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Transcript of Www.brooksrand.com Metals Speciation as a Tool for Addressing Environmental Issues Michelle Briscoe...
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Metals Speciation as a Tool for Addressing Environmental Issues
Michelle BriscoePresident/CEO, Brooks Rand [email protected]
Presented at the DOECAP ASP Workshop, Albuquerque, NM, September 17, 2014
MEANINGFUL METALS DATAwww.brooksrand.com
206-632-6206 [email protected]
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!
MEANINGFUL METALS DATAwww.brooksrand.com
206-632-6206 [email protected]
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
MEANINGFUL METALS DATAwww.brooksrand.com
206-632-6206 [email protected]
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
MEANINGFUL METALS DATAwww.brooksrand.com
206-632-6206 [email protected]
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
MEANINGFUL METALS DATAwww.brooksrand.com
206-632-6206 [email protected]
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)
MEANINGFUL METALS DATAwww.brooksrand.com
206-632-6206 [email protected]
Metals SpeciationTools to Support a Wide Variety of Project Types
Different Species have Different
Properties
Risk Assessment
Treatment Technologies
Transport & Mobility
Bioavailability
MEANINGFUL METALS DATAwww.brooksrand.com
206-632-6206 [email protected]
Typical Landfill Gas Power Plant
Courtesy City of Vancouver BC
MEANINGFUL METALS DATAwww.brooksrand.com
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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
MEANINGFUL METALS DATAwww.brooksrand.com
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Total Arsenic Analysis
Incoming Municipal WaterTotal Arsenic 0.14 µg/L
Power Plant EffluentTotal Arsenic 1,560 µg/L
MEANINGFUL METALS DATAwww.brooksrand.com
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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
MEANINGFUL METALS DATAwww.brooksrand.com
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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)
MEANINGFUL METALS DATAwww.brooksrand.com
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EPA Method 1632AManual Analysis for Arsenic Speciation
120 °C
20 mL
MEANINGFUL METALS DATAwww.brooksrand.com
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IC-ICP-MSAutomated Analysis for Arsenic Speciation
Sour
ce:
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w.s
peci
ation
.net
MEANINGFUL METALS DATAwww.brooksrand.com
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IC-ICP-MS Chromatogram
As(III)
DMAs MMAs
As(V)
MEANINGFUL METALS DATAwww.brooksrand.com
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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
MEANINGFUL METALS DATAwww.brooksrand.com
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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
MEANINGFUL METALS DATAwww.brooksrand.com
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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
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5-Step SSE Sample Preparation
MEANINGFUL METALS DATAwww.brooksrand.com
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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
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Treatment of Oak Ridge Y-12 Site SoilsAll samples were “spiked” with 10,000 mg/kg Hg(0)
MEANINGFUL METALS DATAwww.brooksrand.com
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Coal-Fired Power Plant with Flue Gas Desulfurization (FGD)
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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 DATAwww.brooksrand.com
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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 DATAwww.brooksrand.com
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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)
MEANINGFUL METALS DATAwww.brooksrand.com
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Selenium SpeciationBRL SOP BR-0061 (IC-ICP-DRC-MS)
MEANINGFUL METALS DATAwww.brooksrand.com
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Metals Speciation…
A powerful tool to help address metals-related environmental issues