1. 1 / 9 ASTM D19 Method Validation Procedures William Lipps Analytical & Measuring Instrument Division July, 2015

2. This presentation is the opinion of the author. The author is a volunteer member of ASTM

3. All methods begin with an idea

4. An idea can be introduced by anyone at a sub committee meeting Determine if new standard is needed Identify and gather key stakeholders Appoint a Task Group Chair Register a Work Item Subcommittee decides on title and scope

5. By registering as a Work Item, ASTM: Provides a tracking number, “WK5432” Alerts other members Initiates a time table and process

6. In this presentation we are referring to “Standardized ” Methods Technique Scientific Principle, such as GCMS Method Adaptation of a technique to a measurement problem ASTM Method A method of known precision issued by ASTM

7. Validation of methods that measure the same analyte as other methods needs to establish: Equivalency Same result as approved method (interference free) Same QC Same detection (wet chemistry) Same extraction (GC) Existing Method New

8. Validation of the method must include Calibration MDL DOC Single Lab Study (matrices) Precision Spike Recoveries Multi-Lab study Precision

9. Validation of a New Method Preliminary Literature Search Design Phase Development Phase Validation Phase Evaluation Phase

10. The design phase occurs before significant amounts of data are collected: Literature search Draft “method” Scope Summary Technique Matrices Concentration Range (estimate) Optional vote at Subcommittee level

11. The Development phase collects preliminary data Single or two lab studies Proof of concept “preliminary data” Vote at Subcommittee level

12. The Validation phase includes collection of the following information: Selectivity Correctly ID analyte in matrices Calibration Technique and model Repeatability At a range of concentrations In numerous matrices Bias Compare to known matrices Spike samples Compare to other techniques Ruggedness What can change results

13. Before an inter-laboratory study is carried out the draft must pass subcommittee balloting Evaluation Phase Prefer 9 labs Prefer 9 matrices for CWA Minimum 3 matrices for SDWA 3 Youden Pairs (optional)

14. Validation of ASTM D7781 Test Method For Nitrite-Nitrate in Water by Nitrate Reductase Literature Search - justification Analytical methods using nitrate reductase have been previously reported,,, however, these investigators limited testing to surface and ground waters without evaluating complex matrices such as wastewater

15. A specific “technique” was chosen This new ASTM nitrate method is a discrete analyzer method. Discrete analyzers are defined in the standard

16. Selectivity was verified by showing nitrite and nitrate are recovered equally

17. Comparison with another method and evaluation of preservatives was made Sample #Commercial Laboratory Results, Analysis Method EPA 335.2 (mg NO 3 +NO 2 -N/L) Analysis by Reductase (mg NO 3 +NO 2 - N/L) Non- Preserved 10.80.940.88 2<0.10.050.06 3<0.10.240.55 40.660.680.58 511.811.6Lost 60.780.790.77 72.43.112.88

18. Since the method is for an existing EPA pollutant (nitrate plus nitrite) with established sampling and preservation guidelines, D19.05 did not perform a holding time study.

19. Potential interferences were evaluated (partial list) Species Added (mg/L) Unspiked Sample Result (mg/L) Spiked Sample Results (mg/L) Spike Added (mg/L) % Recovery Cl - 500 0.020.230.200105 0.172.542.5095 F-F- 5000.010.220.200105 Br - 500 <0.010.210.200100 0.152.652.50100 PO 4 -3 500 0.010.220.200105 0.142.542.5096 SO 4 -2 500 <0.010.210.200105 0.142.532.5096

20. Inter-Laboratory study carried out after successful subcommittee ballot 10 laboratories Four different discrete analyzer manufacturers One manufacturer had several different models

21. Each lab calculated reduction efficiency Lab Mg/L NO2-N (Found) Mg/L NO3-N (found) % Efficiency 12.462.51 102 22.452.48101 32.382.55107 42.222.59117 52.482.62 106 62.462.56104 72.422.51104 82.432.49102 93.04*3.0098.7 102.482.60 105

22. Each lab evaluated an LCS and control limits were established average1011.23 Standard Deviation2.660.67 Lower Limit (99% CI)92.90 Upper Limit (99% CI)1093

23. Single Lab precision was plotted

24. Multiple Lab precision was plotted

25. Sample Matrix Mean (mg/L) Standard Deviation No. of Laboratories No. of Results Multi- laboratory %RSD High TDS (500 ppm)0.770.025352.28% High TOC (2 ppm)1.120.025351.36% ERA #698 WS6.590.174282.51% USGS N1160.440.026425.09%

26. Sample MatrixMean (mg/L) Standard Deviation No. of Results Single Operator %RSD WW treatment 0.030.01313022.9% treatment plant effluent #1 7.730.3181301.03% treatment plant effluent #2 0.230.0126302.92% Paper Mill waste stream effluent 0.040.01563014.9% metal finisher wastewater effluent 27310.2342424.3% commercial laundry wastewater effluent 4.900.21233013.3% ERA #507 Hardness 0.020.01443036.8% Confined Animal Feeding Operation (CAFO) effluent 13.90.46233012.6% Low Nutrient Seawater 0.020.01123031.7%

27. ASTM method validation procedures produce methods of defined precision and accuracy

28. Thank You, for more information contact me wclipps@shimadzu.com