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Electrochemical Approaches for Chemical and Biological Analysis on Mars Samuel P

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Electrochemical Approaches for Chemical and Biological Analysis on Mars Samuel P Electrochemical Approaches for Chemical and Biological Analysis on Mars Samuel P. Kounaves*[a] Obtaining in situ chemical data from planetary bodies such as meltwater for a variety of inorganics and chemical parameters. By Mars or Europa can present significant challenges. The one analyzing the chemistry locked in the layers of dust, salt, and ice, analytical technique that has many of the requisite characteristics geologists will be able to determine the recent history of climate, to meet such a challenge is electroanalysis. Described here are water, and atmosphere on Mars and link it to the past. Finally, three electroanalytical devices designed for in situ geochemical and electroanalysis shows its abilities in the detection of possible biological analysis on Mars. The Mars Environmental Compatibility microorganism on Mars or elsewhere in the solar system. To Assessment (MECA) was built and flight qualified for the now identify an unknown microorganism, one that may not even use cancelled NASA Mars 2001 Lander. Part of MECA consisted of four Earth-type biochemistry, requires a detection scheme which makes ™cells∫ containing arrays of electrochemical based sensors for minimal assumptions and looks for the most general features. measuring the ionic species in soil samples. A next-generation Recent work has demonstrated that the use of an array of MECA, the Robotic Chemical Analysis Laboratory (RCAL), uses a electrochemical sensors which monitors the changes in a solution carousel-type system to allow for greater customization of via electrical conductivity, pH, and ion selective electrodes, can be analytical procedures. A second instrument, proposed as part of used to detect minute chemical perturbations caused by the the 2007 CryoScout mission, consists of a flow-through inorganic growth of bacteria and with the correct methodology provide chemical analyzer (MICA). CryoScout is a torpedo-like device unambiguous detection of such life forms. designed for subsurface investigation of the stratigraphic climate record embedded in Mars' north polar cap. As the CryoScout melts KEYWORDS: its way through the ice cap, MICA will collect and analyze the bacteria ¥ electroanalysis ¥ electrochemistry ¥ geochemistry ¥ sensors During the past 40 years, a variety of scientific instruments have GCMS would not have been able to detected the degradation been usedfor missions to investigatedplanetary bodieswithin products from several million bacterial cells per gram of Martian our solar system. Most of these missions have reliedon remote soil at the ppb level.[6] The life detection and GCMS results form sensing, typically based on optical or radiation detection the basis for the prevalent opinion within the scientific techniques. Mars has been the focus of a large number of such community that it is probably unlikely that any microbial life missions.[1] The first successful flyby of Mars in 1964 returned21 forms were detected on the surface of Mars, and that, in photos with subsequent flyby missions adding more. It was not addition, the chemical and physical conditions are such that it is until 1976, with the success of the two Viking Landers, and in probably unlikely that any organic-basedlife form couldexist on 1997, with the Pathfinder Lander and Rover, that we obtained a the unprotectedsurface. detailed close up view of the surface and its chemical and Unlike Viking, Pathfinder was the first mission to focus on physical properties.[2, 3] Martian geochemistry andmineralogy. Its instruments and The instruments on the Viking I and II Landers included three mobile rover were designed not to directly detect life but to biology experiments, a gas chromatograph/mass spectrometer primarily provide close up optical observation and determine (GCMS), andan X-ray fluorescence spectrometer (XRFS). The the elemental chemical composition of the Martian rocks and results of the biology experiments have been interpretedby a surface material over hundreds of square meters using the alpha majority of the science community as ruling out microbial life on proton X-ray spectrometer (APXS). The Viking XRFS and Path- the surface of Mars.[4] However, there are still some who are finder APXS data have provided a reasonably clear picture of the convincedthe results leave no other conclusion but the elemental composition of the surface material. Even though the presence of life.[5] The big surprise though was that the GCMS detected no organics in the soil samples down to the parts-per- billion (ppb) levels. Many hypotheses have been advanced to [a] Prof. S. P. Kounaves account for the absence of organics andthe possible chemicals Department of Chemistry andreactions that couldaccount for the ambiguous biology Tufts University experiments. These have included reactions involving oxidants Medford, MA 02155 (USA) Fax: (1) 617-627-3443 such as hydrogen or superperoxides, smectite clays, and super- http://planetary.chem.tufts.edu oxide radical ions. A recent study has shown that the Viking E-mail:samuel.kounaves(at)tufts.edu 162 ¹ 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1439-4235/03/04/02 $ 20.00+.50/0 CHEMPHYSCHEM 2003, 4, 162 ± 168 Chemical and Biological Analysis on Mars ELECTROCHEMISTRY SPECIAL analyses were from different areas they present a picture of a ppb levels. An array of microfabricatediridiumultramicroelec- rather homogeneous surface composition. The combinedresults trodes was included in the recent MECA instrument for assessing of the Viking andpathfindershow the surface material to be the concentration of such potential toxic metals. The sensor roughly composedof 45% SiO 2, 18% FeO2 ,8%MgO,6%SO3 , measures only millimeters in size andcan easily withstandharsh [7, 8] 7% Al2O3, 1.8% NaO, and0.6% Cl. environments. There are no other devices available which ™in total∫ can fit in a 50 mL volume, consume milliamps of electricity, The Advantages of Electroanalytical Devices andsupply the concentration of metals such as mercury and cadmium at sub-ppb levels. Chemical andbiological analyses are routinely performedon Earth, however, to obtain validin situ analytical datafrom remote harsh environments on planetary bodies, such as Mars or The Mars Environmental Compatibility Europa, presents a truly unique andformidablechallenge. Not Assessment (MECA) only do constraints on such instrumentation include power, size, The MECA instrument was originally designed, built, and flight mass, cost, androbustness, but they it must also be able to qualifiedfor the 2001 Mars Landermission. The mission was survive high g-forces, an eight-month journey through a subsequently cancelled due to the loss of the Mars Polar Lander radiation permeated environment, and possible temperature in 1999. The MECA, anda newer version, the Robotic Chemical variations ranging from 60 to À100 8C. Sensors basedon Analysis Laboratory (RCAL), have been proposedfor the 2007 electrochemical transduction schemes have many of the pre- launch opportunity. MECA was designed to evaluate potential requisite properties andcan withstandthe environmental risks geochemical andenvironmental hazardsto which future Mars that will enable them to return significant scientific data under explorers might be exposedandto return datathat wouldhelp such severe constraints. in understanding the geology, geochemistry, paleoclimate, and Because of the history andcomposition of Mars, electro- exobiology of Mars. The MECA instrument package containeda chemical sensors may also be especially well suitedin providing wet chemistry laboratory, an optical andatomic force micro- useful geochemical analyses andbroaderplanetary scientific scope, an electrometer to characterize the electrostatics of the results. The surface of Mars, as described above, appears to soil andits environment, andan array of material patches to contain a large fraction of sulfur andchlorine. These two study the abrasive and adhesive properties of soil grains. elements are most likely in the form of sulfate andchloridesalts. Because of payloadlimitations, the entire MECA package was Basedon what is known about the evolution of the solar system limitedto a mass of 10 kg, a peak power of 15 W, anda volume of andthe evidence returnedby the Mars missions, planetary 35 Â 25 Â 15 cm3. The development of MECA for analyzing the geologists have hypothesizedthat some time in its past Mars surface material in a remote hostile environment poseda unique was coveredby massive oceans andlakes that were eventually set of challenges, especially for remote chemical analysis and desiccated by some planetwide catastrophe or environmental more specifically for electrochemical analysis. change. Geochemical signatures of this wet periodin Mars' history shouldbe preservedin the form of layeredsalt-rich evaporite deposits that would have resulted from such large The Wet Chemistry Laboratory (WCL) Cell bodies of water and also from the geochemical weathering and transport of soluble minerals. Salts wouldalso have been the Containedwithin MECA are four WCLs, each consisting of a byproducts of volcanic gases acting on the Martian soil or thermally insulated, single-use, independent analysis cell, cap- perhaps in areas where microbial activity existed. pedwith a 30 mL pressurizedwater reservoir andactuator The simplest technique for qualitative andquantitative assembly. The actuator assembly consists of a water tank with a analysis of ionic species is the use of potentiometric ion-selective puncture valve, a sample loading drawer, a stirrer, and a solid electrodes (ISEs). These
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