Evaluating Synchrotron-Based Scanning Laue Microdiffraction for

Sep 26, 2018 - In this manuscript, three constructed mineral mixtures and two ... rather than a pure franklinite phase in a Zn smelter-contaminated so...
0 downloads 0 Views 8MB Size
Download PDF
Article Cite This: ACS Earth Space Chem. XXXX, XXX, XXX−XXX

http://pubs.acs.org/journal/aesccq

Evaluating Synchrotron-Based Scanning Laue Microdiffraction for Mineralogy Mapping in Heterogeneous Samples Jordan G. Hamilton,*,† Joel W. Reid,‡ Renfei Feng,‡ and Derek Peak† †

Department of Soil Science, University of Saskatchewan, 51 Campus Drive, Saskatoon, Saskatchewan S7N 5A8, Canada Canadian Light Source, Incorporated, 44 Innovation Boulevard, Saskatoon, Saskatchewan S7N 2V3, Canada

‡

Downloaded via UNIV OF NEW ENGLAND on October 12, 2018 at 13:26:04 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

S Supporting Information *

ABSTRACT: Synchrotron Laue microdiffraction imaging (MDI) is a well-used technique in material science research and environmental research to determine the strain/stress and orientation of quartz and calcite crystallites. However, Laue MDI has unrealized potential to provide spatially resolved mineralogical information for geochemical and contaminated site samples. In this manuscript, three constructed mineral mixtures and two environmental samples were analyzed with Laue MDI to illustrate the strengths, limitations/challenges, and applicability of the technique for environmental research. Mixture 1 (quartz, calcite, and magnetite), mixture 2 (quartz, calcite, magnetite, and clinochlore), and mixture 3 (calcite, hematite, sphalerite, and arupite) were constructed to highlight the potential limitations of the technique. The mixtures illustrate the potential of Laue MDI and X-ray fluorescence imaging for clearly identifying environmentally relevant contaminant and sorbent minerals while demonstrating that minerals smaller than the incident beam are challenging to index. Two environmental samples were then used for comparison to the synthetic mixtures. Laue MDI analysis was successful in identification of a Zn-substituted magnetite/non-stoichiometric franklinite rather than a pure franklinite phase in a Zn smelter-contaminated soil. Laue MDI was also crucial in the evaluation of the particle size of carbonates to distinguish between parent material (calcite) and secondary carbonate minerals (dolomite) in a calcareous soil undergoing phosphorus nutrient applications to stimulate hydrocarbon remediation. Despite challenges and limitations, Laue MDI, when correctly used, is a valuable technique for earth and environmental science researchers. KEYWORDS: Laue diffraction, microdiffraction imaging, constructed mineral mixtures, powder X-ray diffraction, X-ray fluorescence imaging

■

INTRODUCTION Recent advances in synchrotron beamline optics allow for the collection of high-resolution spatially resolved X-ray diffraction (XRD) data of crystalline and polycrystalline samples at micrometer and sub-micrometer resolution.1−5 Laue microdiffraction imaging (MDI) is not a new technique for the analysis of environmentally relevant samples because there are a number of studies regarding the strain/stress of quartz and calcite crystallites.6−9 However, there is a limited number of applications of Laue MDI to study the spatial distribution and fate of contaminants/contaminant mineral phases in the environment. A knowledge gap currently exists regarding the potential applications of Laue MDI for characterizing the spatial mineralogy and contaminant fate of polycrystalline environmental and geological samples. One environmental example of Laue MDI is strain and orientation imaging of quartz.6,7 Chen and co-authors used Laue MDI to study the residual stress/strain in quartz fragments from the San Andreas fault, specifically using Laue MDI to determine the stress derived from the lattice distortions.6 Similarly, the stress of crystal lattice distortions can be useful in determining mineralogical processes, including helping to determine the processes behind the formation of Bastogne boudins.7 Additionally, © XXXX American Chemical Society

strain and stress imaging with Laue MDI has been both used on both environmental calcite minerals from earthquake fault lines and Antarctic ice core samples.8,9 However, MDI of geochemical systems has typically used a monochromatic incident X-ray beam to collect a diffraction pattern at each data point.10−16 Polychromatic MDI is fundamentally a single-crystal technique, requiring minerals to be larger than or close in size to the incident beam, whereas monochromatic MDI is generally a polycrystalline technique, which allows for much smaller mineral particles (clays) to be imaged.16 For a more in-depth comparison of mono- and polychromatic MDI, see the study by Tamura and Kunz.16 One of the major advantages of synchrotron MDI for environmental and geochemical research is the simultaneous collection with X-ray fluorescence imaging (XFI), providing both spatially resolved mineralogical and elemental images.17 The combination of mineralogical and elemental imaging provides geochemical information that may otherwise be Received: Revised: Accepted: Published: A

May 16, 2018 September 7, 2018 September 26, 2018 September 26, 2018 DOI: 10.1021/acsearthspacechem.8b00063 ACS Earth Space Chem. XXXX, XXX, XXX−XXX

Article

ACS Earth and Space Chemistry

(SiO2), magnetite (Fe3O4), and calcite (CaCO3). These mineral components were chosen for several reasons: they all have mean particle sizes greater than 5 μm; they all strongly scatter X-rays; and they are composed of elements measurable within the XFI constraints of the beamline. Mixture 2 is similar to mixture 1 with an additional component of the clay mineral clinochlore [(Mg,Fe2+)5Al2Si3O10(OH)8]. The addition of clinochlore to mixture 2 is designed to highlight the ability/limitations of Laue microdiffraction to identify clay mineral components. Mixture 3 combines minerals typically associated with mining/smelter mineral systems undergoing remediation: calcite, hematite (Fe2O3), sphalerite (ZnS), and arupite [Ni3(PO4)2·8H2O]. Each mineral component has a distinct elemental signature to help distinguish the spatial distribution of each mineral phase. The composition of each mixture was calculated by mass using an analytical balance, and the relative abundance was also determined via Bragg XRD and subsequent Rietveld refinement. All measurements were conducted at the Canadian Light Source (CLS) synchrotron located in Saskatoon, Saskatchewan, Canada. Synchrotron powder X-ray diffraction (SP-XRD) measurements were conducted at the CMCF-BM (08B1-1) beamline.21 Powder diffraction measurements of the constructed mixtures were conducted at room temperature and using a Rayonix MX300-HE wide area detector with an incident X-ray beam of 18 keV and a wavelength of 0.688 88 Å. The constructed mineral mixtures were loaded into polyimide tubing for SP-XRD measurement. The two-dimensional (2D) diffraction patterns were calibrated using a LaB6 standard prior to integration. Data processing was completed using the GSAS-II software package.22,23 Verification/phase identification and the crystallographic information used during Laue diffraction analysis of each constructed mixture and natural sample were completed using X’Pert HighScore Plus (PANalytical). Rietveld refinements were completed on the constructed mixtures using GSAS-I to verify and determine the relative composition of each mixture.24,25 Laue microdiffraction and XFI were collected simultaneously at the very sensitive elemental and structural probe employing radiation from a synchrotron (VESPERS, 07B2-1) beamline using a polychromatic “pink” beam ranging in energy from 6 to 25 keV.26 Laue microdiffraction measurements were collected with a 2D PILATUS 1M detector with an active area array of 1043 × 981 pixels. Measurements at the VESPERS beamline were made with a 5 × 5 μm incident beam spot size, with each spot collected with a 1 s dwell, and the detector was located 180 mm from the sample for all measurements. Laue microdiffraction was collected in reflective geometry with the sample surface aligned at a 45° angle to the incident beam, with the detector making a 90° angle with the incident beam. Each Laue microdiffraction and X-ray fluorescence (XRF) image map was collected to be 300 × 300 μm in size, with a 5 μm step between each data point. XRF images were collected using a singleelement Vortex silicon drift detector. The constructed mineral mixtures were mounted for analysis as powders between layers of Kapton tape. Spatially resolved XFI data was processed using Sam’s microprobe analysis kit (SMAK) software (Sam Webb, Stanford Synchrotron Radiation Lightsource), which included subtracting the inline I0 correction, producing elemental intensity, and generating tricolor images. Laue diffraction images were sequentially analyzed using X-ray microdiffraction analysis software (XMAS).1,18,20,27 Each Laue diffraction image was indexed by XMAS using the crystallographic information determined through phase identification of the Bragg SP-XRD

unavailable, only inferred, or determined through multiple analysis techniques. Measuring Laue diffraction patterns at the micrometer scale allows for the matching/indexing of Laue reflections with patterns calculated from crystal structures to indicate the presence/absence of a mineral.3,18 The resulting mineralogical heat maps can be directly correlated to the relative elemental concentrations obtained with XFI. These mineral heat maps are generated by the analysis software matching theoretical “expected” reflections of a particular crystal structure with the location of the measured Laue reflections from the powder sample.3,5,18 In large part, Laue MDI may largely be an underused technique for environmental contaminant research as a result of a combination of experimental and hardware limitations. From an experimental standpoint, Laue MDI is highly constrained by the size of minerals of interest and beamline incident beam spot size. Minerals can be identified when they are single crystals similar or larger than the incident beam size or large enough to provide enough reflections to index.18 As an example, a microprobe beamline with a spot size of 5 × 5 μm may limit the utility of the technique because many environmentally relevant minerals may be below detection limits. A Laue diffraction beamline with, for example, a 100 nm2 spot size would image a much larger fraction of clay constituents of a soil, improving the applicability of the technique for soil and environmental science research. Unfortunately, most synchrotron beamlines capable of stepwise measurement of Laue MDI currently operate in the micrometer range best suited for larger crystal sizes.3,18 Heterogenous environmental samples present several experimental challenges because they commonly contain a wide range of mineral phases with multiple orientations contributing Laue reflections. Mineral orientation of heterogeneous samples can affect the analysis because of the difficulty in accounting for all of the possible orientations and unit cell variations of natural samples. Mineral overlap in samples can result in a higher number of reflections that can obscure the reflections of other minerals of interest, lowering confidence in spatial identification. Use of a representative crystal structure for each mineral is extremely important for the correct indexing of Laue reflections.19,20 Incorrect or incomplete mineral identification will result in poor results during the indexing of Laue reflections in MDI analysis. The objective of this manuscript is to highlight the validity of Laue MDI as a valuable technique for characterizing mineralogical samples relevant to earth science and geochemical research. A variety of environmentally relevant constructed mineral mixtures were analyzed to highlight the strengths and weaknesses associated with Laue MDI on environmental samples. The capabilities of Laue MDI are also highlighted with two real world environmental samples, where the technique provided valuable chemical information: (1) mineral characterization from a smelter-contaminated soil environment and remediation study and (2) carbonate mineral characterization from a calcareous subsoil receiving phosphorus nutrient amendments.

■

MATERIALS AND METHODS Three constructed mineral mixtures were produced to investigate and highlight the capability of Laue MDI to determine the spatial colocation of environmentally relevant minerals. All minerals were ground to a uniform particle size with a mortar and pestle prior to mixing to reduce the largest particle sizes while not necessarily reducing the particle size of the smallest particles. Mixture 1 is a three-component mixture of quartz B

DOI: 10.1021/acsearthspacechem.8b00063 ACS Earth Space Chem. XXXX, XXX, XXX−XXX

Article

ACS Earth and Space Chemistry Table 1. Rietveld Refinements for Each of the Constructed Mixtures mineral component (wt %) sample

quartz

magnetite

calcite

hematite

sphalerite

mixture 1 mixture 2 mixture 3

41 29

23 13

35 27 37

15

23

clinochlore

arupite

31 25

Figure 1. (Left) Laue microdiffraction tricolor image of mixture 1 (300 × 300 μm) consisting of magnetite, quartz, and calcite collected at a 5 × 5 μm incident beam spot size. (Right) Corresponding XRF image color plot of Ca and Fe is collected simultaneously, providing elemental spatial distributions to aid in identifying mineral colocations.

indexed during automated analysis. The VESPERS beamline is unable to directly measure the Si fluorescence under atmospheric conditions; nonetheless, quartz spatial distributions in Laue MDI do not correlate to either calcite or magnetite. Further evidence that all mineral components have been correctly indexed is that they are mapped as discrete mineral particles. The particle sizes of the minerals in mixture 1 were all much larger than the incident beam of the VESPERS beamline. Significant mineral overlap/colocation of minerals would likely have been due to the sequential data analysis process in XMAS, because a high number of Laue reflections from a mineral, such as quartz, may result in incidentally indexed reflections for other minerals during the automated sequential analysis of large Laue data sets. This overlap may also be the result of grain-mounted samples, with the X-ray beam probing three-dimensionally into the sample. Mixture 2 is designed to challenge Laue MDI by attempting to index a clay mineral component in a multi-mineral mixture. Mixture 2 is a four-component mixture similar to mixture 1 (quartz, magnetite, and calcite) with the addition of the clay mineral clinochlore as a component with a particle size smaller than that of the incident X-ray beam. Rietveld refinement of mixture 2 (Table 1) found that mineralogy (as weight percent) consists of 29% quartz, 13% magnetite, 27% calcite, and 31% clinochlore. As in mixture 1, the results (Figure 2) of mixture 2 establish fairly distinct spatial distributions between calcite, magnetite, and quartz. However, the clinochlore mineral component could not be separately identified from the main three mineral components, because the clinochlore reflections all correlate with other mineral particles. The areas where clinochlore is indexed coincide with a large number of total Laue reflections from one of the other three mineral components rather than distinct clinochlore particles. This demonstrates a limitation of Laue MDI for environmental samples when the mineral is smaller than the incident beam: a bleed-through effect from minerals, such as quartz, can persist even in samples where the target mineral is being correctly indexed. It is therefore extremely important in environmental/earth science samples to

data. In short, using the automated XMAS features, a background was subtracted from each Laue image prior to a peak search and the indexing of Laue reflections for each crystal phase. The software parameters selected prior to analysis of the Laue images can have a significant influence on the results. One key parameter is the intensity threshold for detecting Laue reflections. The threshold setting controls the number of reflections detected for any given Laue image, excluding reflections below the set intensity threshold.20 A low threshold setting will allow for the detection of weak reflections, increasing the number of reflections possible for indexing.20 If this parameter is set too low, the potential exists for the number of randomly indexed reflections to increase, making it difficult to differentiate the mineral of interest. In contrast, a threshold set too high excludes all but the most intense reflections (i.e., quartz in soils). The threshold setting should be determined for each sample and then fixed for the analysis of each mineral component in that sample. As a determination of the software threshold setting, select an image from the data set with distinct reflections not belonging to quartz. Manually adjust the software threshold setting while indexing each known mineral component until a match is achieved between the number of detected reflections and the number of indexed reflections. Use this threshold value throughout the automated analysis for each mineral structure.

■

RESULTS AND DISCUSSION Constructed Mineral Mixtures. Constructed mixtures were analyzed with SP-XRD, and the relative mineral composition of each mixture (Table 1) was calculated using Reitveld refinement. Mixture 1 (three components) had a relative composition of 41% quartz, 23% magnetite, and 35% calcite. This mixture is designed to highlight the potential of Laue MDI for environmentally relevant and commonly reactive mineral samples under ideal conditions (Figure 1). Mineral and elemental spatial colocations (Figure 1) of Ca/calcite and Fe/ magnetite illustrate that these minerals have been correctly C

DOI: 10.1021/acsearthspacechem.8b00063 ACS Earth Space Chem. XXXX, XXX, XXX−XXX

Article

ACS Earth and Space Chemistry

Figure 2. Laue microdiffraction tricolor images of mixture 2 (300 × 300 μm) consisting of magnetite, quartz, calcite, and clinochlore. (Top left and bottom center) Laue diffraction images highlight the limitation of identifying clay minerals. (Bottom center) Clinochlore indexed reflections appear to correlate to the indexed reflections of the associated mineral phases. (Top right) Corresponding XRF image color plot of Ca and Fe providing elemental spatial distributions.

valuable chemical information on contaminant minerals is from a smelter-contaminated soil environment.28 Laue MDI provided an invaluable link between X-ray absorption spectroscopy (XAS), XFI, and bulk SP-XRD measurements to determine Zn speciation in this smelter/heavy metal-contaminated soil.28 Franklinite was found to be one of the Zn species that dominated XAS linear combination fits and was identified with SP-XRD as a major mineral phase. However, when XFI was preformed, Zn hotpots failed to correlate with Fe, which was expected in a system dominated by franklinite. Instead, the most concentrated Zn hotpots were determined with micro-X-ray absorption near edge structure (μXANES) to be sphalerite (ZnS), a minor component of the bulk LCF models. Performing Laue MDI allowed for the elucidation that Fe correlates to the presence of franklinite without significant overlapping concentrations of Zn. These spatial correlations of Fe indicated that either franklinite produced during the smelting process and deposited in the landscape is a non-stoichiometric form of franklinite, with respect to Zn, or the identified franklinite species may be a Zn-substituted magnetite species that neither bulk SP-XRD nor XAS is able to differentiate in environmental samples.28 This Zn-substituted magnetite phase may be more susceptible to oxidation and mineral dissolution than pure franklinite minerals, thus increasing the release of labile Zn into the environment. The second environmental example of Laue MDI for environmental applications highlights the ability to further characterize soil mineralogy (specifically, the carbonate mineralogy of calcareous soils). This example (Figure 5) is from a calcareous soil that is receiving phosphorus nutrient additions to promote in situ bioremediation of petroleum hydrocarbon contaminants.

use XFI to help differentiate between real and erroneously indexed reflections during automated analysis. Mixture 3 is a four-component mixture of sphalerite, hematite, arupite, and calcite. These minerals each have a distinct XFI signature to help identify spatial elemental distributions: Zn/ sphalerite, Fe/hematite, Ni/arupite, and Ca/calcite. The goal of this mixture was to investigate the performance of Laue MDI for contaminant minerals. Rietveld refinement (Table 1) indicates that the mixture consists of 37% calcite, 15% hematite, 23% sphalerite, and 25% arupite. Elemental and mineralogical spatial distribution of mixture 3 is illustrated in Figure 3. Sphalerite, calcite, and arupite minerals are relatively well-resolved as particles ∼20−50 μm in size. Although hematite is much smaller in particle size (∼5−10 μm), the hematite hotspots appear to be well-resolved and correlate to Fe in XFI, suggesting that this mineral is correctly indexed. Sphalerite (Zn) and calcite (Ca) have good correlations between their respective mineralogical and elemental images. Calcite generally appears to be present as fewer but larger particles, while sphalerite particles tend to be more numerous. Arupite distributions are generally consistent with the Ni fluorescence image, but there are a few examples of bleed through, where arupite particles overlap with sphalerite in locations with low Ni fluorescence. Laue MDI on Environmental Samples. In contrast with our synthetic mineral mixtures with high relative mineral abundances, contaminants in natural samples are typically present in lower relative abundance. It is also important to demonstrate the applicability of Laue MDI for determining the geochemical fate of contaminants in natural systems. One example where Laue MDI has successfully been used (Figure 4) to provide D

DOI: 10.1021/acsearthspacechem.8b00063 ACS Earth Space Chem. XXXX, XXX, XXX−XXX

Article

ACS Earth and Space Chemistry

Figure 3. (Top left and right) XRF images and (bottom left and right) Laue microdiffraction images of mixture 3 consisting of hematite, calcite, sphalerite, and arupite (300 × 300 μm).

Figure 4. Environmental example of XFI elemental and Laue MDI of a smelter-contaminated soil from the study by Hamilton et al.,28 illustrating the 2D spatial distribution (300 × 300 μm) of Zn, Fe, and Ca with the corresponding mineral maps of quartz, franklinite/magnetite, and dolomite.

component that has formed from secondary geochemical or biogeochemical processes. On the basis of the particle size difference, calcite is expected to play a smaller role in influencing P speciation than dolomite, which has both a much smaller particle size and a higher relative abundance. Additionally, Mg present in dolomite would play an important role in P speciation, because P sorption to dolomite would decrease crystalline calcium phosphate mineral formation as well as the rate of formation through the poisoning of the nucleation sites, favoring more soluble calcium phosphate species.29−32 Using Laue MDI makes it possible, in this case, to speculate about the chemical fate and potential effectiveness of P amendments applied to these soils, even without direct measurement of P species.

The contribution of Laue MDI to carbonate mineral characterization provided information on the particle size and elemental colocations that can be used to help infer the chemical fate of phosphorus amendments applied to these soils. For the soil imaged in Figure 5, SP-XRD and Rietveld refinements determined the soil to be composed of two carbonate mineral components: dolomite (6%) and calcite (2%). Using Laue MDI, it was observed that calcite particles are larger, upward of >50 μm, while dolomite particles were not clearly indexed. As with clinochlore in mixture 2, this is likely due to dolomite being smaller than the incident polychromatic X-ray beam (5 × 5 μm). The presence of calcite as large particles indicates that it is likely a component of the parent material of the soil, whereas claysized dolomite might indicate that it is a secondary mineral E

DOI: 10.1021/acsearthspacechem.8b00063 ACS Earth Space Chem. XXXX, XXX, XXX−XXX

Article

ACS Earth and Space Chemistry

Figure 5. Environmental example of XFI elemental and Laue MDI of a calcareous subsurface soil (300 × 300 μm), revealing the 2D spatial relationships between elemental XFI (Ca, Fe, and Ti) and mineralogical imaging (calcite, quartz, and dolomite).

Considerations for Environmental Sample Analysis. Some of the challenges associated with Laue MDI analysis of environmental samples cannot be corrected with software parameters alone during analysis. One of the most crucial aspects to successfully map environmental samples is a strong understanding of the geochemical conditions of the samples, and thus, Laue MDI is a complementary technique to both bulk monochromatic powder diffraction analysis and XFI. Laue MDI relies upon the crystallographic information determined through powder XRD. The mineral components and crystal structures determined during phase identification provide the unit cell parameters used to calculate the theoretical Laue reflections matched to the experimentally measured reflections. The crystal structure and unit cell parameters determined through XRD can be used to create the necessary crystal structure files for environmental samples. These crystal structure files can be important for environmental samples that may have elemental substitutions in the mineral lattice that results in a deviation from the original crystal structure parameters. Similarly, XFI is an essential complementary technique for challenging samples analyzed with automated analysis to help determine whether indexed reflections are due to the mineral or if they result from extraneously indexed reflections. While not the only method for checking false positives, comparing the spatial elemental and mineral distributions provides a check on whether the mineralogical maps contain false positives. It is likely that false positives will be present to some extent in all samples analyzed with automatic data processing; comparing the expected elemental contribution of that mineral (stoichiometric ratios) to its XFI helps minimize false positives during data interpretations. Additionally, it is helpful to compare all of the mineralogical images during analysis to determine whether mineral overlap is truly occurring. While the Laue MDI data presented in this research are from ground powered samples, the preparation of micrometer thick thin sections would limit the potential grain overlap, providing increased confidence in mineral/elemental spatial overlap. An important consideration before designing and incorporating synchrotron MDI into a research study is the resulting time requirements for data analysis. Dependent upon computational power, the automatic processing of XMAS can range for each separate Laue image from seconds to minutes; i.e., a 300 × 300 μm mineralogical map is the result of the analysis of ∼3700 Laue diffraction patterns. With the automatic analysis running sequentially/individually for each crystal structure, the analysis

time required for a sample can range from days to weeks. The extensive analysis time limits the effectiveness of MDI as a broad characterization technique, where large sample numbers may be required. Thus, it is best suited for focused experimental questions. Despite these limitations, Laue MDI has novel research applications for geochemical environmental systems, as demonstrated in our two examples. For researchers to properly integrate Laue MDI into their studies, it is important to have a clear understanding of how Laue MDI will provide additional information to achieve research objectives.

■

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsearthspacechem.8b00063. Synchrotron powder diffraction and Reitveld refinements of the constructed mineral mixtures (Figure S.1) and an additional Laue MDI diffraction figure of mixture 1 (Figure S.2) (PDF)

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Jordan G. Hamilton: 0000-0003-4782-9230 Renfei Feng: 0000-0001-8566-4161 Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS The authors appreciate the thoughtful and detailed comments from reviewers, which greatly improved the revised manuscript. Research described in this paper was performed at the CLS, which is supported by the Canadian Foundation for Innovation, the Natural Sciences and Engineering Research Council of Canada, the University of Saskatchewan, the Government of Saskatchewan, the Western Economic Diversification Canada, the National Research Council Canada, and the Canadian Institutes of Health Research.

■

ABBREVIATIONS CLS = Canadian Light Source MDI = microdiffraction imaging

F

DOI: 10.1021/acsearthspacechem.8b00063 ACS Earth Space Chem. XXXX, XXX, XXX−XXX

Article

ACS Earth and Space Chemistry

(17) Gräfe, M.; Klauber, C.; Gan, B.; Tappero, R. V. Synchrotron Xray Microdiffraction (μXRD) in Minerals and Environmental Research. Powder Diffr. 2014, 29, S64−S72. (18) Tamura, N.; MacDowell, A. A.; Spolenak, R.; Valek, B. C.; Bravman, J. C.; Brown, W. L.; Celestre, R. S.; Padmore, H. A.; Batterman, B. W.; Patel, J. R. Scanning X-ray Microdiffraction with Submicrometer White Beam for Strain/Stress and Orientation Mapping in Thin Films. J. Synchrotron Radiat. 2003, 10 (2), 137−143. (19) Ravelli, R. B. G.; Hezemans, A. M. F.; Krabbendam, H.; Kroon, J. Towards Automatic Indexing of the Laue Diffraction Pattern. J. Appl. Crystallogr. 1996, 29 (3), 270−278. (20) Tamura, N. XMAS: A Versatile Tool for Analyzing Synchrotron X-ray Microdiffraction Data. In Strain and Dislocation Gradients from Diffraction; Barabash, R., Ice, G., Eds.; Imperial College Press: London, U.K., 2014; Chapter 4, pp 125−155, DOI: 10.1142/ 9781908979636_0004. (21) Fodje, M.; Grochulski, P.; Janzen, K.; Labiuk, S.; Gorin, J.; Berg, R. 08B1−1: An Automated Beamline for Macromolecular Crystallography Experiments at the Canadian Light Source. J. Synchrotron Radiat. 2014, 21 (3), 633−637. (22) Larson, A. C.; Von Dreele, R. B. General Structure Analysis System; Los Alamos National Laboratory: Los Alamos, NM, 2004; Los Alamos National Laboratory Report LAUR 86-748. (23) Toby, B. H.; Von Dreele, R. B. GSAS-II: The Genesis of a Modern Open-Source All Purpose Crystallography Software Package. J. Appl. Crystallogr. 2013, 46 (2), 544−549. (24) McCusker, L. B.; Von Dreele, R. B.; Cox, D. E.; Louër, D.; Scardi, P. Rietveld Refinement Guidelines. J. Appl. Crystallogr. 1999, 32, 36− 50. (25) Toby, B. H. EXPGUI, a Graphical User Interface for GSAS. J. Appl. Crystallogr. 2001, 34 (2), 210−213. (26) Feng, R.; Gerson, A.; Ice, G.; Reininger, R.; Yates, B.; McIntyre, S. VESPERS: A Beamline for Combined XRF and XRD Measurements. Synchrotron RadiatroV7 Instrum. Ninth Int. Conf. 2006, 872−874. (27) Tamura, N.; Kunz, M.; Chen, K.; Celestre, R. S.; MacDowell, A. A.; Warwick, T. A Superbend X-ray Microdiffraction Beamline at the Advanced Light Source. Mater. Sci. Eng., A 2009, 524 (1−2), 28−32. (28) Hamilton, J. G.; Farrell, R. E.; Chen, N.; Reid, J.; Feng, R.; Peak, D. Effects of Dolomitic Limestone Application on Zinc Speciation in Boreal Forest Smelter-Contaminated Soils. J. Environ. Qual. 2016, 45 (6), 1894. (29) Cao, X.; Harris, W. Carbonate and Magnesium Interactive Effect on Calcium Phosphate Precipitation. Environ. Sci. Technol. 2008, 42 (2), 436−442. (30) Cao, X.; Harris, W. G.; Josan, M. S.; Nair, V. D. Inhibition of Calcium Phosphate Precipitation under Environmentally-Relevant Conditions. Sci. Total Environ. 2007, 383 (1−3), 205−215. (31) Hesterberg, D. Macroscale Chemical Properties and X-ray Absorption Spectroscopy of Soil Phosphorus. In Synchrotron-Based Techniques in Soils and Sediments; Singh, B., Gräfe, M., Eds.; Elsevier: Amsterdam, Netherlands, 2010; Developments in Soil Science, Vol. 34, Chapter 11, pp 313−356, DOI: 10.1016/S0166-2481(10)34011-6. (32) Xu, N.; Yin, H.; Chen, Z.; Liu, S.; Chen, M.; Zhang, J. Mechanisms of Phosphate Retention by Calcite: Effects of Magnesium and pH. J. Soils Sediments 2014, 14, 495−503.

SP-XRD = synchrotron powder X-ray diffraction VESPERS = very sensitive elemental and structural probe employing radiation from a synchrotron XAS = X-ray absorption spectroscopy XFI = X-ray fluorescence imaging XRD = X-ray diffraction XRF = X-ray fluorescence μXANES = micro-X-ray absorption near edge structure

■

REFERENCES

(1) Hofmann, F.; Song, X.; Jun, T.-S.; Abbey, B.; Peel, M.; Daniels, J.; Honkimäki, V.; Korsunsky, a.M. High Energy Transmission MicroBeam Laue Synchrotron X-ray Diffraction. Mater. Lett. 2010, 64 (11), 1302−1305. (2) Tamura, N.; Padmore, H. A.; Patel, J. R. High Spatial Resolution Stress Measurements Using Synchrotron Based Scanning X-ray Microdiffraction with White or Monochromatic Beam. Mater. Sci. Eng., A 2005, 399 (1−2), 92−98. (3) Ice, G. E.; Pang, J. W. L. Tutorial on X-ray MicroLaue Diffraction. Mater. Charact. 2009, 60 (11), 1191−1201. (4) Moffat, K.; Szebenyi, D.; Bilderback, D. X-ray Laue Diffraction from Protein Crystals. Science 1984, 223 (4643), 1423−1425. (5) Budiman, A. S. Probing Crystal Plasticity at the Nanoscales: Synchrotron X-ray Microdiffraction; Springer: Singapore, 2015; SpringerBriefs in Applied Sciences and Technology, DOI: 10.1007/978-981287-335-4. (6) Chen, K.; Kunz, M.; Tamura, N.; Wenk, H. R. Residual Stress Preserved in Quartz from the San Andreas Fault Observatory at Depth. Geology 2015, 43 (3), 219−222. (7) Chen, K.; Kunz, M.; Li, Y.; Zepeda-Alarcon, E.; Sintubin, M.; Wenk, H. R. Compressional Residual Stress in Bastogne Boudins Revealed by Synchrotron X-ray Microdiffraction. Geophys. Res. Lett. 2016, 43 (12), 6178−6185. (8) Rybacki, E.; Janssen, C.; Wirth, R.; Chen, K.; Wenk, H. R.; Stromeyer, D.; Dresen, G. Low-Temperature Deformation in Calcite Veins of SAFOD Core Samples (San Andreas Fault)Microstructural Analysis and Implications for Fault Rheology. Tectonophysics 2011, 509 (1−2), 107−119. (9) Weikusat, I.; Miyamoto, A.; Faria, S. H.; Kipfstuhl, S.; Azuma, N.; Hondoh, T. Subgrain Boundaries in Antarctic Ice Quantified by X-ray Laue Diffraction. J. Glaciol. 2011, 57 (201), 111−120. (10) Manceau, A.; Marcus, M. A.; Tamura, N. Quantitative Speciation of Heavy Metals in Soils and Sediments by Synchrotron X-ray Techniques. Rev. Mineral. Geochem. 2002, 49 (1), 341−428. (11) Courtin-Nomade, A.; Rakotoarisoa, O.; Bril, H.; Grybos, M.; Forestier, L.; Foucher, F.; Kunz, M. Weathering of Sb-Rich Mining and Smelting Residues: Insight in Solid Speciation and Soil Bacteria Toxicity. Chem. Erde 2012, 72 (Supplement 4), 29−39. (12) Soler, J. M.; Boi, M.; Mogollón, J. L.; Cama, J.; Ayora, C.; Nico, P. S.; Tamura, N.; Kunz, M. The Passivation of Calcite by Acid Mine Water. Column Experiments with Ferric Sulfate and Ferric Chloride Solutions at pH 2. Appl. Geochem. 2008, 23 (12), 3579−3588. (13) Brinza, L.; Schofield, P. F.; Hodson, M. E.; Weller, S.; Ignatyev, K.; Geraki, K.; Quinn, P. D.; Mosselmans, J. F. W. Combining MXANES and MXRD Mapping to Analyse the Heterogeneity in Calcium Carbonate Granules Excreted by the Earthworm Lumbricus Terrestris. J. Synchrotron Radiat. 2014, 21 (1), 235−241. (14) Gräfe, M.; Klauber, C.; Gan, B.; Tappero, R. V. Synchrotron Xray Microdiffraction (ΜXRD) in Minerals and Environmental Research. Powder Diffr. 2014, 29, S64−S72. (15) Tamura, N.; Celestre, R. S.; MacDowell, a. a.; Padmore, H. a.; Spolenak, R.; Valek, B. C.; Meier Chang, N.; Manceau, a.; Patel, J. R. Submicron X-ray Diffraction and Its Applications to Problems in Materials and Environmental Science. Rev. Sci. Instrum. 2002, 73 (3), 1369. (16) Tamura, N.; Kunz, M. A Concise Synchrotron X-ray Microdiffraction Field Guide for the Earth Scientists. Bol. Soc. Geol. Mex. 2015, 67 (3), 467−478. G

DOI: 10.1021/acsearthspacechem.8b00063 ACS Earth Space Chem. XXXX, XXX, XXX−XXX