March 28, 2012

MEMORANDUM

SUBJECT: Meeting notes for the March 28, 2012 meeting with AF&PA

FROM: John Bradfield

TO: Docket EPA

- HQ

- OAR

- 2007

- 0544

This memorandum summarizes the meeting between The American Forest and Paper Association (AF&PA) and the EPA on March 28, 2012. This meeting was requested in response to the Risk and Technology Review (RTR) of the National Emission Standards for Hazardous Air Pollutants (NESHAP) for the pulp and paper industry.

Meeting Attendees:

Bill Schrock

- EPA Brit tany Robinson

- URS Ashok Jain

- NCASI Jeff Shumaker

- IP Guy Martin

- Domtar Mark Aguilar

- GP Tim Hunt

- AF&PA Vipin Varma

- NCASI Jim Taylor

- MWV John Pinkerton

- NCASI Rich Garber

- Boise Inc. Nick Swanson

- EPA Kelley Spence

- EPA John Bradfield

- EPA Corey Gooden

- RTI Tom Holloway

- RTI Katie Hanks

- RTI Ann Crapo

- NCASI (via phone) Zach Emerson

- NCASI (via phone) Paul Noe

- AF&PA (via phone) Robin Dunkins

- EPA (via phone)Discussion Points:

• Discussions followed the slides in Attachment 1

.

• P oints made by industry representatives during the meeting that may not be reflected on the slides are as follows:

o The cost to install activated sludge treatment systems is on the order of $30 to 40 million.

o Hard pipes to route condensates to wastewater treatment are mad e of stainless steel and can be over a mile long.

o Mills keep tra ck of time associated with the excess emission s allowances and are not measuring emission. However, emissions are typically estimated applying NCASI emission factors and a variety of site

- spe cific considerations (e.g., location of vents; estimates of apportioned emissions for the various vents in the system). Such emission estimates are often included in annual emissions inventories, and were included in the Part II survey responses.

o Some Sta tes a gencies have time limits after which reporting of venting episodes are required (e.g., events adding up to over 5 minutes of time)

• Three additional presen t ations were provide d by AF&PA prior to the meeting but were not discussed.
T hese include:

o He xachloroethane Emissions from Brownstock Washers and Bleach Plant Scrubbers (Attachment 2)

o Pre

- and Post

- MACT Paper Machine HAP Emission Tests for Residual Risk Assessment Review (Attachment 3)

o Wastewater Treatment System HAP Emissions (Attachment 4)

• Further discussions. If EPA has additional technical clarifications, tentative plans were made for a follow up meeting May 2 nd 2012Attachment 1

AF&PA Meeting Material Discussed on March 28

## Pulp & Paper Residual Risk and Technology Review 

## Proposal

Industry Meeting with OAQPS
Research Triangle Park, NC

March 28, 2012

# Agenda

Cost analyses

Excess Emission Allowances

Start

- up & Shutdown

Other issues

– if time
Next Steps/Wrap

- up

2

## Cost Estimates for Proposed Increased

Treatment Standards

# Cost Considerations

What do facilities need to do to achieve 94% treatment efficiency

Treatment System Upgrades
Assumed all facilities will need to upgrade their wastewater treatment systems to achieve 94% Will CAA Mills be able to utilize this option or will the 

### demonstration fall apart?
For conservatism, cost estimates assumed CCA mills will still be able to demonstrate compliance with 94% (AF&PA Methodology)

4

## Facility Treatment Options & Upgrade Assumptions

5 Treatment Option Number of Units Upgrade Assumptions

Stripper Only 43 • Mills under 96% treatment efficiency will need to upgrade their units.

• All mills will need to increase O&M Cost Biological Treatment Only 39 • All mills will need to increase surface or diffused aeration and have nutrient addition [26 ASBs, 12 other (UNOX, AST), 1 Anaerobic] Biological Treatment & Stripping 9 • 1/2 the mills that have treatment efficiency under 96% will need to upgrade their units (assume upgrade is to the stripper). All strippers will need to increase O&M costs. Recycle 5 • Assume no upgrades required

Thermal Oxidizer 1 • Assume no upgrades required

TOTAL 97 • Assume that 91 mills are affected (less recycle & thermal oxidizer)

NOTE: Assumed that mills can still utilize the CCA option, but will need to upgrade their control systems and redemonstrate compliance with CCA via an IPT. This is a conservative assumption as it is expected that several CCA Mills will not be able to utilize this option under this methodology

## Cost Estimate to treat to 94% : Assumptions (AF&PA Methodology: 10.4/6.8 lb/ODTP)

Stripper Assumptions
More energy , trays, and steam contact area
N eed compliance margin

– units with < 96% 20% are integrated with evaporators
Assume 10% downtime remains

- no backup 

### Wastewater Treatment System Assumptions

I ncrease in aeration and nutrient addition would be sufficient Added nutrients may impact water quality standards All systems impacted

6

## Cost Estimate to treat to 94% : Strippers (AF&PA Methodology: 10.4/6.8 lb/ODTP)



## EPA Estimate
8 stripper upgrades

$2.7 M/each 

## AF&PA Estimate
27 strippers (96% and below)
23 Strippers (only treatment device)

4 Strippers for facilities with dual treatment (1/2 of these units)



### $2.9 M/each for non

integrated units $5.8 M/each for integrated units

7

## Cost Estimate to treat to 94% : Biological Treatment (AF&PA Methodology: 10.4/6.8 lb/ODTP)

EPA Estimate

7 systems (at or below 94%)

Capital costs range from $1

– 4 M/each 

## AF&PA Estimate

39 systems (all with biological treatment)

26 ASBs 12 UNOX, AST, etc. will also need increased aeration 1 Anaerobic System

– Will need an upgrade

– Assumed similar cost to other systems



### Capital cost of $6M/each

8

## Cost Estimate to treat to 94% : O&M Costs (AF&PA Methodology: 10.4/6.8 lb/ODTP)

Strippers Increased energy : 12 MMBtu/hr x 8390 hr/yr x $3/MMBtu

I ncreased maintenance to maintain efficiency: one additional outage per year at $100K 

## Biological Treatment Systems

– all affected
Increased energy: $2.3 M/year/facility Maintenance costs for aerators: $220K/year/facility


### C ost for chemicals only (nutrient): $60K/year/facility

9

## Cost Estimate to treat to 94% : Biological Treatment (AF&PA Methodology: 10.4/6.8 lb/ODTP)

10 

### Cost Range ($M) Average Cost

($M) Aeration Installation Costs (Capital) $1.5

– $12.5 $6

Annual Power Cost Increase $0.6

– $5 $2.3

Annual Maintenance Cost Increase $0.06

- $0.5 $0.22

## Cost Estimate to treat to 94% (AF&PA Methodology: 10.4/6.8 lb/ODTP)

11



### Number of Units Affected Capital

Costs ($M) Annual

Energy Costs ($M) Annual

O&M Costs ($M) Stripper Upgrade 27 $94 $8 $3

Current Strippers 25

-- $8 $3

Aeration 39 $230 $90 $9
Nutrient Addition 39

-- -- $2

TOTAL

-- $324 $106 $17

## Cost Estimate to treat to 94% : Comparison (AF&PA Methodology: 10.4/6.8 lb/ODTP)

12 

## EPA Estimate 

## AF&PA

Estimate Number of Facilities Affected 15 91
Capital Cost ($M) $36 $324 Annualized Capital Cost ($M) $4.1 $30.4
Annual O&M Costs ($M) $0.15 $123

Annualized Cost ($M) $4.25 154
Cost /Ton (Using 4092 tons/yr) $1,000 $38,000

## Excess Emission Allowances

# Excess Emission Allowances

Necessary due to Inherent Process Variability, Design, and Technology Reasons

– Not SSM
Generally not due to equipment breakdown/repair

P rocess variability and safety interlocks cause release 

## Part of the “MACT Floor”

- best performing units could not meet the standards at all times Technology and operations have not changed to allow for safe operations without these provisions

14

## Excess Emission Allowances: LVHC & HVLC Systems

Gases are potentially explosive and cannot be burned safely without supplemental fuel

Flame safety system will not permit the gases to be admitted until the burner is operating on supplemental fuel and ignition is proven (criteria for safe operation, known as “permissives,” must be met) Generally 9

– 15 interlocks Safety interlocks are required by both Factory Mutual Insurance and the National Fire Protection Association for burning of these non

- condensable gases. When these gases are burned in a recovery furnace, there are safety guidelines issued by the Black Liquor Recovery Advisory Committee.

15

## Excess Emission Provisions: LVHC & HVLC Systems

Example Events

Loss of Flame or Burner Permissive Typically short in duration and quickly resolved
Example: Temporarily loss of permissive due to cleaning oil gun(s)
Process Variation
Variation causes a “domino effect” in the mill
Example: Paper Machine Trip causes a swing in steam header pressure and vent at digester system
Loss of Permissive and Back

- up Control Device Not Readily Available (LVHC systems)

Backup control device undergoing maintenance or not a “hot” backup 

### Note: Emergency Shutdowns can actually result in increased emissions rather than allowing the permissive to resolve

16

## Excess Emission Allowance: Emission Estimates LVHC & HVLC Systems
Not possible to quantify emissions on a site

- or event

- specific basis Not aware of any successful measurements of releases from vents during these circumstances
Limited data available from collection systems prior to control devices during normal operations 

### Emissions will vary based on the cause, location, and source
Vary between facilities and within facility at similar source Vary based on the circumstances of the release 

### Sampling these events is not feasible

Events cannot be anticipated Generally short duration so difficult to respond to sample Generally unsafe to sample these events

Some vents are not accessible

17

## Excess Emission Allowances: Vent

- less Transfer LVHC & HVLC Systems


## Some units cannot be designed for vent

- less transfer Systems with recovery furnaces Systems that have different types of boilers as the Primary and Back

- up Control Devices (i.e., one boiler is under positive pressure and the other boiler is under negative pressure) Systems such as oxidizers that were installed as Back

- up Control Only ( these units are typically not 

## maintained in a “hot” state)

18

## Excess Emission Allowances: Steam Strippers
Almost all facilities do not have backup strippers Downtime needed for Stripper tray damage or plugging Efficiency losses in the stripper due to contamination of condensate with fiber or black liquor Steam supply downtime Combustion control device downtime Stripper maintenance

19

## Excess Emission Allowances: HVLC/LVHC Cost Estimate Assumptions

HVLC Control Devices
Assume all facilities have one control device and elimination of excess emission allowance will require routing gases to a back

up control device. Assumes that the facility has an available back

- up option This is not the cost in previous estimates for CCA mills to install the piping for collection and treatment of HVLC gases to a single control device. 

## LVHC Control Devices All systems have a primary and backup control device

– no routing to an additional control device necessary 

## LVHC/HVLC Collection Systems Systems collect gases from equipment in the pulping process areas. Assume a backup collection system (piping) will be necessary to collect any “vents” from equipment

20

## Excess Emission Allowances: Stripper Cost Estimate Assumptions

Back

- up Stripper will be required to accommodate stripper downtime due to maintenance
Without back

- up systems, mills will need to shutdown the pulping process equipment during stripper downtime Based on the proposed regulations, EPA wants to require higher treatment standards which will require additional maintenance on control systems and increased downtime 

### Installation of a Collection Tank for Long

- Term Storage is Not a Solution
Tanks are suitable for short

- term downtime periods (trips, etc.)

– not maintenance outages Volume generated by strippers is such that long

- term storage is not realistic Systems are maxed out on volume (flow) Storage of condensates during long

- term downtime events would require an increase in flow (throughput) to compensate for the condensates being generated and treatment of stored condensates

21

## Excess Emission Allowances: Capital Cost Estimates

• Assumes all 97 Mills subject to the collection requirements will need to install ductwork to route HVLC to a backup control device (and a backup control device is available) and ductwork for redundant LVHC/HVLC collection systems.

• Assumes all 52 mills with strippers will need to install a backup stripper.

NOTE: Even with these systems, facilities cannot guarantee 100% compliance due to process variability and safety considerations.

22 

### AF&PA Estimate ($M)
HVLC Redundant Control Costs $500 Redundant LVHC/HVLC Collection Systems $700 Backup Strippers $400
TOTAL $1,600

# Targeted Excess Emissions and SSM Survey is being Planned

Survey will attempt to provide more details on the following

Circumstances for excess emissions

Whether they qualify as SSM events AND if not, why not

General categorization of excess emissions events (and causes)
Differentiating between excess emissions events and SSM events
Frequency and duration of occurrences to reflect an overall industry snapshot (would be difficult to estimate or quantify emissions, given the challenges described earlier)
Compilation of prevalent monitoring procedures and work practices 

### Lastly, why excess emission periods are needed for technology or operational reasons AND how all events cannot be avoided (e.g., permissive and interlock events)

23

## Startup & Shutdown

# Startup & Shutdown

EPA assumed operations (and emissions) are not different during startup & shutdown vs. normal operation
Nothing in the record to support No known data available for emissions during SS events Regulations prohibit using data for compliance purposes collected during SS events

25

# Startup & Shutdown

Examples where emissions could be different:

Control device may be less efficient:
Until it reaches operating temperature

W hen the pollutant concentrations are lower than during steady

- state operation Until a process reaches steady

- state operation, that process may generate substantially higher emissions, either on a total mass 

### basis or on a mass per unit of production basis Venting of LVHC/HVLC systems due to system “permissives” not being met 

## Legal issues covered in comments

26

## Other Topics of Concern

# Other Topics of Concern

Concentration limit for Bleached Mills should be 258 ppmv
Proposed rule states 210 ppmv which is inconsistent with the docket 

### Electronic Reporting is unreasonable
Subpart S Performance Tests are unlike Stack Tests 

### Compliance Deadline should be 3 years for all changes to the rules
Including electronic reporting and affirmative defense 

### EPA’s proposed requirement that the Administrator specify test conditions is unreasonable

Test under normal conditions

28

## Cost Estimates IF Over

- collection with

Pound per Ton Option

## Cost Estimate to treat to 94%: Assumptions ( EPA Methodology : 12.8/8.3 lb/ODTP)



## Assumptions The lb/ODTP treatment option not viable
The Clean Condensate Alternative not viable
Need to treat additional condensates will negate current compliance demonstrations Install collection system at $15M/facility
Assumes that 4% HVLC allowance remains in place

30

## Cost Estimate to treat to 94% ( EPA Methodology : 12.8/8.3 lb/ODTP)

31



### Number of Units Affected 

### Capital

Costs ($M) 

### Annual

Energy Costs ($M) 

### Annual

O&M Costs ($M) Stripper Upgrade 27 $94 $8 $3
Current Strippers 25

-- $8 $3

Aeration 39 $230 $90 $9

Nutrient Addition 39

-- -- $2

HVLC to Single Treatment 

### Device 34 $510

-- --

TOTAL

-- $834 $106 $17

## Cost Estimate to treat to 94% : Comparison (AF&PA vs. EPA Methodology)

32 

## EPA Estimate 

## AF&PA

Estimate

Number of Facilities 

## Affected 15 91

Capital Cost ($M) $36 $834

Annualized Capital Cost ($M) $4.1 $48 + 30 = 78

Annual O&M Costs ($M) $0.15 $123

Annualized Cost ($M) $4.25 $202

## Clean Condensate Alternative

## Compliance Approaches used by CCA Mills

Facilities with cleaner condensates on Brownstock Washer showers either

Over

- collect condensates for treatment in Steam Strippers OR

Route additional condensates to the ASB for treatment


### Emission reductions are

Incremental reductions achieved from a “baseline” that reflects MACT I Phase 1 compliance

From the use of cleaner condensates on HVLC sources
Due to improved treatment in wastewater treatment systems realized through voluntary upgrades 

### For CCA mills, collection and treatment levels reported in the 2011 ICR reflect ongoing compliance with MACT I Phase 1 and CCA

34

## CCA strategies as grouped by EPA in their October 21, 2011 memo

35 CCA Technology Number of Units Affected Upgrade Assumptions

Steam Stripper, Biological Treatment, & Collect Additional Condensates 21 • These mills collect additional condensates and send to the steam stripper or biological treatment systems for treatment Clean Shower Water, Clean Condensates, & Substitution 7 • These mills collect additional condensates and send to the steam stripper or biological treatment systems for treatment Wastewater Treatment System Upgrades Only 6 • Assumed these facilities would need the upgrades to achieve the 94% treatment efficiency and could not use credits for CCA.
Other Alternatives 4 • Assumed these facilities could still utilize the CCA option as we do not have information for these sites.

## Compliance Approaches used by CCA Mills using over

collection and additional treatment

Over

- collect and over

- treat condensates in Steam Strippers to clean up HVLC source condensates for emission reductions
Eight unbleached mills

Three bleached mills


### WWTP area emission reductions

Eleven mills

– over
- collection and additional treatment in ASB through voluntary upgrades | sewer diversion credits

Three mills

- no over
- collection but voluntary upgrades that result in additional treatment | sewer diversion credits

Three mills

– additional treatment not significant


### Six mills confirmed as adopting other “equivalency” projects

Four mills

– more detailed info being sought (non

- member companies)

3637 HVLC Sources Contaminated Condensate

Clean Condensate HVLC CCA

HVLC B ase


## F bio MACT 1 Phase 1 Wastewater (WW1) Baseline Emissions = (WW1 + P1) x (1

– F bio )

Phase 1 Condensates (P1)

Phase 1 Compliance: P1 ≥ 11.1 and (P1 x F bio ) ≥ 10.2

Additional Condensates in Hard Pipe (P2) Additional Treatment Higher F bio Wastewater (WW CCA )
Phase 1 Condensates (P1) CCA Emissions = (WW CCA + P1 + P2) x (1

– F bio, CCA )

= baseline = CCA

Facility hardpiping additional condensates and operating biotreatment system at Higher F bio in order to use the CCA option
Higher Fbio achieved through voluntary treatment system upgrades 

## Example Bleached Mill with CCA

– Compliance ApproachHVLC Source emissions = 1.4 lb/ODTP
Wastewater Treatment system loadings

Baseline: WW 1 = 10 lb/ODTP; P1 = 12.2 lb/ODTP

CCA: WW CCA = 7 lb/ODTP; P1 = 12.2 lb/ODTP; P2 = 3 lb/ODTP

MACT I Phase 1 Fbio = 92 % (baseline)

Fbio , CCA = 95%

38 Baseline HAP, lb/ton CCA Emissions, lb/ton

HVLC Sources 1.40 0.50

Wastewater Treatment System (10 + 12.2) x 0.08 =

1.78 (7 + 12.2 + 3) x 0.05 =

1.11

Total 3.18 1.66

Required Control from HVLC Sources = 0.98 x 1.4 = 1.37

Emission Reductions from CCA = 3.18

– 1.66 = 1.52 || 1.52 > 1.37 

## Example Bleached Mill with CCA

– Compliance CalculationsHVLC Source emissions = 1.4 lb/ODTP
Wastewater Treatment system loadings

Baseline: WW 1 = 10 lb/ODTP; P1 = 12.2 lb/ODTP

CCA: WW CCA = 7 lb/ODTP; P1 = 12.2 lb/ODTP; P2 = 3 lb/ODTP

MACT I Phase 1 Fbio = 94% (baseline)

Fbio , CCA = 95%

39 Baseline HAP, lb/ton CCA Emissions, lb/ton

HVLC Sources 1.40 0.50

Wastewater Treatment System (10 + 12.2) x 0.06 =

1.33 (7 + 12.2 + 3) x 0.05 =

1.11

Total 2.73 1.66

Required Control from HVLC Sources = 0.98 x 1.4 = 1.37

Emission Reductions from CCA = 2.73

– 1.66 = 1.07 || 1.07 < 1.37

CCA BREAKS DOWN 

### Example Bleached Mill with CCA

– Compliance Calculations with Proposed 94% StandardPHASE 1

Demonstrate that P1 is ≥ 11.1 lb/ODTP

Over

- collection is sometimes built into the permit language as a requirement for Phase 1
Demonstrate that P1 x MACT I Phase 1 Fbio (baseline) ≥ 10.2 lb/ODTP PHASE 2 through CCA

Demonstrate that (P1+P2) is ≥ (11.1+3) = 14.1 lb/ODTP

O ver
- collection and averaging times also needed here to increase compliance probability
Measure Fbio, CCA

Demonstrate that Emission Reductions at Fbio, CCA ≥ (0.98 x 1.4) lb/ODTP

40 

## Example Bleached Mill with CCA

– Compliance Elements

## Example Bleached Mill with CCA

– Biotreatment Performance is a Requirement under CCA



## Takeaways

Higher F bio 

### under CCA required for Phase 2 compliance
For CCA mills, the ICR data on biotreatment performance reflects the Higher F bio 

### The calculated lb/ODTP treated also cannot be compared against Phase 1 requirements



### Performance data from CCA mills therefore cannot be compared against Phase 1 requirements

41

## Proposed Increase in Treatment Efficiency

from 92% to 94%

1. 

### Historical compliance data does not support sustained over

- performance

2. 

### The proposed increase is more than a marginal improvement and presents achievability and compliance issues

## Historical Compliance Data does not reflect sustained over

- performance

Only a limited number of mills with performance data reflective of MACT I Phase 1 compliance
Cannot be the basis for concluding over

- performance and revising standards Higher levels of collection and treatment are for compliance margins and driven by the need to maximize compliance probability

Not indicative of over

- performance Increasing the treatment requirement would dramatically reduce this compliance probability Current treatment device performance needed to ensure compliance at the current 92% standard
Design factors are integral in Steam strippers Actual Fbio, methanol in ASBs already at 94%

- when considering operational variability, current data is not indicative of over

- performance

43

## Biotreatment Systems

– 92% to 94% is more than a marginal improvement

Proposed increase in biotreatment efficiency (F bio,adj 

## ) from 92% to 94% would mean

An increase in actual F bio, methanol 

### to 96%
Facilities would need major treatment system upgrades to achieve sustainable and ongoing treatment of 96% Upgrades would be prohibitively expensive in many cases


### Given 

## F bio 

## variability, sustained operation at 96% 

## would be infeasible Would result in additional compliance demonstration issues

44

## Steam Strippers

– 92% to 94% is more than a marginal improvement

The need to preserve compliance margins and compensate for fouling etc. would mean upgrades and (in some cases) rebuilds

M ore energy, trays, and steam contact area
All units operating @ < 96 % expected to need upgrades

45Attachment 2

Hexachloroethane Emissions from Brownstock Was hers and Bleach Plant Scrubbers

# Hexachloroethane Emissions from Brownstock Washers and Bleach Plant Scrubbers

Ashok Jain and Dr. Zach Emerson NCASI March 28, 2012

# Hexachloroethane Emissions

• Hexachloroethane (HCE) emissions were a significant contributor to Subpart S risk for a few facilities

– Brownstock Washers

– Bleach Plant Scrubbers



# • Most of these facilities appear to have used emissions data in the NCASI Air Toxics Database to estimate their emissions

# HCE Emission Factors BSW

– Vacuum Drum

Source Code Year Notes Emissions (lb/ADTUBP)

BSWIF 1993 Softwood 5 Hood Vents < 4.3 E

- 02

BSWIG1 1993 Softwood 3 Hood Vents < 8.4 E

- 02

BSWIG2 1993 Hardwood 3 Hood Vents < 1.0 E

- 01

Data taken from NCASI Air Toxics Database, 2011 Revision

# HCE Emission Factors BSW

– “Other”

Source Code Year Notes Emissions (lb/ADTUBP)

BSWIC1 1993 Hardwood 1 Diffusion Washer Vent 1.3 E

- 01

BSWIG1 1993 Softwood 1 Diffusion Foam Tank Vent 3.2 E

- 02

Mean = 8.0 E

- 02 lb/ADTUBP

Data taken from NCASI Air Toxics Database, 2011 Revision

# HCE Emission Factors Bleach Plant Scrubber

Source Code Year Notes Emissions (lb/ADTBP) BPIC1a 1993 Non

- ECF < 2.2 E

- 02 BPIC3 1 

### 1993 ECF 2.5 E

- 02

BPIF2 1993 Non

- ECF < 4.1 E

- 02 BPIG 1993 Non

- ECF < 1.5 E

- 02
BPIJ1 1993 Non

- ECF < 1.9 E

- 02
BPIJ2 1993 Non

- ECF <3.8 E

- 02
BPIF1 1993 Non

- ECF <6.8 E

- 02 Non

- ECF

< 1.5 E

- 02 to <6.8 E

- 02 ECF 2.5 E

- 02 Data taken from NCASI Air Toxics Database, 2011 Revision

# HCE Emission Factors

• BSW

– Vacuum Drum (all non

- detect, 11 total vents)

– “Other” (2 detects at 2 diffusion washer vents at the same facility)



# • Bleach Plant Scrubber

– Non

- ECF (6 non

- detects)

# HCE Emission Factors

• Available data are pre

- MACT (1993)

• Testing Issues

– Method 18 (GC

- FID in the field)

– Short column times, co

- elution of other compounds, results not confirmed on MS



# • BSW

– “Other” and Bleach Plant Scrubber

– ECF Emission factors labeled “suspect” in database and in TB 973 (2010)

# HCE Emissions Studies

• Modified BHA Method

– Added hexane to impinger solution prior to sampling



## • Lab Trials of Method Performance

– Demonstrated ~100% HCE
recovery

– Achieved 10 ppbvd detection levels **“Low” Spike Recovery**  **(%) “High” Spike**  **Recovery (%)**  Spiked Concentration 0.95 ppm 5.2 ppm

Run 1 106 90

Run 2 97 100

Run 3 115 106

Run 4 104 107

Run 5 98 107

Average Recovery 104 102

# HCE Emissions Studies Mill D

• Field Testing at Mill D

– Bleached Mill

– 2 Pulp Lines



# • No. 1 Pulp Line

– Bleach Plant Scrubber



# • No. 2 Pulp Line

– Vacuum Drum Brownstock Washer

– Pressure Diffusion Washer

# Mill D Results No. 2 Line Vacuum Drum Washer

Run No. Production Rate (ADTUBP/day) Vent Flow Rate (DSCFM) Vent Concentration (ppbvd) Emission Factor (lb/ADTUBP)

1 1035.6 1166 15.1 1.47 E

- 05

2 1043.5 1178 12.1 1.19 E

- 05

3

- A 1
1035.6 1166 16.0 1.56 E

- 05

3

- B 1 10.9 1.06 E

- 05

1 Runs 3

- A and 3

- B were collected simultaneously in dual sample trains

# Mill D Results No. 2 Line Diffusion Washer

Run No. Production Rate (ADTUBP/day) Vent Flow Rate (DSCFM) Vent Concentration (ppbvd) Emission Factor (lb/ADTUBP)

1 1035.6 380 <10.3 <3.26 E

- 06

2 1043.5 363 <12.4 <3.71 E

- 06

3

- A 1

1035.6 415 <9.7 <3.36 E

- 06

3

- B 1 <10.2 <3.55 E

- 06

1 Runs 3

- A and 3

- B were collected simultaneously in dual sample trains

# Mill D Results No. 1 Bleach Plant Scrubber

Run No. Production Rate (ADTBP/day) Vent Flow Rate (DSCFM) Vent Concentration (ppbvd) Emission Factor (lb/ADTBP)

1 658.9 8584 < 9.6 < 1.09 E

- 4

2 657.1 8584 < 11.3 < 1.28 E

- 4

3

- A 1

655.2 8617 < 9.8 < 1.11 E

- 4

3

- B 1 < 9.7 < 1.11 E

- 4

1 Runs 3

- A and 3

- B were collected simultaneously in dual sample trains

# HCE Emissions Studies Mill D

• HCE not detected at the Diffusion Washer or at the Bleach Plant Scrubber

• HCE detected at very low level at the Vacuum Washer

Mill D Source Source Category Mill D Result NCASI Database
Emission Factor # of Sources Emission Factor No. 2 Line Vacuum Washer BSW

– Vacuum Drum Type 1.32 E

- 05 3 <4.3 E

- 01

No. 2 Line Diffusion Washer BSW

– Other <3.48 E

- 06 2 8.1 E

- 02

No. 1. Line Bleach Plant Scrubber Bleach Plant

- ECF <1.16 E

- 04 1 2.5 E

- 02

# HCE Emissions

• Hexachloroethane emissions from 1 facility are much lower than pre

- MACT testing

• Where detected, HCE levels are extremely low

– Unlikely to be present due to pulping

– HCE source may be process water chlorination, in the process of examining process water practices at Mill D



# • If warranted, can pursue further testing at other facilities to develop post

- MACT emission factorsAttachment 3

Pre

- and Post

- MACT Paper Machine HAP Emission Tests for Residual Risk Assessment Review

# Pre

- and Post

- MACT Paper Machine HAP Emission Tests for Residual Risk Assessment Review

Ashok Jain and Rob Crawford, NCASI March 28, 2012

# BHA Method

• Analytes: Acetaldehyde, Acrolein, Formaldehyde, Proprionaldehyde

• NCASI Method ISS/FP

- A105.01 (BHA Method) Previously Developed for Solid Wood Products Manufacturing Sources

• NCASI Methods Manual

23 

# BHA Method (Cont’d)

• Chilled Aqueous Impinger Sampling

• Aqueous Impinger Solution Contains

o

- benzylhydroxylamine (BHA)

• BHA Reacts with Aldehydes to form Aldehyde Oximes

• Aldehyde Oximes are Extracted with Hexane

• Analysis with GC/NPD (Nitrogen

Phosphorous Detector)

# BHA Method for Paper Machine Sources

• Method Modifications

– Increased Sampling Flow Rate from 0.5 L/min to 2 L/min

– Decreased Hexane Extraction Volume from 30 mL to 15 mL

– Source Gas Quantitation Limits: 0.01 to 0.03 ppmv as Compared to ~0.2 ppm

4

# Duplicate, Unspiked Sampling Train Results for Acetaldehyde

5 0.00 0.05 0.10 0.15 0.20 0.25

VSE VPE HBE TWE FC2 DE1 DE3 AS1 FOE WE6 VE2 DV1 DV2 DV3Acetaldehyde Emissions, ppmv



### Paper Machine Emission Source Sample Train 1
Sample Train 2

# Duplicate, Unspiked Sampling Train Results for Formaldehyde

6 0.00 0.02 0.04 0.06 0.08 0.10 0.12

VSE VPE HBE TWE FC2 DE1 DE3 AS1 WE6 VE2 DV1 DV2 DV3Formaldehyde Emissions, ppmv



### Paper Machine Emission Source Sample Train 1
Sample Train 2

# Duplicate, Unspiked Sampling Train Results for Acrolein

7 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10

WE6 VE2Acrolein Emissions, ppmv



### Paper Machine Emission Source Sample Train 1
Sample Train 2

# Run Spike Concentration Ranges

8 

### Compound Concentration Range, ppmv
Low High Acetaldehyde 0.6

– 0.9 7.9

– 9.1
Acrolein 0.02

– 0.05 0.2

– 0.3 Propionaldehyde 0.06

– 0.09 0.4

– 0.5 Formaldehyde 0.09

– 0.13 0.9

– 1.0

# Run Spike Results

Compound Low Spike High Spike

No. of Spiked Source Tests* Avg. Rec., % No. of Spiked Source Tests* Avg. Rec., % Acetaldehyde 15 85 16 93

Acrolein 0 NA 15 95 Propionaldehyde 7 92 16 90 Formaldehyde 14 80 16 88

9

*only includes samples with spike concentrations ≥ the source concentration

# Integrated Kraft Mill Sources Tested

Unbleached Mills B and H

• Linerboard Machines

• Clean Condensate and Fresh Water on Final BSW Stage Showers

• Mill H Tested in Original MACT I Study

Bleached Mills C and D

• Bleached Uncoated Paper Machine Tested at Mill C

• Bleached Pulp Dryer Tested at Mill D

10

# Pre

- and Post

- MACT Paper Machine Acetaldehyde Emissions

11 0.0E+00 2.0E

- 02 4.0E

- 02 6.0E

- 02 8.0E

- 02 1.0E

- 01 1.2E

- 01

TB 858 B H C DEmissions, lb/ADTFP Unbleached

Bleached

Pre

- MACT Averages Post

- MACT Paper Machines

# Pre

- and Post

- MACT Paper Machine Formaldehyde Emissions

12 0.0E+00 5.0E

- 03 1.0E

- 02 1.5E

- 02 2.0E

- 02 2.5E

- 02

TB 858 B H C DEmissions, lb/ADTFP

Unbleached

Bleached

Pre

- MACT Averages Post

- MACT Paper Machines

# Methanol Emissions from all MACT I Study and Post

- MACT Study Machines

13 y = 0.0049x + 0.056 R2 = 0.9689

0 0.2 0.4 0.6 0.8

1 1.2 1.4 1.6 1.8

0 50 100 150 200 250 300 350Emissions, lb/ADTFP

White Water Concentration, mg/L MACT I Study

Post

- MACT, Unbleached

Post

- MACT, Bleached

# Methanol Emissions from all MACT I Study and Post

- MACT Study Machines with White Water Methanol Concentrations <50 mg/L

14 y = 0.0059x + 0.0153 R2 = 0.9475

0 0.05

0.1 0.15

0.2 0.25

0.3 0.35

0 5 10 15 20 25 30 35 40 45 50Emissions, lb/ADTFP

White Water Concentration, mg/L MACT I Study, Unbleached

Post

- MACT Study, Unbleached

Post

- MACT Study, Bleached

MACT I Study, Bleached Mill D Pulp Dryer

Mill C Paper Machine

# Total Machine Acetaldehyde and Formaldehyde Emissions vs White Water Concentrations for the Post

- MACT Study Machines

15 y = 0.0069x + 0.0035 R2 = 0.886

0.0E+00 2.0E

- 03 4.0E

- 03 6.0E

- 03 8.0E

- 03 1.0E

- 02

0 0.5 1 1.5 2Emissions, lb/ADTFP

White Water Concentration, mg/L Acetaldehyde

Formaldehyde

# Summary

• Post

- MACT Tests at Two Unbleached and Two Bleached Machines

• Acetaldehyde Emissions from Post

- MACT Unbleached and Bleached Machines were 7% and 12% of Pre

- MACT Averages, Respectively

• Formaldehyde Emissions from Post

- MACT Unbleached and Bleached Machines were 8% and 36% of Pre

- MACT Averages, Respectively

• Acrolein Emissions were Essentially Unchanged for Both the Unbleached and Bleached Machines

16Attachment 4

Wastewater Treatment System HAP Emissions

# Wastewater Treatment System HAP Emissions

Dr. Zach Emerson, Ashok Jain NCASI

March 28, 2012

# Refining Wastewater Treatment Plant Emission Estimates

• Develop/modify methods for measuring acetaldehyde, formaldehyde, acrolein and naphthalene content of effluents

• Conduct site

- specific modeling of selected treatment systems with new effluent concentration data

2

# Emissions Estimates from WWTP

• Often estimated using procedures used in NCASI SARA Handbook

• Calculations for emissions from a WWT unit take the form: E = Load · F air



## Load Emissions Emissions

Load

# Emissions Estimates from WWTP

HAP Loads from SARA Handbook (2010 Revision)

Acetaldehyde Pulp Mill Sewer *Based upon Condensate Handling Practices Bleach Plant (n=10) 0.5

– 12.3 Mean = 1.86 mg/L

Formaldehyde HW Bleach Plant (n=1) 0.21

– 0.32 Mean = 0.25 mg/L

SW Bleach Plant (n=1) 1.5

– 1.8 Mean = 1.65 mg/L

Naphthalene Bleached Pulp Mill (n=3) ND (5)

– 67.3 Mean = 24.3 μ g/L

Unbleached Pulp Mill (n=3) ND (5 μ g/L )

Acrolein Pulp Mill Sewer ND (1 mg/L)

# Emissions Estimates from WWTP

• Emissions estimates are model

- based

– Presented as fraction of inlet load that is volatilized

SARA Handbook: WATER9 3

- Basin ASB f

Air AST f

Air
Methanol 5.0 %* < 0.1 % Acetaldehyde 23.9 % 8.6 % Formaldehyde 0.3 % < 0.1 % Naphthalene 17.8 % 7.4 %

# Analytical Method Development Studies

• Developed procedures for acetaldehyde, formaldehyde, acrolein and naphthalene appropriate for wastewater

• Achieved lower aqueous detection levels

• Demonstrated analyte recovery and stability

6

# Method Development

• Sample Collection:

– Based upon NCASI Method DI/MEOH

- 94.03

• “Methanol in Process Liquids and Wastewaters by GC/FID”



# • Sample Analysis:

– Acetaldehyde, Formaldehyde & Acrolein: NCASI Method ISS

- FP

- A105.1

• “Derivatization method for Aldehydes, Ketones and Select Polar Compounds”



## – Naphthalene: MS

7

# Method Development

• Aqueous Detection Levels

– * Current detection levels are sample

- specific

• Spike Recovery and Precision Trials

8 Previous Work Current* Acetaldehyde 1 ppm 0.02

– 0.1 ppm Formaldehyde 1 ppm 0.03

– 0.1 ppm

Acrolein 0.1 ppm 0.1

– 0.2 ppm Naphthalene 5 ppb 0.3

– 1.8 ppb

Spike Recovery in Wastewater Precision

Acetaldehyde 80

- 103% 5.4

– 8.7% Formaldehyde 97

– 136 % 7.6

– 9.8%

Acrolein 79

– 97 % N/A Naphthalene 108 % N/A

# NCASI Wastewater Study Focus

• Assist Facilities with Inventory Update

– Correct emissions locations, conditions and parameters

– Update WWTS emissions calculations

• Where appropriate, update loads to WWT

• Create site

- specific multi

- zone emissions models

9

# NCASI Wastewater Study Features

• Multi

- facility Study

– 24 US kraft mills, 9 bleached and 15 unbleached (1 combined)

– Sample collection by mill staff, analysis by SRC



# • Multi

- scale

– 13 Mills

- Samples collected from throughout treatment system

– 11 Mills

- Inlets to primary and/or secondary
treatment

10

# NCASI Wastewater Study Results

• Effluent Concentrations

– Updated Post

- MACT HAP concentrations

– Primary effluent, bleach plant sewer



# • Site

- Specific Emissions Modeling

– Appendix C

– Profile based model

– WATER9

– Influent based model

11

# Effluent Concentrations

Acetaldehyde SARA 313 Winter 2010 Study Pulp Mill Effluent

- Bleached N/A < 0.03

– 6.45 Mean = 0.19 mg/L Pulp Mill Effluent

- Unbleached N/A < 0.03

– 0.44 Mean = 0.19 mg/L

Bleach Plant Sewer 0.5

– 12.3 Mean = 1.86 mg/L 0.01

– 0.38 Mean = 0.15 mg/L

Formaldehyde SARA 313 Winter 2010 Study Pulp Mill Effluent

- Bleached N/A < 0.03

– 0.44 Mean = 0.15 mg/L Pulp Mill Effluent

- Unbleached N/A < 0.03

– 0.32 Mean = 0.14 mg/L

Bleach Plant Sewer 0.21

– 0.32 Mean = 0.25 mg/L 0.03

– 0.42 Mean = 0.19 mg/L Bleach Plant Sewer 1.5

– 1.8 Mean = 1.65 mg/L

# Effluent Concentrations

Naphthalene SARA 313 Winter 2010 Study Pulp Mill Effluent

– Bleached ND (5)

– 67.10 Mean = 24.3 μ g/L 0.38

– 3.91 Mean = 0.683 μ g/L Pulp Mill Effluent

– Unbleached ND (5) μ g/L

Acrolein * SARA 313 Winter 2010 Study Pulp Mill Effluent N/A ND [0.09 mg/L]

Bleach Plant Sewer N/A ND [0.05 mg/L]

* Acrolein was not detected in any wastewater sample

# Site

- Specific Emissions Modeling

• Appendix C: Form XIII Approach

– Based upon in

- pond HAP concentrations

– Site specific system specs

– Similar to hard

- pipe compliance calculations



# • WATER9

– Site specific or industry typical inlet HAP concentrations

– Site specific system specs

– Similar to hard

- pipe compliance calculations



# • Examples

14

# Emissions Estimates from WWTP

• HAP Loading

– May be based upon facility

- generated data

– Some effluent concentrations presented in NCASI SARA Handbook



## • F air



### – Estimated using emissions models (i.e. Water9) or pond

- profile data

– Factors presented in SARA Handbook for a “typical” mill



## Load Emissions Emissions

Load

# Appendix C: Form XIII Approach Zone Emissions Model

( C HAP 

### ) Measured 

## K GL 

## Emissions from Zone 1

Appendix C approach uses in

- pond measurements to calculate flux at the surface. (C HAP 

## ) Measured 

## K GL 

## Emissions from Zone 2

# WATER9 Approach

• Model tool that simulates emissions and biological destruction of HAPs for given load and system specs

17 

## HAP Load HAP Emissions

# Appendix C Example: Mill A

18 Clarifier Emissions
Acet = 0.17 TPY Form = 0.0 TPY Naph = 0.0 TPY ASB Emissions
Acet = 3.84 TPY Form = 0.01 TPY Naph = 0.0 TPY



## Effluent Load Concentration Acet = 0.33 ppm Form = 0.03 ppm Naph = < 2.0 ppb

Pond Concentration Acet = 0.06 ppm Form = 0.04 ppm Naph = < 2.0 ppb

##  

# Appendix C Model built from site

- specific dimensions, aeration, etc.

 

# HAP concentrations from 3

- days of sampling (8 sample locations)

 

# Naphthalene not detected in any sample 

# Appendix C Example: Mill A Comparison

Site

– Specific Emission Rate 2010 RTR Database Value Acetaldehyde 3.84 TPY 5.97 TPY Formaldehyde 0.01 TPY 0.042 TPY Naphthalene 0.0 TPY N/A

19

# WATER9 Example: Mill D

20 Primary Clarifier Emissions
Acet = 0.01 TPY Form = 0.0 TPY UNOX Emissions
Acet = 0.1 TPY Form = 0.01 TPY



## Effluent Measured Load Concentration

Acet = < 0.024 ppm Form = < 0.024 ppm Secondary Clarifier Emissions
Acet = 0.0 TPY Form = 0.0 TPY

##  

# WATER9 Model built from site

- specific dimensions, aeration, etc.

 

# Inlet HAP concentrations from 3

- days of sampling 

# Appendix C Example: Mill D Comparison

Site

– Specific Emission Rate 2010 RTR Database Value Acetaldehyde 0.11 TPY 3.03 TPY Formaldehyde 0.003 TPY N/A

21

# Revised Modeling Example Results

Estimation Approach Concentration Data Estimated Emission Rates (TPY) 2010 RTR Database Values

(TPY)

Mill A App C Full Profile Acet = 3.84 Form = 0.01 Naph =0.0 Acet = 5.97 Form = 0.042 Naph = N/A

Mill B App C Full Profile Acet = 1.45 Form = 0.02 Naph = 0.0 Acet = 5.74 Form = 0.054 Naph = N/A

Mill C App C Full Profile Acet = 2.64 Form = 0.11 Naph = 0.0 Acet = 0.91 Form = 0.24 Naph = 0.732

22

# Revised Modeling Example Results

Estimation Approach Concentration Data Estimated Emission Rates (TPY) 2010 RTR Database Values

(TPY)

Mill D WATER9 Inlet Data Acet = 0.11 Form = 0.003 Naph = N/A Acet = 3.03 Form = N/A Naph = N/A

Mill E WATER9 Inlet Data Acet = 7.7 Form = 0.007 Naph = 0.009 Acet = 15.2 Form = N/A Naph = 0.225

Mill F WATER9 “Industry Typical” Acet = 1.8 Form = 0.01 Naph = 0.006 Acet = 11.0 Form = 0.09 Naph = 0.25

23

# Site

- Specific Emissions Modeling

• Site

- Specific Emissions Models for 32 facilities

– 17 Detailed Appendix

- C type models

– 15 WATER9 models

– Updated inlet concentrations (without modeling) for 9 other facilities



# • Emissions Results

– Acetaldehyde generally lower, sometimes higher

– Formaldehyde & Naphthalene always lower

24

# Wastewater HAP Study

• Wastewater treatment system influent concentrations of formaldehyde, acetaldehyde and naphthalene were lower than previous studies

• Acrolein was not detected in any wastewater sample

• Successfully modeled many facilities

– In most cases, new estimated emission rates were lower than those in EPA’s initial risk modeling

25