NSLS-II User Workshop, July 2007 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)

NSLS-II User Workshop, July 2007

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 5 th.

NSLS-II User Workshop, July 2007 Why an X-ray microprobe: Distinct advantages over many analytical techniques by allowing analyses to be done in-situ and/or in-vivo, for example being the ability to determine chemical speciation of a wide variety of toxic elements in moist soils and biological specimens with little or no chemical pretreatment, low detection limits, and minimal beam interaction. 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) 10 keV (ph/s) µXRFµXANESµEXAFSfCMT NSLS X26A Bending Magnet (2.8 GeV) 5-82 x ppm ppm1000 ppm -1 % ppm APS 13-ID Undulator (7 GeV) 14 x ppb1-10 ppm ppm1-100 ppm

NSLS-II User Workshop, July 2007 X-ray opticDiffractive OpticsReflective OpticsRefractive Optics Numerical aperture High NA possibleLimited NA Resolution limit < 1 nm?− KB: ~ 16 nm − Wolter:~3nm CRL: ~ 20 nm A-CRL: ~ 2 nm Efficiency20% - 30% (60%- 80%) 70% - 90%20% - 30% Chromaticityf ~ 1/λNon-chromaticf ~ 1/λ 2 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 errorsSmall working distance at high resolution Modified from Jörg Maser, 2006 X-ray Focusing and Imaging – Current State of the Art

NSLS-II User Workshop, July 2007 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

NSLS-II User Workshop, July 2007 Combined capabilities for small spot size, achromatic focusing, large gain and long working distance. Achromatic focusing - focus/beam position is retained during an energy scan Large gain - gains of > 10 5 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)

NSLS-II User Workshop, July 2007 KB Optics NSLS Bend (X26A) f19msource to optic distance f2 (H)0.075moptic to sample distance f2 (V)0.2moptic to sample distance m(H)120horizontal demag m(V)45vertical demag xx mhorizontal source size yy mvertical source size S' (H)5.16E-05msource size S' (V) msource size 'T'T 1.00E-06radians1.00E-07radianstotal angular RMS deviation from perfect ellipse D(H) deviation from perfect in horizontal D(V) deviation from perfect in vertical FWHM(H)9.09microns9.09microns FWHM(V)4.79microns4.70microns agrees with observations. Also, the mirror imperfections are negligible compared to the angular source size

NSLS-II User Workshop, July 2007 KB Optics NSLS-II Hard X-Ray Undulator (U19) f140msource to optic distance f2 (H)0.075moptic to sample distance f2 (V)0.2moptic to sample distance m(H) horizontal demag m(V)200vertical demag xx mhorizontal source size yy 2.6E-06mvertical source size S' (H)7E-07msource size S' (V)6.5E-08msource size 'T'T 1.00E-06radians1.00E-07radianstotal angular RMS deviation from perfect ellipse D(H) deviation from perfect in horizontal D(V) deviation from perfect in vertical FWHM(H)0.37microns0.13microns FWHM(V)0.94microns0.10microns 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

NSLS-II User Workshop, July 2007 KB Optics NSLS-II Three Pole Wiggler f140msource to optic distance f2 (H)0.075moptic to sample distance f2 (V)0.2moptic to sample distance m(H) horizontal demag m(V)200vertical demag xx mhorizontal source size yy 1.57E-05mvertical source size S' (H)3.4E-06msource size S' (V)3.93E-07msource size 'T'T 1.00E-06radians1.00E-07radianstotal angular RMS deviation from perfect ellipse D(H) deviation from perfect in horizontal D(V) deviation from perfect in vertical FWHM(H)0.70microns0.60microns FWHM(V)0.96microns0.21microns

NSLS-II User Workshop, July 2007 Zone plate based HXR µprobe An example is beamline 2ID-D at the APS 100 nm-width tin oxide nanobelt

NSLS-II User Workshop, July 2007 NSLS II Sources

NSLS-II User Workshop, July 2007 NSLS II Sources

NSLS-II User Workshop, July 2007 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 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 (  - Fe 2 O 3 ) and maghemite (  -Fe 2 O 3 ). 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 (  -Fe 2 O 3 ) and maghemite (  -Fe 2 O 3 )

NSLS-II User Workshop, July 2007 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 (  - Fe 2 O 3 ) and maghemite (  - Fe 2 O 3 ). Chemical mapping of individual grains (µ-XRF). Understand bioavailability, predict long-term stability, design remediation to ensure As immobility.

NSLS-II User Workshop, July 2007 Influence of Plutonium Oxidation State on Long-Term Transport through a Subsurface Sediment 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) 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 Optical Image Pu “hot spots” located by microXRF mapping Pu L MicroXANES M. C. Duff, D. Kaplan, Savannah River National Laboratory (SRNL), B. Powell, Clemson U., A. Lanzirotti and S. Sutton (U. Chicago, CARS)

NSLS-II User Workshop, July 2007 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

NSLS-II User Workshop, July 2007 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) 10  m Sutton, S.R., et al. (2000) Lunar Planet. Sci. XXXI,1857.

NSLS-II User Workshop, July 2007 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 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)

NSLS-II User Workshop, July 2007 Absorption Tomograms cotyledons radicle seed coat

NSLS-II User Workshop, July 2007 Fluorescence Tomograms Col-Oatvit1-1 Fe Mn Zn 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.