Canadian Centre canadien Light de rayonnement Source synchrotron

The Canadian Light Source: A New Tool for Mining and Environmental Headaches

J.N. Cutler Canadian Light Source Inc.

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Light lets you see!

Interaction of light with matter is very simple, that’s why scientists use it.

The energy of light determines what it lets you “see”

Visible light let you see “large” things X-rays let you see “through” things

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The Construction Site

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ESRF Animation

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1. E-gun 2. Transfer Line & Booster ring

3. Storage ring 4. Beamline &

end station

Synchrotron Facility Components

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Booster Ring First injection in June > 10 mA ramped to 2.9

GeV and extracted. Commissioning

complete

1x2mm

Synchrotron Hall, Main Floor

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Electromagnetic Spectrum angstrom micron millimetre

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Sample Microprobe Beamline Layout

ASI

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Canadian Light Source Inc. Vision

To advance Canadian scientific and industrial capabilities by operating the Canadian Light Source facility as the national synchrotron research and development centre of excellence.

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Multi-disciplinary Opportunities Advanced materials – hybrid materials, stress, transistors, foams

Metals/ceramics, coatings, fibers, polymers, pulp/paper, welding Information technologies (IT), storage, semi-conductors, sensors MEMS (micro-electrical-mechanical systems); Nano-technologies

Health & Life Sciences – biotech (human, animal, plant) Designer pharmaceuticals, medical imaging (cell chemistry) Genome & proteomics (protein functionality) Viruses; treatment therapies; diagnostics; implantable devices

Earth Sciences – geology, mining, industrial processing Environmental geo-chemistry, bio-active stability analysis Oil tribology, fingerprinting, soils in situ, corrosion Remediation assessments, waste management

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IR Microscopy of a fluid inclusion

Bantignies et. al. , SR News 11,31-37, 1998

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Infrared Study of Organic Material on Marine Sediment

Bare silica, low PAH Clay, OM, high PAH

20 microns SEM image of a silica particle. (Right) IR image of organic material on the silica particles. Red and yellow areas indicate high PAH concentration.

• PAHs present on silica particles were found associated with organic carbon locations. These organic matter regions containing PAHs are colonized by bacteria during biodegradation studies.

Upal et al., Environ. Sci. Technol., 2000, 34, 1729.

PresenterPresentation NotesThis is analysis of PAH uptake in a sediment/marine environment: This silica particle has clay attached, and trying to locate the PAH distribution on it was the project, finding that the Bacteria were also localised there was important to know. Microscale Location, Characterization, and Association of Polycyclic Aromatic Hydrocarbons on Harbor Sediment Particles UPAL GHOSH, J . SEBGILLETTE, RICHARD G . LUTHY ,RICHARD N . ZAREEnviron. Sci. Technol. 2000, 34, 1729-1736

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17.65 8.83 5.90 4.43 3.55 2.97 2.56d-Scale(A)

x10^3

10

20

30

40

50

60

Inte

nsity

(Cou

nts)

CuKa (0.01 deg/step), 50kV 200mA

Synchrotron x-ray (0.01 deg/step), 0.7 A

Comparing synchrotron & lab results

17.65 8.83 5.90 4.43 3.55 2.97 2.56d-Scale(A)

x10^3

10

20

30

40

50

60

Inte

nsity

(Cou

nts)

CuKa (0.01 deg/step), 50kV 200mA

Synchrotron x-ray (0.01 deg/step), 0.7 A

CANMET/Devon

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hν Atom1 Atom2

E0 e

X-ray Absorption Spectroscopy (XAS) using Synchrotron Light

)()()()(

0

0

EEEE

µµµχ −≡

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Soil Chemistry

2465 2470 2475 2480 2485 2490 2495

AMAB014

Photon Energy (eV)

Sulphide

Sulphonic acid

S K-edge

Sulphate

Sulphoxide

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Determination of Sulphur in Soil

2465 2470 2475 2480 2485 2490 2495

0.0

0.5

1.0

1.5

2.0

2.5

3.0 ASD10908 LFH Sulphide (40%) Sulphoixde (6%) Sulphonic Acid (40%) Sulphate (14%) Fit

µx (a

rb. u

nits

)

Photon Energy (eV)

• quantification of sulphur in soil

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XPS of S 2p of FeS2 c

SR at 206 eV

Schaufuss, Nesbitt , Bancroft, et al. , J.Elect. Spect. . 1998 Nesbitt et al . Amer. Min, 2000, 2001

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Synchrotron Experimental Set-up

A

A

A

I0

I

I

SR ring

Au mesh

Sample

Total Electron Yield (top 50 Å)

Fluorescence Yield (top 500 Å)

hν

µx=log (I0/I)

hν’

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Environmental; Mine Tailings

Rj Neighbour in jth shell

hν

Photoelectron wave

Scattered e wave

Nature & bio-availability of heavy metals in mine waste

Examine diffusion of materials into surrounding eco-system

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11.8 12.0 12.2 12.4 12.6 12.8 13.0 13.2

12.4 12.8 13.2

Photon Energy (keV)

• Element specific

• Sensitive to local structure

• Non-invasive

• Applicable to all sample physical states

• In Situ

Characteristic X-ray Absorption Spectra from Raffinate, Leach Residue and Tailings

As K

Se K

Pb LIII

Tailing Sample Gypsum dissolution

Leach Residue

Raffinate Fe/As 3.5

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Determination of Chemical States Using Arsenic X-ray Absorption Spectroscopy

• Position of maximum absorption is related to oxidation state of arsenic

• Tailing samples show a broadening due to a mixture of oxidation states

11.86 11.87 11.88 11.89

As K FeAsS As2O3 FeAsO4 Tailing

As+5As+3As-1

Photon Energy (keV)

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Characterization of Chemical States within Leach Residue

• XANES spectroscopy can be used to determine oxidation states within a sample

• Leach residue is a mixture of at least 3 different oxidation states

11.86 11.87 11.88 11.890.0

0.5

1.0

1.5

2.0 As-1 31%

As3+ 19%As5+ 50%

Photon Energy (keV)

Leach Residue FeAsS As2O3 "Amorphous" FeAsO4 Sum

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2 3 4 5 6 7 8 9 10

-0.2

-0.1

0.0

0.1

0.2

0.3 "Amorphous" FeAsO4 Raffinate Tailing

k[Å-1]

XAFS Comparison of Reference Compound to Raffinate and Tailing Samples

χ(k)

• Raffinate and tailings are different than “amorphous” FeAsO4

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XAFS Comparison of Reference Compounds to Raffinate and Tailings

Crystalline FeAsO4

Arsenate adsorbed on FeOOH

FeAsO4

Raffinate

Tailing

2 4 6 8 10 12k[Å-1]

k3χ(

k)

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Structural Environment around Arsenic within a Raffinate & Tailing Sample

• Tailings & raffinate are different

• Raffinate appears to contain some “amorphous” FeAsO4

2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.40.00

0.02

0.04

0.06

0.08

0 1 2 3 4 5 6 7 80.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

0.20

0.22

Mag

nitu

de o

f Fou

rier T

rans

form

of k

3 χ(k

)

Crystalline FeAsO4 "Amorphous" FeAsO4 Arsenate adsorbed on FeOOH Neutralized raffinate Tailing

R (Å)

As-Fe

As-O

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11.86 11.88 11.90

11.88

Microprobe Study of Mine Tailings

11.86 11.90

Energy (keV)

As(0) + As(III) As(V)

Nickel Map Arsenic Map

Iron Map Calcium Map

500 µm

500 µ

m

Energy (keV)

As(0) + As(III)

As(V)

Photon Energy: 12 keV Spot size: 5µm

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Selenium in the Environment

12645 12650 12655 12660 12665 12670 12675 1268012650 12660 12670 12680

CRC 292800-4200 ppb Se

Se(+VI)Se(+IV)

Se(0)Se(-II)

CRC 30800-1300 ppb Se

CRC 341600-1700 ppb Se

Photon Energy (eV)

http://www.uky.edu/%7Ersilver/CommunityService/coal.jpg

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Effects of Earthworms on Soil Manganese Picture of the studied worm burrow.

Mn K-edge micro-XANES spectra.

• Earthworms move materials through soils

• Fecal matter often contains higher levels of metals than surrounding soil

• Not only do worms move material but they change the speciation of the metals

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Toxic Metal Attenuation by Root-borne Carbonate Nodules

•Zn and Mn correlate with nodules •Fe and Pb are fairly uniformly distributed •As is heterogenous and poorly correlated with epidermis

S. Fendorf, C. Hansel, GeoCARS APS

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Cadmium-Challenged Corn Roots

Distance (microns, Arb. zero)

1750 1800 1850 1900 1950 2000 2050 2100 2150 2200

Nor

mal

ized

Cou

nts

Distance (microns, Arb. zero)

50 100 150 200 250 300 350

Nor

mal

ized

Cou

nts

Control Cadmium-Challenged

Ca maps

Cu map Naftel et al.

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Micro-Imaging and Tomography Uranium fuel particle from Chernobyl B. Salbu, K.

Janssens, T. Krekling, A. Simionovici, M. Drakopoulos, C. Raven, I. Snigireva, A. Snigirev, O. C. Lind, D. H. Oughton, F. Adams, V.a. Kashparov

ESRF

Chernobyl West

Chernobyl North

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glucose

cellulose

Using SR to see the wood from the trees

• measurement of microfibril angle within wood

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Opportunities • Characterization (oxidation states and mineralogy) of

metals in solids – tailings – sludges from water treatment plants – sediments from limnocorrals – wetland uptake

• sulphur associated with ARD • biochemistry of SRBs and

bioreactors

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Conclusion

The uses of synchrotron light are as limitless as your

imagination is!

www.cls.usask.ca

www.lightsource.ca

Slide Number 1The Canadian Light Source: A New Tool for Mining and Environmental HeadachesLight lets you see!The Construction SiteESRF AnimationSynchrotron Facility ComponentsBooster RingSynchrotron Hall, Main FloorElectromagnetic SpectrumSample Microprobe Beamline LayoutCanadian Light Source Inc. VisionMulti-disciplinary OpportunitiesIR Microscopy of a fluid inclusionInfrared Study of Organic Material on Marine SedimentComparing synchrotron & lab resultsX-ray Absorption Spectroscopy (XAS) using Synchrotron LightSoil ChemistryDetermination of Sulphur in SoilXPS of S 2p of FeS2Synchrotron Experimental Set-upEnvironmental; Mine TailingsCharacteristic X-ray Absorption Spectra from Raffinate, Leach Residue and TailingsDetermination of Chemical States Using Arsenic X-ray Absorption SpectroscopyCharacterization of Chemical States within Leach ResidueXAFS Comparison of Reference Compound to Raffinate and Tailing SamplesXAFS Comparison of Reference Compounds to Raffinate and TailingsStructural Environment around Arsenic within a Raffinate & Tailing SampleMicroprobe Study of Mine TailingsSelenium in the EnvironmentEffects of Earthworms on Soil ManganeseToxic Metal Attenuation by Root-borne Carbonate NodulesCadmium-Challenged Corn RootsMicro-Imaging and TomographySlide Number 35OpportunitiesConclusionwww.cls.usask.ca