Issued 2012 Chloroform

(Last Updated March 2012) p. 1



## ncasi
Pulp and Paper Mills 

## PART II. CHEMICAL-SPECIFIC INFORMATION FOR CHLOROFORM

SECTION 1. TOXIC CHEMICAL IDENTITY

1.1 CAS Number

- 67 -66-3

1.2 Toxic Chemical or Chemical Category Name - Chloroform

SECTION 3. ACTIVITIES AND USES OF THE TOXIC CHEMICAL AT THE

FACILITY

3.1 Manufacture the toxic chemical:

Chloroform is produced as a byproduct in the C, E and H stages of pulp bleaching and during pulping, chemical recovery and chlorination of water.

Estimates for virgin pulp bleach plant chloroform emissions based on NCASI laboratory studies and field data are presented in Table 1 and Table 2 (NCASI 1988; NCASI file information). Table 1 gives the chloroform emissions from bleach plant vents and chloroform released to bleach plant sewers for bleaching sequences that include the use of hypochlorite. Table 2 provides estimates for total chloroform formed and released in the bleach plant for essentially hypochlorite-free bleaching sequences. From Technical Bulletin No. 558 (NCASI 1988) and other data in NCASI files (NCASI file information),

of the total chloroform formed in the bleach plant an average of 52 percent (range 6 to 90 percent) was found to be released through the bleach plant vents, with the remaining 48 percent (range 6 to 94 percent) discharged with the bleach plant effluent to the waste treatment facility.

Table 3 contains NCASI test data (NCASI 1993; NCASI file information) on chloroform formation during hypochlorite bleaching of repulped and deinked pulps. Although the

data in Table 3 would suggest that as compared to bleaching of virgin fibers less chloroform is produced during hypochlorite bleaching of recovered fibers, the virgin fiber chloroform generation data in Table 1 include nearly 0.3 lb/ODTP of chloroform formed in the chlorination stage of virgin fiber bleaching. Excluding the impact of the chlorination stage, the chloroform generation estimates for recovered fibers in Table 3 seem to be consistent with the chloroform generation estimates for virgin fibers in Table

1 . Thus, if no mill specific information is available, one may estimate the amount of chloroform generated in recovered fiber bleaching by using the estimates for virgin fibers

in Table 1 , with a decrease of 0.3 lb CHCl 3 

## /ODTP in the absence of a chlorination stage in the recovered fiber bleaching sequence.Issued 2012 Chloroform

(Last Updated March 2012) p. 2



## ncasi
Pulp and Paper Mills 

### TABLE 1 BLEACH PLANT CHLOROFORM FORMATION ESTIMATES FOR SEQUENCES WITH HYPOCHLORITE

BLEACHING SEQUENCE

HYPOCHLORITE USE* CHLOROFORM, lb/ODT BROWNSTOCK

Air Emissions from Vents Discharge to Waste Treatment Facility Total Range Average Range Average Range Average
0.1 to <0.5 percent 0.07 to 0.73 0.26 0.08 to 0.76 0.24 0.3 to 1.0 0.5 0.5 to 2 percent 0.12 to 1.10 0.52 0.14 to 1.14 0.48 0.5 to 1.5 1.0 >2 percent 0.24 to 2.19 0.78 0.27 to 2.28 0.72 1.0 to 3.0 1.5
*Percent hypochlorite use includes the hypochlorite generated by scrubbing Cl 2 

### from ClO 2 

### generator gases and used in the E stage. It is expressed as (lb available chlorine used/lb OD brownstock pulp) x 100. If sodium hypochlorite usage rates are known, then the following conversion applies:Issued 2012 Chloroform

(Last Updated March 2012) p. 3



## ncasi
Pulp and Paper Mills 

### TABLE 2 BLEACH PLANT CHLOROFORM FORMATION ESTIMATES FOR  0.1 PERCENT HYPOCHLORITE SEQUENCES

PULP SPECIES, CHLORINATION STAGE CONDITIONS* TOTAL CHLOROFORM RELEASED, lb/ODT BROWNSTOCK

Hardwood,  70% Substi tution 1.83 x Chlorine Factor

- 0.06 eq. 1
Softwood, Chlorine Factor  0.15, Zero Chlorine Dioxide Substitution, or Simultaneous Addition of Chlorine and Chlorine Dioxide, or <40 Percent of Tot al Available Chlorine Applied as Chlorine Dioxide is Added Before Chlorine. Total Substitution May or May Not be Higher than 40 Percent. 4.06 x Chlorine Factor

- 0.50 eq. 2

Softwood, Chlorine Factor <0.15, Zero Chlorine Dioxide Substitution, or Simultaneous Addition of Chlorine and Chlorine Dioxide, or <40 Percent of Total Available Chlorine Applied as Chlorine Dioxide is Added Before Chlorine. Total

Substitution Between Zero and 90 Percent. 0.74 x Chlorine Factor eq. 3

Softwood,  40 Percent of Total Available Chlorine Applied as Chlorine Dioxide

is Added Before Chlorine. Total Substitution  40 Percent and  70 Percent ( 2.91 x Chlorine Factor)

- 0.09 eq. 4

100 Percent ClO 2 

### Substitution, All Conditions 0.005Issued 2012 Chloroform

(Last Updated March 2012) p. 4



## ncasi
Pulp and Paper Mills 

### TABLE 3 CHLOROFORM FORMATION IN RECYCLED PULP BLEACHING

MILL SECONDARY

FIBER

S OURCES BLEACH

SEQUENCE WEIGHT

PERCENT

HYPO USED** CHLOROFORM DISCHARGED, lb/ODTP

Vents Sewers Total
A (2) Repulped H 1.10 0.07 0.62 0.69 B (2) Deinked H 0.56 <0.01 0.58 0.58 C (2) Repulped H 0.95 0.54 0.24 0.78 D (2) Repulped CH 1.92 2.03 1.27 3. 30 E (3) Deinked H 0.25 0.07 0.04 0.11 F (3) Deinked HY* 0.30 0.01 0.29 0.30
*Y - hydrosulfite bleaching stage

** - weight percent hypo as defined in Table 1



## Chloroform is also produced in trace quantities during the chlorination of water. According to EPA (EPA 1984), 3.4 lbs. of chloroform /10 9 

## gallons of water are formed and emitted during the chlorination of “once-through” cooling water systems. Additionally, 25.5 lb/10 6 

## gallons and 0.34 lb/10 6 

## gallons of chloroform are formed and emitted during the chlorination of “recirculating” cooling water systems, and drinking water, respectively.

Trace quantities of chloroform have also been measured in various pulp and paper mill

vents and these are summarized in Table 4 (NCASI 2010 ).

For an unbleached mill or a mill practicing 100 percent ClO 2 

## substitution, based on the amount of chloroform generated in bleaching (Table 2 ) and emission estimates for most major sources (Table 4 ), the total amount of CHCl 3 

## inadvertently manufactured and emitted is likely to be <0.0 3 lb/ADTUBP.

Sample Calculation for Threshold Determination :

A kraft mill produces 1100 ADTUBP/day which is then bleached (100 percent ClO 2 

## substitution) after O 2 

## delignification to produce 1000 ADTBP/day. At this mill, brown stock washer ven t gases are collected and treated in an incineration device. The pulping process generates 3300 lb BLS/ADTUBP which is fired in DCE furnaces and 0.275 ton CaO is regenerated in the lime kiln per ADTUBP. The mill operates a 500 x 10 6 

## Btu/hr wood-fired boiler and a 50 tpd tall oil plant. The final product is 1000 tons of bleached paper per day. The mill operates all 365 days/yr and discharges 20 x 10 6 

## gpd.

Table 5 shows the amounts of chloroform emitted from several major operations at this example mill as estimated using factors given in Table 4

. Table 5 also shows the amount of chloroform manufactured and present in (1) in uncontrolled NCGs, (2) strong black liquors beforeIssued 2012 Chloroform

(Last Updated March 2012) p. 5



## ncasi
Pulp and Paper Mills 

### TABLE 4 PULP AND PAPER MILL VENTS - EMISSIONS OF CHLOROFORM (NCASI 2010)

VENT DESCRIPTION UNITS NO. OF

SOURCES *DETECTED

MIN MAX MEDIAN MEAN STD DEVTESTEDINCLUDED

Kraft Mill Sources Black Liquor Oxidation Tank lb/T BLS 10 3 3 1.30E

- 06 3.90E

- 05 3.80E

- 06 1.48E

- 05 2.12E

- 05

Brownstock Washer

- All Other a lb/ADTUBP 8 6 2 <1.6E

- 06 2.50E

- 04 1.80E

- 06 4.32E

- 05 9.25E

- 05

Brownstock Washer

- Vacuum Drum Type (>300 ppm) b lb/ADTUBP 29 17 14 3.20E

- 06 2.30E

- 02 4.00 E

- 04 2.81E

- 03 5.99E

- 03

Brownstock Washer

- Vacuum Drum Type ( < 300 ppm) b lb/ADTUBP 5 5 4 3.20E

- 06 1.90E

- 03 9.51E

- 05 4.04E

- 04 8.78E

- 04

ClO 2 Generator Scrubber lb/T ClO 2 4 4 2 <1.1E

- 03 1.10E

- 02 2.00E

- 03 5.08E

- 03 7.30E

- 03

Decker lb/ADTUBP 8 1 1

-- -- 3.60E

- 05 3.60E

- 05

-- Deknotter lb/ADTUBP 5 2 2 1.40E

- 06 2.20E

- 06 1.80E

- 06 1.80E

- 06

-- Lime Kiln lb/T CaO 34 11 4 <8. 6E

- 05 1.80E

- 03 9.98E

- 05 3.91E

- 04 4.53E

- 04

NCG Thermal Oxidizer lb/ADTUBP 6 1 1

-- -- 1.00E

- 07 1.00E

- 07

-- Oxygen Delignification System lb/ADTUBP 10 7 5 1.10E

- 06 9.00E

- 04 5. 12 E

- 0 5 2.55E

- 04 3.50E

- 04 Paper Machine

- Bleached Paper & Pulp lb/ADTFP 7 5 3 7. 70E

- 07 5.80E

- 04 1.59E

- 04 2.02E

- 04 2.46E

- 04 Paper Machine

- Unbleached Linerboard lb/ADTFP 2 2 0 <1.2E

- 02 <4.3E

- 02

-- -- -- Prewasher Screen lb/ADTUBP 2 2 0 <9.1E

- 05 <1.1E

- 04

-- -- -- Recovery Furnace, DCE lb/T BLS 20 9 4 8.00E

- 06 7.90E

- 03 2. 08 E

- 0 4 1.10E

- 03 2.45E

- 03 Recovery Furnace, NDCE lb/T BLS 27 14 3 7.70E

- 06 5.30E

- 04 1.42E

- 05 4.79E

- 05 1.34E

- 04

Slaker&Causticizer

– Combined e lb/T CaO 4 4 0 <2.5E

- 06 <9.7E

- 04

-- -- -- Smelt Dissolving Tank e lb/T BLS 32 12 4 <7.6E

- 06 2.10E

- 04 7.10E

- 06 3.00E

- 05 5.5 9E

- 05

Solvent Based Silicone Coater lb/ADTFP 1 1 0 <1.3E

- 02 <1.3E

- 02

-- -- -- Tall Oil Reactor lb/T TO 7 7 3 1.50E

- 04 8.00E

- 02 1.8 0E

- 0 3 1.16E

- 02 2.79E

- 02 Miscellaneous Kraft Mill Vents Batch Digester Fill Exhaust lb/ODT chips 4 4 1 <2.4E

- 05 3.20E

- 03 4 .80E

- 05 8.00E

- 04

-- Continuous Digester Chip Bin Exhaust lb/ODT chips 3 1 1

-- -- 8.20E

- 07 8.20E

- 07

-- Unbleached Pulp Storage Tank lb/hr/tank 5 4 3 1.30E

- 04 9.40E

- 02 4.83 E

- 0 3 2.37E

- 02 4.06E

- 02 Weak Black Liquor Storage Tank lb/hr/tank 7 2 1 <1.1E

- 06 1.10E

- 06 8.34E

- 07 8.34E

- 07

-- Strong Black Liquor Storage Tank lb/hr/tank 9 6 4 <1.4E

- 06 1.00E

- 03 5.44 E

- 0 5 2.03E

- 04 3.60E

- 04 Green Liquor Clarifier e lb/T CaO 1 1 0 <5.6E

- 05 <5.6E

- 05

-- -- --Issued 2012 Chloroform

(Last Updated March 2012) p. 6



## ncasi
Pulp and Paper Mills 

### TABLE 4 (Cont’d) PULP AND PAPER MILL VENTS - EMISSIONS OF CHLOROFORM (NCASI 2010)

VENT DESCRIPTION UNITS NO. OF

SOURCES *DETECTED

MIN MAX MEDIAN MEAN STD DEVTESTEDINCLUDED

Dregs Filter Hood Exhaust e lb/T CaO 2 2 0 <1.9E

- 05 <3.6E

- 05

-- -- -- Green Liquor Surge Tank e lb/T CaO 1 1 1

-- -- 2.00E

- 06 2.00E

- 06

-- White Liq./Weak Wash Pressure Filter e lb/T CaO 1 1 0 <5.9E

- 04 <5.9E

- 04

-- -- -- White Liquor Pressure Filter Tank e lb/T CaO 1 1 0 <5.8E

- 04 <5.8E

- 04

-- -- -- Lime Mud Dilution Tank e lb/T CaO 1 1 0 <7.5E

- 05 <7.5E

- 05

-- -- -- Lime Mud Mix Tank e lb/T CaO 1 1 0 <6.1E

- 06 <6.1E

- 06

-- -- -- Lime Mud Pressure Filter e lb/T CaO 1 1 0 <2.1E

- 05 <2.1E

- 05

-- -- -- White Liquor Oxidation Tank e lb/ ADTUBP 2 2 0 <2.5E

- 05 <1.5E

- 04

-- -- -- Lime Mud Precoat Filter e lb/T CaO 5 2 2 8.60E

- 06 1.90E

- 05 1.40E

- 05 1.40E

- 05

-- Precoat Filter Vacuum Pump Exhaust e lb/T CaO 3 3 1 <2.8E

- 06 1.10E

- 04 5.06E

- 05 5.06E

- 05

-- Slaker Scrubber Vent lb/T CaO 3 3 0 <8.8E

- 07 <9.6E

- 04

-- -- -- Saltcake Mix Tank lb/T BLS 3 3 0 <6.6E

- 07 <1.4E

- 05

-- -- -- UNOX System Vent lb/ADTUBP 1 1 1

-- -- 1.73E

- 04 1.73E

- 04

-- Uncontrolled Kraft Pulp Mill NCGs Low Volume High Conc. NCGs c lb/ADTUBP 5 5 2 <2.2E

- 03 3.70E

- 02 1.50E

- 03 1.62E

- 02 1.47E

- 02 Stripper Off

- Gases c lb/ADTUBP 3 2 2 1.10E

- 03 2.20E

- 03 1.60E

- 03 1.60E

- 03

-- Sulfite Mi ll Sources All Pulping & Recovery Sources lb/ADTUBP 4 3 3 2.73E

- 04 4.91E

- 03 4.73E

- 04 1.87E

- 03 2.60E

- 03

Bleach Plant Scrubber lb/ADTBP 2 2 2 3.00E

- 03 1.45E

- 02 8.59E

- 03 8.59E

- 03

-- Recovery Furnace lb/T RLS 4 2 2 9.00E

- 05 1.90E

- 04 1.42E

- 04 1.42E

- 04

-- Semi

- Chemical Mill Sources Paper Machine, Corrugated lb/ADTFP 1 1 0 <3.1E

- 02 <3.1E

- 02

-- -- -- Non

- Chemical Mill Pulping Area Sources Deinking (With Bleaching) Operations lb/ADTP 6 6 4 <3.1E

- 05 1.20E

- 01 5.49 E

- 0 3 3.69E

- 02 4.78E

- 02 OCC & Recycled Paperb oard Stock Preparation lb/ADTP 1 1 1

-- -- 4.98E

- 05 4.98E

- 05

-- Pressurized Groundwood Pulping lb/ADTP 1 1 1

-- -- 9.80E

- 06 9.80E

- 06

-- Stone Groundwood Pulping lb/ADTP 5 5 2 <2.8E

- 04 7.70E

- 03 5.60E

- 04 2.90E

- 03 2.40E

- 03 Thermomechanical Pulping lb/ADTP 9 8 7 4.50E

- 06 1.50E

- 03 1.01E

- 04 3.84E

- 04 5.35E

- 04Issued 2012 Chloroform

(Last Updated March 2012) p. 7



## ncasi
Pulp and Paper Mills 

### TABLE 4 (Cont’d) PULP AND PAPER MILL VENTS - EMISSIONS OF CHLOROFORM (NCASI 2010)

VENT DESCRIPTION UNITS NO. OF

SOURCES *DETECTED

MIN MAX MEDIAN MEAN STD DEVTESTEDINCLUDED

Non

- Chemical M ill Paper Machines 100% Secondary Fiber Furnish lb/ADTFP 7 7 5 6.15E

- 06 1.51E

- 02 2.29E

- 03 3.22E

- 03 9.03E

- 03 Nonintegrated Mill lb/ADTFP 1 1 1

-- -- 4.87E

- 04 4.87E

- 04

-- Secondary Fiber & Other d Furnish lb/ADTFP 1 1 0 <1.3E

- 02 <1.3E

- 02

-- -- -- Virgi n Mech. & Chem. Pulp Furnish lb/ADTFP 11 8 5 <3.2E

- 04 2.20E

- 03 2.24E

- 04 6.18E

- 04 6.54E

- 04
Boilers (emissions after PM control devices)

Coal lb/ton

-- -- -- -- -- 5.90E

- 05 5.90E

- 05

-- Wood Residues lb/10 6 Btu 6 4 3 2.55E

- 06 4.70E

- 05 3.52E

- 05 2.59E

- 05 2.5 9E

- 05

Notes: a Other washers - diffusion, pressure, belt and baffle; b uncontrolled” emissions for VDWs with > or < 300 ppm methanol in final stage shower water (< 300 ppm methanol indicative of clean condensate or fresh water use); c same for mills with batch & continuous digesters; d Other – includes virgin chemical, groundwood and thermomechanical pulp e applies only to “Mills not using fresh water for mud washing”

ADT & ODT - air dry & oven dry ton; FP - finished product; BP & UBP – bleached & unbleached pulp; BLS & RLS – black & red liquor solids; TO – tall oil *“No. of sources - Tested” represents total number of sources that were tested; “No. of sources - Included” represents sources for which data were included in the analysis for estimating averages; the difference represents sources whose data were rejected mainly because they were non-detects with detection limits exceeding the highest detected observation – occasionally, an observation confirmed to be a statistical “outlier” was also rejectedIssued 20 12 Chloroform

(Last Updated March 2012) p. 8



## ncasi
Pulp and Paper Mills 

### TABLE 5 1 

### THRESHOLD DETERMINATION FOR CHLOROFORM MANUFACTURED - SAMPLE CALCULATION

PROCESS UNIT EMISSIONS MULTIPLIER TO GET lb/yr TOTAL MANUFACTURED, lb/yr Rate, mean Units

BLO Tank 1.48E

- 05 lb/T BLS (3300/2000)*1100*365 10

Bleach Plant 2.60E

- 03 a 

### lb/ADTBP (1000/1100)*1100*365 949

Brownstock Washers 2.81E

- 03 lb/ADTUBP b 

### 1100*365 1,128

Deckers 3.60E

- 05 lb/ADTUBP 1100*365 14

Lime Kilns 3.91E

- 04 lb/T CaO 0.275*1100*365 43

NCG Thermal Oxidizer 1.00E

- 07 lb/ADTUBP 1100*365 0 Oxygen Delignif

ication 2.55E

- 04 lb/ADTUBP 1100*365 102
Paper Dryer 2.02E

- 04 lb/ADTFP (1000/1100)*1100*365 74 DCE Recovery Furnaces 1.10E

- 03 lb/T BLS (3300/2000)*1100*365 729

Slaker/Causticizer Vents (2.50 E

- 06 /2) d 

### lb/T CaO 0.275*1100*365 0 Smelt Dissolving Tank 3.00E

- 05 lb/T BLS (3300/2000)*1100*365 20

Tall Oil Reactor 1.16E

- 02 lb/T TO (50/1100)*1100*365 212

Wood

- Fired Boilers 2.59E

- 05 lb/10 6 

### Btu (500 x 24/1100)*1100*365 113

Uncontrolled NCGs 1.62E

- 02 lb/ADTUBP 1100*365 6,504

Uncontrolled SOGs 1.60E

- 03 lb/ADTUBP 11 00*365 642

TOTAL MANUFACTURED AND EMITTED 10,541

AMOUNT RELEASED TO WWTP c 

### = 876 lb/yr (from bleach plant) 876
AMOUNT IN STRONG BLACK LIQUOR = 1100 ADTUBP/d X 365 d/yr x (3300/2000) ton BLS/ADTUBP x 0.0 lb/ton BLS 0

TOTAL MANUFACTURED 11,417

a 

### 52% of CHCl 3 

### generated in bleach plant is emitted; 0.52 x 0.005 = 2.6E-03 lb/ADTBP

b 

### estimates for brown stock washer vent gases before collection and control

c 

### 48% of CHCl 3 

### generated in bleach plant is released in effluent; 0 .48 x 0.005 x 1000 x 365 = 876 lb/yr

d 

### using 1⁄2 detection limit for NDs

1 

### If there are no mill-specific air emission measurements for chloroform, the information in Table 4 may be used. Table 4 presents both medians and means. In sample calculations presented here, means are used. Individual mills should select the approach with which they are most comfortable.Issued 2012 Chloroform

(Last Updated March 2012) p. 9



## ncasi
Pulp and Paper Mills 

## combustion and (3) WWTP untreated effluents. For this example mill, based on the total amount of chloroform manufactured and either emitted or released to the WWTP, a SARA 313 report does not have to be filed as the amount does not exceed 25,000 lb/yr.

3.2 Process the toxic chemical:

The SARA Section 313 regulations define “processing” as an incorporative activity. Chloroform is generally not processed in this industry.

3.3 Otherwise use the toxic chemical:

This would be the sum of all the chloroform used at the manufacturing site. Chloroform

is not used in this industry.

SECTION 4. MAXIMUM AMOUNT OF THE TOXIC CHEMICAL ON-SITE AT

ANY TIME DURING THE CALENDAR YEAR

4.1 _____ (Enter two-digit code from instruction package.)

Chloroform is expected to be present on the mill site only in the waste treatment plant (WWTP). For a kraft mill, in the absence of mill-specific information, the average concentration in the mill WWTP may be assumed to be 25 percent of the WWTP influent

c oncentration. The WWTP influent concentration is estimated in Tables 1, 2 or 3.

S ECTION 5. RELEASES OF THE TOXIC CHEMICAL TO THE

ENVIRONMENT ON-SITE

5.1 Fugitive or non-point air emissions

Fugitive or non

- point air emissions of chloroform are e xpected mainly from the

wastewater treatment plant ( WWTP ). Fugitive emissions may also occur from wastewater conveyance systems that are open to the atmosphere. Fugitive emissions from the WWTP are commonly modeled using the WATER9 software tool develope d by US EPA. WATER9 ( http://www.epa.gov/ttn/chief/software/water/ ) utilizes empirical correlations that relate mass transfer to the organic compound properties, WWTP characteristics, wind speed, etc. More details about typical parameters used to run this model are provided in Appendix 4.A of the SARA 313 Handbook. The following

se ctions deal an approach one could use to estimate fugitive emissions from various

c omponents of a mill’s WWTP.

(a) P rimary Clarifier

– Fugitive emissions from primary clarifiers are a function of the effluent flow rate, residence time, temperature, clarifier diameter, weir drop height, wind speed, and organic compound properties. WATER9 can be used to estimate fugitive emissions from clarifiers but has not been verified by field data. The reliability of estimates obtained using WATER9 is unknown at the presentIssued 2012 Chloroform

(Last Updated March 2012) p. 10



## ncasi
Pulp and Paper Mills 

## time. Results of application of WATER9 to an example primary clarifier (175 ft diameter, 12 ft depth, effluent temperature = 36  C, weir drop height = 10 inches, wind speed = 5 miles/hr) receiving 11 MGD of pulp mill effluent are shown in

Table 6 of Appendix 4.A. It should be noted that site-specific parameters for the clarifier could have a significant influence on these estimates. Thus, the use of site-specific parameters to arrive at these estimates is recommended.

(b) Secondary WWTP

– Fugitive emissions from secondary WWTP are a function of the WWTP characteristics, wind speed, and organic compound properties.

Table 6 provides estimates of chloroform partitioning in the secondary WWTP based on application of WATER9 to an example Aerated Stabilization Basin (ASB) and an Activated Sludge Treatment (AST) system. The characteristics of the ASB and AST used as model inputs in the WATER9 model are also provided in Appendix 4.A.

TABLE 6 WWTP PARTITIONING OF CHLOROFORM USING TYPICAL WATER9 PREDICTIONS

Aerated Stabilization Basin (ASB) a, b 

### Activated Sludge Treatment (AST) a 

### One Basin Two Basin Three Basin

Perce nt Volatilized 47.0 53.8 56.7 33.5 Percent Biodegraded 50.3 45.2 43.2 65.1

Percent in Effluent 2.7 1.0 0.1 1.4

Percent Overall Removal 97.3 99.0 99.9 98.6

a 

### Appendix 4.A

b 

### The one-basin model treats the WWTP as one well-stirred tank. The two-basin model treats three quarters of the WWTP as well stirred (with all the aeration HP) and the last quarter as a quiescent section (zero HP). The three-basin model treats the first 35% of the WWTP to be stirred with 50% of total HP, the next 40% to be stirred with the remaining 50% of total HP, and the last 25% to be quiescent. The two-basin and three-basin models are perhaps better representations of actual WWTP operation.



## Sample Calculations :

Case 1 - Bleaching Sequence with >0.1 Percent Hypochlorite

A mill bleaching 1000 ODT brownstock per day operates 365 day/yr, uses 1 percent hypochlorite in the bleach plant, and operates an aerated stabilization basin.Issued 2012 Chloroform

(Last Updated March 2012) p. 11



## ncasi
Pulp and Paper Mills 

## From Table 1 , CHCl 3 

## sent to the waste treatment system

= (0.48 lb CHCl 3 

## /ton pulp)(1000 tpd)(365 d/yr) = 175,200 lb/yr

CHCl 3 

## volatilized from the treatment basin using WATER9 predictions (three-basin model from

T able 6 )

= 0. 567 x 175,200 lb/yr = 99338 lb/yr

Case 2 - A Mill Bleaching 1,000 ODT Brownstock per day Operates 365 day/yr, Uses a 100%

ClO 2 

## Sub stitution Bleaching Sequence, and Operates an Aerated Stabilization Basin.

CHCl 3 

## formation

= 0.005 lb/ODT brownstock

CHCl 3 

## to the waste treatment system

= 0.48 x 0.005 lb/ODT brownstock = 0.0024 lb/ODT brownstock

CHCl 3 

## volatilized from the waste treatment system (using WATER9 three-basin model from

T able 6 )

= 0.0024 x 0.567 = 0.0014 lb/ODT brownstock

Annual fugitive emissions of CHCl 3 

## from the treatment basin

= 1000 ODT brownstock/day x 365 day/yr x 0.0014 lb/ODT brownstock = 511 lb/yr

Case 3 - A Mill Bleaching 1,000 ODT Brownstock per day Operates 365 day/yr, Uses a less

than 100% ClO 2 

## Substitution Bleaching Sequence with  0.1 Percent Hypochlorite Use, and Operates an Aerated Stabilization Basin.

Example 1

– Simultaneous addition of 50 lb Cl 2 

## and 19 lb ClO 2 

## per odtbs to softwood pulp Kappa No. 28, Kappa Factor = 0.179, Chlorine Factor = 0.089

Mixer Pulp

ClO 2 

### - 19 lb/ODTBS

Cl 2 

### - 50 lb/ODTBSIssued 2012 Chloroform

(Last Updated March 2012) p. 12



## ncasi
Pulp and Paper Mills 

## For the above bleach plant,

ClO 2 

## substitution, calculated as Cl 2 

## equivalent (ClO 2 

## has 2.63 times the oxidizing power of chlorine on a lb per lb basis)

Since the chlorine factor is <0.15 and all ClO 2 

## is applied simultaneously with Cl 2 

## , equation 3 of

Table 2 would apply.

CHCl 3 

## formation

= 0.74 x 0.089 lb/ODT brownstock = 0.066 lb/ODT brownstock

CHCl 3 

## to the waste treatment system

= 0.48 x 0.066 lb/ODT brownstock = 0.028 lb/ODT brownstock

CHCl 3 

## volatilized from the waste treatment system (using NOCEPM three-basin model from

Table 6 )

= 0.028 x 0.567 = 0.016 lb/ODT brownstock

Annual fugitive emissions of CHCl 3 

## from the treatment basin

= 1000 ODT brownstock/day x 365 day/yr x 0.016 lb/ODT brownstock = 5840 lb/yr

Example 2

– Addition of 11.4 lb ClO 2 

## per odtbs followed by addition of 70 lb Cl 2 

## to softwood pulp, Kappa No. 28, Kappa Factor = 0.179, Chlorine Factor = 0.125

For the above bleach plant, Pulp Mixer 1 Mixer 2 ClO 2 

### - 11.4 lb/ODTBS

Cl 2 

### – 70 lb/ODTBSIssued 2012 Chloroform

(Last Updated March 2012) p. 13



## ncasi
Pulp and Paper Mills 

## ClO 2 

## substitution prior to Cl 2 

## application, calculated as Cl 2 

## equivalent

Since the chlorine factor is <0.15 and ClO 2 

## substitution prior to Cl 2 

## application is less than 40 percent, equation 3 from Table 2 would apply.

CHCl 3 

## formation

= 0.74 x 0.125 lb/ODT brownstock = 0.0925 lb/ODT brownstock

CHCl 3 

## to the waste treatment system

= 0.48 x 0.0925 lb/ODT brownstock = 0.039 lb/ODT brownstock

CHCl 3 

## volatilized from the waste treatment system (using NOCEPM three-basin model from

Table 6 )

= 0.039 x 0.567 = 0.0 22 lb/ODT brownstock

Annual fugitive emissions of CHCl 3 

## from the treatment basin
= 1000 ODT brownstock/day x 365 day/yr x 0.022 lb/ODT brownstock = 8030 lb/yr

Example 3

- Addition of 26.6 lb ClO 2 

## per ODTBS followed by addition of 30 lb Cl 2 

## to softwood pulp, Kappa No. 28, Kappa Factor = 0.179, Chlorine Factor = 0.054

Pulp Mixer 1 Mixer 2

ClO 2 

### - 26.6 lb/ODTBS

Cl 2 

### - 30 lb/ODTBSIssued 2012 Chloroform

(Last Updated March 2012) p. 14



## ncasi
Pulp and Paper Mills 

## For the above bleach plant,

ClO 2 

## substitution prior to Cl 2 

## application

Since ClO 2 

## substitution prior to Cl 2 

## application is greater than 40 percent and ClO 2 

## substitution is greater than 40 percent, equation 4 from Table 2 would apply.

CHCl 3 

## formation

= (2.91 x 0.054 - 0.09) lb/ODT brownstock = 0.067 lb/ODT brownstock

C HCl 3 

## to waste treatment system

= 0.48 x 0.067 lb/ODT brownstock = 0.028 lb/ODT brownstock

CHCl 3 

## volatilized from the waste treatment system (using NOCEPM three-basin model from

Table 6 )

= 0.028 x 0.567 = 0.0 16 lb/ODT brownsto ck

Annual fugitive emissions of CHCl 3 

## from the treatment basin

= 1000 ODT brownstock/day x 365 day/yr x 0.016 lb/ODT brownstock = 5840 lb/yr

Example 4

- Same as example 3, split addition of ClO 2



### Pulp ClO 2 - 19.0 lb/ODTBS



### Cl 2 

### - 30 l b/ODTBS 

### Mixer 1 Mixer 2 ClO 2 

### - 7.6 lb/ODTBSIssued 2012 Chloroform

(Last Updated March 2012) p. 15



## ncasi
Pulp and Paper Mills 

## For the above bleach plant,

ClO 2 

## substitution prior to Cl 2 

## application

Since ClO 2 

## substitution prior to Cl 2 

## application is greater than 40 percent, equation 4 from

Table 2 would apply.

CHCl 3 

## formation

= (2.91 x 0.054 - 0.09) lb/ODT brownstock = 0.067 lb/ODT brownstock

C HCl 3 

## to the waste treatment system

= 0.42 x 0.067 lb/ODT brownstock = 0.028 lb/ODT brownstock

CHCl 3 

## volatilized from the waste treatment system (using NOCEPM three-basin model from

Table 6 )

= 0.028 x 0.567 = 0.0 16 lb/ODT brownstock

Annual fugitive emissions of CHCl 3 

## from the treatment basin

= 1000 ODT brownstock/day x 365 day/yr x 0.016 lb/ODT brownstock = 5840 lb/yr

Example 5

– Same as example 2, but split addition of ClO 2 

## ; 7.6 lb per odtbs followed by 3.8 lb per odtbs and 70 lb per odtbs Cl 2 

## , Kap pa No. 28, Kappa Factor = 0.179, Chlorine Factor =

0.125

Pulp ClO 2 

### - 7.60 lb/ODTBS

Cl 2 

### - 70 lb/ODTBS ClO 2 

### - 3.80 lb/ODTBS

Mixer 2 Mixer 1Issued 2012 Chloroform

(Last Updated March 2012) p. 16



## ncasi
Pulp and Paper Mills 

## For the above bleach plant,

ClO 2 

## substitution prior to Cl 2 

## application

Since the chlorine factor is <0.15 and ClO 2 

## substitution prior to Cl 2 

## application is less than 40 percent, equation 3 from Table 2 would apply.

CHCl 3 

## formation

= 0.74 x 0.125 lb/ODT brownstock = 0.0925 lb/ODT brownstock

CHCl 3 

## to the waste treatment system

= 0.42 x 0.0925 lb/ODT brownstock = 0.039 lb/ODT brownstock

CHCl 3 

## volatilized from the waste treatment system (using WATER9 three-basin model from

T able 6 )

= 0.039 x 0.567 = .0 22 lb/ODT brownstock

Annual fugitive emissions of CHCl 3 

## from the treatment basin

= 1000 ODT brownstock/day x 365 day/yr x 0.022 lb/ODT brownstock = 8030 lb/yr

(c) Surface impoundments and flow-through settling ponds – If a mill sends its

WWTP residuals (before dewatering) or weak spent liquors to a surface impoundment on-site, or sends its effluent through a flow-through settling basin

or lagoon, small amounts of fugitive emissions of chloroform would result. Fugitive emissions from these sources are a function of the effluent flow rate, residence time, temperature, exposed surface area, wind speed, and organic compound properties. These site-specific characteristics can be used in WATER9 models to estimate such emissions (See discussion in Appendix 4.A).

5.2 Stack or point air emissions

The only major source of stack or point air emissions of chloroform is the bleach plant

vent. These emissions can be estimated from Tables 1, 2 and 3 . Other minor sources of air emissions can be estimated from factors given in Table 4

.Issued 2012 Chloroform

(Last Updated March 2012) p. 17



## ncasi
Pulp and Paper Mills 

## Case 1 - Bleaching Sequence with >0.1 Percent Hypochlorite

From Table 1 , for the plant described above in section 5.1 (b) Case 1, the air emissions of CHCl 3 

## from t he bleach plant

= (0.52 lb CHCl 3 

## /ton pulp)(1000 tpd)(365 day/yr)
= 189,800 lb/yr

Case 2 - Bleaching Sequence with 100% ClO 2 

## Substitution

From Table 2 , for the plant described above in 5.1 (b) Case 2, the amount of CHCl 3 

## formed in the bleach plant

= 0.005 lb/ODT brownstock

Air emissions of CHCl 3 

## from bleach plant (using 52 percent emission from bleach plant vents)

= 0.52 x 0.005 lb/ODT brownstock = 0.0026 lb/ODT brownstock

Annual emissions of CHCl 3 

## from bleach plant vents

= 1000 ODT brownstock/day x 365 day/yr x 0.0026 lb/ODT brownstock = 949 lb/yr

Case 3 - Bleaching Sequence Using <100% ClO 2 

## Substitution & <0.1 Percent Hypochlorite

From Table 2 , for the plant described above in 5.1 (b) Case 3, Example 1, the amount of CHCl 3 

## forme d in the bleach plant

= 0.066 lb/ODT brownstock

Air emissions of CHCl 3 

## from bleach plant (using 52 percent emission from bleach plant vents)

= 0.52 x 0.066 lb/ODT brownstock = 0.034 lb/ODT brownstock

Annual emissions of CHCl 3 

## from bleach plant vents

= 1000 ODT brownstock/day x 365 day/yr x 0.034 lb/ODT brownstock = 12,410 lb/yr

If kraft noncondensible gases are partially vented based on the operational characteristics of the incinerator, then the emission factors given in Table 4 2 

## may be used to estimate emissions of chloroform from the noncondensible gas handling system. They are not expected to be significant.

2 

### See footnote on page 4.Issued 2012 Chloroform

(Last Updated March 2012) p. 18



## ncasi
Pulp and Paper Mills 

## Sample Calculation :

A kraft mill manufactures 1100 ATDUBP/day and burns pulping and evaporator NCGs and noncondensible stripper -off gases. They are vented to the atmosphere during 2 percent of the annual operating time.

Amount of chloroform in NCGs and SOGs being burn ed (from Table 4 , assuming batch digesters and using median with ND = 0)

= 1100 ADTUBP/d x 365 d/yr x (0.011 + 0.0016) lb/ADTUBP = 5,059 lb/yr

Chloroform vented to the atmosphere

= 0.02 x 5,059 = 101 lb/yr

5.3 Discharges to receiving streams or water bodies

Typical applications of the WATER9 three-basin ASB model (as shown in section 5.1 ( b )) show that from 0.1 percent of the chloroform is discharged with the effluent.

Sample Calculations :

Case 1 - Bleaching Sequence with >0.1 Percent Hypochlorite

For the plant described in 5.1 (b) Case 1, 175,200 lb/yr of CHCl 3 

## was shown to be sent to the waste treatment system. CHCl 3 

## discharged with the final effluent

= 0.001 x 175,200 lb/yr

= 175.2 lb/yr

Case 2 - Bleaching Sequence with 100% ClO 2 

## Substitution

For the plant described in 5.1 (b) Case 2, chloroform formed in the bleach plant

= 0.005 lb/ODT brownstock

Chloroform discharged to the waste treatment system

= 0.005 x 0.48 = 0.0024 lb/ODT brownstock

Chloroform discharged with the effluent

= 0.001 x 0.0024 lb/ODT brownstock = 2.4 x 10 -6 

## lb/ODT brownstock

Annual discharge of CHCl 3 

## with effluents

= 1000 ODT brownstock/day x 365 day/yr x 2.4 x 10 -6 

## lb/ODT brownstock = 0.88 lb/yrIssued 2012 Chloroform

(Last Updated March 2012) p. 19



## ncasi
Pulp and Paper Mills 

## Case 3 - Bleaching Sequence Using <100% ClO 2 

## Substitution & <0.1 Percent Hypochlorite

For the plant described in 5.1 (b) Case 3, Example 1, chloroform formed in the bleach plant

= 0.066 lb/ODT brownstock

Chloroform discharged to the waste treatment system

= 0.066 x 0.48 = 0.032 lb/ODT brownstock

Chloroform discharged with the effluent

= 0.001 x 0.032 lb/ODT brownstock = 0.00003 lb/ODT brownstock

Annual discharge of CHCl 3 

## with effluents

= 1000 ODT brownstock/day x 365 day/yr x 0.00003 lb/ODT brownstock = 11.0 lb/yr

5.4 Underground injections on-site

This does not typically apply to most mills.

5.5 Releases to land on-site

Discharges to land on-site could occur either through primary and/or secondary WWTP residuals (sludges). The primary and secondary sludges may be pumped to a surfaceimpoundment, such as a holding pond or lagoon, or dewatered and sent to either an onsite landfill or a combustion device. Published reports and data available to NCASI show that the chloroform content of sludges ranges from 0 to 63.5 ppm on a dry basis, with a mean of 1.1 ppm (NCASI file information, Warzyn 1980; NCASI 1984). These data can be used to estimate chloroform losses with primary and secondary sludges.

5.5.1 B Other landfills

Sample Calculation :

A mill produces 50 tons/day of sludge containing 40 percent solids. The sludge is sent to a landfill 365 day/yr.

Chloroform released with the sludge

= (50 tons wet sludge/day)(365 day/yr)(0.4 ton dry/ton wet)
x (1.1 x 10

- 6 

## ton CHCl 3 

## /ton dry sludge)(2000 lb/ton) = 16 lb/yrIssued 2012 Chloroform

(Last Updated March 2012) p. 20



## ncasi
Pulp and Paper Mills 

## 5.5.2 Land treatment/application farming

If a mill landspreads WWTP residuals (sludges) on-site, then the amount of chloroform in

these sludges needs to be reported in this section. These calculations are shown in section

5.5.1.

5.5.3 B Other surface impoundments

If a mill sends its primary and/or secondary WWTP residuals (sludges) to a surface

im poundment on-site, such as a holding or settling pond, lagoon, etc., then the amount of

c hloroform in sludges sent to this impoundment needs to be reported under this section.

The amount of CHCl 3 

## in sludges sent to the impoundment may be estimated in a manner

similar to that shown in section 5.5.1.

5.5.4 Other disposal

Any chloroform released to land on-site that does not fit under the previous three categories should be reported here.

SECTION 6. TRANSFERS OF THE TOXIC CHEMICAL IN WASTES TO

OFF-SITE LOCATIONS

These can be estimated from chloroform concentrations in waste streams such as WWTP residuals and mill effluent leaving the mill boundary. Note that this section only applies to toxic chemicals in waste streams. Thus, if a mill does not consider its spent liquor to be a waste stream, off-site transfers of spent liquor would not have to be reported in this

section.

6.1 Discharge to Publicly Owned Treatment Works (POTWs)

The quantity of reportable chemical transferred and basis of estimate should be provided for each wastewater discharge sent to a POTW. The amount of chloroform in untreated wastewater streams sent to POTWs may be estimated from the WWTP influent

c oncentrations given in Tables 1, 2 or 3

.

6.2 Transfers to other off-site locations

According to EPA guidance, the EPA identification number (EIN), name and address for each off-site location to which the facility ships or transfers wastes containing the reportable chemical, needs to be reported in this section. The amount of reportable chemical transferred, basis of estimate, and the types of waste management (treatment / disposal/recycling/energy recovery) should be provided for each off-site location.

For mills that transfer spent liquors to other locations (mills) and consider such liquors to be “waste” streams, the transfer of chloroform (if present) in these liquors needs also to

be considered in this section. The transfer of chloroform in other wastes such as WWTPIssued 2012 Chloroform

(Last Updated March 2012) p. 21



## ncasi
Pulp and Paper Mills 

## residuals to off-site locations should also be considered in this section. (For example, the off-site transfer of residuals for land-spreading or landfilling.)

SECTION 7. ON -SITE WASTE TREATMENT, ENERGY RECOVERY AND

RECYCLING METHODS

This section deals with the methods of waste treatment, energy recovery and recycling applied to the reported toxic chemical in “wastes” on site. Thus, if a mill does not consider a stream that contains a toxic chemical to be a “waste” and this stream is treated, burned for energy recovery, or recycled, this section does not apply to such a stream. For example, if a mill does not consider its spent liquor to be a “waste,” then the burning of

thi s liquor in recovery furnaces for chemical or energy recovery should not be considered in this section. Furthermore, the applicability of this section to a waste stream that passes through a pollution control device when such a device was clearly not designed to treat or

remove the toxic chemical contained in the waste stream is somewhat unclear. One interpretation is that if the overall percent removal efficiency for the toxic chemical in the

wa ste stream passing through a pollution control device is expected to be close to zero, this section does not apply. A second interpretation is that this section applies to such a waste stream and the toxic chemical in it even when the percent removal efficiency throug h the control device is close to zero. The examples shown in this section assume

the f irst interpretation.

SECTION 7A. ON -SITE WASTE TREATMENT METHODS AND EFFICIENCY

7A.1 Feed to Waste Treatment Systems

7A.1a W

7A.1b Waste Treatment Method(s) Sequence

H123 and H081

7A.1c Waste Treatment Efficiency Estimate

The overall treatment efficiency given by the WATER9 three-basin ASB

model in Table 5 is 99.9 % (range E3).

SECTION 7B. ON -SITE ENERGY RECOVERY PROCESSES

If a mill considers spent liquors to be “waste” streams and burns these liquors in recovery furnaces, this activity is covered under section 7B and the quantity of chloroform in the liquors (chloroform expected to be present only in bleach plant spent liquors) burned should be reported in this section (check for consistency with section 8.2).

If noncondensible gases (NCGs) containing chloroform are burned in a boiler (or

re covery furnace) then this may be considered as energy recovery. However, if NCGsIssued 2012 Chloroform

(Last Updated March 2012) p. 22



## ncasi
Pulp and Paper Mills 

## (including stripper gases) are burned in a lime kiln or thermal oxidizer (TO) then this may be considered as energy recovery or treatment (see section 8.6). In either case, note that

this section needs to be consistent with section 8.2.

If a mill burns waste treatment plant residuals containing chloroform in a boiler on-site

a nd considers this to be energy recovery and not treatment, the recovery code is U03 (check for consistency with section 8.2). This section would not apply if the mill

considers the residual to be a boiler fuel and not a waste stream.

SECTION 7C. ON -SITE RECYCLING PROCESSES

NA

SECTION 8. SOURCE REDUCTION AND RECYCLING ACTIVITIES

It should be noted that, with the exception of section 8.1 which deals with total releases to the environment, sections 8.2 through 8.7 apply to source reduction and recycling activities concerned with “waste” streams only.

8.1 Quantity released - Column B

In this section, facilities report disposal and other releases. This includes onsite disposal and other releases in Section 5 and off-site disposal and other releases in Section 6 (releases plus transfers for disposal and transfers to POTWs of metals and metal compounds), but excludesquantities reported in Section 5 and 6 due to remedial actions, catastrophic events, or nonproduction related events (see the discussion on Section 8.8.)

Sections 8.1a and 8.1b - Toxic chemicals disposed or otherwise released on site are reported in 8.1a or 8.1b as appropriate.

8.1a Quantity released - Column B – Current Reporting Year

Total on-site disposal to Class I Underground Injection Wells, RCRA Subtitle C landfills,

and other landfills

§ 8.1a = § 5.4.1 + § 5.5.1A + § 5.5.1B – § 8.8 (on-site release or disposal due to catastrophic events) 3



## 8.1b Quantity released - Column B – Current Reporting Year

Total other on- si te disposal or other releases

§ 8.1b = § 5.1 + § 5.2 + § 5.3 + § 5.4.2 + § 5.5.2 + § 5.5.3A + § 5.5.3B + § 5.5.4 – § 8.8 (on-site release or disposal due to catastrophic events)

3 

### §8.8 includes quantities of toxic chemicals disposed or otherwise released onsite or managed as a waste off site due to remedial actions, catastrophic events, or one time events not associated with the production process.Issued 2012 Chloroform

(Last Updated March 2012) p. 23



## ncasi
Pulp and Paper Mills 

## Sections 8.1c and 8.1d - Toxic chemicals transferred off site to POTWs or other off-site

loca tions that remain untreated 4 

## should be reported in 8.1c or 8.1d as appropriate. For example, quantities of a toxic chemical sent to a POTW and subsequently sent to a landfill, or quantities of a toxic chemical sent to other off-site landfills that remain untreated, are reported in Section 8.1c. Quantities of a toxic chemical disposed or otherwise released by a POTW or other off-site locations to a stream are reported in Section 8.1d. Quantities of the toxic chemical sent to a

POTW or other o ff

-site locations and subsequently treated are reported in Section 8.7. Metals and metal category compounds sent to POTWs or other off-site locations should be reported in either section 8.1c or 8.1d and should not be reported as treated for destruction in Section 8.7.

8.1c Quantity released - Column B

Total off-site disposal to Class I Underground Injection Wells, RCRA Subtitle C landfills, and other landfills

§ 8.1c = § 6.1 (portion 5 

## of transfer that is untreated and ultimately disposed of in UIC

Class I Wells, RCRA Subtitle C landfills, and other landfills) + § 6.2 (quantities associated with M codes M64, M65 and M81) – § 8.8 (off-site disposal due to catastrophic events)

8.1d Quantity released - Column B

Total other off-site disposal or other releases.

§ 8.1d = § 6.1 (portion of transfer that is untreated and ultimately disposed of in UIC Class II-V wells, and land disposal other than to landfills) + § 6.2 (quantities associated with M codes M10, M41, M62, M66, M67, M73, M79, M82, M90, M94, M99) – § 8.8 (off-site disposal due to catastrophic events)

Sample Calculation :

For the mill described in section 5.1 (b) Case 1, section 5.2, Case 1, and section 5.3, Case 1, it

w as shown that chloroform discharged with treated effluents was 526 lb/yr, the fugitive emissions of chloroform were 164,338 lb/yr, and the total point source air emissions were 189,800 lb/yr. For the mill described in section 5.5.1, the quantity of chloroform in the sludge sent to an on-site landfill was 16 lb/yr. In addition, if the mill sent a portion of its effluent containing 100,000 lb/yr of chloroform to a POTW for treatment, then

(i) Quantity of chloroform released on-site

= 526 lb + 164,338 lb + 189,800 lb + 16 lb = 354,680 lb

4 

### Metals and metal category compounds are not treated in a POTW. In addition, some chemicals might not be fully treated for destruction at a POTW. If you are able to quantify the amounts of a toxic chemical sent to a POTW that are treated for destruction and disposed or released from the POTW untreated, you should divide the amount reported in Section 6.1 between Sections 8.1c and 8.1d and 8.7 (quantity treated off site), as appropriate. Otherwise, report the entire amount in Section 8.7.Issued 2012 Chloroform

(Last Updated March 2012) p. 24



## ncasi
Pulp and Paper Mills 

## (ii) Quantity of chloroform sent off-site for disposal

= 100,000 lb

(iii) Total quantity of chloroform released on-site or off-site
= (354,680 + 100,000) lb = 454,680 lb

8.1 Quantity released - Columns C and D

These estimates can be based on projected bleached pulp production rates and source

reduction activities.

8.2 Quantity used for energy recovery on-site

0 lb/yr. If the mill uses any of the interpretations in section 7B, the quantities should be reported here.

8.3 Quantity used for energy recovery off-site

0 lb/yr

8.4 Quantity recycled on- si te

0 lb/yr

8.5 Quantity recycled off-site

0 lb/yr

8.6 Quantity treated on-site - Column B

This section requires the quantity of chloroform treated on-site.

Sample Calculation :

For the mill described in section 5.1(b) Case 1, the mill sent 175,200 lb of chloroform to the

w aste treatment system. When the WATER9 (three-basin ASB model) was used for chloroform, it

w as determined that 43.2 percent of chloroform was biodegraded.

(i) Quantity of chloroform treated on-site in the waste treatment system

= 75686 lb

8.6 Quantity treated on-site - Columns C and D

These can be estimated based on projected bleached pulp production rates and source

reduction activities.Issued 2012 Chloroform

(Last Updated March 2012) p. 25



## ncasi
Pulp and Paper Mills 

## 8.7 Quantity treated off-site

This section requires the quantity of chloroform sent off-site for treatment (6.1 + 6.2 (treatment only)), minus the quantity reported as sent for off-site treatment under section 8.8. Thus, if a mill’s effluent were sent to a POTW, the total quantity of chloroform in the effluent sent to the POTW would be reported in this section. Similarly, if a mill sends

its WWTP residuals containing chloroform to be land-applied off-site and all of this chloroform is biodegraded, the amount of chloroform in the residuals should be reported

under this section.

8.8 Quantity released to the environment as a result of remedial actions, catastrophic events, or one-time events not associated with production processes

This would be the amount of chloroform released, prior to any treatment, as a result of catastrophic events, remedial actions, or other one-time events not associated with other normal or routine production processes.

8.9 Production ratio or activity index

This section requires the reporting of a production ratio or activity index in the reportin g year. The ACT requires that this ratio should most closely reflect all activities involving the toxic chemical. Since the major contributor to chloroform release (especially in a

non -hypochlorite bleaching sequence) is the amount of bleached pulp produced, one could possibly report the ratio of bleached pulp production in the reporting year to bleached pulp production in the previous year.

8.10 Source reduction activities (Column 1)

Data Elements 8.10.1, 8.10.2, 8.10.3, 8.10.4

The following is a partial list of activities which would be considered source reduction

activities for chloroform:

(i) Reduction in hypochlorite usage in the bleach plant (Activity W58).

(ii) Reduction in chlorine factor in the bleach plant through increased ClO 2 

## substitution or other changes in the bleach plant (Activity W42).

(iii) Modification of the Cl 2 

## and ClO 2 

## addition sequences so that a higher fraction of

ClO 2 

## is added after Cl 2 

## has been applied (Activity W58).

(iv) Operating the hypochlorite stage at an elevated temperature to reduce the amount of chloroform leaving that stage (Activity W58).

(v) Changing product specifications so that a lower brightness pulp requiring less chlorine is used and the modified bleaching sequence produces less chloroform (Activity W81).Issued 2012 Chloroform

(Last Updated March 2012) p. 26



## ncasi
Pulp and Paper Mills 

## 8.10 Methods to identify activity (Columns 2, 3, and 4)

Data Elements 8.10.1, 8.10.2, 8.10.3, 8.10.4

Enter one or more of the codes from T01 to T11 if they apply.

8.11 Source Reduction, Recycling, or Pollution Control Activities

This is an optional section within EPA’s TRI-ME reporting software. It has a text box feature that allows brief reporting of applicable source reduction, recycling, and other pollution control techniques and activities undertaken for the chemical. Facilities may also submit hard copies of more detailed source reduction information.

REFERENCES

Environmental Protection Agency (U.S.). 1984. Locating and estimating air emissions from sources of chloroform . EPA-450/4-84 -007c. pp. 57-60. Research Triangle Park, NC: U.S. Environmental Protection Agency.

National Council for Air and Stream Improvement, Inc. (NCASI). 1984. The land application and related utilization of pulp and paper mill sludges. Technical Bulletin No. 439. Research Triangle Park, NC: National Council f or Air and Stream Improvement, Inc.

. 1988. Results of field measurements of chloroform formation and release from pulp bleaching . Technical Bulletin No. 558. Research Triangle Park, NC: National Council

for Air and Stream Improvement, Inc.

. 1993. An investigation of factors that influence chloroform generation from recovered paper fiber bleaching with hypochlorite . Technical Bulletin No. 649. Research Triangle Park, NC: National Council for Air and Stream Improvement, Inc.

. 2010. Compilation of ‘air toxic’ and total hydrocarbon emissions data for pulp and paper mill sources –

a second update . Technical Bulletin No. 973. Research Triangle Park, NC: National Council for Air and Stream Improvement, Inc.

Warzyn Engineering, Inc. 1980. Documentation report: lime pits abandonment and mill refuse disposal site preparation . June 1980. Addison, IL:Warzyn Engineering, Inc.