Appendix A4 - Not Classifiable as a Human Carcinogen.

Process Description

Literature describes adding an acid hardener, such as a chromium (III) nitrate solution, to

PVA resin formulations in con centrations from 0.5 to 10 perc ent (Brabetz et al., 1978a). No specific information concerning engineering cont rols and PPE was found in the literature.

Exposure Assessment for Chromium (III)

No inhalation exposure data were found for chromium (III) in PVA resin manufacturing or other downstream life cycle stages. Inhalation e xposures are expected to be negligible because chromium (III) nitrate is used in solution, used as a component of a liquid resin, and then

entrained in the cured resin.

In an example found in the literature, a satu rated solution of chromium nitrate was added to the PVA resin (Brabetz et al., 1978a). Sin ce saturation depends on a number of variables, exposure to 100 percent chromium is presented as a conservative estimate. Dermal exposures to 100 percent chromium would be expected to be 8.4 to 25 mg/kg/day, using the EPA/OPPT 2- Hand Dermal Contact with Liquid Model (see Section 3.2.2). During CWP manufacturing, the

concentration of chromium in the PVA resin is less than ten percent, the resulting dermal exposure for chromium is up to 2.5 mg/kg/day. Dermal exposures are not quantifiable after CWP manufacturing because the chromium salts cros slink with the PVA upon curing (Frihart, 2005a).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 66

General facility estimates for resin manufact uring in Section 6.1.2 estimate 8 hours of exposure per day over 250 exposure days per year.

Uncertainty in Exposure Assessment

The estimate for the amount of chromium salt added to PVA resin is based on a patent

from 1978. The actual industrial us e of chromium salts in PVA resin and downstream products is unclear. Additionally, the specific concentration of the chromium salt solution is unknown; only a conservative dermal exposure estimate was possi ble. Overall data limitations and uncertainties

are discussed in Section 5.0.

Environmental Releases of Chro mium and Chromium Compounds

As reported to the TRI for reporting year 2008, Table 7-31 presents releases during PVA resin manufacturing and Table 7-32 presents rele ases from downstream product manufacturing. Releases during downstream product manufacturi ng may be due to non-CWP sources, such as welding or metal components in the downstream products. Note that the TRI data are not limited to chromium (III) compounds.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 67Table 7-31. Release of Chromium and Chromium Compounds during PlasticsMaterial and Resin Manufacturing Reported in TRIfor Reporting Year 2008PrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers for Release (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotal AirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWateraIncinerationCHROMIUM325211(3 sites)Plastics Material and ResinManufacturing 9 250 259 0 70 329 14 186 200 529 0 0CHROMIUM COMPOUNDSb325211(10 sites)Plastics Material and ResinManufacturing 605 392 997 13,000 407,379421,376 77,901 322 78,223 499,599 10 0Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedor transferred off site for treatment in wastewater and incineration units. It does not include quantitiessent to on- and off-site waste management such as recycling and reuse.a - Off-site water transfer includes Publicly Owned TreatmentWorks (POTWs) and Waste Water Treatment Plants (WWTPs).b - Releases for chromium compounds only include the portion of the compound that is elemental chromium.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 68Table 7-32. Releases of Chromium and Chromium Compounds during DownstreamProduct Manufacturing Reported in TRI forReporting Year 2008PrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers for Release (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotal AirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWateraIncinerationCHROMIUM337127(4 sites)Institutional FurnitureManufacturing 5 255 260 0 0 260 501 0 501 761 250 0337212(3 sites)Custom ArchitecturalWoodwork and MillworkManufacturing 0 2 2 0 0 2 182 72 254 256 0 0337215(4 sites)Showcase, Partition,Shelving, and LockerManufacturing 0 250 250 1 0 251 0 0 0 251 0 0CHROMIUM COMPOUNDSb321911(2 sites)Wood Window and DoorManufacturing 22 0 22 0 0 22 826 7,191 8,017 8,039 252 0337127(1 site)Institutional FurnitureManufacturing 6 4 10 0 0 10 0 0 0 10 16 0Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedor transferred off site for treatment in wastewater and incineration units. It does not include quantitiessent to on- and off-site waste management such as recycling and reuse.a - Off-site water transfer includes Publicly Owned TreatmentWorks (POTWs) and Waste Water Treatment Plants (WWTPs).b - Releases for chromium compounds only include the portion of the compound that is elemental chromium.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 69

7.8 Ammonia

Ammonia may be used in a variety of industr ies, including the manu facture of synthetic fibers, plastics and resins. In the CWP industr y, ammonia may include use as a post-treatment additive to reduce formaldehyde emissions (Manns ville, 2005a). Table 7- 33 lists current OELs

for ammonia.

Table 7-33. Exposure Limits for Ammonia (CASRN 7664-41-7)

Source Limit Type Exposure Limit

OSHA PEL 8-hour TWA 50 ppm (35 mg/m 3 )

NIOSH REL TWA for up to a 10-hour workday during a 40-hour workweek 25 ppm (18 mg/m 3 )

STEL 35 ppm (27 mg/m 3 )

ACGIH TLV For a normal 8-hour workday and a

40-hour workweek. 25 ppm (18 mg/m 3 )

STEL 35 ppm (27 mg/m 3 )

Source: OSHA, 2006; NIOSH, 2005; ACGIH, 2009.

7.8.1 Ammonia in CWP Manufacture

Literature suggests that a mmonia may be used as a s cavenger to reduce the free formaldehyde emissions, including treatment of th e CWP with ammonia gas or ammonia salts.

Process Description

Two post-treatment methods to reduce form aldehyde release from CWPs use ammonia gas: the Verkor FD-EX and the RYAB methods.

The FD-EX method is a two-step procedure that is done in a three-chambered plant. In the first chamber, the CWP is treated with an excess of ammonia gas at temperatures between 30 and 35 degrees Celsius, reducing the formal dehyde by the formation of hexamethylene tetramine. In the second chamber, most of the ex cess ammonia is desorbed. In the third chamber, the rest of the ammonia reacts with formic acid and other wood compounds to be fixed as ammonium salt in the board. As a consequence of the last reaction ch amber, no ammonia odor should be present to lessen the suita bility of the finished boards. However, the literature suggests that the relatively high cost of the FD-EX meth od has hindered its wider distribution in industry (Pizzi, 1989a).

The RYAB method treats the CWP with ammonia gas in a single step. The treatment takes place in a special chamber using a pressu re gradient. The reaction is completed during storage of the treated board. The reaction is th e same as in the FD-EX method. However, the ammonia odor can remain on the CWPs for weeks (Pizzi, 1989a).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 70

Another post-treatment is the ASSI met hod, which uses such ammonia salts are ammonium carbonate, ammonium bicarbonate or ammonium carbamate as scavenging agents. The ammonia is slowly liberated from the salts a nd acts as a scavenger. The salts can be added to the adhesive or sprayed as solids or solutio ns on the surface of the boards. (Pizzi, 1989a).

No additional information on the use of engineering controls and PPE during ammonia use in CWP production or dow nstream uses was found.

Exposure Assessment for Ammonia

No monitoring data were found for amm onia in CWP manufacturing. However, therefore, inhalation exposures are expected to gaseous ammonia. Because no monitoring data are available, a “what-if” expos ure concentrations were calcula ted using the OSHA PEL and are

shown in Table 7-34.

As discussed in Section 6.2.2 for composite wood product manufacturing, the frequency of exposure is assessed to be 250 days per year a nd the duration of exposure is assessed to be 8 hours per day.

Table 7-34. Estimated “What-If” Average Daily Concentrations of Ammonia Based on the

OSHA PEL

Source Limit Type Ammonia Exposure Limit (mg/m 3 ) Average Daily

Concentration ( μ g/m 3 ) Lifetime Average Daily Concentration ( μ g/m 3 )

OSHA PEL 8-hour TWA 35 8,000 4,600

Based on the potential post-treatment methods described in the li terature, workers will likely contact ammonia in gaseous form. De rmal exposures to gaseous ammonia are nonquantifiable (see Section 3.2.2).

Uncertainty in Exposure Assessment

There is a lack of monitoring data for ammonia during CWP manu facturing. Exposure estimates are based on OSHA PELs and may over estimate or underestimate current conditions, depending on the level of compliance in industry. Additionally, literature id entifies several types of ammonia treatment for CWPs, involving both ga seous ammonia and ammonia salts. However, it is unclear whether any of these methods can be considered “typical” for the industry.

Environmental Releases of Ammonia

Table 7-35 presents ammonia releases during Hardwood Veneer and Plywood Manufacturing (NAICS 321211) and Reconstitu ted Wood Product Manu facturing (NAICS 321219) as reported to the TRI fo r reporting year 2008. Note that TRI lists a “qualifier” for ammonia, stating that 100 per cent anhydrous ammonia must be re ported, but only 10 percent of aqueous ammonia is reportable. Ammonia releases from reconstituted wood product manufacturing are considerably higher than in HWPW manufacturing.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 71

7.8.2 Downstream Product Manufacture and Commercial/ Consumer Use

Ammonia exposures are not expected to be significant durin g downstream product

manufacture and commercial us e because nitrogen-based scave nger additives (e.g., ammonia) with low molecular weight may have the potential to diffuse from the wood matrix in the final product, but the physical-chemical properties of these neat chem icals would generally preclude much volatility. In addition, should the additives react with formaldehyde, as intended, the corresponding adducts will be much more likely to irreversibly bind to the wood chemical moieties (USEPA, 2011c). Therefor e, exposures of residual a mmonia are expected to be negligible for these life cycle st ages. Additionally, no release data for ammonia were found in any downstream product manufacturing or commerc ial use industries. Since consumer use would be in this set of life cycl e stages, consumer exposure is exp ected to be negligible as well.Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 72Table 7-35. Environmental Releases of Ammonia during Hardwood Veneer and Plywood Manufacturing (NAICS Code321211) and Reconstituted Wood Product Manufacturing (NAICSCode 321219) Reported in TRI for Reporting Year 2008aPrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers for Release (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotalAirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWaterbIncineration321211(1 site)Hardwood Veneer andPlywood Manufacturing 0 5 5 0 0 5 0 0 0 5 0 0321219(7 sites)Reconstituted WoodProduct Manufacturing 272,885 1,285 274,170 1,295 751 276,216 314 0 314 276,530 0 0Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedor transferred off site for treatment in wastewater and incineration units. It does not includequantities sent to on- and off-site waste management such as recycling and reuse.a - TRI lists a “qualifier” for ammonia, indicating that 100 percent of anhydrous ammonia must be reported, but only 10 percentof aqueous ammonia isreportable.b - Off-site water transfer includes Publicly Owned Treatment Works (POTWs) and Waste Water Treatment Plants (WWTPs).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 73

7.9 Phenol

Phenol (CASRN 108-95-2) is primarily used as an intermediate in the manufacture of bisphenol-A and in the synthesis of phenolic resins. Phenol exists as a crystalline solid at room temperature but is normally sold as a heated li quid in bulk quantities (M annsville, 2008a; KirkOthmer, 2005c). Table 7-36 lists es tablished OELs in the U.S.

Table 7-36. Occupational Exposure Li mits for Phenol (CASRN 108-95-2)

Source Limit Type Exposure Limit

OSHA PEL a 8-hour TWA 5 ppm (19 mg/m 3 )

NIOSH REL a TWA for up to a 10-hour workday during a 40-hour workweek 5 ppm (19 mg/m 3 )

STEL 15.6 ppm (60 mg/m 3 )

ACGIH TLV a TWA for a normal 8-hour workday

and a 40-hour workweek. 5 ppm (19 mg/m 3 )

Source: OSHA, 2006; NIOSH, 2005; ACGIH, 2009. a – OSHA, NIOSH and ACGIH also assign a "Skin" notation to phenol.

7.9.1 Manufacture of Phenol-Formaldehyde Resin

Phenolic resins were initially used mainly fo r exterior applications, while UF resins were used for interior applications. However, the concern over formaldehyde emissions has caused some replacement of UF by phenol–formaldehyde adhe sives. Phenolic resins typically comprise 5–25% by weight of plywood, particleboard, wafe rboard, and fiberboard . (Kirk-Othmer, 2003a).

Process Description

Batch processes for most phenolic resins ( novolaks, resols) employ the equipment shown in Figure 7-2. Reactants are added into the sti rred reaction vessel through weigh tanks. Reactions are typically carried out under vacuum or an in ert gas (Kirk-Othmer, 2003a). Typically, resols remain liquid and are drummed at temperatures less than 25°C. Resols contain free (unreacted) phenol up to 15% (EU, 2006a).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 74

Figure 7-2. Typical Phenolic Resin Pr oduction Unit (Kirk-Othmer, 2003a)

Exposure Assessment for Phenol in Manufacture of PF Resin

Inhalation exposure to phenol during PF resin manufacturing is expect ed during filling, transfer, sampling, drumming as well as during cl eaning, maintenance and repair work. The final PF resins with free phenol content up to 15% are an additional source of exposure, particularly when they cool down from elevated temperatur e outside the closed sy stems (EU, 2006a).

The EU Risk Assessment provided limited m onitoring data for phenol exposures during phenolic resin manufacturing, which are provid ed in Table 7-37. The OSHA IMIS database contained two data points from 1980 and 1985 for potential exposures to phenol during Plastics

Material and Resin Manufactur ing (NAICS code 325211). However, both of these data points reported values of “NF,” or not found; therefor e, only the EU Risk Assessment data were included in this report. All monitoring data pr esented are below or equal to the established exposure limit of 5 ppm (19 mg/m 3 ) established by OSHA, NIOSH, and ACGIH (shown in Table 7-36).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 75

Table 7-37. Inhalation Monitoring Data from 2006 EU Risk Assessment for Phenol during Phenolic Resin Manufacturing

Type of Sampling Work

Area/Activities Year Number of

Measurements Range of

Measured

Values (mg/m 3 ) a Mean (mg/m 3 ) 90 th

Percentile

(mg/m 3 ) Duration

and Frequency

Unknown Phenolic Resin Manufacturing 1997 10 0 – 1.2 0.1 0.4 unknown

Source: EU, 2006a

a – Limit of detection is unknown.

Table 7-38 presents the estimated ADC a nd LADC for phenol during phenolic resin manufacturing based on monitoring data from the EU Risk Assessment.

Table 7-38. Estimated Average Daily Concentratio ns for Data Representing Phenol during Phenolic Resin Manufacturing

Industry Worker Activity Description Concentration

Level Monitored

Phenol

Concentration (mg/m 3 ) Average Daily

Concentration ( μ g/m 3 ) Lifetime Average Daily

Concentration ( μ g/m 3 )

Phenolic Resin Manufacturing Unknown Maximum 1.2 270 160

Mean 0.1 23 13

Minimum < 0.041 a < 9.4 < 5.3

a – The EU Risk Assessment reported a concentration of zero, as shown in Table 7-37. The limit of detection is

unknown; therefore EPA assesses a mi nimum concentration of 0.041 mg/m 3 based on the limit of detection specified for phenol in OSHA Analytical Method No. 32.

For the large scale production of resins, the EU Risk Assessment assumes that automated processes are employed. In an automated large- scale process, worker activities are limited to loading the bags on conveyer belts. The furt her steps, opening and emptying the bags, are performed automatically. In a ddition to large scale production , smaller amounts of specialty resins are produced. In a small-scale specialty pr ocess, phenol is manually dumped into reaction vessels. PF resins containing ≥ 3% unreacted phenol are considered corrosive; therefore, workers typically avoid daily dermal exposure and skin contact is limited to occasional events (EU, 2006a).

The EU performed a quantitative assessment of dermal exposures using the EASE model. Exposure was assessed to be between 2.1 and 21 mg/worker/day for the handling of corrosive phenol and corrosive resins ( ≥ 3% phenol) (EU, 2006a). The EPA/OPPT 2-Hand Dermal Contact with Liquid Model is assessed as conservative, which estimates a dermal exposure of 1.3 to 3.8 mg/kg/day (see Section 3.2.2) for a con centration of 15%, (EU, 2006a) although actual exposures may be less due to the corrosive nature of phenol.

As discussed in Section 6.1.2 for general re sin manufacturing, the frequency of exposure is assessed as 250 days per year and the durati on of exposure is assesse d as 8 hours per day.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 76

Uncertainty in Exposure Assessment

The quality of the monitoring data presente d in the EU Risk Assessment is uncertain.

There were limited data availa ble from 1997 and the data may not be representative of current conditions in the U.S. Additionally, due to the hea lth effects of phenol, expos ures are expected to be mitigated with PPE. Actual exposures to phenol are uncertain. Overall data limitations and

uncertainties are discussed in Section 5.0.

Environmental Releases of Phenol during the Manufacture of PF Resin

Table 7-39 presents releases of phenol during NAICS Code 325211 (Plastics Material and Resin Manufacturing), as reported to the TRI for reporting year 2008. The large majority of releases are incinerated off site (2.5 million pounds).Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 77Table 7-39. Environmental Releases of Phenol during Plastics Material and Resin Manufacturing Reported in TRI forReporting Year 2008PrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers forRelease (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotalAirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWateraIncineration325211(52 sites)Plastics Material andResin Mfg139,001137,432276,4332,149286278,868826,294167,525993,8191,272,687153,0122,582,288Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedto the environment or transferred off site for treatment inwastewater and incineration units.It does not include quantities sent to on- and off-site waste management such as recycling and reuse.a - Off-site water transfer includes Publicly Owned TreatmentWorks (POTWs) and Waste Water Treatment Plants (WWTPs).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 78

7.9.2 Phenolic Resins in CWP Manufacturing

Seventy five percent of phenolic resins were then used in orient ed strand board (OSB) manufacture and 25 percent were for other us es such as plywood manufacture (Mannsville 2008b). Different phenolic resins are used for di fferent types of wood; for example, plywood and PB adhesives contain liquid resol resins. Other types of wood pr oducts such as waferboard and

OSB are bonded with solid re sins (Kirk-Othmer, 2003a).

Process Description

The general processes for CWP manufactur ing is expected to follow the general processes described in Section 6.2.1.

Exposure Assessment for Phenolic Resins in CWP Manufacturing

As stated previously, phenolic resins (re sols) may contain <1% to 15% free phenol. The EU Risk Assessment indicated that during the hard ening process, some free phenol is chemically bound and some is released. Occupational exposur e to vapors is assumed during mixing of phenol-containing preparations a nd processing of resins at elevated temperatures. Dermal exposures are also possible through direct handling of phenolic resins (EU, 2006a).

Limited monitoring data was provided in th e EU Risk Assessment provided for phenol exposures during the use of phenolic resins. Measurements taken from 1990 to 1995 were provided for the use of phenolic resins in the plastics processing and w oodworking industries, as

shown in Table 7-40. The OSHA IMIS database did not provide any data for the use of phenol in CWP manufacturing. All monitoring data presen ted are below or equal to the established exposure limit of 5 ppm (19 mg/m 3 ) established by OSHA, NIOSH, and ACGIH (shown in Table 7-36).

Table 7-40. Inhalation Monitoring Data from 2006 EU Risk Assessment for Phenol during Phenolic Resin Processing

Type of Sampling Activities Year Number of Samples (number of premises) Specific

Conditions 50 th

Percentile

(mg/m 3 ) 90 th

Percentile

(mg/m 3 ) 95 th

Percentile

(mg/m 3 )

8-hr TWA Processing of phenolic resins in the plastics processing and woodworking

industries 1990-

1995 329 (136) Total <1.0 a 1.0 1.3

196 (91) No local

exhaust

ventilation <1.0 a 1.0 2.0

128 (56) Local

exhaust

ventilation <1.0 a 1.0 1.0

Source: EU, 2006a a – These measurements were below the detection limit of 1 mg/m 3

.

Table 7-41 presents the estimated ADC and LADC for phenol during the use of phenolic resins based on monitoring data from the EU Risk Assessment.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 79

Table 7-41. Estimated Average Daily Concentratio ns for Data Representing Phenol during CWP Manufacturing

Industry Specific

Conditions Concentration

Level Monitored

Phenol

Concentration (mg/m 3 ) Average Daily

Concentration ( μ g/m 3 ) Lifetime Average Daily

Concentration ( μ g/m 3 )

Processing of phenolic resins in the plastics processing and woodworking

industries a Total 95 th Percentile 1.3 300 170

90 th Percentile 1.0 230 130

50 th Percentile <1.0 b <230 <130

No local

exhaust

ventilation 95 th Percentile 2.0 460 260

90 th Percentile 1.0 230 130

50 th Percentile <1.0 b <230 <130

Local exhaust

ventilation 95 th Percentile 1.0 230 130

90 th Percentile 1.0 230 130

50 th Percentile <1.0 b <230 <130

a – Specific worker activities are unknown. b – These measurements were below the detection limit of 1 mg/m 3

.

The EU Risk Assessment indicated that dermal contact with re sins classified as corrosive ( ≥ 3% phenol) is limited and skin contact to non- corrosive resins (<3% phenol) may occur daily. Exposure measurements from a 1999 study during plywood production indicated potential dermal between 0.31 and 2.663 mg/hr for th e whole body and between 0.012 and 0.127 mg/hr for the hands. The shift average was estimated to be 22 mg/day. The EU Risk Assessment also included an assessment of dermal exposures using the EASE model. Dermal exposure was assessed to be between 1.3 and 13 mg/worker/da y for non-corrosive resins and between 0.3 and 3 mg/worker/day for corrosive resins (EU, 2006a ). The EPA/OPPT 2-Hand Dermal Contact with Liquid Model is assessed as conservative, whic h estimates a dermal exposure of 1.3 to 3.8 mg/kg/day (see Section 3.2.2) for a concentration of 15% phenol.

As discussed in Section 6.1.2 for general re sin manufacturing, the frequency of exposure is assessed as 250 days per year and the durat ion of exposure is assessed as 8 hours per day.

Uncertainty in Exposure Assessment

The quality of the monitoring data presented in the EU Risk Assessment is unclear. There

were limited data available from 1990 to 1995 and th e data may not be repr esentative of current conditions in the U.S. The data are a general set of data for phenolic resins in the plastics and woodworking industries and may not all be appl icable to the specific CWPs of interest. Additionally, due to the health e ffects of phenol, exposures are expected to be mitigated with PPE. Actual exposures to phenol are uncertain. Overall data limitations and uncertainties are

discussed in Section 5.0.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 80

Environmental Releases of Phenol during CWP Manufacturing

Table 7-39 presents releases of phe nol during Reconstituted Wood Product Manufacturing (NAICS Code 321219), as reported to the TRI for reporting year 2008. The large majority of releases are sent through stack air (300,000 pounds).Formaldehyde Substitutes Exposure and Release Assessment – Draft FinalOctober, 2011 – draft deliberative – do not cite or quotePage 81Table 7-42. Environmental Releases of Phenol during Reconstituted Wood Product Manufacturing Reported in TRI forReporting Year 2008PrimaryNAICSCodeNAICS DescriptionOn-Site Releases (lb)Off-Site Transfers forRelease (lb)TotalReleases(lb)Off-Site Transfers (lb)StackAirFugitiveAirTotalAirSurfaceWaterLandTotalOn-SiteReleasesLandOtherTotalOff-SiteReleasesWateraIncineration321219(10 sites)Reconstituted WoodProduct Mfg305,8142,472308,28621155308,46257057308,519 0 0Source: USEPA, 2009a. TRI data were obtained from the 2008 Pubic Data Release (PDR), which was frozen on September 17, 2009 andreleased to the public inDecember 2009. These data only include quantities that are releasedto the environment or transferred off site for treatment inwastewater and incineration units.It does not include quantities sent to on- and off-site waste management such as recycling and reuse.a - Off-site water transfer includes Publicly Owned TreatmentWorks (POTWs) and Waste Water Treatment Plants (WWTPs).Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 82

7.9.3 Downstream Product Manufacturing and Commercial/ Consumer Use

Exposure information on the use of compos ite wood products cont aining phenol was not found. Because the initial resin-making reacti on occurs with excess fo rmaldehyde, the phenol is limiting regent and is consumed for purposes of exposure (USEPA, 2011c). Therefore, exposures are expected to be negligible or non-quantifiable for these life cycle steps. Additionally, no release data fo r phenol were found in any downstream product manufacturing or

commercial use industries. Since consumer use would be in this set of life cycle stages, consumer exposure is expected to be negligible as well.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 83

8.0 K EY U NCERTAINTIES AND L IMITATIONS OF E XPOSURE E STIMATES

The daily worker exposure inhalation con centrations, ADCs and LADCs, generated in this report are highly uncertain and present si gnificant limitations for their use. The air concentration parameters used to estimate the associated daily exposure concentrations come from a variety of sources, and their representati veness of actual typical air concentrations in workplaces in the CWP life cycle chain is not kn own. The daily exposure concentrations are most suitable for a qualitative overview of work er exposure issues and identification of data gaps. Some of the most significant uncerta inties and limitations are summarized below.

Worker monitoring data were ge nerally sparse in readily-avai lable sources used for this assessment, resulting in few data points on which to estimate representative ADCs and LADCs. Several of the European sources’ data sets we re robust, but how well these data sets may represent exposures to substitute chemicals in th e various CWP life cycle stages in the U.S. is uncertain, due to potential differences in expos ure limits, regulations, emissions controls, etc .

OSHA IMIS data could only be characteri zed on an industry-specific level, based on NAICS codes. For example, UF resin manuf acturing is classified under NAICS code 325211 (Plastics Material and Resin Ma nufacturing); however, there are several other types of resins

manufactured under this code. It was not possible to distinguish wh ether available data for this NAICS code was for UF resin manufacturing or for one of the many other types of resin manufacturing. Similarly, it was not possible to distinguish the number of sites within each

NAICS code that were associated with each fo rmaldehyde substitute. EU Risk Assessments and

OECD SIDS data were also available but were not able to address all of the data gaps within the scope of this assessment.

Furthermore, the characterizations of the da ily inhalation concentrations (e.g., average, 95th percentile, single point value, assumed high-e nd) were not consistent for the each chemical.

These uncertainties and limitations, as related to worker inhalation exposure concentrations in this report, indicate that direct quantitative co mparison between various chemicals and life cycle stages is likely to be imprecise and is not recommended.

There is information that suggests that subst itute chemicals are used in substitute resins or in UF resins to reduce formaldehyde emissi ons. However, there was no industry information that indicated the preval ence of the use of substitute chem icals, and there was limited specific

information found in literature sources for this re port that indicated the amount or concentration of chemical used in their resp ective processes. Prevalence of use could impact a variety of parameters examined in this re port, including inhalati on exposure concentrati ons and numbers of exposed workers and consumers.

Dermal exposure estimates are also uncertain. Because literature sources’ information on processes, worker activities, and concentrations of substitute chemicals in materials handled by workers were limited, the assumptions used for dermal exposure modeling are uncertain. The prevalence of glove use in the assessed workpl aces is unknown, and where gloves are used, the model results are overestimates. When used, th e same dermal models were applied to all chemicals and life cycle steps in this asse ssment, making their use and dermal exposureFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 84

estimates consistent and comparable to the exte nt that the assumptions used in employing the

models are correct.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 85

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US Census Bureau, 2002a. U.S. Census Bureau . 2002 Economic Census Industry Series Reports – Manufacturing. (NAICS codes refe renced are listed in Table 2-2). http://www.census.gov/econ/cen sus02/guide/INDRPT31.HTM

USDA, 2007a. US Department of Agriculture (USDA). U.S. Forest Products Annual Market Review and Prospects, 2004-2008. FPL-RN-0305. August 2007.

USEPA, 1991a. U.S. Environmen tal Protection Agency, Office of Pollution Prevention and Toxics, Chemical Engineering Branch. CEB Manual for the Preparation of Engineering Assessment , Volume 1. Washington DC . Contract No. 68-D8-0112. February 1991.

USEPA, 1992a. U.S. Environmenta l Protection Agency (USEPA). Guidelines for Exposure

Assessment. Risk Assessment Forum, Washi ngton, DC, EPA/600/Z-92/001, 1992.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 89

USEPA, 1997a. Memorandum: Exposure Descript ors for CEB Reports - Final. From the Chemical Engineering Branch (CEB) Chief to CEB Staff. January, 1997.

USEPA, 1997b. Exposure Factors Handbook. US E nvironmental Protection Agency, Office of Research and Development, National Ce nter for Environmental Assessment. EPA/600/P-95/002. August 1997.

USEPA, 2000. U.S. Environmen tal Protection Agency (USEPA), Office of Pollution Prevention and Toxics, Chemical Engineering Branch. Options for Revising CEB’s Method for Screening-Level Estimates of Dermal Exposure – Final Report . Washington

DC. June 2000.

USEPA, 2002a. U.S. Environmenta l Protection Agency (USEPA). AP-42 Chapter 10.6.2 – Wood Products Industry – Particleboard Manufacturing. June 2002.

USEPA, 2002b. U.S. Environmenta l Protection Agency (USEPA). AP-42 Chapter 10.6.3 – Wood Products Industry – Medium De nsity Fiberboard Manufacturing . August

2002.

USEPA, 2002c. U.S. Environmenta l Protection Agency (USEPA). AP-42 Chapter 10.6.1 – Wood Products Industry – Waferboard/Or iented Strand Board Manufacturing

. March 2002.

USEPA, 2009a. U.S. Environmenta l Protection Agency (USEPA). Toxic Release Inventory

. 2008 Public Data Release. http://www.epa.gov/triexplorer/

USEPA, 2009b. U.S. Environmenta l Protection Agency (USEPA). Risk Assessment Guidance for Superfund Volume I: Human Hea lth Evaluation Manual (Part F, Supplemental Guidance for Inhalation Risk Assessment). January 2009.

USEPA, 2011a. U.S. Environmenta l Protection Agency (USEPA). HUMAN HEALTH

HAZARDS OF ALTERNATIVE RESIN TECHNOLOGIES REPLACING UREAFORMALDEHYDE RESIN . August 2011.

USEPA, 2011b. U.S. Environmenta l Protection Agency (USEPA). Assessment of Occupational Exposure to Formaldehyde from Composite-Wood Products . October 2011.

USEPA, 2011c. U.S. Environmenta l Protection Agency (USEPA). Chemistry Report Analyzing the Substitutes for Urea-Formaldehyde (U F) Resins to Reduce Emissions from Composite Wood Products . July 2011.

USITC, 2008a. US Internationa l Trade Commission (USITC). Wood Flooring and Hardwood Plywood: Competitive Conditions Affecting the U.S. Industries . USITC Publication 4032. August 2008.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page 90

VAC, 2010a. Vinyl Acetate Council (VAC). Vinyl Acetate Safe Handling Guide

. April 2010.Appendix A

DEFINITION OF TERMSFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page A-1

Definition of Terms

American Conference of

Governmental Industrial Hygienists (ACGIH) ACGIH is a member-based organization of industrial hygienists whose goal is to advance occupational and environmental health. ACGIH performs individual lab tests and develops with their own exposure limits that are sometimes used as suggested standards.

Average Daily Concentration (ADC) The exposure concentration of a chemical, averaged over 365 days per year and 24 hours per day.

Ceiling Limit (C) The air concentration for a s ubstance that should not be exceeded during any part of the working exposure.

Composite-Wood Products (CWPs) The manufacture of most composite-wood products involves a pressing operation where the wood material is bonded with a resin. Because the resulting product is “pressed,” the term “pressed-wood” has also been used to refer to plywood, particleboa rd, fiberboard, and larger engineered wood products. Hardwood plywood, mediumdensity fiberboard, and partic leboard are termed compositewood products in this report.

Downstream Product Manufacturing The manufacture of commerci al or consumer products, such as cabinets, panels, and furniture, from HWPW, MDF,

and PB.

Exposure Contact with a substance by inhalation, dermal contact, or ingestion.

Exposure Assessment The process of determining how people come into contact with a substance, how often and for how long they are in contact with the substance, a nd how much of the substance they are in contact with.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page A-2

Exposure Pathway The route a substance takes from its source (where it began) to its end point (where it ends), and how people can come into contact with (or ge t exposed to) it. An exposure pathway has five parts: a sour ce of contamination (such as a pressed-wood product); an environmental media and transport mechanism (such as the off-gassing of formaldehyde through air); a point of exposure (such as an individual’s breathing zone ); a route of exposure (inhalation), and a receptor population (people potentially or actually exposed). When all five parts are present, the exposure pathway is termed a completed exposure pathway.

Hardwood Plywood (HWPW) A hardwood or decorative panel that is: i. intended for interior use; and ii. composed of (as determined under the standard numbered ANSI/HPVA HP–1–2009) an assembly of layers or plies of veneer, joined by an

adhesive with: I. lumber core; II. particleboard core; III. medium-density fiberboard core; IV. hardboard core; or V. any other special core or special back

material.

This does not include: i. military-specified plywood; ii. curved plywood; or iii. any other product specified in— I. the standard entitled ‘Voluntary Product Standard—Structural Plywood’ and numbered PS1–07; or II. the standard entitled ‘Voluntary Product

Standard—Performance Standard for Wood-

Based Structural-Use Panels’ and numbered

PS 2–04.

Life Cycle All stages of a product’s deve lopment, from manufacture and processing to distributi on, use, and disposal and recycling.

Lifetime Average Daily Concentration (LADC) The exposure concentration of a chemical, averaged over 70 years, 365 days per year, and 24 hours per day, assuming 40 years of exposure.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page A-3

MDI Resin A resin containing methylene di phenyl diisocyanate (MDI) – see polymethylene diis ocyanate (pMDI).

Medium-Density Fiberboard (MDF) A panel composed of cellulosic fibers made by dry forming and pressing a resinated fiber mat (as determined under the standard numbered ANSI A208.2–2009)

MF Resin A resin containing melamine and formaldehyde monomers.

MUF Resin A resin containing melamine, urea, and formaldehyde

monomers.

National Institute for Occupational Safety and Health (NIOSH) As part of the Centers for Disease Control, NIOSH is responsible for conducting research and making recommendations for the prevention of work-related illnesses and injuries.

Occupational Exposure Contact with a substance as a result of one’s work

environment.

Occupational Safety and Health Administration (OSHA) OSHA is the main federal agency charged with the enforcement of safety and health legislation. OSHA has the regulatory authority to set exposure limits for specific chemicals or groups of chemicals.

OSHA Integrated Management Information System (IMIS) IMIS is an on-line data entry and information retrieval system designed to collect , process, re trieve, and communicate penalty assessment, arbitration, and collection information rega rding OSHA's inspections.

Particleboard (PB) A panel composed of cellulosic material in the form of discrete particles (as distingui shed from fibers, flakes, or strands) that are pressed togeth er with resin (as determined under the standard numbered ANSI A208.1–2009)

This does not include any produc t specified in the standard entitled ‘Voluntary Produc t Standard—Performance

Standard for Wood-Based St ructural-Use Panels’ and

numbered PS 2–04.

Permissible Exposure Limit (PEL) PELs are regulatory limits issu ed by OSHA for the amount or concentration of a substance in the air. They may also contain a skin designation. OS HA PELs are based on an 8- hour time weighted average (TWA) exposure.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page A-4

pMDI Resin A polymeric resin comprised of methylene diphenyl diisocyanate (MDI) monomers.

PVA Resin A resin comprised of vinyl acetate monomers (VAM).

Recommended Exposure Limit (REL) Unless noted otherwise, RELs are time-weighted average (TWA) concentrations for up to a 10-hour workday during a 40-hour workweek. Unlike PELs, which are regulatory limits, RELs are recommended limits issued by NIOSH.

Release Quantity of chemical released to the environment, including disposal (e.g., to landfills and underground injection wells). Release types include on-site to air, water, and land (with multiple sub-types for each); and off site transfers to water and land (no estimates of off-site transfers that result in air releases).

Short-Term Exposure Limit (STEL) A STEL is defined as a 15-minute TWA exposure that should not be exceeded at any time during the work day

even if the 8-hr TWA is within established limits. An averaging period other than 15 minutes may be utilized when this is warranted by observed biological effects.

It is recommended that exposures beyond the timeweighted average limit (whether regulatory or otherwise) up to the STEL should not occur more than 4 times per day

with at least 60 minutes betw een successive exposures in this range.

Threshold Limit Value (TLV) TLVs are recommended exposure limits that are issued by

the ACGIH. TLVs are airborne concentrations of substances to which it is believed that nearly all workers may be repeatedly exposed da y after day without adverse effect. There are three categories of TLVs: TLV-TWA; TLV-STEL; and TLV-C.

Time-Weighted Average (TWA)

Concentration Average air concentration of a substance based on a normal 8-hour work day and a 40-hour work week. OSHA PELs are based on an 8-hour time-weighted average (TWA)

exposure.

UF Resins A resin comprised of urea and formaldehyde monomers.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page A-5

Waste Management Activities Recycle, Energy Recovery, and Treatment (destruction, and/or removal depending upon the context).

What-If Type Estimate An estimate based on a set of hypothetical conditions or under a set of conditions for which actual exposure or release parameter data are incomplete or nonexistent. The calculated exposure, dose, or release quantity is not intended to provide information about how likely the combination of exposure or release parameter values might be in the actual population or about how many, if any, persons might actually be subjected to the calculated exposure or release.Appendix B

DATA QUALITY PREFERENCE CRITERIA SPECIFICATIONSFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page B-1

Table B-1. Data Quality Preference Criteria Specifications

Criterion Description/Definition Specification Currency Is the information up to date? Does it

reflect current conditions? Process Desc.: Year of source is 1990 or after

Number of Sites and Production Data: Year of

source is 2000 or after and correlates with

number of sites

Exposure Data: Priority - Year of source is 2005 or after

Consider – Most recent data before 2005.

Geographic Scope Does the information reported reflect

an area relevant to the assessment? All Data: Priority – sources describing U.S. sites

When U.S. data are no t available, consider sources from countries with geographic proximity that may adopt similar processes or from other developed countries that may have similar regulations and standards.

Process Description: Consider – sources describing Canadian, Mexican, or European processes.

Number of Sites and Production Data: Consider – North American sites (and interpolate to estimate U.S. sites and production)

Exposure Data: Consider – Canadian or European data.

Accuracy/Reliability Is the information or data from a peer-reviewed, government, or industry-specific source? Is the source published? Is the author engaged in a relevant field such that competent knowledge is expected (i.e., the author writes for an industry trade association publication versus a general newspaper)? All Data: U.S. or other government publication

For an academic researcher:

 Publication in peer-reviewed journal

 Presentation at a technical conference

 Source has documented qualifications/ credentials to discuss particular topic

For an industry expert or trade group:

 Presentation at a technical conference where the information is subject to review by other industry experts

 Source has documented qualifications/ credentials to discuss particular topic

 Source represents a large portion of the industry of interest

Unbiased Is the information objective towards a particular product or outcome? All Data:

 Objective of the information is clear.Formaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page B-2

Table B-1. Data Quality Preference Criteria Specifications

Criterion Description/Definition Specification

 Methodology is designed to answer a specific question.

Comparability Are the data comparable to other

sources that have been identified or are they significantly different than

other sources? Production Data, Exposure Data, and Number of

Sites: Values are within the same order of magnitude of each other.

Process Description: Matches or is similar to other information for the same industry and will be evaluated on a case-by-case basis.

Representativeness Do the data reflect typical industry practices? All Data: Information is relevant to the industry and from a reputable source with qualifications in the industry of interest.

Data are based on a large industry survey or study, as opposed to a case study or sample from

a limited number of sites. Applicability For surrogate data, are the data expected to be similar for the industry of interest? Surrogate data used to fill data gaps must be judged to be similar to the data of interest:

 Industry is similar in size

 Same types of chemicals are utilized

 Similar processes and activities are performed

 Similar levels of engineering controls and personal protective equipment are

usedAppendix C

DATA SUMMARY INFORMATIONFormaldehyde Substitutes Exposure a nd Release Assessment – Draft Final October, 2011 – draft deliber ative – do not cite or quote Page C-1

The key data used for this report include OSHA IMIS data, TRI data, and US Census Bureau data. Table C-1 presents a summary of the raw data files and the primary data fields

included. Table C-1. Key Data Source Summary

Data Source Filename Key Data

OSHA IMIS OSHA_IMIS_Data_Jan1979_Apr2010_Formaldehyde_Substitutes.xls SIC Code

NAICS Code

Establishment Name Inspection Type Sample Data Job Description

Number of Workers Exposed Exposure Frequency Category

Substance Code Sample Type Exposure Type Exposure Level Exposure Level Units

TRI TRI_Releases_2008_Formaldehyde_Substitutes.xls TRIFID

Plant Name

CAS Number

NAICS Code

Point Source Air

Emissions Fugitive Air Emissions

Total Air Releases

Surface Water Discharges

Total On-site Land

Releases

Total On-site Releases

Total Off-site Land

Releases

Other Off-site Releases

Total Releases

Off-site Water Transfers

Incineration

U.S.

Economic

Census US Census Bureau 2002.xls NAICS Code NAICS Description Number of Companies

Number of

Establishments

Number of Production

Workers Aggregate Production

Hours Worked