Correction Factors for Freshwater Dissolved and Total Nutrients for 1998 and 2006 Instrument and Method Changes by the King County Environmental Laboratory March 2016 Alternate Formats Available Correction Factors for Freshwater Dissolved and Total Nutrients for 1998 and 2006 Instrument and Method Changes by the King County Environmental Laboratory Submitted by: Timothy Clark Science and Technical Support Section King County Water and Land Resources Division Department of Natural Resources and Parks Correction Factors for Freshwater Dissolved and Total Nutrients Acknowledgements I would like to express my gratitude to the current and past employees of the King County Environmental Laboratory; their constant drive to improve their methods of analysis is inspiring and a tremendous asset to the Division. My thanks to Sally Abella, Debra Bouchard, Curtis DeGasperi, and Jim Simmonds for their review of this document. Citation King County. 2016. Correction Factors for Dissolved and Total Nutrients for 1998 and 2006 Instrument and Method Changes by the King County Environmental Laboratory. Prepared by Timothy Clark, Water and Land Resources Division. Seattle, Washington. King County Science and Technical Support Section i March 2016 Correction Factors for Freshwater Dissolved and Total Nutrients Table of Contents Executive Summary............................................................................................................................................. vi Acronyms and Abbreviations ......................................................................................................................... vii 1.0 Introduction .............................................................................................................................................. 1 1.1 Summary of King County’s Freshwater Monitoring Program .......................................... 2 1.2 Summary of Method and Instrument Changes and Subsequent Side-By-Side Analyses ................................................................................................................................................ 3 1.2.1 1998 Digestion Method Change ............................................................................................. 3 1.2.2 2007 Instrument and Digestion Method Change ............................................................. 4 2.0 Methods ...................................................................................................................................................... 5 2.1 Statistical Methods ............................................................................................................................ 5 2.1.1 Tests for Normality and Paired Difference Tests ............................................................ 5 2.1.2 Segmented Robust Linear Regression ................................................................................. 6 2.1.3 Trend Analysis .............................................................................................................................. 6 2.2 Impacts of Dilution ............................................................................................................................ 6 3.0 1998 Freshwater Total Phosphorus Digestion Change Analysis ......................................... 8 3.1 Data Used .............................................................................................................................................. 8 3.2 Normality and Paired Difference ................................................................................................. 8 3.3 Regression Results ..........................................................................................................................10 3.4 Heteroscedasticity ...........................................................................................................................11 3.5 Dilution of Samples .........................................................................................................................11 4.0 2006 Freshwater Total Phosphorus Instrument Change Analysis ...................................13 4.1 Data Used ............................................................................................................................................13 4.2 Normality and Paired Difference ...............................................................................................13 4.3 Regression Results ..........................................................................................................................15 4.4 Heteroscedasticity ...........................................................................................................................16 4.5 Dilution of Samples .........................................................................................................................16 5.0 2006 Freshwater Total Nitrogen Instrument Change Analysis ..........................................18 5.1 Data Used ............................................................................................................................................18 5.2 Normality and Paired Difference ...............................................................................................18 5.3 Regression Results ..........................................................................................................................20 King County Science and Technical Support Section ii March 2016 Correction Factors for Freshwater Dissolved and Total Nutrients 5.4 Heteroscedasticity ...........................................................................................................................21 5.5 Dilution of Samples .........................................................................................................................21 6.0 2006 Freshwater Orthophosphate Instrument Change Analysis ......................................23 6.1 Data Used ............................................................................................................................................23 6.2 Normality and Paired Difference ...............................................................................................23 6.3 Regression Results ..........................................................................................................................25 6.4 Heteroscedasticity ...........................................................................................................................26 6.5 Dilution of Samples .........................................................................................................................26 7.0 2006 Freshwater Nitrate/Nitrite Instrument Change Analysis .........................................28 7.1 Data Used ............................................................................................................................................28 7.2 Normality and Paired Difference ...............................................................................................28 7.3 Regression Results ..........................................................................................................................30 7.4 Heteroscedasticity ...........................................................................................................................30 7.5 Dilution of Samples .........................................................................................................................31 8.0 2006 Freshwater Ammonia Instrument Change Analysis ....................................................32 8.1 Data Used ............................................................................................................................................32 8.2 Normality and Paired Difference ...............................................................................................32 8.3 Regression Results ..........................................................................................................................33 9.0 Trend Analysis .......................................................................................................................................34 9.1 Total Phosphorus .............................................................................................................................35 9.2 Total Nitrogen ...................................................................................................................................36 9.3 Orthophosphate ................................................................................................................................37 9.4 Nitrate/Nitrite ...................................................................................................................................38 10.0 Summary and Recommendations ..................................................................................................39 References .............................................................................................................................................................42 Figures Figure 1. Comparison of TOTP.Single and TOTP.Combined for all freshwater programs. ........................................................................................................................................ 9 Figure 2. One-breakpoint model for TOTP.Single regressed on TOTP.Combined. ..............10 Figure 3. Comparison of TOTP.API and TOTP.OI for all data pairs above the MDL threshold.