Emily Lakdawalla

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  CheMin’s funnel is equipped with a mesh screen with wires spaced 1 millimeter apart, to

  protect the instrument from too-large particles. When CHIMRA delivers a sample, CheMin

  vibrates three piezoelectric actuators around the funnel to encourage all of the sample to

  pass through without sticking. The sample cells are mounted in pairs on a wheel. The

  wheel holds 27 sample cells and 5 reference standards. Fourteen of the sample cells have

  Kapton windows, and 13 have Mylar windows. The Mylar-windowed cells provide cleaner

  results, having little observable effect on the diffraction patterns produced by CheMin. But Mylar scratches easily and can be damaged by acidic samples. The Kapton-windowed

  cells will last longer, but Kapton produces a peak in the diffraction patterns that could

  interfere with the detection of some clay minerals.

  MAHLI routinely images the CheMin inlet and mesh screen to make sure that all deliv-

  ered material has passed through. When MAHLI observes any material clumping on the

  screen, CheMin can be commanded to run the piezoelectric actuators on its funnel to

  encourage any sticking material to drop. See Table 5.4 for a summary of MAHLI CheMin inlet imaging.

  CHIMRA delivers a maximum of 76 cubic millimeters of sample to a sample cell. Each

  sample cell has a miniature funnel-shaped reservoir with a volume of 400 cubic millime-

  ters, directing sample into a 10-cubic-millimeter active cell. The space within the active

  part of the cell is a very thin disk 8 millimeters in diameter and 175 micrometers deep.

  That depth is optimal for the 150-micrometer limit of sample powder size. The require-

  ment of <150 micrometer powder is defined as the maximum crystal size that provides

  good diffraction.

  9.4 CheMin: Chemistry and Mineralogy 321

  Figure 9.14. Components of the CheMin instrument. Top: installation of CheMin, June 15, 2010 (NASA/JPL-Caltech release PIA13231). The rover body and CheMin are upside down.

  Middle: dual-cell assembly, otherwise known as a “tuning fork,” showing both Kapton and Mylar window materials (from Blake et al. 2012 ). Bottom left: sample wheel assembly (Blak e et al. 2012 ). Bottom right: Sample inlet with inlet cover opened, showing 1 mm mesh (NASA/

  JPL-Caltech/MSSS release PIA16163).

  322 Curiosity’s Chemistry Instruments

  Each pair of sample cells has a piezoelectric actuator, referred to as a “piezo.” To get

  the grains inside a sample cell moving, CheMin uses the piezos to vibrate them at a range

  of frequencies, with the goal of getting the sample cell to vibrate at its resonant frequency, like a tuning fork. The vibrations of the two tines of the fork – the two sample cells in each pair – balance each other out so that little of the vibratory energy gets transmitted to the rest of the instrument. The intense vibration makes the mineral grains circulate like a boil-ing liquid, tumbling them randomly to present all orientations of all minerals to the X-ray beam. The dynamics of the vibration are extremely important. If the vibration happens at

  too low an intensity, grains could separate by density. It’s also possible for grains to

  agglomerate into immobile masses wedged between the two sides of the cell; once formed,

  such agglomerations tend to grow. To prevent both of these from occurring, CheMin peri-

  odically shakes the cells at very high intensity for a few seconds, breaking up the agglom-

  erations and mixing up the grains that may have separated by density. Vibration of the

  powdered sample in the cells had to be tested out at Mars gravity, tests that the CheMin

  team performed, 3 to 4 seconds at a time under microgravity created in a Piper Cherokee

  aircraft performing parabolic flights over the Pacific Ocean. Occasionally, the vibration

  turns out to be too intense, encouraging sample to bounce up and out of the cell, so CheMin is sometimes commanded to vibrate one of the cells next to the one that actually contains

  the sample in order to move the sample around more gently, a method that the CheMin

  team calls “kumbayatic” mode. (Seriously.)

  Samples are usually analyzed for 20 to 40 hours over many sols, although usable data can

  be obtained in about 2 to 3 hours. Longer analysis times improve detection of minor minerals and improve the quality of the data. Once analysis is complete, the wheel rotates 180° to

  dump the sample into an internal sump, vibrating the cell to encourage the sample to fall out.

  The reusable sample cells have no covers, so dumping happens automatically as a result of

  rotating the wheel. The reference standard sample cells are covered with high-efficiency

  particulate air filters to prevent their powdered contents falling out with wheel rotation.

  There are five standards. One is amphibole, an iron-rich silicate mineral sourced from

  Gore Mountain, New York, selected because it has a range of intense peaks in its X-ray

  diffraction pattern, as well as several closely-spaced peaks that allow the CheMin team to

  monitor how well they are resolving close peaks. Two other standards are mixtures of

  synthetic beryl and quartz in different proportions, selected because beryl has clearly

  defined widely-spaced peaks, allowing the team to monitor the crispness of individual

  peak profiles; the intermixed quartz helps them check how well they can determine rela-

  tive mineral abundances, especially for minor minerals. One standard is synthetic arcanite, a potassium sulfate that also has well-defined diffraction and is strongly X-ray fluorescent, with precisely known sulfur and potassium content. Finally, a doped ceramic standard was

  made from a mix of the clay mineral nontronite with numerous salts, providing a standard

  with a wide variety of fluorescence peaks.

  9.4.2.2 The CheMin X-Ray Source

  CheMin’s X-ray tube emits a cone of X-radiation using a cobalt anode. The X-rays have

  an energy of 6.925 keV. A pinhole plate allows only a 70-micrometer-wide beam of radia-

  tion to exit the source and pass through the center of the sample cell. The narrow beam

  9.4 CheMin: Chemistry and Mineralogy 323

  illuminates just 0.02% of the volume of material in the sample cell, but by vibrating the

  sample cell, different grains move in and out of the analysis area at different, random orientations. After passing through the cell, the direct beam falls onto a beam trap on the

  detector. The X-ray source has a power supply that is pressurized with a mixture of sulfur

  hexafluoride and nitrogen gas.

  9.4.2.3 The CheMin Detector, X-Ray Diffraction, and X-Ray Fluorescence

  The detector is a 600-by-1182-pixel CCD, of which 600-by-582 pixels is an active area.

  The pixels are unusually large for a CCD (40 micrometers square). An impinging X-ray

  photon deposits thousands of electrons in the CCD in a cloud that is tens of microns in

  diameter; the large size of the pixels means that almost all of this charge is usually cap-

  tured in one pixel, rather than being spread across several pixels, so that each time an

  X-ray photon hits the detector, the detector records not only the position but also the

  energy of the photon. A filter in front of the detector prevents it from being exposed to

  visible-wavelength photons. A cryocooler brings the temperature of the detector down to

  at least 48°C below the interior of the rover, thereby minimizing dark current on the CCD.

  X-ray diffraction happens when X-rays interact with crystalline lattices of atoms and

  constructively interfere, producing diffraction spikes at certain angles away from the

  direction of the X-ray beam. The an
gle of diffraction, the sum of the theta angle of inci-

  dence and the equal theta angle of reflection (hence 2-theta), depends on the wavelength

  of the X-ray and the spacing between atoms in the crystal lattice. The CheMin detector can

  record diffracted X-rays at 2-theta angles ranging from 5–50°, with an angular resolution

  of 0.30–0.35°.

  When CheMin is operating, the CCD typically records 30-second exposures, called

  “frames.” In that short period, any given pixel on the detector usually records at most one incident X-ray; therefore, a single CheMin frame records not only the position but also the intensity of individual events. CheMin can store up to 2730 such images in memory (or

  about 22 hours of data). But that would be too much data to transmit to Earth, so the rov-

  er’s main computer can stack 10 to 200 individual exposures into a single image, called a

  “minor frame.” Only pixels whose values correspond to the 6.925-keV energy of the X-ray

  source are selected for inclusion in the minor frame. On Earth, some or all of the minor

  frames from a single sample can be stacked into a “major frame.” Then the pixel values

  can be summed around the concentric circles of the 2-D diffractogram, producing a 1-D

  diffractogram (see figure 9.15 for examples). The CheMin team uses these 1-D patterns for analysis of mineral composition, but they also downlink the 2-D diffractograms to diagnose problems, such as blobs caused by mineral grains that became stuck during vibration.

  Individual peaks in the diffractogram can be diagnostic of specific minerals, but each

  mineral has a set of peak positions and intensities that reveal the crystal structure. The

  team uses all the peaks to determine mineral abundances. If there are non-crystalline

  (amorphous) materials present in the sample, they show up in the diffractogram as a very

  broad hump upon which the narrower diffraction spikes are superimposed. The team can

  use the shape and height of the hump to quantify the amount of amorphous materials pres-

  ent, but with larger analytical error than for crystalline minerals.

  324 Curiosity’s Chemistry Instruments

  Figure 9.15. Example CheMin data from the Windjana sample. Left: A CheMin 2-D diffractogram. Black semicircle at center of the left edge is the CheMin beam stop. Light circles are from diffraction in lattice planes in minerals. Right: CheMin 1-D diffractogram produced by summing all the values of the pixels with diffracted cobalt radiation at a given distance (angle) from the X-ray beam. Sharp peaks identify specific crystalline minerals. Broad hump (dashed red line) indicates the presence of amorphous (noncrystalline) material. After

  Treiman et al. ( 2016 ).

  The CheMin CCD can also function as an X-ray fluorescence detector. The pixel energy

  values in each frame serve as a measure of the energy of the X-rays that hit the detector.

  Many of these X-rays are diffracted ones with the same energy as the cobalt source, but

  other, lower-energy X-rays come from X-ray fluorescence. The energy of the fluoresced

  X-rays depends on the elements present. CheMin is not sensitive to elements lower in

  mass than potassium. CheMin reports this data in the form of a histogram (counts of pixel

  energy values). As with the diffractograms, to conserve downlink volume, the rover com-

  puter merges information from many CheMin CCD frames to produce histograms before

  transmitting the results to Earth. While mineral abundances from diffraction are quantita-

  tive (with mineral detection limits of 1 to 2% by weight) chemical composition from X-ray

  fluorescence is qualitative.

  Over time, the CCD will accumulate damage from cosmic rays as well as from the

  neutrons emitted by the MMRTG. The effects of this damage can be reduced by shorten-

  ing exposure times or by binning the data before processing it. CCD health is checked

  periodically (about every 18 months), and as of 2017 there has been no detectable degrada-

  tion in CCD performance. 40

  9.4.3 Using CheMin

  CheMin analysis is usually performed overnight, at a time when the rover operates at

  cooler temperatures. A typical overnight analysis takes 10 hours. The analysis is usually

  repeated over multiple nights to improve counting statistics, so most samples are analyzed

  40 David Vaniman, personal communication, email dated April 5, 2017

  9.4 CheMin: Chemistry and Mineralogy 325

  Figure 9.16. Schematic diagram of the CheMin sample wheel showing which cells have been used as of sol 1800. Information courtesy David Vaniman and Elizabeth Rampe.

  for a total of 20 to 40 hours. CheMin can continue to analyze a sample in this way until a

  new sample is ready for delivery, at which point the instrument usually dumps the old

  sample in order to receive the new one. Occasionally, CheMin accepts two samples in

  adjacent “tuning forks,” permitting it to continue analyses on both. CheMin kept both John

  Klein and Cumberland in adjacent cells for about 200 sols, and also stored the Mojave2/

  Telegraph Peak, Greenhorn/Big Sky, and Lubango/Okoruso sample pairs in this way. As

  the mission has proceeded, the team has begun to reuse Mylar-windowed cells, keeping

  unused cells in reserve against a future date when the rover will encounter different rock

  types (e.g. Vera Rubin Ridge and the clay- and sulfate-rich rocks beyond it).41 Sol 640 was the first test of re-using a sample cell. Figure 9.16 is a schematic of the CheMin sample wheel showing sample cell use.

  41 David Vaniman, personal communication, email dated March 8, 2017

  326 Curiosity’s Chemistry Instruments

  Table 9.4. Summary of CheMin sample analyses, organized approximately in order of stratigraphy, from stratigraphically highest to lowest (as in a stratigraphic column). Data are from the CheMin releases to NASA’s Planetary Data System.

  t

  y

  e

  l

  e

  e

  lfat

  lfid

  te

  p

  le so

  e

  etit

  m su

  e

  iu

  mp

  me

  a

  agioclase feldspar

  n su

  mati

  lc

  ay

  Grou

  Sa

  CheMin deliver

  CheMin analysis star

  CheMin cell

  Na

  olivin

  pyroxene

  pl

  alkali feldspar

  silic

  magn

  iro

  he

  ca

  akaganeite

  jarosite

  apatit

  cl

  amorphous

  Modern

  74

  77

  79

  1a Rocknest (scoop 4)

  13

  22

  33

  0

  1

  2

  0

  0

  2

  0

  0

  0

  0

  27

  basaltic

  93

  94

  95

  7a Rocknest (scoop 5)

  16

  20

  29

  1

  1

  1

  0

  1

  1

  0

  0

  0

  0

  29

  sand

  1224

  1226

  1236

  7a Gobabeb (scoop 1)
/>   18

  21

  24

  0

  0

  2

  0

  0

  1

  0

  0

  0

  0

  34

  1321

  1323

  1325

  8a

  Lubango**

  0

  4

  11

  0

  1

  3

  0

  1

  6

  0

  0

  0

  0

  75

  Stimson

  1332

  1334

  1335

  7b

  Okoruso

  0

  21

  27

  2

  1

  11

  0

  1

  1

  0

  0

  1

  0

  35

  formation 1137 1139 1140 8a Greenhorn*

  0

  6

  21

  0

  51

  9

  0

  3

  10

  0

  0

  0

  0

  0

  1119

  1121

  1122

  7b

  Big Sky

  0

  26

  37

  0

  3

  10

  0

  2

  1

  0

  0

  0

  0

  20

  1495

  1496

  1496

  4b

  Sebina

  1

  2

  12

  2

  0

  0

  0

  6

  7

  0

  1

  0

  51

  19

  1464

  1466

  1470

  5a

  Quela

  2

  2

  14

  2

  0

  0

  0

  6

  5

  0

  0

  0

  52

  16

  1422

  1425

  1425

  8b

  Marimba

  2

  1

  17

  3

  0

  0

  0

  6

  7

  0

  1

  0

  40

  23

  Murray

  1361

  1362

  1363

  12a Oudam

  0

  5

 

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