ROCKDALE OPERATIONS

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# A

National Emission Standards for Hazardous Air Pollutants for Primary Aluminum Reduction Plants

Implementation Plan

Potlines

Alcoa Inc. Rockdale Operations adin Works Rockdale, Texas

Prepared by:

Alcoa Inc.

PO Box 472 Rockdale, TX 76567

Cre ated: April 6, 2001 Updated: June 10 , 2008ROCKDALE OPERATIONS

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TABLE OF CONTENTS

TABLE OF CONTENTS

................................ ................................ ................................ .............. 2

1.0 INTRODUCTION

................................ ................................ ................................ .................... 4

2.0 EMISSION SOURCE IDENTIFICATION

................................ ................................ ........... 5

2.1 A

- 398s

2.2 Wet Scrubbers

2.3 ESPs 2.4 Baghouses

3.0 EMISSI ON LIMIT

................................ ................................ ................................ .................. 6

4.0 APPLICABILITY AN D CONTROL DEVICES

................................ ................................ .. 8

5.0 SITE

- SPECIFIC TEST PLAN

................................ ................................ ............................... 8

5.1 Test Program Summary

5.2 Test Schedule 5.3 Sample Location 5.4 Sampling/Analytical Procedures 5.5 Data Quality Objectives 5.6 Internal Quality Assurance Program

5.7 External Quality Assurance Program 5.8 Exceptions to EPA Methodology

6.0 CONTROL DEVICE M ONITORING PLAN

................................ ................................ .... 1 6

6.1 Criteria For Parameter Selection

6.2 Alumina Flow

6.3 Air Flow Limit

6.4 Water Flow 6.5 Voltage 6.6 Secondary Current

7.0 COMPLIANCE DEMO NSTRATION

................................ ................................ ................. 19ROCKDALE OPERATIONS

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Table 1

– Summary of Abatement Devices By Potline

Table 2

– Summary of Sampling and Laboratory Methods

Table 3

– Summary of Estimated Accuracy and Precision Objectives

Table 4

– Summary of Internal Quality Control Checks, Frequenci es, Acceptance Criteria

and Corrective Action for Total Fluoride Analysis

Table 5

– Potroom Parametric Monitoring

FIGURES Figure No. 1

– Potline 3 Primary and Secondary Emission Control Systems Figure No. 3

– Potline 4 Primary and Secondary Emission C ontrol Systems Figure No. 4

– Potline 5 Primary and Secondary Emission Control Systems Figure No. 5

– Potline 6 Primary and Secondary Emission Control Systems Figure No. 6

– Potline 7 Primary and Secondary Emission Control Systems Figure No. 7

– Potline 8 Primary and Secondary Emission Control Systems

APPENDICES Appendix A

– EPA Test Methods Appendix B

– EPA

- Approved Alternate Air Flow Methodology Appendix C

– Alternate Measurement Site StudyROCKDALE OPERATIONS

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On October 7, 1997, the United States Enviro nmental Protection Agency promulgated National Emissions Standards For Hazardous Air Pollutants (NESHAP) for Primary Aluminum Reductions Plants under 40 CFR Part 63, Subpart LL . These regulations, which are applicable to primary aluminum reduction operati ons, establish total fluoride (TF) emission limits for existing potlines and TF and polycyclic organic matter (POM) emission limits for anode bake furnaces. In addition to the emissions limits, the Primary Aluminum NESHAP also requires the installation

an d operation of monitoring equipment for certain control devices and process operating parameters. The Primary Aluminum NESHAP became applicable to the anode bake furnace in

1999

, to the green mill in 2000, and per Alcoa’s request for an extension was appl icable to the potlines in October 2001.

The approved August 3, 1999 Parametric Monitoring Plan and Site Specific Test Plan for the anode bake furnace and green mill control devices at Alcoa Rockdale were to be modified to include the potlines upon applica bility of 40 CFR Part 63 Subpart LL to the potlines. However, since the potlines are implementing the emissions averaging, per §63.846, this Implementation Plan has been prepared separate from those two documents. The Parametric Monitoring Plan and

Site Specific Test Plan w ere modified to reflect that this Implementation Plan is a separate

document.

This Implementation Plan has been prepared for regulatory authority review and approval in accordance with 40 CFR Part 63, Subpart LL §63.846(d). The purp ose of this Implementation

Plan is as follows:

Illustrate that the parametric monitoring demonstrates proper operation and maintenance of each control device; and

Perform reference method testing and record production data to demonstrate compliance with the average emission limit for the potlines.

The plan is prepared in accordance with §63.846 that requires the following sections, as appropriate:

Section 2

– Identify emission sources in the average;

Section 3

– Assign TF emission limit for the Alcoa Rockdale potlines;

Section 4

– Outline specific control technology used for each emission source in the averaging group and the date of its application;

Section 5

– Prepare a Site

- Specific Test Plan for the measurement of TF emissions in

accordance with t he requirements in §62.847(b);ROCKDALE OPERATIONS

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– Outline operating parameters to be monitored for each control system per §63.848(f) and describe how the operating limits were determined; and

Section 7

– Demonstrate that compliance with the applicable emission l imit were achieved under representative operating conditions.

2.0 EMISSION SOURCE IDENTIFICATION

There are 12 potrooms comprising 6 potlines at Alcoa Rockdale (two potrooms form one potline). Emissions at each potline consist of fugitive roof emission s (secondary emissions) and emissions from the primary control system. Table 1 summarizes abatement equipment, control

devi ces and EPNs for each potline.

Fugitive roof emissions are generated in the potrooms when sections of the pot fume control hooding is removed for anode changing and other operating procedures. Fugitive emissions within each potline exit through roof vents.

Each pot is equipped with a hooding and manifold system that captures and directs the emissions to the primary control syste m. The primary control systems vary between potlines at Rockdale which are illustrated on Figures 1 through 6 for potlines 3 through 8, respectively. Potline 3 has three electrostatic precipitators (ESPs) and one bag h ouse, with each ESP and baghouse havi ng two wet scrubbers. Potline 4 has three baghouses, where the first baghouse has four wet scrubbers, the second baghouse has three wet scrubbers, and the third baghouse has two wet scrubbers. Potline 5 has nine dry alumina scrubbers (A

- 398s). Potline 6 has six ESPs with each ESP having two wet scrubbers. Potlines 7 and 8 both have twelve A

- 398s. These primary control systems vent emissions through either a scrubber tower or A

- 398 stack(s). A description of each type of abatement equipment at Alcoa Ro ckdale is provided below.

2.1 A

- 398s

Alcoa

- designed A

- 398s operate by introducing smelting grade alumina into one end of

the A

- 398 reactor and removing reacted alumina from the other end. The reacted alumina is used as feed material in the pots during the alumina reduction process. The alumina fluidizes by blowing clean air and potline fume exhaust into the reactor through a series of perforated plates. Gaseous fluoride adsorbs (and condenses) onto the alumina surface and fabric filters positioned

on top of the reactor compartments that collect entrained alumina particles and other particulate matter present in the gas stream.ROCKDALE OPERATIONS

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Wet scrubbers are open spray towers that operate by introducing water into the top of the tower and po tline fume exhaust from the bottom of the tower. Gaseous fluoride adsorbs (and condenses) onto the lime/water mixture. The water and lime mixture is removed from the

bottom of the tower and is sent to the Scrubber Water Treatment Plant for water treatmen t. The

treated water from the Scrubber Water Treatment Plant is reused in the wet scrubbers.

2.3 ESPs

ESPs operate by introducing an electrical current across a wire hanging between grounded plates. Potline fume exhaust passes around the charged wi res and between the grounded plates caus ing the particulates to become ionized and attract ed to the plates. The air

entrained particulates contain fluoride. The particulates collect onto the plates that are periodically rapped, causing the particulates t o drop to the hopper. ESP catch is removed.

2.4 Baghouses

Baghouses operate by passing potline fume exhaust through a fabric to filter out entrained particulates. The air

- entrained particulates contain fluoride. After the particulates have collect ed onto the filter fabric, the particulates are removed. Each baghouse exhausts to a wet scrubber.

3.0 EMISSION LIMIT

Alcoa Rockdale Operations currently operate s six potlines. These potlines are defined as

center

- worked prebaked two (CWPB2) pots. P er §63.846(b), the average monthly TF emission limit for CWPB2 pots with 6 operating lines is 2.6 pounds of TF per ton of aluminum produced (lb TF/ton Al). The emission average (E T ) over the six potlines are calculated per §63.846(b)(2) by taking the sum of the emissions from the active potlines and dividing by the total monthly production of the plant, as illustrated in Equation 1 below. The total emissions from each potline

are calculated by summing the emissions from the fugitive roof emissions with th e potroom control system emissions, as illustrated in Equation 2 below.ROCKDALE OPERATIONS

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E T = E 3 + E 4 + E 5 + E 6 + E 7 + E 8

P
n

Where:

E T = Average emission rate of TF from Rockdale Operations (lbs TF/ton Al);

E 3 = Emission rate of TF from potline 3 (lb TF/month);

E 4 = Emission rate of TF from potline 4 (lb TF/month)

E 5 = Emission rate of TF from potline 5 (lb TF/month);

E 6 = Emission rate of TF from potline 6 (lb TF/month);

E 7 = Emission rate of TF from potline 7 (lb TF/month); and

E 8 = Emission rate of TF from potline 8 (lb TF/month).

P
n = Aluminum production rate for all potlines (ton Al/month);

Equation 2

E
n = [(C pn x Q pn ) + (C fn x Q fn )]

Where:

E
n = Emission rate of TF for potline n, where n equals 3 through 8 (lb TF/month);

C pn = TF concent ration from the primary control system (p) for potline n, (lb TF/dscf); Q pn = Effluent gas volumetric flow rate from the primary control system (p) for potline n (dscf/month);

C fn = TF concentration measured for secondary fugitive roof monitor emissions (f ) for potline n, (lb TF/dscf); and Q fn = Effluent gas volumetric flow rate from the secondary fugitive roof monitors (f) for potline n, dscf/month.

Total fluoride concentrations, either from the primary control system (C pn ) or from the

roof monitor emissi ons (C fn ), are determined by calculating a monthly average TF concentration per potline using testing results obtained in accordance with the appropriate method. Effluent volumetric flow rates, either from the primary control system (Q pn ) or from the roof monitor (Q fn ), are determined by calculating a monthly average volumetric flow rate per potline using testing results obtained in accordance with the appropriate method.

As discussed in Section 2.0, each individual potline has the same type of abatemen t equipment within the primary control system, except for potline 3. When a potline has different types of abatement equipment operating at variable timeframes within a month, the average monthly primary control system TF concentrations are account ed for the operating time of each type of abatement equipment.ROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM 4.0 APPLICABILITY AND CONTROL DEVICES

The TCEQ granted Alcoa Rockdale’s request for an extension of MACT LL applicability to potlines 1 through 8 until October 07, 2001. Potlines 1 and 2 were dism antled in the early 2000s leaving Potlines 3 through 8 operational . As of October 7, 2001 MACT LL applies to

P otlines 3 through 8 at Alcoa Rockdale

.

Primary emissions from each potline are treated through abatement equipment that comprise of one or tw o control devices per potline. Emissions generated from potline 3 are routed through one control device consisting of three ESPs, one baghouse and eight wet scrubbers. Emissions from potline 4 are routed through two control devices: 1) one control

devic e consists of one baghouse with four wet scrubbers, and 2) the second control device consists of two baghouses with five wet scrubbers. Emissions generated from potline 5 are routed through one control device that consists of nine A

- 398s. Emissions gener ated from potline 6 are routed through one control device that consists of six ESPs and twelve wet scrubbers before venting to the atmosphere. Emissions generated from potline 7 are routed through two control devices

– both control devices consist of six A

- 398s. Likewise, emissions generated from potline 8 are routed through two control devices that each consists of six A

- 398s.

Each control device are tested to determine the appropriate number of pieces of abatement equipment that are required to be oper ational at any one time per potline to meet the average TF

emission limit for Rockdale.

5.0 SITE

- SPECIFIC TEST PLAN

Applicable emissions testing requirements of the Primary Aluminum NESHAP include two requirements: 1) “initial” performance testing and 2 ) “ongoing” performance testing. Following the initial performance test, “on

- going” emissions testing have been implemented for potroom fugitive emissions and from each control device emissions. Sampling, analysis and quality control procedures to be use d for both the initial performance test and the on

- going compliance testing are described in this section of the Implementation Plan.

The following subsections of this Plan were prepared pursuant to the requirements in §62.847(b) and comply with §63.7. Section 5.1 provides a test program summary; Section 5.2 discusses the test schedule; Section 5.3 discusses the sampling locations; Section 5.4 discusses the sampling and analytical procedures; Section 5.5 provides data quality objectives; Section 5.6

pro vides internal quality assurance program; Section 5.7 discusses the external quality assurance program; and Section 5.8 describes any exceptions to EPA methodology.ROCKDALE OPERATIONS

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Alcoa Rockdale currently operates six aluminum reduction potlin es to which applicable emission limits under the Primary Aluminum NESHAP apply. Initial performance testing of the fugitive roof emissions and the potline control device emissions was completed in the early 2000s as required. All previous performance tes ts as well as ongoing performance test s were and

are conducted under normal operating procedures.

On

- going performance testing consist s of testing fugitive roof monitor emissions and primary control device emissions. Fugitive roof monitor emissions ar e tested at least three times per month per potline using either EPA Method 14 (potlines 4, 6 and 8) or EPA Method 14A (potlines 3, 5 and 7) protocol. Potline control device emissions are tested at three emission points annually using EPA Method 13B. If a control device has different abatement equipment, then a minimum of one emission point per year is tested from each type of abatement equipment.

Fluoride concentrations are measured in the laboratory usin g either EPA Method 13B or 4076

.

5.2 Test Sched ule

Initial performance tests on the potline primary control systems as well as fugitive roof monitor emissions was completed in the early 2000s.

5.2.1 Initial Performance Test

I nitial performance test included conducting emissions testing on the fugi tive roof monitor emissions and the potline control device emissions. Per §63.847(c), the “initial” performance tests for potroom fugitive roof emissions and the control system device emissions

were implemented during the first month following the applica bility of the Primary Aluminum NESHAP. Per §63.847(c), if performance tests are conducted on each primary control system within the 12 months prior to the compliance date, the results of that performance test may be used to determine initial compliance. Each initial performance test was conducted under normal process operating conditions.

A minimum of three test runs were performed to determine fugitive roof emissions from each potline per month. In accordance with §63.847(b)(8) of the NESHAP, at leas t one test run

was performed before the 15 th of the month, one run was performed after the 15 th and there were be at least 6 days between two of the three runs.ROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM In accordance with §63.847 of the Primary Aluminum NESHAP, a minimum of three test

run s wer e performed for each potline control device. For each test run, an emission point from a control device (i.e., wet scrubber or A

- 398) was selected and tes ted

. All of the stacks of the

selected abatement device were sampled for an equal time period using a single sample train as

discussed in Section 5.3.2.

All sampling and analytical methods listed in Table 2 are in accordance with the requirements of §63.847of the Primary Aluminum NESHAP. Fluoride concentrations were determined by EPA Method 13B or Al coa Methods 4075A/4076. Potroom fugitive TF emissions

were measured over an entire potroom cycle (48 hours) using EPA Method 13B, 14 or 14A. Methods 4075A/4076 are approved EPA alternate methods for total fluoride.

5.2.2 On

- Going Compliance Tests

As required, potroom fugitive roof emissions are sampled each month and each potroom primary control device is tested on an annual basis. All compliance testing is conducted under normal process operating conditions.

A minimum of three test runs are perfor med monthly to determine fugitive roof emissions from each potline. Monthly fugitive emissions testing is performed with at least one test run

before the 15 th of the month, one run after the 15 th and at least 6 days between two of the three

runs.

A mi nimum of three test runs are performed annually on each control device per §63.847(b)(2). For a control device that contains different types of abatement equipment, a

minimum of test s are performed on each type of abatement equipment annually. As discuss ed in Section 5.3.2, emission points with multiple stacks are sampled on an equal time period using a single sample train.

5.3 Sample Locations

Sample locations consist of roof monitors and A

- 398 and wet scrubber stacks. Samples

are collected using appropriate EPA or other approved methods. Copies of the reference methods are provided in Appendix A.ROCKDALE OPERATIONS

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Roof monitor sampling at Alcoa Rockdale are conducted in a ccordance with EPA Method 14, Method 14A, or an alternate method appro ved by EPA for the measurement of

fluoride and total airflow.

Three of the six potlines (potlines 4, 6 and 8) at Rockdale are equipped with EPA Method 14 sampling manifolds which are used to determine secondary total fluoride emissions. The sampling m anifold consists of eight roof monitor nozzles connected to a downcomer duct as required by Method 14. The sampling location consists of a nominal 12

- inch diameter duct with two test ports 90 o apart and located greater than 10 duct diameters downstream an d greater than 3 duct diameters upstream from the nearest flow disturbance. At some future date Alcoa may conduct a study to demonstrate that a single sample point collects a representative sample using the EPA 14 protocol. A discussion of the single

- poi nt sampling study is provided in Section 5.8.

Three of the six potlines, 3, 5 and 7, are equipped with cassettes to determine secondary total fluoride emissions per EPA Method 14A. Eight cassettes are located at equal intervals

across one room for each potline.

5.3.2 Potline Control Devices

Potline primary control system emissions are measured at the A

- 398 stacks and the wet scrubber stacks. There are currently two different stack and sampling location configurations on

the A

- 398s. The A

- 398s on pot line 7 and one A

- 398 on potline 5 have a single stack. For each test run, a Method 13B sample, or other appropriate method, is collected from the stack. The sampling location on each stack consists of two test ports 90 o apart. Each duct is the appropria te duct diameters upstream and downstream of any flow disturbances.

The remaining eight A

- 398s on potline 5 and the twelve A

- 398s on potline 8 have three stacks. Devices with multiple stacks, where each stack within the control device is of similar desig n, the approach of collecting a composite sample from each stack provide s a representative sample of the single piece of equipment. For example, each A

- 398 at potline 8 contains three stacks, referred to in this example as Stacks A, B & C. Each test run on the A

- 398 is conducted by placing a sample train on Stack A for one

- third of the test time, Stack B for one

- third of the test time, and Stack C for one

- third of the test time. The sampling location on each stack consists of two test ports 90 o apart. E ach duct is the appropriate duct diameters upstream and downstream of any flow disturbances.ROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM Potfume emissions from potlines 3, 4 and 6 are tested from wet scrubber stacks using

EPA Method 13 for total fluoride concentrations and EPA Methods 1 and 2 for air flow. Each wet scrubber is similar in construction and operation. Typically a wet scrubber consists of an 84

- inch diameter stack that is 96

- inches high. The two sampling ports are at 90 o to each other located approximately 60 to 72 inches downstream of the nearest flow disturbance, the top of the

15

- foot diameter scrubber tower. As discussed in Section 5.8, air flow velocities from the wet

scrubbers are measured using an Alternate Measurement Site per EPA Method 1, Section 2.5.

5.4 Sampling/Analyt ical Procedures

Alcoa Method 4075A/4076 or EPA Method 13B is used to determine total fluoride emissions from the potroom primary control system. Total fluoride emissions from the potroom

roof monitor are determined using EPA Method 14 or EPA Method 14A.

5.4.1 EPA Method 13B

An EPA Method 13B sampling train is used to determine total fluoride emissions from the potroom control systems. The sampling train c onsist s of a stainless

- steel nozzle and probe; a heated quartz

- fiber filter; impingers containin g de

- ionized (DI) water and silica gel; and an EPA Method 5 pump and sampling console. Sampling is performed isokinetically and the filter
temperature is maintained at 250 + 25 o F. A Teflon filter support may be used in place of the stainless steel support

.

The samples are analyzed for total fluoride according to EPA Method 13B. According to this procedure, the particulate fraction of the sample (the particulate filter and two probe rinses) is dried, ashed, and fused with NaOH. The fused sample is allowe d to cool and is then combined

with the back

- half or gaseous fraction prior to sample distillation and selectiv e ion electrode (SIE) analysis. The analysis is carried out in a way that provides separate gaseous and particulate

fluoride emissions.

5.4.2 EPA Method 14

According to EPA Method 14, gaseous and particulate fluoride emissions are drawn from the potroom roof monitor using a permanent sampling manifold with eight large nozzles. The sample is transported from the sampling manifold to ground leve l through a duct where sampling is performed to determine total fluoride concentrations. Effluent velocity and volumetric flowrate are determined using anemometers located in the roof monitor.ROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM As an alternative to the propeller anemometers described in M ethod 14, A lcoa may use scintillation anemometers to determine effluent velocity and volumetric gas flowrate through the roof monitors. Scintillation anemometers are optical

- based systems that use scintillation effects (the apparent position or brightness of an object when viewed through the atmosphere) to measure path

- averaged velocity. EPA has approved this methodology as an alternate method for determining total air flow as applicable to 40 CFR 60 Subpart LL. Appendix B contains a copy of the approved alternate methodology.

5.4.3 EPA Method 14A

According to EPA Method 14A, gaseous and particulate fluoride emissions are drawn from the potroom roof monitor into a specific cassette arrangem ent prior to exiting the roof . The cassettes are connected by tubing to flowmeters and a manifold system that allows for the equal distribution of volume pulled through each cassette, and finally to a dry gas meter. The cassettes are arranged with one unaltered cellulose filter and support pad in the first section f or solid fluoride retention and two cellulose filters with support pads that are impregnated with sodium formate for the chemical absorption of gaseous fluorides in the following two sections. Effluent velocity and volumetric flowrate are determined using anemometers located in the roof monitor. Three potlines, 3, 5 and 7 have EPA Method 14A equipment installed.

5.4.4 Alcoa Method 4075A

Total fluoride concentrations in the EPA Method 14 duct and the potline primary control

device stacks are determine d using Alcoa Method 4075A. This method is an EPA

- approved

alternative to Method 13B for the determination of total fluoride concentration. The Method 4075A sampling train consists of a stainless steel nozzle; an in

- stack cellulose thimble; stainless

ste el probe; impingers containing a 0.1N NaOH solution and silica gel; and an EPA Method 5 pump and sampling console.

The sample is analyzed by selective ion electrode according to Alcoa Method 4076A. According to this procedure, the particulate fraction o f the sample (the thimble and nozzle rinse) is first dried, ashed, and fused with NaOH and then distilled prior to analysis by ion selective electrode to determine particulate fluoride. Gaseous fluoride is determined from the impinger

solution. The solut ion is evaporated to dryness, and the residue is fused with NaOH, distilled

and anal yzed by ion selective electrode or automated F analyzer. Whereas the method allows for the determination of the weight fraction of particulate matter, Alcoa Rockdale has chosen not to take advantage of the option.ROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM 5.5 Data Quality Objectives

Data quality object ives are the pretest expectations of precision, accuracy, and completeness of data. The data quality objectives for each major measurement parameter are
present ed in Table 3. The precision and accuracy objectives for particulate matter, velocity, temperature molecular weight, and moisture are based on results from EPA collaborative tests. Accuracy and precision estimates for EPA Method 13B and Alcoa Method 4075 A are based on Alcoa’s experience with these methods. Achievement of the total fluoride objectives are assessed on an on

- going basis through the QA/QC activities described in Sections 5.6 and 5.7 of this test plan.

5.6 Internal Quality Assurance Progr am

5.6.1 Sampling Activities

Quality control (QC) for sample collection is based on adherence to EPA Reference and Alcoa method requirements for equipment calibration, sample train leak checks, isokinetic sampling and sample recovery. Acceptance criteri a specified for these activities in the applicable

test methods are used to access data quality and validate test data. For example, pre

- and post

test meter calibrations should be within + 5%, sample train leak rates should be < 0.02 cfm and sampling rates should be within 100 + 10% of isokinetic.

5.6.2 Analysis Activities

Quality control (QC) for sample analysis is based on adherence to sample preparation procedures specified in the EPA Reference and Alcoa methods, proper instrument calibration and analys is of QC samples.

Total Fluoride (Methods 13B and 4076 )

- Analysis for total fluoride is performed by selective ion electrode (SIE) using a Technicon II auto

- analyzer. A 5

- point calibration (zero plus four upscale points) is performed on the instrument with each batch of fluoride samples. Internal quality control consist s of reagent blanks, QC sample analyses and duplicate sample analyses. Analysis frequencies, acceptance criteria and corrective action for the internal quality control samples are summa rized in Table 4. The analytical QC sample is a sample of known concentration (approximately 0.5 ug/mL) prepared from a stock solution that is independent of the solution used to prepare the calibration standards. The duplicate analysis is performed by taking two sample aliquots from a randomly selected field sample.ROCKDALE OPERATIONS

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Following the initial compliance test, audit samples will be requested from EPA or the Texas Commission on Environmental Quality (TCEQ) . These sa mples will be analyzed with samples collected in the month following the date when the performan ce samples are received by

Alcoa . Performance audit samples will be requested for total fluoride (Methods 13B a nd 4075A/4076A). Audit results will be reported to the TCEQ Regional Office.

5.8 Exceptions to EPA Methodology

There are two exceptions to EPA methodologies:

Single point sampling alternative to Method 14; and

Alternative Measurement Sites at the wet scrubbers.

Alcoa Rockdale will implement sing le

- point sampling verification study to meet the requirements specified in EPA Method 14 Section 2.2.1. This protocol, when approved, will be implemented during sampling the ducts at potlines 4, 6 and 8. EPA approved Alcoa’s validation

test conducted at another Alcoa facility. The TCEQ approved the proposed study in 1999. Alcoa Rockdale will conduct the validation test, per the approved plan, and submit these results to the TCEQ and EPA Region 6 prior to implementing the single point sampling protocol a t Rockdale.

Sampling locations for all of the wet scrubbers do not meet the requirements of EPA Method 1. The sampling port locations are less than the minimum allowable distance of 2.0 duct

diameters downstream of the scrubber exit and less than the mi nimum distance of 0.5 duct diameters upstream from the top of the stack. Alcoa contracted Fossil Energy Research Corporation of Laguna Hills, California (FERC) to conduct an alternate measurement site

evaluation test on the wet scrubbers at Rockdale. FER C conducted three

- dimensional ang l e and velocity measurement tests on the exhaust gas of six scrubber tower exhaust stacks. The tests were performed under the provisions of EPA Method 1, Section 2.5, in which a sample location

that does not meet the norma l Method 1 specification for distances from flow disturbances can be qualified as an Alternative Measurement Site. The results showed that all six stacks met the Method 1 criteria for acceptability as an Alternative Measurement Site. FERC concluded that

“ Because the untested stacks are identical in design and because the test results are similar for the stacks tested, it is Fossil Energy Research Corp’s opinion that the flow angles on all 27 scrubber tower stacks at Rockdale meet the requirements of Metho d 1 to be classified as

Alternative Measurement Sites ”. A copy of this report is attached as Appendix C.ROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM 6.0 CONTROL DEVICE MONITORING PLAN

This section of the Implementation Plan details the criteria used to select each parameter

used to monitor the operation and maintenance of each abatement device. A discussion of the relationship of each parameter to control device performance, and the selected monitoring parameters along with the upper and/or lower operating limits, as appropriate, are included for the potline emission control devices at Rockdale. Table 5 summarizes the proposed monitoring parameters, frequencies and operating limits for the potline control devices.

6.1 Criteria For Parameter Selection

The criteria used by Alcoa when selecting the parameters to monitor each device was the regulatory requirement of 40 CFR Part 63.848(f), which requires the owner/operator to monitor the following parameters for each control device:

A

- 398s

– alumina flow and air flow;

Wet scrubbers

– water flow a nd air flow; and

ESPs

– voltage and secondary current.

The specific parameters proposed in this plan are measurements of control device operating variables that directly relate to the parameters specified by the regulation. These
parameters are monitor ed for each control device during normal operating procedures. In addition to these parameters, per §63.848(g), the exhaust stack of each control device is inspected daily for evidence of any visible emissions indicating abnormal operations.

Specific u pper and/or lower operating limits, as appropriate, were determined during the initial performance test and/or from historical data recorded during previous performance tests

conduc ted with EPA

- approved methods.

If a monitoring device for primary emission control devices for the potline measures a parameter outside of the operating limit(s) established, Alcoa will initiate corrective action procedures within one hour. The corrective action procedures are contained in the startup, shutdown, and malfunction plans located at Rockdale Operations. Per §63.848(i), only one parametric exceedance will be attributed to a given 24

- hour period. Per EPA 1

, “An exceedance during a startup, shutdown, or malfunction is not counted provided you demonstrate that you

opera ted and maintained the affected process and control equipment according to the procedures in your startup, shutdown, and malfunction plan. {§63.848(i)}”

1 U.S. Environmental Protection Agency . Plain Language Guide to the Primary aluminum NESHAP

– 40 CFR Part 63, Subpart LL. EPA

- 453/R

- 99

- 011. October 1999. Page 12.ROCKDALE OPERATIONS

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Wei reports that high alumina surface area in dry alumina scrubbers is neces sary to achieve high hydrogen fluoride removal efficiencies. 2 The surface area available for the removal of hydrogen fluoride is directly proportional to the amount of alumina fed into the primary

emission control device. The A

- 398 system is designed to provide a large excess capacity for fluoride adsorption under normal operation. However, continuous operation with too low an alumina flow rate will result in reduced gaseous fluoride removal efficiency. Therefore, Alcoa

establish ed a lower limit for alu mina flow for each A

- 398 primary control device. No upper limit

was established for alumina flow because the addition of more alumina would only serve to increase fluoride adsorption capacity of the reactor bed.

The potline control device low alumina flow limit was established by operating the control device at a reduced alumina flow rate for a period of approximately 24 hours. After the

low flow conditions were established, then total fluoride emissions were sampled from the control device. Rotary v ane feeder revolutions were used to determine alumina flow. The low

alumina flow rate was established as cumulative hertz per potroom cycle . The length of a potroom cycle at Rockdale is 24 or 48 hours.

Alumina is fed to the control device using a rotary vane feeder. Rotation of the feeder is determined by continuously monitoring the feeder shaft using a proximity switch. In the event that the rotary vane feeder is shut off, a bypass valve is opened and alumina flow is manually adjusted. A relationship between feeder Hertz from the variable speed drive and flow meter pounds per hour was developed. Rockdale u se s an Allen Bradley Model 160

- BA03NSF1P1 Hertz signal follower or similar system to measure the blower motor loads in amps. The accuracy of alumi na flow rate through a rotary vane feeder depends primarily on variations in the bulk density of alumina, which typically varies + 5% across 6 standard deviations.

6.3 Air Flow Limit

Guidelines published by USEPA for use by States when developing fluorid e emission standards for existing primary aluminum plants reported that exhaust rate is important for efficient primary fluoride collection. Exhaust rates that are too low result in low collection efficiency. 3 Therefore, Alcoa establish ed a lower limit f or air flow to ensure the proper

2 In: Anthony J. Buonicor and Wayne T. Davis, Air Pollution Engineering Manual , (New York: Van Nostrand Reinhold, 1992), p. 597

. 3 U. S. Environmental Protection Agency. Primary Aluminum: Guidelines for Control of Fluoride Emissions from Existing Primary Aluminum Plants. EPA

- 450/2

- 78

- 049b. December 1979. p. 6

- 19.ROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM collection, operation and efficiency of the A

- 398 and wet scrubber primary emission control devices. No upper air flow limit was established because high gas flow reportedly does not cause a negative impact on the control system performance. High gas flow is also limited by control device fan capacity and normal operation is at full capacity.

The lower air flow limit was established by operating the potroom control device at

minimum air flow conditions. After the low a ir flow limits were established, the total fluoride

emissions were sampled. A measure of fan amperage (amps) was used as a direct indicator of gas flow. The lower gas flow limit was established as cumulative fan amps for any potroom cycle

. Fan amps are m easured using a relay attached to each motor.

Centrifugal blower motors are used to regulate the flow of exhaust gas to control system. The blower motors deliver flow that is both predictable and repeatable according to a fan curve that is provided by t he manufacturer. The fan curve uses motor amps as a key variable to determine air flow expressed in cfm, or unit volume per unit time. Rockdale use s an Acromag Model 1701 current transmitter or similar system to measure the blower motor loads in amps.

T ypical amp meter accuracy is + 10%.

6.4 Water Flow

Water flow rate is an important parameter in wet scrubber control devices for the efficient primary fluoride collection. Flow rates that are too low result in low collection efficiency. Alcoa

establish ed a lower limit for water flow to ensure the proper collection, operation and efficiency of the wet scrubber primary emission control devices. No upper water flow limit w as established because high water flow reportedly does not cause negative impact on the control system performance.

The lower water flow limit was established by operating the potroom control device at

minimum water flow condition. After the low flow conditions were established, the total

fluoride emissions were sampled. An ultrasoni c Panametrics Model XMT868 or Dynasonics Series 901 flow meter, or other similar device, is used to measure water flow. The lower water

flow limit was established as cumulative gallons per minute per control device per potroom cycle

.

6.5 Voltage

Volt age is an important parameter in ESP control devices for the efficient primary fluoride collection. Voltages that are too low result in low collection efficiency. Alcoa

establish ed a lower limit for voltage to ensure the proper collection and operation e fficiency of the ESP primary control devices. No high voltage limit was established because high voltage reportedly does not cause negative impact on the control system performance.ROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM The lower voltage limit was established by operating the potroom contro l device at minimum voltage condition. After the low voltage conditions were established, the total fluoride

emissions were sampled. Voltage was measured using a Power Guard Model SQ

- 300 precipitator controller or similar operating device that measures v oltage at the transformer rectifier sets of the ESP. The lower voltage limit was established as cumulative volts per control device per potroom cycle

.

6.6 Secondary Current

Secondary current is an important parameter in ESP control devices for the e fficient primary fluoride collection. Secondary currents that are too low result in low collection efficiency. Alcoa establish ed a lower limit for secondary current to ensure the proper collection, operation efficiency of the ESP primary control devices. No high secondary current limit was established because high secondary current reportedly does not cause negative impact on the control system performance.

The lower secondary current limit was established by operating the potroom control

device at mini mum current conditions. After the low current conditions were established, the

total fluoride emissions were sampled. Secondary current is measured using a Power Guard Model SQ

- 300 precipitator controller or similar operating device that measures amps at the transformer rectifier sets of the ESP. The lower secondary current limit was established as cumulative amps per control device per potroom cycle

.

7.0 COMPLIANCE DEMONSTRATION

The initial demonstration of c ompliance was conducted in the early 20 00s and submitted to both the state and federal regulatory agencies. Ongoing testing as previously described in this document are occurring.ROCKDALE OPERATIONS

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### TABLESROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM Table 1. Summary of Abatement Devices by Potline

Potline Equipment On the Number of Equipment Per Control EPN Numb ers

Potline Control Device Abatemen t Equipment Roof Monitors

Devices

3 3 Electrostatic Precipitators
8 Wet Scrubbers 1 Baghouse 1 1 ESP & 2 Wet Scrubbers
1 ESP & 2 Wet Scrubbers
1 ESP & 2 Wet Scrubbers 1 Bagho use & 2 Wet
Scrubbers 10C1, 10C2, 10C3, 10C4, 10C5, 10C6, 10C7, 10C8 F10C1, F10C2, F10C3,
F10C4

4 3 Baghouses
9 Wet Scrubbers 2 1 Baghouse & 4 Wet Scrubbers 10D1, 10D2, 10D8, 10D9 F10D1, F10D2, 2 Baghouses & 5 Wet
Scrubbers 10D3, 10D4, 10D5, 10D6, 1 0D7 F10D3,
F10D4

5 9 Dry Alumina
Scrubbers 1 9 Dry Scrubbers 10E1, 10E2, 10E3, 10E4, 10E5, 10E6, 10E7, 10E8, 10E9 F10E1, F10E2, F10E3,
F10E4

6 6 Electrostatic Precipitators
12 Wet Scrubbers 1 6 ESPs &
12 Wet Scrubbers 10F1, 10F2, 10F3, 10F4, 10F5, 10F6, 10F7, 10F8, 10F9, 10F10, 10F11, 10F12 F10F1, F10F2, F10F3,
F10F4

7 12 Dry Alumina
Scrubbers 2 6 Dry Scrubbers 10G1, 10G2, 10G3, 10G4, 10G5, 10G6 F10G1, F10G2, 6 Dry Scrubbers 10G7, 10G8, 10G9, 10G10, 10G11, 10G12 F10G3,
F10G4

8 12 Dry Alumin a Scrubbers 2 6 Dry Scrubbers 10H1, 10H2, 10H3, 10H4, 10H5, 10H6 F10H1, F10H2, 6 Dry Scrubbers 10H7, 10H8, 10H9, 10H10, 10H11, 10H12 F10H3,
F10H4ROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM Table 2. Summary of Sampling and Laboratory Test Methods

Potline Para m eter Roof Monitors EPA Sample Collection
Method Control Device

EPA Sample Collection
Method EPA Laboratory
Test Method

3 Fluoride 14A 13B or 4075A 13B or 4076A

Air Flow Scintillation

Anemometer (1) 1 and 2 NA

4 Fluoride 14 13B or 4075A 13B or 4076A

Air Flow Scintil lation

Anemometer (1) 1 and 2 NA

5 Fluoride 14A 13B or 4075A 13B or 4076A

Air Flow Scintillation

Anemometer (1) 1 and 2 NA

6 Fluoride 14 13B or 4075A 13B or 4076A

Air Flow Scintillation

Anemometer (1) 1 and 2 NA

7 Fluoride 14 A 13B or 4075A 13B or 4076A

Air Flow Scintillation

Anemometer (1) 1 and 2 NA

8 Fluoride 14 13B or 4075A 13B or 4076A

Air Flow Scintillation

Anemometer (1) 1 and 2 NAROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM Table 3. Summary of Estimated Accuracy and Precision Objectives

Parameter (Method) Precision Accuracy

Total Fluoride (Method 13B) ±10% b ±15% c

Total Fluoride (Method 4075A/4076A) ±10% b ±15% c

Velocity/volumetric flow (Methods 1 and 2) ±6% a ±10% a

Gas Molecular Weight (Method 3 ) ± 10 % a ± 2 0% a

Gas Moisture Content (Me thod 4) ±20% a ±10% a

a Precision and accuracy estimates based on results of EPA collaborative tests.
b Relative percent difference (RPD) based on duplicate analyses, where

[( First_Value) 1

- (Second

_ Value) 2 ] *2
RPD=

____________________________ __ x 100%

( First_Value) 1 + (Second

_ Value) 2

c Relative error (%) for control sample analyses, where

Measured_Value

– Theoretical_Value Relative error = __________________________________ x 100% Theoretical_Value

d Pr ocedures for this m ethod similar to EPA Method 5. Precision and accuracy estimated based on EPA collaborative tests for Method 5.ROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM Table 4. Summary of Internal Quality Control Checks, Frequencies, Acceptance Criteria

and Corrective Action for Total Fluoride Analysis

Q uality Control Check Frequency Acceptance Criteria Corrective Action

Filter reagent blank (M13B) Once per lot of
filters <0.015 mgF/cm 2 1. Repeat reagent blank 2. Obtain alternate supply of low

- F filters 3. Repeat reagent blank

Thimble reagent bla nk (4076A) One every 3
months <0.8 mgF/thimble 1. Repeat reagent blank 2. Obtain alternate supply of cellulose
thimbles 3. Repeat reagent blank NaOH reagent blank (0.1N NaOH solution

– 4076A) One every 3
months ≤ 0.06 mg/L 1. Repeat reagent blank
2. Ob tain alternate supply of NaOH 3. Repeat reagent blank

QC sample analysis Once with each
batch of samples ± 15 % agreement with QC value 1. Repeat QC sample analysis

2. If still unacceptable, repeat instrument
calibration

Duplicate analysis Once with eac h
batch of samples Relative percent

difference of ±10% 1. Repeat duplicate analysis 2. If still unacceptable, service instrumentROCKDALE OPERATIONS

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Print Date/Time 5/27/2011 6/13/2008 8:58 AM 1:28:40 PM Table 5. Potroom Parametric Monitoring

Parameter Measurement Compliance Frequency

Alumina Flow Rotary Vane Fee der Operations Cumulative cycles (hertz) per control device per potroom cycle

Air Flow Fan Amperage Cumulative amps per control device per potroom cycle

Water Flow Water Flow Meters Cumulative gallons per control device per potroom cycle

ESP Pri mary Voltage Volt Meter in Motor Control Centers Cumulative volts per control device per potroom cycle

ESP Secondary Current Amp Meter in Motor Control
Centers Cumulative ESP Milliamps per potroom cycleROCKDALE OPERATIONS

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### FIGURESROCKDALE OPERATIONS

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### APPENDIX A

EPA TEST METHODSROCKDALE OPERATIONS

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### APPENDIX B

EPA

- APPROVED ALTERNATE AIR FLOW METHODOLOGYROCKDALE OPERATIONS

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### APPENDIX C

ALTERNATE MEASUREMENT SITE STUDYROCKDALE OPERATIONS

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