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United States Environmental Protection Agency



# Preliminary Study of Carbon Disulfide Discharges from Cellulose Products Manufacturers

December 2011This page intentionally left blank.

# U.S. Environmental Protection Agency Office of Water (4303T) 1200 Pennsylvania Avenue, NW Washington, DC 20460

EPA-821-R-11-009This page intentionally left blank.Preliminary Study of Regenera ted Cellulose Manufacturers

i CONTENTS

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1.0 S TUDYING D ISCHARGES FROM R EGENERATED C ELLULOSE M ANUFACTURERS ................... 1 1.1 Introduction............................................................................................................. 1 1.2 Background – Manufacturing Process.................................................................... 1 1.3 Background - Existing Effluent Guide lines and Regenerated Cellulose Manufacturing......................................................................................................... 2 1.3.1 40 CFR Part 414.......................................................................................... 2 1.3.2 40 CFR Part 463.......................................................................................... 3 1.3.3 Potential New Subcategories for the OCSPF Category.............................. 4 1.3.4 NPDES Permit Basis................................................................................... 4 1.4 Background – Industry Profile of U. S. Cellulose Manufacturers........................... 5

2.0 C ARBON D ISULFIDE P ROPERTIES ......................................................................................... 7 2.1 Chemical Properties of Carbon Disulfide............................................................... 7 2.2 Carbon Disulfide - Potential Path ways into the Environment................................ 9

3.0 W ASTEWATER S OURCES ...................................................................................................... 9 3.1 Unloading and Storage............................................................................................ 9 3.2 Process Steps......................................................................................................... 11 3.3 Air Pollution Control ............................................................................................ 12

4.0 R EGENERATED C ELLULOSE P ROCESS W ASTEWATER T REATMENT .................................... 13

5.0 F ACILITY D ISCHARGE D ATA .............................................................................................. 15 5.1 Innovia Films, Inc in Tecumseh, KS .................................................................... 15 5.1.1 Waste Streams........................................................................................... 15 5.1.2 Wastewater Treatment .............................................................................. 16 5.1.3 Discharge Data.......................................................................................... 17 5.2 Viskase Corporation in Loudon, TN..................................................................... 19 5.2.1 Wastewater Source and Treatment ........................................................... 19 5.2.2 Discharge Data.......................................................................................... 19

6.0 C ONCLUSIONS .................................................................................................................... 20

7.0 R EFERENCES ...................................................................................................................... 20Preliminary Study of Regenera ted Cellulose Manufacturers

ii LIST OF TABLES

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Table 1. Applicability of Subcat egories in the PMF Category........................................................3

Table 2. Existing ELGs for Regenerated Cellulose Materials.........................................................4

Table 3. Operating U.S. Cellulose Products Manufacturers and Corresponding 2009 TRI and DMR Discharges..................................................................................................................6

Table 4. Closed or Idled Cellulose Manufacturers in the United States..........................................7

Table 5. Chemical Properties of Car bon Disulfide, Acetone, and Ethanol .....................................7

Table 6. Inhalation Exposure Limits for Carbon Disulfide, Acetone, and Ethanol.........................8

Table 7. TRI 2009 Carbon Disulfide Air Emissi ons and Water Discharges for Cellulose Products Manufacturers .......................................................................................................9

Table 8. Facility Carbon Disulfide Unload ing and Storage Practices as of 2000..........................11

Table 9 . Cellulose Products Wastewater Treatment......................................................................13

Table 10. Confirmed Sources of Wastewater and Wastewater Treatment at Cellulose Manufacturing Facilities ....................................................................................................14

Table 11. Innovia Films, Inc Waste Streams .................................................................................15

Table 12. 2008, 2009, and 2010 Carbon Disulfide C oncentration Data for Innovia Films, Inc. .....................................................................................................................................17

Table 13. Carbon Disulfide Concentration Da ta for Viskase Corporation in Loudon, TN...........19

Table A-1. Applicability of Sub categories in the OCPSF Category ...............................................1Preliminary Study of Regenera ted Cellulose Manufacturers

1 1.0 S TUDYING D ISCHARGES FROM R EGENERATED C ELLULOSE M ANUFACTURERS

1.1 Introduction

EPA is studying wastewater discharges fr om regenerated cellulose manufacturers because these facilities report large discharges of carbon disulfide (CS 2 ) (U.S. EPA, 2006, U.S. EPA, 2010). Currently no existing regulation sets federal effluent limitations for CS 2 discharges from the seven regenerated cellulose manufacturer s that operate in the United States. Cellulose products manufacturers use CS 2 in the viscose process to break down aged alkali cellulose prior to regeneration. CS 2 can enter the wastewater stream at these facilities from CS 2 unloading and storage, the viscose process, CS 2 recovery, and/or ai r pollution control.

The main pollutant of concern disc harged from these facilities, CS 2 , is a volatile organic compound. EPA researched how the CS 2 enters the wastewater and its fate in the facilities’ existing wastewater treatment systems. EP A also collected data on whether the CS 2 discharges would impact human health or aquatic life. EPA continues to resolve the overall question of how significant concentrations of CS 2 remain in the wastewater, although CS 2 is highly volatile.

1.2 Background – Manufacturing Process

Regenerated cellulose products manufacturers us e the viscose process to form cellulose film, sponge, food casings, and rayon from dissolv ing-grade wood pulp. In the viscose process, sheets of dissolving-grade cellulose pulp are sa turated with caustic (e .g., sodium hydroxide) to convert the cellulose into alkali cellulose. The alkali cellulose pa rtially oxidizes and degrades by aging in ambient air. Gaseous CS 2 is mixed with the aged alkali cellulose in a vessel to form sodium cellulose xanthate. The sodium cellulose xanthate is dissolved in aqueous caustic solution, creating the viscose solution. The viscos e solution is ripened, filtered, degassed, and extruded, and then sulphuric acid is added to th e viscose solution to form regenerated cellulose (Schmidtke, 2000). Figure 1 presents a simplified flow diagram of the general viscose process and the different process steps for each type of regenerated cellulos e (cellulose f ilm or cellophane, sponge, food casings, and rayon) (Schmidtke, 2000).Preliminary Study of Regenera ted Cellulose Manufacturers

Figure 1. Simplified Process Flow Diagram for the Generic Viscose Process and Regenerated Cellulose Products

1.3 Ba ckground - Existing Effluent Guid elines and Regenerated Cellulose Manufacturing

The regenerated cellulose manufacturing proc ess is closely relate d to two effluent limitation guidelines and standard s (ELGs) point source categories: Organic Chemicals, Plastics, and Synthetic Fibers (OCPSF, 40 CFR Part 414) and Plastics Molding and Forming (PMF, 40 CFR Part 463). However, wastewater discharges from the manufacture of several cellulose products are not covered by any existing cate gorical ELGs or pretreatment standards.

1.3.1 40 CFR Part 414

The OCPSF ELGs (40 CFR Part 414, Subpart B) apply to wastewater discharged from the ma nufacture of rayon, a regene rated cellulose fiber. However, these regulations specifically exclude discharges from the manufacture of cel lulose film, sponge, and meat casings (40 CFR §414.20 ). Further, these regulations do not include limitations for CS 2 and there are no rayon facilities currently operating in the United Stat es. Appendix A includes further information on the applicability and subp arts of 40 CFR Part 414.

2Preliminary Study of Regenera ted Cellulose Manufacturers

3 1.3.2 40 CFR Part 463

The PMF industry includes facilities that are engaged in blending, molding, for ming, or other types of processing of plastic materials. These proces ses commonly include extrusion, coating and laminating, thermoforming, calenda ring, casting, foaming, cleaning, and finishing (U.S. EPA, 1984). EPA first promulgated ELGs for the PMF Category (40 CFR Part 463) on December 17, 1984 (49 FR 49040). There are three subcategories, all of which have best practicable control technology (B PT), new source performance standards (NSPS), pretreatment standards for existing sources (PSES), and pret reatment standards for new sources (PSNS) limitations.

The manufacture of cellulose products are not covered by Part 463 (the PMF Category). The product is made of regenerate d cellulose using the viscose pr ocess, and Part 463 specifically excludes products manufactured from regenerated cellulose, as well as the molding and forming of regenerated cellulose (U.S. EPA, 1984).

40 CFR §463.1(g) Processes used to regenerate cellulose and to produce a product (e.g., rayon) from the regenerated cellulose are not subject to the effluent limitations guidelines and standards in this part. Processes that mold or form cellulose derivatives (e.g., cellulose acetate) are subject to the effluent limitations guidelines and standards in this part if they discharge process water.

The regenerated cellulose manu facturing process is similar to the operations regulated by 40 CFR Part 463 because water contacts extrusion equipment and regenerated cellulose products for cooling, cleaning, and finishi ng; however, regenerated cellulose s are not plastic materials and are not regulated by the PMF ELGs. Table 1 describes the three subc ategories regulated by the PMF ELGs.

Table 1. Applicability of Subcat egories in the PMF Category

Subpart Description Applicability

A Contact Cooling and Heating Water Processes wh ere water contacts plastic material or plastic products for the purpose of heat transfer.

B Cleaning Water Processes where wate r contacts the plastic products or shaping equipment for the purpose of cleaning.

C Finishing Water Processes where water contacts plastics products during finishing.

Source: Preliminary Review of Prioritized Categories of Industrial Discharger s (U.S. EPA, 2005a)

The Technical Development Document for Effluent Limitations Guidelines and New Source Performance Standards for the Plastics Molding and Forming Point Source Category (PMF TDD) provides the rationale for excludin g regenerated cellulose manufacturers from the PMF ELGs. It states that plasti c materials are a group of synthe tic, organic materials composed of high molecular weight, long chain molecules. The definition of plastic materials in the PMF regulation also includes natural polymers that are combined with synthetic organic materials,Preliminary Study of Regenera ted Cellulose Manufacturers

4 such as cellulose acetate. However, wholly na tural organic materials, such as regenerated cellulose, are not included in the PMF definition of plastic materials.

The PMF TDD also states that the final step in the xanthate proce ss used to regenerate cellulose is to wash the regenerated cellulose to remove dissolved salts and sulfur compounds within the product. Process water us ed in this step is not consider ed cleaning water as defined in the final PMF ELGs because it does more than just clean the surface of th e regenerated cellulose.

Therefore, wastewater discha rges from the manufacture of several cellulose products, including film, sponge, and food casings, are not covered by any existing categorical ELGs or pretreatment standards. Table 2 provides an overview of the cellu lose products that are covered by existing ELGs and corresponding CS 2 limitations.

Table 2. Existing ELGs for Regenerated Cellulose Materials

Regenerated Cellulose Product 40 CFR Part 414 (OCPSF) 40 CFR Part 463 (PM&F) Rayon a Included, but no CS 2 limits Excluded Cellulosic Film (Cellophan e) Excluded Excluded Cellulosic Sponge Ex cluded Excluded Food Casing Excluded Excluded Source: 40 CFR §414.20 and 40 CFR §463.1(g) a – There are not rayon manufacturers cu rrently operating in the United States.

1.3.3 Potential New Subcategories for the OCSPF Category

EPA reviewed the information provided in Tables 1 and 2 and determ ined that the cellulose products manufacturers using the viscos e process to manufactur e cellophane, cellulosic sponge, and food casings have proc esses, operations, wastewaters, and pollutants identical to the rayon manufacturers regulated by the OCPSF Cate gory (Subpart B – Rayon Fibers). The end products at these facilities are all considered re generated cellulose materials and are all produced using the same viscose process. For future screening level data review, EPA will classify the discharges from these facilities as a pot ential new subcategory of the OCPSF Category.

1.3 .4 NPDES Permit Basis

Because wastewater discharges from the manufacture of several cellulose products, including film, sponge, and food casings are not covered by any existing categorical ELGs or pretreatment standards, permit writers have us ed state water quality standards, historical performance effluent data (HPED), other sim ilar ELGs (i.e., OCSPF Subpart D – Thermoplastic Resins BPT), and best professiona l judgment (BPJ) as the basis for permit limits. The permits for wastewater discharges from ce llulose products manufacturing in clude limits for the following pollutants: biological oxygen demand (BOD), to tal suspended solids (TSS), ammonia, ammonia nitrogen, total residual chlorines, oil and grease, and tota l organic carbon.

Only one NPDES permit (for Innovia Film s, Tecumseh, KS, a cellulose products manufacturer), includes m onitoring requirements for CS 2 . Innovia Films is required to monitor CS 2 to avoid process upsets to the facility’s act ivated sludge treatment system. Other permitted facilities are not required to monitor CS 2 , likely because there are no national water quality criteria for it, and other similar ELGs do not have limitations for CS 2
.Preliminary Study of Regenera ted Cellulose Manufacturers

5 1.4 Background – Industry Profile of U.S. Cellulose Manufacturers

EPA identified seven cellulose products manuf acturers operating in the U.S. as of 2009. The final products of these facili ties compete in markets with products made from alternative materials, especially plastics. Cellulose products have generally been declining in market share over time as newer non-cellulose products have been introduced (Beach, et al., 2000). The cellophane manufacturing industr y has been declining since th e 1950s due to new regulations and economic issues. The domestic market for rayon has also been eliminated because textile production has moved out of the United States (Beach, Houtven, Buckley, and Depro, 2000). Table 3 lists the operating U.S. cellulose products ma nufacturers and their discharges from the 2009 TRI and DMR databases, in pounds per year (LBY) and toxic-weighted pound equivalents (TWPE). Table 4 lists those manufacturing op erations that appear to ha ve been idled or closed prior to 2009.Preliminary Study of Regenerated Cellulose ManufacturersTable 3. Operating U.S. Cellulose Products Manufacturers and Corresponding 2009 TRI and DMR Discharges2009 TRI Data2009 DMR DataFacilityaLocationProduct TypeDischargeTypebBasis ofEstimatecCS2PoundsReleasedfromFacilitydCS2PoundsReleased toStreameCS2TWPEAverageFlow(MGD)CS2LBYCS2TWPE13MCorporationElyria, OHCellulosicSpongesIndirectM2NRNRNRNANRNR23MCorporationTonawanda,NYCellulosicSpongesIndirectO4,7007522,105NANRNR3Innovia FilmsInc.Tecumseh,KSCellophaneDirectM226,50026,50074,3002.2224,10053,1004Spontex Inc.Columbia,TNCellulosicSpongesDirectM22232236240.38NRNR5ViscofanUSA Inc.Danville, ILFood CasingsIndirectM214,0002,2406,270NANRNR6ViskaseCorporationOsceola, ARFood CasingsDirectO4734731,3201.16NRNR7ViskaseCorporationLoudon, TNFood CasingsIndirectM213,0002,0805,820NANRNRSource:Industry Profile of the Cellulose Products Manufacturing Facilities in the U.S.(Schmidtke, 2000),DMRLoads2009_v2,TRIReleases2009_v2.a – Cellulose manufacturing facilities that are currently operating in the United States.b – ELGs control pollutant discharges at the point of discharges from industrial facilities and cover discharges directly to surface water (direct discharges) anddischarges to POTWs (indirect discharges).c – Basis of Estimate Descriptions: M1: continuous monitoring data or measurements; M2: periodic or random monitoring data or measurements; C: mass balancecalculations, such as calculation of the amount of the toxic chemical in streams entering and leaving process equipment; E: published emission factors; E2: sitespecific emission factors; and O: other approaches, such as engineering calculations.d – Discharges include transfers to POTWs and do not account for POTW removals.e – Discharges include transfers to POTWs and account for POTW removals.NR – No data reported.6Preliminary Study of Regenera ted Cellulose Manufacturers

7 Table 4. Closed or Idled Cellulose Manufacturers in the United States

Facility Name Location Product Type Facility Status in 2011 Type of Discharger a Lenzing Fibers Corp. Axis, AL Rayon Closed Direct Lenzing Fibers Corp. Lowland, TN Rayon Closed Direct 3M Corporation Prairie du Chien, WI Cellulosic Sponges Idled Indirect

Sou rce: Industry Profile of the Cellulose Products Manufacturing Facilities in the U.S. (Schmidtke, 2000)

2 .0 C ARBON D ISULFIDE P ROPERTIES
All cellulose products manufacturers use CS 2 in the viscose process to regenerate cellulose. The CS 2 is used to react with aged alkali cellu lose to form sodium cellulose xanthate. CS 2 is an extremely flammable and highly volatile chem ical that is slightly soluble in water.

2.1 Chemical Properties of Carbon Disulfide

Table 5 presents chemical properties for CS 2 compared to acetone and ethanol. The Henry’s Law Constant for CS 2 is 1,748 Pa m 3 /mol at 25o C (Love, 2011). Henry’s Law Constant is the measure of the solubility of a gas in a liqui d at a particular temperat ure, proportional to the pressure of that gas above the liquid (Kotz and Treichel, 1999). Chemicals with a higher Henry’s Law Constant are more volatile. For example, CS 2 is highly volatile: th e gas constant for CS 2 is approximately 403 times higher than that for acetone (4.02 Pa m 3 /mol).

Table 5. Chemical Properties of Carbon Disulfide, Acetone, and Ethanol

Chemical Properties CS 2 Acetone Ethanol Henry’s Law Constant at 25oC 1,748 Pa m 3 /mol 4.02 Pa m 3 /mol 0.585 Pa m 3 /mol Water Solubility 0.2% at 20o C Soluble Miscible Evaporation Rate a 22.6 5.7 NA National Fire Protection Association (NFPA) Flammability Rating b 4 3 3

Sources: EPA On-line Tools for Site Assessment Calculation; Fischer Scientific MSDS for Acetone and Ethanol; Love, 2011; Ohio EPA, 2010; and OSHA Guidelines for Carbon Disulfide. a – The rate at which a material will vaporize when co mpared to the known standa rd rate of butyl acetate (evaporation rate = 1.0). b – The NFPA flammability rating ranks the relative danger for a chemical. The higher the rating, the higher danger associated with the chemical flammability.

CS 2 is also hazardous to humans when inhaled. Table 6 presents the Occupational Safety & Health Ad ministration (OSHA) and National In stitute for Occupational Safety and Health (NIOSH) established permissible exposure li mits (PELs) and recommended exposure limits (RELs) for CS 2 , acetone, and ethanol. These exposure limits correspond to the amount or concentration of the substance in the air and may also contain sk in designation. As part of the Occupation Safety and Health Guid elines, OSHA also established CS 2 PELs of 30 ppm (acceptable peak concentration for a 30 minute exposure) and 100 ppm (instantaneous maximum peak). NIOSH RELs also include a 10 ppm short-tem exposure limit.Preliminary Study of Regenera ted Cellulose Manufacturers

8 Table 6. Inhalation Exposure Limits for Ca rbon Disulfide, Acetone, and Ethanol

Exposure Limits CS 2 Acetone Ethanol OSHA PELS (TWA) a 20 ppm b 1000 ppm 1000 ppm NIOSH RELs (TWA) a 1 ppm 250 ppm 1000 ppm Sources: Fischer Scientific MSDS for Acetone and Etha nol and OSHA Guidelines for Carbon Disulfide. a – Time weighted average. b – OSHA PEL for CS 2 is an 8-hour time weighted average (TWA) concentration.

B ecause CS 2 is highly volatile and flammable, f acilities take additional precautions to reduce emissions to the air and sp arks during the transfer of CS 2 . These precautions include submerging the pipelines from storage tanks to the process in water trenches, transporting recovered CS 2 underground from the process to st orage tanks, and transferring CS 2 by gravity or magnetically sealed pumps.

EPA contacted the Carbon Disulfide Coalition to determine its toxicity levels and fate and transport in water. The Akzo Nobel cont act, a Carbon Disulfide Coalition member and a manufacturer of CS 2 , provided the following fres hwater toxicity levels:

 Freshwater, acute: 3 mg/L; and

 Freshwater, chronic: 1 mg/L.

The Akzo Nobel contact also stated that CS 2 volatilizes quickly from water. Historically, Carbon Disulfide Coalition scientists had difficulty measuring the solubility of CS 2, due to the rapid volatilization of free CS 2 into the vapor space. They found that the dissolved levels quickly dropped during the experiment. The Coalition co ncluded that the fate and transport of CS 2 in water would be volatiliza tion, i.e., none would stay in solution (Love, 2011).

Table 7 presents the total air emissions and water discharges (to surface water or POTW) for the seven cellulose products ma nufacturers. Th e reported data confirm that the majority of the CS 2 evaporates, which corresponds with the physical/chemical properties. However, the estimated concentration of CS 2 in the water discharged from four facilities exceeds the CS 2 solubility at 25o C (0.2 %) (Love, 2011).Preliminary Study of Regenera ted Cellulose Manufacturers

9 Table 7. TRI 2009 Carbon Disulfide Air Emissi ons and Water Discharges for Cellulose Products Manufacturers

Facility Location Discharge Type a Water Releases % of Total CS 2

Discharges Total CS 2 Air Emissions CS 2 Discharge before POTW

Removals 1 3M Corporation Elyria, OH Indirect NA 187,000 NR 2 3M Corporation Tonawanda, NY Indirect 1.22 % b 379,000 4,700 3 Innovia Films Inc. Tecumseh, KS Direct 3.1 % b 820,000 26,500 4 Spontex Inc. Columbia, TN Direct 0.03 % 618,000 223 5 Viscofan USA Inc. Danville, IL Indirect 0.41 % b 3,360,000 14,000 6 Viskase Corporation Osceola, AR Direct 0.05 % 924,000 473 7 Viskase Corporation Loudon, TN Indirect 0.68 % b 1,890,000 13,000 Source: TRIReleases2009_v2

. a – ELGs control pollutant discharges at the point of di scharges from industrial facilities and include discharges directly to surface water (direct discharges) an d discharges to POTWs (indirect discharges). b – The estimated CS 2 concentrations discharged to wa ter from these fac ilities exceeds the CS 2 solubility at 25o C (0.2 %) NR – No data reported. NA – Not applicable.

2.2 Carbon Disulfide - Potential Pathways into the Environment

Releases of CS 2 from manufacturing facili ties are almost exclusively to the atmosphere (ATSDR, 1996). However, facilities transfer CS 2 to wastewater during feedstock unloading and storage and air pollution control. Other than cellu lose products manufacturing, industries that use CS 2 as a raw material or form it as a by-product include the manufacturi ng of soil disinfectant, development restrainer for instant color phot ography, aging of roasting coffee, pesticide intermediates, degreasing, chemi cal analysis, electroplating of gold and nickel, oil extraction, and dry cleaning (ATSDR, 1996) . Natural sources of CS 2 in the environment include anaerobic ocean floors, wetlands, microbial activity in soli ds, certain crop plants and trees, volcano and marsh emissions, and vapor space above liquid sulfur (ATSDR, 1996).

3 .0 W ASTEWATER S OURCES
At cellulose products manufact uring facilities, the primar y sources of wastewater containing CS 2 are railcar unloading, storage, viscose process steps, and air pollution control (Schmidtke, 2000). After reviewing the av ailable data, the ma jority of the CS 2 enters the wastewater from the viscose processes used to regenerate the cellulose (KDHE, 2005; Martin, 2011).

3.1 Unloading and Storage

Most cellulose products manuf acturing facilities receive CS 2 in the liquid or gas form by railcar. Because CS 2 is highly flammable, facilities unload CS 2 by water and/or nitrogen displacement to prevent fire or explosion. Wa ter displacement is a method of unloading liquid CS 2 from railcars where water enters the railcar at the same flow rate that the CS 2 is expelled to the storage container. Nitrogen displacement is the same process; however, the inert gas fills the railcar as CS 2 is expelled. Facilities use water and/or nitroge n displacement to preventPreliminary Study of Regenera ted Cellulose Manufacturers

flammable, gaseous CS 2 emissions to the atmosphere and to preclude contact with oxygen (§40 CFR 63.5610).

Once in the storage pool and/or tank, water or inert gas is again used to contain the CS 2
. If nitrogen is used, a nitrogen blanket is ap plied with enough pre ssure to keep the CS 2 in liquid form. If water is used, the liquid CS 2 is more dense than water, and a water blanket will also keep the CS 2 in liquid form. The liquid CS 2 remains at the bottom and is recovered or discharged to the wastewater treatment system. CS 2 does not evaporate from the unloading/storage system because the systems are closed to the atmosphe re and are not mixed/aerated, the process that allows CS 2 to volatilize. Figure 2 shows the CS 2 unloading and storage processes by displacement.

Figure 2. CS 2 Unloading and Storage System Using Containment Pool/Tank

F acilities using water displacement for raw material unloading generate CS 2 -saturated wastewater during railcar unloadi ng; water displaced from the CS 2 storage tank is sent to the facility’s wastewater treatm ent system (Schmidtke, 2000).

A fter unloading CS 2 , facilities store pressurized, liquid CS 2 in large tanks. Because CS 2 is extremely flammable, the faciliti es store the tanks with one or a combination of the following methods:
10Preliminary Study of Regenera ted Cellulose Manufacturers

11  Su bmerged under water in a containment pool;

 Raised above a water containment pool; or

 Covered by a nitrogen blanketing system.

Because liquid CS 2 has a higher specific gr avity than water, any CS 2 that leaks during storage will settle to the bottom of the containment pool that a st orage tank is submerged in or stored above.

In addition to underwater or ni trogen blanket storage, the faci lities use a water or nitrogen padding system to fill headspace in the tank and further prevent contact with oxygen. The water or nitrogen padding is displaced into the water pool as CS 2 is loaded into the storage vessel. Conversely, the water or nitrogen padding in the storage tank fills the headspace as CS 2 is expelled for use in the manufacturing process, also shown in Figure 2

. Any water that is displaced from the unloadi ng or storage in the pool and water padding is sent to the wastewater tr eatment system (Schmidtke, 2000). Table 8 presents the unloading and storage practices for each cellulose products ma nufacturing facility.

Table 8. Facility Carbon Disulfide Unl oading and Storage Practices as of 2000

Facility Unloading Procedures Facility Storage Procedures

Facility Facility Location Unloading System Water Displacement a Tank Location Padding System 1 3M Corporation Elyria, OH N 2 NA Submerged in Water Pool Water

2 3M Corporation Tonawanda, NY N 2 Yes Mounted Over Water Dike Water

3 Innovia Films Inc. b Tecumseh, KS N 2 No Mounted Over Water Dike N 2

4 Spontex Inc. Columbia, TN Water NA NA Water 5 Viscofan USA Inc. Danville, IL N 2 No Submerged in Bottom Sloped

Water Pool Water

6 Viskase Corporation Osceola, AR N 2 NA Submerged in Water Pool N 2

7 Viskase Corporation Loudon, TN N 2 Yes Submerged in Water Pool N 2

Source: Schmidtke, 2000 a – Some facilities use nitrogen to displace CS 2 from the railcar into storage tanks, but use a water dike or pool for the storage tank. Therefore, they create a wastewater stream as CS 2 enters the storage tank. b – I nnovia Films is the only facility where the CS 2 is not directly in contact with water as part of the unloading or storage processes at the facility. The facility contact confirmed that the majority of the facility’s discharges are from the viscose processes and CS 2 recovery at the plant.

3.2 Process Steps

CS 2 is combined with aged alkali cellulose to form sodium cellulose xanthate. After this reaction, the sodium cellulose xanthate is co mbined with liquid caustic and water in a coagulation bath. In order to control the sodium sulfate levels of the coagulation bath, water is continuously drained from this process step. Becau se the sodium cellulose xanthate contains some CS 2 from previous process steps, CS 2 is discharged with the wastewater (Martin, 2011).Preliminary Study of Regenera ted Cellulose Manufacturers

12 Any wastewater overflow from the vi scose solution steps also contains CS 2 discharges (Schmidtke, 2000). At this time, EPA is unable to determine what causes overflow from the viscose solution steps or the amount of wastewater that results from process overflow.

At one facility, CS 2 used in the viscose process is recovered through condensation. The facility uses steam to condense the CS 2 , which is ultimately sent to the recovery plant. The CS 2 not captured from condensation is oil-sc rubbed and recovered. Because some CS 2 is soluble in water, the steam condensate may contain CS 2 . The steam condensate is sent to the facility’s
wastewater treatment plant (Martin, 2011).

3.3 Air Pollution Control

On June 11, 2002, EPA promulgated a NESHAP for Cellulose Products Manufacturing (40 CFR Part 63, Subpart UUUU, 67 FR 40055) . The Cellulose Products Manufacturing NESHAP regulates the Miscellaneous Viscose Processes and Cellulose Ethers Production Categories. The Miscellaneous Viscose Process category include s cellulose food casings, rayon, cellulosic sponge, and cellophane manufacturing facilities. The NE SHAP established emissions limits for hazardous air pollutants (HAPs), such as CS 2 , carbonyl sulfide, ethylene oxide, methanol, methyl chloride, propylene oxide, and toluene. The resulting additional air pollution control may be tr ansferring more CS 2 to the water via scrubbers (U.S. EPA, 2006).

Gaseous by-products formed during the rege neration of cellulose, including hydrogen sulfide and CS 2 , are off-gassed from the process equipment. Facilities control emissions of these toxic gases using either a wet ga s scrubber, a direct-contact condens er, or a biofilter system. In a wet gas scrubber, the air pollutants are absorb ed by an aqueous solution. The wet scrubber removal efficiency for CS 2 varies depending on facility specifi c operations. For example, some systems can remove up to 65 percent of CS 2 prior to the stack (Marsha ll, 1998). The majority of the scrubbed CS 2 is either recovered or sent to wast ewater treatment as scrubber effluent wastewater. At other facilities, CS 2 removal is low but the scr ubber effluent wastewater may contain some CS 2 (Schmidtke, 2000).

In d irect-contact condensers, water vapors are condensed out of the vent stream. The condensed water is sent to the wastew ater treatment system. The remaining CS 2 vapors are pulled by a vacuum jet to a second direct-contact condenser. The CS 2 condenses because of the decrease in temperature and is sent to a se ttling tank with other process by-products. The condensed CS 2 is piped underground to the storage ta nks in the water containment pool. The CS 2 emission reduction for these condenser sy stems is 99 percent (Schmidtke, 1998a).

Biofilters are also used as air pollution control at cellulose products manufacturing facilities. Each biofilter (bed) has a plenum at the bottom (air space), a midsection that contains grating and media that contain microbes, and a cover on top. The gases enter the bottom of the bed and exit from the top. The removal efficien cy of the biofilter varies based on process conditions; however, normal CS 2 reductions across the bed ar e approximately 80 percent (Nicholson, 2000). Wastewater from the bi ofilter, which may contain some CS 2 , is sent to wastewater treatment facilities. The spent media from the biofilter are neutralized with lime and hauled offsite (Nicholson, 2000).Preliminary Study of Regenera ted Cellulose Manufacturers

13 4.0 R EGENERATED C ELLULOSE P ROCESS W ASTEWATER T REATMENT

Table 9 summarizes the wastewater treatme nt used by the three cellulose products manufacturers where EPA obtai ned data (Schmidtke, 2000). Table 10 summarizes the possible sources of wastewater contain ing CS 2 and the methods of wastewater treatment specific to each plant.

Table 9. Cellulose Products Wastewater Treatment

Product Pretreatment Used by Indirect Dischargers Treatment Used by Direct Dischargers Cellophane NA Neutralization, settling, equalization, second neutralization, aeration, and clarification (i.e., activated sludge) Food Casings Neutralization, filtration and settling. Achieved CS 2 concentrations of 5-20 parts per million (ppm). Neutralization using lime, equalization, and clarification.

Cellulosic Sponges Neutralization and oxidizatio n Equalization, aeration, and clarification (activated sludge). Source: Industry Profile of the Cellulose Products Manufacturing Facilities in the U.S. (Schmidtke, 2000). NA – Not applicable.

In addition to wastewater treatment, facility management practices also affect how much CS 2 is discharged in wastewater. For example, the Loudoun, TN Viskase facility formerly used a water blanket during CS 2 unloading. This led to 10,000 gallons of CS 2 saturated water being discharged to the wastewater tr eatment facility every time CS 2 was unloaded. By converting to the nitrogen blanket system, the Viskase faci lity eliminated a significant source of CS 2 wastewater discharges (Schmidtke, 1998b).Preliminary Study of Regenerated Cellulose ManufacturersTable 10. Confirmed Sources of Wastewater and Wastewater Treatment at Cellulose Manufacturing FacilitiesFacility NameLocationProductTypePossible Sources of WastewaterWastewaterTreatmentType ofDischargera13MCorporationElyria, OHCellulosicSponges- Biofilter- Oxidation- Neutralization- Holding tanksIndirect23MCorporationTonawanda,NYCellulosicSponges- Storage tank displaced water- Rotary vacuum filters- NeutralizationIndirect3Innovia FilmsInc.Tecumseh, KSCellophane- Viscose steps- Extrusion/regeneration- Neutralization- Settling basin- Equalization basin- Activated SludgeDirect4Spontex Inc.Columbia, TNCellulosicSponges- Storage tank displaced water- Railcar blowoff- H2S scrubber vacuum pump discharge- Equalization- Activated SludgeDirect5Viscofan USAInc.Danville, ILFoodCasings- Overflow of storage tank submersion water- Viscose steps (slurry, ripening, filtration)- Extrusion/regeneration- Washing- Acid systems (acid recovery, basement systems,anhydrous department)- Mixing basin- Neutralization- Settling basins- Discharge basin(stack)Indirect6ViskaseCorporationOsceola, ARFoodCasings- Viscose steps (ripening room trenches)- Extrusion/regeneration (extrusion wash water, extrusionacid)- Deaerator condensate- Waste handling- Neutralization(lime)- Equalization- ClarifiersDirect7ViskaseCorporationLoudon, TNFoodCasings- Extrusion/regeneration- WashingIndirect- Filter- NeutralizationSource:Industry Profile of the Cellulose Products Manufacturing Facilities in the U.S.(Schmidtke, 2000).a – ELGs control pollutant discharges at the point of discharges from industrial facilities and cover discharges directly to surface water (direct discharges) anddischarges to POTWs (indirect discharges).14Preliminary Study of Regenera ted Cellulose Manufacturers

15 5.0 F ACILITY D ISCHARGE D ATA

E PA reviewed all available CS 2 concentration data for facilities presented in Table 3

. EPA located wastewater treatment infor mation for two facilities: I nnovia Films, Inc in Tecumseh, KS and Viskase Corporation in Loudon, TN.

5.1 Innovia Films, Inc in Tecumseh, KS

Innovia Films, Inc in Tecumseh, KS manufact ures cellophane used primarily in food packaging. EPA obtained 2009 discharge monitoring re port (DMR) data for this facility, the only cellulose products manufacturing fac ility required to monitor for CS 2 . EPA obtained facilityspecific waste stream and wastewater treatment da ta from the facility’s permit and fact sheet.

5.1.1 Waste Streams

Acid, alkaline, and neutral waste streams are generated from the cellulose production process. All process wastewater s are commingled, treated, and di scharged through the treatment plant discharge (outfall 001). Approximately 2.0 MGD wastewater is treated and discharged through Outfall 001. Table 11 describes the facility waste streams and typical flow.

Table 11. Innovia Films, Inc Waste Streams

Waste Stream Description Typical Flow (MGD) Alkaline Domestic waste flows and alkaline waste streams from the mix house, finishing, coating, casting, and the viscose manufacturing areas (VMA) 0.67

Acid Acid waste process flows from casting areas and the powerhouse a 0.6

Neutral Condensate flow from the hot well area 0.68 Source: Facility Fact Sheet (KDHE, 2005).

a – The powerhouse discharge also in cludes water from reverse osmosis cleaning and demineralizer washes.

C S 2 enters the wastewater from differen t processes at the plant (Martin, 2011):

 Start up procedures that call for the du mping of liquid viscose (alkaline waste stream);

 Overflow from the viscose process, whic h results in various losses of CS2 as liquid viscose (alka line waste stream);

 Continuous dumping of the coagulation bath solution to the wa stewater treatment system, which is dumped to control the ba lance of sodium sulfate in the viscose process (alkaline waste stream);

 Casting area water and wash wa ter (acid waste stream); and

 CS2 recovery system (neutral waste stream), which is described below.

Becau se CS 2 is volatile valuable feedstock, th e facility recovers volatilized CS 2 used in the process in the CS 2 recovery system (Martin, 2011). Th e following process steps result in excess or liberated CS 2 air emissions:Preliminary Study of Regenera ted Cellulose Manufacturers

16  The xanthation step in the viscose process, where CS 2 is sprayed on alkali cellulose to produce xanthate (an intermed iate product in the cellophane process);

 The extrusion/casting step, where the viscos e solution is soaked in concentrated and dilute sulfuric acid baths, which liberates CS 2 and hydrogen disulfide; and

 Th e extrusion/casting step where the cellu lose is washed in a hot water bath, which also liberates CS 2
.

At the CS 2 recovery plant, the facility uses steam to recover the CS 2 . Although the majority of the CS 2 is recovered, the facility contact stated that some CS 2 is captured in the steam condensate which is transferred to the wa stewater treatment system (Martin, 2011).

5.1.2 Wastewater Treatment

The plant uses an activated sludge extended ae ration process to treat the wa stewater. The acid wastestream is first neutra lized using hydrated lime in settl ing pond #1. The neutralized acid stream is then commingled with the alkaline and neutral wastestreams in settling pond #2. The combined wastestream is pumped to the equaliza tion basin. As the wastestream is pumped from the equalization basin to the ac tivated sludge aeration basin, th e plant adds phosphoric acid and ammonium hydroxide to provide supplemental nutrients for biological treatment. The excess activated sludge is settled in clarifiers, and the tr eated effluent is discharged to the Kansas River through a long outfall sewer. The sludge is c oncentrated by a centrifuge and land applied (KDHE, 2005). Figure 3 diagrams the Innovia Films wastewater treatment system (Mester, 2011).Preliminary Study of Regenera ted Cellulose Manufacturers

Settling Basin #1 Lime

Acid Wastestream

Holding Ponds Settling Pond #2 Neutral Wastestream Alkaline Wastestream

Equalization Tank Post Neutralization

Sodium Hydroxide (if necessary) Post Neutralization

Diversion Tank Aeration Basin

Splitter Box

60' Clarifier 100' Clarifier

Waste Sludge (Hauled Offsite) Clarifier Overflow (Effluent) Discharge

to Kansas RiverReturn ActivatedSludge

Figure 3. Block Diagram of Innovia Films Wastewater Treatment System

5.1.3 Discharge Data

Innovia Films’ per mit requires the facility to monitor for CS 2 because concentrations at 35 mg/L or greater inhibit the act ivated sludge process. The permit requires remedial action if the CS 2 concentration exceeds 17.5 mg/L. The facility analyzes the CS 2 samples using EPA Method 624.

The facility samples for CS 2 at the splitter box, which rece ives flow from the aeration basin and feeds the flow to the clarifiers. The overflow (treated effluent) from the clarifiers is piped underground by gravity to the outfall. The outfall discharges to the receiving stream approximately 7,000 feet from the splitter box. Table 12 shows the 2008, 2009, and 2010 CS 2 concentration data for Innovia Films, Inc.

Table 12. 2008, 2009, and 2010 Carbon Disulfide Concentration Data for Innovia Films, Inc.

Outfall Date Monthly Minimum Concentration (mg/L) Monthly Average Concentration (mg/L) Monthly Maximum Concentration (mg/L) 001 31-Jan-08 0.63 2.03 2.86 001 29-Feb-08 1.58 4.98 8.45

17Preliminary Study of Regenera ted Cellulose Manufacturers

18 Table 12. 2008, 2009, and 2010 Carbon Disulfide Concentration Data for Innovia Films, Inc.

Outfall Date Monthly Minimum Concentration (mg/L) Monthly Average Concentration (mg/L) Monthly Maximum Concentration (mg/L) 001 31-Mar-08 7.11 9.48 12.5 001 30-Apr-08 0.56 0.56 0.56 001 31-May-08 0.52 0.74 0.98 001 30-Jun-08 0.13 0.55 0.99 001 31-Jul-08 0.26 0.36 0.56 001 31-Aug-08 0.75 0.75 0.75 001 30-Sep-08 3.23 5.76 8.29 001 31-Oct-08 0 0 0 001 30-Nov-08 3.51 8.34 13.1 001 31-Dec-08 0 2.14 4.29 001 31-Jan-09 6.02 9.77 17.1 001 28-Feb-09 5.19 5.19 5.19 001 31-Mar-09 6.63 10.67 14.5 001 30-Apr-09 0.25 0.39 0.52 001 31-May-09 0.21 0.66 1.53 001 30-Jun-09 0.07 0.22 0.33 001 31-Jul-09 0.06 0.86 1.67 001 31-Aug-09 0.25 0.25 0.25 001 30-Sep-09 0.1 0.15 0.21 001 31-Oct-09 0.16 0.85 1.55 001 30-Nov-09 0 0.12 0.25 001 31-Dec-09 4.14 4.14 4.14 001 31-Jan-10 1.18 2.79 4.62 001 28-Feb-10 1.74 3.22 4.7 001 31-Mar-10 2.42 2.42 2.42 001 30-Apr-10 0.88 1.54 2.14 001 31-May-10 2.84 2.84 2.84 001 30-Jun-10 0 0.07 0.14 001 31-Jul-10 0.28 0.42 0.55 001 31-Aug-10 0.24 0.27 0.30 001 30-Sep-10 0.88 0.88 0.88 001 31-Oct-10 0.79 0.84 0.88 001 30-Nov-10 0.52 1.10 1.79 001 31-Dec-10 2.94 3.50 4.07 Sourc e: Envirofacts

As s hown in Table 12 , a total of 10 average concentrati ons (28 percent) exceed 3 mg/L, the acu te freshwater toxicity level for CS 2, and a total of 17 average concentrations (47 percent) exceed 1 mg/L, the chronic freshwater toxicity level for CS 2 (Love, 2011). There are no concentrations above the 17.5 mg/L permit m onitoring concentration. The Carbon Disulfide Coalition finds these concentrations are incons istent with their experiences. The coalition reviewed analytical values from a wastewater treatment system consisting of aeration and neutralization only. The concentrations of CS 2 at the discharge points were less than 1 mg/L, with an overall CS 2 removal over 99 percent (Love, 2011). Th e final effluent concentrations are likely less than those taken at the splitter box, becaus e after the sampling poi nt, the wastewater goes through clarification and travels over 1.3 mile s through a pipe to the surface water, allowing for further volatilization.Preliminary Study of Regenera ted Cellulose Manufacturers

19 5.2 Viskase Corporation in Loudon, TN

T he Viskase Corporation in Loudon, TN is a food casings manufacturer, one of two operated by Viskase Corporation, the world’s la rgest producer of sma ll-sized food casings (Schmidtke, 1998b).

5.2.1 Wastewater Source and Treatment

The Viskase Corporation plant uses approxi ma tely 1.95 MGD of water. Wastewater from the extrusion, regeneration, and washing areas is sent to the wastewater treat ment facility. At the wastewater treatment plant, coarse material s are removed from the waste stream and the wastewater is neutralized with lime. The wastewat er is sent off site for treatment at a POTW. The CS 2 levels in the wastewater sent to the POTW typically vary between 5 and 20 ppm (Schmidtke, 1998b).

5.2.2 Discharge Data

In 2009, EPA contacted Viskase Corporation an d the local pretreatme nt coordinator to confirm CS 2 discharges. The facility’s i ndustrial user permit limit for CS 2 is 5 mg/L. Viskase collects samples at the point where the discharge l eaves the facility and enters a pipe connected to the adjacent POTW. In addition, the POTW collects samples at the other end of this pipe, where the Viskase discharge enters the POTW. These samples are analyzed for CS 2 . The combined data show that the facili ty releases close to 100,000 pounds of CS 2 to the POTW, but the POTW receives less than 3,000 pounds per year from the discharge pipe per year. This decrease in pollutant load suggests the po ssible volatilizatio n of 97,000 pounds per year of CS 2 within the discharge pipe (Birkholtz, 2009; Glarrow, 2009; U.S. EPA, 2009).

The POTW provided CS 2 concentration measurements ta ken at the influent to their treatment system. Table 13 shows the results of these sampling events.

Table 13. Carbon Disulfide Concentration Data for Viskase Corporation in Loudon, TN

Date POTW Measurement at Treatment Works Influent (mg/L) Discharge Limit (mg/L) 13-Feb-06 12 5 14-Aug-06 <0.001 5 20-Feb-07 <0.001 5 19-Sept-07 1.1 5 1-Apr-08 1.4 5 19-Aug-08 <0.001 5 3-Feb-09 <0.001 5 S ource: Facility Contact (Birkholz, 2009).

T he CS 2 concentrations for Viskase Corporati on do not exceed the discharge limit of 5 mg/L, except for the February 2006 concentration. More importantly, these discharges represent the CS 2 concentrations prior to treatment through the POTW. Therefore, the CS 2 concentrations are likely below levels of detection in the POTW effluent, and are likely of no concern to human health and aquatic life.Preliminary Study of Regenera ted Cellulose Manufacturers

20 6.0 C ONCLUSIONS

T he conclusions of the cellulose produc ts manufacture review are as follows:

 From available data, EPA identified seven active regenerated cellulose manufacturers in the U.S. These faci lities use and discharge wastewater containing CS 2 generated from CS 2 storage, recovery, and the viscose process. EPA continues to resolve the overall questi on of how significant concentrations of CS 2 (ranging from values below detection to 17.1 mg/L) remain in the water after treatment, although CS 2 is highly volatile (430 time s more volatile than acetone, for example).

 There are three direct dischargers, bu t only one facility collects data on CS 2 in their wastewater. This facility, Innovia Films, Inc, di scharges up to 17.1 mg/L of CS 2 after activated sludge wastewater tr eatment. There are 17 of 36 monthly average concentrations in the facility’s 2008 through 2010 CS 2 data that are above the chronic freshwater toxicity leve l of 1 mg/L. The concentration of CS 2 entering the receiving stream is likely lower, b ecause the sample point is more than one mile from the final discharge point, allowing for further CS 2 volatilization in the discharge pipe. The measurements reported by Innovia Films are inconsistent with information receiv ed from the Carbon Disulfide Coalition. Based on Coalition solubility a nd volatility data, the CS 2 concentrations would be less than 1 mg/L following aeration.

 There are four indirect dischargers, but EPA obtained data from only one facility on CS 2 in their wastewater. Becau se facilities pre-treat th eir wastewater, and it is processed through a POTW, CS 2 concentrations for indirect dischargers likely are well below aquatic life criteria.

 T he cellulose products manufacturers usi ng the viscose process include a small number of U.S. facilities. For this reason, EPA considers these discharges are best controlled by facility-specific permitting assistance.

EPA prioritizes point source categories with existing regulations for potential revision based on the greatest estimated toxicity to human health and the environment, measured as TWPE. Based on the above conclusions, EPA will categorize these discharges with Part 414, OCPSF for future annual reviews. EPA is assigning this catego ry with a lower priority for revision (i.e., this category is marked with “(3)” in the “Findings” column in Table V-1 in the Federal Register notice that presents the 2011 an nual review of existing effluent guidelines and pretreatment standards).

7.0 R EFERENCES

1. Acetone . MSDS No. 00140 [Online]; Fischer Scie ntific: Fair Lawn, NJ. February 28, 2008, http://fscimage.fishersci.com/msds/00140.htm (accessed August 2, 2011).Preliminary Study of Regenera ted Cellulose Manufacturers

21 2. Agency for Toxic Substances and Disease Registry (ATSDR). 1996. Toxicological Profile for Carbon Disulfide . Atlanta, GA. U.S. Depart ment of Health and Human Services, Public Health Serv ice. EPA-HQ-OW-2010-0824. DCN 07673.

3. Beach, Robert, et al. 2000. Economic Analysis of Ai r Pollution Regulations: Miscellaneous Cellulose Manufactu ring Industry, Industry Profile . Research Triangle Institute. (February). EPA-HQ-OW-2010-0824. DCN 07674.

4. Birkholtz, Dave. 2009. Telephone conversation with Dave Bi rkholtz of City of Loudoun, TN POTW and Eleanor Codding of Eastern Research Group, Inc. “Carbon Disulfide Discharges Reported to TRI by Viskase F acility in Loudoun, TN.” (March 12). EPA-HQOW-2008-0517 DCN 07300.

5. ERG, 2010. Quality Assurance Project Plan for the Plastics Molding and Forming Preliminary Category Review . (November). EPA-HQ-OW-2010-0824. DCN 07675.

6. Ethanol . MSDS No. 91467 [Online]; Fischer Scie ntific: Fair Lawn, NJ. September 26, 2007, http://fscimage.fishersci.com/msds/91467.htm (accessed August 2, 2011).

7. Glarrow, Patrick. 2009. Telephone communication with Patrick Glarrow of Viskase in Loudoun, TN and Eleanor Codding of Eastern Research Group, Inc. “Carbon Disulfide Discharges Reported to TRI by Viskase F acility in Loudoun, TN.” (March 10). EPA-HQOW -2008-0517-0074.

8. KDHE, 2005. Kansas Department of Health and Environment – Bureau of Water. NPDES Permit Fact Sheet for Innovia F ilms, Inc. NPDES KS0003204. Tecumseh, KS. (September). EPA-HQ-OW-2010-0824. DCN 07676.

9. Kotz, John and Treichel, Paul. 1999. Chemistry and Chemical Reactivity, Fourth Edition

. Saunders College Publishing. pp. 653-654.

10. Love, Brian. 2011. Notes from E-mail Communi cation between Brian Love, Akzo Nobel, and Elizabeth Sabol, ERG. “RE: Carbon Disulfide - Fate and Transport.” (July 1). EPAHQ-OW-2010-0824. DCN 07677.

11. Marshall, Amy and Rebecca Nicholson. 1998. Site Visit Notes from 3M Corporation, (NESHAP for the Miscellaneous Cellulose Manufacturing Industr y). Tonawanda, NY. (November 3). EPA-HQ-OW-2010-0824. DCN 07678.

12. Martin, Tony. 2011. Notes from Telephone Communication between Tony Martin, Innovia Films, Inc, and Elizabeth Sabol, ER G. “RE: Carbon Disulfide – Wastewater Discharges and Recovery System.” (August 1). EPA-HQ-OW-2010-0824. DCN 07679.

13. Mester, Joe. 2011. Notes from Telephone Co mmunication between Joe Mester, KDHE, and Elizabeth Sabol, ERG. “RE: Carbon Disulf ide - Wastewater Discharges at Innovia Films, Inc.” (July 22). EPA-HQ-OW-2010-0824. DCN 07680.

14. Nicholson, Rebecca and Amy Marshall. 2000. Site Visit Notes from Nylonge Corporation, (NESHAP for the Miscellaneous Cellulose Manu facturing Industry). Elyria, OH. (May 1, 2000). EPA-HQ-OW-2010-0824. DCN 07681.Preliminary Study of Regenera ted Cellulose Manufacturers

22 15. Ohio EPA, 2010. National Pollu tant Discharge Eliminati on System (NPDES); BADCT Limits for Volatile Organic Compou nds. (November 8). EPA-HQ-OW-2010-0824. DCN 07683.

16. OSHA, 1994. Guidelines for Carbon Disulfide. Available online at: http://www.osha.gov/SLTC/healthguidelin es/carbondisulfid e/recognition.html

17. Schmidtke, Karen and Rebecca Nicholson. 1998a. Site Visit Notes from Lenzing Fibers Corporation in Lowland, TN (Miscellane ous Cellulose Manufacturing Industry NESHAP). Lowland, TN. (May 22). EPA-HQ-OW-2010-0824. DCN 07682.

18

. Schmidtke, Karen and Rebecca Nicholson. 1998b. Site Visit Notes from Viskase Corporation in Loudon, TN (Miscellaneous Ce llulose Manufacturing Industry NESHAP). Loudon, TN. (August 4). EPA-HQ-OAR-2003-0193-0006.

19

. Schmidtke, Karen and Thomas Holloway. 2000. Industry Profile of the Cellulose Products Manufacturing Facilities in the U .S. Prepared for U.S. EPA National Emissions Standards for Hazardous Air Pollutants: Cellulose Products Manufacturing . Cary, NC. (April 11). EPA-HQ-OAR-2003-0193-0004.

20

. U.S. EPA. EPA On-line Tools for Site A ssessment Calculation. Available online at: http://www.epa.gov/athens/learn2model/par t-two/onsite/sparcproperties.html

21

. U.S. EPA. 1984. Development Document for Effluent Limitations Guidelines and New Source Performance Standards for the Plas tics Molding and Forming Point Source Category . EPA 440/1-84/069. Washington, DC. (December).

22

. U.S. EPA. 1987. Development Document for Effluent Limitations Guidelines and Standards for the Organic Chemical, Plas tics, and Synthetic Fibers Point Source Category - Final . EPA 4401-87-009. Washington, DC. (October).

23

. U.S. EPA. 2005a. Preliminary Review of Prioriti zed Categories of Industrial Discharger s. EPA-821-B-05-004. Washington, DC. (August). EPA-HQ-OW-2004-0032- 0053.

24. U.S. EPA. 2005b. Product and Product Group Discharges Su bject to Effluent Limitations and Standards for the Organic Chemicals, Pl astics, and Synthetic Fibers Point Source Category - 40 CFR 414 . Washington, DC. EP A-HQ-OW-2004-0032-0941.

25. U.S. EPA. 2006. Technical Support Document for the 2006 Effluent Guidelines Program Plan . EPA-821-R-06-018. Washington, DC . (December). EPA-HQ-OW-2004-0032- 2782.

26. U.S. EPA. 2009. Technical Support Document for the Preliminary 2010 Effluent Guidelines Program Plan . EPA-821-R-09-006. Washingt on, DC. (October). EPA-HQOW-2008-0517-0515.

27. U.S. EPA. 2011. Technical Support Document for the 2010 Effluent Guidelines Program Plan. Washington, D.C. (October). EPA-820R-10-021. EPA-HQ-OW-2008-0517 DCN 07320.Preliminary Study of Regenera ted Cellulose Manufacturers

A-1 APPENDIX A 40 CFR Part 414

EPA first promulgated ELGs for the OCPSF Category (40 CFR Part 414) on November 5, 1987 (52 FR 42568). This category consists of seven subcategories that apply to the manufacture of products and product groups, as shown in Ta ble A-1 with corresponding Standard Industrial Classification (SIC) code s and applicability. Subparts B through H have limitations for biochemical oxygen demand (BOD 5 ), total suspended solids (TSS), and pH. The regulation also includes limitati ons and/or pretreatment standard s for certain toxic pollutants in three additional subparts:

Subpart I — Direct Discharge Point Sources That Use End-of-Pipe Biological Treatment; Subpart J — Direct Discharge Point Sources That Do Not Use End-of-Pipe Biological Treatment; and Subpart K — Indirect Discharge Point Sources.

Table A-1. Applicability of Subcat egories in the OCPSF Category

Subpart Subcategory Title Corresponding SIC Code(s) a Subcategory Applicability B Rayon Fibers 2823: Cellulosic Manmade Fibers Cellulosic manmade fiber (Rayon) manufactured by the Viscose process. C Other Fibers 2824: Synthetic Organic Fibers, Except Cellulosic All other synthetic fibers (except Rayon) including, but not limited to, products listed in Section 414.30. D Thermoplastic Resins 28213: Thermoplastic Resins Any plastic product classified as a thermoplastic resin including, but not limited to, products listed in Section 414.40. E Thermosetting Resins 28214: Thermosetting Resins Any plastic product classified as a thermosetting resin including, but not limited to, products listed in Section 414.50. F Commodity Organic Chemicals 2865: Cyclic Crudes and Intermediates, Dyes and Organic Pigments 2869: Industrial Organic Chemicals, NEC Commodity organic chemicals and commodity organic chemical groups including, but not limited to, products listed in Section 414.60.

G Bulk Organic Chemicals 2865: Cyclic Crudes and Intermediates, Dyes and Organic Pigments 2869: Industrial Organic Chemicals, NEC Bulk organic chemicals and bulk organic chemical groups includ ing, but not limited to, products listed in Section 414.70.

H Specialty Organic Chemicals 2865: Cyclic Crudes and Intermediates, Dyes and Organic Pigments 2869: Industrial Organic Chemicals, NEC All other organic chemicals and organic chemical groups includ ing, but not limited to, products listed in the OCPSF Development Document (Vol. II, Appendix II-A, Table VII). Source: Product and Product Group Discharges Subject to Effluent Limitations and Standards for the Organic Chemicals, Plastics, and Synthetic Fibers Point Source Category — 40 CFR 414 , Table 2-2 (U.S. EPA, 2005b). a – During the 2009 annual review EPA developed a cros swalk between SIC codes and NAICS codes. Because there is not a direct match EPA did not report NAICS codes. NEC – Not elsewhere classified.