## SOURCE TEST REPORT 2010 NITRIC ACID PLANT EPA INFORMATION COLLECTION REQUEST AGRIUM U.S., INC. SACRAMENTO NITROGEN OPERATIONS WEST SACRAMENTO, CALIFORNIA

Prepared For: 

### Agrium U.S., Inc. 3961 Channel Drive West Sacramento, California 95691

For Submittal To: 

### US Environmental Protection Agency US EPA Mailroom (D243-02) 109 T.W. Alexander Drive Research Triangle Park, NC 27711

Prepared By:

Michael J. Miller 

### The Avogadro Group, LLC 2825 Verne Roberts Circle Antioch, California 94509 (925) 680-4300

June 21, 2010Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C iii 

### SUMMARY INFORMATION

Source Information
Source Location: Agrium U.S., Inc. West Sacramento Nitrogen Operations 3961 Channel Drive West Sacramento, California 95691 Contact: Mr. John Killey, Environmental Specialist Company: Agrium U.S., Inc. Telephone: (916) 375-6160 Facsimile: (916) 375-6109 Regulatory Agency: U.S. Environmental Protection Agency

Unit: Nitric Acid Plant Purpose: To provide nitrogen oxide data to the USA EPA Applicable Regulations: Section 114 of the Clean Air Act (CAA) Procedures: EPA Methods 1, 2, 3A, 4, and 320


### Testing Company Information
Testing Firm: The Avogadro Group, LLC 2825 Verne Roberts Circle Antioch, California 94509 Certification: ARB Independent Tester Contact: Michael J. Miller, QSTI Erick Mirabella, QSTI Project Manager General Manager Telephone: (925) 680-2654 (925) 680-0935 Facsimile: (925) 680-4416 (925) 680-4416 Test Date (s): May 12, 2010Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C iv 

### TABLE OF CONTENTS

SECTION PAGE

1.0 INTRODUCTION ..................................................................................................1

2.0 SOURCE LOCATION INFORMATION ...........................................................3 2.1 FACILITY AND SOURCE DESCRIPTION ..............................................3 2.2 SAMPLING LOCATION ............................................................................3

3.0 TEST DESCRIPTION ...........................................................................................4 3.1 PROGRAM OBJECTIVES .........................................................................4 3.2 TEST CONDITIONS...................................................................................4 3.3 TEST PROCEDURES .................................................................................4 3.3.1 Diluent Gas Measurements .............................................................5 3.3.2 Fourier Transformed Infrared Spectroscopy ....................................6 3.3.3 Volumetric Flow Rates ..................................................................10 3.3.4 Process Data ...................................................................................10

4.0 RESULTS .............................................................................................................11

APPENDICES

A MEASUREMENT PROCEDURES .................................................................... A B QUALITY ASSURANCE .................................................................................... B B.1 Quality Assurance Program Summary and ARB Certification B.2 Equipment Calibration Data

C FIELD DATA ........................................................................................................ C C.1 Sampling Location C.2 Avogadro CEMS Data C.3 FTIR Data C.4 Field Data Sheets C.5 Process Data

D EMISSIONS CALCULATIONS ......................................................................... D D.1 General Emissions Calculations D.2 Emissions Spreadsheets D.3 ICR Enclosure Spreadsheets

E ERT TEST PLAN PRINTOUT ........................................................................... EAgrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 1 

### SECTION 1.0

INTRODUCTION

The Avogadro Group, LLC (Avogadro) was contracted by Agrium U.S. Inc. Sacramento Nitrogen Operations (Agrium SN O) to perform a series of emission source tests at their facility in West Sacramento, California. The tests were conducted to address the following regulatory item:

 Section 114 of the Clean Air Act (C AA) Information Collection Request (ICR) Letter
The testing program was performed on Ma y 12, 2010 by Michael Miller and Robert Odell of Avogadro. The tests were not ob served by any regulatory personnel. Operations were coordinated by John Killey of Agrium SNO. The tests were performed to determine the following emission parameters:

 NO X - ppmvd @ 0% O 2 , lb/hr, lb/ton

 O 2 and CO 2 , - % volume dry (for mole cular weight and dilution calculations)

 Stack gas moisture content and volumetric flow rate
This report presents the test results a nd supporting data, the testing procedures, descriptions of the facility and sampling loca tion, and a summary of the quality assurance procedures used by Avogadro. The average emissions test results are summarized in Table 1-1. Detailed results for individual te st runs are presente d in Section 4.0. The appendices contain the supporting data used to calculate the final test results, including the raw data, the field data sheets, and calculation spreadsheets.Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 2 

### TABLE 1-1 SUMMARY OF RESULTS INFORMATION COLLECTION REQUEST AGRIUM U.S., INC. - SNO MAY 12, 2010

Parameter Average Results Notes

Plant Production, tons/hr 8.2 --
Stack Conditions

O 2 , % volume dry 0.625 -- CO 2 , % volume dry 0.737 -- Moisture, % 2.4 -- Stack Temperature, oF 292.9 -- Volumetric Flow Rate, acfm 22,938 --
NO X Emissions

ppm volume dry [<45.09] DLL ppm @ 0% O 2 [<46.42] DLL lb/hr as NO 2 [<5.058] DLL lb/ton as NO 2 [<0.618] DLL

Note: Detailed results can be found in S ection 4.0 and in the appendix. “DLL” and [<X] denotes that at least one, but not all, values used to report an in-stack emissions value are less than the laboratory’s reported detection limit.Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 3 

### SECTION 2.0

SOURCE LOCATION INFORMATION

2.1 FACILITY AND SOURCE DESCRIPTION
Agrium U.S., Inc. operates a nitric acid plant located at 3961 Channel Drive in West Sacramento, California. The plant oxidizes a mmonia to make nitric acid as part of the production of nitrogen fertilizers.
The nitric acid plant uses the DuPont high-pr essure process for the oxidation of ammonia with air to make nitric acid. The mixed ammonia/air gas passes over a platinum gauze catalyst for conversion into NO and H 2 O. Hot process gas from the converter is cooled by a series of exchangers and waste heat boi lers. Cool process ga s then flows to the absorber where the nitric acid-formi ng reactions are taken to completion.
The tail gas from the absorber passes through a demister and has natural gas added before entering the NO 2 decomposer. The natural gas reacts wi th the tail gas in the decomposer to reduce the NO 2 concentration in the tail gas. Th e tail gas then passes through a waste heat boiler and turbine befo re being vented to atmosphere. The amount of NO X and CO emitted depends on the amount of natural gas used in the decomposer.



### 2.2 SAMPLING LOCATION
The tail gas exhausts through a vertical, cylindrical stack 25 inches in diameter and approximately 55 feet tall. Two 3-inch samp ling ports are located 90 degrees apart in the same horizontal plane, greater than 8 st ack diameters downstream and 16 diameters upstream from flow disturbances. The por ts are properly placed per EPA Method 1, and are accessible by a catwalk approxim ately 25 feet above ground level.
A total of 12 sampling traverse points we re located according to EPA Method 1, as specified for flow traverses. Six points we re traversed from each of the two sampling ports.Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 4 

### SECTION 3.0

TEST DESCRIPTION

3.1 PROGRAM OBJECTIVES
The tests were conducted to pr ovide information to the US EPA about the emissions from a nitric acid plant. The test program incl uded measurement of concentrations of NO

, NO 2 , O 2 and CO 2 . Stack gas volumetric flow rate and moisture content were also measured and used in conjunction with pollutant concen tration to calculate emission rates of NO X in units of lb/hr and lb/to n of nitric acid produced.



### 3.2 TEST CONDITIONS

Process conditions were established and unit operating data were collected by Agrium personnel. Printouts from the analog reco rding systems were pr ovided to Avogadro and are included in this final report. Testing wa s conducted shortly afte r the plant had started up after being down for an extended period of time for emergency maintenance.



### 3.3 TEST PROCEDURES
The specific test procedures used in th is program are summarized in Table 3-1. Additional information on speci fic applications of and m odifications to standard procedures are presented in the following sub- sections. Where any conflicts exist in the descriptions, the specific descriptions here in Section 3.3 will take precedence.



### TABLE 3-1 TEST PROCEDURES FOR AGRIUM U.S., INC.

Parameter Measurement Principle Reference Method Detection Limit O 2 Paramagnetism EPA 3A < 2% of full scale
CO 2 Nondispersive infrared EPA 3A < 2% of full scale
NO X FTIR EPA 320 < 2% of full scale Volumetric flow rate Pitot / temperature traverse EPA 1, 2 --

Moisture content Impinger weight gain EPA 4 --Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 5 3.3.1 Diluent Gas Measurements
Three 60-minute diluent gas (O 2 and CO 2 ) test runs were performed at the exhaust stack of the tail gas absorber during normal full-load conditions.
Concentrations were measured using Avoga dro’s dry extractive continuous emissions monitor system (CEMS) described in Appendix A. This system meets the requirements of EPA and CARB methods for gaseous spec ies. A heated Teflon line and chilled knockout system were used to remove moisture from the sample gas stream prior to being introduces to the analyzers.
The sample conditioning and delivery sy stem includes components to extract a representative sample from the source, rem ove the moisture and particulate matter from the sample stream, and transport the sample to the analyzers. The primary components of this subsystem are:

1) A quartz , titanium , stainless steel or glass probe - heated or insulated as necessary to avoid condensation, 2) Sample filtration – filters located on the probe, pump, and prior to all of the analyzers for removal of particulate matter, 3) Teflon tubing - connecting the prob e to the sample conditioner and the sample conditioner to the analyzer ma nifold - heated or insulated as necessary to avoid condensation, 4) Sample conditioner - glass or stainless steel flasks immersed in an ice bath to remove the moisture from the sample gas stream, 5) Vacuum pump - a leak-free pump with Teflon diaphragm to transport the sample gas through the system, 6) Sample manifold - a distribution syst em, constructed of stainless steel and Teflon tubing, to direct sample gas to the analyzers, and 7) Sample flow rate control - a seri es of rotameters, vacuum gauges and pressure gauges connected to the manifold used to maintain the appropriate sample flow rates.

The calibration gas system utilizes only EPA Protocol gases to verify the operation, linearity, and range settings of the electronic analyzers. The sample gas system allows for the introduction of the protocol gases to the analyzers either directly through the manifold (calibration error check - performe d once daily) or thr ough the sampling system (system bias check - performed with each run).
The electronic analyzers are rack-mounted and are maintained in the mobile lab. The data recording and acquisition system is based on a digital system known as STRATA. ItAgrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 6 includes software for contro lling the collection of calib ration and emission monitoring data, and hardware for connection of the anal yzer outputs to the reco rding system. Test results are provided in the form of on -site printouts of the digitized data.

3.3.2 Fourier Transformed Infrared Spectroscopy

Introduction
Extractive Fourier Transform infrared (FTIR) spectroscopic testing for nitric oxide and nitrogen dioxide was performed on the exha ust of a nitric acid plant at the Agrium facility in Sacramento, CA. Testing was performed on May 12, 2010 by The Avogadro Group, LLC. The FTIR results of this test ha ve been presented in Appendix C.3 of this report.
FTIR spectrophotomer
The FTIR spectrometer used for this test was equipped with a (nominal) 10-meter absorption cell. The spectrometer operated at 0.5 cm -1 spectral resolution. It employed a Michelson interferometer, mercury-cadmium-te lluride (MCT) detector cooled to liquid nitrogen temperature (77 K), beam splitter, and cell windows of zinc selenide (ZnSe), hot-wire infrared radiation source, and front-surface opt ical transfer mirrors.
The 10-meter pathlength “White” absorption ce ll used gold-surface internal mirrors. The interior cell walls were made of polished st ainless steel and minimize potential chemical interactions between the sample and the cell. Transducers and thermocouples (Type J) connected directly to the insulated sample cells provided the pressures and temperatures of the sample streams. During testing, the temperature was 121  ̊ C at all times. This elevated temperature prevented gas condensa tion within the cell and minimized analyte adhesion to the cell walls and mirrors.
Gas Sampling and Spectral Collection
For each test period, sample gas continuously passed through the sampling system at a sample flow rate of 2 liters per minute. Sa mple spectra were recorded (based on 64 coadded interferograms). At least one 128-s can background spectrum was recorded using compressed continuous emission monitoring zero grade nitrogen every 4-6 hours. AutoQuant ProTM (Version 4.0.0.130) was used to collect and analyz e all the infrared field data. The program allows the developm ent and storage of analytical methods for analysis of spectral data (absorbance) files.Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 7 Quality Assurance
Calibration Transfer Standards and Absorption Path Lengths
Before sampling, a calibration tr ansfer standard (CTS) gas wa s introduced to the FTIR system to determine the effective absorp tion pathlengths by comp aring the field CTS spectra to a fundamental CTS spectrum reco rded in a well-known, physically measured absorption path. A cylinder of ethylene in nitrogen (20.2 ppm) served as the CTS. All the pre- and post-test absorp tion pathlengths varied by less than 2 percent. The pathlength results are presented in Table 4- 3. The overall average pathlength was 10.09

m.
Reference Spectra
The concentration of the analytes of the extracted samples where determined by comparing the samples’ absorbance spectra to a set of single-component reference spectra representing the analytes at similar, well-known concentrations.

Leak Checks
On-site test personnel performed leak checks. The leak check procedure was to 1) plug the probe tip, 2) evacuate the entire sampli ng system, including the FTIR absorption cell to a total (absolute) pressure of approximately 5 psi, 3) isolate the sampling system from the pump, and 4) observe the pressure in the sampling system over approximately one minute. In all cases, the pressure of the evacuated isolated sampling systems changed by less than 0.1 psi per minute.

Data Storage
A dedicated computer controlled the FTIR spectromete r; the hard drives of the computers served as the primary data storage media. During testing, on-site staff created and maintained backup and archive copies of th e spectral data (interferograms, single beam spectra, and absorbance spectra ) on USB memory devices.
Minimum Analytical Uncertainties (MAU)
EPA Method 320 specifies a number of analytical uncertainty parameters that the analyst may calculate to characterize the FTIR system performance. Described in Table 4-2 is the uncertainty results for nitr ic oxide and nitrogen dioxide.

Data Reviews
The spectroscopic data and analytical results have been subject to several levels of review. First, the field instrument operators inspect the instruments’ outputs to ensureAgrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 8 their appropriate performance during the sa mpling runs. Second, our laboratory manager examines the sample spectra and the quantitativ e analytical results, and also spot-checks the analysis results by hand; these examinations include visual comparisons of the sample and reference spectra. Examples of the refe rence and sample spectra are illustrated in Figure 3-1.

Test Method Validation

EPA Method 320, Measurement of Vapor Phase Organic and Inorganic Emissions By Extractive FTIR Spectroscopy , U.S. Code of Federal Re gulations (40 CFR 61, Appendix B) allows validation of FTIR-based meas urements by a pair-wise comparison between the results of two FTIR systems. One FT IR was used to measure “native” (or “unspiked”) and a second FTIR was used to m easure spiked concentrations of the target analytes (nitric oxide and nitrogen dioxide) in twelve independent samples. The results of the method validati on are presented below.
Spike gas was introduced into the sampling system by injecting gas from cylinder standard of 10000 ppm nitric oxide and 599.9 ppm sulfur hexafluoride (tracer gas) at the back end of the sample probe. The spike ga s flow rate was controlled using a NIST certified 0-500 mL per minute mass flow contro ller set at 200 mL pe r minute so that the spike gas represented approximate ly 10% of the total instrument sample flow rate. Using sulfur hexafluoride as a tracer gas, the d ilution factor was determined to be 0.098. The actual mean spiked concentration of nitric oxide was S m = 1109 ppm and the mean analyte concentration was S u = 65.20 ppm. Thus, the expected concentration was CS = 1037 ppm nitric oxide. So the bias in the proposed method is B = 71.41 ppm. This yielded a correction fact or of CF = 0.936 and t-test value of t = 1.388. Therefore, the test method is valid for nitric oxide since th e correction factor is in the range 0.7 ≤ CF ≤ 1.3 and t-test value is insignifi cant at a 97.5% confidence level ( 12 samples). Results of the method validation are presented in Table 4-4.
Spike gas was introduced into the sampling system by injecting gas from cylinder standard of 10080 ppm nitrogen dioxide and 60 0.0 ppm sulfur hexafluoride (tracer gas) at the back end of the sample probe. The spike gas flow rate was cont rolled using a NIST certified 0-500 mL per minute mass flow contro ller set at 200 mL pe r minute so that the spike gas represented approximate ly 10% of the total instrument sample flow rate. Using sulfur hexafluoride as a tracer gas, the d ilution factor was determined to be 0.099. The actual mean spiked concentratio n of nitrogen dioxide was S m = 993.7 ppm and the mean analyte concentration was S u = 0.000 ppm. Thus, the expected concentration was CS = 1001 ppm nitrogen dioxide. So the bias in the proposed method is B = -7.067 ppm. This yielded a correction fact or of CF = 1.007 and t-test value of t = 1.362. Therefore, the test method is valid for nitrogen dioxide since the correction factor is in the range 0.7 ≤ CF ≤ 1.3 and t-test value is insigni ficant at a 97.5% confidence level (12 samples). Results of the method validation are presented in Table 4-4.Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 9 

# 1915 1910 1905 1900 1895 1890 1885 1880 1875 Sample

NO

H 2 

# O

2930 2920 2910 2900 2890 2880 2870 2860 Sample

NO 2



# H 2 

# O

Wavenumber (cm

‐ 1 

# )
Figure 3-1. Selected Spectra. Red: Sample spectrum, Green: Ni tric Oxide reference spectrum, Purple: Nitrogen Dioxide reference spect rum, Blue: Water reference spectrumAgrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 10 3.3.3 Volumetric Flow Rates

The mass emission rate for NO X was determined by calculations based on measurements of stack gas volumetric flow rate and mo isture content using EPA Methods 2 and 4 respectively. The calculated flow rate was used with the measured emission concentrations to calculate mass emission ra tes in units of lb/h r and lb/ton. These emission rates in conjunction with process ra te data in units of tons/day allowed calculation of emission rate s in terms of lb/ton.

3.3.4 Process Data
Process operating data were collected by Ag rium personnel. Manual readings were taken from the plant’s calibrated nitric acid producti on meter. The plant nitric acid production rates were used to document process rate a nd in the calculation of mass emission rates in units of lb/ton.Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 11 

### SECTION 4.0

RESULTS

The average emission results are presented in Ta ble 1-1. The results of the individual test runs are presented in Tables 4-1 through 4-5. The results have been calculated in units consistent with the ICR requirements. US EPA “Standard Condition(s)” are 29.92 inches of mercury and 68 oF.

Additional information is included in the appendices. Appendix A contains generic descriptions of standard measurement pro cedures. Appendix B pr esents the quality assurance information, including instrument calibration data. Raw field data sheets, process data, FTIR data, and CEMS data are included in Appe ndix C. Appendix D presents the general and specific equations us ed for calculating emissions, and computer spreadsheet calculations. A copy of the ER T Test Plan can be found in Appendix E.Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 12 

### TABLE 4-1 GASEOUS EMISSIONS RESULTS INFORMATION COLLECTION REQUEST AGRIUM U.S., INC. MAY 12, 2010

Parameter Run 1 Run 2 Run 3 Average Results

Date 5/12/10 5/12/10 5/12/10 -- Time 2028-2131 2151-2254 2311-2413 -- Plant Production, tons/hr 8.2 8.0 8.3 8.2
Stack Conditions

O 2 , % vol. dry 0.575 0.630 0.670 0.625 CO 2 , % vol. dry 0.706 0.752 0.753 0.737 Moisture, % 1.7 2.1 3.5 2.4 Temperature, oF 292.4 293.5 292.8 292.9 Volumetric Flow Rate, acfm 22,907 22,890 23,017 22,938 NO X Emissions

ppm volume dry [<91.91] [<26.75] [<16.61] [<45.09] ppm @ 0% O 2 [<94.51] [<27.58] [<17.16] [<46.42] lb/hr as NO 2 [<10.31] [<2.993] [<1.868] [<5.058] lb/ton as NO 2 [<1.255] [<0.373] [<0.225] [<0.618] Note: [<X] denotes that at least one, but not all, values used to report an in-stack emissions value are less than the laboratory’s re ported detection limit.Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 13 

### TABLE 4-2 MINIMUM ANALYTICAL UNCERTAINTIES

INFORMATION COLLECTION REQUEST AGRIUM U.S., INC

. 

### MAY 12, 2010

Compound Nitric Oxide Nitrogen Dioxide
Reference Optical Density, ppm-m 4056 466.5 Upper Analytical Range Endpoint (FU, cm -1 ) 1913.93 2935.68 Lower Analytical Range Endpoint (FL, cm -1 ) 1851.40 2842.75 RMSD Noise Level (RMSSm, abs) 2.859 x 10 -4 5.818 x 10 -4 Noise Absorbance Area (abs, cm -1 ) 0.013 0.017 Reference Absorbance Area (abs, cm -1 ) 4.400 1.091 Sample Absorbance Pathlength (L, m) 10.09 10.09 MAU (ppm) 1.192 0.706Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 14 

### TABLE 4-3 EFFECTIVE PATHLENGTHS INFORMATION COLLECTION REQUEST AGRIUM U.S., INC

. 

### MAY 12, 2010

Date Path length (m) Averages (m)
5/10/2010 20:33 10.16 5/10/2010 20:34 10.14 5/10/2010 20:35 10.18 5/10/2010 20:36 10.11 5/10/2010 20:37 10.14 5/10/2010 20:38 10.09 5/10/2010 20:40 10.11 5/10/2010 20:41 10.14 10.13 5/12/2010 9:07 9.99 5/12/2010 9:08 10.02 5/12/2010 9:09 9.98 5/12/2010 9:10 9.92 5/12/2010 9:11 10.05 5/12/2010 9:12 10.02 5/12/2010 9:14 9.97 9.99 5/12/2010 16:56 10.03 5/12/2010 16:57 10.05 5/12/2010 16:58 10.12 5/12/2010 16:59 10.11 5/12/2010 17:00 10.08 10.08 5/12/2010 19:18 10.08 5/12/2010 19:20 10.03 5/12/2010 19:21 10.10 5/12/2010 19:22 10.12 5/12/2010 19:23 10.04 10.07 5/12/2010 21:40 10.21 5/12/2010 21:41 10.18 5/12/2010 21:42 10.15 5/12/2010 21:43 10.23 5/12/2010 21:44 10.16 10.19 5/12/2010 22:59 10.00 5/12/2010 23:00 10.10 5/12/2010 23:02 10.12 5/12/2010 23:03 10.09 5/12/2010 23:04 10.06 10.07

Overall Pathlength 10.09Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 15 

### TABLE 4-4 NITRIC OXIDE TEST METHOD VALIDATION AGRIUM U.S., INC

. MAY 12, 2010

Measured Analyte Concentrations Concentrations (ppm) Sample S s SF 6 (spk) Unspiked S i 1 1079 58.53 44.00 1035 2 1103 58.92 46.31 1056 3 1089 58.89 34.26 1055 4 1084 58.96 104.4 979 5 1195 59.27 271.5 923 6 1079 58.24 20.95 1058 7 1091 58.30 5.787 1085 8 1091 57.53 5.066 1086 9 1091 57.83 16.26 1075 10 1187 59.46 120.0 1067 11 1111 59.39 13.16 1098 12 1102 58.92 100.8 1001 S m = 1109 SD = 51.44 where: S s Measured concentration of the analyte in the spiked samples (ppm) SF 6 (spk) Measured concentration of the tr acer gas in the sp iked samples (ppm) Unspiked Measured concentration of the analyte in the native (unspiked) samples (ppm) S i S s – Unspiked (ppm) S m Mean concentration of the analyte in the spiked samples (ppm) SD Standard deviation of the S i values (ppm)
Dilution Factor (DF), Expected Concentration (CS) and Bias (B) DF = 0.098 Dilution factor where DF = SF 6 (spk) / SF 6 (dir)
SF 6 (dir) = 599.9 ppm Mean measur ed concentration of tracer gas SF 6 (spk) = 58.69 ppm Mean measured concen tration of tracer gas in spiked samples Spike (dir) = 10000 ppm Mean measured concentration of th e nitric oxide spike blend

Unspike = 65.20 ppm Mean measur ed concentration of analyte in the native (unspiked) samples
CS = 1037 ppm Expected concentration of the spiked samples where CS = DF x Spike (dir) + Unspike (1 – DF) B = 71.41 ppm Bias at spike level where B = S m - CS
Statistical Significance of Bi as using the t-statistic (t) |B| = 71.41 ppm Absolute value of Bias SD = 51.44 ppm Standard deviation of S i

t = 1.388 t-statistic where t = |B|/SD If t < 2.201 (for 12 samples), app lication of correction factor (CF) is not required

. If t > 2.201 (for 12 samples), app lication of correction factor (CF) is required

. Correction Factor (CF, if required) CF = 1 / (1 + (B / CS)) = 0.936Agrium U.S., Inc. - SNO June 21, 2010 2010 Nitric Acid Plant EPA Information Collection Request

10088.0C 16 

### TABLE 4-5 NITROGEN DIOXIDE TEST METHOD VALIDATION AGRIUM U.S., INC

. MAY 12, 2010

Measured Analyte Concentrations Concentrations (ppm) Sample S s SF 6 (spk) Unspiked S i 1 989.6 59.35 0.000 989.6 2 985.9 59.94 0.000 985.9 3 996.3 59.91 0.000 996.3 4 994.9 59.29 0.000 994.9 5 992.7 59.79 0.000 992.7 6 998.7 58.56 0.000 998.7 7 994.4 59.90 0.000 994.4 8 1001 59.74 0.000 1001 9 993.5 59.56 0.000 993.5 10 1002 58.84 0.000 1002 11 988.2 60.03 0.000 988.2 12 987.3 59.90 0.000 987.3 S m = 993.7 SD = 5.189 where: S s Measured concentration of the analyte in the spiked samples (ppm) SF 6 (spk) Measured concentration of the tr acer gas in the sp iked samples (ppm) Unspiked Measured concentration of the analyte in the native (unspiked) samples (ppm) S i S s – Unspiked (ppm) S m Mean concentration of the analyte in the spiked samples (ppm) SD Standard deviation of the S i values (ppm)
Dilution Factor (DF), Expected Concentration (CS) and Bias (B) DF = 0.099 Dilution factor where DF = SF 6 (spk) / SF 6 (dir)
SF 6 (dir) = 600.0 ppm Mean measur ed concentration of tracer gas SF 6 (spk) = 59.57 ppm Mean measured concen tration of tracer gas in spiked samples Spike (dir) = 10080 ppm Mean measured concentration of th e nitric oxide spike blend

Unspike = 0.000 ppm Mean measur ed concentration of analyte in the native (unspiked) samples
CS = 1001 ppm Expected concentration of the spiked samples where CS = DF x Spike (dir) + Unspike (1 – DF) B = 7.067 Bias at spike level where B = S m - CS
Statistical Significance of Bi as using the t-statistic (t) |B| = 7.067 ppm Absolute value of Bias SD = 5.189 ppm Standard deviation of S i

t = 1.362 t-statistic where t = |B|/SD If t < 2.201 (for 12 samples), app lication of correction factor (CF) is not required

. If t > 2.201 (for 12 samples), app lication of correction factor (CF) is required

. Correction Factor (CF, if required) CF = 1 / (1 + (B / CS)) = 1.007