# Presentation: 565229

## NSLS-II Environmental Sciences Breakout Session

| Antonio  Lanzirotti (U. Chicago) | Welcoming Remarks |  |
| --- | --- | --- |
|  | Review of NSLS Molecular Environmental Sciences statistics. How are MES researchers utilizing the NSLS. |  |
|  | Overview of U.Chicago CARS MES research and future directions | (10 minutes) |
| Richard Reeder (Stony Brook U.) | EnviroSync MES community efforts |  |
|  | Overview of Stony Brook MES synchrotron research and future directions | (10 minutes) |
| Jeff Fitts (BNL Env. Sciences) | BNL EnviroSuite initiative | (10 minutes) |
| Satish Myneni (Princeton U.) | Overview of Princeton U. Molecular Environmental Chemistry synchrotron research and future directions | (10 minutes) |
| Matt Ginder-Vogel (U. Delaware) | Overview of U. Delaware Environmental Soil Chemistry synchrotron research and future directions | (10 minutes) |
| Unscheduled Presentations | Open Presentations by Attendees | (15 minutes) |
| NSLS-II Techincal Review | Brief Overview of proposed capabilities of NSLS-II. Impact for the MES community | (10 minutes) |
| Open Discussion | What are the requirements of the community for continued high quality MES research at NSLS-II?
What new research that will be made possible by NSLS-II?
Of the techniques potentially available at NSLS-II, which are the highest priorities? 
What is the preferred mode of access for the community?  Dedicated beamlines? General User access only? How should planning/design/proposal writing/operations teams be organized/supported?   
What existing equipment is likely to be transferable? | (30 minutes) |
| Closeout | Recommendations of the community to NSLS-II | (15 minutes) |

## Slide 2

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## NSLS-II Workshop Deliverables

- What are the key scientific drivers? What experiments will NSLS-II enable that are not presently possible?
- What technical capabilities will these require? (Beamlines, endstations, undulators...)
- Estimate of community size.
- What detector requirements does this field have? Do these require R+D?
- What software and computing infrastructure requirements are there? (Control, data acquisition, analysis)
- Any particular accelerator requirements?
- Any particular conventional facility requirements?
- Report Summarizing what was learned will be sent to DOE by COB August 5th.

## Synchrotron Hard X-Ray Microprobe in Environmental Sciences

**Multiple Complimentary Techniques**
**μXRF and elemental mapping:** Spot XRF analyses of trace element composition.
**μXAFS:** Spot XANES and EXAFS determinations of oxidation state and speciation.
**μXRD:** In-situ phase identification and correlation with elemental and speciation information.
**Fluorescence Microtomography:**  Internal 2D and 3D elemental imaging.

**Synchrotron Hard X-Ray Microprobe in Environmental Sciences**

| Two KB-Mirror Based X-Ray Microprobes |  |  |  |  |  |  |  |
| --- | --- | --- | --- | --- | --- | --- | --- |
| Beam
Line | Source | Beam Size 
(μm) | Flux @ 10 keV (ph/s) | μXRF | μXANES | μEXAFS | fCMT |
| NSLS
X26A | Bending Magnet
(2.8 GeV) | 5-8 | 2 x 108 | 1 ppm | 10-100 ppm | 1000 ppm -1 % | 10-100 ppm |
| APS
13-ID | Undulator
(7 GeV) | 1 | 4 x 1011 | 100 ppb | 1-10 ppm | 100-1000 ppm | 1-100 ppm |

## X-ray Focusing and Imaging – Current State of the Art

| X-ray optic | Diffractive Optics | Reflective Optics | Refractive Optics |
| --- | --- | --- | --- |
| Numerical aperture | High NA possible | Limited NA | Limited NA |
| Resolution limit | < 1 nm? | − KB: ~ 16 nm
− Wolter:~3nm | CRL: ~ 20 nm
A-CRL: ~ 2 nm |
| Efficiency | 20% - 30% (60%-80%) | 70% - 90% | 20% - 30% |
| Chromaticity | f ~ 1/λ | Non-chromatic | f ~ 1/λ2 |
| Features | • Monochromatic beam
• On-axis geometry
• Any x-ray energy | • White (pink) beam (non-ML)
• Grazing inc. geometry
• Any x-ray energy
• KB: working distance! | • Monochromatic beam
• On-axis geometry
• Limited energy range
• Long lenses |
| Limitations | •(High aspect ratio/tilt)
•Positioning-alignment | Figure errors | Small working distance at high resolution |

- Modified from Jörg Maser, 2006

***X-ray Focusing and Imaging – Current State of the Art***

## State of the art in x-ray imaging and focusing (2D focus):

-  Refractive Optics: δ ~ 50 nm (E = 21 keV) (*Schroer, APL, 2005*)
-  Reflective Optics: δ ~ 40 nm (E ~ 15 keV) (*Mimura, JJAP 2005*)
-  Diffractive Optics: δ ~ 15 nm, (E = 0.8 keV) (*Chao, Nature, 2005*)
**What is the ultimate resolution limit for x-ray focusing?**
-  Diffractive optics: ~ 1 nm (Kang, 2006); Å feasible?
-  Reflective Optics: ~ 16 nm (KB), 3 nm (Wolter) (non-ML)
-  Refractive Optics: ~ 2 nm (β = 0, Schroer, 2005)

***X-ray Focusing and Imaging – Current State of the Art***

## Advantages of KB Microfocusing

**Achromatic focusing** - focus/beam position is retained during an energy scan
**Large gain** - gains of > 105 achievable, high elemental sensitivity
**Long working distance** - simplifies use of detectors, optical viewing systems, special sample chambers, etc.
**Disadvantage** - beam sizes ~ 0.1 micrometer currently unachievable for hard x-rays

**Advantages of KB Microfocusing**

- KB Microfocusing System Designed by P. Eng (U. Chicago)

## KB Optics NSLS Bend (X26A)

| f1 | 9 | m | source to optic distance |  |  |  |  |  |  |  |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |
| f2 (H) | 0.075 | m | optic to sample distance |  |  |  |  |  |  |  |
| f2 (V) | 0.2 | m | optic to sample distance |  |  |  |  |  |  |  |
| m(H) | 120 |  | horizontal demag |  |  |  |  |  |  |  |
| m(V) | 45 |  | vertical demag |  |  |  |  |  |  |  |
| x | 0.000464 | m | horizontal source size |  |  |  |  |  |  |  |
| y | 0.00009 | m | vertical source size |  |  |  |  |  |  |  |
| S' (H) | 5.16E-05 | m | source size |  |  |  |  |  |  |  |
| S' (V) | 0.00001 | m | source size |  |  |  |  |  |  |  |
| 'T | 1.00E-06 | radians | 1.00E-07 | radians | total angular RMS deviation from perfect ellipse |  |  |  |  |  |
|  |  |  |  |  |  |  |  |  |  |  |
| D(H) | 1.000752 |  | 1.00001 |  | deviation from perfect in horizontal |  |  |  |  |  |
| D(V) | 1.019804 |  | 1.0002 |  | deviation from perfect in vertical |  |  |  |  |  |
|  |  |  |  |  |  |  |  |  |  |  |
| FWHM(H) | 9.09 | microns | 9.09 | microns |  |  |  |  |  |  |
| FWHM(V) | 4.79 | microns | 4.70 | microns |  |  |  |  |  |  |
| agrees with observations.  Also, the mirror imperfections are negligible compared to the angular source size  |  |  |  |  |  |  |  |  |  |  |

## KB Optics NSLS-II Hard X-Ray Undulator (U19)

| f1 | 40 | m | source to optic distance |  |  |   |   |   |   |   |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |
| f2 (H) | 0.075 | m | optic to sample distance |  |  |  |  |  |  |   |
| f2 (V) | 0.2 | m | optic to sample distance |  |  |  |  |  |  |   |
| m(H) | 533.3333 |  | horizontal demag |  |  |  |  |  |  |   |
| m(V) | 200 |  | vertical demag |  |  |  |  |  |  |   |
| x | 0.000028 | m | horizontal source size |  |  |  |  |  |  |   |
| y | 2.6E-06 | m | vertical source size |  |  |  |  |  |  |   |
| S' (H) | 7E-07 | m | source size |  |  |  |  |  |  |   |
| S' (V) | 6.5E-08 | m | source size |  |  |  |  |  |  |   |
| 'T | 1.00E-06 | radians | 1.00E-07 | radians | total angular RMS deviation from perfect ellipse |  |  |  |  |  |
|   |  |  |  |  |  |  |  |  |  |   |
| D(H) | 3.027089 |  | 1.04002 |  | deviation from perfect in horizontal |  |  |  |  |   |
| D(V) | 30.78548 |  | 3.23534 |  | deviation from perfect in vertical |  |  |  |  |   |
|   |  |  |  |  |  |  |  |  |  |   |
| FWHM(H) | 0.37 | microns | 0.13 | microns |  |  |  |  |  |   |
| FWHM(V) | 0.94 | microns | 0.10 | microns |  |  |  |  |  |   |
| both vertical and horizontal are improved with better mirrors and benders;  |  |  |  |  |  |  |  |  |  |   |
| close to linear esp. vertical. Improve deviation by factor of 3 and beam gets smaller by ~ that amount |  |  |  |  |  |  |  |  |  |   |

## KB Optics NSLS-II Three Pole Wiggler

| f1 | 40 | m | source to optic distance |  |  |   |   |   |   |   |
| --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |
| f2 (H) | 0.075 | m | optic to sample distance |  |  |  |  |  |  |   |
| f2 (V) | 0.2 | m | optic to sample distance |  |  |  |  |  |  |   |
| m(H) | 533.3333 |  | horizontal demag |  |  |  |  |  |  |   |
| m(V) | 200 |  | vertical demag |  |  |  |  |  |  |   |
| x | 0.000136 | m | horizontal source size |  |  |  |  |  |  |   |
| y | 1.57E-05 | m | vertical source size |  |  |  |  |  |  |   |
| S' (H) | 3.4E-06 | m | source size |  |  |  |  |  |  |   |
| S' (V) | 3.93E-07 | m | source size |  |  |  |  |  |  |   |
| 'T | 1.00E-06 | radians | 1.00E-07 | radians | total angular RMS deviation from perfect ellipse |  |  |  |  |  |
|   |  |  |  |  |  |  |  |  |  |   |
| D(H) | 1.160181 |  | 1.00173 |  | deviation from perfect in horizontal |  |  |  |  |   |
| D(V) | 5.192739 |  | 1.12234 |  | deviation from perfect in vertical |  |  |  |  |   |
|   |  |  |  |  |  |  |  |  |  |   |
| FWHM(H) | 0.70 | microns | 0.60 | microns |  |  |  |  |  |   |
| FWHM(V) | 0.96 | microns | 0.21 | microns |   |   |   |   |   |   |

## Zone plate based HXR μprobe

- An example is beamline 2ID-D at the APS

- 100 nm-width tin oxide nanobelt

## NSLS II Sources

## NSLS II Sources

## Technique: X-ray Micro- Fluorescence, Spectroscopy, Diffraction

**Technique:** X-ray Micro- Fluorescence, Spectroscopy, Diffraction
**Researchers:**
- H. Jamieson, S. Walker, C. Andrade, (Queen’s University, Canada), A. Lanzirotti and S. Sutton (U. Chicago, CARS)
**Publication:**
- Walker, S.R., Jamieson, H.E., Lanzirotti, A. and Andrade, C.F.   (2005) Determining arsenic speciation in iron oxides: Application of synchrotron micro-XRD and micro-XANES at the grain scale. Canadian Mineralogist, v. 43, p. 1205-1224

**Synchrotron-based μ-XRF mapping, μ-XANES and μ-XRD of arsenic-rich gold mine tailings and lacustrine sediments from Yellowknife Bay, Canada**

- Characterize As bearing solids in roaster residue and roaster-derived iron oxides in a subareal weathered tailings horizon
- Oxidation state and bonding mechanisms at the scale of individual particle (μ-XANES).
- Phase identification (μ-XRD) of individual grains. Objective is to distinguish hematite (-Fe2O3) and maghemite (-Fe2O3).
- Chemical mapping of individual grains (μ-XRF).
- Understand bioavailability, predict long-term stability, design remediation to ensure As immobility.

- Field of view 0.16mm x 0.10mm
- Complex zoning at micron scales

- hematite (-Fe2O3) and maghemite (-Fe2O3)

## Synchrotron-based μ-XRF mapping, μ-XANES and μ-XRD of arsenic-rich gold mine tailings and lacustrine sediments from Yellowknife Bay, Canada

**Synchrotron-based μ-XRF mapping, μ-XANES and μ-XRD of arsenic-rich gold mine tailings and lacustrine sediments from Yellowknife Bay, Canada**

- H. Jamieson, S. Walker, C. Andrade, (Queen’s University, Canada), A. Lanzirotti and S. Sutton (U. Chicago, CARS)

- Characterize As bearing solids in roaster residue and roaster-derived iron oxides in a subareal weathered tailings horizon
- Oxidation state and bonding mechanisms at the scale of individual particle (μ-XANES).
- Phase identification (μ-XRD) of individual grains. Objective is to distinguish hematite (-Fe2O3) and maghemite (-Fe2O3).
- Chemical mapping of individual grains (μ-XRF).
- Understand bioavailability, predict long-term stability, design remediation to ensure As immobility.

##  Pu(IV) and Pu(VI) were placed in Savannah River Site lysimeters (1980) exposed to natural weather conditions, with the intent of evaluating the long-term environmental fate of Pu.

-  Pu(IV) and Pu(VI) were placed in Savannah River Site lysimeters (1980) exposed to natural weather conditions, with the intent of evaluating the long-term environmental fate of Pu.
-  Pu in the Pu(VI)-amended lysimeter traveled ~10 times faster (12.5 cm yr-1) than the Pu(IV)-amended lysimeter (1.1 cm yr-1)
-  MicroXANES showed Pu oxidation state was IV in IV-amended system (undetectable oxidized species)

- Yucca Mtn Tuff soak experiment

- M. C. Duff, D. Kaplan, Savannah River National Laboratory (SRNL), B. Powell, Clemson U., A. Lanzirotti and S. Sutton (U. Chicago, CARS)

## Interplanetary Dust Particles

-  Potentially most primitive solar system solids
-  Meteoritic material least altered by atmospheric entry
-  Hosts of interstellar grains

- 1 μm

-  Total mass ~ 30 picogram (trillionths of a gram)

**Interplanetary Dust Particles**

## IDPs: Fluorescence Microtomography

-  Are the volatile element enrichments indigenous or stratospheric contamination?
-  Fluorescence tomography images show that volatile elements (Zn and Br) are not strongly surface-correlated, suggesting that these elements are primarily indigenous rather than from atmospheric contamination
-   Information on the host phases of trace elements (e.g., Zn, the first element lost during entry heating, is isolated in a few spots, probably ZnS identified by TEM in IDPs; Sr in carbonate)

- Sutton, S.R., et al.  (2000) Lunar Planet. Sci. XXXI,1857.

## Ionomics: the study of how genes regulate ions in cells.

Fe deficiency most common nutritional disorder in the world

2 billion (mainly in developing countries) are anemic

A number of the key genes involved in iron uptake in plants have been identified. Armed with this knowledge, it should now be possible to engineer or breed plants with improved iron uptake abilities and in more bioavailable forms.

Use synchrotron x-ray microprobe techniques to assign functions to metal homeostasis genes whose phenotypes could not be observed using volume-averaged metal analysis techniques

- Fe deficiency most common nutritional disorder in the world
- 2 billion (mainly in developing countries) are anemic
- A number of the key genes involved in iron uptake in plants have been identified. Armed with this knowledge, it should now be possible to engineer or breed plants with improved iron uptake abilities and in more bioavailable forms.
- Use synchrotron x-ray microprobe techniques to assign functions to metal homeostasis genes whose phenotypes could not be observed using volume-averaged metal analysis techniques

**Genomics to Ionomics: Metal homeostatis in plants**

**Technique:** X-ray Fluorescence Computed Micro-Tomography
**Researchers:**
- T. Punshon and M. L. Guerinot (Dartmouth U.), A. Lanzirotti (U. Chicago, CARS)
**Publication:**
- S. Kim, T. Punshon, A. Lanzirotti, L. Li, J. Alonso,
- J. Ecker, J. Kaplan and M. L. Guerinot (2006) Localization of Iron in Arabidopsis Seed Requires the Vacuolar Membrane
- Transporter VIT1, *Science*.

*Arabidopsis thaliana* (Mouse-Eared Cress)
- genome sequenced (2000)

## Absorption Tomograms

## Fluorescence Tomograms

**Fluorescence Tomograms**

-  Synchrotron x-ray fluorescence microtomography shows that the majority of iron is precisely
- localized to the provascular strands of the embryo. This localization of iron is completely
- abolished when the vacuolar iron uptake transporter VIT1 is disrupted, making vacuoles
- a promising target for increasing the iron content of seeds.