# Timberline Ammonia

- 001

Determination of Inorganic Ammonia by

Continuous Flow Gas Diffusion and

Conductivity Cell Analysis

Prepared By: Dr. Edward F. Askew

Date: June 24 , 2011

## Page 2 of 54 

# Table of Contents

1. SCOPE and APPLICATION

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

2. SUMMARY

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

3. DEFINITIONS

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

4. INTERFERENCES

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

5. SAFETY

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

6. EQUI PMENT AND SUPPLIES

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

7. REAGENTS AND STANDARDS

................................ ................................ ............... 7

Table 1: Ammonia Stock Standards

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

Table 2: Membrane Dynamic Range

................................ ................................ .................. 9

8. SAMPLE COLLECTION, PRESERVATION, SHIPMENT, DIGESTION and

STORAGE

................................ ................................ ................................ .............................. 9

9. QUALITY CONTROL

................................ ................................ ................................ . 9

10. PROCEDURE

................................ ................................ ................................ ............. 11

11. CALCULATIONS / DATA REDUCTION

................................ ................................ 13

12. METHOD PERFORMANCE

................................ ................................ ..................... 15

13. POLLUTION CONTROL

................................ ................................ .......................... 16

14. WASTE MANAGEMENT

................................ ................................ ......................... 16

15. REFERENCES / BIBLIOGRAPHY

................................ ................................ ........... 16

16. ATTACHMENTS

................................ ................................ ................................ ....... 18

Table A: General Instrument Parameters

................................ ................................ .......... 19

Table B: 4 in ch Membrane Pooled MDLs for Individual Laboratories and All

Laboratories

................................ ................................ ................................ ...................... 20

Table C: 10 inch Membrane Pooled MDLs for Individual Laboratories and All

Laboratories

................................ ................................ ................................ ...................... 25

Table D: LFM/LFMD Recoveries

................................ ................................ .................... 27

Table E: 4 Inch Membrane LFM/LFMD Calculations

................................ ..................... 28

Table F:10 Inch Membrane LFM/LFMD Calculations

................................ .................... 29

Table G 1: 4 inch Membrane

- LFB Overall Percent Recovery

................................ ....... 30

Table G 2: 4 inch membrane

- LFB Overall Percent Recovery

................................ ........ 31

Table H 1: 10 inch Membrane

- LFB Overall Percent Recovery

................................ ..... 32

## Page 3 of 54 Table H 2: 10 Inch Membrane

- LFB Overall Percent Recovery

................................ ..... 33

Table I 1: 4 Inch Membrane LFB Bias and Precision

................................ ...................... 34

Table I 2: 4 Inch Membrane LFB Bias and Precision

................................ ...................... 35

Table I 3: 4 Inch Membrane LFB Bias and Precision

................................ ...................... 36

Table J 1: 10 Inch Membrane LFB Bias and Precision

................................ .................... 37

Tab le J 2: 10 Inch Membrane LFB Bias and Precision

................................ .................... 38

Table J 3: 10 Inch Membrane LFB Bias and Precision

................................ .................... 39

Table K 1: 4 Inch Membrane Calibration Verification

................................ ..................... 40

Table K 2: 4 Inch Membrane Calibration Verification

................................ ..................... 42

Table L: 10 Inch Membrane Calibration Verification

................................ ...................... 43

Tab le M 1: 4 Inch Membrane Initial and Ongoing Precision and Recovery

.................... 44

Table M 2: 4 Inch Membrane Initial and Ongoing Precision an d Recovery

.................... 45

Table N 1: 10 Inch Membrane Initial and Ongoing Precision and Recovery

................... 46

Table N 2: 10 Inch Membrane Initial and Ongoing Precision and Recovery

................... 47

Table O 1: CCV Low Standard Bias and Precision 4 Inch Membrane

............................ 48

Table O 2: CCV High Standard Bias and Precision 4 Inch Membrane

............................ 49

Table P: CCV Low and High Standard Bias and Precision 10 Inch Membrane

.............. 50

Table Q: Youden Pair Recovery

- 4 Inch Membrane

................................ ......................... 51

Table R: Single Operator Standard Deviation and %RSD

– 4 Inch Membrane

............... 51

Table S:Youden Pair Recovery

- 10 Inch Membrane

................................ ......................... 52

Table T: Single Operator Standard Deviation and %RSD

– 10 Inch Membrane

............. 52

Table U: Laboratory Reagent Blank

– Instrument Detection Limit 4 Inch Membrane

.... 53

Table V: Laboratory Reagent Blank

– Instrument Detection Limit 10 Inch Membrane

.. 54

## Page 4 of 54 

# 1. SCOPE and APPLICATION

1.1. Ammonia gas permeation through a hydrophobic membrane is used to determine

ammonia concentration in aqueous solution s

.

1.2. For the determination of total ammonia from solutions that contain organic nitrogen

( Kjeldahl nitrogen) and inorganic ammonia in aqueo us and solid samples, a Kjeldahl

digestion is required prior to analysis.

1.3. Detection limits and linear ranges for organic and inorganic ammonia will vary with the

matrices. Tables B and C in Section 16 provide pooled results for method detection limit

(MDL) and minimum level (ML) determined from the inter

- laboratory method

validation study for 4 inch or 10 inch membranes . However, actual method detection

limits and linear working ranges will be dependent on the sample matrix,

instrumentation, and selected op erating conditions.

1.4. Users of the method data should state the data

- quality objectives prior to analysis. Users

of the method must document and have on file the required initial demonstration of

capability data described in Section 9.2 prior to using the me thod for analysis

.



# 2. SUMMARY

2.1. An aqueous s ample is combined with 1

- 15 % sodium hydroxide to attain a pH above 11

producing ammonia in a non

- ionized form in solution

.

NH 4 + (aq) 

## + OH

- (aq) 

## → NH 3(g) 

## + H 2 

## O (aq)



## 2.2. This solution is conveyed to a membrane assembly and the gaseous ammonia in the

aqueous sample migrates through the hydrophobic membrane into the borate buffer

absorption solution, which is transported to a conductivity cell.

2.3. The measured changes in condu ctivity are used to quantitate ammonia in the sample

using an external calibration.



# 3. DEFINITIONS

3.1. Ammonia Stock Standard Solution : A concentrated solution containing method analyte

prepared in the laboratory using assayed reference materials or purchased fro m a

reputable commercial source.

3.2. Calibration Blank: A volume of reagent water acidified with the same acid matrix as in

the calibration standards. The calibration blank is a zero standard and is used to calibrate

the ammonia analyzer

.

3.3. Calibration Standard : A solution prepared from the dilution of stock standard solutions.

The se solutions are used to calibrate the instrument response with r espect to analyte

concentration.

3.4. Continuing Calibration Verification (CCV) : Ammonia standard that has a concentration

between the lower calibration standard and upper calibration standard. A CCV will be

run at least once per batch.

## Page 5 of 54 3.5. Control Charts: Graphical charts that contain the expected value (the central line) and the

acceptable range of occurrence . The acceptable ran ge is determined from the control

limits and warning limits. Refer to Part 1000 of Standard Methods for the Examination

of Water and Wastewater for further explanation and guidance.

3.6. Dynamic Range ( DR) : The concentration range over which the instrument resp onse to

an analyte is second order quadratic

. This range is defined by the concentration range

between the lowest concentration standard and the highest concentration standard.

3.7. Instrument Detection Limit (IDL) : The concentration equivalent to the analyte s ignal

which is equal to replicate measurements of the calibration blank.

3.8. Initial Demonstration of Capability (IDC) also called a Initial Precision and Recovery

(IPR) : IDC/IPR are run by analysts with no experience with this method before they run

any sampl es to v erify their capability with the method or w hen significant maintenance

or modifications are performed on the instrument

. A laboratory fortified blank (LFB ) is

analyzed four times, the mean recovery and standard deviation are calculated and

compare d to the limits listed in this method for IDC/ IPR

.

3.9. Instrument Performance Check (IPC) Solution : A solution of method analyte, used to

evaluate the performance of the instrument system with respect to a defined set of

method criteria.

3.10. Labo ratory Fortified B lank (LFB): An aliquot of ammonia free reagent water to which

known q uantities of ammonia is added in the laboratory. The LFB is analyzed exactly

like a sample, and its purpose is to determine whether the methodology is in control and

whether the laborator y is capable of making accurate and precise measurements.

3.11. Laboratory Fortified Sample Matrix/Duplicate (LFM/LFMD) also called a Matrix

Spike/Duplicate (MS/MSD) : An aliquot of an environmental sample to which known

quantities of ammonia is added in the labo ratory. The LFM /LFMD are analyzed exactly

like a sample, and there purpose is to determine whether the sample matrix contributes

bias to the analytical results. The background concentrations of the analytes in the

sample matrix must be determined in a separate aliquot and the measured values in the

LFM /LFMD corrected for background concentrations.

3.12. Laboratory Reagent Blank (LRB) : An aliquot of reagent water or other blank matrices

that are treated exactly as a sample including exposure to all glassware, equipment,

solvents, reagents, and internal standards that are used wi th other samples. The LRB is

used to determine if method analytes or other interferences are present in the laboratory

environment, reagents or apparatus.

3.13. Method Detection Limit (MDL) : The minimum concentration of an analyte that can be

identified, measure d, and reported with 99% confidence that the analyte conc entration is

greater than zero

. Full requirements are listed in 40 CFR Part 136 Appendix B

.

3.14. Minimum Level (ML): Minimum level is determined by multiplying the MDL by 3.18

and rounding the product to the number nearest to 1 or 2 or 5 x 10 n 

## , where n is a positive

or negative integer. The minimum level is used to determine the lowest standard

concentration that can be used for the instrument.

## Page 6 of 54 3.15. Ongoing Demonstration of Capability (ODC) also called Ongoing Precision and

Recovery (OPR) : ODC/OPR are performed at least once per sample batch to

demonstrate proficiency with the method

. Reagent water is spiked with known quantities

of ammonia . Its purpose is to assure that the results produced by the laboratory re main

within the limits specified in this method for precision and recovery

.

3.16. Sample Batch : A group of samples which behave similarly with respect to the sampling

or the testing procedures being employed and which are processed as a unit. For QC

purposes, if the number of samples in a group is greater than 20, then each group of 20

samples or less will all be handled as a separate batch. A batch cannot span between

laboratory work days (24 hrs). New batches must be started each laboratory work day.

3.17. Solid Samp le : For the purpose of this method, a sample taken from material classified as

soil, sediment or sludge that is digested by the Total Kjeldahl Nitrogen method

.

3.18. Total Kjeldahl Nitrogen: Digestion method of water or solid samples by methods

currently approve d in 40 CFR 136, Table IB.

3.19. Water Sample : For the purpose of this method, a sample taken from one of the following

sources: surface, ground, storm runoff, industrial or domestic wastewater.



# 4. INTERFERENCES

4.1. Volatile amines can diffuse through the hydrophobic m embrane to produce a

conductivity response. Generally, interference from low molecular weight amines is not

a practical problem because their natural occurrence is so limited.

4.2. Chloramines can decompose to produce ammonia.

4.3. Deionized water used in reagents a nd standards must be high quality and ammonia

- free

to avoid interference.



# 5. SAFETY

5.1. This method does not address all safety issues associated with its use. The laboratory is

responsible for maintaining a safe work environment and a current awareness file of

OSHA regulations regarding the safe handling of any chemicals specified in this method.

A reference file of material safety data sheets (MSDSs) should be available to all

personnel involved in these analyses

.



# 6. EQUIPMENT AND SUPPLIES

6.1. S ample Containers: As pe r current 40 CFR Part 136 Table II , polyethylene,

fluoropolymer or glass.

.

6.2. Class A V olumetric Flasks: various sizes used for preparation of standards.

6.3. T est Tubes: 15 x 85 mm; used in autosampler.

6.4. Analytical Balance: analytical, capable of accurately weighing to 0.0 0 01 ± 0.00 0 05 g.

6.5. p H METER: double junction electrode; used when adjusting the pH of the boric acid

solution

.

## Page 7 of 54 6.6. Ammonia Analyzer with gas permeation cell and conductivity detector: Timberline

Instruments TL

- 28 00 Ammonia Analyzer or an equivalent instrument that uses the same

chemistry/determinative techniques and can meet the QC performance criteria set in the

method.



# 7. REAGENTS AND STANDARDS

7.1. Reagent Water

– Deionized water that does not contain measurable quantities of

ammonia above the detection level of the dynamic range or any interfering volatile

conductive compounds . This water will be used for all standards, calibration zero, LRB,

LFB, and sample dilutions preparation.

(Note: P rolonged s torage of reagent water will expose it to ammonia absorption from

the laboratory environment. Prepare fresh as needed.)

7.2. Caustic Solution: Sodium Hydroxide (NaOH ) or Potassium Hydroxide

- 50% (w/v )

solution. P repare by weighing a known amoun t of ACS or better grade sodium

hydroxide or potassium hydroxide to the nearest gram and add slowly to a known

volume of reagent water in mL with the ratio of 1 gram sodium hydroxide or potassium

hydroxide to 1 mL of reagent water. Mix thoroughly in a beak er with a magnetic stirrer.

(Caution: Reaction produces excessive heat and is caustic to unprotected skin.

Prolonged storage of reagent water will expose it to ammonia absorption from the

laboratory environment. Prepare fresh as needed.)

7.3. Caustic Working S olutions

– 1

- 15% (w/v ). Select caustic solution as needed per sample

characteristics. Selection is based on the caustic solutions ability to raise the pH of the

sample to a point that free ammonia is formed to diffuse through the membrane.

Typically, with most ammonia concentrations, the 5% caustic solution is utilized. Other

caustic solution concentrations may be needed based on higher ammonia concentrations,

lower ammonia concentration or water matrix. Final caustic solution concentration will

be based on ammonia concentration in the sample, the water matrix and QC performance

requirements.

7.3.1. 1 %: Dilute 20 ml of 50% (w/w) sodium hydroxide or potassium hydroxide

solution to 1 L with reagent water. Mix well by inversion. Prepare fresh weekly

7.3.2. 5 %: Dilute 100 m l of 50 % (w/w) sodium hydroxide or potassium hydroxide

solution to 1 L with reagent water. Mix well by inversion. Prepare fresh weekly.

7.3.3. 10%: Dilute 200 ml of 50 % (w/w) sodium hydroxide or potassium hydroxide

solution to 1 L with reagent water. Mix well by inversion. Prepare fresh weekly

.

7.3.4. 15%: Dilute 300 ml of 50% (w/w) sodium hydroxide or potassium hydroxide

solution to 1 L with reagent water. Mix well by inversion. Prepare fresh weekly.

7.4. Boric Acid Solution 10,000 ppm boric acid (H 3 

## BO 3 

## ). Add 10 ± 0.001 g of ACS grade or

better boric acid in a 1 L volumetric flask and dilute to volume with reagent water. Mix

until the boric acid has completely dissolved in the solution.

(Note: Prolonged storage of Boric Acid will expose it to ammonia absorption from the

lab oratory environment. Prepare fresh as needed.)

## Page 8 of 54 7.5. Ammonium Hydroxide (NH 4 

## OH )

- 1.0 N . Transfer 1 35 mL of 28% ACS grade or better

ammonium hydroxide to ~ 100 mL of reagent water in a 1 L volumetric flask. Dilute to

the mark with reagent water and mix well. Mak e fresh monthly.

7.5.1. Ammonium Hydroxide Working Solutions

- 0. 0 1 N Ammonium hydroxide

. Transfer 1 mL of 1 N ammonium hydroxide to 100 mL volumetric flask. Dilute to

volume with reagent water. Mix well by inversion. Prepare fr e sh weekly.

7.6. Buffer Solutions

– pH a djusted Boric acid, Select boric acid solution as needed per

sample characteristics. Typically, with most ammonia concentrations, the 250 ppm

Buffer Solution is utilized. Other Buffer Solution concentrations may be needed based

on higher ammonia concentrat ions (100 ppm ammonia or greater) or lower ammonia

concentration (0.1 ppm or lower). Final Buffer Solution concentration will be based on

ammonia concentration in the sample and QC performance requirements.

7.6.1. 100 ppm. Transfer 10 mL of the 10,000 ppm boric acid solution to a 2 L beaker.

Add ~ 975 mL of reagent water. While stirring adjust the pH to 6.5

- 7 using 0.01

or 0.02 N ammonium hydroxide solution. Prepare fresh weekly

7.6.2. 250 ppm. Transfer 25 mL of the 10,000 ppm boric acid solution to a 2 L beaker.

Add ~ 930 mL of reagent water. While stirring adjust the pH to 6.5

- 7 using 0.01

or 0.02 N ammonium hydroxide solution. Prepare fresh weekly.

7.6.3. 4 00 ppm. Transfer 4 0 mL of the 10,000 ppm boric acid solution to a 2 L beaker.

Add ~ 875 mL of reagent water. While stirring adjust the pH to 6.5

- 7 using 0.01

or 0.02 N ammonium hydroxide solution. Prepare fresh weekly.

7.7. Ammonia Standard Solutions

7.7.1. Calibration Blank: Reagent water. Replace daily or per analytical batch.

7.7.2. Ammonia Stock Solution: Accurately weigh out, to the nearest 0.001 ± 0.0005 g,

dried (at 100 o C) ACS grade ammonium sulfate (NH 4 

## ) 2 

## SO 4 

## or ammonium

chloride (NH 4 

## Cl) to make the desired ammonia concentration in Table 1, below.

Transfer the reagent to a 1L volumetric flask and dilute to volume with reagent

wate r. Mix well by inversion. Prepare fresh monthly.

Table 1: Ammonia Stock Standard s

Ammonium Salt Ammonium Chloride Ammonium Sulfate

Molecular Weight 53.49 132.14

Ammonia

- N Concentration Ammonia Salt Weight (g)

2000 mg/L 7.641 18.877

500 mg/ L 1.910 4.719

100 mg/ L 0.382 0.944

10 mg/ L 0.038 0 .094



## 7.7.3. C alibration Standards

– A minimum of 5 calibration concentrations along with a

calibration blank will be required to prepar e the initial calibration curve and

## Page 9 of 54 ongoing calibration curve

. The calibration curve fit can be either linear or

quadratic , but must have a R value of 0.995 or higher. Prepare the calibration

standards over the dynamic range of interest as defined in Table 2 from dilutions

of the ammonia stock solution. The calibratio n standards must be prepared usin g

regent grade water and prepared fresh weekly

.

Table 2: Membrane Dynamic Range

Membrane Type Membrane Length (Inches) Concentration Calibration

Dynamic Range

(Ammonia

- N mg/L)

High Sensitivity 10 2

- 0.02 0

Standard 4 5 0 0

- 0.05 00



# 8. SAMPLE COLLECTION, PRESERVATION, SHIPMENT, DIGESTION and

STORAGE

8.1. Sample Collection

8.1.1. Coll ect and store ammonia or Kjeldahl samples in glass or high density

polyethylene bottles. Most reliable results are obtained on fresh samples.. For

preservation for up to 28 d, preserve samples by acidifying to pH <2 with sulfuric

acid upon collection and store at 6°C to just above 0°C, without freezing

8.2. Total Kjeldahl Nitrogen Digestion

8.2.1. Digest Kjeldahl sample as per approved method in 40 CFR Part 136 Table IB

(e.g. 4500

- N

org 

## - 1997)

. Digested sample is stored in a covered borosilicate

container at room temperature until analyzed. Analyze within 4 hours of digestion

completion.



# 9. QUALITY CONTROL

9.1. O ngoing data quality checks are compared with established performance criteria to

determine if the results of analyses meet the performance characteristics of the method.

Control charts of each QC check will be kept and appropriate control limits calculated.

A ny QC result that fails to meet cont rol criteria must be documented and corrective

action, including a root cause analysis, must be performed.

9.2. Initial Demonstration of Capability: A laboratory fortified blank whose concentration is

between the 10% and 50% of the dynamic range is analyzed four times. The mean

recovery and standard deviation are calculated and evaluated for acceptance.

9.2.1. Acceptance Criteria: IDC control lim it for the laboratory is based on the limits

determined in this method and s hall not exceed 82%

- 110 % with a percent

Relative Standard Deviation less than 8%

.

9.2.2. Corrective Action: If the IDC recovery falls outside of these limits, the analyst

or in strument is judged to be out of control. A root cause analysis must be

performed, corrective action taken, all findings recorded and the IDC repeated

until passed.

## Page 10 of 54 9.3. Continuing Cali bration Verification : At least one CCV standard will be prepared so as to

have a concentration in the dynamic range of the instrument

. The CCV will be run at

leas t once per each batch. The C CV percent recovery is calculated and evaluated for

acceptance.

9.3.1. Acceptance Criteria: CCV control limit for the laboratory is based on the limits

determined in this method and shall not exceed 90 %

- 110 %.

9.3.2. Corrective Action: If th e CCV recovery falls outside of these limits, the batch is

judged to be out of control. A root cause analysis must be performed, corrective

action taken, all findings recorded and the sample batch repeated.

9.4. Laboratory Reagent Blank : A LRB is analyzed as a sample at least once per batch . The

LRB concentration result will be evaluate for acceptance.

9.4.1. Acceptance Criteria : The LRB concentration result will be below the lowest

calibration standard in the dynamic range.

9.4.2. Corrective Action: If the LRB falls outside of the acceptance limit , the batch is

judged to be out of control. A root cause analysis must be performed, corrective

action taken, all findings recorded and the sample batch repeated

.

9.5. Laboratory Fortified Blank: A LFB with a concentration of ammonia betw een 10% and

50% of the dynamic range is analyzed at least once per batch. The L F B concentration

result will be evaluate for acceptance.

9.5.1. Acceptance Criteria: LFB percent recovery is based on the limits determined in

this method and shall not exceed 87 %

- 104 %.

9.5.2. Corrective Action: If the LFB recovery falls outside of these limits, the batch is

judged to be out of control. A root cause analysis must be performed, corrective

action taken, all findings recorded and the sample batch repeated

.

9.6. Laboratory Fortified Sample Matrix Spikes (LFM/ LFMD ) : A duplicate set of ammonia

or Kjeldahl samples are spiked with a known amount of ammonia with a concentration

that is between 10% and 50% of the dynamic range

9.6.1. Acceptance Criteria: The LFM/ LFMD percent recovery is based on the limits

determined in this method and shall not exceed 84%

- 115 %. The relative

percent difference (RPD) shall not exceed 20%.

9.6.2. Corrective Action: If the LFM and LFMD percent recovery or the RPD fall

outside of these limits , the batch is judged to be out of control. A root cause

analysis must be performed, corrective action taken, all findings recorded and

the sample batch repeated

.

9.7. Ongoing Demonstration of Capability (ODC): A LFB with a concentration of ammonia

between 10% and 50% of the dynamic range is analyzed at least once per batch. The

LFB percent recovery will be charted by control charts and be evaluated for acceptance

.

9.7.1. Acceptance Criteria: LFB percent recovery must stay within the control limits

calculated for the control chat s.

9.7.2. Corrective Action: If the LFB percent recovery falls outside of these control

## Page 11 of 54 limits, the batch is judged to be out of control. A root cause analysis must be

performed, corrective action taken, all findings recorded and the sample batch

repeated

.



# 10. PROC EDURE

10.1. Sample Analysis Sequence: Typical sample analysis sequence .

10.1.1. Instrument Start Up

10.1.2. Calibration zero

10.1.3. Calibration standards, 1

- 5

10.1.4. LRB

10.1.5. LFB

10.1.6. Sample used for LFM/LFMD

10.1.7. LFM

10.1.8. LFMD

10.1.9. Samples (First half of batch)

10.1.10. CCV

10.1.11. Samples (Second half of batch)

10.1.12. Repeat CCV (Option al)

10.2. Instrument Preparation

10.2.1. Start the instrument as per the Timberline TL2800 instrument manual ( or an

equivalent instrument that uses the same chemistry/determinative techniques

and can meet the QC performance criteria set in the method. ).

10.2.2. Prepare quality control samples.

10.3. Sample Preparation

10.3.1. Remove refrigerated samples from the refrigerator and warm to room

temperature.

10.3.2. Kjeldahl d igested samples are diluted 10:1 with the reagent water to achieve a

nominal 10% (wt) sulfuric acid.

10.3.3. Spike the LFB and LFM/LFMD pe r QC spiking requirement.

10.3.4. Prepare CCV standard.

10.3.5. Prepare LRB water.

10.3.6. Prepare a calibration zero that is ammonia free water.

10.3.7. Prepare five (5) calibration standards that bracket the dynamic range of the

analysis. The lowest concentration standard must be at or above the ML.

10.3.8. Transfer aliquots of all samples to autosampler tubes.

## Page 12 of 54 10.4. Initial Calibration:

10.4.1. Initial calibration is performed a t the beginning of each batch.

10.4.2. Calibrate instrument with calibration zero and five calibration standards of

ammonia

.

10.4.3. Apply linear or polynomial curve

- fitting statistics, as appropriate, to analyze the

concentration

– instrument response relationship.

10.4.3.1. Acceptance Criteria: The linear or nonlinear correlation coefficient for

standard concentrati on

- to

- instrument response shall b e greater than or

equal to 0.99 5

.

10.4.3.2. Corrective Action: If the correlation coefficient falls outside of the limit

, the initial calibration is judged to be out of control. A root cause analysis

must be performed, corrective action taken, all findings r ecorded and the

initial calibration repeated.

10.4.4. Back calculate the standard concentration of each calibration point using the

calibration equation determined by the curve fitting statistics

.

10.4.4.1. Acceptance Criteria: The back

- calculated and true concentrations s hould

agree within ± 10% and cannot exceed ± 15%.

10.4.4.2. Corrective Action: If the standard back calculations fall outside of the

limits , the initial calibration is judged to be out of control. A root cause

analysis must be performed, corrective action taken, all findings recorded

and the initial calibration repeated.

10.5. Continuing Calibration Verification:

10.5.1. A CCV is analyzed at the midpoint of the batch sample set. The CCV is prepared

from a different source (chemical lot) than that used for the calibration standards

.

10.5.1.1. Acceptance Criteria: CCV control limit for the laboratory is based on the

limits determined in this method and shall not exceed 90%

- 110 %.

10.5.1.2. Corrective Action: If the CCV recovery falls outside of these limits, the

batch is judged to be out of control. A root cause analysis must be

performed, corrective action taken, all findings recorded and the sample

batch repeated.

10.6. Sample Analysis

10.6.1. Operate the instrument as per manual instructions.

10.6.2. Report the values of all samples and QC samples analyzed.

10.6.3. Determine the appropriate timing parameters and integration times for the peaks.

10.6.4. Load the filled autosampler tubes into the autosampler and start the injection

sequence.

10.6.5. Calibrate the system by generating a calibration curve with 5 standards and an

instrument blank.

## Page 13 of 54 Not e: (For Kjeldahl samples) T he samples need to be run with a 10

- 15% (w/v) NaOH

solution to neutralize the acid (22.5% molar excess).

10.6.6. Analyze the samples and QC checks. The sample concentration should not exceed

the range of the initial calibration curve. If the sample does fall outside the range

of the calibration, a new calibration curve should be run to include the range of

the sample or the sample should be diluted with reagent water to a concentration

within the dynamic range

.



# 11. CALCULATIONS / DATA REDUCTI ON

11.1. Calculate the ammonia concentrations using the initial calibration curve generated. The

batch should be reviewed for any incorrect peak identification or poor integration.

11.2. Samples and QC sample final concentrations are calculated as follow :

11.2.1. (s x DilutedSampleConcentration) = Sample Concentration

s=Dilution Correction



## 11.3. Laboratory Reagent B lank (LRB) ; The LRB will be run at a minimum of once per

sample batch. Results are r eported as sample concentration and should be at or below the

ML. Laboratory Fortified B lank (LFB) : The LFB percent recovery is calculated as

follows:

11.3.1. Percent Recovery for LFB

Experimental Value *100= Percent Recovery LFB

Expected Value

Experimental Value = LFB Concentration det ermined experimentally

Expected Value = Known LFB concentration      



## 11.4. Initial Demonstration of Capability (IDC) is determined by calculating for four LFBs,

the mean percent recovery and standard deviation.

11.4.1. 

# ( )

i i 

### (Mean)=

n 

# x x ∑

11.4.2. 1

n 2 2

i

i=1

= 

## (StandardDeviation) 

# (X -X)

n-1 

# s   ∑        

11.4.3. 

# ( ) % Relative Standard Deviation = S/x ×100

11.5. Laboratory Fortified Sample Matrix

- Laboratory Fortified Sample Matrix D uplicate

( LFM

- LFMD ) : The LFM/LFMD percent recoveries and RPD are calculated as follows:

## Page 14 of 54 11.5.1. Percent Recovery for LFM

Spiked Value-(s x Unspiked Value) *100= Percent Recovery LFM Concentration of Spike

Spiked Value = LFM concentration determin ed experimentally

Unspiked Value = Concentration of sample before spiking

s=Diluti      

on Correction



## 11.5.2. Relative Percent Difference (RPD)



# ( )

LFM-LFMD

*100 = RPD

LFM+LFMD

2

LFM = Concentration determined for LFM

LFMD = Concentration determined for LFM duplicate      

   

     

11.6. Continuing Calibration Verification (CCV): Check standards will be prepared so as to

have a concentration between the lower and upper calibration of the dynamic range

.

11.6.1. CCV Value - InitialStandard Value 100 Percent Difference

InitialStandard Value ∗ =



## 11.7. Control C harts : Control charts will be kept for LFB and LFM percent recovery per

sample batch, LFM and LFMD RPD per sample batch, and LRB concentration. Trends

will be calculated to show whether the values determined go outside the control limits . If

th ese trends exceed control limits of this method, then corrective action (Root Cause

Analysis) must be performed.

11.8. Corrective A ction (Root Cause Analysis) : The laboratory analyst(s) and laboratory

management will perform a root cause analysis for any QC fail ures. The analysis will

have at a minimum the following areas described in detail:

11.8.1. Identify the problem : Ident i fy the QC failure. Include instrument, reagent,

sampling, personnel and any other problems.

11.8.2. Investi gate to identify the root cause : Determine how each problem identified

interacted with each other to create the QC problem.

11.8.3. Come up with the solution : Develop an encompassing solution to address all

problems that created the QC failure.

11.8.4. Implement the solution : Develop an implementation plan that includes all

components of the developed solution and have laboratory management

implement it.

11.8.5. Document the solution : Document all corrective action steps taken under

laboratory management implementation of the corrective action.

## Page 15 of 54 11.8.6. Communicate the solution : Develop training and management programs to

communicate and evaluate all personnel included in the corrective action

solution.

11.8.7. Evaluate th e effectiveness of the solution: Document QC results in trend charts

and laboratory staff performance to va lidate corrective action solution.



# 12. METHOD PERFORMANCE

12.1. Method Detection Limit and Method Limit Study (MDL

- ML):

12.1.1. MDL and ML are determined for the initial start

- up of the instrument prior to

any sample analysis and when the instrument has had maintenance or repairs of

the membrane, detector or any other internal analytical components. These

requirements do not include consumable supplies or reagents. Analytical

procedures for the MDL and ML are listed in the current promulgated 40 CFR

136 Appendix B

.

12.1.2. Prepare seven samples at three to five times the estimated MDL concentration.

The MDL samples are prepared in the Synthetic

12.1.3. Prepare and analyze the MDL standards as described in Section 10.

12.1.4. Calculate the average concentration found in μg/L or mg/L, and the standa rd

deviation of the concentration(s) for each analyte

.

12.1.5. The MDL is calculated as Students t for the 99th percentile times the standard

deviation of the MDL replicate results, following the procedure at 40 CFR 136,

Appendix B.

12.1.6. The ML is calculated as per “ G uidelines Establishing Test Procedures for the

Analysis of Pollutants Under the Clean Water Act; National Primary Drinking

Water Regulations; and National Secondary Drinking Water Regulations:

Analysis and Sampling Procedures ”.

12.1.7. (MDL x 3.18) = ML



## 12.2. I nstrument Detection Limit Study:

12.2.1. Prepare three laboratory reagent blanks.

12.2.2. Analyze the IDL blanks as per Section 10.

12.2.3. The IDL is calculated as per Standard Methods for the Examination of Water

and Wastewater Part 1000.

12.2.4. LRB

LRB 

## Instrument Detection Limit = (3 × S )

S = Standard Deviation of Laboratory Reag ent Blanks



## 12.3. Demonstration of Capabilities

12.3.1. All laboratory personnel are required to perform an initial demonstration of

capability (IDC) on the instrument they will be using for analysis prior to

testing samples. Ongoing demonstration of capability must be demonstrated by

## Page 16 of 54 control charts with LFBs being analyzed at least once per sample batch. Initial

and ongoing demonstrations of capabilities are conducted as follows.

12.3.2. Initial Demonstration of Capability Analyst Proficiency

- Four LFBs are

analyzed using the same instrum ental conditions and procedures used to

analyze samples. Using these four LFBs demonstrates the analyst’s ability to

optimize and calibrate the instrument and to prepare analytical solutions.

Calculate the average percent recovery and standard deviation of the recovery

.

12.3.2.1. Acceptance Criteria: IDC control limit for the laboratory is based on the

limits determined in this method and shall not exceed 82%

- 110 % with a

percent Relative Standard Deviation less than 8%.

12.3.2.2. Corrective Action: If the IDC recovery falls outside of these limits, the

analyst or instrument is judged to be out of control. A root cause analysis

must be performed, corrective action taken, all findings recorded and the

IDC repeated until passed.

12.3.3. Ongoing Demonstration of Capability Analyst Profic iency : A LFB is analyzed

using the same instrumental conditions and procedures us ed to analyze samples

at least once per batch. The LFB percent recovery will be charted by control

charts and be evaluated for acceptance.

12.3.3.1. Acceptance Criteria: LFB percent rec overy must stay within the control

limits calculated for the control chats.

12.3.3.2. Corrective Action: If the LFB percent recovery falls outside of these

control limits, the batch is judged to be out of control. A root cause

analysis must be performed, correctiv e action taken, all findings recorded

and the sample batch repeated

.



# 13. POLLUTION CONTROL

13.1. It is the laboratory’s responsibility to comply with all federal, state, and local regulations

governing waste management, particularly the hazardous waste identification rules and

land disposal restrictions, and to protect air, water, and land by minimizing and control

all releases from fume hoods and bench operations. Compliance with all sewage

discharge permits and regulations is also required

.



# 14. WASTE MANAG EMENT

14.1. There are no standards or reagents used in this method at the concentrations required that

pose a threat to the environment . Refer to Local, State or Federal for correct disposal of

all chemicals.



# 15. REFERENCES / BIBLIOGRAPHY

15.1. EPA, Guidelines Establishing Test Proceedures for the Analysis of Pollutants Under the

Clean Water Act; National Primary Drinking Water Regulations; and National

Secondary Drinking Water Regulations: Analysis and Sampling Proceedures. 2007.

72 (47): p. 11200

- 11249.

## Page 17 of 54 15.2. EPA, 40 CFR Part 136

- Guidelines Establishing Test proceedures for the Analysis of

Pollutants, Appendix B , 1984.

15.3. EPA, Protocol for EPA Approval of New Methods for Organic and Inorganic Analytes

in W a stewater and Drinking Water

. 1999

.

15.4. Eaton, E., Clesceri, L., Rice , E., , ed. Standard Methods for the Examination of Water

and Wastewater, 21st Edition . 2005, APHA, AWWA, WEF.

15.5. ASTM, Standard Test Methods for Ammonia Nitrogen In Water D1426

- 03 A . 2003,

ASTM International.

15.6. ASTM, Standard Practices for determination of Precision and Bias of Applicable Test

Methods of Committee D19 In Water D2777

- 0 6 200 6 , ASTM International

15.7. EPA. Draft 2009 Update of Aquatic Life Ambient Water Quality Criteria for Ammonia

-

Freshwater 2010; Available from:

http://www.epa.gov/waterscience/criteria/ammonia/factsheet2.html

.

15.8. Bruce O. Mansell, L.D.V., Edward D. Schroeder Automated Separation and

Conductimetric Determination of Inorganic Nitrogen. Journal of Envior nmental

Engineering, 2000. 126 (8): p. 778

- 780.

15.9. Skoog, D.A., et al, “Fundamentals of Analytical Chemistry” , Eighth Edition, 2004,

Thomson, Brooks/Cole.

## Page 18 of 54 

# 16. ATTACHMENTS

Note: All concentrations are for Ammonia

- N

16.1. Table A : General Instrument Parameters

16.2. Table B : 4 inch Membrane Pooled MDLs for Individual Laboratories and All

Laboratories

16.3. Table C : 10 inch Membrane Pooled MDLs for Individual Laboratories and All

Laboratories

16.4. Table D : LFM/LFMD Recoveries

16.5. Table E : 4 Inch Membrane LFM/LFMD Calculations

16.6. Table F :10 Inch Membrane LFM/LFMD Calculations

16.7. Table G 1

- 2 : 4 I nch membrane LFB Overall Percent Recovery

16.8. Table H 1

- 2 : 10 Inch Membrane LFB Overall Percent Recovery

16.9. Table I 1

- 3 : 4 Inch Membrane LFB Bias and Precision

16.10. Table J 1

- 3 : 10 Inch Membrane LFB Bias and Precision

16.11. Table K 1

- 2 : 4 Inch Membrane Calibration Verification

16.12. Table L : 10 Inch Membrane Calibration Verification

16.13. Table M 1

- 2 : 4 Inch Membrane Initial and Ongoing Precision and Recovery

16.14. Table N 1

- 2 : 10 Inch Membrane Initial and Ongoing Precision and Recovery

16.15. Table O 1

- 2 : CCV Low Standard Bias and Precision 4 Inch Membrane

16.16. Table P : CCV Low and High Standard Bias and Precision 10 Inch Membrane

16.17. Table Q : Youden Pair Recovery

- 4 Inch Membrane

16.18. Table R : Single Operator Standard Deviation and %RSD

– 4 Inch M embrane

16.19. Table S :Youden Pair Recovery

- 10 Inch Membrane

16.20. Table T : Single Operator Standard Deviation and %RSD

– 10 Inch Membrane

16.21. Table U : Laboratory Reagent Blank

– Instrument Detection Limit 4 Inch Membrane

16.22. Table V : Laboratory Reagent Blank

– Instrument De tection Limit 10 Inch Membrane

## Page 19 of 54 Table A : General Instrument Parameters

Lab 1 2 3 4 5 6 7 8 9 10 9 6

Timberline

Instrument

Model # TL

- 200 2800 TL

- 2800 TL

- 201 TL

- 2800 / SN

121209001 TL 2800 TL2100 TL 2800 TL

- 2800 TL

- 2100 TL

- 2800 TL 2800

Membrane

Length (Inches) 4 Inches 4 Inches 4 Inches 4 Inches 4 Inches 4 Inches 4 Inches 4 Inches 4 Inches 10 Inches 10 Inches 10 inch

Gain (# or

Letter) C 1 C 10 1 1000 D 10 10 10 100 1000

Attenuation

(# or Letter) 2 2 1 4 div 4 div 8 N/A div 8 div 4 div 1 div 4 div 2

Buffer

Concentration

and pH 150 ppm Boric

Acid pH 7.2 .1g boric acid

per liter of

water pH =

7.02 0.1 g/L Boric

Acid at pH of

7.0 pH=7.2 | 28

-

30%

NH3OH=3.0m

L/L 3.75 ml of

that Liter +

0.1g Boric

Acid 250 ppm / pH

= 6.5 250 ppm pH

6.51 Conc = 0.01%

PH = 6.99 250 ppm, pH

6.9 400 ppm boric

acid, pH 6.0 100 mg/L, pH

6.5 400ppm boric

acid, pH 6.0 400 ppm pH

6.51

Caustic

Concentration 0.05 10g DTPA

and 25g

potassium

hyd r oxide per

liter of water 25 g/L

Potassium

Hydroxide and

10 g/L of

DTPA 0.97N NaOH

(38.9g)

11.1g/L DTPA 5% NaOH 0.05 5 % KOH +

2 % DTPA 15% NaOH 5% KOH 0.10% 1% KOH 1%

Injection Time

(seconds) 15 20 15 20 seconds 10 s 20 24 seconds 15 sec 25 20 25 20 sec

Pump speed

(rpm) 45 29 40 50 28 rpm 30 45 (rpm) 28 40 28 40 30

Sample Matrix

Type 40 CFR 442

Commercial

Truck Wash Raw POTW

Influent Final POTW

Effluent

Dechlorinated 40 CFR 430

Paper Pulp

Mill Effluent POTW Return

Waste

Activated

Sludge

Centrifugation

Liquor 40 CFR 433

Metal Finisher

Effluent POTW

Primary

Clarifier

Effluent TKN

Waste Water

Manure

Lagoon POTW

Effluent, Non

Disinfected POTW

Receiving

Watershed POTW

Eff luent Non

Disinfected

. 40 CFR 433

Metal Finisher

Effluent

## Page 20 of 54 Table B : 4 inch Membrane Pooled MDLs for Individual Laboratories and All Laboratories

Lab

1Standard or SampleSample Concentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageMeasurement 1Measurement 1Calc 1AverageMeasurement 2Measurement 2Calc 1AverageMeasurement 3Measurement 3Calc 1Sum NIndividualLaboratoriesIndividualLaboratoryPooled StandardDeviationIndividualLaboratoriesStudent TIndividual LaboratoryPooled MDLTotal LaboratoriesMDLTotal Laboratories MLReporting ML

MDL Sample 1 50 49.8 48.9 49.3 42.1 268.116366 40.9 262.1394838 40.5 260.1670487 18 6.626641929 2.552 17 14 4 6 5 E+0 1

MDL Sample 2 50 51.6 47.9 46.6 42.1 40.9 40.5

MDL Sample 3 50 45.0 45.5 44.9 42.1 40.9 40.5

MDL Sample 4 50 39.5 39.3 39.0 42.1 40.9 40.5

MDL Sample 5 50 35.7 32.7 31.5 42.1 40.9 40.5

MDL Sample 6 50 37.2 35.7 36.6 42.1 40.9 40.5

MDL Sample 7 50 36.0 36.2 35.4 42.1 40.9 40.5

2Standard or SampleSample Concentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageMeasurement 1Measurement 1Calc 1AverageMeasurement 2Measurement 2Calc 1AverageMeasurement 3Measurement 3Calc 1Sum NIndividualLaboratoriesIndividualLaboratoryPooled StandardDeviationIndividualLaboratoriesStudent TIndividual LaboratoryPooled MDL

MDL Sample 1 50 46.3 45.1 34.0 46.4 22.10172622 48.8 278.643543 42.8 609.387987 18 7.110763579 2.552 18

MDL Sample 2 50 46.2 44.0 33.1 46.4 48.8 42.8

MDL Sample 3 50 44.4 40.9 34.4 46.4 48.8 42.8

MDL Sample 4 50 44.0 47.6 40.8 46.4 48.8 42.8

MDL Sample 5 50 46.4 50.3 45.4 46.4 48.8 42.8

MDL Sample 6 50 49.5 56.0 54.6 46.4 48.8 42.8

MDL Sample 7 50 48.2 58.0 57.5 46.4 48.8 42.8

## Page 21 of 54 3Standard or SampleSampleConcentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageMeasurement 1Measurement 1Calc 1AverageMeasurement 2Measurement 2Calc 1AverageMeasurement 3Measurement 3Calc 1Sum NIndividualLaboratoriesIndividualLaboratoryPooled StandardDeviationIndividualLaboratoriesStudent TIndividual LaboratoryPooled MDL

MDL Sample 1 50 36.5 39.5 29.7 47.8 1000.816948 42.3 2200.645448 55.7 1363.948179 18 15.92588838 2.552 41

MDL Sample 2 50 39.2 28.9 39.6 47.8 42.3 55.7

MDL Sample 3 50 63.7 39.2 66.8 47.8 42.3 55.7

MDL Sample 4 50 49.3 38.5 63.6 47.8 42.3 55.7

MDL Sample 5 50 33.6 73.0 67.9 47.8 42.3 55.7

MDL Sample 6 50 66.3 18.4 57.2 47.8 42.3 55.7

MDL Sample 7 50 46.0 58.5 65.1 47.8 42.3 55.7

4Standard or SampleSampleConcentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageMeasurement 1Measurement 1Calc 1AverageMeasurement 2Measurement 2Calc 1AverageMeasurement 3Measurement 3Calc 1Sum NIndividualLaboratoriesIndividualLaboratoryPooled StandardDeviationIndividualLaboratoriesStudent TIndividual LaboratoryPooled MDL

MDL Sample 1 50 33.4 36.2 38.2 35.3 295.9283579 36.0 442.95748 35.5 175.0779986 18 7.125711802 2.552 18

MDL Sample 2 50 29.3 22.5 33.0 35.3 36.0 35.5

MDL Sample 3 50 31.0 38.3 37.3 35.3 36.0 35.5

MDL Sample 4 50 37.7 36.2 31.9 35.3 36.0 35.5

MDL Sample 5 50 30.9 30.6 36.0 35.3 36.0 35.5

MDL Sample 6 50 49.9 50.8 44.6 35.3 36.0 35.5

MDL Sample 7 50 34.6 37.5 27.6 35.3 36.0 35.5

## Page 22 of 54 5Standard or SampleSampleConcentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageMeasurement 1Measurement 1Calc 1AverageMeasurement 2Measurement 2Calc 1AverageMeasurement 3Measurement 3Calc 1Sum NIndividualLaboratoriesIndividualLaboratoryPooled StandardDeviationIndividualLaboratoriesStudent TIndividual LaboratoryPooled MDL

MDL Sample 1 50 53.8 52.5 50.2 49.8 67.595018 50.5 54.274461 49.8 40.76319743 18 3.005852407 2.552 8

MDL Sample 2 50 53.9 50.3 53.6 49.8 50.5 49.8

MDL Sample 3 50 50.1 51.3 50.4 49.8 50.5 49.8

MDL Sample 4 50 51.2 55.5 50.2 49.8 50.5 49.8

MDL Sample 5 50 48.0 48.5 47.4 49.8 50.5 49.8

MDL Sample 6 50 46.4 47.2 45.6 49.8 50.5 49.8

MDL Sample 7 50 45.6 47.9 51.6 49.8 50.5 49.8

6Standard or SampleSampleConcentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageMeasurement 1Measurement 1Calc 1AverageMeasurement 2Measurement 2Calc 1AverageMeasurement 3Measurement 3Calc 1Sum NIndividualLaboratoriesIndividualLaboratoryPooled StandardDeviationIndividualLaboratoriesStudent TIndividual LaboratoryPooled MDL

MDL Sample 1 50 52.5 53.8 52.8 50.9 13.4269972 50.1 33.26565203 49.8 18.15411917 18 1.89805117 2.552 5

MDL Sample 2 50 50.0 48.2 49.3 50.9 50.1 49.8

MDL Sample 3 50 50.1 50.4 49.4 50.9 50.1 49.8

MDL Sample 4 50 50.3 49.5 48.2 50.9 50.1 49.8

MDL Sample 5 50 51.1 49.8 49.7 50.9 50.1 49.8

MDL Sample 6 50 53.4 51.7 51.3 50.9 50.1 49.8

MDL Sample 7 50 49.2 47.3 47.7 50.9 50.1 49.8

## Page 23 of 54 7Standard or SampleSampleConcentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageMeasurement 1Measurement 1Calc 1AverageMeasurement 2Measurement 2Calc 1AverageMeasurement 3Measurement 3Calc 1Sum NIndividualLaboratoriesIndividualLaboratoryPooled StandardDeviationIndividualLaboratoriesStudent TIndividual LaboratoryPooled MDL

MDL Sample 1 50 52.2 53.4 48.7 52.9 56.08613904 53.6 23.69668369 52.1 47.21292083 18 2.656185063 2.552 7

MDL Sample 2 50 54.6 50.3 48.4 52.9 53.6 52.1

MDL Sample 3 50 46.7 54.2 50.9 52.9 53.6 52.1

MDL Sample 4 50 52.6 54.5 54.0 52.9 53.6 52.1

MDL Sample 5 50 56.2 52.3 52.5 52.9 53.6 52.1

MDL Sample 6 50 53.3 55.9 54.7 52.9 53.6 52.1

MDL Sample 7 50 54.7 54.6 55.3 52.9 53.6 52.1

8Standard or SampleSampleConcentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageMeasurement 1Measurement 1Calc 1AverageMeasurement 2Measurement 2Calc 1AverageMeasurement 3Measurement 3Calc 1Sum NIndividualLaboratoriesIndividualLaboratoryPooled StandardDeviationIndividualLaboratoriesStudent TIndividual LaboratoryPooled MDL

MDL Sample 1 50 50.4 30.6 48.7 48.0 86.49537546 41.3 609.6544895 47.3 17.89875795 17 6.480961362 2.567 17

MDL Sample 2 50 † 50.6 44.3 48.0 41.3 47.3

MDL Sample 3 50 44.1 49.2 48.0 48.0 41.3 47.3

MDL Sample 4 50 53.1 39.1 48.7 48.0 41.3 47.3

MDL Sample 5 50 42.0 35.9 45.6 48.0 41.3 47.3

MDL Sample 6 50 49.9 42.8 47.4 48.0 41.3 47.3

MDL Sample 7 50 48.5 41.0 48.6 48.0 41.3 47.3

## Page 24 of 54 9Standard or SampleSampleConcentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageMeasurement 1Measurement 1Calc 1AverageMeasurement 2Measurement 2Calc 1AverageMeasurement 3Measurement 3Calc 1Sum NIndividualLaboratoriesIndividualLaboratoryPooled StandardDeviationIndividualLaboratoriesStudent TIndividual LaboratoryPooled MDL

MDL Sample 1 50 52.4 48.9 51.1 47.7 71.10356752 46.0 148.0760933 45.5 157.3451706 18 4.57362506 2.552 12

MDL Sample 2 50 46.6 48.0 48.2 47.7 46.0 45.5

MDL Sample 3 50 49.9 54.2 46.9 47.7 46.0 45.5

MDL Sample 4 50 45.8 42.3 40.5 47.7 46.0 45.5

MDL Sample 5 50 43.5 42.4 38.9 47.7 46.0 45.5

MDL Sample 6 50 44.5 43.7 51.3 47.7 46.0 45.5

MDL Sample 7 50 51.1 42.1 41.8 47.7 46.0 45.5



### †: Data value determined to be an outlier

## Page 25 of 54 Table C : 10 inch Membrane Pooled MDLs for Individual Laboratories and All Laboratories

Lab

10Standard or SampleSample Concentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageMeasurement 1Measurement 1Calc 1AverageMeasurement 2Measurement 2Calc 1AverageMeasurement 3Measurement 3Calc 1Sum NIndividual LaboratoriesIndividualLaboratory PooledStandard DeviationIndividual LaboratoriesStudent TIndividual Laboratory PooledMDLTotal Laboratories MDLTotal Laboratories MLReporting ML

MDL

Sample 1 20 20.2 20.4 20.7 19.1 10.22363599 19.3 4.685146617 19.4 4.310019405 18 1.033301129 2.552 3 2 7 1.E+01

MDL

Sample 2 20 18.4 18.3 20.0 19.1 19.3 19.4

MDL

Sample 3 20 21.3 20.6 20.0 19.1 19.3 19.4

MDL

Sample 4 20 18.9 18.8 18.5 19.1 19.3 19.4

MDL

Sample 5 20 18.8 19.0 19.3 19.1 19.3 19.4

MDL

Sample 6 20 19.1 19.2 18.8 19.1 19.3 19.4

MDL

Sample 7 20 17.3 18.8 18.5 19.1 19.3 19.4

9SampleConcentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageMeasurement 1Measurement 1Calc 1AverageMeasurement 2Measurement 2Calc 1AverageMeasurement 3Measurement 3Calc 1Sum NIndividual LaboratoriesIndividualLaboratory PooledStandard DeviationIndividual LaboratoriesStudent TIndividual Laboratory PooledMDLSampleConcentration(PPB N as Ammonia)

MDL

Sample 1 20 18.1 23.0 20.5 20.0 14.00052526 20.5 16.54387347 19.7 14.37793392 18 1.579773764 2.552 4

MDL

Sample 2 20 22.5 20.5 19.6 20.0 20.5 19.7

MDL

Sample 3 20 20.8 21.5 22.5 20.0 20.5 19.7

MDL

Sample 4 20 20.5 18.2 18.3 20.0 20.5 19.7

## Page 26 of 54 MDL

Sample 5 20 20.2 18.9 20.3 20.0 20.5 19.7

MDL

Sample 6 20 18.3 20.9 18.7 20.0 20.5 19.7

MDL

Sample 7 20 19.8 20.6 18.1 20.0 20.5 19.7

6SampleConcentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageMeasurement 1Measurement 1Calc 1AverageMeasurement 2Measurement 2Calc 1AverageMeasurement 3Measurement 3Calc 1Sum NIndividualLaboratoriesIndividualLaboratory PooledStandard DeviationIndividual LaboratoriesStudent TIndividual Laboratory PooledMDLSampleConcentration(PPB N as Ammonia)

MDL

Sample 1 20 23.1 23.1 23.0 20.4 13.27821238 20.2 14.4486110 9 20.1 16.10179668 18 1.56042409 2.552 4

MDL

Sample 2 20 20.0 19.2 18.1 20.4 20.2 20.1

MDL

Sample 3 20 20.1 18.8 19.7 20.4 20.2 20.1

MDL

Sample 4 20 20.7 20.6 18.5 20.4 20.2 20.1

MDL

Sample 5 20 20.1 19.4 20.7 20.4 20.2 20.1

MDL

Sample 6 20 20.7 19.0 20.7 20.4 20.2 20.1

MDL

Sample 7 20 18.1 21.0 19.8 20.4 20.2 20.1

## Page 27 of 54 Table D : LFM/LFMD Recoveries

4 Inch Membrane Matrix Spike Recovery Matrix Spike Duplicate

Recovery Relative Percent Difference

1 40 CFR 442, Commercial Truck Wash 114.00% 125.04% 9.24%

2 Raw POTW Influent 111.77% 91.80% 19.61%

3 Final POTW Effluent, Dechlorinated 132.73% 95.99% 32.12%

4 40 CFR 430, Paper Pulp Mill Effluent 96.06% 98.83% 2.85%

5 POTW Return Waste Activated Sludge Centrifugation Liquor 111.96% 111.05% 0.82%

6 40 CFR 433, Metal Finisher Effluent 115.96% 118.08% 1.81%

7 POTW Primary Clarifier Effluent 100.06% 98.23% 1.85%

8

Manure Lagoon Waste Water (TKN) 118.38% 119.13% 0.64%

9 POTW Effluent, Non Disinfected. 102.92% 111.82% 8.28%

10 Inch Membrane Matrix Spike Recovery Matrix Spike Duplicate

Recovery Relative Percent Difference

10 POTW Receiving Watershed 101.12% 107.96% 6.54%

6 40 CFR 433, Metal Finisher Effluent 100.15% 92.63% 7.80%

9 POTW Effluent, Non Disinfected. 106.27% 98.58% 7.50%

## Page 28 of 54 Table E : 4 Inch Membrane LFM/LFMD Calculations

LFM

- LFMD Percent Recovery MS/MSD Calculation

Lab Matrix Spike

Recovery Matrix Spike

Duplicate

Recovery Individual

Laboratory

Mean Individual

Laboratory

Standard

Deviation Individual

Laboratory

Relative

Percent

Difference

(RPD) All Laboratory

Mean Pooled Within

Laboratory

Standard

Deviation (sw) Between

Laboratory

Standard

Deviation of the

Mean Results

(sb) RSD IPR(max) IPR Combined

Standard

Dev iation (sc) All Laboratory

MS/MSD

Lower Limit All Laboratory

MS/MSD

Upper Limit

1 114.00% 125.04% 119.52% 7.81% 9.24% 109.66% 10.45% 8.56% 30.50% 11.67% 83.99% 135.32%

2 111.77% 91.80% 101.79% 14.12% 19.61%

3 132.73% 95.99% 114.36% 25.98% 32.12%

4 96.06% 98.83% 97.44% 1.96% 2.85%

5 111.96% 111.05% 111.51% 0.65% 0.82%

6 115.96% 118.08% 117.02% 1.50% 1.81%

7 100.06% 98.23% 99.14% 1.29% 1.85%

8 118.38% 119.13% 118.76% 0.53% 0.64%

9 102.92% 111.82% 107.37% 6.29% 8.28%

## Page 29 of 54 Table F : 10 Inch Membrane LFM/LFMD Calculations

LFM

- LFMD Percent Recovery MS/MSD Calculation

Lab Matrix Spike

Recovery Matrix Spike

Duplicate

Recovery Individual

Laboratory

Mean Individual

Laboratory

Standard

Deviation Individual

Laboratory

Relative

Percent

Difference

(RPD) All Laboratory

Mean Pooled Within

Laboratory

Standard

Deviation (sw) Between

Laboratory

Standard

Deviation of the

Mean Results

(sb) RPD (max) IPR Combined

Standard

Deviation (sc) All Laboratory

MS/MSD

Lower Limit All Laboratory

MS/MSD

Uppe r Limit

10 101.12% 107.96% 104.54% 4.84% 6.54% 101.12% 5.20% 4.23% 23.15% 6.11% 87.67% 114.57%

6 100.15% 92.63% 96.39% 5.32% 7.80%

9 106.27% 98.58% 102.43% 5.43% 7.50%

## Page 30 of 54 Table G 1 : 4 inch Membrane

- LFB Overall Percent Recovery

LFB Recovery Percent RecoveryLabIPR Reading1IPR Reading2IPR Reading3IPR Reading4OPR Reading1OPR Reading2OPR Reading3OPR Reading4OPR Reading5Standard Value(PPB N)NIPR Reading1IPR Reading2IPR Reading3IPR Reading4OPR Reading1OPRReading2OPR Reading3OPR Reading4OPR Reading5

1 985.75 1018.92 1025.69 1029.08 852.95 886.68 1039.77 898.00 1000.00 8 98.58% 101.89% 102.57% 102.91% 85.30% 88.67% 103.98% 89.80%

2 933.71 865.26 839.73 990.04 814.57 790.78 815.64 1043.32 1038.35 1000.00 9 93.37% 86.53% 83.97% 99.00% 81.46% 79.08% 81.56% 104.33% 103.83%

3 973.94 1041.90 1057.47 952.63 933.53 1014.73 964.00 1009.15 1000.00 8 97.39% 104.19% 105.75% 95.26% 93.35% 101.47% 96.40% 100.92%

4 1053.00 1062.00 1046.00 1046.00 1040.00 1030.00 1000.00 1000.00 1000.00 8 105.30% 106.20% 104.60% 104.60% 104.00% 103.00% 100.00% 100.00%

5 990.56 973.42 956.67 974.06 942.77 940.92 940.13 931.70 1000.00 8 99.06% 97.34% 95.67% 97.41% 94.28% 94.09% 94.01% 93.17%

6 1022.21 1069.33 990.91 987.07 1016.58 1018.54 1027.27 1035.52 1000.00 8 102.22% 106.93% 99.09% 98.71% 101.66% 101.85% 102.73% 103.55%

7 914.39 904.69 899.01 884.62 954.38 999.53 891.61 912.52 1000.00 8 91.44% 90.47% 89.90% 88.46% 95.44% 99.95% 89.16% 91.25%

8 951.92 977.21 1021.87 947.83 921.95 961.28 857.54 902.88 1000.00 8 95.19% 97.72% 102.19% 94.78% 92.20% 96.13% 85.75% 90.29%

9 911.86 909.63 892.98 889.47 879.27 851.10 852.64 841.43 1000.00 8 91.19% 90.96% 89.30% 88.95% 87.93% 85.11% 85.26% 84.14%

## Page 31 of 54 Table G 2 : 4 inch membrane

- LFB Overall Percent Recovery

Lab Single Lab Average % Recovery Single Lab Standard Deviation Total Lab Average % Recovery Total Lab STANDARD DEVIATION

1 96.71% 0.08 95.67% 0.07

2 90.35% 0.10

3 99.34% 0.04

4 103.46% 0.02

5 95.63% 0.02

6 102.09% 0.03

7 92.01% 0.04

8 94.28% 0.05

9 87.85% 0.03

## Page 32 of 54 Table H 1 : 10 inch Membrane

- LFB Overall Percent Recovery

LFB recovery Percent Recovery

LabIPRReading1IPR Reading2IPR Reading3IPR Reading4OPR Reading1OPR Reading2OPR Reading3OPR Reading4Standard Value(PPB N)NIPR Reading1IPR Reading2IPR Reading3IPR Reading4OPR Reading1OPR Reading2OPR Reading3OPR Reading4

10 48.48 48.05 46.91 46.79 47.78 46.51 47.60 49.04 50.00 8 96.96% 96.10% 93.81% 93.59% 95.56% 93.02% 95.19% 98.07%

6 51.33 48.78 46.65 47.49 48.84 50.28 48.13 49.09 50.00 8 102.66% 97.55% 93.30% 94.97% 97.68% 100.56% 96.26% 98.19%

9 51.38 49.48 46.51 47.76 51.17 46.04 44.42 43.61 50.00 8 102.76% 98.97% 93.03% 95.51% 102.34% 92.09% 88.85% 87.22%

## Page 33 of 54 Table H 2 : 10 Inch Membrane

- LFB Overall Percent Recovery

Single Lab Average % Recovery Single Lab S tandard D eviation Total Lab Average % Recovery Total Lab S tandard Deviation

95.29% 0.02 96.01% 0.04

97.65% 0.03

95.10% 0.06

## Page 34 of 54 Table I 1 : 4 Inch Membrane LFB Bias and Precision

LFB Recovery DifferenceLabIPR Reading1IPR Reading2IPR Reading3IPR Reading4OPR Reading1OPR Reading2OPR Reading3OPR Reading4OPR Reading5StandardValue(PPB N)NIPR Reading1IPR Reading2IPR Reading3IPR Reading4OPR Reading1OPR Reading2OPR Reading3OPR Reading4OPR Reading5

1 985.75 1018.92 1025.69 1029.08 852.95 886.68 1039.77 898.00 1000.00 8

- 14.25 18.92 25.69 29.08

- 147.05

- 113.32 39.77

- 102.00

2

933.71 865.26 839.73 990.04 814.57 790.78 815.64 1043.32 1038.35 1000.00 9

- 66.29

- 134.74

- 160.27

- 9.96

- 185.43

- 209.22

- 184.36 43.32 38.35

3

973.94 1041.90 1057.47 952.63 933.53 1014.73 964.00 1009.15 1000.00 8

- 26.06 41.90 57.47

- 47.37

- 66.47 14.73

- 36.00 9.15

4c 1053.00 1062.00 1046.00 1046.00 1040.00 1030.00 1000.00 1000.00 1000.00 8 53.00 62.00 46.00 46.00 40.00 30.00 0.00 0.00

5

990.56 973.42 956.67 974.06 942.77 940.92 940.13 931.70 1000.00 8

- 9.44

- 26.58

- 43.33

- 25.94

- 57.23

- 59.09

- 59.87

- 68.30

6

1022.21 1069.33 990.91 987.07 1016.58 1018.54 1027.27 1035.52 1000.00 8 22.21 69.33

- 9.09

- 12.93 16.58 18.54 27.27 35.52

7

914.39 904.69 899.01 884.62 954.38 999.53 891.61 912.52 1000.00 8

- 85.61

- 95.31

- 100.99

- 115.38

- 45.62

- 0.47

- 108.39

- 87.48

8

951.92 977.21 1021.87 947.83 921.95 961.28 857.54 902.88 1000.00 8

- 48.08

- 22.79 21.87

- 52.17

- 78.05

- 38.72

- 142.46

- 97.12

9

911.86 909.63 892.98 889.47 879.27 851.10 852.64 841.43 1000.00 8

- 88.14

- 90.37

- 107.02

- 110.53

- 120.73

- 148.90

- 147.36

- 158.57

## Page 35 of 54 Table I 2 : 4 Inch Membrane LFB Bias and Precision

LFB Squared DifferenceLabIPR Reading1IPR Reading2IPR Reading3IPR Reading4OPR Reading1OPR Reading2OPR Reading3OPR Reading4OPR Reading5

1 203.0625 357.9664 659.9761 845.6464 21623.7025 12841.4224 1581.6529 10404.0000

2 4394.2315 18155.9455 25687.1140 99.1817 34383.9140 43773.4268 33988.6096 1876.5358 1470.6458

3 678.9464 1755.7022 3302.6630 2243.7085 4418.2077 216.9140 1296.0144 83.8049

4c 2809.0000 3844.0000 2116.0000 2116.0000 1600.0000 900.0000 0.0000 0.0000

5 89.1891 706.7091 1877.4022 672.7280 3274.8151 3491.0372 3584.2972 4665.5730

6 493.2467 4806.1822 82.6159 167.2118 275.0603 343.8976 743.8574 1261.6790

7 7329.6234 9084.5813 10198.1459 13311.9767 2081.5138 0.2174 11748.0453 7653.3925

8 2311.8787 519.2018 478.1220 2721.2916 6091.6464 1499.0835 20293.7119 9431.7117

9 7769.3261 8165.9240 11453.9940 12216.1353 14575.5897 22171.7288 21716.3306 25144.3472

## Page 36 of 54 Table I 3 : 4 Inch Membrane LFB Bias and Precision

LFB Bias and PrecisionLabSingle LabBias (PPB)Single LabPrecision(PPB)Total LabBias (PPB)Total LabPrecision(PPB)

1

- 33 83

- 43 88

2

- 97 143

3

- 7 45

4c 35 44

5

- 44 51

6 21 34

7

- 80 94

8

- 57 79

9

- 121 133

## Page 37 of 54 Table J 1 : 10 Inch Membrane LFB Bias and Precision

LFB Recovery DifferenceLabIPR Reading1IPR Reading2IPR Reading3IPR Reading4OPR Reading1OPR Reading2OPRReading3OPR Reading4Standard Value(PPB N)NIPR Reading1IPR Reading2IPR Reading3IPR Reading4OPR Reading1OPR Reading2OPR Reading3OPR Reading4

10 48.48 48.05 46.91 46.79 47.78 46.51 47.60 49.04 50.00 8

- 1.52

- 1.95

- 3.09

- 3.21

- 2.22

- 3.49

- 2.40

- 0.96

6 51.33 48.78 46.65 47.49 48.84 50.28 48.13 49.09 50.00 8 1.33

- 1.22

- 3.35

- 2.51

- 1.16 0.28

- 1.87

- 0.91

9 51.38 49.48 46.51 47.76 51.17 46.04 44.42 43.61 50.00 8 1.38

- 0.52

- 3.49

- 2.24 1.17

- 3.96

- 5.58

- 6.39

## Page 38 of 54 Table J 2 : 10 Inch Membrane LFB Bias and Precision

LFB Squared Differen c eLabIPR Reading1IPR Reading2IPR Reading3IPR Reading4OPR Reading1OPR Reading2OPR Reading3OPR Reading4

10 2.3036 3.7950 9.5652 10.2801 4.9356 12.1640 5.7762 0.9306

6 1.7654 1.4962 11.2075 6.3225 1.3452 0.0785 3.5004 0.8230

9 1.9093 0.2660 12.1602 5.0388 1.3731 15.6511 31.0815 40.8576

## Page 39 of 54 Table J 3 : 10 Inch Membrane LFB Bias and Precision

Bias and PrecisionLabSingle LabBias (PPB)Single LabPrecision(PPB)Total LabBias (PPB)Total LabPrecision(PPB)

10

- 2 3

- 2 3

6

- 1 2

9

- 2 4

## Page 40 of 54 Table K 1 : 4 Inch Membrane Calibration Verification

Lab Standards Response Calibration factor Single Laboratory

STDS50010002000400050005001000200040005000AverageStandardDeviation% RSD

1 0.01692 0.03551 0.07341 0.14591 0.18247 3.38E

- 05 3.55E

- 05 3.67E

- 05 3.65E

- 05 3.65E

- 05 3.58053E

- 05 1.19219E

- 06 3.33%

STDS1000200030004000600010002000300040006000AverageStandardDeviation% RSD

2 0.237583 0.497794 0.75085 0.993456 1.466973 0.000238 0.000249 0.00025 0.000248 0.000244 0.000245925 5.13344E

- 06 2.09%

STDS100020004000600010000100020004000600010000AverageStandardDeviation% RSD

3 0.043165 0.0861 0.168219 0.255619 0.396178 4.32E

- 05 4.31E

- 05 4.21E

- 05 4.26E

- 05 3.96E

- 05 4.20981E

- 05 1.45372E

- 06 3.45%

STDS5001000200050001000050010002000500010000AverageStandardDeviation% RSD

4 0.05077 0.113035 0.203516 0.489053 0.915959 0.000102 0.000113 0.000102 9.78E

- 05 9.16E

- 05 0.000101148 7.81357E

- 06 7.72%

STDS500200050001000050000500200050001000050000AverageStandardDeviation% RSD

## Page 41 of 54 5 0.004156 0.016651 0.041184 0.085338 0.402447 8.31E

- 06 8.33E

- 06 8.24E

- 06 8.53E

- 06 8.05E

- 06 8.29141E

- 06 1.74723E

- 07 2.11%

STDS200500100050001000012000200500100050001000012000AverageStandardDeviation% RSD

6 0.008189 0.019293 0.039304 0.191422 0.384201 0.448755 4.08E

- 05 3.86E

- 05 3.93E

- 05 3.83E

- 05 3.84E

- 05 3.73963E

- 05 3.88069E

- 05 1.1705E

- 06 3.02%

STDS5050010002000500050500100020005000AverageStandardDeviation% RSD

7 0.00059 0.0068 0.01388 0.02783 0.06628 1.18E

- 05 1.36E

- 05 1.39E

- 05 1.39E

- 05 1.33E

- 05 1.32902E

- 05 8.74082E

- 07 6.58%

STDS10002500500010000150001000250050001000015000AverageStandardDeviation% RSD

8 0.003584 0.008852 0.018227 0.035949 0.055657 3.58E

- 06 3.54E

- 06 3.65E

- 06 3.59E

- 06 3.71E

- 06 3.61511E

- 06 6.50166E

- 08 1.80%

STDS100250100025005000100250100025005000AverageStandardDeviation% RSD

9 0.02058 0.057636 0.220735 0.58131 1.189081 0.000206 0.000231 0.000221 0.000233 0.000238 0.000225484 1.2622E

- 05 5.60%

## Page 42 of 54 Table K 2 : 4 Inch Membrane Calibration Verification

All LaboratoriesRSD (pooled)RSD Cal Maxk verificationk (ver) RSD(pooled)

4.45% 7.12% 2.2 16%

## Page 43 of 54 Table L : 10 Inch Membrane Calibration Verification

Lab Standards Response Calibration Factor

(CF) Single Laboratory All Laboratories

STDS840100200400840100200400AverageStandardDeviation% RSDRSD (pooled)RSD Cal Maxk verificationk (ver) RSD(pooled)

10 22.08433 120.8571 309.8668 653.16 1215.643 2.760541 3.021427 3.098668 3.2658 3.039108 3.037109 0.182228548 6.00% 9.00% 16.20% 2.4 39%

STDS20501002005002050100200500AverageStandardDeviation% RSD

6 0.057592 0.130322 0.265185 0.546313 1.428785 0.00288 0.002606 0.002663 0.002725 0.002858 0.002746 0.00011958 4.35%

STDS25501002002502550100200250AverageStandardDeviation% RSD

9 0.110323 0.163399 0.33528 0.655487 0.86072 0.004413 0.003268 0.003353 0.003277 0.003443 0.003551 0.000487036 13.72%

## Page 44 of 54 Table M 1 : 4 Inch Membrane Initial and Ongoing Precision and Recovery

LFB recovery LFB Percent Recovery IPR

- OPR Calculation

LabIDC Reading 1IDC Reading 2IDC Reading 3IDC Reading 4ODC Reading 1Individual LaboratoryMeanIndividual LaboratoryStandard DeviationReading 1Reading 2Reading 3Reading 4ODC Reading 1Individual LaboratoryMeanIndividual LaboratoryStandard DeviationIndividual LaboratoryIPRLower LimitIndividualLaboratoryIPRUpper Limit

1 985.75 1018.92 1025.69 1029.08 852.95 982.48 74.42320115 98.58% 101.89% 102.57% 102.91% 85.30% 98.25% 7.44% 58.80% 137.69%

2 933.71 865.26 839.73 990.04 814.57 888.66 72.00515175 93.37% 86.53% 83.97% 99.00% 81.46% 88.87% 7.20% 50.70% 127.03%

3 973.9434 1041.9011 1057.4688 952.6322 933.53 991.90 54.9335672 97.39% 104.19% 105.75% 95.26% 93.35% 99.19% 5.49% 70.07% 128.30%

4 1053 1062 1046 1046 1040.00 1049.40 8.414273587 105.30% 106.20% 104.60% 104.60% 104.00% 104.94% 0.84% 100.48% 109.40%

5 990.556 973.416 956.671 974.063 942.77 967.50 18.2913463 99.06% 97.34% 95.67% 97.41% 94.28% 96.75% 1.83% 87.06% 106.44%

6 1022.209158 1069.326634 990.9106709 987.0689604 1016.58 1017.22 32.94564572 102.22% 106.93% 99.09% 98.71% 101.66% 101.72% 3.29% 84.26% 119.18%

7 914.38678 904.68693 899.01413 884.62246 954.38 911.42 26.32204961 91.44% 90.47% 89.90% 88.46% 95.44% 91.14% 2.63% 77.19% 105.09%

8 951.918 977.214 1021.866 947.834 921.95 964.16 37.74385319 95.19% 97.72% 102.19% 94.78% 92.20% 96.42% 3.77% 76.41% 116.42%

9 911.8562 19 909.634498 892.976666 889.473373 879.27 896.64 13.84618297 91.19% 90.96% 89.30% 88.95% 87.93% 89.66% 1.38% 82.33% 97.00%

## Page 45 of 54 Table M 2 : 4 Inch Membrane Initial and Ongoing Precision and Recovery

All Laboratory Mean Pooled Within

Laboratory Standard

Deviation (sw) Between Laboratory

Standard Deviation of

the Mean results (sb) RSD IPR(max) IPR Combined

Standard Deviation

(sc) All Laboratory IPR

Lower Limit All Labor atory IPR

Upper Limit OPR Combined

Standard Deviation

(sc) All Labor atory OPR

Lower Limit All Laboratory OPR

Upper Limit

96.33% 4.41% 5.50% 7.79% 5.88% 82.79% 109.86% 7.02% 81.59% 111.06%

## Page 46 of 54 Table N 1 : 10 Inch Membrane Initial and Ongoing Precision and Recovery

LFB recovery LFB Percent Recovery IPR

- OPR Calculation

LabIDC Reading 1IDC Reading 2IDC Reading 3IDC Reading 4ODC Reading 1Individual LaboratoryMeanIndividual LaboratoryStandard DeviationReading 1Reading 2Reading 3Reading 4ODC Reading 1Individual LaboratoryMeanIndividualLaboratoryStandard DeviationIndividual LaboratoryIDC Lower LimitIndividual LaboratoryIDC Upper Limit

10 48.48 48.05 46.91 46.79 47.78 47.60 0.73 96.96% 96.10% 93.81% 93.59% 95.56% 95.21% 1.46% 87.44% 102.97%

6

51.33 48.78 46.65 47.49 48.84 48.62 1.77 102.66% 97.55% 93.30% 94.97% 97.68% 97.23% 3.55% 78.44% 116.02%

9

51.38 49.48 46.51 47.76 51.17 49.26 2.12 102.76% 98.97% 93.03% 95.51% 102.34% 98.52% 4.24% 76.02% 121.02%

## Page 47 of 54 Table N 2 : 10 Inch Membrane Initial and Ongoing Precision and Recovery

All Laboratory Mean Pooled Within

Laboratory Standard

Deviation (sw) Between Laboratory

Standard Deviation of

the Mean results (sb) RSD IPR(max) IPR Combined

Standard Deviation

(sc) All Laboratory IDC

Lower Limit All Laboratory IDC

Upper Limit OPR Combined

Standard Deviation

(sc) All Laboratory OPR

Lower Limit All Laboratory OPR

Upper Limit

96.99% 3.30% 1.67% 6.36% 2.07% 90.37% 103.60% 3.53% 87.81% 106.16%

## Page 48 of 54 Table O 1 : CCV Low Standard Bias and Precision 4 Inch Membrane

CCV Reading Difference Squared Difference Bias and precision

Lab CCV Low

Reading 1 CCV Low

Reading 2 CCV Low

Reading 3 Standard

Value

(PPB N) N CCV Low

Reading 1 CCV Low

Reading 2 CCV Low

Reading 3 CCV Low

Reading 1 CCV Low

Reading 2 CCV Low

Reading 3 Single Lab Bias Single Lab Precision Total Lab Bias Total Lab Precision

1 538.83 498.04 486.29 500.00 3 38.83

- 1.96

- 13.71 1507.77 3.84 187.96 8 29

- 30 70

2 997.41 992.91 986.34 1000.00 3

- 2.59

- 7.09

- 13.66 6.69 50.24 186.49

- 8 11

3 989.36 995.65 1001.16 1000.00 3

- 10.64

- 4.35 1.16 113.29 18.89 1.34

- 5 8

4 50.00 40.00 50.00 50.00 3 0.00

- 10.00 0.00 0.00 100.00 0.00

- 3 7

5 507.53 505.67 506.16 500.00 3 7.53 5.67 6.16 56.73 32.19 37.92 6 8

6 186.62 189.29 191.72 200.00 3

- 13.38

- 10.71

- 8.28 179.12 114.64 68.60

- 11 13

7 468.15 454.21 469.00 500.00 3

- 31.85

- 45.79

- 31.00 1014.11 2097.14 961.03

- 36 45

8 897.63 893.72 909.99 1000.00 3

- 102.37

- 106.28

- 90.02 10480.23 11295.23 8102.70

- 100 122

9 2358.15 2332.34 2434.52 2500.00 3

- 141.85

- 167.66

- 65.48 20120.93 28109.15 4287.61

- 125 162

## Page 49 of 54 Table O 2 : CCV High Standard Bias and Precision 4 Inch Membrane

CCV Reading Difference Squared Difference Bias and precision

Lab CCV High

Reading 1 CCV High

Reading 2 CCV High

Reading 3 Standard

Value

(PPB N) N CCV High

Reading 1 CCV High

Reading 2 CCV High

Reading 3 CCV High

Reading 1 CCV High

Reading 2 CCV High

Reading 3 Single Lab Bias Single Lab Precision Total Lab Bias Total Lab Precision

1 1894.70 1936.85 1904.56 2000.00 3

- 105.30

- 63.15

- 95.44 11088.09 3987.92 9108.79

- 88 110

- 55 136

2 1992.30 1984.49 1987.97 2000.00 3

- 7.70

- 15.51

- 12.03 59.31 240.44 144.65

- 12 15

3 1966.67 2001.25 1932.49 2000.00 3

- 33.34 1.25

- 67.51 1111.22 1.57 4557.96

- 33 53

4 510.00 530.00 510.00 500.00 3 10.00 30.00 10.00 100.00 900.00 100.00 17 23

5 1915.45 1921.10 1926.91 2000.00 3

- 84.55

- 78.91

- 73.09 7148.70 6226.00 5342.44

- 79 97

6 501.14 486.86 495.04 500.00 3 1.14

- 13.14

- 4.96 1.30 172.69 24.62

- 6 10

7 947.53 859.03 874.55 1000.00 3

- 52.47

- 140.97

- 125.45 2753.04 19873.54 15738.41

- 106 139

8 2560.87 2554.64 2539.59 2500.00 3 60.87 54.64 39.59 3704.67 2985.42 1567.37 52 64

9 4961.73 4741.15 4591.29 5000.00 3

- 38.27

- 258.85

- 408.71 1464.39 67000.83 167047.58

- 235 343

## Page 50 of 54 Table P : CCV Low and High Standard Bias and Precision 10 Inch Membrane

CCV Difference Squared Difference Bias and Precision

Lab CCV

Low

Reading

1 CCV

Low

Reading

2 CCV

Low

Reading

3 CCV

Low

Reading

4 Standard

Value

(PPB N) N CCV

Low

Reading

1 CCV

Low

Reading

2 CCV

Low

Reading

3 CCV

Low

Reading

4 CCV

Low

Reading

1 CCV

Low

Reading

2 CCV Low

Reading 3 CCV

Low

Reading

4 Single Lab Bias Single Lab Precision Total Lab Bias Total Lab Precision

10 8.68 8.88 8.81 8.20 8.00 4 0.68 0.88 0.81 0.20 0.46 0.77 0.66 0.04 0.64 0.80

- 2.28 4.90

6 17.95 18.87 18.18 20.00 3

- 2.05

- 1.13

- 1.82 4.21 1.27 3.31

- 1.67 2.10

9 191.32 196.78 191.54 200.00 3

- 8.68

- 3.22

- 8.46 75.28 10.35 71.61

- 6.79 8.87

CCV Difference Squared Difference Bias and Precision

Lab CCV

High

Reading

1 CCV

High

Reading

2 CCV

High

Reading

3 CCV

High

Reading

4 Standard

Value

(PPB N) N CCV

High

Reading

1 CCV

High

Reading

2 CCV

High

Reading

3 CCV

High

Reading

4 CCV

High

Reading

1 CCV

High

Reading

2 CCV High

Reading 3 CCV

High

Reading

4 Single Lab Bias Single Lab Precision Total Lab Bias Total Lab Precision

10 38.80 38.49 37.86 38.28 40.00 4

- 1.20

- 1.51

- 2.14

- 1.72 1.45 2.28 4.58 2.96

- 1.64 1.94

- 0.10 10.00

6 45.64 48.25 46.37 50.00 3

- 4.36

- 1.75

- 3.63 19.00 3.06 13.19

- 3.25 4.20

9 272.92 253.23 239.15 250.00 3 22.92 3.23

- 10.85 525.19 10.44 117.62 5.10 18.07

## Page 51 of 54 Table Q : Youden Pair Recovery

- 4 Inch Membrane

Lab Youden A

(Experimental Value ) Youden B

(Experimental Value ) Youden A

(Actual Value ) Youden B

(Actual Value ) Youden A

(Percent Recovery) Youden B

(Percent Recovery)

4 2.51 9.02 2.45 8.80 102.45% 102.46%

8 9.67 2.68 8.80 2.45 109.91% 109.30%

1 0.82 3.88 0.68 3.68 121.02% 105.54%

2 0.62 8.48 0.68 8.80 90.92% 96.31%

3 3.85 2.66 3.68 2.45 104.64% 108.66%

5 3.72 0.67 3.68 0.68 101.15% 98.68%

8 0.73 2.51 0.68 2.45 107.11% 102.43%

9 3.34 2.25 3.68 2.45 90.65% 91.67%

6 10.54 1.05 10.66 1.10 98.84% 95.46%



### Table R : Single Operator Standard Deviation and %RSD

– 4 Inch Membrane

M 2 2 2

2(M

- 1) 2 2 2

Difference (Di) 6.51 3.0609 1.19

6.99 3.0511 1.09

Mean (D) 6.75 3.0560 1.14

Di

- D 0.05933625 2.40002 E

- 05 0.002434069

0.05933625 2.40002 E

- 05 0.002434069

Single Operator So (Standard Deviation) 0.24 0.0049 0.049336281

Single Analyst %RSD 4.08% 0.22% 1.63%

## Page 52 of 54 Table S : Youden Pair Recovery

- 10 Inch Membrane

Lab Youden A

(Experimental Value ) Youden B

(Experimental Value ) Youden A

(Actual Value ) Youden B

(Actual Value ) Youden A

(Percent Recovery) Youden B

(Percent Recovery)

9 88.39 164.27 86.10 162.10 102.66% 101.34%

10 156.04 80.29 162.10 86.10 96.26% 93.25%

6 112.17 53.40 105.37 52.69 106.45% 101.35%



### Table T : Single Operator Standard Deviation and %RSD

– 10 Inch Membrane

M 2

2(M

- 1) 2

Difference (Di) 75.89

75.75

Mean (D) 75.82

Di

- D 0.004657716

0.004657716

Single Operator So (Standard Deviation) 0.07

Single Analyst %RSD 0.06%

## Page 53 of 54 Table U : Laboratory Reagent Blank

– Instrument Detection Limit 4 Inch Membrane

Laboratory Reagent Blank Data Difference Squared Difference Bias and Precision Instrument Detection Limit

LabStandard or SampleSampleConcentrationMeasurement 1Measurement 2Measurement 3AverageStandard DeviationNBlank Reading 1Blank Reading 2Blank Reading 3Blank Reading 1Blank Reading 2Blank Reading 3Single Lab BiasSingle Lab PrecisionTotal Lab BiasTotal Lab PrecisionSquare Blank Reading 1Difference from MeanSquare Blank Reading 2Difference from MeanSquare Blank Reading 3Difference from MeanTotal Lab AveragePooled StandardDeviationInstrument DetectionLimits

1 Blank 0 3.2 2.2 3.4 3.0 0.6 3 3.17 2.24 3.45 10.07 5.00 11.87 2.95 3.67 7 19 0.05 0.51 0.24 7.3 14.7 44.0

2 Blank 0

- 31.9 36.6 46.2 17.0 42.6 3

- 31.93 36.63 46.24 1019.54 1341.82 2138.16 16.98 47.43 2392.24 386.14 856.15

3 Blank 0 11.6 2.8 14.9 9.8 6.2 3 11.61 2.84 14.92 134.68 8.07 222.67 9.79 13.52 3.30 48.28 26.34

4 Blank 0 4.5 13.0

- 2.7 5.0 7.8 3 4.55 12.99

- 2.69 20.66 168.85 7.21 4.95 9.92 0.16 64.68 58.32

6 Blank 0

- 0.2 1.1 3.4 1.4 1.8 3

- 0.17 1.12 3.38 0.03 1.25 11.40 1.44 2.52 2.59 0.10 3.74

6 Blank 0 4.1 5.6 3.0 4.2 1.3 3 4.06 5.55 3.00 16.51 30.81 9.01 4.21 5.31 0.02 1.81 1.45

7 Blank 0 5.5 6.5 6.8 6.3 0.7 3 5.47 6.52 6.81 29.92 42.56 46.44 6.27 7.71 0.64 0.06 0.30

8 Blank 0

- 1.3 3.7

- 1.3 0.4 2.9 3

- 1.26 3.73

- 1.26 1.59 13.89 1.59 0.40 2.92 2.77 11.06 2.77

9 Blank 0 21.1 16.7 18.3 18.7 2.2 3 21.14 16.71 18.25 446.98 279.23 333.18 18.70 23.02 5.95 3.97 0.20

## Page 54 of 54 Table V : Laboratory Reagent Blank

– Instrument Detection Limit 10 Inch Membrane

Laboratory Reagent Blank Data Difference Squared Difference Bias and Precision Instrument Detection Limit

LabStandard or SampleSampleConcentration(PPB N as Ammonia)Measurement 1Measurement 2Measurement 3AverageStandard DeviationNBlank Reading 1Blank Reading 2Blank Reading 3Blank Reading 1Blank Reading 2Blank Reading 3Single Lab BiasSingle Lab PrecisionTotal Lab BiasTotal Lab PrecisionSquare Blank Reading 1Difference from MeanSquare Blank Reading 2Difference from MeanSquare Blank Reading 3Difference from MeanTotal Lab AveragePooled Standard DeviationInstrument Detection Limits

10 Blank 0

- 0.5 0.4 0.4 0.1 0.5 3

- 0.49 0.40 0.44 0.24 0.16 0.20 0.12 0.55

- 0.05 0.37 0.37 0.08 0.10

- 0.05 0.31 0.9

6 Blank 0

- 0.3

- 0.1

- 0.3

- 0.3 0.1 3

- 0.34

- 0.10

- 0.34 0.12 0.01 0.12

- 0.26 0.35 0.01 0.03 0.01

8 Blank 0 0.0 0.0 0.0 0.0 0.0 3 0.00 0.01 0.01 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.00