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, 2010

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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, 2010 
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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 ........................................................................... E 
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SECTION 1.0 

INTRODUCTION

The Avogadro Group, LLC (Avogadro) was contracted by Agrium U.S. Inc. Sacramento 

Nitrogen Operations (Agrium SNO) 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 (CAA) Information Collection Request 

(ICR) Letter 

The testing program was performed on May 12, 2010 by Michael Miller and Robert 

Odell of Avogadro. The tests were not observed by any regulatory personnel. 

Operations were coordinated by John Killey of Agrium SNO. The tests were performed 

to determine the following emission parameters: 

 NOX - ppmvd @ 0% O2, lb/hr, lb/ton 

 O2 and CO2, - % volume dry (for molecular weight and dilution 

calculations) 

 Stack gas moisture content and volumetric flow rate 

This report presents the test results and supporting data, the testing procedures, 

descriptions of the facility and sampling location, 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 test runs are presented 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. 
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TABLE 1-1 

SUMMARY OF RESULTS 

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AGRIUM U.S., INC. - SNO 

MAY 12, 2010 

Parameter Average Results Notes 

Plant Production, tons/hr 8.2 -- 

Stack Conditions 

O2, % volume dry 0.625 -- 

CO2, % volume dry 0.737 -- 

Moisture, % 2.4 -- 

Stack Temperature, oF 292.9 -- 

Volumetric Flow Rate, acfm 22,938 -- 

NOX Emissions 

ppm volume dry [<45.09] DLL 

ppm @ 0% O2 [<46.42] DLL 

lb/hr as NO2 [<5.058] DLL 

lb/ton as NO2 [<0.618] DLL 

Note: Detailed results can be found in Section 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.
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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 ammonia to make nitric acid as part of the 

production of nitrogen fertilizers. 

The nitric acid plant uses the DuPont high-pressure 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 H2O. Hot process gas from the converter is cooled 

by a series of exchangers and waste heat boilers. Cool process gas then flows to the 

absorber where the nitric acid-forming reactions are taken to completion. 

The tail gas from the absorber passes through a demister and has natural gas added before 

entering the NO2 decomposer. The natural gas reacts with the tail gas in the decomposer 

to reduce the NO2 concentration in the tail gas. The tail gas then passes through a waste 

heat boiler and turbine before being vented to atmosphere. The amount of NOX 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 sampling ports are located 90 degrees apart in the 

same horizontal plane, greater than 8 stack diameters downstream and 16 diameters 

upstream from flow disturbances. The ports are properly placed per EPA Method 1, and 

are accessible by a catwalk approximately 25 feet above ground level. 

A total of 12 sampling traverse points were located according to EPA Method 1, as 

specified for flow traverses. Six points were traversed from each of the two sampling 

ports. 
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SECTION 3.0 

TEST DESCRIPTION

3.1 PROGRAM OBJECTIVES 

The tests were conducted to provide information to the US EPA about the emissions from 

a nitric acid plant. The test program included measurement of concentrations of NO, NO2, 

O2 and CO2. Stack gas volumetric flow rate and moisture content were also measured 

and used in conjunction with pollutant concentration to calculate emission rates of NOX

in units of lb/hr and lb/ton 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 recording systems were provided to Avogadro and 

are included in this final report. Testing was conducted shortly after 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 this program are summarized in Table 3-1. 

Additional information on specific applications of and modifications 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 

O2 Paramagnetism EPA 3A < 2% of full scale 

CO2 Nondispersive infrared EPA 3A < 2% of full scale 

NOX FTIR EPA 320 < 2% of full scale 

Volumetric flow rate Pitot / temperature traverse EPA 1, 2 -- 

Moisture content Impinger weight gain EPA 4 -- 
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3.3.1 Diluent Gas Measurements

Three 60-minute diluent gas (O2 and CO2) test runs were performed at the exhaust stack 

of the tail gas absorber during normal full-load conditions. 

Concentrations were measured using Avogadro’s dry extractive continuous emissions 

monitor system (CEMS) described in Appendix A. This system meets the requirements 

of EPA and CARB methods for gaseous species. 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 system includes components to extract a 

representative sample from the source, remove 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 probe to the sample conditioner and the 

sample conditioner to the analyzer manifold - 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 system, constructed of stainless steel and 

Teflon tubing, to direct sample gas to the analyzers, and 

7) Sample flow rate control - a series 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 - performed once daily) or through 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. It 
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includes software for controlling the collection of calibration and emission monitoring 

data, and hardware for connection of the analyzer outputs to the recording 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 exhaust 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 have 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-telluride (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 optical transfer mirrors. 

The 10-meter pathlength “White” absorption cell used gold-surface internal mirrors. The 

interior cell walls were made of polished stainless 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 condensation 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. Sample spectra were recorded (based on 64 coadded interferograms). At least one 128-scan 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 analyze all the infrared 

field data. The program allows the development and storage of analytical methods for 

analysis of spectral data (absorbance) files. 
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Quality Assurance 

Calibration Transfer Standards and Absorption Path Lengths

Before sampling, a calibration transfer standard (CTS) gas was introduced to the FTIR 

system to determine the effective absorption pathlengths by comparing the field CTS 

spectra to a fundamental CTS spectrum recorded 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 absorption 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 sampling 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 spectrometer; 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 the 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 nitric 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 ensure 
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their appropriate performance during the sampling runs. Second, our laboratory manager 

examines the sample spectra and the quantitative 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 reference 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 Regulations (40 CFR 61, Appendix 

B) allows validation of FTIR-based measurements by a pair-wise comparison between 

the results of two FTIR systems. One FTIR was used to measure “native” (or “unspiked”) and a second FTIR was used to measure spiked concentrations of the target 

analytes (nitric oxide and nitrogen dioxide) in twelve independent samples. The results 

of the method validation 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 gas flow rate was controlled using a NIST 

certified 0-500 mL per minute mass flow controller set at 200 mL per minute so that the 

spike gas represented approximately 10% of the total instrument sample flow rate. Using 

sulfur hexafluoride as a tracer gas, the dilution factor was determined to be 0.098. The 

actual mean spiked concentration of nitric oxide was Sm = 1109 ppm and the mean 

analyte concentration was Su = 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 factor of CF = 0.936 and t-test value of t = 1.388. Therefore, the test 

method is valid for nitric oxide since the correction factor is in the range 0.7 ≤ CF ≤ 1.3 

and t-test value is insignificant 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 600.0 ppm sulfur hexafluoride (tracer gas) at 

the back end of the sample probe. The spike gas flow rate was controlled using a NIST 

certified 0-500 mL per minute mass flow controller set at 200 mL per minute so that the 

spike gas represented approximately 10% of the total instrument sample flow rate. Using 

sulfur hexafluoride as a tracer gas, the dilution factor was determined to be 0.099. The 

actual mean spiked concentration of nitrogen dioxide was Sm = 993.7 ppm and the mean 

analyte concentration was Su = 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 factor 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 insignificant at a 97.5% confidence level (12 samples). Results of 

the method validation are presented in Table 4-4. 
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1915 1910 1905 1900 1895 1890 1885 1880 1875 

Sample

NO

H2O

2930 2920 2910 2900 2890 2880 2870 2860 

Sample

NO2

H2O

Wavenumber (cm‐1)

Figure 3-1. Selected Spectra. 

Red: Sample spectrum, Green: Nitric Oxide reference spectrum, 

Purple: Nitrogen Dioxide reference spectrum, Blue: Water reference spectrum 
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3.3.3 Volumetric Flow Rates

The mass emission rate for NOX was determined by calculations based on measurements 

of stack gas volumetric flow rate and moisture content using EPA Methods 2 and 4 

respectively. The calculated flow rate was used with the measured emission 

concentrations to calculate mass emission rates in units of lb/hr and lb/ton. These 

emission rates in conjunction with process rate data in units of tons/day allowed 

calculation of emission rates in terms of lb/ton. 

3.3.4 Process Data

 Process operating data were collected by Agrium personnel. Manual readings were taken 

from the plant’s calibrated nitric acid production meter. The plant nitric acid production 

rates were used to document process rate and in the calculation of mass emission rates in 

units of lb/ton. 
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SECTION 4.0 

RESULTS

The average emission results are presented in Table 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 procedures. Appendix B presents the quality 

assurance information, including instrument calibration data. Raw field data sheets, 

process data, FTIR data, and CEMS data are included in Appendix C. Appendix D 

presents the general and specific equations used for calculating emissions, and computer 

spreadsheet calculations. A copy of the ERT Test Plan can be found in Appendix E. 
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TABLE 4-1 

GASEOUS EMISSIONS RESULTS 

INFORMATION COLLECTION REQUEST 

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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 

O2, % vol. dry 0.575 0.630 0.670 0.625 

CO2, % 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 

NOX Emissions 

ppm volume dry [<91.91] [<26.75] [<16.61] [<45.09] 

ppm @ 0% O2 [<94.51] [<27.58] [<17.16] [<46.42] 

lb/hr as NO2 [<10.31] [<2.993] [<1.868] [<5.058] 

lb/ton as NO2 [<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 reported detection limit. 
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TABLE 4-2 

MINIMUM ANALYTICAL UNCERTAINTIES 

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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 0.706 
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TABLE 4-3 

EFFECTIVE PATHLENGTHS 

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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 10.09 
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TABLE 4-4 

NITRIC OXIDE TEST METHOD VALIDATION 

AGRIUM U.S., INC. 

MAY 12, 2010 

Measured Analyte Concentrations 

 Concentrations (ppm) 

Sample Ss SF6 (spk) Unspiked Si

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 

Sm = 1109 SD = 51.44 

 where: 

Ss Measured concentration of the analyte in the spiked samples (ppm) 

SF6 (spk) Measured concentration of the tracer gas in the spiked samples (ppm) 

Unspiked Measured concentration of the analyte in the native (unspiked) samples (ppm) 

Si Ss – Unspiked (ppm) 

Sm Mean concentration of the analyte in the spiked samples (ppm) 

SD Standard deviation of the Si values (ppm) 

Dilution Factor (DF), Expected Concentration (CS) and Bias (B) 

DF = 0.098 Dilution factor where DF = SF6 (spk) / SF6 (dir) 

SF6 (dir) = 599.9 ppm Mean measured concentration of tracer gas 

SF6 (spk) = 58.69 ppm Mean measured concentration of tracer gas in spiked samples 

Spike (dir) = 10000 ppm Mean measured concentration of the nitric oxide spike blend 

Unspike = 65.20 ppm Mean measured 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 = Sm - CS 

Statistical Significance of Bias using the t-statistic (t) 

|B| = 71.41 ppm Absolute value of Bias 

SD = 51.44 ppm Standard deviation of Si

t = 1.388 t-statistic where t = |B|/SD 

If t < 2.201 (for 12 samples), application of correction factor (CF) is not required. 

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

Correction Factor (CF, if required) 

CF = 1 / (1 + (B / CS)) = 0.936 
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TABLE 4-5 

NITROGEN DIOXIDE TEST METHOD VALIDATION 

AGRIUM U.S., INC. 

MAY 12, 2010 

Measured Analyte Concentrations 

 Concentrations (ppm) 

Sample Ss SF6 (spk) Unspiked Si

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 

Sm = 993.7 SD = 5.189 

 where: 

Ss Measured concentration of the analyte in the spiked samples (ppm) 

SF6 (spk) Measured concentration of the tracer gas in the spiked samples (ppm) 

Unspiked Measured concentration of the analyte in the native (unspiked) samples (ppm) 

Si Ss – Unspiked (ppm) 

Sm Mean concentration of the analyte in the spiked samples (ppm) 

SD Standard deviation of the Si values (ppm) 

Dilution Factor (DF), Expected Concentration (CS) and Bias (B) 

DF = 0.099 Dilution factor where DF = SF6 (spk) / SF6 (dir) 

SF6 (dir) = 600.0 ppm Mean measured concentration of tracer gas 

SF6 (spk) = 59.57 ppm Mean measured concentration of tracer gas in spiked samples 

Spike (dir) = 10080 ppm Mean measured concentration of the nitric oxide spike blend 

Unspike = 0.000 ppm Mean measured 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 = Sm - CS 

Statistical Significance of Bias using the t-statistic (t) 

|B| = 7.067 ppm Absolute value of Bias 

SD = 5.189 ppm Standard deviation of Si

t = 1.362 t-statistic where t = |B|/SD 

If t < 2.201 (for 12 samples), application of correction factor (CF) is not required. 

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

Correction Factor (CF, if required) 

CF = 1 / (1 + (B / CS)) = 1.007