Multiple methods promulgated by the EPA for compliance monitoring of mercury in wastewater were investigated and compared to cold vapor inductively coupled plasma mass spectrometry. This study was performed to identify the limitations and benefits associated with each analytical method and to identify how varying waste streams can induce method failures.

1. Intercomparison of Different Technologies for the Quantitation of Total Mercury in Complex Waste Streams Russell Gerads ( [email_address] ) Hakan Gürleyük ( [email_address] ) [email_address] www.appliedspeciation.com APPLIED SPECIATION AND CONSULTING, LLC

5. Cold Vapor Atomic Fluorescence Spectrometry (CV-AAS) EPA Method 245.1 2009 International Water Conference

8. Cold Vapor Atomic Absorption Spectrometry (CV-AFS) EPA Method 1631 2009 International Water Conference

11. Cold Vapor Atomic Fluorescence Spectrometry (CV-AFS) EPA Method 1631 Manual Method 2009 International Water Conference

12. Cold Vapor Atomic Fluorescence Spectrometry (CV-AFS) EPA Method 1631 Automated Method 2009 International Water Conference

13. Cold Vapor Atomic Fluorescence Spectrometry (CV-AFS) EPA Method 1631 Why use CV-AFS? They told us to… Benefits: Few spectral interferences Very low detection limits Limitations: Chemical interferences Sample with high TDS Samples with high concentrations of VOC Samples with high transition element concentrations 2009 International Water Conference

14. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) 2009 International Water Conference

15. Schematic for CV-ICP-MS Computer Waste ICP-MS NaBH 4 Autosampler Oxidized Sample 2009 International Water Conference

16. Cold Vapor Inductively Coupled Plasma Mass Spectrometry (CV-ICP-MS) Why use CV-ICP-MS? Benefits: Few spectral interferences Very low detection limits Isotope confirmation Limitations: Sample with high TDS All Hg species must be converted to Hg(0) during reduction 2009 International Water Conference

17. Cold Vapor Atomic Fluorescence Spectrometry (CV-AFS) EPA Method 1631 APPLIED SPECIATION AND CONSULTING, LLC

18. FGD Purge Line APPLIED SPECIATION AND CONSULTING, LLC At instrument 0.97ng/L At instrument 73.2ng/L At instrument 0.354ng/L At instrument 2ng/L

19. Refinery Sour Water APPLIED SPECIATION AND CONSULTING, LLC At instrument 2630ng/L At instrument 6.78ng/L At instrument 405ng/L At instrument 325ng/L

20. FGD Effluent APPLIED SPECIATION AND CONSULTING, LLC At instrument 2400ng/L At instrument 233ng/L At instrument 4.6ng/L At instrument 150ng/L

21. Encountered Interferences Why is there a discrepancy? Limitations: Chemical interferences Sample with high TDS Samples with high concentrations of VOC Samples with high transition element concentrations 2009 International Water Conference

22. Encountered Interferences Isn’t AFS the most sensitive detection method? Answer: No 2009 International Water Conference

25. Problems with ICP ICP was always thought to be a species independent detection method due to the ionization capacity of the plasma. Not true!!! 2009 International Water Conference

26. Species Independent Method?

28. General Conclusion Existing methods prone to failure for complex matrices Are you prepared to comply with new methods? Will your treatment system comply with standards after new methods are enforced? 2009 International Water Conference

29. Acknowledgements Dr. Hakan Gurleyuk (ASC Senior Scientist) Jacob Meyer (ASC Lab Manager) Ben Wozniak (ASC Senior Project Manager) Collaborative industrial clients 2009 International Water Conference