## USEPA Validation Study Report for Hach Method 8026 Copper

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

November 201 5Hach Company Validation Study Report

Measurement of Copper in Water

, Method 8026

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 8026

, 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 concentration of

copper in the sample. Cupric 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 8026 for the Spectrometric Measurement of

Copper uses a simple and inexpensive chemical analysis to measure copper.

Scope of Method

Method 8026 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 1

appended to this report.

Study Implementation

Study Sponsor

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

Study Participants

1 Hach Validation Study Plan, March 201 5Hach Company Validation Study Report

Measurement of Copper in Water

, Method 8026

3 The participants, laboratories, and test matrices were selected from geographically diverse

regions of the United States a nd are listed in the following table.

Treated Drinking

Water Matrix

Facility Laboratory Source of Treated

Test Water

Loveland, Colorado Hach Company , TestAmerica

- 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

DR 1 900 or DR 50 00 spectrophotometer 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 validation 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 data were collected at the Hach laboratory and are included in Table 1

. The

quantitation ran ge and method reporting limits for this method are 0.1

– 5.0 0 mg/L Cu.Hach Company Validation Study Report

Measurement of Copper in Water

, Method 8026

4 Table 1

– Initial Demonstration of Capability for Hach Method 8026Hach Company Validation Study Report

Measurement of Copper in Water

, Method 8026

5 Table 2

– Loveland Colorado Tap Water Performance ResultsHach Company Validation Study Report

Measurement of Copper in Water

, Method 8026

6 Table 3

– Cedar Falls Tap Water Summary ResultsHach Company Validation Study Report

Measurement of Copper in Water

, Method 8026

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.Hach Company Validation Study Report

Measurement of Copper in Water

, Method 8026

8 Table 5

– Quality Control Performance Criteria for Hach Method 8026

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. 02 mg/L to 0. 07 mg/L for the Hach

Method 8026 . 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. 05 mg/L for the Hach Method

8026 . 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 8 026 were determined to be 0. 0 3 mg/L

for low ionic strength matrix water and 0. 03 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 (MC L)

.

Initial Precision and Recovery Results

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 97 .3 % to

106 % mg/L for Hach Method 8026

. The IPR average recovery results for high ionic strengthHach Company Validation Study Report

Measurement of Copper in Water

, Method 8026

9 matrix water ranged from 88.4 % to 101 % for EPA Reference Method EPA 200.7 , and 93.8 % to

105 % for the Hach Method 8026 . The pooled low ionic strength matrix recovery results for EPA

Reference Method EPA 200.7 ranged from 82.7 % to 1 18 % with a 95% precision of 0.0 1 and

84.9 % to 117 % with a 95% precision of 0.0 2 for Hach Method 8026 . 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 76.4 % to 121 % with a 95% precision of 0.0 1 for Hach

method 8026

.

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 91. 3 % to 100 % for Hach method 8026 . 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 6.1 for Hach method 8026

. The pooled matrix spike results of recovery

ranged from 77.6 % to 11 3 % for EPA Reference Method EPA 200.7 and 79.5 % to 110 % for Hach

Method 8026

. The 95% Precision of Recovery results for the EPA Reference Method EPA 200.7

and Hach Method 8026 were determined to be 0.0 2 and 0. 15 respectively.

Conclusion

A validation study was conducted to compare the performance of Hach Method 8026 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 8026 is equally effective to that of th e EPA Reference

Method EPA 200.7 for Safe Drinking Water Act

, monitoring and compliance reporting programs.