1. www.brooksrand.com Metals Speciation as a Tool for Addressing Environmental Issues Michelle Briscoe President/CEO, Brooks Rand Labs michelle@brooksrand.com Presented at the DOECAP ASP Workshop, Albuquerque, NM, September 17, 2014

2. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Brooks Rand Labs Specialty Trace Metals Analytical Laboratory Certified Small Business located in Seattle, Washington DOECAP Audited Lab DoD Accredited NELAC Accredited ISO 17025 Accredited Performing Metals Speciation Analyses since 1988!

3. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Scope of Services Niche services exclusively for metals analyses Low-Level Trace Metals Analyses Metals Speciation Services Accurate Results in Complex Matrices Supported by Outstanding Customer Service and Decades of Experience

4. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Scope of Services Niche services exclusively for metals analyses Low-Level Trace Metals Analyses Metals Speciation Services Accurate Results in Complex Matrices Supported by Outstanding Customer Service and Decades of Experience

5. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Commonly Speciated Metals Arsenic – As(III), As(V), MMAs, DMAs, AsB Mercury – MeHg, Inorganic Hg (Hg 2+ ), EtHg, Fractionation in Soils/Sediments Selenium – Se(IV), Se(VI), SeCN, SeMet, MeSe Chromium – Cr(III), Cr(VI) Iron – Fe(II), Fe(III) Manganese – Mn(II), Mn(IV) at Brooks Rand Labs

6. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Common Speciated Metals Arsenic – As(III), As(V), MMAs, DMAs, AsB Mercury – MeHg, Inorganic Hg (Hg 2+ ), EtHg, Fractionation in Soils/Sediments Selenium – Se(IV), Se(VI), SeCN, SeMet, MeSe Chromium – Cr(III), Cr(VI) Iron – Fe(II), Fe(III) Manganese – Mn(II), Mn(IV)

7. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Metals Speciation Tools to Support a Wide Variety of Project Types Different Species have Different Properties Risk Assessment Treatment Technologies Transport & Mobility Bioavailability

8. Case Study: Arsenic Speciation for Wastewater Treatment at Landfill Gas Power Plant

9. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com

10. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Typical Landfill Gas Power Plant Courtesy City of Vancouver BC

11. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Problem: High Arsenic in Wastewater from Landfill Gas Power Plant Background: Wastewater from a landfill gas electric power plant in New England was very high in arsenic (~1500 μg/L) Arsenic levels were not reduced through standard wastewater treatment technologies

12. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Total Arsenic Analysis Incoming Municipal Water Total Arsenic0.14 µg/L Power Plant Effluent Total Arsenic1,560 µg/L

13. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Arsenic Speciation Analysis Incoming Municipal Water Total Arsenic0.14 µg/L As(III)Non-detect As(V)0.14 µg/L MMAsNon-detect DMAsNon-detect Power Plant Effluent Total Arsenic1,565 µg/L As(III)9.1 µg/L As(V)4.8 µg/L MMAs0.93 µg/L DMAs1,550 µg/L

14. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Arsenic Speciation Surface Water, Ground Water, Seawater Total As, Inorganic As, Organic As, As(III), As(V), MMAs, and DMAs Soils/Sediment All of the Above Animal Tissues/Plants/Biomonitoring/Food All of the Above plus Arsenobetaine (AsB)

15. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com EPA Method 1632A Manual Analysis for Arsenic Speciation 120 °C 20 mL

16. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com IC-ICP-MS Automated Analysis for Arsenic Speciation Source: www.speciation.net

17. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com IC-ICP-MS Chromatogram As(III) DMAs MMAs As(V)

18. Mercury Speciation for Source Identification Case Study:

19. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com USGS Study of High Mercury Levels in Coastal Redwood Streams [1] [1] Rytuba (2014), Goldschmidt Conference Presentation [2] Weiss-Penzias et al (2012) Geophys Res Letters, 39, L03804, 1-5. 1/3 of water from summer fog MeHg in Fog 10 ng/L (Rain ≈ 0.2 ng/L) [2] MeHg in coastal redwood needles is significantly higher than needles from Evergreens that don’t receive coastal fog

20. Rytuba (2014), Goldschmidt Conference Presentation

21. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com USGS Study of High Mercury Levels in Coastal Redwood Streams MeHg in Streams (high-flow): Elevated High soil (TSS) content, soils high in MeHg due to decomposition of needles MeHg in Streams (low-flow): Normal MeHg retained by needles

22. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Mercury Speciation Surface Water, Ground Water, Seawater Total Hg, MeHg, Hg(II)/Acid-Labile, Hg(0) Tissues/Biota/Biomonitoring/Food Total Hg, MeHg, EtHg Air/Natural Gas Total Hg, Particulate Hg, Gaseous Hg Soils/Sediment Total Hg, MeHg, Hg(0), 5-Step SSE Procedure All Methods are CV-AFS

23. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com 5-Step SSE Sample Preparation

24. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Mercury Speciation in Soils FractionDescriptionExtractantTypical Compounds F0Volatile Hg(0)DIW, then headspace measurement Volatile Hg(0), potentially DMeHg F1Water Soluble HgDIWHgCl 2, HgSO 4 F2Weak-acid Soluble HgpH 2 HCl/AcOHHgO F3Organo-Complexed Hg1 M KOHHg-humics, Hg 2 Cl 2 CH 3 Hg (MeHg) F4Strongly-Complexed Hg12 M HNO 3 mineral lattice Hg 2 Cl 2 Hg(0) - liquid elemental F5Mineral-Bound HgAqua RegiaHgS, m-HgS HgSe, HgAu “5-Step” Selective Sequential Extraction Procedure

25. Mercury Speciation for Stabilization Treatment Optimization Case Study:

27. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Treatment of Oak Ridge Y-12 Site Soils All samples were “spiked” with 10,000 mg/kg Hg(0)

28. Selenium Speciation for Wastewater Treatment Optimization Case Study:

29. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Coal-Fired Power Plant with Flue Gas Desulfurization (FGD)

30. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Se(IV) →

31. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Se(IV) → Se(IV) → Se(VI)?

32. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Se(IV) → Se(IV) → Se(VI)? Standard chemical treatments remove Se(IV), but not Se(VI) More costly bioreactors are efficient at removing Se(VI)

33. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Treatment of FGD Wastewater Understanding the selenium speciation at each step in the FGD wastewater generation process saves time and money in engineering the optimal treatment technologies for Selenium Removal

34. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Selenium Speciation Surface Water, Ground Water, Wastewater Total Se Inorganic Se, Organic Se Selenite {Se(IV)} Selenate {Se(VI)} Selenocynate (SeCN) Selenomethionine (SeMet) Methylseleninic Acid (MeSe)

35. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Selenium Speciation BRL SOP BR-0061 (IC-ICP-DRC-MS)

36. MEANINGFUL METALS DATA www.brooksrand.com206-632-6206brl@brooksrand.com Metals Speciation… A powerful tool to help address metals-related environmental issues

37. Thank You! Questions? Contact Info: Michelle Briscoe michelle@brooksrand.com