## USEPA Validation Study Report for Hach Method 10272

Spectro photo metric Measurement of Copper in Drinking Water

Submitted by:

Hach Company 5600 Lindbergh Drive Loveland Colorado 8053 8

Cary Jackson and Luke Johnson

December 201 5Hach Company Validation Study Report Measurement of Copper in Water
, Method 10272

2 Background

Purpose of Study The purpose of this study is to evaluate the proposed Hach Company Measurement of Copper ( C u ) in Water
, Method 10272
, against USEPA R eference Copper Method EPA 200.7 for approval and use in USEPA regulatory water compliance and reporting programs.

Method Summary The Hach Cu chemistry uses 2,2’

- biquinoline

- 4,4’

- dicarboxylic acid (bicinchoninic acid) for color development. Cuprous copper complexes with bicinchoninic acid to form a purple colored complex. The inten sity of the color of this complex is proportional to the concentrati on of copper in the sample. Cu pric copper is chemically reduced. Metal and hardness interferences are overcome through the addition of a chelating agent. Test results are measured at 56 0 nm.

Method Justification EPA reference method EPA 200.7 requires an expensive analytical instrument for the measurement of copper. Proposed Hach Method 10272 for the Spectrometric Measurement of Copper uses a simple and inexpensive chemical analysis t o measure copper.

Scope of Method
Method 10272 is applicable for use in drinking water.

Study Design and Objectives

The design and objectives of this validation study are detailed in the Validation Study Plan

0F 1 appended to this report.

Study Implementation

Study Sponsor The organizational sponsor responsible for managing this study is Hach Company.

Study Participants The participants, laboratories, and test matrices were selected from geographically diverse regions of the United States and are listed in the following table.

1 Hach Validation Study Plan, March 201 5Hach Company Validation Study Report Measurement of Copper in Water
, Method 10272

3 Treated Drinking

Water Matrix Facility Laboratory Source of Treated Test Water
Loveland, Colorado Hach Company , Test America

- Pittsburgh Surface Water Cedar Falls , Iowa Test America

- Cedar Falls Surface Water Brighton
, Colorado ALS Environmental Ground Water

Sample Collection and Distribution Matrix samples for this validation study were collected, preserved, and stored per EPA 200.7 protocols.

Analysis Description The description of the type and number of analyses are described in the Validation Study Plan appended to this report.

Data Reporting and Validation

Data Collection, Laboratory Submission, and Validation For each laboratory performing analyses, results from each test measurement were read from a
SL1000 analyzer with built

- in calibration, and manually transferred to an electronic spread sheet. Each laboratory then submitted the electronic spread sheet to the Hach Study Director for review and statistical evaluation.

Results

Summary results of the vali dation study are listed in Tables 1

- 5

. Initial demonstration of capability is demonstrated by accuracy (bias) and precision data which are generated throughout the calibration range and at the maximum contaminant level (MC L) in several
matrices. These da ta were collected at the Hach laboratory and are included in Table 1

. The quantitation range and method reporting limits for this method are 0. 1

– 5.75 mg/L Cu.Hach Company Validation Study Report Measurement of Copper in Water
, Method 10272

4 Table 1

– Initial Demonstration of Capability for Hach Method 10272

Parameter Concentration (mg/L)

LIS 250 mg/L CO 3 250 mg/L CaCO 3 2.5 mg/L TOC
Method Blank 0 0.00 0.01 0.02 0.01

LIS 250 mg/L CO 3 250 mg/L CaCO 3 2.5 mg/L TOC
0.5 4.0 4.7 0.0 4.0 1.3 6.9 4.9 2.1 1.0 5.0 8.1 7.6 3.2 6.6

LIS 250 mg/L CO 3 250 mg/L CaCO 3 2.5 mg/L TOC
0.5 3.3 3.2 0.0 3.8 1.3 0.7 1.8 0.9 1.6 5.0 0.6 0.7 0.7 0.3

Loveland DW Brighton DW Keokuk DW
Low 2.0 4.7 0.0 Mid 2.6 1.3 1.3 High 4.4 3.9 4.9

Loveland DW Brighton DW Keokuk DW
Low 1.1 2.3 1.1 Mid 0.4 0.7 1.3 High 0.2 0.5 0.7 Matrix Spike Precision Average Percent Recovery by Matrix

Average Percent Bias by Matrix

Accuracy (bias)

Percent Relative Standard Deviation by Matrix

Precision

Average Percent Bias by Matrix

Matrix Spike Accuracy (bias)

Percent Relative Standard Deviation by MatrixHach Company Validation Study Report Measurement of Copper in Water
, Method 10272

5 Table 2

– Loveland Colorado Tap Water Performance Results

Method Detection Limit (mg/L) Method Detection Limit (mg/L)

Low Ionic Strength Reagent Water 0.006 0.03

High Ionic Strength Reagent Water 0.007 0.03

Average Percent (%)

Recovery Percent Bias Standard Deviation Average Percent (%)

Recovery Percent Bias Standard Deviation

Low Ionic Strength Reagent Water 104 4 0.3 100 0 0.3

High Ionic Strength Reagent Water 88.4 12 0.3 94.8 5 1.0

Average Percent (%)

Recovery Relative
Percent Difference Average Percent (%)

Recovery Relative
Percent Difference
88.5 0.4 87.5 4.5 Matrix Spike Analysis Matrix Spike Analysis Matrix EPA 200.7 Hach Method 10272

Initial Precision and Recovery Initial Precision and Recovery

Loveland Treated Tap WaterHach Company Validation Study Report Measurement of Copper in Water
, Method 10272

6 Table 3

– Cedar Falls Tap Water Summary Results

Method Detection Limit (mg/L) Method Detection Limit (mg/L)

Low Ionic Strength Reagent Water 0.005 0.04

High Ionic Strength Reagent Water 0.006 0.02

Average Percent (%)

Recovery Percent Bias Standard Deviation Average Percent (%)

Recovery Percent Bias Standard Deviation

Low Ionic Strength Reagent Water 95.0 5 1.1 95.8 4 5.2

High Ionic Strength Reagent Water 94.8 5 1.2 97.1 3 9.1

Average Percent (%)

Recovery Relative
Percent Difference Average Percent (%)

Recovery Relative
Percent Difference
97.8 0.0 93.5 2.1 Matrix EPA 200.7 Hach Method 10272

Initial Precision and Recovery Initial Precision and Recovery

Cedar Falls Treated Tap Water Matrix Spike Analysis Matrix Spike AnalysisHach Company Validation Study Report Measurement of Copper in Water
, Method 10272

7 Table 4

– Brighton Colorado Drinking Water Plant Summary Results

Development of QC Acceptance Criteria

Quality control acceptance criteria for method detection limit (MDL), initial precision and recovery (IPR), and matrix spike recovery are described in Table 5

. Calibration verification is demonstrated through the accuracy (bias) data. These criteria are based on intra

- laboratory
data. Method Detection Limit (mg/L) Method Detection Limit (mg/L)

Low Ionic Strength Reagent Water 0.007 0.01

High Ionic Strength Reagent Water 0.009 0.02

Average Percent (%)

Recovery Percent Bias Standard Deviation Average Percent (%)

Recovery Percent Bias Standard Deviation

Low Ionic Strength Reagent Water 103 3 0.5 101 1 1.9

High Ionic Strength Reagent Water 101 1 0.5 90.5 10 0.8

Average Percent (%)

Recovery Relative
Percent Difference Average Percent (%)

Recovery Relative
Percent Difference
99.3 1.0 85.0 0.0 Matrix

Brighton Treated Tap Water Matrix Spike Analysis Matrix Spike Analysis EPA 200.7 Hach Method 10272

Initial Precision and Recovery Initial Precision and RecoveryHach Company Validation Study Report Measurement of Copper in Water
, Method 10272

8 Table 5

– Quality Control Performance Criteria for Hach Method 10272

Data Analysis/Discussion

MDL Results

The low ionic strength MDL results for each of the three facilit ies ranged from 0. 0 0 4 mg/L to
0.0 1 mg/L for the EPA Reference Method EPA 200.7 and 0. 0 1 mg/L to 0. 0 4 mg/L for the Hach
Method 10272 . The high ionic strength matrix MDL results ranged from 0. 0 1 mg/L to 0. 0 1 mg/L
for the EPA Reference Method EPA 200.7 and 0. 0 2 mg/L to 0. 0 3 mg/L for the Hach Method
10272 . The pooled MDL results for EPA Reference Method EPA 200.7 w ere determined to be
0. 0 1 mg/L for low ionic strength m atrix water and 0. 0 1 mg/L for high ionic strength matrix water. The pooled MDL results for the Hach Method 10272 were determined to be 0. 0 2 mg/L for low ionic strength matrix water and 0. 0 2 mg/L for high ionic strength matrix water. The regulatory limit established by USEPA for this validation study is ≤ 1. 3 mg/L as this is the maximum contaminant level (MCL )

.

Initial Precision and Recovery Results Low Ionic Strength Reagent Water
High Ionic Strength Reagent Water

Initial Precision and Recovery Analysis Average Percent (%) Recovery Percent Bias Lower Limit of % Recovery Upper Limit of % Recovery 95% Precision of Recovery Average Percent (%) Recovery Percent Bias Lower Limit of % Recovery Upper Limit of % Recovery 95% Precision of Recovery Low Ionic Strength Reagent Water 101 1 82.7 118 0.01 99.0 1 88.4 110 0.06

High Ionic Strength Reagent Water 94.8 5 71.0 119 0.02 94.1 6 81.7 107 0.11

Average Percent (%) Recovery Percent Bias Lower Limit of % Recovery Upper Limit of % Recovery 95% Precision of Recovery Average Percent (%) Recovery Percent Bias Lower Limit of % Recovery Upper Limit of % Recovery 95% Precision of Recovery

95.2 5 77.6 113 0.02 88.7 11 74.9 102 0.11 Method Detection Limit (MDL) mg/L

0.005

0.006 Method Detection Limit (MDL) mg/L

0.02

0.02

Matrix Spike Recovery Matrix EPA 200.7 Hach Method 10272

Initial Precision and Recovery (IPR) Initial Precision and Recovery (IPR)

Drinking Water Matrix Analysis Matrix Spike RecoveryHach Company Validation Study Report Measurement of Copper in Water
, Method 10272

9 The IPR average recovery results for low ionic strength matrix water for each of the three facilities ranged from 95 .0 % to 10 4 % for EPA Reference Method EPA 200.7 and 9 5.8 % to
101 % mg/L for Hach Method 10272

. The IPR average recovery results for high ionic strength
matrix water ranged from 88.4 % to 101 % for EPA Reference Method EPA 200.7 , and 90.5 % to
97 .1 % for the Hach Method 10272 . The pooled low ionic strength matrix recovery results for EPA Reference Method EPA 200.7 ranged from 8 2.7 % to 1 18 % with a 95% precision of 0.0 1 and
88.4 % to 11 0 % with a 95% precision of 0.0 6 for Hach Method 10272 . The pooled high ionic strength matrix recovery results for the EPA Reference Method EPA 200.7 ranged from 71.0 %

to 11 3 % with a 95% precision of 0.0 2 and 81.7 % to 107 % with a 95% precision of 0. 1 1 for Hach method 10272

.

Matrix Spike Results

The average matrix spike recovery results of the three facilities ranged from 88 .5 % to 99.3 % for EPA Reference Method EPA 200.7 and 85.0 % to 93.5 % for Hach method 10272 . The relative percent difference for matrix spike recoveries ranged from 0. 0 to 1.0 for EPA reference method
EPA 200.7 and 0. 0 to 4.5 for Hach method 10272

. The pooled matrix spike results of recovery ranged from 77.6 % to 11 3 % for EPA Reference Method EPA 200.7 and 74.9 % to 1 02 % for Hach Method 10272

. The 95% Precision of Recovery results for the EPA Reference Method EPA
200.7 and Hach Method 10272 were determined to be 0.0 2 and 0. 1 1 respectively.

Conclusion

A validation study was conducted to compare the performance of Hach Method 10272 for the measurement of copper in water to that of the EPA Reference Method EPA 200.7

. The results of the study indicate that Hach M ethod 10272 is equally effective to that of th e EPA Reference Method EPA 200.7 for Safe Drinking Water Act monitoring and compliance reporting programs.