Voyager infrared spectrometer - American Chemical Society

Figure 1. iris spectrometer. Interferometer is to right of primary mirror. Each of the two Voyager spacecraft currently exploring the outer reaches of...
0 downloads 0 Views 14MB Size
Voyager Infrared Spectrometer by Stuart A. Borman

Flgure 1. IRIS spectrometer. Interferometer is to right of primary mirror Each of the two Voyager spacecraft currently exploring the outer reaches of our solar system carries sophisticated infrared and ultraviolet spectrometers. In this month’s INSTRUMENTATION, the Voyager Fourier transform infrared (FTIR) interferometer spectrometer will be described. The spectrometer was developed in a joint effort spearheaded by the National Aeronautics and Space Administration (NASA) Goddard Space Flight Center, with the participation of research and development groups from the University of Michigan and Texas Instruments, Inc. The instrument, named IMS for infrared interferometer spectrometer, flew on the Nimbus 3 and Nimbus 4 meteorological satellites in earth orbit and on the Mariner 9 spacecraft that orbited Mars, in addition to the Voyager spacecraft. One individual who has participated in the development of IRIS from the 1544A

ANALYTICAL CHEMISTRY. VOL. 53, NO. 13, NOVEMBER 1981

very beginning is Rudolf A. Hanel of the Goddard Space Flight Center’s Laboratory for Extraterrestrial Physics. Hanel is presently in charge of the infrared spectrometer investigation on the two Voyager spacecraft.

Interferometry An FTIR spectrometer like IRIS acquires a signal called an interferogram in the time domain, instead of direct acquisition in the frequency domain, as with grating instruments, for example. An interferogram is a plot of the autocorrelation function of electromagnetic radiation as a function of time. If monochromatic light were involved, for example, the time domain signal would be a sine wave. A much more complicated interferogram results when polychromatic light is analyzed. Unfortunatelv. there is no transduc. er with a s u f f i c i h y rapid response time to follow the oscillations of elec0003-2700181~A351-1544$010010 1981 A m I a n Chemacal Soclew

62

Instrumentation

I Flgute 2. IRIS spectrometer. Interferometer at center. radiometer at left

tromagnetic radiation in the infrared region. What is needed is a black box able to “slow down” the electromagnetic radiation so it can be detected, without distorting the information carried in the original signal. The Michelson interferometer operates on electromagnetic radiation to “slow it down” in just this way-a process known as modulation. As mentioned above, if a single frequency is incident on an interferometer, the time domain signal generated, the interferogram, will consist of one pure sine wave whose frequency is proportional to but much lower than the frequency of the incident radiation. But most radiation sources in the real world (or real universe) contain a mixture of many frequencies. These different frequencies added together form a complex interferogram that often looks something like a decaying transient disturbance. One might think that such a pattern could not

possibly contain any useful information. But this jumble of frequencies can be deconvoluted by the mathematical process of Fourier transformation, converting the information contained in the interferogram from the time domain to the frequency domain. A power vs. time signal is thus converted to a sDectrum of radiance vs. frequency. An excellent descriDtion of Fourier transform spectromeiry and the Michelson interferometer can be found in Reference 1. Other books containing more detailed information include References 2,s. and 4. IRIS

The IHISinstrument on the Voyager spacecraft does not operate like a conventional infrared laboratory spectrometer, with a source, a sample, and a detector, in that order. With IRIS, the sample is also the source, because the instrument measures thermal (in-

frared) emission. Since infrared emission from molecules at low temperature is very weak, it is evident why a Michelson interferometer, with its high signal-to-noise ratio, was chosen for the Voyager mission. This higher S/N ratio, the “Fellgett advantage” Michelson interferometers possess over prism or grating instruments, arises from the fact that the deteetor in the Michelson interferometer sees all spectral intervals simultaneously instead of sequentially. The instrument and its optical layout are shown in Figures 1,2, and 3. The most prominent feature in Figure 1is the spectrometer’s telescope. Radiation collected by the 50-cm-diameter primary and the secondary mirror is directed through a field stop (Figure 3) to a spherical dichroic mirror (5). The interferometer itself can he seen behind the primary mirror in Figure 1. It is also clearly visible in Figure

ANALYTICAL CHEMISTRY, VOL. 53, NO. 13, NOVEMBER 1981

1545A

“The

Project SEED summer program gave me a chance to learn about research

Flgure 3. Optical layout of the Voyager IRIS. Reprinted from Reference 5 with permission of the Optical Society of America

This summer, thanks to Project S E E D , over 130 economically disadvantaged high school students like Angela Odom had a chance to work and learn in a number of academic research labs throughout t h e U.S.

Your contributions, which are used 100% for student stipends, are needed for SEED t o continue helping students prepare for making vitally important decisions about their future education and work. 11111111111

Project SEED ACS, 1155 16th SI., N.W Washington, D.C. 20036

Yes, I’d like to help these students learn what is required for success as college students. Name: Address:

Contribution: 0 $50 0 $20 0 $10 Other 1

1

1540A

1

1

1

1

1

1

1

1

1

2. The device behind the dichroic mirror (on the left in Figure 2) is a radiometer for measurements in the visible and near-infrared regions. Radiation reflected by the spherical dichroic mirror is directed to a beam splitter (Figure 3), and thence to the fixed and stationary mirrors of the interferometer. The interferometer modulates the incident radiation by splitting it into two beams. One beam is directed to a fixed mirror and the other to a movable mirror called the Michelson mirror. The two beams are then recombined at the beam splitter, and an interference pattern generated by the interaction of the two beams is focused on a thermopile detector. For clarity, in Figure 3 both the main and reference interferometers are rotated 90’ about an axis between the main interferometer beam splitter and the dichroic mirror; also, the reference interferometer is not to scale. For the interferometer to operate properly, the instrument’s temperature must be held constant, in this case at 200 0.5 K. Therefore, the optical components of the Voyager IRIS (except the active surface of the primary) are wrapped in multilayer thermal blankets for the flight. A thermal radiator mounted on the interferometer cools the instrument by radiating to deep space. Three sets of heaters provide fine thermal control for the instrument. In addition to tberwal protection, considerable effort was invested in radiation-hardening the instrument, to ensure proper operation in the high-energy particle environment of Jupiter’s magnetosphere. The reference interferometer (Figure 3) contains a neon source, from which the 5852 8, line is isolated by a narrow-band interference filter. The moving mirror of the reference inter-

*

ANALYTICAL CHEMISTRY, VOC. 53. NO. 13, NOVEMBER 1981

ferometer is operated by the same linear motor that operates the moving mirror of the main interferometer. The interferogram generated by the reference interferometer is a pure sine wave. The reference interferometer serves two functions: It provides feedback control of the Michelson mirror motion, and, by sensing the zero crosings of the neon sine wave, it initiates the sample and bold commands needed for the acquisition of discrete data points in the interferogram. Each interferogram is acquired in 45.6 s with a rate of 80 words s-l. Each interferogram thus contains 3648 digital words. Hundreds of individual spectra are averaged to produce an emission spectrum of high S/N ratio for scenes under study. The output of the detector is quantized and temporarily stored in the spacecraft for transmission to earth, where the data are processed in a digital computer. The interferogram is Fourier-transformed to yield an amplitude and a phase spectrum. The amplitude in each channel is proportional to the net spectral radiance between the instrument and the scene within the field of view. This raw amplitude vs. frequency spectrum must then be corrected for phase and calibrated against an absolute radiance source. The phase of the signal in each spectral interval of the raw amplitude spectrum depends on whether the scene is warmer or Folder than the instrument. The phase of a colder source is 180’ from the phase of a warmer source. After the amplitude spectrum has been phase-corrected, it is calibrated. Two points are used in the calibration: deep space, assumed to be a perfect beat sink, is one point, and the accurately known temperature of the instrument (200 K) is the other. With (continued on page 1550 A)

-

will do anvtninn

/’

except Take th

I

The PHM83 Autocal DH Meter with the uniaue simplicity of a u t o cacbration a n d advanced o p g a t o r information. Micro processor controlled for precise measurement of pH, mV a n d temperature. O n e key calibration with automatic recognition of specified buffer. 20 C h a r a c t e r alpha-numeric display, Permanent memory retains calibration d a t a even when power is switched off. Built-in test a n d service programs. Optional output module for connection t o orinter. recorder a n d titration systems.

4 digit ~ C j dai p l a y 800 hour -. .. .-_batteru . - - - - - - = lif See the new PHMKi a n d all the fine quality Radiometer pH meters in o u r new “pH Family” brochure. Get your copy today. Call (800)321-9484. In Ohio, Alaska .and Hawaii call (216) 871-8900. The London Company, subsidialy of Radiometer Copenhagen, 811 S h a r o n Drive, Cleveland, Ohio 44145.

RADIOMETER COPENHAGEN

When you cant afford tObeWrong. CIHCLL 183 ON READER StRVlCt CARD

I

I

N 0 one c

Nicolet delivers unmatched infrared performance and versatility while giving you the widest selectio of FT-IR instruments. Whether you require maximum infrared capabilit and data handling or simply an instrument for precise routine analysis, Nicolet has the FT-IR to meet your needs.

Nicolet FF-IR improves your analytical productivity.

~

Fourier transform infrared is fast becoming the instrumentation of preference over conventional dispe sive infrared instrumentation. Superior sensitivity and resolution, rapid sample measurement, absolut wavelength accuracy, versatile spectral processing, and total automation of complex analyses are some basic reasons why the world is turning tu FT-IR and to Nicolet, the leading supplier of Fourier transform spectroscopy instrumentation.

includes the EPA vapor-phase libraries, AIdricNNicolet libraries of solids md liquids, Sadtler gas and solid libraries, and numerous libraries of specialty compounds. Nicolet has also 3eveloped a full package of sophisticated programs for spectral library searching and spectral interpretation.

Automatic GC-IR Analysis, Search, and Identification. Nicolet’s GC-IR software provides for automated analysis of a GC-IR run, including data collection, GramSchmidt chromatogram reconstruction, peak location and computation of the spectrum for edch chromatographic peak, and spectral search and identification for each component in the GC-IR run. Nicolet FT-IR systems show excellent performance with both capillary and packed-column chromatographs.

-

1

Library Search and Spectral Identification Features. Fully-developed library search capabilities provide a quick and COI venient means for identifying samples of interest. Nicolet has assembled a comprehensive FT-IR data base that Raster-scan display of a series of spectra acquired during a GC-IR run. This display allows real-time observation of absorbance peaks during elution.

IR run, for performing spectral subtraction and other spectral manipulations, and for comparing an unknown spectrum with “best match’ spectra from a library search operation. This display is standard with Nicolet 7199, 6000, 8000, and 3600 systems; a colorgraphics data terminal is available as an option with the Mx-S and MX-1 systems.

Nicolet

Top-of-the-Line FT-IR Series Unrivaled in performance, this powerful FT-IR series finds applications in sophisticated research and development applications as well as in production and quality control laboratories.

Nicolet 7199, the established performance standard in high-grade research infrared spectroscopy. The 7199 is a dual-beam, purgeable Jystem with facilities for dual sources switchable under computer control. Highly sensitive IR detectors and beamsplitters combine with variable control of the moving mirror to provide optimum sensitivity for any application. The 7199 is capable of constant 0.06 cm.’ resolution, with a spectral range of 25,000 to 10 cm‘’. The advanced Nicolet IR-80 data sys-

‘ 1 New color raster-scan display.

Rasterxan display of library search and retrieval. Top spectrun (yellow) is the unknown, wbile tk red spectra are tbe closest matcbes f*und in tbe Aldricb libray.

This display provides a bright, flicker-free image of superb quality. The display significantly aids the spectroscopist in identifying, compa ing, and manipulating spectral data. The color raster scan display monitc allows simultaneous display of man) spectra, valuable for displaying successive spectra acquired during a GI

Nicolet 7199 FTIR system

USA I Nicalet Instrument Corporation 15225.1 Verona Road I Madison. Wisconsin USA 5371 1 I TWX: 910-286-2736 PaclIlc-Ash I Nicolet instrument Corporation 1522 5-1 Verona Road I Madison, Wisconsin USA 5371 1 I TWX: 910-2862736 U.K. I Nicolet Instrument Ltd. I Budbrooke Road I Warwick, Warwickshire I England I TWX: 851-31 I 1 3 5 West Germany I Nicolet Instrument GmbH I Senefeiderstrasse 162 I D-6050 Offenbach am Main i West Germany I T Prance I Nicole1 Instrumenrs SARL I Rue Elsa Triolet i 2.1. Les Gatines 178370-PLA ISlR I France I TWX: 842-698777 NetherlandslNicolet Instrument B.V.IZuiderinsldgb 13871 MRHoevelakenINetherlandsITWX: 8 4 4 ~ 7 9 3 7 0

tem provides capabilities for simdta neow data acquisition, processing, and plotting for greater sample throughput. The n99C can be used with the full range of accessories available from Nicolet. This includes GC-IR, LC-IR, photoacoustic, and reflectance accessories.

i capable of 0.5 cm" resolution iroughout the mid-IR.

'fie large-scale Mx-80 data system ' provides for storage and recall of

I

a single-beam version, the 6oooc. ?hii system uses the same Interferometer as its "big brother" n m , however, the 6oooc has one sample path, resulting in a slightly smaller 6oooc can be W ~ P with the full range of FT-IR applicarions accessories. The 6ooOc can alsc accommodate dual computer-selecta. ble sou~cesand detectors,and can b~ oprimized for any spectral region from 25,000 to 10 an.'.

&onomicd 1 Nicolet MX Series I Remarkably low capital expendi-

~ f brings e you a Nicolet MX-1 or LX-S FT-IR system. These are ideal for

II

indusuial, commercial, or academic labs that might now be using disperFive IR 63th increasingly large sample Joorkloads, however, labs need he fast throughput of FCIR at an

N h l e t 6OOOC Vacuum

Fr-XR. is designed to provlde vuly e x c e p and sensitivity performance throughout the spectral range of 25,000 to 8 cm.'. Used primarily for highresolution h - I R measurements, the 8oooc employs 4" optics and a highly sensitive heliumcooled bolometer.

New MX-S spechwmetw

I

1 ,

;

' 1, ' !

Nicolet

r r-IRSystem

ux.1 spectrometer

N i c o k t Ildx-1.

A versatile performer, our MX-

I

The economical ean/-to-use MX-I provides the analytical laboratory with a more user-interactive FT-IR inqru. nent at a price still within most budg ts. The MX-1 is capable of measuring pectra with a constant resolution of cm" throughout the spectral range $4800 to 400 UTI.' (extendable to '26 UTI.').

The Mx.S is affor&ble, compact, sensitive, and easy to operate. MX-S can be conveniently operated from a standard laboratory benchtop, and requires no utilities other than a standard electrical outlet This instrument employs the same rugged and compact interferometer design used in several space missions. Thus, the Mx-S is extremely reliable in performance. It is also easily operated from one convenient touch panel. The MX-S provides these state-of-thean FT-IR capabilities at a price every laboratory can afford. &I,

4

t i 4 resolution

handing capabilities, Nicolet has developed a system tha~is economical and convenient to operate while providing versatuity for demanding re@ applications as well as rcu. tine laborarory studies. The 36OOC

NCWN k o l e t MX-S. -

~

*

3600C meets a remarkable variety 01 anatytical needs. By combining a compact optical bench with powerfd data

is accomplished via a convenient touch-panel. The MX-1 also has a comprehensive quantitative package. The h4x-I can be equipped with floppy diskette storage system and color-graphic dara terminal, providing extended capabilities such as library searching routines.

I

Nicolct 6-C. Nicolet has incorporated the essential features of the 7l9PC system into

-.

several spectra. pull operation of the system, including data manipulation,

Am unparalleled srpport network. Nicolet provides complete applications mistance, technical service, and scientific suppon worldwide. Contact us for details.

NlCOLET ANALYTICAL INSTRUMENTS Worldwide sales, rm,ico. appltcalions sup@%%

slsdcn,Roruq, PhImad, Iceland INICOlet-IIWTWMDl A.B. I P.O. Box 432 IS-184-00AkcrsbcrgaISwedcnI T W X : 854.1 1528 D a m u A I N i c o h InstrwncntAPS/MolkS(racdc 5 IDK-3400 HillerodIDenmarkITWX: 855-42169 J q m ~ I N l c o l nImurumenIJapnCOT. / M h o BulldingI8-76Chomc INtshi-NWaihna, Yodogawa-Ku / O s a k a , J a pITWX. 781-5233285 cpmdr /NIcoln lnstnrmcni Canach / I . I200 Acrowuood Dr. I Missbaugr. Ontario L4W 2S7 I C a n a h I TELEX.06%0126 IYLx(e0 INIcdcr Lnscrwnn1osS.A. dc C.V. I Luimna49 I M ~ x i c o18 D.F. Zip Code03812 /Tclcphonc(W5l 5434Ml2

these two calibration points, relative amplitudes can be converted to absolute radiance units. Ice Clouds on Mars The infrared emission spectrum of the atmosphere of a planet is a difficult thing to interpret, since spectral radiance reaching the interferometer is a complicated composite of emission and absorption. For instance, emitted radiation by CO2 in one atmospheric layer may be reabsorbed by C02 molecules higher up in the atmosphere. As Hanel put it, “The primary goal of remote sensing in the infrared is to extract the chemical composition and physical parameters . from the measurement of spectral radiances. In the early days of evolution of this technique, the problem was often compared to the task of unscrambling an omelet and reconstructing the eggs” ( 6 ) . One spectrum Hanel and his associates were able to unscramble is shown in Figures 4a and 4b (7). Figure 4a shows Mariner 9 IRIS measurements of the lower Arcadia region of Mars under clear weather conditions and of the Tharsis Ridge region under conditions of partial cloudiness. Although it had been suspected that clouds of the type that appeared in the Tharsis Ridge region that day were composed of water ice, no direct spectral evidence had been found. c The spectrum measured over lower I Arcadia showed an approximately constant brightness temperature, except for the C02 absorption band centered at 667 cm-1 and the rotational water vapor absorption lines below 400 cm-’. In contrast, the Tharsis Ridge spectrum exhibited a strikingly broad absorption feature extending from 550 to 950 cm-l, with a second RXC the unique, new Whatman Rapid Analysis Chromatogbroad absorption feature between 225 raphy column saves you time . and money. How? and 350 cm-’. Superimposed on the by being fast. Optimized efficiency and selectivity, but a t speeds up latter was a sharp spike near 227 to four times faster than standard LC analytical columns. This cm-l. The theoretical water ice cloud means greater throughput a t a fraction of the cost per analysis. spectrum (Figure 4b) had similar features. These spectroscopic data by being durable. Low back pressure, even at flow rates of 5.0 strongly indicated that the Tharsis ml/min, minimizes internal friction. Results: a longer-lasting column Ridge clouds were composed of water with precise quantitation, analysis after analysis. ice. by being convenient. No need for expensive, space-consuming auxVoyager iliary equipment. RAC is immediately compat@le with all standard Voyager 1 IRIS spectra of the planet LC instrumentation. And translation is fast. RAC chemistry is idenJupiter showed clear evidence of a tical to that of the columns you’re probably now using. number of compounds in the Jovian Faster speeds . , , lower costs. Compare R k with the column atmosphere, including hydrogen, you’re using. Available in highly stable Partisil 5, Partisil 5 CCS/C8 methane, acetylene, ethane, ammonia, and Partisil 5 ODs-3. phosphine, water, CH3D, and GeH4. Pearl et al. (8) painstakingly identiCall Whatman 800-631-7290 or send today for complete technical fied the presence of SO2 on Jupiter’s information. volcanic moon, Io, by comparing tiny blips on spectra from Io’s atmosphere -to peaks in a synthesized spectrum of

Faster LC at

...

..

..

...

...

--

---

iir m a t m a n

Whatman Chemical Separation’Inc. 9

s02.

Bridewell Place, Clifton, New Jersey 07014

CIRCLE 231 ON READER SERVICE CARD

1550A

ANALYTICAL CHEMISTRY, VOL. 53, NO. 13, NOVEMBER 1981

During the passage of Voyager I through the Saturn system, IRIS ac-

CDCIMILTON

ROY

Another Way 01 Looking at HPI LDC pioneered the modular ap chromatography with the der of HPLC pump

LDC/ LABORATORY DATA CONTROL, DIV. OF MILTON ROY CO.

ClRCLE 129 ON READER SERVHX C A R D .

'

'

.

.

I-

.---

Who made S ctraMetrics tgleader in hi h-resolution p asma emission spectroscopy? The leaders in industry.

Is

We've installed more high-resolution plasma emission spectrometers, worldwide, than any other company. Our family of Spectraspan analytical instruments includes models for elemental analysis hy both DCP and ICP emission techniques, something offered only by SpectraMetrics. Available in several configurations, such as the Dual-Source SpectraSpan pictured above, these versatile instruments meet a wide range of analytical needs and budgets. Because they can accommodate varied and difficult samples, Spectraspan systems are cost-effective tools in such diverse fields as geology, environmental science, metallurgy and petrochemistry, and perhaps in your particular field as well. Discover for yourself what the leaders in industry know. SpectraMetrics, Inc., a subsidiary of Beckman Instruments, Inc., 204 Andover Street, Andover, Massachusetts 01810,

(617) 475-7015.

THE LEADER IN HIGH-RESOLUTION PLASMA EMISSION TECHNOLOGY.

CIRCLE 199 ON READER SERVICE CARD

200400

BM)

0

800

Wavenumber (crn-l) Figure 4. (a) Marlner 9 IRIS spectra from Mars. Arcadia spectrum is offset for clarity. (b) Theoretical water Ice clod spectrum. Brightness temperature (y axis) is a function of spectral radiance. Reprinted from Reference 7, copyright 1973 by the American Association for the Advancement of Science

I

&HI \

130

HCN,

quired data on the planet, its rings, Titan, and other satellites. Infrared spectra of Saturn indicated the presence of hydrogen, methane, ammonia, phosphine, acetylene, ethane, and possibly methyl acetylene (C3H4)and propane (CsH8). On Titan, positive identifications were made for methane, acetylene, ethylene, ethane, and HCN, but again only tentative identifications could at first be made for methyl acetylene and propane. Positive identification of these last two components had to wait for a more detailed analysis of Titan spectra, as shown in Figure 5 (9). At the top of Figure 5 are spectra acquired from the center of Titan’s disk and from its north pole. At the bottom of the fiiure are spectra of propane and methyl acetylene taken in the laboratory. The average disk spectrum shows weak but definite spectral features of the propane fundamentals at 748,922,1054,and 1158 cm-I. The disk spectrum and, to a greater extent, the polar spectrum show the fundamentals of methyl acetylene at 328 cm-I and at 633.2 cm-1. These data provided convincing evidence for the existence of these gases in the atmosphere of Titan. Voyager 2 made its closest approach to Saturn on Aug. 25,1981. Due to a rare planetary alignment occurring only once every 175 years, Voyager 2 should he able to continue on to a rendezvous with Uranus in January 1986,and perhaps even Neptune in August 1989.Eventually the Voyager spacecraft and their remarkable spectrometers will leave the solar system. But instruments like IRIS will no douht fly again when new opportunities for the spectrometric exploration of space present themselves. ThanLe to Rudolf H a e l for reviewing this material and to Ron Joho of Hewlett-Packard far suggesting the topic.

References (1) Skoog, Dou las A.; West, Donald Mi, “Principles of Instrumental ~na~ysla, 2nd ed.; Saunders CollegetHolt, Rinehart and Winston: Philadelphia, 1980;

-Ea

241-54. (2) Bell, Robert John: “Introductory Fou-

0.4

ti1:::

D9

rier TransformSpectroscopy”; Academia Press: New York, 1972. (3) Griffiths, Peter R.“Chemical Infrared Fourier Transform S ectroscopy”;John Wiley & Sons: New Ark, 1975. (4) Griffiths, Peter R.,Ed. “Transform Techniques in Chemistry”;Plenum Press: New York, 1978. (5) Hanel, R. A,, et al. Appl. Opt. 1980,19,

8.0 0.0

I

200

400

600

800

1003

1200

1400

16W

1391-1400. (6) Hanel, R. A., “Cpmical Eyolution 09

the Giant Planets ,Academic Press: New York, 1976; Chapter 13. (7) Curran, Robert J.,et al. Science 1973,

Wavmurnber (em-’)

182,381-3.

Flgure 5. Comparison of ObSeNed Titan spectrum with laboratoly spectra of propane and methyl abtylene. Reprinted frcin Reference9 by permission of Macmllian Journals Ltd.

(8)Pearl, J., et al. Nature 1979,280,7558. (9) Maguire, W. C., et al. Nature 1981. 292,6834.

ANALYTICAL CHEMISTRY. VOL. 53. NO. 13, NOVEMBER 1981

1553A