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

MEANINGFUL METALS DATA Brooks Rand Labs Specialty Trace Metals Analytical Laboratory Certified Small Business located in Seattle, Washington DOECAP Audited Lab DoD Accredited NELAC Accredited ISO Accredited Performing Metals Speciation Analyses since 1988!

MEANINGFUL METALS DATA 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

MEANINGFUL METALS DATA 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

MEANINGFUL METALS DATA 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

MEANINGFUL METALS DATA 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)

MEANINGFUL METALS DATA Metals Speciation Tools to Support a Wide Variety of Project Types Different Species have Different Properties Risk Assessment Treatment Technologies Transport & Mobility Bioavailability

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

MEANINGFUL METALS DATA

MEANINGFUL METALS DATA Typical Landfill Gas Power Plant Courtesy City of Vancouver BC

MEANINGFUL METALS DATA 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

MEANINGFUL METALS DATA Total Arsenic Analysis Incoming Municipal Water Total Arsenic0.14 µg/L Power Plant Effluent Total Arsenic1,560 µg/L

MEANINGFUL METALS DATA 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

MEANINGFUL METALS DATA 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)

MEANINGFUL METALS DATA EPA Method 1632A Manual Analysis for Arsenic Speciation 120 °C 20 mL

MEANINGFUL METALS DATA IC-ICP-MS Automated Analysis for Arsenic Speciation Source:

MEANINGFUL METALS DATA IC-ICP-MS Chromatogram As(III) DMAs MMAs As(V)

Mercury Speciation for Source Identification Case Study:

MEANINGFUL METALS DATA 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, /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

Rytuba (2014), Goldschmidt Conference Presentation

MEANINGFUL METALS DATA 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

MEANINGFUL METALS DATA 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

MEANINGFUL METALS DATA 5-Step SSE Sample Preparation

MEANINGFUL METALS DATA 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

Mercury Speciation for Stabilization Treatment Optimization Case Study:

MEANINGFUL METALS DATA Treatment of Oak Ridge Y-12 Site Soils All samples were “spiked” with 10,000 mg/kg Hg(0)

Selenium Speciation for Wastewater Treatment Optimization Case Study:

MEANINGFUL METALS DATA Coal-Fired Power Plant with Flue Gas Desulfurization (FGD)

MEANINGFUL METALS DATA Se(IV) →

MEANINGFUL METALS DATA Se(IV) → Se(IV) → Se(VI)?

MEANINGFUL METALS DATA 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)

MEANINGFUL METALS DATA 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

MEANINGFUL METALS DATA 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)

MEANINGFUL METALS DATA Selenium Speciation BRL SOP BR-0061 (IC-ICP-DRC-MS)

MEANINGFUL METALS DATA Metals Speciation… A powerful tool to help address metals-related environmental issues

Thank You! Questions? Contact Info: Michelle Briscoe