www.brooksrand.com metals speciation as a tool for addressing environmental issues michelle briscoe...

www.brooksrand.com

Metals Speciation as a Tool for Addressing Environmental Issues

Michelle BriscoePresident/CEO, Brooks Rand Labsmichelle@brooksrand.com

Presented at the DOECAP ASP Workshop, Albuquerque, NM, September 17, 2014

MEANINGFUL METALS DATAwww.brooksrand.com

206-632-6206 brl@brooksrand.com

Brooks Rand LabsSpecialty 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!

Scope of ServicesNiche 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

Scope of ServicesNiche 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

Commonly Speciated MetalsArsenic – As(III), As(V), MMAs, DMAs, AsBMercury – MeHg, Inorganic Hg (Hg2+), EtHg,

Fractionation in Soils/SedimentsSelenium – Se(IV), Se(VI), SeCN, SeMet,

MeSeChromium – Cr(III), Cr(VI)Iron – Fe(II), Fe(III)Manganese – Mn(II), Mn(IV)

at Brooks Rand Labs

Common Speciated Metals

Arsenic – As(III), As(V), MMAs, DMAs, AsBMercury – MeHg, Inorganic Hg (Hg2+), EtHg,

Fractionation in Soils/SedimentsSelenium – Se(IV), Se(VI), SeCN, SeMet,

MeSeChromium – Cr(III), Cr(VI)Iron – Fe(II), Fe(III)Manganese – Mn(II), Mn(IV)

Metals SpeciationTools 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

Typical Landfill Gas Power Plant

Courtesy City of Vancouver BC

Problem: High Arsenic in Wastewater from Landfill Gas Power PlantBackground:

• 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

Total Arsenic Analysis

Incoming Municipal WaterTotal Arsenic 0.14 µg/L

Power Plant EffluentTotal Arsenic 1,560 µg/L

Arsenic Speciation AnalysisIncoming Municipal WaterTotal Arsenic 0.14 µg/L

As(III) Non-detect

As(V) 0.14 µg/L

MMAs Non-detect

DMAs Non-detect

Power Plant EffluentTotal Arsenic 1,565 µg/L

As(III) 9.1 µg/L

As(V) 4.8 µg/L

MMAs 0.93 µg/L

DMAs 1,550 µg/L

Arsenic SpeciationSurface 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)

EPA Method 1632AManual Analysis for Arsenic Speciation

120 °C

IC-ICP-MSAutomated Analysis for Arsenic Speciation

IC-ICP-MS Chromatogram

As(III)

DMAs MMAs

Mercury Speciation for Source Identification

Case Study:

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

Rytuba (2014), Goldschmidt Conference Presentation

USGS Study of High Mercury Levels in Coastal Redwood Streams

MeHg in Streams (high-flow): ElevatedHigh soil (TSS) content, soils high in MeHg due to decomposition of needles

MeHg in Streams (low-flow): NormalMeHg retained by needles

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

5-Step SSE Sample Preparation

Mercury Speciation in Soils

Fraction Description Extractant Typical Compounds

F0 Volatile Hg(0) DIW, then headspace measurement

Volatile Hg(0), potentially DMeHg

F1 Water Soluble Hg DIW HgCl2, HgSO4

F2 Weak-acid Soluble Hg pH 2 HCl/AcOH HgO

F3 Organo-Complexed Hg 1 M KOH Hg-humics, Hg2Cl2

CH3Hg (MeHg)

F4 Strongly-Complexed Hg 12 M HNO3 mineral latticeHg2Cl2

Hg(0) - liquid elemental

F5 Mineral-Bound Hg Aqua Regia HgS, m-HgSHgSe, HgAu

“5-Step” Selective Sequential Extraction Procedure

Mercury Speciation for Stabilization Treatment Optimization

Case Study:

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

Selenium Speciation for Wastewater Treatment Optimization

Case Study:

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

Se(IV) →

Se(IV) → Se(VI)?

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)

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

Selenium SpeciationSurface Water, Ground Water,

Wastewater• Total Se• Inorganic Se, Organic Se• Selenite {Se(IV)}• Selenate {Se(VI)}• Selenocynate (SeCN)• Selenomethionine (SeMet)• Methylseleninic Acid (MeSe)

Selenium SpeciationBRL SOP BR-0061 (IC-ICP-DRC-MS)

Metals Speciation…

A powerful tool to help address metals-related environmental issues

Thank You!

Questions? Contact Info:Michelle Briscoe

michelle@brooksrand.com

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